CN109266938B - A kind of high temperature cemented carbide material and preparation method thereof - Google Patents
A kind of high temperature cemented carbide material and preparation method thereof Download PDFInfo
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- CN109266938B CN109266938B CN201811344866.9A CN201811344866A CN109266938B CN 109266938 B CN109266938 B CN 109266938B CN 201811344866 A CN201811344866 A CN 201811344866A CN 109266938 B CN109266938 B CN 109266938B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
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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
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
Abstract
The invention discloses a kind of high temperature cemented carbide materials, belong to technical field of alloy material.The cemented carbide material is made of hardening phase, metal adhesive and additive;Wherein, the hardening is mutually made of the raw material below according to parts by weight: 40-60 parts of WC, 5-10 parts of HfC, 8-15 parts of BN;The metal adhesive is made of the raw material below according to parts by weight: Mo, Ni mixture 5-20;The additive is made of the raw material below according to parts by weight: Nb2O54-10 parts, 1-5 parts of La, 2-8 parts of graphite oxide;The WC is superfine tungsten carbide.The invention also discloses the preparation methods of the cemented carbide material.The present invention is by while obtained cemented carbide material has the characteristics that high rigidity, high intensity and high tenacity, also possessing excellent high temperature resistance under the compounding and synergy between each component.
Description
Technical field
The present invention relates to technical field of alloy material, specifically a kind of high temperature cemented carbide material and preparation method thereof.
Background technique
Hard alloy is using the carbide of high rigidity refractory metal as primary raw material, made of powder metallurgical technique
A kind of alloy material.Since hard alloy has the excellent properties such as high-intensitive, high rigidity and high-wearing feature, thus can be widely used as
The cutter material of cutting cast iron etc..
Hard alloy currently on the market is WC-Mo alloy mostly, and this hard alloy can possess higher at 1000 DEG C
Hardness and strength, not excessive operating temperature reaches 1000 DEG C or more, and thermohardening will start to reduce, and carbon at high temperature
Compound is easy part and is oxidized, and also results in its intensity and other degradations.Although in the prior art, passing through past WC-Mo
Be added in alloy the carbide such as some dystectic TiC or TaC can the heat-resisting quantity to alloy slightly improve, but it is this
Method is only merely the fusing point for improving alloy, the feelings for still not can avoid hard alloy at high temperature and will appear deformation, being oxidized
Condition, therefore it is difficult to be promoted in the steel-making industry for needing hot environment to operate.
Summary of the invention
The purpose of the present invention is to provide a kind of high temperature cemented carbide materials and preparation method thereof, to solve above-mentioned background
The problem of being proposed in technology.
To achieve the above object, the invention provides the following technical scheme:
A kind of high temperature cemented carbide material, is made of hardening phase, metal adhesive and additive;Wherein, described hard
Change and be mutually made of the raw material below according to parts by weight: 40-60 parts of WC, 5-10 parts of HfC, 8-15 parts of BN;The metal bonding
Agent is made of the raw material below according to parts by weight: Mo, Ni mixture 5-20;The additive is by below according to the original of parts by weight
Material composition: Nb2O54-10 parts, 1-5 parts of La, 2-8 parts of graphite oxide;The WC is superfine tungsten carbide.
As a further solution of the present invention, the BN is hexagonal boron nitride.
As the present invention, further scheme, the fusing point of the HfC are 3880 DEG C -3890 DEG C;The Nb2O5Fusing point
It is 1480 DEG C -1490 DEG C.
As further scheme of the invention, Mo and Ni mass ratio is 1:2-1:6 in Mo, Ni mixture,
Middle Ni is extra-fine nickel powder.
As the present invention, further scheme, the graphite oxide are by crystalline flake graphite by strong oxidizer oxidation
What reason obtained.
As the present invention, further scheme, the hardening are mutually made of the raw material below according to parts by weight: WC 55
Part, 8 parts of HfC, 10 parts of BN;The metal adhesive is made of the raw material below according to parts by weight: Mo, Ni mixture 14
Part;The additive is made of the raw material below according to parts by weight: Nb2O58 parts, 3 parts of La, 6 parts of graphite oxide.
A kind of preparation method of high temperature cemented carbide material, includes the following steps:
(1) ingredient is carried out by the mass ratio of above-mentioned each component, then the raw material prepared is put into V-type blender and is filled
Divide mixing, wherein V-type blender revolving speed is 15-40 revs/min;
(2) mixed raw material and organic solvent one are reinstated into ball mill and carries out ball milling, wherein raw material, organic solvent and ball
Volume ratio be 2:(0.5-1.2): (3-5), organic solvent are made of ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether;
(3) by slurry obtained above it is spray-dried after, sieving obtain material grain, then will material grain compression moulding pressed
Base;
(4) green compact is placed in sintering furnace, is first heated under vacuum conditions, heat preservation when rising to 800 DEG C -1000 DEG C
1-3h carries out pre-sintering processing, is then passed through hydrogen into sintering furnace again, is continuously heating to 1500 DEG C -1800 DEG C, is sintered
After handling 2-6h, room temperature is naturally cooled to, cemented carbide material can be obtained.
