.

A ~OUNTAIN

PHOTOBOOK

BASIC

PHOTOGRAPHIC

CHEMISTRY

BASIC HOTOGRAPHIC CHEMISTRY

by

Keith M. Hornsby

I
THE
I II 1-: III I T I H

{I
FOUNTAIN
in conjunction Vi h

PRESS
0 F PHO TOG RAP H Y

J0

U'R N A L

Fi1'st Published 1956 Copyright 1956 by the Fountain Press 46-47, Chancery Lane, London, W.C.2

CONTENTS
/ "1'/'I~r II( REWORD CIIEMICAL
U.S. Representatives: 76, West Chelten Avenue, Philadelphia

Page 9

PRINCIPLES

..

11 11

Rayelle Publications,

44, Pa, U.S.A.

III Elements ulen y 'olllUon Chomical Principles ,Ids and Bases 1\, Ids and Alkaline Salts ()"Idalion and Reduction hemistry .. ()'f(I\nic (;lflllpS and Radicals
'I

Reactions

12 12 13 14 14 16 17 19 23 23 25 26 26 28 29 29

IIII~ EMULSION
I hI Binder I IIf Sensitive Salt I II itivity .. ( oIClation ( ,I'lnlin Modifiers '1i111111s rs 1\11 It isors

IIII!, SE

SITISING

DYES
Dyes

MI'T!lcyanines I h I\. .tion of the Sensitising III1lIra nsitisers

31 33 35 36 37 37 38 39 41 42 44 45 47

III E DEVELOPING

AGENTS

P1<INTED ~N GREAT BRITAIN BY

THI! MARSHALL PRESS LIMITED,

7.

MILFORD

LANE,

STRAND,LONDON,

W.C.2.

I'!ty I 0.1 and Chemical Development IIIlpl Inorganic Developing Agents (Ii I inlc Developing Agents I' fll'c't of Nuclear Substitution lilt tl 1I nts in the Amino Group 1\ 1111 I ar Developing Agents lit VIloplng Agents in Practice I'Wild tnry Developers

--

----=------

-"-----=--=

--

Chapter

5 THE DEVELOPMENT PROCESS

Physical and Chemical Development The Effect of pH .. .. .. Sodium Sulphite Reduction of Fog .. The Metol-Hydroquinone Developer Developer Types .. .. .. Fine Grain Developers .. Other Developing Agents .. Phenidone Developers Pyro Developers . . .. .. Concentrated Developers .. .. Special Development Techniques .. Physical Development Technique Forced Development .. ..

Page 49 49 50 51 55
56

h"I,lrf

OLOUR DEVELOPMENT
rimary Colour Development Secondary Colour Development olour Developing Agents olour Couplers olour Coupling Reaction Stability of Dyestuffs Treatment after Development Colour Development Accelerators

Page 96 96 97 97 99 104 105 107 108 109 109 110 110 111 112 113 115 117 120 125 125 126 128 129 130 130 131 132 133 134 135 137 137 138 139 140 140 140 141

57 59 62 63 63 64 64
65

10 I TEGRAL TRIPACKS
Tripack Principle .. tripping Tripacks .. olour Transparency Tripacks Kodachrome llford Colour Tripacks Containing Non-Diffusing Couplers olour Accuracy olour Masking oloured Colour Couplers .. LI

66 69 69 71 71
72

6 FIXATION AND WASHING

Stop-Baths .. Fixation .. The Thiosulphates as Fixing Agents Completion of Fixation .. .. Fixing Bath Additions Hardening Fixing Baths Washing Hypo Eliminators ..

73 75

76 76
78 78 79 79 81
82 82

MISCELLANEOUS PROCESSES
Print-Out Emulsions Reversal Processing Processes Not Using Silver Salts .. Blue-Print Processes Oiazonium Salt Processes .. Semi-Wet Developed Materials Dry Development Method The Carbon and Carbro Processes Imbibition Processes Dye-bleach Processes Image Diffusion Processes ..

7 INTENSIFICATION

A D REDUCTION

Chromium Intensifier Sulphide Intensifier Mercury Intensifiers Miscellaneous Intensifiers . . .. The Quinone-thiosulphate Intensifier Physical Intensifiers .. .. Reduction .. Photographic Effect of Intensification and Reduction

83 83 85 85 87 88 89 89 90 91 92 93

8 TONING PROCESSES
Silver Salt Images .. Direct Sulphide Toning .. Selenium and Tellurium Toning Metallic Toning Metallic Ferrocyanides Two-stage Methods Other Metal Salt Images Dye-Toning.. .. Dye-Toning Technique

l:l SOLUTION PREPARATION

I~quipment .. The Balance Mixing Vessels M asuring Vessels Storage of Solutions Water Thermometers

Page

APPENDIX:

COMMON RADICALS

143 143
144 144

Monovalent Radicals Bivalent Radicals " Trivalent Radicals, ,

FOREWORD
INDEX
145 FAR as simple books are concerned, photographic chemistry is probably the most neglected of all photographic subjects, In writing this book it has been my aim to present to the Indent or technically minded photographer-whether amateur III professional-a relatively simple outline of the basic pi mciples of the chemical reactions involved in the photoWa phic process, It seemed desirable to supplement the usually r n.nty outlines given in most general photographic text-books .u.d fill the gap between these books and the advanced books 1111 photographic science, which are written for the photo/{,.Iphic scientist and are therefore worded for the scientist Iiilher than the photographer. I make no apology for introducing chemical terminology 1111 a popular book in order to avoid the ambiguity and .Iurnsiness whioh would be associated with any attempt to r-xplain a scientific subject wholly in everyday language, I have, however, endeavoured to explain the unfamiliar terms, "lid photographers do not, in general, appear to object to II'iLI'nand use scientific expressions, I~xperience has taught me that personal notes on technique !IIII'll find thei.r way into the margins of practical books, or .t 1'0 jotted down on scraps of paper or committed imperfectly 10 memory, To discourage these habits I have set aside overal pages at the end of this book in the hope that ludividual observations based on practice will be given more 11I'I'manent and more readable form, I would like to take this opportunity of thanking Mr. rt h ur J, Dalladay , the Editor of the British Journal of f'l/OtagraPhy and his staff for their invaluable help in the prtparation of the material as it appeared in serial form in llinl journal. KEITH M, HORNSBY,

As

Chapter

CHEMICAL

PRINCIPLES

1
II

The Elements HE bricks which the chemist uses to build his complicated chemical compounds are the elements, which are the simplest form of matter. Almost ninety of them exist in nature, and during the nineteenth century, those which had 110 in discovered were carefully classified according to their ch .mical and physical properties. They were also given ymbols which in many cases were the initial letter of the l'lc'ment's name, with, in most cases, a second letter to' differntiate between two elements with the same initial letter. The commonest elements usually have only the initial letter, and I h less common have the second letter. We all know that an uom of hydrogen is represented by the letter H and oxygen hy O. Barium and aluminium have the symbols Ba and AI. , me symbols are derived from the Latin names for the I lern nts. The symbol for silver is Ag from argentum and Iron is Fe from ferrum. When two or more elements combine to form a compound III symbols show the ratio in which the elements are present. Thus hydrogen and oxygen combine to form two compounds water and hydrogen peroxide. In water, two atoms of hydrogen combine with one atom of oxygen to give the Inmiliar H20. Hydrogen peroxide is a compound of two uoms of hydrogen and two atoms of oxygen, and has the mbol H20,. The combination of two or more atoms is termed a tuolcoule, and the group of symbols which represents a mole1111 is the [ormula, Atoms are the smallest of the units, IllIl rarely exist alone. The inert gases exist in the monatomic 111I m, but the majority 01 gases form diatomic molecules, for I ample, nitrogen=-Nj. oxygen-O 2' and hydrogen-H 2' These simple formul<e-H.O for example-are termed "III/)il'icalformulCl'-they show only the relationship between I hll numbers of various atoms in a molecule. More complex r umpounds-c-par'ticularly organic compounds-have a more elc'lail d formula, the structural formula, which is a picture

11

II

ili

12

BASIC PHOTOGRAPHIC

CHEMISTRY

II,I,MTCAL

PRINCIPLES

13

of the way in which the individual atoms are arranged. The later section on organic chemistry will illustrate this type of formula. Valency When the atoms of different elements combine to form a compound, they do not always combine atom for atom. Each element has a valency number which is the number of atoms of hydrogen which will combine with, or replace, one atom of the particular element. Chlorine, for example, is monovalent, as one atom will combine with one atom of hydrogen to give hydrogen chloride H-Cl. Sodium also has a valency of one. as one atom will replace one atom of hydrogen from hydrogen chloride, to give sodium chloride-NaCI. Oxygen, by combining with two atoms of hydrogen, H20, has a valency of 2, and calcium is also bivalent as it will replace these two hydrogen atoms to give CaO. Nitrogen and aluminium, by combining with, or replacing, three hydrogen atoms have valencies of three, and carbon has a valency of four. Some of the elements have a variable valency. Iron, for example, forms three oxides-the normal FeO, and also two others which contain more oxygen, Fes04 and Fe.Os' Photographically these variable valency elements are of great importance, having been used at one time as developers, and currently in most processes where the silver image is to be altered-for example, intensifiers, reducers, and toning solutions. These applications will be more fully discussed in the appropriate chapters. The properties of a compound differ greatly from those of the parent elements. The familiar sodium chloride-e-common salt-is a hard crystalline material which is essential to life. Its parent compounds are quite dissimilar. Sodium is a soft white metal and chlorine is a greenish gas. Both are very corrosive and poisonous. Solution When sodium chloride crystals are added to water they disappear. The water dissolves the salt to give a solution in which the crystals lose their large rigid form and split into the single sodium chloride molecules. Some of these single molecules change still further; they dissociate into ions
NaCI
sodium chloride molecule

The signs on the ions tell us several properties of the ion. p sitive sign tells us that the ion is a cation and a negative I harge that it is an anion. The number of signs indicate the v d incy of the ion (e.g., H+, Na+, Al +++ and Cl ", S- -). '1'110 presence of the sign also differentiates an ion from an ct m. A sodium ion Na+ differs from a sodium atom Na as it has one less electron and therefore carries a positive charge. Conversely, a chlorine ion CI- has one more electron than III' chlorine atom CI and so carries a negative charge. Not rll compounds which dissolve in water dissociate. It is only Iho salts, bases and acids which do this. Also, not all compounds which dissociate do so to the same ,I gree. The double arrow in the equation indicates that there , an equilibrium between the dissociated and the undissoci.u d molecules. The degree of dissociation depends mainly upon the particular compound, but it is also dependent upon III dilution. In general the weaker the solution, the greater Ihe percentage of dissociated molecules. An ion need not consist of only one atom. Sodium nitrate, Jor example, has a negative ion with four atoms:
NaNOs
sodium
nitrate

Na+
sodium
ion

NO,nitrate
ion

Water itself is dissociated to a very small degree giving hydrogen and hydroxyl ions:
H.OH (HoD) ~ H+

OH-

In a litre of pure water the amount of hydrogen ions is very mall-about O.OOOOOOlg. his figure is called the hydrogen T 10'1'1 concentration, and is extremely important. It is an r-xpression of the acidity or alkalinity of a' solution. To , press it as the actual concentration in grams per litre is uiconvenient. so it is expressed in a way which gives an easy II(.(ure,known as the pH. The way this figure is obtained 1 -I garithm of concentration
10 appreciate

of H+.

For water this gives a is necessary

Na+
sodium ion

CIchloride ion

II/{ureof seven, but no knowledge of mathematics the meaning of pH.

~I

14

BASIC

PHOTOGRAPHIC

C}ffiMISTRY

II ICMJCAL PRINCIPLES

15 acid.

Acids and Bases Acids and bases are substances which alter the pH when they are dissolved in water. Hydrochloric acid, for example, dissociates to give HCI ~ H++ CIand obviously gives a solution with a higher concentration of hydrogen ions=-asolution with a low pH. Sodium hydroxide is a base, or alkali. It also dissociates when dissolved in water: NaOH ~ Na+ + OHIn this case it is the hydroxyl ion concentration of the water which increases, causing the hydrogen ion concentration to decrease. The pH is increased. Acids which dissociate almost completely when dissolved produce a large increase in hydrogen ion concentration. These are the strong acids, for example, hydrochloric and nitric acids. Other acids dissociate less and are, therefore, weaker acids. Most of the hydroxide bases which dissolve in water dissociate strongly. These are the strong alkalis, for example, sodium and potassium hydroxides. Ammonium hydroxide does not dissociate to the same extent-it is a weak alkali. Acid and Alkaline Salts If the salt of a strong acid and a strong base, 'or a weak acid and a weak base, is dissolved in water, the change in pH will not be very great. But if the salt of a strong acid and a weak base-ammonium chloride for example-is dissolved in water the solution will be slightly acid. Conversely, if sodium borate (borax), the salt of a strong base-sodium hydroxide-and a weak acid-boric acid-is dissolved in water, the solution will be alkaline. As there are many weak acids, many sodium and potassium salts are alkaline. When hydrochloric acid is dissolved in water we have one hydrogen ion and one chloride ion. If this solution is mixed with an equivalent solution of sodium hydroxide we have the reaction NaOH -+ NaCI HCI + + H.O (H+ + CI-) (Na+ + OH-) (Na+ + CI-) (H+ + OH-)
hydrogen
chloride sodium hydroxide sodium chloride I

'l'h ' hydrogen atom of one molecule of hydrochloric acid is

(placed by a monovalent base. It is a monobasic Sulphuric acid dissociates in the following way H2SO, ~ 2H+ + SO.--

'I'wo sodium atoms are needed to replace the two hydrogen toms. Sulphuric acid is dibasic, Phosphoric acid-H .PO,I tribasic. These polybasic acids need not be completely converted to t II' corresponding salts. The conversion proceeds in stages
j

H2SO, + NaOH -+ NaHSO. + H.O

sodium

bisulphate

II

NaHSO. + NaOH -+ Na2SO. + H.O

sodium sulphate

H.PO, + NaOH -+ NaHPO. + H,O

sodium

dihydrogen phosphate

NaH.PO, + NaOH

-+

Na2HPO. + H.O
disodium

hydrogen phosphate

Na.HPO, + NaOH -+ Na.PO. + H.O

trisodium phosphate

water

These acid salts have a pH between that of the acid and t It normal salt. The salt, despite its name acid salt, need not necessarily have an acid reaction. It is acid because it vontains a replaceable hydrogen atom. When two ionic solutions are mixed, the solid obtained if t h! water is removed is not necessarily a mixture of the two C nn ponent salts. In cases where no gaseous or insoluble "' l rials are formed the solid will probably be a mixture of ( v ral compounds. For example-solutions of sodium r hloride and potassium nitrate are mixed and "the resulting 11111 lion is evaporated to dryness. The solid will be a mixture of odium chloride, sodium nitrate, potassium chloride, and potassium nitrate. The proportions of the individual compWl nts will vary with the ionic concentrations, and the nlubilities of the possible salts. In general the salts of lower nluhility will be preferentially produced.

16

BASIC

PHOTOGRAPHIC

CHEMISTRY

('lmMICAL

PRINCIPLES

17

When two of the ions produce an insoluble salt, or a gas or volatile liquid, these compounds are no longer present in the ionic system, and therefore alter its equilibrium, and will usually predominate in the final reaction products. For example: CuSO. + Na.S ~ CuS + Na.SO.
copper sodium copper sodium

sulphate

sulphide

sulphide

sulphate

Copper sulphide- is the insoluble material in this reaction and as long as copper and sulphide ions are present the reaction will proceed to the right. It cannot, under normal circumstances proceed in the reverse direction. Similarly where one of the products is removed as a gas the reaction cannot be reversed. Oxidation and Reduction Reactions Reactions of this type are very important in photographic processes. In the simplest forms the superficial meaning is correct. Copper when heated in oxygen is osidised to copper oxide2Cu
.

As we have seen, ferric chloride will oxidise finely divided silver, but the now obsolete ferrous oxalate developer reduces silver chloride, the ferrous ion being oxidised to the ferric. The brief explanations given should help the reader to Iollow most of the following text, apart from organic chemistry, but for those who wish to study somewhat deeper, Electronic Theory and Chemical Reactions is recommended, '" in addition to the normal chemistry text-books. Organic Chemistry Organic chemistry is the chemistry of carbon compounds. In simple carbon compounds, such as sodium carbonateNa.C03-carbon behaves in a similar manner to other clements with a valency of four. But carbon compounds can be prepared in which carbon plays a part unlike other clements. The feature of carbon which is remarkable, is its ability to combine with- itself. Diamond and graphite are nothing more than carbon atoms arranged in the form of gigantic three- or two-dimensional molecules. Other elements may be included in these large structures, and to understand the properties of these compounds it is necessary to know not only the proportions in which the various elements are present, but also the way in which they are arranged. This is why the ' picture' or structural formulas mentioned earlier are so important. They show the properties of the compound. The simplest organic compounds are the hydrocarbons, and, as their name implies, consist of carbon and hydrogen. The carbon atoms may be arranged as a chain

O. ~

2 CuO
heat

which, if then heated in hydrogen, is reduced back to copper CuO

+ H.

Cu

+ HaC

Oxidation and reduction always accompany each other. An oxidising agent is one which is reduced relatively easilyconversely a reducing agent is easily oxidised. Oxidation and reduction is not necessarily accompanied by transfer of oxygen or hydrogen. Ferric chloride is reduced by, or alternatively will oxidise, finely divided silver
Ag

+ FeCls

AgCI

+ FeCI.

-d-d-d-dI I I I
or the terminal atoms may join up to form a ring

The silver is oxidised to silver chloride-it loses an electron ; whilst the ferric chloride is reduced to ferrous chloride by gaining an electron. Iron is one of the elements which has variable valency, and the majority of inorganic oxidising and reducing agents depend. upon variable valency for their action. We can write the equation
Ag
silver
atom

Fe+ + + =<= Ag+

ferric:
ion

Fe+ +
errous
Ion

silver
ion

which implies that the reaction can proceed in either direction, depending upon conditions.

R. W. Stott,

Longmans,

Green & Co. Ltd.

-----~----------~--

18

BASIC PHOTOGRAPHIC

CHEMISTRY

, III ~IICAL

PRINCIPLES

19

The links which join the carbon atoms to each other, or to atoms of other elements are termed bonds. These bonds may each be connected to a single atom of carbon or hydrogen

11111

H H H-b-t-~-t-H
H H

simplify structural Iormulze the I11dividualatoms- are n rrnally drawn in aromatic compounds. Instead, a unpl ring is drawn to represent the benzene nucleus
I'll

H I H-C~C"C,H
, II

WC~C/_C-H

when the compound is said to be saturated. If all the bonds are not used, then two bonds instead of one will join two atoms.

I'r
II II

i 1st two rings represent naphthalene. H

I II

H
I

H_C~C"C/C""CH
to give an unsaturated compound. lhe same division may be used with the ring or cyclic compounds H ,

H/C""c /C" C~c..H

H
Groups and Radicals

H,C./'

~H"""H C
W
H

wC"~
C

IH

'H

I
unsatu rated

I'HIIlS
III

Wh n a number of atoms arranged in a definite system a part of a more complex molecule, it is called a group a radical, for example II

;C'H

H
saturated but with an important difference. The saturated hydrocarbons are very resistant to chemical attack, but the unsaturated chain compounds, because" all the bonds are not fully occupied, are weak, and readily attacked by reagents. The cyclic unsaturated compounds, such as benzene in the above figure, are not readily attacked, and are almost as stable as saturated compounds. The alternate double and single bond structure is now known to be inaccurate. All the bonds are of the same type and _are called aromatic bonds, as the compounds of this type are the aromatic compounds. The straight chain compounds are termed aliphatic and the non-aromatic ring compounds are alicylic,

C-H
H

methyl group

C- C- C-H , , ,
H
1111\

H H H
H

propyl group

-C

-0 ;c-~
H

phenyl group

~C=<

C-H
H

woups being joined together

II

via the unoccupied bonds

II-~

-0

methyl benzene = phenyl methane = toluene

II

---

-~-

---

-------

- -

---

--

-------"------

20
H

BASIC

PHOTOGRAPHIC

CHEMISTRY

, III',MICAL

PRINCIPLES

21 bromine and iodine-are the

The symbols for these groups may be further abbreviated

The

halogens-chlorine,

.ummonest single valency element substituents, and replace

-C-H

-CHs

-Me

Ii drogen in the same way as monovalent groups. CH3-CI methyl chloride

~
. Other elements than carbon and hydrogen may be present In, or even constitute, a group. Those which are most common in photographic chemistry are the

amino group-NH2 hydroxyl group-OR carboxylic acid group-CO. OR sulphonic acid group-SO,R nitro group-NO.
The above groups are all groups which can replace one hydrogen atom, and are therefore similar to the monovalent atoms, which can also be considered with the groups. These examples show how the groups are attached to the hydrocarbon radical

o
Br

brornob en zene

The bivalent atoms and groups can be introduced in ovcral ways, oxygen for example can give the ether group, , as in C2HS 0 - C.Hs diethyl ether III an replace two hydrogen atoms from the same carbon .uorn to give the carbonyl or ketone group

o
\I

-Clilt

i .h is itself a bivalent

radical

o
H-~-CO

.I

_OH)

acetic acid
ollie

II CH. - C - CH3 dimethyl ketone or acetone itrogen, being normally a tervalent element, can be introd into the aromatic radical to give, for example H , H'C/S::~C-H

CHs- CO.OH H H H-t-t-OH

1
J
ethyl alcohol

I H

I H

II I or H,C.'N~CH
( r-li
IlilH

O
N

pyridine

C,HsOH

benzene sulphonic acid

I I Ot-!

compounds in which all of the atoms actually in the are carbon, are termed carbocyclic, whilst pyridine and imilar compounds with one or more other elements in the IIIIKH are termed heterocyclic. '111se groups can give to organic compounds properties uui lar to the inorganic acids and bases. The hydroxyl group I l h equivalent of the inorganic hydroxide, and compounds I uulnining this group-the alcohols and phenols-react With I u lioxylic acids to give compounds like the salts called
r 1(,I's

6
------

hydroxybenzene or phenol
propionic

acid

methyl alcohol

methyl
propionate

water

_.

--

~--

-----

------~

22

BASIC PHOTOGRAPHIC

CllEMISTR Y

Once again we have a reversible reaction. The reaction to .the right is known as esterfication and that to the left is hydrolysis. The amines are also basic and react with carboxylic acids to form the acid amides which have the carbonamide grouping-NH-COR-NH-CO-Rl

Chapter

T.HE EMULSION

The capital lefters Rand R' denote a radical of a specified type, and together with other letters are frequently used to simplify structural formulas. In this case they could be aliphatic (alkyl) groups or aromatic (aryl) groups. Sulphonic acids also form compounds-the sulphonic esters -with hydroxyl bases
R-O-SO.Rl

'THE

photographic emulsion consists of three main partsthe binder, the sensitive salts, and the' finals.' The finals are small quantities of substances which improve III emulsion, and are normally added immediately prior to roating. The Binder

and sulphonamides

with. the amino bases

R-NH-SO.-Rl

The preparation of organic compounds with various groups in the desired positions is a very specialised field. Substitution is not always straightforward, and it is frequently necessary to adopt roundabout methods to produce the required compound.

In all normal emulsions the binder is gelatin, but many nth r materials have been used in the past. They all fall into the class of materials known as colloids. These are materials which either consist of very large moleI III s which do not dissolve to form a true solution; or they nro insoluble materials-even metals-which stay suspended in a liquid because they are divided into extremely small pnrticles, The colloids used in emulsions are all large-moleI 1110 materials. Some can form viscous solutions known as sot in the fluid state, or gels in the solid or semi-solid state. Colloids which have been used in emulsions include various water-soluble gums, starches and proteins such as albumen "lId gelatin. Gelatin has several characteristics which have I osulted in its great photographic importance. (.1) When dry it is strong and tough, and secures the silver halide grains :firmly to the support. This toughness also protects the grains from physical damage caused by abrasion. (I It also protects the grains from chemical action (an emulsion made without a binder would be completely fogged in a normal developer). (I') The change from a sol to a gel in aqueous solution is at a convenient temperature for coating, and is reversible:ta.30c

Gel ~

Sol

(d) Substances present in gelatin have a favourable influence on the photographic characteristics of the emulsion. 23

24

BASlC PHOTOGRAPHIC

CHE7STRY

1111';

EMULSION

25

The manufacture of photographic gelatin from animal hides is a very complicated process, and the details are the guarded secrets of gelatin manufacturers. The first stage in manufacture, after thoroughly cleaning the hides, is to remove the inorganic materials which make the hides hard. This step is relatively simple, and is common to the manufacture of all types of gelatin for culinary and industrial use. The gelatin at "this stage would be quite useless for photographic work as it contains many substances which would fog an emulsion. It is the removal of these substances which is the great difficulty. Some of these substances which cause fog when present in large quantities can have very beneficial effects on the speed and contrast of the emulsion when they are present in small quantities. The great difficulty, then, is to reduce the amount of these materials present to such a level that a fog-free emulsion can be prepared, yet leave sufficient to give a gelatin with the required photographic characteristics. The process is further complicated by variations in the natural raw materials. It is, of course, impossible to obtain identical batches of hides, so the gelatins prepared from each batch of hides will vary to some extent. However, by skilful blending of different batches a remarkable degree of consistency is present in the final product. Gelatins are available in a wide variety of types suited to different emulsion characteristics. Some are inert gelatins from which all the substances affecting photographic characteristics have been removed or neutralised. Others are blends in which the quantity of substances increasing speed or contrast are widely varied. The presence of sulphur compounds -such as allyl isothiocyanate-produces emulsions of greater sensitivity due to the formation of sensitivity centres of silver sulphide. Too much of the sulphur compounds, however, results in a foggy emulsion. Proteins such as albumen, or the addition of bisulphites or sulphur dioxide affect the ripening of the emulsion. Of gelatin itself, little can be discussed in simple chemical terms. The chemical structure which results in the peculiar physical properties of gelatin is very complex. The gelatin molecule itself is very large, consisting of many long-chain units containing both amino and acidic groups. The gigantic molecules of gelatin are composed of large numbers of these simpler amino-acid groups-not all of the same type-linked together in many different ways.

