CN101565825B - Treatment method of magnesium or magnesium alloy surface - Google Patents
Treatment method of magnesium or magnesium alloy surface Download PDFInfo
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- CN101565825B CN101565825B CN2009100721771A CN200910072177A CN101565825B CN 101565825 B CN101565825 B CN 101565825B CN 2009100721771 A CN2009100721771 A CN 2009100721771A CN 200910072177 A CN200910072177 A CN 200910072177A CN 101565825 B CN101565825 B CN 101565825B
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Abstract
A treatment method of magnesium or magnesium alloy surface relates to the treatment method of metal material surface and solves the problems of the existing magnesium or magnesium alloy in application, such as severe mechanical property loss, excessive degradation speed and local pH value increase caused by the generation of large numbers of hydrogen bubbles accompanied with the degradation process. The method comprises the steps of: firstly, washing and drying parent metal; secondly, using NaOH solution for treating the parent metal after washing; and thirdly, forming a dicalcium phosphate dehydrate layer on the surface of the parent metal. Adopting the NaOH solution for treatment, the method can adjust the magnesium or magnesium alloy surface state and transplants parent material for forming hydroxylapatite into a human body, the mechanical property loss is reduced, the degradation speed is slowed, and the pH value is not changed basically; and the method has simple technique and canform uniform hydroxylapatite on the surface of the parent material, without the falling-off phenomenon.
Description
Technical field
The present invention relates to the treatment process of metal material surface.
Background technology
Stainless steel and titanium alloy are as the widespread use of os osseum tissue implanting material clinically.But, so not only bring misery, and cost is very high to the patient because it can not degrade and need second operation to take out.Magnesium and magnesium alloy thereof are because of can be used as the degradable hard tissue implanting material, the magnesium ion that degraded product has biocompatibility and release is useful to tissue growth, especially because magnesium and magnesium alloy thereof have lower Young's modulus, approaching with people's bone more, to significantly reduce stress-shielding effect, so the mechanical property of magnesium and magnesium alloy thereof has been well positioned to meet the requirement as orthopedic implanting material, but at present but there are mechanical property loss serious (because of seriously corroded causes) in magnesium and magnesium alloy thereof on using, cause too fast the reaching of degradation speed supervening a large amount of bubble hydrogens in the degradation process fast, the problem that causes the local pH value to raise causes bad influence and is unfavorable for the recovery of osseous tissue the human body environment.
Summary of the invention
The present invention seeks to have in order to solve existing magnesium and magnesium alloy thereof that the mechanical property loss is serious, degradation speed is too fast and supervening the problem that a large amount of bubble hydrogens causes the local pH value to raise in the degradation process fast on using, and magnesium or treatment method on surface of magnesium alloy are provided.
First kind of magnesium or treatment method on surface of magnesium alloy are carried out according to the following steps: one, mother metal placed acetone or ethanol solution ultrasonic cleaning 1～10min, use distilled water flushing then 2 times, and dry again; Two, to place concentration be that 0.05～5.0mol/L, pH value are that 12～14 NaOH solution is handled 0.5～24h to the mother metal after step 1 is handled, and uses distilled water flushing then 2 times, again drying; Three, the mother metal after step 2 is handled is placed ca nitrate soln, be 5～7 in the pH value then, temperature is under 20～47 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, then leave standstill 10min～8h, the mother metal surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again, promptly finish the processing of magnesium or Mg alloy surface; Wherein mother metal is magnesium or magnesium alloy in the step 1.
Second kind of magnesium or treatment method on surface of magnesium alloy are carried out according to the following steps: one, mother metal placed acetone or ethanol solution ultrasonic cleaning 1～10min, use distilled water flushing then 2 times, and dry again; Two, the mother metal after step 1 is handled is placed ca nitrate soln, be 5～7 in the pH value then, temperature is under 20～47 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, then leave standstill 10min～8h, the mother metal surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again, promptly finish the processing of magnesium or Mg alloy surface; Wherein mother metal is magnesium or magnesium alloy in the step 1.
