氧化锆陶瓷表面原位生成多晶粒及对其粘接性能的影响

Zirconia ceramic been widely used in crown and bridge restorations, however, the bond strength between zirconia-porcelain and zirconia-adhesive is being a subject of study. In our previous study, the in situ synthesized polycrystalline particulates improved the bonding strength of resin to zirconia ceramic. In this study, Zirconia ceramic before final sintered with the characteristics of high porosity and poor chemical stability is used. The zirconia green block surface reacts with HF generates ZrF4, ZrF4 reacts with CaCl2 generates ZrOCl2, and ZrOCl2 generates Zr(OH)4 by treating with alkali heat, polycrystal particulates in-situ synthesis were produced on zirconia ceramic surface while zirconia ceramic restorations are densely sintered. The structure and distribution of the polycrystal particulates will be studied by the reaction solution concentration, reaction time and alkali heat treating temperature. The polycrystal particulates will be observed and characterized by SEM, EDS, XRD and XPS, the effects of the polycrystal particulates on its bonding properties will be tested by porcelain and resin adhesive. The polycrystal particulates will improve the bond strength of ZrO2, and solve the problem of ZrO2 ceramic surface difficult-treating, easy-causing phase transition. The in-situ synthesis polycrystal particulates will be well combined with the base material, and this method is not restricted by the form of base material either. This study provides an effective method for zirconia ceramics surface modification, and may be applied in other fields.

氧化锆陶瓷已广泛应用于冠、桥等固定修复,但其与烤瓷及粘接剂之间的粘接存在问题。在前期研究氧化锆陶瓷表面的多晶粒改善了其与树脂粘接性能的基础上，本研究拟用氧化锆陶瓷致密烧结前孔隙率高、化学稳定性较差的特点，使其表面与HF反应，生成ZrF4，ZrF4与CaCl2反应生成ZrOCl2，经碱热处理生成Zr(OH)4，最终伴随氧化锆陶瓷修复体的致密烧结，在氧化锆陶瓷表面原位生成多晶粒，并探讨多晶粒的结构及分布与反应液的浓度、反应时间及处理温度等的关系，通过SEM、EDS、XRD及XPS等的观察、表征确认表面结构、形态及成分；并用烤瓷、树脂粘接剂检测该多晶粒对氧化锆陶瓷粘接性能的影响，期望该多晶粒能够改善氧化锆的粘结性能，克服氧化锆陶瓷表面处理难、易引起相变等问题。原位生成多晶粒可与基体结合良好，并且不受基材形状的限制。本项目创新性地提供了一种氧化锆陶瓷表面改性的有效方法,并有可能应用于其它领域。

氧化锆性能优良，但其与烤瓷及粘接剂之间的粘接，学者们一直在探索。本研究在氧化锆陶瓷表面原位合成多晶粒，改善氧化锆与饰面瓷及树脂粘接剂的结合。. 根据氧化锆坯体在HF溶液中浸泡时间，分为I1(10s), I3(30s), I5(50s), I7(70s)和I9(90s)组， CaCl2溶液中浸泡90s， NaOH溶液中水浴加热到80℃，保持2h。C为对照组。致密烧结后SEM显示实验组表面晶粒较均匀，随着在HF中浸泡时间延长，晶粒分布密度增加；I7(1.47±0.31μm)和I9(1.54±0.37μm)粗糙度的明显高于其他组。烤瓷后SEM观察未见氧化锆多晶粒与基底分界。对照组氧化锆-瓷界面硬度变化明显，过渡区较窄；实验组随着试件在HF中浸泡时间的增加，硬度明显的降低变缓，过渡区增宽。氧化锆与饰面瓷剪切强度依次:I1 (23.49±3.56MPa), I3(24.59±1.59MPa), I5(26.52±2.22MPa)和I7(27.02±2.44MPa)，高于对照组(20.86±1.13MPa C), I7组最高。三点弯强度实验组和C组相比无明显降低。.选择I3, I5和I7做树脂粘接剂剪切强度, I5（17.84+6.21Mpa）和I7(16.27+5.87Mpa)较对照组C(7.88±1.94Mpa)相比有明显提高。.选择I3，I5和I7,涂布粘接剂后是施加负压（-0.04 MPa），氧化锆和树脂之间的剪切强度随着多晶颗粒分布密度的增加和负压的施加而显著增加。.MC3T3-E1细胞对多晶颗粒表面改性氧化锆的生物学反应，细胞在多晶颗粒改性的氧化锆I7表面附着良好，与对照组相比显示出更高的增殖活性，其碱性磷酸酶活性也明显增高。.硅-锆溶胶溶液浸泡在氧化锆表面制备氧化锆-氧化硅涂层，显著增高氧化锆与树脂粘接剂的剪切强度。.氧化锆Ca-P渗透改性改善氧化锆的生物活性。通过液体渗透改性的方法，以CaCl2•2H2O 及 NaH2PO4•2H2O为Ca源和P源，致密烧结后表面形成O, Ca和P的黑色簇状物质MTT结果显示，钙磷改性氧化锆水热处理前后均能促进成骨细胞的增殖。.负压改善氧化锆陶瓷与树脂的粘接强度，在涂布粘接剂后施以0.04MPa的负压，可以增加粘接剂与氧化锆之间的微观渗透，提高其剪切强度，尤其是粗糙的表面。