Conservation of painted pottery from Cucuteni culture with

macromolecular substances
Expert restorer Eng Ligia Otilia Teodor
Centre for Research and Restoration -Conservation of Cultural Heritage Iasi
The technological progress, both in research and discovery of ne substances, as ell as
increasing pollution and !uantities of har"ful substances in the environ"ent, deter"ined the
introduction of ne "ethods and substances ith superior perfor"ance in the case of
conservation and restoration of heritage ob#ects$
This paper is an overvie of the "ost effective "acro"olecular substances used in the
painted pottery restoration and conservation in our country laboratories and abroad, substances
that provide a loo% at the end of operations as close to original, and hich also correspond to
the restoration and preservation basic principles$
Evolving on our country territory beteen &'()-*+)) ,C, belonging to the vast cultural
areas (,))) years ago -.riu/d- Cucuteni -Tripoli co"plex0, Cucuteni culture is located in the
final period of polished stone age and is considered by the specialists one of the finest 1eolithic
cultures in Europe, the highest expression of ancient decorative art of the local pottery$
2peciali3ation and indisputable artistic value of the potters of this period is reflected by
the high !uality of the preparation and "odeling clay, oxidative co"bustion at high
te"perature up to 4*))
o
C and painted decoration of the vessels$ It turned out that after
"odeling, the pieces ere i""ersed in a broth of clay and 5 or a hite paste, decorated ith
"ineral pig"ents and then placed in the firing %iln$ The used dyes are6
- red -he"atite 7e
*
O
&
and hydrated iron oxides - goetite or li"onite
-bron - "anganese ferrous oxides-in the ,istrita river -8n
*
O
&,
8n7eO
9,
8n
&
O
9,
8nO-OH0
-hite - a thic% paste of CaCO
&,
that turned into CaO and 2iO
*
by burning :4;
The se!uencing of color as hite, thin layer over the surface of the vessel, then blac%-
bron and finally red$
<ue to the re"ar%able appearance of the orna"ent and the thorough "ethod through that
has been achieved, the conservation of this category of cera"ic frag"ents is a very i"portant
step in the restoration of 1eolithic vessels$
Therefore, depending on frag"ent si3e and degree of preservation of the painting on
the", deter"ined by the !uality of pulp and especially by the co"bustion te"perature, e use
to "ethods of preservation of the frag"ents or vessels6 brushing or dipping$
The cera"ics protection is achieved by i"pregnation ith resins or ith solutions
obtained by dissolving other "acro"olecular substances in organic solvents$
The i"pregnation "ethod of cera"ic frag"ents ith "acro"olecular substances to
strengthen decor involves in a first phase a good flo of the substance used, by heating in case
of resins or by suitable dissolution in case of other types of poly"ers$
,efore conservation, a strict drying of the frag"ents is needed to avoid ater
condensation under the protective layer$
In so"e cases, pre-heating the piece to be preserved is elco"e, especially hen cera"ic
is co"pact and ell-fired or the "acro"olecular substance used poly"eri3e at high
te"peratures$
Then the frag"ents i"pregnation is "ade ith the chosen substance by i""ersion for
resin or by brush or dip for poly"ers in solution$
The "ethod of resins or%ing is si"ple$ The frag"ents or the ob#ects of decorated
pottery are i""ersed in a bath of "olten ax for about an hour$ The bath te"perature "ust be
ther"ostatic stabili3ed ith "ore than (
o
C above the ax "elting point$ .fter re"oving the
ob#ects fro" the bath, the ax in excess is re"oved fro" the vessel surface, leaving the ob#ect
a fe "inutes in an oven or by passing a current of ar" air and iping surface ith absorbent
paper$ .s resins for i"pregnation e using beesax, paraffin ax, "icrocrystalline ax,
polyethylene and polyglycolethylene axes, the "a#ority of the" being found in anhydrous
for"$
The conservation of decorated pottery using poly"er solutions in solvents is "ostly by
