CN111705310B - Preparation method of composite metal coating foam metal material - Google Patents
Preparation method of composite metal coating foam metal material Download PDFInfo
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- CN111705310B CN111705310B CN202010426184.3A CN202010426184A CN111705310B CN 111705310 B CN111705310 B CN 111705310B CN 202010426184 A CN202010426184 A CN 202010426184A CN 111705310 B CN111705310 B CN 111705310B
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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Abstract
The invention discloses a preparation method of a composite metal coating foam metal material, which comprises the following steps: (1) modified polyurethane foam; (2) preparing a chemical plating solution A, an electroplating solution and a chemical plating solution B; (3) chemical plating; (4) electroplating; (5) heat treatment; (6) heating and reducing; (7) and chemically plating the solution to obtain the composite metal plating layer foam metal material. The invention adopts a mode of combining chemical plating and electroplating, and the prepared composite metal plating layer foam metal material has bright and compact plating layer, controllable metal content and plating layer thickness, certain strength, large specific surface area, good oxidation resistance and corrosion resistance.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a preparation method of a foam metal material.
Background
The nickel-iron foam metal material is used as a structural and functional material which develops rapidly, is widely applied to the aspects of catalysts, catalyst carriers, high-temperature liquid filters, heat exchangers and other functional materials, and can also be used as a structural material in the fields of automobiles, buildings and the like. However, in the conventional method for preparing the foam nickel-iron material, polyurethane sponge is usually subjected to pretreatment steps such as oil removal, acid washing, sensitization and activation, and then is subjected to chemical plating or electroplating, and an alloy layer such as nickel-iron is plated on the surface of the foam material, so that the nickel-iron foam metal is prepared. In the nickel-iron foam metal material prepared by the method, under the environment of corrosive media such as acid, alkali and the like, after the surface anticorrosive layer is corroded, the middle metal layer is exposed to the corrosive media, so that the material fails.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology, and provide a preparation method of a composite metal plating layer foam metal material with strong corrosion resistance and good oxidation resistance. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a composite metal coating foam metal material comprises the following steps:
(1) carrying out oil removal, acidification, sensitization and activation treatment on the polyurethane foam to obtain modified polyurethane foam; the optimal oil removing effect can be achieved by adjusting the soaking time, concentration and temperature; more nucleation sites are provided for the subsequent formation of the composite plating layer through sensitization and activation treatment, so that the formation of the composite plating layer is facilitated; the acidification, sensitization and activation treatment can provide pretreatment for the surface chemical plating of the composite metal coating, which is beneficial to the easier plating of the composite metal coating on the surface;
(2) stirring nickel sulfate, nickel chloride and a reducing agent to obtain a chemical plating solution A; stirring nickel sulfate, ferrous sulfate, sodium citrate, boric acid and sodium dodecyl sulfate to obtain an electroplating solution; stirring nickel sulfate, stannic chloride, sodium citrate, chromium chloride, lactic acid, sodium hypophosphite and a reducing agent to obtain a chemical plating solution B;
(3) immersing the modified polyurethane foam into the chemical plating solution A for chemical plating, continuously stirring to ensure the uniformity of the thickness and components of a plating layer, taking out the product after the reaction is finished, repeatedly washing the product to be neutral by deionized water, removing redundant water by physical extrusion, and drying (drying at 80 ℃ for 24 hours) to obtain a nickel-plated foam material;
(4) immersing the nickel-plated foam material into an electroplating solution for electroplating to thicken the thickness of a plating layer, continuously stirring, taking out a product after the reaction is finished, repeatedly washing the product with deionized water to be neutral, and drying (drying at 80 ℃ for 24 hours) to obtain a nickel-iron foam metal material;
(5) carrying out heat treatment on the nickel-iron foam metal material in an air atmosphere to obtain the nickel-iron foam metal material without polyurethane foam, and simultaneously realizing hardening;
(6) under the reducing atmosphere, heating and reducing to remove the nickel-iron foam metal material of the polyurethane foam, and obtaining the foam metal material with compact metal plating; in the reduction treatment process, reducing gas easily enters the pores, and mutual diffusion can occur between alloy elements in the plating layer in the heat treatment and reduction treatment processes, so that the plating layer becomes more compact, and a compact foam metal material with a better metal plating layer is obtained;
(7) and immersing the foam metal material with the compact metal coating into the chemical plating solution B for chemical plating, continuously stirring, taking out the product after the reaction is finished, repeatedly washing the product with deionized water to be neutral, and drying (drying at 80 ℃ for 24h) to obtain the composite metal coating foam metal material.
