CN111187938B - TiC-alloy steel composite material and preparation method thereof - Google Patents
TiC-alloy steel composite material and preparation method thereof Download PDFInfo
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- C22C29/06—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 based on carbides, but not containing other metal compounds
- C22C29/10—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 based on carbides, but not containing other metal compounds based on titanium carbide
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- C22C37/08—Cast-iron alloys containing chromium with nickel
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- 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
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- B22F2003/248—Thermal after-treatment
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention relates to a TiC-alloy steel composite material and a preparation method thereof. The TiC-alloy steel composite material comprises a ceramic phase and a metal phase; the mass ratio of the ceramic phase to the metal phase is 30-50: 50-70; the ceramic phase comprises the following components in percentage by mass: 80-95% of TiC, 1-5% of ZrC, 1-5% of NbC, 1-5% of VC and Cr3C21 to 5 percent; the metal phase comprises the following components in percentage by mass: 2-15% of Cr, 2-10% of Ni, 2-8% of Co, 0.5-3% of Cu, 0.5-3% of Ti, 1-4% of Mo, 0.6-3% of C, 0.1-0.5% of rare earth elements and 53.5-91.3% of Fe. The TiC-alloy steel composite material has the characteristics of high hardness and high strength, and is excellent in wear resistance and corrosion resistance.
Description
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a TiC-alloy steel composite material and a preparation method thereof.
Background
The ceramic-metal composite material has good application prospect in the fields of tools, dies and wear-resistant parts because the ceramic-metal composite material can combine the high hardness of ceramic and the high toughness of metal. One of the ceramic-metal composite materials is a composite material composed of WC and TiC as ceramic phase and alloy steel as metal phase, and is called cermet or steel-bonded cemented carbide. The performance of the steel bonded hard alloy is between that of high-speed steel and common WC-Co alloy, and the gap between the two materials is filled. When steel is used as a binding phase, the prepared composite material can have heat treatment property and processability after heat treatment, so that the application of the ceramic-metal composite material is greatly expanded.
However, in addition to the requirements for the hardness and toughness of the composite material, new requirements for the wear resistance and corrosion resistance of the ceramic-metal composite material are also provided in the actual demands, and the existing products at home and abroad still cannot realize good wear resistance and corrosion resistance.
Disclosure of Invention
Based on this, one of the objects of the present invention is to provide a TiC-alloy steel composite material having high hardness and high strength, and being excellent in wear resistance and corrosion resistance.
The specific technical scheme is as follows:
a TiC-alloy steel composite material comprises a ceramic phase and a metal phase;
the mass ratio of the ceramic phase to the metal phase is 30-50: 50-70;
the ceramic phase comprises the following components in percentage by mass: 80-95% of TiC, 1-5% of ZrC, 1-5% of NbC, 1-5% of VC and Cr3C21-5%;
The metal phase comprises the following components in percentage by mass: 2-15% of Cr, 2-10% of Ni, 2-8% of Co, 0.5-3% of Cu, 0.5-3% of Ti, 1-4% of Mo, 0.6-3% of C, 0.1-0.5% of rare earth elements and 53.5-91.3% of Fe. The invention also aims to provide a preparation method of the TiC-alloy steel composite material, which comprises the following steps:
(1) mixing the components of the ceramic phase with a wet grinding medium and a dispersing agent, and carrying out ball milling;
(2) after ball milling, adding the components of the metal phase, the binder and the dispersant, and continuing ball milling to obtain mixed slurry;
(3) drying and granulating the mixed slurry to obtain a mixture;
(4) and pressing and forming the mixture, and then sintering, annealing, quenching and tempering.
