CN108440018B - Concrete surface protection method and obtained surface protection type concrete - Google Patents
Concrete surface protection method and obtained surface protection type concrete Download PDFInfo
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- CN108440018B CN108440018B CN201810544804.6A CN201810544804A CN108440018B CN 108440018 B CN108440018 B CN 108440018B CN 201810544804 A CN201810544804 A CN 201810544804A CN 108440018 B CN108440018 B CN 108440018B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
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Abstract
The invention discloses a concrete surface protection method and the obtained surface protection type concrete, the protection steps are as follows: preparing graphene oxide aqueous dispersion liquid, covering the dispersion liquid on the surface of concrete until the thickness of a graphene oxide layer on the surface of the concrete is more than or equal to 10 microns, and reducing the concrete covered with the graphene oxide layer on the surface to obtain the hydrophobic graphene surface protective layer. The method disclosed by the invention has the advantages that the single graphene oxide is used as the raw material for carrying out concrete surface protection, the operation is simple, the cost is low, the thought is novel, the water absorption of the concrete subjected to surface protection treatment is greatly reduced, the concrete has excellent erosion resistance and longer service life, and a new research thought is provided for the surface protection work of the cement-based material.
Description
Technical Field
The invention relates to a concrete surface protection method, in particular to a simple, convenient, low-cost and environment-friendly concrete surface protection method and obtained surface protection type concrete, and belongs to the technical field of building material protection.
Background
Concrete material is one of the most popular artificial engineering materials used in the world, and is widely applied to basic facilities such as national defense protection, hydroelectric engineering and the like. The durability of the concrete material is closely related to the external conditions, and the service life of the concrete material is influenced by the physical and chemical actions such as freeze-thaw cycle, alternation of dryness and wetness, alkali aggregate reaction and the like. Generally, the concrete performance is affected by environmental factors through a process from the outside to the inside, and a part directly contacting with the external environment is rapidly degraded and the inside is slowly degraded. Therefore, the surface protection performance of the concrete material is improved, and the concrete material has a remarkable effect of improving the environmental impact resistance of the whole structure.
Generally, the protection of the concrete surface is improved by coating the concrete surface with organic and inorganic protective materials. The organic material mainly includes epoxy resin, organic silicon and the like, and the inorganic material mainly includes water glass and the like. Although both organic and inorganic materials can provide good surface protection, they have considerable disadvantages. For example, organic materials have poor weather resistance and are prone to aging and peeling under long-term exposure; inorganic materials have high dependency on environmental conditions, and the contained alkali metal ions are at risk of accelerating the deterioration of material properties.
Graphene is the thinnest and hardest two-dimensional nanomaterial currently found. In recent years, a plurality of cement technologists try to introduce graphene into cement-based materials, and improve the related performance of the cement-based materials by utilizing the excellent mechanical, electrical and thermal properties of the graphene. Most researches are conducted by doping graphene into a cement-based material through dispersion methods such as high-speed stirring, so that the influence rule of the graphene on the cement performance is researched, and the research focus is on performance change caused by the fact that the graphene is dispersed in a cement matrix. In addition, researches have been made on doping graphene into a coating matrix such as epoxy resin and applying the graphene modified coating to the surface of materials such as metal and concrete for protection, but the method is complicated and the coating matrix has a certain pollution effect on the environment. At present, no other application mode of graphene in cement-based materials is found.
Disclosure of Invention
In view of various defects of the existing concrete surface protection technology, the invention provides a concrete surface protection method, which has the advantages of simple operation, less raw materials, low cost, low water absorption of the obtained protection layer, strong weather resistance, good corrosion resistance and small environmental influence.
