CN110724941A - Method for preparing porous metal film by chemical plating process - Google Patents

Abstract

The invention discloses a method for preparing a porous metal film by a chemical plating process, which comprises the following steps: (1) preparing a catalytic solution: preparing a mixed solution of first silane, second silane, ethanol, a water-based polymer solution and water, adding ammonia water to adjust the pH value to 9 in the stirring process, stirring at normal temperature for 1-30min, adjusting the pH value to 7 by using citric acid, adding a 1-200g/L catalyst ion solution, stirring for 1-30min, and adding isopropanol to obtain a catalytic solution; (2) activating the substrate: uniformly coating the catalytic solution on the surface of a substrate, and drying at 60-150 ℃ for 1-30min to obtain an activated substrate; (3) chemical plating: immersing the activated base material into a plating solution for plating, wherein the plating time is 15-60min, and the temperature is 60-90 ℃; (4) and washing the plated base material with water and carrying out ultrasonic treatment to obtain the porous metal film.

Description

Method for preparing porous metal film by chemical plating process

technical field

The invention relates to the technical field of coatings, in particular to a method for preparing a porous metal film by an electroless plating process.

Background technique

Porous metal membrane has the advantages of simple process flow, controllable pore size, low relative density, high specific strength, high specific surface area, light weight, sound insulation, heat insulation, good permeability and high adhesion, etc. It has potential application value in many fields such as industry.

At present, most of the porous metal films prepared with HDH titanium powder have a pore size that decreases with the increase of sintering temperature. This patent prepares a porous metal film with controllable pore size, easy process control, simple equipment and low cost. . For example: Patent CN201410176004.5 discloses a porous metal film prepared by using stainless steel fiber sintered felt and its preparation method. In this method, the surface of the stainless steel sintered felt is first oxidized, and then placed in a mixed solution of urea and nickel nitrate. According to the reaction conditions such as the reaction temperature and time, the nickel-iron hydrotalcite film is grown in situ on the surface of the stainless steel sintered felt substrate. Although the porous metal membrane prepared by this method greatly reduces the pore size ratio of the porous metal membrane to the matrix, the separation precision is low and can only be used for solid-liquid separation, so its application field is greatly reduced. Patent CN201410834347.6 discloses a preparation method of a high gradient porous metal film. The porous metal matrix is first blocked with pre-prepared inorganic powder, and then coated with metal powder, and then sintered at high temperature under hydrogen or an inert atmosphere to obtain The impurity-containing gradient porous membrane is finally washed with chemical reagents (or vacuum infiltration) or ultrasonic technology to remove residual impurities in the membrane matrix to obtain a high gradient porous metal membrane. Although the porous metal film prepared by this method has good integrity and high gradient, the process is complicated and has obvious technical differences with the present invention.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a method for preparing porous metal film by chemical plating process to solve the deficiencies in the prior art, which can enrich the current preparation method of porous metal film, and can also prepare metal film with complex shape.

The invention provides a method for preparing a porous metal film by an electroless plating process, comprising the following steps:

(1) Configure a catalytic solution: configure a mixed solution of the first silane, the second silane, ethanol, an aqueous polymer solution and water, add ammonia water to adjust the pH to 9 during the stirring process, and stir at room temperature for 1-30 minutes, then use lemon The pH of the acid is adjusted to 7, the catalyst ion solution of 1-200g/L is added, and isopropanol is added after stirring for 1-30min to obtain the catalyst solution;

(2) Activating the substrate: uniformly coat the above-mentioned catalytic solution on the surface of the substrate, and bake at 60-150° C. for 1-30 minutes to obtain an activated substrate;

(3) Electroless plating: the activated substrate is immersed in the plating solution for plating, the plating time is 15-60 min, and the temperature is 60-90 °C;

(4) The plated substrate is washed with water and ultrasonically treated to obtain a porous metal film.

Preferably, the first silane in step (1) is at least one of dimethyldimethoxysilane and methyldiethoxysilane.

Preferably, the second silane in step (1) is γ-(2,3-glycidoxy)propyltrimethoxysilane.

Preferably, the mass fraction of the aqueous polymer solution in step (1) is 1-10%.

