• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A method of producing a composite comprising a self-supporting polycrystalline material obtained by oxidation reaction of a molten parent metal (2) with a vapor-phase oxidant comprising infiltrating a filler (3) exhibiting inter-particle pore volume with a parent me­tal (2) under conditions which control the respective rates of said metal infiltration and said oxidation reaction.
    公开号:SU1830057A3
    申请号:SU874203283
    申请日:1987-09-14
    公开日:1993-07-23
    发明作者:T Klaar Dennis；Dzh Gesing Adam；D Post Stiven；Dzh Sobchik Merek；S Ragkhavan Narasima；K Kreber Dejv；S Negelberg Alan
    申请人:Lanxide Technology Co Ltd；
    IPC主号:
    专利说明:

    UNION OF SOVIET
    SOCIALIST
    REPUBLIC
    S and „„ 1830057 AZ (51) 5 С 04 В 35/65 ________________________
    STATE PATENT
    DEPARTMENT OF THE USSR (GOSPATENT USSR)
    DESCRIPTION OF THE INVENTION
    TO THE PATENT
    mgeish Bull. No. 27 (31) 907 927 (22) 16.09.86 (33) US (71) Lanksid Technology Company, LP. (US) (72) T. Dennis Claar (US), Adam J. Gesing, Stephen D. Post, Merek J. Sobchik, Narasima S. Raghawan, Dave K. Kreber (SA) and Alan S. Negelberg (US) ( 56) EP Ns 0169067, cl. C 04 V 35/65, published. 01/22/86.
    EP Ns 0193292, CL C 04 V 35/65, published. 09/03/86.
    (54) METHOD FOR PRODUCING A POLYCRYSTALLINE COMPOSITE MATERIAL (57) Purpose: the invention relates to the production of ceramic and composite structures and methods for their preparation. The inventive method for producing a composite consisting of a hardened polycrystalline material consists in oxidizing a parent metal melt with a vapor-phase oxidizing agent, said method comprising infiltrating a parent metal into a filler having internal voids, the method being implemented under conditions providing controlled regulation of the rates of infiltration mentioned metal and oxidation. 10 s.p. f-ly, 5 ill. 3 tab.
    The invention in a broad aspect relates to new complex structural materials and new methods for their preparation, and specifically, the invention relates to composite ceramic and cermet structures containing a filler infiltrated with a polycrystalline matrix, as well as methods for producing such structures - materials by implementing a metal oxidation reaction - the basis in the volume of porous voids of the permeable mass of the filler material.
    Proposed in the framework of this invention, a method of manufacturing ceramic products eliminates a number of typical disadvantages of technological problems characteristic of known methods.
    A brief description of illustrative materials.
    FIG. 1 is a cross-sectional diagram of a reaction working vessel in which the claimed method can be carried out.
    FIG. 2 is a cross section AA of the tank of FIG. 1. which shows the filler partially impregnated with the melt (the image is enlarged so that it is possible to clearly illustrate the various phase states of the filler).
    FIG. 3 is a micrograph of a polycrystalline material obtained by the method of the present invention and having a matrix of a pronounced ceramic type.
    FIG. 4 is a microphotograph of a composite structure of the type shown in FIG. 3, immediately after the start of the initial metal infiltration, when the channels between the particles of the filler particles are partially filled with the porous chemical oxidation product.
    FIG. 5 is a microphotograph of a polycrystalline ceramic material obtained by the method of the present invention and having a metal matrix.
    This invention essentially provides for the production of a self-hardening polycrystalline ceramic product by controlling the rate of impregnation of the filler with the molten parent metal and the oxidative reaction of the molten metal with the oxidizer in the vapor phase. The formation of a chemical oxidation product occurs on the surface of individual filler particles while maintaining the passage channels for the vapor-phase oxidizer, and at any given time, oxidation reactions occur in a sufficiently large volume of gaps between the filler particles. The molten source metal, wetting the filler particles, leaks relatively quickly (compared with the course of oxidation reactions). The total pore volume of the permeable mass of the filler is sufficient to accept the infiltrated metal and vapor-phase oxidizer.
    Absorbed molten metal forms a film on the filler particles. The product of oxidative interaction is formed at the interface between the infiltrated metal melt and the vapor-phase oxidizer. This product, when formed, grows in two opposite directions relative to the orientation of the interface at a given point in space, namely: outward, i.e. into the vapor phase inside the pore volume between the filler particles, and inward, i.e. into a film of molten metal. As it is obvious, when this oxidation product grows inward, it dissolves in the mentioned metal until the melt is saturated, and when the saturation state is reached, the product falls out of the saturated solution.
    The foregoing is illustrated in FIG. 1 and 2.
    In FIG. 1 schematically shows a cross-section of the installation in which the claimed process is carried out. The mass of the source metal, having an appropriate size and shape, is placed in form 2 from a disjoint powder filler located in the working tank 3. The specified tank is heated to a temperature exceeding the melting point of the source metal, part of which is infiltrated into the filler in the molten state. The shaded part of the metal blank means the melt remaining in its original position. The dashed line 4 approximately separates the zone of metal infiltration into the filler.
    FIG. 2 is a cross-sectional view along the secant plane AA shown in FIG. 1, to the border of infiltration
    4. This cross-section for clarity of the image is given with high magnification. Filler particles are indicated by 5, 6, 7 and 8. The direction of flow of the vapor-phase oxidizer is shown by arrows 9.
    On particles 5, 6 (with the exception of filler particles 7 and 8), a film of molten base metal passed into the filler was formed. This film is shown by a peripheral shaded rim around said filler particles in an intermediate pore volume. In addition, as shown by internal hatching, the molten metal passes into the pore volume inside the particles themselves (position 5, but not position 6 and
    7). Particle 8 does not have such pores, having complete continuity.
    Short arrows 10 show the directions of the internal and external growth of the product of the oxidative interaction at the interface between the initial metal melt and the vapor-phase oxidizing agent. Obviously, these directions vary depending on the orientation of the interface at any given point in space.
    From the foregoing, it follows that in the case under consideration there is no flat front of chemical interaction and that this interaction takes place within a significant part of the void volume between the particles of the impregnated filler.
    The fundamental positive difference of this invention compared with the prior art is based on the inventive concept of controlled regulation of the volume of a system of pores or channels within the permeable mass of the filler. The voids between the filler particles should be large enough so that the molten metal film is freely distributed over the surface of these particles, which together form an easily permeable mass of filler. At the same time, interconnected hollow channels should not be completely filled with molten metal. In certain cases, the filler particles may have porosity with a smaller flow area than voids between the particles. During infiltration, the pores in the particles are filled with metal. In order for the formation of the oxidation product to occur along the part of the filler impregnated with molten metal, it is necessary that the porosity in it, having a relatively large volume, be distributed evenly. During the course of the oxidation reaction (s), the channels in the filler are gradually filled with the resulting product of the chemical interaction, which also has a porosity of a small cross section. The newly formed small pores are filled with new portions of the starting metal and thus, the process continues until a microstructure with a relatively high density is formed.
