CN109402544A - A method of improving the resistance to bioerodible of magnesium alloy bone plate - Google Patents
A method of improving the resistance to bioerodible of magnesium alloy bone plate Download PDFInfo
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- CN109402544A CN109402544A CN201811319385.2A CN201811319385A CN109402544A CN 109402544 A CN109402544 A CN 109402544A CN 201811319385 A CN201811319385 A CN 201811319385A CN 109402544 A CN109402544 A CN 109402544A
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- Prior art keywords
- bone plate
- magnesium alloy
- alloy bone
- laser
- resistance
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/80—Cortical plates, i.e. bone plates; Instruments for holding or positioning cortical plates, or for compressing bones attached to cortical plates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Abstract
The present invention relates to a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate, S1: establishing magnesium alloy bone plate finite element model, and identified sign concentrates position；S2: grinding magnesium alloy bone plate sand for surface paper, and using dry after acetone cleaning；S3: pasting aluminium foil absorbed layer for magnesium alloy bone plate stress concentration portion position and be clamped in the robot of laser peening system, sets laser parameter and shot-peening path, concentrates position to carry out shot peening strengthening stress；S4: the magnesium alloy bone plate after shot-peening is placed in ultrasonic cleaning in dehydrated alcohol or acetone, is then dried with nitrogen；S5: the magnesium alloy bone plate after drying is dipped in electrolyte as anode, using differential arc oxidation stainless steel electrolytic cell as cathode, using constant voltage mode, electrolyte reacts 5min under the conditions of being lower than 40 DEG C, after take out bone plate, it is dry after being rinsed using deionized water.The laser peening method that the present invention uses can effectively promote the resistance to biological corrosion performance of magnesium alloy.
Description
Technical field
The present invention relates to the composite modified fields of metal surface laser, refer in particular to a kind of resistance to biological corrosion of raising magnesium alloy bone plate
The method of property.
Background technique
Magnesium alloy mechanical performance is quite similar with skeleton and biocompatibility is excellent, has in biologic medical field
Wide application prospect.The backing material for selecting magnesium alloy to restore as postoperative bone, it is possible to reduce stress shielding effect reduces
The occurrence probability of chronic inflammation.Simultaneously because the biodegradable performance of magnesium alloy, the second operation after can avoid bone healing.
However, since corrosion phenomenon is serious in body fluid for magnesium alloy, and the hydrogen that Corrosion Behaviors of Magnesium Alloys generates can cause complication, limit it
Clinical application.Many schemes have been proposed at present to improve the corrosion resistance of magnesium alloy, such as with biodegradable polymerization
Object coating, alloyage process etc..The shortcomings that above method, is that they cannot be by Optimal Parameters come control corrosion rate rate, and gives birth to
Production. art is complicated.
Laser peening reinforcement technique, in workpiece surface, is made using high power density, short-pulse laser induction shock wave
Forced plasticity deforming occurs in a very short period of time for test specimen surface layer.Laser peening strengthen macroscopically show as material surface it is higher,
Deeper residual compressive stress shows as the formation of the lattice defects such as refinement and dislocation, the twin of surface layer grain on microcosmic.Material
The residual compressive stress and lattice defect generated in material is an important factor for influencing corrosion rate, parameter appropriate to be selected to carry out laser
The accurate control to corrosion rate may be implemented in bead.
Hydroxyapatite (HA) is naturally occurring apatite mine substance, due to the structure and chemical phase of itself and bone mineral
Excellent biocompatibility and bioactivity are shown like property, is often used as biomedical material.Hydroxyapatite coating layer exists
It is degradable in physiological environment, and shows good early stage interaction between implantation material and tissue.To magnesium
And its common preparation method of hydroxyapatite coating layer includes electro-deposition, aerosol deposition and chemical solution deposition etc. on alloy.
Summary of the invention
It can not be mentioned in bone tissue healing stage to overcome existing magnesium alloy bone plate to corrode too fast in environment in vivo
For the defect of sufficient intensity, the present invention provides a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate, can be widely applied
In the surface treatment of magnesium alloy materials, magnesium alloy parts is made to obtain better corrosion resistance.
