Alvar and Butvar: The Use of Polyvinyl Acetal Resins for the Treatment of the Wooden

Artifacts from Gordion, Turkey

Author(s): Krysia E. Spirydowicz, Elizabeth Simpson, Robert A. Blanchette, Arno P.
Schniewind, Mauray K. Toutloff and Alison Murray
Source: Journal of the American Institute for Conservation, Vol. 40, No. 1 (Spring, 2001),
pp. 43-57
Published by: Taylor & Francis, Ltd. on behalf of The American Institute for Conservation
of Historic & Artistic Works
Stable URL: http://www.jstor.org/stable/3180012
Accessed: 12-12-2017 12:12 UTC

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 ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL
RESINS FOR THE TREATMENT OF THE WOODEN
ARTIFACTS FROM GORDION, TURKEY

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A.

BLANCHETTE, ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF,
AND ALISON MURRAY

ABSTRACT-Archaeological excavations con- sions when called upon to treat dry archaeological
ducted by the University of Pennsylvania Museum ofwood.
Archaeology and Anthropology from 1950 to 1973 atTITRE-L'Alvar et le Butvar: l'utilisation des resines
the ancient capital of Gordion in central Anatolia d'ac&tal de polyvinyl pour le traitement d'objets en
uncovered impressive remains of the material culturebois du site de Gordion, en Turquie. RESUME-Les
of ancient Phrygia. During the early years of thefouilles arch0ologiques effectu&es de 1950 a 1973 par
project, the exploration of three massive earthen le University of Pennsylvania Museum of Archaeol-
burial mounds or tumuli in the royal necropolis led ogy and Anthropology (mus&e d'archeologie et d'an-
to the discovery of one of the most important collec-thropologie de l'universite de Pennsylvanie) '
tions of wooden furniture and objects to emergeGordion, capitale de la Phrygie antique en Anatolie
from the ancient Near East. centrale, ont mis a jour des vestiges importants de
Composed of a surprising variety of woods, the
cette culture ancienne. Durant les premieres ann&es
artifacts ranged in condition from poor to excellent.
des fouilles, trois enormes tumuli de la n&cropole
Initial attempts to treat the furniture and woodenroyale ont ete explores, ce qui mena a la d&couverte
objects on-site included the application of Alvar,d'une
a des plus importantes collections de meubles et
d'objets en bois du Proche-Orient antique.
polyvinyl acetal resin. Soon after, most of the pieces
were transferred to the Museum of Anatolian Civi- Les artefacts sont composes d'une vari&ti ton-
lizations in Ankara, where they remained in storage
nante d'essences en bois et leur &tat varie du pietre a
until a rescue program was initiated by the Univer-
l'excellent. Les essais initiaux de traitement des objets
en bois et des meubles sur le site meme inclurent
sity of Pennsylvania Museum of Archaeology and
Anthropology in 1981. Consolidation of the wood l'utilisation d'Alvar, une resine a base d'ac&tal de
polyvinyl. Peu apres leur traitement, la plupart des
with Butvar B-98, a polyvinyl butyral resin, was the
procedure adopted after testing to successfully retreat
objets furent transf&ers au mus&e de la civilisation
37 pieces of ancient furniture and more than 50 small
anatolienne a Ankara. Ils y demeurerent en reserve
wooden objects from the three royal tombs. jusqu'en 1981, lorsque le mus&e d'archeologie et
An assessment of the effects of both resins on the d'anthropologie de l'universite de Pennsylvanie
ancient woods is presented here, followed by a entreprit a leur 6gard un programme de conservation
description of recent scientific tests conducted on d'urgence.Apres des essais preliminaires, 37 pi&ces de
samples of Butvar B-98. These tests include scanning mobilier ancien et plus de 50 petits objets en bois
electron microscope studies to determine the extent provenant des trois tombes royales furent consolides &
of penetration of Butvar B-98 into treated samples, nouveau et avec succes a l'aide du Butvar B-98, une
hardness testing to assess the strengthening effects of resine ' base de butyral de polyvinyl.
the consolidant on the wood, and exposure to intense Cet article presente une evaluation de l'effet des
environmental conditions to determine the aging deux resines sur les bois anciens, ainsi qu'une descrip-
characteristics of Butvar B-98 films. tion d'essais scientifiques effectues r&cemment sur des
The treatment of the Gordion wood has &chantillons de Butvar B-98. Ces essais incluent des
provided a unique opportunity to document and
examens au microscope electronique a balayage afin
characterize the behavior of two related wood de verifier le degre de penetration de cette resine
dans le bois; des mesures de durete afin d'6valuer les
consolidants over a 40-year period. This contribution
to the growing body of literature on the subject
caract&ristiques de consolidation que la resine impar-
should assist conservators in making informed deci-
tit au bois; et enfin l'exposition de couches minces de

JAIC 40 (2001):43-57

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44

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A. BLANCHETTE,

ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF, AND ALISON MURRAY

cette resine a des conditions environnementales

extremes, afin de determiner ses caracteristiques de

vieillissement.

Le traitement du bois provenant de Gordion fut

une occasion unique de documenter et caract&riser le
comportement sur une p&riode de 40 ans de deux
consolidants de composition voisine. Au moyen de
cette contribution a la litterature sur le sujet (qui ne
cesse d'ailleurs de croitre), les auteurs cherchent '
fournir des renseignements utiles aux restaurateurs
charges d'entreprendre le traitement d'objets en bois
sec provenant de fouilles archeologiques. Fig. 1. Tumulus MM during excavation in 1957

