CN107287464A - A kind of composite porous preparation method of titanium-based of the ceramics containing nano TiN - Google Patents
A kind of composite porous preparation method of titanium-based of the ceramics containing nano TiN Download PDFInfo
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- CN107287464A CN107287464A CN201710567350.XA CN201710567350A CN107287464A CN 107287464 A CN107287464 A CN 107287464A CN 201710567350 A CN201710567350 A CN 201710567350A CN 107287464 A CN107287464 A CN 107287464A
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- 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
- C22C1/08—Alloys with open or closed pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The invention provides a kind of composite porous preparation method of titanium-based of the ceramics containing nano TiN, it uses powder metallurgy pore creating material technology, by the high pure nitrogen that certain pressure intensity is passed through in titanium valve ball milling, prepare the composite powder precast body of the ceramic particle containing nano TiN, be incorporated a certain amount of absolute ethyl alcohol and uniformly mixed with corynebacterium urea as intermixture and binding agent, suppress that green compact, cryogenic vacuum are sintered, high temperature solid-phase sintering has prepared that composition is controllable, titanium-based with certain voidage is composite porous；The inventive method has high intensity using the titanium-based prepared by the composite granule of mechanical ball mill fabricated in situ particle containing nano TiN is composite porous, the excellent porous titanium matrix composite of comprehensive mechanical property, make it have stronger high-temperature-resistant and anti-corrosion performance, extend the wear life of porous titanium matrix composite, a kind of new material technology approach is provided for the application in the fields such as sewage purification, biological implantation material, with extraordinary application prospect.
Description
Technical field
The present invention relates to the technical field of hard alloy powder metallurgical, and in particular to a kind of titanium-based of the ceramics containing nano TiN
Composite porous preparation method.
Background technology
Hole, assigns porous material brand-new excellent properties, it is possessed the incomparable function of dense material, hole
Feature causes metal material to be provided simultaneously with the double grading of structural material and functional material, the utilization for substantially having three aspects.One
Aspect be function and usage such as：Filter with separating, heat exchange, porous electrode, catalytic reaction, energy-absorbing damping, noise elimination noise reduction etc.；One side
Face be structural applications such as：Space flight and aviation industry, auto industry, build also, mechanical part etc.；One side biomedical applications.Exactly
Field and wide market prospects are widely used because porous metals have, the concern of researcher is caused in recent years.And
Porous titanium matrix composite（Abbreviation TMC）It is, using Titanium as matrix, plus the second as reinforcement, the composite wood of composition
Material.For titanium matrix composite, because ceramic phase has high-melting-point, corrosion-resistant, high modulus of elasticity, good intensity etc.
Characteristic.Ceramics have widely been applied among titanium matrix composite as enhancing in recent years, common ceramic enhancement phase master
There are SiC, TiC, B4C、TiB2、ZrB2、TiAl；These ceramic enhancement phases are introduced all by methods such as additional or fabricated in situ
The different degrees of room-temperature property for improving titanium base material, high-temperature behavior, antioxygenic property, wear resistance etc., is greatly expanded
The purposes of material and extend service life.
But TiN is same as a kind of refractory ceramics, with high fusing point, the features such as high specific strength, specific stiffness, but will
TiN ceramic phases are incorporated into the system of titanium-based porous material by it as the also few relevant reports of reinforcement of Ti based composites
It is standby above to have not been reported.But on micron, the enhancing of nanoscale TiN particles are incorporated into other metal optimizing process,
Occur in that more report and practice.
Old et al. the TiN particles that have studied strengthen the interface microstructure of AgCuTi alloy brazed CBN abrasive materials, in composite soldering
The TiN of addition 8%（Size is less than 5 μm）Particle, finds not only to make micro- group of Ag-Cu-Ti solder alloys after adding TiN particles
Knit and obtained obvious refinement, and form using TiN particles as enhancing phase, the metal-based compound material based on silver-base alloy
Material, and significantly improve the hardness of bonding agent layer.Liu et al. is prepared for the TiN of variable grain content using powder metallurgic methodP/
Cu series composite materials.TiN particles be have studied to TiNP/ Cu hardness, yield strength, electric conductivity and frictional behaviour abrasiveness
The influence of energy.As a result TiN is shownP/ Cu hardness, yield strength, friction and wear behavior are substantially better than fine copper.Lee et al. have studied
Influence of the TiN-Ti fining agents to fine aluminium and Al-4Cu alloy structures and performance, discovery adds ultra-fine in aluminium and aluminium alloy melt
Ceramic particle can provide substantial amounts of dispersoid particle to promote Heterogeneous Nucleation so that tissue substantially refines the ratio for causing equiax crystal
Significantly improve, the α-Al phase averages sizes of addition 0.2wt%TiN/Ti fining agents are refined to 131 μm by 161 μm, its tensile strength
103.1% and 155.4% has been respectively increased than the Al-4Cu alloy samples for addition fining agent respectively with yield strength.King et al. grinds
The industrial experiment that nanoscale TiN particles are added in 55SiMnMo steel is studied carefully, has as a result shown to add the 55SiMnMo of nano TiN particle
The yield strength of steel of the steel than being not added with nano TiN particle improves 10.0%, and bainite size has a certain degree of refinement, its
Middle TiN is mainly serving heterogeneous nuclei, pinning and precipitation enhancement in the tissue so that pure material is pure.TiN as can be seen here
Particle has obtained relatively broad utilization in metallic composite, is especially improving metal structure form, mechanical property, resistance to height
There is obvious action in terms of temperature, wear resistance.
