CN113136539A - Method for accelerating plasma nitriding assisted by rare earth compound - Google Patents

Method for accelerating plasma nitriding assisted by rare earth compound Download PDF

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Publication number
CN113136539A
CN113136539A CN202110322311.XA CN202110322311A CN113136539A CN 113136539 A CN113136539 A CN 113136539A CN 202110322311 A CN202110322311 A CN 202110322311A CN 113136539 A CN113136539 A CN 113136539A
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rare earth
earth compound
plasma nitriding
sample
assisted
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杨阳
张世宏
周祥
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Anhui University of Technology AHUT
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Anhui University of Technology AHUT
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

The invention relates to the technical field of plasma nitriding, in particular to a rare earth compound auxiliary plasma nitriding technology, which comprises the steps of firstly polishing a sample to a mirror surface and cleaning the sample, then preparing a rare earth compound precursor solution, preparing a rare earth compound film on the surface of an alloy by using a suspension coating method or a blade coating method, and finally carrying out plasma auxiliary nitriding technical treatment on the alloy; the method for accelerating plasma nitriding with the assistance of the rare earth compound solves the problems that the temperature is increased to increase the thickness of a carburized layer during plasma nitriding, so that the crystal grains of a nitrided layer grow, the energy consumption is increased, and the production efficiency is reduced.

