CN116441533A - High-nitrogen titanium powder, high-performance titanium workpiece and preparation method thereof - Google Patents
High-nitrogen titanium powder, high-performance titanium workpiece and preparation method thereof Download PDFInfo
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- CN116441533A CN116441533A CN202211380359.7A CN202211380359A CN116441533A CN 116441533 A CN116441533 A CN 116441533A CN 202211380359 A CN202211380359 A CN 202211380359A CN 116441533 A CN116441533 A CN 116441533A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 14
- 239000010936 titanium Substances 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 132
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 94
- 238000000498 ball milling Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 30
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000011049 filling Methods 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008117 stearic acid Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003350 kerosene Substances 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000005121 nitriding Methods 0.000 claims description 14
- 238000001192 hot extrusion Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000009694 cold isostatic pressing Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000005674 electromagnetic induction Effects 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005429 filling process Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 claims 1
- 239000006104 solid solution Substances 0.000 abstract description 9
- 150000004767 nitrides Chemical class 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
- 238000009461 vacuum packaging Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
Classifications
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- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/02—Nitrogen
-
- 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
Abstract
The preparation method of the high-nitrogen titanium powder adopts planetary ball milling of titanium nitride and titanium alloy powder, and comprises the following steps: selecting titanium and titanium alloy powder as raw material powder; placing the raw material powder into a ball milling tank, adding grinding balls, selectively adding stearic acid, aviation kerosene or alcohol as a ball milling medium, vacuumizing the ball milling tank, filling nitrogen atmosphere, and performing planetary ball milling to obtain nitrided powder; vacuum drying the obtained nitrided powder to obtain dry powder; and classifying and screening the dried powder. The invention also provides a preparation method of the high-performance titanium alloy product and the product thereof. According to the invention, titanium alloy powder reacts with nitrogen in the tank under the action of a planetary ball mill, a nitride film is generated on the surface of the titanium powder by controlling the ball milling process parameters, a stable structure with uniformly distributed nitrogen elements is obtained by adopting cold press sintering, high-temperature thermal deformation of a powder blank is realized, and finally the nitrogen solid solution reinforced high-performance titanium alloy is obtained.
Description
Technical Field
The invention relates to a powder metallurgy technology, in particular to a method for preparing high-nitrogen titanium powder by high-efficiency ball milling and preparing high-performance titanium parts by thermal deformation of a powder blank and a finished product prepared by the method.
Background
The titanium alloy has wide application prospect in the fields of aerospace, ocean engineering, automobile manufacturing and the like due to the excellent performances of high specific strength, corrosion resistance, high temperature resistance and the like. The method for preparing the titanium alloy by near-net forming of powder metallurgy avoids the solid-liquid phase change problem of the traditional preparation process, greatly reduces the manufacturing difficulty of titanium parts, and simultaneously has uniform and fine structure and excellent mechanical property.
With the rapid development of the high and new technical field, the demand for high-strength titanium parts is more and more urgent. The light element nitrogen is a gap element of titanium, and can be dissolved in gaps in titanium crystal lattices to bring about obvious solid solution strengthening effect, so that the mechanical strength of the titanium workpiece is greatly improved. However, the conventional heat treatment nitriding method consumes a large amount of energy, so that the production cost is greatly increased.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problem to be solved by the invention is to provide high-nitrogen titanium powder, a high-performance titanium workpiece and a preparation method thereof, wherein the strength of the titanium alloy is obviously improved through nitrogen solid solution strengthening, and then the low-cost high-performance titanium workpiece is prepared through a short flow by a powder blank thermal deformation method.
In order to achieve the above object, the present invention provides a method for preparing high nitrogen titanium powder, wherein planetary ball milling titanium nitride and titanium alloy powder is adopted, comprising the following steps:
s100, selecting titanium and titanium alloy powder as raw material powder;
s200, placing the raw material powder into a ball milling tank, adding grinding balls, selectively adding stearic acid, aviation kerosene or alcohol as a ball milling medium, vacuumizing the ball milling tank, filling nitrogen atmosphere, and performing planetary ball milling to obtain nitrided powder;
s300, carrying out vacuum drying on the obtained nitriding powder to obtain dry powder; and
s400, classifying and screening the dry powder.
In the above method for preparing high nitrogen titanium powder, in step S100, the titanium alloy powder is vacuum packaging powder which is not exploded after hydrogenation and dehydrogenation.
The preparation method of the high nitrogen titanium powder, wherein in the step S200, further comprises:
s201, selecting zirconium oxide as a material of the grinding ball, wherein the diameter of the grinding ball is 6-10 mm, and the ball-to-material ratio is 3:1-9:1;
s202, vacuumizing the ball milling tank until the vacuum degree is 10 -3 ～10 -1 Pa, and then filling nitrogen into the tank, wherein the air pressure of the nitrogen is controlled to be 0.6-1.2MPa;
s203, repeating the vacuumizing and nitrogen filling processes in the step S202 three times to avoid pollution of interstitial oxygen; and
s204, ball milling is carried out at a rotating speed of 160-300 r/min, the total duration is 5-10 h, and the ball milling process is set to stop for 3min every 5min of work.
In the preparation method of the high-nitrogen titanium powder, in the step S300, the vacuum drying temperature is 40-80 ℃ and the drying time is 0.5-3 h.
In the preparation method of the high-nitrogen titanium powder, in the step S400, a 325-mesh screen is used for classifying and screening the powder, so as to obtain the titanium alloy powder with minus 325 meshes after ball milling, wherein the nitrogen content of the powder is 0.15-0.4 wt.%.
In order to better achieve the aim, the invention also provides ball-milling high-nitrogen titanium and titanium alloy powder obtained by the preparation method of the high-nitrogen titanium powder.
In order to better achieve the object, the invention also provides a preparation method of the high-performance titanium alloy part, wherein a powder blank thermal deformation body is adopted, and the preparation method comprises the following steps:
s1, taking high nitrogen titanium and titanium alloy powder as raw material powder, wherein the raw material powder is the ball-milling high nitrogen titanium and titanium alloy powder of claim 5 packaged in vacuum;
s2, filling the raw material powder into a silica gel mold, and preparing a powder compact by cold isostatic pressing, wherein the pressure maintaining pressure of the cold isostatic pressing is 150-300 MPa, and the pressure maintaining time is 5-60 min;
s3, sintering the powder compact under the protection of vacuum or inert gas Ar to obtain a titanium alloy sintered compact;
and S4, performing high-temperature hot extrusion deformation on the titanium alloy sintered blank to obtain a high-performance titanium alloy workpiece.
The preparation method of the high-performance titanium alloy part, wherein the step S3 further comprises the following steps:
s31, heating the powder pressed compact from room temperature to 600-650 ℃ at a speed of 1-5 ℃/min, and preserving heat for 1-2 h;
s32, continuously heating to 1100-1250 ℃ at 1-5 ℃/min, and keeping the temperature for 1-4 h; and
s33, cooling to 800 ℃ at a speed of 1-5 ℃/min, and furnace cooling after heat preservation for 1-4 hours.
The preparation method of the high-performance titanium alloy product comprises the step S4 of carrying out high-temperature hot extrusion deformation in a sealed glove box under the protection of high-purity argon with the purity of more than or equal to 99.999 percent.
According to the preparation method of the high-performance titanium alloy workpiece, the oxygen content of the box body of the sealed glove box is less than or equal to 100ppm, the titanium alloy sintered blank is heated to 1100-1300 ℃ by an electromagnetic induction heating mode, and the temperature is kept for 1-10 min; rapidly transferring the mixture into a die preheated to 400-500 ℃, rapidly extruding at an extrusion speed of 15-25 mm/s, wherein the extrusion ratio is 9-16:1, and demoulding after the die is cooled to room temperature.
In order to better achieve the purpose, the invention also provides a titanium alloy part obtained by the preparation method of the high-performance titanium alloy part.
The titanium alloy product is a titanium alloy extrusion bar or pipe, the titanium alloy product has an equiaxed structure with grain size smaller than 3 mu m, and nano-scale beta particles are dispersed and distributed in an alpha-phase area.
The invention has the technical effects that:
according to the invention, titanium alloy powder reacts with nitrogen in the tank under the action of a planetary ball mill, a nitride film is generated on the surface of the titanium powder by controlling the ball milling process parameters, a stable structure with uniformly distributed nitrogen elements is obtained by adopting cold press sintering, high-temperature thermal deformation of a powder blank is realized, and finally the nitrogen solid solution reinforced high-performance titanium alloy is obtained. The preparation method of the high-nitrogen titanium powder comprises the steps of efficiently covering a uniform nitriding layer on the surface of titanium alloy powder through planetary ball milling, so that the nitrogen content of the powder is greatly improved; the high-performance titanium product is prepared by adopting a high-temperature heat deformation technology of a titanium powder blank, enabling nitrogen to be uniformly distributed in the sintering and heat deformation process by a powder surface nitriding layer, refining crystal grains, simultaneously providing high-temperature heat deformation capability, and combining a high-efficiency solid solution strengthening effect short flow of nitrogen element; the titanium alloy product with the grain size smaller than 3 mu m and the equiaxial alpha structure with dispersed beta phase attached on the surface is prepared, and the room temperature mechanical property is extremely excellent and far exceeds the level of the titanium alloy product in the prior art.
The invention will now be described in more detail with reference to the drawings and specific examples, which are not intended to limit the invention thereto.
Drawings
FIG. 1 is a diagram showing the morphology of a scanning electron microscope of Ti-6Al-4V alloy powder after ball milling nitridation in example 1;
FIG. 2 is a photograph of a microstructure of example 1 showing a low magnification of the powder blank after hot extrusion;
FIG. 3 is a photograph of a high magnification microstructure of the powder blank of example 1 after hot extrusion.
Detailed Description
The structural and operational principles of the present invention are described in detail below with reference to the accompanying drawings:
the preparation method of the high nitrogen titanium powder and the ball-milling high nitrogen titanium and titanium alloy powder obtained by the preparation method adopt planetary ball-milling titanium nitride and titanium alloy powder, and the preparation method of the high nitrogen titanium powder comprises the following steps:
step S100, raw material preparation: titanium and titanium alloy powder are selected as raw material powder, and the titanium alloy powder is preferably vacuum packaging powder which is not exploded after hydrogenation and dehydrogenation;
step S200, ball milling packaging: placing the raw material powder into a ball milling tank, adding grinding balls, selectively adding stearic acid, aviation kerosene or alcohol as a ball milling medium, vacuumizing the ball milling tank, filling nitrogen atmosphere, and performing planetary ball milling to obtain nitrided powder;
step S300, powder drying: vacuum drying the obtained nitriding powder to obtain dry powder, wherein the vacuum drying temperature is preferably 40-80 ℃, and the drying time is preferably 0.5-3 h; and
step S400, screening powder: classifying and screening the dry powder, wherein a 325-mesh screen is preferably used for classifying and screening the powder, so as to obtain the titanium alloy powder with minus 325 meshes after ball milling, wherein the nitrogen content of the powder is 0.15-0.4 wt.%.
Wherein, in step S200, further comprising:
step S201, selecting zirconium oxide as a material of the grinding ball, wherein the diameter of the grinding ball is 6-10 mm, and the ball-to-material ratio is 3:1-9:1;
step S202, vacuumizing the ball milling tank until the vacuum degree is 10 -3 ～10 -1 Pa, and then filling nitrogen into the tank, wherein the air pressure of the nitrogen is controlled to be 0.6-1.2MPa;
step S203, repeating the vacuum pumping and nitrogen filling processes in step S202 three times to avoid pollution of interstitial oxygen; and
and step S204, ball milling is carried out at a rotating speed of 160-300 r/min for 5-10 h, and the ball milling process is set to stop for 3min every 5min in order to avoid the overhigh ball milling temperature.
The invention also provides a preparation method of the high-performance titanium alloy part, which adopts a powder blank thermal deformation process and comprises the following steps:
step S1, raw material preparation: taking high nitrogen titanium and titanium alloy powder as raw material powder, wherein the raw material powder is ball-milled high nitrogen titanium and titanium alloy powder prepared by the steps of vacuum packaging;
step S2, forming: filling the raw material powder into a silica gel mold, and preparing a powder compact by cold isostatic pressing, wherein the pressure maintaining pressure of the cold isostatic pressing is 150-300 MPa, and the pressure maintaining time is 5-60 min;
step S3, sintering: sintering the powder pressed compact under the protection of vacuum or inert gas Ar to obtain a titanium alloy sintered compact;
step S4, hot working: carrying out high-temperature hot extrusion deformation on the titanium alloy sintered blank to obtain a high-performance titanium alloy workpiece, wherein the high-temperature hot extrusion deformation is carried out in a sealed glove box under the protection of high-purity argon with the purity of more than or equal to 99.999%, the oxygen content of the box body of the sealed glove box is less than or equal to 100ppm, and the titanium alloy sintered blank is heated to 1100-1300 ℃ at the speed of 100 ℃ per minute in an electromagnetic induction heating mode, and is kept for 1-10 minutes; rapidly transferring the mixture into an H13 die preheated to 400-500 ℃, rapidly extruding at an extrusion speed of 15-25 mm/s, wherein the extrusion ratio is 9-16:1, and demoulding after the die is cooled to room temperature.
Wherein, step S3 further comprises:
step S31, heating the powder pressed compact from room temperature to 600-650 ℃ at a speed of 1-5 ℃/min, and preserving heat for 1-2 h;
step S32, continuously heating to 1100-1250 ℃ at a speed of 1-5 ℃/min, and keeping the temperature for 1-4 h; and
and step S33, cooling to 800 ℃ at a speed of 1-5 ℃/min, and cooling in a furnace after heat preservation for 1-4 h.
The invention also provides an extremely fine equiaxed titanium alloy part obtained by the preparation method of the high-performance titanium alloy part, wherein the titanium alloy part is preferably a titanium alloy extrusion bar or pipe, the titanium alloy part has an equiaxed structure with grain size smaller than 3 mu m, and nano-scale beta particles are dispersed and distributed in an alpha phase area.
Experiments prove that by adopting the powder nitriding process and the powder blank thermal deformation preparation method, the titanium alloy product with uniform structure and obviously refined grain size can be obtained, wherein the density of the titanium alloy product is close to 100 percent, and the mechanical property is excellent.
The method for producing the high nitrogen titanium alloy powder and the high performance titanium alloy will be described in detail by way of specific examples.
Example 1
Referring to FIGS. 1 to 3, FIG. 1 is a graph showing the morphology of a Ti-6Al-4V alloy powder scanning electron microscope after ball milling nitriding in example 1, FIG. 2 is a photograph showing the microstructure of a powder blank after hot extrusion in example 1, and the graph shows the morphology of a Ti-6Al-4V alloy powder scanning electron microscope3 is a high magnification microstructure photograph of the powder billet of example 1 after hot extrusion. The raw material used in the planetary ball milling nitriding process is Ti-6Al-4V prealloyed powder which is vacuum packaged after hydrogenation and dehydrogenation. Putting the titanium alloy powder into a ball milling tank, adding zirconia grinding balls with the diameter of 6mm in a ratio of 6:1, adding stearic acid, and vacuumizing the ball milling tank to 10 -3 Pa, filling nitrogen into a ball milling tank, controlling the air pressure to be 0.8MPa, vacuumizing and filling N 2 The process was repeated three times and ball-milled for 8 hours at a rotational speed of 200r/min, wherein each run was stopped for 3min at 5 min. The powder after ball milling was dried in vacuo at 80℃for 2 hours, and after sieving, a-325 mesh titanium nitride alloy powder was obtained, with a nitrogen content of 0.28wt.%.
Filling the high nitrogen titanium alloy powder into a mould, preparing a powder compact by using 250MPa cold isostatic pressing, and keeping the pressure for 10min. Sintering the powder pressed compact, heating to 650 ℃ at a speed of 5 ℃/min, and preserving heat for 1h; then raising the temperature to 1200 ℃ at 5 ℃/min, and keeping the temperature for 2 hours; then cooling to 800 ℃ at 5 ℃/min, and preserving heat for 1 hour and then cooling in a furnace. In a sealed glove box (with the box oxygen content less than or equal to 100 ppm) under the protection of high-purity argon (with the purity more than or equal to 99.999%), heating the sintered blank to 1150 ℃ at 100 ℃/min in an electromagnetic induction heating mode, preserving heat for 8min, rapidly transferring the sintered blank into an H13 die preheated to 450 ℃, rapidly extruding at an extrusion speed of 20mm/s, wherein the extrusion ratio is 16:1, and demoulding after the die is cooled to room temperature. Obtaining the high-nitrogen Ti-6Al-4V extrusion bar.
The same preparation process as in example 1 was used in examples 2 to 6, except that the ball milling parameters, the forming, sintering and hot extrusion process parameters, etc. were all used, and the preparation process parameters in examples 1 to 6 were summarized and shown in tables 1 to 2.
Table 1 summary of powder nitridation process parameters in examples 1-6
Table 2 summary of cold isostatic pressing, sintering and hot extrusion process parameters in examples 1-6
The titanium alloy articles prepared by the preparation methods in examples 1 to 6 and the titanium alloy articles prepared by other preparation processes were subjected to performance comparison experiments.
1. Experimental objects
Comparative example 1
The preparation process in comparative example 1 is described with reference to example 1, but differs from example 1 in that: the raw material powder used was not subjected to ball milling nitriding treatment.
Comparative example 2
The preparation process in comparative example 2 is described with reference to example 1, but differs from example 1 in that: filling N 2 The air pressure of (2) was controlled at 0.4MPa.
Comparative example 3
The preparation process in comparative example 3 is described with reference to example 1, but differs from example 1 in that: the rotational speed during the ball milling process was 500r/min.
Comparative example 4
The preparation process in comparative example 4 is described with reference to example 1, but differs from example 1 in that: heating to 650 ℃ at a speed of 5 ℃/min in the sintering process, and preserving heat for 1h; raising the temperature to 1350 ℃ at 5 ℃/min, and keeping the temperature for 2 hours; then cooling to 800 ℃ at 5 ℃/min, and preserving heat for 1 hour and then cooling in a furnace.
2. Experimental method
The titanium alloy articles prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to performance measurement by conventional inspection methods of the prior art.
And (3) performance detection:
(1) And (3) testing the content of gap elements: the ball-milled powders prepared in examples 1 to 6 and comparative examples 1 to 3 were tested for nitrogen content.
(2) Mechanical property test: the titanium alloy articles prepared in examples 1 to 6 and comparative examples 1 to 4 were respectively subjected to room temperature tensile strength and elongation measurement.
3. Experimental results
The titanium alloy parts prepared by the preparation methods in examples 1-6 are detected to have uniform structures and equiaxed alpha structures smaller than 3 mu m.
The results of the experiments of examples 1 to 6 and comparative examples 1 to 4 are summarized in Table 3.
TABLE 3 comparison of the Properties of the titanium alloys prepared in examples 1 to 6 and comparative examples 1 to 4
As is clear from the data analysis in Table 3, in comparative example 1, a fully dense titanium alloy was obtained by heat deformation of the powder compact as well, but since there was no solid solution strengthening of nitrogen element and the hot extruded structure was distributed in a lamellar manner, the strength and plasticity were lower than those in examples 1 to 6 of the present invention. The invention is characterized in that nitrogen element is introduced, the lattice axial ratio of the titanium alloy is changed through interstitial solid solution, and nitrogen element is pinned to dislocation in the bearing process, so that the strength of the titanium alloy is obviously improved, and even and stable structure is formed into fine equiaxed grains under high-temperature thermal deformation, so that the titanium alloy product has excellent plasticity. The nitrogen pressure was reduced in comparative example 2, so that the nitrogen content of the obtained powder was reduced, and the properties of the obtained titanium alloy were also reduced after the subsequent thermal deformation of the powder compact. In comparative example 3, since the ball milling speed selected was too high, the powder was crushed and deformed during the preparation of the powder, and even if the high nitrogen titanium alloy powder was obtained, the mechanical properties of the equiaxed structure were still severely deteriorated due to the decrease in the powder formability. In comparative example 4, since the sintering temperature was too high, the structure grains grew excessively, and even if the powder was subjected to hot extrusion densification after nitriding, a large lamellar structure was formed, resulting in a decrease in alloy strength.
Therefore, the change of any technological parameter in the invention directly affects the powder nitriding condition and the thermal deformation process, and a uniform structure with good strong plasticity matching cannot be obtained. According to the invention, titanium alloy powder reacts with nitrogen in the tank under the action of a planetary ball mill, a nitride film is generated on the surface of the titanium powder by controlling the ball milling process parameters, a stable structure with uniformly distributed nitrogen elements is obtained by adopting cold press sintering, high-temperature thermal deformation of a powder blank is realized, and finally the nitrogen solid solution reinforced high-performance titanium alloy is obtained. The preparation method of the high-nitrogen titanium powder comprises the steps of efficiently covering a uniform nitriding layer on the surface of titanium alloy powder through planetary ball milling, so that the nitrogen content of the powder is greatly improved; the high-performance titanium product is prepared by adopting a high-temperature heat deformation technology of a titanium powder blank, enabling nitrogen to be uniformly distributed in the sintering and heat deformation process by a powder surface nitriding layer, refining crystal grains, simultaneously providing high-temperature heat deformation capability, and combining a high-efficiency solid solution strengthening effect short flow of nitrogen element; the titanium alloy product with the grain size smaller than 3 mu m and the equiaxial alpha structure with dispersed beta phase attached on the surface is prepared, and the room temperature mechanical property is extremely excellent and far exceeds the level of the titanium alloy product in the prior art.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. The preparation method of the high-nitrogen titanium powder is characterized by adopting planetary ball milling of titanium nitride and titanium alloy powder and comprises the following steps:
s100, selecting titanium and titanium alloy powder as raw material powder;
s200, placing the raw material powder into a ball milling tank, adding grinding balls, selectively adding stearic acid, aviation kerosene or alcohol as a ball milling medium, vacuumizing the ball milling tank, filling nitrogen atmosphere, and performing planetary ball milling to obtain nitrided powder;
s300, carrying out vacuum drying on the obtained nitriding powder to obtain dry powder; and
s400, classifying and screening the dry powder.
