CN106834878A - 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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- CN106834878A CN106834878A CN201710212374.3A CN201710212374A CN106834878A CN 106834878 A CN106834878 A CN 106834878A CN 201710212374 A CN201710212374 A CN 201710212374A CN 106834878 A CN106834878 A CN 106834878A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- 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
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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)
Abstract
The invention discloses a kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material, its step is：Microwave synthetic reaction sample processed；Dress sample：Compact specimen is loaded into vacuum microwave reacting furnace；Vacuumize；It is synthesized：Adjustment input power；Insulation：When reaction completely arrives at assigned temperature, stove is cold after insulation a period of time；Come out of the stove：In vacuum microwave stove it is cold, take out, obtain 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 relatively low, and method is simple to operate, safe and reliable, energy- and time-economizing, environment-friendly.
Description
Technical field
The present invention relates to a kind of microwave synthesis method of high-entropy alloy-base composite material, particularly a kind of endogenous entropy high is closed
The microwave process for synthesizing of auri composite, belongs to field of material preparation.
Background technology
Microwave sintering synthesis high-entropy alloy-base composite material refers to replace traditional heat source mode of heating to add with heating using microwave
The good sample of hot mixing, the reaction temperature of the method generation reinforcement is lower than the temperature of traditional heating generation reinforcement, prepares
High-entropy alloy sample tissue compactness it is good.The method be it is environment friendly and pollution-free, and it is simple to operate have good stability, while have again
There is reinforcement to be evenly distributed, the advantages of matrix is tightly combined.Most importantly the material property for preparing is more superior, is molded energy
Power is strong.High-entropy alloy-base composite material has high rigidity because of it, and high-wearing feature, oxidation resistance, high temperature resistant softening power is subject to
The extensive concern of researcher.With TiB2The addition of reinforcement, a small amount of nanometer Cu phases can be separated out in intergranular, and its yield strength has
Increased, played toughening effect.Electric conductivity and hardness can also be correspondingly improved.High-entropy alloy-base composite material is in abrasion-resistant part
It is widely used in preparation, in addition also there is a small amount of application in the preparation of high temperature resistant element and shock resistance element.
Document one is combined using the high-entropy alloy AlCoCrCuFeNi/TiC that vacuum electromagnetic induction melting has synthesized six pivots
Material, time-consuming more long, energy consumption is higher, and the melting requirement to raw material is (Sheng Hongfei, China Science ＆ Technology University, 2014) high.More
Common electric arc melting technology, for example with FeCrCoNiCuTi/ prepared by the bad synthetic method being used in mixed way of powder agglomates and metal
TiC high-entropy alloys composite (Lu Suhua, Harbin Institute of Technology, 2008), it is also difficult to avoid reinforcement from being distributed in the base
It is uneven, the poor shortcoming of interfacial combined function, although anti-wear performance increases, but yield strength has 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.
The content of the invention
Present invention aim at the method that a kind of microwave sintering of offer prepares endogenous high-entropy alloy-base composite material, the work
Skill is simple to operate, safe and reliable, energy- and time-economizing, environment-friendly, and tiny TiB2Enhancing particle be reaction in-situ generation, surface without
Pollution, clean interfaces.The present invention is relatively low using powder microwave sintering activation energy, temperature is synthesized relatively low.
Realize that the object of the invention technical solution is：A kind of microwave sintering prepares endogenous high-entropy alloy-base composite material
Method, comprise 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 reinforcement volume fraction adjustment needed for target composite；
Second step, by the powder drying after ball milling, be squeezed into base sample, after sample is inserted into vacuum microwave, vacuumize；
3rd step, control heating rate, to ensure that temperature plateau rises, are heated in 20-50K/min, microwave intermittent heat
During to 450~700 DEG C to sample generation generation enhancing precursor reactant, now there is thermal explosion, temperature is instantaneously raised, heating curve slope
Change, microwave operational is stopped immediately to ensure that sample autologous tissue densification process is not influenceed by microwave, question response temperature
When voluntarily falling back to former setting heating curve, sintered at continuing to be warmed up to 1100~1200 DEG C；
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, described ball powder mass ratio is 5：1；Rotational speed of ball-mill is 250-300p.r.m；Ball-milling Time
It is 6~8h.
Preferably, in second step, drying temperature is 110~120 DEG C；It is evacuated to 10- 4~10- 3Pa, in crowded under 180MPa
It is pressed into base sample.
Preferably, in the 3rd step, sintered 10 minutes at continuing to be warmed up to 1100~1200 DEG C.
