面向等离子体材料用先进钨复合材料的改性研究进展与趋势

罗来马; 颜硕; 刘祯; 昝祥; 吴玉程

doi:10.19591/j.cnki.cn11-1974/tf.2022030012

面向等离子体材料用先进钨复合材料的改性研究进展与趋势

罗来马^{1, 2, 3, ,},
颜硕¹,
刘祯¹,
昝祥^{1, 2, 3},
吴玉程^{1, 2, 3}

1.
合肥工业大学材料科学与工程学院, 合肥 230009
2.
合肥工业大学有色金属与加工技术国家地方联合工程研究中心, 合肥 230009
3.
合肥工业大学高性能铜合金材料及成形加工教育部工程研究中心, 合肥 230009

基金项目: 国家重点研发磁约束聚变能发展专项资助项目（2019YFE03120002）；安徽省重点研发项目（202104a05020045）；安徽省自然基金杰出青年基金资助项目（2108085J21）

详细信息

通讯作者:
罗来马: E-mail: luolaima@126.com

中图分类号: TG146.1
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出版历程
- 收稿日期: 2022-08-06
- 录用日期: 2022-08-06
- 网络出版日期: 2022-08-06
- 刊出日期: 2023-02-27

Research progress and trend of advanced tungsten composite modification used for plasma facing materials

LUO Laima^{1, 2, 3, ,},
YAN Shuo¹,
LIU Zhen¹,
ZAN Xiang^{1, 2, 3},
WU Yucheng^{1, 2, 3}

1.
School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China
2.
National-Local Joint Engineering Research Centre of Nonferrous Metals and Processing Technology, Hefei University of Technology, Hefei 230009, China
3.
Engineering Research Center of High Performance Copper Alloy Materials and Processing, Ministry of Education, Hefei University of Technology, Hefei 230009, China

More Information

Corresponding author:
LUO Laima: E-mail: luolaima@126.com

摘要

摘要:
核聚变能是解决未来社会能源危机的有效途径之一，但面向等离子体材料在聚变堆体中面临着来自等离子体严重的辐照和热冲击损伤。纯钨因其高热导率、良好的高温强度、低溅射和低蒸气压而被认为是最有希望的面向等离子体候选材料。纯钨在聚变堆工况条件下具有严重的脆性风险，因而对面向等离子体材料用先进钨材料的改性成为近年来的研究热点。钨基复合材料的改性方法主要包括合金化、第二相强化、纤维增韧和复合强化。本文综述了近年来国内外针对核聚变反应堆面向等离子体材料用钨基复合材料的改性方法及其性能，分析了钨基复合材料的改性机制，并展望了面向等离子体材料用钨基复合材料的发展方向。
- 聚变反应堆 /
- 面向等离子体材料 /
- 钨基复合材料 /
- 改性方法 /
- 性能
Abstract:
Fusion energy is one of the effective ways to solve the energy crisis in the future, but the plasma-facing materials (PFMs) face the serious radiation and thermal shock damage from the plasma in the fusion reactor. At present, the pure tungsten is considered as the most promising PFM candidate materials because of the high thermal conductivity, good high-temperature strength, low sputtering, and low vapor pressure. Pure tungsten has the serious brittleness risk under the fusion reactor condition, so the modification of the advanced tungsten materials for PFMs has become the research hotspot in recent years. The modification methods of tungsten matrix composite include alloying, second phase strengthening, fiber reinforcement, and composite toughening. In this paper, the modification methods and performance of the tungsten matrix composites as PFMs used in the nuclear fusion reactors at home and abroad in recent years were reviewed, the modification mechanism of tungsten matrix composites was analyzed and summarized, and the development direction of tungsten matrix composites as PFMs was prospected.
- fusion reactor /
- plasma-facing materials /
- tungsten composites /
- modification methods /
- performance

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硬质合金是以难熔金属碳化物（WC、TiC、TaC等）为硬质相，以过渡金属元素（Co、Ni、Fe等）为粘结相，采用粉末冶金方法制备的复合材料^[1‒2]。硬质合金具有高强度、高硬度、高弹性模量、高耐磨损、高耐腐蚀、低热膨胀系数以及高化学稳定性等优点，被广泛地应用于拉丝模具、机械加工、耐磨耐腐蚀零件以及结构部件等领域，被誉为“工业的牙齿”^[3‒6]。

