CN103058630A - Construction ceramic body - Google Patents
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Abstract
本发明涉及一种新型建筑陶瓷坯体，更进一步，涉及一种建筑陶瓷坯体的熔剂系统，属于建筑陶瓷领域。本发明建筑陶瓷坯体，由石英、熔剂、粘土等原料组成，其中,所述的熔剂为一种合成熔剂，该熔剂包含以下组分：以摩尔百分数计，SiO245.0～70.0%，Al2O31.0～8.0%，碱金属氧化物1.0～10.0%，碱土金属氧化物0.0～40.0%，B2O35.0～20.0%。采用本发明合成熔剂等量替代长石熔剂后，建筑陶瓷的外观质量没有任何改变，但烧成温度降低30～80℃，抗弯强度提高30～50%。实现了建筑陶瓷生产低温快速烧成和高性能的完美统一。
The invention relates to a novel building ceramic body, and further relates to a flux system for a building ceramic body, which belongs to the field of building ceramics. The building ceramic body of the present invention is composed of raw materials such as quartz, flux, clay, etc., wherein the flux is a synthetic flux, and the flux contains the following components: by mole percentage, SiO 2 45.0-70.0%, Al 2 O 3 1.0-8.0%, alkali metal oxide 1.0-10.0%, alkaline earth metal oxide 0.0-40.0%, B 2 O 3 5.0-20.0%. After the feldspar flux is replaced by the synthetic flux of the present invention, the appearance quality of architectural ceramics remains unchanged, but the firing temperature is reduced by 30-80°C, and the bending strength is increased by 30-50%. It realizes the perfect unity of low-temperature rapid firing and high performance in the production of architectural ceramics.
Description
技术领域technical field
本发明涉及一种新型建筑陶瓷坯体，更进一步，涉及一种建筑陶瓷坯体的新型熔剂系统，属于建筑陶瓷领域。The invention relates to a novel architectural ceramic body, and further relates to a novel flux system for the architectural ceramic body, which belongs to the field of architectural ceramics.
背景技术Background technique
建筑陶瓷是指用于建筑物饰面或作为建筑构件的陶瓷制品，它是由各种矿物原料及添加的其它原料等按一定的配比经粉碎、混合、成型、或施釉及烧结而成的陶瓷材料。建筑陶瓷除具备抗冲击性、防水性、防污性等常规性能外，近年来还向抗菌性、无放射性、抗噪性等特殊性能方向发展，而且建筑陶瓷造型美观、种类繁多、外观新颖，装饰图案多样化，因而在建筑装饰领域广泛应用。Architectural ceramics refer to ceramic products used for building decoration or as building components. It is made of various mineral raw materials and other added raw materials according to a certain ratio by crushing, mixing, molding, or glazing and sintering. Ceramic material. In addition to conventional properties such as impact resistance, water resistance, and antifouling properties, architectural ceramics have also developed in the direction of special properties such as antibacterial, non-radioactive, and noise resistance in recent years. The decorative patterns are diversified, so they are widely used in the field of architectural decoration.
建筑陶瓷业是建材工业的重要组成部分。与传统陶瓷相比，建筑陶瓷除继承传统陶瓷特性外，还展现出诸多新的性能。然而，建筑陶瓷与其它建材一样，始终未能改变高污染、高能耗、高排放的“三高”局面。The building ceramics industry is an important part of the building materials industry. Compared with traditional ceramics, architectural ceramics not only inherit the characteristics of traditional ceramics, but also exhibit many new properties. However, architectural ceramics, like other building materials, have not been able to change the "three highs" situation of high pollution, high energy consumption, and high emissions.
2007年我国建材工业能源消耗总量1.95亿吨，成为仅次于电力和冶金行业的能源消耗大户，节能降耗形势严峻。这种粗放型增长的工业发展模式将使我国能源、资源和环境不堪重负。In 2007, the total energy consumption of my country's building materials industry was 195 million tons, becoming the second largest energy consumer after the electric power and metallurgical industries, and the situation of energy conservation and consumption reduction is severe. This industrial development model of extensive growth will make my country's energy, resources and environment overwhelmed.