For achieving the above object, the technical scheme adopted by the invention is as follows: a kind of resistance to biology of raising magnesium alloy bone plate
Corrosive method, comprising the following steps: S1: magnesium alloy bone plate finite element model is established, its stress and determination are analyzed
Stress concentration portion position；S2: grinding magnesium alloy bone plate sand for surface paper, and using dry after acetone cleaning；S3: by magnesium alloy
Bone plate stress concentration portion position is pasted aluminium foil absorbed layer and is clamped in the robot of laser peening system, setting laser parameter and
Shot-peening path starts laser peening system, concentrates position to carry out shot peening strengthening stress；S4: by the magnesium alloy synthetism after shot-peening
Plate is placed in ultrasonic cleaning in dehydrated alcohol or acetone, is then dried with nitrogen；S5: by the magnesium alloy bone plate after drying
It is dipped in electrolyte as anode, using differential arc oxidation stainless steel electrolytic cell as cathode, using constant voltage mode, electrolyte is being lower than
React 5min under the conditions of 40 DEG C, after take out bone plate, it is dry after being rinsed using deionized water.In above scheme, step S3
In, the laser parameter of laser peening are as follows: optical maser wavelength 1064nm, laser pulse width 10-30ns, laser energy density 1-
1.25GW/cm2, spot diameter 1-2mm, for laser facula using without continuous overlapping arrangement is spaced, adjacent spots coverage rate is 67-
75%.In above scheme, in step S3, laser facula overlay area center is overlapped with screw hole region of stress concentration center, laser
Shot-peening peripheral distance region of stress concentration center is not less than 3.5mm, and beam spot scans direction is in Z-shaped by export-oriented region of stress concentration
Trend.In above scheme, in step S3, laser facula is in three layers of gradient distribution, and the 1st to the 3rd time in bone plate width direction
Hot spot row/column number is respectively x, 0.5x, 0.25x, and wherein x is size of the screw hole apart from bone plate edge.
In above scheme, in step S5, differential arc oxidation electrolyte solution is prepared by deionized water, consisting of Na2SiO3:
10-15g/L, Na3PO4: 2-3g/L, NaOH:2-4g/L, glycerol: 5-10mL/L.
In above scheme, in step S5, the hydroxyapatite concentration being added in electrolyte is 0.5-2g/ L, hydroxyl phosphorus
The average-size of lime stone powder is 0.25-0.5 μm；Electrolyte should be sonic oscillation 10-20 minutes before differential arc oxidation, to ensure
Hydroapatite particles are well dispersed into entire electrolyte.
In above scheme, in step S5, the equipment for differential arc oxidation includes the pulse power, electrolytic cell and stirring cooling system
System can automatically control electrolyte temperature lower than 40 DEG C.
In above scheme, in step S5, using constant voltage mode, the electrical parameter that is related to are as follows: 400V anode voltage, 80V cathode
Voltage, 1500Hz frequency and 50% duty ratio.
The beneficial effects of the present invention are: (1) laser peening intensive treatment and bioactivity coatings is prepared work by this method
Skill combines, and laser peening strengthens the mechanics mechanical performance and corrosion resistance that magnesium alloy can be improved, differential arc oxidation preparation
Bioactivity coatings can be further improved the resistance to biological corrosion performance of magnesium alloy, therefore to magnesium alloy bone plate in medical bio
Application in environment is of great significance.(2) residual compressive stress and microstructure of laser peening induction are conducive to the viscous of coating
Knotting strength, and prepare hydroxyapatite coating layer simple process using differential arc oxidation, at the same the hydroxyl apatite coating for preparing and
Magnesium alloy bone plate can degrade in physiological environment, be not necessarily to second operation.(3) this method parameter is controllable, and technique is more flexible,
And process velocity is faster, production process does not have harmful substance generation, is expected to be applied in actual production.
Detailed description of the invention
Fig. 1 is the flow chart of the method for the present invention.
Fig. 2 is the magnesium alloy bone plate structural schematic diagram of embodiment.
Fig. 3 is the policy map that Fig. 2 dotted portion region of stress concentration uses laser peening.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the invention will be further described.
The process of the present invention " a method of improve the resistance to bioerodible of magnesium alloy bone plate " is as shown in Figure 1, main packet
Include following steps.
(1) as shown in Fig. 2, establishing ZK60 magnesium alloy bone plate finite element model, analyzing it, stress is simultaneously in human body
Identified sign concentrates position.
(2) 280#, 500#, 800#, 1200#, 1500# are used respectively, and 2000# sand paper polishing ZK60 magnesium alloy bone plate is gone
It is placed in progress ultrasonic cleaning 10min in acetone except oxide on surface and surface scratch, then by bone plate, then uses deionized water
It washes and dries.
