CN112174670A - 一种石墨材料致密化改性的制备方法、由此得到的致密化石墨材料及其应用 - Google Patents
一种石墨材料致密化改性的制备方法、由此得到的致密化石墨材料及其应用 Download PDFInfo
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Abstract
本发明涉及一种石墨材料致密化改性的制备方法包括将天然鳞片石墨、人造石墨和纳米级炭黑混合得到干粉混料;将粘结剂添加到干粉混料中混捏均匀后得到预制石墨粉;压制预制石墨粉形成坯体;将坯体进行炭化处理和石墨化处理得到致密化石墨材料;纳米级炭黑的质量为天然鳞片石墨、人造石墨和粘结剂的总质量的1‑20%。本发明得到的致密化石墨材料,其平均孔径为50‑500nm。本发明的致密化石墨材料的应用,其在反应堆中作为燃料元件燃料层的基体材料、在反应堆中作为燃料元件外壳层的材料、或在相变储热元件中作为封装材料。根据本发明的致密化石墨材料,平均孔径小、抗熔盐浸渗能力高、热导率高、热膨胀系数低。
Description
技术领域
本发明涉及石墨材料,更具体地涉及一种石墨材料致密化改性的制备方法、由此得到的致密化石墨材料及其应用。
背景技术
传统石墨材料的制备工序较多,工艺复杂。一般采用炭骨料(如人造石墨、天然石墨等)与粘结剂为原料,按一定比例混合。经混捏、挤条、破碎和筛分等工序,先制得粉体原料。再将粉体原料经模压或等静压(或准等静压)工艺制得坯体。然后根据实际热处理需要,将坯体进行炭化处理和进一步的石墨化处理,得到所需制品。现有技术中已知的此类石墨材料为用于高温气冷堆的球形燃料元件基体石墨。当该燃料元件用于熔盐冷却反应堆时,存在体密度大,不利于元件浮动在线装卸料等缺点。另外,用于高温气冷堆的球形燃料元件的外壳层石墨孔径分布在1μm左右,不利于阻隔冷却剂熔盐的浸渗(M.W.Rosenthal,P.N.Haubenreich,R.B.Briggs.The development status of molten-salt breederreactors.ORNL-4812.1972.报道:为阻隔熔盐浸渗,孔径应控制在1μm以下)。
发明内容
为了解决上述现有技术中的石墨材料的平均孔径较大等问题,本发明提供一种石墨材料致密化改性的制备方法、由此得到的致密化石墨材料及其应用。
根据本发明的一个方面,石墨材料致密化改性的制备方法包括以下步骤:S1,将天然鳞片石墨、人造石墨和纳米级炭黑混合得到干粉混料;S2,将粘结剂添加到干粉混料中混捏均匀后得到预制石墨粉;S3,压制预制石墨粉形成坯体;S4,将坯体进行炭化处理和石墨化处理得到致密化石墨材料;其中,纳米级炭黑的质量为天然鳞片石墨、人造石墨和粘结剂的总质量的1-20%。
根据本发明的制备方法首创性地提出通过纳米级炭黑的添加来实现石墨材料致密化改性。实践表明,纳米级炭黑作为优质前驱体,呈球形且具有一定的颗粒分布,容易在压力下实现紧密堆积,具有较好的填充孔隙作用。特别地,非纳米级的炭黑无法应用于本发明中起到致密化的作用。
优选地,纳米级炭黑的平均粒径为10-500nm。在优选的实施例中,该纳米级炭黑的平均粒径为250nm。
优选地,纳米级炭黑的质量为天然鳞片石墨、人造石墨和粘结剂的总质量的5-10%。
优选地,天然鳞片石墨、人造石墨和粘结剂的质量百分数之比为55%-65%:5%-20%:15%-25%。
优选地,天然鳞片石墨、人造石墨和粘结剂的质量百分数之比为64%:16%:20%。
优选地,粘结剂为酚醛树脂。应该理解,该粘结剂还可以是煤焦油、煤沥青、环氧树脂、蒽油和中间相沥青中的一种或多种,只要能够提高压坯的强度或防止粉末偏析的可在烧结前或烧结过程中除掉的物质均可。
特别地,本发明的制备方法在步骤S1中将天然鳞片石墨、人造石墨和纳米级炭黑干粉混匀,防止直接加入液体粘结剂产生团聚等分散不均匀的现象。根据本发明的制备方法在步骤S2中,在混捏设备内,将液体粘结剂添加到干粉混料中再进行混捏。优选地,根据本发明的制备方法在步骤S2中,将粘结剂添加到干粉混料中混捏均匀得到糊状料,经挤条切粒、干燥、破碎、筛分得到预制石墨粉。根据本发明的制备方法在步骤S3中,通过等静压压制、准等静压压制或单向模压压制形成坯体。例如片状的材料可采用定型模压的压制方法。
优选地,根据本发明的制备方法的压制压力为30-250MPa。
优选地,根据本发明的制备方法的炭化温度为600-1000℃,石墨化温度为1850-2800℃。在一个优选的实施例中,根据本发明的制备方法的炭化温度为800℃,石墨化温度为2800℃。
根据本发明的另一个方面,根据上述的制备方法得到的致密化石墨材料,致密化石墨材料的平均孔径为50-500nm。在优选的实施例中,致密化石墨材料的平均孔径为92-306nm。应该理解,根据上述的制备方法得到的致密化石墨材料为混合物,这里的孔径为平均孔径。通常,平均孔径超过500nm的致密化石墨材料混合物中出现大孔的概率明显较大,至少比平均孔径小于500nm的致密化石墨材料混合物中出现大孔的概率大,也就是说,平均孔径超过500nm的致密化石墨材料很有可能无法有效阻隔熔盐浸渗。
优选地,致密化石墨材料的孔隙率为10%-20%,体积密度为1.77-1.9g/cm3。在优选的实施例中,致密化石墨材料的孔隙率为12.0%-16.2%,体积密度为1.8-1.87g/cm3。据此,相对于不添加纳米级炭黑的石墨材料,本发明的纳米级炭黑具有良好的孔隙填充效果。
优选地,致密化石墨材料在700℃下在熔盐中浸渗20小时的临界浸渗压强为1-10MPa。在优选的实施例中,致密化石墨材料在700℃下在熔盐中浸渗20小时的临界浸渗压强为1.20-7.55MPa。据此,相对于不添加纳米级炭黑的石墨材料,本发明的纳米级炭黑能够有效提高石墨材料的抗熔盐浸渗能力。
优选地,致密化石墨材料的热导率为10-42W/(m.K)。在优选的实施例中,致密化石墨材料的热导率为14-36W/(m.K)。应该理解,根据上述的制备方法通过不超过20%的纳米级炭黑来防止热导率的降低。
优选地,致密化石墨材料的热膨胀系数为4.15×10-6K-1-4.52×10-6K-1。应该理解,根据上述的制备方法通过不超过20%的纳米级炭黑来防止热膨胀系数的升高。
根据本发明的又一个方面,根据上述的致密化石墨材料的应用,其在反应堆中作为燃料元件燃料层的基体材料、在反应堆中作为燃料元件外壳层的材料、或在相变储热元件中作为封装材料。
根据本发明的致密化石墨材料,平均孔径小、抗熔盐浸渗能力高、热导率高、热膨胀系数低,各向异性度低,适于在反应堆中作为燃料元件燃料层的基体材料和外壳层材料,同时适用于多种相变储热材料的封装材料。根据本发明的制备方法,工艺简单,成本低廉。
具体实施方式
下面给出本发明的较佳实施例,并予以详细描述。
在以下实施例中,纳米级炭黑购自天津天一世纪化工产品科技发展有限公司,其平均粒径为250nm;天然鳞片石墨购于中钢集团新型材料(浙江)有限公司,其参数为:松装密度为0.52-0.53g/cm3,粒度D50为19-23μm,水份为0.02%,真密度为2.258-2.275g/cm3;人造石墨购于中钢集团新型材料(浙江)有限公司,其参数为:松装密度为0.55g/cm3,粒度D50为18-22μm,水份为0.02%,真密度为2.235-2.258g/cm3;酚醛树脂购于上海华夏化工材料有限公司,其型号为PF211,其参数为:分子量690,软化点101℃,熔点97℃,pH值为6,残炭量50wt%,灰度(ppm)为1。
在以下实施例中,热导率测试采用激光热导仪(耐驰);孔径分布测试采用压汞法,国标:GB/T 21650.1-2008压汞法和气体吸附法测定固体材料孔径分布和孔隙率第一部分:压汞法。
实施例1
将64g天然鳞片石墨、16g人造石墨和1g纳米级炭黑混合得到干粉混料。
将20g酚醛树脂添加到干粉混料中混捏均匀,经挤条切粒、干燥、破碎、筛分得到预制石墨粉。
采用SH(Semihydrostatiche pressverfahren)准等静压法压制形成球形坯体。具体地,将上述的预制石墨粉加入准等静压用硅胶模具内,以200MPa准等静压压成形,压制时,硅胶模具模腔内产生准各向同性的压力,使得椭球腔内的原料粉体被压制成球体,得到球形坯体。
将坯体进行800℃炭化处理,2800℃石墨化处理,得到致密化石墨材料。
实施例2
将64g天然鳞片石墨、16g人造石墨和5g纳米级炭黑混合得到干粉混料。
将20g酚醛树脂添加到干粉混料中混捏均匀,经挤条切粒、干燥、破碎、筛分得到预制石墨粉。
采用SH准等静压法压制形成球形坯体。具体地,将上述的预制石墨粉加入准等静压用硅胶模具内,以200MPa准等静压压成形,压制时,硅胶模具模腔内产生准各向同性的压力,使得椭球腔内的原料粉体被压制成球体,得到球形坯体。
将坯体进行800℃炭化处理,2800℃石墨化处理,得到致密化石墨材料。
实施例3
将64g天然鳞片石墨、16g人造石墨和10g纳米级炭黑混合得到干粉混料。
将20g酚醛树脂添加到干粉混料中混捏均匀,经挤条切粒、干燥、破碎、筛分得到预制石墨粉。
采用SH准等静压法压制形成球形坯体。具体地,将上述的预制石墨粉加入准等静压用硅胶模具内,以200MPa准等静压压成形,压制时,硅胶模具模腔内产生准各向同性的压力,使得椭球腔内的原料粉体被压制成球体,得到球形坯体。
将坯体进行800℃炭化处理,2800℃石墨化处理,得到致密化石墨材料。
实施例4
将64g天然鳞片石墨、16g人造石墨和15g纳米级炭黑混合得到干粉混料。
将20g酚醛树脂添加到干粉混料中混捏均匀,经挤条切粒、干燥、破碎、筛分得到预制石墨粉。
采用SH准等静压法压制形成球形坯体。具体地,将上述的预制石墨粉加入准等静压用硅胶模具内,以200MPa准等静压压成形,压制时,硅胶模具模腔内产生准各向同性的压力,使得椭球腔内的原料粉体被压制成球体,得到球形坯体。
将坯体进行800℃炭化处理,2800℃石墨化处理,得到致密化石墨材料。
实施例5
将64g天然鳞片石墨、16g人造石墨和20g纳米级炭黑混合得到干粉混料。
将20g酚醛树脂添加到干粉混料中混捏均匀,经挤条切粒、干燥、破碎、筛分得到预制石墨粉。
采用SH准等静压法压制形成球形坯体。具体地,将上述的预制石墨粉加入准等静压用硅胶模具内,以200MPa准等静压压成形,压制时,硅胶模具模腔内产生准各向同性的压力,使得椭球腔内的原料粉体被压制成球体,得到球形坯体。
将坯体进行800℃炭化处理,2800℃石墨化处理,得到致密化石墨材料。
对比例
将64g天然鳞片石墨和16g人造石墨混合得到干粉混料。
将20g酚醛树脂添加到干粉混料中混捏均匀,经挤条切粒、干燥、破碎、筛分得到预制石墨粉。
采用SH准等静压法压制形成球形坯体。具体地,将上述的预制石墨粉加入准等静压用硅胶模具内,以200MPa准等静压压成形,压制时,硅胶模具模腔内产生准各向同性的压力,使得椭球腔内的原料粉体被压制成球体,得到球形坯体。
将坯体进行800℃炭化处理,2800℃石墨化处理,得到未致密化石墨材料。
