resources

Article
The Potential Use of Oyster Shell Waste in New
Value-Added By-Product
Thamyres H. Silva 1 , Joana Mesquita-Guimarães 1,2, * , Bruno Henriques 1,2 , Filipe S. Silva 2
and Márcio C. Fredel 1
1 Ceramic and Composite Materials Research Group (CERMAT), Department of Mechanical Engineering,
Federal University of Santa Catarina (UFSC), Florianopolis 88040-900, SC, Brazil;
thamyhellens@gmail.com (T.H.S.); bruno.henriques@ufsc.br (B.H.); m.fredel@ufsc.br (M.C.F.)
2 Center for MicroElectroMechanical Systems (CMEMS), Department of Mechanical Engineering,
University of Minho (UMinho), 4800-058 Guimarães, Portugal; fsamuel@dem.uminho.pt
* Correspondence: mesquitaguimaraes@dem.uminho.pt; Tel.: +351-25-351-0732




Received: 21 November 2018; Accepted: 20 December 2018; Published: 5 January 2019


Abstract: Calcium carbonate is one of the most used raw materials in various industries, such as
construction materials, food supplement, pharmaceutics, animal feed, plastic production, and
others. Calcium carbonate can derive from marine wastes, like crustaceans and bivalve’s shells.
The worldwide demand for new sources of food has increased exponentially, and following that
tendency, the mariculture—especially the oyster culture—has been increasingly resorting to farming
techniques. In 2016, 438 billion tons of oysters were produced. The majority of the shells were unduly
discarded, presenting a public health problem. This article offers a solution based on the reuse and
recycling of oyster shell residues in the production region of Florianópolis, SC, Brazil. The presented
solution is an oyster shell by-product developed by a local company which produces artificial stone.
The main component of the artificial stone is a composite material made of oyster shells incorporated
in a polymeric resin. The mechanical properties, such as its flexural strength, hardness, Weibull
modulus, and fracture analysis, were held in the artificial stone. The mechanical results of the new
artificial stone were compared with other natural stones, such as granite and marble, and other
commercial artificial stones. This material owns suitable mechanical properties for table tops and
workbenches. Using this product as an artificial stone represents an innovation in the development
of a new product and adds commercial value to local waste. This product is an excellent example
of a circular economy for local producers who care about the environment, and it encourages the
reduction of extraction of natural stone, such as granite and marble.

Keywords: oyster shells; recycling; potential applications; value-added product

1. Introduction
With the exponential population growth in the 20th century and the demand for increased
food production, the previous typical handcraft-based sectors began to focus their investment in
the industrialisation of food production. Aquaculture has experienced considerable growth on the
global scale, and mariculture is one of the most significant industries [1–3]. Mariculture is related to
the production of aquatic organisms in marine waters, which involves the cultivation (via farming
techniques) of sea fish, crustaceans, and molluscs [4]. Seafood production sustains a part of the global
economy, where the commercialisation of molluscs is in second place on a worldwide level, e.g.,
“with 16.1 million tons of molluscs (19 billion USD) produced annually”. According to the Food and
Agriculture Organization of the United Nations (FAO), the value of the global production of this
species for the year 2016 was 3.69 billion USD [5,6].

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In In
thethe
oyster
oystermarket,
market,thethemost
mostproduced
produced species is Crassostreagigas,
is Crassostrea gigas,widely
widelyknownknown asasthethe Pacific
Pacific
oyster. The Pacific oyster has become the cultivated oyster of choice in many
oyster. The Pacific oyster has become the cultivated oyster of choice in many regions of the world, regions of the world, due
to due
its speedy growthgrowth
to its speedy and itsand
resilience to many
its resilience diverse
to many environmental
diverse environmental conditions. In 2003,
conditions. the world
In 2003, the
world production
production of C. gigasof C. gigas reached
reached about 4.4about 4.4 million
million tons; their
tons; their shellsshells represent
represent more more
thanthan70%70% of
of their
their weight,
weight, resulting resulting
in 3.08inmillion
3.08 million
tons oftons of shell
shell waste.waste.
TheseThese numbers
numbers indicatethe
indicate theneed
needto todispose
dispose of
of these
these residues residues
properly, properly, and tothe
and to assess assess
chancesthe ofchances
reuse and of their
reuseintroduction
and their introduction to new
to new manufacturing
manufacturing
processes [5,7,8]. processes [5,7,8].
Based
Based on onaa geographic
geographic overview
overviewofofthethe oyster
oysterproduction
production and andenvironmental
environmental impacts, the
impacts,
following map (Figure 1a) presents the regions of the highest production of
the following map (Figure 1a) presents the regions of the highest production of the C. gigas (referringthe C. gigas (referring to
the year of 2016) [9]. Since the 1950s, the world panorama of the production of C. gigas exhibited a
to the year of 2016) [9]. Since the 1950s, the world panorama of the production of C. gigas exhibited
remarkable tendency with a steady increase. There were, however, some decreases in production,
a remarkable tendency with a steady increase. There were, however, some decreases in production,
sometimes related to environmental conditions, such as water temperature, or even ocean currents
sometimes related to environmental conditions, such as water temperature, or even ocean currents
carrying micro-organisms that contaminated (or were also caused by the excessive death of) the
carrying micro-organisms that contaminated (or were also caused by the excessive death of) the marine
marine animals in a given region. Finally, in 2014, the market reached 625.925 tons, as illustrated in
animals in a given region. Finally, in 2014, the market reached 625.925 tons, as illustrated in Figure 1b.
Figure 1b. According to the FAO, Asia has become the most important producer of molluscs,
According
followedto bythe FAO,and
Europe Asiathe
has become [5],
Americas theasmost important
illustrated producer
in Figure of molluscs,
1c. Chile followed
is the leading by Europe
producer in
and the Americas [5], as illustrated in Figure 1c. Chile is the leading producer
the Americas and ranks ninth in the world, and Brazil is the second largest producer in the Americasin the Americas and ranks
ninth
andinisthein world, and Brazil
14th place in theisworld
the second largest
ranking; theirproducer
marketsinweighthe Americas
1227.4 and and 934.8
is in 14th placetons,
million in the
world ranking; their markets weigh 1227.4 and 934.8 million tons, respectively
respectively [5]. In this production sector, one of the most worrying factors is the amount of residue [5]. In this production
sector, one of and
generated, the most
this isworrying factorsto
directly related is the
the volume
amountof ofoyster
residue generated,
shells produced.andMost
this isofdirectly
the waste related
is
to deposited
the volumeinoflandfills,
oyster shells produced.
abandoned Most or
on land, of the waste to
returned is deposited
the sea, thus in landfills,
causing abandoned
incalculableon
land, or returned impacts.
environmental to the sea, thuswaste
These causing incalculable
products, when environmental
deposited in theimpacts. These waste
soil, contaminate and products,
attract
animals
when due tointhe
deposited thestrong odour. When
soil, contaminate andthe oyster
attract shell waste
animals due toisthe deposited in the When
strong odour. sea, itthe causes
oyster
grounding
shell waste is and infectsinthe
deposited themarine population.
sea, it causes The lack
grounding and of regulation
infects and population.
the marine inspection inThe several
lack of
oyster-producing
regulation countries
and inspection reflect aoyster-producing
in several significant environmental impact agenerated
countries reflect significantbyenvironmental
this sector
[10,11].
impact generated by this sector [10,11].

