纯钛铸件表面氮化处理的实验研究
|
摘要
钛具有良好的机械力学性能,化学稳定性和生物相容性,已在航空航天、航海、军事和生物医学领域广泛应用。纯钛在口腔医学中主要用于制作义齿支架、冠与固定桥、正畸托槽、种植体及钛烤瓷修复体等。钛是自钝化性金属,常温下表面形成一层稳定而致密的氧化膜,因而具有良好的耐腐蚀性。但纯钛的硬度偏低,耐磨性差,纯钛修复体在口腔中行使功能时,钛表面氧化膜在磨擦力、剪切力等应力作用下,容易受到擦伤和磨损,龋齿预防剂如含氟牙膏、凝胶对这层氧化膜亦有一定的破坏作用。本课题研究对铸造纯钛进行表面改性处理,以增强其耐磨性和耐腐蚀性,改善表面颜色,从而提高口腔纯钛修复体的性能和美学效果。
一、铸造纯钛等离子氮化处理的实验研究
纯钛TA2常规铸造、机械抛光后置于等离子氮化炉中,在氨气气氛中进行辉光等离子渗氮处理,辉光电压700V,电流13～15A,炉内真空度150Pa,渗氮温度700℃,渗氮时间1～4h,研究等离子渗氮对纯钛显微硬度、耐磨性和耐腐蚀性的影响。
纯钛铸件等离子氮化处理后,表面呈现淡黄色,边界部分颜色较淡,这是辉光放电的“边界效应”造成的。显微硬度、耐磨性及在人工唾液中的耐腐蚀性显著提高,主要是由于渗氮过程中,表面形成渗氮复合层,渗氮复合层含有TiN和Ti_2N相,TiN和Ti_2N的硬度较高,渗氮复合层下方为氮扩散层,含有大量氮原子向钛基体扩散形成的间隙固溶体,渗氮复合层与钛基体的结合强度较高,渗氮复合层和扩散层的形成大大提高了纯钛的显微硬度与耐磨性。
随着等离子渗氮时间的增加,纯钛铸件的显微硬度、耐磨性与耐腐蚀性逐渐增强,主要原因是钛表面渗氮复合层的厚度逐渐增大。等离子渗氮用于纯钛主要存在的问题是颜色不均匀,渗氮时间较长,要在纯钛表面形成有效的渗层,渗氮时间一般大于1h。
二、铸造纯钛表面氮化钛镀膜的实验研究
应用脉冲真空电弧离子镀技术,在铸造纯钛表面制备TiN膜。钛铸件经机械抛光、超声清洗后置于镀膜机真空室中,抽真空至4×10-3Pa时充入氩气,将试件溅射清洗5min,然后充入氮气,制备氮化钛薄膜。改变镀膜工艺参数,对不同条件下制备的TiN薄膜的特征进行表征。其中弧源电流分别设置为55A、75A、90A和110A,基体偏压分别为50V、100V和150V,氮分压分别为1.1×10-1, 1.5×10-1,1.7×10-1和1.9×10-1Pa,钛基体的温度分别为300、400、500和600℃。
钛铸件表面沉积氮化钛膜后,呈金黄色外观,显微硬度、耐磨性和耐腐蚀性明显提高;牙刷磨耗实验机摸拟口腔环境,用含氟牙膏分别刷洗镀氮化钛膜的钛铸件和未镀膜钛铸件,结果显示:刷洗后未镀膜的钛铸件出现了失泽和变色,而表面镀氮化钛膜的钛铸件则无明显的颜色改变,表明镀膜的钛铸件颜色稳定性较好;表面镀氮化钛膜的钛铸件表面形貌无明显改变,而未镀膜的钛铸件表面粗糙度增大,表面形貌有较大的改变,表明氮化钛膜对钛铸件有较好的磨损保护作用。
改变氮分压,氮化钛膜可呈现不同的颜色。当氮分压为1.7×10-1Pa,弧源电流55A,基体偏压100V时,制备的TiN薄膜呈金黄色。增大氮分压,TiN薄膜颜色偏向红黄,减小氮分压,TiN薄膜颜色偏向淡黄。氮分压增大,TiN薄膜的显微硬度开始增大,氮分压为1.7×10-1Pa时,薄膜硬度达到最大值,继续增大氮分压,薄膜硬度开始下降。薄膜硬度的改变与薄膜相结构的改变有关,氮分压低时,氮化钛膜的主要结构为Ti_2N、TiN多相共存,随着氮分压的增高,氮化钛膜逐渐转变为TiN结构。氮分压为1.7×10-1Pa时,薄膜硬度达到最大,此时薄膜中有大量的Ti_2N,这种多相共存的结构提高了薄膜的硬度。
电弧离子镀兼具真空蒸镀的沉积速率高和溅射镀膜沉积粒子能量高的特点,还具有膜层与基体结合力强,金属离化率高,绕射性好等优点;缺点是镀膜过程中易产生液滴。基体施加脉冲偏压代替直流偏压,应用磁过滤器,可使薄膜中大颗粒的尺寸和数量明显减少,提高薄膜质量。脉冲电弧离子镀同等离子渗氮相比,具有明显的优势:可在纯钛表面形成均匀的氮化钛薄膜,镀膜过程中基体温度较低,镀膜时间较短,一般为30min。缺点是薄膜的耐磨性低于等离子渗氮。
将等离子渗氮和脉冲真空电弧离子镀结合起来,钛铸件镀膜前先进行等离子渗氮,可以获得较厚的与基体结合牢固的表面硬化层,对离子镀硬质氮化钛膜起到强有力的支撑,不仅可使膜层的抗变形能力提高,而且使膜层到基体的应力分布连续性较好,从而提高膜基结合力。对纯钛进行复合表面处理,可以克服等离子渗氮颜色不均匀和电弧离子镀制备的TiN膜耐磨性差的缺点,达到理想的表面改性效果。
对义齿钛支架进行等离子渗氮、电弧离子镀氮化钛复合表面处理后,表面光滑,呈金黄色外观,色彩稳定性较好,耐磨性和耐腐蚀性显著提高,具有较大的临床意义。
Titanium and its alloys are widely used in many areas such as aerospace, marine and biomedical areas due to their outstanding properties such as good mechanical property, chemical stability and biocompatibility. Pure titanium has been used to make crowns and fixed partial denture, denture framework, implants and orthodontic brackets. Titanium is easily passivated and a condense and stable oxide film formed on its surface at room temperature, so it has excellent corrosion resistance. The main problem in using titanium as medical materials is its low hardness and wear resistance. When titanium prosthesis functions in the oral environment, the surface passivation layer is easily destroyed by frictional force, shearing force and other forms of stress. Carries preventive agent such as fluoride-containing toothpaste, gel can also destroy the passivation film to some extent. TiN is known to possess high hardness, good tribological properties, excellent chemical stability and biocompatibility. TiN can be produced either by nitriding on the Ti alloys or by some coating techniques such as physical vapor deposition (PVD), chemical vapor deposition(CVD). In this study plasma nitriding and PVD (arc ion-plating) were used to improve wear and corrosion resistance, surface color of pure cast titanium, the results is expected to improve properties of denture made from titanium.
1 Plasma nitriding of pure cast titanium
CP Ti (TA2) was cast in dental titanium casting machine (LZ-2), the specimens were placed into nitriding chamber after being mechanically polished and ultrasonically cleaned and then plasma nitrided in the NH3 atmosphere. The nitriding temperature was 700℃, glow voltage 700V, current intensity 13-15A, chamber pressure 150Pa and nitriding time 1-4h.
After plasma nitrided, the titanium specimens appeared dark golden in color, it was not uniform and reduced to the edges due to the“edges effect”of glow discharge. Microhardness, wear resistance and corrosion resistance in artificial saliva improved significantly. During the process of nitriding, a compound nitriding layer containing TiN and Ti_2N formed on the specimen surface, underneath the compound layer was diffusion layer that consisted of an interstitial solution of nitrogen in theα-Ti, the compound layer adhered to the substrate well, the formation of diffusion layer and compound layer increased the wear and corrosion resistance of pure cast titanium greatly.
