CN107881447A - Pure titanium of a kind of thread crystal grain of high-strength tenacity and preparation method thereof - Google Patents

Pure titanium of a kind of thread crystal grain of high-strength tenacity and preparation method thereof Download PDF

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CN107881447A
CN107881447A CN201711173272.1A CN201711173272A CN107881447A CN 107881447 A CN107881447 A CN 107881447A CN 201711173272 A CN201711173272 A CN 201711173272A CN 107881447 A CN107881447 A CN 107881447A
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crystal grain
thread
pure titanium
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titanium
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CN107881447B (en
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黄崇湘
王艳飞
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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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Abstract

The invention discloses a kind of pure titanium of the thread crystal grain of high-strength tenacity; microstructure is mixed with equi-axed crystal and formed by thread crystal grain or thread crystal grain; the major axis of wherein thread crystal grain and the length ratio of short axle are more than 40 and minor axis dimension is 10 μm~10nm, and equi-axed crystal is recrystallization Ultra-fine Grained.A kind of preparation method of the pure titanium of the thread crystal grain of high-strength tenacity is also disclosed, is comprised the following steps：(1) crystal grain that pure titanium is adjusted with 12 passage Equal-channel Angular Pressings is orientated, and obtains stud material；(2) again stud material obtained by step (1) cut after multi-pass is swaged, obtain the titanium plate material that cross section is rectangle；(3) multi-pass controlled rolling of annealing is carried out to the circulation of titanium plate material again；(4) anneal to obtain the pure titanium of the thread crystal grain of high-strength tenacity.The mechanical property of the pure titanium of the present invention is suitable with titanium alloy, the elements such as expensive cost, complicated technology and Al, the V harmful to organism of alloy is avoided, preferably as joint type, gear division class and support class organism embedded type structural material.

Description

Pure titanium of a kind of thread crystal grain of high-strength tenacity and preparation method thereof
Technical field
The invention belongs to organism surgery embedded type structural material field, and in particular to a kind of silk with high-strength tenacity energy Pure titanium material of shape crystal grain and preparation method thereof.
Background technology
Cured with biologies such as Ti-xAl-yV, Ti-xAl-yNb, Ti-wSn-xNb-yTa-zPb and Ti-wZr-xNb-yTa-zPb Treat alloys in common use titanium to compare, pure titanium not only has more preferable biocompatibility, corrosion resistance, it is thus also avoided that alloy it is expensive into Originally, the element such as complicated technology and Al, the V harmful to organism, preferably plants as joint type, gear division class and support class organism Enter type structural material.But due to lacking the invigoration effect of alloying element, conventional pure titanium shows relatively low yield strength and resistance to Mill property.Such as standard GB/T 13810-2007 (ISO 5832-2 2012) defined TA1 (Grade 1) and TA2 (Grade 2) yield strength of pure titanium is respectively 170MPa and 275MPa, the 860MPa far below Ti-6Al-4V.Surpass so exploitation has The pure titanium of high-strength tenacity energy is to expand it as bearing type structural material institute urgent problem to be solved.
