CN101027262A - 减少渗出的氧化铝-氧化锆-二氧化硅产品 - Google Patents
减少渗出的氧化铝-氧化锆-二氧化硅产品 Download PDFInfo
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Abstract
一种AZS型熔铸耐火材料产品,其具有下述化学组分,按重量百分数计:ZrO2:15.5%~22%;SiO2:10.5%~15%;Na2O+K2O+Li2O:1.0%~2.5%;杂质:<1%。所述产品在玻璃熔炉,特别是其上部结构和炉顶部的应用。
Description
技术领域
本发明涉及一种AZS(氧化铝-氧化锆-二氧化硅)型熔铸耐火材料产品,所述产品在应用其的玻璃熔炉的操作温度下玻璃相少量渗出。本发明还涉及所述产品在玻璃熔炉上部结构上的应用。
背景技术
可以通过在电弧炉融解一种适当的原料的混合物,或者通过使用任何其它适合所述产品的熔融技术来得到AZS型熔铸耐火材料产品。随后将熔融液体浇注到模具中以直接获得成型件。一般而言,产品然后经历一个受控冷却循环以降至环境温度而不发生破裂。这一操作在本领域被称作“退火”。
对将AZS产品应用于玻璃熔炉中的了解已经有几十年了,其在熔炉中和熔融的玻璃接触。已经有致力于提高熔融玻璃的抗裂性和耐腐蚀性的研究。
美国专利US-A-2 271 366描述了制造这类产品的第一个实例。对所述实例的晶体学分析显示了在玻璃基(或“相”)中的氧化锆和金刚砂的晶体,即,α氧化铝。美国专利US-A-2 271 366没有研究碱性氧化物的影响。另外,专利US-A-2 271 366表1中的实例表明当氧化锆的含量低于22.1%时,会出现结晶的莫来石相,而这导致耐腐蚀性被熔融玻璃所降低。
美国专利US-A-2 438 552描述了AZS产品,按重量计,其包含45%~70%的Al2O3,14%~40%的ZrO2,9%~12%的SiO2,1%~2.2%的Na2O,0.4%~1.7%的氧化铁和0.2%~0.8%的MgO+CaO。然而,这些包括了大量氧化物的产品,制造昂贵。美国专利US-A-2 438 552没有提示任何这些氧化物是可以选择的。
美国专利US-A-2 271 366,相当于法国专利FR-A-0 883 990,涉及AZS产品,其包含大于75%的Al2O3+ArO2,可选地,含有碱性的种类,例如Na2O。二氧化硅的含量因此必须小于10%。
然而,美国专利US-A-2 271 366,美国专利US-A-2 438 552和美国专利US-A-2 271 366中没有一个解决了玻璃相渗出的问题,而这正是造成玻璃缺陷的原因。
欧洲专利EP-B1-0 939 065提出通过添加B2O3,P2O5和至少一种氧化物来减少从含有20%~59%的氧化锆的AZS产品中渗出的量,所述氧化物选自SnO2,ZnO,CuO和MnO2。添加在常规原料中不作为杂质的所述氧化物,导致生产超成本并可能产生着色的问题。
现今市场上可以买到的AZS产品,例如由Saint-Gobain SEFPRO制造的ER-1681,ER-1685或者ER-1711含有,按重量计45%~50%的Al2O3,32%~40%的ZrO2,12%~16%的SiO2和大约1%的Na2O。所述产品适合玻璃熔炉制造,特别是适合与熔融玻璃接触的区域,上部结构,即,炉顶部下面不与熔融玻璃接触的壁,和玻璃熔炉的炉顶部。然而,为了减少缺陷的数量并因此提高产量,目前用于上部结构和炉顶部的产品并不完全让人满意。在使用该产品的玻璃熔炉的操作温度时,即,上部结构的温度在1500℃左右,其玻璃相渗出的问题会突然出现。
发明内容
因此,需要一种新的熔铸AZS耐火产品,其含有最少量的不同组分和在1500℃左右具有低的渗出量。
本发明的目的就是要满足这一需求。
根据本发明,这一目的是通过一种熔铸AZS耐火产品而实现,值得注意的是,所述产品具有下述化学组分,按重量百分数计:
ZrO2: 15.5%~22%;
SiO2: 10.5%~15%;
Na2O+K2O+Li2O: 1.0%~2.5%;
杂质: <1%;
Al2O3: 补充到100%。
令人惊奇地,发明人因此发现,通过调节常规AZS产品不同组分之间的比率,而不需要添加额外的种类就可以使AZS产品的渗出减少。其制造因此简化并且便宜。
所生产的部件也具有良好的工业可行性,在下面将详细描述关于本发明的产品的化学分析。
除非另有说明,所有的百分数均是按重量计的百分数。
术语“杂质”指下述存在于使用的原料或者由制造产品产生的组分:卤素,例如氟,氯等等;氧化钙;镁;硼;磷;铬;钛和铁。杂质的总量小于1%,并且优选地,每种杂质的量小于0.5%。更优选地,杂质的总量小于0.5%和/或每种杂质的量小于0.1%。
