CaO–Al2O3–SiO2复合烧结助剂添加量对ZrO2/Al2O3复相陶瓷性能的影响

冯杰; 赵介南; 凌可君

doi:10.19591/j.cnki.cn11-1974/tf.2019.03.003

CaO–Al₂O₃–SiO₂复合烧结助剂添加量对ZrO₂/Al₂O₃复相陶瓷性能的影响

doi: 10.19591/j.cnki.cn11-1974/tf.2019.03.003

沈阳大学机械工程学院, 沈阳 110044

详细信息

通讯作者:
赵介南, E-mail:185154734@qq.com

中图分类号: TQ174
计量
- 文章访问数: 349
- HTML全文浏览量: 84
- PDF下载量: 13
- 被引次数: 0
出版历程
- 收稿日期: 2018-09-11
- 刊出日期: 2019-06-27

Effect of addition contents of CaO–Al₂O₃–SiO₂ composite sintering aids on the properties of ZrO2/Al2O3 composite ceramics

School of Mechanical Engineering, Shenyang University, Shenyang 110044, China

More Information

Corresponding author: ZHAO Jie-nan, E-mail:185154734@qq.com

摘要

摘要: 以Al(NO₃)₃·9H₂O、Ca(NO)₂·4H₂O、C₈H₂₀O₄Si为原料, 采用高分子网络法制备出成分均匀、粒度分布为3~7μm、高活性的CaO–Al₂O₃–SiO₂复合烧结助剂; 将质量分数为3%、5%、7%、9%的CaO–Al₂O₃–SiO₂复合烧结助剂添加到Al₂O₃和ZrO₂原料粉体中, 经干压成型, 在1450℃烧结温度、保温4h的工艺条件下进行常压烧结制备得到ZrO₂/Al₂O₃复相陶瓷试样, 研究烧结助剂添加量对复相陶瓷力学性能和显微组织结构的影响。结果表明:当添加质量分数为5%的CaO–Al₂O₃–SiO₂复合烧结助剂时, ZrO₂/Al₂O₃复相陶瓷的综合性能最达到佳, 相对密度为94%, 显微维氏硬度为1204 MPa, 抗弯强度为321 MPa, 断裂韧性为4.52 MPa·m^1/2。
- 烧结助剂 /
- 复相陶瓷 /
- 常压烧结 /
- 力学性能 /
- 高分子网络法
Abstract: The CaO–Al₂O₃–SiO₂ composite sintering aids were prepared by polymer network method using Al(NO₃)₃·9H₂O, Ca (NO) 2·4 H₂O, and C₈H₂₀O₄Si as the raw materials, showing the uniform constituent and high activity in the particle sizes of 3~7 μm.The Al₂O₃ and ZrO₂ raw powders were mixed and dry pressed with the CaO–Al₂O₃–SiO₂ composite sintering aids in the mass fraction of 3%, 5%, 7%, and 9%, and then the ZrO₂/Al₂O₃ composite ceramics samples were pressureless sintered at 1450 ℃ for 4 h.The effect of addition contents of CaO–Al₂O₃–SiO₂ composite sintering aids on the mechanical properties and microstructures of ZrO₂/Al₂O₃ composite ceramics were studied.The results show that, the comprehensive properties of ZrO₂/Al₂O₃ composite ceramics added with the CaO–Al₂O₃–SiO₂ composite sintering aids in the mass fraction of 5% are the optimal as the relative density of 94%, the micro-Vickers hardness of 1204 MPa, the flexural strength of 321 MPa, and the fracture toughness of 4.52 MPa·m^1/2.
- sintering aids /
- composite ceramics /
- pressureless sintering /
- mechanical properties /
- polymer network method

HTML全文

图 1 陈化12 h凝胶前驱体中各元素面分布: (a)凝胶前驱体; (b) Al; (c) Ca; (d) Si

Figure 1. Surface distribution of elements in gel precursor after aging for 12 h: (a) gel precursor; (b) Al; (c) Ca; (d) Si

