US20020004105A1 - Laser fabrication of ceramic parts - Google Patents

Laser fabrication of ceramic parts Download PDF

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Publication number
US20020004105A1
US20020004105A1 US09/859,232 US85923201A US2002004105A1 US 20020004105 A1 US20020004105 A1 US 20020004105A1 US 85923201 A US85923201 A US 85923201A US 2002004105 A1 US2002004105 A1 US 2002004105A1
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ceramic
powder
substrate
laser
article
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US09/859,232
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English (en)
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Joseph Kunze
Chaolin Hu
Frank Kuchinski
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Triton Systems Inc
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Triton Systems Inc
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Priority to US09/859,232 priority Critical patent/US20020004105A1/en
Assigned to TRITON SYSTEMS, INC. reassignment TRITON SYSTEMS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HU, CHAOLIN, KUCHINSKI, FRANK, KUNZE, JOSEPH M.
Publication of US20020004105A1 publication Critical patent/US20020004105A1/en
Assigned to AIR FORCE, UNITED STATES reassignment AIR FORCE, UNITED STATES CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: TRITON SYSTEMS, INC.
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/50—Means for feeding of material, e.g. heads
    • B22F12/52—Hoppers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/50—Means for feeding of material, e.g. heads
    • B22F12/55—Two or more means for feeding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention resides in the field of laser fabrication of parts, and more particularly relates to methods of shaping ceramic powder materials to form such parts.
  • Bourell is directed to the production of parts from (1) powders mixed together, such as a mixture of fluorophosphate glass powders and alumina powders; and (2) coated ceramic powders, such as aluminum silicate or silica coated with a polymer (see Column 8, lines 45-60).
  • powders mixed together such as a mixture of fluorophosphate glass powders and alumina powders
  • coated ceramic powders such as aluminum silicate or silica coated with a polymer
  • the selective sintering process of Bourell produces a ceramic part having a density of about 40% to about 65%.
  • a further process/step is required to remove the bonding layer (polymer/wax)—otherwise the part would remain soft and unstable.
  • the further processing step comprises placing the ceramic part in a furnace for post-deposition heating to remove the bonding layer. As the bonding layer is removed, the ceramic particles bond to themselves, but the particles are not melted together.
  • Ceramic parts having a high density and good mechanical properties have not heretofore been produced using a single-step laser deposition method.
  • a novel method and articles obtained by the method are disclosed, where a high density ceramic part is produced by melting together ceramic particles without the use of a bonding agent.
  • the laser power is varied to allow sufficient bonding of the ceramic layer(s) together and to a substrate.
  • the power is controlled in order to prevent plasma reactions which can occur in ceramic powders and cracking of the solid ceramic part.
  • the method employing a laser deposition process, builds the part layer-by-layer in a predetermined configuration.
  • the present invention utilizes the Laser Engineered Net Shaping (LENS) process, in conjunction with one or more ceramic powders, for direct fabrication of a high density ceramic structure or part.
  • the ceramic part is formed by transporting one or more ceramic materials in powder form to a laser device where the ceramic powder(s) are melted and deposited on a substrate to form a ceramic part of high density.
  • the density of the ceramic part can be greater than about 90% to about 100%, and is preferably from about 96% to about 100% dense.
  • Such a high density is achieved according to a method which provides for varying the power of the laser beam during the deposition process.
  • a highly dense ceramic part can be produced by a single laser deposition process, without requiring further steps such as post-deposition heating of the ceramic part in a furnace.
  • a substrate made of a metal, a metal alloy, or a ceramic serves as a base to support the formation of one or more layers of ceramic materials.
  • the ceramic layers are formed by a laser deposition process, where one or more ceramic powders are fed from hopper(s) toward the substrate. A laser beam is directed at the substrate and the powder feed such that ceramic powder is deposited in the desired shape on the substrate. Successive layers of ceramic material are built upon the substrate and the laser beam is adjusted under CAD/CAM control to form a near net shape part in the desired shape. Custom designed cellular structures and complex geometric shapes can be formed.
  • the laser power can be varied during the laser deposition process, in order to create a part having high density in which successive layers bond to one another and the substrate.
  • the laser power is initially set at a high level to create a melt pool.
  • the laser power is gradually reduced so that the powder melts but does not undergo a plasma reaction.
  • the absorptivity of ceramic materials is significantly higher than the metal substrate, and thus reduced heat (and a lower laser power) is required to melt and bond the particles to form layers.
  • the laser power can be selectively varied during the various steps of the laser deposition process.
  • multiple ceramic powder feeds can be employed to create a hybrid ceramic part.
  • a plurality of hoppers can feed different types of ceramic particles, and the hoppers can be selectively controlled to feed an appropriate amount of one or more types of ceramic powders.
  • the multiple feeds can be selectively graded to form a hybrid part having different regions corresponding to different ceramic powders.
  • FIG. 1 is a schematic representation of a laser fabrication process used to form ceramic parts according to the present invention
  • FIG. 2 is an example of a failed ceramic part construction, where a ceramic substrate and ceramic layers were formed at a constant, high laser power;
  • FIG. 3 is a solid, flat specimen made of Al 2 O 3 according to the method of the present invention.
  • FIG. 4 is a solid, tensile specimen made of Al 2 O 3 according to the method of the present invention.
  • FIG. 5 is a hollow, flat specimen with a thin wall made of Al 2 O 3 according to the method of the present invention
  • FIG. 6 is a hybrid ceramic structure made of 50% Al 2 O 3 and 50% AlN according to the method of the present invention.
  • FIG. 7 is a schematic representation of a hybrid ceramic part graded from 100% Al 2 O 3 gradually up to 100% AlN made according to the method of the present invention
  • FIG. 8 is a hybrid ceramic part made according to the specifications of FIG. 7;
  • FIGS. 9 ( a ) and 9 ( b ) are schematic representations of two steps in a method of joining a ceramic deposited material to a hybrid substrate, using the laser deposition process;
  • FIG. 10 is a schematic representation of a particular arrangement for grading ceramic materials in a saw-tooth formation using the laser deposition process.
  • FIG. 11 is a schematic representation of another arrangement for grading ceramic materials using the laser deposition process.
  • Ceramic parts and structures with high density and good mechanical properties are provided according to a method of the present invention.
  • One preferred method of forming the ceramic parts and structures is illustrated in FIG. 1.
  • the method of the present invention is carried out using a laser fabrication apparatus 10 having a first hopper 12 containing ceramic powder 14 , where the first hopper deposits the powder 14 in a feed zone 24 beneath a laser 16 .
  • a laser beam 18 is directed at the feed zone to heat and melt the powder to form a deposition in a structure or part 26 .
  • Material is added to previous depositions formed upon a substrate 30 to gradually build the structure/part.
  • the substrate can be preheated before receiving depositions of the structure/part, but preheating is not required according to the present invention.
  • the powder 14 comprises particles which are preferably of approximately uniform size and consisting of one type of ceramic.
  • the appropriate size of the particles can be determined by one skilled in the art for the materials and equipment used in the laser deposition process.
  • different ceramic powders can be mixed in the first hopper 12 .
  • Ceramic powders which are preferred for use in the present invention include aluminum oxide Al 2 O 3 (also known as “alumina”) and aluminum nitride AlN.
  • Other ceramics which can be used in the present invention are various oxides and non-oxides such as carbides, nitrides, and borides.
  • Ceramics include, but are not limited to the following: ZrO 2 , TiO 2 , MgO, SiC, B 4 C, BN, SiO 2 , Si 3 N 4 , WC, TiC, TiB, TiB 2 , TiN, 3Al 2 O 3 -2SiO 2 , and MgO-Al 2 O 3 .
  • the substrate 30 can be made of a metal, a metal alloy, or a ceramic.
  • the substrate can include a hybrid of one or more of these materials.
  • the substrate can be arranged such that one portion of the substrate comprises Material A and another portion of the substrate comprises Material B (see FIG. 9( a )).
  • the laser 16 is preferably used in the Laser Engineered Net Shaping (LENS) process.
  • the laser is guided under computer control to follow a predetermined pattern to build the structure or part.
  • the laser is operated using computer aided design/computer aided manufacture (CAD/CAM) techniques, where the two-dimensional plane of the substrate 30 contains imaginary x- and y-axes, and the laser moves longitudinally toward and away from the substrate along an imaginary z-axis under control of a computer 28 .
  • CAD/CAM computer aided design/computer aided manufacture
  • Laser fabrication provides for rapid cooling, as the laser beam 18 produces intense heat directed at relatively local regions of the deposited material. Due to the relatively large surface area of the melted material compared to its volume, energy can be removed rapidly and fast cooling is achieved. Fine grain structure is achieved in the part due to the rapid cooling. Because near net shape processing is obtained, the part requires minimal post machining. In fact, no additional steps or processes are required to produce a highly dense part.
  • the substrate 30 is preferably made of a metal or a metal alloy.
  • the substrate can comprise a well known titanium based alloy such as Ti-6Al-4V, also known as Ti64.
  • the laser power is initially set sufficiently high to melt the metal material at the surface of the substrate, thereby creating a melt pool.
  • a laser deposition process e.g. the LENS process
  • Ceramic powder 14 is dispensed through the hopper 12 in a controlled manner. As the powder is deposited in the feed area 24 , the laser 14 is guided under computer control to heat and shape the powder in one or more layers, thereby building the ceramic part 26 .
  • the laser power is varied and thus the amount of heat directed at the substrate and ceramic powder can be controlled.
  • the laser power is initially set at a high level, generally in a range of about 150 W to about 550 W, at a level which can readily be determined by one skilled in the art to melt the substrate to thereby create a melt pool. It is important that a melt pool be created, in order for the ceramic material to bond with the substrate material. As ceramic powder flows into the feed area 24 , the ceramic material forms a layer of ceramic material and bonds with the substrate. Successive layers of ceramic material are deposited on each other and the substrate.
  • the laser power is gradually reduced from the initially high level required to melt the metal substrate to a lower level for melting the ceramic material.
  • the absorptivity of ceramic materials is significantly higher than the metal substrate, so a reduced laser power is required to melt the ceramic powder without vaporizing it.
  • the ceramic substrate is heated to a temperature sufficient to melt the substrate, and then the laser power is adjusted to an appropriate level to melt the ceramic powder as it is deposited.
  • the laser power is reduced during deposition of the ceramic powder, to a level suitable for the type of ceramic powder to be deposited.
  • the laser power should be set at a sufficient level to melt the ceramic powder without causing damage to the ceramic material.
  • a high powered laser beam is directed at the ceramic powder, the powder turns a deep, dark color, indicating a plasma reaction has occurred which results in material evaporation and a porous structure.
  • Such a reaction can be avoided by setting the laser power at a level only high enough to melt the ceramic powder to allow the ceramic powder to bond together.
  • FIG. 2 illustrates an example of problems which can be encountered when attempting to use a laser deposition process to build a ceramic part upon a ceramic substrate.
  • a ceramic substrate made of Al 2 O 3 was used.
  • the substrate was preheated to 500° F. using a hot plate, in order to help prevent cracking of the substrate.
  • a high laser power 375 W
  • the result was thermal shock due to the focus of a high powered laser on a portion of the solid ceramic structure.
  • the thermal shock caused cracking of the ceramic substrate.
  • a ceramic powder made of Al 2 O 3 was fed to the substrate using a laser deposition process.
  • the substrate remained intact, but the deposited material turned to a dark color (black), indicating a plasma reaction had occurred.
  • the laser power was further reduced to 60 W, the deposited material appeared less dark.
  • the deposited layers peeled off the substrate, as there was insufficient bonding between the ceramic substrate and the deposited ceramic material.
  • both the high laser power required to initially create a melt pool on the substrate, and the lower laser power preferred to avoid a plasma reaction in the deposited ceramic material are taken into consideration in selecting reaction parameters.
  • a minimum laser power of approximately 30 W is typically required for the laser fabrication device described with reference to FIG. 1 to function properly.
  • a solution to the above-described problems is to initially set the laser power at a high level and gradually reduce the power as the deposited ceramic material bonds to the substrate.
  • a metallic substrate Ti-6Al-4V alloy, also known as “Ti64” was selected.
  • a minimum power of about 150 W is required to melt the Ti64, which is beyond the acceptable range of laser power for heating the ceramic powder.
  • the laser was initially set at about 250 W to melt the Ti64 surface, and the power was gradually reduced to about 60 W during ceramic powder deposition. Parts fabricated according to this method are shown in FIGS. 3 - 5 .
  • FIG. 3 is a photograph of a solid, flat bar which was fabricated from Al 2 O 3 ceramic powder.
  • FIG. 4 is a photograph of a solid, tensile cylindrical bar also fabricated from Al 2 O 3 ceramic powder.
  • the part depicted in FIG. 4 shows that the laser deposition process can be used to produce parts with complex geometric shapes. Parts with delicate geometries can also be produced, as shown in FIG. 5.
  • FIG. 5 is a hollow, flat specimen made from Al 2 O 3 ceramic powder, the final part having external dimensions of 3 in. ⁇ 0.5 in. ⁇ 0.08 in. with a thin wall less than 1 mm thick prepared using the laser deposition process.
  • the density of the above fabricated parts was measured using the standard water absorption method (ASTM designation: C373-56) well known in the art for obtaining accurate and reliable density calculations.
  • the average density of the above fabricated Al 2 O 3 parts is 3.80 g ⁇ cm 3 which indicates 0.962 densification of the theoretical density of Al 2 O 3 (3.95 g ⁇ cm 3 ).