Compared with the prior art, the invention has the following beneficial effects:
the invention selects proper components of ceramic phase and metal phase, combines the optimal proportion, and prepares the alloy with high hardness, high strength, high wear resistance and high corrosion resistance under the action of all the componentsA ceramic-metal composite. In the ceramic phase, ZrC, NbC, VC and Cr are selectively added3C2And the composite material is matched with TiC, so that the strength, hardness and wear resistance of the composite material are improved. Wherein ZrC and NbC are diffused in TiC to play a role in strengthening TiC; and VC and Cr3C2The wear resistance of the metal phase can be further improved. In the metal phase, the Cr, Ni, Co and Cu are matched to improve the acid and alkali corrosion resistance and the temperature resistance of the composite material; further, the toughness of the metal phase can be improved by the incorporation of carbon. The addition of rare earth elements can refine grains and improve the comprehensive performance of the material. Meanwhile, Ti is added into the metal phase to reduce TiC dissolution and precipitation, so that TiC crystal grains are refined, and the strength and toughness of the composite material are further improved.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A TiC-alloy steel composite material comprises a ceramic phase and a metal phase;
the mass ratio of the ceramic phase to the metal phase is 30-50: 50-70;
the ceramic phase comprises the following components in percentage by mass: 80-95% of TiC, 1-5% of ZrC, 1-5% of NbC, 1-5% of VC and Cr3C21-5%;
The metal phase comprises the following components in percentage by mass: 2-15% of Cr, 2-10% of Ni, 2-8% of Co, 0.5-3% of Cu, 0.5-3% of Ti, 1-4% of Mo, 0.6-3% of C, 0.1-0.5% of rare earth elements and 53.5-91.3% of Fe.
In some embodiments, the metal phase comprises the following components in percentage by mass: 2-15% of Cr, 2-10% of Ni, 2-8% of Co, 0.5-3% of Cu, 0.5-3% of Ti, 1-4% of Mo, 0.6-3% of C, 0.1-0.5% of rare earth elements and the balance of iron.
In some embodiments, the ceramic phase comprises the following components in percentage by mass: TiC 87-93%, ZrC 1-3%, NbC 3-5%, VC 1-2% and Cr3C22-3%;
The metal phase comprises the following components in percentage by mass: 3-12% of Cr, 4-7% of Ni, 3-6% of Co, 0.5-1.5% of Cu, 0.5-2.5% of Ti, 2-3% of Mo, 0.6-1.2% of C, 0.1-0.2% of rare earth elements and 66.6-86.3% of FeC.
In some embodiments, the metal phase comprises the following components in percentage by mass: 3-12% of Cr, 4-7% of Ni, 3-6% of Co, 0.5-1.5% of Cu, 0.5-2.5% of Ti, 2-3% of Mo, 0.6-1.2% of C, 0.1-0.2% of rare earth elements and the balance of iron.
In some of these embodiments, the mass ratio of the ceramic phase to the metal phase is 30-40: 60-70;
the ceramic phase comprises the following components in percentage by mass: TiC 89-91%, TiC 1.5-2.5%, NbC3.5-4.5%, VC 1-2% and Cr3C22-3%;
The metal phase comprises the following components in percentage by mass: 6-10% of Cr, 4-6% of Ni, 3-5% of Co, 0.5-1.5% of Cu, 1-2% of Ti, 2-3% of Mo, 0.7-0.9% of C, 0.1-0.2% of rare earth element and the balance of Fe.
In some of these embodiments, the rare earth element comprises at least one of Ce and La.
A preparation method of a TiC-alloy steel composite material comprises the following steps:
(1) mixing the components of the ceramic phase with a wet grinding medium and a dispersing agent, and carrying out ball milling;
(2) after ball milling, adding the components of the metal phase, the binder and the dispersant, and continuing ball milling to obtain mixed slurry;
(3) drying and granulating the mixed slurry to obtain a mixture;
(4) and pressing and forming the mixture, and then sintering, annealing, quenching and tempering.
In some of these embodiments, the dispersant includes at least one of oleic acid, lauric acid, and ammonium citrate.
In some of these embodiments, the binder includes at least one of paraffin wax and rubber.
