CN112195474B - Metal surface modification process and application thereof - Google Patents
Metal surface modification process and application thereof Download PDFInfo
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- CN112195474B CN112195474B CN202011095781.9A CN202011095781A CN112195474B CN 112195474 B CN112195474 B CN 112195474B CN 202011095781 A CN202011095781 A CN 202011095781A CN 112195474 B CN112195474 B CN 112195474B
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
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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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
- C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
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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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
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Abstract
The invention relates to the technical field of metal surface modification, in particular to a metal surface modification process and application thereof. Which comprises the following steps: (1) carrying out extrusion treatment on the surface of a metal material; (2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent; (3) Spraying a nano conditioning additive on the surface of the metal material; (4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive; (5) Carrying out low-temperature tempering treatment at 120-160 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 51-75 wt% of nano metal powder, 10-45 wt% of dispersant composite material and 0.01-5 wt% of auxiliary agent. Through the surface treatment process provided by the invention, a micron-sized non-static surface layer can be formed on the surface of a metal workpiece, so that the characteristics of hardness, wear resistance and the like of the surface of the workpiece are obviously improved, the wear loss of the workpiece is reduced to be one-fifteenth lower than that of the original workpiece, and the service life of the workpiece is obviously prolonged.
Description
Technical Field
The invention relates to the technical field of metal surface modification, in particular to a metal surface modification process and application thereof.
Background
The rapid development of economy creates a huge market demand for industrial products, and at the same time, increasingly higher requirements are placed on the product performance. In the process of continuously improving the product quality, the surface quality and the internal quality of the product are found to have important influence on the reliability and the service life of parts or products. For example, bearing parts require high hardness, uniformity of hardness, dynamic and static strength, high contact fatigue strength, certain toughness, certain hardenability, and have to reduce internal defects that are liable to cause flaking, and also have to prevent structural changes and dimensional changes caused by various stresses over a long period of time, and since many bearing parts are used under environmental conditions that do not allow the use of additives such as lubricating oil and grease, the parts are liable to be damaged without dry friction operation under high temperature environments.
The surface strengthening technology is a high-tech technology means which comprehensively applies knowledge of materials science, tribology, polymer chemistry, high-energy physics and the like. Foreign practice proves that the surface strengthening technology of the metal workpiece is an effective means for prolonging the service life of the workpiece, reducing the friction torque of the workpiece such as a bearing and the like and improving the reliability of the bearing. The surface of the metal part is strengthened by various methods, such as carburizing, nitriding, surface coating, physical or chemical deposition, surface alloying and the like, so as to adjust the surface components; some of them achieve surface hardening by phase change, including ordinary flame quenching and induction quenching. For conventional bearing parts, the surface treatment methods commonly used at present are chemical deposition, electroplating and the like. However, these approaches are costly and the effects of wear resistance are to be improved.
Disclosure of Invention
In view of the above technical problems, a first aspect of the present invention provides a metal surface modification process, which includes the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out low-temperature tempering treatment at 120-160 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 51-75 wt% of nano metal powder, 10-45 wt% of dispersant composite material and 0.01-5 wt% of auxiliary agent.
As a preferable technical solution, the nano metal powder includes one or more selected from nano chromium, nano copper, nano zinc, nano molybdenum, nano nickel, nano tin and nano iron.
As a preferable technical scheme, the particle size of the nano metal powder is not higher than 50nm.
As a preferable technical scheme, the nano metal powder is composed of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel; the weight ratio of the components is (2.2-3): (1-1.5): (1-1.2): (0.2-0.6): (0.2-0.5).
As a preferable technical scheme, the particle size of the nano chromium is 35-45 nm; the particle size of the nano molybdenum and the nano nickel is not higher than 20nm.
As a preferable technical scheme, the particle diameters of the nano copper and the nano zinc are the same.
As a preferable technical proposal, the laser power of the laser irradiation in the step (4) is 1.5 to 2.2kW.
As a preferable embodiment, the laser scanning speed of the laser irradiation in the step (4) is 5 to 20mm/s.
As a preferred technical solution, the dispersant composite comprises a metal-organic framework material and an anionic surfactant.
