CN1044802A - 将陶瓷复合体粘结于第二物体的方法与此法生产的制品 - Google Patents
将陶瓷复合体粘结于第二物体的方法与此法生产的制品 Download PDFInfo
- Publication number
- CN1044802A CN1044802A CN90100134A CN90100134A CN1044802A CN 1044802 A CN1044802 A CN 1044802A CN 90100134 A CN90100134 A CN 90100134A CN 90100134 A CN90100134 A CN 90100134A CN 1044802 A CN1044802 A CN 1044802A
- Authority
- CN
- China
- Prior art keywords
- parent metal
- metal
- norbide
- boron
- reactive
- 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.)
- Pending
Links
Classifications
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
-
- 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
- C04B35/653—Processes involving a melting step
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
-
- 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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
-
- 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
- C04B35/64—Burning or sintering processes
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
- C04B35/652—Directional oxidation or solidification, e.g. Lanxide process
-
- 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
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/001—Joining burned ceramic articles with other burned ceramic articles or other articles by heating directly with other burned ceramic articles
-
- 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
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
- C04B37/006—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of metals or metal salts
-
- 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
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/021—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles in a direct manner, e.g. direct copper bonding [DCB]
-
- 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
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
- C04B37/026—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of metals or metal salts
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
- C04B2237/121—Metallic interlayers based on aluminium
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
- C04B2237/122—Metallic interlayers based on refractory metals
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/12—Metallic interlayers
- C04B2237/123—Metallic interlayers based on iron group metals, e.g. steel
