structural properties of ha:al2o3:sio2 glass ceramics ... · formed by pressing the powder in...

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International Journal of Civil Engineering and Technology (IJCIET)

Volume 10, Issue 05, May 2019, pp. 590-603, Article ID: IJCIET_10_05_063

Available online at http://www.iaeme.com/ijmet/issues.asp?JType=IJCIET&VType=10&IType=5

ISSN Print: 0976-6308 and ISSN Online: 0976-6316

© IAEME Publication

STRUCTURAL PROPERTIES OF HA:AL2O3:SIO2

GLASS CERAMICS SYSTEMS FOR BIO

APPLICATIONS

Mohammed Falih Majid*

University of Wasit, Collage of Science, Wasit, Iraq.

Abbas Fadhel Essa

University of Wasit, Collage of Science, Wasit, Iraq.

Shatha Shammon Batros

Ministry of Science and Technology, Baghdad, Iraq.

*Corresponding Author

ABSTRACT

In this research the solid state technique was used to syntheses five systems of

glass-ceramic by combining of Hydroxyapatite, Alumina and Silica in different molar

percent. The X-ray diffraction analysis for all systems before and after sintering was

present and discussed in this research, the morphology of those systems also

investigated by scanning electron microscope (SEM), the composition of each system

was analyzed by the energy dispersive x-ray diffraction (EDS). Exploitation of the

Fourier Transform Infrared (FTIR) spectra to identify the chemical bonds as well as

functional groups in the compound for all systems. The results present new phases

such as Mullite (Al6Si2O13) and Anorthite (CaAl2Si2O8) that mean the components of

these system was interacted very well. The in-vitro study also discussed by immersing

the samples within the simulated body fluid (SBF). The XRD results proved the

consistence of the apatite layer on the samples after immersion it in SBF.

Key words: Glass-ceramics, in-vitro, Hydroxyapatite, Alumina, Silica.

Cite this Article: Mohammed Falih Majid, Abbas Fadhel Essa and Shatha Shammon

Batros, Structural Properties of HA:Al2O3:SiO2 Glass Ceramics Systems for Bio

Applications, International Journal of Civil Engineering and Technology 10(5), 2019,

pp. 590-603.

http://www.iaeme.com/IJCIET/issues.asp?JType=IJCIET&VType=10&IType=5

1. INTRODUCTION

Since 1969, many investigators notified the different types of glasses and ceramics designed

for bio applications as a group called "bioceramics". Bioceramics include glass, glass-

ceramics, zirconia (ZrO2), alumina (Al2O3), thin film coatings, Hydroxyapatite (HA) and bio-

absorbable calcium phosphates. They have mainly been used for dental, skeletal and

Structural Properties of HA:Al2O3:SiO2 Glass Ceramics Systems for Bio Applications


orthopedic applications. This is on account of the chemical compatibility between the

composition of certain ceramic materials and that of tissues such as bone and teeth [1-5].

Bioceramics are characterized by their nontoxicity, chemical constancy in biological mediums

and biocompatibility. The purposes of bioceramics can be separated into bioinert, bioactive

and bioresorbable, so this research combined this three types of bioceramics. Although

traditional bioceramics exhibit brittleness and fatigue, their careful mechanical aspects can

lead to many potential applications [6-10]. Some applications of functional bioceramics are

dental encores, root canal cares, rebuilding the alveolar ridge, middle ear operation, spine

surgery, facial and cranial bones, filling mastoid defects and to treat the defects of bone [11],

substitute for hard tissue replacement, load-bearing implants, bone remodeling, as parts of

devices installed in the body, skeletal and vertebral implants. Amongst the bioceramics other

than glass ceramics of HA, HA has the property for usage in different forms (dense, coatings

on metals, granules, putty) for biomedical applications depending on its inertness to foreign

body reactions and its ability to frame new bonding with the bone and it has the properties of

bioresorbable ceramics [11]. The important properties of α-alumina are chemical inertness

