CN106567062A - Surface modified magnesium alloy material with good corrosion resistance and biocompatibility and preparation method and application thereof - Google Patents
Surface modified magnesium alloy material with good corrosion resistance and biocompatibility and preparation method and application thereof Download PDFInfo
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- CN106567062A CN106567062A CN201610915197.0A CN201610915197A CN106567062A CN 106567062 A CN106567062 A CN 106567062A CN 201610915197 A CN201610915197 A CN 201610915197A CN 106567062 A CN106567062 A CN 106567062A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
Abstract
The invention relates to a surface modified magnesium alloy material with good corrosion resistance and biocompatibility and a preparation and application of the surface modified magnesium alloy material. The surface modified magnesium alloy material comprises magnesium alloy and a modified coating, wherein the modified coating grows on the surface of the magnesium alloy in situ, is of a nanosheet structure and contains magnesium hydroxide and magnalium layered double hydroxide. The prepared surface modified magnesium alloy material can lower the concentration of chloride ions near the alloy and protect the magnesium alloy. In addition, the modified magnesium alloy surface is more beneficial to cell adhesion, spreading and proliferation, and has good cytocompatibility.
Description
Technical field
The present invention relates to a kind of modified magnesium alloy materials in surface and its surface modifying method, particularly relate to a kind of employing
Hydro-thermal process carries out the modified method in surface to magnesium alloy, belongs to technical field of metal material surface modification.
Background technology
Magnesium alloy has good mechanical performance, elastic modelling quantity and bone tissue closely and catabolite can be with
In the new old generation of human body, excretes, and is ideal hard tissue alternate material and angiocarpy bracket material.Magnesium alloy is regarded
For biomaterial for medical purpose of future generation.Current most of medical material, such as medical material such as titanium alloy, Nitinol is all not
Degradation material.Second operation is needed to take out implant, this can bring heavy spirit and economic pressures to patient.Therefore, send out
Exhibition novel degradable medical material has critically important social and Research Significance.
The electrochemical potential of magnesium alloy is too low, and corrosion rate is too fast.Due to too fast corrosion, magnesium alloy can prematurely lose it
Mechanical performance, so as to cause implantation failure.Still further aspect, due to the hydrogen and surrounding tissue liquid pH of generation in corrosion process
The change of value, can cause inflammatory reaction, increase the pain of patient.How by the morphology and chemistry of change magnesium alloy
Structure is also considerably less come the report for improving its corrosion resistance and cell compatibility.
Magnesium alloy surface when being corroded can generate one layer of loose magnesium hydroxide layer, simultaneously because the too high chlorine of body fluid from
Sub- concentration can destroy magnesium hydroxide layer, so the magnesium hydroxide layer for generating by magnesium alloy self-corrosion merely can not prevent corrosion
The further etched the matrix of liquid.
The content of the invention
The present invention is too fast for the degradation rate for solving magnesium alloy presence, and the imperfect problem of superficial cell compatibility,
There is provided it is a kind of with modified magnesium alloy materials in surface for improving corrosion resistance of magnesium alloy and cell compatibility and preparation method thereof and
Using.
Here, on the one hand, the present invention provides a kind of modified magnesium in surface with good corrosion resistance and cell compatibility and closes
Golden material, including magnesium alloy and growth in situ in the Mg alloy surface with nanometer chip architecture containing magnesium hydroxide and
The modified coating of magnalium laminar double-metal hydroxide (Mg-Al LDH).
The modified magnesium alloy materials in the surface of the present invention, have fine and close magnesium hydroxide and magnalium laminar bimetallic hydrogen on surface
Oxide skin(coating).Nitrate anion, boric acid in the high corrosive liquid of chlorine ion concentration, due to magnalium laminar double-metal hydroxide interlayer
Root plasma be able to can be swapped with chlorion, so as to reduce the concentration of alloy surface chlorion, it is suppressed that chlorion pair
The corrosion of fine and close magnesium hydroxide layer, it is final to realize protection magnesium so as to the contact completely cut off between corrosive liquid and base magnesium alloy
The effect of alloy.That is, the modified magnesium alloy materials in surface of the invention can reduce the concentration of chlorion near alloy, realize to magnesium
The protection of alloy.Additionally, being more beneficial for the adhesion of cell through modified Mg alloy surface, sprawling and rise in value, with good
Cell compatibility.
