Results in Physics 12 (2019) 743–747

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Fabrication of Alumino-Silicate-Fluoride based bioglass derived from waste T

clam shell and soda lime silica glasses
⁎
Nadia Asyikin Abdul Rahmana, Khamirul Amin Matoria,b, , Mohd Hafiz Mohd Zaida,
Norhazlin Zainuddinc, Sidek Ab Aziza, Mohammad Zulhasif Ahmad Khirib, Rohaniah Abdul Jalila,
Wan Nurshamimi Wan Jusoha
a
Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
Material Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
c
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Through the traditional approach of the melt-water quenching technique, it is seen that Alumino-Silicate-
Bioglass Fluoride (ASF) bioglass system is assembled. Through the very investigation of this paper, it is noted that pre-
Melt-water quenching paration of ASF bioglass is composed of Clam Shells (CS), Soda Lime Silicate (SLS), CaF2, P2O5, and Al2O3 with
Soda lime silica the empirical formula [xCS⋅(45 − x)SLS⋅15CaF2⋅20P2O5⋅20Al2O3] where x= 5, 10, 15 and 20 (wt%). The waste
Clam shell
materials used to produce ASF bioglass were CS and SLS. The physical and structural properties of bioglass are
Waste materials
Fluorapatite
obtained through Energy X-ray (EDX), density (ρ), molar volume (Vm), X-ray diffraction (XRD), Fourier
Transform Infrared (FTIR) and Field Emission Scanning Electron Microscopy (FESEM) spectroscopy. Such
measured physical parameters like density and molar volume were found to vary linearly with increasing the
CaO content in the bioglass composition. X-ray powder diffractrogram showed that the ASF bioglass samples
with higher amount of CaO content are in amorphous phase, but a small and sharp peak crystal phase was
observed and known as fluorapatite (Ca5(PO4)3F). Meanwhile, FTIR spectroscopy revealed various bonds such as
SieOeSi, PeOeP, CeO and OeH, indicated to the formation of ASF bioglass before sintering occurred. FESEM
analysis showed non-uniform particle distribution, irregular in shape and random grain size of the bioglass.
Although this type of bioglass is well established for dental application, its effect on waste materials such as CS
and SLS for used in dental field has not been extensively studied. Revealed various bonds, stretching and bending
vibrations within the samples before sintering occurred.

Introduction stomatology and orthopaedics in form of their putting together glass

and glass substances [4–9]. Bioactive glass ceramics are prevalently
A variety of bioglass have been established during the last three utilized through the field of stomatology in two ways; in the form of
decades for biomaterial and dental applications. Bioglass is a bioactive implants to place dentures on, as well as the manufacture of dentures
glass composed of calcium and phosphate which were present in a too [10–14]. Bioglass dentures proceed its substances used prior
proportion that is similar to the bone hydroxyapatite. This glass bonds through aesthetics, biological compatibility, mechanical strength, as
to the tissue and it is biocompatible [1]. Meanwhile, bioactivity is de- well as performance. To ensure an excellent performance of biological
fined as the property to form tissue on the surface of biomaterial, es- compatibility, bioactive as well as inert substances are utilized as it is
tablishing an interface which is able to support mechanical solicitations possible for these substances to take the place of teeth and any bone
[2]. The pinnacle in the manufacturing of glass stems from the in- present that occur naturally.
novations of glass which is in close relation to the design of bioglass The options present whilst choosing the correct parent glass-forming
substances. The first bioglass that used in medical applications today as well as glass-modifier system aid to modify the glass matrix to suf-
was invented at the University of Florida. The composition of bioglass ficiently reach the requirement’s particular needs [15–17]. In view of its
45S5 consists of 45 wt% SiO2, 24.5 wt% Na2O, 24.4 wt% CaO and 6 wt thermal stability as well as its inflated chemical durability, the oxide
% P2O5 [3]. A great surge of attention has been shown in the fields of glasses serve a better purpose as host materials in their pragmatic uses

⁎
Corresponding author at: Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.
E-mail address: khamirul@[Link] (K.A. Matori).

