CN105734316B - A kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders - Google Patents
A kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders Download PDFInfo
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- CN105734316B CN105734316B CN201610128648.6A CN201610128648A CN105734316B CN 105734316 B CN105734316 B CN 105734316B CN 201610128648 A CN201610128648 A CN 201610128648A CN 105734316 B CN105734316 B CN 105734316B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000010936 titanium Substances 0.000 title claims abstract description 98
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 98
- 239000000843 powder Substances 0.000 title claims abstract description 70
- 239000011159 matrix material Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000007493 shaping process Methods 0.000 title claims abstract description 22
- 229910000048 titanium hydride Inorganic materials 0.000 title claims abstract description 22
- -1 titanium hydride Chemical compound 0.000 title claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 238000001125 extrusion Methods 0.000 claims abstract description 30
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 43
- 239000012535 impurity Substances 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 description 36
- 150000004678 hydrides Chemical class 0.000 description 36
- 238000011065 in-situ storage Methods 0.000 description 16
- 238000007596 consolidation process Methods 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000011812 mixed powder Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000005728 strengthening Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001192 hot extrusion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000012857 repacking Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910033181 TiB2 Inorganic materials 0.000 description 2
- 229910007948 ZrB2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241001417495 Serranidae Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000000080 chela (arthropods) Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0073—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only borides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders, comprise the following steps：Base：Titanium hydride powders and additive are subjected to mixed merga pass molding powder compact is made；Dehydrogenation：Powder compact is heated, heating rate maintains 50 200 DEG C/min, until powder compact temperature rises to 900 1500 DEG C, and is incubated 5 minutes to 30 minutes at selected temperature；Shaping：Powder compact after heating is moved into pressurizing unit, extruding is carried out under certain pressure and extrusion ratio makes powder compact be consolidated into titanium matrix composite by extrusion die, shaping；Cooling：After the completion of extruding, titanium matrix composite is cooled to room temperature under 10 100 DEG C/min of speed, then taken out.The present invention reduces cost of material, shortens technological process, reduces the introducing of impurity during following process.The present invention has the characteristics of dehydrogenation speed is fast, and product consistency is high and mechanical property is good.
Description
Technical field
The present invention relates to a kind of method for preparing composite, and in particular to one kind using the quick dehydrogenation of titanium hydride powders and
The method that hot consolidation directly prepares shaping titanium matrix composite, belongs to technical field of nonferrous metal processing.
Background technology
Titanium is as a kind of important nonferrous materials, and because its density is low, specific strength is high, decay resistance, high-temperature mechanics
The features such as performance, good antifatigue and croop property, in recent years, in the manufacture of the military products such as aerospace flight vehicle, naval vessels and weapons
Application it is increasingly extensive.In addition, titanium also has huge application to dive in industries such as automobile, medical treatment, chemical industry, the energy and current consumptions
Power, therefore, titanium are also referred to as " the 3rd metal to emerge " and " 21 century metal ".
However, because the mechanical strength of pure titanium is relatively low, the main interstitial element (N, O, H etc.) by being solid-solution in titanium of its intensity
To provide, the content of interstitial element is higher, and the intensity of titanium is higher.But because these interstitial elements have very high consolidate in titanium
Solubility and extremely strong affinity, therefore they also are difficult to be removed during following process, such as when titanium and its alloy containing
When being heated in the aerobic and environment of nitrogen, one layer of firm hardened layer can be not only formed on surface, and oxygen and nitrogen can also be to
Material internal, which spreads, causes the lattice of material to be distorted, and causes the moulding reduction of material.Therefore, in order to meet development in science and technology pair
The growing needs of material high-performance, people always want to while purity higher titanium material is obtained, pass through a variety of works
Skill means are continuously increased the mechanical property of material to meet the needs of different field.
A kind of effective method for strengthening titanium mechanical property is that the fiber or particle of the second phase are added into Titanium base, is prepared
Go out the titanium matrix composite (Titanium Matrix Composites, TMCs) with higher intensity.Titanium matrix composite can
It will effectively be combined, make with the characteristics of high intensity and high-modulus of enhancing phase the advantages of the high ductibility and low-density of Titanium
It is standby go out titanium matrix composite possess higher specific strength and high temperature resistant property compared to matrix titanium material, it is more preferable it is antifatigue with it is anti-
Cutting performance.
