纳米抗紫外线氧化物在颌面赝复硅橡胶中的应用研究
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摘要
硅橡胶已成为临床上最常用的颌面赝复材料，但由于受其理化性能局限及所处自然环境影响，硅橡胶会发生老化，出现变硬、变脆、褪色，甚至导致无法使用。纳米抗紫外线氧化物具备良好的紫外线屏蔽性能，而且稳定性好，不降解，增韧补强性能优异。本课题组首次将其与颌面赝复硅橡胶复合以提高硅橡胶抗老化性能，证实了此方法的可行性。但是无机纳米级氧化物表面具有强极性,与有机硅橡胶基质分散不均匀的问题急需解决。本研究首先筛选出有效的偶联剂表面处理方法，继而对纳米氧化物改性后硅橡胶的各项理化性能，色彩稳定性能，生物安全性能进行全面测试，以获得新型颌面赝复硅橡胶抗老化添加剂的合理配方及添加比例。新方法能够有效改善自然环境因素及局部应力对颌面赝复体机械性能、色彩造成的不利影响，可以长期防止赝复体老化，从而延长赝复体寿命，减少患者医疗花销。
第一部分纳米TiO_2和纳米ZnO表面偶联剂改性的研究
包括3部分内容：①使用硅烷偶联剂KH-570对纳米TiO_2和纳米ZnO分别进行表面有机改性，采用多种表征方法对表面改性前后的纳米TiO_2和纳米ZnO进行评价，同时研究KH-570在纳米TiO_2和纳米ZnO表面的存在形式和键合状态。②对表面改性后的纳米TiO_2和纳米ZnO紫外屏蔽性能进行测定。③将偶联剂表面改性后的纳米TiO_2和纳米ZnO以不同添加量加入硅橡胶A-2186中，检测纳米TiO_2和纳米ZnO添加量对硅橡胶机械性能的影响。
研究结果如下：
①KH-570对纳米TiO_2和纳米ZnO进行有机改性，能够使纳米TiO_2和纳米ZnO表面由亲水性变为疏水性，并以牢固的化学键合方式结合在纳米TiO_2和纳米ZnO表面，形成有机包覆层；KH-570在纳米TiO_2和纳米ZnO表面包覆的最大量约为5wt%。
②表面改性后的纳米TiO_2和纳米ZnO紫外屏蔽性能良好，纳米TiO_2，ZnO悬浮液在紫外光区(190～400nm)的吸收明显强于可见光区(400～800nm)。
③硅烷偶联剂表面改性后的纳米TiO_2和纳米ZnO添加量对硅橡胶的物理机械性能有显著性影响。5wt%硅烷偶联剂处理后的纳米TiO_2添加量为2wt%，纳米ZnO添加量为2.5wt%时，均可以获得较佳的硅橡胶机械性能。
第二部分不同老化方式下，纳米TiO_2和纳米ZnO与硅橡胶复合材料机械性能及色彩稳定性能的评价
①纳米TiO_2、ZnO与硅橡胶复合材料经过人工模拟老化后机械性能的改变；
研究结果如下：
a)拉伸强度：与对照组相比，老化后纳米TiO_2实验组和纳米ZnO实验组硅橡胶的拉伸强度均有所改善；纳米ZnO实验组中，添加量为2.5wt%时，硅橡胶拉伸强度变化最小。
b)撕裂强度：老化后，纳米TiO_2实验组中，添加比为2.5wt%时，硅橡胶撕裂强度变化最大；纳米ZnO实验组中，添加比为1wt%时，硅橡胶撕裂强度变化最小。
c)扯断伸长率：老化后，纳米TiO_2与纳米ZnO实验组间有明显统计学差异；纳米TiO_2实验组中，添加比为2wt%时，硅橡胶扯断伸长率变化最小。
d)邵氏硬度：老化后，纳米TiO_2和纳米ZnO实验组邵氏硬度有所升高，但仍在理想值范围内；对照组邵氏硬度变化值是所有实验组邵氏硬度变化值的4-7倍。
以上结果表明纳米TiO_2、纳米ZnO可有效改善硅橡胶抗老化的机械性能。
②纳米TiO_2、ZnO与硅橡胶复合材料经过人工模拟老化及自然环境老化（1个月、3个月、6个月、12个月）后色彩稳定性能的改变；
研究结果如下：
a)人工加速老化
所有纳米TiO_2和纳米ZnO黄色颜料组老化前后色差值最大，3.7-8.4；当三种颜料混合成为混合颜料组时，纳米TiO_2实验组中，添加比为2wt%和2.5wt%时，老化前后色差值最小。所有实验组老化前后色差值均低于50:50%可接受色差值3.0；
b)自然环境老化
不同的暴晒周期之间色差值有统计学差异，其中，暴晒周期为12个月的实验组色差值最大；无颜料实验组中，纳米ZnO实验组中，添加比为1wt%时，色差值最小；但当加入混合颜料时，混合颜料实验组中：纳米TiO_2添加比为2.5wt%，色差值最小；与对照组相比，所有混合颜料实验组色差值均低于50:50%可接受色差值3.0；
以上结果表明，无论是否添加内着色颜料，纳米TiO_2和纳米ZnO均可以提高硅橡胶的色彩稳定性；不同自然老化暴晒周期可导致硅橡胶发生不同程度的颜色变化。硅橡胶自然老化比人工老化后导致的颜色变化更大。
