CN106694890A - Ball-milling-high-pressure torsion method for circulatory solidification of waste titanium cuttings - Google Patents

Ball-milling-high-pressure torsion method for circulatory solidification of waste titanium cuttings Download PDF

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Publication number
CN106694890A
CN106694890A CN201611014536.4A CN201611014536A CN106694890A CN 106694890 A CN106694890 A CN 106694890A CN 201611014536 A CN201611014536 A CN 201611014536A CN 106694890 A CN106694890 A CN 106694890A
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China
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titanium
chip
cuttings
ball
pressure torsion
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罗蓬
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Shanghai Dianji University
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Shanghai Dianji University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F8/00Manufacture of articles from scrap or waste metal particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07Metallic powder characterised by particles having a nanoscale microstructure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies

Abstract

The invention provides a ball-milling-high-pressure torsion method for circulatory solidification of waste titanium cuttings. The method comprises the following steps: (1) recovery and pretreatment of the titanium cuttings: washing the titanium cuttings to remove oil and impurities; (2) ball-milling of the pretreated titanium cuttings: conducting ball-milling on the of the titanium cuttings pretreated in step (1); and (3) room-temperature high-pressure torsion solidification treatment of the milled titanium cuttings: conducting high-pressure torsion solidification treatment of the titanium cuttings subjected to ball-milling in step (2). According to the method, firstly, micron-sized refining of the outline of the titanium cuttings is realized according to the ball milling process, surface oxides of the titanium cuttings are sufficiently crushed and diffused under the action of collision and grinding of steel balls, and ultra-fine tissues are formed in the treated titanium cuttings; and then, the obtained crystalline grains are further refined under the recombination action of axial ultrahigh pressure and crosswise severe sheering of the high-pressure torsion technology at room temperature, high-pressure torsion of tissues in the solidification process of the cuttings is realized, and full densification of a remanufactured titanium material is realized.

Description

Ball milling-high pressure torsion the method for the discarded chip circulation solidification of titanium
Technical field
The present invention relates to metal material processing technology, more particularly to ball milling-high pressure that a kind of discarded chip circulation of titanium solidifies Torsion method.
Background technology
The conventional art of discarded metal chip circular treatment is high temperature founding.However, high temperature founding energy consumption is big, pollute weight, Efficiency is low, and cast sturcture's coarse grains, and mechanical performance is poor.To avoid high temperature founding, solid phase circulation and stress technology is developed. Found by literature search to prior art, by Equal-channel Angular Pressing (Equal channel angular pressing, Abbreviation ECAP) technology is applied to process borings, can crystal grain thinning, improvement remanufactures the microstructure form of material, carries High-mechanical property.Lapovok etc. exists《Journal of Materials Science》Send out on 1193-1204 pages of volume 49 within 2014 Table " Multicomponent materials from machining chips compacted by equal-channel The texts of angular pressing (multi-component material is prepared by Equal-channel Angular Pressing chip formation) ", it was recently reported that cut by aluminium Bits and magnesium chip are mutually mixed, by ECAP circular regeneration multi-component alloys materials;Luo etc. exists《Journal of Materials Science》" Recycling of titanium machining are delivered on 4606-4612 pages of volume 45 within 2010 Chips by severe plastic deformation consolidation (follow by the severe plastic deformation solid-state of titanium chip Ring) " text, propose to remanufacture block by reclaiming discarded 2 grades of titaniums (ASTM Grade 2) chip, and circulated by ECAP technologies Body material.
High pressure torsion (High-pressure torsion, abbreviation HPT) is that another kind prepares block nanometer metal material Severe plastic deformation technology.Valiev and Langdon exist《Advanced Engineering Materials》2010 volume 12 " The art and science of tailoring materials by nano- are delivered on 677-691 pages Structuring for advanced properties using SPD techniques " (realize material using SPD technologies Nanostructured regulation and control and the science and technique of high performance) text, it is indicated that HPT technologies are very effective for nanocrystalline preparation.For example, Ultra-fine microcosmic group less than 100nm is obtained in the pressure and the passage of rotation processing 5 at room temperature of 6GPa to fine copper using HPT technologies Knit.In comparison, according to ECAP technical finesse fine copper, microstructure is only refined to~200nm after 12 passages.Obviously, The refining efficiency of HPT technologies is higher than ECAP technologies.And, HPT is capable of achieving material at depressed temperatures, or at room temperature under super-pressure effect Plastic working.For example, the close-packed hexagonal titanium of high intensity its plastic forming ability is far inferior to copper, plasticity change is difficult at room temperature Shape.Zhao etc. exists《Scripta Materialia》" Microstructure and are delivered on 542-545 pages of volume 59 within 2008 properties of pure titanium processed by equal-channel angular pressing at The texts of room temperature " (room temperature Equal-channel Angular Pressing prepares the micro-structure and property of pure titanium), use at room temperature ECAP deformation process titanium a time.But in order to reduce resistance of deformation, ECAP moulds angle increases to 120 degree by 90 degree, and squeezes Pressure speed is relatively low (0.5mm/s), it reduces the Rate of strain accumulation and processing efficiency of ECAP.In contrast, HPT technologies can be high Realize to effect the room temperature processing of titanium.
Ball milling (Ball milling, abbreviation BM) is a kind of severe plastic deformation for being widely used in and preparing superfine powdery material Technology.Retrieval to prior art literature finds that Mahboubi Soufiani etc. exist《Materials and Design》2012 " Formation mechanism and characterization of are delivered on 152-160 pages of volume 37 of year (prepared by mechanical alloying for nanostructured Ti6Al4V alloy prepared by mechanical alloying The Forming Mechanism and sign of Ti6Al4V alloy nanostructures) " one text, report with titanium, aluminium, vanadium powder and micron as raw material, by BM Technology is synthetically prepared to have the Ti-6Al-4V alloy materials of nanoscale (being less than 100nm).Additionally, Zadra exists 《Materials Science and Engineering A》" Mechanical is delivered on 105-113 pages of volume 583 within 2013 The texts of alloying of titanium (mechanical alloying of titanium) ", Ti powder of the initial feed using average grain diameter less than 150 μm End, first by BM treatment, obtains the pure titanium superfines less than 25 μm, and successfully obtain block by discharge plasma sintering Titanium.
The circulation of discarded metal resource is with to remanufacture be one of the key of realizing sustainable development.Titanium is smelting cost high Metals resources, its biocompatibility is excellent, corrosion resistance is good, mechanical property is suitable, is manufacture medicine equipment, joint prosthesis, large-scale The important materials of derived energy chemical container etc..But, in order to manufacture high precision titanium structure, larger allowance need to be designed, largely Raw material translate into discarded chip.Traditional high temperature founding treatment energy consumption is big, pollution weight, and efficiency is low, and cast sturcture is brilliant Thick, the poor-performing of grain.Therefore, it is necessary to the discarded chip processing method of titanium is improved, to overcome drawbacks described above.
The content of the invention
It is an object of the invention to provide a kind of ball milling-high pressure torsion method of the discarded chip circulation solidification of titanium, by discarded titanium The block super hard nano titanium of full densification is prepared in chip, realizes efficient, the cleaning recycling of discarded titanium chip.
The present invention is for the solution technical scheme that is used of its technical problem,
Ball milling-high pressure torsion the method for the discarded chip circulation solidification of titanium, comprises the following steps:
(1) titanium chip recycling pretreatment:Cleaning titanium chip, goes to degrease and impurity;
(2) the ball milling processing of titanium chip:The pretreated titanium chip of step (1) is carried out into ball milling processing;
(3) room temperature high-pressure of titanium chip reverses curing process:It is high that titanium chip after step (2) ball milling is processed carries out room temperature Pressure reverses curing process.
The detailed process of step (1) is, the titanium chip generated with 2 grades of titaniums of end mill is cleaned as raw material using ultrasonic wave Device is cleaned, to remove the greasy dirt in raw material and impurity;Wherein, ultrasonic cleaning equipment is made using 99.9% ethanol It is cleaning solution.
The detailed process of step (2) is to insert in the ball mill container of ball mill the pretreated titanium chip of step (1), Ball mill running speed is 300rpm, and ball mill operation total duration is 15 hours, often runs 1 hour and suspends 12 minutes;Wherein, Mass ratio is 15 between chip and steel ball:1, a diameter of 10mm of steel ball;Meanwhile, to the tristearin that 1wt.% is added in ball mill container Acid is filled with argon gas as protection atmosphere as process control agent.
The detailed process of step (3) is that the titanium chip after step (2) ball milling is processed is put into oven drying, then inserts High pressure torsion mould, puts into the titanium chip in mould and is put between the upper punch of high pressure torsion device and lower anvil block, passes through Hydraulic system axially applies super-pressure in upper punch, and is rotated by lower anvil block;Wherein, oven temperature is 60 DEG C, and drying time is 30 minutes;Mould external diameter Internal diameterHeight 60mm;Super-pressure is 5Gpa, and number of revolutions is 5 times.
The method is raw material with discarded Ti chips, is combined by BM and HPT technologies, and large scale, block are prepared in circulation High hardness nanocomposite Ti materials.In BM-HPT technologies of the invention, the fine of Ti chips is realized by BM technologies first.Chip table Oxide (the TiO in face2) thoroughly crushed under the collision of steel ball, stranding stone roller.Then, carry out BM-Ti by HPT techniques at room temperature to cut The solidification of bits and nano-crystallization.In HPT systems, the super-pressure of 5GPa is applied in y direction.Meanwhile, supported by rotating The active friction of (lower anvil block) acts on material cross-section and applies a moment of torsion, produces the group by being compressed axially and lateral shear is constituted Plastic strain is closed, after extruding torsion operation, dependent variable gradually increases, the final nanocrystalline material for obtaining even tissue is real The full compact curing of existing BM-Ti chips, thoroughly eliminates porosity defects.
The advantage of the invention is that:
The conventional art of discarded metal chip circular treatment is remelting+casting.However, high temperature founding energy consumption is big, pollute weight, Efficiency is low, and cast sturcture's coarse grains, and mechanical performance is poor.To avoid high temperature founding, solid phase processing mode can be used.But It is that, when solid phase processes Ti chips, existing ECAP and BM technologies respectively have it to limit to.Ti is easy to oxidation, the oxidation of its chip surface Thing is with TiO2Form is present, strong but pliable in texture, although can be crushed to a certain extent, more by multi-pass ECAP treatment rear oxidation things Dissipate, but, the continuously distributed metallurgical imperfection that will be formed in microstructure of larger oxide weakens the mechanical performance of material.Together When, there is the refinement limit in ECAP processing, i.e., when dynamic recrystallization reaches balance with strain refinement effect, then ECAP will be difficult to make Microstructure is further refined to nanoscale.On the other hand, although BM technologies can effectively prepare superfine powder.But, at BM After reason, must carry out hot pressed sintering or powder squeeze/the subsequent treatment operation such as forging and stamping to obtain block materials, and in these operations, Because heating (sintering) time is long, and the factor such as dynamic recrystallization influence, will there is grain coarsening, the weakening strength of materials.This A little technical problems are not yet solved well at present.
BM-HPT technical schemes proposed by the present invention overcome above-mentioned limitation, can realize the technique effect described in invention.It is first First, the micron order for realizing Ti chip profile sizes by BM techniques is refined.Chip surface oxide (TiO2) in the collision of steel ball Rub with the hands and grind lower fully broken disperse, super fine organization is also formed inside chip.Then, at room temperature by HPT technologies by axially super The compound action of high pressure and horizontal intensive shear, further crystal grain thinning realizes the tissue nanosizing in chip solidification process.Phase Compared with high-temperature technologies such as founding and powder metallurgy, room temperature HPT technologies can further refine the super fine organization of BM treatment, and super High pressure (5GPa) effect is lower thoroughly to eliminate microdefect, and realization remanufactures the full densification of Ti materials.Additionally, BM-HPT rapidoprints Texture it is weaker, the isotropism level of performance is high, and this for being also easy to produce the close-packed hexagonal Ti of texture there is important technology to anticipate Justice.According to the method, from 2 grades of Ti (ASTM Grade 2) chip, remanufactured by implementing BM-HPT, obtain full densification Block Ti materials, its microhardness~3GPa, hence it is evident that higher than 2 grades of hardness (~1.4GPa) of Ti business bars.After prepared by BM-HPT, Regeneration Ti materials are significantly improved in terms of hardness and uniformity.
Brief description of the drawings
Fig. 1 is the HPT techniques that ball milling-high pressure torsion method that the discarded chip circulation of titanium proposed by the present invention solidifies is used Apparatus structure schematic diagram, in figure, 1, Ti chips, 2, upper punch, 3, lower anvil block.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below Diagram and specific embodiment are closed, the present invention is expanded on further.
Ball milling-specific the operation of high pressure torsion method of the discarded chip circulation solidification of method titanium proposed by the present invention includes:Ti The room temperature HPT curing process of chip recycling pretreatment, Ti chip BM treatment and BM-Ti chips.
1st, Ti chip recyclings pretreatment:The chip generated with 2 grades of Ti of end mill (ASTM Grade 2) is collected as raw material After chip, using inductively coupled plasma atomic emission spectrum (Inductively coupled plasma atomic Emission spectroscopy, abbreviation ICP-AES) its chemical composition (mass percent, wt.%) is analyzed, analysis result is such as Shown in table 1.As shown in Table 1, through 2 grades of Ti chips of Milling Process, its chemical composition (oxygen content) meets ASTM standard scope.Together When, Ti chips are cleaned in ultrasonic activation groove using 99.9% ethanol, to remove the greasy dirt in raw material and impurity etc..
2nd, the BM processing of Ti chips:Steel BM containers are inserted into the Ti chips obtained by step (1), chip is (straight with steel ball Footpath 10mm) between mass ratio be 15:1.Meanwhile, the stearic acid of 1wt.% is added as process control agent, and BM containers are filled with Argon gas as protection atmosphere, to prevent chip over oxidation during BM.The rotating speed of planetary BM machines is 300rpm;BM is transported Row total duration is 15 hours.In BM runnings, Ti chips steel ball shock, rub stone roller with the hands and issue raw food weldering, hardening and broken. Processed by BM, the appearance and size and oxide on surface of Ti chips are able to significantly refine.Meanwhile, pass to liquid by external container Nitrogen cycle is to reduce the friction temperature of chip-steel ball, and machine often runs 1 hour and will suspend 12 minutes.After BM terminates, use ICP-AES analyzes the chemical composition of chip, and analysis result is as shown in table 1.As shown in Table 1, through the Ti chips of BM processing in argon gas Under protection, its oxygen content only slightly rises (rising to 0.17wt.% by 0.15wt.%), and Fe contents are risen to by 0.10wt.% 0.64wt.%.
3rd, the room temperature HPT curing process of BM-Ti chips:HPT curing process devices are as shown in Figure 1.BM-Ti chips are put into Baking oven, dries 30 minutes at a temperature of 60 DEG C, then inserts disc HPT mould (the mould external diameters of steelIt is interior FootpathHeight 60mm).Put into the BM-Ti chips 1 in mould be put into HPT devices upper punch 2 and lower anvil block 3 it Between, then by hydraulic system upper punch axially apply super-pressure (5GPa), and by lower anvil block rotate 5 times it is strong to provide Radial shear is strained, and high-compactness sample is produced under pressure-the cut composite strain effect of axle-radial direction.
The chemical composition of BM-HPT samples is analyzed using ICP-AES, its result is as shown in table 1.As shown in Table 1, BM-HPT The oxygen content for remanufacturing Ti materials rises to 0.17wt.% by the 0.15wt.% of original chip, still conforms to 2 grades of Ti (ASTM Grade 2) oxygen content, and N content (<It is 0.01wt.%) constant.HPT procedure of processings do not interfere with the chemical composition of material.By micro- Hardometer tests hardness, and BM-HPT remanufactures the average hardness~3GPa of Ti materials, i.e., in the level of approximate 2 grades of Ti oxygen content, Obtain the yield strength (~1.4GPa) higher than 2 grades of Ti business bars (ASTM Grade 2).
Table 1 is that BM treatment (BM-Ti) and BM-HPT remanufacture (BM-HPT using the initial Ti chips of ICP-AES technical Analysis Ti) the chemical composition of chip afterwards.
Table 1
The compound re-manufacturing technology that the method is combined using BM and HPT, successfully prepares block high rigidity Ti materials.Fully The advantage of BM and HPT technologies is played, by implementing BM techniques, chip surface oxide (TiO2) is crushed completely;In HPT processing During, the shape of material keeps constant, therefore can multiple dependent variable of the reprocessabilty to be designed, thoroughly eliminate metallurgical scarce Fall into, realization remanufactures Ti materials and is densified entirely.And, the implementation of HPT is carried out at room temperature, compared to high temperature founding (~1200 DEG C), powder metallurgy (~900 DEG C), or the technology such as ECAP (~600 DEG C), HPT can efficiently realize crystal grain nanosizing.
BM-HPT complex techniques controllability is strong, both obtains nano-structure, and metallurgical imperfection segregation in the material is eliminated again.BM- Ti chips, due to axial super-pressure and the compound action of horizontal intensive shear, realize chip solidification process in follow-up HPT processing The nanosizing of middle microstructure, its form is able to further reform and refinement.The isotropism level of material is improved, and this is right It is significant in the close-packed hexagonal Ti for easily forming texture.Therefore, the hardness (~3GPa) of BM-HPT regeneration Ti materials is significantly high In business Ti materials (~1.4GPa) with similar oxygen content level (ASTM Grade 2)
BM-HPT technologies of preparing make regrown material be significantly improved on hardness performance, it is to avoid high temperature founding, are one Low cost is planted, and the metals resources of high-efficiency cleaning recycle technology, it is applied to the smelting cost high carried out with Ti as representative The Recycling and reuse of metals resources.
Embodiment of above only technology design and feature to illustrate the invention, its object is to allow those skilled in the art Member understands present disclosure and is carried out, and it is not intended to limit the scope of the present invention, all according to spirit of the invention The equivalent change or modification that essence is done, should all cover within the scope of the present invention.

