CN107186208A - A kind of high-entropy alloy feeding and its preparation method and application - Google Patents
A kind of high-entropy alloy feeding and its preparation method and application Download PDFInfo
- Publication number
- CN107186208A CN107186208A CN201710372217.9A CN201710372217A CN107186208A CN 107186208 A CN107186208 A CN 107186208A CN 201710372217 A CN201710372217 A CN 201710372217A CN 107186208 A CN107186208 A CN 107186208A
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- feeding
- present
- entropy
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
-
- 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
- B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a kind of high-entropy alloy feeding and its preparation method and application, the high-entropy alloy feeding is composed of the following components by volumn concentration：High-entropy alloy powder 40 70%；High polymer binder 30 60%.The feeding has the excellent properties of high-entropy alloy, high-entropy alloy can be introduced into metal injection molding technology with this, adds the application surface of high-entropy alloy.High-entropy alloy feeding is applied in metal injection molding technology by the present invention, product stability in process of injection molding can be improved, obtained high-entropy alloy product has more than 97.5% sintered density, the high-entropy alloy parts for being conducive to the complicated, excellent performance of production, required precision high.With good economic benefit and application prospect.
Description
Technical field
The present invention relates to metal charge body preparation field, and in particular to a kind of high-entropy alloy feeding and preparation method thereof and should
With.
Background technology
Traditional theory thinks that easier formation intermetallic compound becomes the structure of alloy when the pivot of alloy is more
Obtain more complicated, and then make it that the performance of alloy is significantly affected.This traditional view has been broken in the appearance of high-entropy alloy.
There is high-entropy alloy microstructure to simplify, be not inclined to and intermetallic compound occur, with nano-scaled precipitate and amorphous structure
Etc. feature, and then obtain the premium properties such as high intensity, high rigidity, resistance to temper softening, wear-resisting, this causes high-entropy alloy once going out
Extensive concern is now just obtained, its application is more and more extensive.
A kind of essential element of the conventional alloys typically all containing atomic percent higher than 50%, and all masters in high-entropy alloy
Want that the atom percentage content of element is substantially suitable, they play a role jointly.So high-entropy alloy, also referred to as many high entropys of pivot are closed
Gold, i.e., this kind alloy is made up of a variety of essential elements, and its element species is general at five kinds or more than five kinds, and every kind of host element
Atom percentage content all should mainly have five host element systems on high-entropy alloy at present between 5%-35%：Al-Co-Cr-
Fe-Ni、Fe-Si-Al-Ni-Co、W-Nb-Ta-Mo-V；Six host element systems：V-Zr-Hf-Ti-Cr-Mn、Fe-Cr-Mo-Ti-
Mn-Cu、W-Nb-Ta-Mo-V-Ti、Al-Co-Cr-Fe-Ni-Ti；Seven host element systems：W-Nb-Cr-Ti-V-Co-Mn.
Alloy is distinguished with the entropy of mixing, can using 0.693R and 1.609R as boundary line (actually this is boundary line about)
It is divided into low entropy alloy, middle entropy alloy, high-entropy alloy.A kind of alloy based on element is low entropy alloy, and the alloy of 2-4 host elements is
Alloys more than middle entropy alloy, 5 kinds of host elements is high-entropy alloy.Thermodynamically, the increase of randomness or entropy, then can make system
Free energy reduction and stably.The Experience in Development of conventional alloys is thought, can be produced when the element species of component alloy are more a variety of
Intermetallic compound, is not only difficult to analyze and material easily becomes fragile, without application.And classical Gibbs phase rules think,
The number p=n+1 for the balance phase that the alloy system of n kind elements can be generated, the phase p formed in nonequilibrium freezing>n+l.And
In high-entropy alloy most noticeable phenomenon, this kind of alloy being made up of multielement does not occur tradition three after solidification
Similar multiphase, many Intermetallic compounds or a variety of crystal structures in member, quaternary alloy, but be more likely to form simple crystal knot
Structure, such as simple body-centered cubic, even simple face-centered cubic, non-crystal structure, the quantity of Intermetallic compound is also far less than pre-
Phase, the situation of this and classical Gibbs phase rules description is runed counter to completely.These phenomenons are summed up as the effect of high entropic effect, i.e.,：By
The entropy of mixing for forming high-entropy alloy is caused to be greater than to form the entropy of Intermetallic compound in the element for forming alloy is more, so as to suppress
The formation of Intermetallic compound in system, promotes to form simple crystal structure between element.The conjunction of the monoclinic crystal structure so formed
Gold tends to nanosizing, with many excellent special performances.From thermodynamic analysis, a master is not present in solid-state high-entropy alloy
Long-range diffusion in the matrix element wanted, its phase separation is very slow, and the change type of element spreads very in alloy
Difficulty, the interaction of diffusion particle, greatly reduces the nucleation rate and the speed of growth of crystal during along with distribution, so that closing
The crystal grain of gold is very tiny.
