TWI262109B - Stabilized grain size refractory metal powder metallurgy mill products - Google Patents

Abstract

A powder metal (P/M) mill product and the method of fabrication such product made out of low oxygen (<= 400 ppm) refractory metal, or alloys thereof, using oxide additive (such as MgO, SiO2, and Y2O3) for co-fabrication to achieve refractory metal grain size stabilization as required in high temperature applications. One such product is a sheet with small grain size containing oxide particles as grain size stabilizers. The product has good mechanical properties, low oxygen content in refractory metal fiber derivatives of the powder within the mill product and it is available as large pieces of sheet (lateral dimensions). The metal powder is consolidated to a sheet bar by different methods, which may weigh 50 pounds or more.

Description

1262109 A7 B7 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Field of the Invention The present invention relates generally to metal rolled products (and preforms) made of powders of refractory metals comprising elemental metals and alloys thereof, more specifically The use of an oxide dopant for the purpose of stabilizing the crystal grain size of the rolled product and the preform in the X-South temperature application and/or high-temperature process. Prior Art Refractory metal users have long been interested in using Sharp instead of Syria. To replace the group, the driving force lies in the price of the group and its limited availability. Many dairy 10 products involve exposure to high temperature environments during manufacturing and/or use. High temperatures can cause crystal growth. In the various accounts, the large grains caused by such grain growth hinder the performance of the material. This is a limiting factor in replacing the group with 铌. Other limiting factors include the low strength and hardness of the bismuth and its alloys in the finished state. For today's eye-catching areas include the production of hybrid 15 parts, sintered discs and deep-drawn cups. These products require materials of small grain size. Hose parts require materials with low grain growth over their service life to prevent premature deterioration of mechanical properties. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. Today's materials for metal wires or sheets are stabilized grain sizes due to alloying additives or other artifacts. In an embodiment or interaction state 20 1 ', Si 〇 2 is used as a - grain stabilizer. The disadvantage of this method of manufacturing a grain size stabilized niobium powder/powder (P/Μ) material (resistance to sintering) is that it is limited to the weight of the crucible and the amount of each batch of about 15 pounds. We expect to make a batch of up to 1000 pounds and 5 pounds. Today's large P/Μ sheet size/strip length manufacturing methods do not provide large sheets or long rolls with the same low oxygen content and good mechanical properties. S-*~~ _ ___ The paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇 X 297 public Chu) 1262109

V. INSTRUCTIONS (2) The powder metallurgy of the invention belongs to the production of low-calorie content and large quantities of fossil fuels. 5 The finished content of the finished product is rolled. Small and grain-formed, rolled products P/Μ source and grain Osaki final product. μ + made of general refractory metal, especially sharp and alloy. The target and other objects and advantages of the invention are as follows Pot = for the production of a metal dairy product from a refractory metal powder / fire = i, (a) provide a low-oxygen refractory metal powder; (b) at the end of the lower 4 of the powder Adding - grain growth inhibitors, =) Hunting is carried out by high temperature isostatic squeezing or other heat machining procedures to make the powder solid 15 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 20 25 . And d) subjecting the lye powder to a subsequent sensible treatment, thereby forming the dairy product. The invention also relates to products made by this method. • The grain growth inhibitor is added to the sharp powder by adding an inhibitor (for example, Si0々γ2〇3) before the consolidation operation or by adding a residue of the deoxidation procedure, wherein magnesium is added to the deoxidation procedure. The cerium powder captures oxygen and forms magnesium oxide. The powder is consolidated by high temperature isostatic pressing (HIPING), extrusion or other thermal machining. These consolidation methods are capable of providing suitable P/Μ thin slabs up to hundreds of pounds (e.g., five hundred pounds, one thousand pounds or more). The p/ refractory metal obtained in this manner is then treated with a P/Μ sheet followed by a heat engine similar to the metal from the ingot source. The present invention inhibits grain growth of a 铌P/Μ sheet during high temperature exposure. A hypoxic powder (&lt;400 ppm' is preferably &lt; about 200 ppm) is required as a standard for the paper. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) is used. 3) = a higher content powder cannot be consolidated to full density and/or does not produce a good embodiment 5 10 15 20 , the invention relates to a method for producing a metal rolled product from a refractory metal powder, which comprises a) providing a low-oxygen refractory metal powder; (8) adding the powder to the powder prior to consolidation of the oxygen-fossil metal powder - grain growth inhibition = by high temperature isostatic pressing, extrusion or another thermomechanical processing procedure Solid (4) Qian Yucai accepts Lai _ treatment, and forms a job product. The invention also relates to products made by this method. The low-oxygen powder tree is any powder that meets the requirements of the present invention according to the present invention. The stabilized grain size metal powder of the present invention is preferably "Wu Guo Patent No. 6, 261, 337". The program makes this patent incorporated herein in its entirety. Niobium alloys can also be used. In other embodiments, a powder made of a fusible metal selected from the group consisting of molybdenum, rhenium, rhenium, ruthenium, crane, vanadium, and a mismetal is used instead of _. Further, an alloy of the above metals may also be used. So, as shown in Figure 1, the hypoxic and grain growth inhibitor powders (for example, (10) 2 σ &quot; this heterogeneously formed low-oxygen powder with a grain size inhibitor. Figure Η shows the main, the consolidation step of the material. And the physical process of consolidation allows the grain growth inhibiting particles to be distributed in the powder metal sheet. The powders are manufactured by the order of U.S. Patent No. 6,261,337 and as described in this specification. Mixing produces the desired alloy composition. The powder is then sealed in a vacuum tank, heated to a desired temperature, and squeezed to a ratio of &gt; 8.1. When this is completed, it is completely followed by the Wei powder and The inhibitor contained. The -S - 25

The 1262109 tank can be removed before the rolling operation or after the rolling operation. The above procedure can provide more stable grain size in the final material, more material properties (such as ultimate tensile strength and hardness), lower production costs, better control of fiber and quasi-size, and modification of alloys. Sex and feature control have greater flexibility. A sheet made of a powdery mixture of cerium and a crystallite inhibitor such as cerium was tested for Xs daily growth rate, ultimate tensile strength, and hardness. The test results are listed in the table below. °1065t® 1150°C@ 1300°C@ Ultimate tensile hardness (ppm) 90 minutes 180 minutes 180 minutes strength (VICKERS) (ASTM) -——__ (ASTM) (ASTM) ( KSI) 0 9.5 9.5 7.5 49.3 114 150 9.5 9.0 8.0 50.3 117 300 9.5 9.5 8.5 49.5 125 Nb I/Μ 5.5 &lt;1 &lt;1 32 72 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Print 10 Enable 0, 150 and The P/Μ sheet of 300 ppm grain growth inhibitor (preferably Shi Xi) was heat treated to a thickness of 0. 015 inches and annealed at 100 ° C for 90 minutes to produce grains of approximately ASTM 9.5. size. Under the same annealing heat treatment conditions, an ingot metallurgy (Ι/M) method was used to produce a crucible sheet having a grain size of about ASTM 5.5. The P/Μ and Ι/M test samples are subjected to additional annealing heat treatment, and the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied to the -6 - paper scale. 1262109 A7 B7 V. Invention Description (5 It was carried out at 1150 ° C for 180 minutes and at 13 () (rCit line (10) minutes. The p/M test sample produced a grain size larger than ASTM 7, 0, which was greater than the grain size produced by the I/M test sample by ASTM 1 or more. Therefore, the higher P/Μ ultimate tensile strengths of 49·3 KSI, 5〇·3 KS and 49·5 KSI and 114 VHN and 125 VHN are significantly better than the 32 KSI ultimate tensile resistance of conventional I/M materials. Strength and hardness of 72 qing. The fine grain size and improved tensile strength and hardness of the p/M material after heat treatment require a lot of deformation during the manufacturing process than the bismuth material (such as deep-drawing diamond cup or capacitor can). Another advantage is the case. 10 Alternatively, as shown in Figure 2, the hybrid powders can be isostatically pressed into a bar before canning and extrusion. The advantage of this method is that it is extruded. Before the larger weight starts, it helps to consolidate and increase the output of each extrusion. Now return to Figure 1, the hydrogenation sharp The vacuum chamber is also housed in a vacuum chamber containing a pair of oxygen-affinitive metals such as calcium or magnesium, preferably the latter. The gas content of the starting hydride powder is less than about 1 Torr. 〇〇 ppm. The chamber is heated to a dehydrogenation temperature to remove hydrogen and then heated to a deoxygenation temperature to produce a mesh having a thickness of less than about 400 ppm (preferably less than about 2 ppm and more preferably less than about 1 〇〇 ρρηι).裇 Low-oxygen bismuth powder or bismuth alloy powder. Then remove the oxygen-containing 20 mg from the metal powder by evaporation, followed by selective chemical leaching or dissolution of the powder printed by the Ministry of Economic Affairs. In other words, a cerium powder having an oxygen content of less than 400 ppm is produced by performing a hydrogenation depolarization treatment under a partial pressure of argon. The cerium hydride powder is mixed with 〇·3 weight percent of magnesium and placed in a In the vacuum furnace tank, the crucible tank is evacuated and recharged with argon 25. The pressure in the furnace is set to be about 1 μmicrons under the condition of argon flow and vacuum pump operation. (CNS) M Specifications (10) χ 2 97 1262109 A7 B7 V. Description of invention (6) 5 10 15 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative 20 The temperature of the furnace will rise to about 65 (rc) at an interval of about 50 °C, maintaining this temperature to equilibrium. It then ramps up to g5 〇 ° C at an elevated temperature of about 50 ° C. When the temperature is balanced at 950 C, the temperature is maintained for about two hours. After the incubation, the furnace is turned off. Once the furnace is cooled, its powder contents are removed from the crucible. The can is removed. The oxygenated magnesium is then removed from the metal powder by acid leaching to produce a finished cerium powder having an oxygen content of less than 300 ppm. As described in the month, in the process of making a formed tantalum powder metal product, the metal hydride powder is deoxygenated to an oxygen content of less than about 4 Å. The powder is consolidated to form a sharp or alloyed product having an oxygen content of less than about shed, or less than about _ or less than about 200 ppn or less than about 1 〇〇, but for many powder metallurgy Between 1〇〇ppm and 150 _. According to the present invention, a shaped stellar metal product (sharp product) having a stabilized grain size can be produced by any known powder metallurgy technique using a metal hydride powder treated as described above. Examples of powder metallurgy techniques used to form scale products are as follows, the steps of which are listed in It. The following single-technical or technical sequence# can be used in this month. Low temperature pressure, sintering, occupation, high temperature isostatic pressure and low temperature isostatic pressing, sintering, high temperature, etc., low temperature isostatic么,封^^等静性热机处理;low temperature isostatic pressing, material 1 temperature isostatic = loading and (4) test; low temperature pressure, sintering, block, masking and sputum treatment, low temperature isostatic pressing, sintering, extrusion Pressure, and heat machine ^, M sr / dish isostatic two 'and extrusion; low temperature isostatic pressing, encapsulation, extrusion and heat treatment; low dish isostatic pressing, packaging and _; packaging and extrusion; machine _ pressure, Translation: Low temperature isostatic pressing 'sintering' package, forging and heat machine ° heart. And rolling IL; packaging and forging; county and rolling; low temperature rotary sintering and 25

The paper size 剌 Chinese national standard specifications ((10)x 297 public) 1262109 A7 B7 V. Invention description (10 15 20 25 heat treatment; mechanical stamping and sintering; and mechanical stamping, sintering, re-stamping and re-sintering, can also be applied Other combinations of junction, heating and deformation. A shaped crucible product having a stabilized grain size is produced by low temperature isostatic pressing of various known niobium powders followed by a high temperature isostatic pressing (HIPmg) step. To make the denser denser, then heat-treat the powder denser to make the bonding more compact, as shown in Figure 3. Preferably, it will have a weight of 60,000 pounds per square inch and room temperature. The bismuth powder of the grain size inhibitor is subjected to low temperature isostatic pressing treatment to have a rectangular cross section (or better, a circular break), and then hermetically sealed and 4 〇, 〇〇〇 pound weight / square It is subjected to four hours of high temperature isostatic pressing (HIPed). The dense high temperature isostatically treated dense material is decapsulated and converted into a sheet or foil by a heat treatment step. 4, a use of oxygen content A similar procedure for 3 〇〇ppm 铌 powder and only low temperature isostatic pressing, sintering and heat treatment was obtained by low temperature isostatic pressing at 60 000 lbs/ft 2 to make the bismuth powder a rod Preform. In a vacuum environment of less than 0.001, the crucible is sintered at 15 〇 (rc for two hours to produce a density of about 95% of the theoretical density (Th) and the oxygen content is less than the shed ppm. Preform. The sintered preform is converted into a lap by a heat treatment step. It is known that high temperature extrusion and heat treatment will be used as a starting material with an oxygen content of less than 4 〇〇ppm. The sharp powder is made into a stable grain. The shape of the sharp sheet or the pre-form. The powder is hermetically sealed and then extruded at a temperature of 10 ° C through a rectangular or preferably circular pole to produce an oxygen content lower than the shed The product is converted into a sheet by a heat engine or (4). ^ The sheet or foil containing less than 400 ppra of oxygen is made by low temperature isostatic pressing, high -9 - Scale Timely Country_Standard (CNS) A4 (2ig X π Public Love) A7 B7 1262109 V. Invention Description (8) Temperature The extrusion and heat treatment steps are carried out. The dense substance caused by the low temperature and the like can be hermetically sealed and then extruded at HKKTC to produce an extruded product having an oxygen content of about _, which is processed by a heat engine. The steps are converted into sheets or sheets. Products with a stable grain size range are prepared by mechanical thief, sintering, re-punching and 5 re-sintering. The use of sharp powder hybrids with oxygen content below 400 ppm is used as a starting point. The powder was placed in a mold and mechanically dusted with a uniaxial pressure. The stamping block was then sintered for 15 hours at 15 Torr in a vacuum to a pressure of less than 0.001 Τοιτ. The sintered block was then stamped again and sintered again for 5 hours at 5 Torr in a vacuum environment with a pressure of about 10 to less than 0.001 Torr. This re-sintered block will have an oxygen content of less than about the side ppm and is suitable for thermal processing to produce a shaped tantalum product. In one embodiment, a copper or steel container is filled with tantalum powder, evacuated, hermetically sealed, and extruded through a die to impart a compression ratio of 1 : i. The copper container was removed in an acid manner and the extruded bar was heat treated into a sheet-like plate. In another embodiment, the -steel container is filled with sharp powder, evacuated, and the airtight vessel is subjected to high temperature treatment. The steel container was mechanically turned and the high temperature isostatically treated member was heat treated into a sheet-like plate. Printed by the Ministry of Economic Affairs' Intellectual Property Office employee consumption cooperative, although it may not be necessary - final annealing operation, 2 〇 annealing can be used between two deformation steps to improve the processability of the material or to adjust the grain size and structure through recrystallization. Texture. When the powder has a crucible during consolidation (usually to protect it from the harsh environment), the can adheres to the sharp. In another embodiment, the program provides a large (&gt; shredded) P/M sheet with good mechanical properties and a small and stable grain size, which yields higher yields than conventionally produced sheet materials. The program (- is usually 5 mash or less). The Chinese National Standard (CNS) A4 specification (21〇χ297 mm) is applied to every -10- paper scale described in this manual. 1262109 B7 15 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed V. Invention Description (9) A low-gas (less than 400 ppm, preferably less than 150 ppm) bismuth powder with non-spherical particles and a size smaller than 250 μm and a Fisher Average Particle Diameter (FAPD). The powder with a higher oxygen content cannot be consolidated. To full density and/or does not produce good mechanical properties. The powder is consolidated to full density by static pressure or extrusion at elevated temperatures, etc. Both methods provide suitable P/Μ sheets up to hundreds of pounds in weight. The heat treatment of the P/Μ slab is similar to the standard procedure. It is obvious that many variants and modifications can be made without departing from the invention. Therefore, it should be clearly understood that the form of the invention described in this specification is merely an example. It is to be understood that the scope of the invention is not limited thereto. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of a method for producing a stabilized grain size powder of the present invention; and Figures 2-4 are constructed to stabilize Grain ruler Made of an example of a flowchart of the consolidation step of the powdered product. This paper -11- applies China National Standard Scale (CNS) A4 size (210 X 297 mm)

Claims (1)

1262109 C8 1262109 VI. Patent Application A8 B8 C8 D8 The device is less than 400 ppm. 8. The method of claim </ RTI> wherein the low oxygen content is less than about 300 ppm. 9. The method of claim U, wherein the low oxygen sharp powder has an oxygen content of less than about 200 ppm. 10. The method of claim 1, wherein the oxygen content of the low oxygen sharp powder In the range of about 100 ppm to about 15 〇 ppm. 11. The method of claim 2, wherein the hypoxic powder has an oxygen content of less than about 100 ppm. The method wherein the dry product is a sheet containing oxide particles. 13. The method of claim 5, wherein the dry product is a foil. 15 14 · as claimed in claim 1 The method wherein the rolled product is a sheet having a weight of about 100 lbs. 15. A rolled product comprising a stabilized grain size, the method of manufacture comprising: (a) providing a low-oxygen refractory metal powder; Printed by the Intellectual Property Office Staff Consumer Cooperative 20 (b) Adding a grain growth inhibitor to the powder prior to consolidation of the low-oxygen refractory metal powder; (c) isothermal pressing, extrusion or another heat machining The procedure consolidates the powder; and (d) The consolidated powder is subjected to subsequent heat treatment to thereby form the rolled product. 25 16· The rolled product of claim 15 wherein the fire resistant gold-13 - the paper scale is suitable for the financial standard (CNS) A4 size (10) X 297 1262109 A8 B8 C8 D8 VI. The scope of patent application is a sharp or a sharp alloy. 17. The rolled product of claim 15 wherein the refractory metal is composed of the following Selected: 铪 'indium, bismuth, group, crane, hunger, and wrong metal, alloy of the above metals, and combinations thereof. 5 18. The rolled product of claim 15 wherein the powder is consolidated Previously, the grain growth inhibitor was added to the powder by (i) an inhibitor component mixed with the powder or (ii) a residue of a deoxygenation procedure. 19. Rolling as in claim 15 The product, wherein the residue 10 is a residue formed in a deoxygenation process, wherein magnesium is added during the deoxygenation process to capture oxygen from the tantalum powder and form magnesium oxide. 2 (h as claimed in claim 18 Rolled product The inhibitor component is selected from the group consisting of: S i 〇 2, Y 2 O 3 , and a mixture thereof. 15 21. The rolled product of claim 15 wherein the hypoxic yttrium powder The oxygen content is less than about 400 ppm. 22. The rolled product of claim 15 wherein the low-oxygen bismuth powder has an oxygen content of less than about 300 ppm. Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs. A rolled product of claim 15 wherein the rolled product is a sheet or a foil. 24. A method of making a metal rolled product from tantalum powder, comprising: (a) providing a low oxygen sharp powder having an oxygen content of less than about 400 ppm; (b) prior to consolidating the low oxygen niobium powder (i) an inhibitor component is mixed with the powder or (ii) a grain growth inhibitor is added to the powder by using a residue of one of the deoxygenation procedures, wherein the -14 - paper scale applies to the Chinese national standard ( CNS) A4 size (210x297 mm) 1262109 3 C8 _D8_ VI. Residue of the patent application range is a residue formed in a deoxygenation process in which magnesium is added during the deoxidation process to capture oxygen from the tantalum powder and form oxidation. (C) the powder 5 is consolidated by high temperature isostatic pressing, extrusion or another heat machining procedure; and (d) the consolidated powder is subjected to subsequent heat treatment to thereby form the rolled product. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm).