CN109082689B - Surface is covered with magnesium alloy implant material of nanometer crystal zinc plating and preparation method thereof - Google Patents
Surface is covered with magnesium alloy implant material of nanometer crystal zinc plating and preparation method thereof Download PDFInfo
- Publication number
- CN109082689B CN109082689B CN201810761659.7A CN201810761659A CN109082689B CN 109082689 B CN109082689 B CN 109082689B CN 201810761659 A CN201810761659 A CN 201810761659A CN 109082689 B CN109082689 B CN 109082689B
- Authority
- CN
- China
- Prior art keywords
- zinc
- magnesium alloy
- plating
- time
- nano
- 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.)
- Active
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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses the magnesium alloy implant materials and preparation method thereof that surface is covered with nanometer crystal zinc plating, the material includes magnesium alloy implant material, being covered in the crystallite dimension on magnesium alloy implant material is 1~10 μm, with a thickness of 1~10 μm of coarse-grain zinc pre-plating layer；And the crystallite dimension being covered on coarse-grain zinc pre-plating layer is 30~100nm, with a thickness of 10~100 μm of nanometer crystal zinc plating.The preparation method comprises the following steps: magnesium alloy implant material matrix being added in zinc pre-plating solution and carries out first time electroplating processes, is directly added in Nano-Zinc electroplate liquid after washing and carries out second of electroplating processes, then wash.Material produced by the present invention contains Nano-Zinc, good biocompatibility, it is at low cost, easy to operate, be easy to be mass produced；Nanometer crystal zinc plating is also biodegradable, therefore, the control to magnesium alloy implant material active time can be realized by the design to its crystallite dimension and thickness.
Description
Technical field
The invention belongs to Surface Engineering and technical field of surface, and in particular to surface is covered with the magnesium of nanometer crystal zinc plating
Alloy is implanted into material and preparation method thereof.
Background technique
With the raising that the acceleration and patient of aging of population process require quality of life after healing, medical magnesium is closed
Gold is received significant attention as the excellent enhancing of human body disease damage bone tissue, reparation and alternate material.It is excellent that this mainly has benefited from its
The performances such as different biocompatibility, mechanical strength and easy processing.But the chemical property of magnesium is extremely active, the electrode potential of magnesium
For -2.36V (relative to saturated calomel electrode), which dictates that magnesium alloy all can in inorganic acid, organic acid and neutral medium
Corrode.And the pH value of human body is about 7.4, postoperative metabolic adsorption process may cause second level acidosis, make
The pH value of vivo environment is lower than 7.4, further speeds up the corrosion of magnesium alloy, leads to graft failure, need to carry out second operation removal
It is implanted into material, this will cause secondary insult to patient.Although absorbing excessively also can be right in addition, magnesium is the common elements of human body
Tissue damages, this limits it in the application in body implanting material field to a certain extent.Therefore, how to improve
The corrosion resisting property of magnesium alloy body implanting material becomes urgent problem to be solved.
Magnesiumalloy surface modifying remain its it is original composition, structure it is constant in the case where, can significantly improve its table
Face mechanical strength, wear and corrosion resistance become the key problem in technology for pushing medical magnesium alloy development.Existing Mg alloy surface changes
In property method, electrodeposition process is because its is easy to operate, easily prepared, does not damage and is not limited by material shape to material structure
The advantages that processed, is considered to be the modified optimal path of medical magnesium alloy surface.By taking electrodepositing zinc as an example, the standard electrode EMF of zinc
(- 0.76V) just than magnesium；Hardness is higher than magnesium (zinc 412MPa, magnesium 260MPa)；Price is cheaper than magnesium；More importantly zinc is also
The microelement of needed by human body has not replaceable effect in the metabolic processes of human body.Therefore, electrodepositing zinc is not only
Mechanical strength, wear-resisting property and the corrosion resisting property that can significantly improve medical magnesium alloy have been also equipped with as body implanting material
Necessary biocompatibility.Existing scholar attempts in Mg alloy surface electrodepositing zinc at present, and has achieved significant achievement
(Electrochimica Acta,2009,55(2):560-571；Electrochimica Acta,2009,55(2):560-
571；Materials and Corrosion,2010,61(10):860-865).
