CN1080612C - 生产实心的成型体的方法 - Google Patents
生产实心的成型体的方法 Download PDFInfo
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/624—Sol-gel processing
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Compositions Of Oxide Ceramics (AREA)
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Abstract
通过制备粉末的含水浆料从金属和陶瓷等不同的粉末成型实心的、均匀的或多孔的、成型体,该浆料含有室温下可溶于水、加热到不超过90℃的温度能形成不可逆的凝胶的蛋白质物质。该蛋白质物质如清蛋白的用量足以形成凝胶。通过注模法、流延法或滴落法并加热到至少相当于蛋白质的凝胶化温度,把浆料成型为要求形状的坯体。
Description
本发明涉及从金属粉末、陶瓷粉末等不同的无机粉料形成实心的成型体的方法。更具体地,本发明涉及这样一种方法,即,从含有无机粉末和加热时能形成凝胶的蛋白质的含水浆料,形成均匀的、致密的、实心的坯体或多孔的、实心的坯体。
已知有几种方法用于从不同的无机粉料形成成型体,既可成型均匀的、致密的坯体,也可成型多孔坯体。致密的坯体的最简单的温法成型方法是注浆法。作为一个惯例,注浆中不需要加入粘结剂,该方法用于没有太精确尺寸要求的相当简单的产品,如,卫生洁具。用于生产切削刀具、耐磨部件、导丝器、压电激励器(piezo activators)等技术产品和结构产品的其他成型方法,可能需要粘结剂,以便使坯体结合得足够紧密,能够从模具中取出和/或输送到下一道工序,所考虑的类型的粉末的产品通常需要在800~2200℃的温度下烧结,这取决于各粉末的熔点。除了粘结剂以外,形成坯体的浆料通常还含有粉末的分散剂。通常使用浸入粉末浆料的具有泡沫结构的有机预成型体制备成型的、多孔的和泡沫的、实心的坯体。然后干燥获得的结构、烧掉所说的预成型体、最后烧结该制品。根据更新的技术,利用在浆料中与水反应的聚合物形成二氧化碳,从而导致泡沫的形成和产生交联的可能性。多孔坯体在绝热材料、过滤材料和催化剂载体等应用中特别有用。
几种不同类型的粘结剂,如蜡、合成的和天然的聚合物(例如,聚乙烯醇、乙烯-丙烯酸共聚物和甲基纤维素和羟乙基纤维素等纤维素衍生物),已经被建议并用于增强生坯。大家还知道用凝胶形成物质来形成生坯,例如,在冷却时可以形成凝胶的琼脂糖,或者单一官能团和两个官能团的丙烯酰胺和两个官能团和多个官能团的丙烯酸盐的合成的单体或单体混合物,它们在加热时可以聚合和交联,形成聚合物凝胶基质,粉料分散在这种基质中。此外,已知某些蛋白质类物质用于生坯的形成。某些蛋白质物质,如明胶和酪素,已经被用作或提出用作水溶液的常规粘结剂物质。在欧洲专利申请0 087 160中,提出了“胶凝剂”和“稳定剂”在制备多孔的金属坯体中的应用。根据该申请,使用了羧甲基纤维素、聚乙烯吡咯烷酮、聚乙烯醇、清蛋白或琼脂,据说其存在对于加入金属粉末时不破坏泡沫结构是必要的。但是,为了固化该泡沫结构,一种稳定剂是必要的,优选的是从混入泡沫中的单体形成的聚氨基甲酸乙酯。所以,在这种方法中,所谓的胶凝剂仅用于泡沫的形成,而硬质凝胶的形成是通过聚氨基甲酸乙酯获得的。明胶也被建议用作凝胶形成体。因此美国专利5,279,994提出了使用明胶作为凝胶形成物质的流延法成型的一种方法。为此使用的明胶需要加热整个浆料使明胶溶解,然后冷却使其成为凝胶。类似地,日本专利申请94-226718提出了使用明胶的凝胶形成特性。根据这个说明书,通过把含有加热溶解的明胶的粉末的浆料浇注到模型中,然后冷却使其凝胶化,形成一种坯体。在该说明书中还提到其他蛋白质也可以使用,例如,清蛋白,但是其中提出的方法严格地是用加热使蛋白质溶解,冷却使其凝胶化的一种方法,即,明胶所要求的条件而不是其他蛋白质物料所必须的凝胶形成条件。使用合成聚合物的凝胶形成提出是不利的,因为聚合物基质的形成需要很高的温度,同时,除去有机物质也需要很高的温度。明胶作为凝胶形成体有一些缺点,即,凝胶的形成是可逆的,并且要求整个浆料的加热,这涉及到高的能量消耗。此外,明胶导致浆料的稠化,这会引起处理上的困难。
