Accepted Manuscript

Effect of different waste filler and silane coupling agent on the mechanical properties
of powder-resin composite

Heriyanto, Farshid Pahlevani, Veena Sahajwalla

PII: S0959-6526(19)30979-5
DOI: https://doi.org/10.1016/j.jclepro.2019.03.269
Reference: JCLP 16273

To appear in: Journal of Cleaner Production

Received Date: 29 July 2018

Revised Date: 22 March 2019
Accepted Date: 24 March 2019

Please cite this article as: Heriyanto , Pahlevani F, Sahajwalla V, Effect of different waste filler and silane
coupling agent on the mechanical properties of powder-resin composite, Journal of Cleaner Production
(2019), doi: https://doi.org/10.1016/j.jclepro.2019.03.269.

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 ACCEPTED MANUSCRIPT

Material recovery from urban Functional

Functional RawRaw Materials
Materials Powder-resin composite

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waste stream
Paper filler

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Glass Resin, hardener
powder and silane
coupling agent
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Effect of different waste filler and silane coupling agent on the mechanical
properties of powder- resin composite

Heriyanto*, Farshid Pahlevani, Veena Sahajwalla

Centre for Sustainable Materials, Research and Technology (SMaRT)

School of Materials Science & Engineering, UNSW SYDNEY, NSW, 2052, Australia

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Abstract

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This study reports an innovative pathway for successfully synthesizing composite panels
using various waste input. For this purpose, seven types of powder from waste or widely

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available filler i.e. Quartz off-cut, sand, waste seashell, dolomite, limestone aggregates,
concrete waste and limestone dust were used. The study aims to assess the effectiveness and

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mechanical properties of the various waste powder in the production of powder-resin
composites. The panels were then compared with the novel polymeric glass composite (PGC)
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in the previous study (Heriyanto, 2018). Following the same procedure in PGC, the filler was
individually grounded to 64-108 µm and chemically treated with amino silane coupling agent
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(CA). The powder filler (untreated or treated) is then mixed with the resin binder with a ratio
of 80/20 respectively, followed by hot pressing the mixture at the pressure of 550 bar at 65oC
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for 1 hour. The final composite slab is then further cut for mechanical testing. It was found in
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the study that when CA was not added, surface roughness of the powder particles affected the
flexural strength of the final panel significantly. High surface roughness particles such as in
Quartz, sand and seashell adhere effectively with the resin binder which led to higher
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strength. On the contrary, other factors like smooth particle morphology in glass, dolomite
and limestone as well as porous structure in concrete and clump of very fine powder in
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limestone dust degrade the strength of the final panels. With CA addition, adhesion between
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resin and powder filler were improved significantly. Flexural strength after the CA treatment
was found to be much affected by particle characteristics. Silica-based panels i.e. quartz, sand
and glass which consist of high strength and hardness of silica particles perform better
compared to that of calcium carbonate-based panels. Compression strength, toughness,
stiffness, scratch resistance, density and water absorption were also reported in this study.
The properties of all the treated panels are found to be comparable, or if not, much better than

*
Corresponding author.
E-mail address: Heriyanto@unsw.edu.au (Heriyanto)

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natural stones. These new approaches of using waste filler in powder - resin based
composites can be a new alternative to produce green materials that deliver economic and
environmental benefits.

Keywords: Powder-resin composite; waste recovery; silane coupling agent; green materials.

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1. Introduction

A growing number of man-made stone products are widely available nowadays. Their

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roles have evolved from humble beginning as decorative wall panels to structural use as
countertops, bathroom vanities, and floor tiles. Demand for engineered stones in Australia

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alone is expected to reach 4.15 million m2 in 2021 (The Freedonia group, 2017). Engineered
stones are often preferred over natural stones due to its less porous and stain resistant

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properties, less susceptible to mildew and superior bending and compression strength,
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making them very suitable for kitchen and bathroom environment.
Industrially, engineered stones are manufactured mainly from resin binder and
crushed stones. In the previous study (Heriyanto et al., 2018), a similar approach to use waste
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materials in the production of engineered stones has been done. The artificial stones, namely
polymeric glass composites (PGCs) have been successfully produced from waste glass
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powder, coupling agent and resin binder with superb mechanical properties and water
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resistance. The panels were also made with cheaper processing conditions and do not require
vacuum vibrator compressions. Following its success, an innovative approach to use other
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types of powder filler will be conducted in this study. For this purpose, seven types of powder
from waste or widely available filler i.e. Marble/limestone off-cut, dolomite, Quartz, sand,
seashell, concrete and limestone dust will be used.
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Marble, travertine and dolomite are metamorphic rocks as a result of the

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transformation of limestones (Malpani et al., 2014). The rocks have been used intensively
mainly as decorative slabs in buildings and monuments (Soliman, 2013). Prior to slab
production, the natural rocks were usually mined and processed by the stone industries. The
mining unit involves extraction and block production, while the latter involves trimming to
slab, cutting and polishing. The waste generation during mining alone was estimated to be
approximately 60-70% when conventional blasting techniques were used or 30-40 % using
the wire saws technique. The waste produced in the mining segment can range from stone
fragments to various shape and size blocks from trimming and shaping the rocks to blocks. In

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the processing unit, according to the natural stone council (2009), approximately 75% of the
block were discarded as wastes. The stone wastes were generated from rock sawing of the
block to slabs, cutting, grinding and polishing, and they are usually found in the forms of
stone fragments, wastewater sludge, screening residual and fine powder (Natural stone
council, 2009). Additionally, due to the strict demand for visual appearance, monument
construction also generates a huge quantity of wastes. The wastes are from the rejection of

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fractured and unwanted blocks. It is estimated that only approximately 70 out of 1000 tonnes
of these natural stone were used in completed building or monument. For instance, as a

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matter of fact, in the United States alone, due to the high amount of waste generated during
excavation and processing, the amount of waste crushed stones can reach up to 175 million

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tonnes annually (Natural stone council, 2009). Additionally, quartz off-cut is also a common
type of waste found in stone industries. Quartz is known for its high crystallinity, hardness,
durability and strength. Quartz off-cut is no longer considered as waste due to its high

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demand for engineered stone manufacture. In this study, Quartz powder will, however, still
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be included for a means of comparison. Other silica-based powder such as sand and glass will
also be used as powder filler to produce the composite panel. Sand is not considered waste
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but will be included in this study due to its wide availability. The relationship between
crystallinity and chemical bond of Quartz/ sand-based panels will also be studied thoroughly
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and compared alongside with the glass powder composite panels from the previous study.
Besides the natural stone aggregates, waste concrete fragments from building
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construction and demolition (C&D) are of the author’s interest. Based on the C&D status
report (Hyder, 2009), a total of 12 million tonnes of waste concrete was generated in
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Australia in the period of 2008-2009. An effort to reuse and recycle concrete waste were
relatively remarkable in Australia, but still leaving 35% or approximately 3.5 million tonnes
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of concrete waste unused and disposed in the landfill.