Although the Ultra-fine Grained or nanocrystalline structure that are formed by severe plastic deformation can effectively improve the strong of metal material Degree, but the lattice defect such as the dislocation of saturation, crystal boundary seriously limits follow-up plastic deformation ability so that the type material yield Soon fracture failure afterwards.In addition, deposited under room temperature condition using the pure titanium of large plastometric set method refinement close-packed hexagonal structure Deform difficult, easy crack initiation the problem of.Although the form that patent CN 103981472B are wrapped up in by copper-clad uses equal channel angular Extruding realizes crystal grain refinement, but the technique needs first to be wrapped up in copper-clad, multi-pass Equal-channel Angular Pressing, removes parcel again Copper, it is extremely inefficient, it is unsuitable for large-scale production.According to multi-modal crystal grain strengthening and toughening mechanism of, patent CN 102703756B combine high Energy ball milling and discharge plasma sintering process have prepared mechanical property preferably coarse-grain/fine grain bimodal crystal grain Ti-6Al-4V. But processing step complexity and high energy consumption, even if promoting the preparation for pure titanium, the limited Strengthening and Toughening of multi-modal grainiess Ability is also difficult to the intensity for making the intensity of pure titanium reach alloy type material.X.L.Wu et al. (Heterogeneous Lamella Structure Unites Ultrafine-Grain Strength with Coarse-Grain Ductility.Proceedings of the national academy of sciences,2015；112:14501- 14505.) non-homogeneous stratiform structural mechanics incoordination strengthening and toughening mechanism of is utilized, passes through asymmetrical rolling and the method for subsequent anneal The preferably pure titanium of toughness and tenacity is prepared, but its integral material tensile strength is still below 700MPa, and only 300 μm of block size, It is difficult to practicality.A.V.Panin et al. (The effect of ultrasonic impact treatment on the deformation behavior of commercially pure titanium under uniaxial tension.Materials and design,2017；117:371-381.) it is tough according to refined crystalline strengthening and gradient-structure coupling Change mechanism, nanometer gradient layer is prepared on pure titanium surface using high-energy shot processing mode, but because nanometer gradient thickness degree is too thin, Yield strength only improves 60MPa and plasticity is greatly reduced.In addition, material prepared by the machinery nanosizing class method of surface is whole Body intensity improves seldom, and surface roughness is excessive, is unfavorable for production and practicality.
So far, pure titanium is still by force in the wide variety of bottleneck in the fields such as biologic medical, Aero-Space, war industry equipment Toughness is relatively low.Obtained by according to the mechanism such as refined crystalline strengthening, multi-modal crystal grain Strengthening and Toughening, gradient coupling and intensifying and its related process Pure titanium can not realize tough comprehensive mechanical property significantly break through in the case of, it is necessary to explore new Strengthening and Toughening microstructure and Its industrialized process for preparing.
The content of the invention
For the tough mechanical property of pure titanium it is low the problem of, it is intended to provide a kind of thread crystalline substance of high-strength tenacity from microstructure angle The pure titanium of grain.The tough mechanical property that the pure titanium has and titanium alloy is suitable, and with more preferable biocompatibility, corrosion-resistant Property, avoid the elements such as the expensive cost of alloy, complicated technology and Al, V for being harmful to organism, preferably as joint type, Gear division class and support class organism embedded type structural material.Present invention also offers a kind of system of the pure titanium of the thread crystal grain of high-strength tenacity Preparation Method.
The present invention is achieved through the following technical solutions：
A kind of pure titanium of thread crystal grain of high-strength tenacity, microstructure are mixed with equi-axed crystal by thread crystal grain and formed, wherein silk The major axis of shape crystal grain and the length ratio of short axle are more than 40 and minor axis dimension is 10 μm~10nm, and equi-axed crystal is ultra-fine to recrystallize It is brilliant.
For the volume fraction of thread crystal grain more than 80%, the misorientation between thread crystal grain major axis is less than 10°。
Equi-axed crystal is the isometric ultra-fine grain that partial, re-crystallization formation occurs through short-cycle annealing for severe plastic deformation structure.
The preparation method of the pure titanium of the foregoing thread crystal grain of high-strength tenacity, comprises the following steps：
(1) crystal grain that pure titanium is adjusted with 1-2 passages Equal-channel Angular Pressing is orientated, and obtains stud material；
(2) again stud material obtained by step (1) cut after multi-pass is swaged, obtain the titanium plate that cross section is rectangle Material；
(3)-multi-pass controlled rolling of annealing is carried out to the circulation of titanium plate material again；
(4) anneal to obtain the pure titanium of the thread crystal grain of high-strength tenacity.
The corner of Equal-channel Angular Pressing mould therefor is 120 ° in step (1).
Dependent variable≤1.4 swaged in step (2) per a time, multi-pass are swaged accumulation strain amount >=2.5.
Recovery annealing is annealed into step (3), temperature is 300~400 DEG C, and annealing time is 60s~1h each time.
