一氧化钛基金属陶瓷仿金材料的开发及相关机理研究
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摘要
仿金材料代替稀贵的黄金用于装饰，具有巨大的市场需求和广阔的应用前景。本文研制出的一氧化钛基金属陶瓷仿金新材料综合性能优良，克服了仿金Cu易变色、硬度低和TiN基金属陶瓷仿金材料制备难度大、价格昂贵的缺点。
采用XRD和EDS，详细研究了Ti、TiO_2固-固反应合成TiO_x的工艺，从理论上深入分析了固-固反应动力学机制及各因素对反应速度的影响。首次采用“机械活化-低温合成”工艺，并以TiH_2代替Ti为还原剂，极大促进了固-固合成反应，在较低温度下得到了O分布十分均匀的金黄色一氧化钛。不仅避免了Ti的高温挥发，保证了体系Ti、O量比的稳定，而且降低了TiO_x的合成成本。
运用量子化学、晶体场及化学成键理论，深入分析了中间化合物及一氧化钛的相对稳定性。Ti的外层电子结构、电离势、轨道分裂特性和YiO、Ti_2O_3歧化反应自由能计算结果，证明一氧化钛具有较高的稳定性。
利用XRD辅以EDS，比较准确地确定出非化学计量TiO_x的氧指数范围：x=0.828±0.002～1.185±0.004。设计、制造了固体表面颜色测量装置，首次利用分光光度法详细研究了TiO_x的颜色及其随氧指数的变化规律。通过不同氧指数TiO_x、24KAu波长-反射率曲线及TiO_x与24KAu间色度差的测定，确定出颜色最接近24KAu的TiO_x氧指数范围为1.14～1.16，该范围内TiO_x与24KAu间的色度差为仿金Cu或TiN的60％左右。量子化学理论分析表明，一氧化钛发生电荷跃迁的能量大于可见光光子能量，且不存在n→n或л→л跃迁机制，而其电子的d-d跃迁是自旋允许的，一氧化钛的金黄色是Ti~(2+)外层电子发生d-d跃迁的结果。随TiO_x氧指数增大，O~(2-)场强度增加，造成分裂后的Ti~(2+)的3d轨道间能量差增加，引起TiO_x金黄色逐渐向偏红方向转变。
一氧化钛在大气、家庭气氛、泥土、人工汗液、K金腐蚀剂、NaCl溶液、浓氨水中的抗变色、耐腐蚀实验结果表明，其抗变色、耐腐蚀性能远优于仿金Cu、TiN基金属陶瓷仿金材料。一氧化钛在稀HCl和稀H_2SO_4中腐蚀十分缓慢，不变色。一氧化钛的颜色、抗变色等性能研究，充分肯定了其用作高档仿金材料的可行性，为开发一氧化钛的应用新领域提供了实验和理论依据。
首次采用高温座滴法详细研究了Fe、Co、Ni、Cu、Al、Si、Mn、FeCr、Fe-C在TiO_(1.0)、TiO_(1.14)上的润湿性，借助XRD和EDS对润湿界面和润湿机理进行了深入分析，为一氧化钛陶瓷粘结相的开发和金属／陶瓷涧湿性研究提供了原始资料和理论依据。Fe、Co、Ni、Al、Mn与TiO_x中的“Ti”(而不单是O)的亲和力和相互作用，对它们在YiO_x上
中南大学博士学位论文
中文摘要
的润湿性和界面结合强度产生了很大影响;Al/TIO、间化学亲和力强，且存在界面反应，
但其润湿性却很差;C讨TIOx、51/TIOx润湿虽然都存在相间溶解，但C口TIOx润湿性较S订TIOx
却相差甚远。这些现象在金属/陶瓷润湿性研究中应引起重视。
FeCr合金耐蚀性好，但与TIO、润湿性不良、界面结合强度差。本研究通过添加合
金元素使其接触角降至30“以下，并得到了坚固的界面结合，开发出在TIO、上润湿性
好、界面结合强度高、耐蚀性强、热膨胀系数匹配的FeCr困i)si合金粘结相。借助XRD、
SEM、EDS等分析方法，通过界面相成分分析、对界面处元素的面扫描、线扫描，深入
研究了合金元素的分布及其改善润湿、形成坚固界面结合的作用机理。从热力学、动力
学和量子化学角度分析了元素Si与TIO、的界面作用。
运用DTA和XRD，分析了Ti01.14一FeCr困i)Si在烧结过程中粘结相的合金化及其润
湿过程，确定了体系液相的出现和形成温度。通过对烧结体强度、密度的测量，确定了
不同成分的金属陶瓷粘结相中最低Si含量要求。研究了原始粉末粒度、烧结工艺、粘结
相含量对金属陶瓷组织与性能的影响。随着粘结相含量增加，金属陶瓷组织细化，强、
韧性提高，但其金黄色饱和度降低(粘结相含量12%以下，其颜色优于仿金Cu和TIN)。
利用SEM对金属陶瓷的断口进行了研究，发现粘结相的加入对一氧化钦陶瓷起到了明
显的增韧作用，其断裂为脆性解理断裂和塑性相韧性断裂并存。粘结相中si、Cr的存在
使金属陶瓷的高温抗氧化性能有所提高。详细研究了TIOI.，4一FeCr(Ni)si金属陶瓷的性能，
探讨了其晶粒长大和塑性相增韧机理。最后在自行设计的装置上测定了
Tiol.14一FeCr(N 1)51导电率，证明了其采用电火花线切割加工的可能性。
研制出的TIOI.14--8%FeCr(Ni)Si仿金材料，横向抗弯强度达到600MPa左右，具有较
高的硬度(Hvgoo左右)和韧性(可达9.3MNm一3与，较低的密度，颜色优于仿金cu和
TIN，抗变色性能较仿金Cu、TIN基金属陶瓷仿金材料高几十至几百倍。是一种高档次
的仿金材料。
Imitated gold used for decorative purpose instead of rare and costly gold possesses of large market demand and widest application foreground. TiO-based cermet imitated gold with excellent integrative properties, developed in this research, avoided discoloration, low hardness of Cu-based imitated gold and difficulty in production, costliness of high quality cermet imitated gold based on TiN.