    As a permeable filler, elements such as filaments, wires, plates, tubes, thin rods, rods, powder molded aggregates, including briquettes of spherical particles, powders, granules, such as whiskers, flakes and tubular particles, continuous or discrete fiber bodies such as single fibers, fiber tows, tow, tow, yarn, fabric, felt, and the like. highly porous structural formations, including spongy materials and / or foams.
    In all of the above cases, the porosity of the filler mass is characterized by pore size distribution. It should be noted that in the description below, only powder materials will be considered as filler, but it is also possible to use other types of materials.
    Filler particles may or may not have pores. Particles with pores can contain them as penetrating channels or in the form of intermediate channels - voids between individual small particles of agglomerate or crystals forming a particulate (granule). Such particles or crystals may in some cases be equiaxed. Unbalanced particles can consist of wires, flakes, whiskers, etc. Internal porosity in granules (agglomerates) is formed by gaps between crystallites or relatively small particles.
    During infiltration, the starting metal fills the fine porosity inside the filler particles and the intermediate hollow channels formed between relatively large agglomerate particles. If the filler consists of non-porous particles, they must be large enough so that the channels between them can absorb a wetting film of molten metal and gaseous oxidizing agent.
    The geometry of the filler is one of the most critical factors affecting the relative rates of infiltration of molten metal and the progress of oxidative reactions. The rate of the oxidation process is interconnected with the total surface area of the gas-metal contact, the rate of transportation of the vapor-phase oxidizer through the permeable mass of the filler to its part saturated with molten metal and with the rate of transportation of molten metal through the portion of the filler filled by it.
    During infiltration, the metal is either distributed in the form of a film along the surface of non-porous particles, or fills the pores contained in them, while the initial total contact surface area between the gas and the metal on which the oxidative chemical interaction occurs is equal to the surface area in the spaces between the particles of the infiltrated part of the filler . The indicated surface area of the chemical interaction increases with decreasing particle size of the filler. This takes place to the point where the gaps between the particles become so small that they are completely filled with a film of infiltrated metal melt. In this case, there is a sharp decrease in the surface area of chemical interaction and the formation of a composite with a metal matrix. Above this level or point, an increase in the surface area of the gas-metal chemical interaction leads to an increase in the rate of oxidative interaction and the volume content of the oxidation product.
    The rate of passage of the vapor-phase oxidizer through the permeable mass of the filler is interconnected with the total pore volume and size distribution in the uninfiltrated part of the filler, as well as with residual porosity in the infiltrated part. An increase in pore size and volume leads to an increase in the gas permeability of the filler mass, increasing access to the vapor-phase oxidizing agent, which is naturally accompanied by a higher
    Ί lower rate of chemical reactions.
    The rate of expansion of the infiltration zone in the volume of the filler is determined either by the speed of passage of the molten metal, or by the conditions of wetting along the edge of the contact zone with the uninfiltrated part of the filler. The source metal in the form of a melt seeps through the pores inside the filler particles or along their surface in the intermediate channels. An increase in the pore volume inside the filler particles and / or a decrease in the volume of voids between these particles leads to an increase in the passage through the molten metal и and, accordingly, to an increase in the rate of infiltration.
    By selecting the pore size and the shape of the particles in the filler mass, it is possible to control the melt infiltration rate and oxidative interaction with sufficiently high efficiency, forming the necessary microstructure of the resulting product. In the idealized case, the infiltrate zone spreads into the filler mass at a speed that allows filling the volume of the gaps between its particles with the product of oxidative chemical interaction. The acceleration of the infiltration of molten metal leads to the appearance of porous structures.
    A sufficiently complete volumetric impregnation of the filler particles with the starting metal is provided when the internal pore size in the particles is less than 20 microns, and preferably 5 microns. Accordingly, the required transverse size of the intermediate channels between the filler particles, providing unhindered passage of the vapor-phase oxidizer, is at least 20 μm with an upper limit of 100 μm. These preferred dimensions of the porous permeability of the filler can be realized through the use of powders with the appropriate particle size and their respective packing density. In general, particles with a diameter of 20-2000 microns are acceptable. The internal porosity of the particles depends on their physical and geometric characteristics, making up, in permissible cases, in a relative volume of 1-98%, where O% corresponds to completely impermeable particles, and 98% to foams. The porosity of agglomerate particles (granules) with isosceles grains is 40-60%, while the interparticle porosity in the intervals of non-isosceous whiskers approaches 60-90%.
    In a typical case, to achieve the objectives of the present invention, the maximum porosity inside the filler particles is a passage size of 5 μm.
    The use of a filler with porous particles is preferable in those cases when it is necessary to carry out oxidative interaction of the largest possible part of the starting metal with a powder filler with a relatively small particle size. The use of such a filler ultimately contributes to a product with high mechanical properties. In this preferred embodiment, the oxidation product can be obtained both inside the filler particles themselves and in the spaces between them due to the processes of external and internal growth discussed above. In most cases, the product obtained inside the pores of the filler particles has the same mechanical properties as the product formed in the porous voids between these particles.
    If necessary, the filler can be made in the form of a compacted briquette of powder, incoherent particles. In turn, the filler particles can be bonded together into a permeable, uniformly shaped preform with the size and shape of the desired composite product.
    As noted above, to control the rate of infiltration of molten metal - the base into the filler and the rate of oxidation of this metal, appropriate technological methods and technological support tools can be used.
    In addition to this, the rate of infiltration of the melt of the starting metal into the filler can be controlled by exposure to this metal with increased or decreased static (hydrostatic) pressure. This pressure can increase due to the amplification of the gas to the surface of the melt. Accordingly, this increase can be realized through the use of a hydrostatic column of melt over the bulk. The latter means an increase in the rate of melt infiltration. Hydrostatic pressure can be reduced by placing the mass of molten metal below the mass of the filler so that capillary forces counteract the forces of gravity. In this case, the rate of infiltration decreases. At the same time, the amount of molten metal filling the void channels between the filler particles decreases.
    In addition, the oxidation rate of the parent metal can be controlled by changing the pressure of the vapor-phase oxidizer. A decrease in the partial pressure of this oxidizing agent is accompanied by a decrease in the rate of oxidative interaction. Conversely, an increase in partial pressure leads to an increase in the rate of chemical interactions.
    The partial pressure can be lowered by diluting the gaseous oxidizer with an inert gas. This, in turn, will lead to a decrease in the oxidation rate. When oxygen is used as the vapor-phase oxidizing agent, nitrogen is the preferred diluent thereof. In turn, if the oxidizing agent is nitrogen, it is advisable to use argon as a diluent.
