TABORATORIO NACIONAL DE ENCENHARIA CIVIL

Proceedings of the

InternationaI Symposim u

Stone consolidation cultural in heritage
Editors Delgado Rodrigues José Manuel Mimoso Joáo L l s b o n . 6 -M a y2 0 0 8 7 ,

research oractice and

no em ñário r€aliado LNEC Maio2003 Sem

AC NAC DE copyrtghr LABoRATÓR|O ONAL ENCENI-IAR V L, . P @ CienlfiGe Técnica Div¡sáo DivulSaeáo de L 101 av Do BRASIL . 1700-066 SBOA

E¡itor:LNEC Nacionaú nremaconas e Reunióes Colecqáo

coñ8re$ / hte¡natonaL / hefitaSe NatufaLrone stoneconsolidation / DescriptoK cuLtufat int€ma'onaL de de natuGl/ ConseNa!áo Pedra coNrur6o / Co¡8re$o o coLtural/ Pedra Dscritores: Patri.nón intehalonaL de PierenatureLLe / Consolidation la Plereá batn/ congr¿s Descripteuu ParimonecuLtural/ cDU lsBN 6912,620r97(063X100) 97A-97249 2135-a

Evaluation Cyclododecane a temporary of as consolidant CulturalHeritage for mater¡als
ChiaraAnselmi PhD Chen¡sfry/PastDoc, SMAArt c/o Dip¡i4imento di Chinica, Uniyersít¿' degli Stu.li di Perugia,Pe¡"ugia, Iralt, chiaruaús@ínwínd.ít BrendaDoh¿ y PhD Chenistry/PosfDoc, 5tr4,4,4rt Dípaúimento.li Chimica, Uníwrsit¿ deBli Stu.Ji c/o di Perusia,Pe¡"usia, Italy, b.bd.daherr'@tdtkz t.con Federica Presciütti PhD Chemisttj, /PostDac, ktifuto CNRdi Scicnzee Tecnolagíe Malecalari (ISTM, Dipatinento di Chinica, Uniyersitáde&liStudí¡li Perugia,Perugíe,Iab), fe¡ler ica@thch.unips. iI Costanza Miliani PhD Chenisúy /Researcher, Istituto CNRdi Scienze eTecnologieMole¿olari (ISTM, Dipartimen¡adi Chinica, Untuersit¿deglí Studi di Perugia,Perugia,Ifaly, miliani@rhch.un ¡t ¡pg. BrunettoBrunetti Professor/Chemist¡yPlatessar, Uniyersía degli Studi di Per gia, Petueia, Italy, bruno@drn.unips. il AntonioSgamellotti Professor /Chemistt),Prcfessor, Unirersüá degli Studidi Perugia,Perug¡a,Laly. sgan@thch.unipg.il

SUMMARY: Cyclododecane,(Ct,Hu), has been investisated Ior furure use in the lield af consenatbn as a tenporuty consolidanr for fragile nater¡als af art hitraric inpartance in situatiotls oJ energency ftdnspoú, excayation or handling. Thís contributian has prinarily established the citeia Ior sobent applicdfíon of white spir¡ts a d cyclohetune \|here assessnent of subsequent sublímation hds been fa owed util¡zing partable mid,Infrarcd ReÍectance Spectrascapy. Furthet dnatyses bj Prcfle NMR-MOUSE (Mobile Unílersat Su¡face Exploret) were use¿ to sdín infomation on the depths of penetratían af the cyclododecane h dillercnt stone matices as well a: to folow its eyaporaríon fTon within the nast potous oJsystens. KEI WORDS: Cycla¡lodecane, temporary porrahI e instrunentatian cansoliddrían, water repellent, transpotL

INTRODUCTION
(CDD) a vol¿rile Cyclododecane, (CrrHr,r), been(seldon)adopted use cyclicalkane has for in th€ fi€ld of conservationin the last 15 years as a temporary consolialant, sealanta,nd prol€ctive hydrophobic coating ftagilematerials situations transpor, for in of excavation or handling Literalure showseveral potential usesof cyclodod€cane situatio¡s for where Í11.

