摘要
稀土在硬质合金中定向迁移与在合金烧结体表面的富集现象在国际上尚未见其他类似报道。本课题组的前期研究主要集中在稀土独立掺杂WC-Co合金烧结过程中稀土的表面富集条件、富集形式与富集机理。前期研究结果表明,烧结过程中稳定存在于合金内部的高活性稀土在一定服役条件下可以向合金工具工作表面产生定向迁移,在工作表面原位形成Ln2O2S(Ln:稀土)薄膜,从而明显改善合金使用性能。本研究主要包括以下三个方面:RE(RE:特指以La、Ce为主体成分,含Pr、Nd的高活性混合稀土)在Cr/V-RE联合掺杂WC-Co合金烧结过程中的定向迁移行为;La在Cr/V-La2O3联合掺杂WC-Co合金烧结过程中的定向迁移行为以及WC-Co合金烧结体表面稀土弥散相形成机理及其相成份、相结构影响机理与功能作用。本研究的主要目的是通过对稀土在Cr/V联合掺杂WC-Co合金烧结过程中的定向迁移行为与机理研究,实现对稀土在硬质合金中定向迁移行为的有效控制。因La/Ce原子与W/Co原子的原子半径相差29.36~48.97%,如何激活与控制稀土在硬质合金烧结过程中的定向迁移行为不仅具有重要的科学意义,而且对稀土在硬质合金中作用机理研究、稀土改善硬质合金使用性能机理研究以及(自润滑)功能导向型高性能超细硬质合金的开发均具有重大意义。
选用RE-Co预合金粉与高纯纳米La2O3作为稀土掺杂原料;利用扫描电镜、能谱分析仪、X射线衍射仪与光学显微镜,采用合金烧结体表面观察与分析法,结合合金内部组织结构观察与分析、合金热力学分析等手段,研究了稀土在Cr/V联合掺杂WC-Co合金烧结过程中的定向迁移行为与机理。
研究结果表明,对Cr/V-RE联合掺杂WC-Co合金,烧结过程中合金中的稀土可以产生定向迁移,在合金中呈弥散分布的稀土相中的部分La、Ce、Pr、Nd原子可以脱离其原始结合状态,通过定向迁移在合金烧结体表面形成新的稀土弥散相。对Cr//V-La2O3联合掺杂WC-Co合金,当合金为WC+β+η三相组织时,烧结过程中合金中的La可以产生定向迁移,在合金烧结体表面形成稀土弥散相。无论是以液态形式迁移还是以固态形式迁移,稀土原子/离子的定向迁移必须在合金内部体系(存在高活性游离C原子)与外部环境(烧结炉内气氛中存在S、O等微量杂质元素)同时满足一定条件下才能发生,因此稀土原子/离子的迁移行为是可控的。同时满足在Co中具有较高溶解度以及高碳碳化物分解为低碳碳化物激活能低的碳化物均具有高活性游离C原子供给能力,因而可成为稀土迁移活性的激活基元。由于WC骨架结构的存在,即使稀土原子以液态形式迁移,也不可避免遇到WC迁移壁垒,因此稀土的原子极化是稀土原子/离子穿越WC晶格从而产生快速迁移的必要条件。存在稀土原子极化的条件下,由于La系收缩效应以及Ce4+、Pr4+离子的存在,当原子尺寸因素成为迁移速度的主要影响因素时,与La比较,Ce、Pr、Nd具有快速迁移优势。WC-Co合金中稀土原子产生极化与定向迁移所需的激活能与掺杂稀土的原始活性有关。当WC-Co合金含碳量正常时,Cr、V高碳碳化物分解为低碳碳化物的驱动力降低,La2O3中La的迁移活性难以得到激发。随烧结炉内气氛中S相对逸度的增加,合金烧结体表面依次可形成LnCoO3、Ln2O2S、Ln2S3等稀土弥散相。因Ce2O2S与Ce2S3的ΛfGVO(单位体积生成自由能变化)明显较相应的La2O2S与La2S3低,在Cr/V-RE联合掺杂WC-Co合金的烧结过程中更有利于Ce2O2S或Ce2S3型晶体结构稀土弥散相的形成。在体系中S相对逸度较高的条件下,S向合金内部的迁移速度增加。与La、Pr、Nd相比,因Ce更易与S形成化合物,随着S原子的向合金内部迁移以及S原子与部分Ce原子的优先结合,Ce较La的定向迁移优势被削减,Ce原子的迁移总量降低。与此同时,迁移通道的开启有利于加快La的定向迁移速度,因此导致了合金烧结体表面高La/Ce比Ln2S3弥散相的形成。合金表面原位形成的稀土弥散相具有较好的耐磨性,与合金基体具有较好的结合强度,能赋予合金自润滑功能与高耐热性能。
The directional migration and enrichment phenomena of Ln (Ln: rare earth) on the sinter skin of Ln doped cemented carbide have been discovered for the first time by our research group. Similar report has not appeared worldwide. During the early stage research, we mainly concentrated on the study of the existing form of Ln both in the alloy and on the sinter skin, the conditions and mechanism of the enrichment of Ln on the sinter skin of Ln solo doped WC-Co alloy. It was shown that a Ln2O2S film can be formed in situ on the working faces of the as-sintered cemented carbide tool under some kind of service condition, when Ln can be confined in the alloy during the sintering process. As a result, the performance of the alloy can be effectively improved. This research mainly focus on the following aspects:the directional migration behavior of La, Ce, Pr and Nd in Cr/V-RE jointly doped WC-Co alloy during the sintering process, where RE represents mischmetal containing La, Ce, Pr and Nd with La and Ce as the main composition and is added in the form of RE-Co alloy; the directional migration behavior of La in the Cr/V-La2O3 jointly doped WC-Co alloy during the sintering process;the mechanisms for the formation of the Ln containing dispersed phase(s) and for the variation of the phase composition and structure, as well as the self lubrication function of the Ln containing phases. This research is aimed at the full controlling of the migration behavior of rare earth in the alloy. As is known, there are huge difference in the atomic radius between La/Ce and W/Co,29.36~48.97%. Therefore, how to stimulate and get control over the directional migration behavior is not only of great scientific significance, but also very important in the study of the mechanisms for the effect of Ln on the microstructure and properties, the performance improvement of cemented carbide in service, as well as the development of the self-lubricated function oriented ultrafine cemented carbide with high performance.
