CN1980721A - 低热膨胀制品 - Google Patents

低热膨胀制品 Download PDF

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CN1980721A
CN1980721A CNA2005800100028A CN200580010002A CN1980721A CN 1980721 A CN1980721 A CN 1980721A CN A2005800100028 A CNA2005800100028 A CN A2005800100028A CN 200580010002 A CN200580010002 A CN 200580010002A CN 1980721 A CN1980721 A CN 1980721A
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ceramic
oxide
composition
mixture
honeycomb ceramics
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D·M·比尔
M·J·德内卡
C·L·鲍威尔
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Corning Inc
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Abstract

揭示适用于高温应用如汽车排气处理的低热膨胀的组合物和制品,以及这种制品的制造方法。

Description

低热膨胀制品
本申请要求于2004年3月31日由Dejneka等提交的标题为“低热膨胀制品”的美国临时申请No.60/558,165的权益。
发明领域
本发明涉及低热膨胀组合物,由这些组合物制成的制品以及制造这种制品的方法。
背景技术
低热膨胀的耐热冲击制品能用于尤其例如在高温循环期间极需保持产品尺寸的应用,诸如汽车排气处理应用。具体地,低热膨胀制品已被用作流体过滤器,如柴油机微粒过滤器,以及用作催化转化器的基材。典型的这类制品包括一种蜂窝体,并且需经受苛刻的环境,这要求高的耐热冲击性和耐机械冲击性以及低热膨胀。要在预定环境中在相当长一段时间内保持这些性质,因而淘汰了许多有可能有用的耐火材料
堇青石蜂窝状基材可用于许多高温应用,包括催化剂转化器、NOx吸附器、电加热催化剂、熔融金属过滤器、预热器芯体、化学处理基材、用于加氢脱硫、氢化裂解或氢化处理的催化剂、柴油机微粒过滤器,部分是由于堇青石的高耐热冲击性。耐热冲击性与热膨胀系数呈反比关系。即堇青石的蜂窝体具有良好的耐热冲击性,能承受应用中所遇到的大的温度波动。但是,在某些情况,堇青石基材的性能并不能令人满意。作为理想地结合低CTE(对耐热冲击性)、低压降(对发动机效率)、高过滤效率(为从排气流中除去大部分的微粒)、高强度(能承受加工、装罐,以及使用中的振动)和低成本的柴油机微粒过滤器(DPF),在堇青石DPF的情况下已证实难以做到高耐热冲击性与很低压降的结合。此外,堇青石与基于钾的NOx吸附剂不相容,这种吸附剂与堇青石发生化学反应,破坏了该吸附剂也破坏了堇青石载体。
因此,需要提供另一种能承受高温应用所经历的热冲击和陡的热梯度的低热膨胀耐火材料。
发明概述