Electro-deposition nanometer crystal zinc plating is a kind of table for being expected to substitute traditional electrodepositing zinc technique developed in recent years
Face technology for modifying, the research in relation to Mg alloy surface electro-deposition nanometer crystal zinc plating and its wear-corrosion resistance but not yet appear in the newspapers
Road.This is mainly due to the electrode potential of magnesium alloy is low, electro-chemical activity is high, is easy and the Zn in electrolyte2+It is anti-that displacement occurs
It answers, hardly results in fine and close zinc sedimentary, needless to say require deposition potential extremely stringent Nano-Zinc.
Summary of the invention
It is on active service in fluid environment for above-mentioned magnesium alloy implant material the too fast problem of degradation rate encountered, it is of the invention
It is designed to provide surface and is covered with magnesium alloy implant material of nanometer crystal zinc plating and preparation method thereof.The present invention is using nanometer electricity
Deposition technique prepares Nano-Zinc in medical magnesium alloy surface, is not only able to realize to its surface peening, additionally it is possible to it is wear-resisting to improve its
Corrosion energy is of great significance to pushing it to develop with application to substantially prolong the active time of magnesium alloy implant material.
The purpose of the invention is achieved by the following technical solution:
A kind of surface is covered with the magnesium alloy implant material of nanometer crystal zinc plating, including magnesium alloy implant material, is covered in magnesium
Alloy is implanted into the coarse-grain zinc pre-plating layer on material；And it is covered in the nanometer crystal zinc plating on coarse-grain zinc pre-plating layer.
Preferably, the coarse-grain zinc pre-plating layer crystallite dimension is 1~10 μm, with a thickness of 1~10 μm；The nanocrystalline zinc plating
Layer crystal particle size is 30~100nm, and with a thickness of 10~100 μm, roughness is less than 230nm.
A method of in magnesium alloy implant material surface electro-deposition biocompatibility Nano-Zinc, comprising the following steps:
Magnesium alloy implant material matrix is added in zinc pre-plating solution and carries out first time electroplating processes, it can be in matrix surface shape
At one layer of coarse-grain zinc pre-plating layer；It will be directly added into Nano-Zinc electroplate liquid after the matrix for being covered with coarse-grain zinc pre-plating layer washing and carry out the
Second time electroplating processing, washing obtain the magnesium alloy implant material for being covered with coarse-grain zinc pre-plating layer and nanometer crystal zinc plating；
Temperature is 40~60 DEG C in the first time electroplating processes, and electroplating time is 1~10min；
Temperature is 15~60 DEG C in second of electroplating processes, and electroplating time is 10~120min；
The ingredient of the zinc pre-plating solution are as follows: 20~100g/L of zinc sulfate, 60~300g/L of sodium pyrophosphate and sodium fluoride 5~
20g/L, solvent are water；The zinc pre-plating solution pH is 9~11；
The Nano-Zinc electroplating bath components are as follows: 50~300g/L of zinc sulfate, 10~40g/L of boric acid and grain refiner 0.3
~3g/L, solvent are water；The Nano-Zinc electroplate liquid pH is 1~3.
According to the difference of magnesium alloy matrix surface greasy dirt state, dish washing liquid, cleanser, acetone, alcohol, gasoline etc. can be used
Organic solvent carries out ultrasonic 5~10min of oil removing to it, is then rinsed with deionized water；Magnesium alloy is carried out using ethanedioic acid again
Derusting, according to the difference of Mg alloy surface corrosion degree, the processing time is generally 10~60s at room temperature, then spends
Ionized water rinses.