结果显示氧化锆的量主要影响渗出并且必须控制在22%以下,优选19%以下。
可是,它也不能太低,否则产品在使用中失去其抗性。事实上,氧化锆是高耐火组分,其具有非常良好的高温耐化学性。根据本发明,ZrO2的含量大于15.5%,优选大于16%。
发明人还发现Al2O3/ZrO2的重量比影响抗渗性的效力。优选地,Al2O3/ZrO2的重量比为2.9或更大,优选地大于3,更优选为3.7。根据本发明,Al2O3/ZrO2的重量比优选为5.5或更小。
二氧化硅的含量是10.5%或者更多,优选是12%。有利地,生产的可行性因此提高。可行性是在制造后没有表现出不适合用于玻璃熔炉的裂纹的部件的数量所代表。
二氧化硅的含量是15%或者更少。有利地,高温(即大于1500℃)的机械强度因此被提高。
二氧化硅是玻璃相的基本组分。优选地,玻璃相的含量是17%或者更多,优选19%,和/或24%或更少,优选22%,按重量百分比计。
钠和/或钾和/或锂的氧化物在AZS产品中的存在对于本领域已是公知的。惯常地需要提供具有适当的物理和化学性质的玻璃相。根据本发明,Na2O+K2O+Li2O的含量必须在1%~2.5%的范围内。
优选地,SiO2/(Na2O+K2O+Li2O)的重量比是大于7和/或小于9,更优选小于8。有利地,本发明的产品的抗渗性因此得到提高。
由于成本原因,优选氧化钠。
本发明的产品与常规AZS产品的不同之处在于其特别的结晶组分。它们全部由晶体金刚砂和玻璃相游离氧化锆组成并且不含低熔点氧化铝-氧化锆晶体。
具体实施方式
为了说明本发明给出下述非限定实施例。
这些实施例所制造的产品全部由“常规”原料制造。具体地,使用氧化铝,锆砂,碳酸钠和Ssint-Gobain ZIRPRO出售的CC10氧化锆。
在很大程度上,杂质由钙和镁的氧化物组成。
通过在一个Héroult型电熔炉中融解原料得到产品。使用长弧加热原料批料。
在通过吹入氧气加热时,持续氧化条件并搅拌。
表1提供了被测试产品的组分以及对于该产品进行测试的结果。
实施例1对应于一种参考的产品。“PV”指“玻璃相”,和“ND”指“未测定”。
如果一个尺寸为250×20×250mm(毫米)的块没有“贯穿”(through)的裂纹和/或长度大于20mm,则判定其可行性为“良好”。所述缺陷可导致当用于玻璃熔炉时块的完全碎裂。
试验A允许对产品抗渗性进行测定。测试产品的样品,以长度是100mm和直径是24mm的棒的形式,在1500℃经历4h的两个循环,温度的升高和降低为100℃/h。在这两个循环后样品体积变化(按%)进行测定,对应于渗出值,以%表示。如果所述体积变化小于1.5%,而参考产品的值为3.5%,则认为该产品特别有利。
试验B测定在气相中的耐腐蚀性。玻璃熔炉由于在形成玻璃的组分中的一些成分的气化作用而具有腐蚀性空气。所述腐蚀性空气使产品在高温下变形并使产品变软,这可能导致产品在操作中解构。在腐蚀性空气,1500℃,100h的条件下进行试验B。表1显示变形带的厚度,以mm计。只有在所述厚度比由参考产品获得的厚度小时,即小于5.5mm,认为该产品是可接受的。
试验C允许对产品在负载下抗崩塌性进行测定。其由在以250℃/h快速升温,直至高达1745℃,对受到0.2MPa负载时样品的形变进行测定所组成。表1中以℃给出温度。只有在所述温度至少和由参考产品获得的温度一样高时,即1740℃,认为该产品是可接受的。
表1
N° | Al2O3 | ZrO2 | SiO2 | Na2O | PV(%) | Al2O3/ZrO2 | SiO2/Na2O | 可行性 | 试验A(%) | 试验B(mm) | 试验C(℃) |
1 | 53.6 | 31 | 14 | 1.4 | 21 | 1.7 | 10 | 良好 | 3.5 | 5.5 | 1740 |
2 | 52.9 | 30.1 | 15 | 2.0 | 24 | 1.8 | 7.5 | 良好 | 4.8 | ND | ND |
3 | 61.4 | 26.6 | 10.3 | 1.7 | 17 | 2.3 | 6.1 | 裂纹 | ND | ND | ND |
4 | 60.6 | 25.8 | 12.0 | 1.6 | 19.2 | 2.3 | 7.5 | 良好 | 3.3 | ND | ND |
5 | 62.0 | 24.3 | 12.0 | 1.7 | 19.5 | 2.6 | 7.1 | 良好 | 2.8 | ND | ND |
6 | 62.3 | 23.1 | 13.3 | 1.3 | 20 | 2.7 | 10.6 | 良好 | 1.7 | ND | ND |
7 | 63.2 | 22.4 | 12.8 | 1.6 | 20 | 2.8 | 8 | 良好 | 1.6 | ND | ND |
8 | 64.4 | 21.6 | 12.9 | 1.1 | 18.5 | 3.0 | 11.7 | 良好 | 1.2 | ND | ND |
9 | 63.6 | 21.6 | 12.8 | 2.0 | 21.5 | 2.9 | 6.5 | 良好 | 0.9 | 3.5 | ND |
10 | 68.1 | 21.0 | 10.0 | 0.9 | 17 | 3.2 | 11.1 | 裂纹 | ND | ND | ND |
11 | 62.8 | 21.0 | 15.0 | 1.2 | 21 | 3.0 | 12.5 | 良好 | 0.8 | ND | >1745 |
12 | 64.8 | 20.7 | 12.6 | 1.8 | 22.0 | 3.1 | 7.0 | 良好 | 0.9 | ND | ND |
13 | 65.6 | 20.5 | 11.3 | 1.6 | 19.5 | 3.2 | 7.1 | 良好 | 0.6 | ND | ND |
14 | 66.8 | 19.9 | 9.7 | 1.7 | 16.7 | 3.4 | 5.8 | 裂纹 | ND | ND | ND |
15 | 65.7 | 19.8 | 13.2 | 1.3 | 19.5 | 3.3 | 10.1 | 良好 | 0.7 | ND | ND |
16 | 65.5 | 19.7 | 13.3 | 1.5 | 20.5 | 3.3 | 8.6 | 良好 | 1.0 | ND | ND |
17 | 65.8 | 19.4 | 13.7 | 1.1 | 19.0 | 3.4 | 12.5 | 良好 | 1.0 | ND | ND |
18 | 66.7 | 18.4 | 13.1 | 1.8 | 21 | 3.6 | 7.3 | 良好 | 0.1 | 3.5 | ND |
19 | 66.4 | 18.4 | 13.5 | 1.7 | 21.5 | 3.6 | 7.9 | 良好 | 0.4 | ND | ND |
20 | 66.4 | 18.1 | 14.2 | 1.3 | 20.5 | 3.7 | 10.6 | 良好 | 0.8 | ND | ND |
21 | 66.2 | 18.0 | 14.1 | 1.7 | 22.0 | 3.7 | 8.2 | 良好 | 0 | ND | ND |
22 | 67.0 | 17.8 | 13.3 | 1.8 | 21.5 | 3.8 | 7.2 | 良好 | 0 | ND | ND |
23 | 66.5 | 17.8 | 13.9 | 1.8 | 22.0 | 3.7 | 7.9 | 良好 | 0 | 3.0 | ND |
24 | 68.3 | 17.8 | 12.0 | 1.9 | 20.0 | 3.8 | 6.3 | 良好 | 0.1 | ND | ND |
25 | 68.8 | 17.3 | 12.7 | 1.2 | 19.0 | 4.0 | 10.7 | 良好 | 0.6 | ND | ND |
27 | 67.3 | 17.2 | 13.7 | 1.8 | 22 | 3.9 | 7.7 | 良好 | 0 | ND | ND |
28 | 72.2 | 17.2 | 9.8 | 0.8 | 14.0 | 4.2 | 12.0 | 裂纹 | ND | ND | ND |
29 | 65.8 | 16.9 | 15.2 | 2.1 | 24.5 | 3.9 | 7.2 | 良好 | 0 | ND | 1730 |
30 | 68.2 | 16.9 | 13.1 | 1.8 | 21.5 | 4.0 | 7.1 | 良好 | 0 | ND | ND |
31 | 69.6 | 16.8 | 12.0 | 1.6 | 19.0 | 4.1 | 7.7 | 良好 | 0 | ND | ND |
32 | 70.3 | 16.5 | 12.1 | 1.1 | 17.5 | 4.3 | 11.2 | 良好 | 1.3 | ND | ND |
33 | 69.1 | 16.1 | 13.0 | 1.8 | 21.5 | 4.3 | 7.1 | 良好 | 0 | ND | ND |
34 | 70.4 | 16 | 12.6 | 1.0 | 17.5 | 4.4 | 12.6 | 良好 | 0.7 | ND | ND |
35 | 67.6 | 16 | 14.0 | 2.4 | 23 | 4.2 | 5.8 | 良好 | 0 | ND | ND |
36 | 70.1 | 15.9 | 12.3 | 1.7 | 20 | 4.4 | 7.4 | 良好 | 0 | ND | ND |
37 | 70.1 | 15.8 | 12.3 | 1.7 | 20.0 | 4.4 | 7.2 | 良好 | ND | 3.0 | ND |
38 | 73.2 | 15.8 | 9.7 | 1.3 | 16.0 | 4.6 | 7.5 | 裂纹 | ND | ND | ND |
40 | 67.3 | 15.5 | 15.0 | 2.1 | 24.5 | 4.3 | 7 | 良好 | 0 | ND | 1723 |
41 | 70.5 | 15.5 | 12.4 | 1.6 | 20 | 4.5 | 7.6 | 良好 | 0 | ND | 1744 |
42 | 68.6 | 15.2 | 13.4 | 1.7 | 21 | 4.5 | 7.9 | 良好 | 0 | 5.7 | ND |
43 | 70.9 | 14.4 | 12.8 | 1.8 | 21 | 4.9 | 7.1 | 良好 | 0 | 6.1 | ND |
通过表1,可以得出下述结论:
当二氧化硅的含量大于10.5%时,优选大于12%和当玻璃相的质量大于19%时,产品的可行性良好。
当氧化锆的含量小于22%时,试验A的结果比参考产品有显著提高。当氧化锆的含量小于19%,特别是如果二氧化硅的含量与钠氧化物的量的比率小于9,优选小于8时,试验A具有渗出物小于0.5%的非常好的结果。
结果最好的产品具有Al2O3/ZrO2的比率是2.9或更高。优选地,本发明的产品具有Al2O3/ZrO2的比率是4.5或更小。
由试验B测定的气相耐蚀性相对于参考产品的值有所提高。由于这个原因,氧化锆的含量必须控制在大于15.5%。
为了制造至少和试验C中的参考产品相当的产品,玻璃相的量必须小于24%,优选小于22%。
试验B和C的结果证明在上部结构或者玻璃熔炉顶部使用本发明的产品的可能性。
另外,发明人观察到,和参考的AZS产品相比,本发明的产品的膨胀现象有所改善,由边界的氧化锆变形引起的体积收缩会很少。有利地,打开两个块之间接缝的问题因此而得以改进。
本发明产品的结晶学分析大体上显示为15.5%~22%的游离氧化锆晶体,17%~23%的玻璃相,其余为金刚砂。按孔体积和总的表面的体积的比率所测量的孔率小于5%。
可以清晰地看到,本发明的产品渗出减少和具有良好的工业可行性。有利地,本发明的产品可以仅使用AZS产品的常规组分制造,而不用添加额外的物质。制造因此被简化并减少了成本。
明显地,本发明不被作为说明的,非限制性实施例所描述和展现的过程所限制。
特别地,本发明不被制造工艺或者使用的熔炉所限制。任何用于融合和铸造AZS产品的常规工艺均可以使用。
法国专利FR-A-1208 577描述了一个用于融解原料的适当工艺的实例。在该工艺中,调节弧长度以便使其还原作用最小,弧或者起泡气体,优选氧化气体,例如空气或者氧气,提供了对熔融体的搅拌。作为实施例,弧长可以与啸声电弧现象相符。
Claims (10)
1.一种AZS型熔铸耐火材料产品,其特征在于所述产品具有下述化学组分,按重量百分数计:
ZrO2: 15.5%~22%;
SiO2: 10.5%~15%;
Na2O+K2O+Li2O: 1.0%~2.5%;
杂质: <1%;
Al2O3: 补充到100%。
2.根据权利要求1的产品,其特征在于Al2O3/ZrO2的重量比是2.9或更大和/或是5.5或更小。
3.根据权利要求1或2的产品,其特征在于SiO2/(Na2O+K2O+Li2O)的重量比小于9。
4.根据权利要求3的产品,其特征在于SiO2/(Na2O+K2O+Li2O)的重量比小于8。
5.根据上述任意一项权利要求所述的产品,其特征在于SiO2/(Na2O+K2O+Li2O)的重量比大于7。
6.根据上述任意权利要求的产品,其特征在于按重量百分比计,ZrO2的含量是19%或更小。
7.根据上述任意一项权利要求所述的产品,其特征在于按重量百分比计,杂质的总量小于0.5%和/或任何一种杂质的量小于0.1%。
8.根据上述任意一项权利要求所述的产品,其特征在于玻璃相的含量是17%或更大和/或是24%或更小。
9.根据权利要求8的产品,其特征在于玻璃相的含量是1 9%或更大和/或是22%或更小。
10.根据上述任意一项权利要求所述的耐火材料产品在玻璃熔炉的上部结构或炉顶部的应用。
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FR0409914A FR2875497B1 (fr) | 2004-09-20 | 2004-09-20 | Produits azs a exsudation reduite |
FR0409914 | 2004-09-20 | ||
PCT/FR2005/002277 WO2006032757A1 (fr) | 2004-09-20 | 2005-09-14 | Produit azs a exsudation reduite |