The technology of TiOx synthesis by reaction between solid Ti and TiOi was studied in detail with the aid of XRD and EDS. Penetrating theory analyses on mechanisms of the reaction kinetics and influence of every factor on the reaction speed were made. The synthesis reaction between solid phases was greatly improved and golden TiO with very well-proportioned O distribution was obtained in lower temperature for the first time by using "mechanical activation-lower temperature synthesis" technology, Titk used as reducer instead of Ti. Not only the volatilization of Ti was avoided, the fixedness of Ti/O get guarantee but also the cost was reduced.
The relative stabilities of intermediate compounds and titanium monoxide were examined deeply with quantum chemistry, crystal field and chemical bond theory. Outer layer electron structure, ionization potentials and track division of Ti and AG?of the dismutation reactions of TiO and Ti2O3 proved that titanium monoxide was stable.
The range of oxygen index of nonstoichiometric titanium monoxide was determined accurately, TiO o.828?.002-TiO 1.185.?.004, by means of XRD assisted of EDS. A device for solid surface color measuring was designed. It was the first time that the color characteristics of TiOx with different "x" value and its changing law along with the oxygen index were studied in detail with spectrophoto-method. The range of the oxygen index, with which TiOx had the closest color with 24KAu was determined, ranged from 1.14 to 1.16, by determinations of wavelength-reflection rate curves of TiOx and 24KAu, chromatisms between TiOx and 24KAu. The chromatisms of TiOx when x was within this range was about 60% of the ones of Cu-based imitated gold or TiN. Theoretical examination with quantum chemistry views indicated that the energy needed by taking charge transition of titanium monoxide was more than that of the photons of visible light, there was no n-n* or - * transition in titanium monoxide. The golden color of titanium mo
noxide was created because of the d-d transitions of outer layer electrons of Ti2+. Its color turned to golden with slightly red along with increasing of the energy difference among 3d tracks of Ti2+ because of strengthening of O2- field caused by TiOx's oxygen index increase.
Anti-discoloration and anti-corrosion experiment results of titanium monoxide in air, family atmosphere, mud, artificial sweat, etch used for KAu, NaCl solution, thick ammonia indicated that it was far superior to Cu-based imitated gold and TiN-based cermet imitated gold in anti-discoloration
and anti-corrosion properties. It was etched very slowly in thin HC1 and H2.SO4 solution and its color did not change. Studies of the color and anti-discoloration etc. of titanium monoxide confirmed the possibility to be used as high-grade imitated gold, and offered experiment and theoretical basis for developing new application fields of titanium monoxide.
