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THE HISTORY OF IRON PROTECTION.

DESCRIPTION OF MATERIALS AND EVALUATION OF THEIR PROPERTIES

Heikki Hyh EVTEK Institute of Art and Design Department of Conservation Lummetie 2 01300 Vantaa Finland A stra!t Iron "as een noti!ed as eing a ver# vulnera le material sin!e anti$uit#% Corrosion and ele!tro!"emi!al p"enomena &ere 'no&n in an!ient Eg#pt and (esopotamia% Eviden!e of t"is is !opper !oated potter# found in Eg#pt) &"i!" indi!ates t"at pre!ious metal !oating te!"ni$ues &ere in use some 2*00 #ears ago +Aromaa) 1,,*)1-.% T"e Eg#ptians developed varnis"es) &"i!" &ere !om inations of natural resins +sandara! or masti!. and oils% T"ese varnis"es &ere applied "ot as prote!tive !oatings for iron +/radle# 0 /urns) 1,**) 312.% T"e a!tual reasons for !orrosion) alt"oug" not understood &ere e3plained a!!ording to t"e 'no&ledge availa le at t"at time% In an!ient 4ree' p"ilosop"# all su stan!es !onsisted of four elements5 eart") fire) air and &ater and !orrosion &as e3plained as t"e element eart") &"i!" tends to !ome out from metal%

Ke#&ords Iron) prote!tion) organi! !oating

History of Iro Prote!tio

Alt"oug" !orrosion &as not understood some pra!ti!al met"ods &ere in use to prote!t iron from !orrosion% T"e 6omans 'ne& t"at iron) !opper and lead !orroded and developed met"ods to prevent it% A!!ording to t"e literature 7lin# t"e elder +2381, A%D%. re!orded some re!ipes% 9e suggested a mi3ture of itumen) pit!") &"ite lead and plaster for iron prote!tion and a mi3ture of turpentine and pit!" for ron:es + Aromaa) 1,,*)1-.% A!!ording to /radle# and /urns) "is re!ipe for iron prote!tion is as follo&s5 ;If #ou desire to prote!t iron from rust) give it a varnis" of !eruse) plaster and tar; +/radle# 0 /urns) 1,**) 312.% <n t"e ot"er "and =ease mentions t"at 7lin# does not reveal e3a!t !onservation met"ods +=ease) 1,,-) 1*1.% Iron &"i!" needed prote!tion &as mainl# t"at of &arrior>s &eapons and t"e follo&ing re!ipe for armor &as given # a 4erman aut"or in 1-1-5; 7our olive oil in a "eav# mortar) stir it &ell &it" a pestle until it &arms itself) put &"ite lead to it and ru it again until it e!omes la!'% 7our a little oil of tartar in it and &it" ?eat>s foot oil or old fat ma'e a salve% =mear t"e armor &it" t"e salve; +/radle# 0 /urns) 1,**) 312.% T"is &as t"e level of prevention of !orrosion in Europe for nearl# 1200 #ears% In !ontrast to t"is) la!$uering as a form of metal prote!tion &as in use "undreds of #ears efore t"e C"ristian era in t"e Far East% T"e inding medium &as mainl# 6"us verni!ifera) &"i!" "ardens to an insolu le film% < @e!ts treated in t"is &a# "ave een ver# &ell preserved +/radle# 0 /urns) 1,**) 31,.%

De"e#o$%e t of Corrosio Theory

T"e fa!t t"at iron !orroded $uite $ui!'l# &as 'no&n ut t"e a!tual me!"anism &as not understood% T"is &as e3emplified in 4erman# &"ere &ater pipes &ere first made from mallea le iron in 1A12% T"ese iron pipes !orroded and &ere repla!ed &it" &ooden ones +Aromaa) 1,,*) 11.% T"e manufa!turing of large !ast iron o @e!ts egan during t"e 11t" !entur# and t"e me!"anism of t"eir !orrosion &as slo&l# eing reali:ed% T"e !on!ept ; !orrosion ; !ame into use around 12*0% T"e s!ientifi! stud# of !orrosion egan in t"e earl# 20t" !entur# &"en it &as reali:ed t"at !orrosion pro!esses !ould e ele!tro!"emi!al in nature +Ba'o sen) 1,22) *-.% La!' of 'no&ledge also e3a!er ated various !orrosion pro lems% For e3ample in