The Sensitive alt I'he individual crystals of silver halide consist of many thounnds of silver and halide ions arranged in a crystal lattice, which, however, is not quite the perfect lattice pictured h re.!.2.

The silver halide grain is always prepared with an excess of halide present. This makes sure that the outermost ions are .ilways halide ions, which, being negatively charged, form a 1\ igatively charged" sheath" around the grain. At normal It.mperatures this lattice vibrates, and some silver ions are u-leased from their original positions and wander about in the , rystal. When light strikes the grain. some of it is absorbed, converting bromide ions to bromine atoms. In doing this, an loctron is released, and this also moves about in the crystal. It is now that the gelatin impurities, which contain sulphur, Ii their work. When the emulsion is prepared, these sulphur compounds react with silver salts to form minute specks of liver sulphide, mainly on the surface of the grain in norxpal r-mulsions. These sulphide specks-or sensitivity specks-take up the free electrons and therefore become negatively charged.

,.
26
BASIC PHOTOGRAPHIC CHEMIST I liE EMULSION OUTLINE OF THE PREPARATION SILVER OF A SLOW TO MEDIUM

27
SPEED

In this condition they attract the wandering positive l' ver ions, converting them to silver atoms and neutralisirig the charge. Further electrons and then silver ions are attracted in a similar way to produce more silver atoms near the sensitivity speck. When sufficient silver atoms are present in one portion of the crystal (the number has been estimated at about two hundred), the protective sheath of negatively charged bromide ions is disturbed. If the grain now comes in contact with a developer ion which is also negatively charged, the developing agent ion will not be repelled by the group of silver atomscalled the development centre-as at this part of the crystal surface there is no repelling negative charge. The developing agent can now reduce the rest of the silver halide in the grains' to metallic silver. Sensitivity A large silver halide grain will, because of its larger projected area, absorb more light than a small grain. The number of silver atoms produced will therefore be greater than in a small grain if the two are exposed to light of equal intensity. A development centre will, therefore, be more easily produced. In other words, a large grain will be made developable by a lower light intensity than a smaller grain. Its sensitivity is greater. Gradation If the grains in the emulsion could be all of the same sensitivity, then the emulsion would have the maximum possible contrast. Although light of different intensity may fall upon different parts of the emulsion, the emulsion would not discriminate between the different intensities. A given light intensity would either make all of the grains developable, or would not make any developable. In practice, emulsions made in the normal way have grains of a variety of sizes. The large grains will absorb the necessary light to form a development centre at a lower intensity than the small grains. As the intensity of light increases, the number of developable grains will also increase. This emulsion will respond differently to each light intensity, and will give an image with gradation. The emulsion maker can control the gradation (and incidentally the speed) of an emulsion quite easily, within limits. If we follow the course of typical emulsion technique the relevant points can be illustrated.

lODO-BROMIDE

EMULSION.

I. Swell 40 gm, of gelatin in

200 c.c. water for 3 hrs. 2. Heat to 50 degs. C. on water bath. 3. Add 20 gm. ammonium bromide and 2 gm. potassium iodide in 200 c.c. water. 4. Add, with constant stirring, 30 gm. silv-er ni tra te in 100 c.c. water at 45 degs. C.

Type of gelatin (slow, medium, fast; soft, medium, hard) will depend upon type of emulsion

requir-ed.
Choice of halides will depend upon type of emulsion. The time of addition of this solution will depend upon the contrast required-1 min. for a slow contrasty emulsion in which all the grains are nearly the same size, up to ~O mins. for a soft, fast emulsion with a great variation in grain size. First ripening stage. The time varies according to the gelatin and the emulsion type. This addition is to enable the emulsion to be set to a firm jelly for washing. The preparation of chloride emulsions, which are frequently unwashed, ends here.

5. Continue heating at degs, C. 10-60 mins.

50

6. Stir in 20 gm. gelatin and continue stirring until completely dissolved. (This gelatin may be inert.) 7. Cool the emulsion as rapidly as possible and leave in refrigerator overnight. 8. Cut the emulsion into small pieces. 9. Wash to remove unwanted salts - e.g., ammonium nitrate and the excess bromide which would hinder the after-ripening stage.

This is to enable the washing operation to be performed efficiently. There are many possible ways of telling when an emulsion' is washed. When ammonium halide is used (as in this case) the washing is continued until ther-e is no reaction with an ammonium salt test. Other methods are to determine the amount of free bromide in the emuls-ion shreds, or to measure the electrical conductivity.

28
10. Digest or after-ripen the emulsion at 60 degs. C.

BASIC PHOTOGRAPHIC

CHEMISTRY

THE EMULSIO:s'

29

This operation increases the speed and contrast of the emulsion. Heating is usually continued until the emulsion shows very slight fog in the case of negative emulsions ; or is stopped short of fog for positive emulsions. Unless previous information on the particular emulsion is available the time must be determined empirically.

development much more simple, as the softening of the emulsion due to developer alkali is reduced. Among the organic hardeners which are commonly used are aldehydes such as formaldehyde and glyoxal, often together with other compounds which either increase their efficiency or reduce their tendency to fog the emulsion. Spreading and wetting agents, such as saponin and various sulphonated fatty alcohols and oils, are added to make coating easier, particularly when a non-absorbent base, such as glass or celluloid, is used. Stabilisers To digest the emulsion it is necessary to remove almost all of the excess halide by washing. In this condition the emulsion will become foggy when stored at normal temperatures, and particularly so at high temperatures. This is in part due 1(' continued digestion. Further additions of potassium bromide will make the emulsion more stable. The addition of bromide will also alter the characteristics of the emulsion to some extent, usually reducing the sensitivity and the contrast. Organic stabilisers have been developed which give stability without adversely affecting the emulsion characteristics. These are usually heterocyclic compounds which are capable of forming silver salts of very low solubility, normally less than that of silver bromide. Sensitisers These can be divided into two groups-the "chemical" sensitisers and the " optical" sensitisers. As we have seen, the formation of the latent image depends on the presence of sensitivity specks-particles of impurities in the structure of the grain. Following the isolation of one of the compounds in gelatin which produces these specks-allyl isothiocyanate-many organic and inorganic sulphur compounds have been investigated with a view to increasing emulsion sensitivity. Another method which appears to be used extensively is the inclusion of salts of gold, platinum and palladium, frequently together with a sulphur compound such as potassium thiocyanate. It seems possible that small metallic specks can behave in an analogous manner to sulphide sensitivity specks. The colour sensitivity of an emulsion can be increased by dyeing the halide grains. As we have seen, it is the absorbed

The proportions of the different constituents may vary greatly from the example given. Some very high-speed emulsions have only a small amount of gelatin present during precipitation-about 1 per cent.-to enable the grains to increase in size rapidly as a high concentration of gelatin slows down the first ripening process. In the case of negative and high-contrast emulsions the silver nitrate is frequently converted to silver hydroxide by adding ammonia, and dissolving in excess ammonia. This method also results in more rapid ripening, but all traces of ammonia must be removed during the washing stage. Ammonia emulsions are usually prepared at lower temperatures than neutral or acid types. Although ammonium bromide was specified in the example, it is not essential for ammonium salts to be present. Paper emulsions are usually prepared by using sodium, potassium or cadmium halides, frequently in slightly acid solution. The chemical sensitisers (sulphur compounds and precious metal salts) referred to later, are usually added before or during after-ripening. After the addition of the "finals" the emulsion will be ready for coating. Some of these compounds are added to the majority of emulsions. Others only to special types. Gelatin Modifiers Chrome alum, or an organic hardening agent, is a necessity in all emulsions except those which are to remain soft (physically) for special purposes. Usually only a small quantity of hardener can be added to the emulsion before coating, further hardening after development being the practice. This small quantity of hardener, however, does make

30

BASIC PHOTOGRAPHIC

CHEMISTRY

light which produces photochemical action in the grain to give a latent image. Normally the silver halides reflect all but the blue light. By adding certain dyes, the grains can be made to absorb light of all colours, and so be more sensitive. These dyes are added in very small quantity to the emulsion, and do not colour it appreciably. Attempts to explain the mechanism of optical sensitisation in electronic terms, on the lines of the Gurney-Mott latent image theory, have not yet attained the perfection of the latter theory, and cannot therefore be readily summarised. Until 1945 no information on the preparation of commercial types of emulsion was available. As a result of the investigations on German industries carried out after the war by British and American teams, such information is now available to the public in reports available from the Stationery Office".

Chapter

THE SENSITISING

DYES

NTIL 1873 the sensitivity of photographic materials was limited to the blue, violet, and ultra-violet spectral regions. In that year, however, Vogel found that collodion dry plates manufactured in England by Wortley were sensitive to green light. He rightly attributed this to the presence in the emulsion of the yellow dye, corraline, which Wortley had added to reduce halation. The green sensitivity of these plates was very slight, but two years later, Waterhouse Iound that eosin was a more efficient green sensitiser. 1884 saw two important advances-Eder's use of erythrosin, and Vogel's discovery of the sensitising action of cyanine blue. Erythrosin is closely related to Waterhouse's eosin, and was used commercially for the production of the cheaper orthochromatic roll-films until 1939. The discovery of cyanine blue's sensitising action, however, was the first step in the researches Iinanced by most of the photographic manufacturers which have resulted in an enormous number of cyanine sensitisers being disclosed in patents. The cyanines and their related dyes are now used universally to the exclusion of the commoner dyes, as the sensitising efficiency of the cyanines is so great. Generally speaking, the cyanines have no practical application apart from their use as photographic sensitisers They can be used (or dyeing textiles, but are not fast to light. The structure of the cyanines is

.,z\ .
I
~n

rZ2i

y- N=C - (CH=CH\-CH= C-N-X

A
REFERENCES MOlt and Gurney-Electronic Processes in Ionic Crystals, Soc., 1938 ; 164A, 15!. 2 Berg, W. F.-Discovery, Oct., 1950; Vol. II, pp. 314-318. 3 B.I.O.S. Final Report No. 1355.
1

also Proc.

Roy.

Z' and Z2 represent the atoms necessary to complete heterocyclic nuclei, X and Yare hydrocarbon groups, and A is an n id radical: n is 0, 1, 2, 3, 4 or 5. Among the heterocyclic nuclei in common use are: 31

II

~I"

-.

32

ex)

BASIC PHOTOGRAPHI

CHE~IISTRY

THE SENSITISING

DYES

33

0,quinaldine

((

CN"v

benzoxazole

WCH-CH=CH-W /" C1.HS I I C2HS

8-

lepidine

(X
i.e.,

S,
N"v

C -

benzthiazole

and their substitution

products,

aD
S CH:D , CH

O,
C5-phenylbenzoxazole

N~

C-

5-6 dimethylbenzthiazole

N~

The number of - (CH=CH) - groups represented by the symbol n depen~s on the sensitising range required. For example, 1 : l'-dlethyl pseudocyanine iodide (n = 0)

sensitises with a maximum at 640mj.t. The nature of the heterocyclic nucleus also influences the sensitisation range. For example carbocyanines-that is dyes with one - (CH=CH) - group-s-which have two benzoxazole nuclei-the oxacarbocyanines-sensitise with a maximum at 515mj.t, with benzthiazole nuclei-the thiacarbocyanines-the maximum is at 582mj.t; the parent carbocyanine, as we have seen, sensitises with a maximum at 640mu; and when both nuclei are lepidine, 1: l'-diethyl4 : 4':carbocyanine-commonly called kryptocyanine-is produced, and this dye sensitises in the near infra-red with a maximum at about 745m~L. The presence of substituents in the nucleus also shifts the maximum of sensitivity towards the longer wavelengths. As the inclusion of more - (CH =CH) - groups extends the sensitisation to longer wavelengths, the majority of current sensitisers for the infra-red contain several of these groupsthe practical maximum being five in the pentacarbocyanines which sensitise up to 1200mj.t. The use of cyanines containing two different nuclei usually results in a band of sensitivity roughly midway between the bands of symmetrical dyes containing each nucleus. Thus, lhiacarbocyanine sensitises with a maximum at 582mj.t and Iho maximum sensitisation from kryptocyanine is at 745mj.t. A carbocyanine containing one benzthiazole and one lepidine 1111 I us should, and in fact does, sensitise with a maximum ,d about 660mj.t. Merocyanines The most effective of the cyanines are those which contain n azole nucleus, and until the mid-thirties the fastest orthochromatic and panchromatic contained these dyes. Then a new class of sensitisers was discovered independently by Kendall, of Ilford, and Brooker, of Kodak. As these dyes contained half of a cyanine dye, they were named the merocyanines. Unlike the cyanines in which the quaternary nitrogen atom having an acid radical attached to it

sensitises with a maximum at 570m~L' whereas pinacyanol 1 : l'-diethyl-2 : 2'-carbocyanine iodide (n = 1)

or is an essential feature, the merocyanines

)N<

acid

contain

only

E"

_ __

-_______

__~_

34

BASIC PHOTOGRAPHIC

CHEMISTRY

1111'; SENSlTISING

DYES

35

trivalent nitrogen in the cyanine type nucleus, the other nucleus containing essentially a carbonyl group >C=O. As there are many heterocyclic nuclei containing this group the number of merocyanines available is very great. Two typical ones are

The Action of the Sensitising Dyes According to the Grotthus-Draper law, in photochemical reactions it is only the absorbed light which 'has any chemical effect, and it is therefore not surprising that silver bromide, wnich is yellowish and therefore absorbs only blue, violet, and ultra-violet radiation, is only sensitive in this spectral region. The optical sensitisers extend the sensitivity of photographic emulsions by enabling the halide grains to absorb light of other colours. The verification of the relationship between absorption and sensitivity was not possible for some time, as dye solutions have absorption curves differcnt from those of the dyed grains, and the absorption curves of the dyed grains could not be measured satisfactorily, beause the light used for measurement produced photolytic silver which altered the absorption. By using Hardy's rapid working photoelectric spectrophotometer, Leermakers, Carroll, and Staud' were, in 1937, able to prove that optically sensitised emulsions do absorb light to which they are sensitive. The reasons why some dyes sensitise and others do not are n t fully known. The first requirement of a sensitising dye is that it should be adsorbed on to the surface of the halide grain, and so dye it and enable it to absorb light which the undyed grain does not absorb, Relatively few of the availnble dyestuff types are adsorbed in this way without possessing undesirable properties also (fogging, desensitising, etc.), nnd those that are free from these disadvantages are not n cessarily efficient sensitisers. Kendall' has proposed a /{ neral formula for sensitisers in which an anionic oxygen, sulphur, selenium, or nitrogen atom is linked to a cationic o ygen, sulphur, selenium, or nitrogen atom via a conjugated chain of an uneven number of unsaturated carbon atoms

1-phen y1-3-methyl-4 (3'-ethylbenzthiazoylidene) and

-5-pyrazolone

5-( l'-ethylquinaldin-2-ethylidene) -rhodanine. While these merocyanines are, in themselves, useful sensitisers, those containing a >C=S grouping, like the rhodanine compound above, can be converted to more complex dyes, for example by condensing with a further rhodanine nucleus to give the dye

which is itself capable of further similar condensation. Alternatively the simple merocyanine can be condensed with a salt of a basic nitrogenous heterocyclic compound to produce a dye similar to a carbocyanine, having a rhodanine nucleus in the methine chain

~e

0'1fl

-(C=C)n-C=

{O
~

-'

. --

36

BASIC PHOTOGRAPHIC

CHEMISTRY

This formula, however, gives no clue to the efficiency of a sensitiser, and many dyes which fit the formula are photographically inert. In the same paper, Kendall says that at the moment it is not possible to forecast whether a dye will actually be a sensitiser, even though it may possess the required features. One of the main difficulties is the lack of knowledge of the way in which the light absorbed by the dye or superficial silver halide-dye complex produces the energy necessary to produce a latent image in the grain. It is unlikely that the dye undergoes a permanent change, and therefore the energy produced when the dye absorbs light must be transferred to the halide crystal, or be lost. The arrangement of the sensitiser ions or molecules on the crystal surface appears to have a strong influence on the efficiency of energy transfer, and the action of supersensitisers further emphasises the importance of this energy transfer process. Supersensitisers In 1920 Bloch and Renwick' published an account of the action of auramine, a dye almost devoid of sensitising action, on optically sensitised emulsions. When incorporated in very small quantities it produced greatly enhanced colour sensitivity. Up to that time it had been assumed on the evidence of practical tests that sensitiser mixtures were generally less efficient than the individual sensitisers. This action of auramine was apparently neglected until 1937 when Mees patented a number of sensitiser combinations which produced greater sensitivity than the individual sensitisers. Now the number of patents claiming supersensitising action is as great as, if not greater than, the number of patent specifications which describe normal sensitisers. Many patentees, in fact, claim both sensitising and supersensitising action for their inventions. Supersensitisers do not necessarily have any sensitising action when used alone; some in fact are not even coloured, so their action would seem to be connected with increasing the efficiency of the transfer of energy from the light absorbing compound, rather than a simple increase in light absorption.
REFERENCES: Leerrnakers, Carrol and Staud. J. Chern. Pill's. 1937:5:878 Kendall. Cllem. and Ind. 1950; February. Block and Renwick. Photo Jour. 1920:60:145.

Chapter 4

THE DEVELOPING

AGENTS

To

the chemist, the developing agents are reducing agents. It is unfortunate that to the photographer, a reducer is a substance which dissolves metallic silver. It is just the opposite of a reducing agent-an oxidising agent. However, all reducing agents are not developers. Sodium sulphite and ordinary' hypo' are reducing agents, but will not develop. Stannous chloride and sodium llydrosulphite are also reducing agents, but they reduce the unexposed as well as the exposed silver halide grains. Therefore they are not developers. The standards for the photographer are that the exposed grains should be reduced as completely as possible, but that the unexposed grains should not be reduced. Other factors which have some importance in certain cases are the contrast, grain size, and colour of the image. But these factors depend more upon the constitution of the developing solution than upon the reducing agent alone. Some types of developing agents, of course, are more suitable for particular development processes, and this does influence the choice of developing agent. Physical and Chemical Development The action of developers can be roughly divided into two types-physical development, and chemical development. The basic difference between them is that the physical developers contain a soluble silver salt which is deposited from the solution on to the development centres, whereas the chemical developers merely reduce the silver halide adjacent to the development centres. The majority of developers in urrent use combine the two types of developing action, for although they contain no soluble silver salts, they contain sufficient silver halide solvent to dissolve some of the fine grains, and deposit silver on to the exposed and partially developed grains. In the days of the wet plate and the collodion dry plate it was customary to use a developer of the physical type containing pyrogallol, an organic acid, and silver nitrate (although 37

-.----..

38

BASIC PHOTOGRAPHIC

CHEMISTRY

rus

DEVELOPING

AGENTS

39

the latter was frequently present in the emulsion). Silver is readily deposited from this solution by reduction of the silver nitrate by the pyrogallol. Any metallic silver present will act as .a.prec~pitation centre. The small groups of silver atoms compnsmg the development centres will do this, but it is necessary for the precipitation centres to be much larger than for , chemical' development, i.e., the exposure must be increased. In 1861, an English photographer's assistant, Wardley, found that the acid and the silver nitrate were not essential, but that pyrogallol alone would develop the latent image in a dry collodion plate. This idea was elaborated by other workers, who made other additions to the solution, and who used different developing agents, to give the developer types which we use to-day. Simple Inorganic Developing Agents Although all the developing agents in common use are organic compounds, there are three types of inorganic compounds which will, under certain conditions, develop a latent image. In the first group are metallic ions which can form stable compounds in different degrees of oxidation-that is, metals of variable valency. Some salts of vanadium, chromium, molybdenum, tungsten and iron have developing properties, but only iron salts have had any practical use. >I< For many years before the general use of alkaline organic developers, the ferrous oxalate developer was very popular. The active agent is the complex ferro-oxalate cation Fe(e.O.)., and its action can be summarised by the equation ;Ag + Fe(C.O.h- - -+ Ag + Fe(C.O.).silver
ion

Such solutions could have no practical use because of the instability of sodium hydrosulphite. . The third group of inorganic developers also has no practical use, but they are of interest as they contain the basic groups of the main types of organic developing agents. There are three of these compounds, hydrogen peroxide HO-OH, hydroxylamine HO-NH., and hydrazine H2N-NH2 Hydrogen peroxide and hydrazine will only develop in strongly alkaline solutions, and both hydroxylamine and hydrazine form small bubbles of nitrogen in the emulsion. Organic Developing Agents If an organic radical-usually a phenylene radical-is present between the two active groups in the above three ompounds, we have the three basic organic developers-the dihydroxybenzenes, the aminophenols and the aminoanilines (or phenylenediamines).
OH
--'>

HO-OH

6
OH

0H

."d

o-dihydroxybenzene (pyrocatechol)

OH p-dihydroxybenzene (hydroquinone)

ferro-oxalate
ion

silver
atom

fer ri-exalaee
ion

HO-NH2

-->

This developer was studied at some length by Sheppard and Mees.' The statement above that sodium hydrosulphite is too powerful a reducing agent to be classed as a developer is true for normal emulsions, as hydrosulphite does not discriminate sufficiently between the exposed and unexposed grains. It will, however, develop silver iodide emulsions which are not easily developed with normal developers. The addition of bisulphite and bromide has been claimed to reduce its potency to such an extent that ~lormal emulsions can be developed.
Two describe vanadous of these solution recent Kodak patent specifications (B.P .. ? 17,040 and B.P. 720,235) the use of developing solutions contammg ferrous titanous and salts as the active reducing agents. It appears that an ~ssential feature methods is the continuous electrolytic regeneration of the developing which implies that the method is unsuitable for small-scale work.

6
NH2

NH
and

'

o-aminophenol

p-aminophenol

~ 6

NH '
and

o o o
NH2 NHZ

o-aminoaniline (o-phenylene diamine)

p-aminoaniline (p-phenylene diamine)

40

BASIC

PHOTOGRAPHIC

CHEMISTRY

TilE

DEVELOPING

AGENTS

41

The para compounds are much more extensively used than the ortho compounds as they are more powerful and efficient. The dihydroxy benzenes require a more alkaline developing solution than do the compounds containing an amino group. It will be noticed that the meta or 1:3 compounds are not in the above table. They are not developers. There have been several attempts to define developing agents by means of a simple formula and rule. The most generally applicable of these is Kendall's rule. The formula is:rx - (C = C) - rxl in which
(X

Effect of Nuclear

Substitution

If the nucleus is substituted by a further active developing function (which must be in an ortho or para position to one of the groups already present) the result will be an increase in developing power, thus H

and

(Xl

are the active developing functions-either amino or hydroxyl substituted and

amino or substituted

-N<~
0(

I :2:3-trihydroxybenzene (pyrogallol)

OH 0

is more powerful than

1-2-dihydroxybenzene (pyrocatechol)

OH

OH is more powerful than

hydroxyl-O-R and n is zero or a whole number. Where n =0 we have hydrazine, hydroxylamine hydrogen peroxide. Where n =1 we have the ortho compounds

r\ y
NH~
p-aminophenol

O~d
I

2:4 diaminophenol (amidol base)

Halogen atoms also increase the developing power

and where n =2, the para compounds 0<

(""r
(.,::>(

is more powerful than OH

chlorhydroquinone

r\ IV
OH
hydroquinone

OH

~,
In the case of meta compounds n = 1t and therefore does not fit the rule. Other organic radicals than the phenylene radical have been used in developers but apart from the polynuclea.r aromatic radicals which will be dealt with later, none have had any practical application. The majority of developing agents are based upon the six types above, and are usually these developers with substituents in either the nucleus or in the amino group.

A second chlorine atom in the 5-position

(IV
OH
2 :5-dichlorhyd roq ui none

~(I

increases the developing power still further, whilst a bromine atom in the nucleus

/
42
BASIC PHOTOGRAPHIC CHEMISTRY TilE DEVELOPING AGENTS

43

6
bromhydroquinone

is much. more powerful than

NH.CH3

p-methylaminophenol (metol base)

p-aminophenol

results in an even greater increase in developing power. In ad~ition to increasi~g the developing power, halogen SU?Shtut.lOnhas a fu.r~her Important practical effect. Hydroquinone IS very.sensIhve to cha~lges in development temperature-.m technical language, It has a high temperature coefficient. Chlorhydroquinone is far less sensitive. The .other type of substituent which increases developing power IS a lower alkyl group, for example, a methyl or ethyl group. OH

HsCI.-N-CZHs
p-diethylaminoaniline

is more powerful than

p-aminoaniline

o o
NHz NHz

c)CHl
NHz
3-methylp-aminophenol

is more powerful than

(tHl
NH2
2-methylp-aminophenol

which is more powerful than

This alkyl group is sometimes substituted in its turn to give the compounds greater solubility in alkali, or to red~ce the toxic effect upon the skin. In the most popular developmg agent which has this substituent-glycin-the methyl. gro~p of p-methylaminophenol is substituted by a carboxylic acid group.

p-aminophenol

Acid nuclear substituents generally decrease the developing power-in some cases even produce a substance which does not develop. Examples of such groups are: carboxylic and sulphonic acid radicals, and nitro and sulphone groups.

NHCHzCOOH
acetic acid

p-hydroxyphenylamino (glycin)

p-diethylaminoaniline is a common colour-coupling developer but it can cause severe dermatitis. If one of the ethyl groups is further substituted with a hydroxyl group

Substituenrs in the Amino Group The amino group of the aminophenols, and one of the amino groups of the aminoanilines are frequently substituted with one or two methyl or ethyl groups. This substitution, like the alkyl group substituent in the nucleus, increases the developing power-in some cases very greatly.