A second aspect of the invention provides the use of the metal surface modification process as described above in the field of mechanical articles.
Has the beneficial effects that: through the surface treatment process provided by the invention, a micron-sized non-static surface layer can be formed on the surface of a metal workpiece, so that the characteristics of hardness, wear resistance and the like of the surface of the workpiece are obviously improved, the wear loss of the workpiece is reduced to be one-fifteenth lower than that of the original workpiece, and the service life of the workpiece is obviously prolonged. In addition, by the process, the bonding force between the amorphous phase surface layer formed on the surface of the workpiece and the workpiece on the surface of the workpiece is also obviously improved, the phenomena of cracking, peeling and the like can not occur during use, and the wearability is stable. And through the process in the application, the corrosion resistance of the workpiece is further improved, and the service life is further prolonged.
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FIG. 1 is a graph showing the results of the friction coefficient and the timely temperature change with time in the high-temperature friction test of the part in experiment 2.
FIG. 2 is a graph showing the results of the friction coefficient and the timely temperature change with time in the high-temperature friction test of the part in experiment 1.
FIG. 3 is a graph showing the results of the experiment of friction coefficient of the part in experiment 3 in the high-temperature friction experiment and the change of the temperature in time with time.
FIG. 4 is a graph showing the results of the experiment of friction coefficient of the part of experiment 4 in the high temperature friction experiment and the change of the temperature in time with time.
FIG. 5 is an electron microscope image of the surface layer of the article of experiment 2.
FIG. 6 is an electron microscope image of the surface layer of the article of experiment 1.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including 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. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
The invention may take form in various alternative variations and step sequences, unless expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The first aspect of the invention provides a metal surface modification process, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material subjected to the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out low-temperature tempering treatment at 120-160 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 51-75 wt% of nano metal powder, 10-45 wt% of dispersant composite material and 0.01-5 wt% of auxiliary agent.
When the surface treatment is avoided for the metal part, the surface of the part is extruded firstly, a large amount of micro dislocation structures are formed inside the metal part through the extrusion treatment, the surface energy of the surface of the metal part is changed, the metal part can better interact with the nano conditioning additive components, the bonding force between an amorphous protective layer formed on the surface of the metal part and the surface of the metal part after the surface treatment process is improved, and the problems that the protective layer cracks with the surface of the metal part in the use process of the part and the like are solved. In the present invention, the extrusion treatment method is not particularly limited, and the extrusion treatment may be performed according to a conventional method. The metal material in the present invention is preferably steel material, including but not limited to 35GrMo, GCr15, 9Cr18, etc.
The organic solvent used for cleaning the surface of the metal material in the present invention is not particularly limited, and a conventional organic solvent known to those skilled in the art may be used for cleaning. Including but not limited to alcohol, gasoline, acetone, ethyl acetate and the like, and can also be added with organic acid/inorganic acid, organic alkali/inorganic alkali and other components according to actual needs to adjust the acidity and alkalinity of the cleaning agent so as to achieve good cleaning effect, and can also improve the cleaning efficiency by means of heating and the like so as to clean grease, oil stains and the like on the surface of the metal workpiece.
The spraying method of the nano conditioning additive in the present invention is not particularly limited, and the nano conditioning additive may be sprayed according to a method known to those skilled in the art. In addition, the nano conditioning additive can also be arranged on the surface of the metal material in a manual/automatic brushing mode and the like. In addition, the spraying thickness of the nano conditioning additive is not specially limited, and can be adjusted according to actual needs, and the spraying thickness can be 1-1000 microns; or 10-500 microns; or 20 to 400 microns; or 20 to 200 microns; or 20 to 100 microns; or 40 to 80 microns; or 50 to 60 microns.
The content of the nano metal powder in the nano conditioning additive is 51-75 wt%; or 10 to 60wt%; or 15 to 60wt%; or 20 to 50wt%; or 30 to 45wt%; or 35 to 40wt%. The specific choice of the nano metal powder in the invention is not particularly limited, and various metal powders known to those skilled in the art can be selected, and the nano metal powder in the invention comprises carbon-doped nano metal powder, and the doping content of carbon in the nano metal powder can be adjusted according to actual needs.