Mischmetal and cobalt pre-alloyed powder with high activity, and high pure nano sized La2O3 with low activity were selected as Ln doping raw materials. SEM, EDS, X-ray diffractometer and optical microscope were used as the observation measures. The sinter kin observation and analysis method, coped with the inner microstructure observation and analysis, as well as the thermodynamic analysis were used in the study of the Ln atoms/ions directional migration behavior and the related mechanism.
It is shown that during the sintering process of Cr/V-RE jointly doped WC-Co alloy, La, Ce, Pr and Nd can migrate directionally, the Ln containing dispersed phase (M) in the alloy with WC+β+M microstructure is thermodynamically unstable and part of the La, Ce, Pr and Nd atoms can reunion on the sinter skin, forming in situ a new Ln containing dispersed phase. During the sintering process of Cr/V-La2O3 jointly doped WC-Co alloy with WC+β+ηmicrostructure, La can migrate directionally, forming in site La containing dispersed phase. Whether the Ln atoms/ions is in the form of liquid or solid, the directional migration of Ln atoms/ions must meet both the internal and external environment conditions, i.e. there exist free carbon atoms with high activity in the alloy and there exist S and O impurity atoms in the sintering atmosphere. Therefore, the directional migration behavior of Ln atoms/ions is controllable. Carbide with high solubility in cobalt and with lower stimulation energy for the decomposition of high carbon type into low carbon type can be the stimulation primitive unit of the migration activity of Ln atoms/ions for its offering ability of free carbon atoms with high activity. Because of the existence of WC skeleton structure and the resulted migration barrier, even if the migration of Ln atoms is in the state of liquid, the polarization of Ln atoms is the requisite for the migration of Ln atoms through WC lattice and the resulted fast migration. Under the situation of the polarization, compared with La, Ce and Pr and Nd have the advantage of fast migration when the atomic size factor becomes the controlling one for the migration, because of the lanthanide contraction and the existence of the Ce4+ and Pr4+ irons. The activation energies of the Ln atoms polarization and migration are related to their original activity. For La2O3 doped WC-Co alloy with normal carbon content and the resulted WC+βtwo phase structure, the driving force for the decomposition of Cr3C2 or/and VC into the lower carbon type is decreased;as a result, the migration activity of La ions cannot be activated. With the increasement of the fugacity of S in the sintering atmosphere, LnCoO3, Ln2O2S and Ln2S3 dispersed phase(s) can be formed in turn on the sinter skin of Ln-Cr/V unitedly doped WC-Co alloy. Compared with the values ofΔfGv0 of La2O2S and La2S3, the respective ones of Ce2O2S and Ce2S3 are lower; therefore, the crystal structure of Ln2O2S and Ln2S3 on the sinter skin of Cr/V-RE jointly doped WC-Co alloy are Ce2O2S and Ce2S3 type, respectively. In the situation of relatively higher fugacity of S in the sintering atmosphere, the migration speed of S atoms into the alloy can be accelerated. As a result, parts of the Ce atoms in the alloy combine preferentially with the S atoms for the lower Gibbs free energy compared with the ones of La, Pr and Nd. The advantage of the migration of Ce atoms is thereby cut down and the migration total amount of Ce atoms is deduced. In the mean while, the opening of the migration channel facilitates the fast migration of La atoms; therefore, the Ln2S3 dispersed phase with higher La/Ce ratio than the one in RE-Co powder can be formed. There is good combining strength between the Ln containing dispersed phase and the WC+βmatrix and good wear resistance of Ln containing dispersed phase. The formation of Ln containing dispersed phase on the skin, no mater it is in the form of LnCoO3, Ln2O2S or Ln2S3 can endow the alloy with self lubrication and high heat resistance functions.
