CN110590377B - 一种高β相致密氮化硅陶瓷及低温制备方法 - Google Patents
一种高β相致密氮化硅陶瓷及低温制备方法 Download PDFInfo
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Abstract
本发明属于氮化硅陶瓷技术领域,涉及一种高β相含量致密氮化硅陶瓷及低温制备方法。涉及的一种高β相含量致密氮化硅陶瓷的制备原料包括Si3N4粉和烧结助剂;烧结助剂为LixMOy型锂盐以及一种或多种其它氧化物组成的复合烧结助剂;其中LixMOy型锂盐为LiAlO2、LiYO2、LiNbO3、Li2ZrO3、LiYbO2、Li2SiO3中的一种,其它氧化物为稀土氧化物或金属氧化物,Y2O3、CeO2、Yb2O3、MgO、CaO、MgAl2O4中的一种或多种;所述复合烧结助剂中LixMOy型锂盐和其它氧化物质量比为4~12:0~8;所述Si3N4粉与复合烧结助剂质量比为85~94:6~15。本发明大大降低了烧结温度,减少了氮化硅陶瓷的挥发,更好的保持氮化硅陶瓷的优异性能。
Description
技术领域
本发明属于氮化硅陶瓷技术领域,涉及一种高β相含量致密氮化硅陶瓷及低温制备方法。
背景技术
氮化硅陶瓷具有良好的耐磨耐蚀性、高的抗弯强度、良好的断裂韧性、极大的硬度而且理论热导率值较高(200–300Wm-1·K-1),因此被广泛用于现代工业中(汽车发动机零部件、核反应堆支撑、刀具、陶瓷装甲以及航空航天等领域)。致密氮化硅陶瓷的烧结制备一直是研究的热点,因为氮化硅是一种强共价键材料,也因此导致其难以固相烧结,必须加入烧结助剂通过液相作为传质媒介促进其致密化烧结;目前氮化硅陶瓷制品的生产大多依靠热压和气压烧结等高成本的烧结方式,同时对烧结温度的要求十分高(1700-1900℃),且在氮化硅烧结制备过程中存在一个α相向β相的转变,这个相转变对于氮化硅陶瓷的致密化程度及力学性能的改善有决定性的影响,而在低温段很难完成较高的相转变,也因此极大限制了高性能氮化硅陶瓷在许多高新技术领域的工业化生产和普及应用。
关于氮化硅的制备大多采用高温下的热压或气压方式进行烧结:例如:张辉的专利“一种致密化氮化硅陶瓷材料的制备办法”(公开号CN103553632A)采用的烧结温度为1750℃~1850℃,烧结温度高导致所需设备及成本也急剧加大。赵振威的专利“一种提高氮化硅材料性能一致性的烧结方法”(公开号CN104119079A)利用气压和热压烧结的方式,导致制备成本高、效率低。于方丽的专利“一种氮化硅陶瓷及制备方法”(公开号CN105859301A)采用气压烧结方式,烧结温度也达到1800℃,从而导致成本过高。
氮化硅陶瓷由于其烧结温度过高,生产设备要求苛刻等问题,致使其工业化生产效率大大降低,目前低温制备高β相致密氮化硅陶瓷技术的相关研究十分少,因此研究一种低温制备高性能氮化硅陶瓷制备技术变得极其重要。
发明内容
为解决上述技术问题,本发明的目的在于提供一种关于高β相致密氮化硅陶瓷及低温制备方法。
本发明为完成上述发明目的采用如下技术方案:
一种高β相含量致密氮化硅陶瓷,高β相含量致密氮化硅陶瓷的制备原料包括Si3N4粉和烧结助剂;烧结助剂为LixMOy型锂盐以及一种或多种其它氧化物组成的复合烧结助剂;其中LixMOy型锂盐为LiAlO2、LiYO2、LiNbO3、Li2ZrO3、LiYbO2、Li2SiO3中的一种,其它氧化物为稀土氧化物或金属氧化物,Y2O3、CeO2、Yb2O3、MgO、CaO、MgAl2O4中的一种或多种;所述复合烧结助剂中LixMOy型锂盐和其它氧化物质量比为4~12:0~8;所述Si3N4粉与复合烧结助剂质量比为85~94:6~15。
所述的单相LixMOy型锂盐由Li2O与另外一种氧化物复合而成;所述合成单相LixMOy型锂盐的两种氧化物和其它氧化物中必须包含至少一种稀土氧化物。
另外一种氧化物为Al2O3、Y2O3、Nb2O5、ZrO2、Yb2O3或SiO2中的一种。
优选的,所述LixMOy型锂盐和其它氧化物质量比为6~10:2~6。
优选的,所述Si3N4粉与烧结助剂质量比为88~92:8~12。
一种高β相致密氮化硅陶瓷的低温制备方法,包括以下步骤:
步骤A:将合成单相LixMOy型锂盐的Li2O与另外一种氧化物按1.02~1.5的摩尔配比称取并进行球磨混合;
步骤B:将球磨过的混合粉体在加热炉中在800~1400℃的温度下煅烧2~4h进行预合成得到单相LixMOy型锂盐粉体;
步骤C:将预合成的单相LixMOy型锂盐粉体和其它稀土或金属氧化物按配比与Si3N4粉混入乙醇并进行高能球磨;
步骤D:将混合后的粉体进行干燥、喷雾造粒和成型;
步骤E:将成型后的生坯在不高于1650℃下进行烧结,得到所述的Si3N4陶瓷。
步骤A和C磨球和粉料质量比为3~10:1,磨球材质为氮化硅,球磨时间为12h~48h。
步骤B预合成温度为900℃~1300℃,保温2~3h。
步骤D喷雾造粒的工艺条件为氮气气氛,进口温度130~190℃,出口温度65~95℃。
步骤D成型为等静压成型,压力大小200~240MPa,保压15~30min。
步骤E烧结方法为氮气气氛烧结或空气埋粉无压烧结,空气埋粉无压烧结是将成型的生坯放入埋有氮化硅粉的石墨坩埚中,然后将石墨坩埚放入埋有石墨的氧化铝匣钵中进行空气气氛无压烧结。
步骤E烧结温度为1550~1650℃,保温时间为4h~10h,升温速度为2℃/min~10℃/min。
综上所述,本发明提供了一种高β相含量的致密Si3N4陶瓷的低温制备方法,由该方法可制得高β含量、高致密、力学性能优异且近净型的氮化硅陶瓷制品。
与现有技术相比,本发明具有下述优势特点:
(1)本发明采用新型低熔点的LixMOy型锂盐以及一种或多种其它金属或稀土氧化物组成的复合烧结助剂,使烧结温度大大降低,从而减少了氮化硅陶瓷的挥发,更好的保持氮化硅陶瓷的优异性能。
(2)本发明在低温无压烧结的同时能够促进氮化硅相转变,极大提高了β-氮化硅相含量,从而在一定程度上提高了氮化硅陶瓷的力学性能。
(3)本发明的氮化硅陶瓷生产设备要求不高且极大节约能源,可广泛用于各领域工业化生产,使氮化硅陶瓷广泛使用于高中低端产业。
附图说明
图1是本发明制备的高β相致密氮化硅陶瓷典型显微形貌图。
图2是本发明制备的高β相致密氮化硅陶瓷典型的X射线衍射分析图谱。
具体实施方式
下面结合实施例对本发明作进一步说明,本发明的方式包括但不仅限于以下实施例。
实施例1:
按所述Li2O(原料为Li2CO3)和Al2O3摩尔比为1.02:1进行配比,然后在行星式球磨机上进行球磨6h,球磨介质为氮化硅磨球,球料比为5:1。
将球磨后的混合粉体烘干,放入氧化铝坩埚中进行1000℃煅烧2h。
将煅烧后得到的单相LiAlO2研磨过40目筛与Y2O3和Si3N4粉体按质量比10:2:88进行配比,在行星式球磨机上进行球磨24h,球磨介质为氮化硅磨球,球料比为5:1。
然后将混合均匀的粉体进行喷雾造粒,工艺为N2气氛,设定进口温度160℃,出口温度80℃,得到Si3N4造粒粉。
将造粒过后的Si3N4粉放入等静压模具中,在220MPa冷等静压压力下进行成型。
最后将成型的生坯放入石墨坩埚中埋入氮化硅粉进行氮气气氛无压烧结。以3℃/min的升温速率升温至1650℃,并保温4h,制得所述氮化硅陶瓷。
本实例所制得的氮化硅陶瓷气孔率为0.5%,相对密度97.67%,β-Si3N4转化率为83%。
实施例2:
按所述Li2O(原料为Li2CO3)和Al2O3摩尔比为1.02:1进行配比,然后在行星式球磨机上进行球磨6h,球磨介质为氮化硅磨球,球料比为7:1。
将球磨后混合粉体烘干,放入氧化铝坩埚中进行900℃煅烧3h。
将煅烧后得到的单相LiAlO2破碎过40目筛与Y2O3和Si3N4粉体按质量比8:4:88进行配比,在行星式球磨机上进行球磨24h,球磨介质为氮化硅磨球,球料比为7:1。
然后将混合均匀的粉体进行喷雾造粒,工艺为N2气氛,设定进口温度180℃,出口温度90℃,得到Si3N4造粒粉。
将造粒过后的Si3N4粉放入等静压模具中,在200MPa冷等静压压力下进行成型。
最后将成型的生坯放入石墨坩埚中并用氮化硅粉填埋,把石墨坩埚放入刚玉莫来石质匣钵中在空气条件下进行无压烧结。以3℃/min的升温速率升温至1650℃,并保温8h,制得所述Si3N4陶瓷。
本实例所制得的氮化硅陶瓷气孔率为0.7%,相对密度为98.01%,β-Si3N4转化率为82%。
实施例3:
按所述Li2O(原料为Li2CO3)和Y2O3摩尔比为1.5:1进行配比,然后在行星式球磨机上进行球磨12h,球磨介质为氮化硅磨球,球料比为10:1。
将球磨后的烧结助剂混合粉体烘干后,放入氧化铝坩埚中进行1300℃煅烧2h。
将煅烧后的单相LiYO2破碎过40目筛与MgO和Si3N4粉体按质量比4:8:88进行配比,在行星式球磨机上进行球磨24h,球磨介质为氮化硅磨球,球料比为10:1。
然后将混合均匀的粉体进行喷雾造粒,工艺为N2气氛,设定进口温度180℃,出口温度90℃,得到Si3N4造粒粉。
将造粒过后的Si3N4粉放入等静压模具中,在240MPa冷等静压压力下进行成型。
最后将成型的生坯放入石墨坩埚中埋入氮化硅粉进行氮气气氛烧结。以5℃/min的升温速率升温至1650℃,并保温4h,制得所述Si3N4陶瓷。
本实例所制得的氮化硅陶瓷气孔率为2.36%,相对密度为96.69%,β-Si3N4转化率为78%。
实施例4:
按所述Li2O(原料为Li2CO3)和ZrO2摩尔比为1.05:1进行配比,然后在行星式球磨机上进行球磨6h,磨球材质为氮化硅磨球,球料比为5:1。
将球磨后的烧结助剂混合粉体烘干后,放入氧化铝坩埚中进行800℃煅烧2h。
将煅烧后的单相Li2ZrO3破碎过40目筛与Y2O3和Si3N4粉体按质量比4:8:88进行配比,在行星式球磨机上进行球磨24h,球磨介质为氮化硅磨球,球料比为5:1。
然后将混合均匀的粉体进行喷雾造粒,工艺为N2气氛,设定进口温度180℃,出口温度90℃,得到Si3N4造粒粉。
将造粒过后的Si3N4粉放入等静压模具中,在220MPa压力下保压15min进行成型。
最后将成型的生坯置于氮气气氛进行烧结。以3℃/min的升温速率升温至1650℃,并保温10h,制得所述Si3N4陶瓷。
本实例所制得的氮化硅陶瓷气孔率为0.8%,相对密度为97.17%,β-Si3N4转化率为90%。
实施例5:
按所述Li2O(原料为Li2CO3)和Al2O3摩尔比为1.02:1进行配比,然后在行星式球磨机上进行球磨6h,磨球材质为氮化硅磨球,球料比为5:1。
将球磨后的烧结助剂混合粉体烘干后,放入氧化铝坩埚中进行1000℃煅烧2h。
将煅烧后的单相LiAlO2破碎过40目筛与Y2O3、CaO和Si3N4粉体按质量比6:4:2:88进行配比,在行星式球磨机上进行球磨24h,球磨介质为氮化硅磨球,球料比为5:1。
然后将混合均匀的粉体进行喷雾造粒,工艺为N2气氛,设定进口温度180℃,出口温度90℃,得到Si3N4造粒粉。
将造粒过后的Si3N4粉放入等静压模具中,在240MPa冷等静压压力下进行成型。
最后将成型的生坯放入石墨坩埚中埋入氮化硅粉进行氮气气氛无压烧结。以3℃/min的升温速率升温至1650℃,并保温8h,制得所述Si3N4陶瓷。
本实例所制得的氮化硅陶瓷气孔率为0.83%,相对密度为97.69%,β-Si3N4转化率为88%。
本发明将不会被限制于本文所示的这些实施例,而是符合与本文所公开的原理和优势特点相一致的范围都应受到保护。
Claims (3)
1.一种高β相含量致密氮化硅陶瓷,其特征在于:高β相含量致密氮化硅陶瓷的制备原料包括Si3N4粉和烧结助剂;烧结助剂为LixMOy型锂盐以及一种或多种其它氧化物组成的复合烧结助剂;其中LixMOy型锂盐为LiAlO2、LiYO2、LiNbO3、Li2ZrO3、LiYbO2中的一种,其它氧化物为稀土氧化物或金属氧化物,Y2O3、CeO2、Yb2O3、MgO、CaO、MgAl2O4中的一种或多种;所述复合烧结助剂中LixMOy型锂盐和其它氧化物质量比为6~10:2~6;所述Si3N4粉与烧结助剂质量比为88~92:8~12;所述的单相LixMOy型锂盐由Li2O与另外一种氧化物复合而成;所述合成单相LixMOy型锂盐的两种氧化物和其它氧化物中必须包含至少一种稀土氧化物。
2.如权利要求1所述的一种高β相含量致密氮化硅陶瓷,其特征在于:另外一种氧化物为Al2O3、Y2O3、Nb2O5、ZrO2、Yb2O3中的一种。
3.制备权利要求1-2任一所述的一种高β相致密氮化硅陶瓷的低温制备方法,制备方法包括以下步骤:
步骤A:将合成单相LixMOy型锂盐的Li2O与另外一种氧化物按1.02~1.5的摩尔配比称取并进行球磨混合;
步骤B:将球磨过的混合粉体在加热炉中在800~1400℃的温度下煅烧2~4h进行预合成得到单相LixMOy型锂盐粉体;
步骤C:将预合成的单相LixMOy型锂盐粉体和其它氧化物按配比与Si3N4粉混入乙醇并进行高能球磨;
步骤D:将混合后的粉体进行干燥、喷雾造粒和成型;
步骤E:将成型后的生坯在不高于1650℃下进行烧结,得到所述的Si3N4陶瓷;其特征在于:步骤E烧结方法为空气埋粉无压烧结,空气埋粉无压烧结是将成型的生坯放入埋有氮化硅粉的石墨坩埚中,然后将石墨坩埚放入埋有石墨的氧化铝匣钵中进行空气气氛无压烧结;步骤E烧结温度为1550~1650℃,保温时间为4h~10h,升温速度为2℃/min~10℃/min。
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