Enhancing in titanium matrix composite is mutually the main reason for improving material mechanical performance.According to enhancing phase pattern,
The difference of volume fraction and content, the effect for strengthening phase in composite mainly hinder the motion of dislocation and growing up for crystal grain,
Play a part of the stress that meets with stresses and transmit simultaneously, so as to improve the intensity of material in itself, high-temperature behavior and creep resistant
Ability.Generally, following condition should be met by strengthening the selection of phase：With mechanical performances such as higher intensity, rigidity and hardness.Generally
Enhancing mutually occupies certain volume fraction, it is necessary to undertake load of the part from outside in the base, mutually sufficiently fine when strengthening
It is small and when reaching certain amount, there is the dispersion-strengtherning for hindering dislocation migration to become particularly significant；With higher heating power
Stability is learned, because titanium has higher fusing point, strengthening during hot worked accordingly has preferable thermodynamic stability
And it should not react to each other or be dissolved among matrix with matrix material；Enhancing mutually and matrix between should have good wellability with
Chemical compatibility, and without serious interfacial chemical reaction；In addition, the thermal coefficient of expansion of enhancing phase should be similar to matrix material,
With reduce due to during hot-working and follow-up use due to thermal coefficient of expansion mismatch and caused by micro-flaw.At present,
It is believed that ideal titanium matrix composite enhancing mutually mainly includes TiB, TiC, SiC, B4C and ZrB2Deng.
Addition or generating mode of the preparation method of titanium matrix composite according to reinforcement, can be divided into outer addition and original position
Two kinds of method of formation (in-situ).Outer addition is mutually to be added directly into final enhancing in metallic matrix to carry out synthetic composite material,
And in-situ preparation rule refers to that the enhancing in composite is mutually in subsequent preparation process, pass through the change of outer added elements and matrix
Learn reaction and generate.The element of the stable enhancing phase of the generation that can be reacted with titanium mainly includes B, C, TiB2、B4C、Cr3C2
And Si3N4Deng.
In the last few years, the research for being prepared titanium and titanium alloy product for raw material using titantium hydride is on the increase, using titantium hydride
Cost of material can be reduced by directly preparing titanium article, reduce technological process, improve sintered density.However, at present prepared by people
Mostly from pure titanium or titanium alloy as matrix material, titanium matrix composite still is prepared using hydride powder for titanium matrix composite
Research is also in the starting stage.N.Peillon et al. mutually mixes the TiC particles of titanium hydride powders and 10vol% and 20vol%
Close, then by cold moudling and TiC is prepared by the method freely sintered between 800-1375 DEG C under vacuum conditions
Strengthen titanium matrix composite.With utilizing the composite phase for being atomized titanium valve and hydrogenation dehydrogenation titanium powder and being prepared for raw material under same technique
Than using titantium hydride to reduce sintering temperature for raw material and improving the consistency of final material.Woong Lee et al. will be hydrogenated
Titanium valve and 0-60vol% TiC particles mix, and are then heated to by way of hot pressing under 60MPa pressure
1000-1150 DEG C, prepare TiC enhancing titanium matrix composites and the transformation to its microscopic structure is studied.Existing
In research report, the time that the dehydrogenation of titantium hydride needs is longer, and can still have some residual holes in final material, it is necessary to enter
The aftertreatment technology of one step improves the consistency of material.
Prior art has the following disadvantages：
1st, conventional casting techniques prepare titanium matrix composite, and preparation temperature is on the fusing point of matrix titanium, due to pure titanium
Fusing point is up to 1660 DEG C, it is therefore desirable to expends the substantial amounts of energy.Further, since it is inclined to produce composition during cooling
Analysis, it is therefore desirable to which the uniform of composition is reached by multiple founding.
2nd, powder metallurgic method prepares titanium matrix composite and uses titanium valve as raw matrix materials more, but due to the chemism of titanium
It is very high, it is easy to reacted at high temperature with impurity elements such as H, O, C, N in environment, therefore it is right in titanium valve production process
The requirement of surrounding environment is harsh, and the titanium valve production cost of high-purity is very high.
3rd, it is using pressure when pressureless sintering or sintering mostly to use hydride powder to prepare titanium matrix composite for raw material at present
Power is relatively low, and due to titantium hydride, the release of hydrogen can make material internal produce certain space in certain embodiments, therefore use hydrogen
Change the product consistency that titanium is directly prepared to be difficult to reach the requirement used, it is necessary to which follow-up further processing (is such as forged, rolled
System, extruding etc.) improve the consistency of material, add processing step.