It is preferred that magnalium atomicity ratio is (2～9) in the modified coating：1.Refer specifically to containing magnesium hydroxide and
Magnalium atomic ratio in the modified coating of magnalium laminar double-metal hydroxide.
It is preferred that the thickness of nanometer sheet is 10～40nm in the modified coating.
It is preferred that the thickness of the modified coating is 1～5 μm.
It is preferred that the magnesium alloy is the one kind in JDBM, AZ31, AZ91.
On the other hand, the preparation method of magnesium alloy materials the invention provides a kind of surface is modified, including：
Magnesium alloy is placed in reactor, adds the alkaline solution containing silicon source to make its submergence magnesium alloy, the water at 60～160 DEG C
Heat treatment 5～15 hours, obtains the modified magnesium alloy materials in the surface.
The present invention directly can be dropped in the growth of magnesium alloy materials surface in situ by hydro-thermal process by ion exchange
The Mg (OH) of low-alloy surrounding medium chlorine ion concentration2And Mg-Al LDH, afterwards material surface is removed by deionized water remaining
Hydro-thermal medium.The preparation method of the present invention is simple, with low cost, and obtained stability of material is good, safe.
It is preferred that source of aluminium is at least one in aluminum nitrate, aluminum sulfate, aluminum acetate.Wherein the moon of source of aluminium from
Son is corresponding with anion between magnalium laminar double-metal hydroxide layer structure.
It is preferred that middle aluminium ion concentration is 0.01～0.05mol/L in the alkaline solution of the containing a source of aluminum.
It is preferred that the pH value of the alkaline solution is 9～12.
It is preferred that the compactedness of the reactor is 30～70%.
Another further aspect, present invention also offers a kind of modified magnesium alloy materials in above-mentioned surface are in manufacture medical magnesium alloy device
In application.
The modified magnesium alloy materials in surface of the present invention compared with untreated magnesium alloy materials, its corrosion resistance and cell phase
Capacitive is significantly improved.Corrosion potential confirms that the short-term corrosion resistance of modified magnesium alloy is still long-term with collecting gas
Corrosion resistance all increases significantly.After modified sample corrodes one day in cell culture medium, its surface topography is still protected
Hold complete, and any corrosive shake do not occur.Toxicity all reduction of the modified sample of the toxicity of cell immersion liquid to cell.Carefully
Born of the same parents' skeleton Coloration experiment and increment experiment confirm that modified material is conducive to cell to sprawl and rise in value.Data above shows, changes
Magnesium alloy after property has good corrosion resistance and cell compatibility.
Description of the drawings
Fig. 1 is Mg alloy surface scanning electron microscope (SEM) photograph ((a), (b), (c)) and the cross-sectional view after process modified by this invention
((d), (e), (f)), wherein (a), (d) represent that hydro-thermal liquid pH value is 10 and the not magnesium alloy of containing a source of aluminum hydro-thermal process, (b), (e)
Represent that hydro-thermal liquid pH value is 12 and the not magnesium alloy of containing a source of aluminum hydro-thermal process, (c), (f) represent that hydro-thermal liquid pH value is 12 and containing aluminium
The magnesium alloy of source hydro-thermal process；
Fig. 2 is the XRD spectra of the Mg alloy surface after before processing modified by this invention, and wherein JDBM represents that untreated magnesium is closed
Gold, HT1# represent hydro-thermal liquid pH value be 10 and not the magnesium alloy of containing a source of aluminum hydro-thermal process, HT2# represent hydro-thermal liquid pH value for 12 and
The magnesium alloy of containing a source of aluminum hydro-thermal process, HT3# do not represent that hydro-thermal liquid pH value is 12 and the magnesium alloy of containing a source of aluminum hydro-thermal process；
Fig. 3 is corrosion potential figure (a) of magnesium alloy after before processing modified by this invention in 37 DEG C of PBS,
And surface sweeping electron microscope (b) of corresponding corrosion area；
Fig. 4 is magnesium alloy after the before processing modified by this invention hydrogen-separating quantity (a) in 37 DEG C of PBS, and thus
The average corrosion rate (b) for calculating；
Fig. 5 is the impact test result of magnesium alloy after before processing modified by this invention to osteoblast activity, wherein (a) is to sweep
Face electron microscope, (b) are cell quantification test result；
Fig. 6 is the Toxic test results of the leaching liquor to cell of the magnesium alloy after before processing modified by this invention, wherein (a) is the
Test result, (b) are the 4th day test result within 1 day；
Fig. 7 sprawls test result for the adhesion of Mg alloy surface of the Gegenbaur's cell after before processing modified by this invention, wherein (a-
1), (a-4), (a-24) are respectively the adhesion of untreated Mg alloy surface and sprawl 1 hour, 4 hours, the test knot of 24 hours
Really, (b-1) it is 10 and the not adhesion of the Mg alloy surface of containing a source of aluminum hydro-thermal process that, (b-4), (b-24) are respectively hydro-thermal liquid pH value
Sprawl 1 hour, 4 hours, the test result of 24 hours, (c-1), (c-4), (c-24) be respectively hydro-thermal liquid pH value 12 and not contain
1 hour, 4 hours, the test result of 24 hours are sprawled in the adhesion of the Mg alloy surface of silicon source hydro-thermal process, (d-1), (d-4),
(d-24) be respectively hydro-thermal liquid pH value be 12 for hydro-thermal liquid pH value and the adhesion of the magnesium alloy of containing a source of aluminum hydro-thermal process to sprawl 1 little
When, 4 hours, the test result of 24 hours.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, and the unrestricted present invention.
