CN111303738B - Super-hydrophobic-lubricating composite anti-icing coating with porous structure and preparation method thereof - Google Patents
Super-hydrophobic-lubricating composite anti-icing coating with porous structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of new materials, and particularly relates to a super-hydrophobic-lubricating composite anti-icing coating with a porous structure and a preparation method thereof. The coating is composed of a foamed porous super-hydrophobic coating and a bionic joint lubricating liquid, and the super-hydrophobic-lubricating composite anti-icing coating with the super-hydrophobic foamed porous structure is prepared by compounding low-molecular polybutadiene, polyacrylamide, waterborne polyurethane and alkyl ketene dimer and heating and foaming the mixture by using p-toluenesulfonyl hydrazide. The blending component of the bionic joint lubricating liquid and the low molecular polybutadiene of the obtained coating can obviously reduce the adhesion of the ice layer, so that the adhesion of the ice layer is reduced to be below 5kPa, and an excellent anti-ice effect is achieved.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a super-hydrophobic-lubricating composite anti-icing coating with an anti-icing effect.
Background
Freezing and cold weather cause billions of losses in China every year, and relates to the field of delay and loss of space transportation, public transportation, infrastructure and even electric power transportation. The ice coating of the circuit can make the timely dredging of the electric power department extremely challenging, and the ice coating of the circuit is more influential in the world in the big country serving as the ground and the living things in China. In addition, the effects of icing on aircraft wings are of paramount importance. Severe icing can even cause the wings to stall, causing an air crash. On the aspect of roads, the lifting of the trip safety is started from the anti-skidding and anti-icing of tires and rails, and the icing brings huge hidden dangers to the property and the safety of people to a great extent. Therefore, the research on the super-hydrophobic anti-icing coating material is of great social significance.
The lotus leaf has self-cleaning, anti-icing and drag reduction characteristics, so that the lotus leaf has good super-hydrophobicity. The "lotus effect" is also the most well known phenomenon of superhydrophobicity. Research shows that the micro/nano structure of natural organism has important significance for researching anti-icing material. For example, the lotus leaf surface contains a micro/nano composite mastoid structure, so that the surface is super-hydrophobic [ Barthlott, W.; neinhuis, c.planta 1997,202, 1; feng, l.; li, s.h.; li, y.s.; li, h.j.; zhang, l.j.; zhai, j.; song, y.l.; liu, b.q.; jiang, l.; zhu, d.b. advanced Materials 2002,14,1857. Later researchers were inspired to produce a number of superhydrophobic coatings. Therefore, the damage of the external force action on the micro-nano structure of the super-hydrophobic surface can directly influence the super-hydrophobic effect and the anti-icing characteristic of the surface. It was found that the low surface energy lubricating fluid-containing surface of the imitation nepenthes exhibited excellent compression characteristics as well as good anti-icing performance [ Wong, t. -s.et al.nature 2001,477,443; kim, p.et al.acs Nano 2012,6, 6569; liu, Q.et al.applied Surface Science 2015,346,68 ]. The porous structure is constructed on the surface by using an electrochemical corrosion method, so that the low-surface-energy lubricating liquid is adsorbed, and the low-surface-energy lubricating liquid is prevented from flowing away. The adhesion of such surfaces to objects is extremely low, and the adhesion of such lubricated surfaces to objects is extremely low, and both water and ice can slide off the surface under the action of gravity, resulting in less external force. The difficulty of this solution is to improve the durability of the anti-icing material, because as the number of uses increases, the amount of surface lubricant decreases, the adhesion increases, and the anti-icing effect is lost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the super-hydrophobic-lubricating composite anti-icing coating with the foaming porous structure and the preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the super-hydrophobic-lubricating composite anti-icing coating with the porous structure is characterized by being prepared by mixing low-molecular polybutadiene, polyacrylamide, waterborne polyurethane and an alkyl ketene dimer solubilizer, heating and foaming the mixture by virtue of p-toluenesulfonyl hydrazide, and spraying the mixture.