Compared with prior art, the beneficial effects of the present invention are:
(1) fusing point of hard alloy can be improved by the way that the components such as HfC, BN are added in the present invention;By the way that metal Mo, Ni is added
Mixture can increase and harden the wetability mutually and between metal binding agent and additive, to improve the comprehensive of hard alloy
Close performance;The inoxidizability of hard alloy can be improved by the way that rare-earth metal La is added;In addition, Nb of the invention2O5Component exists
Meeting full-fusing, matches with metal binding agent in sintering process, can reinforce the dispersion of hardening phase and other additives, to mention
The performances such as high Cemented Carbide Hardness, toughness and temperature tolerance.
(2) present invention, in the case where compound and is synergistic with other components, is obtained by the way that graphite oxide component is added
Cemented carbide material can guarantee while possess high rigidity, high intensity and high tenacity at normal temperature, also have high-melting-point, strong anti-
The features such as oxidisability, strong thermal conductivity and low thermal coefficient of expansion, also can guarantee that hard alloy possesses good performance at high temperature.
(3) present invention passes through addition ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether etc. in hard alloy preparation process
Organic solvent carrys out auxiliary material ball milling, and the dispersibility between each component can be improved and reduce the oxygen content in hard alloy;
Specific embodiment
Technical solution of the present invention is described in more detail With reference to embodiment.
Embodiment 1
A kind of high temperature cemented carbide material, is made of hardening phase, metal adhesive and additive;Wherein hardening mutually by with
Under according to parts by weight raw material form: 60 parts of WC, 5 parts of HfC, 8 parts of BN;Metal adhesive is by below according to the original of parts by weight
Material composition: Mo, Ni mixture 5;Additive is made of the raw material below according to parts by weight: Nb2O54 parts, 1 part of La, graphite oxide
2 parts;Wherein, WC is superfine tungsten carbide, and BN is hexagonal boron nitride, and the fusing point of HfC is 3880 DEG C, Nb2O5Fusing point be 1482
DEG C, Mo and Ni mass ratio is 1:2 in Mo, Ni mixture, and Ni is extra-fine nickel powder, and graphite oxide is by crystalline flake graphite by Strong oxdiative
Agent oxidation processes obtain.
A kind of preparation method of high temperature cemented carbide material, includes the following steps:
(1) ingredient is carried out by the mass ratio of above-mentioned each component, then the raw material prepared is put into V-type blender and is filled
Divide mixing, wherein V-type blender revolving speed is 15 revs/min;
(2) mixed raw material and organic solvent one are reinstated into ball mill and carries out ball milling, wherein raw material, organic solvent and ball
Volume ratio be 2:0.5:3, organic solvent is made of ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether;
(3) by slurry obtained above it is spray-dried after, sieving obtain material grain, then will material grain compression moulding pressed
Base;
(4) green compact is placed in sintering furnace, is first heated under vacuum conditions, 1h is kept the temperature when rising to 800 DEG C and is carried out
Pre-sintering processing, is then passed through hydrogen into sintering furnace again, is continuously heating to 1500 DEG C, after being sintered 2h, naturally cold
But room temperature is arrived, cemented carbide material can be obtained.
Embodiment 2
A kind of high temperature cemented carbide material, is made of hardening phase, metal adhesive and additive;Wherein hardening mutually by with
Under according to parts by weight raw material form: 50 parts of WC, 8 parts of HfC, 12 parts of BN;Metal adhesive is by below according to the original of parts by weight
Material composition: Mo, Ni mixture 18;Additive is made of the raw material below according to parts by weight: Nb2O56 parts, 2 parts of La, oxidation stone
5 parts of ink;Wherein, WC is superfine tungsten carbide, and BN is hexagonal boron nitride, and the fusing point of HfC is 3885 DEG C, Nb2O5Fusing point be 1485
DEG C, Mo and Ni mass ratio is 1:4 in Mo, Ni mixture, and Ni is extra-fine nickel powder, and graphite oxide is by crystalline flake graphite by Strong oxdiative
Agent oxidation processes obtain.
