CN115074710A - Preparation method of super-hydrophobic structural material - Google Patents
Preparation method of super-hydrophobic structural material Download PDFInfo
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- CN115074710A CN115074710A CN202210446621.7A CN202210446621A CN115074710A CN 115074710 A CN115074710 A CN 115074710A CN 202210446621 A CN202210446621 A CN 202210446621A CN 115074710 A CN115074710 A CN 115074710A
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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
- C23C18/38—Coating with copper
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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- Y02T70/10—Measures concerning design or construction of watercraft hulls
Abstract
The invention provides a preparation method of a super-hydrophobic structure material. The method comprises the following steps: firstly, preprocessing a substrate; secondly, chemical copper plating; thirdly, preparing Cu (OH) 2 A pinpoint micro/nano structure; and fourthly, modifying by low surface energy substances. The invention utilizes the characteristic that dopamine is self-polymerized in an alkaline environment and can be adhered to various matrixes, silver is reduced under the assistance of polydopamine, silver particles catalyze chemical copper plating, and long-chain mercaptan, fatty acid or siloxane can be utilized for post-treatment, so that the problems of poor universality of the existing super-hydrophobic coating matrix, single modification selection of substances with low surface energy and the like are solved, the water drop angle on the surface of the prepared material is larger than 150 degrees, and the prepared material has an excellent oil-water separation effect.
Description
Technical Field
The invention belongs to the technical field of super-hydrophobic interface materials, and particularly relates to a preparation method of a super-hydrophobic structure material.
Background
The super-hydrophobic interface material refers to a stable water drop angle of more than 150 degrees and a rolling angle of less than 10 degrees on the surface of the material. The super-hydrophobic material has been widely used in various fields such as oil-water separation, antifogging, anti-icing, self-cleaning, ship drag reduction, etc.
From the research on the phenomenon that lotus leaves are not polluted but have silt, a series of phenomena in the nature are related to the super-hydrophobic material, such as that geckos can be adsorbed to walls to walk vertically, insects such as water striders, dragonflies and the like walk on water surfaces, and the like.
The method for obtaining the super-hydrophobic property needs to construct a micro/nano rough structure, and mainly adopts methods such as chemical etching and plasma treatment at present, but the chemical etching is only suitable for several metal materials such as copper, zinc and the like, and is not suitable for other metal, corrosion-resistant base materials and non-metal base materials, and the plasma etching method needs expensive plasma treatment equipment, has high requirement conditions, expensive equipment and complex process and does not have universality. Therefore, the construction method of the super-hydrophobic coating with substrate universality is developed without the help of expensive equipment, materials and complex processes, and has a great application prospect.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a super-hydrophobic structure material, which comprises the following steps:
taking a substrate to be treated, and carrying out substrate pretreatment based on dopamine autopolymerization on the substrate to be treated to obtain a polydopamine pretreatment product;
carrying out chemical copper plating on the polydopamine pretreatment product to obtain a copper plated product;
preparing Cu (OH) on the copper plated product 2 Preparing a needle point-shaped microstructure to obtain a microstructure copper plated product;
and carrying out low surface energy substance modification on the microstructure copper-plated product to obtain the super-hydrophobic structural material.
Preferably, the method for preparing the polydopamine pre-treatment product comprises the following steps of:
preparing a buffer solution;
dissolving dopamine in the buffer solution to obtain a solution of the dopamine;
immersing the substrate into the dopamine solution for a first reaction, taking out after the reaction, and washing with water until the dopamine solution is colorless to obtain a reaction product after the substrate reaction;
immersing the reactant into a silver ammonia solution for a second reaction, and then washing to obtain the polydopamine pretreatment product;
preferably, the pH of the buffer is 8.5;
preferably, the concentration of the dopamine solution is 0.5-5 mg/mL;
preferably, the substrate is immersed in the dopamine solution to carry out a first reaction, wherein the reaction conditions of the first reaction are that the reaction is carried out for 6-48 hours at a stirring speed of 100-1000 rpm;
preferably, the concentration of the silver ammonia solution is 1-10 g/L;
preferably, the reaction time of the second reaction is 5 to 240 min.
Preferably, the buffer is tris-hydrochloric acid solution.
