CN100349826C - 硅化钼型加热元件的制造方法和一种加热元件 - Google Patents
硅化钼型加热元件的制造方法和一种加热元件 Download PDFInfo
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- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910021344 molybdenum silicide Inorganic materials 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 30
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000005275 alloying Methods 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000278 bentonite Inorganic materials 0.000 abstract 2
- 239000000440 bentonite Substances 0.000 abstract 2
- 239000004927 clay Substances 0.000 abstract 2
- 229910001182 Mo alloy Inorganic materials 0.000 abstract 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 229910016006 MoSi Inorganic materials 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
本发明涉及基本由硅化钼和这种基本材料的合金组成的加热元件的制造方法。本发明的特征在于通过以本身已知的方式混合铝硅化钼Mo(Si1-yAly)2和膨润土来生产主要包含Mo(Si1-xAlx)2和Al2O3的材料，其中使该膨润土包含硅化钼不会与其发生合金化且使硅化钼的晶格对称性得到保持的杂质或掺杂物质，其总含量小于2000ppm。本发明还涉及一种加热元件。
Description
本发明涉及硅化钼型加热元件的制造方法并同时涉及一种加热元件。
瑞典专利说明书0003512-1和0004329-9中描述了硅化钼型电阻元件。根据专利说明书0003512-1，该加热元件的电阻材料包含Mo(Si1-xAlx)2，并使其包含铝达一定水平以便在该水平上基本阻止有害物的形成。
已发现当在400-600℃范围的温度下对这种材料进行操作时，没有或者仅有微量的有害物形成。有害物的形成是由于MoSi2与O2形成了MoO3。
有害物的形成显著减少或消除的原因是由于在该元件表面上形成Al2O3。
根据一个优选的实施方案，使x处于0.2-0.6的范围之内。
另一个专利说明书0004329-9提出了提高加热元件的使用寿命的方法，该元件主要由硅化钼和这种基本材料的合金组成并且在高温下工作。
根据这个专利说明书，使该加热元件包含铝达一定水平从而能够在该加热元件的表面上维持稳定，缓慢生长的氧化铝层。
根据一个优选的实施方案，使该加热元件的材料包含Mo(Si1-xAlx)2，其中x处于0.2-0.6的范围之内。
已发现包含铝的硅化钼型材料在低温和高温下都具有改良的腐蚀性能。
通常，通过混合物MoSi2粉和氧化性(oxidic)原料例如铝硅酸盐来制造这种材料。当该原料是膨润土时得到了相对低的熔点这有助于所谓的熔融相烧结，该烧结可产生包含MoSi2和相当于15-20体积百分比的一部分铝硅酸盐的致密材料。
膨润土具有不同的组成。一些膨润土包含60wt％的SiO2而一些包含略大于70wt％的SiO2。虽然Al2O3的含量不等，但其通常处于13-20wt％的范围之间。该熔点可以在约1200-1400℃之间不等。
主要包含SiO2的膨润土可用于生产包含Mo(Si1-xAlx)2的加热元件。当与铝合金化硅化物进行烧结时，可发生化学置换反应，其中氧对Al的亲和力比对Si大的从而导致Si离开铝硅酸盐并进入硅化物，因为Al离开硅化物而被氧化物相吸收。这个置换反应还有助于该复合材料烧结性能的改良。最终的材料包含基本不含铝的Mo(Si1-xAlx)2，其中该氧化物相基本上包含Al2O3。
标准的制造工序包括混合粉末形式的钼，硅和铝并通常在保护气氛下烧成该粉末混合物。这可产生材料Mo(Si1-yAly)2的团块(cake)，其中作为所述置换反应的结果y大于x。该反应是放热反应。然后将该团块粉碎并研磨成通常为大约1-20μm的细颗粒尺寸。将该粉末与膨润土混合以便形成湿的陶瓷材料。对该材料进行挤压和干燥形成杆状，该杆的直径对应于随后加热元件的直径。然后在超过所包含成分的熔化温度的温度下对该材料进行烧结。
然而，这种类型的元件存在一个缺点。该问题是在元件表面上形成的氧化物即Al2O3在循环操作的情形下有时会从元件的表面剥离或剥落，也就是变松。
剥离的氧化物会对铝的随后的氧化提供较为不良的保护，且铝在该元件的外表面耗尽的更快。此外，剥离的氧化物会玷污安装有该元件的烘箱，而且在具有这种元件的烘箱中进行热处理的产品会具有性能和外观严重受损的风险。这限制了这种元件在加热处理中的使用。
本发明解决了这个问题。
本发明因此涉及基本由硅化钼型和这种基本材料的合金组成的加热元件的制造方法，其特征在于通过以本身已知的方式混合铝硅化钼(Mo(Si1-yAly)2)和膨润土来生产主要包含Mo(Si1-xAlx)2和Al2O3的材料，其中使该膨润土包含硅化钼不会与其发生合金化且使硅化钼的晶格对称性得到保持的杂质，其总含量小于2000ppm，其中使x处于0.4-0.6的范围内。
本发明还涉及这种类型的加热元件，其特征在于所述元件主要由材料Mo(Si1-xAlx)2和Al2O3组成；其中该材料包含硅化钼不会与之发生合金化且使硅化钼的晶格对称性得到保持的杂质，其总含量小于2000ppm，其中使x处于0.4-0.6的范围之内。
在下文中将对本发明进行更详细的说明。
根据本发明，原则上通过上面所述的方法来制造主要由硅化钼型和这种基本材料的合金组成的加热元件。由此产生了主要包含Mo(Si1-yAly)2的粉末，并使该粉末与包含Al2O3的膨润土混合。
根据本发明，使膨润土包含硅化钼不会与之发生合金化的杂质，使晶格对称性得到保持，其总含量小于2000ppm。可以在已知的化学净化工艺的帮助下，通过对该膨润土进行纯化来生产具有这些低杂质含量的膨润土。
与这种方法不同，可以用Re或W部分取代材料Mo(Si1-xAlx)2中的钼而不改变该晶格的对称性。
根据本发明的一个优选实施方案，使杂质物质Mg，Ca，Fe，Na和K的总含量低于2000ppm。
根据本发明的另一个优选实施方案，使所述杂质物质的含量低于1000ppm。
意外发现获得了具有低杂质含量的氧化物，在室温到高温如1500℃之间该氧化物在循环操作之后不会发生剥落。
根据一个实施方案，使x处于0.4-0.6的范围之内。
根据一个优选的实施方案，使x处于0.45-0.55的范围之内。
本发明因此解决了介绍中所提到的问题并使得本元件适用于烘箱而不会对在烘箱中进行处理的材料造成损害。
由于在所附权利要求的范围内可以做出改变，因此不应认为本发明局限于前述的实施方案。
Claims (10)
1.制造基本由硅化钼型材料和该硅化钼型材料的合金组成的加热元件的方法，其特征在于以本身已知的方式通过混合铝硅化钼Mo(Si1-yAly)2和膨润土来生产主要包含Mo(Si1-xAlx)2和Al2O3的材料，其中使该膨润土包含硅化钼不会与之发生合金化且使硅化钼的晶格对称性得到保持的杂质，其总含量小于2000ppm，其中使x处于0.4-0.6的范围之内。
2.根据权利要求1的方法，其特征在于使杂质Mg，Ca，Fe，Na和K的总含量小于2000ppm。
3.根据权利要求1或2的方法，其特征在于使所述杂质的总含量小于1000ppm。
4.根据权利要求1或2的方法，其特征在于使x处于0.45-0.55的范围之内。
5.根据权利要求1或2的方法，其特征在于用Re或W部分取代材料Mo(Si1-xAlx)2中的钼。
6.基本由硅化钼型材料和该硅化钼型材料的合金组成的电加热元件，其特征在于所述元件主要由材料Mo(Si1-xAlx)2和Al2O3组成；其中该材料包含硅化钼不会与之发生合金化且使硅化钼的晶格对称性得到保持的杂质，其总含量小于2000ppm，其中使x处于0.4-0.6的范围之内。
7.根据权利要求6的加热元件，其特征在于使杂质Mg，Ca，Fe，Na和K的总含量小于2000ppm。
8.根据权利要求6或7的加热元件，其特征在于使所述材料的杂质含量小于1000ppm。
9.根据权利要求6或7的加热元件，其特征在于使x处于0.45-0.55的范围之内。
10.根据权利要求6或7的加热元件，其特征在于用Re或W部分取代材料Mo(Si1-xAlx)2中的钼。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE0201043A SE521796C2 (sv) | 2002-04-05 | 2002-04-05 | Förfarande för tillverkning av ett värmeelement av molybdensilicidtyp jämte ett värmeelement |
| SE02010437 | 2002-04-05 |
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| Publication Number | Publication Date |
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| CN1642874A CN1642874A (zh) | 2005-07-20 |
| CN100349826C true CN100349826C (zh) | 2007-11-21 |
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| CNB038074729A Expired - Fee Related CN100349826C (zh) | 2002-04-05 | 2003-03-06 | 硅化钼型加热元件的制造方法和一种加热元件 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7166823B2 (zh) |
| EP (1) | EP1492741B1 (zh) |
| JP (2) | JP4913988B2 (zh) |
| KR (1) | KR100635963B1 (zh) |
| CN (1) | CN100349826C (zh) |
| AU (1) | AU2003210093A1 (zh) |
| SE (1) | SE521796C2 (zh) |
| WO (1) | WO2003087015A1 (zh) |
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| CN102405198A (zh) * | 2009-05-05 | 2012-04-04 | 山特维克知识产权股份有限公司 | 加热元件 |
| CN102173814B (zh) * | 2011-03-04 | 2013-02-06 | 郑州嵩山电热元件有限公司 | 一种二硅化钼基电热元件及其制备方法 |
| EP3394001B1 (en) * | 2015-12-21 | 2019-11-06 | Sandvik Intellectual Property AB | A new molybdenum silicide based composition |
| PL3768653T3 (pl) * | 2018-03-18 | 2022-06-20 | Kanthal Ab | Element grzejny zawierający części dikrzemku molibdenu |
| US11932579B2 (en) | 2018-11-16 | 2024-03-19 | Kanthal Ab | Process for manufacturing a chromium alloyed molybdenum silicide portion of a heating element |
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| US5611953A (en) * | 1994-05-13 | 1997-03-18 | Micropyretics Heaters International, Inc. | Sinter-homogenized heating products |
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| JPH01313362A (ja) * | 1988-06-09 | 1989-12-18 | Ngk Spark Plug Co Ltd | セラミック発熱体およびその製造方法 |
| JPH03141162A (ja) * | 1989-10-26 | 1991-06-17 | Riken Corp | 二珪化モリブデン発熱体の製造法 |
| AU2606895A (en) | 1994-05-13 | 1995-12-05 | Micropyretics Heaters International | Sinter-homogenized heating products |
| SE504235C2 (sv) * | 1995-04-11 | 1996-12-09 | Kanthal Ab | Elektriskt motståndselement av molybdensilicidtyp |
| EP0992470B1 (en) * | 1995-08-03 | 2006-03-08 | Ngk Insulators, Ltd. | Aluminium nitride sintered bodies and their use as substrate in an apparatus for producing semiconductors |
