CN113787192B - 一种Cu相呈指状梯度分布的W-Cu复合板的制备方法 - Google Patents

一种Cu相呈指状梯度分布的W-Cu复合板的制备方法 Download PDF

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CN113787192B
CN113787192B CN202111209149.7A CN202111209149A CN113787192B CN 113787192 B CN113787192 B CN 113787192B CN 202111209149 A CN202111209149 A CN 202111209149A CN 113787192 B CN113787192 B CN 113787192B
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程继贵
周锐
魏邦争
陈鹏起
郑肃
喻新喜
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Hefei University of Technology
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Abstract

本发明公开了一种Cu相呈指状梯度分布的W‑Cu复合板的制备方法，是在W粉中加入以偏钨酸铵为原料通过燃烧合成方法获得的WOX粉末，并加入粘结剂和造孔剂制成浆料，然后通过流延、水中浸泡、烧结获得孔隙呈指状分布的W骨架，再经熔渗Cu获得目标产物。本发明方法制备的W‑Cu复合材料中Cu相由熔渗表面至试样内部呈指状梯度分布，且Cu相与W相相互钉扎，W‑Cu界面有良好的结合强度；本发明的方法具有材料成分性能可调控、工艺简单、成本低、适合规模化生产等特点。

Description

一种Cu相呈指状梯度分布的W-Cu复合板的制备方法
技术领域
本发明涉及一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，属于金属基复合材料制备领域。
背景技术
功能梯度材料(FGM)是指通过连续地改变两种或两种以上性质不同的材料的结构、组成、密度等，使其内部界面减小甚至消失，从而得到材料成分非均匀变化而性能呈梯度变化的新型非均质复合材料。FGM的研究包括材料设计、材料合成(制备)和材料特性评价，这三部分相辅相成，缺一不可，其核心部分是材料制备。
W-Cu FGM结合了Cu的良好导电、导热和抗腐蚀性以及W的高硬度、强度和热稳定性，同时沿截面由高W(纯W)逐渐过渡至高Cu(纯Cu)层，具备了多种优异性能，在电子封装、航空航天中有良好的应用前景。然而，由于W和Cu之间熔点相差大，且互不相溶，通过粉末冶金工艺制备高致密的W-Cu FGM工艺难度较大且梯度成分分布难以有效控制。目前W-Cu梯度材料多采用叠层法制备，所得的W-Cu梯度复合材料大多为层状结构，其层与层之间仍有明显的界面，这种界面在极端的工作环境下容易因层与层之间的热膨胀差异而在界面处产生开裂等现象，从而影响其使用寿命，M.Richou等人设计的W-Cu层状梯度复合材料在经过972次热循环之后出现开裂现象(M.Richou,F.Gallay,B.
Figure BDA0003308181920000011
et al.FusionEngineering and Design,2020,157.111610)。魏邦争等人以不同粒度W粉为原料、聚乙烯醇缩丁醛(PVB)为粘结剂、无水乙醇为溶剂制备浆料，而后通过沉降、排胶和预烧得到孔隙呈连续梯度分布的W骨架，随后渗Cu，得到了Cu含量由28.03％至44.47％分布的W-Cu功能梯度材料(Wei BZ,Yu XX,Chen RZ,et al.A Novel Approach to Fabricate W-CuFunctionally Graded Materials via Sedimentation and Infiltration Method[J].Materials Science and Engineering:A,2021.)。江大发等人对比了原始界面、纳米波纹界面、微立方体界面以及微坑界面四种界面之间W、Cu之间的粘结强度，得出W、Cu微坑界面全面提高了W、Cu接头的抗拉强度、剪切强度、传热能力、耐热应力和热疲劳寿命(Jiang D,Long J,Han J,et al.Materials Science and Engineering:A,2017,696(JUN.1):429-436.)。
综上，目前制备W-Cu梯度复合材料方面大多是层状结构，而像Cu相呈指状梯度分布的W-Cu梯度复合材料的研究较少。
发明内容
