阅读说明：本技术 一种混凝土防腐涂层及其制备方法 (Concrete anticorrosive coating and preparation method thereof ) 是由 尹兵 侯东帅 徐天元 王鑫鹏 张悦 于 2019-09-09 设计创作，主要内容包括：本发明提供了一种混凝土防腐涂层及其制备方法,属于混凝土防护领域。本发明提供的制备方法包括以下步骤：1)利用多巴胺溶液对混凝土进行修饰改性,在混凝土表面形成改性诱导层；2)将所述步骤1)得到的混凝土和阳离子矿化剂溶液进行螯合反应后,再和阴离子矿化剂溶液进行矿化反应,在混凝土改性诱导层表面生成仿生矿化层；3)将所述步骤2)得到的混凝土和硅烷乙醇溶液进行硅烷化处理,在混凝土仿生矿化层表面生成低表面能层,得到混凝土防腐涂层,混凝土防腐涂层与混凝土的界面结合好,防腐涂层的结构缺陷少,同时具有优良的疏水、防水性能、涂层硬度较高、耐磨性能较好。(The invention provides a concrete anticorrosive coating and a preparation method thereof, belonging to the field of concrete protection. The preparation method provided by the invention comprises the following steps: 1) modifying and modifying the concrete by utilizing a dopamine solution, and forming a modified induction layer on the surface of the concrete; 2) carrying out chelation reaction on the concrete obtained in the step 1) and a cation mineralizer solution, and then carrying out mineralization reaction on the concrete and an anion mineralizer solution to generate a bionic mineralized layer on the surface of the concrete modified induction layer; 3) performing silanization treatment on the concrete obtained in the step 2) and a silane ethanol solution to generate a low surface energy layer on the surface of the bionic mineralization layer of the concrete, so as to obtain the concrete anticorrosive coating, wherein the concrete anticorrosive coating is well combined with the interface of the concrete, the structural defects of the anticorrosive coating are few, and the concrete anticorrosive coating has excellent hydrophobic and waterproof properties, high coating hardness and good wear resistance.)

1. The preparation method of the concrete anticorrosive coating is characterized by comprising the following steps of:

1) modifying and modifying the concrete by utilizing a dopamine solution, and forming a modified induction layer on the surface of the concrete;

2) Carrying out chelation reaction on the concrete obtained in the step 1) and a cation mineralizer solution, and then carrying out mineralization reaction on the concrete and an anion mineralizer solution to generate a bionic mineralized layer on the surface of the concrete modified induction layer;

3) Performing silanization treatment on the concrete obtained in the step 2) and a silane ethanol solution to generate a low surface energy layer on the surface of the bionic mineralization layer of the concrete, so as to obtain a concrete anticorrosive coating;

The anion in the anion mineralizer solution is CO 32-or SiO 32-.

2. The method according to claim 1, wherein the dopamine solution has a mass concentration of 0.4 to 5.0 g-L "1.

3. The preparation method according to claim 1, wherein the temperature of the modification is 5-40 ℃ and the time is 8-48 h.

4. The method according to claim 1, wherein the molar concentration of the cationic mineralizer solution is 0.02 to 2.0 moL-L "1.

5. the method according to claim 1, wherein the chelating reaction is carried out at a temperature of 1 to 45 ℃ for 10 to 120 seconds.

6. the method according to claim 1, wherein the molar concentration of the anionic mineralizer solution is 0.02 to 2.0 moL-L "1.

7. The method according to claim 1, wherein the temperature of the mineralization reaction is 1-45 ℃ and the time is 10-120 s.

8. The method according to claim 1, wherein the concentration of silane in the silanolate solution is 0.1-5% by mass.

9. The method according to claim 1, wherein the silylation treatment is carried out at a temperature of 1 to 45 ℃ for 1 to 12 hours.

10. The concrete anticorrosive coating prepared by the preparation method of any one of claims 1 to 9, which is characterized by comprising a modified induction layer, a bionic mineralization layer and a low surface energy layer which are sequentially attached to the surface of concrete.