In the preparation process of titanium matrix composite main method be outer addition and in-situ synthesis, but outer addition by
High in reinforcement price, reinforcement and matrix wetability are poor, thermodynamic instability, Presence of an interface chemically react, interface cohesion is strong
Spend low shortcoming, it is difficult to applied to large-scale industrial production.
The content of the invention
For above shortcomings in the prior art, it is an object of the invention to provide a kind of cost is low, reinforcement grain
Degree is small, be uniformly dispersed, the system that interface bond strength is high, a kind of titanium-based of the ceramics containing TiN of excellent material performance is composite porous
Preparation Method, it is existing to solve to overcome TiN enhancings and the defect that titanium-based basal body interface bond strength is low, material property is poor
Titanium-based porous material corrosion resistance obtained by the POROUS TITANIUM preparation technology of technology is poor, material property deteriorates, service life is short, technique
The problems such as complexity, high energy consumption.
To achieve the above object, present invention employs following technical scheme：
A kind of composite porous preparation method of titanium-based of the ceramics containing nano TiN, comprises the steps：
1）Weigh titanium valve to be fitted into advance with washes of absolute alcohol and dried high-energy ball milling tank, ratio of grinding media to material is 10 ~ 20：1；
2）The high-energy ball milling cover that will be equipped with titanium valve is good, the tank body more than 3 times for washing ball grinder is filled with nitrogen, to discharge in ball grinder
Air, nitrogen is then filled with into ball grinder, be filled with nitrogen pressure be 5 × 105~20×105Pa；
3）It is filled with into ball grinder after nitrogen, multiple mechanical ball mill is carried out to the titanium valve in ball grinder, each Ball-milling Time is
30 ~ 60 minutes, the interval time per adjacent ball milling twice was 10 ~ 30 minutes, and ball milling total time is 4 ~ 8 hours；Obtained after ball milling
Composite granule containing nano TiN particle；Then, treat that tank body is cooled to after normal temperature, composite granule is taken out from ball grinder；
4）Composite granule obtained above is mixed by its 1.5 times of volumes with urea in grinding body, every kilogram is pressed in mixed process
Ratio of the mixing beyond the region of objective existence of composite granule and urea with 10 ~ 15mL absolute ethyl alcohols adds absolute ethyl alcohol；Wherein, the granularity of urea is
0.8 ~ 1.38mm, mixing time is 20 ~ 30min, obtains compound；
5）With steel die by the compound isostatic pressing obtained by back, pressing pressure is 200 ~ 250MPa, dwell time
For 60 ~ 90s, the demoulding obtains green compact；
6）Green compact are put into vacuum carbon tube furnace and are sintered, sintering process is divided into cryogenic vacuum sintering and high-temperature solid sintering two
Step is carried out；In cryogenic vacuum sintering process, it is 1 × 10 to control vacuum in vacuum carbon tube furnace-2~1×10-2Pa, control heating speed
Rate is that 2 ~ 5 DEG C/min is sintered from room temperature to 400 DEG C, and 45 ~ 60min is incubated at 400 DEG C；Subsequently into high-temperature solid
Sintering process, temperature is increased to 1100 ~ 1150 DEG C, is 1 × 10 in vacuum-31.5 ~ 2h is sintered under Pa environment；After the completion of sintering,
The titanium-based that furnace cooling obtains the particle containing nano TiN to taking-up after room temperature is composite porous.
In the composite porous preparation method of titanium-based of the above-mentioned ceramics containing nano TiN, preferably, the step 1）
Employed in the purity of titanium valve be more than 99.5%, the grain diameter of titanium valve is less than 50 μm.
In the composite porous preparation method of titanium-based of the above-mentioned ceramics containing nano TiN, preferably, the step 2）
In the purity of nitrogen used be more than 99.99%.
In the composite porous preparation method of titanium-based of the above-mentioned ceramics containing nano TiN, preferably, the step 3）
In, the drum's speed of rotation for carrying out ball milling is 400 ~ 600r/min.
In the composite porous preparation method of titanium-based of the above-mentioned ceramics containing nano TiN, preferably, the step 4）
In, the urea uses chemical pure needle-like urea.
Compared to prior art, the present invention has the advantages that：
1st, in the composite porous preparation method of the titanium-based of present invention ceramics containing nano TiN, in the high pure nitrogen of certain pressure
In atmosphere, pass through ball-milling technology so that titanium valve is during ball mill crushing, under high-speed impact, fine titanium powder particles and nitrogen point
Son contact generation nano TiN particle, and Dispersed precipitate is with powder, utilizing low cost feedstock, in-situ preparation TiN containing nanoscale potteries
The multiple fore-put powder of porcelain enhancing, the effect with optimization titanium base material performance of a certain amount of nano TiN ceramic particle, to prepare titanium-based
Composite porous preparation provides a kind of economic and practical new method.
2nd, the composite porous preparation method of titanium-based of the particle of the invention containing nano TiN, using powder metallurgy boring technique,
Fore-put powder is mutually combined using nanoscale TiN enhancings and has prepared that titanium-based is composite porous, and the material has special space
Structure, with high specific strength, high temperature resistant, anticorrosive, and its good connectedness can apply to the filtering of waste water, biological plants
Enter material etc., a kind of new technological approaches is provided to prepare the porous titanium matrix composite of high intensity multipurpose, with very good
Application prospect.
3rd, titanium-based porous material preparation method of the invention, using needle-like urea as pore creating material, is made using absolute ethyl alcohol
For intermixture and binding agent, easily removing, and the subtractive process of urea will not introduce other impurity；And urea and absolute ethyl alcohol
Removing will not produce the material of pollution environment, while also there is low raw-material cost.And using needle-like urea as making
Hole agent, can prepare the higher porous material of space percent opening.