    In addition, pressure reduction can be implemented;
    by placing the apparatus that implements the proposed method in a chamber connected to a vacuum pump and, accordingly, by pumping this chamber to a reduced pressure or in a sealed vacuum-tight chamber, in which the vapor-phase oxidizer is gradually absorbed during the reaction-oxidative interaction of the starting components with the formation of an oxidation product at the same time, the pressure is controlled by the inlet of an additional vapor-phase oxidizer with a controlled speed.
    In turn, to increase the rate of oxidative interaction, the indicated pressure may increase. For this, the working apparatus can be placed in a pressure chamber connected to an appropriate means providing an increase in pressure above atmospheric.
    In accordance with the inventive task, the preferred range of partial pressures of the vapor-phase oxidizer, necessary for the implementation and the required increase or decrease in the rate of oxidative interaction, is 0.01-2 ati. Higher pressures can be provided in special heating isostatic compression chambers. Such increased pressures may be appropriate in the sense of increasing the proportion of the product of the oxidative interaction formed during internal growth in the molten metal.
    As noted in the accompanying copyright applications, the rate of oxidative interaction of the melt of the parent metal can be increased through the use of an appropriate additive. Such an additive or additive may be an alloying element introduced into said metal. In turn, a coating material placed between said metal and filler can be used as such an additive. It is also possible the introduction of filler materials in the form of powders in the mass of the filler, for example, by mixing with its particles. In addition, the filler additive may be introduced into the filler in the form of a coating applied or applied to the surface of the filler particles.
    Some additives under the action disrupt the continuity of the ceramic part of the product of the oxidative interaction, thereby increasing the rate of the oxidation reaction. Others act as wetting agents on the filler or oxidation product through the parent metal, which allows you to adjust the rate of infiltration of the latter.
    Another objective aspect of this invention is to obtain a polycrystalline composite material containing an oxide matrix formed by the chemical interaction of the parent metal with oxygen, air or oxygen-containing gas mixtures and a filler material embedded in this matrix.
    In the aforementioned accompanying applications, which belonged to the authors of this invention, the entire group of metals in the filler material is given, which can be used for the implementation of the considered purposes in combination with an oxygen-containing vapor-phase oxidizing agent. The nature of the processes taking place in this case is explained below using aluminum as the starting metal, and alumina as a powder, granular filler.
    When developing this invention, the influence of the chemical composition of the starting metal, temperature, the composition of the gaseous oxidizing agent and the particle size of the alumina filler on the nature of the process of formation of cermet was revealed. In the course of studies, it was found that under certain conditions, when a ceramic product grows into a filler mass, substantially porous structures can be formed that are bonded together by a relatively thin film of an oxide matrix, while channels are maintained that provide vapor-phase oxidizer access over almost the entire volume of the infiltrated (impregnated with the molten source metal) ) parts of the briquette from the filler. A change in the above process parameters leads to a change in the microstructure of the resulting product; in some cases, an impermeable composite material with a high density, which is practically pore-free, is obtained. The composition of the starting metal and the gas oxidizer has the greatest effect on the nature of the porosity of the resulting ceramic product. Aluminum-based alloys containing a relatively large amount of silicon dopant, when used as starting material, tend to form denser microstructures than alloys with a lower silicon content for a given oxygen content in the oxidizing agent. Further, it should be noted that a decrease in the oxygen content in the vaporous oxidizer also reduces the rate of oxidative interaction, contributing to the formation of a more porous microstructure. A change in temperature also affects the rate of oxidation. In this sense, there is an optimum temperature, which corresponds to the maximum rate of oxidation reactions. At or near this temperature, microstructures with minimal porosity are obtained. In addition, the temperature affects the ratio of the oxide and metal phases in the matrix. A decrease in the particle size of the filler also slightly reduces the rate of oxidation, however, this effect is less pronounced than the influence of the partial pressure of oxygen. This aspect of the invention is illustrated in Example 1.
    A further objective aspect of the present invention is the production of polycrystalline materials containing a nitride matrix formed by chemical nitriding of the parent metal using a vapor-phase nitriding agent. The composition of these materials also includes a filler material embedded in said matrix.
    The sequence of processes necessary for the implementation of such a reaction nitration is similar in general to that discussed above. This analogy is manifested in the fact that the relative rates of infiltration of the starting metal into the indicated filler and the mentioned chemical interaction are such that at any given time the specified interaction takes place in a significant amount of the infiltrated part of the specified filler.
    The group of preferred starting metals includes silicon, aluminum and titanium. If silicon is used as the starting metal, silicon nitride, aluminum nitride and titanium nitride are preferred fillers. Among suitable non-nitrogen fillers, silicon carbides and titanium should be mentioned. If aluminum is used as the starting metal, it is advisable to use aluminum nitride, aluminum oxide, silicon carbide, titanium carbide and boron carbide as components of the filler. From a commercial point of view, materials giving the same nitration product as the filling material are desirable. This results in the production of a material with a monoceramic phase, but in some cases with a residual content of unreacted starting metal. Examples of such composite products with one ceramic phase are, in particular, cermet with a matrix of silicon nitride and a filler of the same nitride and cermet with a matrix of aluminum nitride and a filler of the same nitride. In turn, inert fillers can be used to realize any specific properties of the composite obtained. For this purpose, mixtures of filler materials with different chemical compositions, as well as mixtures with filler particles with different size and shape of crystals, can be used.
    For example, pre-prepared fibers of silicon carbide mixed with agglomerated porous isosceles particles consisting of displaced crystals of silicon carbide can be introduced into the structure of the nitriding product of silicon nitride.
    As indicated above, in the analysis of the oxidation reaction, the relative amounts of nitride and non-nitride starting metals in the matrix of the composite product can be controlled by selecting appropriate filler materials having an appropriate volume of porosity.
    Ij
    It should be emphasized that without additional operations, the above procedure by itself may not provide for the infiltration and growth of the nitride-ceramic matrix. may interfere with the process of impregnation of the filler and / or nitration of the source metal. The operations that are necessary to prevent the occurrence of harmful impurities and / or to remove existing impurities are discussed in detail below. Carrying out these operations gives a significant increase in the efficiency of the proposed technological process in comparison with the currently used processes.
    Harmful impurities that may be present in the mass of the filler, the parent metal base or in a nitrating atmosphere prevent the filler from wetting the melt of the specified metal or lead to the formation of a passivating impermeable coating on the surface of the metal melt. Typical harmful impurities, in this sense, are oxygen and water vapor, absorbed by the surface of the filler particles or chemically introduced into it by hydrolysis.
