Progress in Organic Coatings, 4 (1976) 161 - 188 0 ELsevier Sequoia S.A.

, Lausanne - Printed in the Netherlands

161

ASSESSMENT

OF PIGMENT

DISPERSION

W. CARR

Pigments Division, Ciba-Geigy Plastics & Additives Wythenshawe, Manchester M23 9ND (Gt. Britain)

Company,

Roundthorn

Industrial

Estate,

Contents
Introduction, Criteria, 162 Classification, 163 161

Wet systems, 164 4.1 Indirect methods, 164 4.1.1 Flow properties 4.1.2 Dielectric properties 4.1.3 Optical densities 4.1.4 Hindered settling 4.2 Direct methods, 169 4.2.1 Electronic methods 4.2.2 Sedimentation methods 4.2.3 Photosedimentometer attachment Dry systems, 180 5.1 Indirect methods, 180 5.1.1 Colour strength
5.1.2 Gloss

5.2

5.1.3 Optical densities Direct methods, 184 5-2.1 Electron microscope 188 188

Conclusion, References,

1. Introduction From measurements of nitrogen surface areas and densities, the order of magnitude of the basic particle sizes of pigments can be readily calculated from the simple formula: SC 6
Pd

where S is the nitrogen surface area, p is the density, and d is the mean diameter of the basic particles.
.._

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The calculations show that the basic particle size of most pigments is below 1 pm. With many organic pigments and most carbon blacks, the basic particle size is below 0.1 pm. These figures are the diameters of equivalent spheres. On the other hand, in the full strength powder pigments sold commercially, the smallest speck of powder must be at least 20 pm in size, otherwise the Pigments would not be a powder but would be in the form of a dust or smoke. In the commercial powder forms of pigments, therefore, the basic particles must be present in the form of closely packed aggregates, each speck of powder containing at least lo6 basic particles. In use, the pigment is incorporated into a suitable vehicle and the system is ground, or milled or dispersed in order to break down these aggregates as far as possible. This process takes equipment, energy and time, and requires supervision; it therefore costs money and there is a strong financial inducement to control the dispersion process to avoid unnecessary cost. As the dispersion proceeds, the technological properties of the system alter. The colour strength increases, as does the brightness and gloss. These improvements are usually welcome. Less welcome may be increases in viscosity, greater deviation from Newtonian flow, and possible decreases in opacity. To get the correct combination of properties, and to ensure standardisation from batch to batch, again requires control of the dispersing process. The control of the dispersion process is therefore important, both from the cost and performance angles. Control requires measurement of the dispersion state so that the process can be stopped at any desired stage. It is the purpose of this paper to survey actual and potential methods of assessing pigment dispersion and to comment critically and impartially on their suitability. The assessment of pigment dispersion in any system means, in practice, the determination of the actual size of the pigment particles or the aggregztes of particles present in the system. If the particles or aggregates are not uniform in size, then the particle size distribution has to be measured.

2. Criteria A considerable number of methods have been described or suggested in the literature for determining the particle sizes of solid particles in suspension, whether they are pigmentary or non-pigmentary. A useful survey of this field was published in 1963 by the Particle Size Group of the Society for Analytical Chemistry [ 11, and it is understood that this survey is currently being brought up to date. To help decide whether any particular technique is or would be suitable for pigments, we need some criteria by which the technique can be judged. These criteria readily select themselves to anyone familiar with pigment technology. They are: (i) sensitivity, (ii) versatility, and (iii) applicability.

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The first criterion, sensitivity, is the most important one as it is basic. It is now well established, from a variety of techniques, that in practical pigmented systems, the pigment particles are in the sub-micron range. Accordingly, any method of size determination will not be suitable for pigments if it cannot deal with the sub-micron range. The second criterion, versatility, stems from the wide variety of pigments and vehicles that are met with in practice. The pigments comprise organics, inorganics and carbon blacks. Organic pigments include azos, toners and specialities such as phthalocyanines, quinacridones, dioxazines, carbazole violets, isoindolinones and many others. Inorganics include titanium dioxide, oxides of iron, chromes and cadmium pigments among others. Together with carbon blacks, these constitute a very varied range, and if the proposed method for particle size analysis involves any chemical analysis of pigments to determine the amount in specific size fractions, many of the pigments on this list would present difficult problems. The vehicles can be aqueous,emulsion, oil based or solvent based systems. They will usually include resins in appreciable quantities and other materials such as surfactants, driers, etc. in minor quantities. Suitable methods for pigmented systems must therefore be capable of use with all types of vehicles, aqueous and non-aqueous, and be unaffected by the presence of solutes. The third criterion, applicability, stems from the colloidal nature of pigment dispersions. As already mentioned, in most systems the pigment particles are less than 1 pm and the system is wholly or partly in the colloidal range. This means that a pigmented system is an equilibrium system, representing a balance between the forces of attraction and repulsion. Ideally, any particle size determination technique for pigments should not involve any alteration to the system, to ensure that the equilibrium is not affected. If the system has to be diluted. for the purpose of the experiment, then there is always a possibility of dilution shock occurring which will give coarser size distributions than the original true one. If the measuring technique involves the application of shear to the system, then it is possible that the size distributions obtained will be finer than the original true one. This susceptibility of the pigmented system to the effect of external forces and alterations must always be kept in mind. 3. Classification Using these three criteria, we can now survey various size-measuring techniques to determine their suitability for application to pigmented systems. To ensure clarity and order, the foilowing classification wiIl be used: (i) wet systems, (ii) dry systems. As the name implies, the wet systems will include materials such as paints, printing inks, paper-coating mixtures, etc. before they are applied and while they are still in a fluid state. The dry systems will include the films

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derived from such products, as well & mass pigmented products-such as plastics, rubber and viscose. In each of these ttio major classifications, two sub-divisions will be used, namely: (i) indirect, (ii) direct. Indirect methods deal with the measurement of some property of the system, other than particle size, which is connected in some known way with the particle size of the pigments. Direct methods deal with the actual physical measurements of the size or size distributions of the pigment particles in the system.

