CN117466618B - 稀土改性低变形率卫生陶瓷泥料及其制备方法和应用 - Google Patents
稀土改性低变形率卫生陶瓷泥料及其制备方法和应用 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 47
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 18
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 rare earth compound Chemical class 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 16
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 16
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 14
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052656 albite Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 229910010293 ceramic material Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 10
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 9
- 229910052863 mullite Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
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- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- BEDFIBPNPHRGDO-UHFFFAOYSA-N yttrium;hydrate Chemical compound O.[Y] BEDFIBPNPHRGDO-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供了一种稀土改性低变形率卫生陶瓷泥料及其制备方法和应用，包括成品瓷泥、稀土复合物、粘结剂和水，稀土复合物的添加量占成品瓷泥质量的4%‑40%；粘结剂的添加量占成品瓷泥质量的0.1%‑1%；水的添加量占成品瓷泥质量的0.1%‑30%。本发明所述的泥料可以达到煅烧后产品的形变量在20 mm以下，且外表光滑，大大减少了瓷泥与釉料的用量，节约了生产成本。
Description
技术领域
本发明属于陶瓷泥料制备领域，尤其是涉及一种稀土改性低变形率卫生陶瓷泥料及其制备方法和应用。
背景技术
陶瓷是陶器与瓷器的统称，同时也是我国的一种工艺美术品，质高形美，具有较高的艺术价值。传统陶瓷包括建筑卫生陶瓷、日用陶瓷、工业美术陶瓷、化工陶瓷等。随着高新技术工业的兴起，各种新型特种陶瓷得到了发展，陶瓷已日趋成为卓越的功能材料应用于生活的各个领域。
稀土是我国最具特色的优势资源，被广泛应用于冶金、机械、石化、玻璃、陶瓷、纺织等领域。稀土元素被称为工业维生素，被广泛用作增强材料性能的掺杂剂，但在稀土元素改性瓷泥性能这方面的应用却少有报道。
经研究调查发现，现有制备陶瓷技术还有很多缺点，例如，工艺复杂使陶瓷的生产成本大大提高，高温煅烧后的陶瓷形变较大，其次，生产出来的陶瓷色泽暗淡。本发明旨在利用稀土元素的掺杂来改善陶瓷形变严重的问题。
发明内容
有鉴于此，本发明旨在克服现有技术中的缺陷，提出一种稀土改性低变形率卫生陶瓷泥料及其制备方法和应用。
为达到上述目的，本发明的技术方案是这样实现的：
第一方面，一种稀土改性低变形率卫生陶瓷泥料，包括成品瓷泥、稀土化合物、粘结剂和水，稀土复合物的添加量占成品瓷泥质量的4%-40%；粘结剂的添加量占成品瓷泥质量的0.1%-1%；水的添加量占成品瓷泥质量的0.1%-30%；所述稀土复合物由锆酸镧、碳酸铈、氧化钇复配而得。
优选地，所述稀土复合物中锆酸镧、碳酸铈、氧化钇的质量比（5-20）： （2-10）：（1-10）。
优选地，所述粘结剂为硅溶胶、PVA、PVB中的一种或几种的混合物。
优选地，所述成品瓷泥为高岭土、钠长石、钾长石、粘土中一种或几种的混合物。
优选地，所述稀土改性低变形率卫生陶瓷泥料的烧成变形量为20 mm以下。
第二方面，本发明还提供了上述稀土改性低变形率卫生陶瓷泥料的制备方法，包括如下步骤：