根据本发明,已经发现,在作为原料的粉末浆料中加入在加热时形成不可逆的凝胶的水溶性蛋白质,对于形成实心成型体是特别合适的。在本方法中使用的蛋白质物质具有不超过90℃的凝胶形成温度,或凝固温度。凝胶形成温度的低限应该足以使处理容易进行而不会凝固。合适的凝胶形成温度在40℃~70℃范围内。通过用蛋白质物质使浆料凝胶化,粉末颗粒可以紧密地结合在一起,均匀地分布在凝胶中,可以令人满意地保证产生的坯体的形状,并且有足够的湿坯强度使得进一步的处理和加工可以进行而不会产生不可接受的变形。使用这种蛋白质的优点不仅在于形成了不可逆的凝胶,而且在于可以在室温下(约20℃-25℃)制备浆料,通过加热到中等高的温度下进行凝胶化。因此不需要加热整个浆料,而只需要加热模型中或其他成型位置中的浆料,考虑到能量消耗,这种方法是有利的。由于只使用中等高的温度进行凝胶化,也避免了水蒸发的危险,水的蒸发可能导致缺陷。此外,蛋白质不仅可以作为凝胶形成体,而且可以作为分散剂,从而可以避免使用在该技术中提出使用的单独的分散剂。据信清蛋白等球形蛋白质的结构用于分散作用中。例如,蛋白质物质可以是从其任何不同的来源得到的清蛋白,如牛奶和蛋,但是也可以使用具有要求特性的其他球形蛋白质。一个实例是溶菌酶。含有大量蛋白质并适用于本方法的蛋白质物质的实例可以提到血浆蛋白制品和乳清蛋白制品。这类商业产品含有大量的蛋白质和少量的脂肪等其他物质。出于经济方面的原因,考虑到其根据本发明的应用领域,优选的蛋白质是清蛋白。但是,考虑到最近几年中生物化学领域内的技术进步,合理价格的其他具有合适性质的蛋白质变得可以得到是非常可能的。
蛋白质物质是指一种蛋白质或一种含有蛋白质的物质,如上述的血浆蛋白和乳清蛋白制品。对于蛋白质物质的要求是该蛋白质在室温下溶于水,并且在低于90℃凝胶化。由于根据本发明使用的蛋白质是可溶于水的天然物质并且是可生物降解的,其使用不会引起任何环境问题或职业疾病。
因此,本发明涉及从一种任选地增强的无机粉末形成实心的、均匀的或多孔的坯体的方法,所说的无机粉末选自由金属、金属间化合物、硬质金属、金属陶瓷和/或陶瓷的粉末组成的组中。
用于本方法中的粉末是金属粉末、金属间化合物粉末、硬质金属粉末、金属陶瓷粉末或陶瓷粉末。这里所用的术语“金属”包括合金。例如,金属粉末的实例包括铝、镍、铜、钴、钛、硅、黄铜和青铜的粉末。金属间化合物的实例包括硅化物和铝化物,如硅化钼。硬质金属(烧结的碳化物)是各种碳化物的粉末,如,碳化钨和碳化钛。在本说明书中使用的术语“陶瓷”是指无机非金属材料。陶瓷粉末可以是任何金属氧化物,如氧化硅、氧化铝、氧化钇和氧化锆,氮化物,如氮化硅、氮化铝和氮化硼,也可以是硼化钛、碳化硅、碳化硼和莫来石(即Al6Si2O13)。在本发明方法中用来成型致密坯体的特别合适的粉末有氮化硅,赛龙(由Si、Al、O和N元素形成的粉末)。对于多孔坯体,优选的粉末是氧化铝,钛酸 铝,碳化硅,氧化锆和堇青石(2MgO·2Al2O3·5SiO2)。虽然在大多数产品的生产中使用单一种类的粉末或意义明确的混合物,使用粉末的任意混合物(其中各种颗粒之间可能会相互反应)当然也在本发明的范围内。虽然本发明的方法应用于不增强的粉料是优选的,但是把该方法应用于增强的陶瓷材料当然是可能的,因此这也在本发明的范围内。例如,这样的陶瓷基复合材料可以包括传统的、通常用量的晶须、纤维、颗粒和板片形式的增强材料。
制备该浆料的粉末的颗粒尺寸通常在1nm~1mm的较宽范围内。实际的颗粒尺寸在很大程度上由烧结方法决定,较小的颗粒更容易烧结,而较大的颗粒需要热压或热等静压。此外,非常小的颗粒会产生非常粘稠的浆料。对于陶瓷粉末0.1μm~100μm的颗粒尺寸范围具有特别的技术上的意义,对于金属粉末和金属合金粉末,相应的颗粒尺寸范围是1μm~300μm。
