CN1668430A - 陶瓷材料平板及面板制造工艺及其产品 - Google Patents

陶瓷材料平板及面板制造工艺及其产品 Download PDF

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CN1668430A
CN1668430A CNA02829551XA CN02829551A CN1668430A CN 1668430 A CN1668430 A CN 1668430A CN A02829551X A CNA02829551X A CN A02829551XA CN 02829551 A CN02829551 A CN 02829551A CN 1668430 A CN1668430 A CN 1668430A
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CN100352636C (zh
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M·通切利
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Maria Luisa Salvaraggio
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Abstract

在按照意大利专利1,311,858中所述真空振动压缩方法制造陶瓷材料平板和面板时，使用粒度小于2.5mm、优选地小于1mm的陶瓷砂和陶瓷粉末与浓度大于24°波美比重计且呈硅酸钠水溶液的粘合添加剂一起形成初始混合物，还在该混合物中加入难熔透明无机材料－优选地为难熔玻璃－纤维。所获得的平板除了不开裂和没有微小裂缝外，还具有改善的机械强度、减少的气孔和改善的美观性。

Description

陶瓷材料平板及面板制造工艺及其产品
技术领域
本发明涉及陶瓷平板制造工艺及其产品。
背景技术
陶瓷平板是已知的，并且以商标Lapitech生产。Lapitech平板的生产使用一种不同于陶瓷领域中所用的传统技术的真空振动压缩法，在现有技术中，通常利用必须产生很高压力的压力机所施加的唯一压力作用而形成平板和面板，这说明了为什么现有技术在所生产的平板或面板的尺寸-实际上非常有限-方面存在限制。
Lapitech工艺构成意大利专利No.1,311,858的主题，并且为了制造陶瓷材料平板而设想制备一由通过天然或陶瓷石料(技术行话也称为“耐火火黏土”或“预焙土”)粒化而获得的优选地为砂状的颗粒和由与水基无机粘合剂混合而具有充分流动性的陶瓷粉末构成的粘结相构成的混合物。
关于该初始混合物的成分，必须指出：
-该颗粒(最大粒度不小于2.5mm)可以由天然材料例如长石、斑岩、花岗岩、黑花岗石、玄武岩组成，但如下所述，它们的应用产生问题，并且优选地使用陶瓷材料例如瓷和粗陶；
-粘结相由陶瓷粉末和耐火粘合剂构成，其中：
(i)陶瓷粉末(粒度小于0.04mm)为与粘土和/或磁土混合的长石、霞石和黑花岗石，和如此获得的还添加有其它成分的混合物。这些粉末经最后烘焙后形成最终平板的连续陶瓷基体。
(ii)该耐火粘合剂优选地由水溶液形式的硅酸钠(可溶玻璃)构成，也可为其它类型的耐火粘合剂，并且在干燥阶段被引入。
在当前实际实现这一工艺的过程中，通常只使用陶瓷砂，因为天然材料的颗粒由于在高温下不稳定而带来困难，这使得实际上无法制造所述产品：热循环期间的尺寸变动或熔合在产品中产生细微裂缝或纹孔。
因此预焙陶瓷砂的使用数量必须能够充分稳定所述产品，即避免可能产生裂缝的过度收缩，所述数量构成接近最终成分的约60％。
