CN111575605A - Stainless steel-based valve seat ring material for CNG engine and preparation method thereof - Google Patents
Stainless steel-based valve seat ring material for CNG engine and preparation method thereof Download PDFInfo
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- CN111575605A CN111575605A CN202010427562.XA CN202010427562A CN111575605A CN 111575605 A CN111575605 A CN 111575605A CN 202010427562 A CN202010427562 A CN 202010427562A CN 111575605 A CN111575605 A CN 111575605A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/04—Hardening by cooling below 0 degrees Celsius
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
- F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
Abstract
The invention relates to a stainless steel-based valve seat ring material for a natural gas engine and a preparation method thereof. The material is characterized by comprising the following components in percentage by weight: ta 2-12 wt.%, W2-6 wt.%, Cr 23-30 wt.%, Mo 2-5 wt.%, Cu 5-15 wt.%, Ni 2-15 wt.%, B0.07-0.15 wt.%, and the balance of Fe. The material has optimized wear resistance, high temperature oxidation corrosion resistance and heat conductivity, and can obviously improve the service performance of the valve seat ring, so that the valve seat ring is suitable for the working environment with higher working temperature and lower lubrication in a natural gas engine.
Description
Technical Field
The invention relates to powder metallurgy stainless steel and a preparation method thereof. The material has great performance advantages and potential in the application field of valve seat rings for high-power engines and natural gas engines. The friction and wear behavior of the seat ring can be improved, and the service life of the seat ring is prolonged.
Background
Engineering engines are moving towards high power, low energy consumption, low emissions and long life. As the core of the automobile industry, the improvement of the performance of the automobile engine can significantly improve the energy conversion efficiency, pollution emission and the like of the automobile. And under the environment that the environmental protection requirement is increasingly improved and the petroleum resource is increasingly exhausted, the natural gas engine is developed to have greater market potential and value.
Compared with the traditional diesel/gasoline engine, the natural gas engine has the advantages of less emission, low cost, stable combustion and the like; but also the engine shows the disadvantages of short life, frequent stops and major repairs due to high combustion temperatures and lack of lubrication. Among them, the inlet/exhaust valve and the valve seat ring are one of the most important friction pairs of the engine, and the abrasion and the failure of the valve seat are the keys influencing the sealing performance, the combustion temperature, the compression ratio and the service life of the engine. Research shows that the natural gas engine valve and the valve seat ring are in a severe environment with high impact stress (the highest detonation pressure is more than 20 MPa), high temperature (average 500-600 ℃, instantaneous 700-800 ℃), high abrasion, high oxidation and corrosion when working, so that the natural gas engine valve and the valve seat ring are more easily abraded, cracked and sunk and deformed than the traditional gasoline and diesel engines. And with the further improvement of the performance requirement of the engine, the working environment of the engine is further deteriorated. Thus, there is a need to optimize and develop valve seats for high performance natural gas engines in conjunction with their wear failure modes.
Patent CN102996196A discloses a powder metallurgy iron-based engine valve seat ring, which comprises 0.6-1.2 wt.% of C, 1-3 wt.% of Ni, 3-6 wt.% of Cr, 4-7 wt.% of Mo, 8-11 wt.% of Co, 0.5-2.5 wt.% of W, 1-3 wt.% of Mn, 0.2-1 wt.% of Ca and the balance of Fe, wherein the hardness of the valve seat ring is 284-332 Hv, the wear loss is 31-95 μm, the valve seat ring has excellent wear resistance, but the influence of the GNC engine working environment on chemical corrosion of the valve seat ring is not considered. The patent CN103589967A discloses a rare earth-containing powder metallurgy natural gas engine valve seat ring, which adopts an alloy system with high cobalt, molybdenum, tungsten and chromium (the total amount is up to 91%), wherein the high chromium component can effectively enhance the corrosion resistance of the valve seat ring in the working environment, but cobalt and nickel are currently used as important strategic materials in the world, and the high cobalt content in the alloy system can increase the manufacturing cost of the valve seat ring.
Disclosure of Invention
In summary, from the viewpoint of simultaneously optimizing the density, purity and alloy content of the material, the invention aims to simultaneously optimize the density, purity, alloy element content and tempering resistance of the seat ring material through a new alloy system and a new preparation process, thereby improving the service performance of the seat ring material in a natural gas engine.
The invention is realized by the following technical scheme:
a stainless steel-based valve seat ring material for a natural gas engine, wherein the composition of the material is as follows (weight percentage): 1, Ta 2-16 wt.%, W1-6 wt.%, Cu 5-15 wt.%, Cr 18-25 wt.%, Mo 2-5 wt.%, Ni 2-15 wt.%, B0.07-0.15 wt.%, and the balance of Fe.