44

BASIC PHOTOGRAPHIC

CHEMISTRY

THE DEVELOPING

AGENTS

45

to give p-(hydroxyethylochylamino)aniline the toxic effect on the skin is reduced. . Th~se two compounds show, in a very pronounced way, the different effect of nuclear and amino group substitution by the same group. A hydroxyl substituent in the nucleus us.ually results in an increase in power-s-the hydroxyl substituent in 'p-die.thylamin~aniline reduces the power. Usually a carboxylic acid group m the nucleus seriously reduces, if not destroys, the -developing power, but glycin is a very useful, though somewhat slow acting, developer. Binuclear Developing Agents Many years ago, developing agents containing a naphthalene nucleus were popular. Among them were Eikonogen

Also of purely academic interest are developing compounds such as phenylhydrazine

ONH-NH
phenylhydroxylamine and hydrazobenzene.

ONH-OH
These compounds hydroxylamines. behave as substituted hydrazines and

~OH

S03Na~
Sodium salt Diogen, of l-amino-2-naphthol-6-sulphonic acid and

'~OH

S03Na~S03H
mono-sodium salt of l-amino-2-naphthol-3:6-disulphonic acid. Inclusion of sulphonic acid groups in the molecule are ~ecessary as l-amino-2-naphthol is not soluble enough for use In an aqueous developing solution. It will be noted that these developers contain sulphonic acid groups but despite this are efficient presumably due to the use of a naphthalene instead of a benzene nucleus. Many other binuclear compounds have been found to have developing properties, but have had no practical application. The two nucl~i may be as the above ones-naphthalene systems; or biphenyl may be the aromatic radical.

00
Another type has one or both of the developing joining two radicals-e.g., hydrazobenzene below. systems

Developing Agents in Practice The developing agent types which have so far been mentioned can obviously be expanded into a very large number of relatively simple, distinct developing agents. The majority of these would be efficient, yet very few have found their way into the darkroom. Metol and hydroquinone are by far the most widely used of the developing agents. Their manufacture is not difficult, therefore they are cheap. Their efficiency is high, especially when they are used together. Also-and this is a most important property-they are very versatile. Both metol and metol-hydroquinone mixtures are used with mild alkalis in the majority of fine grain negative developers where maximum emulsion speed is essential (D.76, D.23, DK.20, etc.). 'When a carbonate alkali is used, developers for almost every purpose can be prepared-fast working negative developers; lantern slide, positive film, and paper developers; high contrast developers for aero and X-ray films. Hydroquinone with a strong alkali (sodium or potassium hydroxide) is used for process and line work. Information from a large chemical manufacturer shows that about four times as much hydroquinone as metol is used; but that compared "nth these two developing agents the amounts of other developers sold is negligible.

THE

DEVELOPING

AGENTS

47
time be cut short, or unduly

46

BASIC

PHOTOGRAPHIC

CHEMISTRY

Pyrogallol-at one time the only developer used for negatives-is now rarely used apart from press work. It has one property which is sometimes desirable. When used alone or with metol in a developer containing little sulphite, a yellowish stain image is produced together with the silver image. This treatment can be used in cases of known under exposure, to give increased contrast. Amidol is used mainly in print developers. The developer can be easily prepared as only three ingredients are normally used=-amidol, sulphite and bromide. Its main disadvantages are that it does not keep in solution, and it stains the hands and equipment badly. p-aminophenol has two main uses-in concentrated developers, and as a substitute for metol in cases where the user is prone to metol poisoning. Developers made with p-aminophenol, bisulphite and a caustic alkali can be prepared as a stock solution forty times as strong as the working solution. These very concentrated solutions keep well in small stoppered bottles ( Azol, Certinal, Koclinol, Rodinal, etc.). Some people have skins which are very sensitive to metol, and are unable to handle developers which contain it. In such cases p-aminophenol is recommended as a substitute. This works well with paper developers, but is not so efficient as a negative developer. However, by using a developing tank it is unnecessary to touch a negative developer; with a print developer there is no convenient way of entirely avoiding contact with the solution. The one-time popularity of p-phenylene diamine for finegrain development appears to have faded somewhat. Even when used in combination with glycin it is necessary to increase the exposure two or three times to secure adequate shadow detail. A further fault which is sometimes attributed to p-phenylene cliamine developers is that the tone separation of the resulting negative is not good. In general it is better to use an inherently fine-grain emulsion and a normal finegrain developer, rather than attempt to obtain very finegrain results on a normally coarse-grain emulsion. Apart from its use in p-phenylene-diamine fine-grain developers, glycin's main use is in print developers. While it is not the purpose of this book to discuss the aesthetic points about glycin developed prints, it can be said that developers containing glycin (frequently together with metol and hydroquinone) do produce prints of a good colour,

even though the development protracted.

Proprietary Developers From time to time new developing agents, or compound~d developers, come on to the market-particular~y fine-gra~n developers. In many cases the extra:ragant claims made in advertisements are not borne out by mdependent labora~~ry tests. Four proprietory developers which are on the Brit.ish market are worthy of mention as they have been proved in practical work. , . , f Ilf d These are the developing agents Phemdone rom or Ltd and' Meritol ' of Messrs. Johnson & Sons Ltd., and the aCked developers 'Promicrol' and 'Microdol' o.f May ~ Baker Ltd., and Kodak Ltd., respectively. Mentol,. as is well known, is an addition compound of p-phenyl~ne dla:ne and pyrocatechol.2 It can be used with no alkali o~her an sulphite to give a very .:fine-grain d~veloper, or wit'h other additions to obtain maximum emulsion speed. . Phenidone is a more recent addition to the range of available developers. It is I-phenyl-3-pyrazohdone H2.C--CO

I
HC" N/

I'

and is a general purpose developing agent, particularl~ .usef~~ as a replacement for metol in M.Q. developers. In ~ IS r~ e f it is more efficient than metol, only about 7 per cen . 0 e wei ht of hydroquinone being required as a~al1lst up ~o 40 cr gcent. of metol. Packed developers. conta~l11ng Ph~l1ldone ~re available, the most noteworthy bemg '~'bcrophen , ~ fine zrain developer which gives increased emulsion speed wltho~t ~oarser grain than M.Q.-Borax developers. ~enerally spea.kin heterocyclic compounds such as Phenidone are mo~e ex~ensive than the customary types, but the efficlenc~ of ~~~s articular compound is great enough to make up or I~ ~isadvantage, as usually only half a gram or less IS used per litre.

NH

48
. BASIC PHOTOGHAPHIC CHEMISTHY

Nothing definite is know b t packed developers Both n a ou .the constitution of the two fine-grain develop~rs so compames have recent patents on connection. we can reasonably expect Some The May & Baker patent in th . Covers the use of 2-(~-h clr e names Field and ] ohn! y oxyethyl) ammophenol sulphate. OH ONH-(2H,-OH

Chapter 5

THE DEVELOPMENT

PROCESS

As would be expected from the group, this is not a powerful de rre.sence of the hydroxyl suggests glycin as an accel ve opmg agent. The patent The grain size is claimed to b:r:i::' :nd fia carbonate alkali. dlamme-sulphite develo os as. ne as a p-phenylene speed is slight comparel~~thb~~ ~:Q~~s~r: effective emulsion The developing agents clai d J h x type of developer. substituted p-phenylene diarnf!le m. th e Kodak patent- are Ines WIt the structure ,~C2, Hq-NH- SO.2-CH,3

E have already briefly discussed the latent image and its formation. Many theories have been proposed to explain the precise function of the groups of silver atoms on the surface-and to some extent in the interior-of the grain, in starting the development reaction.' Electron microscope photographs have shown that it is at these minute specks of metallic silver on the exposed grain that development starts. Without these specks-or development centres-the silver halide grain will not be reduced at all in a normal developer. As this book is concerned only with photographic chemistry, we will leave the photographic physicists and physical chemists to argue out the exact part played by the development centre.

yVx
NHZ In this formula R represent I ethyl, and X or Y or both must ban a kyl radical-normally methoxy (CH3-0-) or ethoxy (C _'b~tlkOxy group, such as 2 These substituted p-phen I d5 . much more active than th ene lammes are claimed to be phonamide grouping (_N:r~~~nt compou':1d. The sulsol:rbility, and reduces the toxic eff o~) also mcreases the claims regarding emulsion speed oec of.tJ;1ecompound. No the paten.t. r grallllness are made in

Physical

and Chemical Development

There are two possible ways in which the visible image can be formed-that is, in which silver can be reduced adjacent to the silver latent image speck. In the so-called , chemical' development process, the developer ion, which is negatively charged, is repelled by the protective sheath around the silver grain, but at the development centre on the surface the developer ion is not repelled. It can give its free electrons to the silver speck. The silver speck is then negatively charged, attracts the wandering silver ions in the halide crystal lattice, and neutralises them to form more silver; the cycle can be repeated. In ' physical' development, on the other hand, the presence of the halide grain is unnecessary. Fixed emulsions can be physically developed provided the exposure is sufficient and the fixing bath does not dissolve the latent image. The silver specks merely serve as precipitation centres .. The developing solution consists of a developing agent and a soluble silver salt. The solution is very unstable and must be mixed immediately prior to use. This solution will deposit silver

Sh

Pr~ces:r)pard ; ~hnson

. REFERENCES: and M~es-Illvestigation On the Theory

& Sons Ltd.-B.P.

of

the

K~J.: l:~~e(W~~~brrgi~~ &GI .

466625 JOhO&), .P. 644,249. B ass Vittum). B.P. 651,749.

Photographic

49

50

BASIC PHOTOGRAPHIC

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3

51

freely on certain substances, and the minute silver specks serve as excellent precipitation centres. , Normal' development is probably a combination of these two reactions, as developers usually contain substances which dissolve silver halides and give, therefore, an appreciable concentration of dissolved silver in the emulsion layer. Most, if not all, of the methods which restrict the process to either particular type are inefficient, requiring increased exposure, and usually increased developing time also. Apart from the physical development method which will be given later, we shall only concern ourselves here with normal development methods. The active organic reducing agents were discussed previously, but not the conditions which control their action. In general, the nature of the developer is governed as much by these conditions as by the choice of developing agent. The popular combination of metol and hydroquinone can be used in all types of developer solution, from the energetic and contrasty document or process developer to the other extreme -the slow, soft working fine grain developer. The most important condition governing the type of developing action is the pH-or degree of acidity or alkalinity-of the solution. The Effect of pH In general, the developing solution must be alkaline for .the efficient reduction of silver halide, and this table illustrates the way in which developer type and pH are related. pH
VALUES OF DIFFERENT DEVELOPERS

presence of a strong alkali. In fact, Levenson and Frotschner consider it questionable whether hydroquincne will develop at all unless a catalyst is present; but in the presence of air and strong alkali, oxidat~on products are formed which are suitable catalysts. Metol is a very effective agent for activating hydroquinone, and this action will be discussed later. It is immaterial whether a large quantity of a mild alkali or a small quantity of a strong alkali is used, provided the pH is correct. In practice, however, it is usually desirable to use as large a bulk of alkali as possible, as this results in a better buffered developer. That is, the developer will be less sensitive to the addition of acids or alkalis, and inaccuracies in the amount of alkali added will be less serious. The change due to the acid liberated during development will be minimised. The alkalis in general use at present, in order of descending pH are: sodium hydroxide (caustic soda); sodium phosphate, tribasic; sodium carbonate;. amn:onium hydroxide; sodium metaborate (Kodalk); sodium bib orate (borax). Sodium sulphite has a slightly alkaline re~ction and in some fine-grain developers it serves as an alkali. It also has a very good buffer action when use~ with stronger ~lkalIS. rganic amines (e.g., triethanolamme) are occasionally suggested as mild alkalis. Potassium salts are n:equently included, but offer no advantage apart ~rom increased s lubility which permits a higher concerrtrat ion to be used. It has been stated that the presence of both sodium and potassium ions in the developing solution reduces fog, but there is no general acceptance of this statement. Sodium Sulphite Our simplest developer, then, is a soluti?n in. water of .a d vcloping agent with sufficient .alkah to aC~lva~eIt; but this c1 v I per will be of little practical use,. as It .WIlll?e unstable :~IIUinefficient. The main reason for instability IS that the nolution will quickly absorb oxygen. from t~e ai~, which will oxidiso the developing agent. ThIS reaction IS known as uu loxidation. * Although many organic and inorganic reducin r agents such as hydroxylamine, sodium formaldehyde
Tho term' autoxidation' is, strictly s~aking,. incorrect, It is, however, con .. y III ru to use it for oxidation by the air, to differentiate this re~tlOn fr<;>ID normal the ",Idllli n of a developing agent during use-e-oxidation by Sliver halides.

Caustic Process Developer M.Q.-Carbonate Print Developer M.Q.-Bora;x F.G. Negative Developer Metol or P.P.D. Extra F.G. Developer) Amidol Print Developer Acid Amidol ' Depth' Developer

r'

10.5-11 10.0-10.3 9.2 69-90

Amidol is the only common developing agent which can be used in acid solution, and-then only in special applications. Metol is next on the list, and can be used as a low contrast fine grain developer at a pH of 6.9," but development is slow and there is some loss of emulsion speed. Hydroquinone when used alone in the developer will only reduce in the

52

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53

sulphoxylate, cyclohexanone- and even hydroquinone are used in special developers, sodium sulphite, because of its many advantages, is used exclusively in black and white developers. Apart from technical advantages, the low price of sulphite cannot be overlooked from the user's point of view. A small quantity of sulphite will reduce the autoxidation rate greatly. For- example, one part of sulphite to twenty parts of metol in solution is sufficient to reduce the rate of oxygen absorption to one-tenth.' An increase in concentration will not reduce the rate appreciably, but as the sulphite is itself oxidised, a very large excess is usually included in any developer which is to be kept. Another advantage of sulphite over substances such as hydroxylamine, is that it is too mild a reducing agent to have any reducing effect on the photographic emulsion. The reaction between hydroquinone-which we will take as a typical developing agent-and silver bromide can be represented by the equation

It is in this role of a remover of development oxidation products that sodium sulphite fulfils its second function in the developer. It converts the quinone (or other oxidation product) to a stable, unreactive sulphonic acid salt:

6
o
quinone

+ H,O + No,SO, ~

6
. OH
sodium
hydroquinone

S~No

'
+NaOH

water

sodium sulphite

sodium

hydroxide

sulphonate

hydroquinone

silver

quinone

silver

hydrogen
bromide

bromide

The double arrows indicate that quinone and hydrogen bromide will, under certain conditions, convert silver to silver bromide. As the reaction which we wish to take place is the reaction to the right we must avoid conditions which make the reaction go to the left. Without outside influence the reaction would, as we say, reach an equilibrium with some of the silver bromide reduced, and some in its original state. As our reaction takes place in an alkaline solution, the hydrogen bromide (or hydrobromic acid) will be quickly neutralised. But this alkaline solution will cause the quinone to react to form undesirable complexes, which stain the gelatin and tan it, in addition to restraining development.

The term 'unreactive' just used is, of course, relative. Although under normal conditions of temperature and pH most of these sulphonic acid salts will not act as developers, sodium metol sulphonate will develop to some extent, but the activity is low compared with metol. The reaction between quinone and sodium sulphite is rapid, and is effective in keeping down the quinone concentration. Our development reaction can then proceed smoothly to reduce the silver bromide. The third important function of sulphite in the developer is that of a silver halide solvent. For a developer to function at all silver ions must be present. They may be the ' interstitial ' or wandering silver ions of the halide crystal lattice, or they may be present in the solution. Silver halides are normally considered to be insoluble in water, but they do dissolve slightly and dissociate to give a solution containing silver ions:
Ag Br
silver

Ag+
sil v er ion

Brbromide
ion

bromide

For the silver ion to become a silver atom, its positive charge must be neutralised. It must acquire an electron.
Ag+
silve r
ion

Ag
silver
atom

electron

S4

BASIC PHOTOGRAPHIC

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SS

The developing agent also ionises in solution:

(5
OH
hydroquinone quinone ion

hydrogen
ions

ions for the' physical' reaction will be inadequate, while the supply of interstitial silver ions 'within the crystal would be limited by, among other causes, the rate at which bromine atoms could escape from the crystal. Other more powerful solvents than sodium sulphite are occasionally used, such as ammonia, thiocyanates, and even thiosulphates. If too many silver ions are in solution the protective action of the gelatin will be overcome, and silver atoms will be deposited more or less evenly throughout the emulsion layer. TIllS deposition of silver where there has been no light action is called fog, and we have already discussed some of its causes in the chapter on emulsions. Reduction of Fog

and ~ we see from the equation, the developing agent ion is negatively charged. It is a donor of electrons. V!e ~ave, then, a s~stem of ions with opposite charges, which IS u~stable. If It were not for the protective action of. t~e gelatin, all of the silver grains would be reduced indiscriminately, The gelatin slows down this reaction to such a~ extent that unless the developer is too energetic the grains WIth no development centres will not be reduced. As we have :,aId p~evlOusly, there are many attempts to explain the way III which the dev~lopmen~ ce~tres work, but it is generally accepted that theIr function IS to accelerate this reduction and overcome the protective action of the gelatin. The unstable system then becomes stable:

0-

0
0quinone ion

+ 2AS +

-- 0
0
quinone molecule

+ 2Ag

silver
ions

silver
atoms

and

H+
hydrogen
ion

-I-

Brbromide ion

.....>.

...-

HBr
hydrogen
bromide molecule

. This explanati~:m shows that an adequate supply of silver ions must be available. If no SLIverhalide solvent is present the development process will proceed very slowly, as water Itself has such a slight solvent action that the supply of silver

The amount of fog which can be tolerated depends on the use of the emulsion. In developing negatives it is usual to tolerate a fog density up to 0.2 in order to keep the maximum speed of the emulsion. In the first development of a reversal process the fog is often greater, as a large amount of solvent is used to make sure that all of the exposed grains are developed. As this first image is always removed, the fog is unimportant, providing it is not so high that the reversal image is reduced in density. With printing materials, however, it is essential that there is no visible fog as this would reduce the brilliance of the highlights. The low pH fine grain developers do not develop an objectionable amount of fog for negative work. But for print making, and where more vigorous negative developers are used, a fog reducing agent must be included in the developing solution. The high pH developers will overcome the protective action of the gelatin more readily than the less energetic developers. Since the earliest days of the use of alkaline developers it has been customary to add a soluble bromide to the developer, to reduce fog. The presence of potassium bromide not only increases the strength of the protective sheath around the grain, and therefore tends to restrict the access of the developer, but also suppresses the ionisation of dissolved silver bromide and so reduces the rate of 'physical' development. Unfortunately the bromide does not restrict its action to the unexposed grains, but also hinders the development of the grains containing development centres. It is for this

56

BASIC

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THE

DEVELOPMENT

PROCESS

57

reason that the fog developed by negative developers is tolerated. The fog could easily be reduced to a negligible amount, but it would be at the expense of emulsion speed. When prints are made the loss in speed is relatively unimportant, and is willingly sacrificed to obtain minimum fog. Also we find that the emulsions which are used for print making are not in themselves so liable to fog. Of recent years other' antifoggants' than bromides have been more extensively used. They have a similar structure to the emulsion stabilisers previously mentioned, and their action is also similar. The best of these materials have the advantage over bromide that for a given degree of fog reduction their effect on the latent image is less. When stale bromide paper is used-sometimes unavoidable in the amateur darkroom-these compounds are especially valuable in reducing fog due to bad storage. Compounds suitable for this purpose are heterocyclic nitrogen or sulphur organic compounds such as 6-nitro-benzimidazole and 2-mercaptobenzthiazole. There are innumerable materials for this purpose described in patents taken out by the photographic material manufacturers in recent years. Some of these compounds such as chlorobenztriazole, some quinoline derivatives, and quinine will modify the image colour to blue-black. The effect is not entirely predictable, for in one recent patent it is claimed that a 4-hydroxy quinoline will modify the image colour to warm black. 6 Some of the other developer additions which are intended to increase the development rate will be described in connection with their main application-s-colour development. The Metol-Hydroquinone Developer

therefore oxidised. The metol oxidation product reacts with sulphite very slowly, but reacts with hydroquinone much more rapidly. The metol oxidation product is regenerated to metol, the hydroquinone being oxidised. The oxidation product of hydro quinone then reacts quickly with sulphite and is removed as the sulphonate. Developer Types Although a great deal of information on this subject is available in books and almost every issue of popular photographic magazines, some of the normal developer types will now be examined with reference to the points already discussed, starting with the most energetic developers-the process solutions. The main requirements are the maximum possible contrast and freedom from fog. As:the process emulsions have inherently fine grain and high resolving power, no emphasis on these points is necessary when compounding the solution. The main points require a high pH solution with a relatively high quantity of restrainer. Owing to the high pH the mixed solution will not keep under normal conditions, and it is therefore usual to prepare two stock solutions containing the developing agent and preservative, and the alkali and restrainer respectively. To ensure rapid development and good tone separation the quantity of developing agent is normally high. The sulphite concentration is not critical, for, as we have seen, in its use as a preservative a high concentration is unnecessary. The other function of the sulphite in this :type of solution is the removal of developer oxidation products, and here again a moderate sulphite concentration is adequate. Hydroquinone is the developing agent normally used in process developers, as it is very efficient at high pH values. A developer recipe which fully illustrates these characteristics is Kodak D.153. For the purpose of these illustrations, working solution recipes will be given throughout, although in many cases concentrated or two-part stock solutions are used. D.153 Hydroquinone 12.5 gm Potassium metabisulphite 12.5 gm Potassium bromide 12.5 gm Potassium hydroxide 25.0 gm 1 litre Water to

It was mentioned earlier that metol is an efficient activating agent in a hydroquinone developer. This effect has been thoroughly investigated by Levenson.! The majority of his paper is devoted to the results, both to the image and to the solution, of varying the concentration of the individual components of the developing solution. He found that if the pH of his solution were below 9.2, hydroquinone was ineffective in the absence of metol. But the presence of hydroquinone in a metol developer even at this pH was effective in increasing the development rate. He proposed the following explanation. Metol is the active agent in reducing the silver halide, and is

58

BASIC PHOTOGRAPHIC

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59

For high, but not extreme, contrast, many of th.e proc.ess characteristics are retained, but a carbonate alkali ill high concentration replaces the hydroxide. This gives a high contrast developer which is used for contin~ous tone. pr?cess work as well as for X-ray, aerial, and techmcal applications. The absence of halftone--desirable in linework and pbotomechanical reproduction processes-would in the~e cases be a disadvantage. A further advantage of this type of developer is that -it will keep fairly well in a tank. Kodak D.19b is a high contrast solution, and has, as would be expected, high concentrations of develop~g agents and bromide, as well as alkali. The use of metol with the hydroquinone is advantageous at its lower working pH. D.19b Metol Sodium sulphite (anhyd.) H ydroquinone Sodium carbonate (anhyd.) Potassium bromide Water to ... 2.2 72.0 8.8 48.0 4.0 1 gm gm gm gm gm litre

The general purpose developers fall into the next group. They are used at varying dilutions for different materialsthe more concentrated solutions, used for contact papers, differ only slightly from the previous group. The ~rincipal difference is in bromide concentration. Slow emulsions are inherently less foggy than negative materials, therefore the bromide can be reduced. At dilutions suitable for enlarging papers and negatives, the reduction in. energy of the developer is sufficient to make the low bromide content adequate. Kodak D.163 is a popular general purpose developer. D.163 Metol Sodium sulphite (anhyd.) Hydroquinone Sodium carbonate (anhyd.) Potassium bromide Water to Contact Papers 1.1 gm 37.5 gm 8.5 gm 32.5 gm 1.4 gm I litre Bromide Papers and Negatives 0.55 gm 18.75 gm 4.25 gm 16.25 gm 0.7 gm lItre

efficiency at lower pH values. These developing solutions are not suitable for paper developm.ent as .they do ~ot produce images of good colour, or of high maximum den~lty unless the development time is protracted, w~en the li~elihood of fog and stains is increased. D.61a is a ne~ative developer recommended for use in deep tanks. It will be noted that the metol-hydroquinone ratio is I to 2 compared with about 1 to 8 for D.163. The sulphite-carbonate ratio of 7t to I is aiso very different from the D.I?3 ratio of lit~e more than 1 to 1. The still lower workmg pH of this developer, which reduces the development rate, enables a lower bromide content to be used. D.6Ia Metol 0.75 gm Sodium sulphite (anhyd.) ... 22.2 gm Sodium bisulphite 0.5 gm Hydroquinone 1.5 gm Sodium carbonate (anhyd.) 3.0 gm Potassium bromide 0.4 gm Water to ... 1 litre The sodium bisulphite in this recipe is presumably used to give a better buffered solution, as the alkali content is so low. Fine Grain Developers The developing solutions with a lower pH than D.6Ia generally fall, with the exception of amidol developers, into the class known as fine grain developers. The developed image consists of much larger grains than those of the unexposed emulsion. It has been suggested' that the heat produced by the reduction of silver halide to silver, is sufficient to cause local disruption of the gelatin surroundmg the individual grains. This allows individual grains to move slightly and to form ' clumps' of metallic silver which give the image its grainy appearance. If this theory is correct, then a reduction in development rate would also reduce the rate at which heat is generated. This would permit the heat to be dissipated more easily and prevent local high temperatures, which in turn would reduce the clumping of grains, and therefore the graininess of the developed image. Other factors alter graininess, but the rate of development is the most important. Even the energetic high alkali developers will produce finer grain if they are dil.uted by upwards of ten times, with increased development times.