4th, titanium-based porous material preparation method of the invention, employs two-part sintering process；Rank is sintered in cryogenic vacuum
Section vacuum abjection, high-temperature vacuum sintering stage the advantage is that to the sintering of matrix material, and cryogenic vacuum sintering stage is by urea
The gas of decomposition is quickly drawn out body of heater, it is to avoid pollution of the furnace gas to sample, and the removing time for shortening urea shortens preparation
In the cycle, the consumption of the energy is reduced, cost is reduced；Meanwhile, high-temperature vacuum sintering stage uses vacuum for 1 × 10-3Pa environment
Lower protection sintering, it is ensured that sintered specimen is not oxidized in body of heater.
5th, titanium-based porous material preparation method of the invention, it is only necessary to utilize electronic scale, grinding body, high energy ball mill, steel
The equipment such as grinding tool, press, vacuum carbon tube furnace just can be implemented, and equipment is simple, easy to operate, it is easy to accomplish, be conducive to big rule
The commercial introduction of mould.
Brief description of the drawings
Fig. 1 is the process chart of the composite porous preparation method of titanium-based of present invention ceramics containing nano TiN.
Fig. 2 detects collection of illustrative plates for the microscopic appearance scanning electron microscope (SEM) photograph and XRD of titanium valve.
Fig. 3 is composite granule microscopic appearance scanning electron microscope (SEM) photograph of the high-energy ball milling after 6 hours.
Fig. 4 is the XRD spectrum of prefabricated composite granule of the high-energy ball milling after 2 hours and 6 hours.
Fig. 5 is the macro morphology scanning electron microscope (SEM) photograph of acicular morphology granular urea.
Fig. 6 is temperature control curve of the compacting gained green compact in sintering process in the embodiment of the present invention 1.
Fig. 7 is the shape appearance figure of the porous titanium matrix composite of gained in the embodiment of the present invention 1.
Fig. 8 is the hole wall microscopic appearance figure of the porous titanium matrix composite of gained in the embodiment of the present invention 1.
Fig. 9 is the differential thermal analysis curve figure of urea.
Figure 10 is the incompressible stress-strain curve of the resulting materials of the embodiment of the present invention 1.
Embodiment
Crystal grain thinning, enhancing Metal Mechanic Property, anticorrosive, anti-are had based on micron, nanoscale TiN particles in a metal
Remarkable result in terms of polishing machine, it is contemplated that using nano TiN ceramics further improve POROUS TITANIUM mechanics, it is anticorrosive,
The performance such as wear-resisting.In-situ synthesis makes reinforcement in preparation process by the original that chemically reacts by adding reactive element powder
Position synthesis, with raw material is cheap, excellent performance letter valency ratio.In order to avoid there is particle surface pollution and matrix table in outer addition
The problems such as chemical reaction between face, it may be considered that compatibility, interface cohesion are prepared by the method for fabricated in situ excellent
The titanium-based of the ceramics containing nano TiN is composite porous, and carries out systematic research to it, the use for extending porous titanium material
Field and had far-reaching significance using model.This is directed to, the invention provides a kind of titanium-based of the ceramics containing nano TiN is porous multiple
Condensation material preparation method, to solve the industrially prepared problem that the ceramic titanium-based containing nano TiN is composite porous.
The present invention containing nano TiN ceramics the composite porous preparation method flow of titanium-based as shown in figure 1, specifically include as
Lower step：
1）Weigh titanium valve to be fitted into advance with washes of absolute alcohol and dried high-energy ball milling tank, ratio of grinding media to material is 10 ~ 20：1.
It is former for the titanium-based ceramic containing nano TiN for ensureing preparation composite porous purity and performance in the step
In material as Titanium base material titanium valve purity more preferably greater than 99.5%, also, preferably titanium valve grain diameter be less than 50 μm,
Preferably 38 ~ 48 μm, because titanium is as material matrix, its granule size has very big shadow to the mobility during powder pressure-like
Ring, after testing, this particle size range is optimum range, is conducive to absorption of the titanium valve particle to nitrogen in subsequent step, so that more
Good participation reacts to form reinforcement.
2）The high-energy ball milling cover that will be equipped with titanium valve is good, the tank body more than 3 times for washing ball grinder is filled with nitrogen, to discharge ball milling
Air in tank, is then filled with nitrogen into ball grinder, and the pressure for being filled with nitrogen is 5 × 105~20×105Pa。
In the step, the tank body more than 3 times for washing ball grinder is filled using nitrogen, it is ensured that the discharge that air goes out in tank body,
Then nitrogen is filled with as protective gas into tank body again so that mechanical milling process is carried out in a nitrogen atmosphere, can effectively prevent
The formation of oxide and the solid solution of oxygen atom, keep the cleanliness of material.Meanwhile, nitrogen is reaction generation TiN enhancer
Critical reactants, therefore the purity of nitrogen used is preferably more than 99.99%, it is to avoid introduce impurity；And nitrogen is filled with into ball grinder
The pressure of gas ensures 5 × 105~20×105Pa, be in order to build ball milling produce reinforcement Tooth preparation air pressure environmental condition.
3）It is filled with into ball grinder after nitrogen, multiple mechanical ball mill is carried out to the titanium valve in ball grinder, during each ball milling
Between be 30 ~ 60 minutes, per adjacent ball milling twice interval time be 10 ~ 30 minutes, ball milling total time be 4 ~ 8 hours；After ball milling
Obtain the composite granule containing nano TiN particle；Then, treat that tank body is cooled to after normal temperature, by composite granule from ball grinder
Take out.
