JURNAL TEKNIK POMITS Vol. 2, No.
1, (2015) ISSN: 2337-3539 (2301-9271 Print)
New Alternative to The Development of Dental
Filling Material Made from {CH-CaCO3-(C-
HA)-MMA} Resulted from The Recycling of
Organic Material
Yuli Setiyorini, Fanny Leestiana, dan Agung Purniawan
Department of Materials and Metallurgical Engineering, Faculty of Industrial Technology, Institut
Teknologi Sepuluh Nopember (ITS)
Jl. Arief Rahman Hakim, Surabaya 60111 Indonesia
e-mail: yulisetiyorini@yahoo.com
Abstract— According to WHO, approximately 72% -
80% of Indonesian residents and 60% - 90% of world’s population
have dental cavities. This problem gives rise to the demand of
dental filling material. Aware of the opportunity, this research
aimed to develop new alternative for dental filling material
synthesized from the recycling of organic waste that is chitosan,
calcium carbonate, carbonate-hydroxyapatite {CH-CaCO3-(C-
HA)} derived from shrimp shells waste, eggshell, and cow bone
with MMA (Methyl Metacrylate) as the bonding matrix for these
materials. The methodology used in this research was by finding
out the effect of various composition of {CH-CaCO3-(C-HA)-
MMA} ratio in the form of filler and matrix. The mechanical
strength of the sample was characterized by hardness test (VHN)
and compression test. The highest result was obtained from G7525
sample with hardness number of 88,04 VHN. Antibacterial test
was carried out to discover the effect of the utilization of chitosan
as anti-bacterial material. The results using Streptococcus mutans
bacteria were positive in every samples with inhibition zone equal
to or higher than 1mm. Based on all test results obtained, material
from chitosan, calcium carbonate, carbonate-hydroxyapatite {CH-
CaCO3-(C-HA)} derived from shrimp shells waste, eggshell, and
cow bone with MMA (Methyl Metacrylate) has potential to be used
as dental filler.
Keywords—calcium carbonate, carbonate-hydroxyapatite,
chitosan, dental filler, MMA.
I. PREFACE
A malgam is the well widely-known dental filler since a long
time ago. Other than its strong property, which is the
consequence of being a material made from the mixture of
mercury metal, silver, copper, and tin, amalgam is the cheapest
dental filler known. Unfortunately, the constituents of amalgam
can cause allergic reaction to some of its users, hence people
started to create new dental filler with saver, heavy metal-free
composite materials. However, the newly developed dental
filler faces another problem despite having color that resembles
the color of the teeth, those are; easy to be worn out, and
expensive [1]. Due to these problems, innovations to improve the
composite of dental filler are needed.
It is known that tooth is composed of enamel and dentine.
The enamel contains nearly 95% of inorganic material, of
which 90%-92% is hydroxyapatite. The dentine, which is the
1
bone of the tooth, contains about 75% of the inorganic material,
most of which is also crystalline hydroxyapatite, 20% organic
matter which is almost 90% in the form of collagen, and 5%
water. With the knowledge of the dental composition, it is
known that the reinforcing particle in natural teeth is in the form
of hydroxyapatite [2].
Apatite (Ca10 (PO4)6(OH,F,Cl)2) is one of the types of
calcium phosphate which can be applied to the bone and tooth
healing process because it has properties such as;
biocompatible, has the same composition as the original bone,
biodegradable , non-toxic, and has good mechanical ability.
These qualities make apatite even more important in the field
of hard tissue engineering [3]. Because of the many qualities that
can be obtained from apatite, a lot of researches are undertaken
to synthesize apatite from nature [4]. The structure of
conventional apatite that are widely available on the market are
many micro-sized and available in various forms, including
powders, porous blocks, and others [5].
Chitosan is preferred for use because, like collagen, it can be
absorbed by human body, easy to be obtained from nature, and
able to help the healing process (wound healing) [6]. In addition,
chitosan also has good antibacterial property [7]. The application
of chitin and chitosan in the dental field has been fairly well
done, such as the making of calcium phosphate cement-
chitosan composite [8], in which chitosan is selected because it
can improve the elasticity property of the ceramics used as the
material for dental filler. Bioactive β-chitin hydrogel / nBGC
composite can be utilized as bone filling material and coating
material for dental implants as it can produce materials which
have ideal characteristics as tissue engineering, in which cells
can be attached and proliferate well [9].
The above explanations have made it known that chitosan,
calcium carbonate, and carbonate-hydroxyapatite have
respective considerable potentials in both the field of tissue
engineering and dental material. Previous researches related to
this topic are among others; chitosan fibers modified by Hap/β-
TCP nanoparticle [10] and chitosan starch composite filled with
micro and nano-sized hydroxyapatite powder for hard tissue
engineering [11].
The increasing awareness of the importance of oral and
dental health has increased the demand of dental filling material
and this research’s proposed material can be the next candidate
JURNAL TEKNIK POMITS Vol. 2, No. 1, (2015) ISSN: 2337-3539 (2301-9271 Print) 2