The non fine-grain negative developer normally has an even lower content of all substances except sulphite, and the metol-hydroquinone ratio is higher to ensure development

60

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61

The usual way to compound a fine gr~in developer i.s, however, to reduce the activity by reducing the pH still further. This necessitates a change of alkali as D.61a with only 3 grammes per litre of carbonate is 1;11e low limit for a carbonate developer. With less carbonate the developer would probably be unstable. Borates are frequently used, in conjunction with high sulphite concentrations. These solutions have adequate stability. Not only does' the high sulphite concentration assist in producing a well buffered solution, it also increases the solvent power of the solution. This appears to be desirable for fine-grain developers aajhe developing rate is increased , without increasing the grain size. The solvent action is, of course, very slight in comparison with a fixing bath. Too high a solvent action would give low image density and high fog. Semi-fine grain developers of the M.Q. Borax type are' published by most of the sensitised material manufacturers. They are usually based on the original Kodak D.76 recipe formulated by Capstaff : D.76 Metol Sodium sulphite Hydroquinone Borax Water to
2 gm

D.23 and D.25 are the latest solutions devised by Crabtree and Henn at the Kodak Research Laboratories. D.23 is the simplest developer yet recommended for general work, D.23 Metal Sodium sulphite Water to ... (anhyd.) 7.5 gm 100 gm 1 litre

and is an excellent compromise between fine grain ::ud .high emulsion speed. It produces negatives with clean hlghl~gh~ and apparently higher contrast than normal. ThIS ~s because of the long straight-line part .of the ~h~racteTl~tic curve, which does not flatten off at high densities to grve the poor highlight tone separation characteristic of many fine grain developers. D.25 is a lower pH developer of tlle. same type, but here the loss in emulsion speed must be considered when making the exposure. D.25 Metol Sodium sulphite (anhyd.) Sodium bisulphite Water to ... 7.5 gm 100 gm 15 gm 1 litre

(anhyd.)

100 5 2 1

gm gm gm litre

Other more recent Kodak developers which give finer grain. at the expanse of emulsion speed are DK.20, D.23, and D.25. DK.20 uses the proprietary alkali Kodalk (sodium metaborate) .and the inclusion of a small quantity of thiocyanate augments the solvent action of the sulphite, but also increases fog to some extent-hence the inclusion of potassium bromide. DK.20 Metal Sodium sulphite (anhyd.) Kodalk Potassium thiocyanate Potassium bromide Water to 5 gm 100 gm 2 gm 1 gm 0.5 gm 1 litre

D.25, to develop with sufficient energy for practical purposes, must be used at 25 deg. C. The extra exposure needed with these developers varies to some extent with the emulsion used, but for DK.20 about half a stop extra is recommended, and for D.25 about one stop extra. In practice DK.20 can be used with J?-0rma~y exposed film as the latitude of modern emulsions WIll e,\slly accommodate this very slight underexposure. D.23 gives the normal emulsion rating, although laboratory tests show that there is a loss of speed, but so slight that the average shutter and diaphragm calibration inaccuracies exceed it. Although all the developers quoted are from the Kodak range, it has not been the writer's intention to bias the reader towards developer recipes originating 'in the Kodak Laboratories. They were selected merely to illustrate the dev~loper types which can be prepared using metol and hydroqumone as developing agents. The majority of the larger manufaclurers publish a similar comprehensive range of developer recipes.

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Other Developing Agents It has already been stated that the use of developing agents other than metol and hydroquinone is very restricted. The figures are, presumably, based upon total usage, .th~ ma;iority of which is in the motion picture and photo-finishing industries. When individual treatment, as against mass production, is the rule, special developers. to meet individual requirements are frequently used. Fine grain and paper-print developers often specify developing agents other than metol and hydroquinone. Objectively, there may be no advantage over the developer types quoted above, but as the small user will have no scientific method of assessing the efficiency of a developer -if indeed such a method exists-his preference may lie in the direction of the unusual in his choice of developers. Amidol is one of the most powerful developers known. Without the addition of alkali, a developer of the D.163 type can be prepared D.170 Sodium sulphite (anhyd.) Amidol Potassium bromide Water to

usually on unreliable information. Admittedly, these developers do frequently give fine-grain results-but usually at the expense of good gradation or emulsion speed. The writer's recipe for fine grain is an inherently fine grain emulsion and a D.76 or D.23 type of developer. Phenidone Developers In general, Phenidone can replace metol in all types of M.Q developers. The quantity, however, is much reduced compared with metol. The following universal developer illustrates this difference, and also the inclusion of an organic anti-foggant to reduce the objectionably high fog level which Phenidone developers give with some materials. It will be seen that the developer (which is given at bromide paper and negative strength) is not unlike the previously quoted D.l6.3 diluted for the same materials. . ID-62 Sodium sulphite (anhyd.) 12.5 gm Hydroquinone 4 gm Sodium carbonate (anhyd.) 15 gm Phenidone ... 0.125 gm Potassium bromide 0.5 gm Benzotriazole 0.05 gm Water to 1 litre The Ilford recommended recipe for a fine grain developer using Phenidone is also very similar to the corresponding M.Q Borax type. Again there is less Phenidone than metol, and whilst the sulphite, hydroquinone and borax concentrations are unchanged, the solution contains boric acid, to reduce the activity but still have a well-buffered developer, and bromide -an unusual ingredient in a low pH negative developer. Sodium sulphite (anhyd.) 100 gm Hydroquinone 5 gm Borax ... 2 gm Boric acid 1 gm Potassium bromide 1 gm Phenidone 0.2 gm Water to 1 litre Pyro Developers Whilst pyro developers for normal negative development do not have any particular advantage over M.Q developers, the staining type of pyro developer giving high contrast without

25 4.5 1 1

gm gm gm litre

which is suitable for negative and print development. Owing to its poor keeping qualities in solution, and its tendency to stain the hands-and anything else which comes in contact with it-the use of amidol is restricted to the occasional user. Amidol-developed prints usually have strong blueish black images which appeal to many users. As a negative develope~, amidol has no particular virtues. It does not develop particularly fine grain images, although the negatives are crisp in general appearance. Chlorhydroquinone is more expensive than its parent hydroquinone which it frequently replaces. It is somewhat more active, and does not suffer from one of the disadvantages of hydroquinone-great sensitivity to temperature changes. It is specified in some :fine grain developers and print baths, but generally its doubtful advantages do not justify the higher price. Glycin, p-phenylenediamine and o-phenylenediamine are usually used in the 'fancy' fine grain developers, about which there is always a great deal of controversy-based

64

BASIC PHOTOGRAPHIC

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PROCESS

therefore excessive graininess, and negatives, is of interest. Pyro Metol Potassium metabisulphite Sodium carbonate (anhyd.) potassium bromide ... Water to

useful for under-exposed 3 gm 2.6 gm 7 gm 18 gm 3.2 gm 1 litre

6, fore develop more fully, and give adequate shadow deta.' The distorted characteristic curve will result in poorer qualll for the majority of subjects. I~ Somewhat similar results can be obtained by dipping tb negative in a vigorous de:veloper for about a minute, Q I then leaving It undisturbed III a water bath for several minut~'1 repeating the process if necessary. Again the developrnent e.~, the dense areas ceases before development in the shadows ijtl to local exhaustion. II Physical Development Technique At one time extravagant claims were made in respect fine grain for physical methods of development. That'~ methods in which the image silver is provided by add' IS, silver salts to the developer, and depositing this silver on ~\ development centre, rather than reducing the emulsion sil" \ halide. A great deal of work on physical development"" el carried out by Odella and further developments were made;\ Baur and Imhof" and by Turner.'" } . The origin~l O~ell .method used an amidol developer a Furner's modification IS 111 the use of metol and hydroqUino:q which can be kept in solution, whereas the Odell fOTrn/' 'ailed for the addition of solid amidol immediately before 11Slq Th first step in this method is to prevent the elllu!.1 e, h lid from participating in the development process. It 'WOn stated earlier that a fixed emulsion containing a latent irn a~ could be developed, but as silver halide solvents also atl g the very fine photolytic silver deposit of the latent image Ih.k method is unreliable. Instead, a potassium iodide for~l I is used, which converts the silver bromide or iodobronjj silver iodide, which is not reduced in normal develop--, Physical Development Forebath Potassium iodide Sodium sulphite (anhyd.) ... Water to The time of treatment in this bath is from 30 second 3 minutes. The short time gives higher emulsion speed coarser grain. The finer grain obtained with the largel mersion is at the expense of a reduction of emulsion 91 to one-fifth. The writer believes that in the case of the I immersion times, conversion to silver iodide is incon, I and some normal development takes place. The physical development working solution is obtaUtel1 diluting a stock hypo-sulphite-silver nitrate solution

Concentrated Developers tr ted developer contains Th most popular type 0 f concen a. . lk li e th d loping agent With a caustic a a 1. p_aminoph~nol as ~ eved d in the diluted solution and No appreClable fog IS pro uce . .' therefore bromide is omitted. A tYPical recipe IS . Stock Workmg Solution Solution 1 : 19 p_aminophenol ~Cl . ... 50 gm 2.5 gm Potassium metabisuiphite .. , 150 gm 7.5 gm 70 gm 3.5 gm d roxiid e Potassium hy 1 litre 1 litre Water to ... .,. ... 'f it is stored in The stock solution will keep for manYdyear~l ~ Ib~t once the ith bber bungs or waxe COl{ , full bott 1 WI ru 'd't es h uld be used fairly quickly otherbottle has been opene ISO wise it will deteriorate. Special Development Techniques . 1 dInt methods which have been Of the many S)?eCla. eve op:eare suitable for normal use, proposed at vanous~~;~thf~ethod. For this the developer except perhaps the rt containing the developing agents is split int? two ~a t;;-~~;er the alkali. The method is to and sulphlte an 1 ing agent solution-which is usually of a soak up the eve ?PI normal-into the emulsion, and higher concentrah0!l ~an lkali when it will be developed. then put tge .film l~fUe o~;ortunity for control of contrast,. as Thhet~eth? !~~~Sb~th can usually be varied within quite wI~de t e irnes in . 11 It' th result It has been sai limits without ~ras~f s~bjec~:mfhiS emethod will enable .the that for hars y 1 ed without blocking up the highs,hadows b~e;~~6p!e;~~~nt present in the emulsion ~Ii.ring lights. e. . tl lkali-is soon exhausted 1D the the developmg ~~~lo~~ne~~ s~ops, whereas in the light density ~~~~: f~:a~~~~loping agent is used less rapidly, and can there-

i~

66 adding the following: developing

TURNER-ODELL

BASIC PHOTOGRAPHIC

CHEMISTRY

THE DEVELOPMENT

PROCESS

67

agent

stock

solution
DEVELOPER

to

give

the

PHYSICAL

Metol 2.2 gm Sodium sulphite (anhyd.) 22'.0 gm Hydroquinone 4.5 gm Sodium hydroxide 4.5 gm Sodium thiosulphate 30.0 gm Silver nitrate. 3.0 gm Water to 1 litre Physical development is of academic rather than practical interest, but the method has been recommended where good tone separation is required. Forced Development Great caution must be exercised when assessing the sometimes fantastic claims made for special developers or developing techniques in respect of high emulsion speed. The effect of such treatment is not to increase the actual emulsion speed, but make an under-exposed negative-where the majority of gradations are on the flat toe of the characteristic curve-of a higher contrast suitable for printing. While this method of forcing development may give a printable negative when there has been gross under-exposure, it cannot be claimed that the quality of the print will be equal to that obtained by using normal exposure and development. A similar effect can also be achieved by using an intensifier such as quinonethiosulpha te. One way of working is simply to develop for a greatly extended time-with or without an increase in temperature. The inconvenience of this method is sometimes avoided in the the commercial 'high speed' developers by formulating a rapid working solution. The M.Q Borax and metol-sulphite fine-grain developers are frequently used for forcing development without too great an increase in grain. The characteristic curves show how the , extra speed' is achieved. In the figure, A is the characteristic curve of HP3 35-mm film developed in D.23 to a y of .8 which takes about 18 minutes. B is the curve of the same material developed to the yoo-about 1.2-of this material. This takes about one hour, Further development will produce only an increase in fog. The distance x represents the exposure range of a normal (32:1) subject; y represents the same subject, with

one-eight of the exposure given to x. Both the negative density ranges a-a' and b--b' will be about 1,0, but whereas the whole of the range x lies on the straight part of the curve, only the highlights of y will be on the straight line. The shadows will be on the toe. The resulting print, although of adequate density range, will have high contrast highlights and shadows with poor gradation.

2.

......

_-----..,. :t

The portion of curve A marked c-c' which will be obtained Ir m under-exposure and normal development will have a negative density range of only 0.6, and, in addition to having I he bad qualities of b-b', will not yield an acceptable print. '1he method therefore has its use in cases of unavoidable under-exposure. and it must be conceded that the harsh highliKhlS and blocked-up shadows may increase the dramatic quality of some subjects.

68

BASIC

PHOTOGRAPHIC

CHEMISTRY

Johnson's' Capitol' developer has the remarkable property that forced development does not produce extreme contrast, although the results are rather grainy if development is prolonged to obtain maximum speed. The constitution of Capitol is not known.

N.B .-The developer recipes included in the text are to illustrate the particular developer types. In some cases the worhing solutions quoted are not stable and more concentrated or even divided solutions must be prepared for storage.

Chapter 6

FIXATION

AND WASHING

REFERENCES Mees, C. E. K. Theory of the Photographic Process, pp. 305-328. Henn, R. W., and Crabtree, J.1. Photo Jour. 85B.: p. 109. Levenson, G. 1. P. Photo Jour. 89B.: p. 17. B.P. 626,998. 6 Mees, C. E. K. Theory of the Photographic Process p. 387. 6 B.P. 637,847. 7 Lowe, E. W.: What YOIl Want to Know About Developers, p. 71. 'Odell, A. F.: The New Photo Miniature, Vol. 2. Baur and Imhof: Kinotechnik, September, 1933. 10 Turner, P. K.: Brit. Jour. Phor., Vol. 85 (July, 1938), p. 405.
1
2 3

FTER development, the gelatin emulsion layer still contains unreduced silver halide, in addition to the silver image. If this were not removed, it would, on exposure 10 light-and particularly if the developer were not washed out -gradually darken. Development is usually followed either by a rinse in water, or treatment in an acid stop-bath. The purpose is the same in both cases-to remove, or render inactive, the developing reagents present in the emulsion layer. This prevents conlamination of subsequent treating baths. Rinsing requires no special explanation. The unused developer and the soluble- development by-products rapidly diffuse out of the gelatin layer. A very prolonged wash would be necessary to remove all traces of developer reagents, but a rinse of about one minute in running water is normally quite ad quate. Stop-Baths The stop-bath, on the other hand, prevents continued 1 velopment and contamination of the fixing bath by neutralising the alkali in the developer. Not only is 'further development prevented, but there is less discoloration of the gelatin clue to aerial oxidation of the developing agent. The pH of the stop-bath should be low enough to neutralise th alkali in the developer, but not so low that the emulsion is damaged, A pH value between 4 and 6 is normally used. Although a solution with this pH could be obtained by using i~ very dilute solution of a strong acid, this solution would be r pidly neutralised. What is required is a solution which is only slightly acid, but whose pH is not greatly raised by the addition of alkali. There are two ways of obtaining such a

solution.
In the case of a solution of a weak acid such as acetic acid, only a small proportion of the acid is present in the disHO iated form. As soon as alkali is added, which neutralises I h hydrogen ion, further molecules dissociate to maintain the It drogen ion concentration. So although only a little acid is

69

70

BASIC PHOTOGRAPHIC

CHEMISTRY

FIXATION AND WASIDNG BUFFERED ACETIC ACID STop-BATH

71 10 .cc 25 gm 1 litre

present in an active form, there is a large reserve of. acidity ready to restore the pH as the active. form is ?eutralised. . Buffer solutions, and acid salts such as sodium bls~lphate and potassium metabisulilh.ite, f~lfil a similar purpose in providing a large reserve acidity without having a strongly acid solution. When thick emulsions are being processed (negative, X-ray and colour materials) the stop-bath used after a carbonate developer should not be too acid. If it is, then the. carbon dioxide evolved when the carbonate is neutralised Will form bubbles instead of dissolving in the solution and then diffusing out of the film. With. a milder stop-bath .the neutralising action of the stop-bath Will be slower, .allowmg some or t.he alkali to diffuse from the layer before it IS neutralised. Carbon dioxide is sligh tly soluble in water, and the slo~er rate. of generation of this gas permits It to diffuse out in solution before it forms bubbles. A brief rinse between developer and stop-bath will also help to prevent bubbles by removing part of the alkali. .' When developers using phosphate alkalis are used, either acid phosphate or citric acid stop~baths must be used or a scum will be formed on the emulsion. If a phosphate stopbath is used, a short wash is necessary before fixation for the same reason. For black-and-white work a solution of acetic acid is commonly used for a stop-bath. SB.I Acetic acid (glacial) 17 cc Water to 1 litre For a hardening stop-bath, a solution of ch:rome alum is affective and cheap, although chrome alum solutions once used will not keep well.
c

Acetic acid (glacial) Sodi urn acetate (cryst.) Water to

Fixation Whilst a stop-bath or rinse, though desirable, is not absolutely necessary, it is essential to remove the residual ~alide from the emulsion if permanent results are to be obtained. * Many substances al'e known which will dissolve silver halides -alkali thiosulphates, thiocyanates and cyanides, thiourea, thiosinamine, potassium iodide and ammonium hydroxide. In practice, however, only the thiosulphates and cyanides are normally used. The other materials are either too slow in their action or they soften the gelatin excessively. The alkali metal cyanides are excellent fixing agents, but as they are extremely poisonous they are not normally used, except in process laboratories where iodide emulsions are ~sed. Silver iodide does not dissolve easily in thiosulphate solutions, and so iodide emulsions fix very slowly in ordinary fixing baths. Cyanides on the other hand are good solvents f.or silver iodide and fix iodide emulsions quickly. Another disadvantage of cyanides as fixers is that they attack the silver image-particularly the low densities. For line work t~is is unimportant and may even be an advantage, but the quality of continuous tone work would suffer if the low densities were removed. This leaves the thiosulphates as the only practical fixing agents. The Thiosulphates as Fixing Agents Sodium thiosulphate-commonly known as ' hypo '-is used for all normal photographic fixing. It is an efficient silver halide solvent, and is both cheap and innocuous. The .unmonium salt is sometimes used where speed of fixing is of paramount importance, but higher cost and Instability preclude its more general use. The old theory of thiosulphate fixation was based upon the assumption that first the sparingly soluble silver thiosulphate was formed: tho 'lOt Iho Recently Kodak have taken out patents which describe methods of stabilising silver halide WIthout actually removing It. As the reagents which are used are harmful to the image. the long wash which is usually necessary to remove hypo from the emulsion is avoided.

SB.3

30 gm Potassium chrome alum I litre Water to When a less vigorous stop-bath than plain acetic acid is required sodium or potassium dihydrogen phosphate can be used.
AGFACOLOR STop-BATH

Potassium dihydrogen phosphate ... Water to or alternatively the plain acetic acid bath with sodium acetate,

50 gm I litre can be buffered

72 2 Ag Hal
silver

BASIC PHOTOGRAPHIC

CHEMISTR

lllXATION

AND WASHING

73

-I-

Na2S.O.
sodium

Ag.S.os
silver

-I-

2 Na Hal
sodium

halide

thiosulphate

thiosulphate

halide

In the presence of excess thiosulphate, double salts of sodium and silver thiosulphate were then assumed to be formed, Ag.S.O. + Na2S20. ~ Ag2S.03 Na.S.03 Ag.S.O a : Na.S.03 + Na.S.03 ~ Ag.S.03 2 Na.S.O. and so on, whose solubility increases as the ratio of sodium to silver thiosulphal.e increases. More recent work, however, has indicated that the solvent action is more likely to be due to the formation of complex salts. In these salts the silver is present in the complex cation, and therefore does not form silver ions in solution. There is strong evidence to show the existence of several of these argentothiosulphate ions(AgS.os)-' (Ag[S.osJ.)- - -, (Ag[S.oSJ3)- - - - The sodium salt of the monobasic ion is only slightly soluble in water, but the salts of the polybasic ions are readily soluble. Completion of Fixation Although the above equations indicate that thiosulphate solutions should dissolve a large quantity of silver halide, in practice it is not possible to utilise more than a small part of the potential solvent action. Not only does the fixing time increase greatly as the concentration of silver in the solution rises, but the presence of appreciable quantities of silver salts can cause other troubles. If the concentration of silver salts is above a certain limit (depending on the constitution of the bath and the material being processed) the silver salts will become adsorbed either by the silver grains, the gelatin, or the base material, if this is permeable. The result is, that although there is no usual indication of the presence of silver salts in the emulsion, they are present and are not removed by washing. On storing, the clear portions become discoloured due to the reduction of the complex silver salts, and the liberated thiosulphate attacks the silver image. The usual rule of thumb for negative fixing is to allow the emulsion to remain in the bath for twice the clearing time. This is a very practical rule. 'When a fresh bath is used the negative can be removed from the fixer as soon as all cloudiness disappears. But as soon as any appreciable concentration of silver salt is present, a longer time is necessary.

With papers, the olearing time cannot be noted, and an arbitrary fixing time is chosen. This is many times longer than the clearing time. Paper fibres absorb silver-containing salts very readily when the silver concentration is high. Obviously, the solution which is present in the emulsion layer during fixation does contain a higher proportion of silver than the bulk of the fixing bath. At this concentration, the paper would retain considerable quantities of silver salts, resulting in rapid fading and discoloration. But if the emulsion is left in the fixing bath, most I these salts containing a lot of silver will diffuse out of the mulsion and the paper, and will be replaced by salts containing less silver. These latter salts can be removed by washing. The surest way to ensure complete fixation-apart, of course, from the extravagant use of a fresh solution for each negative or print-is to use two fixing baths. The first bath converts the silver halide to thiosulphate complexes and removes the bulk of them from the emulsion. It can contain a much higher proportion of silver salts than a normal single-bath fixer, as the material is then transferred to a comparatively fresh second bath. As this second bath never has to remove more than n. very small proportion of the silver salts, its silver con centrat ion is always low. It can, therefore, remove the last traces o( silver salts, or at least convert them to a form which can b easily washed out. When the first bath is discarded, it is r placed by the second bath. A fresh solution is then used for t he second bath. In addition to being very efficient, the twobath method uses far less thiosulphate than the single-bath method, as the discarded solution-the first bath-can conlain at least two or three times the silver concentration of a single-bath solution without giving trouble. Fixing Bath Additions Even when a rinse or stop-bath is used, small quantities of developer are bound to be carried into the fixing bath. A plain thiosulphate fixing bath will rapidly become discoloured. There are two causes of this. Firstly, the developing agents will be oxidised rapidly as the concentration of preservative is very low, and secondly, the sodium argentothiosulphates are slowly reduced to colloidal silver by developing agentsoven in a neutral solution. Both causes of discoloration an be prevented by acidifying the fixing bath.

74
The majority of acids thiosulphate solutions :acid

BASIC PHOTOGRAPHIC

CHEMISTRY

nXATION

AND WASHING

75 Fixing Baths

will

precipitate

sulphur

from

Hardening

SPa - thiosulphate
ion

--+

SO. - sulphite
ion

S
sulphur

Sulphurous acid does not decompose thiosulphate and is therefore the acid' which is used for this purpose. It is added as an acid sulphite as sulphurous acid itself is not stable. Sodium or potassium metabisulphites are commonly used. These react with water to form bisulphites Na2SZOS

Hp
water

--+

2 Na HSOa
sodium bisulphite

sodium metabisulphite

which in solution can exist as a mixture and sulphurous acid :2 Na H~Oa ~ NazSO.

of normal sulphite HZS03

Another convenient way to produce sulphurous acid which is frequently used is to acidify a solution of sodium sulphite with a weak acid (usually acetic acid) Na2SO. -I- CHa CO . OH the bisulphite
-?;

The majority of developing solutions are alkaline, and therefore soften the gelatin. A hardening step is therefore desirable in the processing procedure. As some of the hardening agents function efficiently at the working pH of the acid fixing bath, they are often included. Chrome and potassium alums are the usual hardeners. Potassium alum is the more frequently used as it is more reliable, but chrome alum is a better hardener. Fresh chrome alum baths are purple by transmitted light. Heat or age may turn them green when they do not harden, but old solutions may not harden even though they are still purple. Potassium (or potash) alum is colourless, and is not affected by heat or age to the same extent. A chrome alum fixing bath which is recommended for use in hot weather is KODAK F.16 Sodium thiosulphate (cryst.) 240 gm Sodium sulphite (anhyd.) ... 15 gm Potassium chrome alum 15 gm Sulphuric acid (concentrated) 2 cc Water to . 1 litre The chrome alum and sulphuric acid are kept separate from the hypo and sulphite until the solution is required, as the working solution keeps for only about a day. When potassium alum is used as a hardener, it is convenient to add a concentrated acid hardener stock solution to a plain hypo solution. KODAK F.53 Sodium sulphite (anhyd.) 50 gm Acetic acid (glacial) 75 cc 100 gm Potassium alum 1 litre Water to '" ... This solution is added to a plain hypo solution in portion of 50 cc to each 100 gm of hypo, giving a solution :Sodium thiosulphate 240 Sodium sulphite (anhyd.) 6 Acetic acid (glacial) 9 Potassium alum 12 1 Water to '" the proworking gm gm cc gm litre

CH s : CO . ONa -I- NaHS03 acid.

in turn yields sulphurous

An acid fixing bath is somewhat slower in its action than a plain fixer, and in addition the safe 'limit of silver concentration is lower. But in practice, a plain fixing bath becomes discoloured long before the silver content becomes high enough to cause trouble. The life of the acid fixer is, therefore, greater. Typical of non-hardening acid fixing baths is:-

KODAK

F.52 250 gm 25 gm 1 litre

Sodium thiosulphate (cryst.) Potassium metabisulphite Water to

76

BASIC PHOTOGRAPHIC

CHEMISTRY

FIXATION

AND WASHING

77

Washing After fixation the film or paper must be thoroughly washed to remove the fixing bath reagents and any silver complexes . which have not diffused into the fixing bath. In the case of plates and film, whose base is non-absorbent, the operation is simple. Only the thin gelatin layer needs washing, and six minutes in running water is sufficient to reduce the thiosulphate concentration to about five parts in ten thousand -quite a safe figure for normal work. It is very important to change the wash water quickly. A large, deep tank is very inefficient as the water cannot be renewed quickly. A small, tank or a shallow dish in which the water can be rapidly circulated is best. It is better still if a spray of water is directed on to the emulsion and allowed to run to waste without having any sort of container. . If an efficient running-water washing device cannot be used, the best method is to drain and refill the tank or dish a dozen times, allowing each change of water to remain about half a minute. With papers, washing is more difficult. The fibrous paper base holds the salts much more strongly than does the thin gelatin layer. At least an hour in running water is recommended, but even this may be insufficient in the case of thick papers. If really permanent prints are required, then a hypo eliminator is necessary. Hypo Eliminators These are divided into two types-those whose action is mainly physical in releasing the salts from the gelatin or paper, and those which oxidise the thiosulphate to relatively harmless salts. Ammonia is the most common reagent in the first group, and hydrogen peroxide and potassium permanganate are useful oxidising agents. The permanganates have been used for many years, but they have the disadvantage that they stain due to the formation of manganese dioxide. Kodak recommend the use of a mixture of ammonia and hydrogen peroxide
KODAK HE.! Water Hydrogen peroxide (!O vol.) Ammonia solution (.880) Water to

The paper is washed for thirty minutes after fixation, then treated in HE.! for six minutes, and again washed for ten minutes. Hypo eliminators will only remove the last traces of hypo after a good wash, to ensure permanent results. They are not

a substitute for washing.

