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CN115745599A - 一种氧化锆基抗菌义齿材料及其制备方法 - Google Patents

一种氧化锆基抗菌义齿材料及其制备方法 Download PDF

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CN115745599A
CN115745599A CN202211412647.6A CN202211412647A CN115745599A CN 115745599 A CN115745599 A CN 115745599A CN 202211412647 A CN202211412647 A CN 202211412647A CN 115745599 A CN115745599 A CN 115745599A
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oxide
zirconia
parts
based antibacterial
denture material
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CN115745599B (zh
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李宗育
刘威
张宇
刘建君
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Shenzhen Yurucheng Oral Material Co ltd
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Shenzhen Yurucheng Oral Material Co ltd
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Priority to EP23200343.4A priority patent/EP4368597A1/en
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Abstract

本发明公开了一种氧化锆基抗菌义齿材料及其制备方法，包括质量份数如下的组分：75‑80份氧化锆、2‑5份纳米氧化银、3‑5份纳米氧化锌、1‑3份纳米氧化镧、1‑3份纳米氧化钇、1‑2份氧化铈、1‑2份尺寸控制剂，抗菌效果好、强度高。

Description

一种氧化锆基抗菌义齿材料及其制备方法
技术领域
本发明涉及义齿技术领域，尤其涉及一种氧化锆基抗菌义齿材料及其制备方法。
背景技术
义齿就是人们常说的“假牙”，医学上是对上、下颌牙部分或全部牙齿缺失后制作的修复体的总称，义齿分为可摘与固定两种。固定义齿不能由患者自己取戴的，而可摘义齿可以由患者方便地取戴。
义齿打破了原有的口腔生态环境平衡，使其作为口腔中的异物，比真牙更容易藏污纳垢，如果清洁不及时，就会在义齿及天然牙表面形成牙菌斑，其中的产酸菌如果长时间存留在牙釉质表面，引发如龋齿、牙龈炎、牙周病、义齿性口炎等口腔疾病，更严重者，附着在假牙上的其它病原菌可能通过口咽部进入呼吸系统，还有引发细菌性肺炎等感染性疾病的风险，因此，亟需具有抗菌性能的抗菌义齿材料，以解决现有的义齿佩戴后打破了口腔生态平衡，引起口腔疾病问题。
现有技术中，通常利用义齿表面处理和自身处理两种方式进行抗菌，前者是对义齿表面进行电荷改变或形成聚电解质多层膜等，但这种方式在使用过程中，由于义齿的长期磨损会降低其抗菌性，而后者是在义齿成型过程中加入抗菌剂例如氧化锌，但是由于氧化锌的带隙是3.3ev，只能波长吸收小于385nm的紫外光，在可见光或黑暗环境下并不能很好的发挥其抗菌作用，因此此类抗菌义齿的抗菌效果也有待提升。
发明内容
有鉴于此，本申请提供一种氧化锆基抗菌义齿材料及其制备方法，抗菌效果好、强度高。
为达到上述技术目的，本申请采用以下技术方案：
第一方面，本申请提供一种氧化锆基抗菌义齿材料，包括质量份数如下的组分：75-80份氧化锆、2-5份纳米氧化银、3-5份纳米氧化锌、1-3份纳米氧化镧、1-3份纳米氧化钇、1-2份氧化铈、1-2份尺寸控制剂。
优选的，尺寸控制剂为硅酸钙。
优选的，氧化银与氧化锌的质量之和与氧化钇的质量比为5:0.5-1。
优选的，氧化锆的粒径小于等于30nm。
第二方面，本申请提供一种氧化锆基抗菌义齿材料的制备方法，包括以下步骤：
S1.按比例称取氧化锆、氧化银、氧化锌、氧化镧、氧化钇、氧化铈、尺寸控制，经球磨混合，得到陶瓷粉料；
S2.将陶瓷粉料装入模具中预压，得到抗菌义齿瓷块前体；
S3.依次对抗菌义齿瓷块前体进行冷等静压、预烧结、高温烧结处理，得到氧化锆基抗菌义齿材料。
优选的，冷等静压成型的压力100-300MPa，保压时间60-600s。