In the above production method, preferably, the polyurethane foam has a purity of 99.9% and a through-hole ratio of 85 to 90%. The through hole rate and the purity have great influence on the performance of the generated composite metal coating foam metal material, and the through hole rate and the purity can ensure the comprehensive performance of the composite metal coating foam metal material.
In the above preparation method, preferably, in the electroless plating solution a, the concentration of nickel sulfate is 10-60g/L, the concentration of nickel chloride is 20-50g/L, and the concentration of the reducing agent is 20-80 g/L; in the electroplating solution, the concentration of nickel sulfate is 10-30g/L, the concentration of ferrous sulfate is 10-60g/L, the concentration of sodium citrate is 10-50g/L, the concentration of boric acid is 30-70g/L, and the concentration of sodium dodecyl sulfate is 0.1-0.6 g/L; in the chemical plating solution B, the concentration of nickel sulfate is 10-60g/L, the concentration of stannic chloride is 20-50g/L, the concentration of sodium citrate is 20-50g/L, the concentration of chromium chloride is 5-50g/L, the concentration of lactic acid is 10-40g/L, the concentration of sodium hypophosphite is 5-20g/L, and the concentration of reducing agent is 10-80 g/L. The research shows that the proportional relation of each element in the plating layer has great influence on the performance of the plating layer, and the proportion of each element can be adjusted through chemical plating and electroplating to obtain the plating layer with better comprehensive performance.
In the above preparation method, preferably, the reducing agent is at least one of hydrazine hydrate, formaldehyde, sodium potassium tartrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, lactol, triethanolamine, glycerol, tannic acid, and metol.
In the above preparation method, preferably, the reducing agent is tannic acid and metol in a mass ratio of 1: 5, mixing the components. The research shows that the chemical plating system has good matching performance with the reducing agents in the ratio and the reducing agents are mutually synergistic, so that the comprehensive performance of a plating layer can be ensured to be more excellent and the corrosion resistance is better. Especially, in the chemical plating solution B, the synergistic effect of tannic acid, metol and sodium hypophosphite is utilized, so that the effect is better. More preferably, the mass ratio of the tannic acid to the metol to the sodium hypophosphite is 1: 5: 10.
in the above preparation method, preferably, in the step (3), the chemical plating is performed by heating in a water bath to 50-70 ℃ and controlling the pH value to 3.0-5.0; in the step (7), the chemical plating is carried out by heating to 60-90 ℃ in a water bath, and controlling the pH value (adjusted by sodium hydroxide solution and dilute sulfuric acid) to be 3.5-5.5.
In the above preparation method, preferably, during the electroplating in the step (4), the pH value of the electroplating process is controlled to be 3.0-5.0, the temperature is 50-70 ℃, and the current density is 1-5A/dm2。
In the above preparation method, preferably, the calcination temperature is controlled to be 200-500 ℃ for 0.5-3.5h during the heat treatment in the step (5).
In the above preparation method, preferably, in the step (6), the reduction reaction is performed in an atmosphere containing hydrogen during the heating reduction treatment, the reduction temperature is controlled to be 600-800 ℃, and the reduction time is 1-4 h. The reduction temperature is favorable for the diffusion of elements in the plating layer, so that the plating layer becomes more compact. The compactness is difficult to ensure due to overhigh or overlow temperature.
In the preparation method, preferably, the oil removing treatment is that the polyurethane foam is put into 20-150g/L alkaline solution (potassium hydroxide solution), heated to 70-90 ℃ for treatment for 15-45min, and then washed to be neutral by deionized water; the acidification is pickling by using 1-5g/L oxalic acid solution; the sensitization treatment is that the polyurethane foam after the acidification treatment is added into a sensitization liquid for ultrasonic treatment, and then the polyurethane foam is diluted by deionized water and washed to the middleDrying at 70-90 deg.C for 12-24 hr; the sensitizing solution is a mixed solution of stannous chloride and hydrochloric acid; adding the sensitized polyurethane foam into an activating solution for ultrasonic treatment for 30-120min, diluting with deionized water, washing to be neutral, and drying to obtain modified polyurethane foam; the activating solution is PdCl of 10-200mg/mL2And (3) solution.
The invention takes polyurethane as raw material, nickel iron and the like are simultaneously plated on the surface of polyurethane foam by electroplating and chemical plating methods, then the polyurethane foam with a composite metal plating layer plated on the surface is subjected to heat treatment, and the polyurethane foam is removed to finally prepare the nickel iron foam metal material. The invention plates a metal plating layer containing ferronickel and the like on the surface of the polyurethane foam, wherein the thickness of the plating layer and the element content proportion in the plating layer are controllable; the polyurethane foam has a three-dimensional space structure, can retain the original structural characteristics after heat treatment to form three-dimensional reticular metal foam, and is beneficial to the application of the polyurethane foam in the aspects of aeroengine oil gas filters, light rail transit, catalysts, catalyst carriers and the like; and the whole process is simple, the device is simple and convenient, the operation is convenient, the energy is saved, the environment is protected, and the mass production can be realized. The invention adopts a mode of combining chemical plating and electroplating, and the prepared composite metal plating layer foam metal material has bright and compact plating layer, controllable metal content and plating layer thickness, certain strength, large specific surface area, good oxidation resistance and corrosion resistance.
Compared with the prior art, the invention has the advantages that:
1. the invention adopts a one-step reduction method to directly carry out electroplating and chemical plating on the surface of the polyurethane sponge after roughening, pickling, sensitizing and activating treatment, and has simple process steps, easy operation and convenient maintenance.
2. The electroplating and chemical plating solution has the advantages of few chemical materials, low cost, high deposition speed, capability of obtaining bright composite coatings with different thicknesses and less environmental pollution due to the plating solution, and realizes continuous autocatalytic deposition of nickel and iron on a polyurethane sponge substrate.
3. In the chemical plating process, chemical elements such as phosphorus, tin and the like are further added, so that the corrosion resistance of the plating layer can be further improved; and metal oxides are also formed on the coating layer during the heat treatment process, so that the corrosion resistance of the coating layer is improved.
4. The composite metal plating layer foam metal material obtained by the invention has the advantages of certain hardness and strength, light weight, large specific surface area, high through hole rate, strong oxidation resistance and corrosion resistance and the like.
5. The preparation method has the advantages of simple experimental process, safety, reliability, simple equipment and easy realization of continuous preparation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic process flow diagram of the preparation method of the composite metal plating foam metal material of the present invention.
FIG. 2 is an SEM photograph of a composite metal plated foam metal material of example 3.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
as shown in fig. 1, a method for preparing a composite metal-plated foam metal material includes the following steps:
(1) carrying out oil removal, acidification, sensitization and activation treatment on polyurethane foam (15cm multiplied by 10cm multiplied by 1cm) to obtain modified polyurethane foam; wherein the oil removing treatment is to remove oil stain of polyurethane foam by using a potassium hydroxide solution with the concentration of 50g/L, the oil removing time is 20min, and the temperature is 70 ℃. The acidification treatment is to treat the polyurethane foam after oil removal in 1g/L oxalic acid solution for 20min, and then to wash the polyurethane foam to be neutral by deionized water to obtain the polyurethane foam after the acidification treatment; sensitizing treatment, namely treating the pickled polyurethane foam in a mixed solution of 5g/L stannous chloride and 5ml/L hydrochloric acid for 15min, and then cleaning the treated polyurethane foam to be neutral by using deionized water to obtain sensitized polyurethane foam; the activation treatment is that the sensitized polyurethane foam is treated in 10mg/mL palladium chloride solution for 120min at the temperature of 40 ℃, and then is washed to be neutral by deionized water to obtain modified polyurethane foam;
(2) magnetically stirring 10g/L nickel sulfate, 20g/L nickel chloride and 40g/L sodium hypophosphite to obtain a chemical plating solution A; magnetically stirring 10g/L nickel sulfate, 10g/L ferrous sulfate, 10g/L sodium citrate, 30g/L boric acid and 0.1g/L sodium dodecyl sulfate to obtain an electroplating solution; magnetic stirring is carried out on a mixed solution of 10g/L nickel sulfate, 20g/L crystallized stannic chloride, 20g/L sodium citrate, 10g/L lactic acid, 5g/L chromium chloride, 5g/L sodium hypophosphite and 10g/L sodium borohydride to obtain a chemical plating solution B;
(3) immersing the modified polyurethane foam in the chemical plating solution A to carry out a chemical plating process, and ensuring the uniformity of the plating solution through mechanical stirring so as to ensure the uniformity of the thickness and components of a plating layer; the pH value in the chemical plating process is 3.0, the temperature is 50 ℃, and the reaction time is 4 hours; after the reaction is finished, repeatedly washing the obtained product in deionized water to be neutral, removing excessive water through physical extrusion, and drying to obtain the nickel-plated foam material;
(4) immersing the nickel-iron foam material in an electroplating solution to carry out an electroplating process, and ensuring the uniformity of the electroplating solution through mechanical stirring so as to ensure the uniformity of the thickness and components of a plating layer; the pH value in the electroplating process is 3.0 and the temperature isAt 50 ℃ and a current density of 1A/dm2(ii) a Repeatedly washing the obtained product in deionized water to be neutral after the reaction is finished, and drying and carrying out heat treatment to obtain the nickel-iron foam metal material;
(5) calcining the nickel-iron foam metal material in an air atmosphere at the calcining temperature of 200 ℃ for 2h to obtain the polyurethane foam-removed nickel-iron foam metal material; carrying out reduction treatment in a hydrogen atmosphere at the treatment temperature of 600 ℃ for 2h to obtain a foam metal material with a compact metal coating;
(6) and (3) placing the foam metal material with the compact metal plating layer and the chemical plating solution B in a beaker, heating to 60 ℃ by adopting a water bath in the reaction process, plating for 40h, keeping the pH value at 3.5 in the plating process, repeatedly washing the obtained foam metal material in deionized water to be neutral after the reaction is finished, and drying to obtain the composite metal plating layer foam metal material.
The composite metal plating layer foam metal material obtained by the embodiment 1 is integrally in a three-dimensional network structure, is gray-white and semi-bright in appearance, is high in specific surface area, is compact in plating layer structure, is 85-90% in through hole rate, and has certain hardness, good oxidation resistance and good corrosion resistance.
Example 2:
a preparation method of a composite metal coating foam metal material comprises the following steps:
(1) carrying out oil removal, acidification, sensitization and activation treatment on polyurethane foam (15cm multiplied by 10cm multiplied by 1cm) to obtain modified polyurethane foam; wherein the degreasing treatment is to remove oil stains of polyurethane foam by using a potassium hydroxide solution with the concentration of 100g/L, the degreasing time is 10min, and the temperature is 70 ℃. The acidification treatment is to treat the polyurethane foam after oil removal in 3g/L oxalic acid solution for 20min, and then to wash the polyurethane foam to be neutral by deionized water to obtain the polyurethane foam after the acidification treatment; sensitizing treatment, namely treating the pickled polyurethane foam in a mixed solution of stannous chloride 8g/L and hydrochloric acid 10ml/L for 10min, and then cleaning the treated polyurethane foam to be neutral by using deionized water to obtain sensitized polyurethane foam; the activation treatment is that the sensitized polyurethane foam is treated in 100mg/mL palladium chloride solution for 120min at the temperature of 50 ℃, and then is washed to be neutral by deionized water to obtain modified polyurethane foam;
(2) magnetically stirring nickel sulfate with the concentration of 20g/L, nickel chloride with the concentration of 30g/L and formaldehyde as a reducing agent with the concentration of 20g/L to obtain a chemical plating solution A; stirring 20g/L nickel sulfate, 40g/L ferrous sulfate, 30g/L sodium citrate, 50g/L boric acid and 0.3g/L sodium dodecyl sulfate by magnetic force to obtain an electroplating solution; magnetic stirring is carried out on a mixed solution of 30g/L nickel sulfate, 45g/L crystallized stannic chloride, 30g/L sodium citrate, 30g/L lactic acid, 20g/L chromium chloride, 15g/L sodium hypophosphite and 20g/L sodium borohydride to obtain a chemical plating solution B;
(3) immersing the modified polyurethane foam in the chemical plating solution A to carry out a chemical plating process, and ensuring the uniformity of the plating solution through mechanical stirring so as to ensure the uniformity of the thickness and components of a plating layer; the pH value in the chemical plating process is 4.0, the temperature is 60 ℃, and the reaction time is 4 h; after the reaction is finished, repeatedly washing the obtained product in deionized water to be neutral, removing excessive water through physical extrusion, and drying to obtain the nickel-plated foam material;
(4) immersing the nickel-iron foam material in an electroplating solution to carry out an electroplating process, and ensuring the uniformity of the electroplating solution through mechanical stirring so as to ensure the uniformity of the thickness and components of a plating layer; the pH value in the electroplating process is 4.0, the temperature is 60 ℃, and the current density is 3A/dm2(ii) a Repeatedly washing the obtained product in deionized water to be neutral after the reaction is finished, and drying and carrying out heat treatment to obtain the nickel-iron foam metal material;
(5) calcining the nickel-iron foam metal material in an air atmosphere at the calcining temperature of 300 ℃ for 1.5h to obtain the polyurethane foam-removed nickel-iron foam metal material; carrying out reduction treatment in a hydrogen atmosphere at the treatment temperature of 650 ℃ for 2.5h to obtain a foam metal material with a compact metal coating;
(6) and (3) placing the foam metal material with the compact metal plating layer and the chemical plating solution B in a beaker, heating to 75 ℃ by adopting a water bath in the reaction process, plating for 60 hours, keeping the pH value at 4.5 in the plating process, repeatedly washing the obtained foam metal material in deionized water to be neutral after the reaction is finished, and drying to obtain the composite metal plating layer foam metal material.
The composite metal plating layer foam metal material obtained in the embodiment 2 is integrally in a three-dimensional network structure, is gray-white and semi-bright in appearance, is high in specific surface area, is communicated with holes, is compact in plating layer structure, is 85-90% in through hole rate, and has certain hardness, good oxidation resistance and good corrosion resistance.
Example 3:
a preparation method of a composite metal coating foam metal material comprises the following steps:
(1) carrying out oil removal, acidification, sensitization and activation treatment on polyurethane foam (15cm multiplied by 10cm multiplied by 1cm) to obtain modified polyurethane foam; wherein the oil removing treatment is to remove oil stain of polyurethane foam by using a potassium hydroxide solution with the concentration of 120g/L, the oil removing time is 5min, and the temperature is 75 ℃. The acidification treatment is to treat the polyurethane foam after oil removal in 5g/L oxalic acid solution for 10min, and then to wash the polyurethane foam to be neutral by deionized water to obtain the polyurethane foam after the acidification; sensitizing treatment, namely treating the pickled polyurethane foam in a mixed solution of 10g/L of stannous chloride and 10ml/L of hydrochloric acid for 10min, and then cleaning the treated polyurethane foam to be neutral by using deionized water to obtain sensitized polyurethane foam; the activation treatment is that the sensitized polyurethane foam is treated in 200mg/mL palladium chloride solution for 120min at the temperature of 50 ℃, and then is washed to be neutral by deionized water to obtain modified polyurethane foam;
(2) magnetically stirring 60g/L nickel sulfate, 50g/L nickel chloride and 30g/L potassium sodium tartrate to obtain a chemical plating solution A; magnetically stirring 30g/L nickel sulfate, 60g/L ferrous sulfate, 50g/L sodium citrate, 70g/L boric acid and 0.6g/L sodium dodecyl sulfate to obtain an electroplating solution; magnetic stirring is carried out on a mixed solution of 60g/L nickel sulfate, 50g/L crystallized stannic chloride, 50g/L sodium citrate, 40g/L lactic acid, 40g/L chromium chloride, 20g/L sodium hypophosphite and 30g/L potassium sodium tartrate to obtain a chemical plating solution B;
(3) immersing the modified polyurethane foam in the chemical plating solution A to carry out a chemical plating process, and ensuring the uniformity of the plating solution through mechanical stirring so as to ensure the uniformity of the thickness and components of a plating layer; the pH value in the chemical plating process is 5.0, the temperature is 70 ℃, and the reaction time is 4 hours; after the reaction is finished, repeatedly washing the obtained product in deionized water to be neutral, removing excessive water through physical extrusion, and drying to obtain the nickel-plated foam material;
(4) immersing the nickel-iron foam material in an electroplating solution to carry out an electroplating process, and ensuring the uniformity of the electroplating solution through mechanical stirring so as to ensure the uniformity of the thickness and components of a plating layer; the pH value in the electroplating process is 5.0, the temperature is 70 ℃, and the current density is 5A/dm2(ii) a Repeatedly washing the obtained product in deionized water to be neutral after the reaction is finished, and drying and carrying out heat treatment to obtain the nickel-iron foam metal material;
(5) calcining the nickel-iron foam metal material in an air atmosphere at the calcining temperature of 500 ℃ for 1h to obtain the polyurethane foam-removed nickel-iron foam metal material; carrying out reduction treatment in a hydrogen atmosphere at the treatment temperature of 750 ℃ for 3.5h to obtain a foam metal material with a compact metal coating;
(6) and (3) placing the foam metal material with the compact metal plating layer and the chemical plating solution B in a beaker, heating to 90 ℃ by adopting a water bath in the reaction process, plating for 60 hours, keeping the pH value at 5.5 in the plating process, repeatedly washing the obtained foam metal material in deionized water to be neutral after the reaction is finished, and drying to obtain the composite metal plating layer foam metal material.
As shown in fig. 2, the composite metal-plated foamed metal material obtained in example 3 has a three-dimensional network structure, a gray-white semi-bright appearance, a high specific surface area, through holes, a dense plating layer structure with a through hole rate of 85 to 90%, and a certain hardness, oxidation resistance and corrosion resistance.
Example 4:
a method for preparing a composite metal plating layer foam metal material, which is the same as the embodiment 3, and is characterized in that the reducing agent in the chemical plating solution B is tannic acid and metol, and the mass ratio of the tannic acid to the metol to the sodium hypophosphite is 1: 5: 10.
Claims (7)
1. the preparation method of the composite metal coating foam metal material is characterized by comprising the following steps of:
(1) carrying out oil removal, acidification, sensitization and activation treatment on the polyurethane foam to obtain modified polyurethane foam;
(2) stirring nickel sulfate, nickel chloride and a reducing agent to obtain a chemical plating solution A; stirring nickel sulfate, ferrous sulfate, sodium citrate, boric acid and sodium dodecyl sulfate to obtain an electroplating solution; stirring nickel sulfate, stannic chloride, sodium citrate, chromium chloride, lactic acid, sodium hypophosphite and a reducing agent to obtain a chemical plating solution B;
(3) immersing the modified polyurethane foam into the chemical plating solution A for chemical plating, continuously stirring, taking out the product after the reaction is finished, repeatedly washing and drying to obtain a nickel-plated foam material;
(4) immersing the nickel-plated foam material into an electroplating solution for electroplating, continuously stirring, taking out the product after the reaction is finished, repeatedly washing and drying to obtain a nickel-iron foam metal material;
(5) carrying out heat treatment on the nickel-iron foam metal material in an air atmosphere to obtain the nickel-iron foam metal material without polyurethane foam;
(6) under the reducing atmosphere, heating and reducing to remove the nickel-iron foam metal material of the polyurethane foam, and obtaining the foam metal material with compact metal plating;
(7) immersing the foam metal material with a compact metal coating into the chemical plating solution B for chemical plating, continuously stirring, taking out the product after the reaction is finished, repeatedly washing and drying to obtain the composite metal coating foam metal material;
in the chemical plating solution A, the concentration of nickel sulfate is 10-60g/L, the concentration of nickel chloride is 20-50g/L, and the concentration of a reducing agent is 20-80 g/L; in the electroplating solution, the concentration of nickel sulfate is 10-30g/L, the concentration of ferrous sulfate is 10-60g/L, the concentration of sodium citrate is 10-50g/L, the concentration of boric acid is 30-70g/L, and the concentration of sodium dodecyl sulfate is 0.1-0.6 g/L; in the chemical plating solution B, the concentration of nickel sulfate is 10-60g/L, the concentration of stannic chloride is 20-50g/L, the concentration of sodium citrate is 20-50g/L, the concentration of chromium chloride is 5-50g/L, the concentration of lactic acid is 10-40g/L, the concentration of sodium hypophosphite is 5-20g/L, and the concentration of a reducing agent is 10-80 g/L;
during the heat treatment in the step (5), the calcination temperature is controlled to be 200-;
in the step (6), the reduction reaction is carried out in the atmosphere containing hydrogen during the heating reduction treatment, the reduction temperature is controlled to be 600-800 ℃, and the reduction time is 1-4 h.
2. The method according to claim 1, wherein the polyurethane foam has a purity of 99.9% and a porosity of 85 to 90%.
3. The method according to claim 1, wherein the reducing agent is at least one of hydrazine hydrate, formaldehyde, sodium potassium tartrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, lactol, triethanolamine, glycerol, tannic acid, or metol.
4. The preparation method according to claim 3, wherein the reducing agent is tannic acid and metol in a mass ratio of 1: 5, mixing the components.
5. The production method according to any one of claims 1 to 4, wherein in the step (3), the electroless plating is carried out by heating the solution to 50 to 70 ℃ in a water bath, and controlling the pH value to be 3.0 to 5.0; in the step (7), the chemical plating is carried out by heating to 60-90 ℃ in a water bath and controlling the pH value to be 3.5-5.5.
6. The production method according to any one of claims 1 to 4, wherein the pH value of the plating process is controlled to 3.0 to 5.0, the temperature is controlled to 50 to 70 ℃, and the current density is controlled to 1 to 5A/dm in the plating in the step (4)2。
7. The production method according to any one of claims 1 to 4, wherein the degreasing treatment is a treatment of a polyurethane foamPutting into 20-150g/L alkaline solution, heating to 70-90 deg.C, treating for 15-45min, and washing with deionized water to neutrality; the acidification is pickling by using 1-5g/L oxalic acid solution; the sensitization treatment is that the polyurethane foam after the acidification treatment is added into a sensitization liquid for ultrasonic treatment, then the polyurethane foam is diluted by deionized water and washed to be neutral, and the polyurethane foam is dried for 12 to 24 hours at the temperature of 70 to 90 ℃; the sensitizing solution is a mixed solution of stannous chloride and hydrochloric acid; adding the sensitized polyurethane foam into an activating solution for ultrasonic treatment for 30-120min, diluting with deionized water, washing to be neutral, and drying to obtain modified polyurethane foam; the activating solution is PdCl of 10-200mg/mL2And (3) solution.
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