牙科Y-TZP陶瓷的制作工艺、颜色调控及其半透明性研究

发布时间：2018-05-23 09:29

本文选题：钇稳定氧化锆 + 颜色　；参考：《中国人民解放军医学院》2014年博士论文

【摘要】：钇稳定氧化锆陶瓷（Y-TZP）在室温条件下，通过应力作用可以发生马氏体相变因而具有较佳的力学特性，其优良的生物安全性、耐磨性能和抗腐蚀性能，使Y-TZP成为理想的牙科陶瓷材料，Y-TZP与其它牙科陶瓷材料相比较，具有理想的机械力学性能。目前未着色Y-TZP呈现出白色或象牙色，半透明性较差，虽然可以模拟天然牙颜色，，但在临床上并不能满足口腔医生和患者对修复体美观性能的要求，Y-TZP的表面常常需要遮色，这会让材料近一步降低其半透明性，然而如果Y-TZP颜色被调整到与拟修复牙齿相接近，这将会让牙齿配比颜色的过程变得简单，同时改善Y-TZP的半透明性，将获得良好的质感。Y-TZP着色一般通过两种方法，一是外着色，将初烧结Y-TZP块浸入染色液中浸泡，然后烧结；另一种方法是内着色，在Y-TZP粉体中添加着色剂。将Y-TZP块放入染色液中浸泡的外着色方法操作简单，但容易发生Y-TZP块着色不均匀，着色结果受操作影响大，同时不能将同样的操作程序应用于其它品牌。在生产过程中，将着色氧化物加入Y-TZP粉体中的内着色方法，可以使Y-TZP块着色后，颜色准确均一，并且对Y-TZP半透明性影响较小，目前Y-TZP内着色是一种较理想的Y-TZP颜色解决方案。Y-TZP底层材料尽管具有优良的机械力学性能，但是其半透明性能较差。在齿科常用陶瓷中氧化锆晶体的折射率较高，光的散射大，可见光透射率较低，无法满足修复体特别是前牙区修复的美学要求。如果使用Y-TZP制作的基底冠的颜色和半透明性可以与牙体组织的颜色相匹配，那么齿科技师在修复体制作过程中通过降低饰面瓷的厚度，减少备牙量，最终可以让修复体达到预期的美学效果。本论文采用添加着色氧化物粉体的方式对Y-TZP进行内着色，试制出了颜色与VITA-3D Master比色板相近的内着色Y-TZP修复体材料，并对其粉体加工工艺、微观结构和材料光学性能进行了研究。本研究的主要目的是选取适合的着色氧化物对Y-TZP粉体进行内着色，系统研究加工工艺和着色剂对Y-TZP最终颜色和半透明性的影响，Y-TZP颜色参考VITA-3D Master比色板，对颜色进行测定，以期获得临床上符合前牙美学要求的Y-TZP材料。结果如下： 1.本实验分析了影响Y-TZP浆料性质的浆料固含量、PVA加入量、球磨时间三个因素，分析得出浆料固含量对浆料的流变性具有显著的影响，PVA加入量、球磨时间长度对Y-TZP浆料的平均粘度和沉降度均没有显著的影响。 2.喷雾造粒浆料的粘度和沉降度都是不可忽视的要素，要便于大规模工业化的生产需求，浆料的固含量为50wt%。根据正交试验结果以及生产工艺验证试验，确定PVA的加入量为3wt%。本实验主要目的是要试制着色均匀的并有一定半透明性的Y-TZP齿科用修复材料。根据工业化生产经验及生产工艺验证，确定球磨时间长度为24h。本实验分析得到的最好喷雾造粒浆料的方案为A3B3C3，即固相含量为50wt%；PVA加入量为3wt%；球磨时间长度为24h。通过工艺验证，造粒后得到的粉体颗粒大多成球形，边缘较圆滑，粉体内无气泡、球体几乎无破碎。 3.未着色Y-TZP、0.15wt%Fe2O3着色Y-TZP、4wt%CeO2着色Y-TZP的造粒粉体颗粒大致分布在40-120μm之间。同时颗粒分布较窄，60-90μm左右的粉体颗粒较多。造粒后的粉体颗粒粒度不是完全一致，有一定的尺寸级配。Fe2O3作为着色剂进行内着色对颗粒的粒径产生一定的影响，D50比未着色的Y-TZP要大，但影响不明显。 4. Fe2O3、CeO2作为Y-TZP的内着色剂，对造粒粉体的流动性、成球性能和预烧结体的密度影响不大。 5.0.15wt%Fe2O3着色Y-TZP、4wt%CeO2着色Y-TZP终烧结后，晶相主要为四方相ZrO2，XRD的衍射峰中均未出现Fe2O3、CeO2峰。0.15wt%Fe2O3着色Y-TZP、4wt%CeO2着色Y-TZP终烧结后，着色Y-TZP烧结致密，晶粒大小均匀，晶粒尺寸约为0.5-0.7μm。着色Y-TZP的断裂方式为穿晶断裂和沿晶断裂。 6. Fe2O3添加量的增加，Y-TZP的明度值从84下降到75左右，明度值逐渐下降。伴随着明度的下降，a*、b*色调值同时增大，b*值的增幅比a*值大。b*值从10.76增加到23.65。当Fe2O3添加量超过0.06wt%后，a*、b*值都有较明显的增加。Fe2O3对a*值的影响不是很大，对b*值影响较大。随着CeO2含量的增加，着色Y-TZP的b*增加，但幅度较小，着色作用比较弱。a*值随着CeO2含量的增加而稍有降低，总体波动范围不大。CeO2含量的变化对着色Y-TZP的明度影响较小。 7.未着色Y-TZP和着色Y-TZP的可见光透射率具有波长依赖性，在400-700nm可见光区域内，透射率单调一致，随波长的增加，透射率也增加。未着色Y-TZP的透射率曲线几乎为一条直线，可见光透射率明显高于着色Y-TZP。 8.未着色Y-TZP组和0.03wt%Fe2O3着色Y-TZP组之间有统计学差异（P＜0.05），0.03wt%Fe2O3着色Y-TZP组和0.15wt%Fe2O3着色Y-TZP组之间有统计学差异（P＜0.05），未着色Y-TZP组和0.15wt%Fe2O3着色Y-TZP组之间有统计学差异（P＜0.05）。可见光透射率，未着色Y-TZP＞0.03wt%Fe2O3着色Y-TZP＞0.15wt%Fe2O3着色Y-TZP。 9.未着色Y-TZP组和1wt%CeO2着色Y-TZP组之间有统计学差异（P＜0.05），1wt%CeO2着色Y-TZP组和4wt%CeO2着色Y-TZP组之间有统计学差异（P＜0.05），未着色Y-TZP组和4wt%CeO2着色Y-TZP组之间有统计学差异（P＜0.05）。可见光透射率，未着色Y-TZP＞1wt%CeO2着色Y-TZP＞4wt%CeO2着色Y-TZP。
