CN1543446A - 由玻璃纤维废料制备产品的方法 - Google Patents
由玻璃纤维废料制备产品的方法 Download PDFInfo
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- CN1543446A CN1543446A CNA028129598A CN02812959A CN1543446A CN 1543446 A CN1543446 A CN 1543446A CN A028129598 A CNA028129598 A CN A028129598A CN 02812959 A CN02812959 A CN 02812959A CN 1543446 A CN1543446 A CN 1543446A
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- Prior art keywords
- glass
- additive
- waste
- ceramic
- glass powder
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- 239000002699 waste material Substances 0.000 title claims abstract description 81
- 239000003365 glass fiber Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 97
- 239000000843 powder Substances 0.000 claims abstract description 67
- 239000011521 glass Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000004927 clay Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000011361 granulated particle Substances 0.000 claims abstract 3
- 239000011152 fibreglass Substances 0.000 claims description 63
- 239000011230 binding agent Substances 0.000 claims description 50
- 239000000945 filler Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011449 brick Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 229910052570 clay Inorganic materials 0.000 claims 1
- 239000011362 coarse particle Substances 0.000 claims 1
- 239000010433 feldspar Substances 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000006063 cullet Substances 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 6
- 238000006062 fragmentation reaction Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000005356 container glass Substances 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 239000011363 dried mixture Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- -1 polyoxyethylene Polymers 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011491 glass wool Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000010811 mineral waste Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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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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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- C03C1/026—Pelletisation or prereacting of powdered raw materials
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
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- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/82—Asbestos; Glass; Fused silica
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Abstract
本发明提供通过一种低成本的加工过程将大量的玻璃纤维废料转变成有用的陶瓷产品的方法。所述方法包括将玻璃纤维废料减小至玻璃粉末;将玻璃粉末与添加剂混合形成一种玻璃-添加剂混合物;对玻璃-添加剂混合物颗粒化处理,使之成为颗粒状粒子;将颗粒状粒子成型为陶瓷制品生坯;以及将该陶瓷制品生坯加热成为陶瓷产品。该处理过程中可以包含水和粘土。仅仅需要一个烧结步骤,而且,其峰值烧结温度低,为约700-1000℃。与粘土基传统陶瓷的制造相比,所述方法节省能源和天然资源。由本发明可以制备高质量的不可渗透的陶瓷产品。
Description
相关申请的相互参照
我要求2001年6月28日提交的美国临时申请60/301,959的权益。
发明背景
本发明涉及由玻璃纤维废料制备的陶瓷产品;由玻璃纤维废料制备陶瓷产品的粉料配合料配方;以及由玻璃纤维废料制备陶瓷产品的方法。能够由本发明制备的陶瓷产品的实例有瓦和砖,但是也可以制造其它陶瓷产品。本发明涉及两个当前面临的问题:陶瓷工业的能源消耗需要降低;以及需要新技术来将玻璃纤维废料重新加工成有用的产品。
陶瓷工业尤其在烧结期间会消耗大量的能源。要求烧结温度高于1200℃(2200°F),以便将典型陶瓷原料烧结成致密产品。改变原料配方可导致烧结温度降低,但是,由于所使用的原料类型,这种改善很有限。大多数的传统陶瓷产品如瓦和砖,主要由粘土基原料构成,这类原料本身就要求高的烧结温度。其它的陶瓷制造步骤,例如干燥过程,其耗能也很高。耗能成本构成整个制造成本的主要部分,因此,降低能耗的新方法对于陶瓷工业意义重大。
玻璃纤维工业产生大量的玻璃纤维废料,这些废料目前从经济角度看还不能再利用,因此只能掩埋处理。玻璃纤维废料在纤维成型期间产生,而且也在纤维产品制造期间产生。玻璃纤维废料可能通过重新熔化形成新的玻璃纤维来加以再利用。但是,玻璃纤维废料一般不进行重新熔化,原因是在成型过程中,源自于废料的杂质在纤维中的含量高得无法接受,会导致纤维断裂。重复利用的玻璃(指的是碎玻璃)在多种玻璃产品的制造中通常作为原料的20-35%加以利用。碎玻璃在一些玻璃纤维的制造中也使用,但是其主要来源于容器和平板玻璃。
两种主要的玻璃纤维是用于绝缘产品的玻璃棉和用于纺织产品的连续纤维。玻璃棉通过对玻璃熔体快速纺丝,使其通过旋转柱状容器中的孔制备而成。连续玻璃纤维通过将玻璃熔体拉过贵重金属坩埚制备而成。这两种方法中,纤维被空气或者蒸汽送风机快速冷却。然后,进行称作上浆的有机化学处理,以便最大程度地减轻纤维与纤维在加工过程中的磨损,并且提供特殊产品应用所必需的涂层。
在加工过程中,会周期性出现产生废料的各种故障,例如纤维断裂。纤维上的上浆涂层阻碍废料作为碎玻璃马上重新使用,因为浆料会在熔体中形成不可接受数量的残存碳。可以在熔化之前,采用附加的处理步骤来除掉浆料,但是,与使用成批的原料相比,该附加处理不经济。研究进一步表明:甚至当除掉所述浆料时,还会存在其它的污染物,这些污染物在成型期间会造成纤维的断裂率很高。由于存在这些问题,大量的玻璃纤维废料目前挖坑掩埋处理。需要新技术来将这种工业废料重新加工成有用的产品。