Figure1. 1. General
Figure General panorama
panorama of countries,
countries, increasing
increasing market
marketandandthe
theprincipal
principalproducers
producers of of
Crassostrea
Crassostrea gigassince
gigas sincethe
the 1950s:
1950s: (a)
(a)Worldwide
Worldwidemap mapof of
thethe
panorama of the
panorama of producing countries;
the producing (b)
countries;
(b)Global
Globalamount
amount ofof
C.C.
gigas produced
gigas produced since the the
since 1950s; (c) Worldwide
1950s; overview
(c) Worldwide overviewof mollusc farming;
of mollusc (d)
farming;
Destination of the waste of oyster shells after cultivation. Adapted from [5,10].
(d) Destination of the waste of oyster shells after cultivation. Adapted from [5,10].
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The first reported case of a public health problem related to careless disposal of oyster residues
was made known by the begging of the oyster farming process in the early 1980s in South Korea.
The statistical data shows that 300,000 tons of oyster shells were annually disposed, and over time
microbial decomposition occurred and developed very toxic gases such as NH3 and H2 S [12,13].
The South Korean government, alarmed with the state of public health, financed a project to define new
strategies for recycling these wastes. Within these programs were created factories for calcium and
fertilisers production with the purpose of increasing the number of recycled oyster shells. However,
only 30% of the discarded shells were reused by the companies [13,14].
The Brazilian production of oysters has shown exponential growth, so there is a strong incentive to
conduct research in this area [15]. The southern region of Brazil, in Santa Catarina, Florianopolis, is the
area with the highest mollusc production in the country. In 2014, according to EPAGRI (Agricultural
research company and rural extension of Santa Catarina), 21,554 tonnes of oysters were produced [16].
Based on studies developed in this area, the graph of Figure 1c shows that only 10% oyster shell
residues are reintroduced into the industry. Most of this waste is collected by the company that treats
the city’s solid waste and destined for landfills. Other amounts are thrown into the sea, or disposed of
in a wasteland [15].
The cleaned oysters can be reused in several applications. The principal component
(approximately 96%) of oyster shells is calcium carbonate (CaCO3 ), which can be used in various
sectors; for example, the construction industry, as an aggregate of limestone for cement, and even the
pharmaceutical industry, as a calcium-enriched supplement [4,13].
In this work, the authors present a specific commercial product that reuses the oyster shells to
manufacture an artificial stone to use in tabletops and workbenches. In collaboration with the local
company, the CERMAT/UFSC research group made a complete mechanical characterisation of the
product using 4-point bending flexural tests, determining the Weibull modulus, performing a fracture
analysis by observing the fracture lines in a scanning electron microscope, and measuring the hardness
of the different materials of the composite. Based on the extreme potential of the oyster shell residue
as a raw material, it was analysed in order to encourage the local companies of the producer countries
to use this inexpensive source of material.

