CN116393705B - Titanium alloy material for 3D printing and preparation method thereof - Google Patents
Titanium alloy material for 3D printing and preparation method thereof Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 69
- 239000000956 alloy Substances 0.000 title claims abstract description 63
- 238000010146 3D printing Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000010936 titanium Substances 0.000 claims abstract description 73
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 68
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 238000000227 grinding Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000003723 Smelting Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000005554 pickling Methods 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 51
- 238000000498 ball milling Methods 0.000 claims description 44
- 229910000756 V alloy Inorganic materials 0.000 claims description 32
- HIMLGVIQSDVUJQ-UHFFFAOYSA-N aluminum vanadium Chemical compound [Al].[V] HIMLGVIQSDVUJQ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 239000012300 argon atmosphere Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 229910052689 Holmium Inorganic materials 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 238000010298 pulverizing process Methods 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 238000005121 nitriding Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000007873 sieving Methods 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- -1 and the like Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001238 wet grinding 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
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- 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
- B22F1/142—Thermal or thermo-mechanical treatment
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/023—Hydrogen absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/10—Pre-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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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
- 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
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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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
- 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
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- B22—CASTING; POWDER METALLURGY
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- 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
- B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
- B22F2009/046—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling by cutting
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- 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
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Abstract
The application relates to the technical field of 3D printing materials, in particular to a titanium alloy material for 3D printing and a preparation method thereof, and the preparation method comprises the following processes: smelting titanium sponge for 2-5 times; cogging, rolling and straightening the obtained cast ingot, turning oxide skin and cleaning; turning the obtained powder preparation rod at a low speed to obtain titanium scraps; heating titanium scraps to 500-700 ℃, grinding in a grinding machine, and screening to obtain titanium powder; and (3) pickling and dehydrogenating the titanium powder to obtain the titanium alloy material. According to the application, through improving the content of oxygen element in chemical component in the raw material titanium sponge, the phenomenon of oxygen increasing exceeding standard caused by smelting is relieved, and the content of impurity element in the titanium alloy material is reduced, so that the plasticity index of the manufactured 3D printing product is improved. The titanium powder is formed into balls by low-temperature heating mechanical grinding of titanium scraps, so that the equiaxial degree of a structure in a 3D printing product made of the titanium alloy material is improved, and the structure of the product is more uniform and finer.
Description
Technical Field
The application relates to the technical field of 3D printing materials, in particular to a titanium alloy material for 3D printing and a preparation method thereof.
Background
Currently, metal powder materials for 3D printing include titanium alloys, aluminum alloys, bronze alloys, nickel alloys, and the like, and titanium alloy powder is the most important part of the 3D printing industry of metal parts and is also the most valuable. Titanium alloy is the most commonly used metal material in 3D printing, has the characteristics of small density, high specific strength, good heat resistance, excellent corrosion resistance, good biocompatibility and the like, and is widely applied to the fields of aerospace, industry, national defense, medical treatment, electronics and the like. Based on excellent comprehensive performance and higher technical maturity, the additive manufacturing titanium alloy TC11 is widely applied to typical complex structural parts of various airplanes at home and abroad and aero-engine parts, and has obvious advantages of low cost, high efficiency and the like. The application field of titanium alloy 3D printing is gradually beyond the application range of aerospace, and the application field begins to expand to the fields of automobiles and large industries, and the domestic titanium alloy 3D printing powder market is developing vigorously. However, the existing titanium alloy powder in the conventional production process has two defects, namely, the chemical components of impurities are easy to exceed standard, and the titanium powder is non-spherical, so that the quality of a 3D printing product is seriously affected. Therefore, we propose a titanium alloy material for 3D printing and a preparation method thereof.
Disclosure of Invention
The application aims to provide a titanium alloy material for 3D printing and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the application provides the following technical scheme: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step one, preparing cast ingots: smelting titanium sponge for 2-5 times; cooling to below 400 ℃ after smelting is completed, and taking out to obtain an ingot;
step two, preparing a powder preparation rod: cogging, rolling, straightening, turning oxide skin and cleaning the cast ingot obtained in the previous step to obtain a powder-making rod;
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps;
heating titanium scraps to 500-700 ℃, grinding in a grinding machine, and screening to obtain titanium powder;
and (3) pickling and dehydrogenating the titanium powder to obtain the titanium alloy material.
Further, the titanium sponge is 0A grade small particle titanium sponge with the particle size of 0.83-12.7 mm and is from Liaoning Yangchen Hongyu metallurgical materials Co;
the purity of Ti in the titanium sponge is more than or equal to 99.8 percent (mass percent), fe is less than or equal to 0.03 percent, si is less than or equal to 0.01 percent, cl is less than or equal to 0.06 percent, mn is less than or equal to 0.01 percent, mg is less than or equal to 0.01 percent, ni is less than or equal to 0.01 percent, cr is less than or equal to 0.01 percent, O is less than or equal to 0.050 percent, C is less than or equal to 0.008 percent, N is less than or equal to 0.0045 percent, and H is less than or equal to 0.003 percent. The element content needs to meet the middle limit requirement in the GB/T3620.1 standard. Through the control of the chemical components of the titanium sponge, the lower oxygen content can provide oxygenation space for repeated smelting, and the ultralow control of the particle size of the titanium sponge and C, N, H element can provide plasticity space for 3D printing products made of titanium alloy materials.
Further, smelting in the first step is performed in a small tonnage vacuum consumable arc furnace, and the specific process is as follows: the smelting voltage is 28-35V, the argon atmosphere is protected, and the vacuum degree is 0.10-0.01 Pa. The chemical components of the manufactured powder rod can be uniformly distributed through multiple smelting.
Further, the dimensions of the titanium chip are: the thickness is 1-2 mm, and the width is 0.5-1.0 cm.
Further, the powder is placed in a pulverizer to be subjected to coarse grinding, semi-fine grinding and fine grinding in sequence, and then screening is carried out to obtain titanium powder with the particle size smaller than 100 mu m.
In the technical scheme, the grinding process of the titanium scraps is carried out after the titanium scraps are heated to 500-700 ℃, and the oxide layer on the surfaces of the titanium scraps is thinner in the temperature range, so that the influence on the material components is small; and the deformation resistance of titanium scraps at the temperature is improved, so that the grinding machine is more convenient for preparing spherical powder. The subsequent acid washing process can remove the oxide layer generated when titanium scraps are heated to prepare powder. The hydrogen removal adopts vacuum annealing to remove the hydrogen element exceeding the standard possibly caused by acid washing.
According to the application, through improving the content of oxygen element in chemical component in the raw material titanium sponge, the phenomenon of oxygen increasing exceeding standard caused by smelting is relieved, and the content of impurity element in the titanium alloy material is reduced, so that the plasticity index of the manufactured 3D printing product is improved.
By the heating treatment in the grinding process, the prepared titanium powder is enabled to be spherical, the equiaxial degree of the structure in the 3D printing product prepared from the titanium alloy material is improved, and the structure of the product is enabled to be more uniform and finer.
Further, ball milling is carried out before acid washing, and the ball milling process is as follows:
mixing titanium powder with aluminum-vanadium alloy, molten salt and medium, ball milling in argon atmosphere for 18-24 hr in ball-to-material ratio of 6-10 to 1.
Further, the mass ratio of the titanium powder, the aluminum-vanadium alloy, the molten salt and the medium is (9.0-9.8): 1 (0.5-1.8): 1.5-2.9.
Further, the molten salt comprises the following mass components: 11-28 parts of sodium chloride, 9-24 parts of potassium chloride and 1 part of potassium fluotitanate.
Further, the molten salt comprises the following mass components: 17-21 parts of magnesium chloride, 13-18 parts of holmium and 1-3 parts of potassium fluotitanate.
Further, three stainless steel grinding balls with different particle sizes are adopted for ball milling, the radius is 20mm, 10mm and 6mm in sequence, the mass ratio is 2:3:5, and the rotating speed is 450-550 rpm.
Further, the medium is deionized water, absolute ethyl alcohol or a mixture of the deionized water and the absolute ethyl alcohol.
Further, 40wt% of V is contained in the aluminum-vanadium alloy, the impurity O is less than or equal to 0.12wt%, the particle size is 1-3 mm, and the aluminum-vanadium alloy is derived from Henan Pond special alloy materials; and the surface nitriding treatment is carried out, and the specific process is as follows:
placing aluminum-vanadium alloy into a closed resistance furnace, introducing nitrogen gas, heating to 800-900 ℃, preserving heat for 60-90 min, and cooling;
the nitrogen flow rate in the heating stage is 20-30 sccm, and the heating rate is 4-5 ℃/min; the nitrogen flow rate in the heat preservation stage is 50-60 sccm; the nitrogen flow rate in the cooling stage is 15-20 sccm.
Further, hydrogenation is carried out before ball milling, and the hydrogenation process is as follows: vacuum-pumping to pressure 10 in argon atmosphere -2 ～10 -3 Pa, heating to 240-270 ℃, preserving heat for 100-150 min, and drying the raw materials; continuously heating to 400-450 ℃, introducing hydrogen, controlling the air pressure to be 0.1-0.2 MPa, preserving heat for 28-30 min.
Further, the pickling process comprises the following steps: a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 15-20 deg.c for 6-10 min, washing with deionized water, alcohol and acetone, and drying.
Further, the dehydrogenation is vacuum high-temperature dehydrogenation, and the specific process comprises the following steps: pressure 10 -2 ～10 -3 Pa, the temperature is 600-700 ℃, and the heat preservation time is 4-8 h.
In the technical scheme, the aluminum-vanadium alloy is firstly subjected to partial nitridation on the surface of the aluminum-vanadium alloy by a direct nitridation method to generate the aluminum nitride doped aluminum-vanadium alloy. Then mixing with titanium powder, molten salt and wet grinding medium for ball milling, in the system, the potassium fluotitanate is ball milled to decompose Ti 4+ Can react with simple substance titanium in titanium powder to obtain Ti 2+ And generating simple substance titanium through disproportionation reaction, depositing the simple substance titanium on the surface of aluminum nitride of aluminum-vanadium alloy, generating solid-solid interface reaction between the simple substance titanium and aluminum nitride in a ball milling system to generate stable compound titanium nitride and titanium-aluminum intermetallic compound, introducing the titanium nitride into a titanium alloy material system, realizing the composite enhancement of the titanium alloy material by the aluminum nitride and the titanium nitride, relieving the randomness and the non-uniformity when directly adding an enhancement phase, reducing the granularity of the enhancement phase in the titanium alloy, and promoting the refinement, the uniformity and the improvement of the mechanical property of the structure of the manufactured 3D printing product.
Magnesium chloride and holmium in molten salt react in ball milling to generate elemental magnesium and holmium chloride, and in the ball milling process, the elemental magnesium can be used as a deoxidizer of titanium powder, so that the oxygen content in the titanium powder is reduced, and the generated magnesium oxide reacts with a reaction accelerator holmium chloride to obtain holmium deoxidization product (HoOCl), so that the deoxidization of the magnesium oxide is promoted, and the oxygen content of the titanium powder is further reduced. The use of the medium (deionized water and absolute ethyl alcohol) can dissolve molten salt, so that the molten salt can enter the pores of the powder such as titanium powder, aluminum-vanadium alloy and the like, the material exchange is promoted, and the formation and development of products are accelerated. Under the continuous ball milling process, the titanium powder and the aluminum-vanadium alloy are subjected to adhesion agglomeration, the edges and corners on the surface of the powder are reduced, the morphology tends to be spherical, and mechanical alloying is carried out in the repeated impact of ball milling, so that the titanium alloy material is obtained.
The hydrogenation before ball milling ensures that the titanium powder is embrittled, can promote the size refinement in the ball milling process, and can promote the diffusion of alloy elements in the aluminum-vanadium alloy in titanium in the ball milling process, thereby realizing prealloying. And (3) carrying out acid washing after ball milling to remove salt, deoxidized products and the like on the surface of the prepared titanium alloy material. Finally, the hydrogen element in the titanium alloy material is removed by utilizing vacuum high temperature, meanwhile, the diffusion between element titanium and aluminum can be promoted, the alloying uniformity is promoted, tiAl intermetallic compounds are formed, the metallurgical bonding is more precise, and the strong plasticity of the titanium alloy material is improved.
Compared with the prior art, the application has the following beneficial effects:
1. according to the titanium alloy material for 3D printing and the preparation method thereof, through improving the content of the chemical component oxygen element in the raw material titanium sponge, the phenomenon of exceeding oxygen increasing standard caused by smelting is relieved, and the content of impurity elements in the titanium alloy material is reduced, so that the plasticity index of the prepared 3D printing product is improved. The titanium powder is formed into balls by low-temperature heating mechanical grinding of titanium scraps, so that the equiaxial degree of a structure in a 3D printing product made of the titanium alloy material is improved, and the structure of the product is more uniform and finer.
2. According to the titanium alloy material for 3D printing and the preparation method thereof, the titanium powder and the aluminum-vanadium alloy are mixed and ball-milled to generate adhesion agglomeration, so that the angles of the powder surface are reduced, the morphology tends to be spherical, and mechanical alloying is generated, so that the titanium alloy material with high strength and plasticity is obtained.
3. According to the titanium alloy material for 3D printing and the preparation method thereof, the surface of the aluminum-vanadium alloy is partially nitrided, interfacial reaction is carried out under the action of molten salt to generate stable compounds titanium nitride and titanium-aluminum intermetallic compounds, and the titanium nitride is introduced into a titanium alloy material system, so that the composite reinforcement of the aluminum nitride and the titanium nitride to the titanium alloy material is realized, the randomness and the non-uniformity of the direct addition of the reinforcing phase can be relieved, the granularity of the reinforcing phase in the titanium alloy is reduced, and the refinement, the uniformity and the mechanical property improvement of the structure of the manufactured 3D printing product are promoted.
4. According to the titanium alloy material for 3D printing and the preparation method thereof, magnesium chloride and holmium are selected as molten salts, and in the ball milling process, elemental magnesium and holmium chloride are generated through reaction, and the elemental magnesium can be used as a deoxidizer of titanium powder, so that the oxygen content of the titanium powder is reduced. The use of the medium dissolves the molten salt, so that the molten salt can enter the pores of the powder such as titanium powder, aluminum-vanadium alloy and the like, the substance exchange is promoted, and the formation and development of products are accelerated.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the embodiment, the titanium sponge is 0A grade small particle titanium sponge with the particle size of 0.83-12.7 mm and is from Liaoning Yangchen Hongyu metallurgical materials Co;
the purity of Ti in the titanium sponge is more than or equal to 99.8 percent (mass percent), fe is less than or equal to 0.03 percent, si is less than or equal to 0.01 percent, cl is less than or equal to 0.06 percent, mn is less than or equal to 0.01 percent, mg is less than or equal to 0.01 percent, ni is less than or equal to 0.01 percent, cr is less than or equal to 0.01 percent, O is less than or equal to 0.050 percent, C is less than or equal to 0.008 percent, N is less than or equal to 0.0045 percent, and H is less than or equal to 0.003 percent.
The aluminum-vanadium alloy contains 40wt% of V, the impurity O is less than or equal to 0.12wt%, the grain size is 1-3 mm, and the alloy is from Henan Pond special alloy materials Co., ltd;
the number "parts" below represents 100g.
Example 1: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step one, preparing cast ingots: the sponge titanium is taken and smelted for 3 times, and the smelting is carried out in a small-tonnage vacuum consumable arc furnace, and the specific process comprises the following steps: smelting voltage is 30V, argon atmosphere is used for protection, and vacuum degree is 0.5Pa; cooling to 300 ℃ after smelting is completed, and taking out to obtain an ingot;
step two, preparing a powder preparation rod: cogging, rolling and straightening the cast ingot obtained in the previous step, turning oxide skin and cleaning;
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
heating titanium scraps to 600 ℃, placing the titanium scraps in a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving the titanium scraps with a 155-mesh sieve to obtain titanium powder;
titanium powder is pickled by mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 18deg.C for 8min, washing with deionized water, alcohol, and acetone, and drying; the process for removing hydrogen comprises the following steps: pressure 5X 10 -3 Pa, the temperature is 650 ℃, and the heat preservation time is 6 hours, so as to obtain the titanium alloy material.
Example 2: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step one, preparing cast ingots: the sponge titanium is taken and smelted for 2 times, and the smelting is carried out in a small-tonnage vacuum consumable arc furnace, and the specific process comprises the following steps: the smelting voltage is 35V, the argon atmosphere is protected, and the vacuum degree is 0.10Pa; cooling to 400 ℃ after smelting is completed, and taking out to obtain an ingot;
step two, preparing a powder preparation rod: cogging, rolling and straightening the cast ingot obtained in the previous step, turning oxide skin and cleaning;
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the size of the titanium scraps is as follows: the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
heating titanium scraps to 500 ℃, placing the titanium scraps in a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving the titanium scraps with a 155-mesh sieve to obtain titanium powder;
(1) Hydrogenation: taking titanium powder, and vacuumizing to the pressure of 10 in an argon atmosphere -2 Pa, heating to 240 ℃, preserving heat for 100min, and drying the raw materials; continuously heating to 400 ℃, introducing hydrogen, controlling the air pressure to be 0.1MPa, and preserving heat for 28min;
(2) Nitriding: placing aluminum-vanadium alloy in a closed resistance furnace, introducing nitrogen, heating to 800 ℃, preserving heat for 60min, and cooling; the nitrogen flow rate in the heating stage is 20sccm, and the heating rate is 4 ℃/min; the nitrogen flow rate in the heat preservation stage is 50sccm; the nitrogen flow rate in the cooling stage is 15sccm;
(3) Ball milling: 9.0 parts of titanium powder is mixed with 1 part of aluminum-vanadium alloy, 0.5 part of molten salt (0.27 part of magnesium chloride+0.21 part of holmium+0.02 part of potassium fluotitanate) and 1.5 parts of medium deionized water, ball milling is carried out in an argon atmosphere, the ball-material ratio is 6:1, and the ball milling time is 18 hours; the ball milling adopts three stainless steel grinding balls with different particle sizes, the radius is sequentially 20mm, 10mm and 6mm, the mass ratio is 2:3:5, and the rotating speed is 450rpm;
(4) Acid washing with a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 15deg.C for 10min, washing with deionized water, alcohol, and acetone, and drying;
(5) The process for removing hydrogen comprises the following steps: pressure 10 -2 Pa, the temperature is 600 ℃, and the heat preservation time is 4 hours, so as to obtain the titanium alloy material.
Example 3: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step one, preparing cast ingots: the sponge titanium is taken and smelted for 3 times, and the smelting is carried out in a small-tonnage vacuum consumable arc furnace, and the specific process comprises the following steps: smelting voltage is 30V, argon atmosphere is used for protection, and vacuum degree is 0.5Pa; cooling to 300 ℃ after smelting is completed, and taking out to obtain an ingot;
step two, preparing a powder preparation rod: cogging, rolling and straightening the cast ingot obtained in the previous step, turning oxide skin and cleaning;
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
heating titanium scraps to 600 ℃, placing the titanium scraps in a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving the titanium scraps with a 155-mesh sieve to obtain titanium powder;
(1) Hydrogenation: taking titanium powder, vacuum pumping to 5×10 pressure in argon atmosphere -3 Pa, heating to 255 ℃, preserving heat for 120min, and drying the raw materials; continuously heating to 425 ℃, introducing hydrogen, controlling the air pressure to be 0.15MPa, and preserving heat for 29min;
(2) Nitriding: placing aluminum-vanadium alloy in a closed resistance furnace, introducing nitrogen gas, heating to 850 ℃, preserving heat for 75min, and cooling; the nitrogen flow rate in the heating stage is 25sccm, and the heating rate is 4.5 ℃/min; the nitrogen flow rate in the heat preservation stage is 55sccm; the nitrogen flow rate in the cooling stage is 18sccm;
(3) Ball milling: 9.4 parts of titanium powder, 1 part of aluminum-vanadium alloy, 1.2 parts of molten salt (0.63 part of magnesium chloride+0.50 part of holmium+0.07 part of potassium fluotitanate) and 2.2 parts of medium deionized water are mixed, ball milling is carried out in an argon atmosphere, the ball-material ratio is 8:1, and the ball milling time is 21 hours; the ball milling adopts three stainless steel grinding balls with different particle sizes, the radius is sequentially 20mm, 10mm and 6mm, the mass ratio is 2:3:5, and the rotating speed is 500rpm;
(4) Acid washing with a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 18deg.C for 8min, washing with deionized water, alcohol, and acetone, and drying;
(5) The process for removing hydrogen comprises the following steps: pressure 5X 10 -3 Pa, the temperature is 650 ℃, and the heat preservation time is 6 hours, so as to obtain the titanium alloy material.
Example 4: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step one, preparing cast ingots: the sponge titanium is taken and smelted for 5 times, and the smelting is carried out in a small-tonnage vacuum consumable arc furnace, and the specific process comprises the following steps: the smelting voltage is 28V, the argon atmosphere is protected, and the vacuum degree is 0.01Pa; cooling to 400 ℃ after smelting is completed, and taking out to obtain an ingot;
step two, preparing a powder preparation rod: cogging, rolling and straightening the cast ingot obtained in the previous step, turning oxide skin and cleaning;
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
heating titanium scraps to 700 ℃, placing the titanium scraps in a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving the titanium scraps with a 155-mesh sieve to obtain titanium powder;
(1) Hydrogenation: taking titanium powder, and vacuumizing to the pressure of 10 in an argon atmosphere -3 Pa, heating to 270 ℃, preserving heat for 150min, and drying the raw materials; continuously heating to 450 ℃, introducing hydrogen, controlling the air pressure to be 0.2MPa, and preserving heat for 30min;
(2) Nitriding: placing aluminum-vanadium alloy in a closed resistance furnace, introducing nitrogen gas, heating to 900 ℃, preserving heat for 90min, and cooling; the nitrogen flow rate in the heating stage is 30sccm, and the heating rate is 5 ℃/min; the nitrogen flow rate in the heat preservation stage is 60sccm; the nitrogen flow rate in the cooling stage is 20sccm;
(3) Ball milling: 9.8 parts of titanium powder, 1 part of aluminum-vanadium alloy, 1.8 parts of molten salt (0.90 part of magnesium chloride+0.77 part of holmium+0.13 part of potassium fluotitanate) and 2.9 parts of absolute ethyl alcohol medium are mixed, ball milling is carried out in an argon atmosphere, the ball-material ratio is 10:1, and the ball milling time is 21 hours; three stainless steel grinding balls with different particle sizes are adopted for ball milling, the radius is sequentially 20mm, 10mm and 6mm, the mass ratio is 2:3:5, and the rotating speed is 450-550 rpm;
(4) Acid washing with a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 20deg.C for 6min, washing with deionized water, alcohol, and acetone, and drying;
(5) The process for removing hydrogen comprises the following steps: pressure 10 -3 Pa, the temperature is 700 ℃, and the heat preservation time is 8 hours, so as to obtain the titanium alloy material.
Example 5: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step one, preparing cast ingots: the sponge titanium is taken and smelted for 5 times, and the smelting is carried out in a small-tonnage vacuum consumable arc furnace, and the specific process comprises the following steps: the smelting voltage is 28V, the argon atmosphere is protected, and the vacuum degree is 0.01Pa; cooling to 400 ℃ after smelting is completed, and taking out to obtain an ingot;
step two, preparing a powder preparation rod: cogging, rolling and straightening the cast ingot obtained in the previous step, turning oxide skin and cleaning;
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
heating titanium scraps to 700 ℃, placing the titanium scraps in a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving the titanium scraps with a 155-mesh sieve to obtain titanium powder;
(1) Hydrogenation: taking titanium powder, and vacuumizing to the pressure of 10 in an argon atmosphere -3 Pa, heating to 270 ℃, preserving heat for 150min, and drying the raw materials; continuously heating to 450 ℃, introducing hydrogen, controlling the air pressure to be 0.2MPa, and preserving heat for 30min;
(2) Nitriding: placing aluminum-vanadium alloy in a closed resistance furnace, introducing nitrogen gas, heating to 900 ℃, preserving heat for 90min, and cooling; the nitrogen flow rate in the heating stage is 30sccm, and the heating rate is 5 ℃/min; the nitrogen flow rate in the heat preservation stage is 60sccm; the nitrogen flow rate in the cooling stage is 20sccm;
(3) Ball milling: 9.8 parts of titanium powder, 1 part of aluminum-vanadium alloy, 1.8 parts of molten salt (0.95 part of sodium chloride+0.80 part of potassium chloride+0.05 part of potassium fluotitanate) and 2.9 parts of absolute ethyl alcohol medium are mixed, ball milling is carried out in an argon atmosphere, the ball-material ratio is 10:1, and the ball milling time is 21 hours; three stainless steel grinding balls with different particle sizes are adopted for ball milling, the radius is sequentially 20mm, 10mm and 6mm, the mass ratio is 2:3:5, and the rotating speed is 450-550 rpm;
(4) Acid washing with a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 20deg.C for 6min, washing with deionized water, alcohol, and acetone, and drying;
(5) The process for removing hydrogen comprises the following steps: pressure 10 -3 Pa, the temperature is 700 ℃, and the heat preservation time is 8 hours, so as to obtain the titanium alloy material.
Comparative example 1: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the size of the titanium scraps is as follows: the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
heating titanium scraps to 500 ℃, placing the titanium scraps in a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving the titanium scraps with a 155-mesh sieve to obtain titanium powder;
(1) Nitriding: placing aluminum-vanadium alloy in a closed resistance furnace, introducing nitrogen, heating to 800 ℃, preserving heat for 60min, and cooling; the nitrogen flow rate in the heating stage is 20sccm, and the heating rate is 4 ℃/min; the nitrogen flow rate in the heat preservation stage is 50sccm; the nitrogen flow rate in the cooling stage is 15sccm;
(2) Ball milling: 9.0 parts of titanium powder is mixed with 1 part of aluminum-vanadium alloy, 0.5 part of molten salt (0.27 part of magnesium chloride+0.21 part of holmium+0.02 part of potassium fluotitanate) and 1.5 parts of medium deionized water, ball milling is carried out in an argon atmosphere, the ball-material ratio is 6:1, and the ball milling time is 18 hours; the ball milling adopts three stainless steel grinding balls with different particle sizes, the radius is sequentially 20mm, 10mm and 6mm, the mass ratio is 2:3:5, and the rotating speed is 450rpm;
(3) Acid washing with a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 15deg.C for 10min, washing with deionized water, alcohol, and acetone, and drying;
(4) The process for removing hydrogen comprises the following steps: pressure 10 -2 Pa, the temperature is 600 ℃, and the heat preservation time is 4 hours, so as to obtain the titanium alloy material.
Comparative example 2: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the size of the titanium scraps is as follows: the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
heating titanium scraps to 500 ℃, placing the titanium scraps in a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving the titanium scraps with a 155-mesh sieve to obtain titanium powder;
(1) Ball milling: 9.0 parts of titanium powder is mixed with 1 part of aluminum-vanadium alloy, 0.5 part of molten salt (0.27 part of magnesium chloride+0.21 part of holmium+0.02 part of potassium fluotitanate) and 1.5 parts of medium deionized water, ball milling is carried out in an argon atmosphere, the ball-material ratio is 6:1, and the ball milling time is 18 hours; the ball milling adopts three stainless steel grinding balls with different particle sizes, the radius is sequentially 20mm, 10mm and 6mm, the mass ratio is 2:3:5, and the rotating speed is 450rpm;
(2) Acid washing with a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 15deg.C for 10min, washing with deionized water, alcohol, and acetone, and drying;
(3) The process for removing hydrogen comprises the following steps: pressure 10 -2 Pa, the temperature is 600 ℃, and the heat preservation time is 4 hours, so as to obtain the titanium alloy material.
Comparative example 3: the preparation method of the titanium alloy material for 3D printing comprises the following steps:
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps; the size of the titanium scraps is as follows: the average thickness of the titanium scraps is 1.5mm, and the average width is 0.7cm;
putting titanium scraps into a pulverizer to sequentially perform coarse grinding, semi-fine grinding and fine grinding, and then sieving with a 155-mesh sieve to obtain titanium powder;
acid washing with a mixed solution of hydrofluoric acid and nitric acid (5 wt% HF+20wt% HNO) 3 ) Pickling at 15deg.C for 10min, washing with deionized water, alcohol, and acetone, and drying; the process for removing hydrogen comprises the following steps: pressure 10 -2 Pa, the temperature is 600 ℃, and the heat preservation time is 4 hours, so as to obtain the titanium alloy material.
Experiment
Taking the titanium alloy materials obtained in examples 1-5 and comparative examples 1-3, preparing samples, respectively detecting the performances thereof and recording the detection results:
carrying out laser 3D printing on the titanium alloy material, and obtaining a sample by adopting laser power of 200W, scanning speed of 6mm/s, powder laying thickness of 1mm, defocusing amount of positive defocusing of 2mm and gas flow of 5L/s in a 93% argon+7% nitrogen atmosphere;
tensile mechanical property test: the tensile property test is carried out on the test sample by adopting an electronic universal tester, the test sample is dumbbell-shaped with the dimensions of 100mm multiplied by 10mm multiplied by 5mm, and the strain rate is 1 multiplied by 10 -4 S, the experimental temperature is 25 ℃;
and (3) compactness test: the volume of the sample was measured by a drainage method, the mass of the sample was divided by the volume to obtain the density of the sample, and the density of the sample was divided by the density of the pure titanium to obtain the density of the sample, which was 4.506g/cm 3.
From the data in the above table, the following conclusions can be clearly drawn:
the titanium alloy materials obtained in examples 1 to 5 were compared with the titanium alloy materials obtained in comparative examples 1 to 3, and it was found that,
compared with the titanium alloy materials in the examples 1/5 and the comparative examples 1-3, the titanium alloy materials obtained in the examples 2-4 have higher tensile strength and density data and better elongation data, which fully demonstrates that the strength and toughness of the 3D printing product prepared by the titanium alloy materials are improved.
Compared with example 3, the titanium powder in example 1 is not subjected to hydrogenation, ball milling and other processes; the molten salt composition in example 5 was different. In comparison with example 2, the titanium powder in comparative example 1 was not hydrogenated; the titanium powder in comparative example 2 was not hydrogenated and the aluminum vanadium alloy was not nitrided. Compared with example 1, the titanium powder preparation in comparative example 3 is not carried out under heating, and the tensile strength and density data and elongation data of examples 1/5 and comparative examples 1-3 are deteriorated, and it is understood that the preparation process of the titanium alloy material and the arrangement of the required components thereof according to the present application can promote the improvement of the strength and toughness of the 3D printed product made of the titanium alloy material.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (5)
1. A preparation method of a titanium alloy material for 3D printing is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing cast ingots: smelting titanium sponge for 2-5 times; cooling and taking out to obtain an ingot;
step two, preparing a powder preparation rod: cogging, rolling, straightening, turning oxide skin and cleaning the cast ingot obtained in the previous step to obtain a powder-making rod;
step three, pulverizing: turning the powder preparation rod obtained in the last step at a low speed to obtain titanium scraps;
heating titanium scraps to 500-700 ℃, grinding in a grinding machine, and screening to obtain titanium powder;
pickling titanium powder and removing hydrogen to obtain a titanium alloy material;
the titanium powder is ball-milled before acid washing, and the ball-milling process comprises the following steps:
mixing titanium powder with aluminum-vanadium alloy, molten salt and medium, and ball milling in argon atmosphere for 18-24 hr in the ball-to-material ratio of (6-10) of 1;
the mass ratio of the titanium powder, the aluminum-vanadium alloy, the molten salt and the medium is (9.0-9.8) 1 (0.5-1.8) 1.5-2.9; the medium is deionized water, absolute ethyl alcohol or a mixture of the deionized water and the absolute ethyl alcohol;
the molten salt comprises the following mass components: 17-21 parts of magnesium chloride, 13-18 parts of holmium and 1-3 parts of potassium fluotitanate;
the content of vanadium in the aluminum-vanadium alloy is 40wt%, the impurity O is less than or equal to 0.12wt%, and the grain diameter is 1-3 mm; and through surface nitriding treatment, the nitriding process is as follows:
placing aluminum-vanadium alloy into a closed resistance furnace, introducing nitrogen gas, heating to 800-900 ℃, preserving heat for 60-90 min, and cooling;
the nitrogen flow rate in the heating stage is 20-30 sccm, and the heating rate is 4-5 ℃/min; the nitrogen flow rate in the heat preservation stage is 50-60 sccm; the nitrogen flow rate in the cooling stage is 15-20 sccm;
the titanium powder is hydrogenated before ball milling, and the hydrogenation process is as follows: vacuum-pumping to pressure 10 in argon atmosphere -2 ～10 -3 Pa, heating to 240-270 ℃, preserving heat for 100-150 min, and drying the raw materials; continuously heating to 400-450 ℃, introducing hydrogen, controlling the air pressure to be 0.1-0.2 MPa, and keepingThe temperature is 28-30 min.
2. The method for preparing the titanium alloy material for 3D printing according to claim 1, wherein the method comprises the following steps: the titanium sponge is 0A grade small particle titanium sponge with the particle size of 0.83-12.7 mm.
3. The method for preparing the titanium alloy material for 3D printing according to claim 2, wherein the method comprises the following steps: the purity of Ti in the titanium sponge is more than or equal to 99.8%, fe is more than or equal to 0.03%, si is more than or equal to 0.01%, cl is more than or equal to 0.06%, mn is more than or equal to 0.01%, mg is more than or equal to 0.01%, ni is more than or equal to 0.01%, cr is more than or equal to 0.050%, O is more than or equal to 0.008%, C is more than or equal to 0.0045%, and H is more than or equal to 0.003%.
4. The method for preparing the titanium alloy material for 3D printing according to claim 1, wherein the method comprises the following steps: the dehydrogenation is vacuum high-temperature dehydrogenation, and the dehydrogenation process comprises the following steps: pressure 10 -2 ～10 -3 Pa, the temperature is 600-700 ℃, and the heat preservation time is 4-8 h.
5. A titanium alloy material for 3D printing produced by the production method according to any one of claims 1 to 4.
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| CN103433488A (en) * | 2013-08-12 | 2013-12-11 | 南昌大学 | Preparation method of titanium nitride-ferrous metal ceramics |
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| CN107760897A (en) * | 2017-10-30 | 2018-03-06 | 东北大学 | To hydrogenate method of the titanium sponge as raw material manufacture titanium and titanium alloy and its parts |
| CN115536051A (en) * | 2022-09-27 | 2022-12-30 | 赣州中蓝稀土新材料科技有限公司 | Preparation method of nitride series red powder |
| CN115725944A (en) * | 2022-12-05 | 2023-03-03 | 基迈克材料科技（苏州）有限公司 | Preparation method of tungsten-titanium sputtering target material |
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| JP2000192111A (en) * | 1998-12-24 | 2000-07-11 | Agency Of Ind Science & Technol | Hydrogen-containing titanium-aluminum alloy powder, production of the alloy powder, titanium-aluminum alloy sintered body and production of the sintered body |
| CN101111616A (en) * | 2005-01-27 | 2008-01-23 | 派鲁克（私人）有限公司 | A method of producing titanium |
| CN102787266A (en) * | 2012-09-04 | 2012-11-21 | 四川大学 | Titanium carbonitride based metal ceramic based on high-entropy alloy binder phase and preparation method of metal ceramic |
| CN103433488A (en) * | 2013-08-12 | 2013-12-11 | 南昌大学 | Preparation method of titanium nitride-ferrous metal ceramics |
| CN104936729A (en) * | 2013-12-30 | 2015-09-23 | 宁夏东方钽业股份有限公司 | Inter-device communication authorization and data sniffing in wireless communication systems |
| CN104511595A (en) * | 2014-12-30 | 2015-04-15 | 中南大学 | Preparation method of high-purity titanium powder |
| CN105983688A (en) * | 2015-03-04 | 2016-10-05 | 海南大学 | Fast preparation method for Ti(C1-x, Nx) (0<=x<=1)-Fe composite powder |
| CN106077675A (en) * | 2016-06-27 | 2016-11-09 | 无锡新大力电机有限公司 | A kind of preparation method of holmium ferrum nitrogen rare earth permanent-magnet powder |
| CN107760897A (en) * | 2017-10-30 | 2018-03-06 | 东北大学 | To hydrogenate method of the titanium sponge as raw material manufacture titanium and titanium alloy and its parts |
| CN115536051A (en) * | 2022-09-27 | 2022-12-30 | 赣州中蓝稀土新材料科技有限公司 | Preparation method of nitride series red powder |
| CN115725944A (en) * | 2022-12-05 | 2023-03-03 | 基迈克材料科技（苏州）有限公司 | Preparation method of tungsten-titanium sputtering target material |
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