Preferably, the chemical copper plating of the polydopamine pretreatment product is performed to obtain a copper plated product, and the chemical copper plating process comprises the following steps:
preparing chemical copper plating solution, and adding a reducing agent into the chemical copper plating solution to obtain reduced copper plating solution;
immersing the polydopamine pretreatment product into the reduction copper plating solution for electroless copper plating;
taking out the polydopamine pretreated product after electroless copper plating, and washing the polydopamine pretreated product with water to obtain a copper plated product;
preferably, the electroless copper plating conditions are:
the copper plating temperature is 30-60 ℃;
the copper plating time is 1-12 hours.
Preferably, the preparation method of the electroless copper plating solution comprises the following steps:
mixing 20-100mM of ethylenediamine tetraacetic acid, 20-100mM of copper chloride and 0.02-0.5M of boric acid to obtain a first mixed solution; and adjusting the pH value of the first mixed solution to 7 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution; alternatively, the first and second electrodes may be,
mixing 15-40g/L disodium ethylene diamine tetraacetate, 15-50g/L copper sulfate pentahydrate and 5-30g/L potassium sodium tartrate tetrahydrate to obtain a second mixed solution; and regulating the pH value to 12-13 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution.
Preferably, the reducing agent is 0.01M to 0.2M dimethylamine borane; or 5-30mL/L formaldehyde.
Preferably, said preparing Cu (OH) on said copper plated product 2 The method for preparing the microstructure copper-plated product with the pinpoint microstructure comprises the following steps:
preparing aqueous solution of sodium hydroxide and potassium persulfate;
immersing the copper-plated product in the aqueous solution of sodium hydroxide and potassium persulfate to produce Cu (OH) 2 A pin-shaped microstructure;
taking out the copper plated product immersed in the aqueous solution of sodium hydroxide and potassium persulfate, and washing with water to obtain the microstructure copper plated product;
preferably, the copper-plated product is immersed in the aqueous solution of sodium hydroxide and potassium persulfate to produce Cu (OH) 2 Immersing the needle-point-shaped microstructure for 1-120 minutes;
preferably, the concentration of sodium hydroxide is 1-3M; the concentration of the potassium persulfate is 0.05-0.3M.
Preferably, the low surface energy substance modification is performed on the microstructure copper-plated product to obtain the superhydrophobic structure material, and the method includes:
soaking the microstructure copper-plated product in a low-surface-energy substance solution to obtain a soaked substance;
drying the soaked substance to obtain the super-hydrophobic structural material;
preferably, the soaking time for soaking the microstructure copper-plated product in the low-surface-energy substance solution is 5-720 minutes;
preferably, the soaked substance is dried in a vacuum drying mode, and the drying temperature is 20-100 ℃.
Preferably, the low surface energy material comprises a long carbon chain thiol, fatty acid, siloxane or fluorochemical silane;
preferably, the carbon chain length of the low surface energy substance is 9-20; the concentration of the low surface energy substance is 5-40 mM.
In addition, in order to solve the problems, the application further provides a super-hydrophobic structural material, and the super-hydrophobic structural material is prepared by the preparation method of the super-hydrophobic structural material.
The invention discloses a preparation method of a super-hydrophobic structure material. Wherein the method comprises the following steps: firstly, preprocessing a substrate; secondly, chemical copper plating; thirdly, preparing Cu (OH) 2 A pinpoint micro/nano structure; and fourthly, modifying by low surface energy substances. The invention utilizes the characteristic that dopamine is self-polymerized in an alkaline environment and can be adhered to various matrixes, silver is reduced by the aid of polydopamine, silver particles catalyze chemical copper plating, and long-chain mercaptan, fatty acid or siloxane can be utilized for post-treatment, so that the problems of poor universality of the existing super-hydrophobic coating matrix, single modification selection of substances with low surface energy and the like are solved, and the water drop angles (water contact angles) on the surfaces of the prepared materials are all larger than 150 degrees, and the prepared materials have excellent oil-water separation effect.
The method has the advantages that the simple pretreatment step of chemical copper plating coarsening-sensitization is replaced by the dopamine autopolymerization treatment matrix, so that the process is more environment-friendly and simpler; the micro/nano structure suitable for various substrates is prepared by utilizing the characteristic that polydopamine can be adhered to various substrates, and the application prospect is wide. Cu (OH) 2 Can form chemical bonds with low surface energy substances such as long-chain mercaptan, fatty acid or siloxane and the like to be tightly combined, so that the super-hydrophobic material is more stableThe processing method is more various.