    Although the mechanism of the negative effect of oxygen and water vapor on the oxidizing process of the formation of composite metal ceramics has not yet been fully studied, at this stage it can be reasonably assumed that if silicon is used as the starting metal and silicon nitride is used as a filler as a result of oxygen absorption or hydrolysis reactions, a surface enriched with silicon oxide is formed. Such a surface (or surfaces) is less wettable by silicon alloys compared to pure silicon nitride and, under the conditions of the nitration process, prevents the infiltration of molten metal into the filler. Similarly, oxygen and water vapor disrupt the oxidation process if they are present in a nitriding atmosphere. These harmful impurities enter into chemical interaction with both the starting metal and the filler, impairing the wetting and the course of nitration reactions. There are several potential sources of oxygenated chemicals in the process under consideration. These include: the residual content of such substances in the nitriding gas, their output or saturation by them in a drying column or special oxygen scavengers used to clean the gas stream, incomplete removal of air from the furnace insulation as a result of purging or pumping out with re-filling with nitriding gas, desorption of oxygen or water steam from the insulation surface of the nitriding furnace, the exit of volatile oxide or suboxide compounds from the oxide refractory of the furnace or its other oxide elements as a result of direct Paired, for example B2O3, or partial reduction by contact with carbon-containing elements or furnaces with parent metal vapors. Even carbon monoxide, which is one of at least effective oxidizing agents, can be chemically reduced by molten parent metal. In this case, in particular, the formation of both solid metal carbide and oxide and volatile suboxide is possible. The formation of such solid carbides on the surface of the initial metal melt was repeatedly observed during experiments. It impairs the ability of a metal melt to flow and seep into the filler.
    The degree of purification from the considered harmful impurities necessary for the effective formation of a nitration product is different and depends on such parameters as the ratio of the specifically selected starting metal and filler, their affinity for oxygen and / or hydrolysis, as well as on the wetting ability of the oxide and nitride with respect to the initial to metal. For example, aluminum nitride is very easily oxidized and hydrolyzed, forming a surface layer of aluminum oxide. At the same time, both aluminum oxide and aluminum nitride are quite easily wetted by an aluminum-magnesium alloy (if used as a starting metal). Such a system works effectively at low levels of oxygen pollution, i.e. until these levels are high enough to form an oxide shell on the initial alloy, preventing its flow. For example, a nitrogen gas stream with a content of 8 ppm of oxygen and 250 ppm of water acts as an effective nitriding agent, providing the formation of compounds with a matrix of aluminum nitride. But at the same time, when the content of impurity oxygen is at the level of the order of 1%, nitriding and melt infiltration completely cease.
    Permissible levels of impurity oxygen content in the case of using a silicon-base alloy and a filler in the form of silicon nitride as the starting metal have not been accurately determined. However, it is obvious that they should be lower than in the case of the use of the component system aluminum-aluminum nitride. As can be assumed, a prerequisite for this is the lower ability of silicon-base alloys to wet the surface of silicon nitride containing silicon oxide.
    Acid,., Ed and / or moisture may be present as side impurities in a commercially available, industrial nitrogen gas. Therefore, when using gaseous nitrogen as the chemical component of the vapor-phase nitrating medium, it is necessary to use only high-purity commercial nitrogen, in which the aforementioned impurities are present in very small quantities.
    Harmful impurities may also be present in the molten parent metal. Typical impurities when using a silicon-base metal and silicon nitride as a filler remain boron and aluminum. Both of these elements have nitrides that are more stable than silicon nitride, and if they are present in the initial alloy and in a noticeably high concentration, they form their own nitrides in the upper layer of the melt, thus blocking the formation of silicon nitride. Aluminum at concentrations of more than 1% tends to interact with the S13N4 filler, restoring silicon from it and forming aluminum nitride does not affect the impregnating effect in the silicon-nitride-silicon system under consideration, and, in this case, the filler can be impregnated until an aluminum nitride film is formed on molten starting metal. At aluminum concentrations of less than 1%, silicon does not manifest any negative effects. Commercially available silicon of metallurgical production containing about 0.5% aluminum is fully suitable for use in this method. It should be noted that the aluminum impurity that appears in such silicon as a result of the melting of silicon ingots in alumina molds practically does not affect the development of chemical processes in the preparation of the ceramic in question. Unlike aluminum, boron has a significantly greater negative effect. It affects the wettability in the silicon-nitride-silicon system and prevents the infiltration of molten metal into the filler. In the absence of effective contact between the filler and the starting metal, the filler is practically removed from participation in the reaction-exchange interaction on the melt, a passivating shell of boron nitride is formed.
    Surface contamination of the filler with oxide by-product impurities can be eliminated by carrying out high-temperature pre-treatment. This can be done before the briquette is formed or pressed from the filler, while its material is still in a loose state. It is in this case that reliable contact interaction between the treatment medium and each filler particle can be ensured. Such pre-treatment can be carried out by impregnating the initial briquette of the filler in a stream of a nitrating or inert atmosphere or gaseous hydrogen. Subsequently, precautionary measures should be taken in order to exclude the possibility of re-contamination of the filler with water vapor, atmospheric oxygen, or components of technical binders used to obtain primary unconsolidated briquettes. All this relates to storage conditions, preparation for production and the direct implementation of its technical operations. In an alternative embodiment, immediately after the preliminary processing of the source material to remove harmful impurities, a permeable, but at the same time, necessarily compacted, working blank of filler, corresponding in shape to the manufactured product, can be molded. Thus, re-introduction of impurities can be minimized. However, in this case, it is possible to increase the required duration of pretreatment, since the rate of removal of impurities is sharply reduced due to a decrease in the permeability of the compacted preform relative to the treated medium and a weakening of the diffusion yield of impurities from the preform material.
    An example of the above is the process of removing oxide impurities from the surface of filler particles from silicon nitride. Commercially available silicon has a wide range of particle sizes.
    It should be borne in mind that relatively large particles are usually porous agglomerate granules of individual crystals with a size of 1-10 microns. At the same time, for the purposes of this invention, i.e. to obtain permeable briquette preforms of the filler, it is recommended in the preferred embodiment, use isosceles particles with a size of 50-150 microns. When using a commercially available powder filler, its particles have surface impurities in the form of a layer of silicon oxide formed as a result of surface hydrolysis and oxygen adsorption. If such a powder is used without preliminary treatment as a filler in contact with the silicon-base parent metal, there will be no metal infiltration first: at a temperature in the reaction zone of the order of 1550-1650 ° С and using the atmosphere of the corresponding gas necessary for vapor-phase nitration, the infiltration will occur only a few hours later. Effective wetting conditions are created after the specified exposure time. Under these conditions, metal infiltration and the development of nitration reactions begin.