[Link]
Received 4 October 2018; Received in revised form 5 December 2018; Accepted 8 December 2018
Available online 13 December 2018
2211-3797/ © 2018 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
([Link]
N.A.A. Rahman et al. Results in Physics 12 (2019) 743–747

[18]. The addition of CaO in the composition helps to promote the Universiti Putra Malaysia and cleaned as well as CS. Both materials
formation of the crystalline phase in the glass system [19–21]. Other were crushed separately using a stainless steel plunger and then sieved
than that, to make good bioglass materials, apatite phase Ca3(PO4)2 until the formation of fine powder that measure at 45 μm. The powder
ought to be present in order the materials can interact well with the live of CS, SLS, CaF2, P2O5 as well as Al2O3 was weighed through that of an
bone tissue or teeth; as this is a part of natural bones and it gives rise to electronic balance with ± 0.001 g accuracy and then mixed thoroughly
the capability to supply strength as well as the capability to grow based on an empirical formula. The mixed powder was ground in a dry
[22–27]. A subset of the hydroxyapatites group, fluorapatite stems from milling container to make the powder mixture homogeneous. After
the substitution of F− ions with that of a hydroxylic group (OH−), in that, the mixture was placed straight to an alumina crucible as well and
which it causes the solubility to go down, invigorate bone genesis as subsequently melted with a temperature of 1500 °C for 4 h through the
well as to raise compression strength. Bonds of greater affinity come to use of an electrical furnace. The molten mixture was then poured into
light through ions that were extracted from bones encircling it, as it the water where a transparent bioglass frit was formed. After that, the
synergistically imbues strengths to tissue adjacent to the implant [28]. bioglass frits were ground and sieved to produce fine bioglass powder
Perhaps the assumption can be that calcium phosphate phase is stabi- (< 45 μm) before sending for characterization.
lized by F− ions. Meanwhile, the addition of Al3+ to the bioglass
composition improves strength but decreases bioactivity [29]. In this Characterization
study, the amount of Al element remains constant for all batches of
bioglass samples. By using Energy X-ray (EDX) analysis, the elemental of the bioglass
Solid waste is one of the major environmental problems that was was determined. The samples powder is analysed by using FEI (model
faced by Malaysians as approximately 18,000 tons of waste disposed NOVA NanoSEM 230).
per day. It is estimated by the year 2020, more than 30,000 tons solid With Archimedes’ Principle, a few parameters of the bioglass sample
waste disposed daily in Peninsular Malaysia [30]. In this country, more was measured, namely it’s weight in air (Wair), and that of the sample
than 90% of total waste products were dumped off into landfills since it immerse in liquid (distilled water) (Wwater), which represents water’s
was the most economical waste disposal option in Malaysia. However, density (ρwater) 1.00 g/cm3; all of which were measured at room tem-
these landfills filled up at a much faster rate due to lack of resource perature. The aforementioned parameters were computed with the use
recovery such as recycling. of an electronic weighing machine with the accuracy of 0.001 g.
Nowadays, researchers used certain waste products to obtain spe- Bioglass’ (ρbioglass) density is shown through the equation:
cific elements that can be used to produce new product as one way of
recycling. For example, the food waste such as CS contains a large weight of bioglass in air
ρbioglass =
amount of CaCO3 while SLS glass waste contains SiO2. Pure CaO and weight of bioglass in water − weight of bioglass in air
silicate are expensive to use especially in the industry due to the high × ρwater (1)
amount needed for certain product. Hence, waste CS and SLS glass were
used to obtain large amount of pure substance needed and reduce the In this study, the molar volume (Vm) was measured in cubic centi-
cost of production. The mixture of these two elements with a few other metre per mole (cm3/mol). The molar volume of substance can be
compositions can lead to the bioglass production. Thus, the main pur- found by measuring its molar mass and density. The equation can be
pose of this project is to utilize the waste materials which are CS and express as:
SLS into ASF bioglass. MT
Accordingly, this study’s aim is to prepare a series of ASF based Vm = Σ × ρwater
ρ (2)
bioglass which includes the compositions of CaO, SiO2, CaF2, P2O5 and
Al2O3 through conventional melt-water quenching technique. Besides, where MT represents the multi-component bioglass system’s total mo-
it is this study’s purpose of looking into the consequence seen from the lecular weight and expressed through
amount of CaO content towards the physical and structural ASF based MT = x i Zi (3)
bioglass attributes with low production cost by using waste materials
th th
such as clam shells and glass bottle. Nowadays, bioglass are the better where xi is i oxide’s mole fraction and Zi represents i oxide’s mole-
alternatives since they have better compressive strength, high corrosion cular weight. However, the relative increment in the molecular weight
resistance and relatively low density and low weight [31]. This work appears to be more than that of density’s increase.
contributes toward a better understanding of the relationship between Such is an amorphous/crystalline nature of the bioglass samples
the bioglass structures, physical performances and provides knowledge that is confirmed by XRD (PANalytical, Philips X’pert PRO PW 3040
for the fabrication of future biomaterials such as glass-ionomer cement MPD X-ray powder diffractometer) accompanied by Ni-filtered Cu Kα
(GIC). radiation position 2θ, ranging from 20° to 80° through the use of 0.02°
steps.
Experimental procedure FTIR (Perkin Elmer Spectrum 100 series) absorption spectra of the
bioglass samples were recorded using a Perkin Elmer FTIR in
Preparation of precursor glass Attenuated Total Reflectance (ATR) mode on powdered of
sizes < 63 μm, FTIR (Perkin Elmer Spectrum 100 series) absorption
A series of ASF based bioglass system were fabricated using con- spectra of the bioglass samples were recorded. The results were mea-
ventional melt-water quenching method. The total bioglass serial spe- sured with 400–4000 cm−1.
cimens were constructed through the combination of the listed weights: Meanwhile, through the use of field emission scanning electron
CaF2 (99.95%, R&M Chemicals), P2O5 (99.99%, Alfa Aesar), Al2O3 microscopy (FESEM, FEI NOVA NanoSEM 230), the bioglass samples
(99.5%, Alfa Aesar), CS waste powder and SLS waste glass powder. The microstructure can be thoroughly looked at and reviewed.
preparation of ASF bioglass is composed of Clam Shells (CS), Soda Lime
Silicate (SLS), CaF2, P2O5, and Al2O3 with the empirical formula [xCS⋅ Results and discussion
(45 − x)SLS⋅15CaF2⋅20P2O5⋅20Al2O3] where x = 5, 10, 15 and 20 (wt
%). Firstly, CS are collected from fresh market in Seremban, Negeri Bioglass samples’ chemical composition were analysed through the
Sembilan and cleaned to remove dirt and impurities. After that, the CS use of an Energy X-ray (EDX) analysis. Present in Table 1, all the ele-
had been calcined at 900 °C for 3 h. Meanwhile, SLS glass wastes from ments were measured and listed down in the forms of element. The
Jalen brand soy sauce bottle; collected from the local restaurant near elements detected were O, Al, Si, Ca, P, Na, F and C in the precursor

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N.A.A. Rahman et al. Results in Physics 12 (2019) 743–747

Table 1
Chemical composition CS, SLS and bioglass composition (wt%).
Elements Weight composition (wt%)

CS before CS after SLS B1 B2 B3 B4

calcination calcination

Si − − 56.361 9.73 9.08 6.36 6.63

Ca 97.696 99.520 23.323 9.14 12.84 13.82 27.06
Na − − 14.523 3.20 2.79 2.36 1.48
Al − − 2.835 13.49 11.07 11.83 12.55
S 0.307 − 1.107 − − − −
C − − − 3.10 3.41 3.62 5.23
O − − − 48.48 50.85 53.74 38.56
F − − − 8.28 2.48 1.32 1.22
P − − − 4.58 7.48 6.95 7.29
Fe − − 0.865 − − − −
K 0.469 − 0.620 − − − −
Sc 0.354 − − − − − −
Zr − − 0.105 − − − −
Cr − − 0.086 − − − −
Zn 0.664 − 0.070 − − − − Fig. 1. ASF bioglass samples’ density as well as molar volume (B1 5 wt% CaO,
Sr 0.265 0.347 0.054 − − − − B2 10 wt% CaO, B3 15 wt% CaO, and B4 20 wt% CaO).
Ho − 0.095 − − − − −
Cu 0.244 0.038 0.520 − − − −
that molar volume of the bioglass samples decreased gradually with
M
increasing density based on the formula, Mv = ρ . The rates of change
bioglass samples. As shown as in the table, B4 shows the highest Ca for the bioglass samples’ density and molecular weight result in an al-
element content, which is 27.06 wt% and the lowest Ca element content teration of molar volume. On the other hand, the findings demonstrate
is 9.14 wt% which comes from B1. Besides, the result of the calcination that the increase in density proves to be no greater that of molecular
showed that the CaCO3 turned into CaO. During calcination process, weight’s relative growth.
raw CS which is rich in calcium carbonate, CaCO3 released carbon di- Fig. 2 shows the XRD pattern for all batch at room temperature
oxide gas, CO2 to form calcium oxide, CaO by thermal decomposition which is before sintering process. From the figure, it can be observed
process at high temperature. Table 1 present the percentage of element that there was fluorapatite (Ca5(PO4)3F) phase peak existed in B3 and
contained in CS before and after calcined. The percentage of main B4, while amorphous phase for B1 and B2 before the mixture being
element Ca is 99.520 wt% while the remaining Sr, Ho and Cu contribute sintered. B1 and B2 bioglass samples were found to show no continuous
to 0.48 wt% of CS composition. From previous research, it has been or discrete sharp peaks which reflect the characteristic of amorphous
found that there were about 44% of the CaCO3 loose from its original bioglass structure. The XRD pattern show that fluorapatite has the
weight during the calcination process [32]. It was seen that SLS glasses’ highest peak at 2θ = 32°. This happens due to unstable chemical
chemical make-up are from common domestic sources as a well as in- composition causing appearance of peak in the XRD analysis of B3 and
dustrial. Elements Na, Ca, Si, Al, K and other elements make up a B4. For B4, which had the highest amount of CaO content, contributed
majority of SLS glasses in the commercial market. As from the waste to the highest crystalline peak. Besides that, the intensity of the peak is
materials, a great deal of both Si, as well as Al, demonstrates its ability low as compared to the bioglass ceramics.
to form glass as the substances make up a great deal of the matrix. It is FTIR spectra in ASF bioglass samples are shown in Fig. 3 for fre-
required to possess a certain ratio of oxides that form networks for glass quency range 400–2000 cm−1. In order to obtain further data on the
to form. It is pertinent to have at least the lowest levels of oxide specimen, infrared spectra are utilized. The authors of this study com-
modifiers that may alter attributes of the final product: CaO that in- pile their work on authors doing similar studies with different vitreous
creases the durability as well as Na2O that decreases the melting point. compounds; the results are shown in Table 2.
In order to have enough following of glass (former and modifier),
combining the chemical elements are important. To avoid adverse ef-
fects of the final products, (namely durability and properties) the oxides
levels have to be lower than a predetermined limit. SLS waste glass
consists of three major components which are Si (56.361 wt%), Ca
(23.323 wt%) and Na (14.523 wt%), as Table 1 demonstrates.
The density, ρ as well as molar volume, M of the bioglass samples
such as B1, B2, B3 and B4 was shown in Fig. 1. By referring to the
graph, it can be clearly seen that the densities of the bioglass samples
increased linearly with increasing of CaO content in the bioglass mix-
ture. The density depends on molecular weight of its single constituent
[33]. The increasing in density of the glasses is due to the heavier
calcium (Ca) atomic mass (40.078 u) compared to the other elements in
the bioglass samples [34]. Decrease in CaO content results in the for-
mation of amorphous phase. Bioglass with high CaO content such as B3
and B4, tend to be crystallised spontaneously to fluorapatite
(Ca5(PO4)3F) phase during melt-water quenching, hence contributed to
higher density. This can be supported by the XRD analysis that obtained
before sintering.
There ought to be a conflicting action seen between density as well
as the molar volume [35]. Molar volume, M is inversely proportional to
density, ρ. Therefore, by referring to the graph, it can be clearly seen Fig. 2. ASF bioglass samples’ X-ray diffraction.

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CeO bond exists in all batches which indicate that the carbonate group
existed in CaO. In the spectrum display a new OeH bending band ap-
peared, displaying ∼1633 cm−1 at B4 where this result is in the range
of OeH bending band.
FESEM analysis was performed to study the micrograph images that
include grain size, shape and morphologies of the glass samples. Fig. 4
shows FESEM images of bioglass samples with different amount of CaO
content in the composition before sintering process. FESEM analysis
reported that all the bioglass samples were observed to be non-uniform
particle distribution, irregular in shape and random grain size. The
difference is the amount of CaO content in the compositions does not
affects the crystallinity growth in the samples. As it can be seen in the
figure, all the glass samples show clear glassy surfaces with no crystal
growth were observed.

Conclusion

In this study, ASF bioglass samples were successfully prepared using

conventional melt-water quenching technique. The chemical composi-
Fig. 3. FTIR spectra of ASF bioglass samples. tion of bioglass, clam shells and SLS glass waste were measured using
EDX technique. The density of samples increases with increasing CaO
content in the bioglass mixture. However, molar volume shows the
Table 2
opposite trend. XRD results show that the sample are in glassy structure
FTIR spectral band assigned to the vibrational modes.
and amorphous phase, but small and sharp peak observed in Batch 1
Wavenumbers (cm−1) Assignment of vibrational mode References and 2 known as fluorapatite (Ca5(PO4)3F) although before sintering
∼720–760 Symmetric PeOeP bond [36,37]
process. Meanwhile, FTIR spectra had proven the presence of various
∼860–940 SieOeSi stretching mode [38,39] bonds such as SieOeSi, PeOeP, CeO and OeH, indicated to the for-
∼1400–1500 CeO stretching mode [40,32] mation of ASF bioglass. The micrographs of FESEM showed that the
∼1600–1650 OeH bending mode [32,41] samples had irregular shape with a sharp particle edge of glass.
Therefore, this ASF bioglass derived from clam shells and SLS glass
bottle as calcium oxide and silica source respectively appears to be
promising for the use in dental application.

Acknowledgments

The researchers acknowledged with gratitude and thankful for the

fiscal support for this work by the Malaysian Ministry of Higher
Education (MOHE), Malaysian Ministry of Education (MOE) and
Universiti Putra Malaysia (UPM), each under the grant research
Fundamental Research Grant Scheme and Inisiatif Putra Siswazah. The
authors would like to also acknowledge the contributions of the re-
viewers of this paper toward ensuring quality in both presentation and
substance.

References

[1] Farooq I, Imran Z, Farooq U, Leghari A, Ali H. Bioactive glass: material for the
future. World J Dent 2012;3(2):199–201.
[2] Huang AW, Santos C, Magnago RO, Silva RFF, Strecker K, Daguano JKMF. Sintering
alumina ceramics reinforced with bioactive glass of 3CaO.P2O5-Sio2-MgO system.
Ceramica 2015;61:160–7.
[3] Hench LL, Andersson O. Bioactive glasses. An introduction to bioceramics
2013:49–69.
[4] Kokubo T, Shigernatsu M, Nagashima Y, Tashiro M, Nakamura T, Yaniamuro T.
Apatite- and wollastonite-containing glass-ceramics for prosthetic application. Bull
Fig. 4. FESEM micrograph of ASF bioglass samples before sintered.
Inst Chem Res 1982;60:260–8.
[5] Kokubo T, Kim HM, Kawashita M, Nakamura T. Novel ceramics for biomedical
applications. J Aust Ceram Soc 2000;36:37–46.
Said specimen samples’ IR spectrum contained three absorption [6] Karlsson KH. Bioactivity of glass and its relation to glass structure. Glass Phys Chem
bands (Fig. 3) that reflect the bioglass’ vibration mode, that appear at 1998;24:280–4.
frequency ranges 600–800 cm−1, 800–1000 cm−1, 1300–1500 cm−1, [7] Kokubo T, Ito S, Shigematsu M, Sakka S, Yamamuro T. Fatigue and life-time of
bioactive glass-ceramic A-W containing apatite and wollastonite. J Mater Sci
as well as 1600–1800 cm−1. The band located at ∼680 cm−1 only exist 1987;22:4067–70.
in B1 is the symmetric PeOeP bond, while broad bands at ∼930 cm−1 [8] Kokubo T, Ito S, Shigematsu M, Sakka S, Yamamuro T. Mechanical properties of a
exist in all batch where this band referred to the SieOeSi stretching new type of apatite-containing glass-ceramic for prosthetic application. J Mater Sci
1985;20:2001–4.
mode. Silica being present in SLS glass powder, added towards the IR
[9] Likitvanichkue S, Lacource WC. Apatite-wollastonite glass-ceramics. J Mater Sci
absorption bands and PeO bond exist indicated the formation of crys- 1998;33:5901–4.
tallization CaeP phase [42]. The band located at ∼1390 cm−1 was [10] Nakamura T, Yamamuro T, Higashi S, Kokubo T, Itoo S. A new glassceramic for
identified as the CeO stretching mode. The carbonate existing in the bone replacement: evaluation of its bonding to bone tissue. J Biomed Mater Res
1985;19:685–98.
powder may be due to the dissolution of CO2 from the atmosphere. This

