COLLAGE Project

Intelligent System for Analysis and Diagnosis of Collagen-Based Artefacts

www.collage.com.ro

collage

Elena Badea Project Director

Mid term results

COLLAGE Consortium

collage

Coordinator Institution - National Research & Development Institute for

Textile and Leather (INCDTP), ICPI Division, Bucharest Team Leader: Lucretia Miu; Team members: Claudiu Sendrea, Elena Poiana,

Gabriela Neagulov, Marius Purcea

P1 - National Institute for Research & Development in Electrical

Engineering (ICPE-CA), Bucharest

Team Leader: Petru Budrugeac; Team members: Andrei Cucos, Laura Chiose,

Carmen Stafanescu

P2 - National Museum of Romanian History, Centre of Research &

Scientific Investigation, Bucharest

Team Leader: Irina Petroviciu; Team members: Cristina Carsote

P3 - Faculty of Electronics, Telecommunications & Information

Technology, University Politehnica of Bucharest

Team Leader: Ovidiu Grigore; Team members: Valentin Velican, Ionut Bornoiu

P4 - Mira Telecom s.r.l., Bucharest

Team Leader: Silviu Ciobanu; Team members: Oana Miu

THE PREMISES

Historical and cultural objects made of collagen include; parchment, in the form of scrolls,

documents and codices; leather, in a huge variety of items such as bindings, wall tapestry,

storage vessels, musical instruments, luggage, objects of personal use such as shoes and

garments, and mummified skins of animals or humans.

Documents made of parchment are the most important bearers of our recorded history from

early times such as the Dead Sea Scrolls (408 BC - 318 AD) and the Magna Carta (1215)

until the modern U.S. Declaration, Constitution, and Bill of Rights (1787), and present important

state documents and parliamentary records.

Leather objects are an infinite source of information of historical and cultural interest; they

illustrate the evolution of social customs, habits,

aesthetics and technology, but also the

perpetuation of popular and religious traditions.

On the other hand, collagen is an integral part of the human

body and the study of mummies can supply new informed

directions for anthropological, paleopathological, genetic and

medical research.

All these objects and artefacts represent repositories of tangible-intangible cultural heritage

which can offer answers on the state of health and beliefs of past civilisations.

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THE CHALLENGE OF THE COLLAGE PROJECT FILLING THE GAP BETWEEN RESEARCH AND ITS APPLICATIONS FOR

CULTURAL HERITAGE PRESERVATION

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COLLAGE MAIN OBJECTIVE aims to develop a unified kit of assessment tools for conservators, conservation

scientists and scientists to evaluate the level of damage in collagen-based heritage and

archaeological objects using a multi-disciplinary and multi-scale approach ranging from

molecular, nano and mesoscale to macro scale visual assessment.

Additionally, the project

(i) takes advantage of previous results from national, international and EU projects and

develop a parchment and leather damage database

(ii) critically reviews practices in the preparation of archival material and their

conservation and restoration treatments in order to trace differences in traditions in

different geographical areas and establish markers for identification and anti-

counterfeiting purposes .

2002 – 2005 EC FP5 Framework

2006 – 2009 CIPE - Italy

2006 - 2008 2008 - 2011 2007 – 2009

THE CHALLENGE COLLAGE – SPECIFIC OBJECTIVES

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1. Development of a new measurement system for the automatic

detection of shrinkage activity of collagen fibres in laboratory

and in situ: imageMHT system

2. Development of an intelligent system for assisted damage

diagnosis CLEAR diagnostic software

3. Development of a comprehensive parchment and leather

damage database

4. Establishment of a unified calibrated measurement protocol

enabling inter-laboratory comparison

5. Identification of analytical markers for early damage

identification and anti-counterfeiting purposes

6. Definition of quantitative protocols for damage quantification

THE APPROACH c

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Accelerated

Ageing / Exposure

temperature

humidity

UV and Vis light

air pollutants

(NOx, SO2)

Parchment

- New calf and goat parchment

- Historical parchment

Leather

- New calf and sheep leather - (tannins: mimosa bark, quebracho wood,

chestnut wood)

- Historical leather

1-32 weeks 8 - 64 days

THE APPROACH c

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Molecular level Multiscale analyses: Fibre level

fibre bundles

100-500 m

SEM, DSC ATR/FTIR NMR MHT method

fibres morphology

thermal denaturation

Badea E., Della Gatta G. et al. Study of deterioration of historical parchments by various thermal analysis techniques, complemented by

SEM, FTIR, UV-Vis-NIR and unilateral NMR investigations, J. Therm. Anal. Calorim. 91, 17-27 (2008).

