94 P. Bera, N. Guptha, K.P. Dasan and R.

Natarajan
2012 Advanced Study Center Co. Ltd.
Rev. Adv. Mater. Sci. 32 (2012) 94-105
Corresponding author: K. Priya Dasan, e-mail: k.priya@vit.ac.in
RECENT DEVELOPMENTS IN SYNTHETIC
MARBLE PROCESSING
Payel Bera, Neha Guptha, K. Priya Dasan and R. Natarajan
CO
2
Research Centre, VIT University, Tamil Nadu, India - 632014
Received: April 3, 2012
Abstract. Cultured or synthetic marble is a cheaper alternative for real marble. It is a composite
of resins like acrylate, polyester and fillers. Fillers can be silica, calcium carbonate etc. Fillers
and resin are mixed, followed by curing and molding to yield marble. Various techniques like slip
casting, isostatic pressing, dry casting are also used to cast marble. The real marble look is
simulated using pigments, chips etc. Onyx is another compound similar to marble but with more
transparency containing aluminium trihydroxide, glass frits as fillers. A detailed description of the
works carried out on the various processing techniques, fillers, polymers used and the resulting
properties such as mechanical behaviour, appearance such as color and pattern is presented
here.
1. INTRODUCTION
Cultured marble or synthetic marble also known as
'engineered composite', is formed by mixing high
strength resin, marble dust and catalyst. Natural
marble is generally heterogeneous with impurities
and fractures. They are available in remote areas
and require extensive handling in shaping and
finishing. This increase the price for these stones.
To overcome these difficulties, synthetic marble is
produced artificially. The desirable properties in an
artificial marble are high mechanical strength, ex-
cellent weather resistance, flexural strength, im-
proved surface hardness, heat resistance, stain re-
sistance and an excellent processability. Cultured
marble offers a number of advantages over natural
marble. These include lesser cost and incredible
design flexibility compared to stone. They have uni-
formity in colour and no random variations occur as
in natural stone. Natural marble is limited to flat
surfaces while cultured marble can easily be formed
to one piece bath tub, shower stall etc. Despite the
several advantages offered by artificial marble, it also
inherits certain disadvantages. For instance, the
marble surface can be scratched and care should
be taken to avoid placing objects on it that might
cause scratches. Minor scratches or cigarette
scorch marks may be removed by using 600 grit
wet or dry sandpaper followed by rubbing and buff-
ing with standard auto body rubbing compound.
However, it is highly recommended that minor dents
or nicks be repaired by trained persons familiar with
the proper techniques. The resin material in the
synthetic marble is not impervious to burns and
might melt, scar, or the glossy marble surface might
get damaged. Excessive tightening of plumbing fix-
tures could result in cracking of marble. However,
the safety of marble sinks can be increased by con-
trolling a number of parameters like defoaming time,
resin ratio, hardener amount, oven time, oven tem-
perature and amount of transparent glue (Wang et
al., 2009).
2. CHEMICAL COMPOSITION
The raw materials required for making cultured
marble are filler, resin, gel coat, solid or liquid pigment
and catalyst. Filler acts as an aggregate and must
95 Recent developments in synthetic marble processing
be present upto 85% to 95% by weight (Steven and
Larry 2002). Fillers used can be like aluminium
hydroxide, calcium carbonate and silica. The resin
acts like a glue and thereby strengthening the
marble. Resin content in synthetic marble is
generally about 12 to 15%. Based on the resin type,
artificial marbles can be acrylic or polyester or
polycarbonate type. Artificial marbles are prepared
by mixing fillers, pigment and a curing agent with a
syrup of a monomer/ polymer, e.g., methyl
methacrylate, polymethyl methacrylate, polyester
etc. This is followed by molding the mixture in a
mold or a continuous steel belt, and curing the
molded' mixture. A study on the complex and
multiple interactions between filler and polymers
revealed that intrinsic properties of the stone
substrate, like composition, porosity, and crystalline
characteristics, play a relevant role together with
the factors related to the polymeric system (Poli et
al. 2004). Pigment is added to get the desired color.
Pre-determined designs can well be included in
these and can be made to resemble the veining and
color of natural marble. The color and pattern occurs
throughout its thickness. Decorative additives are
distinguished from stone fillers primarily by the
amount present in the composition. Quantities of
decorative material used depend on fashion, design.
It generally do not exceed 5% by weight, and
preferably, should not exceed 2% by weight (Steven
and Larry 2002). These artificial marbles require gel
coats since castings made without gel coats are
susceptible to stress cracking and have a tendency
to stain. Many of these materials retain the
properties of the plastic matrix and are subjected to
some hot water whitening due to fissure at the filler/
resin bond, and/or under-cured or incompletely cured
resin (containing residual monomer). There are
many other minor constituents involved in marble
production - additives like initiators, activators,
adhesion promoters, fluidizing agents, viscosity
control agents, curing agents, antioxidants, catalyst
etc. The coupling agent is a small molecule that
aids in the dispersion of a solid particulate material
into a liquid medium. They are of the following types:
silanes, titanates, and zirconates. Initiators produce
free radicals which are required for polymerization.
E.g. Peroxides such as, peroxydicarbonates,
peroxyesters, and dialkyl peroxides. Azo type
initiators that also thermally decompose may be
used (Steven and Larry 2002).
Artificial marble formation involves recrystalliza-
tion during curing under high temperature and pres-
sure. Evolution of grain size in synthetic marbles
was traced from compaction of unconsolidated pow-
der, through primary recrystallization and normal
grain growth, to a size stabilized by second phases
(Olgaard and Evans 1988). Reagent grade CaCO
3
was used in the experiment. It was mixed with 0, 1,
and 5 volume % mica and heat-treated under pres-
sure with added water. Negligible recrystallization
occurred within one hour at 500 C and 500 MPa
confining pressure. Primary recrystallization oc-
curred at 500550 C, causing increases of grain
size of factors of 25. Resulting samples had uni-
form grain size, gently curved grain boundaries and
near-equilibrium triple junctions; they were used
subsequently for normal grain growth studies. Nor-
mal grain growth occurred above 550 C, till 800 C.