Lastly, waste shell powder filler will also be included in the study. Waste shell also
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poses a substantial challenge on the shellfish processing industries. Despite the numerous
potential uses of shells in the craft sector, there are, however, no ideal solutions to reuse and
recycle them in large quantity (Fitzgerald, 2007). Shellfish industries tend to depend on the
disposal services that charged up as much as $150/ton of shells (Yan et al., 2015).
To encounter this problem, the present work studied the possibility of using different
waste powder filler to produce engineered stones. The different filler used might differentiate
the quality of the composites from one another. To confirm this hypothesis, in this study, a

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thorough observation on the characteristics of powder filler particle and the produced panels
will be investigated.
The processing condition will follow the same method in the previous study
(Heriyanto et al., 2018). With the same processing condition, a thorough side by side
comparison among various filler on influencing the mechanical properties of the powder-
resin composite panels can be investigated. The study aims to present a set of mechanical

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strength data that allow manufacturers to use the suitable filler for each specifically designed
product depending on its usage. Combination of such fillers can also be made to achieve a

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product with distinguished colour and unique properties. Relation of crystallinity and
chemical bond with mechanical strength will also be studied thoroughly. Coupling agent will

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also be added to improve adhesion and strength between the inorganic powder and the
organic resin.

2. Materials and Methods

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2.1. Material characterisation
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In this study, eight types of powder from waste or widely available filler i.e. Quartz
off-cut, sand, waste seashell, dolomite, limestone aggregates, concrete waste and limestone
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dust were used. Waste window glass, limestone, sand and concrete were collected from local
building demolition sites with waste sea shell and Quartz/marble stones sourced from the fish
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market and stone suppliers respectively. This section will cover a comprehensive study of the
elemental analysis of the corresponding powder. This will allow a better understanding of the
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raw materials and might be useful in identifying the different mechanical properties of the
composite panels later on. Furthermore, the characteristics of the resin binder and coupling
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agent will also be included in this section.

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2.1.1. Powder filler

The powder elemental composition in Table 1 was obtained by X-ray fluorescence

spectrometer. It is observed that Quartz, sand and glass powder consist mainly of SiO2 with a
minor percentage of Na2O in the glass. The structure of the silica-based powder was also
reported by X-ray diffraction with Quartz and sand having crystalline configuration and glass
being amorphous (The LibreTexts libraries. 2016). Other types of stones i.e marble,

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limestone and seashell composed of mainly calcium oxide with dolomite and concrete
contain both CaO and SiO2.

Table 1
Waste powder filler composition in weight percent (%)
Compound Na2O MgO SiO2 CaO Al2O3 LOI (CO2)

Quartz 0.000% 0.000% 99.000% 0.000% 0.000% 0.82%

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Sand 0.082% 0.034% 94.744% 0.021% 1.821% 0.52%

Glass 11.70% 2.96% 72.66% 6.9% 0.87% 0.91%

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Sea shell 1.003% 0.241% 0.022% 53.348% 0.000% 45.335%
Limestone 0.032% 0.586% 1.867% 52.770% 0.557% 46.245%

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Dolomite 0.100% 20.38% 5.221% 31.943% 0.0030% 42.980%

Concrete 0.230% 1.247% 15.51% 45.854% 3.655% 29.760%

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Limestone dust 0.030% 0.360% 0.321%
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The main characteristics of the powder filler i.e. particle size and shapes affect the
bulk density, surface area, flowability, and adhesiveness with the resin substrates. For the
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purpose of this study, the granulometry of the fine powder was kept constant. All the powder
filler, except for limestone dust (Low-density CaCO3 / LD CaCO3), was shifted through metal
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screening to size between 64-108 µm. Fine particle size in this range is intended to form a
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homogenous colour mixture when mixed with resin. It was also observed in this study that
limestone dust with particles smaller than 64 µm tends to clump. A thorough mixture of
powder and resin are therefore difficult to achieve with normal mixing.
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Particle morphology of the powder filler was identified using Scanning Electron
Microscope (SEM) analysis and will be explained later in the result section.
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2.1.2. Resin binder

Marine-based epoxy, namely Clear Cast from Alumilite with properties of being non-
toxic, high abrasion and chemical resistance were used as the composite binder. The resin is
designed for bar top casting and flooring and is highly resistant to UV. The resin has a
medium viscosity of 2600 cps when combined with hardener at a volume fraction of 1:1. The
decomposition temperature of the resin was analysed by PerkinElmer STA 6000 to be 350oC.
Moreover, despite their uses for indoor application, the produced composite panels were
designed to resist certain degree of UV degradation. The clear resin used in this study was

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observed to demonstrate a minor coloration with its 42 days-yellowish discolouration index
being comparable to the 2 days-discolouration index in general craft epoxy.