England t"e lo&er "ull of fast sailing oats &as !overed &it" !opper plates and after a ver# s"ort period of time t"e iron mounting of t"e rudder !orroded +Aromaa) 1,,*) 11.% T"e s!ien!e of ele!tro!"emistr# developed during t"e 20t" !entur# and !reated a asis for t"e effe!tive prevention of !orrosion% IRON CONSERVATION IN MUSEUMS& History

Ar!"aeologi!al e3!avations in =!andinavia egun on a larger s!ale in t"e eginning of t"e 1,t" !entur#) alt"oug" smaller s!ale e3!avations "ad alread# produ!ed a !olle!tion of o @e!ts% At t"is time t"e !onservation of ar!"aeologi!al material &as !arried out # sele!ted !raftsmen &"o &ere familiar &it" t"e materials +4il erg) 1,21) 10- C Ba'o sen) 1,22) *1.% Conservation re!ords in =!andinavia date a!' to t"e end of t"e 1,t" !entur#% T"e treatments predating t"is period !an e found from letters and ot"er unpu lis"ed sour!es onl#% In general it !an e said t"at treatment met"ods &ere largel# empiri!al and not ne!essaril# ased on s!ientifi! prin!iples +4il erg 1,21) 10-.% In t"e !onservation of anti$uities t"e greatest advan!es &ere a!"ieved at t"e end of t"e1,t" !entur#% Friedri!" 6at"gen e!ame t"e first dire!tor of t"e !"emi!al la orator# of t"e 6o#al (useums in /erlin &"en it &as founded in 1222% 9is la orator# &as t"e first museum resear!" la orator# in t"e &orld +4il erg) 1,21) 10- C Ba'o sen) 1,22) **.% 6at"gen &as t"e first one &"o reali:ed t"at treatment met"ods s"ould e developed spe!ifi!all# in t"e field of !onservation for progress to ta'e pla!e% CONSERVATION TREATMENTS& Histori!'# o"er"ie(

6at"gen des!ri es old met"ods ased on impregnation% T"e o @e!ts &ere treated &it"

materials su!" as s"ella!) linseed oil) !opal varnis") Vaseline) &a3es) fats and ru moisture and ot"er "armful !omponents in t"e air%

er %

T"ese treatments &ere supposed to ind loose pie!es and to prote!t t"e o @e!ts from 6at"gen also states t"at t"ese !oatings on t"eir o&n are effe!tive if t"e !orrosion la#er is free from !"lorides +6at"gen) 12,2) 1-811.% A!!ording to 6at"gen t"e est prote!tion against moisture in t"e atmosp"ere is pure melted paraffin) &"i!" does not !ontain stearin +6at"gen) 12,2) 12.% In =!andinavia e3amples !an e found in ?or&a# and Denmar'% In 1230 t"e !urator of t"e /ergen (useum in ?or&a#) Dil"elm C"ristie) treated all iron o @e!ts in t"e museum &it" linseed oil +9ansen 1,,1) 1--.% In 1210 <luf 6#g") ar!"aeologist and founder of ;T"e Eniversit# Colle!tion of ?ordi! Anti$uities;) re!ommended t"at iron o @e!ts s"ould e oiled in a mi3ture of 1*F linseed oil and 2*F &a3 +9ansen) 1,,1) 112.% In t"e ?ational (useum of Denmar' C"ristian Burgensen T"omsen "ad diffi!ulties &it" e3!avated iron o @e!ts as eviden!ed in "is letters% In 12** "e &rote to a !olleague) L% Lindens!"midt in (ain:) as'ing &"at 'ind of treatments t"e# used in 4erman# and des!ri es a ne& !onservation met"od in use in Denmar') namel# oiling iron o @e!ts in stearin) &"i!" gives a etter appearan!e t"an varnis" at t"e time +/rin!" (adsen) 1,21) 3AA.% Anot"er person &or'ing in Denmar' &as C%F% 9er st) &"o &as an assistant in earl# e3!avations and in fa!t !arried out most of t"e !onservation treatments for e3!avated o @e!ts% 9e suggested in 12-0 t"at iron o @e!ts s"ould e a'ed in linseed oil if t"ere is an iron !ore preserved% =ome #ears later +12-1. "e re!ommended &a3 &it" en:oin and mentions also treatment &it" "#dro!"lori! a!id and gl#!erine +/rin!" (adsen) 1,21) 3A*.% In Finland o3idation &as also elieved to e t"e main !ause of !orrosion and 9@almar Appelgren &rote in 12,* in t"e Finnis" (useum t"at e3!avated iron o @e!ts s"ould e treated &it" a solution of s"ella! in al!o"ol% Anot"er met"od "e mentioned &as "eating t"e iron o @e!ts in a solution of !opal varnis" and linseed oil +Appelgren) 12,*) **8*-.%

