cn a pie su 208 Chemical Degradation of Cellulose in Paper over 500 Years 4y DAVID ERHARDT & CHARLES S, TUMOSA Paper had been intodcod into Bure by te 12" century by Arabi who in ura had obtined the wehoology fom the Chine much carer! The development ofthe printing pros grea incremed the quantity of paper seid nd by the end ofthe 13" cetury cnsierable mounts of popes ad been produce, Printed upon and bourd ito books. The lage amounts of paper aval fom The 10 century onwards provide am opportuni to examine the chemi ad pyle changes brought about by ume and sentalyncontoled environ ‘meat. These changes, tr, llow sto evant How changes inthe man Face of paper flected it ageing bein. Daopmen i th papermaing rs By the 15° century paper comisted primary of beste, souked and macerated linen fibers Caton fibers were abo becoming an important component. Oxer ‘matsals have been wed but in general the Bet paper as mide on ie nd extn ag fibers, Italy, both te pulping process and the conversion of pp 1 paper were low mandal rocenes Flac or rags were rte and Benched in the won. proces that eouH ake mont, Ihe mater was pulped wing pele nd movtat,o later using mechanical sapere sper war ote produced nese ‘ounain rears that provided th clean water nade for the proces In Earp, ‘uch water was oflen hard, caning line, which conte tothe allalinty snl permanence of the esukng paper elon sng was applied by cpg the pape ina olution of gelatin. The tbs of sing were subject wo spoing. Around 1K, de addon of alums to che sizing soliton wae ierodaeeé The sum had som sng abby of te on, bot primary served wo aden the gelatin and pre ‘ent the slut fiom puuelsng. Uniotanately, alm usally contnined sme resal safe ac, and alumszed paper was not as permanent. Faster, more Aes 8-40 Hee ee 15)(Chena Deaton of Clie m Paper e500 Yar fins and lager scale mechanical process gradually were developed. The Hollnder bear was ioduced 1680. Iwas much fer and mote poe te than mochaneal stampers, but i plpng ation reed in che fibers “Around 1748, "backing and erafing, treatment with alla flowed by mil ‘id (uch os sour muh was introdsed. Laer, fri cil was used to peed up the proces! n 1774 Seecle discovered chlorine, and chlorine bach soon fa lowe: tok a whe fr the Bleaching process to be pile, lament, and ‘quanis of paper were produced that were either unable or crumbled soon afer ‘manufctr. By the 1 century de der for paper was such da her sures of else burs, such as sia and grass, wee Being explored. The develop ‘ment ofthe coston gin in 174 made much grater amet fection ber wv ale. and redoced the urgeacy of develop other fiber sources for some time “The demand for paper kept mcreasing though, especially withthe inoduction ‘tthe Fourier machine for the contour, rather than batch pradcion of paper. By the mid Inte 1M century methods end procenes were developed ‘hat enabled the us of wood, the largest single reer of cllove, a source of paper fbes, Because mechanical esiment of wood sane dd not prodhice ‘ory good quality pulp or paper, chemical pocenes were developed to remove some of the noneelsie components such gn and colored teil to ‘rovice higher quality paper. These acide the sada process the TAs, the sulpte proces inthe 1570-18, and the slp Kra} proces a the end he 1800, “The proces of making paper fibers changed withthe nrodation of ne lee sources new chemical and physical paling process andthe adoption of cher cal bleaching techniques. A mere tarogh Ghewsic ofthe development sted hove well ar other development nthe manufacture of pape, can be found inthe rice by Clapp. These changes sigan altered the ageing behav ‘of paper: These changes canbe roughly ded ino thee eateries changes 0 the Sher sours and adie), changes inthe mechanical production af pulp and paper arid changes inthe coma westment ofthe pulp Chemica chang dering aging Papers a mixture of ellos Abas: Other component such a hemicelloss {nd lignin (om wood) may also be presat depending onthe commpiniion of the Fier sources used for a specie paper. Added components ince such materi 4s ran casa carbonate cianum dxde or cay walter the properties