The preparation method of the stainless steel-based valve seat ring material specifically comprises the following steps:
step 1: weighing raw material powder according to the component ratio, performing mechanical ball milling, and performing compression molding under the pressure of 150MPa to obtain a green compact;
step 2: sintering the pressed blank obtained in the step 1 in a vacuum furnace, wherein the highest temperature is 1000-1175 ℃, and keeping the temperature for 120-180 min;
and step 3: carrying out high-temperature quenching on the blank obtained after sintering in the step 2 in a vacuum gas quenching mode, and quenchingThe fire temperature is 1050-1200 ℃; after the oil is cooled to room temperature, carrying out primary-80-120 ℃ cryogenic treatment in a liquid nitrogen cryogenic box for 120 min; after returning to room temperature at N2And carrying out one-time tempering at 700-800 ℃ in a protective atmosphere for 180 min.
The prepared stainless steel-based valve seat ring material is characterized in that the raw materials are added with high-purity hydroxyl iron powder, nickel powder, tungsten powder, tantalum powder, copper powder, molybdenum powder, chromium powder, ferroboron and other metal powder, the particle size range is 10-80 mu m, the oxygen content of the powder is lower than 0.1%, and stearic acid is used as a binder.
The prepared stainless steel-based valve seat ring material is characterized in that the step 1 can realize the large addition of W, Ta, Cr and Cu elements and the elimination of impurities such as S, P and the like, and can replace copper infiltration in the traditional preparation process to realize the near-net-shape sintering full densification.
The prepared stainless steel-based valve seat ring material is characterized in that high-temperature quenching is carried out in a vacuum gas quenching mode in the step 3, the quenching temperature is 1050-1200 ℃, and oil cooling is carried out to the room temperature.
The prepared stainless steel-based valve seat ring material is characterized in that after high-temperature quenching in the step 3, cryogenic treatment is carried out in a liquid nitrogen cryogenic box at-80-120 ℃ for 120min, and the temperature in the box is recovered to room temperature.
The prepared stainless steel-based valve seat ring material is characterized in that after deep cooling treatment in the step 3, tempering is carried out at 700-800 ℃ for 180min in an argon or nitrogen protective atmosphere with purity not less than 99.9%, and air cooling is carried out to room temperature.
The principle and the beneficial effects of the invention are as follows:
1. the invention adopts a powder mixing method, and corresponding alloy types and proportions can be added according to the required requirements. The quantitative addition of the copper element and the dispersion distribution of the copper element in the alloy improve the heat conductivity of the material and reduce the influence on the wear resistance of the material.
2. The tantalum has the advantages of high melting point, small thermal expansion coefficient, strong corrosion resistance and the like, and can ensure that the valve seat ring is suitable for the working environment with higher working temperature and lower lubrication in a natural gas engine. The two atomic structures of tantalum and tungsten are similar, so that an alternative continuous solid solution can be formed, but the shear modulus difference of the two elements of tantalum and tungsten is large, so that the dislocation energy is changed, and the yield strength and the hardness of the alloy material are enhanced.
3. The addition of ferroboron can obviously improve the hardenability of the material, ensure the high-temperature strength and hardness of the material after heat treatment and prevent the valve or the seat ring from being preferentially worn.
4. The invention adopts the direct preparation process of the powder metallurgy stainless steel, can prevent the valve seat ring from being over-tempered in the service process, and further ensures the hardness and the wear resistance of the material.
5. Compared with the composite material of the traditional valve seat ring, the composite material has the advantages of uniform and fine structure, high fatigue strength, good compression strength, tensile strength and wear resistance after heat treatment, and can prevent the valve seat from generating larger sinking amount in the service process.
The specific implementation mode is as follows:
the preparation and processing properties of the present invention are illustrated by specific examples, and the advantages and effects of the present invention will be fully understood by those skilled in the art from the disclosure of the present specification.
Example 1:
1) adding 10 wt.% Ta powder, 1 wt.% W powder, 10 wt.% Cu powder, 23 wt.% Cr powder, 4 wt.% Mo powder, 9 wt.% Ni powder, 0.4 wt.% ferroboron powder and the balance of hydroxyl iron powder and paraffin accounting for 5% of the total mass into a Fe-Cr stainless steel ball milling tank, placing the tank into a planetary ball mill for mixing and wet milling, wherein the granularity is 10-80 microns, the oxygen content is less than 0.1%, the ball milling time is 72 hours, and the rotating speed of the ball mill is set to 250r/min, and the ball milling time is 5 hours;
2) rapidly drying the powder mixture slurry obtained in the step 1 in a vacuum drying oven in a negative pressure drying mode, wherein the drying temperature is 78.3 ℃, the drying time is determined according to the total mass of the powder (for example, 8 hours are needed for 400g of powder), then carrying out pre-oxidation for a certain time and temperature in a low-oxygen partial pressure drying oven, and sieving with a 40-mesh sieve for granulation to obtain mixed powder;
3) and (3) pressing the mixed powder obtained in the step (2) on an oil pressure press, wherein the pressure is 150Mpa, the pressure is slowly increased, and the pressure maintaining time is 20s, so that a pressed blank body is obtained.
