WC-Al_2O_3纳米复合粉末制备及烧结技术研究
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摘要
硬质合金因其具有高硬度、高强度、高弹性模量、低热膨胀系数等优点,在切削刀具、开采工具、石油与地质矿山勘探、耐磨零件和精密模具等领域有着举足轻重的作用。WC-Co硬质合金是该领域产品的主体,其中WC作为硬质相是材料高硬度的保证,金属Co是材料韧性的保证。但Co是稀有昂贵、不可再生的战略性资源,且由于其优良的物理、化学和力学性能,在陶瓷、食品添加剂、催化剂、电池、电子部件等方面的需求量也迅速增加。另一方面,由于Co熔点低、化学活性高,高温时易软化、易与其他元素发生反应扩散等,硬质合金硬度和耐蚀性会受到影响。因此,研制兼具高硬度和高韧性、原料易得的新型WC基硬质合金,以代替WC-Co,具有必要性和紧迫性。
本文中,以Al2O3作为Co的替代材料,从粉末制备和热压烧结两个方面开展制备WC-Al2O3复合材料的研究工作。研制过程中,系统设计了复合粉末的配方和热压烧结工艺,对复合粉末在球磨过程中的物相变化、球磨后纳米复合粉末的热力学、热压烧结过程中物相变化、烧结制度及增韧机理、添加剂MgO和CeO2对烧结试样的影响和二阶段热压烧结制度进行了深入的探讨,主要研究结果如下：
1.以WC和无定形态Al2O3为原料,利用机械合金化法和普通热压烧结法制备WC-Al2O3复合材料(WA1)；通过物相分析研究球磨和热压烧结过程中Al2O3的相变,通过微观组织观察和力学性能测试,研究热压烧结工艺和Al2O3含量对复合材料的影响,并探讨其增韧机理。研究结果表明：球磨过程中,复合粉末不断细化,无定形态Al2O3未发生相变；在烧结过程中,A1203发生了相变,当烧结温度为961℃时,无定形态Al2O3和过渡形态Al2O3转化为γ-Al2O3,当烧结温度为1100℃时,完全转化为α-Al2O3; WC-40vol.%Al2O3复合粉末在烧结温度为1540℃,保温时间为90min,压力为39.6MPa的热压烧结条件下获得的综合力学性能最好,其致密度可达97.98%,维氏硬度为18.65GPa,断裂韧性为10.43MPa·m1/2,抗弯强度为756.34MPa; WC-Al2O3复合材料中增韧机理主要为第二相颗粒增韧机理、基体WC和第二相Al2O3颗粒热膨胀系数失配产生的残余应力增韧机理和Al2O3相变增韧机理；这些机理综合作用使裂纹搭桥、偏转,二次裂纹和侧生裂纹增多,从而提高复合材料的韧性。
2.以WC和α-Al2O3为原料,以3：2体积比的配方,在烧结温度为1540℃,保温时间为90min,压力为39.6MPa的热压烧结条件下制备WC-40vol.%α-Al2O3复合材料(WA2)；对比分析以不同种类Al2O3为原料制备的WC-Al2O3复合材料的微观组织和力学性能,探讨Al2O3相变对复合材料力学性能的影响及其增韧作用。研究结果表明：WC-40vol.%α-Al2O3复合材料致密度为98.38%,维氏硬度为16.55GPa,断裂韧性为8.52MPa·m1/2,抗弯强度为881.35MPa。WA1中AlOOH相变产生的少许水残留在试样中形成孔隙,是WA1致密度和抗弯强度较WA2低的原因；γ-Al2O3向α-Al2O3的相变消耗系统能量,从而减少WC氧化脱碳的能量,是WA1中脆性相W2C的形成被抑制的原因；γ-Al2O3向α-Al2O3的相变过程有24vol.%的体积缩小,从而获得较小的Al2O3颗粒,是WA1微观组织的细化、维氏硬度和断裂韧性较WA2高的原因；
3.为提高WA1和WA2复合材料的力学性能,研究添加剂MgO和稀土氧化物CeO2对复合材料微观组织和力学性能的影响及其机理。研究结果表明：添加MgO和CeO2未能提高WA1复合材料的力学性能；而对于WA2复合材料,分别添加MgO和CeO2时,最佳含量均为0.1wt.%,二者均可起到提高复合材料的致密度、抑制晶粒长大、改善颗粒之间的结合状态的作用；另外,活泼的稀土元素吸附复合粉末中的杂质氧,有效抑制WC的脱碳；CeO2在烧结过程中被还原成Ce2O3,并与Al2O3形成新的化合物,提高复合材料的结合强度。当同时添加0.05wt.%MgO和0.05wt.%CeO2时,WA2复合材料的综合性能达到最佳,致密度为99.04%TD,维氏硬度为18.18GPa,断裂韧性为10.14MPa·m1/2,抗弯强度为1155.38MPa。