  • the finished ceramic parts were, on average, about 96% dense.
  • the density of parts or structures fabricated according to the present invention are preferably greater than about 90%, and are up to about 100% dense, but preferably in the range of from about 96% to about 100% dense.
  • the high density of ceramic parts produced according to this method is achieved by using a metallic substrate and varying the power of the laser beam as discussed herein.
  • Ceramic powder comprising Al 2 O 3 is useful with the present invention, because Al 2 O 3 powders generally have good fluidity and are commonly used for a variety of applications. While Al 2 O 3 is one preferred type of ceramic powder suitable for use in the present invention, other types of ceramic powders can also be used, either alone or in conjunction with Al 2 O 3 .
  • Another preferred ceramic powder is AlN, which often includes some fine particulates which tend to clog up the hoppers and feed system. Thus, when using AlN powder, the powder can be filtered and treated with a sufficient amount of fluid and dispersant to remove the fine particles. The remaining powder has a much better fluidity and can be successfully used in the laser fabrication device.
  • a multiple feed laser fabrication apparatus is shown, where the apparatus includes a second hopper 20 containing a second ceramic powder 22 which can be controllably released toward the feed area 24 .
  • the second hopper can contain the same type of ceramic powder as the first hopper 12 , in order to allow for continuous part fabrication when building, e.g., a large part or a plurality of uniform parts.
  • the second hopper 20 can also be used to store particles corresponding to a different type of ceramic powder from that stored in the first hopper 12 .
  • FIG. 6 is a photograph of a part produced by this method. As shown in FIG. 6, approximately the first one-half of the length of the part was fabricated using Al 2 O 3 powder; the other half was fabricated using a dual feed mixture of about 50% Al 2 O 3 and about 50% AlN. As described herein, the graded structures are made from powders with approximately the stated percentage of the material. It is possible that a small amount of impurities can be present in the finished part.
  • the first hopper 12 contained Al 2 O 3 powder and the second hopper 20 contained AlN powder.
  • the fabrication process involved feeding exclusively from the first hopper, while approximately the other half was produced with simultaneous feeding from the first and second hoppers.
  • the result was a solid graded part with no visible defects and a smooth interface between the 100% Al 2 O 3 and the 50% Al 2 O 3 /50% AlN sections.
  • FIG. 7 depicts a specification for a part graded from 100% Al 2 O 3 gradually to 100% AlN.
  • the specification calls for a 100% Al 2 O 3 section, followed by a 50% Al 2 O 3 /50% AlN section, and then a 25% Al 2 O 3 /75% AlN section, where each of these sections is produced using a laser power of 125 W.
  • the next section is 100% AlN produced under a laser power of 14-5 W.
  • the change in laser power for the AlN section is motivated by the different physical properties of AlN.
  • Aluminum nitride has a higher thermal conductivity and a lower laser energy absorption than alumina.
  • FIG. 8 is a photograph of a graded ceramic part produced according to the specification of FIG. 7. As seen in FIG. 8, the transitions between the various graded sections are smooth. Only the 25% Al 2 O 3 /75% AlN experienced some bonding problems, which was likely due to insufficient laser power caused by the higher percentage of AlN as compared to the other sections having Al 2 O 3 .
  • the laser power can be varied according to the present invention to allow for an increase in laser power for the 25% Al 2 O 3 /75% AlN section, where the applied laser power would be in the range of approximately 125 W-145 W.
  • FIGS. 9 ( a ) and 9 ( b ) illustrate two steps in a process of depositing a ceramic material on a hybrid substrate.
  • the starting substrate material comprises “Material A” and “Material B” which can be metals, metal alloys, or ceramic materials. Metals or metal alloys are preferred, in order to provide sufficient bonding with the deposited ceramic material, for reasons stated above.
  • the “deposited material” can be a ceramic material deposited by the aforementioned laser deposition process.
  • the ceramic material can also comprise a graded ceramic structure.
  • the ceramic materials graded in a structure or part can be deposited in a variety of formations.
  • FIG. 10 illustrates a saw tooth formation with “Ceramic C” on one side and “Ceramic D” on the other side of the structure.
  • the grading can be arranged using interlocking teeth, with “Ceramic E” on one side and “Ceramic F” on another side of the structure.
  • the method and article produced according to the present invention are not limited to the above-mentioned graded parts or structures.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Laser Beam Processing (AREA)
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US20090293672A1 (en) * 2008-06-02 2009-12-03 Tdy Industries, Inc. Cemented carbide - metallic alloy composites
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