ofthe Final sheets of paper Al these components change with me orale the ag Ing cuacterstes of other components ofthe pap. The present eenibon of ld meDavao ERHARDT & CHARLES. ToMOSA paper acted by a numberof fatows: dhe component fibers (and sds the poces of manaactar, the cumeative fleet of ue and he sorageenvit0n. rmertand nally the handling ofthe paper as tltarian obec. Except for con cdot of extreme hea or drys, the pinay deterioration mechani ide fiom boii atack a ht RH) ishydrolyss. Tas resus in depolymerzaion ‘of the colulose chain, and the sealing products include gacose ithe base ‘chem compound frm which cellulase it devived) and oligomers hort chan polymers) conning tvo or more nts of glucose. Simin, other sagas such ‘sion nd arabinose el rom the hydolysover ie of component ch ‘xj and hemcelalone ‘iper samples panning the ane period fom the te 1 centary tothe present were analysed to determine the amounts ofgacese and nese produced from the alluiose polymer and xylan, especively sth paper ages Over the coun ‘of eaturies Hycolyss ofthe celle to yield gucove ax inal product an expected reacion of cello with absorbed water, and gucote serves as an Indator of the extent of hydrolysis ofthe emia unit ofthe cellule i paper Sims xylose serves aban indietor both ofthe presence of xan esl fiom wood pup] and is hydrolysis. In an ital antermpt eo determine te Bo polymere sigar oncentations varied in any dacerable fashion, wax deided toeamine a range of papers of arying properties EXRERIMENTAL ETHODS apa was acquled ftom dcaded document books, oF Fagments of books that ‘had ao hnown pir weuimens, Aas were sumpled ner the edge of the shee, voiding areas wth obviows water sinng foxng ot mechanical damage, Sam les ested were approximately 0. to | gems in weight. All of the specimens ‘wecein a reasonable atte of preservation, and conld be handled and ied wth ‘ut gail precations, ‘Cu cematngaphic anajiee af ecchavides were peefrmad fer aquacu ‘eanon anda wostep derivation to cnvert carbons! groups to Osim and to tinea reactive hydroxy! groupe as described previously’, Mente iw of components as made by compaiaon of retention kines with standard ‘syle. Concenratons were determined by compuison of petk areas wit ha fw internal sandard (O-phenytf-D scopyranove. This method allawed the ‘desion and quniication of simple sas 28 wel as thei oligomers pt eta meron sugar wits) in length “Miroxepie examination was wed 10 dont the composition ofthe paper Aber 153Chena Degradation of Claes in Paper os 500 Yeo SS is = CT a a a a Date tring a. Comatose eas in pane sang Hote vrs oo pring, Oa ot ‘ronan Gelman te papermaking paces re ao mate RESULTS AND DISCUSSION Fg shows x plot ofthe solble cose content of papers fom the 15 to the 20 ceturies Th data show thatthe earls papers pre-1650) have produced the lowe amounts of gucre even though they have aged fot over 200 yars longer than mos ofthe other papers. As the demand for paper increased tough the entare, changes inthe procening of paper ocied. The newer papers (modly ost 106) have produced mach more ghcave han the cde paper Sine thee sper come fom a variety of sources iis nly thatthe ferences are du to pos-praducon eeament, we, or ervizoament. The diferences are more Ukly ‘due tothe changes in papermaking th oie ring ih ve span, a aunber ff wench cou els ager nouns of licose ung ageing. "The elder pro Comer may have removed much more af the easly daly component (ps "bly though fermentiton} than tbe newer proces in which the pulp nat foaled for nearly a lng and in which biloyeal growth is minimized or po ‘ented. The gester degree of mechanical maceration ard shorter Aber length Sthieved bythe Hellander beter may have lio rated in shorter ellos cain lengths, meaning more end unis exposed to bydrolyi. Mont Lely, though, i the act tat the newer processes ether created or depested acidic compen that ete hyolst. Am sting, lr rosin sing (and les, aluminum su 1Davin EanaRor& CHARLES. Tustosn ben sissy eae Bee] mnie ‘nn eee pe tar ine 82 Connon of nyse h page anges posed varus dle lpg Dales ot "ron cevecpnens nt peoermsing paces Sco ca fe rosin