INCDTP

Particular problems in leather and Particular problems in leather and parchmentparchmentparchment parchment

conservation and restoration conservation and restoration

Lucretia MIU, Ciprian CHELARU

INCDTP – Division: LEATHER AND FOOTWEAR RESEARCH INSTITUTE (INCDTP - ICPI)

Bucharest ROMANIABucharest, ROMANIA

GENERALITIESGENERALITIESLeather and Footwear Research Institute (ICPI) is the division of

h R h d D l N i l I i f T ilthe Research and Development National Institute for Textileand Leather (INCDTP).

ICPI has been established in 1951 in Bucharest, having uniqueexpertise and R&D facilities in the field of leather processing,shoe manufacturing and allied fields.g

Being a National State Institute it is coordinated by the Ministryof Education Research and Youth (MECT) and is in permanentof Education Research and Youth (MECT) and is in permanentcontact with the industrial sector and with the Ministry ofEconomy and Finance which coordinate the industry.

Main activities of ICPI are:Research & developmentTechnical services in the following fields:g

hides/skins processingfootwear and components designing

bb drubber goodscollagen based biomaterialschemical and physical mechanical investigationschemical and physical-mechanical investigations

Dissemination of technical - scientifical Dissemination of technical scientifical information through: “Leather and Footwear Industry” Revue, news letters, conferences and yworkshops organisation;

ICPI has participated in over100 research projects realised in collaboration with other R&D institutes, universities, museums libraries and industrial partners specially SMEsmuseums, libraries and industrial partners, specially SMEs

ICPIICPI isis membmembeerr inin 88 RomanianRomanianspecializedspecialized associationsassociations andand inin 77internationalinternational asasssociatiociationsons//networksnetworks andand hashas aa goodgoodnetworksnetworks andand hashas aa goodgoodcollaborationcollaboration withwith 22 EuropeanEuropeanorganizationorganization inin itsits fieldfield ofoforganizationorganization inin itsits fieldfield ofofactivityactivity..

DEVELOPMENTS IN RESEARCH OF THE LEATHERDEVELOPMENTS IN RESEARCH OF THE LEATHERDEVELOPMENTS IN RESEARCH OF THE LEATHERDEVELOPMENTS IN RESEARCH OF THE LEATHERAND PARCHMENT HISTORICAL OBJECTSAND PARCHMENT HISTORICAL OBJECTS

ICPI institute has been collaborate with museumsand libraries to protect the historical and culturalh it l th bj theritage leather objects.

Leather chemists from ICPI have cooperated andoffered support museums (specially for identifyingl th i i l i d t ti hi t i lleather origin, cleaning and treating historicalleather objects) from 70s.

Beginning with 2001, in the framework of NationalR&D Programs the collaborations became constantinitiated by our institute.

Different projects on ICPI:

M ltidi i li t di t bli hi th d t i ti Multidisciplinary studies on establishing the deterioration mechanisms in historical and cultural parchment documents - PERGAMO (2006 - 2008)

Durable materials and technologies for leather cultural heritage objects conservation and restoration, to ensure g j ,viable cultural inheritance at community level (2007 - 2010)

N d bl t i l f ti d t tiNew durable materials for conservation and restorationof leather and parchment patrimony objects (2007 –2009) – Bilateral cooperation with Ukraine

Complex techniques for investigation, evaluation, conservation and restoration for collagenic ethnographic conservation and restoration for collagenic ethnographic materials (2008 - 2011) - in progress

ROMANIAN PARTNERSR&D institutes:

ROMANIAN PARTNERS

INCD IE-ICPE-Advanced Research, Bucharest: Thermal analyses(TG, DTG, DTA, DSC)Institute of Macromolecular Chemistry “Petru Poni” Iasi:Institute of Macromolecular Chemistry Petru Poni , Iasi: Microscopic SEM and TEM analysesNational R&D Institute for Optoelectronics, Magurele, Ilfov: Multispectral Investigations and non-conventional treatments)Multispectral Investigations and non-conventional treatments)National Research Institute for Conservation and Restoration, Bucharest: ATR investigations

University

University “Politehnica“ Bucharest: Modern spectral analyses:FT – IR spectroscopy; UV – VIS spectroscopy ;FT IR spectroscopy; UV VIS spectroscopy ;UV –VIS – NIR spectroscopy; diffuse light reflective spectroscopy;chemo luminescence investigation techniquechemo-luminescence investigation technique.