In this step, mechanical ball mill causes titanium valve constantly impact friction, shock mutually in ball grinder with stainless steel ball,
The effect of the broken and crystal grain refinement of titanium valve particle is reached, is conducive to improving the surface energy of titanium valve powder, while in shattering process
Middle titanium valve powder have accumulated substantial amounts of lattice defect, such as room, distortion, dislocation；Meanwhile, pass through control in Mechanical Milling Process
Nitrogen pressure pressure, ball milling method and the Ball-milling Time of tool mechanical milling process so that the height of the nanometer titanium power obtained by after ball milling
Specific surface area absorption nitrogen, the nitrogen adsorbed forms nanoscale reinforcement with the directly reaction of titanium valve seed activity surface, obtains
Composite granule containing nano TiN particle.In order to reach more preferable ball milling and adsorption reaction effect, the ball mill for carrying out ball milling turns
Speed is preferably 400 ~ 600r/min.
4）Composite granule obtained above is mixed by its 1.5 times of volumes with urea in grinding body, by every in mixed process
Ratio of the mixing beyond the region of objective existence of kilogram composite granule and urea with 10 ~ 15mL absolute ethyl alcohols adds absolute ethyl alcohol；Wherein, the grain of urea
Spend for 0.8 ~ 1.38mm, mixing time is 20 ~ 30min, obtains compound.
It is that, as pore creating material, urea is preferred to use acicular morphology particle that urea is added in the step, and its surface area is squeezed with anti-
Pressure energy power is less than traditional circular urea, can reduce pore creating material and frictional force of the powder in pressing process so that raw pressed compact
Stress is more uniformly distributed, more easy-formation.It is due to material in foamed material mesoporous character for the selection of urea size scope
Performance has conclusive influence, and the granularity selection of urea is 0.8 ~ 1.38mm, helps sintering finished pore structure uniformly, subtracts
Frictional force in small pressing process, so as to reduce internal flaw.
5）With steel die by the compound isostatic pressing obtained by back, pressing pressure is 200 ~ 250MPa, pressurize
Time is 60 ~ 90s, and the demoulding obtains green compact.
During compressing, pressurize is conducive to effective transmission of pressure so that raw pressed compact is more densified, increase life
The intensity of pressed compact, it is to avoid the generation of arch bridge effect between particle.
6）Green compact are put into vacuum carbon tube furnace and are sintered, sintering process is divided into cryogenic vacuum sintering and high-temperature solid burns
The step of knot two is carried out；In cryogenic vacuum sintering process, it is 1 × 10 to control vacuum in vacuum carbon tube furnace-2~1×10-2Pa, control rises
Warm speed is that 2 ~ 5 DEG C/min is sintered from room temperature to 400 DEG C, and 45 ~ 60min is incubated at 400 DEG C；Subsequently into high temperature
Solid state sintering process, temperature is increased to 1100 ~ 1150 DEG C, is 1 × 10 in vacuum-31.5 ~ 2h is sintered under Pa environment；Sinter
Cheng Hou, after furnace cooling to room temperature take out obtain the particle containing nano TiN titanium-based it is composite porous.
Heat treatment of the step to green compact has been divided into cryogenic vacuum sintering and high-temperature solid sinters two steps and carried out.It is true in low temperature
In empty sintering process, when temperature reaches 400 DEG C, urea is substantially completely decomposed, and in cryogenic vacuum sintering stage, heating rate
Preferably relatively slow, it is optimal in 2 ~ 5 DEG C/min to control heating rate, is caused with avoiding urea from decomposing the too fast raw pressed compact expansion of release
Cave in；In cryogenic vacuum sintering process, it is 1 × 10 to control vacuum in vacuum carbon tube furnace-1~1×10-2Pa, purpose in order that
The gas for obtaining pore creating material decomposition is extracted into outside body of heater rapidly, it is to avoid pollution sample, 45 ~ 60min is incubated at 400 DEG C, it is therefore an objective to really
Protect urea completely out.In high-temperature solid sintering process, vacuum is used for 1 × 10-3In 1100 ~ 1150 DEG C of temperature under Pa environment
Carry out protection sintering, it is ensured that sintered specimen is not oxidized in body of heater, meanwhile, in the high-temperature solid sintering process, in sintering
Neck length megastage, TiN ceramic particles can be as nucleating agent, and promotion forms heterogeneous nucleation and carrys out crystal grain thinning, while hindering crystal boundary
Growth reduce crystal grain coarsening rate, crystal grain thinning can effectively improve the strong of material in porous titanium matrix composite
Degree, this is that other intensifying methods can not compare, under identical external force, with strain facies pair near crystal boundary inside small grains
Smaller, deformation is uniform, comparatively, and stress, which is concentrated, causes the chance of cracking also less so that gained titanium-based porous material energy
It is enough that larger deformation is born before cracking；On the other hand, during material stress and deformation, TiN can bear higher load
Lotus, to hinder the extension of crackle or change its extension approach, strengthens Crack Extension energy, so as to improve the intensity of titanium-based porous material
And toughness so that the comprehensive mechanical property of titanium-based porous material is improved.The high-melting-point, corrosion-resistant of TiN ceramic particles simultaneously
Characteristic can further improve high temperature resistant, the corrosion resistance of titanium base material, greatly improve the service life of titanium-based porous material, energy
Enough further expand the use field for preparing gained titanium-based porous material and use scope.
Illustrate the inventive method with embodiment below.It should be understood that these embodiments are only used for into one
Step explanation embodiment of the present invention, rather than for limiting the present invention.