The influence of high entropic effect is not present in Conventional wisdom, in high-entropy alloy, causes alloy when element number is more
When the entropy of mixing of system is higher than the Entropy Changes for forming intermetallic compound, high entropic effect will suppress the appearance of intermetallic compound,
And promote the mixing between element, ultimately form simple solid solution structure.Current studies have shown that is in the situation without host element
Under, various elements can mutual solid solution into single structure, whether as cast condition high-entropy alloy or the alloy firm of spraying plating state, are all inclined to
In the solid solution for forming simple body-centered cubic or face-centred cubic structure, or subsidiary amorphous phase or ordered solid solution structure.High entropy
Because the high entropy of mixing causes the low free degree in alloy, thus the solid solution of simple structure is easily formed, with simple micro- knot
Its superiority of the solid solution alloy of structure is obvious；And understand seldom to answer in high-entropy alloy from conventional research
Dephasign.
For other alloys, high-entropy alloy has the advantage of structure and performance, it is therefore necessary to expand its application.
Metal injection molding technology includes preparing the steps such as feeding, injection moulding, degreasing, sintering, is that one kind efficiently prepares metallic article
Technique.But not yet high-entropy alloy is incorporated into metal injection molding technology by someone in the prior art.
The content of the invention
In order to solve the above technical problems, the invention provides a kind of high-entropy alloy feeding and its preparation method and application, obtaining
A kind of feeding with high-entropy alloy excellent properties has been arrived, and then high-entropy alloy is introduced into metal injection molding technology, has been conducive to
The high high-entropy alloy parts of the complicated, excellent performance of production, required precision, add the application surface of high-entropy alloy.
To reach this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of high-entropy alloy feeding, the high-entropy alloy feeding by volumn concentration by
Following components is constituted：High-entropy alloy powder 40-70%；High polymer binder 30-60%.
The present invention kneads high-entropy alloy powder and organic high polymer binder, has obtained the high entropy with excellent properties
Alloy feeding, metal injection molding technology is introduced as medium using high-entropy alloy as raw material, with reference to the superiority of raw material
The characteristics of energy and technique, the high-entropy alloy product of excellent performance can be obtained.
According to the present invention, based on volumn concentration, the content of the high-entropy alloy powder can be 40%, 42%,
45%th, the tool between 48%, 50%, 52%, 55%, 57%, 60%, 63%, 65%, 68% or 70%, and above-mentioned numerical value
Body point value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, based on volumn concentration, the content of the high polymer binder can be 30%, 32%,
35%th, the tool between 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or 60%, and above-mentioned numerical value
Body point value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, based on volumn concentration, high-entropy alloy powder and the high polymer binder sum is
100%.
According to the present invention, the high-entropy alloy is that alloy-type high-entropy alloy, mixed powder type high-entropy alloy or prealloy type are high
Any one in entropy alloy.
High polymer binder of the present invention is prepares feeding when institute with metal-powder mixing in metal injection molding technology
Conventional binding agent.
According to the present invention, the high polymer binder includes following components by weight/mass percentage composition：Macromolecule bonds host
49-95%；Macromolecule bonds assistant agent 4.7-47%；Auxiliary agent 0.3-4%.
Based on weight/mass percentage composition, the content that the macromolecule bonds host can be 49%, 50%, 55%, 60%,
65%th, the specific point value between 70%, 75%, 80%, 85%, 90% or 95%, and above-mentioned numerical value, as space is limited and for
Concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
Based on weight/mass percentage composition, the content that the macromolecule bonds assistant agent can be 4.7%, 5%, 10%, 15%,
20%th, the specific point value between 25%, 30%, 35%, 40%, 45% or 47%, and above-mentioned numerical value, as space is limited and for
Concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
Based on weight/mass percentage composition, the content of the auxiliary agent can be 0.3%, 5%, 1%, 1.5%, 2%, 2.5%,
3%th, the specific point value between 3.5% or 4%, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer
The specific point value that scope described in exclusive list includes.
According to the present invention, based on weight/mass percentage composition, the macromolecule bond host, macromolecule bond assistant agent and auxiliary agent it
With for 100%.
According to the present invention, the macromolecule bond host be paraffin, Brazil wax, polyformaldehyde, ethylene ethyl acrylate,
Ethylene-vinyl acetate copolymer, polyethylene glycol, polyethylene terephthalate, ethyl cellulose, cellulose acetate, low nitrogen nitre
Cellulose, ethylene butene cellulose, polyethylene terephthalate, polyethylene glycol diacrylate fat, DPG first mystery
In acetate or 2-Pyrrolidone any one or at least two combination, for example can be paraffin, Brazil wax, poly- first
Aldehyde, ethylene ethyl acrylate, ethylene-vinyl acetate copolymer, polyethylene glycol, polyethylene terephthalate, ethyl cellulose
Element, cellulose acetate, collodion cotton, ethylene butene cellulose, polyethylene terephthalate, polyethylene glycol dipropyl
Any one in olefin(e) acid fat, DPG first mystery acetate or 2-Pyrrolidone；Typical but non-limiting is combined as：Paraffin
And Brazil wax；Polyethylene glycol and polyethylene glycol diacrylate fat；Ethyl cellulose and cellulose acetate；Low nitrogen nitrocellulose
Element and ethylene butene cellulose；Ethylene ethyl acrylate and ethylene-vinyl acetate copolymer etc., as space is limited and for simplicity
Consider, the present invention no longer exclusive list.