A kind of preparation method of high temperature cemented carbide material, includes the following steps:
(1) ingredient is carried out by the mass ratio of above-mentioned each component, then the raw material prepared is put into V-type blender and is filled
Divide mixing, wherein V-type blender revolving speed is 30 revs/min;
(2) mixed raw material and organic solvent one are reinstated into ball mill and carries out ball milling, wherein raw material, organic solvent and ball
Volume ratio be 2:1:4, organic solvent is made of ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether;
(3) by slurry obtained above it is spray-dried after, sieving obtain material grain, then will material grain compression moulding pressed
Base;
(4) green compact is placed in sintering furnace, is first heated under vacuum conditions, 2h is kept the temperature when rising to 900 DEG C and is carried out
Pre-sintering processing, is then passed through hydrogen into sintering furnace again, is continuously heating to 1700 DEG C, after being sintered 5h, naturally cold
But room temperature is arrived, cemented carbide material can be obtained.
Embodiment 3
A kind of high temperature cemented carbide material, is made of hardening phase, metal adhesive and additive;Wherein hardening mutually by with
Under according to parts by weight raw material form: 40 parts of WC, 10 parts of HfC, 15 parts of BN;Metal adhesive is by below according to parts by weight
Raw material composition: Mo, Ni mixture 20;Additive is made of the raw material below according to parts by weight: Nb2O510 parts, 5 parts of La, oxidation
8 parts of graphite;Wherein, WC is superfine tungsten carbide, and BN is hexagonal boron nitride, and the fusing point of HfC is 3890 DEG C, Nb2O5Fusing point be
1490 DEG C, Mo and Ni mass ratio is 1:6 in Mo, Ni mixture, and Ni is extra-fine nickel powder, and graphite oxide is by crystalline flake graphite through too strong
What oxidizing processing obtained.
A kind of preparation method of high temperature cemented carbide material, includes the following steps:
(1) ingredient is carried out by the mass ratio of above-mentioned each component, then the raw material prepared is put into V-type blender and is filled
Divide mixing, wherein V-type blender revolving speed is 40 revs/min;
(2) mixed raw material and organic solvent one are reinstated into ball mill and carries out ball milling, wherein raw material, organic solvent and ball
Volume ratio be 2:1.2:5, organic solvent is made of ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether;
(3) by slurry obtained above it is spray-dried after, sieving obtain material grain, then will material grain compression moulding pressed
Base;
(4) green compact is placed in sintering furnace, is first heated under vacuum conditions, 3h is kept the temperature when rising to 1000 DEG C and is carried out
Pre-sintering processing, is then passed through hydrogen into sintering furnace again, is continuously heating to 1800 DEG C, after being sintered 6h, naturally cold
But room temperature is arrived, cemented carbide material can be obtained.
Embodiment 4
A kind of high temperature cemented carbide material, is made of hardening phase, metal adhesive and additive;Wherein hardening mutually by with
Under according to parts by weight raw material form: 55 parts of WC, 8 parts of HfC, 10 parts of BN;Metal adhesive is by below according to the original of parts by weight
Material composition: Mo, Ni mixture 14;Additive is made of the raw material below according to parts by weight: Nb2O58 parts, 3 parts of La, oxidation stone
6 parts of ink;Wherein, WC is superfine tungsten carbide, and BN is hexagonal boron nitride, and the fusing point of HfC is 3885 DEG C, Nb2O5Fusing point be 1485
DEG C, Mo and Ni mass ratio is 1:5 in Mo, Ni mixture, and Ni is extra-fine nickel powder, and graphite oxide is by crystalline flake graphite by Strong oxdiative
Agent oxidation processes obtain.
A kind of preparation method of high temperature cemented carbide material, includes the following steps:
(1) ingredient is carried out by the mass ratio of above-mentioned each component, then the raw material prepared is put into V-type blender and is filled
Divide mixing, wherein V-type blender revolving speed is 30 revs/min;
(2) mixed raw material and organic solvent one are reinstated into ball mill and carries out ball milling, wherein raw material, organic solvent and ball
Volume ratio be 2:1:4, organic solvent is made of ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether;
(3) by slurry obtained above it is spray-dried after, sieving obtain material grain, then will material grain compression moulding pressed
Base;
(4) green compact is placed in sintering furnace, is first heated under vacuum conditions, 2h is kept the temperature when rising to 900 DEG C and is carried out
Pre-sintering processing, is then passed through hydrogen into sintering furnace again, is continuously heating to 1700 DEG C, after being sintered 5h, naturally cold
But room temperature is arrived, cemented carbide material can be obtained.
Comparative example 1
Except same as Example 4 without containing graphite oxide component, other components and its content and preparation method.
Comparative example 2
Except without containing Nb2O5Component, other components and its content and preparation method are same as Example 4.