Multi-pass controlled rolling process in step (3) is the synchronous symmetry rolling along panel length direction, i.e., rolls up and down The size and speed of roller are all identical and mill speed is not higher than 50mm/s.
The temperature range of step (3) multi-pass controlled rolling process is -196~400 DEG C, the dependent variable of single passage≤ 0.1, and accumulation strain amount≤0.5 of multi- pass rolling is carried out between adjacent twice annealing.
Annealing process in step (4) is the partial, re-crystallization annealing under critical recrystallization temperature, and temperature is 400~450 DEG C, the time is 30~600s.
Texture of the thread crystal grain of the obtained pure titanium of thread crystal grain along long axis direction is oriented to the soft orientation of crystallography, and waits Axialite grain is discrete to be distributed between thread crystal grain.
There is the pure titanium of thread crystal grain the reason for high-strength tenacity energy to be：(1) the thread crystal grain of ultra-fine/nano-scale and Equi-axed crystal has high density crystal boundary, can effectively improve material yield strength；(2) state or recrystallization state crystal grain are replied relative to play Strong plastic deformation crystal grain has relatively low dislocation density, and more lattice defect memory space is provided for following process hardening；(3) The discrete sub-micron being distributed between thread crystal grain and/or nanometer equiax crystal are not assisted between effectively alleviating thread crystal grain because deforming Along the stress concentration of crystal boundary caused by tune, the spatial dimension along crystal boundary strain gradient is widened, promotes structure Strengthening and Toughening；(4) compare In isometric Ultra-fine Grained or nanocrystalline, dislocation has a sufficiently long sliding path along thread crystal grain long axis direction, and in this direction soft Orientation texture is advantageous to starting for slip system, promotes material that uniform plastic deformation occurs.
At present, the agglomerate body metal material that still no microstructure is made up of thread crystal grain in scientific research and industrial circle.Its Reason is：(1) under thermoplasticity environment, crystal grain is difficult to spontaneously one direction growth；(2) conventional severe plastic deformation method Can change mother metal grain shape, but complicated dislocation multiplication, bury in oblivion, regrouping process makes crystal grain refinement obvious and is intended to be formed Isometric dislocation structure or new crystal grain.Such as Equal Channel Angular Pressing, although having circumferential confined pressure, the big shearing of corner Deformation promotes original grain fracture fragmentation and significantly can not unidirectionally elongated；The simple accumulation operation of rolling can form elongation Sheet grainiess, but the major diameter of these crystal grain is smaller；Drawing forming process does not have sufficiently large accumulation strain amount, institute The draw ratio for forming crystal grain is also very small.So the preparation of filament not only needs to accumulate sufficiently high plastic strain, also need Suitably to be plastically deformed speed and path.
The purpose of a small number of passage Equal-channel Angular Pressing steps, which is to apply bar, to be strained greatly and carries out texture adjustment, is dropped Angle between low grain sliding system and rod length direction, be advantageous to crystal grain in follow-up rotary swaging process and elongate change along rod length direction Shape.Technique of swaging can not only apply uniform circumferential confined pressure, the concentric half-duplex channel of its calibre-changeable and control single pass strain Amount is all to ensure that the key factor of axle fracture does not occur etc. for thread crystal grain.In order to avoid bar crystal grain of swaging is because of accumulated plastic strain It is excessive with torsional shear stress and be broken fragmentation, and further increase the draw ratio of thread crystal grain, it is pure after multi-pass is swaged Titanium is recycled for annealing and controlled rolling.
The pure titanium of thread crystal grain prepared by methods described, its mechanical characteristics are：There is excellent intensity and plasticity simultaneously Deformability, its tensile yield strength are more than 770MPa, and tensile strength is more than 900MPa, and Uniform Tension plasticity is more than 5%, had no progeny Elongation is more than 10%.
The strain quantity algorithm of rotary swaging process is ε1=ln (A0/ A), wherein A0It is the sectional area of pure titanium rod material before swaging, A is The sectional area of pure titanium rod material after swaging.
