CN109439984A - A kind of primary micro/nano level titanium carbide and amorphous alloy are total to reinforced magnesium alloy composite material and preparation method - Google Patents

A kind of primary micro/nano level titanium carbide and amorphous alloy are total to reinforced magnesium alloy composite material and preparation method Download PDF

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CN109439984A
CN109439984A CN201811091941.5A CN201811091941A CN109439984A CN 109439984 A CN109439984 A CN 109439984A CN 201811091941 A CN201811091941 A CN 201811091941A CN 109439984 A CN109439984 A CN 109439984A
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powder
amorphous alloy
alloy
magnesium
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CN109439984B (en
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彭建洪
杨永潇
毛多鹭
李海琴
李海宾
韩精卫
许珂琳
周德华
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Qinghai Nationalities University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0408Light metal alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder

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Abstract

The invention discloses a kind of primary micro/nano level titanium carbides and amorphous alloy to be total to reinforced magnesium alloy composite material and preparation method, key step are as follows: by titanium valve and graphite powder, ball milling obtains primary titanium carbide (TiCp) alloy powder in proportion;Magnesium powder or aluminium powder or titanium valve are mixed into high-energy ball milling with other alloying elements in proportion and obtain magnesium-based/aluminium base/titanium-based amorphous alloy powder;TiCp alloy powder is proportionally added into amorphous alloy powder, high-energy ball milling obtains the mixed powder of TiCp and amorphous alloy, then mixed powder is added in magnesium alloy-powder by a certain percentage, adds alcohol, mechanical stirring is carried out in the way of ultrasonic wave added, is dried again after mixing;The composite granule of drying is subjected to high pressure compression, obtains fine and close composite block blank, then low temperature hot-press sintering;The composite block that sintering is obtained carries out hot extrusion, and the primary micro/nano level titanium carbide and amorphous alloy for finally obtaining high-strength and high ductility are total to reinforced magnesium alloy composite material.

Description

A kind of primary micro/nano level titanium carbide and amorphous alloy are total to reinforced magnesium alloy composite wood Material and preparation method thereof
Technical field
The present invention relates to a kind of light metal composite material, in particular to a kind of hard carbide and amorphous alloy strengthen magnesium altogether Alloy composite materials and preparation method thereof.
Background technique
Magnesium alloy materials are since its density is low, specific strength is high, specific stiffness is high, damping capacity is good, thermal conductivity is good, is easily recycled The features such as utilization, is widely used in the fields such as Aeronautics and Astronautics, vehicle, 3C electronic product.However, due to most of magnesium alloys It is close-packed hexagonal (HCP) crystal structure, HCP structure has less independent slide system, and magnesium alloy is caused to have lower room Warm plasticity and toughness, in addition the mechanical strength of magnesium alloy and creep-resistant property are also all lower, these all limit the wide of magnesium alloy materials General application.
According to strengthening mechanism, using with high rigidity, high-modulus micro/nano level particle and fine grain magnesium alloy materials carry out It is compound, the comprehensive mechanical property of magnesium alloy materials can be significantly improved.Currently, studying the document report of magnesium-based composite material both at home and abroad In road, more commonly used reinforcement mainly has silicon carbide, oxide (aluminium oxide, silica etc.), boron carbide, titanium carbide, boron Change titanium, graphene, whisker/fibre, carbon nanotube etc., and preparation method mainly has stir casting, squeeze casting method, powder smelting Jin Fa, mechanical alloying method, pressure-free impregnation method, plasma agglomeration method, friction rabbling welding etc..Chinese patent (CN107523727A) Disclose the SiC reinforcement magnesium-based composite material (the maximum tensile strength that good mechanical performance is prepared by squeeze casting method 8.25%) 305MPa, elongation reach.Chinese patent (CN201710138404.0) discloses a kind of nano titanium carbide particle increasing The preparation method of strong magnesium-based composite material, precast body is added in liquid magnesium alloy, the doping to being warming up to 70 DEG C of fusing point or more The synchronous mechanical stirring applied under ultrasonic vibration effect of the magnesium alloy fused mass of nano titanium carbide particle precast body, efficiently solves and receives Rice titanium carbide granule is uniformly distributed problem, realizes additional nano titanium carbide particle and is uniformly distributed, the maximum tensile strength reaches To 345MPa, while it ensure that composite material has good plasticity and toughness (elongation reaches 18%).Chinese patent (application number 201710900751.2) disclose a kind of mixed phase enhancing magnesium-based composite material and preparation method thereof, main technological steps: right Magnesium alloy powder, Nano diamond particle, magnesium borate crystal whisker are pre-processed, and mixed-powder is prepared, and are made through mixing and ball milling Mixed powder after ball milling, then vacuum hotpressing is at base and hot extrusion.The mixed phase that the invention is prepared enhances magnesium-based composite wood The friction and abrasion and tension and compression symmetry of material significantly improve, comprehensive mechanical property also have highly significant raising (stretch/ The yield strength of compression is respectively 390MPa and 433MPa;Highest stretching/compressing intensity is respectively 418MPa and 480MPa;It draws Stretch/compression strain rate is respectively 6.2% and 10.1%).
