CN111517797B - 一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法 - Google Patents
一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法 Download PDFInfo
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Abstract
本发明涉及一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法，以涂层的形式应用于需要耐高温、抗氧化及耐腐蚀等防护性能的领域。其技术特征在于步骤为调配高纯SiC料浆、刷涂和低温无压烧结。本发明所提供的技术方案通过调控高纯SiC料浆配方来控制SiC涂层的纯度和烧结温度，实现高纯SiC涂层在1750～1800℃的常压烧结和工业化制备生产。本发明中高纯SiC的料浆配方及刷涂和烧结过程灵活可控，涂层与基体结合良好，无明显剥落和裂纹，工艺过程操作简单，耗时短，大幅度降低了成本。
Description
技术领域
本发明属于碳化硅(SiC)陶瓷材料领域，涉及一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法。
背景技术
SiC陶瓷因其高硬度、高耐磨损性、高抗弯强度和优良的抗氧化性、耐酸碱腐蚀性及高温力学性能被广泛应用于航天、航空、微电子、汽车、激光、矿业及原子能等领域。而高纯SiC涂层在这些领域起着高温防护、抗氧化及耐腐蚀的重要作用，SiC涂层的纯度越高，在极端严苛工况下，由杂质引起的污染越小，防护性能越优异。目前，国内对低成本产业化高纯SiC陶瓷涂层的制备与使用还处于探索阶段，主要存在制备工艺复杂、设备昂贵，SiC涂层烧结温度高、纯度不易控制，成本耗费大的问题。
SiC作为防护涂层，常见的制备方法有固渗法(包埋法)、溅射法、化学气相沉积法和涂刷法。如中国专利CN 105948822A提供了一种SiC基复合材料表面SiC涂层的制备方法，将硅粉包埋于碳化硅基复合材料表面，在过量的碳源中高温热处理得到SiC涂层；中国专利CN 102373417A提供了一种在石墨材料表面制备抗氧化SiC涂层的方法，采用超高真空多功能磁控溅射镀膜设备，在石墨材料表面制备硅(Si)涂层，经真空热处理得到抗氧化SiC涂层；中国专利CN 105503270A提供了通过化学气相沉积和先驱体浸渍裂解的方法制备SiC涂层；中国专利CN 107082651B提供了一种涂刷法制备的SiC涂层，分为内覆层和外覆层，内覆层以SiC粉、Si粉为主，涂覆于含碳材料表面，外覆层以硅化浆料为主涂覆于内覆层表面，真空烧结得到SiC涂层。采用固渗法制备的SiC涂层与基体没有明显的界面，可以缓解基体与涂层热膨胀系数不匹配的问题，但存在涂层不致密、纯度不高、含杂质较多，制备工艺复杂的问题，从而影响了SiC涂层的使用；溅射法和化学气相沉积法制备的SiC涂层与基体结合度好，有良好的工艺可重复性，可在大面积的基体材料表面制备厚度均匀的涂层，但设备昂贵、生产成本高，工艺复杂；涂刷法借助表面粘结的方法先形成预涂层，然后烧结成功能涂层，工艺简便、生产成本低，不需要专门的设备，可操作性高，适用于大型复杂构件表面涂层的工业化生产，相比较其他方法在工业化应用上具有很大的优势。
由于SiC是基本晶体结构单元为Si-C四面体的强共价键化合物，共价键约占88％，离子键占12％，这种强共价键性使得SiC在烧结时自扩散速率低，烧结驱动力很小，不易获得足够的能量形成晶界，而且不添加烧结助剂时，SiC的烧结温度约为2100～2200℃，对设备及使用环境要求极高，限制了其在工业上的应用。目前，国内外对SiC陶瓷材料的烧结进行了多方面的研究，主要有常压烧结、热压烧结和反应烧结。常压烧结可分为固相烧结和液相烧结，固相烧结一般以碳(C)或硼(B)作为烧结助剂促进SiC在常压下的烧结致密化，所需温度超过2000℃，液相烧结则是引入金属或金属氧化物等在高温时形成液相促进烧结，所需温度约为1800～1950℃。热压烧结即在烧结的同时进行加压，一般引入与常压烧结类似的烧结助剂，是目前常用的SiC陶瓷的快速烧结制备方法。反应烧结是将有反应活性的熔融硅在毛细管力作用下，向含有C的陶瓷素坯内的孔隙浸渗，通过C和Si发生反应生成SiC，常存在体积分数为5～30％的游离Si。但对于高纯SiC的烧结来说，液相烧结会引入较多的金属杂质，反应烧结会有5％及以上游离Si的存在，均无法保证SiC陶瓷材料的纯度，热压烧结温度大于1750℃，所需压力不等，通常对设备要求高，制备条件苛刻，工业化生产成本高。因此，综合考虑产业化高纯SiC涂层的制备，优先选择常压烧结，烧结过程不需要加压，工艺相对简单，适用范围广，可有效节约成本。
发明内容
要解决的技术问题
为了避免现有技术的不足之处，本发明提出一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法，针对高纯SiC陶瓷涂层纯度不易控制、烧结温度高，制备工艺复杂，生产成本大的应用局限性。
技术方案
一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法，其特征在于步骤如下：
步骤1.调配高纯SiC料浆：将纯度≥99％的高纯SiC粉溶于乙醇和丁酮中，加入质量分数2％的磷酸三乙酯，然后转移到球磨罐，用玛瑙球球磨8～12小时后，继续加入质量分数3％的聚乙烯醇缩丁醛、质量分数3％、混合比1:1的丙三醇和邻苯二甲酸二辛酯、质量分数5％的高纯Si粉和质量分数2％的碳化硼粉，接着球磨8～12小时形成的高纯SiC料浆；
步骤2.刷涂：将高纯SiC料浆刷涂于基体表面，室温干燥形成预涂层；
步骤3.低温无压烧结：将得到的预涂层在惰性气氛下进行烧结，升温速率2.5℃/min，烧结温度1750℃～1800℃，保温2～3小时后，自然降温完成高纯SiC陶瓷涂层的低温常压烧结。
所述乙醇和丁酮混合比为1:1。
所述高纯SiC粉的粒度为3～5μm、500nm。
有益效果
本发明提出的一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法，目的是有效控制SiC涂层的纯度，在常压烧结的条件下降低SiC陶瓷涂层的烧结温度，制备出高纯SiC涂层，简化工艺，有效降低生产成本。本发明的思想在于通过调控高纯SiC料浆配方来控制SiC涂层的纯度和烧结温度，从料浆的制备、刷涂到烧结过程不引入任何其他金属杂质等，实现高纯SiC陶瓷涂层的常压低温烧结和批量制备。
本发明的有益效果有以下几点：
(1)相比较其他常用的SiC涂层的制备方法，本发明通过调控高纯SiC料浆的配方来控制SiC涂层的纯度，料浆以≥99％的高纯SiC粉为原料，溶剂均为有机溶剂且易挥发，不引入其他金属杂质等，从刷涂到烧结过程由惰性气氛保护，有效实现了SiC涂层纯度的可控性。
(2)通过在高纯SiC料浆配方里加入一定比例的高纯Si粉和碳化硼粉实现了该涂层在1750～1800℃的烧结。
(3)采用涂刷和常压烧结法制备的高纯SiC涂层与基体结合良好，无明显的剥落和裂纹，层厚约为100μm，与磁控溅射法和化学气相沉积法对比，本发明使用的方法可灵活控制高纯SiC涂层厚度，且操作简便，详见表1。
(4)每平方米刷涂料浆成本低，从制备料浆到烧结仅需2～3天，工艺过程操作简单，耗时短，相比较溅射法和沉积法，采用该方法大幅降低了设备及制备成本，可以实现高纯SiC涂层的量产，详见表1。
(5)本发明使用的高纯SiC涂层的制备方法适用于需要具有耐高温、抗氧化及抗腐蚀等防护性能的基体及复杂构件，相比较磁控溅射法适用范围广，详见表1。
附图说明
图1.是本发明可量产的高纯SiC涂层低温常压烧结制备方法图。
图2.是本发明实施例1、实施例2和实施例3的高纯SiC涂层。
(a)实施例1中的高纯SiC涂层；(b)实施例2中的高纯SiC涂层；(c)实施例3中的高纯SiC涂层
图3.是本发明实施例1、实施例2和实施例3的高纯SiC涂层扫描电镜(SEM)图。
(a)实施例1中的高纯SiC涂层；(b)实施例2中的高纯SiC涂层；(c)实施例3中的高纯SiC涂层
图4.是本发明实施例1、实施例2和实施例3的高纯SiC涂层X射线衍射(XRD)图。
(a)实施例1中的高纯SiC涂层；(b)实施例2中的高纯SiC涂层；(c)实施例3中的高纯SiC涂层
图5.是实用构件上刷涂法低温常压烧结制备的高纯SiC涂层。
具体实施方式
现结合实施例、附图对本发明作进一步描述：
实施例1.
