CN106834878B - A kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material - Google Patents
A kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material Download PDFInfo
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- CN106834878B CN106834878B CN201710212374.3A CN201710212374A CN106834878B CN 106834878 B CN106834878 B CN 106834878B CN 201710212374 A CN201710212374 A CN 201710212374A CN 106834878 B CN106834878 B CN 106834878B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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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
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
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Abstract
The invention discloses a kind of methods that microwave sintering prepares endogenous high-entropy alloy-base composite material, the steps include: microwave synthetic reaction sample processed；It fills sample: compact specimen is packed into vacuum microwave reacting furnace；It vacuumizes；Reaction synthesis: adjustment input power；Heat preservation: when fully reacting reaches assigned temperature, furnace is cold after keeping the temperature a period of time；Come out of the stove: furnace is cold in vacuum microwave, takes out, and obtains endogenous high-entropy alloy-base composite material.Present invention process synthesizes interior raw type high-entropy alloy-base composite material by the way of microwave sintering, wetability is good between the reinforcement and matrix of microwave synthesis, it is small that sample is heated evenly thermal stress, reaction activity is low, synthesis temperature is lower, and method is easy to operate, safe and reliable, energy- and time-economizing, environmental-friendly.
Description
Technical field
The present invention relates to a kind of microwave synthesis method of high-entropy alloy-base composite material, especially a kind of high entropy of endogeny is closed
The microwave process for synthesizing of auri composite material, belongs to field of material preparation.
Background technique
Microwave sintering synthesis high-entropy alloy-base composite material, which refers to, replaces traditional heat source heating method with microwave heating, to add
The good sample of hot mixing, the reaction temperature that this method generates reinforcement is lower than the temperature that traditional heating generates reinforcement, preparation
High-entropy alloy sample tissue compactness it is good.This method, that is, environment friendly and pollution-free, but it is easy to operate have good stability, while having again
There is reinforcement to be evenly distributed, the advantages that matrix is tightly combined.Most importantly the material property prepared is more superior, forms energy
Power is strong.High-entropy alloy-base composite material is because it is with high rigidity, high-wearing feature, oxidation resistance, high temperature resistant softening power by
The extensive concern of researcher.With TiB2A small amount of nanometer Cu phase can be precipitated in intergranular in the addition of reinforcement, and yield strength has
Increased, plays toughening effect.Electric conductivity and hardness can be also correspondingly improved.High-entropy alloy-base composite material is in abrasion-resistant part
It is widely used in preparation, in addition to this also there is a small amount of application in the preparation of high temperature resistant element and shock resistance element.
Document one is compound using the high-entropy alloy AlCoCrCuFeNi/TiC that vacuum electromagnetic induction melting has synthesized six pivots
Material takes a long time, and energy consumption is higher, requires high (Sheng Hong flies, China Science & Technology University, 2014) to the melting of raw material.More
Common electric arc melting technology, for example, by using the FeCrCoNiCuTi/ for the synthetic method preparation that powder agglomates and metal are badly used in mixed way
TiC high-entropy alloy composite material (Lu Suhua, Harbin Institute of Technology, 2008), it is also difficult to reinforcement be avoided to be distributed in the base
Unevenly, the poor disadvantage of interfacial combined function, although wear-resisting property increases, yield strength is declined.It is so far
The open research report of applied microwave sintering synthesis high-entropy alloy-base composite material is not only found also.
Summary of the invention
It is an object of that present invention to provide a kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material, the works
Skill is easy to operate, safe and reliable, energy- and time-economizing, environmental-friendly, and tiny TiB2Enhance particle be reaction in-situ generate, surface without
Pollution, clean interfaces.The present invention is lower using powder microwave sintering activation energy, and reaction synthesis temperature is lower.