The importance of fixing and washing is often underestimated. Just as much care should be taken in these steps as in development, or the results will not be permanent.

500 cc 125 cc 9 cc 1 litre

INTENSIFICATION

AND

REDUCTION

79
2 AgCI

and the bleaching reaction is

2 Ag 2 Ag

K~Crp7 K2CrP7

2 HCI 2 HCI

-+ -+

2 KCrO.

+ HP +
HP

and not Chapter 7

2 AgCrOs

2 KCI

INTENSIFICATION AND REDUCTION

LTHOUGH intensification and reduction are normal practice in some process methods, in general these steps are used only to correct faults in negatives (and to a very small degree, in prints). There are three methods of intensifying an image : (a) changing the light absorption power of the silver image, (b) converting the silver to a more opaque silver salt, (c) adding material to the silver image. It is probable that the common chromium intensifier works to some extent, if not completely, by method (a); but most intensifiers actually add material to the image. In group (b) we have sulphide toner intensifiers, and in group (c) the silver and mercury intensifiers, and stain-image methods. Chromium Intensifier The silver image is bleached in a dichromate solution acidified with hydrochloric acid, and is then redeveloped. During the bleaching operation it is unlikely that the dichromate serves any purpose other than as an oxidising agent which breaks up the silver grain structure. There is no evidence that chromium metal or salt is deposited in situ with the grain, although the density increase is sometimes attributed to a chromium deposit." The disruption of the grain structure gives a more disperse image on redevelopment, which has greater light-scattering power than the original image, and therefore a higher density. Any normal developer can be used for the redevelopment stage. A typical chromium intensifier bleach is IN.4 Potassium dichromate 9.0 gm 6.4 cc Hydrochloric acid (conc.) Water to 1 litre
If the bleach solution is not thoroughly washed out of the emulsion. an overall-not imagewise--deposit of a chrorruum salt will be produced on development. This will give an increase in density. without affecting printing qualities -other than increasing prinung exposure.

Sulphide Intensifier The conversion of the silver image to a silver sulphide image is a useful, though not widely used, method of intensification. The silver sulphide image does not necessarily appear to be more dense than the original silver image, but owing to its brown colour, its printing density is greater. Mercury Intensifiers Although mercury salts are extremely POiSOllOUS, these intensifiers are very widely used. Two types are usedthe single bath and the two bath, the latter being more popular. A mercuric halide is the active bleaching agent
Ag

HgCI2

-+

AgCI

HgCI

'I

and is usually used in the presence of excess halide to ensure complete conversion to halide. The insoluble mixture of silver and mercurous chlorides is darkened with sodium sulphite, a developer, ammonia or silver potassium cyanide. In this order the intensification is progressively greater. The plain sulphite reduces all the silver chloride and half of the mercurous chloride, the rest of the mercury passing into solution. Developing solutions should give a denser image than plain sulphite solutions, but the writer has found that an M.Q. carbonate negative developer gives less intensification than a 10 per cent. sulphite solution. This is presumably due to the relatively high sulphite content of the developer, causing sulphite reduction to be predominant; but due to other factors--e.g., the low concentrations of active ingredients and the presence of bromide-reduction is not as complete as with 10 per cent. sulphite. The obsolete ferrous oxalate developer (recommended by Chapman Jones for permanent images) avoids the use of a sulphite-containing solution for blackening. This developer. reduces all the silver and all the mercury. Ammonia darkens only the mercury salt and gives an opaque image of silver chloride, mercury, and the compound Cl-HgNH3 whieh is rather unstable. The silver potassium cyanide also gives a very dense complex image.

78

80

BASIC PHOTOGRAPHIC

CHEMISTRY

INTENSIFICATION

AKD REDUCTION

81

The normal typ~ of ?1ercury intensified image -Ag-Hg can be treated agam with the bleach to give :_
AgHg

2 HgCI.

-+
Ag.

AgCI.

3 HgCI

which when reduced gives

AgCI . 3 HgCI

-+

The single solution intensifiers give brownish images which are not stable. The solution consists of the mercury halide, xcess halide-usually potassium iodide-and sodium thiosulphate or sulphite, which reduces the insoluble salts as they are formed. Miscellaneous Intensifiers

3 Hg

This can b: bleached againAg . 3 Hg

4 HgCI

-+

AgCl.

7 HgCI

and so on.

A great many toning methods can be used to some extent as intensifiers, as the coloured images which they give are more opaque to printing light than the original image. The most popular of these methods is the uranium intensifier. This gives an image of uranium ferrocyanide which is reddish brown in colour. Details of this method will be given when we deal with toning. Lead intensifiers work on a similar principle, and produce very dense deposits of silver and lead ferrocyanides
4 Ag

l-

>-

2 Pb3 [Fe(CN)al.

-+

Ag,Fe(CN).

3 Pb,Fe(CN)a

v;
Z

o
I

LU

These salts are then darkened to give the silver and lead sulphides in 5 per cent. sodium sulphide. The degree of intensification is greater than for the mercury intensifiers, and the method is normally used only for line work.
, B.J.' LEAD INTENSIFIER BLEACH

Comparative

effect of some Common intensifiers on an HP3MQ.

Borax image.

Lead nitrate Potassium Ierricyanide Acetic acid (glacial) Water to

45 gm 68 gm 19 cc 1 litre

Frequently, the bleaching solution contains a soluble bromide, w.ith the mercuric chloride. This will give a bleached Image of silver bromide and mercurous bromide, which may be an advantage as these salts are less soluble than the chlorides and ri~k o~ image attack during the thorough wash afte; bleachl1:g IS reduced. The Kodak recipe for a mercury bleach IS

IN.!
Potassium bromide Mercuric chloride Water to 22.5 gm 22.5 gm 1 litre

Another possibility which has not been exploited to any appreciable extent, is to bleach the image to silver halide and then redevelop in a colour developer. The only requirement of the dye image is that it should be as opaque as possible to blue light. Many colour couplers which would be unsuitable for colour photographic work could be used. Some of the yellow couplers, which give images which are too orange or brown for three colour use, would be very suitable as intensiJiers. The stain image which is obtained with a sulphitefree pyrogallol developer has been suggested for intensification. Naturally the silver image is not removed as it is in colour work.

82

I NT!;NSIFICATION

AND REDUCTION

83

BASIC

PHOTOGRAPHIC

CHEMISTRY

The Quinone-Thiosulphate

Intensifier

Reduction The photographic reducer is, contradictorily, an oxidising I~cnt. It converts the silver image into either a soluble s~lt 01" into a silver salt which is soluble in a solvent, present In uithcr the reducing solution or in a separate ba~h. . Examples of the solutions which dissolve the SIlver directly II"' dichromate and sulphuric acid, or permanganate and ulphuric acid :10 Ag + 2 KMnO. + 8 H2SO. -+ K.SO. + 2 MnSO. + 5 Ag.SO. + 8 H.O Ccric salts with sulphuric acid behave in precisely the opposite way to ferrous salts used as developers. They lose an electron to ionise a silver atom and are converted to cerous salts of lower valency 2 Ca(SO.lo
eerie sulphate

This intensifier was investigated by Lumiere, and following work by Crabtree, was reintroduced by Kodak. In the paper- which describes the method of use, no mention is made of the constitution of the intensified image, but it appears to be composed of hydroquinone oxidation products, as it is soluble in an acid fixing bath. The degree of intensification produced in the low densities is extremely great, and results in a great apparent increase in effective emulsion speed. As one would expect, the increase in graininess is as great as the speed increase; but as normally unprintable negatives can yield satisfactory prints, this is tolerated. The working solution, which must be prepared by careful mixing of three stock solutions, has a life of only about 15 minutes, and contains IN.6 Sulphuric acid (cone.) Potassium dichromate Sodium bisulphite Hydroquinone Sodium thiosulphate Water to , Physical ' Intensifiers Solutions of a soluble mercury or silver salt, in tile presence of a developing agent and a weak acid or a silver solvent, are used as intensifiers. The metallic salt is reduced by the developer and the metal is deposited on the silver grains already present, which act as precipitation centres. The great advantage of these intensifiers is that their action can be watched, and stopped when the required density is obtained. The silver intensifier recommended by Kodak is mixed from four stock solutions to the working solution IN.5 Silver nitrate 10 gm Sodium sulphite (anhyd.) . . 18 gm Sodium thiosulphate (cryst.) 9 gm Metol 12 gm Water to 1 litre which keeps for only 30 minutes. Fixing in plain hypo after intensification is recommended with a thorough wash before drying. 7.5 cc 5.5 gm 1.0gm 4.0gm 5.5 gm 1 litre

2 Ag
silver

-+

Ag.SO.
silver sulphate

+ c-,

(SO.}.

cerous sulphate

A.sMees points out', the reactions of photogr~phic reducing olntions on the silver image have not been sufficiently studied. 1 he simple equations do not necessarily represent the exact IOllrse of the reactions. . Th reactions of the persulphate reducer have been st~dled Ily both Sheppard and Higson, who find that the SImple II l book reaction 2 Ag + (NH.).S.oa -+ Ag.SO, + (NH.).SO.
sllvcr
ammonium silver ammonium

persulphate

sulphate

sulphate

not a true representation of the reactio~ .. Their arguments III to involved for discussion here, but It IS sufficient to say Ih. L both workers come to the general conclusion that firstly t II( P 'l"sulphate ion is reduced and evolves atomic oXY!5e~. t h active oxygen attacks the NH. group. to form n.ltnc IIIIII. It also attacks silver to give the oxide .. The SIlver II Ide and nitric acid react to give silver nitrate and water. Photographic Effect of Intensification and Reduction

'I'll outline of the chemical reactions of intensification an.d I. cillt'lion which has been given, may indicate .that, their \I I il II is proportional. That is, that each density ~n the IIIflld lvc is increased or decreased by an amount directly ell pond nt upon the original density.

84

BASIC PHOTOGRAPHIC

CHEMISTRY

Those who have used these solutions, however, know that this is not strictly true. The main reason for this is the effect on the solution of the by-products, or simply exhaustion of the solution. In most cases these factors will tend to reduce the rate of reaction more in the dense than in the light areas. For example, if two Farmer's reducer solutions are prepared with different quantities of Ierricyanide, the solution with less ferricyanide will have a smaller effect on the high densities, due to local exhaustion and the restraining action of the byproduct, ferrocyanide. In the low densities where the solution will not be exhausted so rapidly, and where less ferrocyanide is formed, the reaction rate will be maintained longer. -Several of the intensifiers and reducers have a comparable action. The persulphate reducers are, however, affected in the opposite way. The dissolved silver accelerates the reducing action, so the reduction is greater in the high than in the low densities.

Chapter

,r

TONING

PROCESSES

HE most common way of altering the colour of a silver, image is to convert It to silver sulphide. ~he colour of a silver sulphide image varies from p~rplish black to dilly yellow, depending mainly On the phYSIcal state of the 01 iginal silver image. The colour of the l~age can also be tll( red by varying the composition of the.tomng ~ath, or baths. fully developed bromide pap~r print, whIch. has been Iltmoughly fixed and washe.d, will be co~ver~e~ .m a wellI'loportioned toner to a pleasing brown or sepia Image. Silver Salt Images The most convenient way of doing this is to conve.rt, the rlvcr image to an insoluble silver salt, and then treat It 111.a ulution of a soluble sulphide. There are many ways in whi h the silver image can be converted into .a sui?-bl~ silver rll , Normally a solution of potassium ferricyanide IS u~ed III oxidise the image, in the presence of potassium bromld.e whi h precipitates silver bromide. A typical bleach bath IS T.52 Potassium ferricyanide 50 gm I) tassium bromide 50 gm Water to 1 litre rt cr bleaching the print is washed to remove the. excess II III yanide and the ferrocyanide by~product, and IS then tOIlxl in a 1 per cent solution of sodium sulphjde. 'I'h reactions produced by these baths are Ag
liver

K3Fe(CN)s
potassium ferricyanide

+
2 sodium

KBr
potassium bromide

-+

AgBr

K.Fe(CN)e
potassium ferrocyanide

sbirlvoemr"de

2 AgBr
silver

Na S

-+

Ag2S
silver

2 NaBr
sodium

REFERENCES 1 Photographic JO"l'IIol, 1946, 8SB. Mees, C. E. K. The Theory of the Photographic

bromide Process, p. 546.

sulphide

sulphide

bromide

III LIl ry, any method of converting the silver image. to ,III 11l~ luble silver salt can be used. Among methods which 85

86

TONING BASIC PHOTOGRAPHIC CHEMISTRY

PROCESSES

87

have been suggested is to expose a damp print to the action of chlorine gas or bromine vapour.t-s-a method which is said to give excellent results, but which cannot be recommended as a practical procedure. Other oxidising agents which are used in solution are potassium permanganate with hydrochloric acid, potassium dichromate with hydrochloric acid, quinone and quinone sulphonic acid with an acid and a halide, and mercuric or cupric salts. Practical considerations are against many of these methods, as they are either unstable in solution, unpleasant to use, or expensive. The toning bath, on the other hand, is not nearly so stereotyped, and is capable of considerable improvement. Dilute sodium sulphide solution is not stable, and should not be used in the darkroom. A considerable amount of hydrogen sulphide is evolved, which, apart from being extremely unpleasant-s-even dangerous-will ruin any unexposed photographic materials. Toning solutions proposed by Triepel- which are odourless consist of an organic sulphur compound in strongly alkaline solutions. A suitable bath is : Thiourea 1 gm Sodium hydroxide .. 4 gm Water to 1 litre and the reaction with silver bromide :2 AgBr + (NH,hCS + 2 NaOH -+
silver thiourea sodium

silver halide solvent, or when the image is underdeveloped or incompletely fixed. The processing faults giving a fine grain image, or colloidal or soluble silver, can be prevented with care, but an inherently fine grain image has to be treated differently .. Direct Sulphide Toning The method used for fine-grain prints consists of reacting the silver image directly with sulphur. This can be done in several ways. The simplest, but least practical, is to boil a chloride print-well hardened of course-in water to which a little flowers of sulphur has been added. The print tones very slowly as the silver reacts with the sulphur. 2 Ag + S -+ Ag2S A more practical method is to precipitate sulphur directly in the gelatin in a molecular state of subdivision. The print is transferred directly from the fixing bath to a dilute solution of hydrochloric acid, when sulphur is precipitated: Na.SoG. + 2 HCI -+ 2 NaCI + S + H.SO.
sodium hydrochloric sodium sulphur sulphurous

thiosulphate

acid

chloride

acid

bromide

hydroxide

Ag.S
silver sulphide

(NH.).CO
urea

2 NaBr
sodium bromide

HoG
water

Most other substitutes for sodium sulphide are not odourless in dilute solutions, and some of them produce differently coloured images due to the precipitation of other substances in addition to silver sulphide. For example, sodium thioantimoniate gives an orange-brown image, as antimony pentasulphide is precipitated with the silver sulphide; and yellowish images are produced by polysulphides due to the co-precipitation of sulphur. When fine-grain emulsions such as chloride and chlorobromide papers are toned by this indirect method unpleasant yellowish images are produced, due to the silver sulphide being in a very finely divided state. The same fault also occurs when the paper or solution is contaminated with a

The sulphur remains in the gelatin when the by-products are washed out, and if the prints are left in a damp condition for twenty-four hours at normal temperature the sulphur and silver react, as in the previous reaction, to give a brown image. The normal toning method for chloride prints is the hypoalum method. In principle it is the same as the acidified hypo method, but is much quicker. The solution is prepared by precipitating some of the sulphur from a 20 per cent solution of sodium thiosulphate with about 4 per cent of potassium alum. The mixture is boiled for a few minutes and then allowed to cool to about 65 degs C when a small quantity of a soluble silver salt is added, followed by a soluble halide. The precipitated silver halide assists in producing the toned image quickly. The well-hardened print, which need not be thoroughly washed after fixing, is toned at between 50-60 degs C for about 20 minutes. As the bath contains a considerable proportion of solid matter the print should be wiped after toning, and then thoroughly washed. Fixing after toning has been suggested, to remove any silver salts which have been taken up from the bath. The hypo-alum method, and indeed any direct method,

/
88
BASIC PHOTOGRAPHIC CHEMIs-IRY TONING PROCESSES

89 Metallic Toning

usually gives a less yellow image than the indirect method. This is probably because the indirect methods alter the grain structure of the image to a much greater extent than do the direct methods. Other direct toning methods use alkali polysulphides, prepared by dissolving sulphur in a solution of a normal sulphide. The polysulphides readily part with the loosely attached extra sulphur atoms, which react with the silver image. A further method which has .been frequently suggested is to bathe the print in a sodium sulphide solution, and then transfer it, without washing, to an oxidising solution such as potassium ferricyanide. The sulphide is oxidised, releasing active sulphur, which reacts slowly with the silver. Selenium and Tellurium Toning

In the Chroma tone process for making three-colour prints (fully des~ribe8. in Making Colour Prints by J. H. Coote) the three Images are composed of a nickel-iron ferrocyanide for the blue-green, lead chromate or cadmium sulphide for the yellow and a complex nickel-organic salt for the magenta. These three methods cover the range of metallic toning processes and we will examine them separately. Metallic Ferrocyanides Some of the. insoluble m~t~llic ferrocyanides are brightly coloured when 111 a finely divided state, and the substitution of the silver image by these materials is, even for monochrome work, a popular toning method. A much wider range of colours can be. obtained than with sulphide toning methods. Most of th~ tonmg baths are compounded in a similar way, and compnse a.soluble metal salt, a soluble ferricyanide, and usually an acid and a buffer salt which prevents the precipitation of the metal ferricyanide. Among the metal ferrocyanides which are commonly used are:

Both of these methods rely on the properties of complex s~lphur-selenium and sulphur-tellurium salts to part readily ;'I'lth the selenium or tellurium, as in the polysulphide method Just mentioned. Selenium toning is a popular method, used either alone or together with sulphide toning. The bath is of sodium selenosulphite and is prepared by dissolving selenium powder in a boiling solution of sodium sulphite: Na2SO. + Se ~ Na2SSeO. The toning reaction is quite simple Na,SSeO. + 2 Ag ~ Ag2Se + Na.SO. . Tellurium does n~t dissolve in sodium sulphite, but is used 111 a sodium sulphide solution to form a solution exactly analogous to a polysulphide. S.elenium toning is frequently followed by indirect sulphide toning to convert any residual silver to sulphide. Very beautiful and .permanent results .can be obtained in this way, as the yellowish results sometimes obtained with indirect sulphide toning are avoided, and all the silver is combined with ~ither su!phur or selenium. The sulphides, selenides and tellurides of silver are much more resistant to chemical attack than the original silver image, and therefore the prints are more permanent . . The colours produced by all these methods are, as previously stated, from purple-black, through brown, to dirty yellow colour depending upon the factors noted. For brighter images and other colours different methods must be used introducing other metals in place of the silver. '

Metal
Copper Uranium Iron Vanadium

Image colour

Red brown to chalk red. Red brown-richer than copper. Blue-green. Yellowish-usually used with iron to give greens. Typical of these toners is the following copper toner: Copper sulphate 3.5 gm Potassium citrate (neutral) 28 gm Potassium ferricyanide 3 gm Water to 1 litre Two stock solutions are mixed just before use as the mixture is not stable, even with the citrate present. Without the citrate, copper ferricyanide would be precipitated immediately. The toning reaction is as follows: 4 K,Fe(CN).
potassium ferricyanide

2 CuSO.
copper sulphate

4 Ag ~
silver

2 Ag.SO.
silver
sulphate

Cu2Fe(CN)c
copper
ferrocyanide

3 K.Fe(CN).
potassium
(errocyanide

90

BASIC PHOTOGRAPHIC

CHEMISTRY TONING PROCESSES

With uranium and iron toners there is no tendency for the metallic ferricyanide to precipitate from the toning solutions, so the citrate is unnecessary. Two stock solutions are usually used to secure the best keeping properties, although the Kodak iron toner, T.l1, is a stable single solution toner, but its preparation requires care. T.ll Ammonium persulphate .. Iron ammonium sulphate (ferric alum) Oxalic acid .. Potassium ferricyanide Ammonium alum Hydrochloric acid (10 per cent solution) Water to 0.5 1.4 3.0 1.0 5.0 1.0 1 gm gm gm gm gm cc litre

91

Each of the solid chemicals is dissolved in a small quantity of water and these solutions are mixed in the order given. The solution should be pale yellow and quite clear. In the copper toner above, the silver image is dissolved away as the sulphate, but in solutions where a halide is present, or if the solution is made up in tap water containing halide, some, or all, of the silver will be precipitated as halide. This involves a further fixing step in hypo before washing and drying. Two-stage Methods In order to overcome difficulties due to unstable single toning solutions, two-stage methods are sometimes used, particularly with iron toners. The silver image is first bleached in a ferricyanide bleach, to which it may be necessary to add a little ammonia to speed up bleaching. On no account must a soluble halide be present, or the silver will, as in the first equation above, be precipitated as silver halide. TIm; gives an image of silver ferrocyanide. 4 K.Fe(CN)6
potassium ferricyanide

This two-stage method is limited in use to those cases where the metallic ferrocyanide in question is less soluble than silver ferrocyanide. The method used for the blue-green image in the Chromatone process is a modification of this method. The silver image is first converted to yellowish nickel ferrocyanide in the following unstable bath, which is kept as two stock solutions: Nickel nitrate 25 gm Potassium citrate 150 gm Citric acid .. 15 gm Formaldehyde (40 per cent sol.) . . 50 cc Potassium ferricyanide 15 gm Water to 1 litre After washing the print is treated for 5 minutes in 5 per cent ferric chloride, then in hydrochloric acid before fixing and drying. The colour of the image produced in this way is distinctly greener than that produced using a plain ferricyanide bleach, and probably consists of a mixture of nickel and ferric ferrocyanides. These ferrocyanide images, unlike the sulphide ones, are far less stable than the original silver image. They are all decomposed by alkalis, particularly the uranium and iron images. In these two cases even slightly alkaline tap water will decompose them, and it is often recommended that the wash water should have a little weak acid added to it, to avoid decomposition of the image. Other Metal Salt Images This replacement of the silver image by a metallic ferrocyanide is sometimes used as an intermediate stage in the production of highly coloured images composed of other insoluble salts. Many metallic ferrocyanides can replace the silver image, but are not suitable as final images because they are colourless or only slightly coloured. In some cases the ferrocyanide radical can now be replaced by another radical which will give a highly coloured image. For example, cadmium and lead ferrocyanides are relatively useless as final images, but can be converted to bright yellow salts by treating with sodium sulphide, and potassium dichromate respectively. Cd2Fe(CN). + 2 Na2S -+ Na.Fe(CN). + 2 CdS
cadmium (errocyanide sodium sulphide sodium ferrocyanide cadmium sulphide

+ +

4 Ag -+
silve r

Ag.Fe(CN).
silver ferrocyanide

3 K,Fe(CN)a
potassium ferrocyanide

[he silver ferrocyanide 3 Ag,Fe(CN)6

silver
ferrocyanide

is then reacted with ferric chloride. Fe,[Fe(CN).Js

ferric
ferrocyanide

4 FeCI. -+
ferric
chloride

12 AgCI
silver chloride

In this case, the silver chloride must be fixed out before washing to render the image permanent.