2.1.3. Coupling agent

Amino-based coupling agent (CA) with a chemical formula of 3-

aminopropyltriethoxysilane was chosen in this study. The CA was supplied from Double

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Peach Fine Chemical Corporation in Guangzhou. The CA was used to provide surface
modification of non-polar materials and improves its wettability with the resin binder. The

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CA is best suited for epoxy resin and inorganic fillers, typically silica-based components
(Shin-Etsu Silicon. 2017, Gelest, 2018). According to the research conducted by Demjen et

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al., amino functional silane coupling agent also has the capability to adhere well to CaCO3
filler surface and resin (1997). The CA act as a bridge between the polymer matrix and

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inorganic filler and help in improving adhesion as well as load and stress transfer. The
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interface modification of CA to glass powder is presented in Fig. 1 below.
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Fig. 1. Surface treatment of inorganic substrate with coupling agent (Arkles, 1977)

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The reaction of the silane with the powder filler involves four-steps. The process
consists of hydrolysis, condensation, hydrogen bonding and bond formation. Initially, when
mixing the CA with water, hydrolysis of the three labile groups occurs. The diluted CA is
then mixed with powder filler to promote reaction 2. Upon mixing with a mixer, the reactive
groups of silane CA that possess a hydrolytically sensitive centre will bind with the surface of

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the inorganic materials, forming a hydrogen bond. It is then followed by heating the mixture
at 120oC for 90 min to remove the water. At this stage, covalent bonds will form, break and

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reform to release the internal stress forming compounds in reaction 4 (Arkles, 1977, Gelest,
2016). When mixing the treated powder compound with resin, the organic end of the CA will

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react with the polymer matrix (Arkles, 1977). The overall bonding result in high mechanical
properties as described in the result section below.

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2.2. Production method
Fig. 2 explains the method used to synthesise the powder-resin composite panels. The
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method was invented by the author and was similar to that in the previous study (Heriyanto et
al., 2018). The merit of this method is that it does not require vacuum vibrator compressions
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– a common machine used by engineered stone industries to remove the air bubble from the
wet stone-resin mixture. In this new method, the removal of air bubble is done by adjusting
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the viscosity of resin-powder dough to a wet sand consistency and pressed at certain
temperature and pressure to produce a defect free product. The correlation between the
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viscosity and air bubble in the final products were explained in detail in previous study
(Heriyanto et al., 2018). The author also added coupling agent to improve the adhesion
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between the waste filler and resin and, consequently, improve the mechanical properties of
the final products. The step by step process were explained below.
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At first, the stone aggregates, concrete blocks, glass cullet and seashell were ground
individually by pulveriser into fine powders and shifted through metal screening to a size
between 64-108 µm. The powder filler was then oven-dried at 100oC overnight to remove
any remaining moisture. The powder filler is labelled as PF1 in the diagram. Additional
treatment is required when a silane coupling agent (CA) is incorporated. When powder filler
size of 64-108 µm was used, it was found from the previous study that two percent of CA
(calculated relative to the weight of the powder filler) are the optimum ratio to enhance the

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mechanical properties of powder-resin composite (Heriyanto et al., 2018). The PF1 was first
mixed in diluted ethanol and silane solution to a slurry consistency. The mixture was oven-
dried for 24 hours to remove the ethanol. A white compact of powder cluster was formed and
was then pulverized to form powder filler 2 (PF2).
The powder filler (PF 1 or 2) along with the resin binder was combined with a ratio of
80 to 20 respectively to form a dough-like consistency. The ratio 80/20 was found from the

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previous study to be the optimum ratio for creating a product free of trapped air bubbles when
the particle size of 108 µm was used (Heriyanto et al, 2018). The resin and powder were then

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mixed vigorously with a high-speed mixer for 15 minutes to assure uniformity in the blend.
A releasing agent was applied to a 240x240 mm carbon steel mould before the wet

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mixture was hand laid in the mould. The mould was then completely sealed and compacted
under a high compression pressure of 550 bars, and at a temperature of 65ºC (Heriyanto et al,
2018). Finally, the samples were removed and polished to a smooth finish.

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Fig. 2. Schematic of experimental procedure of powder-resin composite panel

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2.3. Mechanical and physical testing methods

The final composite panels were then cut to certain dimensions for mechanical
testing. The panels were tested based on American Society for Testing and Materials (ASTM)
standards and were designed for use in tabletop and kitchen benchtop. These tests include
flexural, compression, water permeability, thermal decomposition and scratch resistant test.
At least 5 specimens were prepared for each test with the average values presented in the
result.

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2.3.1. Flexural strength testing

Flexural strength is defined as the resistance of material against bending/ deformation
when placed under a load, usually measured by 3- or 4-point bending test. This property is
imperative for structural materials that were sustained by two or more beam’s support points.
The maximum flexural stress or modulus of rupture (MOR), along with the modulus of

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elasticity (MOE) of the specimens was measured in this study by 4-point bending test using
Instron 5982. The sample’s dimension and span were evaluated according to the thickness of

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the corresponding samples. In this study, all the samples were cut to 250 x 100 x 20 mm with
lower and upper span of the bending jig set to 200 and 100 mm respectively, following

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ASTM C880/880M. A constant loading speed of 0.067 MPa/s was applied to the sample until
fracture. The diagram of the four-point bending setup is presented in Fig. 3 below.

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Fig. 3. Schematic of flexural testing

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2.3.2. Compressive test

The compressive test assesses the limit state of a specimen’s strength under a constant
compressive load and was evaluated by dividing the maximum load by the cross-section of
the specimen. The test criteria were evaluated following ASTM C170/C170-16 and were
measured by using Instron 5892 at a constant load rate of 0.5 MPa/s to fracture. In this study,
all the samples were sized to cubes of 18x18x18 mm3, with 10% maximum difference
allowed between the horizontal and vertical axis.

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2.3.3. Water permeability test

The water permeability test assesses the amount of water a material absorbed after
immersion in water overnight. This absorption property is usually affected by the type of
materials, porosity and length of exposure. High water absorption in a material can lead to a

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potential problem related to thickness swelling, strength dropping and staining. The water
absorption test in this study was evaluated by soaking the specimen for 24 hours. The

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specimen was then removed, patted dry, and weighed. The water absorption value is reported
in weight percentage with the formula as following.

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( )
% Water absorption = 100

2.3.4. Thermal decomposition test

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The thermal decomposition of the specimens was evaluated by a thermogravimetric
analyser, namely PerkinElmer STA 6000. The machine records the weight loss of the
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specimens over time as temperature increases. For the purpose of this study, the specimen
was gradually heated from room temperature up to 1000oC in a nitrogen atmosphere at 20
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litres/minutes flow rates. The test allows determination of the minimum temperature when
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the specimen weight starts to decrease or the maximum service temperature of the
specimen. This property is especially important for polymer-based materials where
degradation happens at a relatively low temperature.
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2.3.5. Scratch testing

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Scratch testing determines the hardness of the samples and is an important property to
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identify how well a material can stand up against hard and sharp objects. The test is
performed by a Macro scratch tester. A sharp diamond tip stylus was used to scratch
specimen’s surfaces at progressing loads from 0-100 N within a 5 mm gouge mark. The
penetration depth profile was then recorded and compared among the samples.