下载: 全尺寸图片幻灯片

图 2 陈化24 h凝胶前驱体中各元素面分布: (a)凝胶前驱体; (b) Al; (c) Ca; (d) Si

Figure 2. Surface distribution of elements in gel precursor after aging for 24 h: (a) gel precursor; (b) Al; (c) Ca; (d) Si

下载: 全尺寸图片幻灯片

图 3 陈化36 h凝胶前驱体中各元素面分布: (a)凝胶前驱体; (b) Al; (c) Ca; (d) Si

Figure 3. Surface distribution of elements in the gel precursor after aging for 36 h: (a) gel precursor; (b) Al; (c) Ca; (d) Si

下载: 全尺寸图片幻灯片

图 4 复合烧结助剂前驱体热重‒差热分析曲线

Figure 4. TG–DTA curve for gel precursors of composite sintering aids

下载: 全尺寸图片幻灯片

图 5 CaO–Al₂O₃–SiO₂复合烧结助剂显微组织形貌: (a) ×2000; (b) ×7000

Figure 5. Microstructures of CaO–Al₂O₃–SiO₂ composite sintering aids: (a) ×2000; (b) ×7000

下载: 全尺寸图片幻灯片

图 6 煅烧温度为600℃时复合烧结助剂显微组织形貌(a)和区域1处的能谱分析(b)

Figure 6. SEM image (a) and EDS analysis of area 1 (b) of CaO–Al₂O₃–SiO₂ composite sintering aids calcined at 600℃

下载: 全尺寸图片幻灯片

图 7 ZrO₂/Al₂O₃复合陶瓷相对密度、断裂韧性与烧结助剂质量分数关系

Figure 7. Relationship of relative density, fracture toughness, and sintering aid content by mass of ZrO₂/Al₂O₃composite ceramics

下载: 全尺寸图片幻灯片

图 8 ZrO₂/Al₂O₃复合陶瓷维氏硬度、和抗弯强度与烧结助剂质量分数关系

Figure 8. Relationship of Vickers-hardness, flexural strength, and sintering aid content by mass of ZrO₂/Al₂O₃composite ceramics

下载: 全尺寸图片幻灯片

图 9 添加不同质量分数烧结助剂的ZrO₂/Al₂O₃复合陶瓷断口显微形貌: (a) 3%; (b) 5%; (c) 7%; (d) 9%

Figure 9. Fracture morphology of ZrO₂/Al₂O₃ composite ceramic with different contents of sintering aids by mass: (a) 3%; (b) 5%; (c) 7%; (d) 9%

下载: 全尺寸图片幻灯片

图 10 ZrO₂/Al₂O₃复相陶瓷X射线衍射图谱

Figure 10. XRD patterns of ZrO₂/Al₂O₃ composite ceramics

下载: 全尺寸图片幻灯片

表 1 不同陈化时间对凝胶前驱体的影响实验设计方案

Table 1. Experimental design of aging time effect on gel precursor

实验编号	水含量/ mL	陈化时间/ h	丙烯酰胺与N, N-亚甲基双丙烯酰胺质量比	过硫酸铵/ g
1	150	12	6:1	0.1
2	150	24	6:1	0.1
3	150	36	6:1	0.1

下载: 导出CSV

表 2 ZrO₂/Al₂O₃复相陶瓷原料成分

Table 2. Composition of raw materials for ZrO₂/Al₂O₃ composite ceramics

编号	α–Al₂O₃ / g	ZrO₂ / g	CaO–Al₂O₃–SiO₂ / g
试样1	87.00	15.00	3
试样2	82.65	14.25	5
试样3	80.91	13.95	7
试样4	79.17	13.65	9

下载: 导出CSV

参考文献(17)