drd ¿re of anJ LUn\olid¿r.on rmp-egnJrionlrrdre m Icralsur ob'ecr' de':r¿ble .empordq arLn¡eorog'cal ol pooo*d ¡rd 'poraJhall) c'red. br rhe'e(Lnnts LrJtsrre hr,c bee¡ g a u / e' r e ' s , n " ' . ' ' , ' ¡ " p o r e r o n o r ¡ ¿ ' l p a r r r i n ¡ ' r n a c $ ' r l -a l ' ) e f " f i m p ' c g n ¡ r e d " of peitonneaon mediawirh diflerentdegrees water t.eatments ¿".i.g "q'.""s andp¿per its useon architectur¿l stucturesl2-sl This waxv and "."t..ii* l.n"ir;'irv *.¡ i" t"*r¡.s due furtherasrouli¡e in lbis discipline exploitert coulábe greatlv ."riJ .á.. within an ", "-p*"*"uupou.p..'rui. which permiis it to subhne completelv i" li" or operalions "¡."o*i'ii. o¡ bv removal phvsical chemical tnne t6l elimi¡arinssubsequenr appropiate or by-pfoducts of treatmeDt residues unnecessary ñlnl-fonringpropefies'lorvmelting m be ideallyLLlillzed lhis field ¿si1hasgoo{t CDD mav a 5, ' s ¡ o . ' i r . i r ' o l u b i l n in ¡ d r e r . o l u b r l i ti)1 o r g d r ' r c ¡ l ' r 1 r s ¡ d l i r r l e r 1 o " "',,",,'"í lhr' t)diocrúr1 J ed'rrv re\ersible or ior^rn 71.Yer ron iTponrnr'vi" appricar rs rr no'tporar 'i;;ii.'br;.' tut, .¡i oe ,porie¡ ,i 'n"r'* '','. or .¿1 be üi"o'\e'r erh'n' The or f)d-oLJrbons peLrole'n h.loseldred -l'f"''*.¡r'*"i,'*."'"'."i. "' or,b) i. io|medeir\erb1 ruoIng v" rle n'olen.rtulerra' ,urrl filo of c)cloooJc,"ne rre ior' ¿ salJrared Jlrol ul c]croJooecrne r' Lenllú e\Jpñ'¿re atlolirp lheor|rarrc "u rrelrirspoinr' one urrl d l'igl b\ '.i1.'.,i"" .r;¡. blrJer' c¿nbe erarded choosns 'be e':l' o\jccr rn a con,a'ned keeorru rre¿red srdre. ,r In a norrer ¿ppl)'ns :T:1",i: e' 'etrperatu ql ll har been Dr;r;.r';q rhe rcareduL ecr Fonr e\po'r're o elerated r" úhicl-rr-i"¿pplied ol r"rn.'"i ¡",'hL filll 'unlb-.' ro hc ropograph¡ rheslbsrrJre rg on lhedpll'¿ ron lrethoJ'Lhoier'Lne rin) lló. uhe¡e.r. c\¡¿c¡err'rrcs vaD deperJ elle(r' ln e D o r o s ro f l h e ' J b s r r " l r r d l h e r a r t o l f i l f i o r m a l r o ) l l l l ' i c n rh ) d r o p b o b f \ lou 'vrrl a melror \ol¿rrebildrngtidordo- n solLlrons-urrh boilil' l;-úJ;,"1."" ol L\roofalron sol\err produ'<'a lrlrn-olvcr) lrnc Irgnry .o,veir\ ,rhere.por,r¿reou\ arilg \tl\en's 'onsisrol larJecorr'¡ cosr¿r: frllr' Irom "lo$l) erdDo o"cleJ cr\slr''. ro ivhichmakethempemeable waler[5] for application wlite spüilsand of the selting, prelhinary melho{ts solvent in a laboratory The havebeeninvesrigated. fonnalioD porosities of ón cvclohexane diveÁestones varving 1o densitvthal is nodified in accordance ¿ndnet$'ork frucrlLfe oi the differingc¡ystalline with oplicalmlcroscopv solvenlhasbeenobserved of the selecled rhe rateof evftoration m subhnation of io an¿iompa¡e¿ trnt orthe lnolte¡ CDD. The assessment rhe subsequenr bv Spectroscopv ** followed ulilizins portablemid lnfrared Refleclance ","1 ""i" NMF \4OUSl l\4obile b) ¿nJl\'es Profile .i"',.".i;i"g 'h. m"¿e'o .r¡rariur'l-unher ol e rte deprh' ol penelrJ'rul rne Uri'e.al sLIf¡ce t\plorerr úere L'ed lo ob'c in eachstoncnatrix as well as to lollow its resurrn! froí eachsolvent ;;ú;"";." ofsvstems wilhin ¡hemostporous fron1 evaporalion optimumcriterialbr the.use of has This coDt¡ibution soughtto developand establish a ' r t e á t ¡ " ' r ' e u l t u n r r < o f l h a r i o rr o r r ¡ r e i " l ' u f J " l ' i ' r o r h c v co ¿ o ¡ c . " r e " i yrparrrrng.. r lh¿l 'e{rile,. and bu',drnü' 5cLlptule' rn l le rdrc ar.hieclJr¿l e! In ponrlL nrnc ano 'afe inlefverrr'on r"ll) 'l rfdgrle o- rn e'pe' nmedarednJ reqJfe r¡'e ol cnergen,r "1 ofconservation a direstale

