技术领域Technical field
本发明涉及耐火材料技术领域，具体涉及一种锡槽底砖及其制备方法。The invention relates to the technical field of refractory materials, and in particular to a tin bath bottom brick and a preparation method thereof.
背景技术Background technique
锡槽底砖是浮法成形的关键耐火材料，锡槽底砖等围成的槽池里盛着熔融的锡液，为了保护锡液不被氧化，锡槽内充满了氮氢保护气，玻璃液在锡液上摊开，在拉边机或挡边轮的作用下成形；锡槽底砖的质量的好坏直接影生产的响浮法玻璃质量，发明一种强耐腐蚀性和高保温性的锡槽底砖，使其避免反应层的剥落，不易形成霞石，提高浮法玻璃生产质量并延长锡槽底砖的使用寿命；该锡槽底砖导热系数小，在生产过程中有较高保温性能，可减少生产过程中的能源消耗，具有节能减排的作用。为保证浮法玻璃的生产质量和效率，需要一种综合性能比较好的锡槽底砖。The tin bath bottom brick is the key refractory material for float forming. The tank surrounded by the tin bath bottom bricks and other bricks contains molten tin liquid. In order to protect the tin liquid from being oxidized, the tin bath is filled with nitrogen and hydrogen protective gas. Glass The liquid is spread on the tin liquid and formed under the action of the edge puller or the edge wheel; the quality of the bottom brick of the tin bath directly affects the quality of the float glass produced. Invent a kind of strong corrosion resistance and high thermal insulation The tin bath bottom brick can avoid the peeling off of the reaction layer and prevent the formation of nepheline, improve the quality of float glass production and extend the service life of the tin bath bottom brick; the thermal conductivity of the tin bath bottom brick is small, and it has High thermal insulation performance can reduce energy consumption during the production process and has the effect of energy saving and emission reduction. In order to ensure the production quality and efficiency of float glass, a tin bath bottom brick with better comprehensive performance is needed.
中国发明专利CN1480416A公开了一种锡槽底砖的制作方法，采用高铝水泥作为结合剂，而不采用生粘土，改变基质矿物结构，该方法有效增加了锡槽底砖的闭气孔率，减少霞石化，有效抵抗碱性腐蚀；但该方法会使锡槽底砖的导热系数增加，从而使保温性能有所降低；另一中国发明专利CN104909542A公开了一种锡槽底砖制作方法，该锡槽底砖可有效防止反应层剥落上浮，但其内部组分经过高温烧结使得莫来石相减少，耐高温性能降低。目前所存在的锡槽底砖的性能比较单一。Chinese invention patent CN1480416A discloses a method for making tin bath bottom bricks. It uses high alumina cement as the binding agent instead of raw clay to change the matrix mineral structure. This method effectively increases the closed porosity of the tin bath bottom bricks and reduces nepheline, which effectively resists alkaline corrosion; however, this method will increase the thermal conductivity of the tin bath bottom brick, thereby reducing the thermal insulation performance; another Chinese invention patent CN104909542A discloses a method for making tin bath bottom bricks. The bottom brick of the tank can effectively prevent the reaction layer from peeling off and floating, but its internal components are sintered at high temperature, which reduces the mullite phase and reduces the high temperature resistance. The performance of the currently existing tin bath bottom bricks is relatively single.
综上所述，急需通过改变各成分配比、结合剂与添加剂的成分以及改变硅铝熟料的加工方法，以此来获得一种新型的强耐蚀型和高温使用性的锡槽底砖及其制备方法。In summary, there is an urgent need to obtain a new type of tin bath bottom brick with strong corrosion resistance and high temperature usability by changing the proportion of each component, the composition of binders and additives, and changing the processing method of silicon-aluminum clinker. and preparation method thereof.
发明内容Contents of the invention
本发明目的在于提供一种具有强耐蚀型和高温使用性的锡槽底砖及其制备方法，应用本发明中的锡槽底砖能够提高锡槽使用寿命和热效率，达到节能的效果。The purpose of the present invention is to provide a tin bath bottom brick with strong corrosion resistance and high temperature usability and a preparation method thereof. The use of the tin bath bottom brick in the present invention can improve the service life and thermal efficiency of the tin bath and achieve energy saving effects.
为了实现上述目的，本发明锡槽底砖采用的技术方案如下：In order to achieve the above object, the technical solution adopted by the tin bath bottom brick of the present invention is as follows:
一种锡槽底砖，包括以下重量份数的原料制成：硅铝熟料60～80份、纯铝酸钙水泥1～5份、高铝细粉6～20份、粘土粉2～4份、硅微粉1～5份、减水剂0.1～0.3份。A tin bath bottom brick is made of the following raw materials in parts by weight: 60 to 80 parts of silicon-alumina clinker, 1 to 5 parts of pure calcium aluminate cement, 6 to 20 parts of high alumina fine powder, and 2 to 4 parts of clay powder parts, 1 to 5 parts of silica powder, and 0.1 to 0.3 parts of water reducing agent.
优选的，所述原料还包括硅溶胶1～3份、铝溶胶1～3份。所述硅溶胶SiO2的质量分数为30～35％，颗粒大小在10～20纳米。所述铝溶胶Al2O3的质量分数为20～25％，颗粒大小在50～70纳米。在原料中采用的硅溶胶和铝溶胶是耐火性很强的粘合剂，能够使各原料组成能结合在一起，不会使各原料组成在高温烧结使脱落，使锡槽底砖具有较强的耐蚀性。Preferably, the raw materials further include 1 to 3 parts of silica sol and 1 to 3 parts of aluminum sol. The mass fraction of the silica sol SiO2 is 30-35%, and the particle size is 10-20 nanometers. The aluminum sol Al2 O3 has a mass fraction of 20 to 25% and a particle size of 50 to 70 nanometers. The silica sol and aluminum sol used in the raw materials are highly fire-resistant adhesives, which can bind the raw material components together and prevent them from falling off due to sintering at high temperatures, making the tin bath bottom bricks have a strong corrosion resistance.
优选的，所述硅铝熟料的体积密度为2.2～2.4g/cm3。将硅铝熟料的体积密度控制在上述范围之内，能够使本锡槽底砖的硅铝熟料相较于其他普通的硅铝熟料流动性更好，同时也使显气孔率在合适的范围内，有利于提高锡槽底砖的耐蚀性，不会使材料在高温及长期使用中发生损坏，延长使用寿命。Preferably, the bulk density of the silicon-alumina clinker is 2.2-2.4g/cm3 . Controlling the volume density of the silicon-alumina clinker within the above range can make the silicon-alumina clinker of this tin bath bottom brick have better fluidity than other ordinary silicon-alumina clinkers, and also keep the apparent porosity at an appropriate level. Within the range, it is conducive to improving the corrosion resistance of the tin bath bottom brick, preventing the material from being damaged at high temperatures and long-term use, and extending the service life.
优选的，所述硅铝熟料中Al2O3的质量分数为48～75％，Fe2O3的质量分数不大于0.8％。将硅铝熟料的Al2O3和Fe2O3控制在上述范围内，能够降低硅铝熟料的体积密度和导热系数，使锡槽底砖更加轻量化、导热系数减小，能提高锡槽底砖的保温性。Preferably, the mass fraction of Al2 O3 in the silicon-alumina clinker is 48 to 75%, and the mass fraction of Fe2 O3 is not more than 0.8%. Controlling the Al2 O3 and Fe2 O3 of the silicon-alumina clinker within the above range can reduce the volume density and thermal conductivity of the silicon-alumina clinker, make the tin bath bottom bricks lighter, reduce the thermal conductivity, and improve Thermal insulation of tin bath bottom bricks.
优选的，所述硅铝熟料由包括以下步骤制得：Preferably, the silicon-alumina clinker is prepared by including the following steps:
(1)将配料搅拌均匀混合，得到均匀混合物料，所述配料包括以下重量份数的材料：高岭土细粉50～70份、粘土细粉15～25份、工业氧化铝细粉14～22份、重量矿化剂1～3份、水7～13份；(1) Stir the ingredients evenly to obtain a uniform mixture. The ingredients include the following parts by weight: 50 to 70 parts of kaolin fine powder, 15 to 25 parts of clay fine powder, and 14 to 22 parts of industrial alumina fine powder. , 1 to 3 parts of mineralizer and 7 to 13 parts of water by weight;
(2)将均匀混合物料通过挤压成型制作成坯体；(2) Make the uniform mixture of materials into a green body through extrusion molding;
(3)将坯体在100～120℃烘干，再在1400～1600℃烧制11～13h；(3) Dry the green body at 100~120℃, and then fire it at 1400~1600℃ for 11~13h;
(4)将烧制后的坯体粉碎，筛选，则获得硅铝熟料成品。(4) The fired green body is crushed and screened to obtain the finished silicon-alumina clinker product.
将烧制的温度控制在1500℃更有利于各组分进行均匀的相变，使得组织结构连结更加紧密。Controlling the firing temperature at 1500°C is more conducive to the uniform phase transformation of each component, making the organizational structure more closely connected.
优选的，在1400～1600℃烧制11～13h在梭式窑中进行，可使坯体在烧成过程中受热均匀。Preferably, the firing is carried out in a shuttle kiln at 1400-1600°C for 11-13 hours, so that the green body can be heated evenly during the firing process.
优选的，所述纯铝酸钙水泥中Al2O3的质量分数75～85％，且Al2O3能够与水反应生成Al-OH键，能够增强材料的强度，纯铝酸钙水泥中Al2O3的含量较高且适中，能够使材料的强度和稳定性都有所提高。Preferably, the mass fraction of Al2 O3 in the pure calcium aluminate cement is 75 to 85%, and Al2 O3 can react with water to form Al-OH bonds, which can enhance the strength of the material. In pure calcium aluminate cement, The content of Al2 O3 is high and moderate, which can improve the strength and stability of the material.
优选的，本发明的锡槽底砖主要由以下重量份数的原料制成：硅铝熟料60～80份、纯铝酸钙水泥1～5份、高铝细粉6～20份、粘土粉1～4份、硅微粉1～5份、减水剂0.1～0.3份；所述硅铝熟料由粒径不大于1mm的小粒径硅铝熟料、粒径大于1mm且不大于3mm的中等粒径硅铝熟料和粒径大于3mm且不大于5mm的大粒径硅铝熟料组成；所述小粒径硅铝熟料、中等粒径硅铝熟料和大粒径硅铝熟料的质量比为0.6～1.1：0.9～1.2。采用上述颗粒级配的硅铝熟料能够使材料的内部结构更稳定。Preferably, the tin bath bottom brick of the present invention is mainly made of the following raw materials in parts by weight: 60 to 80 parts of silicon-alumina clinker, 1 to 5 parts of pure calcium aluminate cement, 6 to 20 parts of high alumina fine powder, clay 1 to 4 parts of powder, 1 to 5 parts of silica powder, and 0.1 to 0.3 parts of water-reducing agent; the silicon-aluminum clinker is composed of small-particle silicon-alumina clinker with a particle size of no more than 1 mm, and a particle size of more than 1 mm and no more than 3 mm. It is composed of medium particle size silicon aluminum clinker and large particle size silicon aluminum clinker with a particle size greater than 3 mm and not greater than 5 mm; the small particle size silicon aluminum clinker, medium particle size silicon alumina clinker and large particle size silicon alumina The mass ratio of clinker is 0.6~1.1:0.9~1.2. Using the silicon-aluminum clinker with the above particle gradation can make the internal structure of the material more stable.
另外，本发明还提出了一种上述锡槽底砖的制备方法，技术方案如下：In addition, the present invention also proposes a method for preparing the above-mentioned tin bath bottom brick. The technical solution is as follows:
一种锡槽底砖制备方法，步骤如下：A method for preparing tin bath bottom bricks, the steps are as follows:
(1)称取指定份量各原料并加入水搅拌混合混匀；(1) Weigh the specified amount of each raw material and add water and stir to mix;
(2)在温度为15～20℃的环境下，通过浇注振动成型获得坯体，然后将坯体放在烘烤窑里，以2℃/小时的升温速度升到150℃，然后保温24h进行烘干；(2) In an environment with a temperature of 15 to 20°C, obtain a green body through pouring and vibration molding, then place the green body in a baking kiln, raise it to 150°C at a temperature rise rate of 2°C/hour, and then keep it warm for 24 hours. drying;
(3)烘干后的坯体分四阶段进行烧制，第一阶段以3℃/小时的升温速度从150℃升到350℃，保温24h；第二阶段以5℃/小时的升温速度从350℃升到600℃，保温24h；第三阶段以10℃/小时的升温速度从600℃升到900℃，保温12h；第四阶段以10℃/小时的升温速度从900℃升到1200～1300℃，保温24h得到烧制品；(3) The dried green body is fired in four stages. In the first stage, the temperature rises from 150℃ to 350℃ at a rate of 3℃/hour and is kept warm for 24 hours. In the second stage, the temperature rises from 150℃ to 350℃ at a temperature rise rate of 5℃/hour. 350℃ to 600℃, keep warm for 24 hours; in the third stage, raise the temperature from 600℃ to 900℃ at a heating rate of 10℃/hour, and keep it warm for 12 hours; in the fourth stage, raise the temperature from 900℃ to 1200℃ at a heating rate of 10℃/hour. 1300℃, heat preservation for 24h to obtain fired products;
(4)将烧制品切割打磨成规整形状，打包成品。(4) Cut and polish the fired products into regular shapes and package the finished products.