3. Results and discussion

3.1.Powder-resin composite

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When manufacturing engineered stone, besides the strength, aesthetic appearances are
equally one of the most vital aspects required. To satisfy modern architectural requirements,
the engineered stones produced are made available in an array of different colours, patterns
and textures. The composite panels in this study are designed to replicate the natural look of
marble, granite, travertine, terrazzo and solid colour panels. In this paper, however, the focus
will only be made on the production of solid colour and marble-like panels using different

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powder fillers.

B(i)

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A Flexural strength Stone beads Delamination

30 26.3 26.1
Flexural strength (MPa)

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15 11.8 Stone beads

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PGC PGC with powder PGC with liquid
pigment pigment
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Sample with different pigment

Fig. 4. (A) Flexural strength of polymeric glass composite (PGC) panel with different types of pigment
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(B) Fracture surface of PGC with (i) liquid pigment (ii) powder pigment
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Liquid pigment has been a preferred material for craft maker when colouring resin.
Usage of no more than 2% of pigment loading is usually recommended to prevent strength
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deprivation. To prove this hypothesis, an evaluation of pigment addition on the mechanical

performances of powder-resin was conducted. In this study, liquid or powder pigment was
added in the glass powder-resin mixture during mixing prior to casting and hot pressing to the
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final products. The cured panel was then cut and its flexural/bending stress was measured by
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a 4-point bending test. It was observed that the flexural stress of the composite panels
degraded from 26.3 to only 11.8 MPa when liquid pigment was used. The degradation might
be due to weak interfacial bonding among the binder and filler after liquid pigment addition.
This was observed from the particle pulling-out on the composite panel when loaded under
flexural test (Fig. 4B (i)). On the contrary, no significant difference in bending stress was
observed with the addition of the powder pigment. The fracture surface in Fig.4B(ii) shows
better adhesion between the aggregates and the matrix with no delamination or particle pull-
out.

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Besides powder pigment, wastes and off-cut from the stone manufacturer can actually
be alternative materials to yield different aesthetic outcome. As shown in Fig. 5A, all the
different materials collected produce different colour panels. The mechanical properties are
also varied. This study will summarize the possibility and the mechanical strength value of
each of the composites made from these powder fillers. The panels in Fig. 5B were made
from combined fillers listed in Fig. 5A. The swirling effect like marble was created by partial

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mixing of at least two different coloured powder-resin dough prior to hot pressing. Different
powder pigment such as cobalt and hematite can also be used to add blue and red colour.

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A

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Limestone
B Quartz Sand Glass Sea shell Limestone Dolomite Concrete

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Fig. 5. (A) Solid coloured panel from different waste filler (B) Marble like panel from combined waste filler and
pigment

3.2. Flexural strength and stiffness (MOE and MOR)

Flexural strength evaluates the resistance of the materials against bending and is an
imperative property especially for structural materials i.e. tabletops where beam system is
used. In the beam system, the slab is usually sustained by two or more beam’s support points

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(National Ready Mixed Concrete Association, 2003). A tabletop company often prefer to use
slabs with higher flexural strength. Low flexural strength panels i.e. marble and granite are
often made thicker, usually ranging from 30-40 mm thickness, to increase the breaking load.
The stones are also often installed with a shorter span between the two-supporting legs to
compensate the weak bending strength. On the contrary, panels with high flexural strength
tend to have high breaking load and can be made larger and thinner, with a longer span.

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Commercial engineered stones usually have flexural strength ranging from 37-53 MPa which
consequently, allows the panels to be produced in 15-20 mm thickness. The resulted tabletop

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therefore requires less raw materials and become more cost-effective. Furthermore, thinner
and lightweight slabs are also easy to be transported from one location to another. Fig. 6

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summarizes the maximum flexural strength of the produced panels in this study. The PGC
panels were labelled as “glass” in the graph and compared alongside with the other composite
panels.

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Flexural strength
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51.2 No CA
47.8
50
CA
Flexural strength (MPa)

38.3
40 35.2 35.8 35
33.4 32.3
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30 26.3 27.8
26.2
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18 16.919.7
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Quartz Sand Glass Seashell Dolomite CaCO3 LD CaCO3 Concrete

Samples
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Fig. 6. Flexural strength of powder-resin composite with varying powder filler and silane coupling agent

3.2.1. Effect of powder morphology on the MOR of powder-resin composites

When the coupling agent is not used, surface roughness of the powder filler is an
essential factor determining the binding capability with resin. The properties and hardness of
the powder were observed to be irrelevant to the improvement in strength. During flexural

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testing, cracks propagate through the weakest point of the panel. The coherence of resin and
powder when untreated with compatibilizer are relatively poor. Under load, cracks will
extend through the resin matrix and bridge between the powder filler particles. It is the resin-
powder interfacial adhesion that determines the flexural strength of the composites.

