CN106835219A - A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof - Google Patents
A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof Download PDFInfo
- Publication number
- CN106835219A CN106835219A CN201710039436.5A CN201710039436A CN106835219A CN 106835219 A CN106835219 A CN 106835219A CN 201710039436 A CN201710039436 A CN 201710039436A CN 106835219 A CN106835219 A CN 106835219A
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- super
- finishing coat
- micro
- deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention provides a kind of super-hydrophobic stainless steel watch finishing coat, super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, micro-nano structure includes micron order pointed cone and nanoscale whisker, outwards radiation forms petal-like structures to nanoscale whisker centered on micron order pointed cone, and the material of micro-nano structure includes at least one in nickel, copper and mickel copper alloy.The super-hydrophobic stainless steel watch finishing coat that the present invention is provided can effectively intercept corrosive medium, bacterium, the erosion of albumen and stick, such that it is able to realize anticorrosion and antifouling performance.Present invention also offers a kind of preparation method of super-hydrophobic stainless steel watch finishing coat, including super-hydrophobic stainless steel watch finishing coat is prepared in surface of stainless steel Direct precipitation by orienting electrodeposition process；Preparation method of the present invention is not limited by stainless steel material shape without template, is modified without by organic low-surface energy substance, reduces cost, reduces technological process, and can regulate and control growth and the size of deposit.
Description
Technical field
The present invention relates to super hydrophobic material field, and in particular to a kind of super-hydrophobic stainless steel watch finishing coat and its preparation side
Method.
Background technology
Research of the China in Seawate-corrosive-resisting steel field is started late, the foundation of marine material system and imperfection, tradition
Material 316L stainless steels are still widely used as marine engineering equipment material, but this material is in hot and humid Nan Haihai
Occur in that serious corrosion failure in foreign environment, it is dirty that reason is mostly derived from more active marine microorganism under the conditions of high humidity hyperpyrexia
Damage activity accelerates the spot corrosion to 316L stainless steels.
The anticorrosion and antifouling of current marine engineering equipment metal material is mainly using the method for paint spraying.Traditional anti-corrosion is prevented
It is main anti-fouling agent that dirty coating is mainly with organotin and cuprous oxide, and the addition of these anti-fouling agents is caused to the marine eco-environment
Very serious destruction.Recently, preparing super hydrophobic surface in metal material surface can also realize anticorrosion and antifouling performance.At present,
The main method for preparing super hydrophobic surface both at home and abroad includes：Self-assembly method, etching method, sol-gal process, chemical vapor deposition, electricity
Chemical deposition, electrochemistry anodic oxidation and mechanical processing method etc..But the above method has apparatus expensive needed for preparation, technique is multiple
It is miscellaneous, need to be modified using expensive low-surface energy substance silicon fluoride, high cost, the defect such as environment is unfriendly.
The content of the invention
To solve the above problems, the invention provides a kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof.This hair
The preparation method process is simple of bright super-hydrophobic stainless steel watch finishing coat, the super-hydrophobicity of obtained super-hydrophobic stainless steel watch finishing coat
Can be good with decay resistance.
First aspect present invention provides a kind of super-hydrophobic stainless steel watch finishing coat, the super-hydrophobic stainless steel watch finishing coat
Including the micro-nano structure being arranged in array, the micro-nano structure includes micron order pointed cone and nanoscale whisker, and the nanoscale is brilliant
Must outwards be radiated centered on the micron order pointed cone and form petal-like structures, the material of the micro-nano structure include nickel, copper and
At least one in monel.
Preferably, the surface of the micro-nano structure has oxide layer, and the thickness of the oxide layer is 10nm-100nm.
Preferably, the height of the micron order pointed cone is 0.1 μm -0.7 μm, and average diameter is 0.4 μm -0.6 μm, adjacent institute
The distance between micron order pointed cone is stated for 0.2 μm -0.3 μm.
Preferably, the length of the nanoscale whisker is 100nm-250nm.
The super-hydrophobic stainless steel watch finishing coat that first aspect present invention is provided includes the micro-nano structure being arranged in array, its essence
Thin micro-nano two-dimensional structure has played the effect of entrapped air with low-surface-energy characteristic, can intercept corrosive medium, bacterium, albumen
Erosion and stick, so as to realize anticorrosion and antifouling performance.
Second aspect present invention provides a kind of preparation method of super-hydrophobic stainless steel watch finishing coat, including：
(1) stainless steel material is provided, the stainless steel material is pre-processed；
(2) it is immersed in pretreated stainless steel material as negative electrode in the electrodeposit liquid containing nickel salt and/or mantoquita, will
Nickel plate or platinum sheet carry out first time electro-deposition, the temperature of the first time electro-deposition as anode in the surface of stainless steel
It is 40-80 DEG C to spend, and current density is 0.1-5A/dm2, electrodeposition time is 50-1000s；
(3) surface of stainless steel obtained in step (2) carries out second electro-deposition, the temperature of second electro-deposition
It is 40-80 DEG C to spend, the big 7-10A/ of current density of first time electro-deposition described in the current density ratio of second electro-deposition
dm2, second electrodeposition time be shorter than first time electrodeposition time；After electro-deposition terminates, in the stainless steel material table
Face is obtained the micro-nano structure being arranged in array, so as to obtain super-hydrophobic stainless steel watch finishing coat；
The super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, and the micro-nano structure includes micron
Level pointed cone and nanoscale whisker, outwards radiation forms petal-shaped knot to the nanoscale whisker centered on the micron order pointed cone
Structure, the material of the micro-nano structure includes at least one in nickel, copper and mickel copper alloy.