According to the present invention, the macromolecule bond assistant agent be polyethylene, it is polypropylene, polyvinyl butyral resin, poly- to benzene two
It is any in formic acid butanediol ester, polyethylene terephthalate, ethylene-vinyl acetate copolymer, polystyrene or nylon
It is a kind of or at least two combination, for example can be polyethylene, polypropylene, polyvinyl butyral resin, poly terephthalic acid fourth two
Any one in alcohol ester, polyethylene terephthalate, ethylene-vinyl acetate copolymer, polystyrene or nylon；Typical case
But non-limiting is combined as：Polyethylene and polypropylene；Polyvinyl butyral resin and polybutylene terephthalate (PBT)；Gather to benzene
Naphthalate and ethylene-vinyl acetate copolymer；Polystyrene and nylon；Polyethylene, polypropylene and polyvinyl alcohol contracting
Butyraldehyde；Polybutylene terephthalate (PBT), polyethylene terephthalate and ethylene-vinyl acetate copolymer etc., are limited to a piece
Width and the consideration for simplicity, the present invention no longer exclusive list.
According to the present invention, the auxiliary agent is stearic acid, polyisobutene, PIBA, Tissuemat E, polypropylene wax or anti-
In oxygen agent B215 any one or at least two combination, for example can be stearic acid, polyisobutene, PIBA, poly-
Any one in ethylene waxes, polypropylene wax or antioxidant B215；Typical but non-limiting is combined as：Stearic acid and poly- isobutyl
Alkene；PIBA and Tissuemat E or polypropylene wax；Stearic acid and antioxidant B215；Stearic acid and polypropylene wax；Stearic acid,
Polyisobutene and Tissuemat E；Stearic acid, polypropylene wax and antioxidant B215 etc., as space is limited and for concise consideration, sheet
Invention no longer exclusive list.
Second aspect, the present invention provides a kind of preparation method of high-entropy alloy feeding as described in relation to the first aspect, the side
Method is：High-entropy alloy powder and high polymer binder are kneaded by formula ratio, high-entropy alloy feeding is obtained.
According to the present invention, the temperature of the mixing is 165-175 DEG C, for example can be 165 DEG C, 166 DEG C, 167 DEG C, 168
DEG C, 169 DEG C, 170 DEG C, 171 DEG C, 172 DEG C, 173 DEG C, 174 DEG C or the specific point value between 175 DEG C, and above-mentioned numerical value, be limited to
Length and the consideration for simplicity, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, the time of the mixing is 0.5-2h, for example can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h,
It is specific between 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
The third aspect, the present invention provides a kind of application of high-entropy alloy feeding as described in relation to the first aspect, and the high entropy is closed
Golden feeding is applied in metal injection molding technology.
Preferably, the application comprises the following steps：
(1) the high-entropy alloy feeding is granulated to form particle；
(2) the particle injection moulding for obtaining step (1), obtains green compact；
(3) green compact for obtaining step (2) carry out degreasing；
(4) green compact obtained after step (3) degreasing are sintered, high-entropy alloy product is obtained after the completion of sintering.
According to the present invention, the particle diameter of step (1) described particle is 3mm-5mm, for example can be 3mm, 3.2mm, 3.5mm,
Specific point value between 3.8mm, 4mm, 4.2mm, 4.5mm, 4.8mm or 5mm, and above-mentioned numerical value, as space is limited and for letter
Bright consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, the temperature of step (2) described injection is 160-210 DEG C, for example can be 160 DEG C, 165 DEG C, 170
DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, it is specific between 205 DEG C or 210 DEG C, and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, the pressure of step (2) described injection is 85-120MPa, for example can be 85MPa, 90MPa,
Specific point value between 95MPa, 100MPa, 105MPa, 110MPa, 115MPa or 120MPa, and above-mentioned numerical value, as space is limited
And for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, the method for step (3) described degreasing can or water de- for solution-off, acid it is de- in any one.