According to the method, the graphene oxide is fixed on the surface of the concrete by utilizing the mechanism that calcium ions dissolved out by hydration of cement and carboxyl groups in the graphene oxide are subjected to complexing action, and then the hydrophilic graphene oxide is reduced into hydrophobic graphene by a reduction method, so that the surface protection effect is achieved. Graphene consists of a layer of carbon atoms and has excellent chemical stability and corrosion resistance. The lamellar structure of the graphene can be overlapped and staggered layer by layer, a compact shielding layer is formed on the surface of the concrete, infiltration, permeation and diffusion of corrosive media can be effectively inhibited, and the protective performance of the surface of the concrete to harmful media is improved. According to the invention, the excellent barrier property of graphene is utilized, and the protection of the concrete surface can be realized only through single graphene, so that the method has great significance for prolonging the service life of concrete and saving natural resources such as gravel. The scheme of the invention is simple and efficient, and has good popularization and application values and wide prospects. The technical disclosure is not seen at present, and the method is pioneering.
The specific technical scheme of the invention is as follows:
a method of protecting a concrete surface, the method comprising the steps of:
(1) dispersing graphene oxide in water, and fully and uniformly dispersing to obtain a graphene oxide aqueous dispersion liquid;
(2) coating the graphene oxide aqueous dispersion liquid on the surface of concrete in a soaking or coating mode until the thickness of the graphene oxide layer on the surface of the concrete is more than or equal to 10 microns;
(3) and (3) carrying out reduction treatment on the concrete coated with the graphene oxide layer on the surface, and removing most hydrophilic groups in the graphene oxide to obtain the hydrophobic graphene surface protective layer.
The invention is convenient, simple and convenient, and can be suitable for various types of concrete. The concrete can be precast concrete or cast-in-place concrete. The precast concrete refers to a concrete structure cast elsewhere rather than at the last construction site, and the cast-in-place concrete refers to a concrete structure cast at the construction site. The concrete may be various shapes, concrete structures used in various fields, such as houses, outer walls, roads, bridges, dams, and the like.
Further, the concrete is a concrete structure which has reached a final setting time, and surface protection can be performed as long as the concrete loses plasticity and has a certain mechanical strength.
Furthermore, the graphene oxide used in the invention has the sheet diameter of 0.5-6 μm, the oxygen content of 25-50% and 1-10 layers.
Further, in the step (1), the graphene oxide is preferably dispersed by using an ultrasonic method. When the ultrasonic dispersion is carried out, the power is 300-1200W, and the frequency is 40-100 KHz. Generally, the dispersion can be uniformly dispersed after 5-240 min of ultrasonic treatment.
Further, in the step (2), the graphene oxide aqueous dispersion liquid may be coated on the surface of the concrete by soaking or coating, and the coating may be spraying, brushing or printing. When the concrete area is small and can be moved, any one of soaking and coating can be adopted, and when the concrete is used and can not be moved, only the coating mode can be adopted. Tests prove that the thickness of the graphene oxide layer on the surface of the concrete is increased along with the increase of the soaking or coating time, and the water absorption of the surface of the concrete tends to be reduced, namely the protective performance is increased. When the thickness is less than 10 μm, the protective effect is low, and when the thickness is 10 μm or more, the protective effect satisfies the requirements. Preferably, the protective effect is better when the thickness is 20 μm or more. During coating, the concentration of the graphene oxide aqueous dispersion liquid cannot be too low, too low time is too long, effective adhesion of graphene cannot be realized, too high time is not too long, too high graphene oxide has poor dispersibility, and uneven coating is easily caused. Generally, the concentration of graphene oxide in the aqueous graphene oxide dispersion is preferably 0.01 to 0.5 mg/mL. At this concentration, a graphene oxide layer thickness of 10 μm or more can be achieved within 1 hour, preferably within 20 min.
Further, in the step (3), the concrete coated with the graphene oxide layer is subjected to reduction treatment to remove most of hydrophilic groups such as carboxyl groups and hydroxyl groups in the graphene oxide, so that the graphene oxide is changed into graphene, is in a hydrophobic state, and plays a role in protection. The reduction treatment may be a thermal reduction treatment, or a chemical reduction treatment or infrared lamp irradiation. The thermal reduction is to treat the concrete with the graphene oxide layer at 40-105 ℃, preferably 40-60 ℃, and the treatment time is generally 1-24 h, preferably 2-6 h. The chemical reduction is to treat the concrete with the graphene oxide layer on the surface with a chemical reagent, wherein the chemical reagent can be vitamin C and the like, and the specific operation mode can refer to the prior art. In view of ease of handling and protection of concrete, thermal reduction treatment is preferably employed.