2. Materials and Methods

A local company (Florianopolis, SC, Brazil) provided samples of artificial stone. Regarding the
information on the technical data, reinforcement material of the artificial stone is the region’s oyster
shells after being properly clean, milled, and mixed with unsaturated polyester resin. It was also
reported that a step of vibration precedes the compression procedure. These are the typical information
presented in catalogues of identical artificial stones reinforced with marble [17] or glass [18].
The CERMAT/UFSC lab performed the compositional, mechanical, and thermal analysis
characterisation. The typical oyster shells of the region and the artificial stone samples provided
by the company are shown in Figure 2.
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Figure
Figure 2. Images
2. Images of of bothsides
both sidesof
ofshells
shells from
fromCrassostrea
Crassostreagigas oysters
gigas (a), (b);
oysters samples
(a,b); of the
samples of artificial
the artificial
stone made from oyster shells residues (c) and detail of the homogenous dispersion of the crushed
stone made from oyster shells residues (c) and detail of the homogenous dispersion of the crushed
oyster shells in the resin matrix (d).
oyster shells in the resin matrix (d).
2.1. Technical
Technical AnalysisAnalysis
The samples were characterised by using several technical analyses. A low-vacuum scanning
The samples were characterised by using several technical analyses. A low-vacuum scanning
electronic microscope (TM3030, Hitachi, Japan) was used to inspect the oyster shell parts,
electronic microscope (TM3030, Hitachi, Japan) was used to inspect the oyster shell parts,
microstructure, and fracture. A microanalysis system of energy dispersive X-ray spectroscopy (EDX)
microstructure,
(Swift ED3000,andOxford
fracture. A microanalysis
Instruments, system UK)
High Wycombe, of energy dispersive
that allows for the X-ray spectroscopyof(EDX)
semi-quantification
(Swiftthe
ED3000,
existentOxford
elementsInstruments,
on the samples High
wasWycombe,
attached toUK) that allows for the semi-quantification of the
the microscope.
existent elements on thetests
The mechanical samples was attached
were performed to the
taking microscope.
in account the typical tests done for this variety of
commercial
The mechanicalmaterials.
testsMechanical properties
were performed analysis
taking was done
in account theby accessing
typical teststhe flexural
done strength
for this variety of
and hardness
commercial of the Mechanical
materials. artificial stone. The flexural
properties strength
analysis was was assessed
done using thethe
by accessing 4-point bending
flexural strength
tests, which
and hardness ofsimulates the load
the artificial of aThe
stone. flexural force strength
flexural in an areawasof the sample.using
assessed More the
than4-point
15 samples
bending
tests,with
whichthe size of 70 × 30 × 20 mm3 were tested. A universal testing machine (DL 2000, EMIC, Brazil)
simulates the load of a flexural force in an area of the sample. More than 15 samples with
was employed using a cell load of 20 kN and the following test conditions: a loading rate of 1
the size of 70 × 30 × 20 mm3 were tested. A universal testing machine (DL 2000, EMIC, Brazil) was
mm/min, a distance between support pins of 42 mm, and the distance between loader pins of 21 mm.
employed using
The a cell
statistic load
tool of 20 kN
of Weibull and the
modulus wasfollowing
applied totest
the conditions: a loading
flexural strength results.rate
Thisof 1 mm/min,
modulus
a distance between support pins of 42 mm, and the distance between loader pins of 21 mm.
indicates that 63.2% of the fractures will occur at a critical strength, σ0. The critical strength indicates
The statistic
with tool of that
higher certainty Weibull modulus
the material willwas applied
withstand to strength
this the flexural strength
without results. This modulus
fracturing.
indicates that 63.2% of the fractures will occur at a critical strength, σ0 . The critical strength indicates
with higher certainty that the material will withstand this strength without fracturing.
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Hardness was determined on different points of the artificial stone by using a microhardness
HMV-2 (Shimadzu, Kyoto, Japan). The applied load was 100 g for 10 s.
With the aim of identifying future applications for this oyster powder as a form of calcium oxide,
a differential thermal analysis was done in order to determine the temperature of calcination and the
quantity of calcium oxide that is obtained after calcination. For this purpose, we used an SDT 2860
simultaneous DSC-TGA (TA Instruments, New Castle/DE, USA), using a heating rate of 10 ◦ C/min
until 1000 ◦ C.
A list of the tested method realised to explain the sequential procedure of analysis in this study is
presented in Table 1.

Table 1. List of the tested method realised in this study.

Technical Analysis Objectives

Inspection of the oyster shell parts, microstructure of the
Scanning Electronic Microscope
composite material, and the type of fracture of the artificial stone.
Confirm the chemical elements of the sample, as Ca, C, and O,
Energy dispersive X-ray spectroscopy
without contaminations.
Determine the flexural strength of the product samples.
4-point bending flexural test Use of the statistical analysis of Weibull modulus on the
flexural results.
Determine the hardness of the composite, as well as the hardness
Microhardness test
of each component.
Differential thermal analysis and Determine the calcination temperature of the residues and the
thermogravimetry amount of CaO generated in this process.

This sequential procedure of analysis was done to evaluate the quality of the samples, analyse
possible contaminations, and define the mechanical tests. The microstructural and chemical analysis
revealed a good quality of the samples product. The flexural tests were done, and the flexural
strength was determined and compared with commercial stones. As a consequence, the Weibull
modulus was obtained. This parameter indicates the critical strength and the reproducibility of the
fracture, which is a quality parameter. Afterwards, the hardness of different parts of the component
was determined and compared with the commercial ones. Finally, the differential thermal analysis
and thermogravimetry were done to compare the calcium transformation of the residues with the
commercial calcium carbonate in order to analyse the potential of the residues as raw material.