746
N.A.A. Rahman et al. Results in Physics 12 (2019) 743–747

[11] Park JB. Biomaterials science and engineering. New York: Plenum Press; 1987. [27] He Y, Bao WM, Song CL. Microstructure and leach rates of apatite glass-ceramics as
[12] Suchanek W, Yoshimura M. Processing and properties of hydroxyapatite-based a host for Sr high-level liquid waste. J Nucl Mater 2002;305:202–8.
biomaterials for use as hard tissue replacement implants. J Mater Res [28] Bogdanov BI, Pashev PS, Hristov IG, Markovska. Bioactive fluorapatite-containing
1998;13:94–117. glass ceramics. Ceram Int 2009;35:1651–5.
[13] Kokubo T. Recent progress in glass-based materials for biomedical applications. J [29] De Caluwe T, Vercruysse CWJ, Ladik I, Convents R, Declercq H, Martens LC, et al.
Ceram Soc Jpn 1991;99(1154):965–73. Addition of bioactive glass to glass ionomer cements: effect on the physico-chemical
[14] Yanianiuro T, Hench LL, Wilson J. AAV glass-ceramic: clinical applications. An properties and biocompatibility. Dent Mater 2017;33:186–203.
introduction to bioceramics. Singapore: World Scientific; 1993. p. 89–103. [30] Jereme IA, Begum RA, Talib B, Siwar C, bAlam M. Assessing problems and prospects
[15] Sharma YK, Surana SSL, Singh RK, Dubedi RP. Spectral studies of erbium doped of solid waste management in Malaysia 2017.
soda lime silicate glasses in visible and near infrared regions. Opt Mater [31] Urist MR, Johnson RW. Healing of fracture in man under clinical conditions. J Bone
2007;29:598. Joint Surg 1941;25:375–426.
[16] Scott D, Mountjoy G. Rotational invariants of network former and modifier cations [32] Galván-Ruiz M, Hernández J, Baños L, Noriega-Montes J, Rodríguez-García ME.
in silicate glasses. J Non-Cryst Solids 2014;54:401. Characterization of calcium carbonate, calcium oxide, and calcium hydroxide as
[17] Zaid MHM, Matori KA, Sidek HAA, Azmi BZ, Sabri MGM. Effect of ZnO on the starting point to the improvement of lime for their use in construction. J Mater Civ
physical properties and optical band gap of soda lime silicate glass. Int J Mol Sci Eng 2009;21(11):694–8.
2012;13:7550–8. [33] Almasri KA, Sidek HAA, Matori KA, Zaid MHM. Effect of sintering temperature on
[18] Lin H, Pun EYB, Liu XR. Erbium-activated aluminium fluoride glasses: optical and physical, structural and optical properties of wollastonite based glass-ceramic de-
spectroscopic properties. J Non-Cryst Solids 2001;283:27–33. rived from waste soda lime silica glasses. Results Phys 1941;7:2242–7.
[19] El-Meliegy E, Noort R. Glasses and glass ceramics for medical applications. New [34] Hurt JC, Phillips CJ. Structural role of zinc oxide in glasses in the system Na2O-ZnO-
York: Springer Science & Business Media, LL; 2011. SiO2. J Am Ceram Soc 1970;53(5):269–73.
[20] He F, Tian S, Xie J, Liu X, Zhang W. Research on microstructure and properties of [35] Zaid MHM, Matori KA, Wah LC, Sidek HAA, Halimah MK, Wahab ZA, et al. Elastic
yellow phosphorous slag glass ceramics. J Mater Chem Eng 2013;1:27–31. moduli prediction and correlation in soda lime silicate glasses containing ZnO. Int J
[21] Li B, Qing Z, Li Y, Li H, Zhang S. Effect of CaO content on structure and properties of Phys Sci 2011;6(6):1404–10.
low temperature co-fired glass-ceramic in the Li2O–Al2O3–SiO2 system. J Mater Sci- [36] Knubovets R. Structural mineralogy and properties of natural phosphates. Chem
Mater Electron 2016;27(3):2455–9. Eng 1993;9(3–4):161–216.
[22] Holand W, Rheinberger V, Apel E, yan’t Hoen C. Principles and phenomena of [37] Kuzielová E, Palou M, Lokaj J, Kozánková J. Bioactivity investigation of glass and
bioengineering with glass-ceramics for dental restoration. J Eur Ceram Soc glass ceramics in Li2O–SiO2–CaO–P2O5–CaF2 system. Adv Appl Ceram
2007;27:1521–6. 2008;107(4):203–9.
[23] Holand W, Rheinberger V, Apel E, yan’t Hoen C, Hoeland M, Dommann A, et al. [38] Chen X, Chen X, Brauer DS, Wilson RM, Hill RG, Karpukhina N. Novel alkali free
Clinical applications of glass-ceramics in dentistry. J Mater Sci-Mater Med bioactive fluorapatite glass ceramics. J Non-Cryst Solids 2014;402:172–7.
2006;17:1037–42. [39] Peitl O, Zanotto ED, Hench LL. Highly bioactive P2O5–Na2O–CaO–SiO2 glass-cera-
[24] Hill R, Calver A, Skinner S, Stamboulis A, Law R. A MAS-NMR and combined mics. J Non-Cryst Solids 2001;292(1–3):115–26.
Rietveldt study of mixed calcium/strontium fluorapatite glassceramics. Key Eng [40] Montazeri N, Jahandideh R, Biazar E. Synthesis of fluorapatite-hydroxyapatite na-
Mater 2006;309:305–8. noparticles and toxicity investigations. Int J Nanomed 2011;6:197.
[25] Stamboulis A, Hill RG, Calver A, Bubb N, Manuel P. Real time neutron diffraction [41] Hong Z, Merino EG, Reis RL, Mano JF. Novel rice-shaped bioactive ceramic nano-
studies of apatite glass ceramics. Key Eng Mater 2006;309:309–12. particles. Adv Eng Mater 2009;11(5):B25–9.
[26] Freeman CO, Brook IM, Johnson A, Hatton PV, Stanton K. Crystallization modifies [42] Al-Bader RM, Ziadan KM, Al-Ajely MS. New glass compositions based on calcium-
osteoconductivity in an apatite-mullite glass-ceramic. J Mater Sci-Mater Med fluoroaluminosilicate for dental composite. J Adv Chem 2015;10(5):2743–52.
2003;14:985–90.

747