随着时代的发展，特别是节能减排、绿色建筑等社会重大需求的提出，对建筑陶瓷乃至整个建筑材料产业提出了新的要求。迫切需要实现制造过程的清洁节约生产、“三废”减排治理及资源的综合利用，以缓解日益严重的资源、能源和环境危机With the development of the times, especially the proposal of major social demands such as energy saving and emission reduction and green building, new requirements have been put forward for architectural ceramics and even the entire building materials industry. It is urgent to achieve clean and economical production in the manufacturing process, "three wastes" emission reduction treatment and comprehensive utilization of resources to alleviate the increasingly serious crisis of resources, energy and the environment
建筑陶瓷的节能减排措施之一是大力发展节能型产品。在建筑陶瓷节能发展上，许多科技人员做出了大量的研究工作，主要集中在实现建筑陶瓷低温快烧方面，例如，增加熔剂性成分和含量,选用适于快烧的原料(如硅灰石、透辉石)等。One of the energy-saving and emission-reduction measures for building ceramics is to vigorously develop energy-saving products. In the energy-saving development of building ceramics, many scientific and technical personnel have done a lot of research work, mainly focusing on the realization of low-temperature fast burning of building ceramics, for example, increasing the flux component and content, and selecting materials suitable for fast burning (such as wollastonite , diopside), etc.
实现低温快烧是烧成节能的有效途径。高温烧成能耗最高，烧成温度如从1280℃降到1180℃，烧成能耗可降低近30%。Realizing low-temperature fast firing is an effective way to save energy in firing. High temperature firing consumes the most energy. If the firing temperature is lowered from 1280°C to 1180°C, the firing energy consumption can be reduced by nearly 30%.
低温快烧目前国内已取得长足进步。但是，增加熔剂性成分和含量，片面降低烧成温度，也带来了严重的不利影响。大量熔剂产生的高温熔体低温下全部转变为玻璃相，会严重降低建筑陶瓷的理化性能，如强度、热稳定性等，导致产品质量的大幅下滑。Low-temperature fast burning has made great progress in China. However, increasing the flux component and content, one-sidedly lowering the firing temperature, also brought serious adverse effects. The high-temperature melt produced by a large amount of flux will completely transform into a glass phase at a low temperature, which will seriously reduce the physical and chemical properties of architectural ceramics, such as strength and thermal stability, resulting in a sharp decline in product quality.
因此说，建筑陶瓷的低温快烧和产品质量的提高是一对长期困惑产业界的矛盾。Therefore, the low-temperature rapid firing of architectural ceramics and the improvement of product quality are a pair of contradictions that have puzzled the industry for a long time.
发明目的及内容The purpose and content of the invention
本发明的目的在于解决上述现有技术的不足，而提供一种新型建筑陶瓷坯体组成，进一步讲，是提供一种新型熔剂系统，该熔剂系统，一方面可以完全替代长石熔剂实现建筑陶瓷坯体的低温液相烧结，另一方面，在瓷胎冷却过程中，该熔剂可以几乎全部晶化，转变为极细小晶体，这样在不改变建筑陶瓷瓷外观质量的前提下，将建筑陶瓷瓷胎中的玻璃相几乎全部转变为极细小晶体，显著提升其瓷胎的理化性能，尤其是机械强度和热稳定性，从而有效解决了建筑陶瓷的低温快烧和产品质量的提高的矛盾。The purpose of the present invention is to solve the above-mentioned deficiencies in the prior art, and to provide a new type of building ceramic body composition, further speaking, to provide a new type of flux system, the flux system, on the one hand, can completely replace the feldspar flux to realize architectural ceramics Low-temperature liquid-phase sintering of the green body. On the other hand, during the cooling process of the porcelain body, the flux can be almost completely crystallized and transformed into extremely fine crystals. The glass phase in the body is almost completely transformed into very fine crystals, which significantly improves the physical and chemical properties of the body, especially the mechanical strength and thermal stability, thus effectively solving the contradiction between the low-temperature fast firing of building ceramics and the improvement of product quality.
本发明的目的可以通过以下技术措施来实现：The purpose of the present invention can be achieved through the following technical measures:
本发明建筑陶瓷坯体，由石英、熔剂、粘土等原料组成，其中，所述的熔剂为一种合成熔剂，该熔剂包含以下组分：以摩尔百分数计，SiO245.0～70.0%，Al2O31.0～8.0%，碱金属氧化物1.0～10.0%，碱土金属氧化物0.0～40.0%，B2O35.0～20.0%。The building ceramic body of the present invention is composed of raw materials such as quartz, flux, clay, etc., wherein the flux is a synthetic flux, and the flux contains the following components: by mole percentage, SiO 2 45.0-70.0%, Al 2 O 3 1.0-8.0%, alkali metal oxide 1.0-10.0%, alkaline earth metal oxide 0.0-40.0%, B 2 O 3 5.0-20.0%.
或者，所述的熔剂包含以下化学组分：以质量百分数计，SiO245.0～70.0%，Al2O33.0～12.0%，碱金属氧化物2.0～10.0%，碱土金属氧化物0.0～42.0%，B2O35.0～20.0%。Alternatively, the flux includes the following chemical components: by mass percentage, SiO 2 45.0-70.0%, Al 2 O 3 3.0-12.0%, alkali metal oxide 2.0-10.0%, alkaline earth metal oxide 0.0-42.0% , B 2 O 3 5.0～20.0%.
其中，所述的碱金属氧化物为氧化锂、氧化钾、氧化钠中的任意一种或其任意组合；所述的碱土金属氧化物为氧化钙、氧化镁、氧化锌、氧化钡、氧化锶中的任意一种或其任意组合。Wherein, the alkali metal oxide is any one of lithium oxide, potassium oxide, sodium oxide or any combination thereof; the alkaline earth metal oxide is calcium oxide, magnesium oxide, zinc oxide, barium oxide, strontium oxide any one or any combination of them.
另外，本发明所述建筑陶瓷坯体的熔剂还包含二氧化钛、二氧化锆、硅酸锆、氟化钙、骨灰、磷酸钙中的任意一种或其任意组合，其含量以摩尔百分数计为0～10.0%。In addition, the flux of the building ceramic body according to the present invention also contains any one or any combination of titanium dioxide, zirconium dioxide, zirconium silicate, calcium fluoride, bone ash, calcium phosphate, and its content is 0 in mole percent. ~10.0%.
或者，所述的熔剂还包含二氧化钛、二氧化锆、硅酸锆、氟化钙、骨灰、磷酸钙中的任意一种或其任意组合，其含量以质量百分数计为0～15.0%。Alternatively, the flux further includes any one of titanium dioxide, zirconium dioxide, zirconium silicate, calcium fluoride, bone ash, calcium phosphate or any combination thereof, the content of which is 0-15.0% by mass percent.
优化选择，本发明所述建筑陶瓷坯体所用的合成熔剂包含以下组分：以摩尔百分数计，SiO255.0～65.0%，Al2O33.0～6.0%，碱金属氧化物3.0～7.0%，碱土金属氧化物8.0～25.0%，B2O38.0～15.0%。Optimally selected, the synthetic flux used in the building ceramic body of the present invention includes the following components: by mole percentage, SiO 2 55.0-65.0%, Al 2 O 3 3.0-6.0%, alkali metal oxide 3.0-7.0%, Alkaline earth metal oxide 8.0-25.0%, B 2 O 3 8.0-15.0%.
或者，所述的合成熔剂包含以下化学组分：以质量百分数计，SiO250.0～65.0%，Al2O34.5～10.0%，碱金属氧化物4.0～9.0%，碱土金属氧化物10.0～30.0%，B2O39.0～16.0%。Alternatively, the synthetic flux includes the following chemical components: by mass percentage, SiO 2 50.0-65.0%, Al 2 O 3 4.5-10.0%, alkali metal oxide 4.0-9.0%, alkaline earth metal oxide 10.0-30.0% %, B 2 O 3 9.0-16.0%.
本发明所述建筑陶瓷坯体所用的合成熔剂的制备方法是：将所述化学组分对应的各种原料预先混合均匀后，在1250～1650℃温度下熔融、水淬后，便得到所述的合成熔剂。The preparation method of the synthetic flux used in the building ceramic body of the present invention is: after mixing the various raw materials corresponding to the chemical components uniformly in advance, melting at a temperature of 1250-1650 ° C, and water quenching, the described flux is obtained. synthetic flux.
所述的合成熔剂在建筑陶瓷坯体中的用量，以质量百分数计，为5～30%。The amount of the synthetic flux used in the building ceramic body is 5-30% by mass percentage.
本发明与现有技术相比，具有以下技术特点和效果：Compared with the prior art, the present invention has the following technical characteristics and effects:
1、本发明采用SiO2-Al2O3-R2O-RO-B2O3系统为熔剂系统的基础组成，并且辅以各种引晶剂和细晶剂，如TiO2、ZrO2、ZrSiO4、氟化钙、骨灰、磷酸钙，等，既保证了熔剂系统在高温下可以具有长石熔剂相同的烧结行为（熔体高温粘度、高温粘度随温度变化的速率），完全可以替代长石熔剂，实现建筑陶瓷的低温液相烧结，又保证了熔剂系统在瓷胎冷却过程中能够整体析晶，且析出的晶体为极细小晶体，从而保证了本发明目的的实现。1. The present invention adopts the SiO 2 -Al 2 O 3 -R 2 O-RO-B 2 O 3 system as the basic composition of the flux system, and supplemented with various seeding agents and fine crystal agents, such as TiO 2 , ZrO 2 , ZrSiO 4 , calcium fluoride, bone ash, calcium phosphate, etc., which not only ensure that the flux system can have the same sintering behavior as feldspar flux at high temperature (melt viscosity at high temperature, rate of change of viscosity at high temperature with temperature), and can completely replace The feldspar flux realizes low-temperature liquid-phase sintering of architectural ceramics, and ensures that the flux system can crystallize as a whole during the cooling process of the porcelain body, and the precipitated crystals are extremely fine crystals, thereby ensuring the realization of the purpose of the present invention.
本发明合成熔剂的SEM照片、XRD图片和差热-失重曲线见附图所示。The SEM pictures, XRD pictures and differential thermal-weight loss curves of the synthetic flux of the present invention are shown in the accompanying drawings.
2、在建筑陶瓷坯体中，采用本发明合成熔剂等量替代长石熔剂后，建筑陶瓷制品的外观质量没有任何改变，但烧成温度显著降低，实验表明，可以降低30～80℃；烧成过程中瓷胎的变形度降低，有利于瓷胎规整度的提高。2. In the body of architectural ceramics, after the synthetic flux of the present invention is used to replace the feldspar flux in an equivalent amount, the appearance quality of architectural ceramic products does not change, but the firing temperature is significantly reduced. Experiments show that it can be reduced by 30-80°C; The degree of deformation of the porcelain body is reduced during the forming process, which is beneficial to the improvement of the regularity of the porcelain body.
3、采用本发明合成熔剂等量替代长石熔剂后，建筑陶瓷瓷胎的理化性能得到大幅度提高。实验表明，建筑陶瓷的机械抗弯强度可以提高30～50%，性能提高非常显著。3. After the synthetic flux of the present invention is used to replace the feldspar flux in equal amounts, the physical and chemical properties of the building ceramic body are greatly improved. Experiments have shown that the mechanical flexural strength of building ceramics can be increased by 30-50%, and the performance improvement is very significant.
4、实现了建筑陶瓷生产低温节能烧成和高性能的完美统一。4. Realize the perfect unity of low-temperature energy-saving firing and high performance in the production of architectural ceramics.
附图说明Description of drawings
附图1本发明合成熔剂的SEM照片；The SEM photograph of accompanying drawing 1 synthetic flux of the present invention;
附图2本发明合成熔剂的XRD图片；Accompanying drawing 2 is the XRD picture of synthetic flux of the present invention;
附图3本发明合成熔剂的差热-失重曲线。Accompanying drawing 3 is the differential heat-loss curve of the synthetic flux of the present invention.
具体实施方式Detailed ways
下面结合附图对本发明作进一步详细的说明。The present invention will be described in further detail below in conjunction with the accompanying drawings.
实施例1：Example 1:
本发明建筑陶瓷坯体，由石英、熔剂、粘土等原料组成，所述的熔剂为一种合成熔剂，包含以下化学组分：以摩尔百分数计，SiO263.5%，Al2O33.2%，K2O3.1%，CaO4.0%，MgO3.2%，ZnO3.1%，B2O312.7%，氟化钙2.4%，氧化锆4.8%。或者，以质量百分数计，SiO257.0%，Al2O34.8%，K2O4.5%，CaO3.3%，MgO1.9%，ZnO3.9%，B2O313.1%，氟化钙2.7%，氧化锆8.8%。The building ceramic body of the present invention is composed of quartz, flux, clay and other raw materials. The flux is a synthetic flux and contains the following chemical components: SiO 2 63.5%, Al 2 O 3 3.2%, in molar percentages, K 2 O 3.1%, CaO 4.0%, MgO 3.2%, ZnO 3.1%, B 2 O 3 12.7%, Calcium Fluoride 2.4%, Zirconia 4.8%. Or, by mass percentage, SiO 2 57.0%, Al 2 O 3 4.8%, K 2 O 4.5%, CaO 3.3%, MgO 1.9%, ZnO 3.9%, B 2 O 3 13.1%, fluorinated Calcium 2.7%, Zirconia 8.8%.