本发明提供一种陶瓷制品,其在250-800℃温度范围热膨胀小于20×10-7/℃,具有包含x(A)+y(Z2O5)的组合物,其中,x和y是各组分的摩尔分数,使x+y=1,0≤x≤0.80,0.20≤y≤1.00,其中,A选自下组的氧化物:RO、RO’2、R”2O3、RO3、R’2O5和它们的混合物,Z选自铌(Nb)、钽(Ta)、钒(V)、磷(P)或它们的混合物。优选0.10≤x≤0.50,更优选0.20≤x≤0.30,并优选0.50≤y≤0.90,更优选0.70≤y≤0.80。
依据包含A的氧化物,满足下面条件:(a)对RO,R选自镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镍(Ni)、锌(Zn)或锰(Mn),且0≤x≤0.40;(b)对R’O2,R’选自钛(Ti)或锆(Zr),且当R’的Ti时,0.15≤x≤0.80,R’是Zn时,0.05≤x≤0.76;(c)对R”2O3,R”选自硼(B)、铝(Al)、镓(Ga)、镧(La)或铁(Fe),且0≤x≤0.40;(d)对RO3,R选自钼(Mo)或钨(W),且0≤x≤0.50;(e)对R′2O5,R′是磷(P),且0≤x≤0.25。此外,对组分Z,满足下面条件:(a)Nb2O5,0≤y≤0.95;(b)对Ta2O5,0≤y≤0.85;(c)对V2O5,0≤y≤0.50;(d)对P2O5,0≤y≤0.25。
在优选的实施方式中,(a)对RO,当R选自Mg、Ca、Sr或Ba时,则0≤x≤0.30;当R是Ni时,则0≤x≤0.15;当R是Mn时,则0≤x≤0.24;(b)对R’O2,当R’是Ti时,则0.15≤x≤0.30,更优选0.20≤x≤0.30;当R’是Zr时则0.10≤x≤0.30,更优选0.10≤x≤0.2;(c)对R”2O3,当R”选自B、Al、Ga或Fe时,则0≤x≤0.20,更优选当R”选自B、Al或Ga时,则0≤x≤0.05;(d)对RO3,当R是Mo时,则0≤x≤0.01;当R是W时,则0≤x≤0.05;(e)当R’的磷(P)时,则0≤x≤0.1;(f)对Nb2O5,0.45≤y≤0.90,更优选0.65≤y≤0.80;(g)对Ta2O5,0≤y≤0.10,更优选0≤y≤0.01;(h)对V2O5,0≤y≤0.10;(i)对P2O5,0≤y≤0.10。
本发明的另一个实施方式中,组合物还可以包含选自以下的添加剂:(a)碱金属,如Li2O、Na2O、K2O、Rb2O和CS2O,其量为0-0.10摩尔分数,优选为0-0.02,更优选0-0.01;(b)稀土金属氧化物,如Y2O3和La2O3,其量为0-0.20摩尔分数,优选0-0.10,更优选0-0.01。
本发明的陶瓷制品特别适用于柴油机排气过滤,因为它提供了对发动机的低压降和低背压,以及在热循环期间的耐久性的应用。柴油机微粒过滤器包括堵塞的壁流式蜂窝体。一个实施方式中,这种蜂窝体由具有由x(A)+y(Nb2O5)所形成的组合物的陶瓷构成,其中A选自TiO2和ZrO2,且0.25≤y≤0.50,和0.50≤y≤0.75。优选该蜂窝体由具有由0.25(TiO2)+0.75(Nb2O5)所形成的组合物的陶瓷构成,其中所述陶瓷具有Ti2Nb10O29的主相。
另一个实施方式中,DPF包含由具有Ti2Nb10O29主相的铌酸钛陶瓷材料构成的蜂窝体,并具有下面性质:CTE(25-800℃)为-5至+5×10-7/℃;孔隙率为50-75体积%;中值孔径为10-25微米;断裂模量在300-600psi范围,所述断裂模量采用四点法,在沿平行于孔道方向从所述蜂窝体切出的多孔棒(cellularbar)上进行测定,所述蜂窝体的孔密度为200个孔/英寸2(cpsi),且壁厚为0.015英寸;对孔密度为200 cpsi,孔壁厚为0.015英寸的直径2英寸,长6英寸的样品,在26 scfm(标准立方英尺/分)流速下,人造含碳烟炱加载量最多为5g/L时的压降为4-5.5 kPa或更小。