Drawings
FIG. 1 is a reaction scheme showing a first reaction and a second reaction which are carried out when a superhydrophobic structure material is prepared according to the present invention;
FIG. 2 is a water drop angle test of the superhydrophobic construction material prepared in example 1 of the invention;
FIG. 3 is a water drop angle test of the superhydrophobic construction material prepared in example 2 of the invention;
FIG. 4 is a water drop angle plot of a superhydrophobic construction material prepared in example 3 of the invention;
FIG. 5 is a water drop angle plot of a superhydrophobic construction material prepared in example 4 of the invention;
FIG. 6 is a water drop angle plot of a superhydrophobic construction material prepared in example 5 of the invention;
FIG. 7 is a water drop angle plot of a superhydrophobic construction material prepared in example 6 of the invention;
FIG. 8 is a water drop angle plot of a superhydrophobic construction material prepared in example 7 of the invention;
FIG. 9 is a scanning electron microscope image of a pinpoint-shaped micro/nano structure of the superhydrophobic structure material prepared in example 4 of the invention.
Reference numerals:
a substrate-1; polydopamine-2; ag particles-3.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise below, all technical and scientific terms used in the detailed description of the present invention are intended to have the same meaning as commonly understood by one of ordinary skill in the art. While the following terms are believed to be well understood by those skilled in the art, the following definitions are set forth to better explain the present invention.
As used herein, the terms "comprising," "including," "having," "containing," or "involving" are inclusive or open-ended and do not exclude additional unrecited elements or method steps. The term "consisting of …" is considered to be a preferred embodiment of the term "comprising". If in the following a certain group is defined to comprise at least a certain number of embodiments, this should also be understood as disclosing a group which preferably only consists of these embodiments.
Where an indefinite or definite article is used when referring to a singular noun e.g. "a" or "an", "the", this includes a plural of that noun.
The term "about" in the present invention denotes an interval of accuracy that can be understood by a person skilled in the art, which still guarantees the technical effect of the feature in question. The term generally denotes a deviation of ± 10%, preferably ± 5%, from the indicated value.
Furthermore, the terms first, second, third, (a), (b), (c), and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
The following is provided merely to aid in understanding the invention. These definitions should not be construed to have a scope less than understood by those skilled in the art.
The technical solution of the present invention is further described in detail by way of the following specific embodiments, but the present invention is not limited thereto, and any limited number of modifications made by anyone within the scope of the claims of the present invention are still within the scope of the claims of the present invention.
This example provides a method for preparing a superhydrophobic structure material for constructing Cu (OH) on surfaces of multiple substrates 2 A superhydrophobic structure comprising:
taking a substrate to be treated, and carrying out substrate pretreatment based on dopamine autopolymerization on the substrate to be treated to obtain a polydopamine pretreatment product;
carrying out chemical copper plating on the polydopamine pretreatment product to obtain a copper plated product;
preparing Cu (OH) on the copper plated product 2 Preparing a needle point-shaped microstructure to obtain a microstructure copper plated product;
and carrying out low surface energy substance modification on the microstructure copper-plated product to obtain the super-hydrophobic structure material.
As mentioned above, the substrate to be treated may include, but is not limited to, rush, cotton thread, rubber band, polyurethane sponge or melamine resin sponge.
The dopamine autopolymerization is the oxidative autopolymerization reaction of dopamine on the surface of a substrate to be treated, and polydopamine is formed on the surface of the substrate to be treated, so that a polydopamine pretreatment product is formed. Specifically, the process of oxidative autopolymerization of dopamine to form polydopamine is shown below.
The poly-dopamine has stronger biocompatibility and stronger material adhesion, and the embodiment utilizes the poly-dopamine to prepare the micro/nano structure suitable for various matrixes, thereby having wide application prospect.
Surface energy means that surface particles have an additional potential energy, called surface energy, than bulk particles because the bond energy of surface layer atoms facing outward is not compensated for.
The internal energy changes due to the change of the surface area of the object, and the value of the surface energy per unit area and the surface tension are the same, but the two physical meanings are different. For example: the surface area of the object is reduced due to the dust adhesion on the surface of the object, so that the surface energy of the object is reduced; in another example, crushing the stone increases the surface energy of the stone. The low surface energy material is a material with low surface energy, and mainly comprises an organic polymer, a long-chain compound and the like.
Above, Cu (OH) 2 The pinpoint microstructure is Cu (OH) 2 A pinpoint micro/nano structure as shown in fig. 1.
The super-hydrophobic interface material refers to a stable water drop angle of more than 150 degrees and a rolling angle of less than 10 degrees on the surface of the material. The super-hydrophobic material has been widely used in various fields such as oil-water separation, antifogging, anti-icing, self-cleaning, ship drag reduction, etc. From the research on the phenomenon that lotus leaves are not polluted but have silt, a series of phenomena in the nature are related to the super-hydrophobic material, such as that geckos can be adsorbed to walls to walk vertically, insects such as water striders, dragonflies and the like walk on water surfaces, and the like.
At present, micro/nano rough structures are required to be constructed for obtaining super-hydrophobic performance, and methods such as chemical etching, plasma treatment and the like are mainly used at present. However, chemical etching is only applicable to one type or some other type of substrate.
For example, 1: xu dynag (CN 105220155B) and the like, ammonia water is used for etching the surface of the cupronickel to obtain a rough structure, and then the method is only suitable for several metal materials such as copper, zinc and the like and is not suitable for other metals, corrosion-resistant base materials and non-metal base materials. The plasma etching method requires expensive plasma processing equipment and is not universal.
For example, 2: the method comprises the steps of treating the surface of a substrate by using plasma equipment (CN 105648770B), modifying the substrate by using 2-perfluorododecyl ethyl methacrylate, wherein the plasma equipment is expensive, and fluorine-containing low-surface-energy substances are expensive and easily cause environmental pollution.
Therefore, the construction method of the super-hydrophobic coating with substrate universality is developed without the help of expensive equipment, materials and complex processes, and has a great application prospect.
The embodiment discloses a preparation method of a super-hydrophobic structural materialThe method comprises the following steps: firstly, preprocessing a substrate; secondly, chemical copper plating; thirdly, preparing Cu (OH) 2 A pinpoint micro/nano structure; and fourthly, modifying by low surface energy substances. The embodiment utilizes the characteristic that dopamine is self-polymerized in an alkaline environment and can be adhered to various substrates, silver is reduced under the assistance of polydopamine, silver particles catalyze electroless copper plating, and long-chain mercaptan, fatty acid or siloxane can be utilized for post-treatment, so that the problems that the super-hydrophobic coating substrate is poor in universality, single in modification selection of low-surface-energy substances and the like are solved, the surface water drop angle of the prepared material is larger than 150 degrees, and the prepared material has an excellent oil-water separation effect.
In the embodiment, the pretreatment step of chemical copper plating coarsening-sensitization is replaced by the simple dopamine autopolymerization treatment matrix, so that the process is more environment-friendly and simpler; the micro/nano structure suitable for various substrates is prepared by utilizing the characteristic that polydopamine can be adhered to various substrates, and the application prospect is wide. Cu (OH) 2 And the hydrophobic material can form chemical bonds with low surface energy substances such as long-chain mercaptan, fatty acid or siloxane and the like to be tightly combined, so that the super-hydrophobic material is more stable, and the treatment method is more diversified.
Preferably, the method for preparing the polydopamine pre-treatment product comprises the following steps of:
preparing a buffer solution;
dissolving dopamine in the buffer solution to obtain an inverted dopamine solution;
and immersing the substrate into the dopamine solution for a first reaction, taking out the substrate after the reaction, and washing the substrate with water until the dopamine solution is colorless to obtain a reaction product after the substrate is reacted.
The first reaction, namely the dopamine autopolymerization reaction on the substrate, is described above with reference to the front part of the reaction scheme of fig. 1.
And immersing the reactant into a silver ammonia solution for a second reaction, and then washing to obtain the polydopamine pretreatment product.
The second reaction, i.e., the reduction reaction of the silver ammonium ion with respect to the reactant, is described above with reference to the rear part of the reaction route of fig. 1. Wherein, polydopamine phenolic hydroxyl has weak reducibility and adsorbability, and reduces silver ammonia ions into silver particles.
Preferably, the pH of the buffer is 8.5;
preferably, the concentration of the dopamine solution is 0.5-5 mg/mL;
preferably, the substrate is immersed in the dopamine solution to carry out a first reaction, wherein the reaction conditions of the first reaction are that the reaction is carried out for 6-48 hours at a stirring speed of 100-1000 rpm;
preferably, the concentration of the silver ammonia solution is 1-10 g/L;
preferably, the reaction time of the second reaction is 5 to 240 min.
Preferably, the buffer is tris-hydrochloric acid solution.
The washing with water may be with deionized water, and the number of times of washing may be 3.