With the increase of nitriding time, microhardness, wear resistance and corrosion resistance in artificial saliva increased gradually. The main reason is that the thickness of compound layer increased with the increase of nitriding time. The main problem of plasma nitriding is that the color is not uniform and treatment time is long. In order to acquire useful nitrided layer, the nitriding time is 1h at least.
2 Deposition of TiN film on pure cast titanium by pulsed bias arc ion plating
Pulsed vacuum arc ion plating was used to deposit TiN film on surface of pure cast titanium. The cast titanium specimens were mechanically polished, ultrasonically cleaned before being placed into vacuum chambers. The base pressure of the vacuum chamber before operation was 8×10-3Pa, the Ar gas was introduced and the specimens were cleaned by Ar ion bombardment for 15min, then deposition of Ti began at a substrate bias of 400V with an arc current of 70A for 3min. After that deposition of TiN began by introducing N2 into the vacuum chamber and the substrate bias was 100V. The deposition lasted for 30min and the arc current was controlled at 70A. The processing parameters were adjusted and the TiN film was characterized deposited at different conditions, the arc current was controlled at 55A, 70A and 90A , the substrate bias at 50V, 100V and 150V, nitrogen pressure at 1.1×10-1, 1.5×10-1, 1.7×10-1 and 1.9×10-1Pa,the substrate temperature was controlled at 400, 500 and 600℃respectively. The film was characterized using a range of analytical and measurement techniques, including scanning electron microscopy (SEM), X-ray diffraction(XRD), XPS, and nanoindentation, etc.
After TiN film was deposited on the surface of cast titanium specimens, the specimens appeared bright and golden, microhardness, wear resistance and corrosion resistance improved significantly. Oral environment was simulated by a toothbrushing wear testing machine in which untreated titanium samples and TiN coated samples were toothbrushed with fluoride-containing toothpaste slurry, after being brushed, to the untreated titanium samples, surface roughness increased, surface morphologies changed obviously, discoloration and tarnish could be observed, while surface morphologies and color of TiN coated samples didn’t change significantly indicating TiN has good color stability and can protect cast titanium from excessive abrasion.
Color of TiN film was different when the N2 pressure was changed, it appeared bright and golden in color when N2 pressure was 1.7×10-1Pa, arc current 55A and substrate bias 100V, the color leaned to red yellow when N2 pressure increased and to light yellow when N2 pressure decreased. Microhardness of TiN increased when N2 pressure increased, the hardness was largest when N2 gas pressure was 1.7×10-1Pa, then the hardness began to decrease when N2 gas pressure continued to increase. The change of hardness is related with the change of phase structure. If the N2 gas pressure was low, the film was mixed with Ti_2N and TiN, the phases changed to TiN structure gradually with the increase of N2 gas pressure. The maximum hardness was attained when N2 pressure was 1.7×10-1Pa, there were plenty of Ti_2N phases at this time and the multiphase structure increased the film hardness.
Arc ion plating possess the advantage of evaporation coating(high deposition rate) and sputtering coating(high energy deposition particles), besides it has the advantage of high ioning rate, good film substrate adhesion and . The drawback of ion plating is the formation of macrodroplet during coating process. The use of magnetron filter and pulsed substrate bias instead of direct bias can decrease size and quantity of macroparticle and improve film property. Compared with plasma nitriding, pulsed bias arc ion plating has many advantages including an even TiN film formed on surface of titanium specimens, the temperature of substrate was low and treatment time was short, usually the deposition time was 30min. But the wear resistance of ion-plated TiN film needs improving.
Combined with plasma nitriding and pulsed bias arc ion plating is a good way to improve film property, it can overcome the color ununiformity problem of plasma nitriding and improve the wear resistance of ion plated TiN film. Cast titanium is plasma nitrided before TiN film deposition to acquire surface hardening layer which adheres to the substrate well, the layer acts as an interlayer and can support the hard TiN film without plastic deformation when subjected to a high-intensity loading, it can also optimize the stress distribution from the film to the substrate and enhance the film adhesion.
After titanium framework of denture was plasma nitrided and TiN coated, its surface was smooth and appeared bright and golden, it had good color stability, its wear and corrosion resistance improved significantly, so the compound surface treatment of pure titanium has major significance in stomatology.
一、铸造纯钛等离子氮化处理的实验研究
纯钛TA2常规铸造、机械抛光后置于等离子氮化炉中,在氨气气氛中进行辉光等离子渗氮处理,辉光电压700V,电流13～15A,炉内真空度150Pa,渗氮温度700℃,渗氮时间1～4h,研究等离子渗氮对纯钛显微硬度、耐磨性和耐腐蚀性的影响。
纯钛铸件等离子氮化处理后,表面呈现淡黄色,边界部分颜色较淡,这是辉光放电的“边界效应”造成的。显微硬度、耐磨性及在人工唾液中的耐腐蚀性显著提高,主要是由于渗氮过程中,表面形成渗氮复合层,渗氮复合层含有TiN和Ti_2N相,TiN和Ti_2N的硬度较高,渗氮复合层下方为氮扩散层,含有大量氮原子向钛基体扩散形成的间隙固溶体,渗氮复合层与钛基体的结合强度较高,渗氮复合层和扩散层的形成大大提高了纯钛的显微硬度与耐磨性。
随着等离子渗氮时间的增加,纯钛铸件的显微硬度、耐磨性与耐腐蚀性逐渐增强,主要原因是钛表面渗氮复合层的厚度逐渐增大。等离子渗氮用于纯钛主要存在的问题是颜色不均匀,渗氮时间较长,要在纯钛表面形成有效的渗层,渗氮时间一般大于1h。
二、铸造纯钛表面氮化钛镀膜的实验研究
应用脉冲真空电弧离子镀技术,在铸造纯钛表面制备TiN膜。钛铸件经机械抛光、超声清洗后置于镀膜机真空室中,抽真空至4×10-3Pa时充入氩气,将试件溅射清洗5min,然后充入氮气,制备氮化钛薄膜。改变镀膜工艺参数,对不同条件下制备的TiN薄膜的特征进行表征。其中弧源电流分别设置为55A、75A、90A和110A,基体偏压分别为50V、100V和150V,氮分压分别为1.1×10-1, 1.5×10-1,1.7×10-1和1.9×10-1Pa,钛基体的温度分别为300、400、500和600℃。
钛铸件表面沉积氮化钛膜后,呈金黄色外观,显微硬度、耐磨性和耐腐蚀性明显提高;牙刷磨耗实验机摸拟口腔环境,用含氟牙膏分别刷洗镀氮化钛膜的钛铸件和未镀膜钛铸件,结果显示:刷洗后未镀膜的钛铸件出现了失泽和变色,而表面镀氮化钛膜的钛铸件则无明显的颜色改变,表明镀膜的钛铸件颜色稳定性较好;表面镀氮化钛膜的钛铸件表面形貌无明显改变,而未镀膜的钛铸件表面粗糙度增大,表面形貌有较大的改变,表明氮化钛膜对钛铸件有较好的磨损保护作用。
改变氮分压,氮化钛膜可呈现不同的颜色。当氮分压为1.7×10-1Pa,弧源电流55A,基体偏压100V时,制备的TiN薄膜呈金黄色。增大氮分压,TiN薄膜颜色偏向红黄,减小氮分压,TiN薄膜颜色偏向淡黄。氮分压增大,TiN薄膜的显微硬度开始增大,氮分压为1.7×10-1Pa时,薄膜硬度达到最大值,继续增大氮分压,薄膜硬度开始下降。薄膜硬度的改变与薄膜相结构的改变有关,氮分压低时,氮化钛膜的主要结构为Ti_2N、TiN多相共存,随着氮分压的增高,氮化钛膜逐渐转变为TiN结构。氮分压为1.7×10-1Pa时,薄膜硬度达到最大,此时薄膜中有大量的Ti_2N,这种多相共存的结构提高了薄膜的硬度。
电弧离子镀兼具真空蒸镀的沉积速率高和溅射镀膜沉积粒子能量高的特点,还具有膜层与基体结合力强,金属离化率高,绕射性好等优点;缺点是镀膜过程中易产生液滴。基体施加脉冲偏压代替直流偏压,应用磁过滤器,可使薄膜中大颗粒的尺寸和数量明显减少,提高薄膜质量。脉冲电弧离子镀同等离子渗氮相比,具有明显的优势:可在纯钛表面形成均匀的氮化钛薄膜,镀膜过程中基体温度较低,镀膜时间较短,一般为30min。缺点是薄膜的耐磨性低于等离子渗氮。
将等离子渗氮和脉冲真空电弧离子镀结合起来,钛铸件镀膜前先进行等离子渗氮,可以获得较厚的与基体结合牢固的表面硬化层,对离子镀硬质氮化钛膜起到强有力的支撑,不仅可使膜层的抗变形能力提高,而且使膜层到基体的应力分布连续性较好,从而提高膜基结合力。对纯钛进行复合表面处理,可以克服等离子渗氮颜色不均匀和电弧离子镀制备的TiN膜耐磨性差的缺点,达到理想的表面改性效果。
对义齿钛支架进行等离子渗氮、电弧离子镀氮化钛复合表面处理后,表面光滑,呈金黄色外观,色彩稳定性较好,耐磨性和耐腐蚀性显著提高,具有较大的临床意义。
Titanium and its alloys are widely used in many areas such as aerospace, marine and biomedical areas due to their outstanding properties such as good mechanical property, chemical stability and biocompatibility. Pure titanium has been used to make crowns and fixed partial denture, denture framework, implants and orthodontic brackets. Titanium is easily passivated and a condense and stable oxide film formed on its surface at room temperature, so it has excellent corrosion resistance. The main problem in using titanium as medical materials is its low hardness and wear resistance. When titanium prosthesis functions in the oral environment, the surface passivation layer is easily destroyed by frictional force, shearing force and other forms of stress. Carries preventive agent such as fluoride-containing toothpaste, gel can also destroy the passivation film to some extent. TiN is known to possess high hardness, good tribological properties, excellent chemical stability and biocompatibility. TiN can be produced either by nitriding on the Ti alloys or by some coating techniques such as physical vapor deposition (PVD), chemical vapor deposition(CVD). In this study plasma nitriding and PVD (arc ion-plating) were used to improve wear and corrosion resistance, surface color of pure cast titanium, the results is expected to improve properties of denture made from titanium.