The wettabilities of Fe, Co, Ni, Cu, Al, Si, Mn, FeCr and Fe-C on TiOi.o and TiOi.w were studied in detail for the first time using high-temperature sessile drop method. Their wetting interfaces and wetting mechanisms were deeply examined with aid of XRD and EDS. Source materials and theoretical basis were offered for development of the binding alloy of titanium monoxide and wettibility study of metal/ceramic. The affinity and action between Ti(not only O) in TiOx and Fe, Co, Ni, Al or Mn remarkably influenced their wettabilities on TiOx and the interface binding strength. The chemical affinity between Al and TiOx was strong and the interface reactions existed, but wettability of Al on TiOx was very poor. Dissolution between phases existed
采用XRD和EDS，详细研究了Ti、TiO_2固-固反应合成TiO_x的工艺，从理论上深入分析了固-固反应动力学机制及各因素对反应速度的影响。首次采用“机械活化-低温合成”工艺，并以TiH_2代替Ti为还原剂，极大促进了固-固合成反应，在较低温度下得到了O分布十分均匀的金黄色一氧化钛。不仅避免了Ti的高温挥发，保证了体系Ti、O量比的稳定，而且降低了TiO_x的合成成本。
运用量子化学、晶体场及化学成键理论，深入分析了中间化合物及一氧化钛的相对稳定性。Ti的外层电子结构、电离势、轨道分裂特性和YiO、Ti_2O_3歧化反应自由能计算结果，证明一氧化钛具有较高的稳定性。
利用XRD辅以EDS，比较准确地确定出非化学计量TiO_x的氧指数范围：x=0.828±0.002～1.185±0.004。设计、制造了固体表面颜色测量装置，首次利用分光光度法详细研究了TiO_x的颜色及其随氧指数的变化规律。通过不同氧指数TiO_x、24KAu波长-反射率曲线及TiO_x与24KAu间色度差的测定，确定出颜色最接近24KAu的TiO_x氧指数范围为1.14～1.16，该范围内TiO_x与24KAu间的色度差为仿金Cu或TiN的60％左右。量子化学理论分析表明，一氧化钛发生电荷跃迁的能量大于可见光光子能量，且不存在n→n或л→л跃迁机制，而其电子的d-d跃迁是自旋允许的，一氧化钛的金黄色是Ti~(2+)外层电子发生d-d跃迁的结果。随TiO_x氧指数增大，O~(2-)场强度增加，造成分裂后的Ti~(2+)的3d轨道间能量差增加，引起TiO_x金黄色逐渐向偏红方向转变。
一氧化钛在大气、家庭气氛、泥土、人工汗液、K金腐蚀剂、NaCl溶液、浓氨水中的抗变色、耐腐蚀实验结果表明，其抗变色、耐腐蚀性能远优于仿金Cu、TiN基金属陶瓷仿金材料。一氧化钛在稀HCl和稀H_2SO_4中腐蚀十分缓慢，不变色。一氧化钛的颜色、抗变色等性能研究，充分肯定了其用作高档仿金材料的可行性，为开发一氧化钛的应用新领域提供了实验和理论依据。
首次采用高温座滴法详细研究了Fe、Co、Ni、Cu、Al、Si、Mn、FeCr、Fe-C在TiO_(1.0)、TiO_(1.14)上的润湿性，借助XRD和EDS对润湿界面和润湿机理进行了深入分析，为一氧化钛陶瓷粘结相的开发和金属／陶瓷涧湿性研究提供了原始资料和理论依据。Fe、Co、Ni、Al、Mn与TiO_x中的“Ti”(而不单是O)的亲和力和相互作用，对它们在YiO_x上
中南大学博士学位论文
中文摘要
的润湿性和界面结合强度产生了很大影响;Al/TIO、间化学亲和力强，且存在界面反应，
但其润湿性却很差;C讨TIOx、51/TIOx润湿虽然都存在相间溶解，但C口TIOx润湿性较S订TIOx
却相差甚远。这些现象在金属/陶瓷润湿性研究中应引起重视。
FeCr合金耐蚀性好，但与TIO、润湿性不良、界面结合强度差。本研究通过添加合
金元素使其接触角降至30“以下，并得到了坚固的界面结合，开发出在TIO、上润湿性
好、界面结合强度高、耐蚀性强、热膨胀系数匹配的FeCr困i)si合金粘结相。借助XRD、
SEM、EDS等分析方法，通过界面相成分分析、对界面处元素的面扫描、线扫描，深入
研究了合金元素的分布及其改善润湿、形成坚固界面结合的作用机理。从热力学、动力
学和量子化学角度分析了元素Si与TIO、的界面作用。
运用DTA和XRD，分析了Ti01.14一FeCr困i)Si在烧结过程中粘结相的合金化及其润
湿过程，确定了体系液相的出现和形成温度。通过对烧结体强度、密度的测量，确定了
不同成分的金属陶瓷粘结相中最低Si含量要求。研究了原始粉末粒度、烧结工艺、粘结
相含量对金属陶瓷组织与性能的影响。随着粘结相含量增加，金属陶瓷组织细化，强、
韧性提高，但其金黄色饱和度降低(粘结相含量12%以下，其颜色优于仿金Cu和TIN)。
利用SEM对金属陶瓷的断口进行了研究，发现粘结相的加入对一氧化钦陶瓷起到了明
显的增韧作用，其断裂为脆性解理断裂和塑性相韧性断裂并存。粘结相中si、Cr的存在
使金属陶瓷的高温抗氧化性能有所提高。详细研究了TIOI.，4一FeCr(Ni)si金属陶瓷的性能，
探讨了其晶粒长大和塑性相增韧机理。最后在自行设计的装置上测定了
Tiol.14一FeCr(N 1)51导电率，证明了其采用电火花线切割加工的可能性。
研制出的TIOI.14--8%FeCr(Ni)Si仿金材料，横向抗弯强度达到600MPa左右，具有较
高的硬度(Hvgoo左右)和韧性(可达9.3MNm一3与，较低的密度，颜色优于仿金cu和
TIN，抗变色性能较仿金Cu、TIN基金属陶瓷仿金材料高几十至几百倍。是一种高档次
的仿金材料。
Imitated gold used for decorative purpose instead of rare and costly gold possesses of large market demand and widest application foreground. TiO-based cermet imitated gold with excellent integrative properties, developed in this research, avoided discoloration, low hardness of Cu-based imitated gold and difficulty in production, costliness of high quality cermet imitated gold based on TiN.
