Research progress on the effects of binder and powder characteristic on the feeding properties of metal injection molding
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摘要:
在金属注射成形工艺中，金属粉末需要和粘结剂充分混合得到喂料后进行注射、脱脂和烧结。喂料中的粉末特性和粘结剂是金属注射成形的核心，对喂料的流变性能和粉末装载量有很大影响，进而影响注射、脱脂和烧结环节，是金属注射成形的研究热点。本文以粘结剂组分优化、金属粉末改性和喂料性能提升为出发点，阐述了粘结剂各组分的作用以及粘结剂中添加剂、金属粉末形状、粉末粒径、粉末表面改性对于喂料流变性能和粉末装载量的影响。为改善喂料性能所添加的添加剂包括增塑剂、稳定剂、表面活性剂等。添加剂的加入、粒度分布与形状的优化以及粉末表面改性可以使喂料的粘度、流变参数等流变性能以及粉末临界装载量得到明显改善。
Abstract:In the metal injection molding process, the metal powders need to be fully mixed with the binders to get the feeds before injection, degreasing, and sintering. The powder characteristic and binders of the feeds are the core of the metal injection molding, which have the great impact on the rheological properties and powder loading capacity of the feeds, and then affect the injection, degreasing, and sintering. Based on the optimization of binder components, the metal powder modification, and the improvement of feeding performance, the effects of binder components, additives in binders, powder shape, powder particle size, and surface modification on the rheological properties and loading capacity of the feeds were described. The additives in binders were added to improve the feed performance, including plasticizers, stabilizers, and surfactants. The addition of additives, the optimization of particle size distribution and shape, and the surface modification of the powders could significantly improve the rheological properties of the feeds, such as feed viscosity, rheological parameters, and the critical loading capacity of the powders.
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钨基高密度合金也被称作“重钨合金（WHAs）”，一般由质量分数88%～99%的钨和熔点相对较低的过渡金属（Ni、Fe和Co）组成，其中体心立方结构的W晶粒均匀地分散在具有面心立方结构的γ-(Ni、Fe)粘结相中[1−2]，这种W相和γ-(Ni、Fe)相构成的两相合金具有许多优良特性，如高密度（17～18.5 g·cm−3）、高力学强度、良好的耐腐蚀性和无辐射污染。这些优异的特性使得重钨合金在航天、航空和军事领域有着广泛的应用，可用作动能穿透器候选材料和屏蔽材料[3−4]。
在利用传统粉末冶金技术制备WHAs时，将预成形样品置于氢气气氛中进行液相烧结，烧结温度通常高于
1465 ℃，且烧结时间长，导致WHAs中W晶粒非常粗大（40～60 μm）[5−6]，这限制了合金性能的进一步提高。弥散强化是目前提升WHAs性能的主要手段之一。在WHAs中添加高硬度、高强度的陶瓷相颗粒（Y2O3、La2O3、ZrB2、Al2O3等），弥散分布的陶瓷相颗粒能降低通过相应界面处的原子传输速率，阻碍晶界迁移，细化晶粒。此外，弥散的陶瓷相颗粒也能够钉扎位错，提升材料对位错的存储能力，进而提高WHAs力学性能[7−9]。碳化锆（ZrC）硬度高（～20 GPa）、熔点高（～3445 ℃），并且能与W形成共格界面，可被应用于制备弥散强化纯钨材料。Li等[10−11]在钨中加入0.5%ZrC（质量分数）进行弥散强化，晶粒尺寸从纯钨的100 μm细化到W−ZrC复合材料的30 μm，拉伸强度从250 MPa提升到了460 MPa。此外，采用纳米粉末原料能够有效增加各成分的混合均匀性并且降低复合粉末的尺度，有利于提升烧结后合金的组织均匀性和降低烧结后WHAs的W晶粒尺度。因此，选用纳米级粉体为原料成为制备重钨合金重要的发展趋势[12−14]。本文选用纳米级W、NiO、Fe2O3、ZrC粉末为原料制备纳米W−Ni−Fe−ZrC纳米复合粉体，并通过
1500 ℃液相烧结制备了含不同质量分数ZrC（0、1%、2%）的增强90W−7Ni−3Fe−xZrC（90W−ZrC）合金，研究了ZrC质量分数对90W−ZrC合金组织结构及力学性能的影响。1. 实验材料及方法
使用W、NiO、Fe2O3、ZrC纳米粉为原料，粉末平均粒径、纯度及形貌如图1和表1所示。将这四种原料按90W−7Ni−3Fe−xZrC（x=0，1%，2%）质量比称重，然后以250 r·min−1的速度在氧化锆球磨罐中球磨混合12 h，球磨介质为无水乙醇，球料质量比为6:1。球磨后的混合粉末经70 ℃干燥后，分别在550 ℃和800 ℃下氢还原1 h，获得90W−7Ni−3Fe−xZrC（90W−ZrC）纳米复合粉末。将纳米复合粉末填充到直径为10 mm的圆柱模具中，在250 MPa压力下模压成形。将成形后的胚料在
1500 ℃氢气气氛下烧结2 h，制备出90W−7Ni−3Fe−xZrC（90W−ZrC）合金。![]()
图 1 粉末原料显微形貌：（a）W；（b）NiO；（c）Fe2O3；（d）ZrCFigure 1. SEM images of the powder raw materials: (a) W; (b) NiO; (c) Fe2O3; (d) ZrC表 1 粉末原料晶粒尺寸及纯度Table 1. Grain size and purity of the raw material powders原料 晶粒尺寸 / nm 纯度 / % W 100～200 ＞99.9 NiO 50～100 ＞99.9 Fe2O3 50～100 ＞99.9 ZrC 50～100 ＞99.9 烧结样品经SiC砂纸（80～2000目）打磨和金刚石软膏抛光后进行金相腐蚀，采用10%铁氰化钾溶液（K3Fe(CN)6）和10%氢氧化钠（NaOH）溶液按照80 mL K3Fe(CN)6 + 20 mL NaOH配制腐蚀剂，腐蚀时间30～60 s。采用配有能谱仪（energy disperse spectroscope，EDS）的韩国库塞姆公司EM30AX+台式扫描电子显微镜（scanning electron microscope，SEM）对粉末原料、纳米复合粉体及90W−ZrC合金组织结构进行表征，加速电压5～25 kV。利用Nano Measurer处理90W−ZrC合金显微形貌图，获得W晶粒尺寸。使用Bruker D8 ADVANCE型X射线衍射仪（X-ray diffraction，XRD）对纳米复合粉末及90W−ZrC合金的物相进行分析，扫描速度10°·min−1，其中块体试样测试前经过抛光处理。
压缩样品是直径3.0 mm、高度4.5 mm的小圆柱。在Instron8871型电子万能试验机上完成室温压缩变形实测，压缩变形速率为10−3 s−1，取断裂前最高应力值或40%变形量时的最高应力值为抗压强度，以产生0.2%残余变形的应力值作为屈服强度。通过CMT5105型数显韦氏硬度测试仪测量合金硬度，设置加载重量为0.5 kg，保持载荷15 s，对单个样品的5个不同位置测量其硬度，取平均值。在烧结过程中，合金生胚逐渐致密，利用阿基米德排水法统计含不同质量分数ZrC的合金实际密度，合金理论密度计算如式（1）所示。将实际密度除以理论密度得到合金的相对密度，在6次重复测试下取平均值。
$$ \frac{{100}}{\rho }{\text{ = }}\sum {\frac{{W_i}}{{\rho _i}}} $$ (1) 式中：ρ是合金理论密度，Wi是各成分质量分数，ρi是各成分理论密度。
2. 结果与讨论
2.1 90W−ZrC复合粉体相貌及物相成分
90W−ZrC复合粉体显微形貌和能谱表征如图2所示。三种复合粉末粒度分布均匀，平均粒径均小于200 nm，这得益于纳米粉末原料。如图2（b）～图2（c）能谱分析所示，Zr元素分布均匀，没有明显的富集现象。这是因为采用了纳米尺寸的ZrC粉末原料，若采用粗大的ZrC原料，在低能球磨下难以达到各元素均匀分布的效果，并且可能存在粗大的ZrC颗粒，这种复合不均匀的粉末在烧结后容易造成合金中组织不均匀和元素偏析，进而导致合金的强度和塑性下降，因此，选用细小的纳米粉末原料制备小尺度均匀复合粉体对于提高WHAs的性能极为重要。此外，W元素与Ni、Fe元素分布均匀，Ni、Fe元素的分布高度重合，这可能是由于在800 ℃氢还原过程中，混合粉末中的Fe原子固溶到Ni中形成了γ-(Ni、Fe)相。
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图 2 添加不同质量分数ZrC的90W−ZrC复合材料粉体显微形貌和能谱分析：（a）0；（b）1%；（c）2%Figure 2. SEM images and EDS patterns of the 90W−ZrC composite powders with different mass fraction of ZrC: (a) 0; (b) 1%; (c) 2%对90W−ZrC复合粉末进行X射线衍射分析，研究ZrC质量分数对复合粉末物相的影响，结果如图3所示。由图可知，三种复合粉末都形成了γ-(Ni, Fe)相，这与前文Ni、Fe元素分布高度重合结果一致。Lee等[15]在对球磨粉末进行还原时也发现，450 ℃温度下γ-(Ni, Fe)相己经形成，随着温度升至600 ℃，形成了稳定的γ-(Ni, Fe)相。此外，在添加1%ZrC的复合粉末中并没有检测出ZrC，但在添加2%ZrC的复合粉末中检测出了ZrC，这说明ZrC含量较低，X射线衍射可能无法检测出其物相。同时可以明显观察到，三种复合粉末的W相以及γ-(Ni, Fe)相的峰强基本一致。
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图 3 添加不同质量分数ZrC的90W−ZrC复合粉体X射线衍射图谱Figure 3. XRD patterns of the 90W−ZrC composite powders with different mass fraction of ZrC2.2 90W−ZrC合金组织结构变化
90W−ZrC合金相对密度如图4所示。由图可知，90W−ZrC合金相对密度随ZrC质量分数的增加呈现下降趋势，且ZrC含量越高，相对密度下降的幅度越大。未添加ZrC的90W合金相对密度为99.01%，当添加质量分数1%ZrC时，合金相对密度为98.4%，当ZrC质量分数增加到2%，合金相对密度下降到97.6%。这是因为聚集于W晶界周围的ZrC阻碍其扩散，在细化晶粒的同时，也限制了合金长大带来的致密化。
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图 4 90W−ZrC合金相对密度和W−W连接度Figure 4. Relative density and the W−W contiguity of the 90W−ZrC alloysW晶粒之间的接触（连接）被称为W−W连接度，W−W连接度（CW−W）是决定W合金或W合金复合材料力学性能的关键因素，可以由式（2）得出[16]。
$$ {C_{{\text{W}} - {\text{W}}}} = \frac{{2{N_{{\text{W}} - {\text{W}}}}}}{{{N_{{\text{W}} - {\text{M}}}} + 2{N_{{\text{W}} - {\text{W}}}}}} $$ (2) 式中：NW−W和NW−M分别是W与W连接的数量以及W和基体结合界面的数量，可使用线截距法确定，在显微形貌图上放置任意直线，并对至少100次测量的平均接触点数量进行计数。如图4所示，在未添加ZrC时，90W合金的W−W连接度为0.431，当ZrC质量分数为2%时，W−W连接度已经下降到了0.407，随着ZrC含量的增加，W−W连接度下降的幅度加大，这与前述相对密度下降的规律一致。