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/16—Silicon interlayers
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/36—Non-oxidic
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/40—Metallic
- C04B2237/401—Cermets
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/61—Joining two substrates of which at least one is porous by infiltrating the porous substrate with a liquid, such as a molten metal, causing bonding of the two substrates, e.g. joining two porous carbon substrates by infiltrating with molten silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Products (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明通常涉及生产复合体的新方法与此法生产的新型产物。更具体地说,本发明涉及一种通过熔融母体金属反应性地渗透含有碳化硼以及视具体情况而定存在的一种或多种惰性填料的床层或块料并且使残余或过量母体金属仍然粘结于所形成的自撑体从而生产包含一种或多种含硼化合物。例如硼化物或硼化物和碳化物的自撑体的方法。此后,可以利用残余或过量金属在所形成的复合体与另一物体(如金属或陶瓷体)之间形成键。
Description
本发明通常涉及生产复合体的新方法与此法生产的新型产物。更具体地说,本发明涉及一种通过熔融母体金属反应性地渗透含有碳化硼以及视具体情况而定存在的一种或多种惰性填料的床层或块料並且使残余或过量母体金属仍然粘结于所形成的自支撑体从而生产包含一种或多种含硼化合物。例如硼化物或硼化物和碳化物的自支撑体的方法。此后,可以利用残余或过量金属在所形成的复合体与另一物体(如金属或陶瓷体)之间形成键。
近年来,陶瓷代替金属在建筑上的应用已愈来愈引起人们的关注。原因是,与金属相比,陶瓷在某些性能方面如耐腐蚀性,硬度,耐磨性,弹性模数和耐火性能具有相对优越性。
但是,陶瓷用于上述目的的一个主要问题是制造所需陶瓷结构的可行及其造价。例如,利用热压法,反应烧结法和反应热压法制造面取得某些有限的进展,但仍然需要一种更有效和更经济的方法制造致密的含硼化物材料。
另外,陶瓷用于建筑上的第二个主要问题是陶瓷通常缺乏韧性(即损坏容限或抗断裂性)。在应用时,缺乏韧性往往容易在中度拉应力情况下引起陶瓷突然的灾难性断裂。这种缺乏韧性在整块陶瓷硼化物中是特别常见的。
解决上述问题的一个方法是使用与金属化合的陶瓷,例如金属陶瓷或金属基复合材料。这种公知方法的目的是要获得陶瓷最佳性能(例如硬度和/或刚性)和金属最佳性能(例如延展性)的综合平衡。尽管在生产硼化物金属陶瓷领域取得了一些一般性进展,但仍需要更有效更经济的含硼化物材料的制备方法。
Danny R.White,Michael K.Aghajanian和T.Dennis Claar在1987年7月15日申请的共同未决美国专利申请073,533(题为“自支撑体的制备方法及其所制备的产品”)叙述了与生产含硼化物材料有关的许多上述问题。
简要归纳申请书′533的内容可知,自一支撑陶瓷体是在碳化硼存在下,利用母体金属渗透作用和反应方法(即,反应性渗透作用)制备的。特别地,碳化硼床层或碳化硼体被熔融的母体金属渗透和反应,而床层可全部由碳化硼组成,因此,所得自一支撑体包括一种或多种母体金属含硼化合物,该化合物包括母体金属硼化物或母体金属碳化硼或两者,一般还包括母体金属碳化物。该申请还披露:待渗透的碳化硼体还可含有一种或多种与碳化硼混合的惰性填料。因此,通过结合惰性填料,所得产物将是一种具有基体的复合体,该基体是利用母体金属的反应性渗透作用制备的。所说基体包括至少一种含硼化合物,还可以包括母体金属碳化物,该基体嵌入惰性填料。还应注意,在上述方案中不论哪种情况(即,有填料或无填料),最终复合体产物均可以包括残余金属,如原始母体金属的至少一种金属成分。
从广义上讲,在申请书′533公开的方法中,含碳化硼体放置在与熔融的金属体或金属合金体相邻或接触的位置上,熔融的金属体或金属合金在一个特定的温域内、在基本惰性环境中熔化。熔融的金属渗透碳化硼体并与碳化硼反应生成至少一种反应产物。碳化硼可被熔融母体金属至少部分还原,从而生成母体金属含硼化合物(例如,在该工艺温度条件下,生成母体金属硼化物和/或硼化合物)。典型情况下,还生成母体金属碳化物,而在特定情况下,生成母体金属碳硼化物。至少部分反应产物与金属接触,并利用毛细作用使熔融的金属吸到或迁移到未反应的碳化硼。迁移的金属形成另外的母体金属,硼化物,碳化物和/或碳硼化物并且陶瓷体维续形成或扩展直到或是母体金属或碳化硼已被消耗掉或是反应温度变化到反应温域以外的温度。所得结构物包括一种或多种母体金属硼化物,母体金属硼化合物,母体金属碳化物,金属(如申请书′533所述,包括合金和金属互化物)或空隙或上述任意组合。而且,这几相在整个陶瓷体中可以或不以一维或多维相互连接。可以通过改变一种或多种条件,例如改变碳化硼体的初密度,碳化硼和母体金属的相对含量,母体金属的合金用填料稀释碳化硼,温度和时间,控制含硼化合物(即硼化物和硼化合物)、含碳化合物和金属相的最终体积分数以及互连度。碳化硼转化为母体金属硼化物、母体金属硼化合物和母体金属碳化物的转化率较好是至少约50%,最好是至少约90%。
在申请书′533中采用的典型环境或气氛是在该工艺条件下相对惰性或非反应性的环境或气氛。该申请特别指出,例如氩气或真空是适宜的工艺气氛。而且,据披露,如果使用锆作为母体金属,则所得复合体包括二硼化锆,碳化锆和残余的金属锆。该申请还披露,如果在该方法中使用铝母体金属,则所得产物是碳硼化铝如Al3B48C2,AlB12C2和/或AlB24C4,并残存铝母体金属和其他未反应、未氧化母体的金属成分。在该工艺条件下其他适用的母体金属还披露有硅,钛,铪,镧,铁,钙,钒,铌,镁和铍。
共同未决的美国专利申请137,044(以下称作“申请书′044”)是申请书′533的继续部分申请,〔申请人:Terry Dennis Claar,Steven Michael Mason,Kevin Peter Pochopien和Danny Ray White,申请日:1987年12月23日,题为“自一支撑体的制备方法及其所制备的产品”。〕申请书′044披露,在某些情况下,将碳给予体(即,含碳化合物)加到将要被熔融母体金属渗透的碳化硼床层或碳化硼体中是理想的。具体讲,据该申请书公开,碳给予体能够与母体金属反应生成母体金属碳化物相,这种相能改进所得复合体的机械性能(与没有使用碳给予体所制备的复合体比较)。因此,据透露可改变或控制反应物浓度和工艺条件以获得含有不同体积百分数的陶瓷化合物、金属和/或孔隙的陶瓷体。例如,通过向碳化硼体加碳给予体(如石墨粉或碳黑),可以调节母体金属硼化物/母体金属碳化物的比率。特别是,如果使用锆作为母体金属,则会降低ZrB2/ZrC的比率(即,由于向碳化硼体加入碳给予体可产生更多的ZrC)。
申请书′044还公开了石墨模具的使用,该石墨模具有适当数量的、具有特定尺寸、形状和位置的通气孔,这些通气孔起着排气的作用,能在母体金属反应性渗透前沿渗透预型坯时除去例如预型坯或填料中收集到的任何气体。
在另一个相关申请,共同未决美国专利申请137,382(以下称作“申请书′382”)中,公开了其他改进方案。该申请是Terry Dennis Claar和Gerhard Hans Schiroky于1987年12月23日申请的,题为“利用渗碳法改性陶瓷复合体的方法及其制品”。具体讲,申请书′382公开的是:按申请书′533介绍的方法制备的陶瓷复合体暴露于气体渗碳物中能得到改性。例如,通过将复合体包埋在石墨床中并使至少部分石墨床在控制气氛炉中与潮气或氧气反应能制得上述气物渗碳物。但是炉内气氛一般应主要由非反应性气体如氩气构成。还不清楚是否氩气中的杂质提供了必要需的O2以形成渗碳物,还是氩气仅起着含有杂质的媒介作用(这些杂质是在石墨床或复合体中某些成份挥发而产生的)。此外,气体渗碳物可以在加热复合体过程中直接引入控制气氛炉内。
一旦气体渗碳物被引入控制气氛炉内,应按如此方式设计组件以使渗碳物能与至少一部分埋在散填石墨粉中的复合体表面接触,据认为,渗碳物中的碳或来自石墨床层中的碳将溶解在相互连接的碳化锆相中,然后溶解的碳迁移遍布基本上所有的复合体(如果需要可以利用空位扩散法)。而且,申请书′382还披露:通过控制时间、复合体暴露在渗碳物的程度和/或发生渗碳作用时的温度,可在复合体表面形成渗碳区或渗碳层。利用这种方法可形成一层包覆有高金属含量和高断裂硬度的复合材料的坚硬、耐磨表面。
因此,如果生成的复合体含有约5~30%(体积)的残余母体金属相,则能利用后渗碳处理改性这种复合体,使所形成的复合体含有约0~2%(物积),典型是约0.5~2%(体积)的母体金属。
上述每篇共同所有的美国专利申请的内容在此作为参考文献引用。
基于上述内容完成了本发明,本发明克服了先有技术的缺陷,本发明提供一种用于使金属层粘结于借助反应性渗透技术而形成的复合体(本文有时称其为“反应性渗透体”)之上的方法。该金属层还会与诸如陶瓷体或金属体之类的第二物体粘结。第二种物体可以是借助类似的或完全不同的技术制成的另一种陶瓷体。此外,第二种物体可以是其化学组成与粘结于反应性渗透体的金属相比基本上相同或基本上不同的金属。
在第一优选实施方案中,为了有效地形成粘结力,需要提供数量超出实现基本上完全反应性渗透待渗透碳化硼块料所需母体金属数量的熔融母体金属。因此当存在这一过量熔融母体金属时,所得到的便是一个复杂的复合体。其中通过反应性渗透形成的复合体直接粘结于过量母体金属上。此外,反应性渗透体可以作为外表面或内表面形成于金属的基底之上,金属相对于反应性渗透体的厚度可以变化。因此可以形成厚壁或薄壁金属和/或反应性渗透体。
在第二种使金属与反应性渗透体粘结的优选方法中,首先按照例如申请′533所述内容制备一复合体,该反应性渗透体对于与用作反应性渗透过程母体金属的金属相比相似、以及在某些情况下基本上不同的金属具有特殊的亲和力,由于这种金属与所形成的复合体之间的亲和力,可以将金属熔化并且使其与反应性渗透体的至少一个表面相接触,从而使金属与反应性渗透体直接粘合。在此第二种优选实施方案中,还可以制成宏观复合体,其中金属粘结在另一陶瓷体或另一金属体上。
因此,本发明提供一种制备宏观复合体的方法,(例如,将组成相似或不同的两个物质粘结在一起)。
