CN112811882A - 一种高稳定传感器陶瓷材料及其制备方法 - Google Patents
一种高稳定传感器陶瓷材料及其制备方法 Download PDFInfo
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Abstract
本发明提供一种高稳定传感器陶瓷材料及其制备方法,所述材料的分子结构式为(1‑x)[(1‑y)LiAmO8‑yBaBnO8]‑xBiAlO3,其中0.01≤x≤0.03,0.35≤y≤0.65,1≤m≤5,1≤n≤4;A为Fe、Mn、Ni、Ti中的一种或几种;B为Mg、Co、Cr或La中的一种或几种;所述(1‑y)LiAmO8‑yBaBnO8为内层材料,所述BiAlO3为外层材料。本发明材料环保无毒,能够提供具有极低的漏电电流,通过外层涂覆BiAlO3凝胶树脂后热处理后,获得尖晶石相的压电材料,改变了整体的陶瓷材料的晶体结构,稳定的晶体结构可以获得高磁性转变点的压电性能。
Description
技术领域
本发明属于压电材料技术领域,具体涉及一种高稳定传感器陶瓷材料及其制备方法。
背景技术
铅基压电陶瓷因其优异的压电性能,已广泛应用于加速器、传感器、驱动器和传感器等电子产品中。然而,由于铅基压电陶瓷中有毒铅的环境问题,近几十年来,无铅压电陶瓷引起了人们的广泛关注,但是现有技术中的压电材料均具有较低的磁性转变点,陶瓷材料很容易转变为顺磁体,进而其磁场容易随着周围磁场的改变而改变,磁性转变点由物质的化学成分和晶体结构决定。
现有技术中的压电陶瓷材料的压电性能过低,且具有较低的转变点,容易导致压电材料无法承受较高的磁场转变,急需一种高稳定性能的压电陶瓷材料。
发明内容
本发明针对上述缺陷,提供一种具有高磁性转变点、静态压电系数、机械耦合系数、和相对介电常数的尖晶石相稳定性高的压电陶瓷材料。
本发明提供如下技术方案:一种高稳定传感器陶瓷材料,所述材料的分子结构式为(1-x)[(1-y)LiAmO8-yBaBnO8]-xBiAlO3,其中0.1≤x≤0.3,0.35≤y≤0.65,1≤m≤5,1≤n≤4;A为Fe、Mn、Ni、Ti中的一种或几种;B为Mg、Co、Cr或La中的一种或几种;所述(1-y)LiAmO8-yBaBnO8为内层材料,所述BiAlO3为外层材料;所述内层材料采用固相合成法制备,所述外层材料涂覆聚合于所述内层材料外;
所述(1-y)LiAmO8-yBaBnO8的制备方法包括以下步骤:
S1:将Li2O、A元素的金属氧化物、BaCO3、B元素的金属氧化物按照化学计量式进行添加,保证Li、A元素、Ba和B元素的摩尔比为(1-y):(1-y)×m:y:y×n,球磨18~24h,球磨过程中加入乙醇溶液,乙醇溶液中加入氧化锆球,得到浆料;
S2:将所述步骤1)得到的浆料在100℃~150℃下干燥,在800℃~1000℃下煅烧4~6h,得到混合粉末;
S3:将所述步骤2)得到的混合粉末与聚乙烯醇溶液混合,所述混合粉末与所述聚乙烯醇的重量体积比为5wt%~10wt%,得到混合粉末凝胶,在90MPa~100MPa压力下,将混合粉末凝胶压制成直径为10mm~15mm的坯体;
S4:将所述步骤3)得到的坯体在1000℃~1200℃温度下烧结3h~3.5h,然后快速冷却至25℃~27℃。
进一步地,所述内层材料(1-y)LiAmO8-yBaBnO8的结构为四菱形空间立方体结构。
进一步地,所述陶瓷材料的内层材料(1-y)LiAmO8-yBaBnO8经过外层材料BiAlO3涂覆聚合改性后,整体陶瓷材料(1-x)[(1-y)LiAmO8-yBaBnO8]-xBiAlO3为尖晶石立体结构。
进一步地,所述陶瓷材料的静态压电系数为200pC/N~230pC/N、机械耦合系数为50%~65%、磁性转变点为450℃~550℃、1kHz的相对介电常数为40000~42000。
本发明还提供一种高稳定传感器陶瓷材料的制备方法,包括以下步骤:
S1:采用固相合成法制备内层材料(1-y)LiAmO8-yBaBnO8坯体;
S2:制备外层材料BiAlO3的涂覆聚合溶液;
S3:将所述S1步骤得到的内层材料(1-y)LiAmO8-yBaBnO8坯体浸没于所述S2步骤得到的涂覆聚合溶液中,逐步滴加弱碱性溶液调节pH在9.0~10.0之间,采用100℃~120℃油浴加热使所述坯体与所述涂覆聚合溶液产生聚酯化反应,得到覆有BiAlO3凝胶树脂层的坯体;
S4:将所述S3步骤得到的覆有BiAlO3凝胶树脂层的坯体于200℃~250℃下煅烧,得到覆有固体外层材料的内层材料坯体;
S5:将所述S4步骤得到的覆有固体外层材料的内层材料坯体在750℃~800℃下热处理2h~2.5h,得到分子结构式为(1-x)[(1-y)LiAmO8-yBaBnO8]-xBiAlO3的高稳定传感器陶瓷材料,其中0.1≤x≤0.3,0.35≤y≤0.65,1≤m≤5,1≤n≤4;A为Fe、Mn、Ni、Ti中的一种或几种;B为Mg、Co、Cr或La中的一种或几种。
进一步地,所述S1步骤具体包括以下步骤:
S1.1:将Li2O、A元素的金属氧化物、BaCO3、B元素的金属氧化物按照化学计量式进行添加,保证Li、A元素、Ba和B元素的摩尔比为(1-y):(1-y)×m:y:y×n,球磨18~24h,球磨过程中加入乙醇溶液,乙醇溶液中加入氧化锆球,得到浆料;
S1.2:将所述步骤S1.1得到的浆料在100℃~150℃下干燥,在800℃~1000℃下煅烧4~6h,得到混合粉末;
S1.3:将所述步骤S1.2得到的混合粉末与聚乙烯醇溶液混合,所述混合粉末与所述聚乙烯醇溶液的重量体积比为5wt%~10wt%,得到混合粉末凝胶,在90MPa~100MPa压力下,将混合粉末凝胶压制成直径为10mm~15mm的坯体;
S1.4:将所述步骤S1.3得到的坯体在1000℃~1200℃温度下烧结3h~3.5h,然后快速冷却至25℃~27℃。
进一步地,所述S2步骤具体包括以下步骤:
S2.1:将Bi2(SO4)3、Al2(SO4)3溶于0.3M~0.6M H2SO4溶液中,采用磁力搅拌于150rpm~200rpm转速下混合均匀,得到混合原料溶液;
S2.2:将浓度为1.5M~2M的柠檬酸溶于乙二醇溶液中,得到柠檬酸乙二醇溶液;
S2.3:将所述S2.1步骤得到的混合原料溶液中加入所述S2.2步骤得到的柠檬酸乙二醇溶液,于40℃~50℃下以100rpm~200rpm转速磁力搅拌均匀,得到所述涂覆聚合溶液。
进一步地,所述S3步骤的弱碱性溶液为NH4OH、Na2CO3或NaHCO3中的一种或几种。
进一步地,所述S5步骤的热处理采用等离子热处理炉以100℃/min的升温速度预升温至750℃~800℃后进行恒温热处理2h~2.5h。
本发明的有益效果为:
1、铝酸铋BiAlO3具有优异的铁电性能,并且其组分元素廉价易获得,在室温下具有菱形对称性,利用前驱体聚合物制备方法制备出纳米级别的BiAlO3凝胶树脂,涂覆于经过固相合成法制备的LiAmO8-yBaBnO8内层材料,可以利用BiAlO3对LiAmO8-yBaBnO8改性,经过热处理后最终得到尖晶石相的压电陶瓷材料,进而进一步提高材料的压电性能和铁电性能,降低材料的介电损耗。
2、本发明采用固相合成法合成制备了具有四菱形立体结构的(1-y)LiAmO8-yBaBnO8内层材料,其制备材料没有利用铅元素原料,因而制备的材料环保无毒性,同时其内部的四菱形立体结构具有一定的稳定性,能够提供具有极低的漏电电流,提供了一个良好的压电材料的基础。通过外层涂覆同样具有菱形立体结构的BiAlO3凝胶树脂后热处理后,获得尖晶石相的压电材料,通过BiAlO3对其进行改性,改变了整体的陶瓷材料的晶体结构,稳定的晶体结构可以获得高磁性转变点的压电性能。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
本实施例提供的一种高稳定传感器陶瓷材料,所述材料的分子结构式为0.7[0.65LiFe5O8-0.35BaMg4O8]-0.3BiAlO3,所述0.65LiFe5O8-0.35BaMg4O8为内层材料,BiAlO3为外层材料;内层材料采用固相合成法制备,外层材料BiAlO3涂覆聚合于内层材料0.65LiFe5O8-0.35BaMg4O8外;
其中,内层材料0.65LiFe5O8-0.35BaMg4O8的结构为四菱形空间立方体结构。陶瓷材料0.7[0.65LiFe5O8-0.35BaMg4O8]-0.3BiAlO3的内层材料0.65LiFe5O8-0.35BaMg4O8经过外层材料BiAlO3涂覆聚合改性后,整体陶瓷材料为尖晶石立体结构。
陶瓷材料的静态压电系数为230pC/N、机械耦合系数为65%、磁性转变点为550℃、1kHz的相对介电常数为42000。
本实施例还提供上述一种高稳定传感器陶瓷材料的制备方法,包括以下步骤:
S1:采用固相合成法制备内层材料0.65LiFe5O8-0.35BaMg4O8坯体,具体如下:
S1.1:将Li2O、Fe2O3、BaCO3、MgO按照化学计量式进行添加,保证Li、Fe、Ba和Mg的摩尔比为0.65:3.25:0.35:1.4,球磨24h,球磨过程中加入乙醇溶液,乙醇溶液中加入氧化锆球,得到浆料;
S1.2:将步骤S1.1得到的浆料在150℃下干燥,在1000℃下煅烧6h,得到混合粉末;
S1.3:将步骤S1.2得到的混合粉末与聚乙烯醇溶液混合,混合粉末与聚乙烯醇的重量体积比为10wt%,得到混合粉末凝胶,在100MPa压力下,将混合粉末凝胶压制成直径为15mm的坯体;
S1.4:将步骤S1.3得到的坯体在1200℃温度下烧结3.5h,然后快速冷却至27℃。
S2:制备外层材料BiAlO3的涂覆聚合溶液,具体如下:
S2.1:将Bi2(SO4)3、Al2(SO4)3溶于0.6M H2SO4溶液中,采用磁力搅拌于200rpm转速下混合均匀,得到混合原料溶液;
S2.2:将浓度为2M的柠檬酸溶于乙二醇溶液中,得到柠檬酸乙二醇溶液;
S2.3:将S2.1步骤得到的混合原料溶液中加入S2.2步骤得到的柠檬酸乙二醇溶液,于50℃下以200rpm转速磁力搅拌均匀,得到所述涂覆聚合溶液;
S3:将S1步骤得到的内层材料0.65LiFe5O8-0.35BaMg4O8坯体浸没于所述S2步骤得到的涂覆聚合溶液中,逐步滴加浓度为0.1M的弱碱性溶液NH4OH调节pH在9.0,采用120℃油浴加热使所述坯体与所述涂覆聚合溶液产生聚酯化反应,得到覆有凝胶树脂层的坯体;
S4:将S3步骤得到的覆有凝胶树脂层的坯体于250℃下煅烧,得到覆有固体外层材料的内层材料坯体;
S5:将S4步骤得到的覆有固体外层材料的内层材料坯体采用等离子热处理炉以100℃/min的升温速度预升温至800℃后进行恒温热处理2.5h,得到结构式为0.7[0.65LiFe5O8-0.35BaMg4O8]-0.3BiAlO3的高稳定传感器陶瓷材料。
实施例2
本实施例提供的一种高稳定传感器陶瓷材料,所述材料的分子结构式为0.5[0.5LiMn3O8-0.5BaLa2.5O8]-0.5BiAlO3,所述0.5LiMn3O8-0.5BaLa2.5O8为内层材料,BiAlO3为外层材料;内层材料采用固相合成法制备,外层材料BiAlO3涂覆聚合于内层材料0.5LiMn3O8-0.5BaLa2.5O8外;
其中,内层材料0.5LiMn3O8-0.5BaLa2.5O8的结构为四菱形空间立方体结构。陶瓷材料0.5[0.5LiMn3O8-0.5BaLa2.5O8]-0.5BiAlO3的内层材料0.5LiMn3O8-0.5BaLa2.5O8经过外层材料BiAlO3涂覆聚合改性后,整体陶瓷材料为尖晶石立体结构。
陶瓷材料的静态压电系数为214pC/N、机械耦合系数为57.5%、磁性转变点为500℃、1kHz的相对介电常数为41580。
本实施例还提供上述一种高稳定传感器陶瓷材料的制备方法,包括以下步骤:
S1:采用固相合成法制备内层材料0.5LiMn3O8-0.5BaLa2.5O8坯体,具体如下:
S1.1:将Li2O、MnO2、BaCO3、La2O3按照化学计量式进行添加,保证Li、Mn、Ba和La的摩尔比为0.5:1.5:0.5:1.25,球磨21h,球磨过程中加入乙醇溶液,乙醇溶液中加入氧化锆球,得到浆料;
S1.2:将步骤S1.1得到的浆料在120℃下干燥,在905℃下煅烧5h,得到混合粉末;
S1.3:将步骤S1.2得到的混合粉末与聚乙烯醇溶液混合,混合粉末与聚乙烯醇的重量体积比为7wt%,得到混合粉末凝胶,在95MPa压力下,将混合粉末凝胶压制成直径为13mm的坯体;
S1.4:将步骤S1.3得到的坯体在1100℃温度下烧结3.25h,然后快速冷却至26℃。
S2:制备外层材料BiAlO3的涂覆聚合溶液,具体如下:
S2.1:将Bi2(SO4)3、Al2(SO4)3溶于0.45M H2SO4溶液中,采用磁力搅拌于175rpm转速下混合均匀,得到混合原料溶液;
S2.2:将浓度为1.75M的柠檬酸溶于乙二醇溶液中,得到柠檬酸乙二醇溶液;
S2.3:将S2.1步骤得到的混合原料溶液中加入S2.2步骤得到的柠檬酸乙二醇溶液,于45℃下以150rpm转速磁力搅拌均匀,得到所述涂覆聚合溶液;
S3:将S1步骤得到的内层材料0.5LiMn3O8-0.5BaLa2.5O8坯体浸没于S2步骤得到的涂覆聚合溶液中,逐步滴加浓度为0.13M的弱碱性溶液Na2CO3调节pH在9.6,采用110℃油浴加热使所述坯体与所述涂覆聚合溶液产生聚酯化反应,得到覆有凝胶树脂层的坯体;
S4:将S3步骤得到的覆有凝胶树脂层的坯体于220℃下煅烧,得到覆有固体外层材料的内层材料坯体;
S5:将S4步骤得到的覆有固体外层材料的内层材料坯体采用等离子热处理炉以100℃/min的升温速度预升温至770℃后进行恒温热处理2.2h,得到结构式为0.5[0.5LiMn3O8-0.5BaLa2.5O8]-0.5BiAlO3的高稳定传感器陶瓷材料。
实施例3
本实施例提供的一种高稳定传感器陶瓷材料,所述材料的分子结构式为0.4[0.9LiTi2O8-0.1BaCr2O8]-0.6BiAlO3,所述0.9LiTi2O8-0.1BaCr2O8为内层材料,BiAlO3为外层材料;内层材料采用固相合成法制备,外层材料BiAlO3涂覆聚合于内层材料0.9LiTi2O8-0.1BaCr2O8外;
其中,内层材料0.9LiTi2O8-0.1BaCr2O8的结构为四菱形空间立方体结构。陶瓷材料0.4[0.9LiTi2O8-0.1BaCr2O8]-0.6BiAlO3的内层材料0.9LiTi2O8-0.1BaCr2O8经过外层材料BiAlO3涂覆聚合改性后,整体陶瓷材料为尖晶石立体结构。
陶瓷材料的静态压电系数为200pC/N、机械耦合系数为50%、磁性转变点为450℃、1kHz的相对介电常数为40050。
本实施例还提供上述一种高稳定传感器陶瓷材料的制备方法,包括以下步骤:
S1:采用固相合成法制备内层材料0.9LiTi2O8-0.1BaCr2O8坯体,具体如下:
S1.1:将Li2O、TiO2、BaCO3、Cr2O3按照化学计量式进行添加,保证Li、Ti、Ba和Cr的摩尔比为0.9:1.8:0.1:0.2,球磨18h,球磨过程中加入乙醇溶液,乙醇溶液中加入氧化锆球,得到浆料;
S1.2:将步骤S1.1得到的浆料在100℃下干燥,在800℃下煅烧4h,得到混合粉末;
S1.3:将步骤S1.2得到的混合粉末与聚乙烯醇溶液混合,混合粉末与聚乙烯醇的重量体积比为5wt%,得到混合粉末凝胶,在100MPa压力下,将混合粉末凝胶压制成直径为10mm的坯体;
S1.4:将步骤S1.3得到的坯体在1000℃温度下烧结3h,然后快速冷却至25℃。
S2:制备外层材料BiAlO3的涂覆聚合溶液,具体如下:
S2.1:将Bi2(SO4)3、Al2(SO4)3溶于0.3M H2SO4溶液中,采用磁力搅拌于150rpm转速下混合均匀,得到混合原料溶液;
S2.2:将浓度为1.5M的柠檬酸溶于乙二醇溶液中,得到柠檬酸乙二醇溶液;
S2.3:将S2.1步骤得到的混合原料溶液中加入S2.2步骤得到的柠檬酸乙二醇溶液,于40℃下以100rpm转速磁力搅拌均匀,得到所述涂覆聚合溶液;
S3:将S1步骤得到的内层材料0.9LiTi2O8-0.1BaCr2O8坯体浸没于所述S2步骤得到的涂覆聚合溶液中,逐步滴加浓度为0.2M的弱碱性溶液NH4OH调节pH在10.0,采用100℃油浴加热使所述坯体与所述涂覆聚合溶液产生聚酯化反应,得到覆有凝胶树脂层的坯体;
S4:将S3步骤得到的覆有凝胶树脂层的坯体于200℃下煅烧,得到覆有固体外层材料的内层材料坯体;
S5:将S4步骤得到的覆有固体外层材料的内层材料坯体采用等离子热处理炉以100℃/min的升温速度预升温至750℃后进行恒温热处理2h,得到结构式为0.4[0.9LiTi2O8-0.1BaCr2O8]-0.6BiAlO3的高稳定传感器陶瓷材料。
对比实施例1
采用本发明实施例1-3的制作方法分别制作具有高磁导率的微波介电陶瓷材料,并采用中国专利201710886220.2中实施例1的制备方法制作的Li系微波介电陶瓷材料,按照GB/T 5593-2015《电子元器件结构陶瓷材料》中引用的标准,采用北京精科智创科技有限公司的ZJ-6型压电陶瓷准静态d33测量仪分别检测压电常数,采用日本日置HIOKI型号为IM3570阻抗分析仪检测机械品质因数、机电耦合系数、介电常数和介电损耗。结果见表1。
表1
由表1可知,本申请所采用的尖晶石相压电陶瓷材料具有优异的压电性能、机械品质因数、几点耦合系数和相对介电常数,交底的介电损耗,通过固相合成法制备具有四菱形的内层材料(1-y)LiAmO8-yBaBnO8,然后再通过前驱体聚合方法涂覆具有菱形对称结构的外层材料BiAlO3,进而对内层材料改性得到具有稳定性的尖晶石相压电材料,提高了磁性转变点和压电性能。
对比实施例2
采用本发明实施例1-3的制作方法分别制作具有高磁导率的微波介电陶瓷材料;
按照0.7[0.65LiFe5O8-0.35BaMg4O8]-0.3BiAlO3的摩尔比添加Li2O、Fe2O3、BaCO3、MgO、Bi2O3、Al2O3,并按照中国专利201310000183.2制备介质材料方法制备0.7[0.65LiFe5O8-0.35BaMg4O8]-0.3BiAlO3材料,作为对比实施例2中的对比例2.1;
按照0.5[0.5LiMn3O8-0.5BaLa2.5O8]-0.5BiAlO3的摩尔比添加Li2O、MnO2、BaCO3、La2O3、Bi2O3、Al2O3,并按照中国专利201310000183.2制备介质材料方法制备0.5[0.5LiMn3O8-0.5BaLa2.5O8]-0.5BiAlO3材料,作为对比实施例2中的对比例2.2;
按照0.4[0.9LiTi2O8-0.1BaCr2O8]-0.6BiAlO3的摩尔比添加Li2O、TiO2、BaCO3、Cr2O3、Bi2O3、Al2O3,并按照中国专利201310000183.2制备介质材料方法制备0.4[0.9LiTi2O8-0.1BaCr2O8]-0.6BiAlO3,作为对比实施例2中的对比例2.3;
按照GB/T 5593-2015《电子元器件结构陶瓷材料》中引用的标准,采用北京精科智创科技有限公司的ZJ-6型压电陶瓷准静态d33测量仪分别检测压电常数,采用日本日置HIOKI型号为IM3570阻抗分析仪检测机械品质因数、机电耦合系数、介电常数和介电损耗。结果见表2。
表2
由表2可知,不采用本发明提供的采用内核、外核结构的微波介电陶瓷材料,具有较低的压电常数、机械品质因数、磁性转变点温度、机电耦合系数和介电常数,导致其陶瓷材料内部微观结构不稳定,极易受到外界温度等环境的变化,导致其微波介电性能在极短时间内快速下降,造成介电性能不稳定,且其介电损耗相对本发明提供的内部构造内核结构(1-y)LiAmO8-yBaBnO8,外部通过离子涂覆方法制备BiAlO3层,形成稳定的尖晶石结构的压电陶瓷材料更加的高,进而导致仅仅通过Bi2O3、Al2O3与内核材料中的其他元素的氧化物进行混合、球磨通过固相合成法合成的压电陶瓷材料具有更稳定的晶体结构,可以获得高磁性转变点的压电性能。
虽然已经参考优选实施例对本发明进行了描述,但在不脱离本发明的范围的情况下,可以对其进行各种改进并且可以用等效物替换其中的部件。尤其是,只要不存在结构冲突,各个实施例中所提到的各项技术特征均可以任意方式组合起来。本发明并不局限于文中公开的特定实施例,而是包括落入权利要求的范围内的所有技术方案。
Claims (9)
1.一种高稳定传感器陶瓷材料,其特征在于,所述材料的分子结构式为(1-x)[(1-y)LiAmO8-yBaBnO8]-xBiAlO3,其中0.1≤x≤0.3,0.35≤y≤0.65,1≤m≤5,1≤n≤4;A为Fe、Mn、Ni、Ti中的一种或几种;B为Mg、Co、Cr或La中的一种或几种;所述(1-y)LiAmO8-yBaBnO8为内层材料,所述BiAlO3为外层材料;所述内层材料采用固相合成法制备,所述外层材料涂覆聚合于所述内层材料外;
所述(1-y)LiAmO8-yBaBnO8的制备方法包括以下步骤:
S1:将Li2O、A元素的金属氧化物、BaCO3、B元素的金属氧化物按照化学计量式进行添加,保证Li、A元素、Ba和B元素的摩尔比为(1-y):(1-y)×m:y:y×n,球磨18~24h,球磨过程中加入乙醇溶液,乙醇溶液中加入氧化锆球,得到浆料;
S2:将所述步骤1)得到的浆料在100℃~150℃下干燥,在800℃~1000℃下煅烧4~6h,得到混合粉末;
S3:将所述步骤2)得到的混合粉末与聚乙烯醇溶液混合,所述混合粉末与所述聚乙烯醇的重量体积比为5wt%~10wt%,得到混合粉末凝胶,在90MPa~100MPa压力下,将混合粉末凝胶压制成直径为10mm~15mm的坯体;
S4:将所述步骤3)得到的坯体在1000℃~1200℃温度下烧结3h~3.5h,然后快速冷却至25℃~27℃。
2.根据权利要求1所述的一种高稳定传感器陶瓷材料,其特征在于,所述内层材料(1-y)LiAmO8-yBaBnO8的结构为四菱形空间立方体结构。
3.根据权利要求1所述的一种高稳定传感器陶瓷材料,其特征在于,所述陶瓷材料的内层材料(1-y)LiAmO8-yBaBnO8经过外层材料BiAlO3涂覆聚合改性后,整体陶瓷材料(1-x)[(1-y)LiAmO8-yBaBnO8]-xBiAlO3为尖晶石立体结构。
4.根据权利要求1所述的一种高稳定传感器陶瓷材料,其特征在于,所述陶瓷材料的静态压电系数为200pC/N~230pC/N、机械耦合系数为50%~65%、磁性转变点为450℃~550℃、1kHz的相对介电常数为40000~42000。
5.一种高稳定传感器陶瓷材料的制备方法,其特征在于,包括以下步骤:
S1:采用固相合成法制备内层材料(1-y)LiAmO8-yBaBnO8坯体;
S2:制备外层材料BiAlO3的涂覆聚合溶液;
S3:将所述S1步骤得到的内层材料(1-y)LiAmO8-yBaBnO8坯体浸没于所述S2步骤得到的涂覆聚合溶液中,逐步滴加弱碱性溶液调节pH在9.0~10.0之间,采用100℃~120℃油浴加热使所述坯体与所述涂覆聚合溶液产生聚酯化反应,得到覆有BiAlO3凝胶树脂层的坯体;
S4:将所述S3步骤得到的覆有BiAlO3凝胶树脂层的坯体于200℃~250℃下煅烧,得到覆有固体外层材料的内层材料坯体;
S5:将所述S4步骤得到的覆有固体外层材料的内层材料坯体在750℃~800℃下热处理2h~2.5h,得到分子结构式为(1-x)[(1-y)LiAmO8-yBaBnO8]-xBiAlO3的高稳定传感器陶瓷材料,其中0.1≤x≤0.3,0.35≤y≤0.65,1≤m≤5,1≤n≤4;A为Fe、Mn、Ni、Ti中的一种或几种;B为Mg、Co、Cr或La中的一种或几种。
6.根据权利要求5所述的一种高稳定传感器陶瓷材料的制备方法,其特征在于,所述S1步骤具体包括以下步骤:
S1.1:将Li2O、A元素的金属氧化物、BaCO3、B元素的金属氧化物按照化学计量式进行添加,保证Li、A元素、Ba和B元素的摩尔比为(1-y):(1-y)×m:y:y×n,球磨18~24h,球磨过程中加入乙醇溶液,乙醇溶液中加入氧化锆球,得到浆料;
S1.2:将所述步骤S1.1得到的浆料在100℃~150℃下干燥,在800℃~1000℃下煅烧4~6h,得到混合粉末;
S1.3:将所述步骤S1.2得到的混合粉末与聚乙烯醇溶液混合,所述混合粉末与所述聚乙烯醇溶液的重量体积比为5wt%~10wt%,得到混合粉末凝胶,在90MPa~100MPa压力下,将混合粉末凝胶压制成直径为10mm~15mm的坯体;
S1.4:将所述步骤S1.3得到的坯体在1000℃~1200℃温度下烧结3h~3.5h,然后快速冷却至25℃~27℃。
7.根据权利要求5所述的一种高稳定传感器陶瓷材料的制备方法,其特征在于,所述S2步骤具体包括以下步骤:
S2.1:将Bi2(SO4)3、Al2(SO4)3溶于0.3M~0.6M H2SO4溶液中,采用磁力搅拌于150rpm~200rpm转速下混合均匀,得到混合原料溶液;
S2.2:将浓度为1.5M~2M的柠檬酸溶于乙二醇溶液中,得到柠檬酸乙二醇溶液;
S2.3:将所述S2.1步骤得到的混合原料溶液中加入所述S2.2步骤得到的柠檬酸乙二醇溶液,于40℃~50℃下以100rpm~200rpm转速磁力搅拌均匀,得到所述涂覆聚合溶液。
8.根据权利要求5所述的一种高稳定传感器陶瓷材料的制备方法,其特征在于,所述S3步骤的弱碱性溶液为NH4OH、Na2CO3或NaHCO3中的一种或几种。
9.根据权利要求5所述的一种高稳定传感器陶瓷材料的制备方法,其特征在于,所述S5步骤的热处理采用等离子热处理炉以100℃/min的升温速度预升温至750℃~800℃后进行恒温热处理2h~2.5h。
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CN113387695A (zh) * | 2021-06-08 | 2021-09-14 | 杭州电子科技大学 | 一种5g通信用低介高品质微波介质陶瓷及其制备方法 |
Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5990605A (en) * | 1997-03-25 | 1999-11-23 | Pioneer Electronic Corporation | Electron emission device and display device using the same |
AU2878300A (en) * | 1997-03-28 | 2000-08-29 | Callaway Golf Company | Low spin golf ball comprising a metal, ceramic, or composite mantle or inner layer |
CN1926926A (zh) * | 2004-04-06 | 2007-03-07 | 出光兴产株式会社 | 电极基板及其制造方法 |
CN101591461A (zh) * | 2009-06-24 | 2009-12-02 | 四川大学 | 无铅压电陶瓷-聚合物压电复合材料及其制备方法 |
CN102260080A (zh) * | 2010-05-31 | 2011-11-30 | 中国科学院上海硅酸盐研究所 | 一种改性CaBi2Nb2O9铋层状结构压电陶瓷材料及其制备方法 |
CN102714315A (zh) * | 2009-08-09 | 2012-10-03 | 美洲锂能公司 | 电活性颗粒及由其组成的电极和电池 |
CN103000879A (zh) * | 2012-12-19 | 2013-03-27 | 南开大学 | 一种具有一维多孔结构的尖晶石型锂镍锰氧的制备方法 |
WO2013058604A2 (ko) * | 2011-10-21 | 2013-04-25 | 한국생산기술 연구원 | 전기자동차용 리튬이차전지용 고에너지밀도의 양극 복합소재 합성 및 전극 제조기술 |
CN103154739A (zh) * | 2010-08-05 | 2013-06-12 | 雅培医护站股份有限公司 | 磁免疫传感器和使用方法 |
KR101333792B1 (ko) * | 2012-06-05 | 2013-11-29 | 한국세라믹기술원 | 비스무스 기반의 무연 압전 세라믹스 및 그 제조방법 |
CN103664227A (zh) * | 2013-12-16 | 2014-03-26 | 东南大学 | 利用微生物矿化捕获co2的水泥基材料表面覆膜防护剂及其使用的方法 |
CN104086172A (zh) * | 2014-07-16 | 2014-10-08 | 武汉理工大学 | 一种超宽温高稳定无铅电容器陶瓷介质材料及其制备方法 |
US20160126544A1 (en) * | 2009-08-09 | 2016-05-05 | Jiang Fan | High capacity electroactive particles, and electrodes and batteries comprising the same |
CN107311643A (zh) * | 2017-07-06 | 2017-11-03 | 湖北大学 | 宽工作温区高介电性能的无铅电子陶瓷材料及制备方法 |
CN108516826A (zh) * | 2018-05-18 | 2018-09-11 | 西华大学 | 一种含Sn中介微波介质陶瓷材料及其制备方法 |
CN109265167A (zh) * | 2018-09-05 | 2019-01-25 | 佛山市亿强电子有限公司 | 一种低温烧结pzt压电陶瓷的方法及压电陶瓷 |
CN110330266A (zh) * | 2019-07-16 | 2019-10-15 | 湖南省美程陶瓷科技有限公司 | 新能源动力电池继电器陶瓷材料及其制备方法 |
CN110330315A (zh) * | 2019-07-04 | 2019-10-15 | 新化县顺达电子陶瓷有限公司 | 一种低温烧结氧化铝黑色陶瓷及其制备方法 |
CN111094985A (zh) * | 2017-09-08 | 2020-05-01 | 布利斯脱大学 | 传感器 |
CN111517803A (zh) * | 2020-04-25 | 2020-08-11 | 湖南省美程陶瓷科技有限公司 | 一种微波磁控管用陶瓷支持体及其制备方法 |
CN111732430A (zh) * | 2020-07-16 | 2020-10-02 | 长沙麓桥科技有限公司 | 一种Sm和Eu共掺杂CaBi8Ti7O27陶瓷的制备方法及其产品及应用 |
-
2021
- 2021-01-11 CN CN202110028552.3A patent/CN112811882B/zh active Active
Patent Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5990605A (en) * | 1997-03-25 | 1999-11-23 | Pioneer Electronic Corporation | Electron emission device and display device using the same |
AU2878300A (en) * | 1997-03-28 | 2000-08-29 | Callaway Golf Company | Low spin golf ball comprising a metal, ceramic, or composite mantle or inner layer |
CN1926926A (zh) * | 2004-04-06 | 2007-03-07 | 出光兴产株式会社 | 电极基板及其制造方法 |
CN101591461A (zh) * | 2009-06-24 | 2009-12-02 | 四川大学 | 无铅压电陶瓷-聚合物压电复合材料及其制备方法 |
US20160126544A1 (en) * | 2009-08-09 | 2016-05-05 | Jiang Fan | High capacity electroactive particles, and electrodes and batteries comprising the same |
CN102714315A (zh) * | 2009-08-09 | 2012-10-03 | 美洲锂能公司 | 电活性颗粒及由其组成的电极和电池 |
CN102260080A (zh) * | 2010-05-31 | 2011-11-30 | 中国科学院上海硅酸盐研究所 | 一种改性CaBi2Nb2O9铋层状结构压电陶瓷材料及其制备方法 |
CN103154739A (zh) * | 2010-08-05 | 2013-06-12 | 雅培医护站股份有限公司 | 磁免疫传感器和使用方法 |
WO2013058604A2 (ko) * | 2011-10-21 | 2013-04-25 | 한국생산기술 연구원 | 전기자동차용 리튬이차전지용 고에너지밀도의 양극 복합소재 합성 및 전극 제조기술 |
KR101333792B1 (ko) * | 2012-06-05 | 2013-11-29 | 한국세라믹기술원 | 비스무스 기반의 무연 압전 세라믹스 및 그 제조방법 |
CN103000879A (zh) * | 2012-12-19 | 2013-03-27 | 南开大学 | 一种具有一维多孔结构的尖晶石型锂镍锰氧的制备方法 |
CN103664227A (zh) * | 2013-12-16 | 2014-03-26 | 东南大学 | 利用微生物矿化捕获co2的水泥基材料表面覆膜防护剂及其使用的方法 |
CN104086172A (zh) * | 2014-07-16 | 2014-10-08 | 武汉理工大学 | 一种超宽温高稳定无铅电容器陶瓷介质材料及其制备方法 |
CN107311643A (zh) * | 2017-07-06 | 2017-11-03 | 湖北大学 | 宽工作温区高介电性能的无铅电子陶瓷材料及制备方法 |
CN111094985A (zh) * | 2017-09-08 | 2020-05-01 | 布利斯脱大学 | 传感器 |
CN108516826A (zh) * | 2018-05-18 | 2018-09-11 | 西华大学 | 一种含Sn中介微波介质陶瓷材料及其制备方法 |
CN109265167A (zh) * | 2018-09-05 | 2019-01-25 | 佛山市亿强电子有限公司 | 一种低温烧结pzt压电陶瓷的方法及压电陶瓷 |
CN110330315A (zh) * | 2019-07-04 | 2019-10-15 | 新化县顺达电子陶瓷有限公司 | 一种低温烧结氧化铝黑色陶瓷及其制备方法 |
CN110330266A (zh) * | 2019-07-16 | 2019-10-15 | 湖南省美程陶瓷科技有限公司 | 新能源动力电池继电器陶瓷材料及其制备方法 |
CN111517803A (zh) * | 2020-04-25 | 2020-08-11 | 湖南省美程陶瓷科技有限公司 | 一种微波磁控管用陶瓷支持体及其制备方法 |
CN111732430A (zh) * | 2020-07-16 | 2020-10-02 | 长沙麓桥科技有限公司 | 一种Sm和Eu共掺杂CaBi8Ti7O27陶瓷的制备方法及其产品及应用 |
Non-Patent Citations (5)
Title |
---|
LI HE等: ""A Novel Magnetodielectric Solid Solution Ceramic 0.4LiFe5O8–0.6Li2MgTi3O8 with Excellent Microwave Dielectric Properties"", 《J. AM. CERAM. SOC.》 * |
MUTLUULUTAGAY-KARTIN等: ""Synthesis, structure, and magnetic properties of two quasi-low-dimensional antiferromagnets, NaMnAsO4 and β-NaCuPO4"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
周佳骏: ""铌酸钾钠基无铅压电陶瓷的相结构和性能调控"", 《中国博士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
岑侦勇等: ""BiAl03改性对BF-BT压电陶瓷电性能与皿日度稳定性的影响"", 《人工晶体学报》 * |
张晓燕等: ""(1-x)LiNbO3-xBiAlO3(x=0~0.7)陶瓷的制备及性能"", 《稀有金属材料与工程》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113387695A (zh) * | 2021-06-08 | 2021-09-14 | 杭州电子科技大学 | 一种5g通信用低介高品质微波介质陶瓷及其制备方法 |
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