In some of these embodiments, the wet milling medium comprises at least one of gasoline, ethanol, and cyclohexane.
In some embodiments, in step (4), the sintering temperature is 1380-1440 ℃; the sintering vacuum degree is 5-20 Pa; the sintering time is 1-2 h.
In some embodiments, the annealing temperature in step (4) is 800-; and/or the quenching temperature is 1000-1100 ℃; and/or the temperature of the tempering is 200-300 ℃.
In some of the embodiments, in step (1), the mass of the dispersant is 1-2% of the mass of the ceramic phase component; in the step (2), the mass of the dispersant is 1-2% of that of the metal phase component; and/or, the mass of the binder in the step (2) is 2-3% of the mass sum of the ceramic phase component and the metal phase component.
In some embodiments, in step (1), the ball-milling has a ball-to-material ratio of 6:1 to 8:1, and the ball-milling time is 24 to 36 hours; in the step (2), the ball-milling ball-material ratio is 4:1-6:1, and the ball-milling time is 24-36 hours.
The present invention will be described in further detail with reference to specific examples.
The embodiment of the invention relates to the following raw materials:
TiC、ZrC、NbC、VC、Cr3C2cr, Ni, Co, Cu, Ti, Mo, C, rare earth elements Ce and La, Fe: purchased from national drug reagent net.
Example 1
A TiC-alloy steel composite material comprises the following raw material components in parts by weight:
the mass ratio of the ceramic phase to the metal phase is 30: 70.
the ceramic phase comprises the following components in percentage by mass: TiC87 wt.%, ZrC 3 wt.%, NbC 5 wt.%, VC2wt, Cr3C23wt.%;
The mass percentages of the components of the metal phase are as follows: 12% of Cr, 4% of Ni, 6% of Co, 0.5% of Cu, 2.5% of Ti, 3% of Mo, 1.2% of C, 0.2 wt% of rare earth elements Ce and La and the balance of Fe;
the preparation method comprises the following steps:
(1) firstly, adding the ceramic phase component and the steel balls into a ball mill in a ball-to-material ratio of 8:1, and then adding a wet grinding medium ethanol and dispersant oleic acid with the mass of 1 wt.% of the ceramic phase component, wherein the ball milling time is 24 hours;
(2) adding metal phase powder into a ball mill, simultaneously adding binder rubber accounting for 2 wt.% of the mass of all raw materials (metal phase components and ceramic phase components) and dispersant oleic acid accounting for 1 wt.% of the mass of the metal phase components, continuously adding balls and a wet grinding medium ethanol in the ball mill to enable the ball-to-material ratio to be 6:1, and continuously performing ball milling for 24 hours to obtain raw material mixed slurry;
(3) stirring and drying the raw material mixed slurry subjected to ball milling by using a vacuum drier, and after drying, wiping a sieve for granulation and screening to obtain a mixture;
(4) pressing and forming the mixture to obtain a pressed compact, and performing vacuum sintering in a vacuum sintering furnace at 1380 ℃ and under the condition of 5Pa of vacuum degree, wherein the sintering time is 1 h; and annealing the sintered product at 800 ℃, quenching at 1000 ℃ and tempering at 200 ℃ under a vacuum condition to obtain a final product.
Example 2
A TiC-alloy steel composite material comprises the following raw material components in parts by weight:
the mass ratio of the ceramic phase to the metal phase is 50: 50.