F)rther *e"e#o$%e t

<n a!!ount of resear!" and as a etter understanding of t"e nature of !orrosion advan!ed iron !onservation met"ods &ere developed% T"ese met"ods !onsisted of soa'ing in &ater) "eat treatment) a!id stripping) ele!tro!"emi!al and ele!trol#ti! treatments% Friedri!" 6at"gen e3plains t"ese met"ods in "is 9and oo's5 Die Konservirung von Altert"umsfunden +12,2 and 1,2A.% T"e engineer A3el Krefting in ?or&a# pu lis"ed t"e results of "is investigations in 12,2 !on!erning t"e influen!e of solu le salts on metals% /eginning in 122- "e used "is met"od !alled ele!trol#ti! redu!tion% 9is invention &as signifi!ant e!ause it &as more gentle t"an a!id stripping and "eat treatments )ma'ing it possi le to reveal inla#s and ins!riptions for t"e first time +Appelgren) 12,-) --812 CBa'o sen)1,22) *A.% <n t"e ot"er "and Krefting t"oug"t t"at !oatings li'e oils and varnis"es !ould !ause !orrosion% After !leaning "e prote!ted t"e o @e!ts &it" paraffin &a3 +Ba'o sen) 1,22) *A.% Krefting gave permission to use "is met"od in 9elsin'i and 9@almar Appelgren adopted it in 1221 +Appelgren) 12,-) 3383*.% T"e most !ommon prote!tive !oating for iron anti$uities after !onservation treatments &as paraffin &a3% A!!ording to Appelgren a prote!tive la#er &as applied # "eating t"e iron up to 2*0 GC to evaporate all t"e &ater from t"e pores% T"en it &as soa'ed in a solution of 200 g pure paraffin in one liter of refined petroleum +Appelgren) 12,-) 3*.% In Denmar' 4ustaf 6osen erg &rote a out iron !onservation in 1,11% 9e immersed pre8 "eated iron in melted paraffin until u ling !eased +si3 to fourteen "ours.% D"en t"e paraffin solidified +at *-GC. t"e o @e!t &as pla!ed on filter paper and t"e e3!ess paraffin &as removed +6osen erg) 1,11) A18A2.% <ne ver# important person in ar!"aeologi!al !onservation &as 9arold 7lenderleit" &"o re!ommended lanolin +&ool fat. for prote!tion of urnis"ed steel ut if a non8 sti!'# surfa!e &as needed "e re!ommended a t"in la#er of non8sti!'# &a3 +7lenderleit") 1,*-) 211.%

Co !#)sio s

T"ere seems to e a lot of !onfusion) misunderstanding and a la!' of su!!ess in t"ese earl# treatments% T"e !orrosion me!"anism of iron &as poorl# understood and rust# iron proved to e a ver# diffi!ult material to deal &it"%

T"ese treatments &ere insuffi!ient % After a ver# s"ort period it &as o vious t"at iron &as unsta le and man# o @e!ts "ad to e retreated) ut t"ere &ere also e3!eptions% OR+ANIC COATIN+ MATERIALS& I tro*)!tio