THE APPROACH Translate analytical data into practically relevant measures

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Historical samples

Shrinkage activity of collagen fibres

Parchment bindings, Ordinati Collection (1325 to

TO109_1 TO106_1

TO108_1 TO102_1 TO102_2

TO104_2 TO108_2

TO102_2 TO109_1

TO107_2 TO102_2 TO111_2 TO108_1

TO106_1 TO104_2

TO106_2 TO108_2

TO111_1 TO109_2

TO102_1

TO107_1 TO102_2

TO102_1 TO111_2

TO107_1 TO104_1

TO106_2 TO107_2

TO111_1

TO111_2 TO108_1

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T1/ms

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NMR longitudinal relaxion time T1 of historical

parchments bindings, Ordinati Collection (1325 to

1499) Historical Archives of the City of Turin

DSC denaturation of collagen fibrils in

parchment samples exposed to 80 °C and

40% and 80% RH in alternate days

1800 1600 1400 1200 1000

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Wavenumber / cm-1

new parchment

CR14: NO2 2 weeks

CR15: NO2 4 weeks

CR16: NO2 8 weeks

CR17: NO2 16 weeks

ATR-IR spectra of parchments exposed to

NOx(50 ppm) for 2 to 16 weeks

microscopic

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mesoscopic

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nanoscopic

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molecular

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Damage assessment: from macro to nanoscale

Damage quantifying Early damage detection Fake identification

gelatine

ordered triple helix

Collagen denaturation & gelatinisation

Molecular manifestation

disordered

triple helix

3D packing

loose

peptide chains

conformational change

fragmentation

Differential Scanning Calorimetry

(micro DSC)

ordered triple helix

disordered

triple helix

gelatine

microDSC peak of a historical parchment binding

The State Archives of Florence, Italy

Total Damage Ranking Equation

Stot = 0.2 S[Td] + 0.5 S[DH] + 0.3 S[IS]

E. Badea, G. Della Gatta, T. Usacheva, Effects of temperature and relative humidity on fibrillar collagen within parchment: a micro

Differential Scanning Calorimetry (micro DSC) study, Polymer Degradation and Stability, 97, 346-353 (2012).

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Damage assessment: from macro to nanoscale

Damage quantifying by DSC and SEM

Ranking of a group of archival bookbindings in 4 damage categories:

(1) no damage; (2) minor damage; (3) medium damage and (4) heavy damage

Sample no. 4 comprehensively displays increasing damage of its flap (F4), cover (C4) and spine (S4)

E. Badea, G. Della Gatta, L. Miu, C. Carşote, I. Petroviciu, R. Larsen, M. Odlyha, A. Braghieri, S. Benedetto, Damage assessment

of historical parchments: a protocol for preventive conservation. Restitutio, Bilingual Conservation-restoration bulletin, No. 5-6, p.

61-74, Muzeul Satului “Dimitrie Gusti”, Bucureşti (2012), ISSN 2065-2992.

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Damage assessment: from macro to nanoscale

Damage quantifying Early damage detection Fake identification

deteriorated sample

I(AI)/I(AII) ~ 1 new parchment / leather

deteriorated material

Δν~ 90 cm-1 new parchment / leather

deteriorated material

I(AI)/I(AII) ~ 1 new parchment / leather

E. Badea, W. Vetter, I. Petroviciu, C. Carsote, L. Miu, M. Schreiner, G. Della Gatta, How parchment responds to temperature and

relative humidity: a combined micro DSC, MHT, SEM and ATR-FTIR study, in Proceedings Book of ICAMS 2012 (SCOPUS indexed

volume), Certex, ISSN 2068-0783, Bucharest, p. 487-492 (2012).

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Damage assessment: from macro to nanoscale

Damage quantifying Early damage detection Fake identification

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Dehydration

Denaturation

ENDO

New vegetable leather

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Gospel - Bucharest - XVIII century

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Dehydration

Denaturation 1

Denaturation 2

ENDO

1 2 3 4

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1- new parchments

2- old parchments

3 - new leathers

4 - old leathers

Td/0

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Heavily damaged old leathers: Td< 227

0C Damaged old leathers:

2270C ≤ Td ≤2340C

New and artifcially aged Td > 234

0C.

P. Budrugeac, A. Cucos, L. Miu, Use of thermal analysis methods to

asses the damage in the bookbindings of some religious books from

XVIII century, stored in Romanian libraries, J Therm Anal Calorim

(2014) 116:141–149.