TITULO-Alvar y Butvar: el uso de resinas de acetalseguido de una descripci6n de pruebas cientificas

de polivinilo para el tratamiento de artefactos de recientes Ilevadas a cabo sobre muestras de Butvar B-
madera de Gordion, Turquia. RESUMEN-Las 98. Estas pruebas incluyen estudios de microscopia
excavaciones arqueol6gicas l1evadas a cabo por el electr6nica de barrido para determinar la extensi6n
Museo de Arqueologia y Antropologia de la Univer- de la penetraci6n de Butvar-98 dentro de las mues-
sidad de Pensilvania desde 1.950 hasta 1.973 en la tras tratadas, pruebas de dureza para examinar los
efectos de fortalecimiento del consolidante sobre la
antigua capital de Gordion, en Anatolia Central, reve-
laron restos impresionantes de material cultural madera
de la y exposici6n a condiciones ambientales
antigua Frigia. Durante los primeros afios intensas
del para determinar las caracteristicas de enve-
jecimiento
proyecto, la exploraci6n de tres grandes entierros en de las peliculas de Butvar B-98.
El tratamiento de la madera de Gordion ha ofre-
barro, tipo monticulos o tumulos, en la Necr6polis
cido una oportunidad uinica para documentar y
Real llev6 al descubrimiento de una de las mis
caracterizar
importantes colecciones de mobiliario y objetos en el comportamiento de dos consolidantes
de madera relacionados, y durante un periodo de 40
madera provenientes del antiguo Cercano Oriente.
Compuestos de una sorprendente variedad afios.
de Esta contribuci6n al volumen creciente de
literatura
maderas, las condiciones de los artefactos variaban de sobre la materia, ayudara a los conser-
vadores
pobre a excelente. Intentos iniciales para tratar el a tomar decisiones bien fundamentadas al

tratar
mobiliario y objetos de madera in-situ incluyeron la madera arqueol6gica seca.
aplicaci6n de Alvar, una resina de acetal de polivinilo.
1. INTRODUCTION
Seguidamente, la mayoria de las piezas fueron trans-
feridas al Museo de las Civilizaciones Anatolianas, en
Between 1950 and 1973, the archaeological site
Ankara, donde permanecieron en almacenamiento
hasta que se inici6 un programa de rescate hechoGordion
por in central Turkey was excavated by th
el Museo de Arqueologia y Antropologia deUniversity
la of Pennsylvania Museum of Archaeolo
Universidad de Pensilvania en 1.981. Despubsand
de Anthropology under the direction of archaeol
gist
reaplicar exitosamente Butvar B-98, una resina de Rodney S.Young. Gordion was the capital of t
butiral de polivinilo, a 37 piezas de mobiliario
ancient kingdom of Phrygia, ruled at the height of
power in the 8th century B.C. by the great Ki
antiguo y a mis de 50 objetos pequefios de madera
Midas.
provenientes de tres tumbas reales, se adopt6 este Three of the richest tombs from the Gordion
necropolis-Tumulus
procedimiento para la consolidaci6n de la madera MM, Tumulus P, and Tumu
durante el proyecto. W-date to this period. Tumulus MM, the larg
El resultado de los efectos de ambas resinas sobre tomb at Gordion, is thought to be the tomb of Mid
la madera antigua es presentado en este trabajo, himself (fig. 1).

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 45

ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL RESINS FOR THE
TREATMENT OF THE WOODEN ARTIFACTS FROM GORDION, TURKEY

led to the search for more suitable alternatives.

The three burials contained many exceptional
works of art, including wooden household objects
Soluble thermoplastic resins appeared to offer a
and a collection of fine wooden furniture. More than number of significant advantages over thermosetting
37 pieces of furniture and more than 50 small resins. In 1980, Grattan examined a number of
wooden objects were excavated from these burials, commercially available thermoplastic resins and
now recognized as the most important collection offound polyvinyl butyral and various acrylic resins to
ancient Near Eastern wooden artifacts ever recov- be the most promising consolidants (Grattan 1980).
ered. In the following year, Barclay (1981) employed
After the excavation of the three tombs between
polyvinyl butyral to successfully consolidate a
1956 and 1959, the furniture and wooden objects wooden fire engine dating to the 18th century.
were conserved using available methods, and studied Barclay's results influenced Robert Payton, the first
briefly. Some were placed in storage at Gordion, but conservator for the Gordion Furniture Project, to
most of the collection was taken to the Museum of consider the use of polyvinyl butyral as a potential
Anatolian Civilizations in Ankara. Research contin- consolidant for the ancient wood. However, Payton
ued on the finds, which were published in Young's
selected Butvar B-98 for testing rather than Butvar
posthumous excavation report (Young 1981). It was
B-90, the grade used by Barclay. Payton deliberately
chose to experiment with the grade of resin that
during the preparation ofYoung's volume that many
offered the lowest molecular weight and lowest
of the original interpretations and drawings of the
wooden objects were found to be incorrect (Simp-
viscosity in solution in order to promote the highest
son 1996; Simpson and Spirydowicz 1999). degree of penetration. When tests confirmed the
Further attempts to study the objects revealedsuitability of Butvar B-98, Payton used it to consoli-
that the wood was deteriorating, with some piecesdate
so an ornate inlaid table from Tumulus MM
fragile that they could not be handled. Because of the
(Payton 1984a). The treatment originated by Payton
importance of the collection, the University of Penn-
was further developed and refined by an interna-
sylvania Museum initiated a rescue project in 1981 tional
to group of conservators in subsequent seasons to
restudy, conserve, and republish the furniture and
successfully treat all of the ancient wooden furniture
wooden objects from Gordion. found in the three great early tumuli at Gordion
(Spirydowicz 1996; Simpson and Spirydowicz 1999).
2. BRIEF HISTORY OF THE TREAT- During the mid-1980s, scientific testing of ther-
MENT OF DRY ARCHAEOLOGICAL moplastic resins was proceeding. In 1985, Wang and
WOOD Schniewind evaluated improvements in strength and
stiffness in samples of bacterially degraded wood after
A relatively large body of literature treatment
now existswith a variety of consolidants, including
concerning the treatment of waterloggedpolyvinyl
wood frombutyral, Paraloid B-72, and polyvinyl
archaeological sources. However, the acetate
number of (Wang and Schniewind 1985). This
resins
publications dealing with the treatment
work of
wasdry
followed by an assessment of the adhesive
archaeological wood remains small. During the 1960s
qualities of thermoplastic resins used as consolidants
and 1970s, thermosetting synthetic resins such
(Sakuno asSchniewind 1990) and, in the same
and
epoxies and polyesters were proposed foryear,
the by
consol-
an analysis of the effects of solvent retention
idation of degraded wooden artifacts andafter
structures
consolidation with thermoplastic resins (Carl-
(for example, Schaffer 1971, 1974; Munnikendam
son and Schniewind 1990). Scanning electron
and Wolschrijn 1969). However, their microscopy
significantwas used to study the distribution of
disadvantages, including lack of reversibility, unsatis-
synthetic resin consolidants in samples of degraded
factory surface appearance, and the difficulty of
wood (Schniewind and Eastman 1994) as well as to
control during curing (Schaffer 1971; Munnikendam
evaluate changes caused by the introduction and
1978; Grattan 1980), were soon recognized, which
subsequent extraction of consolidants (paraffin wax

