• Journal of the Korean Ceramic Society
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• v.29 no.9
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• pp.729-738
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• 1992

The glass formation and structural change with the glass compositions were investigated in the CaO-P2O5-SiO2 system with less than 40 wt% of P2O5. The glass formation range was determined by XRD, SEM and EDS techniques for water quenched specimens. The structural analyses were made for binary CaO-SiO2 glasses and ternary CaO-P2O5-SiO2 glasses by using FT-IR and Raman spectroscopy. The glass formation was affected by CaO/SiO2 mole ratio, P2O5 content and primary crystalline phase. The stable glass formation range was found when the transformed CaO/SiO2 mole ratio (new factor derived from structural changes) was in the range of 0.72~1.15 with less than 10 mol% of P2O5. The structural analyses of CaO-SiO2 glasses indicated that as the CaO/SiO2 ratio was increased, the nonbridging oxygens in the structural unit of the glasses were increased. With addition of P2O5 to CaO-SiO2 glasses, the P2O5 enhanced the polymerization of [SiO4] tetrahedra unit in CaO-SiO2 glasses, which contained a large portion of nonbridging oxygen. The phosphate eliminated nonbridging oxygens from silicate species, forcing polymerization of silicate structures and produced in [PO4] monomer in glasses. When added P2O5 was kept constant, the structural change with various CaO/SiO2 ratio was very similar to that of CaO-SiO2 glasses.

• Journal of the Korean Ceramic Society
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• v.30 no.4
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• pp.289-298
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• 1993

Properties in terms of the variation of the glass compositions, which were density (p), molar volume(Vm), atom/ion packing density (Dp), refractive index (nD), transformation temperature (Tg), dilatometric softening point (Td), thermal expansion coefficient (α), Young's modulus (E), and knoop hardness (KHN) were investigated in CaO-SiO2 glasses and CaO-P2O5-SiO2 glasses containing less than 10mole% of P2O5. Those properties were measured by density measurement kit, Abbe refractometer, dilatometer, ultrasonic pulse echo equipment, and micro hardness tester. When CaO content was increased in CaO-SiO2 glasses, p, Dp, nD, Tg, Td, α, E and KHN were increased, while Vm was decreased. When P2O5 was added to the CaO-SiO2 glasses with constant CaO/SiO2 ratio as 1.07, p, Dp, nD, Tg, Td, α, E and KHN were decreased, while Vm was increased. When the amount of P2O5 in glasses was kept constant, the changes of the properties with variation of CaO content in the CaO-P2O5-SiO2 glasses were very similar to those of CaO-SiO2 glasses. These phenomena could be explained by the structural role of P2O5 in the CaO-P2O5-SiO2 glasses, which was polymerization of siicate structures and resulted in [PO4] monomer structure in glasses. Due to this structural characteristics, the bond strength and packing density were changed with compositions. Proportional relationships between 1) np and Dp, 2) Tg, Td, α and CaO content, 3) E and Vm-1, and 4) KHN and P2O5 content were evaluated in this investigation.

• Journal of the Korean Ceramic Society
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• v.30 no.6
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• pp.433-440
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• 1993

The bioactivity of glasses in the CaO-SiO2 system and CaO-P2O5-SiO2 system with less than 10mol% of P2O5 was investigated by in vitro test in simulated body flood(SBF). The formation of Ca.P film and hydroxyapatite on the surface of glasses after in vitro test was analysed by X-ray photoelectron spectoscopy (XPS), fourier transform infrared reflection spectroscopy (FT-IRRS), energy dispersive X-ray spectroscopy (EDS), and scanning electron microscopy (SEM) observation. In the early stage of Ca.P film formation after in vitro test for CaO-SiO2 and CaO-P2O5-SiO2 glasses, the rate of Ca.P film formation on the surface of the glasses was dependent of structural parameter (Y) evaluated from the glass composition. First, in the case of the glasses having Y value below 2, Ca.P film and SiO2-rich layer were formed simultaneously, and there were no differences of the rate of Ca.P film formation in terms of the Y values. Second, in the case of the glasses having Y value above 2, the SiO2-rich layer was formed, and then Ca.P.Si mixed layer was formed in the silica gel structure of the SiO2-rich layer, and finally the Ca.P film on the surface of SiO2-rich layer. The rate of Ca.P film formation delayed as the Y values increased. The rate of hydroxyapatite formation of glasses (the rate of transformation from Ca.P film to hydroxyapatite) seems to be propotional to the rate of Ca.P film formation and Y value. The rate of hydroxyapatite formation of glasses belonging to the second group was delayed as structural parameter increased, and the hydroxyapatite crystal showed spherical growth in the early reaction stage, and then showed silkworm-like linear growth as the reaction time increased.