本发明还涉及制造陶瓷制品的方法,所述陶瓷制品在25-800℃温度范围显示小于20×10-7/℃的低热膨胀,适合用于高温应用,该方法包括下面步骤:(a)配制选自氧化物、碳酸盐、硝酸盐、氟化物、磷酸和硼酸的原料的批料;(b)将原料批料与加工助剂混合,形成均匀并塑化的混合物,所述加工助剂选自增塑剂、润滑剂和粘合剂;(c)通过挤出,将所述均匀并塑化的混合物成形为坯体,如蜂窝体结构的坯体;(d)加热至最高温度为1200-1650℃,保持1-24小时,优选1350-1425℃保持1-24小时。
本发明还涉及制造陶瓷制品的方法,所述陶瓷制品在25-800℃温度范围显示小于30×10-7/℃的低热膨胀,适合用于高温应用,该方法包括下面步骤:(a)配制包含磷酸以及一种或多种选自氧化物、碳酸盐、硝酸盐、氟化物和硼酸的的原料的批料,(b)将原料批料与加工助剂混合,形成均匀并塑化的混合物,所述加工助剂选自增塑剂、润滑剂和粘合剂;(c)通过挤出,将所述均匀并塑化的混合物成形为坯体;(d)加热坯体至最高温度为300-1450℃,优选300-600℃保持1-24小时。
附图简述
参照附图结合下面的详细说明,能更完全地理解本发明,其中:
图1是本发明陶瓷材料的微结构照片,该陶瓷材料是以25摩尔%TiO2和75摩尔%Nb2O5配制的,具有Ti2Nb10O29的主相;
图2是本发明陶瓷材料的微结构照片,该陶瓷材料是以50摩尔%TiO2和50摩尔%Nb2O5配制的,具有TiNb2O7主相;
图3是本发明陶瓷材料的微结构照片,该陶瓷材料是以25摩尔%ZrO2和75摩尔%Nb2O5配制的,具有ZrNb14O37的主相;
图4是本发明陶瓷材料的微结构照片,该陶瓷材料是以50摩尔%ZrO2和50摩尔%Nb2O5配制的,具有Nb2Zr6O17的主相;
图5是热膨胀随TiO2-Mb2O5和ZrO2-Nb2O5体系中R’O2的摩尔%变化的图。
图6是对包含Ti2Nb10O29陶瓷材料的柴油机微粒过滤器,在26.25 cfm(立方英尺/分)的气体流速下进口与出口之间的压降(即压降差,kPa)值随含碳烟炱加载量(g/L)变化的图。
发明详述
本发明的各种实施方式提供了热膨胀系数低的材料、方法和制品。具体而言,本发明的材料具有通式x(A)+y(Z2O5)表示的组合物,其中x和y是各组分的摩尔分数,使x+y=1。具体地,0≤x≤0.80,优选0.10≤x≤0.50,更优选0.20≤x≤0.30,而0.20≤y≤1.00,优选0.50≤y≤0.90,更优选0.70≤y≤0.80。
组分A选自下组的氧化物:RO、RO’2、R”2O3、RO3、R’2O5和它们的混合物。对氧化物RO,R选自镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镍(Ni)、锌(Zn)或锰(Mn)。对氧化物R’O2,R’选自钛(Ti)或锆(Zr)。对氧化物R”2O3,R”选自硼(B)、铝(Al)、镓(Ga)、镧(La)或铁(Fe)。对氧化物RO3,R选自钼(Mo)或钨(W)。对氧化物R’2O5,R’是磷(P)。
组分Z选自铌(Nb)、钽(Ta)、钒(V)、磷(P)或它们的混合物。
对RO或R”2O3氧化物,x在以下范围:对MgO、CaO、SrO、BaO为0-0.40,优选0-0.30;对NiO为0-0.15,对MnO为0-0.24,对B2O3、Al2O3、Ga2O3、Fe2O3为0-0.20,更优选对B2O3、Al2O3、Ga2O3为0-0.05。当A是TiO2时,x在0.15-0.80范围,优选0.15-0.30,更优选0.20-0.30。对ZrO2,x在0.05-0.76范围,优选0.10-0.30,更优选0.10-0.20。当组分A包含RO3氧化物时,对MoO3,x在0-0.50范围,优选0-0.30,更优选0-0.01,对WO3为0-0.05。当组分A包含P2O5时,x在0-0.25范围。
