CN107699034B - Graphene anticorrosive paint for photovoltaic equipment and preparation method - Google Patents
Graphene anticorrosive paint for photovoltaic equipment and preparation method Download PDFInfo
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- CN107699034B CN107699034B CN201711022759.XA CN201711022759A CN107699034B CN 107699034 B CN107699034 B CN 107699034B CN 201711022759 A CN201711022759 A CN 201711022759A CN 107699034 B CN107699034 B CN 107699034B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/043—Drying and spraying
Abstract
The invention belongs to the technical field of preparation of anticorrosive coatings, and provides a graphene anticorrosive coating for photovoltaic equipment and a preparation method thereof. According to the method, paraffin is prepared into paraffin emulsion, graphene is prepared into graphene suspension, polyquaternium flocculant is added after the graphene suspension and the paraffin emulsion are mixed according to a proportion, the paraffin filler loaded with the graphene is obtained through emulsion coprecipitation, suction filtration and micro-crosslinking granulation, the paraffin filler can be added into the coating before the coating is used, the coating is coated after being uniformly stirred, good corrosion resistance is endowed to the coating, and the coating can be used for photovoltaic equipment. Compared with the traditional method, the graphene coating prepared by the preparation method disclosed by the invention is good in dispersion uniformity, compactness and stability, good in corrosion prevention effect, stable in coating performance, simple in whole preparation process, low in raw material cost and processing cost, and capable of being popularized and applied.
Description
Technical Field
The invention belongs to the technical field of preparation of anticorrosive coatings, and provides a graphene anticorrosive coating for photovoltaic equipment and a preparation method thereof.
Background
in the era of resource exhaustion at present, the prospect of popularization and application of solar energy resources as emerging resources is very wide, and the photovoltaic industry rapidly rises under the condition of energy and environmental crisis. The photovoltaic industry is an emerging industry in China, and is a high-tech and capital-intensive industry. Since the 21 st century, the development of the photovoltaic industry in China is rapid, and the yield of the photovoltaic cell in China accounts for about one third of the total yield in the world by 2008. The development of photovoltaic equipment ranges from the construction of silicon material production, silicon wafer processing, solar cell and component production and corresponding pure water preparation, environmental protection treatment and purification engineering to the construction of detection equipment, simulators and the like corresponding to a photovoltaic industrial chain, and the development scale and the development prospect are wide. The popularization and use of photovoltaic equipment on a large scale are accompanied by increasingly important equipment maintenance work, and particularly, an antirust and anticorrosion technology is an extremely important item.
The existing photovoltaic equipment, especially a battery panel bracket and a shell are mostly made of aluminum alloy materials, and the antirust and anticorrosion materials are mainly painted by paint, but the common paint is easy to fall off under the conditions of outdoor direct solar radiation, rainwater, temperature change and the like, so that the antirust and anticorrosion imitating effect is poor. The wide and unique performance of graphene shows great potential in the field of metal material corrosion prevention, and the graphene gradually becomes a medium flow grinding column in a metal corrosion-prevention and rust-prevention material. The graphene anticorrosive paint has multiple functions of physical corrosion prevention and electrochemical corrosion prevention. The conjugated structure of the graphene sheet layer is overlapped layer by layer in the coating to form a compact isolation layer, so that the infiltration and the permeation of moisture to the coating are blocked, the physical anticorrosion effect is realized, and the waterproof permeability is enhanced by the hydrophobic characteristic of the surface of the graphene. Electrochemical corrosion prevention function: the anodic reaction of the steel substrate leads Fe to lose electrons and be gradually corroded, and the conductivity of the graphene can prevent the Fe → Fe3+ reaction and prevent rust from generating. Besides the excellent anticorrosion function, the graphene coating has excellent effects in the aspects of antistatic property, flame retardance, heat conduction and heat dissipation and chemical resistance, and is very suitable for the anticorrosion and antirust technologies of photovoltaic equipment.
