生物活性梯度多孔钛的制备及生物学评价
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摘要
多孔钛不仅具有优良的生物相容性,也因其孔结构的存在而能有效降低弹性模量,且能为组织提供大量的生长空间,利于植入体的固定。然而,过高的孔隙率会降低抗压强度等力学性能,且钛本身属于生物惰性材料。因而,如何解决孔隙率与力学性能之间的矛盾以及如何给具有复杂几何形貌的多孔钛赋予生物活性是值得研究的问题。
添加造孔剂法是制备多孔材料的一种传统方法,操作简便、成本低、对设备要求不高,且孔的很多参数如孔隙度和孔径尺寸等可通过对造孔剂的调整来进行控制。因此,本文选用该方法来制备多孔钛。通过对单一孔隙率的多孔钛烧结工艺的考查及孔隙率与力学性能的评价,得出较为合理的烧结工艺方案,并以此合理的工艺,制备了“外疏内密”的梯度多孔钛,并对其相关力学性能进行了表征。通过电化学方法及化学方法对多孔钛进行活化处理并评价了其生物活性。建立了大型动物负载部位全缺损模型并利用力学性能优异的双层多孔钛对缺损部位进行了修复,考察了不同时间的修复情况。以羟基磷灰石粉和钛粉为原材料,通过添加造孔剂的方式烧结制备出生物陶瓷／钛多孔复合材料,评价了其力学性能及生物活性。
首先对造孔剂添加量、保温时间、烧结温度等工艺参数对多孔钛孔隙率、抗压强度和弹性模量进行了研究。结果表明,当造孔剂添加量为35%、40%、50%和60%时,多孔钛的孔隙率分别为50%、58%、67%和72%,抗压强度分别为160MPa、105MPa、40MPa和25MPa,弹性模量分别为2.68GPa、2.00GPa、0.75GPa和0.55GPa;保温时间和烧结温度均对多孔钛的孔隙率和抗压强度有影响,烧结温度的提高和保温时间的延长有助于抗压强度的提高。
通过调整各层造孔剂的添加量制备出双层和三层多孔钛,在温度为1300℃下保温2小时制备的双层和梯度多孔钛外层孔隙率可达67%,其最大抗压强度、抗弯强度及弹性模量分别为245.85MPa、64.54MPa及3.98GPa。力学性能与骨组织相匹配,解决了高孔隙率与抗压强度等力学性能之间的矛盾,为承载部位硬组织修复提供了可能。
通过电化学方法和化学方法对多孔钛进行表面改性处理,构建多级微纳结构。结果表明,经过阳极氧化再热处理的多孔钛表面形成排列整齐的锐钛矿型纳米管；经过微弧氧化后的多孔钛表面形成含微孔结构的TiO薄膜；而经过碱处理后的多孔钛表面形成较复杂的微结构。体外仿生矿化结果表明,上述三类经改性后的多孔钛均能诱导羟基磷灰石的形成。
通过动物体内实验进一步考察了改性前后多孔钛骨修复的能力。结果表明,添加造孔剂法制备的多孔钛具有良好的骨传导性和生物相容性。具有锐钛矿型TiO2纳米管的多级微结构多孔钛及经碱处理后的多孔钛可以增强骨形成能力,且植入体内6个月时,都比未处理多孔钛具有更高的骨结合力。为了考察承载部位的骨修复效果,建立了狗股骨中段全缺损模型,利用具有优异力学性能的双层梯度多孔钛对缺损部位进行修复,考察其在1、3和6个月时对骨的修复情况。结果表明,以钢板加螺钉的固定方式在1个月时固定良好,且有骨组织长入孔内；而在3个月固定实效,植入体移位,修复失败,表明该固定方式有待于进一步改进。此外,在肌肉内考察了改性前后多孔钛的骨诱导性能。实验结果表明,锐钛矿型Ti02纳米管的多孔钛及经碱处理后的多孔钛均能促进骨形态发生蛋白(BMP-2)的表达,表现出潜在的骨诱导能力。
最后,在真空中烧结制备出HA/Ti复合材料并对其力学性能进行表征。结果表明,抗压强度随Ti添加量的增加而增加,HA/Ti值为1：15时,其抗压强度达181.89MPa,且该比例下的复合材料能诱导羟基磷灰石的形成；通过调整造孔剂添加量制备出外层高孔隙率且具有优异力学性能的双层梯度多孔生物活性复合材料,可以作为一种新型的骨替换材料。
Porous titanium has excellent biocompatibility and can reduce the Young's modulus because of the pore structure. Meanwhile, the pore structure can provide much space for tissue ingrowth, which can strengthen the bonding between the implant and tissue. However, the mechanical properties such as compressive strength will be decreased as the too high porosity. Further more, the titanium is a biologically inert material. Thus, how to solve the contradiction between porosity and compressive strength, and how to activate the porous titanium with comples topography is a problem to be solved.
The space holder method is a fabrication process that can produce porous materials. As this method is simple, low cost and no expensive equipment needed, meanwhile, the size, shape and porosity can be adjusted by choosing the space holder particles, it was used to preparation of porous titanium implants in this paper. The optimized process parameter can be determined through investigating the process parameters by fabricating the porous titanium with sole porosity. And the effect of the parameters on the porosity and mechanical properties were also investigated. Then, the graded porous titanium with higher porosity in outer layer was fabricated and the mechanical properties were characterized. Subsequently, electrochemical treatments and chemical treatments were conducted to activate the surface and the biological activity of the treated porous titanium was studied in vitro and in vivo. In addition, the full-defect model in the bearing part was established by creating defects in the middle femur of the dogs. Then, the double graded porous titanium implants were used to repair the defect and the results were invested at different time. In this study, steel plates and screws were used to fix the implants. Finally, porous HA/Ti was processed using titanium and hydroxyapatite powder by space holder method, and the mechanical properties and biological activity of the porous composites were investigated.
Firstly, the impact of addition of space holder, sintering temperature and holding time on porosity, compressive strength and Young's modulus were studied in this paper. When the addition of space holder was35%、40%/50%and60%, the porosity of porous titanium was 50%、58%、67%and72%, the compressive strength was160MPa、105MPa、40MPa and25PMa, the Young's modulus was2.68GPa、2.00GPa、0.75GPa and0.55GPa, respectively. When sintering temperature increased and the holding time extended, the compressive strength increased.
In this study, graded porous titanium scaffolds containing the double layer or three layers were prepared at1300℃for2hours. And the porosity in outer layer was approximately67%. Moreover, the compressive strength, flexural strength and Young's modulus are245.85MPa,64.54MPa and3.98GPa, respectively, matching the bone. The results indicated that the graded porous titanium can be used to repair the hard tissue in bearing part.
Multi-level micr-nano porous structure was forming on the surface of porous titanium by electrochemical method and chemical methods, and the results showed that anatase TiO2nanotubes were presented after anodize treatment and heat treatment. And TiO film containing microporous structure was presented after micro-arc oxidation. When the porous titanium was treated in the NaOH solution, plush-like suface containing Na, O, etc was presented. Biomimetic results showed that the three types of modified porous titanium can induce the formation of hydroxyapatite.
Animal experiment was conducted to study the effects of the porous titanium before and after modification on bone integration. The results showed that the porous titanium had good conduction capacity and biocompatibility. Anatase nanotubes had significant effect on the growth of bone tissue and promoted bone ingrowth into the pores. When implanted in the animals for6months, the porous titanium with anatase nanotubes showed the higher bonding strength and bone ingrowth area rate than the untreated implants.
The full-defects model was established to investigate the bone repair in the part of the bearing part. The double layer porous titanium was used to repair the bone defect. The results showed that the implants were fixed well by steel plate and screws in a month. However, the implants were loose in3and6months. It indicated that the fix method needs to be improved. In addition, the bone induction capability of the porous titanium was investigated through implanting the implants into the muscles. Results showed that the anatase TiO2nanotubes promoted expression of the bone morphogenetic protein (BMP-2). And so did the surface of implants treated by NaOH solution. It indicated that the modified surface had the potentital bone induction ability.
Finally, the HA/Ti composites was prepared and the mechanical properties were characterized. The results showed that the compressive strength increased with the addition of the titanium. When the quality ratio of the hydroxyapatite and titanium is1:15, the compressive strength is181.89MPa. Meanwhile, the composites can induce the formation of hydroxyapatite. Moreover, the double layer graded porous composites with excellent mechanical properties can be prepared by adjusting the space holder addition. The graded porous composites with higher porosity in outer layer can be used as a new kind of bone-substitute materials.
