EP1380809B1 - Corps composite céramique - Google Patents

Corps composite céramique Download PDF

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Publication number
EP1380809B1
EP1380809B1 EP20030015441 EP03015441A EP1380809B1 EP 1380809 B1 EP1380809 B1 EP 1380809B1 EP 20030015441 EP20030015441 EP 20030015441 EP 03015441 A EP03015441 A EP 03015441A EP 1380809 B1 EP1380809 B1 EP 1380809B1
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Prior art keywords
region
metal
silicon carbide
composite body
carbide particles
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German (de)
English (en)
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EP1380809A2 (fr
EP1380809A3 (fr
Inventor
Bodo Benitsch
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SGL Carbon SE
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SGL Carbon SE
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0414—Layered armour containing ceramic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249956—Void-containing component is inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249956—Void-containing component is inorganic
    • Y10T428/249957—Inorganic impregnant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967—Inorganic matrix in void-containing component
    • Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249981—Plural void-containing components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/24999—Inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2615—Coating or impregnation is resistant to penetration by solid implements
    • Y10T442/2623—Ballistic resistant

Definitions

  • the invention relates to ceramic composite bodies comprising at least two layers, in particular for protective armor, which are suitable for civil and military applications.
  • the invention relates to bodies of a multilayer material composite containing predominantly silicon carbide (SiC), comprising an outer material layer composed essentially of SiC bound in a matrix of free silicon (Si) and an inner material layer containing loosely bound SiC ceramic powder, and a method for their preparation and uses of these composites.
  • SiC silicon carbide
  • the protective armor component In the military sector, a threat of high-speed and large-caliber missiles and explosive missiles is assumed. Although the demands on the component thickness and installation depth are lower than in the civil sector, a low specific weight of the armor material is of crucial importance here, too, because of the extremely high demands on the energy absorbing effect, the protective armor component must generally be made very thick.
  • An armor made of one or more armor steel plates is usually treated so that at least the threat facing side is extremely hard and thus bullet-breaking.
  • the side facing away from the threat is ductile or toughened to absorb the energy of the projectile through material deformation. From this results also the structure typical for armor plates from other materials.
  • the ceramic materials have the advantage of higher hardness and lower specific weight. Since the monolithic ceramic shows a typical brittle fracture behavior during firing, ceramic plates (monolithic ceramics) burst to form many coarse to fine splinters. The use of ceramic plates without additional backing (support material and splinter trap) on the side facing away from the entrance of the projectile is not useful due to the splitter exit during firing. The bombardment generally completely destroys the respective ceramic plate. A multiple shot (multi-hit) can then no longer be held.
  • An armor with ceramic materials consists for these reasons preferably of two layers.
  • the front panel of monolithic ceramics as possible has the task of deforming the rest of the bullet and possibly breaking the hard core.
  • a deformable reinforcement, the backing, attached behind the ceramic plate, has the task of catching or absorbing the bullet, scraps and ceramic fragments and the remaining ceramic plate stabilize. It is also called absorber layer in the following.
  • the backing generally consists of highly stretchable and tear-resistant fabrics (aramid fiber fabric, HDPE fabric, etc.), metal or plastics.
  • a multilayer armor plate which consists of a conventional ceramic plate as a front plate and an underlying absorber plate of so-called chemically bound ceramic.
  • the chemically bonded ceramic consists of hard fillers, such as fibers or ceramic powders, and a binder phase (or matrix) of cements modified with organic or inorganic polymers, which cure at low temperatures.
  • the hard fillers lead to a blunting, deflection and fragmentation of the projectile.
  • a composite body having the features of the preamble of claim 1 is known from US-A 2002028294.
  • a composite body comprising at least two layers, characterized in that an outer bullet-breaking ceramic layer (front panel) consists essentially of a carbide and a carbide-forming metal, preferably SiC and Si (material layer A), and one with this firmly bonded inner layer (material layer B) containing weakly or loosely bound ceramic powder consisting essentially of SiC.
  • an outer bullet-breaking ceramic layer front panel
  • a carbide-forming metal preferably SiC and Si
  • material layer B preferably weakly or loosely bound ceramic powder consisting essentially of SiC.
  • a method for producing such a composite body in which the multilayer composite material is produced by the liquid infiltration of a porous green body of ceramic particles and carbon material by a carbide-forming metal, in particular silicon metal, wherein the liquid metal infiltration in a single common process step both the outside Ceramic layer of carbide and carbide-forming metal, preferably SiC and Si (material layer A), as well as the inner layer of weakly or loosely bound ceramic powder of predominantly SiC (material layer B) is formed, and both layers are firmly bonded together chemically.
  • a carbide-forming metal in particular silicon metal
  • the invention is based on the finding that powdered or particulate ceramic, similar to a sand bed, a very favorable absorption behavior against ballistic action shows, if the powdery material is mechanically stabilized, or held together.
  • This cohesion is achieved according to the invention by the chemically firmly bonded ceramic layer (material layer A), as well as by the sintering process of the ceramic mixture of the green body in the region of the material layer B taking place during the metal melt infiltration.
  • the composite body according to the invention therefore comprises at least two layers, an outer material layer A containing phases of a carbide-forming metal and the carbide of this metal, preferably reaction bonded silicon carbide (SiC) and silicon, also referred to as SiSiC, and an underlying material layer B, through Sinter loosely bound SiC ceramic powder or optionally contains additional layers arranged behind it, in particular of the material A or of fiber-containing backing. Through these additional layers, the energy-absorbing effect of the armor is further improved. Under loosely bonded ceramic powder, or particles in particular material is to be understood, the strength of which is at least 20% below that of the material of the material layer A.
  • liquid metal infiltration - preferably with a silicon melt - a ceramic is formed in the material layer A by reaction of the carbide-forming metal with carbon, which in addition to very high hardness has a good fracture toughness or damage tolerance.
  • the infiltration metal used is preferably an alloy containing at least a mass fraction of 50% silicon, with particular preference being given to technical silicon or pure silicon.
  • Fe, Cr, or Ni is preferably formed from the carbon contained in the precursor of the material layer A silicon carbide.
  • titanium carbide preferably forms in addition to silicon carbide from the carbon.
  • the particles of silicon carbide and nitrides contained in the material layer B are sintered together at the temperature of infiltration with the liquid metal at the points of contact, forming a loose structure with pores.
  • the non-volatile pyrolysis products of the organic binder of the raw material mixture also contribute to the strength of the material layer B.
  • the material layer A preferably contains a mass fraction of at least 70% of SiC particles embedded in a matrix of free silicon.
  • the mass fraction of SiC is preferably above 75% and particularly preferably above 85%.
  • the mass fraction of free silicon which is to be understood as including all mixed silicon phases with other metallic elements, above 2.8%.
  • the mass fraction of free silicon is preferably in the range from 3 to 21% and particularly preferably in the range from 3 to 15%.
  • the Material layer A is constructed so that the highest possible hardness is achieved, which can be achieved, for example, by the highest possible density, ideally the theoretical density.
  • the porosity (volume fraction of the pores in the entire volume) of the material layer A is below 20% or the density at least 2.1 g / cm 3, and more preferably the porosity is below 10% or the density above 2.2 g / cm 3 .
  • the material A still free carbon, and optionally ceramic aggregates in mass fractions of about 0.5 to 15%.
  • Particularly preferred ceramic additives used according to the invention are particularly hard nitride-based ceramics. These include in particular the nitrides of the elements Si, Ti, Zr, B and Al.
  • the average particle size of the SiC which can be used for both the material layer A and for the material layer B, is typically in the range of 20 to 750 microns. Since, in general, a homogeneous green body (preliminary body of the metal infiltration) is generally produced from the ceramic powders for reasons of process, the particle sizes in the material layers A and B only differ insignificantly. Likewise, it is also possible to provide different particle sizes for the layers, in which case the material layer A preferably contains finer material than the material layer B. The average particle size in layer A is then more preferably below 50 ⁇ m and in layer B above 50 ⁇ m.
  • the material layer B is preferably constructed predominantly of SiC particles.
  • the mass fraction of SiC particles is preferably above 70% and particularly preferably above 90%.
  • the content of ceramic aggregates is also comparable to those in layer A.
  • the material layer B preferably contains at least one of the nitrides of the elements Si, Ti, Zr, B and Al in mass fractions of 0.05 to 15%.
  • Substantially different from the material A is the material in the material layer B, the ceramic, or their ceramic particles, not reaction bound by silicon, there is almost no matrix of silicon or a silicon alloy.
  • the mass fraction of free silicon or of silicon / metal phases is typically below 5%, preferably below 2.5% and particularly preferably below 1%.
  • the ceramic particles in the material layer B are only weakly bound, partly via carbon binder phases, partly directly via sintered bridges with one another.
  • the material layer B therefore has a comparatively high porosity, which typically ranges from 5% to 35%, and is preferably in the range of 12 to 27%.
  • the density of the material layer B is generally below 2.55 g / cm 3 , preferably below 2.05 g / cm 3 and more preferably below 1.96 g / cm 3 .
  • the porosity in the material layer B is at least 7% higher than in the material layer A.
  • the only loose bond between the ceramic particles is essential. Among other things, this prevents the crack propagation typical of the brittle fracture through large areas of a contiguous workpiece part, while nevertheless utilizing the hardness of the ceramic particles. This effect is also achieved if the pores in this layer are filled by material which is much softer than the ceramic.
  • the spaces between the ceramic particles in the material layer B are filled with a soft material.
  • a plastic or a metal is used as a soft material, wherein the metal has a hardness on the Mohs scale of at most 5.
  • thermoplastic polymers, resins, adhesives, elastomers or aluminum are particularly suitable.
  • at least half of the space formed between the ceramic particles is filled with the soft material.
  • the application of the composite body according to the invention is in the field of protective armor, in particular against ballistic action. Due to the good thermal properties, in particular the high melting or decomposition point of SiC, the composite material also shows good suitability as armor material in safe and protective building construction.
  • Components of the composite bodies according to the invention are usually designed so that the total thickness of the material layers A and B is in the range of 6 to 300 mm.
  • Other layers, in particular of the material A or fiber-containing backing can be arranged behind the layer of the material B.
  • the layer thickness of the material A is usually above 1 mm, for armor plates preferably above 3 mm.
  • the layer thickness ratio of the material layers A and B is typically below 1:50, preferably below 1:10, whereby only the front side of the material A facing the firing side and the subsequent layer of the material B are to be understood here.
  • the material layer A merges into the material layer B, wherein the transition is generally to be recognized by a significant decrease in the content of silicon in the matrix.
  • Fig. 1 shows a microscopic cross-section of the interface between the material layers A and B of a composite body according to the invention.
  • the gray areas (1) are SiC particles which are distributed approximately uniformly over the entire area.
  • the SiC regions are connected by a continuous light phase (2). This is the matrix of silicon.
  • the lower half (B), which corresponds to the material B, has pores instead of the matrix (black areas, 3).
  • the other constituents of carbon or nitride particles can not be distinguished in this illustration from the other materials.
  • the layer sequence of a front plate made of the material A, an absorber zone made of the material B and back plate (or backing) made of the material A is particularly preferred for flat components.
  • the composite bodies are produced by the metal-liquid infiltration of SiC, carbon and nitride-containing porous green bodies.
  • the porous carbonaceous green body In the preparation of the porous carbonaceous green body, a mixture of the solids containing silicon carbide, nitrides, optionally carbon and organic binder is first prepared. This mixture is shaped according to the usual methods of the ceramics industry (including pressing, injection molding, slurrying) in which the curing of the organic binder is responsible for the strength of the resulting body. The cured body is then carbonized by a temperature treatment in the range of about 650 to 1600 ° C, preferably 1000 ° C.
  • the organic binder is carbonizable, that is, when heated under non-oxidizing conditions, the binder is not completely volatilized, but forms a carbon residue.
  • the resulting body, the green body now consists of the solids used, in particular the ceramic particles, which are held together by a binder phase of pyrolytically generated carbon.
  • the composition of the starting mixture is preferably selected such that the mass fraction of silicon carbide in the porous carbon-containing green body is at least 50%, preferably at least 65%.
  • the mass fraction of carbon, of carbonized binder and solids used is typically above 4% and preferably above 8%, the content by mass of nitrides above 1%, preferably above 3% and particularly preferably between 3 and 12%.
  • the nitrides are in particular selected from at least one of the nitrides of the following elements: Ti, Zr, Si, B and Al.
  • the solid carbon material is selected from coal, coke, natural graphite, engineering graphite, carbonized organic material, carbon fibers, glassy carbon and coking products. Particularly suitable are natural graphite or synthetic graphite.
  • An essential advantage of the invention is that expensive carbon fibers can be dispensed almost completely or completely.
  • the invention it is also possible to produce a multilayer green body from different starting mixtures.
  • preference is given to compositions in which the region corresponding to the later material layer B has a higher content of nitrides. This advantageously influences the ballistic behavior of the multilayer composite body.
  • step b) the feeding of a molten metal, a carbide-forming metal is infiltrated into the porous green body.
  • the infiltration is assisted by the capillary action and the chemical reaction between the free carbon of the green body with the carbide-forming metal taking place during the infiltration.
  • the infiltration is carried out at reduced pressure or vacuum, at temperatures of about 150 ° C above the melting temperature of the infiltration metal.
  • infiltration metal silicon alloys typically of Si and at least one of the elements Ti, Fe, Cr and Mo, and particularly preferably technically pure Si are preferably used.
  • the pores of the green body are filled with infiltration metal and its reaction products with carbon in the outer region, while the inner region remains substantially free of infiltration metal and / or its reaction products with carbon.
  • the mass fraction of infiltration metal supplied by the infiltration inside the composite material according to the invention, corresponding to the material layer B, is typically below 1%, and the mass fraction of metal carbide newly formed by the infiltration metal is below 3%.
  • the chemical composition and the porosity of the green body and the infiltration metal offer are selected so that the green body is only partially infiltrated.
  • the ratio of carbides, carbon and nitrides the depth of infiltration can be controlled specifically.
  • the nitrides worsen the wetting of the green body with the molten silicon. In particular, this reduces the infiltration depth of the silicon-containing melt and controls the degree of conversion of the green body.
  • step c) the reaction of at least part of the free carbon with the infiltration metal takes place.
  • the temperature and process duration of the turnover can be controlled.
  • the material layers A and B are formed.
  • a dense ceramic of reaction-bonded metal carbide in the preferred case of infiltration with liquid silicon, ie SiSiC, is formed.
  • a sintering reaction takes place between the ceramic particles at the temperature of step c), which inter alia leads to a mechanical stabilization of the material layer.
  • the strength (breaking strength) must only be so high that the material B is manageable and does not readily decay.
  • the actual mechanical stabilization of the material layer B takes place via the firmly bonded material layer A.
  • the strength of the layer B can be increased if sintering aids which preferably contain Si compounds or powder are added to the mixture for the green body.
  • the molten metal is usually supplied via wicks or metal powder spills. Typically, the metal infiltration takes place substantially over the entire surface, so that the material layer A results in a closed material surface. If plate-shaped green bodies are used, the result is a component which, in the direction of the surface normal, the preferred direction of the ballistic threat, has the layer sequence of the material layers ABA.
  • the mechanical stability of the material layer B can be improved without losing the typical properties of a loose powder bed similar properties of the invention, if the pores of the material B are additionally filled by a soft material.
  • a soft material This can be achieved, for example, by melt infiltration with a thermoplastic polymer or by liquid infiltration with a polymer resin.
  • the pores are filled with polyolefins or epoxy resins at least 30%.
  • the pores are infiltrated with adhesives, which are particularly suitable for bonding with a backing.
  • backing materials made of aramid fibers are particularly suitable.
  • the composite body in particular the material layer B, with a light metal, in particular Al, infiltrated.
  • the residual porosity of the layer B is preferably below 15%.
  • the filling of the pores of the material layer B with a polymer can be used particularly advantageously for bonding with a backing, in particular a backing made of fiber mats or fabrics.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Products (AREA)
  • Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Claims (21)

  1. Corps composite contenant des particules de carbure de silicium et un liant carbonisé ,
    une partie extérieure A du corps composite étant infiltrée avec un métal formant un carbure, de telle sorte qu'existe dans cette partie extérieure des phases constituées de ce métal et de son produit de réaction avec le carbone,
    caractérisé en ce que
    il existe, dans une partie intérieure B du corps composite exempte de métal d'infiltration, une structure lâche constituée de particules de carbure de silicium liées par des ponts de frittage et les résidus de pyrolyse non volatils du liant carbonisé, qui présente une fraction volumique de pores de 10 % à 35 %,
    la partie extérieure A et la partie intérieure B s'interpénètrent, et
    la résistance de la matière dans la partie B est d'au moins 20 % inférieure à la résistance de la matière dans la partie A.