Zinc pre-plating solution of the invention contains zinc sulfate, sodium pyrophosphate and sodium fluoride, and effectively magnesium can be inhibited to Zn2+'s
Metathesis forms zinc transition zone of the layer crystal particle size in micro-scaled range in Mg alloy surface, thus after ensure that
Continuous electro-deposition nanometer crystal zinc plating is gone on smoothly.
Zinc sulfate, boric acid and the macromolecule amide groups as grain refiner are contained in Nano-Zinc plating solution of the invention
Object is closed, plating solution has the characteristics that dispersibility is good, covering power is strong, conductivity is moderate, composition is simple, convenient for safeguarding, and is free of
Noxious material, it is environmentally protective, nanometer crystal zinc plating can be successfully being prepared through pre- zinc-plated medical magnesium alloy surface.
Using nanometer galvanizing flux of the invention, using through pre- zinc-plated medical magnesium alloy matrix, as cathode, zine plate is anode, In
Crystallite dimension can be obtained in 100nm zinc coating below under conditions of limiting in the present invention, and can be by forming to Nano-Zinc plating solution
Optimization with electro-deposition parameter realizes that crystallite dimension is controllable in 30~100nm.
In Nano-Zinc plating solution of the invention, zinc sulfate mainly influences the growth of crystal grain as main salt, and concentration is greater than 300g/L
When, coating coarse grains, hexagonal sheet；When concentration is lower than 50g/L, current efficiency can be made to be remarkably decreased.Boric acid is as slow
Electuary plays the role of stable bath pH value in the plating process；A kind of high molecular weight amido compounds are as grain refiner
Promotion is primarily served into nuclear reaction, inhibits the effect of nucleus growth, concentration is easy to be precipitated when being higher than 3g/L, and again to crystallite dimension
It has no significant effect.
Nano-Zinc plating solution of the invention, it is necessary to which the pH value range for being maintained at certain is interior could to stablize use.When pH is too low, plating
Layer is uneven, is in grey black；When pH is excessively high, coating is coarse, cannot get nanocrystalline.
Nano-Zinc plating solution of the invention, normal range of operation can be used smoothly, temperature is low at room temperature between 15~60 DEG C
Zinc sulfate is easy crystallization precipitation when 15 DEG C, and then coating is coarse for temperature drift.
Preferably, the grain refiner is one of following compound:
A) molecular weight is the amphoteric ion type macromolecule amido compounds of 500-1200 ten thousand；
B) molecular weight is the non-ionic macromolecule amido compounds of 200-1500 ten thousand；
C) molecular weight is the anionic macromolecule amido compounds of 300-2200 ten thousand；
D) molecular weight is the cationic high-molecular amido compounds of 500-1200 ten thousand.
It is furthermore preferred that the grain refiner passes through aqueous solution by acrylamide and acrylyl oxy-ethyl-trimethyl salmiac
Free radical copolymerization synthesis.
Preferably, be stirred in the first time electroplating processes and second of electroplating processes, stirring rate be 600~
2600r/min；Agitating mode includes magnetic force Stirring, plating solution circulation stirring, air stirring, ultrasonic agitation or movable cathode.
The size of stirring rate can influence the dispersing uniformity of plating solution and eliminate the degree of concentration polarization, and then influence the surface of coating
Pattern.Strong stirring can be improved the current density upper limit, improve current efficiency.