It was observed that minor amounts of pores or mica
particles inhibited normal grain growth and lead to a
stabilized grain size, which depended on the size
of the second phases and the inverse of their vol-
ume fraction being raised to a power between 0.3
and 1. Once stabilized grain size was reached, nor-
mal growths continued only if second phases were
mobile or coarsen, or if new driving forces were
introduced that could cause unpinning of bound-
aries.
Artificial marble can be classified as acrylic or
unsaturated polyester artificial marble depending
upon the base resin it contains. Organic base resin
leads to low weather resistance (Goh et al. 1996).
On the contrary, inorganic artificial marbles have
more colour resistance and durability. Fillers are
generally calcium carbonate, dolomite or aluminium
tetrahydrate (ATH). Theses components are all
mixed and filled in a mould and followed by a curing
process. Conventionally hand lay up moulding and
spray molding had been used (Amekawa 2001).
Otherwise compression moulding can also be done
using sheet moulding compound (SMC) or bulk
moulding compound (BMC) (Hayashi and Kameda
2002). Unsaturated Polyester is a major component
of these SMC and BMC. Researches are going on
to provide SMC or BMC with high productivity, ex-
cellent handling property, molding processability and
storage stability (Koyanagi et al. 2001). In one par-
ticular work by (Shingi et al. 1999), a SMC or BMC
had been developed by kneading an acrylic mono-
mer or acrylic syrup, an inorganic filler and a poly-
mer powder containing a remaining emulsifier in an
amount from 0.01 to 0.95 wt.%, and if desired, an
inorganic filler-containing resin particle, at a knead-
ing temperature from 20 to 70 C for 20 minutes or
less (Shinji et al. 2001).
96 P. Bera, N. Guptha, K.P. Dasan and R. Natarajan
2.1. Acrylic marble
Acrylic resins offer greater transparency. The acrylic
monomer can be methyl acrylate, ethyl acrylate,
butyl acrylate, methyl methacrylate, ethyl methacry-
late, butyl methacrylate, acrylic acid derivatives or
a mixture thereof. Acrylic artificial marbles show
good workability like wood and superior weather
resistance. They are lightweight and nonporous. In
addition, acrylic artificial marbles have an elegant
color tone, high strength and excellent weather re-
sistance like natural marbles (Sung et al. 2009).
But there are certain disadvantages too. The acrylic
syrup has a lower boiling point. So the curing tem-
perature must be sufficiently low to prevent boiling
off of the resin. This increases the curing time. Hence
productivity decreases (Koyanagi et al. 2001). Yet,
methacrylic resin as the matrix resin has attracted
attention because of its good transparency and
mechanical strength. Methacrylic resin is now used
as the matrix resin more frequently than unsatur-
ated polyester resin or epoxy resin (Uchida et al.
1992). The stresses built up by the mismatch in
thermal expansion coefficients between the poly-
mer and stone filler are related to temperature. When
a composite is heated, the acrylic polymer is able
to relieve these stresses more easily than unsatur-
ated polyester. It is considered that the acrylic poly-
mer possesses a mechanical response with an
improved strain to failure. The improved tempera-
ture performance with respect to crack initiation is
delayed as the polymer is slightly tougher (as char-
acterized by the work to break results) and the
stresses that are built up can be absorbed more
readily (Steven and Larry 2002). Hayashi and
Kameda (1992) used methacrylate resin for their
work. Various fillers like magnesium hydroxide,
magnesium carbonate and aluminium oxide were
incorporated with the resins. Fillers comprised 30
to 90% based on weight. The curable component
formulated by them was a combination of a
pol yfunctional al lylcarbonate monomer or
itsprecondensate
2.2. Unsaturated polyester marbles
The unsaturated polyester resin can be obtained by
conventional polycondensation reaction between an
unsaturated dicarboxylic acid such as maleic acid,
maleic anhydride, fumaric acid, etc., and a polyol
component such as ethylene glycol, diethylene
glycol, propylene glycol, dipropylene glycol, 1,3-
butanediol, 1,6- hexanediol, neopentyl glycol, 1,4-
cyclohexanediol, glycerine, pentaerythritol, etc.
(Rha et al. 2006). In unsaturated polyesters, cross-
linking occurs between growing styrene homopoly-
mer and the unsaturation sites in the polyester.
Unsaturation sites occur where maleic anhydride is
copolymerized with the polyester. The degree of
cross linking can be controlled by regulating the
concentration of maleic anhydride (Steven and Larry
2002). These have poor weather resistance and heat
resistance and difficult thermoforming over acrylic
artificial marbles (Sung et al. 2009). Unsaturated
polyester based marbles have lesser transparency.
Hence the visibility of the internal patterns and de-
signs is very less (Hayashi and Kameda 2002). Also
unsaturated polyester resin of the above composi-
tion poses a problem of lesser durability and lesser
resistance to hot water. Hence polyester resin is
inferior to polyacrylic resin. Ikezoe and Motomiya
(1994) worked on unsaturated polyester consisting
essentially of an acid component and an alcohol
component that offered superior impact resistance
and thermal shock resistance; moreover has supe-
rior hot water resistance and chemical resistance.