The nano metal powder in the invention refers to metal powder components with average grain diameter/size of about 500nm or less; in some preferred embodiments, the particle size of the nano-metal powder is no greater than 50nm; preferably, the particle size is not higher than 40nm. The particle size in the present invention is the average particle size of the powder well known to those skilled in the art.
In some embodiments, the nano-metal powder comprises one or more selected from nano-chromium, nano-copper, nano-zinc, nano-molybdenum, nano-nickel, nano-tin, and nano-iron.
In some preferred embodiments, the above-described nano metal powders are used in combination; preferably, the nanometer chromium, the nanometer copper, the nanometer zinc, the nanometer molybdenum and the nanometer nickel are used in combination.
In some preferred embodiments, the nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel; the weight ratio of the components is (2.2-3): (1-1.5): (1-1.2): (0.2-0.6): (0.2-0.5).
Further preferably, the content of the nano copper and the content of the nano zinc are the same.
Further preferably, the weight ratio of the nano chromium to the nano copper to the nano zinc to the nano molybdenum to the nano nickel is 2.6:1.2:1.2:0.4:0.3.
the applicant finds that the regulation and control of the components in the nano metal powder in the nano conditioning additive are beneficial to improving the content of an amorphous part of a film layer formed on the surface of a metal workpiece, so that the nano conditioning additive is quickly melted and covered on the surface of the metal workpiece to form the amorphous layer under the action of laser irradiation treatment, and the characteristics of hardness, wear resistance and the like of the surface of the workpiece are obviously improved. The applicant speculates that the five nano metals are melted under the action of laser irradiation, and in the process of re-cooling after the laser is removed, due to the fact that the lattice structures of the components and the energy required by crystallization are greatly different, the components are mutually restricted and are prevented from crystallizing, and under the rapid cooling, the components cannot be orderly arranged into specific lattices to form crystals, so that the content of an amorphous layer on the surface of a product is increased, and the characteristics of hardness, wear resistance and the like of the product are improved.
In some embodiments, the nanopowder comprises a large particle size nanopowder and a small particle size nanometal powder; in some embodiments, the nano-chromium is a large particle size nano-metal powder and the nano-molybdenum and nano-nickel are small particle size nano-metal powders.
In some preferred modes of execution, the average grain diameter of the nano chromium is 35-45 nm; the average grain diameter of the nano molybdenum and the nano nickel is not higher than 20nm.
In some preferred embodiments, the average particle size of the nano molybdenum and the nano nickel is 10 to 20nm.
In some embodiments, the particle size of the nano-copper and nano-zinc is the same.
In some preferred embodiments, the average particle size of the nano-copper and nano-zinc is 25 to 35nm.
The applicant finds that the adjustment of the particle size of specific nano metal powder in the nano conditioning additive is helpful for further improving the amorphous layer structure performance of the surface of a workpiece and improving the amorphous layer forming capability. Because the specific surface areas of the nanometer metal powders with different grain diameters are different and the heating capacities under the action of laser irradiation are different, the critical cooling speed parts required by the melting energy cooling and the amorphous phase formation are different, and when the five metal powders are adopted, the specific grain diameters are adopted, a certain balance can be achieved, the crystallization capacity of the metal phase is weakened, and the crystallization content is reduced.
The laser irradiation treatment in the invention is to irradiate the surface of the metal material for a specific time by adopting a certain power and laser, so as to heat and melt the surface of the metal material, and then cool the surface to form a protective layer, thereby improving the surface characteristics of the product.
In some embodiments, the laser power of the laser irradiation in step (4) is 1.5 to 2.2kW.
More preferably, the laser power for laser irradiation in step (4) is 1.8 to 2.0kW.
In some embodiments, the laser scanning speed of the laser irradiation in the step (4) is 5 to 20mm/s.
More preferably, the laser scanning speed of the laser irradiation in the step (4) is 5 to 10mm/s; further preferably, the scanning speed is 8mm/s.