4. Wet systems This field would include paints, printing inks, paper-coating mixtures, stainers and pigment pastes. 4-l Indirect methods 4.1 .I Flow properties It is known from practical experielice that as the level of pigment dispersion increases, the flow properties of the resultant dispersion can alter. The alteration appears to be greater with higher pigment concentration. Measurement of flow properties would therefore appear to offer a means of following pigment dispersion and measuring it. Such an approach has many obvious attractions. In the first place, no dilution of the systems would be involved and therefore no danger of dilution shock. Secondly, any shear applied to the system would only be small and therefore unlikely to affect the dispersion level. Thirdly, flow measurements using modern instruments are quick and easy. Sophisticated cone and plate instruments such as the Shirley Ferranti viscometer and the Weissenberg Rheogoniometer are available, as well as concentric cylinder instruments such as the Rheomat and Brookfield viscometers. These only require small amounts of the material, are rapid in use, can be made recording instruments and will cover a wide range of applied shears. As a technique, flow measurement can be applied equally well to aqueous and non-aqueous systems and to all types of pigments, organic, inorganic and-carbon blacks, because there are no analytical steps involved. The advantages of this indirect method are therefore many and obvious and much work has and is being done in this field 12). The only major drawback to this method is in the interpretation of the results, that is, in relating the flow properties of the system ,to the dispersion levels of the pigment in the system. Many workers have attempted to derive a theoretical relationship between-flow properties and pigment dispersion, but with only limited succ&s~ and an acceptable .welI-def&d relirtionshiphas not yet emerged,-This is not altogether surprising considering.the variables -~ ~. ; involved.. These include: 1 ._
.~ .-

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~1~~~~
0.1 02 0.3 C5Cr% dhneter in microns
0.4

,oo

L_

1 I I

;tTi_r--;t-r;
i
. i

---;--IT--?,

i--i.-;-~+-&;--T~j0.4

) jy-

0.1 0.2 0.3 Xl% diameter in microns

Fig. 1. Flow properties of Blue GLSM lithographic inks. 25 C, 7000 dyne cme2. Pigment 10%. --25%, - - - - 20%, - .--- 15%, concentration: Fig. 2. Flow properties of Rubine concentration; - - - - 22.570, --4BP lithographic inks, 25 C. 7000 dyne crnm2. Pigment 15%,-----10%. 20%, -.-.17.5%, -

(a) the rate of shear applied (b) the pigmentation level (c) the dispersion level (d) the interaction between the surface of the pigment particles and the actual vehicle. With regard to this interaction, it is commonly assumed that, in nonaqueous systems, dispersion stability is obtained by adsorption of long-chain molecules from the vehicle on to the surface of the pigment. The effect of this type of absorption on flow properties is difficult to predict in the light of present knowledge. Experimentally, the type of results, found in the authors laboratories 133 and shown in Figs. 1 and 2, illustrate the difficulties experienced in relating fiow to dispersion levels. These graphs show the relationship between apparent viscosity and dispersion at different levels of pigmentation for a &phthalocyanine blue and a calcium 4B toner in a lithographic varnish. The viscosity was measured at a shear stress of 7000 dynes cm- on a Shirley Ferranti viscometer. The dispersion levels were determined using an indirect method of Colour measurement described later. From the graphs for both pigments, it can be seen that at low concentrations the viscosity is indepe_ndentof particle size. As the pigment concentration rises, the viscosity is independent of particle size until a certain size
-.>

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is reached, and further reduction in the size markedly increases the viscosity. At high levels of pigmentation, the viscosity is very dependent on size throughout the whole size range. Curves of the type illustrated in Figs. 1 and 2 demonstrate another fact. Even if the relationship between dispersion level and flow properties is well known, flow properties are only a sensitive guide to dispersion levels at high pigmentation levels. In the examples shown, the flow properties would give little information on dispersion levels at pigmentation levels of 15% and below. To sum up, the measurement of flow properties as a guide to assessing dispersion level has many attractions but some weaknesses. If the relationship between the two could be more clearly defined, then the use of flow measurements would be a valuable guide to dispersion, particularly in systems which normally use a high level of pigmentation. These would include lithographic inks, ball mill bases, and speciality pigment pastes. 4.1.2 Dieiec tric properties At various times it has been suggested that the dispersion process is probably accompanied by changes in dielectric properties of the system, and therefore measurement of these changes in dielectric properties would provide a convenient method for following the dispersion process. if this idea worked, it would have some important advantages. There would be no necessity for diluting the system, therefore there would be no danger of dilution shock. There would be no necessity to apply any form of shear to the system. On the other hand, shear could be applied to the system deliberately, in order to break down thixotropy, while measurements were actually in progress, and this might give an important and valuable insight into thixotropy. It was envisaged that a condenser would be set up with the pigmented system as the dielectric medium between the plates. The capacitance of the cell could then be readily measured by known techniques. If a stirrer was present in the dielectric medium, it could be switched on and off at controlled intervals, to follow the development of any structure. It was felt that this technique would enable the dispersion process to be monitored, as well as the build-up of structure with time. These theoretical advantages seem attractive enough to warrant some investigation, but there is little published work on the subject. Some preliminary work at the Paint Research Station was reported at a Seminar held there in 1974. This preliminary work seemed to indicate that although dielectric changes did occur in some pigmented systems as dispersion progressed, the extent of the changes varied markedly from pigment to pigment. With most pigments, the extent of the changes was so small as to make the method unsuitable. With the other pigments, although the overall changes were considerable, the pattern of the changes was not well suited to following dispersion. In the regions of coarse dispersion, say from 5 pm down to 1 pm, as the dispersion improved, there was appreciable change in dieiectric properties, but the rate of change decreased as the dispersion improved. Con-

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sequently, in systems where the particles were less than 1 pm, the dielectric properties varied little as dispersion was improved Further. Consequently the sensitivity of dielectric changes as a measure of dispersion level is very poor in the sub-micron range. This is a major drawback, as all practical experience confirms that this is the important region of dispersion. It is also believed that dielectric measurements are best suited to non-aqueous iystems and least to aqueous systems. This specificity with regard to pigments and vehicles, coupled with poor sensitivity in the sub-micron area, if confirmed, would be major drawbacks. The potential attractions of such a technique, however, would appear to warrant a thorough and authoritative investigation. 4. I .3 Optical densities The optical density of a suspension can be measured on a transmission spectrophotometer in a suitable optical cell. The optical density of different concentration suspensions can be measured and plotted against the concentration of the dispersed phase. if the graph is linear, the extinction coefficient can be calculated from its slope. For a pigment, the extinction coefficient is a function of the optical constants of the pigment and its particle size in the suspension. The extinction coefficient will tnerefore be related to the particle size of the pigment particles in suspension. Experimentally, optical densities can be measured readily on transmission spectrophotometers using cells of known path lengths. With pigmented systems, the measurement should be carried out at the wavelength of maximum absorption of the pigment. The main problem is reducing the optical density of the system to a level at which it can be conveniently measured. Most commercial pigmented systems are far too concentrated for the purpose, even when a short path-length cell is used. Consequently, they have to be diluted, and the degree of dilution is considerable. Using a cell of 100 nrn path length, pigmented systems have to be diluted to a concentration of 0.5% pigment or less. The optical densities of dilutions with 0.5% pigmentation, and lower levels, are measured and the optical densities are plotted against pigment concentration. The resultant graphs should be linear and the extinction coefficients can be calculated from their slope,. c The extinction coefficient for any given pigment is related to its particle size. The exact nature of this relationship can be determined empirically or theoretically. Empirically, the particle sizes of the pigment dispersions have to be determined directly by another method such as centrifugal sedimentation ].4]. Extinction coefficients can then be plotted against particle size to give a master curve for the particular pigment. With a subsequent dispersion of the same pigment, the extinction coefficient is obtained from optical density measurements and the corresponding particle size is read off from the master curve of extinction coefficient uersus particle size. Theoretically, if the optical constants n, the refractive index, and 12,the absorption coefficient, are known, it is possible to calculate the relationship between extinction coefficient and particle size using the hlie theory [5], and hence a theoretical