第三部分纳米TiO_2和纳米ZnO与硅橡胶复合材料生物学性能评价
按照国家标准GB/T16175-1996医用有机硅材料生物学评价试验方法标准的要求，选取并进行了如下生物学试验：①细胞毒性试验（MTT法）：试验结果表明纳米TiO_2、ZnO与硅橡胶复合材料的细胞毒性分级为0级，可认为复合材料无细胞毒性反应；②原发性皮肤刺激试验：试验结果表明，纳米TiO_2、ZnO与硅橡胶复合材料的原发性刺激指数均值为0，仅有极轻微刺激反应类型发生。因此硅橡胶复合材料对受试动物皮肤无刺激。③皮内刺激试验：试验结果表明纳米TiO_2、ZnO与硅橡胶复合材料的皮内刺激反应阴性，硅橡胶复合材料对受试动物皮肤无刺激。④过敏试验：试验结果表明纳米TiO_2、ZnO与硅橡胶复合材料实验组去除敷料后，皮肤无红斑，无水肿；过敏反应记分均为0级，无反应。致敏反应为阴性。⑤口腔粘膜刺激试验：实验结果显示：纳米TiO_2、ZnO与硅橡胶复合材料接触的局部口腔粘膜有无色泽异常、充血、糜烂和渗出等异常现象，组织学切片显示金黄仓地鼠颊囊组织细胞形态正常，上皮连续性完好。
上述结果表明添加纳米TiO_2、ZnO与硅橡胶制成的硅橡胶复合材料具有良好的生物安全性。
Extraoral maxillofacial prostheses are widely used for restoring missing facialstructures due to resection, trauma, or congenital anomalies. Materials used forthis purpose are silicone elastomers. However, because of their limitations ofphysical properties and certain environmental factors, they usually becomeaging, harder and color degradation. Nano oxide, as a kind of ultraviolet lightabsorber, is more stable and has better property of enhancing silicone elastomer.Our group firstly introduces it into maxillofacial elastomer, and investigates thetentative confirmation. The purpose of of our research focus on the effects onthe physical properties, color stability and biological safety performance ofmaxillofacial elastomer after adding surface modified nano-oxides by properconcentrations. When patients wear the maxillofacial prosthesis, the compoundmaterials can resist outdoor environmental factors and partial mechanical forcein order to avoid aging in long term. Then the service life of prosthesis can be extended.
Part I Study of surface modification of nano-sized TiO_2and ZnOwith silicane coupling agent.
This part consists of3experiments:
①Nano-sized TiO_2and ZnO were treated with different content of KH-570.The nano-sized TiO_2and ZnO before and after modification werecharacterized by virtue of several analysis means.