Preferably, the chemical copper plating of the polydopamine pretreatment product is performed to obtain a copper plated product, and the chemical copper plating process comprises the following steps:
preparing a chemical copper plating solution, and adding a reducing agent into the chemical copper plating solution to obtain a reduction copper plating solution;
immersing the polydopamine pretreatment product into the reduction copper plating solution for electroless copper plating;
taking out the polydopamine pretreated product after electroless copper plating, and washing the polydopamine pretreated product with water to obtain a copper plated product;
preferably, the electroless copper plating conditions are:
the copper plating temperature is 30-60 ℃;
the copper plating time is 1-12 hours.
The washing with water may be with deionized water, and the number of times of washing may be 3.
Preferably, the preparation method of the electroless copper plating solution comprises the following steps:
mixing 20-100mM of ethylenediamine tetraacetic acid, 20-100mM of copper chloride and 0.02-0.5M of boric acid to obtain a first mixed solution; and adjusting the pH of the first mixed solution to 7 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution; alternatively, the first and second electrodes may be,
mixing 15-40g/L disodium ethylene diamine tetraacetate, 15-50g/L copper sulfate pentahydrate and 5-30g/L potassium sodium tartrate tetrahydrate to obtain a second mixed solution; and regulating the pH value to be alkali 12-13 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution.
Preferably, 40-60mM of ethylenediamine tetraacetic acid, 40-60mM of copper chloride and 0.08-0.12M of boric acid are taken to obtain a first mixed solution, and the pH value is adjusted to 7 by using 1M of sodium hydroxide solution to obtain the chemical copper plating solution; alternatively, the first and second electrodes may be,
taking 15-20g/L disodium ethylene diamine tetraacetate, 15-25g/L copper sulfate pentahydrate and 12-18g/L potassium sodium tartrate tetrahydrate to obtain a second mixed solution, and adjusting the pH value to 12-13 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution.
Preferably, the reducing agent is 0.01M to 0.2M dimethylamine borane; or 5-30mL/L formaldehyde.
Preferably, said preparing Cu (OH) on said copper plated product 2 The preparation method of the copper-plated product with the pinpoint microstructure comprises the following steps:
preparing aqueous solution of sodium hydroxide and potassium persulfate;
immersing the copper-plated product in the aqueous solution of sodium hydroxide and potassium persulfate to produce Cu (OH) 2 A pin-shaped microstructure;
taking out the copper plated product immersed in the aqueous solution of sodium hydroxide and potassium persulfate, and washing with water to obtain the microstructure copper plated product;
the washing with water may be with deionized water, and the number of times of washing may be 3.
Preferably, the copper-plated product is immersed in the aqueous solution of sodium hydroxide and potassium persulfate to produce Cu (OH) 2 Immersing the needle-point-shaped microstructure for 1-120 minutes;
preferably, the concentration of sodium hydroxide is 1-3M; the concentration of the potassium persulfate is 0.05-0.3M.
Preferably, the modifying the microstructure copper-plated product with a low surface energy substance to obtain the superhydrophobic structure material comprises:
soaking the microstructure copper-plated product in a low-surface-energy substance solution to obtain a soaked substance;
drying the soaked substance to obtain the super-hydrophobic structural material;
preferably, the soaking time for soaking the microstructure copper-plated product in the low surface energy substance solution is 5-720 minutes;
preferably, the soaked object is dried in a vacuum manner, and the drying temperature is 20-100 ℃.
Preferably, the low surface energy material comprises a long carbon chain thiol, fatty acid, siloxane or fluorochemical silane;
preferably, the carbon chain length of the low surface energy substance is 9 to 20; the concentration of the low surface energy substance is 5-40 mM.
Preferably, the carbon chain length is 12-16 mM, and the concentration is 5-20 mM.
The soaked material is prepared by using a low surface energy material substance, as shown in fig. 2.
In addition, in order to solve the problems, the application further provides a super-hydrophobic structural material, and the super-hydrophobic structural material is prepared by the preparation method of the super-hydrophobic structural material.
The invention is further illustrated by the following specific examples, but it should be understood that these examples are included merely for purposes of illustration in more detail and are not intended to limit the invention in any way.