Preferably, the current density of second electro-deposition is 8-15A/dm2, the time of second electro-deposition is
1s-500s。
Preferably, by the surface that step (3) is obtained have the stainless steel material of micro-nano structure coating be placed in temperature for 10 DEG C-
40 DEG C and humidity are to store 5d-30d in the environment of 10%-50%, the surface of the micro-nano structure is oxidized, super thin so as to obtain
Water stainless steel watch finishing coat.
Preferably, in the electrodeposit liquid nickel salt and/or the concentration of mantoquita is 0.1-3mol/L.
Preferably, the crystallization modifier of complexing agent and 0.1-3mol/L of the electrodeposit liquid also including 0.1-1mol/L,
The complexing agent is one or more in citrate, borate and acetate, and the crystallization modifier is ethylenediamine hydrochloric acid
Salt.
Preferably, the pH value of the electrodeposit liquid is 1.0-7.0.
The preparation method of a kind of super-hydrophobic stainless steel watch finishing coat that second aspect present invention is provided, by orienting electro-deposition
Method is in surface of stainless steel Direct precipitation prepares coating, and preparation method is simple to operation, without template, and does not receive stainless steel
Material shape limitation, obtained super-hydrophobic stainless steel surfaces coating surface is made up of micron order pointed cone and nanoscale whisker, in array
Shape is distributed, and with preferable ultra-hydrophobicity and antibacterium Adhesion property, is modified without by organic low-surface energy substance, reduces
Cost, reduces technological process, and can regulate and control growth and the size of deposition morphology.
To sum up, beneficial effect of the present invention includes the following aspects：
1st, the super-hydrophobic stainless steel watch finishing coat that the present invention is provided includes the micro-nano structure that is arranged in array, and its is fine micro-
Two-dimensional structure of receiving has played the effect of entrapped air with low-surface-energy characteristic, can intercept the erosion of corrosive medium, bacterium, albumen
With stick, so as to realize anticorrosion and antifouling performance；
2nd, the preparation method of the super-hydrophobic stainless steel watch finishing coat that the present invention is provided, preparation method is simple to operation, reduces
Cost, reduces technological process, and can regulate and control growth and the size of deposition morphology.
Brief description of the drawings
Fig. 1 is the microscopic appearance figure of super-hydrophobic stainless steel watch finishing coat obtained in the embodiment of the present invention 1；
Fig. 2 is the shape appearance figure that micron order pointed cone obtained in the embodiment of the present invention 1 passes through atomic force microscope observation；
Fig. 3 is the hydrophily macro-test and contact angle of super-hydrophobic stainless steel watch finishing coat obtained in the embodiment of the present invention 1
Test chart.
Specific embodiment
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
In a first aspect, the invention provides a kind of super-hydrophobic stainless steel watch finishing coat, super-hydrophobic stainless steel watch finishing coat bag
The micro-nano structure being arranged in array is included, micro-nano structure includes micron order pointed cone and nanoscale whisker, and nanoscale whisker is with micron order
Outwards radiation forms petal-like structures centered on pointed cone, and the material of micro-nano structure includes at least in nickel, copper and mickel copper alloy
Kind.
In the present invention, super-hydrophobic stainless steel watch finishing coat is arranged on surface of stainless steel.
In the present invention, the height of micron order pointed cone is 0.1 μm -0.7 μm.
In the present invention, the height of micron order pointed cone is 0.4 μm -0.6 μm.
In the present invention, the average diameter of micron order pointed cone is 0.4 μm -0.6 μm.
In the present invention, the average diameter of micron order pointed cone is 0.4 μm, 0.5 μm or 0.6 μm.
In the present invention, the distance between adjacent micron order pointed cone is 0.2 μm -0.3 μm.
In the present invention, the length of nanoscale whisker is 100nm-250nm.
In the present invention, the length of nanoscale whisker is 200nm.
In the present invention, the surface of micro-nano structure has oxide layer, and the thickness of oxide layer is 10nm-100nm.
In the present invention, the thickness of oxide layer is 10nm-50nm.
In the present invention, the thickness of oxide layer is 10nm-20nm.
In the present invention, oxide layer is nickel oxide and/or cupric oxide.
In the present invention, super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, and micro-nano structure includes micro-
The surface of meter level pointed cone and nanoscale whisker, micron order pointed cone and nanoscale whisker is oxidized to form oxide layer, the table of oxide layer
Face can be relatively low, can intercept corrosive medium, bacterium, the erosion of albumen and stick.
The super-hydrophobic stainless steel watch finishing coat that first aspect present invention is provided, nanoscale whisker is centered on micron order pointed cone
Outwards radiation forms petal-like structures, and its fine micro-nano two-dimensional structure has played the work of entrapped air with low-surface-energy characteristic
With can effectively intercept corrosive medium, bacterium, the erosion of albumen and stick, such that it is able to realize anticorrosion and antifouling performance.