Technical Field

The invention belongs to the field of concrete protection, and particularly relates to a concrete anticorrosive coating and a preparation method thereof.

background

Concrete is a porous hydrophilic material and is easily degraded by the influence of the harsh and complex environment of the coast. The commonly adopted concrete protection means is to coat an anticorrosive coating on the surface of the concrete, and by isolating water, carbon dioxide, ions and the like from invasion, the service cycle of the reinforcing steel bar is prolonged, the durability of the concrete is improved, and the engineering life is prolonged.

the traditional concrete anticorrosion coating has the following defects: 1) the defect that the durability of the concrete under the load action is influenced by the heterogeneous porous structure of the concrete is difficult to make up; 2) the interface bonding of the coating is poor, and the material has structural and performance defects due to the difficult chemical modification and reaction between the micro-nano structure and the pore channel; 3) organic systems are difficult to withstand long term aging tests.

The inorganic mineralized material can block the microstructure of the surface layer of the concrete, improve the strength of the cement-based material, delay and repair the crack development, and prevent the invasion of external moisture and harmful ions, thus being an ideal concrete anti-corrosion reinforcing material. However, the material has high requirements on application process, humidity, treatment time and the like when being used as a concrete coating; the mineralization process has low controllability, and particularly, the in-situ precise mineralization modification and protection of micro-nano spaces are difficult; the introduced mineralization treatment agent is easy to damage the microstructure of the concrete, and the performance and the strength of the concrete are reduced. These make it difficult to achieve the desired protective effect.

Marine mussel organisms secrete adhesive proteins through byssus and can also exhibit superior adhesive capacity in humid environments. Mussel adhesive proteins have two distinct characteristics: firstly, the film can be adhered to the surface of almost all materials; secondly, the surface of the formed film contains a large number of active functional groups, a series of reactions can occur, and favorable conditions can be provided for further modification. However, the use of an adhesive protein derivative represented by dopamine as an interface material is limited by severe curing conditions, few functional considerations, low aging resistance, low mechanical strength, and the like.

Disclosure of Invention

In view of the above, the invention aims to provide a concrete anticorrosive coating and a preparation method thereof.

In order to solve the above object, the present invention provides the following technical solutions:

The invention provides a preparation method of a concrete anticorrosive coating, which comprises the following steps:

A preparation method of a concrete anticorrosive coating comprises the following steps:

1) Modifying and modifying the concrete by utilizing a dopamine solution, and forming a modified induction layer on the surface of the concrete;

2) Carrying out chelation reaction on the concrete obtained in the step 1) and a cation mineralizer solution, and then carrying out mineralization reaction on the concrete and an anion mineralizer solution to generate a bionic mineralized layer on the surface of the concrete modified induction layer;

3) Performing silanization treatment on the concrete obtained in the step 2) and a silane ethanol solution to generate a low surface energy layer on the surface of the bionic mineralization layer of the concrete, so as to obtain a concrete anticorrosive coating;

The anion in the anion mineralizer solution is CO 32-or SiO 32-.

Preferably, the mass concentration of the dopamine solution is 0.4-5.0 g.L < -1 >.

Preferably, the temperature of the modification is 5-40 ℃, and the time is 8-48 h.

Preferably, the molar concentration of the cation mineralizer solution is 0.02-2.0 mol.L < -1 >.

preferably, the temperature of the chelation reaction is 1-45 ℃ and the time is 10-120 s.

Preferably, the molar concentration of the anion mineralizer solution is 0.02-2.0 mol.L < -1 >.

Preferably, the temperature of the mineralization reaction is 1-45 ℃ and the time is 10-120 s.

Preferably, the mass concentration of the silane in the silane ethanol solution is 0.1-5%.

Preferably, the temperature of the silanization treatment is 1-45 ℃, and the time is 1-12 h.

the invention also provides a concrete anticorrosive coating prepared by the preparation method in the technical scheme, which is characterized by comprising a modified induction layer, a bionic mineralization layer and a low surface energy layer which are sequentially attached to the surface of concrete.