At present, certain effect is achieved in the aspect of graphene anticorrosive paint at home and abroad. In the background bin and the like, a preparation method of a graphene-based anticorrosive coating (Chinese invention patent application No. 201710153171.1) is disclosed, wherein graphene oxide is firstly put into water or an oily solvent for ultrasonic dispersion to obtain a pre-dispersion liquid; adding graphene into the pre-dispersion liquid, and performing ultrasonic dispersion treatment to enable graphene oxide to adsorb graphene and uniformly disperse the graphene to obtain a composite dispersion liquid; carrying out suction filtration on the composite dispersion liquid to obtain composite slurry; the composite slurry is added into water-based resin or oil-based resin, and an auxiliary agent is added and stirred to obtain the graphene-based anticorrosive paint, but the preparation process of the method is complex and the problem of graphite dispersibility cannot be well solved. In addition, the Huqiflower and the like invent a modified graphene and a coating containing the modified graphene (Chinese patent application No. 201610997544.9), the method comprises the steps of adding graphene oxide into an organic solvent, adding glucose, polyvinylpyrrolidone and a silane coupling agent after ultrasonic dispersion treatment, and stirring for 10-20 minutes to obtain a primary mixed solution; and then, carrying out centrifugal washing on the primary mixed solution by using an organic solvent, wherein the residual solid substance obtained by the centrifugal washing is the modified graphene, and then adding the coating for use.
Therefore, in the prior art, the graphene coating has the defect that the graphene coating is difficult to disperse when applied and coated due to the fact that the graphene self-aggregates to destroy the dispersion uniformity and compactness of the graphene coating, the anticorrosive effect and the barrier property of the coating cannot be guaranteed, and the graphene anticorrosive coating specially applied to photovoltaic equipment is not available temporarily.
Disclosure of Invention
The invention aims to provide a graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof, the method prepares paraffin into paraffin emulsion, prepares graphene into graphene suspension, mixes the graphene and the graphene in proportion, adds a polyquaternium flocculant, and performs emulsion coprecipitation, suction filtration and micro-crosslinking granulation to obtain the paraffin filler loaded with the graphene, can be added into the paint before the paint is used, and is coated after being uniformly stirred, so that the paint has good anticorrosive performance, can be used for the photovoltaic equipment, can solve the problem that the traditional graphene paint has the defect of difficult dispersion when being applied and the paint due to the self-agglomeration of the graphene and the damage to the dispersion uniformity and compactness of the graphene, and ensures the anticorrosive effect and the barrier property of the prepared paint.
the invention relates to a specific technical scheme as follows:
A preparation method of graphene anticorrosive paint for photovoltaic equipment comprises the steps of preparing paraffin into paraffin emulsion, preparing graphene into graphene suspension, mixing the paraffin emulsion and the graphene suspension in proportion, adding a polyquaternium flocculant, carrying out emulsion coprecipitation, suction filtration and micro-crosslinking granulation to obtain a graphene-loaded paraffin filler, adding the graphene-loaded paraffin filler into the paint before the paint is used, stirring uniformly, and then coating, so that the paint has good anticorrosive performance and can be used for photovoltaic equipment; the preparation method comprises the following specific steps:
(1) Slowly stirring and heating paraffin with a certain mass while heating the paraffin to melt the paraffin, adding a certain proportion of emulsifier, simultaneously increasing the stirring speed to fully and uniformly mix the paraffin with the emulsifier, then adding emulsified water with the same temperature, adding the emulsified water once every 1min until white pasty emulsion is obtained, then cooling the temperature to the normal temperature, slowing down the stirring speed, adding a certain amount of tackifier, and uniformly stirring the mixture to obtain paraffin emulsion;
(2) Mixing graphene dry powder, a surfactant and an organic solvent according to a certain mass ratio, and performing ultrasonic dispersion to prepare a graphene suspension;
(3) Mixing the paraffin emulsion obtained in the step (1) with the graphene suspension obtained in the step (2), adding a certain amount of flocculant, carrying out emulsion coprecipitation to load graphene in heat storage material paraffin, carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the filtrate by adopting a spray drying method to obtain the paraffin filler loaded with graphene;
(4) And (4) adding the filler obtained in the step (3) into the coating according to a certain mass ratio, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
Preferably, the paraffin wax in step (1) is at least one of microcrystalline paraffin, polyethylene wax or chlorinated paraffin.