浆料的实际制备可以通过蛋白质物质的水溶液和无机粉末(干的或水中的)的简单混合,或把干的蛋白质物质加入的粉末的浆料中。为了得到具有足够尺寸稳定性的坯体,蛋白质物质通常的用量为至少3wt%,按蛋白质计算,以含水相为基。通常不超过20wt%,因为更高的加入量趋于得到太粘的浆料。加入量还取决于粉末的有效面积。蛋白质的加入量的合适的范围是10~15wt%,以含水相为基。浆料中粉末的干基含量通常是20~90vol%,大多数情况下为30~70%。对于具有较大的颗粒尺寸,即具有较小的表面的和/或较宽的颗粒尺寸分布范围的粉末,可以使用较高的干基含量而不会不可接受地增大粘度。干基含量在某种程度上也取决于成型方法。简单的搅拌通常足以制备浆料,例如,通过浆式搅拌器或类似的搅拌设备进行搅拌。如果粉末中存在团聚,可能需要高能量的处理,例如,球磨或超声波处理。已经发现,即使浆料经过相当长时间的高能量处理,如球磨,也不会对蛋白质的凝固能力产生不良的影响。对于均匀的、致密的坯体的生产,为了防止在空气分散进入浆料时形成泡沫,通常需要在浆料中加入消泡剂。合适的消泡剂的实例是脂肪醇(如辛醇)和硅油。消泡剂的量通常为至少0.1wt%,以含水相为基。对于发泡的、多孔坯体的生产,使用蛋白质物质的泡沫形成特性及其形成凝胶的能力。在这种情况下,允许通过搅拌混入空气使蛋白质形成泡沫,自然不用消泡剂。通过搅拌程度控制最终的气孔率在理想的范围内。气孔的尺寸可以非常细小,即20~1000μm。已经发现形成的泡沫是稳定的并且有较高的泡沫高度。该泡沫可以容易地充入各种形状和尺寸的模型中。
可以在浆料中掺入通常用量的传统的添加剂,例如脱模剂、生物杀伤剂、和润滑剂,当然前提是它们对蛋白质的凝固没有不良的影响。也可以包括传统的无机粉末的分散剂,例如聚丙烯酸。但是,一般不需要加入单独的分散剂是本发明的方法的一个优点,因为用于凝胶形成的蛋白质物质也有分散剂的作用。不需要额外的分散剂的事实意味着需要从坯体中除去较少的有机物。蛋白质的作用使得不需要添加其他粘结剂和/或凝胶形成剂,根据本发明的一个优选的实施方案,没有做这样的添加。此外,为了最大地利用蛋白质物质的性质,不使用额外的分散剂,使得浆料中的有机物的量最小化。根据本发明,通过使用蛋白质物质作为分散剂和“粘结剂”,还可以避免由于粘结剂在粉末上的竞争吸收导致的失稳。
在形成实心坯体(无论是致密的还是多孔的)的本方法中,可以使用任何已知的从浆料或悬浮体成型的湿法技术。因此可以根据本发明通过任何注模法或浇注法成型制品,例如,通过热压注和凝胶化或浇注和凝胶化进行成型。也可能使用流延法成型技术和滴落成型(dropforming)技术。在流延法成型中,含有凝胶形成蛋白质的浆料可以浇注在支持带上,通过加热支持带和浆料层进行凝胶化。在滴落成型技术中,通过滴落含有蛋白质的浆料到充满溶剂(该溶剂不是浆料的溶剂,如加热的硅油)的罐中,形成基本为球形的料滴或料珠,在加热时使料滴凝胶化。优选的成型方法是热压注-凝胶法和浇注-凝胶法。后一种方法是特别优选的,可以用于成型接近净尺寸的成型制品,例如,与最终烧结的产品具有基本相同的形状的生坯。热压注-凝胶法特别适合于复杂形状的制品的生产,如喷嘴、耐磨部件、涡轮增压器转子和医学植入部件,浇注-凝胶法特别适合于多孔坯体的生产。
这里的术语“成型体”包括简单形状的产品,如带和珠,以及更复杂形状的产品。
干燥根据本方法生产的生坯以除去水分并处理以除去蛋白质和其他有机物。可以在单独的步骤或在最后的烧结的早期阶段进行这种蛋白质和有机物的去除。蛋白质的最后去除是非常快的,因为与粉料量相比,坯体内含有非常少的蛋白质。因此,在500~600℃空气中加热30分钟通常足以除去所有的蛋白质。为了形成实心的、致密的坯体,把生坯烧结。烧结温度、时间和其他条件在粉料技术中都是已知的。取决于粉料,烧结可以在空气中进行,如Al2O3,或者更常见的是在氮气等保护气氛中进行,如Si3N4,保护气氛也可以是还原性的。众所周知,烧结可以在常压或减压下进行。可以提到某些实例,Al2O3通常在空气中在约1600℃烧结1~2小时,Si3N4通常在1850℃氮气氛下烧结2小时,SiC可以在约2100℃氩气氛下烧结1小时,不锈钢在真空中在1200~1250℃烧结2小时。最终烧结的坯体可以按常规进行加工。
在下面的实施例中进一步说明本发明,都是不意味着限制本发明。除非有另外的说明,份和百分数对应于重量的份和重量百分数。
实施例1
