CN109279897A - 一种非氧化物陶瓷及其制备方法 - Google Patents
一种非氧化物陶瓷及其制备方法 Download PDFInfo
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Abstract
本发明属于超高温陶瓷技术领域,公开了一种非氧化物陶瓷及其制备方法,所述非氧化物陶瓷是将Al粉和非氧化物陶瓷粉混合,得到Al粉包裹非氧化物陶瓷粉混合粉体;将混合粉体暴露在空气中,使Al表面形成致密的氧化膜,再加入稀土氧化物Re2O3和光敏树脂,采用DLP光固化成型,经过450~500℃脱脂,在1700~2100℃烧结制得。本发明通过利用金属Al包裹非氧化物陶瓷粉,形成的混合粉体表面形成一层致密氧化膜,再通过光固化技术制备复杂形状非氧化物陶瓷。
Description
技术领域
本发明属于陶瓷材料技术领域,更具体地,涉及一种非氧化物陶瓷及其制备方法。
背景技术
非氧化物陶瓷材料作为一种结构材料,具有优异的力学性能,例如高硬度、高强、耐磨、耐高温、物理化学稳定性等优异性能,可广泛应用于结构件、刀具切削、航空航天等方面,但是正因为其优异的力学性能限制了其加工多样化,对于复杂形状的陶瓷材料依靠传统的加工工艺无法得到。考虑到其巨大的应用场景,亟待开发一种可实现任意复杂形状的陶瓷材料的成型。
目前,非氧化物陶瓷成型工艺有:注射成型、注凝成型、压滤成型、压力成型、凝胶注模成型等。但是这些技术难以满足对个性化、精细化、轻量化和复杂化的高端产品快速制造的需求,限制了高性能陶瓷产品的开发与应用。虽然目前增材制造已经应用于陶瓷成型,其中,比较成熟的技术主要是3D打印光固化成型,但光固化成型主要可用于氧化物陶瓷,由于非氧化物陶瓷与光敏树脂的折射率相差较大,对于非氧化物陶瓷的光固化成型具有较大的挑战。因此,急需寻求一种可通过光固化成型实现非氧化物陶瓷的制备。
发明内容
为了解决上述现有技术存在的不足和缺点,提供一种非氧化物陶瓷。
本发明的另一目的在于提供上述非氧化物陶瓷的制备方法。该通过利用金属Al包裹非氧化物陶瓷粉,形成的混合粉体表面形成一层致密氧化膜,再通过光固化技术制备复杂形状非氧化物陶瓷。
本发明的目的通过下述技术方案来实现:
一种非氧化物陶瓷,所述非氧化物陶瓷是将Al粉和非氧化物陶瓷粉混合,得到Al粉包裹非氧化物陶瓷粉混合粉体;将混合粉体暴露在空气中,使Al表面形成致密的氧化膜,再加入稀土氧化物Re2O3和光敏树脂,采用DLP光固化成型,经过450~500℃脱脂,在1700~2100℃烧结制得。
优选地,所述非氧化物陶瓷粉:Al的摩尔比为(20~200):1。
优选地,所述非氧化物陶瓷粉为SiC、Si3N4、TiB2、ZrB2、HfB2、TiC、ZrC、TiN、ZrN或TiCN中一种以上。
优选地,所述混合的时间为2~40h;所述烧结的时间为1~10h。
优选地,所述光敏树脂包括单体、低聚物、光引发剂、光敏剂、增感剂和消泡剂;所述单体、低聚物、光引发剂、光敏剂、增感剂和消泡剂的质量比为(2~18):(2~18):(0.02~1):(0.02~1):(0.02~1):(0.02~1)。
优选地,所述单体为已二醇二丙烯酸酯、烷氧基丙烯酸酯、聚氨酯二丙烯酸酯、聚氨酯丙烯酸酯、聚氨酯六丙烯酸酯、季戊四醇丙烯酸酯或三丙二醇二丙烯酸酯中的一种以上;
所述低聚物为丙烯酸酯、丙烯酸胺或硅烷丙烯酸酯中的一种以上;
所述光引发剂为(2,4,6-三甲基苯甲酰基)二苯基氧化膦、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基磷酸乙酯、双2,6-二氟-3-吡咯苯基二茂铁、2-异丙基硫杂蒽酮、4-苯基二苯甲酮或2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮中的一种以上;