    In practice, of course, it is advisable to exclude the indicated incubation period of exposure by pretreatment of the silicon nitride filler with the removal of surface impurities from the material and ensuring non-exposure wettability by the molten source metal. Such pretreatment is carried out either in a reactor with a stationary or threaded loading using a stream of nitrating or inert atmosphere, passed through a mass of material in the reactor in order to liquefy this material and remove impurities from it. The removal of these impurities is facilitated by vapor-phase additives selected so that the formation of volatile products occurs when interacting with the surface layer of aluminum oxide. Such additives include aluminum, silicon and magnesium in the vapor state, as well as hydrogen, fluorine, chlorine, hydrogen chloride and hydrogen fluoride. The first four of these additives are reducing agents, which, when applied, reduce the partial pressure of oxygen in the working atmosphere to the level at which decomposition of silicon oxide S1O2 into the volatile SiO compound occurs. Other additives are oxidizing agents which, in combination with hydrogen in the atmosphere used, react with silicon oxide to form volatile compounds SiF4, SiCU and fluoroxide or chloroxide. Subsequently, these volatile products can be relatively easily removed from the reactor by lowering the total pressure therein using conventional mechanical pumps. For this purpose, in most cases, it is sufficient to create a vacuum at the level of 10 ' 4 -10' 5 atm. The required temperature range for the treatment in question is 1550-1800 ° C. Although the process of removing impurities is accelerated at higher temperatures, their use is impractical, since at such extremely high temperatures decomposition of the silicon nitride filler will occur. The time required to clean the filler starting material, from 20, varies from one to five hours depending on the temperature, pressure, and the nature of the gaseous additives. The powder material thus treated should be stored and used during processing in an inert, dry atmosphere.
    The molding binders used in the manufacture of preforms (briquettes) of the filler must also be deoxygenated. This is necessary in order to 30 prevent the re-introduction of impurities into the filler. Paraffin-type hydrocarbons may be used as binders.
    Another alternative solution in obtaining a porous deoxygenated nitride preform or briquette 35 is to carry out chemical interactions in the corresponding starting material. This material can be 40 metal. In some cases, it may even have the same chemical composition as the molten parent metal used in the reaction-infiltration operation. With the 45 implementation of such a technological variant, the process of manufacturing a briquette preform for manufactured ceramics consists in: mixing a metal powder, scraps of fibers, wire, chips or 50 flakes with an inert filling material, giving the obtained initial mixture the necessary shape using conventional technological methods of powder metallurgy. The semi-finished product thus obtained 55 is then subjected to chemical interaction (processing) with the formation of the necessary chemical substance, while the dimensions and porosity of the obtained pre-fabricated product must be kept the same. as in the primary midpoint. An advantage of such a reaction-bonded preform is that the source metal necessary for the formation of composite ceramics is brought into contact with this preform without any contact with air or some other sources of harmful impurities. For example, a chemically vulcanized billet of silicon nitride can be made by nitriding a profiled molded briquette of silicon powder using nitrogen gas, ammonia, or molding gas (a mixture of nitrogen and 5% hydrogen) at a temperature of 12001400 ° C, which does not exceed the melting point of silicon. As a result, hard silicon is formed - silicon nitride core. Then the temperature rises to above 1450 ° C. At this temperature, the remaining silicon melts and the nitration rate increases. The workpiece thus obtained is free of oxygen impurities.
    Another alternative process for obtaining a porous deoxygenated nitride preform - the base is to mechanically fabricate a blank in the form of a blank - a rod and a matrix of a given profile from a solid source metal, followed by backfilling the obtained metal form with an inert filler, which is in an incoherent state in the form of powder or granules. Then the first heating operation is carried out and, accordingly, reaction conditions are formed that lead to the formation of a porous composite microstructure. The porous product thus obtained is then removed from the filler mass. At this moment, it has an internal cavity that reproduces in shape the outer surface of the bar blank from the source metal and is similar in mechanical properties to ordinary burnt unglazed ceramic materials. At this stage, in some cases, it may be appropriate to carry out additional machining of the outer surface of the workpiece in order to bring it to a precisely defined shape. Such treatment should be carried out in a dried nitrogen atmosphere. The result is a blank - a frame with precisely defined external and internal surfaces with a minimum amount of harmful impurities. Then this preform is infiltrated by the product of nitration interaction under conditions optimized in accordance with the above principles so that a sufficiently dense and non-porous microstructure is formed.
    As shown in the aforementioned accompanying patent applications, in some cases, for the effective implementation of the reactions of formation of ceramic material, the use of appropriate additives is required.
    Despite the fact that when implementing the method under consideration, it is not necessary to introduce additives to stimulate the reaction nitration of silicon or aluminum-containing starting metals, in the general case, the introduction of such additives into the molten starting metal or into the permeable filler mass accelerates the nitration reactions. As shown, the introduction of filler additives in the form of iron and copper is advisable for nitration of the silicon-base metal.
    In the implementation of the inventive method, ingots of a silicon-iron alloy and a silicon-copper alloy were used, containing in each case up to 10% by weight of the alloying element. The use of iron-copper additives led to an increase in the amount of the substance involved in the nitration reaction at a temperature of 1550 ° C compared with the nitration regime on pure silicon under the same technological conditions. Even with smaller amounts of iron (from 0.8% iron, typical for industrially produced silicon, and up to 0.0018% in various alloys), it exhibits a rather high filler (alloying-catalytic) activity, giving almost the same positive result in stimulating the process nitration.
    Magnetic additives are applicable to an aluminum-containing parent metal. These additives can be introduced either into the parent metal or into the filler in the various ways described above.
    Both for aluminum and for silicon used as starting metals. the positive effect of the considered additive additives is manifested in accelerating the kinetics of chemical interactions, obtaining a less porous microstructure and a higher degree of conversion of the starting metal into an intrid ceramic matrix.
    Realized modes of oxidative (nitrating) chemical interaction in certain cases can be implemented so as to limit the amount of product of this interaction. This was stated above. In these cases, a metal matrix composite is formed with unreacted starting metal in the filler.
    In accordance with another aspect of the invention, it is possible to further improve the physical properties of the metal matrix, and hence the final composite product, by additionally introducing into the starting metal a reagent of one or more alloying elements of the corresponding type. Such elements can be selected in order to carry out solid-solution or dispersion hardening of the metal, to convert the metal phase into intermetallic compounds with a high melting point, or to increase the melting point of the residual metal. When using silicon as the starting metal and silicon nitride as the filler, the amount of residual metal in the resulting ceramics can be controlled by the addition of iron, copper, manganese, titanium, nickel, or calcium.
    When implementing the method of this invention, the additional introduction of these alloying elements into the mass of the filler or the starting metal can be used for a controlled change in the composition of the residual metal in the final product. A positive aspect of this alloying is that the alloying elements do not form nitrides, ultimately manifesting themselves as silicides or intermetallic phases in a metal. Such alloying additives, if necessary, can be introduced directly into the starting metal. Or they can be used as reducing compounds in the form of a powder, an injectable filler. Similarly, if aluminum is used as the starting metal component and oxygen is used as the vapor-phase oxidizing agent, alloying additives can be used in the form of one or more oxides of the corresponding metal capable of being reduced by aluminum (for example, copper, silicon or titanium oxides) . Such oxides can be introduced into the filler in granular powder form. Alternatively, they can be pulverized, finely ground, suspended in an appropriate aqueous or organic medium, and then used as a coating or coating on the surface of the filler particles.
    In accordance with another embodiment of the invention, one or more shielding, barrier compounds can be included in the filler as a layer forming the outer surface on the resulting composite product of a given composition. Such barrier compounds inhibit the growth or development of the product of oxidative interaction behind the barrier layer formed by them in contact with the infiltrated medium.
    As such barrier additives, an appropriate chemical element, composition, and the like can be used, which, under the conditions of the method under consideration, maintains continuity, is non-volatile and preferably permeable to a vapor-phase oxidizing agent, while at the same time possessing the ability to local inhibition, absorption and termination of chemical processes in combination with blocking the current mass growth of the product of oxidative interaction. Recommended barrier additives in the case of using aluminum as the starting metal are calcium sulfate, calcium silicate and Portland cement, as well as from a mixture that is best used in the form of a paste or suspension applied to the surface of the filler. Recommended barrier materials when used as starting metal silicon include alumina, silica and their compounds and mixtures. Non-volatile boron compounds, such as boron nitride, are also suitable in this sense. Such a barrier additive may also include appropriate hot or volatile material removed from the initial mixture of the resulting ceramic when heated, or material that decomposes upon heating. Such material is necessary to increase the porosity and permeability of the formed barrier. Further, the considered barrier additive may include an appropriate refractory powder designed to reduce the shrinkage or cracking that may occur during the implementation of the considered method. In this practical aspect, a powder material is desired that has an expansion coefficient close to that of the filler or preform of the manufactured article. For example, if the preform and the ceramics obtained from it consist of alumina, the barrier material can be used in admixture with powdered alumina, preferably with a particle size corresponding to sieves No. 20-1000, or less. Other recommended barrier materials23 may include refractory ceramic or metal coating shells open at least at one end in order to provide vapor-phase oxidizer access to the filler mass and molten metal component.
    As noted above, alumina and silica are the most suitable barrier materials in relation to the infiltration of molded preforms from a filler with a silicon-silicon nitride matrix material. This recommendation is confirmed by appropriate tests. The acceptability of alumina and silicas is due primarily to the fact that these materials are not wetted by silicon, used as the starting metal. Aluminosilicate minerals such as mullite or kaolin can also be recommended as barrier materials. It is also possible to use oxides and other metals that are less inert than silicon and therefore cannot be reduced by it. These include alkali and alkaline earth metals and their compounds with each other and with aluminum oxide and silicon. The melting point of the oxide compound selected as a barrier additive should exceed the temperature of nitration reactions, and at this temperature the barrier material should not sinter into a dense mass that is not permeable to gas.
    It was noted above that nonvolatile boron compounds, such as pure boron nitride, can be used as a barrier material to limit the zone of infiltration and accumulation of silicon nitride. Boron itself worsens the wetting in the silicon-nitride-silicon system, thus preventing the filling of the filler with molten metal.
    A further embodiment of the invention essentially provides for a time-controlled termination of oxidation reactions due to the addition of an appropriate deoxidizing material introduced either into the melt of the starting metal reagent or into the gas atmosphere. In the case of using a silicon-base parent metal, it is recommended to use metallic boron and its volatile compounds, including boron oxides, haploid compounds or hydrides, as blocking materials under consideration.
    The action of the blocking materials of deoxidizers can be reversed by the addition of a chemical element that forms fairly stable boron compounds. In the case of the use of silicon-base metal, the introduction of calcium and its compounds leads to the resumption of nitration of this metal. Elemental calcium with a weight concentration of 10% can be added to the silicon-base metal as an alloying additive. It is also possible to use calcium nitride with the same weight concentration as an additive to the filler of silicon nitride. The result of this is the formation of calcium hexaboride in the form of a solid precipitate, which removes boron from the alloy of the parent metal, reducing its concentration in the liquid solution to a level at which the formation of compound BN stops and the wettability of the filler sharply improves.
    Based on the analysis of the composition and nature of the action of impurities that have a blocking or interrupting effect on the oxidation reaction, they can be effectively used to control this reaction. So, the reaction can be stopped at a certain moment by introducing the corresponding impurity — the additive into the molten metal or into the gas atmosphere, and then resume again with the introduction of the corresponding alloying (catalytic) additive.
    Example 1. To obtain an aluminum oxide semi-crystalline composite according to the method of the present invention, industrial pure aluminum with a 3% silicon and magnesium content was used as the starting metal reagent. The operating temperature in the reaction medium was 1250 ° C. As a filler was used alumina Norton 38 Alundum. Oxygen was used as a vapor-phase oxidizer.
    Four series of control tests were carried out, during which a filler of two types of granular ™ was used (two particle sizes) at two different levels of the partial pressure of the oxidizing agent. The results are shown in table. 1.
    The effect of increasing the partial pressure of oxygen on the rate of chemical reactions is significantly higher than the effect of increasing the particle size of the filler. The order of increasing the reaction rate is characterized as follows: 4 <3 <2 <1 (lowest) (maximum)
    Example 2. To obtain a polycrystalline composite of silicon nitride as the starting metal was used high-purity metallic silicon. The working temperature of chemical reactions was 1650 ° C. The filler used was industrial silicon nitride manufactured by Kema Norm Company. Nitrogen was used as a vapor-phase oxidizer.
    Two tests were conducted. One test was conducted on the resulting filler without processing. This filler material consists of quasi-isosceles particles of irregular shape with a size of 150-250 microns, each particle is an agglomerate (granule) of small crystals with a size of 1-10 microns. Such agglomerate particles for the most part had porosity, which was very different. In another test, the starting filler material was milled, as a result of which the agglomerate particles were separated into individual crystals with a size of 10 μm. In the compacted mass of such a filler, only small inter-intermediate voids were formed; large interconnected channels did not have a system. Such crushed powder material was used as a dusting layer compacted around a silicon ingot.
    According to the test results, the results are shown in table. 2.
    From the above data it follows that the use of fine-grained filler, characteristic for test No. 2, leads to significantly less formation of the oxidation product, i.e. to increase the proportion of unreacted metal, even with an increase in the time of chemical reactions by three times while maintaining the same temperature (in comparison with test No. 1).
    In FIG. 3, with a brevity of magnification 100, the structure of a sample of silicon nitride filler in the form of porous agglomerate particles is shown. We used a sample obtained immediately after the completion of silicon melt infiltration during Test No. 1. The gray areas correspond to silicon nitride, the light unreacted silicon starting metal, and the black to pores. In this image, the initial particles of silicon nitride and their internal pores filled with infiltrated metal silicon are clearly visible. Each particle is surrounded by a layer of dense reaction product in the form of silicon nitride. In the volume between the filler particles there were voids.
    In FIG. 4 shows a micrograph of the composite material obtained during test No. 1. The state of this sample corresponds to the completion of the nitration reaction.
    FIG. 5 is a micrograph of the composite material obtained from test results No. 2. (The brevity of enlargement of the images of FIGS. 4 and 5 is 100). In both images, the initial filler particles are still quite clearly visible in the structure. In the microstructure shown in the snapshot of FIG. 4, the gaps between the particles are filled with a silicon nitride chemical product. This microstructure is practically non-porous.
    From consideration of FIG. 5, it follows that an attempt to carry out reactive infiltration (impregnation) of the applied filler with a molten silicon led to an uneven filling of large volumes of the filler with metal with the formation of an unorganized infiltrated matrix structure.
    The following examples illustrate the effect of the use of additives on the nitration of highly pure silicon.
    Example 3. According to the method of the present invention, silicon nitride polycrystalline composites were obtained using the following starting metals (alloys):
    1) high-purity silicon (ct-type Gn),
    2) silicon 90% concentration with 10% iron supplement,
    3) silicon 90% concentration with 10% copper addition.
    Chemical reactions were carried out at a temperature of 1550 ° С for 16 h using 150-250 tons of granular silicon nitride produced by Ken Nord Company as a filler.
    From the above data it follows that a significant increase in weight gain, i.e. the degree of nitration of metallic silicon is associated with the use of copper and iron as additives.
    权利要求:
    Claims (11)
    [1]
    Claim
    1. A method of producing a polycrystalline composite material, comprising placing a permeable refractory inert filler in contact with a starting metal from the group: Si, Sn, Ti, Zr, Al doped, heating in a gaseous reaction medium to a temperature exceeding the melting point of the metal but lower than the melting temperature the product of its interaction with the gaseous medium, and exposure for the time necessary for the migration of the metal and its oxidation product into the filler to form a compact, characterized in that, with Giving the compact the desired properties and increasing the interaction efficiency, they control the rate of filtration of the molten metal and the rate of the oxidation reaction by reducing the partial pressure of the gaseous reactant in the range of 0.1-1 atm, or increasing it to at least 2 atm, or applying hydrostatic pressure to the metal , or the use of a filler with a particle size varying within 2-2000 microns, and an internal porosity varying within -98%.
    [2]
    2. The method of pop. 1, characterized in that the filler consists of a compacted layer of unbound particles.
    [3]
    3. The method of pop. 1, characterized in that the filler consists of a workpiece of bound particles.
    [4]
    4. The method of pop. 3, characterized in that the filler has a spongy structure.
    [5]
    5. The method of pop. 2, characterized in that the unbound particles of the filler are in the form of rods, whiskers or platelets.
    [6]
    6. The method of pop. 1, characterized in that the pressure is increased due to the pressure of the gas acting on the melt to increase the rate of infiltration.
    [7]
    7. The method of pop. 1, characterized in that the pressure is increased by maintaining the column of melt of the source metal in the riser, communicating with the filler above the surface of the latter.
    [8]
    8. The method of pop. 1, characterized in that the pressure is reduced by placing the mass of the melt below the filler in contact with it so that the gravitational and capillary forces act in opposite directions.
    [9]
    9. The method of pop. 1, characterized in that the reduced partial pressure is realized by diluting the oxidizing agent with an inert gas.
    [10]
    10. The way to pop. 9, characterized in that the inert gas is argon.
    [11]
    11. The method of Pop. 1, characterized in that the reduced partial pressure is realized by carrying out a working process in a sealed chamber, in which an oxidizing agent is reduced in an expendable manner during the course of the oxidation reaction, and also by introducing an oxidizing agent into the sealed chamber at a controlled speed.
    Table 1
    Oxidizing agent Number 1100% Sourkind Number 2100% SourROD No. 310% oxygen90% argon Number 410% oxygen90% argon Filler 200 microns 50 microns 200 microns 50 microns compacted compacted - - Microstructure Without pores Without pores Porous Porous reaction rate accelerated accelerated delayed delayed
    table 2
    Test Filler Time h Weight gain,% of theoretical maximum Matrix 1 Porous agglomerate hours 16 62 Nitride cream 150 to 250 size niya μm 48 38 Metal 2 Free crystals (por st), size - 10 microns
    Table 3
    Test Source metal Weight gain from theoretical maximum,% 1 High purity silicon 65 2 90% silicon - 10% iron 85 3 90% silicon - 10% iron 75
    FIG. 2
    Fig.z Fig 9
    Figure 5
    . Compiled by G. Zhukov Editor Tehred M. Morgenthal Corrector N. Milyukova
    Order 2489 Circulation Subscription
    VNIIIPI of the State Committee for Inventions and Discoveries at the State Committee for Science and Technology
    113035. Moscow, Zh-35, Raushskaya nab., 4/5
    Production and Publishing Combine Patent, Uzhgorod, 101 Gagarin St.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR0134960B1|1998-04-18|How to make self-supporting ceramic composite
    JP2905521B2|1999-06-14|Method of forming metal matrix composite with variable filler loading
    JP2905513B2|1999-06-14|Method of forming a metal matrix composite containing a three-dimensionally interconnected co-matrix
    FI91608C|1994-07-25|A method of joining at least two pieces together
    CZ151487A3|1993-02-17|Process for producing self-supporting body containing boride of the base metal
    EP0261062B1|1992-04-22|Modified ceramic structures and methods of making the same