本发明的目的在于提供一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，首先制备具有指状孔隙分布的W骨架，而后在熔渗烧结炉中，在N2或H2气氛保护下，将紫Cu块或Cu粉末压坯置于具有指状孔的W骨架表面，并加热使Cu熔化，Cu熔液在毛细管力的作用下渗入W骨架的指状孔中，最终得到Cu相由熔渗表面至试样内部呈指状梯度分布的复合板，且Cu相与W相相互钉扎，W、Cu界面有良好的结合强度。
为实现目的，本发明采用如下技术方案：
一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特点在于，按如下步骤进行：
(1)将WOX粉末与W粉混合，获得粉末混合料；将所述粉末混合料与粘结剂聚醚砜、造孔剂聚乙烯吡咯烷酮一起加入N-甲基吡咯烷酮溶剂中，在行星式球磨机中球磨混合均匀，得到浆料；
(2)将所述浆料在PET膜上流延得到生坯，所得生坯与PET膜一起在水中浸泡以部分除去溶剂N-甲基吡咯烷酮，随后将生坯与PET膜分离，而后烘干；
(3)在H2气氛下，先将所得生坯在500～800℃预烧以脱除粘结剂并还原，再升温至800～2000℃烧结以得到孔隙呈指状分布的W骨架；
(4)对所述W骨架进行熔渗Cu，然后随炉冷却，即获得Cu相呈指状梯度分布的W-Cu复合板。
进一步的，所述WOX粉末是采用偏钨酸铵、硝酸铵、甘氨酸、乙二胺四乙酸为原料，加去离子水分散后放入马弗炉里恒温200℃通过燃烧合成方法获得。采用WOX粉末的目的，是为了防止脱除粘结剂并还原之后碳残留在材料中与W形成过量WC，从而影响最终材料的性能；所述WOX粉末是采用偏钨酸铵为原料通过燃烧合成方法获得的，这种方式获得的WOX粉末有着特殊的表面结构、化学活性最高，适用于超细颗粒钨粉以及各类纳米级钨化合物的生产。
进一步的，步骤(1)中，所述WOX粉末占所述粉末混合料质量的0～50wt.％；所述聚醚砜与所述聚乙烯吡咯烷酮的加入量各自独立的占所述粉末混合料质量的1～6％；所述浆料的固含量为50～85wt.％。
进一步的，步骤(1)中，所述球磨的转速为100～400r/min、球磨时间为2～48h。
进一步的，步骤(2)中，经流延所得生坯的厚度为200μm～2mm。
进一步的，步骤(2)中，所得生坯与PET膜一起在水中浸泡时，以PET膜在下、生坯在上并保证样品与水平面平行，从而控制生坯中的孔隙分布，浸泡时间为12～48h。
进一步的，步骤(2)中，所得生坯与PET膜一起在水中浸泡时，在生坯上表面与水的界面处发生水和N-甲基吡咯烷酮交换，并且水渗透到生坯中，形成指状孔。
进一步的，步骤(3)中，所得生坯在500～800℃的预烧时间为1～4h，在800～2000℃的烧结时间为1～4h，通过控制骨架烧结温度从而控制最终W-Cu复合板中梯度成分分布。
进一步的，步骤(4)中，对W骨架进行熔渗Cu是在熔渗烧结炉中，在N2或H2气氛保护下，将纯紫Cu块或电解Cu粉末压坯置于具有指状孔的W骨架表面，并加热使Cu熔化，Cu熔液在毛细管力的作用下渗入W骨架的指状孔中，熔渗Cu的温度范围为1200～1500℃、时间为1～4h。
本发明的有益效果体现在：
1、本发明方法制备的W-Cu复合材料中Cu相由熔渗表面至试样内部呈指状梯度分布，且Cu相与W相相互钉扎，W-Cu界面有良好的结合强度；本发明的方法具有材料成分性能可调控、工艺简单、成本低、适合规模化生产等特点。
2、本发明是以偏钨酸铵为原料通过燃烧合成方法制得WOX粉末，原料成本低、易获得，所得WOX粉末有着特殊的表面结构、化学活性最高，适用于超细颗粒钨粉以及各类纳米级钨化合物的生产。
3、本发明通过单向渗水而后脱除粘结剂预烧获得的W骨架具有指状孔隙的特殊结构。
4、本发明的方法，可以通过控制固含量从而控制指状孔隙的大小来控制梯度分布：当固含量较小时，溶液的扩散速度较快，形成的新核数量多尺寸小，此时形成的孔结构是海绵状；固含量较大时，溶液的扩散速度较慢，形成的新核持续长大，则形成的孔结构为指状孔。
5、本发明的方法中，通过脱除粘结剂并还原工艺获得指状孔隙分布的W骨架中，其指状孔隙由小到大，细粒度W粉具有更好的烧结活性，在较低温度下即可致密，所以通过控制烧结工艺，可以扩大W骨架中的孔隙分布范围，能够获得由纯W层到W-Cu层过渡的梯度材料，满足其在高温下的工作稳定性。
附图说明
图1为Cu相呈指状梯度分布的W-Cu复合板的结构示意图；
图2为实施例1中所得WOX粉末的SEM照片；
图3为实施例1中所得W骨架的SEM照片；
图4为实施例1中所得W-Cu复合板的SEM照片；
图5为实施例1中所得W-Cu复合板的EDS能谱图及含量分布。
具体实施方式
下面结合附图对本发明的实施例作详细说明，下述实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