the ceramic phase comprises the following components in percentage by mass: TiC 93 wt.%, ZrC 1 wt.%, NbC3 wt.%, VC1wt wt.%, Cr3C22wt.%;
The mass percentages of the components of the metal phase are as follows: cr 3 wt.%, Ni 7 wt.%, Co 3 wt.%, Cu 1.5 wt.%, Ti 0.5 wt.%, Mo 2 wt.%, C0.6 wt.%, rare earth elements Ce and La 0.1 wt.%, and the balance Fe;
the preparation method comprises the following steps:
(1) firstly, adding the ceramic phase component and the steel ball into a ball mill, wherein the ball-material ratio is 6:1, adding wet grinding medium gasoline and dispersant ammonium citrate with the mass of 2 wt.% of the ceramic phase component, and carrying out ball milling for 36 hours;
(2) adding metal phase powder into a ball mill, simultaneously adding binder paraffin accounting for 3 wt.% of the mass of all raw materials (metal phase components and ceramic phase components) and dispersant ammonium citrate accounting for 2 wt.% of the mass of the metal phase powder, continuously adding balls and wet grinding medium gasoline into the ball mill, enabling the ball-to-material ratio to be 4:1, and continuously performing ball milling for 36 hours to obtain raw material mixed slurry;
(3) carrying out spray drying granulation on the raw material mixed slurry subjected to ball milling to obtain a mixture;
(4) pressing and forming the mixture to obtain a pressed compact, and performing vacuum sintering in a vacuum sintering furnace at 1440 ℃ and under the condition that the vacuum degree is 20Pa, wherein the sintering time is 2 hours; and annealing the sintered product at 900 ℃, quenching at 1100 ℃ and tempering at 300 ℃ under a vacuum condition to obtain the final product. The hardness reaches HRC70, and the bending strength reaches 1700 MPa.
Example 3
A TiC-alloy steel composite material comprises the following raw material components in parts by weight:
the mass ratio of the ceramic phase to the metal phase is 35: 65;
the ceramic phase comprises the following components in percentage by mass: TiC 90 wt.%, ZrC 2 wt.%, NbC 4 wt.%, vc1.5 wt.%, Cr3C22.5wt.%;
The mass percentages of the components of the metal phase are as follows: cr 8 wt.%, Ni 5 wt.%, Co 4 wt.%, Cu 1.0 wt.%, Ti 1.5 wt.%, Mo 2.5 wt.%, C0.8 wt.%, rare earth elements Ce and La 0.15 wt.%, the remainder being Fe;
the preparation method comprises the following steps:
(1) firstly, adding the ceramic phase component and the steel balls into a ball mill, wherein the ball-material ratio is 7:1, adding wet grinding medium cyclohexane and 1.5 wt.% of dispersant lauric acid of the ceramic phase component, and carrying out ball milling for 30 hours;
(2) adding metal phase powder into a ball mill, simultaneously adding 2 wt.% of binder rubber and 2 wt.% of dispersant lauric acid based on the mass of all raw materials (metal phase components and ceramic phase components), continuously adding balls and a wet grinding medium into the ball mill to enable the ball-to-material ratio to be 5:1, and continuously ball-milling for 30 hours to obtain raw material mixed slurry;
(3) stirring and drying the raw material mixed slurry subjected to ball milling by using a vacuum drier, and after drying, wiping a sieve for granulation and screening to obtain a mixture;
(4) pressing and forming the mixture to obtain a pressed compact, and performing vacuum sintering in a vacuum sintering furnace at 1420 ℃ and under the condition that the vacuum degree is 10Pa, wherein the sintering time is 1.5 h; annealing the sintered product at 860 ℃, quenching at 1050 ℃ and tempering at 250 ℃ under a vacuum condition to obtain a final product.
Comparative example 1
The TiC-alloy steel composite material in the comparative example is different from that in example 3 in that the metal phase does not include metal Ti, and the rest components and the preparation method are the same as those in example 3.
Comparative example 2
The TiC-alloy steel composite material in the comparative example is different from that in the example 3 in that the metal phase does not contain rare earth elements Ce and La, and the rest components and the preparation method are the same as those in the example 3.
Comparative example 3
The TiC-alloy steel composite material of the comparative example is different from that of the example 3 in that Mn is used for replacing Cr in the metal phase, and the rest components and the preparation method are the same as those of the example 3.
Physical Property test
The test method comprises the following steps: measuring the hardness of the composite material by using a Rockwell hardness tester; and (3) measuring the strength of the composite material by adopting a universal material testing machine.
