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CN1117169C - 电阻加热元件 - Google Patents

电阻加热元件 Download PDF

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CN1117169C
CN1117169C CN00807344A CN00807344A CN1117169C CN 1117169 C CN1117169 C CN 1117169C CN 00807344 A CN00807344 A CN 00807344A CN 00807344 A CN00807344 A CN 00807344A CN 1117169 C CN1117169 C CN 1117169C
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马茨·松德贝里
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Abstract

本发明涉及一种电阻元件，其主要包含化学式为Mo(Si1-xAlx)2的硅化物相，这种物相在元件的表面上形成氧化铝。这种元件将用于有关金属粉末烧结的领域。由于它具有在表面上形成氧化铝层的令人惊异的优越能力，这种材料在超过1500℃高温下，在还原性和氧化性两种气氛中均表现出很强的抗腐蚀性。

Description

电阻加热元件
本发明涉及一种新的硅化钼型电阻加热元件，以及将这种元件用于有关金属粉末烧结的领域。
自从二十世纪五十年代以来，上述种类的电阻加热元件就已存在，例如商标为Kanthal Super的电阻加热元件。这些元件通常主要含有如MoSi2相或是MoxW1-XSi2相以及硅酸铝的氧化物相类型的金属。类似的材料能在氧化性气氛中在元件温度高达1900℃时使用。
使其能在高温下工作的因素，除所述的材料具有超过2000℃的高熔点之外，是二氧化硅的氧化层，氧化层形成后即迅速地使基材钝化阻止了氧化加快，由此使加热元件能够具有较长的使用寿命。这种表面层能在多种熔炉内和热处理气氛下给与一种持久的保护，如在空气、氧气、氮气/氢气、裂化氨等等条件下。在这些气氛中经常限制使用的情况是，在高温下的元件同时处于极低含量的氧，或者极低的露点这种气氛下。如果元件的露点和温度之比例超过临界条件，氧化硅层会变得不稳定，并在经过一定时间之后会失去对基材的任何保护。例如在氢气中，当露点低于约-30℃，元件温度达1300℃时，这种情况就会发生。为使氧化硅层在元件温度达1450℃时维持稳定，露点须超过+20℃，即氢气含量须超过2.3体积％。氧化硅的稳定性造成元件在某些方面使用的限制。
在一个应用实施例中，这些限制在烧结金属粉末生产不锈钢时充分表现出来。AISI316L级不锈钢的零件最主要是通过粉末压制，或者通过金属粉末注模(injection moulding)制成。在粘合剂于低温下蒸发以后，最后的烧结经常需要在温度为1300-1360℃的还原气氛中进行。这种还原性气体可以是纯氢，其露点为-40℃至-60℃，分别相当于水含量为0.01至0.001体积％。为了在烧结过程中还原金属氧化物，必须采用这种低露点，并由此导致生成一种具有高密度和良好机械性能的材料。在这样一个应用实例中，取决于元件形状和炉子设计，元件温度应该达到1400℃和1550℃之间。而在那些条件下，在以MoSi2为基料的加热元件上的氧化硅层肯定是不稳定的。
今天，在温度超过1250-1300℃范围下烧结金属粉末的许多熔炉中，其所使用的加热元件主要是由钼制造的，但也有由钨制造的。这种材料的局限性是，除其在熔炉中的总成本比较高之外，还需要在所有超过400℃的情况下，在缺乏氧的气氛中保持元件避免发生有害的纯钼金属的氧化作用。例如在熔炉泄漏或者其他的故障中那些元件可能因此而损坏。
在这些条件下用于电阻加热元件的其它材料可以是如FeCrAl、NiCr和MoSi2(例如上述的Kanthal Super)等合金和金属间化合物。MoSi2材料的局限性如上所述。FeCrAl和NiCr在空气中使用时分别在表面上形成氧化物Al2O3和Cr2O3。在还原气氛如干的氢气中，FeCrAl的使用温度范围限制在约1400℃，NiCr(例如商标Nicrothal 80)的使用温度范围限制在约1250℃。
对于NiCr合金，Cr2O3在高于这种温度之上时是不稳定的。对于FeCrAl，Al2O3层的确维持了稳定，可是由于接近约1500℃的熔炼温度，这种材料在此温度下的使用寿命受到限制。这样，如果需要用FeCrAl来烧结316L，对元件耐高温的要求将导致其使用寿命很有限。
需要使用一种能在表面上形成氧化铝同时熔解温度明显高于1500℃的材料，并且如有必要，它可以交替地用于还原性气氛和氧化性气氛中。此外，因为这种钼加热元件不一定总是用于缺乏氧气的气氛中，而那时它的缺点就可消除。
现已令人吃惊地发现，通过将MoSi2与充足数量的铝以及氧化铝相掺和，可得到一种铝硅化钼相(molybdenum alumina silicide)Mo(Si1-XAlx)2，它在高温下的干的氢气中是稳定的。例如在1450℃的氢气中对复合材料MoSi1.6Al0.4/Al2O3进行腐蚀性试验，在200小时以后它并未显示出任何腐蚀，但是重量上有0.2％的轻微增加，这归因于铝硅化物中的铝氧化成三氧化二铝。用Kanthal Super 1800(由MoSi2和约20体积％硅酸铝组成)进行的比较试验表明，在相同条件下它被还原的重量约为30％。在这种情况下除二氧化硅层之外，MoSi2相、Mo5Si3和Mo3Si以及含有粘合剂的硅酸铝也都被还原。
可以设想，甚至使用其他的组合物也可得到相似的结果。例如，已经表明：在1200℃的空气中，MoSi1.75Al0.25/Al2O3氧化形成了Al2O3。在x为0.1-0.6时，这种六方晶系即所谓的Mo(Si，AI)2的C-40相，是稳定的。有理由设想甚至可以用那些组合物完成本发明。x的值应在0.10-0.60，优选0.20-0.55。毫无疑问地，在烧结金属粉末仍保持合乎需要的性质的条件下，可以由钨代替钼，形成Mo1-yWySi1-xAlx。此方法的y值应该在0-0.4范围内，优选0.05-0.20。在用W取代Mo后，晶体结构C11可维持不变，并且用MO1-yWySi2组合物增加了这种加热元件的使用温度。这被应用于例如商标名为Kantahl Super 1900的加热元件中，它与Kanthal Super 1800类似，在表面上形成了SiO2。甚至熔入铝并用钨取代钼的合金Mo1-yWySi1-xAlx中也形成了类似于C-40相。在钼-硅-铝体系中，较高x值下形成的其余相是如钼的铝化物(aluminide ofmolybdenum)，其在图1所示相图中出现在1823°K。
与本发明相关的实验工作表明：合适的硅化物相重量应为该电阻元件总重量的65-95重量％，优选75-85重量％。
如上所述，该电阻元件除硅化物相之外还包含0-40体积％的氧化铝，优选10-20体积％的氧化铝。
余量为SiO2，一般在0-1重量％之间。
以上所述的发明还可以用于其他的烧结应用中，其中需要低含量的氧气或者低露点。有时这种情况出现在钨重合金、某些钛合金和金属间化合物以及低合金钢的粉末烧结中。例如重合金(heavy alloy)钨-铜就可在-36℃露点下在1400℃的氢气中烧结而成。
预计上述形成的氧化铝在高达约1595℃时是稳定的，这一温度是SiO2-3Al2O3-2SiO2(富铝红柱石)体系的低共熔温度(eutectic temperature)。预计这种氧化物有不同于纯氧化铝的抗腐蚀性能。当元件温度高达至少约1595℃时，这种材料可用作钼型加热元件的一般替代物。

Claims (17)

