CN108660378A - A kind of high nitrogen alloy steel and preparation method thereof - Google Patents
A kind of high nitrogen alloy steel and preparation method thereof Download PDFInfo
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0068—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
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- 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
- C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
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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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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Abstract
The present invention relates to a kind of high nitrogen alloy steel and preparation method thereof, belong to the manufacturing technology field of ferrous alloy.The preparation method of the high nitrogen alloy steel of the present invention, includes the following steps:Include the following steps:1) mixed raw material powder is subjected to mechanical alloying processing, obtains composite granule;The mixed raw material powder includes nitride powder, carbon source powder and iron powder;The carbon source powder is at least one of carbide powder, carbon dust;2) by the composite granule compression moulding of gained, sintering, it is cooling to get.Mechanical alloying, powder metallurgical technique are organically combined, can fast and efficiently obtain high nitrogen alloy steel, and effectively reduce production cost by the preparation method of the high nitrogen alloy steel of the present invention;And nitride particles Dispersed precipitate plays pinning effect to dislocation, crystal boundary, effectively improves matrix strength and hardness, and control crystal grain is grown up, and high performance high nitrogen alloy steel is finally obtained.
Description
Technical field
The present invention relates to a kind of high nitrogen alloy steel and preparation method thereof, belong to the manufacturing technology field of ferrous alloy.
Background technology
Traditional concept thinks that nitrogen is harmful element in steel, may result in the brittle fracture of steel.To early 20th century, nitrogen
Advantageous effect in steel is just found, and especially in World War II, due to the shortage of metallic nickel, scientific research personnel is first by manganese and nitrogen
Element matches to replace expensive nickel element to achieve the purpose that the austenite in stabilized steel.In recent years, as people are in steel
Nitrogen research deepens continuously, and effect of the nitrogen in steel is increasingly taken seriously.
Nitrogen is strong among the austenite stabilizing elements, and moreover, nitrogen can also substantially expand austenite phase field, the stabilization of nitrogen
Ovshinsky ability of immigrants is only second to carbon, about the 18 of nickel times.Invigoration effect of the nitrogen in steel and carbons are solution strengthening seemingly, but nitrogen
It can cause the higher distortion of matrix, therefore, the invigoration effect of nitrogen is greater than carbon.In addition, being easy to be precipitated in intergranular when carbon is excessively high
Such issues that carbide reduces the toughness and resistance to corrosion of material, and nitrogen is then not present.
But solubility very little of the nitrogen in ferrite, it will necessarily be overflowed from matrix during solidification of molten steel, because
This, it is difficult to obtain high nitrogen steel by traditional method of smelting, at present common practice be by improve nitrogen killer such as chromium in steel,
The content of manganese, nickel etc., or solubility of the nitrogen in steel is improved by nitrogen partial pressure in raising process of setting.Such as Authorization Notice No.
A kind of preparation method of high nitrogen steel is disclosed for the Chinese invention patent of CN104862447B, is by austenitic stainless steel in vacuum
Under be heated to fusing after, control the degree of superheat of molten steel, be filled with nitrogen, after nitrogen in molten metal reach saturation after begin to cool;It will be golden
Category, which is cooled in semi-solid temperature section, to be kept the temperature, and after heat preservation, is cooled to room temperature with the furnace and is obtained high nitrogen steel.Both the above
Method needs that more expensive alloying elements are added, or needs special pressurization smelting apparatus so that high nitrogen steel is manufactured into
The complexity of this and manufacturing process remains high.
Invention content
In order to overcome the problems, such as that traditional smelting technology prepares that high nitrogen alloy steel technology difficulty is big, production cost is high, the present invention
Provide a kind of preparation method of high nitrogen alloy steel.
The present invention also provides a kind of using high nitrogen alloy steel made from above-mentioned preparation method.
In order to achieve the goal above, technical solution used by the preparation method of the high nitrogen alloy steel of the present invention is:
A kind of preparation method of high nitrogen alloy steel, includes the following steps:
1) mixed raw material powder is subjected to mechanical alloying processing, obtains composite granule;The mixed raw material powder includes
Nitride powder, carbon source powder and iron powder;The carbon source powder is at least one of carbide powder, carbon dust;
2) by the composite granule compression moulding of gained, sintering, it is cooling to get.