Second aspect, the invention provides a kind of preparation method of super-hydrophobic stainless steel watch finishing coat, including：
(1) stainless steel material is provided, stainless steel material is pre-processed；
(2) it is immersed in pretreated stainless steel material as negative electrode in the electrodeposit liquid containing nickel salt and/or mantoquita, will
Nickel plate or platinum sheet carry out first time electro-deposition as anode in surface of stainless steel, and the temperature of first time electro-deposition is 40-80
DEG C, current density is 0.1-5A/dm2, electrodeposition time is 50-1000s；
(3) surface of stainless steel obtained in step (2) carries out second electro-deposition, and the temperature of second electro-deposition is
40-80 DEG C, the big 7-9A/dm of current density of the current density ratio first time electro-deposition of second electro-deposition2, second electro-deposition
Time is shorter than first time electrodeposition time；After electro-deposition terminates, the micro-nano knot being arranged in array is obtained in surface of stainless steel
Structure, so as to obtain super-hydrophobic stainless steel watch finishing coat；
Super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure that is arranged in array, micro-nano structure include micron order pointed cone and
Nanoscale whisker, outwards radiation forms petal-like structures, the material of micro-nano structure to nanoscale whisker centered on micron order pointed cone
Including at least one in nickel, copper and mickel copper alloy.
In the present invention, stainless steel material is austenitic stainless steel.
In the present invention, stainless steel material is 316L stainless steels.
In the present invention, the pretreatment of stainless steel material is that stainless steel material is carried out at oil removal treatment and acid-wash activation successively
Reason.
In the present invention, the temperature of oil removal treatment is 70 DEG C -90 DEG C, and the time is 5min-20min.
In the present invention, the temperature of acid-wash activation is room temperature, and the time is 1min-6min.
In the present invention, it is that stainless steel material is placed in alkaline degreaser to remove that oil removal treatment is carried out to stainless steel material
Oil, alkaline degreaser includes that concentration is 10g/L-40g/L NaOH, 20g/L-50g/L sodium carbonate, 10g/L-30g/L phosphoric acid
Sodium and 5g/L-10g/L alkyl polyoxyethylene ethers.
In the present invention, the solvent in alkaline degreaser is distilled water.
In the present invention, acid-wash activation is carried out to stainless steel material and is processed as being placed in acid-wash activation liquid by stainless steel material
Row acid-wash activation treatment, acid-wash activation liquid includes that volume ratio is the hydrochloric acid solution of 5mL/L-20mL/L, the vinegar of 5mL/L-10mL/L
The phosphoric acid solution of acid solution and 5mL/L-10mL/L.
In the present invention, the concentration of hydrochloric acid solution is 35%, and the concentration of acetum is 99.3%, and the concentration of phosphoric acid solution is
85.0%.
After being pre-processed to stainless steel material, the quality and electro-deposition modified layer of subsequent electrodeposition modified layer can be improved
With the adhesion of material.
In the present invention, nickel salt is nickeliferous or nickeliferous and its alloying metal ions salt.
In the present invention, nickel salt is at least one in nickeliferous sulfate, chlorate or acetate.
In the present invention, mantoquita is at least one in sulfate, chlorate or the acetate of cupric.
In the present invention, the concentration of nickel salt and/or mantoquita in electrodeposit liquid is 0.1-3mol/L.
In the present invention, the crystallization modifier of complexing agent and 0.1-3mol/L of the electrodeposit liquid also including 0.1-1mol/L, network
Mixture is one or more in citrate, borate and acetate, and crystallization modifier is ethylenediamine-hydrochloride.
In the present invention, the pH value of electrodeposit liquid is 1.0-7.0.
In the present invention, the pH value of electrodeposit liquid is 1.0,2.0,3.0,4.0,5.0,6.0 or 7.0.
In the present invention, crystallization modifier is contained in electrodeposit liquid, in deposition process, crystallization modifier is to metal difference crystal face
Effect with Characteristic Adsorption, makes the speed of growth of the crystal on different crystal faces different, so as to be easily formed petal-like structures.
In the present invention, stainless steel material, nickel plate or platinum sheet and constant-current supply are connected into by loop by wire.
In the present invention, electro-deposition electric current may be selected direct current or pulse current.
In the present invention, the current density of second electro-deposition is 8-15A/dm2。
In the present invention, the time of first time electro-deposition is 500s-1000s.
In the present invention, the time of second electro-deposition is 1s-500s.
In the present invention, the time of second electro-deposition is 1s-400s.
In the present invention, the time of second electro-deposition is 1s-50s.
In the present invention, there is the stainless steel material of micro-nano structure coating to be placed in temperature the surface that step (3) is obtained is 10
DEG C -40 DEG C and humidity are to store 5d-30d in the environment of 10%-50%, the surface of micro-nano structure is oxidized, super thin so as to obtain
Water stainless steel watch finishing coat.After electro-deposition, under condition of storage of the invention, in micron order pointed cone and nanoscale nickel whisker
Surface forms oxide layer, and the surface of oxide layer can be relatively low, steady in surface of stainless steel formation ultra-hydrophobicity so as to contribute to
Fixed face coat, the presence of simultaneous oxidation layer does not interfere with the pattern of micro-nano structure.