The modified magnesium alloy materials in the surface of the present invention form one layer mainly by magnesium hydroxide and magnalium layer in Mg alloy surface
Modified layer that shape double-metal hydroxide is constituted (or the modified material surface for obtaining is by magnesium hydroxide and magnalium laminar bimetallic hydrogen
The mixed phase of oxide (Mg-Al LDH) is constituted).Wherein, in coating magnalium laminar double-metal hydroxide interlayer anion
Predominantly nitrate anion, borate etc. (add other anion, such as sulfate radical).The modified layer can be in magnesium alloy materials table
Face is generated in-situ.Fig. 1 illustrates the HT1# and HT2# of the modified magnesium alloy HT3# of the present invention and its control group pure cerium hydroxide magnesium layer
Surface topography map and cross-sectional view.(c), (f) in Fig. 1, by magnesium hydroxide and magnalium laminar double-metal hydroxide
The modified layer of composition is in flaky nanometer structure, and the thickness of nanometer sheet is evenly distributed in 10～40nm.The thickness of coating is 1～5
μm。
As shown in Fig. 2 illustrating the modified magnesium alloy materials (HT1#, HT2#, HT3#) in surface of three examples of the invention in Fig. 2
And the XRD spectra of unmodified JDBM Mg alloy surfaces, it can be seen that HT1#, HT2# material surface oikocryst phase constituent is
Mg(OH)2, HT3# material surface oikocrysts phase constituent is Mg (OH)2With Mg-Al LDH.
In the modified magnesium alloy materials in the surface of the present invention, the magnalium atomicity ratio of modified surface is (2～9)：1.
The modified magnesium alloy materials in the surface of the present invention can be passed through due to the presence of magnalium laminar double-metal hydroxide phase
Ion exchange reduces the chlorine ion concentration of material surface, with good corrosion resistance.Magnalium laminar double-metal hydroxide layer
Between anion there is the nitrate anion of substitutability, particularly interlayer, borate plasma to be particularly easy to be handed over chlorion
Change.Mg alloy surface chlorine ion concentration is reduced by this ion exchange property, so as to realize protecting magnesium hydroxide layer not broken
Bad purpose.
Wherein, Fig. 2 illustrates the XRD spectra of the Mg alloy surface after before processing modified by this invention.JDBM represents untreated
Magnesium alloy, HT1# represents that hydro-thermal liquid pH value is 10 and the not magnesium alloy of containing a source of aluminum hydro-thermal process, and HT2# represents hydro-thermal liquid pH value
For 12 and the not magnesium alloy of containing a source of aluminum hydro-thermal process, HT3# represents that hydro-thermal liquid pH value is 12 and the magnesium of containing a source of aluminum hydro-thermal process is closed
Gold.As can be seen from Figure 2 the surface for there was only HT3# samples detects characteristic peak at 12 ° and 24 ° or so.This explanation only exists
Just there is the generation of Mg-Al LDH on the surface of HT3# samples, and all at 12 ° without characteristic peak, 18 degree have characteristic peak to HT1 and HT2#, say
Bright surface both all only has magnesium hydroxide, and without Mg-Al LDH.
Fig. 3 illustrates that the magnesium alloy materials that the modified magnesium alloy materials in the surface of three examples of the present invention are modified with non-surface exist
Corrosion potential figure (a) in 37 DEG C of PBS, and surface sweeping electron microscope (b) of corresponding corrosion area.From Fig. 3
In it can be seen that compare it is material modified with only pure cerium hydroxide magnesium protective layer with unmodified magnesium alloy materials, by magnesium hydroxide
There is higher corrosion potential and lower corrosion current with the modified layer that magnalium laminar double-metal hydroxide is constituted, from corresponding
The surface sweeping electron microscope of corrosion area can more intuitively find out that its corrosion resistance has significant raising.
Fig. 4 illustrates the hydrogen-separating quantity (a) in 37 DEG C of PBS of the magnesium alloy after before processing modified by this invention,
And the average corrosion rate (b) for thus calculating.As can be seen from Figure 4 by magnesium hydroxide and magnalium laminar bimetal hydroxide
The modified layer that thing is constituted has preferably long-term corrosion resistance.
Fine and close magnesium hydroxide and magnalium laminar double-metal hydroxide are mixed in the modified magnesium alloy materials in the surface of the present invention
The micro-nano structure of conjunction phase is also beneficial to the adhesion of cell and sprawls and rise in value, therefore with good cell compatibility.Wherein, Fig. 5
It is impact test result of the magnesium alloy after before processing modified by this invention to osteoblast activity.As can be seen from Figure 5 into
The Mg alloy surface appreciation rate highest that osteocyte is modified in magnesium hydroxide and magnalium laminar double-metal hydroxide, and from Electronic Speculum
Figure as can be seen that only HT3# be observed that cell, other three groups of surfaces be all corroded product covering.Fig. 6 is Jing of the invention
Toxic test results of the leaching liquor of the magnesium alloy before and after modification to cell.As can be seen from Figure 6 magnesium hydroxide and magnesium
The cytotoxicity of the leaching liquor of the modified magnesium alloy of aluminium layered double hydroxide is minimum.Fig. 7 be Gegenbaur's cell Jing this
Test result is sprawled in the adhesion of the Mg alloy surface before and after bright modification.As can be seen from Figure 7 magnesium hydroxide and magnalium layer
The modified Mg alloy surface cell of shape double-metal hydroxide 24 as a child sprawled it is best.When 4 hours, other three groups of cells
Stretch, but by 24 hours, just all atrophy was gone back, and this shows that the cell state after 24 hours is very poor.
The preparation method of the modified magnesium alloy materials in surface that the explanation present invention in following exemplary ground is provided.
The present invention uses hydro-thermal treatment method and reduces material by ion exchange in the above-mentioned energy of Mg alloy surface construction
The modified layer of surface chlorine ion concentration.Specifically, magnesium alloy materials are carried out at hydro-thermal by hydro-thermal medium of alkaline aqueous solution
Reason.As an example, first hydro-thermal process is carried out to the magnesium alloy respectively through alcohol ultrasound and deionized water after ultrasonic, afterwards
Cleaned using deionized water immediately, so as to take out the hydro-thermal liquid for remaining in Mg alloy surface.
Above-mentioned hydro-thermal medium be pH value for 9-12 (preferred 10-12) deionized water and containing aluminium ion concentration 0.01～
The silicon source solution of 0.05mol/L.Source of aluminium solution can be aluminum nitrate, aluminum sulfate, at least one in aluminum acetate.Using alkalescence
Solution adjusts pH value and is more than 10.Wherein, the alkaline solution is chosen as at least one in NaOH, potassium hydroxide, ammoniacal liquor,
For example it is chosen as the sodium hydroxide solution of 1-10mol/L.The temperature of hydro-thermal process is 60～160 DEG C.The time of hydro-thermal process can
For 5-15 hours.The compactedness of aforesaid reaction vessel can be 30～70%.
The corrosion resistance and cell compatibility of the magnesium alloy obtained through method of modifying of the present invention process has been obtained significantly
Improve.Corrosion potential is tested and collecting gas confirm, the shot and long term corrosion resistance of modified magnesium alloy is all substantially better than and changes
Magnesium alloy before property.Cytotoxicity experiment, cell proliferation experiment and cytoskeleton Coloration experiment all confirm modified material
It is more beneficial for cell proliferation and adhesion is sprawled.Data above shows, modified magnesium alloy have good corrosion resistance and
Cell compatibility.In addition, present invention gives the good corrosion resistance of magnesium alloy and biocompatibility, can be widely used in
The surface of magnesium alloy medicine equipment is modified.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
1mm is thick, and length and width are all the JDBM magnesium alloy plates of 10mm, clean with alcohol, deionized water and ultrasonic cleaning successively, every time
15min.NaOH with 1mol/L will be transferred to 10 in the pH value of 50 milliliters of ultra-pure waters, and the solution is used as hydro-thermal medium.Reaction
The compactedness of kettle is 35%.120 DEG C of hydrothermal temperature, the time is 8h.After hydro-thermal terminates, with substantial amounts of deionized water sample is scrubbed.
