CN109956754B - 石墨烯纳米片增韧TiB2基陶瓷刀具材料及其制备工艺 - Google Patents

石墨烯纳米片增韧TiB2基陶瓷刀具材料及其制备工艺 Download PDF

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CN109956754B
CN109956754B CN201711420900.1A CN201711420900A CN109956754B CN 109956754 B CN109956754 B CN 109956754B CN 201711420900 A CN201711420900 A CN 201711420900A CN 109956754 B CN109956754 B CN 109956754B
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殷增斌
袁军堂
徐伟伟
闫诗雨
刘奎
叶佳冬
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种石墨烯纳米片增韧TiB2基陶瓷刀具材料及其制备工艺。该材料组分质量配比为:硼化钛(TiB2):64.5‑74.9%,碳化钛(TiC):25‑35%,石墨烯纳米片(GnS):0.1‑0.5%。利用放电等离子烧结技术,在低温快速烧结条件下制备TiB2基陶瓷刀具材料。本发明制得的TiB2基陶瓷刀具材料不含金属粘结相、完全致密、且具有较高的断裂韧度和硬度,性能满足切削刀具的使用要求;同时本发明制备工艺先进,生产效率高,成本低,易于工业化生产,具有推广价值。

Description

石墨烯纳米片增韧TiB2基陶瓷刀具材料及其制备工艺
技术领域
本发明涉及放电等离子烧结材料技术领域,尤其涉及到一种石墨烯纳米片增韧TiB2基陶瓷刀具材料及其制备工艺。
背景技术
作为一种超高温陶瓷,TiB2具有高硬度、高弹性模量、耐磨损和良好的化学稳定性等优异的性能。TiB2基陶瓷特别适宜于制造在恶劣环境中工作的耐磨损部件,其中TiB2基陶瓷刀具在高速切削刀具中具有很强的应用潜力。然而,TiB2陶瓷难烧结、脆性大又限制了其作为刀具在高速切削加工中的应用。
TiB2熔点高达2980℃,自扩散系数小,且为共价键连接,这使得TiB2陶瓷很难达到完全致密。为了获得高的致密度,现阶段TiB2陶瓷刀具材料的制备多采用热压烧结。Zou(B.Zou et al. Mechanical properties and microstructure of TiB2-TiC compositeceramic cutting tool material. International Journal of Refractory Metals andHard Materials 35 (2012) 1-9.)和Song(J. Song et al. 2014. Effects of TiCcontent and melt phase on microstructure and mechanical properties of ternaryTiB2-based ceramic cutting tool materials. Materials Science and Engineering:A 605 (2014) 137-143.)分别采用热压烧结制备了TiB2-TiC-Ni和TiB2-TiC-WC-Ni-Mo陶瓷刀具材料,材料的相对密度分别达到99.4%和99.3%。
但是,为了获得高致密度,热压烧结通常需要高的烧结温度(1650-2100℃)、长的保温时间(0.5-2h)和低的升温速率(≤50℃/min),高温和长时间保温导致晶粒异常长大,不利于力学性能提高,同时长的烧结周期浪费能源,生产效率低。
现阶段为提高TiB2陶瓷的致密度和力学性能,通常加入各种金属相(Ni, Mo, Co,Fe, Ti, Ta)。实验证明加入金属相后TiB2陶瓷的烧结温度降低,相对密度可达99%以上,强度和断裂韧度也得到大幅度提高(Chlup et al. Effect of metallic dopants on themicrostructure and mechanical properties of TiB2. Journal of the EuropeanCeramic Society 35 (2015) 2745-2754.)。一般来说,金属含量越多,TiB2陶瓷的断裂韧度越大。然而,在高温环境下,由于金属软化,界面结合强度降低,晶界易产生滑移,造成TiB2陶瓷的强度、断裂韧度、硬度急剧下降,刀具耐磨损和破损能力降低。因此,含金属相的TiB2陶瓷并不是理想的高速切削刀具。
发明内容
本发明的目的在于克服采用传统热压烧结技术制备TiB2基陶瓷刀具材料效率低、耗能高,TiB2陶瓷脆性大,以及添加金属相容易削弱高温力学性能的弊端,提供一种石墨烯纳米片增韧TiB2基陶瓷刀具材料及其放电等离子制备工艺。
本发明的基本构思是通过建立复合陶瓷刀具材料理论抗弯强度与增强颗粒含量的关系模型,以及石墨烯纳米片的增韧补强机理,通过理论计算确定材料组分最优配比。采用放电等离子烧结方法,并通过优化粉末处理工艺、烧结温度、保温时间等工艺参数,制备出全致密高韧性的TiB2基陶瓷刀具材料。
实现本发明目的的技术解决方案是:本发明所述的全致密高韧性TiB2基陶瓷刀具材料,其组分质量配比(wt.%)为:硼化钛(TiB2):64.5-74.9%,碳化钛(TiC):25-35%,石墨烯纳米片(GnS):0.1-0.5%。
更优选的,本发明所述的全致密高韧性TiB2基陶瓷刀具材料,其组分质量配比(wt.%)为:硼化钛(TiB2):67.8-71.9%,碳化钛(TiC):28-32%,石墨烯纳米片(GnS):0.1-0.2%。
上述石墨烯纳米片增韧TiB2基陶瓷刀具材料的制备工艺为:
(1)按比例称取TiB2和TiC粉末,同时加入分散后的石墨烯纳米片悬浮液中,以硬质合金球湿混球磨;
(2)将球磨后的粉料在真空干燥,真空冷却至室温后过筛;