The surface protective concrete can be obtained by adopting the method, and the surface protective concrete also falls into the protection scope of the invention. The concrete structure with the graphene layer coated on the surface is characterized in that: the concrete surface protection layer is prepared by the method for concrete surface protection. The concrete is various precast concrete or cast-in-place concrete prepared by adopting the prior art.
Further, in the surface protection type concrete, the hydrophobic graphene surface protection layer is located on at least one surface of the concrete matrix.
According to the invention, the single graphene oxide is used as a raw material to protect the surface of the concrete, calcium ions in the concrete can be dissolved out on the surface of the concrete due to cement hydration, and the graphene oxide and the calcium ions can generate a complex flocculation reaction in water, so that the graphene oxide is firmly fixed on the surface of the concrete, and the adhesion problem of the protective layer is solved. And then, the hydrophilic functional groups in the graphene oxide are removed through reduction treatment, so that the hydrophilic graphene oxide is changed into hydrophobic graphene, and the protection of the surface of the concrete material to an erosion medium is effectively improved. After the treatment of the invention, the water absorption of the concrete is greatly reduced, the resistance of the concrete surface to erosion media is greatly improved, the graphene protective layer is firmly combined with the concrete and is not easy to age and fall off, no alkali metal ions exist in the protective layer, the concrete structure cannot be damaged, and the defects of poor weather resistance and large environmental influence of the existing inorganic and organic protective materials are overcome. The concrete surface protection method is simple to operate, low in cost and novel in concept, the concrete subjected to surface protection treatment has excellent erosion resistance and longer service life, and a new research concept is provided for the surface protection work of cement-based materials.
Detailed Description
The present invention will be further described below with reference to specific examples for better understanding of the technical content of the present invention, but the technical content of the present invention is not limited to only the following embodiments.
Example 1
The concrete raw materials were prepared according to the conventional method, cast into cubic concrete test pieces (150 × 150 mm), and the test pieces were cured for 28 days in a conventional manner with a strength standard of C40.
Taking graphene oxide with the sheet diameter of 2-4 mu m, the oxygen content of 40% and 2-6 layers, adding the graphene oxide into water, and performing ultrasonic dispersion for 10min under the conditions of the ultrasonic power of 600W and the frequency of 100 KHz to obtain a uniformly dispersed graphene oxide aqueous dispersion liquid, wherein the content of the graphene oxide is 0.05 mg/mL.
And (3) taking 7 concrete test pieces which are cured for 28 days, putting the concrete test pieces into the graphene oxide aqueous dispersion liquid, soaking for 0min, 1min, 3min, 10min, 20min, 30min and 50min at normal temperature, taking out, and measuring the thickness of the graphene oxide to be 0 mu m, 2 mu m, 4 mu m, 10 mu m, 15 mu m, 22 mu m and 38 mu m respectively.
And (3) placing the concrete test piece coated by the graphene oxide into a drying box, and treating for 6h at 60 ℃ to obtain hydrophobic surface protective layers on the surfaces of the concrete test piece, wherein the concrete test piece becomes a surface protection type concrete test piece.
In order to verify the protection performance of the Method, the concrete Test piece after protection treatment is subjected to a water absorption performance Test (see ASTMC1585-13 Standard Test Method), and the lower the water absorption rate is, the lower the probability of the external harmful substance entering the concrete is, and the better the protection performance is.
The water absorption of each concrete sample was as follows:
from the above table data, it can be seen that: the concrete for protecting the graphene surface has lower water absorption rate than the concrete without protection, and the water absorption rate is lower when the thickness of the protection layer formed for a longer time is larger under the condition that the concentration of the graphene oxide is unchanged. Wherein the water absorption of the concrete with the 10 mu m thick protective layer is reduced by 24.03 percent compared with the untreated concrete, the water absorption of the concrete with the 20 mu m thick protective layer is reduced by 44.16 percent compared with the untreated concrete, and the water absorption of the concrete with the 38 mu m thick protective layer is reduced by 46.75 percent compared with the untreated concrete. The reduction of the water absorption of the concrete shows that a compact graphene protective layer is formed on the surface of the test block, so that the invasion of harmful media is effectively reduced, which shows that the method can play a good role in protecting the surface of the concrete. From the change in water absorption, the water absorption of the overcoat layer at 20 μm or more can be made very low, and the water absorption does not change significantly with the increase in thickness after exceeding 20 μm.