1 Plasma nitriding of pure cast titanium
CP Ti (TA2) was cast in dental titanium casting machine (LZ-2), the specimens were placed into nitriding chamber after being mechanically polished and ultrasonically cleaned and then plasma nitrided in the NH3 atmosphere. The nitriding temperature was 700℃, glow voltage 700V, current intensity 13-15A, chamber pressure 150Pa and nitriding time 1-4h.
After plasma nitrided, the titanium specimens appeared dark golden in color, it was not uniform and reduced to the edges due to the“edges effect”of glow discharge. Microhardness, wear resistance and corrosion resistance in artificial saliva improved significantly. During the process of nitriding, a compound nitriding layer containing TiN and Ti_2N formed on the specimen surface, underneath the compound layer was diffusion layer that consisted of an interstitial solution of nitrogen in theα-Ti, the compound layer adhered to the substrate well, the formation of diffusion layer and compound layer increased the wear and corrosion resistance of pure cast titanium greatly.
With the increase of nitriding time, microhardness, wear resistance and corrosion resistance in artificial saliva increased gradually. The main reason is that the thickness of compound layer increased with the increase of nitriding time. The main problem of plasma nitriding is that the color is not uniform and treatment time is long. In order to acquire useful nitrided layer, the nitriding time is 1h at least.
2 Deposition of TiN film on pure cast titanium by pulsed bias arc ion plating
Pulsed vacuum arc ion plating was used to deposit TiN film on surface of pure cast titanium. The cast titanium specimens were mechanically polished, ultrasonically cleaned before being placed into vacuum chambers. The base pressure of the vacuum chamber before operation was 8×10-3Pa, the Ar gas was introduced and the specimens were cleaned by Ar ion bombardment for 15min, then deposition of Ti began at a substrate bias of 400V with an arc current of 70A for 3min. After that deposition of TiN began by introducing N2 into the vacuum chamber and the substrate bias was 100V. The deposition lasted for 30min and the arc current was controlled at 70A. The processing parameters were adjusted and the TiN film was characterized deposited at different conditions, the arc current was controlled at 55A, 70A and 90A , the substrate bias at 50V, 100V and 150V, nitrogen pressure at 1.1×10-1, 1.5×10-1, 1.7×10-1 and 1.9×10-1Pa,the substrate temperature was controlled at 400, 500 and 600℃respectively. The film was characterized using a range of analytical and measurement techniques, including scanning electron microscopy (SEM), X-ray diffraction(XRD), XPS, and nanoindentation, etc.
After TiN film was deposited on the surface of cast titanium specimens, the specimens appeared bright and golden, microhardness, wear resistance and corrosion resistance improved significantly. Oral environment was simulated by a toothbrushing wear testing machine in which untreated titanium samples and TiN coated samples were toothbrushed with fluoride-containing toothpaste slurry, after being brushed, to the untreated titanium samples, surface roughness increased, surface morphologies changed obviously, discoloration and tarnish could be observed, while surface morphologies and color of TiN coated samples didn’t change significantly indicating TiN has good color stability and can protect cast titanium from excessive abrasion.
Color of TiN film was different when the N2 pressure was changed, it appeared bright and golden in color when N2 pressure was 1.7×10-1Pa, arc current 55A and substrate bias 100V, the color leaned to red yellow when N2 pressure increased and to light yellow when N2 pressure decreased. Microhardness of TiN increased when N2 pressure increased, the hardness was largest when N2 gas pressure was 1.7×10-1Pa, then the hardness began to decrease when N2 gas pressure continued to increase. The change of hardness is related with the change of phase structure. If the N2 gas pressure was low, the film was mixed with Ti_2N and TiN, the phases changed to TiN structure gradually with the increase of N2 gas pressure. The maximum hardness was attained when N2 pressure was 1.7×10-1Pa, there were plenty of Ti_2N phases at this time and the multiphase structure increased the film hardness.
Arc ion plating possess the advantage of evaporation coating(high deposition rate) and sputtering coating(high energy deposition particles), besides it has the advantage of high ioning rate, good film substrate adhesion and . The drawback of ion plating is the formation of macrodroplet during coating process. The use of magnetron filter and pulsed substrate bias instead of direct bias can decrease size and quantity of macroparticle and improve film property. Compared with plasma nitriding, pulsed bias arc ion plating has many advantages including an even TiN film formed on surface of titanium specimens, the temperature of substrate was low and treatment time was short, usually the deposition time was 30min. But the wear resistance of ion-plated TiN film needs improving.
Combined with plasma nitriding and pulsed bias arc ion plating is a good way to improve film property, it can overcome the color ununiformity problem of plasma nitriding and improve the wear resistance of ion plated TiN film. Cast titanium is plasma nitrided before TiN film deposition to acquire surface hardening layer which adheres to the substrate well, the layer acts as an interlayer and can support the hard TiN film without plastic deformation when subjected to a high-intensity loading, it can also optimize the stress distribution from the film to the substrate and enhance the film adhesion.
After titanium framework of denture was plasma nitrided and TiN coated, its surface was smooth and appeared bright and golden, it had good color stability, its wear and corrosion resistance improved significantly, so the compound surface treatment of pure titanium has major significance in stomatology.
引文
1.郭天文主编.口腔科用钛理论和技术.北京,人民军医出版社,2005,4-25.
2. M. Geetha, A.K. Singh, R. Asokamani, A.K. Gogia. Ti based bi(materials, the ultimate choice for orthopaedic implants - A review. Progress in Materials Science, 2009; 54(3): 397-425.
3. Stefano Piscanec, Lucio Colombi Ciacchi, Erik Vesselli, Giovanni Comelli, Bioactivity of TiN-coated titanium implants. Acta Materialia, 2004; 52(5): 1237-1245.
4.魏宝明主编.金属腐蚀理论及应用.北京,化学工业出版社,1984,1-350.
5. Satendra Kumar, T.S.N.Sankara Narayanan. Corrosion behaviour of Ti-15Mo alloy for dental implant applications. Journal of De n t i s t r y; 2 0 0 8; 3 6:5 0 0-5 0 7.
6.师昌绪主编.材料科学技术百科全书.北京,中国大百科全书出版社,1995.98-100.