4) And (3) putting the blank obtained in the step (3) into a degreasing-sintering integrated vacuum graphite sintering furnace for degreasing-sintering, wherein the final sintering temperature is 1150 ℃, and the heat preservation time is 120 min.
5) Quenching the sintered blank obtained in the step 4 in a vacuum gas quenching mode, wherein the quenching temperature is 1050 ℃; then, carrying out primary-120 ℃ cryogenic treatment in a liquid nitrogen cryogenic box for 120 min; after returning to room temperature at N2And (3) tempering at 700 ℃ for 180min once in a protective atmosphere to obtain the required powder metallurgy stainless steel.
The powder metallurgy stainless steel prepared by the method is subjected to performance test.
Example 2:
1) adding 15 wt.% Ta powder, 3 wt.% W powder, 15 wt.% Cu powder, 25 wt.% Cr powder, 4 wt.% Mo powder, 15 wt.% Ni powder, 0.6 wt.% ferroboron powder and the balance of hydroxyl iron powder and paraffin accounting for 5% of the total mass into a Fe-Cr stainless steel ball milling tank, putting the tank into a planetary ball mill for mixing and wet milling, wherein the granularity is 10-80 microns, the oxygen content is less than 0.1%, the ball milling time is 96 hours, and the ball milling tank is prepared into powder mixture slurry, and the tank is put into a ball milling machine for mixing and wet milling, absolute ethyl alcohol is used as a ball milling medium, hard alloy balls are used as milling balls, the ball-to-material ratio is 5:1, the rotating speed of the ball mill is set to 200 r/min;
2) rapidly drying the powder mixture slurry obtained in the step 1 in a vacuum drying oven in a negative pressure drying mode, wherein the drying temperature is 80 ℃, the drying time is determined according to the total mass of the powder (for example, 8 hours are needed for 400g of powder), then pre-oxidizing the powder mixture slurry in a low-oxygen partial pressure drying oven for a certain time and temperature, and sieving the powder mixture slurry with a 40-mesh sieve for granulation to obtain mixed powder;
3) and (3) pressing the mixed powder obtained in the step (2) on an oil pressure press, wherein the pressure is 200Mpa, the pressure is slowly increased, and the pressure maintaining time is 10s, so as to obtain a pressed blank body.
4) And (3) putting the blank obtained in the step (3) into a degreasing-sintering integrated vacuum graphite sintering furnace for degreasing-sintering, wherein the final sintering temperature is 1075 ℃, and the heat preservation time is 180 min.
5) Quenching the sintered blank obtained in the step 4 in a vacuum gas quenching mode, wherein the quenching temperature is 1050 ℃; then, carrying out primary-80 ℃ cryogenic treatment in a liquid nitrogen cryogenic box for 120 min; after returning to room temperature at N2And (3) tempering at 600 ℃ for 180min in a protective atmosphere to obtain the required powder metallurgy stainless steel.
The powder metallurgy stainless steel prepared by the method is subjected to performance test.
Example 3:
1) adding 12 wt.% Ta powder, 1 wt.% W powder, 10 wt.% Cu powder, 18 wt.% Cr powder, 4 wt.% Mo powder, 9 wt.% Ni powder, 0.28 wt.% ferroboron powder and the balance of hydroxyl iron powder and paraffin accounting for 5% of the total mass into a Fe-Cr stainless steel ball milling tank, placing the tank into a planetary ball mill for mixing and wet milling, wherein the granularity is 10-80 microns, the oxygen content is less than 0.1%, the ball milling speed is set to 250r/min, the ball milling time is 96 hours, and preparing powder mixture slurry;
2) rapidly drying the powder mixture slurry obtained in the step 1 in a vacuum drying oven in a negative pressure drying mode, wherein the drying temperature is 80 ℃, the drying time is determined according to the total mass of the powder (for example, 8 hours are needed for 400g of powder), then pre-oxidizing the powder mixture slurry in a low-oxygen partial pressure drying oven for a certain time and temperature, and sieving the powder mixture slurry with a 40-mesh sieve for granulation to obtain mixed powder;
3) and (3) pressing the mixed powder obtained in the step (2) on an oil pressure press, wherein the pressure is 300Mpa, the pressure is slowly increased, and the pressure maintaining time is 10s, so as to obtain a pressed blank body.