通常由上述硅酸钠水溶液构成的粘合添加剂的添加量必须能够填满粉末之间的空隙。
该平板或面板制造工艺包括一成形步骤，在该步骤中，在使混合物振动的同时通过一压力机的撞锤对该混合物加压并产生一定的真空。
对于如此获得的产品，首先进行干燥，然后在高温下烘焙，以得到具有陶瓷材料典型特征的平板。特别是它具有约0.30-0.35％重量百分比的低吸水率。
在干燥阶段，硅酸钠中所含水分蒸发，以使该产品进行约1.1％的线性收缩。在其后的烘焙步骤中，产生5-6％的线性收缩，这意味着总收缩值为约18％体积百分比。
在干燥阶段，形成陶瓷粉末的颗粒由于硅酸钠的作用而粘合在一起，使干燥平板的刚性和强度达到允许该平板被处理的程度；虽然构成预焙土的颗粒互相移近，但非常重要的是它们不会互相接触，因为这可以防止平板进一步收缩而产成裂缝。
迄今为止，为了避免在干燥步骤中出现不希望的裂缝，预焙土颗粒的粒度必须有一范围，其最大值必须优选地大于3mm，即使2.5mm也可接受。
相反，最大粒度小于2-2.5mm时，平板将裂开。
按照貌似有理的说法，进行干燥时陶瓷颗粒具有稳定产品的作用，但粒度减小到小于上述值时将在干燥产品时造成裂缝。
为了避免这一问题，可以考虑在该混合物中加入纤维以强化和稳定该混合物，从而避免在干燥时开裂。因而预焙土在最终合成物中的百分比可以减小到远小于60％重量。
纤维在干燥过程中并因而在初始收缩中起到强化混合物的作用；随着混合物失去水分，无机粘合剂起粘合作用，因此，在干燥步骤结束时平板具有明显的密实性，然后由于粘合剂的难熔性该密实性在烘焙步骤期间在滚子炉(温度高达约1200℃)中得以保持。首先考虑使用有机纤维，它在烘焙步骤开始(约400℃)时由于热量而燃烧并消失；但是所述纤维的缺点是在该材料中产生小凹部，这在(平板)表面上产生明显的外观瑕疵。
为了克服该缺点，还考虑制备成分相同的混合物以形成上下两层，此时将有机纤维加到下层中，而上层不加有机纤维。显然，下层适于形成平板成品的不可见表面(因为该表面上有瑕疵)，而没有瑕疵的上层适于形成平板成品的可见表面。因而得到一合成产品，其中，下层(在干燥阶段)用作上层的支承件，以避免出现裂缝。
显然，相应的工艺较复杂，并且平板成品的机械性能可能不均匀。
后来采用无机纤维如玻璃纤维。但是，即使使用普通玻璃纤维，它们虽然在干燥步骤中起强化作用以避免出现裂缝，但在其后的烘焙中将熔化，从而产生造成瑕疵的可见凹部。
此外，使用具有上述粒度即粒度通常大于2.5mm的陶瓷砂会造成下列缺点：
-在成品中可清楚看到大颗粒的陶瓷砂，并且这对外观有负面影响；
-不能产生显现纹理的效果；
-形成在粉末基体与陶瓷砂颗粒之间的化学键由于缺乏完全兼容性而不是非常坚固，因此其机械强度虽然令人满意但不是很高，抗弯-抗拉强度只有20-25N/mm2。
为了在保持该粒度的同时使外观漂亮，必须使用其颜色与基体颜色相同的砂；但是，在这种情况下，每当要改变颜色时，必须使用颜色不同的砂，因而一方面要改变砂的生产过程，另一方面使生产设备变复杂。
但是，即使使用其颜色与粉末基体颜色相同的砂，颗粒仍然显而易见。
如果减小颗粒度，可以大大减小砂对外观的影响，从而可使用单色-(半透明)透明白-砂并根据所需效果在混合物中加入色料以形成最终颜色。但是，迄今为止，由于平板中如上所述出现裂缝，这尚不可行。
但是，如果使用细砂，平板的机械强度将大大提高。
发明内容
本发明的主要目的是解决上述问题和缺点，特别是使用上述真空振动压缩方法利用预焙陶瓷粉末和砂状陶瓷制造尺寸很大、厚度可能有限的陶瓷材料平板，其中陶瓷砂在平板成品中的含量减小，特别是不大于成品的60-65％体积百分比，而且陶瓷砂的粒度减小到远小于2.5mm。
本发明的一特别目的是使用上述陶瓷粉末制造上述平板，从而一方面改善所得成品的外观，另一方面，不但不会在所制成的平板材料中出现裂纹或裂缝，而且所得材料的机械强度大大提高。
用于陶瓷材料平板制造的本发明工艺可实现这些和其它目的，在该工艺中，制备由数量不大于干燥产品的60％体积的砂状陶瓷材料和由前述陶瓷粉末和作为添加剂的水溶液形式的硅酸钠构成的粘结相构成的混合物，该混合物经受一优选地如意大利专利No.1,311,858所述的真空振动压缩作用，其特征在于：
-所述陶瓷砂的粒度小于2.5mm，优选地小于1mm，甚至较优选地在0.3mm和0.5mm之间；
-所述硅酸钠水溶液的浓度大于24°波美比重计，优选地大于36°波美比重计；以及
-在所述混合物中加入难熔无机透明纤维，优选地为难熔玻璃纤维。
在本发明一优选实施例中，所述难熔玻璃纤维具有在3mm和14mm之间的长度，并且加入初始混合物中的数量为约2％体积百分比。
按照另一实施例，为了制造具有上述特性并且还具有抗压坏性的平板，在制造所述平版时，通过相继在成形模具中分布两层上述成分的混合物、在两层材料之间随机布置不锈钢(可镀镍)钢丝或在烘焙高温下不氧化的金属合金(例如因科内尔合金)丝(长约20mm，直径约0.6mm)而制造所述平板。可选地，也可以使用同种材料制成的抗压坏网。
在上述定义中，术语“难熔纤维”应理解为耐火无机纤维，它在用于烘焙干燥阶段供应的平板的温度下不熔化而是最多软化，因此不会产生造成上述外观瑕疵的效果。此外，具有这些特征的无机纤维在干燥步骤中不会阻止平板收缩。
已证明市场上销售的商标为“Cemfil”的难熔玻璃纤维(具有氧化锆)对于本发明尤其有利。
至于硅酸钠水溶液，根据本发明，已发现当硅酸钠浓度为36°波美比重计时可得到特别有利的结果。
对于干燥阶段的粘合作用，大于48°波美比重计的浓度有利得多，但此时干燥时间大大延长。
最后要指出的是，初始混合物中的陶瓷砂的较小尺寸提高了其与陶瓷粉末(适于形成连续陶瓷基体)的粘附性，并因而提高了产品的机械强度使该机械强度在抗弯-抗拉断裂测试中达到40N/mm2。
此外，陶瓷砂粒度的大幅度减小(在优选实施例中从大于2.5mm减小到0.3-0.5mm)不仅在防止个别陶瓷颗粒在表面上可见这一方面使外观效果大大改善，而且可以获得与天然材料非常类似的显现纹理的效果。
因此，根据本发明，陶瓷材料平板的特征在于其外观由于没有表面瑕疵以及陶瓷颗粒砂不明显而得到改善，但是却具有显现纹理的效果。
而且其特征还在于机械强度得到改善，在抗弯-抗拉断裂试验中该机械强度达到40N/mm2。
该平板的另一重要特征是其气孔减少；实际上它们的吸水率为约0.10％重量百分比。
最后将指出的是，这些平板可以制成尺寸较大，这对于地板和墙面覆层特别有用；在用作墙面覆层时还可以结合在极端情况(例如地震)下防止该平板破裂成从墙上脱落并落到地面上的碎块的抗压坏性。
现在通过非限制性示例提供本发明的两实施例：
示例1
砂/粉末比为60/40的混合物的体积构成：
    36°波美比重计的硅酸钠     22.8％
    陶瓷粉末的混合物     30.0％
    陶瓷砂(粒度0-0.6mm)     45.2％
    “Cemfil”纤维     2.0％
示例2
砂/粉末比为50/50的混合物的体积构成：
    36°波美比重计的硅酸钠     26.5％
    陶瓷粉末的混合物     35.8％
    陶瓷砂(粒度0-0.6mm)     45.2％
    “Cemfil”纤维     2.0％
已结合优选实施例对本发明进行了说明，应该理解的是，概念上等同的改变及变型是可以的并且落入所附权利要求的范围内。
例如，如上所述，可使用也为水溶液形式的其它耐火粘合剂取代硅酸钠水溶液。