According to the present invention, when the form in step (3) using solution-off carries out degreasing, it is stone that the macromolecule, which bonds host,
It is any in wax, Brazil wax, polyformaldehyde, ethylene ethyl acrylate, ethylene-vinyl acetate copolymer, polyethylene glycol or resin
It is a kind of or at least two combination, for example can be paraffin, Brazil wax, polyformaldehyde, ethylene ethyl acrylate, ethylene vinyl acetate
Any one in ethylene copolymer, polyethylene glycol or resin；Typical but non-limiting is combined as：Paraffin and babassu
Wax；Polyformaldehyde and ethylene ethyl acrylate；Ethylene-vinyl acetate copolymer and polyethylene glycol；Paraffin, ethylene ethyl acrylate and
Resin；Polyformaldehyde, ethylene ethyl acrylate and ethylene-vinyl acetate copolymer etc., as space is limited and for concise consideration, sheet
Invention no longer exclusive list.
According to the present invention, when carrying out degreasing using the de- form of acid in step (3), it is poly- that the macromolecule, which bonds host,
Formaldehyde, polyethylene terephthalate, ethyl cellulose, cellulose acetate, collodion cotton or ethylene butene fiber
In element any one or at least two combination, for example can be polyformaldehyde, polyethylene terephthalate, ethyl cellulose
Any one in element, cellulose acetate, collodion cotton or ethylene butene cellulose；Typical but non-limiting combination
For：Polyformaldehyde and polyethylene terephthalate；Ethyl cellulose and cellulose acetate；Collodion cotton and ethene fourth
Alkene cellulose；Polyformaldehyde, polyethylene terephthalate and ethyl cellulose；Cellulose acetate, collodion cotton and
Ethylene butene cellulose etc., as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, when the form taken off in step (3) using water carries out degreasing, it is poly- that the macromolecule, which bonds host,
Ethylene glycol, polyethylene terephthalate, polyethylene glycol diacrylate fat, DPG first mystery acetate, 2-Pyrrolidone
In any one or at least two combination, typical but non-limiting is combined as：Polyethylene glycol and poly terephthalic acid second
Diol ester；Polyethylene glycol diacrylate fat and DPG first mystery acetate；Polyethylene glycol and 2-Pyrrolidone；Polyethylene glycol,
Polyethylene terephthalate and polyethylene glycol diacrylate fat；Polyethylene glycol, DPG first mystery acetate and 2- pyrroles
Alkanone etc., as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the temperature of step (4) described sintering is 950-1350 DEG C, for example can be 950 DEG C, 1000 DEG C,
Specific point value between 1050 DEG C, 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C or 1350 DEG C, and above-mentioned numerical value,
As space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, the time of step (4) described sintering is 2-4h, for example can be 2h, 2.3h, 2.5h, 2.8h,
Specific point value between 3h, 3.2h, 3.5h, 3.8h or 4h, and above-mentioned numerical value, as space is limited and for concise consideration, sheet
The specific point value that scope described in invention no longer exclusive list includes.
According to the present invention, described be sintered in reducing atmosphere or inert atmosphere of step (4) is carried out, the reducing atmosphere
For hydrogen, the inert atmosphere is argon gas.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention has obtained a kind of with high entropy by being kneaded high-entropy alloy as raw material and high polymer binder
The feeding of alloy excellent properties, and then high-entropy alloy can be introduced metal injection molding technology, add answering for high-entropy alloy
Use face.
(2) present invention can improve the stability of product in process of injection molding, and obtained high-entropy alloy product has
More than 97.5% sintered density, the high-entropy alloy parts for being conducive to the complicated, excellent performance of production, required precision high.
(3) high-entropy alloy feeding is applied in metal injection molding technology by the present invention, is conducive in high-entropy alloy part
Degreasing after injection moulding, degreasing time is short, efficiency high and degreasing completely, reduce production cost.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
The present embodiment prepares high-entropy alloy feeding in accordance with the following methods：
(1) by D10, D50 and D90 particle diameter it is respectively 5 μm, 11 μm, 25 μm of high-entropy alloy mixed-powder and macromolecule
Binding agent is well mixed, and wherein the useful load of mixed-powder is 63vol%, and the useful load of high polymer binder is 37vol%；Institute
High-entropy alloy is stated for five host element systems：Al-Co-Cr-Fe-Ni；The high polymer binder is by 84wt% polyformaldehyde, 6wt%
High density polyethylene (HDPE), 6wt% ethylene-vinyl acetate copolymers, 3.5wt% stearic acid and 0.5wt% antioxidant B215 compositions；
(2) the high-entropy alloy mixed-powder and the mixture of high polymer binder obtained step (1) is placed in kneading machine,
1.5h is kneaded at 165 DEG C, the rotating speed of mixing kneading machine at initial stage is 15r/min, after control mixing after high polymer binder fusing
The rotating speed of machine is 25r/min, and high-entropy alloy feeding is obtained after the completion of mixing；
The high-entropy alloy feeding that the present embodiment is obtained is applied to metal injection molding technology, comprises the following steps：
(1) the high-entropy alloy feeding is granulated through comminutor, obtained with the particle that particle diameter is 3mm-5mm；
(2) particle for obtaining step (1) is 210 DEG C in temperature, and pressure obtains to be injected under conditions of 120MPa
The green compact of shaping；
(3) green compact for obtaining step (2) are placed in debinding furnace, and it is 115 DEG C to control temperature, are taken off by medium acid filling of nitric acid
Fat 5h；
(4) green compact obtained after step (3) degreasing are placed in sintering furnace, under the atmosphere of argon gas, are warming up to 950 DEG C of sintering
4h, obtains high-entropy alloy product.
