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JAIC 1998, Volume 37, Number 1, Article 6 (pp.

69 to 87)

FILLS FOR WHITE MARBLE: PROPERTIES OF


SEVEN FILLERS AND TWO THERMOSETTING
RESINS
ELEONORA E. NAGY

ABSTRACT—The purpose of this article is to evaluate thermosetting resin-based fills


for compensation of white marble and similar stones in the outdoor environment. The
article describes seven commercially available fillers, tested in two thermosetting resin
formulations for structural fill on dense, whitish, translucent marble and similar
calcerous stones.The influence of the concentration, color, refractive index, density,
particle size and shape, and microstructure of each filler on the color, translucency,
texture, density, elasticity, plasticity, reversibility, water sensitivity, and working
properties of their composites will be described. A total of 187 samples were tested for
density, water absorption, color, and stress-strain at break. Results of the tests show
that fillers, when used in high concentration, will significantly influence the visual and
mechanical properties of composites. The properties of glass microballoons
(Microspheres and Eccospheres), marble dust, and Globe-o-sil fillers were found to be
preferable to those of calcium carbonate, mica, and Cab-o-sil fillers. The most
promising results were obtained using the hollow, glass sphere fillers (Microspheres,
Eccospheres) in a Sikadur epoxy resin-to-filler w/v concentration range of 1–30%.

TITRE—Produits de restauration pour le marbre blanc: Les proprietes de sept


produits, de reparation et de deux resines thermodurcissables. RÉSUMÉ—Le but de
cet article est d'évaluer les matériaux de réparation thermodurcissables à base de résine
pour compense les pertes sur le marbre blanc et sur des pierres similaires restant à
l'extérieur. Cette étude décrit sept produits disponibles sur le marché commercial,
testés dans deux formules de résines thermodurcissables pour les réparations
structurelles des marbres blanchâtres et translucides denses et des pierres
calcareuses.L'influence de la concentration de la couleur, de l'indice de réfraction, de
la densité, de la taille et de la forme des particules et de la microstructure de chaque
produit sur la couleur, la translucidité, la texture, la densité, l'élasticité, la plasticité, la
réversibilité, la sensibilité à l'eau et leurs propriétés actives seront décrits. Un total de
187 échantillons ont été testés pour mesurer la densité, l'absorption de l'eau, la couleur
et la tolérance à la cassure. Les résultats du test montrent que ces produits de
réparation, utilisé à haute concentration, influenceront, d'une manière très marquée, les
propriétés visuelles et mécaniques des composés. Les propriétés des produits de
restauration de microballons en verre (Microsphères et Eccosphères), de la poussière
de marbre et de Globe-o-sil étaient préférables à ceux de calcium carbonate, du mica
et du Cab-o-sil. Les résultats les plus prometteurs furent obtenus avec les sphères
creuses en verre (Microsphères, Eccosphères) dans une résine époxyde Sikadur une
p/v d'une concentration de l'ordre de 1 à 30%.

TITULO—Materiales para relleno faltantes de mármol blanco: Caracteristicas de siete


llenadores y dos resinas de termosetting. RESUMEN—La intención de este papel es
evaluar rellenos basadas de resinas termosetting por compensación de mármol blanco
y piedras similares al aire libre. El papel describe siete llenadores disponibles
comercialmentes, probaron en dos formulaciones de la resina del termosetting por
relleno estructural en denso, blanquecino, mármol translúcido y piedras similares del
calcáreo.La influencia de la concentración, color, índice de refracción, densidad,
dimensiones y forma de la partícula, y microstructura de cada relleno en el color,
translucidad, textura, densidad, elasticidad, plasticidad, revocabilidad, susceptibilidad
del agua, y se describirán propiedades del funcionamiento de sus compuestas. Un
número total de 167 muestras se probaron por densidad, absorción del agua, color, y
fuerza-tensión a rotura. Los resultados de las pruebas muestran que llenadores, cuando
se usan en concentración alta, influirá las propiedades visuales y mecánicas de
compuestas significativamente. Las propiedades de micro-globos del vidrio
(Microspheres y Eccospheres), polvo del mármol y Globe-o-sil se encontraron ser
preferible a aquéllos llenadores de carbonato del calcio, mica, y Cab-o-sil. Los
resultados más prometedores se lograron usando los vacios, llenadores de la esfera del
vidrio (Microspheres, Eccospheres) en un Sikadur resina-a-llenador del epoxy p/v
esfera de la concentración de 1–30%

1 INTRODUCTION

1.1 SELECTION OF PROPERTIES AND METHODS FOR TESTING

Fillers have been used primarily as extenders, and the full range of their benefits has
not been extensively explored. This article investigates how properties of fillers such
as shape, size, color, microstructure, density, and translucency affect the appearance
(color, texture, translucency) and physical properties (density, hardness, elasticity,
plasticity, mechanical reversibility, water sensitivity) of their composites. The
evaluation of these properties is addressed for fills intended to compensate white
translucent marble or similar stones (alabaster, limestones) in the outdoor
environment. It is hoped that the conclusions of this study will provide some guidance
for the use of fillers in sculpture and architectural conservation.

To determine important parameters and testing methods in relation to optimal fills for
whitish translucent calcareous stones exposed to the outdoor environment, the
following properties are considered: density, water sensitivity, color, refractive index,
elasticity, and plasticity.

