Journal of Cultural Heritage 7 (2006) 236–243

http://france.elsevier.com/direct/CULHER/

Original article

Water dispersed polymers for textile conservation: a molecular,

thermal, structural, mechanical and optical characterisation
Mariacristina Coccaa, Lucia D’Arienzoa, Loredana D’Oraziob, Gennaro Gentileb,
Carlo Mancarellab, Ezio Martuscellia,*, Carmen Polcaroa
a
CAMPEC s.c.r.l, P. le E. Fermi, c/o CRIF, 80055 Portici, Italy
b
Istituto di Chimica e Tecnologia dei Polimeri del CNR, Via Campi Flegrei, 34, Fabbricato 70, 80078 Pozzuoli, Napoli, Italy

Received 28 November 2005; accepted 15 May 2005

Abstract
With the aim of identifying new water dispersed polymers for textile conservation, the structure and properties of three commercial polya-
crylates and one commercial polyvinylacetate were analysed. The characteristics of these materials, not previously used in the conservation and
restoration fields, were compared with that shown by Primal AC33 and Mowilith DMC2 and SDM5, widely used as consolidating or adhesive
agents of ancient textiles. To achieve a thorough characterisation of each polymer, molecular, thermal, structural and mechanical investigation
techniques were applied on film samples, obtained from polymer water dispersions through water casting at room temperature and/or compres-
sion moulding. The photo-oxidative resistance of these materials was also assessed by artificial weathering of water cast films and by measuring
the Yellowing Index (YI) as a function of the exposure time under xenon-arc lamp. Collected data were used to appropriately compare the
performances shown by these polymers when applied on artefacts consisting of natural fibres. In particular it was found that, among the products
not previously used in the conservation and restoration fields, a high potential for carrying out treatments on textiles is shown by the samples
commercialised with the trade names of Acrilem RP6005 and Acrilem 30WA. These products, in fact, exhibit properties that make them suitable
as substitutes for Primal AC33 and Mowilith DMC2 and SDM5, respectively, depending upon conservation needs. It was very interesting to note
that Acrilem 30WA, also after aging, shows YI values lower than that shown by Mowilith DMC2 and SDM5.
© 2006 Published by Elsevier Masson SAS.

Keywords: Polyacrylates; Polyvinylacetates; Textile conservation; Adhesive; Durability

1. Research aims application with no risks for the operators. Currently there are
no commercial polymers that simultaneously fulfil all of the
Synthetic polymers have been widely used as consolidating above-mentioned requirements and often products largely
agents or adhesives in the conservation and restoration of Cul- used by conservators and restorers are discontinued.
tural Heritage consisting of natural fibres, such as textiles, The performances shown by different materials cannot be
books, papyri and parchment. Depending upon conservation appropriately compared owing to the fact there are few scien-
needs, polymeric material should be characterised by physico- tific data on their chemical constitution, composition, structure
chemical properties suitable for binding damaged fibres and and properties. Thus it would be very useful to identify new
yarns, imparting physical strength to the artefact or improving polymer formulations with improved properties, and to set up
the adhesion between the artefact and a support fabric [1–3]. characterisation methods to assess suitability and efficiency of
The ideal properties should be flexibility, transparency, adhe- polymeric materials for conservation and restoration of textile
sion, cohesion, lack of colour, long-term durability, reversibil- items.
ity, possibility of reactivation for adhesives, ease and rapid In this paper we report on results of investigations carried
out to compare physico-chemical properties and aging resis-
* Correspondingauthor. Tel.: +39 081 750 2621; fax: +39 081 750 2618. tance shown by polymers widely used for conservation pur-
E-mail address: [email protected] (E. Martuscelli). poses (such as Primal AC33, Mowilith DMC2 and SDM5)
1296-2074/$ - see front matter © 2006 Published by Elsevier Masson SAS.
doi:10.1016/j.culher.2005.11.002
 M. Cocca et al. / Journal of Cultural Heritage 7 (2006) 236–243 237