所述光敏剂为间-四羟基苯基二氢卟酚、初卟啉锡、苯卟啉衍生物、苯并卟啉衍生物单酸、亚甲苯兰、酞青类或N-天门冬酰基二氢卟酚中的一种以上;
所述增感剂为脂肪族叔胺、乙醇胺类叔胺、叔胺型苯甲酸酯或丙烯酰氧基叔胺中的一种以上;所述消泡剂为巴斯夫-8034A、巴斯夫-NXZ以或毕克-555中的一种以上。
优选地,所述稀土氧化物Re2O3中为Re为Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu中一种以上。
优选地,所述稀土氧化物为混合粉体的1~10wt%,所述混合粉体为稀土氧化物、非氧化物陶瓷粉和Al粉的总和,所述混合粉体占陶瓷浆料总量的20~60wt%,所述的陶瓷浆料为混合粉体和光敏树脂的总和。
优选地,所述非氧化物陶瓷的相对密度为95~99.9%,硬度为18~45GPa,断裂韧性为6~15MPa·m1/2,抗弯强度为800~1200MPa。
所述的非氧化物陶瓷的制备方法,包括如下具体步骤:
S1.将Al粉和SiC粉按摩尔比为1:(20~200)混料,以WC球为球磨介质,在高能球磨机上混合10~40h,得到金属Al包裹SiC混合球形粉体;
S2.将混合球形粉体暴露在空气中1~20min,将氧化后混合球形粉体陶瓷颗粒与光敏树脂混合,制得陶瓷浆料;
S3.采用DLP陶瓷3D设备印将所得陶瓷浆料制成坯体,将坯体在450~500℃进行脱脂,在1700~2100℃烧结,制得非氧化物陶瓷。
与现有技术相比,本发明具有以下有益效果:
1.本发明采用光固化3D打印实现任意非氧化物陶瓷的成型,通过高能球磨实现了氧化膜均匀包裹非氧化物陶瓷。
2.本发明可实现任意复杂形状非氧化物致密件的制备。
附图说明
图1为增材制造过程中粉体分布与反应原理图。
具体实施方式
下面结合具体实施例进一步说明本发明的内容,但不应理解为对本发明的限制。若未特别指明,实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.制备:
(1)将Al粉(纯度为99%,粒径为5μm)和SiC粉(纯度为99%,粒径10μm)按摩尔比为1:30混料,以WC球为球磨介质,在高能球磨机上混合25h,得到金属Al包裹SiC混合球形粉体;
(2)将混合球形粉体在空气中暴露10min,将氧化后混合球形粉体陶瓷颗粒与光敏树脂(70wt%已二醇二丙烯酸酯、29.5wt%丙烯酸胺、0.1wt%(2,4,6-三甲基苯甲酰基)二苯基氧化膦、0.1wt%间-四羟基苯基二氢卟酚、0.2wt%脂肪族叔胺和0.1%巴斯夫-NXZ)混合,陶瓷颗粒含量为陶瓷浆料总质量的50wt%,制得陶瓷浆料。
(3)采用DLP陶瓷3D设备印所得陶瓷浆料(黏度为200mPa·S,)制成坯体,将坯体在500℃进行脱脂,在1800℃烧结制备复杂形状的SiC陶瓷。
2.性能测试:SiC陶瓷的硬度为35GPa,抗弯强度为1000MPa,断裂韧性为10MPa·m1 /2。
实施例2
1.制备:
(1)以金属Al粉(纯度为99%,粒径为5μm)和ZrB2(纯度为99%,粒径10μm)按Al:ZrB2的摩尔比为1:50混合,以WC球为球磨介质,在高能球磨机上混合25h,得到金属Al包裹ZrB2混合球形粉体;
(2)将混合球形粉体在空气中暴露10min,将氧化后混合球形粉体陶瓷颗粒与光敏树脂(70wt%已二醇二丙烯酸酯、29.5wt%丙烯酸胺、0.1wt%(2,4,6-三甲基苯甲酰基)二苯基氧化膦、0.1wt%间-四羟基苯基二氢卟酚、0.2wt%脂肪族叔胺和0.1%巴斯夫-NXZ)混合,陶瓷颗粒含量为陶瓷浆料总质量的50wt%,制得陶瓷浆料。
