CN117125994A - 一种抗热震碳化硅电热元件及其加工工艺 - Google Patents
一种抗热震碳化硅电热元件及其加工工艺 Download PDFInfo
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- CN117125994A CN117125994A CN202310843191.7A CN202310843191A CN117125994A CN 117125994 A CN117125994 A CN 117125994A CN 202310843191 A CN202310843191 A CN 202310843191A CN 117125994 A CN117125994 A CN 117125994A
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 70
- 238000005485 electric heating Methods 0.000 title claims abstract description 51
- 230000035939 shock Effects 0.000 title claims abstract description 42
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 239000013384 organic framework Substances 0.000 claims abstract description 54
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 239000002070 nanowire Substances 0.000 claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 claims abstract description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006255 coating slurry Substances 0.000 claims abstract description 24
- 238000005336 cracking Methods 0.000 claims abstract description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
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- 239000005711 Benzoic acid Substances 0.000 claims abstract description 9
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 40
- 229910000831 Steel Inorganic materials 0.000 claims description 36
- 239000000835 fiber Substances 0.000 claims description 36
- 239000010959 steel Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 10
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- 239000005995 Aluminium silicate Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
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- 239000000395 magnesium oxide Substances 0.000 claims description 8
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007849 furan resin Substances 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
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- -1 zirconium ions Chemical class 0.000 abstract description 8
- NKGVKOKMGTWFIZ-UHFFFAOYSA-N 6,6-diamino-3-phenylcyclohexa-2,4-diene-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)C(N)(N)C=CC(C=2C=CC=CC=2)=C1 NKGVKOKMGTWFIZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 abstract description 5
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- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 101100096719 Arabidopsis thaliana SSL2 gene Proteins 0.000 description 1
- 101100366560 Panax ginseng SS10 gene Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及电热元件领域,具体是一种抗热震碳化硅电热元件及其加工工艺,用聚碳硅烷、二茂铁修饰有机框架合成原位纳米线增韧碳化硅作为电热元件原件,然后依次经过化学气相渗透、先驱体浸渍裂解转化,大幅提高碳化硅的韧性及抗热震性,用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料,在电热元件原件表面构建具有致密堇青石‑莫来石表面;用4,4‑二氨基‑1,1‑联苯‑3,3‑二羧酸、苯甲酸为配体,与锆离子、钛离子合成有机框架,然后与二茂铁甲醛继续反应生成二茂铁修饰有机框架。
Description
技术领域
本发明涉及电热元件领域,具体是一种抗热震碳化硅电热元件及其加工工艺。
背景技术
电热元件是电热器的核心部件,电热元件的好坏决定电热器的性能和使用寿命,为了提高电热元件的耐高温性,通常在电热元件表层涂刷陶瓷涂层,来提高电热元件的高温抗氧化的效果,但是涂层与基件同样存在热膨胀系数不匹配,结合力不足,从而导致涂层脱落失效的问题。
碳化硅是目前具有应用潜力的高温热结构材料之一,但是其本身具有本征脆性和低延展性,在高低温热循环中容易出现开裂和灾难性失效,即碳化硅的抗热震与韧性较差,限制了其在电热元件中的应用。
发明内容
本发明的目的在于提供一种抗热震碳化硅电热元件及其加工工艺,以解决现有技术中的问题。
为了解决上述技术问题,本发明提供如下技术方案:
一种抗热震碳化硅电热元件的加工工艺,包括以下步骤:
S1:用聚碳硅烷、二茂铁修饰有机框架制备原位纳米线增韧碳化硅;
S2:将原位纳米线增韧碳化硅依次经过化学气相渗透、先驱体浸渍裂解转化,得到改性碳化硅;
S3:用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料;
S4:将涂层浆料涂覆在改性碳化硅表面,烧结,得到一种抗热震碳化硅电热元件。
进一步的,化学气相渗透的工作条件为:以甲烷为先驱体,氮气为稀释气体,在950-1000℃进行沉积,沉积压力为6kPa,沉积时间24h。
进一步的,先驱体浸渍裂解转化的工作条件为:采用质量分数为45%的热固型呋喃树脂作为先驱体,浸渍压力为3MPa,时间1h,浸渍完成后于175℃保温3h,然后升温至1000℃保温1.5h。
进一步的,二茂铁修饰有机框架的制备包括以下步骤:
1)氯化锆、4,4-二氨基-1,1-联苯-3,3-二羧酸、苯甲酸、N,N-二甲基甲酰胺混合,搅拌50-60min,升温至120℃加热12h,加入钛酸四丁酯与N,N-二甲基甲酰胺的混合液,升温至120℃加热12h,冷却、离心、洗涤,得到有机框架;
2)将有机框架和二茂铁甲醛、三氯甲烷混合,搅拌器6-7h,洗涤,烘干,得到二茂铁修饰有机框架。
进一步的,原位纳米线增韧碳化硅的制备包括以下步骤:
(1)将聚碳硅烷研磨过200目筛,加热至300℃保温3h,冷却后加入二茂铁修饰有机框架与二甲苯的混合液,研磨过200目筛,获得前驱体粉末;
(2)将前驱体粉末置于模具中,15MPa下冷压成型,获得前驱体粉末压片,然后采用石墨纸包裹前驱体粉末压片,包埋于活性炭粉中,在氩气气氛下升温至1300℃保温2h,得到原位纳米线增韧碳化硅。
进一步的,以质量份数计,涂层浆料的组成为:基础釉料14-16份、二茂铁修饰有机框架2-5份、聚乙烯醇11-13份。
进一步的,以质量份数计,基础釉料的组成为:电熔莫来石10-20份、高岭土38-40份、活性α-Al2O3微粉2-3份、水合氧化铝1-2份、氧化镁粉5-6份、改性钢纤维2-3份。
进一步的,改性钢纤维的制备包括以下步骤:
将铝粉和硅粉混合,加入钢纤维、热固性酚醛树脂、乙二醇的混合液,超声搅拌1-2h,放置2h,180℃保温8h,冷却,粉碎,过200目筛,得到改性钢纤维。
进一步的,钢纤维的尺寸为20-40μm,铝粉的尺寸为5-10μm,硅粉的尺寸为5-10μm。
本发明制备的碳化硅电热元件与金属电热元件相比,具有使用温度高、抗氧化、耐腐蚀、寿命长、抗热震等特点。根据实际需求,本发明的电热元件可按需在模具中加工成粗端部、等直径硅碳棒,如直型棒、U型棒、枪型棒、槽型棒、单螺纹棒、双螺纹棒等规格型号,其直径范围为6-45mm。
本发明的有益效果:
本发明提供一种抗热震碳化硅电热元件及其加工工艺,用聚碳硅烷、二茂铁修饰有机框架合成原位纳米线增韧碳化硅作为电热元件原件,然后依次经过化学气相渗透、先驱体浸渍裂解转化,大幅提高碳化硅的韧性及抗热震性,用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料,在电热元件原件表面构建具有致密堇青石-莫来石表面,从而大幅增强碳化硅电热元件的抗热震性及力学强度。
用聚碳硅烷研磨,过筛,在空气环境中预氧化形成交联结构,加入用4,4-二氨基-1,1-联苯-3,3-二羧酸、苯甲酸为配体,与锆离子、钛离子合成有机框架,然后与二茂铁甲醛继续反应生成二茂铁修饰有机框架,随加热温度的上升,二茂铁修饰有机框架中的铁原子与钛均促进碳化硅纳米线的形核及生长,随着聚碳硅烷的逐渐裂解生成了中密度碳化硅,裂解过程中释放的含Si和C的硅烷分子与Fe原子、钛原子、锆离子结合形成催化剂液滴,从而原位生长纳米线,然后依次经过化学气相渗透、先驱体浸渍裂解转化,将中密度碳化硅进一步致密化,获得结构致密的原位纳米线增韧碳化硅,原位生长的碳化硅纳米线通过纳米线桥连和拔出增韧机制缓解碳化硅制备及高低温交变过程中的应力集中,从而减少裂纹数量和尺寸,进而提升陶瓷断裂韧性和抗热震性能。
通过控制涂层浆料中组成及含量限定,使涂层浆料在烧结后在电热元件原件的表面形成热膨胀系数相似,耐高温、致密化的堇青石-莫来石表面,从而大幅提高其抗热震性。
选择电熔莫来石、高岭土、活性α-Al2O3微粉、水合氧化铝、氧化镁粉、改性钢纤维作为基础釉料,以高岭土为原料合成堇青石结合莫来石质浇注料,引入第二相改性钢纤维,利用不同材料热膨胀系数的差异性,在内部形成微裂纹以达到改善电热元件抗热震性能的目的。
通过控制铝粉与硅粉的用量,用铝粉与硅粉包覆钢纤维,在高温下原位形成针状、纤维状AlN、Al4C3、SiC,有效降低Si的熔点,促进了表面碳化硅的生成,使颗粒成为类链球结构,将颗粒与基质桥接起来,强化颗粒与基质的结合,从而改善钢纤维与基础釉料中其他成分结合性能,起到协同增强增韧作用,且纤维状Al4C3、AlN具有低膨胀、高热导性,舒缓内热应力,改善电热元件的热震稳定性。
在涂层浆料中引入二茂铁修饰有机框架,使浆料能平整地铺展在原件表面,减少凹坑,减少表面气泡,有助于提升釉面的弹性性能,提高烧结后形成的釉面光滑度。
具体实施方式
下面将结合本发明的实施例,对本发明中的技术方案进行清楚、完整的描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
另外,各个实施例之间的技术方案可以相互结合,但是必须是以本领域普通技术人员能够实现为基础,当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在,也不在本发明要求的保护范围之内。
以下结合具体实施例对本发明的技术方案作进一步详细说明,应当理解,以下实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:一种抗热震碳化硅电热元件的加工工艺,包括以下步骤:
S1:用聚碳硅烷、二茂铁修饰有机框架制备原位纳米线增韧碳化硅,制备包括以下步骤:
(1)将10g聚碳硅烷研磨过200目筛,加热至300℃保温3h,冷却后加入1g的二茂铁修饰有机框架与20mL二甲苯的混合液,研磨过200目筛,获得前驱体粉末;
(2)将前驱体粉末置于模具中,15MPa下冷压成型,获得前驱体粉末压片,然后采用石墨纸包裹前驱体粉末压片,包埋于活性炭粉中,在氩气气氛下升温至1300℃保温2h,得到原位纳米线增韧碳化硅;
二茂铁修饰有机框架的制备包括以下步骤:
1)0.176mmol氯化锆、0.352mmol4,4-二氨基-1,1-联苯-3,3-二羧酸、3.5mmol苯甲酸、7mLN,N-二甲基甲酰胺混合,搅拌50min,升温至120℃加热12h,加入0.176mmol钛酸四丁酯与10mLN,N-二甲基甲酰胺的混合液,升温至120℃加热12h,冷却、离心、洗涤,得到有机框架;
2)将16mg有机框架和80mg二茂铁甲醛、10mL三氯甲烷混合,搅拌器6h,洗涤,烘干,得到二茂铁修饰有机框架;
S2:将原位纳米线增韧碳化硅依次经过化学气相渗透、先驱体浸渍裂解转化,得到改性碳化硅;
化学气相渗透的工作条件为:以甲烷为先驱体,氮气为稀释气体,在950℃进行沉积,沉积压力为6kPa,沉积时间24h;
先驱体浸渍裂解转化的工作条件为:采用质量分数为45%的热固型呋喃树脂作为先驱体,浸渍压力为3MPa,时间1h,浸渍完成后于175℃保温3h,然后升温至1000℃保温1.5h;
S3:用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料;
以质量份数计,涂层浆料的组成为:基础釉料14份、二茂铁修饰有机框架2份、聚乙烯醇11份;
以质量份数计,基础釉料的组成为:电熔莫来石10份、高岭土38份、活性α-Al2O3微粉2份、水合氧化铝1份、氧化镁粉5份、改性钢纤维2份;
改性钢纤维的制备包括以下步骤:
将2g铝粉和2g硅粉混合,加入100g钢纤维、10g热固性酚醛树脂、10g乙二醇的混合液,超声搅拌1h,放置2h,180℃保温8h,冷却,粉碎,过200目筛,得到改性钢纤维;
钢纤维的尺寸为20μm,铝粉的尺寸为5μm,硅粉的尺寸为5μm;
S4:将涂层浆料涂覆在改性碳化硅表面,1100℃烧结4h,得到一种抗热震碳化硅电热元件。
实施例2:一种抗热震碳化硅电热元件的加工工艺,包括以下步骤:
S1:用聚碳硅烷、二茂铁修饰有机框架制备原位纳米线增韧碳化硅,制备包括以下步骤:
(1)将10g聚碳硅烷研磨过200目筛,加热至300℃保温3h,冷却后加入1g的二茂铁修饰有机框架与20mL二甲苯的混合液,研磨过200目筛,获得前驱体粉末;
(2)将前驱体粉末置于模具中,15MPa下冷压成型,获得前驱体粉末压片,然后采用石墨纸包裹前驱体粉末压片,包埋于活性炭粉中,在氩气气氛下升温至1300℃保温2h,得到原位纳米线增韧碳化硅;
二茂铁修饰有机框架的制备包括以下步骤:
1)0.176mmol氯化锆、0.352mmol4,4-二氨基-1,1-联苯-3,3-二羧酸、3.5mmol苯甲酸、7mLN,N-二甲基甲酰胺混合,搅拌55min,升温至120℃加热12h,加入0.176mmol钛酸四丁酯与10mLN,N-二甲基甲酰胺的混合液,升温至120℃加热12h,冷却、离心、洗涤,得到有机框架;
2)将16mg有机框架和80mg二茂铁甲醛、10mL三氯甲烷混合,搅拌器6.5h,洗涤,烘干,得到二茂铁修饰有机框架;
S2:将原位纳米线增韧碳化硅依次经过化学气相渗透、先驱体浸渍裂解转化,得到改性碳化硅;
化学气相渗透的工作条件为:以甲烷为先驱体,氮气为稀释气体,在980℃进行沉积,沉积压力为6kPa,沉积时间24h;
先驱体浸渍裂解转化的工作条件为:采用质量分数为45%的热固型呋喃树脂作为先驱体,浸渍压力为3MPa,时间1h,浸渍完成后于175℃保温3h,然后升温至1000℃保温1.5h;
S3:用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料;
以质量份数计,涂层浆料的组成为:基础釉料15份、二茂铁修饰有机框架4份、聚乙烯醇12份;
以质量份数计,基础釉料的组成为:电熔莫来石15份、高岭土39份、活性α-Al2O3微粉2.5份、水合氧化铝1.5份、氧化镁粉5.5份、改性钢纤维2.5份;
改性钢纤维的制备包括以下步骤:
将2g铝粉和2g硅粉混合,加入100g钢纤维、10g热固性酚醛树脂、10g乙二醇的混合液,超声搅拌1.5h,放置2h,180℃保温8h,冷却,粉碎,过200目筛,得到改性钢纤维;
钢纤维的尺寸为30μm,铝粉的尺寸为6μm,硅粉的尺寸为6μm;
S4:将涂层浆料涂覆在改性碳化硅表面,1100℃烧结4h,得到一种抗热震碳化硅电热元件。
实施例3:一种抗热震碳化硅电热元件的加工工艺,包括以下步骤:
S1:用聚碳硅烷、二茂铁修饰有机框架制备原位纳米线增韧碳化硅,制备包括以下步骤:
(1)将10g聚碳硅烷研磨过200目筛,加热至300℃保温3h,冷却后加入1g的二茂铁修饰有机框架与20mL二甲苯的混合液,研磨过200目筛,获得前驱体粉末;
(2)将前驱体粉末置于模具中,15MPa下冷压成型,获得前驱体粉末压片,然后采用石墨纸包裹前驱体粉末压片,包埋于活性炭粉中,在氩气气氛下升温至1300℃保温2h,得到原位纳米线增韧碳化硅;
二茂铁修饰有机框架的制备包括以下步骤:
1)0.176mmol氯化锆、0.352mmol4,4-二氨基-1,1-联苯-3,3-二羧酸、3.5mmol苯甲酸、7mLN,N-二甲基甲酰胺混合,搅拌50-60min,升温至120℃加热12h,加入0.176mmol钛酸四丁酯与10mLN,N-二甲基甲酰胺的混合液,升温至120℃加热12h,冷却、离心、洗涤,得到有机框架;
2)将16mg有机框架和80mg二茂铁甲醛、10mL三氯甲烷混合,搅拌器7h,洗涤,烘干,得到二茂铁修饰有机框架;
S2:将原位纳米线增韧碳化硅依次经过化学气相渗透、先驱体浸渍裂解转化,得到改性碳化硅;
化学气相渗透的工作条件为:以甲烷为先驱体,氮气为稀释气体,在1000℃进行沉积,沉积压力为6kPa,沉积时间24h;
先驱体浸渍裂解转化的工作条件为:采用质量分数为45%的热固型呋喃树脂作为先驱体,浸渍压力为3MPa,时间1h,浸渍完成后于175℃保温3h,然后升温至1000℃保温1.5h;
S3:用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料;
以质量份数计,涂层浆料的组成为:基础釉料16份、二茂铁修饰有机框架5份、聚乙烯醇13份;
以质量份数计,基础釉料的组成为:电熔莫来石20份、高岭土40份、活性α-Al2O3微粉3、水合氧化铝2份、氧化镁粉6份、改性钢纤维3份;
改性钢纤维的制备包括以下步骤:
将2g铝粉和2g硅粉混合,加入100g钢纤维、10g热固性酚醛树脂、10g乙二醇的混合液,超声搅拌2h,放置2h,180℃保温8h,冷却,粉碎,过200目筛,得到改性钢纤维;
钢纤维的尺寸为40μm,铝粉的尺寸为10μm,硅粉的尺寸为10μm;
S4:将涂层浆料涂覆在改性碳化硅表面,1100℃烧结4h,得到一种抗热震碳化硅电热元件。
对比例1:以实施例3为对照组,在S1中用二茂铁(F408:Merck试剂)替换二茂铁修饰有机框架,其他工序正常。
对比例2:以实施例3为对照组,没有进行化学气相渗透,其他工序正常。
对比例3:以实施例3为对照组,没有进行先驱体浸渍裂解转化,其他工序正常。
对比例4:以实施例3为对照组,没有加入基础釉料,其他工序正常。
对比例5:以实施例3为对照组,用钢纤维替换改性钢纤维,其他工序正常。
对比例6:以实施例3为对照组,涂层浆料中没有加入二茂铁修饰有机框架,其他工序正常。
实施例与对比例中,改性碳化硅为直径为8mm的等直径硅碳棒,涂层浆料在改性碳化硅表面形成的厚度为250μm。
所用原料来源:
聚碳硅烷62306-27-8:(阿尔法)郑州阿尔法化工有限公司;氯化锆221880、苯甲酸242381、N,N-二甲基甲酰胺227056、钛酸四丁酯244112、铝粉GF40979773、二茂铁甲醛122459、聚乙烯醇475904-M:Merck试剂;4,4-二氨基-1,1-联苯-3,3-二羧酸2130-56-5:河南威梯希化工科技有限公司;热固型呋喃树脂(98%):湖北恒景瑞化工有限公司;电熔莫来石:新密市正阳铸造材料厂;高岭土K7375:西格玛奥德里奇(上海)贸易有限公司;活性α-Al2O3微粉1344-28-1:浙江亚美纳米科技有限公司;水合氧化铝1333-84-2:湖北信康医药化工有限公司;氧化镁粉1202001:福斯曼科技(北京)有限公司;硅粉69012-64-2:上海源叶生物科技有限公司;钢纤维SS10:东莞市金世祥塑胶原料有限公司;热固性酚醛树脂30344:东莞市苏广塑胶原料有限公司;二甲苯、三氯甲烷、乙二醇,分析纯:国药集团试剂。
性能测试:
通过阿基米德排水法测量吸水率;通过万能材料试验机测定抗弯强度,跨距为30mm,加载速度为0.5mm/min;根据GB/T30873-2014测试陶瓷抗热震性能,将样品在1500℃条件下保温30min后取出,风冷至18℃,循环5次测吸水率与抗弯强度;具体数据如下表;
本发明提供一种抗热震碳化硅电热元件及其加工工艺,用聚碳硅烷、二茂铁修饰有机框架合成原位纳米线增韧碳化硅作为电热元件原件,然后依次经过化学气相渗透、先驱体浸渍裂解转化,大幅提高碳化硅的韧性及抗热震性,用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料,在电热元件原件表面构建具有致密堇青石-莫来石表面,从而大幅增强碳化硅电热元件的抗热震性及力学强度。
通过实施例1-3可知,经过抗热震性能测试,电热元件的吸水率不升反而降低,抗弯强度大幅增加,说明本发明制备对的碳化硅电热元件具有较高的抗热震性。
实施例3与对比例1进行对比,用聚碳硅烷研磨,过筛,在空气环境中预氧化形成交联结构,加入用4,4-二氨基-1,1-联苯-3,3-二羧酸、苯甲酸为配体,与锆离子、钛离子合成有机框架,然后与二茂铁甲醛继续反应生成二茂铁修饰有机框架,随加热温度的上升,二茂铁修饰有机框架中的铁原子与钛均促进碳化硅纳米线的形核及生长,随着聚碳硅烷的逐渐裂解生成了中密度碳化硅,裂解过程中释放的含Si和C的硅烷分子与Fe原子、钛原子、锆离子结合形成催化剂液滴,从而原位生长纳米线,原位生长的碳化硅纳米线通过纳米线桥连和拔出增韧机制缓解碳化硅制备及高低温交变过程中的应力集中,从而减少裂纹数量和尺寸,进而提升陶瓷断裂韧性和抗热震性能。
实施例3与对比例2、对比例3进行对比,依次经过化学气相渗透、先驱体浸渍裂解转化,将中密度碳化硅进一步致密化,获得结构致密的原位纳米线增韧碳化硅。
实施例3与对比例4进行对比,选择电熔莫来石、高岭土、活性α-Al2O3微粉、水合氧化铝、氧化镁粉、改性钢纤维作为基础釉料,以高岭土为原料合成堇青石结合莫来石质浇注料,引入第二相改性钢纤维,利用不同材料热膨胀系数的差异性,在内部形成微裂纹以达到改善电热元件抗热震性能的目的。
实施例3与对比例5进行对比,通过控制铝粉与硅粉的用量,用铝粉与硅粉包覆钢纤维,在高温下原位形成针状、纤维状AlN、Al4C3、SiC,有效降低Si的熔点,促进了表面碳化硅的生成,使颗粒成为类链球结构,将颗粒与基质桥接起来,强化颗粒与基质的结合,从而改善钢纤维与基础釉料中其他成分结合性能,起到协同增强增韧作用,且纤维状Al4C3、AlN具有低膨胀、高热导性,舒缓内热应力,改善电热元件的热震稳定性。
