Patent ID: 12209324

DETAILED DESCRIPTION OF THE EMBODIMENTS

Various exemplary embodiments of the present application are now described in detail and this detailed description should not be considered a limitation of the present application, but should be understood as a further detailed description of certain aspects, features and embodiments of the present application.

It should be understood that the terminology described in the present application is only for describing specific embodiments and is not used to limit the present application. In addition, for the numerical range in the present application, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. The intermediate value within any stated value or stated range and every smaller range between any other stated value or intermediate value within the stated range are also included in the present application. The upper and lower limits of these smaller ranges are independently included or excluded from the range.

Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this present application relates. Although the present application only describes the preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference to disclose and describe methods and/or materials related to the documents. In case of conflict with any incorporated document, the contents of this specification shall prevail.

It is obvious to those skilled in the art that many improvements and changes are available to the specific embodiments of the present application without departing from the scope or spirit of the present application. Other embodiments will be apparent to the skilled person from the description of the present application. The description and embodiments of the present application are exemplary only.

The terms “including”, “comprising”, “having” and “containing” used in this specification are all open terms, which means including but not limited to.

A method for adjusting pH values in the embodiments of the present application is as follows: depending on the acidity or alkalinity of the solution, alkaline substances (sodium hydroxide) or acidic substances (diluted sulfuric acid) are added to the solution to adjust the pH of the solution.

The fissures in the embodiments of the present application are manually scratched fissures using an insulin needle and are approximately 20-40 micrometers (μm) in diameter.

The present application provides a preparation method of a composite membrane with self-repairing function, including following steps as shown inFIG.11:step1, adding cobalt salt, tungsten salt, complexing agent and buffering agent into water to obtain a mixed solution, and adjusting a pH value to acidity to obtain an acidic solution;step2, adding cerium oxide and surfactant into the acidic solution to obtain an electrolyte system; andstep3, placing a metal substrate in the electrolyte system for electrodeposition to obtain the composite membrane with self-repairing function.

Embodiment 1

step1, cobalt sulfate, sodium tungstate, diammonium hydrogen citrate and ammonium acetate are sequentially added into solvent water to be mixed and dissolved, and evenly stirred, where the concentrations of each component are: cobalt sulfate 16.9 grams per liter (g/L), sodium tungstate 9.9 g/L, diammonium hydrogen citrate 27.1 g/L and ammonium acetate 4.6 g/L respectively; the temperature of the mixed solution is controlled to be constant at 25 degrees Celsius (° C.), and the pH value of the mixed solution is adjusted to be 4.7 to obtain an acidic solution;step2, in a reactor with a constant temperature of 50° C., cerium dioxide particles with a particle size of 1 μm are added to the above acidic solution (the concentration of cerium dioxide particles in the solution is 1.0 g/L), and sodium dodecyl sulfate is added to the above solution under stirring conditions (the concentration of sodium dodecyl sulfate in the solution is 8 g/L), and the solution is fully stirred and dispersed, and left to stand for 24 hours (h) to obtain an electrolyte system;step3, the metallic material is electrodeposited over an area of 2.0×2.0 centimeters (cm) and the non-deposited part of it is wrapped with insulating tape to obtain the treated metallic material; andstep4, the above treated metallic material is immersed in the electrolyte system prepared in step2and the composite electrodeposition is carried out using a constant potential, with the counter electrode being a platinum sheet (the counter electrode platinum sheet is immersed in concentrated nitric acid for 15 minutes (min) before use and then removed, washed with water and dried naturally), and a three-electrode system consisting of a saturated potassium chloride solution, a salt bridge and a glycerol electrode is used for the deposition under stirring conditions at a speed of 100 r/min with a potential of −1.2 Volts (V) for 3,600 seconds (s); the composite membrane with a self-healing function is obtained after taking it out, washing it with water and blowing it dry with a cooler.

The surface morphology of the composite membrane prepared by this embodiment is observed under the scanning electron microscope, and the results are shown inFIG.1. It can be seen fromFIG.1that the surface of the composite membrane prepared by this embodiment is dense and free of fissures. The thickness of the composite membrane prepared by this embodiment is tested to be 7.46 μm and the hardness is 223.96 Vickers Hardness (HV).

If there are fissures, the membrane is placed in 3.5 wt. % NaCl solution for 7 days and the fissures are healed. The composite membrane placed in 3.5 wt. % NaCl solution for 7 days is again observed under the scanning electron microscope for the surface morphology, with the results as shown inFIG.2, which show that the fissures on the surface of the composite membrane are healed after treatment with NaCl solution.

If there are fissures, the immersion in NaCl solution is omitted and the surface morphology of the membrane is observed under scanning electron microscopy after 7 days of exposure to air, and the results of the scanning electron microscopy test show that the composite membrane fissures are not healed.

