CN101501231B - 无水泥的耐火混合物、无水泥耐火制品及其制备方法 - Google Patents
无水泥的耐火混合物、无水泥耐火制品及其制备方法 Download PDFInfo
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- CN101501231B CN101501231B CN2007800289471A CN200780028947A CN101501231B CN 101501231 B CN101501231 B CN 101501231B CN 2007800289471 A CN2007800289471 A CN 2007800289471A CN 200780028947 A CN200780028947 A CN 200780028947A CN 101501231 B CN101501231 B CN 101501231B
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- 238000000034 method Methods 0.000 title claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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Abstract
本发明描述了无水泥耐火混合物。该混合物包含pH缓冲剂和含有金属或气相法氧化硅的组分。水可以赋予该混合物以良好的流动特性并且可以产生有效的低温固化。在提高的温度下,使用该混合物形成的制品具有优异的耐火性能和物理性能。
Description
发明领域
本发明涉及耐火混合物。该混合物包含pH缓冲剂和气相法氧化硅或硅金属。可以通过常规技术将该混合物成形以产生耐火制品。该制品可具有优异的物理性能,包括比具有水泥基粘合剂或化学粘合剂的材料更大的耐火度。
发明背景
发明背景
耐火制品包括预成形产品和原位成形产品。预成形产品包括罩、管、板和砖。成形产品可用作容器、管或通道的衬里,并且通常作为在适当位置(in place)捣固(ram)、喷补、抹涂(trowel)、喷涂、振实或浇注的混合物而提供。
耐火制品必须抵抗热侵蚀、化学侵蚀和机械侵蚀。热侵蚀包括通常高于1000C的高温和快速改变制品温度引起的热冲击。经常地,使用该制品的应用包括或产生具有损害性的化学物质。例如,钢铸造中存在的熔渣化学侵蚀耐火制品,使得与熔渣接触的制品通常包含抗熔渣氧化物例如氧化锆。类似地,用于铝镇静钢的耐火管必须抵抗氧化铝的积累,否则该积累能够阻塞所述管。最后,耐火制品必须足够坚固以抵抗机械力例如压缩应力、拉伸应力和扭转应力。
通常,耐火制品由耐火骨料和粘合剂的结合体形成。粘合剂将骨料保持在适当位置。骨料和粘合剂均可以显著地影响制品的性质。常见骨料包括氧化硅、氧化锆、碳化硅、氧化铝、氧化镁、尖晶石、煅烧白云石、铬镁砂、橄榄石、镁橄榄石、莫来石、蓝晶石(kyanmite)、红柱石、耐火粘土熟料、碳、铬铁矿和它们的组合。
粘合剂分为两个宽的种类,水泥质的和“化学的”。化学粘合剂包括有机和无机化学物质例如酚类、糠醛、有机树脂、磷酸盐(phosphate)和硅酸盐(silicate)。通常必须将制品烧制以活化化学物质和引发粘合剂。水泥质粘合剂包括水泥或其它可水合的陶瓷粉末例如铝酸钙水泥或可水合氧化铝。它们通常不需要加热来活化粘合剂,但确实需要添加水。水与水泥质粘合剂反应从而硬化混合物。水还充当细粉末的分散介质。干粉末具有差的流动性并且不适合于在不存在高压时形成耐火制品。水降低混合物的粘度,从而允许骨料/粘合剂混合物流动。遗憾的是,耐火制品中水的存在会具有灾难性的影响,即该制品在暴露于提高的温度时发生开裂和甚至在耐火温度下发生爆炸性气化。具有水泥质粘合剂的制品通常需要干燥步骤来消除残留的水。
耐火骨料/粘合剂混合物典型地包括至少70重量%骨料和至多约15重量%水泥粘合剂。按足以产生形成耐火制品所需流动的量加入水以补足混合物的余量。水可以直接加入或者以水合物加入。例如,欧洲专利申请公开No.0064863以在提高的温度下分解的无机水合物加入水。US 6,284,688包括微包封硅酸钠中的水。
制品的孔隙率影响干燥速度和爆炸性气化的危险,因为孔隙允许水从制品蒸发或挥发。现有技术通过加入金属粉末提高混合物的孔隙率。JP 38154/1986教导了包含骨料、水泥和铝粉末的耐火混合物。铝粉末与加入的水反产生氢气。鼓泡气体形成孔隙,通过该孔隙可发生干燥并可释放蒸汽。铝反应产生很多的热量,该热量进一步有助于干燥。有铝粉末相关的问题包括反应的强放热性质、易燃氢气的释放、制品中微裂纹的形成和铝粉末的有限贮存期限。为了控制这种反应性,US 5,783,510和US 6,117,373教导了包含耐火骨料、耐火粉末和反应性金属粉末的整体耐火组合物。所述耐火粉末包括高铝水泥用以结合骨料,从而向由该组合物形成的制品赋予物理强度。所述反应性金属包括铝、镁、硅及它们的合金。对反应性金属的量进行选择以控制氢气的产生,从而控制孔隙率。作为替代,日本未审专利公开No.190276/1984教导了使用纤维来形成细通道,水可通过所述细通道逃逸。遗憾的是,纤维难以均匀分散在混合物中并且会降低流动性。制品孔隙率的提高还伴随对制成制品的物理性能的有害影响。
耐火制品可以包括化学的即非水泥质的粘合剂,该粘合剂可消除对水的需要。粘度典型地非常高并且骨料/化学粘合剂混合物通常流动得不好。化学粘合剂典型地通过在提高的温度下加热或烧制得以活化,并且例如用于干燥的可振实混合物和多种预成形的制品。US6,846,763包括作为粘合剂的粒状沥青,以及耐火骨料、可燃金属粉末和油。加热该混合物引燃金属粉末,这使油燃烧,并且使沥青熔化和焦化。结果是碳结合的耐火制品。典型的组合物包括70重量%骨料、6重量%硅、7重量%油和13重量%沥青。虽然需要高温来形成碳结合体,但该制品基本上无水。碳结合的制品不如氧化物结合的制品稳定。除非保持在还原性气氛中,碳结合的制品在提高的温度下还对氧化敏感。
US 5,366,944教导了同时使用低温粘合剂和高温粘合剂的耐火组合物。未向该组合物中加入水。低温粘合剂包括有机粘合剂例如酚醛树脂。高温粘合剂包括铝、硅、镁、它们的合金及混合物的金属粉末。制品可由该组合物形成并在低温下固化以活化低温粘合剂。低温粘合剂将制品维持在一起,直到制品被安装和高温粘合剂活化。直到达到耐火温度,金属粘合剂才能活化。有利地,金属粘合剂比水泥基粘合剂产生具有更高耐火度的制品。
需要具有低水含量和低孔隙率的非水泥基耐火混合物,以产生在高温下具有高强度的耐火制品。
发明概述
本发明涉及产生耐火组合物的混合物,所述耐火组合物可用于例如各种冶金容器如熔炉、浇包、中间包和坩埚的衬里。该组合物还可全部或部分用于导引液体金属流动的制品。该混合物比常规水泥基体系需要较少的水,从而减少干燥时间和爆炸风险。该混合物不需要烧制来实现初始固化。在与水泥基混合物相比时,该混合物还有利地提高所得制品的耐火度和强度。
在宽的方面,本发明包括耐火骨料和产生pH缓冲剂的物质的无水泥混合物。该混合物可以含有粘合剂,所述粘合剂含有细粉状 金属组分。本申请述及原料的选择和分级,例如耐火骨料和粘合剂的化学组成和颗粒尺寸。认为具有大表面积的骨料组分例如气相法氧化硅产生凝胶,该凝胶在具有低水含量和低水孔隙率的耐火材料的形成中起作用。在本文作为骨料组分提及的气相法氧化硅应理解为属于干燥的气相法氧化硅,这有别于胶体氧化硅。还认为产生pH缓冲剂的物质例如氧化镁、氧化铝、氧化锆或非水泥质钙化合物、或这些材料的组合的存在,对具有低的水含量和低的水孔隙率的耐火材料的形成起作用。
本发明的混合物比常规水泥基混合物需要更少的水。此外,与水泥基混合物相比,向骨料/粘合剂混合物中加入给定量的水产生更大的流动性。与水泥基制品相比,制品的物理性能还较少地依赖于加入的水量。
在一个实施方案中,混合物包含耐火骨料和0.5重量%-5重量%的具有-200目或更细颗粒尺寸的金属粉末。根据应用,向该混合物中加入足量的水。调节混合物的pH,使得氢气的放出得以防止或降低到可接受的低水平。正如本领域技术人员已知,缓冲剂可用于维持pH。任选地,可加入抗絮凝剂以改善流动特性或降低需水量。然后可将骨料/粘合剂/水共混物成形为任何所需形状。该成形物变硬形成制品。在窑炉中或者在使用温度下,加热产生氧化物结合的制品。
在可浇注耐火制剂中优选使用粘合剂。粘合剂还可以用于其它类型的耐火材料例如塑料材料、捣固材料、砖和压制成形物。本领域技术人员理解需要调节贮存期和成形顺序以便以合适的时间间隔获得一组结合体。
在具体的实施方案中,将包含耐火粘土骨料和气相法氧化硅的耐火骨料与1重量%铝粉末、0.5重量%氧化镁缓冲剂和0.2重量%抗絮凝剂结合。以5重量%加入水并且成形为所需形状。pH的控制降低氢气放出和所产生的孔隙率。烧制产生具有降低的孔隙率的致密氧化物基制品。
发明详述
本发明的混合物含有骨料和产生pH缓冲剂的物质。本发明的混合物产生耐火组合物而不使用水泥。根据本发明的无水泥混合物含有小于3.3重量%的本文所给对比例中的水泥并且可含有小于0.2重量%的水泥。
在本发明中可以将粘合剂与陶瓷骨料特别是耐火陶瓷骨料结合使用。该粘合剂是无水泥的并且可基本上由金属粉末构成。形成包含骨料、金属粉末粘合剂和pH缓冲剂的混合物。向该混合物中加入足量的水。然后将包含水的混合物成形为制品。不同于水泥基粘合剂,本发明的粘合剂具有类似于或大于骨料的耐火度。使用该金属粘合剂制得的制品的物理性能还可超过使用常规粘合剂体系制得的制品。
本发明不限于任何特定的陶瓷骨料,即该陶瓷骨料可以具有任何合适的化学组成或者颗粒尺寸、形状或分布。常见的骨料包括氧化硅、氧化锆、碳化硅、氧化铝、氧化镁、尖晶石和它们的组合。这些骨料可包括气相法材料。在本发明的一个实施方案中,该骨料含有气相法氧化硅和产生pH缓冲剂的物质例如氧化铝、氧化镁、氧化锆或非水泥质钙化合物、或这些材料的组合。其中有待使用该耐火制品的应用很大程度上决定了耐火骨料的组成。该结合体同样适合于产生可用于非耐火用途中的可浇注物。合适的金属和骨料可用于产生能够用于环境温度结构中的可浇注物。典型的应用是土木工程结构(桥梁、建筑物、道路等)、特种混凝土和修补材料。
粘合剂可基本上由金属粉末构成并且不含水泥例如铝酸钙水泥,其典型地比陶瓷骨料具有更低的强度和耐火度。金属粉末包括任何能够与水反应以在骨料颗粒之间形成基质的金属。所述基质例如可以是氢氧化物凝胶。金属粉末不应具有过大的反应性从而使与水的反应速率不可控制。反应性至少取决于溶液的pH、所使用的金属和该金属的尺寸及形状。例如,碱金属与水剧烈地反应而与pH无关。金属粉末还必须不具有过大的惰性从而使固化时间过长或不存在。非反应性的金属包括具有低化学势的贵金属和其它过渡金属。
用于粘合剂的合适金属包括但不限于铝、镁、硅、铁、铬、锆、它们的合金及混合物。可通过调节各种因素控制这些金属的反应性,所述因素包括pH和金属粉末的颗粒尺寸。在与水混合后形成凝胶,该凝胶将制品粘合起来,直到在提高的温度下形成将制品粘合在一起的氧化物结合体。氧化物结合体比铝酸钙水泥及许多其它结合技术更加耐火。
必须控制骨料/粘合剂/水混合物的pH,从而使氢气的放出保持在可接受的限度内。氢气产生可极度地且爆炸性地放热。放出氢气的另外有害影响包括氢氧化物凝胶基质的提高的孔隙率和过早的分解。控制氢气放出所需的pH将取决于所使用的金属。该pH是可计算的并且是基于金属的化学势。可以选择能够维持pH的骨料。作为替代,缓冲剂可必须维持所需的pH。合适的缓冲剂对于本领域技术人员是已知的,并且包括氧化镁、氧化铝、氧化锆和非水泥质钙化合物及这些物质的组合。优选地,缓冲剂将是本身耐火的或者将在使用温度下分解并挥发。可加入螯合剂例如柠檬酸或硼酸以控制固化时间。可用pH不大于10.0的混合物实施本发明。
还可通过金属粉末的颗粒尺寸控制金属/水反应的动力学。金属粉末的反应性与可用表面积成比例。较大的表面积产生较大的反应性。金属粉末的有效颗粒尺寸为-70目(212微米)或更小。过大的颗粒尺寸限制反应性,而过小的颗粒尺寸可使反应的动力学难以控制。适宜的尺寸为-200目(75微米)至-325目(45微米)。颗粒尺寸仅是控制表面积的一种手段。还可改变金属粉末的形状和组织。作为替代,金属粉末的表面可涂覆有钝化剂例如聚合物、蜡或氧化物。
金属粘合剂的量特别随预期应用、耐火骨料、金属和期望的固化速度而改变。粘合剂典型地为混合物的0.5重量%-5重量%。少至0.1重量%已经是有效的并且大至10重量%是预期到的。较低量的粘合剂可降低固化速度和制成制品的强度。混合物中应包括足量的粘合剂以获得所需性能。较高量的粘合剂增加费用和自发反应的风险。对于铝金属,约1重量%的浓度对于可浇注应用起到令人满意的作用。如 果使用某些骨料组分例如气相法氧化硅,则可制得本发明的混合物而不使用金属粘合剂。具体地,可制得根据本发明的混合物而不使用铝合金粉末。
任选地,可纳入各种添加剂以便在制品制备期间或之后改善物理性能。可加入抗絮凝剂以改善流动和减少需水量。可例如以炭黑或柏油(pitch)形式加入碳以抵抗工作期间的熔渣渗透。抗氧化剂例如碳化硼或硅保护碳不被氧化。其它添加剂对本领域技术人员是熟知的。
实施例
制备两种可浇注骨料/粘合剂混合物。两种混合物均旨在作为高炉铁槽和浇道的耐火衬里。第一混合物是典型的“超低”水泥可浇注物,该可浇注物包含74重量%氧化铝、17.5重量%碳化硅、3.3重量%铝酸钙水泥、2.5重量%气相法氧化硅和0.2重量%金属粉末。第二混合物是本发明的无水泥组合物,该组合物包含69重量%氧化铝、22.5重量%碳化硅、6重量%气相法氧化硅、0.75重量%硅和0.5重量%铝。
向两种混合物中加入水。水泥基混合物需要4.25-6.25重量%水来获得20-100%的ASTM C-1445流动。无水泥混合物仅需要2.75-3.75重量%水来获得20-100%流动。无水泥组合物需要约一半量的水来获得所需流动。
使混合物和水固化。在固化期间,第一混合物中的水泥将pH提高到高于10.0,从而有利于铝粉末和水之间的水解反应。该反应产生氢气和热。氢气从混合物中脱出并且产出孔隙和空洞。热加速干燥时间。相反,第二混合物的pH维持低于10.0,部分是因为不存在水泥。因而在脱气时检查水解。无水泥混合物的密度高于水泥基混合物。干燥的超低水泥混合物的孔隙率为16-24%。无水泥混合物的孔隙率为13-15%。
超低水泥和无水泥的混合物在使用前应干燥以除去任何残 留的水。有利地,如上文所述,无水泥制品中需要的水量显著小于水泥基混合物,因此有利于干燥。一旦干燥并且达到高于800C的使用温度,无水泥材料比超低水泥材料显示出更高的热断裂模量(HMOR)。根据ASTM C-583进行HMOR。在800、1100、1370和1480C下无水泥可浇注物的HMOR分别为10.3、20.7、8.6和2.8MPa。超低水泥可浇注物在每种温度下都具有更低的HMOR,即在800、1100、1370和1480C分别为6.2、4.8、5.5和2.1MPa。
虽然对本发明就其特定实施方案进行了描述,但许多其它变体和改变及其它应用对本领域技术人员而言将变得明显。本发明不局限于本文的具体公开内容。
Claims (10)
1.用于制备耐火制品的耐火混合物,该混合物的组成如下:
a)pH缓冲剂,所述pH缓冲剂选自氧化锆、氧化铝、氧化镁、非水泥质钙化合物、和它们的组合;
b)碳化硅;
c)气相法氧化硅;
d)金属粘合剂,其选自铝、硅、镁、铬、锆、铁、它们的组合或合金;
e)任选的抗絮凝剂;
f)任选的碳;和
g)任选的螯合剂,所述螯合剂选自柠檬酸和硼酸。
2.权利要求1的混合物,其特征在于该金属粘合剂包含颗粒尺寸不大于70目的金属。
3.权利要求2的混合物,其中a)pH缓冲剂和c)气相法氧化硅的组合为至少65重量%且金属粘合剂的量为0.1-10重量%。
4.权利要求2的混合物,其特征在于所述金属粘合剂选自铝、硅、它们的合金或混合物。
5.权利要求1的混合物,其特征在于当与水混合产生具有所需流动性的混合物时pH不大于10.0。
6.根据权利要求1的混合物,包含69重量%氧化铝、22.5重量%碳化硅、6重量%气相法氧化硅、0.75重量%硅和0.5重量%铝。
7.耐火制品,该耐火制品由包含如下步骤的方法制成:
a)将根据权利要求1-6中任一项的混合物进行混合;
b)加入足量的水以产生具有所需流动性的混合物;
c)将所述混合物成形为制品;
d)使所述制品固化;和
e)干燥成形物以除去过量的水。
8.权利要求7的耐火制品,其特征在于所述方法还包括干燥后将该制品加热至使用温度的步骤。
9.制造耐火制品的方法,包括步骤:
a)将根据权利要求1-6中任一项的混合物进行混合;
b)加入足量的水以产生具有所需流动性的混合物;
c)将所述混合物成形为制品;
d)使所述制品固化;和
e)干燥成形物以除去过量的水。
10.据权利要求9的方法,还包括干燥后将该制品加热至使用温度的步骤。
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US60/818,799 | 2006-07-06 | ||
PCT/US2007/072927 WO2008006053A2 (en) | 2006-07-06 | 2007-07-06 | Cement-free refractory |
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US (1) | US20100009840A1 (zh) |
EP (1) | EP2041329A2 (zh) |
JP (2) | JP5823666B2 (zh) |
KR (1) | KR20090031447A (zh) |
CN (1) | CN101501231B (zh) |
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AU (1) | AU2007269073B2 (zh) |
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EA (1) | EA013714B1 (zh) |
MX (1) | MX2009000161A (zh) |
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TWI421227B (zh) * | 2006-07-06 | 2014-01-01 | Vesuvius Crucible Co | 無水泥耐火物 |
EP2565173A1 (en) * | 2011-09-02 | 2013-03-06 | Calderys France | Castable refractory composition |
DE202013011886U1 (de) * | 2013-06-28 | 2014-09-03 | Refratechnik Holding Gmbh | Feuerfestes Erzeugnis |
CN107188583B (zh) * | 2017-07-12 | 2020-09-15 | 瑞泰科技股份有限公司 | 一种用于cfb锅炉内衬裂缝的填缝料 |
CN112851306A (zh) * | 2021-01-13 | 2021-05-28 | 湖南湘钢瑞泰科技有限公司 | 一种rh用快速烧结喷补料及其制备方法 |
JP7368648B1 (ja) * | 2023-03-13 | 2023-10-24 | 黒崎播磨株式会社 | 不焼成塩基性れんがの製造方法 |
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WO2008006053A2 (en) | 2008-01-10 |
MX2009000161A (es) | 2009-01-23 |
KR20090031447A (ko) | 2009-03-25 |
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TW200808678A (en) | 2008-02-16 |
EP2041329A2 (en) | 2009-04-01 |
US20100009840A1 (en) | 2010-01-14 |
JP5823666B2 (ja) | 2015-11-25 |
CA2656695A1 (en) | 2008-01-10 |
BRPI0714034A8 (pt) | 2018-01-02 |
EA200900148A1 (ru) | 2009-06-30 |
CA2656695C (en) | 2016-04-12 |
AR061827A1 (es) | 2008-09-24 |
UA95290C2 (uk) | 2011-07-25 |
AR098449A2 (es) | 2016-05-26 |
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BRPI0714034A2 (pt) | 2012-12-04 |
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