Description

Method for accelerating plasma nitriding assisted by rare earth compound
Technical Field
The invention relates to the technical field of plasma nitriding, in particular to a method for assisting in accelerating plasma nitriding by using a rare earth compound.
Background
Alloy materials such as steel materials, titanium alloy materials and the like are widely applied to various fields such as machinery, automobiles, aerospace and the like due to excellent mechanical properties. In order to improve the service performance of the materials, a plasma nitriding technology is applied to improve the hardness, the frictional wear performance, the corrosion resistance, the fatigue performance and the like of the materials. The final service performance of the alloy material directly depends on the thickness and performance of the infiltrated layer, and particularly the fatigue performance depends on the thick infiltrated layer. The traditional methods for increasing the thickness of the nitriding layer are to increase the nitriding temperature and prolong the nitriding time, and from the material performance aspect, the methods can cause the growth of the crystal grains of the nitriding layer and reduce the performance of the nitriding layer; from a process perspective, these approaches increase energy consumption and reduce production efficiency. Therefore, the development of a new method for accelerating the plasma nitriding has important application value.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
The invention aims to solve the problems that the grain growth of a nitrided layer is caused, the energy consumption is increased and the production efficiency is reduced in order to improve the diffusion layer during plasma nitriding, and provides a method for assisting in accelerating the plasma nitriding by using a rare earth compound.
In order to achieve the purpose, the invention discloses a method for accelerating plasma nitriding assisted by a rare earth compound, which comprises the following steps:
s1: grinding the sample by using sand paper, further polishing the sample to a mirror surface state, and cleaning the sample in acetone or alcohol solution;
s2: preparing a rare earth compound precursor solution;
s3: coating the rare earth compound precursor solution obtained in the step S2 on the surface of the sample obtained in the step S1 to prepare a rare earth compound film;
s4: and (4) putting the sample obtained in the step (S3) into a furnace, introducing nitrogen-containing gas and protective gas, and performing plasma nitriding on the sample.
The sample in the step S1 is one of steel, titanium alloy and aluminum alloy.
The rare earth compound precursor solution in step S2 includes a perovskite-type compound; the perovskite type compound is LaFeO3、LaMnO3、LaCoO3、CeFeO3、CeMnO3And LaCoO3Any one or more mixtures thereof.
In the step S3, the rare earth compound precursor solution is coated on the surface of the sample in a suspension coating or blade coating mode; the thickness of the prepared film is less than 5 mu m.
The nitrogen-containing gas in the step S4 is one of ammonia gas or nitrogen gas; the protective gas is one of hydrogen or argon.
The rare earth compound film must be bombarded by plasma to be broken during the plasma nitriding process in the step S4; the adopted method is to carry out protective gas pre-bombardment cleaning on the sample or prolong the nitriding time of the plasma.
The plasma nitriding method comprises pulse glow plasma nitriding, hollow cathode plasma nitriding, hot wire arc plasma nitriding, cathode arc plasma nitriding and the like.
Compared with the prior art, the invention has the beneficial effects that: aiming at the low nitriding efficiency of the material, the invention provides a method for accelerating plasma nitriding by the aid of a rare earth compound, which can improve the nitriding efficiency of the material, reduce the nitriding cost and energy consumption, improve the hardness of a plasma nitriding surface layer, improve the wear resistance, increase the thickness of a plasma nitriding layer assisted by the rare earth compound at the same temperature and time, ensure that the gradient distribution of the hardness of the nitriding layer is more uniform, and is favorable for improving the bearing capacity of a material part.
Drawings
FIG. 1 is a surface micro-topography of 38CrMoAl steel after rare earth assisted plasma nitriding in example 1 of the present invention;
FIG. 2 shows the metallographic microstructure after the rare earth-assisted plasma nitriding of 38CrMoAl steel in example 1 of the present invention and the plasma nitriding of 38CrMoAl steel in the comparative example;
FIG. 3 is the microhardness distribution after rare earth assisted plasma nitriding of 38CrMoAl steel in example 1 of the present invention and plasma nitriding of 38CrMoAl steel in a comparative example;
FIG. 4 is the microhardness distribution after rare earth assisted plasma nitriding of 38CrMoAl steel in example 2 of the present invention and plasma nitriding of 38CrMoAl steel in a comparative example;
FIG. 5 is the microhardness distribution after rare earth assisted plasma nitriding of 38CrMoAl steel in example 3 of the invention and plasma nitriding of 38CrMoAl steel in a comparative example.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
Step 1: grinding the 38CrMoAl steel sample by using sand paper, further polishing the sample to a mirror surface state, and cleaning the sample in acetone or alcohol solution;
step 2: weighing La (NO)3)3·6H2O(99.99％，0.02mol)、Fe(NO3)3·9H2O (98.5%, 0.02mol) to ensure that the molar ratio of lanthanum ions to iron ions is 1:1, adding 50mL of distilled water, continuously stirring to dissolve the main salt, adding excessive citric acid (10g), stirring for two hours to fully complex the iron ions and the lanthanum ions, and standing for 48 hours to form a transparent rare earth compound LaFeO3Precursor solution;
and step 3: preparing a rare earth compound film (the thickness is less than 5 mu m) on the surface of the sample in the step 1 by using a suspension coating method (a suspension coater 4000 r/min);
and 4, step 4: and (3) putting the sample into a furnace, introducing nitrogen and hydrogen, and performing plasma nitriding on the sample coated in the step three, wherein the nitriding temperature is 520 ℃ and the nitriding time is 4 hours.
The surface micro-morphology of the obtained 38CrMoAl steel subjected to the rare earth auxiliary plasma nitriding is shown in figure 1, and the fact that a rare earth compound film on the surface has cracks is found, EDS shows that no rare earth element exists in a crack area (a position), and a small film area (b position) contains elements such as La, O and the like.
Example 2
Step 1: grinding the 38CrMoAl steel sample by using sand paper, further polishing the sample to a mirror surface state, and cleaning the sample in acetone or alcohol solution;
step 2: weighing La (NO)3)3·6H2O(99.99％，0.02mol)、Fe(NO3)3·9H2O (98.5%, 0.02mol) to make the molar ratio of lanthanum ion and iron ion 1:1, adding 50ml distilled water, stirring continuously to dissolve main salt, adding excessive citric acid (10g), stirring for two hours to make iron ion and lanthanum ion fully complex, standing for 48 hours to form transparent rare earth compound LaFeO3Precursor solution;