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46

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A. BLANCHETTE,

ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF, AND ALISON MURRAY

collapsed earlier in its history), the position of the

objects in the tombs, and whether the objects had
:i been affected by water.Young's use of a water-cooled
drilling rig in the initial exploration ofTumulus MM
ra had caused a significant amount of water to enter the
tomb (Young 1957). In addition, Blanchette attrib-
uted the development of soft rot in the log coffin
from Tumulus MM to the earlier presence of water in
the tomb, possibly at the time of its completion
(Blanchette and Simpson 1992).
The fragile state of many of the wooden objects
when
Fig. 2. Plain table 1 on removal from Tumulus MM. White discovered led the archaeologist Rodney
deposits on the surface are evidence of an Alvar coating
Young to seek advice on preservation techniques.
applied while the wood was still damp, hence the blanching
effect. While a few of the most important pieces, including
the inlaid table and two inlaid serving stands from
and Paraloid B-72) from samples of ancient Egyptian Tumulus MM, were treated by immersion in a bath
wood dating to the 12th Dynasty (Hatchfield and of wax dissolved in gasoline, most of the furniture
Koestler 1987). was coated with a dilute solution ofAlvar, a polyvinyl
Over the past 30 years, the deterioration of acetal resin, dissolved in acetone (Spirydowicz 1996;
archaeological wood has been more fully character- Simpson and Spirydowicz 1999) (fig. 2).Young's field
ized. In a comprehensive study of samples of ancient notebooks revealed that members of the field crew as
wood recovered from Egyptian tombs and areas well as the excavation foreman were assigned the task
along the Nile Valley, Blanchette utilized transmission of "painting" the wood with an Alvar solution, an
electron microscopy to reveal stages of decay at the activity that no doubt resulted in many treatment
cellular level as well as to identify biological and variables (Young 1957).Young made it clear that this
chemical agents of degradation (Blanchette et al. method was employed primarily as a first-aid meas-
1994). This followed earlier studies conducted by ure so that the pieces could be removed safely from
Blanchette and others, including an overview of the the royal tombs.
microbial deterioration of wood with reference to When the wood was reexamined in 1981, many
of the pieces previously coated with Alvar were
archaeological samples (Blanchette et al. 1990) and an
examination of the log coffin from Tumulus MM found
at to be in a fragile state (Simpson and Spiry-
Gordion (Blanchette and Simpson 1992). dowicz 1999). In most cases, it appeared that the
solution ofAlvar had not penetrated much below the
3. USE OF ALVAR AND BUTVAR ON surface, so there was little strengthening effect.When
THE WOODEN ARTIFACTS FROM the three-legged banquet tables found in Tumulus
GORDION MM were examined, the only evidence for a previ-
ously applied coating was the presence of whitish or
At the time of excavation, the state ofgrayish patches on of
preservation the deteriorated surfaces of the
the wooden objects from Gordionwalnut
varied
tops,from
possibly due to application of Alvar
while the woodP)
excellent (e.g., boxwood serving stand,Tumulus was
tostill damp. However, on some
poor (e.g., walnut tops of the plain pieces,
tables, suchTumulus
as the serving stand from Tumulus W, the
MM).This range was due to a complexAlvar coating was of
interaction clearly evident and, as such, had
helped to
factors, including the inherent resistance topreserve
decayan essential decorative feature of
of
the individual wood species used, the the
state
piece.of
Duepreser-
to the thickness of the Alvar layer, the
vation of the log tombs (e.g., the structure in decorating
bronze studs Tumu- the front face of this remark-
lus MM was intact and standing when it was able piece of furniture were still in situ when the frag-
discovered, whereas the tomb in Tumulus P had ments were recovered after many years of storage in

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 47

ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL RESINS FOR THE
TREATMENT OF THE WOODEN ARTIFACTS FROM GORDION, TURKEY