204

EXPERIMENTAL Reagents samplepreparat¡on and
gr¿de wherepossible and usedas received. Al1 chemical reagenls usedwere of analytical from PHASE Cyclododecane purchased was ftom CTSs.r.l.Italy.Whjtespiritwasacquired and liom J.T. B¿ker. s.r.l.Italy, specialized producfs in utilizedin restoration cyclohexane Stone samples obtained from a local manufaclurer, Pemgia, of Canara marble paper (240 C). The CDD scmx5cnax2cm werc polishedusing a gmdedsilicon carbide wasprepared ulilizing l/l w/v in solvent, followedby gentleheating andaccurate solulion splayins overtheeniireavailable surface.

Methods character¡zat¡on of
Portable mid-lnfrared Retleclance Spectroscopy portable IR Non inv¿sive in$aredinvestigaiions havebeencalriedouf with a compact FT wirh VIR ar00 qpec'rophoromerer Lm: equipped d fiber JASCO r50x50\5U J5 kg weighl'. a lhe source, optic exlension. opticalbenchis madeof a Midac llluminatorIR radiation Telluride) Michelson interferometer, a liquidnitrogen and cooled MCT (Mercury Cadmium deleclor.The Remspec mid-in&ared fiber optic probe consistsof a bifurcatedcable glassñbers,7 of which car¡y the infraredradiafio¡frorn the 19 containing chalcogenide 1() while the other 12 collectthe radiationreflecledotT the sample' source the sample, surface. acquirable T}le specl¡al range 7000-900 is cri' at a resolution of4 cm r. The fible (0"/0' geon€try)al a dislance about"2-4 of opticprobeis kept perpendicular the su¡face to is mm.Theinv€stigated sample area, deteminedbytheprobediameler. aboul20mm'. as R, diftuseandspecular components, measured is Thetotalreflectivily, due10th€ combi¡€d The &on an aluminiumminor plale for background cotTectioD. usi¡g the speclJuln intensily wasdefined the pseudo as absorbance whereA' - log (l/R). Due 10 A' spectrum samplingprobe geometrycollected signals may confain bolh diftuse a¡d specülar reflections. While difTuse reflection cause can only slightshiftsin absorplion bandposilion, may caus€ as compa¡ed transmission ro speclra, specular ditTusioD derivaiiveor inverled bandshape(,"¿srsr,,ari effect). el? (an lo baseline the pseudo and absorbance average of Thedatahavebeentrealed a conslant 3 pointswith relevánlerors at eachtimely interval)hasbeenfollowedfor characteristic matrix. bands ofCDD film andlhemarbl€ Profile NMR-MOUSE(Mobile [Jniversal Surface Explorer) NMR sensor eqüipped with a sinsle-sided TheProfileNMR MOUSE[1] 12] is a portable permanent generaling uniformslaticmagnetic a field gradient suitable magnel anangement placed p.ofilingup to depths ofabout7 nrm &om objects nearby. for highresohüion sampte is Its size is approximafely 100 ' 100 x 80 mn1r.The working frequ€ncy 11.6MH4 th€reforethe signalis dueto the decayof hydrogennucleus-The NMR signalde¡ivesftom a parallelto its surf¿ce, wher€the field st€ngthis thin slicecentered nlm above device 7 the The slicevolumeextends 0.411T and the gradient 20 T/In alongthe depthdirection. is of abou!10 x 10m¡rr alongthe lateral directions, sizethai is detemined thegeomet¡y a by

205

on in depends coil whilethe thickness thedepthdireclion theradio ftequency of thesensor, parametels canrangefrom I 80 to 2.1 FÍI. and the setling of the measurement js wifh a precision 10 Fm to scan of on The sensor moünted a lift, which canbe positioned sliceltuoughthe object.Fot eachslice the tansverse the profile by shiftingthe sensitive to irain.The measued signalis r€duced decay collected is with a multj-echo magnetization prorondensilylvithir the sensilive sliceby pafial i¡tegrationof the echo a T2 weighted NMR as The ofthesenumbers ¿ fmclion ofdepih formsthe neasured envelope. collection to by depthprofile. T1 weightingcan also be introduced the measuremenl varying the large By the delayis chosen subsequent acquisitions. default, recycle recycle delaybetween from the profilea¡¡plitude eachdepfhwascomputed at to The enough avoidTl weighling. jD echotair. sumoflhe maxina oI ihe firstechoes theacquired Optical m¡croscope equjpped with a Digilal CaneÉ LeicaDC 300 hasbeen A LeicaDMR OpticalMicroscope used. lmages have been captu¡€dusing polarizedvisible light to observesuperficial through subhnalion. moryhology changes film form¿tion on

AND DISCUSSION RESULTS
lbr elhanol, acetone ofcentralimportance or is in like The insolubility polarsolvents warer, this thai It of the application CDD in the field of resto.¿1ion.is only rhrough characlerislic a wateror other fealures a protection as against volatilesealingor addingof hydrophobic with the possible. in methodstarted polar solvenls becomes knprovenents the applicative pri¡narilyon thet low toxicily whichwasbased of non selection opportune polarsolvenls, solvents aronatjoor halogen¿ied or non loxicity [13]. This choiceilmedialely excluded then, due to iheir great of because lheir provenleve1s toxicily. Alkan€sand ethers, of structural ¿fiinity with CDD and, wilh few exceptions,a relalively low loxiciq7, were the is because to This compound class€s investigate. proteciion nol reached seer:ringly suitable and alone.The consolidatiltg preseFative of the insolubilityof CDD in polar systems propeliesof CDD depend the nalureof the filrn formed¡s a dir€clresultofhow it is on tbe havesuggested 1() that avoidwaterpenetration, applied overa surface. obseNalions Our to structure bul ideál fibn shouldbe not needle'like rarhersimilarto a glassamoryhous wilhoutthe holesth¿tcanbe foundin needlelike coverage ofthe surface ensue compl€1e thanbrushi¡gandappears most on rather c¡yslalnels.This typeoffihn is produced spraying concluding that in general, similar to the nolten CDD, repo¡l€din rec€ntpublications providedbe[er proiectionthan so]venl-hsedspplication[]l as molten cyclododecane in obseFed figurela-d. and ofers rhe bestsuface coverage such It was obsenedthat a iow boiling poini solvent appearsto h¿ppenbecauseof the evaporalionrale, that when too fast does not appearto we the For and leaveenough time for crysialgrowth, hence betlerfilm coverage. thisreason first tried to employ solventsnam€ly ¡-butyl melhyl elher and pelroleumether wilh boiling goodsohbility, ahhough showing pointsof 50"Cand40 60"C respectively. Both solvenis, to have demonstraied be 1oo volaú1efor our applicativepurposesas the resuhing in of lo with its overallincre¿se thepresence highly sublimation appears havebeenaffected Thus, our attentionwas tumed 1()higher boiling poiDt ones ln volatil€ agentsnal. thal paíicular,we haveinvesligaled behavior the ofcyclohexane. is knownto be muchless

toxic than its acyclicanalogue hexa¡econsidered z insieadto be a neurotoxic solvent. Cyclohexane's boilingpoinl (81'C) appeared be ableto conjugate ease application to the of to ¿ sufficiently fast evaporalion.I¡deed we found the crystalsfomed wilh cycloh€xane to be nore squamous like than ¡reedle like, ensuringbefter surface coveragevisually. Funhemore, different concentrations CDD in cyclohexane of have beenexanined, finding l/i w/v to be the nore satisfyingratio. Becausethis concentration represenls an overs¿tuated solution, gentle heating for a few secondsis necessary obtain a 10 homogeneous sohfion.

Figu¡e l¿ d: Opticalmiooscopeiñaeesxl00 mag.a) natml Caran marble,b) CDD brushed application, CDD moltenandporredon surface CDD spruyed c) d) atplicatio¡.

In the effort of conparison, white spirits, a solvent nomally employed in restoration envirorn¡ents,afthoughdisplaying a greatertoxiciry, was utiliz€d to monitor the different behaviorof solvents.wlite spirits is a linear and branchedalkanemixture wil¡ a v¿riable (19% in our case)with a boiling ra¡ge betw€en150-185"C. was content aromatics of It observed, imagesat the optical microscope, by that the solventroo canhavea large effect on the resulting morphology ofthe c¡ystals l15l (figure2a-b)ofrhe CDD film whenthe latler is sprayedin solulion. This is consideredas an effeci of the parureterc in .he gowing crystal system,such as the crystal bulk, solution buik and the boündarylayer betweenlhe crystal solution and bulk containing interface the can 1o [16].Thesolvent be assumed reduce the growih rate of cryslals and has 1obe removedfiom the surfacebefore the crylal face Throughout trialsof application solventchojce,fiber optic mid-FTIRwas ableto the and the define efiiciency ofthe film, i.e.whelher not theresulting or filrn covered underlying the marblematrix sufiiciently, the presence absence characfedstic by or of bandsof both the CDD and the marble. Fisure 3 displays speclraof a) natural Canara marble where,in the

207

ñom 16001o1400cm ', thev3tundamental siretching vibmtionof spectalregionextending which causes Thisbehaviour mainly,the specular is, compo¡enl, the COr' ion is obsened. major distofions to occur in the spectra,andevid€nt in this caseis the so calledre.ststrdhl¿n chatacteristic bánds band[17]. Figure3b) showsa spectrrmofpure CDD, wiih numerous to from 950-1500 cmr at 966, 1041, 1076, 1162and 1245 cmr mosfly attributed c) C-C sl¡etching modes ofvibration 1181. Spectrum showsthe marbletreated asymnetric coverage the marblematrix. d) insteadshows¿ of with CDD, indicafingthe complete with CDD afteronew€ek,wheretheCDD is nearlyall sublimed specfümof maóle treated reveali¡s the marbleundemeath.

imagcs x100mag.of CDD aplied after24h in a) cyclohexane, Fisu.e2á-brOpticalmicroscope

I

I --*b

--tlt
/

t'"^

(

t1 \

J

I

L
Wavénumb6.(cm )

Figu¡e 3a-d: FTIR reflectdce spectE of a) natunl Camra teaiedúarbleandd) sublimcd CDD on márble.

CDD sta¡da.d. c) CDD

From this. olher lhan lhe chemical nature ol lhe CDD aDd solveDlcompositionsll9l, rhe film fonnalion a¡d subsequent sublimation of the CDD ca¡ be monjtored through ba¡ds j, both charactcristicof tbe CDD, such as the afbre¡¡cnlioDed band at 1245 cn1 and of Lhe marble subfrate al 1562 cm', hig¡1ighled in figure 3, that play inporraDt roles in conLrollingthe surfacesl¡uctureof the film which can si'nply defe¡minethe efticie¡cy oflhe film fomed with eachsolvenl (ilgure 4). From figure 4a, it is possibte liotn lbe ch¡racte stic peak of CDD to Dote that both the solutions of CDD/whiie spirils aDd CDD/cyclohexane behave differently on the marble surfaceuDderroom lenperalure a¡d pressure, where the rate of lbnnalion ofthe CDD film is relatedto the evaporation oftbe solventwhich is obse¡\,ed slabilizeaftef circa 6 hou¡s. 1(]

É ¡. ¡

$ 1 s

Flgure Plol ofpscudo 4: absorbance oflnfraredpeakal a)1245 r andb) 1562cm againr Lime cm (hou6)ofmarblebeared rvithCDD/Fhitcspi|its¡¡d CDDhyclohexán€ reqrcctivcly Following such.tbe monltoring oIlhe CDD/cycbhexa¡e film sublimalionoccurs consta¡tly afler 72 hours and the peak at 1245 c111' no loDger obseNed afte¡ 96 hours. The optical is microscope gives an insjghl of this subhnálior lvhere the film is punctured $,ilh holes creali¡s i¡creasinsly large lslandsolexposed marble (fisure 5a).

FiSn¡e b: Opticai 5a ¡ric.oscolennages xl00 mag.ofCDD ¡ptlied alter9ó houNnr a) cyclohcranc, rvhite b) spnits.

209

Inslead with CDD/white spi¡its the film appea$ constantfor 72 hou¡s, afte¡ which it too sublimes completely after 144 hours. This filnl asain obse¡vedwith optical microscopy of shows a similar sublimation,wilh the pres€nce small holes that incr€aseand exposethe u¡derlying marble (figure sb). Following rhe same time scale for the appearance the of cha.acterjsticbánd of narble (figure ab), il can be observedthai this baÍd grows as the leavingthe marble exposed. CDD/cyclohexane The to CDD fil¡¡ sublimes subsháte begins noticeably exposelhe maaix atur 72 hours, yet is consideredcornpletebeyond 160 hours when rhe mal¡ix is more €xposed. The CDD/while spirits süblimationis more lapid a[ef 12 hours¿fterwhich natrix becones the increasingly obseNed 144hours. 10 Profile-NMR-MOUSE can be very usetul in measuringthe thicl¡ess of the CDD layer which forms on the surfaceofthe stoDe, well as nr offering indicationsofils penetralion as insidethe sloneandfollowing its disappearance ñnction of time. in The plofiles of CDD/white spiriis on Carraramarble in tunction of time are repoÍed in figure 6a. tt is importanr to obse e that the first profile is very different in shapeand in amplitudewith respectto the others,probably because high boiling poi¡t solventis sli1l the p¡esent in ihe CDD film and this fact can relevantly alTect the NMR measuremenls. Thereforeit is impossible1oestimatethe startingthicknessofthe layer, but it is evidentthat after 24 hoursihe solventis completelyevaporated the thicknessis around270 pm. The and proñles are characterized an increasinsly thimer layer becauseúe CDD subsequent by startsio sublime;after 144hoursthe CDD visibly disappeanexceptfor a small island which fal1s lheneasured in are¿ lcm'. of

t j I
E
6E

0 100 2¡I0 300 ¡O0 500 600 700 depth(!¡m) depth(pm) Figure b:D?thprofiles measu¡ed 6a onCDD layerapplied Cararundble at differe¡tiimes a) on in in whitespirit¡,b) cycloh€xa¡e. Eachprofileis obtainedusi¡g CPMG" sequence orderto collect tn¡sversemag¡etiz¿tion decays s'ith an echotlme rE=0.052 rR= 0.15 s, and 256 scans ms, (depthrcsoluflo¡ 40 pn). The results collected for CDD/cyclohex¿ne are repofed in figure 6b. tt is noliceable that the low boiling solvent is alreadyevaporated affer 6 hours and the lhicknessoflhe CDD l¿yer is arcund 470 pm. The CDD siarts to sublime and the layer becomes thinner. After 96 hours the thicknessis around 280 pm, thereforethe layer has nanowed approximately200 pm. In both casesthe CDD does not seem10 be penetratinginsjde the stone,most likely due to the Car¡aG marble's characteristic 1ow Dorositv.

ro0 t00 100 200 300 t|oo 500 500 700 300

210

coNcLUstoNs
It has been possible to prelininarily study ihe applicajive mefbods of clctododecane in differ€nl solvenlsso as 1o acquirean emcienr consolidaringfilm for an appropriare amounl oftime. In order to p¡oducean emergencyprolocol for the applicationofcyclododecaneto marble su{aces it has bce¡ possibleto slirdy rhe €ffecr ofdifferenr sotveDts the duratioD on lJ1 the film. From the numerous solvents studied, resutts have b€en given for rhe use of cyclohexa¡e and common white spirits. These ¡esulrs show that lhc CDD/cyclohexa¡e soluiion createsa fi1m thaLcaü be observedwirh FTIR and profile-NMR MOUSE unril ar least 96 hours, wh€¡easthe CDD/while spi¡i1 solufion can be observedup to 140 hours. IL has also been possible1oobseNe the decrcasingofthe thicknessofrhe layer and the vhuai eil¿cls ofsublimalion, suggesti¡gthat rhe CDD sublincs, leaving behind i¡creasingly l¡rye islands of exposed undc.lying marble. It is shown thár rhe characrerisrjcs the fit¡¡ aie of decisive. l'he thick¡css and duration ofthe fiim and its morphologicalcharacre¡isrics the .rre mosl critical facto¡sfor its effeclive¡ess. CurcDl researchhas taken these p¡ch¡inary resutts iúo accounl and nume¡ous orh€r solvents are being lesled for thei¡ du.abiliry of lhe CDD consolidáringfilm formalion. Prescntstudieson a Droreporous slone (37.5%) comp¿redro thar of marble (t%) indicate üat the evaporalionrlte doesnol only dependon rhe chemical nature ofthe compoa¡{t bui also o¡ the sfruclureoflhe impregnatedsyslem.Penet.atinginto ¿ nrore porous syrem [20] or r¡to a more degradedsystemappcarsto imply a more prolonged evapomtionmle rhanon non porous sound systems.Extemál factors aftecting Lherate ofsubhnalion are also being tale¡ i o conside¡alion. such as varialions in temperalure. humidity a¡d ventilatjon.

BIBLIOGRAPHIC REFERENCES
D [1] Keynan , ryb creens.. waacNewderer22 (2000)3 pa¡r I . ,Resr¿,,o5: 995)3 I + 19. H mii Bjrdemiitetn. (| l2l Hanslcircr, M., E¡fahrungcn fliichtigen par H¡ngleit€r,ll.M, Erf¡hrdng€n flüchtige¡B¡rdcmifteln. 2 ¡es¡alf¿7r(1998) mit Jll 46E 7.]. H E., E., Bnrdcnirtel.2r(1995).185 [,+]Hangleite., M., Jágers and.¡ágc¡s Flüchrige 92. Bi¡demitielCyclododcca¡. (1991)g.-nj. n¿rtuuro2: [5] Itiby, G., Dasfliichtigc MurosV., Hin J.,JAIC 2004. Vollñe.11, Numberl. Afictc 6 75 89. [6] I7l BrucklcR, Thomro¡J.. Nichoh K.. Sr.ickle.C., JAIC 1919, Vol¡me 38, Nnnbcr 2, Aficle 4 . 162175. p¿per E., E., Occasio¡al [8] Jagcrs Jage.s In: BritisbMuseum, no.l3j, 1999Ed.OddyA., Caroll S.. E., [9] MajshJ.P,Risse. I^IC 4l (2002)127-1.17. Ricdl,N., andG Hilbcrt., Cyclododecan Purzgefiidge. in (1998) l0l nesr¿r,¿1: 494 99. P.olilesrvith microscopic .esolurion si.sle{idcd NMR, J. Magn.Reson.l7ó. by Illl PerloJ. er a1., (2005) - 70. 64 Spnnger, Bcdin,2005. ll2l Blünich B.. EssentialNMR, prosEmon cbemicalsafeq,. I l3 ] NIOSHAVHO/l¡tcr¡ational tntemei: hlt!lhnw cdc.gov/¡iosltipcs/italian.html P., N. L ll4l KuzmnraN. M¡rynenkoL. L, Chugerov V., Zairseva C.. G¡igoriev N.,. Yakushevich N, Joumal A. A. ofAlloys andConponnds (2000)158 162. 308 L, J., ll5l weissbuch Leiserorvitz LahavM.. H6 in: ^. Mesñann (!d.), Crystatlizatio¡ Tech¡ology l landbook, Ma..el Dckkcr, New Yo.k, 1 995.

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R.M., van Rosmalena G.M., Joufral of CrysialGrowrh230 (2001) 116lte. Hosta J.H.,Cee¡lmanb 277 281. A., B.G.,Sgamelloul Talúta 69 (2006)l22l 1226 [17] RicciC..Mllidi C..Brunetri Acta K. T., [18] Michaelia¡ H., Hall R. H., Bulm€rJ. Spectochimica PartA 59 (2003)8l l- 82441724181. P.. 47 Majumdar websterD.C.,Polymer (2006) [19] 355-169 M.. [20] Stei¡R.,KimmelJ.,Marincola K1eñn F.,JAIC 39 (2000)

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