Example (b):
the preparation method comprises the following steps:
step 10: taking a substrate to be treated, and carrying out substrate pretreatment based on dopamine autopolymerization on the substrate to be treated to obtain a polydopamine pretreatment product;
step 11, preparing a buffer solution;
step 12, dissolving dopamine in the buffer solution to obtain an inverted dopamine solution;
step 13, immersing the substrate into the dopamine solution for a first reaction, taking out the substrate after the reaction, and washing the substrate with water until the dopamine solution is colorless to obtain a reaction product after the substrate reaction;
step 14, immersing the reactant into a silver ammonia solution for a second reaction, and then washing to obtain the polydopamine pretreatment product;
step 20: carrying out chemical copper plating on the polydopamine pretreatment product to obtain a copper plated product;
step 21, preparing a chemical copper plating solution, and adding a reducing agent into the chemical copper plating solution to obtain a reduction copper plating solution;
step 22, immersing the polydopamine pretreatment product into the reduction copper plating solution for electroless copper plating;
step 23, taking out the chemically copper-plated polydopamine pretreatment product, and washing the product with water to obtain the copper-plated product;
the preparation method of the electroless copper plating solution comprises the following steps:
(method a), mixing 20-100mM ethylene diamine tetraacetic acid, 20-100mM copper chloride and 0.02-0.5M boric acid to obtain a first mixed solution; and adjusting the pH value of the first mixed solution to 7 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution; alternatively, the first and second electrodes may be,
(method b), mixing 15-40g/L disodium ethylene diamine tetraacetate, 15-50g/L copper sulfate pentahydrate and 5-30g/L potassium sodium tartrate tetrahydrate to obtain a second mixed solution; and regulating the pH value to 12-13 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution.
Step 30: preparing Cu (OH) on the copper plated product 2 Preparing a needle point-shaped microstructure to obtain a microstructure copper plated product;
step 31: preparing aqueous solution of sodium hydroxide and potassium persulfate;
step 32: immersing the copper-plated product in the aqueous solution of sodium hydroxide and potassium persulfate to produce Cu (OH) 2 A pin-shaped microstructure;
step 33: taking out the copper plated product immersed in the aqueous solution of sodium hydroxide and potassium persulfate, and washing with water to obtain the microstructure copper plated product;
step 34: soaking the microstructure copper-plated product in a low-surface-energy substance solution to obtain a soaked substance;
step 35: drying the soaked substance to obtain the super-hydrophobic structural material;
step 40: and carrying out low surface energy substance modification on the microstructure copper-plated product to obtain the super-hydrophobic structure material.
The specific parameters are as follows:
the experimental results are as follows:
the test method comprises the following steps: water drop angle test (contact angle).
Testing an instrument: contact angle measuring instrument. The device mainly comprises a light source, an injection unit, a sample stage, an acquisition system and analysis software, and adopts the principle of optical imaging.
The water drop angle (Contact angle) is the tangent to the gas-liquid interface at the intersection of the gas, liquid and solid phases, the angle between the liquid-side and the solid-liquid boundary, and is given by the symbol: the contact angle measuring instrument is an instrument for detecting the angle of a water drop by using the surface property at present. Water drop angles greater than 150 deg. are believed to provide superhydrophobic behavior.
The experimental results are as follows: examples 1 to 7 experiments water drop angle experiments show that the following table (see fig. 1 to 7) shows the results, wherein the water drop angles of the hydrophobic structural materials prepared in examples 1 to 7 all reach 150 ° or more, and it can be seen that the superhydrophobic structural materials prepared by the method provided by the present invention all have excellent oil-water separation effect. In addition, the scanning electron microscope image of the pinpoint-shaped micro/nano structure of the hydrophobic structure material prepared in example 4 is taken, and the appearance of the synthetic material can be clearly seen from fig. 8.
In a word, the invention discloses a preparation method of a super-hydrophobic structure material. The method utilizes the characteristic that dopamine is self-polymerized in an alkaline environment and can be adhered to various substrates, silver is reduced under the assistance of polydopamine, silver particles catalyze electroless copper plating, and long-chain mercaptan, fatty acid or siloxane can be utilized for post-treatment, so that the problems that the existing super-hydrophobic coating substrate is poor in universality, single in modification selection of low-surface-energy substances and the like are solved, the surface water drop angle of the prepared material is larger than 150 degrees, and the prepared material has an excellent oil-water separation effect. The simple pretreatment step of chemical copper plating coarsening-sensitization is replaced by the dopamine autopolymerization treatment matrix, so that the process is more environment-friendly and simpler; the micro/nano structure suitable for various substrates is prepared by utilizing the characteristic that polydopamine can be adhered to various substrates, and the application prospect is wide. Cu (OH) 2 And the hydrophobic material can form chemical bonds with low surface energy substances such as long-chain mercaptan, fatty acid or siloxane and the like to be tightly combined, so that the super-hydrophobic material is more stable, and the treatment method is more diversified.