Embodiment 2

step1, cobalt sulfate, sodium tungstate, diammonium hydrogen citrate and ammonium acetate are sequentially added into solvent water to be mixed and dissolved, and evenly stirred, where the concentrations of each component are: cobalt sulfate 16.9 g/L, sodium tungstate 9.9 g/L, diammonium hydrogen citrate 27.1 g/L and ammonium acetate 4.6 g/L respectively; the temperature of the mixed solution is controlled to be constant at 25° C., and the pH value of the mixed solution is adjusted to be 4.7 to obtain an acidic solution;step2, in a reactor with a constant temperature of 50° C., cerium dioxide particles with a particle size of 500 nm are added to the above acidic solution (the concentration of cerium dioxide particles in the solution is 1.6 g/L), and sodium dodecyl sulfate is added to the above solution under stirring conditions (the concentration of sodium dodecyl sulfate in the solution is 8 g/L), and the solution is fully stirred and dispersed, and left to stand for 24 h to obtain an electrolyte system;step3, the metallic material is electrodeposited over an area of 2.0×2.0 cm and the non-deposited part of it is wrapped with insulating tape to obtain the treated metallic material; andstep4, the above treated metallic material is immersed in the electrolyte system prepared in step2and the composite electrodeposition is carried out using a constant potential, with the counter electrode being a platinum sheet (the counter electrode platinum sheet is immersed in concentrated nitric acid for 15 min before use and then removed, washed and dried naturally), and a three-electrode system consisting of a saturated potassium chloride solution, a salt bridge and a glycerol electrode is used for the deposition under stirring conditions at a speed of 100 r/min with a potential of −1.2 V for 3,600 s; the composite membrane with a self-healing function is obtained after taking it out, washing it with water and blowing it dry with a cooler.

The surface morphology of the composite membrane prepared by this embodiment is observed under the scanning electron microscope, and the results are shown inFIG.3. It can be seen fromFIG.3that the surface of the composite membrane prepared by this embodiment is dense and free of fissures. The thickness of the composite membrane prepared by this embodiment is tested to be 6.26 μm and the hardness is 221.71 HV.

If there are fissures, the membrane is placed in 3.5 wt. % NaCl solution for 7 days and the fissures are healed. The composite membrane placed in 3.5 wt. % NaCl solution for 7 days is again observed under the scanning electron microscope for the surface morphology, with the results shown inFIG.4, which show that the fissures on the surface of the composite membrane are healed after treatment with NaCl solution.

Embodiment 3

step1, cobalt sulfate, sodium tungstate, diammonium hydrogen citrate and ammonium acetate are sequentially added into solvent water to be mixed and dissolved, and evenly stirred, where the concentrations of each component are: cobalt sulfate 16.9 g/L, sodium tungstate 9.9 g/L, diammonium hydrogen citrate 27.1 g/L and ammonium acetate 4.6 g/L respectively; the temperature of the mixed solution is controlled to be constant at 25° C., and the pH value of the mixed solution is adjusted to be 4.7 to obtain an acidic solution;step2, in a reactor with a constant temperature of 50° C., cerium dioxide particles with a particle size of 500 nm are added to the above acidic solution (the concentration of cerium dioxide particles in the solution is 1.2 g/L), and sodium dodecyl sulfate is added to the above solution under stirring conditions (the concentration of sodium dodecyl sulfate in the solution is 8 g/L), and the solution is fully stirred and dispersed, and left to stand for 24 h to obtain an electrolyte system;step3, the metallic material is electrodeposited over an area of 2.0×2.0 cm and the non-deposited part of it is wrapped with insulating tape to obtain the treated metallic material; andstep4, the above treated metallic material is immersed in the electrolyte system prepared in step2and the composite electrodeposition is carried out using a constant potential, with the counter electrode being a platinum sheet (the counter electrode platinum sheet is immersed in concentrated nitric acid for 15 min before use and then removed, washed and dried naturally), and a three-electrode system consisting of a saturated potassium chloride solution, a salt bridge and a glycerol electrode is used for the deposition under stirring conditions at a speed of 100 r/min with a potential of −1.2 V for 3,600 s; the composite membrane with a self-healing function is obtained after taking it out, washing it with water and blowing it dry with a cooler.

The surface morphology of the composite membrane prepared by this embodiment is observed under the scanning electron microscope, and the results are shown inFIG.5. It can be seen fromFIG.5that the surface of the composite membrane prepared by this embodiment is dense and free of fissures. The thickness of the composite membrane prepared by this embodiment is tested to be 6.40 μm and the hardness is 233.31 HV.

The composite membrane prepared in this embodiment is subjected to the same fissure repair test as in Embodiment 1, and the results show that after the composite membrane develops fissures and being placed in a 3.5 wt. % NaCl solution for 7 days, the fissures are healed.

