CN106947963A - A kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface - Google Patents
A kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface Download PDFInfo
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- CN106947963A CN106947963A CN201710192543.1A CN201710192543A CN106947963A CN 106947963 A CN106947963 A CN 106947963A CN 201710192543 A CN201710192543 A CN 201710192543A CN 106947963 A CN106947963 A CN 106947963A
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/081—Iron or steel solutions containing H2SO4
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
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Abstract
The present invention relates to a kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface, belong to technical field of surface.A kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface, methods described deposits phosphate coating by chemical deposition on the surface of ultra-low-carbon steel matrix first, the surface of ultra-low-carbon steel matrix is deposited phosphate coating, the surface roughness of ultra-low-carbon steel matrix surface is reached 1.7~2.6 μm；Then the ultra-low-carbon steel matrix that being deposited using the saturated fatty acid with more than 12 carbon atoms to surface has phosphate coating carries out hydrophobic modified.The present invention, which is realized, forms certain phosphate coating and hydrophobic surface in matrix surface, with the performance such as automatically cleaning and anti-corrosion, it is widely used in auto industry and electrical equipment industry, such as the anti-corrosive properties, the corrosion resistance of home appliance panel, non-stick of vehicle plate surface, it especially relatively effective can improve the anti-corrosion time of processed matrix and surface is had no effect.
Description
Technical field
The present invention relates to a kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface, belong to technical field of surface.
Background technology
At present, known ultra-low-carbon steel is a kind of new automotive sheet, is characterized in adding in ultra-low-carbon steel and fits
Amount alloying element is allowed to the compound stable with steel interstitial atoms (C, N) formation, the solid solution of steel intermediate gap is reduced as much as possible former
Sub- content.This steel have yield strength it is low, without strain-aging, other good characteristics such as elongation percentage is big, plastic strain ratio is high.It is super
Mild steel is a kind of steel grade with high added value and good deep drawability, is current punching performance most excellent automobile steel
Plate, has been widely used for the manufacturing industry of the products such as automobile, pop can.But, because IF is in storage and transportation, often
Due to being contacted with air, surface is caused the phenomenon of corrosion often occur.And user to the quality requirements of steel products increasingly
Height, for the corrosion resistance of cold-reduced sheet, its corrosion phenomena is especially prominent, directly affects the place for using and increasing user of material
Manage cost.
Production both at home and abroad for ultra-low-carbon steel and use situation, generally take and the ultra-low-carbon steel produced are adopted at present
Its corrosion is reduced with the mode necessarily post-processed.For example：Now with take certain density pickling carried out to steel surface
Processing, finally reaches the purpose for delaying corrosion, but shortcoming is also that obviously cost is higher, waste liquid is difficult to handle etc..
In addition, some companies, which take, carries out certain Nickel Plating Treatment to steel, so also roll up cost.And the above two processing
Mode will carry out certain change to existing production line, so will virtually increase cost and the expansion of production line
The place that existing production line occupies, and it is all extremely difficult that production line is changed in reality production and expands place.Oiling,
The ripe method such as dry is kept, has been used.But applying oil processing has certain limitation for the application of steel, such as is entering
The cleaning treatments such as degreasing are wanted before row production, cost and pollution is added.
Measure above not only rolls up the cost of manufacturer and its improves process, and effect is undesirable.Carry again
Go out slight acid treatment after annealing.But the problems such as due to the production line speed of service, time of pickling is general longer, thus using also compared with
For difficulty.
Metal surface has higher surface free energy, is typical intrinsic hydrophilic material.Almost all of liquid is all
It can easily be sprawled in metal surface, and soak metal surface.The wetability of the surface of solids depend on it chemical composition (or
Surface free energy) and geometry fine structure (or surface roughness).The preparation of metal super-hydrophobic surface is usually required in Metal Substrate
Coarse structure is built on body, and surface chemistry is carried out to rough surface using low-surface-energy material (such as various organic fluorocompounds)
Modify to reduce the surface free energy of metal material.Method common at present includes：(1) etching method (2) LBL self-assembly (3)
Sol-gal process, (4) chemical vapour deposition technique (5) ultraviolet light polymerization method (6) organic polymer phase separation method (7) electrostatic spinning exists
Micron is prepared to the polymer fiber of nanoscale, is a kind of simple and flexible method, but relative to ultra-low-carbon steel table
Face, the heat endurance and mechanical stability of organic-matter chemical decorative layer is poor, is easily destroyed, entered in exceedingly odious environment
And cause the forfeiture of metal surface superhydrophobic.In addition, excessive processing can also influence the subsequent treatment of material in itself, such as table
The Spraying technique in face etc..The current super-hydrophobic processing on ultra-low-carbon steel surface, high cost is studied inadequate system, is very difficult to apply in
In actual industrial.
The content of the invention
In order to overcome existing treatment technology cost than larger, and the deficiency such as damage ratio is larger, production line is difficult to change, this
The purpose of invention is that a kind of simple, equipment investment of offer is less, the system with higher deposition efficiency and relatively low producing cost
Preparation Method.It is pollution-free it can in addition contain save substantial amounts of processing cost.
The present invention provides a kind of raising ultra-low-carbon steel (C≤0.08；Si≤0.03；Mn≤0.40；P≤0.025；S≤
0.020；AI≤0.070；Ti≤0.20, remaining composition be Fe) corrosion resistance of surface new method.The present invention uses composite solution
It is engaged with the solution containing hydrophobic grouping, composite solution active ingredient is carried out reactive deposition in matrix surface；And containing thin
The solution of water base group forms certain hydrophobic layer in matrix surface, finally forms hydrophobic effect on surface.The present invention is by above-mentioned
The methods such as chemical reaction, which are realized, forms certain phosphate coating and hydrophobic surface in matrix surface, with the property such as automatically cleaning and anti-corrosion
Can, be widely used in auto industry and electrical equipment industry, such as the anti-corrosive properties of vehicle plate surface, the corrosion resistance of home appliance panel,
Non-stick, especially relatively effective can improve the anti-corrosion time of processed matrix and surface is had no effect.
A kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface, methods described is first by chemical deposition ultralow
The surface deposition phosphate coating of plain steel, makes the surface of ultra-low-carbon steel matrix deposit phosphate coating, makes ultra-low-carbon steel matrix surface
Surface roughness reaches 1.7~2.6 μm；Then there is phosphatization to surface deposition using the saturated fatty acid with more than 12 carbon atoms
The ultra-low-carbon steel matrix of layer carries out hydrophobic modified.
" ultra-low-carbon steel " of the present invention refers in particular to the ultra-low-carbon steel being made up of following component：C≤0.08；Si≤0.03；Mn
≤0.40；P≤0.025；S≤0.020；AI≤0.070；Ti≤0.20, remaining composition is Fe.
In all technical schemes of the present invention, the preferably described saturated fatty acid with more than 12 carbon atoms is C12~C18's
Saturated fatty acid.Further, it is preferable to which the saturated fatty acid with more than 12 carbon atoms is stearic acid, laurate, 14
Alkanoic acid or palmitic acid.
The present invention be described in technical scheme, preferably methods described first by chemical deposition in ultra-low-carbon steel matrix
Surface deposits phosphate coating, the surface roughness of ultra-low-carbon steel matrix surface is reached 1.872~2.436 μm.
The present invention is described in technical scheme, and preferably described chemical deposition is：The immersion of ultra-low-carbon steel matrix is compound molten
In liquid, 5~15min is handled at 55~70 DEG C of temperature,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate：30~50g/L, nickel nitrate：8~12g/L,
Tartaric acid：1~3g/L.
Further, it is preferable to which the composite solution is made up of following components：Zinc dihydrogen phosphate：35~45g/L, nickel nitrate is used
Measure as 8~12g/L, tartaric acid：1~3g/L.
The present invention is described in technical scheme, preferably described hydrophobic modified to carry out as follows：Surface deposition is had
The ultra-low-carbon steel matrix of phosphate coating soaks more than 2min in the ethanol solution of the saturated fatty acid with more than 12 carbon atoms, does
It is dry.
Further, it is preferable to which the concentration of the ethanol solution of the saturated fatty acid with more than 12 carbon atoms is
0.01mol/L~0.04mol/L.
The present invention is described in technical scheme, the step of preferably including to pre-process ultra-low-carbon steel matrix, to remove
The greasy dirt and oxide of ultra-low-carbon steel matrix surface.
Further, the pre-treatment step is：By ultra-low-carbon steel matrix be placed in alkali lye at 60~80 DEG C immersion 3~
Deionized water rinsing is used after 5min, taking-up；Dilute H that concentration is 0.4~0.5mol/L is placed in again2SO420~40s is soaked in solution,
After taking-up, deionized water rinsing is used；
Wherein, described alkali lye constitutes Na by following components2CO3：10~20g/L, NaOH：25~40g/L, Na4P2O7·
10H2O：90~100g/L, emulsifier op-10：2~3g/L.
It is of the present invention super-hydrophobic film is prepared on ultra-low-carbon steel surface one preferred technical scheme of method be：
A kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface, including following processing steps：
Step one：Ultra-low-carbon steel matrix surface is pre-processed
Ultra-low-carbon steel matrix is pre-processed, the pre-treatment step is：Ultra-low-carbon steel matrix is placed in 60 in alkali lye
3~5min is soaked at~80 DEG C, deionized water rinsing is used after taking-up；Dilute H that concentration is 0.4~0.5mol/L is placed in again2SO4It is molten
20~40s is soaked in liquid, after taking-up, deionized water rinsing is used；
Wherein, described alkali lye constitutes Na by following components2CO3：10~20g/L, NaOH：25~40g/L, Na4P2O7·
10H2O：90~100g/L, emulsifier op-10：2~3g/L.
Step 2：Phosphorating treatment
The ultra-low-carbon steel matrix that gained is handled through step one is immersed in composite solution and carries out phosphorating treatment, temperature 55~70
5~15min of immersion treatment at DEG C；After phosphatization terminates, with deionized water rinsing ultra-low-carbon steel matrix surface, dry, obtain phosphatization
Ultra-low-carbon steel matrix afterwards,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate：30~50g/L, nickel nitrate：8~12g/L,
Tartaric acid：1~3g/L.
Step 3, surface hydrophobicity processing
By the ultra-low-carbon steel matrix after phosphatization, soaked in the ethanol solution of the saturated fatty acid with more than 12 carbon atoms
More than 2min is modified, and is dried, is obtained ultra-low-carbon steel surface ultra-hydrophobic water film.
The principle of the invention is a phosphatization sedimentary will to be formed on ultra-low-carbon steel surface, and forms low-surface-energy on surface
Layer, it is this to utilize the low superficial layer of formed phosphatization, improving the corrosion proof projection for making full use of phosphorization membrane surface simultaneously
And pit, and mutual conduction between projection and pit, such structure is conducive to low-surface-energy in the expansion of matrix surface, and
Higher adhesion is obtained, relatively good hydrophobic performance and preferable hydrophobic effect is obtained.
, can be on the basis of certain roughness and phosphating coat is compounded in after matrix surface, can by saturated fatty acid
Material hydrophobic degree is improved, hydrophobic angle reaches 151~159 °, so as to reach surface hydrophobicity and improve corrosion proof double effectses.
The present invention can adjust the concentration of chemicals, the concentration of saturated fatty acid, the treatment time of chemical solution and temperature
The parameters such as degree realize different anti-corrosion hydrophobic membrane requirements.It can carry out handling simultaneously in all surfaces, hydrophobic efficiency is higher, effect
Good, the adaptability used is stronger.
The present invention has no special requirements to the shape need for handling workpiece, can handle for ultra-low-carbon steel cold-reduced sheet, column
Body class, housing class ultra-low-carbon steel surface etc..
Material surface pattern feature is after chemical deposition and saturated fat acid treatment of the present invention：Pattern is uniformly random
Then, roughness value is 1.872~2.436 μm, and hydrophobic angle value is big.
It is of the invention to be had the following advantages compared with other sufacings：
Material surface after the hydrophobic film preparation of hydrophobic membrane technical requirements typically has following two indices：Roughness Ra, dredge
Water angle.
Compared with etching method, etching method is the common technology for preparing super hydrophobic surface, and it is accurate by Surface Structures
Design and operate, construction micro nano structure or multilevel hierarchy to regulate and control surface hydrophobic, main method include nanosphere etching,
Soft lithograph and photoengraving etc., but technics comparing is complicated, cost is of a relatively high and is unable to the preparation of rapid large-area.The present invention
Advantage be to be compounded in by chemical solution after surface, can reduction roughness on the basis of, can by saturated fatty acid
The corrosion resistance and hydrophobic deg of material are improved, it is simple to operate, invest less, performance indications are that roughness value is 1.272~2.436 μ
M, hydrophobic angle may achieve 151~159 °.
Compared with LBL self-assembly, LBL self-assembly is using the principle of successively alternating deposit, and molecular cell is by identification, dress
Match somebody with somebody and Multiple Combination, construct the process of functional film materials, LBL self-assembly prepare superhydrophobic surface structure be easily and
Economic method.But durability and hydrophobic effect are poor.
Compared with sol-gal process, organo-siloxane compound is formed of different sizes by sol-gal process after hydrolysis, condensation
Nano-particle be coated in substrate, rough surface is formed after drying, to prepare super-hydrophobic surface coating.The method can pass through
Change the change of reactant conditions and reactant species, to control the form of its surface, but the complexity higher time is longer, and
It is whard to control.The anti-corrosion hydrophobic membrane preparation method of the present invention is relatively easy, and technique be able to can both have been controlled by simple operations
System.
Compared with chemical vapour deposition technique, chemical vapour deposition technique is that reactant is formed into ion and freedom under gas phase
Base, by precipitin to solid film surface, obtained durability preferably micro-/ nano coarse structure film.The method shortcoming
Exactly prepare complicated and unstable, of the invention anti-corrosion hydrophobic membrane preparation method relatively easy, and technique can pass through letter
Single operation can both be controlled, and all have preferable durability by electrochemistry and salt spray test, salt spray test can reach 720
Hour.
Compared with ultraviolet light polymerization method, ultraviolet light polymerization method is to use solvent resistant microfluidic device photocuring PFPE
A kind of technology, method simple possible but durability is poor.The present invention has preferably resistance to by electrochemistry and salt spray test
Long property, salt spray test can reach 720 hours.
Compared with electrostatic spinning, electrostatic spinning and EFI coating method are two similar but different technologies, be may serve to
Prepare micro-/ nano coarse structure face coat.Electrostatic spinning is preparing micron to the polymer fiber of nanoscale, is a kind of
Simple and flexible method, molecular weight, solution concentration when polymer, can be effective where appropriate, form uniform and stable tunica fibrosa
Prepare with micro-/ nano dual structure based superhydrophobic thin films, but solution control it is bad be easy to occur separate particles and
Molecule interchain is entangled with.The preparation technology of the present invention is very simple, is not susceptible to the decomposition in later stage, with preferable hydrophobicity and
The stability of friction.
Brief description of the drawings
Fig. 1 is implements the method structural representation that chemical reaction deposit surface of the present invention prepares hydrophobic membrane, and reference is such as
Under：(1) constant temperature passage；(2) workpiece；(3) agitating device；(4) thermostat；(5) composite solution.
Fig. 2 is the flow chart of process implementing.
Fig. 3 is untreated samples electromicroscopic photograph.
Fig. 4 is by the sample electromicroscopic photograph after pre-treatment.
Fig. 5 is the specimen surface electromicroscopic photograph after the phosphorating treatment of embodiment 1.
Fig. 6 is the surface of embodiment 1 by sample electron microscopic picture modified STA.
Fig. 7 is the contact angle test chart of specimen surface after chemical reaction phosphorating treatment
Fig. 8 is the test chart of the specimen surface contact angle after modification.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments, unless otherwise specified, is conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Referring to Fig. 1, the implementation of the hydrophobic method of deposition surface is as follows：Composite solution (5) is stirred using agitating device (3)
Uniformly, composite solution (5) is heated to 55~70 DEG C.Workpiece (2) is put into thermostat (4).Can be by constant temperature for holding constant temperature
The water vapour of degree is passed through constant temperature steam pipeline (1).Composite solution (5) reacts to form certain thickness in ultra-low-carbon steel matrix surface
Phosphorization membrane, and the effect of certain roughness is formed, eventually pass through saturated fatty acid and be modified to form the pattern with hydrophobic function.
Composite solution is made up of following components：30~50g/L of zinc dihydrogen phosphate, preferably 35~45g/L；Nickel nitrate 8~
12g/L；1~3g/L of tartaric acid.
Workpiece is ultra-low-carbon steel steel plate.
Concrete technology step is as follows：
Step one：Ultra-low-carbon steel matrix surface is pre-processed
Ultra-low-carbon steel matrix is pre-processed, the pre-treatment step is：Ultra-low-carbon steel matrix is placed in 60 in alkali lye
3~5min is soaked at~80 DEG C, deionized water rinsing is used after taking-up；Dilute H that concentration is 0.4~0.5mol/L is placed in again2SO4It is molten
20~40s is soaked in liquid, after taking-up, deionized water rinsing is used；
Wherein, described alkali lye constitutes Na by following components2CO3：10~20g/L, NaOH：25~40g/L, Na4P2O7·
10H2O：90~100g/L, emulsifier op-10：2~3g/L.
Step 2：Phosphorating treatment
The ultra-low-carbon steel matrix that gained is handled through step one is immersed in composite solution and carries out phosphorating treatment, temperature 55~70
5~15min of immersion treatment at DEG C；After phosphatization terminates, with deionized water rinsing ultra-low-carbon steel matrix surface, dry, obtain phosphatization
Ultra-low-carbon steel matrix afterwards,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate：30~50g/L, nickel nitrate：8~12g/L,
Tartaric acid：1~3g/L.
Step 3, surface hydrophobicity processing
By the ultra-low-carbon steel matrix after phosphatization, soaked in the ethanol solution of the saturated fatty acid with more than 12 carbon atoms
More than 2min is modified, and is dried, is obtained ultra-low-carbon steel surface ultra-hydrophobic water film.
Embodiment 1
Ultra-low-carbon steel matrix is ultra-low-carbon steel steel plate,
Step one：Ultra-low-carbon steel matrix surface is pre-processed
Ultra-low-carbon steel matrix is pre-processed, the pre-treatment step is：Ultra-low-carbon steel matrix is placed in 60 in alkali lye
Deionized water rinsing is used after 5min, taking-up are soaked at DEG C；Dilute H that concentration is 0.4mol/L is placed in again2SO440s is soaked in solution,
After taking-up, deionized water rinsing is used；
Wherein, described alkali lye constitutes Na by following components2CO3：20g/L, NaOH：40g/L, Na4P2O7·10H2O：
100g/L, emulsifier op-10：3g/L.
Step 2：Phosphorating treatment
The ultra-low-carbon steel matrix that gained is handled through step one, immerse in composite solution and carry out phosphorating treatment, 55 DEG C of temperature
Lower immersion treatment 5min；After phosphatization terminates, with deionized water rinsing ultra-low-carbon steel surface, dry, obtain the material base after phosphatization
Body,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate 30g/L, nickel nitrate 8g/L, tartaric acid 1g/
L。
Step 3：Surface hydrophobicity processing
By the ultra-low-carbon steel matrix after phosphatization, immersion 2min enters in concentration is 0.01mol/L stearic ethanol solution
Row is modified, and is dried, is obtained ultra-low-carbon steel surface ultra-hydrophobic water film.
The hydrophobic pattern of ultra-low-carbon steel matrix surface is such as shown in (Fig. 6) after modification technology processing：It can be seen that after modification technology processing
Material surface pattern feature is：The uniform concavo-convex size of pattern is without fixed rule, and roughness value is 2.574 μm, and hydrophobic angle is 159 °
(Fig. 8).
Embodiment 2
Ultra-low-carbon steel matrix is ultra-low-carbon steel steel plate.
Step one：Be the same as Example 1.
Step 2：Phosphorating treatment
The ultra-low-carbon steel matrix that gained is handled through step one, immerse in composite solution and carry out phosphorating treatment, temperature 60 C
Lower immersion treatment 10min；After phosphatization terminates, with deionized water rinsing ultra-low-carbon steel surface, dry, obtain the material base after phosphatization
Body,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate 35g/L, nickel nitrate 9g/L, tartaric acid 1g/
L。
Step 3, surface hydrophobicity processing
By the ultra-low-carbon steel matrix after phosphatization, immersion 2min enters in concentration is 0.02mol/L lauric ethanol solution
Row is modified, and is dried, is obtained ultra-low-carbon steel surface ultra-hydrophobic water film.
Ultra-low-carbon steel substrate surface topographical feature is after modification technology processing：The uniform concavo-convex size of pattern without fixed rule,
Roughness value is 2.257 μm, and hydrophobic angle is 155 °.
Embodiment 3
Ultra-low-carbon steel matrix is ultra-low-carbon steel steel plate.
Step one：Be the same as Example 1.
Step 2：Phosphorating treatment
The ultra-low-carbon steel matrix that gained is handled through step one, immerse in composite solution and carry out phosphorating treatment, 65 DEG C of temperature
Lower immersion treatment 15min；After phosphatization terminates, with deionized water rinsing ultra-low-carbon steel surface, dry, obtain the material base after phosphatization
Body,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate 45g/L, nickel nitrate 10g/L, tartaric acid 2g/
L。
Step 3, surface hydrophobicity processing
Ultra-low-carbon steel matrix after phosphatization is soaked into 2min in ethanol solution of the concentration for 0.03mol/L tetradecanoic acid
It is modified, dries, obtain ultra-low-carbon steel surface ultra-hydrophobic water film.
Ultra-low-carbon steel substrate surface topographical feature is after modification technology processing：Surface topography is uniform, the no rule of sags and crests,
The size of roughness value is：2.036 μm, hydrophobic angle is 153.
Embodiment 4
Ultra-low-carbon steel matrix is ultra-low-carbon steel steel plate.
Step one：Be the same as Example 1.
Step 2：Phosphorating treatment
The ultra-low-carbon steel matrix that gained is handled through step one, immerse in composite solution and carry out phosphorating treatment, temperature 60 C
Lower immersion treatment 15min；After phosphatization terminates, with deionized water rinsing ultra-low-carbon steel surface, dry, obtain the material base after phosphatization
Body,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate 50g/L, nickel nitrate 12g/L, tartaric acid 3g/
L。
Step 3, surface hydrophobicity processing
By the ultra-low-carbon steel matrix after phosphatization, immersion 2min enters in ethanol solution of the concentration for 0.04mol/L palmitic acid
Row is modified, and is dried, is obtained ultra-low-carbon steel surface ultra-hydrophobic water film.
Ultra-low-carbon steel substrate surface topographical feature is after modification technology processing：Surface topography is uniform, the no rule of sags and crests,
The size of roughness value is：1.872 μm, hydrophobic angle is 151 °.
The present invention can adjust the basic of concentration, modification liquid concentration, phosphating time, the temperature of main sedimentary phosphor chemical conversion point etc.
Parameter realizes different hydrophobic effect requirements.Whole ultra low carbon steel slab can simultaneously be handled, deposition efficiency is high, effect
Good, strong adaptability.It present invention can be suitably applied to ultra-low-carbon steel cold-reduced sheet, column class, the surface-hydrophobicized place of housing class ultra-low-carbon steel
Reason.
Claims (8)
1. a kind of method for preparing super-hydrophobic film on ultra-low-carbon steel surface, it is characterised in that：Methods described is heavy by chemistry first
Area method deposits phosphate coating on the surface of ultra-low-carbon steel matrix, the surface roughness of ultra-low-carbon steel matrix surface is reached 1.7~2.6
μm；Then the ultra-low-carbon steel matrix for having phosphate coating is deposited to surface using the saturated fatty acid with more than 12 carbon atoms to be dredged
It is watersoluble modified.
2. according to the method described in claim 1, it is characterised in that：It is described there are more than 12 carbon atoms saturated fatty acid be
C12~C18 saturated fatty acid.
3. method according to claim 2, it is characterised in that：The saturated fatty acid with more than 12 carbon atoms is hard
Resin acid, laurate, tetradecanoic acid or palmitic acid.
4. according to the method described in claim 1, it is characterised in that：The chemical deposition is：Ultra-low-carbon steel matrix is immersed
In composite solution, 5~15min is handled at 55~70 DEG C of temperature,
Wherein, the composite solution is made up of following components：Zinc dihydrogen phosphate：30~50g/L, nickel nitrate：8~12g/L, winestone
Acid：1~3g/L.
5. method according to claim 4, it is characterised in that：The composite solution is made up of following components：Biphosphate
Zinc：35~45g/L, nickel nitrate consumption is 8~12g/L, tartaric acid：1~3g/L.
6. according to the method described in claim 1, it is characterised in that：It is described hydrophobic modified to carry out as follows：By surface
The ultra-low-carbon steel matrix that depositing has phosphate coating soaks 2min in the ethanol solution of the saturated fatty acid with more than 12 carbon atoms
More than, dry.
7. method according to claim 6, it is characterised in that：The second of the saturated fatty acid with more than 12 carbon atoms
The concentration of alcoholic solution is 0.01mol/L~0.04mol/L.
8. according to the method described in claim 1, it is characterised in that：Methods described is first by chemical deposition in ultra-low-carbon steel
The surface deposition phosphate coating of matrix, makes the surface roughness of ultra-low-carbon steel matrix surface reach 1.872~2.436 μm.
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| CN114686865A (en) * | 2018-11-29 | 2022-07-01 | 鲁东大学 | Metal covered with fatty acid salt coating |
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| CN107893223A (en) * | 2017-10-27 | 2018-04-10 | 华南理工大学 | A kind of preparation method of the super-hydrophobic phosphide composite film layer of zinc layers surface high-corrosion-resistance automatically cleaning |
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| CN114717544A (en) * | 2022-05-16 | 2022-07-08 | 陈兴锋 | Durable super-hydrophobic coating for metal corrosion prevention and preparation method thereof |
| CN114717544B (en) * | 2022-05-16 | 2024-02-20 | 广东合胜实业股份有限公司 | Durable super-hydrophobic coating for metal corrosion prevention and preparation method thereof |
| CN117512745A (en) * | 2024-01-08 | 2024-02-06 | 聊城大学 | Preparation method of metal surface coating structure suitable for ocean strong corrosion environment |
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