While the preferred embodiment and the corresponding examples of the present invention have been described, it should be understood that various changes and modifications, including but not limited to, adjustments of proportions, flows and amounts, which are within the scope of the invention, may be made by those skilled in the art without departing from the inventive concept thereof. While the preferred embodiment and the corresponding examples of the present invention have been described, it should be understood that various changes and modifications, including but not limited to, adjustments of proportions, flows and amounts, which are within the scope of the invention, may be made by those skilled in the art without departing from the inventive concept thereof.
Claims (10)
1. A preparation method of super-hydrophobic structure material is characterized in that,
taking a substrate to be treated, and carrying out substrate pretreatment based on dopamine autopolymerization on the substrate to be treated to obtain a polydopamine pretreatment product;
carrying out chemical copper plating on the polydopamine pretreatment product to obtain a copper plated product;
preparing Cu (OH) on the copper plated product 2 Preparing a needle point-shaped microstructure to obtain a microstructure copper plated product;
and carrying out low surface energy substance modification on the microstructure copper-plated product to obtain the super-hydrophobic structure material.
2. The preparation method of the superhydrophobic structure material according to claim 1, wherein the step of taking a substrate to be treated and carrying out substrate pretreatment based on dopamine autopolymerization on the substrate to be treated to obtain a polydopamine pretreatment product comprises the following steps:
preparing a buffer solution;
dissolving dopamine in the buffer solution to obtain a solution of the dopamine;
immersing the substrate into the dopamine solution for a first reaction, taking out after the reaction, and washing with water until the dopamine solution is colorless to obtain a reaction product after the substrate reaction;
immersing the reactant into a silver ammonia solution for a second reaction, and then washing to obtain the polydopamine pretreatment product;
preferably, the pH of the buffer is 8.5;
preferably, the concentration of the dopamine solution is 0.5-5 mg/mL;
preferably, the substrate is immersed in the dopamine solution to carry out a first reaction, wherein the reaction conditions of the first reaction are that the reaction is carried out for 6-48 hours at a stirring speed of 100-1000 rpm;
preferably, the concentration of the silver ammonia solution is 1-10 g/L;
preferably, the reaction time of the second reaction is 5 to 240 min.
3. The method for preparing the superhydrophobic structure material of claim 2, wherein the buffer solution is a tris-hcl solution.
4. The method for preparing the superhydrophobic structure material of claim 1, wherein the step of performing electroless copper plating on the polydopamine pretreatment product to obtain a copper plated product comprises:
preparing a chemical copper plating solution, and adding a reducing agent into the chemical copper plating solution to obtain a reduction copper plating solution;
immersing the polydopamine pretreatment product into the reduction copper plating solution for electroless copper plating;
taking out the polydopamine pretreated product after electroless copper plating, and washing the polydopamine pretreated product with water to obtain a copper plated product;
preferably, the electroless copper plating conditions are:
the copper plating temperature is 30-60 ℃;
the copper plating time is 1-12 hours.
5. The method for preparing the superhydrophobic structure material according to claim 4,
the preparation method of the electroless copper plating solution comprises the following steps:
mixing 20-100mM of ethylenediamine tetraacetic acid, 20-100mM of copper chloride and 0.02-0.5M of boric acid to obtain a first mixed solution; and adjusting the pH of the first mixed solution to 7 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution; alternatively, the first and second electrodes may be,
mixing 15-40g/L disodium ethylene diamine tetraacetate, 15-50g/L copper sulfate pentahydrate and 5-30g/L potassium sodium tartrate tetrahydrate to obtain a second mixed solution; and regulating the pH value to 12-13 by using 1M sodium hydroxide solution to obtain the chemical copper plating solution.
6. The method for preparing the superhydrophobic structure material of claim 4, wherein the reducing agent is 0.01M to 0.2M dimethylamine borane; or 5-30mL/L formaldehyde.
7. The method for preparing the superhydrophobic structure material of claim 1, wherein the Cu (OH) is prepared on the copper-plated product 2 The preparation method of the copper-plated product with the pinpoint microstructure comprises the following steps:
preparing sodium hydroxide and potassium persulfate aqueous solution;
immersing the copper-plated product in the aqueous solution of sodium hydroxide and potassium persulfate to produce Cu (OH) 2 A pin-shaped microstructure;
taking out the copper plated product immersed in the aqueous solution of sodium hydroxide and potassium persulfate, and washing with water to obtain the microstructure copper plated product;
preferably, the copper-plated product is immersed in the aqueous solution of sodium hydroxide and potassium persulfate to produce Cu (OH) 2 Immersing the needle-point-shaped microstructure for 1-120 minutes;
preferably, the concentration of sodium hydroxide is 1-3M; the concentration of the potassium persulfate is 0.05-0.3M.