In the first time electroplating processes electric source modes be constant current, temperature be 40~60 DEG C, average current density be 0.5~
10A/dm2, electroplating time is 1~10min；
In second of electroplating processes electric source modes be constant current, temperature be 15~60 DEG C, average current density be 0.5~
10A/dm2, electroplating time is 10~120min；
Preferably, the first time electroplating processes and second electroplating processes using constant current, high frequency forward pulse current or
High frequency Bipolar pulse current, wherein the constant current average current density is 0.5~10A/dm2；The high frequency forward pulse current
Specific process parameter are as follows: 0.1~1ms of conduction time, 0.4~1ms of power-off time, 500~2000Hz of pulse frequency, pulse duration
Than 10~30%, 0.5~10A/dm of average current density2；The high frequency bidirectional pulse power supply, specific process parameter are as follows: be powered
0.1~1ms of time, 0.4~1ms of power-off time, pulse 0.5~2ms of make and break period, 500~2000Hz of pulse frequency, pulse account for
Empty ratio 10~30%, 0.5~10A/dm of Mean Forward Current density2, reversed 0.05~1A/dm of average current density2, when plating
Between 10~120min.
The nanometer crystal zinc plating of high frequency forward pulse current preparation is compared to nanometer crystal zinc plating prepared by DC electrodeposition
Crystallite dimension is more tiny.High frequency Bipolar pulse current uses the crystallite dimension and high frequency forward direction arteries and veins of the nanometer crystal zinc plating of preparation
The crystallite dimension for rushing the nanometer crystal zinc plating prepared under electric current is close, but its surface appearance compares direct current and high frequency forward direction arteries and veins
The zinc coating for rushing power supply preparation is more smooth.
Compared with the existing technology, the present invention has the advantage that
1. nanometer crystal zinc plating produced by the present invention falls off for bend test 20 times through 90 ° without zinc；Meet national standard
Requirement of the coating adhesive strength test method to electro-deposition and chemical deposition coating on GB5270-200X metallic matrix.
2. Nano-Zinc electroplating technology of the invention can be obviously improved corrosion resisting property of the magnesium alloy in body fluid, coating is in mould
Corrosion potential in quasi- body fluid can reduce about 30%, and 1/4 or so of corrosion rate when corrosion rate is only not electroplated.
3. magnesium alloy nanometer electrodeposition technology of the invention, good through amplification test proving effect, can be in area
10dm2Mg alloy surface prepare uniform nanometer crystal zinc plating, crystallite dimension and corrosion resisting property are kept constant.
Detailed description of the invention
Fig. 1 is the surface topography and EDS map for the magnesium alloy implant material that surface is covered with nanometer crystal zinc plating, wherein (a)
It is composed for the surface topography and EDS of AZ31 magnesium alloy, is (b) surface topography of zinc pre-plating layer and EDS spectrum, (c) is plated for nanocrystalline zinc
Surface topography and the EDS spectrum of layer.
Fig. 2 is open circuit potential curve of the electrodeposited Nano-Zinc front and back of AZ31 magnesium alloy in simulated body fluid.
Fig. 3 is Tafel curve of the electrodeposited Nano-Zinc front and back of AZ31 magnesium alloy in simulated body fluid.
Fig. 4 is the surface topography that nanometer crystal zinc plating is made under different current-modes: wherein a and d is DC electrodeposition system
Obtain the surface topography of nanometer crystal zinc plating；B and e is the surface shape that nanometer crystal zinc plating is made in the electro-deposition of high frequency forward pulse current
Looks；C and f is the surface topography that nanometer crystal zinc plating is made in the electro-deposition of high frequency Bipolar pulse current.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
Nano-Zinc electroplating technology of the invention specific steps are as follows:
One, the magnesium alloy to be plated having a size of 2.5cm × 2.5cm is cleaned by ultrasonic in acetone soln 8min, then spent
Ionized water rinses, premenstrual treated Mg alloy surface pattern, shown in (a) as shown in figure 1；
Two, derusting 1min is carried out to matrix using ethanedioic acid (15g/L) at room temperature, is then rushed with deionized water
It washes；
Three, zinc pre-plating solution is prepared by zinc sulfate 35g/L, sodium pyrophosphate 145g/L and sodium fluoride 10g/L, solvent is deionization