By test, the relative sintered density of obtained high-entropy alloy product is 98.1%.
Embodiment 2
The present embodiment prepares high-entropy alloy feeding in accordance with the following methods：
(1) by D10, D50 and D90 particle diameter it is respectively 5 μm, 11 μm, 25 μm of high-entropy alloy mixed-powder and macromolecule
Binding agent is well mixed, and wherein the useful load of mixed-powder is 63vol%, and the useful load of high polymer binder is 37vol%；Institute
High-entropy alloy is stated for five host element systems：Al-Co-Cr-Fe-Ni；The high polymer binder is by 84wt% paraffin and cohune
Palmitic acid wax (the two ratio is any), 12wt% polystyrene, 2wt% stearic acid and 2wt% Tissuemat Es composition；
(2) the high-entropy alloy mixed-powder and the mixture of high polymer binder obtained step (1) is placed in kneading machine,
1h is kneaded at 175 DEG C, the rotating speed of mixing kneading machine at initial stage is 20r/min, and kneading machine is controlled after high polymer binder melts
Rotating speed be 30r/min, high-entropy alloy feeding is obtained after the completion of mixing.
The high-entropy alloy feeding that the present embodiment is obtained is applied to metal injection molding technology, comprises the following steps：
(1) the high-entropy alloy feeding is granulated through comminutor, obtained with the particle that particle diameter is 3mm-5mm；
(2) particle for obtaining step (1) is 170 DEG C in temperature, and pressure obtains to be injected under conditions of 90MPa
The green compact of shaping；
(3) green compact for obtaining step (2) are placed in debinding furnace, and it is 80 DEG C to control temperature, are soaked by medium of normal heptane
10h；
(4) green compact obtained after step (3) degreasing are placed in sintering furnace, under the atmosphere of argon gas, are warming up to 1350 DEG C of burnings
3h is tied, high-entropy alloy product is obtained.
By test, the relative sintered density of obtained high-entropy alloy product is 97.8%.
Embodiment 3
The present embodiment prepares high-entropy alloy feeding in accordance with the following methods：
(1) by D10, D50 and D90 particle diameter it is respectively 5 μm, 11 μm, 25 μm of high-entropy alloy mixed-powder and macromolecule
Binding agent is well mixed, and wherein the useful load of mixed-powder is 70vol%, and the useful load of high polymer binder is 30vol%；Institute
High-entropy alloy is stated for six host element systems：Fe-Cr-Mo-Ti-Mn-Cu；The high polymer binder by 60wt% polyethylene glycol,
6wt% polyethylene glycol diacrylates fat, 25.5wt% polyvinyl butyral resins, 5.5wt% polyethylene terephthalates,
2.5wt% stearic acid and 0.5wt% antioxidant B215 compositions；
(2) the high-entropy alloy mixed-powder and the mixture of high polymer binder obtained step (1) is placed in kneading machine,
1.2h is kneaded at 170 DEG C, the rotating speed of mixing kneading machine at initial stage is 10r/min, after control mixing after high polymer binder fusing
The rotating speed of machine is 20r/min, and high-entropy alloy feeding is obtained after the completion of mixing.
The high-entropy alloy feeding that the present embodiment is obtained is applied to metal injection molding technology, comprises the following steps：
(1) the high-entropy alloy feeding is granulated through comminutor, obtained with the particle that particle diameter is 3mm-5mm；
(2) particle for obtaining step (1) is 160 DEG C in temperature, and pressure obtains to be injected under conditions of 85MPa
The green compact of shaping；
(3) green compact for obtaining step (2) are placed in debinding furnace, and it is 65 DEG C to control temperature, are soaked by medium of deionized water
Steep 14h；
(4) green compact obtained after step (3) degreasing are placed in sintering furnace, under the atmosphere of hydrogen, are warming up to 1200 DEG C of burnings
3.5h is tied, high-entropy alloy product is obtained.
By test, the relative sintered density of obtained high-entropy alloy product is 97.5%.