The invention provides a preparation method of a concrete anticorrosive coating, which comprises the following steps: 1) modifying and modifying the concrete by utilizing a dopamine solution, and forming a modified induction layer on the surface of the concrete; 2) carrying out chelation reaction on the concrete obtained in the step 1) and a cation mineralizer solution, and then carrying out mineralization reaction on the concrete and an anion mineralizer solution to generate a bionic mineralized layer on the surface of the concrete modified induction layer; 3) performing silanization treatment on the concrete obtained in the step 2) and a silane ethanol solution to generate a low surface energy layer on the surface of the bionic mineralization layer of the concrete, so as to obtain a concrete anticorrosive coating; the anion in the anion mineralizer solution is CO 32-or SiO 32-. The method comprises the steps of firstly adopting a dopamine solution to modify and modify the concrete, attaching a layer of bionic adhesive protein film on the surface of the concrete to form a modified induction layer, and utilizing the specific molecular structure and rich active groups (amino, benzene ring, hydroxyl and catechol) of the bionic adhesive protein film to carry out precise chemical modification and modification on the internal microstructure of the concrete so as to provide a template and a carrier for the subsequent induction process and mineralization reaction; then the bionic adhesion protein film is used for absorbing and inducing cations in the cation mineralizer solution, so that the cations and the bionic adhesion protein film are subjected to chelation reaction and then subjected to in-situ mineralization reaction with CO 32-and SiO 32-in the anion mineralizer solution, and the generated mineralized crystal particles endow the mineralized layer with a micro/nano structure; on the basis, the silane ethanol solution is adopted to carry out modification reaction of functional molecules on the generated bionic mineralized layer to generate a low surface energy layer, and the concrete anticorrosive coating is obtained. The concrete anticorrosive coating prepared by the preparation method provided by the invention has good interface combination with concrete, has few structural defects, and simultaneously has excellent hydrophobic and waterproof properties, high coating hardness and good wear resistance. The preparation method provided by the invention is mild and controllable, and the preparation of the anticorrosive coating can be realized through an integrated technology. The results of the examples show that the interface bonding between the concrete anticorrosive coating prepared by the invention and the concrete is good, the structural defects of the anticorrosive coating are few, the contact angle with water drops is 150-156 degrees, the rolling angle is 8-10 degrees, and the water absorption rate is less than or equal to 0.36 percent, which indicates that the concrete anticorrosive coating has excellent hydrophobic and waterproof properties, the Vickers hardness of the surface layer of the mortar standard block prepared in the examples is 93-HV 117, and the hardness of the concrete anticorrosive coating is high, and the concrete anticorrosive coating has good wear resistance.

Drawings

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

fig. 1 is a schematic structural diagram of a concrete anticorrosive coating provided by the present invention, wherein 1 is a concrete substrate, 2 is a modification inducing layer, 3 is a biomimetic mineralized layer, 4 is a low surface energy layer, and 5 is water drops;

FIG. 2 is an SEM image of the biomimized layer generated in example 1, wherein a is an SEM image of the biomimized layer at 3000 times and b is an SEM image of the biomimized layer at 2000 times;

FIG. 3 is a graph showing the hydrophobic property test of the concrete anticorrosive coating obtained in example 1;

FIG. 4 is a comparison of water absorption of the mortar standard block prepared in example 1, a mortar standard block coated with a commercially available silane coating, and a conventional mortar standard block;

FIG. 5 is an SEM image of a biomimetic mineralized layer generated in example 2;

FIG. 6 is a graph showing the hydrophobic property test of the concrete anticorrosive coating obtained in example 2;

FIG. 7 is a comparison of water absorption of the mortar standard block prepared in example 2 and that of a conventional mortar standard block;

FIG. 8 is an SEM image of a biomimetic mineralized layer generated by example 3;

FIG. 9 is a graph showing the hydrophobic property test of the concrete corrosion protective coating obtained in example 3;

FIG. 10 is a comparison of water absorption of the mortar standard block prepared in example 3 and that of a conventional mortar standard block;

FIG. 11 is an SEM image of a biomimetic mineralized layer generated by example 4;

FIG. 12 is a graph showing a test of the hydrophobic property of the concrete corrosion protective coating obtained in example 4;