在本实施例中制备致密的坯体。把由92%的Si3O4(S85H,来自Permascand AB,Sweden),6%的Y2O3和2%的Al2O3组成的、粒径为0.1~2μm的粉末混合物加入到牛血清清蛋白(A4503,来自Sigma,DE)的10%的水溶液中,直到粉末的干基含量达到32vol%。按含水相计算,加入0.1%的消泡剂(Kontraspum Konz.(一种脂肪醇)来自Zsc himmer&Schwarz,Germany)。使用球磨机用Si3N4球球磨该浆料使其均匀化并去团聚。然后把浆料在搅拌时脱气,并浇注到小模型中,然后用塑料薄膜覆盖所说的小模型。把该模型加热到65℃使蛋白质凝固,然后快速冷却到室温。得到的尺寸稳定的坯体可以容易地脱模。在室温下干燥后,在600℃空气中,在5分钟内烧掉坯体中的蛋白质。在1820℃,在氮气氛和大气压力下,把粉末的坯体烧结3小时成为致密的坯体。
实施例2
通过在仔细的螺旋桨搅拌过程中,添加56g的Al2O3粉末(Alcoa 152SG)到29.3g的含有10wt%的蛋清蛋白质的水溶液中,形成一种浆料。用移液管把得到的浆料滴入充满加热到80℃到硅油的罐中,在短时间后,料滴凝固成为固体。当把它们从油浴中取出时,它们能保持其刚度而不变形。为了降低原始浆料的粘度,加入少量的(约5g)水。所有的料滴在空气中以5℃/min的加热速度加热到600℃烧掉蛋白质。在1600℃空气中烧结60分钟。
实施例3
在本实施例中制备多孔的坯体。用0.3wt%的一种分散剂(Dispex A40,来自Allied Colloids,US的一种聚丙烯酸)通过球磨把平均粒径为0.4μm的Al2O3粉末先分散在水中。浆料的干基含量为37vol%,然后在进行5分钟的1000rpm的磁力搅拌的过程中,加入15wt%的,以含水相为基的,与实施例1所用的相同的牛血清清蛋白。在剧烈的搅拌过程中,空气混入浆料形成稳定的泡沫。然后把浆料浇注到铝箔制成的小模型中,并用铝箔覆盖该模型。把该模型放在60℃~70℃的干燥室中,使其形成凝胶。干燥凝胶化的结构,然后在1500℃烧结30分钟,加热速度为1℃/min到500℃,然后以10℃/min的加热速度加热到最高温度。
得到的烧结的,多孔的坯体的密度为0.57g/cm3,考虑到Al2O3的密度为3.90g/cm3,这相当于约15%的理论密度。
实施例4
在本实施例中,用蛋白质作发泡剂,生产了多孔的不锈钢坯体。相当于固体含量为33.8vol%的不锈钢粉末(316L,90%<22μm,OspreyMetals Ltd,USA),在搅拌的情况下加入到13.0wt%的牛血清清蛋白(A-4503,DIGMA Chemical Co.,USA)的水基溶液中。然后通过5分钟的高速搅拌使浆料发泡,使体积增大一倍。为了避免由于钢粉末的高密度(8.0g/cm3)导致的沉淀,必须把浆料稠化。通过在搅拌过程中加入稀盐酸把pH值从5.2降低到2.6,可以做到这一点。把发泡的浆料浇注到模型中,在70℃凝胶化。没有凝胶化坯体的沉淀或偏析的迹象。测得的气孔体积约为80%。
实施例5
在本实施例中,比较了牛血清清蛋白与明胶和琼脂酸的分散效果。
通过在螺旋桨搅拌过程中,在蒸馏水的烧杯中混合Si3N4粉末(UBE-E10-UBE Industries,Japan),制备三种固相含量为20vol%的Si3N4浆料。在两小时的搅拌后,用来自StressTech,Sweden的流变仪,在100s-1到剪切速率下测定粘度。对于浆料之一,在25℃(牛血清清蛋白的加工温度)测定粘度,其他两种在45℃测定粘度(对于明胶和琼脂酸的选定的加工温度)。明胶和琼脂酸在40℃以下形成凝胶。把牛血清清蛋白(A-4503,SIGMA Chemical Co.,USA)逐渐混入“25℃测定粘度”的浆料中,并在每次加入后测定粘度。把明胶(粉末,食品添加剂)和琼脂酸(A-0169,SIGMA Chemical Co.,USA)在室温下添加到其他两种溶液中。为了完全溶解添加剂,把这两种溶液加热到95℃,然后冷却到45℃。固相含量调整到20%,然后在45℃测定粘度。粘度的测定得到下列结果:
不加添加剂的浆料:≈150mPa·s。
加入明胶的浆料:在添加0.25wt%明胶时(基于含水相计算)的粘度为1350mPa·s。
加入琼脂酸的浆料:在添加0.25wt%时(基于含水相计算)的粘度为381mPa·s。
加入清蛋白的浆料:在添加0.25wt%时(基于含水相计算)的粘度为139mPa·s。更高的添加量时,粘度降低,在添加2wt%时粘度为49.8mPa·s。