The applicant finds that the laser power and the scanning speed in the laser irradiation process have a crucial influence on the amorphous phase content of the surface of a workpiece, when the power during laser irradiation is too high or too low, the amorphous layer structure performance of the surface of the workpiece is seriously reduced, and the amorphous phase content of the surface layer of the workpiece can be obviously improved and the wear resistance and other characteristics of the workpiece can be improved only under the power of 1.5-2.2 kW, particularly under the power of 1.8-2.0 kW and at the scanning speed of 5-10 mm per second. When the power is too low, the generated heat is less, so that the nano metal powder is not enough to be fully melted, a large amount of metal powder crystals remain on the surface layer of the workpiece, and the cooling speed is not fast enough after the laser is removed, so that the metal powder can form a complete crystal structure, and the surface layer formed on the surface of the workpiece is still a crystal phase which is easy to wear and has low hardness. When the laser power is too high, a thicker heat affected zone is formed on the surface of the workpiece under the action of laser, so that the amorphous phase formed in the nano conditioning additive is further crystallized, the content of the amorphous phase is reduced, and the structure performance of the amorphous phase structure is affected, thereby being not beneficial to the improvement of the characteristics of wear resistance and the like.
In some embodiments, the dispersant composite comprises a metal-organic framework material and an anionic surfactant.
The metal-organic framework material is a novel porous framework material formed by self-assembling metal ions and organic ligands, and generally has larger porosity and specific surface area.
In some embodiments, the metal-organic framework material has a particle size (average size) of no more than 10 μm.
Further preferably, the particle size (average size) of the metal-organic framework material is not higher than 5 μm.
In some preferred embodiments, the pore size of the metal-organic framework material is 1 to 1.5nm.
In some preferred embodiments, the metal ion in the raw material for preparing the metal-organic framework material is a divalent magnesium ion.
Further preferably, the organic ligand structure in the raw material for preparing the metal-organic framework material comprises a benzene ring.
Further, the organic ligand is a dicarboxylic acid comprising a benzene ring.
Furthermore, the organic ligand structure contains hydroxyl.
Further preferably, the organic ligand is 2, 5-dihydroxyterephthalic acid.
The metal-organic framework material of the present invention can be prepared according to methods well known to those skilled in the art, for example, by a method comprising the steps of:
dissolving 2.0mmo of magnesium chloride in 30-40 ml of DMF and mixed solvent, and mixing according to the weight ratio of magnesium chloride: the molar ratio of 2, 5-dihydroxyterephthalic acid is 1: (0.8-1.5), dissolving 2, 5-dihydroxyterephthalic acid in the solution, stirring for 45 minutes at normal temperature, transferring the mixture into a polytetrafluoroethylene lining, sealing, reacting in an oven at 130-150 ℃ for 18-48 hours, cooling to room temperature after the reaction is finished, ultrasonically washing the obtained product for several times by using deionized water, and drying to obtain the finished product.
The metal-organic framework material of the present invention can also be obtained from commercial sources, for example, MOF-74 of qiangsu xiaofeng nano materials science and technology ltd.
Applicants have discovered that the addition of certain levels of metal-organic framework materials as dispersant composites to a nano-conditioning additive can contribute to a significant improvement in the thickness and structural properties of the amorphous phase on the surface of the part. On one hand, probably because a large number of organic ligands on the metal-organic framework material structure can form a stable complexing system with a nano metal powder workpiece, the surface tension of a melt formed by melting the nano conditioning additive on the surface of the workpiece is reduced, so that the contact angle between the surface of the workpiece and a cladding layer workpiece is favorably improved, the nano conditioning additive can more uniformly form a stable cladding layer on the surface of the workpiece under the action of laser irradiation, and a surface layer with stable and uniform tissue performance is formed after the laser is removed. On the other hand, magnesium ions in the metal-organic framework material and specific groups such as hydroxyl groups and carboxyl groups in the organic ligand help to hinder the generation of crystal nuclei in a crystallization system, thereby contributing to the stability of an amorphous phase structure, the improvement of the content of the amorphous phase structure, and the characteristics of the surface layer, such as the bonding force with the surface of a product, the corrosion resistance and the like.
