CN108358624A - 一种低膨胀磷酸盐陶瓷材料及其制备方法 - Google Patents

一种低膨胀磷酸盐陶瓷材料及其制备方法 Download PDF

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CN108358624A
CN108358624A CN201810199180.9A CN201810199180A CN108358624A CN 108358624 A CN108358624 A CN 108358624A CN 201810199180 A CN201810199180 A CN 201810199180A CN 108358624 A CN108358624 A CN 108358624A
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ceramic material
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aqueous solution
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刘福田
汪洋
周媛媛
宋圆圆
杨路平
韩卓群
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University of Jinan
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Abstract

本发明涉及一种可耐高温的低膨胀NZP族磷酸盐陶瓷材料及其制备方法，属于低膨胀陶瓷领域。本发明的陶瓷材料为可耐高温、抗热震且热膨胀系数较低的NZP族固溶体型Ca0.5Sr0.5Zr4‑ xTixP6O24（简称CSZTP）磷酸盐陶瓷材料，当0<x≤0.2时，其平均热膨胀系数为2.5~3.2×10‑6/℃。本发明采用反序共沉淀法制备CSZTP陶瓷粉料，此法克服了固相合成法的煅烧温度太高、煅烧时间长、第二相难以消除以及组成分布不均匀的劣势，同时，也克服了水热法和溶胶‑凝胶法的合成周期长、产率低的缺点。此法制备的粉体物相组成较纯，粉体粒度较均匀，并且合成时间较短，还具有生产工艺简单等优点，便于推广应用。本发明所制备的磷酸盐陶瓷材料保持了较低的热膨胀系数，同时还具有致密性较好（相对密度达到了90%以上）、烧结温度较高、高温性能好、抗热震性能好等优点，可以应用在许多重要的高温领域。