为了确定经
1500 ℃烧结后90W−ZrC合金的物相，对其进行X射线衍射分析，结果如图5所示。由图可知，合金中仅有W相和γ-(Ni, Fe)粘结相存在，并没有生成金属间化合物，这与合金元素的比例有关，当粘结相Ni:Fe=7:3（质量比）时，不会出现影响合金性能的Ni4W[17]。与复合粉末物相不同，烧结后90W−2%ZrC合金中也没有检测到ZrC峰。![]()
图 5 添加不同质量分数ZrC的90W−ZrC合金X射线衍射图谱Figure 5. XRD patterns of the 90W−ZrC alloys with different mass fraction of ZrC如图6所示，经
1500 ℃烧结后90W−ZrC合金内W晶粒呈现出圆润的球形形貌，这是典型的液相烧结特征，从能谱分析来看，γ-(Ni, Fe)粘结相均匀的分布在W晶粒四周，将其包覆。90W−ZrC合金内W晶粒随着ZrC含量的增加，呈现出逐渐细小化的趋势，并且ZrC含量的增加导致W晶粒出现分布不均匀的特征。W晶粒的细化是由于聚集在W晶粒晶界周围的ZrC颗粒起到“钉扎”作用，阻碍高温烧结过程中晶界迁移，降低W晶粒的长大速率。可参考90W−ZrC合金的形貌与元素分布分析不同尺寸W晶粒分布不均匀的原因，在ZrC颗粒相对集中的区域，晶粒细化程度较大，而在ZrC颗粒较为稀少的区域，晶粒甚至没有被细化的现象，如图6（c）所示，这种现象随着添加ZrC含量的增加越发显著。![]()
图 6 添加不同质量分数ZrC的90W−ZrC显微形貌和能谱分析：（a）0；（b）1%；（c）2%Figure 6. SEM images and EDS patterns of the 90W−ZrC alloys with different mass fraction of ZrC: (a) 0; (b) 1%; (c) 2%图7是90W−ZrC合金W晶粒尺寸分布。随着ZrC质量分数的增加，W平均晶粒尺寸呈现下降趋势，小尺寸W晶粒数量逐渐增多，这与显微相貌结果一致。当小尺寸W晶粒数量累计达到晶粒数量总量的50%时，W晶粒尺寸随ZrC含量的增加减小。90W−2%ZrC合金小尺寸晶粒最多，并且大尺寸W晶粒也因ZrC含量的增大，从最大45～50 μm降低到最大35～40 μm，细化效果较为显著。90W−2%ZrC合金中W晶粒平均尺寸为20.69 μm，相比未添加ZrC的90W合金，W晶粒尺寸为23.77 μm，下降了13%。
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图 7 添加不同质量分数ZrC的90W−ZrC合金中W晶粒尺寸分布：（a）0；（b）1%；（c）2%Figure 7. W grain size distribution in the 90W−ZrC alloys with different mass fraction of ZrC: (a) 0; (b) 1%; (c) 2%2.3 90W−ZrC合金力学性能与断口分析
图8所示为90W−ZrC合金经
1500 ℃烧结后的压缩力学性能。如图8（a）所示，不添加ZrC时，在40%变形量下90W合金的屈服强度和抗压强度分别为730 MPa、1570 MPa；当ZrC质量分数为1%时，在40%压缩变形量下90W−ZrC合金的屈服强度和强度分别为791 MPa、2179 MPa，相对于未添加ZrC的90W合金分别提升了8.35%、38.7%。当ZrC质量分数为2%时，90W−ZrC合金的屈服强度提升最大，达到了861 MPa，但相较未添加ZrC的90W合金也仅提升了18%，并且合金的塑性下降极大，在25%变形量下断裂，强度仅有1679 MPa。90W−ZrC合金硬度变化规律与屈服强度表现一致。如图8（b）所示，不添加ZrC时，合金硬度为HV 302，ZrC质量分数为2%时，合金硬度提升到HV 380，相比未添加ZrC的90W合金提升了25%。随ZrC含量的增加，合金的屈服强度有所提升，但提升不大，而合金的塑性却下降极大。综上所述，添加1%ZrC合金的强塑性匹配效果最佳。![]()
图 8 90W−ZrC合金压缩屈服强度与硬度：（a）屈服强度曲线；（b）平均硬度Figure 8. Compressive yield strength and hardness of the 90W−ZrC alloys: (a) yield strength curves; (b) average hardness90W−ZrC合金力学性能如表2所示。弥散强化90W−ZrC合金的抗压强度提升幅度极大，在添加1%ZrC后，屈服强度提升了38.7%。这是因为ZrC颗粒对加工硬化有积极影响，当塑性变形在基体中积累到一定程度后，W晶粒和基体相同时进一步变形，产生高密度位错，由于晶间ZrC颗粒的存在，有效地对位错“钉扎”，阻碍其滑移和攀移[18]，从而提高了90W−ZrC合金抗压强度。但是，当添加过量ZrC时（如添加质量分数2%ZrC），晶界处会聚集大量ZrC颗粒，这导致90W合金的抗压强度提升幅度极低且密度和塑性大大降低。
表 2 90W−ZrC合金晶粒尺寸及力学性能Table 2. Grain size and mechanical properties of the 90W−ZrC alloys合金 相对密度 / % 平均晶粒尺寸 / μm W−W连接度 平均硬度，HV 压缩屈服强度 / MPa 抗压强度 / MPa 90W 99.0±0.14 23.77 0.431±0.027 302.4±7.3 730 1570 （40%变形）90W−1%ZrC 98.4±0.21 22.17 0.414±0.022 351.3±8.7 791 2179 （40%变形）90W−2%ZrC 97.6±0.24 20.69 0.407± 0.0283 380.9±9.4 861 1679 （25%变形)WHAs屈服强度通常与基体的体积分数、W晶粒尺寸、W−W连接度、相对密度和均匀性密切相关。Lee等[19]研究表明，WHAs的压缩屈服强度主要是由Ni−Fe基体变形引起，可以用修正的Hall-Petch方程[20]表示，如式（3）所示。
$$ {\sigma _{\text{y}}} = {\sigma _0} + K\left[ {\frac{{{C_{{\text{W}} - {\text{W}}}}\left( {1 - {V_{\text{M}}}} \right)}}{{{G_{\text{W}}}{V_{\text{M}}}}}} \right] $$ (3) 式中：σy为WHA屈服强度，σ0和K是常数，CW−W是W−W连接度，GW为钨晶粒尺寸，VM为基体体积分数。ZrC−90W的屈服强度随W−W连接度上升与W晶粒减小而提高，ZrC对合金的压缩屈服强度没有额外的强化效果[19]，因此添加2%ZrC时，合金屈服强度也仅提升了18%。
高密度的WHAs性能一般和其断裂方式密切相关。两相合金的WHAs断裂方式分成四种模型：W晶粒与W晶粒晶面断裂（W−W）、W与基体相界面断裂（W−M）、W晶粒穿晶断裂（W）和基体相界面延性撕裂（M），其中W−W界面结合力最弱，裂纹一般在此产生。Gong等[21]研究表明，WHAs的断裂模式与W晶粒和基体相之间的界面强度密切相关，如果W−M界面强度较低，则基体相首先变形，随后应力转移到W晶界面上，导致微裂纹在W−W界面形成并扩展，直至断裂。粘结相在流动应力作用下发生形变硬化，对钨晶粒产生足够的拉应力，这可能导致断裂优先发生在W晶粒上。因此，如果在WHAs断口中存在大量W−W断裂就可以确定合金的塑性较差。90W−ZrC合金断口形貌如图9所示，90W合金内部W晶粒呈球形，与前文显微形貌结果一致，说明
1500 ℃已经完全达到液相烧结温度，90W断口主要以W−M界面断裂为主，存在部分W−W晶面断裂。随着ZrC添加，断口形貌发生改变，W−W晶面断裂逐渐增多，在添加ZrC至1%时，断裂模式已经基本转变为W−W晶面断裂。当ZrC添加至2%时，不仅断裂模式以W−W晶面断裂为主，而且在断口内W晶粒附近粘结相中出现了孔洞，如图9（c）所示，这意味着过量的ZrC会影响合金的致密化并且降低合金的塑性。![]()
图 9 添加不同质量分数ZrC的90W−ZrC合金断口形貌：（a）0；（b）1%；（c）2%Figure 9. Fracture morphology of the 90W−ZrC alloys with different mass fraction of ZrC: (a) 0; (b) 1%; (c) 2%3. 结论
（1）采用纳米级W、NiO、Fe2O3、ZrC粉末作为原料，制备出元素分布均匀的W−Ni−Fe−ZrC纳米复合粉末。球磨后的混合粉末在800 ℃氢还原过程中形成了稳定的γ-(Ni, Fe)相。
（2）90W−ZrC合金的W−W连接度、相对密度以及W晶粒尺寸都随ZrC质量分数增加而下降。当ZrC质量分数为2%时，W−W连接度从0.431下降到0.407，相对密度从99.0%下降到97.6%，W晶粒细化明显，晶粒尺寸从23.77 μm降低到20.69 μm。
（3）当添加质量分数2%ZrC时，90W−ZrC合金的压缩屈服强度和抗压强度分别达到861 MPa、
1679 MPa，但在25%的变形下便断裂。在90W中添加1%ZrC能达到较好的强塑性匹配效果，屈服强度和抗压强度可达791 MPa、2179 MPa，相较未添加ZrC的90W分别提高了8.35%、38.7%。（4）90W−ZrC合金抗压强度因弥散分布的ZrC对位错的“钉扎”大幅提升。ZrC含量增加对90W屈服强度的提升作用较低，90W−ZrC合金屈服强度的提升主要通过晶粒的细化，并且过量的添加ZrC会使合金的塑性大幅下降。
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表 1 金属注射成形技术在不同行业的应用
Table 1 Application of the metal injection molding in different industries
行业 金属材料 粘结剂 优势 参考文献 生物医疗 316L不锈钢 PW–PP–CW–SA 具有良好的生物相容性 [16] Co–Cr–Mo PW–PP–SA [17–19] Fe CW–NR–SA–DCP [20] Cp-Ti PEG–PMMA–SA [21] 航空航天 Ti–6Al–4V POM–EVA–LDPE–SA 尺寸精度高、可以生产形状复杂的产品 [22] 汽车制造 Ti–48Al–2Cr–2Nb PW–HDPE–PP–SA 生产效率和材料利用率高 [23] Fe PW–LDPE–SA [24] 注：PW为石蜡，PP为聚丙烯，CW为巴西棕榈蜡，SA为硬脂酸，NR为天然橡胶，DCP为过氧化二异丙苯，PEG为聚乙二醇，Cp-Ti为商业纯钛，PMMA为聚甲基丙烯酸甲酯，POM为聚甲醛，EVA为乙烯–乙酸乙烯共聚物，LDPE为低密度聚乙烯，HDPE为高密度聚乙烯。 
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表 2 金属注射成形金属零件喂料组成（粘结剂体系）
Table 2 Feed composition of the metal parts produced by MIM (binder system)
主要粘结剂 骨架粘结剂 表面活性剂 其他 粉末 参考文献 PW PP SA SEBS 316L [40] PP CW 4605 钢[14,41] PP — Fe、Ni [42] LLDPE — Mn、Zn、Fe [43] PP、PE — W、Cu [44] PP、PE — Fe、Ni、Cu [45] HDPE、PP — Ti、Al [23] PEG PMMA SA — Ti [34] PPC、PMMA PVAc Ti [33] PW AW 316L [35] CAB — Fe、Ni [36] TPS LLDPE SA CA 316L [39] POM HDPE、EVA SA HPN202 Ti、Al、V [46] C 316L [47] — 316L [48] 注：PW为石蜡，PE为聚乙烯，SEBS为氢化苯乙烯–丁二烯嵌段共聚物，PEG为聚乙二醇，PP为聚丙烯，HDPE为高密度聚乙烯，EVA为乙烯–乙酸乙烯共聚物，PMMA为聚甲基丙烯酸甲酯，CW为巴西棕榈蜡，POM为聚甲醛，SA为硬脂酸，PVAc为聚醋酸乙烯酯，PPC为聚碳酸亚丙酯，AW为乙烯双硬脂酰胺，CA为纤维素乙酸酯，HPN202为超支化聚酰胺，TPS为热塑性淀粉，CAB为醋酸丁酸纤维素，LLDPE为线性低密度聚乙烯。
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表 3 文献报道的316L不锈钢粉末的不同粉末装载量与相对密度
Table 3 Different powder loading and relative density of 316L stainless steel powder
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