②The evaluation of UV-ray shieding properties of surface modifiednano-sized TiO_2and ZnO;
③Evaluations of mechanical properties of silicone elastomer by addingsurface modified nano-sized TiO_2and ZnO with different concentrations.The results are showed as follows:
①The surface performance of nano-sized TiO_2and ZnO modified with silanecoupling reagent (KH-570) had changed from hydrophilic to hydrophobic,the KH-570was bound on the surface of nano-sized TiO_2and ZnO particles,a firm chemical bonding of KH-570to nano-sized TiO_2and ZnO and a layerof organic coating layer formed. The best concentration of KH-570coatedon the surface of nano-sized TiO_2and ZnO was about5wt%.
②Both of nano-sized TiO_2and ZnO have the better UV-sheildingperformance.
③KH-570surface modified nano-sized TiO_2and ZnO at concentrations of2.0wt%and2.5wt%improved the overall mechanical properties of thesilicone A-2186maxillofacial elastomer.
Part II After different aging conditions, the evaluations of mechanical properties and color stability of silicone elastomerA-2186by adding nano-sized TiO_2and ZnO
①The evaluation of mechanical properties of silicone elastomer A-2186byadding nano-sized TiO_2and ZnO after artificial aging
The results showed below:
a) For tensile strength, compared with control group, both ZnO groups andTiO_2groups improved the tensile strength before and after artificial aging(p<0.05); ZnO with2.5wt%concentration groups showed the smallestchanges (p<0.05);
b) For tear strength, TiO_2at2.5wt%concentration with no pigments group hadthe greatest changes (p<0.05); When mixed with pigments, ZnO at1.0wt%showed smallest changes (p<0.05);
c) For elongation, there was significant difference among the type ofnano-oxides (p<0.05); control group had the greatest changes after artificialaging (p<0.05); TiO_2at2.0wt%concentration group had the smallestchanges (p<0.05);
d) For hardness, after artificial aging, specimens of control groups become4-7times harder than all nano-oxide groups (p<0.001).
Above all results, the conclusion was: Both of nano-sized TiO_2and ZnOimproved mechanical properties of silicone elastomer A-2186after subjected toartificial aging.
②The evaluation of color stability of silicone elastomer A-2186by addingnano-sized TiO_2and ZnO after artificial aging and outdoor aging
a) Artificial aging condition Yellow pigments mixed with all three nano-oxides at all intervals increased E*values significantly from3.7up to8.4. When mixed pigment groups wereconsidered, TiO_2at2.0wt%, and2.5wt%exhibited the smallest color changes,followed by ZnO respectively (p<0.001).The smallest color differences,observed for nano-oxides groups, were recorded for TiO_2at2.0wt%and2.5wt%.When the nano-oxides were tested at all concentrations, TiO_2groups had theleast color change. All E*values of the mixed pigment groups were below the50:50%acceptability threshold (E*=1.2–2.3, below3.0).
b) Outdoor aging conditionFor the exposure periods, there were significant differences from each other. Allspecimens of12months exposure showed the greatest color changes (p<0.001);Nano ZnO at1.0wt%concentration with no pigments showed the smallest colorchange; however, after mixed with three pigments, nano TiO_2at2.5wt%showedthe smallest color differences; Compared with control group, all E*values ofthe mixed groups were below the50:50%acceptability threshold (E*=0.6-2.6,below3.0).
Above all results, the conclusion were: Nano TiO_2and nano ZnO protected bothpigmented and nonpigmented silicone A-2186from color degradation. Exposureperiods had significantly affected the color change. Outdoor aging made greatercolor changes than artificial aging.
Part III Evaluations on the biocompatibility of silicone elastomerA-2186with nano TiO_2and nano ZnO
Before the clinical application, a series of experiments should be done todetermine the biological safety of silicone elastomer A-2186with nano TiO_2and nano ZnO according to standards GB/T16175-1996. The results of biological
tests were as below:
①Cytotoxicity test, the result showed that the cytotoxicity index of siliconeelastomer A-2186with nano TiO_2and nano ZnO were in grade I, whichindicated that the materials had no cytotoxicity;
②Skin irritation tests, the primary irritation index of silicone elastomerA-2186with Nano TiO_2and nano ZnO were all zero. The response types ofirritation tests were all minimal. The data showed that these materials didn’thave skin irritaion under the experimental condition.
③Intracutaneous irritation tests, the results showed there were no obviousintracutaneous irritations.
④Skin sensitization tests, the scores of skin reaction of silicone elastomerA-2186with Nano TiO_2and nano ZnO were all zero. Sensitization rates ofthe two groups were also zero. There are no potential of skin sensitizationunder the experimental conditions.
⑤Oral mucous membrane irritation tests, there were no local or systemicabnormal response in the groups of Nano TiO_2and nano ZnO. The scores oferythematous response were all zero and the histopathological findings werealso normal. There had no irritating response to oral mucous membraneunder the experimental conditions.
第一部分纳米TiO_2和纳米ZnO表面偶联剂改性的研究
包括3部分内容：①使用硅烷偶联剂KH-570对纳米TiO_2和纳米ZnO分别进行表面有机改性，采用多种表征方法对表面改性前后的纳米TiO_2和纳米ZnO进行评价，同时研究KH-570在纳米TiO_2和纳米ZnO表面的存在形式和键合状态。②对表面改性后的纳米TiO_2和纳米ZnO紫外屏蔽性能进行测定。③将偶联剂表面改性后的纳米TiO_2和纳米ZnO以不同添加量加入硅橡胶A-2186中，检测纳米TiO_2和纳米ZnO添加量对硅橡胶机械性能的影响。
研究结果如下：
①KH-570对纳米TiO_2和纳米ZnO进行有机改性，能够使纳米TiO_2和纳米ZnO表面由亲水性变为疏水性，并以牢固的化学键合方式结合在纳米TiO_2和纳米ZnO表面，形成有机包覆层；KH-570在纳米TiO_2和纳米ZnO表面包覆的最大量约为5wt%。
②表面改性后的纳米TiO_2和纳米ZnO紫外屏蔽性能良好，纳米TiO_2，ZnO悬浮液在紫外光区(190～400nm)的吸收明显强于可见光区(400～800nm)。
③硅烷偶联剂表面改性后的纳米TiO_2和纳米ZnO添加量对硅橡胶的物理机械性能有显著性影响。5wt%硅烷偶联剂处理后的纳米TiO_2添加量为2wt%，纳米ZnO添加量为2.5wt%时，均可以获得较佳的硅橡胶机械性能。
第二部分不同老化方式下，纳米TiO_2和纳米ZnO与硅橡胶复合材料机械性能及色彩稳定性能的评价
①纳米TiO_2、ZnO与硅橡胶复合材料经过人工模拟老化后机械性能的改变；
研究结果如下：
a)拉伸强度：与对照组相比，老化后纳米TiO_2实验组和纳米ZnO实验组硅橡胶的拉伸强度均有所改善；纳米ZnO实验组中，添加量为2.5wt%时，硅橡胶拉伸强度变化最小。
b)撕裂强度：老化后，纳米TiO_2实验组中，添加比为2.5wt%时，硅橡胶撕裂强度变化最大；纳米ZnO实验组中，添加比为1wt%时，硅橡胶撕裂强度变化最小。
c)扯断伸长率：老化后，纳米TiO_2与纳米ZnO实验组间有明显统计学差异；纳米TiO_2实验组中，添加比为2wt%时，硅橡胶扯断伸长率变化最小。
d)邵氏硬度：老化后，纳米TiO_2和纳米ZnO实验组邵氏硬度有所升高，但仍在理想值范围内；对照组邵氏硬度变化值是所有实验组邵氏硬度变化值的4-7倍。
以上结果表明纳米TiO_2、纳米ZnO可有效改善硅橡胶抗老化的机械性能。
②纳米TiO_2、ZnO与硅橡胶复合材料经过人工模拟老化及自然环境老化（1个月、3个月、6个月、12个月）后色彩稳定性能的改变；
研究结果如下：
a)人工加速老化
所有纳米TiO_2和纳米ZnO黄色颜料组老化前后色差值最大，3.7-8.4；当三种颜料混合成为混合颜料组时，纳米TiO_2实验组中，添加比为2wt%和2.5wt%时，老化前后色差值最小。所有实验组老化前后色差值均低于50:50%可接受色差值3.0；
b)自然环境老化
不同的暴晒周期之间色差值有统计学差异，其中，暴晒周期为12个月的实验组色差值最大；无颜料实验组中，纳米ZnO实验组中，添加比为1wt%时，色差值最小；但当加入混合颜料时，混合颜料实验组中：纳米TiO_2添加比为2.5wt%，色差值最小；与对照组相比，所有混合颜料实验组色差值均低于50:50%可接受色差值3.0；
以上结果表明，无论是否添加内着色颜料，纳米TiO_2和纳米ZnO均可以提高硅橡胶的色彩稳定性；不同自然老化暴晒周期可导致硅橡胶发生不同程度的颜色变化。硅橡胶自然老化比人工老化后导致的颜色变化更大。
第三部分纳米TiO_2和纳米ZnO与硅橡胶复合材料生物学性能评价
按照国家标准GB/T16175-1996医用有机硅材料生物学评价试验方法标准的要求，选取并进行了如下生物学试验：①细胞毒性试验（MTT法）：试验结果表明纳米TiO_2、ZnO与硅橡胶复合材料的细胞毒性分级为0级，可认为复合材料无细胞毒性反应；②原发性皮肤刺激试验：试验结果表明，纳米TiO_2、ZnO与硅橡胶复合材料的原发性刺激指数均值为0，仅有极轻微刺激反应类型发生。因此硅橡胶复合材料对受试动物皮肤无刺激。③皮内刺激试验：试验结果表明纳米TiO_2、ZnO与硅橡胶复合材料的皮内刺激反应阴性，硅橡胶复合材料对受试动物皮肤无刺激。④过敏试验：试验结果表明纳米TiO_2、ZnO与硅橡胶复合材料实验组去除敷料后，皮肤无红斑，无水肿；过敏反应记分均为0级，无反应。致敏反应为阴性。⑤口腔粘膜刺激试验：实验结果显示：纳米TiO_2、ZnO与硅橡胶复合材料接触的局部口腔粘膜有无色泽异常、充血、糜烂和渗出等异常现象，组织学切片显示金黄仓地鼠颊囊组织细胞形态正常，上皮连续性完好。
上述结果表明添加纳米TiO_2、ZnO与硅橡胶制成的硅橡胶复合材料具有良好的生物安全性。
Extraoral maxillofacial prostheses are widely used for restoring missing facialstructures due to resection, trauma, or congenital anomalies. Materials used forthis purpose are silicone elastomers. However, because of their limitations ofphysical properties and certain environmental factors, they usually becomeaging, harder and color degradation. Nano oxide, as a kind of ultraviolet lightabsorber, is more stable and has better property of enhancing silicone elastomer.Our group firstly introduces it into maxillofacial elastomer, and investigates thetentative confirmation. The purpose of of our research focus on the effects onthe physical properties, color stability and biological safety performance ofmaxillofacial elastomer after adding surface modified nano-oxides by properconcentrations. When patients wear the maxillofacial prosthesis, the compoundmaterials can resist outdoor environmental factors and partial mechanical forcein order to avoid aging in long term. Then the service life of prosthesis can be extended.
Part I Study of surface modification of nano-sized TiO_2and ZnOwith silicane coupling agent.
This part consists of3experiments:
①Nano-sized TiO_2and ZnO were treated with different content of KH-570.The nano-sized TiO_2and ZnO before and after modification werecharacterized by virtue of several analysis means.
②The evaluation of UV-ray shieding properties of surface modifiednano-sized TiO_2and ZnO;
③Evaluations of mechanical properties of silicone elastomer by addingsurface modified nano-sized TiO_2and ZnO with different concentrations.The results are showed as follows:
①The surface performance of nano-sized TiO_2and ZnO modified with silanecoupling reagent (KH-570) had changed from hydrophilic to hydrophobic,the KH-570was bound on the surface of nano-sized TiO_2and ZnO particles,a firm chemical bonding of KH-570to nano-sized TiO_2and ZnO and a layerof organic coating layer formed. The best concentration of KH-570coatedon the surface of nano-sized TiO_2and ZnO was about5wt%.
②Both of nano-sized TiO_2and ZnO have the better UV-sheildingperformance.