of dental filling material. Furthermore, the currently Compression test was done with 100kN load and crosshead
commercial dental filling materials still urge the use of many speed of 10mm /min, this generated the force required to press
kind of chemical substances in their manufacturing process, the sample to break. Equation (1) is used to find the
thus are non-qualified as environmentally-friendly materials compressive strength [12].
and may cause harm to human body. Table 1. Chemical Composition
Based on this need and with support from the properties Composition
owned by chitosan, calcium carbonate, and carbonate- Code
C CHA CC MMA
hydroxyapatite as previously explained, the material
synthesized from the mixture of these three substances is C 50wt% - -
possible to be an alternative material in the field of dental filler. CC - - 50wt%
CHA - 50wt% - 50wt%
II. METHODOLOGY G2575 10wt% 10wt% 30wt%
G5050 10wt% 20wt% 20wt%
A. Material
G7525 10wt% 30wt% 10wt%
The materials used in this research were powder filler that
was consisted of carbonate-hydroxyapatite (CHA) powder, 9,807
Rc = F x …. (1)
homemade with purity of 97% and Ca/P ratio of 1.68, calcium 𝐴
carbonate (CC) powder, homemade with purity of 97% and Where Rc is the compressive strength (MPa),
Ca:C:O ratio of 1:1:3, and chitosan (C), homemade with density F is the load (kgf), and
of 1.314 gr/cm3, molecular weight of 38.91 gr/mol, and DD A is the sample cross-sectional area (mm2)
78.5, and also monomer resin. The tested samples (G2575, G5050, and G7525) were
The monomer resin used was MMA (methyl methacrylate) cylindrical with dimensions of 5 mm height and 5 mm in
with molecular weight of 100.12 g/mol and density of 0.936 diameter. So the area of cross section is
g/cm3 at 25°C, containing MEHQ less than 30 ppm as inhibitor. A = π r2
BisGMA matrix (Bispenol A – Glycidylmethacrylate) with = 19,63496 mm2.
molecular weight of 364.43 g/mol. The initiator used is BPO
(Benzoyl peroxide), with molecular weight of 242.23 and
D. Antibacterial Testing
concentration of 60-100%, EGDMA (Ethylene Glycol
Dimethacrylate) serves as crosslinker with molecular weight of Antibacterial testing was done by diffusion method using
198.22, concentration of 98%, and 4,N,N-Trimethylaniline as Streptococcus mutans bacteria, the cause of secondary caries,
the activator with molecular weight of 135.21 and purity of that was bred in NA (Nutrient Agar) or Blood Agar Plate for
18-24 hours along with the sample to be tested.
>98.5%. All of these products were manufactured by Sigma
After 18-24 hours, the diameter of the inhibition zone formed
Aldrich, Singapore.
around the sample was measured using a caliper. Inhibition
zone was calculated using equation .... (2)
B. Synthesis of Dental Filler
(𝑙𝑎𝑟𝑔𝑒𝑠𝑡 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟+𝑠𝑚𝑎𝑙𝑙𝑒𝑠𝑡 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟)
The process of dental filler synthesis began by mixing MMA Inhibition zone = …. (2)
2
(methyl methacrylate) monomer and EGDMA (Ethylene Glycol
Dimethacrylate) crosslinker, BisGMA (Bispenol A –
Glycidylmethacrylate) matrix powder was then added to the III. RESULTS AND DISCUSSION
mixture. The mixing of these three materials was done at a ratio A. Mechanical Ability
of 1wt% : 1wt% : 1wt%. BPO (Benzoyl peroxide) 0,1 wt%
initiator was added subsequently. The prepared solution was Table 2 shows the hardness value of the G2575 sample is
then mixed with carbonate-hydroxyapatite powder, calcium 33.6 VHN, sample G5050 is 64.78 VHN, and sample G7525 is
carbonate, and chitosan according to the composition. After the 88.04 VHN, signifying that the hardness values of the three
mixture had turned into paste, it was put in the mold and 1-2 samples, G2575, G5050, and G7525 are still less than the
drop(s) of 4,N,N-Trimethylaniline was added as the activator hardness of tooth enamel which value can reach 274.8 VHN.
which caused the paste to harden after 60 seconds. The mixing Even so, the value has exceeded the hardness of dentine, which
was carried out according to the compositions specified in is only 65.6 VHN. The hardness value of the three samples were
Table 1. compared to commercial products, Belleglass and Solidex,
which have hardness value of 72 VHN and 43 VHN
C. Sample Characterization respectively. Compared to the commercial dental filler
products, the hardness values of G5050 and G7525 samples are
Hardness testing using micro Vickers standard was performed better. The trends of hardness test results in Table 2 also shows
by using hardness test machine Mitutoyo, HM 200 series Japan.
that the increase in carbonate-hydroxyapatite composition
Indentation load of 300 g was used with a total time of 12
contributes to the increasing hardness value of the sample.
seconds for indentation preparation, indentation, and hardness
measurement [1].
JURNAL TEKNIK POMITS Vol. 2, No. 1, (2015) ISSN: 2337-3539 (2301-9271 Print) 3