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Interdisciplinary approach

Analytical outcomes (chemistry, technology)

Image algorithms (ICT)

Software Hardware Con serva tion

Sus taina ble

Unification of all these assessment methods to create a reference toolkit

for conservators and scientists alike to assess the healthiness of objects /

artefacts, the impact of past and future conservation treatments, and of

climate change.

Applications Development

Image MHT system

• image capturing device (ICD)

• precisely controlled heating block (HP)

• software commanding both heating

element and image capturing

CLEAR diagnostic system • analytical database

• software tool for evaluation and

ranking damage, identifying main

causes of deterioration, fingerprint the

studied object

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Image MHT system vs classic MHT method

MHT method: thermal microscopy technique that measures the shrinkage activity of collagen fibres

Shrinkage is the macroscopic manifestation of thermal denaturation

triple helix random coil

In the first two intervals, A1 and B1,

shrinkage discretely occurs in

individual fibers and generally display

higher activity in B1 interval. Fiber

mass cooperatively shrinks in the C

interval.

The starting temperature of this

interval is the shrinkage temperature,

Ts. Generally, shrinkage activity levels

off through B2 and A2 intervals.

New collagen-based samples undergo the following changes as a function of temperature:

no activityA1B1CB2A2complete shrinkage

E. Badea, D.V. Poulsen Sommer, K. Mühlen Axelsson, R. Larsen , A. Kurysheva, L. Miu, G. Della Gatta, Damage ranking in historical

parchments: from microscopic study of fibres structure to collagen denaturation assessment by micro DSC, e-Preservation Science,

9, 97-109 (2012).

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Image MHT system vs classic MHT method

MHT method: a simple test for evaluating collagen deterioration

Shrinkage is visualised through a stereo microscope using reflected light as the

motion of the fibres dispersed in water under constant heating rate (2 °C min-1).

MHT measurement system

1: Caloris heating plate

1a: window slot for inserting the sample

placed on a microscope slide with a

concavity. Fibres are preliminary thoroughly

wetted and separated in demineralised water

for 10 min.

1b: window for viewing under the microscope

2: FP90 Central Processer for temperature

programming

3: Steromicroscope equipped with a digital

camera

4: PC

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Image MHT system and classic MHT method

Mid Term Results

- Hardware: prototype of the precisely controlled heating block

- Software: experimental model for collagen fibres tracking and shrinkage intervals

automatic detection

- Testing of the experimental model

imageMHT method: automated system that measures the shrinkage activity of collagen fibres using image processing techniques

Advantages

- More reliable results secured by:

- ALGORITHMS QUALITY, higher number of observed fibres, lower heating rate

which enables to better discriminate between various motion types

- AVOID HUMAN ERRORS ( poor experience, fatigue, sight variability/problems,

bad mood, etc.)

- Dramatic reduction of the operator time

- Portability and in-situ measurements

- Patentability

imageMHT – mainstream analytical technique for the primary evaluation of collagen-based artefacts, historical and archaelogical objects

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Image MHT system

Heating block prototype

Improved features

•Heating/cooling interval: DT = 15 – 120 °C

(Mettler Toledo heating plate: DT = 25 – 100 °C, but the system is

stable only above 30 °C)

• Variable temperature increment: 1, 2, 5 and 10 °Cmin-1

(Mettler Toledo heating plate: 2 Cmin-1 )

New functionalities

• Quick cooling to room temperature

• Miniaturized low-cost system

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Image MHT system

Image experimental model

Optical flow algorithms

Step 1: Finding the “good features to track”

As fibers are almost transparent and have thus the color of the background the

best features to be tracked are their edges.

Step 2: Tracking the interest points in each sequence using the optical flow tracker.

Automatic detection of shrinkage intervals using

image algorithms for movement detection

Optical flow is the distribution of apparent velocities of movement of brightness

patterns in an image.

E. Badea, O.A. Miu, V. Velican, C. Sendrea, Intelligent system for damage diagnosis of collagen based artefacts. Presentation at the

11th Mediterranean Conference on Calorimetry and Themal Analysis, Athens, Greece, 12-15 June 2013, not yet published.

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ImageMHT test results Ts detected by optical flow algorithms (orange)

compared with Ts detected by the human eye (brown)

The mean absolute error of the estimated Ts value was 1.1 °C for a series of 38 historical leather samples,

less than the experimental accuracy of 2 °C determined for the classic MHT method by R. Larsen

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Sample number

E. Badea, C. Carsote, O.A. Miu, V. Velican, G. Della Gatta, Damage assessment approaches for collagen-based artefacts: simple

tests and sophisticated analyses. Invted lecture at the 2nd Conference “Men and Books: From Microorganisms to Mega-

organisms” 28 April - 1 May 2014. Published in Cnference Proceedings Book, Verlag Berger, Horn, Austria (in print, expected for

the second half of 2014).