4.依据WC-40vol.%α-Al2O3复合材料致密化速率和晶粒长大速率的变化情况,设计合理的二阶段热压烧结工艺；考察各工艺对试样微观组织和力学性能的影响并确定最佳烧结制度,探讨二阶段热压烧结对复合材料性能影响的机理。研究二阶段热压烧结法和添加剂MgO、CeO2共同作用对WC-40vol.%α-Al2O3复合材料组织和力学性能的影响。研究结果表明：TSS4烧结制度下(T1=1600℃,T2=1450℃,t2=6h)制备的WC-40vol.%α-Al2O3烧结试样的力学性能优于普通热压烧结制度CS1下(1540℃保温90min)所得烧结试样的力学性能。在TSS4和添加剂MgO、CeO2的共同作用下,WC-40vol.%α-Al2O3复合材料力学性能进一步提高,其致密度为99.42%TD,晶粒尺寸为2.921μm,维氏硬度为19.22GPa,断裂韧性为11.21MP·m1/2,抗弯强度为1236.78MPa,与热压烧结法制备的WC-Co硬质合金的力学性能相当。
5.研究以WC和无定形态Al2O3为原料的WC-40vol.%Al2O3复合材料的二阶段热压烧结工艺,探讨Al2O3相变和二阶段烧结技术对复合材料微观组织和力学性能的影响。研究结果表明：Al2O3的相变在第一阶段烧结后即已完成,则该材料第二阶段烧结开始时,起始颗粒尺寸较小,有利于获得匀细的微观组织；以WC和无定形态Al2O3为原料的WC-40vol.%Al2O3复合材料的最佳二阶段热压烧结工艺为TSS4(T1=1600℃,T2=1450℃,t2=6h)；在TSS4制度下制备试样的力学性能与CS1制度下制备试样的力学性能相比,致密度从97.98%TD增加至99%TD,WC晶粒尺寸从2.79gm减小至2.38gm,维氏硬度从18.65GPa提高至19.71GPa,断裂韧性从10.43MPa·m1/2提高至12MPa·m1/2,抗弯强度从881.35MPa提高至1285.08MPa。
本文中,作者率先采用无定形Al2O3和α-Al2O3代替Co,通过高能球磨、普通热压烧结法和二阶段热压烧结法制备新型WC-Al2O3复合材料,利用现代测试技术,对复合材料球磨和烧结过程中物相、热力学、微观结构和力学性能的变化进行表征,探讨复合材料致密化和增韧机理,及添加剂对复合材料的微观组织和力学性能的影响,为WC-Al2O3复合材料的进一步研究和应用奠定了坚实的基础。
Cemented carbide with superior hardness and strength, high elastic modulus and low thermal expansion coefficient, has been playing an important part in the areas of cutting tools, drilling and mining equipments, wear resistance parts and precision molds. Among hard alloys, WC-Co composites find the widest applications; The WC element is the assurance of high hardness, and the Co element is the guarantee of its fracture toughness. However, Co is rare, expensive and non-renewable strategic resource. Meanwhile, due to its excellent physical, chemical and mechanical properties, the demand of Co in ceramics, food additive, catalyst, batteries, electronic components and other aspects is increasing rapidly. Moreover, because of the low melting point and high chemical activity of Co, it will be soften and react with other elements easily, deteriorating the hardness and corrosion resistance of WC-Co composite. Therefore, it is of great significance and urgency to consolidate new WC matrix composite with cheap raw materials but high hardness and strength to instead of the WC-Co composite.