Realize the object of the invention technical solution are as follows: a kind of endogenous high-entropy alloy-base composite material of microwave sintering preparation
Method, comprising the following steps:
The first step, high-purity Al, Ni, Ti, Cr, Co, Mo, Cu, Fe, B powder is mixed after ball milling, wherein mixed proportion is pressed
According to the required reinforcement volume fraction adjustment of target composite material；
Second step, by the powder drying after ball milling, be squeezed into base sample, by sample be placed in vacuum microwave after, vacuumize；
In 20-50K/min, microwave intermittent heat is heated with guaranteeing that temperature plateau rises for third step, control heating rate
When occurring to generate enhancing precursor reactant to 450~700 DEG C to sample, thermal explosion occurs at this time, temperature instantaneously increases, heating curve slope
It changes, stops microwave operational immediately to guarantee that sample autologous tissue densification process is not influenced by microwave, to reaction temperature
When voluntarily falling back to former setting heating curve, continue to be warming up at 1100~1200 DEG C being sintered；
After 4th step, 30~60min of preserving heat after reaction ends, high-entropy alloy-base composite material is obtained.
Preferably, in the first step, by high-purity Al, Ni, Ti, Cr, Co, Mo, Cu, Fe, B powder equimolar than ball after mixing
Mill.
Preferably, in the first step, the ball powder mass ratio is 5:1；Rotational speed of ball-mill is 250-300p.r.m；Ball-milling Time
For 6~8h.
Preferably, in second step, drying temperature is 110~120 DEG C；It is evacuated to 10- 4~10- 3Pa is squeezed under 180MPa
It is pressed into base sample.
Preferably, in third step, continue to be warming up to being sintered 10 minutes at 1100~1200 DEG C.
Compared with prior art, remarkable advantage of the invention is: (1) being lower than conventional heating side using microwave synthesized activation energy
Formula, reaction temperature is lower, and technological operation is simple, safe and reliable, energy- and time-economizing, environmental-friendly.(2) due to heating rate fast response
Process is short, it is suppressed that microstructure coarsening, this method can significant thinning microstructure, simultaneously because reaction concentrate, the high fever for reacting generation can
Effectively purification matrix is conducive to the performance for improving material.(3) spinodal decomposition and crystalline substance mutually occur for the high-entropy alloy matrix that reaction generates
Stress relaxation deformation of the lattice twisted effect to hinder material to occur since lattice is mobile.(4) high-entropy alloy-base that reaction generates
For composite material at single face-centred cubic structure, institutional framework does not generate complicated intermetallic compound phase simply, organizes established practice
Then single-phase or two-phase solid solution structure.
Detailed description of the invention
Fig. 1 is the XRD diffraction image of the high-entropy alloy-base composite material of the embodiment of the present invention 1.
Fig. 2 is the matrix SEM scanned photograph of the high-entropy alloy-base composite material of the embodiment of the present invention 1.
Fig. 3 is the conventional heating and microwave heating heating curve of the high-entropy alloy-base composite material of present example example 1.
Specific embodiment
The method that microwave sintering of the present invention prepares endogenous high-entropy alloy-base composite material, specifically includes following step
It is rapid:
(1) system reaction sample: selected reaction system Al-Ni-Ti-Cr-Co-Fe-Mo-Cu-B, because in microwave reaction system
Heating up simultaneously outside, specimen temperature gradient is smaller, and sintering temperature is low, with violent exothermic reaction.By Al, Ni, Ti, Cr, Co, Fe,
Ball milling after the mixing of Mo, Cu and B powder, wherein the molar ratio of Ni, Ti, Al and B are according to chemical equation: 4Al+2Ti+3B+Ni →
AlNi+Al3Ti+TiB2, and with reaction product (TiB2) be reinforcement, allow Al, Ni, Ti and remaining other elements as matrix
Phase, the intermetallic compound phase for reacting generation can decompose generation solid solution at high temperature, by calculating final matrix phase composition powder
End is weighed according to molar ratio, and ball powder ratio is (4-5): 1, revolving speed 250-300p.r.m, Ball-milling Time 360-480min, then will
Powder after ball milling is squeezed into base, and reaction sample is made.
(2) dress sample vacuumizes: compact specimen being packed into reaction unit, guarantees the full mistake of the top clear observing response of Judas-hole
Journey is evacuated down to 10 after reaction unit is placed in vacuum drying oven- 4~10- 3Pa。
(3) reaction synthesis: adjustment input power obtains the heating rate of 20-50K/min, observes sample by Judas-hole
Change procedure of the color in warm；
(4) it keeps the temperature: when the color generation cataclysm of reaction sample, being warming up to 1100 degree of heat preservations, reduce input power and protected
Temperature stops power input after keeping the temperature 10~20min；
(5) it comes out of the stove: taking out reaction sample after furnace is cold, obtain high-entropy alloy-base composite material block materials.
(6) it polishes: being gone out surface small amounts layer with grinder buffing；
Embodiment 1:Al-Ni-Ti-Cr-Co-Fe-Mo-B reaction system
(1) system reaction Sample A l powder, Ni powder, Ti powder, Cr powder, Co powder, Fe powder, Mo powder, B powder molar ratio be 1:1:1:1:
Then 1:1:0.5:0.7 is placed them into ball grinder, with the ball powder ratio of mass ratio 5:1,300p.r.m revolving speed ball milling mixing,
Compact specimen is made at base with 120MPa pressure extrusion again；
(2) dress sample, which is vacuumized, is placed in microwave vacuum reacting furnace for compact specimen, is evacuated to 10- 4-10- 3Pa；
(3) reaction synthesis adjusts input power 3Kw, and heating rate 20K/min is warming up to 600 DEG C of compact specimens and chemistry occurs
Reaction generates reinforcement phase；
(5) heat preservation is continuously heating to 1200 DEG C of adjustable low input powers, and heat preservation after ten minutes, stops power input.
(6) blow-on samples after cooling is come out of the stove when being furnace-cooled to room temperature.
XRD diffraction is carried out to high-entropy alloy-base composite material obtained in (6), as shown in Fig. 1, SEM scanning analysis is such as
Shown in attached drawing 2.The high-entropy alloy-base composite material matrix made as shown in Figure 1 is mainly simple face-centered cubic phase high-entropy alloy-base
Body, enhancing item are TiB2 ceramic particle.It is different two-phase groups that spinodal decomposition, which mutually occurs, for the face-centered cubic matrix known to attached drawing 2
At, respectively richness Cr, Fe, Mo face-centered cubic phase and richness AlTiNi face-centered cubic phase, visible small enhancing particle in SEM scanning.
Attached drawing 3 shows that microwave heating synthesis high-entropy alloy-base composite material activation energy is low compared with low reaction temperatures and occurs instead at 400 DEG C or so
Heat generation reinforcement phase should be released, and conventional heating reaction activity high reaction temperature height just reacts close to 700 DEG C
Heat release generates reinforcement phase.
Embodiment 2:Al-Ni-Ti-Cr-Co-Fe-Mo-Cu-B reaction system
(1) system reaction Sample A l powder, Ni powder, Ti powder, Cr powder, Co powder, Fe powder, Mo powder, Cu powder, B powder molar ratio be 1:
1:1:1:1:1:1:0.5:0.7 then placing them into ball grinder, with the ball powder ratio of 4.5:1,280p.r.m revolving speed ball milling is mixed
It closes, then compact specimen is made at base with 120MPa pressure extrusion；
(2) dress sample, which is vacuumized, is placed in vacuum reaction furnace for compact specimen, is evacuated to 10- 4-10- 3Pa；
(3) reaction synthesis adjusts input power, with heating rate 25K/min heating, until chemistry occurs for 780 DEG C of compact specimens
Reaction；
(5) heat preservation adjusts input power 3Kw, and heating rate 20K/min is warming up to 600 DEG C of compact specimens and chemically reacts
Generate reinforcement phase；
(6) blow-on samples after cooling is come out of the stove when being furnace-cooled to room temperature.
Electron-microscope scanning is carried out to interior crystalline substance multiphase granules powder obtained in (9), as shown in Figure 2.
Claims (4)
1. a kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material, which comprises the following steps:
The first step, high-purity Al, Ni, Ti, Cr, Co, Mo, Cu, Fe, B powder is mixed after ball milling, wherein mixed proportion is according to mesh
Mark the required reinforcement volume fraction adjustment of composite material；
Second step, by the powder drying after ball milling, be squeezed into base sample, by sample be placed in vacuum microwave after, vacuumize；
In 20-50K/min, microwave intermittent heat is heated to 450 to guarantee that temperature plateau rises for third step, control heating rate
~700 DEG C to sample occur generate enhancing precursor reactant when, thermal explosion occurs at this time, temperature instantaneously increases, heating curve slope occur
Change, stops microwave operational immediately to guarantee that sample autologous tissue densification process is not influenced by microwave, voluntarily to reaction temperature
When falling back to former setting heating curve, continue to be warming up to being sintered 10 minutes at 1100~1200 DEG C；
After 4th step, 30~60min of preserving heat after reaction ends, high-entropy alloy-base composite material is obtained；The composite material is mainly
Use the high-entropy alloy of microwave synthesis Al-Ni-Ti-Cr-Co-Mo-Cu-Fe-B system for matrix and with particle TiB2For reinforcement group
At the hard wearing composite material of height.
2. the method as described in claim 1, which is characterized in that in the first step, Al powder, Ni powder, Ti powder, Cr powder, Co powder, Fe
Powder, Mo powder, Cu powder, B powder molar ratio be 1:1:1:1:1:1:1:0.5:0.7.
3. the method as described in claim 1, which is characterized in that in the first step, ball powder mass ratio is 5:1；Rotational speed of ball-mill is
250-300r. p. m；Ball-milling Time is 6~8h.
4. the method as described in claim 1, which is characterized in that in second step, drying temperature is 110~120 DEG C；It is evacuated to
10- 4~10- 3Pa is squeezed into base sample under 180MPa.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107254595A (en) * | 2017-06-14 | 2017-10-17 | 南京理工大学 | Raw type nanometer TiB in sensing heating synthesis2The method of granule reinforced copper base composite material |
| CN107267845A (en) * | 2017-06-21 | 2017-10-20 | 南京理工大学 | Nano particle TiC strengthens the microwave synthesis method of high-entropy alloy-base composite material |
| CN109694979B (en) * | 2017-10-20 | 2021-05-07 | 南京理工大学 | High-entropy alloy-based composite material prepared by vacuum induction melting and preparation method thereof |
| CN108375905A (en) * | 2018-03-09 | 2018-08-07 | 三峡大学 | A kind of segmented charge ratio course control method for use based on activation energy analysis |
| CN108504890B (en) * | 2018-05-17 | 2022-04-29 | 哈尔滨工业大学 | Basal high-entropy alloy composite material and preparation method thereof |
| CN108690929A (en) * | 2018-05-24 | 2018-10-23 | 南京理工大学 | The preparation method of interior raw type nano-particle reinforcement high-entropy alloy-base composite material |
| CN110042295B (en) * | 2019-04-25 | 2020-12-15 | 北京理工大学 | Preparation method of nano high-entropy alloy block material |
| CN111304479A (en) * | 2020-03-18 | 2020-06-19 | 南昌航空大学 | Preparation method of VCrNbMoW refractory high-entropy alloy |
| CN112342418B (en) * | 2020-09-09 | 2022-02-15 | 江苏大学 | Face-centered cubic boron-containing high-entropy alloy prepared by microwave sintering and preparation method thereof |
| CN112723862B (en) * | 2020-12-29 | 2022-11-22 | 太原理工大学 | Method for preparing high-entropy oxide ceramic material simply and with low consumption |
| CN112876237A (en) * | 2021-03-09 | 2021-06-01 | 郑州航空工业管理学院 | Preparation method of sintered transition metal high-entropy ceramic oxide composite material |
| CN117070934B (en) * | 2023-08-22 | 2024-03-12 | 安徽工业大学 | High-entropy alloy coating with wide hardness gradient and preparation method thereof |
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