Three kinds of samples were used: prepared composite samples with various fillers;
two different pure thermosetting resins; and natural marble samples. The latter two
were used as controls. Testing methods listed below were carried out on a total of 187
samples.
1.1.1 Density

The density of a fill should be close to or less than that of the original material. This
density permits reversibility of the fill by mechanical means and has a potentially
faster rate of deterioration than the original stone. A possible direct correlation
between the density of the filler and its resulting composite was also investigated.

1.1.2 Water Sensitivity

The water absorption and drying rate of a fill should be close to that of the object, so
that a wet fill does not introduce moisture and therefore potential decay in the original
stone. A fill should also follow the changing hues of the wet-dry cycle of the object.
Although a 48-hour water immersion test is extreme relative to normal ambient
external conditions on stone surfaces, such a test will indicate comparative wetting and
drying patterns of stones and fills. Considering time restrictions and the relatively
small size and number of samples in this study, immersion may also draw attention to
possible long-term weathering effects sooner than a capillary rise procedure.

1.1.3 Color and Texture

An acceptable color and texture match between the fill and the surrounding stone is an
important requirement for camouflaged stone repairs. Evaluation of texture was
accomplished empirically. Color matching was rated by both empirical and
instrumental methods.

1.1.4 Refractive Index

Translucency is one of the most difficult requirements when matching white marble.
On translucent stones, the factor that determines the appearance of a crack, gap, or
filled lacuna is the difference in refractive index (RI) between the original stone and
its fill. A material has only one RI if the physical properties of its particles are the
same in every direction (isotropic). When the RI of an isotropic material matches that
of the surroundings, the material is described as transparent. Anisotropic materials
have more than one RI (birefringence) and are often indicated by average refractive
indices. With the exception of the Microsphere and Eccosphere fillers, which are
isotropic crystals, the fillers used in this experiment are not uniform crystals and have
more than one refractive index.
1.1.5 Elastic and Plastic Behavior

A fill should allow expansion and contraction of the repaired stone without damaging
the original material, thereby making the fill mechanically reversible. Should both
materials be exposed to the same range of strain (deformation) and stress (compressive
force), once the force is released, the fill may show some signs of permanent plastic
deformation sooner (enter its plastic deformation range at lesser stress) than does the
stone, which would still return fully to its original state (elastic deformation). To
assess elastic and plastic behavior, each composite and control was tested for
compressive strength and percent strain at break. Composites were sought that
exhibited lower compressive strength and similar or greater strain at break (“longer”
performance in the plastic region) as compared to the original stone (i.e., natural
marble).

1.2 SELECTION OF MATERIALS AND THEIR COMBINATION

Thermosetting resins have considerably greater strength and hardness than other resins
used in conservation, making their use for structural repairs of stone very common
(Larson 1978; Domaslowski 1988; Barclay and Mathias 1989; Nagy 1991; Naudé
1991; Domaslowski 1995; Technology Organization 1995;). This was the primary
factor for testing thermosetting resins here. Two stone adhesives, Sikadur 35 Hi-Mod
LV epoxy and Akemi Marmorkitt 1000 Transparent/Clear Flowing polyester resins,
were chosen for testing. Both were developed for exterior use and are widely used in
architectural and sculpture conservation.

Seven fillers—calcium carbonate, Cab-o-sil, mica, marble dust, Globe-o-sil,


Microspheres, and Eccospheres—were chosen because they are white or translucent
and are inert. Both resins were combined with each of the seven fillers, and each resin
was mixed with a filler in 3, 4, or 5 different concentrations. These composite
concentrations are listed in tables 1–4, where each concentration represents the mean
of 3–5 samples. To the total number of 173 composite samples, add 8 natural marble
specimens (4 fresh and 4 decayed) and 6 pure resin samples (3 of each resin) that were
used as controls, making the total number of samples used in this study 187.

TABLE 1. EFFECT OF FILLERS ON THE DENSITY OF RESINS

TABLE 2. PERCENTAGE OF WATER ABSORPTION AND DRYING RATE

TABLE 3. AVERAGE CIELAB MEASUREMENTS

TABLE 4. EFFECT OF FILLERS ON THE COMPRESSIVE STRENGTH OF THE


PURE RESIN

Pigments, typically used as coloring agents, may be considered as fillers when used in
large volumes. However, the investigation of pigments as fillers is not included in this
article.

2 MATERIALS AND SAMPLE PREPARATION

2.1 SOURCES OF MATERIALS AND THEIR DATA

Materials were provided directly by their manufacturers. Fresh natural calcite marble
and marble dust were obtained from a commercial distributor (see Sources of
Materials). The decayed marble originated from a broken gravestone.

Particle sizes for each material were measured by the author. Refractive indices for the
two thermosetting resins were kindly provided by Christopher W. McGlinchey. All
other information was obtained through literature or communication with the
manufacturer.

Sikadur 35, Hi-Mod LV—A two-component, solvent-free, very low viscosity (375
centipoise [cps]), high-strength, multipurpose epoxy resin adhesive. It has a clear
amber color and a pot life of about 25–30 minutes. The full cure of the resin is close to
complete in 72 hours but absolutely complete only in 7 days. The resin-to-hardener
mixing ratio is 2:1. The RI of the cured resin is 1.567.

