CN102333741A - 钛酸铝系陶瓷烧结体的制造方法及钛酸铝系陶瓷烧结体 - Google Patents
钛酸铝系陶瓷烧结体的制造方法及钛酸铝系陶瓷烧结体 Download PDFInfo
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- CN102333741A CN102333741A CN2010800093383A CN201080009338A CN102333741A CN 102333741 A CN102333741 A CN 102333741A CN 2010800093383 A CN2010800093383 A CN 2010800093383A CN 201080009338 A CN201080009338 A CN 201080009338A CN 102333741 A CN102333741 A CN 102333741A
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Abstract
本发明的目的在于,提供可以在低于1500℃的低烧结温度下制造能实现低热膨胀性和高机械强度的同时,由于烧结所导致的尺寸变化小的钛酸铝系陶瓷的方法。本发明涉及钛酸铝系陶瓷的制造方法,其包括制造含有含钛源粉末、铝源粉末和硅源粉末的前体混合物和有机类粘合剂的陶瓷可塑性捏合土,并成型为预定形状的步骤,和将成型了的陶瓷可塑性捏合土在900~1350℃的温度范围以每小时的温度变化为-50~+50℃/h保持3小时以上后,升温至1400℃以上的温度,在该温度下烧结的步骤。本发明还涉及通过该制造方法得到的气孔率为30~60%的钛酸铝系陶瓷烧结体。
Description
技术领域
本发明涉及钛酸铝系陶瓷烧结体的制造方法以及钛酸铝系陶瓷烧结体。
背景技术
柴油机用的废气过滤器是对废气中含有的煤等进行过滤、捕集的过滤器,通常由具有高气孔率的陶瓷烧结体形成。若该由多孔质陶瓷形成的过滤器中捕集一定量的煤则气体的流通阻力增大,因此进行使堵塞的煤在过滤器上燃烧的再生处理。此时,在过滤器内产生急速的温度升高,过滤器暴露在高温下的同时,受到大的热冲击。因此,对于柴油机用的废气过滤材料要求高的耐热冲击性和由于热疲劳所导致的特性劣化小。
钛酸铝(Al2TiO5)作为表现出高熔点、低热膨胀性的陶瓷已知,作为废气过滤材料受到瞩目。然而,钛酸铝通常机械强度低,在接近过滤器的使用温度范围的900~1100℃附近的热稳定性差(分解为TiO2和Al2O3)。以往的钛酸铝中,尝试加入各种添加元素来维持其低热膨胀性的同时改善机械强度和热稳定性。
作为钛酸铝、钛酸铝镁等钛酸铝系陶瓷烧结体的制造方法,要求可以制造热膨胀系数小的钛酸铝系陶瓷烧结体的方法。制造热膨胀系数小的钛酸铝镁时,可以在更高的温度、例如1500℃以上的温度下将前体混合物烧结。然而,在工业性规模的实施中,优选烧结温度低。
现有技术文献
专利文献
专利文献1:日本专利3612943号说明书
专利文献2:日本特开平11-060240号公报。
发明内容
为了实现钛酸铝的低热膨胀性,高温下的热处理是不可欠缺的。然而,已知高温下的热处理损害钛酸铝的机械强度。作为多孔性的钛酸铝的制法,专利文献1中提出了将氧化钛、氧化铝、二氧化硅等原料粉末与有机粘合剂一起直接成型,通过一次热处理得到多孔体的方法,专利文献2中提出了由钛酸铝的粉末得到多孔性的烧结体的方法。然而,若将通过这些方法得到的成型体在高温下烧结,则虽然可以实现低热膨胀性,但是伴随着烧结收缩的体积变化大,机械强度也显著降低。
因此,本发明人为了开发可以在低于1500℃的低烧结温度下制造能实现低热膨胀性和高机械强度的同时,由于烧结所导致的尺寸变化小的钛酸铝系陶瓷烧结体的方法而进行了精心研究,结果完成本发明。
即,本发明的钛酸铝陶瓷烧结体的制造方法包括将含有含钛源粉末、铝源粉末和硅源粉末的前体混合物和有机类粘合剂的陶瓷可塑性捏合土(練り土)成型为预定形状的步骤,和将成型了的陶瓷可塑性捏合土在900~1350℃的温度范围以每小时的温度变化为-50~+50℃/h保持3小时以上后,升温至1400℃以上的温度,在该温度下烧结的步骤。本说明书中,本发明的方法中得到的“钛酸铝系陶瓷烧结体”包括含有钛酸铝和铝硅酸盐的复合材料。
本发明的方法中,硅源粉末优选熔点为800~1350℃的无定形的铝硅酸盐,更优选为1000~1200℃。此外,上述铝硅酸盐优选屈服点为700~1000℃的玻璃。