Treatment process of the present invention forms the dicalcium phosphate dihydrate layer with excellent anticorrosive performance at magnesium or Mg alloy surface, all can be in physiological environment solidity to corrosion and biological activity be greatly improved (cell can the magnesium after handling through the present invention or Mg alloy surface growth and can be dead), mechanical property loss reduction (magnesium or magnesium alloy after the present invention handles do not have corrosion phenomenon) degradation speed slows down, excludes the bubble hydrogen of generation and the pH value is remained unchanged substantially in degradation process in the implant into body.Surface treatment method technology among the present invention is simple, can obtain on magnesium or Mg alloy surface surface by nano particle form evenly, fine and close, surperficial flawless dicalcium phosphate dihydrate layer, no obscission, the one deck that obtains than the corrosion potential of dicalcium phosphate dihydrate layer by-1.6～-1.7V is elevated to-.09V, also there is passivation region in addition, even can reaches 0V.Current density is from-4A/cm
2Be reduced to-4.8～-5A/cm
2About.
Description of drawings
Fig. 1 is the polarization curve of treated material and unprocessed contrast material in the embodiment 17, and wherein "-" is the polarization curve of unprocessed contrast material, and " *-" is the polarization curve of treated material; Fig. 2 is 5000 times of electron-microscope scanning figure of treated material in the embodiment 17; Fig. 3 is 500 times of electron-microscope scanning figure that handle material without embodiment 17; The material that Fig. 4 forms hydroxyapatite for the Mg alloy surface after embodiment 29 is handled places the environment electron microscope photo scanning of cell growth behind the simulated body fluid.
Embodiment
Embodiment one: present embodiment magnesium or treatment method on surface of magnesium alloy are carried out according to the following steps: one, mother metal placed acetone or ethanol solution ultrasonic cleaning 1～10min, uses distilled water flushing then 2 times, and dry again; Two, to place concentration be that 0.05～5.0mol/L, pH value are that 12～14 NaOH solution is handled 0.5～24h to the mother metal after step 1 is handled, and uses distilled water flushing then 2 times, again drying; Three, the mother metal after step 2 is handled is placed ca nitrate soln, be 5～7 in the pH value then, temperature is under 20～47 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, then leave standstill 10min～8h, the mother metal surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again, promptly finish the processing of magnesium or Mg alloy surface; Wherein mother metal is magnesium or magnesium alloy in the step 1.
Employed reagent grade is analytical pure in the present embodiment.
In the present embodiment in the step 1 magnesium alloy be any alloy of magnesium.
Embodiment two: that present embodiment and embodiment one are different is ultrasonic cleaning 5min in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment and embodiment one are different is that to place concentration in the step 2 be that 0.5～4.0mol/L, pH value are that 12.5～13.5 NaOH solution is handled 3～20h.Other step and parameter are identical with embodiment two.
Embodiment four: present embodiment and embodiment one are different is that to place concentration in the step 2 be that 3.0mol/L, pH value are that 13 NaOH solution is handled 10h.Other step and parameter are identical with embodiment one.
Embodiment five: present embodiment and embodiment one are different is that to place concentration in the step 2 be that 2.0mol/L, pH value are that 12 NaOH solution is handled 8h.Other step and parameter are identical with embodiment one.
Embodiment six: what present embodiment and embodiment one to five were different is the bubble that step 2 preceding 0.5～3h in treating processes gets rid of surface in the solution.Other step and parameter are identical with embodiment one to five.
In the present embodiment in the solution surface bubble be H
2
Embodiment seven: what present embodiment and embodiment one to five were different is the bubble that step 2 preceding 1.5～2.5h in treating processes gets rid of surface in the solution.Other step and parameter are identical with embodiment one to five.