| JPH10324571A (ja) * | 1997-05-23 | 1998-12-08 | Riken Corp | 二珪化モリブデン系セラミックス発熱体及びその製造方法 |
| JP3657800B2 (ja) * | 1998-02-20 | 2005-06-08 | 株式会社リケン | 二珪化モリブデン系複合セラミックス発熱体及びその製造方法 |
| SE512980C2 (sv) * | 1998-10-22 | 2000-06-12 | Flaekt Ab | Filteranordning för luftkanaler eller luftbehandlingsaggregat |
| SE520251C2 (sv) * | 1999-05-20 | 2003-06-17 | Sandvik Ab | Motståndselement av molybdensilicidtyp för sintring av metallpulver |
| SE9904170L (sv) * | 1999-11-18 | 2000-12-11 | Sandvik Ab | Molybdensilicid-material med hög hållfasthet |
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| SE520149C2 (sv) * | 2000-09-29 | 2003-06-03 | Sandvik Ab | Förfarande för att öka livslängden hos värmeelement av molybdensilicidtyp vid lägre temperatur |
| SE520148C3 (sv) * | 2000-11-24 | 2003-07-16 | Sandvik Ab | Förfarande för att öka livslängden hos värmeelement av molybdendisilicidtyp vid värmebehandling av elektroniska keramer |
| SE521882C2 (sv) * | 2001-06-21 | 2003-12-16 | Sandvik Ab | Förfarande för framställning av en enfassammansättning innefattande metall |
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2002
- 2002-04-05 SE SE0201043A patent/SE521796C2/sv unknown
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2003
- 2003-03-06 CN CNB038074729A patent/CN100349826C/zh not_active Expired - Fee Related
- 2003-03-06 JP JP2003583974A patent/JP4913988B2/ja not_active Expired - Fee Related
- 2003-03-06 KR KR1020047015774A patent/KR100635963B1/ko active IP Right Grant
- 2003-03-06 WO PCT/SE2003/000380 patent/WO2003087015A1/en active Application Filing
- 2003-03-06 EP EP20030746180 patent/EP1492741B1/en not_active Expired - Lifetime
- 2003-03-06 AU AU2003210093A patent/AU2003210093A1/en not_active Abandoned
- 2003-03-06 US US10/510,146 patent/US7166823B2/en not_active Expired - Lifetime
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2010
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| GB751294A (en) * | 1953-12-31 | 1956-06-27 | Metro Cutanit Ltd | Improvements in and relating to methods of making tubular heating elements from powdered materials |
| US5611953A (en) * | 1994-05-13 | 1997-03-18 | Micropyretics Heaters International, Inc. | Sinter-homogenized heating products |
| US5965051A (en) * | 1995-01-24 | 1999-10-12 | Fuji Electric Co., Ltd. | Ceramic heating element made of molybdenum disilicide and silicon carbide whiskers |
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Also Published As
| Publication number | Publication date |
|---|---|
| US7166823B2 (en) | 2007-01-23 |
| US20050242083A1 (en) | 2005-11-03 |
| JP2005522402A (ja) | 2005-07-28 |
| JP4913988B2 (ja) | 2012-04-11 |
| SE521796C2 (sv) | 2003-12-09 |
| EP1492741A1 (en) | 2005-01-05 |
| EP1492741B1 (en) | 2015-04-22 |
| JP2011020920A (ja) | 2011-02-03 |
| SE0201043D0 (sv) | 2002-04-05 |
| AU2003210093A1 (en) | 2003-10-27 |
| CN1642874A (zh) | 2005-07-20 |
| WO2003087015A1 (en) | 2003-10-23 |
| KR100635963B1 (ko) | 2006-10-19 |
| KR20040105845A (ko) | 2004-12-16 |
| SE0201043L (sv) | 2003-10-06 |
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