The magnesium alloy scanning electron microscopic picture (Fig. 1 (a)) obtained referring to the modification of the present embodiment 1 and cross section picture (Fig. 1
(d)), there it can be seen that surface is the nanostructured of sheet after processing, the thickness of nanometer sheet is distributed equal in 20nm or so
Even, the thickness of coating is 1.8 μm or so.HT1# is the XRD spectra of the material surface that the modification of the present embodiment 1 is obtained in Fig. 2,
Modified through the present embodiment, the oikocryst phase constituent of material surface is changed into Mg (OH)2。
Embodiment 2
1mm is thick, and length and width are all the JDBM magnesium alloy plates of 10mm, clean with alcohol, deionized water and ultrasonic cleaning successively, every time
15min.NaOH with 1mol/L will be transferred to 12 in the pH value of 50 milliliters of ultra-pure waters, and the compactedness of reactor is 35%.It
Laggard water-filling heat treatment, its specific process parameter is as described in Example 1..
The scanning electron microscopic picture (Fig. 1 (b)) of the magnesium alloy obtained referring to the modification of the present embodiment 2 and cross section picture
(Fig. 1 (e)), it can be seen that process after surface for sheet nanostructured, the thickness of nanometer sheet in 20nm or so, and
It is evenly distributed, the thickness of coating is 2.3 μm or so.HT1# is the material surface that the modification of Jing the present embodiment 2 is obtained in Fig. 2
XRD spectra, modified through the present embodiment, the oikocryst phase constituent of material surface is changed into Mg (OH)2。
Embodiment 3
1mm is thick, and length and width are all the JDBM magnesium alloy plates of 10mm, clean with alcohol, deionized water and ultrasonic cleaning successively, every time
15min.NaOH with 10mol/L will be transferred to 12 in the pH value of the aluminum nitrate of 50 milliliters of 0.02mol/L.Reactor is filled out
Degree of filling is 35%.Hydro-thermal process is carried out afterwards, and its specific process parameter is as described in Example 1.
The magnesium alloy scanning electron microscopic picture (Fig. 1 (c)) obtained referring to the modification of the present embodiment 3 and cross section picture (Fig. 1
(f)), it can be seen that surface is the nanostructured of sheet after processing, the thickness of nanometer sheet is distributed in 20nm or so
Uniformly, the thickness of coating is 2 μm or so.JDBM and HT3# are modified without any process and Jing the present embodiment 3 in Fig. 2
The XRD spectra of the material surface that process is obtained, as we can see from the figure for undressed sample, from its XRD spectrum only
The characteristic peak of Mg can be seen.And it is modified through the present embodiment 3, the oikocryst phase constituent of material surface is changed into Mg-Al LDH and Mg
(OH)2。
Embodiment 4
The sample obtained to above-described embodiment carries out x-ray photoelectron power spectrum (XPS) test, (XPS, PHI-5000C ESCA
system PerkinElmer,USA)。
Table 1 (see the end of writing) is the sample surfaces element composition that above-described embodiment is obtained.The He of embodiment 1 as can be seen from the table
The essential element on the surface of embodiment 2 is magnesium and oxygen, has no and detects aluminium element.And aluminium element, and magnalium are contained in the surface of embodiment 3
Atomicity ratio is 2.919：1.
Table 1 is Elements Atom percentage (the coating surface element of the coating of magnesium alloy surface after process modified by this invention
Composition)：
Embodiment 5
Corrosion potential figure test is carried out to the sample that unmodified sample and above-described embodiment are obtained：Test sample be working electrode,
Graphite rod be to electrode, calomel electrode be reference electrode, using electrochemical workstation (Shanghai occasion China CHI760C) test material
Corrosion resistant performance.