Comparative example 3
Each component and content are same as Example 4, but use following preparation method:
(1) ingredient is carried out by the mass ratio of above-mentioned each component, then the raw material prepared is put into V-type blender and is filled
Divide mixing, wherein V-type blender revolving speed is 30 revs/min;
(2) mixed raw material is subjected to ball milling with ball mill;
(3) powder obtained above is sieved to obtain material grain, material grain compression moulding is then obtained into green compact;
(4) green compact is placed in sintering furnace, is first heated under vacuum conditions, 2h is kept the temperature when rising to 900 DEG C and is carried out
Pre-sintering processing, is then passed through hydrogen into sintering furnace again, is continuously heating to 1700 DEG C, after being sintered 5h, naturally cold
But room temperature is arrived, cemented carbide material can be obtained.
By the hard of cemented carbide material made from above-described embodiment 1-4 and comparative example 1-3 and the YT trade mark of the prior art
Alloy presses professional standard under identical condition and carries out correlated performance test.Wherein, thermal conductivity, the thermal expansion of hard alloy are obtained
Coefficient, oxygen content, hardness, the test data of bending strength and hardness and bending strength at high temperature are as follows:
According to cemented carbide material made from 1-4 of the embodiment of the present invention, Yao Bixian it can be seen from the test result of upper table
The hard alloy of some YT trades mark possesses more excellent heat-resisting quantity, while counter-bending under hardness at normal temperature and room temperature
Intensity is also better than the YT trade mark.
In addition, from the test result of comparative example 1-2 and embodiment 4 can be seen that the present invention by be added graphite oxide and
Nb2O5Component, and in the case where compound and is synergistic with other components, obtained cemented carbide material can guarantee at normal temperature
While possessing high rigidity and high tenacity, also there is high-melting-point, strong anti-oxidation, strong thermal conductivity and low thermal coefficient of expansion etc.
Feature also can guarantee that hard alloy possesses good performance at high temperature.
In addition, can be seen that the present invention in hard alloy preparation process from the test result of comparative example 3 and embodiment 4
By organic solvents such as addition ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether come auxiliary material ball milling, hard conjunction can be reduced
Oxygen content in gold, and the performances such as heat-resisting quantity for improving hard alloy.
Better embodiment of the invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be without departing from the purpose of the present invention
Various changes can be made.
Claims (6)
1. a kind of high temperature cemented carbide material, is made of, which is characterized in that described hardening phase, metal adhesive and additive
Hardening mutually be made of the raw material below according to parts by weight: 40-60 parts of WC, 5-10 parts of HfC, 8-15 parts of BN;The metal
Binder is made of the raw material below according to parts by weight: Mo, Ni mixture 5-20;The additive is by below according to parts by weight
Raw material composition: Nb2O54-10 parts, 1-5 parts of La, 2-8 parts of graphite oxide;The WC is superfine tungsten carbide;The hard
The preparation method of alloy material, includes the following steps:
(1) ingredient is carried out by the mass ratio of above-mentioned each component, then the raw material prepared is put into V type mixer and is carried out sufficiently
Mixing, wherein V-type blender revolving speed is 15-40 revs/min;
(2) mixed raw material and organic solvent one are reinstated into ball mill and carries out ball milling, wherein the body of raw material, organic solvent and ball
Product is than being 2:(0.5-1.2): (3-5), organic solvent are made of ethyl alcohol, citric acid and fatty alcohol polyoxyethylene ether;
(3) by slurry obtained above it is spray-dried after, sieving obtain material grain, then will material grain compression moulding obtain green compact;
(4) green compact is placed in sintering furnace, is first heated under vacuum conditions, keeps the temperature 1-3h when rising to 800 DEG C -1000 DEG C
Pre-sintering processing is carried out, is then passed through hydrogen into sintering furnace again, 1500 DEG C -1800 DEG C is continuously heating to, is sintered
After 2-6h, room temperature is naturally cooled to, cemented carbide material can be obtained.
2. a kind of high temperature cemented carbide material according to claim 1, which is characterized in that the BN is six sides nitridation
Boron.
3. a kind of high temperature cemented carbide material according to claim 1, which is characterized in that the fusing point of the HfC is
3880℃-3890℃;The Nb2O5Fusing point be 1480 DEG C -1490 DEG C.
4. a kind of high temperature cemented carbide material according to claim 1, which is characterized in that Mo, Ni mixture
Middle Mo and Ni mass ratio is 1:2-1:6, and wherein Ni is extra-fine nickel powder.
5. a kind of high temperature cemented carbide material according to claim 1, which is characterized in that the graphite oxide be by
What crystalline flake graphite was obtained by strong oxidizer oxidation processes.
6. a kind of high temperature cemented carbide material according to claim 1, which is characterized in that the hardening is mutually by following
It is formed according to the raw material of parts by weight: 55 parts of WC, 8 parts of HfC, 10 parts of BN;The metal adhesive is by below according to parts by weight
Raw material composition: 14 parts of Mo, Ni mixture;The additive is made of the raw material below according to parts by weight: Nb2O58 parts, La
3 parts, 6 parts of graphite oxide.
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