    FI91494C|1994-07-11|A method of making a metal matrix composite and a composite made according to the method
    PT92856B|1995-12-29|Process for the production of self-supporting bodies with controlled porosity and graded properties
    SU1830057A3|1993-07-23|Process for producing polycrystalline composite material
    KR0134957B1|1998-04-18|A method of modifying ceramic composite bodies by a post-treatment process and articles produced thereby
    FI91492C|1994-07-11|A method of making a metal matrix composite
    PT92260B|1995-09-12|METHOD FOR MODELING A BODY CONTAINED WITH METAL MATRIX BY A SPONTANEOUS INFILTRATION TECHNIQUE
    FI91495C|1994-07-11|A method of making a metal matrix composite from molten matrix metal and a substantially non-reactive filler
    EP0368782B1|1993-10-27|A method of forming metal matrix composite bodies by utilizing a crushed polycrystalline oxidation reaction product as a filler, and products produced thereby
    JP2905519B2|1999-06-14|Method of forming metal matrix composite
    FI88022B|1992-12-15|FOERBAETTRAD METOD FOER FRAMSTAELLNING AV SAMMANSATTA KERAMISKA STRUKTURER GENOM ANVAENDNING AV METALLSLAGG
    JP2905514B2|1999-06-14|Inverted shape replication method for forming metal matrix composites
    US4981632A|1991-01-01|Production of ceramic and ceramic-metal composite articles incorporating filler materials
    JP3482480B2|2003-12-22|Graphite-silicon carbide composite having excellent oxidation resistance and method for producing the same
    US5435966A|1995-07-25|Reduced metal content ceramic composite bodies
    WO1992000939A2|1992-01-23|Reduced metal content ceramic composite bodies
    Kevorkijan1998|An advanced foundry method for the light alloy metal matrix composites based on a chemically activated wetting
    同族专利:
    公开号 | 公开日
    KR880003857A|1988-05-30|
    NO873827L|1988-03-17|
    DK481287D0|1987-09-15|
    FI873883A|1988-03-17|
    CN1036191C|1997-10-22|
    TR23693A|1990-06-15|
    DK481287A|1988-03-17|
    NZ221750A|1990-08-28|
    HUT46630A|1988-11-28|
    CS275617B6|1992-03-18|
    EP0261055A2|1988-03-23|
    PT85704A|1987-10-01|
    AU600973B2|1990-08-30|
    AU7834187A|1988-03-24|
    ZA876903B|1988-09-28|
    IL83858D0|1988-02-29|
    DE3782304T2|1993-03-25|
    DE3782304D1|1992-11-26|
    PH25259A|1991-03-27|
    AT81647T|1992-11-15|
    YU172387A|1989-06-30|
    CN87106244A|1988-03-30|
    PL156554B1|1992-03-31|
    US4824625A|1989-04-25|
    MX165196B|1992-10-30|
    PL267690A1|1988-07-21|
    KR950008595B1|1995-08-03|
    BR8704766A|1988-05-03|
    IE60943B1|1994-09-07|
    IN168487B|1991-04-13|
    EP0261055B1|1992-10-21|
    BG47031A3|1990-04-16|
    HU204244B|1991-12-30|
    IE872480L|1988-03-16|
    IL83858A|1991-08-16|
    NO873827D0|1987-09-14|
    PT85704B|1990-08-31|
    DK169917B1|1995-04-03|
    YU46715B|1994-04-05|
    CA1307386C|1992-09-15|
    JPS6379770A|1988-04-09|
    EP0261055A3|1990-02-07|
    FI873883A0|1987-09-08|
    JP2612577B2|1997-05-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2663146C1|2017-09-19|2018-08-01|Федеральное государственное бюджетное учреждение науки Институт физики твердого тела Российской академии наук |Key material for high-temperature applications|US2741822A|1951-01-29|1956-04-17|Carborundum Co|Preparation of refractory products|
    US2792214A|1953-11-12|1957-05-14|United States Steel Corp|Furnace lining|
    US3255027A|1962-09-07|1966-06-07|Du Pont|Refractory product and process|
    US3298842A|1963-03-22|1967-01-17|Du Pont|Process for preparing hollow refractory particles|
    US3296002A|1963-07-11|1967-01-03|Du Pont|Refractory shapes|
    US3419404A|1964-06-26|1968-12-31|Minnesota Mining & Mfg|Partially nitrided aluminum refractory material|
    US3473987A|1965-07-13|1969-10-21|Du Pont|Method of making thin-walled refractory structures|
    DE1567844A1|1965-08-13|1970-10-22|Tokyo Shibaura Electric Co|Method of making a sintered mass of aluminum nitride|
    US3421863A|1966-03-04|1969-01-14|Texas Instruments Inc|Cermet material and method of making same|
    US3437468A|1966-05-06|1969-04-08|Du Pont|Alumina-spinel composite material|
    US3789096A|1967-06-01|1974-01-29|Kaman Sciences Corp|Method of impregnating porous refractory bodies with inorganic chromium compound|
    US3473938A|1968-04-05|1969-10-21|Du Pont|Process for making high strength refractory structures|
    US3864154A|1972-11-09|1975-02-04|Us Army|Ceramic-metal systems by infiltration|
    US3973977A|1973-11-01|1976-08-10|Corning Glass Works|Making spinel and aluminum-base metal cermet|
    JPS5217837A|1975-07-31|1977-02-10|Sumitomo Electric Ind Ltd|Path for transmitting leakage light|
    GB1595280A|1978-05-26|1981-08-12|Hepworth & Grandage Ltd|Composite materials and methods for their production|
    US4600481A|1982-12-30|1986-07-15|Eltech Systems Corporation|Aluminum production cell components|
    DE3381519D1|1983-02-16|1990-06-07|Moltech Invent Sa|SINTERED METAL-CERAMIC COMPOSITES AND THEIR PRODUCTION.|
    NZ211405A|1984-03-16|1988-03-30|Lanxide Corp|Producing ceramic structures by oxidising liquid phase parent metal with vapour phase oxidising environment; certain structures|
    NZ212704A|1984-07-20|1989-01-06|Lanxide Corp|Producing self-supporting ceramic structure|
    US4851375A|1985-02-04|1989-07-25|Lanxide Technology Company, Lp|Methods of making composite ceramic articles having embedded filler|
    JPS6283378A|1985-10-07|1987-04-16|Toyota Motor Corp|Manufacture of enhanced silicon nitride sintered body|US5340655A|1986-05-08|1994-08-23|Lanxide Technology Company, Lp|Method of making shaped ceramic composites with the use of a barrier and articles produced thereby|
    US5162273A|1986-05-08|1992-11-10|Lanxide Technology Company, Lp|Shaped ceramic composites and methods of making the same|
    US4828008A|1987-05-13|1989-05-09|Lanxide Technology Company, Lp|Metal matrix composites|
    US4956319A|1987-11-03|1990-09-11|Lanxide Technology Company, Lp|Compliant layer|
    EP0632844B1|1990-05-09|1998-01-07|Lanxide Technology Company, Lp|Production methods for metal matrix composites|
    US6103651A|1996-02-07|2000-08-15|North American Refractories Company|High density ceramic metal composite exhibiting improved mechanical properties|
    DE102006010289B4|2006-03-02|2010-07-01|Deutsches Zentrum für Luft- und Raumfahrt e.V.|Cleavage of sulfuric acid|
    TWI632705B|2013-12-03|2018-08-11|皇家飛利浦有限公司|A method of manufacturing a ceramic light transmitting barrier cell, a barrier cell, a light source and a luminaire|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/907,927|US4824625A|1986-09-16|1986-09-16|Production of ceramic and ceramic-metal composite articles incorporating filler materials|
    [返回顶部]