Fig. 3 (a) is the corrosion potential analysis chart of each group sample that above-described embodiment modification is obtained, can from figure
For the sample obtained to after through implementing 1 and the process of embodiment 2 is compared with JDBM, corrosion potential all forward directions are moved.And embodiment 3
The sample etches current potential obtained after process is positive mobile maximum.Illustrate the Mg (OH) of densification2With certain altitude corrosion resistance.Jing
Cross the modified Mg of Mg-Al LDH (OH)2It is anticorrosive more preferable.Fig. 3 (b) is the ESEM for having surveyed corrosion potential post-etching region
Figure, can intuitively find out that the corrosion resistance of embodiment 3 is best from figure.
Embodiment 6
Collecting gas test is carried out to the sample that unmodified sample and above-described embodiment are obtained.Sample is immersed in PBS solution,
Per group of 3 samples, using upside down funnel the hydrogen burst size during sample degradation is collected.Surface area of sample and PBS solution body
Product is than being 25ml/cm2.Whole test process is carried out under 37 DEG C of constant temperature.
Fig. 4 is liberation of hydrogen result figure (a) that above-described embodiment modification is obtained and thus calculated average corrosion
Rate diagram (b).As can be seen from Figure 4 for the sample for obtaining after enforcement 1 and embodiment 2 are processed is compared with JDBM, hydrogen-separating quantity
All decrease.And the sample hydrogen-separating quantity reduction that embodiment 3 is obtained after processing is most.Illustrate the corrosion resistance of embodiment 3 most
Good, this is consistent with the result of corrosion potential analysis.
Embodiment 7
Closed using mouse bone-forming cell MC3T3-E1 in vitro culture experimental evaluations above-described embodiment 1,2 and 3 modifications gained magnesium
Impact of the golden material to normal cytoactive.Using ALMA indigo plant (AlamarBlueTM, AbDserotec Ltd, UK) kit
Proliferative conditions of the detection cell in material surface.Method is as follows：
1) will be put in 24 well culture plates through the sample of 12h ultraviolet sterilizations, it is 5 × 10 that 1mL density is added dropwise per hole4cell/mL
Cell suspension；
2) Tissue Culture Plate is put into into 5%CO236.5 DEG C of hatchings in the cell culture incubator of saturated humidity；
3) cell culture 4 and after 7 days, sucks original fluid, adds containing the new of 5% ALMA indigo plant (AlamarBlueTM) dye liquor
Nutrient solution, culture plate is placed in incubator and is cultivated after 4h, is taken out 100 μ L nutrient solutions from every hole and is put in 96 orifice plates；
5) using ELIASA (BIO-TEK, ELX800) measure each hole wavelength for 530nm exciting light under, the transmitting at 590nm
Luminous intensity.Its light intensity is proportionate with cell quantity；
Gegenbaur's cell utilizes surface sweeping electron microscopic observation in the pattern of material surface.
Fig. 5 is the modified magnesium alloy of the above-mentioned modified embodiments 1,2,3 of Jing and unmodified magnesium alloy to normal cell
The proliferation experiment of MC3T3-E1 and the result figure of cell morphology, wherein it is cell quantification test knot that (a) is surface sweeping electron microscope, (b)
Really.When (b) can be seen that the 4th day from Fig. 5, increment of the embodiment 1 to cell does not have any effect；Embodiment 2 was at the 4th day
When can promote the increment of cell, but by the 7th day, cell was also substantially all dead；It is only thin on the surface of embodiment 3
Born of the same parents can survive always and also certain increment.(a) is it is also seen that only can on the surface of embodiment 3 from Fig. 5
To be clearly visible that the cell sprawled completely, and embodiment 1 and 2 can only observe the crud for being covered in material surface.
The above results show there is good cell compatibility through the sample of the process of embodiment 3.
Embodiment 8
Closed using mouse bone-forming cell MC3T3-E1 in vitro culture experimental evaluations above-described embodiment 1,2 and 3 modifications gained magnesium
The toxicity of the leaching liquor of golden material.Concrete grammar is as follows：
1) will be put in 24 well culture plates through the sample of 12h ultraviolet sterilizations, per the close culture mediums of hole 2mL；Simultaneously in 96 orifice plates
200 μ L density are added dropwise for 5 × 104Cell/mL cell suspensions；
2) two pieces of growth plates are put into into 5%CO2In 36.5 DEG C of cell culture incubators of saturated humidity；
3) nutrient solution for being placed with the Tissue Culture Plate of sample is taken out, the concentration of the initial leaching liquor of gained is defined as 100%, then uses
Culture medium dilution obtains the leaching liquor of 90%, 60% and 30% concentration.The cell culture fluid in 96 orifice plates is sucked afterwards, and often
Hole adds the leaching liquor of each gradients of 200 μ L；
4) continue to cultivate 1 day and 4 days, with the method test cell quantity of embodiment 6.