FIG. 13 is a comparison of water absorption of the mortar standard block prepared in example 4 and that of a conventional mortar standard block;

FIG. 14 is an SEM image of a biomimetic mineralized layer generated by example 7;

FIG. 15 is a graph showing the test of the hydrophobic property of the concrete corrosion protective coating obtained in example 7;

FIG. 16 is an SEM image of a biomimetic mineralized layer generated by example 8;

FIG. 17 is a graph showing a test of the hydrophobic property of the concrete anticorrosive coating obtained in example 8;

FIG. 18 is an SEM image of a biomimetic mineralized layer generated by example 9;

FIG. 19 is a graph showing a test of hydrophobic property of the concrete corrosion prevention coating obtained in example 9.

Detailed Description

the invention provides a preparation method of a concrete anticorrosive coating, which comprises the following steps:

1) Modifying and modifying the concrete by utilizing a dopamine solution, and forming a modified induction layer on the surface of the concrete;

2) carrying out chelation reaction on the concrete obtained in the step 1) and a cation mineralizer solution, and then carrying out mineralization reaction on the concrete and an anion mineralizer solution to generate a bionic mineralized layer on the surface of the concrete modified induction layer;

3) performing silanization treatment on the concrete obtained in the step 2) and a silane ethanol solution to generate a low surface energy layer on the surface of the bionic mineralization layer of the concrete, so as to obtain a concrete anticorrosive coating;

the anion in the anion mineralizer solution is CO 32-or SiO 32-.

The invention utilizes dopamine solution to modify the concrete, and forms a modified inducing layer on the surface of the concrete.

In the present invention, the concentration of the dopamine solution is preferably 0.4 to 5.0 g.L < -1 >, more preferably 1 to 3 g.L < -1 >, and even more preferably 1.5 to 2.5 g.L < -1 >. In the invention, the dosage ratio of the dopamine solution to the concrete is preferably 2: 1-8: 1, and more preferably 4: 1-6: 1. The invention adopts dopamine solution with specific concentration and dosage to modify and modify concrete, a layer of bionic adhesive protein film is adhered on the surface of the concrete to form a modified inducing layer, the inner microstructure of the concrete is precisely chemically modified and modified by utilizing the specific molecular structure and rich active groups (amino, benzene ring, hydroxyl and catechol) of the bionic adhesive protein film, and the bionic adhesive protein film not only can enhance the interface adhesive force between the concrete and the subsequent coating, but also can induce and adsorb calcium ions, magnesium ions, zinc ions or copper ions to carry out the subsequent chelation reaction, and the inducing process and the mineralization reaction are controllable, and the mineralizer solution is isolated from directly contacting with the basic aggregate in the concrete, so that the reaction between the mineralizer solution and the basic aggregate in the concrete is reduced or prevented, in addition, the bionic adhesive protein film can generate gel with good mechanical property by complexing with the ions, enhancing the ability to withstand shear. In the invention, the modified inducing layer is a bionic adhesive protein film.

In the present invention, the dopamine solution is preferably prepared by a method comprising the following steps: and mixing dopamine hydrochloride with a Tris-hydrochloric acid buffer solution to obtain the dopamine solution. In the invention, the pH value of the Tris-hydrochloric acid buffer solution is preferably 8-9, and the concentration is preferably 0.005-0.02 mol.L < -1 >. In the invention, the dosage ratio of the dopamine hydrochloride to the Tris-hydrochloric acid buffer solution is preferably 0.4-5.0 g: 0.005-0.02 moL. The sources of the dopamine hydrochloride and Tris-hydrochloric acid buffer solution are not particularly limited, and the conventional commercial products in the field can be adopted.

According to the invention, deionized water is preferably adopted to wash the concrete, and then the concrete is mixed with the dopamine solution. In the invention, the cleaning frequency is preferably 3-5 times, and the time is preferably 1-5 min/time.

After the deionized water cleaning is finished, the obtained water cleaning product is preferably cleaned by ultrasonic, and the frequency of ultrasonic cleaning is preferably 3 times. The ultrasonic cleaning condition is not specially limited, and the concrete can be cleaned. The source of the concrete is not particularly limited in the invention, and the concrete can be prepared by adopting a product which is commercially available or prepared by adopting a conventional method in the field.