2. The method for producing high nitrogen titanium powder according to claim 1, wherein in step S100, the titanium alloy powder is vacuum packed powder which is not exploded after hydrogenation and dehydrogenation.
3. The method for producing high nitrogen titanium powder according to claim 1 or 2, wherein in step S200, further comprising:
s201, selecting zirconium oxide as a material of the grinding ball, wherein the diameter of the grinding ball is 6-10 mm, and the ball-to-material ratio is 3:1-9:1;
s202, vacuumizing the ball milling tank until the vacuum degree is 10 -3 ～10 -1 Pa, and then filling nitrogen into the tank, wherein the air pressure of the nitrogen is controlled to be 0.6-1.2MPa;
s203, repeating the vacuumizing and nitrogen filling processes in the step S202 three times to avoid pollution of interstitial oxygen; and
s204, ball milling is carried out at a rotating speed of 160-300 r/min, the total duration is 5-10 h, and the ball milling process is set to stop for 3min every 5min of work.
4. The method for preparing high nitrogen titanium powder according to claim 1 or 2, wherein in the step S300, the vacuum drying temperature is 40 to 80 ℃ and the drying time period is 0.5 to 3 hours.
5. The method for producing high nitrogen titanium powder according to claim 1 or 2, wherein in step S400, a 325 mesh sieve is used for classifying and sieving the powder to obtain a-325 mesh titanium alloy powder after ball milling, and the nitrogen content of the powder is 0.15 to 0.4wt.%.
6. A ball-milled high nitrogen titanium and titanium alloy powder obtained by the method for producing high nitrogen titanium powder according to any one of claims 1 to 5.
7. The preparation method of the high-performance titanium alloy workpiece is characterized by adopting a powder blank thermal deformation body and comprising the following steps of:
s1, taking high nitrogen titanium and titanium alloy powder as raw material powder, wherein the raw material powder is the ball-milling high nitrogen titanium and titanium alloy powder of claim 5 packaged in vacuum;
s2, filling the raw material powder into a silica gel mold, and preparing a powder compact by cold isostatic pressing, wherein the pressure maintaining pressure of the cold isostatic pressing is 150-300 MPa, and the pressure maintaining time is 5-60 min;
s3, sintering the powder compact under the protection of vacuum or inert gas Ar to obtain a titanium alloy sintered compact;
and S4, performing high-temperature hot extrusion deformation on the titanium alloy sintered blank to obtain a high-performance titanium alloy workpiece.
8. The method of producing a high performance titanium alloy article according to claim 7, wherein step S3 further comprises:
s31, heating the powder pressed compact from room temperature to 600-650 ℃ at a speed of 1-5 ℃/min, and preserving heat for 1-2 h;
s32, continuously heating to 1100-1250 ℃ at 1-5 ℃/min, and keeping the temperature for 1-4 h; and
s33, cooling to 800 ℃ at a speed of 1-5 ℃/min, and furnace cooling after heat preservation for 1-4 hours.
9. The method for producing a high-performance titanium alloy article according to claim 7 or 8, wherein the high-temperature hot extrusion deformation in step S4 is performed in a sealed glove box under the protection of high-purity argon gas having a purity of 99.999% or more.
10. The method for preparing a high-performance titanium alloy product according to claim 9, wherein the oxygen content of the box body of the sealed glove box is less than or equal to 100ppm, and the titanium alloy sintered blank is heated to 1100-1300 ℃ at 100 ℃/min by means of electromagnetic induction heating, and is kept for 1-10 min; rapidly transferring the mixture into a die preheated to 400-500 ℃, rapidly extruding at an extrusion speed of 15-25 mm/s, wherein the extrusion ratio is 9-16:1, and demoulding after the die is cooled to room temperature.
11. A titanium alloy article obtained by the method for producing a high-performance titanium alloy article according to any one of claims 7 to 10.
12. The titanium alloy article of claim 11, wherein the titanium alloy article is a titanium alloy extruded rod or tube, the titanium alloy article has an equiaxed structure with grain sizes less than 3 μm, and the alpha phase regions are dispersed with nano-sized beta particles.
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