In this paper, Al2O3was chose as the substitute of Co, and WC-Al2O3composite had been consolidated through high energy ball milling and the following hot pressing. The content ratio of elements and the hot pressing parameters were systematically analyzed, the phase transformation of Al2O3during ball milling and hot pressing process, the thermodynamic of as milled powders, the hot pressing schedules and the toughening mechanisms had been investigated in details. Some significant original results are as follows:
Firstly, WC-Al2O3composites (WA1) were prepared by high energy ball milling and the following hot pressing. The tungsten carbide (WC) and commercial alumina (Al2O3) powders composed of amorphous Al2O3, boehmite (AlOOH) and χ-Al2O3were used as the starting materials. XRD was used to analyze the phase transformation during the ball milling and hot pressing process. The optimum hot pressing schedule, optimum content of Al2O3and the toughening mechanisms were clarified according to the investigation of microstructure and mechanical properties of the hot pressed bulk samples. The results showed that the powder size decreased and there was no phase transformation during the ball milling process, while during the hot pressing process, the amorphous and transitional Al2O3transformed to γ-Al2O3at961℃, and completely to α-Al2O3at1100℃. The WA1composites combined a relative density of97.98%and an excellent Vickers hardness of18.65GPa with an acceptable fracture toughness of10.43MPa-m1/2when hot pressed at1540℃for90min with a pressure of39.6MPa The second phase toughening mechanism, residual stress toughening mechanism and phase transformation of Al2O3were main toughening mechanisms in WA1composites. The crack bridging, crack deflection and the generation of secondary crack and lateral crack were the main reasons for the high fracture toughness and strength of WA1composites.
Secondly, WC-40vol.%α-Al2O3composites (WA2) were hot pressed at1540℃for90min under the pressure of39.6MPa. The toughening effects of phase transformation of Al2O3were investigated by comparison of microstructure and mechanical properties of WAI and WA2. The results showed that a relative density of98.38%and a maximum hardness of16.55GPa, combining a fracture toughness of8.52MPa-m1/2with an improved flexural strength of881.35MPa were obtained for the WA2composites. The relative density and the flexure strength of WA2were higher than that of WA1due to the residual pores induced by the water generated during the phase transformation of Al2O3in WA1; The decarburization of WC in WA1was suppressed may be attributed to the lowered energy provided for it, because many of the system energy was consumed by the phase transformation of Al2O3. The refined microstructure and higher hardness and fracture toughness were due to the decreased volume of Al2O3particles during the phase transformation.
Thirdly, to improve the mechanical properties of WA1and WA2, influence of MgO and CeO2additives on the microstructure and mechanical properties, and the mechanisms were investigated. The results showed that adding MgO and CeO2to WA1composite did not improve its mechanical properties; while for the WA2composite, when the MgO and CeO2were added separately, the optimum content was0.1wt.%, they could promote the microstructural refinement and improve the interface coherence of the WC matrix and Al2O3leading to the enhancement of the mechanical properties. Trace MgO mainly acted as an effective grain growth inhibitor for the WC-Al2O3composites and trace CeO2could suppress the decarburization of WC as well due to the unique properties of rare earth elements such as high surface activity and large ionic radius. The synergistic effect of0.05wt.%MgO and0.05wt.%CeO2added in WC-40vol.%α-Al2O3composites resulted in the achievement of a relative density of99.04%with an excellent Vickers hardness of18.18GPa, combining a fracture toughness of10.14MPa-m1/2with an acceptable flexural strength of1158.38MPa.
Fourthly, two step sintering (TSS) regimes were designed according to the densification rate and the grain growth rate of WC-40vol.%α-Al2O3composite. Microstructure and mechanical properties of WC-40voI.%α-Al2O3samples under each regime with different T1,, T2and t2were compared and analyzed to obtain the optimum TSS regime, the densification and toughening mechanisms of the composites under TSS regimes were discussed. Then WC-40vol.%α-Al2O3-0.05wt.%MgO-0.05wt.%CeO2powders were hot pressed under the optimum TSS regime to investigate the synergistic effect of additives and TSS regime. The results showed that the mechanical properties of samples under TSS4regime (T1=1600℃, T2=1450℃for6h) were improved compared with samples consolidated under CS1regime (1540℃for90min). WC-40vol.%α-Al2O3-0.05wt.%MgO-0.05wt.%CeO2powders hot pressed under TSS4regime achieved a relative density of99.42%TD with a grain size of2.92μm, combining an excellent Vickers hardness of19.22GPa, a fracture toughness of11.21MPa-m1/2with an acceptable flexural strength of1236.78MPa. The flexural strength was comparable with that of the WC-(3-8)wt.%Co cemented hard alloys (1150-1650MPa).
