CN110791682B - Preparation method of powder metallurgy titanium alloy - Google Patents

Preparation method of powder metallurgy titanium alloy Download PDF

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CN110791682B
CN110791682B CN201911296652.3A CN201911296652A CN110791682B CN 110791682 B CN110791682 B CN 110791682B CN 201911296652 A CN201911296652 A CN 201911296652A CN 110791682 B CN110791682 B CN 110791682B
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powder
parts
sintering
auxiliary agent
titanium alloy
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CN110791682A (en
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张威劲
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SUZHOU ZHONGYAO TECHNOLOGY Co.,Ltd.
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • B22F1/0003
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02Compacting only
    • B22F3/04Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1003Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007Atmosphere
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • C22C1/051Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • C22F1/183High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Abstract

The invention relates to a preparation method of a powder metallurgy titanium alloy, belonging to the technical field of alloys. The invention improves the sintering formability of the blank by adding the additive formed by mixing feldspar and fluorite, further adopts a vacuum hot pressing sintering method, further improves the compactness of the sintered titanium alloy, reduces the number of pores in the sintered titanium alloy, simultaneously can ensure that nitrogen reacts with partial metal elements in the titanium alloy to form nitride metal for deposition on the surface because of the adoption of the sintering in a nitrogen protection mode, simultaneously can further improve the sintering performance and remove partial impurities through the addition of the auxiliary agent because of the addition of the auxiliary agent, and also adds the mixed powder formed by mixing boron oxide, rare earth compound and sodium cobaltate, so that beta-Ti phase and alpha-Ti phase are both refined by the boron element and the rare earth compound in the sintering process, and the alpha-Ti sheet is obviously converted to the form similar to equiaxial grains, thereby facilitating ductility.

Description

Preparation method of powder metallurgy titanium alloy
Technical Field
The invention relates to a preparation method of a powder metallurgy titanium alloy, belonging to the technical field of alloys.
Background
Titanium alloys are advanced structural materials that have a range of desirable properties that are not easily achieved with any other material. These desirable properties include excellent corrosion resistance to seawater environments, high specific strength and fracture toughness, good compatibility with composites, long-term durability with little maintenance, excellent biocompatibility, and the like. However, such alloys may have very low yields due to the production difficulties involved with conventional ingot metallurgy-based processes. Powder metallurgy overcomes many of these disadvantages by requiring only a few finishing steps to produce the component.
Of the many powder metallurgy processes, conventional pressing and sintering or cold compression molding and sintering powder metallurgy processes are the most technically simple and economically attractive near-net shape fabrication processes. The process generally uses a mixed powder process involving mixing titanium powder with various alloy powders followed by compression molding and sintering. The method provides a number of advantages including flexibility in using inexpensive raw material powders, high throughput and simple process, which can result in significant cost savings compared to conventional ingot-based metallurgical manufacturing methods.
Further cost reductions in powder metallurgy Ti components also depend on the availability of low cost powder metallurgy titanium alloys that can provide the desired properties. From an alloy design perspective, various alloying elements can be incorporated into titanium for various alloying purposes. However, from a cost perspective, it is preferable to use lower cost or inexpensive alloying elements such as iron, aluminum, silicon, copper, and the like. Small amounts of more costly alloying elements, such as rare earth compounds, may be required to achieve the desired microstructure and/or mechanical properties.
Existing commercial grade titanium alloys are not designed for powder metallurgy processing; it is therefore difficult to form these alloys to near pore-free densities (e.g., > 99% of theoretical density) by simple pressing and sintering methods; and titanium alloys in the sintered state generally do not have sufficient ductility (e.g., tensile elongation < 4%), or even lack ductility due to the high oxygen content and the presence of large pores as discussed previously.