In the invention, the modification mode is preferably oscillation, and the frequency of the oscillation is preferably 100-200 r.min < -1 >.

In the invention, the temperature of modification is preferably 5-40 ℃, more preferably 20-30 ℃, and the time is preferably 8-48 h.

After the modification is finished, the invention preferably sequentially washes and dries the obtained modified product by deionized water, and then forms a modification inducing layer on the surface of the concrete.

In the present invention, the number of washing is preferably 3 to 5. In the invention, the drying temperature is preferably 5-80 ℃, and the drying time is preferably 4-24 h. The drying method is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.

After a modified induction layer is formed on the surface of the concrete, the obtained concrete is mixed with a cation mineralizer solution for chelation reaction, and then mixed with an anion mineralizer solution for mineralization reaction, so that a bionic mineralized layer is formed on the surface of the modified induction layer of the concrete.

in the invention, the cation mineralizer solution preferably comprises a calcium chloride solution, a calcium acetate solution, a calcium lactate solution, a calcium bromide solution, a calcium nitrate solution, a magnesium chloride solution, a magnesium nitrate solution, a magnesium bromide solution, a magnesium sulfate solution, a zinc chloride solution, a zinc nitrate solution, a zinc chloride solution, a zinc sulfate solution, a zinc acetate solution, a copper chloride solution, a copper sulfate solution or a copper nitrate solution, and the molar concentration of the cation mineralizer solution is preferably 0.02-2.0 mol.L < -1 >, more preferably 0.2-1.0 mol.L < -1 >, and more preferably 0.3-0.7 mol.L < -1 >. In the invention, the dosage ratio of the cationic mineralizer solution to the concrete is preferably 2: 1-8: 1, and more preferably 4: 1-6: 1. The specific source of the cationic mineralizer solution is not particularly limited in the present invention, and any product that is commercially available or prepared by a method that is conventional in the art may be used. According to the invention, the cation mineralizer solution with specific concentration and dosage is adopted, calcium ions, magnesium ions, zinc ions or copper ions in the cation mineralizer solution can be attached to the surface of the bionic adhesive protein film, and generate chelation reaction with the bionic adhesive protein film, and perform in-situ mineralization reaction with CO 32-and SiO 32-in subsequent mineralized liquid, so that a defect-free bionic mineralized layer is generated.

in the present invention, the chelation reaction is preferably carried out under the impregnation condition. The impregnation method of the present invention is not particularly limited, and any impregnation method known to those skilled in the art may be used. In the invention, the time of the chelation reaction is preferably 10-120 s, the temperature is preferably 1-45 ℃, and the further preferably 20-30 ℃. After the chelation reaction is finished, the obtained chelation product is preferably washed and dried in sequence, and then is mixed with a mineralizer solution for mineralization reaction. In the invention, the washing is preferably carried out in deionized water, and the washing time is preferably 20-60 s. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. In the invention, the drying temperature is preferably 5-80 ℃. The drying method is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.

In the invention, the anion mineralizer solution is preferably a Na2CO3 solution, a Na2SiO3 solution or a K2CO3 solution, and the molar concentration of the anion mineralizer solution is preferably 0.02-2.0 mol.L < -1 >, more preferably 0.2-1.0 mol.L < -1 >, and more preferably 0.3-0.7 mol.L < -1 >. In the invention, the dosage ratio of the anionic mineralizer to the concrete is preferably 2:1 to 8:1, and more preferably 4:1 to 6: 1. The specific source of the anionic mineralizer solution is not particularly limited in the present invention, and any product that is commercially available or prepared by a method that is conventional in the art may be used. According to the invention, an anion mineralizer solution with specific concentration and dosage is adopted, CO 32-and SiO 32-in the anion mineralizer solution can carry out mineralization reaction with calcium ions, magnesium ions, zinc ions or copper ions, and then diffusion crystallization is carried out to generate mineralized products and mineralized layers, the generation speed of the mineralized products, the size of crystal particles of the mineralized products and the structure and shape of the mineralized product layers can be controlled according to the concentrations of the calcium ions, the magnesium ions, the zinc ions or the copper ions and CO 32-or SiO32-, and the generated mineralized crystal particles have compact structures, so that the coatings and the concrete surface layers can be endowed with stronger mechanical strength, and the stability of the coatings can be enhanced.