引文
[1]Xu Chong-hai, Ai Xing, Huang Chuan-zhen. Research and development of rare-earth cemented carbides. International Journal of Refractory Metals and Hard Materials,2001,19:159-168
[2]羊建高,熊继,刘熠.稀土硬质合金的国内外研究综述.硬质合金,1993,10(1):46-49
[3]Walter Dubel, Walter Flurschutz, Rudolf Kohlermann. Hard metal alloy. U.K. patent, U.K.1077921,1967-08-02
[4]Walter Dubel, Walter Flurschutz, Rudolf Kohlermann. Hartmetall-legierung. German patent, Deutsche 1243399,1967-06-29
[5]井寄裕介,高桥纪雄.超硬合金.日本公开特许,昭59-41440,1984-03-07
[6]Chen Li-min, Lin Cheng-guang, Gerhard Groboth et al. Rare earth (RE) doped cemented carbides. P/M science and Technology Briefs,1999,1(5):11-15
[7]Akerman Jan, Ericson Thomas. Cemented carbide body with improved high temperature and thermomechanical propertyes. Europe patent, EP0819777A1, 1998-01-21
[8]Akerman Jan, Ericson Thomas. Cemented carbide body with improved high temperature and thermomechanical propertyes. USA patent, US 6126709, 2000-10-03
[9]Akerman Jan, Ericson Thomas. Cemented carbide body with improved high temperature and thermomechanical propertyes. USA patent, US 6423112, 2002-07-23
[10]Akerman Jan, Ericson Thomas. Cemented carbide body with improved high temperature and thermomechanical properties. US Patent,6,692,690, 2004-02-17
[11]汪有明,贺从训,赵伯琅.中国含稀土元素的硬质合金研究.中国钨业,1999,14(5-6):186-194
[12]张立,陈述,胡顺遂.稀土硬质合金中稀土添加形态与方式的探讨.硬质合金, 1996,13(2):117-120
[13]刘寿荣,梁福起,孙景WC-8Co硬质合金中稀土添加剂的作用.中国稀土学报,1998, 16(1):1-6
[14]龚润生,羊建高,陈军.稀土对硬质合金结构稳定性的影响.中南工业大学 学报,1995,26(4):498-501
[15]龚润生,羊建高,陈军.稀土硬质合金性能稳定性研究.中国有色金属学报,1995,5(2):120-123
[16]贺从训,汪有明,林晨光.含稀土的硬质合金的制造方法.中国专利,CN 1058233A,1992-01-29
[17]贺从训,林晨光,汪有明.含稀土的硬质合金的制造方法.中国专利,CN 1058234A,1992-01-29
[18]贺从训,林晨光,彭刚.含稀土的硬质合金的制造方法.中国专利,CN1058235A,1992-01-29
[19]He Congxun, Lin Chenguang, Wan Youmin. Process for preparing rare earth containing hard alloy. USA patent, US 5248328,1993-09-28
[20]张伟.稀土在YT15硬质合金中的应用.稀土硬质合金发展前景研讨会论文集.无锡:中国钨协硬质合金分会,1993.54-57
[21]李规华.稀土元素对硬质合金性能影响的初步探讨.东工科技, 1983,(2):20-24
[22]陈兆盈,李燕.稀土金属钇对WC-Ni硬质合金性能的影响.硬质合金,1984,(4):25-27
[23]李规华,严兰英,张鸿绪.稀土元素在硬质合金中的应用.粉末冶金技术,1986,4(1):25-29
[24]梁平,苏华.加稀土元素的硬质合金发展概括.硬质合金,1989,6(1):31-33
[25]罗重麟.含稀土元素的WC-TiC-Co硬质合金的显微组织.硬质合金,1989,6(1):26-30
[26]汪有明,贺从训,文献军.微量稀土添加剂在硬质合金中的行为初探.见:第四次全国硬质合金学术会议论文集.张家界:中国钨协硬质合金分会,1989.412-417
[27]邓秋元,罗重麟.稀土元素强化WC-TiC-Co硬质合金的机理.硬质合金,1990,7(1):8-13
[28]尤力平,刘少峰,贺从训.含钇WC-Co系硬质合金中钇相的电子显微镜研究.中国稀土学报,1990,8(4):371-374
[29]汤惠萍.稀土氧化物对硬质合金粘结相相变及机械性能的影响:[硕士学位论文].长沙:中南工业大学,1990
[30]罗重麟.稀土元素对硬质合金性能影响的研究.硬质合金,1991,8(2):12-19
[31]梁平,苏华.添加微量稀土钐对YT15R合金性能的影响.见:1991年全国粉末冶金学术会议论文集.桂林:中国机械工程学会粉末冶金分会,1991. 242-244
[32]罗重麟.稀土元素对YT5R硬质合金使用性能及显微结构的影响.见:1991年全国粉末冶金学术会议论文集.桂林:中国机械工程学会粉末冶金分会,1991.245-251
[33]俞学节.铼、铈对硬质合金组织和性能的影响.见:1991年全国粉末冶金学术会议论文集.桂林:中国机械工程学会粉末冶金分会,1991.236-241
[34]He Congxun, Wang Youmin, Lin Chengguang. Effects of rare earth on properties and structure of WC-8Co cemented carbide. Rare Metal,1991, 10(3):221-225
[35]刘莹.稀土元素对YW1硬质合金组织结构和机械性能的影响:[硕士学位论文].北京:北京科技大学,1992
[36]孙丽虹,贺从训,林晨光.稀土元素对YG8合金晶粒度的影响.中国稀土学报,1992,10(1):83-86
[37]Wang Ruikun, You Liping, Wang Xiaohua. Rare earth compounds in cemented carbide with trace rare earth additions. Rare Metals,1992,11(2):111-114
[38]Lin Chenguang. Composition, morphology and distribution of RE element containing phase in cemented carbide. Refractory Metals and Hard Materials, 1992,11(5):295-302
[39]Wang Ruikun, You Liping, Wang Xiaohua. Effect of Cerium on microstructures of hard alloys. Journal of Rare Earths,1993,11(1):36-40
[40]羊建高.稀土添加剂在WC-Co硬质合金中的作用与机理的研究:[硕士学位论文].长沙:中南工业大学,1993
[41]王兴庆.稀土在硬质合金中的作用.上海工业大学学报,1993,14(3):279-282
[42]袁逸,邬荫芳.稀土对钴基硬质合金的影响.硬质合金,1994,11(1):1-5
[43]羊建高,熊继.稀土添加剂对WC-Co硬质合金孔隙影响的研究.硬质合金,1994,11(1):10-13
[44]He Congxun, Wang Youmin, Lin Chenguang. Effects of rare earth elements on properties and structure of WC-14TiC-8Co cemented carbide. Journal of Rare Earths,1994,12(2):118-122
[45]熊继,羊建高,刘威香.添加稀土的YG8硬质合金拉丝模的研制.粉末冶金技术,1994,12(2):118-121