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Quartz Sand

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Glass Sea shell

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Dolomite CaCO3
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Limestone dust Concrete

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Fig. 7. SEM analysis of powder filler morphology

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From Fig.6, it can be observed that composite made of Quartz and sand have higher
MOR, with an average value of 35.2 and 33.4 MPa respectively. The rough surface
morphology of these crystalline silica compound, shown in Fig.7, can adhere effectively with
resin binder which might improve the bonding and consequently, the strength.
Similarly, panels made from seashell are found to be equally comparable to the sand-
resin panel. The high surface roughness along with its fibrous nature is the reason for the

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superior performance in its bending strength.
When untreated with a CA, panels made from glass, dolomite and CaCO3 have a

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comparable strength of approximately 26 MPa. The powder was observed under SEM to have
a smooth angular surface which provides inferior binding capability with the resin binder and

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therefore lower strength. Panels made from concrete powder and limestone dust were found
to have the least strength. The porous structure of concrete become the weakest area for
cracks to propagate. Similarly, for limestone dust, the clump of fine powder filler result in
degradation in strength.
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3.2.2. Effect of coupling agent on the MOR of powder-resin composite
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To achieve high flexural strength of the composite panels, adhesion between the resin
and the powder filler needs to be improved. Strong adhesion is dictated by good wettability of
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two similar components. The powder fillers used in this study are inorganic and offer poor
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covalent bonding with an organic polymer resin. The weak bonding between these two
components can be improved by coupling agent (CA) addition. The introduction of CA helps
to join both the organic and inorganic functionality within the same molecule. Fig.8 A (i) (ii)
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shows the glass substrate before and after the silane coating respectively. Dispersion of
hydrated silane was observed on the treated glass surface with a contact angle of resin on
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glass substrate decreased from 43.4o to 12.05o. Similarly, improvement in wettability of resin
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on CaCO3 substrate was observed in Fig.8 C with the average contact angle decreased from
60o to 15o.

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A(i) A(ii)

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B(i) B(ii)

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Fig. 8. (A) SEM analysis of inorganic substrate (i) before (ii) after silane treatment
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Contact angle of resin on (B) silica & (C) CaCO3 based substrate (i) before (ii) after silane treatment

From Fig.6, in all tested samples, silane CA was observed to enhance the panel’s
flexural strength significantly. In the non-coupled panels, poor wettability results in a weak
interfacial bonding among the filler particulates and binder. The poor adhesion became the
weakest spot for cracks to initiate and propagate, which resulted in premature failures of the
samples. In contrast, in the treated samples, resin wettability on powder by silane was
enhanced significantly, which result in improved adhesion and compatibility among the

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components. The strong internal bonding allowed maximum stress transfer and
correspondingly, increasing the flexural strength. The improvement can also be seen from
fracture surface analysis under SEM that was done post the flexural testing of the composites.
It is shown in Fig. 9A that the non-treated panels have rougher surfaces with several
pores shown at the fracture surface. The rougher surface might be resulted from the particle
pull-out or delamination from the weak adhesion between the resin and powder filler. On the

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contrary, the fracture surfaces of the treated panels in Fig.9B showed shearing deformation
characteristics. The strong silane adhesion on the resin and filler prevented particle pull-out

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and led to shear yielding before fracture. Higher energy was required for a material to fail in
shear which corresponded to higher bending stress.

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With the improvement in the interfacial adhesion, the mechanical properties of the
powder particulate can work effectively in enhancing the flexural strength of the final
composite panel. From Fig.6 and Fig.10, it is observed that Quartz, sand and glass which

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compose of hard SiO2 particles have flexural strengths of 53.0, 51.2, 47.8 MPa respectively.
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An improvement of more than 50% are observed in both quartz and sand with the highest
increase (81.75%) observed in glass composite panel. The CA enhances the surface adhesion
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between resin and powder significantly, minimizing the weak spots in the panel and allowing
cracks to extend through the resin matrix and bridge through the powder filler particles. As a
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result, high strength is achieved. Similarly, by silane addition, the flexural strength of calcium
carbonate-based composites was also improved to around 35 MPa, with seashell panels
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increased to an average value of 38.3 MPa due to its fibrous nature. The strength
improvements in calcium carbonate slabs are seen in Fig.10 to be in the range of 18 -36%,
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much less compared to silica-based panels. The inferior properties of CaCO3 particulates with
lower strength and hardness (Mohs hardness: 3) compared to SiO2 particles are the reason for
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the slight improvement in the average strength of the final CaCO3-composite panel.
Furthermore, minor improvement in limestone dust and concrete panel were observed in
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Fig.10 with silane addition. Although surface adhesion between powder and resin might
improve with silane CA, the porous structure and the clustering powder in concrete and
limestone dust powder are still the weakest spots in the final composite panel. Under load,
cracks propagate through the body of these weak particles resulting in zero improvements in
strength.

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Fracture surface from non- Fracture surface from

treated panels silane-treated panels

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A B

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CaCO3 – based composite
Low Magnification

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M

SiO2 – based composite

Low Magnification
D
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C EP

SiO2 – based composite

AC

High Magnification

Shear deformation
Delamination and particle characteristics – Translation
pull-out and slippage

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Fig. 9. SEM analysis of powder-resin composite panel (A) before & (B) after silane treatment

Percent improvement of flexural strength

Concrete 16.57

LD CaCO3 16.67

CaCO3 25.90

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Samples

Dolomite 36.64

Seashell 18.58

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Glass
81.75
Sand 53.29

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Quartz 50.57

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00

Percent improvement after addition of coupling agent

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Fig. 10. Percent improvement of powder-resin composite with varying powder filler after silane CA treatment

3.2.3. Effect of coupling agent on the MOE and toughness of powder-resin composite
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A Flexural strength B Shear lip and toughness

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60 160
1*
140
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50 4* 2*
Flexural stress (MPa)

120
Toughness ( MPa)

5* 3* NO CA
40 NO CA
100 6* 1*
2* CA
CA
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30 80 3*
4*
60 5*
20 6*
40 7*
8*
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10 20 7*
8*
0 0
AC

0 2 4 6 0 2 4 6

Extension (mm) Shear lip size (mm)

Fig.11. (A) Flexural testing graph on polymeric glass composite panel

(B) Shear lip and toughness of powder-resin composite panel

From Fig.11A, it is observed that the surface treatment of the inorganic powder by
CA improves the flexural strength, MOE and toughness of the final composite panels.

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MOE is defined as the composite resistance to elastic deformation and is calculated from the
gradient line of the stress-strain curve. Material with low MOE bends substantially when
stress is applied to it. To prevent massive deflection, material set under beam structure
requires high MOE. From Fig.11A, it is shown that the MOE/ stiffness increases with CA
addition, with an improvement of the slope in the stress-strain curve from 5 to 20 MPa. The
long hydrophobic polymer chain of silane CA at the interface of resin and powder filler

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provides better stress transfer among these components, resulting in higher stiffness and
strength. Similar study by Wong also showed a linear correlation between MOE and silane

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addition (Wong et al.,1994).
The improved stiffness and strength due to silane CA ensured high energy absorption

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during the deformation which also correspondingly enhanced the composite toughness.
Toughness is the material’s ability to deform plastically before fracture. The toughness of the
composite was measured in this study from the area under the flexural strength-strain curve.