Fifthly, the optimum TSS regime of WC-40vol.%Al2O3composite with WC and amorphous Al2O3was investigated. Influence of Al2O3phase transformation and TSS regimes on the microstructure and mechanical properties of this WC-40vol.%Al2O3composite were illustrated. The results showed that Al2O3phase transformation had been completed when the sample was hot pressed under the first step sintering (1600℃for3min), resulting in the smaller particle size of Al2O3beneficial for the refined microstructure. When the as milled WC-40vol.%Al2O3powders were hot pressed under TSS4regime, a relative density of99%and a grain size of2.38μm were obtained, and an excellent Vickers hardness of19.71GPa was achieved, combining a fracture toughness of12MPa-m1/2with an acceptable flexural strength of1285.03MPa. Compared with the nearly full densified samples consolidated under CS1regime (1540℃for90min), the grain size decreased (2.79μm for the CS1sample), the Vickers hardness, fracture toughness and the flexural strength were all improved (18.65GPa,10.43MPa·m1/2,756.34MPa for the CS, sample) due to the refined microstructure and the transgranular fracture mode.
In this paper, amorphous Al2O3and α-Al2O3were used as the substitute of Co. WC-Al2O3composites were consolidated through high energy ball milling, the following hot pressing and two step hot pressing. Modern analytical technologies were used respectively to investigate the phases, thermodynamics and microstructure of the samples. The densification and toughening effects, as well as the influence of additives were illustrated. This paper has made a solid foundation for the further investigation and application of WC-Al2O3composites.
本文中,以Al2O3作为Co的替代材料,从粉末制备和热压烧结两个方面开展制备WC-Al2O3复合材料的研究工作。研制过程中,系统设计了复合粉末的配方和热压烧结工艺,对复合粉末在球磨过程中的物相变化、球磨后纳米复合粉末的热力学、热压烧结过程中物相变化、烧结制度及增韧机理、添加剂MgO和CeO2对烧结试样的影响和二阶段热压烧结制度进行了深入的探讨,主要研究结果如下：
1.以WC和无定形态Al2O3为原料,利用机械合金化法和普通热压烧结法制备WC-Al2O3复合材料(WA1)；通过物相分析研究球磨和热压烧结过程中Al2O3的相变,通过微观组织观察和力学性能测试,研究热压烧结工艺和Al2O3含量对复合材料的影响,并探讨其增韧机理。研究结果表明：球磨过程中,复合粉末不断细化,无定形态Al2O3未发生相变；在烧结过程中,A1203发生了相变,当烧结温度为961℃时,无定形态Al2O3和过渡形态Al2O3转化为γ-Al2O3,当烧结温度为1100℃时,完全转化为α-Al2O3; WC-40vol.%Al2O3复合粉末在烧结温度为1540℃,保温时间为90min,压力为39.6MPa的热压烧结条件下获得的综合力学性能最好,其致密度可达97.98%,维氏硬度为18.65GPa,断裂韧性为10.43MPa·m1/2,抗弯强度为756.34MPa; WC-Al2O3复合材料中增韧机理主要为第二相颗粒增韧机理、基体WC和第二相Al2O3颗粒热膨胀系数失配产生的残余应力增韧机理和Al2O3相变增韧机理；这些机理综合作用使裂纹搭桥、偏转,二次裂纹和侧生裂纹增多,从而提高复合材料的韧性。
2.以WC和α-Al2O3为原料,以3：2体积比的配方,在烧结温度为1540℃,保温时间为90min,压力为39.6MPa的热压烧结条件下制备WC-40vol.%α-Al2O3复合材料(WA2)；对比分析以不同种类Al2O3为原料制备的WC-Al2O3复合材料的微观组织和力学性能,探讨Al2O3相变对复合材料力学性能的影响及其增韧作用。研究结果表明：WC-40vol.%α-Al2O3复合材料致密度为98.38%,维氏硬度为16.55GPa,断裂韧性为8.52MPa·m1/2,抗弯强度为881.35MPa。WA1中AlOOH相变产生的少许水残留在试样中形成孔隙,是WA1致密度和抗弯强度较WA2低的原因；γ-Al2O3向α-Al2O3的相变消耗系统能量,从而减少WC氧化脱碳的能量,是WA1中脆性相W2C的形成被抑制的原因；γ-Al2O3向α-Al2O3的相变过程有24vol.%的体积缩小,从而获得较小的Al2O3颗粒,是WA1微观组织的细化、维氏硬度和断裂韧性较WA2高的原因；