The test results are shown in table 1:
TABLE 1
Hardness HRC | Strength of | |
Example 1 | 67 | 2200MPa |
Example 2 | 70 | 1700MPa |
Example 3 | 68 | 1950MPa |
Comparative example 1 | 57 | 1400MPa |
Comparative example 2 | 64 | 1200MPa |
Comparative example 3 | 61 | 1250MPa |
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A TiC-alloy steel composite material is characterized by comprising a ceramic phase and a metal phase;
the mass ratio of the ceramic phase to the metal phase is 30-50: 50-70;
the ceramic phase comprises the following components in percentage by mass: 80-95% of TiC, 1-5% of ZrC, 78-5% of NbC1, 1-5% of VC and Cr3C2 1-5%;
The metal phase comprises the following components in percentage by mass: 2-15% of Cr, 2-10% of Ni, 2-8% of Co, 0.5-3% of Cu, 0.5-3% of Ti, 1-4% of Mo, 0.6-3% of C, 0.1-0.5% of rare earth elements and 53.5-91.3% of Fe, wherein the rare earth elements are Ce and La;
the TiC-alloy steel composite material is prepared by the following steps:
(1) mixing the components of the ceramic phase with a wet grinding medium and a dispersing agent, and carrying out ball milling, wherein the ball-material ratio of the ball milling is 6:1-8:1, and the ball milling time is 24-36 hours;
(2) adding the components of the metal phase, the binder and the dispersant after ball milling, and continuing ball milling, wherein the ball-to-material ratio of ball milling is 4:1-6:1, and the ball milling time is 24-36 hours, so as to obtain mixed slurry;
(3) drying and granulating the mixed slurry to obtain a mixture;
(4) pressing and forming the mixture, then sintering, annealing, quenching and tempering,
wherein, the sintering temperature is 1380-1440 ℃, the sintering vacuum degree is 5-20Pa, the sintering time is 1-2h, the annealing temperature is 800-900 ℃, the quenching temperature is 1000-1100 ℃, and the tempering temperature is 200-300 ℃.
2. The TiC-alloy steel composite material preparation method of claim 1, characterized by consisting of the following steps:
(1) mixing the components of the ceramic phase with a wet grinding medium and a dispersing agent, and carrying out ball milling, wherein the ball-material ratio of the ball milling is 6:1-8:1, and the ball milling time is 24-36 hours;
(2) adding the components of the metal phase, the binder and the dispersant after ball milling, and continuing ball milling, wherein the ball-to-material ratio of ball milling is 4:1-6:1, and the ball milling time is 24-36 hours, so as to obtain mixed slurry;
(3) drying and granulating the mixed slurry to obtain a mixture;
(4) pressing and forming the mixture, then sintering, annealing, quenching and tempering,
wherein, the sintering temperature is 1380-1440 ℃, the sintering vacuum degree is 5-20Pa, the sintering time is 1-2h, the annealing temperature is 800-900 ℃, the quenching temperature is 1000-1100 ℃, and the tempering temperature is 200-300 ℃.
3. The production method according to claim 2, wherein the dispersant is at least one of oleic acid, lauric acid, and ammonium citrate.
4. The production method according to claim 2, wherein the binder is at least one of paraffin and rubber.
5. The method of claim 2, wherein the wet milling medium is at least one of gasoline, ethanol, and cyclohexane.
6. The preparation method according to claim 2, wherein in the step (1), the mass of the dispersant is 1-2% of the mass of the ceramic phase component; in the step (2), the mass of the dispersing agent is 1-2% of the mass of the metal phase component, and the mass of the binder is 2-3% of the sum of the mass of the ceramic phase component and the mass of the metal phase component.
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CN109022869A (en) * | 2018-08-23 | 2018-12-18 | 东北大学 | A kind of high alloy parent metal ceramic composite and preparation method thereof |
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