After treatment a prote!tive !oating is normall# applied to iron% =u!" !oatings are supposed to e3!lude moisture and s"ould prevent or retard furt"er !orrosion + Keene) 1,21) 1.% T"e performan!e of organi! !oatings is determined # t"e p"#si!al stru!ture of t"e !oating and "o& it alters upon aging% <t"er fa!tors are t"e !ondition of t"e metal surfa!e) ad"esion of t"e !oating to t"e metal) !ontinuit# of t"e film and t"e presen!e of a !orrosion in"i itor in t"e !oating + /radle# 0 /urns) 1,**) A-, C Keene) 1,2A) 10A. In order to a!"ieve a reall# effe!tive !oating) t"e metal surfa!e must e ver# !lean and free of !orrosion and grease% In pra!ti!e t"ese !onditions are ver# rarel# a!"ieved espe!iall# &it" ar!"aeologi!al iron% <ne of t"e ma@or pro lems is t"at t"e !oating sti!'s to t"e !orrosion la#er and not t"e metal !ore +Keene) 1,21) 1.% Impregnation is ver# rarel# !omplete and one reason for t"at mig"t e t"e ound &ater) &"i!" is given off from t"e !orrosion la#er &"en t"e o @e!t is "eated to *008 -00 GC during impregnation% A means to avoid t"is mig"t e to pre"eat t"e o @e!t to *008 -00 GC efore introdu!ing t"e impregnanting agent%

Oi#s, f'ts ' * ('-es

<ils) fats and &a3es are su stan!es of plant or animal origin% T"e# are nonvolatile) insolu le in &ater and oil# or greas# to t"e tou!"% C"emi!all#) fats and oils are !ompounds produ!ed # a rea!tion et&een an al!o"ol !alled gl#!erol and !ertain mem ers of a group of !ompounds !alled fatt# a!ids% T"ere are no essential !"emi!al differen!es et&een oils and fats% 7"#si!all# t"ere is a differen!e) sin!e at normal room temperature oils are li$uid and fats are solid% T"e p"#si!al and !"emi!al properties of fats are determined # t"e fatt# a!ids &"i!"

are in!luded in t"e !omposition% Lipid is a mu!" roader term t"at ma# e used to in!lude all of t"e et"er8solu le) &ater8 insolu le su stan!es o taina le from plant and animal sour!es% Fats form a ma@or su group of lipids +(ills 0 D"ite) 1,21) 2- C (ass!"elein H Kleiner) 1,21) *0C 9orie) 1,21) 1*0.% Dr#ing oils "ave een used for impregnation% T"e most !ommon of t"ese "as een linseed oil ut ot"er oils "ave also een used) for e3ample normal !lo!' oil% Even in anti$uit# it &as 'no&n t"at dissolving a resinous material in t"e oil !ould "arden an oil film% =o8!alled !opal varnis"es or la!$uers !ontained fossil resins su!" as Congo gum or Kauri% 6e!ent resins in use "ave een s"ella! and dammar% In general resins !an !over details and e!ome rittle +/radle# 0 /urns) 1,**) 3,38 A00C 9orie) 1,21) 22 C Keene) 1,21) 2.% T"e most !ommon dr#ing oil is linseed oil t"at "as een &idel# used for iron prote!tion and !onsolidation% It is e3tra!ted from t"e seeds of Limu usitatissimum% Linseed oil !onsists of mi3ed gl#!erides of saturated and unsaturated fatt# a!ids% T"e dr#ing !omponents are linolei! and linoleni! a!ids% To a!!elerate t"e dr#ing rea!tion of linseed oil it !an e "eated to 1*081-0GC &it" t"e addition of !o alt8) manganese8 or lead salts% T"is treatment a!!elerates t"e o3idation and pol#meri:ation pro!ess !ausing t"e oil to dr# faster &it" a lo&er vis!osit# +/radle# 0 /urns) 1,**) 3,AC (ass!"elein H Kleiner) 1,21) *-8*2.% Da3es do not form a !"emi!all# "omogenous group% T"e !omponent parts ma# e "#dro!ar ons) fatt# al!o"ols) fatt# a!ids) esters of fatt# al!o"ols) esters of gl#!erine or et"ers and t"eir de!omposition produ!ts% It !an e said t"at a ;true; &a3 is an ester of a "ig"er mono asi! fatt# a!id &it" a "ig"er mono"#dri! fatt# al!o"ol% ?atural &a3es ma# e of animal) vegeta le) mineral or animal origin +CollierIs) 1,2A) 3-1 C (ills 0 D"ite) 1,21) A18A* C (ass!"elein8Kleiner) 1,21) -08--C 9orie) 1,21) 2*82,.% Da3 is not an effi!ient &ater vapor arrier ut it remains sti!'# and in t"eor# !an spread itself to form an even !oating after damage +/radle# 0 /urns) 1,**) 3,38A00C 9orie) 1,21) 22 C Keene) 1,21) 2.% <ne animal &a3 is lanolin or &ool &a3% Dool from un&as"ed s"eep !ontains a greas# su stan!e% It also !ontains salts of long !"ain fatt# a!ids% After purifi!ation t"e produ!t is !alled lanolin) a mi3ture of esters of fatt# a!ids and long8!"ain al!o"ols t"at is a lipid% Lanolin "as een used as a !orrosion8 in"i iting !oating for iron o @e!ts% It

dissolves in !"lorinated "#dro!ar ons and "eated al!o"ols% Its melting point is 32 8 A2 GC +(ass!"elein8Kleiner) 1,21) -1 8-2 C 9orie) 1,21) 1*3 C (ills 0 D"ite) 1,21) A3.% T"e most !ommon mineral &a3 is paraffin% 7etroleum in a !rude form is a !omple3 mi3ture of t"ousands of !ompounds) most of &"i!" are "#dro!ar ons li'e paraffins) olefins) nap"t"enes and aromati!s% 7araffin &a3 is produ!ed # distillation from petroleum% 6efined paraffin &a3 is a translu!ent) perfe!tl# &"ite material% 7araffin &a3es form large !r#stals &"en solid &"i!" e3plains t"eir rittleness% T"e softening point of paraffin &a3 is A08-*G!% 7araffin &a3 &ill dissolve in ordinar# fat solvents &"en &arm% +CollierIs) 1,2A) 3-1 C (ills 0 D"ite) 1,21) A* C (ass!"elein8Kleiner) 1,21) -18-2C 9orie) 1,21) 1,2.% Co !#)sio s

It &ill e $uite diffi!ult to @udge t"e effe!tiveness of t"ese organi! !oatings% T"ere are man# fa!tors) &"i!" "ave to e ta'en into !onsideration5 Das t"e o @e!t !leaned efore !oating and to &"at degree J D"ere t"ere an# solu le salts remaining after t"e !leaningJ Das t"e !ontinuit# of t"e !oating film !ompleteJ D"at is t"e "istor# of t"e o @e!t after t"e first treatmentJ A!!ording to Keene it is unli'el# t"at t"e !onsolidants and la!$uers used for ar!"aeologi!al iron &ould "ave mu!" effe!t on t"e sta ilit# of t"e o @e!ts% <n t"e ot"er "and) t"ese treatments do serve as a strengt"ening fun!tion and "elp to prevent t"e total disintegration of t"e o @e!ts +Keene) 1,2A) 10*810-.% Refere !es Appelgren) 9%) 12,*% Konserveringsmetoder fKr metallsa'er%Fins' (useum% Fins'a FornminnesfKreningens (Lnads lad ?5o II 12,*% 9elsingfors% Appelgren) 9%) 12,-% Kreftings metod fKr rengKrning o!" 'onservering af metallsa'er% I8II% Fins' (useum% Fins'a FornminnesfKreningens (Lnads lad ?5o *8- o!" 12,-% 9elsingfors% Aromaa) B%) 1,,*% Korroosion @a sM"'K'emian 'urssi% Enpu lis"ed manus!ript% /radle#) D 0 /urns) 6%) 1,**% 7rote!tive !oatings for metals% T"ird Edition 1,**% ?e& Nor'5 6ein"old 7u lis"ing Corporation% /rin!" (adsen)9%) 1,21% Artefa!ts Conservation in Denmar' at t"e /eginning of t"e 1810