Embodiment eight: present embodiment and embodiment one to five are different be step 2 in treating processes before 2h get rid of the bubble on surface in the solution.Other step and parameter are identical with embodiment one to five.
Embodiment nine: present embodiment and embodiment one to five are different be step 2 in treating processes before 1h get rid of the bubble on surface in the solution.Other step and parameter are identical with embodiment one to five.
Embodiment ten: what present embodiment and embodiment six to nine were different is that the pH value is 6 in the step 3.Other step and parameter are identical with embodiment six to nine.
Embodiment 11: what present embodiment and embodiment one, two, three, four, five or ten were different is that temperature is 25～40 ℃ in the step 3.Other step and parameter are identical with embodiment one, two, three, four, five or ten.
Embodiment 12: what present embodiment and embodiment one, two, three, four, five or ten were different is that temperature is 35 ℃ in the step 3.Other step and parameter are identical with embodiment one, two, three, four, five or ten.
Embodiment 13: what present embodiment was different with embodiment 11 or 12 is that time of repose is 1～6h in the step 3.Other step and parameter are identical with embodiment 11 or 12.
Embodiment 14: what present embodiment was different with embodiment 11 or 12 is that time of repose is 3h in the step 3.Other step and parameter are identical with embodiment 11 or 12.
Embodiment 15: what present embodiment was different with embodiment 11 or 12 is that time of repose is 5h in the step 3.Other step and parameter are identical with embodiment 11 or 12.
Embodiment 16: what present embodiment was different with embodiment 11 or 12 is that time of repose is 4h in the step 3.Other step and parameter are identical with embodiment 11 or 12.
Embodiment 17: the treatment process of present embodiment magnesium surface is carried out according to the following steps: one, magnesium placed acetone ultrasonic cleaning 5min, uses distilled water flushing then 2 times, and dry again; Two, to place concentration be that 3.0mol/L, pH value are that 13 NaOH solution is handled 10h to the magnesium after step 1 is handled, and uses distilled water flushing then 2 times, again drying; Three, the mother metal after step 2 is handled is placed ca nitrate soln, with the rate of titration be that 3mL/min, pH value are 6 then, temperature is under 30 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, leave standstill 6h then, the mother metal surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again, promptly finish the processing of magnesium surface.
Placing simulated body fluid at magnesium after surface treatment in the present embodiment is finished, is that 37 ℃, pH value are that magnesium surface forms hydroxyapatite layer after soaking 15 days under 7.4 the condition in temperature, and the contrast material of handling without the present invention (pure magnesium); Test through galvanic corrosion, as seen from Figure 1, passivation region does not appear in the polarization curve anode part of the contrast material of handling without the present invention, corrosion potential is-1.6～-1.7V, and tangible passivation phenomenon appears in the polarization curve anode part of treated material in the present embodiment, by contrast, the corrosion potential raising is elevated to-.09V, even can reach 0V.Current density is from-4A/cm
2Be reduced to-4.8～-5A/cm
2About.
Handle back magnesium by present embodiment and will form corrosion resistant hydroxyapatite layer on the surface, thus magnesium directly contact with simulated body fluid (corrosive liquid), so, can not make the pH change even the generation bubble is measured also considerably lessly.
Handle back magnesium by present embodiment and will form corrosion resistant hydroxyapatite layer on the surface, as shown in Figure 2, as can be seen from Figure 2, hydroxyapatite layer is evenly distributed, fine and close, surperficial flawless.Fig. 3 is the pattern after pure magnesium surface directly soaks in simulated body fluid without any processing.From Fig. 3, can clearly must find out pure magnesium surface skewness and crackle is arranged.