7. Screenivas K, Michael ER, Thomas JB, et al. Microbial colonization of dental implants in partially edentulous subjects. J Prosthet Dent, 1993, 70(2): 141-143.
8.宋应亮,徐君伍,马轩祥.Aay4对钛及钛75合金表面失泽腐蚀的研究,中华口腔医学杂志,2000;35(4):256-258.
9.宋应亮,徐君伍,马轩祥.白色念珠菌对铸钛、Co-Cr合金、Ni-Cr合金修复体失泽腐蚀的影响. 实用口腔医学杂志, 2000; 16(2):111-114.
10.宋应亮,徐君伍,马轩祥.牙龈卟啉菌381对纯钛及钛75合金种植体表面失泽的腐蚀,第四军医大学学报;2000; 21(8):916-917.
11.宋应亮,徐君伍,马轩祥.远缘链球菌ｇ型对铸钛、钴铬合金、镍铬合金修复体腐蚀失泽的研究,华西口腔医学杂志, 2002; 20(1):14-17.
12. Schiff N, Grosgogeat B, Lissac M, etc. Influence of fluoride content and pH on the corrosion resistance of titanium and its alloys. Biomaterials, 2002, 23:1995.
13. Nakagawa M, Matsuya S. Shiraishi T. Ohta M. Effect of fluoride concentration and pH on corrosion behavior of titanium for dental use. J Dent Res. 1999; 78(9): 1568-1572.
14. A. Bloyce. P.-Y. Qi. H. Dong. T. Bell. Surface modification of titanium alloys for combined improvements in corrosion and wear resistance. Surf. Coat. Technol. 1998:107: 125.
15. P. Stratton, J. Boodey, Proceedings of the 1st ASM International Surface Engineering and the 13th IFHTSE Congress, ASM International, 2003, p.22.
16. Xinhua Wu. A. Huang. D. Hu. M.H. Loretto. Oxidation-induced embrittlement of TiAl alloys. Intermetallics. 2009; 17(7): 540-552
17. A.N. Minkevich, Thermo-chemical Treatment of Metals and Alloys, Mashinostroene Press, Moscow, 1965, p.325.
18. P.Stratum, J. Boodey, Proceedings of the 1st ASM International Surface Engineering and the 13th IFHTSE Congress, ASM International,2003, p.22.
19. Y. Kasukabe, S. Nishida. S. Yamamoto, M. Yoshikawa, Y Fujino. Atomistic nitriding processes of titanium thin films due to nitrogen-implantation. Applied Surface Science, 2008, 254(23): 7942-7946.
20. Wei Sha, Ak Muhd Fu'Ad Pg Haji Ali. Xiaomin Wu. Gas nitriding of titanium alloy Timetal 205. Surface and Coatings Technology, 2008; 202(24): 5832-5837.
21. W. Sha, M.A. Haji Mat Don, A. Mohamed. X. Wu, B. Siliang, A. Zhecheva. X-ray diffraction, optical microscopy, and microhardness studies of gas nitrided titanium alloys and titanium aluminide. Materials Characterization. 2008; 59(3): 229-240.
22．孙荣禄，郭立新，董尚利，杨德庄．钛及钛合金表面耐磨热处理．宇航材料工 艺，1999(5)：15-18
23. D.P. Shashkov, Metallovedenie i Termicheskaya Obrabotka Metallov 6(2001)
24. K.T. Rie, T. Stucky, R.A. Silva, E. Leitao, Plasma surface treatment and PACVD on Ti alloys for surgical implants. Surf. Coat. Technol. 1995; (74-75): 973-980.
25. B.S. Yilbas, A.Z. Sahin, A.Z. Al-Garni, S.A.M. Said, Z. Ahmed B.J.Abdulaleem, M. Sami, Plasma nitriding of Ti-6A1-4V alloy to improve some tribological properties. Surf. Coat. Technol. 1996; 80(3): 287-292.
26. A. Fleszar, T. Wierzchon, Sun Kyu Kim, J.R. Sobiecki, Properties of surface layers produced on the Ti-6Al-3Mo-2Cr titanium alloy under glow discharge conditions. Surf. Coat Technol. 2000; 131(1-3): 62-65.
27. S. Gokul Lakshmi, D. Arivuoli, B. Ganguli, Surface modification and characterisation of Ti-Al-V alloys. Mater. Chem. Phys. 2002; 76(2): 187.
28. F. Galliano, E. Galvanetto, S. Mischler, D. Landolt, Tribocorrosion behavior of plasma nitrided Ti-6A1-4V alloy in neutral NaCl solution. Surf. Coat Technol. 2001; 145 (1-3): 121-131.
29. N. Renevier, P. Collignon, H. Michel, T. Czerwiec, Low temperature nitriding of AISI 316L stainless steel and titanium in a low pressure arc discharge. Surf. Coat Technol. 1999;111(2-3): 128.
30. T.Bell, W.Bergman, J.Lanagan, PH. Morton, A.M.Staines, Microstructure and microhardness of gas nitrided surface layers in Ti-8Al-lMo-lV and Ti-10V-2Fe-3Al alloys Surf Eng. 1986; 2:133.
31. L. Xue, M.U. Islam, A.K. KouL W. Wallace, M. Bibby, Mater Manuf. Process. 1997;12 (5):799.
32. L. Xue, M.U. Islam, A.K. KouK W. Wallace, M. Bibby, Laser Gas Nitriding of Ti-6A1-4V Part 2: Characteristics of Nitrided Layers. Adv. Perform. Mater. 1997; 4:389-408.
33. S. Mridha, T.N. Baker, Effects of nitrogen gas flow rates on themicrostructure and properties of laser-nitrided IMI318 titanium alloy (Ti-4V-6A1). J. Mater. Process. Technol. 1998; 77 (1-3):115-121.
34. Yue He, Jizhong Zhang. Wenqing Yao, Dexing Li, Xu Teng. Effect of temperature on residual stress and mechanical properties of Ti films prepared by both ion implantation and ion beam assisted deposition. Applied Surface Science, 2009; 255(8): 4484-4490.
35. Stefan Krischok, Claudia Blank. Michael Engel. Richard Gutt. Gernot Ecke, Jens Schawohl. Lothar SpieB. Frank Schrempel. Gerhard Hildebrand. Klaus Liefeith. Influence of ion implantation on titanium surfaces for medical applications. Surface Science, 2007; 601(18): 3856-3860.
36. Takeo Nakano. Ken'ichiroh Hoshi. Shigeru Baba. Effect of background gas environment on oxygen incorporation in TiN films deposited using UHV reactive magnetron sputtering. Vacuum. 2008; 83(3): 467-469
37. Stefan Wrehde, Marion Quaas. Robert Bogdanowicz, Hartmut Steffen. Harm Wulff, Rainer Hippler. Optical and chemical characterization of thin TiNx films deposited by DC-magnetron sputtering. Vacuum. 2008; 82(10): 1115-1119
38. Sankar Moni Borah. Arup Ratan Pal. Heremba Bailung, Joyanti Chutia. Optimization of plasma parameters for high rate deposition of titanium nitride films as protective coating on bell-metal by reactive sputtering in cylindrical magnetron device. Applied Surface Science, 2008;254(18): 5760-5765
39. N. Ichimiya, Y Onishi, Y Tanaka. Properties and cutting performance of (Ti,V)N coatings prepared by cathodic arc ion plating. Surface and Coatings Technology, 2005;200(5-6): 1377-1382.
40. Qiang RU. Shejun HU. Nacan HUANG Lingzhi ZHAO, Xiuli QIU. Xianqi HU. Properties of TiAlCrN coatings prepared by vacuum cathodic arc ion plating. Rare Metals, 2008;27(3): 251-256
41. M. Uchida, N. Nihira, A. Mitsuo, K. Toyoda. K. Kubota, T. Aizawa. Frictionand wear properties of CrAlN and CrVN films deposited by cathodic arc ion plating method. Surface and Coatings Technology, 2004;(177-178)30: 627-630
42. A. Mubarak, E. Hamzah, M.R.M. Toff. Study of macrodroplet and growth mechanisms with and without ion etchings on the properties of TiN coatings deposited on HSS using cathodic arc physical vapour deposition technique. Materials Science and Engineering: A, 2008;474(l-2):236-242
43．多弧离镀技术与应用，张钧，赵彦辉编著，冶金工业出版社，北京，2007第1版，p12．
44. I. Shishkovsky, Yu. Morozov, I. Yadroitsev, I. Smurov. Titanium and Aluminum Nitride Synthesis via layer by layer LA-CVD. Applied Surface Science, In Press, Accepted Manuscript, Available online 22 April 2009.