Mechanical alloying, powder metallurgical technique are organically combined, pass through machine by the preparation method of the high nitrogen alloy steel of the present invention
Tool Alloying Treatment makes that mixed raw material powder tissue, ingredient is uniform, grain size is regular, and being then sintered again can quickly, efficiently
Ground obtains high nitrogen alloy steel, and effectively reduces production cost;After mixed raw material powder is carried out mechanical alloying processing procedure, close
Gold element is evenly distributed, and especially nitrogen is added as alloying element in low-alloy steel, and solid solution, Neng Gouqi are formed with matrix
To the effect of solution strengthening, the intensity of low-alloy steel is effectively promoted;And nitride particles Dispersed precipitate plays dislocation, crystal boundary
To pinning effect, matrix strength and hardness are effectively improved, control crystal grain is grown up, and high performance high nitrogen alloy steel is finally obtained;This
Outside, moreover it is possible to increase substantially the content of the nitrogen in low-alloy steel, obtain the high nitrogen of mechanical property and excellent anti-corrosion performance
Steel alloy.
The valuable fixed nitrogen alloying element such as excessive Cr, Ni need not be added just in the preparation method of the high nitrogen alloy steel of the present invention
The nitrogen element content in steel can be effectively promoted, the manufacture crafts such as low-alloy steel foundry alloy melting, powder by atomization are not needed yet, it can
Effectively reduce high nitrogen steel production cost.The present invention high nitrogen alloy steel preparation method, suitable for prepare low-alloy high nitrogen steel,
Alloy high nitrogen steel and high alloy high nitrogen steel.The low-alloy high nitrogen steel refers to that total alloying element content is less than 5%, nitrogen element content
For 0.08~0.1% steel.The middle alloy high nitrogen steel refers to that total alloying element content is not less than 5% and is not higher than 10%, nitrogen
The steel that constituent content is 0.1~0.4%.The high alloy high nitrogen steel refers to that total alloying element content is higher than 10%, and nitrogen contains
Steel of the amount more than 0.4%.
Mechanical alloying processing carries out under vacuum or atmosphere protection.Compression moulding, sintering process are in vacuum or atmosphere
Protection is lower to be carried out.Mechanical alloying processing, compression moulding, sintering are carried out under atmosphere protection or vacuum, can prevent preparation
Alloying element loses caused by the reasons such as oxidation in the process so that this method is more smart to the Composition Control of high nitrogen alloy steel
It is accurate.
Preferably, the mixed raw material powder further include alloying element simple substance powder and/or alloying element between formed
Compound powder.The simple substance powder of alloying element refers to the simple substance powder of the alloying element in addition to carbon and nitrogen.It closes
The powder of the compound formed between gold element refers to the compound powder between the alloying element in addition to carbon and nitrogen.
In mixed raw material powder simultaneously the simple substance powder containing alloying element and formed between alloying element compound powder when, composition
The alloying element of simple substance powder can be one or more in the alloying element for be formed compound, also can be totally different to be formed
The alloying element of compound.
The average grain diameter of the mixed raw material powder is 0.1~100 μm.
The nitride powder is aluminium nitride, boron nitride, silicon nitride, titanium nitride, zirconium nitride, chromium nitride, nitrogenized manganese, nitridation
At least one of vanadium, nitrided ferromanganese, nitrided ferro-chromium, rare earth nitride.
The carbide powder is silicon carbide, manganess carbide, chromium carbide, molybdenum carbide, tungsten carbide, vanadium carbide, boron carbide, carbonization
At least one of titanium, zirconium carbide, niobium carbide, ramet, high carbon ferro-chrome, high carbon ferromanganese.
The simple substance powder is silica flour, manganese powder, chromium powder, nickel powder, molybdenum powder, vanadium powder, aluminium powder, copper powder, titanium valve, tungsten powder, boron powder
At least one of.
The compression moulding is sintered to hot pressed sintering.Hot pressed sintering can improve the consistency of high nitrogen alloy steel.It is pressed into
Type, sintering other than the process of compression moulding and sintering is completed at the same time by the technique that hot pressed sintering may be used, can also first by
Composite granule compression moulding, is then sintered again.
The hot pressed sintering be by composite granule at 1000~1280 DEG C, 5~70MPa 10~300min of heat-insulation pressure keeping.
Preferably, the time that heat-insulation pressure keeping is carried out during hot pressed sintering is 20~120min.
Before hot pressed sintering, composite granule is first kept the temperature to 10~120min at 800~1000 DEG C.It, will be compound before hot pressed sintering
Powder is kept the temperature at 800~1000 DEG C, is contributed to the abundant diffusion of each element in composite granule, is promoted the uniform of component distributing
Degree.