对Nb2O5,y在0.20-0.95范围,优选0.45-0.90,更优选0.65-0.80。对Ta2O5,y在0-0.80范围,优选0-0.10,更优选0-0.01。对V2O5,y在0-0.50范围,优选0-0.10。对P2O5,y在0-0.25范围,优选0-0.10。
组合物还包含添加剂,如碱金属氧化物和稀土金属氧化物。合适的碱金属氧化物包括Li2O、Na2O、K2O、Rb2O和Cs2O,其量为0-0.10摩尔分数,优选0-0.02,更优选0-0.01。合适的稀土金属氧化物包括Y2O3和La2O3,其量为0-0.20摩尔分数,优选0-0.10,更优选0-0.01。
本发明的陶瓷材料具有如图1-4所示的针状形态。图1和图2是TiO2-Nb2O5体系的陶瓷材料的微结构的照片。图1所示的陶瓷材料是以25摩尔%TiO2和75摩尔%Nb2O5配制的,并具有Ti2Nb10O29的主相。图2所示的陶瓷材料是以50摩尔%TiO2和50摩尔%Nb2O5配制的,并具有TiNb2O7的主相。
图3和图4所示是ZrO2-Nb2O5体系的陶瓷材料的微结构的照片。图3所示的陶瓷材料是以25摩尔%ZrO2和75摩尔%Nb2O5配制的,并具有ZrNb14O37的主相。图4所示的陶瓷材料是以50摩尔%ZrO2和50摩尔%Nb2O5配制的,并具有Nb2Zr6O17的主相。虽然不希望受该理论的束缚,但是,相信针状形态是粗的微结构,这种结构能产生微裂纹,并因此使各向异性颗粒构成的所得陶瓷体为低的负热膨胀。
因此,本发明的陶瓷材料的CTE在-15至20×10-7/℃范围,优选-10至15×10-7/℃,更优选-5至5×10-7/℃。下面参见图5,图中所示是对TiO2-Nb2O5和ZrO2-Nb2O5体系,热膨胀随摩尔%RO2变化的图。CTE随TiO2和ZrO2的摩尔%提高而增加,在约80摩尔%RO2后成为不合格的。
除了低CTE外,本发明的材料还具有高强度,使这种材料能适合于汽车排气处理应用。一个实施方式中,柴油机微粒过滤器包含堵塞的壁流式过滤体,该过滤体由本发明的TiO2-Nb2O5体系的陶瓷材料组成。优选TiO2-Nb2O5材料具有Ti2Nb10O29的主相。
蜂窝过滤体具有进口端和出口端,并有许多个从进口端延伸到出口端的孔,所述的孔具有多孔壁,其中,孔的总数中有一部分在进口端沿其部分长度被堵塞,其余部分在进口端敞开的孔在出口端沿其部分长度被堵塞,使发动机排气流从进口端至出口端通过蜂窝体的孔,流入开孔,通过孔壁,并通过出口端的开孔离开该蜂窝体结构。适合于柴油机微粒过滤器的孔密度在70-800个孔/英寸2(10.9-24个孔/厘米2)。
在优选的实施方式中,本发明的柴油机微粒过滤器的CTE(25-800℃)为-5至+5×10-7/℃;孔隙率为50-75体积%;中值孔径为10-25微米;断裂模量在300-600磅/英寸2(psi)范围,该断裂模量采用四点法,在沿平行于孔道方向从所述蜂窝体切出的多孔棒(cellular bar)上进行测定,所述蜂窝体的孔密度为200个孔/英寸2(cpsi),且壁厚为0.015英寸;对孔密度为200cpsi,孔壁厚为0.015英寸的直径2英寸,长6英寸的样品,在26scfm流速下,人造含碳烟炱加载量最多为5g/L时的压降为4-5.5kPa或更小。
本发明的材料可以采用常规高温烧结原料或预反应的材料来合成。烧制温度为1200-1650℃,可依据组成进行选择,但优选在1350-1425℃范围。制造本发明制品的一般方法包括混合适当的批料,较好是平均粒度为5-50微米粒度的批料来获得低热膨胀体。已经发现,很细的亚微米级TiO2粉末会导致大于10%的过度烧结收缩和低孔隙率,但是,当需要致密体时它又是非常有用的。
然后,包含最终化合物如氧化物、碳酸盐、硝酸盐、氟化物、磷酸或硼酸的来源的混合粉末与有机加工助剂如增塑剂、润滑剂、粘合剂和溶剂混合。典型的有机加工助剂包括甲基纤维素粘合剂、油酸/三乙醇胺表面活性剂和作为溶剂的水。该混合物然后通过挤出或其他适当的成形方法成形为坯体,任选干燥,并烧制成硬的多孔结构。磷酸,特别是当磷酸占总混合物的足够部分时,即达到2-5%的P2O5(在最终制品中),可以在低温如低于400℃与其他组分氧化物反应,使该部件具有更高的强度。因此,使用这种范围量的磷酸,能够采用低至300℃的烧制温度,可根据磷酸的百分量变化,而产生的结构还具有可接受的强度特性。然而,应注意到,使用在此范围之内量的磷酸时,如果烧制温度低于1350℃,则制成的制品的CTE在25-800℃范围,可能从小于20×10-7/℃增加到小于30×10-7/℃。表I列出了含不同百分数磷酸的各混合物的例子,以及在不同温度下烧制由含这些混合物的坯体所得到的相应CTE和强度。
根据本发明的一个特定实施方式,提供一种用于改进的柴油机排气过滤的柴油机微粒过滤器。将所述混合物挤出通过蜂窝体模头进行成形,形成蜂窝体结构,然后在进口端和出口端堵塞一部分孔,如壁流式过滤器领域所公知的。在孔的端部通常只堵塞约1-20毫米的深度,虽然该深度可以改变。在出口端但与进口端的孔不对应的部分的孔被堵塞,反之亦然。因此,每个孔只在一端被堵塞。优选的排列是在给定面的每隔一个孔以方格(checkered)图形被堵塞。
为更充分地说明本发明,提供了下面的非限制性实施例。
实施例
适合于形成本发明的低CTE材料的无机粉末批料混合物示于表II并按摩尔%列出其量。称量约30-40克的氧化物来源粉末的批料,然后干混合约15分钟,来形成样品组合物。加入0.5-1.0ml的异丙醇,有助于形成该组合物。然后将该批料均匀加入5/2×3/8×1/2英寸(64.2×9.6×12.1毫米)的模具中,施加10,000磅/英寸2(psi)压力,并保持约5秒。从模具中推出该棒,置于在炉子内的Pt箔上,在8小时内加热至1400℃,然后在6小时内冷却。然后,将该棒机加工为长2.00英寸(25.4毫米),在差示热膨胀计中,根据低膨胀标准,测定热膨胀。CTE在25-800℃温度范围的单位为10-7/℃。
形成的样品为TiO2-Nb2O5和ZrO2-Nb2O5体系,并分别具有Ti2Nb10O29、TiNb2O7,和Nb2Zr6O17、ZrNb14O37的主相。测定的CTE在-9.3至+0.3×10-7/℃范围。
表III列出挤出为蜂窝体结构并对柴油机排气过滤进行测试的批料混合物的例子。氧化物原料是以25摩尔%TiO2和75摩尔%Nb2O5配制的。然后加入包含4重量%Methocel F240(Dow Chemical)和1重量%硬脂酸钠的有机添加剂。该干批料然后在一混合机内进行研磨,同时缓慢添加足量的水,使批料变软,根据原料的粒度,水量通常为10-30重量%,更优选20-22重量%。
混合后,将该批料加入挤出机中,脱气,然后挤出成通心粉条状。将该批料三次挤出成通心粉条状,以确保混合和可加工性。挤出时的压力可在500-5000psi范围,可依据水含量、粒度、粘合剂含量和挤出机尺寸改变。挤出的蜂窝体的尺寸为,直径2英寸,孔的几何条件为200/16cpsi。接下来,该部件在高频干燥器中部分加热,使甲基纤维素(methocel)胶凝,然后在90℃干燥至少2天,除去残余的水分。然后,干燥的蜂窝体结构在最高1400℃烧制8小时,然后在6小时内冷却。