[1–6], with those exhibited by selected commercial acrylate ples for mechanical analysis (UNI 882) were also obtained
and vinylacetate polymers. In fact Primal AC33 and Mowilith from the water cast films. For Acrilem ST1997, homogeneous
products have been applied on artworks [4–8] for their films cannot be obtained either by water casting or by com-
physico-chemical properties (good transparency and glass tran- pression moulding, while for Acrilem 674 homogeneous
sition temperature close to the environmental temperature), films can be obtained by compression moulding at 70 °C.
although they show some limitations. In particular Primal Moreover the films cast from the dispersion of Mowilith
AC33 has been discontinued by Rohm and Haas and research SDM5 were too soft for performing mechanical analysis.
works are still in progress [9] to find the best substitute;
furthermore Mowiliths are products not easily available and
2.2. Techniques
their photo-oxidative aging behaviour is not well understood.
Films of each polymer, cast from the commercial water dis-
persions at room temperature, have been investigated applying 2.2.1. Fourier Transform Infrared Analysis (FTIR)
Fourier Transform Infrared Spectroscopy (FTIR), Differential FTIR spectra were obtained with a Perkin Elmer spectro-
Scanning Calorimetry (DSC), Thermogravimetric Analysis meter (model Paragon 500) using 16 scans summation and a
(TGA), Wide Angle X-ray Scattering (WAXS) and Colori- nominal resolution of 4 cm−1. The analysis was carried out on
metric techniques. Mechanical properties of these materials at thin films obtained by dissolving Acrilem 30WA, 674,
room temperature has been investigated by means of a tensile RP6005, Primal AC33, Mowilith DMC2 and SDM5 samples
testing machine. Finally photo-oxidative resistance of each in chloroform and then casting these solutions directly on
polymer has been determined by artificial weathering of NaCl or KBr disks. FTIR analysis of Acrilem ST1997 sample
water cast films and by measuring their Yellowing Index (YI) was performed on dry polymer powder mixed with anhydrous
[10,11] as a function of the exposure time under xenon-arc KBr.
lamp.
2.2.2. Differential Scanning Calorimetry (DSC)
2. Experimental
The thermal behaviour of the investigated polymers was
2.1. Materials and sample preparation analysed by means of a Differential Scanning Calorimeter Met-
tler DSC 30 equipped with a control and programming unit
Mettler TC 11. Film samples were heated under nitrogen
The following commercial polymers have been charac-
terised: flow from –50 °C to a temperature below the temperature cor-
responding to the starting of degradation processes (run I),
cooled with a scanning rate of 50 °C min–1 and finally heated
● AC1: a polyethylacrylate used in fabric finishing, commer-
cialised with the trade name Acrilem RP6005; again from – 50 to 400 °C with a scanning rate of 10 °C min–1
(run II).
● AC2: an ethylacrylate-co-methylmethacrylate polymer used
as coating for stiff curtains, commercialised with the trade
name Acrilem 674; 2.2.3. Thermogravimetric Analysis (TGA)
● VA1: a vinylacetate-co-vinylversatate polymer used as bin- TGA was carried out on film samples, using a Mettler
der for water-based paints and wall coatings, commercia- microbalance equipped with a Mettler Thermogravimetric Ana-
lised with the trade name Acrilem 30WA; lyser model TG 50. The measurements were performed with a
● AC3: a copolymer styrene-acrylonitrile-buthylacrylate used heating rate of 10 °C min–1 from 50 to 600 °C in air and nitro-
as binder for non-woven textiles, commercialised with the gen atmosphere in order to determine the decomposition tem-
trade name Acrilem ST1997; perature.
● AC4: Primal AC33: an ethylacrylate-co-methylmethacrylate
polymer; 2.2.4. Wide Angle X-ray Scattering (WAXS)
● VA2: Mowilith DMC2: a vinylacetate-co-di-n-butylmaleate
WAXS investigations were carried out on film samples by
polymer;
means of a PW 3020/00 Philips diffractometer (Cukα Ni-
● VA3: Mowilith SDM5: a vinylacetate-co-n-butylacrylate
filtered radiation) equipped with a sample holder for sample
polymer.
spinning. The high voltage was 40 kV and the tube current
was 30 mA. A standard sample was employed to determine
The products coded as Acrilem are synthesised as water dis-
the instrumental broadening.
persions and sold by ICAP SIRA, Parabiago (MI, Italy); they
have been never used for conservation purposes previously.
Primal AC33 is made and sold as a water dispersion by 2.2.5. Mechanical analysis
Rohm and Haas, whereas Mowilith DMC2 and SDM5 are Uniaxial tensile tests were carried out in agreement with
made by Hoechst and sold by Kremer Pigment. UNI 8422, by means of an Instron 5564 tensile testing machine
Films of each polymer were prepared from the water disper- operating with a crosshead speed of 10 mm min–1 at the tem-
sions by casting at room temperature. Dumbbell-shaped sam- perature of 25 °C and 50% of relative humidity.
238 M. Cocca et al. / Journal of Cultural Heritage 7 (2006) 236–243