Fig. 6 is the leaching liquor of the modified magnesium alloy of the above-mentioned modified embodiments 1,2,3 of Jing and unmodified magnesium alloy to cell
Toxic test results, be (a) the 1st day test result, (b) be the 4th day test result.As can be seen from Figure 6 the 1st day when,
The leaching liquor toxicity of embodiment 1,2,3 is all big than unmodified magnesium alloy, but has no significant difference.By the 4th day, embodiment
3 cytotoxicity is significantly less than other embodiment and unmodified magnesium alloy.Result above shows, the cytotoxicity of embodiment 3
Minimum, cell compatibility is best.As a result it is consistent with cell proliferation experiment.
Embodiment 9
Using mouse bone-forming cell MC3T3-E1 in vitro cultures and the modified place of fluorescent staining experimental evaluation above-described embodiment 1,2 and 3
The impact that reason gained magnesium alloy materials are sprawled to cell adherence.Concrete grammar is as follows：
1) will be put in 24 well culture plates through the sample of 12h ultraviolet sterilizations, it is 5 × 10 that 1mL density is added dropwise per hole4cell/mL
Cell suspension；
2) Tissue Culture Plate is put into into 5%CO236.5 DEG C of hatchings in the cell culture incubator of saturated humidity；
3) after cultivating 1,4 and 24 hours, cell is dyeed with FITC and DAPI, and with laser confocal microscope (CLSM)
Observation.
Fig. 7 is the leaching liquor of the modified magnesium alloy of the above-mentioned modified embodiments 1,2,3 of Jing and unmodified magnesium alloy to cell
Adhesion test result.Whether 1 hour, 4 hours or 24 hours as can see from Figure 7, be all the modified magnesium of embodiment 3
It is best that the cell of alloy surface is sprawled, and by 24 hours, the cell of the modified Mg alloy surface of embodiment 1 and 2 was sprawled
Situation is roughly the same with unmodified magnesium alloy, does not show the effect for promoting cell to sprawl.Result above shows, only
The magnesium alloy for having embodiment 3 modified can be effectively promoted the adhesion of cell and sprawl, and show good cell compatibility.
Industrial applicability：Present invention gives the excellent corrosion resistance of magnesium alloy and cell compatibility, extensively can should
Surface for bio-medical medicine equipment is modified.
Claims (10)
1. modified magnesium alloy materials in a kind of surface with good corrosion resistance and biocompatibility, it is characterised in that including magnesium
Alloy and growth in situ are in the Mg alloy surface with nanometer chip architecture containing magnesium hydroxide and the double gold of magnalium laminar
The modified coating of category hydroxide.
2. modified magnesium alloy materials in surface according to claim 1, it is characterised in that magnalium atom in the modified coating
Counting ratio is（2～9）：1.
3. modified magnesium alloy materials in surface according to claim 1 and 2, it is characterised in that nanometer in the modified coating
The thickness of piece is 10～40nm.
4. the modified magnesium alloy materials in surface according to any one of claim 1-3, it is characterised in that the modified coating
Thickness be 1～5 μm.
5. the preparation method of the modified magnesium alloy materials in a kind of surface as any one of claim 1-4, it is characterised in that
Including：
Magnesium alloy is placed in reactor, adding the alkaline solution of containing a source of aluminum makes its submergence magnesium alloy, the hydro-thermal at 60～160 DEG C
Process 5～15 hours, obtain the modified magnesium alloy materials in the surface.
6. preparation method according to claim 5, it is characterised in that source of aluminium is in aluminum nitrate, aluminum sulfate, aluminum acetate
At least one.
7. the preparation method according to claim 5 or 6, it is characterised in that aluminium ion in the alkaline solution of the containing a source of aluminum
Concentration is 0.01～0.05mol/L.
8. the preparation method according to any one of claim 5-7, it is characterised in that the pH value of the alkaline solution is 9
～12.
9. the preparation method according to any one of claim 5-8, it is characterised in that the compactedness of the reactor is 30
～70%.
10. a kind of modified magnesium alloy materials in surface any one of claim 1-4 are in manufacture medical magnesium alloy device
Application.
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