The anionic surfactant in the invention contains hydrophilic groups and hydrophobic groups in the structure, and can generate hydrophobic anions in water.
In some embodiments, the anionic surfactant is a mixture of a sulfonate and a fatty acid salt.
In some preferred embodiments, the fatty acid salt is an unsaturated fatty acid salt.
Further, the unsaturated fatty acid salt is potassium oleate.
In some preferred embodiments, the sulfonate salt is an alkylbenzene sulfonate salt.
Further, the alkylbenzene sulfonate is branched alkylbenzene sulfonate and/or linear alkylbenzene sulfonate.
Further, the alkylbenzene sulfonate is branched-chain sodium dodecyl benzene sulfonate. The branched-chain sodium dodecylbenzene sulfonate of the present invention can be obtained commercially, for example, BABSA sodium salt from Lossen chemical Co., ltd.
In some preferred embodiments, the weight ratio of the sulfonate to the fatty acid salt is (2-3): 1.
further preferably, the weight ratio of the sulfonate to the fatty acid salt is 2.2:1.
in some embodiments, the weight ratio of the metal-organic framework material to the anionic surfactant is 3:1.
the applicant finds that the regulation and control of the components and the proportion of the anionic surfactant in the dispersant composite material are beneficial to improving the wear resistance of a workpiece. Probably, the sulfonate and the fatty acid salt (especially the branched alkylbenzene sulfonate and the potassium oleate with the weight ratio of 2.2.
The auxiliary agents described in the present invention include antioxidants, metal corrosion inhibitors, friction modifiers.
The antioxidant is not particularly limited in the present invention, and various antioxidants known to those skilled in the art may be used, including but not limited to organic borate esters, aniline, dinonylbenzylamine, and the like.
The metal corrosion inhibitor of the present invention is not particularly limited, and various metal corrosion inhibitor components known to those skilled in the art may be selected, including, but not limited to, fatty acid amides, succinimides, borides of succinimides, and the like.
The friction modifier is not particularly limited in the present invention, and various types of anti-friction ingredients well known to those skilled in the art may be selected, including, but not limited to, boronated fatty acid esters, imidazole amine salts, benzotriazole fatty amine salts (CAS No.: 95-14-7), and the like.
A second aspect of the invention provides the use of the metal surface modification process as described above in the field of mechanical articles.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out 140 ℃ low-temperature tempering treatment on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 70wt% of nano metal powder, 28wt% of dispersant composite material and 2wt% of auxiliary agent. The laser power of laser irradiation in the laser irradiation treatment is 1.8kW, and the laser scanning speed is 8mm/s. The nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel, and the weight ratio of the nano metal powder is 2.6:1.2:1.2:0.4:0.3; the average grain size of the nano chromium is 40nm, the average grain size of the nano molybdenum is the same as that of the nano nickel and is 20nm, and the grain size of the nano copper is the same as that of the nano zinc and is 30nm.
The dispersant composite material is a mixture of a metal-organic framework material and an anionic surfactant, and the weight ratio of the dispersant composite material to the anionic surfactant is 3:1; the anionic surfactant is a mixture of sulfonate and fatty acid salt, and the weight ratio of the anionic surfactant to the fatty acid salt is 2.2:1, wherein the fatty acid is potassium oleate, and the sulfonate is branched-chain sodium dodecyl benzene sulfonate; the metal-organic framework material is MOF-74 of Jiangsu Xiancheng nano material science and technology Limited; the auxiliary agent consists of an antioxidant, a metal corrosion inhibitor and a friction modifier which are equal in weight, wherein the antioxidant is dinonyl benzylamine, the metal corrosion inhibitor is succinimide, and the friction modifier is benzotriazole fatty amine salt.
Example 2: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material subjected to the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out 140 ℃ low-temperature tempering treatment on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 70wt% of nano metal powder, 28wt% of dispersant composite material and 2wt% of auxiliary agent. The laser power of laser irradiation in the laser irradiation treatment is 2.0kW, and the laser scanning speed is 8mm/s. The nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel, and the weight ratio of the nano metal powder is 2.6:1.2:1.2:0.4:0.3; the average particle size of the nano chromium is 40nm, the average particle size of the nano molybdenum and the average particle size of the nano nickel are the same and are 20nm, and the average particle size of the nano copper and the average particle size of the nano zinc are the same and are 30nm.