本发明锡槽底砖的制备方法工艺流程简单，生产成本低，可靠性高，实用性好。The preparation method of tin bath bottom bricks of the present invention has simple technological process, low production cost, high reliability and good practicability.
优选的，烘干后的坯体在隧道窑中进行烧制。隧道窑内的烧制温度很稳定，可减少能耗，而且还能使锡槽底砖稳定的进行微观结构重组，避免热应力集中。Preferably, thedried green body is fired in a tunnel kiln. The firing temperature in the tunnel kiln is very stable, which can reduce energy consumption, and also allows the tin bath bottom bricks to reorganize their microstructure stably to avoid thermal stress concentration.
应用本发明的技术方案，具有以下有益效果：Applying the technical solution of the present invention has the following beneficial effects:
(1)在本发明中，锡槽底砖以硅铝熟料为主要原料，通过添加纯铝酸钙水泥、高铝细粉、粘土粉、硅溶胶、铝溶胶和减水剂，各原料合理调配、协同作用，减少水泥的使用，增加硅铝溶胶的使用，使锡槽底砖具有较适当的体积密度、较低的显气孔率、较好的高温使用性能；由于减少矿物质的使用，改变了底砖基质的矿物结构，使锡槽底砖具有霞石化降低的特性、使用寿命延长；同时具有较低的导热系数、保温效果好，减少热损失，能够显著提高热利用效率，实现节能减排的目的。(1) In the present invention, the tin bath bottom brick uses silica-alumina clinker as the main raw material. By adding pure calcium aluminate cement, high-aluminum fine powder, clay powder, silica sol, aluminum sol and water-reducing agent, each raw material is reasonably Mixing and synergy reduce the use of cement and increase the use of silica-alumina sol, so that the tin bath bottom bricks have a more appropriate volume density, lower apparent porosity, and better high-temperature performance; due to the reduced use of minerals, The mineral structure of the bottom brick matrix is changed, so that the tin bath bottom brick has the characteristics of reducing nepheline and extending the service life; at the same time, it has a lower thermal conductivity, good thermal insulation effect, reduces heat loss, can significantly improve the heat utilization efficiency, and achieve energy saving. the purpose of reducing emissions.
(2)在本发明中，锡槽底砖的纯铝酸钙水泥含量较少，从而可以减少水泥带入较多的CaO，在高温烧结过程中可以适当增加莫来石相，使其高温使用性能增强。作为结合剂，少量使用可减少杂质引入，从而使锡槽底砖的各组分高温结合性能更好和避免高温使用过程中玻璃液渗入气孔与其它组分发生反应，产生霞石，腐蚀锡槽底砖，并可减少其表面层脱落。(2) In the present invention, the tin bath bottom brick has less pure calcium aluminate cement content, which can reduce the amount of CaO brought into the cement. During the high-temperature sintering process, the mullite phase can be appropriately increased to enable high-temperature use. Performance enhancements. As a binding agent, a small amount of use can reduce the introduction of impurities, thereby making the high-temperature bonding performance of each component of the tin bath bottom brick better and preventing the glass liquid from penetrating into the pores and reacting with other components during high-temperature use to produce nepheline and corrode the tin bath. Bottom bricks, and can reduce the shedding of the surface layer.
(3)在本发明中，硅溶胶与铝溶胶作为结合剂在制备锡槽底砖时产生的作用是，烧结过程实现铝溶胶中的活性Al2O3与硅溶胶和材料中的SiO2反应或烧结过程实现硅溶胶中的活性SiO2与铝溶胶和材料中的Al2O3反应，提高材料的抗震效果和耐高温性；其中含有Al-OH键和Si-OH键，能够提高材料强度；同时硅溶胶和铝溶胶具有较强的粘结性，可使各组分粘结强度进一步提高。(3) In the present invention, the role of silica sol and aluminum sol as binding agents in preparing tin bath bottom bricks is that the sintering process realizes the reaction between the active Al2 O3 in the aluminum sol and the SiO2 in the silica sol and material. Or during the sintering process, the active SiO2 in the silica sol reacts with the aluminum sol and Al2 O3 in the material to improve the material's earthquake resistance and high temperature resistance; it contains Al-OH bonds and Si-OH bonds, which can improve the material strength ; At the same time, silica sol and aluminum sol have strong adhesion, which can further improve the bonding strength of each component.
(4)在本发明中，所述硅铝熟料中Al2O3的质量分数为48～75％，Fe2O3的质量分数不大于0.8％。将硅铝熟料的Al2O3和Fe2O3控制在上述范围内，能够降低硅铝熟料的体积密度和导热系数，使锡槽底砖更加轻量化、导热系数减小，能提高锡槽底砖的保温性。(4) In the present invention, the mass fraction of Al2 O3 in the silicon-alumina clinker is 48 to 75%, and the mass fraction of Fe2 O3 is not more than 0.8%. Controlling the Al2 O3 and Fe2 O3 of the silicon-alumina clinker within the above range can reduce the volume density and thermal conductivity of the silicon-alumina clinker, make the tin bath bottom bricks lighter, reduce the thermal conductivity, and improve Thermal insulation of tin bath bottom bricks.
(5)在本发明中，所述硅溶胶SiO2的质量分数为30～35％，颗粒大小在10～20纳米。所述铝溶胶Al2O3的质量分数为20～25％，颗粒大小在50～70纳米。将硅溶胶的SiO2和铝溶胶的Al2O3控制在上述范围内，能够使各原料组成能结合在一起，不会使各原料组成在高温烧结使脱落，使锡槽底砖具有较强的耐蚀性。(5) In the present invention, the mass fraction of the silica sol SiO2 is 30 to 35%, and the particle size is 10 to 20 nanometers. The aluminum sol Al2 O3 has a mass fraction of 20 to 25% and a particle size of 50 to 70 nanometers. Controlling the SiO2 of the silica sol and the Al2 O3 of the aluminum sol within the above range can enable the raw material components to be combined together without causing the raw material components to fall off during high-temperature sintering, making the tin bath bottom bricks have stronger corrosion resistance.
(6)在本发明中，所述硅铝熟料的体积密度为2.2～2.4g/cm3。将硅铝熟料的体积密度控制在上述范围之内，能够使本锡槽底砖的硅铝熟料相较于其他普通的硅铝熟料流动性更好，同时也使显气孔率在合适的范围内，有利于提高锡槽底砖的耐蚀性，不会使材料在高温及长期使用中发生损坏，延长使用寿命。(6) In the present invention, the bulk density of the silicon-alumina clinker is 2.2-2.4g/cm3 . Controlling the volume density of the silicon-alumina clinker within the above range can make the silicon-alumina clinker of this tin bath bottom brick have better fluidity than other ordinary silicon-alumina clinkers, and also keep the apparent porosity at an appropriate level. Within the range, it is conducive to improving the corrosion resistance of the tin bath bottom brick, preventing the material from being damaged at high temperatures and long-term use, and extending the service life.
(7)在本发明中，锡槽底砖坯体的制备方法采用振动浇注成型法，此方法相较于机压法的锡槽底砖的制备方法，排气效果较好，避免锡槽底砖内部发生断裂，增加锡槽底砖的强度；相较于捣打法的制备方法，可以有效解决锡槽底砖内部分层，发生层裂，导致锡槽地砖的组织结构不均匀，减小强度，相较于石膏模浇注法，有效避免坯体硬化和造成坯体断面出现裂纹增加成品率，减小成本。(7) In the present invention, the preparation method of the tin bath bottom brick body adopts vibration casting method. Compared with the preparation method of the tin bath bottom brick by machine pressing method, this method has better exhaust effect and avoids the problem of tin bath bottom brick. Internal fractures will increase the strength of the tin bath floor tiles; compared with the preparation method of ramming, it can effectively solve the internal delamination and cracking of the tin bath floor tiles, resulting in uneven organizational structure of the tin bath floor tiles and reducing the strength. , compared with the plaster mold casting method, it can effectively avoid the hardening of the body and cracks in the cross section of the body, increase the yield and reduce the cost.
具体实施方式Detailed ways
以下结合具体实施方式对本发明的技术方案作进一步的说明。The technical solution of the present invention will be further described below in conjunction with specific implementation modes.
实施例1：Example 1:
本实施例公开了一种锡槽底砖及其制备方法，所述锡槽底砖包括以下重量份数的组分：硅铝熟料70份、纯铝酸钙水泥(主要成分为Al2O3，其中Al2O3含量为78～85％)5份、高铝细粉(主要成分为Al2O3，其中Al2O3含量为86～88％)18份、粘土粉(高岭石类)3份、硅微粉(主要成分为SiO2，其中SiO2含量不低于99％)2份、硅溶胶2份、铝溶胶1份、减水剂0.1份；This embodiment discloses a tin bath bottom brick and a preparation method thereof. The tin bath bottom brick includes the following components by weight: 70 parts of silicon-alumina clinker, pure calcium aluminate cement (main component is Al2 O3 , of which the Al2 O3 content is 78 to 85%), 5 parts of high-aluminum fine powder (the main component is Al2 O3 , of which the Al2 O3 content is 86 to 88%), 18 parts of clay powder (kaolin Stones) 3 parts, 2 parts of silica powder (the main component is SiO2 , of which the SiO2 content is not less than 99%), 2 parts of silica sol, 1 part of aluminum sol, and 0.1 part of water reducing agent;
所采用的不同粒径硅铝熟料的重量份数：粒径为0.1～1mm的硅铝熟料为20份、粒径大于1mm且不大于3mm的硅铝熟料为25份，粒径大于3mm且不大于5mm的硅铝熟料为25份；The parts by weight of silicon-alumina clinker with different particle sizes used: 20 parts for silicon-alumina clinker with a particle size of 0.1 to 1 mm, 25 parts for silicon-alumina clinker with a particle size greater than 1 mm and not greater than 3 mm, and 25 parts for silicon-alumina clinker with a particle size greater than 1 mm. 25 parts for silicon-aluminum clinker of 3mm and not larger than 5mm;
本实施例的锡槽底砖制备方法，包括以下步骤：The preparation method of tin bath bottom bricks in this embodiment includes the following steps:
(1)取配方量的各原料，加入原料总质量6％的水搅拌混匀；(1) Take the formula amount of each raw material, add 6% water of the total mass of the raw materials, and mix well;
(2)浇注到模具中振动成型，成型之后，脱模，得到坯体；然后将坯体放在烘烤窑里，用150℃温度烘干24h；(2) Pour into the mold and vibrate for molding. After molding, demould to obtain a green body; then place the green body in a baking kiln and dry it at 150°C for 24 hours;
(3)然后放入隧道窑中1200℃烧制24h；(3) Then put it into a tunnel kiln and bake it at 1200°C for 24 hours;
(4)最后进行切割、打磨，包装。(4)Finally cutting, polishing and packaging.
本发明还提供了实施例2～5，所述实施例2～5与实施例1的区别在于：(1)各组分的重量份数不同；(2)采用小径、中径和大径3种不同粒径硅铝熟料的重量份数不同；(3)在隧道窑中烧制温度不同；具体参见表1、表2和表3：The present invention also provides Examples 2 to 5. The difference between Examples 2 to 5 and Example 1 is that: (1) the weight parts of each component are different; (2) the use of small diameter, medium diameter and large diameter 3 The weight portions of silicon-alumina clinker with different particle sizes are different; (3) the firing temperatures in the tunnel kiln are different; see Table 1, Table 2 and Table 3 for details:
表1本发明中实施例1～5提供的锡槽底砖各组分的重量份数Table 1 The weight parts of each component of the tin bath bottom brick provided in Examples 1 to 5 of the present invention
表2本发明中实施例1～5采用不同粒径硅铝熟料的重量份数Table 2 The weight parts of silicon-alumina clinker with different particle sizes used in Examples 1 to 5 of the present invention
表3锡槽底砖在隧道窑中烧制温度Table 3 Firing temperatures of tin bath bottom bricks in tunnel kiln
实施例2：Example 2:
本实施例公开了一种锡槽底砖及其制备方法，所述锡槽底砖由以下重量份数的组分组成：硅铝熟料70份、纯铝酸钙水泥2份、高铝细粉16份、粘土粉3份、硅微粉3份、硅溶胶3份、铝溶胶3份、减水剂0.1份；This embodiment discloses a tin bath bottom brick and a preparation method thereof. The tin bath bottom brick is composed of the following components by weight: 70 parts of silicon-alumina clinker, 2 parts of pure calcium aluminate cement, high-aluminum fine 16 parts of powder, 3 parts of clay powder, 3 parts of silica powder, 3 parts of silica sol, 3 parts of aluminum sol, 0.1 part of water reducing agent;
所采用的不同粒径硅铝熟料的重量份数：粒径为0.1～1mm的硅铝熟料为15份、粒径大于1mm且不大于3mm的硅铝熟料为25份，粒径大于3mm且不大于5mm的硅铝熟料为30份；The parts by weight of silicon-alumina clinker with different particle sizes used: 15 parts for silicon-alumina clinker with a particle size of 0.1 to 1 mm, 25 parts for silicon-alumina clinker with a particle size greater than 1 mm and not greater than 3 mm, and 25 parts for silicon-alumina clinker with a particle size greater than 1 mm. 30 parts for silicon-aluminum clinker of 3mm and not larger than 5mm;
本实施例的锡槽底砖制备方法和实施例1相同，此处不再赘述。The preparation method of the tin bath bottom brick in this embodiment is the same as that in Embodiment 1, and will not be described again here.
实施例3：Example 3:
本实施例公开了一种锡槽底砖及其制备方法，所述锡槽底砖由以下重量份数的组分组成：硅铝熟料70份、纯铝酸钙水泥3份、高铝细粉13份、粘土粉4份、硅微粉5份、硅溶胶2份、铝溶胶3份、减水剂0.1份；This embodiment discloses a tin bath bottom brick and a preparation method thereof. The tin bath bottom brick is composed of the following components by weight: 70 parts of silicon-alumina clinker, 3 parts of pure calcium aluminate cement, high-aluminum fine 13 parts of powder, 4 parts of clay powder, 5 parts of silica powder, 2 parts of silica sol, 3 parts of aluminum sol, 0.1 part of water reducing agent;
所采用的不同粒径硅铝熟料的重量份数：粒径为0.1～1mm的硅铝熟料为20份、粒径大于1mm且不大于3mm的硅铝熟料为20份，粒径大于3mm且不大于5mm的硅铝熟料为30份；The parts by weight of silicon-alumina clinker with different particle sizes used: 20 parts for silicon-alumina clinker with a particle size of 0.1 to 1 mm, 20 parts for silicon-alumina clinker with a particle size greater than 1 mm and not greater than 3 mm, and 20 parts for silicon-alumina clinker with a particle size greater than 1 mm. 30 parts for silicon-aluminum clinker of 3mm and not larger than 5mm;
本实施例的锡槽底砖制备方法和实施例1相同，此处不再赘述。The preparation method of the tin bath bottom brick in this embodiment is the same as that in Embodiment 1, and will not be described again here.
实施例4：Example 4:
本实施例公开了一种锡槽底砖及其制备方法，所述锡槽底砖由以下重量份数的组分组成：硅铝熟料75份、纯铝酸钙水泥3份、高铝细粉11份、粘土粉3份、硅微粉4份、硅溶胶1份、铝溶胶2份、减水剂0.1份；This embodiment discloses a tin bath bottom brick and a preparation method thereof. The tin bath bottom brick is composed of the following components by weight: 75 parts of silicon-alumina clinker, 3 parts of pure calcium aluminate cement, high-aluminum fine 11 parts of powder, 3 parts of clay powder, 4 parts of silica powder, 1 part of silica sol, 2 parts of aluminum sol, 0.1 part of water reducing agent;
所采用的不同粒径硅铝熟料的重量份数：粒径为0.1～1mm的硅铝熟料为20份、粒径大于1mm且不大于3mm的硅铝熟料为25份，粒径大于3mm且不大于5mm的硅铝熟料为30份；The parts by weight of silicon-alumina clinker with different particle sizes used: 20 parts for silicon-alumina clinker with a particle size of 0.1 to 1 mm, 25 parts for silicon-alumina clinker with a particle size greater than 1 mm and not greater than 3 mm, and 25 parts for silicon-alumina clinker with a particle size greater than 1 mm. 30 parts for silicon-aluminum clinker of 3mm and not larger than 5mm;
本实施例中的锡槽底砖制备方法，包括以下步骤：The tin bath bottom brick preparation method in this embodiment includes the following steps:
(1)取配方量的各原料，加入原料总质量6％的水搅拌混匀；(1) Take the formula amount of each raw material, add 6% water of the total mass of the raw materials, and mix well;
(2)浇注到模具中振动成型，成型之后，脱模，得到坯体；然后将坯体放在烘烤窑里，用150℃温度烘干24h；(2) Pour into the mold and vibrate for molding. After molding, demould to obtain a green body; then place the green body in a baking kiln and dry it at 150°C for 24 hours;
(3)然后放入隧道窑中1250℃烧制24h；(3) Then put it into a tunnel kiln and bake it at 1250℃ for 24 hours;
(4)最后进行切割、打磨，包装。(4)Finally cutting, polishing and packaging.
实施例5：Example 5:
本实施例公开了一种锡槽底砖及其制备方法，所述锡槽底砖由以下重量份数的组分组成：硅铝熟料75份、纯铝酸钙水泥2份、高铝细粉13份、粘土粉2份、硅微粉3份、硅溶胶3份、铝溶胶2份、减水剂0.1份；This embodiment discloses a tin bath bottom brick and a preparation method thereof. The tin bath bottom brick is composed of the following components by weight: 75 parts of silicon-alumina clinker, 2 parts of pure calcium aluminate cement, high-aluminum fine 13 parts of powder, 2 parts of clay powder, 3 parts of silica powder, 3 parts of silica sol, 2 parts of aluminum sol, 0.1 part of water reducing agent;
所采用的不同粒径硅铝熟料的重量份数：粒径为0.1～1mm的硅铝熟料为20份、粒径大于1mm且不大于3mm的硅铝熟料为25份，粒径大于3mm且不大于5mm的硅铝熟料为30份；The parts by weight of silicon-alumina clinker with different particle sizes used: 20 parts for silicon-alumina clinker with a particle size of 0.1 to 1 mm, 25 parts for silicon-alumina clinker with a particle size greater than 1 mm and not greater than 3 mm, and 25 parts for silicon-alumina clinker with a particle size greater than 1 mm. 30 parts for silicon-aluminum clinker of 3mm and not larger than 5mm;
本实施例中的锡槽底砖制备方法，包括以下步骤：The tin bath bottom brick preparation method in this embodiment includes the following steps:
(1)取配方量的各原料，加入原料总质量6％的水搅拌混匀；(1) Take the formula amount of each raw material, add 6% water of the total mass of the raw materials, and mix well;
(2)浇注到模具中振动成型，成型之后，脱模，得到坯体；然后将坯体放在烘烤窑里，用150℃温度烘干24h；(2) Pour into the mold and vibrate for molding. After molding, demould to obtain a green body; then place the green body in a baking kiln and dry it at 150°C for 24 hours;
(3)然后放入隧道窑中1300℃烧制24h；(3) Then put it into a tunnel kiln and bake it at 1300°C for 24 hours;
(4)最后进行切割、打磨，包装。(4)Finally cutting, polishing and packaging.
对比例1：Comparative example 1:
在实施例1的基础上，提供对比例1，对比例1与实施例1的区别主要在于：硅铝熟料的制备方法不同。On the basis of Example 1, Comparative Example 1 is provided. The difference between Comparative Example 1 and Example 1 mainly lies in the preparation method of silicon-alumina clinker.
对比例1中硅铝熟料的制备方法如下：The preparation method of silicon-aluminum clinker in Comparative Example 1 is as follows:
(1)烧制：以天然的煤矸石块为原料经过1400℃烧制12h后；(1) Firing: Using natural coal gangue blocks as raw materials, after firing at 1400°C for 12 hours;
(2)获得成品：将烧制的坯体粉碎，筛选，则获得硅铝熟料成品。(2) Obtain the finished product: crush and screen the fired body to obtain the finished silicon-aluminum clinker product.
对比例2：Comparative example 2:
在实施例2的基础上，提供对比例2，对比例2与实施例2的区别主要在于：锡槽底砖各组分和不同粒径硅铝熟料的重量份数不同。On the basis of Example 2, Comparative Example 2 is provided. The main difference between Comparative Example 2 and Example 2 is that the weight parts of each component of the tin bath bottom brick and the silicon-alumina clinker of different particle sizes are different.
本对比例的锡槽底砖，由以下重量份数的组分组成：硅铝熟料65份、纯铝酸钙水泥8份、高铝细粉15份、粘土粉3份、硅微粉2份、硅溶胶1份、铝溶胶1份、减水剂0.2份；The tin bath bottom brick of this comparative example is composed of the following components by weight: 65 parts of silica-alumina clinker, 8 parts of pure calcium aluminate cement, 15 parts of high-aluminum fine powder, 3 parts of clay powder, and 2 parts of silica powder , 1 part of silica sol, 1 part of aluminum sol, 0.2 part of water reducing agent;
所采用的不同粒径硅铝熟料的重量份数：粒径为0.1～1mm的硅铝熟料为20份、粒径大于1mm且不大于3mm的硅铝熟料为20份，粒径大于3mm且不大于5mm的硅铝熟料为25份。The parts by weight of silicon-alumina clinker with different particle sizes used: 20 parts for silicon-alumina clinker with a particle size of 0.1 to 1 mm, 20 parts for silicon-alumina clinker with a particle size greater than 1 mm and not greater than 3 mm, and 20 parts for silicon-alumina clinker with a particle size greater than 1 mm. Silicon-aluminum clinker with a diameter of 3mm and not larger than 5mm is 25 parts.
对比例3：Comparative example 3:
在实施例3的基础上，提供对比例3，对比例3与实施例3的区别主要在于：锡槽底砖各组分重量份数不同。On the basis of Example 3, Comparative Example 3 is provided. The main difference between Comparative Example 3 and Example 3 is that the weight parts of each component of the tin bath bottom brick are different.
本对比例的锡槽底砖，由以下重量份数的组分组成：硅铝熟料70份、纯铝酸钙水泥8份、高铝细粉13份、粘土粉4份、硅微粉5份、减水剂0.2份。The tin bath bottom brick of this comparative example is composed of the following components by weight: 70 parts of silica-alumina clinker, 8 parts of pure calcium aluminate cement, 13 parts of high-aluminum fine powder, 4 parts of clay powder, and 5 parts of silica powder , 0.2 parts of water reducing agent.
对比例4：Comparative example 4:
在实施例4的基础上，提供对比例4，对比例4与实施例4的区别主要在于：锡槽底砖各组分重量份数不同。On the basis of Example 4, Comparative Example 4 is provided. The main difference between Comparative Example 4 and Example 4 is that the weight parts of each component of the tin bath bottom brick are different.
本对比例的锡槽底砖，由以下重量份数的组分组成：硅铝熟料75份、纯铝酸钙水泥4份、高铝细粉11份、粘土粉3份、硅微粉4份、铝溶胶3份，减水剂0.2份。The tin bath bottom brick of this comparative example consists of the following components by weight: 75 parts of silica-alumina clinker, 4 parts of pure calcium aluminate cement, 11 parts of high-aluminum fine powder, 3 parts of clay powder, and 4 parts of silica powder , 3 parts of aluminum sol, 0.2 parts of water reducing agent.
对比例5：Comparative example 5:
在实施例5的基础上，提供对比例5，对比例5与实施例5的区别主要在于：锡槽底砖各组分重量份数不同。On the basis of Example 5, Comparative Example 5 is provided. The main difference between Comparative Example 5 and Example 5 is that the weight parts of each component of the tin bath bottom brick are different.
