CN111719115B - Composite anti-corrosion wear-resistant layer for steel substrate - Google Patents
Composite anti-corrosion wear-resistant layer for steel substrate Download PDFInfo
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
- C23C10/54—Diffusion of at least chromium
- C23C10/56—Diffusion of at least chromium and at least aluminium
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention provides a composite anti-corrosion wear-resistant layer for a steel substrate and application thereof. The composite anti-corrosion wear-resistant layer comprises a multi-element permeable layer, and the permeable agent for the multi-element permeable layer comprises the following components: 12-32 parts of zinc-aluminum alloy powder, 1-10 parts of nickel-chromium alloy powder, 0-5 parts of zinc-bismuth alloy powder, 0-2 parts of bismuth powder, 0.3-2 parts of ammonium chloride, 0.1-1 part of rare earth catalyst powder and the balance of filling powder, wherein the total parts are 100 parts; wherein the mass ratio of zinc to aluminum in the zinc-aluminum alloy powder is 78: 22; the mass ratio of nickel to chromium of the nichrome powder is 40: 18; the mass ratio of zinc to bismuth in the zinc-bismuth alloy powder is 95: 5. The composite anti-corrosion wear-resistant layer can also comprise a passivation film layer and/or a sealing paint layer.
Description
Technical Field
The invention belongs to the field of metal corrosion prevention, and particularly relates to a composite corrosion-resistant wear-resistant layer for a steel substrate, which comprises a metal infiltrated layer and a passivation film layer.
Background
The metal and the contacted medium change the metal property through chemical reaction, and the metal equipment is greatly damaged, namely metal corrosion. The problem of metal corrosion is a problem that is always encountered during the service life of metal equipment and must therefore be solved before the metal equipment is put into use.
The most common method for preventing corrosion of metal materials (devices) is to cover the metal surface with a metal, nonmetal or metal-nonmetal composite film as a protective layer by a physical, chemical or electrochemical process to prevent or slow down the chemical reaction between the metal and the contacted medium. The related anticorrosion technologies comprise thermal spraying alloy, electro-galvanizing, a zinc-chromium coating (Dacromet), a zinc-nickel seeping layer, surface phosphating treatment, organic paint and the like.
The zinc-nickel infiltration layer technology is a low (middle) temperature chemical heat treatment technology in a ferrite state. Under a certain condition, the steel part is fully contacted and heated with a plurality of elements such as zinc, nickel, aluminum, rare earth and the like, so that the atoms of the multi-element metals such as zinc, nickel, aluminum and the like are uniformly adsorbed to the surface of the steel product, a zinc-nickel-iron alloy layer is generated on the surface of the steel through adsorption, absorption, reaction and diffusion, and meanwhile, the atoms of zinc and nickel are diffused into the steel matrix to form a corrosion-resistant diffusion layer in the steel matrix. Therefore, the binding force between the anticorrosive coating produced by the zinc-nickel coating technology and the steel substrate is strong, and the defects of poor binding force between other anticorrosive coatings and the substrate and low collision resistance are overcome. And no organic solvent is used in the process of generating the zinc-nickel seeping layer, so that the method has the characteristic of environmental friendliness. The Chinese invention patent application CN 109136828A (published 2019, 1 month and 4 days) discloses a Zn-Al-Ni anticorrosive function infiltration layer prepared in a low-temperature environment of 450 ℃, and the proportion of an infiltration agent is as follows: 20-50 parts of zinc powder for penetrating agent, 5-25 parts of aluminum powder for penetrating agent, 0.5-5 parts of nickel powder for penetrating agent, 0.1-2 parts of ammonium chloride as activator, 0.1-2 parts of rare earth as catalyst and the balance of Al as filler2O3Powder material; the total parts are 100 parts.
The national engineering construction development remarkably promotes the requirements on large bridges, engineering facilities, equipment and the like, and many large-scale capital construction projects occur in environments with rather severe geological conditions, such as plateau frozen soil zones, coastal areas and the like, so that the metal equipment facilities are in a severe corrosion environment, and further higher requirements are put forward on the corrosion prevention technology of metal materials (equipment).
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a composite anticorrosive coating for a steel substrate and a preparation method thereof.
