CN116375459B - 一种高硅功能瓷及其制备方法 - Google Patents
一种高硅功能瓷及其制备方法 Download PDFInfo
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Abstract
本发明涉及陶瓷生产,尤其涉及一种高硅功能瓷及其制备方法,所述高硅功能瓷由以下质量百分比的原料组成:乌兰茶晶石40~50%、石英18~20%、黏土30~42%。所述高硅功能瓷的化学组成包括:SiO270‑85%,Al2O316‑22%,CaO≤2%,MgO≤1%,Fe2O3≤0.1%,TiO2≤0.1%,K2O2‑4%,Na2O1‑2.5%。本发明的功能陶瓷,以乌兰茶晶石、黏土、石英为原料,乌兰茶晶石中SiO2大部分是以熔融玻璃态二氧化硅存在,解决了高硅瓷体在石英(SiO2)晶型转换点的炸瓷问题,可实现规模化生产应用,适用于高硅瓷的批量生产;同时所得陶瓷成品合格率高、抗热震性好、低热胀冷缩性能,沿用现有工艺成熟的陶瓷生产设备即可,有助于推广应用,具有很高的实用价值和应用前景。
Description
技术领域
本发明涉及陶瓷生产,尤其涉及一种高硅功能瓷及其制备方法。
背景技术
原料是陶瓷之根本,且陶瓷原料是不可再生资源。目前,陶瓷原料资源的开采缺乏科学合理的规划和综合利用措施,致使其资源利用率极低、陶瓷制品原料成本高,极大制约了陶瓷行业的可持续发展。
高硅质瓷作为一种多元硅酸盐陶瓷,具有良好的化学稳定性、耐磨性能和较高的抗性,有利于长期稳定工作、耐磨抗冲击等优异特性。高硅质瓷具有良好的耐热性和低温强度,在较高温度下仍具有较低的熔化点,具有良好的热稳定性。此外,由于高硅质瓷制品具有较高的物理强度,可承受较高的压力和抗冲击性,使其在航空、军事、船舶等行业中得到广泛的应用。
陶瓷抗热震性是在陶瓷制备过程中的关键。陶瓷抗热震性指材料在承受急剧温度变化时,评价其抗破损能力的重要指标,当承受温度激烈变化而引起内部温度梯度时,在材料内部会因收缩或膨胀受阻产生热应力,当热应力超过材料强度极限时,产生开裂、破坏和机械强度降低等现象。陶瓷的抗热震性与热膨胀系数相关,热膨胀系数越小,材料因温度变化而引起的体积变化小,相应产生的温度应力小,抗热震性越好。有许多类型的陶瓷材料,每一种材料都有不同的性能和抗热震性。因此,研究陶瓷抗热震性的重要性也就显而易见了。
一般日用瓷都是以控制最终产物中的二氧化硅的含量(65%~75%)来提高热稳定性,防止炸瓷;高硅陶瓷中,二氧化硅的含量远远高于75%,存在易炸裂、不易进行规模化生产的行业难题。因此,如何提高高硅陶瓷的热稳定性,是亟待解决的问题。
发明内容
本发明提供一种高硅功能瓷及其制备方法,用以解决高硅陶瓷在烧成过程炸瓷问题。本发明制备的功能瓷制品具有成品合格率高、抗热震性好、低热胀冷缩性能。
为了实现上述目的,本发明采用的技术方案是:
一方面,本发明提供一种高硅功能瓷,由以下质量百分比的原料组成:乌兰茶晶石40~50%、石英18~20%、黏土30~42%。
进一步的,所述高硅功能瓷的化学组成包括:SiO270-85%,AL2O316-22%,CaO≤2%,MgO≤1%,Fe2O3≤0.1%,TiO2≤0.1%,K2O 2-4%,Na2O 1-2.5%。
优选的,所述高硅功能瓷的化学组成包括:SiO270-81%,AL2O316-22%,CaO≤2%,MgO≤1%,Fe2O3≤0.1%,TiO2≤0.1%,K2O 2-4%,Na2O 1-2.5%。
更具体的,所述高硅功能瓷的化学组成中还包括微量元素,结果如下表所示:(单位:mg/kg)
本发明的高硅功能瓷,以乌兰茶晶石、石英、黏土为原料制备,得到的功能瓷的二氧化硅含量高,且具有高强度、透光度好、表面硬度高、低热胀冷缩性等特点。传统的高硅瓷,在烧制过程中,会因石英在573℃时晶型转变引起烧成过程炸瓷问题,导致未得到规模化生产应用,不能适用于大生产。本发明的高硅功能瓷,选用乌兰茶晶石作为原料之一,由于乌兰茶晶石中的二氧化硅大部分是以熔融玻璃态二氧化硅存在,巧妙的解决了瓷体在石英(SiO2)晶型转换温度的炸瓷问题。同时利用乌兰茶晶石中存在的丰富的稀土元素作为促晶剂,在烧成过程中可以在同等氧化硅和氧化铝含量及比例条件下更容易形成莫来石晶体,使得制备得到的功能瓷强度和韧性更好,有效的解决了产品抗急冷急热的热稳定性问题。另外,利用乌兰茶晶石中丰富的稀土元素的相互激发与耦合和与基体成分间发生激发与被激发作用而产生的高能态物质具有明显的黑体性质,进而提高功能瓷的导热系数,宏观表现为较高的导热性能。因此,本发明原料制备得到的高硅功能瓷在具有高硅含量的前提下,可解决炸瓷问题,实现规模化大生产。
另一方面,本发明的高硅功能瓷,以乌兰茶晶石为主要原料,利用乌兰茶晶石中多组分稀土元素和铷元素的存在,使得功能瓷具有较高的抗菌性能。乌兰茶晶石中的稀土元素在烧成过程中自身之间发生耦合与激发以及和基体成分间发生激发与被激发作用,产生高能态物质,使得价带电子进入导带更容易产生电子溢出,从而在瓷体表面产生负氧离子和羟基,形成表面抗菌杀菌机制。
进一步地,黏土为高岭石粘土、蒙脱石粘土中的至少一种。
另一方面,本发明还提供一种功能瓷制备方法,具体包括以下步骤:
S1、取乌兰茶晶石、石英、黏土混匀,进行球磨,球磨后过筛除铁,再进行滤泥,然后进行真空炼泥及泥的陈腐,成型后修坯得备用成型坯;
S2、修坯后进行素烧,再经过打磨抛光得到光滑细腻无杂物素烧产品;
S3、将S2所得的素烧产品进行施釉,施釉后釉烧制得功能瓷。
具体地,本发明提供的功能瓷的制备方法包括以下步骤:
(1)泥料制备
取乌兰茶晶石、石英、黏土按照配方混合均匀装磨球磨,球磨时间21~26h,球磨细度D50为4.5~5.2μm后,进行放磨处理,放入预备井,然后除铁过筛,用高强度除铁器(15000~20000Gs)除掉泥浆中的铁,同时用250目万孔筛,经过两道除铁过筛系统后,进行滤饼处理,然后把泥饼进行三遍搅泥,按照成型要求生产对应直径的泥条。
(2)成型成坯制备
将上述的泥料进行生产,先出毛坯,然后进行修边打磨,最后进行修验,制得合格的成坯。
(3)素烧
将上述合格的成坯匹配对应器型的匣钵,按照器型分类进入到相应烧成区域进行烧成,素烧时间8~10h,烧成温度1200~1260℃,得到素烧产品。
(4)施釉
将合格素烧产品进行抛光,抛光后的产品进入烘干房进行干燥处理,待干燥后进行施釉,根据器型分类施釉,控制单位施釉重量为0.035~0.04g/cm2,将施釉后的产品放入半成品区域内,以供釉烧成入窑。
(5)釉烧
将施釉后的半成品釉坯进行装釉窑,釉烧时间为3.25~4h,烧成温度1110~1140℃,得到功能瓷。
进一步地,素烧和釉烧工艺完成后以及施釉前对产品进行检选与分类,分为合格品,返修品,残品,并分别放入指定区域。返修后的产品再次进行检选,合格后存入合格品区域。
与现有技术相比,本发明的有益效果是:
(1)本发明以乌兰茶晶石、黏土、石英为原料,乌兰茶晶石中SiO2大部分是以熔融玻璃态二氧化硅存在,解决了高硅瓷体在石英(SiO2)晶型转换点的炸瓷问题,可实现规模化生产应用,适用于高硅瓷的批量生产;同时本发明所用原料种类少,优化了原料成本,降低了因原料种类多引起的混合、调配不均等问题的出现概率,降低了生产成本,提高了产品的质量稳定性。
(2)本发明制备的功能陶瓷,生产工艺简单易控,所得陶瓷成品合格率高、抗热震性好、低热胀冷缩性能,沿用现有工艺成熟的陶瓷生产设备即可,有助于推广应用,具有很高的实用价值和应用前景。
附图说明
为了更清楚的说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单的介绍,显而易见的,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其它附图。
图1为实施例1乌兰茶晶石的SEM-EDS图;
图2为本发明实施例1所制陶瓷的SEM图;
图3为本发明对比例1所制陶瓷的SEM图。
具体实施方式
下面将结合具体实施例,对本发明的技术方案进行清楚、完整的描述,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,本领域普通的技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例,都属于本发明的保护范围。
实施例1
本实施例中的高硅功能瓷,由以下质量百分比的原料组成:乌兰茶晶石50%、石英20%、淘洗龙岩土25%、于寺土5%。
本实施例的功能瓷的制备方法包括以下步骤:
(1)泥料制备
按照质量百分比计,取乌兰茶晶石50%、石英20%、淘洗龙岩土25%、于寺土5%,将上述原料按照配方混合均匀装磨球磨,球磨时间23h,之后进行放磨处理,放入预备井,然后除铁过筛,用高强度除铁器(15000~20000Gs)除掉泥浆中的铁,同时用250目万孔筛,经过两道除铁过筛系统后,进行滤饼处理,然后把泥饼进行三遍搅泥,按照成型要求生产对应直径的泥条。
(2)成型成坯制备
将上述的泥料进行生产,先出毛坯,然后进行修边打磨,最后进行修验,制得合格的成坯。
(3)素烧
将上述合格的成坯匹配对应器型的匣钵,按照器型分类进入到相应烧成区域进行烧成,素烧时间9.5h,烧成温度1250℃,得到素烧产品。
(4)施釉
将合格素烧产品进行抛光,抛光后的产品进入烘干房进行干燥处理,待干燥后进行施釉,根据器型分类施釉,控制单位施釉重量为0.035~0.04g/cm2,将施釉后的产品放入半成品区域内,以供釉烧成入窑。
(5)釉烧
将施釉后的半成品釉坯进行装釉窑,釉烧时间为3.5h,烧成温度1120℃,得到功能瓷。
实施例2
本实施例包括实施例1中大部分操作步骤,其不同之处在于,由以下质量百分比的原料组成:乌兰茶晶石45%、石英20%、龙岩土25%、球土5%、唐县土3%、卯都土2%。
实施例3
本实施例包括实施例1中大部分操作步骤,其不同之处在于,由以下质量百分比的原料组成:乌兰茶晶石40%、石英18%、原矿龙岩土7%、淘洗龙岩土30%、于寺土2%、唐县土3%。
对比例1
本对比例包括实施例1中大部分操作步骤,其不同之处在于,由以下质量百分比的原料组成:石英60%、淘洗龙岩土25%、于寺土15%。
对实施例1-3与对比例1中制备得到的功能瓷的相关理化指标进行测试,采用《日用瓷器》GB/T 3532-2022为依据进行测试,同时对功能瓷中二氧化硅含量进行测试。
其中,抗热震性检测标准为:180-20℃水热交换一次不裂;微波炉适应性检测标准为:经微波炉试验,一次循环不裂和无电弧产生;冰箱到微波炉适应性检测标准为:从冰箱(-8℃)到微波炉试验,一次循环不裂和无电弧产生。
测试结果如表1所示:
表1产品理化指标检测
将实施例1-3和对比例1的实验数据相比可知:本发明制备的高硅功能瓷,在较高的二氧化硅含量下,200-20℃水热交换一次不裂,抗热震性能更优,同时其低热胀冷缩性能效果显著。
图1为实施例1中乌兰茶晶石原料的SEM-EDS图,可以看出乌兰茶晶石为硅氧化物和铝氧化物组分,同时二氧化硅大部分以熔融玻璃态二氧化硅存在,使得瓷体在石英(SiO2)晶型转换点的炸瓷问题,使得功能瓷能够批量生产。
由图2和图3扫描电镜图对比可以看出,在烧成过程中以同等氧化硅和氧化铝含量及比例条件下,添加乌兰茶晶石更容易形成莫来石晶体,对应得到的功能瓷的强度和韧性更好。
实施例4-8
本实施例包括实施例1中大部分操作步骤,其不同之处在于:磨球时间和细度不同,具体见表2。
对比例2-3
本对比例包括实施例1中大部分操作步骤,其不同之处在于:磨球时间和细度不同,具体见表2。
对实施例4-8、对比例2-3的产品的球磨工艺参数进行检测,检测结果如表2所示:
表2磨球工艺参数检测
组分 | 球磨时间/h | 泥浆性能 |
实施例1 | 23 | 泥浆不沉降,符合泥浆使用性能 |
实施例4 | 22 | 泥浆不沉降,符合泥浆使用性能 |
实施例5 | 24 | 泥浆不沉降,符合泥浆使用性能 |
实施例6 | 25 | 泥浆不沉降,符合泥浆使用性能 |
实施例7 | 26 | 泥浆流动性渐弱,稍发脑 |
实施例8 | 21 | 泥浆不沉降,符合泥浆使用性能 |
对比例2 | 20 | 泥浆沉降,不符合泥浆使用性能 |
对比例3 | 27 | 泥浆流动性弱,发脑 |
