Graphene modified coating anti-icing agent and preparation method thereof

Abstract

The application relates to a graphene modified anti-freezing agent and a preparation method thereof. The anti-freezing agent is composed of a particle core, an inner coating layer and an outer coating layer. The particle core is composed of the following components and weight fractions: metal chloride, organic acetate and auxiliary materials. The inner coating layer is prepared from the following raw materials with the following percentage contents: graphene organic dispersion liquid, buffer gel agent, compatibilizer and silane coupling agent. The outer coating layer is composed of the following components and weight fractions: high permeability material, polyolefin elastomer, curing agent, calcium magnesium acetate and hard asphalt. The application has the ability of actively resisting and removing ice and snow without changing the asphalt mixture ratio and construction process. The inner coating layer is modified by adding the graphene organic dispersion liquid, so that the asphalt pavement has the functions of not softening at high temperature in summer, not hardening and cracking at low temperature in winter, and the service life of the pavement can be effectively prolonged.

Description

Technical Field

[0001] This invention relates to the field of snow melting materials technology, specifically to a graphene-modified anti-icing agent and its preparation method. Background Technology

[0002] With technological advancements and the demands of economic development, ensuring vehicle safety and comfort on roads is a crucial component of the transportation sector. In the cold winter months in Northwest my country, snowfall often results in widespread snow accumulation and icing on roads, significantly impacting driving safety and road capacity. Furthermore, maintenance and repair often require substantial manpower. Therefore, developing efficient anti-icing and snow-melting technologies is of great practical significance.

[0003] Currently, the main methods for snow removal and de-icing include physical and chemical methods. Physical methods mainly include manual snow removal and mechanical snow removal. Physical methods are often labor-intensive and inefficient, and are often ineffective for icy road sections covered by snow. Chemical methods mainly use various de-icing agents to achieve the purpose of melting snow and de-icing. For example, traditional external application of salt-based de-icing agents can cause corrosion to the road surface and damage to roadside vegetation. Existing chloride-based anti-icing materials perform poorly in terms of hydrophobicity and salt retention capacity, resulting in rapid salt loss and a short service life. Summary of the Invention

[0004] Based on this, the purpose of this invention is to provide a graphene-modified anti-icing agent and its preparation method, which has the ability to resist and remove ice and snow without softening at high temperatures in summer and without hardening or cracking at low temperatures in winter.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] A graphene-modified anti-icing agent, characterized in that the anti-icing agent is composed of a core, an inner coating layer, and an outer coating layer. The core comprises the following components and weight percentages: 30-45 parts metal chloride salt, 45-60 parts organic acetate, and 10-20 parts excipients. The inner coating layer is prepared from the following raw materials in the following percentages: 85%-90% graphene aqueous dispersion, 5%-10% buffer gel agent, 2%-5% compatibilizer, and 1%-4% silane coupling agent. The outer coating layer comprises the following components and weight percentages: 25-35 parts high-permeability material, 3-6 parts polyolefin elastomer, 3-6 parts curing agent, 3-5 parts calcium magnesium acetate, and 50-60 parts hard asphalt.

[0007] As a preferred technical solution, the metal chloride salt includes any one or a combination of multiple of ferric chloride, calcium chloride, magnesium chloride, and manganese chloride.

[0008] As a preferred technical solution, the organic acetate includes any one or a combination of calcium acetate, magnesium acetate, sodium acetate, potassium acetate, sodium hydrogen acetate, and potassium hydrogen acetate.

[0009] As a preferred technical solution, the auxiliary materials include at least one of blast furnace slag powder, silica fume powder, diatomaceous earth, and fly ash.

[0010] As a preferred technical solution, the graphene organic dispersion is prepared from graphene powder, organic solvent and surfactant, wherein the surfactant concentration is 6mg / mL-8mg / mL.

[0011] As a preferred technical solution, the surfactant is a ternary compound surfactant, which is composed of 1.5% TW80, 2% PVP and 1.5% SDBS with solid contents of 1.116, a potential value of -33.25mV, the organic solvent is NMP solvent, and the graphene powder is prepared by physical method from expandable graphite and pure water.

