CN107723706A - A kind of material surface process for hydrophobicizing - Google Patents
A kind of material surface process for hydrophobicizing Download PDFInfo
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- CN107723706A CN107723706A CN201710850528.1A CN201710850528A CN107723706A CN 107723706 A CN107723706 A CN 107723706A CN 201710850528 A CN201710850528 A CN 201710850528A CN 107723706 A CN107723706 A CN 107723706A
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- reaction chamber
- hydrophobicizing
- initiator
- material surface
- reactant
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention discloses a kind of material surface process for hydrophobicizing, is related to surface syntype coating technique field.This method is completed in material microcosmic surface syntype coating system, is comprised the following steps that：1) pretreatment to be plated；2) material to be plated is placed on sample stage；3) ON cycle water cooling system；4) vacuum-control(led) system is opened；5) lectrothermal alloy wire heating system is opened；6) air inlet feed system is opened, the reactant monomer after gasification and initiator are each led into reaction chamber by preset flow, sets the reaction time, the reactant plates nanoscale hydrophobic film coating in material surface.The invention has the advantages that：1) film layer that this method is formed is nanoscale, and the film coating can be controllable with raw material syntype, dense uniform, thickness；2) high vacuum environment is not needed, operable scope is wide；3) it is simple to operate；4) hydrophobically modified effect is fine.
Description
Technical field
The invention belongs to surface syntype coating technique field, is related specifically to a kind of material surface process for hydrophobicizing.
Background technology
Hydrophobicity is one of key character of material surface, and it is common by the chemical composition and surface geometry of material
Determine.Its property is generally evaluated with water contact angle.In general, water claims on surface of the surface of solids contact angle more than 90 °
For hydrophobic surface.When water in the contact angle of the surface of solids more than 150 ° when, the surface is referred to as super hydrophobic surface.
With the development of society, the requirement more and more higher in industrial and life to material hydrophobic.For waterproof garment,
For many applications such as packaging material, waterproof electronic product, self-cleaning surface, antifogging surface, higher water contact angle is hydrophobic
The maximally effective key foundation of property.The hydrophobic function for such product need to be improved at present, and this is also that each manufacturing enterprise puts forth effort
The technical problem of solution.
The method of material surface hydrophobically modified mainly has Physical and chemical method.The result of physical modification is modifying agent and material
Be present the interaction force between Van der Waals force, hydrogen bond force equimolecular in material, but acted in the absence of covalent bond or ionic bond, modified effect
Fruit is unstable.Chemical modification is primarily referred to as modifying agent and chemically reacted with material surface, the stable hydrophobic film of forming properties
Layer.It is the most frequently used hydrophobically modified method wherein to carry out graft modification to material surface using silicon fluoride, silane coupler etc..[K
Sirichai,Li K.Preparation and characterization of hydrophobic ceramic hollow
fiber membrane[J].Journal of Membrane Science,2007,291(1):70-76] utilize perfluor ethoxy
Base silane (FAS) is to Al2O3Ceramic hollow fibrous membrane is modified, and ceramic membrane surface contact angle reaches close to 120 °.Chinese patent
CN103088629A utilizes cetyl trimethylammonium bromide using polyethylene terephthalate (PET) fabric as raw material
PET non-woven fabrics is pre-processed with strong alkali compound etc., is then placed in silane precursor, adds hydrophobic alkyl silanization afterwards
Compound, the hydrophobic surface that water contact angle is more than 150 ° is obtained after heat treatment.However, nearly all traditional liquid phase thin film coated side
Method is all prepared by wet method.The shortcomings that wet-process modified is operating time length, and operation sequence is cumbersome；Amount of reagent consumption required for modified
Greatly, coating procedure generally requires to use organic solution, therefore is not suitable for base material (such as plastics sensitive to organic solution
Deng)；More difficult control film thickness, the nanoscale film to form uniform syntype is difficult on baroque surface.
Chemical vapor deposition (CVD, Chemical Vapor Deposition) is another method of chemical modification,
It is containing other gases introducings needed for the gaseous reactant or the steam of liquid reactants and reaction for forming film element
Reative cell, chemically reacted in substrate surface, and solid product is deposited to the process of Surface Creation film.It includes 4
Main Stage：1. reacting gas spreads to material surface；2. reacting gas is adsorbed on the surface of material；3. produced in material surface
Chemical reaction；4. gaseous by-product departs from material surface.
Conventional chemical vapor deposition mainly includes plasma reinforced chemical vapour deposition (PECVD) and laser chemistry gas phase is sunk
Product (LCVD) etc..Plasma reinforced chemical vapour deposition is to carry out intensified response thing by plasma caused by gas glow discharge
The chemism of matter, promote the chemical reaction between gas.But plasma generation process can attach higher energy, to surface
Fluoro-containing group needed for hydrophobically modified has larger destruction, and the chemical constitution of film can not accurately control and required functional group
It is not easy to maintain；Also higher is required to the heatproof of required hydrophobically modified material.In addition, the energy needed for PECVD reactions is higher, it is unfavorable
In the control of surface hydrophobicity modified condition and modified cost.