(3) magnesium alloy bone plate after the drying need to strengthen position and paste aluminium foil absorbed layer and be clamped in laser peening system
Robot on, set laser parameter, wherein laser wavelength is 1064nm, laser pulse width 20ns, and laser energy density is
1.25GW/cm2, spot diameter 1.5mm, laser facula uses without being spaced continuous overlapping arrangement, and adjacent spots coverage rate is
67%, laser facula overlay area center is overlapped with screw hole region of stress concentration center, and laser peening peripheral distance stress is concentrated
Region is 3.5mm, as shown in figure 3, laser facula is in three layers of gradient distribution, the 1st to the 3rd hot spot in bone plate width direction
Columns is respectively 8,4,2, and beam spot scans direction is moved towards by export-oriented region of stress concentration in Z-shaped.
(4) the magnesium alloy bone plate after shot-peening is placed in dehydrated alcohol or acetone after ultrasonic cleaning and is done with nitrogen
It is dry.
(5) bone plate in step (4) after surface laser impact is strengthened is dipped in electrolyte as anode, with the differential of the arc
Stainless steel electrolytic cell is aoxidized as cathode, using WHD-30 micro-arc oxidation device, setting electrical parameter is 400V anode voltage, 80V
Cathode voltage, 1500Hz frequency and 50% duty ratio, using constant voltage mode, starting device carries out coating deposition, at room temperature instead
5min is answered, is spontaneously dried after taking-up is rinsed with deionized water after reaction.
Further, differential arc oxidation electrolyte solution is prepared by deionized water in step (5), is mainly organized as Na2SiO3
(10g/L), Na3PO4(3g/L), NaOH(2g/L) and glycerol (10mL/L).
Further, the concentration for the HA being added in electrolyte in step (5) is selected as 0.6g/L, hydroxyapatite powder
Average-size is 0.5 μm.Electrolyte should before differential arc oxidation sonic oscillation 10 minutes, to ensure that hydroapatite particles are good
Ground is dispersed in entire electrolyte.
Further, it is cooled down for the equipment (WHD-30) of differential arc oxidation by the pulse power, electrolytic cell and stirring in step (5)
System composition can be automatically controled electrolyte temperature lower than 40 DEG C.
Through detecting, there is extremely strong resistance to bioerodible, Neng Gouguang using magnesium alloy bone plate made from above-described embodiment
It is general to be applied to biologic medical field.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (8)
1. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate, which comprises the following steps:
S1: establishing magnesium alloy bone plate finite element model, analyzes its stress and identified sign concentrates position；
S2: grinding magnesium alloy bone plate sand for surface paper, and using dry after acetone cleaning；
S3: aluminium foil absorbed layer is pasted into magnesium alloy bone plate stress concentration portion position and is clamped in the robot of laser peening system
On, laser parameter and shot-peening path are set, laser peening system is started, concentrates position to carry out shot peening strengthening stress；
S4: the magnesium alloy bone plate after shot-peening is placed in ultrasonic cleaning in dehydrated alcohol or acetone, is then done with nitrogen
It is dry；
S5: the magnesium alloy bone plate after drying is dipped in electrolyte as anode, using differential arc oxidation stainless steel electrolytic cell as
Cathode, using constant voltage mode, electrolyte differential arc oxidation under the conditions of being lower than 40 DEG C reacts 5min, after take out bone plate, make
It is dry after being rinsed with deionized water.
2. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate according to claim 1, which is characterized in that step
In rapid S3, the laser parameter of laser peening are as follows: optical maser wavelength 1064nm, laser pulse width 10-30ns, laser energy density 1-
1.25GW/cm2, spot diameter 1-2mm, for laser facula using without continuous overlapping arrangement is spaced, adjacent spots coverage rate is 67-
75%。
3. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate according to claim 1, which is characterized in that step
In rapid S3, laser facula overlay area center is overlapped with screw hole region of stress concentration center, laser peening peripheral distance stress
Concentrated area center is not less than 3.5mm, and beam spot scans direction is moved towards by export-oriented region of stress concentration in Z-shaped.
4. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate according to claim 1, which is characterized in that
In step S3, laser facula be in three layers of gradient distribution, the 1st to the 3rd time in bone plate width direction hot spot row/column number be respectively
X, 0.5x, 0.25x, wherein x is size of the screw hole apart from bone plate edge.
5. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate according to claim 1, which is characterized in that step
In rapid S5, differential arc oxidation electrolyte solution is prepared by deionized water, consisting of Na2SiO3:10-15g/L, Na3PO4: 2-3g/L,
NaOH:2-4g/L, glycerol: 5-10mL/L.
6. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate according to claim 1, which is characterized in that step
In rapid S5, the hydroxyapatite concentration being added in electrolyte is 0.5-2g/ L, and the average-size of hydroxyapatite powder is
0.25-0.5μm；Electrolyte should be sonic oscillation 10-20 minutes before differential arc oxidation, to ensure hydroapatite particles well
It is dispersed in entire electrolyte.
7. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate according to claim 1, which is characterized in that step
In rapid S5, the equipment for differential arc oxidation includes the pulse power, electrolytic cell and stirring cooling system, can automatically control electrolyte
Temperature is lower than 40 DEG C.
8. a kind of method for improving the resistance to bioerodible of magnesium alloy bone plate according to claim 1, which is characterized in that step
In rapid S5, using constant voltage mode, the electrical parameter that is related to are as follows: 400V anode voltage, 80V cathode voltage, 1500Hz frequency and 50%
Duty ratio.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811319385.2A CN109402544A (en) | 2018-11-07 | 2018-11-07 | A method of improving the resistance to bioerodible of magnesium alloy bone plate |
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| CN201811319385.2A CN109402544A (en) | 2018-11-07 | 2018-11-07 | A method of improving the resistance to bioerodible of magnesium alloy bone plate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110093650A (en) * | 2019-04-30 | 2019-08-06 | 西安建筑科技大学 | A kind of preparation method of high-wearing feature high-hardness titanium alloy composite bushing |
| CN110952122A (en) * | 2019-11-07 | 2020-04-03 | 西安工业大学 | Preparation method of heat-insulating, corrosion-resistant and fatigue-resistant composite protective layer made of metal and composite material |
| CN113512746A (en) * | 2021-07-08 | 2021-10-19 | 济南大学 | Preparation method of medical titanium alloy bone plate surface nano coating |
| WO2023240729A1 (en) * | 2022-06-13 | 2023-12-21 | 江苏大学 | Absorption layer-adjustable laser peening forming device and method |
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| CN101032632A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | Material for bone tissue engineering scaffold and making method thereof |
| CN106119750A (en) * | 2016-06-22 | 2016-11-16 | 浙江工业大学 | Laser-impact and differential arc oxidation are combined in Mg alloy surface and prepare biological coating method |
| CN106267332A (en) * | 2016-08-29 | 2017-01-04 | 上海交通大学 | A kind of porous magnesium alloy is as carrier application medically |
| CN106902390A (en) * | 2016-12-30 | 2017-06-30 | 浙江工业大学 | A kind of titanium alloy is implanted into composite material and its preparation and application |
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- 2018-11-07 CN CN201811319385.2A patent/CN109402544A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| CN101032632A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | Material for bone tissue engineering scaffold and making method thereof |
| CN106119750A (en) * | 2016-06-22 | 2016-11-16 | 浙江工业大学 | Laser-impact and differential arc oxidation are combined in Mg alloy surface and prepare biological coating method |
| CN106267332A (en) * | 2016-08-29 | 2017-01-04 | 上海交通大学 | A kind of porous magnesium alloy is as carrier application medically |
| CN106902390A (en) * | 2016-12-30 | 2017-06-30 | 浙江工业大学 | A kind of titanium alloy is implanted into composite material and its preparation and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110093650A (en) * | 2019-04-30 | 2019-08-06 | 西安建筑科技大学 | A kind of preparation method of high-wearing feature high-hardness titanium alloy composite bushing |
| CN110952122A (en) * | 2019-11-07 | 2020-04-03 | 西安工业大学 | Preparation method of heat-insulating, corrosion-resistant and fatigue-resistant composite protective layer made of metal and composite material |
| CN113512746A (en) * | 2021-07-08 | 2021-10-19 | 济南大学 | Preparation method of medical titanium alloy bone plate surface nano coating |
| WO2023240729A1 (en) * | 2022-06-13 | 2023-12-21 | 江苏大学 | Absorption layer-adjustable laser peening forming device and method |
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Application publication date: 20190301 |