CN111575685A - Preparation method of Ni-Sn-P-Cr porous alloy foam metal material - Google Patents

Preparation method of Ni-Sn-P-Cr porous alloy foam metal material Download PDF

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CN111575685A
CN111575685A CN202010423896.XA CN202010423896A CN111575685A CN 111575685 A CN111575685 A CN 111575685A CN 202010423896 A CN202010423896 A CN 202010423896A CN 111575685 A CN111575685 A CN 111575685A
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polyurethane foam
solution
metal material
foam
reducing
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甘雪萍
赵琪
刘晨虹
李周
周科朝
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Central South University
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Central South University
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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
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)

Abstract

The invention discloses a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material, which comprises the following steps of: (1) pretreating polyurethane foam; (2) preparing a main salt solution A and a reducing solution B; (3) immersing the modified polyurethane foam into the main salt solution A, heating and continuously stirring, synchronously dropwise adding the reducing solution B while stirring, taking out the product after the reaction is finished, repeatedly washing and drying to obtain the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer; (4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to remove polyurethane foam to obtain a primary foam metal material; (5) and heating and reducing the primary foam metal material in a reducing atmosphere to obtain the Ni-Sn-P-Cr porous alloy foam metal material. The reduction mode adopted in the invention can ensure that Ni-Sn-P-Cr in the composite plating layer is diffused mutually, so that the plating layer is more compact and smooth, and the oxidation resistance of the composite plating layer is improved.

Description

Preparation method of Ni-Sn-P-Cr porous alloy foam metal material
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 foam metal is a special metal material with a large number of holes distributed inside. Due to the unique three-dimensional network structure, the foam metal has a series of excellent structural and functional double characteristics of large specific surface area, high porosity, electromagnetic shielding, sound absorption, energy absorption and the like, so the foam metal not only can be used as a structural material, but also can be used as a functional material, and is a novel material gradually developed along with human science and technology. At present, the metal foam material is widely applied to the fields of aircraft engine oil gas filtration, light rail transit, catalysts and catalyst carriers, heat preservation, electromagnetic shielding materials and the like.
The foam metal has the advantages that the traditional metal material does not have: high porosity, large specific surface area, regular three-dimensional structure and controllable pore size design. In recent years, research and application of metal foams have focused primarily on metallic nickel foams. However, the nickel foam is not only easily oxidized but also has poor corrosion resistance, and the application of the nickel foam is greatly limited due to the insufficiency of the performance. Moreover, the preparation process of the foam nickel is mainly an electrodeposition method, but the electrodeposition process requires that the substrate is conductive, and the uneven shape and the uneven distribution of the charge of the substrate probably cause the uneven deposition of the coating. Therefore, in order to widen the application range of the nickel foam, the key point is to find a method capable of introducing a second metal element into the nickel foam to obtain excellent structural and functional characteristics, and to develop a new preparation process of the nickel foam.
At present, the research of Ni-Sn-P-Cr quaternary plating layer arouses the wide attention of researchers at home and abroad. Electroless plating is an effective surface modification method that can be applied not only to conductive and nonconductive parts, but also to the geometry of the substrate without special requirements. The chemical plating method is less in relevant research on preparation of the Ni-Sn-P-Cr porous alloy foam, and the prepared Ni-Sn-P-Cr porous alloy foam has poor oxidation resistance and other performances.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background technology and provide a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material with 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 Ni-Sn-P-Cr porous alloy foam metal material comprises the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam; the oil removal can remove oil stains on the surface of polyurethane foam, and the optimal oil removal effect can be achieved by adjusting the soaking time, concentration and temperature; the activation and sensitization treatment is beneficial to the easier plating of the composite metal plating layer on the surface of the polyurethane foam;
(2) stirring nickel sulfate, stannic chloride, sodium citrate, chromium chloride and lactic acid to obtain a main salt solution A; mixing a reducing agent containing sodium hypophosphite with water, and uniformly mixing by ultrasonic oscillation to obtain a reducing solution B;
(3) immersing the modified polyurethane foam into the main salt solution A, heating and continuously and mechanically stirring, synchronously dropwise adding the reducing solution B during stirring, taking out the product after the reaction is finished, repeatedly washing and drying to obtain the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer; the stirring can ensure the uniformity of the thickness of the plating layer in the plating process;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer in a tube furnace to remove polyurethane foam to obtain a primary foam metal material;
(5) and heating and reducing the primary foam metal material in a reducing atmosphere to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
In the above preparation method, preferably, the polyurethane foam has a purity of 99.9%, a porosity of 10 to 50PPI, and a thickness of 0.4 to 0.5 mm. The porosity and the thickness have great influence on the performance of the generated Ni-Sn-P-Cr porous alloy foam metal material, and the porosity and the thickness can ensure the oxidation resistance of the Ni-Sn-P-Cr porous alloy foam metal material.