本发明的方法中的前体混合物优选进一步含有镁源粉末。
本发明的方法中,优选换算成SiO2的硅源粉末的用量与换算成氧化物的前体混合物的用量的重量比为2~10%,且硅源粉末是按氧化物的重量比计为SiO2=70~80%、Al2O3=5~15%、(Na2O+K2O)=5~25%、MgO=0~3.0%、作为不可避免的杂质(CaO+SrO+BaO)<4.0%的无定形的铝硅酸盐。更优选硅源的重量比为2~4%。
本发明还提供通过上述任意一项中记载的方法得到的气孔率为30~60%的钛酸铝系陶瓷烧结体。
本发明的钛酸铝系陶瓷烧结体中,硅源优选熔点为800~1350℃的无定形的铝硅酸盐,更优选为1000~1200℃。上述铝硅酸盐优选屈服点为700~1000℃的玻璃。
本发明的钛酸铝系陶瓷烧结体的制造中,前体混合物优选进一步含有镁源粉末。
此外,本发明的钛酸铝系陶瓷烧结体优选换算成SiO2的硅源粉末的用量与换算成氧化物的前体混合物的用量的重量比为2~10%,且硅源粉末是按氧化物的重量比计为SiO2=70~80%、Al2O3=5~15%、(Na2O+K2O)=5~25%、MgO=0~3.0%、作为不可避免的杂质(CaO+SrO+BaO)<4.0%的无定形的铝硅酸盐。更优选硅源的重量比为2~4%。
本说明书中,换算成Al2O3(氧化铝)的铝源粉末的重量x1通过下式(A)求得。
x1=N10×x10 (A)。
式(A)中,N10表示Al2O3的分子量,x10表示换算成Al2O3(氧化铝)的铝源粉末的摩尔量。换算成Al2O3(氧化铝)的铝源粉末的摩尔量x10通过下式(A-1)求得。
x10=(w1×M1)/(N1×2) (A-1)。
式(A-1)中,w1表示铝源粉末的用量(g),M1表示1摩尔铝源粉末中的铝的摩尔数,N1表示所使用的铝源粉末的分子量。本发明中使用两种以上铝源粉末时,通过式(A-1)求出各铝源粉末换算成Al2O3(氧化铝)的摩尔量,将各摩尔量合计,由此可以求出所使用的铝源粉末换算成Al2O3(氧化铝)的摩尔量。
换算成TiO2(二氧化钛)的钛源粉末的重量x2通过下式(B)求得。
x2=N20×x20 (B)。
式(B)中,N20表示TiO2的分子量,x20表示换算成TiO2(二氧化钛)的钛源粉末的摩尔量。换算成TiO2(二氧化钛)的钛源粉末的摩尔量x20通过下式(B-1)求得。
x20=(w2×M2)/N2 ( B-1)。
式(B-1)中,w2表示钛源粉末的用量(g),M2表示1摩尔钛源粉末中的钛的摩尔数,N2表示所使用的钛源粉末的分子量。本发明中使用两种以上钛源粉末时,通过式(B-1)求出各钛源粉末换算成TiO2(二氧化钛)的摩尔量,将各摩尔量合计,由此可以求出所使用的钛源粉末换算成TiO2(二氧化钛)的摩尔量。
换算成MgO(氧化镁)的镁源粉末的重量x3通过下式(C)求得。
x3=N30×x30 (C)。
式(C)中,N30表示MgO的分子量,x30表示换算成MgO(氧化镁)的镁源粉末的摩尔量。换算成MgO(氧化镁)的钛源粉末的摩尔量x30通过下式(C-1)求得。
x30=(w3×M3)/N3 ( C-1)。
式(C-1)中,w3表示镁源粉末的用量(g),M3表示1摩尔镁源粉末中的镁的摩尔数,N3表示所使用的镁源粉末的分子量。本发明中使用两种以上镁源粉末时,通过式(C-1)求出各镁源粉末换算成MgO(氧化镁)的摩尔量,将各摩尔量合计,由此可以求出所使用的镁源粉末换算成MgO(氧化镁)的摩尔量。
换算成SiO2(二氧化硅)的硅源粉末的重量x4通过下式(D)求得。
x4=N40×x40 (D)。
式(D)中,N40表示SiO2的分子量,x40表示换算成SiO2(二氧化硅)的硅源粉末的摩尔量。换算成SiO2(二氧化硅)的硅源粉末的摩尔量x40通过下式(D-1)求得。
x40=(w4×M4)/N4 (D-1)。
式(D-1)中,w4表示硅源粉末的用量(g),M4表示1摩尔硅源粉末中的硅的摩尔数,N4表示所使用的硅源粉末的分子量。本发明中使用两种以上硅源粉末时,通过式(D-1)求出各硅源粉末换算成SiO2(二氧化硅)的摩尔量,将各摩尔量合计,由此可以求出所使用的硅源粉末换算成SiO2(二氧化硅)的摩尔量。
使用铝硅酸盐作为硅源粉末时,换算成SiO2(二氧化硅)的重量x4’通过下式(D’)求得。
x4’=R(AS)×W(AS)。