实施例3与对比例6进行对比,在涂层浆料中引入二茂铁修饰有机框架,使浆料能平整地铺展在原件表面,减少凹坑,减少表面气泡,有助于提升釉面的弹性性能,提高烧结后形成的釉面光滑度。
以上所述仅为本发明的为实施例,并非因此限制本发明的专利范围,凡是在本发明的发明构思下,利用本发明说明书所做的等效结构变换,或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。
Claims (10)
1.一种抗热震碳化硅电热元件的加工工艺,其特征在于,包括以下步骤:
S1:用聚碳硅烷、二茂铁修饰有机框架制备原位纳米线增韧碳化硅;
S2:将原位纳米线增韧碳化硅依次经过化学气相渗透、先驱体浸渍裂解转化,得到改性碳化硅;
S3:用基础釉料、二茂铁修饰有机框架、聚乙烯醇制备涂层浆料;
S4:将涂层浆料涂覆在改性碳化硅表面,烧结,得到一种抗热震碳化硅电热元件。
2.根据权利要求1所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,化学气相渗透的工作条件为:以甲烷为先驱体,氮气为稀释气体,在950-1000℃进行沉积,沉积压力为6kPa,沉积时间24h。
3.根据权利要求1所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,先驱体浸渍裂解转化的工作条件为:采用质量分数为45%的热固型呋喃树脂作为先驱体,浸渍压力为3MPa,时间1h,浸渍完成后于175℃保温3h,然后升温至1000℃保温1.5h。
4.根据权利要求1所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,二茂铁修饰有机框架的制备包括以下步骤:
1)氯化锆、4,4-二氨基-1,1-联苯-3,3-二羧酸、苯甲酸、N,N-二甲基甲酰胺混合,搅拌50-60min,升温至120℃加热12h,加入钛酸四丁酯与N,N-二甲基甲酰胺的混合液,升温至120℃加热12h,冷却、离心、洗涤,得到有机框架;
2)将有机框架和二茂铁甲醛、三氯甲烷混合,搅拌器6-7h,洗涤,烘干,得到二茂铁修饰有机框架。
5.根据权利要求1所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,原位纳米线增韧碳化硅的制备包括以下步骤:
(1)将聚碳硅烷研磨过200目筛,加热至300℃保温3h,冷却后加入二茂铁修饰有机框架与二甲苯的混合液,研磨过200目筛,获得前驱体粉末;
(2)将前驱体粉末置于模具中,15MPa下冷压成型,获得前驱体粉末压片,然后采用石墨纸包裹前驱体粉末压片,包埋于活性炭粉中,在氩气气氛下升温至1300℃保温2h,得到原位纳米线增韧碳化硅。
6.根据权利要求1所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,以质量份数计,涂层浆料的组成为:基础釉料14-16份、二茂铁修饰有机框架2-5份、聚乙烯醇11-13份。
7.根据权利要求1所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,以质量份数计,基础釉料的组成为:电熔莫来石10-20份、高岭土38-40份、活性α-Al2O3微粉2-3、水合氧化铝1-2份、氧化镁粉5-6份、改性钢纤维2-3份。
8.根据权利要求1所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,改性钢纤维的制备包括以下步骤:
将铝粉和硅粉混合,加入钢纤维、热固性酚醛树脂、乙二醇的混合液,超声搅拌1-2h,放置2h,180℃保温8h,冷却,粉碎,过200目筛,得到改性钢纤维。
9.根据权利要求8所述的一种抗热震碳化硅电热元件的加工工艺,其特征在于,钢纤维的尺寸为20-40μm,铝粉的尺寸为5-10μm,硅粉的尺寸为5-10μm。
10.一种抗热震碳化硅电热元件,其特征在于,由权利要求1-9中任一种所述加工工艺加工得到。
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