The content of the invention
The technical problems to be solved by the invention are：
1st, how to simplify technique, reduce production cost, prepare enhancing phase equally distributed titanium-based composite wood in the base
Material, while reduce influence of the introducing of impurity element in process to final products performance.
2nd, how quickly the hydrogen in titantium hydride to be removed, the hydrogen in product is reduced in tolerance interval.
3rd, how to be that raw material directly prepares the titanium matrix composite section bar with high-compactness using titantium hydride.
To achieve the above object, hydride powder is mutually mixed and is cold-pressed into base by the present invention with enhancing, in repacking certainly
In Multifunctional powder consolidation system, mix powder pressed compact is heated to certain temperature by sensing heating and carried out of short duration
Hot extrusion is carried out after insulation immediately, can directly prepare with higher-density and the titanium-based of cross sectional shape with needed for is compound
Material extrudate, The present invention reduces cost of material, shortens technological process, reduces drawing for impurity during following process
Enter.In addition, the present invention it is compound can to realize that outer addition or in-situ synthesized prepare titanium-based by changing the enhancing phase species added
The preparation of material, while the present invention has the characteristics of dehydrogenation speed is fast, and product consistency is high and mechanical property is good.Technical scheme is such as
Under：
A kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders, is comprised the following steps：
Step 1, base：Titanium hydride powders and additive are subjected to mixed merga pass molding powder compact is made；Additive
Mutually or for in-situ preparation can be reacted with titanium or titantium hydride strengthen the addition phase of phase for directly enhancing；
Step 2, dehydrogenation：Powder compact is heated, heating rate maintains 50-200 DEG C/min, until powder pressure
Base temperature rises to 900-1500 DEG C, and is incubated 5 minutes to 30 minutes at selected temperature；
Step 3, shaping：Powder compact after heating is moved into pressurizing unit, entered under certain pressure and extrusion ratio
Row extruding makes powder compact be consolidated into titanium matrix composite by extrusion die, shaping；
Step 4, cooling：After the completion of extruding, titanium matrix composite is cooled to room under 10-100 DEG C/min of speed
Temperature, then take out.
Preferably, directly enhancing is mutually selected from TiC, TiB in step 12Or one kind among graphene, addition are mutually selected from stone
One kind among ink, CNT, graphene or boron.
Preferably, powder compact is heated using load coil in step 2.
Preferably, pressurizing unit and extrusion die temperature are maintained between 450-550 DEG C in step 3.
Preferably, in step 3 pressure between 50-300MPa.
Preferably, in step 3 extrusion ratio 5:1-100:Between 1.
Preferably, extruding rate is 15-100mm/s in step 3.
Preferably, extrusion die shape requires to determine according to titanium article in step 3.
Preferably, step 2 is heated and step 3 extrusion process is carried out in sealed environment, is continually fed into sealed environment
Argon gas, it is ensured that oxygen content is not higher than 200ppm in sealed environment.
Preferably, the whole technical process for preparing titanium matrix composite is no more than 30 minutes.
Compared with prior art, the present invention has the advantages that：
1st, cost of material is low, uses the intermediate product of hydrogenation and dehydrogenization to hydrogenate titanium valve as raw material, its cost is compared to pure titanium valve
Substantially reduce.
2nd, reaction speed is fast, and powder compact is that higher temperature is heated rapidly in open environment so that titantium hydride
In hydrogen can be removed substantially in 30 minutes.In addition, in the original location in spontaneous enhancing phase system, in the process for heating up and being incubated
In, enhancing can be mutually quickly generated.
Fig. 2 is hydride powder and 1vol.% CNTs (CNTs) mixed-powder pressed compact (being designated as TiH2-1CNTs) and should
Titanium matrix composite (being designated as TiH2-1CNTs-1200-5min) after pressed compact is incubated 5 minutes at 1200 DEG C obtained by extruding
XRD spectrum contrasts.It can be seen that titantium hydride is completely transformed into pure titanium after extruding, while generate In-sltu reinforcement phase.
3rd, technique, raising efficiency are simplified.Traditional titanium valve is replaced using hydride powder in the present invention, titantium hydride is taken off
The consolidation shaping of hydrogen, the in-situ authigenic (or additional enhancing phase) for strengthening phase and material is combined together, and is not required to separately through hydrogenation
Titanium powder dehydrogenation powder, greatly shortens and simplifies the process that first powder processed consolidates last reshaping again in conventional preparation techniques, carry
High production efficiency is high, reduces the possibility that material pollute by ambiance, can be prepared in 30 minutes with high cause
The titanium matrix composite product of density and strong mechanical performance.
