CN1867699A - 防止部件在高温下受到腐蚀和氧化的防护层以及部件 - Google Patents
防止部件在高温下受到腐蚀和氧化的防护层以及部件 Download PDFInfo
- Publication number
- CN1867699A CN1867699A CNA200480030556XA CN200480030556A CN1867699A CN 1867699 A CN1867699 A CN 1867699A CN A200480030556X A CNA200480030556X A CN A200480030556XA CN 200480030556 A CN200480030556 A CN 200480030556A CN 1867699 A CN1867699 A CN 1867699A
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- China
- Prior art keywords
- protective layer
- rhenium
- parts
- powder
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
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Images
Classifications
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- C22C—ALLOYS
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
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Abstract
本发明涉及用于防止部件在高温下受到腐蚀和氧化的防护层。以前公知的防护层中具有很高含量的Al和/或Cr,并加入Re来辅助加强,这样的防护层形成脆性相,在使用过程中,由于碳的影响,进一步强化了脆性。本发明的防护层由下列成分构成:0.5-2%铼,24-26%钴,1 5-21%铬,9-11.5%铝,0.05-0.7%钇和/或至少一种等同的金属,该等同的金属选自的组包括钪和稀土元素,0.0-1%钌,余量为钴和/或镍及生产条件下的杂质。所述防护层几乎不会由于Cr/Re沉淀而导致脆性化。
Description
技术领域
本发明涉及如权利要求1所述的用于在高温下防止部件受到腐蚀和氧化的防护层,所述部件特别是一种燃气轮机部件,本发明还涉及如权利要求6所述的部件和如权利要求7所述的方法。
本发明尤其涉及一种由镍基或钴基超耐热合金(superalloy)制成的部件的防护层。
背景技术
用于提高金属部件的抗腐蚀性和/或抗氧化性的防护层在现有技术中是大量公知的。多数这些防护层都是以集合名MCrALX而公知的。在此,M表示包括铁、钴、镍的组中的至少一种元素,其它的基本成分为鉻、铝以及X=钇,其中的最后一项也可以完全或部分由一种等同元素替代,该等同元素选自包括钪和稀土元素的组。
典型的这种涂层在美国专利US4005989和US4034142中予以公开。
此外,EP-A0194392中公开了很多用于上述种类防护层的特定组分,其中还为不同的应用目的而加入另外的元素。在那里也提到了可以加入至多10%重量百分比的元素铼以及选择加入很多其它的元素。然而,对于可用的添加物缺少进一步明确的范围,所以,所述的防护层都不能胜任特殊的环境,例如用于进气温度很高并且必须长时间运行的燃气轮机的动叶片和导流叶片。
在US5154885、EP-A0412397、DE69401260T2和WO91/02108A1中也公开了包含铼的防护层。由这些文献共同揭示的关于铼的作用被整体归入本次公开的范围之内。
EP1306454A1也公开了一种由镍、钴、鉻、铝、铼、钇构成的防护层。但没有提到镍和钴的含量。
US6346134B1公开了一种McrAlY层,其中的鉻含量为20-35%重量百分比,铝含量为5-15%重量百分比,余量为铪、铼、镧或钽,以及高达4-6%重量百分比的钇。
US6280857B1公开了一种高温防护层,其公开了镍基上的元素钴、鉻、和铝,并选择性地加入铼以及必须加入钇和硅。
从EP025375491中可以得知将防护层施加于燃气轮机的承受高温负荷的部件上的实施形式。
尽力提高进气温度,这在燃气轮机领域有很重要的意义,不仅对于固定的燃气轮机是这样,对于飞机发动机也是如此,因为进气温度是燃气轮机所获得的热动力效率的重要参数。通过采用专门开发的合金作为动叶片和导流叶片等高热负荷部件的基本材料,尤其是采用单晶超耐热合金,可以使进气温度明显地高于1000℃。对于固定的燃气轮机,现有技术允许950℃和更高些的进气温度,对于作为飞机驱动装置的燃气轮机,允许1100℃或更高的进气温度。
在WO91/01433A1中给出了具有单晶基质的涡轮叶片的结构的例子,这种叶片可能会是很复杂的。
尽管目前研发的高负荷部件的基本材料对于有可能更高的进气温度的物理承受能力不会有大的问题,但必须借助于防护层来获得充分的抗氧化和抗腐蚀性。防护层不仅在1000℃量级的燃气侵蚀下要有足够的化学稳定性,还要有良好的机械性能,尤其是防护层与基本材料之间的相互机械作用。特别是,防护层要有足够的延展性,以便随着基材发生必要的变形,并且不出现断裂,因为断裂会带来氧化和腐蚀的侵蚀点。因此,通常出现一个问题,那就是,像铝和鉻这样的元素的含量提高了,虽然可以增加防护层的抗氧化性和抗腐蚀性,但却导致防护层延展性的损害,所以,在燃气轮机中通常出现的机械负荷下可能会出现机械故障,尤其是形成裂纹。在现有技术中,由于元素鉻和铝而使防护层的延展性降低的例子是公知的。
WO01/09403A1公开了一种用于一个基层的含有铼的超耐热合金。该文件中描述了由铼形成的金属间相减小了超耐热合金的长时间稳定性。这种影响可以通过添加钌来减轻。
发明内容
因此,本发明的基本任务是提供一种防护层,其在抗腐蚀和抗氧化方面具有良好的高温耐受性,并具有良好的长期稳定性,此外,能够很好地适应在高温的燃气轮机中需承受的机械应力。
这一任务通过如权利要求1所述的防护层和如权利要求7所述的制造防护层的方法来完成。
在从属权利要求中进一步给出了有利的措施。
在各项从属权利要求中给出的措施可以以有利的方式方法相互结合。
另外,本发明基于这样的认识,即,所述防护层在层中和层与基材之间的过渡区域具有脆性的鉻铼沉淀(Precipitate)。这种随着时间和使用中的温度而逐渐增多的脆性相会在运行时导致在层中以及层与基本材料之间出现明显的纵向裂纹,并进一步导致层的脱离。通过与从基本材料中扩散到层中,或者在热处理时在炉中通过表面扩散到层中的碳的相互作用,也会提高Cr-Re沉淀的脆性。随着鉻铼相的氧化,加剧了裂纹的扩散。
在这样的关系下,确定热和机械性能的钴的影响也是重要的。
本发明的另一任务在于提供一种增强的抗腐蚀和抗氧化的部件。
这一任务通过如权利要求6所述的部件来完成。特别是一种燃气轮机或蒸汽轮机部件,其具有上面所述的防护层,以防止高温下的腐蚀和氧化。
附图说明
下面详细地描述本发明。在附图中:
图1示出了一个具有一防护层的层系。
图2示出了周期负荷实验的实验结果。
图3示出了一台燃气轮机。
图4示出了一个燃烧室。
图5示出了一个涡轮叶片。
具体实施方式
根据本发明,防止部件在高温下受到腐蚀和氧化的防护层7(图1)主要具有如下元素(数量以重量百分比描述):
0.5-2%铼,
15-21%铬,
24-26%钴,
9-11.5%铝,
0.05-0.7%钇和/或至少一种等同的金属,该等同的金属选自的组包括钪和稀土元素,余量为镍及生产条件下的杂质(NiCoCrAlY)。
这里利用了铼在防止脆性相形成方面的有利作用。
需要指出的是,各所述元素的含量是考虑到与元素铼相结合随其作用来调整的。如果所述含量使得没有铬铼沉淀形成,则在使用所述防护层时不会出现脆性相,这是有利的,从而使运行寿命性能得以改善,运行寿命得以延长。这种效果不仅通过低的铬含量来达到,也是考虑了铝在相形成方面的影响,通过精确地确定铝的含量来实现。
选择24-26%的钴带来的效果是,极其显著地并且超比例地改善了所述防护层7的热和机械性能。
将钴的范围选择得这样窄,尤其好地抑制了合金中γ’相的初始和进一步的形成,而这种相通常导致合金的热膨胀系数的峰值。如若不然,该峰值就会在具有所述防护层的部件处于很高温度时(即涡轮机启动时),或者其它温度波动的情况下,在所述防护层7与基层4之间产生机械应力(热不匹配)。
根据本发明选择的钴含量至少可以显著地减小这种现象。
由于脆性在高机械特性的时候的负作用特别大,所以,通过选择钴含量来减小机械应力,并与脆性的减小相结合,从而改善机械性能。通过根据本发明选择的钴含量还特别促进了合金的β相的形成。
在这样的关系下,有利的是,铼的含量为1-1.8%,铬的含量为16-18%,铝的含量为9.5-11%,钇的含量为0.3-0.5%。
在具有较好的抗腐蚀性的同时,所述防护层也具有特别良好的抗氧化性,并以良好的可塑性为特征,所以,尤其适用于在进气温度进一步升高的情况下用于燃气轮机。因为所述防护层几乎不具有在使用过程中变脆的铬铼沉淀,所以在运行过程中几乎不出现脆性化。这种超耐热合金不包含或者最多包含6%体积百分比的铬铼沉淀。
在这种关系下,特别有利的是,铼的含量为大约1.5%,铬的含量为大约17%,铝的含量为大约10%,钴的含量大约为25%,钇的含量大约为0.3%。考虑到大规模的工业化生产,致使存在一定的波动,这意味着,钇的含量为0.2%-0.3%或者0.2-0.4%的情况也被使用并可以得到良好的特性。
在待喷射的粉末中的微量元素也起到了重要的作用,它们形成沉淀,从而导致脆性。
这些粉末通过例如等离子喷射(Plasma spraying)施加(APS、LPPS、VPS、…)。其它方法也可以考虑(PVP、CVD、…)。
特别的,所喷射粉末中的微量元素的总和<0.5%,并且有利的是,这个总和在如下的一些元素中进行分割:碳<250ppm.、氧<400ppm.、氮100ppm.、氢<50ppm。
所述防护层也作为一种超耐热合金的一个粘合层。
其它的层,例如陶瓷绝热层,也可被施加于该粘合层。
在这种部件中,所述防护层优选施加在由镍或钴超耐热合金构成的基层上。特别的,一种适当的基层具有如下的组分(以重量百分比描述):
0.03-0.05%碳,
18-19%铬,
12-15%钴,
3-6%钼,
1-1.5%钨,
2-2.5%铝,
3-5%钛,
选择性地少量加入钽、铌、硼和/或锆,余量为镍。
这种材料作为锻造合金被称之为Udimet520和Udimet720。
可选的,所述基层也可以具有如下的组分(以重量百分比描述):
0.1-0.15%碳,
18-22%铬,
18-19%钴,
0-2%钨,
0-4%钼,
0-1.5%钽,
0-1%铌,
1-3%铝,
2-4%钛,
0-0.75%铪,
选择性地少量加入硼和/或锆,余量为镍。
这种组分作为铸造合金称之为GTD222、IN939、IN6203和UdimetS00。
所述部件的基层的另一种可选形式具有如下的组分(以重量百分比描述):
0.07-0.1%碳,
12-16%铬,
8-10%钴,
1.5-2%钼,
2.5-4%钨,
1.5-5%钽,
0-1%铌,
3-4%铝,
3.5-5%钛,
0-0.1%锆,
0-1%铪,
选择性地少量加入硼,余量为镍。这种组分称之为铸造合金PWA1483SX、IN738LC、GTD111、IN792CC和IN792DS;特别优选IN738LC。
所述部件的基层的又一种可选形式具有如下的组分(以重量百分比描述):
大约0.25%碳,
24-30%铬,
10-11%镍,
7-8%钨,
0-4%钽,
0-0.3%铝,
0-0.3%钛,
0-0.6%锆,
选择性地少量加入的硼,余量为钴。
这种组分也称之为铸造合金,并命名为FSX414、X45、ECY768和MAR-M-509。所述部件上的防护层厚度优选为大约100μm与300μm之间的一个值。
这种防护层特别适合于防止一个部件受到腐蚀或氧化,此时该部件在50℃(对于飞机涡轮发动机来说大致在1100℃)左右的材料温度下暴露于烟道气体中。
因此,根据本发明的防护层特别胜任于保护燃气轮机的部件,特别是导流叶片、动叶片或其它部件,所述部件会暴露于所述燃气轮机的涡轮上游或内部的高温气体中。该防护层可以用作覆盖层(防护层为外层)或黏结层(防护层为中间层)。
图1示出了作为一个部件的一个层系1。所述层系1包括一个基层4。该基层4可以是金属的和/或陶瓷的。特别是对于涡轮机部件,例如涡轮机动叶片120(图2)或导流叶片130(图3、5)、燃烧室里衬155(图4),以及蒸汽轮机或燃气轮机100的其他壳体部分(图5),所述基层4由镍、钴或铁基超耐热合金构成。
在所述基层4上设有根据本发明的防护层7。
该防护层7优选通过LPPS(低压等离子喷射)施加。
该层可用作外层或中间层。
在用作中间层时,在所述防护层7上有一个陶瓷绝热层10。
所述层7可以施加到新部件上,也可以施加到翻新的部件上。翻新意为在部件使用后,必要时进行层(绝热层)分离,并通过例如一种酸处理(酸剥离)方法除去腐蚀和氧化产物,必要时还要对裂纹进行修理,然后对该部件重新施加涂层。进行翻新是因为基层13是很昂贵的。
图2示出了对负荷样品进行周期性负荷实验的实验结果。该样品受到预定的周期性机械负荷(震动负荷)和周期性热负荷(TMF实验)。
图2示出了具有根据本专利申请(本发明)的成分的样品的实验结果和根据现有技术(现有技术)的一个层的实验结果,该层具有根据美国专利US5154885和US5273712或US5268238的成分。
上述实验是在0.51%膨胀量的膨胀控制下进行的。
所述层施加在一个以PWA1484(Pratt&Whitney alloy)命名的基层上。
在图2中,一个坐标是水平方向上测得的裂纹长度,另一个坐标是周期数。非常明显的,所述根据现有技术的层在700周期时就出现了裂纹,而且该裂纹加长的速度比所述根据本申请的层快得多。
所述根据本申请的层在接近900周期时才出现裂纹,而且所述裂纹比所述根据现有技术的层中的裂纹小得多。同时所述裂纹随周期数加长的速度也明显较慢。这显示了根据本发明的层的优越性。
图3以示例方式示出了一台燃气轮机100的局部纵剖面图。
所述燃气轮机100的内部具有一个可绕一旋转轴线102旋转的转子103,也称之为涡轮转子。
沿着所述转子103依次是,一个进气壳体104、一台加压机105、一个例如环面状的燃烧室110,特别是一个环形燃烧室106,其具有多个同轴设置的燃烧器107、一个涡轮108以及排气壳体109。
环形燃烧室106与一个例如环形的高温气体通道111相连。在那里,举例来说,四个连续设置的涡轮级112形成涡轮108。
每个涡轮级112由两个叶片环构成。从工作介质113的流动方向看去,在高温气体通道111中,一个导流叶片排115的后面是一个由动叶片120构成的排125。
导流叶片130固定在一个定子143的内壳体138上,而属于一个排125的动叶片120则例如借助于一个涡轮盘133装在转子103上。在转子103上耦接着一台发电机(未示出)。
在燃气轮机100运行时,加压机105将空气135经进气壳体104吸入并压缩。在加压机105的涡轮端部,经压缩的空气被传送给燃烧器107,并在那里与燃料混合。然后,该混合物在在燃烧室110中燃烧形成工作介质113。
工作介质113从那里流出,沿高温气体通道111,流过导流叶片130和动叶片120。工作介质113在动叶片120处膨胀,将其动量转移,从而使动叶片120驱动转子103,而转子103进而又驱动与其耦接着的发电机。
在燃气轮机100运行时,暴露于高温工作介质113的部件将受到热应力。从工作介质113的流动方向看去,导流叶片130和第一涡轮级112的动叶片以及沿环形燃烧室106排列的隔热砖将受到最强的热应力。为了承受在那里普遍的高温,借助于一种冷却液对这些部件进行冷却。
基层也可以有一种定向的结构,即,其为一种单晶构造(SX结构)或者只有纵向上的晶粒(DS结构)。其采用铁基、镍基或钴基超耐热合金作为材料。例如采用在EP 1204776、EP 1306454、EP 1319729、WO 99/67435或WO00/44949中公开的超耐热合金。这些文件中描述的超耐热合金的组份及优点被作为本次公开的一部分。
动叶片120或导流叶片130具有根据本发明的防腐蚀和防氧化的防护层7(MCrAlx;M为包括铁(Te)、钴(Co)、镍(Ni)的组中的至少一种元素,X代表钇(Y)、硅(Si)和/或至少一种稀土元素)和/或抵抗高温的绝热层。绝热层包括例如ZrO2、Y2O4-ZrO2,即,其由氧化钇和/或氧化钙和/或氧化镁来不加稳定、加以部分稳定或者加以完全稳定。通过适当的涂层方法,例如电子束物理气相沉积(EB-PVD),在绝热层上形成柱状晶粒。
导流叶片130具有一个朝向涡轮108的内壳体138的导流叶片根(未示出)和一个与该导流叶片根相对的导流叶片头。该导流叶片头朝向转子103,并固定在定子143的固定环140上。
图4示出了一个燃气轮机燃烧室110,其可以具有一个层系1。燃烧室110可以是例如所谓的环形燃烧室。若干在圆周方向上围绕着涡轮轴103设置的燃烧器102汇入一个共同的燃烧室空间。为此,燃烧室110整体上为围绕着涡轮轴103定位的环形结构。
为了获得较高的效率,燃烧室110被设计为适合于较高的工作介质M的温度,该温度大约为1000℃-1600℃。为了在这种对于材料不利的运行参数下也可以具有较长的运行寿命,在燃烧室壁153的朝向工作介质M的一侧设有由隔热元件155构成的内衬。各隔热元件155在朝向工作介质的一侧带有特别耐热的防护层,或者由耐高温材料制成并具有如图1所示的防护层7。考虑到燃烧室110内部的高温,还为隔热元件155和/或其保持元件设置了一个冷却系统。
燃烧室壁及其涂层的材料可以与涡轮机叶片120和130的相似。
燃烧室110特别设计为用于检测隔热元件155的损耗。为此,在燃烧室壁153与隔热元件155之间设置若干温度传感器158。
图5示出了叶片120、130的透视图,该叶片具有包括根据本发明的防护层7的层系1。
叶片120、130沿着一纵向轴线121延伸。
叶片120、130沿着纵轴线121依次具有一个固定区域400、一个邻接的叶片台403,以及一个叶身区域406。特别是在叶身406范围内形成一个如图1所示的防护层7或者层系1。
固定区域400中形成一个叶根183,用于将叶片120、130固定在轴上。叶根183被设计为锤头的形状。其它的叶根,例如杉树或燕尾状的叶根也是可以采用的。在传统的叶片120、130中,所有的区域400、403、406内都使用了固态的金属材料。此时,叶片120、130可以使用铸造、锻造、轧制或其结合的方式进行制造。
Claims (13)
1.防止部件高温下腐蚀或氧化的防护层,由下列元素组成(以重量百分比描述):0.5-2%铼,
15-21%铬,
24-26%钴,
9-11.5%铝,
0.05-0.7%钇和/或至少一种等同的金属,该等同的金属选自的组包括钪和稀土元素,
0.0-1%钌,
余量为镍及生产条件下的杂质。
2.如权利要求1所述的防护层,包括:
1-1.8%铼,
16-18%铬,
9.5-11%铝,
0.3-0.5%钇和/或一种等同的金属,该等同金属选自包括钪和稀土元素的组。
3.如权利要求1或2所述的防护层,包括:
1.5%铼,
17%铬,
25%钴,
10%铝,
0.4%钇和/或一种等同金属,该等同金属选自包括钪和稀土元素的组。
4.如权利要求1、2或3中任一项所述的防护层,包括:
容量上最多6%的鉻铼沉淀。
5.如权利要求1、2、3、或4中任一项所述的防护层,所述防护层上施加一绝热层。
6.一个部件,特别是一个燃气轮机的一个部件,所述部件包括一如权利要求1-4中任一项或多项所述的防护层,所述防护层用于防止高温腐蚀和氧化。
7.采用粉末来制备如权利要求1所述的防护层的方法,其特征在于:
所采用粉末中的微量元素含量<0.5%。
8.如权利要求7所述的方法,其特征在于:
所述粉末中的碳含量<250ppm。
9.如权利要求7或8所述的方法,其特征在于:
所述粉末中的氧含量<400ppm。
10.如权利要求7、8或9中任一项所述的方法,其特征在于:
所述粉末中的氮含量<100ppm。
11.如权利要求7、8、9或10中任一项所述的方法,其特征在于:
所述粉末中的氢含量<50ppm。
12.如权利要求7所述的方法,其特征在于:
喷射所述粉末。
13.如权利要求7所述的方法,其特征在于:
蒸发所述粉末。
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EP03023644.2 | 2003-10-17 | ||
EP03023644A EP1524334A1 (de) | 2003-10-17 | 2003-10-17 | Schutzschicht zum Schutz eines Bauteils gegen Korrosion und Oxidation bei hohen Temperaturen und Bauteil |
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CN1867699A true CN1867699A (zh) | 2006-11-22 |
CN100572601C CN100572601C (zh) | 2009-12-23 |
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US (1) | US8025984B2 (zh) |
EP (2) | EP1524334A1 (zh) |
JP (1) | JP4874112B2 (zh) |
CN (1) | CN100572601C (zh) |
AT (1) | ATE497549T1 (zh) |
CA (1) | CA2542763C (zh) |
DE (1) | DE502004012166D1 (zh) |
DK (1) | DK1673490T3 (zh) |
ES (1) | ES2359918T3 (zh) |
PL (1) | PL1673490T3 (zh) |
PT (1) | PT1673490E (zh) |
RU (1) | RU2334022C2 (zh) |
SI (1) | SI1673490T1 (zh) |
WO (1) | WO2005042802A1 (zh) |
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-
2003
- 2003-10-17 EP EP03023644A patent/EP1524334A1/de not_active Withdrawn
-
2004
- 2004-09-08 EP EP04764966A patent/EP1673490B1/de not_active Expired - Lifetime
- 2004-09-08 ES ES04764966T patent/ES2359918T3/es not_active Expired - Lifetime
- 2004-09-08 CN CNB200480030556XA patent/CN100572601C/zh not_active Expired - Lifetime
- 2004-09-08 PL PL04764966T patent/PL1673490T3/pl unknown
- 2004-09-08 DE DE502004012166T patent/DE502004012166D1/de not_active Expired - Lifetime
- 2004-09-08 PT PT04764966T patent/PT1673490E/pt unknown
- 2004-09-08 WO PCT/EP2004/010025 patent/WO2005042802A1/de active Application Filing
- 2004-09-08 JP JP2006534607A patent/JP4874112B2/ja not_active Expired - Fee Related
- 2004-09-08 US US10/575,979 patent/US8025984B2/en active Active
- 2004-09-08 DK DK04764966.0T patent/DK1673490T3/da active
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EP1524334A1 (de) | 2005-04-20 |
CN100572601C (zh) | 2009-12-23 |
CA2542763C (en) | 2010-04-06 |
DE502004012166D1 (de) | 2011-03-17 |
JP4874112B2 (ja) | 2012-02-15 |
PL1673490T3 (pl) | 2011-07-29 |
EP1673490A1 (de) | 2006-06-28 |
RU2006116893A (ru) | 2007-11-27 |
EP1673490B1 (de) | 2011-02-02 |
SI1673490T1 (sl) | 2011-05-31 |
WO2005042802A1 (de) | 2005-05-12 |
JP2007508455A (ja) | 2007-04-05 |
PT1673490E (pt) | 2011-04-20 |
US8025984B2 (en) | 2011-09-27 |
RU2334022C2 (ru) | 2008-09-20 |
US20070065675A1 (en) | 2007-03-22 |
DK1673490T3 (da) | 2011-05-09 |
ES2359918T3 (es) | 2011-05-30 |
ATE497549T1 (de) | 2011-02-15 |
CA2542763A1 (en) | 2005-05-12 |
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