自1923年发展至今，硬质合金的材料体系、WC晶粒尺寸、微观结构类型不断得到丰富与发展^[7‒9]。均匀结构硬质合金是指内部微观结构均匀一致，具有相同成分、组织及性能的硬质合金^[10]。根据WC晶粒大小，均匀结构硬质合金可分为纳米及超细晶硬质合金、超粗晶硬质合金和双晶硬质合金等^[11‒18]。均匀结构硬质合金由陶瓷硬质相和金属粘结相组成，陶瓷硬质相的比例提高有助于硬度和耐磨性的改善，但会造成韧性的降低；反之，当金属粘结相的比例提高时，会出现相反的力学性能变化规律。均匀结构硬质合金存在无法同时提高耐磨性和断裂韧性的局限性。表面改性在硬质合金表层空间尺度上实现微观组织的变化，进而对表面力学性能进行优化调控，最终提高硬质合金工具的使用寿命，满足工业应用不断发展的现状。目前主要通过化学表面改性和物理表面改性获得具有实际工程应用价值的非均匀结构硬质合金。近年来，通过渗碳、脱碳、渗氮或脱氮处理等化学表面改性制备梯度硬质合金或通过物理气相沉积和化学气相沉积等物理表面改性制备涂层硬质合金已成为非均匀结构硬质合金的研究热点。基于物理气相沉积或化学气相沉积涂层方法的多层复合涂层硬质合金已实现大规模商业化应用。

本文针对目前传统均匀结构硬质合金耐磨性和断裂韧性难以同时提升的问题提出改进措施，介绍了不同表面改性处理得到非均匀结构硬质合金的制备机理与研究现状，并对今后的研究方向提出了展望。

1. 化学表面改性

随着硬质合金制备技术的发展，非均匀结构硬质合金的制备方法不断丰富，其中表面改性是制备非均匀结构硬质合金的主要方法。化学表面改性是通过原子扩散、液体流动、化学反应等方法实现硬质合金表面物相及微观组织的改变，进而完成合金表面力学性能的定向改善^[19‒20]。目前通过化学表面改性制备的常见梯度硬质合金如表1所示。

表 1 基于化学表面改性的常见梯度硬质合金

Table 1. Graded cemented carbides based on the chemical surface modification

化学表面改性方法	材料体系特点	梯度结构特征
渗碳处理	缺碳	表层贫Co，芯部含η相
渗碳处理	正常碳的质量分数	表层贫Co，芯部不含η相
脱碳处理	碳的质量分数偏高	表层富Co
渗氮处理	含Ti、Ta、Nb等元素	表层富含立方相
脱氮处理	含N元素	表层富Co，无立方相

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| 显示表格

渗碳或脱碳处理实现梯度结构是基于碳的扩散及碳的质量分数对硬质合金微观组织的影响。如WC–Co合金中只出现WC与Co两相，正常碳的质量分数应分布在富碳上限和缺碳下限之间^[21]，其中富碳上限为（6.13+0.058×Co质量分数）%，缺碳下限为（6.13‒0.079×Co质量分数）%。当合金中的碳质量分数高于富碳上限时，就会出现游离C，也就是石墨相；当合金中的碳质量分数低于缺碳下限时，就会出现η相^[21‒22]。渗氮或脱氮是基于氮的扩散和氮、钛及碳之间的化学反应。氮的扩散实现硬质合金表面物相和微观组织的变化，进而促进梯度结构的形成^[19,23]。

1.1 渗碳处理——表层贫Co且芯部含η相梯度结构

表层贫Co且芯部含η相梯度结构的形成机理分析如下^[24–27]：通过预烧结制备含η相硬质合金，然后进行渗碳液相烧结，渗入合金表面的C原子与表面η相发生反应，生成WC与Co。随着C原子由表及里的迁移，C原子由外向内与η相反应，这种反应导致η相降低甚至消失，Co相增加。C原子浓度在液相Co中呈现出外高内低的梯度，C原子浓度梯度驱动分解出来的W原子往外表层迁移，并且会与液相Co中的C原子反应生成WC。由W原子往外迁移而引起的体积缺陷也会驱动外表层中的液相Co由表及里迁移，因而导致过渡层的Co含量（质量分数）偏高，进而引起过渡层WC晶粒粗化。