Therefore, the invention adopts the following technical scheme:
a composite corrosion-resistant and wear-resistant layer for a steel substrate comprises a multi-element permeable layer, wherein the permeable agent for the multi-element permeable layer comprises the following components: 12-32 parts of zinc-aluminum alloy powder, 1-10 parts of nickel-chromium alloy powder, 0-5 parts of zinc-bismuth alloy powder, 0-2 parts of bismuth powder, 0.3-2 parts of ammonium chloride, 0.1-1 part of rare earth catalyst powder and the balance of filling powder, wherein the total parts are 100 parts; wherein the mass ratio of zinc to aluminum in the zinc-aluminum alloy powder is 78: 22; the mass ratio of nickel to chromium of the nichrome powder is 40: 18; the mass ratio of zinc to bismuth in the zinc-bismuth alloy powder is 95: 5.
Preferably, the composition of the permeating agent for the multielement permeating layer is as follows: 12-18 parts of zinc-aluminum alloy powder, 5-10 parts of nickel-chromium alloy powder, 2-4 parts of zinc-bismuth alloy powder, 0.5-1.5 parts of bismuth powder, 0.8-1.5 parts of ammonium chloride, 0.4-0.8 part of rare earth catalyst and the balance of filling powder, wherein the total parts are 100 parts.
Preferably, the multielement percolated layer has an average thickness of 30-150 μm.
Preferably, the rare earth catalyst is selected from one of lanthanum (La) and cerium (Ce), more preferably lanthanum (La).
Preferably, the filler powder is selected from Al2O3Particles or quartz sand with a particle size of 75-500 μm.
Preferably, the zinc-bismuth alloy powder is prepared by the following method:
zinc and bismuth in mass percent Zn: and Bi is 95%: 5 percent of the raw materials are mixed, the mixture is transferred into a hollow induction furnace for smelting, the smelting temperature is 420-.
Preferably, the particle sizes of the zinc-aluminum alloy powder, the nickel-chromium alloy powder, the zinc-bismuth alloy powder and the bismuth powder are less than 75 micrometers.
Preferably, the ammonium chloride is anhydrous ammonium chloride.
The zinc-aluminum alloy powder, the nickel-chromium alloy powder, the zinc powder, the bismuth powder and the rare earth catalyst powder are all commercially available products. Such as:
the zinc-aluminum alloy powder can be produced by Changsha metal materials GmbH, and has a trade name of S-Zn72Al28 and a granularity of-300 meshes.
The nickel-chromium alloy powder can be produced by Hebeibang cast metal materials Limited, and is DG.
The zinc powder can be produced by New Weiling Metal science and technology Co., Ltd in Hunan, with a particle size of-325 mesh.
The bismuth powder can be bismuth powder produced by Changsha Gu Union chemical technology Limited company, with a trade name of Bi99.99 and a particle size of-300 meshes.
The lanthanum powder can be lanthanum (La) powder with the granularity of 300 meshes, which is produced by Beijing Xinglong source technology limited.
The multielement seeping layer is prepared by the following steps:
1) workpiece surface pretreatment: removing oil stains on the surface of the workpiece, and performing shot blasting treatment by using a steel shot with the diameter of 0.1-0.3mm to expose a base material;
2) preparing a multi-element permeating agent for a permeating layer: according to the formula of the multi-element permeating agent for the permeable layer, all the raw materials are uniformly mixed according to the proportion for standby;
3) mechanical infiltration assistance: uniformly putting 25-35% of the multi-element permeating layer permeating agent at the bottom of a furnace pipe of a zincizing furnace, then putting the workpiece pretreated in the step 1), finally putting the rest multi-element permeating layer permeating agent, wherein the total volume of the workpiece and the multi-element permeating layer permeating agent accounts for 70-80% of the space in the furnace pipe, sealing the furnace pipe, then pushing the furnace pipe into a furnace chamber for co-permeation treatment, raising the temperature to 390-reservoir 435 ℃ at a constant speed within 1h, keeping the temperature of the furnace pipe at a rotating speed of 5-7r/min for 2.5-4.5h under the working condition of forward and reverse alternate rotation;
5) cooling and separating: and (4) withdrawing the furnace from the hearth, keeping the furnace rotating continuously until the furnace is cooled to room temperature in air, stopping rotating, uncovering the furnace, taking out the workpiece, and removing floating ash on the surface to obtain the multi-element infiltration layer deposited on the surface of the workpiece.