本发明中废玻璃指的是任何被废弃的工业玻璃纤维或者使用后的玻璃纤维。任何形式的玻璃纤维,例如用于纺织产品的连续纤维和用于绝缘产品的玻璃棉都可以使用。此外,在本发明中也可以使用产生于玻璃纤维熔化过程的任何其它形式的废玻璃,例如排放掉的玻璃。玻璃纤维废料可以由玻璃纤维制造厂获得,但是也可以使用其它的玻璃纤维来源。针对众多的应用场合,存在各种玻璃纤维组合物。玻璃纤维组合物的软化温度典型地约为650至约800℃。这一独特的软化特性使得由玻璃纤维的细小粉末制成的制品可以通过在比烧结陶瓷产品通常要求的温度低得多的温度下,进行粘相烧结加以致密化。本发明利用玻璃纤维的低温致密化特性,通过节省能源和降低设备以及维护费用,来降低制造成本。
本发明是新颖的,原因是能够低成本由最高达100%的玻璃纤维废料制备出高质量的陶瓷产品。与传统陶瓷加工方法相比,本发明节省能源和天然资源。能够获得一种存在少量孔隙的不可渗透的陶瓷显微结构。不可渗透指的是陶瓷产品具有低于0.5%的极低水吸附量。存在少量孔隙的不可渗透的陶瓷显微结构对于获得高质量的性能很关键。通过本发明可以制备出具有各种颜色和类似上釉的平滑有光泽的表面的陶瓷产品。还可以通过添加填料和/或通过玻璃的部分晶化来调整表面纹理和其它烧结性能。
以前,已发展了各种方法来由废玻璃生产陶瓷产品。美国专利6,340,650回顾了以前方法中存在的处理问题,并且提出了通过在处理过程中避免使用水和粘土来消除这些问题的方法。存在几种玻璃纤维组合物。这些组合物与容器和平板玻璃相比,由于玻璃纤维的表面积大,不易与水发生化学反应。与容器和平板玻璃相比,玻璃纤维与水反应的敏感性较小,使得处理玻璃纤维时的灵活性更大。此外,某些玻璃纤维组合物,例如E-玻璃的软化温度比容器和平板玻璃组合物的软化温度高。软化温度较高允许在粉料配合料配方中存在烧结期间会产生挥发性物质的粘土和其他陶瓷原料,而不会对致密化性能产生不利影响。本发明提供了一种由玻璃纤维废料制造陶瓷产品的方法,该方法中,可以在烧结期间添加水和粘土。
另外,出人意料地,与使用容器或平板玻璃相比,使用玻璃纤维具有其它几种重要优点。这是因为在组成和污染物上存在差异,尤其是因为玻璃形式的不同(纤维与块状玻璃)。将容器或平板玻璃加工成细小粉末包括两个或三个需耗费大量能源的破碎和研磨步骤。玻璃纤维的直径典型地为3-100微米,因此,为了制备细小粉末,仅仅需要将其一个尺寸破断。与粉碎容器和平板玻璃相比,玻璃纤维的切碎和研磨简单得多,而且耗能较少。工业上的玻璃纤维废料与使用后的容器玻璃相比,其组成非常均匀,而且污染物少得多。这样可以对生产的陶瓷产品的颜色和其它性能进行更好地控制。此外,与容器和平板玻璃相比,玻璃纤维组合物的热膨胀系数低得多,因此,能够改善抗热震性能。
与目前的工艺实践相比,本发明具有各种环境方面的优点。本方法将玻璃纤维完全转变成致密的陶瓷产品,因此,消除了将来在处理和废弃纤维时存在的环境问题。通过使用重复利用的玻璃作原料,不需要进行传统原料的采矿、加工和运输。与传统粘土瓦的生产方法相比,特别是与玻璃熔化法生产瓦的方法相比,本发明所需要的能源显著降低。这主要是因为与粘土瓦的1200℃,和熔体瓦的>1500℃的烧结温度相比,本发明的烧结温度显著降低,仅为700-1000℃。
发明简述
本发明提供通过一种低成本的加工方法将大量的玻璃纤维废料转变成有用的陶瓷产品的方法。所述方法包括将玻璃纤维废料减小至玻璃粉末;将玻璃粉末与添加剂混合形成一种玻璃-添加剂混合物;对玻璃-添加剂混合物颗粒化处理,使之成为颗粒状粒子;将颗粒状粒子成型为陶瓷制品生坯;以及将该陶瓷制品生坯加热成为陶瓷产品。该处理方法中可以包含水和粘土。仅仅需要一个烧结步骤,且其峰值烧结温度低,为约700-1000℃。与粘土基传统陶瓷的制造相比,所述方法节省能源和天然资源。由本发明可以制备高质量的不可渗透的陶瓷产品。
发明详述
本发明的粉料配合料配方包括70-100%玻璃纤维废料、0-20%填料和0-10%有机粘结剂。优选的粉料配合料配方包括84-100%废玻璃、0-10%填料和0-6%有机粘结剂。所有的百分数均为重量百分数。还应该了解的是:可以在粉料配合料配方中添加其它常规的陶瓷处理添加剂,例如润湿剂、表面活性剂、抗絮凝剂、促凝剂、絮凝剂、增塑剂、抗发泡剂、润滑剂、防腐剂等,以便在不改变本发明的范围的前提下,进一步优化本处理方法。
有机粘结剂以及其它有机添加剂(如果存在)在烧结期间将会烧光,因此不会成为最终产品的一部分。玻璃纤维废料和填料均是烧结之后仍保留的无机组合物,并且构成最终产品的组成。结果,初始的粉料配合料配方(前面给出)在烧结期间转变成含有80-100%玻璃纤维废料和0-20%填料的最终产品组合物。优选的最终产品组合物含有90-100%废玻璃和0-10%填料。通过从粉料配合料配方中减去有机粘结剂的量,然后,再将余下的组成归一化处理成100%,便确定出最终产品组合物。
本发明中的填料是一种为了改变最终产品的颜色、表面纹理或者任何其它性能,或者作为无机粘结剂而添加的陶瓷原料。无机粘结剂填料,例如粘土或者硅酸钠在颗粒化和压制步骤期间起粘结剂作用,并且减少或者排除了对有机粘结剂的需求。添加填料不是制备高质量陶瓷产品所必需的,但是,可望用于使最终产品获得特定的性能。许多种填料添加剂在本发明中可以单独使用或者组合使用。
为了控制颜色而添加的填料称作着色剂。普通的陶瓷着色剂可以用来由本发明制备具有多种颜色的陶瓷产品。各种氧化物着色剂的实例是用于产生蓝色的氧化钴、产生绿色的氧化铬和产生红色的氧化铁。许多商品着色剂是依据经常被熔化成玻璃料的氧化物的复杂组合制备而成的。除了颜色之外,添加填料还能够控制其它特性和性能,例如表面纹理、结晶特性以及机械、热和化学耐久性能。其它的填料实例是氧化铝、硅石、氧化锆和粘土。
玻璃纤维废料和填料必须以粉末形式用于粉料配合料配方中。所要求的粉末颗粒尺寸取决于要求的最终性能。对于本发明,玻璃纤维废料和填料的粉末颗粒尺寸小于30目(<0.6mm)。优选尺寸小于100目(<0.1mm)。由于纤维直径比要求的尺寸小,因此,玻璃纤维的颗粒尺寸被纤维长度所控制。为了调整最终产品的性能,在粉料配合料配方中还可以存在颗粒尺寸较粗的填料。例如,可以添加较粗的填料,以便产生较粗糙的表面纹理,提高摩擦系数和滑动阻力。
本发明中的有机粘结剂包括为了将无机废玻璃和填料颗粒结合一起可以添加的任何有机粘结剂。有机粘结剂首先与玻璃纤维废料和填料颗粒混合,形成颗粒状自由流动的粉末。然后,将所述粉末成型为陶瓷制品。成型步骤之后,有机粘结剂使制品生坯具有足够的强度,从而能够加以处理和输送至烧结步骤。如果无机粘结剂作为填料添加,则可以减少所需要的有机粘结剂的量或者甚至不使用有机粘结剂。
有机粘结剂的实例有天然树胶、纤维素醚、聚合醇、丙烯酸酯树脂、乙二醇类和蜡。在下面示出的本发明的实施例中,采用聚乙二醇和聚乙烯醇作为有机粘结剂。在不改变本发明的范围的前提下,可以使用其它有机粘结剂。为了有效发挥作用,要求有机粘结剂为液态,这样,无机玻璃纤维和填料颗粒能够被有机粘结剂润温和涂覆。在室温(~20℃)下有机粘结剂或者为液态或者为固态。可以将固态的有机粘结剂溶解在特定液体中,与无机粉末混合,然后进行干燥,将液体去除,获得涂覆有有机粘结剂的无机粉末。本发明中,可以采用水或者非水液体如醇类溶解固态有机粘结剂。如果有机粘结剂为液态,则不需要另外的液体。
下面的段落介绍了本发明方法中每一个步骤的细节。所述方法的第一个步骤包括制备玻璃粉末。工业玻璃纤维废料不管是否涂覆有机浆料,都可以用作制备粉末的原料玻璃。也可以使用任何其它类型或者形式的玻璃纤维废料。本发明的方法对于玻璃纤维废料中正常水平的污染物不敏感,因此,不要求对玻璃进行清洗。玻璃纤维颗粒尺寸被降至<30目(<0.6mm)。优选尺寸<100目(<0.1mm)。
减小颗粒尺寸所采用的步骤取决于玻璃纤维废料的组成,也取决于玻璃纤维废料的形式。多种玻璃纤维组合物可以有许许多多不同形式,这就会产生各种类型的玻璃纤维废料。通过在处理过程中避免使用水的步骤,可以减小所有类型的玻璃纤维废料的颗粒尺寸。对于在处理期间与水发生反应会产生不利影响的玻璃纤维组合物而言,这一点很重要。对于在处理期间与水发生反应不会产生不利影响的玻璃纤维组合物,则可以通过在处理过程中使用水的步骤减小颗粒尺寸。
在减小颗粒尺寸之前,可以对玻璃纤维废料进行加热,以除去可能存在的水。如果温度足够高,则可以在减小颗粒尺寸之前,将有机物质,例如有机浆料除去。加热玻璃纤维废料也可能导致玻璃纤维变得更脆,这就使得纤维更容易断裂和破碎。可以采用任何类型的切断、破碎、研磨、磨制等方法减小玻璃纤维废料的颗粒尺寸。可以使用几种普通的陶瓷处理设备,例如切断机、颚式或锥式破碎机、球磨机、锤磨机、振动磨机、碾磨机、辊磨机等,来减小颗粒尺寸。在将颗粒尺寸减小之后,通过一个30目筛子(对于优选颗粒尺寸,筛子目数为100目)对玻璃纤维粉末进行筛选。
将由所述颗粒尺寸减小方法获得的细玻璃粉末(<30或<100目)与依据所使用的粉料配合料配方确定的要求量的填料和有机粘结剂组合。在天平上称出每种组分的重量,加以组合然后进行混合。由于原始粘结剂是一种液体,或者由于粘结剂被溶解在水或者非水液体如一种醇中,因此,有机粘结剂以液相形式添加。液相的有机粘结剂与玻璃和填料粉末组合,并且在任何一种混合机,例如盘式混合机、锥式混合机、带式混合机、旋转鼓式混合机等中进行混合,产生一种颗粒状的自由流动的粉末。通过在干燥器,例如流态床干燥器中进行干燥,或者通过喷雾干燥,可以将多余的液体去除。但是,优选保持液体含量足够低,这样,就不再需要干燥步骤。