由上可知:球磨时间在21-26h时,符合泥浆使用性能;当球磨时间过短时,泥浆沉降,不符合泥浆使用性能;当球磨时间过长时,泥浆流动性弱,也不符合使用性能。
实施例9-13
本实施例包括实施例1中大部分操作步骤,其不同之处在于:素烧时间和烧成温度不同,具体见表3。
对比例4-5
本对比例包括实施例1中大部分操作步骤,其不同之处在于:素烧时间和烧成温度不同,具体见表3。
对实施例1、9-13与对比例4-5的产品的素烧工艺参数进行检测,检测结果如表3所示:
表3素烧工艺参数检测
组分 | 素烧温度/℃ | 烧成时间/h | 产品性能 |
实施例1 | 1250 | 9.5 | 产品烧结完全,吸水率0.03% |
实施例9 | 1200 | 8 | 产品烧结,吸水率0.20%,刚好达到烧结 |
实施例10 | 1220 | 8 | 产品烧结,吸水率0.20%,刚好达到烧结 |
实施例11 | 1230 | 8.5 | 产品烧结完全,吸水率0.15% |
实施例12 | 1240 | 9 | 产品烧结完全,吸水率0.1% |
实施例13 | 1260 | 10 | 产品出现轻微过火现象,吸水率0.01% |
对比例4 | 1180 | 7 | 产品烧结不完全,吸水率0.3% |
对比例5 | 1280 | 11 | 产品出现过火现象,吸水率0.01% |
从表3的实验数据可知:素烧时间在8~10h,素烧温度在1200~1260℃,本发明所制备的功能瓷产品性能能达到生产要求;当素烧时间短,素烧温度低时,产品烧结不完全,不符合素烧产品标准;当素烧时间长,素烧温度高时,产品烧结过火,也不符合素烧产品标准。
实施例14-16
本实施例包括实施例1中大部分操作步骤,其不同之处在于:釉烧时间和烧成温度不同,具体见表4。
对比例6-7
本对比例包括实施例1中大部分操作步骤,其不同之处在于:釉烧时间和烧成温度不同,具体见表4。
对实施例1、14-16与对比例6-7的产品的釉烧工艺参数进行检测,检测结果如表4所示:
表4釉烧工艺参数检测
从表4数据可知:釉烧时间在3.25~4h,素烧温度在1100~1140℃,本发明所制备的功能瓷产品性能能达到生产要求;当釉烧时间过短,产品外观不够明亮,不符合国标一级标准;当釉烧时间过长时,产品釉面稍粗糙,有多个过火毛孔不符合国标一级标准。
以上借助具体实施例对本发明做了进一步描述,但是应该理解的是,这里具体的描述,不应理解为对本发明的实质和范围的限定,本领域内的普通技术人员在阅读本说明书后对上述实施例做出的各种修改,都属于本发明所保护的范围。
Claims (7)
1.一种高硅功能瓷,其特征在于,由以下质量百分比的原料组成:乌兰茶晶石40~50%、石英18~20%、黏土30~42%,所述高硅功能瓷的化学组成包括:SiO270-85%,Al2O316-22%,CaO≤2%,MgO≤1%,Fe2O3≤0.1%,TiO2≤0.1%,K2O2-4%,Na2O 1-2.5%。
2.根据权利要求1所述的高硅功能瓷,其特征在于,所述黏土为高岭石粘土、蒙脱石粘土中的至少一种。
3.权利要求1~2任一项所述的高硅功能瓷的制备方法,其特征在于,包括以下步骤:
S1、取乌兰茶晶石、石英、黏土混匀,进行球磨,球磨后过筛除铁,再进行滤泥,成型后修坯得备用成型坯;
S2、修坯后进行素烧,再经过打磨抛光得到光滑细腻无杂物素烧产品;
S3、将S2所得的素烧产品进行烘干并施釉,施釉后釉烧制得功能瓷。
4.根据权利要求3所述的高硅功能瓷的制备方法,其特征在于,步骤S1中,球磨时间为21~26h,球磨后细度D50为4.5~5.2μm。
5.根据权利要求3所述的高硅功能瓷的制备方法,其特征在于,步骤S2中,素烧时间8~10h,素烧温度1200~1260℃。
6.根据权利要求3所述的高硅功能瓷的制备方法,其特征在于,步骤S3中,施釉重量为0.035~0.04g/cm2。
7.根据权利要求3所述的高硅功能瓷的制备方法,其特征在于,步骤S3中,釉烧时间为3.25~4h,釉烧温度1110~1140℃。
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