The invention also provides a composite corrosion-resistant and wear-resistant layer for a steel substrate, which comprises the multi-element seeping layer and a passivation film layer, wherein the passivation film layer is arranged on the side, away from the steel substrate, of the multi-element seeping layer.
Preferably, the raw materials of the composite passivation solution comprise 5-25 parts of silane coupling agent, 10-30 parts of lower saturated aliphatic alcohol, 2-15 parts of hydrochloric acid aqueous solution with the mass percentage concentration of 2.5%, 0.1-1 part of graphene aqueous solution with the mass percentage concentration of 8mg/ml, 0.5-10 parts of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT/PSS) aqueous dispersion with the mass percentage concentration of 1.7%, and the balance of water, wherein the total mass of the composite passivation solution for forming the passivation film layer is 100 parts.
Preferably, the silane coupling agent is selected from one or more of methyltriethoxysilane, ethoxytrimethylsilane and gamma-glycidoxypropyltriethoxysilane in any proportion.
Preferably, the lower saturated aliphatic alcohol is selected from one or two of ethanol and n-propanol in any proportion.
The aqueous graphene solution and the aqueous poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT/PSS) dispersion are commercially available products. For example, the graphene aqueous solution can be a single-layer graphene oxide aqueous solution produced by Shenzhen Tuoling evolution technology Limited, with a concentration of 8 mg/ml. The PEDOT/PSS aqueous dispersion liquid produced by Yangchengbo Bohong electronic chemistry Limited company can be selected as the PEDOT/PSS aqueous dispersion liquid, the solid content is 1.7 percent, and the PEDOT/PSS aqueous dispersion liquid has conductive performance and is dark blue liquid.
The composite passivation solution is prepared by the following method:
I. preparing raw materials according to a mixture ratio;
II, uniformly mixing the silane coupling agent, the lower saturated aliphatic alcohol, the hydrochloric acid aqueous solution and water, stirring for 2-6 hours at the temperature of 30-50 ℃, and cooling to room temperature to obtain silane coupling agent hydrolysate;
and III, adding the graphene aqueous solution and the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid aqueous dispersion into the silane coupling agent hydrolysate obtained in the step II under stirring, and uniformly mixing to obtain the composite passivation solution.
The passivation film layer is obtained through the following process: the workpiece covered with the multi-element infiltration layer is dipped or coated by the composite passivation solution, and then dried, thus obtaining the multi-element infiltration layer.
Preferably, the dipping or coating is performed at normal temperature, and the time for dipping or coating is 5 seconds to 5 minutes.
Also preferably, the drying temperature is 60-80 ℃ and the drying time is 5-15 minutes.
The invention provides a composite corrosion-resistant and wear-resistant layer for a steel substrate, which comprises the multielement seeping layer and the passivation film layer, and also comprises a sealing paint layer, wherein the sealing paint layer is arranged on the side, away from the steel substrate, of the passivation film layer.
Preferably, the sealing paint layer is prepared by spraying, dipping or coating the workpiece covered with the multielement seeping layer and the passive film by using a sealing paint commonly used in the field and drying.
Therefore, the composite anti-corrosion wear-resistant layer for the steel substrate provided by the invention can be one of the following structures:
1. the multielement cementation layer; or
2. The multielement diffusion layer + the passivation film layer; or
3. The multielement seeping layer + the passivation film layer + the sealing paint layer.
Therefore, the invention also aims to provide a corrosion-resistant and wear-resistant steel-based workpiece, which comprises the steel-based workpiece and any one of the composite corrosion-resistant and wear-resistant layers attached to the surface of the steel-based workpiece.
In addition, the invention also aims to provide the application of the composite anti-corrosion wear-resistant layer in the corrosion prevention of steel-based workpieces.
Preferably, the steel-based workpiece includes, but is not limited to, a metal part for a concrete bridge in the traffic field; preferably, the metal parts for the concrete bridge in the traffic field comprise a railway simply-supported T-beam sidewalk steel beam, a concrete bridge embedded part, a bridge pier hanging fence, a bridge railing and the like.
In the present specification, the "part" number indicates a ratio relationship between the relevant substances by mass, not an actual mass number of the relevant substances. "1 part" may be any mass number, such as 1 ton, 500kg, 10kg, 5kg, 1kg, 500g, 100g, etc.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention improves the corrosion resistance of the multi-element infiltrated layer by introducing Bi and Cr elements and realizing alloying. Particularly, Bi element is introduced, and the generation of microcracks of a seeping layer is greatly reduced by the characteristic that Bi does not shrink in the cooling process.
2. The melting points of all metal elements in the multi-element infiltration layer provided by the invention are greatly different, such as the melting point of nickel is 1453 ℃, and the melting point of chromium is 1855 ℃; the problem that metals with excessively different melting points cannot be synchronously co-infiltrated is solved by introducing high-melting-point metal elements into the infiltrating agent in an alloy form.
3. The invention prepares the multi-element infiltration layer at the temperature lower than 435 ℃ by regulating and controlling the formula and the process parameters of the infiltration agent, reduces the influence on the performance of a workpiece due to the reduction of the processing temperature, ensures the stability of the production of the infiltration layer, and is energy-saving and environment-friendly.
4. The composite passivation solution provided by the invention can form a uniform and compact passivation film on a metal substrate comprising a multi-element diffusion layer and the like in a film forming mode of spraying, dipping or coating, and the film layer has no crack phenomenon. The composite passivation solution provided by the invention combines the advantages of PEDOT/PSS and silane coupling agent, and both PEDOT/PSS and silane participate in film forming reaction in the process of metal surface passivation film forming. The acid environment of the PEDOT/PSS solution is favorable for promoting silanol generated by hydrolysis of the silane coupling agent to form covalent bonds with the multielement seeping layer, so that the bonding force between the film layer and the multielement seeping layer is favorably improved. The conductive PEDOT/PSS can promote the passivation of the active surface of the metal, and can passivate the surface of the metal again when the passivation film is damaged, so that the repairability of the passivation film on the surface of the metal is realized, and the long-acting protection effect is finally achieved.
It is understood by those skilled in the art that the composite passivation solution provided by the invention can also be applied to the corrosion prevention of steel-based workpieces alone or steel-based workpieces with other metal corrosion prevention layers, such as steel-based workpieces with thermal spraying alloy corrosion prevention layers.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
The experimental procedures in the following examples are all conventional ones unless otherwise specified. The raw materials and reagent materials used in the following examples are all commercially available products unless otherwise specified. Wherein, the purchase conditions of partial reagents and raw materials are as follows:
zinc-aluminum alloy powder: produced by Changsha everlasting metal materials Co., Ltd, the mark is S-Zn72Al28, and the granularity is-300 meshes.
Nickel-chromium alloy powder: NiCr alloy powder of NiCr, trade name DG, NiCr, particle size-325 mesh.
Zinc powder: new Hunan Weiling Metal New Material science and technology GmbH, particle size-325 mesh.
Bismuth powder: changsha Gu union chemical technology Co., Ltd, trade name Bi99.99, particle size-300 mesh.
Lanthanum powder: beijing Xinglong source technology, Inc., particle size 300 mesh.
Cerium powder: changshanjiu metal materials Co., Ltd, the mark Titd-Ce, particle size-200 mesh.
Graphene water solution: the concentration of the single-layer graphene oxide aqueous solution produced by Shenzhen Tuoling evolution technology Limited is 8 mg/ml.
Aqueous dispersion of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT/PSS): the salt city Bohong electronic chemistry Co., Ltd, solid content 1.7%.
Sealing paint: waterborne acrylic amino finishes, by south moon coatings, Jiangsu, Haoyue.
The zinc bismuth alloy powder used in the following examples was prepared by the following method:
zinc powder and bismuth powder according to mass percent Zn: and Bi is 95%: 5 percent of the raw materials are mixed, transferred into a hollow induction furnace for smelting, the smelting temperature is 420-.
Examples 1 to 5A Multi-element impregnation agent
The composition of the multi-element permeating layer permeating agent for the examples 1-5 is shown in the table 1, wherein 1 part is 10 Kg; the preparation method comprises the following steps:
the components are prepared according to the mixture ratio shown in the table 1 and are mixed evenly to obtain the composition.