The dispersant composite material is a mixture of a metal-organic framework material and an anionic surfactant, and the weight ratio of the dispersant composite material to the anionic surfactant is 3:1; the anionic surfactant is a mixture of sulfonate and fatty acid salt, and the weight ratio of the anionic surfactant to the fatty acid salt is 2.2:1, wherein the fatty acid is potassium oleate and the sulfonate is branched-chain sodium dodecyl benzene sulfonate; the metal-organic framework material is MOF-74 of Jiangsu Xiancheng nano material science and technology limited; the auxiliaries are the same as in example 1.
Example 3: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out low-temperature tempering treatment at 140 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 70wt% of nano metal powder, 28wt% of dispersant composite material and 2wt% of auxiliary agent. The laser power of laser irradiation in the laser irradiation treatment is 2.0kW, and the laser scanning speed is 8mm/s. The nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel, and the weight ratio of the nano metal powder is 2.6:1.2:1.2:0.4:0.3; the average particle size of the nano chromium is 40nm, the average particle size of the nano molybdenum and the average particle size of the nano nickel are the same and are 20nm, and the average particle size of the nano copper and the average particle size of the nano zinc are the same and are 30nm.
The dispersant composite is an anionic surfactant; the anionic surfactant is a mixture of sulfonate and fatty acid salt, and the weight ratio of the anionic surfactant to the fatty acid salt is 2.2:1, wherein the fatty acid is potassium oleate and the sulfonate is branched-chain sodium dodecyl benzene sulfonate; the auxiliaries are the same as in example 1.
Example 4: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out low-temperature tempering treatment at 140 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 70wt% of nano metal powder, 28wt% of dispersant composite material and 2wt% of auxiliary agent. The laser power of laser irradiation in the laser irradiation treatment is 2.0kW, and the laser scanning speed is 8mm/s. The nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel in a weight ratio of 2.6:1.2:1.2:0.4:0.3; the average particle size of the nano chromium is 40nm, the average particle size of the nano molybdenum and the average particle size of the nano nickel are the same and are 20nm, and the average particle size of the nano copper and the average particle size of the nano zinc are the same and are 30nm.
The dispersant composite material is a metal-organic framework material; the metal-organic framework material is MOF-74 of Jiangsu Xiancheng nano material science and technology limited; the auxiliaries are the same as in example 1.
Example 5: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out low-temperature tempering treatment at 140 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 70wt% of nano metal powder, 28wt% of dispersant composite material and 2wt% of auxiliary agent. The laser power of laser irradiation in the laser irradiation treatment is 2.0kW, and the laser scanning speed is 8mm/s. The nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel, and the weight ratio of the nano metal powder is 2.6:1.2:1.2:0.4:0.3; the average grain size of the nano chromium is 40nm, the average grain size of the nano molybdenum is the same as that of the nano nickel and is 20nm, and the grain size of the nano copper is the same as that of the nano zinc and is 30nm.
The dispersant composite material is a mixture of a metal-organic framework material and an anionic surfactant, and the weight ratio of the dispersant composite material to the anionic surfactant is 3:1; the anionic surfactant is potassium oleate; the metal-organic framework material is MOF-74 of Jiangsu Xiancheng nano material science and technology limited; the auxiliaries are the same as in example 1.
Example 6: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out low-temperature tempering treatment at 140 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 70wt% of nano metal powder, 28wt% of dispersant composite material and 2wt% of auxiliary agent. The laser power of laser irradiation in the laser irradiation treatment is 2.0kW, and the laser scanning speed is 8mm/s. The nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel, and the weight ratio of the nano metal powder is 2.6:1.2:1.2:0.4:0.3; wherein the average particle size of all of the nano-metals is 50nm.