[Abstract]:Yttrium stabilized zirconia ceramics (Y-TZP) can have better mechanical properties at room temperature by stress action and thus has better mechanical properties. Its excellent biological safety, wear resistance and corrosion resistance make Y-TZP an ideal dental ceramic. Compared with its dental ceramics, Y-TZP has ideal mechanical mechanics. Performance. The current uncolored Y-TZP presents white or ivory color and is less translucent. Although it can simulate natural tooth color, it does not meet the clinical requirements of the dentist and patient on the aesthetic performance of the prosthesis. The surface of the Y-TZP often requires shade, which will reduce the translucency of the material in a near step, however, if the Y-TZP color is colored The adjustment to the proposed restoration of the teeth will make the process of the color matching of the teeth simpler and improve the translucency of the Y-TZP, and the good texture of the.Y-TZP will be obtained by two methods, one is the external coloring, the initial sinter Y-TZP is soaked in the dyeing solution and then sintered; the other is the internal coloring, in the Y-TZP powder. A coloring agent is added to the body. The external coloring method to immerse the Y-TZP block into the dye is simple, but it is easy to have the uneven coloring of the Y-TZP block, the coloring result is influenced greatly by the operation, and the same operating procedure can not be applied to other brands. In the process of production, the coloring of the colored oxygenate into the Y-TZP powder can be used in the production process. After coloring the Y-TZP block, the color is accurate and uniform, and it has little effect on the translucency of Y-TZP. At present, Y-TZP interior coloring is an ideal Y-TZP color solution,.Y-TZP bottom material, although it has excellent mechanical and mechanical properties, but its translucent performance is poor. If the color and translucency of the base crown made with Y-TZP can match the color of the tooth tissue, the dental technician can reduce the thickness of the veneer porcelain and reduce the amount of tooth preparation in the process of making the prosthesis. The restorative body has achieved the desired aesthetic effect. In this paper, the interior coloring of Y-TZP was made by adding coloring oxide powder, and the interior coloring Y-TZP restorer materials with similar color and VITA-3D Master were produced. The processing technology, microstructure and optical properties of the powder were studied. The main purpose of this study was to study the main purpose of this study. The suitable coloring oxide was selected for internal coloring of Y-TZP powder. The effects of processing technology and colorant on the final color and translucency of Y-TZP were systematically studied. Y-TZP color reference VITA-3D Master was used to determine the color in order to obtain the Y-TZP material which was clinically suitable for the anterior tooth aesthetics. The results were as follows:
1. the experiment analyzed the slurry solid content of the Y-TZP slurry, the amount of PVA and the ball milling time three factors. It was found that the solid content of the slurry had a significant influence on the rheological property of the slurry. The amount of PVA and the length of the ball milling time had no significant influence on the average viscosity and the settlement degree of the Y-TZP slurry.