(1)将偏钨酸铵、硝酸铵、甘氨酸和乙二胺四乙酸混合后，加去离子水分散，然后放入马弗炉里空气气氛下200℃恒温燃烧2h，获得WOX粉末；偏钨酸铵、硝酸铵、甘氨酸、乙二胺四乙酸和去离子水的质量比12:19.2:7:0.7:50。图2为所得WOX粉末的SEM照片，可以看出所得粉末为短棒状，直径为0.5～2μm，长度为2～10μm。
称取WOX粉50g、0.8μm W粉100g、聚醚砜4g、聚乙烯吡咯烷酮2.67g、N-甲基吡咯烷酮26.7g，一起加入球磨罐中，球料比1:5，球磨12h，转速400r/min，获得固含量为82％的浆料。
(2)将所得浆料在PET膜上流延得到厚度为2mm的生坯，所得生坯与PET膜一起在水中浸泡以部分除去溶剂N-甲基吡咯烷酮，浸泡时以PET膜在下、生坯在上并保证样品与水平面平行，从而控制生坯中的孔隙分布，浸泡时间为24h，浸泡时在生坯上表面与水的界面处发生水和N-甲基吡咯烷酮交换，并且水渗透到生坯中，形成指状孔。
浸泡结束后，将生坯与PET膜分离，而后烘干。
(3)在H2气氛下，先将所得生坯在500℃预烧4h以脱除粘结剂并还原，再升温至800℃烧结2h以得到孔隙呈指状分布的W骨架。图3为所得W骨架的SEM照片，可以看出从上至下指状孔隙由小到大。
(4)在熔渗烧结炉中，在N2气氛保护下，将纯紫Cu块置于具有指状孔的W骨架表面，并加热使Cu熔化，Cu熔液在毛细管力的作用下渗入W骨架的指状孔中，熔渗Cu的温度为1300℃、时间为2h。
图4为本实施例所得W-Cu复合板的SEM照片，可以看出Cu相呈指状梯度分布，且从上至下梯度由小到大。
图5为本实施例所得W-Cu复合板的EDS能谱图及含量分布，可以看出W相与Cu相之间结合良好。
以上仅为本发明的示例性实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于，按如下步骤进行：
(1)将WOX粉末与W粉混合，获得粉末混合料；将所述粉末混合料与粘结剂聚醚砜、造孔剂聚乙烯吡咯烷酮一起加入N-甲基吡咯烷酮溶剂中，在行星式球磨机中球磨混合均匀，得到浆料；
所述WOX粉末占所述粉末混合料质量的50wt.％及以下，且不为0；所述聚醚砜与所述聚乙烯吡咯烷酮的加入量各自独立的占所述粉末混合料质量的1～6％；所述浆料的固含量为50～85wt.％；
(2)将所述浆料在PET膜上流延得到生坯，所得生坯与PET膜一起在水中浸泡以部分除去溶剂N-甲基吡咯烷酮，随后将生坯与PET膜分离，而后烘干；
(3)在H2气氛下，先将所得生坯在500～800℃预烧以脱除粘结剂并还原，再升温至800～2000℃烧结以得到孔隙呈指状分布的W骨架；
(4)对所述W骨架进行熔渗Cu，然后随炉冷却，即获得Cu相呈指状梯度分布的W-Cu复合板。
2.根据权利要求1所述的一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于：所述WOX粉末是采用偏钨酸铵、硝酸铵、甘氨酸、乙二胺四乙酸为原料，加去离子水分散后放入马弗炉里恒温200℃通过燃烧合成方法获得。
3.根据权利要求1所述的一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于：步骤(1)中，所述球磨的转速为100～400r/min、球磨时间为2～48h。
4.根据权利要求1所述的一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于：步骤(2)中，经流延所得生坯的厚度为200μm～2mm。
5.根据权利要求1所述的一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于：步骤(2)中，所得生坯与PET膜一起在水中浸泡时，以PET膜在下、生坯在上并保证样品与水平面平行，从而控制生坯中的孔隙分布，浸泡时间为12～48h。
6.根据权利要求1所述的一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于：步骤(2)中，所得生坯与PET膜一起在水中浸泡时，在生坯上表面与水的界面处发生水和N-甲基吡咯烷酮交换，并且水渗透到生坯中，形成指状孔。
7.根据权利要求1所述的一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于：步骤(3)中，所得生坯在500～800℃的预烧时间为1～4h，在800～2000℃的烧结时间为1～4h。
8.根据权利要求1所述的一种Cu相呈指状梯度分布的W-Cu复合板的制备方法，其特征在于：步骤(4)中，对所述W骨架进行熔渗Cu是在熔渗烧结炉中，在N2或H2气氛保护下，将纯紫Cu块或电解Cu粉末压坯置于具有指状孔的W骨架表面，并加热使Cu熔化，Cu熔液在毛细管力的作用下渗入W骨架的指状孔中，熔渗Cu的温度范围为1200～1500℃、时间为1～4h。
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