TONING

PROCESSES

92 Pb.Fe(CN).
lead ferrocyanide

BASIC

PHOTOGRAPHIC

CHEMISTRY

93

2 K2Cra07
potassium dlchromaee

-+ K,Fe(CN).
potassium, Ie r rocyanide

2 PbCr,07
I~ad dichromate

Another' way of using the ferrocyanide method of replacing the silver image with another metallic ion ~s to form a :netalorganic complex, again provided that this complex 1S less soluble than the metallic ferrocyanide. The most common way of doing this is, .like the. yellow images above, usually used only in colour prmt J?akir:g. It is to treat the nickel ferrocyanide image (obtamed.m the bleach given earlier) with a solution of the ammonium or sodium salt of dimethylglyoxime. Ni.Fe(CN).
nickel
ferrocyanide

4 Na[(CHa)..C a-N.OH.NO]
sodium dimethylglyoxime

-+

Na.Fe(CN).
sodium ferrocyanide

2 Ni[(CHa) Cs-N.OH.NO].
nickel dimethylglyoxime

This method yields image can be obtained the dimethylglyoxime method to obtain a red p-dimethylaminobenzal

a bluish-red image. An orange-red by using dibenzildioxime in pl~ce of (diacetyl dioxime). AnotI:er s1ml~ar image is to treat a copper Image WIth rhodanine. Dye Toning

For the production of extremely bri~liant colour~d images the easiest method is to dye-tone the Images. ThIS me~hod is normally used for the production of natur~l ?olour prints, but can be used in monochrome work for limited subJ~cts. Some papers may be badly stained by the dye solutl<;H1s used in this method, and if this is the case then the toning must be carried out using a temporary support, and subsequently transferring the gelatin layer which contains the image, to a final paper support. This may, also. apply to some of the toning methods given previously in this chapter. In the dye-toning process, the silver image is converte~ to, or replaced by, a substance which is capable of adsorbing= basic dyestuffs. Many such substances are known, an~ong them are the ferrocyanides and ferricyanides of valladm:TI, copper, silver and uranium; other salts su~h as copper thiocyanates (Namias' Mordant), lead, cobalt, tm, chromium salts
The dye is not absorbed as a sponge absorbs, wa,ter-'!dsorption is a physical bond between two substances which carry opposite electzical charges.

and silver iodide. This silver iodide is probably the most popular as it requires no complex or unstable baths; and the image, although yellowish, is not as highly coloured as the majority of the other mordants. It is also one of the most efficient mordants. The silver iodide mordant was first proposed by Traube in 1906,s and has been developed by other workers, notably Miller.' The main development by Miller was the use of a bleach bath containing a very large excess of potassium iodide over iodine, This does not yield the dense silver iodide image of the Traube bleach, which is granular and opaque, but a more or less transparent image consisting of a silver iodide-potassium iodide complex. The transparency of this image increases with increase in potassium iodide content of the bleach bath, but the solubility of the complex also increases. In extreme cases it is possible to obtain an image which is completely transparent, but unfortunately this is at the expense of sharpness, for the more transparent salt, being more soluble, diffuses from its original position in the gelatin. The Traube image, being in compact crystals, presents only a small surface to the dye solution. It is impossible, with normal treatment times, to dye more than a very small proportion of the crystal. The Miller image, on the other hand, has a much larger surface area for the same quantity of mordant, due to its more finely divided state. The dye can then react with the mordant much more readily. A silver image of much lower contrast and density is therefore needed with the Miller-type mordant as its dye mordanting efficiency is so great. The silver iodide technique is therefore capable of producing a wide range of mordants by varying the potassium iodide concentration. As this is increased the transparency and dye adsorption also increase, but the sharpness decreases. Dye Toning Technique The silver image is exposed and developed to a suitable contrast and density, depending on the type of mordant to which it is to be converted. The Traube mordant requires a fairly hard, dense original image, whereas the more transparent Miller mordant will require a soft, light density image. It is important that the emulsion is not hardened with an alum for, as mentioned above, many salts including chromium and aluminium salts can act as mordants for basic dyes, and

94

BASIC PHOTOGRAPHIC

CHEMISTRY TONING PROCESSES

therefore cause an overall stain. A very thorough wash should follow fixing, and then the image is bleached, or more accurately, converted to silver iodide. Traube's bleach consists of: Iodine 15 gill Potassium iodide 50 gill Acetic acid (glacial) 25 cc Water to 1 litre The Miller bleaches have much less iodine and more iodide. After a brief wash the excess iodine which will have discoloured the gelatin is removed in a bath of sodium bisulphite, which is then removed by a thorough wash. The mordant images are then dyed up in a 1 : 1000 solution of a suitably coloured basic dye which has been acidified with a little acetic acid. The acetic acid, besides helping to dissolve the dye, increases the dyeing rate. The dyeing time depends largely on the type of mordant which is used, but is normally from three to ten minutes. A thorough wash is then necessary to remove the dye which has been retained by the gelatin. A small amount of acetic acid in the wash water assists in the removal of the excess dye. If the Traube mordant has been used the image, although bright by reflected light, will lose a lot of its brilliance when looked through. It is a common procedure to remove the silver iodide mordant by fixing in a plain thiosulphate fixing bath. Before this step the dye must be made insoluble, or it will bleed out. . The mordanting action of silver iodide is not due to a chemical reaction between the mordant and the dye, but to an attraction between the two, partly physical and partly chemical, known as adsorption. If the mordant is dissolved away, the dye would be free to wander. The dye is made insoluble by treating with certain organic or inorganic acids which combine chemically with it. Tannic acid has long been known as a precipitant for basic dyes, but is liable to slain badly unless it is freshly prepared from the pure acid. It has been replaced for this purpose by complex inorganic acids such as phosphomolybdic and phosphotungstic acids. After the image has been treated with one of these acids, the mordant can be fixed out, when a brilliant, transparent image is left.

95

The ~ore transparenit Miller mordants do not, of course, need this treatment as they are already sufficiently transparent. The. silver iodide mordant has been dealt with to the exclusion ?f th~ other mordants mainly because of its wider u~e, especially 111 the making of colour prints. In general With the other mordants, the colour of the mordant itself i~ so strong that brilliant prints cannot be obtained. For mono~hrome photography, of course, many interesting and beautiful results can be obtained by modifying the colour of for .example, a copper ferrocyanide image, by treating with baSIC dyes. .Colour. development processes are normally considered :WIth toning .processes, but because of their great importance m commercial colour processes, the next two chapters are devoted to them.

REFERENCES
Hickman, K. CD, B.J. Phor., 1923, 70, 123. 2 Tnepel, W., 8./. Phot., 1911, 58, 657 (B.P. 24,378/1910). : Traube, A., B.J. Phos., 1906, 53, 94. Miller, B.P. 100,098.
1

64

HASIC PHOTOGRAPHIC

CHEMISTRY

rns

DEVELOPMENT

PHOCESS

65

therefore excessive grall1ll1ess, and negatives, is of interest. Pyro Metol Potassium metabisulphite ... Sodium carbonate (anhyd.) potassium bromide ... Water to

useful for under-exposed 3 gm 2.6 gm 7 gm 18 grn 3.2 grn 1 litre

fore develop more fully, and give adequate shadow detail. The distorted characteristic curve will result in poorer' quality for the majority of subjects. Somewhat similar results can be obtained by dipping the negative in a vigorous developer for about a minute, and then leaving it undisturbed in a water bath for several minutes, repeating the process if necessary. Again the development in the dense areas ceases before development in the shadows due to local exhaustion. Physical Development Technique At one time extravagant claims were made in respect of fine grain for physical methods of development. That is, methods in which the image silver is provided by adding silver salts to the developer, and depositing this silver on the development centre, rather than reducing the emulsion silver halide. A great deal of work on physical development was carried out by Odell' and further developments were made by Baur and Imhof" and by Turner.:" The original Odell method used an ami dol developer and Turner's modification is in the use of metol and hydroquinone, which can be kept in solution, whereas the Odell formula called for the addition of solid amidol immediately before use. The first step in this method is to prevent the emulsion halide from participating in the development process. It was stated earlier that a fixed emulsion containing a latent image could be developed, but as silver halide solvents also attack the very fine photolytic silver deposit of the latent image, this method is unreliable. Instead, a potassium iodide forebath is used, which converts the silver bromide or iodobromide to silver iodide, which is not reduced in normal developers. Physical Development Forebath Potassium iodide ... ... ... ... 10 gm Sodium sulphite (anhyd.)...... 25 gm Water to ... ... 1 litre The time of treatment in this bath is from 30 seconds to 3 minutes. The short time gives higher emulsion speed but coarser grain. The finer grain obtained with the larger immersion is at the expense of a reduction of emulsion speed to one-fifth. The writer believes that in the case of the short immersion times, conversion to silver iodide is incomplete, and some normal development takes place. The physical development 'working solution is obtained by diluting a stock hypo-sulphite-silver nitrate solution and

Concentrated Developers The most popular type of concentrated developer contains p_aminophenol as the developing agent with a caustic alkali. No appreciable fog is produced in the diluted solution and therefore bromide is omitted. A typical recipe is Stock Working Solution Solution 1 : 19 p-aminophenol nci ... 50 grn 2.5 gm Potassium metabisulphite .,. 150 gm 7.5 gm Potassium hydroxide ... 70 gm 3.5 gm Water to .. , ... .., 1 litre 1 litre The stock solution will keep for many years if it is stored in full bottles with rubber bungs or waxed corks, but once the bottle has been opened it should be used fairly quickly otherwise it will deteriorate. Special Development Techniques Of the many special development methods which have been proposed at various times, few are suitable for normal use, except perhaps the two-bath method. For this the developer is split into two parts--one containing the developing agents and sulphite, and the other the alkali. The method is to soak up the developing agent solution-which is usually of a higher concentration than normal-into the emulsion, and then put the film in the alkali when it will be developed. The method gives little opportunity for control of contrast, as the times in each bath can usually be varied within quite wide limits without drastically altering the result. It has been said that for harshly lit subjects this method will enable the shadows to be fully developed without blocking up the highlights. The developing agent present in the emulsion during the developing step-in the alkali-is soon exhausted in the dense areas, so development stops, whereas in the light density areas the developing agent is used less rapidly, and can there-

)
COLOUR DEVELOPMENT

97

Chapter

COLOUR

DEVELOPMENT

ROFESSIONAL motion pictures apart, more colour photographs are produced by the colour development process than by any of the other photographic colourir,tg metho?s. Although this process has only been used commercially during the last twenty years, the first suggestions for its use were ma~e forty years ago. About 1913, attempts to produce colour plCtures based upon the patents of Fischer and Seigrist were unsuccessful. In the early thirties both Kodak and Agfa marketed practical materials which, using quite different methods overcame the difficulties that had prevented the success of the earlier project. These integral tripacks will be fully described in the next chapter. Primary Colour Development The majority of organic developin~ agent? will, when oxidised, produce colonred substances 1 used in developers which contain no sodium sulphite. These coloured substances--which in general are not ve:y solub.le-v~ill be deposited in the gelatin layer tog~ther with the silver image. The silver image is then removed in a neutral solvent such as Farmer's reducer, and the coloured image will be left in the layer. Among the more common de,;eloI?ing agents, :pyrogallol produces the strongest imag~, v\:hich lS of ~ yellm~lsh-brown colour. The chemical constitution of the image is obscure, as pyrogallol produces a wide variety of oxi~ation products. As none of the other common developmg agents are oxidised to brightly coloured images, ne~ substances were sought with this end in view. Homolka in 1906 suggested indoxyl and thioindoxyl as primary colour de,:e~op~rs. These are oxidised to the blue indigo, and the red thioindigo respectively. Owing to the instability of the developing solutions the results were far from satisfactory. Many other leuco bases were tried as developers but with 110 conspicuous success. The leuco bases are formed from a series of dyestuffs known as the vat dyestuffs. These dyestuffs are almost insoluble 96

and are very fast to light, and resistant to chemical action. When used in textile dyeing they are reduced with an alkaline hydrosulphite solution to the soluble, and more or less colourless, leuco base. The fabric is treated with the leuco base solution and is then either left in the air to oxidise, or is treated in an oxidising solution to re-form the vat dyestuff. Many of these leuco bases have developing properties, and are oxidised to dyestuffs by the silver halide. But they are inclined to oxidise spontaneously in the air, and therefore stain the gelatin. Attempts to stabilise the solutions have not been successful. One patentee even suggests that aerial oxidation can be eliminated by working in an atmosphere of nitrogen, the operators being equipped with oxygen breathing apparatus I A few patents dealing with primary colour development have been published, but the range of colours which can be produced by this method is very small, and as secondary colour development has been very fully developed, the primary process has little more than historic interest. Secondary Colour Development In this method, the oxidation product of the developer reacts with a second substance, known variously as a colour coupler, colour former, or dye former, to form a dyestuff. It is the greater flexibility of this type of process which has virtually excluded primary colour development as a practical process. The Colour Developing Agent Although most of the common developing agents will oxidise and couple to give coloured substances, the images obtained are very dull and lacking in density. The developing agents generally used for colour development work are derivatives of p-arninoaniline (p-phenylenediaminej-s-in particular, substitution of one of the amino groups with lower alkyl groups, and nuclear substitution by a lower alkyl group.

C1HS

6
...N,

C2H5

p-diethylaminoaniline

98

BASIC

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COLOUR

DEVELOPMENT

99

C'~NONH'
I C2HS ~-amino-5-diethylaminotoluene Paradiethylaminoaniline in particular is a fairly efficient developing agent, and is readily obtainable pure enough for use as a developer. The bases themselves are not stable and deteriorate when kept for any length of time, and therefore the usual commercial product is a salt-either the sulphate or the hydrochloride. An even more stable form of p-diethylaminoaniline has been developed by May & Baker Ltd., and is marketed under the name of . Genochrome.' Advantage has been taken of the anti-oxidation properties of sulphur dioxide, ar:d a loo~ addition product has been prepared. When dissolved m water the addition compound breaks down to some extent to give a solution of the p-diethylaminoaniline base and sulphurous acid. This solutio~, unlike the solutic:>Ils of the hydrochloride and sulphate, IS very stable, but ~t must be mentioned that solutions of the other salts to which a molecular equivalent of, for example, metabisulphite, has been added, are also quite stable. . . , These developing agents have two dlsadvantages-t~elr reducing power is not great, ,:"hich makes lonl? ,developmg times necessary, and they can give severe dermatitis to people with a sensitive skin, The free base appears to be dissolved by the natural skin oils, and so is absorbed into the tissues, causing severe irritation, The oil-solubility s~lould, therefore be reduced, and if possible the water solubility increased. Unfortunately the normal methods of doing ,this reduce t~e developing potential beyond practical llJ;llts .. />;. partial solution is to use p-(hydroxyethyl-ethyl) arninoaniline,

WhiC~l is l~ss readily absorbed. To obtain a developing solution Wlt~ the same energy as p-diethylaminoaniline, about three times the quantity of developing agent must be used. Several more complex p-diethylaminoaniline derivatives h,a:-rebeen patented which, it is claimed, do not give derma~ltIS,and d~ not decrease, but may even increase, the developmg potential, None of these, of course, are generally available. Halogenated p-aminophenols have been claimed in patents by bot~ Kodak and Agfa as colour developers; but have not ?een WIdely used, perhaps on account of their low solubility in water. Colour' Couplers he, b~sic requirement of a colour coupler is that it contams III Its structure a methylene group which is activated by . a ~trongly electro-negative group, The most common a~tJvatmg groups are carbonyl, nitrile, and other unsaturated nitrogen atom groupings. ,The basic, cou'ple.r groupings-~hich were disclosed by Fischer and Siegrist III 1915, and which were greatly developed prior to the Second World War-are: (1) Phenolic compoundS-blue and green dyestuffs

:r

-the phenols are capable of existing in two forms, the enol form shown above, and the keto form whose structure contains a methylene group:

... , N CzHS CZH40H

c5 6~c5~6
Hz

(2) f3-keto ester derivatives (yellow to orange dyestuffs) R-CO-CH2-CO-Rl

100 (3) acetonitriles (4) 5-pyrazolones

BASIC

PHOTOGRAPHIC

CHEMISTRY

COLOUR

DEVELOPMENT

101

(orange to magenta R-CO-CH.-C= N (red and magenta H.C- C-R

r " ,::C, ... N

dyestuffs) dyestuffs)

using the chlorinated l-naphthols in order to obtai~ a .gre~ner dyestuff. (The dyestuff obtained from I-naphthol IS a bnght blue.)

N r Rl

2-ch lor-I-naphthol

The simpler compounds which contain these groupings do not generally give good dye images. The dyestuffs are often too soluble to remain in the gelatin layer, or they are attacked by chemicals present in either the developer, or in subsequent treating solutions. For example, a dyestuff can be obtained by reacting phenol with p-nitroso diethylaniline (a stable oxidation product of p-dieth ylaminoaniline)

cO
(I

CI
2 : 4-dichlor-l-naphthol

~CI
2 : 3 : 4-trichlor-l-naphthol ~(I (I

Among the many phenolic compounds which have suggested as couplers giving blue-green images are

been

00
but this dye is quite soluble. The coupler must therefore be modified to give an insoluble dyestuff without the coupler itself being insoluble. The most common coupler to do this is I-naphthol

2 : 2'-dihydroxybiphenyl

~ryv
OH OH OH

~Br

2: 6-dibromo-1

: S-dihydroxynaphtholene

bis-I-naphthol

which was suggested by Fischer and Siegrist, who also proposed

102

COLOUR BASIC PHOTOGRAPHIC CHEMISTRY

DEVELOPMENT

103

and a host of phenols and l-naphthols to stabilise the dyestuffs.

which contain groups He proposed in their patents. The grouping .... :C CH. C _ N is most commonly used in cyanacetic ester derivatives and in acetonitriles. The most common magenta coupler, also propose~ by Fischer, is p-nitrophenylacetonitrile (p-nitrobenzyl cyanide)

Fischer could not obtain good yellow images. using acetoacetic ester CH3 CO. CH2. CO. OC2HS benzoyl acetic ester

CO-CHZ-CO-OC2.HS

and their simpler derivatives. It was not until Kodak patented the anilides of these esters CH3-CO-CH2-CO-NH

OCO-CH2-CO-NH

O O

whilst benzoylacetonitrile

that yellow colour developed images were obtained which had good density and hue. Naturally the other manufacturers patented further developments of these compounds, using, for example, morpholine derivatives to replace aniline derivatives CH3-CO-CHz-CO-NH

and the anilides, in particular acetic ester

the p-nitro anilide, of cyan-

O
the

N ,

CHz-CHz '0
/

yield clear orange to magenta images. Du Pont benzoyl l-phen yl-3-methyl-S-pyrazolone is frequently magenta coupler as it is readily available used as a

CHz-CH2 aceto-or

and furoyl acetanilides

acetanilides to replace

Veracol

Ilford patented

the use of monoanilides of malonic ester but the dye image is not very brilliant. Much better images are obtained when the phenyl group is substituted, usually with a nitro group or with halide atoms, or if the methyl

CzHsO - CO - CH2.- O - NHO C whilst Agfa mention terephthaloyl bis-anilides

104

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105

group in the 3-position is replaced by a benzoyl or other more complex group. The structure of colour couplers has been dealt with at some length to show that although the active groups may be well' wrapped up' in complex molecules, the basic essentials have, until recently, not changed since Fischer's original patents. The Colour Coupling Reaction As we saw earlier, when a developing agent ion and a silver ion react, the silver ion is reduced to silver metal, and the developing agent is oxidised. Normally we remove the developing agent oxidation product by including a large quantity of sodium sulphite in the developing solution. In colour development, however, it is the oxidation product which we require, so the sulphite is either omitted, or reduced to such a small quantity that it does not react quickly with the oxidised developer. This is then free to react with the colour coupler NR2. NR:

O+<S~O+6+H+
/

~H CH
<,

NH

~ C

NHz

-,

R
reaction

R
can then

R
be summarised by the

The complete equation

0+
NHz
developing
agent

R
CHz+4AQ
/ +

'R'

.J

(}2A,.- ()+
NHz NH
quinonediimine
ion

coupler

silver
ions

dyestuff

silver
atom

hydrogen
ions

2Ag -+ H

().
NH

/R
CHz

"R'

Q
R' 'R'
leuco base

H+

CH

The leuco base which is formed is readily oxidised to the dye by oxygen in the air, but a more likely oxidising agent is a second quinone diimine ion, which is reduced back to the original developing agent

For the reactions which we have discussed to take place, four silver ions must be reduced to produce one dyestuff molecule. Recent work has shown that rather less silver than this is needed in many cases. It is not unreasonable to assume that in these cases the leuco base is to some extent oxidised by oxygen dissolved in the water used either for the developing solution, or in other baths, or for washing. The oxidising agent which is subsequently used to remove the unwanted silver image may also be responsible to some extent for the oxidation of leuco base molecules to the dyestuff. Stability of Dyestuffs On the whole, the indophenol and azamethine dyestuffs produced by the colour development process have the disadvantage that they are stable neither to light nor to chemicals. There are of course exceptions, but in general any acid processing solutions must be avoided, and especially acid sulphite solutions. A neutral or alkaline fixing bath must therefore be used, which is rapidly discoloured and must be discarded frequently. * Calcium salt deposits on the emulsion are also
Some dye images will be decolorised with an acid fixing bath but will regain their original density after washing and drying.

W6

BASIC

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CHEMISTRY COLOUR DEVELOPMENT

107

difficult to remove without destroying the dye image to some extent. The light fastness of the dyes is so low that it is not advisable to keep them exposed to light. Although most manufacturers-notably Kodak-have produced more stable dyes working along normal lines, by far the most original developments a e from General Aniline. Various approaches have been made by them to obtain other types of dyestuff 'either by using more complex developing agents.' different types of coupler; or both." From the chemist's viewpoint the patent covering the use of substituted m-arninoanilines as colour couplers is the most interesting. The first product of the dye-coupling reaction breaks down-usually spontaneously-to give a dyestuff with a different structure, which when treated with an acid yields a brilliant azine dyestuff. The general scheme of one of these reactions is
NH

Treatment After Development The normal processing following development is insufficient for colour development, and may destroy or degrade the colour image Bisulphites and strong acids in particular must be avoided. This rules out the acid fixer. To give a plain fixer the greatest possible life a thorough wash is essential between development and fixation. A stop-bath of, for example, sodium acid phosphate (NaH2PO,) also helps to remove the developing agent. The essential difference, however, between black-and-white processing and colour development processing is that the silver image must be removed after colour development if a pure dye image is required. Farmer's reducer is commonly suggested but does not, of course, keep well. The oxidising agent can be used in one bath and the solvent in another with a rinse between them. Any acid bleach such l,S permanganate and hydrochloric acid dichromate-sulphuric acid will completely destroy the majority of dye images. The following scheme illustrates normal practice in colour development processing with colour couplers giving acidsensitive dyes. When acid baths-which would not normally affect the dye image-are used it should be noted that solutions yielding sulphur dioxide on acidification are isolated by washing. Development 10 min Wash 5 Stop-bath 1 W~ 5 Hardener (chrome alum) 3 Wash 5 Bleach (ferricyanide and bromide) 5 Rinse 2 Fix 10 Wash 10 The fixation step normally follows bleaching as at this stage both the unused halide and the halide regenerated from the image can be removed together. An alternative procedure is to introduce a fixing stage in place of the stop-bath. This would make washing easier. The silver halide grains in the emulsion adsorb the developing agent, which does not wash out easily, and may still be present at the bleaching stage, when it is oxidised, the oxi-

or

NMez

- C~ON
blue quinoneimine

coupler

developer

NH-SOzO

NMe2

_ C~QN N6N""
orange

HX

C~(iN'
NHA VNMe.
ma&:enta azine dyestuff

NHz

azine anhydride

Thes~ recen~ advan?es, which point to the possibility of producing a wider vanety of dyestuff types without basically altering the mechanics of the colour development process, show that we can expect still more from this process.

108

BASIC PHOTOGRAPHIC

CHEM.ISTRY

dised devel.ope~ coupling with any residual coupler to give an ove:-all stain. If the halide is removed there is nothing to retam. the developing agent, so it is more easily removed by washing, Colour Development coelerators

Chapter

10

INTEGRAL

TRIPACKS

Owing to the low developing potential of colour developer solu~ions, it i~ .desirable to speed up development as far as possible. Raising ~he pH of a developer by using caustic alkali would do this, but may result in degraded colours. ~here are two methods of increasing development rate which can be used in some applications. <?wing to the. low: sulphite content of these developers, their solvent action IS very slight. This can be augmented by including an additional halide solvent-thiocyanate for example-in the developer. Wh~re the co"?pler is used in the developer solution, the dye depo~lt m~y hinder the access of developer to the grain. The inclusion of a small quantity of a dye solvent in the developing s,?lution will often disperse this dye slightly, to allow the.gral.n to be more.readily developed without causing enough diffusion to result in a loss of definition. A suitable solvent is benzyl alcohol.

IKE so many other colour photographic techniques the use of a tripack for obtaining colour separation negatives was proposed by Louis Ducos du Hauron. Du Haurou's tripack comprised three emulsion layers, each on a separate thin base. The front emulsion was blue sensitive, the second green sensitive, and the third red sensitive. It is unlikely that he was able to produce a practical tripack, for high speed colour sensitised emulsions were not available to him, nor was thin transparent film base. A tripack of this type was marketed by Defender up to 1940, but even with high speed emulsions and thin film base it was not a great success. The definition on the rear element (cyan printer) was very poor, and the method has now been abandoned in favour of the integral tripack. Tripack Principle The illustration shows the construction which is common to all integral tripacks, whether they are of the colour development or the stripping type.
blue sensitive
green sensitive

emulsion
emulsion

yellow filter layer red filter layer-optional

red sensitive emulsion

REFERENCES
3

~ B.P. 625664 (BJ. Phot., Feb. 24, 1950, p. 93). - B.P. 633760 (BJ. Phot., June 30, 1950, p. 331). B.P. 649811 (B.l. Phot., June 22,1951, p, 315).

