CN113880589A - 一种ZrB2增韧聚晶立方氮化硼复合片的制备方法 - Google Patents
一种ZrB2增韧聚晶立方氮化硼复合片的制备方法 Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 33
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 27
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 22
- 229910007948 ZrB2 Inorganic materials 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
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- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 abstract description 7
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- 239000011733 molybdenum Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 8
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
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- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910003465 moissanite Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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Abstract
本发明公开了一种ZrB2增韧聚晶立方氮化硼复合片的制备方法，包括：按重量百分比计，称取17～35％的结合剂、1～5％的氮化铝和余量的立方氮化硼混合均匀后置于高温真空环境中净化，所得混合粉料和硬质合金基体置于保温传压介质中，进行高温高压合成，即得；其中，所述的结合剂由碳化硼、锆粉和硅粉按1：3.5～4.5：1～2的重量比组成。本发明以碳化硼、锆粉和硅粉为结合剂，在高温高压烧结过程中和立方氮化硼发生化学反应原位生成新物相二硼化锆、碳化锆以及碳化硅，从而牢固的粘结立方氮化硼颗粒；同时加入的少量氮化铝使烧结体快速致密化和抑制cBN颗粒发生相变的作用，使合成得到的具有优良的韧性和耐磨性。
Description
技术领域
本发明涉及一种超硬复合材料，具体涉及一种ZrB2增韧聚晶立方氮化硼复合片的制备方法。
背景技术
聚晶立方氮化硼(PCBN)复合片是由立方氮化硼(cBN)微粉、结合剂和硬质合金基体在高温高压下烧结而成，其具有较高的硬度与耐磨性，同时具有比金刚石更优的耐热性和化学惰性，特别适用于切削淬硬钢、铸铁、粉末冶金材料和耐热合金等铁基材料。
世界各国都在制造PCBN复合片并研究其性能，目前国外生产的PCBN复合片已系列化，并带来了应用的专业化，复合片的规格也趋向大型化。我国在汽车工业、航空航天等难加工材料切削方面所使用的PCBN复合片大部分还是依赖于进口。
结合剂在PCBN复合片的合成过程中发挥着重要作用，合理的结合剂的加入不但可以降低烧结温度和压力，还可以改善烧结性能。采用金属陶瓷作为结合剂，综合了金属结合剂和陶瓷结合剂的优点，同时结合剂之间以及结合剂和cBN颗粒之间化学反应的发生，生成的新物相可以更好的粘结cBN颗粒，达到提高PCBN刀具强度、韧性、硬度的目的，对开发新型高性能PCBN刀具有实际意义。
公布号为CN 110625123A的发明专利，公开了一种高性能聚晶金刚石复合片，包括硬质合金衬底，以及在硬质合金衬底表面上的碳化硅-金刚石过渡层和聚晶金刚石层，所述聚晶金刚石层由下述重量百分含量的原料组成：金刚石微粉为90～95％、结合剂为5～10％，所述的结合剂由下述重量百分含量的原料组成：金属元素90～95％、非金属元素3～6％、无机非金属晶须1.5～3％、稀土元素0.5～1％；其中，所述的金属元素由下述重量百分含量的原料组成：Co粉84～90％、Ni粉5～7％、Cr粉2～3％、Ti粉1～2％、Zr粉1～2％、W粉0.5～1％、Mo粉0.5～1％；所述的非金属元素为Si或B的一种或两者的混合物，当为Si和B两种的混合物时，混合物中B所占重量百分含量为5～10％。该发明通过化学气相沉积方法在硬质合金衬底表面上沉积碳化硅-金刚石梯度过渡层以有效抑制所述硬质合金衬底的钴元素向所述聚晶金刚石层的扩散，在保证性能优异的同时，大幅度延长了聚晶金刚石层的使用寿命。另一方面，由于所述碳化硅的热膨胀系数(1.8×10-3/K)介于所述硬质合金(4.8×10-3/K)和聚晶金刚石(1.5×10-3/K)之间，缓解了聚晶金刚石层与硬质合金衬底之间应力，提高了硬质合金衬底与聚晶金刚石的结合强度。但该发明中结合剂的组成复杂，制备时需要采用化学气相沉积方法以保证所得复合片产品的性能和使用寿命，工艺较为复杂。
发明内容
本发明要解决的技术问题是提供一种结合剂组成简单、制备工艺简单且性能优良的ZrB2增韧聚晶立方氮化硼复合片的制备方法。
为解决上述技术问题，本发明采用以下技术方案：
一种ZrB2增韧聚晶立方氮化硼复合片的制备方法，包括：按重量百分比计，称取17～35％的结合剂、1～5％的氮化铝(AlN)和余量的立方氮化硼混合均匀后置于高温真空环境中净化，得到混合粉料；将所得混合粉料和硬质合金基体置于保温传压介质中，进行高温高压合成，即得到ZrB2增韧聚晶立方氮化硼复合片；其中，所述的结合剂由碳化硼(B4C)、锆粉(Zr)和硅粉(Si)按1：3.5～4.5：1～2的重量比组成。
本发明所述制备方法中，碳化硼、锆粉和硅粉的加入可以在体系中生成新物相二硼化锆、碳化锆和碳化硅，这些新物相可以牢固的粘结立方氮化硼颗粒，配合氮化铝的加入使制得的PCBN复合片硬度高、强度好，具有优良的韧性和耐磨性。但碳化硼、锆粉和硅粉的加入配比对能否生成新物相二硼化锆、碳化锆和碳化硅有着重要的影响，进一步的，优选碳化硼、锆粉和硅粉的重量比为1：4：1.5。
本发明所述制备方法中，所述立方氮化硼优选是由镀镍立方氮化硼微粉和无镀层立方氮化硼组成，进一步优选是由镀镍立方氮化硼微粉和无镀层立方氮化硼按1：2～5的重量比组成，更优选是由镀镍立方氮化硼微粉和无镀层立方氮化硼按1：4的重量比组成。
本发明所述制备方法中，所述立方氮化硼、碳化硼、锆粉、硅粉和氮化铝的粒径均为现有技术中的常规选择。对于立方氮化硼、碳化硼、锆粉和硅粉而言，它们的粒径通常为微米级，优选的，所述立方氮化硼的平均粒径均为1～22μm，所述碳化硼、锆粉和硅粉的平均粒径均为1～10μm，其中，所述碳化硼的平均粒径均更优选为5～10μm，所述锆粉和硅粉的平均粒径更优选为1～5μm。对于氮化铝而言，其粒径优选为纳米级，更优选氮化铝的平均粒径为50～500nm。
本发明所述制备方法中，采用现有常规的方法实现结合剂、氮化铝和余量的立方氮化硼的混合均匀，如球磨法等。
本发明所述制备方法中，所述高温真空环境中进行净化的操作与现有技术相同，本申请中优选是在为800～1200℃、压力为10-1～10-3Pa的环境中净化1～3h。
本发明所述制备方法中，所述的保温传压介质及后续的高温高压合成等均与现有技术相同，具体的，保温传压介质通常为叶蜡石块，所述高温高压合成的工艺条件优选为：压力为4.5～5.5GPa，温度为1400～1750℃，时间为10～15min。
与现有技术相比，本发明以碳化硼、锆粉和硅粉为结合剂，在高温高压烧结过程中和立方氮化硼发生化学反应原位生成新物相二硼化锆、碳化锆以及碳化硅，从而牢固的粘结立方氮化硼颗粒；同时加入的少量氮化铝作为熔融助烧剂可以在体系中流动使烧结体快速致密化，加速烧结，而且氮化铝还能起到抑制cBN颗粒相变的发生，使合成得到的PCBN复合片硬度高、强度好，具有优良的韧性和耐磨性。
附图说明
图1为本发明实施例1制得的复合片的断面经溶质质量分数为40％的氢氟酸腐蚀60s后的SEM图。
图2本发明实施例2制得的复合片的断面经溶质质量分数为40％的氢氟酸腐蚀60s后的SEM图。
具体实施方式
为了更好的解释本发明的技术方案，下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
1)配料：按比例配置cBN、B4C、Zr、Si和AlN。
其中，立方氮化硼微粉粒径为4～8μm，由镀镍立方氮化硼微粉和无镀层的立方氮化硼微粉按1：4的重量比组成，占粉末总重量的80％；碳化硼粉平均粒径为5μm，锆粉平均粒径为3μm，硅粉平均粒度为3μm，碳化硼、锆粉和硅粉的重量比为1：4：1.5，三者占粉末总重量的17％；氮化铝粉平均粒度为50nm，占粉末总重量的3％。
2)混料：以乙醇作为混合介质，将上述粉料置于球磨机中球磨，其中球料比为3：1，转速150r/min，时间为2h；之后置于80℃环境中干燥12h，干燥后过100目筛，收集筛下物。
3)高温真空处理：将收集的筛下物装入置于温度为1000℃、真空度为10-2Pa的环境中净化处理1h，冷却，得到混合粉料，备用。
4)组装：以从市场上购买的的直径与钼杯内径相匹配的型号为YG12作为硬质合金基体，在规格为
(高)的钼杯中，装入混合粉料4g，铺平、压实后放入硬质合金基体，盖上杯盖。
5)合成：将加盖后的钼杯置于叶腊石块中，进行高温高压合成，高温高压合成工艺条件为：压力5.5GPa，温度1500℃，保温12min，得到ZrB2增韧聚晶立方氮化硼复合片。
本实施例制得的复合片的断面经溶质质量分数为40％的氢氟酸腐蚀60s后的SEM图如图1所示。由图1可观察到结合剂均匀分布在cBN颗粒周围，同时有棒状晶粒的生成，说明复合片有较好强度与韧性。
对比例1-1
重复实施例1，不同的是，步骤1)按下述配方进行配料：
cBN：ZrB2：SiC：ZrC：AlN＝80：13：2.5：1.5：3。
对比例1-2
重复实施例1，不同的是，步骤1)中，碳化硼、锆粉和硅粉的重量比为1：3：1.5。
对比例1-3
重复实施例1，不同的是，步骤1)中，碳化硼、锆粉和硅粉的重量比为1：3：2.5。
对比例1-4
重复实施例1，不同的是，步骤1)中，碳化硼、锆粉和硅粉的重量比为1：4：2.5。
实施例2：
1)配料：按比例配置cBN、B4C、Zr、Si和AlN。
其中，立方氮化硼微粉粒径为4～8μm，由镀镍立方氮化硼微粉和无镀层的立方氮化硼微粉按1：4的重量比组成，占粉末总重量的70％；碳化硼粉平均粒径为5μm，锆粉平均粒径为3μm，硅粉平均粒度为3μm，碳化硼、锆粉和硅粉的重量比为1：4：1.5，三者占粉末总重量的26％；氮化铝粉平均粒度为50nm，占粉末总重量的4％。
2)混料：以乙醇作为混合介质，将上述粉料置于球磨机中球磨，其中球料比为3：1，转速150r/min，时间为2h；之后置于80℃环境中干燥12h，干燥后过100目筛，收集筛下物。
3)高温真空处理：将收集的筛下物装入置于温度为1100℃、真空度为10-2Pa的环境中净化处理1h，冷却，得到混合粉料，备用。
4)组装：以从市场上购买的的直径与钼杯内径相匹配的型号为YG12作为硬质合金基体，在规格为
(高)的钼杯中，装入混合粉料4g，铺平、压实后放入硬质合金基体，盖上杯盖。
5)合成：将加盖后的钼杯置于叶腊石块中，进行高温高压合成，高温高压合成工艺条件为：压力5.5GPa，温度1450℃，保温12min，得到ZrB2增韧聚晶立方氮化硼复合片。
本实施例制得的复合片的断面经溶质质量分数为40％的氢氟酸腐蚀60s后的SEM图如图2所示。由图2可观察到结合剂均匀分布在cBN颗粒周围，同时有棒状晶粒的生成，说明复合片有较好强度与韧性。
对比例2-1
重复实施例2，不同的是，步骤1)按下述配方进行配料：
cBN：ZrB2：SiC：ZrC：AlN＝70：20：4：3：3。
实施例3
1)配料：按比例配置cBN、B4C、Zr、Si和AlN。
其中，立方氮化硼微粉粒径为4～8μm，由镀镍立方氮化硼微粉和无镀层的立方氮化硼微粉按1：4的重量比组成，占粉末总重量的60％；碳化硼粉平均粒径为5μm，锆粉平均粒径为3μm，硅粉平均粒度为3μm，碳化硼、锆粉和硅粉的重量比为1：4：1.5，三者占粉末总重量的35％；氮化铝粉平均粒度为50nm，占粉末总重量的5％。
2)混料：以乙醇作为混合介质，将上述粉料置于球磨机中球磨，其中球料比为3：1，转速150r/min，时间为2h；之后置于60℃环境中干燥12h，干燥后过100目筛，收集筛下物。
3)高温真空处理：将收集的筛下物装入置于温度为850℃、真空度为10-1Pa的环境中净化处理3h，冷却，得到混合粉料，备用；
4)组装：以从市场上购买的的直径与钼杯内径相匹配的型号为YG12作为硬质合金基体，在规格为
(高)的钼杯中，装入混合粉料4g，铺平、压实后放入硬质合金基体，盖上杯盖。
5)合成：将加盖后的钼杯置于叶腊石块中，进行高温高压合成，高温高压合成工艺条件为：压力5.5GPa，温度1400℃，保温15min，得到ZrB2增韧聚晶立方氮化硼复合片。
对比例3
重复实施例3，不同的是，步骤1)按下述配方进行配料：
cBN：ZrB2：SiC：ZrC：AlN＝60：26：5：4：5。
实施例4
重复实施例1，不同的是，步骤1)中，碳化硼、锆粉和硅粉的重量比为1：3.5：2。
实施例5
重复实施例1，不同的是，步骤1)中，碳化硼、锆粉和硅粉的重量比为1：4.5：1.5。
对以上各实施例和对比例制备的复合片的性能进行检测，结果如下述表1所示。
表1
由实施例和对比例的测试结果表明，采用cBN、ZrB2、SiC、ZrC和AlN混合所得粉料与基体合成的复合片的强度、韧性和耐磨性均远低于采用本发明所述方法原位合成生成新物相的复合片。
Claims (10)
1.一种ZrB2增韧聚晶立方氮化硼复合片的制备方法，其特征是，按重量百分比计，称取17～35％的结合剂、1～5％的氮化铝和余量的立方氮化硼混合均匀后置于高温真空环境中净化，得到混合粉料；将所得混合粉料和硬质合金基体置于保温传压介质中，进行高温高压合成，即得到ZrB2增韧聚晶立方氮化硼复合片；其中，所述的结合剂由碳化硼、锆粉和硅粉按1：3.5～4.5：1～2的重量比组成。
2.根据权利要求1所述的制备方法，其特征是，所述的结合剂由碳化硼、锆粉和硅粉按1：4：1.5的重量比组成。
3.根据权利要求1所述的制备方法，其特征是，所述立方氮化硼粉由镀镍立方氮化硼和无镀层立方氮化硼组成。
4.根据权利要求3所述的制备方法，其特征是，所述立方氮化硼由镀镍立方氮化硼和无镀层立方氮化硼按1：2～5的重量比组成。
5.根据权利要求1～4中任一项所述的制备方法，其特征是，所述立方氮化硼、碳化硼、锆粉和硅粉的粒径均为微米级。
6.根据权利要求5所述的制备方法，其特征是，所述立方氮化硼的平均粒径均为1～22μm，碳化硼、锆粉和硅粉的平均粒径均为1～10μm。
7.根据权利要求1～4中任一项所述的制备方法，其特征是，所述氮化铝的粒径为纳米级。
8.根据权利要求7所述的制备方法，其特征是，所述氮化铝的平均粒径为50～500nm。
9.根据权利要求1～4中任一项所述的制备方法，其特征是，所述的高温真空环境为温度为800～1200℃、压力为10-1～10-3Pa的环境。
10.根据权利要求1～4中任一项所述的制备方法，其特征是，所述高温高压合成的工艺条件为：压力为4.5～5.5GPa，温度为1400～1750℃，时间为10～15min。
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