So exploitation a kind of simple to operate, mild condition, process control, applied widely, nanoscale and raw material
The process for hydrophobicizing of surface syntype is extremely important.
The content of the invention
Present situation and existing deficiency for the processing of above material surface, the present invention is directed to propose a kind of technique is simple, sets
Standby simple, mild condition, process control, material surface process for hydrophobicizing applied widely, methods described can be in material
Material surface forms a layer thickness uniformly nanoscale hydrophobicized film, and reaches good syntype effect.
The present invention carries out nanoscale surface syntype hydrophobicity plated film based on chemical vapour deposition technique to material surface.Chemistry
Vapour deposition process is a kind of new functional polymer method for manufacturing thin film of green.It is anti-that it combines traditional liquid phase free radical polymerization
Initiator and function monomer gasification needed for should polymerizeing with chemical vapour deposition technique, method introduce cavity, in relatively low heating
At a temperature of induce initiator cracking, monomer is aggregated into macromolecule membrane and be deposited in substrate.
To reach above goal of the invention, the technical solution adopted by the present invention is：
A kind of material surface process for hydrophobicizing, the processing method are in material microcosmic surface syntype coating system
Complete, the material microcosmic surface syntype coating system includes：Chemical vapour deposition reaction chamber (32), respectively with reaction chamber
The air inlet feed system (1) and vacuum-control(led) system (23), the lectrothermal alloy wire positioned at reaction chamber top that side is connected add
Hot systems (27), the circulating water cooling system (18) positioned at reaction chamber bottom, the quartz observing window at the top of reaction chamber
(30)；Specific material surface silicic acid anhydride step is as follows：
Step 1, material to be plated is pre-processed；
Step 2, pretreated material to be plated is placed into the sample stage of chemical vapour deposition reaction chamber inside bottom
On, lectrothermal alloy wire heating system is then connected, temperature sensor probe is ridden on lectrothermal alloy wire stand, covers reaction chamber
The quartz observing window in ceiling portion；Wherein, sample stage is apart from 20~50mm of lectrothermal alloy wire stand；
Step 3, the circulating water cooling system of chemical vapour deposition reaction chamber bottom is opened, sample stage temperature control is existed
20~40 DEG C；
Step 4, vacuum-control(led) system is opened, the vacuum in chemical vapour deposition reaction chamber is maintained at 10~
4000Pa；
Step 5, lectrothermal alloy wire heating system is opened, by adding for the lectrothermal alloy wire in chemical vapour deposition reaction chamber
Hot temperature control is at 200~300 DEG C；Specific control temperature is determined by used initiator type.
Step 6, air inlet feed system is opened, the reactant monomer after gasification and initiator are pressed 0.1~10:1 flow
Than each leading into chemical vapour deposition reaction chamber, the coated film deposition time is set as 5~90min, reactant monomer is in material
It is 10nm~4 μm that surface, which plates nanoscale hydrophobic film thickness of coating,.Reactant monomer and initiator flow when coated film deposition
The selection of time is relevant with the species of reactant monomer and coating film thickness.
Further, the lectrothermal alloy wire in step 5 in lectrothermal alloy wire heating system is heated by dc source, its
Direct current power source voltage is 3~24V, and dc source electric current is 0.1~5A；The size of specific voltage and current value is drawn by used
Agent species is sent out to determine.
Further, air inlet feed system described in step 6 includes reactant monomer inlet duct and initiator air inlet fills
Put；The reactant monomer inlet duct is filled by water bath heating device, admission line external resistance silk heater and gas flow guiding
Put composition；The temperature of the water bath heating device is 40~100 DEG C, the specific species and boiling point for setting temperature by reactant monomer
Determine；The reactant monomer admission line external resistance silk heater is heated by dc source, direct current power source voltage 1
~10V, dc source electric current are 0.1~3A；The size of specific voltage and current value is determined by used reactant monomer species
It is fixed；The initiator inlet duct keeps room temperature state.
Further, the charge flow rate of reactant monomer described in step 6 and initiator is all controlled in 0.1~3mL/min.
Further, reactant monomer described in step 6 includes perfluoro decanoate, perfluoro capryl acrylate, perfluoro decanoate
Acrylate, 2- (perfluoro capryl)-EMA, divinylbenzene, dimethyldichlorosilane, methyl trichlorosilane,
One or any two or more combination in trichlorosilane or fluoroalkyl silanes；The initiator includes the uncle of peroxidating two
Butyl, tert-butyl peroxide, cumyl peroxide, TBHP or benzoyl peroxide it is therein a kind of or
Any two or more combination.
Further, the material to be plated described in step 1 includes one in the materials such as inorganic material, organic material, metal
Kind is a variety of：The inorganic material is glass, monocrystalline silicon, paper, aluminium oxide ceramics or zirconia ceramics, and organic material is spinning
Fabric, high molecular polymer or tunica fibrosa, the metal material are copper, iron or aluminium alloy.