Embodiment 1：
Present embodiments provide a kind of composite porous preparation method of titanium-based of the ceramics containing nano TiN, its flow reference picture 1
Shown, key step includes as follows：
（1）The preparation of composite granule：
The titanium valve of 110 parts by weight is weighed, is put into advance with washes of absolute alcohol and dried high-energy ball milling tank, according to ball material
Than 15:1 supplying abrading-ball, is more than 99.99% nitrogen cleaning of evaporator three times with purity, the air in discharge tank body, to avoid in high speed ball milling
Process generates other oxidation phases, influences the quality of follow-up sintering sample.It is filled with into ball grinder after nitrogen and makes the gas in spherical tank
Pressure is maintained at 15 × 105Mpa, high gas pressure can increase the production rate that gas density is favorably improved nano TiN particle.
Then multiple mechanical ball mill is proceeded by, drum's speed of rotation is 500r/min, each Ball-milling Time is 40 min, per adjacent two
The interval time of secondary ball milling is 20min, and ball milling total time is 6h, then stops ball milling, ball grinder is placed in vacuum glove box,
Prefabricated composite granule is taken out from ball grinder.In prepared by powder, the granularity of initial titanium valve is more preferably less than 50 μm, and its is microcosmic
Topography scan electron microscope mutually detects collection of illustrative plates with XRD things as shown in Fig. 2 titanium valve is irregular shape and XRD detections are free of other things
The characteristic peak of matter.In mechanical milling process, there is the tiny original particle size of titanium valve higher surface can help to titanium valve table in itself
TiN ceramic particles are generated in face absorption nitrogen, and the shock of abrading-ball in high-speed motion, friction process, TiN particles are improved
Recovery rate, while can also improve grinding efficiency, ball milling obtains that granularity is tiny and uniform prefabricated composite granule after terminating, at this specially
Ratio of grinding media to material 10 ~ 20 in profit：1,400 ~ 600r/min of rotating speed can add the intensity of ball milling, improve the percentage of damage and TiN of powder
The production rate of phase is so as to shorten the time of ball milling, in pulverizing process, using mechanical ball mill technique not only for offer generation
The condition of TiN particles, can also refine powder particles and improve sintering activity.Prolonged ball milling, the TiN particles of generation are with titanium
Powder particles " are rubbed " and are embedded in inside titanium valve particle under the friction, shock of abrading-ball, so not only cause have between out-phase
There is high bond strength, also TiN particle dispersions are distributed in Titanium base.The microcosmic shape of ball milling composite powder after 6 hours
Looks are as shown in figure 3, titanium valve granularity is substantially refined, and occurs in that substantial amounts of nano-scale particle, and the XRD for passing through powder detects such as Fig. 4
It is shown, find the diffraction maximum of ball milling TiN crystal after 6 hours clearly, it is possible to determine that nano TiN is generated in mechanical milling process
Ceramic particle, while Fig. 4 also show in the XRD testing results of the composite granule after 2 hours of ball milling, figure without obvious
TiN crystal diffractions peak occurs, it may be possible to caused due to the shorter generation TiN particles of Ball-milling Time are less, but titanium spreads out
Penetrate peak substantially to broaden step-down compared to starting powder, caused by this is the result of titanium valve crystal grain refinement, this fully shows ball-milling treatment
During titanium valve refined.
（2）Dispensing：
100 parts by weight are weighed out from above-mentioned prefabricated composite granule, are mixed by its 1.5 times of volumes with urea in grinding body.It is mixed
During conjunction absolute ethyl alcohol is added in ratio of the mixing beyond the region of objective existence with 12mL absolute ethyl alcohols of every kilogram of composite granule and urea.Because
There is density contrast in composite granule, add after appropriate absolute ethyl alcohol and wherein cause powder showing for little particle reunion occur with urea
As can so offset batch mixing of the part caused by density contrast uneven.Urea is contributed to more to be evenly distributed in powder
Among body, be conducive to finally obtaining the uniform porous material of hole.But additional absolute ethyl alcohol can excessively cause the reunion of powder
Phenomenon is serious, then is unfavorable for the uniform mixing of material.The granularity of acicular morphology granular urea is 0.8 ~ 1.38mm, as shown in figure 5,
It is due to have conclusive influence on material property in foamed material mesoporous character for the selection of urea size scope,
Because the anisotropy of bar-shaped urea space arrangement, it is favorably improved hole UNICOM and leads.So as to the connective good porous material obtained
Material.At the uniform velocity mix 30min, longer mixing time is to increase the probability that urea is well mixed with powder.Obtain afterwards
Even compound, is follow-up to obtain that pore structure is uniform composite porous to be ready.
（3）Pressed compact：
With steel die that the compound obtained by back is compressing, pressing pressure is 200MPa, and the dwell time is 60s, is taken off
Mould obtains green compact.Pressurize is to be conducive to effective transmission of pressure, and the green compact made are more densified, and increases the intensity of green compact, it is to avoid
The generation of arch bridge effect between particle.
（4）Heat treatment：
Raw pressed compact is placed in vacuum carbon tube furnace and is heat-treated, heat treatment process is divided into cryogenic vacuum sintering and high-temperature solid burns
The step of knot two, carries out heating curve as shown in Figure 6；In cryogenic vacuum sintering process, control in vacuum carbon tube furnace vacuum be 1 ×
10-2~1×10-3Pa, controls heating rate to be sintered for 2 ~ 5 DEG C/min from room temperature to 400 DEG C, is incubated at 400 DEG C
60min；Subsequently into high-temperature solid sintering process, temperature is increased to 1100 DEG C, is 1 × 10 in vacuum-3Sintered under Pa environment
2h；After the completion of sintering, after furnace cooling to room temperature take out obtain the ceramic particle containing nano TiN titanium-based it is composite porous.This
Porous titanium matrix composite pattern obtained by embodiment sintering is as shown in fig. 7, the hole wall under its two kinds of different amplifications is microcosmic
Pattern is as shown in Figure 8.