Embodiment 4
The present embodiment prepares high-entropy alloy feeding in accordance with the following methods：
(1) by D10, D50 and D90 particle diameter it is respectively 5 μm, 11 μm, 25 μm of high-entropy alloy mixed-powder and macromolecule
Binding agent is well mixed, and wherein the useful load of mixed-powder is 55vol%, and the useful load of high polymer binder is 45vol%；Institute
High-entropy alloy is stated for seven host element systems：W-Nb-Cr-Ti-V-Co-Mn；The high polymer binder is by 70wt% ethyl celluloses
Element, 5%wt cellulose acetates, 23% polystyrene, 2% Tissuemat E composition；
(2) the high-entropy alloy mixed-powder and the mixture of high polymer binder obtained step (1) is placed in kneading machine,
2h is kneaded at 168 DEG C, the rotating speed of mixing kneading machine at initial stage is 12r/min, and kneading machine is controlled after high polymer binder melts
Rotating speed be 25r/min, high-entropy alloy feeding is obtained after the completion of mixing.
The high-entropy alloy feeding that the present embodiment is obtained is applied to metal injection molding technology, comprises the following steps：
(1) the high-entropy alloy feeding is granulated through comminutor, obtained with the particle that particle diameter is 3mm-5mm；
(2) particle for obtaining step (1) is 190 DEG C in temperature, and pressure obtains to be injected under conditions of 100MPa
The green compact of shaping；
(3) green compact for obtaining step (2) are placed in debinding furnace, and it is 140 DEG C to control temperature, are taken off by medium acid filling of nitric acid
Fat 4h；
(4) green compact obtained after step (3) degreasing are placed in sintering furnace, under the atmosphere of argon gas, are warming up to 1100 DEG C of burnings
3.2h is tied, high-entropy alloy product is obtained.
By test, the relative sintered density of obtained high-entropy alloy product is 97.9%.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of high-entropy alloy feeding, it is characterised in that the high-entropy alloy feeding is by volumn concentration by following components group
Into：High-entropy alloy powder 40-70%；High polymer binder 30-60%.
2. high-entropy alloy feeding as claimed in claim 1, it is characterised in that the high-entropy alloy be alloy-type high-entropy alloy,
Any one in mixed powder type high-entropy alloy or prealloy type high-entropy alloy.
3. high-entropy alloy feeding as claimed in claim 1 or 2, it is characterised in that the high polymer binder presses quality percentage
Content includes following components：Macromolecule bonds host 49-95%；Macromolecule bonds assistant agent 4.7-47%；Auxiliary agent 0.3-4%.
4. high-entropy alloy feeding as claimed in claim 3, it is characterised in that it is paraffin, Brazil that the macromolecule, which bonds host,
Palm wax, polyformaldehyde, ethylene ethyl acrylate, ethylene-vinyl acetate copolymer, polyethylene glycol, polyethylene terephthalate
Ester, ethyl cellulose, cellulose acetate, collodion cotton, ethylene butene cellulose, polyethylene terephthalate,
In polyethylene glycol diacrylate fat, DPG first mystery acetate or 2-Pyrrolidone any one or at least two group
Close；
Preferably, it is polyethylene, polypropylene, polyvinyl butyral resin, poly terephthalic acid fourth two that the macromolecule, which bonds assistant agent,
In alcohol ester, polyethylene terephthalate, ethylene-vinyl acetate copolymer, polystyrene or nylon any one or extremely
Few two kinds combination；
Preferably, the auxiliary agent is stearic acid, polyisobutene, PIBA, Tissuemat E or polypropylene wax, antioxidant B215
In any one or at least two combination.
5. the preparation method of the high-entropy alloy feeding as described in claim any one of 1-4, it is characterised in that methods described is：
High-entropy alloy powder and high polymer binder are kneaded by formula ratio, high-entropy alloy feeding is obtained.
6. high-entropy alloy feeding as claimed in claim 5, it is characterised in that the temperature of the mixing is 165-175 DEG C；
Preferably, the time of the mixing is 0.8-2h.
7. the application of the high-entropy alloy feeding as described in claim any one of 1-4, it is characterised in that the high-entropy alloy feeding
Applied in metal injection molding technology.
8. application as claimed in claim 7, it is characterised in that the application comprises the following steps：
(1) the high-entropy alloy feeding is granulated to form particle；
(2) the particle injection moulding for obtaining step (1), obtains green compact；
(3) green compact for obtaining step (2) carry out degreasing；
(4) green compact obtained after step (3) degreasing are sintered, high-entropy alloy product is obtained after the completion of sintering.
9. application as claimed in claim 8, it is characterised in that preferably, the particle diameter of step (1) described particle is 3mm-5mm；
Preferably, the temperature of step (2) described injection is 160-210 DEG C；
Preferably, the pressure of step (2) described injection is 85-120MPa；
Preferably, the method for step (3) described degreasing be that solution-off, acid is de- or water it is de- in any one.