Comparative examples 1 to 4 penetrating agent for multielement penetrating layer
The composition of the multi-element impregnation agent for the infiltrated layers of comparative examples 1-4 is shown in table 1 and prepared by the following method:
the components are prepared according to the mixture ratio shown in the table 1 and are mixed evenly to obtain the composition.
TABLE 1 raw material composition (parts) of the multi-element infiltrant for infiltrant layer of examples 1 to 5 and comparative examples 1 to 4
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Zinc-aluminum alloy powder | 12 | 32 | 16 | 20 | 25 | 10 | 33 | 11 | 24 |
| Nickel-chromium alloy powder | 10 | 1 | 10 | 5 | 8 | 13 | 0.8 | 18 | 5 |
| Zn powder | 5 | 0 | 4 | 3 | 2.5 | 6 | 0 | 1 | 2 |
| Zinc bismuth alloy powder | 0 | 3 | 2 | 2 | 2.5 | 0 | 6 | 1 | 2 |
| Bismuth powder | 2 | 0 | 1.5 | 1 | 0.5 | 3 | 0 | 1 | 1 |
| Ammonium chloride | 2 | 0.3 | 1.5 | 1 | 0.8 | 3 | 0.2 | 3 | 4 |
| Lanthanum powder | 0 | 0.1 | 0 | 0.6 | 0 | 0.5 | 0 | 2 | 0 |
| Cerium powder | 1 | 0 | 0.4 | 0 | 0.7 | 0 | 0.05 | 0 | 1.2 |
| Al2O3Granules | 68 | 0 | 64.6 | 0 | 60 | 64.5 | 0 | 63 | 0 |
| Quartz sand | 0 | 63.6 | 0 | 67.4 | 0 | 0 | 59.95 | 0 | 60.8 |
Examples 6 to 10A multielement percolated layer
The multi-element carburized layers described in examples 6 to 10 were formed on the surface of a steel-based workpiece by using the multi-element carburization agent described in examples 1 to 5, respectively, by the following method:
1) workpiece surface pretreatment: removing oil stains on the surface of the workpiece, and performing shot blasting treatment by using a steel shot with the diameter of 0.1-0.3mm to expose a base material;
2) mechanical infiltration assistance: uniformly placing 25-35% of multi-element permeating layer permeating agent at the bottom of a furnace pipe of a zincizing furnace, then placing the workpiece pretreated in the step 1), finally placing the rest multi-element permeating layer permeating agent, wherein the total volume of the workpiece and the multi-element permeating layer permeating agent accounts for 70-80% of the space in the furnace pipe, sealing the furnace pipe, then pushing the furnace pipe into a furnace chamber for co-permeation treatment, raising the temperature to 390 plus-minus 435 ℃ at a constant speed within 1h, keeping the temperature of the furnace pipe at a rotating speed of 5-7r/min for 2.5-4.5h under the working condition of forward and reverse alternate rotation; wherein the multi-element permeating layer permeating agent adopted by each embodiment is shown in a table 2;
3) cooling and separating: and (3) withdrawing the furnace from the hearth, keeping the furnace rotating continuously until the furnace is cooled to room temperature in air, stopping rotating, uncovering the furnace, taking out the workpiece, and removing floating ash on the surface to obtain the target product, wherein the average thickness of the multielement infiltration layer is 60-65 mu m.
Comparative examples 5 to 8 a multielement percolated layer
The multi-element cementation layers described in comparative examples 5 to 8 were formed on the surface of the steel-based workpiece by using the cementation agent for multi-element cementation layers described in comparative examples 1 to 4, respectively, as follows:
1) workpiece surface pretreatment: removing oil stains on the surface of the workpiece, and performing shot blasting treatment by using a steel shot with the diameter of 0.1-0.3mm to expose a base material;
2) mechanical infiltration assistance: uniformly putting 25-35% of multi-element permeating layer permeating agent at the bottom of a furnace pipe of a zincizing furnace, then putting the workpiece pretreated in the step 1), and finally putting the rest multi-element permeating layer permeating agent, wherein the total volume of the workpiece and the multi-element permeating layer permeating agent accounts for 70-80% of the space in the furnace pipe, sealing the furnace pipe, then pushing the furnace pipe into a furnace chamber for co-permeation treatment, heating to 390 plus-material 435 ℃ at a constant speed within 1h, keeping the temperature of the furnace pipe for 2.5-4.5h under the working condition that the furnace pipe rotates at 5-7r/min and rotates forwards and backwards alternately; wherein the multi-element permeating layer permeating agents adopted in each proportion are shown in a table 2;
3) cooling and separating: and (4) withdrawing the furnace from the hearth, keeping the furnace rotating continuously until the furnace is cooled to room temperature in the air, stopping rotating, opening the cover, taking out the workpiece, and removing floating ash on the surface to obtain the target product.
Test example 1 measurement of Multi-element strike-through Properties
The multi-element infiltrated layers obtained in examples 6-10 and comparative examples 5-8 were subjected to performance measurements. Wherein: the neutral salt fog resistance is carried out according to the specification of GB/T10125-; the microhardness is regulated according to GB/T4340.1-2009. The results are shown in Table 2.
TABLE 2 Primary Performance test results for Multi-element infiltrated layers of examples 6-10 and comparative examples 5-8
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Osmosis agent | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Neutral salt spray resistance, h | 840 | 800 | 960 | 860 | 850 | 560 | 470 | 440 | 360 |
| Microhardness, HV0.1 | 310 | 340 | 380 | 350 | 360 | 280 | 297 | 310 | 300 |
The data in table 2 show: compared with each proportion, the neutral salt fog resistance of the multi-element permeable layer per se of each embodiment of the invention is obviously improved; the multielement infiltrated layer of the invention is shown to have outstanding corrosion resistance properties. The microhardness of the infiltrated layer is used for evaluating the wear resistance of the infiltrated layer. The hardness of the surface of the substrate of the non-infiltrated sample was 175HV 0.1. The test results show that the surface hardness of the carburized layer of each example of the invention is 310HV0.1-380HV0.1, while the surface hardness of the zincated layer of the comparative example is 290HV0.1-310HV 0.1. The permeation layer of the invention can improve the wear resistance of the permeation layer to a certain extent.
And (4) conclusion: the multi-element infiltration layer has excellent corrosion resistance and wear resistance, and the adhesion between the infiltration layer and the base material is strong, so that the multi-element infiltration layer can provide a durable corrosion protection effect for the base material, and ensure and prolong the service time of steel equipment.
Examples 11 to 15A composite passivation solution
The compositions of the composite passivates of examples 11-15 are shown in Table 3, and are prepared by the following method:
I. preparing raw materials according to a mixture ratio;
II, uniformly mixing the silane coupling agent, the lower saturated aliphatic alcohol, the hydrochloric acid aqueous solution and water, stirring for 2-6 hours at the temperature of 30-50 ℃, and cooling to room temperature to obtain silane coupling agent hydrolysate;
and III, adding the graphene aqueous solution and the PEDOT/PSS aqueous dispersion liquid into the silane coupling agent hydrolysate obtained in the step II under stirring, and uniformly mixing to obtain the composite passivation solution.
Comparative examples 9 to 12 composite passivation solution
The composite passivates of comparative examples 9-12, see table 3, were prepared by the following method:
I. preparing raw materials according to a mixture ratio;
II, uniformly mixing the silane coupling agent, the lower saturated aliphatic alcohol, the hydrochloric acid aqueous solution and water, stirring for 2-6 hours at the temperature of 30-50 ℃, and cooling to room temperature to obtain silane coupling agent hydrolysate;
and III, adding the graphene aqueous solution and the PEDOT/PSS aqueous dispersion liquid into the silane coupling agent hydrolysate obtained in the step II under stirring, and uniformly mixing to obtain the composite passivation solution.
TABLE 3 formulation of passivation solution used after co-cementation of multicomponent powders of examples 11-15 and comparative examples 9-12
Examples 16 to 20A composite anticorrosive and wear-resistant layer
The composite corrosion-resistant and wear-resistant layer of the embodiment 16-20 comprises a multi-element permeation layer and a passivation film layer, and is prepared by the following method:
and (3) respectively soaking the workpieces with the multi-element seeping layers prepared in the embodiments 6-10 into the composite passivation solution prepared in the embodiments 11-15 for 1 minute +/-10 seconds, taking out, and drying at the temperature of 60-80 ℃ for about 10 minutes to obtain the multi-element passivation solution.
Comparative examples 13 to 16 composite anticorrosive and wear-resistant layer
The composite corrosion-resistant and wear-resistant layers of comparative examples 13 to 16 comprise a multi-element permeation layer and a passivation film layer, and are prepared by the following method:
and (3) respectively soaking the workpieces with the multi-element seeping layers prepared in the comparative examples 5-8 into the composite passivation solution of the comparative examples 9-12 for 1 minute +/-10 seconds, taking out and drying at the temperature of 60-80 ℃ for about 10 minutes to obtain the multi-element seeping layer passivation solution.
Test example 2
The composite anticorrosive wear-resistant layers obtained in examples 16 to 20 and comparative examples 13 to 16 were subjected to performance measurement. Wherein the neutral salt spray resistance is carried out according to the specification of GB/T10125-; the microhardness is regulated according to GB/T4340.1-2009. The results are shown in Table 4.
Table 4 main performance test results of composite anticorrosive wear-resistant layers of examples 16 to 20 and comparative examples 13 to 16
| Example 16 | Example 17 | Example 18 | Example 19 | Example 20 | Comparative example 13 | Comparative example 14 | Comparative example 15 | Comparative example 16 | |
| Osmosis agent | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Composite passivation solution | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Comparative example 9 | Comparative example 10 | Comparative example 11 | Comparative example 12 |
| Neutral salt spray resistance, h | 1840 | 1810 | 1960 | 1930 | 1880 | 1260 | 1170 | 1140 | 1060 |
| Microhardness, HV0.1 | 310 | 340 | 380 | 350 | 360 | 280 | 297 | 310 | 300 |
The above results show that: the passivation film layer formed by the composite passivation solution can further improve the corrosion resistance of the anticorrosive coating without changing the adhesive force and microhardness of the seeping layer. Compared with a comparative example, the composite anticorrosive coatings of the embodiments of the invention have more outstanding and excellent corrosion resistance.
Examples 21 to 25A composite anticorrosive and wear-resistant layer
The composite corrosion-resistant and wear-resistant layer of the embodiment 21-25 comprises a multi-element permeation layer, a passivation film layer and a sealing paint layer, and is prepared by the following method:
taking the workpiece with the multi-element infiltration layer and the passivation film layer prepared in the embodiment 16-20, dipping the workpiece into sealing paint for 90 seconds (from the time when the workpiece enters the bath solution to the time when the workpiece exits the bath solution) by adopting a dip coating process, and drying the workpiece at the temperature of 140 +/-2 ℃ for 15min to obtain the coating.
Claims (11)
1. A composite corrosion-resistant and wear-resistant layer for a steel substrate comprises a multi-element permeable layer, wherein the permeable agent for the multi-element permeable layer comprises the following components: 12-32 parts of zinc-aluminum alloy powder, 1-10 parts of nickel-chromium alloy powder, 0-5 parts of zinc-bismuth alloy powder, 0-2 parts of bismuth powder, 0.3-2 parts of ammonium chloride, 0.1-1 part of rare earth catalyst powder and the balance of filling powder, wherein the total parts are 100 parts; wherein the mass ratio of zinc to aluminum in the zinc-aluminum alloy powder is 78: 22; the mass ratio of nickel to chromium of the nichrome powder is 40: 18; the mass ratio of zinc to bismuth in the zinc-bismuth alloy powder is 95: 5; the rare earth catalyst is selected from one of lanthanum and cerium;
the average thickness of the multielement seeping layer is 30-150 μm.
2. The composite corrosion-resistant wear-resistant layer according to claim 1, wherein the composition of the permeation agent for the multi-element permeation layer is as follows: 12-18 parts of zinc-aluminum alloy powder, 5-10 parts of nickel-chromium alloy powder, 2-4 parts of zinc-bismuth alloy powder, 0.5-1.5 parts of bismuth powder, 0.8-1.5 parts of ammonium chloride, 0.4-0.8 part of rare earth catalyst and the balance of filling powder, wherein the total parts are 100 parts.
3. The composite corrosion and wear resistant layer of claim 1 or 2 wherein the rare earth catalyst is lanthanum.
4. Composite anti-corrosion and wear-resistant layer according to claim 1 or 2, characterized in that the filler powder is selected from Al2O3Particles or quartz sand with a particle size of 75-500 μm.