3. Results and Discussion

3.1. Characterisation of the Oyster Shells and Artificial Stone Samples

The observation of the oyster’s valves revealed that the shells are composed of an internal
leaf-shaped laminated part, and the external part has a porous lattice-shaped structure. Both parts have
as chemical composition calcium carbonate (CaCO3 ), with calcite as a crystalline phase. The outside
of the shell is the last part to be formed, and the calcium carbonate suffers a process of calcination in
order to strengthen the outside part of the shell [14]. Figure 3a illustrates each part of the oyster shell:
(A) is the inner part of the shell which corresponds to the lamellar part; (B) is the outer part of the shell
which corresponds to the porous layer; and (C) shows the lateral section of the shell, as well as the
lamellar layer along with the porous layer.
After the oyster shells were cleaned and powdered by grinding, they were mixed with unsaturated
polyester resin for the processing of the body part of the countertop, named as artificial stone.
In Figure 3b, it is possible to visualise that the mixture of resin oyster powder is well homogenised and
dispersed, taking into account the different sizes and aspect ratio of the powder. Occasionally, some
pores are visible.
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Figure
Figure 3. Schematic
3. Schematic representationusing
representation usingphotographs
photographs and
andSEM
SEMmicrographs
micrographs of:of:
(a) (a)
different partsparts
different of of
the oyster shell: (A) lamellar part, (B) porous side and (C) cross-section and porous-lamellar
the oyster shell: (A) lamellar part, (B) porous side and (C) cross-section and porous-lamellar interface;
andinterface; and (b) artificial stone, (A–C) details of the dispersion of oyster powder component in the
(b) artificial stone, (A–C) details of the dispersion of oyster powder component in the resin matrix.
resin matrix.
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3.2. Mechanical Properties of the Commercial Artificial Stone Samples

3.2. Mechanical Properties of the Commercial Artificial Stone Samples
The mechanical characterisation was performed and indicates the potential of using the oyster
The
shell mechanical
residues in thecharacterisation
conception of a new was value-added
performed and indicatesmainly
by-product, the potential
when aof using the oyster
strength-related
shell residues in the conception of a new value-added by-product, mainly when a
property is needed, as in the case of artificial stone. In this sense, the flexural strength and hardness strength-related
property is needed,
results can as in the
be compared case
with of artificial
other stone.
natural and In thiscommercial
artificial sense, the flexural strength
stones. The andbending
4-point hardness
results can be compared with other natural and artificial commercial stones.
flexural test results of the artificial stone samples are shown in Figure 4. The force-displacementThe 4-point bending
flexural test results of the artificial stone samples are shown in Figure 4. The
curves are shown in Figure 4a. The flexural strength results of the artificial stone and otherforce-displacement curves
arecommercial
shown in artificial
Figure 4a.andThe flexural
natural stonesstrength
are shown results of the
in Figure 4b artificial
in order to stone
allowand
for aother commercial
comparison of
artificial and natural
their values. stonesplot
The Weibull areobtained
shown infromFigure
the 4b in order
statistical to allow for
processing a comparison
of the 4-point bendingof their values.
flexural
The Weibull
tests resultsplot obtained
of the from
artificial theisstatistical
stone shown inprocessing
Figure 4c. of the 4-point bending flexural tests results of
the artificial stone is shown in Figure 4c.

Figure 4. Flexural results of the artificial stone samples: (a) Force-displacement curves, (b) flexural
Figure 4. Flexural results of the artificial stone samples: (a) Force-displacement curves, (b) flexural
strength results for artificial and natural commercial stones. On bold is the marked the flexural strength
strength results for artificial and natural commercial stones. On bold is the marked the flexural
of strength
the newofartificial stone, named ShellStone, and (c) Weibull plots obtained from the 4-point 4P
the new artificial stone, named ShellStone, and (c) Weibull plots obtained from the
bending flexural tests results tests
4-point 4P bending flexural for artificial stone.
results for artificial stone.

TheTheforce-displacement
force-displacement curves curves (Figure
(Figure 4a)4a) show
showaabrittle
brittlebehaviour
behaviourofofthe the fractured
fractured material,
material,
indicating that the contribution of the oyster shell residues influences the
indicating that the contribution of the oyster shell residues influences the fracture behaviour more fracture behaviour more
than
thanthe polyester
the polyesterresin resin[19,20].
[19,20].The
The flexural
flexural strength
strength result 20±±2 2MPa,
resultisis20 MPa,whichwhich is is a median
a median value
value
when compared with other commercial stones (Figure 4b). The artificial
when compared with other commercial stones (Figure 4b). The artificial stone presents higher stone presents higher flexural
strength
flexuralthan the artificial
strength than the stone called Aglostone,
artificial stone calledand then the marble,
Aglostone, and then natural stone. Aglostone
the marble, [17,18]
natural stone.
is Aglostone
a composite material
[17,18] made of marble
is a composite materialpowder
made ofand polyester
marble powderresin. Nonetheless,
and polyester resin.in our daily life
Nonetheless,
marble
in ouris daily
known lifeformarble
its high is resistance,
known forshowing
its high that the same
resistance, property
showing can
that besame
the replicated in ancan
property efficient
be
andreplicated in anway
sustainable efficient
by an and sustainable
artificial stone. way
Onby theanother
artificial stone.
hand, On thestone
artificial otherpresents
hand, artificial
lower stone
flexural
presents
strength lower
when flexural strength
compared when[21],
to Nanoglass compared
which to is aNanoglass
composite[21], whichmade
material is a composite materialand
of glass powder
made of glass
polymeric resin,powder and polymeric
and Marmoglass resin,
[22,23], and is
which Marmoglass
a composite [22,23], which
material madeis a of
composite material
glass microcrystals
made of glass microcrystals and marble powder with a polymeric resin.
and marble powder with a polymeric resin. Taking as reference the increase of resistance between Taking as reference the
increase of resistance between Aglostone to Marmoglass of more
Aglostone to Marmoglass of more than 32 MPa (equivalent to Nanoglass, 30 MPa), the introduction than 32 MPa (equivalent to of
Nanoglass,
glass 30 MPa),
microcrystals on thethe artificial
introduction
stoneofformulation
glass microcrystals on theincrease
can probably artificialthestone formulation
flexural strengthcan up to
probably
50 MPa. increase the flexural strength up to 50 MPa.
The Weibull analysis was performed using the bending test results to determine the Weibull
The Weibull analysis was performed using the bending test results to determine the Weibull
modulus and the critical strength of the product (Figure 4c). The Weibull theory is a continuous
modulus and the critical strength of the product (Figure 4c). The Weibull theory is a continuous
probability distribution of failure, where σ0 , m, and σ are correlated with the density of defects
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probability distribution of failure, where σ0, m, and σ are correlated with the density of defects
presentedininthe
presented thesamples
samples[24].
[24]. Density
Density defects
defects can
canbebeindicated
indicatedbybythe thedispersion
dispersion of of
thethe
fitting line,
fitting line,
where
where theweakest
the weakestsamples
samples determine
determinethe theslope
slopeofof
thethe
line [24,25].
line The The
[24,25]. linear fitting
linear was done
fitting was ondonethe on
theplotted
plotteddata, and
data, andthethe
considered
considered R2 was superior
R2 was to 0.97.
superior to The
0.97.characteristic strength
The characteristic means that,
strength means withthat,
a probability of failure of 63.2%, the samples will fail for that stress value
with a probability of failure of 63.2%, the samples will fail for that stress value [26]. In this case,[26]. In this case, thethe
characteristic
characteristic strengthisissimilar
strength similartotothe
theaverage
averagevalue
valueofofthe
the flexural
flexural strength
strength (20 (20 MPa),
MPa), however,
however,this this is
is not a rule. Regarding the Weibull modulus, the value obtained (m = 11)
not a rule. Regarding the Weibull modulus, the value obtained (m = 11) is similar to ceramic materials is similar to ceramic
materials (approx. m = 10) [27]. It is assumed that ceramic components present defects due to
(approx. m = 10) [27]. It is assumed that ceramic components present defects due to fabrication or
fabrication or usage. Implicitly, the samples present a first defect population, mainly in the volume
usage. Implicitly, the samples present a first defect population, mainly in the volume of the sample,
of the sample, and a second defect population, resulting from the surface, which leads to lower
and a second defect population, resulting from the surface, which leads to lower failure stresses [25].
failure stresses [25]. The scatter results for lower failure stresses indicate that bending stresses are
The scatter results for lower failure stresses indicate that bending stresses are more sensitive to surface
more sensitive to surface defects [25].
defects [25].
In the following micrographs (Figure 5) it is possible to detect the onset of fracture of a random
In theand
sample following micrographs
also identify (Figure
some details 5) it the
about is possible to detect
orientation of thethe onsetshell
oyster of fracture of a random
in the composite
sample and
material. also identify some details about the orientation of the oyster shell in the composite material.

Figure
Figure 5. 5.SEM
SEMmicrographs
micrographsofofthe
thefracture
fracture surface
surface of
of the
theartificial
artificialstone
stone(a).
(a).Detail
Detailofof
thethe
region of the
region of the
onset
onset fracture(b).
fracture (b).Detail
Detailimage
imageof
offractured
fractured lamellae
lamellae surface
surface(c).
(c).

Figure
Figure 5a5a shows
shows a typical
a typical view
view of initial
of the the initial fracture
fracture region.
region. By accessing
By accessing both both
sidessides
of theoffracture
the
fracture
it is it is
possible to possible
identify to
theidentify the place
place where where the
the material material
began began to
to fracture. fracture.
The The
left side hasleft side hasrelief,
a sharper a
sharper relief, showing the material that was pulled out from the right side,
showing the material that was pulled out from the right side, where it has a depression. This type of where it has a
depression.
fracture Thisthat
indicates type
theofmaterial
fracturehas
indicates thatbrittle
a typically the material
fracturehas a typically
by cleavage. Onbrittle fracturesurface
the fracture by
cleavage. On the fracture surface two types of zones are visible: (i) the smoothest zones,
two types of zones are visible: (i) the smoothest zones, which have higher amounts of resin, and (ii) the which have
higher amounts of resin, and (ii) the roughness zones, which correspond to the oyster shell material.
roughness zones, which correspond to the oyster shell material. An example of this zone is shown
in detail in Figure 5b. It is also relevant to illustrate the lamellar region of the oyster shell fracture
 Resources 2019, 8, x FOR PEER REVIEW 9 of 16
Resources 2019, 8, 13 9 of 15
An example of this zone is shown in detail in Figure 5b. It is also relevant to illustrate the lamellar
region of the oyster shell fracture (Figure 5c). The lamellar oyster shell parts correspond to the nacre
(Figure 5c). The lamellar oyster shell parts correspond to the nacre typology. Depending on the fracture
typology. Depending on the fracture orientation, this material can present a cleavage fracture,
orientation, this material can present a cleavage fracture, parallel to lamellas, and perpendicular to
parallel to lamellas, and perpendicular to lamellas, the toughness fracture is higher due crack
lamellas, the[28].
deflection toughness fracture is higher due crack deflection [28].
Additionally,
Additionally,the thehardness
hardness ofof the
the artificial stone was
artificial stone was determined
determinedusingusingthe themicrohardness
microhardness
technique.
technique. The samples received by the manufacturer consisted of two layers: the body body
The samples received by the manufacturer consisted of two layers: the part ofpart
the of
theartificial
artificial stone
stone composed
composed of two
of two materials,
materials, the oyster
the oyster shellsshells and
and the the unsaturated
unsaturated polyester
polyester resin,
resin, and
anda thin top coating layer of the same resin used on the main body. The indentations were made in the in
a thin top coating layer of the same resin used on the main body. The indentations were made
thetop
toplayer
layerand
andononthe theshell/resin
shell/resin composite
composite zones
zones andand
thethe embedded
embedded shells.
shells. The The indentation
indentation andand
hardness
hardness values
valuesofofthe
thecomponent
componentparts
partsofofthe
thefinal
finalproduct
productofofthis
this new
new artificial
artificial stone, is illustrated
illustrated in
in Figure
Figure 6. 6.

Figure 6. Indentation in the main body of the artificial stone (a) and a comparative table of hardness
Figure 6. Indentation in the main body of the artificial stone (a) and a comparative table of hardness
values of
values ofnatural andand
natural artificial stones
artificial (b). On
stones (b).bold
On are marked
bold the measured
are marked values on
the measured the component
values on the
parts of the finished artificial stone.
component parts of the finished artificial stone.

The
Theobtained resultsofofhardness
obtained results hardness for top
for the thelayer
top resin
layer(unsaturated
resin (unsaturated polyester
polyester resin) (343 ± resin)
39
(343 ± 39 MPa) and for oyster reinforcement (853 ±
MPa) and for oyster reinforcement (853 ± 78 MPa) are both in accordance to the literature [29–32].the
78 MPa) are both in accordance to
literature [29–32]. For
For the composite the composite
material (main bodymaterial (main body
of the artificial stone)of the artificial
a hardness stone)
of 1216 ± 120a hardness
MPa was of
1216 ± 120 MPa was obtained. When hardness values are compared to similar materials
obtained. When hardness values are compared to similar materials (i.e., natural and artificial stones), (i.e., natural
and artificial
it is observed stones),
that theit artificial
is observedstonethat the artificial
hardness stone hardness
is equivalent is equivalent
to the granite and similartotothe
thegranite
marble,and
similar
whichtoplaces
the marble, whichinplaces
this product this product
a remarkable in a between
position remarkable position
these between
two options, these two
however, it isoptions,
still
low when
however, compared
it is still low to Marmoglass
when compared artificial stone.
to Marmoglass artificial stone.

3.3. Transformation
3.3. TransformationofofOyster
OysterPowder
Powderinto
into Calcium
Calcium Oxide
Oxide
There
Thereare
area avast
vastnumber
number of of industries that use
industries that use calcium
calciumoxide
oxideasasa araw
rawmaterial
material in in their
their
processes. Knowing that oyster shells have CaCO as a main component of their
processes. Knowing that oyster shells have CaCO3 as a main component of their chemical composition
3 chemical
composition (approximately
(approximately 95–99%) and other95–99%) and other
minerals minerals in insignificant
in insignificant quantities, quantities, it istopossible
it is possible obtain to
pure
obtain oxide
calcium pure calcium
by using oxide by using aprocess
a calcination calcination process
[1,13]. The [1,13]. The differential
differential thermal allows
thermal analysis analysisthe
allows the temperature
temperature reactioncarbonate
reaction of calcium of calciumcalcination
carbonate calcination
and calcium and calcium
oxide oxide formation
formation to be
to be determined,
determined, as illustrated
as illustrated in Figure 7. in Figure 7.
In the calorimetric and thermogravimetric curve, it is possible to see two periods of weight
losses—the first occurred under 100 ◦ C due to the humidity loss and degradation of the organic matter
that can remain in the sample. The second thermal event was at 761.5 ◦ C, in relation to the dissociation
reaction peak of CaCO3 into CaO and CO2 , which is a very typical temperature for this material [1,13].
Typically, the transformation of the shells as a source of calcium carbonate (CaCO3 ) is followed by a
significant loss of carbon dioxide that is related to the chemical decomposition of the calcium carbonate
of the shells. This phenomenon is known as calcination, which results in the formation of two products,
calcium oxide (CaO) and carbon dioxide (CO2 ).

CaCO3 → CaO + CO2

Resources 2019, 8, 13 10 of 15

Also, this calcination step was followed by a lost weight of ~47.5%, which means that for 100 g of
CaCO3 after calcination ~52.5% of pure CaO will be obtained. This result is similar to the result of a
previousResources
research study
2019, 8, that REVIEW
x FOR PEER found 51% of pure CaO was obtained from the calcination 10
process
of 16 [13].

Calorimetric and the ◦

Figure 7.Figure 7. Calorimetric and rmogravimetric
the rmogravimetriccurves (DSC/TG)
curves (DSC/TG) of the
of the of oyster
of oyster shellsshells until
until 1000 °C.1000 C.

4. Current and Potential

In the Applications
calorimetric for Oystercurve,
and thermogravimetric ShellitWastes
is possible to see two periods of weight
losses—the first occurred under 100 °C due to the humidity loss and degradation of the organic
In this section, the waste management process and possible uses for oyster shell residues will
matter that can remain in the sample. The second thermal event was at 761.5 °C, in relation to the
be analysed. Oyster
dissociation shellspeak
reaction are an abundant
of CaCO source of calcium carbonate that may be used for several
3 into CaO and CO2, which is a very typical temperature for this
applications
materialin [1,13].
different areas.the
Typically, The reuse of the
transformation of shells inhibits
the shells the contamination
as a source of the
of calcium carbonate environment
(CaCO 3) is

and represents
followedan by ecologically sustainable
a significant loss solution
of carbon dioxide byisadding
that related tocommercial
the chemicalvalue to the residues
decomposition of the of the
calcium
mariculture carbonate
sector. of theand
The reuse shells. This phenomenon
recycling is known
of oyster shells as calcination,production
for by-products which results in the
have become a
formation of two products, calcium oxide (CaO) and carbon dioxide (CO 2).
very relevant topic around the world [33–38]. Some studies have shown recycling and reuse solutions
for oyster shells residues, as a rich source CaCO → CaOin several
of calcium, CO sectors, for example, in the building
materials industry as aggregate of limestone for cement and even in the pharmaceutical industry as a
Also, this calcination step was followed by a lost weight of ~47.5%, which means that for 100 g
calcium-rich supplement [10,39]. A diagram of the waste management and potential applications for
of CaCO3 after calcination ~52.5% of pure CaO will be obtained. This result is similar to the result of
Resources
oyster shell 2019, 8,
waste isx shown
FOR PEERinREVIEW 11 of 16
a previous research study Figure 8. 51% of pure CaO was obtained from the calcination process
that found
[13].

4. Current and Potential Applications for Oyster Shell Wastes

In this section, the waste management process and possible uses for oyster shell residues will be
analysed. Oyster shells are an abundant source of calcium carbonate that may be used for several
applications in different areas. The reuse of the shells inhibits the contamination of the environment
and represents an ecologically sustainable solution by adding commercial value to the residues of
the mariculture sector. The reuse and recycling of oyster shells for by-products production have
become a very relevant topic around the world [33–38]. Some studies have shown recycling and
reuse solutions for oyster shells residues, as a rich source of calcium, in several sectors, for example,
in the building materials industry as aggregate of limestone for cement and even in the
pharmaceutical industry as a calcium-rich supplement [10,39]. A diagram of the waste management
and potential applications for oyster shell waste is shown in Figure 8.

Figure 8. Diagram of the waste management and potential applications for calcium carbonate and
calciumFigure
oxide8.asDiagram of the waste
raw materials, foundmanagement and potential
on the following applications
references for calcium carbonate and
[40–43].
calcium oxide as raw materials, found on the following references [40–43].
Based on the prospect of the reuse of clean oyster shells for finished products, the authors present
Based on the prospect of the reuse of clean oyster shells for finished products, the authors
a decorative and functional market solution based on artificial stones. In this case, the oyster shells
present a decorative and functional market solution based on artificial stones. In this case, the oyster
are reused forarethe
shells production
reused of tabletops
for the production of and workbenches
tabletops for potential
and workbenches use inuse
for potential home decoration,
in home
laboratory benches,
decoration, and industrial
laboratory benches,kitchens, amongst
and industrial other
kitchens, possibilities.
amongst We hope that
other possibilities. companies
We hope that and
companies and
other researchers will other researchers to
be encouraged willsimilarly
be encouraged
find newto similarly
solutions find
fornew
end solutions
productsforbased
end on the
products
oyster shell. Theirbased on the
re-use oyster
and shell. Their
recycling re-use
are the andoptions
first recycling are the firstwith
associated options associated business.
a profitable with a
profitable business.

4.1. Calcium Carbonate and Calcium Oxide Source

Since the beginning of 2000, the interest in the recycling of oyster shells to obtain calcium
carbonate and calcium oxide has increased. Nowadays, several programs and companies collect the
oyster shell waste together with the producers and restaurants. In Spain, a factory recycles up to
Resources 2019, 8, 13 11 of 15

4.1. Calcium Carbonate and Calcium Oxide Source

Since the beginning of 2000, the interest in the recycling of oyster shells to obtain calcium carbonate
and calcium oxide has increased. Nowadays, several programs and companies collect the oyster shell
waste together with the producers and restaurants. In Spain, a factory recycles up to 80,000 tons of
oyster shells. The industrial process consists of grinding the residue, followed by heating at 500 ◦ C
for eliminating the organic matter, and obtaining calcium carbonate with 90% purity [1]. The use of
calcium carbonate as a raw material is present in several industries: (i) in the cement industry, for
example, in the fill-in for the infrastructural basis of highway construction; (ii) in the agricultural
industry, as soil broker and a component for poultry rations; (iii) for industries where it is mandatory
for the calcium carbonate to be more purified, such as paint, paper, and plastic production industries;
or (iv) the pharmacological industry, as a component of toothpaste and makeup [39,44–47].

4.1.1. Building Materials

Oyster shell waste has been investigated as an alternative material for construction-related
applications, such as a substitute for aggregates in building materials or cement clinker [6,13,48–51].
Some authors studied the replacement of aggregates in the cement manufacture by grinding down
the oyster shells and mixing with sand. The potential use of oyster shells instead of limestone as a
replacement of Portland cement provides the added benefit of a lower the carbon footprint, as it does
not require the use of equipment associated with mining limestone [6,13].
Another alternative for mariculture residues was found by Brazilian researchers from the Federal
University of Santa Catarina (UFSC). They showed the feasibility of the use of oyster and mussel shells
in the manufacture of concrete blocks and blocks for paving. The shells of the molluscs were washed,
sun-dried, and ground by milling. After, the shells were mixed with components of concrete blocks
and pavements. The water absorption and compressive strength results showed that these products
are highly viable and fit the standards of ABNT (Brazilian Association of Technical Standards) [52,53].
Another interesting construction application was demonstrated by Taiwanese researchers who
produced oyster-shell foamed bricks (OSFBs) to neutralise the acidity of recycled rainwater. In Taiwan,
the average annual rainfall is 2.6 times more than the global average. The calcium carbonate in calcined
oyster shells mostly transforms into calcium oxide, which can be used as an anti-acid agent. Based on
that, the oyster shells were calcined, hydrated, and foamed by adding cement and a foaming agent to
produce the oyster-shell foamed bricks [48].