将具有粉料配合料配方的颗粒状的自由流动的粉末成型为陶瓷制品生坯。生坯这里指的是未烧结的陶瓷。可以使用任何成型方法,但是优选采用干压法。干压法中,将粉末放在具有要求形状的金属模中,并且采用压头将粉末压实。然后,将压制成的制品从模具中取出,并且在窑或炉中进行烧结。如果在压制成的制品中存在液体,那么,烧结之前,可以包括一个附加的炉中干燥步骤,以便将残留的液体去除。
烧结过程的初始步骤包括粘结剂的烧尽,以便将有机粘结剂去除。优选地,粘结剂的烧尽在对陶瓷制品进行烧结时的初始加热期间进行。也可以采用单独的粘结剂的烧尽和烧结过程。在上述任意一种情形下,都必须在玻璃粉末软化和烧结之前将有机粘结剂完全除去,以防止在烧结后的产品中产生缺陷。有机粘结剂的典型烧尽温度为约200-400℃。具体的烧结温度和时间规范取决于所使用的粉料配合料配方。优选所要求的温度最低和时间最短,而同时又仍然能够获得差不多为0%的孔隙率。所要求的最大烧结温度范围为约700-1000℃。
下面的段落提供了25个本发明的实施例。
实施例1:实施例1的粉料配合料配方由100%的源自于玻璃纤维制造商的玻璃纤维废料构成。所述废料来自于E-玻璃所用的连续玻璃纤维的生产中,并且涂覆有有机浆料。所述纤维已被玻璃纤维制造商处理成小碎片。在第一个步骤,采用研钵和杵将玻璃纤维废料研磨成细小粉末。然后,采用100目(<0.1mm)筛对粉末进行筛分。使用液压机,在5000磅/平方英寸的压力下,在金属模中,不用粘结剂将筛分后的粉末压制成直径16mm的柱状试样。将压制成的试样在可编程的箱式炉中进行烧结,首先烧尽有机浆料,然后,将玻璃粉末烧结成致密的陶瓷产品。所采用的最高温度为900℃。所获陶瓷产品的密度为2.60g/cm3,该值高于E-玻璃2.61g/cm3理论密度的99%。该陶瓷产品半透明,具有光滑的釉状表面。
实施例2:本实施例也采用与上述实施例1同样的步骤,只是实施例1中使用的玻璃纤维废料被由绝缘产品获得的玻璃纤维棉取代,而且,最高烧结温度变成750℃。获得了与实施例1类似的具有光滑釉状表面的高质量陶瓷产品。
实施例3:本实施例也采用与上述实施例1同样的步骤,只是实施例1中使用的玻璃纤维废料由被排放掉的玻璃(drain glass)取代,而且,玻璃在采用研钵和杵研磨之前,加热至130℃,以便将水分去除。该排放掉的玻璃由玻璃纤维制造商的玻璃纤维熔炉中获得。该排放掉的玻璃的形态为大量的玻璃碎片。获得了与实施例1类似的具有2.61g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例4:本实施例也采用与上述实施例3同样的步骤,只是:如下所述,在玻璃粉末中添加了6%(重量)的聚乙烯醇粘结剂,并且压制出1.25英寸的正方形试样。聚乙烯醇粘结剂首先溶解在水中,然后再与玻璃粉末混合。将该玻璃-粘结剂混合物在烤箱中,约90℃下干燥,以便将水分去除。采用研钵和杵对干燥后的混合物进行研磨,并且采用30目筛进行筛分。在压制和烧结步骤之后,获得了与实施例1类似的具有2.59g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例5:本实施例也采用与上述实施例1同样的步骤,只是实施例1中使用的玻璃纤维废料被第二种E-玻璃连续玻璃纤维废料取代,而且,在采用研钵和杵研磨之前,将玻璃加热至800℃。所述废料由玻璃纤维制造商获得,并且未涂覆有机浆料。所述纤维长约12英寸,比实施例1中使用的玻璃纤维废料的纤维长度大得多。获得了与实施例1类似的具有2.61g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例6:本实施例也采用与上述实施例5同样的步骤,只是:如下所述,在玻璃粉末中添加了6%(重量)的聚乙烯醇粘结剂,并且压制出1.25英寸的正方形试样。聚乙烯醇粘结剂首先溶解在水中,然后再与玻璃粉末混合。将该玻璃-粘结剂混合物在烤箱中,约90℃下干燥,以便将水分去除。采用研钵和杵对干燥后的混合物进行研磨,并且采用30目筛进行筛分。在压制和烧结步骤之后,获得了与实施例1类似的具有2.60g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例7:本实施例也采用与上述实施例1同样的步骤,只是实施例1中使用的玻璃纤维废料被第三种E-玻璃连续玻璃纤维废料取代,而且,在采用研钵和杵研磨之前,将玻璃加热至800℃。所述废料由玻璃纤维制造商获得,并且,与实施例1中使用的玻璃纤维废料相比,涂覆了更多的有机浆料。所述纤维长约12英寸,比实施例1中使用的玻璃纤维废料的纤维长度大得多。获得了与实施例1类似的具有2.60g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例8:本实施例也采用与上述实施例7同样的步骤,只是:如下所述,在玻璃粉末中添加了6%(重量)的聚乙烯醇粘结剂,并且压制出1.25英寸的正方形试样。聚乙烯醇粘结剂首先溶解在水中,然后再与玻璃粉末混合。将该玻璃-粘结剂混合物在烤箱中,约90℃下干燥,以便将水分去除。采用研钵和杵对干燥后的混合物进行研磨,并且采用30目筛进行筛分。在压制和烧结步骤之后,获得了与实施例1类似的具有2.59g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例9:本实施例也采用与上述实施例7同样的步骤,只是在采用研钵和杵研磨之前,将玻璃纤维废料加热至750℃,而不是800℃。获得了与实施例1类似的具有2.63g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例10:本实施例也采用与上述实施例9同样的步骤,只是将6%(重量)的聚乙二醇粘结剂与玻璃混合。聚乙二醇粘结剂室温下为液态,因此未添加附加液体。在压制和烧结步骤之后,获得了与实施例1类似的具有2.60g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例11:本实施例也采用与上述实施例9同样的步骤,只是:如下所述,在玻璃粉末中添加了6%(重量)的聚乙烯醇粘结剂,并且压制出1.25英寸的正方形试样。聚乙烯醇粘结剂首先溶解在水中,然后再与玻璃粉末混合。将该玻璃-粘结剂混合物在烤箱中,约95℃下干燥,以便将水分去除。采用研钵和杵对干燥后的混合物进行研磨,并且采用100目筛进行筛分。在压制和烧结步骤之后,获得了与实施例1类似的具有2.59g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例12-14:这些实施例也采用与上述实施例11同样的步骤,只是采用着色剂填料替代了2.5%(重量)的玻璃纤维废料。对三种市售的陶瓷着色剂(也称作陶瓷染料)进行了评价。实施例12使用的是白色着色剂;实施例13使用的是浅蓝色着色剂;实施例14使用的是深蓝色着色剂。获得了与实施例1类似的高质量陶瓷产品,只是陶瓷产品的颜色与所用的着色剂相对应。所获陶瓷产品的密度范围为2.60-2.63g/cm3。这些实施例证实本发明具有制备不同颜色的陶瓷产品的能力。
实施例15:本实施例也采用与上述实施例7同样的步骤,只是:如下所述,玻璃纤维废料被碾磨破碎,而不是采用研钵和杵进行研磨,而且,如同实施例10,也添加了聚乙二醇粘结剂。在800℃下加热之后,采用带有氧化铝介质的氧化铝球磨机在水中对玻璃纤维废料进行碾磨,然后,采用100目(<0.1mm)筛进行筛分。之后,将该球磨后的玻璃在烤箱中,约115℃下干燥,以便将水分去除。对干燥后的玻璃粉末再次采用100目(<0.1mm)筛进行筛分。在添加粘结剂之后,进行压制和烧结,获得了与实施例1类似的具有2.63g/cm3密度和光滑釉状表面的高质量陶瓷产品。
实施例16-22:这些实施例也采用与上述实施例15同样的步骤,只是采用着色剂填料替代了2.5%(重量)的玻璃纤维废料。对七种市售的陶瓷着色剂(也称作陶瓷染料)进行了评价。实施例16使用的是白色着色剂;实施例17使用的是黄色着色剂;实施例18使用的是绿色着色剂;实施例19使用的是浅蓝色着色剂;实施例20使用的是深蓝色着色剂;实施例21使用的是红色着色剂;实施例22使用的是黑色着色剂。获得了与实施例1类似的高质量陶瓷产品,只是陶瓷产品的颜色与所用的着色剂相对应。所获陶瓷产品的密度范围为2.61-2.66g/cm3。这些实施例证实本发明具有制备各种不同颜色的陶瓷产品的能力。
实施例23-24:这些实施例也采用与上述实施例7同样的步骤,只是:如下所述,玻璃纤维废料被碾磨破碎,而不是采用研钵和杵进行研磨,而且,采用填料替代了5.0%(重量)的玻璃纤维废料。在800℃下加热之后,采用带有氧化铝介质的氧化铝球磨机在水中对玻璃纤维废料进行碾磨,然后,采用100目(<0.1mm)筛进行筛分。之后,将该球磨后的玻璃在烤箱中,约115℃下干燥,以便将水分去除。对干燥后的玻璃粉末再次采用100目(<0.1mm)筛进行筛分,并且,随后与两种填料进行混合。实施例23使用的是硅石粉末填料,而实施例24使用的是氧化铝粉末填料。获得了与实施例1类似的高质量陶瓷产品,只是所获陶瓷产品的表面纹理更粗糙。两个实施例的陶瓷产品的密度均为2.61g/cm3。这些实施例证实利用填料添加剂能够改变由本发明获得的陶瓷产品的表面纹理。
实施例25:本实施例也采用与上述实施例7同样的步骤,只是:如下所述,玻璃纤维废料被碾磨破碎,而不是采用研钵和杵进行研磨,而且,采用填料替代了5.0%(重量)的玻璃纤维废料。在800℃下加热之后,采用带有氧化铝介质的氧化铝球磨机在水中对玻璃纤维废料进行碾磨,然后,采用100目(<0.1mm)筛进行筛分。之后,将该球磨后的玻璃在烤箱中,约115℃下干燥,以便将水分去除。对干燥后的玻璃粉末再次采用100目(<0.1mm)筛进行筛分,并且,随后与高岭粘土填料进行混合。获得了与实施例1类似的高质量陶瓷产品。陶瓷产品的密度为2.58g/cm3。该实施例证实能够在处理过程中利用粘土填料添加剂作为无机粘结剂。
前面通过实施例已对本发明进行了详细介绍。应该了解的是:只要不偏离本发明的范围,本领域的专业人员可以对本发明进行各种其它的改变和修正。例如,如果需要,也可以在陶瓷产品上涂覆釉料,但不是必须的。釉料可以在烧结之前涂覆,这样,仅仅需要一次烧结。釉料也可以在烧结之后涂覆,这时就需要进行第二次烧结。
Claims (26)
1.一种由玻璃纤维废料制备陶瓷产品的方法,所述的方法包括:
将玻璃纤维废料减小至玻璃粉末;
将玻璃粉末与添加剂混合形成一种玻璃-添加剂混合物;
对玻璃-添加剂混合物颗粒化处理,使之成为颗粒状粒子;
将颗粒状粒子成型为陶瓷制品生坯;以及
将该陶瓷制品生坯加热成为陶瓷产品。
2.根据权利要求1的方法,其中,在将玻璃纤维废料减小至玻璃粉末之前,加热玻璃纤维废料。
3.根据权利要求1的方法,其中,在将玻璃纤维废料减小至玻璃粉末之前,加热玻璃纤维废料以除去水分,烧尽有机物质,和/或提高玻璃纤维废料的脆性。
4.根据权利要求1的方法,其中,将玻璃纤维废料减小至玻璃粉末包括将玻璃纤维废料减小至纤维长度小于约0.6mm的碎片。
5.根据权利要求1的方法,其中,将玻璃纤维废料减小至玻璃粉末包括添加液体减小玻璃纤维废料的尺寸。
6.根据权利要求1的方法,其中,将玻璃纤维废料减小至玻璃粉末包括通过添加水减小玻璃纤维废料的尺寸。
7.根据权利要求1的方法,其中,将玻璃纤维废料减小至玻璃粉末包括不需要通过添加液体来减小玻璃纤维废料的尺寸。
8.根据权利要求1的方法,其中,70-100%(重量)的玻璃-添加剂混合物由废玻璃构成,0-20%(重量)的玻璃-添加剂混合物由填料构成,以及0-10%(重量)的玻璃-添加剂混合物由有机粘结剂构成,
9.根据权利要求1的方法,其中,添加剂为填料,所述填料由硅石、氧化铝、氧化锆、粘土、长石和/或任何其它陶瓷原料组成。
10.根据权利要求1的方法,其中,添加剂为填料,所述填料由粘土、硅酸钠和/或其它任何无机粘结剂组成。
11.根据权利要求1的方法,其中,添加剂为填料,所述填料为无机着色剂。
12.根据权利要求1的方法,其中,添加剂为填料,所述填料是为了使陶瓷产品表面纹理粗糙而添加的粗颗粒。
13.根据权利要求1的方法,其中,添加剂为填料,所述填料的添加目的是改善陶瓷产品的性能,包括但不限于机械、化学耐久性以及热性能。
14.根据权利要求1的方法,其中,添加剂为含水有机粘结剂。
15.根据权利要求1的方法,其中,添加剂为无水有机粘结剂。
16.根据权利要求1的方法,其中,玻璃粉末与添加剂形成玻璃-添加剂混合物的混合包括玻璃粉末与添加剂在液体中的混合。
17.根据权利要求1的方法,其中,玻璃粉末与添加剂形成玻璃-添加剂混合物的混合包括玻璃粉末与添加剂在水中的混合。
18.根据权利要求1的方法,其中,玻璃粉末与添加剂形成玻璃-添加剂混合物包括在不添加液体的情况下,玻璃粉末与添加剂的混合。
19.根据权利要求1的方法,其中,对玻璃-添加剂混合物颗粒化处理,使之成为颗粒状粒子包括在干燥器中对玻璃-添加剂混合物进行干燥,干燥器包括但不限于喷雾干燥器或者流化床干燥器。
20.根据权利要求1的方法,其中,将颗粒状粒子成型为陶瓷制品生坯包括压制或者挤出。
21.根据权利要求1的方法,其中,将陶瓷制品生坯加热成为陶瓷产品包括在约700-1000℃的最高温度下烧结陶瓷制品生坯。
22.根据权利要求1的方法,其中,将陶瓷制品生坯加热成为陶瓷产品包括对陶瓷制品生坯进行干燥,以除掉液体,然后,在约700-1000℃的最高温度下进行烧结。
23.根据权利要求1的方法,其中,将陶瓷制品生坯加热成为陶瓷产品会引起陶瓷产品发生部分晶化。
24.根据权利要求1的方法,其中,陶瓷产品包括瓦或砖。
25.根据权利要求1的方法,其中,陶瓷产品具有光滑的有光泽表面。
26.根据权利要求1的方法,其中,陶瓷产品可以通过涂覆釉料加以进一步处理。
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JP (1) | JP2005511459A (zh) |
KR (1) | KR20040030720A (zh) |
CN (2) | CN1919784A (zh) |
BR (1) | BR0210434A (zh) |
CA (1) | CA2449495A1 (zh) |
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- 2002-06-20 CA CA002449495A patent/CA2449495A1/en not_active Abandoned
- 2002-06-20 WO PCT/US2002/019483 patent/WO2003002480A1/en active Application Filing
- 2002-06-20 MX MXPA03011832A patent/MXPA03011832A/es active IP Right Grant
- 2002-06-20 JP JP2003508668A patent/JP2005511459A/ja active Pending
- 2002-06-20 KR KR10-2003-7017159A patent/KR20040030720A/ko not_active Application Discontinuation
- 2002-06-20 CN CNA2006100940629A patent/CN1919784A/zh active Pending
- 2002-06-20 BR BR0210434-2A patent/BR0210434A/pt not_active Application Discontinuation
- 2002-06-20 CN CNB028129598A patent/CN1269764C/zh not_active Expired - Fee Related
- 2002-06-20 EP EP02753345A patent/EP1412305A4/en not_active Ceased
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CN102329065A (zh) * | 2011-06-21 | 2012-01-25 | 重庆国际复合材料有限公司 | 不同玻璃废丝与配合料应用于玻璃纤维生产的方法 |
CN102500609A (zh) * | 2011-10-28 | 2012-06-20 | 巨石集团有限公司 | 玻璃纤维废丝循环利用生产工艺 |
CN110156336A (zh) * | 2019-07-02 | 2019-08-23 | 山东聚源玄武岩纤维股份有限公司 | 一种玄武岩纤维废丝的回炉再利用方法 |
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JP2005511459A (ja) | 2005-04-28 |
EP1412305A1 (en) | 2004-04-28 |
WO2003002480A9 (en) | 2003-02-13 |
CN1919784A (zh) | 2007-02-28 |
US20050242477A1 (en) | 2005-11-03 |
MXPA03011832A (es) | 2004-03-26 |
WO2003002480A1 (en) | 2003-01-09 |
US7416690B2 (en) | 2008-08-26 |
CN1269764C (zh) | 2006-08-16 |
BR0210434A (pt) | 2004-08-17 |
KR20040030720A (ko) | 2004-04-09 |
CA2449495A1 (en) | 2003-01-09 |
EP1412305A4 (en) | 2006-05-24 |
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