式(D’)中,R(AS)表示铝硅酸盐中的SiO2的重量比(重量%),W(AS)表示所使用的铝硅酸盐的重量(g)。R(AS)可以通过荧光X射线分析法(XRF)、ICP发射光谱分析法等方法求得。
根据本发明,可以在低于1500℃的温度下制备热膨胀系数小、机械强度和耐热稳定性优异的钛酸铝系陶瓷烧结体。
具体实施方式
本发明的钛酸铝系陶瓷烧结体的制造方法中,首先将含有含钛源粉末、铝源粉末和硅源粉末的前体混合物和有机类粘合剂的陶瓷可塑性捏合土成型为预定形状。
构成前体混合物的钛源粉末指的是可以形成构成钛酸铝系陶瓷的钛成分的物质的粉末。作为这种钛源粉末,可以举出例如氧化钛(IV)、氧化钛(III)、氧化钛(II)等,优选使用氧化钛(IV)。氧化钛(IV)可以为结晶性或无定形。氧化钛(IV)为结晶性时,作为其结晶类型,可以举出锐钛矿型、金红石型、板钛矿型等。
此外,作为钛源粉末,还可以举出通过在空气中烧制转化成二氧化钛(氧化钛)的物质的粉末。作为上述物质,可以举出例如钛盐、钛醇盐、氢氧化钛、氮化钛、硫化钛、金属钛等。作为钛盐,具体地说可以举出三氯化钛、四氯化钛、硫化钛(IV)、硫化钛(VI)、硫酸钛(IV)等。作为钛醇盐,具体地说可以举出乙醇钛(IV)、甲醇钛(IV)、叔丁醇钛(IV)、异丁醇钛(IV)、正丙醇钛(IV)、四异丙醇钛(IV)和它们的螯合物等。
作为本发明中的钛源粉末,优选为廉价、工业上容易得到的锐钛矿型或金红石型的氧化钛(IV)。
此外,作为构成前体混合物的铝源粉末,可以举出例如氧化铝(氧化铝)的粉末。氧化铝可以为结晶性或无定形。氧化铝为结晶性的情况下,作为其结晶类型,可以举出γ型、δ型、θ型、α型等。作为铝源粉末,优选为α型的氧化铝。
作为铝源粉末,可以举出通过在空气中烧制转化成氧化铝的物质的粉末。作为上述物质,可以举出例如铝盐、铝醇盐、氢氧化铝、金属铝等。铝盐可以为无机盐或有机盐。作为无机盐,具体地说可以举出例如硝酸铝、硝酸铵铝等硝酸盐,碳酸铵铝等碳酸盐等。作为有机盐,可以举出例如草酸铝、乙酸铝、硬脂酸铝、乳酸铝、月桂酸铝等。作为铝醇盐,具体地说可以举出例如异丙醇铝、乙醇铝、仲丁醇铝、叔丁醇铝等。氢氧化铝可以为结晶性或无定形。氢氧化铝为结晶性的情况下,作为其结晶类型,可以举出例如三水铝石型、三羟铝石型、ノロソトランダイト型、勃姆石型、类勃姆石型等。作为无定形的氢氧化铝,可以举出例如将铝盐、铝醇盐等水溶性铝化合物的水溶液水解得到的铝水解物。
作为铝源粉末,优选为廉价、工业上容易得到的氧化铝的粉末,特别优选为α型的氧化铝。
钛源粉末和铝源粉末的用量是分别相对于换算成二氧化钛(TiO2)的钛源粉末的用量、换算成氧化铝(Al2O3)的铝源粉末的用量的总量100重量份,通常换算成二氧化钛的钛源粉末的用量优选为35~55重量份、更优选为40~50重量份,换算成氧化铝的铝源粉末的用量优选为45~65重量份、更优选为50~60重量份。
此外,构成前体混合物的硅源粉末只要是通过在空气中烧制变成SiO2或含有Si的复合氧化物的物质即可,可以举出例如二氧化硅、一氧化硅等氧化硅粉末等。作为本发明中使用的硅源粉末,优选为无定形且熔点为800~1350℃的铝硅酸盐的粉末,更优选为不含有二氧化硅、一氧化硅这样的结晶性化合物的硅源粉末。
作为硅源粉末,还可以使用兼具铝源的功能的物质的粉末。作为这种物质,可以举出例如长石、玻璃料(ガラスフリット)等。
本发明中,为了提高钛酸铝系陶瓷烧结体的机械强度和耐热稳定性,作为硅源粉末,优选使用无定形且熔点为800~1350℃的铝硅酸盐的粉末。特别优选为该铝硅酸盐的熔点优选为900~1100℃、屈服点为700℃~1000℃的铝硅酸盐玻璃。本发明中,铝硅酸盐的熔点指的是通过差示热分析装置(DTA)观测到吸热峰的温度,屈服点指的是在铝硅酸盐的热膨胀曲线的测定中出现热膨胀曲线的拐点(屈曲点)的温度。
使用熔点低于800℃的铝硅酸盐时,钛酸铝的耐热稳定性显著降低。此外,使用熔点超过1350℃的铝硅酸盐或残留有结晶性二氧化硅的铝硅酸盐时,存在耐热稳定性和耐热冲击性的提高效果减小的趋势。
换算成SiO2的硅源粉末的用量相对于换算成氧化物的前体混合物的用量(即,换算成TiO2的钛源粉末的用量、换算成Al2O3的铝源粉末的用量、换算成SiO2的硅源粉末的用量以及根据需要使用的换算成MgO的镁源粉末的用量的总计),按重量比计优选为2~10%,特别优选为2~4%。换算成SiO2的硅源粉末小于2%时,钛酸铝系陶瓷的耐热稳定性、机械强度降低,超过10%时,烧结时的变形增大,存在不能得到均质的钛酸铝系陶瓷烧结体的同时,热膨胀系数也增大的趋势。