4th, new material microscopic structure is generated.Because using titanium hydride powders, as raw material, a certain amount of hydrogen will participate in making
Phase transformation in standby and forming process, Titanium base is caused to generate new microstructure, such as coarse-grain and Ultra-fine Grained double structure.These
New microstructure has high mechanical strength and plasticity by titanium matrix composite is more conducive to.
Brief description of the drawings
Fig. 1 is Multifunctional powder consolidation system schematic diagram used in the present invention；
Fig. 2 is the XRD spectrum of titanium matrix composite made from a preferred embodiment of the present invention；
Fig. 3 is the dehydrogenation and in-situ authigenic reacting flow chart of a preferred embodiment of the present invention；
Fig. 4 is the tensile property curve of titanium matrix composite made from a preferred embodiment of the present invention.
Embodiment
Embodiments of the invention are elaborated below in conjunction with the accompanying drawings, the present embodiment using technical solution of the present invention before
Put and implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to down
The embodiment stated.The core of the present invention is that using titantium hydride be raw material, by titantium hydride dehydrogenation, strengthens phase in-situ authigenic (or outside
Add enhancing phase) with the consolidation collection of material together in same system, any similar hot consolidation technique belongs to the present invention's
Protection domain.
The selection of raw material：
The present invention use hydrogenation and dehydrogenization to prepare intermediate product hydrogenation titanium valve during titanium valve as raw matrix materials, its cost
Substantially reduced relative to pure titanium valve, saved cost of material.Further, since the hydrogen that titantium hydride discharges during dehydrogenation
Reduction reaction can occur with oxide existing for material surface, so as to reduce the oxygen content in final products, there is surface
The effect of cleaning.
Enhancing can mutually select the material for having excellent compatibility with matrix titanium and being stabilized as additional in the present invention
Increase phase, including but not limited to TiB, TiC, SiC, ZrB2Deng；Can also select can be mutual with matrix titanium in heating process
React and the material of in-situ preparation enhancing phase, including but not limited to B, C, TiB2、B4C etc..
Nucleus equipment：
Used nucleus equipment is from the Multifunctional powder consolidation system of repacking, the apparatus sketch such as Fig. 1 in the present invention
It is shown.The equipment is that hydraulic press and load coil collection are mounted in the glove box with atmosphere protection, can be held in glove box
It is continuous to be passed through argon gas and monitor oxygen content therein in real time using oxygen content detector, it is ensured that the oxygen content in glove box is in preparation
During be consistently lower than 200ppm.Powder compact by sensing heating and after being incubated a period of time is quickly moved to is heated to one in advance
Extruded in the extrusion die of constant temperature degree and using hydraulic press.The dehydrogenation of titantium hydride is strengthened the in-situ authigenic of phase by the equipment
It is combined together with the consolidation process of material, simplifies processing technology, reduces contact of the material with impurity element in environment, can
Directly prepare the titanium matrix composite section bar with higher-density.
The technological means and feature of the use of the present invention are as follows：
A. titanium hydride powders are subjected to mixed merga pass molding with a certain amount of enhancing phase powder and powder compact is made.
1st, titanium hydride powders are mixed with 0-50vol% enhancing phase powder by powder mixing machine method, mixes the powder time
According to how much controls of enhancing phase content within 0-100 hours, it can be mutually uniformly distributed with final strengthen in titanium hydride powders
It is defined.
2nd, mixed-powder is pressed into base by being molded, the pressed compact prepared by the step in the range of 300 DEG C in room temperature
Density should be between 75%-95%.
3rd, can be in mixed powder into powder because the increase of enhancing phase content, the mouldability of mix powder can be deteriorated
It is suitably added certain forming agent and helps powder compacting.
B. the mixed-powder pressed compact of titantium hydride/enhancing phase is heated using load coil, heating rate maintains
At 50-200 DEG C/min, until mixed-powder pressed compact temperature rises 900 DEG C -1500 DEG C, and 5 minutes are incubated at selected temperature
To 30 minutes.