表层贫Co且芯部含η相梯度结构示意图如图1所示^[27]，可分为贫Co表层、富Co过渡层和含η相芯部。该梯度硬质合金的Co含量（质量分数）与维氏硬度分布如图2所示^[27]。由图可知，表层Co质量分数低于名义Co质量分数，因而表层硬度高；过渡层的Co质量分数高于名义Co质量分数，因而硬度低，韧性高；芯部含有η相，其Co质量分数是合金的名义Co质量分数。

图 1 表层贫Co且芯部含η相梯度结构示意图^[27]：（a）贫Co表层；（b）富Co过渡层；（c）含η相芯部

Figure 1. Schematic of the graded structure^[27]: (a) the cobalt-depleted surface; (b) the cobalt-rich transition layer; (c) the core with η phase

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图 2 Co质量分数与维氏硬度从表面到中心的分布^[27]

Figure 2. Distribution of Co mass fraction and vickers hardness from the surface to the center^[27]

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1.2 渗碳处理——表层贫Co且芯部不含η相梯度结构

图3所示为WC–10Co硬质合金的W–Co–C相图^[28]。关于表层贫Co且芯部不含η相梯度结构形成机理分析如下^[28‒29]：当温度在1275～1325 ℃区间时，WC、固相Co和液相Co三相共存，在此温度范围内，当C质量分数在5.34%～5.65%范围内增加时，固相Co含量（质量分数）明显减少，而液相Co含量显著增加。因此，当低C含量且不含η相硬质合金在此温度下进行渗碳处理时，C原子逐渐渗入合金的表层，较高的C含量使合金表层首先出现液相Co，进而液相Co从合金表层向合金内部渗入，当保温一定时间，再冷却降温后，所有Co都会以固相Co的形式存在，最终出现表层贫Co的梯度硬质合金。该梯度结构特征如图4所示^[28]，由贫Co的表层和无η相的芯部组成。

图 3 WC–10Co硬质合金的W–Co–C相图^[28]

Figure 3. W–Co–C phase diagram of the WC–10Co cemented carbide^[28]

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图 4 表层贫Co且芯部不含η相梯度结构示意图^[28]：（a）贫Co表层；（b）无η相芯部

Figure 4. Schematic of the graded structure^[28]: (a) the cobalt-depleted surface; (b) the core without η phase

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1.3 脱碳处理——富Co表层梯度硬质合金

富Co表层梯度结构形成机理分析^[30‒32]如下：从图3可以看出，液相Co含量（质量分数）会随着温度和C含量（质量分数）的变化而改变。脱碳处理即在低碳势的气氛下进行烧结，在1300 ℃以下进行脱碳，硬质合金表层的C含量将会率先降低，表层的Co优先从液相到固相发生转变，当液相Co开始凝固时，表层中溶解在液相Co中的C和W溶解度会下降，进而表层中的C和W向合金的内部迁移，最终形成表层富Co层，类似于一层Co覆盖在硬质合金的表层。脱碳处理得到的富Co表层梯度硬质合金如图5所示^[28]。通过脱碳处理制备表层覆盖Co层的梯度硬质合金，对原始合金的C含量（质量分数）要求偏高，否则将会造成合金内部缺C。

图 5 脱碳处理得到的富Co表层梯度硬质合金^[30]：（a）表面形貌；（b）断面形貌

Figure 5. Graded cemented carbides with the cobalt-rich surface obtained by decarburization^[30]: (a) surface morphology; (b) section morphology

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1.4 渗氮处理——表层富含立方相梯度结构

表层富含立方相梯度结构形成机理如图6所示^[19,33‒34]：渗氮促使烧结气氛中的N原子扩散到合金表面，N原子与合金表面的C、Ti原子反应生成Ti(C,N)。该反应促使合金内部区域的Ti原子从里往外迁移。合金次表层的Ti原子向外迁移留下空位，此空位需要其他原子予以填充。金属Co原子在硬质合金材料体系中的扩散系数高，尤其是液相烧结，部分Co相为液相，流动性最好，所以Co原子会定向迁移填充由Ti原子迁移所造成的原子空位。此时，合金的次表层Co含量增加，次表层Co的富集促进次表层WC晶粒通过溶解–析出机制长大粗化，所以次表层富Co且WC晶粒粗大。最终形成表层富立方相、次表层富Co且WC晶粒粗大的梯度结构硬质合金。

图 6 表层富含立方相梯度结构形成机理示意图^[19,33‒34]

Figure 6. Formation mechanism schematic diagram of the graded structure with the surface layer in cubic-rich phase^[19,33‒34]

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1.5 脱氮处理——表层富Co且无立方相梯度结构

表层富Co且无立方相梯度结构形成机理如图7所示^[35‒36]：在无氮或贫氮的烧结气氛下，含氮硬质合金在液相烧结过程中合金表面的氮化物发生分解，即合金表面N原子向烧结气氛中扩散，进而造成合金表层的N原子含量降低。此时，合金内部N原子的浓度大于合金表面N原子的浓度，合金内部的N原子向合金表面扩散。由于N与Ti原子之间存在强烈的亲和力，当合金内部的N原子通过粘结相向合金表面扩散时，合金表面的Ti原子也会通过粘结相向内部扩散，同时液相Co会从合金内部流向表层去填补由TiN分解出现的空位，进而导致合金表层的Co含量增加。直至合金表层TiN几乎全部发生分解，进而形成表层富Co且无立方相梯度结构硬质合金。

图 7 表层富Co无立方相梯度结构形成机理示意图^[35‒36]

Figure 7. Formation mechanism schematic diagram of the gradient structure in the surface layer with cobalt-rich and without cubic phase^[35‒36]

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目前，部分基于化学表面改性方法的结构功能一体化梯度硬质合金材料已实现商业化且制备机理已基本清晰。但在化学表面改性实现梯度结构过程中，关于化学扩散与热扩散原理还缺乏深入研究，需要深入分析原子的迁移驱动力、动力学方程，建立原子在化学势和温度梯度作用下的迁移模型。

2. 物理表面改性

物理表面改性是通过涂覆的方法在硬质合金表面制备单层或者多层复合涂层，从而赋予硬质合金特定的表面性能^[37]。目前，涂层硬质合金主要通过物理气相沉积和化学气相沉积方法在材料表面涂覆高耐磨的难熔金属或非金属化合物^[38]。

2.1 涂层方法分析

国内外研究人员对物理气相沉积和化学气相沉积涂层方法进行了广泛且深入的研究，结果表明两种方法分别具有不同优势^[38‒41]。对于物理气相沉积，沉积温度低，涂层的沉积温度约200～500 ℃，一般对基体影响不大；对于化学气相沉积，由于沉积温度较高（850～1050 ℃），基体通常参与了薄膜成膜初期的化学反应。物理气相沉积涂层表面光滑，内部产生压应力，有助于抗裂纹扩展。对于化学气相沉积，涂层反应源的制备相对比较容易，涂层与基体结合强度高，涂层附着力强、均匀性好，适合用来给复杂形貌工件镀层。化学气相沉积涂层工业化成本低于物理气相沉积涂层。

2.2 涂层结构设计

由于单一涂层难以满足当前机加工对涂层硬质合金刀具的力学性能要求，涂层成分趋于多元化，涂层结构趋于复合化，涂层微观组织趋于纳米化^[38,42]。从目前应用需求分析，机加工对涂层结构的功能性要求越来越高^[42]，复合功能涂层结构已取得广泛应用。

瑞典、美国等国家的著名刀具公司都开发有多层结构的涂层硬质合金刀具。如瑞典Sandvik Coromant公司的GC2015牌号刀具具有TiCN–TiN/Al₂O₃–TiN的三层结构复合涂层，TiCN底层与基体的结合强度高，TiN/Al₂O₃中间层既耐磨又能抑制裂纹的扩展，TiN表层具有较好的化学稳定性且易于观察刀具的磨损^[43]。美国Kennametal Hertel公司的KC9315型刀片上共有三层涂层，底层是Al₂O₃，中间层是TiCN，表面层是TiN。这种多层复合涂层的性能较单层的TiC、TiN涂层及TiC/TiN双层涂层具有明显性能优势。多层复合涂层的功能分析如图8所示^[42]。

图 8 多层复合涂层示意图^[42]

Figure 8. Schematic diagram of the multilayer composite coatings^[42]

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物理表面改性方法解决了硬质合金刀具硬度与强度之间的矛盾，已经在数控车床刀具领域取得广泛应用。涂层的性能取决于材料的微观组织结构与化学成分，除了研究涂层材料、涂层制备技术、涂层工艺之外，还需要重点研究涂层材料与硬质合金材料之间化学成分和热膨胀系数的匹配关系。

3. 总结与展望

硬质合金的主要研究方向已经从均匀结构向非均匀结构转变。对于化学表面改性梯度硬质合金，在研究当前梯度硬质合金微观结构及形成机理的基础上，需要完善其热力学、动力学数据，从微观机制上完整解释梯度结构的形成过程，实现准确调控梯度结构形成的重要参数，为功能梯度硬质合金的制备提供更充分的基础理论指导。对于物理表面改性涂层硬质合金，当前研究主要是在均匀结构硬质合金基体上进行涂层结构复合化设计，对硬质合金基体的梯度结构设计在改善涂层与基体结合强度方面具有潜在技术优势，因此，需要对硬质合金基体的非均匀结构设计开展深入研究。

图 1 Re掺杂对W基体中位错–核心对称性结构的影响^[25]

Figure 1. Effect of Re doping on the dislocations–core symmetry structure in W matrix^[25]

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图 2 W和W₁₅Re在<100>、<110>和<111>方向上的拉伸应力–应变曲线^[26]

Figure 2. Tensile stress-strain curves of W and W₁₅Re in <100>, <110>, and <111> directions^[26]

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图 3 工业纯W、W5Re和W10Re三种测试材料在恒定压痕应变速率下的硬度随相应温度（T/T_m）的变化^[27]

Figure 3. Evolution of hardness with the homologous temperature (T/T_m) for the industrial pure W, W5Re, and W10Re at the constant indentation strain rates^[27]

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图 4 W‒K合金中钾泡三种复合形式：（a）晶间型；（b）晶内型；（c）晶间/晶内型^[16]

Figure 4. Three forms of the potassium bubbles in W‒K alloys: (a) inter-type; (b) intra-type; (c) inter/intra-type^[16]

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图 5 （a）放电等离子烧结制备W–K合金硬度与烧结温度和压力的关系及（b）其金相组织^[31]

Figure 5. （a）Relationship of the hardness, sintering temperature, and pressure of the W–K alloys prepared by SPS and（b） the corresponding metallographic microstructures ^[31]

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图 6 （a）W–5%Mo（质量分数）合金1450 ℃非等温烧结过程中科肯达尔孔隙引起的膨胀和显微组织以及（b）1600 ℃放电等离子烧结W–5%Mo合金相对密度与温度的关系和显微组织^[32]

Figure 6. Expansion and microstructure of the W–5%Mo alloys (mass fraction) caused by Kirkendal pores in the non-isothermal sintering at 1450 ℃ (a) and the relationship between the relative density and temperature and the corresponding microstructure of the W–5%Mo alloys prepared by SPS at 1600 ℃ (b)^[32]

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图 7 纯W和W–5%Ta（质量分数）合金在不同剂量He⁺辐照下的结构损伤^[33]

Figure 7. Structural damage between pure W and W–5%Ta alloys (mass fraction) irradiated with different doses of He^+[33]

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图 8 不同辐照能量的W–Nb合金扫描电镜形貌^[34]：（a）50 eV；（b）80 eV

Figure 8. SEM images of the W–Nb alloys with different irradiation energies^[34]: (a) 50 eV; (b) 80 eV

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图 9 不同氦能W25富钨区高倍透射电镜形貌^[34]：（a）50 eV；（b）80 eV

Figure 9. High-magnification TEM images of W25 in the tungsten rich region with different helium energies^[34]: (a) 50 eV; (b) 80 eV

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图 10 W–Y₂O₃合金显微形貌^[37]：（a）表面结构；（b）室温断口形貌

Figure 10. SEM images of the W–Y₂O₃ alloys^[37]: (a) surface structure; (b) fracture morphology at room-temperature

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图 11 冷冻干燥样品微观结构及粒度分布^[38]：（a）不添加分散剂微观结构；（b）不添加分散剂粒度分布；（c）添加分散剂微观结构；（d）添加分散剂粒度分布

Figure 11. SEM images and particle size distribution of the freeze-dried samples^[38]: (a) SEM images without dispersant; (b) particle size distribution without dispersant; (c) SEM images with dispersant; (d) particle size distribution with dispersant

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图 12 纯W和W–2%Y₂O₃复合材料经氦离子辐照后表面形貌^[39]：（a）纯W表面辐照区；（b）纯W表面非辐照区；（c）W–2%Y₂O₃表面辐照区；（d）W–2%Y₂O₃表面非辐照区

Figure 12. Surface morphology of the pure tungsten and W–2%Y₂O₃ composites irradiated by helium ions^[39]: (a) pure tungsten surface in irradiated zone; (b) pure tungsten surface in non-irradiated zone; (c) W–2%Y₂O₃ surface in irradiated zone; (d) W–2%Y₂O₃ surface in non-irradiation zone

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图 13 纯W和W–La₂O₃合金横截面显微形貌^[41]：（a）纯W；（b）0.1% La₂O₃掺杂W合金；（c）1.0% La₂O₃掺杂W合金；（d）5.0% La₂O₃掺杂W合金

Figure 13. Cross-sectional images of the W and W–La₂O₃ alloys^[41]: (a) pure W; (b) 0.1% La₂O₃ doped W alloys; (c) 1.0% La₂O₃ doped W alloys; (d) 5.0% La₂O₃ doped W alloys

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图 14 不同碳化物掺杂钨合金高温退火后表面显微形貌^[43]：（a）W–10TaC，1600 ℃；（b）W–10ZrC，1600 ℃；（c）W–10TiC，8 h；（d）W–10ZrC，8 h

Figure 14. SEM images of the W alloys doped by different carbides after high-temperature annealing^[43]: (a) W–10TaC, 1600℃; (b) W–10ZrC, 1600 ℃; (c) W–10TiC, 8 h; (d) W–10ZrC, 8 h

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图 15 不同烧结温度下W–0.5ZrC复合材料相对密度^[44]

Figure 15. Relative density of the W–0.5ZrC composites at different sintering temperatures^[44]

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图 16 不同热流密度热冲击后W–ZrC试样的表面及加载区裂纹形貌^[45]：（a）0.22 GW·m⁻²；（b）0.33 GW·m⁻²；（c）0.44 GW·m⁻²；（d）0.22 GW·m⁻²；（e）0.33 GW·m⁻²；（f）0.44 GW·m⁻²；（g）0.22 GW·m⁻²裂纹深度；（h）0.33 GW·m⁻²裂纹深度；（i）0.44 GW·m⁻²裂纹深度

Figure 16. Surface and crack morphology in the loaded areas of the W–ZrC samples after 100 shots with the different heat flux^[45]: (a) 0.22 GW·m⁻²; (b) 0.33 GW·m⁻²; (c) 0.44 GW·m⁻²; (d) 0.22 GW·m⁻²; (e) 0.33 GW·m⁻²; (f) 0.44 GW·m⁻²; (g) cracking depth at 0.22 GW·m⁻²; (h) cracking depth at 0.33 GW·m⁻²; (i) cracking depth at 0.44 GW·m⁻²

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图 17 不同热流密度下试样裂纹宽度扫描电子显微形貌^[45]：（a）0.33 GW·m⁻²；（b）0.44 GW·m⁻²

Figure 17. SEM images of the crack width with the different heat flux^[45]: (a) 0.33 GW·m⁻²; (b) 0.44 GW·m⁻²

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图 18 应变速率5×10⁻⁴ s⁻¹下热等静压压坯拉伸伸长率随TiC质量分数的变化^[46]：（a）W–(0～1.5)TiC–H₂；（b）W–(0～1.5)TiC–Ar

Figure 18. Tensile elongation at the medium strain rate of 5×10⁻⁴ s⁻¹ for the hot isostatic pressing compacts as the function of TiC mass fraction^[46]: (a) W–(0~1.5)TiC–H₂; (b) W–(0~1.5)TiC–Ar

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图 19 钨纤维增韧钨基复合材料光学显微形貌^[48]

Figure 19. Optical image of the tungsten matrix composites toughened by tungsten fibers^[48]

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图 20 纯W及其合金在500 ℃下的应力–应变曲线^[53]

Figure 20. Stress-strain curves of the pure W and the alloys tested at 500 ℃^[53]