进一步地,本发明中使用的硅源粉末优选为按氧化物的重量比计,SiO2=70~80%、Al2O3=5~15%、(Na2O+K2O)=5~25%、MgO=0~3.0%、(CaO+SrO+BaO)<4.0%的无定形的铝硅酸盐。通过使用这种硅源粉末,得到耐热稳定性和机械强度优异的钛酸铝系陶瓷烧结体。
作为相同组成的含硅的氧化物,还可以举出碱长石等天然矿物,它们是由含有结晶性二氧化硅等的多种氧化物构成的混合物。这些天然矿物的熔点、屈服点通常高于本发明的温度范围,用作原料时结晶性二氧化硅有可能残留在钛酸铝系陶瓷的晶界中。结晶性二氧化硅有可能如方英石那样在低温下产生伴随有大的体积变化的相变,这使钛酸铝系陶瓷的强度特性降低。因此,不优选将碱长石等天然矿物用于硅源。硅源粉末中含有的结晶性二氧化硅的量相对于钛酸铝以重量比计优选为0.1%以下。
在上述铝硅酸盐中,SiO2按重量比计小于70%时存在耐热稳定性降低的趋势,而超过80%时存在结晶性二氧化硅析出的趋势。上述铝硅酸盐中的SiO2的重量比更优选为70~75%。
此外,上述铝硅酸盐中,Al2O3小于5%和/或Na2O+K2O超过25%时,存在含硅相的化学性稳定性降低的趋势,Al2O3超过15%时和/或Na2O+K2O小于5%时,存在结晶性二氧化硅、熔点为1350℃以上的含硅的结晶性化合物(例如多铝红柱石等)析出的趋势。优选上述铝硅酸盐中的Al2O3的重量比为7~12%且Na2O+K2O的重量比为10~20%,更优选Na2O与K2O的重量比按Na2O/(Na2O+K2O)计为0.10~0.60。
上述铝硅酸盐中,在不改变玻璃的熔点、粘性的范围内还可以含有不可避免的杂质。作为不可避免的杂质,可以举出Li、B、F、Mg、P、Ca、Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Sr、Y、Zr、Nb、Sn、Ba、La、Ta、Ce、Pb、Bi等,这些杂质的总量按照氧化物换算(F、P是按照纯物质换算)优选为5%以下。特别是Mg、Ca、Sr、Ba由于大幅改变玻璃的特性,按照氧化物换算优选MgO为3.0%以下,优选(CaO+SrO+BaO)小于4.0%,更优选(CaO+SrO+BaO)为3%以下。
本发明中的前体混合物中,为了提高钛酸铝的耐热稳定性、降低烧结温度,除了钛源、铝源、硅源之外,还可以含有镁(Mg)、铁(Fe)的原料粉末,特别优选进一步含有镁源粉末。其中,镁源粉末指的是形成构成钛酸铝镁(Al2(1-x)MgxTi1+xO5)的镁成分的物质的粉末,可以举出例如氧化镁(氧化镁)的粉末。钛酸铝镁为钛酸铝与钛酸镁的固溶体。在本说明书中,本发明的方法中得到的“钛酸铝系陶瓷烧结体”还包括含有钛酸铝镁和铝硅酸盐的复合材料。
作为镁源粉末,还可以举出通过在空气中烧制变成氧化镁的物质。作为上述物质,可以举出例如镁盐、镁醇盐、氢氧化镁、氮化镁、金属镁等。作为镁盐,具体地说可以举出氯化镁、高氯酸镁、磷酸镁、焦磷酸镁、草酸镁、硝酸镁、碳酸镁、乙酸镁、硫酸镁、柠檬酸镁、乳酸镁、硬脂酸镁、水杨酸镁、肉豆蔻酸镁、葡糖酸镁、二甲基丙烯酸镁、苯甲酸镁等。作为镁醇盐,具体地说可以举出甲醇镁、乙醇镁等。
作为镁源粉末,还可以使用兼具镁源和铝源的功能的物质、兼具镁源和钛源的功能的物质。作为这种物质,可以举出例如镁氧尖晶石(MgAl2O4)、钛酸镁(MgTiO3、Mg2TiO5)等,特别是由于镁氧尖晶石廉价、工业上容易得到,优选作为本发明的镁源粉末。
此外,进一步地,对于本发明中的钛酸铝系陶瓷的组成,表示该钛酸铝系陶瓷的组成式:Al2(1-x)MgxTi1+xO5-aAl2O3中,优选分别满足x=0.05~0.30和a=0.0~0.3,特别优选分别满足x=0.10~0.25和a=0.0~0.3。
本发明中的前体混合物中,在不损害本发明效果的范围内,还可以含有钛、铝、镁、硅以外的添加剂粉末。作为添加剂,可以举出例如Li、B、F、P、Ca、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Sr、Y、Zr、Nb、Sn、Ba、La、Ta、Ce、Pb、Bi等,这些添加剂的总量按照氧化物换算(F、P按照纯物质换算)优选为3%以下。