[46]贺从训,汪有明,林晨光.稀土元素对钨钻钛合金性能及组织结构的影响.中国稀土学报,1994,12(3):234-238
[47]李规华,严兰英,张鸿绪.YG6R系与硬质合金的研究.粉末冶金技术,1994,12(3):206-209
[48]熊继,羊建高,李懿.稀土对硬质合金中WC晶粒度和碳含量的影响.硬质合金,1994,11(3):134-137
[49]贺从训,汪有明,马福康.稀土在硬质合金中应用研究.硬质合金,1994,11(3):129-133
[50]阎开印,孟廷会,于军慧.添加稀土元素对硬质合金物理机械性能和切削性能的影响.西南交通大学学报,1995,30(1):46-51
[51]柳春林,颜邦明,范正康.添加稀土的新型矿用硬质合金研究.稀有金属与硬质合金,1995,(2):11-13
[52]袁逸,白元强,冯惠平.钇在钻基合金和硬质合金中的作用.粉末冶金技术,1995,13(2):93-98
[53]柳春林.添加微量稀土元素改善矿用硬质合金性能.硬质合金,1995, 12(3):140-143
[54]程剑兵,于启勋.添加稀土元素硬质合金刀具耐磨性研究.机械工程师,1995,(4):9-10
[55]郝春水,吴凤春.稀土硬质合金刀片切削性能.东北大学学报,1994, 15(5):499-502
[56]羊建高,熊继,郭幸华.YT15R硬质合金切削刀片使用寿命提高原因的探讨.第六次全国硬质合金学术会议论文集.昆明:中国钨协硬质合金分会,1995.287-292
[57]郝庆顺,李规华,严兰英.稀土元素对硬质合金烧结过程的影响.第六次全国硬质合金学术会议论文集.昆明:中国钨协硬质合金分会,1995.250-254
[58]梁平.YT15R硬质合金切削试验的研究.第六次全国硬质合金学术会议论文集.昆明:中国钨协硬质合金分会,1995,278-282
[59]汪新义,袁逸,邬荫芳.稀土对硬质合金粘结相的影响.第六次全国硬质合金学术会议论文集.昆明:中国钨协硬质合金分会,1995.246-249
[60]邬荫芳,袁逸.稀土强化规律及作用机理的研究.第六次全国硬质合金学术会议论文集.昆明:中国钨协硬质合金分会,1995.236-242
[61]李斌书.稀土添加方法对硬质合金物理力学性能和使用寿命的影响.硬质合金,1996,13(1):15-19
[62]柳春林,颜邦明.稀土元素对硬质合金高温性能的影响.硬质合金,1996,13(1):6-8
[63]贺从训,毛昌辉,汪有明.稀土硬质合金切削行为的研究.硬质合金,1996, 13(1):23-29
[64]孙丽虹,贺从训,林晨光.微量稀土元素添加剂对YT14硬质合金粒度的影响.中国稀土学报,1996,14(1):56-60
[65]Wu Yinfang, Yuan Yi. The influence of rare earth on Co-Based alloy. Material Science and Engineering,1996, A209:231-236
[66]Xiong Ji, Yang Jiangao, Guo Xinghua. Application of rare earth elements in cemented carbide inserts, drawing dies and mining tools. Materials Science and Engineering 1996, A209:287-293
[67]邬荫芳,袁逸,汪新义.硬质合金稀土相的研究.粉末冶金材料科学与工程,1997,2(1):1-6
[68]雍志华,汪仕元,王振宁.微量稀土对WC-8Ni硬质合金性能的影响.稀有金属材料与工程,1997,26(2):40-44
[69]Yuan Yi, Wang Xingyi, Wu Yingfang. Mechanism of improving the wearability of WC78-TiC14-Co8 cemented carbide with Yttrium addition. Journal of Rare Earths,1997,15(4):276-281
[70]张立.含稀土的镍代钴新型矿用硬质合金的研究.粉末冶金材料科学与工程,1998,3(2):121-125
[71]孙景,王波,李宝银.添加稀土的WC-20 (Fe/Co/Ni)硬质合金的研究.稀有金属,1998,22(5):289-291
[72]王波,孙景,段积林.稀土添加剂对WC-20 (Fe/Co/Ni)硬质合金性能的影响.粉末冶金技术,1999,17(3):186-190
[73]刘红卫,陈康华,吕海波.稀土对硬质合金线胀系数及粘结相形态的影响.稀有金属与硬质合金,1999,(3):30-32
[74]Zhang Li, Chen Shu. Rare earth doped new cemented carbide with Ni-Co binder for mining. Journal of Central South University of Technology-Science and Technology of Mining and Metallurgy,2000,7(3):143-145
[75]雍志华,汪仕元,程娟WC-8(Fe/Co/Ni)R硬质合金的研究.稀有金属材料与工程,2000,29(4):273-275
[76]尹飞,邬荫芳,张剑.稀土对硬质合金作用机理的研究.中国钨业,2001,16(5-6):96-101
[77]于启勋,武毓芳.新型硬质合金—添加稀土元素的硬质合金.机械工程师,2001,(7):63-65
[78]刘向中.均匀结构YT5R稀土硬质合金综合性能的研究.硬质合金,2004,21(2):86-88
[79]张立,陈述,Schubert W D,黄伯云,吴恩熙.纯氧气氛下硬质合金及其原料的热稳定性研究.中南大学学报(自然科学版),2004,35(6):931-934
[80]Zhang Li, Chen Shu, Schubert W D, Huang Bai-yun. Thermo-stability of rare earth doped cemented carbides and the starting materials in oxygen. P/M Science and Technology Briefs,2004,6(1):15-18
[81]刘沙,刘刚,杨贵彬,黄泽兰. 纳米稀土硬质合金原料粉末的制备及研究.稀有金属与硬质合金,2004,32(1):22-25
[82]Lin Chenguang, Yuan Guansen. Effects of rare earths on the microstructure of nanocrystalline WC-VC-lOCo hardmetals. Kneringer G, Rodhammer P, Wildner H, eds. Proceedings of the 16th International Plansee Seminar, Reutte, Austria:Plansee Holding AG,2005, (2):363-377
[83]杨世莹,贺子凯,黄鑫.添加剂对硬质合金性能的影响.粉末冶金工业,2005,15(6):22-25
[84]史晓亮,杨凯华,汤凤林,邵刚勤.稀土Ce的添加方式对WC-Co硬质合金性能的影响.中南大学学报, 2005,36(2):204-208
[85]Liu Sha, Huang Zelan, Liu Gang, Yang Guibin. Preparing nano-crystalline rare earth doped WC/Co powder by high energy ball milling. Journal of Refractory Metals and Hard Materials,2006,24(6):461-464
[86]刘书祯.超细晶硬质合金晶粒长大抑制剂的研究.稀有金属与硬质合金,2007,35(4):51-56
[87]董学涛,栾道成,杨梨容,向黎,蒲超.高能球磨制备纳米YG8-RE硬质合金研究.纳米加工工艺,2007,4(6):28-32
[88]涂小芳,朱伟鑫,兰世友.提高空气冲旋钻井钻头牙齿使用寿命的试验研究.石油矿场机械,2008,37(9):74-77
[89]张守全.0.2微米级超细晶硬质合金的烧结行为.粉末冶金材料科学与工程,2009,14(4):237-243
[90]Liu Sha. Study on rare-earth doped cemented carbides in China. International Journal of Refractory Metals and Hard Materials,2009,27 (3):528-534
[91]陈庚,栾道成,董学涛,王伟.高能球磨制备纳米WC-8 (Fe/Co/Ni) RE硬质合金研究.西华大学学报,2009,28(3):65-68