Embodiment 18: present embodiment magnesium or treatment method on surface of magnesium alloy are carried out according to the following steps: one, mother metal placed acetone or ethanol solution ultrasonic cleaning 1～10min, uses distilled water flushing then 2 times, and dry again; Two, the mother metal after step 1 is handled is placed ca nitrate soln, be 5～7 in the pH value then, temperature is under 20～47 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, then leave standstill 10min～8h, the mother metal surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again; Three, the mother metal with surface coverage dicalcium phosphate dihydrate layer places simulated body fluid, in temperature is that 37 ℃, pH value are that the mother metal surface forms the layer of even hydroxyapatite after soaking 1～30 day under 7.4 the condition, use distilled water flushing then 2 times, dry again, promptly finish the processing of magnesium or Mg alloy surface; Wherein mother metal is magnesium or magnesium alloy in the step 1.
Embodiment 19: that present embodiment and embodiment 18 are different is ultrasonic cleaning 5min in the step 1.Other step and parameter are identical with embodiment 18.
Embodiment 20: that present embodiment and embodiment 18 are different is ultrasonic cleaning 8min in the step 1.Other step and parameter are identical with embodiment 18.
Embodiment 21: what present embodiment and embodiment 18 were different is that the pH value is 5.5 in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 22: what present embodiment and embodiment 18 were different is that the pH value is 6 in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 23: what present embodiment and embodiment 18 were different is that temperature is 25～40 ℃ in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 24: what present embodiment and embodiment 18 were different is that temperature is 35 ℃ in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 25: what present embodiment and embodiment 18 were different is that time of repose is 1～6h in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 26: what present embodiment and embodiment 18 were different is that time of repose is 3h in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 27: what present embodiment and embodiment 18 were different is that time of repose is 4h in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 28: what present embodiment and embodiment 18 were different is that time of repose is 5h in the step 2.Other step and parameter are identical with embodiment 18.
Embodiment 29: the present embodiment treatment method on surface of magnesium alloy is carried out according to the following steps: one, magnesium alloy placed ethanol solution ultrasonic cleaning 6min, uses distilled water flushing then 2 times, and dry again; Two, the magnesium alloy after step 1 is handled is placed ca nitrate soln, be 6 in the pH value then, temperature is under 35 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, then leave standstill 5h, Mg alloy surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again, promptly finish the processing of Mg alloy surface.
The material that Mg alloy surface after present embodiment handled forms hydroxyapatite places the environment electron microscope photo scanning of cell growth behind the simulated body fluid, and as shown in Figure 4, as can see from Figure 4, cell stretches better, does not see necrocytosis.
Handle the back magnesium alloy by present embodiment and will form corrosion resistant hydroxyapatite layer,,, can not make the pH change even the generation bubble is measured also considerably lessly so magnesium alloy directly contact with simulated body fluid (corrosive liquid) on the surface.
The magnesium alloy of material people bone, synthesizing hydroxylapatite, titanium alloy, stainless steel and the present embodiment of implant into body being handled well by density, Young's modulus, compression yield degree, fracture toughness property compares, and comparative result is as shown in table 1:
Table 1:
| The material of implant into body | Density g/cm 3 | Elastic modulus G pa | Compression yield degree MPa | Fracture toughness property MPam 1/2 |
| People's bone | 1.81～2.1 | 3～20 | 130～180 | 3～6 |
| Synthesizing hydroxylapatite | 3.1 | 73～117 | 600 | 0.7 |
| The magnesium alloy of handling well | 1.74～2.0 | 41～45 | 65～100 | 15～40 |
| Titanium alloy | 4.4～4.5 | 110～117 | 758～1117 | 55～115 |
| Stainless steel | 7.9～8.1 | 189～205 | 170～310 | 50～200 |
Every performance (density, Young's modulus, compression yield degree and fracture toughness property) of the magnesium alloy after the process present embodiment is handled as can be seen by table 1 is more near people's bone.