Table 2. Hardness Test Result

Mechanica Enam Denti G25 G50 G7 BEL SOLI
l Poperties el ne 75 50 52 LEG DEX
[10] [10] 5 LAS [11]
S
[11]
Hardness 274,8 65,6 33,3 64,7 88, 72 43
(VHN) 6 8 04

Table 3. Compression Test Result

Mechanical Enam Denti G25 G50 G75 BEL SOLI
Poperties el ne 75 50 25 LEG DEX
[10] [10] LAS [11]
S
[11]

Compressiv 62,2 193,7 31,6 25,9 23,6 540 314

e Strengths 329 723 41
(MPa)

The results of compression test show the value of Figure 1

Antibacterial Test Result on 1) G2575, 2) G5050, 3) G7525, and 4) chitosan
compressive strength for each samples, those are 31.6329 MPa, as control
25.9723 MPa, and 23.641 MPa for sample G2575, G5050, and
G7525 respectively. These results are much lower than the Table 4. Antibacterial Test Result
compressive strength of the enamel. The largest compressive Sample Inhibition Zone (mm)
strength obtained in sample G2575 only reached half of the G2575 6,0
value of enamel compressive strength. From the data shown in G5050 8,058
Table 3, it is seen that the increase of carbonate-hydroxyapatite G7525 9,258
content resulting a decrease in compressive strength. A CHITOSAN ( Control) 14,967
comparison of compressive strength between the test results
and commercial products such as Belleglass and Solidex shows
even larger difference. As shown in Table 3, Solidex has IV. CONCLUSION
compressive strength of 314 MPa, nearly 5 times larger than the The conclusion of this research is Calcium carbonate,
enamel’s. This is possible due to the difference in the properties carbonate-hydroxyapatite, and chitosan have the potential to be
or the characteristic of the constituents making up the material. the ingredients of dental filling material because they have good
The big difference between the sample’s compressive strength mechanical strength and antibacterial properties. The increase
and the enamel’s is likely due to the difference in testing in carbonate-hydroxyapatite composition will increase the
standards performed. On which the standard used is in hardness value of the dental filler. The composition which has
accordance with ADA (American Dental Association) 27 [13], properties almost similar to enamel’s are samples with code
i.e. cylindrical test specimen with 3mm diameter and 6 mm G5050 and G7525.
height. Crosshead speed on a universal testing machine is
1mm/min. V. DAFTAR PUSTAKA
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treated with pure chitosan filler. Since all samples contain Biomaterialia 6 (2010) 466-476
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