8. The method for preparing the superhydrophobic structure material according to claim 1, wherein the step of modifying the microstructure copper plating product with a low surface energy substance to obtain the superhydrophobic structure material comprises:
soaking the microstructure copper-plated product into a low surface energy substance solution to obtain a soaked substance;
drying the soaked substance to obtain the super-hydrophobic structural material;
preferably, the soaking time for soaking the microstructure copper-plated product in the low-surface-energy substance solution is 5-720 minutes;
preferably, the soaked substance is dried in a vacuum drying mode, and the drying temperature is 20-100 ℃.
9. The method of preparing the superhydrophobic structure material of claim 1, wherein the low surface energy substance comprises a long carbon chain thiol, a fatty acid, a siloxane, or a fluorine-containing silane;
preferably, the carbon chain length of the low surface energy substance is 9 to 20; the concentration of the low surface energy substance is 5-40 mM.
10. An ultrahydrophobic structural material, characterized in that the ultrahydrophobic structural material is obtained by being prepared by the method for preparing the ultrahydrophobic structural material according to any one of claims 1 to 9.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103085380A (en) * | 2013-01-29 | 2013-05-08 | 上海交通大学 | Copper super-hydrophobic surface with decay resistance and preparation method thereof |
| CN103100239A (en) * | 2013-01-04 | 2013-05-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Separation net membrane with super-hydrophilicity/underwater super-lipophobicity as well as preparation method and application thereof |
| CN105821396A (en) * | 2016-03-27 | 2016-08-03 | 华南理工大学 | Palladium-free chemical copper plating method |
| CN106929894A (en) * | 2017-02-20 | 2017-07-07 | 东南大学 | Emulsion separates the method for preparation and use with super infiltration resistant stainless steel fibre felt |
| CN108033479A (en) * | 2017-12-08 | 2018-05-15 | 许昌学院 | A kind of needle-shaped Kocide SD with super-hydrophobicity and preparation method thereof |
| CN111411353A (en) * | 2020-01-20 | 2020-07-14 | 湖北大学 | Method for collecting water mist by using silica gel block material with hydrophilic and sliding surface and tapered copper needle with super-hydrophobic-hydrophilic surface |
| CN112266722A (en) * | 2020-10-29 | 2021-01-26 | 南通大学 | Super-hydrophobic navigation body with resistance reducing function and preparation method thereof |
| WO2021141109A1 (en) * | 2020-01-09 | 2021-07-15 | 国立大学法人北海道大学 | Super-water-repellent surface member, metal copper surface member, and method for manufacturing same |
-
2022
- 2022-04-26 CN CN202210446621.7A patent/CN115074710A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100239A (en) * | 2013-01-04 | 2013-05-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Separation net membrane with super-hydrophilicity/underwater super-lipophobicity as well as preparation method and application thereof |
| CN103085380A (en) * | 2013-01-29 | 2013-05-08 | 上海交通大学 | Copper super-hydrophobic surface with decay resistance and preparation method thereof |
| CN105821396A (en) * | 2016-03-27 | 2016-08-03 | 华南理工大学 | Palladium-free chemical copper plating method |
| CN106929894A (en) * | 2017-02-20 | 2017-07-07 | 东南大学 | Emulsion separates the method for preparation and use with super infiltration resistant stainless steel fibre felt |
| CN108033479A (en) * | 2017-12-08 | 2018-05-15 | 许昌学院 | A kind of needle-shaped Kocide SD with super-hydrophobicity and preparation method thereof |
| WO2021141109A1 (en) * | 2020-01-09 | 2021-07-15 | 国立大学法人北海道大学 | Super-water-repellent surface member, metal copper surface member, and method for manufacturing same |
| CN111411353A (en) * | 2020-01-20 | 2020-07-14 | 湖北大学 | Method for collecting water mist by using silica gel block material with hydrophilic and sliding surface and tapered copper needle with super-hydrophobic-hydrophilic surface |
| CN112266722A (en) * | 2020-10-29 | 2021-01-26 | 南通大学 | Super-hydrophobic navigation body with resistance reducing function and preparation method thereof |
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