Embodiment 4

step1, cobalt sulfate, sodium tungstate, diammonium hydrogen citrate and ammonium acetate are sequentially added into solvent water to be mixed and dissolved, and evenly stirred, where the concentrations of each component are: cobalt sulfate 16.9 g/L, sodium tungstate 9.9 g/L, diammonium hydrogen citrate 27.1 g/L and ammonium acetate 4.6 g/L respectively; the temperature of the mixed solution is controlled to be constant at 25° C., and the pH value of the mixed solution is adjusted to be 4.7 to obtain an acidic solution;step2, in a reactor with a constant temperature of 50° C., cerium dioxide particles with a particle size of 1 μm are added to the above acidic solution (the concentration of cerium dioxide particles in the solution is 1.6 g/L), and sodium dodecyl sulfate is added to the above solution under stirring conditions (the concentration of sodium dodecyl sulfate in the solution is 8 g/L), and the solution is fully stirred and dispersed, and left to stand for 24 h to obtain an electrolyte system;step3, the metallic material is electrodeposited over an area of 2.0×2.0 cm and the non-deposited part of it is wrapped with insulating tape to obtain the treated metallic material; andstep4, the above treated metallic material is immersed in the electrolyte system prepared in step2and the composite electrodeposition is carried out using a constant potential, with the counter electrode being a platinum sheet (the counter electrode platinum sheet is immersed in concentrated nitric acid for 15 min before use and then removed, washed and dried naturally), and a three-electrode system consisting of a saturated potassium chloride solution, a salt bridge and a glycerol electrode is used for the deposition under stirring conditions at a speed of 100 r/min with a potential of −1.2 V for 3,600 s; the composite membrane with a self-healing function is obtained after taking it out, washing it with water and blowing it dry with a cooler.

The surface morphology of the composite membrane prepared by this embodiment is observed under the scanning electron microscope, and the results are shown inFIG.6. It can be seen fromFIG.6that the surface of the composite membrane prepared by this embodiment is dense and free of fissures. The thickness of the composite membrane prepared by this embodiment is tested to be 6.00 μm and the hardness is 243.05 HV.

The composite membrane prepared in this embodiment is subjected to the same fissure repair test as in Embodiment 1, and the results show that after the composite membrane develops fissures and being placed in a 3.5 wt. % NaCl solution for 7 days, the fissures are healed.

Embodiment 5

step1, cobalt sulfate, sodium tungstate, diammonium hydrogen citrate and ammonium acetate are sequentially added into solvent water to be mixed and dissolved, and evenly stirred, where the concentrations of each component are: cobalt sulfate 16.9 g/L, sodium tungstate 9.9 g/L, diammonium hydrogen citrate 27.1 g/L and ammonium acetate 4.6 g/L respectively; the temperature of the mixed solution is controlled to be constant at 25° C., and the pH value of the mixed solution is adjusted to be 4.7 to obtain an acidic solution;step2, in a reactor with a constant temperature of 50° C., cerium dioxide particles with a particle size of 500 nm are added to the above acidic solution (the concentration of cerium dioxide particles in the solution is 2.0 g/L), and sodium dodecyl sulfate is added to the above solution under stirring conditions (the concentration of sodium dodecyl sulfate in the solution is 8 g/L), and the solution is fully stirred and dispersed, and left to stand for 24 h to obtain an electrolyte system;step3, the metallic material is electrodeposited over an area of 2.0×2.0 cm and the non-deposited part of it is wrapped with insulating tape to obtain the treated metallic material; andstep4, the above treated metallic material is immersed in the electrolyte system prepared in step2and the composite electrodeposition is carried out using a constant potential, with the counter electrode being a platinum sheet (the counter electrode platinum sheet is immersed in concentrated nitric acid for 15 min before use and then removed, washed and dried naturally), and a three-electrode system consisting of a saturated potassium chloride solution, a salt bridge and a glycerol electrode is used for the deposition under stirring conditions at a speed of 100 r/min with a potential of −1.2 V for 3,600 s; the composite membrane with a self-healing function is obtained after taking it out, washing it with water and blowing it dry with a cooler.

The surface morphology of the composite membrane prepared by this embodiment is observed under the scanning electron microscope, and the results are shown inFIG.7. It can be seen fromFIG.7that the surface of the composite membrane prepared by this embodiment is dense and free of fissures. The thickness of the composite membrane prepared by this embodiment is tested to be 5.96 μm and the hardness is 252.99 HV.

The composite membrane prepared in this embodiment is subjected to the same fissure repair test as in Embodiment 1, and the results show that after the composite membrane develops fissures and being placed in a 3.5 wt. % NaCl solution for 7 days, the fissures heal.