[0012] As a preferred technical solution, the buffer gel agent is composed of a carboxylic acid water-reducing agent, an organosilicon quaternary ammonium salt, a corrosion inhibitor, and a chitosan hydrogel.

[0013] As a preferred technical solution, the high-permeability material includes any one or a combination of quartz sand, diatomaceous earth, and expanded perlite, and the curing agent is one of hexamethylol melamine or hexamethylol melamine.

[0014] A method for preparing a graphene-modified anti-icing agent, characterized by comprising the following steps:

[0015] S1: Take metal chloride salt, organic acetate and excipients and dissolve them in water in sequence. Mix the mixture and stir and shear it at 40-60℃ for 10-20 minutes. Then dry it and sieve it to obtain core particles with a particle size of 0.5-1mm.

[0016] S2: Under the conditions of 1500-2000 r / min and 80-120℃, the buffer gel is heated to a molten state, and the compatibilizer and silane coupling agent are added in sequence and stirred to obtain a gel-like mixture; under the conditions of 800-1000 r / min and 40-60℃, the graphene organic dispersion is added in sequence. After being mixed evenly, it is added to the core of S1, dried, and then screened to form internally coated particles with a particle size of 2-3 mm.

[0017] S3: Mix the inner-coated particles from S2 with polyolefin elastomer, curing agent, and calcium magnesium acetate under organic solvent conditions to obtain a premix; melt hard asphalt and add high-permeability material, stir evenly and pour into the premix, dry and granulate to obtain secondary-coated graphene-modified anti-icing agent.

[0018] As a preferred technical solution, the graphene-modified anti-icing agent obtained by secondary coating in S3 has a particle size distribution of 4-5 mm.

[0019] The beneficial effects of this invention are as follows: 1. Without significantly altering the asphalt mixture ratio and construction process, it possesses the ability to actively resist and remove snow and ice, ensuring that light snow melts quickly and heavy snow does not freeze. 2. The inner coating layer, modified with graphene dispersion, enables the asphalt pavement to remain unsoftened at high summer temperatures and unhardened and cracked at low winter temperatures, effectively extending the pavement's service life. 3. The rational ratio of chloride and non-chloride salts, along with the coating of the particle core with a slow-release gelling agent, reduces the content of chloride ions without weakening the snow-melting ability, thereby delaying the corrosive effect of chloride ion release on the pavement and improving its service life. Implementation

[0020] To provide a better understanding of the technical means and effects achieved by this invention, a detailed description is provided using preferred embodiments, as follows: Example

[0021] A graphene-modified anti-icing agent is disclosed, comprising a core, an inner coating layer, and an outer coating layer. The core consists of the following components and weight parts: 30 parts of metal chloride salt, 60 parts of organic acetate, and 10 parts of excipients. The inner coating layer is prepared from the following raw materials in the following percentages: 90% graphene organic dispersion, 5% buffer gel agent, 4% compatibilizer, and 1% silane coupling agent. The outer coating layer consists of the following components and weight parts: 25 parts of high-permeability material, 5 parts of polyolefin elastomer, 6 parts of curing agent, 4 parts of calcium magnesium acetate, and 60 parts of hard asphalt.

[0022] In this embodiment, the graphene organic dispersion is prepared from graphene powder, organic solvent and surfactant, with a surfactant concentration of 8 mg / mL.

[0023] A method for preparing a graphene-modified anti-icing agent includes the following steps:

[0024] S1: Take metal chloride salt, organic acetate and excipients and dissolve them in water in sequence. Mix the mixture, stir and shear it at 40℃ for 10 minutes and then dry it. Then sieve the core particles with a particle size of 0.5-1mm.

[0025] S2: Under the conditions of 1500 r / min rotation speed and 80℃ heating temperature, the buffer gel agent is heated to a molten state, and the compatibilizer and silane coupling agent are added in sequence and stirred to obtain a gel-like mixture; under the conditions of 800 r / min rotation speed and 40℃ temperature, the graphene organic dispersion is added in sequence, and after being mixed evenly, it is added to the core of S1, dried and then screened to form internally coated particles with a particle size of 2-3 mm.