本对比例的锡槽底砖，由以下重量份数的组分组成：硅铝熟料75份、纯铝酸钙水泥4份、高铝细粉13份、粘土粉2份、硅微粉3份、硅溶胶2份，减水剂0.2份。The tin bath bottom brick of this comparative example consists of the following components by weight: 75 parts of silica-alumina clinker, 4 parts of pure calcium aluminate cement, 13 parts of high-aluminum fine powder, 2 parts of clay powder, and 3 parts of silica powder , 2 parts of silica sol, 0.2 parts of water reducing agent.
分别对实施例1～5与对比例1～5制备的锡槽底砖的耐蚀性能和高温使用性能进行一个检测，检测的结果如表4所示。The corrosion resistance and high-temperature performance of the tin bath bottom bricks prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were tested respectively. The test results are shown in Table 4.
表4检测结果Table 4 Test results
由表4测试的结果可知，实施例1～5的锡槽底砖相较于对比例的锡槽底砖具有很大的优势，例如导热系数小，具有较好的保温效果，减少工业生产能耗；氢扩散度较低，气孔率较低，具有抗侵蚀能力。It can be seen from the test results in Table 4 that the tin bath bottom bricks of Examples 1 to 5 have great advantages compared to the tin bath bottom bricks of the comparative example, such as small thermal conductivity, good thermal insulation effect, and reduced industrial production capacity. consumption; hydrogen diffusivity is low, porosity is low, and corrosion resistance is available.
具体分析如下：The specific analysis is as follows:
通过实施例1跟对比例1比较分析可知，采用不同原料组分烧制的硅铝熟料对锡槽底砖的性能影响很大，本发明制备的硅铝熟料形成的闭气微孔较多，能够有效防止玻璃液渗入到锡槽底砖，产生霞石，影响锡槽底砖的使用寿命，从而提升锡槽底砖的品质；对比例1采用煤矸石块制备硅铝熟料，形成的开口微孔较多，严重影响锡槽底砖的使用性能。Through comparative analysis between Example 1 and Comparative Example 1, it can be seen that silicon-alumina clinker fired with different raw material components has a great influence on the performance of tin bath bottom bricks. The silicon-alumina clinker prepared in the present invention forms more air-locked micropores. , can effectively prevent the glass liquid from penetrating into the tin bath bottom bricks and producing nepheline, which will affect the service life of the tin bath bottom bricks, thereby improving the quality of the tin bath bottom bricks; Comparative Example 1 uses coal gangue blocks to prepare silicon-alumina clinker, forming There are many open micropores, which seriously affects the performance of the tin bath bottom brick.
通过实施例2与对比例2比较分析可知，本发明的锡槽底砖减少了纯铝酸钙水泥的使用量，然后增加硅溶胶和铝溶胶含量从而增加各组分的结合度，有效降低显气孔率和氢扩散度，使得锡槽底砖的耐蚀性和高温使用性能大幅提升。Through comparative analysis between Example 2 and Comparative Example 2, it can be seen that the tin bath bottom brick of the present invention reduces the usage of pure calcium aluminate cement, and then increases the content of silica sol and aluminum sol to increase the bonding degree of each component, effectively reducing the obvious The porosity and hydrogen diffusivity greatly improve the corrosion resistance and high-temperature performance of the tin bath bottom bricks.
通过实施例3与对比例3比较分析可知，本发明的锡槽底砖中添加硅溶胶和铝溶胶从而增加各组分的结合度，有效降低显气孔率和氢扩散度，提升锡槽底砖的耐蚀性和耐高温性。对比例3中未添加硅溶胶和铝溶胶，相比于实施例3，对比例3中的锡槽底砖各方面性能均有降低。Through the comparative analysis of Example 3 and Comparative Example 3, it can be seen that silica sol and aluminum sol are added to the tin bath bottom brick of the present invention to increase the bonding degree of each component, effectively reduce the apparent porosity and hydrogen diffusivity, and improve the tin bath bottom brick. Corrosion resistance and high temperature resistance. In Comparative Example 3, no silica sol and aluminum sol were added. Compared with Example 3, the performance of the tin bath bottom brick in Comparative Example 3 was reduced in all aspects.
通过实施例4与对比例4比较分析可知，单独使用铝溶剂的对比例4与实施例4比较，锡槽底砖的各方面性能均有降低。Through comparative analysis between Example 4 and Comparative Example 4, it can be seen that compared with Example 4, Comparative Example 4 using aluminum solvent alone has reduced the performance of the tin bath bottom brick in all aspects.
通过实施例5与对比例5比较分析可知，单独使用硅溶剂的对比例5与实施例5比较，锡槽底砖的各方面性能均有降低。Through comparative analysis between Example 5 and Comparative Example 5, it can be seen that compared with Example 5, Comparative Example 5 using silicon solvent alone has reduced the performance of the tin bath bottom brick in all aspects.
