CN115286410A - 一种3d打印碳纳米管增韧碳化硅陶瓷基复合材料浆料及其制备方法 - Google Patents
一种3d打印碳纳米管增韧碳化硅陶瓷基复合材料浆料及其制备方法 Download PDFInfo
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Abstract
本发明属于打印材料技术领域,尤其涉及一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料及其制备方法。本发明所述浆料包括以下重量份的组分:58‑68份粉体颗粒,31.4‑42.5份溶剂,0.8‑1.2份粘结剂,0.3‑1.2份分散剂,所述粉体颗粒为碳化硅、碳黑、碳纳米管。本发明所述浆料在制备过程中加入碳纳米管,大大提高了碳化硅陶瓷基复合材料的力学性能,所得浆料粘度低、固相含量高、流动性好,能满足直写成型3D打印浆料的需要。
Description
技术领域
本发明属于打印材料技术领域,尤其涉及一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料及其制备方法。
背景技术
随着当今社会的不断发展,人们对材料的综合性能要求也越来越高。碳化硅陶瓷作为一种结构材料,因其具有强度硬度高、耐高温、耐磨损、耐腐蚀、抗氧化、弹性模量高、抗压强度大等优点,被广泛应用于车辆机械、微电子、化学工业、航空航天和生物医学工程等领域。但其脆性大、可靠性差和韧性不足等特点却给碳化硅陶瓷的广泛应用和加工成型带来了很多困难。而碳化硅陶瓷基复合材料在保留了碳化硅陶瓷优点的同时,还克服了碳化硅陶瓷可靠性差等缺点,成为了相关领域的研究热点。
碳纳米管的杨氏模量超过1TPa,抗拉强度超过50GPa,超过钢的100倍,而密度却只有钢的1/6,弯曲强度达14GPa,其性能优于当前任何纤维,是理想的增强增韧材料,将其应用到碳化硅陶瓷基复合材料制备中,将大大增强碳化硅陶瓷的强韧性。
随着陶瓷材料的不断广泛应用,人们所需求的陶瓷形状越来越复杂精细,传统陶瓷制备方法难以满足人们的需求。传统的陶瓷制备成型方式主要采用干压成型、等静压成型、注浆成型等方法,由于需要特定形状和尺寸的模具,在制造相对复杂形状和复合结构的产品上具有较大的限制,生产周期长、成本高,并且坯体在脱模过程中很容易受到损坏。因此需要寻找更为可靠的陶瓷成型方式。
浆料直写成型3D打印技术是利用3D结构数据,将陶瓷浆料通过喷嘴挤出进行不断的堆积叠加,得到精细的三维形状,实现预期设定的模型结构成型,具有成型精度高和无模成形等特点,因此浆料直写成型3D打印技术在高性能陶瓷的成型制造领域具有巨大的发展潜力。但这种成型方式对陶瓷浆料的成分和粘度要求较高,需要具有剪切变稀特征的陶瓷浆料。因此我们需要探究合适的浆料配方使浆料满足低粘度、高固相、流动性好的特点来进行直写成型,保证打印精度。
发明内容
为解决上述现有技术中存在的问题,本发明提供了一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,在制备过程中加入碳纳米管,大大提高了碳化硅陶瓷基复合材料的力学性能,所得浆料粘度低、固相含量高、流动性好,能满足直写成型3D打印浆料的需要。
为实现上述目的,本发明采用如下技术方案:
首先,本发明的目的之一是提供一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括58-68份粉体颗粒,31.4-42.5份溶剂,0.8-1.2份粘结剂,0.3-1.2份分散剂。
进一步地,在上述用于3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料中,所述粉体颗粒为碳化硅、碳黑、碳纳米管,碳化硅陶瓷主体是碳化硅,碳化硅粉作为主体,碳粉作为后期反应烧结的反应主体,碳纳米管作为陶瓷增强体,颗粒混合具有陶瓷增韧效果,质量比为8:1:1。
进一步地,在上述用于3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料中,所述碳化硅粉末平均粒径为1微米,纯度>99wt%;所述碳黑粉末平均粒径为3微米,纯度>99wt%;所述碳纳米管粉末平均粒径为3.5纳米,纯度>95wt%,需分散处理后使用。粒径的限定能获得更好的浆料流动性,粒径过大会导致团聚和后期烧结过程中的气孔问题。
进一步地,在上述用于3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料中,所述溶剂为去离子水。
所述粘结剂为海藻酸钠,海藻酸钠粉末加入水中后,微粒间的水合作用使海藻酸钠表面具有粘性,且在同等固相含量下,海藻酸钠作为粘结剂的粘性较为合适,采用海藻酸钠作为粘结剂能够同时满足打印浆料的流动性和塑性要求。
所述分散剂为聚乙二醇400,聚乙二醇400是一种典型的非离子表面活性剂,其分子结构中只有醚基和羟基,易与SiC颗粒表面氢氧键形成较强的氢键,从而在SiC颗粒表面形成吸附层,产生空间位阻效应。获得的效果为选用聚乙二醇400可以使各颗粒表面位阻层间产生空间位阻斥力,阻止颗粒间的碰撞和沉降,从而使SiC颗粒稳定的分散在液相中。
其次,本发明的目的之二是提供一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料的制备方法,包括以下步骤:
步骤一:将溶剂与粘结剂按比例混合,搅拌均匀,静置12小时,制得粘结剂溶液;
步骤二:将碳纳米管与碳纳米管分散剂按质量比1:1加入到分散溶剂中,超声振荡,得到分散处理后的碳纳米管;
步骤三:将碳化硅粉末、炭黑粉末、分散处理后的碳纳米管按质量比8:1:1混合,搅拌均匀,得到预混粉体;
步骤四:在步骤三所得预混粉体中按比例加入分散剂,充分搅拌进行分散,得到分散后粉体;
步骤五:在步骤四得到的分散后粉体中加入步骤一得到的粘结剂溶液,充分搅拌,制得3D打印用碳纳米管增韧碳化硅陶瓷基复合材料浆料。
进一步地,步骤二所述分散溶剂为乙醇,所述碳纳米管分散剂为十二烷基硫酸钠。
进一步地,在上述3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料的制备方法中,步骤一中搅拌速度为200rad/min,搅拌时间为1.5小时;步骤二中振荡时间为30分钟;步骤三中搅拌速度为80rad/min,搅拌时间为30分钟;步骤四中搅拌速度为80rad/min,搅拌时间为30分钟;步骤五中搅拌速度为500rad/min,搅拌时间为3小时。
有益效果
本发明公开了一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料及其制备方法,与现有技术相比本发明的有益效果为:
(1)本发明提供的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,定量的加入粉体颗粒、粘结剂、分散剂和溶剂,所得浆料粘度低、固相含量高、流动性好,能满足直写成型3D打印浆料的需要。
(2)本发明提供的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,在制备过程中加入碳纳米管,大大提高了碳化硅陶瓷基复合材料的力学性能。
附图说明
图1为粘度-分散剂含量变化曲线图;
图2为粘度-固相含量变化曲线图;
图3为本发明所述的碳纳米管增韧碳化硅陶瓷基复合材料浆料用于直写成型3D打印的工艺流程图。
具体实施方式
以下,将详细地描述本发明。在进行描述之前,应当理解的是,在本说明书和所附的权利要求书中使用的术语不应解释为限制于一般含义和字典含义,而应当在允许发明人适当定义术语以进行最佳解释的原则的基础上,根据与本发明的技术方面相应的含义和概念进行解释。因此,这里提出的描述仅仅是出于举例说明目的的优选实例,并非意图限制本发明的范围,从而应当理解的是,在不偏离本发明的精神和范围的情况下,可以由其获得其他等价方式或改进方式。
以下实施例仅是作为本发明的实施方案的例子列举,并不对本发明构成任何限制,本领域技术人员可以理解在不偏离本发明的实质和构思的范围内的修改均落入本发明的保护范围。除非特别说明,以下实施例中使用的试剂和仪器均为市售可得产品。
实施例1
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括60份粉体颗粒,38.31份溶剂,1.14份粘结剂,0.55份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。
将上述原料按如下方法制备浆料:
步骤一:将去离子水与海藻酸钠按比例混合,以200rad/min速度搅拌1.5小时,静置12小时,制得海藻酸钠溶液;
步骤二:将碳纳米管与十二烷基硫酸钠按质量比1:1加入到乙醇溶液,超声振荡30分钟,得到分散处理后的碳纳米管;
步骤三:将碳化硅粉末、炭黑粉末、处理后的碳纳米管按质量比8:1:1混合,以80rad/min速度搅拌30分钟,得到预混粉;
步骤四:在步骤三预混粉体中按比例加入聚乙二醇400,以80rad/min速度搅拌30分钟进行分散;
步骤五:在步骤四得到的分散后粉体中加入步骤一得到的海藻酸钠溶液,以500rad/min速度搅拌3小时,制得3D打印用碳纳米管增韧碳化硅陶瓷基复合材料浆料,记为样品1。
实施例2
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括65份粉体颗粒,33.42份溶剂,0.98份粘结剂,0.6份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品2。
实施例3
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括65份粉体颗粒,33.71份溶剂,0.99份粘结剂,0.3份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品3。
实施例4
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括58份粉体颗粒,31.4份溶剂,0.8份粘结剂,0.3份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品4。
实施例5
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括68份粉体颗粒,42.5份溶剂,1.2份粘结剂,1.2份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品5。
对比例1
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括75份粉体颗粒,23.59份溶剂,0.71份粘结剂,0.7份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品6。
对比例2
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括70份粉体颗粒,28.48份溶剂,0.87份粘结剂,0.65份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品7。
对比例3
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括65份粉体颗粒,34份溶剂,1份粘结剂,0份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品8。
对比例4
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括55份粉体颗粒,43.3份溶剂,1.2份粘结剂,0.5份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品9。
对比例5
一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,按重量计份,包括50份粉体颗粒,48.3份溶剂,1.25份粘结剂,0.45份分散剂;所述粉体颗粒为碳化硅(d50=1μm,purity>99wt%)、碳黑(d50=3μm,purity>99wt%)、碳纳米管(d50=3.5nm,purity>95wt%),质量比为8:1:1,所述溶剂为去离子水;所述粘结剂为海藻酸钠;所述分散剂为聚乙二醇400。上述原料按照实施例1的方法制备浆料,记为样品10。
实验例
图1为粘度-分散剂含量变化曲线图,从图1中可以看出随着分散剂浓度的增大,粘度呈现先减小后增大的趋势,是由于分散剂浓度较小时,分散剂浓度升高,碳化硅表面包覆的分散剂变多,粘度下降,分散剂浓度为1wt%时包覆完全,而当分散剂浓度继续增大后,过多的分散剂游离在浆料中,在浆料流动过程中会出现桥连缠绕现象,致使浆料粘度上升。
图2为粘度-固相含量变化曲线图,从图2中可以看出浆料粘度随着固相含量的增大而增加,当固相含量达到一定值时,浆料粘度急剧增大,此时浆料粘度已无法满足打印的流动性要求,无法打印,故65wt%时既能获得较大的固相含量值又能满足打印流动性要求。
本专利所述浆料中,碳化硅、碳黑是陶瓷主体,碳纳米管起增韧效果
将上述实施例1-5所得样品1-5和对比例1-5所得样品6-10作为浆料进行3D打印直写成型,工艺流程图如图3所示,具体工艺为:
得到适用于直写成型 3D 打印的碳化硅陶瓷基复合材料浆料,浆料倒入料筒后安装到挤出机。之后,将预先建模的三维模型放入Simplify3D 软件中按最优参数进行切片,将切片文件导入打印机进行直写成型。
以上实施例仅用以说明本发明的技术方案,而非对其进行限制;尽管参照前述实施例对本发明进行了详细的说明,对于本领域的普通技术人员来说,依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或替换,并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。
Claims (9)
1.一种3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,其特征在于,包括以下重量份的组分:58-68份粉体颗粒,31.4-42.5份溶剂,0.8-1.2份粘结剂,0.3-1.2份分散剂,所述粉体颗粒为碳化硅、碳黑、碳纳米管。
2.根据权利要求1所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,其特征在于,所述碳化硅、碳黑、碳纳米管的质量比为8:1:1。
3.根据权利要求2所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,其特征在于,所述所述碳化硅粉末平均粒径为1微米,纯度>99wt%;所述碳黑粉末平均粒径为3微米,纯度>99wt%;所述碳纳米管粉末平均粒径为3.5纳米,纯度>95wt%,进行分散处理后使用。
4.根据权利要求1所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,其特征在于,所述粘结剂为海藻酸钠。
5.根据权利要求4所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,其特征在于,所述溶剂为去离子水。
6.根据权利要求5所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料,其特征在于,所述分散剂为聚乙二醇400。
7.权利要求1-6任一所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料的制备方法,其特征在于,包括如下步骤:
步骤一:将溶剂与粘结剂按比例混合,搅拌均匀,静置12小时,制得粘结剂溶液;
步骤二:将碳纳米管与碳纳米管分散剂按质量比1:1加入到分散溶剂中,超声振荡,得到分散处理后的碳纳米管;
步骤三:将碳化硅粉末、炭黑粉末、分散处理后的碳纳米管按质量比8:1:1混合,搅拌均匀,得到预混粉体;
步骤四:在步骤三所得预混粉体中按比例加入分散剂,充分搅拌进行分散,得到分散后粉体;
步骤五:在步骤四得到的分散后粉体中加入步骤一得到的粘结剂溶液,充分搅拌,制得3D打印用碳纳米管增韧碳化硅陶瓷基复合材料浆料。
8.根据权利要求7所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料的制备方法,其特征在于,步骤二所述分散溶剂为乙醇,所述碳纳米管分散剂为十二烷基硫酸钠。
9.根据权利要求7所述的3D打印碳纳米管增韧碳化硅陶瓷基复合材料浆料的制备方法,其特征在于,步骤一中搅拌速度为200rad/min,搅拌时间为1.5小时;步骤二中振荡时间为30分钟;步骤三中搅拌速度为80rad/min,搅拌时间为30分钟;步骤四中搅拌速度为80rad/min,搅拌时间为30分钟;步骤五中搅拌速度为500rad/min,搅拌时间为3小时。
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