The mechanical alloying processing is ball milling.In mechanical milling process, protective gas is filled in ball grinder.It is filled in ball grinder
The protective gas entered is argon gas or nitrogen.The pressure that protective gas is filled in ball grinder is 0.5~10MPa.
The material ball ratio of the ball milling is 1:5~10.The time of the ball milling is 0.5~70h.The ball milling is high-energy ball milling
Before mixed raw material powder is carried out ball milling, mixed raw material powder is first subjected to batch mixing.It first will mixing original before ball milling
It is sufficiently mixed with component in feed powder body, helps to improve the matrix strength and hardness of gained high nitrogen alloy steel.
Technical solution is used by the high nitrogen alloy steel of the present invention:
It is a kind of using high nitrogen alloy steel made from above-mentioned preparation method.
The high nitrogen alloy steel of the present invention, nitride particles Dispersed precipitate play pinning effect, Neng Gouyou to dislocation, crystal boundary
Effect improves matrix strength and hardness, and size of microcrystal is small, has higher plasticity and toughness.
Specific implementation mode
Below in conjunction with specific implementation mode, the following further describes the technical solution of the present invention.
Embodiment 1
The high nitrogen alloy steel of the present embodiment is 42CrMoN low-alloy high nitrogen steels, mainly by the element of following mass percent
Composition:C 0.4%, Cr 1.5%, Mn 1.2%, Mo 0.3%, Si 0.3%, B 0.004%, remaining for Fe, N and it is a small amount of not
Evitable impurity;Preparation method includes the following steps:
1) according to the composition of mixed raw material powder in table 1, the chromium carbide power of formula ratio, aluminium nitride powder, silicon carbide are taken
The average grain diameter of powder, boron nitride powder, molybdenum carbide powder, chromium nitride powder, manganese powder and iron powder, each powder is 0.1 μm, dress
Enter in batch mixer, with the rotating speed batch mixing 2h of 48r/min, obtains mixed raw material powder;
Per the composition of kg mixed raw material powders in 1 embodiment 1 of table
2) it is 10 according to ratio of grinding media to material:1 ratio takes mixed raw material powder to be fitted into ball grinder, abrading-ball is added, in ball grinder
Middle applying argon gas is to 2MPa;Ball grinder is attached to ball milling 30h on planetary ball mill, obtains composite granule;In mechanical milling process, per ball
The full 1h of mill, stops 10min (dwell time is not counted in Ball-milling Time), then reversely rotates and continues ball milling;
3) composite granule is fitted into hot pressing die, is then charged into vacuum sintering funace, vacuumized, heat, wait for temperature
Degree keeps the temperature 2h when rising to 1000 DEG C, then heats to 1100 DEG C, and pressurization waits for that pressure rises to 40MPa, heat-insulation pressure keeping 2h, cooling, takes
Go out to get.
The high nitrogen alloy steel of the present embodiment is made using the preparation method of the present embodiment.
Embodiment 2
The high nitrogen alloy steel of the present embodiment is 20CrMnTiN low-alloy high nitrogen steels, mainly by the member of following mass percent
Element composition:C 0.2%, Cr 1.3%, Mn 1.1%, Ti 0.1%, remaining is Fe, N and a small amount of inevitable impurity;It is made
Preparation Method includes the following steps:
1) it according to the composition of mixed raw material powder in table 2, takes the carbon dust of formula ratio, nitridation chromium powder, nitrogenized manganese powder, nitrogenize
The average grain diameter of titanium valve and iron powder, each powder is 25 μm, is fitted into batch mixer, with the rotating speed batch mixing 10min of 48r/min, is obtained
To mixed raw material powder;
Per the composition of kg mixed raw material powders in 2 embodiment 2 of table
Component | Carbon dust (C) | Chromium nitride (CrN) | Nitrogenized manganese (MnN) | Titanium nitride (TiN) | Iron powder (Fe) |
Quality/g | 2 | 16.5 | 12.57 | 1.28 | 967.65 |
2) it is 7 according to ratio of grinding media to material:1 ratio takes mixed raw material powder to be fitted into ball grinder, abrading-ball is added, in ball grinder
Inflated with nitrogen is to 0.5MPa;Ball grinder is attached to ball milling 0.5h on planetary ball mill, obtains composite granule;In mechanical milling process, often
Ball milling expires 1h, stops 10min (dwell time is not counted in Ball-milling Time), then reversely rotates and continues ball milling;
3) composite granule is fitted into hot pressing die, is then charged into vacuum sintering funace, vacuumized, heat, wait for temperature
Degree keeps the temperature 20min when rising to 800 DEG C, then heats to 1280 DEG C, and pressurization waits for that pressure rises to 5MPa, heat-insulation pressure keeping 5h, cooling,
Take out to get.