X-射线分析表明是Ti2Nb10O29的主相。进一步测试该样品,测定按10-7/℃(使用膨胀计进行测定)的热膨胀、按psi(在沿平行于孔道方向从所述蜂窝体切出的多孔棒(cellular bar)上进行测定,所述蜂窝体的孔密度为200cpsi,且壁厚为0.015英寸)的强度、按体积%的孔隙率和按微米的中值孔径(采用注汞式孔隙率检测法测定)和压降。通过以26scfm流速,在蜂窝体样品上施加人造含碳烟炱(类似于复印机调色剂),对加载量范围最大至5g/L测试压降,测定在进口端和出口端间的压降,以kPa表示。
测试的样品证明,对柴油机排气过滤应用显示优良的性能,包括-4.1×10-7/℃的低CTE;54.8体积%的高孔隙率;10.3微米的大的中值孔径;和300-600psi的MOR强度。图6示出,对具有Ti2Nb10O29主相的许多样品,压降随含碳烟炱的加载量变化。依据含碳烟炱加载量,背压在约1.75-4.75kPa范围变化显示优良结果。
表I
  实施例     组成(摩尔%)  烧制温度(℃)  CTE10-7/℃ 强度(psi)(实心棒,非多孔制品)  主相   次相
  Nb2O5  P2O5(以磷酸配制)   TiO2
  1   75  1   24  500  27 181  Nb2O5(固溶液)
 1350  12.5  Nb2O5(固溶液)
  2   75  5   20  500  27.8 1218  Nb2O5(固溶液)
 1350  15.5  Nb2O5(固溶液)
  3   75  12.5   12.5  500  28 1453  Nb2O5(固溶液)   NbPO5
 1350  9.4  Nb2O5(固溶液)
  4   75  25   0  500  22.5 1184  Nb2O5(固溶液)   Nb(P1.81O7)
 1350  21 3565   PNb9O25   NbPO5
表II
  实施例     组成(摩尔%)   烧制温度(℃) 主相     CTE(10-7/℃)
  Nb2O5   TiO2   ZrO2
  1   75   25   --   1400  Ti2Nb10O29     0.3
  2   50   50   --   1400  TiNbO7     -0.9
  3   75   --   25   1400  ZrNb14O37     -9.3
  4   50   --   50   1400  Nb2Zr6O17     -3.7
表III
原料(摩尔%)  挤出添加剂(重量%)
Nb2O5   TiO2  F240 methocel    硬脂酸钠
75   25  4    1 21
烧制温度(℃)  主相  CTE(10-7/℃) 孔隙率(体积%) MPD(微米)   强度(psi)  压降(kPa)
1400  TixNb10O29   -4.1 54..8 10.3   300-400   4.8-4.9

Claims (20)

1.一种陶瓷制品,其在25-800℃温度范围的热膨胀小于20×10-7/℃,具有包含x(A)+y(Z2O5)的组合物,其中x和y是各组分的摩尔分数,使x+y=1,并且0≤x≤0.80,0.20≤y≤1.00,
其中:
a.A选自下组的氧化物:RO、R’O2、R”2O3、RO3、R””2O5及其混合物,其中:
i.对RO,R选自镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镍(Ni)、锌(Zn)或锰(Mn),且0≤x≤0.40;
ii.对R’O2,R’选自钛(Ti)或锆(Zr),且当R’是Ti时,0.15≤x≤0.80,当R’是Zr时,0.05≤x≤0.76;
iii.对R”2O3,R”选自硼(B)、铝(Al)、镓(Ga)、镧(La)或铁(Fe),且0≤x≤0.40;
iv.对RO3,R选自钼(Mo)或钨(W),且0≤x≤0.50;
v.对R””2O5,R””是磷(P),且0≤x≤0.25;
b.Z选自铌(Nb)、钽(Ta)、钒(V)、磷(P)或它们的混合物,其中::
i.对Nb2O5,0≤y≤0.95;
ii.对Ta2O5,0≤y≤0.85;
iii.对V2O5,0≤y≤0.50;
iv.对P2O5,0≤y≤0.25。
2.如权利要求1所述的陶瓷制品,其特征在于,对RO,当R选自Mg、Ca、Sr或Ba时,则0≤x≤0.30。
3.如权利要求1所述的陶瓷制品,其特征在于,对RO,当R是Ni时,则0≤x≤0.15。
4.如权利要求1所述的陶瓷制品,其特征在于,对RO,当R是Mn时,则0≤x≤0.24。
5.如权利要求1所述的陶瓷制品,其特征在于,对R’O2,当R’是Ti时,则0.15≤x≤0.30。
6.如权利要求1所述的陶瓷制品,其特征在于,对R’O2,当R’是Zr时,则0.10≤x≤0.30。
7.如权利要求1所述的陶瓷制品,其特征在于,对R”2O3,当R”选自B、Al、Ga或Fe时,则0≤x≤0.20。
8.如权利要求1所述的陶瓷制品,其特征在于,对RO3,当R是W时,则0≤x≤0.05。
9.如权利要求1所述的陶瓷制品,其特征在于,对Nb2O5,0.45≤y≤0.90。
10.如权利要求1所述的陶瓷制品,其特征在于,对V2O5,0≤y≤0.10。
11.如权利要求1所述的陶瓷制品,其特征在于,对P2O5,0≤y≤0.10。
12.如权利要求1所述的陶瓷制品,其特征在于,所述组合物还包含选自碱金属氧化物或稀土金属氧化物的添加剂。
13.如权利要求12所述的陶瓷制品,其特征在于,碱金属氧化物选自Li2O、Na2O、K2O、Rb2O和Cs2O。
14.如权利要求12所述的陶瓷制品,其特征在于,稀土金属氧化物选自Y2O3和La2O3
15.一种包含堵塞的壁流式蜂窝体的柴油机微粒过滤器,其特征在于,所述蜂窝体由具有由x(A)+y(Nb2O5)所形成的组合物的陶瓷构成,其中A选自TiO2和ZrO2,且0.25≤y≤0.50,0.50≤y≤0.75。
16.如权利要求15所述的柴油机微粒过滤器,其特征在于,蜂窝体由具有由0.25(TiO2)+0.75(Nb2O5)所形成的组合物的陶瓷构成,该陶瓷具有Ti2Nb10O29的主相。
17.如权利要求15所述的柴油机微粒过滤器,其特征在于,所述柴油机微粒过滤器具有以下性质:
a.CTE(25-800℃)为-5至+5×10-7/℃;
b.孔隙率为50-75体积%;
c.中值孔径为10-25微米;
d.断裂模量在300-600psi范围,所述断裂模量采用四点法,在沿平行于孔道方向从所述蜂窝体切出的多孔棒上进行测定,所述蜂窝体的孔密度为200个孔/英寸2(cpsi),且壁厚为0.015英寸;
e.对孔密度为200cpsi,孔壁厚为0.015英寸的直径2英寸,长6英寸的样品,在26scfm流速下,人造含碳烟炱加载量最多为5g/L时的压降为4-5.5kPa或更小。
18.一种制造陶瓷制品的方法,所述陶瓷制品在25-800℃温度范围具有小于20×10-7/℃的低热膨胀,适用于高温应用,该方法包括以下步骤:
(a)配制选自氧化物、碳酸盐、硝酸盐、氟化物、磷酸或硼酸的原料配制的批料;
(b)将原料批料与加工助剂混合,形成均匀并塑化的混合物,所述加工助剂选自增塑剂、润滑剂或粘合剂;
(c)通过挤出,将所述均匀并塑化的混合物成形为坯体,
(d)加热坯体至最高温度为1200-1650℃,保持1-24小时,形成具有包含x(A)+y(Z2O5)的组合物的陶瓷,其中x和y是各组分的摩尔分数,使x+y=1,并且0≤x≤0.80,0.20≤y≤1.00,
其中:
i.A选自下组的氧化物:RO、R’O2、R”2O3、RO3、R””2O5及其混合物,其中:
(1).对RO,R选自镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镍(Ni)、锌(Zn)或锰(Mn),且0≤x≤0.40;
(2).对R’O2,R’选自钛(Ti)或锆(Zr),当R’是Ti时,0.15≤x≤0.80,当R’是Zr时,0.05≤x≤0.76;
(3).对R”2O3,R”选自硼(B)、铝(Al)、镓(Ga)、镧(La)或铁(Fe),且0≤x≤0.40;
(4).对RO3,R选自钼(Mo)或钨(W),且0≤x≤0.50;
(5).对R””2O5,R””是磷(P),且0≤x≤0.25;
ii.Z选自铌(Nb)、钽(Ta)、钒(V)、磷(P)或它们的混合物,其中::
(1).对Nb2O5,0≤y≤0.95;
(2).对Ta2O5,0≤y≤0.85;
(3).对V2O5,0≤y≤0.50;
(4).对P2O5,0≤y≤0.25。
19.一种制造陶瓷制品的方法,所述陶瓷制品在25-800℃温度范围具有小于30×10-7/℃的低热膨胀,适用于高温应用,该方法包括以下步骤:
(a)配制包含磷酸以及一种或多种选自氧化物、碳酸盐、硝酸盐、氟化物和硼酸的原料的批料,
(b)将原料批料与加工助剂混合,形成均匀并化塑的混合物,所述加工助剂选自增塑剂、润滑剂和粘合剂;
(c)通过挤出,将所述均匀并化塑的混合物成形为坯体;
(d)加热坯体至最高温度为300-1450℃,保持1-24小时,形成具有包含x(A)+y(Z2O5)的组合物的陶瓷,其中x和y是各组分的摩尔分数,使x+y=1,并且0≤x≤0.80,0.20≤y≤1.00,
其中:
i.A选自下组的氧化物:RO、R’O2、R”2O3、RO3、R””2O5及其混合物,其中:
(1).对RO,R选自镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镍(Ni)、锌(Zn)或锰(Mn),且0≤x≤0.40;
(2).对R’O2,R’选自钛(Ti)或锆(Zr),当R’是Ti时,0.15≤x≤0.80,当R’是Zr时,0.05≤x≤0.76;
(3).对R”2O3,R”选自硼(B)、铝(Al)、镓(Ga)、镧(La)或铁(Fe),且0≤x≤0.40;
(4).对RO3,R选自钼(Mo)或钨(W),且0≤x≤0.50;
(5).对R””2O5,R””是磷(P),且0.02≤x≤0.25;
ii.Z选自铌(Nb)、钽(Ta)、钒(V)或它们的混合物,其中::
(1).对Nb2O5,0≤y≤0.95;
(2).对Ta2O5,0≤y≤0.85;
(3).对V2O5,0≤y≤0.50。
20.如权利要求19所述的方法,其特征在于,坯体被加热到300-600℃,持续1-24小时。
CNA2005800100028A 2004-03-31 2005-03-29 低热膨胀制品 Pending CN1980721A (zh)

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