White light passing through the emulsion matically separated into the three primaries, inherent or added sensitivity of the emulsion, of filter layers. The blue component of the white light will sensitive front layer, and will then be absorbed filter layer. The remaining light will pass 109

will be autoby either the or by the use affect the blue by the yellow on, the green

110

BASIC

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CHEMISTRY INTEGRAL TRIPACKS

111

component affecting the green sensitive layer and the red component, the red sensitive layer. It is possible to obtain emulsions which are sensitive to gre~n but not red light, and also to red, but not green light. It IS then not necessary to include a red filter layer in the pack. Sometimes, however, this may be included to give better separation in the red sensitive element. All fast emulsions, however, are sensitive to blue light, and as we want to record the blue light only in the outer layer, its passage through to the green and red recording layers must be prevented. The yellow filter layer does this, and if the colouring material is carefully chosen, it is possible to remove practicall~ the whole of the blue light without substantially reducing the amount of green and red light. Three types of integral tripack are in current use-the stripping tripacks, the materials containing no colour coupler, and those materials which contain a colour coupler anchored in the emulsion. Stripping Tripacks

Kodachrome The basic material corresponds to the diagram wit~. no special departure in structure, bu~ includes a red sensitiser which is not destroyed in a developing bath. After exposure, the film is developed in a normal reversal first de,:e~oper. This is probably an energetic M.Q. develop.er containing a silver halide solvent in addition t? sulphlt~-probably a thiocyanate. The developer is suffiClen~ly aC~Ive to develop all of the exposed grains. For a neg.atr:re thIS. woul~ result in unpleasant graininess, but as this Image IS ultl,mately removed large grain size does not matter. The film IS then washed thoroughly to remove the developing r~agents, .but is not fixed. It is the residual silver halide which provides the positive image. The next step is probably to exp?s.e the film (t~rough the back?) to red light. ~he ~ed sen.s~trve layer, ?Wll1g to the special sensitiser use?, I~ still sensitive to red light, and the residual silver bromide IS made developable. In the. other 1:\:'10 layers, however, the red ~i~ht has no effect .. Development in a colour developer contalmng. a cyaJ?- colour coupler produces a positive silver-plus-dye Im~ge ill the bottom layer. If the film is now exposed to blue light from the front~ on!y the outer layer will be affected as the yellow filter layer IS still present. Colour dev~lopme~t in the presenc~. of ~ yelIo:w colour coupler will give a silver-plus-dye positive Image In the outer layer. Only the residual halide in ~e inte:me?iate layer remains, and this is fogged either by light WhICh IS strong enough. to penetrate the now fairly dense outer layers, or by a fogging solution. This layer is developed i~. a I?agenta colour developer. Both the negative 8;nd positive silver I~~ges are removed by bleaching and fixing to leave a positive dye image. Two points which are of the greatest importance in the processing of 'both Kodachrome and Ilfo~d Colour, are that the re-exposure and development techniques must ensure that there is no developable material left in a layer that has been treated with colour developer. Nor must the developer give any visible image in an unexposed layer. . Secondly, the complete removal of developer reagen~, partlcu~arly col?ur couplers, between each colour developing stage IS essential.

. Thes~ materials have no special significance from the viewpoint of the photographic chemist. The layers between t~e. three emulsions are designed to part under certain conditions. .At present no materials of this type are available commercla~ly, but both Kodak and du Pont are actively engaged with the problem. The Kodak material has been developed for motion picture use, as the complete mechanIsabor: of the motion picture processing laboratory is almost essential." Du Pont marketed for a short time, but then withdrew a modified tripack (the' S.T. Tripack ') with only one stripping layer. Colour Transparency Tripacks

As the use of these materials is the subject of a book (C,0lour ~ransparencies, by C. L. Thomson, Focal Press), we will consIder them only from the chemist's viewpoint. The type of tripack which contains no colour coupler is, in the two commercially available brands-Kodachrome and lIfOI'd COlour, processed by reversal to a positive transparen.cy. . This processing technique is not straightiorward and, If reliable results are to be Obtained, must be left to the manufacturer. As the two materia,ls differ considerably we will treat them separately.

112

BASIC PHOTOGRAPHIC

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TRIPACKS

113 Containing Non-diffusing Couplers

I1ford Coloui: The above notes on the processing of Kodachrome are not 'official,' but are probably reasonably correct. Even less information is available concerning the !lford processing technique. In fact, it is only the study of patent literature that enables the writer to deduce the following possible method, which, though not necessarily the exact method used, illustrates the -broad principles of the way in which this material is processed. In the manufacture of the film, sensitisers which are resistant to developer action are not essential. The main difference between !lford Colour and Kodachrome is in the materials forming the isolating layers between the emulsions. !lford have for these layers a very fine grain slow chloride emulsion, which is not sensitive at the light values used for exposure. Mixed with this emulsion is a non-diffusing fogging agentprobably colloidal silver sulphide. During first development these layers develop to form opaque barrier layers. It is then a relatively simple matter to expose the two outer layers separately, and without affecting either the other outer layer or the inner layer. After first development and thorough washing the sequence of processing steps is probably :_ 1. 2. 3. 4. 5. 6. Expose to light through the base. Colour develop in cyan colour developer. Wash. Expose front emulsion. Colour develop in yellow colour developer. Wash.

Tripacks

Fischel' and Siegrist suggested incorporating colour couplers in the three emulsions of a tripack ; but they were um~,bleto produce satisfactorr results as t~e colour couplers diffused from their appropnate layer dunng devel~pmen~. Even a thick plain gelatin layer between the emulsions did not prevent this, A further difficulty they must have encountered was that some of the couplers crystallise when in?orporated in a gelatin solution which is then coated and dned. Several methods were proposed, with little success, to overcome the difficulty of diffusion, mainly by precipitating the couplers as insoluble salts in the emulsion. T~e difficulty here was that if the insoluble salt broke down dunng development there would still be some coupler diffusion to an adjacent layer. If the salt did not break down, coupling was extremely slow, The first practical solution came from LG. Farbenindustrie A.G., and was finally put on th~ mark~t in 1936 as '.N~w Agfacolor.' Many patents were Issued m the early thirties dealing with methods of modifying colo?r couplers so that they would not diffuse from the appropriate emulsion layer. Generally, the method was to add to the coupler molecule a grouping which .wou~d becom.e physical~y attached to t~e gelatin. If we lm~gme gelatm to <:onslst of long organic chains-usually WIth many cross-Imkages-we can also imagine that a large molecule will become entangled in this chain structure. Merely increasing the coupler molecule IS not the most efficient method. The most successful of the different groupings is a large fatty acid residue containing ,a chain of at least five carbon atoms. The structure of this chain would be, for a l2-carbon atom chain :-

7. Trea t centre layer in chemical fogging solution. 8. Develop in magenta colour developer. 9. Wash. 10. Remove all silver and silver salts. 11. Wash. 12. Dry. In theory it is immaterial whether the front or back layer is treated first, but no doubt in practice the order has some effect on the final result.

HH H HHHH HH H HH couP,er-t-t-t-d-d-d-d-2-2-2-2-2-H
~?~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~

This method is used for anchoring the coupler molecules in the Agfacolor process, full details of which are given in various government reports.s

114

BASIC

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CHEMISTRY

INTEGRAL

TRIPACKS

115

These couplers also contain groups which make them wate~-soluble to facil.itate their inclusion in aqueous coating solut!o?s. The way in which these various groups are introduced into the coupler molecule varies with different types of coupler, but in one of the blue-green substantive couplers= they are introduced stage by staae and serve as a very useful illustration :o

The materials can be developed directly in a colour developer to a colour negative, and subsequently printed upon a similar material on either a film or a paper base. Alternatively they can be processed to a positive by the reversal method. Kodak use a completely different method of ensuring that the couplers stay in their appropriate emulsion layers. The first patent was issued to Martinez in 1937 but the method has been thoroughly developed at the Kodak research labora tories. The coupler is dissolved in either a solution of a resin which mixes with the coupler in all proportions, or in a high boiling point liquid or low melting point solid, which with the coupler forms a thick oil. This is dispersed in the emulsion as minute droplets, so fine that they can only be seen with a microscope. As neither the . oil-former' nor the coupler is water-soluble, tbe coupler cannot readily wander from the emulsion layer. Although in patents it is claimed that the oil-formers themselves restrict diflusion of the coupler, it is far more likely that their presence only enables the insoluble coupler to be dispersed evenly in the emulsion without forming large crystals, Another statement which is usually made in patents is that the oil-formers are water insoluble, but water permeable. In the writer's opinion they are not necessarily water permeable, but are good solvents for the oxidation products of development. The solubility of these oxidation products in water is' not' great, but is much higher in the oil-formercoupler solution. The oxidised developing agent is easily absorbed to react with the coupler and give a dye.

l-hydroxy-2-naphthoic acid
blue-green coupler

octadecylamine long-chain alkyl group

substantive blue-green coupler-not readily soluble

Colour Accuracy
substantive blue-green coupler-alkali soluble

This type of colour coupler is used in Ansco Color, Gevacolor, and Ferraniacolor as well as in Agfacolor.

Couplers

which will not diffuse from the emulsion.

Although the dyes produced by the colour development process are far from ideal, they are quite satisfactory when used in a reversal film-that is, when the dyes are used only once in the production of a positive image. When a colour negative is used to make prints on to a_ similar positive material-that is, when there are two dye stages to reach the final result-the colour distortion due to the imperfections of the dyes becomes very noticeable. Commercial motion

116

BASIC PHOTOGRAPHIC

CHEMISTRY

INTEGRAL

TRIPACKS

117 Colour Masking

pictures demand yet a third or fourth stage for any special effects, and the colour quality then becomes intolerable when compared with processes in which all intermediate stages are via silver separations.

As the magenta colour developed dye image is the most distorted of the three, this image will be used to illustrate the colour masking principle. Theoretically the magenta dye should absorb all green light and transmit all blue and red light,

>t-

o;;
Z

'"
o

500

600

700 400

soo A mf'

600

700

To correct these deficiencies-which are illustrated abovemasking techniques have been used for many years. This method using separate masks is reasonably practical for motion picture work, where registration of the masking image is automatic; and also in photo-mechanical processes where the number of copies produced justifies the expense of mask preparation and manual registration. For amateur and single-copy commercial work, however, methods using external masks would be too expensive. During the last ten years, several methods have been proposed, by means of which masking images are produced in the original negative. The earlier methods merely proposed developing the residual silver halide of the negative to give a low contrast silver positive in one or more of the emulsion layers. This method gives an increase in brilliance in the final print, but no greater hue accuracy. The more elegant methods produce a coloured positive image together with the colour negative, which corrects for hue as well as for brightness in the following way.

although a dye which transmits equal quantities of blue and red light, with strong absorption in the green region would give good results.

>o;;
t-

'"

400

500

600

700

~ =
The typical magenta dye transmission curve, however, transmits most of the red light, and has the necessary green

118

BASIC

PHOTOGRAPHIC

CHEMISTRY

INTEGRAL

TRIPACKS

119

absorption, but has a secondary absorption peak in the blue region of the spectrum: .

fore a yellow image will also be produced .. When the print is balanced to record greys in the subject as greys in the print, this yellow positive image resulting from the magenta negative image will 'make a rednction in the normal yellow image strength necessary. The net result in the print will be that reds will generally be too orange, due to the yellow image associated with the magenta., while yellows will be weak and greens too blue due to the reduction in the strength of the real yellow image. If a positive yellow image is produced together with the negative magenta image, and of such a strength that the maximum blue-filter density of this yellow positive image is the same as the maximum blue-filter density of the magenta image, we will have these curves (ignoring the negligible redfilter densities) :

400

500

600

700 GREEN FILTER DENSITES

If the characteristic curves of an image made from this dye, read through blue, green, and red filters, are plotted, curves similar to these will be obtained:
>-

v;
Z

l-

o
GREEN

>-

z w o

!;;

Log. E The resu It of the negative and positive blue filter images is merely an over all yellow density which with a suitable positive material of higher-than-normal blue sensitivity, is not incon venient. The excessive blue and green absorptions of the cyan dyestuff, although not as serious as the blue absorption of the magenta image, can be similarly counteracted by a red positive masking image corresponding to the negative cyan image. The yellow image dye characteristics are normally adequate without correction. Attempts to produce integral masking images by using the residual silver halide to produce either a silver or a stain

Log.E When a colour negative is printed on to a colour positive, the red filter densities control the blue-green image, the green filter densities, the magenta image, and the blue filter densities, the yellow image. The magenta image of the negative should only produce magenta gradations in the positive, but in the case of this dye there is appreciable blue filter density, there-

(~

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121

image improve colour brilliance and sometimes colour rendering, but, because of the lack of discrimination between the requirements of the various layers, are merely compromise methods, and no real solution. To date, the only effective methods are those in which the residual non-diffusing colour coupler present in the individual emulsion layers is used to form the coloured masking image. Several methods of using these couplers have been proposed, but the most elegant way is to use colour couplers which are themselves coloured. Coloured Colour Couplers Patents covering the use of coloured colour couplers have been obtained by Kodak and LC.Ls Basically, the method is to produce from the parent colour coupler a dyestuff which is of the hue required for the masking image. In the presence of colour developer oxidation products, the group attached to the coupler to prepare this dye is split off, and the coupler couples in the normal way to give the dye image. Kodak use azo dyestuff coloured couplers whilst I.e.I. have covered the use of styryl dyestuff couplers. The following examples show the way in which the coloured images are formed.
I-phenyl-3-methyl-S-pyrazolone

HOON=N-HC-C-CHs
\ 1\

if "N/

which is incorporated in the emulsion when the oxidised developing agent

and which

IS

split

couples to give the magenta image dye

H2C-C-CH

II

9C

"N/

. Red azo dyes from phenolic couplers

is coupled with a p-hydroxyphenyl

diazonium compound

to give the yellow azo dyestuff

are similarly split at the azo linkage when they couple to give blue-green dyes, with the oxidation products of colour developing agents

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R):{ CH,

and during colour coupling the styryl grouping is ruptured when coupling with the oxidised developing agent occurs, to give the magenta image dye

O~N-b-NE"

Et2NQN=C--C-CI7H35
,

The styryl dye -coloured couplers, which are applicable to magenta couplers, are prepared by reacting the parent colour coupler-which in this case contains a long chain alkyl group to restrict diffusion:

CH3 /N O~ "N

.s:

\I

050,NO
Whilst these methods of incorporating the coloured coupler in the emulsion offer the advantage of normal processing, other methods of using the residual colour coupler to form a masking image can be used, and offer certain advantages, One disadvantage of the coloured coupler method is the presence in the layers, during exposure, of unwanted dyes, which could reduce sensitivity.' Also, if the masking dyes are formed during or after normal processing, any effect which they may have on the unexposed emulsion or upon the latent image, is unimportant. The proposals which have so far been made to form masking images from the unused colour couplers convert the couplers to azo or styryl dyestuffs of the same type as the coloured couplers.! The production of a yellow styryl dye mask for the magenta image is quite straightforward. After development the film is treated in a solution of a suitably substituted benzaldehyde, This will react with the residual magenta coupler to give the required yellow positive mask, but the residual cyan and yellow couplers will be unaffected. For the production of azo masking dyes a more elaborate procedure is required. Diazonium salts would react with all three residual couplers if the film were merely bathed in a diazonium salt solution as in the previous method. Suitable dyes would be produced in the lower layers but the top layer image would be unwanted, To overcome this the diazonium com-

with an anil of a p-substituted yellow styryl dye

amino-benzaldehyde

to give a

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pound is added to the emulsion used for the lower layers in such a form that it does not diffuse into the top layer. A further requirement is that the normally unstable diazonium compounds must be used in a stable form. Whilst this azo dye method offers the advantage of masking images in both magenta and cyan layers, it has the disadvantage of being much more awkward in use. It should be emphasised that although the improvement in colour rendering -by using a double masked negative material, such as Ektacolor, is great compared with an unmasked method, the colour reproduction is still not perfect. The highest accuracy is obtainable only in a six-mask system, at every stage which involves colour images. The double masked systems are, however, a very good compromise between high accuracy and simplicity of procedure.

Chapter

11

MISCELLANEOUS

PROCESSES

Print-out Emulsions

F the exposure which produces a latent image is continued, the microscopic silver specks which comprise the latent image become larger and visible. This' print-out' effect was at one time widely used for the production of contact prints. Because of the long exposures necessary-about 15 minutes in bright daylight-the use of this type of material is now very restricted. Even though the development step is unnecessary, printing out is generally considered less convenient than the use of slow contact development papers, which likewise can be handled without elaborate darkroom equipment. The sensitive salt used in these emulsions is normally silver chloride, but they are prepared, not as are development emulsions with an excess of halide, but with an excess of silver salt. This accelerates the photolytic reduction of the silver halide (but would, of course, fog a development emulsion)
2 AgCI -+ 2 Ag

+ CI.

or in ionic form
Ag+

+e

-+ Ag

and
2 CI- 2e -+ CI2

2 3
4 6

REFERENCES Hornsby, K. M., B.J. Phot., 1950, 132. F.I.A.T., Final Report, No. 721. B.P.s, 586,211,598,657,598,174,599,377,673,091. Hanson, W. T., Jour. Opt Soc. Am., March, 1950. B.P.s, 675,797,645,170.

Whilst commercial print-out materials are usually made with gelatin as the binder, home-made papers usually employ colloids such as starches, dextrin, or albumen. A typical method is to paste 40 gm of arrowroot in 100 cc of cold water, add 700 cc of boiling water and boil the mixture until a clear solution is obtained. To this solution, whilst still warm, is added Ammonium chloride 30 gm Citric acid .. 3gm Sodium carbonate (anhyd.) 4 gm Water to 200 cc 125

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The cold jelly is brushed on to good-quality paper and worked well in, and when dry is sensitised with a silver solution, Silver nitrate Citric acid .. Water to 160 gm 45 gm 1 litre

If the developed silver is now removed without affecting

the re.~ainin.g halide, this halide can be developed to produce a positive picture :

.'O';ij;jj,),U/l/
~;.::::: 771~ii/t77

after flm development

which is also brushed on using the same volume as the salt jelly. Tbe paper is exposed to bright dayligbt (not direct sunli.ght) behind a contrasty negative until the print is considerably darker than required, as after fixing (in plain hypo) some density is lost. Plain hypo-s-or even slightly alkaline solutions-must be used as acid bypo would attack the very fine silver image which is formed. This very fine silver deposit also results in an unpleasantly coloured image, which ~o~mally is toned prior to the fixing stage. Before toning It IS also customary to precipitate the excess soluble silver salts by bathing in a weak sodium chloride solution. The following procedure is typical for papers of this type: 1. Expose. 2. Bathe for 5-10 minutes in 1 per cent sodium chloride solution. 3. Wash for 3 minutes. 4. Tone for 5 minutes by immersing in a 1: 10,000 solution of a gold or platinum salt such as gold chloride or sodium chloroplatinite. 5. Wash for 5 minutes. 6. Fix for 10 minutes. 7. Wash for 15 minutes. S.ome commercial p,:pers are 'self-toning,' and the above toning step, and sometimes the salt bath, can be omitted. Reversal Processing ~a.ITow-gauge motion pictures are normally processed to positives by the reversa.l method. Many colour materials are also processed in this way. The method is applicable also to normal materials. When .an eXJ?osed emulsion is developed fully and then washed, It consists of metallic silver and silver halide; the greater the exposure, the more silver and the less residual halide.
after bleaching

TTT".""''''''!Il~ "17m)/~

after second development

The first developer must be very energetic to develop all of the exposed grains. A little fog developed at this stage is unimportant, and to ensure complete development, it is customary to include a solvent-such as a thiocyanate-in the solution. Kodak D.168 is recommended: D.168 Metol 2 gm Sodium sulpbite (anhyd.) 90 gm Hydroquinone 8 gm Sodium carbonate (anhyd.) 44.5 gm Potassium thiocyanate 2 gm Water to 1 litre After washing for about 5 minutes the silver developed in the first developer is removed in a solution of dichromate and sulphuric acid: Sodium dichromate 5 gm Sulphuric acid (cone.) 5 gm Water to 1 litre A further 5 minutes wash is followed by 3 minutes in a solution of a reducing agent to neutralise the dichromate left in the gelatin, and enable the silver complexes to be washed out: Sodium metabisulpbite 20 gm Water to 1 litre White light may be used after the bleach bath, and if the residual halide is blackened by a normal developer, it is necessary to fog it with fairly strong light-usually during

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/'

the wash after bleaching. Any normal M.Q. developer of the universal' or print type may serve for the blackening stage. Alternatively 1 per cent sodium sulphide can be used to give a brown image, or 3-5 per cent sodium hydrosulphite will blacken by reducing the silver, without exposure to white light. Blackening is usually followed by fixing to remove any residual silver halide, and then the usual thorough wash. Many alternative procedures have been suggested, including, for example, hardening baths or chemical fogging solutions. The greatest departures occur in colour film reversal processing. Since in this case the silver produced during colour development is removed, it is customary to defer bleaching of the negative silver image, and remove all the silver at the same time. The Ektachrome technique illustrates this method :
EKTACHROME PROCESSING PROCEDURE

Blue-Print Pr~de$~es Many of the ferric salts of organic acids are 'light-senaitive, the ferric ion acquiring all electron to reduce it to the ferrous state
Fe+++

e ~

Fe++

First development. . Wash *Harden Wash Colour development Wash Harden Wash Clear Wash Bleach Wash Fix .. Wash
Exposure to photoflood

(1950) 15 min 1

Some of these salts-the oxalates, tartrates, and citrates in particular-have sufficient sensitivity to be used for contact printing. In the past, many methods of 'developing '. a visible image have been used, but only one-the conversion of the ferrous ion to prussian blue by reacting with a Ierricyanide-vhas survived. The familiar engineer's blue print is produced in this way. Although commercial blue - print papers may contain a wide variety of substances to stabilise the coating or increase the printing speed, satisfactory results can be obtained with home-prepared papers. Any reasonable quality paper is sensitised by brushing with a sensitising solution such as : Potassium ferricyanide Ferric ammonium citrate .. Water to 50 gm 100 gm 1 litre

4
5 25 1 4 5 5 1 10 1 5 10
light is made during hardening.

and drying. Daylight or very powerful artificial light must be used for the exposure, which changes the ferric ammonium citrate to the ferrous compound. The print is ' developed' by immersing in water, when the ferrous salt reacts with the potassium ferricyanide 3 Fe++R

2 K3Fe (CN)G ~

Fe++3 [Fe(CN)Gh

+2

K.R

Processes Not Using Silver Salts There have been several processes using sensitive materials other thaIl: si.lver halides, but only two are still used apart from speciallised photomechanical printing applications the blueprint and diazo processes. The main use for these processes is for reproduction of drawings, and to a very limited extent, &"eneral documeIl:t copying. The diazo processes are superseding the bluepnnt processes, particularly the dry development types.

to form the pigment ferrous ferricyanide or prussian blue . Sometimes only the photosensitive ferric salt is coated on the paper, and a ferricyanide solution is used to develop .it. In either case the print must be washed after development, but for only a short time as the prussian-blue image is decolorised in alkaline solutions. Tap water in some districts is sufficiently alkaline to attack the image slightly. The blue-print process will give a positive from a negative, and is occasionally used to print from ordinary negatives, but owing to the time taken in printing, and the trouble of making an enlarged negative for enlargements, blue toning of bromide prints is a more convenient process,

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Diazonium Salt Processes If a substituted aromatic amine is treated with nitrous and hydrochloric ~cids at a temperature of 0 degs.-5 degs. C. the ammo group IS converted to a diazonium chloride group:

. Only a very thin coating must be applied, so that the paper coloured a very pale yellow. After drying in subdued light the material is exposed, until the portions which are to be white are completely bleached. It is then developed by applying a small quantity of :
1~

RONH2

-+HN02HCI +

RO~i=N

DMZO

DEVELOPER

In slightly alkaline solutions the diazonium salts will react with phenols, and other compounds containing reactive methylene groups, to give azo dyestuffs:

Borax Sodium thiosulphate Sodium carbonate .. Coupling compound Water to

20 gm 40 gm 20 gm 10 gm 1 litre

RON:ON

H2 -+ RON==N-~H
Y
y

if the substituent R in the aromatic diazonium compound is dialkylamino, the diazonium compound is light sensitivethe diazonium group being destroyed. The light decomposition product will not couple to form an azo dye. By normal photographic standards, the diazonium compounds are not very sensitive, and, like the blue - print materials, the maximum sensitivity is in the violet and ultra violet spectral regions. An exposure of 10-50 seconds at a distance of 1 ft from 'a high-pressure mercury vapour lamp is required to produce a satisfactory print from an average original on an average paper. As the reactive material is destroyed by exposure to light a positive print is produced from a drawing, which is preferably made on translucent material. Two types of material are commercially available-the semi-wet, and the dry developed types. Semi-Wet Developed Materials

The choice of coupling compound depends on the colour of image required: ce-naphthcl Blue. . 2 : 3 dihydroxynaphthalene (Dinol) { phloroglucinol Violet ~-naphthol Red .. I-phenyl-3-meth yl-5-pyrazolone* Yellow aceto acetanili de * Brown resorcinol For production work it is usual to apply the small quantity of developing solution required with a small machine:

Although prints produced by this process are dry enough to handle immediately after development, the' dry-development' method is far more convenient.

The paper is coated with a solution of the diazonium compound, usually with the addition of an organi-c acid, thiourea, and zinc chloride to produce a more stable material. A suitable recipe would be:
DIAZO SENSITISING SOLUTION

Dry Development

Method

p-diethylaminobenzene Citric acid .. Zinc chloride Thiourea Water to

diazonium chloride

10 20 7 20 1

gm gm gm gm litre

Instead of using the coupling component in the developer solution, it is coated together with the diazonium compound. From 5-10 gm of the coupler is added to 1 litre of the above sensitising solution. After exposure the material is merely
It is advisable to dissolve these compounds them to the developer. in a little warm alcohol before adding

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133 Processes

exposed to moist ammonia fumes, which neutralise the acid of the coating solution, and allow the undecomposed diazonium compound to couple with the coupling compound,

Imbibition

I'

Either' of the above methods can be used to obtain photographic prints on other materials than paper--cloth, pottery, wood, and almost any absorbent material can be sensitised. Non-absorbent surfaces can be sensi ised by first coating with a thin layer of hardened gelatin; the sensitising solution is then applied to the gelatin surface after drying. There are other methods of using the photosensitivity of diazonium compounds, reviewed by Murray- : but as these have not been exploited to any appreciable extent they are mainly of academic interest. The Carbon and Carbro Processes If a soft gelatin layer coated on a transparent support is treated with a solution of a dichromate, and then exposed to strong light through a negative placed behind the base, the areas where the light reaches the dichromated gelatin will be hardened. If the gelatin is dyed or pigmented, the unhardened gelatin can be washed off to leave a positive relief image of dyed gelatin. An alternative method is to expose a pigmented stripping paper through the face side, and before hot-water development to transfer it to a suitable support so that the hardened gelatin is adjacent to the support. The hot water treatment will now remove both the original support and the soft gelatin, to leave the hardened image on the new support. The gelatin layers were originally pigmented with carbon black-hence the term 'carbon' for this type of process, regardless of the nature or colour of the pigment. The 'Carbro' process is a development of the carbon method in which the dichromated gelatin layer is squeegeed on to a wet, unsupercoated, bromide print. The silver image reduces the dichromate to harden the gelatin to give the same result as exposure to light. After hardening during which the silver image is bleached, the bromide and pigmented layer are parted. The pigmented layer is fixed to a new support and hot-water developed, as in the carbon process. The bromide print, after washing, can be redeveloped and used again.