MMuseums

National History Museum of RomaniaNational History Museum of RomaniaNational History Museum of RomaniaNational History Museum of RomaniaMuseum of the Bucharest MunicipaltyMuseum of the Bucharest Municipalty;;National Military MuseumNational Military Museum, , BucharestBucharest;;yy ,, ;;National Museums Assembly National Museums Assembly ““MOLDOVAMOLDOVA”, Iasi;”, Iasi;Village Museums: D. Gusti Village Museums: D. Gusti --Bucharest, ASTRA Bucharest, ASTRA -- Sibiu, Sibiu, B i B i SSBucovina Bucovina -- SuceavaSuceava

All these partners have expertise in methodologies for colecting All these partners have expertise in methodologies for colecting g f gg f gsamples, conservation, restoration, cleaning and treatment of samples, conservation, restoration, cleaning and treatment of heritage parchment objects.heritage parchment objects.

EUROPEAN PARTNERSEUROPEAN PARTNERSUniversity of Torino - Chemistry-Physics Department, Italy:Assessment of parchment heritage objects (DSC RMN SEM)Assessment of parchment heritage objects (DSC, RMN, SEM)

The Royal Danish Academy of Fine Arts, School of Conservation,The Royal Danish Academy of Fine Arts, School of Conservation,Copenhagen, Denmark:- Cooperation for IDAP project activities - ICPI have supplied newparchments for studies in the project;parchments for studies in the project;- Workshop IDAP: visual assessment and MHT;- Specialisation on parchment sampling and HPLC analyses.

National Library of Czech Republic (Klementinum), Prague, CzechRepublic: conservation-restoration and investigation of heritage

h t d t ( h i k t t MHT bi l i lparchment documents (shrinkage temperature - MHT, biologicaldamage assessment; part of tests have been made on newparchments supplied by ICPI)

LEATHER AND PARCHMENTSLEATHER AND PARCHMENTS

Leather

Anim

al skinsParchment

Leathers and parchment have a three-dimensional structure characteristic which give it physical-mechanical resistancecharacteristic which give it physical-mechanical resistance.

Diff t t l t (fl d fi th k t ) d hDifferent natural events (floods, fires, earthquake etc.) and human interventions (wars, improper manipulation and storage conditions etc ) have affected the quality of parchment objects and besideetc.) have affected the quality of parchment objects and beside ageing have a negative impact and reduce their lifetime.

LEATHER and PARCHMENT: LEATHER and PARCHMENT: Looking Deep into the Looking Deep into the g pg pStructureStructure

Collagen has a discrete structural Damage to collagen variouslyKennedy C.J., Wess T.J. (2003). Restaurator 24, 61-80

hierarchy that provides strength toliving tissues and to parchment,leather, etc.

distribute on all structural levels ofits hierarchical organisation.

,

Collagen structure deterioration at any or all levels of itshierarchy influence the physical and mechanical properties ofhierarchy influence the physical and mechanical properties ofhistorically important documents.

midIR, NIRmidIR, NIRNMR ProFilerNMR ProFiler

DSC in diluted solutionDSC in diluted solution

DSC in excess waterDSC in excess waterMHTMHT

SEMSEMDSC in dry conditionDSC in dry condition

AA analysisAA analysisAA analysisAA analysisMass spectrometryMass spectrometry

FROM MICRO TO MOLECULAR STRUCTUREFROM MICRO TO MOLECULAR STRUCTURE

PARCHMENT& LEATHER: PARCHMENT& LEATHER: Looking Deep into the StructureLooking Deep into the StructureExperimental approach: systematic, multidisciplinary investigation and correlationbetween changes/alteration of physical-chemical and structural properties of

g pg p

g p y p pparchments at the microscopic, mesoscopic and molecular levels

A twoA two--way classification of investigation methodsway classification of investigation methods

PHYSICO CHEMICAL TECHNIQUESPHYSICO-CHEMICAL TECHNIQUESA MESOSCOPIC TO MOLECULAR APPROACH

mesoscopic to fibrillar molecular levelmesoscopic to nanoscopic levels

fibrillar structure

molecular level

ATR-IR / FT-IRSEM TG-DTADSCatten. total reflection IR Fourier transform IR

ESEMscanning electron

thermogravim.differential thermal

differential scanning calorimetry Fourier transform IR

solid sample/KBr pellet

UV Vis and NIR

electron microscopy

graphite

t e aanalysis

as received

ca o et y

excess waterdry samples UV-Vis and NIR

solid sample

g ap tecovering

as received samples

dry sampleswet samples in O2/N2 flux

FT-IR IFS28(BRUKER)FT-IR 320 (AVATAR)UV-Vis NIR 570 (JASCO)