• Journal of the Korean Ceramic Society
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• v.31 no.5
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• pp.505-512
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• 1994

It has been reported that a biocement obtained by mixing CaO-SiO2-P2O5 glass powder and ammonium phosphate solution has biocompatibility as well as high strength. However, the compositional dependence on its hardening and hydroxyapatite formation phenomena has not been studied. Therefore, the main objective of this work is to study the effects of P2O5, MgO in CaO-SiO2 system glass on the hardening and hydroxyapatite formation. When more than 50 mole% of CaO containing CaO-SiO2 glasses was reacted with ammonium phosphate solution, CaNH4PO4.H2O crystal was formed, but the glass with less than 50 mol% of CaO formed (NH4)2HPO4 and NH4H2PO4 crystals which are derived from ammonium phosphate solution without reacting with the glasses. As the amount of P2O5 in CaO-SiO2-P2O5 glass system was increased, the formation of CaNH4PO4.H2O crystal was enhanced. When those hardened samples were reacted with tris-buffer solution, hydroxyapatite was obtained only for the sample with CaNH4PO4.H2O. While the substitution of MgO for CaO decreased the formation of CaNH4PO4.H2O crystal. MgNH4PO4.H2O crystla was formed in high MgO containing glass, which did not react with tris-buffer solution.

• Journal of Technologic Dentistry
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• v.21 no.1
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• pp.5-14
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• 1999

Glass ceramics for dental crown prosthesis were prepared by crystallization of CaO-MgO-SiO2-$P_2O_5-TiO_2$ glasses. Their crystallization behaviors have been investigated as a function of heattreatment temperature, holding time and chemical composition in relation to mechinical properties. Crystallization peak temperatures were determined by differential thermal analysis(DTA). Crystalline phases and mircostructures of heat-treated sample were determined by the means of powder X-ray diffraction(XRD) and scanning electron microscopy(SEM). The final crystalline phase assemblages and the microstructures of the samples were found to be dependent on glass compositions, heattreatment temperature, and holding time. 1st crystallization peak temperature(TP), affected strongly by apatite, was found to be increased or decreased. From the experiment, the following results were obtained : 1. The crystallization peak temperature($T_P$) formed by apatite increased until adding up to 9wt% $TiO_2$ to base glass composition, then decreased above that. 2. Apatite($Ca_{10}P_6O_{25}$), whitlockite(${\beta}-3CaO-P_2O_5$), $\beta$-wollastonite($CaSiO_3$), magnesium tianate($MaTiO_3$) and diopside(CaO-MgO-$2SiO_2$) crystal phase were precipitated in MgO-CaO-$SiO_2-TiO_2-P_2O_5$ glass system containing 9wt% and 11wt% of $TiO_2$ 3. Vickers hardness of samples increased with increasing heat-treatment temperature and Vickers hardness of S415T9 samples heat-treated at 1075 was approxi-mately 813Kg $mm^{-2}$ as maximum value. 4. Vickers hardness of samples increased due to precipitation of apatite, whitlockite, $\beta$-wollastonite, magnesium titanate, and diopside crystal phases within glass matrix.

• Journal of the Korean Ceramic Society
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• v.31 no.10
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• pp.1231-1239
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• 1994

In this study, gel powder which had relatively high hydration reactivity in CaO and P2O5 rich composition of CaO-P2O5-SiO2-H2O system was prepared by sol-gel process and its hydrated specimen was manufactured. The it was investigated to appropriate calcination temperature in sol-gel process which hydrated specimen of gel powder have proven to strength and the effect of factors influenced strength in hydration process. The major product of before and after hydration reaction was hydroxyapatite, and crystalline phase of C-S-H was already formed during gelation process. After hydration reaction of pressed specimen, crystalline phase of C-S-P-H was formed. It was hydrated product of silicocarnotite (5CaO.P2O5.SiO2). Gel phases of C-S-H and C-S-P-H occured as a result of partial substitution of amorphous silica by P2O5 was formed. The strength of hydrated hardened body is developed by strong bonding and bridging between the gel phases of C-S-H or C-S-P-H and the crystalline products such as hydroxyapatite, Ca(OH)2 C-S-H and C-S-P-H. In addition, the ultrafine gel powder have an great effect on increase of hydration reaction.

• Journal of the Korean Ceramic Society
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• v.37 no.11
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• pp.1105-1113
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• 2000

Bioglass 조성 중 45S5 (46.1SiO$_2$.24.4$Na_2$O.26.9CaO.2.6P$_2$O$_{5}$ : 몰비)를 기본 조성으로 하여 46P4 (46.2SiO$_2$.49.5CaO.4.3P$_2$O$_{5}$ : 몰비), 46SF (46.1SiO$_2$24.4$Na_2$O.16.1CaO.2.6P$_2$O$_{5}$.10.8CaF : 몰비) 그리고 55SF (55.1SiO$_2$.9.2$Na_2$O.27.8CaO.3.4P$_2$O$_{5}$.4.5CaF : 몰비)를 제조하여 tris-완충용액 및 유사 생체용액(simulated body fluid)에서 반응시킨 후 생체활성유리의 표면에 생성되는 아파타이트 결정형에 관하여 연구하였다. 45S5 유리를 tris-완충용액에 반응시켰을 경우 6시간 반응시부터 수산화 아파타이트가 생성되었으나 유사 생체용액에 반응시켰을 경우에는 24시간까지도 수산화 아파타이트 결정이 생성되지 못하고 비정질 상태의 칼슘 인산염만 형성되었다. tris-완충용액에 각 조성의 유리를 200시간 반응시킨 경우 불소를 함유하지 않은 유리에서는 잎사귀 모양의 수산화 아파타이트가, 불소를 함유한 유리에서는 구상의 플루오르 아파타이트가 형성되었다. 그러나 유사 생체용액에 각 조성의 유리를 200시간 반응시켰을 경우 불소를 함유하지 않은 유리에서는 누에고치형의 수산화 아파타이트가 형성되었고 불소를 함유한 유리에서는 무정형의 칼슘 인산염이 생성되었다.

• Korean Journal of Materials Research
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• v.14 no.1
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• pp.67-72
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• 2004

The glass-forming conditions are investigated in the $K_2$O-CaO-$SiO_2$ $-P_2$$O_{5}$ system with 10~65 mole% of$ P_2$$O_{5}$. Thermal properties and dissolution properties were investigated according to variation of the SiO and KO contents in selected compositions. The glass formation condition was determined when $K_2$O/$P_2$$O_{5}$ mole ratio 0~0.24, $SiO_2$/($SiO_2$+$P_2$$O_{5}$ ) mole ratio 0～0.29, and CaO/$P_2$$O_{5}$ mole ratio 0~1.00. In the result of the thermal properties, the glass transition temperature($T_{g}$) and softening temperature($T_{s}$ ) were gradually shifted to the lower temperature range with increase of $K_2$O contents. The maximum value of the chemical durability was shown in $K_2$$PO_2$$O_{5}$ mole ratio 0.17 when the $SiO_2$ contents were changed, and $K_2$O was fixed at 10 mole%. Hence the change of the $K_2$O/$P_2$$O_{5}$ mole ratio was found that a new main factor of the chemical durability.

• Journal of the Korean Ceramic Society
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• v.40 no.11
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• pp.1132-1137
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• 2003

For the application of environment conscious glass-fertilizer, dissolution characteristics of phosphate glass was investigated. In 0.1K₂O-0.1SiO₂-0.6P₂O/sub 5/ glass system, the compositions were designed according to variation of CaO & MgO contents, and glass formation region was confirmed. From the glass composition, the confirmed glasses were investigated to figure out thermal and dissolution properties. It was detected that glass transition & softening temperature of the glasses increased with increasing MgO contents. The dissolution properties of the glasses was affected by CaO and MgO content ratio.

• Proceedings of the Materials Research Society of Korea Conference
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• 2001.11a
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• pp.58-58
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• 2001