Claims (10)
1. magnesium or treatment method on surface of magnesium alloy is characterized in that magnesium or treatment method on surface of magnesium alloy carry out according to the following steps: one, mother metal placed acetone or ethanol solution ultrasonic cleaning 1～10min, use distilled water flushing then 2 times, and dry again; Two, to place concentration be that 0.05～5.0mol/L, pH value are that 12～14 NaOH solution is handled 0.5～24h to the mother metal after step 1 is handled, and uses distilled water flushing then 2 times, again drying; Three, the mother metal after step 2 is handled is placed ca nitrate soln, be 5～7 in the pH value then, temperature is under 20～47 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, then leave standstill 10min～8h, the mother metal surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again, promptly finish the processing of magnesium or Mg alloy surface; Wherein mother metal is magnesium or magnesium alloy in the step 1.
2. magnesium according to claim 1 or treatment method on surface of magnesium alloy, it is characterized in that placing in the step 2 concentration is that 0.5～4.0mol/L, pH value are that 12.5～13.5 NaOH solution is handled 3～20h.
3. magnesium according to claim 1 or treatment method on surface of magnesium alloy, it is characterized in that placing in the step 2 concentration is that 3.0mol/L, pH value are that 13 NaOH solution is handled 10h.
4. according to claim 1,2 or 3 described magnesium or treatment method on surface of magnesium alloy, it is characterized in that step 2 preceding 0.5～3h in treating processes gets rid of the bubble on surface in the solution.
5. according to claim 1,2 or 3 described magnesium or treatment method on surface of magnesium alloy, it is characterized in that step 2 preceding 1.5～2.5h in treating processes gets rid of the bubble on surface in the solution.
6. magnesium according to claim 5 or treatment method on surface of magnesium alloy is characterized in that the pH value is 6 in the step 3.
7. according to claim 1,2,3 or 6 described magnesium or treatment method on surface of magnesium alloy, it is characterized in that temperature is 35 ℃ in the step 3.
8. magnesium according to claim 7 or treatment method on surface of magnesium alloy is characterized in that time of repose is 3h in the step 3.
9. magnesium according to claim 7 or treatment method on surface of magnesium alloy is characterized in that time of repose is 4h in the step 3.
10. magnesium or treatment method on surface of magnesium alloy is characterized in that magnesium or treatment method on surface of magnesium alloy carry out according to the following steps: one, mother metal placed acetone or ethanol solution ultrasonic cleaning 1～10min, use distilled water flushing then 2 times, and dry again; Two, the mother metal after step 1 is handled is placed ca nitrate soln, be 5～7 in the pH value then, temperature is under 20～47 ℃ the condition dipotassium hydrogen phosphate to be added drop-wise in the solution, then leave standstill 10min～8h, the mother metal surface forms layer of even dicalcium phosphate dihydrate layer, use distilled water flushing then 2 times, dry again, promptly finish the processing of magnesium or Mg alloy surface; Wherein mother metal is magnesium or magnesium alloy in the step 1.
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| CN2009100721771A CN101565825B (en) | 2009-06-03 | 2009-06-03 | Treatment method of magnesium or magnesium alloy surface |
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|---|---|---|---|
| CN2009100721771A CN101565825B (en) | 2009-06-03 | 2009-06-03 | Treatment method of magnesium or magnesium alloy surface |
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| CN101565825A CN101565825A (en) | 2009-10-28 |
| CN101565825B true CN101565825B (en) | 2011-02-02 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103205705B (en) * | 2013-04-25 | 2015-06-03 | 哈尔滨工业大学 | Preparation method of controllable, degradable and biocompatible coating on surfaces of magnesium and magnesium alloy |
| WO2017110986A1 (en) * | 2015-12-25 | 2017-06-29 | 日本パーカライジング株式会社 | Surface-conditioning agent, as well as magnesium member or magnesium alloy material with film, and manufacturing method therefor |
| JP6872987B2 (en) * | 2017-06-22 | 2021-05-19 | 日本パーカライジング株式会社 | Magnesium-containing metal material with film |
| CN108531893A (en) * | 2018-04-04 | 2018-09-14 | 天津大学 | A kind of microwave preparation of Mg alloy surface nano whiskers calcium monohydrogen phosphate coating |
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