45. John A.T Norman, Melanie Perez, Stefan E. Schulz, Thomas Waechtler. New precursors for CVD copper metallization. Microelectronic Engineering, 2008;85(10): 2159-2163
46. K.W. Chen, Y.L. Wang, L. Chang, F.Y Li, GJ. Hwang. Effects of plasma treatment in the tungsten process for chemical vapor deposition titanium nitride barrier film beyond nanometer technology. Thin Solid Films, 2006;498(l-2):64-69
47. Yuzuru Ogura, Chikako Kobayashi, Yoshiyuki Ooba, Naoki Yahata, Hitoshi Sakamoto. Low temperature deposition of metal films by metal chloride reduction chemical vapor deposition. Surface and Coatings Technology, 2006;200(10):3347-3350
48．表面科学与技术，姚寿山，李戈扬，胡文彬，北京：机械工业出版社，2005年第1版，p263-267．
49.W J. Meng，GL.Eesley. Growth and mechanical anisotropy of TiN thin films [J]. Thin Solid Films, 1995(271): 108-116.
50.N. Popovic, Z. Bogdanov, B. Goncic, S. Zec, Z. Rakocevic, M. Zlatanovic, D. Perusko. TiN thin films deposited by ion beam sputtering effects ofosited by pulsed direct current magnetron sputtering. Thin Solid Films, 2008;516(21):7294-7298
52. E. Bemporad, M. Sebastiani, C. Pecchio, S. De Rossi. High thickness Ti TiN multilayer thin coatings for wear resistant applications. Surface and Coatings Technology, 2006;201(6):2155-2165
53. F. Borgioli. E. Galvanetto. F.P. Galliano. T. Bacci. Sliding wear resistance of reactive plasma sprayed Ti-TiN coatings. Wear, 2006;260(7-8): 832-837
54. Wenran Feng. Dianran Van, Jining He, Xiangzhi Li. Vanchun Dong. Reactive plasma sprayed TiN coating and its tribological properties. Wear, 2005;258(5-6):806-811
55. J. M. Lackner, W. Waldhauser, R. Berghauser, R. Ebner, B. Major. T. Schoberl. Structural, mechanical and tribological investigations of pulsed laser deposited titanium nitride coatings. Thin Solid Films. 2004; (453-454): 195-202
56. P.J. Kelly, T. vom Braucke, Z. Liu. R.D. ArnelL E.D. Doyle. Pulsed DC titanium nitride coatings for improved tribological performance and tool life. Surface and Coatings Technology, 2007;202(4-7):774-780
57. Hendry J A, Pilliar R M. The fretting corrosion resistance of PVD surface-modified orthopedic implant alloys. J Biomed Mater Res, 2001; 58(2): 156-166.
58. Deyuan Zhang. Weijun Zeng. Zhenjun Zi. Paul K.Chu. Corrosion resistance of TiN coated biomedical nitinol under deformation. Materials Science and Engineering: C. In Press, Corrected Proof, Available online 31 December 2008.
59. Starosvetsky D, Gotman I. Corrosion behavior of titanium nitride coated Ni-Ti shape memory surgical alloy. Biomaterials. 2001; 22(13): 1853-1859.
60．周雅彬，米乃元，李彦，滕伟，范丹妮．氮化钛涂层对牙科合金析出金属离子的影响,中山大学学报（医学科学版）2003; 24(3): 295-297.
61. Wataha J C. Biocompatibility of dental casting alloys: A review. J Prosthet Dent, 2000, 83(2): 223-234.
62. Bordji K, Jouzeau JY, Mainard D, etc. Cytocompatibility of Ti-6A1-4V and Ti-5Al-2.5Fe alloys according to three surface treatments, using human fibroblasts and osteoblasts. Biomaterials, 1996; 17(9): 929-940.
63. Chia-Chi Chien. Kuan-Ting Liu, Jenq-Gong Duh. Kuo-Wei Chang, Kwok-Hung Chung, Effect of nitride film coatings on cell compatibility. Dental materials, 2008; 24: 986-993.
64. Her-Hsiung Huang, Chu-Hui Hsu. Szu-Jung Pan, Ju-Liang He, Chun-Cheng Chen, Tien-Ling Lee, Corrosion and cell adhesion behavior of TiN-coated and ion-nitrided titanium for dental applications. Applied Surface Science, 2005; 244: 252-256.
65. Dion I, Rouais F, Trut L, etc. TiN coating: surface characterization and haemocompatibility. Biomaterials, 1993; 14(3): 169-176.
66. Dion I, Roques X, More N, etc. Ex vivo leucocyte adhesion and protein adsorption on TiN. Biomaterials, 1993; 14(9):712-719.
67. Mitamura Y, Hosooka K, Matsumoto T, etc. J Biomater Appl, 1989; 4(l):33-35.
68. B. Subramanian, M. Jayachandran. Electrochemical corrosion behavior of magnetron sputtered TiN coated steel in simulated bodily fluid and its hemocompatibility. Materials Letters 62 (2008) 1727-1730.
69.陈震,梁峥嵘,时光辉,韩栋伟.氮化钛膜对纯钛表面细菌黏附能力的影响.同济大学学报(医学版), 2008;28(1): 37-40.
70. Scarano A,Piattelli M. Bacterial adhesion on titanium nitride-coated and uncoated implants: an in vivo human study [J].J Oral Implantol, 2003; 29(2):80-85.
71. G Sovak, A Weiss, I Gotman, Osseointegration of Ti6A14V alloy implants coated with titanium nitride by a new method. J Bone Joint Surg (Britishivolume), 2000(2): 290-296.
72.郑晓辉,邓春富,杨彦昌.氮化钛—钛陶瓷复合体颌骨内种植的动物实验 研究.中国医科大学学报,1995;24(1):15-17
73. Pappas MJ, Makris G, Buechel FF. Titanium nitride ceramic film against polyethylene. A 48 million cycle wear test. Clin Orthop Relat Res, 1995; (317):64-70.
74. Rawlings RD, Robinson PB, Rogers PS. The durability of ceramic coated dental instruments. Eur J Prosthdont Restorat Denti. 1995; 3(5): 211-216
75. Rapisarda E, Bonaccorso A, Tripi TR, etc. The effect of surface treatments of nickel-titanium files on wear and cutting efficiency. Oral Medicine Oral Pathology Oral Radiology, Endodontics, 2000; 89(3): 363-368.
76. Schafer E. Effect of Physical Vapor Deposition on Cutting Efficiency of Nickel-Titanium Files. J Endod, 2002; 28(12): 800-802.
77. D. Nolan, S.W. Huang, V. Leskovsek, S. Braun. Sliding wear of titanium nitride thin films deposited on Ti-6A1-4V alloy by PVD and plasma nitriding processes. Surface and Coatings Technology, 2006;200(20-21): 5698-5705.
78.谢紫杰,朱景环.工业纯钛的离子渗氮.热处理,1998;3:21-23.
79. H.C. Man, Z.D. Cui, X.J. Yang, Analysis of laser gas nitrided titanium by X-ray photoelectron spectroscopy, Appl. Surf. Sci. 2002;199:293.
80. S.Malinov, A.Zhecheva, W.Sha, Proceedings of the 1 International Surface Engineering Congress and the 13 IFHTSE Congress, ASM International, Materials Park, OH,2003,p.344.
81.周锋,傅迎庆,高阳.热等离子束照射工业纯钛快速渗氮制备表面氮化层. 稀有金属材料与工程, 2007;36(Suppl2):728-730.
82. K.Wilsdorf, H.-J.Spies, in: Associazione Italiana di Metallurgia,11th Congress of the International Federation for Heat Treatment and Surface Engineering and the 4th ASM Heat Treatment and Surface Engineering Conference in Europe Proceedings, Italy, vol.1. 1998. p.351.
83. A. Zhecheva, S.Malinov, W.Sha, Surface gas nitriding of Ti-6A1-4V and Ti-6Al-2Sn-4Zr-2Mo-0.08Si alloys. Z. Metallk. 2003; 94(1): 19-24.
84. Waheed A. Badawy, Ahlam M. Fathi, Rabab M. El-Sherief, Sahar A. Fadl-Allah. Electrochemical and biological behaviors of porous titania (TiO2) in simulated body fluids for implantation in human bodies. Journal of Alloys and Compounds, 2009; 475(1-2): 911-916.
85. Olbrich W, Fessmann J, Kampschulte G, Ebberink J. Improved control of TiN coating properties using cathodic arc evaporation with a pulsed bias. Surf Coat TechnoL 1991; 49(1-3): 258-262.
86. Aharonov R R, Chhowala M, Dhar S etc. Factors affecting growth defect formation in cathodic arc evaporated coatings. Surf. Coat. Technol.1996; 82:334.
87. Meidong Huang, Guoqiang Lin, Yanhui Zhao, etc. Macro-particle reduction mechanism in biased arc ion plating of TiN. Surf. Coat. Technol. 2003;176:109-114.
88. Yanhui Zhao, Guoqiang Lin, Chuang Dong, etc. Experimental verification of the physical model for droplet cleaning in pulse-bias arc ion-plating. J. Mater. Sci. TechnoK 2005;21(3): 423-426.
89. Oliver W C, Pharr G M Measurement of Hardness and Elastic Modulus by Instrumented Indentation: Advances in Understanding and Refinements to Methodology [J]J Mater Res, 2004;19:3-20.
90. Oliver W C, Pharr GM. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J Mater Res[J], 1992,7(6): 1564-1583.
91. Moody N R, Strojny A, Medlin D L, et al. Substrate composition effects on the interfacial fracture of tantalum nitride films [J]. Journal of Materials Research, 1999; 14(6): 2306-2313.
92. Doerner MF, Nix W D. A method for interpreting the data from depth-sensing indentation instruments J Mater Res [J], 1986;l:601-609.
93. KOHLSCHEEN J, STOCK H, MAYR P. Chemical bonding in magnetron sputtered TiNx coatings and its relation to diamond turnability. [J] Surface and Coatings Technology, 2001;142-144: 992-998.
94．冷永祥’孙鸿，徐禄祥，等．等离子体浸没离子注入和沉积技术制备TiN薄膜研究．真空科学与技术,2003；23(4)：295-225．
95. Ph. Roquiny, F. Bodart, GTerwagne. Color control of titanium nitride coatings produced by reactive magnetron sputtering at temperature less than 100℃. [J] Surface and Coatings Technology, 1999; 116-119: 278-283.
96. J. Stallard, S. Poulat, D.G Teer. The study of the adhesion of a TiN coating on steel and titanium alloy substrates using a multi-mode scratch tester. Tribology International, 2006;39:159-166.
97．周顺，严一心．脉冲真空电弧离子镀沉积类金刚石薄膜的结构和力学性能研究．西安工业学院学报，2004；24(4)：307-310．
98．姚江武主编．现代口腔色彩学．第1版，厦门大学出版社,2000,30-31．
99. Hanawa T, Asami K, Asaoka K. Repassivation of titanium and surfaceoxide film regenerated in stimulated bioliquid. J Biomed Mater Res, 1998;40:530-538.
100.Wataha JC, Lockwood PE, Noda M, Nelson SK, Mettenburg DJ. Effect oftoothbrushing on the toxicity of casting alloys. J Prosthet Dent, 2002;87:94-98.
101.Fraleigh CM, Elhaney JHM, Heiser RA. Toothbrushing force study, J DentRes, 1967; 46: 209-214.
2. M. Geetha, A.K. Singh, R. Asokamani, A.K. Gogia. Ti based bi(materials, the ultimate choice for orthopaedic implants - A review. Progress in Materials Science, 2009; 54(3): 397-425.
3. Stefano Piscanec, Lucio Colombi Ciacchi, Erik Vesselli, Giovanni Comelli, Bioactivity of TiN-coated titanium implants. Acta Materialia, 2004; 52(5): 1237-1245.
4.魏宝明主编.金属腐蚀理论及应用.北京,化学工业出版社,1984,1-350.
5. Satendra Kumar, T.S.N.Sankara Narayanan. Corrosion behaviour of Ti-15Mo alloy for dental implant applications. Journal of De n t i s t r y; 2 0 0 8; 3 6:5 0 0-5 0 7.
6.师昌绪主编.材料科学技术百科全书.北京,中国大百科全书出版社,1995.98-100.
7. Screenivas K, Michael ER, Thomas JB, et al. Microbial colonization of dental implants in partially edentulous subjects. J Prosthet Dent, 1993, 70(2): 141-143.
8.宋应亮,徐君伍,马轩祥.Aay4对钛及钛75合金表面失泽腐蚀的研究,中华口腔医学杂志,2000;35(4):256-258.
9.宋应亮,徐君伍,马轩祥.白色念珠菌对铸钛、Co-Cr合金、Ni-Cr合金修复体失泽腐蚀的影响. 实用口腔医学杂志, 2000; 16(2):111-114.
10.宋应亮,徐君伍,马轩祥.牙龈卟啉菌381对纯钛及钛75合金种植体表面失泽的腐蚀,第四军医大学学报;2000; 21(8):916-917.
11.宋应亮,徐君伍,马轩祥.远缘链球菌ｇ型对铸钛、钴铬合金、镍铬合金修复体腐蚀失泽的研究,华西口腔医学杂志, 2002; 20(1):14-17.
12. Schiff N, Grosgogeat B, Lissac M, etc. Influence of fluoride content and pH on the corrosion resistance of titanium and its alloys. Biomaterials, 2002, 23:1995.
13. Nakagawa M, Matsuya S. Shiraishi T. Ohta M. Effect of fluoride concentration and pH on corrosion behavior of titanium for dental use. J Dent Res. 1999; 78(9): 1568-1572.
14. A. Bloyce. P.-Y. Qi. H. Dong. T. Bell. Surface modification of titanium alloys for combined improvements in corrosion and wear resistance. Surf. Coat. Technol. 1998:107: 125.
15. P. Stratton, J. Boodey, Proceedings of the 1st ASM International Surface Engineering and the 13th IFHTSE Congress, ASM International, 2003, p.22.
16. Xinhua Wu. A. Huang. D. Hu. M.H. Loretto. Oxidation-induced embrittlement of TiAl alloys. Intermetallics. 2009; 17(7): 540-552
17. A.N. Minkevich, Thermo-chemical Treatment of Metals and Alloys, Mashinostroene Press, Moscow, 1965, p.325.
18. P.Stratum, J. Boodey, Proceedings of the 1st ASM International Surface Engineering and the 13th IFHTSE Congress, ASM International,2003, p.22.
19. Y. Kasukabe, S. Nishida. S. Yamamoto, M. Yoshikawa, Y Fujino. Atomistic nitriding processes of titanium thin films due to nitrogen-implantation. Applied Surface Science, 2008, 254(23): 7942-7946.
20. Wei Sha, Ak Muhd Fu'Ad Pg Haji Ali. Xiaomin Wu. Gas nitriding of titanium alloy Timetal 205. Surface and Coatings Technology, 2008; 202(24): 5832-5837.
21. W. Sha, M.A. Haji Mat Don, A. Mohamed. X. Wu, B. Siliang, A. Zhecheva. X-ray diffraction, optical microscopy, and microhardness studies of gas nitrided titanium alloys and titanium aluminide. Materials Characterization. 2008; 59(3): 229-240.
22．孙荣禄，郭立新，董尚利，杨德庄．钛及钛合金表面耐磨热处理．宇航材料工 艺，1999(5)：15-18
23. D.P. Shashkov, Metallovedenie i Termicheskaya Obrabotka Metallov 6(2001)
24. K.T. Rie, T. Stucky, R.A. Silva, E. Leitao, Plasma surface treatment and PACVD on Ti alloys for surgical implants. Surf. Coat. Technol. 1995; (74-75): 973-980.
25. B.S. Yilbas, A.Z. Sahin, A.Z. Al-Garni, S.A.M. Said, Z. Ahmed B.J.Abdulaleem, M. Sami, Plasma nitriding of Ti-6A1-4V alloy to improve some tribological properties. Surf. Coat. Technol. 1996; 80(3): 287-292.
26. A. Fleszar, T. Wierzchon, Sun Kyu Kim, J.R. Sobiecki, Properties of surface layers produced on the Ti-6Al-3Mo-2Cr titanium alloy under glow discharge conditions. Surf. Coat Technol. 2000; 131(1-3): 62-65.
27. S. Gokul Lakshmi, D. Arivuoli, B. Ganguli, Surface modification and characterisation of Ti-Al-V alloys. Mater. Chem. Phys. 2002; 76(2): 187.
28. F. Galliano, E. Galvanetto, S. Mischler, D. Landolt, Tribocorrosion behavior of plasma nitrided Ti-6A1-4V alloy in neutral NaCl solution. Surf. Coat Technol. 2001; 145 (1-3): 121-131.
29. N. Renevier, P. Collignon, H. Michel, T. Czerwiec, Low temperature nitriding of AISI 316L stainless steel and titanium in a low pressure arc discharge. Surf. Coat Technol. 1999;111(2-3): 128.
30. T.Bell, W.Bergman, J.Lanagan, PH. Morton, A.M.Staines, Microstructure and microhardness of gas nitrided surface layers in Ti-8Al-lMo-lV and Ti-10V-2Fe-3Al alloys Surf Eng. 1986; 2:133.
31. L. Xue, M.U. Islam, A.K. KouL W. Wallace, M. Bibby, Mater Manuf. Process. 1997;12 (5):799.
32. L. Xue, M.U. Islam, A.K. KouK W. Wallace, M. Bibby, Laser Gas Nitriding of Ti-6A1-4V Part 2: Characteristics of Nitrided Layers. Adv. Perform. Mater. 1997; 4:389-408.
33. S. Mridha, T.N. Baker, Effects of nitrogen gas flow rates on themicrostructure and properties of laser-nitrided IMI318 titanium alloy (Ti-4V-6A1). J. Mater. Process. Technol. 1998; 77 (1-3):115-121.
34. Yue He, Jizhong Zhang. Wenqing Yao, Dexing Li, Xu Teng. Effect of temperature on residual stress and mechanical properties of Ti films prepared by both ion implantation and ion beam assisted deposition. Applied Surface Science, 2009; 255(8): 4484-4490.
35. Stefan Krischok, Claudia Blank. Michael Engel. Richard Gutt. Gernot Ecke, Jens Schawohl. Lothar SpieB. Frank Schrempel. Gerhard Hildebrand. Klaus Liefeith. Influence of ion implantation on titanium surfaces for medical applications. Surface Science, 2007; 601(18): 3856-3860.
36. Takeo Nakano. Ken'ichiroh Hoshi. Shigeru Baba. Effect of background gas environment on oxygen incorporation in TiN films deposited using UHV reactive magnetron sputtering. Vacuum. 2008; 83(3): 467-469
37. Stefan Wrehde, Marion Quaas. Robert Bogdanowicz, Hartmut Steffen. Harm Wulff, Rainer Hippler. Optical and chemical characterization of thin TiNx films deposited by DC-magnetron sputtering. Vacuum. 2008; 82(10): 1115-1119
38. Sankar Moni Borah. Arup Ratan Pal. Heremba Bailung, Joyanti Chutia. Optimization of plasma parameters for high rate deposition of titanium nitride films as protective coating on bell-metal by reactive sputtering in cylindrical magnetron device. Applied Surface Science, 2008;254(18): 5760-5765
39. N. Ichimiya, Y Onishi, Y Tanaka. Properties and cutting performance of (Ti,V)N coatings prepared by cathodic arc ion plating. Surface and Coatings Technology, 2005;200(5-6): 1377-1382.
40. Qiang RU. Shejun HU. Nacan HUANG Lingzhi ZHAO, Xiuli QIU. Xianqi HU. Properties of TiAlCrN coatings prepared by vacuum cathodic arc ion plating. Rare Metals, 2008;27(3): 251-256
41. M. Uchida, N. Nihira, A. Mitsuo, K. Toyoda. K. Kubota, T. Aizawa. Frictionand wear properties of CrAlN and CrVN films deposited by cathodic arc ion plating method. Surface and Coatings Technology, 2004;(177-178)30: 627-630
42. A. Mubarak, E. Hamzah, M.R.M. Toff. Study of macrodroplet and growth mechanisms with and without ion etchings on the properties of TiN coatings deposited on HSS using cathodic arc physical vapour deposition technique. Materials Science and Engineering: A, 2008;474(l-2):236-242
43．多弧离镀技术与应用，张钧，赵彦辉编著，冶金工业出版社，北京，2007第1版，p12．
44. I. Shishkovsky, Yu. Morozov, I. Yadroitsev, I. Smurov. Titanium and Aluminum Nitride Synthesis via layer by layer LA-CVD. Applied Surface Science, In Press, Accepted Manuscript, Available online 22 April 2009.
45. John A.T Norman, Melanie Perez, Stefan E. Schulz, Thomas Waechtler. New precursors for CVD copper metallization. Microelectronic Engineering, 2008;85(10): 2159-2163
46. K.W. Chen, Y.L. Wang, L. Chang, F.Y Li, GJ. Hwang. Effects of plasma treatment in the tungsten process for chemical vapor deposition titanium nitride barrier film beyond nanometer technology. Thin Solid Films, 2006;498(l-2):64-69
47. Yuzuru Ogura, Chikako Kobayashi, Yoshiyuki Ooba, Naoki Yahata, Hitoshi Sakamoto. Low temperature deposition of metal films by metal chloride reduction chemical vapor deposition. Surface and Coatings Technology, 2006;200(10):3347-3350
48．表面科学与技术，姚寿山，李戈扬，胡文彬，北京：机械工业出版社，2005年第1版，p263-267．
49.W J. Meng，GL.Eesley. Growth and mechanical anisotropy of TiN thin films [J]. Thin Solid Films, 1995(271): 108-116.
50.N. Popovic, Z. Bogdanov, B. Goncic, S. Zec, Z. Rakocevic, M. Zlatanovic, D. Perusko. TiN thin films deposited by ion beam sputtering effects ofosited by pulsed direct current magnetron sputtering. Thin Solid Films, 2008;516(21):7294-7298
52. E. Bemporad, M. Sebastiani, C. Pecchio, S. De Rossi. High thickness Ti TiN multilayer thin coatings for wear resistant applications. Surface and Coatings Technology, 2006;201(6):2155-2165
53. F. Borgioli. E. Galvanetto. F.P. Galliano. T. Bacci. Sliding wear resistance of reactive plasma sprayed Ti-TiN coatings. Wear, 2006;260(7-8): 832-837
54. Wenran Feng. Dianran Van, Jining He, Xiangzhi Li. Vanchun Dong. Reactive plasma sprayed TiN coating and its tribological properties. Wear, 2005;258(5-6):806-811
55. J. M. Lackner, W. Waldhauser, R. Berghauser, R. Ebner, B. Major. T. Schoberl. Structural, mechanical and tribological investigations of pulsed laser deposited titanium nitride coatings. Thin Solid Films. 2004; (453-454): 195-202
56. P.J. Kelly, T. vom Braucke, Z. Liu. R.D. ArnelL E.D. Doyle. Pulsed DC titanium nitride coatings for improved tribological performance and tool life. Surface and Coatings Technology, 2007;202(4-7):774-780
57. Hendry J A, Pilliar R M. The fretting corrosion resistance of PVD surface-modified orthopedic implant alloys. J Biomed Mater Res, 2001; 58(2): 156-166.
58. Deyuan Zhang. Weijun Zeng. Zhenjun Zi. Paul K.Chu. Corrosion resistance of TiN coated biomedical nitinol under deformation. Materials Science and Engineering: C. In Press, Corrected Proof, Available online 31 December 2008.
59. Starosvetsky D, Gotman I. Corrosion behavior of titanium nitride coated Ni-Ti shape memory surgical alloy. Biomaterials. 2001; 22(13): 1853-1859.
60．周雅彬，米乃元，李彦，滕伟，范丹妮．氮化钛涂层对牙科合金析出金属离子的影响,中山大学学报（医学科学版）2003; 24(3): 295-297.