Claims (25)

1.陶瓷材料平板及面板制造工艺，在该工艺中，制备一混合物，该混合物的构成为：
-砂状陶瓷材料，其数量以干燥体积计不大于60％，
-由陶瓷粉末和由水溶液形式的硅酸钠构成的添加剂构成的粘结相，
对该混合物施加真空振动压缩作用，其特征在于，在所述混合物中加入体积百分比为至少1.1％的难熔透明无机纤维。
2.按权利要求1所述的工艺，其特征在于，所述陶瓷砂的粒度小于2.5mm。
3.按权利要求2所述的工艺，其特征在于，所述陶瓷砂的粒度小于1mm。
4.按权利要求3所述的工艺，其特征在于，所述陶瓷砂的粒度在0.3mm和0.5mm之间。
5.按权利要求1所述的工艺，其特征在于，所述陶瓷砂为预焙型。
6.按权利要求1所述的工艺，其特征在于，所述硅酸钠水溶液的浓度大于24°波美比重计。
7.按权利要求6所述的工艺，其特征在于，所述硅酸钠水溶液的浓度为36°波美比重计。
8.按权利要求1所述的工艺，其特征在于，所述难熔透明无机纤维为难熔玻璃纤维。
9.按权利要求8所述的工艺，其特征在于，所述难熔玻璃纤维的长度在3mm和14mm之间，并且其添加量为大约2％体积百分比。
10.按权利要求1所述的工艺，其特征在于，为了具有抗压坏性，如此制造所述平板或面板：在成形模具中相继沉积两层混合物并在所述两层混合物之间随机放置不锈钢丝或在烘焙高温下不氧化的金属合金丝。
11.按权利要求10所述的工艺，其特征在于，所述丝的长度为约20mm，直径为约0.6mm。
12.按权利要求10所述的工艺，其特征在于，所述丝由可镀镍的不锈钢制成。
13.按权利要求10所述的工艺，其特征在于，所述丝由因科内尔合金制成。
14.按权利要求10-13中每一项所述的工艺，其特征在于，所述丝呈预制网状。
15.通过烘焙一初始混合物而形成的陶瓷材料平板，该混合物的构成为：
-砂状陶瓷材料，其数量不大于干燥产品的60％体积，
-由陶瓷粉末和由水溶液形式的硅酸钠构成的添加剂构成的粘结相，
其特征在于，在所述混合物中加入体积百分比为至少1.1％的难熔透明无机纤维。
16.按权利要求15所述的陶瓷材料平板，其特征在于，所述陶瓷砂的粒度小于2.5mm。
17.按权利要求16所述的陶瓷材料平板，其特征在于，所述陶瓷砂的粒度小于1mm。
18.按权利要求17所述的陶瓷材料平板，其特征在于，所述陶瓷砂的粒度在0.3mm和0.5mm之间。
19.按权利要求15所述的陶瓷材料平板，其特征在于，所述硅酸钠水溶液的浓度大于24°波美比重计。
20.按权利要求15所述的陶瓷材料平板，其特征在于，所述硅酸钠水溶液的浓度为36°波美比重计。
21.按权利要求15所述的陶瓷材料平板，其特征在于，所述难熔透明无机纤维为难熔玻璃纤维。
22.按权利要求21所述的陶瓷材料平板，其特征在于，所述难熔玻璃纤维的长度在3mm和14mm之间，并且其添加量为约2％体积百分比。
23.按权利要求15所述的具有抗压坏性的陶瓷材料平板，其特征在于，该陶瓷材料平板由两层所述混合物构成，在进行干燥和烘焙之前，在该两层混合物之间随机分布不锈钢丝或在烘焙高温下不氧化的金属合金丝。
24.按权利要求23所述的具有抗压坏性的陶瓷材料平板，其特征在于，所述丝为预制网状。
25.按权利要求15所述的陶瓷材料平板，其特征在于，在抗弯-抗拉断裂测试中，该陶瓷材料平板具有40N/mm2的值和约0.10％重量百分比的吸水率。
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