上述合成熔剂的制备方法是：The preparation method of above-mentioned synthetic flux is:
将上述化学组分首先计算出各自对应的各种原料（以质量百分数计）：The above chemical components are first calculated to correspond to various raw materials (in mass percentage):
钾长石24%，硅灰石6%，滑石5%，锆英石11.5%，硼酸21%，石英24%，硝酸钾2.5%，氧化锌3.5%，萤石2.5%。Potassium feldspar 24%, wollastonite 6%, talc 5%, zircon 11.5%, boric acid 21%, quartz 24%, potassium nitrate 2.5%, zinc oxide 3.5%, fluorite 2.5%.
将上述原料预先混合均匀后，在1380℃温度下熔融、水淬后，便得到所述的建筑陶瓷坯体烧结用熔剂系统。After the above-mentioned raw materials are pre-mixed uniformly, melted at 1380° C., and water-quenched, the flux system for sintering the building ceramic green body is obtained.
本发明合成熔剂的SEM照片、XRD图片和差热-失重曲线见附图1-3所示。The SEM pictures, XRD pictures and differential thermal-weight loss curves of the synthetic flux of the present invention are shown in Figures 1-3.
从附图1可以看出，本发明合成熔剂高温熔体冷却到室温后，几乎全部转变为细小晶体，晶体大小均匀一致，平均在2um左右。As can be seen from accompanying drawing 1, after the high-temperature melt of the synthetic flux of the present invention is cooled to room temperature, it is almost completely transformed into fine crystals, and the crystal size is uniform, with an average of about 2um.
从附图2XRD曲线亦可以看出，本发明合成熔剂高温熔体冷却到室温后，几乎全部转变为晶相，无玻璃相存在。It can also be seen from the XRD curve of accompanying drawing 2 that after the high-temperature melt of the synthetic flux of the present invention is cooled to room temperature, it is almost completely transformed into a crystal phase, and no glass phase exists.
从附图3可以看出，本发明合成熔剂在测试温度范围内（0-1100℃），其差热曲线为一条平滑DTA曲线，无明显放热峰，这说明在测试条件下（0~1100℃），无法找到合成熔剂熔体的析晶起始温度，即合成熔剂熔体在1100℃以上就已经开始析晶，这与本发明预期的高温快速整体析晶相一致。As can be seen from accompanying drawing 3, in the test temperature range (0-1100 ℃) of the synthetic flux of the present invention, its differential thermal curve is a smooth DTA curve, without obvious exothermic peak, which shows that under test conditions (0-1100 ℃ °C), the crystallization initiation temperature of the synthetic flux melt cannot be found, that is, the synthetic flux melt has already begun to crystallize above 1100 °C, which is consistent with the high-temperature rapid overall crystallization expected by the present invention.
其它实施例见下表所示（所有熔剂组成均以摩尔百分数表示）。Other examples are shown in the table below (all flux compositions are expressed in mole percent).
制备工艺同实施例1。The preparation process is the same as in Example 1.
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| CN106751478A (en) * | 2016-11-28 | 2017-05-31 | 江苏雨燕模业科技有限公司 | A kind of mold materials for producing automobile cylinder and preparation method thereof |
| CN107721376A (en) * | 2017-11-07 | 2018-02-23 | 广西壮族自治区黎塘工业瓷厂 | A kind of high-strength ceramic blank of material and preparation method thereof |
| CN107892553A (en) * | 2017-11-07 | 2018-04-10 | 广西壮族自治区黎塘工业瓷厂 | A kind of low deformation ceramic blank of material |
| CN113831114A (en) * | 2021-10-27 | 2021-12-24 | 德化县后井窑瓷业有限责任公司 | A kind of high-strength anti-fall ceramic product and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106751478A (en) * | 2016-11-28 | 2017-05-31 | 江苏雨燕模业科技有限公司 | A kind of mold materials for producing automobile cylinder and preparation method thereof |
| CN107721376A (en) * | 2017-11-07 | 2018-02-23 | 广西壮族自治区黎塘工业瓷厂 | A kind of high-strength ceramic blank of material and preparation method thereof |
| CN107892553A (en) * | 2017-11-07 | 2018-04-10 | 广西壮族自治区黎塘工业瓷厂 | A kind of low deformation ceramic blank of material |
| CN113831114A (en) * | 2021-10-27 | 2021-12-24 | 德化县后井窑瓷业有限责任公司 | A kind of high-strength anti-fall ceramic product and preparation method thereof |
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