preferably, the initial stirring speed of the paraffin wax in the step (1) is 100-200 r/min, and the heating temperature is 85-90 ℃.
Preferably, the emulsifier in the step (1) is fatty alcohol-polyoxyethylene ether and octadecyl trimethyl ammonium chloride, wherein the addition amount of the fatty alcohol-polyoxyethylene ether is 2-3% of the mass of the paraffin, the addition amount of the octadecyl trimethyl ammonium chloride is 1-2% of the mass of the paraffin, and the stirring speed after the emulsifier is added is 700-900 r/min.
Preferably, the emulsified water in the step (1) is added for the first time in the same amount as the paraffin by mass, and is added for 1g each time thereafter.
Preferably, the stirring speed after the temperature is reduced to the normal temperature in the step (1) is 400-600 r/min.
Preferably, the tackifier in the step (1) is a carboxymethyl cellulose solution, the mass fraction of the carboxymethyl cellulose solution is 4-6%, and the addition amount of the carboxymethyl cellulose solution is 30-60% of the mass of the paraffin.
Preferably, the surfactant in the step (2) is at least one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyvinyl alcohol or sodium lignosulfonate; the organic solvent is at least one of methanol, ethanol, isopropanol, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.
Preferably, in the graphene suspension in the step (2), 3-5 parts by weight of graphene dry powder, 0.05-0.1 part by weight of surfactant and 95-98 parts by weight of organic solvent are used.
Preferably, the ultrasonic dispersion in the step (2) adopts ultrasonic treatment for 2s and stopping for 2s, and then ultrasonic treatment for 2s and stopping for 2s, and the steps are repeated for 20-30 min.
Preferably, the mixing mass ratio of the paraffin emulsion and the graphene suspension in the step (3) is 1: 4-1: 2.
Preferably, the flocculant in the step (3) is a polyquaternary ammonium salt flocculant, more preferably at least one of dialkyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, bis-decyl dimethyl ammonium bromide, alkyl dimethyl benzyl ammonium chloride or alkyl dimethyl ethyl benzyl ammonium chloride, and the addition amount of the flocculant is 2-5% of the mass of the mixture.
Preferably, the spray drying in the step (3) adopts a pressure type, the pressure is 70-200 atmospheric pressures, and the particle size of the prepared microcapsule is 200-300 meshes.
Preferably, the addition proportion of the graphene-loaded paraffin filler in the step (4) accounts for 3-6% of the total mass of the coating.
The invention also provides the graphene anticorrosive paint for the photovoltaic equipment, which is prepared by the preparation method.
The stability of the emulsion system depends mainly on the surface charge of the particles of the polymer and the surface hydration protection layer, and the most common method is to use a flocculating agent to destabilize the precipitation of the emulsion. The essence of destabilizing an emulsion by adding a flocculant is the breaking of the emulsion. Demulsification means that the emulsion is completely broken into two immiscible phases. Demulsification is essentially the process of eliminating emulsion stabilizing conditions, causing dispersed droplets to aggregate and separate. The O/W type emulsion is generally demulsified by a chemical method, or when demulsification is carried out by a mechanical method, the demulsification capability of the O/W type emulsion is enhanced by an auxiliary chemical method. During the emulsion breaking process, some factors that promote the stability of the system must be overcome to polymerize the oil droplets. The oil droplets must be surrounded by an oppositely charged agent so that they remain neutral and the chemical agent can provide the oppositely charged agent. The emulsion breaking method for W/O emulsion includes chemical method and physical method, such as heating, centrifuging, vacuum filtering, etc. The chemical method is to make the water droplets dissolved in the oil unstable or to break the emulsifier. A preferred demulsifying method is to use a demulsifier having both a hydrophilic end and a lipophilic end to convert the W/O emulsion into a hydrophilic mixture. The mechanism is as follows: at the oil-water interface, the former surfactant is replaced by a more reactive surfactant, and this process can be accelerated by heating, which reduces viscosity, increases solubility and increases the diffusion of the surfactant in the oil phase. Because the water droplets in the W/O emulsion have a positive charge, demulsification is typically performed with negatively charged organic demulsifiers. According to the invention, the poly quaternary ammonium salt flocculant is adopted to realize demulsification and precipitation, so that a faster precipitation rate can be obtained, and the graphene is loaded in the heat storage material paraffin. The paraffin has good fluidity and dispersibility in the coating, so that the graphene attached to the paraffin can be driven to be uniformly dispersed. And the graphene is strongly combined with the paraffin, so that the graphene is not easy to fall off, and the possibility of the graphene reunion in the coating can be effectively reduced.
The process of the present invention is compared to other processes (such as in situ polymerization, sol gel or direct blending) as shown in table 1. It can be seen that: the method of the invention is obviously superior to the direct blending method in the anticorrosion effect of the coating and the dispersion effect of the graphene, and is superior to the in-situ polymerization method and the sol-gel method in the preparation cost, so the method of the invention is popularized and applied.
TABLE 1
| Performance index | Indoor corrosion protection grade | Outdoor anticorrosion grade | Dispersion situation | Whether it is easy to agglomerate | Cost of preparation |
| in situ polymerization process | F1～F2 | WF1～WF2 | Good effect | Is not easy to be | Is higher than |
| Sol gel process | F1～F2 | WF1～WF2 | Good effect | Is not easy to be | Is higher than |
| Direct blending process | F1 | W～WF1 | Is poor | Easy to use | Is low in |
| The method of the invention | F2 | WF2 | Good effect | Is not easy to be | is lower than |
The invention provides a graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof, and compared with the prior art, the graphene anticorrosive paint has the outstanding characteristics and excellent effects that:
1. The preparation method provided by the invention overcomes the defect that graphene is difficult to disperse in the coating, can prevent the graphene from self-agglomeration, and is beneficial to maintaining the uniformity, compactness and stability of the dispersion.
2. The coating prepared by the invention has good anticorrosion effect and ideal barrier property, and can be used for anticorrosion of photovoltaic equipment.
3. According to the preparation method disclosed by the invention, the paraffin loaded with the graphene is encapsulated, so that the graphene is prevented from falling off and the paraffin as a heat storage material is prevented from leaking, and the stability of the performance of the coating is ensured.
4. The preparation method disclosed by the invention is simple in process, convenient to operate, low in raw material cost and processing cost, and capable of being popularized and applied.
Drawings
FIG. 1 is an SEM photograph of a coating film obtained in example 1;
Fig. 2 is an SEM image of the coating film obtained in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof are disclosed, wherein the specific process for preparing the anticorrosive paint is as follows:
10kg of polyethylene wax was melted by heating while slowly stirring at a stirring speed of 200r/min and a heating temperature of 85 ℃. Then 0.25kg of fatty alcohol-polyoxyethylene ether and 0.15kg of octadecyl trimethyl ammonium chloride are added as emulsifying agents, and the stirring speed is increased to 900r/min at the same time, so that the components are fully and uniformly mixed. Then adding emulsified water with the same temperature, and adding 1g of water every 1min until white pasty emulsion is obtained. Then cooling to normal temperature, slowing down the stirring speed to 600r/min, adding 5kg of carboxymethyl cellulose solution as a tackifier, and uniformly stirring to obtain paraffin emulsion; mixing 3.9kg of graphene dry powder, 0.1kg of sodium dodecyl benzene sulfonate and 96kg of N, N-dimethylformamide, and performing ultrasonic dispersion for 20min to obtain a graphene suspension; mixing 10kg of paraffin emulsion and 20kg of graphene suspension, adding 0.9kg of dialkyl dimethyl ammonium chloride, carrying out emulsion coprecipitation to load graphene in heat storage material paraffin, then carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the filtrate by adopting a spray drying method to obtain the paraffin filler loaded with the graphene; adding the obtained filler into the coating according to the mass ratio of 6%, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
The indoor anticorrosion grade and the outdoor anticorrosion grade of the graphene anticorrosion paint obtained in example 1 are tested, the dispersion condition of graphene in a coating film is observed by adopting a scanning electron microscope, the obtained data is shown in table 2, and the SEM is shown in fig. 1.