[0026] S3: Mix the inner-coated particles from S2 with polyolefin elastomer, curing agent, and calcium magnesium acetate under organic solvent conditions to obtain a premix; melt hard asphalt and add high-permeability material, stir evenly and pour into the premix, dry and granulate to obtain secondary-coated graphene-modified anti-icing agent. Example

[0027] A graphene-modified anti-icing agent is disclosed, comprising a core, an inner coating layer, and an outer coating layer. The core consists of the following components and weight parts: 35 parts of metal chloride salt, 55 parts of organic acetate, and 10 parts of excipients. The inner coating layer is prepared from the following raw materials in the following percentages: 85% graphene organic dispersion, 10% buffer gel agent, 3% compatibilizer, and 2% silane coupling agent. The outer coating layer consists of the following components and weight parts: 30 parts of high-permeability material, 4 parts of polyolefin elastomer, 6 parts of curing agent, 5 parts of calcium magnesium acetate, and 55 parts of hard asphalt.

[0028] In this embodiment, the graphene organic dispersion is prepared from graphene powder, organic solvent and surfactant, with a surfactant concentration of 7 mg / mL.

[0029] A method for preparing a graphene-modified anti-icing agent includes the following steps:

[0030] S1: Take metal chloride salt, organic acetate and excipients and dissolve them in water in sequence. Mix the mixture and stir and shear it at 50°C for 20 minutes. Then dry it and sieve it to obtain core particles with a particle size distribution of 0.5-1mm.

[0031] S2: Under the conditions of 2000 r / min rotation speed and 100℃ heating temperature, the buffer gel agent is heated to a molten state, and the compatibilizer and silane coupling agent are added in sequence and stirred to obtain a gel-like mixture; under the conditions of 1000 r / min rotation speed and 60℃ temperature, the graphene organic dispersion is added in sequence, and after being mixed evenly, it is added to the core of S1, dried and sieved to obtain internally coated particles with a particle size of 2-3 mm.

[0032] S3: Mix the inner-coated particles from S2 with polyolefin elastomer, curing agent, and calcium magnesium acetate under organic solvent conditions to obtain a premix; melt hard asphalt and add high-permeability material, stir evenly and pour into the premix, dry and granulate to obtain secondary-coated graphene-modified anti-icing agent. Example

[0033] A graphene-modified anti-icing agent is disclosed, comprising a core, an inner coating layer, and an outer coating layer. The core consists of the following components and weight parts: 40 parts of metal chloride salt, 50 parts of organic acetate, and 10 parts of excipients. The inner coating layer is prepared from the following raw materials in the following percentages: 85% graphene organic dispersion, 10% buffer gel agent, 2% compatibilizer, and 3% silane coupling agent. The outer coating layer consists of the following components and weight parts: 35 parts of high-permeability material, 6 parts of polyolefin elastomer, 6 parts of curing agent, 3 parts of calcium magnesium acetate, and 50 parts of hard asphalt.

[0034] In this embodiment, the graphene organic dispersion is prepared from graphene powder, organic solvent and surfactant, with a surfactant concentration of 6 mg / mL.

[0035] A method for preparing a graphene-modified anti-icing agent includes the following steps:

[0036] S1: Take metal chloride salt, organic acetate and excipients and dissolve them in water in sequence and mix them. Stir and shear the mixture at 60℃ for 20 minutes and then dry it. Then sieve the core particles with a particle size distribution of 0.5-1mm.

[0037] S2: Under the conditions of 2000 r / min rotation speed and 120℃ heating temperature, the buffer gel agent is heated to a molten state, and the compatibilizer and silane coupling agent are added in sequence and stirred to obtain a gel-like mixture; under the conditions of 1000 r / min rotation speed and 60℃ temperature, the graphene aqueous dispersion is added in sequence, and after being mixed evenly, it is added to the core of S1, dried and sieved to obtain internally coated particles with a particle size of 2-3 mm.

[0038] S3: Mix the inner-coated particles from S2 with polyolefin elastomer, curing agent, and calcium magnesium acetate under organic solvent conditions to obtain a premix; melt hard asphalt and add high-permeability material, stir evenly and pour into the premix, dry and granulate to obtain secondary-coated graphene-modified anti-icing agent. Example

[0039] A graphene-modified anti-icing agent is disclosed, comprising a core, an inner coating layer, and an outer coating layer. The core consists of the following components and weight parts: 45 parts of metal chloride salt, 45 parts of organic acetate, and 10 parts of excipients. The inner coating layer is prepared from the following raw materials in the following percentages: 90% graphene organic dispersion, 7% buffer gel agent, 2% compatibilizer, and 1% silane coupling agent. The outer coating layer consists of the following components and weight parts: 30 parts of high-permeability material, 3 parts of polyolefin elastomer, 4 parts of curing agent, 3 parts of calcium magnesium acetate, and 60 parts of hard asphalt.

[0040] In this embodiment, the graphene organic dispersion is prepared from graphene powder, organic solvent and surfactant, with a surfactant concentration of 8 mg / mL.

[0041] A method for preparing a graphene-modified anti-icing agent includes the following steps:

[0042] S1: Take metal chloride salt, organic acetate and excipients and dissolve them in water in sequence and mix them. Stir and shear the mixture at 60℃ for 20 minutes and then dry it. Then sieve the core particles with a particle size distribution of 0.5-1mm.

[0043] S2: Under the conditions of 2000 r / min rotation speed and 100℃ heating temperature, the buffer gel agent is heated to a molten state, and the compatibilizer and silane coupling agent are added in sequence and stirred to obtain a gel-like mixture; under the conditions of 1000 r / min rotation speed and 50℃ temperature, the graphene organic dispersion is added in sequence, and after being mixed evenly, it is added to the core of S1, dried and sieved to obtain internally coated particles with a particle size of 2-3 mm.

[0044] S3: Mix the inner-coated particles from S2 with polyolefin elastomer, curing agent, and calcium magnesium acetate under organic solvent conditions to obtain a premix; melt hard asphalt and add high-permeability material, stir evenly and pour into the premix, dry and granulate to obtain secondary-coated graphene-modified anti-icing agent. Example

[0045] A graphene-modified anti-icing agent is disclosed, comprising a core, an inner coating layer, and an outer coating layer. The core consists of the following components and weight parts: 30 parts of metal chloride salt, 50 parts of organic acetate, and 20 parts of excipients. The inner coating layer is prepared from the following raw materials in the following percentages: 85% graphene organic dispersion, 10% buffer gel agent, 2% compatibilizer, and 3% silane coupling agent. The outer coating layer consists of the following components and weight parts: 35 parts of high-permeability material, 3 parts of polyolefin elastomer, 4 parts of curing agent, 3 parts of calcium magnesium acetate, and 55 parts of hard asphalt.

[0046] In this embodiment, the graphene organic dispersion is prepared from graphene powder, organic solvent and surfactant, with a surfactant concentration of 8 mg / mL.

[0047] A method for preparing a graphene-modified anti-icing agent includes the following steps:

[0048] S1: Take metal chloride salt, organic acetate and excipients and dissolve them in water in sequence and mix them. Stir and shear the mixture at 50℃ for 15 minutes and then dry it. Then sieve the core particles with a particle size distribution of 0.5-1mm.

[0049] S2: Under the conditions of 1800 r / min rotation speed and 120℃ heating temperature, the buffer gel agent is heated to a molten state, and the compatibilizer and silane coupling agent are added in sequence and stirred to obtain a gel-like mixture; under the conditions of 800 r / min rotation speed and 60℃ temperature, the graphene organic dispersion is added in sequence, and after being mixed evenly, it is added to the core of S1, dried and sieved to obtain internally coated particles with a particle size of 2-3 mm.

[0050] S3: Mix the inner-coated particles from S2 with polyolefin elastomer, curing agent, and calcium magnesium acetate under organic solvent conditions to obtain a premix; melt hard asphalt and add high-permeability material, stir evenly and pour into the premix, dry and granulate to obtain secondary-coated graphene-modified anti-icing agent.

[0051] Further explanation is needed regarding the preparation method of graphene powder in the graphene organic dispersion in the above embodiments, as follows: Expandable graphite is expanded at 1020℃ in a high-temperature reactor under nitrogen protection, exhibiting a worm-like structure. The expanded material is continuously introduced into a shear emulsifier and mixed with pure water. The addition amount is 1‰-3‰ of the weight of pure water in the emulsification tank. Due to the poor wettability of the expanded graphite powder and the obvious stratification with pure water, it is cyclically sheared and emulsified for 3-5 hours and ultrasonically treated for 12-16 hours to ensure uniform mixing and no obvious stratification of the liquid phase. Then, it is introduced into a high-pressure homogenizer for homogenization at a pressure of 200MPa for 1-3 hours / t. After reaching a stable liquid phase state, the concentration is increased by solid-liquid separation to obtain a graphene slurry of a certain concentration. After the graphene slurry is prepared, the water is removed by drying to obtain the desired graphene powder.

[0052] The preparation process of the graphene organic dispersion is as follows: a certain amount of surfactant is weighed and dissolved in a certain amount of organic solvent (NMP), and emulsified by a shear emulsifier at a high speed (9000-10000 r / min). After emulsification for a period of time (1h-3h), the speed is adjusted to a low speed (2000-3000 r / min) and the prepared graphene powder is added for mixing. After mixing, the shear emulsifier is adjusted to a high speed to make the mixture uniform, and then placed in an ultrasonic bath for ultrasonication for 2h-6h to obtain the graphene organic dispersion.

[0053] The relevant experimental data are as follows:

[0054] Corrosion rate of carbon steel; test temperature range: 21℃-22℃, relative humidity: 45%-49%, the corrosion rate index of carbon steel was determined by the test solution at a ratio of 18% (mass fraction), and the results are shown in Table 1.

[0055] Table 1. Test results of carbon steel corrosion rate

[0056]

[0057] The current performance indicators for halogenated materials in my country require that the corrosion rate of carbon steel be ≤0.11 mm / year. The test results in the table are 0.04 mm / year, which meets the relevant requirements.

[0058] Melting rate and freezing point; test temperature range: 22℃-25℃, relative humidity: 38%-49%, specific test results are shown in Table 2.

[0059] Table 2 Results of melting rate and freezing point tests

[0060]

[0061] The current requirements for the performance of halogenated materials in asphalt mixtures for highways in my country are: melting rate ≥20% and freezing point ≤-5℃. The test results in the table show a melting rate of 21% and a freezing point of -7.5℃, which meets the relevant requirements.

[0062] Residual stability ratio, heat resistance index, and salt release; test temperature range: 19℃-23℃, relative humidity: 36%-45%, specific test results are shown in Table 3.

[0063] Table 3. Results of heat resistance index and salt release tests

[0064]

[0065] The current requirements for the performance of salt-containing materials in my country's highway asphalt mixture de-icing materials are: heat resistance index ≤ 0.5%, salt release ≤ 0.4%, and residual stability ratio ≥ 85%. The test results in the table are: heat resistance index 0.07%, salt release 0.2%, and residual stability ratio 85.9%.

[0066] In practical applications, before the formal mixing of graphene-modified anti-icing agents and asphalt mixtures, the mixing plant needs to conduct a trial adjustment of the production mix ratio. The cold aggregate ratio must be strictly set according to the target mix ratio (i.e., the amount of graphene-modified anti-icing agent added is 4%-8% of the asphalt mixture mass), and the flow rate of the cold aggregate bins must be controlled. The fixed flow rate of each bin can be calculated based on the production capacity of the mixing plant and the target mix ratio; the cold aggregate ratio must not be arbitrarily changed. By selecting different vibrating screen aperture sizes for the mixing plant, it should be matched to the type of mixture being mixed. The equivalent screen aperture size of the vibrating screen of the mixing plant should conform to the following Table 4.

[0067] Table 4 Equivalent screen aperture size (mm) of the vibrating screen for the mixer

[0068]

[0069] During the mixing process, the appearance quality of the mixture can be visually inspected. The mixture exiting the machine should be uniform and consistent, without any white spots, lumps, or segregation of coarse and fine aggregates. When the temperature is below 5℃, hot-mixed materials should not be spread. If spreading is necessary, special measures should be taken to ensure the temperature of the mixture during spreading, i.e., the spreading temperature should not be lower than 125℃.

[0070] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention. The scope of protection claimed by the appended claims and their equivalents is defined.

Claims

1. A graphene-modified anti-icing agent, characterized in that, This anti-icing agent consists of a core, an inner coating layer, and an outer coating layer. The core comprises the following components and weight percentages: 30-45 parts of metal chloride salt, 45-60 parts of organic acetate, and 10-20 parts of excipients. The inner coating layer is prepared from the following raw materials in the following percentages: 85%-90% graphene organic dispersion, 5%-10% buffer gel agent, 2%-5% compatibilizer, and 1%-4% silane coupling agent. The outer coating layer comprises the following components and weight percentages: 25-35 parts of high-permeability material, 3-6 parts of polyolefin elastomer, 3-6 parts of curing agent, 3-5 parts of calcium magnesium acetate, and 50-60 parts of hard asphalt. The buffer gel agent is a mixture of carboxylic acid water-reducing agent, organosilicon quaternary ammonium salt, corrosion inhibitor, and chitosan hydrogel.

2. The graphene-modified anti-icing agent according to claim 1, characterized in that: The metal chloride salt includes any one or a combination of multiple of ferric chloride, calcium chloride, magnesium chloride, and manganese chloride.

3. The graphene-modified anti-icing agent according to claim 1, characterized in that: The organic acetate includes any one or a combination of calcium acetate, magnesium acetate, sodium acetate, potassium acetate, sodium biacetate, and potassium biacetate.

4. The graphene-modified anti-icing agent according to claim 1, characterized in that: The auxiliary materials include at least one of blast furnace slag powder, silica fume powder, diatomaceous earth, and fly ash.

5. The graphene-modified anti-icing agent according to claim 1, characterized in that: The graphene organic dispersion is prepared from graphene powder, organic solvent and surfactant, and the surfactant concentration is 6mg / mL-8mg / mL.

6. The graphene-modified anti-icing agent according to claim 5, characterized in that: The surfactant is a ternary compound surfactant, which is composed of 1.5% TW80, 2% PVP and 1.5% SDBS with solid contents of 1.116 and a potential value of -33.25mV. The organic solvent is NMP solvent. The graphene powder is prepared by physical method from expandable graphite and pure water.

7. The graphene-modified anti-icing agent according to claim 1, characterized in that: The high-permeability material includes any one or a combination of quartz sand, diatomaceous earth, and expanded perlite, and the curing agent is one of hexamethylol melamine or hexamethylol melamine.

8. A method for preparing a graphene-modified anti-icing agent according to any one of claims 1-7, characterized in that, Includes the following steps: S1: Take metal chloride salt, organic acetate and excipients and dissolve them in water in sequence. Mix the mixture and stir and shear it at 40-60℃ for 10-20 minutes. Then dry it and sieve it to obtain core particles with a particle size of 0.5-1mm. S2: Under the conditions of 1500-2000 r / min and 80-120℃, the buffer gel is heated to a molten state, and the compatibilizer and silane coupling agent are added in sequence and stirred to obtain a gel-like mixture; under the conditions of 800-1000 r / min and 40-60℃, the graphene organic dispersion is added in sequence. After being mixed evenly, it is added to the core of S1, dried, and then screened to form internally coated particles with a particle size of 2-3 mm. S3: Mix the inner-coated particles from S2 with polyolefin elastomer, curing agent, and calcium magnesium acetate under organic solvent conditions to obtain a premix; melt hard asphalt and add high-permeability material, stir evenly and pour into the premix, dry and granulate to obtain secondary-coated graphene-modified anti-icing agent.

9. The method for preparing a graphene-modified anti-icing agent according to claim 8, characterized in that: The graphene-modified anti-icing agent obtained by secondary coating in S3 has a particle size distribution of 4-5 mm.

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