The strain quantity algorithm of the operation of rolling is ε2=Δ h/h0, wherein h0It is the thickness of Titanium board material before rolling, Δ h is to roll Titanium board material thickness is relative to h after system0Reduction amount.
The present invention compared with prior art, has the following advantages and advantages：
1st, the processing step and parameter strictly controlled prepares the microstructure of uniqueness, and it is easily broken both to overcome elongation shape crystal grain Fragmentation is split, deformation states structure is it also avoid and recrystallizes and grow up on a large scale；
2nd, it is strong to play fine grain simultaneously for the microstructure being made up of the thread crystal grain of micro-/ nano and ultra-fine equiaxil grain mixing A variety of strengthened mechanisms of change, heterogeneous texture coupling Strengthening and Toughening and texture toughening, the pure titanium with the structure show and closed The suitable mechanical property of golden titanium；
3rd, prepared material is practical, and the thread pure titanium of crystal grain overcomes the bottleneck of toughness and tenacity, can substitute alloy extensively The application of titanium, it is used especially for organism surgery embedded type structural material；
4th, preparation technology flow is simple, cost is low, efficiency high, is produced on a large scale.
Brief description of the drawings
Accompanying drawing described herein is used for providing further understanding the embodiment of the present invention, forms one of the application Point, do not form the restriction to the embodiment of the present invention.In the accompanying drawings：
Fig. 1 is initial raw materials in embodiment 1-3, material and different piece recrystallization annealing before partial, re-crystallization annealing The engineering stress strain curve comparison diagram of thread grain material obtained by condition.
Fig. 2 is the transmission electron microscopy (TEM) that the implementation case 1 completes gained bar cross section after multi-pass is swaged Figure.
Fig. 3 is the three-dimensional metallograph of the pure titanium of the thread crystal grain of high-strength tenacity prepared by embodiment 1, it can be seen that material is by ultra-fine Thread crystal grain is formed.
Fig. 4 is that the pure titanium of the thread crystal grain of high-strength tenacity prepared by embodiment 1 is local 500 × 100 μm2Region it is electron backscattered Diffraction (EBSD) gray-scale map.
Fig. 5 is that the pure titanium of the thread crystal grain of high-strength tenacity prepared by embodiment 1 is local 40 × 35 μm2The EBSD gray-scale maps in region, Black arrow sign recrystallization Ultra-fine Grained.
Fig. 6 is embodiment 4 (dotted line) and the engineering stress strain curve of the thread pure titanium of crystal grain prepared by embodiment 1 (solid line) Comparison diagram.
Fig. 7 is that the pure titanium of the thread crystal grain of high-strength tenacity prepared by embodiment 4 is local 40 × 35 μm2The EBSD gray-scale maps in region.
Fig. 8 is embodiment 5 (dotted line) and the engineering stress strain curve of the thread pure titanium of crystal grain prepared by embodiment 1 (solid line) Comparison diagram.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment and accompanying drawing, to this Invention is described in further detail, and exemplary embodiment of the invention and its explanation are only used for explaining the present invention, do not make For limitation of the invention.
The raw material trade mark is TA2, and technical standard meets GB/T3620.1-2007, and composition is as shown in table 1.Raw material are done Into standard tensile style, as shown in Fig. 1 thin dashed lines, yield strength is quasi-static tensile test gained engineering stress strain curve 280MPa, tensile strength 430MPa, uniform elongation 11.9%, elongation after fracture 27%.
Table 1
Embodiment 1
Raw material：Diameter 32mm pure titanium rod material.
Implement by step in detail below：
(1) twice time Equal-channel Angular Pressing：From the mould that channel diameter is 32mm, initial bar is carried out first Secondary Equal-channel Angular Pressing, the corner of extrusion die is 120 °, and extrusion temperature is 400 DEG C；After bar is rotated about the axis into 180 ° It is put into mould and carries out second time Equal-channel Angular Pressing.