Disclosure of Invention
The invention mainly solves the technical problems of poor ductility and difficult sintering of the existing titanium alloy powder, and provides a preparation method of a powder metallurgy titanium alloy.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of powder metallurgy titanium alloy comprises the following steps:
(1) taking 200-230 parts of titanium powder, 20-22 parts of aluminum powder, 13-16 parts of molybdenum powder, 11-14 parts of mixed powder, 3-8 parts of additive, 2-5 parts of auxiliary agent, 4 parts of auxiliary agent and 1-3 parts of binder according to parts by weight, firstly putting the titanium powder, the aluminum powder, the molybdenum powder and the binder into a ball mill for ball milling, and collecting ball milled materials;
(2) putting the ball-milled material, the mixed powder, the additive, the auxiliary agent and the auxiliary agent into an extruder for extrusion, drying, crushing, sieving, collecting sieved particles, putting the sieved particles into a cold isostatic pressing sleeve, carrying out cold isostatic pressing treatment, wherein the height-diameter ratio of the cold isostatic pressing sleeve is controlled to be 3: 12-18: 4, the pressure during the cold isostatic pressing treatment is controlled to be 192-250 MPa, and the pressure maintaining time is controlled to be 5-8 min, so as to prepare a blank;
(3) putting the blank into a sintering furnace, vacuumizing, filling nitrogen until the pressure is 0.4-0.6 MPa, heating to 140-150 ℃, preheating, heating to 290-310 ℃, keeping for 40min, stopping filling nitrogen, heating to 720-820 ℃, and preserving heat;
(4) and after the heat preservation is finished, heating to 1150-1350 ℃ for sintering to obtain a sintering material, and performing low-temperature thermoplastic deformation treatment on the sintering material, wherein the temperature range is 790-830 ℃, the pass deformation is 13-22%, the inter-pass tempering temperature is 730-850 ℃, and the total deformation of the low-temperature thermoplastic deformation treatment is controlled to be 200-260% to obtain the powder metallurgy titanium alloy.
The mixed powder is formed by mixing boron oxide, a rare earth compound and sodium cobaltate according to a mass ratio of 11: 1-3: 0.2.
The rare earth compound is any one of lanthanum hexaboride powder and yttrium oxide.
The additive is any one of feldspar and fluorite.
The binder is any one of polyurethane binder and acrylate binder.
The adjuvant is polyethylene glycol.
The auxiliary agent is any one of lithium carbonate and lithium chloride.
The beneficial technical effects of the invention are as follows:
the invention improves the sintering formability of the blank by adding the additive formed by mixing feldspar and fluorite, and further adopts a vacuum hot pressing sintering method, thereby improving the compactness of the sintered titanium alloy and reducing the number of pores in the sintered titanium alloy, simultaneously, because the sintering in a nitrogen protection mode is adopted, nitrogen can react with partial metal elements in the titanium alloy to form nitride metal which is deposited on the surface of the nitride metal, the invention can improve the compactness and discharge gas and improve the mechanical property of the alloy, and because the invention adds the auxiliary agent, the sintering property can be further improved and partial impurities are removed by the auxiliary agent, and the invention also adds the mixed powder formed by mixing boron oxide, rare earth compound and sodium cobaltate, so that the beta-Ti phase and the alpha-Ti phase are both refined by the boron element and the rare earth compound in the sintering process, and also significantly transforms the alpha-Ti from a flake to a morphology of approximately equiaxed grains, thereby favoring ductility.
Detailed Description
The mixed powder is formed by mixing boron oxide, a rare earth compound and sodium cobaltate according to a mass ratio of 11: 1-3: 0.2.
The rare earth compound is any one of lanthanum hexaboride powder and yttrium oxide.
The additive is one of feldspar and fluorite.
The adhesive is any one of polyurethane adhesive and acrylate adhesive.
The adjuvant is polyethylene glycol.
The auxiliary agent is any one of lithium carbonate and lithium chloride.
A preparation method of powder metallurgy titanium alloy comprises the following steps:
(1) taking 200-230 parts of titanium powder, 20-22 parts of aluminum powder, 13-16 parts of molybdenum powder, 11-14 parts of mixed powder, 3-8 parts of additive, 2-5 parts of auxiliary agent, 4 parts of auxiliary agent and 1-3 parts of binder according to parts by weight, firstly putting the titanium powder, the aluminum powder, the molybdenum powder and the binder into a ball mill, carrying out ball milling for 2 hours at the speed of 800r/min, and collecting ball milled substances;
(2) putting the ball-milled material, the mixed powder, the auxiliary agent, the additive and the auxiliary agent into an extruder, extruding at 15MPa, drying, crushing, sieving with a 200-mesh sieve, collecting sieved particles, putting the sieved particles into a cold isostatic pressing sleeve, and carrying out cold isostatic pressing treatment, wherein the height-diameter ratio of the cold isostatic pressing sleeve is controlled to be 3: 12-18: 4, the pressure during the cold isostatic pressing treatment is controlled to be 192-250 MPa, and the pressure maintaining time is controlled to be 5-8 min, so as to prepare a blank;
(3) putting the blank into a sintering furnace, vacuumizing, filling nitrogen until the pressure is 0.4-0.6 MPa, heating to 140-150 ℃, preheating for 70min, heating to 290-310 ℃, keeping for 40min, stopping filling nitrogen, heating to 720-820 ℃, and preserving heat for 3 h;
(4) and after the heat preservation is finished, heating to 1150-1350 ℃ for sintering to obtain a sintering material, performing low-temperature thermoplastic deformation treatment on the sintering material, wherein the temperature range is 790-830 ℃, the pass deformation is 13-22%, the inter-pass tempering temperature is 730-850 ℃, and the total deformation of the low-temperature thermoplastic deformation treatment is controlled to be 200-260% to obtain the powder metallurgy titanium alloy.
Example 1
The mixed powder is formed by mixing boron oxide, a rare earth compound and sodium cobaltate according to a mass ratio of 11: 1-3: 0.2.
The rare earth compound is any one of lanthanum hexaboride powder and yttrium oxide.
The additive is one of feldspar and fluorite.
The adhesive is any one of polyurethane adhesive and acrylate adhesive.
The adjuvant is polyethylene glycol.
The auxiliary agent is any one of lithium carbonate and lithium chloride.
A preparation method of powder metallurgy titanium alloy comprises the following steps:
(1) taking 200-230 parts of titanium powder, 20-22 parts of aluminum powder, 13-16 parts of molybdenum powder, 11-14 parts of mixed powder, 3-8 parts of additive, 4 parts of auxiliary agent, 2-5 parts of auxiliary agent and 1-3 parts of binder according to parts by weight, firstly putting the titanium powder, the aluminum powder, the molybdenum powder and the binder into a ball mill, carrying out ball milling for 2 hours at the speed of 800r/min, and collecting ball milled substances;
(2) putting the ball-milled material, the mixed powder, the auxiliary agent, the additive and the auxiliary agent into an extruder, extruding at 15MPa, drying, crushing, sieving with a 200-mesh sieve, collecting sieved particles, putting the sieved particles into a cold isostatic pressing sleeve, and carrying out cold isostatic pressing treatment, wherein the height-diameter ratio of the cold isostatic pressing sleeve is controlled to be 3: 12-18: 4, the pressure during the cold isostatic pressing treatment is controlled to be 192-250 MPa, and the pressure maintaining time is controlled to be 5-8 min, so as to prepare a blank;
(3) putting the blank into a sintering furnace, vacuumizing, filling nitrogen until the pressure is 0.4-0.6 MPa, heating to 140-150 ℃, preheating for 70min, heating to 290-310 ℃, keeping for 40min, stopping filling nitrogen, heating to 720-820 ℃, and preserving heat for 3 h;
(4) and after the heat preservation is finished, heating to 1150-1350 ℃ for sintering to obtain a sintering material, performing low-temperature thermoplastic deformation treatment on the sintering material, wherein the temperature range is 790-830 ℃, the pass deformation is 13-22%, the inter-pass tempering temperature is 730-850 ℃, and the total deformation of the low-temperature thermoplastic deformation treatment is controlled to be 200-260% to obtain the powder metallurgy titanium alloy.
Example 2
The mixed powder is formed by mixing boron oxide, a rare earth compound and sodium cobaltate according to a mass ratio of 11: 1-3: 0.2.
The rare earth compound is any one of lanthanum hexaboride powder and yttrium oxide.
The additive is one of feldspar and fluorite.
The adhesive is any one of polyurethane adhesive and acrylate adhesive.
The adjuvant is polyethylene glycol.
The auxiliary agent is any one of lithium carbonate and lithium chloride.
A preparation method of powder metallurgy titanium alloy comprises the following steps:
(1) taking 200-230 parts of titanium powder, 20-22 parts of aluminum powder, 13-16 parts of molybdenum powder, 11-14 parts of mixed powder, 3-8 parts of additive, 4 parts of auxiliary agent, 2-5 parts of auxiliary agent and 1-3 parts of binder according to parts by weight, firstly putting the titanium powder, the aluminum powder, the molybdenum powder and the binder into a ball mill, carrying out ball milling for 2 hours at the speed of 800r/min, and collecting ball milled substances;
(2) putting the ball-milled material, the mixed powder, the auxiliary agent, the additive and the auxiliary agent into an extruder, extruding at 15MPa, drying, crushing, sieving with a 200-mesh sieve, collecting sieved particles, putting the sieved particles into a cold isostatic pressing sleeve, and carrying out cold isostatic pressing treatment, wherein the height-diameter ratio of the cold isostatic pressing sleeve is controlled to be 3: 12-18: 4, the pressure during the cold isostatic pressing treatment is controlled to be 192-250 MPa, and the pressure maintaining time is controlled to be 5-8 min, so as to prepare a blank;
(3) putting the blank into a sintering furnace, vacuumizing, filling nitrogen until the pressure is 0.4-0.6 MPa, heating to 140-150 ℃, preheating for 70min, heating to 290-310 ℃, keeping for 40min, stopping filling nitrogen, heating to 720-820 ℃, and preserving heat for 3 h;
(4) and after the heat preservation is finished, heating to 1150-1350 ℃ for sintering to obtain a sintering material, performing low-temperature thermoplastic deformation treatment on the sintering material, wherein the temperature range is 790-830 ℃, the pass deformation is 13-22%, the inter-pass tempering temperature is 730-850 ℃, and the total deformation of the low-temperature thermoplastic deformation treatment is controlled to be 200-260% to obtain the powder metallurgy titanium alloy.
Example 3
The mixed powder is formed by mixing boron oxide, a rare earth compound and sodium cobaltate according to a mass ratio of 11: 1-3: 0.2.
The rare earth compound is any one of lanthanum hexaboride powder and yttrium oxide.
The additive is one of feldspar and fluorite.
The adhesive is any one of polyurethane adhesive and acrylate adhesive.
The adjuvant is polyethylene glycol.
The auxiliary agent is any one of lithium carbonate and lithium chloride.