Example 2
A graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof are disclosed, wherein the specific process for preparing the anticorrosive paint is as follows:
10kg of microcrystalline paraffin was heated while slowly stirring to melt the paraffin, the stirring speed was 200r/min, and the heating temperature was 90 ℃. Then 0.3kg of fatty alcohol-polyoxyethylene ether and 0.2kg of octadecyl trimethyl ammonium chloride are added as emulsifying agents, and the stirring speed is increased to 700r/min at the same time, so that the components are fully and uniformly mixed. Then adding emulsified water with the same temperature, and adding 1g of water every 1min until white pasty emulsion is obtained. Then cooling to normal temperature, slowing down the stirring speed to 400r/min, adding 4kg of carboxymethyl cellulose solution as a tackifier, and uniformly stirring to obtain paraffin emulsion; mixing 4.9kg of graphene dry powder, 0.1kg of sodium dodecyl sulfate and 95kg of N-methyl pyrrolidone, and performing ultrasonic dispersion for 20min to obtain a graphene suspension; mixing 10kg of paraffin emulsion with 25kg of graphene suspension, adding 1.1kg of alkyl dimethyl benzyl ammonium chloride, carrying out emulsion coprecipitation to load graphene in heat storage material paraffin, then carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the filtrate by adopting a spray drying method to obtain the paraffin filler loaded with the graphene; adding the obtained filler into the coating according to the mass ratio of 3%, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
the graphene anticorrosive paint obtained in example 2 was tested for its indoor anticorrosive rating and outdoor anticorrosive rating, and the dispersion of graphene in the coating film was observed by scanning electron microscopy, and the obtained data are shown in table 2.
example 3
A graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof are disclosed, wherein the specific process for preparing the anticorrosive paint is as follows:
10kg of chlorinated paraffin was heated to melt it while slowly stirring at a stirring speed of 180r/min and a heating temperature of 90 ℃. Then 0.2kg of fatty alcohol-polyoxyethylene ether and 0.1kg of octadecyl trimethyl ammonium chloride are added as emulsifying agents, and the stirring speed is increased to 800r/min at the same time, so that the components are fully and uniformly mixed. Then adding emulsified water with the same temperature, and adding 1g of water every 1min until white pasty emulsion is obtained. Then cooling to normal temperature, slowing down the stirring speed to 500r/min, adding 3kg of carboxymethyl cellulose solution as a tackifier, and uniformly stirring to obtain paraffin emulsion; mixing 3.9kg of graphene dry powder, 0.1kg of polyvinyl alcohol and 96kg of dimethyl sulfoxide, and dispersing for 25min by adopting ultrasonic to prepare graphene suspension; mixing 10kg of paraffin emulsion with 30kg of graphene suspension, adding 1.2kg of bis-decyl dimethyl ammonium bromide, carrying out emulsion coprecipitation to load the graphene in the heat storage material paraffin, then carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the filtrate by adopting a spray drying method to obtain the paraffin filler loaded with the graphene; adding the obtained filler into the coating according to a mass ratio of 5%, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
The graphene anticorrosive paint obtained in example 3 was tested for its indoor anticorrosive rating and outdoor anticorrosive rating, and the dispersion of graphene in the coating film was observed by scanning electron microscopy, and the obtained data are shown in table 2.
Example 4
A graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof are disclosed, wherein the specific process for preparing the anticorrosive paint is as follows:
10kg of polyethylene wax was melted by heating while slowly stirring at a stirring speed of 120r/min and a heating temperature of 85 ℃. Then 0.25kg of fatty alcohol-polyoxyethylene ether and 0.15kg of octadecyl trimethyl ammonium chloride are added as emulsifying agents, and the stirring speed is increased to 750r/min at the same time, so that the components are fully and uniformly mixed. Then adding emulsified water with the same temperature, and adding 1g of water every 1min until white pasty emulsion is obtained. Then cooling to normal temperature, slowing down the stirring speed to 450r/min, adding 6kg of carboxymethyl cellulose solution as a tackifier, and uniformly stirring to obtain paraffin emulsion; mixing 5kg of graphene dry powder, 0.1kg of sodium lignin sulfonate and 94.9kg of isopropanol, and performing ultrasonic dispersion for 28min to obtain a graphene suspension; mixing 10kg of paraffin emulsion and 35kg of graphene suspension, adding 1.3kg of alkyl dimethyl benzyl ammonium chloride, carrying out emulsion coprecipitation to load graphene in heat storage material paraffin, then carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the filtrate by adopting a spray drying method to obtain the paraffin filler loaded with the graphene; adding the obtained filler into the coating according to a mass ratio of 4%, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
The graphene anticorrosive paint obtained in example 4 was tested for its indoor anticorrosive rating and outdoor anticorrosive rating, and the dispersion of graphene in the coating film was observed by scanning electron microscopy, and the obtained data are shown in table 2.
Example 5
a graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof are disclosed, wherein the specific process for preparing the anticorrosive paint is as follows:
10kg of chlorinated paraffin was heated to melt it while slowly stirring at a stirring speed of 120r/min and a heating temperature of 88 ℃. Then 0.3kg of fatty alcohol-polyoxyethylene ether and 0.1kg of octadecyl trimethyl ammonium chloride are added as emulsifying agents, and the stirring speed is increased to 850r/min at the same time, so that the components are fully and uniformly mixed. Then adding emulsified water with the same temperature, and adding 1g of water every 1min until white pasty emulsion is obtained. Then cooling to normal temperature, slowing down the stirring speed to 550r/min, adding 4kg of carboxymethyl cellulose solution as a tackifier, and uniformly stirring to obtain paraffin emulsion; mixing 5kg of graphene dry powder, 0.1kg of sodium dodecyl sulfate and 94.9kg of ethanol, and performing ultrasonic dispersion for 22min to obtain a graphene suspension; mixing 10kg of paraffin emulsion with 40kg of graphene suspension, adding 1.5kg of alkyl dimethyl ethyl benzyl ammonium chloride, carrying out emulsion coprecipitation to load the graphene in heat storage material paraffin, then carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the filtrate by adopting a spray drying method to obtain the paraffin filler loaded with the graphene; adding the obtained filler into the coating according to a mass ratio of 4%, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
The graphene anticorrosive paint obtained in example 5 was tested for its indoor anticorrosive rating and outdoor anticorrosive rating, and the dispersion of graphene in the coating film was observed by scanning electron microscopy, and the obtained data are shown in table 2.
Example 6
A graphene anticorrosive paint for photovoltaic equipment and a preparation method thereof are disclosed, wherein the specific process for preparing the anticorrosive paint is as follows:
10kg of microcrystalline paraffin was heated while slowly stirring to melt the paraffin, the stirring speed was 200r/min, and the heating temperature was 90 ℃. Then 0.2kg of fatty alcohol-polyoxyethylene ether and 0.2kg of octadecyl trimethyl ammonium chloride are added as emulsifying agents, and the stirring speed is increased to 800r/min at the same time, so that the components are fully and uniformly mixed. Then adding emulsified water with the same temperature, and adding 1g of water every 1min until white pasty emulsion is obtained. Then cooling to normal temperature, slowing down the stirring speed to 600r/min, adding 5kg of carboxymethyl cellulose solution as a tackifier, and uniformly stirring to obtain paraffin emulsion; mixing 4kg of graphene dry powder, 0.1kg of polyvinyl alcohol and 95.9kg of methanol, and dispersing for 25min by adopting ultrasonic to prepare graphene suspension; mixing 10kg of paraffin emulsion with 30kg of graphene suspension, adding 1.2kg of dialkyl dimethyl ammonium chloride, carrying out emulsion coprecipitation to load graphene in heat storage material paraffin, then carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the filtrate by adopting a spray drying method to obtain the paraffin filler loaded with the graphene; adding the obtained filler into the coating according to a mass ratio of 5%, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
The graphene anticorrosive paint obtained in example 6 was tested for its indoor anticorrosive rating and outdoor anticorrosive rating, and the dispersion of graphene in the coating film was observed by scanning electron microscopy, and the obtained data are shown in table 2.
Comparative example 1
and (3) directly adding the graphene dispersion liquid with the corresponding mass into the coating without using paraffin as a carrier, wherein the preparation and addition proportion of the graphene dispersion liquid are consistent with those of the example 6.
And (3) testing the indoor anticorrosion grade and the outdoor anticorrosion grade of the graphene anticorrosion paint obtained in the comparative example 1, wherein the indoor anticorrosion grade is as follows: indoor medium corrosion prevention type F1; indoor strong corrosion prevention type F2; the outdoor anticorrosion grade is as follows: outdoor light corrosion prevention type W; outdoor medium erosion resistant WF 1; outdoor strong corrosion prevention type WF2, and the dispersion condition of graphene in the coating film is observed by adopting a scanning electron microscope, the obtained data are shown in Table 2, and the SEM is shown in FIG. 2.
TABLE 2
| Performance index | Indoor corrosion protection grade | outdoor anticorrosion grade | Dispersion situation | whether it is easy to agglomerate |
| Comparative example 1 | F1 | WF1 | is poor | Easy to use |
| example 1 | F2 | WF2 | Good effect | Is not easy to be |
| Example 2 | F2 | WF2 | Good effect | is not easy to be |
| Example 3 | F2 | WF2 | Good effect | Is not easy to be |
| Example 4 | F2 | WF2 | Good effect | Is not easy to be |
| Example 5 | F2 | WF2 | Good effect | Is not easy to be |
| Example 6 | F2 | WF2 | Good effect | Is not easy to be |
Claims (10)
1. A preparation method of graphene anticorrosive paint for photovoltaic equipment is characterized in that paraffin is prepared into paraffin emulsion, graphene is prepared into graphene suspension, polyquaternary ammonium salt flocculating agent is added after the paraffin emulsion and the graphene suspension are mixed according to a proportion, and the paraffin filler loaded with the graphene is obtained through emulsion coprecipitation, suction filtration and microcapsule granulation, can be added into the paint before the paint is used, is coated after being uniformly stirred, and endows the paint with good anticorrosive performance, and can be used for the photovoltaic equipment, and the preparation method comprises the following specific steps:
(1) Slowly stirring and heating paraffin with a certain mass while adding an emulsifier, simultaneously increasing the stirring speed to fully and uniformly mix the paraffin with the emulsifier, then adding emulsified water with the same temperature, adding the emulsified water once every 1min until white pasty emulsion is obtained, then cooling the temperature to the normal temperature, slowing down the stirring speed, adding a certain amount of tackifier, and uniformly stirring to obtain paraffin emulsion;
(2) Mixing graphene dry powder, a surfactant and an organic solvent according to a certain mass ratio, and performing ultrasonic dispersion to prepare a graphene suspension;
(3) Mixing the paraffin emulsion obtained in the step (1) with the graphene suspension obtained in the step (2), adding a certain amount of polyquaternium flocculant, carrying out emulsion coprecipitation to load graphene in heat storage material paraffin, carrying out suction filtration, removing filtrate, and carrying out microcapsule granulation on the heat storage material paraffin by adopting a spray drying method to obtain the paraffin filler loaded with the graphene;
(4) And (4) adding the graphene-loaded paraffin filler obtained in the step (3) into the coating according to a certain mass ratio, and uniformly stirring to obtain the graphene anticorrosive coating for the photovoltaic equipment.
2. the preparation method of the graphene anticorrosive paint for the photovoltaic device according to claim 1, characterized in that: the paraffin in the step (1) is at least one of microcrystalline paraffin, polyethylene wax or chlorinated paraffin; the initial stirring speed of the paraffin is 100-200 r/min, and the heating temperature is 85-90 ℃.
3. The preparation method of the graphene anticorrosive paint for photovoltaic devices according to claim 1 or 2, characterized in that: in the step (1), the emulsifier is fatty alcohol-polyoxyethylene ether and octadecyl trimethyl ammonium chloride; the addition amount of the fatty alcohol-polyoxyethylene ether is 2-3% of the mass of the paraffin, the addition amount of the octadecyl trimethyl ammonium chloride is 1-2% of the mass of the paraffin, and the stirring speed after the emulsifier is added is 700-900 r/min; the stirring speed after cooling to the normal temperature is 400-600 r/min.
4. The preparation method of the graphene anticorrosive paint for the photovoltaic device according to claim 1, characterized in that: the first adding amount of the emulsified water in the step (1) is the same as the mass of the paraffin, and then 1g of the emulsified water is added every time; the tackifier is a carboxymethyl cellulose solution, the mass fraction of the carboxymethyl cellulose solution is 4-6%, and the addition amount of the carboxymethyl cellulose solution is 30-60% of the mass of the paraffin.
5. The preparation method of the graphene anticorrosive paint for the photovoltaic device according to claim 1, characterized in that: the surfactant in the step (2) is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinyl alcohol or sodium lignosulfonate; the organic solvent is at least one of methanol, ethanol, isopropanol, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.
6. the preparation method of the graphene anticorrosive paint for photovoltaic devices according to claim 1 or 5, characterized in that: in the step (2), the graphene suspension contains 3-5 parts by weight of graphene dry powder, 0.05-0.1 part by weight of surfactant and 95-98 parts by weight of organic solvent.
7. The preparation method of the graphene anticorrosive paint for the photovoltaic device according to claim 1, characterized in that: performing ultrasonic dispersion in the step (2) for 2s and stopping for 2s, and performing ultrasonic dispersion for 2s and stopping for 2s, and repeating the steps for 20-30 min; the mixing mass ratio of the paraffin emulsion to the graphene suspension is 1: 4-1: 2.
8. The preparation method of the graphene anticorrosive paint for the photovoltaic device according to claim 1, characterized in that: the polyquaternium flocculant in the step (3) is at least one of dialkyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, bis-decyl dimethyl ammonium bromide, alkyl dimethyl benzyl ammonium chloride or alkyl dimethyl ethyl benzyl ammonium chloride, and the addition amount of the flocculant is 2-5% of the mass amount of the mixture; the spray drying adopts a pressure type, the pressure is 70-200 atmospheric pressures, and the particle size of the prepared microcapsule is 200-300 meshes.
9. The preparation method of the graphene anticorrosive paint for the photovoltaic device according to claim 1, characterized in that: in the step (4), the addition proportion of the graphene-loaded paraffin filler accounts for 3-6% of the total mass of the coating.
10. the graphene anticorrosive paint for the photovoltaic equipment is prepared by the preparation method of any one of claims 1 to 9.
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