The high nitrogen alloy steel of the present embodiment is made using the preparation method of the present embodiment.
Embodiment 3
The high nitrogen alloy steel of the present embodiment is 09Mn2N low-alloy high nitrogen steels, mainly by the element group of following mass percent
At:C 0.11%, Si 0.4%, Mn 1.8%, remaining is Fe, N and a small amount of inevitable impurity;Preparation method include with
Lower step:
1) according to the composition of mixed raw material powder in table 3, carbon dust, nitrogenized manganese powder, silica flour and the iron powder of formula ratio are taken, respectively
The average grain diameter of powder is 75 μm, is fitted into batch mixer, with the rotating speed batch mixing 4h of 48r/min, obtains mixed raw material powder;
Per the composition of kg mixed raw material powders in 3 embodiment 3 of table
Component | Carbon dust (C) | Nitrogenized manganese (MnN) | Silicon (Si) | Iron powder |
Quality/g | 1.1 | 22.58 | 4 | 972.32 |
2) it is 5 according to ratio of grinding media to material:1 ratio takes mixed raw material powder to be fitted into ball grinder, abrading-ball is added, in ball grinder
Inflated with nitrogen is to 10MPa;Ball grinder is attached to ball milling 10h on planetary ball mill, obtains composite granule;In mechanical milling process, per ball
The full 1h of mill, stops 10min (dwell time is not counted in Ball-milling Time), then reversely rotates and continues ball milling;
3) composite granule is fitted into hot pressing die, is then charged into vacuum sintering funace, vacuumized, heat, wait for temperature
Degree keeps the temperature 10min when rising to 900 DEG C, then heats to 1000 DEG C, pressurization, waits for that pressure rises to 70MPa, heat-insulation pressure keeping 10min, cold
But, take out to get.
The high nitrogen alloy steel of the present embodiment is made using the preparation method of the present embodiment.
Embodiment 4
The high nitrogen alloy steel of the present embodiment is alloy high nitrogen steel in middle manganese, mainly by the element group of following mass percent
At:C0.30%, Si 0.25%, Mn 5.5%, Cr 0.4%, remaining is Fe, N and a small amount of inevitable impurity;It is prepared
Method includes the following steps:
1) according to the composition of mixed raw material powder in table 4, carbon dust, nitrogenized manganese powder, silica flour, the nitrided ferro-chromium of formula ratio are taken
The average grain diameter of powder and iron powder, each powder is 35 μm, is fitted into batch mixer, and with the rotating speed batch mixing 4h of 60r/min, it is former to obtain mixing
Feed powder body;
Per the composition of kg mixed raw material powders in 4 embodiment 4 of table
Component | Carbon dust (C) | Nitrogenized manganese (MnN) | Silicon (Si) | Chromium nitride (CrN) | Iron |
Quality/g | 3 | 69 | 2.5 | 5.08 | 920.42 |
2) it is 7 according to ratio of grinding media to material:1 ratio takes mixed raw material powder to be fitted into ball grinder, abrading-ball is added, in ball grinder
Inflated with nitrogen is to 10MPa;Ball grinder is attached to ball milling 30h on planetary ball mill, obtains composite granule;In mechanical milling process, per ball
The full 1h of mill, stops 10min (dwell time is not counted in Ball-milling Time), then reversely rotates and continues ball milling;
3) composite granule is fitted into hot pressing die, is then charged into vacuum sintering funace, vacuumized, heat, wait for temperature
Degree keeps the temperature 10min when rising to 900 DEG C, then heats to 1000 DEG C, pressurization, waits for that pressure rises to 70MPa, heat-insulation pressure keeping 10min, cold
But, take out to get.
The high nitrogen alloy steel of the present embodiment is made using the preparation method of the present embodiment.