4.1.2. Water and Air Treatment

Additionally, oyster shells are also being used as new recycling material for removing phosphorus
from water and air [41]. The idea is to use the material to act as filters to absorb the phosphorus or NOX
from water or air. For that, the materials need to have a high surface area, which implies high pore
volume. Jung et al. showed that the SO2 removal activity and reaction rate of the calcined/hydrated
waste oyster shells were higher than those of calcined/hydrated limestone. This finding indicates that
absorbents prepared from waste oyster shells are substitutes for commercial limestone and can be
applied directly to industries attempting to reduce their emissions of SO2 and NOX [37,38,54]. Relevant
studies from South Korean researchers showed that after the pyrolysis of oyster shells at a temperature
of 750 ◦ C for 1 hour in a nitrogen atmosphere they become a product that is able to remove phosphates
in wastewater, with an efficiency higher than 98%, thus demonstrating a potentially effective strategy
for the control of the eutrophication of waters [55].

4.1.3. Plastic Production

Polyvinyl chloride (PVC) compounds contain stabilisers, lubricants, fillers, and pigments. Calcium
carbonate (CaCO3 ), with a small particle size (~20 µm), is used as an additive to transform the PVC
from plastic resin to the final product. The use of this additive can reduce the cost of production
Resources 2019, 8, 13 12 of 15

and improve PVC properties, depending on its application [46]. Decathlon sells a Tribord brand of
products, which produces sports and water sports equipment. They have developed a surf bootie
made of thermoplastic elastomer mixed with 15% recycled oyster shells [42].

4.1.4. Food Supplement

Calcium carbonate extracted from oyster shells has been widely used as a food supplement for
calcium replacement in the body. Studies done with the elderly population in Japan confirm that the
carbonate extracted from the shells is efficiently absorbed by the intestine and increases bone mineral
density, especially in the lumbar region in people with deficiency in calcium [56].

4.1.5. Other Applications

The authors have selected other potential applications based on research works found in the
literature where oyster shell sub-products have been studied—for example, recycled oyster shell
powder and polyethene as a plastic material for fire flame control. The use of the oyster shells proved
to be efficient in the transformation of calcium carbonate into calcium oxide and carbon dioxide at
temperatures above 800 ◦ C, which decreases the access of fire to oxygen; this mechanism reduces the
generation of toxic compounds during incineration [57].
There are also several forms of potential medical applications, for example, the oyster shells can be
used for hydroxyapatite production via precipitation synthesis with oyster shells that have previously
been calcined at 1200 ◦ C for two hours in order to obtain pure calcium oxide [58]. Additionally,
oyster shells have antifungal activities and can be used as agriculture fungicide, by affecting the
membrane permeability of the fungus. Furthermore, non-treated oyster shell powder exhibited
significant antifungal activity against Physalospora piricola Nose (P. piricola) and Rhizoctonia solani Kühn
(R. solani) [59]. Finally, the South Korean government implement a recycling program, based on the
creation of fertilizer factories for the recycling of oyster shells [1,14] and to solve problems of water
eutrophication by transforming this material into a sustainable reagent for the efficient removal of
phosphates from wastewaters [37,55,60].

5. Conclusions
In this study, it was possible to analyse the quality of a product produced with oyster shell waste.
This product was created as a reuse solution for the oyster shell waste disposal issue and as a potential
business and economic strategy.
First, with the aims of revealing the potentialities of the reuse solution of oyster shell waste, an
overview of the production and business-related dimensions of the oyster industry was conducted,
and from this analysis, it can be stated that:
• The production of molluscs, particularly the Pacific oyster (Crassostrea gigas), generates thousands
of tons of waste each year.
• The careless disposal of this massive amount of waste impacts the soil, water, and air quality and
represents an environmental and public health problem.
• Governments should focus their attention and resources on general efforts to reduce
environmental damage and special programs for waste treatment.
The authors presented a business solution for the reuse and recycling of oyster shells collected
from the local producers of Florianopolis, in Santa Catarina, Brazil. A local company has developed a
new product, in the form of an artificial stone, where oyster shells waste is mixed into an unsaturated
polyester resin. Based on the experimental component of this study, it can be concluded that:
• This product can be used for tabletops and workbenches, for home decoration, for laboratory
benches, for industrial kitchens, amongst other potential uses.
• In comparing the mechanical results of the new artificial stone with the other natural and artificial
stones, like granite, marble, and Aglostone, it is concluded that the new artificial stone exhibits
Resources 2019, 8, 13 13 of 15

higher mechanical properties. However, other strengthening solutions must be tested in order
to position the new artificial stone at the same level of mechanical resistance as Nanoglass
and Marmoglass.

The authors indicated some examples of reusing and recycling actions to create oyster shell
by-products as well as their use as a source of calcium carbonate and calcium oxide, demonstrating
that it is possible to design a wide range of applications around the use of oyster shell wastes. There is
an excellent opportunity to invest and find solutions for the use of oyster shells in the production of
new products or as partial/total substitutes for raw materials of sub-products and end-products.

Author Contributions: Conceptualization, J.M.-G. and M.C.F.; Methodology, J.M.-G. and B.H.; Investigation,
J.M.-G. and T.H.S.; Data Curation, T.H.S.; Writing-Original Draft Preparation, T.H.S.; Writing-Review & Editing,
J.M.-G. and B.H.; Funding Acquisition, F.S.S. and M.C.F.
Acknowledgments: This research was funded by National Council for Scientific and Technological
Development—PVE/CAPES/CNPq 407035/2013-3 UFSC/UMinho (Portugal) “Development of High-Performance
Bioinspired Functionally Graded Materials for Oral Rehabilitation” and NORTE-01-0145-FEDER-000018-
HAMaBICo “Hybrid Additive Manufacturing for Bio-Inspired Components”.
Conflicts of Interest: The authors declare no conflict of interest.

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