Akemi Marmorkitt 1000/Akemi Marble Filler 1000 Transparent/Clear Flowing—A


water-clear, 680 cps viscosity, two-component polyester adhesive, specifically
produced as an adhesive for stone (“for Carrara marble, Ajax, Onyx translucent, and
Greek Thassos marble”). It has a pot life of approximately 7–10 minutes and a full
cure time of 48 hours (Akemi Plastics 1988). The resin-to-hardener mixing ratio is
100:3, and the cured resin has an RI of 1.525.

Calcium Carbonate (Marble-fil) 151C—A white, low-cost, high-loading filler. This


precipitated type of calcium carbonate has the finest and most uniform particle size of
all the fillers that were tested. The diameter of the anisotropic, rounded hexagonal,
rhombohedral particles is between 0.5–1.5 microns (μ). The RI is between 1.47 to 1.69
(mean 1.66), loose density 2.0 g/cm3.

Cab-o-sil (fumed silica)—An anisotropic, white, extremely lightweight filler


containing 99.9% silicon dioxide. It is practically free of contaminating metallic salts.
The rounded, rough-surfaced agglomerates range from 0.5–120μ in size, the average
being ca. 40μ. The mean RI is 1.54 (1.47–74), loose density 0.03 g/cm3.

Wet-ground Mica 160—A grayish brown mineral additive (H2KAl3[SiO4]3) with a


solid, delaminated, rounded rectangular, transparent flake structure. The average flake
size is 6–10μ. The smallest flakes are 1μ; the largest particles are 30μ in diameter. The
birefringent particles have refractive indices of 1.552, 1.582, and 1.588. The loose
density is approximately 0.3 g/cm3.

Marble Dust—One of the most popular resin additives for marble fills. The average
size of the block-shaped particles is about 250μ, with a large particle size distribution
ranging from approximately 20 to 800μ. The average RI of the birefringent particles is
1.65. Loose density 1.65 g/cm3.

Globe-o-sil G—Has a white granular appearance. The neutral pH, low-density


additive contains 71–75% silicon dioxide. The foamed particles (1–80μ) enclose cells
that are separated by thin, glassy membranes. When mixed with resins, the enclosed
air is held and sealed within the glassy membranes. The anisotropic particles tend to
form lumps (ca. 60μ) that make up the average size particles. The mean RI is 1.45,
loose density 0.11 g/cm3.

Microspheres 409—A brand name for glass microballoons, which are hollow sodium
borosilicate microspheres with a white powdery appearance. The particle size is 1–
140μ, with an average of 50μ. The product contains some broken particles and
impurities. The particles are isotropic, and the RI is 1.52. The loose density is 0.09
g/cm3.

Eccospheres IG 101—Hollow sodium borosilicate glass spheres from 5–150μ in


diameter. The average size of this type of glass microballon is 55μ. The RI of the
isotropic spheres is 1.52. The loose density of Eccospheres is 0.17 g/cm3. The major
difference between Microspheres and Eccospheres filler is that the latter is a more
refined product and does not contain broken spheres or impurities. (Note that some
birefringence is present in both Microspheres and Eccospheres due to the enclosed air
in the hollow spheres.)

Fresh Natural Marble Specimens and Decayed Marble Specimens (4 each)—Used as


a control for the duration of the tests. X-ray diffraction of the fresh natural marble
specimen was performed at the Miller Museum of Geology (Badham 1991), and the
results matched the mineral calcite almost perfectly. Both fresh and decayed marble
specimens had a whitish color with very faint grayish veins. The decayed marble had a
sugary, slightly discolored, grayish crust formation from outdoor exposure
(approximately 1/8 in. thick) on the surface of the stone.

2.2 SAMPLE PREPARATION

All natural marble samples and controls were cut and prepared by the author. For
marble dust, a piece of the fresh calcite marble was crushed using a Jaw Crusher
(Braun Chipmunk VD67) and a Bico Pulverizer (disk mill by Bico, Inc.) at the
Geology Department of Queen's University, Kingston, Canada.

Composites and pure resin samples were made using a Plexiglas lattice open at the
bottom and the top. Components of the resins were mixed according to the
manufacturer's instructions. Then the filler was added, and the mixture was poured or
pressed into the cells of the lattice. Renaissance microcrystalline wax was used as a
separating agent. Samples for a given concentration were usually made in a single
batch. The samples were left to cure for one week, then pressed out from the lattice by
hand.

The surfaces of the samples were sanded using 80 and 120 carat electroplated
finishing sandpaper. The only exception was the sugary crust on the decayed marble.
This weathered surface was not sanded and was used later for test purposes. The final
size of all samples tested was 25.4 × 50.8 × 14.3 mm (1 × 2 × 9/16 in.).

Unexpected mixing difficulties with a number of fillers occasionally resulted in


slightly different filler-to-resin concentrations. These concentrations remained fairly
similar and are still comparable.

Materials for composites and controls were stored in a laboratory environment for 14
days at 73 ± 4°F (23 ± 2°C) at 50% ± 2 relative humidity before sample preparation.
The samples remained in these conditions for the duration of the tests.

Samples are described as weight-volume percent (w/v): weight of resin (gram)/volume


of filler (ml) × 100. A low percentage concentration indicates small amount of resin
with a large amount of filler in the composite. Each datum provided is the mean of a
minimum of three readings for each of the three samples.

3 RESULTS

3.1 WORKING PROPERTIES OF THE MATERIALS TESTED

Both adhesives exhibited color change during mixing and curing. The “clear amber”
pure Sikadur resin turned pink immediately upon mixing, pure Akemi turned greenish.
As the curing proceeded the pure Sikadur gradually changed to a clear amber and the
Akemi resin to a cool clear white hue, indicating that they were close to setting.

None of the fillers appeared to affect the setting time of the resins. Noticeable
shrinkage of about 1 mm in length (longitudinal direction) occurred with all three pure
Akemi samples.

Mixtures of approximately 40% concentration (40% resin content) or greater had


properties of very viscous fluids for all samples. At about 30% concentration or less,
two characteristic types of behavior were noted:

1. Calcium carbonate, mica, and Cab-o-sil composites provided a barely


kneadable paste and resulted in heterogeneous mixtures. These fillers appeared
to “drink up” the resin and the lowest concentration that could be achieved
with them was around 20% (20% resin content). At lower concentrations
kneading became impossible and the mixtures did not set. Perhaps one
component of the two-part resin mixture was preferentially absorbed by these
three fillers, making the particles extremely hard and conglomerate. Also, the
remains of the absorbed component may have induced an accelerated setting of
the resin before the particles could be completely mixed in. Mixtures of these
materials yielded significantly smaller volumes than expected from the
volumes of resin and filler added.
2. Conversely, Globe-o-sil, Microspheres, and Eccospheres fillers were easy to
mix and yielded composites as low as 1.0% (1.0% resin content) concentration,
although, at approximately 10–15% concentration the composites started to fall
apart like bread crumbs and appeared too dry to mix. However, with continued
mixing and kneading by hand, this crumbling texture was overcome, and
further amounts of filler could even be added to the resins. They remained
easily kneadable and cured properly afterward. Mixing large volumes of these
fillers into the resin was found to be easiest using Zip-loc plastic bags. The bag
was filled with the premeasured filler, the thoroughly premixed resin was
poured in, and the bag was sealed. Kneading the putty in this manner helped to
contain the fine airborne particles and provided better distribution of the resin.

Marble dust did not strictly conform to either type of behavior, but it seemed to
behave more similarly to the second group of fillers.

The large difference in the resin-to-hardener ratio (100:3) of the Akemi polyester resin
required more precision in mixing and resulted in increased preparation error as
compared to the Sikadur resin. The 7–10 minutes pot life of the Akemi resin was
found to be too short for uniform distribution of high filler content in the resin. These
mixing difficulties were more relevant when used with the “difficult fillers,” calcium
carbonate, mica, and Cab-o-sil. Stratification of resin concentration in the mixtures
during or after preparation was not noticed in this study. This fact may be due to
several factors, such as the use of relatively filler-rich mixtures, a resin viscosity not
low enough to easily flow in response to gravity, the relatively fast pot life of the
resins, the specific attention paid to proper mixing, or a combination of all these
factors. Although there was an empirically noticeable difference between the
viscosities of the two resins used in the experiment, the viscosity of the pure resin did
not seem to influence the working properties of the mixtures.
3.2 VISUAL OBSERVATIONS

The generally white or off-white fillers yielded a range of colors in the composites,
from brilliant white to yellow, gray, and brown. Composites of Microspheres and
Eccospheres were the whitest samples after curing. Some of these samples looked
whiter than the natural stone controls. Cab-o-sil yielded bluish green composites in
Akemi and yellow in Sikadur resin. Marble dust and Globe-o-sil appeared slightly
gray in both resins, the latter being more distinct. Calcium carbonate was beige and
mica distinctly brown in both resins. None of the calcium carbonate, Cab-o-sil, or
mica samples exhibited any resemblance to white marble. The color of the composite
was determined by the color and concentration of the filler. The color of the resin had
a negligible influence. Only in cases of approximately 30–40% or higher
concentration did the color of the resin become significant. In these resin-rich
mixtures the amber color of the epoxy resin added a slight warm hue, while the clear
transparent Akemi resin tended to modify the color of the composites to a cool blue-
green tint. This was especially obvious for the samples made with Cab-o-sil and
marble dust.

Fillers with only one refractive index, which matches the RI of the resin, were the
most transparent. As glasses and isotropic crystals satisfied this condition, composites
of Microspheres and Eccospheres resembled the most translucent white marble. The
rest of the fillers were not uniform crystals, so the result was generally one of graying
when the average refractive index was close to that of the resin. The greater the RI
difference between the filler and the resin, the greater the opacity of the composite
became. Samples with an RI difference of only 0.05 between an isotropic filler and the
resin exhibited increased transparency, when samples were observed side-by-side with
the naked eye. Around this value, the isotropic filler/resin composites compared very
favorably to the translucency of the natural marble specimens. This was the case with
all glass microballoon (Microspheres and Eccospheres) samples. Anisotropic fillers,
however, were very opaque—even well below this 0.05 RI difference. For example,
the mean RI of mica filler had only an 0.003 RI difference in combination with
Sikadur resin but was distinctly opaque due to the filler's birefringent nature.
Consequently, although natural marble and limestones do contain mica and calcium
carbonate, composites of these birefringent constituents do not produce translucent
fills for stone.

With filler-rich samples (below 30% resin concentration) the texture of the composite
was most similar to marble when the particle size and shape of the filler was closest to
the grain of the stone. The filler-rich composites of Microspheres and Eccospheres
most resembled white marble; these were followed by the samples made with marble
dust. The Globe-o-sil composites resembled the decayed “sugary” marble surface. The
calcium carbonate, mica, and Cab-o-sil samples, all materials with small particle sizes,
had an artificially smooth, densely packed, and dull opaque appearance resembling a
plastic substance rather than natural stone.
3.3 DENSITY

Values obtained for density are shown in table 1. The influence of the fillers on the
density of the composites was the same in both resins. Calcium carbonate, Cab-o-sil,
mica, and marble dust fillers increased the density of the samples. Globe-o-sil,
Microspheres, and Eccospheres radically decreased the density of the samples. (Some
composites of these fillers had densities so low that they floated on water.)

The density of the filler did not seem to be strictly related to the density of the
resulting composite. For example, the extremely low-density Cab-o-sil filler increased
the density of the samples, and they sank immediately when immersed in water. Ball-
shaped or rounded filler with air content in the particles decreased the density of the
composite.

3.4 WATER ABSORPTION

As seen in table 2, a large number of Akemi resin-based composites disintegrated or


were damaged by water during the absorption test. Akemi/Microspheres (6%, 20%,
26%) and Eccospheres (6%, 35%) samples swelled, melted like ice cream, and
disintegrated immediately after immersion. Five to 10 minutes after immersion, other
Akemi/Microspheres and Eccospheres samples of slightly greater concentration
produced less severe but similar reactions. The rate of disintegration slowed with
increasing amount of resin in the sample. The 23% Akemi with mica sample was also
damaged by water. In particular, the corners of the sample became lighter in color and
crumbly. Some of the Akemi/marble dust samples became slightly spotty after drying.
It should be noted that pure Akemi resin did not show signs of damage by water
immersion, and the manufacturer did not indicate the resin's instability in water. Pure
Sikadur resin, or its composites comparable to those of the disintegrated Akemi-based
samples, did not show any signs of damage by water immersion.

The percentage weight gain of the samples, as compared to their original dry weight,
is shown in table 2. As expected, the composites showed the greatest absorption of
water, followed by the decayed marble, fresh marble specimens, and the pure resin
samples.

The drying rate of the samples is indicated in columns 4–10 of table 2. Dramatic
moisture loss for all samples occurred within the first 6 hours of drying. Pure Sikadur
epoxy samples dried the fastest (6 hours). The two types of natural marble specimens
returned to their original dry weight in 6–12 hours. These were followed by the pure
Akemi polyester samples, which dried in 26 hours. All composites took longer to dry
than the stone samples, and some retained a small amount of moisture for 72 hours.

In terms of the drying rate of the composites, two groups could be established.
1. Samples containing calcium carbonate, Cab-o-sil, and mica dried within 26
hours. Marble dust composites returned to dry state shortly thereafter (within
36 hours).
2. Globe-o-sil-, Microspheres-, and Eccospheres-filled composites belonged to
the slower drying group. After the first 6 hours of dramatic moisture loss,
which followed the pattern of natural stones, these composites retained a small
amount of water until about 72 hours after immersion.

3.5 COLORIMETRY

Table 3 illustrates the mean of the readings displayed on the colorimeter. The L∗
readings show that the two pure resins were the darkest of the samples; the difference
between Akemi and Sikadur was subtle though visually perceptible. The Akemi resin
was somewhat on the coolish, blue-green side, and the Sikadur resin was on the
warmer side. The pure resin samples were significantly darker than both the fresh and
decayed natural stone samples. The fresh marble sample was slightly lighter and less
yellow than the decayed marble sample.

Increased concentrations of fillers increased the lightness (L∗) of the composites. The
degree of this increase in lightness could be divided into two groups.

1. The addition of calcium carbonate, Cab-o-sil, Globe-o-sil, and mica did not
lighten the mixtures significantly even when added in large volumes. Calcium
carbonate yielded beige and mica brown color in their composites. Cab-o-sil
was consistently bluish with Akemi and yellowish with Sikadur.
2. The addition of marble dust, Microspheres, and Eccospheres fillers
significantly lightened the composites. For example, 67% concentration of
Sikadur/Microspheres composite (very small amount of fillers) showed
variations of a∗ and b∗ values.

As shown in the last column of table 3, all wet natural marble controls darkened about
10% compared to their dry state. The wet composites decreased in lightness only 0–
5%. Varying the concentrations of a filler did not seem to have any decreasing effect
on the L∗ values of a wet sample. This decrease appeared to be filler-specific and not
concentration-specific for a composite.

3.6 COMPRESSIVE STRENGTH

As seen in table 4, the range of values obtained for compressive strength was
approximately 100 to 17,000 pounds per square inch (psi).

Both pure resin samples had significantly greater compressive strengths


(approximately 11,000–17,000 psi) than any of the marble controls tested (4,000 and
10,000 psi).

Fillers either increased or decreased the compressive strengths of the pure resins and
could be categorized in two basic types:

1. Calcium carbonate, Cab-o-sil, and mica fillers increased the compressive


strength and the brittleness of the composite. For example, the 10,900 psi of
52% Sikadur/calcium carbonate composite compared to the 13,300 psi of the
28% Sikadur/calcium carbonate composite. Under ultimate load these
specimens broke with a loud sound into sharp, shell-like fragments.
2. Fillers of hollow spherical microstructure, such as Microspheres, Eccospheres,
and Globe-o-sil fillers, enormously decreased the compressive strength of the
pure resin (e.g., pure Sikadur resin at 10,800 psi, as compared to the 120 psi of
1% Sikadur/Microspheres samples). Filler-rich, hollow microstructure
composites had a tendency to distort and thicken under compression (load) and
partially recovered their original shape after the load was released. These
samples, when pressed beyond ultimate load, crumbled rather than broke.

4 DISCUSSION: EFFECT OF FILLERS ON COMPOSITES

The addition of fillers influenced all visual and physical properties of the composites
investigated. These properties could also be adjusted by varying the concentration of
the filler. In filler-rich composites, the appearance and physical characteristics of the
composites (color, viscosity, compressive strength, etc.) are determined by the fill
material. A large amount of filler (30% resin concentration or less) will result in a
composite increasingly similar to that filler. In resin-rich mixtures (above 30%
concentration), the properties of the pure resin will determine the properties (including
reversibility), regardless of the fill material. It may also be concluded that when
choosing a thermosetting resin for high-filler-load composite fill, an adhesive with a
long pot life (approximately 30 minutes or more) is preferable. When translucency is
desired, it is advised to choose a resin with an RI as close as possible to that of the
marble (approximately 1.65).

4.1 DENSITY

Contrary to what is expected, the density of the filler does not directly determine the
density of the composite. Instead, the microstructure of the filler should be looked at
when density of the composite is considered. Fillers with hollow sphere microstructure
decrease the density of the resulting composite, while fillers with solid particles
increase it.
4.2 WATER SENSITIVITY

Results of the absorption test showed that hollow microstructure fillers in filler-rich
composites (below 30% resin concentration) seem to encourage slow drying by
retaining a small amount of water for an extended period of time (72 hours) as
compared to the drying rate of natural stones (6 hours). There may be too much filler
in the composite to form a continuous network of resin around the filler particles, so
voids in the resin may retain some water upon drying. Alternatively, water may
penetrate the hollow space inside the balloon particle of the filler, which remains
trapped for a longer period of time. It should be noted that filler-rich, hollow spheres-
based composites will continue to dry up to 66 hours after the complete drying of a
natural stone, therefore keeping the original stone moist. Although, according to the
test results, the retained moisture in the hollow sphere-based composites is relatively
small, for applications such as heavily decayed stone or where susceptible to fungi or
algae growth, this water retention may be a factor for consideration.

A possible explanation of the disintegrated or water-damaged samples is the very short


pot life of the specific Akemi resin used, which may not have permitted proper
mixing. This supposition is supported by the fact that composites of comparable
concentration did not disintegrate when used in the Sikadur resin. Subsequent to the
completition of this study Akemi Plastics has increased the gel time of the “clear
flowing” grade polyester from 7–10 to 15 minutes. This change in the product also
suggests that the importance of allowing sufficient working time for thorough mixing
must not be underestimated. As the disintegration phenomenon was characteristic only
in the most filler-rich samples with the Akemi resin, it is conceivable that the amount
of resin available to bind the large amount of particles may have been insufficient.
Some of the filler particles may have been bound only by the mechanical lock of their
shape within the body of the composite sample. Such flaws in these filler-rich
composites may have remained unnoticed until the water immersion test when the
water penetrated and forced these mechanical locks between the particles apart. The
drastic results of the immersion suggest that a water immersion test may be a simple
and useful qualifying test for predicting weathering performance of composites
intended for exposure in an outdoor environment. The author's impression is that a
capillary rise test, if performed, might not have shown disintegration of such samples
so distinctly. The described water retention and disintegration of some samples
indicate that problems caused by moisture might occur if composites with similar
undetected flaws are used outdoors.

Results of the drying rates suggest that most composites tested will likely appear as
lighter areas on moist stone surfaces.

4.3 TRANSLUCENCY AND COLOR


Anisotropic (birefringent) substances did not lend translucency to a fill. For achieving
translucency of a fill similar to that of white marble, isotropic fillers with an RI
difference of 0.05 or less between the filler and the embedding resin were found to be
preferable. As stated earlier, composites of anisotropic fillers will remain arble does.
As all concentrations made of these fillers showed similar properties in both resins, it
can be concluded that composites of calcium carbonate, mica, and Cab-o-sil fillers are
of excessive compressive strength as compared to natural marble, and therefore are not
recommended for compensation of decayed calcerous stones. The explanation of this
phenomenon is likely to be found in the solid nature of these particles. The very small
size (i.e., 0.5–8μ), rounded shape, and relatively even particle size distribution of these
fills are possible contributing factors.

The other group of fillers tested—Microspheres, Eccospheres, marble dust, and


Globe-o-sil—particularly in concentrations between 1% and 35%, yield composites
that exhibit significantly lower compressive strength (and longer performance in the
plastic region) than that of natural calcareous stones and are good candidates for fills.
As opposed to the other group, particles of these fillers are hollow (Microspheres,
Eccospheres, and Globe-o-sil) or irregularly shaped with relatively large particle size
range (crushed marble dust). These results suggest that for mechanically reversible
composite fills, fillers with hollow or irregularly shaped particles with a large range of
particle size, should be preferred.