Water, adjusting pH by sodium hydroxide is 9~11；
The zinc pre-plating solution contains zinc sulfate, sodium pyrophosphate and sodium fluoride, and effectively magnesium can be inhibited to Zn2+Displacement make
With in zinc transition zone of the Mg alloy surface one layer crystal particle size of formation in micro-scaled range, to ensure that subsequent electricity is heavy
Product nanometer crystal zinc plating is gone on smoothly；
Four, press zinc sulfate 100g/L, boric acid 20g/L and grain refiner 1g/L preparation of nano zinc plating solution, solvent be go from
Sub- water, adjusting pH by dilute sulfuric acid is 1~2；
Specifically, the grain refiner is the amphoteric ion type macromolecule amide groups chemical combination that molecular weight is 500-1200 ten thousand
Object is synthesized with acrylyl oxy-ethyl-trimethyl salmiac by aqueous free radical copolymerization by acrylamide；
In the Nano-Zinc plating solution, zinc sulfate, can be under the premise of guaranteeing current density under the concentration of 100g/L as main salt
Obtain the suitable Nano-Zinc of crystallite dimension；Boric acid plays the role of stable bath pH value as pH buffer in the plating process；
Grain refiner can effectively promote into nuclear reaction under the concentration of 1g/L, inhibit nucleus growth；The plating solution has dispersion energy
Power and the feature that covering power is good, conductivity is moderate, composition is simple, convenient for safeguarding, the nano-carbon material suitable for various structures
Plating, and noxious material is free of, it is environmentally protective；
Five, by warp Step 1: the matrix of two processing, which is put into the zinc pre-plating solution obtained through step 3, carries out electricity for the first time
Plating, is then cleaned with deionized water；Specific process parameter is electroplated are as follows: temperature is 25 DEG C, and electric source modes are constant current, and average current is close
Degree is 3A/dm2, electroplating time 10min, using magnetic agitation, stirring rate 2000r/min；Prepared coarse-grain zinc is pre-
Coating surface morphology, as shown in (b) in attached drawing 1, crystal grain is in laminar structured, and for size at 1~10 μm, thickness is about 10 μ
m；
Six, the matrix handled through step 5 is put into the Nano-Zinc plating solution obtained through step 4 and carries out second of electricity
Plating, specific process parameter are as follows: temperature is 25 DEG C, and electric source modes are constant current, average current density 3A/dm2, electroplating time is
60min, using magnetic agitation, stirring rate 2000r/min；Then it cleaned, dried up with deionized water, that is, complete nanocrystalline zinc
The preparation of coating, the surface topography of obtained nanometer crystal zinc plating, shown in (c) as shown in figure 1, crystal grain is in rice-shaped knot
Structure, size is in 100nm hereinafter, thickness is about 70 μm.Coating obtained falls off for bend test 20 times through 90 ° without zinc, with magnesium alloy
Matrix is well combined.
The corrosion resisting property of coating is tested, as a result as shown in Fig. 2, corrosion of the AZ31 magnesium alloy in simulated body fluid
Potential be about -1461mV, and corrosion potential of the nanometer crystal zinc plating made from the present embodiment in simulated body fluid about -
1092mV, it is clear that electro-deposition Nano-Zinc can be obviously improved the electrochemical stability of magnesium alloy；Separately as shown in figure 3, by this
Corrosion rate (37 μ A cm after the preparation method electro-deposition nanometer crystal zinc plating of invention in simulated body fluid-2) it is only without electricity
Corrosion rate (164 μ A cm when plating-2) 1/4 or so.
Embodiment 2
Plating for the first time and second of plating are permanent using high frequency forward pulse current substitution in the present embodiment step 5 and six
Stream, specific process parameter are as follows: conduction time is 0.2ms in plating for the first time and second of plating, and power-off time is
0.8ms, pulse frequency are 1000Hz, and pulse duty factor is 20%, and average current density is 3A/dm2, it is electroplated for the first time
Time is 10min, and second of electroplating time is 60min；Remaining step and condition are referring to embodiment 1.Prepared nanocrystalline zinc
The surface topography of coating compares the crystalline substance of DC electrodeposition nanometer crystal zinc plating (a and d in Fig. 4) as shown in the b and e in Fig. 4
Grain is more tiny, surface is more smooth, is more advantageous to the corrosion for resisting fluid environment.
Embodiment 3
Plating for the first time and second of plating are permanent using high frequency Bipolar pulse current substitution in the present embodiment step 5 and six
Stream, specific process parameter are as follows: conduction time is 0.2ms in plating for the first time and second of plating, and power-off time is
0.8ms, pulse frequency are 1000Hz, and pulse duty factor is 20%, and Mean Forward Current density is 3A/dm2, reversed flat
Equal current density is 0.3A/dm2, the positive pulse duty cycle is 100ms, and the back pulse duty cycle is 10ms, for the first time
Electroplating time is 10min, and second of electroplating time is 60min；Remaining step and condition are referring to embodiment 1.Prepared nanometer
The surface topography of brilliant zinc coating, as shown in the c and f in Fig. 4, compared to high frequency direct impulse electro-deposition nanometer crystal zinc plating (in Fig. 4
B and e) be equally beneficial for improving to corrosion in body fluid though crystallite dimension is more smooth without further refining its surface
Resilience, can be according to the demand in actual use to nanometer crystal zinc plating active time, by deposition current mould
The selection of formula and parameter regulates and controls the crystallite dimension and surface roughness of nanometer crystal zinc plating, so that it is nanocrystalline to reach control
Corrosion rate of the zinc coating in fluid environment.
Embodiment 4
The present embodiment is unlike the first embodiment: substituted having a size of 2.5cm with the magnesium alloy having a size of 5dm × 2dm ×
The magnesium alloy of 2.5cm.Remaining parameter and step are referring to embodiment 1.Nanometer crystal zinc plating effect same made from amplification test is good
Good, the data of zinc crystallite dimension and corrosion resisting property and embodiment 1 are coincide, it was demonstrated that the present invention can be used for large scale preparation.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (5)
1. a kind of method in magnesium alloy implant material surface electro-deposition biocompatibility Nano-Zinc, which is characterized in that including with
Lower step:
Magnesium alloy implant material matrix is added in zinc pre-plating solution and carries out first time electroplating processes, Nano-Zinc plating is added after washing
Second of electroplating processes is carried out in liquid, then washes the magnesium alloy implantation for obtaining being covered with coarse-grain zinc pre-plating layer and nanometer crystal zinc plating
Material；
Temperature is 40~60 DEG C in the first time electroplating processes, and electroplating time is 1~10min；
Temperature is 15~60 DEG C in second of electroplating processes, and electroplating time is 10~120min；
The ingredient of the zinc pre-plating solution are as follows: 5~20g/L of 20~100g/L of zinc sulfate, 60~300g/L of sodium pyrophosphate and sodium fluoride,
Solvent is water；The zinc pre-plating solution pH is 9~11；
The Nano-Zinc electroplating bath components are as follows: 0.3~3g/ of 50~300g/L of zinc sulfate, 10~40g/L of boric acid and grain refiner
L, solvent are water；The Nano-Zinc electroplate liquid pH is 1~3；
The coarse-grain zinc pre-plating layer crystallite dimension is 1~10 μm, with a thickness of 1~10 μm；The nanometer crystal zinc plating crystallite dimension
For 30~100nm, with a thickness of 10~100 μm, roughness is less than 230nm.
2. a kind of side in magnesium alloy implant material surface electro-deposition biocompatibility Nano-Zinc according to claim 1
Method, which is characterized in that the grain refiner is one of following compound:
A) molecular weight is the amphoteric ion type macromolecule amido compounds of 500-1200 ten thousand；
B) molecular weight is the non-ionic macromolecule amido compounds of 200-1500 ten thousand；
C) molecular weight is the anionic macromolecule amido compounds of 300-2200 ten thousand；
D) molecular weight is the cationic high-molecular amido compounds of 500-1200 ten thousand.
3. according to claim 1 or 2 a kind of in magnesium alloy implant material surface electro-deposition biocompatibility Nano-Zinc
Method, which is characterized in that the grain refiner passes through aqueous solution by acrylamide and acrylyl oxy-ethyl-trimethyl salmiac
Free radical copolymerization synthesis.
4. a kind of side in magnesium alloy implant material surface electro-deposition biocompatibility Nano-Zinc according to claim 1
Method, which is characterized in that be stirred in the first time electroplating processes and second of electroplating processes, stirring rate be 600~
2600r/min。
5. a kind of side in magnesium alloy implant material surface electro-deposition biocompatibility Nano-Zinc according to claim 1
Method, which is characterized in that the first time electroplating processes and second of electroplating processes use constant current, high frequency forward pulse current or height
Frequency Bipolar pulse current, wherein the constant current average current density is 0.5~10A/dm2；The high frequency forward pulse current tool
Body technology parameter are as follows: 0.1~1ms of conduction time, 0.4~1ms of power-off time, 500~2000Hz of pulse frequency, pulse duty factor
10~30%, 0.5~10A/dm of average current density2；The high frequency Bipolar pulse current specific process parameter are as follows: conduction time
0.1~1ms, 0.4~1ms of power-off time, pulse 0.5~2ms of make and break period, 500~2000Hz of pulse frequency, pulse duty factor
10~30%, 0.5~10A/dm of Mean Forward Current density2, reversed 0.05~1A/dm of average current density2, electroplating time 10
~120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810761659.7A CN109082689B (en) | 2018-07-12 | 2018-07-12 | Surface is covered with magnesium alloy implant material of nanometer crystal zinc plating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810761659.7A CN109082689B (en) | 2018-07-12 | 2018-07-12 | Surface is covered with magnesium alloy implant material of nanometer crystal zinc plating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109082689A CN109082689A (en) | 2018-12-25 |
| CN109082689B true CN109082689B (en) | 2019-11-19 |
Family
ID=64837568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810761659.7A Active CN109082689B (en) | 2018-07-12 | 2018-07-12 | Surface is covered with magnesium alloy implant material of nanometer crystal zinc plating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109082689B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111603615B (en) * | 2020-06-08 | 2022-07-01 | 郑州大学 | Controllable degradable high-strength magnesium-based composite stent composite coating and preparation method thereof |
| CN113789554B (en) * | 2021-08-16 | 2022-12-02 | 华中科技大学 | Magnesium alloy with protective coating and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469269A (en) * | 2013-09-16 | 2013-12-25 | 天津大学 | Method for improving corrosion resistance of magnesium-based biomedical material |
| CN107814869A (en) * | 2017-11-10 | 2018-03-20 | 齐鲁工业大学 | Polymer/stannic oxide/graphene nano composite aquogel that is tough and tensile, stretchable, compressible and having fabulous self-healing properties |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7704366B2 (en) * | 2005-08-17 | 2010-04-27 | Trevor Pearson | Pretreatment of magnesium substrates for electroplating |
-
2018
- 2018-07-12 CN CN201810761659.7A patent/CN109082689B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469269A (en) * | 2013-09-16 | 2013-12-25 | 天津大学 | Method for improving corrosion resistance of magnesium-based biomedical material |
| CN107814869A (en) * | 2017-11-10 | 2018-03-20 | 齐鲁工业大学 | Polymer/stannic oxide/graphene nano composite aquogel that is tough and tensile, stretchable, compressible and having fabulous self-healing properties |
Non-Patent Citations (4)
| Title |
|---|
| "AZ31B镁合金的生物医用表面改性研究";颜延亭，;《AZ31B镁合金的生物医用表面改性研究》;20100815(第 08 期);E080-10 * |
| "Insight into the Role and Its Mechanism of Polyacrylamide as an Additive in Sulfate Electrolytes for Nanocrystalline Zinc Electrodeposition";Qingyang Li等，;《Journal of The Electrochemical Society》;20160127;第163卷(第5期);第D127-D132 页 * |
| "Pulse reverse electrodeposition and characterization of nanocrystalline zinc coatings";Qingyang Li 等，;《RSC Adv.》;20141002(第4期);第212-215页 * |
| "镁合金表面电沉积锌的技术探索";张吉阜 等，;《2007 年全 国电子电镀学术年会暨绿色电子制造技术论坛论文集》;20071101;第52562–52570页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109082689A (en) | 2018-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Karimzadeh et al. | A review of electrodeposited Ni-Co alloy and composite coatings: Microstructure, properties and applications | |
| Nakamura et al. | Effects of saccharin and aliphatic alcohols on the electrocrystallization of nickel | |
| El-Sherik et al. | Microstructural evolution in pulse plated nickel electrodeposits | |
| Sajjadnejad et al. | Microstructure-corrosion resistance relationship of direct and pulse current electrodeposited Zn-TiO2 nanocomposite coatings | |
| Pavlatou et al. | Synergistic effect of 2-butyne-1, 4-diol and pulse plating on the structure and properties of nickel nanocrystalline deposits | |
| Li et al. | Ultrasonic-assisted electrodeposition of Ni-Cu/TiN composite coating from sulphate-citrate bath: Structural and electrochemical properties | |
| Rudnik et al. | Effect of gluconate addition on the electrodeposition of nickel from acidic baths | |
| Tian et al. | Microstructure and properties of nanocrystalline nickel coatings prepared by pulse jet electrodeposition | |
| Tuaweri et al. | A study of process parameters for zinc electrodeposition from a sulphate bath | |
| Ghaziof et al. | Electrochemical studies of sol-enhanced Zn–Ni–Al2O3 composite and Zn–Ni alloy coatings | |
| CN101717951B (en) | Cathode-catalyzed electrode producing method in coal electrolyzing, hydrogenizing and liquefying process | |
| CN109082689B (en) | Surface is covered with magnesium alloy implant material of nanometer crystal zinc plating and preparation method thereof | |
| Hansal et al. | Pulse-electrodeposited NiP–SiC composite coatings | |
| Kamnerdkhag et al. | The effects of duty cycles on pulsed current electrodeposition of ZnNiAl2O3 composite on steel substrate: Microstructures, hardness and corrosion resistance | |
| Ved et al. | Composition and corrosion behavior of iron-cobalt-tungsten | |
| Deo et al. | Direct and pulsed current electrodeposition of Zn-Mn coatings from additive-free chloride electrolytes for improved corrosion resistance | |
| CN109082654A (en) | A method of zinc oxide nanowire film is prepared based on nanometer crystal zinc plating hydro-thermal reaction | |
| CN100588748C (en) | High-strength high-plasticity nano nickel and its plating solvent and preparation method | |
| El-Feky et al. | Electrodeposited Ni and Ni-Co alloys using cysteine and conventional ultrasound waves | |
| CN105862096B (en) | A kind of preparation method of FHA bioactivity coatings | |
| Larson et al. | Recent advances in pulsed current electrodeposition: a brief review | |
| CN101717950B (en) | Method for preparing anode-catalyzed electrode for electrolyzing slurry coal | |
| Mohanty et al. | Effect of pyridine and its derivatives on the electrodeposition of nickel from aqueous sulfate solutions Part I: current efficiency, surface morphology and crystal orientation | |
| Vasilakopoulos et al. | Electrochemical codeposition of PMMA particles with zinc | |
| Mahdavi et al. | Effect of TiO2 nano-particles on corrosion behavior of Co-Cr alloy coatings in simulated body fluid |
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 |