In the present invention, in first electrodeposition process, the metal ion under the conditions of cathodic polarization in surface of stainless steel fills
Sufficient supply area, produces shelf depreciation effect, is locally having elemental metals salient point to generate, with the increase of polarized current density,
The extension of polarization time, continues to discharge at metal salient point, forms the growth and focusing of multiple crystal grain.And cannot get metal ion
The region of abundance supply, i.e. concave point, these concave points are distributed between the pointed cone structure that the salient point gradually grown up is formed, and increased micro-
The roughness on micro-nano structure surface, follow-up micro-nano structure surface is covered by low-surface energy substance nickel oxide (NiO), improves micro-nano knot
The hydrophobic performance of structure.Crystallization modifier can be adsorbed in certain particular crystal plane in electrodeposition process, suppress the extension life of the crystal face
It is long.During double electrodeposition under the conditions of larger current electro-deposition cathodic polarization, suction of the crystallization modifier in metal longitudinal direction crystal face
Attached situation is different, and now micron order pointed cone structure slows down in longitudinal growth speed, and the growth in crystal face (100) and (111) is obtained
Must develop, ultimately form petal-like structures.
In the present invention, principles of electro-deposition is oriented using electrochemistry, by regulating and controlling electro-deposition electric current and electrodeposition time twice
The horizontal and vertical growth of micro-nano structure is controlled, so as to obtain super-hydrophobic stainless steel watch finishing coat in stainless steel surfaces.It is super-hydrophobic
Stainless steel watch finishing coat includes the micro-nano structure being arranged in array, and orientation electro-deposition control condition includes：In order to obtain micron order
The longitudinal growth of pointed cone array structure, i.e. micron order pointed cone are deposited first in surface of stainless steel longitudinal growth, implementation, in order to
The cross growth of taper array structure is obtained, i.e. secondary deposition is implemented in the growth of nanoscale whisker.It is in after orientation electro-deposition
The micro-nano structure of array arrangement.
The present invention utilizes simple constant-current supply and electrolytic cell, the friendly electrodeposit liquid of design environment, so as in material list
Face electro-deposition goes out the micro-nano structure of specific morphology, and ultra-hydrophobicity is obtained using specific morphology structure and composition, without the use of appointing
What low-surface energy substance.Apparatus expensive needed for prepared by prior art, complex process are solved, and uses expensive low surface
Can the modification of material silicon fluoride, high cost, the disagreeableness shortcoming of environment.The present invention by using pretreatment activating, in electrodeposit liquid
It is middle addition specific molecular structure and certain concentration crystallization modifier, regulate and control in electrodeposition process different depositing current densities and
It is time, horizontal and vertical in the Characteristic Adsorption and different electro-deposition current regulation micro-nano structures of different crystal faces using crystallization modifier
Discharge growth, obtain the micro-nano super hydrophobic surface of regulatable size and the direction of growth.Solve traditional electro-deposition techniques without
The growth of method regulation and control deposition morphology and the shortcoming of size.
In the present invention, orientation electro-deposition method includes pre-treatment, orients electro-deposition, post processing.Micro-nano used by the present invention
Structure coating can be by orienting electrodeposition process in surface of stainless steel Direct precipitation, without template, not by stainless steel material
Shape is limited, and by having preferable ultra-hydrophobicity after post processing, is modified without by organic low-surface energy substance, is reduced
Cost, reduces technological process.The present invention orients electrodeposition process and obtains coating, and surface is by micrometer nickel pointed cone and nanoscale
Pointed cone whisker is constituted, and is distributed in array-like, with preferable ultra-hydrophobicity and antibacterium Adhesion property.
The preparation method of the super-hydrophobic stainless steel watch finishing coat that second aspect present invention is provided, preparation method is simple, prepares
Cost is relatively low, is adapted to industrialized mass production, has been obtained super thin with preferable ultra-hydrophobicity and antibacterium Adhesion property
Water coating.
Embodiment 1：
A kind of preparation method of super-hydrophobic stainless steel watch finishing coat, including：
(1) 316L stainless steels are provided as matrix material, 316L stainless steel materials are used into 800#, 1000# successively,
2000# silicon carbide papers polishing surface, polishing is cleaned with distilled water and ethanol respectively after finishing, then with acetone and ethanol to 316L
Stainless steel is cleaned by ultrasonic 20min respectively.Oil removal treatment is carried out to stainless steel using alkaline degreaser, alkaline degreaser includes concentration
It is 10g/L NaOH, 20g/L sodium carbonate, 10g/L sodium phosphates and 5g/L alkyl polyoxyethylene ethers, except oil temperature is 70 DEG C, removes
The oily time is 20min.Then acid-wash activation treatment is carried out using acid-wash activation liquid, acid-wash activation liquid includes 5mL/L hydrochloric acid
(35%), 5mL/L acetic acid (99.3%) and 5mL/L phosphoric acid (85.0%), at ambient temperature, the acid-wash activation time is 6min,
Then cleaned with distilled water and ethanol, nitrogen drying is stored stand-by.
