CN116969763B - 一种石墨烯增韧无粘接相wc基硬质合金及其制备方法 - Google Patents
一种石墨烯增韧无粘接相wc基硬质合金及其制备方法 Download PDFInfo
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- CN116969763B CN116969763B CN202311237515.9A CN202311237515A CN116969763B CN 116969763 B CN116969763 B CN 116969763B CN 202311237515 A CN202311237515 A CN 202311237515A CN 116969763 B CN116969763 B CN 116969763B
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于合金材料技术领域，公开了一种石墨烯增韧无粘接相WC基硬质合金及其制备方法，该方法步骤为：将偏钨酸铵、可溶性金属硝酸盐和葡萄糖混合并加入晶粒抑制剂，得WC‑陶瓷粉末前驱体浆料；将前驱体浆料与硅烷偶联剂共同溶解于纯水中，得待用浆料；加热可膨胀石墨，使其膨胀为单层或多层石墨烯；将膨胀后的石墨破碎置于反应釜中并加入待用浆料，滴入氨水调节pH＞7，并将反应釜抽真空搅拌反应，得反应后浆料；将反应后浆料湿式球磨，干燥、碾碎、过筛，得颗粒尺寸≤250 μm的混合粉末；将混合粉末压制成型并进行原位多步烧结，得到WC硬质合金。本发明的方法可以制得高硬度、高韧性和高耐磨的单层或多层石墨烯增韧WC硬质合金。
Description
技术领域
本发明属于合金材料技术领域，具体涉及一种短流程单层石墨烯或多层石墨烯增韧无粘接相WC基硬质合金粉末及其原位烧结制备方法，并且更具体地，涉及一种石墨烯增韧无粘接相WC基硬质合金及其制备方法。
背景技术
WC-Co硬质合金是一种常用的刃具、模具用粉末冶金材料。随着应用工况日趋严峻，例如：高速切削、干式切削以及待加工材料硬度的提高等，传统WC-Co硬质合金变得难以满足现代工业生产对材料加工精度、质量、成本等方面的更高要求。因此，迫切需要研制综合性能更优异的新型WC材料。
石墨烯是一种由单个碳原子构建的二维材料，其具有诸多优异的性质，例如高导电性、高导热性、高强度和高的比表面积等，是一种较理想的增强体。已有研究将其应用于陶瓷材料制备中，其可以在保持较高强度的前提下，显著提高材料的韧性。然而WC与石墨烯的密度太大，传统的机械混合或球磨很难将之分散均匀，若采用超声分散则需要几天的时间，极大的浪费生产时间和资源。
研发新型粘结相以获得更高性能WC材料一直是领域研究热点，采用Ni、Fe、Cu、Cr等金属部分或全部替代Co粘结WC硬质合金的研究也一直经久不衰。然而，Ni、Fe、Cu、Cr 等金属对WC的润湿性更差、与WC相结合强度显著低于Co金属，此类代Co类硬质合金还面临着力学性能差的难题。
此外，传统的WC-Co硬质合金制备过程中还涉及到将APT原料煅烧成钨的氧化物，再通过氢气还原、高温碳化。该生产工艺流程很长，耗时久，能耗大。
目前，国内外现均有采用石墨烯增强WC材料的研究报道。例如，陈奇等的文献（《低压烧结制备石墨烯增强WC-Co 硬质合金》，有色金属材料与工程，2020，41（4））报道了使用静电吸附工艺制备氧化石墨烯增WC-Co硬质合金，在石墨烯质量分数为0.10%时静电吸附较机械混合方法制备的硬质合金弯曲强度稍高8%。虽然他们引入氧化石墨烯的给静电吸附工艺创造了条件，降低了材料分散的难度，但是需要在烧结过程中增加氧化石墨烯转化为石墨烯的步骤。中国专利号为ZL201811062507.4（授权公告号：CN109320249B）的专利文献公开了一种掺杂氧化硼与氧化铝氧化锆复合增韧碳化钨复合材料及其制备方法，该方法是利用放电等离子烧结技术制备氧化硼、氧化铝、氧化锆复合增韧WC硬质合金，获得的复合材料有着良好的硬度和断裂韧性。前期研究证实以氧化硼、氧化铝、氧化锆替代金属粘接相，可克服金属粘结相的不足，然而如何进一步提高材料的断裂韧性以及降低材料的制备成本、制备难度等综合问题，仍是本领域技术人员需要解决的问题。
因此，现有技术有待改进。
发明内容
本发明的目的在于提供一种短流程、低成本生产单层或多层石墨烯增韧WC硬质合金粉末的制备方法以及提供一种通过上述方法制备得到的单层或多层石墨烯增韧WC硬质合金。
为了解决上述技术问题，本发明采用以下技术方案：
根据本发明的一方面，提供一种石墨烯增韧无粘接相WC基硬质合金的制备方法，包括以下步骤：
1）将原料偏钨酸铵、可溶性金属硝酸盐和葡萄糖进行混合并加入晶粒抑制剂，得到WC-陶瓷粉末前驱体浆料；
2）将WC-陶瓷粉末前驱体浆料与硅烷偶联剂共同溶解于纯水中，得到待用浆料；
3）加热可膨胀石墨，使石墨膨胀为单层或多层石墨烯；
4）将膨胀后的石墨破碎后置于反应釜中，并向反应釜中加入待用浆料，滴入氨水调节反应釜中的浆料至pH＞7，然后将反应釜抽真空并进行搅拌反应，得到反应后的浆料；
5）将反应后的浆料进行湿式球磨，然后进行干燥、碾碎、过筛，得到颗粒尺寸≤250μm的混合粉末；
6）将得到的混合粉末加入成型剂压制成型，脱脂后进行原位多步烧结，制备得到石墨烯增韧无粘接相WC基硬质合金。
在本发明的一个实施例中，在步骤1）中，偏钨酸铵的纯度≥99%，偏钨酸铵中WO3的质量分数≥92%，W的质量分数≥73%；可溶性金属硝酸盐包括硝酸锆、硝酸铝、硝酸镁和硝酸钇。
在本发明的一个实施例中，按WC-x wt.%陶瓷相的成分配比等效计算偏钨酸铵和可溶性金属硝酸盐配料的质量，其中0＜x≤12，陶瓷相包括氧化铝、氧化锆、氧化镁和氧化钇；葡萄糖中的C元素摩尔量配比为偏钨酸铵中的W元素摩尔量的3.5-4.0倍。
在本发明的一个实施例中，在步骤1）中，晶粒抑制剂由碳化铬和碳化钒按质量比2：1组成。
在本发明的一个实施例中，在步骤2）中，硅烷偶联剂采用KH570。
在本发明的一个实施例中，在步骤3）中，可膨胀石墨通过高温或微波进行加热，加热时间为30-60秒。
在本发明的一个实施例中，在步骤4）中，反应釜内采用磁力搅拌进行搅拌反应。
在本发明的一个实施例中，在步骤5）中，湿式球磨的条件为：磨球、罐体材质均为WC-Co硬质合金，球磨介质为无水乙醇，球料比为3:1，转速250 r/min。
在本发明的一个实施例中，在步骤6）中，成型剂为分子量4000的PEG，并且烧结采用真空烧结，具体条件如下：
多步烧结的条件为：400℃保温60min，550℃保温60min，750℃保温60min，1000℃保温2h；
烧结升温速率：10-50 ℃/min；
最终烧结温度：1200-1600 ℃；
最终烧结保温时间：60-120 min；
烧结真空度：≤6 Pa。
此外，本发明还提供一种石墨烯增韧无粘接相WC基硬质合金，该硬质合金通过如前所述的石墨烯增韧无粘接相WC基硬质合金的制备方法来制备得到。
通过采用上述技术方案，本发明相比于现有技术具有如下优点：
本发明的方法可以制备得到高硬度、高韧性和高耐磨的单层或多层石墨烯增韧WC硬质合金，开发出单层或多层石墨烯增韧无粘接相WC基硬质合金粉末及块体材料，技术可实现工业应用，使得产品竞争力大幅度提升，产品附加值高；并且本发明方法制备得到的无粘接相硬质合金可以降低我国对进口钴金属的依存度，降低硬质合金的使用成本，具有可观的经济效益和技术显示度。
附图说明
图1示出了本发明提供的一种石墨烯增韧无粘接相WC基硬质合金的制备方法的流程示意图。
具体实施方式
应当理解，在示例性实施例中所示的本发明的实施例仅是说明性的。虽然在本发明中仅对少数实施例进行了详细描述，但本领域技术人员很容易领会在未实质脱离本发明主题的教导情况下，多种修改是可行的。相应地，所有这样的修改都应当被包括在本发明的范围内。在不脱离本发明的主旨的情况下，可以对以下示例性实施例的设计、操作条件和参数等做出其他的替换、修改、变化和删减。
如图1所示，本发明提供的一种石墨烯增韧无粘接相WC基硬质合金的制备方法，包括以下步骤：
S101：将原料偏钨酸铵、可溶性金属硝酸盐和葡萄糖进行混合并加入晶粒抑制剂，得到WC-陶瓷粉末前驱体浆料；
S102：将WC-陶瓷粉末前驱体浆料与硅烷偶联剂共同溶解于纯水中，得到待用浆料；
S103：加热可膨胀石墨，使石墨膨胀为单层或多层石墨烯；
S104：将膨胀后的石墨破碎后置于反应釜中，并向反应釜中加入待用浆料，滴入氨水调节反应釜中的浆料至pH＞7，然后将反应釜抽真空并进行搅拌反应，得到反应后的浆料；
S105：将反应后的浆料进行湿式球磨，然后进行干燥、碾碎、过筛，得到颗粒尺寸≤250 μm的混合粉末；
S106：将得到的混合粉末加入成型剂压制成型，脱脂后进行原位多步烧结，制备得到石墨烯增韧无粘接相WC基硬质合金。
在上述制备方法中，在S101中，偏钨酸铵的纯度≥99%，偏钨酸铵中WO3的质量分数≥92%，W的质量分数≥73%；可溶性金属硝酸盐包括硝酸锆、硝酸铝、硝酸镁和硝酸钇；按WC-x wt.%陶瓷相的成分配比等效计算偏钨酸铵和可溶性金属硝酸盐配料的质量，其中0＜x≤12，陶瓷相包括氧化铝、氧化锆、氧化镁和氧化钇；葡萄糖中的C元素摩尔量配比为偏钨酸铵中的W元素摩尔量的3.5-4.0倍，优选3.75倍；晶粒抑制剂由碳化铬和碳化钒按质量比2：1组成。
在上述制备方法中，在S102中，硅烷偶联剂采用KH570（γ-（甲基丙烯酰氧）丙基三甲氧基）。
在上述制备方法中，在S103中，可膨胀石墨通过高温或微波进行加热，加热时间为30-60秒。
在上述制备方法中，在步骤S104中，膨胀石墨加入量小于球磨粉末总质量的1%，反应釜内采用磁力搅拌进行搅拌反应。
在上述制备方法中，在步骤S105中，干燥是指烘干至溶剂残余量≤1%；湿式球磨的条件为：磨球、罐体材质均为WC-Co硬质合金，球磨介质为无水乙醇，球料比为3:1，转速250r/min。
在上述制备方法中，在步骤S106中，成型剂为分子量4000的PEG，加入量为球磨粉末总质量的1.50%-4.20%，并且烧结采用真空烧结，具体条件如下：
多步烧结的条件为：400℃保温60min，550℃保温60min，750℃保温60min，1000℃保温2h；
烧结升温速率：10-50 ℃/min；
最终烧结温度：1200-1600 ℃；
最终烧结保温时间：60-120 min；
烧结真空度：≤6 Pa。
此外，本发明还提供一种石墨烯增韧无粘接相WC基硬质合金，该硬质合金通过如前所述的石墨烯增韧无粘接相WC基硬质合金的制备方法来制备得到。
下面通过具体实施例来对本发明的上述技术方案进行详细地说明。
实施例1
一种石墨烯增韧无粘接相WC基硬质合金的制备方法，步骤如下：
（1）制备WC-1wt.%Al2O3陶瓷粉末前驱体浆料：将原料粉末偏钨酸铵、硝酸铝和葡萄糖进行混合并加入碳化铬和碳化钒；其中各个物料配料为偏钨酸铵124.03g、硝酸铝4.18g、葡萄糖56.34g、碳化铬0.65g和碳化钒0.32g；
（2）将上述前驱体浆料与KH570硅烷偶联剂8 mL共同溶解于1000 mL纯水中，得到待用浆料；
（3）通过高温或微波加热1g可膨胀石墨 30秒，使之膨胀为多层石墨烯；
（4）将膨胀后的石墨破碎后置于反应釜中，并向反应釜中加入待用浆料，逐滴滴入氨水并保持反应釜中的浆料pH值>7，然后反应釜抽真空并使用磁力搅拌进行反应，得到反应后的浆料；
（5）将上述反应后的浆料置于行星式球磨机中进行湿式球磨，磨球、罐体材质均为WC-Co硬质合金，球磨介质为无水乙醇，球料比为3:1，转速250 r/min，球磨30小时制得混合浆料，然后将混合浆料置于干燥炉内烘干至溶剂残余量≤1%，并碾碎、过筛，得到颗粒尺≤250 μm的WC-1wt.%Al2O3-1wt.%石墨烯混合粉末；
（6）将得到的WC-1wt.%Al2O3-1wt.%石墨烯混合粉末加入分子量4000的PEG进行预压成型，得到直径20mm的待烧结坯，然后将待烧结坯脱脂后采用真空炉对上述圆柱坯进行烧结，其中烧结工艺为：升温速率为20 ℃/min，400℃保温60min，550℃保温60min，750℃保温60min，1000℃保温2h，最终烧结温度为1600 ℃，保温时间为60 min，真空度为4 Pa，制备得到WC-1 wt.% Al2O3-1 wt.%石墨烯硬质合金。
通过上述实施例1，得到的WC-1 wt.% Al2O3-1 wt.%石墨烯硬质合金材料的硬度为23 GPa HV30，横向断裂强度为1300MPa，断裂韧性为7.5MPa·m1/2；抗压强度为1014.5MPa。
实施例2
一种石墨烯增韧无粘接相WC基硬质合金的制备方法，步骤如下：
（1）制备WC-1wt.%Al2O3-1wt.%ZrO2陶瓷粉末前驱体浆料：将原料粉末偏钨酸铵、硝酸铝和葡萄糖进行混合并加入碳化铬和碳化钒；其中各个物料配料为偏钨酸铵122.76g、硝酸铝4.18g、硝酸锆2.75g、葡萄糖55.76g、碳化铬0.65g、碳化钒0.32g；
（2）将上述前驱体浆料与KH570硅烷偶联剂8 mL共同溶解于1000 mL纯水中，得到待用浆料；
（3）通过高温或微波加热1g可膨胀石墨 30秒，使之膨胀为多层石墨烯；
（4）将膨胀后的石墨破碎后置于反应釜中，并向反应釜中加入待用浆料，逐滴滴入氨水并保持反应釜中的浆料pH值>7，然后反应釜抽真空并使用磁力搅拌进行反应，得到反应后的浆料；
（5）将上述反应后的浆料置于行星式球磨机中进行湿式球磨，磨球、罐体材质均为WC-Co硬质合金，球磨介质为无水乙醇，球料比为3:1，转速250 r/min，球磨30小时制得混合浆料，然后将混合浆料置于干燥炉内烘干至溶剂残余量≤1%，并碾碎、过筛，得到颗粒尺≤250 μm的WC-1wt.%Al2O3-1wt.%ZrO2-1wt.%石墨烯混合粉末；
（6）将得到的WC-1wt.%Al2O3-1wt.%ZrO2-1wt.%石墨烯混合粉末加入分子量4000的PEG进行预压成型，得到直径20mm的待烧结坯，然后将待烧结坯脱脂后采用真空炉对上述圆柱坯进行烧结，其中烧结工艺为：升温速率为20 ℃/min，400℃保温60min，550℃保温60min，750℃保温60min，1000℃保温2h，最终烧结温度为1600 ℃，保温时间为60 min，真空度为4 Pa，制备得到WC-1wt.%Al2O3-1wt.%ZrO2-1wt.%石墨烯硬质合金。
通过上述实施例2，得到的WC-1wt.%Al2O3-1wt.%ZrO2-1wt.%石墨烯硬质合金材料的硬度为21 GPa HV30，横向断裂强度为1500MPa，断裂韧性为8.5MPa·m1/2；抗压强度为1773.5MPa。
由上述实施例1-2可以看出，本发明的方法可以制备得到高硬度、高韧性和高耐磨的单层或多层石墨烯增韧WC硬质合金，本发明的方法可以短流程、低成本生产单层或多层石墨烯增韧WC硬质合金粉末。
以上所述仅为本发明的较佳实施例，并非用来限定本发明的实施范围；如果不脱离本发明的精神和范围，对本发明进行修改或者等同替换，均应涵盖在本发明权利要求的保护范围当中。
Claims (10)
1.一种石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，包括以下步骤：
1）将原料偏钨酸铵、可溶性金属硝酸盐和葡萄糖进行混合并加入晶粒抑制剂，得到WC-陶瓷粉末前驱体浆料，其中所述可溶性金属硝酸盐包括硝酸锆、硝酸铝、硝酸镁和硝酸钇中的一种或多种，并且按WC-x wt.%陶瓷相的成分配比等效计算偏钨酸铵和可溶性金属硝酸盐配料的质量，其中0＜x≤12，所述陶瓷相包括氧化铝、氧化锆、氧化镁和氧化钇中的一种或多种；
2）将所述WC-陶瓷粉末前驱体浆料与硅烷偶联剂共同溶解于纯水中，得到待用浆料；
3）加热可膨胀石墨，使石墨膨胀为单层或多层石墨烯；
4）将膨胀后的石墨破碎后置于反应釜中，并向所述反应釜中加入所述待用浆料，滴入氨水调节反应釜中的浆料至pH＞7，然后将反应釜抽真空并进行搅拌反应，得到反应后的浆料；
5）将所述反应后的浆料进行湿式球磨，然后进行干燥、碾碎、过筛，得到颗粒尺寸≤250μm的混合粉末；
6）将得到的所述混合粉末加入成型剂压制成型，脱脂后进行原位多步烧结，制备得到石墨烯增韧无粘接相WC基硬质合金。
2.根据权利要求1所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，在步骤1）中，所述偏钨酸铵的纯度≥99%，所述偏钨酸铵中WO3的质量分数≥92%，W的质量分数≥73%。
3.根据权利要求2所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，所述葡萄糖中的C元素摩尔量配比为偏钨酸铵中的W元素摩尔量的3.5-4.0倍。
4.根据权利要求1所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，在步骤1）中，所述晶粒抑制剂由碳化铬和碳化钒按质量比2：1组成。
5.根据权利要求1所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，在步骤2）中，硅烷偶联剂采用KH570。
6.根据权利要求1所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，在步骤3）中，所述可膨胀石墨通过高温或微波进行加热，加热时间为30-60秒。
7.根据权利要求1所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，在步骤4）中，反应釜内采用磁力搅拌进行搅拌反应。
8. 根据权利要求1所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，在步骤5）中，所述湿式球磨的条件为：磨球、罐体材质均为WC-Co硬质合金，球磨介质为无水乙醇，球料比为3:1，转速250 r/min。
9.根据权利要求1所述的石墨烯增韧无粘接相WC基硬质合金的制备方法，其特征在于，在步骤6）中，成型剂为分子量4000的PEG，并且烧结采用真空烧结，具体条件如下：
多步烧结的条件为：400℃保温60min，550℃保温60min，750℃保温60min，1000℃保温2h；
烧结升温速率：10-50 ℃/min；
最终烧结温度：1200-1600 ℃；
最终烧结保温时间：60-120 min；
烧结真空度：≤6 Pa。
10.一种石墨烯增韧无粘接相WC基硬质合金，其特征在于，通过前述权利要求1-9中任一项所述的石墨烯增韧无粘接相WC基硬质合金的制备方法来制备得到。
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