[1]	La P Q, Zhang X P, Lu X F. Research status of nanocomposite ceramics fabrication techniques. Mater Rev, 2009, 23(4): 25 https://www.cnki.com.cn/Article/CJFDTOTAL-CLDB200907010.htm 喇培清, 张秀萍, 卢学峰.纳米复相陶瓷制备技术的研究现状.材料导报, 2009, 23(4): 25 https://www.cnki.com.cn/Article/CJFDTOTAL-CLDB200907010.htm
[2]	Liu G X, Li K Z, Li G B. Effects of ZrO₂ additive amount on properties of ZrO₂/Al₂O₃ composite ceramics. Ordn Mater Sci Eng, 2015, 38(4): 37 https://www.cnki.com.cn/Article/CJFDTOTAL-BCKG201504012.htm 刘国玺, 李克智, 李国斌. ZrO₂添加量对Al₂O₃/ZrO₂复相陶瓷性能的影响.兵器材料科学与工程, 2015, 38(4): 37 https://www.cnki.com.cn/Article/CJFDTOTAL-BCKG201504012.htm
[3]	Zhao Z M, Wang J J, Zhang L, et al. Self-propagating high-temperature synthesis of nano/micron Al₂O₃/ZrO₂liner composite ceramics. Powder Metall Technol, 2004, 22(4): 218 doi: 10.3321/j.issn:1001-3784.2004.04.006 赵忠民, 王建江, 张龙, 等.纳米/微米Al₂O₃/ZrO₂内衬复相陶瓷的自蔓延高温合成.粉末冶金技术, 2004, 22(4): 218 doi: 10.3321/j.issn:1001-3784.2004.04.006
[4]	Wang B J, Wang X M, La P Q. Effects of sintering temperature on mechanical properties and microstructure of 20%ZrO₂(3Y)/Al₂O₃ composite ceramics. J Mater Eng, 2015, 43(10): 66 doi: 10.11868/j.issn.1001-4381.2015.10.011 王丙军, 王晓民, 喇培清.烧结温对20%ZrO₂(3Y)/Al₂O₃复相陶瓷力学性能和微观结构的影响.材料工程, 2015, 43(10): 66 doi: 10.11868/j.issn.1001-4381.2015.10.011
[5]	Han X L, Liang Z Z, Feng L, et al. Co-precipitated synthesis of A1₂O₃-ZrO₂ composite ceramic nanopowders by precipitant and drying method regulation: A systematic study. Ceram Int, 2015, 41: 505. doi: 10.1016/j.ceramint.2014.08.098
[6]	Zhao R, Sun H W, Liu H J, et al. Effect of composite sintering additives on A1₂O₃-ZrO₂ ceramics relative density. Bull Chin Ceram Soc, 2011, 30(2): 291 https://www.cnki.com.cn/Article/CJFDTOTAL-GSYT201102007.htm 赵冉, 孙洪巍, 刘慧娟, 等.复合烧结助剂对Al₂O₃-ZrO₂陶瓷相对密度的影响.硅酸盐通报, 2011, 30(2): 291 https://www.cnki.com.cn/Article/CJFDTOTAL-GSYT201102007.htm
[7]	Ning F, Fu L H, Deng P, et al. Effects of SiO₂-B₂O₃-A1₂O₃ scaling powder on microstructures and properties of Cu-C-SnO₂ porous materials sintered by powders. Powder Metall Technol, 2018, 36(5): 335 doi: 10.19591/j.cnki.cn11-1974/tf.2018.05.003 倪锋, 傅丽华, 邓攀, 等. SiO₂-B₂O₃-Al₂O₃助焊剂对粉末烧结Cu-C-SnO₂多孔材料组织与性能的影响.粉末冶金技术, 2018, 36(5): 335 doi: 10.19591/j.cnki.cn11-1974/tf.2018.05.003
[8]	Hu J L, Liu X, Ding C Z, et al. Influence of additives on properties of low temperature sintering 95 Alumina ceramics. China Ceram, 2012, 48(2): 11 https://www.cnki.com.cn/Article/CJFDTOTAL-ZGTC201202003.htm 胡继林, 刘鑫, 丁常泽, 等.添加剂对低温烧结95氧化铝陶瓷性能的影响.中国陶瓷, 2012, 48(2): 11 https://www.cnki.com.cn/Article/CJFDTOTAL-ZGTC201202003.htm