上述前体混合物例如可以通过将钛源粉末、铝源粉末和硅源粉末,或钛源粉末、铝源粉末、硅源粉末和镁源粉末混合来得到。混合可以通过干式混合法、湿式混合法中的任意一种,优选通过可以更均匀地混合含有金属元素的物质的方法进行,还可以使用将原料粉末与粉碎介质一起在粉碎容器内粉碎的同时进行混合的方法。此时,作为混合装置,可以举出例如球磨机、V型混合机、振动磨、磨碎机、戴诺磨(Dyno mill)、动态磨等装置。
上述混合方法中,从工业规模上的实施容易的方面考虑,优选使用通过振动磨同时进行前体粉末的混合和粉碎的方法。混合可以通过连续式进行或通过间歇式进行,但是从工业规模上的实施容易的方面考虑,优选通过连续式进行。
作为粉碎容器,通常使用由不锈钢等金属材料构成的粉碎容器,内表面可以被氟树脂、硅树脂、聚氨酯树脂等涂布。
作为粉碎介质,可以举出例如粒径为1~100mm、优选5~50mm的氧化铝珠、氧化锆珠等,从防止杂质混入的方面考虑,优选使用氧化铝珠。
粉碎时,还可以加入分散剂、粉碎助剂、抗絮凝剂等添加剂。作为粉碎助剂,可以举出例如一元醇类(甲醇、乙醇、丙醇等)、二元醇类(丙二醇、聚丙二醇、乙二醇等)等醇类,三乙醇胺等胺类,棕榈酸、硬脂酸、油酸等高级脂肪酸类,炭黑、石墨等碳材料等,它们可以分别单独使用或组合2种以上来使用。
使用添加剂时,其总用量相对于原料粉末(即钛源粉末、铝源粉末、硅源粉末和镁源粉末)的总用量100质量份,通常为0.1~10质量份,优选为0.5~5质量份,进一步优选为0.75~2质量份。
此外,使用添加剂时,还可以从混合后的前体混合物中除去添加剂。除去添加剂时,例如使用可以通过在大气中加热而烧去的添加剂时,通过在大气中加热来烧去即可。此时的加热温度通常为500℃以下。
如此得到含有钛源粉末、铝源粉末和硅源粉末(或钛源粉末、铝源粉末、镁源粉末和硅源粉末)的前体混合物,该前体混合物通过烧制变成钛酸铝(或钛酸铝镁)。
本发明中,将含有上述前体混合物和有机类粘合剂的陶瓷可塑性捏合土成型为预定形状。作为本发明中使用的有机类粘合剂(粘合剂),可以不特别限定地使用以往公知的有机类粘合剂,可以举出例如甲基纤维素、羧甲基纤维素、羧甲基纤维素钠等纤维素类,聚乙烯醇等醇类,木质素磺酸盐等盐,石蜡、微晶蜡等蜡,EVA、聚乙烯、聚苯乙烯、液晶聚合物、工程塑料等热塑性树脂等。
本发明中制造陶瓷可塑性捏合土时,还可以添加造孔剂、润滑剂、上述分散剂、粉碎助剂、抗絮凝剂等燃烧性有机成分。燃烧性有机成分指的是在燃烧性氛围气体中通过一定温度的加热而燃烧的有机成分。作为造孔剂,可以举出例如石墨等碳材料,聚乙烯、聚丙烯、聚甲基丙烯酸甲酯等树脂类,淀粉、坚果壳、核桃壳、玉米等植物类材料,冰或干冰等。
对于包括有机类粘合剂的燃烧性有机成分的配合量不特别限定,但是相对于前体混合物100重量份,优选为1~50重量份、更优选为5~40重量份。燃烧性有机成分的配合量相对于前体混合物100重量份小于1重量份时,由于燃烧性有机成分的比率少,烧结过程中的走样、变形比较少,此外超过50重量份时,存在燃烧性有机成分的燃烧时的放热量增大的趋势。
燃烧性有机成分可以在上述前体混合物的混合时添加,或在上述混合后加入燃烧性有机成分进一步另外进行混合,从制造效率方面考虑优选同时混合。
使用添加剂时,其总用量相对于原料的总用量,即钛源粉末、铝源粉末和硅源粉末(或钛源粉末、铝源粉末、镁源粉末和硅源粉末)的总用量100重量份,通常为0.1~10重量份、优选为0.5~5重量份、进一步优选为0.75~2重量份。
使用添加剂时,还可以从混合后的前体混合物中除去添加剂。除去添加剂时,例如使用可以通过在大气中加热而烧去的添加剂时,通过在大气中加热来烧去即可。此时的加热温度通常为700℃以下。
如此可以得到本发明中使用的前体混合物,该前体混合物通过烧制变成钛酸铝系化合物。
向本发明中使用的前体混合物中加入上述造孔剂、润滑剂、分散剂、粉碎助剂、抗絮凝剂、有机类粘合剂等作为成型原料,将该成型原料混合及捏合,制造陶瓷可塑性捏合土,然后成型为预定的形状,作为用于成型可塑性捏合土的装置,可以举出例如捏和机和挤出成型机组合而成的装置、连续捏合挤出机等。
将上述前体混合物成型为预定的形状。其中,预定的形状可以举出例如,蜂窝形状、颗粒状、平板状等形状,其中由于几何学上表面积大,优选为蜂窝形状。蜂窝形状的截面形状可以举出圆形、椭圆形、四边形、三角形等,蜂窝体整体的形态可以举出圆筒体、方筒体等。
作为成型方法,可以举出例如挤出成型、铸塑成型、注射成型等方法。例如在蜂窝形状的成型体的挤出成型中,通过挤出成型将混合、捏合而塑化为可以进行挤出成型的材料成型为蜂窝形状。挤出成型的方法可以使用已知的方法。