The alcohol component contained at least a glycol
(30 mole % or more) selected from a group consist-
ing of 2-methylpropane-1, 3-diol, 3-methylpentane-
1,5-di ol , 3-methyl -2-pentene-1,5-diol, 2-
isopropylidene-1,3-propanediol, 2-isopropyl-1,3-
propanediol, and 2-methylene-1,3-propanediol. As
cure accelerators, metallic salts of organic acids
were used, in particular cobalt salts, for example,
metallic soaps such as cobalt naphthenate and
cobalt octoate, and amines such as acetylacetone
cobalt, p-diketones, quaternary ammonium salts
such as di methyl benzyl -ammoniachlori de,
dimethylaniline, N-ethyl-metatoluidine, triethanola-
mine, and the like. Independent polymers or copoly-
mers consisting of monomers such as styrene, vi-
nyl chloride, vinyl acetate, and the like were used in
the process. Copolymers consisted of at least one
vinyl monomer and at least one monomer selected
from a group comprising lauryl methacrylate, isovinyl
methacrylate, acrylamide, methacrylamide,
hydroxylalkylacrylate or methacrylate, acrylonitrile,
methacrylonitrile, acrylic acid, methacrylic acid, and
cetylstearylmethacrylate, and in addition, cellulose
acetate butylate, cellulose acetate propionate,
polyethylene, polypropylene, saturated polyester and
the like.
The moulds of unsaturated polyester (UPR),
cracks easily under stress due to shrinkage when
it is being cured. Also when immersed in hot water
they show some colour changes (Goh et al. 1996).
Low shrink agents like lower alkyl esters of acrylic
aci d or methacryl ic aci ds such as methyl
methacrylate, ethyl methacrylate, butyl
97 Recent developments in synthetic marble processing
methacrylate, methyl acrylate, ethyl acrylate, and
the like are often used to minimize such effects
(Ikezoe and Motomiya 1994).
2.3. Epoxy resin
Marble can also be produced by mixing dolomite
and epoxy. In one of the works (Hussin et al. 2006)
70% dolomite and 30% epoxy had been used.
Diamine was used as a hardener. Dolomite was
ground into different range of mesh size 4 mm, 2.36
mm, 1.18 mm, 600 m, 300 m, 150 m, 75 m.
The mixture was poured on mould and cured for
about 6 hrs at room temperature. The produced
marble was named as 'kukum artificial marble'.
Various mechanical tests like three points bending,
modulus of rupture (MOR) and Charpy impact test
were performed to compare it with the other available
stones of market. The dolomite marble had lesser
density than the ceramic tiles and provided several
advantages like flexible style and design, solid
structure with heat, fire and moisture resistance,
good strength and long-lasting, easy to assemble
and easy machining to the desired shape. Starzec
and his co-workers (2006) had done a study on how
temperature cycling initiates changes in the porosity
of fresh and impregnated marbles. The results
indicated that intergranular decohesion was more
pronounced in calcitic marble than dolomitic marble.
This proved that the dolomitic marble is less prone
to weathering.
2.4. Inorganic artificial marbles
Park et al. (2010) formulated an inorganic marble.
Inorganic artificial marble contains inorganic matrix
consisting of an inorganic powder and an activator.
The inorganic powder comprised an alkali metal
hydroxide powder, alkaline earth metal hydroxide
powder, kaolin, brucite or a combination thereof. An
i norganic pol ymer such as pol y(si al ate),
poly(sialate-siloxo), poly(sialate-disiloxo), or a
combination thereof can be used as the polymer
base. Instead of using an organic resin all throughout
the marble, chips were used. In a study by Dutta
Puri (2007), marble of desired shape was produced
by mixing powdered marble, magnesium oxide with
solution of magnesium chloride, and pigment in
appropriate proportion. The fluid was poured on
mould and solidified for 6 to 8 hours. The produced
marble could be used as sanitary ware and for
ornamental purposes. The product did not require
any further treatment like curing, healing etc.
2.5. Onyx
Onyx is a form of chalcedony, part of the quartz
group. Onyx has a smooth, waxy luster. Cultured
Onyx has a semi transparent look like that of natural
onyx. Aluminium trihydrate (ATH) is used as the
filler instead of limestone. ATH has a specific gravity
of 2.4 (Wiener 2000). Cultured onyx differs from
cultured marble in their high degree of translucency.
The refractive index of ATH, the filler, matches well
with the resin. This, together with the little opacity
(due to the pigments added) gives the stone-like
veining, typical to onyx. Other hollow, light weight
fillers are generally not used since they have multiple
surfaces for reflection and refraction. This causes
increased opacity. Air spaces also increase opacity
due to increased differential refractive index (Ross
and Stevens 1984). Aluminium trihydrate gives a three
dimensional pattern to it. Onyx can be found in a
wide range of colors, often layered. Cultured onyx
products are made with a low color, clear,
unsaturated ortho polyester resin and a peroxide-
containing catalyst such as commercially available
methyl ethyl ketone peroxide (MEKP) product.
Conventional cultured onyx has a weight of
approximately 6.5 lbs. for a 1' square, 3/4' thick
sample. In contrast, a sample of cultured marble, 1'
square3/4' thick, typically weighs approximately
8 lbs. The primary difference between the weight of
conventional cultured onyx and conventional cultured
marble is due to the low specific gravity of the ATH
compared to the specific gravity of calcium
carbonate, and the higher percent of resin typically
used in a cultured onyx product (Wiener 2000).
Onyx can also be produced by blending polyes-
ter resins filled with silica, glass frit in a special
manner so as to inter-distribute like polyester
phases. This is then cured to produce onyx. But
there are several disadvantages like non-polishable,
dull surface, excessive weight. This can be mini-
mized by providing gel coats. But these also over
the years allow water seepage and the gel coat
separates off from the base. US Patent 4544584
(Ross and Stevens 1985) provides for a process to
produce onyx and marble with appropriate surface
properties. The structure comprised a locally dis-
continuous phase and a continuous phase. The dis-
continuous phase comprised a synthetic organic
resin portion hardened to the predetermined hard-
ness. The continuous phase comprised a synthetic
organic resin portion (less than about 50 U.S. mesh
in mean average particle size diameter) separately
hardened to the predetermined hardness with the
discontinuous phase intimately distributed therein.