immersed in the solution and allowed to absorb the

consolidant. When the wood sank or floated just

below the surface, indicating that most of the air in
the wood had been replaced by the consolidant solu-
tion, the samples were removed and air-dried.
Measurements taken before and after drying
indicated virtually no shrinkage. This finding agreed
with the results previously obtained by Barclay, who,
in fact, found a minimal amount of expansion in test
samples. In comparing treated and untreated portions
of samples, Payton found that there was little color
change. This result was considered desirable for treat-
ment of those pieces of furniture containing inlay
Fig. 3. Fragment of the mosaic table from Tumuluswhere color contrast between woods was an impor-
P with
thick Alvar coating, prior to surface cleaning tant feature of the overall design. Payton judged that
a 5% concentration of Butvar B-98 imparted suffi-
the depot at Gordion. Similarly, fragments cient
of thestrength to the degraded wood, and he
mosaic table from Tumulus P still retained most of proceeded with treatment of the inlaid table (Payton
their pieces of inlay due to the Alvar coating applied
1984a) and the two ornate inlaid serving stands from
by Young's team (fig. 3). It is also worth noting in
Tumulus MM (Payton 1984b).
both cases that the Alvar coating was still clear and Initially, the consolidation process involved
colorless approximately 30 years after application. immersion of the fragments in solution with the
As pieces were prepared for treatment, the previ-gradual application of vacuum pressure via a hand
ously applied Alvar coatings had to be removed. In
vacuum pump to assist penetration of the consolidant
most cases, this proved to be an easy task, as the Alvar
into the interior of the wood. The objects treated by
was readily soluble in acetone. Removal of the thick
Payton were in fairly sound condition, and thus a
film applied to the face of the serving stand from
relatively low percentage of consolidant was effective
Tumulus W was facilitated by the application of gel
in strengthening the wood. In subsequent seasons, it
poultices consisting of Klucel HF in ethanol or an
became obvious that the more degraded pieces, in
ethanol-acetone mixture. Surface cleaning of the particular the furniture and wooden objects from
serving stand from Tumulus W provided clear Tumulus P, required a higher ratio of consolidant to
solvents. In 1991, a second set of consolidation tests
evidence of the continuing solubility of Alvar over
time. Other pieces of furniture had been treated withwas carried out. Small unprovenanced samples of
more dilute solutions of Alvar. In such cases, it was
Gordion wood were consolidated in varying concen-
more difficult to detect whether the resin was trations of Butvar B-98 (10, 12.5, and 15% w/v in
removed from the surface by the cleaning process.
60:40 ethanol and toluene). As a result of these tests
However, it is likely that any further traces of and
Alvar
the scientific studies detailed below, the original
would have dissolved in the solvents used during the
consolidation procedure was modified and refined to
subsequent consolidation process. Althoughsuccessfully
the treat all of the remaining pieces of furni-
manufacture of Alvar by Shawinigan Products ture (Simpson and Spirydowicz 1999).
Corporation was discontinued many years ago, in
4. ALVAR AND BUTVAR: PROPER-
hindsight, the choice of this resin was fortuitous,
TIES AND USES
based on these observations of its behavior over time.

In 1982, Payton consolidated small, unprove-

nanced cubes of wood from the Gordion tumuli Both Alvar and Butvar belong to the family of
with a 5% w/v solution of Butvar B-98 in equal parts
polyvinyl acetal resins that are formed by the reaction
of ethanol and toluene. The wood samples were
between aldehydes and alcohols. In industry, the

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48

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A. BLANCHETTE,

ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF, AND ALISON MURRAY

reaction is carefully controlled to produce a variety

of polymers containing predetermined proportions
of hydroxyl, acetate, and acetal groups (Skeist 1977).
Polyvinyl acetate, polyvinyl alcohol, and polyvinyl
butyral are examples of polymers produced by this
process.
Alvar was obtained by replacing the acetyl radi-
cals in polyvinyl acetate by acetaldehyde. This resin
was widely available in Great Britain and North
America during the 1950s and 1960s. A brief
overview of the uses of Alvar and other polyvinyl
acetal resins in conservation is provided by Horie
(1987). Alvar served conservators as a component of
a widely used gap-filling material for ceramics
known as AJK Dough. In addition, it became ai to
favorite of paleontologists for the consolidation of
fragile fossil material. However, its manufacture
ceased by the mid-to-late 1960s (Howie 1984).
Product literature dating from 1949 describes the
Alvar class of resins as "exceptionally hard and Fig. 4. Scanning electron micrograph of sound boxwood
showing thick-walled fibers and small diameter vessel
tough." Similarly, strength and toughness are cited as
elements.V = vessel, P = parenchyma cell, F = fiber. Trans-
advantages of the polyvinyl butyrals in the literature
verse section. Bar = 50 tim
of a current manufacturer (Solutia Inc. 1999).
Common solvents for the polyvinyl butyrals include ments consisting of small decayed fragments found in
alcohols, glycol ethers, and certain mixtures of polar Tumulus P were used for these studies, which were
and nonpolar solvents. Alvar was soluble in a similar conducted at the University of Minnesota. Each
range of solvents. Payton selected the polyvinyl piece was divided in two, and half was used for
butyral resin Butvar B-98 on the basis of being able consolidation and the other half left untreated.Vary-
to achieve a low viscosity in solution when a solvent ing concentrations of Butvar B-98 in 60:40 ethanol
mixture of ethanol and toluene was employed. Glass and toluene were used to consolidate the samples.
transition temperature may also be an important Consolidation was carried out either by soaking the
factor in choosing a resin for use in hot climates. The samples in solution or using a combination of soak-
glass transition temperature of Butvar B-98 falls ing and application of vacuum pressure. In the first
between 72?C and 78?C, which is well above that of instance, the sample was lowered into solution and
either Paraloid B-72 (40'C) or PVA resins allowed to slowly absorb consolidant until sinking.
The sample
(18-29'C). The high glass transition temperature of was left in the consolidant for 24 hours,
drained, and then wrapped in polyethylene. In the
Butvar B-98 proved particularly advantageous when
the decision was made in later years to employ
second instance, the sample was lowered slowly into
solution, and a vacuum was pulled in 5 cm (Hg)
Butvar B-98 as the primary adhesive in reconstruct-
ing the wooden artifacts from Gordion. increments to 20 cm (Hg). The sample was left in
solution under vacuum for half an hour, and then the
5. EXPERIMENTAL-SCANNING pressure was released. When the sample had been
ELECTRON MICROSCOPE STUDIES immersed in the solution for a total of 24 hours, it
5.1 METHOD was removed, drained, and then wrapped in polyeth-
ylene. After consolidation and drying, samples were
preparedfrag-
Sixteen samples of miscellaneous furniture for scanning electron microscopy using

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 49

ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL RESINS FOR THE
TREATMENT OF THE WOODEN ARTIFACTS FROM GORDION, TURKEY

Fig. 5. Scanning electron micrographs of decayed boxwood furniture fragments from Tumulus P. Fungal attack in t
eroded cell walls, leaving a thin framework of the inner wall layer (middle lamella) left. V = vessel, P = parenchyma
fiber. Transverse sections. Bar = 50 pmn

were
previously described techniques (Blanchette andgreatly compromised as compared to the
Simpson 1992). strength of sound boxwood. In some samples, the
decayed cells were distorted and had collapsed. Many
5.2 RESULTS AND DISCUSSION adjacent cells were compressed together, while cracks
and voids in the cell structure were observed in other

Furniture samples were identified regions.

microscopi-
Samples
cally to be boxwood.This wood in a sound consolidated by soaking or vacuum
condition
has thick-walled fibers and small-diameter vessel infiltration in 10% Butvar showed most cells to have

elements (fig. 4). The untreated samples of furniture

a thin coating of the consolidant adhering to the cell
examined had cells that were severely decayed walls
(fig. (fig. 6). The cell lumina of some fibers were
filled
5). Most of the fiber cells were eroded with only a with consolidant, but vessel elements were
usually not filled with the consolidant.This treatment
fragile, thin cell wall remaining. In a few cells, distinct
cavities were observed within the fiber secondary
appeared to stabilize the thin middle lamella left after
wall, indicating that a soft-rot form of fungal attack
fungal attack by providing a coating on the surfaces
had caused the decay. The decay had progressed
of to
the decayed walls.After consolidation, the anatom-
such an advanced stage that the entire secondaryical
wallstructure of the wood was still distinct, and the
was destroyed in most cells. This type of decay micromorphological
had features of the wood were still
been identified and characterized previously from
intact. Examination at relatively high magnification
the wooden tomb chamber and coffin found in showed many small-diameter fibers were filled with
Tumulus MM (Blanchette and Simpson 1992; consolidant reinforcing these weakened cells (figs. 6b,
Blanchette 1998). The attack on the secondary6d).
wallThe occluded fiber lumina were interspersed
region of the fibers removed the entire thick-walled
with many cells that had consolidant coating the cell
walls.The consolidant that coated cell walls and filled
region, leaving only a thin framework of middle
lamella. The strength properties of this decayedsome
woodof the fibers provided a network of Butvar that

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50

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A. BLANCHETTE,

ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF, AND ALISON MURRAY

Fig. 6. Scanning electron micrographs of decayed furniture fragments from Tumulus P treated by immersion in 10% Butvar
B-98 solution without vacuum (a and b) and with vacuum applied (c and d). The consolidant can be seen filling some of the
fiber cells, but vessel elements are usually not occluded. Cell walls are coated with the consolidant, adding thickness to the
cells. In the fiber regions between vessels, some cell lumina are completely filled with the consolidant, while others have vary-
ing amounts adhering to the cell walls. V = vessel, P = parenchyma cell, F = fiber. Transverse sections. Bar = 50 Lim

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 51

ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL RESINS FOR THE
TREATMENT OF THE WOODEN ARTIFACTS FROM GORDION, TURKEY

Fig. 7. Scanning electron micrographs of severely decayed wood fragments from Gordion with collapsed and compre
walls after consolidation with 10% Butvar B-98 (a) and 12.5% Butvar B-98 (b). Spaces among the compressed fiber c
filled with the consolidant. Cells with larger pores or voids occurring between collapsed regions are coated with th
idant but not filled with the compound. Increased concentration of Butvar B-98 (12.5%) results in more visible am
the consolidant within the tightly packed compressed cells. However, vessel elements and areas with large void
occluded. Transverse sections. Bar = 50 jtm

visible within the crushed lumina of the fibers, but

stabilized the wood. Thus, increased strength and
due to slightly larger pore size, the vessel elements
stability were imparted to the decayed wood without
significant changes to the wood microstructure. usually did not become totally occluded.
The distribution of the consolidant was visible

only after microscopic examination. In samples5.3

of CONCLUSION
decayed wood with cells that had been crushed and
compressed, the consolidant was found to have accu- The results of the study demonstrate that tre
mulated in the small-diameter spaces between
ment of decayed archaeological wood with 1
Butvar B-98 solution can be carried out without
crushed cells (fig. 7a). Greater numbers of cells were
occluded with the consolidant than in other decayed
significantly altering the micromorphological struc-
wood samples where the morphological structure ture
of of the wood. At relatively high magnifications
the wood had been preserved. Severely decayed with microscopic observations, the consolidant can
wood samples treated with a 12.5% Butvar B-98 be seen to coat the cell walls and fill some of the

solution had even greater amounts of consolidant

lumina of small diameter cells. This type of treatment
evident within the crushed and collapsed wood cells
greatly aids the stability of the decayed wood with-
(fig. 7b). In some samples where the integrity of the
out significant changes to the microstructure.
wood had been so greatly compromised that cracks
6. EXPERIMENTAL-NEEDLE
or voids caused it to be in jeopardy of fragmenting
HARDNESS TESTING
into minute pieces, increased concentrations of
consolidant provided greater binding and increased
strength. The increased amounts of consolidant were
In order to quantify the improvement in strength

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52

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A. BLANCHETTE,

ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF, AND ALISON MURRAY

Table 1. Needle Hardness Test Loads and Improvement Due to Consolidation

Specimen No.* B-98 Treatment Load at 2.4 mm penetration, g Improvement, %
Untreated Consolidated

11 10%, vacuum 236 636 169

16 10%, soaking 354 1212 242
17 10%, vacuum 363 486 34
12 10%, soaking 504 890 77
13 10%, vacuum 549 967 76
15 10%, vacuum 599 1158 93
10 10%, vacuum 604 713 18
14 10%, soaking 740 1230 66
18 10%, vacuum 922 2048 122
* Load values are the average of from two to

imparted by the samples while theyButvar

consolidant were being observed
B-98, with
a
hardness test was devised and carried out at the stereoscopic inspection microscope at 10x. The loa
University of California-Berkeley on a series
wasofrecorded continuously. The loads at 2.4, 4.5, an
sample sets of Gordion wood. While strength5.6 mm needle penetration were marked and
improvement is usually characterized by other
recorded. In some cases, the load at the greater depth
means, the small size of the samples precluded theof
usepenetration could not be determined because o
of other methods such as bending tests. splitting of the wood. For samples that were ver
small, the tests were discontinued after 2.4 mm pene
6.1 MATERIAL tration.

6.3 RESULTS
The samples consisted of wood fragments of AND DISCUSSION
irregular shape ranging in size from as little as 4 x 9
x 8 mm to a maximum of 35 x 70 x 115 mm. All the Results are summarized in table 1 for loads at 2.4

wood was selected from pieces belonging to Tumu- mm needle penetration. Strength improvement was
lus P that could not be identified as belonging to aassessed by comparing mean values of the untreated
specific object or piece of furniture. All the samples and treated samples and expressing the change as a
were cut in half using a coping saw with a fine blade. percentage. All the consolidated samples demon-
Half of each sample was set aside to provide a controlstrated a marked improvement in strength varying
while the other half was treated. A 10% w/v solution from 18% to 242%. Due to the small numbers of test
of Butvar B-98 in 60:40 ethanol and toluene was samples available and the large variability of the data,
used to consolidate the samples. The method it
ofwas not possible to draw any additional conclusions
consolidation consisted of simple soaking orasato whether the strength of the wood was improved
by varying the method of application.
combination of soaking and vacuum impregnation.
Considering the heterogeneous structure of
6.2 METHOD wood, and especially of deteriorated wood, it is not
surprising that considerable variability is present.
An Instron table model testing machine was
Load values range from 236 g to 922 g for untreated
samples and
fitted with a Singer sewing machine needle, from 486 g to 2,048 g for the consoli-
style
dated proce-
2020, size 110/18, no. 2085 (4758). The test ones. There was also variation within speci-
mens.
dure consisted of driving the needle into theThe ratio between the lowest and the highest
wood

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 53

ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL RESINS FOR THE
TREATMENT OF THE WOODEN ARTIFACTS FROM GORDION, TURKEY

value ranged from 1.1 to 3.6, with an averagebetween

of 1.9 and within the polymer chains. Infrar
spectroscopy
for all untreated specimens, and from 1.2 to 1.5 with was used to examine the samples f
an average of 1.4 for all consolidated specimens.This
evidence of cross-linking after exposure.The physi
properties
finding indicates that the consolidation treatment has of color, hardness, and solubility we
measured to detect any differences between t
made the specimens more uniform in their proper-
ties. exposed samples and the control group, due
To investigate whether the great range of chemical changes.
improvement values in needle hardness after consol-
idation was related to the variation in hardness values 7.1 MATERIAL
of the untreated samples, the data of table 1 were
listed in ascending order of the hardness loads of the Sixty samples were produced by casting layers of
untreated specimens. As might be expected, there is a 15% w/v solution of Butvar B-98 in 60:40 ethanol
some degree of inverse correlation between hardness and toluene with an average thickness of 0.03 mm
of the untreated specimens and the improvement onto glass microscope slides. The samples were
obtained. The two specimens with the lowest hard-allowed to dry for seven days to ensure complete
ness showed the greatest improvement, and thesolvent loss.

lowest value of improvement is found in the upper

range of hardness before treatment. It can therefore 7.2 CONDITIONS
be concluded that the consolidation treatment

Groups containing six samples each were

effected significant improvement in needle hardness,
with a tendency toward greatest improvementexposed
of the to different environmental conditions for
weakest pieces, and introduced a degree of unifor-
specific amounts of time: (1) a temperature of 650C
mity within specimens. and a relative humidity (RH) of 50% for 25 days; (2)
a temperature of 650C and 50% RH for 50 days; (3)
7. EXPERIMENTAL-EXPOSURE TO long-wave ultraviolet radiation for 20 days (20-25?C
INTENSE ENVIRONMENTAL CON- and 50-60% RH); (4) long-wave ultraviolet radiation
DITIONS for 40 days (20-25?C and 50-60% RH); and (5) dark
storage (20-25'C and 50-60% RH) for the control.
The purpose of this study conducted at Queen's
A Tenny model TH65 Versa Tenn 65 cu. ft. tempera-
ture-humidity
University, Kingston, was to give preliminary infor-environmental chamber was used to
obtain
mation about the aging characteristics of an environment
Butvar B- of 650C and 50% RH. The
long-wave radiation
98 resin (Toutloff 1999). The material properties of was emitted from a 365 nm
Butvar B-98 can be found in the product literature
long-wave ultraviolet bulb.
(Solutia Inc. 1999); for example, the glass transition
7.3 METHODS
temperature (Tg) is stated as 72-78?C. Both chemi-
cal and physical properties were selected for analysis
after the samples were exposed to intenseInfrared
environ-spectroscopy was performed using a
Perkin-Elmer
mental conditions. These conditions included highModel 983G double-beam ratio
temperature at constant relative humidity,
recordingas infrared
the spectrophotometer. The spectra
were recorded
product literature implies that Butvar B-98 may at a nominal resolution of 4 cm-1. A
cross-link upon exposure to heat. Long-wave ultravi-
KBr pellet was made using 1-2 mg of sample scraped
from the
olet light was also chosen as an experimental Butvar B-98 film.
param-
eter because it would introduce energyAinto the
MacBeth Color-1 Colorimeter measured L*
system, which would increase the probability
(lightness), a*of
(green-red) and b* (blue-yellow), using
chemical reactions that might lead to cross-linking
the standard illuminant D (average daylight, 6500%K),

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54

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A. BLANCHETTE,

ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF, AND ALISON MURRAY

Table 2. Color Changes for Butvar B-98 Samples

Value Control 65"C, 50% RH, 65"C, 50% RH, UV 20 days UV 40 days
25 days 50 days
L* 31.42 31.85 32.49 31.33 30.8
a* -0.10 -0.19 0.19 -0.21 -0.22
b* -2.38 -2.03 -2.88 -2.37 -2.17
AE* 0.56 1.62 0.14 0.67

and the overall change

change, which in The
is consistent with the literature. colo
using the equation AE*
average AE* was over 1 only for the samples exposed =
Ab*)2)l"2. to 650C and 50% measuremen
Three RH for 50 days (AE* = 1.62)
sample for each condition.
(table 2). All samples exposed to ultraviolet light had
Hardness AE* less thanmeasured
was 1. by
Shore DurometerThe results from the hardness
A tests show
Type that D
D2240, which uses
Butvar B-98 a
became only slightly pointed
harder after expo-
ment had a sure to intense environmental conditions. Most
constant of
load-o
deadweight of approximately
the samples showed an increase in hardness of 1 unit
urements were taken from three different areas on (from 15 units), which is very small. There were only
three samples for each condition, for a total of ninetwo exceptions where one of the three areas on the
measurements. samples had an increase of 2 units. These samples had
been exposed
Two methods were used to test for solubility. Theto intense environmental conditions
first involved placing samples in 60:40
forethanol and
the longer times (50 days at 650C and 50% RH,
toluene solvent mixtures. As all samples
and 40dissolved
days of ultraviolet radiation).
The
immediately, a second method was used. A firstthat
swab solubility test demonstrated that the
was saturated with the same solvent mixture was films were extremely soluble in the solvent mixture
and could be considered reversible. The second
passed over the film until the film completely
dissolved. The number of passes was counted. method
The using solvent-saturated cotton swabs showed
experiment was carried out by one person, in that
as samples exposed to 650C and 50% RH for 50
consistent a manner as possible. The measurement
days required 15 passes and were therefore the least
was made twice for each condition. soluble; samples exposed to ultraviolet radiation for
20 days required 13 passes; samples exposed to ultra-
7.4 RESULTS AND DISCUSSION violet radiation for 40 days required 12 passes;
samples exposed to 650C and 50% RH for 25 days
The IR spectra showed little difference before
required 8 passes; and the control required 9 passes.
and after exposure to the intense environments, indi-
7.5
cating that there were no substantial CONCLUSION
chemical
changes. No new peaks appeared after exposure that
would indicate the formation of new bonds due to
The results from the infrared analysis taken i
conjunction with the results of the physical te
cross-linking. A minor change occurred around 1106
indicate that the Butvar B-98 resin film remained
cm-1 and 1138 cm-1 in the samples exposed to high
fairly stable under the intense environmental condi-
heat and humidity for 50 days, most probably indi-
tions of the experiment. The group that showed the
cating absorption of -OH groups due to water from
the humid conditions. most change in all cases was the set exposed to a
Color change was not apparent to the naked eye. temperature of 650C and 50% RH for 50 days.These
The measurements showed that there was minimal results concur with the product literature, which

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 55

ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL RESINS FOR THE
TREATMENT OF THE WOODEN ARTIFACTS FROM GORDION, TURKEY

suggests that the polyvinyl butyral resin may cross-

Queen's University, with regard to the Fourier tran
link upon exposure to heat. Although neither cross-
form infrared spectroscopy is gratefully acknow
edged.
linking nor any other drastic chemical changes were
detected by infrared spectrometry, some changes may
have occurred in the chemical structure of the REFERENCES
Butvar B-98 resin to produce the differences in the
Barclay, R. 1981. Wood consolidation on an eig
results of the physical tests between the sample sets
and the control group.The results show that the resin
teenth century English fire engine. Studies in Conser
vation 26(4):133-39.
underwent only minor changes under the relatively
extreme environmental parameters of the study.
Blanchette, R. A. 1998. A guide to wood deterior
8. CONCLUSION-USE OF BUTVAR tion caused by microorganisms and insects. In T
B-98 AS AN APPROPRIATE CON- structural conservation of panel paintings, ed. K. Dard
SOLIDANT FOR DRY ARCHAEO- and A. Rothe. Los Angeles: Getty Conservation Ins
LOGICAL WOOD tute. 55-68.

The treatment of the Gordion wooden objects

Blanchette, R. is
A., J. E. Haight, R. T. J. Koestler, P B.
now complete (Simpson and Spirydowicz 1999).
Hatchfield, and D. Arnold. 1994. Assessment of dete-
Four of the most ornate pieces of furniture have
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on display
of theat
American Institute for Conservation
the Museum ofAnatolian Civilizations in Ankara. All 33:55-70.

of the remaining wooden objects in the collection

have been repaired and placed in protective storage Blanchette, R. A., T. Nilsson, G. Daniel, and A. Abad.
in the museum.
1990. Biological degradation of wood. In Archaeolog-
The results of scanning electron microscopy
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studies have shown that the use of a 10% w/v solu- M. Rowell and R.J. Barbour. Advances in Chemistry
tion of Butvar B-98 is effective in coating cell walls series 225. Washington, D.C.: American Chemical
and thus significantly improving the stability of Society. 141-74.
severely degraded wood. Needle hardness testing has
demonstrated a marked increase in strength in a Blanchette, R. A., and E. Simpson. 1992. Soft rot and
limited number of test samples. Exposure of films of wood pseudomorphs in an ancient coffin (700 Bc)
Butvar B-98 to intense environmental conditions has from Tumulus MM at Gordion, Turkey. International
indicated that the resin is able to withstand harsh test Association of Wood Anatomists Bulletin 13:201-13.
conditions with few chemical changes occurring. In
the opinion of the authors, the use of Butvar B-98 as Carlson, S., and A. P Schniewind. 1990. Residual
an effective consolidant for the treatment of ancient solvents in wood-consolidant composites. Studies in
wooden artifacts has been demonstrated. The useful Conservation 35:26-32.

properties of polyvinyl butyral resins, including

strength, low viscosity, and versatility, have led to their Grattan, D. W. 1980. Consolidants for degraded and
acceptance as a standard treatment for the conserva- damaged wood. In Proceedings of the Furniture and
tion of dry archaeological wood. Wooden Objects Symposium. Ottawa: Canadian
Conservation Institute. 27-42.
ACKNOWLEDGEMENTS
Hatchfield, P. B., and R. J. Koestler. 1987. Scanning
The contribution of Dr. H. E Shurvell, Professor
electron microscopic examination of archaeological
Emeritus in the Department of Chemistry at altered by consolidation treatments.
wood structure

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56

KRYSIA E. SPIRYDOWICZ, ELIZABETH SIMPSON, ROBERT A. BLANCHETTE,

ARNO P. SCHNIEWIND, MAURAY K. TOUTLOFF, AND ALISON MURRAY

Scanning Microscopy 1(3):1059-69. Conservation 33:247-55.

Horie, C. V. 1987. Materials for conservation. Oxford:

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Howie, E M. P. 1984. Materials used for conserving
fossil specimens since 1930:A review. In AdhesivesSimpson,
and E., and K. Spirydowicz. 1999. Gordion
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national Institute for Conservation of Historic and tion of the furniture and wooden objects from Gordion,
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Payton, R. E. 1984a. The conservation of an eighth

century BC table from Gordion. In Adhesives and
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Wang, Y., and A. P Schniewind. 1985. Consolidation

Payton, R. E. 1984b. The conservation of screensof
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Schaffer, E. 1971. Consolidation of softwood arti-
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KRYSIA E. SPIRYDOWICZ is associate professor
in the Art Conservation Program, Queen's Univer-
Schaffer, E. 1974. Consolidation of painted wooden
artifacts. Studies in Conservation 19(4):212-21. sity, Kingston, Ontario, Canada. From 1979 to 1985,
she held the position of coordinator of the Art
Conservation Techniques Program at Sir Sandford
Schniewind, A. P., and P.Y. Eastman. 1994. Consoli-
dant distribution in deteriorated wood treated with Fleming College, Peterborough, Ontario. Her
soluble resins. Journal of the American Institute forresearch interests include the conservation of

JAIC 40 (2001):43-57

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 57

ALVAR AND BUTVAR: THE USE OF POLYVINYL ACETAL RESINS FOR THE
TREATMENT OF THE WOODEN ARTIFACTS FROM GORDION, TURKEY

facts
wooden artifacts and archaeological materials. in 1982, and has been a member of AIC since
Ms.
Spirydowicz has participated in numerous interna-
1984. He has recently been working on a book on
conservation
tional projects in Italy, Israel, the Sudan, and Iran. of wood artifacts together with a
Since 1990, she has held the position of senior
husband-and-wife team in Germany. Address:
conservator for the Gordion Furniture Project, based
University of California, Forest Products Laboratory,
1301 South 46th St., Richmond, Calif. 94804-4698
at the Museum of Anatolian Civilizations in Ankara,
Turkey. Address: Art Conservation Program, Queen's
MAURAY K. TOUTLOFF received her B.Sc. in
University, Kingston, Ontario K7L 3N6, Canada
biology from the University of Regina in
ELIZABETH SIMPSON, Ph.D., is associate profes-
Saskatchewan in 1996, and her M.A.C. from Queen's
sor ofAncient Art with the Bard Graduate Center for
University in 1999. She is currently working as a
Studies in the Decorative Arts in NewYork. Inprivate
1981, conservator in Victoria, British Columbia.
Address:
she established the Gordion Furniture Project for the 125 Kingston St.,Victoria, British Colum-
bia,V8V
purposes of conservation, research, and publication of1V3, Canada
the royal wooden furniture from Gordion, Turkey. As
ALISON MURRAY is assistant professor in the Art
director of the project, she has published extensively
on the subjects of Phrygian furniture and ancient
Conservation Program at Queen's University,
Kingston,
woodworking technology. In 1995, she organized an Ontario. She received her honors B.Sc. in
important international conference to discusschemistry
issues from McGill University and her M.Sc. and
surrounding the restitution of cultural property
Ph.D. degrees in materials science and engineering
looted during World War II, and she subsequently
with a specialization in conservation science from a
edited the volume of conference papers entitled
joint program between Johns Hopkins University
Spoils of War. Address: Bard Graduate Center
and for
the Smithsonian Institution. She has held fellow-
Studies in the Decorative Arts, 18 West 86th Street,
ships at the Analytical Research Services Division,
NewYork, N.Y. 10024 Canadian Conservation Institute, and in the Scien-
tific Department, National Gallery, London, the latter
ROBERT A. BLANCHETTE, Ph.D., is a professor
funded by the Samuel H. Kress Foundation. Her
in the Department of Plant Pathology at the Univer-
areas of research include the investigation of degra-
sity of Minnesota. His research activities ondation
wood in art objects using microscopy, nondestruc-
microbiology and biodeterioration have focused on
tive methods, and other analytical techniques, as well
as the identification of artists' materials and tech-
elucidating degradation processes in archaeological
wood from different environments. His most recent niques. Address as for Spirydowicz
work involves an assessment of biodeterioration in
extreme environments, ranging from the historic
huts of the Ross Sea Region of Antarctica to the Received for review February 2, 2000. Revised
buried tomb within Tumulus MM at Gordion, manuscript received June 14, 2000. Accepted for
Turkey. Address: Department of Plant Pathology, publication August 10, 2000.
1991 Upper Buford Circle, 495 Borlaug Hall,
University of Minnesota, St. Paul, Minn. 55108-
6030. E-mail: robertb@puccini.crl.umn.edu

ARNO P. SCHNIEWIND is Professor of Forestry,

Emeritus, and has been associated with the Forest
Products Laboratory of the University of California
since 1956. He became interested in the application
of wood science to the conservation of wood arti-

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