在接下来的步骤中,将成型了的陶瓷可塑性捏合土在900~1350℃的温度范围以每小时的温度变化为-50~+50℃/h保持3小时以上、优选保持4小时以上后,升温至1400℃以上的温度,在该温度下烧结,得到钛酸铝系陶瓷烧结体。在本发明中,例如每小时的温度变化为50℃/h指的是保持3小时时的温度变化在900~1350℃的温度范围内为150℃。在900~1350℃的温度范围下保持期间,只要不偏离该温度范围且温度变化在上述范围内,则可以将前体混合物保持在恒定温度,也可以随时改变升温速度或交替重复进行升温和降温。在900~1350℃的温度范围保持前体混合物时,优选以温度变化为0℃/h的方式保持3小时以上。
在上述温度范围以每小时的温度变化为-50~+50℃/h保持3小时以上后,升温至1400℃以上、通常为低于1600℃的温度,在该温度下烧结,由此可以得到目的钛酸铝系陶瓷烧结体。热处理所需的时间只要是前体粉末转换为钛酸铝系陶瓷烧结体的时间即可,虽然根据原料粉末的种类、热处理条件不同而不同,但是通常为10分钟~24小时、优选为3小时以上且小于12小时。
本发明的钛酸铝系陶瓷烧结体的制造方法中,作为硅源,使用铝硅酸盐,在上述900~1350℃的温度范围下以每小时的温度变化为-50~+50℃/h保持3小时以上时,作为前体粉末中含有的硅源的铝硅酸盐熔融,通过毛细管现象,铝硅酸盐熔液均匀地渗透到前体粉末中。通过该现象,原料粉末凝聚,更均匀地、效率良好地进行钛酸铝的生成反应,且上述方法中得到的钛酸铝系陶瓷中的结晶粒子逐个被铝硅酸盐层覆盖。发现通过该铝硅酸盐的覆盖层可以抑制钛酸铝的热分解产生和分解反应的扩大这两方面,从而完成本发明。
在低于上述900~1350℃的温度范围的900℃以下的温度下保持前体粉末时,前体混合物中含有的铝硅酸盐不会熔融,或即使熔融而熔液不具有渗透到粒子间时所需的充分低的粘性,因此钛酸铝系陶瓷内的铝硅酸盐的分布变得不均匀。此外,在1350℃以上的温度下保持前体粉末时,与铝硅酸盐的熔融平行地还进行钛酸铝的生成反应。因此,在900~1350℃的温度范围以外保持前体粉末时,铝硅酸盐不能均匀地分布在所得到的钛酸铝系陶瓷中,且钛酸铝粒子不被铝硅酸盐层覆盖,其耐热稳定性降低的同时,所得到的钛酸铝系陶瓷烧结体的强度也降低。
上述钛酸铝系陶瓷烧结体的制造方法中,在900~1350℃的温度范围下保持前体粉末后,在1400℃以上烧结,由前体粉末生成钛酸铝。此时,若热处理温度为1500℃以上,则在前体粉末中含有镁时,确认该镁在玻璃层中溶出,钛酸铝相的组成改变,因此有可能得不到所需的特性。因此,作为1400℃以上的热处理温度,优选为1400℃以上且低于1500℃,更优选为1430℃~1470℃。
升温到上述温度范围以及保持在该温度范围时的氛围气体通常为大气中,但是根据所使用的原料粉末(即钛源粉末、铝源粉末、镁源粉末和硅源粉末)的种类、用量比,也可以在氮气、氩气等惰性气体中烧结,还可以在一氧化碳气体、氢气等还原性气体中烧结。此外,也可以在降低了水蒸气分压的氛围气体中进行烧结。
烧结通常使用管状电炉、箱式电炉、隧道炉、远红外线炉、微波加热炉、竖炉、反射炉、旋转炉、辊底式炉等通常的加热炉来进行。
如此可以得到钛酸铝、钛酸铝镁等钛酸铝系陶瓷的烧结体。本发明提供这种钛酸铝系陶瓷烧结体。即,本发明的钛酸铝系陶瓷烧结体是通过包括以下步骤的制造方法得到的钛酸铝系陶瓷烧结体,其气孔率为30~60%、优选为40~60%,所述制造方法包括将含有含钛源粉末、铝源粉末和硅源粉末的前体混合物和有机类粘合剂的陶瓷可塑性捏合土成型为预定形状的步骤,和将成型了的陶瓷可塑性捏合土在900~1350℃的温度范围下以每小时的温度变化为-50~+50℃/h保持3小时以上后,升温至1400℃以上的温度,在该温度下烧结的步骤。钛酸铝系陶瓷烧结体的气孔率小于30%时,用作内燃机的废气净化过滤器或催化剂载体时存在压力损失增大的趋势,此外,气孔率超过60%时,机械强度降低,因此不适于用作过滤器、催化剂载体。而且,钛酸铝系陶瓷烧结体的气孔率使用通过水中浸渍进行的阿基米德法( ),通过根据JIS R1634的方法算出。