Heat treatment of the present invention to raw pressed compact has been divided into cryogenic vacuum sintering and high-temperature solid sinters two steps and carried out.Fig. 9 shows
Go out the differential thermal analysis curve figure of urea, shown in figure, when temperature is 400 DEG C, urea is decomposed and finished substantially, therefore by low temperature
The sintering temperature of vacuum-sintering process is determined at 400 DEG C；And in cryogenic vacuum sintering stage, heating rate is preferably relatively slow, control
Heating rate is optimal in 2 ~ 5 DEG C/min, causes to cave in avoid urea from decomposing the too fast raw pressed compact expansion of release；It is true in low temperature
In empty sintering process, it is 1 × 10 to control vacuum in vacuum carbon tube furnace-2~1×10-3Pa, purpose are decomposed in order that obtaining pore creating material
Gas be extracted into outside body of heater rapidly, it is to avoid pollution sample, at 400 DEG C be incubated 45 ~ 60min, it is therefore an objective to ensure urea completely take off
Go out.In high-temperature solid sintering process, in the sintering neck length megastage, TiN ceramic particles can promote to form non-homogeneous as nucleating agent
Forming core carrys out crystal grain thinning, while hindering the growth of crystal boundary to reduce the coarsening rate of crystal grain, is refined in porous titanium matrix composite
Crystal grain can effectively improve the intensity of material, and this is that other intensifying methods can not compare, tiny under identical external force
Strain relatively small near intra-die and crystal boundary, deformation is uniform, comparatively, stress concentrate cause the chance of cracking also compared with
It is few so that titanium-based porous material can bear larger deformation before cracking；On the other hand, in material stress and deformation process
In, TiN ceramic particles can bear higher load, to hinder the extension of crackle or change its extension approach, and enhancing crackle expands
Zhan Neng, so as to improve the intensity and toughness of titanium-based porous material so that the comprehensive mechanical property of titanium-based porous material is improved.
High-melting-point, the corrosion resistance characteristic of TiN ceramic particles can further improve high temperature resistant, the corrosion resistance of titanium base material simultaneously, greatly
The big service life for improving titanium-based porous material.Further expand the use field of porous material, using scope.
As shown in Figure 10, its maximum is anti-for the incompressible load-deformation curve of titanium matrix composite prepared by the present embodiment 1
Compression stress is 187.56Mpa.Initial yield stress be 150.12 Mpa, line smoothing, have obvious elastic deformation area and compared with
Stabilised platform area.
Embodiment 2：
A kind of foam magnesium preparation method for buffering energy-absorbing material is present embodiments provided, shown in its flow reference picture 1, mainly
Step includes as follows：
（1）The preparation of composite granule：
The titanium valve of 110 parts by weight is weighed, is put into advance with washes of absolute alcohol and dried high-energy ball milling tank, according to ball material
Than 10:1 supplying abrading-ball, is more than 99.99% nitrogen cleaning of evaporator three times with purity, the air in discharge tank body.Nitrogen is filled with into ball grinder
After gas and the air pressure in spherical tank is set to be maintained at 15 × 105Mpa, proceeds by multiple mechanical ball mill, and drum's speed of rotation is 400r/
Min, each Ball-milling Time is 30 min, and the interval time per adjacent ball milling twice is 10min, and ball milling total time is 4h, then
Stop ball milling, ball grinder is placed in vacuum glove box, prefabricated composite granule is taken out from ball grinder.
（2）Dispensing：
100 parts by weight are weighed out from above-mentioned prefabricated composite granule, are mixed by its 1.5 times of volumes with urea in grinding body.It is mixed
During conjunction, absolute ethyl alcohol is added in ratio of the mixing beyond the region of objective existence with 10mL absolute ethyl alcohols of every kilogram of composite granule and urea, and
At the uniform velocity mix 20min.
（3）Compacting：
With steel die that the compound obtained by back is compressing, pressing pressure is 250MPa, and the dwell time is 90s, is taken off
Mould obtains green compact.
（4）Heat treatment：
Raw pressed compact is placed in vacuum carbon tube furnace and is heat-treated, heat treatment process is divided into cryogenic vacuum sintering and high-temperature solid burns
In the step of knot two, cryogenic vacuum sintering process, it is 1 × 10 to control vacuum in vacuum carbon tube furnace-2~1×10-3Pa, control heating speed
Rate is that 2 ~ 5 DEG C/min is sintered from room temperature to 400 DEG C, and 60min is incubated at 400 DEG C；Burnt subsequently into high-temperature solid
Knot process, temperature is increased to 1100 DEG C, is 1 × 10 in vacuum-32h is sintered under Pa environment；After the completion of sintering, furnace cooling is arrived
After room temperature take out obtain the ceramic particle containing nano TiN titanium-based it is composite porous,
The incompressible stress-strain test yield stress of titanium matrix composite prepared by the implementation case 2 is 142.65Mpa.