(2) it is immersed in pretreated stainless steel material as negative electrode in the electrodeposit liquid containing nickel salt, the electricity containing nickel salt
Deposition liquid includes that concentration is the nickel sulfate of 0.1mol/L, and concentration is the sodium citrate of 0.1mol/L, and concentration is the second of 0.1mol/L
Diamine hydrochloride, is 1.0 using 10% ammoniacal liquor or 10% hydrochloric acid solution regulation and control electrodeposit liquid pH value；Using platinum sheet as anode, will
Stainless steel material, platinum sheet and constant-current supply connect into loop, apply cathodic polarization electric current to stainless steel material, in stainless steel material
Surface carries out electro-deposition twice, and the temperature of first time electro-deposition is 40 DEG C, and depositing current density size is 5A/dm2, sedimentation time
It is 1000s；The temperature of second electro-deposition is 40 DEG C, and deposition current size is 12A/dm2, sedimentation time is 500s；Electro-deposition
After end, the micro-nano structure being arranged in array is obtained in surface of stainless steel；
(3) stainless steel material that surface is had the micro-nano structure coating of array arrangement is placed in temperature for 10 DEG C and humidity are
30d is stored in 10% environment, the surface of micro-nano structure is oxidized, so as to obtain super-hydrophobic stainless steel watch finishing coat.
Super-hydrophobic stainless steel watch finishing coat obtained in embodiment 1 is used into transmission electron microscope observing, Fig. 1 is the embodiment of the present invention
The microscopic appearance figure of super-hydrophobic stainless steel watch finishing coat obtained in 1；From (a), (b) to (c) successively step by step amplify (scale is followed successively by
1 μm, 200nm, 100nm), from Fig. 1 (a) it can be seen that Ni-based micro-nano structure is presented array distribution, can from Fig. 1 (b) and (c)
Horizontal and vertical development structure is presented to Ni-based micro-nano structure, nanoscale nickel whisker is centered on micrometer nickel pointed cone to external radiation
Form petal-like structures.Wherein, the length of nanoscale whisker is in the range of 100nm-250nm.
Fig. 2 is the shape appearance figure that micron order pointed cone obtained in the embodiment of the present invention 1 passes through atomic force microscope observation；From Fig. 2
In as can be seen that micron order pointed cone height be 0.1 μm -0.7 μm, average diameter be 0.4 μm -0.6 μm, adjacent micron order pointed cone
The distance between be 0.2 μm -0.3 μm.
Embodiment 2：
A kind of preparation method of super-hydrophobic stainless steel watch finishing coat, including：
(1) 316L stainless steels are provided as matrix material, stainless steel material is used into 800#, 1000#, 2000# water successively
Dry sanding paper polishing surface, polishing is cleaned with distilled water and ethanol respectively after finishing, then with acetone and ethanol to 316L stainless steels
It is cleaned by ultrasonic 20min respectively.Oil removal treatment is carried out to stainless steel using alkaline degreaser, alkaline degreaser includes that concentration is 40g/
L NaOH, 50g/L sodium carbonate, 30g/L sodium phosphates and 10g/L alkyl polyoxyethylene ethers, except oil temperature is 90 DEG C, during oil removing
Between be 5min.Then acid-wash activation treatment is carried out using acid-wash activation liquid, acid-wash activation liquid include 20mL/L hydrochloric acid (35%),
10mL/L acetic acid (99.3%) and 10mL/L phosphoric acid (85.0%), at ambient temperature, the acid-wash activation time is 1min, Ran Houyong
Distilled water and ethanol are cleaned, nitrogen drying, are stored stand-by.
(2) it is immersed in pretreated stainless steel material as negative electrode in the electrodeposit liquid containing mantoquita, the electricity containing nickel salt
Deposition liquid includes that concentration is the copper sulphate of 3mol/L, and concentration is the sodium citrate of 1mol/L, and concentration is the ethylenediamine salt of 3mol/L
Hydrochlorate, is 3.0 using 10% ammoniacal liquor or 10% hydrochloric acid solution regulation and control electrodeposit liquid pH value；Using platinum sheet as anode, by platinum sheet and
Constant-current supply connects into loop, and cathodic polarization electric current is applied to stainless steel material, and it is heavy to carry out electricity twice in surface of stainless steel
Product, the temperature of first time electro-deposition is 80 DEG C, and depositing current density size is 0.1A/dm2, sedimentation time is 50s；Second electricity
The temperature of deposition is 80 DEG C, and deposition current size is 8.0A/dm2, sedimentation time is 1s；After electro-deposition terminates, in stainless steel
Material surface is obtained the copper-based micro-nano structure being arranged in array；
(3) stainless steel material that surface is had the micro-nano structure coating of array arrangement is placed in temperature for 40 DEG C and humidity are
5d is stored in 50% environment, the surface of micro-nano structure is oxidized, so as to obtain super-hydrophobic stainless steel watch finishing coat.