2.2.6. Colorimetric analysis Table 1

Characteristics of the water dispersions: pH, viscosity and dry content
Colorimetric analysis of films of all the investigated materi-
Code Commercial name pH Viscosity at Dry content
als was carried out by means of a Minolta 3600d spectrophot-
25 °C (130 °C – 1 h)
ometer. Colour data were calculated using illuminant D65 (mPA*s) (% wt./wt.)
(daylight 6500°K), 10 standard observer, sphere geometry, AC1 Acrilem RP6005 7.5 180 59
specular component included, UV energy included. AC2 Acrilem 674 4.5 125 50
VA1 Acrilem 30WA 5 3000 50
AC3 Acrilem ST1997 4 100 40
2.2.7. Artificial aging of the polymeric film AC4 Primal AC33 9 max 500 46
Polymeric films obtained as reported in Section 2.1 were VA2 Mowilith DMC2 4–5 5000–12,000 55
weathered in an Angelantoni SB3000E solarbox equipped VA3 Mowilith SDM5 4–5 5000–12,000 50
with a xenon-arc lamp. Aging treatments were carried out
with an irradiation of 1000 W m–2, dry bulb temperature that shown by Primal; Mowiliths being characterised by higher
(DBT) of 50 °C, without filters, and with exposure times ran- viscosity value. It is to be remarked that, depending on the
ging from 0 to 500 hours [12]. conservation needs, viscosity could be lowered by dilution or
increased by adding a thickening agent.
3. Results and discussion
3.2. FTIR analysis
3.1. Physico-chemical properties

The main characteristics of the commercial water disper- In Table 2 the main frequencies of the absorption bands,
sions, such as pH, viscosity at 25 °C and material dry content relative intensities and main assignments are reported for
are reported in Table 1. It should be noted that Primal AC33 each investigated polymer and corresponding FTIR spectra
and Acrilem RP6005 are basic whereas Mowiliths, Acrilem are shown in Fig. 1.
674, Acrilem 30WA and Acrilem ST1997 are acidic, thus indi- For all the investigated materials the presence of the C=O
cating that basic dispersions could be useful for application on groups is confirmed by a strong absorption band in the range
cellulose substrata and acidic dispersions on protein substrata. 1740–1735 cm−1 (stretching), while the bands in the range
As far as the viscosity values are concerned, such values fall 1260–1237 cm−1 confirms the presence of the C–O bonds
in a wide range. In particular Acrilem RP6005, 674 and (stretching). The absorption bands at 1372 cm−1 and in
ST1997 exhibit viscosity values more or less comparable to 1432 ± 2 cm−1 are diagnostic of the acetate group.

Table 2
Frequencies of absorption bands, relative intensity and tentative assignments for the investigated polymers
Frequency (cm−1) Polymera Relative intensityb Tentative assignmentsc
2985–2981 AC1, AC2, AC4 S n (CH aliphatic)
2963–2961 VA1, VA2, VA3 S n (CH aliphatic)
2951 AC2, AC4 S n (CH aliphatic)
2935–2926 AC1, VA1, VA2, VA3 S n (CH aliphatic)
2875–2870 AC1, VA1, VA2, VA3 M n (CH aliphatic)
2240 AC3 S nitrile group
1740–1735 AC1, AC2, VA1, AC3, AC4, VA2, VA3 S n (C=O ester)
1544 AC3 M aromatic ring
1496 AC3 M aromatic ring
1465–1445 AC1, AC2, VA1, AC3, AC4, VA2, VA3 S β (CH2 aliphatic)
1433–1430 VA1, VA2, VA3 M β (CH in –OCOCH3)
1385–1379 AC1, AC2, AC3, AC4 M β (CH2 aliphatic)
1372 VA1, VA2, VA3 M β (CH in –OCOCH3)
1240–1237 VA1, VA2, VA3 S n (C–O)
1260–1238 AC1, AC2, AC3, AC4 S n (C–O)
1176–1160 AC1, AC2, AC3, AC4, VA2, VA3 M–W δ (CH aliphatic)
1118 AC3 W aromatic ring
1124–1111 VA1, VA2, VA3 W β (CH2 aliphatic)
1099–1020 AC1, AC2, VA1, AC3, AC4, VA2, VA3 M n (C–C)
950–940 VA1, AC3, VA2, VA3 W n (C–C)
855–846 AC1, AC2, AC4 W n (C–C)
760–754 AC1, AC2, AC4 M–W η (C–H)
762 AC3 S aromatic ring
702 AC3 S aromatic ring
a
AC1: Acrilem RP6005; AC2: Acrilem 674; VA1: Acrilem 30WA; AC3: Acrilem ST1997; AC4: Primal AC33; VA2: Mowilith DMC2; VA3: Mowilith
SDM5.
b
Relative intensity is based on the whole infrared spectrum of a sample at room temperature: S = strong, W = weak, M = medium.
c
Main assignments are: n = stretching, β = bending, δ = bending out-of-plane; η = rocking.
 M. Cocca et al. / Journal of Cultural Heritage 7 (2006) 236–243 239