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图 21 添加TiC的W–K–TiC合金抗拉强度、维氏显微硬度与晶粒尺寸平方根倒数关系^[54]

Figure 21. Relationship of the tensile strength, Vickers micro-hardness, and the square root reciprocal of grain size for the W–K–TiC alloys with TiC addition^[54]

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图 22 W–ZrC–Re试样在不同温度下退火后的断裂表面微观形貌^[57]

Figure 22. SEM images of the fracture surface for the W–ZrC–Re samples after annealing at different temperatures^[57]

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图 23 W–Y₂O₃合金中W晶界氧化物粒子透射电镜高角环形暗场相（high angle annular dark field，HAADF）和能量色散X射线光谱^[58]：（a）La³⁺掺杂HAADF；（b）La³⁺掺杂EDX；（c）Hf⁴⁺掺杂HAADF；（d）Hf⁴⁺掺杂EDX

Figure 23. HAADF images and EDX of the oxide particles at W grain boundary for W–Y₂O₃ alloys^[58]: (a) HAADF of La³⁺ doping; (b) EDX of La³⁺ doping; (c) HAADF of Hf⁴⁺ doping; (d) EDX of Hf⁴⁺ doping

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图 24 试样断口扫描电子显微形貌和平均晶粒尺寸^[59]：（a）W–1TiC；（b）不同Ti含量W–1TiC–xTi平均晶粒尺寸；（c）W–1TiC–0.5Ti；（d）W–1TiC–0.7Ti

Figure 24. SEM micrographs of the fracture surface and the average grain size of samples^[59]: (a) W–1TiC; (b) the average grain size of the W–1TiC–xTi samples with different Ti contents; (c) W–1TiC–0.5Ti; (d) W–1TiC–0.7Ti

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表 1 纯W和W–2%Y₂O₃在氦离子辐照下不同区域的表面粗糙度^[39]

Table 1 Surface roughness of pure tungsten and W–2%Y₂O₃ in different regions under helium ion irradiation^[39]

试样	辐照区 / nm	非辐照区 / nm
纯W	138.5±3.5	84.0±3.5
W–2%Y₂O₃	136.5±3.0	120.5±3.5

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表 2 放电等离子烧结W–3Re–xHfC复合材料的测量密度、理论密度、相对密度和维氏硬度^[55]

Table 2 Measurement density, theoretical density, relative density, and Vickers hardness of W–3Re–xHfC composites prepared by SPS^[55]

试样	平均晶粒尺寸 / μm	测量密度 / (g·cm⁻³)	理论密度 / (g·cm⁻³)	相对密度 / %	维氏硬度，HV	抗压强度 / MPa
W–Re	8.81±0.15	18.92	19.40	97.5	342.6±12.5	250.43±8.61
W–Re–0.5HfC	7.63±0.20	18.94	19.35	97.9	369.4±10.3	305.26±12.42
W–Re–1.0HfC	5.82±0.18	18.95	19.24	98.5	381.8±13.4	400.15±11.05
W–Re–5.0HfC	3.85±0.12	18.57	18.81	98.8	447.1±8.6	605.28±10.61
W–Re–10.0HfC	2.14±0.13	17.68	18.38	96.2	659.4±15.3	852.35±5.62

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1. 化学表面改性
1.1 渗碳处理——表层贫Co且芯部含η相梯度结构
1.2 渗碳处理——表层贫Co且芯部不含η相梯度结构
1.3 脱碳处理——富Co表层梯度硬质合金
1.4 渗氮处理——表层富含立方相梯度结构
1.5 脱氮处理——表层富Co且无立方相梯度结构
2. 物理表面改性
2.1 涂层方法分析
2.2 涂层结构设计
3. 总结与展望

1. 化学表面改性
1.1 渗碳处理——表层贫Co且芯部含η相梯度结构
1.2 渗碳处理——表层贫Co且芯部不含η相梯度结构
1.3 脱碳处理——富Co表层梯度硬质合金
1.4 渗氮处理——表层富含立方相梯度结构
1.5 脱氮处理——表层富Co且无立方相梯度结构
2. 物理表面改性
2.1 涂层方法分析
2.2 涂层结构设计
3. 总结与展望

参考文献(59)

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面向等离子体材料用先进钨复合材料的改性研究进展与趋势

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