Embodiment 3：
A kind of preparation method of super-hydrophobic stainless steel watch finishing coat, including：
(1) 316L stainless steels are provided as matrix material, stainless steel material is used into 800#, 1000#, 2000# water successively
Dry sanding paper polishing surface, polishing is cleaned with distilled water and ethanol respectively after finishing, then with acetone and ethanol to 316L stainless steels
It is cleaned by ultrasonic 20min respectively.Oil removal treatment is carried out to stainless steel using alkaline degreaser, alkaline degreaser includes that concentration is 30g/
L NaOH, 30g/L sodium carbonate, 20g/L sodium phosphates and 8g/L alkyl polyoxyethylene ethers, except oil temperature is 80 DEG C, oil removing time
It is 10min.Then acid-wash activation treatment is carried out using acid-wash activation liquid, acid-wash activation liquid include hydrochloric acid 10mL/L (35%),
8mL/L acetic acid (99.3%) and 8mL/L phosphoric acid (85.0%), at ambient temperature, the acid-wash activation time is 4min, then with steaming
Distilled water and ethanol are cleaned, nitrogen drying, are stored stand-by.
(2) it is immersed in pretreated stainless steel material as negative electrode in the electrodeposit liquid containing nickel salt, the electricity containing nickel salt
Deposition liquid includes that concentration is the nickel sulfate of 2mol/L, and concentration is the sodium citrate of 0.5mol/L, and concentration is the second two of 0.5mol/L
Amine hydrochlorate, is 7.0 using 10% ammoniacal liquor or 10% hydrochloric acid solution regulation and control electrodeposit liquid pH value；Using platinum sheet as anode, by platinum
Plate and constant-current supply connect into loop, and cathodic polarization electric current is applied to stainless steel material, are carried out twice in surface of stainless steel
Electro-deposition, the temperature of first time electro-deposition is 50 DEG C, and depositing current density size is 5A/dm2, sedimentation time is 500s；Second
The temperature of secondary electro-deposition is 50 DEG C, and deposition current size is 15A/dm2, sedimentation time is 50s；After electro-deposition terminates, stainless
Steel material surface is obtained the micro-nano structure being arranged in array；
(3) stainless steel material that surface is had the micro-nano structure of array arrangement is placed in temperature for 20 DEG C is 30% with humidity
Environment in store 20d, the surface of micro-nano structure is oxidized, so as to obtain super-hydrophobic stainless steel watch finishing coat.
Effect example
It is the performance of the obtained super-hydrophobic stainless steel watch finishing coat of the checking present invention, implements present invention also offers effect
Example.
Super-hydrophobic stainless steel watch finishing coat obtained in embodiment 1 is carried out into hydrophily macro-test and contact angle test, knot
Fruit is as shown in figure 3, Fig. 3 is the hydrophily macro-test of super-hydrophobic stainless steel watch finishing coat obtained in the embodiment of the present invention 1 and connects
Feeler test chart.Fig. 3 (a) and (b) are undressed 316L stainless steel surfaces hydrophily macro-test and contact angle test；Figure
3 (c) and (d) is embodiment 1 obtained 316L stainless steel surfaces hydrophily macro-tests and contact with Ni-based micro-nano structure
Angle is tested.The obtained 316L stainless steels with Ni-based micro-nano structure of embodiment 1 have good ultra-hydrophobicity, and contact angle reaches
To 153.74 °, and the contact angle of undressed 316L stainless steels is only 104.65 °.
To sum up, by super-hydrophobic stainless steel watch finishing coat obtained in embodiment of the present invention preparation method, surpass with good
Hydrophobic performance.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of super-hydrophobic stainless steel watch finishing coat, it is characterised in that the super-hydrophobic stainless steel watch finishing coat includes being in array
The micro-nano structure of arrangement, the micro-nano structure includes micron order pointed cone and nanoscale whisker, and the nanoscale whisker is with described micro-
Outwards radiation forms petal-like structures centered on meter level pointed cone, and the material of the micro-nano structure is including in nickel, copper and mickel copper alloy
At least one.
2. super-hydrophobic stainless steel watch finishing coat as claimed in claim 1, it is characterised in that the surface of the micro-nano structure has
Oxide layer, the thickness of the oxide layer is 10nm-100nm.
3. super-hydrophobic stainless steel watch finishing coat as claimed in claim 1, it is characterised in that the height of the micron order pointed cone is
0.1 μm -0.7 μm, average diameter is 0.4 μm -0.6 μm, and the distance between adjacent described micron order pointed cone is 0.2 μm -0.3 μm.