(2) multi-pass is swaged：First passage, which is swaged, swages diameter 32mm bars obtained by step (1) to diameter 24mm, should Variable is about 0.58；It is about 0.81 that second passage, which is swaged and diameter 24mm bars are swaged to diameter 16mm, dependent variable,；3rd passage Swaging, diameter 16mm bars are swaged to diameter 8mm, dependent variable is about 1.39.
(3) it is 6.9 × 4mm the stud of diameter 8mm obtained by step (2) to be cut into cross section2Sheet material, panel length direction Bar length direction is parallel with swaging.
(4) sheet material obtained by step (3) is placed in recovery annealing in vacuum drying oven, temperature is 350 DEG C, time 600s.
(5) milling train is started, regulation roll is highly equal to 4mm, and regulation top and bottom rolls speed is equal and is less than or equal to 50mm/s.
(6) multi-pass room temperature symmetric rolling：Roll is highly lowered into 0.1mm, sheet material is subjected to 2 passes；Change-over panel Material pan feeding direction, sheet material is subjected to 2 passes again.
(7) step (6) is repeated 4 times again, wherein rolling direction is small for the dependent variable of panel length direction and single passage In 0.1.
(8) by pure titanium recovery annealing in vacuum drying oven obtained by step (7), temperature is 350 DEG C, time 600s.
(9) step (6)-step (8) is repeated 5 times again, obtains thickness 1mm Titanium board material.
(10) Titanium board material obtained by abovementioned steps being subjected to partial, re-crystallization annealing in a vacuum furnace, temperature is 450 DEG C, when Between be 300s.
The operation of rolling is room temperature rolling, wherein the rolling dependent variable of single passage is no more than 0.1, between adjacent twice annealing Accumulated plastic strain amount be no more than 0.35, total accumulative plastic strain amount be 0.75.
Fig. 2 is that the implementation case completes the TEM micro-structurals on gained bar cross section after step (2) multi-pass is swaged, It can be seen that grain contours are in the shaft-like such as ultra-fine.
Fig. 3 is the three-dimensional metallograph of the pure titanium of the thread crystal grain of high-strength tenacity prepared by the implementation case, it can be seen that material by Ultra-fine thread crystal grain is formed.
Fig. 4 is the local 500 × 100 μm of pure titanium material prepared by present case2The EBSD gray-scale maps in region.It is it can be seen that micro- The main body for seeing structure is made up of elongated thread crystal grain.Statistical result showed in the region, the average length of thread crystal grain are 166 μm, average aspect ratio 45.7, and composition ratio shared by thread crystal grain is 94%, the misorientation between thread crystal grain major axis is small In 10 °.The length of wherein indivedual thread crystal grain reaches 500 μm, and draw ratio is more than 100.
Fig. 5 is that pure titanium material is local 40 × 35 μm prepared by present case2The EBSD gray-scale maps in region.Black arrow indicates again Ultra-fine Grained is crystallized along the discrete distribution of thread crystal grain.
Fine line in Fig. 1 is quasistatic of the pure titanium of thread crystal grain after present case step (9) completion along rolling direction Extension test engineering stress strain curve, yield strength and tensile strength are respectively 973.7MPa and 1030.3MPa, but are uniformly prolonged The rate of stretching is only 2.1%, and elongation after fracture is more than 7%
Heavy line in Fig. 1 is quasi-static tensile of the thread pure titanium of crystal grain along rolling direction prepared by present case step (10) Testing engineering stress-strain diagram, yield strength 770.5MPa, tensile strength 909.7MPa, uniform elongation 8.3%, Elongation after fracture is more than 15%.
Embodiment 2
The present embodiment and the difference of embodiment 1 are：The partial, re-crystallization annealing temperature of preparation process (10) is 400 DEG C, Time is 480s.
Fine dotted line in Fig. 1 is quasi-static tensile testing engineering of the thread pure titanium of crystal grain along rolling direction prepared by present case Stress-strain diagram, yield strength are up to 838.2MPa, have very big work hardening rate, and tensile strength reaches 964.8MPa, uniform plastic's strain are 6.2%, and elongation after fracture is more than 12%.