Claims (11)
1、从粉末成型实心的、均匀的或多孔的成型体的方法,所说的粉末选自金属、金属间化合物、金属陶瓷和/或陶瓷的粉末的组中,其特征在于该方法包括含水浆料的制备,所说的浆料含有在室温下可溶于水、加热到不超过90℃的温度时能形成不可逆的凝胶的蛋白质物质,蛋白质物质的量以含水相为基至少为3wt%,通过注模法、流延法或滴落法并加热到至少相当于蛋白质的凝胶化温度使所说的浆料成型为要求形状的坯体。
2、根据权利要求1的形成实心的成型体的方法,其特征在于所说的坯体是均匀的、致密的坯体。
3、根据权利要求1的形成实心的成型体的方法,其特征在于所说的坯体是多孔的。
4、根据权利要求1-3的任一项的方法,其特征在于所说的蛋白质物质是球形的蛋白质。
5、根据权利要求4的方法,其特征在于所说的蛋白质物质是清蛋白。
6、根据权利要求1的方法,其特征在于浆料中粉料的干基含量为20~90vol%。
7、根据权利要求2的方法,其特征在于所说的粉末选自氮化硅、赛龙、氧化铝和碳化硅的粉末组中。
8、根据权利要求3或6的方法,其特征在于所说的粉末选自氧化铝、钛酸铝、碳化硅、氧化锆和堇青石的粉末组中。
9、根据权利要求1或3或6的方法,其特征在于所说的浆料不含有任何附加的粘结剂和/或凝胶形成剂。
10、根据权利要求1的方法,其特征在于通过浇注和凝胶化进行坯体的成型。
11、根据权利要求1的方法,其特征在于通过凝胶化成型的坯体进一步通过干燥和烧结进行处理,有机物的去除在烧结前的一个单独的步骤中或作为烧结的一部分进行。
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SE9503413A SE515393C2 (sv) | 1995-10-03 | 1995-10-03 | Sätt att forma kroppar av en uppslamning av pulver i vatten med ett irreversibelt gelbildande protein |
SE9503413-8 | 1995-10-03 |
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CN1151337A CN1151337A (zh) | 1997-06-11 |
CN1080612C true CN1080612C (zh) | 2002-03-13 |
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US (1) | US5972284A (zh) |
EP (1) | EP0767154B1 (zh) |
JP (1) | JP2928486B2 (zh) |
CN (1) | CN1080612C (zh) |
DE (1) | DE69605098T2 (zh) |
SE (1) | SE515393C2 (zh) |
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US6132674A (en) * | 1995-10-12 | 2000-10-17 | Bristol-Myers Squibb Company | Method of making an orthopaedic implant having a porous surface |
SE511834C2 (sv) * | 1998-01-13 | 1999-12-06 | Valtubes Sa | Heltäta produkter framställda genom enaxlig höghastighetspressning av metallpulver |
GB9821663D0 (en) | 1998-10-05 | 1998-11-25 | Abonetics Ltd | Foamed ceramics |
GB9825109D0 (en) | 1998-11-16 | 1999-01-13 | Dytech Corp Ltd | Porous ceramic matrices |