3.为提高WA1和WA2复合材料的力学性能,研究添加剂MgO和稀土氧化物CeO2对复合材料微观组织和力学性能的影响及其机理。研究结果表明：添加MgO和CeO2未能提高WA1复合材料的力学性能；而对于WA2复合材料,分别添加MgO和CeO2时,最佳含量均为0.1wt.%,二者均可起到提高复合材料的致密度、抑制晶粒长大、改善颗粒之间的结合状态的作用；另外,活泼的稀土元素吸附复合粉末中的杂质氧,有效抑制WC的脱碳；CeO2在烧结过程中被还原成Ce2O3,并与Al2O3形成新的化合物,提高复合材料的结合强度。当同时添加0.05wt.%MgO和0.05wt.%CeO2时,WA2复合材料的综合性能达到最佳,致密度为99.04%TD,维氏硬度为18.18GPa,断裂韧性为10.14MPa·m1/2,抗弯强度为1155.38MPa。
4.依据WC-40vol.%α-Al2O3复合材料致密化速率和晶粒长大速率的变化情况,设计合理的二阶段热压烧结工艺；考察各工艺对试样微观组织和力学性能的影响并确定最佳烧结制度,探讨二阶段热压烧结对复合材料性能影响的机理。研究二阶段热压烧结法和添加剂MgO、CeO2共同作用对WC-40vol.%α-Al2O3复合材料组织和力学性能的影响。研究结果表明：TSS4烧结制度下(T1=1600℃,T2=1450℃,t2=6h)制备的WC-40vol.%α-Al2O3烧结试样的力学性能优于普通热压烧结制度CS1下(1540℃保温90min)所得烧结试样的力学性能。在TSS4和添加剂MgO、CeO2的共同作用下,WC-40vol.%α-Al2O3复合材料力学性能进一步提高,其致密度为99.42%TD,晶粒尺寸为2.921μm,维氏硬度为19.22GPa,断裂韧性为11.21MP·m1/2,抗弯强度为1236.78MPa,与热压烧结法制备的WC-Co硬质合金的力学性能相当。
5.研究以WC和无定形态Al2O3为原料的WC-40vol.%Al2O3复合材料的二阶段热压烧结工艺,探讨Al2O3相变和二阶段烧结技术对复合材料微观组织和力学性能的影响。研究结果表明：Al2O3的相变在第一阶段烧结后即已完成,则该材料第二阶段烧结开始时,起始颗粒尺寸较小,有利于获得匀细的微观组织；以WC和无定形态Al2O3为原料的WC-40vol.%Al2O3复合材料的最佳二阶段热压烧结工艺为TSS4(T1=1600℃,T2=1450℃,t2=6h)；在TSS4制度下制备试样的力学性能与CS1制度下制备试样的力学性能相比,致密度从97.98%TD增加至99%TD,WC晶粒尺寸从2.79gm减小至2.38gm,维氏硬度从18.65GPa提高至19.71GPa,断裂韧性从10.43MPa·m1/2提高至12MPa·m1/2,抗弯强度从881.35MPa提高至1285.08MPa。
本文中,作者率先采用无定形Al2O3和α-Al2O3代替Co,通过高能球磨、普通热压烧结法和二阶段热压烧结法制备新型WC-Al2O3复合材料,利用现代测试技术,对复合材料球磨和烧结过程中物相、热力学、微观结构和力学性能的变化进行表征,探讨复合材料致密化和增韧机理,及添加剂对复合材料的微观组织和力学性能的影响,为WC-Al2O3复合材料的进一步研究和应用奠定了坚实的基础。
Cemented carbide with superior hardness and strength, high elastic modulus and low thermal expansion coefficient, has been playing an important part in the areas of cutting tools, drilling and mining equipments, wear resistance parts and precision molds. Among hard alloys, WC-Co composites find the widest applications; The WC element is the assurance of high hardness, and the Co element is the guarantee of its fracture toughness. However, Co is rare, expensive and non-renewable strategic resource. Meanwhile, due to its excellent physical, chemical and mechanical properties, the demand of Co in ceramics, food additive, catalyst, batteries, electronic components and other aspects is increasing rapidly. Moreover, because of the low melting point and high chemical activity of Co, it will be soften and react with other elements easily, deteriorating the hardness and corrosion resistance of WC-Co composite. Therefore, it is of great significance and urgency to consolidate new WC matrix composite with cheap raw materials but high hardness and strength to instead of the WC-Co composite.