综上所述，不使用或者单独使用硅、铝溶胶其中的一种，增大纯铝酸钙水泥的使用量，会使得锡槽底砖的各项性能都有所降低；本发明的锡槽底砖减少了纯铝酸钙水泥的使用量，然后添加硅溶胶和铝溶胶来增加各组分的结合度，有效降低显气孔率和氢扩散度，使得锡槽底砖的耐蚀性和高温使用性能大幅提升。与此同时，本发明的锡槽底砖在保证线性变化率尽可能小时，底砖的显气孔率与氢扩散度也能够稳定在适当值。综上所述，本发明公开的锡槽底砖具有最佳的综合性能。To sum up, if one of silicon and aluminum sol is not used or used alone, and the usage amount of pure calcium aluminate cement is increased, the various properties of the tin bath bottom brick will be reduced; the tin bath of the present invention The bottom brick reduces the usage of pure calcium aluminate cement, and then adds silica sol and aluminum sol to increase the bonding degree of each component, effectively reducing the apparent porosity and hydrogen diffusivity, making the tin bath bottom brick more corrosion-resistant and high-temperature Usage performance is greatly improved. At the same time, the tin bath bottom brick of the present invention can ensure that the linear change rate is as small as possible, and the apparent porosity and hydrogen diffusivity of the bottom brick can also be stabilized at appropriate values. To sum up, the tin bath bottom brick disclosed in the present invention has the best comprehensive performance.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310843555.1ACN116874308A (en) | 2023-07-11 | 2023-07-11 | A tin bath bottom brick and its preparation method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310843555.1ACN116874308A (en) | 2023-07-11 | 2023-07-11 | A tin bath bottom brick and its preparation method |
| Publication Number | Publication Date |
|---|---|
| CN116874308Atrue CN116874308A (en) | 2023-10-13 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310843555.1APendingCN116874308A (en) | 2023-07-11 | 2023-07-11 | A tin bath bottom brick and its preparation method |
| Country | Link |
|---|---|
| CN (1) | CN116874308A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117720359A (en)* | 2023-12-11 | 2024-03-19 | 山东淄博沈淄耐火材料有限公司 | Low thermal conductivity tin bath bottom brick and preparation method thereof |
| CN120271359A (en)* | 2025-06-12 | 2025-07-08 | 山东淄博沈淄耐火材料有限公司 | Composite heat-insulating tin bath bottom brick and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK261579A (en)* | 1978-06-22 | 1979-12-23 | Hoeganaes Ab | REFRACTORY MOLDING MATERIAL FOR THE MANUFACTURE OF MONOLITICAL LININGS AND THEIR MANUFACTURE |
| CN1480416A (en)* | 2002-09-05 | 2004-03-10 | 吕志乾 | Bottom brick in tin pot |
| CN109650919A (en)* | 2019-01-31 | 2019-04-19 | 河南中原特种耐火材料有限公司 | A kind of aggregate being used to prepare bottom brick of molten tin bath and preparation method thereof, bottom brick of molten tin bath |
| CN109851376A (en)* | 2019-01-31 | 2019-06-07 | 河南中原特种耐火材料有限公司 | A kind of bottom brick of molten tin bath and preparation method thereof is used to prepare the composition of bottom brick of molten tin bath |
| CN115636677A (en)* | 2022-10-26 | 2023-01-24 | 中南大学 | Tin bath top cover brick for float glass production and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK261579A (en)* | 1978-06-22 | 1979-12-23 | Hoeganaes Ab | REFRACTORY MOLDING MATERIAL FOR THE MANUFACTURE OF MONOLITICAL LININGS AND THEIR MANUFACTURE |
| US4244745A (en)* | 1978-06-22 | 1981-01-13 | Hoganas Ab | High-strength refractory casting compound for the manufacture of monolithic linings |
| CN1480416A (en)* | 2002-09-05 | 2004-03-10 | 吕志乾 | Bottom brick in tin pot |
| CN109650919A (en)* | 2019-01-31 | 2019-04-19 | 河南中原特种耐火材料有限公司 | A kind of aggregate being used to prepare bottom brick of molten tin bath and preparation method thereof, bottom brick of molten tin bath |
| CN109851376A (en)* | 2019-01-31 | 2019-06-07 | 河南中原特种耐火材料有限公司 | A kind of bottom brick of molten tin bath and preparation method thereof is used to prepare the composition of bottom brick of molten tin bath |
| CN115636677A (en)* | 2022-10-26 | 2023-01-24 | 中南大学 | Tin bath top cover brick for float glass production and preparation method thereof |
| Title |
|---|
| 李红霞: "耐火材料手册（第二版）", 31 January 2021, 冶金工业出版社, pages: 227* |
| 李红霞: "钢铁原辅料生产节能减排先进技术", 31 October 2020, 冶金工业出版社, pages: 363 - 364* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117720359A (en)* | 2023-12-11 | 2024-03-19 | 山东淄博沈淄耐火材料有限公司 | Low thermal conductivity tin bath bottom brick and preparation method thereof |
| CN120271359A (en)* | 2025-06-12 | 2025-07-08 | 山东淄博沈淄耐火材料有限公司 | Composite heat-insulating tin bath bottom brick and preparation method thereof |
| Publication | Publication Date | Title |
|---|---|---|
| CN116874308A (en) | A tin bath bottom brick and its preparation method | |
| CN109851376B (en) | Tin bath bottom brick, preparation method thereof and composition for preparing tin bath bottom brick | |
| CN100509704C (en) | Flame-proof pouring material for hydroted alumina gas suspending roasting furnace furnace liner | |
| CN110423134A (en) | It is a kind of using gold ore tailing as foamed ceramics of raw material and preparation method thereof | |
| CN110028303B (en) | Reinforced porcelain prepared from common domestic ceramic blank and preparation method thereof | |
| CN106431434B (en) | A kind of obturator-type alumina base mullite material and preparation method thereof | |
| CN109851374A (en) | Explosion-proof, long-life bottom brick of molten tin bath and preparation method thereof | |
| CN107266052A (en) | Alumina titanium calcium aluminate carborundum multiple phase refractory material and preparation method thereof | |
| CN1554616A (en) | A preparation method for preparing light-weight and high-strength alumina hollow sphere ceramics | |
| CN105084916B (en) | A kind of anticorrosive magnesium-aluminium fire resistant materials and preparation method thereof | |
| CN101863674A (en) | A corundum hollow sphere structure heat insulation integrated composite brick and its preparation method | |
| CN107892579A (en) | Calcareous glass furnace molten tin bath suspended roof brick of aluminic acid and preparation method thereof | |
| CN108017397A (en) | Refractory brick containing quartz sand and preparation method thereof | |
| CN110204322A (en) | A kind of mullite insulating fire brick and preparation method thereof | |
| CN108002848A (en) | Refractory brick containing magnesium aluminate spinel and preparation method thereof | |
| CN110937906B (en) | A safe and energy-saving smelting furnace body and a smelting device using the furnace body | |
| CN113999024A (en) | Preparation method of light-weight infrared radiation energy-saving coke oven door prefabricated part | |
| CN117720359A (en) | Low thermal conductivity tin bath bottom brick and preparation method thereof | |
| CN114031381B (en) | Silicon brick added with silicon iron nitride and preparation method thereof | |
| CN117164335A (en) | Urban sludge sintered insulating brick and preparation method thereof | |
| CN116396084A (en) | Preparation method of silicon oxynitride-silicon carbide composite brick for producing low-oxygen copper rod | |
| CN115368117A (en) | Aluminum-silicon composite preforms with different densities and preparation method thereof | |
| CN102230740A (en) | High siliceous structure and thermal insulation integrated composite brick and preparation method | |
| CN109650919B (en) | Aggregate for preparing tin bath bottom brick, preparation method of aggregate and tin bath bottom brick | |
| CN102285808A (en) | Alkaliproof structure and thermal insulation integrated composite brick and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20231013 | |
| RJ01 | Rejection of invention patent application after publication |