4) And (3) putting the blank obtained in the step (3) into a degreasing-sintering integrated vacuum graphite sintering furnace for degreasing-sintering, wherein the final sintering temperature is 1175 ℃, and the heat preservation time is 120 min.
5) Quenching the sintered blank obtained in the step 4 in a vacuum gas quenching mode, wherein the quenching temperature is 1050 ℃; then, carrying out primary-100 ℃ cryogenic treatment in a liquid nitrogen cryogenic box for 120 min; after returning to room temperature at N2And tempering at 800 ℃ for 180min once in protective atmosphere to obtain the required powder metallurgy stainless steel.
The powder metallurgy stainless steel prepared by the method is subjected to performance test.
Claims (9)
1. A stainless steel-based valve seat ring material for a natural gas engine, wherein the composition of the material is as follows (weight percentage): ta 2-16 wt.%, W1-6 wt.%, Cu 5-15 wt.%, Cr 18-25 wt.%, Mo 2-5 wt.%, Ni 2-15 wt.%, B0.07-0.15 wt.%, and the balance of Fe.
2. The material according to claim 1, characterized in that it is prepared by a method comprising the following steps:
step 1: weighing raw material powder according to the component proportion of claim 1, carrying out mechanical ball milling, and adopting 150MPa pressure to carry out compression molding to obtain a green compact;
step 2: sintering the pressed blank obtained in the step 1 in a vacuum furnace, wherein the highest temperature is 1000-1175 ℃, and keeping the temperature for 120-180 min;
and step 3: carrying out high-temperature quenching on the blank obtained after sintering in the step 2 in a vacuum gas quenching mode, wherein the quenching temperature is 1050-1200 ℃; after the oil is cooled to room temperature, carrying out primary-80-120 ℃ cryogenic treatment in a liquid nitrogen cryogenic box for 120 min; after returning to room temperature at N2And carrying out one-time tempering at 700-800 ℃ in a protective atmosphere for 180 min.
3. The material of claim 1, wherein the raw material is selected from the group consisting of high purity iron powder, nickel powder, tungsten powder, tantalum powder, copper powder, molybdenum powder, chromium powder, ferroboron powder, etc., the particle size is 10-80 μm, the oxygen content of the powder is less than 0.1%, and stearic acid is used as a binder.
4. The method of claim 3, wherein the step 1 can realize the large addition of W, Ta, Cr and Cu elements and the elimination of impurities such as S and P, and can replace the copper infiltration in the traditional preparation process to realize the near-net-shape sintering full densification.
5. The method as claimed in claim 3, wherein the step 3 is carried out by high-temperature quenching in a vacuum gas quenching mode, wherein the quenching temperature is 1050-1200 ℃, and the oil cooling is carried out to the room temperature.
6. The method according to claim 3, wherein the high-temperature quenching in step 3 is followed by a cryogenic treatment at-80 to 120 ℃ for 120min in a liquid nitrogen cryogenic box, and the temperature in the cryogenic box is returned to room temperature.
7. The method according to claim 3, wherein the deep cooling treatment in step 3 is followed by a tempering at 700-800 ℃ in an argon or nitrogen atmosphere with a purity of 99.9% or more for 180min, and air-cooling to room temperature.
8. The method of claim 3, wherein the addition of ferroboron significantly increases the hardenability of the material, ensures high temperature strength and hardness of the material after the heat treatment of step 3, and prevents preferential wear of the valve or seat ring.
9. The method of claim 3, wherein the material after heat treatment has a uniform and fine texture, high fatigue strength, thermal conductivity, wear resistance and corrosion resistance, and prevents the valve seat from sinking more during service than conventional valve seat insert composites.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010427562.XA CN111575605A (en) | 2020-05-19 | 2020-05-19 | Stainless steel-based valve seat ring material for CNG engine and preparation method thereof |
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| CN202010427562.XA CN111575605A (en) | 2020-05-19 | 2020-05-19 | Stainless steel-based valve seat ring material for CNG engine and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114574774A (en) * | 2022-01-19 | 2022-06-03 | 长沙市萨普新材料有限公司 | Stainless powder metallurgy high-speed steel for wet-type rotary die cutter roller and preparation method thereof |
| CN114622122A (en) * | 2022-03-04 | 2022-06-14 | 长沙市萨普新材料有限公司 | High-niobium iron-based superhard material and preparation method thereof |
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| CN114574774A (en) * | 2022-01-19 | 2022-06-03 | 长沙市萨普新材料有限公司 | Stainless powder metallurgy high-speed steel for wet-type rotary die cutter roller and preparation method thereof |
| CN114622122A (en) * | 2022-03-04 | 2022-06-14 | 长沙市萨普新材料有限公司 | High-niobium iron-based superhard material and preparation method thereof |
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Application publication date: 20200825 |