98 P. Bera, N. Guptha, K.P. Dasan and R. Natarajan
The resulting structure surface was simulative of onyx
and uniformly polishable with undifferentiated phase.
The resin particles (diameter less than about 80 U.S.
mesh) of the discontinuous phase are hardened to
a pre-determined degree before combining. The
discontinuous resin portion particle chips typically
comprise from about 5% to 55% of the weight of the
product, and may be artificially colored. The second
resin portion constituted from 25% to 50% of the
structure by weight. The combined resin is cured
by heating or by catalysis. The best feature of the
invention was that by virtue of the like hardness of
the two resin portion phases it was possible to polish
the surface of the structure to a uniform gloss, without
use of an over layer of gelling resin, i.e. in gel coat
free relation. In one highly useful form of the invention,
water receptacles, such as pullmans, lavatories,
water closets and other receptacle apparatus, the
shaped product includes a passage within the
product, for water or other fluid or for receiving bolts,
screws and other fastening hardware, or for defining
a wall aperture for water flow or insertion of fixtures.
2.6. Processes to manufacture
artificial marble
Conventionally the molding compositions comprising
resin and filler have been mixed in a batch wise
manner to produce a molding mixture. Commercially
available bread dough mixers have been employed
for the batch wise mixing. US Patent 4269798 (Frank
1981) provided for the following process of marble
production. After placing uncatalyzed resin in the
mixing container, catalyst is added and mixed with
the resin. Thereafter, the filler is placed into the mixing
container of the dough mixer. The resin and filler are
then mixed until the resin is evenly dispersed
throughout the filler. Normally, when using a dough
mixer, several minutes are required to evenly
disperse the resin throughout the filler. A measured
amount of pigment is added to the mixture after
dispersing the resins and is partially distributed or
streaked through the mixture, leaving distinct
portions of the mixture free of pigment. Thereafter,
the mixing container is removed to a location where
the molding mixture is poured into a mold and
allowed to cure. Normally the resin is catalyzed so
that it will begin to cross-link shortly after it is poured
into the mold. Consequently, a new batch of resin
cannot be mixed in the container used for a previous
batch as the residue of the molding mixture in the
container will have cross-linked and thus solidified.
For further use, the container as well as the mixing
tool should be cleaned properly with solvent. The
batch wise processes are not labor-efficient because
of the long time required for the resin to be thor-
oughly mixed throughout the filler. Cleaning time is
also required after each batch is poured into a mold.
Moreover, since a substantial amount of time is
required to disperse the resin throughout the filler
(when prior art mixing methods are used), the resin/
filler mixture may begin to cross-link prior to the
time it is thoroughly mixed and placed in a mold.
Over the years, many different processes were
developed to manufacture artificial marble and onyx.
Griggs (1951), devised a method of strain hardening
at room temperature. The deformed material was
then heated to a point of annealing recrystallization.
Recrystallization due to shear strain was found to
provide a highly preferable orientation. A pressure of
5 kilobars was used for the purpose. These
requirements made the process economically
impractical. Rostoker (1969) demonstrated that
marble could even be produced at lower pressures
but in that case, temperature requirement enhances.
He prescribed grinding of calcium carbonate to a
size of lesser than 350 mesh, followed by pressing
the particles to make marble. The pressing was done
in a carbon dioxide environment and at temperatures
of 775 to 1000 C, 1000 to 3000 psi pressure for 10
to 120 minutes. To sustain such high temperatures,
expensive equipments of molybdenum or nickel alloy
was required. But at such operating conditions, the
materials proved to be reactive. Hence a protective
coat was needed for the dies. In another process
by (Rostoker and Bush (1965), calcium carbonate
particles together with a proportionate amount of
alkali carbonate were pressed. Alkalis like lithium,
calcium, sodium carbonate were used in the
process. Mixing the additives could lower the
operation temperature from 775 1000 C to 500-
600 C.
There are several techniques other than the hot
pressing to form a green body. The different
techniques available are: dry pressing, isostatic
pressing or slip casting. A green body formed by
any of these processes, was then sintered. A green
body refers to a ceramic compound, usually clay or
powder, before it has been fired or sintered,
respectively. For this sintering process, the particles
must be compactable. The particles in intimate
contact must get fused together or sintered. The
high temperature and pressure requirement can be
reduced by using CO
2
atmosphere or alkali addi-
tives. The drawback of these two processes was
that they were not economical and hence could not
be adopted at commercial level. Rostoker and Bush
(1965) found that instead of alkali, fluoride fluxes
99 Recent developments in synthetic marble processing
(2%) could be used. Fluoride fluxes could be used
in other forming and sintering processes like slip
cast technique. Fluoride flux (zinc fluoride 79% and
lithium fluoride 21%) meet the specific requirements
of sintering i.e. sintering to occur below calcinations
temperature.
There are several advantages of Slip casting
techniques (Rostoker and Bush 1965). They are the
least expensive and metal anchors and other
fastening devices can be fastened directly to the
body. Also the produced marble is sufficiently porous
and may be impregnated with silicones to make it
impervious. Slip cast can be organic or aqueous
type. In organic type casting the above fluoride flux
works best. But due to handling and manufacturing
difficulties often the aqueous slip is preferred. If
aqueous slip is used, zinc fluoride (water soluble)
should be replaced by other ions like aluminium
fluoride- calcium fluoride mixture.
Another process for marble production is the
Roberts process (Roberts John and William 1983).