10. application as claimed in claim 8, it is characterised in that the temperature of step (4) described sintering is 950-1350 DEG C；
Preferably, the time of step (4) described sintering is 2-4h；
Preferably, described be sintered in reducing atmosphere or inert atmosphere of step (4) is carried out；
Preferably, the reducing atmosphere is hydrogen；
Preferably, the inert atmosphere is argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710372217.9A CN107186208A (en) | 2017-05-23 | 2017-05-23 | A kind of high-entropy alloy feeding and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710372217.9A CN107186208A (en) | 2017-05-23 | 2017-05-23 | A kind of high-entropy alloy feeding and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107186208A true CN107186208A (en) | 2017-09-22 |
Family
ID=59875718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710372217.9A Pending CN107186208A (en) | 2017-05-23 | 2017-05-23 | A kind of high-entropy alloy feeding and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107186208A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107881501A (en) * | 2017-11-22 | 2018-04-06 | 江门职业技术学院 | A kind of compositions of additives for being used to prepare the alloy powder of high-entropy alloy coating |
| CN108097970A (en) * | 2017-12-28 | 2018-06-01 | 东莞华晶粉末冶金有限公司 | Metal powder injection molding feeding and preparation method thereof |
| CN108339973A (en) * | 2018-02-02 | 2018-07-31 | 东莞华晶粉末冶金有限公司 | Hard alloy is injection moulded feeding and preparation method thereof |
| CN108856713A (en) * | 2018-05-29 | 2018-11-23 | 东莞华晶粉末冶金有限公司 | SUS201 stainless steel is injection moulded feeding and preparation method thereof |
| CN109047750A (en) * | 2018-07-18 | 2018-12-21 | 东莞华晶粉末冶金有限公司 | The preparation method of 310 powder of stainless steel feeding of environment-friendly type and 310 powder of stainless steel components |
| CN109047749A (en) * | 2018-07-18 | 2018-12-21 | 东莞华晶粉末冶金有限公司 | The preparation method of environment-friendly type cemented carbide powder feeding and hard alloy components |
| CN109226739A (en) * | 2018-09-05 | 2019-01-18 | 东莞华晶粉末冶金有限公司 | The preparation method of 1Cr17Ni7 stainless steel MIM feeding and its product |
| CN110216278A (en) * | 2019-06-25 | 2019-09-10 | 明阳科技（苏州）股份有限公司 | A kind of high fluidity, lower shrinkage are than feeding and preparation method thereof |
| CN110523916A (en) * | 2019-09-30 | 2019-12-03 | 安徽信息工程学院 | A kind of environmentally friendly release agent and its preparation and application for sand casting mould |
| CN115044793A (en) * | 2022-06-16 | 2022-09-13 | 江苏精研科技股份有限公司 | Manufacturing method for preparing two-phase high-entropy alloy by adopting powder injection molding |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6390813A (en) * | 1986-10-03 | 1988-04-21 | Mitsubishi Metal Corp | Manufacture of rare earth alloy permanent magnet |
| CN1644278A (en) * | 2005-01-12 | 2005-07-27 | 北京科技大学 | Ti6Al4V alloy injection forming method |
| CN101049634A (en) * | 2007-04-29 | 2007-10-10 | 北京科技大学 | Method for preparing intubatton type stainless steel reverser of ball bearing screw rod pair |
| CN101279367A (en) * | 2008-05-28 | 2008-10-08 | 北京科技大学 | Injection forming method for preparing high Niobium containing Ti-Al alloy components |
| CN101456075A (en) * | 2007-12-14 | 2009-06-17 | 比亚迪股份有限公司 | Preparation method of nano-crystal soft magnetic alloy elements |
| US20100132409A1 (en) * | 2008-12-01 | 2010-06-03 | Saint-Gobain Coating Solutions | Coating for a device for forming glass products |
| CN102220026A (en) * | 2011-04-11 | 2011-10-19 | 黄元盛 | High-entropy alloy powder conductive polymer composite material and manufacturing method thereof |
| CN105108154A (en) * | 2015-09-21 | 2015-12-02 | 深圳艾利门特科技有限公司 | Method for preparing special-shaped complex part through powder injection molding technology |
-
2017
- 2017-05-23 CN CN201710372217.9A patent/CN107186208A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6390813A (en) * | 1986-10-03 | 1988-04-21 | Mitsubishi Metal Corp | Manufacture of rare earth alloy permanent magnet |
| CN1644278A (en) * | 2005-01-12 | 2005-07-27 | 北京科技大学 | Ti6Al4V alloy injection forming method |
| CN101049634A (en) * | 2007-04-29 | 2007-10-10 | 北京科技大学 | Method for preparing intubatton type stainless steel reverser of ball bearing screw rod pair |
| CN101456075A (en) * | 2007-12-14 | 2009-06-17 | 比亚迪股份有限公司 | Preparation method of nano-crystal soft magnetic alloy elements |
| CN101279367A (en) * | 2008-05-28 | 2008-10-08 | 北京科技大学 | Injection forming method for preparing high Niobium containing Ti-Al alloy components |
| US20100132409A1 (en) * | 2008-12-01 | 2010-06-03 | Saint-Gobain Coating Solutions | Coating for a device for forming glass products |