Relief images can be used as intermediates in the production of dye copies by soaking the relief in a dye solution and then pressing the stained relief in contact with a gelatin blank. The blank is usually treated to retain or 'mordant' the particular type of dye used. Between 50 and 100 copies can be made from one relief or' matrix' as it is usually known. The method has very little application for monochrome work, but is very widely used for the production of threecolour prints when several copies are required=-for example, Kodak Dye Transfer and the Technicolor motion picture process. The matrix material is a silver bromide emulsion, dyed yellow or red to make the image, and therefore the relief, as compact as possible. The exposure is made through the base, and development is in a ' tanning' developer. It was stated earlier that in the absence of sodium sulphite the hydroquinone oxidation products would tan and stain gelatin. Pyrogallol and catechol oxidation products also have this property. If a developer is compounded to make the fullest use of these imagewise hardening properties, the gelatin adjacent to the silver image is hard enough to resist treatment in hot water, which removes the unhardened emulsion to leave the relief. This washing stage can follow development, as fixing is unnecessary, but steps between development and etching may be used to increase hardening. After drying, the matrices are immersed in suitable dye solutions, and successively squeezed into contact with a treated gelatin layer on paper or film. To receive the acid dyes which are normally used, the gelatin is treated with an aluminium or chromium salt such as chrome alum or aluminium acetate. The time for the dye to transfer varies with the dye used, the temperature, and the condition of the gelatin blank, but about 3 minutes at 40 degs. C. should be used as a basis for experiments. For three-colour prints, suitable dyestuffs are: Yellow-Chlorazol Brilliant Yellow 3G Magenta-Chlorazol Fast Pink BK Cyan-Solway Celestol B Further practical details of Carbon, Carbro and imbibition processes are included in Making Colour Prints by J. H. Coote.

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135

Dye-bleach Processes The action of the finely divided silver which comprises thc normal photographic image in accelerating the bleaching of dyes was disclosed fifty years ago by Schinzel," who proposed a c.omplete monopack sys-tem of sensitised and dyed layers WhICh,after exposure, development, and fixation, was treated i~ hydrogen .peroxide. In the areas where there was a heavy silver deposit, the- dye was rapidly bleached, as compared with the rate of bleaching in the areas where there was no silver image. This resulted in a positive print from a positive original. However, the differential between the rates of bleaching in the presence of silver and in the absence of silver was too small, with the result that if the highlights were completely bleached, the dense areas would also be bleached to some extent, whereas treatment which did not affect the shad~ws would not bleach the highlights completely. In this reaction, the dyes were bleached by oxidation. In 1?18 Christensen3 found that strong reducing agents such as sodium hydrosulphite or stannous chloride would bleach certain dyes only in the presence of the silver image, but no commercial process resulted, as the variables could not at that time be controlled. ~veral other workers ma?e half-hearted attempts to use this type of process, but It IS to Gaspar that the credit for overcoming the practical difficulties of the process must be given. He investigated, with remarkable thoroughness, the bleaching of dyes in the presence of silver to find dyes which would react with the bleaching agent in proportion to the a~oun~ of silver in the image. Then he had to find ways of dispersing these dyes evenly in the emulsion, and finally to w~rk ou~ the .best arrangement of h~s dyed sensitised layers. H~s m<?tl(;ll1 icture process was available in England in the p mid-thirties but was not a commercial success, possibly due to the lack of an adequate camera material or colour camera . . ~par found that the most suitable dyes were those conG taming the azo group -N =N- in conjunction with a reducing ble~ch or a bleach containing thiourea (NH2-CS-NH2) and a red~clllg agent. Th~ azo ?roup. is ruptured by the bleaching solution where there IS a SLIver Image, to produce two more or less colourless compounds, one of which should be soluble and re~dHJ: removed from the emulsion so that subsequent recombination to form the dye is prevented. It is also essential that the dye should not. diffuse from the emulsion

layer during coating or processing. The efficiency of the bleaching process can be increased by adding compounds such as azines and cinnoline to the bleaching solution. Gaspar is at present using the process for the production of prints on a white opaque base from transparencies, but liford, and Bauchet also, appear to regard this process as the answer to the problem of making colour prints from transparencies, whilst General Aniline are also interested in it, 6 Image Diffusion Processes In the last few years three different modifications of the same principle have been marketed for the prepara.tion of direct positives. If an exposed emulsion and a material containing substances which act as efficient development centres (colloidal silver or insoluble metallic sulphides for example) are placed in intimate contact and are treated with a vigorous developer containing a high concentration of a halide solvent such as hypo, two reactions will occur. First, the latent image in the emulsion will be developed, and then the undeveloped silver halide will be dissolved by the developer, and will then diffuse into the layer containing the silver precipitation centres where the silver will be deposited to produce an image of opposite character to the image in the emulsion layer. exposed area-all silver develops unexposed area-silver dissolves and diffuses into transfer layer

----

emulsion layer transfer layer

dissolved silver precipitated on development centres no dissolved silver-no image in transfer layer

In processes such as ' Copyrapid ' and' Ozarapid;' a. d~ument paper is exposed in the normal way for reflex printmg.

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It is then fed into a small developing machine face to face with a sheet of transfer paper. The two papers pass through the developing solution separately and are then passed between two driven rubber rollers which squeeze them together. After about a minute the two sheets are separated and the transfer paper contains a positive image corresponding to the original. - The Polaroid Land Camera uses a similar system, but the negative paper, the transfer paper, and the developer are all contained in the camera back. The negative paper is exposed in the normal focal plane of the camera. When the winding knob is turned the negative paper is brought face to face with the transfer paper which carries a foil' pod' containing a viscous developer. The papers then pass between two rollers which burst the ' pod ' to release the developer and also press the two papers together with the developer paste between them. This also brings the papers into a second compartment in the camera back which is opened to remove the two papers which are torn from the roll and separated. This gives a positive print and also a paper negative from. which further copies can be made later. The Gevaert Diaversal materials have both layers on the same support, the transfer layer adjoining the base and the emulsion on top. After exposure and development the top layer which contains the negative image is removed leaving the positive image in the layer still attached to the base.

Chapter 12

SOL UTION

PREPARATION

NY photographer with an experimental outlook. will find it necessary to prepare his own working solutions from bulk chemicals. A wide range of packed developers, fixers, toners, and so on, is available and the busy professional may find that it is not much more expensive to use these than to buy a balance and weigh out his own chemicals. Other workers, however, prefer the flexibility of making up their own solutions, and as only the commoner solutions are available in the packed form, it may be necessary to make up solutions from time to time. Once the equipment has been bought, it is then more economical to buy bulle chemicals and work with these. As an example of the relative cost, two litres of a stock solution of a popular M.Q. developer cost, as a packed developer, 3s. 9d., whereas the bulle chemicals for the same quantity of solution cost only Is. 7d., although, of course, the weighing time-about 10 minutes-and the capital cost of the balance should not be ignored if an accurate comparison of the economics of the two methods is considered. Equipment The basic essentials for solution preparation are a balance and weights, mixing vessels, measuring vessels and storage vessels. Chemicals and sensitive materials are not cheap, so it is false economy to use low grade equipment for solution preparation. If you cannot afford to buy the necessary items, it is cheaper in the long run to use ready packed chemicals, than to risk spoiling your materials. Not that It is necessary to buy the most elaborate equipment in the photographic supplier's show~oom. Quite frequently adequate equipment can be boug~t 111 general hardware or surgical shops at a much lower pnce than from laboratory furnishers. There can be no doubt at all that the metric system should be used when equipping a darkroom from scratch. Any calculations for altering concentrations or individual constituents or for increasing or decreasing the total volume of 137

REFERENCES
Murray, H. D .. Phot, J., 1933 (April), Supplement. ts.), Phot., 1905, 52, 608. . 3. B.P. 133.03.4.... . 4 e.i. Phot., 1954,101,509. o B.i .Phot., 1955, 102,271.
J

p, 6.

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139

solution to be made are very simple with the decimal system. This certainly cannot be said of the avoirdupois system with its pounds, ounces, grains, gallons and pints! A further confusing point is that recipes originating in the United States will use a 16 oz pint against our 20 oz one, but a litre is the same the world over. The Balance The choice of balance depends on the type of work to he done as well as on the price which can be paid. For the experimenter, the student's type of chemical balance is desirable-the' Microid ' supplied by Griffin and Tatlock is a good example. The capacity of this type of balance is about 250 gm, and weighings to within 0.002 gm can be made. The , Duorider ' type makes weights below 1 gm unnecessary. A more robust balance with an accuracy of 0.1 gm and a capacity of 2 kg is made by Towers, of Widnes. 'With this balance the riders can be used for weighings up to 200 gm. Only for quantities over this amount are separate weights needed. These types of balance, costing upwards of 5, are luxuries for the ordinary photographer. For routine preparation of processing solutions there are several types of small spring and lever balances available whose accuracy of 0.2-0.5 gm is adequate - for example, the typical letter scale, of which small models with a capacity of about 50 gm can be bought for a few shillings. For materials present in small but critical quantities-such as potassium bromide and potassium thiocyanate in developers -a 10 per cent. stock solution can be made, and measured out into the developer. For instance, 0.75 gm potassium bromide would not be weighed accurately on a letter scale, but if 10 gm is weighed out and dissolved in 100 cc of water, the requisite 7.5 cc of solution can be measured with sufficient accuracy. Another method of increasing the effective accuracy of a balance is to make up large quantities of solutions which will keep. To make up 250 cc of the working solution of D.163 the following quantities must be weighed: Metol Sodium sulphite .. Hydroquinone Sodium carbonate Potassium bromide 0.14 4.7 1.06 4.06 0.18 gm gm gm gm gm

for which an accurate balance is needed. If two litres of the stock solution are made, the quantities will be : Metol 4.4 gm Sodium sulphite .. 140 gm Hydroquinone 34 gm Sodium carbonate 120 gm Potassium bromide 5.6 gm -quantities which can be weighed with sufficient accuracy on a simple balance. For routine work an accuracy of 10 per cent. in chemical quantities is adequate for print developers and toning solutions; negative and colour developers should if possible be prepared with errors not greater than 5 per cent. The hypo concentration in fixing baths can vary 20 per cent. without harm, and can be measured by volume if the balance will not accommodate the large weights of hypo usually used. If the bath is used in a process which is carried to completion-i-e.g., fixing or bleaching-a-the accuracy of preparation is usually less critical than for processes which are stopped before completion-negative development for example. Mixing Vessels Laboratory beakers and flasks are the most convenient of mixing vessels, but are too fragile for darkroom use. The more rugged glass measuring jugs supplied for photographic and culinary use are almost as convenient, and will outlast the more fragile beakers. Stoneware' acid jugs' are also excellent for making up solutions. but as with other opaque vessels, dirt or chemical contamination may not be noticed. When stoneware vessels are used it is advisable to avoid using the same vessel for different solutions. as minute cracks in the glaze can result in contamination. Plastic vessels are now readily available. and are both unbreakable and easily cleaned. They do. however. become stained with some solutions. and although safe, look dirty. Polythene vessels, bottles, funnels and so on are strongly recommended. Stirring rods should be of glass or plastic. A small piece of surgical rubber tubing over the end of a glass rod will prevent damage to the mixing vessel. Pressed or welded stainless steel vessels are excellent. though expensive. Some cheap equipment is soft soldered and must be avoided. For large quantities, mechanical stirrers save much of the

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PREPARATION

141

labour in mixing, but in choosing and using a stirrer, it should be remembered that the purpose is to agitate the liquid to dissolve the solid. Stirring which is too vigorous, or which is continued longer than necessary aerates the solution, and this may spoil it. The writer uses a simple stirrer from a surplus rim-drive gramophone motor and as: I reduction gear which cost about 22s. Od. together. In conjunction with a 2 in plastic propeller made from odd scraps of Perspex, volumes up to four litres can be stirred very effectively. Measuring Vessels If graduated jugs are used the mixing vessel is also the measuring vessel. Otherwise the same remarks as those made about mixing vessels apply. Laboratory measuring cylinders, like other laboratory glassware, except in the small sizes, are out of place in darkrooms. Storage bottles marked with a diamond or a file at the appropriate point are quite convenient. Storage of Solutions The most convenient way of storing solutions is in glass bottles. Half-gallon bottles or winchesters are the largest size which are convenient to handle, and can be easily obtained. Aspirators, in glass or stoneware, are more convenient for larger quantities, as they have a tap at the bottom for drawing off solutions. The smaller ones can be kept on a shelf over the workbench, where they are most accessible. Rubber stoppers are the best to use with glass bottles; glass stoppers frequently stick, plastic caps break, and metal ones are dangerous. Another point to remember is that fine grain developers and other pH sensitive solutions should not be stored in bottles which have recently contained strong alkalis or acids. Washing is not enough to remove these solutions. If in doubt leave a ' dummy' developer or a 2 per cent. sulphite solution in the bottle for a week, then wash and use. Water The majority of municipal water supplies in this country are suitable for photographic use. Dirt can easily be removed with a small filter-the' Steralic ' for example . .Dissolved salts and .gases present a different problem. High oxygen content can be cured by boiling, and then cooling before using for solutions. This will also reduce the hardness

to some extent. Calgon-sodium hexametaphosphate-will prevent calcium deposits from developers and other alkaline solutions if added to the water before any of the developer constituents. I gm per litre is sufficient-even for very hard water. If any substances are present which are harmful, and cannot be removed by boiling or by calgon treatment, the only course is to use distilled water. If tap water is suspect, test it by making two batches of the solution in questionone with tap water and the other with distilled. If there is no difference in performance, the tap water can be used safely. If there is a difference, distilled water should be used. It is advisable to buy distilled water from a chemist's shop, as some so-called ' distilled water' from other sources is far dirtier than tap water. Thermometers Although not strictly under the heading of solution preparation, a few notes on thermometers may be useful. Small wide-range ones are almost useless as they cannot be read accurately. The best type would have a range of 1525 C spread over two inches, but the standard size laboratory thermometer if used with care can be accurate enough for general work. Mercury thermometers are the most reliable but are banned from some photographic laboratories because of the possibly adverse effect of mercury or its vapour on photographic materials in the event of breakage. Spirit thermometers are quite safe in this respect, but if used above 50 C (in emulsion making for example) the spirit often evaporates and forms an additional clear section at the high end of the scale, which therefore results in a low reading. The best answer to the problem is to use spirit thermometers in the darkroom and check them weekly against a mercury thermometer, but this is rather an elaborate procedure for any but large establishments. Finally, users of deep tanks will find the floating thermometers invaluable. They are somewhat like fishermen's floats, and avoid losses of thermometer and solution if the thermometer slips out of the operator's fingers into the tank.

AppendL"C

COMMON
Monovalent aceto aldehyde allyl amino amyl benzoyl
-CO.CH, -CHO -C,H~ -NH2 -C.Hll

RADICALS
Radicals methyl
-CH,

-naphthyl

-
CH2 O

c6
CD
-N02

~-naphthyl nitro nitroso phenoxy

benzyl
-

biphenyl butyl carboxylic acid Cyanide} nitrile ethoxy ethyl hydrazine hydroxy mercapto methoxy

00
-C~Ho -CO.OH -C=N -OC2H. -C2H. -NH-NH, -OH -SH -OCH,

phenyl propyl iso propyl stearyl

<: -0
-C,H7 /CH, -CH "CH, -Cl1H,. -CH:CHO

-N=O

styryl sulpho
sulphonlc

acid 143

-SOsH

144 Bivalent

BASIC PHOTOGRAPHIC

CHEMISTRY

Radicals

amido azo

-NHo-phenylene -N-=N-

benzal

o
H .
_-CO.NH-

m-P

6
Q
-502-5-CH=CHH

INDEX
Acetoacetanilide, Acetoacetic Acetonitriles, Acidity, 13 Acids, 14 Acid salts, 14 Agfacolor, Aliphatic Alkaline 113 18 18 51 compounds, salts, 14 13 39 39 Alicyclic compounds, Alkali in developer, Alkalinity, 103 102 Benzoylacetanilide, Benzoylacetic Benzthiazole, Bleaching, Blue-print Borax, Bottles, Bromide, Benzyl alcohol, 107 materials, 140 42 55 68 132 132 41, 62 129 32 108 102 ester, 102 ester, 102

h"y,,,,6

carbonamido ether hydrazo keto carbonyl methylene "\

51, 60

-0p-phenylene -NH-NH-

Bromhydroquinone,

Capitol developer, Carbon process, Carbro process, Colloids, 23

f -co-CH2-

sulphone thio vinyl

Amidol, 41, 46, 50, 62 o-aminoaniline, p-aminoaniline,

Chlorhydroquinone,

Trivalent

Radicals

2-amino-5-diethylamino toluene, 98 o-aminophenol, 39 39, 46, 64 56, 63 18 51 p-arninophenol,

benzo

o
I

Ansco Color, 114 Antifoggants, Aromatic Autoxidation, compounds,

methine

-C-

Colouraccuracy, 115 couplers, 99 coloured, 120 non-diffusing, 113 development, 96, 104, 106, 111, 112, 121, 128 masking, 117 processing, 107, 111, 112, 128 Contrast, Copyrapid, 26, 28 135 25 103

Azo group, 134 Balances, Bases, 14 Benzene, 18 32 145 Ben zotriazole, 63 Benzoxazole, 138

Crystal lattice, Cyanacetanilides, Cyanide, 71 Cyanines, 31 unsymmetrical,

33

146 Cyclic compounds, 18 Cyclohexanone, 51

BASIC

PHOTOGRAPHIC

CHEMISTRY

INDEX

147 p-Hydroxyethyl ethyl aminoaniline, 43, 98 Hydroxylamine, 51 Hydroxyl groups, 39, 41, 43 Hypo, 37, 71, 135 eliminators, 77

Developerscolour, 97 concentrated, 64 fine grain, 45, 46,.50, 59 general purpose, 58 glycin,46 hydroquinone-caustic, 57 high contrast, 58 metol,61 M.Q., 56-60 negative, 58, 59 physical, 37, 65 process, 45, 57 pyro, 45, 64, 133 staining, 64 tanning, 133 viscous, 136 Developing agents, 37 inorganic, 38 colour, 97 Development, 49 centres, 26, 37 colour, 96,104,106,111,112, 121, 128 effect of pH on, 50 forced, 66 physical, 65 reactions of, 52, 104, 106, 121 reversal, Ill, 112, 127, 128 tanning, 133 two bath, 64 water bath, 64 Diaminophenol, 41 Diaversal, 136 Diazoniurn salts, 130

Dibromodih ydroxynaphthalene: 10) Dichlorhydroquinone, 41 Diethylaminoaniline, 43, 97 Digestion, 28 Dihydroxybiphenyl, 101 Dinol, 131 Diogen,45 Dissociation, 12 Dye-bleach process, 134 Dye-line materials, 130 developers, 131 development, 131 dry development, 132 semi-wet, 130 Dyestuffsacid, 133 azamethine, 105 azine, 106, 135 azo, 120, 134 cyanine,31 indophenol, !O5 sensitizing, 31, 36 styryl, 122 vat, 96 Dye Transfer, 133 Eikonogen, 45 Elements, II Emulsion, 23 preparation, 27 stabilisers, 29 unwashed, 27 Ektachrome, 128 Ektacolor, 124 Eosin, 31 Erythrosin,31 Esterification, 22

Ferraniacolor, 114 Ferrous oxalate developer, 38 Fine grain developers, 45, 46, 50, 59 Fixation, 71 before development, 65 reactions, 72 two-bath, 73 Fixing bathsacid,74 for colour materials, 107 hardening, 75 plain, 73 Fog, 28, 35, 55, 63

Gasparcolor, 134 Gelatin, .23, 24, 27, 54 Genochrome, 98 Gevacolor, 114 Glycin, 43, 46, 62 Gradation, 26 Groups, 19, 142

Hardeners, 28, 70, 75 chrome alum, 70 colour processing, 70, 107 emulsion, 28 .fixing baths, 75 formalin, 29 glyoxol,29 stop bath, 70 Heterocyclic compounds, 21, 29, 32, 47 Hydrolysis, 22 Hydroquinonc, 39, 45, 52, 53, 57,60,133

Ilford colour, 112 prints, 135 Image diffusion, 135 Imbibition printing, 133 Indigo, 96 Indoxyl,96 Intensification, 78 chromium, 78 colour development, 81 effect on characteristic curve, 80 lead,81 mercury, 79 quinone-thiosulphate, 82 silver, 82 sulphide, 79 uranium, 81 Ions, 12 developer, 54 silver, 25, 53, 55, 72

Kendall's rule, 40 Kodachrome, 111 Kryptocyanine, 33

Latent image, 25 Lead intensifier, 81 Lepidine, 32

148 Masking, 117 . coloured couplers, Matrix, Mercury Meritol, 133 vessels, intensifier, 47 33 42 140 79 56 Measuring

BASIC PHOTOGRAPHIC

CHEMISTRY INDEX

Phenidone, J.20 Phenols, o-phenylene p-phenylene Pigment Pin Polaroid Potassium cyanol,

47, 63 99 . diarniue, diamine, 33 136 60, 108 thiocyanate, 39, 62 39, 46, 62

149
compounds, 26, 28 25 29 29 metal, 29 18 Storing Structural Sulphonates, Symbols, 11 solutions, formula, 53 36 140 17

Saturated Sensitivity, optical,35 specks, Sensitizers, chemical, precious Silverbromide, 125 chloride, intensifier,

processes,

132

Su persensitisers,

Mercaptobenzthiazole, Merocyanines,

Land camera,

dye, 29, 31 Technicolor, Temperature 27, 52, 53, 54 27, 25 Thiacarbocyanines, Thioindigo, Thioindoxyl, Thiourea, Toning, 55, 108 86 85 96 96 33 82 Thermometers, 133 coefficient, 141 42

Methylaminophenols, Metol, 42, 45, 50, 61 Microdol, 47

Precipitation, 16 of emulsion, 27 Preservative, Print-out 51, 57 47 33 100, 103 39, 133 (pyre), 37, 41, 45, 63, materials,

Microphen, 47
Mixing vessels, Mordants, 92 95 139

Promicrol, Pyrazolones, Pyrocatechol, Pyrogallol 97, 133

halide crystal, iodide, 38, 71

Pseudocyanine,

copper ferrocyanide, imbibition, 133 Miller, 92 Traube, 92

ions, 25, 53, 55, 72 nitrate, solvents, sulphide, 27 halide, 29, 85 51, 60 sulphoxylate,51 38, 97 51 51 37, 51, 133 51

blue, 89, 92 copper, dye, 92 hypo-alum, iron, 89 metallic, nickel, 89 88 85 87 86 86 89 87 89

Naphthol

couplers,

100 56

Quinaldine, Quinone, 52 thiosulphate

32 intensifier, 82

Sodium

biborate,

Nitrobenzimidazole,

carbonate, formaldehyde

51, 60

hydrosulphite, Oil formers, Organic 115 17 33 Radicals, 19, 142 Reducerscerium, 83 dichromate, 83 permanganate,83 persulphate, 83 Reduction Reduction Pentacarbocyanines, pH,13 effect on development, 50 33 (Chemical), 16, 49. 83 (photographic), hydroxide, metaborate, phosphate, sulphite, thiosulphate, Solu tion, 12 preparation, Spreading Stabilisers, Stirrers, 110, lIS, 128 27 . Stop bath,

compounds,

red, 89, 92 selenium, sulphide, direct, thiourea, 29

Oxacarbocyanines,

Oxidation, 16 developer, 51 prevention of, 51, 57 Ozarapid, 135

thioantimony, 137 yellow, 89, 91 Tripacksprinciple separate, 140 stripping,

agents, 29

Reversal, 126 processing, 127 colour materials, Ripening emulsions,

of, 109 109 110 110

139

mechanical,

69, 107

transparency,

ISO Unsaturated compounds, 18

BASIC

PHOTOGRAPHIC

CHEMISTRY

NOTES

IS!

Washing, 76 emulsions, 27 'Vater supplies, filtering, !40 testing, 141 140

Valency, Vanadium

12 toner, 09

158

NOTES

~@pb~.~
, .......... "

the TWO-STAR Developer ',:'

Some developers make a star feature of fine grain, '" " others of high film speed" '",' :' but Ilford Microphen stars both! ' " ... '... ... :. ,,

* produced by gives grain as fine as that microphen typical M,Q. borax developers. * normal "coarsegives higher film speed than microphen grain" developers.
HOW IS IT POSSIBLE P

Ilford Microphen is an outstanding exception to the general rule that fine grain and high film speed cannot be obtained from the same developer. The reason is that Microphen is based on an altogether exceptional developing agent - the efficient and versatile Ilford Phenidone. The properties of this remarkable compound have made it possible to produce a special buffered Phenidone-hydroquinone formula with a speed/grain ratio significantly greater than that of normal developers. So, while producing negatives with grain as fine as that given by M.Q. borax developers, Microphen enables film speed ratings to be increased. In addition, Microphen offers all the advantages shared by other Phenidone- based developers, including better keeping qualities, longer working life and exceptional freedom from the risk of skin irritation. Microphen is supplied in powder form in packings to make the following quantities of working strength solution : 600 c.c. (21 oz.) 2.5litres (88 oz.) (larger packings available if required).

ILFORD

ILFORD
LIMITED

The names MICROPHEN and PHENIDONE are registered trade marks

ILFORD

LONDON

1!

P H 0 T:0"80 OK S
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III",,,,,,

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