CN107385250B - A kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites - Google Patents
A kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites Download PDFInfo
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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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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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
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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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
- C22C1/10—Alloys containing non-metals
- C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- B22F2201/20—Use of vacuum
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Abstract
The invention discloses the preparation methods that a kind of TiC enhances Ultra-fine Grained β titanium niobium based composites, this method uses pure Ti powder, pure Nb powder for raw material, using carbon containing, hydrogen process control agent as the carbon source and process control agent of endogenous TiC, alloy powder is obtained through ball milling, by alloy powder vacuum pre-burning degasification, destressing, then green compact are made, assembling sintering unit is most sintered afterwards through superhigh-pressure high-temp and TiC enhancing Ultra-fine Grained β titanium niobium based composites are made.Carbon source of the process control agent that the present invention uses as endogenous TiC, it is effective to alleviate the reunion of powder and the viscous wall situation of slimeball in mechanical milling process, play the role of refining powder and improves flour extraction, the TiC combination superhigh-pressure high-temps sintering that low temperature presintering generates simultaneously, effectively inhibits growing up for crystal grain, and the TiC of preparation enhances Ultra-fine Grained β titanium niobium based composites, reinforcement is evenly distributed, crystal grain is tiny, and consistency is high, while having high-strength high-plastic wear-resisting feature concurrently.
Description
Technical field
The invention belongs to metal-base composites technical fields, and in particular to a kind of TiC enhancings Ultra-fine Grained β titanium niobium bases are compound
The preparation method of material.
Background technology
Titanium or titanium alloy has density small, and specific strength is high, and corrosion-resistant, high- and low-temperature resistance performance is good, nontoxic excellent performance,
It is widely used in the fields such as aerospace, machinery, medical treatment.Wherein, beta-titanium alloy has preferable plasticity, cold forming outstanding
Property, excellent corrosion resistance and be widely studied.The performance of titanium or titanium alloy is further promoted, such as intensity, wear-resisting, not only
Be applied to prodigious facilitation, and under the background of energy growing tension, can substantially mitigate aircraft, automobile from
Weight reduces energy consumption.Nanocrystalline/Ultra-fine Grained titanium or titanium alloy and titanium matrix composite have very high intensity and excellent
Wear-resisting property, however plasticity is poor even without plasticity, limits its applications in various fields.Therefore, it prepares and has height concurrently
The titanium alloy and titanium matrix composite of specific strength, plasticity and wear-resisting property have become the important topic of scientific research personnel.
The patent (CN201410490300.2) of the Yang Chao of South China Science & Engineering University et al. is prepared using the method for Amorphous Crystallization
Ultra-fine Grained composite construction titanium alloy, solve the problems, such as that titanium alloy is high-strength and high-plastic can not get both.Preparation method is will be former
Material carries out high-energy ball milling in the ball mill, obtains amorphous powder, and most Ultra-fine Grained composite construction titanium is made and closes through sinter afterwards
Gold.However, the preparation of amorphous powder, needs 70~100 hours high-energy ball millings, technique to be difficult to control, is unfavorable for volume production.Liu Zili
Et al. patent (CN20110364856.8) use carbon source of the graphite powder as endogenous TiC, raw material is mixed in the ball mill
It closes, is most sintered afterwards through hollow cathode and TiC granule intensified titaniums-aluminium-molybdenum-manganese alloy is made.The method is simple for process, but the sample prepared
Product consistency is relatively low, is 94%~96%.The patent (CN201510454422.0) of Gu Dongdong et al. uses carbon nanotube conduct
The carbon source of endogenous TiC mixes carbon nanotube and titanium valve in the ball mill, is made finally by laser gain material manufacturing technology
TiC enhances titanium matrix composite.TiC prepared by this method enhances titanium matrix composite, and crystal grain is tiny, and consistency is high, however ball
The method of mill is difficult to be uniformly dispersed in nano level carbon nanotube in tens microns of titanium valve, therefore the TiC prepared holds very much
The case where being easily unevenly distributed.Patent (CN201010178675.7) brave et al. Chen Yu using graphite powder as it is in situ from
The carbon source of raw TiC, graphite powder and titanium valve and other metal powders is simply mixed, later cold moudling, induction melting, to make increasing
Strong body is evenly distributed, and also needs to carry out Homogenization Treatments, twice forging, single hot-roll, twice annealing process twice, and process is complicated,
Cost is higher.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of TiC to enhance the preparation side of Ultra-fine Grained β titanium niobium based composites
Method, this method organically combine the high intensity of TiC and the high-ductility of beta-titanium alloy, and TiC obtained enhances Ultra-fine Grained β titaniums
Niobium based composites have the characteristics that high-strength, high-plastic, wear-resisting.
A kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites of the present invention, includes the following steps：
Step 1：Mechanical alloying
Titanium valve, niobium powder, carbon source are placed in ball milling in vacuum ball grinder, until elemental powders alloying；
The carbon source is the process control agent containing C, H；
The titanium valve, niobium powder additive amount count titanium valve in mass ratio：Niobium powder is 60~75:25~40；
The additive amount of the carbon source is 1~3wt% of titanium valve and niobium powder quality sum；
The ball-milling medium uses the stainless steel ball of a diameter of 8~Φ of Φ 15mm, ratio of grinding media to material 10:1~20:1, rotating speed is
200~280r/min；Ball-milling Time is 10~15h；
Step 2：Pre-burning
Alloy powder obtained by step 1 is put into vacuum sintering furnace, is sintered under vacuum, that is, obtains TiC and titanium-niobium alloy
Powder, the sintering temperature are 450~600 DEG C, and the soaking time is 60~120min, are protected wherein heat preservation can be gradient
Temperature can also be maximum temperature heat preservation, and by the sintering of step 2, the organic matter adhered in powder is decomposed and ball milling introduces
Stress be removed；
Step 3：Sintering
The powder pre-molding that step 2 is obtained is placed in cubic hinge press and is sintered, i.e., after assembling is sintered unit
Obtaining TiC enhances Ultra-fine Grained β titanium niobium based composites；The sintering pressure is 2~5GPa, and sintering temperature is 1100~1200
℃。
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 1, the carbon source is
One kind in stearic acid (CH3 (CH2) 16COOH), alcohol, toluene, normal heptane.As a further preference, the carbon source is hard
One kind in resin acid, alcohol.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 1, the titanium valve, niobium
The grain size of powder is 50~75 μm；The titanium valve, niobium powder purity 99.9% or more.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 1, the carbon source
Additive amount is 2~3wt% of titanium valve and niobium powder quality sum.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 1, the ball milling is adopted
With planetary ball mill, ball grinder is stainless-steel vacuum ball grinder.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 1, the ball milling is situated between
Matter uses the stainless steel ball of a diameter of 10~Φ of Φ 15mm, ratio of grinding media to material 10:1~15:1, rotating speed is 200~240r/min；Ball
Time consuming is 10~12h.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 2, alloy powder is put
After entering vacuum sintering furnace, first stove is vacuumized, until vacuum degree is 5 × 10-2~5 × 10-3Pa, then presses heating rate 5
~8 DEG C/min is warming up to 450~600 DEG C, and it is 5 × 10-2~5 × 10-3Pa that vacuum degree is maintained in sintering process.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, it is described pre- to be pressed into step 3
Type carries out in tablet press machine, and specific molding mode is：The powder that step 2 is obtained is packed into mold, is placed in tablet press machine
On, apply the pressure of 8~10MPa, the dwell time is 10~15min, is prepared into green compact.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 3, sintering unit by
Green compact, insulation tube (hexagonal boron nitride), graphite-pipe, molybdenum sheet, the steel of pre-molding emit and carry out group according to a certain order with pyrophillite
Dress.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 3, sintering process is,
Under the pressure of 2~5GPa, 1100~1200 DEG C, 5~15min of heat-insulation pressure keeping are warming up to the rate of 300~400 DEG C/min,
After heating, continue 3~4min of pressurize, after sample cooling, sample is taken out in pressure release.
A kind of preparation method of present invention TiC enhancing Ultra-fine Grained β titanium niobium based composites, in step 3, sintering atmosphere is
Atmospheric atmosphere.
A kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites of the present invention, prepared TiC enhancings are ultra-fine
In brilliant β titaniums niobium based composites, the shaft-like such as reinforcement TiC is, volume fraction is 25~40%, and grain size is 0.15~0.9 μm,
Even is distributed in titanium niobium matrix.
A kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites of the present invention, prepared TiC enhancings are ultra-fine
Brilliant β titaniums niobium based composites, matrix grain are 0.2~1 μm, consistency>99.3%, hardness is 452.2~552.1Hv, surrender
Intensity is 1660~1930MPa, and breaking strain is 5.2~21.88%.
Compared with prior art, the principle of the present invention is with advantage：
Mechanical alloying is a kind of effective ways of synthesis fine grain alloy powder material.It is prepared using mechanical alloying technique
Material there is uniformly tiny microscopic structure, mechanical property to be better than same type of material prepared by other techniques.However mechanical alloy
The phenomenon that gluing wall there are the reunion of serious powder, caking and slimeball during changing, wants adition process controlling agent, is to slow down thus
Impact strength between abrading-ball, the balance between adjusting powder cold welding and being crushed, can substantially save the energy of ball milling, simultaneously in this way
More tiny alloying powder is obtained, however process control agent generally also has part and dissolves in into alloy powder, influences
The performance of alloy powder.
Then inventor directly using carbon containing, hydrogen process control agent as carbon source, pure Ti powder and with it is excessively program-controlled containing C, H
For preparation during high-energy ball milling, the process control agent in the present invention can be adsorbed on the Ti powder surface containing a large amount of defects, lead to
Ball milling is crossed, machinery can occur for the meeting of the elements such as C, H and Ti powder --- chemical reaction, in the sintering process of low temperature presintering, C, H are simultaneously
It is solid-solution in Ti atoms, generates TiC, TiH2, as temperature increases TiH2It decomposes, final TiC is remained, due in ball
During mill, process control agent is introduced, liquid film is formed in mechanical milling process, effectively alleviates the reunion of powder in mechanical milling process
And slimeball glues wall situation, plays the role of refining powder and improves flour extraction, simultaneously because directly process control agent is used to make
For carbon source, and other impurity are not will produce.
In addition the present invention is small using the gibbs free energy change ratio NbC of TiC, and reaction tendency bigger, reaction product are more stable
Principle controlled in preparation process by proportioning, the synergistic effect of the condition of vacuum-sintering of ballmilling energy, Ti powder and Nb powder,
TiC is only formed as reinforcement.
Beta-titanium alloy usually has excellent plastic deformation ability, therefore the present invention stablizes member by a certain amount of β phases are introduced
Plain Nb, makes matrix be maintained β phases, and β-Ti (Nb) alloy of formation has preferable plasticity, cold formability outstanding.
The present invention carries out pre-burning in the case of low temperature, by the pre-burning of short time, while removing process control agent,
The TiC that in situ generated TiC, and generated under low temperature can inhibit growing up for matrix grain, to make the TiC crystal grain of acquisition more
Small, refined crystalline strengthening makes composite material have superior mechanical property, and sintering process of the present invention is using cubic hinge press sintering system
System, heating rate is fast, while sintering, applies the pressure of superelevation, promotes powder densification, sintering time is short, the sample of preparation
Product crystal grain is tiny, and consistency is high, and reinforcement is evenly distributed, and has high-strength high-plastic wear-resisting feature concurrently.
The present invention can be in Process During High Energy Ball Milling using process control agent, the principle that can be dissolved with powder, using containing C, H
Process control agent is directly as the carbon source of in-situ formation of TiC, the collaboration being sintered by mechanical alloying, pre-burning, superhigh-pressure high-temp
Effect, the high intensity of TiC and the high-ductility of beta-titanium alloy organically combine, and TiC enhancings Ultra-fine Grained β titanium niobium bases obtained are multiple
Condensation material has the characteristics that high-strength, high-plastic, wear-resisting.The TiC of preparation enhances Ultra-fine Grained β titanium niobium based composites, can be used for biology
Medical, aerospace, automobile and sport etc. require specific strength, wear-resisting property relatively high product.Present invention process simultaneously
Simply, easy to spread, it is conducive to industrialized production.
Description of the drawings
Fig. 1 is that superhigh-pressure high-temp is sintered unit assembling figure.
Fig. 2 is the xrd collection of illustrative plates of each stage sample in embodiment 1.
Fig. 3 is the scanning electron microscopic picture that TiC prepared by embodiment 1 enhances Ultra-fine Grained β titanium niobium based composites.
Fig. 4 is the room temperature compression stress strain curve that TiC prepared by embodiment 1 enhances Ultra-fine Grained β titanium niobium based composites.
Fig. 5 is the scanning electron microscopic picture that TiC prepared by embodiment 2 enhances Ultra-fine Grained β titanium niobium based composites.
Fig. 6 is the transmission electron microscope picture that TiC prepared by embodiment 2 enhances Ultra-fine Grained β titanium niobium based composites.
Fig. 7 is the room temperature compression stress strain curve that TiC prepared by embodiment 2 enhances Ultra-fine Grained β titanium niobium based composites.
Fig. 8 is the room temperature compression stress strain curve that TiC prepared by embodiment 3 enhances Ultra-fine Grained β titanium niobium based composites.
Fig. 9 is the scanning electron microscopic picture that TiC prepared by 1 vacuum-sintering of comparative example enhances β titanium niobium based composites.
Specific implementation mode
Below by embodiment, the present invention will be further described, it is noted that protection scope of the present invention is simultaneously
It is not limited to the range of embodiment expression.
Embodiment 1
Raw material：Ti powder, Nb powder are the powder of 50 μm of irregular shape, and purity is in 99.9% or more, CH3(CH2)16COOH is that analysis is pure.
Proportioning weighs：Ti powder：Nb powder is calculated as 60 in mass ratio：40, CH3(CH2)16The additive amount of COOH is Ti powder and Nb powder
The 2wt% of quality sum.
High-energy ball-milling alloying：Load weighted raw material is placed in the stainless-steel vacuum ball grinder of 250ml, abrading-ball is using straight
The stainless steel ball of diameter 15mm, abrading-ball weight are 300g, ratio of grinding media to material 15:1, ball grinder is vacuumized, planetary ball mill is placed in
(QM-3SP2) with the rotating speed ball milling of 240r/min 12 hours in, completely alloyed powder end is made.Pre-burning：The conjunction that ball milling is obtained
Bronze end is placed in vitrified pot, is placed in high vacuum vertical sintering furnace (ZM-30-16), and it is 5 × 10 to be evacuated to vacuum degree- 2Pa, with the heating rate of 5 DEG C/min, in 450 DEG C and 600 DEG C, each heat preservation 1 hour, then furnace cooling is obtained containing in situ
Spontaneous TiC, and the good composite powder of molding effect.
Prepare green compact：The composite powder that pre-burning is obtained is packed into the mold that internal diameter is 10mm, is placed on tablet press machine, is applied
The pressure of 8MPa, dwell time 15min are prepared into the green compact of 10 × 8mm of φ.
Sintering：Green compact, insulation tube (hexagonal boron nitride), graphite-pipe, molybdenum sheet, steel are emitted and assembled with pyrophillite, then
It is put into progress superhigh-pressure high-temp sintering in cubic hinge press.Under the pressure of 3GPa, 1200 are raised to the rate of 300 DEG C/min
DEG C, then heat-insulation pressure keeping 15min, after to be heated, continues the cooling of the samples such as pressurize 4min, sample is taken out in last pressure release.