Last Centur#% In5 6e!ent Advan!es in t"e Conservation and Anal#sis of Artifa!ts% 7reprints of t"e Bu ilee !onservation !onferen!e 7apers% London5 =ummer s!"ool press% CollierIs En!#!lopedia% Volume 23% ?e& Nor'5 (a!millan Edu!ational Compan#% 4il erg) (%) 1,21% Friedri!" 6at"gen5 T"e fat"er of modern ar!"aeologi!al !onservation% AIC Bournal vol 2-% ?o% 2% 1,21% T"e Ameri!an Institute for Conservation of 9istori! and Artisti! Dor's% 9ansen)B%) 1,,1% Konservering av Bernoldsa'er !a% 123081210% ?ors' 'onserverings"istorie% In5 7reprints of Konserverinsmidler 0 Konserveringsmetoder% ?ordis' 'onservatorfor und OIV% Kongress% 9orie) C)% 1,21% (aterials for !onservation%Corn&all5 /utter&ort" 0 Co% Ltd% Ba'o son) T%) 1,2A% Iron !onservation at t"e ?ational (useum of Copen"agen 8 past and present% In5 7reprints of t"e International Counsil of (useums Committee for Conservation% 1t" Triennial (eeting Copen"agen 1,2A% London5 Bames 0 Bames% Ba'o son) T%) 1,22% Iron Corrosion T"eories and t"e Conservation of Ar!"aeologi!al Iron o<@e!ts in t"e 1,t" Centur# &it" an Emp"asis on =!andinavian and 4erman =our!es% In5 Earl# advan!es in Conservation% /ritis" (useum o!!asional paper ?o -*% London5 /ritis" (useum% Kampman +KenttMmaa.) (%) 1,21% 6autaisten (uinaisesineiden =Mil#t#stapo@a% =uomen (useo 1,2081,21% 9elsin'i5 =uomen (uinaismuisto#"dist#s% Keene) =%) 1,2A% T"e 7erforman!e of Coatings and Consolidants Esed for Ar!"aeologi!al Iron% In5 Ad"esives and Consolidants% In 7reprints of t"e Contri utions to t"e 7aris Congress 1,2A% London5 T"e International Institute for Conservation% Keene) =%) 1,21% 7rote!tive !oatings for iron% In5 Bern fremstilling) ?ed r#dning og /evaring% Fortr#' af forelaesninger til ?ordis' Videreddannelse af Konservatorer Ko en"avn 1,21% Ko en"avn5 ?ationalmuseet% (ass!"elein8Kleiner) L%) 1,21% Van"at sideaineet ) la'at @a 'iinnitteet + Liants) vernis et ad"Psifs an!iens% Institut 6o#al du 7atrimoine Artisti$ue% /r#ssel 1,2A.% Finnis" translation 1,21% 9elsin'i5 VA7K% (ills)B% 0 D"ite) 6%) 1,21% T"e <rgani! C"emistr# of (useum < @e!ts% London5 /utter&ort" 0 Co% 7lenderleit") 9% 1,*-% T"e !onservation of Anti$uities and Dor's of Art% Treatment) 6epair and 6estoration% London5 <3ford Eniversit# 7ress%

6at"gen) F%) 12,2% Die Konservirung von Altert"umsfunden% 9and u!"er der KKnigli!"en (useen :u /erlin% /erlin5 D% =pemann% 6at"gen)F%) 1,2A% Die Konservierung von Altertumsfunden% 9and u!"er der =taatli!"en (useen :u /erlin% /erlin und Leip:ig 5 Dalter de 4ru#ter 0 Co% 6osen erg) 4%A%) 1,11% Anti$uitPs en Fer et en /ron:e% Leur Transformation et Leur Conservation% Copen"ague5 4#ldendals'e og"andels sortiment% =ease) C%) 1,,-% A ="ort 9istor# of Ar!"aeologi!al Conservation% In5 Ar!"aeologi!al Conservation and Its Conse$uen!es% 7reprints of t"e Contri utions to t"e Copen"agen Congress 1,,-% London5 T"e International Institute for Conservation%