4. super-hydrophobic stainless steel watch finishing coat as claimed in claim 1, it is characterised in that the length of the nanoscale whisker is
100nm-250nm。
5. a kind of preparation method of super-hydrophobic stainless steel watch finishing coat, it is characterised in that including：
(1) stainless steel material is provided, the stainless steel material is pre-processed；
(2) it is immersed in pretreated stainless steel material as negative electrode in the electrodeposit liquid containing nickel salt and/or mantoquita, by nickel plate
Or platinum sheet carries out first time electro-deposition as anode in the surface of stainless steel, the temperature of the first time electro-deposition is
40-80 DEG C, current density is 0.1-5A/dm2, electrodeposition time is 50-1000s；
(3) surface of stainless steel obtained in step (2) carries out second electro-deposition, and the temperature of second electro-deposition is
40-80 DEG C, the big 7-10A/dm of current density of first time electro-deposition described in the current density ratio of second electro-deposition2, institute
State second electrodeposition time and be shorter than first time electrodeposition time；After electro-deposition terminates, it is obtained in the surface of stainless steel
The micro-nano structure being arranged in array, so as to obtain super-hydrophobic stainless steel watch finishing coat；
The super-hydrophobic stainless steel watch finishing coat includes the micro-nano structure being arranged in array, and the micro-nano structure includes micron order point
Cone and nanoscale whisker, outwards radiation forms petal-like structures to the nanoscale whisker centered on the micron order pointed cone, institute
State at least one that the material of micro-nano structure is included in nickel, copper and mickel copper alloy.
6. the preparation method of super-hydrophobic stainless steel watch finishing coat as claimed in claim 5, it is characterised in that second electricity
The current density of deposition is 8-15A/dm2, the time of second electro-deposition is 1s-500s.
7. the preparation method of super-hydrophobic stainless steel watch finishing coat as claimed in claim 5, it is characterised in that by step (3)
To there is the stainless steel material of micro-nano structure coating to be placed in temperature is that 10 DEG C -40 DEG C and humidity are the ring of 10%-50% on surface
5d-30d is stored in border, the surface of the micro-nano structure is oxidized, so as to obtain super-hydrophobic stainless steel watch finishing coat.
8. the preparation method of super-hydrophobic stainless steel watch finishing coat as claimed in claim 5, it is characterised in that the electrodeposit liquid
In nickel salt and/or mantoquita concentration be 0.1-3mol/L.
9. the preparation method of the super-hydrophobic stainless steel watch finishing coat as described in claim 5 or 8, it is characterised in that the electricity is heavy
The crystallization modifier of complexing agent and 0.1-3mol/L of the hydrops also including 0.1-1mol/L, the complexing agent is citrate, boron
One or more in hydrochlorate and acetate, the crystallization modifier is ethylenediamine-hydrochloride.
10. the preparation method of super-hydrophobic stainless steel watch finishing coat as claimed in claim 5, it is characterised in that the electro-deposition
The pH value of liquid is 1.0-7.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710039436.5A CN106835219B (en) | 2017-01-19 | 2017-01-19 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710039436.5A CN106835219B (en) | 2017-01-19 | 2017-01-19 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106835219A true CN106835219A (en) | 2017-06-13 |
| CN106835219B CN106835219B (en) | 2019-06-14 |
Family
ID=59123445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710039436.5A Active CN106835219B (en) | 2017-01-19 | 2017-01-19 | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106835219B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823617A (en) * | 2018-06-25 | 2018-11-16 | 宁波中材钰翔新材料科技有限公司 | A kind of preparation method of super water repellent metal mesh |
| WO2019015143A1 (en) * | 2017-07-17 | 2019-01-24 | 英诺激光科技股份有限公司 | Method for performing corrosion resistance processing on surface of metal by using laser, and application thereof |
| CN109468668A (en) * | 2018-12-10 | 2019-03-15 | 深圳先进技术研究院 | A kind of preparation method and applications of platinum nano-cone array structure |
| CN110468437A (en) * | 2019-08-15 | 2019-11-19 | 胜利油田金岛实业有限责任公司胜岛石油机械厂 | A kind of preparation method of petroleum stainless steel pipes corrosion resistance structure |
| WO2020119510A1 (en) * | 2018-12-11 | 2020-06-18 | 深圳先进技术研究院 | Superhydrophobic diamond-like composite layer structure and preparation method therefor |
| CN111807314A (en) * | 2020-06-23 | 2020-10-23 | 南开大学 | Copper oxide nano whisker material with rapid sterilization and large contact surface |
| CN111850660A (en) * | 2020-07-15 | 2020-10-30 | 大连理工大学 | Simple device for preparing inner surface of super-hydrophobic pipe based on electroplating method |
| CN112853420A (en) * | 2021-01-14 | 2021-05-28 | 同曦集团有限公司 | Fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and preparation method thereof |
| CN112853414A (en) * | 2020-12-25 | 2021-05-28 | 山东科技大学 | Preparation method and application of decoration-free super-hydrophobic copper layer |
| CN113445107A (en) * | 2021-06-28 | 2021-09-28 | 中国石油大学(华东) | Ni-PTFE-SiC super-hydrophobic anticorrosive coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588164A (en) * | 2013-10-08 | 2014-02-19 | 上海交通大学 | Copper-silver micro-nano multi-stage structure super-hydrophobic surface and production method thereof |
-
2017
- 2017-01-19 CN CN201710039436.5A patent/CN106835219B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588164A (en) * | 2013-10-08 | 2014-02-19 | 上海交通大学 | Copper-silver micro-nano multi-stage structure super-hydrophobic surface and production method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TAO HANG: "Super-hydrophobic nickel films with micro-nano hierarchical structure prepared by electrodeposition", 《APPLIED SURFACE SCIENCE 》 * |
| 徐如人: "《无机合成与制备化学第二版 下册》", 28 February 2009 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019015143A1 (en) * | 2017-07-17 | 2019-01-24 | 英诺激光科技股份有限公司 | Method for performing corrosion resistance processing on surface of metal by using laser, and application thereof |
| CN108823617A (en) * | 2018-06-25 | 2018-11-16 | 宁波中材钰翔新材料科技有限公司 | A kind of preparation method of super water repellent metal mesh |
| CN109468668A (en) * | 2018-12-10 | 2019-03-15 | 深圳先进技术研究院 | A kind of preparation method and applications of platinum nano-cone array structure |
| WO2020119607A1 (en) * | 2018-12-10 | 2020-06-18 | 深圳先进技术研究院 | Preparation method for platinum nanocone array structure and application thereof |
| WO2020119510A1 (en) * | 2018-12-11 | 2020-06-18 | 深圳先进技术研究院 | Superhydrophobic diamond-like composite layer structure and preparation method therefor |
| CN110468437A (en) * | 2019-08-15 | 2019-11-19 | 胜利油田金岛实业有限责任公司胜岛石油机械厂 | A kind of preparation method of petroleum stainless steel pipes corrosion resistance structure |
| CN111807314A (en) * | 2020-06-23 | 2020-10-23 | 南开大学 | Copper oxide nano whisker material with rapid sterilization and large contact surface |
| CN111850660A (en) * | 2020-07-15 | 2020-10-30 | 大连理工大学 | Simple device for preparing inner surface of super-hydrophobic pipe based on electroplating method |
| CN112853414A (en) * | 2020-12-25 | 2021-05-28 | 山东科技大学 | Preparation method and application of decoration-free super-hydrophobic copper layer |
| CN112853414B (en) * | 2020-12-25 | 2021-12-24 | 山东科技大学 | Preparation method and application of decoration-free super-hydrophobic copper layer |
| CN112853420A (en) * | 2021-01-14 | 2021-05-28 | 同曦集团有限公司 | Fluoride-free super-hydrophobic self-cleaning antibacterial mildew-proof antiviral stainless steel and preparation method thereof |
| CN113445107A (en) * | 2021-06-28 | 2021-09-28 | 中国石油大学(华东) | Ni-PTFE-SiC super-hydrophobic anticorrosive coating and preparation method thereof |
| CN113445107B (en) * | 2021-06-28 | 2022-05-13 | 中国石油大学(华东) | Ni-PTFE-SiC super-hydrophobic anticorrosive coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106835219B (en) | 2019-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106835219B (en) | A kind of super-hydrophobic stainless steel watch finishing coat and preparation method thereof | |
| JPH1096095A (en) | Eiectroplating method of tin or tin alloy on metallic substrate | |
| CN110724992B (en) | Method for preparing corrosion-resistant super-hydrophobic film on surface of aluminum alloy | |
| CN103147102B (en) | A kind of pin cone micro-nano twin-stage array structure materials and preparation method thereof | |
| CN108258195B (en) | Method for preparing porous copper foil current collector of lithium ion battery | |
| CN109023462B (en) | Method for preparing polydopamine film layer by magnesium and magnesium alloy surface electropolymerization | |
| Li et al. | Electrodeposition and characterization of nano-structured black nickel thin films | |
| CN104250813A (en) | Method for preparing super-hydrophobic self-cleaned corrosion-resisting surface of magnesium alloy | |
| CN105714360A (en) | Alkaline graphene-nickel electroplating liquid, and preparation method and application thereof | |
| CN113777140B (en) | Modification method for improving chemical activity and stability of graphene, modified graphene prepared by method and application of modified graphene | |
| CN107447235A (en) | A kind of ordered porous nickel composite materials of nano-porous gold@and its preparation method and application | |
| CN102127784B (en) | Electroplated Cu laminated film and preparation method thereof | |
| CN105506693A (en) | Surface nickel coating grain size regulating method capable of improving corrosion resistance | |
| Kalantary et al. | Optimisation of a bath for electroless plating and its use for the production of nickel-phosphorus-silicon carbide coatings | |
| CN1676674A (en) | Method for preparing nickel-phosphor alloy base composite cladding containing nano particle | |
| CN104562111A (en) | Method for improving corrosion resistance of nickel-aluminum bronze | |
| CN101748427A (en) | Titanium plate of a kind of plated with thick gold membrane and preparation method thereof | |
| JP2015529746A (en) | Electrodeposition process of nickel-cobalt coating with dendritic structure | |
| CN103540975B (en) | A kind of method at copper electroplating surface metal manganese | |
| CN112481660A (en) | Preparation method of ordered metal nanowire array | |
| CN104726875A (en) | Method for preparation of super-hydrophobic CuO film on steel surface | |
| Wu | Electrodeposition and thermal stability of Re60Ni40 amorphous alloy | |
| CN113174617B (en) | Method for preparing super-hydrophobic Zn-Fe alloy coating in eutectic ionic liquid through electrodeposition | |
| CN102041543A (en) | Preparation method of fullerene/metal composite film on metal surface | |
| CN113061890A (en) | Method for constant-voltage electrodeposition of Ni-SiC composite coating on aluminum alloy surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |