CN107083102B

CN107083102B - Composite cerium oxide nano hydrophobic particle with multilevel structure and preparation method and application thereof

Info

Publication number: CN107083102B
Application number: CN201710256757.0A
Authority: CN
Inventors: 叶辉; 蒋冠吾; 李卫平
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-04-19
Filing date: 2017-04-19
Publication date: 2021-01-12
Anticipated expiration: 2037-04-19
Also published as: CN107083102A

Abstract

The invention discloses a composite cerium oxide nano hydrophobic particle with a multilevel structure, and a preparation method and application thereof, and belongs to the field of nanotechnology. The preparation method comprises the steps of preparing an amination modified nanoparticle dispersion liquid A and a cerium oxide modifier aqueous solution B; and (3) obtaining the composite cerium oxide nano hydrophobic particles F with a multilevel structure finally by using the composite cerium oxide nano particles C, the dispersion liquid D and the hydrophobic modifier E. The surface of the nano hydrophobic particle is non-smooth and has a strawberry-like multilevel structure, and the monodispersity is good. The composite cerium oxide nano hydrophobic particles with the multilevel structure are added into commercially available resin or common coating to prepare spraying liquid H for the anti-icing coating. The invention can realize hydrophobic modification of the surface, and the contact angle of the surface of the obtained anti-icing film layer is more than 155 degrees, so that the anti-icing effect is good.

Description

Composite cerium oxide nano hydrophobic particle with multilevel structure and preparation method and application thereof

Technical Field

The invention belongs to the technical field of nanometer, and relates to a composite nanometer hydrophobic particle, in particular to a composite cerium oxide nanometer hydrophobic particle with a multilevel structure, which can be directly dispersed into a solvent for spraying and can also be added into a coating for preventing ice coating in the fields of aircraft skin and the like.

Background

The ice coating prevention is that supercooled water drops are difficult to freeze on the surface of an airplane through the characteristic or the structural design of the surface material of an airplane body, and the ice coating prevention coating has the characteristic of actively preventing the water drops from being frozen, so that the ice coating prevention coating has the advantages of low energy consumption, environmental friendliness and wide application range, and is gradually the key point of research in various countries.

The hydrophobic surface may weaken the binding force between ice and a substrate to achieve an anti-icing effect, for reasons including: 1) whether ice can be formed and the contact time of the ice and the surface of the matrix is related to heat exchange and a non-uniform nucleation mechanism, and the liquid drops on the super-hydrophobic surface easily roll off and slide off under the action of natural external force, so that the water hanging amount before freezing and the contact time of the water drops and the surface are greatly reduced; 2) inhibit or retard the formation of ice crystals on the surface of the material: the super-hydrophobic structure can slow down nucleation and improve nucleation free energy. 3) Reducing the adhesion of ice crystals to the contact interface: when the super-hydrophobic surface is frozen, the contact area between the ice crystals and the interface is small, and the adhesive force is small. Therefore, the superhydrophobic anti-icing coating is currently the most active international research direction.

Surfaces with a solid interface water contact angle of more than 150 ° and a rolling angle of less than 10 ° are generally referred to as superhydrophobic surfaces. Surface roughness and low surface energy are two requirements for achieving superhydrophobicity, and therefore superhydrophobic surfaces can be prepared by two methods: one is to construct a rough structure on the surface of a hydrophobic material; the other is to modify the low surface energy substance on the rough surface. Specifically, according to physical and chemical methods, the physical methods mainly include: plasma treatment, laser treatment, phase separation, electrospinning, templating, spin coating, and spray coating. The chemical method mainly comprises the following steps: sol-gel, solvothermal, electrochemical, LBL, self-assembly, in situ synthesis, one-step method, and the like. Although along with the continuous development of research on the direction of superhydrophobicity, a large number of methods for constructing superhydrophobic surfaces emerge. The preparation method has continuous innovation, but in general, most preparation methods have the defects of high process requirement, long time consumption, high cost, large-scale equipment requirement, difficulty in large-area preparation and the like.

Spraying is a common coating preparation method, and is a coating method of dispersing into uniform and fine droplets by a spray gun or a disc atomizer with the aid of pressure or centrifugal force and applying to the surface of an object to be coated. The spraying has the defect that the surface appearance cannot be accurately controlled, so that the preparation of the anti-icing surface directly by using the spraying process depends on the microstructure of the surface of the base material and the surface energy characteristics of the coating, and the large-area hydrophobic anti-icing surface is difficult to directly prepare on different base materials.

Disclosure of Invention

The invention aims to provide a composite cerium oxide nano hydrophobic particle with a multilevel structure and a preparation method thereof. The invention also aims to prepare dispersion liquid by utilizing the cerium oxide nano hydrophobic particles, or add the dispersion liquid into different coatings to prepare super hydrophobic coatings suitable for spraying, and micro-nano surface roughness and low surface energy characteristics can be constructed on the surfaces of different base materials by a spraying method, so that the modification and preparation of large-area anti-icing surfaces of different materials are realized.

The composite cerium oxide nano hydrophobic particle with the multilevel structure prepared by the invention is characterized in that the multilevel structure is a multidimensional nanostructure unit constructed by one or more low-dimensional nanostructure units. The composite cerium oxide nano hydrophobic particle with the multilevel structure has a special spatial structure, not only maintains the inherent physical and chemical characteristics of the nano material, but also can overcome a plurality of adverse effects such as easy agglomeration and the like caused by high surface activity of the nano material.

The composite cerium oxide nano hydrophobic particles with the multilevel structure can be directly dispersed into a solvent for spraying, can also be added into a coating, and can be applied to the ice coating prevention of aircraft skins.

The invention firstly provides a preparation method of a composite cerium oxide nano hydrophobic particle with a multilevel structure, which comprises the following steps:

firstly, adding an amination modifier and nanoparticles into an organic solvent to prepare an amination modified nanoparticle dispersion liquid A;

the mass ratio of the nanoparticles to the organic solvent is 1: 50-1: 100; the mass ratio of the amination modifier to the nanoparticles is 1: 1-1: 10.

Secondly, preparing cerium nitrate, hexamethylenetetramine and water into a cerium oxide modifier aqueous solution B according to the mass ratio of 1:1: 10-1: 5: 50;

thirdly, ultrasonically mixing the aminated modified nanoparticle dispersion liquid A and a cerium oxide modifier aqueous solution B according to the mass ratio of 3: 1-1: 3, and stirring and reacting for 10-12 hours at the temperature of 60-80 ℃; centrifugally separating to obtain composite cerium oxide nanoparticles C;

fourthly, adding the composite cerium oxide nano particles C and a catalyst into an organic solvent, and performing ultrasonic dispersion to obtain a dispersion liquid D;

the mass ratio of the composite cerium oxide nanoparticles C to the organic solvent is 1: 50-1: 100. The mass ratio of the catalyst to the organic solvent is 1: 100-1: 500.

And fifthly, adding a certain amount of hydrophobic modifier into the organic solvent for full dissolution to prepare hydrophobic modifier E.

The mass ratio of the hydrophobic modifier to the organic solvent is 1: 10-1: 20.

Sixthly, reacting the dispersion liquid D, the hydrophobic modifier E and the reactant for 6-18 hours at the temperature of 60-90 ℃ in a protective atmosphere; and (4) performing centrifugal separation to obtain the composite cerium oxide nano hydrophobic particles F with the multilevel structure.

The mass ratio of the hydrophobic modifier E to the composite cerium oxide nanoparticles C is 1: 1-1: 5.

The mass ratio of the reactant to the composite cerium oxide nanoparticles C is 1: 2-1: 10.

The nanoparticles described in the first step may be: silicon dioxide, titanium dioxide, zinc oxide, aluminum oxide, or iron oxide; particle size range of nanoparticles: 100 nm to 250 nm.

The amination modifier may be: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or N-aminoethyl-gamma-aminopropyltrimethoxysilane;

the catalyst can be dibutyltin dilaurate or stannous octoate.

The hydrophobic modifier is selected from common alcohol, acid or amine C_nH_2n+1OH，C_nH_2n+1COOH，C_nH_2n+1NH₂Wherein n is 6,8,10,12,14,16, 18.

The reactant can be isophorone diisocyanate and toluene-2, 4-diisocyanate.

The organic solvent can be toluene, xylene, n-hexane, butyl acetate, cyclohexane, dichloromethane, n-pentane, cyclopentane or tetrahydrofuran.

The invention also provides an application of the composite cerium oxide nano hydrophobic particle with the multilevel structure, in particular to an application of the prepared composite cerium oxide nano hydrophobic particle with the multilevel structure in an anti-icing coating, which comprises the following steps:

the method comprises the following steps: grinding and dispersing the composite cerium oxide nano hydrophobic particles F with the multilevel structure into an organic solvent to prepare a nano particle dispersion liquid G;

the mass ratio of the composite cerium oxide nano hydrophobic particles F with the multilevel structure to the organic solvent is 1: 10-1: 100.

Step two: the nanoparticle dispersion G is added to a commercially available resin or a general coating to prepare a spray coating liquid H.

The mass ratio of the nanoparticle dispersion liquid G to a commercially available resin (or common coating) is as follows: 1:5 to 1: 100.

Step three: and spraying the spraying liquid H on the surface of the material to form an anti-icing hydrophobic film layer.

The invention has the advantages that:

(1) due to the unique electronic structure of the cerium oxide, the cerium oxide has hydrophobicity (the contact angle of the powder after pressing is about 107 degrees) and is suitable for preparing a hydrophobic coating. However, the common cerium oxide particles have low surface activity, are easy to agglomerate and difficult to graft and modify, so that the super-hydrophobic characteristic is difficult to obtain; after the treatment by the method provided by the invention, the super-hydrophobic nano particles can be obtained.

(2) The special multilevel structure of the surface of the prepared composite cerium oxide nano hydrophobic particle improves the surface activity, can realize hydrophobic modification of the surface, obtains the composite cerium oxide nano particle with the multilevel structure and the surface hydrophobic characteristic, and can be directly dispersed and sprayed or added into a commercially available coating for use.

(3) The contact angle of the surface of the obtained anti-icing film layer is more than 155 degrees, and the anti-icing effect is good.

Drawings

FIG. 1 is a microscopic morphology of the multi-stage structured composite cerium oxide nano hydrophobic particles prepared by the present invention.

Fig. 2 is an XRD pattern of the multi-stage structured composite cerium oxide nano-hydrophobic particles prepared in the present invention.

FIG. 3 shows the measurement result of the contact angle of the ice-coating-preventing surface of the multi-stage structured composite cerium oxide nano hydrophobic particle prepared by the present invention.

FIG. 4 is a graph showing the anti-icing effect of the multi-stage composite cerium oxide nano hydrophobic particles prepared by the present invention.

Detailed Description

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

The invention provides a composite cerium oxide nano hydrophobic particle with a multilevel structure, a preparation method and application thereof, which are specifically described by embodiments.

Example 1:

the preparation method of the composite cerium oxide nano hydrophobic particle with the multilevel structure comprises the following specific steps:

step one, adding 1g of dried silicon dioxide with the particle size of 100 nanometers into 50g of butyl acetate, stirring and ultrasonically oscillating to uniformly disperse the nanoparticles in the butyl acetate; the dispersed solution is added into a three-mouth bottle with a condenser tube, then 0.5g of 3-aminopropyl trimethoxy silane is slowly dripped, and the grafting reaction is carried out for 12 hours by heating and refluxing at constant temperature. And after the reaction is finished, centrifugally washing and drying the product. And then the mixture is dispersed into 300ml of ethanol to obtain an amination modified nano particle dispersion liquid A.

And secondly, 1g of cerium nitrate, 1.6g of hexamethylenetetramine and 20g of water are mixed and stirred uniformly to prepare an aqueous solution B serving as a cerium oxide modifier.

Thirdly, ultrasonically mixing the dispersion liquid A and the aqueous solution B according to the mass ratio of 3:1, and stirring for reaction for 10 hours at 80 ℃; drying for 12 hours at 120 ℃ after centrifugal separation to obtain the composite cerium oxide nano particles C with a multilevel structure;

and fourthly, adding 1g of the composite cerium oxide nano particles C and 0.1g of dibutyltin dilaurate into 50g of butyl acetate, and performing ultrasonic dispersion (time is 20min, ultrasonic frequency is 256Hz) to obtain a dispersion liquid D.

Fifthly, 0.4g of dodecanol is added into 5g of butyl acetate to be fully dissolved, and a hydrophobic modifier E is prepared.

And sixthly, adding 0.5g of isophorone diisocyanate into the prepared dispersion liquid D, reacting for 6 hours at 60 ℃, adding a hydrophobic modifier E, continuing to react for 8 hours, and performing centrifugal separation to obtain the composite cerium oxide nano hydrophobic particle F with the multi-stage structure.

The surface morphology of the composite cerium oxide nano hydrophobic particle F with the multilevel structure is observed by adopting a scanning electron microscope (JSM-7500F scanning electron microscope in Japan), and the result is shown in figure 1, and the surface of the nano hydrophobic particle is non-smooth and has a strawberry-like multilevel structure and good monodispersity. The X-ray diffraction pattern of the multi-level structured composite cerium oxide nano hydrophobic particle is shown in fig. 2, and a characteristic peak of cerium oxide can be seen, which indicates that the prepared nano hydrophobic particle is cerium oxide.

The method is characterized in that the composite cerium oxide nano hydrophobic particle F with a multilevel structure is used for an anti-icing coating, and comprises the following specific steps:

step A: grinding and dispersing 0.1G of the composite cerium oxide nano hydrophobic particles F with the multilevel structure into 10G of ethanol to obtain a nano particle dispersion liquid G;

and B: spray coating liquid H was prepared by adding 10G of nanoparticle dispersion liquid G to 50G of a commercially available acrylic resin.

And C: and spraying the spraying liquid H on the surface of the metal pipe by adopting a spraying process to form the ice-coating-proof hydrophobic coating surface.

The prepared ice-coating-proof coating surface was subjected to a hydrophobic property test using a DSA 20 video contact angle measuring instrument of kruss Instruments GmbH, germany, and the results showed that the contact angle and the rolling angle of the ice-coating-proof coating surface were more than 155 ° (as shown in fig. 3) and the rolling angle was less than 5 °. The anti-icing surface hydrophobic coating sample is placed on a freezing layer of a refrigerator, and compared with a common coating, after 60 days, as shown in fig. 4, the common coating on the left side in fig. 4 is seriously frozen, and the surface of the anti-icing surface hydrophobic coating on the right side is not frozen, which shows that the anti-icing coating provided by the invention has a better anti-icing effect.

Example 2:

step one, adding 1g of dried alumina with the particle size of 250 nanometers into 100g of normal hexane, stirring and ultrasonically oscillating to uniformly disperse the nanoparticles in the normal hexane; adding the dispersed solution into a three-necked bottle with a condensing tube, then slowly dropwise adding 0.1g N-aminoethyl-gamma-aminopropyltrimethoxysilane, heating, refluxing and grafting at constant temperature for 12 hours, and centrifugally washing and drying the product after the reaction is finished. And then the mixture is dispersed into 300ml of ethanol to obtain an amination modified nano particle dispersion liquid A.

And secondly, 1g of cerium nitrate, 5g of hexamethylenetetramine and 50g of water are mixed and stirred uniformly to prepare an aqueous solution B serving as a cerium oxide modifier.

Thirdly, ultrasonically mixing the dispersion liquid A and the aqueous solution B, and then stirring and reacting for 10 hours at 80 ℃; drying for 12 hours at 120 ℃ after centrifugal separation to obtain the composite cerium oxide nano particles C with a multilevel structure;

and fourthly, adding 1g of the composite cerium oxide nanoparticles C and 0.2g of stannous octoate into 100g of n-hexane, and performing ultrasonic dispersion (time is 20min, ultrasonic frequency is 256Hz) to obtain a dispersion liquid D.

In the fifth step, 0.5g of hydrophobic modifier C is added₁₀H₂₁COOH was added to 10g of n-hexane and dissolved sufficiently to prepare a hydrophobic modifier E.

And sixthly, adding 0.1g of toluene-2, 4-diisocyanate into the prepared dispersion liquid D, reacting for 4 hours at 90 ℃, adding a hydrophobic modifier E, continuing to react for 6 hours, and performing centrifugal separation to obtain the multi-stage structured composite cerium oxide nano hydrophobic particle F.

step A: grinding and dispersing 1G of the composite cerium oxide nano hydrophobic particles F with the multilevel structure into 10G of n-hexane to obtain a nano particle dispersion liquid G;

and B: 10G of the nanoparticle dispersion G was added to 1000G of a commercially available paint to prepare a spray coating liquid H.

The contact angle and the rolling angle of the surface of the prepared ice-covering-proof coating are 155 degrees, and the rolling angle is less than 8 degrees. And placing the anti-icing surface hydrophobic coating sample on a freezing layer of a refrigerator, wherein the surface of the anti-icing surface hydrophobic coating is not frozen after 45 days.

Example 3:

step one, adding 1g of dried titanium dioxide with the particle size of 150 nanometers into 60g of cyclopentane, stirring and ultrasonically oscillating to uniformly disperse the nanoparticles in the cyclopentane; and adding the dispersed solution into a three-mouth bottle with a condensing tube, then slowly dropwise adding 1g of 3-aminopropyltriethoxysilane, and heating for refluxing and grafting reaction at constant temperature for 12 hours. And after the reaction is finished, centrifugally washing and drying the product. And then the mixture is dispersed into 300ml of ethanol to obtain an amination modified nano particle dispersion liquid A.

And secondly, 1g of cerium nitrate, 3g of hexamethylenetetramine and 30g of water are mixed and stirred uniformly to prepare an aqueous solution B serving as a cerium oxide modifier.

and fourthly, adding 1g of the composite cerium oxide nano particles C and 0.2g of dibutyltin dilaurate into 50g of cyclopentane, and performing ultrasonic dispersion (time is 20min, ultrasonic frequency is 256Hz) to obtain a dispersion liquid D.

In the fifth step, 1g of hydrophobic modifier C is added₆H₁₃NH₂Adding 10g of cyclopentane, fully dissolving, and preparing a hydrophobic modifier E.

And sixthly, adding 0.3g of isophorone diisocyanate into the prepared dispersion liquid D, reacting for 6 hours at 75 ℃, adding a hydrophobic modifier E, continuing to react for 12 hours, and performing centrifugal separation to obtain the composite cerium oxide nano hydrophobic particle F with the multi-stage structure.

The method is characterized in that the composite cerium oxide nano hydrophobic particles with the multilevel structure are used for an anti-icing coating, and the method comprises the following specific steps:

step A: 1G of the composite cerium oxide nano hydrophobic particles F with the multilevel structure are ground and dispersed into 50G of cyclopentane to obtain a nano particle dispersion liquid G;

and B: the nanoparticle dispersion G was added to 1000G of a commercially available acrylic resin to prepare a spray solution H.

And C: and forming the ice-coating-preventing hydrophobic coating surface on the surface of the metal pipe by adopting a spraying process.

The contact angle and the rolling angle of the surface of the prepared ice-covering-proof coating are 160 degrees, and the rolling angle is less than 6 degrees. And placing the anti-icing surface hydrophobic coating sample on a freezing layer of a refrigerator, wherein after 45 days, the common coating is seriously frozen, and the surface of the anti-icing surface hydrophobic coating is not frozen.

Claims

1. A preparation method of composite cerium oxide nano hydrophobic particles with a multilevel structure is characterized by comprising the following steps: the specific steps are as follows,

the mass ratio of the nanoparticles to the organic solvent is 1: 50-1: 100; the mass ratio of the amination modifier to the nanoparticles is 1: 1-1: 10;

the nano particles are silicon dioxide, titanium dioxide, zinc oxide, aluminum oxide or iron oxide; particle size range of nanoparticles: 100 nm to 250 nm;

the mass ratio of the composite cerium oxide nanoparticles C to the organic solvent is 1: 50-1: 100; the mass ratio of the catalyst to the organic solvent is 1: 100-1: 500;

fifthly, adding the hydrophobic modifier into the organic solvent for full dissolution to prepare a hydrophobic modifier E;

the mass ratio of the hydrophobic modifier to the organic solvent is 1: 10-1: 20;

sixthly, reacting the dispersion liquid D, the hydrophobic modifier E and the reactant for 6-18 hours at the temperature of 60-90 ℃ in a protective atmosphere; centrifugally separating to obtain the composite cerium oxide nano hydrophobic particles F with a multilevel structure;

the mass ratio of the hydrophobic modifier E to the composite cerium oxide nanoparticles C is 1: 1-1: 5;

the mass ratio of the reactant to the composite cerium oxide nanoparticles C is 1: 2-1: 10;

the surface of the nano hydrophobic particle is non-smooth and has a strawberry-like multilevel structure, and the monodispersity is good;

the amination modifier is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or N-aminoethyl-gamma-aminopropyltrimethoxysilane; the catalyst is dibutyltin dilaurate or stannous octoate; the hydrophobic modifier is selected from common alcohol, acid or amine C_nH_2n+1OH，C_nH_2n+1COOH，C_nH_2n+1NH₂Wherein n is 6,8,10,12,14,16, 18; the reactant is isophorone diisocyanate, toluene-2, 4-diisocyanate; the organic solvent is toluene, xylene, normal hexane, butyl acetate, cyclohexane, dichloromethane, n-pentane, cyclopentane or tetrahydrofuran;

the application of the composite cerium oxide nano hydrophobic particle is used for an anti-icing coating, and the specific steps are,

the mass ratio of the composite cerium oxide nano hydrophobic particles F with the multilevel structure to the organic solvent is 1: 10-1: 100;

the organic solvent is toluene, xylene, normal hexane, butyl acetate, cyclohexane, dichloromethane, n-pentane, cyclopentane or tetrahydrofuran;

step two: adding the nanoparticle dispersion liquid G into commercially available resin or common coating to prepare a spraying liquid H;

the mass ratio of the nanoparticle dispersion liquid G to the commercially available resin or common coating is as follows: 1: 5-1: 100;