Compared with prior art, remarkable advantage of the invention is：(1) conventional heating side is less than using microwave synthesized activation energy
Formula, reaction temperature is relatively low, and technological operation is simple, safe and reliable, energy- and time-economizing, environment-friendly.(2) due to heating rate fast response
Process is short, it is suppressed that microstructure coarsening, the method can notable thinning microstructure, simultaneously because reaction is concentrated, reacting the hyperpyrexia for producing can
Effectively purification matrix, is conducive to improving the performance of material.(3) there is spinodal decomposition and crystalline substance in the high-entropy alloy matrix phase of reaction generation
Lattice twisted effect deforms so as to hinder material due to the stress relaxation that lattice movement occurs.(4) high-entropy alloy-base of reaction generation
Into single face-centred cubic structure, institutional framework does not generate the intermetallic compound phase of complexity simply to composite, organizes established practice
Then single-phase or two-phase solid solution structure.
Brief description of the drawings
Fig. 1 is the XRD diffraction images of the high-entropy alloy-base composite material of the embodiment of the present invention 1.
Fig. 2 is the matrix SEM scanned photographs of the high-entropy alloy-base composite material of the embodiment of the present invention 1.
Fig. 3 is the conventional heating and heating using microwave 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
Suddenly：
(1) system reaction sample：Selected reaction system Al-Ni-Ti-Cr-Co-Fe-Mo-Cu-B, because in microwave reaction system
Outer intensification specimen temperature gradient simultaneously 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 mol ratio of Ni, Ti, Al and B is according to chemical equation：4Al+2Ti+3B+Ni→
AlNi+Al3Ti+TiB2, and with 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 mol ratio, and ball powder ratio is (4-5)：1, rotating speed is 250-300p.r.m, and Ball-milling Time is 360-480min, then will
Powder after ball milling is squeezed into base, is made reaction sample.
(2) dress sample is vacuumized：Compact specimen is loaded into reaction unit, it is ensured that the full mistake of the clear observing response of top Judas-hole
Journey, after reaction unit is inserted into vacuum drying oven, is evacuated down to 10- 4~10- 3Pa。
(3) it is synthesized：Adjustment input power, obtains the heating rate of 20-50K/min, and sample is observed by Judas-hole
Change procedure of the color in warm；
(4) it is incubated：When the color of reaction sample occurs cataclysm, 1100 degree of insulations are warmed up to, reduce input power and protected
Temperature, power input is stopped after 10~20min of insulation；
(5) come out of the stove：Reaction sample is taken out after stove is cold, high-entropy alloy-base composite material block materials are obtained.
(6) polish：Gone out surface small amounts layer with grinder buffing；
Embodiment 1：Al-Ni-Ti-Cr-Co-Fe-Mo-B reaction systems
(1) system reaction Sample A l powder, Ni powder, Ti powder, Cr powder, Co powder, Fe powder, Mo powder, the mol ratio of B powder are 1:1:1:1:
1:1:0.5:0.7, in then placing them into ball grinder, with mass ratio 5：1 ball powder ratio, 300p.r.m rotating speed ball milling mixings,
Compact specimen is made into base with 120MPa pressure extrusions again；
(2) dress sample is vacuumized and for compact specimen to insert microwave vacuum reacting furnace, is evacuated to 10- 4-10- 3Pa；
(3) regulation input power 3Kw, heating rate 20K/min is synthesized and is warming up to 600 DEG C of compact specimens generation chemistry
Reaction generation enhancing body phase；
(5) insulation is continuously heating to 1200 DEG C of adjustable low input powers, after being incubated 10 minutes, stops power input.
(6) blow-on sampling after cooling comes out of the stove stove when being cooled to room temperature.
High-entropy alloy-base composite material to being obtained in (6) carries out XRD diffraction, and as shown in Figure 1, SEM scanning analysis are such as
Shown in accompanying 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 is TiB2 ceramic particles.It is different two-phase groups to understand that face-centered cubic matrix phase occurs spinodal decomposition by accompanying drawing 2
Into respectively richness Cr, Fe, Mo face-centered cubic phase and richness AlTiNi face-centered cubic phases, visible small enhancing particle in SEM scannings.
Accompanying drawing 3 shows that heating using microwave synthesis high-entropy alloy-base composite material activation energy is low compared with low reaction temperatures to be occurred instead at 400 DEG C or so
Heat generation enhancing body phase should be released, and conventional heating reaction activity high reaction temperature is high is just reacted close to 700 DEG C
Heat release generation enhancing body phase.
Embodiment 2：Al-Ni-Ti-Cr-Co-Fe-Mo-Cu-B reaction systems
(1) system reaction Sample A l powder, Ni powder, Ti powder, Cr powder, Co powder, Fe powder, Mo powder, Cu powder, the mol ratio of B powder are 1:
1:1:1:1:1:1:0.5:0.7, in then placing them into ball grinder, with 4.5：1 ball powder ratio, 280p.r.m rotating speeds ball milling is mixed
Close, then compact specimen is made into base with 120MPa pressure extrusions；
(2) dress sample is vacuumized and for compact specimen to insert vacuum reaction stove, is evacuated to 10- 4-10- 3Pa；
(3) regulation input power is synthesized, is heated up with heating rate 25K/min, chemistry occurs to 780 DEG C of compact specimens
Reaction；
(5) insulation regulation input power 3Kw, heating rate 20K/min are warming up to 600 DEG C of compact specimens and chemically react
Generation enhancing body phase；
(6) blow-on sampling after cooling comes out of the stove stove when being cooled to room temperature.