[9]	Hirota K, Shibaya K, Matsuda H, et al. Fabrication of novel ZrO₂(Y₂O₃)-Al₂O₃ ceramics having high strength and toughness utilising pulsed electric current pressure sintering(PECPS). Adv Appl Ceram, 2014, 113(2): 73. doi: 10.1179/1743676113Y.0000000107
[10]	Ren H L, Long B, Ning J G, et al. Mechanical properties and toughening mechanisms of ZrO₂ toughened Al₂O₃ceramics. Acta Mater Compos Sin, 2015, 32(3): 776 https://www.cnki.com.cn/Article/CJFDTOTAL-FUHE201503021.htm 任会兰, 龙波, 宁建国, 等. ZrO2增韧Al2O3陶瓷的力学性能和增韧机制.复合材料学报, 2015, 32(3): 776 https://www.cnki.com.cn/Article/CJFDTOTAL-FUHE201503021.htm
[11]	Li J S, Zhang C R, Li B. Advances in precursors for the preparation of boron nitride. Bull Chin Ceram Soc, 2011, 30(3): 567 https://www.cnki.com.cn/Article/CJFDTOTAL-GSYT201103019.htm 李俊生, 张长瑞, 李斌.氮化硼陶瓷先驱体研究进展.硅酸盐通报, 2011, 30(3): 567 https://www.cnki.com.cn/Article/CJFDTOTAL-GSYT201103019.htm
[12]	Liu H, Zhang N, Zhang T W, et al. Research progress of boron nitride ceramic composite material produced by hot pressing. Powder Metall Technol, 2014, 24(6): 48 https://www.cnki.com.cn/Article/CJFDTOTAL-FMYG201406019.htm 刘欢, 张宁, 张天文, 等.热压烧结制备BN陶瓷复合材料的研究进展.粉末冶金技术, 2014, 24(6): 48 https://www.cnki.com.cn/Article/CJFDTOTAL-FMYG201406019.htm
[13]	Yang F Y. The Study of BN‒SiC Amorphous Ceramic Powder Preparation[Dissertation]. Shenyang: Shenyang University, 2014 杨非易. BN‒SiC非晶态陶瓷粉体的制备研究, 沈阳: 沈阳大学, 2014
[14]	Zhao J N, Zhang N, Zhou B B, et al. Toughening research and prospect of development on alumina matrix ceramic material. Bull Chin Ceram Soc, 2016, 35(9): 2866 https://www.cnki.com.cn/Article/CJFDTOTAL-GSYT201609029.htm 赵介南, 张宁, 周彬彬, 等. Al₂O₃基陶瓷材料的增韧研究进展.硅酸盐通报, 2016, 35(9): 2866 https://www.cnki.com.cn/Article/CJFDTOTAL-GSYT201609029.htm
[15]	Zhu T B, Xie Z P, Han Y, et al. A novel approach to improve flexural strength of Al₂O₃-20wt%ZrO₂composites by oscillatory pressure sintering. J Am Ceram Soc, 2018, 101: 1397.
[16]	Li C, Wu M, Zhao J L, et al. Research progress on sintering technology of nano-ceramic material. Hot Working Technol, 2012, 41(24): 57 https://www.cnki.com.cn/Article/CJFDTOTAL-SJGY201224017.htm 李翀, 武明, 赵金龙, 等.纳米陶瓷材料烧结技术的研究进展.热加工工艺, 2012, 41(24): 57 https://www.cnki.com.cn/Article/CJFDTOTAL-SJGY201224017.htm
[17]	Zheng Y T, Li H B, Zhou T, et al. Microstructure and mechanical properties of A1₂O₃/ZrO₂ eutectic ceramic composites prepared by explosion synthesis. J Alloys Compd, 2013, 551: 475.