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curve of extinction coefficient uersus particle size can be drawn. Once this has been done for a particular pigment, then, as before, for any given dispersion of that pigment, optical density measurements will give the extinction coefficient, and, with this value, the corresponding mean particle size can be read off from the theoretical master curve. There is no real experimental difficulty in measuring the optical densities of diluted paint stainers, liquid inks or paper-coating systems and in calculating their extinction coefficients. Master curves of extinction coefficients uersus particle size can be determined both empirically and theoretically so that the relationship between the two can be well defined. Optical density measurements can therefore be used as an indirect way of determining the level of pigment dispersion. As a technique it has many attractions. It is fairly rapid and relatively simple, and the apparatus required is standard equipment in many laboratories. The curves of extinction coefficient uersus particle size, whether determined empirically [4] or theoretically [ 53, have quite steep slopes in the sub-micron region, so that the method is sensitive enough for most purposes. It is applicable to all types of systems, aqueous or non-aqueous, and is not affected by the presence of solutes in the liquid phase providing they are colourless. There are, however, three drawbacks to the use of this technique. The system has to be diluted considerably, a master curve is necessary, and the method only gives a mean diameter and not a size distribution. The dilution step is certainly fraught with danger as there is always a possibility of dilution shock. This can be guarded against by diluting in steps, slowly, with stirring, and by incorporating resin or surfactant into the diluting medium. It is interesting to note that in general, aqueous pigmented systems are more resistant to dilution shock than non-aqueous systems [ 61. The dangers associated with diluting must never be overlooked, but in the majority of cases they can be overcome. Master curves are necessary if extinction coefficients are to be translated into particle sizes. Empirical curves require a disc centrifuge or similar instrument for their determination, but once available they can be used indefinitely with that particular pigment. Theoretical master curves can be obtained with the help of a suitable computer programme, from a knowledge of n and k and an understanding of the Mie theory. It is of course possible that, in ftiture, pigment manufacturers may supply master curves as an integral part of their technical data sheets, in the same way that they now supply reflectance curves. Without master curves, extinction coefficients can only be used as comparative measures of dispersion. The extinction coefficient is a function of all the pigment particles present in the dispersion, whether big or small, and can therefore only give a value for the mean particle diameter, It can give no information on the particle size distribution. 4.1.4 Hindered settling This is another technique that can be applied to pigmented systems and which is claimed to give information on the degree of dispersion. To obtain

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hindered settling, the concentration of pigment particles must be 1% or more_ This ensures that the pigment phase tends to settle out en masse rather than as individual particles. There is a boundary line between the pigment phase and the clear medium. The settling takes place under gravity and the rate of settling is measured as well as the final sediment volume. From these measurements it can be deduced whether the pigment particles have flocculated and, if so, whzt the mean size of the flocculates are. If the measurements are carried out on a pigment dispersed in a solvent alone and then dispersed in the solvent containing resin, information can be deduced on the dispersing power of the resin. It has been suggested [7] that this technique could be used to assess dispersion levels of pigments, but no papers have as yet appeared describing such applications. It is believed that
the technique provides a simple, inexpensive way of classifying dispersions as good or bad, but that it cannot be used for following or identifying small changes in dispersion.

4.2 Direct methods In this section we are surveying techniques which can, or may, measure directly the particle size distribution of pigments in pigmented systems while they are still in the fluid state. Again our criteria are sensitivity, versatility and applicability. Possible methods can be discussed under two headings, electronic and sedimentation. 4.2.1 Electronic methods The CouIter Counter is the best known example of electronic size-measuring methods. It is based on the Coulter principle of letting the dispersion flow through a narrow aperture_ Each particle wilI displace its own volume of media, and if there is a difference in the conductivities of the solid and liquid phases, the displacement will give rise to a change in coilductivity that will be proportional to the particle volume. There is a tremendous amount of literature on this principle, and on this instrument and its application to a wide variety of systems. There is no doubt that this instrument represents a major step forward in particle size measurement. It is simple in function, quick and accurate. However, it is fairly generally accepted that it is not sensitive enough to deal with particles in the sub-micron range. On this ground alone, it is not suitable for pigmented systems. It is also doubtful whether it could be used successfully in most commercial non-aqueous systems, because the differences in conductivity between the pigments and the media are much smaller. 4.2.2 Sedimentation methods These methods of size analysis have many attractive features. The theory and practice of free sedimentation, based as it is on Stokes law, is well understood and accepted. Moreover, this theory is applicable to all dispersed systems, whether they are aqueous or non-aqueous, and is not affected by the presence of solutes such as resins, surfactants, etc. in the continuous phase. The one thing that is crucial to all sedimentation work using Stokes
equations is that the sedimentation must be free and unhindered. Each par-

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title must fall freely, independently of its neighbours. In practice this means that the pigment content of the system must be about 0.1% or less, and this means, in turn, that the original system must be diluted considerably. This brings in the danger and possibility of dilution shock, i.e. of coarsening of the dispersion. If this takes place, then the results obtained will not be representative of the original system. The possibility of dilution shock is a real danger and must always be kept in mind. It is a possibility with all techniques and instruments that are based on free sedimentation, whether it is gravity or centrifugal sedimentation. The danger is, however, not sufficient to write off such methods, but tests must always be made to see if dilution shock is present. If it is, steps can usua.lly be taken to guard against it. These steps include the incorporation of resin or surfactant into the diluting media, and making the reduction in steps. Where the system is very viscous, as in, say, some litho inks, then the physical incorporation of the diluting medium into the ink can present problems. Sometimes considerable shear is required to bring about the actual mixing of the viscous ink and the diluent, and this shear could conceivably increase the level of dispersion. One way round this problem is to warm the ink to reduce its viscosity, and to make the dilution in stages. Another requisite of sedimentation techniques in general, which can easily be overlooked, is that the pigment particles should not dissolve in the sedimenting liquid. This does not arise with inorganic pigments and carbon blacks, but it is known that many common azo pigments have a distinct bleed or slight solubility in the systems in which they are used. Arylamide yellows and toluidine reds are important examples of this. Would the bleed of these pigments, while sedimenting at low pigmentation levels, be sufficiently great to vitiate the particle size results? The literature is silent on this subject. The procedure wit.h all sedimentation techniques is fairly standard: dilution to about 0.1% solid phase or less, sampling from a fixed known point at fixed known times, and analysis of the samples to determine the content of the sohd phase. From the depth of the sampling point from the surface and the time of sampling, the maximum size of the pigment particles in the sampIe can be calculated. As the time increases, the maximum size of particles in the samples decreases. From the data a size distribution curve can be built up, although the mathematics can be tedious. Gravity sedimentation is too slow to classify particles which are all in the sub-micron range. Centrifugal sedimentation can separate such particles in a reasonable time if the speed of revolution is high enough. Commercial apparatuses for determining particle size distribution, based on centrifugal sedimentation, are now on the market and have been and are being used with pigmented systems. The best known of these instruments is probably the Joyce Loebl disc centrifuge, and the authors experience with this instrument will be described in order to illustrate the advantages and disadvantages of the technique [8, 91. The instrument consists of a hollow, accurately machined disc, mounted vertically, which can rotate at selected speeds up to 8000 rpm. The original disc was made of Perspex, but solvent-resistant discs are now available.