Fig. 2 is the xrd collection of illustrative plates of each stage sample in embodiment 1, and as shown in Figure 2, after mechanical alloying, powder is β phases；Very
After empty pre-burning, composite powder is made of β phases, α phases and TiC；After superhigh-pressure high-temp is sintered, object is mutually made of β phases and TiC.This
TiC prepared by embodiment enhances Ultra-fine Grained beta Ti-base composite material, and consistency is up to 99.37%, stereoscan photograph such as Fig. 3
It is shown, reinforcement TiC be etc. shaft-like, volume fraction 25%, grain size be 0.15~0.9 μm, be evenly distributed in by Ti, Nb member
In the beta Ti-base body that element is formed.Beta Ti-base body crystal grain is 0.2~1 μm, and hardness is 473.86 ± 16.01Hv, room temperature compression stress
Strain curve is as shown in figure 4, as shown in Figure 4, the surrender of TiC enhancings Ultra-fine Grained beta Ti-base composite material manufactured in the present embodiment is strong
Degree and breaking strain are respectively 1660MPa and 21.88%.
Embodiment 2
Raw material：Ti powder, Nb powder are the powder of 60 μm of irregular shape, and purity is in 99.9% or more, CH3(CH2)16COOH is that analysis is pure.
Proportioning weighs：Ti powder：Nb powder is calculated as 67 in mass ratio：33, CH3(CH2)16The additive amount of COOH is Ti powder and Nb powder
The 2.5wt% of quality sum.
High-energy ball-milling alloying：Load weighted raw material is placed in the stainless-steel vacuum ball grinder of 250ml, abrading-ball is using straight
The stainless steel ball of diameter 10mm, abrading-ball weight are 300g, ratio of grinding media to material 12:1, ball grinder is vacuumized, planetary ball mill is placed in
(QM-3SP2) with the rotating speed ball milling of 220r/min 10 hours in, completely alloyed powder end is made.
Pre-burning：The alloy powder that ball milling obtains is placed in vitrified pot, high vacuum vertical sintering furnace (ZM-30- is placed in
16) in, it is 5 × 10 to be evacuated to vacuum degree-3Pa keeps the temperature 2 hours, then with stove with the heating rate of 6 DEG C/min at 450 DEG C
It is cooling, it obtains containing endogenous TiC, and the good composite powder of molding effect.
Prepare green compact：The composite powder that pre-burning is obtained is packed into the mold that internal diameter is 10mm, is placed on tablet press machine, is applied
The pressure of 10MPa, dwell time 10min are prepared into the green compact of 10 × 8mm of φ.
Sintering：Green compact, insulation tube (hexagonal boron nitride), graphite-pipe, molybdenum sheet, steel are emitted and assembled with pyrophillite, then
It is put into progress superhigh-pressure high-temp sintering in cubic hinge press.Under the pressure of 5GPa, 1200 are raised to the rate of 400 DEG C/min
DEG C, then heat-insulation pressure keeping 15min, after to be heated, continues the cooling of the samples such as pressurize 3min, sample is taken out in last pressure release.
TiC manufactured in the present embodiment enhances Ultra-fine Grained beta Ti-base composite material, and consistency is up to 99.53%, scanning electron microscope
Photo as shown in figure 5, reinforcement TiC be etc. shaft-like, volume fraction 40%, grain size be 0.2~0.8 μm, be evenly distributed in
In the beta Ti-base body formed by Ti, Nb element.Fig. 6 is transmission electron microscope photo, and beta Ti-base body crystallite dimension is 0.2~1 μm, hardness
For 537.76 ± 17.77Hv, room temperature compression stress strain curve is as shown in fig. 7, as shown in Figure 7, the TiC enhancings of the present embodiment are thin
The yield strength and breaking strain of brilliant beta Ti-base composite material are respectively 1880MPa and 10.42%.
Embodiment 3
Raw material：Ti powder, Nb powder are the powder of 75 μm of irregular shape, and for purity 99.9% or more, alcohol is point
It analyses pure.
Proportioning weighs：Ti powder：Nb powder is calculated as 68 in mass ratio；32, the additive amount of alcohol is Ti powder and Nb powder quality sums
2.5wt%.
High-energy ball-milling alloying：Load weighted raw material is placed in the stainless-steel vacuum ball grinder of 250ml, abrading-ball is using straight
The stainless steel ball of diameter 15mm, abrading-ball weight are 300g, ratio of grinding media to material 10:1, ball grinder is vacuumized, planetary ball mill is placed in
(QM-3SP2) with the rotating speed ball milling of 200r/min 10 hours in, completely alloyed powder end is made.