Microstructure is similar with the microstructure of embodiment 1, but reply degree and recrystallization ratio decrease, thread crystalline substance Composition ratio shared by grain reaches about 99%.
Embodiment 3
The present embodiment and the difference of embodiment 1 are：The partial, re-crystallization annealing temperature of preparation process (10) is 475 DEG C, Time is 300s.
Quasi-static tensile test work of the thread pure titanium of crystal grain along rolling direction as prepared by the thick dashed line in Fig. 1 is present case Journey stress-strain diagram.Compared to embodiment 1, filament yield strength prepared by present case reduces about 90MPa, and uniformly moulds Property only increase by 1.7%, elongation after fracture is more than 16%.Thread crystal grain composition ratio is down to 73% in microstructure, and this explanation is thread Crystal grain has significant contribution to the obdurability of material.
Embodiment 4
The present embodiment and the difference of embodiment 1 are：The initial diameter of raw material is 20mm；Extruding used in step (1) The channel diameter of mould is 20mm；The first passage, which is swaged, in step (2) swages diameter 20mm bars obtained by step (1) to diameter 16mm, the second passage, which is swaged, swages diameter 16mm bars to diameter 8mm, total accumulative plastic strain amount only 1.833.Follow-up step Suddenly it is identical with embodiment 1.
Fig. 6 is that the engineering stress of gained filament material before and after partial, re-crystallization strains the present embodiment with embodiment 1 Curve comparison figure.The yield strength of the thread grain material of gained and tensile strength are respectively before the annealing of the present embodiment partial, re-crystallization 740.8MPa and 850.3MPa.Uniform elongation increases to 10.8% after partial, re-crystallization annealing, and elongation after fracture is more than 20%, but Yield strength and tensile strength are respectively 587.2MPa and 707.2MPa, all far below embodiment 1 and the acquired results of embodiment 2.
Fig. 7 is the local 40 × 35 μm of pure titanium material prepared by present case2The EBSD gray-scale maps in region.A small amount of recrystallization is super The discrete distribution of fine grain, most of crystal grain is in thread.But the average minor axis size of thread crystal grain much larger than the acquired results of embodiment 1 and Distribution is extremely uneven, and diameter is from sub-micron span to tens microns.
The present embodiment and the comparative analysis of embodiment 1 can be illustrated：Sufficiently high plasticity is accumulated in step (2) rotary swaging process Strain advantageously forms uniform, tiny thread crystal grain, and the size of thread crystal grain has a strong impact on the tough mechanical property of material, The smaller then strength of materials of diameter of thread crystal grain is higher.
Embodiment 5
The present embodiment and the difference of embodiment 1 are：The temperature of controlled rolling process is liquid nitrogen temperature, that is, -196 ℃；To avoid being formed during low temperature severe plastic deformation crackle, (6) perform 4 altogether to step (8) the step of the operation of rolling Secondary, total accumulated plastic strain amount is 50%, and final gained sheet metal thickness is 2mm.Other steps, parameter and 1 complete phase of embodiment Together.
Fig. 8 is the present embodiment (dotted line) and embodiment 1 (solid line) the gained filament material before and after partial, re-crystallization Engineering stress strain curve comparison diagram.The yield strength of gained filament material is before the annealing of the present embodiment partial, re-crystallization 981.7MPa, it is suitable with the room temperature rolling acquired results of embodiment 1, but obvious processing hardening is shown during deformation after unloading and is resisted Tensile strength reaches 1072.3MPa, and uniform elongation reaches 3.4%, and elongation after fracture is more than 7%.Pass through 450 DEG C of vacuum annealings again The yield strength of filament material obtained by 300s is 808.6MPa, tensile strength 939.9MPa, and uniform elongation increases to 7.4%, elongation after fracture is more than 14%.
It is that the intensity of filament material obtained by the present embodiment is higher than embodiment 1 that low temperature big accumulating plastic deformation induction is twin Where the reason for acquired results.