Claims (10)

1. ball milling-high pressure torsion method that the discarded chip circulation of titanium solidifies, it is characterised in that comprise the following steps:
(1) titanium chip recycling pretreatment:Cleaning titanium chip, goes to degrease and impurity;
(2) the ball milling processing of titanium chip:The pretreated titanium chip of step (1) is carried out into ball milling processing;
(3) room temperature high-pressure of titanium chip reverses curing process:Titanium chip after step (2) ball milling is processed carries out room temperature high-pressure torsion Turn curing process.
2. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 1 solidifies, it is characterised in that step Suddenly in (1), the titanium chip generated with 2 grades of titaniums of end mill is cleaned, to remove original as raw material using ultrasonic cleaning equipment Greasy dirt and impurity in material.
3. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 2 solidifies, it is characterised in that super Sound wave cleaning device is using 99.9% ethanol as cleaning solution.
4. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 1 solidifies, it is characterised in that step Suddenly in (2), the pretreated titanium chip of step (1) is inserted in the ball mill container of ball mill, ball mill running speed is 300rpm, ball mill operation total duration is 15 hours, often runs 1 hour and suspends 12 minutes.
5. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 4 solidifies, it is characterised in that cut Mass ratio is 15 between bits and steel ball:1, a diameter of 10mm of steel ball.
6. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 4 solidifies, it is characterised in that to The stearic acid of 1wt.% is added in ball mill container as process control agent, and is filled with argon gas as protection atmosphere.
7. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 1 solidifies, it is characterised in that step Suddenly in (3), the titanium chip after step (2) ball milling is processed is put into oven drying, then inserts high pressure torsion mould, puts into mould Titanium chip in tool is put between the upper punch of high pressure torsion device and lower anvil block, is axially applied in upper punch by hydraulic system Plus super-pressure, and rotated by lower anvil block.
8. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 7 solidifies, it is characterised in that dry Case temperature is 60 DEG C, and drying time is 30 minutes.
9. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 7 solidifies, it is characterised in that mould Tool external diameterInternal diameterHeight 60mm.
10. ball milling-high pressure torsion method that the discarded chip circulation of titanium according to claim 7 solidifies, it is characterised in that super High pressure is 5Gpa, and number of revolutions is 5 times.
CN201611014536.4A 2016-11-15 2016-11-15 Ball-milling-high-pressure torsion method for circulatory solidification of waste titanium cuttings Pending CN106694890A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110026559A (en) * 2019-04-24 2019-07-19 上海电机学院 The continuous high pressure torsion deformation cycle reproducing method repeatedly of discarded titanium alloy chip
CN111690888A (en) * 2020-05-28 2020-09-22 河南新开源石化管道有限公司 Titanium alloy raw material bulldozes crowded material device
CN116689531A (en) * 2023-08-09 2023-09-05 成都先进金属材料产业技术研究院股份有限公司 Preparation method of high-strength TC4 pipe

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CN103785844A (en) * 2014-01-13 2014-05-14 上海交通大学 Nano-structure block magnesium material and preparation method thereof
CN104511595A (en) * 2014-12-30 2015-04-15 中南大学 Preparation method of high-purity titanium powder
CN105618501A (en) * 2015-12-25 2016-06-01 上海电机学院 Remanufacturing method for scrap titanium chips through ball milling-equal channel angularpressing

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CN103572088A (en) * 2013-11-27 2014-02-12 山东建筑大学 Titanium-based porous sintering composite material with nanocrystal tissues and preparation method thereof
CN103785844A (en) * 2014-01-13 2014-05-14 上海交通大学 Nano-structure block magnesium material and preparation method thereof
CN104511595A (en) * 2014-12-30 2015-04-15 中南大学 Preparation method of high-purity titanium powder
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110026559A (en) * 2019-04-24 2019-07-19 上海电机学院 The continuous high pressure torsion deformation cycle reproducing method repeatedly of discarded titanium alloy chip
CN111690888A (en) * 2020-05-28 2020-09-22 河南新开源石化管道有限公司 Titanium alloy raw material bulldozes crowded material device
CN116689531A (en) * 2023-08-09 2023-09-05 成都先进金属材料产业技术研究院股份有限公司 Preparation method of high-strength TC4 pipe
CN116689531B (en) * 2023-08-09 2023-10-27 成都先进金属材料产业技术研究院股份有限公司 Preparation method of high-strength TC4 pipe

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Application publication date: 20170524