5. The composite corrosion-resistant wear-resistant layer according to claim 1 or 2, wherein the zinc-bismuth alloy powder is prepared by the following method:
zinc and bismuth in mass percent Zn: bi = 95%: 5 percent of the raw materials are mixed, the mixture is transferred into a hollow induction furnace for smelting, the smelting temperature is 420-.
6. The composite anti-corrosion wear-resistant layer according to claim 1 or 2, wherein the particle size of the zinc-aluminum alloy powder, the nickel-chromium alloy powder, the zinc-bismuth alloy powder and the bismuth powder is less than 75 μm.
7. The composite corrosion and wear resistant layer according to claim 1 or 2 wherein the ammonium chloride is anhydrous ammonium chloride.
8. The composite corrosion and wear resistant layer according to claim 1 or 2, wherein said multi-element infiltrated layer is prepared by the steps of:
1) workpiece surface pretreatment: removing oil stains on the surface of the workpiece, and performing shot blasting treatment by using a steel shot with the diameter of 0.1-0.3mm to expose a base material;
2) preparing a multi-element permeating agent for a permeating layer: uniformly mixing the raw materials according to the proportion for later use;
3) mechanical infiltration assistance: uniformly putting 25-35% of the multi-element permeating layer permeating agent at the bottom of a furnace pipe of a zincizing furnace, then putting the workpiece pretreated in the step 1), finally putting the rest multi-element permeating layer permeating agent, wherein the total volume of the workpiece and the multi-element permeating layer permeating agent accounts for 70-80% of the space in the furnace pipe, sealing the furnace pipe, then pushing the furnace pipe into a furnace chamber for co-permeation treatment, raising the temperature to 390-reservoir 435 ℃ at a constant speed within 1h, keeping the temperature of the furnace pipe at a rotating speed of 5-7r/min for 2.5-4.5h under the working condition of forward and reverse alternate rotation;
5) cooling and separating: and (4) withdrawing the furnace from the hearth, keeping the furnace rotating continuously until the furnace is cooled to room temperature in air, stopping rotating, uncovering the furnace, taking out the workpiece, and removing floating ash on the surface to obtain the multi-element infiltration layer deposited on the surface of the workpiece.
9. Use of a composite corrosion and wear resistant layer according to any one of claims 1 to 8 for corrosion protection of steel based workpieces; the steel-based workpiece includes but is not limited to a metal part for a concrete bridge in the traffic field.
10. The use of claim 9, wherein the metal parts for concrete bridges in the traffic field comprise railway simple-supported T-beam sidewalk steel beams, concrete bridge embedded parts, bridge pier hanging fences and bridge railings.
11. An anti-corrosion and wear-resistant steel-based workpiece comprising a steel-based workpiece and the composite anti-corrosion and wear-resistant layer of any one of claims 1 to 8 attached to the surface of the steel-based workpiece.
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| CN114015975A (en) * | 2021-11-08 | 2022-02-08 | 湖南昊宏新材料科技有限公司 | Zinc alloy material for zinc impregnation and corrosion prevention and method |
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| US3497379A (en) * | 1967-12-27 | 1970-02-24 | Du Pont | Process for improving the corrosion resistance of alloy diffusion coated metal articles |
| JP2948004B2 (en) * | 1991-11-29 | 1999-09-13 | 日本カロライズ工業株式会社 | Al-Cr composite diffusion coating method for Ti alloy |
| DE4434593A1 (en) * | 1994-09-28 | 1996-04-04 | Herberts Gmbh | Process for the production of a corrosion-protecting, well-adhering paint and the workpieces thereby obtained |
| CN101665898B (en) * | 2009-10-14 | 2011-07-20 | 北京中路大成科技发展有限公司 | Method for preparing ZnAlNi multi-component alloy anticorrosive coating on workpiece surface |
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| CN107058942A (en) * | 2016-10-13 | 2017-08-18 | 常州大学 | A kind of vacuum machine can help the preparation method of zincizing aluminum chromium layer |
| WO2019006679A1 (en) * | 2017-07-04 | 2019-01-10 | 深圳市长宏泰科技有限公司 | Passivation agent for oil removal, rust removal and passivation, steel and iron component, and passivation treatment method therefor |
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