Embodiment 5
The high nitrogen alloy steel of the present embodiment is Cr12MoVN high alloy high nitrogen steels, mainly by the element of following mass percent
Composition:C 1.50%, Si 0.4%, Mn 0.4%, Cr 12.5%, V 0.25, Mo 0.50, remaining is Fe, N and on a small quantity can not
The impurity avoided;Preparation method includes the following steps:
1) according to the composition of mixed raw material powder in table 5, carbon dust, nitrogenized manganese powder, silica flour and the iron powder of formula ratio are taken, respectively
The average grain diameter of powder is 75 μm, is fitted into batch mixer, with the rotating speed batch mixing 4h of 48r/min, obtains mixed raw material powder;
Per the composition of kg mixed raw material powders in 5 embodiment 5 of table
2) it is 5 according to ratio of grinding media to material:1 ratio takes mixed raw material powder to be fitted into ball grinder, abrading-ball is added, in ball grinder
Inflated with nitrogen is to 10MPa;Ball grinder is attached to ball milling 10h on planetary ball mill, obtains composite granule;In mechanical milling process, per ball
The full 1h of mill, stops 10min (dwell time is not counted in Ball-milling Time), then reversely rotates and continues ball milling;
3) composite granule is fitted into hot pressing die, is then charged into vacuum sintering funace, vacuumized, heat, wait for temperature
Degree keeps the temperature 10min when rising to 900 DEG C, then heats to 1000 DEG C, pressurization, waits for that pressure rises to 70MPa, heat-insulation pressure keeping 10min, cold
But, take out to get.
The high nitrogen alloy steel of the present embodiment is made using the preparation method of the present embodiment.
Experimental example
The grain size of the high nitrogen alloy steel of embodiment 1 and embodiment 5 and performance are tested respectively, and with conventional cast
As a comparison, test result is shown in Table 6 to the 42CrMo and Cr12MoV of method production.
Grain size, average hardness and the average impact flexibility of the different steel grades of table 6
By data in table 6 it is found that the high nitrogen alloy steel of embodiment 1 and embodiment 5 has the crystal grain of fine uniform, and have
There are preferable hardness and impact flexibility.
Claims (10)
1. a kind of preparation method of high nitrogen alloy steel, it is characterised in that:Include the following steps:
1) mixed raw material powder is subjected to mechanical alloying processing, obtains composite granule;The mixed raw material powder includes nitridation
Powder, carbon source powder and iron powder;The carbon source powder is at least one of carbide powder, carbon dust;
2) by the composite granule compression moulding of gained, sintering, it is cooling to get.
2. the preparation method of high nitrogen alloy steel according to claim 1, it is characterised in that:The mixed raw material powder also wraps
Include the compound powder formed between the simple substance powder and/or alloying element of alloying element.
3. the preparation method of high nitrogen alloy steel according to claim 1, it is characterised in that:The nitride powder is nitridation
Aluminium, boron nitride, silicon nitride, titanium nitride, zirconium nitride, chromium nitride, nitrogenized manganese, vanadium nitride, nitrided ferromanganese, nitrided ferro-chromium, rare earth nitrogen
At least one of compound.
4. the preparation method of high nitrogen alloy steel according to claim 1, it is characterised in that:The carbide powder is carbonization
Silicon, manganess carbide, chromium carbide, molybdenum carbide, tungsten carbide, vanadium carbide, boron carbide, titanium carbide, zirconium carbide, niobium carbide, ramet, high-carbon
At least one of ferrochrome, high carbon ferromanganese.
5. the preparation method of high nitrogen alloy steel according to claim 2, it is characterised in that:The simple substance powder be silica flour,
At least one of manganese powder, chromium powder, nickel powder, molybdenum powder, vanadium powder, aluminium powder, copper powder, titanium valve, tungsten powder, boron powder.
6. the preparation method of high nitrogen alloy steel according to claim 1, it is characterised in that:The compression moulding is sintered to
Hot pressed sintering.
7. the preparation method of high nitrogen alloy steel according to claim 6, it is characterised in that:The hot pressed sintering is will be compound
Powder 10~300min of heat-insulation pressure keeping at 1000~1280 DEG C, 5~70MPa.
8. the preparation method of high nitrogen alloy steel according to claim 7, it is characterised in that:It, first will be compound before hot pressed sintering
Powder keeps the temperature 10~120min at 800~1000 DEG C.
9. the preparation method of high nitrogen alloy steel according to claim 1, it is characterised in that:The mechanical alloying is handled
Ball milling;In mechanical milling process, protective gas is filled in ball grinder.
10. high nitrogen alloy steel made from a kind of preparation method using as described in any one of claim 1~9.
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CN110343943A (en) * | 2019-07-01 | 2019-10-18 | 山东钢铁股份有限公司 | A kind of high nitrogen alloy hardening agent and its application |
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CN116790959A (en) * | 2023-08-23 | 2023-09-22 | 江苏美特林科特殊合金股份有限公司 | In-situ self-generated micro-nano double-scale nitride reinforced superalloy and preparation method thereof |
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Application publication date: 20181016 |