(3)采用DLP陶瓷3D设备印所得陶瓷浆料(黏度为50mPa·S),陶瓷颗粒含量为陶瓷浆料总质量的60wt%,打印坯体在500℃进行脱脂,在2000℃烧结制备复杂形状的ZrB2陶瓷。
2.性能测试:ZrB2陶瓷的硬度为35GPa,抗弯强度为800MPa,断裂韧性为8MPa·m1 /2。
实施例3
1.制备:
(1)将Al粉(纯度为99%,粒径为5μm)和TiB2粉(纯度为99%,粒径10μm)按Al:TiB2的摩尔比为1:100混料,以WC球为球磨介质,在高能球磨机上混合25h,得到金属Al包裹TiB2混合球形粉体;
(2)将混合球形粉体在空气中暴露10min,将氧化后混合球形粉体陶瓷颗粒与光敏树脂(70wt%已二醇二丙烯酸酯、29.5wt%丙烯酸胺、0.1wt%(2,4,6-三甲基苯甲酰基)二苯基氧化膦、0.1wt%间-四羟基苯基二氢卟酚、0.2wt%脂肪族叔胺和0.1%巴斯夫-NXZ)混合,陶瓷颗粒含量为陶瓷浆料总质量的50wt%,制得陶瓷浆料。
(3)采用DLP陶瓷3D打印设备进打印所得陶瓷浆料(黏度为50mPa·S),陶瓷颗粒含量为50wt%,打印坯体在500℃进行脱脂,在1950℃烧结制备复杂形状TiB2陶瓷。
2.性能测试:TiB2陶瓷的硬度为30GPa,抗弯强度为850MPa,断裂韧性为10MPa·m1 /2。
实施例4
1.制备:
(1)将Al粉(纯度为99%,粒径为5μm)和Si3N4粉(纯度为99%,粒径10μm)按Al:Si3N4的摩尔比为1:50混料,以WC球为球磨介质,在高能球磨机上混合25h,如图1所示,金属Al作为一种软质相,非氧化物陶瓷作为一种硬质相,在高能球磨过程中软质相变成液相,均匀包裹在非氧化物陶瓷表面,从而得到金属Al包裹Si3N4混合球形粉体;
(2)由于金属Al易氧化生成致密氧化膜的特性,将混合球形粉体在空气中暴露10min,从而得到如图1中所述氧化铝均匀包裹非氧化物陶瓷结构,将氧化后混合球形粉体陶瓷颗粒与光敏树脂(70wt%已二醇二丙烯酸酯、29.5wt%丙烯酸胺、0.1wt%(2,4,6-三甲基苯甲酰基)二苯基氧化膦、0.1wt%间-四羟基苯基二氢卟酚、0.2wt%脂肪族叔胺和0.1%巴斯夫-NXZ)混合,陶瓷颗粒含量为陶瓷浆料总质量的50wt%,制得陶瓷浆料。
(3)采用DLP陶瓷3D打印设备进打印所得陶瓷浆料(黏度为50mPa·S),陶瓷颗粒含量为60wt%,打印坯体在500℃进行脱脂,在1800℃烧结制备复杂形状Si3N4陶瓷。
2.性能测试:Si3N4陶瓷的硬度为18GPa,抗弯强度为1200MPa,断裂韧性为12MPa·m1/2。
实施例5
1.制备:
(1)将金属Al粉(纯度为99%,粒径为5μm)和TiC0.5N0.5粉(纯度为99%,粒径10μm)按Al:TiC0.5N0.5的摩尔比为1:50混料,以WC球为球磨介质,在高能球磨机上混合25h,得到金属Al包裹TiC0.5N0.5混合球形粉体;
(2)将混合球形粉体在空气中暴露10min,将氧化后混合球形粉体陶瓷颗粒与光敏树脂(70wt%已二醇二丙烯酸酯、29.5wt%丙烯酸胺、0.1wt%(2,4,6-三甲基苯甲酰基)二苯基氧化膦、0.1wt%间-四羟基苯基二氢卟酚、0.2wt%脂肪族叔胺和0.1%巴斯夫-NXZ)混合,陶瓷颗粒含量为陶瓷浆料总质量的50wt%,制得陶瓷浆料。
(3)采用DLP陶瓷3D打印设备进打印所得陶瓷浆料(黏度为50mPa·S),陶瓷颗粒含量为60wt%,打印坯体在500℃进行脱脂,在1700℃烧结制备复杂形状TiC0.5N0.5陶瓷样品。