The step is one of core procedure of the present invention, and its principal character is as follows with acting on：
1st, is mixed by powder compact and is heated for titantium hydride/enhancing using load coil, it is characterized in that heating speed
Degree is fast, mixed-powder pressed compact quickly can be heated into extrusion temperature, because the dehydrogenation effect of titantium hydride is more preferable at high temperature, so as to
Dehydrogenation rate (the quick dehydrogenation i.e. in the present invention) is accelerated, while the reduction of dehydrogenation time also reduces titanium and environment after dehydrogenation
The reaction time of middle impurity element.This step is mainly characterized by quickly heating, and low frequency, intermediate frequency are taken according to the big I of sample
Or high-frequency induction heating mode, as long as the rate of heat addition meets to require.Meanwhile, it is capable to the microwave being rapidly heated heats and other
Mode of heating can also be used as and substitute heat protocol.
2nd, the selection of heating-up temperature and soaking time, can be adjusted according to different titantium hydrides/enhancing phase system.For
Additional enhancing phase system, it need to only consider the dehydrogenation situation of titantium hydride.At a lower temperature, the time that the dehydrogenation of titantium hydride needs
Longer, the selection of heating-up temperature and soaking time should be to ensure that hydrogen can remove as basic demand completely；Increase for in-situ preparation
For strong phase system, heating and the insulating process of mixed-powder pressed compact are also that initial feed reacts to each other to be formed with the titanium after dehydrogenation
The process of In-sltu reinforcement phase, therefore also will be according to not with soaking time except the dehydrogenation situation of titantium hydride to be considered, heating-up temperature
Same in-situ authigenic reaction system does appropriate regulation with the enhancing phase size intentionally got.
3rd, the dehydrogenation of titantium hydride, the in-situ authigenic process for strengthening phase are combined with the heating process of pressed compact before extruding, it is simple
Technological process is changed, has reduced the time of contact of titanium and impurity element in environment, the impurity advantageously reduced in final products contains
Amount.
C. the mixed-powder pressed compact after sensing heating is moved rapidly into recipient, and under certain pressure and extrusion ratio
Carrying out extruding makes material be consolidated into the product of titanium matrix composite by the extrusion die with certain cavity shape, shaping.Squeeze
Pressure cylinder and mold temperature are maintained between 450-550 DEG C.Nip pressure is between 50-300MPa, and extrusion ratio is 5:1-100:1 it
Between.Extrusion die shape is fixed according to product requirement, can be bar-shaped, the other shapes of tubulose or customer requirement.
This step is another core procedure of the present invention, and its principal character and effect are as follows：
1st, pressurizing unit is installed on the induction heating apparatus in step B in the glove box of same sealing so that sensing adds
Sample after heat can be moved rapidly into extrusion die, reduce the loss of heat.
2nd, it is to prepare the key point with high-compactness titanium article, titantium hydride using the consolidation of hot extrusion progress material
Due to the precipitation of hydrogen in certain embodiments, it is possible to hole can be formed in material internal so as to reduce the consistency of material.And extrude
Large plastometric set can be produced so that the cave fillings and disappearance that material internal is formed, so as to improve the consistency of material.This
Outside, crimp can also make matrix material and the interface cohesion of enhancing phase more firm, improve the degree of consolidation of composite.
After tested, the consistency of titanium matrix composite is all higher than 99.5% after extruding.Extruded in the present invention using straight barrel type, there is phase
Can be alternatively like the isogonism extruding (Equal Channel Angular Pressing, ECAP) of effect.
3rd, extrusion die can customize as requested, so as to directly prepare the effigurate section bar of tool, including but not office
It is limited to bar-shaped, the shape such as tubulose.Sample after extruding reduces follow-up machining process, can entered close to final products pattern
One step reduces cost.
D. after the completion of extruding, the titanium matrix composite of extrusion is cooled to room temperature under 10-100 DEG C/min of speed, with
After take out.
The performance of final products can be improved by controlling the institutional framework of cooling velocity change final material.Air cooling
Cooling velocity is very fast, and the crystallite dimension of material is relatively small, has higher mechanical strength.By controlling cooling velocity, make material
Expect Slow cooling, the sample with equiaxed structure can be obtained, the moulding of material is lifted on the premise of some strength is sacrificed.
E. heating with extrusion process, argon gas is being continually fed into glove box, it is ensured that oxygen content is not higher than in environment
200ppm.The consolidation forming process of titantium hydride dehydrogenation, enhancing phase in-situ authigenic and titanium matrix composite is completed within a short period of time,
Whole technical process is no more than 30 minutes.