添加造孔剂法是制备多孔材料的一种传统方法,操作简便、成本低、对设备要求不高,且孔的很多参数如孔隙度和孔径尺寸等可通过对造孔剂的调整来进行控制。因此,本文选用该方法来制备多孔钛。通过对单一孔隙率的多孔钛烧结工艺的考查及孔隙率与力学性能的评价,得出较为合理的烧结工艺方案,并以此合理的工艺,制备了“外疏内密”的梯度多孔钛,并对其相关力学性能进行了表征。通过电化学方法及化学方法对多孔钛进行活化处理并评价了其生物活性。建立了大型动物负载部位全缺损模型并利用力学性能优异的双层多孔钛对缺损部位进行了修复,考察了不同时间的修复情况。以羟基磷灰石粉和钛粉为原材料,通过添加造孔剂的方式烧结制备出生物陶瓷／钛多孔复合材料,评价了其力学性能及生物活性。
首先对造孔剂添加量、保温时间、烧结温度等工艺参数对多孔钛孔隙率、抗压强度和弹性模量进行了研究。结果表明,当造孔剂添加量为35%、40%、50%和60%时,多孔钛的孔隙率分别为50%、58%、67%和72%,抗压强度分别为160MPa、105MPa、40MPa和25MPa,弹性模量分别为2.68GPa、2.00GPa、0.75GPa和0.55GPa;保温时间和烧结温度均对多孔钛的孔隙率和抗压强度有影响,烧结温度的提高和保温时间的延长有助于抗压强度的提高。
通过调整各层造孔剂的添加量制备出双层和三层多孔钛,在温度为1300℃下保温2小时制备的双层和梯度多孔钛外层孔隙率可达67%,其最大抗压强度、抗弯强度及弹性模量分别为245.85MPa、64.54MPa及3.98GPa。力学性能与骨组织相匹配,解决了高孔隙率与抗压强度等力学性能之间的矛盾,为承载部位硬组织修复提供了可能。
通过电化学方法和化学方法对多孔钛进行表面改性处理,构建多级微纳结构。结果表明,经过阳极氧化再热处理的多孔钛表面形成排列整齐的锐钛矿型纳米管；经过微弧氧化后的多孔钛表面形成含微孔结构的TiO薄膜；而经过碱处理后的多孔钛表面形成较复杂的微结构。体外仿生矿化结果表明,上述三类经改性后的多孔钛均能诱导羟基磷灰石的形成。
通过动物体内实验进一步考察了改性前后多孔钛骨修复的能力。结果表明,添加造孔剂法制备的多孔钛具有良好的骨传导性和生物相容性。具有锐钛矿型TiO2纳米管的多级微结构多孔钛及经碱处理后的多孔钛可以增强骨形成能力,且植入体内6个月时,都比未处理多孔钛具有更高的骨结合力。为了考察承载部位的骨修复效果,建立了狗股骨中段全缺损模型,利用具有优异力学性能的双层梯度多孔钛对缺损部位进行修复,考察其在1、3和6个月时对骨的修复情况。结果表明,以钢板加螺钉的固定方式在1个月时固定良好,且有骨组织长入孔内；而在3个月固定实效,植入体移位,修复失败,表明该固定方式有待于进一步改进。此外,在肌肉内考察了改性前后多孔钛的骨诱导性能。实验结果表明,锐钛矿型Ti02纳米管的多孔钛及经碱处理后的多孔钛均能促进骨形态发生蛋白(BMP-2)的表达,表现出潜在的骨诱导能力。
最后,在真空中烧结制备出HA/Ti复合材料并对其力学性能进行表征。结果表明,抗压强度随Ti添加量的增加而增加,HA/Ti值为1：15时,其抗压强度达181.89MPa,且该比例下的复合材料能诱导羟基磷灰石的形成；通过调整造孔剂添加量制备出外层高孔隙率且具有优异力学性能的双层梯度多孔生物活性复合材料,可以作为一种新型的骨替换材料。
Porous titanium has excellent biocompatibility and can reduce the Young's modulus because of the pore structure. Meanwhile, the pore structure can provide much space for tissue ingrowth, which can strengthen the bonding between the implant and tissue. However, the mechanical properties such as compressive strength will be decreased as the too high porosity. Further more, the titanium is a biologically inert material. Thus, how to solve the contradiction between porosity and compressive strength, and how to activate the porous titanium with comples topography is a problem to be solved.
The space holder method is a fabrication process that can produce porous materials. As this method is simple, low cost and no expensive equipment needed, meanwhile, the size, shape and porosity can be adjusted by choosing the space holder particles, it was used to preparation of porous titanium implants in this paper. The optimized process parameter can be determined through investigating the process parameters by fabricating the porous titanium with sole porosity. And the effect of the parameters on the porosity and mechanical properties were also investigated. Then, the graded porous titanium with higher porosity in outer layer was fabricated and the mechanical properties were characterized. Subsequently, electrochemical treatments and chemical treatments were conducted to activate the surface and the biological activity of the treated porous titanium was studied in vitro and in vivo. In addition, the full-defect model in the bearing part was established by creating defects in the middle femur of the dogs. Then, the double graded porous titanium implants were used to repair the defect and the results were invested at different time. In this study, steel plates and screws were used to fix the implants. Finally, porous HA/Ti was processed using titanium and hydroxyapatite powder by space holder method, and the mechanical properties and biological activity of the porous composites were investigated.
Firstly, the impact of addition of space holder, sintering temperature and holding time on porosity, compressive strength and Young's modulus were studied in this paper. When the addition of space holder was35%、40%/50%and60%, the porosity of porous titanium was 50%、58%、67%and72%, the compressive strength was160MPa、105MPa、40MPa and25PMa, the Young's modulus was2.68GPa、2.00GPa、0.75GPa and0.55GPa, respectively. When sintering temperature increased and the holding time extended, the compressive strength increased.
In this study, graded porous titanium scaffolds containing the double layer or three layers were prepared at1300℃for2hours. And the porosity in outer layer was approximately67%. Moreover, the compressive strength, flexural strength and Young's modulus are245.85MPa,64.54MPa and3.98GPa, respectively, matching the bone. The results indicated that the graded porous titanium can be used to repair the hard tissue in bearing part.
Multi-level micr-nano porous structure was forming on the surface of porous titanium by electrochemical method and chemical methods, and the results showed that anatase TiO2nanotubes were presented after anodize treatment and heat treatment. And TiO film containing microporous structure was presented after micro-arc oxidation. When the porous titanium was treated in the NaOH solution, plush-like suface containing Na, O, etc was presented. Biomimetic results showed that the three types of modified porous titanium can induce the formation of hydroxyapatite.
Animal experiment was conducted to study the effects of the porous titanium before and after modification on bone integration. The results showed that the porous titanium had good conduction capacity and biocompatibility. Anatase nanotubes had significant effect on the growth of bone tissue and promoted bone ingrowth into the pores. When implanted in the animals for6months, the porous titanium with anatase nanotubes showed the higher bonding strength and bone ingrowth area rate than the untreated implants.
The full-defects model was established to investigate the bone repair in the part of the bearing part. The double layer porous titanium was used to repair the bone defect. The results showed that the implants were fixed well by steel plate and screws in a month. However, the implants were loose in3and6months. It indicated that the fix method needs to be improved. In addition, the bone induction capability of the porous titanium was investigated through implanting the implants into the muscles. Results showed that the anatase TiO2nanotubes promoted expression of the bone morphogenetic protein (BMP-2). And so did the surface of implants treated by NaOH solution. It indicated that the modified surface had the potentital bone induction ability.
Finally, the HA/Ti composites was prepared and the mechanical properties were characterized. The results showed that the compressive strength increased with the addition of the titanium. When the quality ratio of the hydroxyapatite and titanium is1:15, the compressive strength is181.89MPa. Meanwhile, the composites can induce the formation of hydroxyapatite. Moreover, the double layer graded porous composites with excellent mechanical properties can be prepared by adjusting the space holder addition. The graded porous composites with higher porosity in outer layer can be used as a new kind of bone-substitute materials.
引文
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