By the yield strength of the pure titanium of thread crystal grain, tensile strength, elongation after fracture and Chinese state prepared by above-described embodiment The Srgery grafting that family's standard (GB), international standard standardization body (ISO), American society for testing and materials (ASTM) are formulated is with pure The mechanical property standard of titanium or titanium alloy compares, as a result as shown in table 2.
Table 2
Note：Status bar represents material supply state in table, including annealed state (A), casting state (W), cold working state (CW), cold Process simultaneously partial, re-crystallization annealed state (CW+PRA)；Proof strength of non-proportional (R in tablep0.2) refer to corresponding to 0.2% plasticity The intensity of strain, that is, the yield strength described in this patent.
As can be seen from the table, the toughness and tenacity of the pure titanium of thread crystal grain provided by the present invention is used far above conventional surgical implantation The toughness and tenacity of pure titanium, and there is the mechanical property suitable with Ti-6Al-4V, Ti-6Al-7Nb.
Pure titanium of the thread crystal grain of a kind of high-strength tenacity provided by the present invention and preparation method thereof is not limited to the plant of biologic medical surgery Enter the application in terms of type structural material.It is every by a kind of pure titanium of the thread crystal grain of high-strength tenacity provided by the present invention and its preparation side Method belongs to the scope of this patent in the application of any field, industry.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include Within protection scope of the present invention.

Claims (9)

  1. A kind of 1. pure titanium of thread crystal grain of high-strength tenacity, it is characterised in that microstructure by thread crystal grain or thread crystal grain with etc. The mixing of axialite grain is formed, wherein the major axis of thread crystal grain and the length ratio of short axle be more than 40 and minor axis dimension be 10 μm~ 10nm, equi-axed crystal are recrystallization Ultra-fine Grained.
  2. 2. the pure titanium of the thread crystal grain of high-strength tenacity according to claim 1, it is characterised in that the volume fraction of thread crystal grain is big Misorientation between 80%, thread crystal grain major axis is less than 10°。
  3. 3. the preparation method of the pure titanium of the thread crystal grain of high-strength tenacity as described in claim any one of 1-2, it is characterised in that including Following steps：
    (1) crystal grain that pure titanium is adjusted with 1-2 passages Equal-channel Angular Pressing is orientated, and obtains stud material；
    (2) again stud material obtained by step (1) cut after multi-pass is swaged, obtain the titanium plate material that cross section is rectangle；
    (3)-multi-pass controlled rolling of annealing is carried out to the circulation of titanium plate material again；
    (4) anneal to obtain the pure titanium of the thread crystal grain of high-strength tenacity.
  4. 4. preparation method according to claim 3, it is characterised in that Equal-channel Angular Pressing mould therefor in step (1) Corner be 120 °.
  5. 5. preparation method according to claim 3, it is characterised in that the dependent variable swaged in step (2) per a time≤ 1.4, multi-pass is swaged accumulation strain amount >=2.5.
  6. 6. preparation method according to claim 3, it is characterised in that be annealed into recovery annealing, temperature in step (3) For 300~400 DEG C, annealing time is 60s~1h each time.
  7. 7. preparation method according to claim 3, it is characterised in that the multi-pass controlled rolling process in step (3) is Along the synchronous symmetry rolling in panel length direction, i.e., the size of top and bottom rolls and speed are all identical and mill speed is not higher than 50mm/s。
  8. 8. preparation method according to claim 3, it is characterised in that the temperature of step (3) multi-pass controlled rolling process Scope is -196~400 DEG C, dependent variable≤0.1 of single passage, and multi- pass rolling is carried out between adjacent twice annealing Accumulation strain amount≤0.5.