Example 2
The concrete raw materials were prepared according to the conventional method, cast into cubic concrete test pieces (150 × 150 mm), and the test pieces were cured for 28 days in a conventional manner with a strength standard of C40.
Taking graphene oxide with the sheet diameter of 0.5-2 mu m, the oxygen content of 25% and 6-10 layers, adding the graphene oxide into water, and performing ultrasonic dispersion for 30min under the conditions of ultrasonic power of 1200W and frequency of 100 KHz to obtain uniformly dispersed graphene oxide aqueous dispersion liquid. The addition amount of the graphene oxide was controlled so that the content of the graphene oxide was 0.1mg/mL, 0.3mg/mL, and 0.5mg/mL, respectively.
And (3) putting the concrete samples cured for 28 days into the graphene oxide aqueous dispersion liquid with different concentrations, soaking for 10min at normal temperature, and taking out to obtain the graphene oxide with the thicknesses of 13 microns, 17 microns and 21 microns.
And (3) placing each concrete sample coated by the graphene oxide into a drying oven, and treating for 1h at 100 ℃ to obtain a hydrophobic surface protective layer on each surface of the concrete sample, wherein the concrete sample becomes a surface protective type concrete sample.
The concrete samples after the protection treatment were subjected to a water absorption performance Test (see ASTMC1585-13 Standard Test Method), and the water absorption of each concrete sample was as follows:
example 3
The concrete raw materials were prepared according to the conventional method, cast into cubic concrete test pieces (150 × 150 mm), and the test pieces were cured for 28 days in a conventional manner with a strength standard of C40.
Taking graphene oxide with the sheet diameter of 5-6 mu m, the oxygen content of 50% and 2-5 layers, adding the graphene oxide into water, and performing ultrasonic dispersion for 60 min under the conditions that the ultrasonic power is 300W and the frequency is 40 KHz to obtain a uniformly dispersed graphene oxide aqueous dispersion liquid. The addition amount of the graphene oxide was controlled so that the content of the graphene oxide was 0.5mg/mL, respectively.
And (3) taking the concrete sample cured for 28 days, putting the concrete sample into the graphene oxide aqueous dispersion liquid, soaking for 15min at normal temperature, and taking out to obtain the graphene oxide with the thickness of 26 microns.
And (3) placing the concrete sample coated with the graphene oxide into a drying oven, and treating for 2h at 50 ℃ to obtain hydrophobic surface protective layers on the surfaces of the concrete sample, wherein the concrete sample becomes a surface protective type concrete sample.
The concrete Test piece after the protection treatment is subjected to a water absorption performance Test (see ASTMC1585-13 Standard Test Method), and the water absorption of the concrete Test piece is 84g/m2。
Comparative example 1
The method for protecting the surface of concrete by taking inorganic lithium silicate water glass as a protective material comprises the following steps:
the concrete raw materials were prepared according to the conventional method, cast into cubic concrete test pieces (150 × 150 mm), and the test pieces were cured for 28 days in a conventional manner with a strength standard of C40.
Dissolving lithium silicate water glass in water to prepare a solution with the concentration of 0.5mg/mL, soaking a concrete test piece in the solution for 10min, taking out and naturally drying the concrete test piece, and then carrying out water absorption test. Water absorption was measured by the same method as in example 1, and found to be 104g/m2。
Comparative example 2
The method takes a commercially available organic waterproof material as a protective material to protect the surface of concrete, the main component of the material is epoxy resin, and the method comprises the following steps:
the concrete raw materials were prepared according to the conventional method, cast into cubic concrete test pieces (150 × 150 mm), and the test pieces were cured for 28 days in a conventional manner with a strength standard of C40.