Currently, strengthening magnesium-based composite wood altogether about using fabricated in situ micro-nano carbon compound and Amorphous Alloy Grain both at home and abroad The research of material has not been reported.Chinese patent (CN101368242A) discloses a kind of amorphous enhancing magnesium-based composite material and its system Standby technique, which includes amorphous particle NixMyTz(M indicates that Zr, the one or two of Nb, T indicate Ta, Ti, Hf, Ti, Si, At least one of Pd, P, Sn, Co, Mo, B, Cr, Al;30≤x≤70,3≤y≤50,0≤z≤35;80≤a≤100,0≤b ≤ 18,0≤c≤5,0≤d≤3) and magnesium base alloy MgaAlbQcRd(a+b+c+d=100 is weight percentage, 80≤a≤100, 0≤b≤18,0≤c≤5,0≤d≤3, Q indicate that Mn, the one or two of Zn, R indicate Ce, Zr, Cu, Ni, Si, Fe, B, Gd's It is at least one).The invention main processes: magnesium alloy particles are uniformly mixed with Amorphous Alloy Grain, cold pressing compacting, cold pressing Pressure is 30-250MPa, is then sintered in hot-pressed sintering furnace, hot pressing pressure 5-60MPa, sintering temperature 500- 700 DEG C, sintering time 30-180min.The intensity and toughness index for the amorphous enhancing magnesium-based composite material that the invention obtains are equal It is undesirable that (yield strength is up to 145MPa, while its tensile strength is 263MPa, and elongation percentage is 4.3%) possible original It uses higher sintering temperature because being, so the crystallite dimension of matrix is larger (substrate tissue toughness is poor), other amorphous Mutually it is bad with the phase interface binding performance of matrix, cause phase interface in deformation process to be easily destroyed, thus make crackle generate and it is fast Brittle failure occurs for speed extension, composite material.
Summary of the invention
Main thought of the invention is: using mechanical alloying method fabricated in situ preparation have high-specific surface area, high activity, The primary micro/nano level TiC of high rigiditypAnd the light metal-based Amorphous Alloy Grain with high crystallization temperature, high rigidity, then will WC particle carries out high-energy ball milling after mixing with Amorphous Alloy Grain and (reaches large scale TiCpParticle is partially submerged into the conjunction of large scale amorphous In gold particle), make TiC using the churned mechanically method of ultrasonic wave addedpParticle, Amorphous Alloy Grain and magnesium alloy-powder are abundant It is uniformly mixed, then densifies composite granule under high pressure, finally obtain that there is spy using low-temperature sintering and hot extrusion technique The high-strength and high-ductility composite material of magnesium alloy of different three-phase coexistence structure.Major technique innovation of the invention is: (1) in composite wood Special three-phase coexistence structure, i.e., larger-size TiC are formed in materialpParticle be embedded in simultaneously large scale Amorphous Alloy Grain and In magnesium alloy substrate phase, such special construction can play in composite material deformation process hinders amorphous alloy to accompany matrix Crystal grain rotates, while amorphous phase plays the role of hindering dislocation motion, and the phase interface with excellent mechanical property will not Larger shear stress is destroyed again, to greatly improve the effect of composite material integral strength;(2) tiny TiCp And Amorphous Alloy Grain can play good dispersion-strengthened action with Dispersed precipitate in ultra-fine grained magnesium alloy matrix.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is as follows:
Step 1 mixes titanium valve and graphite powder in proportion, and high-energy ball milling obtains high activity, high-ratio surface afterwards for a period of time Long-pending primary TiCpGranular powder;
Light metal magnesium powder or aluminium powder or titanium valve and some other alloying element are mixed in a certain ratio, high energy ball by step 2 Obtain that there is high activity, the magnesium-based of high crystallization temperature or aluminium base or titanium-based amorphous alloy granular powder after mill a period of time;
Step 3, the TiC for obtaining step 1pGranular powder is added to the amorphous alloy that step 2 obtains by a certain percentage In grain powder, TiC is obtained after high-energy ball millingpWith amorphous alloy mixed powder;
Step 4, the TiC for obtaining step 3pIt is added to magnesium alloy powder by a certain percentage with amorphous alloy mixed powder, A certain amount of alcohol is added, and carries out mechanical stirring with ultrasonic wave added mode and obtains uniformly mixed slurry, then by slurry It is put into vacuum drying oven and dries, then obtain composite granule;
Step 5, the composite granule for obtaining step 4 are placed in mold, are carried out using cold isostatic press or four-column hydraulic press High pressure compression obtains fine and close composite block blank;
Step 6, the fine and close composite block blank for obtaining step 5 are put into progress low temperature and pressure burning in vacuum sintering funace Knot, obtains high-densit hot pressing composite block material;
Step 6 is obtained block composite material with the progress hot extrusion of high extrusion ratio by step 7, finally obtains high-strength and high ductility Primary micro-nano/meter level TiCpReinforced magnesium alloy compound walking spa- cial system is total to amorphous alloy.
Further, in the step 1, the molar ratio of titanium valve and graphite powder is 1: 1, carries out high-energy ball milling again after mixing, Make the primary TiC of Ti and C element in-situ reactive synthesis high-specific surface area, high activity using high ballmilling energyp(according to ball milling energy The difference of amount and Ball-milling Time, the degree that in-situ chemical reaction occurs is different, and the range of obtained p is 0.85~1) granular powder Body, Ball-milling Time are 40~80h, ratio of grinding media to material 10: 1~20: 1, revolving speed 300-600r/min.
Further, in the step 2, magnesium powder or aluminium powder or titanium valve and some other alloying element (such as Cu, Ni, Si, Y, One of Fe, Ca, Zn, Nd, B etc. or a variety of) carry out mixing by a certain percentage, obtained after high-energy ball milling magnesium-based or aluminium base or Titanium-based amorphous alloy granular powder (it is required that its breaking strength must not be lower than 800MPa, crystallization temperature must not be lower than 350 DEG C), ball Time consuming is 40~100h, ratio of grinding media to material 10: 1~50: 1, revolving speed 300-600r/min.
Further, in the step 3, TiCpThe mixed proportion of particle and Amorphous Alloy Grain is 1: 6~1: 20, through height TiC can be obtained after ball millingpThe mixed powder of particle and Amorphous Alloy Grain, Ball-milling Time be 20~40h, ratio of grinding media to material 10: 1~ 20: 1, revolving speed 300-600r/min.The purpose of this step is, makes the biggish TiC of portion sizepIt is particle studded to be closed in amorphous In gold particle, and special three-phase coexistence structure, i.e., big TiC are formed in final block composite materialpParticle is inlayed simultaneously In amorphous alloy phase and matrix phase, and the rotation for hindering amorphous phase is played in deformation process in composite material, thus substantially Improve the effect of composite material integral strength;And tiny TiCpWith Amorphous Alloy Grain Dispersed precipitate in magnesium alloy substrate, Play dispersion-strengthened action.
Further, in the step 4, the TiC that is added in magnesium alloy-powderpParticle and Amorphous Alloy Grain, matter Amount accounts for the 0.25~5% and 5~30% of mixed powder gross mass respectively, remaining is magnesium alloy-powder;As long as alcohol additional amount is protected Slurry has enough mobility when card stirring;Ultrasonic power when ultrasonic wave added mechanical force stirs is 100~200Hz, Blade rotational speed is 300~1000rpm, mixing time 30-60min.
Further, in the step 4, the trade mark of magnesium alloy-powder can be Mg-Al system, Mg-Zn system, Mg-Mn system, Mg- One of RE system or Mg-Zn-RE-Zr system.
Further, in the step 4, by the slurry being uniformly mixed carry out vacuum drying, vacuum degree < 100Pa, Baking material temperature is 80 DEG C, and the baking material time is for 24 hours.
Further, in the step 5, mould therefor is stainless steel mould, and isostatic cool pressing or the hydraulic pressure of four columns For 300-600MPa, dwell time 10-30min.
Further, in the step 6, magnesium alloy substrate material crystal grain occurs during the sintering process grows up in order to prevent, Vacuum hotpressing process uses low-temperature sintering, and sintering range is 300~350 DEG C, and pressure is 50~100MPa, and the dwell time is 20min-1h.Low sintering purpose is: (1) preventing magnesium base amorphous alloy from crystallization change occurring in recombination process, to protect Demonstrate,prove invigoration effect of the amorphous phase to final composite material obtained;(2) it is ultra-fine for keeping the magnesium alloy substrate of final composite material Crystalline substance tissue, so that guaranteeing final composite material integrally has good plasticity and toughness.
Further, in the step 7, the temperature of hot extrusion is 280~300 DEG C, extrusion ratio 25: 1, and extruding rate is 0.05-0.2mm/s.The purpose of high extrusion ratio hot extrusion is: further densifying composite material and can refine matrix.
Further, preparation method of the invention can also include common magnesium alloy heat treatment process: the part T1- is dissolved Processing+natrual ageing;T2- casts after annealing;T3- solid solution+cold working;T4- solution treatment;T5- artificial aging;T6- solution treatment+ Artificial aging;T7- solution treatment+stabilization processes;T8- glory processing+cold working+artificial aging.
Detailed description of the invention
Fig. 1 is the preparation that primary micro/nano level titanium carbide and amorphous alloy are total to reinforced magnesium alloy composite material in the present invention Process flow diagram
Fig. 2 is the stress-strain curve of embodiment 1, embodiment 2, embodiment 3.
Specific embodiment
Embodiment 1:
A kind of primary micro/nano level titanium carbide and titanium-based amorphous alloy are total to the preparation method of reinforced magnesium alloy composite material, Its step are as follows:
Step 1. weighs 8g titanium valve and 2g graphite powder, is put into the ball grinder of 250ml, places into 100g ball milling steel ball.It will Ball grinder vacuumizes, and is then passed through argon gas (purity 99.9vol.%) in ball grinder from one end air inlet, and ball milling is canned Enter in ball mill, Ball-milling Time is 60 hours, and the revolving speed of ball mill is 500rpm, has obtained micro/nano level TiCpGranular powder.
Step 2. presses Ti50Zr15Cu15Ni5V5Be10The molar ratio of element in alloy cpd molecular formula, weighs titanium valve, zirconium Powder, copper powder, nickel powder, vanadium powder and beryllium powder (powder gross mass is 25g), are put into the ball grinder of 500ml, place into 250g ball-mill steel Ball.Ball grinder is vacuumized, is then passed through argon gas (purity 99.9v01.%) in ball grinder from one end air inlet, by ball milling It is canned enter ball mill in, Ball-milling Time is 100 hours, and the revolving speed of ball mill is 500rpm, is obtained Ti50Zr15Cu15Ni5V5Be10Amorphous Alloy Grain powder.
Then TiC that step 3. obtains step 1pGranular powder (5g) is added to what step 2 obtained Ti50Zr15Cu15Ni5V5Be10Continuing ball milling in Amorphous Alloy Grain powder, (Ball-milling Time is 20 hours, and ball mill turns Speed is 500rpm), then obtain TiCpParticle and Ti50Zr15Cu15Ni5V5Be10The mixed powder of Amorphous Alloy Grain.
Step 4. takes out the mixed powder that step 3 obtains, and weighs AZ91 magnesium alloy powder 75g, is put into the beaker of 500ml In, it is charged with 200ml alcohol, then carrying out the stirring of ultrasonic wave added mechanical force, (ultrasonic power 100Hz, blade rotational speed are 1000rpm, mixing time 60min);After stirring, uniformly mixed slurry is put into vacuum oven and is dried (vacuum degree 50Pa, baking material temperature are 80 DEG C, and the baking material time is for 24 hours).
The drying composite granule that step 4 obtains is placed in stainless steel mould by step 5., is carried out using four-column hydraulic press high Pressure compacting (pressure 500MPa, dwell time 10-30min) obtains fine and close composite block blank;
The fine and close composite block blank that step 6. obtains step 5, which is put into vacuum sintering funace, carries out hot pressed sintering (sintering pressure 100MPa, temperature are 300 DEG C, and the dwell time is 1 hour), obtains high-densit hot pressing composite block material;
Step 7. by step 6 obtain block composite material with high extrusion ratio carry out hot extrusion (extrusion temperature be 300 DEG C, squeeze Pressure ratio 25: 1, rate of extrusion 0.05mm/s), finally obtain composite material of magnesium alloy bar.
By the finally obtained primary micro-nano/meter level TiC of the present embodimentp(5%) and Ti50Zr15Cu15Ni5V5Be10Amorphous alloy (25%) reinforced magnesium alloy composite material bar is machined out to obtain standard tensile test sample altogether, then tries in omnipotent mechanics It tests and carries out extension test on machine, test result is (see Fig. 2): the yield strength of composite material is 514Mpa, the maximum tensile strength For 546MPa, maximum elongation rate is 6.2%.
Embodiment 2:
A kind of primary micro/nano level titanium carbide and al based amorphous alloy are total to the preparation method of reinforced magnesium alloy composite material, Its step are as follows:
Step 1. weighs 8g titanium valve and 2g graphite powder, is put into the ball grinder of 250ml, places into 100g ball milling steel ball.It will Ball grinder vacuumizes, and is then passed through argon gas (purity 99.9vol.%) in ball grinder from one end air inlet, and ball milling is canned Enter in ball mill, Ball-milling Time is 60 hours, and the revolving speed of ball mill is 500rpm, has obtained micro/nano level TiCpGranular powder.
Step 2. presses Al65Cu20Ti10Y5The molar ratio of element in alloy cpd molecular formula, weigh aluminium, copper powder, titanium valve and Yttrium powder (powder gross mass is 15g), is put into the ball grinder of 500ml, places into 300g ball milling steel ball.Ball grinder is vacuumized, Then argon gas (purity 99.9vol.%) is passed through in ball grinder from one end air inlet, ball grinder is fitted into ball mill, ball Time consuming is 80 hours, and the revolving speed of ball mill is 500rpm, has obtained Al65Cu20Ti10Y5Amorphous Alloy Grain powder.
Then TiC that step 3. obtains step 1pGranular powder (2g) is added to the Al that step 2 obtains65Cu20Ti10Y5It is non- Continue ball milling (Ball-milling Time is 20 hours, and the revolving speed of ball mill is 500rpm) in peritectic alloy granular powder, then obtains TiCpParticle and Al65Cu20Ti10Y5The mixed powder of Amorphous Alloy Grain.
Step 4. takes out the mixed powder that step 3 obtains, and weighs AZ91 magnesium alloy powder 83g, is put into the beaker of 500ml In, it is charged with 200ml alcohol, then carrying out the stirring of ultrasonic wave added mechanical force, (ultrasonic power 100Hz, blade rotational speed are 600rpm, mixing time 60min);After stirring, uniformly mixed slurry is put into vacuum oven and is dried (vacuum degree 50Pa, baking material temperature are 80 DEG C, and the baking material time is for 24 hours).
The drying composite granule that step 4 obtains is placed in stainless steel mould by step 5., is carried out using four-column hydraulic press high Pressure compacting (pressure 500MPa, dwell time 10-30min) obtains fine and close composite block blank;
The fine and close composite block blank that step 6. obtains step 5, which is put into vacuum sintering funace, carries out hot pressed sintering (sintering pressure 100MPa, temperature are 300 DEG C, and the dwell time is 1 hour), obtains high-densit hot pressing composite block material;
Step 7. by step 6 obtain block composite material with high extrusion ratio carry out hot extrusion (extrusion temperature be 300 DEG C, squeeze Pressure ratio 25: 1, rate of extrusion 0.1mm/s), finally obtain composite material of magnesium alloy bar.
By the finally obtained primary micro-nano/meter level TiC of the present embodimentp(2%) and Al65Cu20Ti10Y5Amorphous alloy (15%) Reinforced magnesium alloy compound walking spa- cial system is machined out to obtain standard tensile test sample altogether, then on omnipotent mechanics machine Extension test is carried out, test result is (see Fig. 2): the yield strength of composite material is 416MPa, and the maximum tensile strength is 448MPa, maximum elongation rate are 6.7%.
Embodiment 3:
A kind of primary micro/nano level titanium carbide and magnesium base amorphous alloy are total to the preparation method of reinforced magnesium alloy composite material, Its step are as follows:
Step 1. weighs 8g titanium valve and 2g graphite powder, is put into the ball grinder of 250ml, places into 100g ball milling steel ball.It will Ball grinder vacuumizes, and is then passed through argon gas (purity 99.9vol.%) in ball grinder from one end air inlet, and ball milling is canned Enter in ball mill, Ball-milling Time is 60 hours, and the revolving speed of ball mill is 500rpm, has obtained micro/nano level TiCpGranular powder.
Step 2. weighs 7.30g magnesium powder and 17.70g nickel powder, is put into the ball grinder of 500ml, places into 250g ball-mill steel Ball.Ball grinder is vacuumized, is then passed through argon gas (purity 99.9vol.%) in ball grinder from one end air inlet, by ball milling It is canned enter ball mill in, Ball-milling Time is 80 hours, and the revolving speed of ball mill is 500rpm, has obtained Mg50Ni50Amorphous alloy Grain powder.
Step 3. weighs the TiC that step 1 obtainspGranular powder 0.25g weighs the Mg that step 2 obtains50Ni50Amorphous alloy Granular powder 10g takes AZ91 magnesium alloy powder 89.75g, and these three powders is put into the beaker of 500ml, is charged with Then 200ml alcohol carries out the stirring of ultrasonic wave added mechanical force (ultrasonic power 100Hz, blade rotational speed 600rpm, when stirring Between be 60min);After stirring, uniformly mixed slurry is put into vacuum oven and is dried (vacuum degree 50Pa, baking Material temperature degree is 80 DEG C, and the baking material time is for 24 hours).
The drying composite granule that step 4 obtains is placed in stainless steel mould by step 5., is carried out using four-column hydraulic press high Pressure compacting (pressure 500MPa, dwell time 10-30min) obtains fine and close composite block blank;
The fine and close composite block blank that step 6. obtains step 5, which is put into vacuum sintering funace, carries out hot pressed sintering (sintering pressure 100MPa, temperature are 300 DEG C, and the dwell time is 1 hour), obtains high-densit hot pressing composite block material;
Step 7. by step 6 obtain block composite material with high extrusion ratio carry out hot extrusion (extrusion temperature be 300 DEG C, squeeze Pressure ratio 25: 1, rate of extrusion 0.15mm/s), finally obtain composite material of magnesium alloy bar.
By the finally obtained primary micro-nano/meter level TiC of the present embodimentp(0.25%) and Mg50Ni50Amorphous alloy (10%) is altogether Reinforced magnesium alloy compound walking spa- cial system is machined out to obtain standard tensile test sample, then enterprising in omnipotent mechanics machine Row extension test, test result are (see Fig. 2): the yield strength of composite material is 338Mpa, the maximum tensile strength 418MPa, Maximum elongation rate is 9.6%.

Claims (11)

1. a kind of primary micro/nano level titanium carbide and amorphous alloy are total to reinforced magnesium alloy composite material and preparation method, special Sign is to mainly comprise the steps that
Step 1 mixes titanium valve and graphite powder in proportion, and high-energy ball milling obtains high activity, high-specific surface area afterwards for a period of time Primary titanium carbide (TiCp) granular powder;
Light metal magnesium powder or aluminium powder or titanium valve and some other alloying element are mixed in a certain ratio, high-energy ball milling one by step 2 Obtain that there is high activity, the magnesium-based of high crystallization temperature or aluminium base or titanium-based amorphous alloy granular powder after the section time;
Step 3, the TiC for obtaining step 1pGranular powder is added to the Amorphous Alloy Grain powder that step 2 obtains by a certain percentage In, TiC is obtained after high-energy ball millingpWith amorphous alloy mixed powder;
Step 4, the TiC for obtaining step 3pIt is added to magnesium alloy powder by a certain percentage with amorphous alloy mixed powder, adds A certain amount of alcohol, and carry out mechanical stirring with ultrasonic wave added mode and obtain uniformly mixed slurry, then slurry is put into very It is dried in empty baking oven, then obtains composite granule;
Step 5, the composite granule for obtaining step 4 are placed in mold, carry out high pressure using cold isostatic press or four-column hydraulic press Compacting obtains fine and close composite block blank;
Step 6, the fine and close composite block blank for obtaining step 5 are put into vacuum sintering funace and carry out low temperature hot-press sintering, Obtain high-densit hot pressing composite block;
Step 6 is obtained block composite material with the progress hot extrusion of high extrusion ratio by step 7, finally obtains the primary of high-strength and high ductility Micro-nano/meter level titanium carbide and amorphous alloy are total to reinforced magnesium alloy composite material.
Step 8, can be to the composite material of magnesium alloy for obtaining step 7 heat treatment appropriate.
2. preparation method according to claim 1, it is characterised in that: in the step 1, the molar ratio of titanium valve and graphite powder It is 1: 1, high-energy ball milling obtains the primary TiC of high activity, high-specific surface area afterwards for a period of timep(when according to ballmilling energy and ball milling Between difference, the degree of reaction in-situ is different, and the range of obtained p is 0.85~1) granular powder, Ball-milling Time is 40~ 80h, ratio of grinding media to material 10: 1~20: 1, revolving speed 300-600r/min.
3. preparation method according to claim 1, it is characterised in that: in the step 2, light metal magnesium powder or aluminium powder or titanium Powder and some other alloying element (one of such as Cu, Ni, Si, Y, Fe, Ca, Zn, Nd, B or a variety of) by a certain percentage into Row mixing obtains magnesium-based or aluminium base or titanium-based amorphous alloy granular powder (it is required that its breaking strength is not less than after high-energy ball milling 800MPa, crystallization temperature must not be lower than 350 DEG C), Ball-milling Time is 40~100h, and ratio of grinding media to material 10: 1~50: 1, revolving speed is 300-600r/min。
4. preparation method according to claim 1, it is characterised in that: in the step 3, TiCpParticle and amorphous alloy The mixed proportion of grain obtains TiC 1: 6~1: 20 after high-energy ball millingpThe mixed powder of particle and Amorphous Alloy Grain, ball milling Time is 20~40h, ratio of grinding media to material 10: 1~20: 1, revolving speed 300-600r/min.
5. preparation method according to claim 1, it is characterised in that: in the step 4, be added in magnesium alloy-powder TiCpParticle and Amorphous Alloy Grain, quality account for the 0.25~5% and 5~30% of mixed powder gross mass respectively, remaining is Magnesium alloy-powder;As long as alcohol additional amount guarantees that slurry has enough mobility when stirring;Ultrasonic wave added mechanical force is stirred Ultrasonic power when mixing is 100~200Hz, and blade rotational speed is 300~1000rpm, mixing time 30-60min.
6. preparation method according to claim 1, it is characterised in that: in the step 4, the trade mark of magnesium alloy-powder can be One of Mg-Al system, Mg-Zn system, Mg-Mn system, Mg-RE system or Mg-Zn-RE-Zr system.
7. preparation method according to claim 1, it is characterised in that: in the step 4, the slurry that will be uniformly mixed Vacuum drying, vacuum degree < 100Pa are carried out, baking material temperature is 80 DEG C, and the baking material time is for 24 hours.
8. preparation method according to claim 1, it is characterised in that: in the step 5, mould therefor is stainless steel mold Tool, and isostatic cool pressing or the hydraulic pressure of four columns are 300-600MPa, dwell time 10-30min.
9. preparation method according to claim 1, it is characterised in that: in the step 6, magnesium alloy substrate material in order to prevent Crystal grain occurs during the sintering process and grows up for material, and vacuum hotpressing process uses low-temperature sintering, and sintering range is 300~350 DEG C, Pressure is 50~100MPa, dwell time 20min-1h.
10. preparation method according to claim 1, it is characterised in that: in the step 7, the temperature of hot extrusion is 280~ 300 DEG C, extrusion ratio 25: 1, extruding rate 0.05-0.2mm/s.
11. preparation method according to claim 1, it is characterised in that:, can be to magnesium prepared by the present invention in the step 8 Alloy composite materials carry out heat treatment appropriate, that is, use some common magnesium alloy heat treatment process: the part T1- solution treatment + natrual ageing;T2- casts after annealing;T3- solid solution+cold working;T4- solution treatment;T5- artificial aging;T6- solution treatment+artificial Timeliness;T7- solution treatment+stabilization processes;T8- glory processing+cold working+artificial aging.
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CN110791677A (en) * 2019-11-18 2020-02-14 中国科学院上海硅酸盐研究所 High-performance wear-resistant bronze-based composite material and preparation method and application thereof
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CN114309622A (en) * 2021-11-18 2022-04-12 宁波中乌新材料产业技术研究院有限公司 Preparation method of aluminum alloy powder for multiphase composite additive manufacturing
CN115287513A (en) * 2022-08-06 2022-11-04 刘满全 Red copper particle reinforced magnesium-based composite material and preparation method thereof
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