In the above preparation method, preferably, in the main salt solution a, the concentration of nickel sulfate is 10 to 40g/L, the concentration of tin tetrachloride is 5 to 40g/L, the concentration of chromium chloride is 20 to 50g/L, the concentration of sodium citrate is 10 to 40g/L, and the concentration of lactic acid is 20 to 50 g/L; the reducing agent comprises a mixture of at least one of hydrazine hydrate, formaldehyde, sodium potassium tartrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, lactol, triethanolamine, glycerol, tannic acid or metol and sodium hypophosphite; the concentration of the reducing agent is 10-40 g/L. After the reducing agent is added, controlling the concentration of the reducing agent to be 10-40g/L in each liter of the main salt solution A. 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 so as to obtain the plating layer with better oxidation resistance.
In the above preparation method, preferably, the reducing agent is a mixture of tannic acid, metol and sodium hypophosphite in a mass ratio of 1: 5: 10 are mixed together. The research shows that the comprehensive performance of the plating layer can be ensured to be more excellent and the oxidation resistance to be better by adopting the composition of the reducing agents with the proportion and the mutual synergistic action of the reducing agents.
In the above preparation method, preferably, when the polyurethane foam is removed by heating in the step (4), the heating temperature is controlled to be 300-600 ℃.
In the above preparation method, preferably, in the step (5), the reduction reaction is performed in an atmosphere containing hydrogen when the primary foam metal material is heated and reduced, and the reduction temperature is controlled to be 300-550 ℃, and the reduction time is controlled to be 1-3 h. The reduction temperature is favorable for the diffusion of elements among Ni-Sn-P-Cr in the plating layer to ensure that the plating layer becomes more compact. The compactness is difficult to ensure due to overhigh or overlow temperature.
In the above preparation method, preferably, the drying in the step (3) is drying at 50-80 ℃ for 12-24 h.
In the preparation method, the oil removing treatment is preferably carried out by putting the polyurethane foam into 50-120g/L alkaline solution, heating to 70-90 ℃ for 1-3h, diluting with deionized water and washing to neutrality.
In the preparation method, preferably, the sensitization treatment is that polyurethane foam after oil removal treatment is added into 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.
In the preparation method, preferably, the activation treatment is to add the sensitized polyurethane foam into an activation solution for ultrasonic treatment for 30-120min, then dilute the activated polyurethane foam with deionized water, wash the activated polyurethane foam to be neutral, and dry the diluted polyurethane foam to obtain the modified polyurethane foam; the activating solution is PdCl2Mixed solution with hydrochloric acid.
The Ni-Sn-P-Cr porous alloy foam metal material disclosed by the invention is prepared by taking polyurethane as a raw material, adopting a sodium citrate-lactic acid mixed system, plating Ni-Sn-P-Cr on the surface of polyurethane foam simultaneously by a chemical plating method, then carrying out heat treatment on the polyurethane foam to remove the polyurethane foam, and further reducing the foam metal material without the polyurethane foam in a tubular furnace to form a plating layer, wherein reducing gas easily enters the material, and the Ni-Sn-P-Cr in the plating layer can diffuse among elements during reduction to make the plating layer more compact, so that the foam metal material with the composite metal plating layer with better oxidation resistance is obtained. In addition, in the invention, due to the adoption of a chemical plating mode, the Ni-Sn-P-Cr porous alloy foam metal material with good oxidation resistance can be prepared easily by regulating and controlling the mass fraction ratio of the four elements.
Compared with the prior art, the invention has the advantages that:
1. the preparation method has the advantages of simple experimental process, safety, reliability, simple equipment and easy realization of continuous preparation.
2. The polyurethane foam is used as a matrix, and 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.
3. In the invention, a chemical plating mode is adopted, and the proportion of each element in the composite plating layer and the thickness of the plating layer are regulated and controlled by adjusting the proportion of each metal salt in the main salt solution, so as to obtain the Ni-Sn-P-Cr porous alloy foam metal material with good oxidation resistance. In addition, the Ni-Sn-P-Cr porous alloy foam metal material prepared by the chemical plating method has the characteristics of uniform structure, low friction coefficient, excellent corrosion resistance and oxidation resistance and the like, and has important significance for improving the traditional metal foam nickel material.
4. The reduction mode adopted in the invention can ensure that Ni-Sn-P-Cr in the composite plating layer is diffused mutually, so that the plating layer is more compact and smooth, and the oxidation resistance of the composite plating layer is improved.
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 an SEM photograph of the Ni-Sn-P-Cr porous alloy foam metal material of example 4.
FIG. 2 is a graph showing the oxidation resistance of the Ni-Sn-P-Cr porous alloy foam metal materials of examples 1 to 4.
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:
a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material comprises the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam;
wherein the oil removing treatment is to remove oil stains of polyurethane foam by using a sodium hydroxide solution with the concentration of 50g/L, the oil removing time is 2 hours, and the temperature is 80 ℃. The sensitization treatment comprises the steps of putting the deoiled polyurethane foam into a sensitization liquid for ultrasonic treatment for 60min, diluting the polyurethane foam with deionized water, washing the polyurethane foam to be neutral to obtain sensitized polyurethane foam, and drying the sensitized polyurethane foam for 24h at 70 ℃ to obtain the sensitized polyurethane foam, wherein the sensitization liquid comprises 1L of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37%, and 5.0g of SnCl2Mixing to obtain the final product. The activation treatment is to place the sensitized polyurethane foam into an activation solution for ultrasonic treatment for 60min, dilute the polyurethane foam with deionized water and wash the polyurethane foam to be neutral to obtain the sensitized polyurethane foam, and dry the sensitized polyurethane foam at 70 ℃ for 24h to obtain the pretreated polyurethane foam, wherein the activation solution is 1L of deionized water, 4mL of concentrated hydrochloric acid with the mass fraction of 37%, and 20mg of PdCl2Mixing to obtain;
(2) mechanically stirring 25g/L nickel sulfate, 25g/L stannic chloride, 20g/L chromium chloride, 40g/L sodium citrate solution and 30g/L lactic acid to obtain a main salt solution A; preparing a reducing agent sodium hypophosphite and deionized water into a mixed solution with the concentration of 40g/L, and uniformly mixing through ultrasonic oscillation to obtain a reducing solution B; after the reducing solution B is added, the concentration of the reducing agent in each liter of the main salt solution A is 40 g/L;
(3) selecting modified polyurethane foam with the thickness of 0.5mm and the porosity of 20PPI and a main salt solution A, placing the modified polyurethane foam and the main salt solution A in a beaker, gradually dripping a reducing solution B while mechanically stirring, heating the modified polyurethane foam and the main salt solution A to 50 ℃ by adopting a water bath in the reaction process, repeatedly washing a foam metal material obtained after the reaction in deionized water to be neutral, and drying to obtain a polyurethane foam material plated with a Ni-Sn-P-Cr plating layer;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to 400 ℃ in a tube furnace to remove polyurethane foam to obtain a primary foam metal material;
(5) heating and reducing the primary foam metal material in a tubular furnace to 350 ℃ under argon-hydrogen mixed gas, and preserving the heat for 2 hours to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
Example 2:
a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material comprises the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam;
wherein the oil removing treatment is to remove oil stains of polyurethane foam by using a sodium hydroxide solution with the concentration of 60g/L, the oil removing time is 2 hours, and the temperature is 80 ℃. The sensitization treatment comprises the steps of putting the deoiled polyurethane foam into a sensitization liquid for ultrasonic treatment for 60min, diluting the polyurethane foam with deionized water, washing the polyurethane foam to be neutral, obtaining the sensitized polyurethane foam, and drying the sensitized polyurethane foam for 24h at 70 ℃ to obtain the sensitized polyurethane foam, wherein the sensitization liquid comprises 1L of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37%, and 20g of SnCl2Mixing to obtain the final product. The activation treatment is to place the sensitized polyurethane foam into an activation solution for ultrasonic treatment for 60min, dilute the polyurethane foam with deionized water and wash the polyurethane foam to be neutral to obtain the sensitized polyurethane foam, and dry the sensitized polyurethane foam at 70 ℃ for 24h to obtain the pretreated polyurethane foam, wherein the activation solution is 1L of deionized water, 4mL of concentrated hydrochloric acid with the mass fraction of 37%, and 30mg of PdCl2Mixing to obtain;
(2) mechanically stirring 20g/L nickel sulfate, 10g/L stannic chloride, 30g/L chromium chloride, 15g/L sodium citrate solution and 20g/L lactic acid to obtain a main salt solution A; preparing a mixed solution with the concentration of 20g/L from reducing agents sodium borohydride, sodium hypophosphite and deionized water, and uniformly mixing the mixed solution through ultrasonic oscillation to obtain a reducing solution B; after the reducing solution B is added, the concentration of the reducing agent in each liter of the main salt solution A is 20 g/L;
(3) selecting modified polyurethane foam with the thickness of 0.5mm and the porosity of 30PPI and a main salt solution A, placing the modified polyurethane foam and the main salt solution A in a beaker, gradually dripping a reducing solution B while mechanically stirring, heating the modified polyurethane foam and the main salt solution A to 60 ℃ by adopting a water bath in the reaction process, repeatedly washing a foam metal material obtained after the reaction is finished in deionized water to be neutral, and drying the foam metal material to obtain a polyurethane foam material plated with a Ni-Sn-P-Cr plating layer;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to 450 ℃ in a tube furnace to remove polyurethane foam to obtain a primary foam metal material;
(5) and heating and reducing the primary foam metal material in a tubular furnace to 400 ℃ under argon-hydrogen mixed gas, and preserving the heat for 2 hours to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
Example 3:
a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material comprises the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam;
wherein the oil removing treatment is to remove oil stains of polyurethane foam by using a sodium hydroxide solution with the concentration of 70g/L, the oil removing time is 2 hours, and the temperature is 80 ℃. The sensitization treatment comprises the steps of putting the deoiled polyurethane foam into a sensitization liquid for ultrasonic treatment for 60min, diluting the polyurethane foam with deionized water, washing the polyurethane foam to be neutral to obtain sensitized polyurethane foam, and drying the sensitized polyurethane foam for 24h at 70 ℃ to obtain the sensitized polyurethane foam, wherein the sensitization liquid comprises 1L of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37%, and 40g of SnCl2Mixing to obtain the final product. The activation treatment is to place the sensitized polyurethane foam into an activation solution for ultrasonic treatment for 60min, dilute the polyurethane foam with deionized water and wash the polyurethane foam to be neutral to obtain the sensitized polyurethane foam, and dry the sensitized polyurethane foam at 70 ℃ for 24h to obtain the pretreated polyurethane foam, wherein the activation solution is 1L of deionized concentrated hydrochloric acid 4mL with the mass fraction of 37%, and 40mg of PdCl2Mixing to obtain;
(2) mechanically stirring 30g/L nickel sulfate, 35g/L stannic chloride, 40g/L chromium chloride, 20g/L sodium citrate solution and 20g/L lactic acid to obtain a main salt solution A; preparing a reducing agent of sodium potassium tartrate, sodium hypophosphite and deionized water into a mixed solution with the concentration of 30g/L, and uniformly mixing by ultrasonic oscillation to obtain a reducing solution B; after the reducing solution B is added, the concentration of the reducing agent in each liter of the main salt solution A is 30 g/L;
(3) selecting modified polyurethane foam with the thickness of 0.5mm and the porosity of 40PPI and a main salt solution A, placing the modified polyurethane foam and the main salt solution A in a beaker, gradually dripping a reducing solution B while mechanically stirring, heating the modified polyurethane foam and the main salt solution A to 70 ℃ by adopting a water bath in the reaction process, repeatedly washing a foam metal material obtained after the reaction in deionized water to be neutral, and drying to obtain a polyurethane foam material plated with a Ni-Sn-P-Cr plating layer;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to 550 ℃ in a tube furnace to remove polyurethane foam to obtain a primary foam metal material;
(5) heating and reducing the primary foam metal material in a tubular furnace to 450 ℃ under argon-hydrogen mixed gas, and preserving the temperature for 2h to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
Example 4:
a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material comprises the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam;
wherein the oil removing treatment is to remove oil stains of polyurethane foam by using a sodium hydroxide solution with the concentration of 70g/L, the oil removing time is 2 hours, and the temperature is 80 ℃. The sensitization treatment comprises the steps of putting the deoiled polyurethane foam into a sensitization liquid for ultrasonic treatment for 60min, diluting the polyurethane foam with deionized water, washing the polyurethane foam to be neutral to obtain sensitized polyurethane foam, and drying the sensitized polyurethane foam for 24h at 70 ℃ to obtain the sensitized polyurethane foam, wherein the sensitization liquid comprises 1L of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37%, and 80g of SnCl2Mixing to obtain the final product. The activation treatment is to place the sensitized polyurethane foam into an activation solution for ultrasonic treatment for 60min, dilute the polyurethane foam with deionized water and wash the polyurethane foam to be neutral to obtain the sensitized polyurethane foam, and dry the sensitized polyurethane foam at 70 ℃ for 24h to obtain the pretreated polyurethane foam, wherein the activation solution is 1L of deionized concentrated hydrochloric acid 4mL with the mass fraction of 37%, and 40mg of PdCl2Mixing to obtain;
(2) mechanically stirring 40g/L nickel sulfate, 40g/L stannic chloride, 50g/L chromium chloride, 20g/L sodium citrate solution and 50g/L lactic acid to obtain a main salt solution A; preparing a mixed solution with the concentration of 40g/L by using a reducing agent formaldehyde, sodium hypophosphite and deionized water, and uniformly mixing by ultrasonic oscillation to obtain a reducing solution B; after the reducing solution B is added, the concentration of the reducing agent in each liter of the main salt solution A is 40 g/L;
(3) selecting modified polyurethane foam with the thickness of 0.5mm and the porosity of 50PPI and a main salt solution A, placing the modified polyurethane foam and the main salt solution A in a beaker, gradually dripping a reducing solution B while mechanically stirring, heating the modified polyurethane foam and the main salt solution A to 80 ℃ by adopting a water bath in the reaction process, repeatedly washing a foam metal material obtained after the reaction is finished in deionized water to be neutral, and drying the foam metal material to obtain a polyurethane foam material plated with a Ni-Sn-P-Cr plating layer;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to 550 ℃ in a tube furnace to remove polyurethane foam to obtain a primary foam metal material;
(5) heating and reducing the primary foam metal material in a tubular furnace to 500 ℃ under argon-hydrogen mixed gas, and preserving the heat for 2 hours to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
The SEM image of the Ni-Sn-P-Cr porous alloy foam metal material prepared in the embodiment is shown in FIG. 1.
The oxidation resistance of the Ni-Sn-P-Cr porous alloy foam metal materials obtained in examples 1 to 4 under the same test conditions is shown in FIG. 2.
Example 5:
a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material comprises the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam; the specific operation process is the same as that of example 4;
(2) mechanically stirring 40g/L nickel sulfate, 40g/L stannic chloride, 30g/L chromium chloride, 20g/L sodium citrate solution and 50g/L lactic acid to obtain a main salt solution A; preparing a reducing agent and deionized water into a mixed solution with the concentration of 40g/L, and uniformly mixing by ultrasonic oscillation to obtain a reducing solution B; after the reducing solution B is added, the concentration of the reducing agent in each liter of the main salt solution A is 40 g/L; the reducing agent is prepared from tannic acid, metol and sodium hypophosphite according to a mass ratio of 1: 5: 10, mixing the components;
(3) selecting modified polyurethane foam with the thickness of 0.5mm and the porosity of 50PPI and a main salt solution A, placing the modified polyurethane foam and the main salt solution A in a beaker, gradually dripping a reducing solution B while mechanically stirring, heating the modified polyurethane foam and the main salt solution A to 80 ℃ by adopting a water bath in the reaction process, repeatedly washing a foam metal material obtained after the reaction is finished in deionized water to be neutral, and drying the foam metal material to obtain a polyurethane foam material plated with a Ni-Sn-P-Cr plating layer;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to 550 ℃ in a tube furnace to remove polyurethane foam to obtain a primary foam metal material;
(5) heating and reducing the primary foam metal material in a tubular furnace to 500 ℃ under argon-hydrogen mixed gas, and preserving the heat for 2 hours to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
Example 6:
a preparation method of a Ni-Sn-P-Cr porous alloy foam metal material comprises the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam; the specific operation process is the same as that of example 4;
(2) mechanically stirring 45g/L nickel sulfate, 45g/L stannic chloride, 30g/L chromium chloride, 25g/L sodium citrate solution and 50g/L lactic acid to obtain a main salt solution A; preparing a reducing agent and deionized water into a mixed solution with the concentration of 40g/L, and uniformly mixing by ultrasonic oscillation to obtain a reducing solution B; after the reducing solution B is added, the concentration of the reducing agent in each liter of the main salt solution A is 40 g/L; the reducing agent is prepared from tannic acid, metol and sodium hypophosphite according to a mass ratio of 1: 5: 10, mixing the components;
(3) selecting modified polyurethane foam with the thickness of 0.5mm and the porosity of 50PPI and a main salt solution A, placing the modified polyurethane foam and the main salt solution A in a beaker, gradually dripping a reducing solution B while mechanically stirring, heating the modified polyurethane foam and the main salt solution A to 80 ℃ by adopting a water bath in the reaction process, repeatedly washing a foam metal material obtained after the reaction is finished in deionized water to be neutral, and drying the foam metal material to obtain a polyurethane foam material plated with a Ni-Sn-P-Cr plating layer;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to 550 ℃ in a tube furnace to remove polyurethane foam to obtain a primary foam metal material;
(5) heating and reducing the primary foam metal material in a tubular furnace to 500 ℃ under argon-hydrogen mixed gas, and preserving the heat for 2 hours to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
Examples 5 to 6 used the same test conditions as in examples 1 to 4, and the results showed that the weight loss rate in example 5 was about 85% of that in example 4, and the weight loss rate in example 6 was close to that in example 3 (about 3.5%).

Claims (10)

1. A preparation method of a Ni-Sn-P-Cr porous alloy foam metal material is characterized by comprising the following steps:
(1) degreasing, activating and sensitizing the polyurethane foam to obtain modified polyurethane foam;
(2) stirring nickel sulfate, stannic chloride, sodium citrate, chromium chloride and lactic acid to obtain a main salt solution A; mixing a reducing agent containing sodium hypophosphite with water, and uniformly mixing by ultrasonic oscillation to obtain a reducing solution B;
(3) immersing the modified polyurethane foam into the main salt solution A, heating and continuously stirring, synchronously dropwise adding the reducing solution B while stirring, taking out the product after the reaction is finished, repeatedly washing and drying to obtain the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer;
(4) heating the polyurethane foam material plated with the Ni-Sn-P-Cr plating layer to remove polyurethane foam to obtain a primary foam metal material;
(5) and heating and reducing the primary foam metal material in a reducing atmosphere to obtain the Ni-Sn-P-Cr porous alloy foam metal material.
2. The method of claim 1, wherein the polyurethane foam has a purity of 99.9%, a porosity of 10 to 50PPI, and a thickness of 0.4 to 0.5 mm.
3. The preparation method according to claim 1, wherein in the main salt solution a, the concentration of nickel sulfate is 10 to 40g/L, the concentration of tin tetrachloride is 5 to 40g/L, the concentration of sodium citrate is 10 to 40g/L, the concentration of chromium chloride is 20 to 50g/L, and the concentration of lactic acid is 20 to 50 g/L; the reducing agent comprises a mixture of at least one of hydrazine hydrate, formaldehyde, sodium potassium tartrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, lactol, triethanolamine, glycerol, tannic acid or metol and sodium hypophosphite; the concentration of the reducing agent is 10-40 g/L.
4. The preparation method according to claim 3, wherein the reducing agent is prepared from tannic acid, metol and sodium hypophosphite in a mass ratio of 1: 5: 10 are mixed together.
5. The preparation method as claimed in claim 1, wherein the heating temperature is controlled to be 300-600 ℃ when the polyurethane foam is removed by heating in the step (4).
6. The method as claimed in claim 1, wherein in the step (5), the reduction reaction is performed in an atmosphere containing hydrogen while heating and reducing the primary foam metal material, and the reduction temperature is controlled to be 300-550 ℃ and the reduction time is 1-3 h.
7. The method according to any one of claims 1 to 6, wherein the drying in the step (3) is drying at 50 to 80 ℃ for 12 to 24 hours.
8. The preparation method according to any one of claims 1 to 6, wherein the degreasing treatment is to put polyurethane foam into 50 to 120g/L alkaline solution, heat the solution to 70 to 90 ℃ for 1 to 3 hours, dilute the solution with deionized water and wash the solution to neutrality.
9. The preparation method according to any one of claims 1 to 6, wherein the sensitization treatment is ultrasonic treatment by adding the polyurethane foam after the oil removal treatment into a sensitization liquid, then diluting and washing the polyurethane foam to be neutral by using deionized water, and drying the polyurethane foam for 12 to 24 hours at 70 to 90 ℃; the sensitizing solution is a mixed solution of stannous chloride and hydrochloric acid.
10. The preparation method of any one of claims 1 to 6, wherein the activation treatment is to add the sensitized polyurethane foam into an activation solution for ultrasonic treatment for 30 to 120min, then dilute the activated polyurethane foam with deionized water, wash the diluted polyurethane foam to be neutral, and dry the diluted polyurethane foam to obtain the modified polyurethane foam; the activating solution is PdCl2Mixed solution with hydrochloric acid.
CN202010423896.XA 2020-05-19 2020-05-19 Preparation method of Ni-Sn-P-Cr porous alloy foam metal material Pending CN111575685A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113680390A (en) * 2021-07-29 2021-11-23 佛山市顺德区金磊环保科技有限公司 Foam material with formaldehyde purification function and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113680390A (en) * 2021-07-29 2021-11-23 佛山市顺德区金磊环保科技有限公司 Foam material with formaldehyde purification function and preparation method and application thereof

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