1.一种电阻元件，其主要包含化学式为Mo(Si1-xAlx)2的硅化物相，该物相在所述元件的表面上形成氧化铝，而且所述元件用于有关金属粉末烧结的领域，其中x的值在0.10和0.60之间。
2.如权利要求1所述的电阻元件，其特征在于，钼部分地被钨代替，形成化学式为Mo1-yWy(Si1-xAlx)2的硅化物相，该物相在所述元件的表面上形成氧化铝。
3.如权利要求1所述的电阻元件，其特征在于，x的值在0.20和0.55之间。
4.如权利要求2的电阻元件，其特征在于，y的值在0和0.40之间。
5.如权利要求4的电阻元件，其特征在于，y的值在0.05和0.20之间。
6.如权利要求1-4中任何一项的电阻元件，其特征在于，硅化物相的量为所述电阻元件总重量的65-95重量％。
7.如权利要求6的电阻元件，其特征在于，硅化物相的量为所述电阻元件总重量的75-85重量％。
8.如权利要求1-4中任何一项的电阻元件，其特征在于，所述元件除所述硅化物相之外还包含0-40体积％的Al2O3。
9.如权利要求1-4中任何一项的电阻元件，其特征在于，所述元件除所述硅化物相之外还包含10-20体积％的Al2O3。
10.如权利要求1-4中任何一项的电阻元件，其特征在于，所述元件中除所述硅化物相和Al2O3之外，还包含余量的SiO2。
11.如权利要求1所述的含有Mo(Si1-xAlx)2型硅化物相的电阻元件在烧结金属粉末中的用途。
12.如权利要求11所述的用途，其特征在于，电阻元件中的钼部分地由钨代替，形成一种Mo1-yWy(Si1-xAlx)2材料。
13.如权利要求11所述的用途，其特征在于，x的值在0.20和0.55之间。
14.如权利要求12所述的用途，其特征在于，y的值在0和0.40之间。
15.如权利要求11-14中任何一项所述的用途，其特征在于，所述的金属粉末是铁基粉末。
16.如权利要求15所述的用途，其特征在于，所述的金属粉末是不锈钢粉末。
17.如权利要求11或12所述的用途，其特征在于，所述电阻元件除硅化物相之外还包含数量为10-20体积％的Al2O3。
CN00807344A 1999-05-20 2000-05-04 电阻加热元件 Expired - Lifetime CN1117169C (zh)

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SE99018277 1999-05-20
SE9901827A SE520251C2 (sv) 1999-05-20 1999-05-20 Motståndselement av molybdensilicidtyp för sintring av metallpulver

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CN1350598A CN1350598A (zh) 2002-05-22
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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
SE521796C2 (sv) * 2002-04-05 2003-12-09 Sandvik Ab Förfarande för tillverkning av ett värmeelement av molybdensilicidtyp jämte ett värmeelement
SE524966C2 (sv) * 2002-04-05 2004-11-02 Sandvik Ab Rörformat elektriskt motståndselement
SE521794C2 (sv) * 2002-04-05 2003-12-09 Sandvik Ab Tillverkningsförfarande för ett värmeelement av molybdensilicidtyp, jämte ett värmeelement
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WO2014168977A1 (en) * 2013-04-09 2014-10-16 International Technology Exchange, Inc. High-temperature nanocomposite emitting film, method for fabricating the same and its application
MX380026B (es) * 2015-12-21 2025-03-11 Kanthal Ab Nueva composicion basada en siliciuro de molibdeno.

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AU774202B2 (en) 2004-06-17
KR20020012196A (ko) 2002-02-15
JP2003500812A (ja) 2003-01-07
ES2579431T3 (es) 2016-08-11
EP1198600A1 (en) 2002-04-24
EP1710217A1 (en) 2006-10-11
WO2000071768A1 (en) 2000-11-30
CN1350598A (zh) 2002-05-22
SE520251C2 (sv) 2003-06-17
SE9901827D0 (sv) 1999-05-20
SE9901827L (sv) 2000-11-21
EP1198600B1 (en) 2015-08-05
BR0010352A (pt) 2002-01-08
EP1710217B1 (en) 2016-03-30
US6563095B1 (en) 2003-05-13
KR100683548B1 (ko) 2007-02-15
AU4962700A (en) 2000-12-12
JP3949894B2 (ja) 2007-07-25
ES2548561T3 (es) 2015-10-19

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