The dispersant composite material is a mixture of a metal-organic framework material and an anionic surfactant, and the weight ratio of the dispersant composite material to the anionic surfactant is 3:1; the anionic surfactant is a mixture of sulfonate and fatty acid salt, and the weight ratio of the anionic surfactant to the fatty acid salt is 2.2:1, wherein the fatty acid is potassium oleate and the sulfonate is branched-chain sodium dodecyl benzene sulfonate; the metal-organic framework material is MOF-74 of Jiangsu Xiancheng nano material science and technology limited; the auxiliaries are the same as in example 1.
Example 7: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material subjected to the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out 140 ℃ low-temperature tempering treatment on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 70wt% of nano metal powder, 28wt% of dispersant composite material and 2wt% of auxiliary agent. The laser power of laser irradiation in the laser irradiation treatment is 2.0kW, and the laser scanning speed is 8mm/s. The nano metal powder consists of nano copper, nano zinc and nano nickel, and the weight ratio of the nano metal powder is 1.2:1.2:0.3; wherein the average grain diameter of the nano nickel is the same and is 20nm, and the grain diameters of the nano copper and the nano zinc are the same and are 30nm.
The dispersant composite material is a mixture of a metal-organic framework material and an anionic surfactant, and the weight ratio of the dispersant composite material to the anionic surfactant is 3:1; the anionic surfactant is a mixture of sulfonate and fatty acid salt, and the weight ratio of the sulfonate to the fatty acid salt is 2.2:1, wherein the fatty acid is potassium oleate and the sulfonate is branched-chain sodium dodecyl benzene sulfonate; the metal-organic framework material is MOF-74 of Jiangsu Xiancheng nano material science and technology Limited; the auxiliaries are the same as in example 1.
Example 8: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a layer of nano conditioning additive (the thickness is about 0.25 mm) on the surface of the metal material, and then drying for 2 hours; coating a layer of nano conditioning additive (the thickness is about 0.25 mm), and continuously drying for 2 hours to obtain the product.
Wherein the nano-conditioning additive is the same as in example 2.
Example 9: a metal surface modification process is provided, which comprises the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material subjected to the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive (with the thickness of about 0.5 mm) on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out 140 ℃ low-temperature tempering treatment on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive is the metal nano particle surface conditioning agent I in patent CN101244458A and example 1. The rest of the treatment was the same as in example 2.
Performance test
(1) The applicant carried out high-temperature frictional wear tests on the parts obtained by surface treatment in the above examples, and the test groups are as follows:
experiment 1 the article of example 1 was tested;
experiment 2 the article of example 2 was tested;
experiment 3 the preparation of example 8 was tested;
experiment 4 a control article with an untreated surface was tested.
The results of the change of the temperature and the friction coefficient with time are shown in the attached figures 1 to 4. As can be seen from the attached drawings, the friction coefficients of the products of experiments 3 and 4 are very unstable, and the friction coefficients are changed all the time, especially the friction coefficient change in experiment 4 is very obvious around 90min, which are caused by that the surfaces of the products are repeatedly rubbed and new rough surfaces are repeatedly generated due to the abrasion of the products in the high-temperature friction process. In contrast, the friction coefficients of experiments 1 and 2 are basically very stable between 0.3 and 0.4, and the performance is stable.
(2) The applicant counted the wear quality of the parts in the above examples after the friction test, and the results are shown in table 1 below.
TABLE 1 Performance test Table
(3) The applicant counts the bonding state of the amorphous phase on the surface of the workpiece and the workpiece on the surface of the workpiece after the friction experiment in the embodiment, observes whether the interface of the workpiece has unstable conditions such as peeling, cracking, fault, interface separation and the like, and classifies the unstable conditions into 1-3 grades according to the severity of the unstable conditions, wherein the grade 1 has the best stability, the stable conditions basically do not occur, the grade 3 is the worst, and the unstable conditions such as obvious cracking and the like occur, and the specific results are shown in the following table 2. In addition, the applicant has tested the corrosion resistance of the parts treated in the above examples, and the surface of the parts is immersed in nitric acid with a concentration of 26wt%, and after being placed for 45min, the corrosion degree of the surface is observed, and the parts are classified into grades 1-3 according to the corrosion conditions, wherein the grade 1 corrosion condition is the slightest, no obvious corrosion is caused on the body, and the grade 3 corrosion condition is the most serious, and a large amount of corrosion occurs, and the specific results are shown in table 2 below.