Description

一种低膨胀磷酸盐陶瓷材料及其制备方法
技术领域
本发明涉及一种低膨胀磷酸盐陶瓷材料及其制备方法，属于低膨胀陶瓷领域。该低膨胀磷酸盐陶瓷材料致密性较好、烧结温度较高、高温性能好、抗热震性能好等优点，可以应用在许多重要的高温领域。
背景技术
NZP族磷酸盐陶瓷代表了一族相同结构类型的新型陶瓷材料，其母体为NaZr2(PO4)3(简称NZP)。Na+可以被不同的阳离子取代，产生一系列相同结构类型的衍生物，统称为NZP族化合物。以该化合物为粉体进一步制备的NZP族磷酸盐陶瓷具有低热膨胀性、耐高温性及抗热震性，在催化剂载体、发动机元件以及航天技术涂层方面都有较大应用潜力，为生产高性能、高附加值的磷酸盐陶瓷产品开辟了一条新的途径。
SrZr4(PO4)6与CaZr4(PO4)6这两种材料都具有热膨胀各向异性，并且两者的热膨胀各向异性特征是相反的，可将它们互溶形成固溶体型Ca0.5Sr0.5Zr4P6O24磷酸盐陶瓷材料。虽然Ca0.5Sr0.5Zr4P6O24磷酸盐陶瓷材料有着较低的热膨胀系数，但是其致密度较低，在正常情况下只能达到理论密度的76.69%，严重影响其力学性能。为了提高其致密度，本专利通过掺杂部分Ti4+，形成了Ca0.5Sr0.5Zr4-xTixP6O24磷酸盐陶瓷材料，在保持了较低的热膨胀系数的同时，显著提高了材料的致密度，同时烧结温度较高，耐高温性能好，抗热震性能好，可以应用在许多高温领域。
发明内容
本发明的目的在于以Ca0.5Sr0.5Zr4P6O24陶瓷为基体，由Ti4+取代部分Zr4+，从而制备一种具有低膨胀特性的Ca0.5Sr0.5Zr4-xTixP6O24磷酸盐陶瓷材料，以及提供一种简便的Ca0.5Sr0.5Zr4-xTixP6O24磷酸盐陶瓷材料的制备方法。
本发明的磷酸盐陶瓷材料的化学组成式为Ca0.5Sr0.5Zr4-xTixP6O24，当0<x≤0.2时，其平均热膨胀系数为2.5~3.2×10-6/℃，相对密度达到了90%以上，同时烧结温度较高，耐高温性能好，抗热震性能好，可以应用在许多高温领域。本发明技术方案为：一种简便的Ca0.5Sr0.5Zr4-xTixP6O24磷酸盐陶瓷材料及其制备方法，其中，x取值为0<x≤0.2。
（1）按照设计的配方，分别称取CaCO3、SrCO3、C16H36O4Ti、ZrOCl2·8H2O以及(NH4)2HPO4。将ZrOCl2·8H2O溶解于蒸馏水中，配制成0.5 - 1 mol/L的ZrOCl2·8H2O水溶液；将CaCO3和SrCO3溶解于ZrOCl2·8H2O水溶液中，配制成CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液；将C16H36O4Ti溶解在乙醇中，配制成0.5 - 1 mol/L的C16H36O4Ti乙醇溶液，并将其加入到上述CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液中，形成同时含Ca2+、Sr2+、Ti4+、Zr4+的混合溶液。配制浓度为1 - 1.5 mol/L的 (NH4)2HPO4水溶液，将同时含Ca2+、Sr2+、Ti4+、Zr4+ 的混合溶液逐滴滴加到(NH4)2HPO4水溶液中，并在反应过程中滴加氨水，保持反应在碱性环境（8.5≤ pH ≤ 9）下进行。形成的共沉淀物用蒸馏水洗涤后，再用乙醇进行冲洗，之后将沉淀物干燥至恒重；
（2）共沉淀物经900-1000℃煅烧4 - 6 h后，将煅烧得到的粉体磨细至过60目筛后干燥，然后过筛、造粒、成型，在1400 - 1500℃下烧结。
本发明的有益效果：
用于煅烧后制得原料粉体的前驱体采用共沉淀法制备，此法克服了固相合成法的煅烧温度太高、所需煅烧时间长、第二相难以消除以及组成分布不均匀的劣势；同时，也克服了水热法和溶胶-凝胶法的合成周期长、产率低的缺点。此法制备的粉体组成较纯，粉体粒度较均匀，并且合成时间短，还具有生产工艺简单等优点，便于推广应用。
附图说明
图1为实施例1制备的Ca0.5Sr0.5Zr3.97Ti0.03P6O24粉体的XRD图谱。
图2为实施例2制备的Ca0.5Sr0.5Zr3.9Ti0.1P6O24粉体的XRD图谱。
图3为实施例3制备的Ca0.5Sr0.5Zr3.84Ti0.16P6O24粉体的XRD图谱。
图4中的曲线a为实施例1制备的Ca0.5Sr0.5Zr3.97Ti0.03P6O24的热膨胀系数变化曲线；图4中的曲线b为实施例2制备的Ca0.5Sr0.5Zr3.9Ti0.1P6O24的热膨胀系数变化曲线；图4中的曲线c为实施例3制备的Ca0.5Sr0.5Zr3.84Ti0.16P6O24的热膨胀系数变化曲线。
具体实施方式
下面结合实例对本发明的特点作进一步描述，但是并非仅仅局限于下述实施例。
实施例１
（1）按照x=0.03计算出原料CaCO3、SrCO3、C16H36O4Ti、ZrOCl2·8H2O以及(NH4)2HPO4的质量，然后用天平分别称取。将ZrOCl2·8H2O溶解于蒸馏水中，配制成浓度为0.6mol/L的水溶液；将C16H36O4Ti溶解于乙醇中，配制成0.5mol/L的乙醇溶液；将(NH4)2HPO4溶解于蒸馏水中，配制成浓度为1mol/L的水溶液。将CaCO3和SrCO3溶解于ZrOCl2·8H2O水溶液中，配制成CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液，并将C16H36O4Ti乙醇溶液加入到上述CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液中，形成同时含Ca2+、Sr2+、Ti4+、Zr4+的混合溶液。将上述混合溶液用分液漏斗匀速滴加到(NH4)2HPO4水溶液中，并在反应过程中滴加氨水，保持反应在8.5 ≤pH ≤ 9的碱性环境下进行。经过滤分离后得到的共沉淀物先经过3到4次蒸馏水冲洗，再用乙醇进行冲洗，之后将沉淀物置于电热鼓风干燥箱中在80℃下干燥至恒重；（2）将干燥后的沉淀物，经900℃煅烧4h；将煅烧后的粉体球磨4h后干燥，过60目筛；（3）对粉体进行造粒、压制成型。成型后的坯体在1400℃下保温4h烧结，在降至1000℃之前的过程中保持降温速率为2℃/min，此后随炉冷却至室温。烧结后得到目标产物；对在900℃下煅烧所得的Ca0.5Sr0.5Zr3.97Ti0.03P6O24磷酸盐粉体材料进行XRD分析，其XRD图谱见图1。图1表明，共沉淀产物经高温煅烧后完全转化为Ca0.5Sr0.5Zr3.97Ti0.03P6O24化合物形式的多晶物质。对在1400℃下保温4h烧结得到的Ca0.5Sr0.5Zr3.97Ti0.03P6O24磷酸盐陶瓷材料进行热膨胀测试，得到该材料在0-800℃的平均线膨胀系数为2.6×10-6/℃，其热膨胀系数变化曲线见图4中的曲线a。
实施例2
（1）按照x=0.1计算出原料CaCO3、SrCO3、C16H36O4Ti、ZrOCl2·8H2O以及(NH4)2HPO4的质量，然后用天平分别称取。将ZrOCl2·8H2O溶解于蒸馏水中，配制成浓度为0.8mol/L的水溶液；将C16H36O4Ti溶解于乙醇中，配制成0.6mol/L的乙醇溶液；将(NH4)2HPO4溶解于蒸馏水中，配制成浓度为1mol/L的水溶液。将CaCO3和SrCO3溶解于ZrOCl2·8H2O水溶液中，配制成CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液，并将C16H36O4Ti乙醇溶液加入到上述CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液中，形成同时含Ca2+、Sr2+、Ti4+、Zr4+的混合溶液。将上述混合溶液用分液漏斗匀速滴加到(NH4)2HPO4水溶液中，并在反应过程中滴加氨水，保持反应在8.4 ≤pH ≤ 9.2的碱性环境下进行。经过滤分离后得到的共沉淀物先经过3到4次蒸馏水冲洗，再用乙醇进行冲洗，之后将沉淀物置于电热鼓风干燥箱中在70℃下干燥至恒重；（2）将干燥后的沉淀物，经过950℃煅烧6h；将煅烧后的粉体球磨5h后干燥，过60目筛；（3）对粉体进行造粒、压制成型。成型后的坯体在1400℃下保温4h烧结，在降至1000℃之前的过程中保持降温速率为2℃/min，此后随炉冷却至室温。烧结后得到目标产物；对在950℃下煅烧所得的Ca0.5Sr0.5Zr3.9Ti0.1P6O24磷酸盐粉体材料进行XRD分析，其XRD图谱见图2。图2表明，共沉淀产物经高温煅烧后完全转化为Ca0.5Sr0.5Zr3.9Ti0.1P6O24化合物形式的多晶物质。对在1400℃下保温4h烧结得到的Ca0.5Sr0.5Zr3.9Ti0.1P6O24磷酸盐陶瓷材料进行热膨胀测试，得到该材料在0-800℃的平均线膨胀系数为2.5×10-6/℃，其热膨胀系数变化曲线见图4中的曲线b。
实施例3
（1）按照x=0.16计算出原料CaCO3、SrCO3、C16H36O4Ti、ZrOCl2·8H2O以及(NH4)2HPO4的质量，然后用天平分别称取。将ZrOCl2·8H2O溶解于蒸馏水中，配制成浓度为1mol/L的水溶液；将C16H36O4Ti溶解于乙醇中，配制成0.8mol/L的乙醇溶液；将(NH4)2HPO4溶解于蒸馏水中，配制成浓度为1.2mol/L的水溶液。将CaCO3和SrCO3溶解于ZrOCl2·8H2O水溶液中配制成CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液，并将C16H36O4Ti乙醇溶液加入到上述CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液中，形成同时含Ca2+、Sr2+、Ti4+、Zr4+的混合溶液。将上述混合溶液用分液漏斗匀速滴加到(NH4)2HPO4水溶液中，并在反应过程中滴加氨水，保持反应在8 ≤pH ≤ 8.8的碱性环境下进行。经过滤分离后得到的共沉淀物先经过3到4次蒸馏水冲洗，再用乙醇进行冲洗，之后将沉淀物置于电热鼓风干燥箱中在60℃下干燥至恒重；（2）将干燥后的沉淀物，经过1000℃煅烧4h；将煅烧后的粉体球磨4h后干燥，过60目筛；（3）对粉体进行造粒、压制成型。成型后的坯体在1500℃下保温4h烧结，在降至1000℃之前的过程中保持降温速率为2℃/min，此后随炉冷却至室温。烧结后得到目标产物；对在1000℃下煅烧所得的Ca0.5Sr0.5Zr3.84Ti0.16P6O24磷酸盐粉体材料进行XRD分析，其XRD图谱见图3。图3表明，共沉淀产物经高温煅烧后完全转化为Ca0.5Sr0.5Zr3.84Ti0.16P6O24化合物形式的多晶物质。对在1500℃下保温4h烧结得到的Ca0.5Sr0.5Zr3.84Ti0.16P6O24磷酸盐陶瓷材料进行热膨胀测试，得到该材料在0-800℃的平均线膨胀系数为3.2×10-6/℃，其热膨胀系数变化曲线见图4中的曲线c。

Claims (2)

1.具有低膨胀特性的Ca0.5Sr0.5Zr4-xTixP6O24磷酸盐陶瓷材料，其特征在于该材料为一类新型的可耐高温、抗热震且热膨胀系数较低的NZP族固溶体型磷酸盐陶瓷材料，当0<x≤0.2时，其平均热膨胀系数为2.5~3.2×10-6/℃，相对密度达到了90%以上，致密性较好。
2.权利要求1所述的具有低膨胀特性的CSZTP陶瓷粉体的制备采用反序共沉淀法，其特征在于：
⑴ 以化学纯CaCO3、SrCO3、ZrOCl2·8H2O、(NH4)2HPO4以及C16H36O4Ti为原料；将ZrOCl2·8H2O溶解于蒸馏水中，配制成ZrOCl2·8H2O水溶液，再将CaCO3、SrCO3溶解于ZrOCl2·8H2O水溶液中，配制成CaCO3、SrCO3和ZrOCl2·8H2O盐的水溶液；将C16H36O4Ti溶解在乙醇中，配制成C16H36O4Ti乙醇溶液，并将其加入到上述CaCO3、SrCO3、ZrOCl2·8H2O盐的水溶液中，形成同时含Ca2+、Sr2+、Ti4+、Zr4+的混合溶液；将(NH4)2HPO4溶解于蒸馏水中，配制成(NH4)2HPO4水溶液；共沉淀反应过程中，为了防止共沉淀反应的分步沉淀，采用反加料法，即把配制的同时含Ca2+、Sr2+、Ti4+、Zr4+的混合溶液逐滴滴加到(NH4)2HPO4的水溶液中，并在反应过程中滴加氨水，保持反应在碱性（pH为8.5 - 9）环境下进行；将 (NH4)2HPO4水溶液过量5 ~ 10%，以确保Ca2+、Sr2+、Zr4+和Ti4+能够完全形成沉淀物；
⑵ 反应所生成的沉淀物经蒸馏水洗涤后，再用乙醇进行冲洗，干燥后煅烧；将煅烧得到的粉体磨细后干燥，然后过筛、造粒、成型；
⑶ 该磷酸盐陶瓷的烧结温度为1400~1500℃。
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