1st, titanium easily reacts with elements such as H, O, C, N at high temperature, therefore need to be in whole heating and extrusion process
The impurity content in environment is controlled, inert element argon (Ar) does not react with titanium, is the ideal chose of protective atmosphere.
2nd, whole dehydrogenation, enhancing phase in-situ authigenic and consolidation shaping process control were completed in 30 minutes, were to reduce
The time of contact of impurity element in the titanium matrix composite and environment that are formed after dehydrogenation.Because while in preparation process continue to
Argon gas is filled with glove box to be protected, but can not despumation element completely presence.
Except above-mentioned embodiment, the present invention can also have following alternative solution：
1st, mixing of the hydride powder with strengthening phase powder, can except the method using powder mixing machine, wet mixing, high-energy ball milling etc.
So that enhancing is mutually in titantium hydride, equally distributed technique can be as an alternative.
2nd, mode of heating uses basic, normal, high frequency sensing heating according to the big I of mixed-powder pressed compact, and can also use has soon
The microwave heating of fast heating efficiency or other heating means.
3rd, fashion of extrusion can use straight barrel type to extrude, and can also use the isogonism extruding (ECAP) with similar action, horizontal
A variety of densification modes such as extruding, hot pressing.
4th, material consolidation style can also use forging, rolling etc. to be substituted in addition to selecting to extrude.
5th, except argon gas, can also be protected using other inert gases not reacted with titanium, or in vacuum condition
Lower progress.
6th, the type of cooling removes what is illustrated in above-mentioned embodiment, and water quenching or oil quenching are also alternative.
More specifically embodiment is as follows：
By the use of titanium hydride powders as raw matrix materials in the present embodiment, in-situ authigenic is used as by the use of CNT (CNTs)
The carbon source of reaction, by powder mixing machine, it is cold-pressed into base, the mode of sensing heating and hot extrusion prepares endogenous TiC enhancing
Titanium matrix composite, its detailed process and step are as follows：
1. adding 1vol% CNTs (0.56g) in 100g hydride powders (- 200 mesh), a diameter of 10mm of 200g are added
Stainless steel abrading-ball, powder 4 hours is mixed with 200 revs/min of speed using planetary ball mill at room temperature, utilizes scanning electron
Micro- sem observation finds that now CNTs is well mixed in hydride powder.
2. taking 50g hydride powders and CNTs mixed-powder, single way stempressing pressure is passed through with 500MPa pressure at room temperature
A diameter of 28mm, a height of 25mm mixed-powder pressed compact is made.
3. in the Multifunctional powder consolidation system from repacking, mixed-powder pressed compact is put into induction coil.To closed
The argon gas that purity is 99.99% is passed through in glove box, the oxygen content in glove box is determined using oxygen analyzer, until in glove box
Atmosphere oxygen content is less than 200ppm.Recipient is heated using electric heating coil, extrusion die and pressure ram temperature is risen to 500
℃。
4. regulation intermediate frequency induction heating power supply power heats to mixed-powder pressed compact, maintain its heating rate
100 DEG C/min, until pressed compact temperature rises to 1200 DEG C, then it is incubated 5 minutes at such a temperature.After insulation terminates, high temperature is utilized
Pressed compact is quickly moved in recipient by pincers, and pressure ram then is put into extrusion die, extruded with 500MPa pressure, is extruded
Speed is 12mm/s.During pressed compact heats and extrudes, argon gas need to be persistently filled with into glove box, it is ensured that the oxygen in environment
Content is not higher than 100ppm.Internal diameter of the container used is 30mm in the present embodiment, and extrusion nozzle internal diameter is 10mm, extrusion ratio 9:1.
5. during sensing heating, in-situ authigenic reaction of the dehydrogenation of titantium hydride with strengthening phase is carried out simultaneously, and its is anti-
Answer process as shown in Figure 3.
6. after the completion of extruding, closing mold heat wires, extruded barses is air-cooled to room temperature, then take out, the present embodiment
The tensile property curve of middle titanium matrix composite is as shown in Figure 4.
Preferred embodiment of the invention described in detail above.It should be appreciated that one of ordinary skill in the art without
Creative work can is needed to make many modifications and variations according to the design of the present invention.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical scheme, all should be in the protection domain being defined in the patent claims.