61. Wataha J C. Biocompatibility of dental casting alloys: A review. J Prosthet Dent, 2000, 83(2): 223-234.
62. Bordji K, Jouzeau JY, Mainard D, etc. Cytocompatibility of Ti-6A1-4V and Ti-5Al-2.5Fe alloys according to three surface treatments, using human fibroblasts and osteoblasts. Biomaterials, 1996; 17(9): 929-940.
63. Chia-Chi Chien. Kuan-Ting Liu, Jenq-Gong Duh. Kuo-Wei Chang, Kwok-Hung Chung, Effect of nitride film coatings on cell compatibility. Dental materials, 2008; 24: 986-993.
64. Her-Hsiung Huang, Chu-Hui Hsu. Szu-Jung Pan, Ju-Liang He, Chun-Cheng Chen, Tien-Ling Lee, Corrosion and cell adhesion behavior of TiN-coated and ion-nitrided titanium for dental applications. Applied Surface Science, 2005; 244: 252-256.
65. Dion I, Rouais F, Trut L, etc. TiN coating: surface characterization and haemocompatibility. Biomaterials, 1993; 14(3): 169-176.
66. Dion I, Roques X, More N, etc. Ex vivo leucocyte adhesion and protein adsorption on TiN. Biomaterials, 1993; 14(9):712-719.
67. Mitamura Y, Hosooka K, Matsumoto T, etc. J Biomater Appl, 1989; 4(l):33-35.
68. B. Subramanian, M. Jayachandran. Electrochemical corrosion behavior of magnetron sputtered TiN coated steel in simulated bodily fluid and its hemocompatibility. Materials Letters 62 (2008) 1727-1730.
69.陈震,梁峥嵘,时光辉,韩栋伟.氮化钛膜对纯钛表面细菌黏附能力的影响.同济大学学报(医学版), 2008;28(1): 37-40.
70. Scarano A,Piattelli M. Bacterial adhesion on titanium nitride-coated and uncoated implants: an in vivo human study [J].J Oral Implantol, 2003; 29(2):80-85.
71. G Sovak, A Weiss, I Gotman, Osseointegration of Ti6A14V alloy implants coated with titanium nitride by a new method. J Bone Joint Surg (Britishivolume), 2000(2): 290-296.
72.郑晓辉,邓春富,杨彦昌.氮化钛—钛陶瓷复合体颌骨内种植的动物实验 研究.中国医科大学学报,1995;24(1):15-17
73. Pappas MJ, Makris G, Buechel FF. Titanium nitride ceramic film against polyethylene. A 48 million cycle wear test. Clin Orthop Relat Res, 1995; (317):64-70.
74. Rawlings RD, Robinson PB, Rogers PS. The durability of ceramic coated dental instruments. Eur J Prosthdont Restorat Denti. 1995; 3(5): 211-216
75. Rapisarda E, Bonaccorso A, Tripi TR, etc. The effect of surface treatments of nickel-titanium files on wear and cutting efficiency. Oral Medicine Oral Pathology Oral Radiology, Endodontics, 2000; 89(3): 363-368.
76. Schafer E. Effect of Physical Vapor Deposition on Cutting Efficiency of Nickel-Titanium Files. J Endod, 2002; 28(12): 800-802.
77. D. Nolan, S.W. Huang, V. Leskovsek, S. Braun. Sliding wear of titanium nitride thin films deposited on Ti-6A1-4V alloy by PVD and plasma nitriding processes. Surface and Coatings Technology, 2006;200(20-21): 5698-5705.
78.谢紫杰,朱景环.工业纯钛的离子渗氮.热处理,1998;3:21-23.
79. H.C. Man, Z.D. Cui, X.J. Yang, Analysis of laser gas nitrided titanium by X-ray photoelectron spectroscopy, Appl. Surf. Sci. 2002;199:293.
80. S.Malinov, A.Zhecheva, W.Sha, Proceedings of the 1 International Surface Engineering Congress and the 13 IFHTSE Congress, ASM International, Materials Park, OH,2003,p.344.
81.周锋,傅迎庆,高阳.热等离子束照射工业纯钛快速渗氮制备表面氮化层. 稀有金属材料与工程, 2007;36(Suppl2):728-730.
82. K.Wilsdorf, H.-J.Spies, in: Associazione Italiana di Metallurgia,11th Congress of the International Federation for Heat Treatment and Surface Engineering and the 4th ASM Heat Treatment and Surface Engineering Conference in Europe Proceedings, Italy, vol.1. 1998. p.351.
83. A. Zhecheva, S.Malinov, W.Sha, Surface gas nitriding of Ti-6A1-4V and Ti-6Al-2Sn-4Zr-2Mo-0.08Si alloys. Z. Metallk. 2003; 94(1): 19-24.
84. Waheed A. Badawy, Ahlam M. Fathi, Rabab M. El-Sherief, Sahar A. Fadl-Allah. Electrochemical and biological behaviors of porous titania (TiO2) in simulated body fluids for implantation in human bodies. Journal of Alloys and Compounds, 2009; 475(1-2): 911-916.
85. Olbrich W, Fessmann J, Kampschulte G, Ebberink J. Improved control of TiN coating properties using cathodic arc evaporation with a pulsed bias. Surf Coat TechnoL 1991; 49(1-3): 258-262.
86. Aharonov R R, Chhowala M, Dhar S etc. Factors affecting growth defect formation in cathodic arc evaporated coatings. Surf. Coat. Technol.1996; 82:334.
87. Meidong Huang, Guoqiang Lin, Yanhui Zhao, etc. Macro-particle reduction mechanism in biased arc ion plating of TiN. Surf. Coat. Technol. 2003;176:109-114.
88. Yanhui Zhao, Guoqiang Lin, Chuang Dong, etc. Experimental verification of the physical model for droplet cleaning in pulse-bias arc ion-plating. J. Mater. Sci. TechnoK 2005;21(3): 423-426.
89. Oliver W C, Pharr G M Measurement of Hardness and Elastic Modulus by Instrumented Indentation: Advances in Understanding and Refinements to Methodology [J]J Mater Res, 2004;19:3-20.
90. Oliver W C, Pharr GM. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J Mater Res[J], 1992,7(6): 1564-1583.
91. Moody N R, Strojny A, Medlin D L, et al. Substrate composition effects on the interfacial fracture of tantalum nitride films [J]. Journal of Materials Research, 1999; 14(6): 2306-2313.
92. Doerner MF, Nix W D. A method for interpreting the data from depth-sensing indentation instruments J Mater Res [J], 1986;l:601-609.
93. KOHLSCHEEN J, STOCK H, MAYR P. Chemical bonding in magnetron sputtered TiNx coatings and its relation to diamond turnability. [J] Surface and Coatings Technology, 2001;142-144: 992-998.
94．冷永祥’孙鸿，徐禄祥，等．等离子体浸没离子注入和沉积技术制备TiN薄膜研究．真空科学与技术,2003；23(4)：295-225．
95. Ph. Roquiny, F. Bodart, GTerwagne. Color control of titanium nitride coatings produced by reactive magnetron sputtering at temperature less than 100℃. [J] Surface and Coatings Technology, 1999; 116-119: 278-283.
96. J. Stallard, S. Poulat, D.G Teer. The study of the adhesion of a TiN coating on steel and titanium alloy substrates using a multi-mode scratch tester. Tribology International, 2006;39:159-166.
97．周顺，严一心．脉冲真空电弧离子镀沉积类金刚石薄膜的结构和力学性能研究．西安工业学院学报，2004；24(4)：307-310．
98．姚江武主编．现代口腔色彩学．第1版，厦门大学出版社,2000,30-31．
99. Hanawa T, Asami K, Asaoka K. Repassivation of titanium and surfaceoxide film regenerated in stimulated bioliquid. J Biomed Mater Res, 1998;40:530-538.
100.Wataha JC, Lockwood PE, Noda M, Nelson SK, Mettenburg DJ. Effect oftoothbrushing on the toxicity of casting alloys. J Prosthet Dent, 2002;87:94-98.
101.Fraleigh CM, Elhaney JHM, Heiser RA. Toothbrushing force study, J DentRes, 1967; 46: 209-214.