[13], while this ratio decreases for Acrilem 674, thus indicating
of a comparatively higher amount in the co-monomer MMA.
For Acrilem ST1997 (Fig. 1d) the absorption band at
2240 cm−1 confirms the presence of the acrylonitrile mono-
meric unit; the presence of styrene groups being shown by
the absorption bands at 702, 762, 1496 and 1544 cm−1.

3.3. Thermal analysis

For all the materials the results of thermal analysis obtained

by DSC are summarised in Table 3.
DSC analysis does not reveal melting phenomena, thus sug-
gesting that all the materials are in amorphous structure. All the
investigated materials show glass transition temperatures (Tg),
detected through DSC, between –13 and 42 °C.
In particular Acrilem RP6005 shows a clear Tg located at
–11 °C; such a value is close, within the experimental error,
to the Tg value reported in literature for PEA [14i], thus con-
firming the results of FTIR analysis. Tg values of Acrilem 674
and Acrilem ST1997 are higher than 40 °C, so that they seem
to be unsuitable for textile conservation because they can
induce stiffness on the treated substrata. Moreover it is to be
noted that such a Tg value for Acrilem 674, a poly(ethylacry-
late-co-methylmethacrylate), suggests that the ratio between
the co-monomers EA/MMA is lower than 2; this result con-
Fig. 1. FTIR spectra of: (a) AC1: Acrilem RP6005; (b) AC2: Acrilem 674; (c) firming what has been evidenced by FTIR analysis.
VA1: Acrilem 30WA; (d) AC3: Acrilem ST1997; (e) AC4: Primal AC33; (f) From the DSC trace (I run) obtained for Acrilem 30WA it
VA2: Mowilith DMC2: (g) VA3: Mowilith SDM5. can be noted that this material exhibits a single Tg at 12 °C.
Taking into account that literature [3] gives a Tg value for
The presence of versatate group for Acrilem 30WA cannot PVAc at about 30 °C, it can be deduced that the presence of
be evidenced by FTIR analysis. vinylversatate units results in a lowering of the Tg. This result
FTIR spectrum of Acrilem RP6005 (Fig. 1a) matches the agrees with the trend generally expected for the Tg values of
spectrum of a polyethylacrylate. It can be also noted that vinyl polymers, which decrease with increasing length of the
FTIR spectra of Acrilem 674 (Fig. 1b) and Primal AC33 aliphatic side chains [1].
(Fig. 1e) match spectra of commercial ethylacrylate-co-methyl- Primal AC33 shows a clear Tg at 14 °C with run II
methacrylate polymers reported in literature. For Primal AC33 practically confirming this Tg value. Such a value is close to
the ratio between co-monomers EA/MMA seems to be 2/1 the Tg value reported [14] for poly(ethylacrylate-co-methyl-