Claims (8)
- A kind of 1. method that shaping titanium matrix composite is directly prepared using titanium hydride powders, it is characterised in that including following step Suddenly：Step 1, base：Titanium hydride powders and 1vol% CNTs are subjected to mixed merga pass molding powder compact is made；Step 2, dehydrogenation：The powder compact is heated under protective atmosphere using load coil, heating rate dimension Hold at 50-200 DEG C/min, until the powder compact temperature rises to 1200 DEG C, and 5 minutes are incubated at selected temperature；Step 3, shaping：The powder compact after heating is moved into pressurizing unit, the pressurizing unit adds with the sensing Heat coil collection is mounted in the glove box with atmosphere protection, and extruding is carried out under certain pressure and extrusion ratio makes the powder pressure Base is consolidated into titanium matrix composite by extrusion die, shaping；Step 4, cooling：After the completion of extruding, the titanium matrix composite is cooled to room under 10-100 DEG C/min of speed Temperature, then take out.
- 2. a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders according to claim 1, its It is characterised by, pressurizing unit described in step 3 and the extrusion die temperature are maintained between 450-550 DEG C.
- 3. a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders according to claim 1, its It is characterised by, pressure is between 50-300MPa described in step 3.
- 4. a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders according to claim 1, its It is characterised by, extrusion ratio is 5 described in step 3:1-100:Between 1.
- 5. a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders according to claim 1, its It is characterised by, extruding rate is 15mm/s-100mm/s in step 3.
- 6. a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders according to claim 1, its It is characterised by, the shape of extrusion die described in step 3 determines according to the requirement of the titanium matrix composite.
- 7. a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders according to claim 1, its It is characterised by, step 2 is heated and step 3 extrusion process is carried out in sealed environment, and argon is continually fed into the sealed environment Gas, it is ensured that oxygen content is not higher than 200ppm in the sealed environment.
- 8. a kind of method that shaping titanium matrix composite is directly prepared using titanium hydride powders according to claim 1, its It is characterised by, the whole technical process for preparing the titanium matrix composite is no more than 30 minutes.
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| CN107034375A (en) * | 2017-03-10 | 2017-08-11 | 广东省材料与加工研究所 | A kind of method that utilization hydride powder prepares high-compactness titanium article |
| CN108193064B (en) * | 2017-12-26 | 2020-03-20 | 天钛隆（天津）金属材料有限公司 | Low-cost industrial production method of TiC particle reinforced titanium-based composite material |
| TWI658884B (en) * | 2018-08-24 | 2019-05-11 | 可成科技股份有限公司 | Titanium article and method for manufacturing the same |
| CN110744051B (en) * | 2019-11-28 | 2021-12-21 | 中国有色桂林矿产地质研究院有限公司 | Preparation method of polycrystalline diamond compact |
| CN111822711B (en) * | 2020-07-16 | 2022-04-19 | 东北大学 | High-density titanium or titanium alloy part and powder metallurgy mold filling manufacturing method thereof |
| CN112030024B (en) * | 2020-07-29 | 2021-10-22 | 北京科技大学 | High-strength high-plasticity titanium-based composite material and preparation method thereof |
| CN112226639B (en) * | 2020-09-16 | 2022-04-12 | 华南理工大学 | In-situ ultrafine grain TiC reinforced titanium-based composite material based on cyclohexene ball milling medium and preparation method thereof |
| CN112342419B (en) * | 2020-09-23 | 2022-04-15 | 华南理工大学 | Method for preparing TiC reinforced titanium-based composite material based on cross-linked modified sintered titanium hydride |
| CN113199026B (en) * | 2021-03-31 | 2022-03-29 | 北京科技大学 | Titanium boride reinforced titanium-based composite material and preparation method thereof |
| CN113957288B (en) * | 2021-09-18 | 2022-05-24 | 华南理工大学 | Low-cost high-performance TiBw/Ti composite material and preparation method and application thereof |
| CN114182127B (en) * | 2021-12-09 | 2022-08-12 | 吉林大学 | High-performance in-situ reinforced titanium-based composite material and preparation process thereof |
| CN114603135A (en) * | 2022-03-11 | 2022-06-10 | 华南理工大学 | Hybrid reinforced powder metallurgy titanium-based composite material and preparation method thereof |
| CN115109959B (en) * | 2022-06-21 | 2024-02-23 | 华南理工大学 | Titanium alloy with double-scale equiaxial structure and preparation method and application thereof |
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