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With this instrument a line start technique is used and a sample of the suspension is removed automatically down to a fixed depth by suction through a probe. The time at which the sampling is carried out can be preset and the sampling is done automatically. The maximum size of particles in any sample is determined by the time of spinning and the speed of spinning, and for any given system these are the main operating variables. For a typical experiment, eight to ten spinnings are made giving eight to ten samples representing different size fractions. These samples are analysed for t.heir pigment content, and in this way a complete size distribution curve is obtained_ The line start technique simplifies the mathematics of the calculations. It will be seen from this brief description that the method has three stages: dilution, fractionation, and analysis. The dilution stage is necessary to ensure free unhindered sedimentation, and the dangers inherent in this step have already been pointed out. Again it must be pointed out that the dilution stage is necessary for all sedimentation experiments based on Stokes equations, and does not apply solely to the Joyce Loebl instrument and technique. The fractionation stage is largely automatic and trouble-free and gives a number of samples of pigment suspensions of differing maximum particle sizes. In the analysis stage, the pigment content of each of these fractions has to be determined, and the analysis can present problems. These problems stem from the small amounts of pigments present in each sample and the fact that pigments are by definition substantially insoluble in most solvents. The amount of pigment present in each size fraction is of the order of two milligrams, and the liquid phase may have small amounts of resin, driers and surfactants present. With these small amounts of pigment, dry weight determinations are not sufficiently accurate. Most azo organic pigments can be handled readily enough by getting them into solution and measuring the optical density of the solution under standard conditions. If the liquid phase in the fraction is water, the water is removed by evaporation and the pigment taken up in dichlorobenzene or dimethyl formamide. If the liquid phase is non-aqueous, the same technique can be used. With some pigments, the dissolving solvent can be added directly to the size fraction, but with most, the evaporation stage is required_ The optical densities are converted to pigment weights by the use of a previously determined calibration graph of optical density uersus concentration. For non-azo pigments, such as phthalocyanines, dioxazine and carbazole violets, isoindolinones, etc., a suitable technique is to evaporate off the liquid phase from the fraction and dissolve the pigment in concentrated sulphuric acid. An aliquot of this solution is rapidly diluted with water containing a small amount of surfactant and then the optical density of the resultant clispersion is quickly measured, i.e. within 20 minutes of the dilution. During this time interval, the suspension is fine enough to obey Beers Law. Again, the optical density can be converted into a pigment weight by reference to a previously calibrated graph.

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The reader will appreciate that the analytical problems associated with inorganic pigments are likely to be more difficult because of their greater insolubility. Where the analysis is possible, it is likely to be so tedious and time-consuming as to rule it out of court for practical purposes. With titanium oxide size fractions, for example, the fraction has to be evaporated to dryness; then the residue is submitted to a caustic fusion, and then the mass is extracted with water. This will give the titanium in a soluble form and then it can be treated with a suitable reagent to give a characteristic colour which can be used as a basis for analysis. For day to day purposes, this analytical step is far too lengthy. With carbon black size fractions, the analytical problems seem to be insuperable. The technique of centrifugal sedimentation using a line start technique and sample removal would therefore appear to be restricted to use with organic pigments because of the analytical problems associated with other pigments. We are left with the frustrating position of being able to fractionate all types of pigmented systems into their various size fractions, but unable to determine the amounts of pigment in these size fractions. With organic pigments, optical density measurements represent a convenient and accurate way of measuring the pigment contents of the fractions. The disc centrifuge has worked well with organic pigment dispersions of all kinds, both aqueous and non-aqueous. The method gives size distribution curves which are reproducible down to sizes as low as 0.025 pm, and the theory of the method is sound. The method, therefore, as far as organic pigments are concerned, appears to satisfy our three criteria of sensitivity, versatility and applicability, provided care is taken at the dilution stage. Figures 3 and 4 illustrate size distribution curves that have been obtained in this manner for a number of practical pigmented systems. These bear out the above claims for the technique. On the other hand, the method has a number of weaknesses and limitations. As we have already indicated, the system has to be diluted and therefore dilution shock has to be guarded against. The method is essentially restricted, in practice, to non-bleeding organic pigments because of the analytical problems associated with inorganic pigments. Even with organic pigments, the method is slow. Normally eight to ten separate spinnings have to be carried out in order to get eight to ten different size fractions, then these fractions have to be evaporated to dryness, taken up in a solvent and their pigment content determined by analysis. All this takes time and, from start to finish, a particle size distribution curve will take about one and a half days to determine. This means that the method can only be considered as a research tool. 4.23 Photosedimentometer attachment Many of these drawbacks can be overcome by the use of a Photosedimentometer Attachment (PSA), which was a development designed for use with the disc centrifuge. In this development, a narrow beam of light is shone through the disc and falls on to a photocell. The resulting voltage is amplified

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80

.s
d

c?

60

z .v
40

20

0.01

0.i

1.0

particle

diameter

in microns

Fig. 3.. Particle size distribution curves obtained with a disc centrifuge for Irgazin Violet 6RLT ball-milled paint stainers, after milling for 2 hours (A), 12 hours (33) and 72 hours
(CL

01 part&

diameter m microns

Fig. 4. Particle size distribution curves obtained with a disc centrifuge for a Calcium 4B gravure ink using Ca/Zn resinate in 50/50 SBP5: toluol. Initially x - x, after 3 months o - o.

and fed to a pen recorder which can, therefore, plot a curve of turbidity veisus time. The light passes through the suspension in the disc at the same depth from the surface that the probe reaches. The method of operating the instrument is the same as before and again uses a line start technique. One ml of a diluted suspension is injected into the spinning disc containing a suitable spin fluid and a curve is obtained of turbidity v&rsus time. From the speed of the disc, the instrument constants, the

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densit.y of the pigment and the spin fluid, the time axis can be converted to particle size and the graph is redrawn to give a curve of turbidity uersus particle size, with the latter axis increasing arithmetically. Ideally, this curve should start at zero turbidity and return to zero turbidity, and if it does not, then it is extrapolated to do so. The curve is then normalised. The area under the curve is measured and this is represented as 100% weight of the pigment injected into the disc. To obtain the weight of particles under a given size, the ordinate corresponding to that size is drawn and the area under the curve to the left of the ordinate is measured, and this is expressed as a percentage ratio of the whole area to give the weight percentage of pigment particles below that particular size. By drawing more ordinates and repeating this step, a complete picture of the size distribution can be obtained and an integral curve can be drawn of weight per cent undersize versus particle size. This is the same type of curve that. is obtained by using the earlier technique without the PSA attachment. Let us examine, in detail, the effects of using the PSA technique. In the first place, the actual experimental time is cut down dramatically because only one spinning is required. This one spinning gives the data for a complete size distribution curve, whereas; in the original method, one spinning would only give the data for one point on the size distribution curve. Furthermore, no analytical step is required; this again cuts down the time factor. Also, if the spinning time selected is, say, 45 minutes, the actual experiment, together with the normalising of the resultant curve s, can be completed in about two hours. This compares with one and a half days by the original method. The absence of any analytical stage has an even more significant effect. It immediately widens the scope of the method to include all pigments, whether organic, inorganic or carbon black. Extenders and emulsions and resin dispersions can also be handled. The reduction in time and the extension of technique to include all types of dispersions are very significant advances. The reduction in time means that the technique can be considered for factory control as well as for research purposes. Furthermore, the disc centrifuge, when fitted with a solvent-resistant disc and a photosedimentometer attachment, can handle all the systems normally used in the surface-coating industries, irrespective of the nature of the disperse phase or the continuous phase. It would therefore appear to satisfy completely two of our assessment criteria, namely sensitivity and versatility. It will also satisfy the third criterion, namely applicability, if dilution shock is guarded against when the original system is diluted. As might be expected, the photosedimentometer technique does have some disadvantages. Because it is a sedimentometer technique, the original pigmented systems have to be diluted.pd this always brings on the dangers of dilution shock. Because only one spinning is used, the speed at which this is carried out has to be carefully chosen, so that both coarse and fine particles in the.sys-

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.z = ii =. 5

160 120 80

Time of spinning converted particle diameter (Microns)

to

Fig. 5. Disc centrifuge with PSA. Recorder paint stainer. Faster disc speed. z 5 g
g z F: -k 1.0 0.4 0.3 0.2 to

curve for phthalocyanine

blue decorative

160
120 80 40 0.1

Time of spinning converted particle diameter (Microns)

Fig. 6. Disc centrifuge with PSA. Recorder paint stainer. Slower disc speed.

curve for phthalocyanine

blue decorative

tern can be accurately sized. Experience has shown that most pigmented systems have a fairly wide size distribution varying from, say, 0.05 to 2.0 I_tm, i.e. by a factor of 40. With such systems, a high spinning speed will give a recorder curve of turbidity (T) against time similar to that illustrated in Fig. 5. This means that although the curve drops to zero and all the fine particles are assessed, the coarse end of the.curve is cramped and the measurement of the coarse particles will be inaccurate. On the other hand, a slow spinning speed will give a curve similar to that illustrated in Fig. 6. The coarse end will be opened up, but the time of spinning will be excessively extended to account for the fine particles. An excessive spinning time may bring in other errors such as spin fluid evaporation and temperature rises. To avoid these, the spinning may have to be stopped before the curve reaches zero and considerable extrapolations made. A medium speed will fall in between these two extremes_ In our experience, the photosedimentometer is not suitable for pigmented systems with a very wide range of particle sizes because only one spinning is involved. We restrict its use to systems where the particle sizes range from approximately 0.1 to 1.0 pm. Further evidence for this is given a little later. The method only gives comparative results. As the grinding of any given system proceeds, the weight percentage undersize uersus particle size curves obtained by the photosedimentometer technique become progressively finer, but the curves are only comparative. They do not give absolute size

176

_
TABLE 1

.
Dioxazine violet

Comparison of sizes from absolute and PSA measurements. in alkyd based decorative paint stainer Ball milling time, hours 50% diameter(PSA method), 50% diameter w (absolute

6
0.56 0.35

12
0.42 0.26

24
0.26 0.21

96
0.21 0.18

p method),

distributions. At least the size distributions obtained by this technique differ, and differ considerably, from those obtained for the same dispersions by the original method. An indication of the sort of differences Dbtained is

given in Table 1, where the results for a paint stainer based on dioxazine violet in an alkydiesin system are given:
We believe that the original method gives absolute results while the PS method gives values which are in error because of the uncertainty of the

relationship between concentration and turbidity at low particle sizes. The marked deviation of the PS results from absolute values is a distinct drawback to the wider use of the method. However, it can be largely overcome by the use of calibration curves. For any one specific pigment, for example a /3-phthalocyanine blue, a suitable pigmented system is made up and its particle size distribution is determined both by the original absolute method and by the PS method. To obtain the calibration graph for this pigment, log (c/lzT) is plotted against log d on log-log paper. The value of c, the weight of pigment in the spinning disc whose particles are below d pm in diameter, is derived from the weight percentage undersize results obtained using the absolute method. The term kT is the arbitrary turbidity or optical density reading obtained on the vertical axis of the chart record, and d is calculated from the instrument constants and the time and speed of spinning. The calibration graph for this pigment is shown in Fig. 7, and it will be seen that the graph is linear between sizes 0.1 and 1.0 pm. Other organic pigments give straight-line graphs by this method, although the lines differ markedly in slope. There is a certain amount of scatter about the lines and a very pronounced deviation from linearity at diameters greater than 1.0 pm. This may be due to the collection efficiency of the probe being poor at coarse sizes and/or the turbidity readings for these sizes being inaccurate because the single spinning used in the PS method is too fast for them. The straight lines can be better defined by plotting c/lzT against d on linear graph paper, drawing the best curve through the points and using this curve to obtain the log-log plot. In Table 2, the slopes of the straight lines have been listed for a number of organic pigments representing all parts of the spectrum. The figures in this t.able demonstrate conclusively that there is no single master graph suitable for the calibration of all pigments.

177

O-l

Diameter (microns)

Fig. 7. Calibration TABLE 2

curve for Copper

Phthalocyanine

Blue GLSM.

Slopes of calibration Pigment

graphs C.I. index reference Slope of calibration graph

Green DBN Violet 6RLT Green GLN Blue GLSM Grange F2G Magenta TCB Red M2B Red CBN Yellow GTN Red RLY Rubine 4BP Yellow 2GP Yellow BO Yellow LBAW

Green 8 Violet 34 Green 7 Blue 15 Orange 34 Violet 2 Red 48 Red 53 Yellow 1 Red 49 Red 57 Yellow 17 Yellow 12 Yellow 13

0.42 0.45 0.50 0.60 0.72 0.80 0.83 0.90 0.95 1.02 1.05 1.28 1.37 1.68

Armed with a calibration graph for a pigment, the determination of the size distribution of that pigment in surface coatings becomes relatively straightforward. After diluting to 0.5% pigment content, the dispersion is injected into the spinning disc fitted with the PSA and allowed to settle through a suitable spin fluid. The recorder gives a plot of h T against time. The graph is redrawn, with the time axis converted to particle diameter d. For each selected value of d, the corresponding kT reading is multiplied by the value of c/VT read off from the calibration graph for that size. This gives a term c which is a function of pigment concentrationThe values of c are plotted against the : -1

178 values of d on linear graph paper, and the graph is normalised as before to give a graph of weight per cent undersize uersus particle diameter. The size distribution curve is now an absolute curve. This :an be checked by repeating the experiment using the absolute method without the PSA. Only one spinning has been required and no analytical step was necessary. Armed with the requisite calibration curve, a disc centrifuge fitted with a solvent-resistant disc and a photosedimentometer attachment can give an accurate, absolute size distribution curve of any dispersed system with only one spinning. The time of this spinning, together with the necessary redrawing and normalising of the curve, takes about two hours. Once determined, a calibration curve can be used with all subsequent dispersions and products based on that pigment. To obtain a calibration curve requires particle size determination by both methods. This can be done with organic pigments, as these are well suited to the absolute method. Inorganic pigments are less well s*uitedto the absolute method, due to analytical difficulties. In many cases, however, these can be overcome with time and care, and hence calibration graphs can be drawn for them. The calibration graph for a rutile titanium oxide is shown in Fig. 8. The minimum in this graph is probably associated with the fact that the scattering power of this pigment goes through a maximum as its particle size is reduced. Garbon blacks cannot be measured by the absolute method, so that calibration graphs cannot be directly obtained for them. A way round this difficulty has been suggested recently [lo J , namely to use for carbon blacks the calibration curve obtained for Pigment Green EL If the beam of light used as the sensing mechanism in the photosedimentometer technique is replaced by a stream of X-rays, there is little, if any, difference between the results of the X-ray sedimentation technique and the absolute method. This is probably associated with the fact that the wavelength of the X-rays is much smaller than the particle diameters. However, the absorbing capacity of pigments for X-rays is a function of their atomic numbers, and consequently X-ray instruments only appear to be suitable for inorganic pigments, and not for organic pigments and carbon blacks [ 111. X-ray centrifugal sedimentometers are now available commercially, and are being used, with satisfaction, by the manufacturers of titanium oxides and inorganic pigments. As mentioned earlier, sedimentation experiments for determining particle sizes are based on Stokes law and are therefore believed to be theoretically sound. One criticism of such experiments, when applied to the very small particles met with in pigment technology, has been voiced by one of the writers colleagues [7 3. In dry pigment powders we know that the basic particles are clustered together very tightly. On milling, grinding or dispersing the powders into a liquid phase, the clusters are rapidly broken down into smaller clusters and possibly basic particles. These smaller c!usters, or basic particles, can reaggregate or flocculate through the existence of very short range attractive forces. When they do so, they may well trap some of the

179
10 loc x10- .6 k-T IO -

O-

I I
.l 1 0

I
01

I
l-o 10

Particle diameter (microns)

Fig. 8. Calibratiorr

curve for rutile titanium

dioxide.

liquid phase inside, and the aggregate plus trapped liquid will settle under gravity or centrifugal force as a single entity. The density of this composite will differ from the true density of the pigment and, as it is the true density that is used in the calculations, the particle size distributions obtained will be in error. This criticism cannot be lightly dismissed, but it is difficult to know how to determine the degree of error, if any, that would be introduced in this way. From our experience, based on hundreds of size distribution experiments, the repeatability of the size distributions falls off when the mean diameters are greater than about 0.6 pm, but is very good with dispersions finer than this. The loss in accuracy above 0.6 pm may well be due to the density problem outlined above. Fortunately, the size regions of greatest interest, both practically and theoretically in pigment technology, are from 0.5 pm downwards, and we have always found the reproducibility to be good in this region. We would also expect the incidence of trapped liquid in this size region to be insignificant. We can now sum up both indirect and direct methods of assessing dispersion in the wet state. Indirect methods. Measurement of flow properties is very attractive from many points of view, but the interpretation of the results is uncertain. Optical density measurements are straightforward but require massive dilution. To give absolute results, a master curve is required of extinction coefficient uersus particle size. This can be obtained either theoretically or empirically. Direct methods. Centrifugal sedimentation is the only technique .sensitive enough for the sub-micron range. Using a photosedimentometer attachment, the size distributions of organic pigments can be readily determined. Carbon blacks can be measured to a close approximation. An X-ray centrifugal sedimentometer is much better suited to inorganic pigments.

180 With all sedimentation experiments, dilution shock must be guarded

against. Photo or X-ray sedimentometers are best suited to reasonably narrow size distributions, say from 0.1 to 1.0 pm.
5. Dry systems 5.1 Indirect methods 51.1 Colour strength
It has long been known that as grinding proceeds, colour strength will often increase. For many pigments the increase in colour strength can be considerable. Colour strengths can be compared very accurately by the human eye and they can also be measured instrumentally by a variety of spectrophotometers. Colour strength would, therefore, appear to provide a suitable means for following changes in pigment dispersion. For accurate comparisons, the pigmented specimens must be prepared under identical conditions. For surface coatings, it is preferable that the paint or ink is adequately reduced with a suitable standard opaque white so that the resultant films are opaque and the colour strengths are independent of the film thickness. The film with the higher colour strength contains the more highly dispersed pigment. If colour strength is to be used to measure the absolute degree of dispersion, rather than for purely comparative purposes, then a master curve must be prepared of colour strength uersus particle size, using standardised conditions for measuring the colour strength. Particle size measurements can be carried out using centrifugal sedimentation as already described, and hence the master curves can be determined experimentally_ Their determination is quite lengthy, but their usefulness is considerable. Master curves can also be calculated theoretically using the Mie theory, provided the optical constants of the pigment are known. Figures 9 and 10 give some master curves of colour strength versus particle size for some wellknown organic pigments [12]. The curves for phthalocyanine blue and Pigment Green B are believed to represent the extremes; that is, the master curves for all organic pigments lie between these two curves and follow the same general pattern. This pattern gives a slow, regular increase with reducing particle size in the coarser regions, but as the particle sizes are reduced below about 0.4 Drn, the subsequent increases in colour strength are much greater. These increases can be of the order of 200 - 300% as the particle size reduces from 0.4 to 0.15 pm. This means that the colour strength is a very sensitive indication of dispersion level in this region. The actual instrumental measurement of the colour strength of surface coatings is only a matter of minutes. With paints, however, the films may well require overnight drying. On the other hand, many films can be prepared and allowed to dry simultaneously and can be quickly examined for colour strength the next day.

181
5x

45

4.0

3.5

3.0

iris

25

2x

1.5

1.c

0.1

Fig. 9. Particle size of paint stainers (1:12.5). A, Copper Phthalocyanine x , ball milled; stabilised alpha form

us. colour strength of titanium dioxide reductions Blue: beta form (Irgalite Blue GLS): 3, sand ground;

B, Pigment milled.

Green B (Cl Pigment

(Irgalite Blue BCS): *, sand ground; A, ball milled. Green 8 Irgalite Green DBN): 0, sand ground; 0, ball

Colour strength measurement, as a means of measuring dispersion, is straightforward and very sensitive, particularly in the regions of good dispersion. Essentially a comparative method, it can be converted into an equally sensitive absolute method if a master curve of colour strength uersus particle size is available. On the other hand, it must be appreciated that colour strengths are only indicative of the pi,ment dispersion in the final dry film. It is usually assumed that this dispersion level is the same as that in the wet paint or ink, but recent work has suggested that this is not always the case [ 13]_ Moreover, phenomena can take place in the drying stage, such as flooding of the white or coloured pigment, which will give erroneous values of the colour strength. Colour strength measurements can never give information on the particle size distribution. On the other hand, it is difficult to represent a particle size distribution by a single figure. Mean diameters, however determined, give little information on the size distributions, and it is possible for various pigmented systems to give similar mean diameters while differing markedly in size distributions. Colour strength measurements can give a single figure, usually the value of k/s under standard conditions, which is more representative of the true state of dispersion; k is the absorption coefficient and s the scattering coefficient. Every individual particle or aggregate of particles contributes to the colour strength of the end system, but the smaller particles contribute very much more on a weight basis. The colour strength sums up

0.6

I
I

I
0.5 -

f
I I

0.0

-\ i

OJ

i \ _ _. \ I;
7

0.2

\ . !,
C 3.8 In microns

0.1 -

SO/. diamclcr

Fig. 10. Colour strength

us. particle

size. l/75

bazole Violet (Pigment Violet 34). cyanine Green (Pigment Green 7), -I---

reductions in Beckosol P470. - - - CarMonarch 71 (Pigment Black 7), -. - - - PhthaloDiarylide Yellow (Pigment Yellow 17).

the effect of all the particles, and it is unlikely that systems with equal colour strengths will have any but slight differences in particle size distribution. In our experience, colour strength measurements represent.an easy, straightforward, sensitive and accurate way of assessing pigment dispersion in the sub-micron range, especially for air-drying decorative paints and oil inks, For such systems, only one master curve is needed for absolute values, and this can readily be determined for the paints. The oil inks can be used as stainers or tinters for the white paint [ 3 3 as they are usually fully compatible with it. We suspect that the method is not so suitable for other systems such as stoving paints, emulsion paints, and liquid inks. To apply the technique on an absolute basis to these systems, separate master curves would be required because dispersion levels of the titanium oxide in the reductions would be different. The colour strengths are measured on the final dry films, and there is a possibility that the dispersion levels in these films differ from those in the corresponding wet systems. With the airdrying paints and oil

183

inks, the

evidence to

would seem

indicate that

is no

alteration of pigment dispersion on film drying. Colour strength determinations also have the decided psychological merit that they represent the main property that the user is interested in. 5.1.2 Gloss It is also known in a general way that, as dispersion increases, the gloss of the subsequent films increases. Specular gloss can be readfly measured, and gloss measurements could therefore be used as a technique for following dispersion changes. Published evidence [14] to date, however, shows that with paint films, specular gloss does increase with dispersion in the coarser region but tends to level off once the mean diameter is reduced to about
0.3 - 4 /.lnl. Gloss is therefore not suitable for assessing dispersion levels in the size

regions below 0.4 pm. Gloss is also known to vary with time even when panels are stored in the dark [ 13 3 . It is highly doubtful whether gloss would be of any use at aU in assessing dispersion in surface coatings of low gloss. 5.1.3 Optical densities Provided a film is not opaque in itself, and has been prepared on a transparent substrate, its optical density can be measured if the film thickness is known. The measurement takes only a matter of minutes on a transmission spectrophotometer. If the level of pigmentation is varied, and the experiment repeated, the optical density can be plotted against pigment concentration. If the graph is linear, the extinction coefficient of the pigment in the film can be determined from the slope of the graph. It is dependent on the optical constants n and k of the pigment and the particle size of the pigment in the film. There is, therefore, a direct relationship between the extinction coefficient of the film and the particle size of the pigment in the film. Optical density measurements can therefore be used to compare dispersion levels of a given pigment. They can be used to determine the absolute level of dispersion if the exact relationship between extinction coefficient and particle size is known. As before, this relationship can be determined experimentally or it can be derived from the application of the Mie theory. Experimental determination means measuring the pigment dispersion directly, and this can only be done in the wet product. One has then to make the assumption that, on application and drying, the dispersion level is unaltered. One can then plot a graph of extinction coefficient versus particle size and this is a master curve for that pigment. Subsequent determinations of extinction coefficients can be converted into pigment particle sizes by reading off the corresponding sizes from the master curve. The technique is similar in principle to that used for the wet paints. A suitable substrate for the film is a glass microscope slide. The paint or ink has to be diluted considerably to enable the optical density to be measured. As a satisfactory film has to be prepared from the diluted system, the dilution will usually have to be carried out with the vehicle itself, i.e. with a solution