Table 3
Thermal properties of the investigated polymers
Transition Glass transition (°C) Glass transition (°C) Thermal degradation in Thermal degradation in air
(DSC–run I) (DSC–run II) nitrogen flowa(°C) (TGA) flowa(°C) (TGA)
Sample
AC1: Acrilem –11 –13 365 364
RP6005
b
AC2: Acrilem 41 332 321
674
VA1: Acrilem 12 21 318 326
30WA 477 459
b
AC3: Acrilem 42 356 356
ST1997 530 535
AC4: Primal 14 16 371 375
AC33
VA2: Mowilith 18 15 311 314
DMC2 511 505
VA3: Mowilith 8 4 305 307
SDM5
a
Temperature values corresponding to maximum rates in weight loss.
b
Not clearly detectable.
240 M. Cocca et al. / Journal of Cultural Heritage 7 (2006) 236–243

methacrylate) with a ratio between co-monomers 3.4. WAXS investigation

EA/MMA = 2/1.
Finally DSC traces (run II) of Mowilith DMC2 and SDM5 In Fig. 3 WAXS intensity profiles shown by Acrilem
show Tg values of 15 and 4 °C, respectively. RP6005 and Acrilem 674 are compared with WAXS intensity
In Table 3 and Fig. 2 decomposition temperatures and TGA profile exhibited by Primal AC33, whereas Acrilem 30WA
traces under nitrogen flow are respectively reported for all the WAXS intensity profile is compared with those shown by
investigated polymers. It can be inferred that all the materials Mowilith DMC2 and Mowilith SDM5. In Table 4 the reflec-
show a thermal resistance appropriate for use in conservation tion maxima with the corresponding angles (2θ), spacings (d)
and restoration of Cultural Heritage consisting of natural and relative intensities are listed for all the investigated poly-
fibrous polymers. Furthermore the thermal degradation pro- mers. The materials are characterised by an amorphous struc-
cesses of all the materials are unaffected by oxygen presence: ture, even though certain local regularity is observed.
the temperatures corresponding to the maximum weight loss To be noted is that a comparatively higher local regularity is
rates by heating the materials in air flow is, in fact, very shown by Mowilith DMC2 among the polyvinylacetates and
close to that measured in nitrogen flow. by Acrilem RP6005 among the polyacrylates. As shown by
In conclusion, in order to evaluate the potential of the inves- the WAXS intensity profile, Acrilem 674 sample exhibits
tigated materials for conservation and restoration purposes, Tg four reflections highly convoluted each other, whereas Primal
values must be carefully considered. In fact, a polymer coating AC33 displays three diffuse scattering reflections.
with a Tg value considerably higher than room temperature Fig. 3c,f,g show WAXS intensity profile of Acrilem 30WA,
(which is the use temperature) is unable to respond to changes Mowilith DMC2 and SDM5, respectively. As shown by data
in the dimensions of the item and could thus damage it. In reported in Table 4, three diffuse scattering reflections are
contrast, a polymer coating showing a Tg value noticeably observed both for Acrilem 30WA and Mowiliths. The first
lower than room temperature can be too soft to act as consoli- two, convoluted each other, are in the range between 5° and
dating agent, tending also to pick up dirt. Similar restrictions 35° of 2θ. The last one, very broad and weak in intensity, is
can be applied for the use of these materials as adhesives. between 35° and 60° of 2θ. By comparing the WAXS intensity
profiles and the related data, and considering that Acrilem

Fig. 2. TGA traces of the investigated polymers. Weight residual (WR) and
weight loss rate (WLR): (a) AC1: Acrilem RP6005; (b) AC2: Acrilem 674; (c) Fig. 3. WAXS intensity profiles of: (a) AC1: Acrilem RP6005; (b) AC2:
VA1: Acrilem 30WA; (d) AC3: Acrilem ST1997; (e) AC4: Primal AC33; (f) Acrilem 674; (c) VA1: Acrilem 30WA; (e) AC4: Primal AC33; (f) VA2:
VA2: Mowilith DMC2: (g) VA3: Mowilith SDM5. Mowilith DMC2: (g) VA3: Mowilith SDM5.
 M. Cocca et al. / Journal of Cultural Heritage 7 (2006) 236–243 241

Table 4
X-ray reflection maxima with corresponding angle (2θ), spacing (d) and relative intensity
Material Reflection 1 Reflection 2 Reflection 3
2θ (°) d (Å) Relative 2θ (°) d (Å) Relative 2θ (°) d (Å) Relative
intensitya intensitya intensitya
AC1: Acrilem RP6005 11.7 7.6 s 21.5 4.1 vs 37.1 2.4 vvw
AC2: Acrilem 674 12.5 7.1 vvs 16.4 5.4 s 29.8 3.0 w
VA1: Acrilem 30WA 15.1 5.9 vs 20.8 4.3 vs 40.0 2.3 w
AC2: Acrilem ST1997 8.2 10.8 w 19.9 4.5 vs 40.0 2.3 vw
AC3: Primal AC33 13.1 6.8 vw 20.4 4.3 vw 40.5 2.2 vvw
VA2: Mowilith DMC2 9.3 9.5 s 20.2 4.4 s 44.7 2.0 vw
VA3: Mowilith SDM5 11.9 7.4 vw 21.6 4.1 vw 43.8 2.1 vvw
a
s = strong, w = weak, v = very.