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CLEAR diagnostic system

Analytical database

Features

• component of the diagnosis software

• elaborate and organise a huge amount of data (analytical and descriptive) on collagen

artefacts of the Romanian patrimony with a common standard

• group the sub-samples from the same object and facilitate data correlation

• identify various deterioration patterns and suggest the most appropriate technique and

procedure to detect such a pattern

• accounts for the animal species and age of each object

Leather Object

New/Historical

Sample 1

Reference

Analysis

FTIR1

Results

MicroDSC1

Results

MHT1

Results

DSC1

Results

Sample 2

Artificially Aged

Artificial Aging Procedures

UV

32 hours

Temperature

70°C, 2 weeks

Analysis

FTIR2

Results

MicroDSC2

Results

MHT2

Results

DSC2

Results

Advantage: support for monitoring and managing of the museum/library/archive environment

and prioritization, and selection of the most appropriate methods for conservation to obtain the

longest life for collection with the lowest resource employment

Related research: bilateral collaborations

• Assessment and mitigation of climate impact on library and archival heritage:

experience, research, innovation (LIBER)

Romania – Hungary bilateral collaboration PN II 671/2013

• Quantitative assessment of environmental impact on collagen-based materials for low-

energy climate control in archives and museums (ENVICOLL) Romania – France, bilateral

collaboration PN II 713/2013)

• Advanced techniques and interdisciplinary studies for improved assessment of

historical parchment documents (ParIS)

Romania – Italy, bilateral collaboration PN II 638/2013

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Young researchers career

Enrolment for PhD programmes related to the project topic

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Thesis on Damage assessment of historical parchment and leather

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Thesis on Collagen based materials analysis using unilateral Nuclear Magnetic Resonance

Participation in International Training Schools and Workshops

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Summer School on Thermal Analysis and Calorimetry, 11th Mediterranean Conference on Calorimetry

and Thermal Analysis (MEDICTA 2013), Athens, Greece, 12 – 15 June 2013

•

Ampere Summer School on Analyzing Cultural Heritage using Portable Magnetic Resonance, organised

by the team of Prof Bernhard Blümich (Aachen University) which has been pioneering the field of mobile

NMR and has developed MOUSE, Volterra, Italy, 12-15 June 2013

• Oana Miu

Granted participation in the COST Action TD 1201 (COSCH) Training School on Automated 3D

documentation of CH artefacts with robotized structured light system, Faculty of Mechatronics, Warsaw

University of Technology, Warsaw, 25-27 November 2013

Research stages within the Bilateral Collaboration Projects

•

Hungarian Academy of Sciences (August 2013), University of Turin (October 2013 and April 2014)

•

University of Turin (April 2014)

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Publications (2012-2014)

• ISI articles: 5 published, 1 accepted, 2 submitted

• Peer-reviewed articles : 14 (2 indexed journals; 1 open-access journal;

2 indexed proceedings; 6 ISSN/ISBN conference proceedings; 3 conservation-

restoration bulletins)

• Books: 1

• Patents applications: 1

• Studies, 1; software, 2; informatic services, 1

Dissemination

Conference participation (2012-2014)

• Invited lectures: 8

• Oral presentations: 21

• Poster presentations: 20

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Dissemination & Training Seminar and Workshop organisation

1st International Seminar and Workshop Cultural Heritage–Emerging Technology

and Innovation: Preservation of Parchment, Leather and Textiles, 24–26 Sep 2012, National Museum of Romanian History, Bucharest

Media coverage

TV: Omul si Timpul (6 oct 2012)

Radio Cultural (25 sept 2012)

Press release

http://www.e-conservationline.com/content/view/1093

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Seminar and Workshop organisation

2nd International Seminar and Workshop Cultural Heritage–Emerging Technology

and Innovation: Preventive Conservation: Collections of Parchment, Leather and

Textiles and Their Environment, 3–6 Sep 2013, The Academy Library, Bucharest

Dissemination & Training

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Seminar and Workshop organisation

3rd International Seminar and Workshop Cultural Heritage–Emerging Technology

and Innovation: Advanced Technology for Diagnosis, Preservation and Management of Organic Cultural Heritage, 8 – 10 Oct 2014, CePCoR, ASTRA Museum, Sibiu

You are warmly invited to attend this highly interesting event. Participation is free.

Contact: elena.badea@unito it

Dissemination & Training