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CN103097311A (zh) * | 2010-06-21 | 2013-05-08 | 法商圣高拜欧洲实验及研究中心 | 耐火块及玻璃熔炉 |
CN104603082A (zh) * | 2012-08-24 | 2015-05-06 | 里弗雷克特里知识产权两合公司 | 基于氧化铝、二氧化锆和二氧化硅的熔铸耐火材料及该材料的用途 |
CN108752017A (zh) * | 2018-04-25 | 2018-11-06 | 郑州新光色耐火材料有限公司 | 电熔锆刚玉砖及其制备方法 |
CN111278789A (zh) * | 2017-11-07 | 2020-06-12 | 旭硝子陶瓷株式会社 | 氧化铝/氧化锆/二氧化硅质熔融铸造耐火物和玻璃熔融窑 |
CN111848188A (zh) * | 2020-07-10 | 2020-10-30 | 安徽中材新材料科技有限公司 | 一种零玻璃相渗出的熔铸锆刚玉耐火砖及其制备方法 |
CN113105254A (zh) * | 2021-03-29 | 2021-07-13 | 彰武县联信铸造硅砂有限公司 | 一种新型陶瓷砂及其制备方法 |
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FR2940276B1 (fr) * | 2008-12-22 | 2011-02-04 | Saint Gobain Ct Recherches | Bloc refractaire et four de fusion de verre |
KR20120023054A (ko) * | 2009-05-05 | 2012-03-12 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 티타늄 광석 선광용 내화 라이닝 |
PL3053897T3 (pl) * | 2015-02-09 | 2017-07-31 | Refractory Intellectual Property Gmbh & Co. Kg | Zestaw do wytwarzania wyrobu ogniotrwałego, sposób wytwarzania wyrobu ogniotrwałego, wyrób ogniotrwały oraz zastosowanie wyrobu ogniotrwałego |
JP2019047266A (ja) * | 2017-08-31 | 2019-03-22 | トヨタ自動車株式会社 | アレーアンテナ |
FR3074909B1 (fr) | 2017-12-11 | 2022-03-04 | Saint Gobain Ct Recherches | Procede d'identification de la classe de refractaires electrofondus azs generant des " pierres " dans un produit verrier |
FR3084666B1 (fr) * | 2018-08-01 | 2022-05-13 | Saint Gobain Ct Recherches | Couche de protection pour produit refractaire |
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US2271366A (en) * | 1939-10-20 | 1942-01-27 | Corhart Refractories Co | Cast refractory product |
US2438552A (en) * | 1940-10-14 | 1948-03-30 | Corhart Refractories Co | Cast refractory product |
FR1208577A (fr) * | 1958-07-07 | 1960-02-24 | Electro Refractaire | Perfectionnements à la fabrication de produits réfractaires électrofondus contenant des oxydes minéraux |
US4139394A (en) * | 1974-12-26 | 1979-02-13 | Societe Europeenne Des Produits Refractaires | Linings for pusher ovens |