brush and only if the frag"ents are s"all or are "ade of the cru"bly paste e preserve the" by
sin%ing$ .fter applying the coating solution, the poly"eri3ation usually ta%es place at roo"
te"perature or, in the case of poly"ers such as epoxy resins, at +) =C te"peratures belo IR
la"p$ . special attention should be paid to achieve the poly"er solution and thus the
proportion of solvent used, in order to avoid the appearance of a glossy fil" on the surface of
cera"ics$
,etter results are obtained hen the conservation operation is perfor"ed in a cha"ber
ith lo pressure, possibly under vacuu", to "ini"i3e the a"ount of air fro" the pores and
increase the efficiency of i"pregnation$
The "odern preservation and restoration of decorated cera"ics expected fro" the
"acro"olecular substances used to "eet certain basic principles$ Therefore, substances used in
"useu" laboratories "ust "eet the folloing conditions6
- to be repellent
- to be resistant to che"ical influences of polluted at"osphere
- to ithstand light
- to be inert and not interact ith ob#ects
- to ithstand the attac% of "icroorganis"s
> to be transparent and colorless
> to have good grip and fill the capillaries
> to be non-toxic
- to be che"ically stable
- to hold up ell to aging
- to be reversible$
The choice of poly"er substances used "ust avoid overly co"plex structures that can
undergo internal degrading transfor"ation, the ones ith lo resistance to aging or non-
reversible$
The "ain "acro"olecular substances that can be used for painted cera"ics conservation
in restoration laboratory can be classified by their che"ical structure as follos6
4$ Resins/waxes - are natural or synthetic poly"ers ith resin consistency, so ith
a"orphous structure and are used to preserve various "aterials$ 8ost used are beesax,
paraffin, ceresin ax -a resin that re"ains plastic after cooling0, polyethylene axes and
"icrocrystalline axes -polyglycolethylene0 such as Carboax 9)))$ The beesax is harvested
fro" beehives and is purified by "elting over +)
=
C and filtration$ It is a co"plex "ixture of
hydrocarbons, esters, and free fatty acids$ It dissolves easily in fe solvents and its solubility
increases ith te"perature$ .lthough yello over ti"e due to oxidation, it re"ains soluble
over "illennia$ It is used for ?final? consolidation because his re"oval fro" the pores of
cera"ics is difficult :*;$
The paraffin ax is a version of polyethylene ith lo "olecular eight and "olecular
unbranched chains$ It is over *)@ soluble at a"bient te"perature, especially in
tetrachlorethylene, trichlorethylene, tetrachlor"ethane, "ethylcyclohexane$ The prolonged
exposure to bright light leads to the dissolution of the poly"er lin%s and fading$ It is used as
"aterial for extraction of archaeological sites by pouring "elted over ob#ects , as te"porary
protection for ashing, for fresco, stone and painted cera"ic that does not re!uire further
intervention :*;, :A;$
2. Vinyl polymers$ In the restoration and conservation of cera"ics, for asse"bling the
frag"ents is "ainly used the polyvinyl acetate ithout plastici3er$ 7or preservation can be used
polyvinyl acetate LC in acetone$ The solution is colorless and for"s a very good protective fil"
:9;$
&$ Acrylic resins. 8ost acrylic poly"ers used in conservation are "ade up of to
fa"ilies of "ono"ers6 polyacrylates -acrylic poly"ers0, derived fro" acrylic acid and
poly"ethacrylates -"ethacrylic poly"ers0 - derived fro" "ethacrylic acid$
O O-R O O-R
BB C BB C
C C
D D
---CH > CH
*
-0
n
- ---C > CH
*
-0
n
-
D
CH
&
polyacrylate poly"ethacrylate
.l%yl - R individuali3e each poly"er :A;$
The co""ercial products "ost used are6 Paraloid !! - a poly"ethacrylate, Paraloid
"# or polyisobutyl"ethacrylate - hich contains stabili3er and the "ost i"portant- Paraloid
#2 - a blend of poly"er ith &)@ "ethacrylate and ')@ ethyl"ethacrylat :*;$
Earaloid ,'* hich does not beco"e insoluble and does not degrade significantly in
nor"al environ"ental conditions is one of the "ost stable "acro"olecular "aterials$ It is
transparent, has good "echanical strength and it is reversible, !ualities that derive fro" its
properties presented in the folloing table :&;6
Table 4 - Ehysical and che"ical properties of Earaloid ,'*
- Flass transition te"perature Tg 9) = C
- Tu%on hardness -GH10 4)-44
- Hardness ?2ard roc%er? A)
- Fraphite hardness H
- 2olubility H$&
- Iiscosity -at *(
o
C, 9)@ solution0
- in acetone *))
- in toluene (H)
The Earaloid ,'* solutions are prepared in various solvents, usually xylene, toluene or
acetone$ The best solvent as found to be p-xylene$ If pottery orna"entation is ell preserved
and the paste is ell burned there is danger of appearing a shiny surface fil"$ To avoid this it
can be add splicing agent, such as "icrocrystalline ax -over 9'@ in "ass0 or silicon -"ore
than 4A@ in "ass0 :*;$
Earaloid ,'* is reco""ended for strengthening ea% and friable pottery or for the one
decorated ith paintings poorly preserved, in solution of toluene and acetone, especially hen
intended to be used as an adhesive :';$
9$ Cellulose polymers. ."ong the "acro"olecular substances derived fro" cellulose,
the "ost idely used poly"er is cellulose nitrate. It is prepared fro" cellulose pulp and
concentrated sulfuric and nitric acids$ Jsually contains 44$* to 4*$&@ nitrogen by eight for
use as a varnish or adhesive, so the degree of substitution is fro" * to *$* :*;$
1itro-lac!uer used in conservation is "ade fro" nitrocellulose ith s"all a"ount of
nitrogen and lo degree of poly"eri3ation, using castor oil, butyl phthalate or natural resins as
plastici3er$ .s solvents are used si"ple aliphatic ester "ixed ith toluene and xylene :A;$ It has
high resistance to light and eather and it is in use since nineteenth century as a coverage and
strengthening solution for all types of cera"ic, "etal, stone, clay, fresco, ood and other
organic "aterials$ It can be applied easily, it dries !uic%ly and it is co"pletely soluble after a
long aging$
The co""ercial products best %non are6 $itrolac% &urofix - containing dibutyl
phthalate as plastici3er, &uco Cement% '(' (art :*;$
($ )poxy resins. .n i"portant category of "acro"olecular substances used in
conservation and restoration is for"ed by epoxy resins$ These substances are ther"o-rigid
co"pounds that have epoxide groups at the ends of chains$ ,ecause of these groups, the resin
can be strengthened by adding a"ine, dicarboxylic acids, aliphatic a"ides or acid anhydrides
:A;$
The "ain epoxy resin used is di*lycylether bisphenol A +shorted &,)A -% a viscous
or solid oligo"er :*;, used to produce various types of co""ercial products used in
conservation and restoration$ In this area, the strengthening of the resin should be done ith
dia"ines such as diethylenetria"ine or triethylentetraa"ine, as in these conditions the reaction
runs ithout by-products e"ission and therefore can be perfor"ed at nor"al te"perature and
at"ospheric pressure$ Raising the strengthening te"perature at A)-4))
=
C increases the nu"ber
of "olecules ties, increases the ther"ostability and "echanical strength :($ .s hardening
accelerators are used pri"ary alcohols such as ethylenglycol, hich added at a rate of 9-(@ by
the a"ount of resin double curing speed :+;$
The epoxy resins characteristics are superior to other resins6 they shrin% less than &@,
they have good "echanical and che"ical resistance and they have high adhesion to cera"ics of
all %inds, glass, "arble and "etals$ 7or this reason they are used as adhesives at roo"
te"perature for cera"ics, stone, glass, ferrous and nonferrous "etals$ .lso they can be
successfully used as i"pregnation solution for porous "aterials or ith special proble"s, such
as polychro"e decorated pottery, especially hen the used adhesive belongs to the sa"e class
of substances :*;$
."ong the "ost popular epoxy resins e "ar% out6 &.$/0 1.! +Romanian product0,
ison )poxy and Araldite ran*e2 Ay314 - (y56"% 7y #6# - (y552% 8A 33" - 956"%
AV34: - (V 55:% Cy235 - (y 235% Ay#61 - (y563% 2121 etc..
&.$/0 1.! Ro"anian product is a red-bron li!uid$ <ibutyl phthalate is used as a
plastici3er and the ratio resin5hardener is (54$ It is used only for dar% cera"ic or for
conservation of unexposed areas because of its color$
.;/$ )poxy is a to-co"ponent "ixture containing one part epoxy resin and one part
1 -& di"ethyla"inopropyl0 - 4,&-propylenedia"ine as a hardener$ It is highly transparent and
colorless and hardens in &) "inutes$
Araldite Ay#61 - (y563 is used for i"pregnation because it is very fluid$ The proportion
of use is 4) parts .y'() to 4 part hardener HyH(4 to 4 part dibutyl phthalate as plastici3er$
Araldite AV34: - (V55: is an epoxy resin that has the great advantage that it does not
thin up to 4()
o
C, hich allos i"pregnation of ob#ects after bonding$ It is necessary that the
infrared la"p te"perature does not exceed 4)) =C$ The ratio used is 4)59 resin5hardener$
Araldite 7y#6# - 9552 is a very fluent and colorless resin$ It can be used for cera"ics,
but is used pri"arily for glass bonding and conservation$
Araldite Ay314 - (y56" is a resin often used in our laboratories, both for cera"ic of all
types and glass, as ell as for "etal and stone$ It has superior properties6 it is very fluent,
colorless, it has good "echanical strength and it resist successfully to aging$ It is used the ratio
(54 resin5hardener and the ob#ect heating allos a better and faster i"pregnation$
Araldite 2121 (XW396/XW397) is one of the "ost appreciated to-co"ponent epoxy
resins by specialists in restoration and conservation, because it corresponds to all re!uire"ents
set out in the beginning of this or%, for hich is used successfully in "any laboratories in our
country and abroad$
7ro" the above it is noted that "acro"olecular substances that help %eeping the best
conditions for cera"ics and in particular preserving the polychro"e painted decoration, belong
to various classes of che"ical co"pounds ith physical and che"ical properties very different$
The folloing table presents so"e of these features for described poly"ers :*;$
Table * - Eroperties of "acro"olecular substances used in the conservation of decorated
cera"ics$
1a"e .crony" Tg n< Elasticity 2tability Entry

o
C "odule - years0 year
Eolyethylene -paraffin0 EE -*) 4,(* 4()-&9) ),(-*) 4AA)
Eolyvinyl acetate E.I 4A-*H 4,9+ K 4)) 4H&*
Eoly"ethacrylate E88. 4)( 4,9AH &))) K 4)) 4H&'
Eolyethyl"ethacrylat EE8. +$( 4,9A9 - K 4)) 4H9)
Cellulose nitrate C1 (+ 4,(4 *()) ),(-*) 4AHH
Epoxy resins 4,(+ *)))-9()) ),(-4)) 4H(*
-derivates <FE,.0
Tg,-glass transition te"perature, n<- refractive index
.ll these substances provide protection for preserved ob#ects for a very long period, hen
their storage and exposure occurs in environ"ental conditions established by conservation
rules$ It is necessary to respect these rules because in other conditions of te"perature and
hu"idity, the protective action is insufficient, resulting in da"age to the decoration of cera"ic
vessels in a relatively short ti"e$
,ibliography
4$ Ellis, L$ - LThe Cucuteni-Tripolie Culture, . 2tudy in Technology and the Origin of
Co"plex 2ocietyM, ,.R International 2eries *4',4HA9
*$ Horie, CI- L8aterials for ConservationN Organic consolidants, adhesives and
coatingsM, ,utterorths O Co$ Ltd$, 4HA'
&$ 7eller, RL- LTher"oplastic poly"ers currently in use as protective coatings and
potential directions for further researchM, ICC8 ,ulletin 4) -4HA90, (-4A
9$ Gorody, I$ - ?Elastics that are used in restoration and conservation > training course
($ Fedye, I$ - ?1otes for a short course in Conservation? - The ,ritish 8useu" Research
Laboratory, 4H'&
+$ Elenderleith, HI, Perner, .E.- LThe Conservation of .nti!uites and Por%s of .rtM,
*-nd edition, London 4H'4
'$ Goob, 2E- LThe use of Earaloid ,'* as an adhesive6its application for archeological
cera"ics and other "aterialsM, 2tudies in Conservation &4 -4HA+0, '-49
A$ 1enitescu, C<- ?Organic Che"istry?, Iolu"e II, <idactic and Eedagogic Eublishing
House,,ucharest,4HA)