Dissolving organic waterproof material in water to prepare a solution with the concentration of 0.5mg/mL, soaking the concrete sample in the solution for 10min, taking out the concrete sample, and naturally drying the concrete sampleAnd (5) carrying out water absorption test. Water absorption test method As in example 1, water absorption was 93g/m2。
As can be seen from the comparison between examples 1-3 and comparative examples 1-2, the protective method of the present invention can achieve the same protective effect as organic and inorganic protective materials, and the protective effect of the present invention is better than that of organic and inorganic protective materials. The method is simple in operation process, environment-friendly and low in cost, the graphene is firmly connected with the concrete and cannot fall off due to aging, and the method does not contain alkali metal ions and cannot damage the concrete material.
The technical solutions of the present invention have been described and illustrated above, and it will be apparent to those skilled in the art that the present invention can be modified appropriately without departing from the core concept of the present invention, such as replacing the curing conditions and cycle of concrete, replacing the shape of concrete, replacing the coating mode, replacing the reduction mode, etc., and these operations and modifications also fall within the protection scope of the claims of the present invention.
Claims (5)
1. A method for protecting concrete surface is characterized by comprising the following steps:
(1) dispersing graphene oxide in water, and fully and uniformly dispersing to obtain a graphene oxide aqueous dispersion liquid;
(2) coating the graphene oxide aqueous dispersion liquid on the surface of concrete in a soaking or coating mode until the thickness of the graphene oxide layer on the surface of the concrete is more than or equal to 10 microns;
(3) carrying out reduction treatment on the concrete coated with the graphene oxide layer on the surface, and removing most hydrophilic groups in the graphene oxide to obtain a hydrophobic graphene surface protective layer;
the sheet diameter of the graphene oxide is 0.5-6 mu m, the oxygen content is 25-50%, and the number of layers is 1-10;
in the step (1), the graphene oxide is dispersed in an ultrasonic dispersion mode to be uniformly dispersed in water, wherein the ultrasonic dispersion power is 300-1200W, and the frequency is 40-100 KHz;
in the step (1), the concentration of the graphene oxide in the graphene oxide aqueous dispersion liquid is 0.01-0.5 mg/mL;
in the step (3), the concrete with the graphene oxide layer coated on the surface is subjected to reduction treatment in a thermal reduction mode, wherein the thermal reduction is to treat the concrete with the graphene oxide layer coated on the surface for 1-24 hours at the temperature of 40-105 ℃.
2. The method of claim 1, further comprising: the concrete is precast concrete or cast-in-place concrete, the cast-in-place concrete is a concrete structure cast and formed at a construction site, and the precast concrete is a concrete structure cast and formed elsewhere rather than cast and formed at the last construction site.
3. The method of claim 1, further comprising: in the step (2), the coating mode is spraying, brushing or printing.
4. A surface protection type concrete is characterized in that: the concrete surface protection layer comprises a concrete matrix and a hydrophobic graphene surface protection layer positioned on the surface of the concrete matrix, wherein the hydrophobic graphene surface protection layer is prepared according to the method for protecting the concrete surface of any one of claims 1-3.
5. The surface-protected concrete according to claim 4, wherein: the hydrophobic graphene surface protection layer is positioned on at least one surface of the concrete matrix.
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| CN110229023B (en) * | 2019-06-13 | 2022-02-22 | 辽宁省交通高等专科学校 | Graphene oxide organic composite protective coating for marine concrete and construction method thereof |
| CN112479304B (en) * | 2020-06-11 | 2022-08-30 | 中科远方(北京)科技有限公司 | Porous material with functional graphene oxide film on surface, and preparation method and application thereof |
| CN113235327B (en) * | 2021-04-23 | 2022-05-17 | 东华大学 | Graphene composite waterproof paper capable of being rapidly degraded and preparation method thereof |
| CN114163258B (en) * | 2021-12-27 | 2022-11-15 | 四川省川铁枕梁工程有限公司 | Method for enhancing concrete interface bonding force by graphene/graphene oxide and silica fume |
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