A preparation method of powder metallurgy titanium alloy comprises the following steps:
(1) taking 200-230 parts of titanium powder, 20-22 parts of aluminum powder, 13-16 parts of molybdenum powder, 11-14 parts of mixed powder, 3-8 parts of additive, 2-5 parts of auxiliary agent, 4 parts of auxiliary agent and 1-3 parts of binder according to parts by weight, firstly putting the titanium powder, the aluminum powder, the molybdenum powder and the binder into a ball mill, carrying out ball milling for 2 hours at the speed of 800r/min, and collecting ball milled substances;
(2) putting the ball-milled material, the mixed powder, the auxiliary agent, the additive and the auxiliary agent into an extruder, extruding at 15MPa, drying, crushing, sieving with a 200-mesh sieve, collecting sieved particles, putting the sieved particles into a cold isostatic pressing sleeve, and carrying out cold isostatic pressing treatment, wherein the height-diameter ratio of the cold isostatic pressing sleeve is controlled to be 3: 12-18: 4, the pressure during the cold isostatic pressing treatment is controlled to be 192-250 MPa, and the pressure maintaining time is controlled to be 5-8 min, so as to prepare a blank;
(3) putting the blank into a sintering furnace, vacuumizing, filling nitrogen until the pressure is 0.4-0.6 MPa, heating to 140-150 ℃, preheating for 70min, heating to 290-310 ℃, keeping for 40min, stopping filling nitrogen, heating to 720-820 ℃, and preserving heat for 3 h;
(4) and after the heat preservation is finished, heating to 1150-1350 ℃ for sintering to obtain a sintering material, performing low-temperature thermoplastic deformation treatment on the sintering material, wherein the temperature range is 790-830 ℃, the pass deformation is 13-22%, the inter-pass tempering temperature is 730-850 ℃, and the total deformation of the low-temperature thermoplastic deformation treatment is controlled to be 200-260% to obtain the powder metallurgy titanium alloy.
The examples were sintered density measured by the Archimedes method according to ASTM standard B328, tensile specimens (3 mm. times.4.5 mm cross section and 15mm gauge length) were machined from the as-sintered bars and tested on an Instron screw machine (model 5054, USA) at a crosshead speed of 0.5 mm/min, with the test results given in the following table.
Figure GDA0002703714240000061
In conclusion, the powder metallurgy titanium alloy prepared by the invention achieves better results.

Claims (3)

1. The preparation method of the powder metallurgy titanium alloy is characterized by comprising the following steps:
(1) taking 200-230 parts of titanium powder, 20-22 parts of aluminum powder, 13-16 parts of molybdenum powder, 11-14 parts of mixed powder, 3-8 parts of additive, 2-5 parts of auxiliary agent, 4 parts of auxiliary agent and 1-3 parts of binder according to parts by weight, firstly putting the titanium powder, the aluminum powder, the molybdenum powder and the binder into a ball mill for ball milling, and collecting ball milled substances;
(2) putting the ball-milled material, the mixed powder, the additive, the auxiliary agent and the auxiliary agent into an extruder for extrusion, drying, crushing, sieving, collecting sieved particles, putting the sieved particles into a cold isostatic pressing sleeve, carrying out cold isostatic pressing treatment, wherein the height-diameter ratio of the cold isostatic pressing sleeve is controlled to be 3: 12-18: 4, the pressure during the cold isostatic pressing treatment is controlled to be 192-250 MPa, and the pressure maintaining time is controlled to be 5-8 min, so as to prepare a blank;
(3) putting the blank into a sintering furnace, vacuumizing, filling nitrogen until the pressure is 0.4-0.6 MPa, heating to 140-150 ℃, preheating, heating to 290-310 ℃, keeping for 40min, stopping filling nitrogen, heating to 720-820 ℃, and preserving heat;
(4) after the heat preservation is finished, heating to 1150-1350 ℃ for sintering to obtain a sintering material, performing low-temperature thermoplastic deformation treatment on the sintering material, wherein the temperature range is 790-830 ℃, the pass deformation is 13-22%, the inter-pass tempering temperature is 730-850 ℃, the total deformation of the low-temperature thermoplastic deformation treatment is controlled to be 200-260%, and the powder metallurgy titanium alloy is obtained,
the mixed powder is formed by mixing boron oxide, a rare earth compound and sodium cobaltate according to a mass ratio of 11: 1-3: 0.2;
the additive is any one of feldspar and fluorite;
the auxiliary agent is any one of lithium carbonate and lithium chloride;
the adjuvant is polyethylene glycol.
2. The method according to claim 1, wherein the rare earth compound is one of lanthanum hexaboride powder and yttrium oxide.
3. The method of claim 1, wherein the binder is any one of a polyurethane binder and an acrylate binder.
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