[92]Lin C, Cao R, Li Y. Microstructure evolution of Cr3C2 doped ultrafine WC-Co hardmetals during sintering. Kneringer G, Rodhammer P, Wildner H, eds. Proceedings of the 17th International Plansee Seminar, Reutte, Austria:Plansee Holding AG,2009. (2):HM11 1-10
[93]张立,Schubert W D,黄伯云,吴恩熙.含稀土硬质合金的表面观察.中南工业大学学报,2003,34(5):467-471
[94]Zhang Li, Schubert W D, Huang Bai-yun, Wu En-xi. Surface observation of rare earth doped cemented carbide. P/M Science and Technology Briefs,2003,5(3): 17-21
[95]张立,陈述,Schubert W D,黄伯云.Ce在混合稀土掺杂的硬质合金烧结体表面富集现象的热力学分析.硬质合金,2004,21(2):70-76
[96]张立,黄伯云,陈述,Schubert W D稀土在硬质合金球形粉末烧结体表面的富集现象.中南大学学报(自然科学版),2004,35(5):742-747
[97]张立,黄伯云,陈述,Schubert W D,吴恩熙.稀土在硬质合金球形粉末烧结表面富集现象的观察.粉末冶金材料科学与工程,2004,9(1):1-8
[98]Zhang Li, Schubert W D, Chen Shu, Zhang Chuan-fu, Huang Bai-yun. Rare earth enrichment phenomenon during the sintering process of grainy hardmetal. Materials Science and Engineering:A,2004,384(1-2):395-401
[99]Zhang Li, Schubert W D, Huang Bai-yun, Chen Shu, Zhang Chuan-fu. Cerium enrichment phenomenon on the sinter skin of cemented carbide. Herbert Danninger, Raimund Ratzi, eds. Euro PM 2004 Conference proceedings, Vienna, Austria:European Powder Metallurgy Association,2004.3:455-460
[100]Zhang Li, Chen Shu, Xiong Xiang-jun, Huang Bai-yun, Zhang Chuan-fu. Cerium enrichment on sinter skin of mischmetal doped WC-Co cemented carbide. Journal of Central South University of Technology,2005,12(S1):5-8
[101]Zhang Li, Chen Shu, Huang Bai-yun, Zhang Chuan-fu. Separation Phenomenon of La and Ce during the Sintering Process of Cemented Carbide. Kneringer G, Rodhammer P, Wildner H, eds. Proceedings of the 16th International Plansee Seminar, Reutte, Austria:Plansee Holding AG,2005,(2):574-587
[102]张立,陈述,熊湘君,黄伯云,张传福.稀土在硬质合金烧结体表面富集现象的开发前景.中国钨业,2005,20(2):24-27
[103]Zhang Li, Chen Shu, Xiong Xiang-jun, Yu Xian-wang, Wang Yuan-jie. Directional migration behavior of cerium during the sintering process of mischmetal doped cemented carbide. Journal of Central South University of Technology,2008,15(1):6-10
[104]吴厚平,张立,王振波,陈述,熊湘君.镧、铈在WC-Co合金中赋存状态的研究.中国稀土学报, 2009,27(5):693-697
[105]Zhang Li, Wu Hou-ping, Yu Xian-wang, Chen Shu, Xiong Xiang-jun. Asynchronous migration of La, Ce and in-situ formation of RE2O2S during cutting process of RE doped hardmetal tool. Proceedings of the 17th International Plansee Seminar, Reutte, Austria:Plansee Holding AG,2009. vol 3, AT 17 1-12
[106]吴厚平,张立,余贤旺,陈述,熊湘君.稀土硬质合金刀片切削过程中自润滑功能稀土氧硫化物的原位形成.中国有色金属学报,2009,19(4):670-676
[107]张立,陈述.冶金炉炉内杂质清洁材料.申请号:200610031433.9;授权公告号:CN100462463C.申请日:2006年3月30日;授权公告日:2009年2月18日
[108]Gille G, Szesny B, Dreyer K. Submicron and ultrafine grained hardmetals for microdrills and metal cutting inserts. In:Kneringer G, Rodhammer P, Wildner H, eds.15th International Plansee Seminar. Reutte, Austria:Plansee Holding AG, 2001.2:733-767
[109]Kawakami M, Terada O, Hayashi K. Segregation amount of dopants at WC/Co interface in Cr3C2 and VC+ Cr3C2 doped WC-Co submicro-grained hardmetals. In:Kneringer G, Rodhammer P, Wildner H, eds.16th International Plansee Seminar. Reutte, Austria:Plansee Holding AG,2005.2:653-667
[110]Lay S, Thibault S. Hamar, Lackner A. Location of VC in VC, Cr3C2 codoped WC-Co cermets by HREM and EELS. International Journal of Refractory Metals and Hard Materials,2002,20:61-69
[111]Peter Warbichler, Ferdinand Hofer, Werner Grogger. EFTEM-EELS characterization of VC and Cr3C2 doped cemented carbides. In:Kneringer G, Rodhammer P, Wildner H, eds.15th International Plansee Seminar. Reutte, Austria:Plansee Holding AG,2001.2:65-74
[112]张立,Schubert W D,黄伯云.热压固结与传统液相烧结对WC-2OCo-1Y2O3硬质合金组织结构与性能的影响.粉末冶金材料科学与工程,2003,8(3):179-185
[113]Zhang Li, Chen Shu, Schubert W D, Huang Bai-yun. Microstructures and properties of WC-20Co-1Y2O3 cemented carbide by hot-press and liquid phase sintering. Journal of Central South University of Technology,2004,11(2): 93-98
[114]张立,陈述,张传福,黄伯云.含板状晶WC双模组织结构硬质合金的研究.稀有金属,2004,28(6):979-982
[115]Zhang Li, Chen Shu, Wang Yuan-jie, Yu Xian-wang, Xiong Xiang-jun. Tungsten carbide platelet-containing cemented carbide with yttrium containing dispersed phase. Transactions of Nonferrous Metals Society of China,2008,18(1): 104-108
[116]吴炳乾.稀土冶金学.长沙:中南大学出版社,1997.10-11
[117]戢景文,车韵怡,刘爱生.钢铁中稀土合金化的内耗研究及其理论.中国稀土学报,1996,14(4):350-359
[118]吉泽升,夏立芳,王海波.稀土硼铝共渗初期渗层的相组成.中国有色金属学报,8(S1):66-69
[119]Beiss P, Ruthardt R, Warlimont H. Powder Metallurgy Data. Refractory, Hard and Intermetallic Materials. Springer-Verlag.2002
[120]Hayashi Kozi, Fuke Yasunori, Suzuki Hisashi. Effect of addition carbides on the grain size of WC-Co alloy. Journal of the Japan Society of Powder and Powder Metallurgy,1972,19(2):67-71
[121]Morton C W, Wills D J, Stjernberg K. The temperature ranges for maximum effectiveness of grain growth inhibitors in WC-Co alloys. International Journal of Refractory Metals & Hard Materials,2005,23:287-293
[122]Yamamoto Y, Matsumoto A, Doi Y. Properties of ultrafine tungsten carbide and cemented carbide by direct carburization. In:Kneringer G, Rodhammer P, Wilhartitz P eds. Proceedings of 14th International Plansee Seminar, Reutte, Austria:Plansee Holding AG,1997.2:596-608
[123]Sarin V K. Morphology of ETA phase in cemented carbide. Modern Development in Powder Metallurgy,1977,10:553-565
[124]Uhrenius B, Carlsson B, Franzen T. A study of the Co-W-C system at liquidus temperatures. Scandinavian Journal of Metallurgy,1976,5(2):49-56
[125]陈楚轩.硬质合金生产过程中的质量控制.中国有色金属加工工业协会硬质合金协会.株洲.1998:57
[126]Dreyer K, Rodiger K, Berg H, Kassel D, Orths S. Powder metallurgy and applications of hardmetals. DGM-Seminar "Powdermetallurgy", Aachen: EPMA.2000
[127]Steven G. Moseley. Process steps in the manufacture of hardmetal-from powder to fully dense product. EPMA PM Summer School,31 Aug-6 Sept 2002, Vienna, Austria,310-329
[128]Petrova L A, Effenberg G. Red Book-Phase Diagrams of Metallic Systems, Vol. 35, Part 1. Stuttgart, Germany:Material Science International Services GmbH, 1990
[129]Hugh Baker, Hiroaki Okamoto. ASM Handbook, Vol.3, Alloy Phase Diagrams. Ohio, USA:American Society for Metals,1992.2.151-153
[130]Schubert W D, Neumeister H, Kinger G. Hardness to toughness relationship of fine-grained WC-Co hardmetals. International Journal of Refractory Metals and Hard Materials,1998,16:133-142
[131]Roebuck B, Brewin P. Toughness testing of hardmetals. Powder Metallurgy 2004;47(1):15-6
[132]Shetty D K, Wright I G. On estimating fracture toughness of cemented carbide from Palmqvist crack sizes. Journal of Material Science Letters,1986,5(3): 365-368
[133]Shetty D K, Wright I G, Mincer P N. Indentation fracture of WC-Co cermets. Journal of Material science,1985,20(5):1873-188
[134]Roebuck B, Coles W. Mechanical test discriminability for WC hardmetals. International Journal of Refractory Metals and Hard Materials,1992,11(3): 127-136
[135]Richter V, Rethendorf M V. On hardness and toughness of ultrafine and nanocrystalline hard materials. International Journal of Refractory Metals and Hard Materials,1999,17(1-3):141-152
[136]Kinger G. A study on Palmqvist toughness testing of fine-grained WC-Co alloys: [Diploma Work]. Vienna:TU-Vienna, Austria,1996
[137]Neumeister H. The hardness/toughness relationship of fine-grained WC-Co hardmetals:[Thesis Work]. Vienna:TU-Vienna, Austria,1997
[138]施明哲,董本霞.电子材料分析中的能谱干扰峰.电子产品可靠性与环境试验.2002(4):46-49
[139]EDS. EDS peak indentation chart.www.EDS.com.2009-8-30
[140]张冠星,马全仓,关绍康.富铈混合稀土对5052铝合金流动性及净化效果的影响.材料热处理学报,2008,29(4):83-86
[141]Upadhyaya G S. Materials science of cemented carbides-an overview. Materials and Design,2001,229(6):483-489
[142]Dongtao Jianga, Guy Annea, Jef Vleugelsa, Kim Vanmeensela, Wesley Eeraertsb, Weidong Liub, Bert Lauwersb, Omer Van der Biesta. Residual stresses in hardmetals caused by grinding and EDM machining and their influence on the flexural strength. In:Kneringer G, Rodhammer P, Wildner H, Editors. Proceedings of the 16th International Plansee Seminar. Reutte, Austria: Plansee Holding AG.2005,1075-1085