5 CONCLUSIONS

Isotropic fillers with hollow structures in Sikadur epoxy (with resin/filler w/v
concentration from 1% to 30%) provided the most promising results for matching
whitish translucent calcareous stones. The glass sphere fillers (Microspheres and
Eccospheres) tested here appeared the whitest, with a texture and translucency
resembling white marble or limestone. They exhibited the desired lower strength and
more deformation (deformed sooner and longer) in the plastic region than the natural
stone control specimens, and showed acceptable water sensitivity and color difference
in a wet-dry cycle in relation to the original stone. These samples are also easily
reversible by mechanical means (due to their lower compressive strengths and greater
strain at break than the fresh and decayed natural stones). Parallel tests with
contaminated (Microspheres) and purified versions (Eccospheres) of hollow sphere
glass microballon fillers produced virtually identical results. This suggests that in
choosing hollow sphere fillers, contamination of the product (or broken balloon
fragments in it) is of no consequence. Marble dust and Globe-o-sil fillers showed
results only slightly less promising than those of the hollow sphere fillers.

Calcium carbonate, mica, and Cab-o-sil fillers do not appear to be appropriate choices
for fills of white translucent calcareous stones. Their significant difference in color
and texture from a natural stone and their lack of translucency proves them to be
inappropriate for matching fills for white marble. Composites of these fillers tend to
produce greater compressive strengths than the stone, rendering these fills irreversible
and more likely to cause damage to original stone.

This study did not investigate problems such as aging of thermosetting resins,
yellowing (Down 1986), thermal expansion, resistance to freeze-thaw cycles, and
biodeterioration, all of which could be topics for further study.

ACKNOWLEDGEMENTS

The author would like to thank the Art Conservation Program, Queen's University,
Kingston, Ontario, Canada for its support in carrying out the tests and Christopher W.
McGlinchey, associate research chemist in the Paintings Conservation Department of
the Metropolitan Museum of Art, New York, for kindly providing RI data for the
thermosetting resins.

APPENDIX

1 APPENDIX: ANALYTICAL PROCEDURES

1.1.1 Density

The dimensions of the samples were measured with a metric dial caliper, 0.05 mm–
130 mm, Type 6910. The samples were weighed on a Model 333 Acculab electronic
digital scale with a minimum sensitivity of 0.1g. The density of the samples was
calculated in grams per cubic centimeter (g/cm3).

1.1.2 Water Sensitivity

All dry, conditioned samples and controls were weighed (as described in section 1.1),
then immersed in a distilled-water bath using one plastic screen on the bottom and one
on the top of each sample. The screen was necessary to weigh down the extremely
lightweight samples of Globe-o-sil, Microspheres, and Eccospheres (these floated on
top of the water) and allow sufficient absorption of water from the bottom of the dish.

After 48 hours of immersion, the samples were removed from the bath, dried by
blotting with a dry cloth, and then immediately weighed to the nearest 0.0001 g. For
this purpose a Mettler H20T balance with a weight indication of 0.01 mg to 160 g was
used. The specimens were weighed in the same order every time, at intervals of 6, 12,
19, 26, 33, 48, and 72 hours after immersion. The samples were left on a plastic lattice
to air dry. A sample was considered dry when three successive measurements yielded
the same reading. The first of these readings is indicated as dry state. The percentage
absorption was calculated using a standard absorption formula for water (ASTM
1995a).

1.1.3 Color

The colorimetry of the visible spectrum was carried out on a Macbeth Series 1500
Spectrophotometer using the CIE L∗a∗b∗ 1976 color system (ASTM 1995b).
CIELAB 1976 color space is an analytical color measurement system for comparing
or reproducing colors. In this system the scales on the three orthogonal axes (L∗
lightness, a∗ green-red, b∗ blue-yellow) are relatively uniform in comparison to other
chromatic systems.

Pulsed-xenon CIE65 was used as illumination with average daylight 6500°K


illuminants, which included UV. A white standard (No. 051025) was used for
calibration. The middle area of the largest surface was tested on each sample. The
instrument displayed all L∗,a∗,b∗, and DE∗ values.

Wet colorimetry samples were immersed as described in section 1.1. Readings were
obtained using the spectrometer as described above.

1.1.4 Stress-Strain Behavior (Elasticity and Plasticity)

Most of the samples were tested using a Unite-O-Matic compressive testing machine
with a load of 0.00002–10,000 lbs. For samples of 1.0% concentration, a Wykeham
Farrance Compressive machine equipped with a millivolt reader was used.
Compressive strength and strain tests were conducted at the Engineering Department
at Queen's University, Kingston, Canada.

The samples “stood” in the machine in order to have the long dimension of the
samples parallel to the axis of the compressive force. This meant that in the case of the
natural stone samples the compressive force was parallel to the bedding. Compressive
strengths were calculated using the standard formulas (ASTM 1995c).

The maximum speed of the loading head was 0.05 in./min. for the first and 0.045
in./min. for the second machine.

Readings were taken at every 5 or 10/1000 of an inch load movement, depending on


the strength of the sample.

The percent strain was calculated as follows:

2 STANDARD DEVIATION

Standard deviation values were calculated as follows:


REFERENCES

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grouts and monolithic surfacing, C 413-94. In Annual book of ASTM standards, vol.
6.05. Philadelphia: American Society for Testing and Materials.

ASTM. 1995b. Standard test method for calculation of color differences from
instrumentally measured color coordinates, D 2244-93. In Annual book of ASTM
standards, vol. 6.01. Philadelphia: American Society for Testing and Materials.

Badham, M.1991. X-ray identification of marble. X-ray identification report of the


calcite marble specimen. Kingston, Ontario: Miller Museum of Geology, Queen's
University.

Barclay, R., and C.Mathias. 1989. An epoxy/microballoon mixture for gap filling in
wooden objects. Journal of the American Institute for Conservation28: 31–42.

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deterioration and conservation of stone: Notes from the international Venetian course
on stone restoration, ed.L.Lazzarini and R.Pieper. Rome: UNESCO. 329–49.

Domaslowski, W.1995. Technology of epoxy mortars at low temperature and high


relative humidity. Zabytkoznawstwo I konserwatorstwo15 (189): 33–63.

Down, J. L.1986. The yellowing of epoxy resin adhesives: Report on high-intensity


light aging. Studies in Conservation31:159–70.

Larson, J.1979. The conservation of alabaster monuments in churches. Conservator2


(28):20–25.

Naudé, V.1991. Report on the discussion about stone. AIC Objects Specialty Group
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fabrications of natural stones and to suppliers of products for their care/conservation.
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FURTHER READING

ASTM. 1995c. Standard test method for compressive strength of chemical-resistant


mortars, grouts, monolithic surfacing and polymer concretes, C 579-91. In Annual
book of ASTM standards, vol. 4.05. Philadelphia: American Society for Testing and
Materials.

Brill, T. B.1980. Light: Its interaction with art and antiquities. New York: Plenum.

Clifton, J. R.1984. Laboratory evaluation of stone consolidants. In Adhesives and


consolidants, ed.N.Bromelle, E. M.Pye, P.Smith, and G.Thomson. London: IIC.151–
55.

Grattan, D. W., and R. L.Barclay. 1988. A study of gap-fillers for wooden objects.
Studies in Conservation33:71–86.

Nagy, E. E.1991. Effects of inorganic fillers on two thermosetting resins: Fills for
deteriorated white marble. Unpublished typescript. Queen's University, Kingston,
Ontario.

Remillard, F.1984. The effect of solvents on epoxy resin adhesives. Unpublished


typescript. Queen's University, Kingston, Ontario.

Selwitz, C.1991. The use of epoxy resins for stone consolidation. In Material issues in
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Materials Research Society Proceedings 185. Pittsburgh: Materials Research Society.
181–91.

Selwitz, C.1992. Epoxy resins in stone conservation. Research in conservation, vol. 7.


Los Angeles: Getty Conservation Institute.

SOURCES OF MATERIALS

Sikadur 35, Hi-Mod LV

Sika Canada, Inc., 601 Delmar Ave., Pointe Claire, Quebec H9R 4A9 Canada, (514)
697-2610 (Canada), (800) 933-7452 (U.S.)

Akemi Marmorkitt 1000/Akemi Marble Filler 1000, Transparent/Clear Flowing

Akemi Plastics, 1611 Hault Dr., Eaton Rapids, Mich., (800)365-8191 ext. 112
or

Stone Boss, 26-04 Borough Place, Woodside, N.Y. 11377, (718) 278-2677

Calcium Carbonate (marble fill) 151C

Hastings Plastics Co., 1704 Colorado Ave., Santa Monica, Calif. 90404, (310) 829-
3449, (310) 828-6830 (fax)

Cab-o-sil (Fumed Silica)

Cabot Corporation, 75 State St., Boston, Mass. 02109, (617) 345-0100

Fresh white natural marble

Spada Tile Inc., P.O. Box 431, K7L4W2, Kingston, Ontario KOM 1S0 Canada, (613)
546-9373

Bolender's Ltd., P.O. Box 329, Haliburton, Ontario KOM 1S0 Canada

Decayed white calcite marble

Obtained by the author and originated from a broken decayed gravestone in Kingston,
Ontario, Canada.

Globe-o-sil “G”

Hastings Plastics Co., 1704 Colorado Ave., Santa Monica, Calif. 90404, (310) 829-
3449, (310) 828-6830 (fax)

Microspheres 409, Low Density

Gougeon Brothers, Inc., P.O. Box 908, Bay City, Mich. 48707, (517) 684-7286, (517)
684-1374 (fax)

The production of this product has been discontinued. Similar products are available
from:

3M Scotchlite Glass Bubbles (e.g., Glass Bubbles K37 or S32)

3M Specialty Additives, 3M Center Bldg., 220-8E-04, P.O. Box 33220, St. Paul,
Minn. 55144-1000, (612) 736-4133

ECCOSPHERES IG-101

Emerson & Cuming Composite Materials, Inc., 59 Walpole St., Canton, Mass. 02021,
(617) 821-4250, (617) 821-0737 (fax)

MICA WG 160

KMG Division, P.O. Box 729, Kings Mountain, N.C. 28086, (704) 739-1321, (704)
739-7888 (fax)

Renaissance Micro-Crystalline Wax

Pi-Creator Enterprises Ltd., 44 Park View Gardens, London NW4, U.K., (44) 181-
202-3435

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