称取成品瓷泥、稀土复合物、水、粘结剂依次放入球磨罐中，并使用行星球磨机进行球磨，设置行星球磨机的参数为转速350-400 rpm，旋转时间 10-20min，得到稀土改性低变形率卫生陶瓷泥料。
第三方面，本发明还提供了一种低变形率卫生陶瓷，所述陶瓷由上述泥料为原料煅烧而成。
本发明中添加的稀土复合物（锆酸镧、碳酸铈、氧化钇）在陶瓷烧结过程中，与成品瓷泥中的硅铝等元素反应生成低熔点固熔体，从而限制了莫来石晶粒生长的各向异性，使其在陶瓷内部生长成莫来石晶状体，进而减小了莫来石的收缩形变率。具体来说，因为镧、铈的离子半径与硅铝相当，在与瓷泥混合烧结的过程中，镧、铈离子嵌入到硅铝化合物的骨架中，起到支撑骨架的作用，从而减小陶瓷在烧结时的形变率，钇的离子半径略小，适量添加可以填补晶格间的空隙。另外，铈元素有利于促进莫来石晶相的生成，有利于减小陶瓷煅烧时的形变率。综上所述，本发明所选用的稀土复合物中的锆酸镧、碳酸铈、氧化钇在烧结过程中具有协同配合的作用，降低了瓷泥烧结过程中的收缩率。
相对于现有技术，本发明具有以下优势：
本发明所述的泥料可以达到煅烧后产品的形变量在20 mm以下，且外表光滑，大大减少了瓷泥与釉料的用量，节约了生产成本；同时最终产品无对人体有害物质的溢出，环保健康，这将是卫生陶瓷生产的一个新方向。
附图说明
图1为不同稀土改性瓷泥的XRD图；
图2为实施例1制得的陶瓷的微观电镜图；
图3为对比例1制得的陶瓷的微观电镜图。
具体实施方式
除有定义外，以下实施例中所用的技术术语具有与本发明创造所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂，如无特殊说明，均为常规生化试剂；所述实验方法，如无特殊说明，均为常规方法。
下面结合实施例来详细说明本发明。
实施例1
将质量比为5:5:1的锆酸镧、碳酸铈、氧化钇混合制备得到稀土复合物。按照质量比100:9:25:0.6的比例称取瓷泥、稀土复合物、水、硅溶胶，依次放入球磨罐中，并使用行星球磨机进行球磨。设置行星球磨机的参数为转速400rpm，旋转时间 15 min，得到低变形率泥浆。泥浆缓慢倒入条状模具中，静置12 h成型。将成型的瓷条在110℃下烘干3h，而后以5℃/min的升温速率加热到1150℃煅烧3h，然后缓慢降至室温，得到该陶瓷材料。该样条收缩率为4%，变形量为10mm。按照所述制备方法制成的陶瓷材料，得到以下元素含量：La 1.6%，Ce 1.4%，Y 0.3%，Zr 0.9%，Si 30.0%，Al 22.1%，Mg 0.5%，K 1.4%，Fe 0.9%，Ca 0.6%，无Mn、Cr、Pb等重金属离子渗出。
实施例2
将质量比为10:2:5的锆酸镧、碳酸铈、氧化钇混合制备得到稀土复合物。按照质量比100:15:28:0.1的比例称取瓷泥、稀土复合物、水、PVA，依次放入球磨罐中，并使用行星球磨机进行球磨。设置行星球磨机的参数为转速350-400 rpm，旋转时间 15 min，得到低变形率泥浆。泥浆缓慢倒入条状模具中，静置12h成型。将成型的瓷条在110℃下烘干3h，而后以5℃/min的升温速率加热到1150℃煅烧3h，然后缓慢降至室温，得到该陶瓷材料。该样条收缩率为2%，变形量为5mm。按照所述制备方法制成的陶瓷材料，得到以下元素含量：La 3.3%，Ce0.8%，Y 1.2%，Zr 1.8%，Si 31.0%，Al 20.0%，Mg 0.4%，K 1.2%，Fe 1.0%，Ca 0.6%，无Mn、Cr、Pb等重金属离子渗出。
实施例3
将质量比为20:7:10的锆酸镧、碳酸铈、氧化钇混合制备得到稀土复合物。按照质量比100:30:5:0.8的比例称取瓷泥、稀土复合物、水、PVB，依次放入球磨罐中，并使用行星球磨机进行球磨。设置行星球磨机的参数为转速350-400 rpm，旋转时间 15 min，得到低变形率泥浆。泥浆缓慢倒入条状模具中，静置12h成型。将成型的瓷条在110℃下烘干3h，而后以5℃/min的升温速率加热到1150℃煅烧3h，然后缓慢降至室温，得到该陶瓷材料。该样条收缩率为3%，变形量为8mm。按照所述制备方法制成的陶瓷材料，得到以下元素含量：La5.4%，Ce 2.1%，Y 2.8%，Zr 3.0%，Si 33.2%，Al 21.1%，Mg 0.3%，K 0.9%，Fe 1.1%，Ca 0.5%，无Mn、Cr、Pb等重金属离子渗出。
实施例4