US6759004B1 (en) * | 1999-07-20 | 2004-07-06 | Southco, Inc. | Process for forming microporous metal parts |
WO2003067207A2 (en) * | 2002-02-08 | 2003-08-14 | Hormel Foods Corporation | Pressure indicator |
BE1014697A3 (fr) * | 2002-03-12 | 2004-03-02 | Metal Inject | Procede de mise en forme d'une piece en matiere metallique ou ceramique et piece ainsi obtenue. |
US6689184B1 (en) * | 2002-07-19 | 2004-02-10 | Latitude Manufacturing Technologies, Inc. | Iron-based powdered metal compositions |
US7517490B2 (en) * | 2002-10-16 | 2009-04-14 | Ngk Insulators, Ltd. | Method of manufacturing ceramic green body |
CA2534472A1 (en) * | 2003-09-03 | 2005-03-17 | Apex Advanced Technologies, Llc | Composition for powder metallurgy |
US7481968B2 (en) * | 2004-03-17 | 2009-01-27 | National Institute Of Advanced Industrial Science And Technology | Method for preparing a sintered porous body of metal or ceramic |
DE102004033153B4 (de) * | 2004-06-11 | 2007-03-29 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Glühkerze und Verfahren zu ihrer Herstellung |
US20070016057A1 (en) * | 2005-07-15 | 2007-01-18 | Anthony Dallago | Medical device having gripping layer |
US20080111282A1 (en) * | 2006-11-10 | 2008-05-15 | Baojun Xie | Process for Making Three Dimensional Objects From Dispersions of Polymer Colloidal Particles |
US20110200478A1 (en) * | 2010-02-14 | 2011-08-18 | Romain Louis Billiet | Inorganic structures with controlled open cell porosity and articles made therefrom |
CN104726062B (zh) | 2011-07-12 | 2017-09-29 | 3M创新有限公司 | 陶瓷成形磨粒和成形陶瓷前体粒子 |
US10138127B2 (en) * | 2011-12-21 | 2018-11-27 | Lg Innotek Co., Ltd. | Method of fabricating silicon carbide powder |
US20180009032A1 (en) * | 2016-07-08 | 2018-01-11 | General Electric Company | Metal objects and methods for making metal objects using disposable molds |