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In Fig.11B, an average improvement of 30 to 40 percent was observed in all tested samples,
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except for concrete and limestone dust. Based on the explanation in section 3.2.1, it is the
porous structures and the clustering powder in concrete and limestone dust that results in
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lower mechanical properties. According to Lai et.al, there is a linear correlation between
shear lip size and fracture toughness (Lai et al., 1980). When a semi-ductile material is tested
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to failure under bending test, the crack propagates into 3 stages, similar to the fatigue crack
growth as shown in Fig. 12 C (Total Materia, 2010):
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Stage 1 (Short crack growth propagation stage)

Stage 2 (long cracks)
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Stage 3 (Catastrophic failure)

During stage I, the fracture will exhibit a 45-degree lip. The 45-degree lip is where the
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maximum slippage has occurred between the components in the material. The crack will
continue to propagate at an initial crack growth direction until it is halted by a microstructural
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barrier i.e. inclusion, grain boundary, etc. At this stage, as the stress intensity factor K
increases due to crack growth, the crack will start to propagate perpendicularly to the load
direction, initiating stage II, followed by unstable crack growth (catastrophic rupture) in stage
III.
All of the composites in this study showed 45-degree lips which correspond to
material failing at high shear stress (Total Materia, 2010). Higher toughness materials are
proved in this study to have bigger shear lip size. From Fig.12 B, an addition of around 1 mm
lip size was observed in all samples after the addition of CA. Similar results were also
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justified from the study conducted by previous researchers (Lai et al., 1980, Zulkifi et al.,
2010)

A B C

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+ 1 mm shear lip + 2 – 2.5 mm
shear lip

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Fig. 12. Shear lip of powder-resin composite (A) before (B) after treatment.

(C) Fracture surface schematic of powder resin composite

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3.3. Compression strength
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Fig.13 reports the maximum compressive stress of the powder-resin composite. In the
absence of CA, panels made from Quartz and sand were found to have comparable
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compressive strengths of 129 and 124 MPa respectively. The inferior property of sand
composite was mainly due to its impurity. As reported in the XRF analysis previously in table
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1, there is 94% silica in the sand with 6% of other contaminants such as clay, silt, dust, stone
fragments, and plastic organic matter (Pettijohn et al, 1973). These particle act as a stress
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concentration for cracks to grow under compression loading, resulting in the degradation in
strength.
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Furthermore, it can be observed that glass, dolomite and CaCO3 have a comparable
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strength of approximately 100-110 MPa. Similar to the explanation in section 3.1, it is the
powder smooth angular surface characteristic that results in inferior binding capability with
the resin binder and therefore lower strength. Seashell was observed to have better strength
due to its rough surface and fibrous nature. On the contrary, the clustering of limestone dust
powder and porous concrete particulates result in lower compressive strength.
Similar to the case of flexural test, with improvements in the interfacial adhesion from
the CA, the powder particles can work effectively in enhancing the compressive strength of
the final composite panel. The CA minimizes weak spots in the panel and allows cracks to

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extend through the resin matrix and bridge through the powder filler particles. As a result,
high strength is achieved. The improvement in compressive strength, however, is not as much
compared to the flexural strength, with an improvement of only about 15-20% in silica-based
composite and less than 10% in calcium carbonate-based panels. When low-quality particles
are used, a negligible improvement was again observed in the compressive strength of
concrete and limestone dust composite.

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Compressive strength
180

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No CA
160 153
144 CA
Compressive strength (MPa)

140 129 124 122 %improvement

114119 116

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120 113
108 106
101
100 87 87
81 79
80

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60
40
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18.6 16.1 20.8
20 4.4 7.4 6.6
0.0 -2.5
0
Quartz Sand Glass Seashell Dolomite CaCO3 LD CaCO3 Concrete
M

-20
Samples
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Fig. 133. Compressive strength of powder-resin composite panel with varying powder filler and silane coupling
agent
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3.4. Scratch resistant test

C EP
AC

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Scratch resistant test

100 0

90
-50
80 Load

Penetration depth (µm)

70 Quartz
-100
Sand
60
Load (N)

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Glass
50 -150
seashell
40
Dolomite

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-200
30 CaCO3
20 Concrete
-250

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10 LD CaCO3
Resin
0 -300
0 1 2 3 4 5

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Scratch position(mm)
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Fig. 14. Penetration depth of powder-resin composite with varying powder filler

Fig. 14 reports the scratch depth of the samples from 1 to 100 N within 5 mm scratch
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mark. Quartz and sand composite panels were observed to increase in line from 0- 150 µm at
the corresponding load. The value was fairly equivalent with glass composite with a
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penetration depth of 0 – 160 µm. The slight inferior scratch resistant in glass composite was
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owing to lower strength and hardness of glass particulate (Mohs value 5.5) compared to
Quartz with a Mohs value of 7 (Mineralogical Society of America. 1997). The high strength
and hardness of crystalline SiO2 in Quartz and sand was due to the strong interwoven
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tetrahedral structures between silicon and oxygen. To break the silica, all the bond need to be
broken resulting in higher hardness value (Cronodon, 2017). In a glass, the Na2O structure
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disrupted the crystalline SiO2 by the introduction of oxygen atoms in excess of the well-
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arranged covalent bonds. During the fast cooling process, the SiO2 does not have enough time
to crystalline, forming amorphous with short range (Corey et al., 1983). As a result of the
irregular structure, glass has a slightly lower strength and hardness compared to Quartz/sand.
(Corey et al., 1983).
Furthermore, by comparing to that of silica-based composites, it was observed that the
scratch-resistance in all CaCO3 panels was lower by around 50 µm. Calcium carbonate is
made up of two ions: cation (Ca2+) and (CO32-). The calcium and carbonate ions are held
together by the ionic bond with carbon and oxygen atoms in carbonate ion are held together

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covalently. The ionic bond is formed by the electrostatic attraction of 2 oppositely charged
ions, Ca2+ and CO32-. Such bonding is weaker than covalent bond and therefore only produce
moderate hardness (Mohs hardness: 3) and strength.
It was also observed that seashell and dolomite have better scratch resistance
compared to CaCO3 alone. Seashell, although was made from CaCO3, it was made from 2
different crystal structures, with a layer of calcite on the outside of their shell while building

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an aragonite layer on the inside of their shell. This was proved from XRD analysis in Fig.15.
Aragonite has a structure that is more resistant to stress than calcite. This result in higher

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hardness compared to other calcium carbonate-based panels. In dolomite, the structures were
arranged by an alternated layer of magnesium, calcite and carbonate ions. The significant size

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difference between calcium and magnesium helps the ions to compact better in much stable
arrangement and correspondingly, higher hardness compared to CaCO3.
The penetration depth of the concrete panels was also investigated to stand in parallel

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with the seashell-based panels but with more fluctuation due to the mixed calcium silicate
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content as well as the impurities within. Lastly, limestone dust panel was found to have the
lowest penetration depth compared to the other resin-based composites in this study, with a
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value of -240 µm at 100 N. The low value was due to the clustering powder as well as
slightly higher resin content to cover up the bigger surface area of the smaller particle powder
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filler.
It was also found in this study that no significant difference in scratch resistant was
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observed between the untreated and silane treated panels.

A
C EP
AC

Fig.15. XRD analysis of (A) pure CaCO3 (B) seashell

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3.5. Water absorption

Water absorption
0.006
0.00512

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0.005
0.00426 0.00431 0.00422 0.00421
Water absorption (%)

0.004 0.0038

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0.00298 0.00284 0.00314
0.00284 0.00283
0.003 0.00264 No CA
0.00228
0.00197 CA

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0.002
0.00112 0.00123 0.00131 0.00122 Sealant
0.00103 0.00112 0.00117 0.00111
0.00098 0.00092
0.001

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0
Quartz Sand Glass Seashell Dolomite Limestone LD CaCO3 Concrete
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Samples

Fig. 16. Water absorption of powder-resin composite with varying powder filler, and addition of coupling agent
and sealant
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Fig.16 reports the water intake of the samples in weight percent. It was found that
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non-silane treated panels absorb water in a range from 0.00284 to 0.00512%. The powder in
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this study are inorganic and contain hydroxyl groups (-OH) on its surface (Zhuravlev, L.T.,
2000, Snethlage, R., 2011, Tang et al., 2014). Hydroxyl group are polar/ hydrophilic
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(Department of Chemistry, 2017). The hydrophilic nature of powder on of the final

composite surface tends to be wetted considerably by water. Regardless, the water absorption
in the final product is still less than 0.01% which is due to the hydrophobicity of the resin
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binder used.
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With the addition of CA, improvements in water-resistance are observed to increase

by approximately 60-70 percent. Silane CA has hydrophobic surfaces that prevent wetting on
the powder surface. Fig.17B illustrates an improvement in the hydrophobicity of the
composite panels after the silane treatment with the contact angle increased from 29.7 to
104.85o.

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A B

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Fig.17. Contact angle of water on powder –resin composite (A) before (B) after silane treatment

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The improved water-resistant data in this study due to the addition of CA were
recorded on unpolished products. After the samples were ground and polished, the water-
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resistant properties decrease slightly due to the exposed cross-section of the powder. It is
recommended that the application of the industrial sealant is used. Silane, which breaks down
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to silicon and hydrogen, has a relatively small molecular structure. The sealant will bond with
the composite substrate to narrow any opened channels, and consequently, prevent water
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molecules to penetrate. (Thomas, 1898).

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3.6. Thermal degradation

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It is shown in Fig.18 that weights of all the tested composite start to decrease at around
270oC with maximum weight losses happening at temperatures ranging from 350 to 550 oC.
At the corresponding temperature, the polymer chain of the resin in the composite panels
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starts to break apart and degrade. Except for concrete panels, the weight loss of all the tested
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composites was observed to be 20 % with concrete panels having continuous degradation to

more than 40%. The massive weight loss in the concrete panels was probably due to the
impurities and polymer fibre mesh in the mix. Further degradation of CaCO3-based panels
was also observed at a temperature of 740oC where CaCO3 disintegrate to CaO and CO2.

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Thermal degradation

100

Quartz
80
Sand
Weight (%)

Glass
60

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Seashell
Dolomite
40
Resin

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Eng.Stone
20
CaCO3
Concrete

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0
-50 150 350 550 750 950
Temperature (OC)

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Fig. 18. Thermal degradation of powder-resin composite with varying powder filler
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3.7. Comparison to standard
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Table 2 reports the mechanical and physical performances of commercial stones in the
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market. Except for limestone dust- and concrete- resin panels, it was found that all the treated
samples appeared to have superior performance in bending strength with values ranging from
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35 - 53 MPa, in comparison to granite and marble with a strength of only 14-28 and 6-27
respectively. Additionally, when treated with CA, silica-based panels are comparable to that
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of commercial engineered stones. Besides strength, the breaking load of the panel also
determined by the actual dimension of the finished unit. High flexural strength composites
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can be produced in larger and thinner slab, which can be used to span greater distances with
relatively lightweight. For low flexural strength materials, such as marble and granite, the
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slab needs to be made thicker with a shorter span.

Compression strength of the treated composite panels in this study ranges from 79-
153 MPa when treated with CA. Except for Quartz and sand, most of the produced samples
offer inferior performance in compression strength when compared to granite and engineered
stones. Hard crystalline SiO2 particulates in commercial stones and silica-based panels in this
study are the reason that attributes to the high compression strength. It should be noted that
the compression strength only measures the resistance of the materials to crushing and is

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rarely a problem in construction. For a comparison, a residential and commercial structure
concretes have a compressive strength as low as 17 and 28 MPa respectively.

The water absorption of the produced samples is equivalent to coated marble or

granite as well as engineered stone. The lower water absorption of CaCO3-resin panels
compared to uncoated marble is due to the in-cooperation of the hydrophobic resin.

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For a scratch resistance test, the values depend on the raw materials that make the
composites. SiO2 panels have higher scratch resistance value compared to that of CaCO3. The
resin also degrades the hardness considerably.