The preparation method of the super-hydrophobic-lubricating composite anti-icing coating with the foaming porous structure is characterized by comprising the following steps of:
(1) mixing low-molecular polybutadiene, polyacrylic ester, waterborne polyurethane and alkyl ketene dimer, adding heptane as a solvent, heating, stirring and dissolving at the temperature of 20-30 ℃ for 1h, heating and stirring for foaming by using p-toluenesulfonyl hydrazide, forming a film by using the obtained solution at normal temperature in a spraying mode, and drying at the temperature of 40-60 ℃ to obtain a super-hydrophobic coating with a foamed porous structure;
(2) injecting bionic joint lubricating liquid into the surface of the super-hydrophobic coating with the foamed porous structure prepared in the step (1) to obtain the super-hydrophobic-lubricating composite anti-icing coating with the foamed porous structure.
Further, the mixing weight ratio of the low molecular polybutadiene, the polyacrylic ester, the waterborne polyurethane, the alkyl ketene dimer and the heptane in the step (1) is 1: 2-5: 5-6: 3-6: 7-9.
Further, in the step (1), the addition amount of the tosylhydrazide is 20-50 wt.% of the total mass of the mixture consisting of the low-molecular polybutadiene, the polyacrylic ester, the aqueous polyurethane, the alkyl ketene dimer and the heptane, the heating temperature is 50-80 ℃, and the heating foaming time is 1 hour.
Further, the bionic joint lubricating fluid in the step (2) is nano-graphene modified Hyaluronic Acid (HA), and the nano-graphene is added into the hyaluronic acid to obtain the bionic joint lubricating fluid, wherein the particle size range of the nano-graphene is 70-100 nm, and the addition amount of the nano-graphene is 1-2.5 wt.% of the total mass of the bionic joint lubricating fluid; adding a lubricating liquid to the surface of the super-hydrophobic coating by adopting a micro-injector, wherein the adding amount is 0.3-0.5g/cm2。
Compared with the prior art, the invention has the following remarkable advantages: 1) after a heptane solution of low-molecular polybutadiene, polyacrylic ester, waterborne polyurethane and alkyl ketene dimer is sprayed to form a film, a porous membrane structure is automatically formed after drying, the contact angle of a surface water drop can reach 155 degrees, and the water-repellent polyurethane coating has excellent hydrophobicity. Meanwhile, the preparation process is simple, the equipment requirement is low, and large-scale preparation can be realized; 2) the Hyaluronic Acid (HA) lubricating liquid modified by the nano-graphene is free of fluorine, more environment-friendly and easy to obtain; 3) the blending component of the bionic joint lubricating liquid and the low molecular polybutadiene of the obtained coating can obviously reduce the adhesion of the ice layer, so that the adhesion of the ice layer is reduced to be below 5kPa, and an excellent anti-ice effect is achieved.
Drawings
FIG. 1 shows the contact angle of a water droplet in example 1.
FIG. 2 is the water drop contact angle of example 2.
FIG. 3 is the water drop contact angle of example 3.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
The super-hydrophobic-lubricating composite anti-icing coating with the foaming porous structure provided by the invention has excellent anti-icing performance and can obviously reduce the adhesion of ice. The anti-icing coating is composed of a super-hydrophobic-lubricating composite anti-icing coating with a foaming porous structure and bionic joint lubricating liquid, and the super-hydrophobic-lubricating composite anti-icing coating with the foaming porous structure is prepared by compounding low-molecular polybutadiene, polyacrylic ester, waterborne polyurethane and alkyl ketene dimer.
The preparation method of the anti-icing coating comprises the following steps:
(1) firstly, low molecular polybutadiene, polyacrylic ester, aqueous polyurethane, alkyl ketene dimer, and heptane (solvent) body are mixed according to a weight ratio of 1: 2-5: 5-6: 3-6: 7-9, heating and stirring at 20-30 ℃ for 1h, adding 20-50 wt.% of tosylhydrazide of the total mass of the mixture, foaming at 50-80 ℃ for 1h, spraying at normal temperature to form a film, and drying at 40-60 ℃ to obtain the super-hydrophobic coating with a foamed porous structure;
(2) secondly, adding nano graphene with the particle size of 70-100 nm into Hyaluronic Acid (HA) lubricating liquid according to the weight ratio of 1-2.5 wt.%, and performing ultrasonic dispersion to obtain bionic joint lubricating liquid;
(3) finally, injecting 0.3-0.5g/cm of nano-graphene modified bionic joint lubricating fluid into the surface of the super-hydrophobic coating with the foamed porous structure through a micro-injector2And obtaining the super-hydrophobic-lubricating composite anti-icing coating with a foaming porous structure.
The present invention will be described in further detail with reference to the following examples:
example 1:
(1) low-molecular polybutadiene, polyacrylic ester, waterborne polyurethane, alkyl ketene dimer and heptane are mixed according to the mass ratio of 1: 3: 5: 3: 7, after mixing, heating to 25 ℃, stirring for 1h, adding toluenesulfonyl hydrazide accounting for 20 wt% of the total mass of the mixture, foaming for 1h at 70 ℃, spraying by using a spray gun at normal temperature, and drying at 50 ℃ to obtain the super-hydrophobic-lubricating composite anti-icing coating with a foamed porous structure;
(2) adding nano graphene with the particle size of 90nm into Hyaluronic Acid (HA) lubricating liquid according to the weight ratio of 2 wt.%, and performing ultrasonic dispersion to obtain modified bionic joint lubricating liquid;
(3) injecting nano-graphene modified Hyaluronic Acid (HA)0.3g/cm by using a micro-injector2And then obtaining the composite coating.
The contact angle of a water drop of the prepared super-hydrophobic-lubricating composite anti-icing coating with the foamed porous structure is 120 degrees, as shown in figure 1; the obtained composite coating has a contact area of 1cm at-30 deg.C2And the adhesion of the ice layer on the surface of the ice block with the height of 3cm is 10 kPa.
Example 2:
(1) low-molecular polybutadiene, polyacrylic ester, waterborne polyurethane, alkyl ketene dimer and heptane are mixed according to the mass ratio of 1: 4: 6: 5: 8, mixing, heating to 30 ℃, stirring for 1h, adding 45 wt.% of toluenesulfonyl hydrazide, foaming for 1h at 75 ℃, spraying by using a spray gun at normal temperature, and drying at 40 ℃ to obtain a super-hydrophobic coating with a foamed porous structure;
(2) adding nano graphene with the particle size of 80nm into Hyaluronic Acid (HA) lubricating liquid according to the weight ratio of 1.5 wt.%, and performing ultrasonic dispersion to obtain modified bionic joint lubricating liquid;
(3) injecting nano graphene into Hyaluronic Acid (HA) at 0.4g/cm by using a micro-injector2And then obtaining the composite coating.
The contact angle of a water drop of the prepared super-hydrophobic-lubricating composite anti-icing coating with the foamed porous structure is 130 degrees, as shown in figure 2; the obtained synovial fluid injection type composite coating has a contact area of 1cm at-30 deg.C2And the adhesion of the ice layer on the surface of the ice block with the height of 3cm is 6 kPa.
Example 3:
(1) low-molecular polybutadiene, polyacrylic ester, waterborne polyurethane, alkyl ketene dimer and heptane are mixed according to the mass ratio of 1: 4: 5: 6: 9, mixing, heating to 20 ℃, stirring for 1h, adding 25 wt.% of toluenesulfonyl hydrazide, foaming for 1h at 60 ℃, spraying by using a spray gun at normal temperature, and drying at 50 ℃ to obtain a super-hydrophobic coating with a foamed porous structure;
(2) adding nano graphene with the particle size of 85nm into Hyaluronic Acid (HA) lubricating liquid according to the weight ratio of 1.5 wt.%, and performing ultrasonic dispersion to obtain the modified bionic joint lubricating liquid
(3) Injecting nano graphene into Hyaluronic Acid (HA) at a concentration of 0.35g/cm by using a microsyringe2And then obtaining the composite coating.
The contact angle of a water drop of the prepared super-hydrophobic-lubricating composite anti-icing coating with the foamed porous structure is 155 degrees, as shown in figure 3; the obtained synovial fluid injection type composite coating has a contact area of 1cm at-30 deg.C2And the adhesion of the ice layer on the surface of the ice block with the height of 3cm is 4 kPa.
Comparative example:
a lubricant-infused anti-icing coating was prepared as described in the background of Liquid-infused structured surfaces with extreme anti-ice and anti-front performance by the following steps:
(1) preparing a polypyrazole homopolymer solution with the concentration of 0.1-0.2M;
(2) preparing and obtaining a coating by adopting a constant potential deposition mode;
(3) krytox 100 perfluorolubricant is injected.
The experiment shows that: the coating is obtained only on the metal surface in an electrochemical mode, and the application range is narrow; the prepared coating is easy to evaporate lubricating liquid, so that the coating is ineffective; the coating prepared in the comparative example has a contact area of 1cm at-30 DEG C2And the ice surface adhesion of the ice is up to 20kPa for the ice block with the height of 3cm, which is far higher than the adhesion of the coating prepared by the invention, and the ice resistance effect is poor.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (2)
1. The super-hydrophobic-lubricating composite anti-icing coating with the porous structure is characterized by comprising a foamed porous super-hydrophobic coating and bionic joint lubricating liquid injected to the surface of the super-hydrophobic coating, wherein the super-hydrophobic coating is prepared by mixing low-molecular polybutadiene, polyacrylamide, waterborne polyurethane and an alkyl ketene dimer with a solvent, heating and foaming the mixture by virtue of p-toluenesulfonyl hydrazide and spraying the mixture; the preparation method of the super-hydrophobic-lubricating composite anti-icing coating with the porous structure comprises the following specific steps:
(1) low-molecular polybutadiene, polyacrylamide, waterborne polyurethane, alkyl ketene dimer and heptane are mixed according to the mass ratio of 1: 4: 5: 6: 9, mixing, heating to 20 ℃, stirring for 1h, adding 25 wt.% of p-toluenesulfonyl hydrazide, foaming for 1h at 60 ℃, spraying by using a spray gun at normal temperature, and drying at 50 ℃ to obtain a super-hydrophobic coating with a foamed porous structure;
(2) adding nano graphene with the particle size of 85nm into hyaluronic acid lubricating liquid according to the weight ratio of 1.5 wt.%, and performing ultrasonic dispersion to obtain modified bionic joint lubricating liquid;
(3) using a microsyringe at a concentration of 0.35g/cm2And injecting the modified bionic joint lubricating fluid to obtain the composite coating.
2. The preparation method of the superhydrophobic-lubricating composite anti-icing coating with porous structure according to claim 1
The method is characterized by comprising the following specific steps:
(1) low-molecular polybutadiene, polyacrylamide, waterborne polyurethane, alkyl ketene dimer and heptane are mixed according to the mass ratio of 1: 4: 5: 6: 9, mixing, heating to 20 ℃, stirring for 1h, adding 25 wt.% of p-toluenesulfonyl hydrazide, foaming for 1h at 60 ℃, spraying by using a spray gun at normal temperature, and drying at 50 ℃ to obtain a super-hydrophobic coating with a foamed porous structure;
(2) adding nano graphene with the particle size of 85nm into hyaluronic acid lubricating liquid according to the weight ratio of 1.5 wt.%, and performing ultrasonic dispersion to obtain modified bionic joint lubricating liquid;
(3) using a microsyringe at a concentration of 0.35g/cm2And injecting the modified bionic joint lubricating fluid to obtain the composite coating.
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