Interior brilliant multiphase granules powder to being obtained in (9) carries out electron-microscope scanning, as shown in Figure 2.
Claims (6)
1. a kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material, it is characterised in that comprise 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
The required reinforcement volume fraction adjustment of mark composite；
Second step, by the powder drying after ball milling, be squeezed into base sample, after sample is inserted into vacuum microwave, vacuumize；
3rd step, control heating rate, to ensure that temperature plateau rises, are heated to 450 in 20-50K/min, microwave intermittent heat
~700 DEG C to sample occur generation enhancing precursor reactant when, now there is thermal explosion, temperature is instantaneously raised, heating curve slope occur
Change, microwave operational is stopped immediately to ensure that sample autologous tissue densification process is not influenceed by microwave, question response temperature is voluntarily
When falling back to former setting heating curve, sintered at continuing to be warmed up to 1100~1200 DEG C；
After 4th step, 30~60min of preserving heat after reaction ends, high-entropy alloy-base composite material is obtained.
2. the method for claim 1, it is characterised in that in the first step, by high-purity Al, Ni, Ti, Cr, Co, Mo, Cu,
Fe, B powder equimolar are than ball milling after mixing.
3. the method for claim 1, it is characterised in that in the first step, described ball powder mass ratio is 5：1；Ball milling turns
Speed is 250-300p.r.m；Ball-milling Time is 6~8h.
4. the method for claim 1, it is characterised in that in second step, drying temperature is 110~120 DEG C；It is evacuated to
10- 4~10- 3Pa, in being squeezed into base sample under 180MPa.
5. the method for claim 1, it is characterised in that in the 3rd step, sinters at continuing to be warmed up to 1100~1200 DEG C
10 minutes.
6. the high-entropy alloy-base composite material that the method as described in claim 1-5 is any synthesizes, it is characterised in that described compound
Material is mainly the high-entropy alloy for using microwave to synthesize Al-Ni-Ti-Cr-Co-Mo-Cu-Fe-B systems for matrix and with particle TiB2
It is the hard wearing composite material of the height of reinforcement composition.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN108504890A (en) * | 2018-05-17 | 2018-09-07 | 哈尔滨工业大学 | One kind having base high-entropy alloy composite material and preparation method |
| 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 |
| CN109694979A (en) * | 2017-10-20 | 2019-04-30 | 南京理工大学 | Vacuum induction melting prepares high-entropy alloy-base composite material and its method |
| CN110042295A (en) * | 2019-04-25 | 2019-07-23 | 北京理工大学 | A kind of preparation method of nanometer of high-entropy alloy block materials |
| CN111304479A (en) * | 2020-03-18 | 2020-06-19 | 南昌航空大学 | Preparation method of VCrNbMoW refractory high-entropy alloy |
| CN112342418A (en) * | 2020-09-09 | 2021-02-09 | 江苏大学 | Face-centered cubic boron-containing high-entropy alloy prepared by microwave sintering and preparation method thereof |
| CN112723862A (en) * | 2020-12-29 | 2021-04-30 | 太原理工大学 | Method for preparing high-entropy oxide ceramic material simply and low in 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 |
| CN117070934A (en) * | 2023-08-22 | 2023-11-17 | 安徽工业大学 | High-entropy alloy coating with wide hardness gradient and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109694979A (en) * | 2017-10-20 | 2019-04-30 | 南京理工大学 | Vacuum induction melting prepares high-entropy alloy-base composite material and its method |
| 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 |
| CN108504890A (en) * | 2018-05-17 | 2018-09-07 | 哈尔滨工业大学 | One kind having base high-entropy alloy composite material and preparation method |
| 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 |
| CN110042295A (en) * | 2019-04-25 | 2019-07-23 | 北京理工大学 | A kind of preparation method of nanometer of high-entropy alloy block materials |
| CN111304479A (en) * | 2020-03-18 | 2020-06-19 | 南昌航空大学 | Preparation method of VCrNbMoW refractory high-entropy alloy |
| CN112342418A (en) * | 2020-09-09 | 2021-02-09 | 江苏大学 | Face-centered cubic boron-containing high-entropy alloy prepared by microwave sintering and preparation method thereof |
| 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 |
| CN112723862A (en) * | 2020-12-29 | 2021-04-30 | 太原理工大学 | Method for preparing high-entropy oxide ceramic material simply and low in 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 |
| CN117070934A (en) * | 2023-08-22 | 2023-11-17 | 安徽工业大学 | High-entropy alloy coating with wide hardness gradient and preparation method thereof |
| 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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