实施例1-实施例5制得的致密化石墨材料的平均孔径依次为:306,141,120,105,92nm,对比例制得的未致密化石墨材料的平均孔径为573nm;实施例1-实施例5制得的致密化石墨材料的孔隙率依次为:16.2%,14.9%,15.1%,14.9%,12.0%,对比例制得的未致密化石墨的孔隙率为22.9%;实施例1-实施例5制得的致密化石墨材料的体积密度依次为:1.85,1.87,1.85,1.80,1.84g/cm3,对比例制得的未致密化石墨的体积密度为1.73g/cm3;实施例1-实施例5制得的致密化石墨材料700℃下在熔盐中浸渗20小时的临界浸渗压强分别是:1.20,1.13,1.35,1.35,7.55MPa,对比例制得的未致密化石墨的临界浸渗压强为0.60MPa;实施例1-实施例5制得的致密化石墨材料的热导率依次为:36,35,25,22,14W/(m.K),对比例制得的未致密化石墨的热导率为42W/(m.K);实施例1-实施例5制得的致密化石墨材料的热膨胀系数依次为:4.27×10-6K-1,4.15×10-6K-1,4.52×10-6K-1,4.25×10-6K-1,4.26×10-6K-1,对比例制得的未致密化石墨的热膨胀系数为4.10×10-6K-1。
在上述实施例中,天然鳞片石墨、人造石墨和酚醛树脂为基础配比,在此配比上添加纳米级炭黑。具体地,上述实施例中以质量百分数为64%的天然鳞片石墨、16%的人造石墨和20%的酚醛树脂为基础配比,在此配比上添加1-20%的纳米级炭黑。应该理解,基础配比并不局限于上述比例,55%-65%的天然鳞片石墨、5%-20%的人造石墨和15%-25%的酚醛树脂也是可行的。另外,纳米级炭黑占到基础配比的5%-10%是优选的方案。
以上所述的,仅为本发明的较佳实施例,并非用以限定本发明的范围,本发明的上述实施例还可以做出各种变化。即凡是依据本发明申请的权利要求书及说明书内容所作的简单、等效变化与修饰,皆落入本发明专利的权利要求保护范围。本发明未详尽描述的均为常规技术内容。
Claims (10)
1.一种石墨材料致密化改性的制备方法,其特征在于,该制备方法包括以下步骤:
S1,将天然鳞片石墨、人造石墨和纳米级炭黑混合得到干粉混料;
S2,将粘结剂添加到干粉混料中混捏均匀后得到预制石墨粉;
S3,压制预制石墨粉形成坯体;
S4,将坯体进行炭化处理和石墨化处理得到致密化石墨材料;
其中,纳米级炭黑的质量为天然鳞片石墨、人造石墨和粘结剂的总质量的1-20%。
2.根据权利要求1所述的制备方法,其特征在于,纳米级炭黑的平均粒径为10-500nm。
3.根据权利要求1所述的制备方法,其特征在于,纳米级炭黑的质量为天然鳞片石墨、人造石墨和粘结剂的总质量的5-10%。
4.根据权利要求1所述的制备方法,其特征在于,天然鳞片石墨、人造石墨和粘结剂的质量百分数之比为55%-65%:5%-20%:15%-25%。
5.根据权利要求1所述的制备方法,其特征在于,粘结剂为酚醛树脂。
6.根据权利要求1-5中任一项所述的制备方法得到的致密化石墨材料,其特征在于,致密化石墨材料的平均孔径为50-500nm。
7.根据权利要求6所述的致密化石墨材料,其特征在于,致密化石墨材料的孔隙率为10%-20%,体积密度为1.77-1.9g/cm3。
8.根据权利要求6所述的致密化石墨材料,其特征在于,致密化石墨材料的热导率为10-42W/(m.K)。
9.根据权利要求6所述的致密化石墨材料,其特征在于,致密化石墨材料的热膨胀系数为4.15×10-6K-1-4.52×10-6K-1。
10.根据权利要求6-9中任一项所述的致密化石墨材料的应用,其特征在于,致密化石墨材料在反应堆中作为燃料元件燃料层的基体材料、在反应堆中作为燃料元件外壳层的材料、或在相变储热元件中作为封装材料。
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