本发明的钛酸铝系陶瓷烧结体的强度、耐热稳定性优异,且兼具低的热膨胀系数。本发明中的强度指的是,使用陶瓷用强度试验机,通过根据JIS R1601的方法测定得到的三点弯曲强度。此外,耐热稳定性指的是将钛酸铝系陶瓷烧结体在900~1100℃的温度区域保持规定的时间后的钛酸铝结晶相的残留率。其中,耐热稳定性优异指的是,通过将烧结体在箱式电炉中1100℃下保持48小时,得到热分解评价用样品,利用粉末X射线衍射光谱[XRD]对所得到的热分解评价用样品的构成相进行测定,由2θ=27.4°的位置出现的峰[归属于二氧化钛·金红石相(110)面]的积分强度(I[TiO2])和2θ=33.7°的位置出现的峰[归属于钛酸铝相(230)面]的积分强度(I[AT]),通过式(1)算出的热分解率为1.0%以下。
热分解率(%)=100-100×I[AT] / (I[AT]+I[TiO2]) (1)。
进一步地,这里所称的热膨胀系数指的是,例如将钛酸铝系陶瓷烧结体切出4mm×4mm×12mm的棱柱,使用该试验片,使用热机械性分析装置(SII (株)社制、TMA6300),以600℃/h由室温升温至1000℃时测定得到的热膨胀系数(K-1)。热膨胀系数越低则为耐热冲击性越优异的材料,通过上述测定法得到的热膨胀系数优选为2.0×10-6K-1以下,若为1.8×10-6K-1以下则更优选。
基于与上述相同的理由,本发明的钛酸铝系陶瓷烧结体也优选前体混合物中的硅源为无定形、熔点为900~1350℃的铝硅酸盐。
此外,基于与上述相同的理由,本发明的钛酸铝系陶瓷烧结体中,优选为前体混合物中进一步含有镁源粉末的钛酸铝镁的烧结体。
此外,进一步地,基于与上述相同的理由,本发明的钛酸铝系陶瓷烧结体中,特别优选换算成SiO2的硅源粉末与换算成氧化物的前体混合物的用量的重量比为2~10%,且硅源粉末为无定形、按氧化物的重量比计为SiO2=70~80%、Al2O3=5~15%、(Na2O+K2O)=5~25%、MgO=0~3.0%、(CaO+SrO+BaO)<4.0%的铝硅酸盐。
实施例
以下举出实施例对本发明进行更具体的说明,但是本发明不被这些实验例所限定。
(实施例1)
作为铝源粉末,使用氧化铝(住友化学社制、AT-50)的粒子47.3质量%,作为钛源粉末,使用氧化钛(デュポン社制、R-900)的粒子41.0质量%,作为镁源粉末,使用镁氧尖晶石(サンゴバン社制)的粉末6.2质量%,作为硅源粉末,使用玻璃料(SiO2=75.2%、Al2O3=9.2%、Na2O=3.0%、K2O=7.3%、CaO=2.6%、MgO=2.7%)粒子5.6质量%。所使用的玻璃料的熔点为948℃,屈服点为768℃。相对于这些前体混合粉末100质量份,加入作为造孔剂的聚乙烯粒子(d50=23μm)10质量份、作为粘合剂的甲基纤维素7.5质量份、作为表面活性剂的聚氧亚烷基烷基醚9.3质量份、作为润滑剂的甘油0.8质量份形成成型原料,进一步加入作为分散介质的水38质量份后,用捏合机捏合,制备陶瓷可塑性捏合土,将陶瓷可塑性捏合土挤出成型,制造蜂窝成型体。蜂窝成型体用干燥机在100℃下干燥12小时后,经过用箱式电炉在大气氛围气体中400℃下除去粘合剂的脱脂过程后,以300℃/h升温,在1250℃下保持5小时,进而以300℃/h升温至1450℃,在1450℃烧结5小时,由此得到蜂窝烧结体。
用粉末X射线衍射对实施例1中制造的蜂窝烧结体的粉末进行分析后结果可知,该陶瓷粉末的AT化率为100%。作为构成该粉末的结晶相,仅确认有钛酸铝镁(Al1.84Mg0.08Ti1.08O5)和氧化铝(Al2O3)(以组成式表示为Al1.84Mg0.08Ti1.08O5-0.16Al2O3),未确认有表示SiO2或含Si的氧化物的结晶相的衍射峰。将该粉末在1100℃下热处理48小时后的AT化率也为100%(分解率为0%),确认表现出优异的耐热稳定性。
得到的蜂窝体通过阿基米德法测得的气孔率为42%,干燥后与烧结后的尺寸变化为10%。蜂窝烧结体的热膨胀系数为1.6×10-6K-1。
应该认为本次公开的实施方式和实验例都是举例,而并非进行限制。本发明的范围不是被上述说明而是被权利要求书所公开,包括与权利要求书均等的意义以及在权利要求范围内的全部变更。
工业实用性
上述本发明的钛酸铝系陶瓷烧结体具有低热膨胀性和高的耐热稳定性、优异的机械强度,例如可以合适地用作柴油机等内燃机的废气净化中使用的过滤器、催化剂载体用蜂窝等。
Claims (10)
1.钛酸铝系陶瓷烧结体的制造方法,该方法包括:将含有含钛源粉末、铝源粉末和硅源粉末的前体混合物和有机类粘合剂的陶瓷可塑性捏合土成型为预定形状的步骤,和将成型了的陶瓷可塑性捏合土在900~1350℃的温度范围以每小时的温度变化为-50~+50℃/h保持3小时以上后,升温至1400℃以上的温度,在该温度下烧结的步骤。