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The thermal degradation of the tested panels depends on the polymer resin binder

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used. Similar to engineered stones, they degrade at 350oC. The only advantage of natural
stones over the man-made engineered stone products is that they degrade at a temperature
higher than 800oC.

U Table 2
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Comparison to standard
Flexural Compression Water Scratch Thermal
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strength strength absorption (%) resistance at degradation

(MPa) (MPa) 100 N load temperature
(OC)
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Granite 14 – 28 120 – 131 0.01% (Coated: - 88 > 1000

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0.00123%)
Marble 6 - 17 52 -72 0.04% (Coated -240 > 848
0.00186%)
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Engineered stone 37- 53 129 – 188 0.00145% -162 > 350

Treated Powder- 27 - 53 79 -153 0.00421 - -240 to -146 > 350

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resin composite 0.00112

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3.8. End of life panels

Composite, having made from two or more constituent materials, are specifically
designed to acquire distinct and unique characteristics from its individual components. The
disadvantages, however, lies on its recyclability. The different components tend to become
complex issues in recycling. Separation of each component is not plausible. Current waste
management and environmental legislation require all engineered materials to be properly

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recovered and recycled (Australian Government, 2012). This part of the section aims to find a
solution for end of life powder-resin composite products and off-cuts. This will unravel
solution not only for today but also the future.

The production process of the recycled panels from the end of life panels is similar to
the powder-resin composite production explained in section 3, but high proportion of powder
filler was substituted with the aggregates from the waste panels. The waste panels were cut,

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crushed and sieved using jaw crusher and metal screened to 0.1-1 mm and 1- 4 mm size
aggregates. Fifty percent of the coarse aggregates were then mixed with 30% of fine

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aggregates, along with 10% of fine powder (108 um), 10% mixture of resin and hardener to
form recycled panels. The resulting panels are displayed in Fig.19, imitating the natural look

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of granite stone. The mechanical and physical properties are also presented in Table 3 below
and proved to be still very comparable to that of produced panels in this study. The recycled

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panels can be crushed again and reuse as raw materials for the next production of recycled
panels. So far, the composite panels were only recycled 3 times from the same materials. It was
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found that the third panels produced still have similar mechanical properties compared to the first
two recycled panels. Future studies are still needed to thoroughly understand the mechanical
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behaviour of the recycled panels over multiple recycling cycles.

Table 3
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Mechanical properties of recycled panels

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No. Mechanical properties Mechanical properties

1 Flexural Stress (MPa) 33.9
2 Modulus of elasticity (GPa) 5.35
2 Compression stress (MPa) 113.5
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4 Water absorption (%) 0.0112

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Fig. 19. Recycled panels

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4. Conclusion
This study reported a successful manufacture of high-quality structural slabs from
various waste powder filler. Eight types of powder i.e. Quartz, sand, glass, seashell, dolomite,
limestone, concrete and limestone dust were used. With optimal resin/filler ratio, high
compaction pressure, and heat as well as a coupling agent (CA), a densified powder-resin

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composite panels with high mechanical properties were produced. It was found that without
CA addition, bondings between resin and powder particles are the crucial factor affecting the

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flexural strength. Quartz and sand particles which have high surface roughness adhere
effectively with the resin binder. The better bonding leads to higher strength. Similarly, high

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surface roughness along with the fibrous nature of seashell results in a final panel with
comparable strength. Other powder particles such as glass, limestone and dolomite have a
smoother surface and therefore produce lower strength panels. Porous structure in concrete

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and clump of fine powder in limestone dust also result in inferior flexural strengths.
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With CA addition, adhesion between powder and resin were improved considerably
with Quartz and sand-based panels increased to more than 50 MPa. Glass panel was found in
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this study to have the highest average improvement in flexural strength of 81.75 % from 26.3
to 47.8 MPa. Improvements in calcium carbonate slabs are also observed to be in the range of
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18 -36%. The slight inferior properties of CaCO3 particles with lower strength and hardness
compared to SiO2 particles are the reason for the slight improvement in the average strength
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of the final CaCO3-composite panel. Negligible improvement is found in concrete and

limestone dust due to their inferior particle properties that become the weakest area for cracks
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to propagate. Compression strength, scratch resistance, and water absorption were also
reported in this study. Except for scratch resistance, all the mechanical properties were
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improved with CA addition. Silica-based panels were found to offer superior properties
compared to that of calcium carbonate. Regardless, the strength of all the treated panels,
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except for limestone dust and concrete based resin panel, are much better than natural stones.
These new approaches of using powder filler in resin-based composites can be a new
alternative to produce green materials that provide both environmental and economic
benefits.

Acknowledgements

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The research is based on works supported through the project RP10022 by CRCLCL. We
would like to express a deepest gratitude and appreciation to Mr. Bill Joe who shares his
valuable knowledge on mechanical testing procedures and Dr. Irshad Mansuri for providing
laboratory support and machine training. Their patience and skill in machine operation made
the whole process smooth and easy. Authors are also indebted to many technical staffs. A
special thanks to Sarah Kelloway and Irene Wainwright from XRF laboratory, Karen Private

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and Sigrid Fraser from MWAC electron microscope unit, and George Yang for machine
training and research supports.

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List of abbreviations

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ASTM American Society for Testing and Materials
CA Coupling agent
CSH calcium silicate hydrate
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GP Glass Powder
PGC Polymeric glass composite
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LD Low density
MOE Modulus of elasticity
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MOR Modulus of Rupture

PF Powder filler
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MWAC Mark Wainwright Analytical Centre

SEM Scanning Electron Microscopy
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UV Ultraviolet
XRF X-Ray Fluorescence
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Malpani, R., Jegarkal, S.C., Shepur, R., Kiran, R., & Adi, V.K. 2014. Effect of Marble
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Mineralogical Society of America. 1997. Mohs scale of Hardness.

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Highlights

• A novel hybrid particulate composite slab from local waste materials is proposed.
• The waste powder was mixed with resin to produce marble-like stone composite slab.
• Particle morphology, powder-resin interface, and the slab properties were studied.
• The prototypes showed comparable mechanical performance to natural and
engineered stone.

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