CN105645961A - 一种负温度系数SiC热敏陶瓷及其制备方法 - Google Patents

一种负温度系数SiC热敏陶瓷及其制备方法 Download PDF

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CN105645961A
CN105645961A CN201511025901.7A CN201511025901A CN105645961A CN 105645961 A CN105645961 A CN 105645961A CN 201511025901 A CN201511025901 A CN 201511025901A CN 105645961 A CN105645961 A CN 105645961A
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thermal sensitive
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陈健
黄政仁
刘学建
陈忠明
姚秀敏
袁明
朱云洲
刘岩
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Shanghai Institute of Ceramics of CAS
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Abstract

本发明涉及一种负温度系数SiC热敏陶瓷及其制备方法,所述负温度系数SiC热敏陶瓷由碳化硅和固相烧结过程中原位复合的碳组成,所述碳在所述负温度系数SiC热敏陶瓷的重量百分含量为3~6wt%,所述负温度系数SiC热敏陶瓷热敏感指数β为:20℃-80℃下为6000K-10000K,80℃-220℃下为2000K-3000K,220℃-400℃下为10000K-15000K。本发明提供了一种高导热,高耐腐蚀性负温度系数(negative?temperature?coefficient)NTC碳化硅(SiC)热敏陶瓷,经测试该陶瓷材料具有负温度系数热敏特性,随着温度的升高电阻率降低;在一定电场强度下测定,在温度20℃-400℃之间变化时,电阻率在5-106Ωcm变化。

Description

一种负温度系数SiC热敏陶瓷及其制备方法
技术领域
本发明涉及一种负温度系数SiC热敏陶瓷及其制备方法,属于SiC陶瓷领域。
背景技术
负温度系数(negativetemperaturecoefficient)NTC热敏电阻被广泛地用于测温、设备控温和电路温度补偿,在许多领域得以应用,如汽车、通讯和航空航天等,NTC热敏电阻主要由尖晶石型过渡金属化合物以及过渡金属铁氧体组成,SiC热敏电阻的研究较少,目前文献中报道的一种SiC热敏电阻主要由聚碳硅烷混合SiC陶瓷粉体烧结而成的陶瓷材料,根据文献描述,这一热敏陶瓷材料为简单的重结晶SiC,陶瓷混合粉体中没有添加任何烧结助剂,因此该陶瓷难以致密化,相对密度较低,SiC陶瓷的化学和力学性能优越性无法得到充分的体现。
发明内容
本发明旨在综合固相烧结SiC陶瓷优点,提供一种高致密、高热导、高耐腐蚀性NTCSiC热敏电阻材料及其制备方法。
首先,提供一种负温度系数SiC热敏陶瓷,所述负温度系数SiC热敏陶瓷由碳化硅和固相烧结过程中原位复合的碳组成,所述碳在所述负温度系数SiC热敏陶瓷的重量百分含量为3~6wt%,所述负温度系数SiC热敏陶瓷热敏感指数β为:20℃-80℃下为6000K-10000K,80℃-220℃下为2000K-3000K,220℃-400℃下为10000K-15000K。
较佳地,所述负温度系数SiC热敏陶瓷的密度为3.10~3.16g·cm-3,抗弯强度为300~500Mpa。
较佳地,所述负温度系数SiC热敏陶瓷的室温下热导率≥150W·m-1K-1
本发明还提供了一种上述负温度系数SiC热敏陶瓷的制备方法,包括:
配置原始粉料:碳化硅93~97wt%,烧结助剂7wt%以下、粘结剂加入量为粉体总质量1~10wt%,
将所述原始粉料通过球磨混合,配成固含量为40~45wt%的浆料;
将所得浆料喷雾造粒,依次进行干压成型和等静压成型,获得坯体;
将所得坯体真空脱粘后,在常压惰性气氛条件下于1900~2300℃下烧结1~2小时,得所述负温度系数SiC热敏陶瓷。
本发明中,所述SiC粉体的粒径为0.1~1μm。优选采用高纯SiC粉体,其氧含量≤1.8wt%,Fe含量≤0.02wt%。
本发明中,所述烧结助剂可为C黑、B、B4C至少一种。
本发明中,所述粘结剂可为酚醛树脂或PVA或/和PVB。
较佳地,所述干压成型的压力为15~100MPa。
较佳地,所述等静压的压力为150~210MPa。
本发明提供了一种高导热,高耐腐蚀性负温度系数(negativetemperaturecoefficient)NTC碳化硅(SiC)热敏陶瓷,经测试该陶瓷材料具有负温度系数热敏特性,随着温度的升高电阻率降低;在一定电场强度下测定,在温度20℃-400℃之间变化时,电阻率在5-106Ωcm变化,材料的热敏感指数β为:6000K-10000K(20℃-80℃),2000K-3000K(80℃-220℃),10000K-15000K(220℃-400℃)。
附图说明
图1为不同C含量固相烧结SiC热敏陶瓷电阻随温度的变化曲线;
图2为不同C含量固相烧结SiC热敏陶瓷电阻随电场强度的变化曲线。
具体实施方式
以下结合附图和下述实施方式进一步说明本发明,应理解,附图及下述实施方式仅用于说明本发明,而非限制本发明。
本发明通过在无压固相烧结制备碳化硅陶瓷控制原位复合到其中的碳含量获得高致密、高热导、高耐腐蚀性NTCSiC热敏电阻材料的制备方法。
下面说明本发明的负温度系数SiC热敏陶瓷的示例制备方法。以SiC粉体、烧结助剂、粘结剂(酚醛树脂或PVA和/或PVB)为原料,通过球磨混合配成浆料;然后将浆料喷雾造粒制成粉体,再将粉体经过干压成型和等静压成型制成坯体;在真空脱粘后,坯体在常压惰性气体条件下进行烧结,便可得SiC陶瓷。其中,SiC粉体优选为高纯SiC粉体,其氧含量≤1.8wt%,Fe含量≤0.02wt%,以保证碳化硅粉体在烧结过程中产生不必要的缺陷。以固体粉体的总重量为基准计,烧结助剂优选为C黑、B和B4C中的至少一种,质量百分含量可为0~7wt%,其中C质量百分含量为0~6wt%、B或者B4C质量百分含量可为0~1wt%。粘结剂可选为酚醛树脂或者PVA、PVB等有机物,加入量为粉体总质量的1~10wt%,也可根据需要把粘结剂配成溶液在球磨混时添加。在球磨混合时可选用SiC球作为研磨球,以保证球磨过程中研磨球损料不会作为新的杂质原料出现,其中SiC球质量和原始粉料质量比可为2:1。在球磨过程中添加水或其他溶剂,最后形成粉体质量比为40~45wt%的浆料。干压成型的压力可选为15~100Mpa,时间2min,随后在压力下进行等静压成型处理时压力可选为150~210MPa,保压2min。烧结气氛可选为氩气气氛,烧结温度为1900~2300℃,优选为2100~2200℃,烧结时间为1~2小时。
作为示例,进一步具体地描述负温度系数SiC热敏陶瓷制备过程,包括如下:
(1)本发明的原料为平均粒径为0.1~1μm的SiC粉体,B或B4C(0~1wt%)和C黑(0~6wt%)为烧结助剂,酚醛树脂、PVA、PVB等有机物作为粘结剂;
(2)首先将酚醛树脂或PVA、PVB等有机物根据需要配成溶液,加入量分别为粉体质量的5wt%~10wt%;粉体都配成40~45wt%的浆料,用SiC球作为研磨球,粉料:SiC球=1:2(质量),混合24小时;然后将浆料进行喷雾造粒。得到混合均匀的粉体后,在平板机上以15~100MPa压力进行干压成型,随后在150~210MPa压力下进行等静压;
(3)最后真空脱粘后,在常压Ar气气氛下烧结,烧结温度为1900~2300℃,保温时间为60~120min;
(4)将获得的SiC陶瓷加工成Φ10mm厚度2mm的圆片,并将其两端磨平,在其两端均匀的涂覆上银浆电极,然后将其在马弗炉中750℃保温30min;
(5)经Keithley(吉时利)2450多通道测试系统测试不同碳含量固相烧结SiC陶瓷的电阻率随温度的变化的关系曲线,如图所示不同碳含量固相烧结SiC陶瓷的电阻率随温度的变化;
(6)经Keithley(吉时利)2450多通道测试系统测试不同碳含量固相烧结SiC陶瓷的电阻率随电压变化的关系曲线,如图2所示不同碳含量固相烧结SiC陶瓷的电阻率随电压变化。
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
SiC、烧结助剂B4C(0.6wt%)、碳黑3wt%,一共100g,PVB加入量为粉体总质量的1wt%,将粉体配成固含量为45wt%的浆料,以SiC球200g为球磨介质,混合24h。然后喷雾造粒,得到的粉体在平板硫化机上16MPa压力成型,然后在200MPa压力下等静压。脱粘后在常压Ar气气氛下烧结,烧结温度为2100℃,保温时间为1h,得到的SiC。陶瓷密度为3.12gcm-3,抗弯强度为303MPa,常温热导率160W·m-1K-1。将获得陶瓷制成Φ10mm厚度2mm的小圆片,两端涂覆银浆电极,然后将其在马弗炉中750℃保温30min,获得的电子元件通过马弗炉加热,经Keithley(吉时利)2450多通道测试系统测试其电学性能,获得其20℃时的电阻率为67809Ωcm,400℃时的电阻率为5.76Ωcm。热敏感系数β:8068K(20℃-80℃);2080K(80℃-220℃),10962K(220℃-400℃)。
实施例2
SiC、烧结助剂B4C(0.5wt%)、C黑4wt%,共100g,PVA加入量为粉体总质量的1wt%,将粉体配成固含量为45wt%的浆料,以SiC球200g为球磨介质,混合24h,然后喷雾造粒后,得到的粉体在平板硫化机上16Mpa压力成型,然后在200MPa压力下等静压。脱粘后在常压Ar气气氛下烧结,烧结温度为2200℃,保温时间为1h,密度为3.11gcm-3,抗弯强度为378MPa,常温热导率158W·m-1K-1。将获得陶瓷制成Φ10mm厚度2mm的小圆片,两端涂覆银浆电极,然后将其在马弗炉中750℃保温30min,获得的电子元件通过马弗炉加热,经Keithley(吉时利)2450多通道测试系统测试其电学性能,获得其20℃时的电阻率为259902Ωcm,400℃时的电阻率为6.42Ωcm。热敏感系数β:9461K(20℃-80℃);2338K(80℃-220℃),10113K(220℃-400℃)。
实施例3
SiC、烧结助剂B4C(0.6wt%)、C黑5wt%,共100g,PVB加入量为粉体总质量的1wt%,将粉体配成固含量为45wt%的浆料,以SiC球200g为球磨介质,混合24h,然后喷雾造粒后,得到的粉体在平板硫化机上16Mpa压力成型,然后在200MPa压力下等静压。脱粘后在常压Ar气气氛下烧结,烧结温度为2200℃,保温时间为1h,密度为3.11gcm-3,抗弯强度为420MPa,常温热导率156W·m-1K-1。将获得陶瓷制成Φ10mm厚度2mm的小圆片,两端涂覆银浆电极,然后将其在马弗炉中750℃保温30min,获得的电子元件通过马弗炉加热,经Keithley(吉时利)2450多通道测试系统测试其电学性能,获得其20℃时的电阻率为678035Ωcm,400℃时的电阻率为6.55Ωcm。热敏感系数β:9755K(20℃-80℃);2702K(80℃-220℃),12163K(220℃-400℃)。
实施例4
SiC、烧结助剂B4C(0.6wt%)、碳黑3wt%、酚醛树脂(10wt%,高温裂解可产生相当于3wt%单质碳)一共100g将粉体配成固含量为45wt%的浆料,以SiC球200g为球磨介质,混合24h,然后喷雾造粒后,得到的粉体在平板硫化机上16Mpa压力成型,然后在200MPa压力下等静压。脱粘后在常压Ar气气氛下烧结,烧结温度为2200℃,保温时间为1h,得到的SiC陶瓷。单质碳含量为6wt%,密度为3.10gcm-3,抗弯强度为486MPa,常温热导率158W·m-1K-1。将获得陶瓷制成Φ10mm厚度2mm的小圆片,两端涂覆银浆电极,然后将其在马弗炉中750℃保温30min,获得的电子元件通过马弗炉加热,经Keithley(吉时利)2450多通道测试系统测试其电学性能,获得其20℃时的电阻率为937138Ωcm,400℃时的电阻率为9.87Ωcm。热敏感系数β:6103K(20℃-80℃);2731K(80℃-220℃),13884K(220℃-400℃)。

Claims (9)

1.一种负温度系数SiC热敏陶瓷,其特征在于,所述负温度系数SiC热敏陶瓷由碳化硅和固相烧结过程中原位复合的碳组成,所述碳在所述负温度系数SiC热敏陶瓷的重量百分含量为3~6wt%,所述负温度系数SiC热敏陶瓷热敏感指数β为:20℃-80℃下为6000K-10000K,80℃-220℃下为2000K-3000K,220℃-400℃下为10000K-15000K。
2.根据权利要求1所述的负温度系数SiC热敏陶瓷,其特征在于,所述负温度系数SiC热敏陶瓷的密度为3.10~3.16g·cm-3,抗弯强度为300~500Mpa。
3.根据权利要求1或2所述的负温度系数SiC热敏陶瓷,其特征在于,所述负温度系数SiC热敏陶瓷的室温下热导率≥150W·m-1K-1
4.一种如权利要求1至3中任一项所述负温度系数SiC热敏陶瓷的制备方法,其特征在于,包括:
配置原始粉料:碳化硅93~97wt%,烧结助剂7wt%以下,粘结剂加入量为粉体总质量的1~10wt%;
将所述原始粉料通过球磨混合,配成固含量为40~45wt%的浆料;
将所得浆料喷雾造粒,依次进行干压成型和等静压成型,获得坯体;
将所得坯体真空脱粘后,在常压惰性气氛条件下于1900~2300℃下烧结1~2小时,得所述负温度系数SiC热敏陶瓷。
5.根据权利要求4所述的制备方法,其特征在于,所述SiC粉体的粒径为0.1~1μm。
6.根据权利要求4或5所述的制备方法,其特征在于,所述烧结助剂为C黑、B、B4C中的至少一种。
7.根据权利要求4至6中任一项所述的制备方法,其特征在于,所述粘结剂为酚醛树脂、PVA和/或PVB。
8.根据权利要求4至7中任一项所述的制备方法,其特征在于,所述干压成型的压力为15~100MPa。
9.根据权利要求4至8中任一项所述的制备方法,其特征在于,所述等静压的压力为150~210MPa。
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