and high hardness. Chemical and thermal constancy, relatively high strength, thermal and

electrical insulation features joint with availability in abundance make aluminum oxide Al2O3,

or alumina, attractive for bioengineering applications [12]. Abrasion resistance, strength and

chemical inertness of aluminum oxides make it to be recognized as a ceramic for dental and

bone implants [13]. Silica (SiO2) is the most important and multilateral bioactive ceramic

compound. It is widely existed in raw materials in the earth’s surface, and silica is a

fundamental constituent of a wide range of ceramic products and glasses; its properties

nominated it to be used in high-temperature and corrosive environments and as abrasives,

refractory materials, fillers in paints, optical components and in bio-application materials [14].

2. MATERIALS AND METHODS

This article aims to preparing and studying different systems of glass ceramic from (HA,

Al2O3 and SiO2) as showing in table (1) in different molar percent, mixing the powders by the

mechanical way using the balls miller and by using the handle mill. The second step was done

by adding the deionized water to the mixing powder in a beaker then but on magnetic stirrer

in 40 oC with 1000 r.p.m. for 4 hours, the solved was alkali (PH=9.4). In the next step, the

beaker of solved was laid in ultra sonic (US) cleaner device for 4 hours to increase the

homogeneity. The gel was filtered by using filtering paper for 96 hours and then the matter

was dried in drying oven (Binder FED 53-UL Forced Convection Drying Oven) in 100 oC for

6 hours to remove the moisture. The dried mixture was mailed by using handle mill in two

times to get very fine and mixed powder of system, contained homogenous particles of

hydroxyapatite, alumina, and silica. The powder was put in American Crucible and then put in

the kiln (Shin Sheng furnace, Korea) in 1100 oC for 4 hours to complete the reaction of the

system contents, the mass of reactant powder was reduced because the moisture and the

impurities were vanished. All five system present in table (1) will be prepared in the same

way.

Table 1 The five systems prepared in different molar percent.

The system Hydroxyapatite (HA) % Alumina (Al2O3) % Silica (SiO2) %

1 20 50 30

2 9.5 48 42.5

3 10.5 66 23.5

4 16.5 42 41.5

5 9 65 26

Mohammed Falih Majid, Abbas Fadhel Essa and Shatha Shammon Batros


Glass ceramic pellets were prepared by moistureless pressing a powder that was pan-

granulated using Polypropylene Glycol (PGL) binder. From every system, five pellets were

formed by pressing the powder in hardened steel die of a 10 mm diameter. The heat

processing is one of the significant steps in the ceramic fabrication. Ceramic powder

compacts be subjected to several important changes during heat treatment, this process was

very necessary to completely prepare the glass ceramic system, the samples were sintered in

1250 oC for 3 hours with heating and cooling rate 7 degrees per minute. During sintering

several ceramic structural changes occurs, such as densification and grain growth. Deionized

water was used for mixing and makeup of all aqueous solutions throughout the study. The

density of all pellets was studied from its mass and external dimensions, the bulk density of

composites was determined by Archimedes’ method. The phase compositions of the

composites were examined by X-ray diffraction (XRD; GNR, Instrument Analytical Group,

Explorer, Italy) operated at 60 kV with a 60 mA Cu Kα_ radiation source. A morphology of

systems will be investigated by SEM technique (Zeiss (LEO) 1450VP Scanning Electron

Microscope), the SEM was coupled with an energy dispersive X-ray spectroscopy (EDS). To

determine the elemental composition and the functional groups of all elements, some powder

from every system investigation using the Fourier transform infrared spectroscopy (AVATAR

370 FT:IR Thermo Nocket).

3. RESULTS AND DISCUSSION:

The X-ray diffraction analysis in figure (1) refers that all systems' interaction at 1100 oC

before sintering have the same behaviour and the same phases appear although the change in

molar ratio. The peaks of Silica have the largest value of intensity although that the amount of

Silica less than the amount of Alumina, the reason belong to the fact that the result of reaction

produces the matter of less melting point steady on the composite, the silicon oxide has a very

strong interaction with Alumina and the silicon oxide has the smallest melting point so its

peaks appeared the largest. The effect of Hydroxyapatite appear in slight manner because it

was added in small ratio in all systems.

