CN104909749B - 一种低/无吸水性负热膨胀陶瓷Y2Mo3O12及其固相烧结合成方法 - Google Patents
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Abstract
一种新型低/无吸水性负热膨胀陶瓷Y2Mo3O12及其固相烧结合成方法,属于无机非金属材料技术领域,该陶瓷以Y2O3、MoO3和尿素为原料,采用固相烧结合成方法制得。本发明的有益效果:1.本发明将尿素高温分解结合到Y2Mo3O12的烧结过程中,减少以致避免在降温过程中水分进入,减少甚至彻底消除吸水性,同时获得从室温开始的负热膨胀性能。2.本发明采用固相法烧结,工艺简单,低成本,适合于工业化生产。
Description
技术领域
本发明属于无机非金属材料领域,特别涉及了一种低/无吸水性负热膨胀陶瓷Y2Mo3O12及其固相烧结合成方法。
背景技术
不同材料热膨胀系数存在差异,并且同一材料由表面到内部的不同深度因存在热梯度导致热膨胀不同,在温度剧烈变化或变化较大的场合,不同材料之间或同一材料不同深度会产生热应力。这些热应力常常会引起材料或器件的性能指标变差,如热膨胀仪的系统误差、高温炉管由于温度变化大而出现裂缝或断开、冬季水管或水箱冻裂、高压输电线由于夏季温度升高而伸长并下垂从而增加辅助的线杆的拉力、空间望远镜焦距随温度变化引起成像质量下降、印刷电路板上的铜箔由于受热脱离、激光器因热透镜效应出射光束的发散、航天器隔热层脱落等。为了减少不同材料之间的热应力,必须探索热膨胀系数为零或接近零、或能够匹配的材料,然而零膨胀系数的材料不易寻找。目前制备近零热膨胀材料是通过对负热膨胀材料改性或将负热膨胀材料与正热膨胀材料复合来实现的。
Y2Mo3O12是一种负热膨胀系数大、温区宽的结构稳定的具有应用前景的负热膨胀材料。然而常规的方法(比如固相法、激光快速烧结法等)制备的负热膨胀材料Y2Mo3O12具有明显的吸水性,其负热膨胀性能只有在升高温度后完全释放水后才能表现出来,并且高温烧结的Y2Mo3O12陶瓷块体放在空气中,因为逐步吸水陶瓷块体会慢慢裂开甚至成粉体。为了消除Y2Mo3O12的吸水性,采用离子替代法研究较多:Fe3+ (Z.Y. Li, W.B. Song, E.J.Liang, J. Phys. Chem. C 115 (2011) 17806-17811), Ce3+ (X.S. Liu, Y.G. Cheng,E.J. Liang, M.J. Chao, Phys. Chem. Chem. Phys. 16 (2014) 12848-12857), La3+(H.F. Liu, X.C. Wang, Z.P. Zhang, X.B. Chen, Ceram. Int. 38 (2012) 6349-6352)和 (LiMg)3+ (Y.G. Cheng, X.S. Liu, W.B. Song, B.H. Yuan, X.L. Wang, M.J. Chao,E.J. Liang, Mater. Res. Bull. 65 (2015) 273-278)。然而,替代后的结果是,吸水性消除了,但是负热膨胀现象没有表现出来,表现出来的却是正热膨胀现象。这说明,Y2Mo3O12的吸水性消除并且表现出负热膨胀现象的问题解决仍然具有很大的挑战性。因此,研发一种没有明显吸水性的、成本较低的负热膨胀材料Y2Mo3O12具有重要的实际意义。
发明内容
本发明的目的是提供一种低/无吸水性负热膨胀陶瓷Y2Mo3O12及其固相烧结合成方法。
基于上述目的,本发明采取了如下技术方案:
一种低/无吸水性负热膨胀陶瓷Y2Mo3O12,该陶瓷以Y2O3、MoO3和尿素为原料,采用固相烧结合成方法制得。
进一步地,原料Y2O3、MoO3摩尔比为1︰3,原料尿素的量为Y2Mo3O12物质的量的1~7mol%。
添加尿素的摩尔比达到Y2Mo3O12的5 mol%后,该负热膨胀陶瓷Y2Mo3O12负热膨胀温度区域扩展到室温;添加尿素的摩尔比达到Y2Mo3O12的7 mol%后,该负热膨胀陶瓷的吸水性彻底消除。
上述低/无吸水性负热膨胀陶瓷Y2Mo3O12的固相烧结合成方法,(1)按比例称取Y2O3、MoO3和尿素,将原料研磨混合均匀;(2)将步骤(1)中混合均匀的物料直接烧结或压片后烧结,自然冷却得目标产物,即低/无吸水性负热膨胀陶瓷Y2Mo3O12;其中,烧结条件为:温度为750~850℃,时间为3-5 h,压强为常压,气氛为空气。
本发明的有益效果:
1. 本发明将尿素高温分解结合到Y2Mo3O12的烧结过程中,减少以致避免在降温过程中水分进入,减少甚至彻底消除吸水性,同时获得负热膨胀性能,即:尿素分解得到C3N4,在高温烧结过程中,C3N4包裹着Y2Mo3O12,阻碍了水分在降温过程中进入Y2Mo3O12晶格,从而降低了吸水性,并且Y2Mo3O12负热膨胀温度区间向室温延伸。
2. 本发明采用固相法预处理原料,工艺简单,低成本,适合于工业化生产。
附图说明
图1为实施例1合成的Y2Mo3O12的XRD图谱(850℃, 3 h)。
图2为实施例2原料中掺入1 mol%尿素合成Y2Mo3O12的XRD图谱(800℃, 5 h)。
图3为实施例3原料中掺入3 mol%尿素合成Y2Mo3O12的XRD图谱(800℃, 5 h)。
图4为实施例4原料中掺入5 mol%尿素合成Y2Mo3O12的XRD图谱(750℃, 3 h)。
图5为实施例5原料中掺入7 mol%尿素合成Y2Mo3O12的XRD图谱(750℃, 3 h)。
图6为实施例1、2、3和4所制备的掺入尿素0 mol%、1 mol%、3 mol%、5 mol%、7 mol%陶瓷Y2Mo3O12的相对长度随温度的变化曲线。
具体实施方式
实施例1
将原料Y2O3和MoO3按化学计量摩尔比1:3称取,放到研钵内研磨2 h,用单轴方向压片机200 MPa的压强下压制成直径10 mm,高10 mm的圆柱体。将装有样品的刚玉坩埚放在高温炉中在850℃温度下常压空气中烧结3 h,在空气中自然冷却。产品对应的XRD图谱物相分析见图1,图1的XRD结果显示形成了纯的正交相Y2Mo3O12(XRD中没有杂质相和原料的峰)。
实施例2
与实施例1的不同之处在于:在原料中添加按目标产物Y2Mo3O12的 1 mol%的尿素,烧结温度为800℃,烧结时间是5 h。产品对应的XRD图谱物相分析见图2,图2的XRD结果显示形成了纯的正交相Y2Mo3O12(XRD中没有杂质相和原料的峰)。
实施例3
与实施例1的不同之处在于:在原料中添加按目标产物Y2Mo3O12的3 mol%的尿素,烧结温度为800℃,烧结时间为5 h。产品对应的XRD图谱物相分析见图3,图3的XRD结果显示形成了纯的正交相Y2Mo3O12(XRD中没有杂质相和原料的峰)。
实施例4
与实施例2的不同之处在于:在原料中添加按目标产物Y2Mo3O12的5 mol%的尿素,烧结温度为750℃,烧结时间是3 h。产品对应的XRD图谱物相分析见图4,图4的XRD结果显示形成了纯的正交相Y2Mo3O12(XRD中没有杂质相和原料的峰)。
实施例5
与实施例2的不同之处在于:在原料中添加按目标产物Y2Mo3O12的7 mol%的尿素,烧结温度为750℃,烧结时间是3 h。产品对应的XRD图谱物相分析见图5,图5的XRD结果显示形成了纯的正交相Y2Mo3O12(XRD中没有杂质相和原料的峰)。
膨胀系数测试:
图6是实施例1、2、3、4和5所制备的陶瓷Y2Mo3O12的相对长度随温度的变化曲线。可知: 0%尿素掺入量的Y2Mo3O12的长度随温度的增加先发生减小,再急剧增加然后减小,表明其有两类水分子失去过程,即先释放结合力小的水分子,再释放结合力大的水分子。随着尿素掺入量的增加,结晶水减少(1→3 mol%),其急剧膨胀的过程缩短并且对应的温度也降低,直到结晶水彻底消除 (7 mol%),只有负热膨胀过程。其负热膨胀系数及对应的温度范围分别是:0%:α =-9.51×10-6oC-1 (180-520 oC);1 mol%:α =-9.00×10-5oC-1 (138-520oC);3 mol%: α =-8.71×10-6oC-1 (125-520 oC);5 mol%: α =-6.76×10-6oC-1 (20-520oC);7 mol%: α =-8.24×10-6oC-1 (20-520 oC)。其负热膨胀开始温度依次降低:180 oC→138 oC →125 oC →20 oC,最终降低到室温范围,并且对应结晶水释放过程的热膨胀彻底消除,也就是结晶水彻底消除。
Claims (3)
1.一种低/无吸水性负热膨胀陶瓷Y2Mo3O12,其特征在于:该陶瓷以Y2O3、MoO3和尿素为原料,采用固相烧结合成方法制得,其中,原料Y2O3、MoO3摩尔比为1︰3,原料尿素的量为Y2Mo3O12物质的量的1~7 mol%。
2.如权利要求1所述的低/无吸水性负热膨胀陶瓷Y2Mo3O12,其特征在于:添加尿素的摩尔比达到Y2Mo3O12的5 mol%后,该负热膨胀陶瓷Y2Mo3O12负热膨胀温度区域扩展到室温。
3.如权利要求1或2所述的低/无吸水性负热膨胀陶瓷Y2Mo3O12的固相烧结合成方法,其特征在于:(1)按比例称取Y2O3、MoO3和尿素,将原料研磨混合均匀;(2)将步骤(1)中混合均匀的物料直接烧结或压片后烧结,自然冷却得目标产物,即低/无吸水性负热膨胀陶瓷Y2Mo3O12;其中,烧结条件为:温度为750~850℃,时间为3-5 h,压强为常压,气氛为空气。
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Correlation between AO6 Polyhedral Distortion and Negative Thermal Expansion in Orthorhombic Y2Mo3O12 and Related Materials;Bojan A.Marinkovic et al.,;《CHEMISTRY OF MATERIALS》;20090406;第21卷(第13期);2886-2894页 * |
Negative thermal expansion correlated with polyhedral movements and distortions in orthorhombic Y2Mo3O12;Lei Wang et al.,;《Materials Research Bulletin》;20130430;第48卷;2724-2729页 * |
Negative thermal expansion in Y2Mo3O12;B.A.Marinkovic et al.,;《Solid State Sciences》;20051017(第7期);1377-1383页 * |
Negative Thermal Expansion Materials and Their Applications:A Survey of Recent Patents;Er-Jun Liang;《Recent Patent on Materials Science》;20101231;第3卷(第2期);第106-128页 * |
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