In this, the mould is stored in a heated room at a
constant temperature for e.g. 30 C. A bulk container
of stainless steel with aluminium or stainless steel
blades or aluminium cutter is used to mix resin,
filler, and pigment. The blades are driven by an
electric motor. The mix is then pressurised to
approximately 20 lbs/sq.foot and stored. In the spray
area, the gelcoat is applied on the mould. The
releasing gel helps separation of the mould from
the product after curing. Application of the colored
pattern of pre-determined design on the gelcoated
surface is done using silk screen. Feeder lines of
PVC etc are used to transfer the mix in the bulk
container to the mixing head area. The catalyst is
added to the mix and deposited onto the mould.
The mould is then shifted back to the heated room.
The product is cured for twenty minutes, separated
from the mould and stored in the heated room.
Another method (Sato and Amano 1995) of
manufacturing the artificial marble sheet was defined
in US Patent 5403631. The general method for resin
molded article involves a resin concrete layer having
plasticity to be first formed on a carrier film. The
concrete layer does not contain glass fiber. Next a
SMC layer is formed on a second carrier film. The
resin concrete layer and the SMC layer are then
brought into an intimate contact to each other.
Carrier films are removed from the artificial marble
sheet and press molding is applied under heating
such that the resin concrete layer was located on
the side of the surface of the product. For the
production of artificial marble in the form of a resin
molded article, the SMC (sheet molding compound)
is formed by impregnating a glass fiber or the like
with a resin composition having an inorganic filler or
other bulking agent incorporated therein and
wrapping both the surfaces with a film. BMC (bulk
molding compound) similarly prepared in the form
of a bulk can also be compression-molded to form
marble (Uchida et al. 1992).
2.7. Enhancing mechanical and
surface properties
Dresen and his co worker (1993) carried out a study
on brittle and semi-brittle deformation of synthetic
marbles composed of two phases. It was conducted
on samples formed by isostatic pressing of fine
calcite crystals containing 5-20% rigid inclusions.
Conditions like room temperature, constant strain
rate and pressure of 5-300 MPa were maintained
during the test. Resulting microstructures were
examined by using optical and electron microscopy.
Rigid inclusions caused an increase in the range of
pressure over which the brittle-ductile transition
occurs. In the brittle field, two-phase aggregates
were generally 50 MPa weaker than the pure
material. At 5 MPa confining pressure, pure material
failed catastrophically along a single fault and
aggregates with 20% inclusions showed stable
cataclastic flow. In the semi-brittle field, strength of
the two materials converged at higher pressure. The
strengthening effect of the inclusions was due to
interactions between dispersed particles and
crystals defects. In one study (Eleonora 1998), the
influence of the concentration, color, refractive index,
density, particle size and shape, and microstructure
of filler on the color, translucency, texture, density,
elasticity, plasticity, reversibility, water sensitivity,
and working properties of their composites had been
studied. 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%. As early as 1973,
some manufacturers of cultured marble began using
microspheres to reduce the density of their sinks
and panels. The need for lightweight filler gained
momentum as larger vanities and cultured marble
100 P. Bera, N. Guptha, K.P. Dasan and R. Natarajan
bathtubs increased in popularity. This trend enhanced
the value of microspheres since they not only re-
duce the weight of the cultured marble component,
but also improve its resistance to hydrothermal
shock (www.potterseurope.com). The lustre of artifi-
cial marble is also improved by adding glass beads
and glass flakes. But the process changes the color
of the marble (Masato et al. 2000). The advantages
of glass microspheres are: improved resistance to
hydrothermal shock, weight reduction in the range
of 20 to 35%, greater ease of finishing (drilling,
sawing and sanding), less tool wear, reduced
packaging and shipping costs, increased production
through faster mould turn- around, impact
resistance, pigmentation value (whiter colour) and
reduced catalyst consumption. Glass beads also
improve microviker's hardness, barcol hardness and
heat resistance but pencil hardness of the resin fails
to improve.
In another study (Veronica et al. 2008), an
unsaturated polyester resin (UPR) thin coating
containing styrene monomer was used to
consolidate Marrn emperador marble pieces.
Different amount of nanosilica (0.5-3 wt.%) was
added to improve several properties of marbles
especially mechanical properties. Addition of
nanosilica to UPR-resins caused a noticeable
increase in impact resistance of coated marble
pieces. Studies have shown that improvement in
UPR properties is directly proportional to the
nanosilica loading. This is due to a network created
between the nanosilica and the UPR matrix which
conferred stiffness and toughness to the cured
polymer. The rheological properties of the UPR
solution like viscosity, imparting pseudoplasticity and
thixotropy were also enhanced by adding nanosilica
(more than 2 wt.%). Goh et al. (1996), developed
vinyl ester (VER) which had both improved surface
properties like pigmentability, transparency, lesser
loss of glossiness, color change and improved
mechanical properties like boiling water resistance
etc. The vinyl ester resin was formed by reacting
epoxy resins with methacrylic acid under special
conditions. Vinyl ester had never been used before
because they tend to change color. Hence special
care was taken during the experiment to produce
the desired ester. Several tests were performed on
the obtained resin to evaluate its performance like
yellowness index, hot water resistance test, and
color change in hot water. An artificial marble was
formed with the developed resin (100 parts by
weight), ATH (200 parts by weight) and initiator (2
parts by weight). The higher transmittance by the
new resin gave it more transparency like that of ATH.