30WA, Mowilith DMC2 and SDM5 materials are polyvinyla- Young’s Modulus and a stress at maximum load higher than
cetates, it is confirmed that the local regularity decreases with that shown by the Acrilem 30WA, whereas the strain at break
increasing steric hindrance along the copolymer chain. value is slightly lower. Considering that these materials at
As far as the potential of the investigated polymers for con- room temperature are both close to their Tg, the different
servation and restoration is concerned, it is important to note mechanical responses could be related to the different local
that the local regularity decreases the rubber-like elasticity and regularity already evidenced by WAXS analysis. Finally to be
affects the mechanical behaviour of the material. noted is that Acrilem 674 shows a stress–strain curve typical
for a ductile material (Fig. 4b). During deformation, in fact, the
3.5. Tensile behaviour material undergoes yielding and cold-drawing phenomena
before breaking. Thus, considerably higher elastic modulus,
Typical stress–strain curves obtained at room temperature stress at maximum load as well as lower deformation at break
for Acrilem RP6005 (a), 674 (b), 30WA (c), Primal AC33 (e) are found (see Table 5). Such a tensile behaviour is to be
and Mowilith DMC2 (f) dumbbell-shaped specimens are related to the higher amount of MMA co-monomer in respect
shown in Fig. 4; the tensile properties for each investigated to Primal AC33.
material are summarised in Table 5.
As shown in Fig. 4 and from the data reported in Table 5,
very different uniaxial tensile behaviours are observed. In par-
ticular Acrilem RP6005 and 30WA together with Primal AC33
exhibit stress–strain curves typical of uncrosslinked elastomers.
Note that better properties are shown by Primal AC33, whereas
Acrilem RP6005 shows the lowest values of elastic modulus
and stress at maximum load, the value of the strain at break
being slightly higher than that found for Acrilem 30WA. Tak-
ing into account that Acrilem RP6005 and Primal AC33 are
both acrylic polymers, the different mechanical behaviour can
be related to the different Tg values: at room temperature Pri-
mal AC33 is considerably closer to its Tg (14 °C) than Acrilem
6005 (Tg –11 °C). Mowilith DMC2 shows a stress–strain curve
whose shape is similar to that shown by cross-linked elasto-
mers. In fact this material is characterised by a modulus value
twice as high as that shown by Primal AC33, lower stress at
maximum load and strain at break. By comparing the mechan-
ical behaviour of vinyl polymers (Acrilem 30WA and Mowi-
lith DMC2) it is observed that Mowilith DMC2 shows a
Table 5
Tensile properties shown by Acrilem RP6005, 674, 30WA, Primal AC33 and
Mowilith DMC2
Sample Young's Stress at Strain at break
Modulus maximum load (%)
(MPa) (MPa)
AC1: Acrilem RP6005 0.54 ± 0.07 0.51 ± 0.05 780 ± 90
AC2: Acrilem 674 540 ± 80 20 ± 1 310 ± 30
VA1: Acrilem 30WA 5.5 ± 1.1 1.1 ± 0.1 670 ± 60 Fig. 4. Typical stress–strain curves for: (a) AC1: Acrilem RP6005; (b) AC2:
AC4: Primal AC33 15.4 ± 2.0 5.8 ± 0.6 2500 ± 300 Acrilem 674; (c) VA1: Acrilem 30WA; (e) AC4: Primal AC33; (f) VA2:
VA3: Mowilith DMC2 31.6 ± 2.3 3.3 ± 0.9 640 ± 80 Mowilith DMC2.
242 M. Cocca et al. / Journal of Cultural Heritage 7 (2006) 236–243

On the basis of these results, higher potential for conserva-

tion purposes is shown by Acrilem RP6005 and 30WA, i.e.
ethylacrylate and vinylversatate products, even though they
exhibit poorer mechanical properties in comparison with
those shown by the corresponding polyacrylate (Primal
AC33) or polyvinylacetate (Mowilith DMC2) already used in
conservation.