(3)将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至25-40MPa,在真空环境中,以80-150℃/min的升温速率将温度升至1750-1900℃,并在此温度保温1-10min,然后随炉冷却,制得石墨烯纳米片增韧的TiB2基陶瓷刀具材料。
进一步的,步骤(1)中,石墨烯纳米片悬浮液通过将石墨烯纳米片在酒精介质中超声分散加机械搅拌60min以上得到。
进一步的,步骤(1)中,以硬质合金球湿混球磨12小时以上。
进一步的,步骤(2)中,将球磨后的粉料在120℃以下真空干燥;真空冷却至室温后过100目以上的筛。
本发明与现有技术相比,具有以下显著优点:
(1)本发明利用放电等离子制备TiB2基陶瓷刀具材料,与传统热压烧结相比,升温速率提高了2倍,保温时间缩短了83.3-91.7%。该先进的制备工艺极大地降低了能源消耗,提高了生产效率,有利于降低陶瓷刀具的价格,具有推广价值。
(2)本发明引入石墨烯纳米片作为增韧相,利用其高强度、高弹性模量及独特的二维结构,在添加极少量的情况下获得韧度大幅度提高;且本发明TiB2基陶瓷刀具材料在不添加金属相的情况下得到了完全致密,更适用于高速切削。
附图说明
图1为实施例7制备的石墨烯纳米片增韧TiB2基陶瓷刀具材料断口SEM形貌。
图2为实施例7为制备的石墨烯纳米片增韧TiB2基陶瓷刀具材料裂纹扩展路径。
具体实施方式
本发明为一种石墨烯纳米片增韧TiB2基陶瓷刀具材料及其制备工艺。
石墨烯具有二维结构,弹性模量高,抗拉强度大,只需少量的石墨烯就可以使材料的断裂韧度得到大幅度提高,是一种理想的增韧补强材料。本发明利用放电活化和等离子加速致密的独特优势,通过添加二维增强相——石墨烯纳米片,在低温快速条件下制备全致密的TiB2基陶瓷刀具材料。
实施例1
按TiB2 5.6g、TiC 2.4g、GnS 0g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至30MPa,在真空环境中,以100℃/min的升温速率将温度升至1750℃,并在此温度保温5min,然后随炉冷却。
实施例2
按TiB2 5.592g、TiC 2.4g、GnS 0.008g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至30MPa,在真空环境中,以100℃/min的升温速率将温度升至1750℃,并在此温度保温5min,然后随炉冷却。
实施例3
按TiB2 5.584g、TiC 2.4g、GnS 0.016g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至30MPa,在真空环境中,以100℃/min的升温速率将温度升至1750℃,并在此温度保温5min,然后随炉冷却。
实施例4
按TiB2 5.576g、TiC 2.4g、GnS 0.024g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至30MPa,在真空环境中,以100℃/min的升温速率将温度升至1750℃,并在此温度保温5min,然后随炉冷却。
实施例5
按TiB2 5.568g、TiC 2.4g、GnS 0.032g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至30MPa,在真空环境中,以100℃/min的升温速率将温度升至1750℃,并在此温度保温5min,然后随炉冷却。
实施例6
按TiB2 5.56g、TiC 2.4g、GnS 0.04g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至30MPa,在真空环境中,以100℃/min的升温速率将温度升至1750℃,并在此温度保温5min,然后随炉冷却。
实施例7
按TiB2 5.592g、TiC 2.4g、GnS 0.008g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至30MPa,在真空环境中,以100℃/min的升温速率将温度升至1800℃,并在此温度保温5min,然后随炉冷却。
实施例8
按TiB2 5.592g、TiC 2.4g、GnS 0.008g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至25MPa,在真空环境中,以120℃/min的升温速率将温度升至1850℃,并在此温度保温5min,然后随炉冷却。
实施例9
按TiB2 5.592g、TiC 2.4g、GnS 0.008g进行配料;将称取的石墨烯纳米片在酒精介质中超声分散加机械搅拌60min;将TiB2和TiC粉末连同分散后的石墨烯纳米片悬浮液装入行星球磨机中,以无水乙醇为介质用硬质合金球磨24小时;将球磨后的粉料在真空120℃下干燥,冷却至室温后过100目筛;将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至40MPa,在真空环境中,以100℃/min的升温速率将温度升至1900℃,并在此温度保温3min,然后随炉冷却。
与传统的热压烧结相比,实施例7中的TiB2基陶瓷刀具材料达到完全致密的烧结周期降低了64.6%-75.8%,这极大地降低了能源消耗,提高了生产效率,有利于降低陶瓷刀具的价格,使陶瓷刀具得以推广应用。
实施例1-9的力学性能如表1所示,加入质量分数0.1%石墨烯纳米片的TiB2基陶瓷刀具材料断裂韧度最高,比不加石墨烯纳米片的断裂韧度提高31.7%。实施例7的断口形貌如图1所示,石墨烯纳米片均匀嵌在晶界处,抑制了晶粒长大,晶粒细小,材料微观组织均匀。实施例7的裂纹扩展路径如图2所示,石墨烯纳米片引起的裂纹桥接是主要的增韧机制,相比于传统的颗粒桥接(矩形虚线框),石墨烯的“锚”效应使得桥接区域更大(圆形虚线框),消耗的断裂能更多,这更有利于断裂韧度的提高。
表1为实施例1-9的力学性能参数。
表1 实施例性能参数
Figure 237545DEST_PATH_IMAGE002