Further, the method for pretreatment to be plated is described in step 1：When material is inorganic non-metallic material or organic
During material, material is put into drying and processing in insulating box；When material is metal material, material surface is polished, washed,
Etch, wash again, drying and processing.
Beneficial effects of the present invention are：
1) film layer that this method is formed is nanoscale, described film coating can with raw material syntype, dense uniform,
Thickness is controllable, does not influence the original shape of material and structure.
2) this method does not need high vacuum environment, and operable scope is wide, remains to receive material in low vacuum environment
Meter level syntype plated film.
3) it is simple to operate, eliminate modified solution compared with conventional surface graft modification method etc. or organic precursor is molten
The tedious steps such as liquid preparation, material heat treatment.
4) it is short the time required to preparation process.It is 5~90 the time required to modified for different materials and reactant monomer
Minute, greatly shortened compared with conventional surface graft modification method easily the modification time of tens hours.
5) compared with the high energy vapor phase method such as PECVD, its required energy is seldom, and its mild condition, process control, is applied to
The substrate of any material, and can functional group needed for perfect reservation.
6) hydrophobically modified effect is fine.Compared with traditional surface graft modification etc., film surface produced by the present invention is dredged
Water effect is more preferable, and water contact angle is more than 120 °, and for rough surface, modified surface water contact angle can reach super-hydrophobic level
Not (>150°).
Brief description of the drawings
Accompanying drawing 1 is the schematic diagram for the material microcosmic surface syntype coating system that the present invention uses.
Accompanying drawing 2 is that the dust-free paper surface in embodiment 1 before and after surface syntype hydrophobic membrane coating film treatment carries out hydrophobic effect survey
The test result figure of examination；(a) before processing；(b) after handling.
Accompanying drawing 3 is that the glass sheet surface in embodiment 2 before and after surface syntype hydrophobic membrane coating film treatment carries out water contact angle survey
The test result figure of examination；(a) before processing；(b) after handling.
Accompanying drawing 4 is that the monocrystalline silicon sheet surface in embodiment 3 before and after surface syntype hydrophobic membrane coating film treatment carries out hydrophobic effect
The test result figure of test；(a) before processing；(b) after handling.
Accompanying drawing 5 is that the fabric face in embodiment 4 before and after surface syntype hydrophobic membrane coating film treatment carries out hydrophobic effect test
Test result figure；(a) before processing；(b) after handling.
Accompanying drawing 6 is the Al before and after surface syntype hydrophobic membrane coating film treatment in embodiment 52O3Earthenware slab carries out hydrophobic effect
The test result figure of test；(a) before processing；(b) after handling.
Accompanying drawing 7 is the Al after the syntype hydrophobic membrane coating film treatment of surface in embodiment 52O3Earthenware slab carries out water contact angle survey
The test result figure of examination.
Accompanying drawing 8 is the polyacrylonitrile non-woven constructions tunica fibrosa before and after the syntype hydrophobic membrane coating film treatment of surface in embodiment 6
SEM schemes；(a) before processing；(b) after handling.
Accompanying drawing 9 is the polyacrylonitrile non-woven constructions tunica fibrosa before and after the syntype hydrophobic membrane coating film treatment of surface in embodiment 6
The test result figure of hydrophobic effect test；(a) before processing；(b) after handling.
In figure：1 air inlet feed system；2 initiator outtake tubes；3 air valves；4 initiator air induction conduits；5 initiator gases
Flowmeter；6 initiator inlet ducts；7 trigger agent container；8 reactant monomer inlet ducts；9 water bath heating devices；10 reactants
Monomer container；11 reactant gas flow meters；12 reactant air induction conduits；13 dc sources；14 lectrothermal alloy wires；15 reactants
Outtake tube；16 sample stages；17 materials to be plated；18 circulating water cooling systems；19 water pumps；20 reative cell cooling chambers；21 cooling waters
Groove；22 temperature sensors；23 vacuum-control(led) systems；24 vacuum meters；25 air valves；26 vavuum pumps；27 lectrothermal alloy wire heating systems；
28 temperature sensors；29 dc sources；30 quartz observing windows；31 lectrothermal alloy wire stands；32 chemical vapour deposition reaction chambers.
Embodiment
In order to which the purpose of the present invention, technical scheme and beneficial effect is better described, with reference to embodiments further in detail
The embodiment of the thin narration present invention.It should be understood that described embodiment is merely to illustrate the present invention rather than limitation originally
The scope of invention.
Specifically, it is as shown in Figure 1 material microcosmic surface syntype coating system of the present invention, it includes：Chemistry
Vapour deposition reaction chamber 32, the air inlet feed system 1 being connected with reaction chamber side, the vacuum positioned at reaction chamber side
Control system 23, the lectrothermal alloy wire heating system 27 positioned at reaction chamber top, the recirculated water cooling positioned at reaction chamber bottom
But system 18, the quartz observing window 30 positioned at reaction chamber top.
During the system work, ON cycle water cooling system 18, the temperature of sample stage 16 is set to be maintained at predetermined temperature.Open
Vacuum-control(led) system 23 is opened, reaction chamber 32 is reached predetermined vacuum.Lectrothermal alloy wire heating system 27 is opened, makes electric heating
B alloy wire reaches predetermined temperature.Reactant monomer and initiator gasify in respective container respectively, then gentle by air valve 5
Flowmeter body 6,11 controls both flow-rate ratios respectively, afterwards into chemical vapour deposition reaction chamber 32.Reacting gas passes through
When reaching the lectrothermal alloy wire of predetermined temperature, initiator can be induced to be cracked into free radical, reactant monomer is aggregated into high score
Sub- film, one layer of uniform hydrophobic film coating is formed in substrate surface.
Embodiment 1
Use the material for treating plating coating that use for laboratory dust-free paper is the present embodiment.21.5cm*11cm dust-free paper is put
Enter drying and processing in insulating box, be placed in afterwards on the sample stage of material microcosmic surface syntype coating system.Initiator is peroxidating
Di-t-butyl, molecular formula C8H18O2；Reactant monomer is perfluoro decanoate (PFDA), molecular formula C10HF19O2.Control reaction chamber
The pressure of room is 1200Pa；The temperature of agent container is triggered to be maintained at room temperature；Adjust reactant monomer inlet duct dc source electricity
Flow for 0.7A, voltage 7.1V；The temperature for controlling reactant monomer water bath heating device is 82 DEG C；Adjust lectrothermal alloy wire heating
System dc source current is 3.6A, voltage 19.0V, and the temperature for controlling lectrothermal alloy wire is 220 DEG C；Sample stage temperature is by following
Ring cooling water control is at 20 DEG C.Reactant monomer and initiator are with 0.8:1 flow proportional is passed through reaction chamber, wherein reactant
The flow of monomer is 0.8mL/min, and the flow of initiator is 1mL/min.By 10min reactive deposition time, dust-free paper table
Face forms the thick nanoscale films of about 300nm.Because dust-free paper is relatively thin, tow sides can in a coating process shape
Into hydrophobic film layer.
The dust-free paper that hydrophobic membrane coating film treatment has been completed to the present embodiment carries out hydrophobic effect test.Use disposable dropper
Successively draw deionized water, red ink, blue ink, respectively to surface hydrophobicity before modified after dust-free paper test.Test knot
Fruit is as shown in Figure 2.Fig. 2 (a) is design sketch before modified, and water droplet soaks paper quickly, and it is in hydrophily to illustrate dust-free paper；Fig. 2 (b)
For modified design sketch, drop is assembled in paper surface, into ellipsoid, is not penetrated into paper, illustrate in the present embodiment
Dust-free paper silicic acid anhydride effect is fine.
Embodiment 2
Use the material for treating plating coating that flat glass film is the present embodiment.After 7.5cm*2.5cm sheet glass washing
Drying and processing in insulating box is put into, is placed in afterwards on the sample stage of nanometer grade thickness syntype hydrophobic membrane coating apparatus.Initiator is
Di-t-butyl peroxide, molecular formula C8H18O2；Reactant monomer is perfluoro decanoate (PFDA), molecular formula C10HF19O2.Reaction
The pressure of chamber is controlled in 3200Pa, triggers the temperature of agent container to be maintained at room temperature；Adjust reactant monomer inlet duct direct current
Source current is 0.7A, voltage 7.5V；The temperature control of reactant monomer water bath heating device is at 83 DEG C；Adjust electrothermal alloy
Silk heating system dc source electric current is 3.8A, and voltage 19.5V, the temperature control of lectrothermal alloy wire is at 225 DEG C；Sample stage temperature
Degree is by circulating cooling water management below 35 DEG C.Reactant monomer and initiator are with 1:15 flow proportional is passed through reaction chamber,
Wherein the flow of reactant monomer is 0.8mL/min, and the flow of initiator is 1.2mL/min.The reactive deposition time is 5min.
The sheet glass that hydrophobic membrane coating film treatment has been completed to the present embodiment carries out hydrophobic effect test.Drawn using liquid-transfering gun
2.3 μ L deionized waters to surface hydrophobicity before modified after sheet glass carry out water contact angle test.Test result is as shown in Figure 3.Fig. 3
(a) it is water contact angle test chart before modified, water contact angle is 38 ° or so, and it is in hydrophily to illustrate sheet glass；Fig. 3 (b) is modification
Water contact angle test chart afterwards, water contact angle are 130 ° or so, illustrate the flat glass film silicic acid anhydride effect in the present embodiment
Fruit is fine.
Embodiment 3
Use the material for treating plating coating that monocrystalline silicon piece is the present embodiment.By 0.5cm*1.5cm monocrystalline silicon piece with anhydrous
Natural drying is handled after ethanol washing, is placed in afterwards on the sample stage of nanometer grade thickness syntype hydrophobic membrane coating apparatus.Initiator
For di-t-butyl peroxide, molecular formula C8H18O2；Reactant monomer is perfluoro decanoate (PFDA), molecular formula C10HF19O2.Instead
Answering the pressure of chamber to control in 2700Pa, triggers the temperature control of agent container straight in room temperature, adjustment reactant monomer inlet duct
Stream source current is 0.60A, voltage 7.5V；The temperature control of reactant monomer water bath heating device adjusts electric heating at 81 DEG C
B alloy wire heating system dc source electric current is 3.5A, voltage 18.0V, and the temperature control of lectrothermal alloy wire is at 215 DEG C, sample
Platform temperature is by circulating cooling water management below 30 DEG C.Reactant monomer and initiator are with 2:1 flow proportional is passed through reaction chamber
The flow of room, wherein reactant monomer is 2.0mL/min, and the flow of initiator is 1.0mL/min.The reactive deposition time is
5min。
The monocrystalline silicon piece that hydrophobic membrane coating film treatment has been completed to the present embodiment carries out hydrophobic effect test.Inhaled using liquid-transfering gun
Take 2.5 μ L deionized waters to surface hydrophobicity before modified after monocrystalline silicon piece carry out water contact angle test.Test result such as Fig. 4 institutes
Show.Fig. 4 (a) is water contact angle test chart before modified, and water contact angle is 29 ° or so, and it is in hydrophily to illustrate monocrystalline silicon piece；Fig. 4
(b) it is modified water contact angle test chart, water contact angle is 118 ° or so, illustrates the monocrystalline silicon piece hydrophobization in the present embodiment
Treatment effect is fine.
Embodiment 4
Use the material for treating plating coating that yarn fabric is the present embodiment.7.0cm*4.0cm yarn fabric is put into insulating box
Middle drying and processing, it is placed in afterwards on the sample stage of nanometer grade thickness syntype hydrophobic membrane coating apparatus.Initiator is the uncle of peroxidating two
Butyl, molecular formula C8H18O2；Reactant monomer is perfluoro decanoate (PFDA), molecular formula C10HF19O2.The pressure of reaction chamber
In 4000Pa, the temperature control for triggering agent container is in room temperature, adjustment reactant monomer inlet duct dc source electric current for control
0.65A, voltage 7.5V；The temperature control of reactant monomer water bath heating device is at 81.5 DEG C, adjustment lectrothermal alloy wire heating
System dc source current is 3.6A, and voltage 19.0V, the temperature control of lectrothermal alloy wire is at 220 DEG C, and sample stage temperature is by following
Ring cooling water control is below 25 DEG C.Reactant monomer and initiator are with 1.2:1 flow proportional is passed through reaction chamber, wherein instead
The flow for answering thing monomer is 1.2mL/min, and the flow of initiator is 1.0mL/min.The reactive deposition time is 10min.
The yarn fabric that hydrophobic membrane coating film treatment has been completed to the present embodiment carries out hydrophobic effect test.Use disposable dropper
Successively draw 3.5wt%CuSO4Solution, red ink, blue ink (facilitating direct visual perception), respectively to surface hydrophobicity before modified
Yarn fabric afterwards is tested.Test result is as shown in Figure 5.Fig. 5 (a) is design sketch before modified, and water droplet soaks weaving quickly
Thing, it is in hydrophily to illustrate yarn fabric；Fig. 5 (b) is modified design sketch, and drop is assembled in textile surfaces, into ellipsoid, no
It can penetrate into yarn fabric, illustrate that the yarn fabric silicic acid anhydride effect in the present embodiment is fine.
Embodiment 5
Use Al2O3Earthenware slab is the material for treating plating coating of the present embodiment.By the Al2O3Earthenware slab is put into nanometer
On the sample stage of level thickness syntype hydrophobic membrane coating apparatus.Initiator is di-t-butyl peroxide, molecular formula C8H18O2；Reaction
Thing monomer is perfluoro decanoate (PFDA), molecular formula C10HF19O2.The pressure for controlling reaction chamber is 1000Pa, controls initiator
The temperature of container is room temperature, and adjustment reactant monomer inlet duct dc source electric current is 0.60A, voltage 6.5V；Control is anti-
The temperature for answering thing monomer water bath heating device is 79 DEG C, and adjustment lectrothermal alloy wire heating system dc source electric current is 3.8A, electricity
Press as 19.5V, the temperature for controlling lectrothermal alloy wire is 220 DEG C, and sample stage temperature is by circulating cooling water management below 35 DEG C.Instead
Thing monomer and initiator are answered with 0.5:1 flow-rate ratio is passed through reaction chamber, and the flow of wherein reactant monomer and initiator is respectively
0.6mL/min、1.2mL/min.The reactive deposition time is 10min, thickness of coating 600nm, sedimentation rate 60nm/min.By
Side is contacted in earthenware slab with sample stage not combined with reactant monomer, to ensure that earthenware slab all surface is hydrophobic
Coating coats, and after first time coating process is completed, material is overturn and repeats coating process.
The earthenware slab that hydrophobic membrane coating film treatment has been completed to the present embodiment carries out hydrophobic effect test.Use disposable drop
Pipe successively draws 3.5wt%CuSO4Solution, red ink, blue ink, respectively to surface hydrophobicity before modified after earthenware slab carry out
Test.Test result is as shown in Figure 6.Fig. 6 (a) is design sketch before modified, and water droplet soaks earthenware slab, illustrates ceramic flat quickly
Plate is in hydrophily；Fig. 6 (b) is modified design sketch, and drop, will not in earthenware slab surface aggregation, glomeration or ellipsoid
Penetrate into earthenware slab, illustrate the Al in the present embodiment2O3Earthenware slab silicic acid anhydride effect is fine.
The earthenware slab water contact angle test of hydrophobic membrane coating film treatment is completed to the present embodiment, as shown in Figure 7.Test knot
Fruit shows that earthenware slab surface water contact angle is 160 ° or so after hydrophobic treatment, illustrates the Al in the embodiment2O3Earthenware slab
Silicic acid anhydride effect is very good.
Embodiment 6
Polyacrylonitrile non-woven constructions tunica fibrosa using 14wt% made from method of electrostatic spinning is the painting to be plated of the present embodiment
The material of layer.Polyacrylonitrile non-woven constructions tunica fibrosa is put on the sample stage of nanometer grade thickness syntype hydrophobic membrane coating apparatus.
Initiator is di-t-butyl peroxide, molecular formula C8H18O2；Reactant monomer is divinylbenzene (DVB), and molecular formula is
C10H10.The pressure for controlling reaction chamber is 100Pa, triggers the temperature of agent container to be maintained at room temperature；Adjust reactant monomer air inlet
Device dc source electric current is 0.65A, voltage 7.0V；The temperature for controlling reactant monomer water bath heating device is 40 DEG C；Adjust
Whole lectrothermal alloy wire heating system dc source electric current is 3.6A, voltage 19.0V, and the temperature for controlling heater strip is 225 DEG C；Sample
Sample platform temperature is by circulating cooling water management below 40 DEG C；Reactant monomer and initiator are with 0.1:1 flow-rate ratio is passed through reaction
The flow of chamber, wherein reactant monomer is 0.1mL/min, and the flow of initiator is 1.0mL/min.The reactive deposition time is
90min.Because polyacrylonitrile non-woven constructions tunica fibrosa porosity is up to 90%, fiber film thickness is 100 μm or so, tunica fibrosa
Tow sides can form hydrophobic film layer in a coating process.
The polyacrylonitrile non-woven constructions tunica fibrosa progress SEM image that hydrophobic membrane coating film treatment has been completed to the present embodiment is adopted
Collection.The morphology observations of tunica fibrosa, collection result such as Fig. 8 institutes are carried out using tengsten lamp SEM (QUANTA 450)
Show.Fig. 8 (a) is the tunica fibrosa SEM pictures of surface hydrophobicity before modified, and Fig. 8 (b) is the modified tunica fibrosa SEM figures of surface hydrophobicity
Piece.It can be found that significant change does not occur for the structure snd size of fiber after before modified, illustrate that hydrophobic coating is total to former film surface
Type.
The polyacrylonitrile non-woven constructions tunica fibrosa that hydrophobic membrane coating film treatment has been completed to the present embodiment carries out hydrophobic effect survey
Examination.Test result is as shown in Figure 9.Fig. 9 (a) is design sketch before modified, and water droplet soaks polyacrylonitrile fibre membrane quickly, is illustrated poly-
Dralon film is in hydrophily；Fig. 9 (b) is modified design sketch, and drop is in polyacrylonitrile fibre membrane surface aggregation, balling-up
Shape or ellipsoid, are not penetrated into polyacrylonitrile fibre membrane, illustrate that the polyacrylonitrile non-woven constructions tunica fibrosa in the present embodiment is dredged
Hydration process effect is fine.
The polyacrylonitrile non-woven constructions tunica fibrosa that hydrophobic membrane coating film treatment has been completed to the present embodiment carries out water contact angle survey
Examination, test result show that tunica fibrosa surface water contact angle is more than 150 °, illustrate that the polyacrylonitrile non-woven constructions in the embodiment are fine
It is fine to tie up film silicic acid anhydride effect.
Poly- the third of hydrophobic membrane coating film treatment has been completed to the present embodiment using homemade waterpower osmosis pressure (LEP) test device
Alkene nitrile non-woven constructions tunica fibrosa carries out waterpower osmosis pressure (LEP) test, and it is 0.5mL/min to inject speed.The tunica fibrosa is most
Big LEP values are 15.6psi (108kPa).As a result show, the surface of the polyacrylonitrile non-woven constructions tunica fibrosa in the embodiment is dredged
Hydration process effect is fine.
Embodiment described above is only the preferred embodiments of the invention, and the practical range of the present invention is not limited with this.This
Field it will be appreciated by the skilled person that the change that all shape, principles according to the present invention are made, all should cover in guarantor of the invention
In the range of shield.
Claims (10)
1. a kind of material surface process for hydrophobicizing, it is characterised in that the processing method is in material microcosmic surface syntype
Completed in coating system, the material microcosmic surface syntype coating system includes：Chemical vapour deposition reaction chamber (32), respectively
The air inlet feed system (1) and vacuum-control(led) system (23) being connected with reaction chamber side, the electricity positioned at reaction chamber top
Heat seal spun gold heating system (27), the circulating water cooling system (18) positioned at reaction chamber bottom, at the top of reaction chamber
Quartz observing window (30)；Specific material surface silicic acid anhydride step is as follows：
Step 1, material to be plated is pre-processed；
Step 2, pretreated material to be plated is placed on the sample stage of chemical vapour deposition reaction chamber inside bottom, so
Lectrothermal alloy wire heating system is connected afterwards, and temperature sensor probe is ridden on lectrothermal alloy wire stand, covers reaction chamber ceiling
The quartz observing window in portion；Wherein, sample stage is apart from 20~50mm of lectrothermal alloy wire stand；
Step 3, open the circulating water cooling system of chemical vapour deposition reaction chamber bottom, by sample stage temperature control 20~
40℃；
Step 4, vacuum-control(led) system is opened, the vacuum in chemical vapour deposition reaction chamber is maintained at 10~4000Pa；
Step 5, lectrothermal alloy wire heating system is opened, by the heating temperature of the lectrothermal alloy wire in chemical vapour deposition reaction chamber
Degree control is at 200~300 DEG C；
Step 6, air inlet feed system is opened, the reactant monomer after gasification and initiator are pressed 0.1~10:1 flow-rate ratio is distinguished
It is passed through in chemical vapour deposition reaction chamber, sets the coated film deposition time as 5~90min, reactant monomer is plated in material surface
Upper nanoscale hydrophobic film thickness of coating is 10nm~4 μm.
2. material surface process for hydrophobicizing according to claim 1, it is characterised in that lectrothermal alloy wire in step 5
Lectrothermal alloy wire in heating system is heated by dc source, and its direct current power source voltage is 3~24V, dc source electric current
For 0.1~5A.
3. material surface process for hydrophobicizing according to claim 1 or 2, it is characterised in that air inlet described in step 6
Feed system includes reactant monomer inlet duct and initiator inlet duct；The reactant monomer inlet duct is added by water-bath
Thermal, admission line external resistance silk heater and gas flow guiding dress composition；The temperature of the water bath heating device be 40~
100℃；The admission line external resistance silk heater is heated by dc source, and direct current power source voltage is 1~10V, directly
Stream source current is 0.1~3A；The initiator inlet duct keeps room temperature state.
4. material surface process for hydrophobicizing according to claim 1 or 2, it is characterised in that reacted described in step 6
The charge flow rate of thing monomer and initiator is all controlled in 0.1~3mL/min.
5. material surface process for hydrophobicizing according to claim 3, it is characterised in that reactant described in step 6
The charge flow rate of monomer and initiator is all controlled in 0.1~3mL/min.
6. according to the material surface process for hydrophobicizing described in claim 1 or 2 or 5, it is characterised in that described in step 6
Reactant monomer includes perfluoro decanoate, perfluoro capryl acrylate, perfluoro decanoate acrylate, 2- (perfluoro capryl)-methyl-prop
One in olefin(e) acid ethyl ester, divinylbenzene, dimethyldichlorosilane, methyl trichlorosilane, trichlorosilane or fluoroalkyl silanes
Kind or any two or more combination；The initiator includes di-t-butyl peroxide, tert-butyl peroxide, peroxidating two
Isopropylbenzene, TBHP or benzoyl peroxide one or any two or more combination therein.
7. material surface process for hydrophobicizing according to claim 3, it is characterised in that reactant list described in step 6
Body include perfluoro decanoate, perfluoro capryl acrylate, perfluoro decanoate acrylate, 2- (perfluoro capryl)-EMA,
It is one or any in divinylbenzene, dimethyldichlorosilane, methyl trichlorosilane, trichlorosilane or fluoroalkyl silanes
Two or more combinations；The initiator includes di-t-butyl peroxide, tert-butyl peroxide, cumyl peroxide, uncle
Butylhydroperoxide or benzoyl peroxide one or any two or more combination therein.
8. material surface process for hydrophobicizing according to claim 4, it is characterised in that reactant list described in step 6
Body include perfluoro decanoate, perfluoro capryl acrylate, perfluoro decanoate acrylate, 2- (perfluoro capryl)-EMA,
It is one or any in divinylbenzene, dimethyldichlorosilane, methyl trichlorosilane, trichlorosilane or fluoroalkyl silanes
Two or more combinations；The initiator includes di-t-butyl peroxide, tert-butyl peroxide, cumyl peroxide, uncle
Butylhydroperoxide or benzoyl peroxide one or any two or more combination therein.
9. according to the material surface process for hydrophobicizing described in claim 1 or 2 or 5 or 7 or 8, it is characterised in that step 1
Described in material to be plated include one or more in the material such as inorganic material, organic material, metal：The inorganic material
For glass, monocrystalline silicon, paper, aluminium oxide ceramics or zirconia ceramics, organic material is yarn fabric, high molecular polymer or fiber
Film, the metal material are copper, iron or aluminium alloy.
10. according to the material surface process for hydrophobicizing described in claim 1 or 2 or 5 or 7 or 8, it is characterised in that step 1
The method of the pretreatment to be plated is：When material is inorganic non-metallic material or organic material, material is put into constant temperature
Drying and processing in case；When material is metal material, material surface is polished, washed, is etched, is washed again, drying and processing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110104963A (en) * | 2019-04-19 | 2019-08-09 | 苏州鼎奕通材料科技有限公司 | A kind of ultralow rub resistance coefficient glass cover board Coating Materials and preparation method thereof |
| CN111944363A (en) * | 2020-07-10 | 2020-11-17 | 西北工业大学 | Method for preparing hydrophobic antibacterial antiviral polymer coating by chemical vapor deposition method and application |
| CN113582557A (en) * | 2021-07-16 | 2021-11-02 | 维达力实业（赤壁）有限公司 | Novel application of antifogging agent, optical glass and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379128A (en) * | 2001-04-06 | 2002-11-13 | 中国科学院化学研究所 | Ultra-amphosphobic film and its preparing process |
| CN101962769A (en) * | 2010-10-08 | 2011-02-02 | 中国航空工业集团公司北京航空制造工程研究所 | Method for preparing hydrophobic film on surface of material |
| CN102312226A (en) * | 2011-09-29 | 2012-01-11 | 华东交通大学 | Method of improving hydrophobic stability of nanometer array film |
| CN103695906A (en) * | 2013-12-27 | 2014-04-02 | 东华大学 | Preparation method of super-hydrophobic aluminum or aluminum alloy surface |
| CN104498907A (en) * | 2014-12-03 | 2015-04-08 | 中国科学院宁波材料技术与工程研究所 | Method for preparing hydrophobic carbon film in low-power-consumption and low-air-pressure conditions |
-
2017
- 2017-09-20 CN CN201710850528.1A patent/CN107723706A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379128A (en) * | 2001-04-06 | 2002-11-13 | 中国科学院化学研究所 | Ultra-amphosphobic film and its preparing process |
| CN101962769A (en) * | 2010-10-08 | 2011-02-02 | 中国航空工业集团公司北京航空制造工程研究所 | Method for preparing hydrophobic film on surface of material |
| CN102312226A (en) * | 2011-09-29 | 2012-01-11 | 华东交通大学 | Method of improving hydrophobic stability of nanometer array film |
| CN103695906A (en) * | 2013-12-27 | 2014-04-02 | 东华大学 | Preparation method of super-hydrophobic aluminum or aluminum alloy surface |
| CN104498907A (en) * | 2014-12-03 | 2015-04-08 | 中国科学院宁波材料技术与工程研究所 | Method for preparing hydrophobic carbon film in low-power-consumption and low-air-pressure conditions |
Non-Patent Citations (3)
| Title |
|---|
| ANNA MARIA COCLITE等: "Controlling the Degree of Crystallinity and Preferred Crystallographic Orientation in Poly-Perfl uorodecylacrylate Thin Films by Initiated Chemical Vapor Deposition", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| ANNA MARIA COCLITE等: "Super-Hydrophobic and Oloephobic Crystalline Coatings by Initiated Chemical Vapor Deposition", 《PHYSICS PROCEDIA》 * |
| AYSE ASATEKIN等: "《Modern Applications in Membrane Science and Technology》", 31 October 2011 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110104963A (en) * | 2019-04-19 | 2019-08-09 | 苏州鼎奕通材料科技有限公司 | A kind of ultralow rub resistance coefficient glass cover board Coating Materials and preparation method thereof |
| CN110104963B (en) * | 2019-04-19 | 2021-11-30 | 苏州鼎奕通材料科技有限公司 | Glass cover plate coating material with ultralow friction resistance coefficient and preparation method thereof |
| CN111944363A (en) * | 2020-07-10 | 2020-11-17 | 西北工业大学 | Method for preparing hydrophobic antibacterial antiviral polymer coating by chemical vapor deposition method and application |
| CN113582557A (en) * | 2021-07-16 | 2021-11-02 | 维达力实业（赤壁）有限公司 | Novel application of antifogging agent, optical glass and preparation method and application thereof |
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