The technology of TiOx synthesis by reaction between solid Ti and TiOi was studied in detail with the aid of XRD and EDS. Penetrating theory analyses on mechanisms of the reaction kinetics and influence of every factor on the reaction speed were made. The synthesis reaction between solid phases was greatly improved and golden TiO with very well-proportioned O distribution was obtained in lower temperature for the first time by using "mechanical activation-lower temperature synthesis" technology, Titk used as reducer instead of Ti. Not only the volatilization of Ti was avoided, the fixedness of Ti/O get guarantee but also the cost was reduced.
The relative stabilities of intermediate compounds and titanium monoxide were examined deeply with quantum chemistry, crystal field and chemical bond theory. Outer layer electron structure, ionization potentials and track division of Ti and AG?of the dismutation reactions of TiO and Ti2O3 proved that titanium monoxide was stable.
The range of oxygen index of nonstoichiometric titanium monoxide was determined accurately, TiO o.828?.002-TiO 1.185.?.004, by means of XRD assisted of EDS. A device for solid surface color measuring was designed. It was the first time that the color characteristics of TiOx with different "x" value and its changing law along with the oxygen index were studied in detail with spectrophoto-method. The range of the oxygen index, with which TiOx had the closest color with 24KAu was determined, ranged from 1.14 to 1.16, by determinations of wavelength-reflection rate curves of TiOx and 24KAu, chromatisms between TiOx and 24KAu. The chromatisms of TiOx when x was within this range was about 60% of the ones of Cu-based imitated gold or TiN. Theoretical examination with quantum chemistry views indicated that the energy needed by taking charge transition of titanium monoxide was more than that of the photons of visible light, there was no n-n* or - * transition in titanium monoxide. The golden color of titanium mo
noxide was created because of the d-d transitions of outer layer electrons of Ti2+. Its color turned to golden with slightly red along with increasing of the energy difference among 3d tracks of Ti2+ because of strengthening of O2- field caused by TiOx's oxygen index increase.
Anti-discoloration and anti-corrosion experiment results of titanium monoxide in air, family atmosphere, mud, artificial sweat, etch used for KAu, NaCl solution, thick ammonia indicated that it was far superior to Cu-based imitated gold and TiN-based cermet imitated gold in anti-discoloration
and anti-corrosion properties. It was etched very slowly in thin HC1 and H2.SO4 solution and its color did not change. Studies of the color and anti-discoloration etc. of titanium monoxide confirmed the possibility to be used as high-grade imitated gold, and offered experiment and theoretical basis for developing new application fields of titanium monoxide.
The wettabilities of Fe, Co, Ni, Cu, Al, Si, Mn, FeCr and Fe-C on TiOi.o and TiOi.w were studied in detail for the first time using high-temperature sessile drop method. Their wetting interfaces and wetting mechanisms were deeply examined with aid of XRD and EDS. Source materials and theoretical basis were offered for development of the binding alloy of titanium monoxide and wettibility study of metal/ceramic. The affinity and action between Ti(not only O) in TiOx and Fe, Co, Ni, Al or Mn remarkably influenced their wettabilities on TiOx and the interface binding strength. The chemical affinity between Al and TiOx was strong and the interface reactions existed, but wettability of Al on TiOx was very poor. Dissolution between phases existed
引文
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