Pre-burning：The alloy powder that ball milling obtains is placed in vitrified pot, high vacuum vertical sintering furnace (ZM-30- is placed in
16) in, it is 1 × 10 to be evacuated to vacuum degree-2Pa, at 600 DEG C, keeps the temperature 1 hour, then with stove with the heating rate of 8 DEG C/min
It is cooling, it obtains containing endogenous TiC, and the good composite powder of molding effect.
Prepare green compact：The composite powder that pre-burning is obtained is packed into the mold that internal diameter is 10mm, is placed on tablet press machine, is applied
The pressure of 9MPa, dwell time 12min are prepared into the green compact of 10 × 8mm of φ.
Sintering：Green compact, insulation tube (hexagonal boron nitride), graphite-pipe, molybdenum sheet, steel are emitted and assembled with pyrophillite, then
It is put into progress superhigh-pressure high-temp sintering in cubic hinge press.Under the pressure of 4GPa, 1100 are raised to the rate of 400 DEG C/min
DEG C, then heat-insulation pressure keeping 5min, after to be heated, continues the cooling of the samples such as pressurize 4min, sample is taken out in last pressure release.
The TiC of the present embodiment enhances fine grain beta Ti-base composite material, and matrix grain is 0.2~1 μm, and consistency is up to
99.61%, hardness is 547.46 ± 15.35Hv, and room temperature compression stress strain curve is as shown in figure 8, as shown in Figure 8, this reality
The yield strength and breaking strain for applying the TiC enhancing fine grain beta Ti-base composite materials of example are respectively 1960MPa and 5.2%.
Comparative example 1
Raw material：Ti powder, Nb powder are the powder of 60 μm of irregular shape, and purity is in 99.9% or more, CH3(CH2)16COOH is that analysis is pure.
Proportioning weighs：Ti powder：Nb powder is calculated as 67 in mass ratio：33, CH3(CH2)16The additive amount of COOH is Ti powder and Nb powder
The 2.5wt% of quality sum.
High-energy ball-milling alloying：Load weighted raw material is placed in the stainless-steel vacuum ball grinder of 250ml, abrading-ball is using straight
The stainless steel ball of diameter 10mm, abrading-ball weight are 300g, ratio of grinding media to material 15:1, ball grinder is vacuumized, planetary ball mill is placed in
(QM-3SP2) with the rotating speed ball milling of 200r/min 10 hours in, completely alloyed powder end is made.
Sintering：The alloy powder pre-molding that ball milling is obtained is placed in high vacuum vertical sintering furnace (ZM-30-16), is taken out
Vacuum to vacuum degree is 1 × 10-2Pa is kept the temperature 2 hours at 450 DEG C, is then proceeded to be heated to the heating rate of 5 DEG C/min
1200 DEG C, and 1 hour is kept the temperature, endogenous TiC enhancing beta Ti-base composite material is made in subsequent furnace cooling.
Sample made from the present embodiment contains compared with concrete dynamic modulus, stereoscan photograph as shown in figure 9, TiC crystalline size
It it is 1~2.8 μm, the crystallite dimension of matrix is 2~4 μm, bigger than the crystallite dimension of high-pressure sinter, and its compression experiment shows
For brittle failure, there is not yield point elongation
Comparative example 2
Raw material：Ti powder, Nb powder are the powder of 60 μm of irregular shape, and purity is in 99.9% or more, CH3(CH2)16COOH is that analysis is pure.
Proportioning weighs：Ti powder：Nb powder is calculated as 90 in mass ratio：10, CH3(CH2)16The additive amount of COOH is Ti powder and Nb powder
The 2wt% of quality sum.
High-energy ball-milling alloying：Load weighted raw material is placed in the stainless-steel vacuum ball grinder of 250ml, abrading-ball is using straight
The stainless steel ball of diameter 10mm, abrading-ball weight are 300g, ratio of grinding media to material 15:1, ball grinder is vacuumized, planetary ball mill is placed in
(QM-3SP2) with the rotating speed ball milling of 200r/min 10 hours in, completely alloyed powder end is made.