Preferably, the aqueous polymer solution in step (1) is at least one of sodium carboxymethyl cellulose, polyvinyl alcohol, and polyvinylpyrrolidone aqueous solution.

Preferably, the catalyst ion in step (1) is at least one of palladium, gold, platinum and silver.

Preferably, the mass ratio of the first silane, the second silane, ethanol, the aqueous polymer solution, water, isopropanol and the catalyst ion solution described in step (1) is 1:0.1-5:2:10-150: 0.1-100:10-1000:0.5-50.

Preferably, in step (2), the surface of the substrate contains active groups, and the active groups include hydroxyl groups, carboxyl groups, epoxy groups, and mercapto groups.

Preferably, the electroless plating in step (3) is at least one of electroless copper plating, electroless nickel plating and electroless cobalt plating, and the thickness of the metal plating layer prepared by electroless plating is 2-5 μm.

Preferably, in the ultrasonic treatment in step (4), the temperature is gradually increased from 30°C to 120-150°C at 20°C/min, and the ultrasonic medium is liquid paraffin.

Compared with the prior art, the present invention has the beneficial effects of: using the prepared catalytic solution to catalyze the chemical plating reaction to prepare the metal film, and combining the ultrasonic treatment to realize the separation of the substrate and the metal film. The process of the invention is simple, the pore size and thickness are controllable, and the porous metal film of complex shape can be prepared.

Description of drawings

Fig. 1 is the SEM image of the metal copper porous film of Example 1 of the present invention;

FIG. 2 is an XRD pattern of the metal copper porous film of Example 1 of the present invention.

Detailed ways

The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, but not to be construed as a limitation of the present invention.

A method for preparing a porous metal film by an electroless plating process, comprising the following steps:

(1) Configure a catalytic solution: configure a mixed solution of the first silane, the second silane, ethanol, an aqueous polymer solution and water, add ammonia water to adjust the pH to 9 during the stirring process, and stir at room temperature for 1-30 minutes, then use lemon The pH of the acid is adjusted to 7, the catalyst ion solution of 1-200g/L is added, and isopropanol is added after stirring for 1-30min to obtain the catalyst solution;

(2) Activating the substrate: uniformly coat the above-mentioned catalytic solution on the surface of the substrate, and bake at 60-150° C. for 1-30 minutes to obtain an activated substrate;

(3) Electroless plating: the activated substrate is immersed in the plating solution for plating, the plating time is 15-60 min, and the temperature is 60-90 °C;

(4) The plated substrate is washed with water and ultrasonically treated to obtain a porous metal film.

The first silane in step (1) is at least one of dimethyldimethoxysilane and methyldiethoxysilane.

The second silane in step (1) is γ-(2,3-glycidoxy)propyltrimethoxysilane.

The mass fraction of the aqueous polymer solution in step (1) is 1-10%.

The aqueous polymer solution in step (1) is at least one of sodium carboxymethyl cellulose, polyvinyl alcohol, and polyvinylpyrrolidone aqueous solution.

The catalyst ion in step (1) is at least one of palladium, gold, platinum and silver.

The mass ratio of the first silane, the second silane, ethanol, the aqueous polymer solution, water, isopropanol and the catalyst ion solution described in the step (1) is 1:0.1-5:2:10-150:0.1-100: 10-1000: 0.5-50.

In step (2), the surface of the substrate contains active groups, and the active groups include hydroxyl groups, carboxyl groups, epoxy groups, and mercapto groups.

The electroless plating in step (3) is at least one of electroless copper plating, electroless nickel plating and electroless cobalt plating, and the thickness of the metal plating layer prepared by electroless plating is 2-5 μm.

The ultrasonic treatment in step (4) is to gradually increase the temperature from 30°C to 120-150°C at 20°C/min, and the ultrasonic medium is liquid paraffin.

The metal film is prepared by catalyzing the electroless plating reaction of the prepared catalytic solution, and the separation of the substrate and the metal film is realized by combining with ultrasonic treatment.

(1) Controllable pore size: The silane in the catalytic solution is hydrolyzed into a lipophilic phase (Si-Si long chain), which is incompatible with the hydrophilic phase (hydrophilic resin) in the catalytic solution during the film formation process. During the process, phase separation occurs to form a granular structure. In addition, the boiling points of the solvents (water, ethanol and isopropanol) in the catalytic solution are different, and the volatilization speed is different during the film formation process. The relative content of two phases and different solvents can realize the regulation of particle size.

In the electroless plating process, metal ions are deposited on the surface of the catalytic film under the action of catalytic particles on the surface of the catalytic film. Since the catalytic solution contains epoxy groups (introduced by the second silane), it is the same as the surface of the substrate (rich in active groups). In addition, because only silanol groups, hydroxyl groups and epoxy groups in the catalytic film can adsorb catalyst particles, the coordination bonds between these groups and the catalyst particles are weak, resulting in the adhesion between the coating and the catalytic film. The weaker force causes the metal coating to fall off along the catalytic layer/metal film interface, that is to say, a hole structure is formed on the inner surface of the metal coating, and the size of the holes can be adjusted by the particle size formed on the surface of the catalytic film.

(2) The thickness is controllable: with the increase of the electroless plating time, the thickness of the plating layer increases, and the present invention can prepare the porous metal film with unnecessary thickness by controlling the electroless plating time and the electroless plating parameters.

(3) Porous metal films with complex shapes can be prepared: electroless plating is an in-situ deposition process. As long as a catalytic film is formed on the surface of the substrate, the coating will be deposited on the surface. By controlling the shape of the substrate, porous metal films of different shapes can be prepared. metal film.

Embodiment 1 of the present invention:

A method for preparing a porous metal film by an electroless plating process, comprising the following steps:

The mass fraction of 0.5% hydrophilic polymer aqueous solution and the aqueous solution of γ-(2,3-glycidoxy)propyltrimethoxysilane and silver nitrate with a relative mass ratio of 75:20:5 at 500r/min Stir and mix at a high speed to obtain a primer solution. The above primer solution was printed on the surface of the substrate and dried at 80°C for 10min. The dried substrate was chemically plated with copper. The plating time was 15min and the plating temperature was 60°C. The substrate was washed with water and ultrasonically treated, and the ultrasonic temperature was gradually increased from 30 °C to 120 °C at 20 °C/min, and the ultrasonic medium was paraffin to obtain a porous metal copper film.

As shown in Figure 1, the back of the metal film is a porous structure, and the internal structure of the pores is loose. FIG. 2 is an XRD pattern of the metal film. The diffraction peaks at 2θ of 43°, 51°, and 74° in the XRD spectrum are characteristic peaks of face-centered cubic copper, and the characteristic peaks of Cu have a narrow half-height width, no impurity phase, and good crystallinity. To sum up, it is shown that the porous metal copper film can be prepared through the process described in this invention.

Embodiment 2 of the present invention:

A method for preparing a porous metal film by an electroless plating process, comprising the following steps:

The mass fraction of 10% hydrophilic polymer aqueous solution and the aqueous solution of γ-(2,3-glycidoxy)propyltrimethoxysilane and silver nitrate were mixed at a relative mass ratio of 95:20:5 at 800r/min Stir and mix at a high speed to obtain a primer solution. The above primer solution was printed on the surface of the substrate and dried at 97°C for 15min. The dried substrate was chemically plated with copper. The plating time was 26min and the plating temperature was 65°C. The substrate was washed with water and ultrasonically treated, and the ultrasonic temperature was gradually increased from 30°C to 127°C at 20°C/min, and the ultrasonic medium was paraffin to obtain a porous metal copper film.

Embodiment 3 of the present invention:

A method for preparing a porous metal film by an electroless plating process, comprising the following steps:

The mass fraction of 2% hydrophilic polymer aqueous solution and the aqueous solution of γ-(2,3-glycidoxy)propyltrimethoxysilane and silver nitrate were combined at a relative mass ratio of 115:20:5 at 1100r/min Stir and mix at a high speed to obtain a primer solution. The above primer solution was printed on the surface of the substrate and dried at 114°C for 20min. The dried substrate was chemically plated with nickel. The plating time was 37min and the plating temperature was 70°C. The substrate was washed with water and ultrasonically treated, and the ultrasonic temperature was gradually increased from 30 °C to 134 °C at 20 °C/min, and the ultrasonic medium was paraffin to obtain a porous metal nickel film.

Embodiment 4 of the present invention:

A method for preparing a porous metal film by an electroless plating process, comprising the following steps:

The mass fraction of 4% hydrophilic polymer aqueous solution and the aqueous solution of γ-(2,3-glycidoxy)propyltrimethoxysilane and silver nitrate were combined with the relative mass ratio of 135:20:5 at 1400r/min Stir and mix at a high speed to obtain a primer solution. The above primer solution was printed on the surface of the substrate and dried at 131°C for 25min. The dried substrate was chemically plated with nickel. The plating time was 48min and the plating temperature was 75°C. The substrate was washed with water and ultrasonically treated, and the ultrasonic temperature was gradually increased from 30 °C to 141 °C at 20 °C/min, and the ultrasonic medium was paraffin to obtain a porous metal nickel film.

Embodiment 5 of the present invention:

A method for preparing a porous metal film by an electroless plating process, comprising the following steps:

The mass fraction of 6% hydrophilic polymer aqueous solution and the aqueous solution of γ-(2,3-glycidoxy)propyltrimethoxysilane and silver nitrate were mixed with the relative mass ratio of 155:20:5 at 1600r/min Stir and mix at a high speed to obtain a primer solution. The above primer solution was printed on the surface of the substrate and dried at 150°C for 30min. The dried substrate was chemically plated with cobalt, the plating time was 60min, and the plating temperature was 80°C. The substrate was washed with water and ultrasonically treated, the ultrasonic temperature was gradually increased from 30 °C to 150 °C at 20 °C/min, and the ultrasonic medium was paraffin, that is, the porous metal film cobalt was obtained.

The structure, features and effects of the present invention have been described in detail above according to the embodiments shown in the drawings. The above are only the preferred embodiments of the present invention, but the scope of the present invention is not limited by the drawings. Changes made to the concept of the present invention, or modifications to equivalent embodiments with equivalent changes, shall fall within the protection scope of the present invention as long as they do not exceed the spirit covered by the description and drawings.

Claims (10)

1. A method for preparing a porous metal film by a chemical plating process is characterized by comprising the following steps: the method comprises the following steps:

(1) preparing a catalytic solution: preparing a mixed solution of first silane, second silane, ethanol, a water-based polymer solution and water, adding ammonia water to adjust the pH value to 9 in the stirring process, stirring at normal temperature for 1-30min, adjusting the pH value to 7 by using citric acid, adding a 1-200g/L catalyst ion solution, stirring for 1-30min, and adding isopropanol to obtain a catalytic solution;

(2) activating the substrate: uniformly coating the catalytic solution on the surface of a substrate, and drying at 60-150 ℃ for 1-30min to obtain an activated substrate;

(3) chemical plating: immersing the activated base material into a plating solution for plating, wherein the plating time is 15-60min, and the temperature is 60-90 ℃;

(4) and washing the plated base material with water and carrying out ultrasonic treatment to obtain the porous metal film.

2. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: in the step (1), the first silane is at least one of dimethyldimethoxysilane and methyldiethoxysilane.

3. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: the second silane in the step (1) is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane.

4. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: the mass fraction of the aqueous polymer solution in the step (1) is 1-10%.

5. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: in the step (1), the aqueous polymer solution is at least one of sodium carboxymethylcellulose, polyvinyl alcohol and polyvinylpyrrolidone aqueous solution.

6. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: in the step (1), the catalyst ions are at least one of palladium, gold, platinum and silver.

7. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: in the step (1), the mass ratio of the first silane to the second silane to the ethanol to the aqueous polymer solution to the water to the isopropanol to the catalyst ion solution is 1:0.1-5:2:10-150:0.1-100:10-1000: 0.5-50.

8. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: the surface of the base material in the step (2) contains active groups, wherein the active groups comprise hydroxyl, carboxyl, epoxy and sulfydryl.

9. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: the chemical plating in the step (3) is at least one of chemical copper plating, chemical nickel plating and chemical cobalt plating, and the thickness of the metal plating layer prepared by the chemical plating is 2-5 mu m.

10. The method for preparing a porous metal film according to the electroless plating process of claim 1, wherein: in the step (4), the ultrasonic treatment is to gradually increase the temperature from 30 ℃ to 120 ℃ at a speed of 20 ℃/min and 150 ℃, and the ultrasonic medium is liquid paraffin.

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