In this paper, Al2O3was chose as the substitute of Co, and WC-Al2O3composite had been consolidated through high energy ball milling and the following hot pressing. The content ratio of elements and the hot pressing parameters were systematically analyzed, the phase transformation of Al2O3during ball milling and hot pressing process, the thermodynamic of as milled powders, the hot pressing schedules and the toughening mechanisms had been investigated in details. Some significant original results are as follows:
Firstly, WC-Al2O3composites (WA1) were prepared by high energy ball milling and the following hot pressing. The tungsten carbide (WC) and commercial alumina (Al2O3) powders composed of amorphous Al2O3, boehmite (AlOOH) and χ-Al2O3were used as the starting materials. XRD was used to analyze the phase transformation during the ball milling and hot pressing process. The optimum hot pressing schedule, optimum content of Al2O3and the toughening mechanisms were clarified according to the investigation of microstructure and mechanical properties of the hot pressed bulk samples. The results showed that the powder size decreased and there was no phase transformation during the ball milling process, while during the hot pressing process, the amorphous and transitional Al2O3transformed to γ-Al2O3at961℃, and completely to α-Al2O3at1100℃. The WA1composites combined a relative density of97.98%and an excellent Vickers hardness of18.65GPa with an acceptable fracture toughness of10.43MPa-m1/2when hot pressed at1540℃for90min with a pressure of39.6MPa The second phase toughening mechanism, residual stress toughening mechanism and phase transformation of Al2O3were main toughening mechanisms in WA1composites. The crack bridging, crack deflection and the generation of secondary crack and lateral crack were the main reasons for the high fracture toughness and strength of WA1composites.
Secondly, WC-40vol.%α-Al2O3composites (WA2) were hot pressed at1540℃for90min under the pressure of39.6MPa. The toughening effects of phase transformation of Al2O3were investigated by comparison of microstructure and mechanical properties of WAI and WA2. The results showed that a relative density of98.38%and a maximum hardness of16.55GPa, combining a fracture toughness of8.52MPa-m1/2with an improved flexural strength of881.35MPa were obtained for the WA2composites. The relative density and the flexure strength of WA2were higher than that of WA1due to the residual pores induced by the water generated during the phase transformation of Al2O3in WA1; The decarburization of WC in WA1was suppressed may be attributed to the lowered energy provided for it, because many of the system energy was consumed by the phase transformation of Al2O3. The refined microstructure and higher hardness and fracture toughness were due to the decreased volume of Al2O3particles during the phase transformation.
Thirdly, to improve the mechanical properties of WA1and WA2, influence of MgO and CeO2additives on the microstructure and mechanical properties, and the mechanisms were investigated. The results showed that adding MgO and CeO2to WA1composite did not improve its mechanical properties; while for the WA2composite, when the MgO and CeO2were added separately, the optimum content was0.1wt.%, they could promote the microstructural refinement and improve the interface coherence of the WC matrix and Al2O3leading to the enhancement of the mechanical properties. Trace MgO mainly acted as an effective grain growth inhibitor for the WC-Al2O3composites and trace CeO2could suppress the decarburization of WC as well due to the unique properties of rare earth elements such as high surface activity and large ionic radius. The synergistic effect of0.05wt.%MgO and0.05wt.%CeO2added in WC-40vol.%α-Al2O3composites resulted in the achievement of a relative density of99.04%with an excellent Vickers hardness of18.18GPa, combining a fracture toughness of10.14MPa-m1/2with an acceptable flexural strength of1158.38MPa.
Fourthly, two step sintering (TSS) regimes were designed according to the densification rate and the grain growth rate of WC-40vol.%α-Al2O3composite. Microstructure and mechanical properties of WC-40voI.%α-Al2O3samples under each regime with different T1,, T2and t2were compared and analyzed to obtain the optimum TSS regime, the densification and toughening mechanisms of the composites under TSS regimes were discussed. Then WC-40vol.%α-Al2O3-0.05wt.%MgO-0.05wt.%CeO2powders were hot pressed under the optimum TSS regime to investigate the synergistic effect of additives and TSS regime. The results showed that the mechanical properties of samples under TSS4regime (T1=1600℃, T2=1450℃for6h) were improved compared with samples consolidated under CS1regime (1540℃for90min). WC-40vol.%α-Al2O3-0.05wt.%MgO-0.05wt.%CeO2powders hot pressed under TSS4regime achieved a relative density of99.42%TD with a grain size of2.92μm, combining an excellent Vickers hardness of19.22GPa, a fracture toughness of11.21MPa-m1/2with an acceptable flexural strength of1236.78MPa. The flexural strength was comparable with that of the WC-(3-8)wt.%Co cemented hard alloys (1150-1650MPa).