  9. 9. preparation method according to claim 3, it is characterised in that the annealing process in step (4) is critical recrystallization At a temperature of partial, re-crystallization annealing, temperature be 400~450 DEG C, the time is 30~600s.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019100809A1 (en) * 2017-11-22 2019-05-31 四川大学 High strength and toughness filamentous grain pure titanium and preparation method therefor
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112160029B (en) * 2020-09-27 2022-06-21 南京理工大学 Quasi-single crystal tube and preparation method thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0853726A (en) * 1994-08-09 1996-02-27 Nippon Steel Corp Pure titanium thin sheet for roll forming and its production
CN102232124A (en) * 2008-10-22 2011-11-02 木工技术公司 Commercially pure nanostructured titanium for biomedicine and a method for making a bar thereof
CN105772503A (en) * 2015-12-27 2016-07-20 佛山市领卓科技有限公司 Preparation method for high-strength pure titanium
CN106636747A (en) * 2016-12-29 2017-05-10 广东技术师范学院 Manufacturing method for producing commercial pure titanium plate by adopting double annealing of heavy and medium plate mill

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4000270C2 (en) * 1990-01-08 1999-02-04 Stahlwerk Ergste Gmbh & Co Kg Process for cold forming unalloyed titanium
JPH07124242A (en) * 1993-11-09 1995-05-16 Nikon Corp Implant
JP4686700B2 (en) * 2003-10-01 2011-05-25 独立行政法人産業技術総合研究所 Microstructured titanium and manufacturing method thereof
US20050126666A1 (en) * 2003-12-15 2005-06-16 Zhu Yuntian T. Method for preparing ultrafine-grained metallic foil
US20060213592A1 (en) * 2004-06-29 2006-09-28 Postech Foundation Nanocrystalline titanium alloy, and method and apparatus for manufacturing the same
CN1745922A (en) * 2005-09-15 2006-03-15 上海交通大学 Constant diameter right-angle extruding production of micro/nanometer crustal industrial pure titanium block
CN101219444B (en) * 2008-01-14 2010-12-08 西安建筑科技大学 Isometric bending channel deformation production method for high-strength commercial titanium block at room temperature
JP5166921B2 (en) * 2008-03-10 2013-03-21 株式会社神戸製鋼所 Titanium alloy plate with high strength and excellent formability
CN101624690B (en) * 2009-08-10 2011-04-06 西安建筑科技大学 Preparation method for difficult-to-deformation metal block material room temperature equal-diameter bending passage deformation
CN103981472B (en) * 2014-05-06 2016-01-06 西北工业大学 A kind of Equal-channel Angular Pressing prepares the method for the pure titanium of Ultra-fine Grained
JP2016000848A (en) * 2014-06-11 2016-01-07 株式会社神戸製鋼所 Titanium alloy forged material
JP2016023315A (en) * 2014-07-16 2016-02-08 株式会社神戸製鋼所 Titanium plate and manufacturing method therefor
JP6737686B2 (en) * 2016-10-24 2020-08-12 国立大学法人豊橋技術科学大学 Pure titanium metal wire and its processing method
CN107881447B (en) * 2017-11-22 2019-04-23 四川大学 A kind of pure titanium of high-strength tenacity filiform crystal grain and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0853726A (en) * 1994-08-09 1996-02-27 Nippon Steel Corp Pure titanium thin sheet for roll forming and its production
CN102232124A (en) * 2008-10-22 2011-11-02 木工技术公司 Commercially pure nanostructured titanium for biomedicine and a method for making a bar thereof
CN105772503A (en) * 2015-12-27 2016-07-20 佛山市领卓科技有限公司 Preparation method for high-strength pure titanium
CN106636747A (en) * 2016-12-29 2017-05-10 广东技术师范学院 Manufacturing method for producing commercial pure titanium plate by adopting double annealing of heavy and medium plate mill

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
VLADIMIR V.等: "Microstructure and properties of pure Ti processed by ECAP and", 《MATERIALS SCIENCE AND ENGINEERING A》 *
VLADIMIR V等: "Grain refinement and properties of pure Ti processed by warm ECAP", 《MATERIALS SCIENCE AND ENGINEERING》 *
ZHIGUO FAN等: "Microstructures and mechanical deformation behaviors of ultrafine-grained", 《MATERIALS SCIENCE AND ENGINEERING A》 *
乔珍等: "退火温度对 ECAP+CR 制备的", 《稀有金属材料与工程》 *
罗雷等: "纳米压痕法测量超细晶工业纯钛", 《稀有金属材料与工程》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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