10 20 30 40 50 60 700

1000

2000

3000

4000

**

***

*

I (C

PS

)

2 theta (deg)

(1)

(2)

(3)

(4)

(5)

* SiO2

Al2O

3

CaAl2Si

2O

8

*

Figure 1 The X-ray diffraction analysis for all systems interaction at 1100 oC.



The results after sintering present very high decrees in intensity relative to results before

sintering. The systems present Mullite Al6Si2O13 (Aluminum silicate) [15], and the Anorthite

CaAl2Si2O8 (Calcium Aluminum Silicate) [16, 17] as a result of the interaction of powders in

1250 o

C. From the figures we noted that the peaks of Mullite and Anorthite was increased in

intensity and the peaks of alumina and silica was decreased. By comparing the crystallite size

before and after sintering that a clear decrease in it, which means the particles have a new

form. In figure (2) the Anorthite phase was appear in systems (1) and (4), while the phase

Mullite was appeared in figure (3) in systems (2), (3) and (5). The third system was sintered

in 1400 oC for 4 hours and the result of XRD was present in figure (4), there were no effect of

Hydroxyapatite that mean the systems must sintered in degree less than this temperature.

10 15 20 25 30 35 40 45 50 55 60 65 700

50

100

150

200

250

300

*

*

*

I (cp

s)

2 Theta (deg)

(1)

(4)

CaAl2Si

2O

8

Al2O

3

* SiO2

Figure 2 The X-ray diffraction analysis for (1) and (4) systems sintering at 1250

oC.

10 15 20 25 30 35 40 45 50 55 60 65 70 75 800

20

40

60

80

100

120

140

160

*

*

*

**

I (C

PS

)

2 Theta (deg)

(2)

(3)

(5)

CaAl2Si

2O

8

Al2O

3

* SiO2

Al6Si

2O

13

Figure 3 The X-ray diffraction analysis for (2), (3) and (4) systems sintering at 1250 oC.



10 20 30 40 50 60 70 800

100

200

I (C

PS

)

2 Theta (deg)

(3) 1400 oC

Al6Si

2O

13

Figure 4 The X-ray diffraction analysis for the third system (3) sintering at 1400.

Morphological and crystallographic information of the synthesized systems were studied

by the Scanning Electron Microscopy (SEM), The Scanning electron microscopy images

present in two magnification 100 and 2 µm as shown in figure (5), the particles of the first

system (1) are convergent in size, and they are separated in homogenous form and there were

no very big agglomeration. There are some porous appear in the third (3) and forth (4)

systems, these porous were helpful to interact the simulated body fluid with the system and to

attached with the tissue. The particle consist of many grains, they were distributed uniformly

and in clear manner.

The Energy dispersive x-ray spectroscopy results were present in figure (6) for all

systems. Shows the average elemental composition of the powders that used in synthesized all

systems. The following are the average percentage elemental composition of the raw materials

as evaluated and include, for the first system (1) the elemental composition in weight percent:

O (51.9%), Al (30%), Si (10%), P (3.24%) and Ca (4.38%). For the second system (2) the

elemental composition in weight percent are: O (36%), Al (23.3%), Si (31.9%) and Ca

(8.4%). For the third system (3) the elemental composition in weight percent: O (42.2%), Al

(31%), Si (18%), P (1.51%) and Ca (6.54%). For the fourth system (4) the elemental

composition in weight percent: O (47.8%), Al (22.3%), Si (18%), P (1.02%) and Ca (9.94%).

And the elemental composition for the fifth system (5) was: O (41.05%), Al (34.74%), Si

(17.22%) and Ca (6.99%).



Figure 5 The SEM images of five systems, every system in two ranges 100 and 2 µm.

2-

b

2-a))

3-

a

3-

b

1-a)) 1-

b

5-

a

5-

4-

a

4-

b



Figure 6 The EDS images of the five systems.

1

2

5

4

3



The Fourier Transform Infrared (FTIR) spectra of the synthesized systems in the

wavenumber range of 400-4000 cm-1

which identifies the chemical bonds as well as

functional groups in the compound are present in figures (7) to (11) below show common

bands assigned to various vibrations in the systems, respectively. The IR spectra of all

specimens show broad bands in the high energy region that are probably water related bands

[18-20].

The analysis of these spectra revealed the weak broad band centered at around 3430 cm-1

for first system (1) and fifth system (5), and strong broad band centered at around 3427 cm-1

for second (2) and third (3) systems, and strong broad band centered at around 3448 cm-1

for

fourth (4) system correspond to the overlapping of the O-H stretching bands of hydrogen-

bonded water molecules (H-O-H...H) and SiO-H stretching of surface silanols hydrogen-

bonded to molecular water (SiO-H...H2O) [21]. The weak absorption band and the medium

intense absorption band corresponding to the adsorbed water (H-O-H) molecules deformation

vibrations appear at 1625 cm-1

and 1630 cm-1

in all systems [22]. The very intense band at

1111 cm-1

for third system (3) and very intense band at 1106 cm-1

for (5) system assigned to

the longitudinal optical (LO) modes of the Si-O-Si asymmetric stretching vibrations [23]. A

strong peak centered at 1045 cm-1

transverse optical mode (TO -Si-O-Si). The bonds at

1072 cm-1

corresponds to the symmetric (Al-O-Al) mode of boehmite. The weak shoulder

band at around 693.24 cm-1

and 694 cm-1

appear in all systems is assigned to Si-O stretching

of the SiO2 [24, 25]. A sharp peck at 453 cm-1

corresponding to Si-O-Si band, a weak

absorption at 945 cm-1

were belonged either to Si-O amorphous mode or due to silanol (Si-

OH) stretching vibrations. And the bands at 884, 740, 621 and 479 cm-1

are attributed to the

Al-O bands of boehmite. The sharp peck at 775-790 cm-1

corresponding to Ѳ-alumina (Al2O3)

phase. The pecks between 520 and 530 cm-1

belong to P-O band crystal. A peck at about 600

cm-1

corresponding to and the sharp peck at 560 cm

-1 belong to α-Al2O3 (corundum)

[26]. The differences in spectra between all systems may attributed to the impurities present in

substances or to different ratios of adding.

Figure 7 The FTIR spectroscopy of the first system (1).



Figure 8 The FTIR spectroscopy of the second system (2).

Figure 9 The FTIR spectroscopy of the third system (3).

Figure 10 The FTIR spectroscopy of the fourth system (4).



Figure 11 The FTIR spectroscopy of the fifth system (5).

The bioactivity of the syntheses samples of glass ceramics systems was studied in-vitro by

immersion the samples in the simulated body fluid (SBF). X-ray diffraction can illustrated the

new phases that growth on the surfaces of the sample in comparing it with the results before

immersion. In all systems present in figure (12) to figure (16) that clear the appearing of a

new beaks of Hydroxyapatite, and increasing in the number of beaks of the Anorthite. These

results improve that the small amount of Hydroxyapatite that was added in syntheses of

systems will stimulation the samples to interact with the SBF.

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

0

100

200

*

*

*

I (C

PS

)

2 Theta (deg)

(1)

HA

CaAl2Si

2O

8

Al2O

3

* SiO2

Figure 12 The XRD for the first system (1) after immersion in the SBF.



10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

0

100

200

300

400

500

600

700

800

*

**

I (C

PS

)

2 Theta (deg)

(2)

HA

CaAl2Si

2O

8

Al2O

3

* SiO2

Al6Si

2O

13

Figure 13 The XRD for the second system (2) after immersion in the SBF.

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

0

50

100

150

200

250

*

*

*

*

I (C

PS

)

2 Theta (deg)

(3)

HA

CaAl2Si

2O

8

Al2O

3

* SiO2

Al6Si

2O

13

Figure 14 The XRD for the third system (3) after immersion in the SBF.



10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

0

50

100

150

200

250

300

*

*

*

*

I (C

PS

)

2 Theta (deg)

(4)

HA

CaAl2Si

2O

8

Al2O

3

* SiO2

Figure 15 The XRD for the fourth system (4) after immersion in the SBF.

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

0

200

400

*

*

*

I (C

PS

)

2 Theta (deg)

(5)

HA

CaAl2Si

2O

8

Al2O

3

* SiO2

Al6Si

2O

13

Figure 16 The XRD for the fifth system (5) after immersion in the SBF.



4. CONCLUSIONS

By taking the conditions of syntheses for systems and the results of this study into account,

the following conclusions can be abstracted in:

Ceramics systems with a composition of (HA:Al2O3:SiO2) were successfully synthesized by

the solid state method.

This method has the property to synthesized glass ceramic systems at a minimum

temperature compared with the traditional melting route that requires high

temperature.

The results present new phases such as Mullite (Al6Si2O13) and Anorthite (CaAl2Si2O8) and

there was no effect of adding Hydroxyapatite when sintering at 1400 oC that mean the systems

contain Hydroxyapatite must sintering in temperature less than 1400 oC.

Examination of apatite formation on the surface of a material in SBF is useful for predicting

the in-vivo bone bioactivity of the material, not only qualitatively but also quantitatively. This

method can be used for screening bone bioactive materials before animal testing and the

number of animals used and the duration of animal experiments can be remarkably reduced by

using this method, which can assist in the efficient development of new types of bioactive

materials.

In-vitro bioactivity study carried out in SBF solutions showed the formation of bone-

like apatite layer on the (HA:Al2O3:SiO2) ceramic systems.

REFERENCES

[1] Toni, A., Sudanese, A., Busanelli, L., Zappoli, F. A., Brizio, L., & Giunti, A. (1998).

Cementless arthroplasty using alumina ceramics as a coating and bearing material. Hip

Surgery Materials and Developments. London, Martin Dunitz, 267-276.

[2] Park, J. B., & Bronzino, J. D. (2000). The biomedical engineering handbook. Boca Raton,

FL: CRC Press, 4, 1-8.

[3] Lacefield, W. R., Hench, L. L., & Wilson, J. (1993). An introduction to bioceramics. by L.

L. Hench and J. Wilson, World Sci, 223-38.

[4] Nicholson, J. W. (2002). The chemistry of medical and dental materials (Vol. 3). Royal

Society of Chemistry.

[5] Zhao, X., Liu, Q., Yang, J., Zhang, W. and Wang, Y., (2018). Sintering Behavior and

Mechanical Properties of Mullite Fibers/Hydroxyapatite Ceramic, Materials, 11, 1-14.

[6] Malard, O., Guicheux, J., Bouler, J. M., Gauthier, O., de Montreuil, C. B., Aguado, E., &

Daculsi, G. (2005). Calcium phosphate scaffold and bone marrow for bone reconstruction

in irradiated area: a dog study. Bone, 36(2), 323-330.

[7] Rigo, E. C. S., Boschi, A. O., Yoshimoto, M., Allegrini Jr, S., Konig Jr, B., & Carbonari,

M. J. (2004). Evaluation in vitro and in vivo of biomimetic hydroxyapatite coated on

titanium dental implants. Materials Science and Engineering: C, 24(5), 647-651.

[8] Wahl, D. A., & Czernuszka, J. T. (2006). Collagen-hydroxyapatite composites for hard

tissue repair. Eur Cell Mater, 11, 43-56.

[9] Nakamura, S., Takeda, H., & Yamashita, K. (2001). Proton transport polarization and

depolarization of hydroxyapatite ceramics. Journal of Applied Physics, 89(10), 5386-

5392.



[10] Gittings, J. P., Bowen, C. R., Turner, I. G., Baxter, F. R., & Chaudhuri, J. B. (2008).

Polarisation behaviour of calcium phosphate based ceramics. In Materials Science Forum.

Trans Tech Publications, Vol. 587, pp.91-95.

[11] Kotobuki, N., Kawagoe, D., Nomura, D., Katou, Y., Muraki, K., Fujimori, H., ... &

Ohgushi, H. (2006). Observation and quantitative analysis of rat bone marrow stromal

cells cultured in vitro on newly formed transparent β-tricalcium phosphate. Journal of

Materials Science: Materials in Medicine, 17(1), 33-41.‏

[12] Auerkari, P. (1996). Mechanical and physical properties of engineering alumina

ceramics. Espoo: Technical Research Centre of Finland, pp. 6-24.‏

[13] Thamaraiselvi, T., & Rajeswari, S. (2004). Biological evaluation of bioceramic materials-

a review. Carbon, 24(31), 172.‏

[14] Shackelford, J. F. (2000). Introduction to Materials Science for Engineers. 6th. Upper

Saddle River, NJ: Pearson Prentice Hall, 12(533), 33.

[15] Fernandes, L., & Salomão, R. (2018). Preparation and Characterization of Mullite-

Alumina Structures Formed "In Situ" from Calcined Alumina and Different Grades of

Synthetic Amorphous Silica. Materials Research, 21(3).

[16] Rouabhia, F., Nemamcha, A. & Moumeni, H. (2018). Elaboration and characterization of

mullite-anorthite-albite porous ceramics prepared from Algerian kaolin. Cerâmica 64 126-

‏.132

[17] Pal, M., Das, S., & Das, S. K. (2015). Anorthite porcelain: synthesis, phase and

microstructural evolution. Bulletin of Materials Science, 38(2), pp. 551-555.‏

[18] Fidalgo, A., & Ilharco, L. M. (2001). The defect structure of sol–gel-derived

silica/polytetrahydrofuran hybrid films by FTIR. Journal of Non-Crystalline Solids,

‏.144-154 ,(1-3)283

[19] Patwardhan, S. V., Maheshwari, R., Mukherjee, N., Kiick, K. L., & Clarson, S. J. (2006).

Conformation and assembly of polypeptide scaffolds in templating the synthesis of silica:

an example of a polylysine macromolecular “switch”. Biomacromolecules, 7(2), 491-497.‏

[20] Swann, G. E., & Patwardhan, S. V. (2011). Application of Fourier Transform Infrared

Spectroscopy (FTIR) for assessing biogenic silica sample purity in geochemical analyses

and palaeoenvironmental research. Climate of the Past, 7(1), 65-74.‏

[21] Brinker, C. J., & Scherer, G. W. (2013). Sol-gel science: the physics and chemistry of sol-

gel processing. Academic press, New York, 581.

[22] Socrates, G. (2004). Infrared and Raman characteristic group frequencies: tables and

charts. John Wiley & Sons.‏

[23] Duran, A., Navarro, J. F., Casariego, P., & Joglar, A. (1986). Optical properties of glass

coatings containing Fe and Co. Journal of Non-Crystalline Solids, 82(1-3), 391-399.‏

[24] Bertoluzza, A., Fagnano, C., Morelli, M. A., Gottardi, V., & Guglielmi, M. (1982). Raman

and infrared spectra on silica gel evolving toward glass. Journal of Non-Crystalline Solids,

‏.117-128 ,(1)48

[25] Akl, M. A., Aly, H. F., Soliman, H. M. A., Abd ElRahman, A. M. E., & Abd-Elhamid, A.

I. (2013). Preparation and characterization of silica nanoparticles by wet mechanical

attrition of white and yellow sand. J Nanomed Nanotechnol, 4(183), 2.‏

[26] Gopal, N. O., Narasimhulu, K. V., & Rao, J. L. (2004). EPR, optical, infrared and Raman

spectral studies of Actinolite mineral. Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy, 60(11), 2441-2448.‏

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