in the present invention, the mineralization reaction is preferably carried out under the impregnation conditions. The impregnation method of the present invention is not particularly limited, and any impregnation method known to those skilled in the art may be used. In the invention, the time of the mineralization reaction is preferably 10-120 s, the temperature is preferably 1-45 ℃, and the further preferably 20-30 ℃. After the mineralization reaction is finished, the obtained mineralized product is preferably washed and dried in sequence, and the bionic mineralized layer is generated on the surface of the concrete modified induction layer. In the invention, the washing is preferably carried out in deionized water, and the washing time is preferably 20-60 s. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. In the invention, the drying temperature is preferably 5-80 ℃. The drying method is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.

In the invention, the thickness of the bionic mineralization layer is preferably 10-200 μm, and more preferably 30-100 μm. According to the invention, the chelation reaction and the mineralization reaction are preferably carried out for multiple times in a circulating manner, and the circulating times are preferably 5-15 times. According to the invention, through repeated circulation of the above reactions, the mineralization reaction is thorough, the structural defects of the concrete anticorrosion coating are few, and the required micro-nano composite structure is constructed.

After a bionic mineralized layer is generated on the surface of the concrete modification induction layer, the obtained concrete and the silane ethanol solution are subjected to silanization treatment, and a low surface energy layer is generated on the surface of the concrete bionic mineralized layer, so that the concrete anticorrosive coating is obtained.

In the invention, the mass concentration of silane in the silane ethanol solution is preferably 0.1-5.0%, more preferably 0.5-3.0%, and more preferably 0.7-2.0%, the kind of the silane ethanol solution is preferably long-chain fluoroalkyl silane ethanol solution or long-chain alkyl silane ethanol solution, and the number of carbon atoms of silane in the silane ethanol solution is more than or equal to 8, and more preferably 12-18. The specific source of the silaneethanol solution is not particularly limited in the present invention, and any product which is commercially available or prepared by a method conventional in the art may be used. According to the invention, the silane ethanol solution with a specific concentration is adopted, silane groups in the silane ethanol solution are combined with the mineralized crystal particles, so that the hydrophobic and waterproof properties of the concrete anticorrosive coating are effectively improved, and the formed modified inducing layer, the bionic mineralized layer and organic silicon molecules in the low surface energy layer have good adhesion, so that the interface binding force of the low surface energy molecular layer can be enhanced, and the stability of the coating is improved.

In the invention, the temperature of the silanization treatment is preferably 1-45 ℃, and the time is preferably 1-12 h.

After the silanization treatment is finished, the obtained silanization treatment product is preferably washed and dried in sequence, and the low surface energy layer is generated on the surface of the concrete bionic mineralization layer. In the invention, the washing is preferably carried out in an ethanol solution, and the number of times is preferably 3-5. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. In the invention, the drying temperature is preferably 5-80 ℃. The drying method is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.

The invention also provides a concrete anticorrosive coating prepared by the preparation method in the technical scheme, which is characterized by comprising a modified induction layer, a bionic mineralization layer and a low surface energy layer which are sequentially attached to the surface of concrete.

Fig. 1 is a schematic structural diagram of a concrete anticorrosive coating provided by the invention, wherein 1 is a concrete substrate, 2 is a modification inducing layer, 3 is a bionic mineralized layer, 4 is a low surface energy layer, and 5 is water drops. As shown in FIG. 1, the concrete anticorrosion coating provided by the invention can modify and protect defects such as pores or cracks existing in a concrete structure, water drops are difficult to spread and wet on the surface of the coating, and the coating has a large contact angle.

The concrete anticorrosive coating and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.

In the embodiment of the invention, a standard mortar block is taken as an example to show that the concrete anticorrosive coating prepared by the invention has excellent anticorrosive performance.