优选的，预压压力为5-50MPa，保压时间10-60s。
优选的，预烧结的终温为800-1000℃，升温速率为10-50℃/min，保温时间为1-5h。
优选的，高温烧结的终温为1400-1550℃，升温速率为1-10℃/min，保温时间为1-5h。
优选的，高温烧结过程在磁场环境下进行。
本申请的有益效果如下：本方案中利用氧化锌、氧化镧、氧化铈复配烧结，使得氧化锆基义齿材料具备优异的抗菌性，对大肠杆菌、金黄色葡萄球菌均能有效抑制且抗菌时间长；氧化锆基抗菌义齿材料中的氧化镧、氧化钇、氧化铈及尺寸控制剂的加入克服了由于添加抗菌性材料氧化锌及氧化银引起的降低氧化锆陶瓷力学性能的缺陷；本申请制备氧化锆基抗菌义齿材料的方法简单、快速，且通过调整压力及烧结程序参数能防止在成型过程中出现“崩瓷”的现象。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
氧化锌作为常规的抗菌材料在抗菌陶瓷中已普遍被认可，但少有应用于义齿陶瓷中，其原因在于，氧化锌的带隙是3.3ev，只能波长吸收小于385nm的紫外光，而义齿的使用环境为湿热黑暗或可见光条件居多，因此，氧化锌在义齿材料中并不能完全发挥其抗菌性能；而氧化银虽然也为常规的抗菌材料，但其稳定性及持久性差，作为需要长期使用的义齿而言适用性不强；再者，氧化锆基义齿材料需具备优异的力学性能以防止义齿损坏，而添加软金属类氧化物如氧化银、氧化锌、氧化铜等物质会降低其耐磨损性能，因此，需提供一种既能保证氧化锆基义齿耐磨损性能又能提高其抗菌性能的氧化锆基抗菌义齿材料。
基于此，创立了本发明。
本申请提供一种氧化锆基抗菌义齿材料，包括质量份数如下的组分：75-80份氧化锆、2-5份纳米氧化银、3-5份纳米氧化锌、1-3份纳米氧化镧、1-3份纳米氧化钇、1-2份氧化铈、1-2份尺寸控制剂。
本方案中，为了提高氧化锌对可见光的吸收，可通过掺杂改性其它离子来改变、收窄氧化锌的带隙，同时增大表面缺陷，提高氧化锌的光催化活性，进而增强抗菌能力，经烧结后，氧化锆基抗菌义齿材料中的铈及镧协同促使氧化锌形成纳米纤锌矿晶型的氧化锌和降低禁带宽度值，提高其光催化抗菌活性。同时氧化镧本身也具备抗菌性能与其他抗菌物质协同抗菌，增强抑菌率及广谱性，氧化铈也可与氧化锆形成增强相复合材料提高材料的强度；同时，氧化镧对氧化锌晶粒生长的限制作用，在该限制作用下，可以使银更多量的进入氧化锌晶格内发挥电子接受体和改变半导体能级的作用，使氧化锌产生更多抗菌活性中心，产物中特殊结构氧化锌被证明能够产生诸如羟基自由基、超氧阴离子、双氧水等活性氧物质，杀灭细菌，此过程氧化锌并不会发生变化也不会减少；与此同时，特殊结构氧化锌抗菌剂局部结构或杂化结构还存在纳米效应，以及受控范围内微量锌离子的协同作用，这些都有助于增强其杀菌性能，经活性氧效应、纳米效应、离子效应等的协同增强杀菌机制，最终提高氧化锆基义齿材料的抗菌能力；
另一方面，氧化镧可提高氧化锆基陶瓷的烧结密度，但其烧结温度较高，因此添加氧化钇降低其烧结温度提高其烧结性能，同时氧化镧和氧化钇可协同增强氧化锆基陶瓷的强度，提高其耐磨损性能，同时添加氧化镧和氧化钇提高义齿材料的强度的原因在于，虽然氧化钇也具备该功能，但是单组分的氧化钇浓度不易过高对机械性能不好，因此需氧化镧协同，提高材料的致密度和强度，形成致密、光滑的义齿。
上述组分中，尺寸控制剂为硅酸钙，以控制成型过程中材料的过度膨胀，出现孔隙或崩瓷现象。
氧化银与氧化锌的质量之和与氧化钇的质量比为5:0.5-1，过多的氧化钇会降低义齿材料的机械强度，而在该范围内能保证不会因添加了氧化银、氧化锌或过大浓度造成的义齿材料的强度降低。
氧化锆的粒径小于等于30nm，作为基材，所用的氧化锆为纳米氧化锆，在该粒径下有利于制备过程中材料的混合均匀性。
同时，本申请提供一种氧化锆基抗菌义齿材料的制备方法，包括以下步骤：
S1.按比例称取氧化锆、氧化银、氧化锌、氧化镧、氧化钇、氧化铈、尺寸控制，经球磨混合，得到陶瓷粉料；
S2.将陶瓷粉料装入模具中预压，得到抗菌义齿瓷块前体；
S3.依次对抗菌义齿瓷块前体进行冷等静压、预烧结、高温烧结处理，得到氧化锆基抗菌义齿材料。
冷等静压成型的压力100-300MPa，优选的，冷等静压成型的压力为200-300MPa，保压时间60-600s；预压压力为5-50MPa，优选的，预压压力为40-50MPa，保压时间10-60s。
预烧结的终温为800-1000℃，升温速率为10-50℃/min，优选的，升温速率为10-15℃/min，保温时间为1-5h；高温烧结的终温为1400-1550℃，升温速率为1-10℃/min，优选的，升温速率为1-3℃/min，保温时间为1-5h，在该程序下，即能保证烧结的效率，也能防止因升温过快而崩瓷或出现裂纹。
在一些实施例中，高温烧结过程在磁场环境下进行，能提高各材料组分分布均匀，不仅提高材料各方位实现有效抗菌，不残留卫生死角，还能提高材料的机械强度。
以下通过具体的实施例对本申请进行进一步说明。
实施例1-7
一种氧化锆基抗菌义齿材料，包括如下的组分：氧化锆、纳米氧化银、纳米氧化锌、纳米氧化镧、纳米氧化钇、氧化铈、硅酸钙，实施例1-7的氧化锆基抗菌义齿材料组分配制见表1。
表1实施例1-7中氧化锆基抗菌义齿材料的组分配制
氧化锆 纳米氧化银 纳米氧化锌 纳米氧化镧 纳米氧化钇 氧化铈 硅酸钙
实施例1 75 5 5 3 2 1 2
实施例2 75 5 5 3 2 1.5 2
实施例3 75 5 5 3 2 2 2
实施例4 75 5 5 2 2 2 2
实施例5 75 5 5 1 2 2 2
实施例6 80 5 5 1 3 2 1
实施例7 80 2 3 3 2 2 1
按照表1中的各组分制备氧化锆基抗菌义齿材料，制备步骤如下：
S1.按比例称取氧化锆、氧化银、氧化锌、氧化镧、氧化钇、氧化铈、尺寸控制，经球磨混合，得到陶瓷粉料；
S2.将陶瓷粉料装入模具中预压，预压压力为5-50MPa，保压时间10-60s，得到抗菌义齿瓷块前体；
S3.依次对抗菌义齿瓷块前体进行冷等静压，冷等静压成型的压力100-300MPa，保压时间60-600s，而后进行预烧结，预烧结为800-1000℃，升温速率为10℃/min保温时间为1-5h，最后再在磁场强度为8T的条件下，高温烧结处理，高温烧结温度为1400-1550℃，升温速率为1℃/min，保温时间为1-5h，得到氧化锆基抗菌义齿材料。
实施例8
一种氧化锆基抗菌义齿材料，包括如下的组分：75份氧化锆、5份纳米氧化银、5份纳米氧化锌、3份纳米氧化镧、2份纳米氧化钇、2份氧化铈、2份硅酸钙。
制备氧化锆基抗菌义齿材料，制备步骤如下：
S1.按比例称取氧化锆、氧化银、氧化锌、氧化镧、氧化钇、氧化铈、尺寸控制，经球磨混合，得到陶瓷粉料；
S2.将陶瓷粉料装入模具中预压，预压压力为5-50MPa，保压时间10-60s，得到抗菌义齿瓷块前体；
S3.依次对抗菌义齿瓷块前体进行冷等静压，冷等静压成型的压力100-300MPa，保压时间60-600s，而后进行预烧结，预烧结为800-1000℃，升温速率为10℃/min保温时间为1-5h，最后再高温烧结处理，高温烧结温度为1400-1550℃，升温速率为1℃/min，保温时间为1-5h，得到氧化锆基抗菌义齿材料。
对比例1-6
对比例1-6与实施例3中的原料组分及制备工艺大体相同，所不同的是，对比例1-6中依次不添加组分纳米氧化银、纳米氧化锌、纳米氧化镧、纳米氧化钇、氧化铈、硅酸钙。
测试与评价
测试实施例1-8及对比例1-6中的氧化锆基抗菌义齿材料的抗菌性能及弯曲强度。
抗菌性能测定：将测试样品、空白对照样品分别放入灭菌培养皿中，用微量加样器取100μL菌悬液分别滴加在各样品表面，每组做三个平行样。用灭菌镊子夹起聚乙烯薄膜覆盖在各样品表面，铺平，不得有气泡，使菌液均匀接触样品表面，盖好平皿，在(37±1)℃，相对湿度90％的条件且在自然光或潮湿黑暗条件下接触培养24小时；经接触培养后的样品，分别用20mL生理盐水洗脱液，反复清洗3次样品及覆盖膜(用镊子夹起薄膜冲洗)，将洗脱液充分混匀，10倍系列稀释，以获得适宜的菌落形成单位(colony forming units，CFU)计数，每100μL样液平行接种2个平板培养基，在(37±1)℃，相对湿度90％的条件下培养后进行菌落计数。最后按稀释倍数计算样品的实际回收菌落数。以上实验重复3次，取平均值。抗菌率计算公式为：R(％)＝(A－B)/A×100％，式中：R—抗菌率(％)，A—空白对照样品平均回收菌落数(CFU/mL)，B—测试例中的平均回收菌落数(CFU/mL)，抗菌率结果如下表2。
按照GBT 6569-2006中的方法测试各氧化锆基抗菌义齿材料的弯曲强度，结果如表2所示。
表2抗菌性及抗弯强度测试结果
Figure BDA0003939305660000071
实施例6与实施例3相比，其高温烧结工艺未在磁场条件下进行，由表2可知，磁场的加持有利于抗菌性能及弯折强度的提升，实施例7与实施例3相比，其烧结的升温程序加快，降低了材料的机械性能；实施例1-3中，对氧化铈的含量进行了调整，实施例3-5中，对纳米氧化镧的含量进行了调整，可以看出，在自然光条件下，氧化铈相较于氧化镧对抗菌的影响力更大，提高氧化铈的比例更有利于提高抑菌率，而在黑暗条件下，氧化镧相较于氧化铈对抗菌的影响更大，提高氧化镧的比例更有利于提高抑菌率，且氧化镧的提高有利于材料的抗弯强度，实施例8相较于实施例3，在高温烧结时，未在磁场下进行，可以看出其机械性能有所降低；对比例1-6中以实施例3为基准，对应缺乏纳米氧化银、纳米氧化锌、纳米氧化镧、纳米氧化钇、氧化铈、硅酸钙，可以看出，纳米氧化银、纳米氧化锌与纳米氧化镧及氧化铈有协同抗菌作用，而氧化镧、氧化铈、氧化钇及硅酸钙则有利于提高氧化锆基陶瓷材料的抗弯强度。
以上，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。