Pre-burning：The alloy powder that ball milling obtains is placed in vitrified pot, high vacuum vertical sintering furnace (ZM-30- is placed in
16) in, it is 1 × 10 to be evacuated to vacuum degree-2Pa, with the heating rate of 5 DEG C/min, in 450 DEG C and 600 DEG C, each heat preservation 1 is small
When, then furnace cooling is obtained containing endogenous TiC, and the good composite powder of molding effect.
Prepare green compact：The composite powder that pre-burning is obtained is packed into the mold that internal diameter is 10mm, is placed on tablet press machine, is applied
The pressure of 10MPa, dwell time 15min are prepared into the green compact of 10 × 8mm of φ.
Sintering：Green compact, insulation tube (hexagonal boron nitride), graphite-pipe, molybdenum sheet, steel are emitted and assembled with pyrophillite, then
It is put into progress superhigh-pressure high-temp sintering in cubic hinge press.Under the pressure of 3GPa, 1200 are raised to the rate of 300 DEG C/min
DEG C, then heat-insulation pressure keeping 15min, after to be heated, continues the cooling of the samples such as pressurize 4min, sample is taken out in last pressure release.
TiC enhancings Ultra-fine Grained titanium-based made from the present embodiment is compound, and matrix is α phases, and material compression experiment measures it and bends
It is 1705MPa, breaking strain 3.77% to take intensity.Although enhancing Ultra-fine Grained composite wood using α phases as TiC made from matrix
Expect that intensity is suitable as TiC enhancing ultra-fine crystal composite materials made from matrix with β phases, but its plasticity is significantly lower than the latter.
Comparative example 3
Raw material：Ti powder, Nb powder are the powder of 60 irregular shape, and purity is in 99.9% or more, CH3(CH2)16COOH is that analysis is pure.
Proportioning weighs：Ti powder：Nb powder is calculated as 67 in mass ratio：33, CH3(CH2)16The additive amount of COOH is Ti powder and Nb powder
The 2.5wt% of quality sum.
High-energy ball-milling alloying：Load weighted raw material is placed in the stainless-steel vacuum ball grinder of 250ml, abrading-ball is using straight
The stainless steel ball of diameter 10mm, abrading-ball weight are 300g, ratio of grinding media to material 15:1, ball grinder is vacuumized, planetary ball mill is placed in
(QM-3SP2) with the rotating speed ball milling of 200r/min 8 hours in.
Pre-burning：The powder that ball milling obtains is placed in vitrified pot, is placed in high vacuum vertical sintering furnace (ZM-30-16),
It is 1 × 10 to be evacuated to vacuum degree-2Pa keeps the temperature 2 hours, then furnace cooling with the heating rate of 5 DEG C/min at 450 DEG C.
Prepare green compact：The powder that pre-burning is obtained is packed into the mold that internal diameter is 10mm, is placed on tablet press machine, is applied
The pressure of 10MPa, dwell time 15min are prepared into the green compact of 10 × 8mm of φ.
Sintering：Green compact, insulation tube (hexagonal boron nitride), graphite-pipe, molybdenum sheet, steel are emitted and assembled with pyrophillite, then
It is put into progress superhigh-pressure high-temp sintering in cubic hinge press.Under the pressure of 5GPa, 1200 are raised to the rate of 300 DEG C/min
DEG C, then heat-insulation pressure keeping 15min, after to be heated, continues the cooling of the samples such as pressurize 4min, sample is taken out in last pressure release.
Composite material manufactured in the present embodiment, since Ball-milling Time is shorter, powder fails to fully achieve alloying, sintering system
Sample, there is segregation on ingredient.
Claims (9)
1. a kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites, which is characterized in that include the following steps：
Step 1：Mechanical alloying
Titanium valve, niobium powder, carbon source are placed in ball milling in vacuum ball grinder, until elemental powders alloying；
The carbon source is one kind in stearic acid, alcohol, toluene, normal heptane；
The titanium valve, niobium powder additive amount count titanium valve in mass ratio：Niobium powder is 60~75:25~40；
The additive amount of the carbon source is 1~3wt% of titanium valve and niobium powder quality sum；
The ball-milling medium uses the stainless steel ball of a diameter of 8~Φ of Φ 15mm, ratio of grinding media to material 10:1~20:1, rotating speed 200
~280r/min；Ball-milling Time is 10~15h；
Step 2：Pre-burning
Alloy powder obtained by step 1 is put into vacuum sintering furnace, is sintered under vacuum, that is, obtains TiC and titanium-niobium alloy powder
End, the sintering temperature are 450~600 DEG C, and the sintered heat insulating time is 60~120min；
Step 3：Sintering
The powder pre-molding that step 2 is obtained is placed in cubic hinge press and is sintered, that is, obtain after assembling is sintered unit
TiC enhances Ultra-fine Grained β titanium niobium based composites；The sintering pressure is 2~5GPa, and sintering temperature is 1100~1200 DEG C.
2. a kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites according to claim 1, feature
It is, the carbon source is one kind in stearic acid, alcohol.
3. a kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites according to claim 1, feature exist
In, in step 1, the titanium valve, niobium powder grain size be 50~75 μm；The titanium valve, niobium powder purity 99.9% or more.
4. a kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites according to claim 1, feature exist
In in step 1, the additive amount of the carbon source is 2~3wt% of titanium valve and niobium powder quality sum.
5. a kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites according to claim 1, feature exist
In in step 1, ball-milling medium uses the stainless steel ball of a diameter of 10~Φ of Φ 15mm, ratio of grinding media to material 10:1~15:1, rotating speed
For 200~240r/min；Ball-milling Time is 10~12h.
6. a kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites according to claim 1, feature exist
In, in step 2, after alloy powder is put into vacuum sintering furnace, first stove is vacuumized, until vacuum degree be 5 × 10-2~5 ×
10-3Pa is then warming up to 450~600 DEG C by 5~8 DEG C/min of heating rate.
7. a kind of preparation method of TiC enhancings Ultra-fine Grained β titanium niobium based composites according to claim 1, feature exist
In, in step 3, sintering process is, under the pressure of 2~5GPa, 1100 are warming up to the rate of 300~400 DEG C/min~
1200 DEG C, 5~15min of heat-insulation pressure keeping, after heating, continue 3~4min of pressurize, after sample cooling, sample is taken out in pressure release.
8. a kind of preparation side of TiC enhancing Ultra-fine Grained β titanium niobium based composites according to claim 1-7 any one
Method, which is characterized in that in prepared TiC enhancing Ultra-fine Grained β titanium niobium based composites, the shaft-like such as reinforcement TiC is, volume point
Number is 25~40%, and grain size is 0.15~0.9 μm, is evenly distributed in titanium niobium matrix.
9. a kind of preparation side of TiC enhancing Ultra-fine Grained β titanium niobium based composites according to claim 1-7 any one
Method, which is characterized in that prepared TiC enhances Ultra-fine Grained β titanium niobium based composites, and matrix grain size is 0.2~1 μm, is caused
Density>99.3%, hardness be 452.2~552.1Hv, yield strength be 1660~1930MPa, breaking strain be 5.2~
21.88%.
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| CN111101049A (en) * | 2018-10-26 | 2020-05-05 | 青海民族大学 | In-situ NbC particle and iron-based amorphous alloy synergistically reinforced manganese steel-based composite material and preparation method thereof |
| CN110355375B (en) * | 2019-08-26 | 2020-12-18 | 西北有色金属研究院 | Preparation method of nano carbide in-crystal strengthened medium-high strength niobium alloy powder |
| 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 |
| CN114210981A (en) * | 2021-12-08 | 2022-03-22 | 罗镇霆 | Preparation method of titanium steel composite part |
| CN114438360B (en) * | 2021-12-31 | 2022-06-21 | 哈尔滨工业大学 | In-situ synthesized (TiNb) C reinforced superfine crystal TiNbMo refractory concentrated alloy-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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