Calcium phosphate 결정 성장 최적화를 위한 Ti 표면의 BaTiO_3 박막 형성에 관한 연구
A study on the BaTiO_3 thin film formation on Ti surface for the optimization of calcium phosphate crystal growth
구강과학- 전남대학교 2001년 13권 2호 p.149 ~ 168
조진우, 김원재, 박영준, 황규석, 송종은, 이용렬,
소속 상세정보
조진우 ( ) - 전남대학교 치과대학 보철학교실
김원재 ( ) - 전남대학교 치과대학 보철학교실
박영준 ( ) - 전남대학교 치과대학 보철학교실
황규석 ( ) - 전남대학교 치과대학 보철학교실
송종은 ( ) - 전남대학교 치과대학 보철학교실
이용렬 ( ) - 전남대학교 치과대학 치과재료학교실
KMID : 0988420010130020149
Abstract
This study was purposed to establish an optimized manufacturing process for a negatively charged ferroelectric thin flim on titanium substrate in order to develop a new implant system having the mechanical strength and bone forming ability. Ferroelectric materials show an alignment of positive and negative charges by poling treatment. Based on this property, this study was performed with the assumption that the Ca^2+ ions would be easily attracted on negatively charged surface and the attracted cation might behave as nuclei for bone-like crystal grownth in biological solutions. In order to have an osteoinducibility by the ferroelectric thin film coating, continuous and flawless crystalline thin film should be formed with ferroelectricity, and finally should be adequately poling treated.
In this study, BaTiO_3 (BTO) was selected as a ferroelectric material. Before thin film coating process, most favorable poling condition was investiged with the evaluation of the difference in calcium phosphate (Ca-P) formation in simulated body fluid (SBF). Moreover, the parameters to form an optimum thin film were studied.
Dense bulk BTO disks were fabricate using cold isostatic pressing(CIP) and sintered in air at 1300℃ for 2 hours. Sintered BTO disk was polished, and he crystallinity, microstructure, and ferroelectric characteristics were evaluated using an X-ray diffraction analysis (XRD), a field emission scanning electron microscope (FE-SEM), and an Impedance analyzer.
To find the optimum poling condition for the calcium phosphate crystal formation, sintered bulk BTO specimens were treated with either of following poling conditions; 1) room temperature poling treatment [ polarizing field (Ep) = 25kV/cm, at 25℃ for 2 hours], 2) under Tc medium-temperaturepoling treatment (Ep=20kV/cm, from 85˚C to 25˚C for 2 hour), and 3) above Tc high-temperature poling were immesed in simulated body fluid (SBF) for 30 days, and the formation of calcium phosphate (Ca-P) layer n the surface was evaluated.
The crystallinity, microstructure, and ferroelectric characteristic of BTO thin film were evaluated withthe variation of final heat treatment. It was performed after establishing the starting substance-solvent mixing ratio, coating times, and pre-heating temperature optimal to form continuous and flawless BTO thin film adequate for having ferroelectricity.
Perparation of BTO thin film was made by dipping-pyrolysis technique using metal naphthenates as starting substances. BTO thin films was spin-coated on Ti substrate by dipping-pyrolysis technique using sol obtained by mixing Ba-naphthenate and Ti-naphthenate as starting substances. Pre-firing temperature of BTO thin film was performed at 450℃ because organic-solvent ws completely volatilized without any crystal growth, and the final heat treatment was performed at 600, 700 or 800℃, respectively. The results are as follows;
1. BTO disk sintered at 1300℃ for 2 hours showed average grain size of about 1㎛ and the relative dielectric constant at 1㎑ was abut 3000∼3500.
2. After immersing the sintered bulk BTO poled at respective conditions in SBF for 30 days, Ca-P layers were present on the negatively charged surfaces. In contrary, positively charged Bto surface did not show any noticeable charge of the surface microstructure after SBF immersion.
3. In he case of poling condition 1 and 2 treated with below Tc, Ca/P ratio showed a relatively low value of 1,.2∼1.5. While, in the case of poling condition 3 treated with above Tc, Ca/P ratio was 1.5∼1.67, which is similar to that of biological apatite. This phenomenon demonstrates that poling the BTO above the temperature of Tc is preferable for the Ca-P formation.
4. For thin film BTO coastin, the starting substance was prepared by an equimolar mixing of the Ba and Ti-naphthenate. Dilution of the starting substance with toluene was most appropriate at sol : toluene ratio of 5.2:4.8 Too thin sol produced porosity in film, and too thick sol resulted cracks in the film. By repeating the coating and pre-firing procedure 15 times, homogeneous film of 0.5㎛ thickness could be fabricated, and perfomed well during the poling treatment without breakdown.
5. The heat-treatmen of the BTO thin film at 700℃ produced a homogeneous crystalline structure without heterogeneous TiO2 formation. The BTO thin film heat-treated at 600℃ showed non-crystallinity and no ferroelectricity. Treatment at 800℃ produced heterogeneous TiO2 phase in the film, which is unfavorabe for having ferroelectricity by the distortion of the perovskite structure. The relative dielectic constant at 1 ㎑ was 152 and 112 by heat-treatment at 700 and 800℃, respectively.
In summary, these results demonstrated that poling the ferroelectric B_aT_iO_3 surface negatively is effective for the formation of Ca-P layer in simulated body fluids. Poling condition at a temperature cooling from above Tc down to room temperature is most effective. By optimizing the method of BTO thin film coating on metal substrate for the formation of Ca-P layer, the data of this study might be applied for the manufacture of new bioactive implant system.
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