Claims (10)

1.一种氧化锆基抗菌义齿材料，其特征在于，包括质量份数如下的组分：75-80份氧化锆、2-5份纳米氧化银、3-5份纳米氧化锌、1-3份纳米氧化镧、1-3份纳米氧化钇、1-2份氧化铈、1-2份尺寸控制剂。
2.根据权利要求1所述的氧化锆基抗菌义齿材料，其特征在于，所述尺寸控制剂为硅酸钙。
3.根据权利要求1所述的氧化锆基抗菌义齿材料，其特征在于，所述氧化银与氧化锌的质量之和与氧化钇的质量比为5:0.5-1。
4.根据权利要求1所述的氧化锆基抗菌义齿材料，其特征在于，所述氧化锆的粒径小于等于30nm。
5.一种如权利要求1-4任一项所述的氧化锆基抗菌义齿材料的制备方法，其特征在于，包括以下步骤：
S1.按比例称取氧化锆、氧化银、氧化锌、氧化镧、氧化钇、氧化铈、尺寸控制，经球磨混合，得到陶瓷粉料；
S2.将陶瓷粉料装入模具中预压，得到抗菌义齿瓷块前体；
S3.依次对所述抗菌义齿瓷块前体进行冷等静压、预烧结、高温烧结处理，得到所述氧化锆基抗菌义齿材料。
6.根据权利要求5所述的氧化锆基抗菌义齿材料的制备方法，其特征在于，所述冷等静压成型的压力100-300MPa，保压时间60-600s。
7.根据权利要求5所述的氧化锆基抗菌义齿材料的制备方法，其特征在于，所述预压压力为5-50MPa，保压时间10-60s。
8.根据权利要求5所述的氧化锆基抗菌义齿材料的制备方法，其特征在于，所述预烧结的终温为800-1000℃，升温速率为10-50℃/min，保温时间为1-5h。
9.根据权利要求5所述的氧化锆基抗菌义齿材料的制备方法，其特征在于，所述高温烧结的终温为1400-1550℃，升温速率为1-10℃/min，保温时间为1-5h。
10.根据权利要求5所述的氧化锆基抗菌义齿材料的制备方法，其特征在于，所述高温烧结过程在磁场环境下进行。
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