TABLE 2 Performance test Table
| Bonding state | Corrosion resistance | |
| Example 1 | Level 1 | Level 1 |
| Example 2 | Level 1 | Level 1 |
| Example 3 | Stage 2 | Level 1 |
| Example 4 | Stage 2 | Level 1 |
| Example 5 | Level 1 | Level 1 |
| Example 6 | Stage 2 | Stage 2 |
| Example 7 | Stage 2 | Stage 2 |
| Example 8 | Grade 3 | Grade 3 |
| Example 9 | Stage 2 | Level 1 |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as can be conceived and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (2)
1. A metal surface modification process is characterized by comprising the following steps:
(1) Carrying out extrusion treatment on the surface of the metal material;
(2) Cleaning the surface of the metal material after the extrusion treatment by adopting an organic solvent;
(3) Spraying a nano conditioning additive on the surface of the metal material;
(4) Carrying out laser irradiation treatment on the surface of the metal material sprayed with the nano conditioning additive;
(5) Carrying out low-temperature tempering treatment at 120-160 ℃ on the surface of the metal material subjected to the laser irradiation treatment; the nano conditioning additive consists of 51 to 75 weight percent of nano metal powder, 10 to 45 weight percent of dispersant composite material and 0.01 to 5 weight percent of auxiliary agent;
the nano metal powder consists of nano chromium, nano copper, nano zinc, nano molybdenum and nano nickel;
the weight ratio of the nano chromium to the nano copper to the nano zinc to the nano molybdenum to the nano nickel is 2.6:1.2:1.2:0.4:0.3;
the average grain diameter of the nano molybdenum and the nano nickel is 10-20 nm;
the average grain diameter of the nano copper and the nano zinc is 25-35 nm;
the grain diameters of the nano copper and the nano zinc are the same;
the laser power of the laser irradiation in the step (4) is 1.5-2.2 kW;
the laser scanning speed of the laser irradiation in the step (4) is 5-20 mm/s;
the dispersant composite material is a mixture of a metal-organic framework material and an anionic surfactant, wherein the mass ratio of the metal-organic framework material to the anionic surfactant is 3;
the anionic surfactant is a mixture of sulfonate and fatty acid salt, and the mass ratio of the sulfonate to the fatty acid salt is 2.2:1; the fatty acid is potassium oleate; the sulfonate is branched-chain sodium dodecyl benzene sulfonate;
the metal-organic framework material is MOF-74.
2. Use of the process for modifying the surface of a metal according to claim 1 in the field of mechanical articles.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104947035A (en) * | 2015-06-19 | 2015-09-30 | 沈阳理工大学 | Method for enabling metal surface to penetrate nano powder by laser-induced impact |
| CN106011847A (en) * | 2016-07-22 | 2016-10-12 | 江苏大学 | In-situ non-crystallizing modification method for surface of metal material |
| CN106544475A (en) * | 2016-11-04 | 2017-03-29 | 西安航空动力控制科技有限公司 | A kind of thinning method of metal material surface crystal grain |
| US20180248044A1 (en) * | 2017-02-28 | 2018-08-30 | National Applied Research Laboratories | Flexible substrate structure, flexible transistor and method for fabricating the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947035A (en) * | 2015-06-19 | 2015-09-30 | 沈阳理工大学 | Method for enabling metal surface to penetrate nano powder by laser-induced impact |
| CN106011847A (en) * | 2016-07-22 | 2016-10-12 | 江苏大学 | In-situ non-crystallizing modification method for surface of metal material |
| CN106544475A (en) * | 2016-11-04 | 2017-03-29 | 西安航空动力控制科技有限公司 | A kind of thinning method of metal material surface crystal grain |
| US20180248044A1 (en) * | 2017-02-28 | 2018-08-30 | National Applied Research Laboratories | Flexible substrate structure, flexible transistor and method for fabricating the same |
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