2.如权利要求1所述的方法,其中,硅源粉末是熔点为800~1350℃的无定形的铝硅酸盐。
3.如权利要求2所述的方法,其中,所述铝硅酸盐是屈服点为700~1000℃的玻璃。
4.如权利要求1~3中任意一项所述的方法,其中,前体混合物进一步含有镁源粉末。
5.如权利要求1~4中任意一项所述的方法,其中,换算成SiO2的硅源粉末的用量与换算成氧化物的前体混合粉末的用量的重量比为2~10%,且硅源粉末是按氧化物的重量比计为SiO2=70~80%、Al2O3=5~15%、(Na2O+K2O)=5~25%、MgO=0~3.0%、(CaO+SrO+BaO)<4.0%的无定形的铝硅酸盐。
6.钛酸铝系陶瓷烧结体,其通过权利要求1~5中任意一项所述的方法制造,气孔率为30~60%。
7.如权利要求6所述的钛酸铝系陶瓷烧结体,其中,硅源粉末是熔点为800~1350℃的无定形的铝硅酸盐。
8.如权利要求7所述的钛酸铝系陶瓷烧结体,其中,所述铝硅酸盐是屈服点为700~1000℃的玻璃。
9.如权利要求6~8中任意一项所述的钛酸铝系陶瓷烧结体,其中,前体混合物进一步含有镁源粉末。
10.如权利要求6~9中任意一项所述的钛酸铝系陶瓷烧结体,其中,换算成SiO2的硅源粉末的用量与换算成氧化物的前体混合粉末的用量的重量比为2~10%,且硅源粉末是按氧化物的重量比计为SiO2=70~80%、Al2O3=5~15%、(Na2O+K2O)=5~25%、MgO=0~3.0%、(CaO+SrO+BaO)<4.0%的无定形的铝硅酸盐。
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- 2010-02-24 WO PCT/JP2010/052867 patent/WO2010098348A1/ja active Application Filing
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CN1946653A (zh) * | 2004-04-28 | 2007-04-11 | 王世来股份有限公司 | 钛酸铝镁结晶构造体及其制备方法 |
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CN103145407A (zh) * | 2013-03-14 | 2013-06-12 | 福建工程学院 | 一种刚玉-莫来石-钛酸铝复相陶瓷材料的制备方法 |
CN107367490A (zh) * | 2016-05-12 | 2017-11-21 | 鞍钢股份有限公司 | 一种x射线荧光光谱法分析制样用助研磨添加剂及使用方法 |
CN110315062A (zh) * | 2018-03-30 | 2019-10-11 | 青岛海尔智能技术研发有限公司 | 一种金属陶瓷复合材料热水器内胆及其制备方法和热水器 |
CN112759416A (zh) * | 2021-01-15 | 2021-05-07 | 武汉科技大学 | 一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法 |
CN112759416B (zh) * | 2021-01-15 | 2023-01-17 | 武汉科技大学 | 一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法 |
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EP2402296A1 (en) | 2012-01-04 |
TW201100353A (en) | 2011-01-01 |
JP2010195634A (ja) | 2010-09-09 |
EP2402296A4 (en) | 2012-08-22 |
WO2010098348A1 (ja) | 2010-09-02 |
KR20110128802A (ko) | 2011-11-30 |
US20120034446A1 (en) | 2012-02-09 |
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