FR2627483A1 (fr) * | 1988-02-19 | 1989-08-25 | Produits Refractaires | Pieces ceramiques minces obtenues par fusion et moulage d'une composition du systeme al2o-zro2-sio2-k2o ayant de bonnes proprietes de resistance mecanique et de resistance a l'abrasion |
JP3904264B2 (ja) * | 1996-10-01 | 2007-04-11 | 旭硝子セラミックス株式会社 | アルミナ・ジルコニア・シリカ質溶融耐火物 |
JP4297543B2 (ja) * | 1998-02-26 | 2009-07-15 | Agcセラミックス株式会社 | アルミナ・ジルコニア・シリカ質溶融鋳造耐火物およびそれを使用したガラス溶融窯 |
US6158248A (en) | 1998-02-26 | 2000-12-12 | Asahi Glass Company Ltd. | Fused-cast-alumina-zirconia-silica refractory, methods of making it and glass melting furnace employing it |
FR2810315B1 (fr) * | 2000-06-20 | 2002-08-16 | Produits Refractaires | Produits azs fondus et coules de cout reduit et leurs utilisations |
-
2004
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CN103097311A (zh) * | 2010-06-21 | 2013-05-08 | 法商圣高拜欧洲实验及研究中心 | 耐火块及玻璃熔炉 |
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CN104603082B (zh) * | 2012-08-24 | 2016-11-09 | 里弗雷克特里知识产权两合公司 | 基于氧化铝、二氧化锆和二氧化硅的熔铸耐火材料及该材料的用途 |
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AU2005286391A1 (en) | 2006-03-30 |
KR101205394B1 (ko) | 2012-11-27 |
FR2875497A1 (fr) | 2006-03-24 |
RU2007109346A (ru) | 2008-10-27 |
WO2006032757A1 (fr) | 2006-03-30 |
BRPI0515450A (pt) | 2008-07-29 |
BRPI0515450B1 (pt) | 2016-03-08 |
RU2386602C2 (ru) | 2010-04-20 |
AU2005286391B2 (en) | 2011-04-07 |
ES2343423T3 (es) | 2010-07-30 |
EP1805118A1 (fr) | 2007-07-11 |
EP1805118B1 (fr) | 2010-04-07 |
ATE463470T1 (de) | 2010-04-15 |
PL1805118T3 (pl) | 2010-09-30 |
KR20070057181A (ko) | 2007-06-04 |
US20070270303A1 (en) | 2007-11-22 |
UA89794C2 (ru) | 2010-03-10 |
FR2875497B1 (fr) | 2006-12-08 |
JP2008513328A (ja) | 2008-05-01 |
PT1805118E (pt) | 2010-07-01 |
CN101027262B (zh) | 2011-01-05 |
MX2007003054A (es) | 2007-05-16 |
DE602005020484D1 (de) | 2010-05-20 |
US7642211B2 (en) | 2010-01-05 |
CA2580227A1 (fr) | 2006-03-30 |
JP4890458B2 (ja) | 2012-03-07 |
ZA200702268B (en) | 2008-09-25 |
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