Tip proiect: Proiect de cercetare postdoctoral Numr contract: 27 / 27.07.

2010 Denumirea proiectului: Spectroscopia de vibraie cu transformat Fourier utilizat la caracterizarea pigmenilor din pictur: o ans de autentificare a tablourilor romneti Perioada raportat: Etapa unic/2010 SINTEZA LUCRRII Spectroscopia este o metod analitic important care furnizeaza date, fie din cantiti mici de prob, fie prin analiza direct complet nedistructiv (in-situ). In aceast prim etap a fost aplicat spectroscopia de vibraie cu transformat Fourier, non-distructiv i non-contact, pentru caracterizarea i identificarea pigmenilor i a componenilor picturali pentru realizarea propriei baze de date ce va fi util la caracterizarea compoziiei picturilor n ulei, prezente n colecii muzeale romneti i semnate de pictori romni cu vizibilitate internaional. Unul din cei mai importani factori n identificarea spectral prin spectroscopie vibraional este accesul la spectre de referin corespunznd unor materiale cunoscute. Spectroscopia FT-IR i spectroscopia FT-Raman Principalele metode spectroscopice utilizate pentru detectarea vibraiilor atomilor din molecule se bazeaz pe procesul de absorbie a radiaiilor din domeiul infrarou i a fenomenului de mprtiere inelastic Raman. Aceste metode sunt larg folosite n practic pentru a furniza informaii despre structura molecular, n scopul de a identifica substane pe baza unor amprente spectrale caracteristice (eng. fingerprinting) i pentru a determina cantitativ sau semicantitativ cantitatea de analit dintr-o prob. Probele pot fi examinate ntr-o gam larg de stri fizice precum ar fi n stare solid, lichid sau de vapori, la temperaturi ridicate sau sczute, ca particule microscopice sau n straturi de suprafat, etc. Spectrul FTIR conine informaii privind prezena unor grupri funcionale/tipuri de legturi n moleculele probei studiate [Colthup et al 1978]. Spectroscopia FTIR i spectroscopia Raman sunt tehnici complementare. Vibraiile puternice din spectrul IR sunt de obicei slabe n spectrul Raman i invers. Din punct de vedere calitativ, modurile de vibraie antisimetrice datorate legturilor polare O-H, N-H, C=O au n general benzi proeminente n IR, n timp ce n spectrul Raman apar vibraii implicate n legturi simetrice C=C, C-C, S-S. Tehnica spectral bazat pe fenomenul de mprtiere inelastic Raman este mai puin larg utilizat n practic fa de absorbia n infrarou, n mare datorit unor probleme legate de degradarea probei n anumite condiii experimentale i fenomenul de fluorescen. Totui, progrese recente n tehnologiile ncorporate n spectrometrele Raman mpreuna cu abilitatea acestei tehnici de a examina probe non-distructiv a dus la o cretere rapid a aplicaiilor practice [Smith, Dent 2005].

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Fenomenul de mprtiere inelastic a luminii a fost postulat de Smekal n 1923 [Smekal 1923] i a fost observat experimental pentru prima data n 1928 de ctre Raman i Krishnan [Raman, Krishnan 1928]. De atunci pan n prezent, acest fenomen a fost denumit spectroscopie Raman. Spectroscopia Raman a fost utilizat la ntocmirea unor biblioteci de spectre pentru colecii de pigmeni, minerale, cleiuri i vernisuri utilizate n pictura [Burgio, Clark 2001], pentru caracterizarea tablourilor i a frescelor [Edwards et al 1997, Edwards et al 1999, Goltz et al 2004, Villar et al 2003]. ncercri de autentificare ale tablourilor sau icoane din colecii particulare sau de stat din Romania s-au mai realizat n ar, prin analize de piroliz n stare solid n cuplaj cu cromatografia de gaze (minim distructive, probele prelevate avnd 11,5 mg) [Sandu et al 2007]. Probe testate Pigmeni i materiale picturale A fost caracterizat structura molecular i investigat capacitatea de identificare a pigmenilor i materialelor picturale prin metodele spectroscopice FTIR i FT-Raman pentru o serie de pigmeni (Kremer) i urmtoarele materiale picturale: rini (colofoniu-diterpenoid, dammartriterpenoid, shellac sau lac gumat,) i substane ce conin acizi grasi (ceara de albine, clei de oase, clei de iepure). Principalii pigmeni istorii analizai sunt: pigmeni albi - Creta sau carbonatul de calciu CaCO3 (eng. chalk, germ. Kreide, fr. craie), Gipsul, ipsosul CaSO 4 2H2O (gypsum, terra alba, plaster of Paris), alb de titan sau oxid de titan TiO 2 (titanium white); pigmeni negri - Negrul de os (eng. bone black, animal black); pigmeni roii - Cinabrul HgS sulfur de mercur (eng. vermilion, cinnabar), Miniu (natural) sau rou de plumb (sintetic), (eng. red lead, minium; germ. Mennige) Pb3 O4 - tetraoxid de plumb; pigmeni albatri azurit Azurit (eng. azurite, mountain blue; germ. Bergblau; fr. bleu Paul Veronese, cendre bleu), Albastru ultramarin sintetic (eng. ultramarine; fr. outremer), indigo, Albastru de Prusia (eng.: Prussian blue, Berlin blue, China blue -este o ferocianur feric Fe4 [Fe (CN)6]3; pigmeni verzi - Pmnt verde (eng.: green earth), malachit (eng. malachite), pigmeni galbeni - Pmnturi galben-ocru (eng. ochre), masicot (eng.: massicot; germ.:Bleiglette; fr.:Massicot), Galben de cobalt (aureolin) (eng. cobalt yellow; germ. Kobaltgelb; fr.:jaune decobalt). CoK3(NO2 )6 H2O, Galben de cadmiu (eng.: cadmium yellow) CdS - sulfur de cadmiu; pigmeni bruni - umbra (eng.: raw umber)- pamnt brun [Feller 1986, Ashok 1993, West Fitzhugh 1996, West Berrie 2008, Eastaugh 2004].

Aparatur experimental 2/9

S-a utilizat un spectrometru FT-IR/FT-Raman Bruker Vertex 70 cu interferometru rock solid. Pentru FTIR s-a utilizat un divizor de fascicul din KBr i metoda pastilrii probei sub forma de pulbere (1 mg) cu bromura de potasiu (300 mg) prin presare la 10t/cm 2 i sonda MIR pentru testare nedistructiv pe domeniul spectral 650 4500 cm -1. Spectrometrul este dotat i cu modulul Raman (RAM II) i sond Raman (RAMPROBE) pentru analiza nedistructiv a probelor solide i lichide echipat cu o surs de excitare LASER NIR cu lungimea de und de 1064 nm (Nd:YAG) i putere ajustabil ntre 1 si 500 mW, detector cu semiconductor din Germaniu ultrapur rcit cu azot lichid. Prelucrarea datelor experimentale Spectrele au fost achiziionte i prelucrate n aplicaia software OPUS versiunea 6.0 furnizat de productorul echipamentului prin selectarea domeniul spectral n care existau picurile i corectia liniei de baz. Spectrele FTIR au fost prelucrate prin eliminarea semnalului CO 2 din atmosfer, normare vectorial i corecia liniei de baza. Rezultate i discuii Spectroscopia FT-Raman n figurile 1-23 sunt prezentate spectrele FT-Raman ale pigmenilor. Aceste spectre au fost achiziionate cu o putere variabil n funcie de pigment (1-500mW), 250scans, rezolutie 4cm -1 i s-a examinat domeniul spectral de amprentare. n tabelul 1 sunt prezentate lungimile de unde i intensitile relative ale pigmenilor ce au putut fi analizai cu spectrometrul FT-Raman Bruker (=1064 nm). Table 1. Pigmeni analizai cu spectrometrul FT-Raman Bruker (=1064 nm) Nr. Crt. Nume pigmeni 1. Rou de cadmiu 2. 3. 4. 5. 6. 7. 8. 9. 10. (cadmium red ) Galben de cadmiu (cadmium yellow) Praf de cret (chalk Bologna) Praf de cret (chalk champagne) Crom galben nchis (chromgelb dunkel) Cinabru (cinnabar) Acoperire alb (covering white) Alb (flake white) Indigo Sulfat de plumb Lungime de unde (cm-1) 987/584/462/332/293/241/216/137 988/842/618/595/461/345/298/240/213 1160/1129/1086/1016/1008/713/674/ 627/610/498/416/281/154 1086/795/712/347/282/223/192/155 975/843/404/379/361/342/147 502/421/345/285/254/104 637/514/395/197/144 1364/1051/968/680/414 1701/1632/1577/1462/1366/1313/548 1125/1083/1051/1020/976/961/605 Intensitatea relativ m/w/w/m/w/m/m/m s/w/w/w/m/m/w/m/m w/w/s/w/s/w/w/w/w/ w/w/m/w s/w/w/w/m/w/w/w w/s/w/w/m/w/w w/w/m/w/s/w m/w/w/w/s m/s/w/w/w w/w/s/w/w/w/w w/w/w/w/w/m/w/w/w/ Figura Fig.1 Fig.2 Fig.3 Fig.4 Fig.5 Fig.6 Fig.7 Fig.8 Fig.9 Fig.10 3/9

11. 12. 13. 14. 15. 16.

(lead sulfate) Ocru (lichtocker gebrannt) Praf de marmur (marble just) Masicot (massicot bleihaltie) Minium Molibdat (molybdatrot) Permanentrot hell

435/367/349/182/146/114/105/80 1684/1485/1037/588/134 1749/1436/1087/713/282/155 384/289/143/87/73 1538/1485/1190/1172/1147/800/485/ 220/167/121 826/359/341/153/74 1623/1557/1498/1447/1397/1335/ 1256/1219/1187/1130/988/845/ 724/619/343 1854/1168/482 1702/1616/1387/1287/750/288 1131/1009/416 1439/1090/716/614/450/285/158 1086/1001/549/488/349/189 1413/981/551/376/364

w/w/s/w/w/m w/s/m/w/w w/w/s/w/m/w w/m/s/m/w s/m/s/m/m/m/m/m/m/m s/m/m/w/w s/m/m/m/m/s/m/m/m/m/ w/w/w/w/w m/s/w w/m/w/m/w/w/ w/m/w w/s/w/m/m/m/w w/w/m/w/w/w w/w/s/w/m

Fig.11 Fig.12 Fig.13 Fig.14 Fig.15 Fig.16

17. 18. 19. 20. 21. 22.

Raw siena Ocru (Spanish red ochre) Terra alb Alb de titan (titan weiss) Albastru ultramarin (ultramarine hell) Albastru ultramarin foarte nchis (ultramarine blue, very dark) cromat de zinc (zinkgelb-

Fig.17 Fig.18 Fig.19 Fig.20 Fig.21 Fig.22

23.

944/895/875/777/412/349

m/w/s/w/w/w

Fig.23

zinkchromat) s-strong; m-mediu; w-weak. Spectrele pigmenilor au putut fi confirmate n urma comparrii cu date de literatura [Burgio, Clark 2001, Goltz et al 2004, Villar et al 2003, Edwards et al 1997, Edwards et al 1997, Castro et al 2005]. Nu s-au putut obtine spectre FT-Raman pentru toti pigmenti care prezinta spectre FT-IR fie pentru ca nu pot fi analizati cu un spectrometru cu sursa de excitare LASER YAG cu lungimea de und de excitare de 1064 nm (ex.: Pigmenii malachit i prussian blue), fie datorit culorii nchise i implicit absorbiei (ex. terra di siena geb, terra verde, dark, bone black) [Burgio, Clark 2001, Smith, Dent 2005]. Spectrele FT-Raman pentru ceara de albine, clei de oase, clei de iepure (fig.24 ) au fost achiziionate cu o putere de 500 mW, 250scans i s-a examinat domeniul spectral 250-1800 cm -1. Aceste materiale picturale reprezint amestecuri complexe de compui alifatici (acizi, alcoli, esteri i 4/9

hidrocarburi) ce prezint benzi caracteristice la urmtoarele lungimi de und: ~1240 cm -1 ( (C-H)cis

alchena

), ~1300 cm-1 ( (CH2)2 vibraii de deformare), ~1450 cm-1 ( (CH2), (CH3) vibraii de

forfecare), ~1650 cm-1 ( (C=C)). Spectrele FT-Raman pentru o serie de rini (colofoniu, dammar, shellac) (fig.25) au fost achiziionate cu puterea de 500 mW pentru shellac i 100 mw pentru celelalte dou rini, 250 scans, rezolutie 4cm-1 i s-a examinat domeniul spectral 250-1800 cm -1. Aceste materiale picturale conin compui terpenoizi cu o mulime de legturi duble C=C ce prezint benzi caracteristice la urmtoarele lungimi de und: ~1200 cm-1 ( (C-H)cis alchena ), ~1450 cm-1 ( (CH2), ~1650 cm-1 ( (C=C). Spectrele au putut fi confirmate n urma comparrii cu date de literatur [Vandenabeele et al 2000]. Spectroscopia FT-IR Spectrele FT-IR ale pigmenilor si materialelor picturale sunt comparabile cu datele din literatur [www.irug.org, Silva et al 2006]. n figurile 26-58 sunt date spectrele pigmenilor si materialelor picturale analizate nedistructiv in reflexie cu sonda si spectrele n transmisie obtinute pentru unii dintre pigmenti cu tehnica pastilarii n bromur de potasiu, 250 scans, rezoluie 4 cm -1. n tabelul 2 sunt prezentate lungimile de unde i intensitile relative ale pigmenilor i materialelor picturale analizate cu spectrometrul FT-IR BrukeR. Table 2. Pigmeni si materiale picturale analizate cu spectrometrul FT-IR Bruker Nr. crt. 1. 2. 3. 4. 5. 6. 7. 8. 9. Nume pigmeni Rou de cadmiu (cadmium red ) Galben de cadmiu (cadmium yellow) Praf de cret (chalk Bologna) Praf de cret (chalk champagne) Crom galben nchis (chromgelb dunkel) Cinabru (cinnabar) Acoperire alb (covering white) Alb (flake white) Indigo Lungime de unde (cm-1) 1627/1436/1400/1362/1214/1158/ 1096/98/875/810/714 1633/1437/1400/1207/1161/1101/ 984/862/660 3547/3405/1797/1685/1621/1429/ 1143/876/713/670/602 2984/2874/2512/1796/1426/1032/ 1009/875/713 1628/1385/1105/1070/968/858/628/ 599/437 1998/1869/1792/1734/1716/1684/ 1653/1607/1159/1107/1025/800/696 1641/1453/1259/1222/1160/1023 3536/1737/1409/1045/776/682 1945/1911/1877/1824/1795/1594/ 1465/1398/1222/1160/1098 5/9 Intensitatea relativ m/m/m/w/s/s/s/s/w/w/w m/m/m/s/s/s/s/w/w m/m/w/w/m/s/s/s/m/m/m w/w/m/m/s/w/w/s/m w/w/m/m/w/s/m/m/w w/w/w/w/w/w/w/m/s/m/s/ m/w s/w/w/m/m/w m/w/s/w/w/s w/w/w/w/w/s/w/w/w/w/w Figura Fig.26 Fig.27 Fig.28 Fig.29 Fig.30 Fig.31 Fig.32 Fig.33 Fig.34

10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21.

Sulfat de plumb (lead sulfate) Ocru (lichtocker gebrannt) Praf de marmur (marble just) Masicot plumb (massicot bleihaltie) Minium Molibdat (molybdatrot) Raw siena Ocru (Spanish red ochre) Terra alb Alb de titan (titan weiss) Bleumarin (ultramarine hell) Albastru ultramarine foarte nchis (ultramarine blue, very dark) cromat de zinc (zinkgelb zinkchromat) Terra di siena Malachite dark smalt albastru de prusia (prussian blue) azurite pamant verde negru de os (bone black) damar

3571/1406/1095/1035/598 1821/1646/1397/1159/1110/950/809/ 713 2984/2875/2514/1799/1433/876/713 1737/1397/1159/1103/1047/866/846/ 695/683 1739/1592/1404/1224/1160/1046/ 994/830/684 1635/1385/1128/1109/1064/862/ 628/599 1820/1797/1644/1463/1395/1220/ 1159/1105/1022/945/807/710 3699/3622/3456/1106/1032/913/ 797/695/537/471 3547/3404/3243/1685/1621/1143/ 670/602/458 2513/1798/1428/1027/876/712/509/ 429 3695/3620/2512/1795/1431/1031/ 914/876/712/539/467 2082/1651/122/1159/1109/790/755/ 733

w/m/s/s/s/ w/s/w/m/m/m/m/w w/w/w/w/s/s/m m/s/w/w/w/w/w/w/m w/w/s/w/w/w/w/w/w w/w/m/m/m/s/w/w w/w/s/w/w/m/m/m/w/w/w /w w/w/w/s/s/m//w/ws/s s/s/w/m/m/s/s/s/w w/w/s/w/s/m/w/w m/m/w/w/s/s/w/s/m/m/m/ w/m/s/s/m/w/w/w/

Fig.35 Fig.36 Fig.37 Fig.38 Fig.39 Fig.40 Fig.41 Fig.42 Fig.43 Fig.44 Fig.45 Fig.46

22.

3453/3259/2926/2855/1625/1078/ 951/882/814/715 1685/1621/1429/1115/1035/876/ 670/602/521/469 2541/2431/2362/2336/2165/2077/ 1923/1805/1576/1102/1068/921/828 3695/3620/1009/694/583/538/451 1042/772/472 3259/2092/1612/1416/606/500 3425/1498/1417/1031/954/838/459 3538/990/799/679/491/456/436 2014/1418/1036/874/605/565/471 1732/1594/1468/1394/1221/1160/ 1127/1082/1060/1034/931/898/829

m/m/w/w/w/w/s/s/s/m

Fig.47

23. 24. 25. 26. 27. 28. 29. 30. 31.

w/w/m/w/s/w/m/w/w/w m/m/w/w/w/m/w/w/s/m/ m/w/w w/w/s/m/w/w/s s/w/m w/s/w/w/w/m m/s/s/w/m/m/m m/s/w/w/w/w/w m/m/s/w/m/m/w m/s/m/m/m/w/w/ w/w/w/w/w/w

Fig.48 Fig.49 Fig.50 Fig.51 Fig.52 Fig.53 Fig.54 Fig.55 Fig.56

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32. 33.

shellac colofoniu

1745/1645/1592/1471/1396/1301/ 1263/1220/1160/951/802/733 1738/1727/1592/1469/1392/1222/ 1160/1085/1052/900/830

s/w/w/w/w/w/m/w/w/w/w /w/w m/m/m/m/m/m/w/w/w/w/ w

Fig.57 Fig.58

s-strong; m-mediu; w-weak Concluzii Spectroscopia de vibraie (FT-IR i FT-Raman) este o tehnic util pentru caracterizarea pigmenilor pe de o parte pentru c este non-distructiv, pe de alt parte pentru c informaia despre structura molecular a pigmentului testat obinut cu spectroscopia FT-Raman este complementar cu cea obinut prin spectroscopia FT-IR. Cu aceast tehnic am putut realiza propriile baze de date spectrale FT-IR n transmisie, FT-IR n reflexie i FT-Raman pentru pigmeni i materiale picturale. Bibliografie: Ashok 1993 - Ashok Roy (ed.), Artists' Pigments, A Handbook of Their History and Characteristics, Oxford University Press, New York vol. II, 1993. Burgio, Clark 2001 Burgio L. , Clark R. J. H., Library of FT-Raman spectra of pigments, minerals, pigment media and varnishes, and supplement to existing library of Raman spectra of pigments with visible excitation, Spectrochimica Acta Part A 57,2001, 1491-1521. Castro et al 2005 Castro K., Perez Alonso M., Rodriquez-Laso M., Fernandez L., Madariaga J., On-line FT-Raman and dispersive Raman spectra database of artists materials e-VISART database), Anal Bioanal Chem, 382, 2005, 248-258. Colthup et al 1978 - Colthup N.B., Daly L.H., Wiberly S.E., Introduction to Infrared and Raman Spectroscopy, Academic press, San Diego, 1978. Eastaugh 2004 - Eastaugh N., Walsh V., Chaplin T., Siddal R., The Pigment Compendium. A Dictionary of Historic Pigments. Elsevier, 2004. Edwards et al 1997 - Edwards H. M. E., Gwyer E. R., Tait J. K. F., Fourier Transform Raman Analysis of Pain Fragments from Biodeteriorated Renaissance Frescoes, J. of Raman Spectroscopy 28, 1997, 677-684. Edwards et al 1999 - Edwards H. M. E., Farwell D. W., Newton E. M., Perez, Minium F. R.; FT-Raman nondestructive analysis applied to an historical controversy, The Analyst, Received 21st May 1999, Accepted 13th July 1999. Feller 1986 - Feller Robert L. (ed.), Artists' Pigments, A Handbook of Their History and Characteristics, Oxford University Press, New York vol. I, 1986. Goltz et al 2004 - Goltz D.M., Coombs J., Marion C., Cloutis E., Gibson J., Attas M., ChooSmith L.P., Collins C., Pigment identification in artwork using graphite furnace atomic absorption spectrometry, Talanta 63, 2004, 609-616. 7/9

Raman, Krishnan 1928 - Raman C.V., Krishnan K.S., A New Type of Secondary Radiation , Nature, 121, 1928, 501-502. Sandu et al 2007 Sandu I., Luca C., Sandu I., Vasilache V., Autentificarea picturilor vechi prin identificarea materialelor din straturile policrome, Rev. Chim., 58 (10), 2007, 879-886 Silva et al 2006 Silva C.E., Silva L.P., Edwards H.G.M., F. C. de Oliviera, Diffuse reflection FTIR spectral database of dyes and pigments, Anal. Bioanal. Chem., 386, 2006, 2183-2191 Smekal 1923 - Smekal A.,Zur Quantentheorie der Dispersion, Naturwissenschaften,43,873875. Smith, Dent 2005 - Smith E., Dent G., Modern Raman Spectroscopy A Practical Approach, John Wiley & Sons Ltd, UK 2005. Vandenabeele et al 2000 P. Vandenabeele, L. Moens, H Edwards, Identification and Classification of Natural Organic Binding Media and Varnishes by Micro-Raman Spectroscopy, 15th World Conference on Nondestructive Testing Roma (Italy) 15-21 October 2000. Villar et al 2003 - Villar E. J., Edwards H. M. E., the late David D., Roger Worland M., TFRaman spectroscopic analysis of an Anterctic endolith, International J. of Astrobiology 1 (4), 2003, 349-355. West Fitzhugh 1996 - West Fitzhugh, Elisabeth (ed.), Artists' Pigments, A Handbook of Their History and Characteristics, Oxford University Press, New York, vol. III, 1996. West Berrie 2008 - West Berrie, Barbara Hepburn (ed.), Artists' Pigments, A Handbook of Their History and Characteristics, Oxford University Press, New York vol. IV, 2008. www.irug.org, 2009

Director de proiect, Dr. Maria Mihaela MANEA

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ANEXA

Fig.1 Spectrul FT-Raman al pigmentului rou de cadmiu (cadmium red - 250scans, 500mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\CADMIUM RED LIGHT-250SCANS_500mW.0 CADMIUM RED 11/11/2010 LIGHT-250SCANS_500mW

PI

Page 1/1

Fig.2 Spectrul FT-Raman al pigmentului galben de cadmiu (cadmium yellow 250scans,

H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\CADMIUM YELLOW-250SCANS_500mW.0

500mW)

CADMIUM YELLOW-250SCANS_500mW 11/11/2010

PIGME

Page 1/1

A1/A29

Fig.3 Spectrul FT-Raman al pigmentului praf de cret (chalk Bologna 250 scans, 500mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\chalk bologna_58100-250SCANS_500mW.0 chalk bologna_58100-250SCANS_500mW 19/10/2010

PI

Page 1/1

Fig.4 Spectrul FT-Raman al pigmentului praf de cret (chalk Champagne 250 scans,
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\chalk champagne_58000-250SCANS_250mW.0

250mW)

chalk champagne_58000-250SCANS_500mW 19/10/2010

Page 1/1

A2/A29

Fig.5 Spectrul FT-Raman al pigmentului crom galben nchis (chromgelb dunkel

H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\CHROMGELB DUNKEL-BLEICHROMAT-250SCANS_500mW.0

bleichromat 250 scans, 500 mW)

Page 1/1

22/11/2010 CHROMGELB DUNKEL-BLEICHR

Fig.6 Spectrul FT-Raman al pigmentului cinabru (cinnabar 250scans, 100mW)

H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\cinnabar_10610-250SCANS_100mW.0 cinnabar_10610-250SCANS_100mW 20/11/2010 PIGMENTI

Page 1/1

A3/A29

Fig.7 Spectrul FT-Raman pentru acoperire alb (covering white 250scans, 500mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\CONERING WHITE-250SCANS_500mW.0 CONERING WHITE-250SCANS_500mW 11/11/2010

PIGMEN

Page 1/1

Fig.8 Spectrul FT-Raman al pigmentului alb (flake white 250 scans, 500 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\flake white_46003-250SCANS_500mW.0 flake white_46003-250SCANS_500mW 19/10/2010 PIGMENTI

Page 1/1

A4/A29

Fig.9 Spectrul FT-Raman al pigmentului indigo (indigo 250 scans, 500 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\INDIGO-250SCANS_500mW.0 INDIGO-250SCANS_500mW 12/11/2010 PIGMENTI

Page 1/1

Fig.10 Spectrul FT-Raman al pigmentului sulfat de plumb (lead sulfate 250 scans, 500 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\lead sulfate_46050-250SCANS_500mW.0 lead sulfate_46050-250SCANS_500mW 19/10/2010

PIGMENT

Page 1/1

A5/A29

Fig.11 Spectrul FT-Raman al pigmentului ocru (lichtocker gebrannt 250 scans, 250 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\LICHTOCKER GEBRANNT -250SCANS_250mW.0

LICHTOCKER 22/11/2010 GEBRANNT -250SCANS_250

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Fig.12 Spectrul FT-Raman al pigmentului praf de marmur (marble just 250 scans, 500 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\marble just_58500-250SCANS_500mW.0 marble just_58500-250SCANS_500mW 19/10/2010

PIGMENTI

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Fig.13 Spectrul FT-Raman al pigmentului masicot (massicot bleihaltie 250 scans, 100 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\MASSICOT BLEIHALTIE-250SCANS_100mW.0 MASSICOT24/11/2010 BLEIHALTIE-250SCANS_100mW

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Fig.14 Spectrul FT-Raman al pigmentului minium (minium 250 scans, 500 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\minium_42500-250SCANS_500mW.0 minium_42500-250SCANS_500mW 20/11/2010 PIGMENTI

Page 1/1

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Fig.15 Spectrul FT-Raman al pigmentului molibdat (molybdatrot, bleimolybdat chromat 250 scans, 250 mW)
Page 1/1

H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\MOLYBDATROT, BLEIMOLYBDAT-CHROMAT-250SCANS_250mW.0 22/11/2010MOLYBDATROT, BLEIMOLYBDA

Fig.16 Spectrul FT-Raman al pigmentului permanentrot hell (permanentrot hell 250 scans,
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\PERMANENTROT HELL-250SCANS_500mW.0

500 mW)

PERMANENTROT 10/11/2010 HELL-250SCANS_500mW

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A8/A29

Fig.17 Spectrul FT-Raman al pigmentului raw siena (raw siena 250 scans, 100 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\RAW SIENA -250SCANS_100mW.0 RAW SIENA -250SCANS_100mW 10/11/2010 PIGMENTI

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Fig.18 Spectrul FT-Raman al pigmentului ocru (spanish red ochre 250 scans, 150 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\spanish red ochre_11584-250SCANS_150mW.0 spanish red20/11/2010 ochre_11584-250SCANS_150mW

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Fig.19 Spectrul FT-Raman al pigmentului terra alba (terra white 250 scans, 250 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\terra alba_58300-250SCANS_250mW.0 terra alba_58300-250SCANS_250mW 19/10/2010 PIGMENTI

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Fig.20 Spectrul FT-Raman al pigmentului alb de titan (titan weiss 250scans, 500 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\TITAN WEISS-250SCANS_500mW.0 TITAN WEISS-250SCANS_500mW 22/11/2010 PIGMENTI

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A10/A29

Fig.21 Spectrul FT-Raman al pigmentului bleumarin (ultramarin hell 1000 scans, 500 mW)
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\ULTRAMARIN HELL-1000SCANS_500mW.0 ULTRAMARIN 23/11/2010 HELL-1000SCANS_500mW

PIGM

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Fig.22 Spectrul FT-Raman al pigmentului albastru ultramarin foarte nchis (ultramarine blue,
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\ultramarine blue, very dark_45000-250SCANS_200mW.0

very dark 250 scans, 200 mW)

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ultramarine 20/10/2010 blue, very dark_45000-250SCA

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Fig.23 Spectrul FT-Raman al pigmentului cromat de zinc, galben zinc (zinkgelb zinkchromat
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\ZINKGELB 20, ZINKCHROMAT-250SCANS_500mW.0

250 scans, 500 mW)

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ZINKGELB 22/11/2010 20, ZINKCHROMAT-250SCANS_

Fig.24 Spectrele FT-Raman pentru: clei de oase (sus), clei de iepure (mijloc) i cear de albine (jos) H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\rabbit-glue-250SCANS_500mW-comp.0 rabbit-glue-250SCANS_500mW 07/11/2010
H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\beeswas-250SCANS_500mW.0

H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\clei de oase_250scans-500mW-comp.0

clei de oase_250scans-500mW 07/11/2010

materiale pictural

materiale pictural

beeswas-250SCANS_500mW 07/11/2010 PIGMENTI

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H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\colophoniu-250scans-100mW-comp.0

H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\dammar gum-250scans-100mW-comp.0

Fig.25 Spectrele FT-Raman pentru: colofoniu (sus), dammar (mijloc) i colophoniu-250scans-100mW-comp shellac (jos) 24/11/2010
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FRAGMENT SOLID

dammar gum-250scans-100mW-comp 24/11/2010 shellac_waxes_250scans_500mW 07/11/2010

FRAGMENT S

H:\_DATE_SPECTROSCOPIE_\FT-RAMAN\RAMPROBE\PD\pigmenti_FT-Raman\shellac_waxes_250scans_500mW-comp.0

FRAGMENT S

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\CADMIUM RED LIGHT-1000scans.0

Fig.26 Spectrul FT-IR in reflexie al pigmentului rosu de cadmiu (cadmium red)

Page 1/1

CADMIUM RED LIGHT-1000scans 09/11/2010

pigmenti

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Fig.27 Spectrul FT-IR in reflexie al pigmentului galben de cadmiu (cadmium yellow)

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\CADMIUM YELLOW -1000scans.0 CADMIUM YELLOW 09/11/2010 -1000scans pigmenti

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H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\chalk bologna_58100-1000scans.0 H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D4.0 D4 prafKBr pigmentului depellet creta (chalk Bologna)

Fig.28 Spectrele FT-IR in reflexie (albastru-absorbanta) si in transmisie (rosu-transmitanta) al chalk bologna_58100-1000scans 19/10/2010
21/10/2010

pigmenti

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H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D5.0

Fig.29 Spectrele FT-IR in reflexie (albastru-absorbanta) si in transmisie (rosu-transmitanta)

D5 KBr pellet

21/10/2010 pigmenti

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\chalk champagne_58000-1000scans.0

al pigmentului praf de creta (chalk Champagne)

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chalk champagne_58000-1000scans

Fig.30 Spectrul FT-IR in transmisie al pigmentului crom galben nchis

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\B1.0 B1 pellet (chromgelb dunkel KBr bleichromat) 11/11/2010

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Fig.31 Spectrul FT-IR in reflexie al pigmentului cinabru

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\cinnabar_10610-1000scans.0

(cinnabar)

cinnabar_10610-1000scans 19/10/2010 pigmenti

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Fig.32 Spectrul FT-IR in reflexie pentru acoperire alba (covering white)

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\CONERING WHITE -1000scans.0 CONERING WHITE -1000scans 09/11/2010 pigmenti

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H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\flake white hist_46003-1000scans.0 H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D7.0

Fig.33 Spectrele FT-IR in reflexie (albastru-absorbanta) si in transmisie (rosu-transmitanta) al flake white hist_46003-1000scans 19/10/2010 pigmentului D7 KBr alb pellet (flake white)
Page 1/1
21/10/2010

pigmenti

Fig.34 Spectrul FT-IR in reflexie al pigmentului indigo

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\INDIGO -1000scans.0 INDIGO -1000scans pigmenti 09/11/2010

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Fig.35 Spectrul FT-IR in transmisie al pigmentului sulfat de plumb (lead sulfate)

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D2.0 D2 KBr pellet 21/10/2010

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Fig.36 Spectrul FT-IR in reflexie al pigmentului ocru (lichtocker gebrannt)

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\LICHTOCKER GEBRANNT-1000scans.0 LICHTOCKER09/11/2010 GEBRANNT-1000scans

pigment

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A18/A29

Fig.37 Spectrul FT-IR in transmisie al pigmentului praf de marmura (marble just)

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D6.0 D6 KBr pellet 21/10/2010

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Fig.38 Spectrul FT-IR in reflexie al pigmentului masicot plumb (massicot bleihaltie)

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\MASSICOT BLEIHALTIE-1000scans.0 MASSICOT BLEIHALTIE-1000scans 08/11/2010 pigmenti

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Fig.39 Spectrul FT-IR in reflexie al pigmentului minium

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\minium_42500-1000scans.0 minium_42500-1000scans 19/10/2010 pigmenti

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Fig.40 Spectrul FT-IR in transmisie al pigmentului molibdat

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\B2.0

(molybdatrot, bleimolybdat-chromat)
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B2

KBr pellet

11/11/2010

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Fig.41 Spectrul FT-IR in reflexie al pigmentului raw siena

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\RAW SIENA -1000scans.0 RAW SIENA -1000scans 10/11/2010 pigmenti

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Fig.42 Spectrul FT-IR in transmisie al pigmentului ocru (spanish red ochre)

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\E1.0 E1 KBr pellet 22/10/2010

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Fig.43 Spectrul FT-IR in transmisie al pigmentului terra alba

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D3.0 D3 KBr pellet 21/10/2010

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Fig.44 Spectrul FT-IR in transmisie al pigmentului alb de titan (titan weiss)

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\A11.0 A11 KBr pellet 09/11/2010

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Fig.45 Spectrul FT-IR in transmisie al pigmentului bleumarin (ultramarin hell)

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\B3.0 B3 KBr pellet 11/11/2010

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Fig.46 Spectrul FT-IR in reflexie al pigmentului ultramarin foarte inchis

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\ultramarine blue, very dark_45000-1000scans.0

(ultramarine blue, very dark)

Page 1/1

ultramarine 19/10/2010 blue, very dark_45000-1000scans

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Fig.47 Spectrul FT-IR in transmisie al pigmentului cromat de zinc, galben zinc

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\A15.0

(zinkgelb zinkchromat)
Page 1/1

A15

KBr pellet

11/11/2010

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\A4.0 H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\A5.0 H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\B5.0

Fig.48 Spectrele FT-IR in transmisieA4 ale pigmentilor terra di siena geb (sus), terra di siena nat KBr pellet 08/11/2010 (mijloc) si terra verde (jos) B5 KBr pellet
Page 1/1
A5 KBr pellet 08/11/2010 11/11/2010

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Fig.49 Spectrul FT-IR in transmisie al pigmentului malachit

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\MALACHIT -1000scans.0 MALACHIT -1000scans 08/11/2010 pigmenti

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Fig.50 Spectrul FT-IR in transmisie al pigmentului dark

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D9.0 D9 KBr pellet 21/10/2010

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Fig.51 Spectrul FT-IR in transmisie al pigmentului smalt

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D10.0 D10 KBr pellet 20/10/2010

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Fig.52 Spectrul FT-IR in transmisie al pigmentului albastru de Prusia (prussian blue)

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D11_REPETAT.0 D11_REPETAT KBr pellet 22/10/2010

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H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\D12.0

Fig.53 Spectrul FT-IR in transmisie al pigmentului azurite D12 KBr pellet

Page 1/1

22/10/2010

Fig.54 Spectrul FT-IR in transmisie al pigmentului pamant verde (russian green earth)
H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\E3.0 E3 KBr pellet 20/10/2010

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Fig.55 Spectrul FT-IR in transmisie al pigmentului negru de os (bone black)

H:\_DATE_SPECTROSCOPIE_\FT-IR\_FTIR-TRANS_\PD\E4.0 E4 KBr pellet 20/10/2010

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Fig.56 Spectrul FT-IR in reflexie al damarului

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\MATERIALE PICTURALE_FT-IR\DAMMAR GUM-1000scans.0 DAMMAR04/11/2010 GUM-1000scans

MATERIALE

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Fig.57 Spectrul FT-IR in reflexie pentru shellac

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\MATERIALE PICTURALE_FT-IR\SHELLAc waxes-1000scans.0 SHELLAR-1000scans 04/11/2010

MATERIALE PIC

Page 1/1

H:\_DATE_SPECTROSCOPIE_\FT-IR\FOCALIZARE VERTICALA\PD\PIGMENTI_FT-IR\COLOFONIU-1000scans.0

Fig.58 Spectrul FT-IR in reflexie al colofoniului

Page 1/1

COLOFONIU-1000scans

10/11/2010 pigmenti

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