[143]Santana Y Y, Renault P O, Sebastiani M, Barbera J G L, Lesage J, Bemporad B, Bourhis E L, Puchi-Cabrera E S, Staia M H. Characterization and residual stresses of WC-Co thermally sprayed coatings. Surface and Coatings Technology,2008,202:4560-4565
[144]Hegemana J B J W, Hosson J Th M De, With G De. Grinding of WC-Co hardmetals. Wear,2001,248(1-2):187-196
[145]Spirina S I, Sverdlova B M, Spirina N I. Influence of residual stresses on the static strength of hard alloys of the VK type [tungsten carbide-cobalt]. Strength of Materials,1975,7(9):1105-1111
[146]Roebuck B. The tensile strength of hardmetals. Journal of Materials Science, 1979,14:2837-2844
[147]吴冲浒WC-Co系硬质合金Co相的熔点.硬质合金,1999,16(4):201-205
[148]Gille G, Szesny B, Dreyer K. Submicron and ultrafine grained hardmetals for microdrills and metal cutting inserts. International Journal of Refractory Metals and Hard Materials,2002,20(1):3-22
[149]Briesecka M, Bohnb M, Lengauera W. Diffusion and solubility of Cr in WC. Journal of Alloys and Compounds,2010,489(2):408-414
[150]张世荣,涂赣峰,张成祥, 任存治, 李春材.氧化镧碳化行为的研究.稀土,1997,18(5):24-26
[151]《无机化学编写组》.无机化学.上海:人民教育出版社,1979.21,70,175,288,322,346
[152]Gschneidner Jr Karl A, Eyring Le Roy. Handbook on the physics and chemistry of rare earths-Volume 3. New York, Oxford:North-Holland Publishing Company, Amsterdam,1978,173-232,233-336,299-336
[153]《稀土编写组》.稀土(上册).北京:冶金工业出版社,1978.40
[154]中山大学金属系编.稀土物理化学常数.北京:冶金工业出版社,1978
[155]张质贤.物理学常用数表.北京:科学出版社,1979
[156]冯端.金属物理学第一卷结构与缺陷.北京:科学出版社,1998.14
[157]钟华仁.钢的稀土化学热处理.北京:国防工业出版社,1998.187-189
[158]《稀有金属手册》编辑委员会.稀有金属手册.北京:冶金工业出版社,1992.16
[159]余瑞璜.固体与分子经验电子理论.科学通报,1978, 23(4):217-224
[160]余瑞璜.固体与分子经验电子理论—等效价电子假定.科学通报,1981,26(4):206-209
[161]张瑞林.固体与分子经验电子理论.长春:吉林科学技术出版社,1993
[162]王绍铿,吕振家.La系金属结合能的计算.科学通报,1980,26(4):220-223
[163]刘志林.合金价电子结构与成分设计.长春:吉林科学技术出版社,1990
[164]李培杰,刘树勋,曾大本.余氏理论在液态合金结构研究中的应用.铸造,2001,50(6):325-328
[165]朱兴元.低硫低合金钢中铈合金化作用规律的研究:[博士学位论文].北京:北京科技大学,2000
[166]吉泽升.钢的硼铝共渗层组织结构及稀土的影响:博士学位论文].哈尔滨:哈尔滨工业大学,1999
[167]许育东,石敏,刘宁(Ti, Me) (C, N)/Ni的润湿性及其价电子结构.复合材料学报,2005,22(4):75-80
[168]王世清.稀土元素在化学热处理中的应用研究.金属热处理,1988,(3):52-59
[169]连亚峰,党鸿辛.稀土元素的摩擦学研究发展概括.摩擦学报,1993,13(2):183-190
[170]虞澜.金—稀土合金电刷丝的磨损机理研究.摩擦学学报,2002,22(4):282-285
[171]翟光杰,刘家浚,朱宝亮.稀土元素对镍基喷焊合金层摩擦表面形成氧化物膜的影响.摩擦学学报,1996,16(1):21-27
[172]吴凯,刘国权,王蕾,许伯藩.2Cr13不锈钢的稀上催渗循环离子渗氮工艺研究.材料热处理学报,2008,29(2):131-134
[173]张金柱,杨宗伦,魏可媛.稀土元素在化学热处理中的催渗和扩散机理研究.材料导报,2006,20(4):223-225
[174]Jiang Jinghua, Jiang Jianqing, Ma Aibin, Tu Yiyou, Fang Feng. Application of low temperature liquid sulfurization catalyzed with rare earth on Cr12 impacting die. Journal of Rare Earths,2007,25(2):220-226
[175]徐进,朱坤.稀土对一种固体渗硼剂渗硼动力学的影响.热处理,2007,22(4):16-18
[176]李彬.稀土催渗剂的配制及其催渗机理的探讨.热处理,2001,16(4):16-19
[177]杜晓东.稀土催渗的锆硼共渗研究.稀有金属与硬质合金,2001,(144):15-18
[178]陈方生,刘玉先,徐军.稀土催渗离子渗氮机理的研究.金属热处理,1999. (2):7-9
[179]王豫,施世龙,吴忠义20CrMnTi钢稀土催渗渗碳研究.稀土,1998,19(6):35-38
[180]宋绪丁,张翔,王利捷.2Cr13马氏体不锈钢稀土催渗离子SNC共渗的研究.西安公路交通大学学报,1996,16(4):98-101
[181]冯承明,许斌,华磊.渗硼过程的稀土催渗与共渗研究进展.金属热处理,1995,(6):3-5
[182]张松,王佳华,朱荆璞.45钢稀土催渗气体氮—碳—硼多元共渗的研究.沈阳工业大学学报,1994,16(4):58-62
[183]Khie Hong Cho, Wan lee Joo, In Sang Chung. A study on the formation of anomalous large WC grain and the eta phase. Material Science and Engineering A,1996, A209(1-2):298-301
[184]Anthonysamy S, Ananthasivan K, Kaliappan I, Chandramouli V, Vasudevarao P R, Mathews C K, Jacobk T. Gibbs Energies of Formation of Chromium Carbides. Metallurgical and Materials Transactions A,1996,27:1919-1924
[185]Du Sichen. Standard Gibbs energies of formation of the carbides of vanadium by Emf measurements. Metallurgical Transactions B,1990,21(2):313-320
[186]Wang Jinshu, Zhou Meiling, Zuo Tieyong, Zhang Jiuxing, Nie Zuoren. A study of the effect of chemical state of lanthanum on the emission properties of La2O3-Mo filament. Journal of Alloys and Compounds,2003,348(1-2): 332-336