③KH-570surface modified nano-sized TiO_2and ZnO at concentrations of2.0wt%and2.5wt%improved the overall mechanical properties of thesilicone A-2186maxillofacial elastomer.
Part II After different aging conditions, the evaluations of mechanical properties and color stability of silicone elastomerA-2186by adding nano-sized TiO_2and ZnO
①The evaluation of mechanical properties of silicone elastomer A-2186byadding nano-sized TiO_2and ZnO after artificial aging
The results showed below:
a) For tensile strength, compared with control group, both ZnO groups andTiO_2groups improved the tensile strength before and after artificial aging(p<0.05); ZnO with2.5wt%concentration groups showed the smallestchanges (p<0.05);
b) For tear strength, TiO_2at2.5wt%concentration with no pigments group hadthe greatest changes (p<0.05); When mixed with pigments, ZnO at1.0wt%showed smallest changes (p<0.05);
c) For elongation, there was significant difference among the type ofnano-oxides (p<0.05); control group had the greatest changes after artificialaging (p<0.05); TiO_2at2.0wt%concentration group had the smallestchanges (p<0.05);
d) For hardness, after artificial aging, specimens of control groups become4-7times harder than all nano-oxide groups (p<0.001).
Above all results, the conclusion was: Both of nano-sized TiO_2and ZnOimproved mechanical properties of silicone elastomer A-2186after subjected toartificial aging.
②The evaluation of color stability of silicone elastomer A-2186by addingnano-sized TiO_2and ZnO after artificial aging and outdoor aging
a) Artificial aging condition Yellow pigments mixed with all three nano-oxides at all intervals increased E*values significantly from3.7up to8.4. When mixed pigment groups wereconsidered, TiO_2at2.0wt%, and2.5wt%exhibited the smallest color changes,followed by ZnO respectively (p<0.001).The smallest color differences,observed for nano-oxides groups, were recorded for TiO_2at2.0wt%and2.5wt%.When the nano-oxides were tested at all concentrations, TiO_2groups had theleast color change. All E*values of the mixed pigment groups were below the50:50%acceptability threshold (E*=1.2–2.3, below3.0).
b) Outdoor aging conditionFor the exposure periods, there were significant differences from each other. Allspecimens of12months exposure showed the greatest color changes (p<0.001);Nano ZnO at1.0wt%concentration with no pigments showed the smallest colorchange; however, after mixed with three pigments, nano TiO_2at2.5wt%showedthe smallest color differences; Compared with control group, all E*values ofthe mixed groups were below the50:50%acceptability threshold (E*=0.6-2.6,below3.0).
Above all results, the conclusion were: Nano TiO_2and nano ZnO protected bothpigmented and nonpigmented silicone A-2186from color degradation. Exposureperiods had significantly affected the color change. Outdoor aging made greatercolor changes than artificial aging.
Part III Evaluations on the biocompatibility of silicone elastomerA-2186with nano TiO_2and nano ZnO
Before the clinical application, a series of experiments should be done todetermine the biological safety of silicone elastomer A-2186with nano TiO_2and nano ZnO according to standards GB/T16175-1996. The results of biological
tests were as below:
①Cytotoxicity test, the result showed that the cytotoxicity index of siliconeelastomer A-2186with nano TiO_2and nano ZnO were in grade I, whichindicated that the materials had no cytotoxicity;
②Skin irritation tests, the primary irritation index of silicone elastomerA-2186with Nano TiO_2and nano ZnO were all zero. The response types ofirritation tests were all minimal. The data showed that these materials didn’thave skin irritaion under the experimental condition.
③Intracutaneous irritation tests, the results showed there were no obviousintracutaneous irritations.
④Skin sensitization tests, the scores of skin reaction of silicone elastomerA-2186with Nano TiO_2and nano ZnO were all zero. Sensitization rates ofthe two groups were also zero. There are no potential of skin sensitizationunder the experimental conditions.
⑤Oral mucous membrane irritation tests, there were no local or systemicabnormal response in the groups of Nano TiO_2and nano ZnO. The scores oferythematous response were all zero and the histopathological findings werealso normal. There had no irritating response to oral mucous membraneunder the experimental conditions.
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