184

of resin in a solvent. Dilution with a solvent itself will give a system whose viscosity may be too low for satisfactory film formation, A pigmentation level of 0.5% or less is usually adequate with film thicknesses ranging from 25 to 100 pm. With liquid inks, the incorporation of a plasticiser may be necessary to obtain a satisfactory film. The films can usually be applied by a bar coater or block applicator to give films of known wet film thickness. Films can also be applied to the glass by spraying, in which case the film thickness can be determined from weighings of the slide before and after. As in the wet state, the curves of extinction coefficient versus particle size have quite steep slopes in the sub-micron region, so that the method is sensitive. Again, it is applicable to all types of systems, aqueous or nonaqueous. Again, the system has to be diluted drastically and the films have to be prepared on a transparent substrate. One of the most interesting things about using optical density measurements as a measure of dispersion levels is that it is probably the only technique that can be applied to both the wet and dry states. It does, therefore, offer a means whereby dispersion levels in the dry films can be directly compared with the corresponding dispersion levels in the wet products from which were derived. It be used study the of mechanisms pigment Direct methods 5.2.1 Electron nz icroscope If a photograph of the pigment dispersion in the dry state can be obtained, whether from a surface coating or a mass pigmented product, the size of the particles can be measured at leisure and a size distribution curve can be obtained. For particles known to be in the sub-micron region, optical microscopy is not adequate and electron microscopy is required. With suitable microtomes, very thin cross-sections of surface-coating films and segments of mass pigmented products can be obtained and electron micrographs prepared. Some outstanding photographs of pigmented systems have been obtained in this way and published in the literature. The photographs give permanent records and can be studied at leisure. Many classes of pigments have been examined in this way in various types of systems. Electron microscopy as a direct method of assessing pigment dispersion scores on the grounds of sensitivity, versality and applicability. However, it is not without drawbacks. The equipment is still expensive. It requires a specialist operator to get the best results, and in this field the operator should also have a good knowledge of pigment technology. It is not a rapid method, because the preparation of specimens for the electron microscope is a delicate task which cannot be hurried. Even when satisfactory photographs have been obtained, there are considerable difficulties to be faced. These arise from the fact that the pigment particles are never uniform in size; there is always a size distribution. Even in

185

Fig. 11. Electron micrograph of decorative alkyd resin. 50% diameter = 0.15 p.

paint film (X 10,000).

Dioxazine

Violet

in

186
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~
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~-:~ ~ , ~ . . . ~ , . ~ . ~ . ~ . - .

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- w , - ~ . . - . ~ ~

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Fig. 12. E l e c t r o n m i c r o g r a p h o f d e c o r a t i v e p a i n t film (x 1 0 , 0 0 0 ) . D i o x a z i n e V i o l e t in a l k y d resin. 5 0 % d i a m e t e r = 0 . 2 5 / ~ n .

187

very well-dispersed systems, the range of sizes is usually 25-fold, going from, say, 0.04 to 1.0 pm. This sort of size distribution introduces two problems.
Firstly, in systems where the mean particle sizes are known to be fairly close together (from other methods of assessment), the eye can see little difference in the photographs and finds it difficult to decide which is the better dispersion. This is illustrated in the two electron micrographs shown in Figs. 11 and 12. These micrographs are of cross-sections of films of decorative paint stainers based on a dioxazine violet in an alkyd resin system. There is little difference between the dispersion levels visible to the eye. The mean particle sizes (50% wjw diameter) of the pigments in the two paints are 0.15 and 0.25 pm respectively, and their colour strengths (h/s values) when measured as l/75 reductions with titanium oxide are 0.42 and 0.28, respectively. The two stainers are markedly different in terms of the so-called flocculation test. Despite these differences in mean diameters, colour strengths and application behaviour, the eye can detect little, if any, difference between them in terms of dispersion or particle size. This is because the difference in mean diameters is small compared with the range of sizes present in both. Secondly, to determine a size distribution from a micrograph, the sizes of a considerable number of particles, taken at random, have to be measured [lo]. The number of measurements to be made will depend on the degree of accuracy and the actual range of sizes in the picture. In most cases at least 1000 individual particles will have to be measured, and usually the figure will be much more. To carry this out by hand is out of the question as a regular procedure,

and it is commonly agreed among microscopists that size distributions can only be obtained from electron micrographs when the counting and sizing
can be done automatically [ 151. Automatic scanners, analysers and counters are available commercially, but they are very expensive. The area of the cross-section of a film viewed in a single photograph is small, and consequently quite a number should be prepared from different areas of the specimen in order to get a truly representative size distribution. This increases the time taken and emphasises the need for automatic counting. Given the necessary equipment, and this includes, besides the microscope, the preparation equipment and an automatic scanner and counter, particle size distributions can be determined directly for pigmented films and mass pigmented systems A specialist operator is reqquired, and even then the whole procedure is fairly slow and it is difficult to see it being used on a routine basis. It might be argued that the best role for electron microscopy in the field of particle size measurement would be to act as a check on other quicker and less sophisticated methods. Certainly, comparisons of this nature would help to demonstrate the soundness or limitations of other methods. The literature to date, however, does not give any comparisons of this nature in the sub-micron region.

188

6. Conclusion

The authors views on the position at the present time regarding the assessment of pigment dispersions in the sub-micron region are as follows. For wet systems, centrifugal sedimentation has proved itself, in practice, to have the necessary sensitivity and versatility for organic pigments. When fitted with a light beam as the sensing mechanism, the experimental time is dramatically reduced. The technique is very suitable for organic pigments and
carbon blacks in all types of systems. When an X-ray beam is used as a sensing

mechanism, the technique is very suitable for inorganic pigments. For dry systems, colour strength measurement is a very useful indirect technique well suited for day to day work. For direct accurate measurement, electron microscopy and sophisticated counting and scanning equipment are required. For comparisons of dispersion levels, in the wet and dry forms of the same pigmented system, optical density measurement would appear to be theonly method available, as this is the only technique that can be applied to both wet and dry systems. References
1 2 3 4 5 6 7 8 9 10 11 12 13 Classification of methods for determining particle size, Analyst, 88 (1963) 156. C. C. Mill (Ed.), Rheology of Disperse Systems, Pergamon Press, New York, 1959. W. Carr, J. Oil Colour Chem. Assoc., 55 (1972) 794. W. Car-r, Proc. XIIIth FATIPEC Congr., 1976, p. 164. G. Mie, Ann. Phys., 25 (1908) 377. W. Car-r, J. Oil Coiour Chem. Assoc., 54 (1971) 155. R. B. McKay, J. Appl. Chem. Biotechnol., 26 (1976) 55. E. Atherton, A. C. Cooper and M. R. Fox, J. Sot. Dyers Coiour., 80 (1964) 521. M. Mermann and B. Honigmann, Farbe Lack, 75 (1969) 337. G. A. Lombard and W. Car-r, J. Oil Colour Chem. Assoc., 58 (1974) 246. T. Alien and L. Svarovsky, Powder Technoi., 10 (1974) 23. W. Can-, J. Paint Technol., 42 (1970) 694. W. Car-r, Paper presented at an O.C.C.A. Symposium in Manchester, April 1976 (in the press). 14 W. Car-r, J. Oil Colour Chem. Assoc., 54 (1971) 1093. 15 L. J. Venuto and W. Hess, Am. Ink Maker, 45 (1967) 42.