Claims (4)

1.增韧TiB2基陶瓷刀具材料的制备工艺,其特征在于,包括如下步骤:
(1)按比例称取TiB2和TiC粉末,同时加入分散后的石墨烯纳米片悬浮液中,以硬质合金球湿混球磨,所述石墨烯纳米片悬浮液通过将石墨烯纳米片在酒精介质中超声分散加机械搅拌60min以上得到;
(2)将球磨后的粉料在真空干燥,真空冷却至室温后过筛;
(3)将过筛的粉料装入石墨模具,放入放电等离子烧结炉中,并施压至25-40MPa,在真空环境中,以80-150℃/min的升温速率将温度升至1750-1900℃,并在此温度保温1-10min,然后随炉冷却,制得石墨烯纳米片增韧的TiB2基陶瓷刀具材料;
所述组分质量配比为:硼化钛TiB2:64.5-74.9%,碳化钛TiC:25-35%,石墨烯纳米片GnS:0.1-0.5%。
2.如权利要求1所述的制备工艺,其特征在于,所述组分质量配比优化为:硼化钛TiB2:67.8-71.9%,碳化钛TiC:28-32%,石墨烯纳米片GnS:0.1-0.2%。
3.如权利要求1所述的制备工艺,其特征在于,步骤(1)中,以硬质合金球湿混球磨12小时以上。
4.如权利要求1所述的制备工艺,其特征在于,步骤(2)中,将球磨后的粉料在120℃以下真空干燥;真空冷却至室温后过100目以上的筛。
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