Fifthly, the optimum TSS regime of WC-40vol.%Al2O3composite with WC and amorphous Al2O3was investigated. Influence of Al2O3phase transformation and TSS regimes on the microstructure and mechanical properties of this WC-40vol.%Al2O3composite were illustrated. The results showed that Al2O3phase transformation had been completed when the sample was hot pressed under the first step sintering (1600℃for3min), resulting in the smaller particle size of Al2O3beneficial for the refined microstructure. When the as milled WC-40vol.%Al2O3powders were hot pressed under TSS4regime, a relative density of99%and a grain size of2.38μm were obtained, and an excellent Vickers hardness of19.71GPa was achieved, combining a fracture toughness of12MPa-m1/2with an acceptable flexural strength of1285.03MPa. Compared with the nearly full densified samples consolidated under CS1regime (1540℃for90min), the grain size decreased (2.79μm for the CS1sample), the Vickers hardness, fracture toughness and the flexural strength were all improved (18.65GPa,10.43MPa·m1/2,756.34MPa for the CS, sample) due to the refined microstructure and the transgranular fracture mode.
In this paper, amorphous Al2O3and α-Al2O3were used as the substitute of Co. WC-Al2O3composites were consolidated through high energy ball milling, the following hot pressing and two step hot pressing. Modern analytical technologies were used respectively to investigate the phases, thermodynamics and microstructure of the samples. The densification and toughening effects, as well as the influence of additives were illustrated. This paper has made a solid foundation for the further investigation and application of WC-Al2O3composites.
引文
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[1]Duran P, Capel F, Tartaj J, Moure C. Sintering behavior and electrical properties of nanosized doped-ZnO powders produced by metallorganic polymeric processing. J. Am. Ceram. Soc. 2001,84:1661-1668.
[2]Chen I W, Wang X H. Sintering dense nanocrystalline ceramics without final-stage grain growth. Nature 2000,404:168-171.
[3]Lee Y I, Kim Y W, Mitomo M, Kim D Y. Fabrication of dense nanostructured silicon carbide ceramics through two-step sintering. J. Am. Ceram. Soc.2003,86:1803-1805.
[4]Brook R J. Controlled Grain Growth; in Treatise on Materials Science and Technology, Vol.9. 1976. Edited by F. F. Y. Wang. Academic Press, New York, pp.331-364.
[5]Wang C J, Huang C Y, Wu Y C. Two step sintering of fine alumina-zirconia ceramics. Ceram. Int.2009,35:1467-1472.
[6]Mazaheri M, Zahedi A M, Sadrnezhaad S K. Two-step sintering of nanocrystalline ZnO compacts:effect of temperature on densification and grain growth. J. Am. Ceram. Soc.2008, 91(1):56-63.
[7]Mazaheri M, Valefi M, Razavi Hesabi Z, Sadrnezhaad S K. Two-step sintering of nanocrystalline 8Y2O3 stabilized ZrO2 synthesized by glycine nitrate process. Ceram. Int. 2009,35:13-20.
[8]Chen P L, Chen I W. Sintering of fine oxide powder:Ⅱ:sintering mechanisms. J. Am. Ceram. Soc.1997,80(3):637-645.
[9]Zhao J H, Harmer M P. Effect of pore distribution on microstructure development:Ⅰ, Matrix pores. J.Am. Ceram. Soc.1988,71(2):113-120.
[10]Zhao J H, Harmer M P. Effect of pore distribution on microstructure development:Ⅱ, First-and Second-generation pores. J. Am. Ceram. Soc.1988,71(7):530-539.
[11]Zhao J H, Harmer M P. Effect of pore distribution on microstructure development:Ⅲ, Model experiments, J. Am. Ceram. Soc.1992,75(4):830-843.
[12]Wang X H, Chen P L, Chen I W. Two-step sintering of ceramics with constant grain-size. I. Y2O3. J. Am. Ceram. Soc.2006,89:431-437.
[13]Bodisova K, Sajgalik P, Galusek D, Svancarek P. Two step sintering of Alumina with submicrometer grain size. J. Am. Ceram. Soc.2007,90(1):330-332.
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