and step 3: preparing a rare earth compound film (the thickness is less than 5 mu m) on the surface of the sample in the step 1 by using a suspension coating method (a suspension coater is 6000 r/min);
and 4, step 4: and (3) putting the sample into a furnace, introducing nitrogen and hydrogen, and performing plasma nitriding on the sample coated in the step three, wherein the nitriding temperature is 520 ℃ and the nitriding time is 4 hours.
Example 3
Step 1: grinding the 38CrMoAl steel sample by using sand paper, further polishing the sample to a mirror surface state, and cleaning the sample in acetone or alcohol solution;
step 2: weighing Ce (NO)3)3·6H2O(99.99％，0.02mol)、Fe(NO3)3·9H2O (98.5%, 0.02mol) to make the molar ratio of lanthanum ion and iron ion 1:1, adding 50ml distilled water, stirring continuously to dissolve the main salt, adding excessive citric acid (10g), stirring for two hours to fully complex iron ion and cerium ion, standing for 48 hours to form a transparent rare earth compound CeFeO3Precursor solution;
and step 3: preparing a rare earth compound film (the thickness is less than 5 mu m) on the surface of the sample in the step 1 by using a suspension coating method;
and 4, step 4: and (3) putting the sample into a furnace, introducing nitrogen and hydrogen, and performing plasma nitriding on the sample coated in the step three, wherein the nitriding temperature is 520 ℃ and the nitriding time is 4 hours.
Comparative example
Step 1: grinding the 38CrMoAl steel sample by using sand paper, further polishing the sample to a mirror surface state, and cleaning the sample in acetone or alcohol solution;
step 2: and (3) putting the sample into a furnace, introducing nitrogen and hydrogen, and performing plasma nitriding on the sample in the step (1), wherein the nitriding temperature is 520 ℃ and the nitriding time is 4 h.
The appearance of the metallographic gastric tube after the 38CrMoAl steel rare earth auxiliary plasma nitriding in the example 1 and the comparative example is shown in FIG. 2, wherein (a) is the metallographic microstructure after the 38CrMoAl steel rare earth auxiliary plasma nitriding, and (b) is the metallographic microstructure after the 38CrMoAl steel plasma nitriding, and the layer thickness of the rare earth auxiliary plasma nitriding layer in the example is obviously shown in the figure.
The microhardness distributions after the rare earth-assisted plasma nitriding of the 38CrMoAl steel in example 1 and the plasma nitriding of the 38CrMoAl steel in the comparative example are shown in FIG. 3, and it can be seen that the surface hardness of the carburized layer is higher and the carburized layer is thicker in the rare earth-assisted plasma nitriding in example 1.
The microhardness distribution after the rare earth-assisted plasma nitriding of the 38CrMoAl steel in example 2 and the plasma nitriding of the 38CrMoAl steel in the comparative example is shown in FIG. 4, and it can be seen that the surface hardness of the carburized layer is higher and the carburized layer is thicker in the rare earth-assisted plasma nitriding in example 2.
The microhardness distributions after the rare earth-assisted plasma nitriding of the 38CrMoAl steel in example 3 and the plasma nitriding of the 38CrMoAl steel in the comparative example are shown in FIG. 5, and it can be seen that the surface hardness of the carburized layer is higher and the carburized layer is thicker in the rare earth-assisted plasma nitriding in example 3.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method for accelerating plasma nitriding assisted by rare earth compounds is characterized by comprising the following steps:
s1: polishing the sample, further polishing the sample to a mirror surface state, and cleaning the sample in acetone or alcohol solution;
s2: preparing a rare earth compound precursor solution;
s3: coating the rare earth compound precursor solution obtained in the step S2 on the surface of the sample obtained in the step S1 to prepare a rare earth compound film;
s4: and (4) putting the sample obtained in the step (S3) into a furnace, introducing nitrogen-containing gas and protective gas, and performing plasma nitriding on the sample.
2. The method for accelerating plasma nitriding assisted by a rare earth compound according to claim 1, wherein the sample in step S1 is one of steel, titanium alloy, and aluminum alloy.
3. The method for accelerating plasma nitridation with the aid of a rare earth compound, according to claim 1, wherein said rare earth compound precursor solution in step S2 includes a perovskite-type compound.
4. The method for accelerated plasma nitridation aided by a rare earth compound according to claim 3, wherein the perovskite-type compound is LaFeO3、LaMnO3、LaCoO3、CeFeO3、CeMnO3And LaCoO3Any one or more mixtures thereof.
5. The method for accelerating plasma nitriding assisted by a rare earth compound according to claim 1, wherein the rare earth compound precursor solution is applied to the surface of the sample by means of suspension coating or blade coating in step S3.
6. The method for accelerating plasma nitriding assisted by a rare earth compound according to claim 1, wherein the thickness of the film prepared in step S3 is less than 5 μm.
7. The method for accelerating plasma nitriding assisted by a rare earth compound according to claim 1, wherein the nitrogen-containing gas in step S4 is one of ammonia gas and nitrogen gas.
8. The method for accelerating plasma nitriding with assistance of rare earth compounds according to claim 1, wherein the shielding gas in step S4 is one of hydrogen or argon.
9. The method for accelerating plasma nitriding assisted by a rare earth compound according to claim 1, wherein the rare earth compound film must be bombarded to be broken by plasma during plasma nitriding in step S4.
10. The method for accelerating plasma nitriding assisted by rare earth compounds according to claim 9, wherein the bombardment rupture of the rare earth compound film in step S4 is performed by performing protective gas pre-bombardment cleaning on the sample or prolonging the plasma nitriding time.
CN202110322311.XA 2021-03-25 2021-03-25 Method for accelerating plasma nitriding assisted by rare earth compound Pending CN113136539A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413642A (en) * 1992-11-27 1995-05-09 Alger; Donald L. Processing for forming corrosion and permeation barriers
CN105483604A (en) * 2015-12-30 2016-04-13 武汉材料保护研究所 Catalytic permeation method for increasing austenite stainless steel low-temperature gas carburizing speed
CN106967945A (en) * 2016-01-14 2017-07-21 杭州巨星科技股份有限公司 Rare earth-sulfide for stainless steel urges the QPQ techniques for oozing low temperature QPQ compositions and stainless steel knife altogether
CN110747430A (en) * 2019-10-25 2020-02-04 西南交通大学 Low-pressure gas rapid nitriding method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413642A (en) * 1992-11-27 1995-05-09 Alger; Donald L. Processing for forming corrosion and permeation barriers
CN105483604A (en) * 2015-12-30 2016-04-13 武汉材料保护研究所 Catalytic permeation method for increasing austenite stainless steel low-temperature gas carburizing speed
CN106967945A (en) * 2016-01-14 2017-07-21 杭州巨星科技股份有限公司 Rare earth-sulfide for stainless steel urges the QPQ techniques for oozing low temperature QPQ compositions and stainless steel knife altogether
CN110747430A (en) * 2019-10-25 2020-02-04 西南交通大学 Low-pressure gas rapid nitriding method

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