sing), bucking and erfting, and he sulte and salle process all wove ientment with adi materials Uh rest beng washed out rng ene fucure. Chlorine bleaching, aswell may oxidize the celludone tnd poco ear bony acid groups Is ineesing Yo note that the se of groundwond docs net byte scm et in pater aman of gow, ince, wih on eeepc ‘igh valu, al ofthe glcose concentrations nth tested wood pup papers te iin he low range of vale for rg papeer manufactured daring the ome tne Spa. The incense in te ate of yleosepredntes the invocation of ground ‘ood an probably doe more tothe intthcion of acide proce espely {he we of alum and alum rosin sing. Alo of nate is that he ineretae ewe or «ton, made pssible by the development ofthe cattn gn dd not tel fw sic dora in lacse levels eaeep pay fot heer papers eh the lower levels are more likely thereat of shorter ageing times The gone evcepion i that the “bes” paper is made rom eon, beau itis the paren aural occur oure of ces bers general avalible: As wi he po pon tat wood pulp papers are inhereny bad, the perception that coven Papers arc consstetly beter also not uniformly tue The primary for that stems the ageing behaviour of paper is whether or notte manufacturing rotes ees in an acide paper. More extemive ten, epecilly of paper 'manwfactared daring the 1600-1800 ime period shoul allow beter cortemooe ‘of changes in processes wich changes in ageing bdo 1sChnical Degradation of Clon Paper 500 You Fig. 2 shows pt of he soluble xylose conte of papers Fam the 15° to the 20° centres, The amount of xylose in the ealot papers wea fond tobe sundetecnbe, or minimal when compared to moe feceat specimens of paper From the 1 and 20 centuries. Tio factors may expan thie Ft with he sul for glaose, the nor-eliiose, xylene containing material may have been more effectively removed during the prolonged reting and anocated Lateral eon. Second, the generally alkaline ealy processes, s oppsed toler ace process, esl less acd-atalyaed hycrolis of any xose-conaining ma ‘eral that remains. Unlike the rests fr glucose, however, ros ofthe papers tri dhe highest levels of xylose ae wood palpcontining papers. This 0 be spaced expecially tr wond pulp papers that were minimally procened and i (chick mach of the woods, nomeluosie materi remains. is possible, through ‘more severe chemial an mechanical eimen, to remove moa ofthe woody ‘tater, akough auch westment ako reste in shorter fibers and wesket (although “cleane™ pape, Ths probaly the case with the wood pulp papers thac have evel of xylose comparable to non-wood papers Coneusion “Te plot of the amounts of gare ver eof rnfcte show tread and icons that my be explained by change in paper manucring materials tnd proces, The oldest papers ipre-1680) were probably produced by snr procedien, and i is intersting thatthe amounts of both slucose and xylan these papers are bok consent and very Tow despite the age ofthe papers. This is probably de wa papermaking proce that tended wo produce at lle pa et that contained Ite non cellule materi Later papers tend to have Inger ‘mont of bath lacve and xylose, even hough they hive aged or ssa Storer times The higher levels are probably die to the inradaction of new ‘hemi and mechanical process that rested in mote degraded fers and Acidic pecs that canine more nor-ealllsie mates. The primary fst i the sy of papers produced by the newer process, a demented By £00 steal high levels the sugars ony fer the introduction of aid proceses, bat bath befve and fer she intoduction of ther ber and mechani paper = "Rag and linen papers contain almost ao xylose, while the amour in wood pulp popes ange fom very lage amounts o stall amounts comparable rag Tapers. Testing of more semper may alow beter cortelasons of glucose and ‘low evel with changes nth papermaking process, Hewever, even the eis far have demon hell's ofthe changes, 156Davi ERHARDT & CHARLES, THMOSA “The authors wold lke wo thank Joseph A. Coles forthe microscopic analyses, Seaesanes Gael deedation fle paper er 500 ys Caen of ese ge ling ee adhe popes red oer a ‘anyone mre dried. 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