CN108329835A - Low-melting point metal alloy modified super-hydrophobic material and its preparation method and application - Google Patents
Low-melting point metal alloy modified super-hydrophobic material and its preparation method and application Download PDFInfo
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- CN108329835A CN108329835A CN201810240579.7A CN201810240579A CN108329835A CN 108329835 A CN108329835 A CN 108329835A CN 201810240579 A CN201810240579 A CN 201810240579A CN 108329835 A CN108329835 A CN 108329835A
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F2009/0804—Dispersion in or on liquid, other than with sieves
- B22F2009/0812—Pulverisation with a moving liquid coolant stream, by centrifugally rotating stream
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses low-melting point metal alloy modified super-hydrophobic materials and its preparation method and application, belong to technical field of inorganic material.Modified super-hydrophobic material is prepared using metal alloys such as stabilization, the relatively low gallium kirsite of nontoxic and fusing point, gallium-indium alloy, gallium-indium-tin alloy, gallium indium red brass, indium sn-bi alloy, low-melting point metal alloy easily disperse and high intensity and good stability in solid-state in liquid is dexterously utilized, preparation process is simplified, simple for process, low manufacture cost, preparation efficiency are high, the super hydrophobic material being prepared has compared with high abrasion resistance strength and long service life, further promotes super hydrophobic material and more widely applies.
Description
Technical field
The present invention relates to a kind of super hydrophobic materials, and in particular to low-melting-point metal modified super-hydrophobic material and preparation method thereof
And application, belong to inorganic chemistry or material chemistry technical field.
Background technology
Super hydrophobic material refers to that water is less than 10 ° of functional materials in its surface contact angle more than 150 °, roll angle.It is super thin
The performance of water material depends primarily on two aspects：The micro-nano roughness and low-surface-energy of material surface, therefore super-hydrophobic material
There are two the preparation strategy of material is main：Material micro-nano grade rough surface using low-surface energy substance (such as dimethyl silicone polymer,
Fluorine containing silane etc.) carry out modification and the micro-nano roughening preparation of material lower-surface-free-energy surface.The preparation method of super hydrophobic material
Mainly there are template, etch, plasma etching method, sol-gel method, electrochemical method, phase separation method, chemical vapor deposition
The methods of method.Super hydrophobic material has the critical functions such as waterproof, antifog, snow defence, anti-pollution, anti-oxidant, anticorrosion and automatically cleaning,
There is extremely wide application prospect in the numerous areas such as scientific research and industrial production, life, traffic, national defence.
During at present prepared by super hydrophobic material, obtained using the method for micro-nano granules construction material micro-nano rough surface
It is widely applied, the micro-nano granules material used in this method includes silica, titanium dioxide, zirconium dioxide, natural mine
Object powder, copper oxide, zinc oxide, iron, copper, silver, gold etc..This method presently, there are the problem of mainly have：One, this method needs to utilize
Various preparation means first prepare micro/nano level particle and are applied again so that the preparation process of super hydrophobic material is cumbersome, is produced into
This height, production efficiency are low；Two, the surface micro-nano compound structure of the super hydrophobic material prepared is very fragile, is easy by the external world
It acts on and damages, use intensity is inadequate, and service life is short.
Therefore, it is simple to find a kind of manufacture craft, low manufacture cost has compared with high abrasion resistance strength and long service life
Super hydrophobic material becomes the hot spot of super hydrophobic material technical field research.
Invention content
In order to solve the deficiencies in the prior art, the present invention provides a kind of low-melting point metal alloy modified super-hydrophobic material and
Preparation method and application.
A kind of low-melting point metal alloy modified super-hydrophobic material, it is characterised in that：Static contact angle >=155 °, roll angle≤
2°。
A kind of low-melting point metal alloy modified super-hydrophobic material preparation method, including：The first step obtains micro-nano using alloy
Rice solid metal alloy powder solution, second step are coated on substrate surface, it is characterised in that：Alloy is using low melting point gold
Belong to alloy.
Further, in the above-mentioned technical solutions, the first step includes following operation：By low-melting point metal alloy, low surface
Can modified material, adhesive and solvent mixing, under heating by liquid low-melting point metal alloy high degree of dispersion be tiny micro/nano level
Ultrasound is made micro/nano level low-melting point metal alloy droplet solidification be high degree of dispersion micro and nano powders metal by drop under then cooling down
Powder.
Further, in the above-mentioned technical solutions, the heating liquid dispersed or cooling solid dispersion process are using manual
Violent concussion, magnetic agitation, mechanical agitation, whirlpool mixing or ultrasonication is single or combination.
Further, in the above-mentioned technical solutions, first step preferred operations scheme is：By low-melting-point metal, low-surface-energy
Modified material, adhesive, solvent are by mixing, and obtained mixture is under the conditions of slightly above low-melting-point metal melting temperature
Liquid low-melting-point metal is made in the solution using manual acutely concussion, magnetic agitation, mechanical agitation, whirlpool mixing or ultrasonication
High degree of dispersion is tiny micro/nano level drop, and obtained mixture continues concussion while cooling, ultrasound makes micro/nano level
Low-melting-point metal droplet solidification be high degree of dispersion micro and nano powders metal powder.
Further, in the above-mentioned technical solutions, second step includes following operation：Micro and nano powders metal powder solution is logical
Lifting is crossed, impregnate or sprays the surface for making it be coated on base material, then cooling lower heat preservation to solvent volatilization, adhesive cures bonding
Low-melting-point metal micro-nano grade particles, the constructing of micro-nano surface, the modification of micro-nano surface low-surface-energy are completed at the same time, and are obtained super thin
Water material.Wherein, cooling preferably using less than low-melting-point metal melting temperature environment.
Further, in the above-mentioned technical solutions, the low-melting point metal alloy is fusing point metal between 28-100 DEG C
Alloy.
Further, in the above-mentioned technical solutions, it is preferable that low-melting point metal alloy be selected from gallium kirsite, gallium-indium alloy,
It is one or more in gallium-indium-tin alloy, gallium indium red brass and indium sn-bi alloy.
Further, in the above-mentioned technical solutions, the solvent is selected from water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, dichloro
At least one of methane, chloroform, tetrahydrofuran, n-hexane, ethyl acetate and N,N-dimethylformamide；
Further, in the above-mentioned technical solutions, the low-surface-energy modified material includes C8-C18 silane, perfluor C8-
It is one or more in C18 silane, fluoro containing polymers polymer and dimethyl silicone polymer.
Further, in the above-mentioned technical solutions, it includes Organic adhesive, inorganic gluing that the adhesive, which includes adhesive,
Agent and poly-dopamine biogum.Organic adhesive is selected from epoxy resin, polyurethane, silicon rubber, organosilicon etc., inorganic adhesive choosing
From alumino-silicate, copper oxide etc..
Further, in the above-mentioned technical solutions, the base material includes natural fiber, glass fibre, quartz fibre, carbon fiber
Dimension, organic polymer fiber, wire, glass plate, quartz glass plate, metal foil, glass fabric, quartz fiber cloth, carbon fiber
Wei Bu, organic polymer fiber cloth, organic polymer non-woven fabrics, cotton, flaxen fiber cloth, stainless (steel) wire, copper mesh, nickel screen, titanium net,
Aluminium net, foam or sponge material.
Further, in the above-mentioned technical solutions, it is preferable that the natural fiber includes cotton fiber, flaxen fiber, You Jiju
It includes nylon etc. to close fibres cloth, foam and sponge material include foam copper, foamed iron, nickel foam, foam iron-nickel, titanium foam,
Foam silver, polyurethane sponge, poly- melamine sponge, polyimides sponge, cellulose sponge etc..
Invention advantageous effect
The application super hydrophobic material manufacture craft is simple, low manufacture cost, and the super hydrophobic material prepared is with higher resistance to
Grind intensity and long service life.Using stabilization, the relatively low gallium kirsite of nontoxic and fusing point, gallium-indium alloy, gallium-indium-tin alloy, gallium indium
The metal alloys such as red brass, indium sn-bi alloy prepare super hydrophobic material as modified material, and low melting point is dexterously utilized
Easily disperse of the metal in liquid and the high intensity in solid-state and good stability so that prepare super hydrophobic material process
The super hydrophobic material durability enhancing for simplifying to improve preparation efficiency, while being prepared, may advantageously facilitate super hydrophobic material
More widely apply.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 1, and scale is 300 microns；
Fig. 2 is the scanning electron microscope (SEM) photograph of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 1, and scale is 20 microns；
Fig. 3 is the scanning electron microscope (SEM) photograph of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 1, and scale is 5 microns；
Fig. 4 is the contact angle of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 2, and scale is 300 microns；
Fig. 6 is the scanning electron microscope (SEM) photograph of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 2, and scale is 30 microns；
Fig. 7 is the scanning electron microscope (SEM) photograph of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 2, and scale is 5 microns；
Fig. 8 is the contact angle of super-hydrophobic stainless (steel) wire made from the embodiment of the present invention 2.
Specific implementation mode
To keep the embodiment of the present invention technical problems to be solved, technical solution and advantage clearer, below to specific
Embodiment is described in detail.But the present invention is limited to absolutely not these examples.It is as described below to be only the preferred embodiment of the present invention, only
Only to explain the present invention, therefore the limitation of the scope of the claims of the present invention can not be interpreted as.It should be pointed out that all in this hair
The all any modification, equivalent and improvement etc. done within bright spirit and principle, should be included in protection scope of the present invention
Within.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Super hydrophobic material surface is tested for the property, its static contact angle and roll angle are detected.The present invention is according to as follows
Method carries out the ultra-hydrophobicity test of super hydrophobic material：
Contact angle test method is that sample to be tested is fixed on measuring table, and 2pL pure water is dripped in specimen surface, waits for water
After pearl is static, measured with KRUSSDSA100 contact angle testers.
Roll angle test method is that sample to be tested is fixed on measuring table, and 2pL pure water is dripped in specimen surface, waits for water
After pearl is static, gradual inclination measurement platform is until water droplet rolls, and platform inclination angle is roll angle at this time.
Embodiment 1
It is 60 DEG C of indium sn-bi alloy 5g, dimethyl silicone polymer (PDMS) performed polymer 3.0g, curing agent to weigh fusing point respectively
0.3g, epoxide-resin glue 3g, tetrahydrofuran 100mL, directly mix in 250ml beakers, and beaker is placed in 75 DEG C of water temperatures
Heating and ultrasound 10min in ultrasonic cleaner, it is vertical after promoting liquefied indium sn-bi alloy high degree of dispersion in liquid to be droplet
Beaker is placed in the ultrasonic cleaner for containing cold water and cools down and continue ultrasound, waits for mixture temperature falling head in beaker
The indium sn-bi alloy droplet of dispersion stops ultrasound after being frozen into the solid powder of high degree of dispersion.Pre-wash is dried
300 mesh, 316 stainless (steel) wire of each 5cm of length and width is soaked into the solution in beaker to be taken out after 3min, and solution is drained above beaker
Afterwards, the super-hydrophobic of obtained low melting point indium sn-bi alloy enhancing in 24 hours is dried in vacuo in 55 DEG C preheated in advance of vacuum drying oven
Stainless (steel) wire, 157 ° of static contact angle, 1 ° of roll angle ﹤, characterize data is shown in attached drawing 1-4.
Embodiment 2
It is 81 DEG C of gallium kirsite 5g, perfluoro capryl trimethoxy silane 2g, acrylic adhesive 3g, N, N- to weigh fusing point respectively
Dimethylformamide 100mL is directly mixed in 250mL beakers, and beaker is placed in heating in 100 DEG C of water-baths and machinery stirs
Mix 10min, promote liquefied gallium kirsite in liquid high degree of dispersion be droplet after, immediately by beaker be placed in contain cold water water
It is cooled down in bath and continues to stir, wait for that the gallium kirsite droplet that mixture temperature falling head is disperseed in beaker is frozen into height point
Stop stirring after scattered solid powder.The polyurethane foam of each 5cm of the dried length and width of pre-wash, high 1cm are soaked into burning
3min in solution in cup, during which repeatedly extrudes polyurethane foam, after draining solution above beaker after taking-up, is preheated in advance
75 DEG C of vacuum drying oven in be dried in vacuo the super hydrophobic polyurethane foam of obtained low melting point gallium kirsite enhancing in 24 hours, it is static
155 ° of contact angle, 2 ° of roll angle ﹤, characterize data is shown in attached drawing 5-8.
Embodiment 3
Low-melting-point metal made from embodiment 1 is modified the circle that super-hydrophobic stainless (steel) wire is cut into a diameter of 4.2cm, is placed in
Among two fixtures, pinch seal, fixture upper and lower side connects the glass tube of outer diameter 4.2cm, and oily-water seperating equipment is vertical, and (separation is close
Oil of the degree more than water) or be clamped on firm iron stand at 30 ° of angles the oil of water (partition density be less than) with horizontal plane, pour into oil
Water mixed liquid, oil can enter the receiver of lower part quickly through stainless (steel) wire, and water can be arrested in the glass tube of upper end.The present invention
Low-melting-point metal obtained be modified super-hydrophobic stainless (steel) wire can efficiently and rapidly detach including dichloromethane, chloroform, n-hexane,
The oil water mixtures such as petroleum ether, isooctane and peanut oil, soybean oil, corn oil, separative efficiency is respectively 99.0 ± 0.3%,
98.6 ± 0.2%, 98.4 ± 0.3%, 98.0 ± 0.2%, 99.1 ± 0.4%, 98.8 ± 0.2%, 98.9 ± 0.3%, 98.6
± 0.3%.
Embodiment 4
By low-melting-point metal modification made from embodiment 2, super hydrophobic polyurethane sponge is cut into a diameter of 4.2cm, thickness is
The thin rounded flakes of 0.5cm are placed among two fixtures, pinch seal, and fixture upper and lower side connects the glass tube of outer diameter 4.2cm, oil
Water separation device vertical (partition density is more than the oil of water) is clamped in horizontal plane at 30 ° of angles (partition density is less than the oil of water)
On firm iron stand, oil-water mixture is poured into, oil can enter the receiver of lower part quickly through polyurethane sponge, and water can hinder
It is stagnant in the glass tube of upper end.Low-melting-point metal produced by the present invention is modified super hydrophobic polyurethane sponge and can efficiently and rapidly detach
Including the oil water mixtures such as dichloromethane, chloroform, n-hexane, petroleum ether, isooctane and peanut oil, soybean oil, corn oil, separation
Efficiency is respectively 98.4 ± 0.2%, 98.9 ± 0.3%, 98.6 ± 0.4%, 99.1 ± 0.2%, 98.5 ± 0.3%, 98.7 ±
0.3%, 98.8 ± 0.4%, 98.6 ± 0.2%.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of low-melting point metal alloy modified super-hydrophobic material, it is characterised in that：Static contact angle >=155 °, roll angle≤
2°。
2. a kind of preparation method of low-melting point metal alloy modified super-hydrophobic material, including：The first step obtains micro-nano using alloy
Rice solid metal alloy powder solution, second step are coated on substrate surface, it is characterised in that：Alloy is using low melting point gold
Belong to alloy.
3. the preparation method of low-melting point metal alloy modified super-hydrophobic material according to claim 2, which is characterized in that first
Step includes following operation：Low-melting point metal alloy, low-surface-energy modified material, adhesive and solvent are mixed, by liquid under heating
State low-melting point metal alloy high degree of dispersion is tiny micro/nano level drop, keeps micro/nano level low melting point golden ultrasound under then cooling down
Belong to alloy liquid droplet and is solidified as high degree of dispersion micro and nano powders metal powder.
4. the preparation method of low-melting point metal alloy modified super-hydrophobic material according to claim 3, it is characterised in that：Heating
Liquid dispersed or cooling solid dispersion process are using acutely concussion, magnetic agitation, mechanical agitation, whirlpool mixing or ultrasound are broken manually
Broken single or combination.
5. the preparation method of low-melting point metal alloy modified super-hydrophobic material according to claim 2, which is characterized in that second
Step includes following operation：Micro and nano powders metal powder solution makes it be coated on the surface of base material by lifting, immersion or spraying,
Then cooling lower heat preservation to solvent volatilization, adhesive solidification bonding low-melting-point metal micro-nano grade particles, the constructing of micro-nano surface,
The low-surface-energy modification of micro-nano surface is completed at the same time, and obtains super hydrophobic material.
6. according to the preparation method of any one low-melting point metal alloy modified super-hydrophobic material of claim 1,2 or 3,
It is characterized in that：Low-melting point metal alloy is selected from 28-100 DEG C of metal alloy of fusing point.
7. according to the preparation method of any one of the claim 2-5 low-melting point metal alloy modified super-hydrophobic materials, feature
It is, the low-melting point metal alloy is selected from gallium kirsite, gallium-indium alloy, gallium-indium-tin alloy, gallium indium red brass and indium tin bismuth
It is one or more in alloy.
8. the preparation method of low-melting point metal alloy modified super-hydrophobic material according to claim 3, it is characterised in that：Solvent
Selected from water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, dichloromethane, chloroform, tetrahydrofuran, n-hexane, ethyl acetate or N, N- bis-
At least one of methylformamide；Low-surface-energy modified material is selected from C8-C18 silane, perfluor C8-C18 silane, fluoro containing polymers
It is one or more in polymer and dimethyl silicone polymer.
9. the preparation method of low-melting point metal alloy modified super-hydrophobic material according to claim 3, it is characterised in that：Gluing
Agent includes Organic adhesive, inorganic adhesive and poly-dopamine biogum；Base material includes natural fiber, glass fibre, quartz fibre
Dimension, carbon fiber, organic polymer fiber, wire, glass plate, quartz glass plate, metal foil, glass fabric, quartz fibre
Cloth, carbon cloth, organic polymer fiber cloth, organic polymer non-woven fabrics, cotton, flaxen fiber cloth, stainless (steel) wire, copper mesh, nickel
Net, titanium net, aluminium net, foam or sponge material.
10. application of the low-melting point metal alloy modified super-hydrophobic material in preparing water-oil separating material.
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| CN108570254A (en) * | 2018-05-28 | 2018-09-25 | 北京梦之墨科技有限公司 | A kind of preparation method of liquid metal nonstick layer and the utensil of non-sticky attached liquid metal |
| CN109589408A (en) * | 2018-12-04 | 2019-04-09 | 江苏省原子医学研究所 | A kind of meter of shape liquid metal nanoparticle and its synthetic method and application |
| CN110349926A (en) * | 2019-07-18 | 2019-10-18 | 深圳前海量子翼纳米碳科技有限公司 | A method of reducing liquid metal for conducting heat piece thermal resistance |
| CN110434350A (en) * | 2019-09-12 | 2019-11-12 | 中国科学院理化技术研究所 | A kind of metal powder with low melting point and its preparation method and application |
| CN110465672A (en) * | 2019-09-17 | 2019-11-19 | 中国科学院理化技术研究所 | A kind of metal powder with low melting point and its preparation method and application |
| CN110791175A (en) * | 2019-11-13 | 2020-02-14 | 岳宗乐 | Super-smooth anti-drag coating and application method thereof |
| CN115351285A (en) * | 2022-10-21 | 2022-11-18 | 陕西斯瑞新材料股份有限公司 | Method for preparing CuCrNb powder for additive manufacturing based on EIGA process |
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