Embodiment 6

step1, cobalt sulfate, sodium tungstate, diammonium hydrogen citrate and ammonium acetate are sequentially added into solvent water to be mixed and dissolved, and evenly stirred, where the concentrations of each component are: cobalt sulfate 16.9 g/L, sodium tungstate 9.9 g/L, diammonium hydrogen citrate 27.1 g/L and ammonium acetate 4.6 g/L respectively; the temperature of the mixed solution is controlled to be constant at 25° C., and the pH value of the mixed solution is adjusted to be 4.7 to obtain an acidic solution;step2, in a reactor with a constant temperature of 50° C., cerium dioxide particles with a particle size of 1 μm are added to the above acidic solution (the concentration of cerium dioxide particles in the solution is 1.2 g/L), and sodium dodecyl sulfate is added to the above solution under stirring conditions (the concentration of sodium dodecyl sulfate in the solution is 8 g/L), and the solution is fully stirred and dispersed, and left to stand for 24 h to obtain an electrolyte system;step3, the metallic material is electrodeposited over an area of 2.0×2.0 cm and the non-deposited part of it is wrapped with insulating tape to obtain the treated metallic material; andstep4, the above treated metallic material is immersed in the electrolyte system prepared in step2and the composite electrodeposition is carried out using a constant potential, with the counter electrode being a platinum sheet (the counter electrode platinum sheet is immersed in concentrated nitric acid for 15 min before use and then removed, washed and dried naturally), and a three-electrode system consisting of a saturated potassium chloride solution, a salt bridge and a glycerol electrode is used for the deposition under stirring conditions at a speed of 100 r/min with a potential of −1.2 V for 3,600 s; the composite membrane with a self-healing function is obtained after taking it out, washing it with water and blowing it dry with a cooler.

The surface morphology of the composite membrane prepared by this embodiment is observed under the scanning electron microscope, and the results are shown inFIG.8. It can be seen fromFIG.8that the surface of the composite membrane prepared by this embodiment is dense and free of fissures. The thickness of the composite membrane prepared by this embodiment is tested to be 6.50 μm and the hardness is 241.02 HV.

The composite membrane prepared in this embodiment is subjected to the same fissure repair test as in Embodiment 1, and the results show that after the composite membrane develops fissures and being placed in a 3.5 wt. % NaCl solution for 7 days, the fissures heal.

Comparative Embodiment 1

Same as Embodiment 1, except that the addition of sodium dodecyl sulfate in step2is omitted.

The surface morphology of the composite membrane prepared by this comparative embodiment is observed under the scanning electron microscope, and the results are shown inFIG.9. It can be seen fromFIG.9that the surface of the composite membrane prepared by this comparative embodiment is dense and free of fissures. The thickness of the composite membrane prepared by this comparative embodiment is tested to be 5.10 μm and the hardness is 218.28 HV.

The composite membrane prepared in this comparative embodiment is tested for fissure repair in the same manner as Embodiment 1, and the results show that after the composite membrane develops fissures and is placed in a 3.5 wt. % NaCl solution for 7 days, the fissure healing rate decreases and the healing performance is poor.

Comparative Embodiment 2

Same as Embodiment 1, except that the addition of cerium dioxide particles and sodium dodecyl sulfate in step2is omitted.

The surface morphology of the composite membrane prepared by this comparative embodiment is observed under the scanning electron microscope, and the results are shown inFIG.10. It can be seen fromFIG.10that the surface of the composite membrane prepared by this comparative embodiment is very dense and free of fissures. The thickness of the composite membrane prepared by this comparative embodiment is tested to be 2.5 μm and the hardness is 132.81 HV.

The composite membrane prepared in this comparative embodiment is tested for fissure repair in the same manner as Embodiment 1, and the results show that after the composite membrane develops fissures and is placed in a 3.5 wt. % NaCl solution for 7 days, the fissures do not change and do not heal.

Comparative Embodiment 3

Same as Embodiment 1, except that the particle size of the cerium dioxide particles in step2is 500 nm.

The surface morphology of the composite membrane prepared by this comparative embodiment is observed under scanning electron microscopy, which shows that the surface of the composite membrane is flat with a few fissures. The thickness of the composite membrane is tested to be 5.70 μm and the hardness is 184.06 HV.

When fissures are present (same as in Embodiment 1, manual scratching of fissures with an insulin needle, about 20-40 μm in diameter), the membrane is placed in a 3.5 wt. % NaCl solution for 7 days and the fissures are healed.

The embodiments described above are only a description of the preferred way of the present application and are not intended to limit the scope of the present application. Without departing from the design spirit of the present application, all kinds of variations and improvements made to the technical schemes of the present application by persons of ordinary skill in the art shall fall within the scope of protection determined by the claims of the present application.