CN107116210B (zh) * | 2016-10-27 | 2018-11-27 | 北京科技大学 | 石墨片定向层状排列的铜基复合材料散热片及其制备方法 |
US20180362957A1 (en) * | 2017-06-14 | 2018-12-20 | R. J. Reynolds Tobacco Company | RuBisCO Protein-Based Films |
CN107352781B (zh) * | 2017-06-22 | 2020-01-10 | 上海极率科技有限公司 | 一种氮化硅多孔陶瓷材料快速固化成型的制备方法 |
RU2714452C1 (ru) * | 2019-09-28 | 2020-02-17 | ООО "Т-Сфера" | Способ получения порошков диоксида циркония со сфероидальной формой частиц |
CN111299596B (zh) * | 2019-12-04 | 2021-07-23 | 东北大学 | 蛋白质发泡制备生物医用可降解多孔锌的方法 |
DE102023206925A1 (de) | 2022-07-26 | 2024-02-01 | Alumina Systems Gmbh | Verfahren zur Fertigung eines metallischen Bauteils |
CN117285344B (zh) * | 2023-09-21 | 2024-04-16 | 株洲火炬安泰新材料有限公司 | 一种igzo靶材及其制备方法 |
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- 1996-09-27 CN CN96113091A patent/CN1080612C/zh not_active Expired - Fee Related
- 1996-09-30 EP EP96850165A patent/EP0767154B1/en not_active Expired - Lifetime
- 1996-09-30 DE DE69605098T patent/DE69605098T2/de not_active Expired - Fee Related
- 1996-10-01 JP JP8278557A patent/JP2928486B2/ja not_active Expired - Fee Related
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JPS6116012A (ja) * | 1984-06-30 | 1986-01-24 | Tdk Corp | 磁気記録媒体および磁気記録方法 |
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Also Published As
Publication number | Publication date |
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EP0767154B1 (en) | 1999-11-10 |
JPH09202673A (ja) | 1997-08-05 |
CN1151337A (zh) | 1997-06-11 |
SE515393C2 (sv) | 2001-07-23 |
DE69605098T2 (de) | 2000-04-13 |
SE9503413D0 (sv) | 1995-10-03 |
DE69605098D1 (de) | 1999-12-16 |
US5972284A (en) | 1999-10-26 |
SE9503413L (sv) | 1997-04-04 |
JP2928486B2 (ja) | 1999-08-03 |
EP0767154A1 (en) | 1997-04-09 |
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