Embodiment 3：
A kind of foam magnesium preparation method for buffering energy-absorbing material is present embodiments provided, shown in its flow reference picture 1, mainly
Step includes as follows：
（1）The preparation of composite granule：
The titanium valve of 110 parts by weight is weighed, is put into advance with washes of absolute alcohol and dried high-energy ball milling tank
In, according to ratio of grinding media to material 20:1 supplying abrading-ball, is more than 99.99% nitrogen cleaning of evaporator three times with purity, the air in discharge tank body.
It is filled with into ball grinder after nitrogen and the air pressure in spherical tank is maintained at 20 × 105Mpa, proceeds by ball milling, drum's speed of rotation
For 600r/min, each Ball-milling Time is 60 min, and the interval time per adjacent ball milling twice is 30min, and ball milling total time is
8h, then stops ball milling, and ball grinder is placed in vacuum glove box, and prefabricated composite granule is taken out from ball grinder.
（2）Dispensing：
100 parts by weight are weighed out from above-mentioned prefabricated composite granule, are mixed by its 1.5 times of volumes with urea in grinding body.It is mixed
During conjunction, absolute ethyl alcohol is added in ratio of the mixing beyond the region of objective existence with 15mL absolute ethyl alcohols of every kilogram of composite granule and urea, and
At the uniform velocity mix 30min.
（3）Compacting：
With steel die that the compound obtained by back is compressing, pressing pressure is 200MPa, and the dwell time is 60s, is taken off
Mould obtains green compact.
（4）Heat treatment：
Raw pressed compact is placed in vacuum carbon tube furnace and is heat-treated, heat treatment process is divided into cryogenic vacuum sintering and high-temperature solid burns
In the step of knot two, cryogenic vacuum sintering process, it is 1 × 10 to control vacuum in vacuum carbon tube furnace-2~1×10-3Pa, control heating speed
Rate is that 2 ~ 5 DEG C/min is sintered from room temperature to 400 DEG C, and 45min is incubated at 400 DEG C；Burnt subsequently into high-temperature solid
Knot process, temperature is increased to 1150 DEG C, is 1 × 10 in vacuum-31.5h is sintered under Pa environment；After the completion of sintering, furnace cooling
After to room temperature take out obtain the ceramic particle containing nano TiN titanium-based it is composite porous,
The incompressible stress-strain test yield stress of titanium matrix composite prepared by the implementation case is 138.78Mpa, still
With higher mechanical property.But its intensity is less than case 1 but composite porous higher than the titanium-based prepared by case 2, explanation
When gas pressure intensity parameter and all higher ball milling parameter, the TiN of generation excessively can cause the mechanical property of material to decrease,
Main cause is that milling intensity is improved so that precast body powder height plastic deformation, hardening cause formability during isostatic cool pressing
Reduction, so as to after by compressing and sintering process, more inside fine cracks occur so that porous titanium-based is combined
The intensity of material has declined.But from the point of view of porous material angle, the actual hole for improving material of fine crack of a certain amount
Gap rate and connectedness.
From above-described embodiment it can be seen that, the composite porous Preparation Method of titanium-based of the particle containing nano TiN of the invention is utilized
Powder metallurgy pore creating material technology, by being passed through the high pure nitrogen of certain pressure intensity in titanium valve ball milling, is prepared containing nano TiN ceramics
The composite powder precast body of particle, is incorporated a certain amount of absolute ethyl alcohol and is uniformly mixed with corynebacterium urea as intermixture and binding agent
Close, compacting green compact, cryogenic vacuum sintering, high temperature solid-phase sintering have prepared that composition is controllable, titanium-based with certain voidage is more
Hole composite material.The inventive method utilizes the titanium prepared by the composite granule of mechanical ball mill fabricated in situ particle containing nano TiN
Base porous compound material has high intensity, and the excellent porous titanium matrix composite of comprehensive mechanical property makes it have relatively strong resistance to height
Warm corrosion resistance, extends the wear life of porous titanium matrix composite, is sewage purification, and biological implantation material etc. is provided
A kind of new technological approaches, with extraordinary application prospect.
In summary, compared with existing porous titanium products preparation method for material, the present invention passes through mechanical ball mill fabricated in situ system
The method of the titanium enhancing titanium-based porous material of the standby ceramics containing nano TiN has following outstanding advantages：First, titanium-based of the invention
Porous material preparation method technique is simple, and flow is short, and energy resource consumption is low, while being advantageously implemented mass production so that strong
Quality more lightweight in the case that degree does not drop；Second, in the high pure nitrogen atmosphere of certain pressure, by ball-milling technology,
So that titanium valve is during ball mill crushing, under high-speed impact, fine titanium powder particles contact generation nano TiN with nitrogen molecule
In grain, and Dispersed precipitate and powder, using low cost feedstock, fore-put powder is mutually answered in in-situ preparation TiN containing nanoscale enhancings, necessarily
The effect with optimization titanium base material performance of nano TiN particle is measured, is provided to prepare the composite porous preparation of titanium-based
A kind of economic and practical new method；3rd, urea is used as pore-creating as the use of pore creating material compared with NaCl, starch, magnesium metal etc.