步骤一：以纯度≥99％，粒度500nm的高纯SiC粉为原料，溶于混合比1:1的乙醇与丁酮中，加入质量分数2％的磷酸三乙酯，然后转移到球磨罐，用玛瑙球球磨8～12小时后，继续加入质量分数3％的聚乙烯醇缩丁醛，质量分数3％、混合比1:1的丙三醇和邻苯二甲酸二辛酯，质量分数5％的高纯Si粉，质量分数2％的碳化硼粉，继续球磨8～12小时。
步骤二：将步骤1形成的高纯SiC料浆均匀的刷涂于反应烧结SiC基体表面，室温干燥形成预涂层。
步骤三：将步骤2得到的预涂层在惰性气氛下进行烧结，升温速率2.5℃/min，烧结温度1750℃～1800℃，保温2～3小时后，自然降温。
实施例2.
步骤一：以纯度≥99％，粒度3～5μm的高纯SiC粉为原料，溶于混合比1:1的乙醇与丁酮中，加入质量分数2％的磷酸三乙酯，然后转移到球磨罐，用玛瑙球球磨8～12小时后，继续加入质量分数3％的聚乙烯醇缩丁醛，质量分数3％、混合比1:1的丙三醇和邻苯二甲酸二辛酯，质量分数5％的高纯Si粉，质量分数2％的碳化硼粉，接着球磨8～12小时。
步骤二：将步骤1形成的高纯SiC料浆均匀的刷涂于反应烧结SiC基体表面，室温干燥形成预涂层。
步骤三：将步骤2得到的预涂层在惰性气氛下进行烧结，升温速率2.5℃/min，烧结温度1750℃～1800℃，保温2～3小时后，自然降温。
实施例3.
步骤一：以纯度≥99％，粒度500nm的高纯SiC粉为原料，加入5％的高纯SiC晶须，溶于混合比1:1的乙醇与丁酮中，加入质量分数2％的磷酸三乙酯，然后转移到球磨罐，用玛瑙球球磨8～12小时后，继续加入质量分数3％的聚乙烯醇缩丁醛，质量分数3％、混合比1:1的丙三醇和邻苯二甲酸二辛酯，质量分数5％的高纯Si粉，质量分数2％的碳化硼粉，接着球磨8～12小时。
步骤二：将步骤1形成的高纯SiC料浆均匀的刷涂于反应烧结SiC基体表面，室温干燥形成预涂层。
步骤三：将步骤2得到的预涂层在惰性气氛下进行烧结，升温速率2.5℃/min，烧结温度1750℃～1800℃，保温2～3小时后，自然降温。
表1本发明使用的涂刷+低温常压烧结高纯SiC涂层法与其他几种SiC涂层制备方法对比
Claims (1)
1.一种可量产的高纯SiC陶瓷涂层的低温常压烧结制备方法，其特征在于步骤如下：
步骤1.调配高纯SiC料浆：将纯度≥99％的高纯SiC粉溶于乙醇和丁酮中，其中乙醇和丁酮混合比为1:1，加入质量分数2％的磷酸三乙酯，然后转移到球磨罐，用玛瑙球球磨8～12小时后，继续加入质量分数3％的聚乙烯醇缩丁醛、质量分数3％、混合比1:1的丙三醇和邻苯二甲酸二辛酯、质量分数5％的高纯Si粉和质量分数2％的碳化硼粉，接着球磨8～12小时形成的高纯SiC料浆；
步骤2.刷涂：将高纯SiC料浆刷涂于基体表面，室温干燥形成预涂层；
步骤3.低温无压烧结：将得到的预涂层在惰性气氛下进行烧结，升温速率2.5℃/min，烧结温度1750℃～1800℃，保温2～3小时后，自然降温完成高纯SiC陶瓷涂层的低温常压烧结；
所述高纯SiC粉的粒度为3～5μm或500nm。
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