将质量比为15:10:3的锆酸镧、碳酸铈、氧化钇混合制备得到稀土复合物。按照质量比100:10:30:1的比例称取瓷泥、稀土复合物、水、硅溶胶，依次放入球磨罐中，并使用行星球磨机进行球磨。设置行星球磨机的参数为转速350-400 rpm，旋转时间 15 min，得到低变形率泥浆。泥浆缓慢倒入条状模具中，静置12h成型。将成型的瓷条在110℃下烘干3h，而后以5℃/min的升温速率加热到1150℃煅烧3h，然后缓慢降至室温，得到该陶瓷材料。该样条收缩率为4%，变形量为12mm。按照所述制备方法制成的陶瓷材料，得到以下元素含量：La1.6%，Y 1.1%，Ce 0.4%，Zr 1.1%，Si 33.1%，Al 22.6%，Mg 0.4%，K 1.3%，Fe 0.9%，Ca 0.6%，P 1.4%，无Mn、Cr、Pb等重金属离子渗出。
实施例5
将质量比为4:5:1的锆酸镧、碳酸铈、氧化钇混合制备得到稀土复合物。按照质量比100:4:10:0.5的比例称取瓷泥、稀土复合物、水、硅溶胶，依次放入球磨罐中，并使用行星球磨机进行球磨。设置行星球磨机的参数为转速350-400 rpm，旋转时间 15 min，得到低变形率泥浆。泥浆缓慢倒入条状模具中，静置12 h成型。将成型的瓷条在110℃下烘干3h，而后以5℃/min的升温速率加热到1150℃煅烧3h，然后缓慢降至室温，得到该陶瓷材料。该样条收缩率为7%，变形量为20mm。按照所述制备方法制成的陶瓷材料，得到以下元素含量：La0.58%，Ce 0.65%，Zr 0.34%，Si 33.1%，Al 22.6%，Mg 0.4%，K 1.3%，Fe 0.9%，Ca 0.6%，P1.4%，无Mn、Cr、Pb等重金属离子渗出。
对比例1
该对比例的泥浆的组分及配比以及陶瓷材料的制备方法与对比例1相同，不同之处在于泥浆的组分和配比为：质量比100:9:25:0.6的比例称取瓷泥、锆酸镧、水、硅溶胶。得到的样条收缩率为9%，变形量为25mm。
对比例2
该对比例的泥浆的组分及配比以及陶瓷材料的制备方法与对比例1相同，不同之处在于泥浆的组分和配比为：质量比100:9:25:0.6的比例称取瓷泥、碳酸铈、水、硅溶胶。得到的样条收缩率为8%，变形量为22mm。
对比例3
该对比例的泥浆的组分及配比以及陶瓷材料的制备方法与对比例1相同，不同之处在于泥浆的组分和配比为：质量比100:9:25:0.6的比例称取瓷泥、氧化钇、水、硅溶胶。得到的样条收缩率为9%，变形量为23mm。
对比例4
该对比例的泥浆的组分及配比以及陶瓷材料的制备方法与对比例1相同，不同之处在于泥浆的组分和稀土复合物配比为：质量比为1:1的锆酸镧、碳酸铈混合制备得到稀土复合物。按照质量比100:9:25:0.6的比例称取瓷泥、稀土复合物、水、硅溶胶。得到的样条收缩率为8%，变形量为22mm。
对比例5
该对比例的泥浆的组分及配比以及陶瓷材料的制备方法与对比例1相同，不同之处在于泥浆的组分和配比为：质量比100:25:0.6的比例称取瓷泥、水、硅溶胶。得到的样条收缩率为11%，变形量为30mm。
由图1可知，锆酸镧、碳酸铈、氧化钇共掺杂改性后的陶瓷有较为明显的莫来石晶相的峰，说明三种物质共掺杂改性陶瓷时，产生了相互作用，更有利于将瓷泥中的铝转化为莫来石相。对比图2和图3我们可以看出，在LaCeY三种元素混合作用下，煅烧的陶瓷生成了棒状的莫来石晶须，而莫来石晶须对瓷泥的层状结构有稳定作用，大大减小了陶瓷的收缩率。
以上所述仅为本发明创造的较佳实施例而已，并不用以限制本发明创造，凡在本发明创造的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明创造的保护范围之内。
Claims (4)
1.一种稀土改性低变形率卫生陶瓷泥料，其特征在于：包括成品瓷泥、稀土复合物、粘结剂和水，稀土复合物的添加量占成品瓷泥质量的4%-40%；粘结剂的添加量占成品瓷泥质量的0.1%-1%；水的添加量占成品瓷泥质量的0.1%-30%；所述稀土复合物由锆酸镧、碳酸铈、氧化钇复配而得；
所述稀土复合物中锆酸镧、碳酸铈、氧化钇的质量比（5-20）： （2-10）：（1-10）；
所述成品瓷泥为高岭土、钠长石、钾长石、粘土中一种或几种的混合物；
所述稀土改性低变形率卫生陶瓷泥料的烧成变形量为20 mm以下。
2.根据权利要求1所述的稀土改性低变形率卫生陶瓷泥料，其特征在于：所述粘结剂为硅溶胶、PVA、PVB中的一种或几种的混合物。
3.权利要求1或2所述的稀土改性低变形率卫生陶瓷泥料的制备方法，其特征在于：包括如下步骤：
称取成品瓷泥、稀土复合物、水、粘结剂依次放入球磨罐中，并使用行星球磨机进行球磨，设置行星球磨机的参数为转速350-400 rpm，旋转时间10-20 min，得到稀土改性低变形率卫生陶瓷泥料。
4.一种低变形率卫生陶瓷，其特征在于：所述陶瓷由权利要求1或2所述的泥料为原料煅烧而成。
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