SPRING 2003: NUMBER 43

Standard Materials for Corrosiveness Testing

Boris Pretzel Materials Scientist Nobuko Shiba a!a"ello#$ %onser&ation Research 'no# at the Metro(olitan Museu!$ Ne# )ork* +his article outlines research o, -corrosi&eness tests. as carrie/ out at the 0ictoria an/ 1lbert Museu! to test !aterials ,or (ossible interactions #ith !useu! arte,acts2 +he !a3orit o, the (ractical #ork #as un/ertaken b Nobuko Shiba a!a$ as (art o, her "ello#shi( #hilst at the 041 in 56672 Si!(le corrosi&eness tests are accelerate/ a8ein8 tests o, the t (e #i/el /escribe/ in corrosion literature since the !i/ 5670.s 5 an/ no# re,ine/ in British Stan/ar/ BS603 '569:*22 +he are co!!onl kno#n as -;// +ests. as the #ere intro/uce/ into !useu!s b 1n/re# ;// in the 56:0.s3 2 Sa!(les o, test !aterial are (lace/ in a seale/ en&iron!ent at ele&ate/ te!(erature an/ hu!i/it to8ether #ith !etal test cou(ons as in/icators2 Possible hazar/s are then in/icate/ b the se&erit o, corrosion on the test cou(ons2 +he tests use/ at the 041 are base/ on the test as /escribe/ b ;// 2 Each !aterial bein8 teste/ is (lace/ in three se(arate reaction &essels containin8 a sil&er$ co((er$ an/ lea/ cou(on$ res(ecti&el $ !aintaine/ at 500 < rh2 +he &essels are (lace/ in an o&en at 70=% an/ the !etal cou(ons are ins(ecte/ ,or si8ns o, corrosion at #eekl inter&als o&er the course o, 29 /a s2 1t the en/ o, this (erio/$ the are re!o&e/ ,ro! the reaction &essels an/ the se&erit o, corrosion on the cou(ons is cate8orise/2

+able 52 1/&anta8es an/ /isa/&anta8es o, si!(le corrosi&eness tests 'click i!a8e ,or lar8er &ersion* 1lthou8h the test has se&eral a/&anta8es 'see +able 5*$ there are also si8ni,icant (roble!s2 1 British Museu! sur&e co!(arin8 -;// testin8. in nu!ber o, /i,,erent conser&ation laboratories sho#e/ that there #as si8ni,icant &ariation in the a((earance o, !etal cou(ons a,ter the test an/$ e&en #hen this &ariation is e>clu/e/$ there #as also si8ni,icant &ariation in the inter(retation o, the result42 +he stu/ conclu/e/ that ti8hter s(eci,ications o, the (rotocol$ #ith (articular e!(hasis on (re?treat!ent$ (ositionin8$ an/ (urit o, the cou(ons an/ #a s o, sealin8 the test &essel$ increases the consistenc o, the

/ata2 @o#e&er$ the inter(retation o, the results still re!ains &er sub3ecti&e an/ the !ost /i,,icult (art o, the test2 1lso$ !an institutions e&aluate the results ,or each t (e o, cou(on se(aratel $ an/ relate the! to s(eci,ic !useu! ob3ects2 @o#e&er$ the cou(ons are o, (ure ele!ents$ unlike !ost !useu! arte,acts$ an/ #ere chosen because the #ill re&eal the (resence o, a &ariet o, /a!a8in8 &a(ours b corro/in82 Inter(retin8 the corrosion occurrin8 on$ sa $ a (ure sil&er cou(on in ter!s o, risks to actual sil&er arte,acts is not entirel strai8ht,or#ar/2 +his /i,,icult beco!es e&en !ore serious #hen consi/erin8 the i!(lication o, test results ,or non!etallic arte,acts2 In this stu/ $ re,erence !aterials #ere sou8ht #hich #oul/ allo# the test to be Auanti,ie/ as a ,irst ste( to i!(ro&in8 consistenc 2 +he !aterials nee/ to contain reactants re(resentati&e o, those causin8 /eleterious interactions #ith arte,acts$ but !ust also ha&e (recisel /eter!ine/ an/ consistent co!(ositions2 Boo/?base/ (ro/ucts #ere re3ecte/ because$ althou8h the are kno#n to e!it a #hole cocktail o, corrosi&e 8ases$ the /o not ha&e (recisel /e,ine/ (ro(erties an/ are si8ni,icantl a,,ecte/ b seasonin8 an/ other treat!ents2 1s natural !aterials are unlikel to ,ul,il the criteria o, ha&in8 (recise an/ consistent co!(ositions$ certi,ie/ !aterials ,ro! co!!ercial sources #ere e>a!ine/2 %ellulose /iacetate '8eneral laborator 8ra/e #ith 3629< acet l content$ ,ro! 1l/rich %he!ical %o!(an * an/ harbour !arine se/i!ent 'certi,ie/ re,erence !aterial P1%S?5 su((lie/ b Caborator o, the Go&ern!ent %he!ist* #ere ,inall chosen2 %ellulose /iacetate (ro/uces acetic aci/ on h /rol sis an/ this reacts (articularl #ith the lea/ an/ co((er cou(ons2 +he harbour !arine se/i!ent #as chosen as it contains sul(hur an/ chlorine that react !ainl #ith sil&er an/ co((er2 1ctual corrosion (ro/ucts on the cou(ons #ere i/enti,ie/ usin8 D?ra /i,,raction 'DRE*2 +he results are su!!arize/ in +able 22

+able 22 Ma3or corrosi&e s(ecies ,or the /i,,erent cou(ons$ as /eter!ine/ b DRE2 'click i!a8e ,or lar8er &ersion* +ests #ere carrie/ out usin8 these stan/ar/ !aterials to e>a!ine #hether a threshol/ coul/ be set ,or the a!ount o, !aterial causin8 si8ni,icant interaction #ith the cou(ons in the reaction &essels2 1ll tests #ere run in /u(licate to assure re(ro/ucibilit #ithout e>ten/in8 the resource co!!it!ents unacce(tabl 2 +he e>(eri!ents sho#e/ that F !8 or !ore o, harbour !arine se/i!ent cause/ unacce(table corrosion o, the co((er an/ sil&er cou(ons #hile 02F !8 or less 8a&e no interaction2 +he threshol/ ,or the !arine harbour se/i!ent there,ore lies bet#een F !8 an/ 02F !82 +he threshol/ ,or interaction bet#een the cellulose /iacetate an/ lea/ cou(ons #as /eter!ine/ to be about 5 !82 Unacce(table corrosion occurre/ ,or both co((er an/ lea/ cou(ons e>(ose/ to F0 !8 o, cellulose /iacetate #hile onl a &er sli8ht 'an/ &ariable* interaction #ith lea/ cou(ons #ere note/ ,or Auantities o, 5 !8 or less2

Both o, the !aterials chosen as stan/ar/s are corrosi&e an/ &er s!all Auantities o, these !aterials cause cou(on ,ailure2 It is /i,,icult to set a !ore (recise threshol/ than those Auote/ abo&e as the re(ro/ucibilit o, the tests see!s to re/uce as the a!ount o, !aterial is re/uce/2 +he re(ro/ucibilit see!s (oor ,or Auantities less than 5 !82 +his is no /oubt /ue (artiall to the /i,,icult in #ei8hin8 out such s!all !asses re(ro/ucibl G less reacti&e !aterials !i8ht ,or! better stan/ar/s2 ;ne (ossibilit #oul/ be to /ilute the re,erence !aterials #ith kno#n (ro(ortions o, suitabl inert ,illers$ there,ore increasin8 the threshol/ !asses accor/in8l 2 +he use o, a cou(on to re(resent non?!etallic arte,acts #as also in&esti8ate/2 1 hi8h (urit acellulose (a(er #as chosen as the cou(on !aterial2 Eeterioration o, the cellulose b o>i/ation or h /rol sis shoul/ increase the (ro(ortion o, carbo> lic an/ al/eh /ic 8rou(s in the sa!(le2 1s the o>i/isation increases$ /i,,use absor(tion ban/s in the lo# ener8 '600 c!?5H5400 c!?5* re8ions o, the in,ra?re/ s(ectru! also a((ear2 Both o, these chan8es shoul/$ in theor $ be /etectable b in,rare/ s(ectrosco( 2 +o test the use,ulness o, cellulosic cou(ons$ the #ere e>(ose/ to F00 !8 o, each o, cellulose /iacetate an/ harbour !arine se/i!ent 'si8ni,icantl !ore than the /eter!ine/ -threshol/s. ,or !etal cou(ons*2 In,ra re/ s(ectra o, the (a(er cou(ons a8e/ in the (resence o, either !aterial ha/ increase/ absorbance ,or the ban/s in the 3350 c!?5 an/ 5500 c!?5 re8ions2 +he increase in absorbance at 3350 c!?5 is consistent #ith the a//ition o, e>tra h /ro> 8rou(s as the cellulose chain is clea&e/$ thou8h re/uction o, absorbance in this re8ion is o,ten re(orte/ in the literature ,or a8e/ cellulose2 +he absorbance (eak at 5550 c!?5 is attribute/ to 8lucosi/e linka8es an/ coul/ be in/icati&e o, clea&a8e o, the cellulose chains2 @o#e&er$ althou8h the a8ein8 con/itions #ere Auite se&ere$ the resultant s(ectral chan8es #ere onl s!all$ an/ ,urther #ork in this area #oul/ be nee/e/2 %ou(ons #ere also e>a!ine/ b U0?0is?NIR s(ectrosco( but no s ste!atic chan8es on e>(osure to corrosi&e !aterials #ere /etecte/2 1 ,inal (art o, the current stu/ #as brie,l to e>a!ine the e,,ect o, the &olu!e o, the test &essel2 1lthou8h /i,,erences #ere note/ '#ith cou(ons in s!aller test &essels a((arentl ha&in8 a 8reater sensiti&it to corrosion$ as !i8ht be e>(ecte/* the results are b no !eans conclusi&e2

Discussion
Si!(le corrosi&eness tests are &aluable in !useu!s ,or Auick e&aluation o, (ossible /eleterious interactions o, !aterials #ith arte,acts2 @o#e&er these tests$ #hich ha&e beco!e so ubiAuitous in !useu!s$ ha&e a !a3or /ra#back in that the a((ear &er si!(le to (er,or! but their inter(retation to real en&iron!ents an/ real arte,acts is ,ar ,ro! strai8ht,or#ar/2 +he a((arent si!(licit o, the tests is also$ no /oubt$ res(onsible ,or !uch o, the !isuse o, results ,ro! such tests 'such as usin8 the cou(ons in/i&i/uall as !o/els ,or arte,acts*2 "urther$ s!all /iscre(ancies in !etho/olo8 ha&e a si8ni,icant e,,ect on the results o, the test$ lea/in8 to (oor re(ro/ucibilit 2 Cuckil $!ost ina/&ertent !istakes 'such as usin8 conta!inate/ reaction &essels* are likel to #orsen a !aterial.s a((arent (er,or!ance2 It !i8ht be ho(e/$ there,ore$ that the results ,ro! these t (es o, tests #oul/ err on the si/e o, caution$ althou8h there are se&eral (ossible !echanis!s ,or

a((arentl re/ucin8 an si8ns o, corrosion on the cou(ons 'such as not cleanin8I/e8reasin8 the !etal cou(ons su,,icientl or ,ailin8 to !aintain the hu!i/it in the &essels*2 Stan/ar/ !aterials are essential i, the &ariabilit o, tests is to be e&aluate/ an/ se(arate/ ,ro! &ariabilit /ue to$ ,or instance$ &ariations in the actual co!(osition o, a test !aterial2 +he stan/ar/ !aterials chosen here are a &er use,ul startin8 (oint2 +he (recision #ith #hich the threshol/ ,or the onset o, unacce(table corrosion on the cou(ons #as /eter!ine/ !i8ht be i!(ro&e/ #ith ,urther e>(eri!ents an/ b usin8 less a88ressi&e stan/ar/ !aterials$ althou8h it is a co!!on ,eature o, corrosion e>(eri!ents that results sho# 8reater &ariabilit as the Auantities o, reacti&e s(ecies are re/uce/2 'In ,act$ it !i8ht be interestin8 to establish re8ions #here the re(ro/ucibilit re/uces belo# a 8i&en (oint an/ use this to /eter!ine the threshol/ ,or onset o, unacce(table interactions2* +he threshol/s allo# calculation o, the concentration o, '(articular* (ollutants that cause unacce(table corrosion to the cou(ons in the test en&iron!ent in the ti!e o&er #hich the tests are run2 +his$ in turn$ hel(s to /eter!ine the e>tent to #hich the /ata can be e>tra(olate/ back to realistic en&iron!ental con/itions2 "urther #ork is nee/e/ to assess (ossible non !etallic cou(ons2 1lthou8h in,rare/ s(ectra o, (a(er cou(ons sho#e/ absorbance increases in the 3350 c!?5 an/ 5500 c!?5 re8ions the chan8es #ere not su,,icientl ob&ious e&en ,or the &er e>a88erate/ a!ounts o, corrosi&e !aterials use/2

Acknowledgements
+his #ork #oul/ not ha&e (ro8resse/ #ithout the su((ort an/ encoura8e!ent o, other !e!bers o, the %onser&ation Research +ea!2 In (articular$ the contribution o, Ea&i/ "or/ is ackno#le/8e/2

References
5 %larke$ S2G2$ an/ Con8hurst$ E2E2$ +he corrosion o, !etals b aci/ &a(ours ,ro! #oo/$ J2 1((l2 %he! 55$ No&e!ber 5675$ (( 43F?443 2 BS 603:13::569:$ Metho/s o, testin8 &ulcanize/ rubberG (art 13:G /eter!ination o, a/hesion to an/ corrosion o, !etals$ +he British Stan/ar/ Institute$ Con/on2 3 ;// $ 12$ 1n unsus(ecte/ /an8er in /is(la $ Museu!s Journal :3 '5*$ 56:32 (( 2:?29 4 Green$ C2R2 an/ +hickett$ E2$ +estin8 !aterials ,or use in the stora8e an/ /is(la o, antiAuities H a re&ise/ !etho/olo8 $ Stu/ies in %onser&ation 40$ 566F2 (( 54F?5F2