按照本发明,通过使熔融母体金属与碳化硼发生反应性渗透形成包括母体金属与碳化硼的反应产物以及一种或多种母体金属组分的含多晶陶瓷物体来制备自撑体。碳化硼,在过程条件下一般为固体,以细碎颗粒或粉末状为佳。该方法选用的环境或气氛在过程条件下相对而言呈惰性或非反应性。举例来说,氩气或真空气氛适用于本发明。所得到的产物包含一种或多种(a)母体金属硼化物,(b)硼化合物,(c)通常为母体金属碳化物、以及(d)金属、产物中的组分与组成在很大程度上取决于所选用的母体金属及其组成与反应条件。此外,所生产的自撑体可以具备孔隙或空隙。
在本发明的优选实施方案中,使母体金属与含有碳化硼的块料或床层彼此接近以便使反应性渗透沿着指向床层的方向定向发生。可以经过预成型处理的床层包括诸如补强填料之类的填充物,在过程条件下它们基本上呈惰性。在基本上不进行搅动或移动其位置的条件下反应产物可以生长进入床层。因此,没有必要借助会对床层配置带来干扰与破坏的外力并且没有必要采用令人棘手或成本昂贵的高温高压条件和设备生产反应产物。母体金属反应性渗透以颗粒或粉末状为佳的碳化硼可以形成通常含有母体金属硼化物和母体金属硼化合物的复合体。采用铝作为母体金属,产物可以含有碳化铝硼(例如:Al2B48C2、AlB12C2,AlB24C4),并且还可以包括金属例如铝,以及其它未反应或未氧化的母体金属组分。如果选用锆为母体金属,所得到的复合体包括硼化锆和碳化锆。此外,复合体中还可以存在锆金属。作为可选择的另一方式,若选用钛/锆合金作为母体金属,所得到的复合体含有硼化钛,碳化钛,硼化锆和碳化锆。另外,复合体中还可以存在一些作为残余或未反应母体金属的钛/锆合金。
虽然下文具体描述其中母体金属包括锆或铝在内的特定优选实施方案,但是这只是为了便于描述。还可以选用诸如硅、钛、铪、镧、铁、钙、钒、铌、镁、铬、铍与钛/锆合金之类的其它母体金属,下文给出了几种这类母体金属的实例。
应该理解,操作温度或优选温度并非就是高于母体金属的熔点並且低于反应产物熔点的整个温度范围。该温度范围在很大程度上取决于诸如所得到的复合体中母体金属的组成与所需相之类因素。熔融金属与碳化硼接触,形成反应产物母体金属硼化物(例如二硼化锆)和母体金属碳化物(例如碳化锆)。一旦继续暴露于碳化硼中,残余的熔融金属逐渐沿着含碳化硼块料的方向通过反应产物以便在熔融金属与碳化硼的交界面连续形成反应产物。该方法制备的产物含有母体金属与碳化硼的反应产物或者含有陶瓷-金属复合体以便还包括一种或多种未反应的或未氧化的母体金属组分。大量碳化硼发生反应从而形成反应产物,其参加反应的数量以至少约50%为佳,以至少约为90%为最佳。作为该方法反应产物的陶瓷晶体可以是或不是内连的,但是以三维内连为佳,产物中的金属相和任何空隙通常至少是部分内连的。虽然任何空隙都易于由部分或几乎完全耗尽母体金属相而产生以便形成附加的反应产物(正如存在化学计量反应物或过量碳化硼的情况下),但是空隙的体积百分率取决诸如温度,时间,母体金属种类与碳化硼块料的空隙之类因素。
业已发现,采用锆、钛和铪作为母体金属按照本发明制备的产品为以片状结构为特征的母体金属硼化物。这些片晶典型地为未排列好的或随机取向的。由破裂挠度和/或拔拉机理可以看出这一片状结构与金属相至少在很大程度上导致复合体具备非常高(约为12×106Pa·m1/2或更高)的断裂韧性。
本发明的另一方面提供了一种包括复合体在内的自撑体其中包含一种嵌入基本上惰性的填料之中的反应产物以及视具体情况存在的金属组分的基质。该基基质通过母体金属反应性渗透与碳化硼紧密混合的填料床或块料而形成,填料可以任意大小或形状存在,只要反应产物产生的方向指向並且可能淹没至少一部分填料而不会将其扰动或移动,那么母体金属便可以任何方式取向。填料可以由诸如陶瓷和/或金属纤维,须晶,颗粒,粉末,棒材,金属丝,金属丝布,耐火布,片材,片晶,网状泡沫结构,实心或中空球体之类任何适宜的材料所构成。特别适用的填料为氧化铝,不过,依据原料及所需的目的特性还可以采用其它氧化物及陶瓷填料。填料可以被松散地放置或粘结在一起,其间具有空隙之类的空间从而使填料可被熔融母体金属渗透。此外,填料可以是均相或非均相物质,必要的话,可以用任何适宜的,不会干扰本发明的反应并且不会在复合体成品内残留任何不需要的副产物的粘合剂(例如Aricil PH105,FMC公司出品)将填料粘结在一起。可以涂敷在加工期间易于与碳化硼或熔融金属过度反应的填料以便使填料对加工环境呈惰性。举例来说,如果与作为母体金属的铝组合使用的话,作为填料的碳纤维便易于与熔融铝反应,不过,如果先用例如氧化铝涂敷纤维的话,该反应便可以避免。
采用适宜的耐火容器盛放母体金属和混合有碳化硼的填料床层,经过适当地取向以便使母体金属反应性渗透填料床并且形成适宜的复合体,将该容器放入炉中,将此组装体加热至高于母体金属熔点的温度。此时,熔融母体金属通过毛细作用渗透可渗透填料並且与碳化硼反应,从而生成所需陶瓷或陶瓷金属复合体。此外,为了有助于减少成品机加工与精整操作,可以用阻档材料包围预型体。在与由诸如碳化硼,氮化硼,硼和碳之类材料构成的预型体组合应用之时,对于诸如锆、钛或铪之类的母体金属来说,特别适用的阻挡层为石墨模具。此外,通过在上述石墨模具中,打通数目适当,具有特定尺寸与形状的透孔可以减少通常出现在按照本发明制备的复合体中的空隙。典型地,在模具的底部或朝向发生反应性渗透的部分设有许多孔。这些孔的作用是排放例如在母体金属反应性渗透前沿渗透预型体之时被截留在预型体中的氩气。