[187]Wang Jinshu, Zhou Meiling, Zuo Tieyong, Zhang Jiuxing, Nie Zuoren. A study of chemical behavior of lanthanum in La2O3-Mo thermionic cathode materials. Journal of Alloys and Compounds,2002,339(1-2):293-298
[188]Wang Jinshu, Zhou Meiling, Nie Zuoren, Zhang Jiuxing, Zuo Tieyong, Wang Yiman. A study of diffusion behavior of elements lanthanum and oxygen in Mo-La2O3 cathode. Journal of Alloys and Compounds,2000,311(1):82-85
[189]Lee W B, Kwon B D, Jung S B. Effects of Cr3C2 on the microstructure and mechanical properties of the brazed joints between WC-Co and carbon steel. International Journal of Refractory Metals and Hard Materials,2006,24: 215-221
[190]Luo X X, Cao W H. Ethanol-assistant solution combustion method to prepare La2O2S:Yb, Pr nanometer phosphor. Journal of Alloys and Compounds,2008, 460:529-534
[191]Madelung O, Rossler U, Schulz M. La2S3:crystal structure, physical properties. Berlin:Springer-Verlag.2000
[192]Andreev O V, Mitroshin O Y, Razumkova I A. Phase diagrams of the systems Sc2S3-Ln2S3 for Ln=La, Nd, or Gd. Russian Journal of Inorganic Chemistry, 2007,52(7):1161-1164
[193]Orlovskaya N, Gogotsi Y, Reece M, Cheng BL, Gibson I. Ferroelasticity and hysteresis in LaCoO3 based perovskites. Acta Materialia,2002,50 (4):715-723
[194]Vahed A, Kay D A R. Thermodynamics of rare earths in stellmaking. Metallurgical transactions B,1976,7(3):375-383
[195]Romero S, Mosset A, Macaudiere P, Trombe J C. Effect of some dopant elements on the low temperature formation of γ-Ce2S3. Journal of Alloys and Compounds,2000,302(1-2):18-127
[196]Hirai S, Shimakage K, Saitou Y, Nishimura T, Uemura Y, Mitomo M, Brewer L Synthesis and Sintering of Cerium(Ⅲ) Sulfide Powders. Journal of the American Ceramic Society,1998,81(1):145-151
[197]汪复兴.金属物理.北京:机械工业出版社,1981,175
[198]李正伟,何业东,齐慧滨,等.金属氧(硫、碳、氮)化物单位体积标准生成自由能图.中国有色金属学报,1998,8(Suppl.1):55-60
[199]Kumar R V, Kay D A R. Thermodynamics of the Ca-S-O, Mg-S-O, and La-S-0 systems at high temperatures. Metallurgical and Materials Transactions B,1985,16(2):285-294
[200]Parida S C, Singh Z, Dash S, Prasad R, Venugopal V. Standard molar Gibbs energies of formation of the ternary compounds in the La-Co-O system using solid oxide galvanic cell method. Journal of Alloys and Compounds,1999, 285(1-2):7-11
[201]Kitayama K. J. Thermogravimetric study of the Ln2O3-Co-Co2O3 system. Journal of Solid State Chemistry,1997,131(1)18:18-23
[202]Niu Y, Fu G Y, Gesmundo F. The corrosion of a Co-15 wt% Ce alloy in mixed oxidizing-sulfidizing gases at 600-800℃. Corrosion Science,1999,41(9): 1791-1815
[203]Akila R, Jacob K T, Shukla A K. Standard free energies of formation of rare earth sesquisuiphides. Journal of Materials Science,1987,22:2085-2093
[204]Ferrizz R M, Gorte R J, Vohs J M. Determining the Ce2O2S-CeOx phase boundary for conditions relevant to adsorption and catalysis. Applied Catalysis B:Environmental,2003,43(3):273-280
[205]Lohsoontorn P, Brett D J L, Brandon N P. Thermodynamic predictions of the impact of fuel composition on the propensity of sulphur to interact with Ni and ceria-based anodes for solid oxide fuel cells. Journal of Power Sources,2008, 175(1):60-67
[206]Windiks R, Wimmer E, Pourovskii L, Biermann S, Georges A. Structure and optical properties of α- and γ-cerium sesquisulfide. Journal of Alloys and Compounds,2008,459(1-2):438-446
[207]Pauwels D, Demourgues A, Laronze H, Gravereau P, Guillen F, Isnard O, Tressaud A. Structural features of new rare earth-based mixed anions (O, S, F) compounds:relationships between optical absorption and rare earth environment. Solid State Sciences,2002,4:1471-9
[208]Hansteen O H, Fjellvag H, Hauback B C. Crystal structure, thermal and magnetic properties of La3Co3O8. Phase relations for LaCoC3-δ(0.00(?)δ(?)0.50) at 673 K. Journal of Materials Chemistry,1998,8(9):2081-2088
[209]吴厚平,张立,赵晓兆,陈述,王振波La、Ce、Pr、Nd混合稀土掺杂的硬质合金刀具工作表面含稀土富集相的能谱分析.粉末冶金材料科学与工程,2010,15(2):117-122