Also the linear expansion coefficient of the formu-
lated marble was much lesser than that using the
traditional VER. Hence deformation due to tempera-
ture was much lesser. Clouding also occurred after
a much later time compared to traditional VER. A
prototype bath tub was made out of the above marble
of about 1.2 m in length and could be moulded within
30 minutes without any cracks. Thus productivity
was greatly enhanced. It had excellent translucency
and pigmentability. The bath tub was tested for hot
water resistance (24 cycles). Each cycle included
supplying hot water at 90 C for 8 hrs followed by
cooling down to ambient temperature. Changes were
observed with naked eye. There were no cracks or
blisters and very little color changes and loss in
glossiness were found. Koyanagi et al. (2001) for-
mulated a new resin comprising an unsaturated
monomer having atleast two double bonds, copoly-
merized with another unsaturated polymer 0.01 to
5% by weight of a radical polymerization initiator,
0.1 to 20% by weight of a resin having a methyl
methacrylate unit 50 to 85% by weight of an inor-
ganic filler and 1 to 20% by weight of a cross-linked
resin particle. The resin had excellent handling prop-
erty and easy moldability. Patent 5164425 (Uchida
et al. 1992) disclosed a composition for artificial
marble having a deep appearance characteristic of
marble and having a high strength and high abra-
sion resistance. It comprised (a) 10 to 60% by weight
of an allyl-terminated oligomer, (b) 40 to 86% by
weight of an inorganic filler and (c) 0 to 30% by
weight of a reactive monomer. Accelerated weath-
ering studies are conducted to evaluate the in-ser-
vice performance of marble (Crump 1996). In one
study progressive loss of cohesion along grain
boundaries was found to occur in widely used White
Macael marble due to thermal changes along with
humidity (Luque et al. 2010). US Patent 4871596
(Kamiya et al. 1989) offered a process to produce
artificial marble with a good stability in dimensions
and suitable to apply to a composite panel or a deco-
rative laminate panel. The marble did not show tear-
ing even after long time use. For the production of
marble, an unmodified melamine resin or an alco-
hol-etherified melamine resin was used. In the etheri-
fied resin, formaldehyde-to-melamine molar ratio was
in between 1.2 to 3.0. This resin together with a
modifier (alcohol, glycol, acrylic monomer, acrylic
oligomer and vinyl acetate monomer) was impreg-
nated into a porous substrate. Artificial marble was
produced by laminating many of such pre-impreg-
nated sheets. The melamine resin composition
might be incorporated with a variety of fillers to im-
part desired characteristic properties. Examples of
101 Recent developments in synthetic marble processing
the fillers included silicon dioxide to improve white-
ness, aluminium hydroxide to improve clearness,
and aluminium dioxide to improve wear resistance.
The porous substrate was paper made of .alpha.-
cellulose fiber or linter fiber. The cellulose fiber might
be incorporated with 1 to 50 wt.%, preferably 5 to
30 wt.%, of glass fiber, carbon fiber, polyester fiber,
nylon fiber, or the like as reinforcing fiber. The di-
mensional change was found to be smaller than
0.5% in both the lateral and longitudinal directions.
nclusion of p-toluenesulfonamide, lactam,
benzoguanamine resin, or methyl glucoside in the
melamine resin caused an improvement of crack
resistance and fabricability for bending. The rein-
forcing fiber improved the crack resistance and
warpage resistance of the molded product.
Reinforcing fiber in excess of 50 wt.% greatly
reduced the strength of the substrate because of
poor.
2.8. Developing color and patterns in
artificial marble
Works have been done to mimic the surface
appearance of marble. In one particular work
(Ohtsuka and Oishi 1996), granular surface
appearance like that of marble was obtained by
mixing and dispersing 0.001-10 parts by weight of a
thermosetting resin with 100 parts by weight of a
thermoplastic resin. Thermosetting epoxy resins,
thermosetting phenolic resins, etc., could be used
for the purpose. It overcame the problem faced in
conventional processes li ke poor surface
appearance, while using polycarbonate resins (a
thermoplastic resin). Artificial marble or granite
having many qualities (Traverso and Renzi 1994)
like excellent aesthetic properties, patterns and
tonalities can also be prepared from a composition
containing a polymerizable poly (allyl carbonate) of
a pol yol in a l imited quantity and mi neral
filler(carbonate type in the case of marble , and
silicate or silica type in the case of granite). The
filler is in the form of particles of which at least 40%
to 100% by weight have a particle size greater than
0.5 mm. Works have also been done to simulate
the fissured look of natural travertine marble into
the artificial marble. (Mentzer and Nancy 1989)
simulated the travertine marble. Slurry of magnesium
or calcium carbonate in water was prepared and
screened through a screen having a specified
thickness and mesh openings onto a casting surface
to deposit carbonate on casting. Castings of glass,
fiber glass-reinforced polyester, polycarbonate or
acrylic polymer were used. The deposits were dried
and framed as per the desired configuration and
height of the simulated marble article. Two compo-
nents: (i) a reaction solution of alumina, phosphoric
acid and water and (ii) a mixture of magnesium ox-
ide and calcium silicate were made. The two com-
ponents were mixed at a specific temperature and
for a period necessary to provide a viscosity of the
mix between 350,000 and 600,000 poises. When
the mix solidified carbonate deposits generated
carbon dioxide to produce a substantially solid ar-
ticle having a fissured surface, resembling traver-
tine marble.
Later chips were developed to form patterns and
designs. Transparent chips give the ability to provide
the artificial marble with different patterns. The chips
are conventionally made of the same material as
that of the artificial marble. The chips can also be of
a thermoplastic resin, such as polyvinyl chloride
(PVC) or polystyrene (PS), or a thermosetting resin,
such as epoxy resin or unsaturated polyester.
Conventional chips are single-colour chips in fine
powder form or having a size of 2.5 mesh or less.
The patterns obtained by mixing these with resin
fail to resemble natural ones. This happens due to
the colour difference between the chips and the resin
used for artificial marble. Also chips in conventional
artificial marble, have excessively low transparency
regardless of the material of the chips. So the final
product has a limited transparent effect (Kim and
Choi 2007). The specific density of the chip should
match that of the artificial marble. Hence inorganic
filler is used. If this is not present in chips, they
float and do not come in contact with the rear end
on the steel. Problem in surface physical properties
occur due to the difference in distribution between
the upper and the lower face. To prevent chip
separation the specific density of the chips should
be equal to that of the base material. But to maintain
transparency like natural material, filler should not
be added. Transparency gives a marvellous three
dimensional feel to the material. (Kim and Choi 2007)
came up with a solution for this. They developed a
novel quartz chip with transparent look and same
specific density as that of the marble. Quartz chips
were prepared by crushing a flat plate made of a
mixture of the transparent chips and a composite
for the artificial marble, which contained inorganic
filler. Thus the specific gravity of the quartz chips,
and the artificial marble was made uniform. The
artificial marble was then prepared by applying the
quartz chips to a raw material composite for the
artificial marble. Marbles resembling more to the
natural stone can be made using multicolour chips
(Sung et al. 2009). For this different colored slurries
102 P. Bera, N. Guptha, K.P. Dasan and R. Natarajan
need to be prepared using different pigments. These
are then mixed partially in batch mixer, cured and
crushed to produce multicolour chips. Optimum size
of chips is between 0.1 mm and 10 mm. Beyond 10
mm, cracks can develop between the chips and a
base. Also the chips can get caught in an impeller
of a batch mixer. Chip size larger than 10 mm may
also adversely affect the flowability of raw materials.
The reason for the limited size is because the
multicolour chips are commonly made into a flat
plate having a thickness of about 14 mm. Although
relatively smaller chips are advantageous in use over
relatively larger chips, larger chips are better in terms
of manifestation of designs in the final product. So
the multicolor chips are crushed to various sizes
and mixed before molding to prepare an artificial
marble. US Patent 3670060 (Cuffaro et al. 1972)
provided a method to produce artificial marble with
good light-fastness and high resistance to weathering
and can be easily machined and polished. It claimed
to reproduce the colors, the patterns and lustre of
valuable natural marbles perfectly. The procedure
according to the invention consisted essentially of
the following operations: intimate mixing of ground
stones with thermosetting resins, pigments, a
catalyst for the resins and a dispersant for the
pigments; pouring of the mixture into forms; heating
of the mixture under pressure to the complete
hardening of the resin, removal of the products so
obtained from their forms, and, if needed, their
finishing. Single mixture was formed with 82-85%
of powdered natural stones, preferably limestone,
15-11% resins using paratoluene sulphonic acid,
oxalic acid, phthalic anhydride, preferably zinc
sulphate as a catalyst 0.20-1.66% of pigments with
dispersants. Many single mixtures of the above
composition with different pigments were used.
These color components were mixed together
partially so that separate streaks, bandings or veins
could be visualized. The layers and shapes of the
color components in the mixture were modified and
altered by pouring the mixture once or repeatedly
into other containers. Pressure in the range of 140-
180 kg/cm
2
was used, with a starting temperature
of 10-30 C and a hardening temperature of 145-
160 C. Oh et al. (2007) were successful to produce
an artificial marble using chips made of a low
specific gravity material via a lamination or crunch
technique. This gave it a natural stone-like texture.
They also developed a process for preparing the
artificial marble. In one process, a high specific
gravity layer containing high specific gravity inorganic
filler was laminated on a low specific gravity layer
made of a low specific gravity material to form a flat
board. The flat board was then crushed to produce
chips. In another process, low specific gravity re-
gions made of a low specific gravity material was
coated with a high specific gravity slurry containing
a high specific gravity inorganic filler, to produce
crunch chips. Thus, a low specific gravity material,
which could not be used conventionally, was used
to produce artificial marble. Rha et al. (2006)
developed transparent chips. Colors or metals like
Au, Ag, Al, Ni, etc. are deposited. The amount of
these transparent surface treated marble chips varied
between 0.1 to 150 parts by weight, per 100 parts
by weight of acrylic resin for aesthetic appeal. The
composition was cured in a conveyer belt or under
hot blast. The cured material was then sanded to a
certain depth to remove the top coat as well to
provide a smooth surface. This gave a three
dimensional look as if gems studded in the marble
since the colors were visible from the top transparent
face. Few processes have been tried for decorating
cultured marble. Earlier objects like metal, wood,
glass etc were laid and moulded together with the
marble. But the surface had to be treated further.
Gaps had to be stoned with cement and then
polished or enamelled. This proved to be quite time
consuming. Seifert et al. (1985) proposed a new
technique in 1983 to include floral designs etc as
integral part of the cultured marble and not as an
added fabric. Hand-made designs were made using
acrylic paint over the gelcoat. This was followed by
pouring of the marble mix and its hardening. Such
process prevented any distortion of the designs
during the curing process. Some other works like
US Patent 9899125 (Lin 2003) discusses on forming
of patterns on marble using polymers. In general
there are three methods for producing patterned
marble. Either by hand digging or by computer
controlled tools designs are sculpted into the marble
and then filled with the decorative material. In the
last process, the marble is split into pieces. These
pieces are then fitted together to form the pattern.
The above-mentioned methods all can produce
patterned marble/granite/solid surface material.
However, there are several disadvantages existing
such as production methods, product cost, product
quality etc. these methods are time consuming,
labour intensive and often very expensive. Manual
fitting produces uneven, rough surface, improper
fitting. Also computer controlled tools fails to produce
certain angles, and complex designs. Hand tooling
is not suited for small patterns and lot of residue is
produced which cannot be used. This patent
disclosed a procedure to produce patterned marble.
First a mould with a pattern was formed. Two
103 Recent developments in synthetic marble processing
materials- basic material and pattern material were
formed. The component of the basic material of the
artificial marble/granite/solid surface material was
composed of one kind of resin like acrylic resin,
epoxy resin, or unsaturated polyester (10 to 90%),
at least one kind of filler material (10 to 90%) and
an accelerating reagent mixed in different
proportions. The filler materials were natural marble
powder, agate powder, aluminum hydroxide powder
and calcium carbonate powder. The pattern material
also contained the same components but in different
proportions. However, some additives (1 to 30%)
such as colorful plastic grains, marble pebbles,
granite pebbles were selectively added into the
pattern material to make the pattern material vivid.
The patterned artificial marble was formed by
multicasting basic and pattern material. This
process offered several advantages. Processing time
could be controlled by the concentration of the
accelerating agent. Raw materials were cheap and
not wasted. The mould allowed each single piece
to be of same size, pattern with fine trimmed edges.
Also no redundant material was left to cause
environmental problem.
2.9. Gel coat
The gel coat selection determines the look of the
composite product over the years. The performance
of a gel coat should be considered at two levels:
(Crump 1996).
At the time of manufacture of the composite
(application performance)
During the usage of the composite (in-use
performance)
The different application performances may include
good sag resistance, no porosity, must cure well,
should sand/buff well etc. In-service performance
refers to properties like good weather resistance,
water resistance, crack resistance etc. (Crump
1996). The basic generic types of gel coats are:
1. Orthophthalic based systems. These are the
oldest base polyesters used in industry. Their
benefits are
excellent handling characteristics
very low in cost.
But these have 'lousy' thermo-shock properties.
A thermal shock value of <100 is 'normal' for this
type of gel coat system.
Orthophthalic NPG based polyester gel coats
have better properties than the straight Ortho/PG/
DEG types of gel coats. They tend to be a bit tougher
and less brittle and have better water resistance
than the non-NPG type systems. The Orthophthalic/
NPG gel coats can be expected to have better ther-
mal shock properties than the conventional non-NPG
Orthophthalic-based gel coat systems. In general
they will provide thermal shock properties in the
range of 550 to 650 cycles when used with a good
quality matrix system. The Orthophthalic/NPG gel
coats are probably the most common types of cul-
tured marble gel coat in use today.
Isophthalic/Propylene Glycol systems are, and
have been for many years, the workhorse of good
marine gel coats and some cultured marble gel
coats. They demonstrate good toughness, fair to
good water resistance and good thermal shock
properties. They are somewhat higher in cost than
the Orthophthalic/PG systems and are slightly
higher in cost than the Ortho/NPG gel coat systems.
Handling properties tend to indicate that these
products are a bit less easy to use than the
Orthophthalic systems or the Orthophthalic/NPG
systems. A typical clear cultured marble gel coat
prepared from an Isophthalic-Propylene Glycol type
of system will typically provide thermal shock values
in the 700 to 800 cycle range.
NPG/Isophthalic Systems. Currently the best
polyester 'backbone' for both clear and pigmented
gel coat systems that are used in the cultured marble
industry is based on NPG/Isophthalic polyesters.
While a little more sensitive, handling wise, than
are the Orthos and some Isophthalic systems, the
little extra effort is well worth it when properties such
as chemical resistance, abrasion resistance, and
water resistance are considered. Thermal shock
values of 2500-8000 cycle range are often obtained
with these systems. This type of resin is the basis
for 'G'series clear cultured marble gel coats .' (HK
Research Corporation Product).
A study had been carried out by Tommaso Poli
et al. (2004) about the surface treatment of stone
materials which helps in protecting those materials
from the attack of environmental pollutants. Natural
and synthetic waxes, acrylic and siloxane resins,
perfluoropolyethers, fluorinated polyolefin and
fluoroelastomers are some of the most used
commercial products employed as protective
coatings for stone materials. These products are
applied not only to prevent the attack of the
environmental pollutants but also the penetration
of water, with the connected risks of freezing and
thawing cycles and the crystallization of salt
solutions, in order to slow the stone degradation
processes. The easiest way is, through the
deposition method, on the stone surface, and
possibly deeper beyond the surface, of a coating
layer able to modify the interaction of the stone with
104 P. Bera, N. Guptha, K.P. Dasan and R. Natarajan
water, turning the partial hydrophilic character of the
stone surface into a high hydrophobic interface. This
modification should be achieved by affecting only
the thermodynamic superficial potentials, but leaving
unaltered, as long as possible, the superficial aspect,
morphology, open porosity and roughness. The
coating materials do not react with the stone
material in order to respect its natural chemistry.
Stability and resistance to the photoxidative and
thermal ageing of the different polymeric classes
are other crucial problems: Sometimes a long term
chemical integrity does not correspond to a similar
protection efficacy. After applying a polymer to a
stone surface, physical rearrangements could occur
to the protective layer, reducing the shielding
efficacy but leaving the chemical structure unaltered.
3. CONCLUSION
The light weight, beautiful cheaper cultured marble
has become a competitive alternative for natural
marble. Conventionally, resins like acrylate,
polyester etc. are mixed with fillers, pigments and
applied on molds followed by curing to yield artificial
marble. Besides this conventional process, many
other processes exist like strain hardening at room
temperature, isostatic pressing, slip casting,
Robert's process. The mechanical and aesthetic
properties of artificial marble depend on the resin
and filler composition together with other decorative
substances like pigments, chips etc. Many works
have been done to simulate the look of natural marble
as closely as possible. Transparent chips have been
used to give a transparent surface so that the inner
veining is visible. Cultured marble can be easily
made into one piece shower stall or bath tubs.
Despite these several advantages, it also has some
drawbacks like lower hydro thermal shock
resistance and proneness of surfaces to easily get
scratched. Yet its grand look and cheaper price
makes it very attractive
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