2. the viscosity and the settlement degree of the spray granulation slurry are all factors which can not be ignored. To facilitate the production demand of large-scale industrialization, the solid content of the slurry is 50wt%. based on the orthogonal test results and the production process verification test. The main purpose of the experiment is to determine the PVA's addition of 3wt%.. The main purpose of this experiment is to try to make a homogeneous and translucent Y with a uniform color. -TZP dental repair materials. According to the industrial production experience and production process verification, the best spray granulation slurry obtained by the ball milling time length is 24h., which is A3B3C3, that is, the solid content is 50wt%, the PVA addition is 3wt%, the ball milling time is 24h. through process verification, and the particle size is large after granulation. It is more spherical, with smooth edges and no bubbles in the powder, and the ball almost has no breakage.
3. uncoloured Y-TZP, 0.15wt%Fe2O3 coloring Y-TZP, and 4wt%CeO2 colored Y-TZP granulation particles are roughly distributed between 40-120 mu m. The particle distribution is narrower and the particle size is more than 60-90 mu m. The particle size of the powder after granulation is not exactly the same, and a certain size graded.Fe2O3 is used as the colorant for inner coloring particles. The diameter has a certain effect. D50 is larger than unstained Y-TZP, but the effect is not obvious.
4. Fe2O3, CeO2 as the internal colorant of Y-TZP, has little effect on the fluidity, pelletizing property and density of pre sintered powders.
After the 5.0.15wt%Fe2O3 coloring Y-TZP and the final sintering of 4wt%CeO2 coloring Y-TZP, the crystal phase is mainly ZrO2 of the Quartet phase, and there is no Fe2O3 in the diffraction peak of XRD, CeO2 peak.0.15wt%Fe2O3 coloring Y-TZP, 4wt%CeO2 coloring Y-TZP after sintering, the coloring is compact and the grain size is uniform, and the fracture mode of grain size inch is about the transgranular fracture. Crack and intergranular fracture.
6. Fe2O3 added, the brightness value of Y-TZP decreased from 84 to about 75, and the brightness value decreased gradually. With the decrease of brightness, a*, b* hue value increased at the same time, the b* value increased from 10.76 to 23.65. when the Fe2O3 added more than 0.06wt%, a*, b* values had a significant increase in the value. With the increase of CeO2 content, the b* of coloring Y-TZP increases with the increase of the content of Y-TZP, but the amplitude is smaller, and the weaker.A* value decreases slightly with the increase of CeO2 content, and the variation of the overall fluctuation range is less.CeO2 content than the brightness of the color Y-TZP.
7. the visible light transmittance of uncoloured Y-TZP and coloring Y-TZP has wavelength dependence. In the 400-700nm visible region, the transmittance is monotonous and the transmittance increases with the increase of wavelength. The transmittance curve of the uncoloured Y-TZP is almost a straight line, and the visible light transmittance is obviously higher than that of the coloring Y-TZP..
There was a statistical difference between the 8. unstained Y-TZP group and the 0.03wt%Fe2O3 colored Y-TZP group (P < 0.05). There was a statistical difference between the 0.03wt%Fe2O3 colored Y-TZP group and the 0.15wt%Fe2O3 coloring Y-TZP group (P < 0.05). There was a statistical difference between the non coloured Y-TZP group and the 0.15wt%Fe2O3 pigmented Y-TZP group (0.05). 2O3 coloring Y-TZP > 0.15wt%Fe2O3 coloring Y-TZP.
There were statistical differences between the 9. unstained Y-TZP group and the 1wt%CeO2 colored Y-TZP group (P < 0.05). There was a statistical difference between the 1wt%CeO2 colored Y-TZP group and the 4wt%CeO2 coloring Y-TZP group (P < 0.05). There was a statistical difference between the non coloured Y-TZP group and the 4wt%CeO2 pigmented Y-TZP group (0.05). %CeO2 coloring Y-TZP.
【学位授予单位】：中国人民解放军医学院
【学位级别】：博士
【学位授予年份】：2014
【分类号】：R783.1

【参考文献】