  2. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce que
    la partie A présente une fraction volumique de pores inférieure à 20 % et la partie B, une fraction volumique de pores de 5 à 35 %.
  3. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce que
    la partie B présente une fraction volumique de pores de 12 à 27 %.
  4. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce que
    la partie A présente une masse volumique supérieure à 2,1 g/cm3 et la partie B une masse volumique inférieure à 2,55 g/cm3.
  5. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce qu'
    il est infiltré de plusieurs côtés avec le métal formant un carbure, de telle sorte qu'il comporte trois parties, les parties extérieures A étant infiltrées avec du métal et la partie intérieure B étant essentiellement exempte de métal d'infiltration.
  6. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce que
    la partie B contient une fraction massique d'au moins 70 % de carbure de silicium.
  7. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce qu'
    au moins la partie B contient des nitrures d'au moins un des éléments silicium, titane, zirconium, bore et aluminium.
  8. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 7,
    caractérisé en ce que
    les parties A et B présentent la même fraction massique de nitrures.
  9. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 7 ou 8,
    caractérisé en ce que
    la fraction massique des nitrures se trouvant dans la (les) partie(s),A et/ou B est de 0,05 à 15 %.
  10. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce que
    la partie A présente une fraction massique d'au moins 70 % de carbure de silicium.
  11. Corps composite contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce qu'
    au moins une partie du volume non rempli de SiC dans la partie B est remplie par des plastiques, des résines plastiques, des élastomères, des colles ou des métaux d'une dureté maximum de 5 sur l'échelle Mohs.
  12. Procédé de production de corps composites contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1,
    caractérisé en ce que
    dans une première étape se trouve produite une ébauche qui contient du carbure de silicium et un nitrure métallique sous forme d'une poudre et un liant organique carbonisable,
    on carbonise cette ébauche dans une deuxième étape par chauffage dans une atmosphère non oxydante à des températures situées dans la plage de 650°C à 1800°C pour former un corps de carbone poreux , et
    dans une troisième étape, on infiltre le corps de carbone depuis un ou plusieurs côté(s) avec un métal fondu contenant du silicium, en choisissant la température de telle sorte qu'au moins une partie du carbone réagisse avec le métal et/ou le silicium pour former des carbures,
    la quantité de métal fondu et de nitrure métallique étant choisie de telle sorte que la partie intérieure du corps reste essentiellement exempte du métal et/ou du silicium.
  13. Procédé selon la revendication 12,
    caractérisé en ce que
    le métal fondu contenant du silicium contient une fraction massique d'au moins 25 % de silicium.
  14. Procédé selon la revendication 12,
    caractérisé en ce que
    les nitrures métalliques dans l'ébauche sont choisis parmi le nitrure de titane, le nitrure de zirconium, le nitrure de silicium, le nitrure de bore ou le nitrure d'aluminium.
  15. Procédé selon la revendication 12,
    caractérisé en ce que
    l'ébauche contient en outre du carbone sous forme de coke, graphite naturel, graphite synthétique, matière organique carbonisée ou carbone vitreux.
  16. Procédé selon la revendication 12,
    caractérisé en ce que
    la porosité restant dans le corps composite après l'infiltration avec un métal fondu contenant du silicium, est remplie au moins partiellement avec un plastique, une résine plastique, des élastomères, une colle ou un métal d'une dureté maximum de 5 sur l'échelle de Mohs.
  17. Utilisation de corps composites contenant des particules de carbure de silicium et un liant carbonisé selon la revendication 1, sous forme de plaques comme blindage de protection.
  18. Utilisation selon la revendication 17,
    caractérisée en ce que
    l'épaisseur totale des plaques avec les parties A et B se trouve dans une plage de 6 à 300 mm.
  19. Utilisation selon la revendication 17 ou 18 ,
    caractérisée en ce que
    le rapport d'épaisseurs de la partie A orientée vers la direction de sollicitation et de la partie B est au maximum de 1/20.
  20. Utilisation selon la revendication 18,
    caractérisée en ce qu'
    on utilise des plaques qui, dans la direction de la menace balistique, ont une partie A infiltrée avec un métal formant un carbure suivie d'une partie B essentiellement exempte de métal d'infiltration et d'une partie A infiltrée avec un métal formant un carbure.
  21. Utilisation selon la revendication 18 ou 20,
    caractérisée en ce que
    le côté des plaques opposé à la direction de sollicitation est renforcé avec une couche de matière fibreuse ou de textiles.
EP20030015441 2002-07-10 2003-07-09 Corps composite céramique Expired - Lifetime EP1380809B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10231278 2002-07-10
DE2002131278 DE10231278A1 (de) 2002-07-10 2002-07-10 Keramische Verbundkörper

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EP1380809A2 EP1380809A2 (fr) 2004-01-14
EP1380809A3 EP1380809A3 (fr) 2004-05-26
EP1380809B1 true EP1380809B1 (fr) 2006-10-11

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US (1) US7128963B2 (fr)
EP (1) EP1380809B1 (fr)
AT (1) ATE342485T1 (fr)
DE (2) DE10231278A1 (fr)
ES (1) ES2274146T3 (fr)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR876M (fr) 1960-10-12 1961-10-16
CA2483231C (fr) * 2004-09-30 2011-11-29 Aceram Technologies Inc. Systeme de blindage en ceramique avec revetement de diamant
US7661228B1 (en) 2005-05-06 2010-02-16 Kontek Industries, Inc. Armored building modules and panels
US20110113950A1 (en) * 2006-01-10 2011-05-19 Reed Charles K Composite material having a layer including entrained particles and method of making same
DE102006031113B4 (de) * 2006-06-28 2009-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines keramischen Verbundwerkstoffes
US8689671B2 (en) 2006-09-29 2014-04-08 Federal-Mogul World Wide, Inc. Lightweight armor and methods of making
JP4327190B2 (ja) * 2006-10-11 2009-09-09 日本碍子株式会社 Ｓｉ−ＳｉＣ質焼結体及びその製造方法
US9116428B1 (en) 2009-06-01 2015-08-25 Hrl Laboratories, Llc Micro-truss based energy absorption apparatus
US8087339B2 (en) * 2007-07-24 2012-01-03 Foster-Miller, Inc. Armor system
BRPI0817615A2 (pt) * 2007-09-28 2015-03-31 Gen Dynamics Land Systems Inc Aparelho, métodos e sistemas para aperfeiçoar proteção de blindagem leve
US8105967B1 (en) 2007-10-05 2012-01-31 The United States Of America As Represented By The Secretary Of The Navy Lightweight ballistic armor including non-ceramic-infiltrated reaction-bonded-ceramic composite material
US7685922B1 (en) 2007-10-05 2010-03-30 The United States Of America As Represented By The Secretary Of The Navy Composite ballistic armor having geometric ceramic elements for shock wave attenuation
US8155496B1 (en) * 2009-06-01 2012-04-10 Hrl Laboratories, Llc Composite truss armor
JP5735501B2 (ja) * 2009-07-07 2015-06-17 モーガン・アドヴァンスト・マテリアルズ・アンド・テクノロジー・インコーポレイテッドＭｏｒｇａｎ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ Ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃ． 硬質非酸化物又は酸化物セラミック／硬質非酸化物又は酸化物セラミック複合体ハイブリッドシール部品
JP5737547B2 (ja) * 2009-09-04 2015-06-17 東洋炭素株式会社 炭化ケイ素被覆黒鉛粒子の製造方法及び炭化ケイ素被覆黒鉛粒子
USD630385S1 (en) 2010-01-11 2011-01-04 Soldier Technology and Armor Research Industries, LLC Shin guard protection system
USD644380S1 (en) 2010-01-11 2011-08-30 Soldier Technology and Armor Research Industries, LLC Upper arm protection system
USD628753S1 (en) 2010-01-11 2010-12-07 Soldier Technology and Armor Research Industries, LLC Forearm protection system
USD638583S1 (en) 2010-01-11 2011-05-24 Soldier Technology and Armor Research Industries, LLC Torso protection assembly
US20110231985A1 (en) * 2010-01-12 2011-09-29 Bishop Lyman J Body Armor Protection System
US9696122B2 (en) 2011-06-30 2017-07-04 Imi Systems Ltd. Antiballistic article and method of producing same
IL213865A (en) 2011-06-30 2017-02-28 Bergman Ron Anti-ballistic product and method of manufacture
US9366506B2 (en) 2012-09-19 2016-06-14 Aps Materials, Inc. Coated ballistic structures and methods of making same
IL230775B (en) 2014-02-02 2018-12-31 Imi Systems Ltd Pre-stressed curved ceramic panels/tiles and a method for their production
FR3053776B1 (fr) 2016-07-11 2019-04-05 Saint-Gobain Centre De Recherches Et D'etudes Europeen Plaque de blindage
WO2019077310A1 (fr) * 2017-10-20 2019-04-25 Bae Systems Plc Ensemble blindage
EP3473965A1 (fr) * 2017-10-20 2019-04-24 BAE SYSTEMS plc Ensemble de blindage
KR20220035439A (ko) * 2019-07-17 2022-03-22 필립스 66 컴퍼니 배터리에 적합한 전극 입자
FR3112201B3 (fr) 2020-07-02 2022-07-01 Saint Gobain Ct Recherches Element de blindage profile
CN113912405A (zh) * 2020-07-09 2022-01-11 南京航空航天大学 一种混编纤维预制体增强的复合材料及其制备方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954483A (en) * 1974-01-08 1976-05-04 General Electric Company Dense polycrystalline silicon carbide
US4120731A (en) * 1976-02-23 1978-10-17 General Electric Company Method of making molten silicon infiltration reaction products and products made thereby
WO1986005482A1 (fr) * 1985-03-12 1986-09-25 Kitamura Valve Co., Ltd. Soupape a corps de soupape en un compose ceramique
EP0287918A1 (fr) * 1987-04-13 1988-10-26 Cemcom Corporation Matériau de blindage céramique formé par liaison chimique
FR2642419A1 (fr) * 1988-12-19 1990-08-03 Europ Propulsion Materiau de protection a structure ceramique multi-couches
US5432253A (en) * 1989-12-18 1995-07-11 General Electric Company Composite containing fibrous material
JPH05221723A (ja) * 1992-02-07 1993-08-31 Toshiba Ceramics Co Ltd Ｓｉ−ＳｉＣ複合材料
US5580834A (en) * 1993-02-10 1996-12-03 The Morgan Crucible Company Plc Self-sintered silicon carbide/carbon graphite composite material having interconnected pores which may be impregnated and raw batch and process for producing same
DE4438456C2 (de) * 1994-10-28 2002-07-11 Deutsch Zentr Luft & Raumfahrt Reibeinheit
DE19642506C1 (de) * 1996-10-15 1997-10-23 Sibco Gmbh Erzeugnis auf der Basis von Kohlenstoff und Kohlenfaserstoffen, Karbiden und/oder Di-Karbiden und Verfahren zu seiner Herstellung sowie Verwendung des Erzeugnisses
JP4014254B2 (ja) * 1997-07-18 2007-11-28 日本碍子株式会社 Ｓｉ濃度段階的変化型Ｓｉ−ＳｉＣ材料及びＳｉ濃度段階的変化型ＳｉＣ繊維強化Ｓｉ−ＳｉＣ複合材料並びにこれらの製造方法
JP3652900B2 (ja) * 1997-12-16 2005-05-25 日本碍子株式会社 繊維複合材料およびその用途
DE19834018C1 (de) * 1998-07-28 2000-02-03 Deutsch Zentr Luft & Raumfahrt Verfahren zum Erzeugen einer Siliziumkarbid enthaltenden Schutzschicht
DE19947731B4 (de) * 1999-10-05 2005-06-23 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahren zur Herstellung eines Bauteils aus SiC-Keramik sowie danach hergestelltes Halbzeug

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Publication number Publication date
US7128963B2 (en) 2006-10-31
EP1380809A2 (fr) 2004-01-14
DE50305325D1 (de) 2006-11-23
ATE342485T1 (de) 2006-11-15
DE10231278A1 (de) 2004-02-05
ES2274146T3 (es) 2007-05-16
EP1380809A3 (fr) 2004-05-26
US20040197542A1 (en) 2004-10-07

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