3.6. Colorimetric analysis

For the measure of the optical properties we used the Yel-

lowing Index (YI). YI is a measure of the yellowing phenom-
ena of the film normalised with respect to the thickness of the
film. YI is calculated using the formula
YI ¼ ðA380
A600 Þ  0:1mm=T

where:
T = thickness of the film in mm;
A380 = Absorbance of the film at 380 nm;
A600 = Absorbance of the film at 600 nm.
For each polymeric film YI values calculated before xenon-
arc lamp exposure are reported in Table 6. To be noted is that
the only material showing a relevant yellowing is Acrilem
ST1997 (Table 6). All the remaining materials show conver-
sely excellent optical properties of colourlessness and transpar-
ency, thus indicating that the aesthetic of objects should be
minimally affected by using such polymers as coating.
Moreover films of each polymer, except for Acrilem
ST1997, artificially aged in solarbox as described in Section Fig. 5. YI of polymeric films versus exposure time (hours) under xenon-arc
2.2, were undergone to colorimetric analysis. In Fig. 5 the lamp: (a) AC1: Acrilem RP6005; (b) AC2: Acrilem 674; (c) VA1: Acrilem
30WA; (e) AC4: Primal AC33; (f) VA2: Mowilith DMC2: (g) VA3: Mowilith
curves of YI as a function of the exposure time (hours) are SDM5.
reported for each material. As expected, after the aging treat-
ment, acrylate polymers show more relevant yellowing phe- 4. Conclusion
nomena, while vinyl based materials show lower yellowing.
It is interesting to observe that, among acrylic polymers, the With the aim of identifying new water dispersed polymers
YI shown by the ethylacrylate material Acrilem RP6005 is with consolidating and/or adhesive properties for textile arte-
comparable to the one shown by Primal AC33 through the facts, seven different commercial polymers have been selected
whole exposure period. Concerning vinyl polymers, it is to be and characterised by applying molecular, thermal, structural
noted that the best performing is the vinylversatate polymer and mechanical investigation techniques on polymeric films.
Acrilem 30WA; in fact this material shows YI values constant In particular the properties of polyacrylates and polyvinylace-
throughout the whole exposure period, thus suggesting that this tate not previously used in conservation have been compared
material offers a satisfactory durability. with those shown by polyacrylates and polyvinylacetates used
as consolidating or adhesive agents for ancient textiles, such as
Table 6
YI of the films obtained by compression moulding (Acrilem 674 and ST1997) the discontinued Primal AC33 and the not easily available
and by water casting (Acrilem RP6005, 30WA, Primal AC33, Mowilith DMC2 Mowilith DMC2 and SDM5. The photo-oxidative resistance
and SDM5) before exposure treatments under xenon-arc lamp of such products has also been investigated through artificial
Code Sample YI weathering of water cast films and measuring the YI as a func-
AC1 Acrilem RP6005 0.0052 ± 0.0004 tion of the exposure time under a xenon-arc lamp.
AC2 Acrilem 674 0.0021 ± 0.0003
VA1 Acrilem 30WA 0.0029 ± 0.0003
To be remarked is what follows:
AC3 Acrilem ST1997 0.0506 ± 0.0018
AC4 Primal AC33 0.0018 ± 0.0003 ● through water casting at room temperature, transparent and
VA2 Mowilith DMC2 0.0108 ± 0.0012 homogeneous films are formed from the commercial poly-
VA3 Mowilith SDM5 0.0051 ± 0.0009
mer dispersions, thus indicating that polymers, when used
 M. Cocca et al. / Journal of Cultural Heritage 7 (2006) 236–243 243

as coatings, would minimally affect the aesthetics of the product, Acrilem 30WA, also after aging, shows YI lower than
artefacts; that shown by Mowilith DMC2 and SDM5.
● the chemical constitution of each polymer has been con-
firmed by means of FTIR, showing moreover the extent of Acknowledgements
same molecular similarity among investigated products;
● as far as the thermally induced degradation is concerned, it The authors would like to thank Dr. Marco Cerra (ICAP
has been shown by TGA that all the materials, irrespective SIRA) for the materials supplied and the scientific support
of chemical composition, are appropriate for use in conser- offered.
vation and restoration of Cultural Heritage consisting of nat-
ural fibres; References
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