For agent, with more obvious advantage because urea just easily decomposition under relatively low heating-up temperature, continuous vacuum abjection and
The subtractive process of urea will not introduce other impurity so that gained titanium-based porous material easy control of components, urea has simultaneously
Environment is not polluted after abjection and advantage that price is cheap；4th, the porous composite wood of titanium-based of the particle of the invention containing nano TiN
Preparation method for material, using powder metallurgy boring technique, being mutually combined fore-put powder using nanoscale TiN enhancings, to have prepared titanium-based more
Hole composite material, the material has special gap structure, possesses higher specific strength, high temperature resistant, anticorrosive, extends pure many
The use time of hole titanium, solves the titanium-based porous material corrosion resistance in the prior art obtained by POROUS TITANIUM preparation technology well
The problems such as difference, material property deterioration, hardly possible control of, complex process short compared with wear life, composition, it is combined to prepare high intensity, porous titanium-based
Material provides a kind of new technological approaches, with extraordinary application prospect.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to skill of the invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (5)
1. a kind of composite porous preparation method of titanium-based of the ceramics containing nano TiN, it is characterised in that comprise the steps：
1）Weigh titanium valve to be fitted into advance with washes of absolute alcohol and dried high-energy ball milling tank, ratio of grinding media to material is 10 ~ 20：1；
2）The high-energy ball milling cover that will be equipped with titanium valve is good, the tank body more than 3 times for washing ball grinder is filled with nitrogen, to discharge in ball grinder
Air, nitrogen is then filled with into ball grinder, be filled with nitrogen pressure be 5 × 105~20×105Pa；
3）It is filled with into ball grinder after nitrogen, multiple mechanical ball mill is carried out to the titanium valve in ball grinder, each Ball-milling Time is
30 ~ 60 minutes, the interval time per adjacent ball milling twice was 10 ~ 30 minutes, and ball milling total time is 4 ~ 8 hours；Obtained after ball milling
Composite granule containing nano TiN particle；Then, treat that tank body is cooled to after normal temperature, composite granule is taken out from ball grinder；
4）Composite granule obtained above is mixed by its 1.5 times of volumes with urea in grinding body, every kilogram is pressed in mixed process
Ratio of the mixing beyond the region of objective existence of composite granule and urea with 10 ~ 15mL absolute ethyl alcohols adds absolute ethyl alcohol；Wherein, the granularity of urea is
0.8 ~ 1.38mm, mixing time is 20 ~ 30min, obtains compound；
5）With steel die by the compound isostatic pressing obtained by back, pressing pressure is 200 ~ 250MPa, dwell time
For 60 ~ 90s, the demoulding obtains green compact；
6）Green compact are put into vacuum carbon tube furnace and are sintered, sintering process is divided into cryogenic vacuum sintering and high-temperature solid sintering two
Step is carried out；In cryogenic vacuum sintering process, it is 1 × 10 to control vacuum in vacuum carbon tube furnace-2~1×10-2Pa, control heating speed
Rate is that 2 ~ 5 DEG C/min is sintered from room temperature to 400 DEG C, and 45 ~ 60min is incubated at 400 DEG C；Subsequently into high-temperature solid
Sintering process, temperature is increased to 1100 ~ 1150 DEG C, is 1 × 10 in vacuum-31.5 ~ 2h is sintered under Pa environment；After the completion of sintering,
The titanium-based that furnace cooling obtains the particle containing nano TiN to taking-up after room temperature is composite porous.
2. according to claim 1 containing the ceramic composite porous preparation method of titanium-based of nano TiN, it is characterised in that institute
State step 1）Employed in the purity of titanium valve be more than 99.5%, the grain diameter of titanium valve is less than 50 μm.
3. according to claim 1 containing the ceramic composite porous preparation method of titanium-based of nano TiN, it is characterised in that institute
State step 2）In the purity of nitrogen used be more than 99.99%.
4. according to claim 1 containing the ceramic composite porous preparation method of titanium-based of nano TiN, it is characterised in that institute
State step 3）In, the drum's speed of rotation for carrying out ball milling is 400 ~ 600r/min.
5. according to claim 1 containing the ceramic composite porous preparation method of titanium-based of nano TiN, it is characterised in that institute
State step 4）In, the urea uses chemical pure needle-like urea.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385677A (en) * | 2021-06-04 | 2021-09-14 | 孙晓华 | Stirring ball-milling pretreatment method for titanium powder particles of vacuum sintering porous titanium coating |
| CN116475416A (en) * | 2023-06-20 | 2023-07-25 | 紫金矿业集团黄金珠宝有限公司 | Manufacturing process of precious metal ornament with fragrance storage function |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319270A (en) * | 2016-09-05 | 2017-01-11 | 重庆大学 | Preparation method of nano-TiN-reinforced Ti-based composite |
| CN106521219A (en) * | 2017-01-05 | 2017-03-22 | 重庆大学 | Preparation method for TiC particle reinforced titanium-based porous material |
-
2017
- 2017-07-12 CN CN201710567350.XA patent/CN107287464A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319270A (en) * | 2016-09-05 | 2017-01-11 | 重庆大学 | Preparation method of nano-TiN-reinforced Ti-based composite |
| CN106521219A (en) * | 2017-01-05 | 2017-03-22 | 重庆大学 | Preparation method for TiC particle reinforced titanium-based porous material |
Non-Patent Citations (1)
| Title |
|---|
| 宝鸡有色金属研究所: "《粉末冶金多孔材料 上册》", 30 November 1978, 冶金工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385677A (en) * | 2021-06-04 | 2021-09-14 | 孙晓华 | Stirring ball-milling pretreatment method for titanium powder particles of vacuum sintering porous titanium coating |
| CN113385677B (en) * | 2021-06-04 | 2023-10-31 | 孙晓华 | Titanium powder particle stirring ball milling pretreatment method for vacuum sintering porous titanium coating |
| CN116475416A (en) * | 2023-06-20 | 2023-07-25 | 紫金矿业集团黄金珠宝有限公司 | Manufacturing process of precious metal ornament with fragrance storage function |
| CN116475416B (en) * | 2023-06-20 | 2023-09-19 | 紫金矿业集团黄金珠宝有限公司 | Manufacturing process of precious metal ornament with fragrance storage function |
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