Stereoscan420(LEICA)

TG-DTA/DSC Apparatus (NETZSCH)

MicroDSC III(SETARAM)DSC111(SETARAM)

( )( )(SETARAM)DSC 204 (NETZSCH)

OPTICAL MICROSCOPY

Surface morphology evaluation S f d f tSurface defectsFibers defects

Animal type identificationAnimal type identificationSurface aspect

PigPigSheepGoat etc

FIBERS DEFECTSFIBERS DEFECTS

undamaged frayed splitted flat 1 flat 2

cracked shrunk bundle gel-like dissolvingR. Larsen, D.V. Poulsen, F. Juchauld, H. Herosch, M. Odlyha, J. de Groot, T. Wess, J. Hill, C. Kennedy, G. Della Gatta,

E. Badea, A. Mašić, S. Boghosian, D. Fessas,

Damage assessment of parchment: Complexity and relations at different structural levels, in Preprints of ICOM Committee

for Conservation 14th Triennial Meeting, The Hague, James & James Ed., London, 2005, vol. 1, p.199-208.

Surface aspectGoat – leather – 20x

Surface aspectGoat – parchment – 20x

Surface aspectSheep – leather – 20x

Surface aspectSheep – parchment – 20x

Surface aspectPig – leather – 20x

Surface aspectPig – parchment – 20x

Surface aspectCalf – leather – 20x

Surface aspectCalf – parchment – 20x

EXPERIMENTAL PROCEDUREEXPERIMENTAL PROCEDUREWettingWetting: a sample of around 0.1 mg. Fibres from the corium part (flesh side) ofth h t i tt d ith d i li d t i lid iththe parchment is wetted with de-mineralised water on a microscope slide witha concavity - 10 to 20 minutes

SamplingSampling: only few fibresare taken for the measurement.

MeasurementMeasurement ofof TTss: the slide isplaced on the hot table andplaced on the hot table andheated at a rate of 2° C/min.

MHT device – Leica Stereomicroscope and Caloris Micro Hot Table

Micro-Hot Table techniqueSh i k t t

Micro-Hot Table techniqueShrinkage temperature

Interval A1−A2: Distinct shrinkage activity is observed in individual fibres.Interval B −B : Shrinkage activity in one fibre (occasionally more) isInterval B1−B2: Shrinkage activity in one fibre (occasionally more) is immediately followed by shrinkage activity in another fibre.Interval C: At least two fibres show simultaneous and continuous shrinkage activity.

no activity − A1 − B1 − C − B2 − A2 − complete shrinkage

Micro-Hot Table techniqueT BA

Micro-Hot Table techniqueTin B1A1

C

AB2 TfinA2B2 Tfin

SHRINKAGE TEMPERATURE FOR SOME HISTORICAL ROMANIAN PARCHMENTS (XVI-XVIIIth Century)

58.1 °C 51.3 °C

47 6 °C49 7 °C 47.6 °C49.7 °C

The use of FTIR and XRF in a parchment musical score investigationmusical score investigation

PERGAMO PERGAMO Project Project (CEEX 165/200(CEEX 165/20066))

LL.. MiuMiuLeather and Footwear ResearchLeather and Footwear Research InstituteInstitute (ICPI)

D. D. ŞŞecleclăăman, man, II.. PetroviciuPetroviciu, , GG.. NiculescuNiculescu, M. Georgescu, , M. Georgescu, CC..C tC tCarşoteCarşote

National Museum of Romanian History (MNIR)

Musical score investigationMusical score investigationParchment investigation

Id tifi ti f t i l front side

Identification of materials used in parchment processing

(FTIR (FTIR -- ATR)ATR) ((XRFXRF))

Evaluation of parchment

(FTIR (FTIR -- ATR)ATR) Shrinkage temperatureShrinkage temperature

degradation level

(( )) Shrinkage temperatureShrinkage temperature

back side

Identification of materials added to parchment

((XRFXRF))(FTIR (FTIR -- ATR)ATR) (( ))(( ))

Resultsesu ts

Identification of materials used in parchment processing

Parchment investigation

calcium carbonate + aluminosilicatescalcium carbonate + aluminosilicates

Identification of materials used in parchment processing32

84.0

1

2923

.38

1638

.65

1543

.80

1416

.43

1238

.72

1028

.65

874.

34

100.

12

Pergament - fata 1-2

10

12

14

Ca

Cu Element ppm +/-S 49701 9968Ca > 10%0.

000.

020.

040.

060.

080.

Abso

rban

ce U

nits

Pergament - fata 1-1

2

2.5

3

Ca Element ppm +/-Fe 3203 183Cu 420 45Zn 220 27Hg 721 40

0

2

4

6

8

-5 0 5 10 15 20 25 30 35 40 45

E (keV)

AU

Fe

S Cr

Cr 117 35Fe 2264 81

C:\DATA\IRINA\2007\PERGAMO\Coperti\Pergament Crina\pergament Crina fata cu albastru2-IR-Helios-ATR.0 pergament Crina fata cu albastru28/03/2007

500100015002000250030003500Wavenumber cm-1

0

0.5

1

1.5

-5 0 5 10 15 20 25 30 35 40 45

E (keV)

AU

P

S

Fe

Cu

Zn

HgPb

Pb 344 24

Evaluation of parchment degradation level*

Parchmen AI/AII Δν 1730 cm-1

t1

front side 1,1 93 (+)

back side 1,2 95 (+)

Shrinkage Shrinkage temperature (MHT)temperature (MHT)

4545ooCC

Ref. DSS 1-1,1 <91

DSS* 1.3 - 1.6 94 - 114degraded degraded

*Derrick Michele (1991), Evaluation of the State of Degradation of Dead Sea Scroll (DSS) Samples Using FT-IR Spectroscopy, American Institute for Conservation vol 10

Identification of materials added to parchment

azuriteazuritePergament - albastru 2

60

70

80

90

100

CAzurit

Element ppm +/-S 48766 10664Ca > 10%F 33 212

azuriteazurite cinnabarcinnabar

0

10

20

30

40

50

-5 0 5 10 15 20 25 30 35 40 45E (keV)

AU

Ca

Fe

C

Fe 5733 212

Pergament - litera S rosu - 1

25

30

Hg

H

Cinabru

3421

.77

1646

.46

1406

.83

1082

.67

952.

36

827.

52

607.

27

3430

.73

1424

.78

957.

52

835.

21

0.8

1.0

1.2

1.4

1.6

banc

e U

nits

5

10

15

20

AU

Ca

Fe

Cu

Zn

Hg

PbPb

Hg

Hg

Element ppm +/-Fe 20572 852Cu 5161 234Zn 759 89Hg 43914 1583Pb 527 51

C:\IRUG database\MP\IMP00294.DX IMP00294 Azurite, Forbes, display 86, SCC, tran tran, [sample preparation (29)]

C:\DATA\IRINA\2007\PERGAMO\Coperti\Pergament Crina\pergament Crina albastru-IR-Helios-ATR.0 pergament Crina albastru pergame 28/03/2007

5001000150020002500300035004000Wavenumber cm-1

0.2

0.4

0.6

0A

bsor

b

0-5 0 5 10 15 20 25 30 35 40 45

E (keV)

Pergament - cerneala 1

6

7

8

Fe

Cu

Pergament - cerneala 2

30

35

Fe

1

2

3

4

5

AU

S

Ca

Ti

FeCu

Zn

Hg

Hg

Hg

Pb

Element ppm +/-Fe 25290 784Cu 7833 255Zn 888 58Hg 5999 191Pb 629 30 iron gall inkiron gall ink

5

10

15

20

25

AU

Ca

S

Fe

Cu

Element ppm +/-S 77334 10006Ca > 10%Fe 15021 460

0-5 0 5 10 15 20 25 30 35 40 45

E (keV)

0-5 0 5 10 15 20 25 30 35 40 45

E (keV)

ConclusionConclusionFTIR and XRF:

very useful in non-destructive very useful in non destructive investigation of parchment (including materials added to parchment)

l i f icomplementary informationFTIR:

f l i l i f h d d iuseful in evaluation of parchment degradation level – good correlation with shrinkage temperature measured with MicroHotTabletemperature measured with MicroHotTable

Acknowledgements:

An artist's impression of Ötzi's right shoe

Reconstruction of how Ötzi may have looked when alive

YYTHANK YOU FOR THANK YOU FOR

ATTENTIONATTENTION !!ATTENTIONATTENTION !!

CONTACT DETAILS:

INCDTP – ICPI93, ION MINULESCU, 031215, sector 3,

BUCHAREST, ROMANIABUCHAREST, ROMANIAPhone/Fax: + 40 21 323 52 80

e-mail: icpi@icpi.ro Web: www.icpi.ro