| CN102220026A (en) * | 2011-04-11 | 2011-10-19 | 黄元盛 | High-entropy alloy powder conductive polymer composite material and manufacturing method thereof |
| CN105108154A (en) * | 2015-09-21 | 2015-12-02 | 深圳艾利门特科技有限公司 | Method for preparing special-shaped complex part through powder injection molding technology |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107881501A (en) * | 2017-11-22 | 2018-04-06 | 江门职业技术学院 | A kind of compositions of additives for being used to prepare the alloy powder of high-entropy alloy coating |
| CN108097970A (en) * | 2017-12-28 | 2018-06-01 | 东莞华晶粉末冶金有限公司 | Metal powder injection molding feeding and preparation method thereof |
| CN108339973A (en) * | 2018-02-02 | 2018-07-31 | 东莞华晶粉末冶金有限公司 | Hard alloy is injection moulded feeding and preparation method thereof |
| CN108856713A (en) * | 2018-05-29 | 2018-11-23 | 东莞华晶粉末冶金有限公司 | SUS201 stainless steel is injection moulded feeding and preparation method thereof |
| CN109047750A (en) * | 2018-07-18 | 2018-12-21 | 东莞华晶粉末冶金有限公司 | The preparation method of 310 powder of stainless steel feeding of environment-friendly type and 310 powder of stainless steel components |
| CN109047749A (en) * | 2018-07-18 | 2018-12-21 | 东莞华晶粉末冶金有限公司 | The preparation method of environment-friendly type cemented carbide powder feeding and hard alloy components |
| CN109226739A (en) * | 2018-09-05 | 2019-01-18 | 东莞华晶粉末冶金有限公司 | The preparation method of 1Cr17Ni7 stainless steel MIM feeding and its product |
| CN110216278A (en) * | 2019-06-25 | 2019-09-10 | 明阳科技（苏州）股份有限公司 | A kind of high fluidity, lower shrinkage are than feeding and preparation method thereof |
| CN110523916A (en) * | 2019-09-30 | 2019-12-03 | 安徽信息工程学院 | A kind of environmentally friendly release agent and its preparation and application for sand casting mould |
| CN115044793A (en) * | 2022-06-16 | 2022-09-13 | 江苏精研科技股份有限公司 | Manufacturing method for preparing two-phase high-entropy alloy by adopting powder injection molding |
| CN115044793B (en) * | 2022-06-16 | 2023-09-08 | 江苏精研科技股份有限公司 | Manufacturing method for preparing two-phase high-entropy alloy by powder injection molding |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107186208A (en) | A kind of high-entropy alloy feeding and its preparation method and application | |
| US8652399B2 (en) | Sputtering target for producing metallic glass membrane and manufacturing method thereof | |
| CN100581690C (en) | Injection forming method for preparing high Niobium containing Ti-Al alloy components | |
| CN111570802B (en) | 3D printing manufacturing process of ultrathin metal-based diamond cutting blade | |
| CN110935878A (en) | Injection molding method of titanium alloy part | |
| CN110527857B (en) | Sintered titanium alloy and preparation method thereof | |
| CN111558904A (en) | 3D printing manufacturing process of metal ceramic bond CBN grinding wheel | |
| CN114086078A (en) | Fe-Mn-Al-C light steel, preparation method thereof, terminal, steel structural member and electronic equipment | |
| JP3861556B2 (en) | Method for producing sintered body and sintered body | |
| CN111451506A (en) | 3D printing manufacturing process of metal ceramic bonding agent CBN ultrathin cutting blade | |
| CN110436945B (en) | Binder for injection molding compositions | |
| CN103667843B (en) | A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material | |
| CN113399667A (en) | Titanium alloy metal powder injection molding feed and preparation method thereof | |
| JP2001158925A (en) | Method for producing metallic sintered body and metallic sintered body | |
| CN107971485B (en) | Sintering process of tungsten-titanium alloy | |
| JPH03193801A (en) | Sintering additive powder for intermetallic compound and sintering method thereof | |
| CN105728733A (en) | Method for preparing nanometer Co-CeO2 composite powder through mechanical alloying | |
| CN115255351B (en) | Diamond-metal matrix three-dimensional forming composite material, wire, preparation thereof and application thereof in FDM printing | |
| KR101525095B1 (en) | Injection molding method using powder | |
| CN117531998B (en) | Feeding material for preparing kovar alloy by metal injection molding, kovar alloy and preparation method thereof | |
| JPH11181501A (en) | Production of metal powder and sintered body | |
| JPS5926653B2 (en) | How to form cemented carbide | |
| JPH0513762B2 (en) | ||
| WO2006048075A2 (en) | Method for the production of objects from a metallic composite material | |
| JPH07300648A (en) | High strength sintered w-base alloy and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170922 |
|
| RJ01 | Rejection of invention patent application after publication |