2.性能测试:TiC0.5N0.5陶瓷的硬度为20GPa,抗弯强度为800MPa,断裂韧性为8MPa·m1/2。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种非氧化物陶瓷,其特征在于,所述非氧化物陶瓷是将Al粉和非氧化物陶瓷粉混合,得到Al粉包裹非氧化物陶瓷粉混合粉体;将混合粉体暴露在空气中,使Al表面形成致密的氧化膜,再加入稀土氧化物Re2O3和光敏树脂,采用DLP光固化成型,经过450~500℃脱脂,在1700~2100℃烧结制得。
2.根据权利要求1所述的非氧化物陶瓷,其特征在于,所述非氧化物陶瓷粉:Al的摩尔比为(20~200):1。
3.根据权利要求1所述的非氧化物陶瓷,其特征在于,所述非氧化物陶瓷粉为SiC、Si3N4、TiB2、ZrB2、HfB2、TiC、ZrC、TiN、ZrN或TiCN中一种以上。
4.根据权利要求1所述的非氧化物陶瓷,其特征在于,所述混合的时间为2~40h;所述烧结的时间为1~10h。
5.根据权利要求1所述的非氧化物陶瓷,其特征在于,所述光敏树脂包括单体、低聚物、光引发剂、光敏剂、增感剂和消泡剂;所述单体、低聚物、光引发剂、光敏剂、增感剂和消泡剂的质量比为(2~18):(2~18):(0.02~1):(0.02~1):(0.02~1):(0.02~1)。
6.根据权利要求6所述的非氧化物陶瓷,其特征在于,所述单体为已二醇二丙烯酸酯、烷氧基丙烯酸酯、聚氨酯二丙烯酸酯、聚氨酯丙烯酸酯、聚氨酯六丙烯酸酯、季戊四醇丙烯酸酯或三丙二醇二丙烯酸酯中的一种以上;
所述低聚物为丙烯酸酯、丙烯酸胺或硅烷丙烯酸酯中的一种以上;
所述光引发剂为(2,4,6-三甲基苯甲酰基)二苯基氧化膦、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基磷酸乙酯、双2,6-二氟-3-吡咯苯基二茂铁、2-异丙基硫杂蒽酮、4-苯基二苯甲酮或2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮中的一种以上;
所述光敏剂为间-四羟基苯基二氢卟酚、初卟啉锡、苯卟啉衍生物、苯并卟啉衍生物单酸、亚甲苯兰、酞青类或N-天门冬酰基二氢卟酚中的一种以上;
所述增感剂为脂肪族叔胺、乙醇胺类叔胺、叔胺型苯甲酸酯或丙烯酰氧基叔胺中的一种以上;所述消泡剂为巴斯夫-8034A、巴斯夫-NXZ以或毕克-555中的一种以上。
7.根据权利要求1所述的非氧化物陶瓷,其特征在于,所述稀土氧化物Re2O3中为Re为Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu中一种以上。
8.根据权利要求1所述的非氧化物陶瓷,其特征在于,所述稀土氧化物为混合粉体的1~10wt%,所述混合粉体为稀土氧化物、非氧化物陶瓷粉和Al粉的总和,所述混合粉体占陶瓷浆料总量的20~60wt%,所述的陶瓷浆料为混合粉体和光敏树脂的总和。
9.根据权利要求1所述的非氧化物陶瓷,其特征在于,所述非氧化物陶瓷的相对密度为95~99.9%,硬度为18~45GPa,断裂韧性为6~15MPa·m1/2,抗弯强度为800~1200MPa。
10.根据权利要求1-9任一项所述的非氧化物陶瓷的制备方法,其特征在于,包括如下具体步骤:
S1.将Al粉和SiC粉按摩尔比为1:(20~200)混料,以WC球为球磨介质,在高能球磨机上混合10~40h,得到金属Al包裹SiC混合球形粉体;
S2.将混合球形粉体暴露在空气中1~20min,将氧化后混合球形粉体陶瓷颗粒与光敏树脂混合,制得陶瓷浆料;
S3.采用DLP陶瓷3D设备印将所得陶瓷浆料制成坯体,将坯体在450~500℃进行脱脂,在1700~2100℃烧结,制得非氧化物陶瓷。
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