依据填料的特性,可以借助诸多制备陶瓷体的传统方法中的任何一种(如单轴压制法,等静压制,粉浆浇铸、沉积浇铸,带式浇铸,注塑,纤维丝绕制等)制备用于本发明的预型体。通过采用不会干扰本发明方法或不会使成品具有不需要的副产物的各种有机或无机粘合材料或者通过轻度烧结可以在进行反应性渗透之前使填料颗粒、须晶,纤维等出现初步粘结。被制成的预型体具备充分的形状完整性与生坯强度並且可以被熔融金属渗透,其孔隙率以大约5-90%(体积)为佳,以大约25~75%(体积)为更佳。在使用铝作为母体金属时,适宜的填料包括,举例来说,碳化硅,二硼化钛,氧化铝和十二硼化铝(被包含于其它物质之中),作为颗粒、其典型的筛目大小约14~1000,不过,可以选用任意的填料混合物与筛目大小。随后使熔融母体金属与预型体的一个或多个表面接触足够的时间从而使基质完全渗透预型体的表面边界。其结果是产生其形状确切地代表成品所需形状的陶瓷金属复合体。这样便最大限度地减少或完全消除了代价昂贵的成品机加工或研磨操作。
业已发现,存在于填料中的碳化硼有助于母体金属渗透填料。业已证实少量硼源的存在可以产生功效,但是其最低用量要取决于诸如碳化硼的种类与粒径,母体金属的种类,填料的种类和过程条件之类的许多因素。因此,填料中碳化硼的浓度可以在很大的范围内变化,但是,其浓度越低,基质中金属的体积百分比就越高。当选用数量很少的碳化硼时,例如其用量以碳化硼与填料的总重为基准计为1~3%(重)时,所得到的基质为内连金属和数量有限的母体金属硼化物以及分散于金属之中的母体金属碳化物。在无碳化硼存在时,便不会发生填料的反应性渗透,在未采取诸如施加外压从而迫使金属进入填料之类特定步骤时,渗透也不会发生。
由于适用于本发明方法的填料中碳化硼浓度的取值范围较宽,所以能够通过改变碳化硼的浓度和/或床层的组成来控制或调节成品的特性。如果相对于母体金属的数量只存在少量碳化硼从而使块料中含有低密度碳化硼的话,那么,由于基质中主要含有金属,因而使得复合体或基质的特性、最典型的为可塑性与韧性受到母体金属特性的限制。这种产物适用于低温或中温条件下。当采用大量碳化硼时,例如当含有碳化硼颗粒的混合物紧密充填在填料周围或占据填料颗粒间大量空间时,所产生的基质的特性将取决于母体金属硼化物和任何母体金属碳化物,此时基质会更加坚硬或更不易于延展或者韧性更低。如果严密控制化学计量以便使母体金属基本上完全转化,那么,所形成的产物将含有很少或不含有金属,这样便使该产物适用于高温条件下。此外,碳化硼易于与存在于产物中的残余或未氧化金属如铝反应,由于硼化物反应产物比碳化硼稳定,所以母体金属基本上完全转化在某些高温应用场合尤为重要。
必要时,可以使一种供碳材料(例如单质碳)与含有碳化硼与视具体情况存在的填料的碳化硼床层或预型体混合。这些过量碳典型地约为床层总量的5~10%(重),它们与母体金属反应从而保证了金属基本上反应完全。金属与碳之间发生的反应在很大程度上取决于碳的用量,种类(例如碳黑或石墨)以及结晶度。在这些极限特性中进行甄选对于满足这些产品的不同的潜在应用需求是十分必要的。例如,通过将约5~75,以约为5~50为佳,%(重)炭黑添加至B4C预型体中並且用锆金属反应性渗透该预型体,可以降低ZrB2/ZrC之比(即:形成更多的ZrC)。
此外,还可以使一种供硼材料(例如单质或粉末硼)与碳化硼床或预型体相混合。具体地说,业已发现,选用铝作为母体金属有助于进行反应性渗透。与单纯的碳化硼床层相比,这种混合物可以减少床的费用,导致含有诸如碳化铝硼之类(具备与硼化铝相似特性)碳化硼的产物形成并且防止在水分存在下不稳定,因而使产物的结构特性变坏的碳化铝形成。然而,供硼材料的存在还可以起到调节母体金属硼化物/母体金属碳化物比值的作用。举例来说,当选用锆作为母体金属时,ZrB2/ZrC之比便会增大(即,形成更多的ZrB2)。
通过控制渗透条件可以使复合体的特性出现附加的变化。可被控制的变量包括碳化硼材料的性质与粒径,渗透温度与渗透时间。举例来说,低温下在最少暴露时间内对大颗粒碳化硼进行反应性渗透会导致碳化硼部分地转化为母体金属硼和母体金属碳混合物。这样,以微观结构残留下来的未反应的碳化硼材料在某些应用场合会赋于成品以必要的特性。在高温下长时间地(或许甚至在渗透完成之后保温一段时间)渗透碳化硼颗粒有助于使得母体金属基本上完全转化为母体金属硼化物和碳化合物。碳化硼转化为母体金属硼化物,母体金属硼化合物和母体金属碳化物的转化率以至少约为50%为佳,以至少约为90%为最佳。高温渗透(或进行后续高温处理)同样会通过烧结法使某些复合体组分致密化。此外,如上所述,如果减少适用母体金属的数量并且使其低于形成硼和碳化合物並且充填所形成的空隙所必要的数量,同样会形成适用的多孔体。在该复合体中,取决于上述多种因素或条件,孔隙率的取值范围约为1~25%(体积),有时会更高。
在每一个上述实施方案中,用于反应性渗透的母体金属的数量可以多于使所有碳化硼和/或任何添加组分基本上反应完全所需数量。在第一个优选实施方案中,通过利用数量超出实现基本上完全反应性渗透待渗透碳化硼块料所需数量的熔融母体金属可以产生有效的粘结。因此,在存在过量熔融母体金属时,便会形成复杂的复合体,通过反应性渗透而形成的该复合体会直接粘结在过量母体金属上。此外,反应性渗透体以外表面或内表面的形式处于金属的基底上,金属相对于反应性渗透体的厚度可以改变。因此,可以制备厚壁或薄壁金属和/或反应性渗透体。
在用于将金属粘结于反应性渗透体的第二个优选方法中,首先按照例如申请533的内容制备复合体。这种反应性渗透体对于与反应性渗透过程期间被用作母体金属的金属相似以及在某些情况下基本上不同的金属具有特殊的亲和力。由于这一亲和力,金属可以熔化並且与反应性渗透体至少一个表面相接触,从而使金属与反应性渗透体直接粘结。在该第二个优选实施方案中,还可以制备一种宏观复合体,其中金属粘结于另一个陶瓷体或另一个金属体。
因此,本发明提供一种制备宏观复合体的方法(例如,粘结两个组成相同或不同的物体)。
Claims (3)
1、一种生产自撑体的方法,该方法包括通过下述步骤制备第一复合体。
选择母体金属;
在基本上呈惰性的气氛中将所述的母体金属加热至高于其熔点的温度以便使熔融的母体金属渗透包含碳化硼的块料,从而使熔融的母体金属与所述的碳化硼反应以便形成至少一种含硼化合物;
使上述渗透反应继续进行足够的时间以便制备包含至少一种含有母体金属硼的化合物的自撑体;
在所述自撑体的至少一个表面上提供过量金属以便使所述自撑体粘结第二个物体。
2、一种制备自撑宏观复合体的方法,该方法包括:
用母体金属反应性渗透包含碳化硼的块料,所述的反应性渗透发生在基本上呈惰性的气氛中,所述的碳化硼与所述的母体金属反应从而在反应性渗透体中形成至少一种含硼化合物,以及提供过量的母体金属以便使母体金属一旦被冷却便保留下来並且粘结于反应性渗透体之上,从而形成宏观复合体。
3、一种制备自撑宏观复合体的方法,该方法包括:
选择母体金属;
在基本上呈惰性的气氛中将所述的母物金属加热至高于其熔点的温度以便使熔融的母体金属渗透包含碳化硼的块料,从而使熔融的母体金属与所述的碳化硼反应以便形成至少一种含硼化合物;
使上述渗透反应继续进行足够的时间以便制备包含至少一种含有母体金属硼的化合物的自撑体,以及随后使至少一部分所述制得的自撑体与另一种金属相互接触並粘结,从而形成一种宏观复合体。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US29683789A | 1989-01-13 | 1989-01-13 | |
US296,837 | 1989-01-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1044802A true CN1044802A (zh) | 1990-08-22 |
Family
ID=23143790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN90100134A Pending CN1044802A (zh) | 1989-01-13 | 1990-01-11 | 将陶瓷复合体粘结于第二物体的方法与此法生产的制品 |
Country Status (18)
Country | Link |
---|---|
EP (1) | EP0378501B1 (zh) |
JP (1) | JP2911937B2 (zh) |
KR (1) | KR0134959B1 (zh) |
CN (1) | CN1044802A (zh) |
AT (1) | ATE96414T1 (zh) |
AU (1) | AU628907B2 (zh) |
BR (1) | BR9000087A (zh) |
CA (1) | CA2007603A1 (zh) |
DE (1) | DE69004104T2 (zh) |
FI (1) | FI900199A0 (zh) |
IE (1) | IE900112L (zh) |
IL (1) | IL92395A0 (zh) |
MX (1) | MX173565B (zh) |
NO (1) | NO900144L (zh) |
NZ (1) | NZ232044A (zh) |
PH (1) | PH26573A (zh) |
PT (1) | PT92855A (zh) |
ZA (1) | ZA90221B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006086184A1 (en) | 2005-02-09 | 2006-08-17 | Honeywell International Inc. | Method of making 1,1,1-trifluoroethane |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4885131A (en) * | 1989-01-13 | 1989-12-05 | Lanxide Technology Company, Lp | Process for preparing self-supporting bodies and products produced thereby |
DE69107079T2 (de) * | 1990-07-12 | 1995-06-01 | Lanxide Technology Co Ltd | Verbindungsmethoden für keramische verbundkörper. |
US5098870A (en) * | 1990-07-12 | 1992-03-24 | Lanxide Technology Company, Lp | Process for preparing self-supporting bodies having controlled porosity and graded properties and products produced thereby |
JP3987201B2 (ja) | 1998-05-01 | 2007-10-03 | 日本碍子株式会社 | 接合体の製造方法 |
CN102285296A (zh) * | 2011-07-08 | 2011-12-21 | 波特·史蒂芬·戴尔 | 一种陶瓷香水工艺品及其制造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1229505B (de) * | 1964-01-23 | 1966-12-01 | Kempten Elektroschmelz Gmbh | Verfahren zur Herstellung von Erdalkalimetallboriden und -carbiden |
US4702770A (en) * | 1985-07-26 | 1987-10-27 | Washington Research Foundation | Multipurpose boron carbide-aluminum composite and its manufacture via the control of the microstructure |
US4718941A (en) * | 1986-06-17 | 1988-01-12 | The Regents Of The University Of California | Infiltration processing of boron carbide-, boron-, and boride-reactive metal cermets |
DD279466A5 (de) * | 1986-09-16 | 1990-06-06 | ��������@��������@����������@���k�� | Verfahren zur herstellung eines selbsttragenden keramischen verbundkoerpers |
US4824008A (en) * | 1986-09-16 | 1989-04-25 | Lanxide Technology Company, Lp | Surface bonding of ceramic bodies |
US4900699A (en) * | 1986-09-16 | 1990-02-13 | Lanxide Technology Company, Lp | Reservoir feed method of making ceramic composite structures and structures made thereby |
US4885131A (en) * | 1989-01-13 | 1989-12-05 | Lanxide Technology Company, Lp | Process for preparing self-supporting bodies and products produced thereby |
-
1989
- 1989-11-22 IL IL92395A patent/IL92395A0/xx not_active IP Right Cessation
-
1990
- 1990-01-04 PH PH39835A patent/PH26573A/en unknown
- 1990-01-08 AU AU47796/90A patent/AU628907B2/en not_active Ceased
- 1990-01-08 NZ NZ232044A patent/NZ232044A/en unknown
- 1990-01-10 BR BR909000087A patent/BR9000087A/pt not_active Application Discontinuation
- 1990-01-11 DE DE90630011T patent/DE69004104T2/de not_active Expired - Fee Related
- 1990-01-11 CN CN90100134A patent/CN1044802A/zh active Pending
- 1990-01-11 AT AT90630011T patent/ATE96414T1/de not_active IP Right Cessation
- 1990-01-11 EP EP90630011A patent/EP0378501B1/en not_active Expired - Lifetime
- 1990-01-11 CA CA002007603A patent/CA2007603A1/en not_active Abandoned
- 1990-01-11 IE IE900112A patent/IE900112L/xx unknown
- 1990-01-11 NO NO90900144A patent/NO900144L/no unknown
- 1990-01-12 FI FI900199A patent/FI900199A0/fi not_active IP Right Cessation
- 1990-01-12 ZA ZA90221A patent/ZA90221B/xx unknown
- 1990-01-12 MX MX019123A patent/MX173565B/es unknown
- 1990-01-12 PT PT92855A patent/PT92855A/pt not_active Application Discontinuation
- 1990-01-12 JP JP2003707A patent/JP2911937B2/ja not_active Expired - Fee Related
- 1990-01-12 KR KR1019900000335A patent/KR0134959B1/ko not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006086184A1 (en) | 2005-02-09 | 2006-08-17 | Honeywell International Inc. | Method of making 1,1,1-trifluoroethane |
Also Published As
Publication number | Publication date |
---|---|
PH26573A (en) | 1992-08-19 |
JPH02275775A (ja) | 1990-11-09 |
JP2911937B2 (ja) | 1999-06-28 |
IE900112L (en) | 1990-07-13 |
ZA90221B (en) | 1991-09-25 |
MX173565B (es) | 1994-03-16 |
AU628907B2 (en) | 1992-09-24 |
PT92855A (pt) | 1990-07-31 |
DE69004104D1 (de) | 1993-12-02 |
CA2007603A1 (en) | 1990-07-13 |
BR9000087A (pt) | 1990-10-16 |
EP0378501A1 (en) | 1990-07-18 |
DE69004104T2 (de) | 1994-03-17 |
IL92395A0 (en) | 1990-07-26 |
KR0134959B1 (ko) | 1998-04-18 |
NO900144L (no) | 1990-07-16 |
FI900199A0 (fi) | 1990-01-12 |
NZ232044A (en) | 1992-02-25 |
EP0378501B1 (en) | 1993-10-27 |
KR900011683A (ko) | 1990-08-01 |
NO900144D0 (no) | 1990-01-11 |
AU4779690A (en) | 1990-07-19 |
ATE96414T1 (de) | 1993-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1022033C (zh) | 自支承陶瓷体的生产方法 | |
CN1022102C (zh) | 自支承陶瓷体的制备方法 | |
AU629281B2 (en) | A process for preparing self-supporting bodies and products produced thereby | |
US5019539A (en) | Process for preparing self-supporting bodies having controlled porosity and graded properties and products produced thereby | |
US5011063A (en) | Method of bonding a ceramic composite body to a second body and articles produced thereby | |
US5017334A (en) | Process for preparing self-supporting bodies and products produced thereby | |
JP2911939B2 (ja) | 自己支持性セラミック複合体の製造方法 | |
PH26405A (en) | Process for preparing self-supporting bodies and products made thereby | |
US5010044A (en) | Process for preparing self-supporting bodies and products produced thereby | |
US4978644A (en) | Process for preparing self-supporting bodies and products made thereby | |
CN1044802A (zh) | 将陶瓷复合体粘结于第二物体的方法与此法生产的制品 | |
US5614308A (en) | Macrocomposite bodies | |
CN1035104A (zh) | 生产陶瓷复合材料体和改进其性能的方法 | |
CN1044803A (zh) | 陶瓷复合体的制备方法 | |
US5187128A (en) | Process for preparing self-supporting bodies |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
AD01 | Patent right deemed abandoned | ||
C20 | Patent right or utility model deemed to be abandoned or is abandoned |