CN107190255A - A kind of super-hydrophobic magnesium or magnesium alloy materials and its preparation method and application - Google Patents
A kind of super-hydrophobic magnesium or magnesium alloy materials and its preparation method and application Download PDFInfo
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- CN107190255A CN107190255A CN201710232076.0A CN201710232076A CN107190255A CN 107190255 A CN107190255 A CN 107190255A CN 201710232076 A CN201710232076 A CN 201710232076A CN 107190255 A CN107190255 A CN 107190255A
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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
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Abstract
The present invention relates to a kind of super-hydrophobic magnesium or magnesium alloy materials and its preparation method and application.The super-hydrophobic magnesium or magnesium alloy materials include：Magnesium or magnesium alloy and the super-hydrophobic coat for being formed at the magnesium or Mg alloy surface, the super-hydrophobic coat include the magnesium hydroxide and magnalium laminar double-metal hydroxide mixed phase and the enuatrol of the surface scion grafting in the mixed phase of nano-sheet.Present invention gives the good corrosion resistance of magnesium or magnesium alloy and biocompatibility, the surface that can be widely used in magnesium or magnesium alloy medicine equipment is modified.
Description
Technical field
The present invention relates to a kind of biologic medical magnesium or the surface modifying method of magnesium alloy, one kind is particularly related to by water
The method for building ultra-hydrophobic high sticking power structure in material surface is heat-treated, belongs to technical field of metal material surface modification.
Background technology
Currently, medicine equipment is being undergone from non-degradable to degradable evolution.It is stainless with Ti and its alloy
Steel, Co-Cr alloys etc. are highly developed in clinical practice for the non-degradable medical metal material of representative, and its target is
Cause host immune response less as far as possible on the basis of matching is replaced organization mechanicses performance.However, Long-term clinical tracking and
Research finds that the problem of non-degradable implant at this stage is primarily present is to need second operation to take non-degradable implant
Go out, otherwise implant is easy to cause host response, and second operation further adds spirit and the financial burden of patient.
Therefore, the magnesium or magnesium alloy being close with complete biodegradability and modulus of elasticity with bone tissue turn into current research
Focus, and it is described as " biomedical metallic material of future generation ".The shortcoming of magnesium or magnesium alloy as medical material is electrochemical potential
Too low, corrosion rate is too fast.Quickly on the one hand corrosion can cause magnesium or magnesium alloy prematurely to lose mechanical performance, in addition a side
Face can also cause acute variation and inflammatory reaction of implant surrounding tissue liquid pH value etc..Therefore, how to improve magnesium or magnesium is closed
The corrosion resistance of gold, makes its degradation rate match with diseased region Healing Rate, while its surface can again had well
Cell compatibility is medical magnesium or the emphasis and difficult point of magnesium alloy research.
The content of the invention
The present invention is for too fast, the cell phase that solves current medical degradable magnesium or magnesium alloy degradation rate in clinical practice
Capacitive is not good enough, and there is provided a kind of new ultra-hydrophobic high sticking power magnesium or magnesium alloy materials for the problem of being easily caused implantation failure
And preparation method thereof.
The application provides a kind of ultra-hydrophobic high sticking power magnesium or magnesium alloy with good corrosion resistance and cell compatibility
Material, it includes：Magnesium or magnesium alloy and the super-hydrophobic coat for being formed at the magnesium or Mg alloy surface, the super-hydrophobic painting
Layer includes magnesium hydroxide and magnalium laminar double-metal hydroxide mixed phase and the surface in the mixed phase of nano-sheet
The enuatrol of scion grafting.
According to foregoing invention, magnesium or Mg alloy surface by nano-sheet magnesium hydroxide and magnalium laminar bimetal hydroxide
Thing mixed phase is constituted, and the surface scion grafting of mixed phase enuatrol.In the oleic acid of coarse Nanosurface and low surface free energy
Under the collective effect of sodium, modified magnesium or magnesium alloy materials has super-hydrophobic property.Super-hydrophobic coat is effectively improved
The corrosion resistance of material, meanwhile, the enuatrol of the most no biotoxicity of top layer scion grafting causes material to have good cytocompatibility
Property.Modified magnesium or the corrosion resistance of magnesium alloy are significantly improved, and its corrosion current has obvious reduction, and certainly
Corrosion potentials have obvious rise.The general super hydrophobic surface constructed according to lotus leaf effect, water droplet is in one kind and not infiltrated completely
State, it is easy to slid from material surface, therefore be unfavorable for cell in the adhesion of material surface and sprawl.And structure in the present invention
The super hydrophobic surface made, due to the special micro-nano structure in its surface, similar to petal effect, water droplet is in one on coarse surface
The state of kind of half infiltration, macroscopically shows as the adhesion superpower to water droplet, therefore the adhesion of cell will not be sprawled and cause very
Big influence.Further, since its corrosion resistance is obviously improved, and the magnesium hydroxide in coating, magnalium laminar bimetallic
Hydroxide and enuatrol etc. are all the fabulous materials of biocompatibility, therefore cell is after material surface adhesion is sprawled, also table
Reveal good multiplication rate, and the toxicity of its leaching liquor is substantially reduced.
It is preferred that the radial dimension of the flaky nanometer structure is 400~600nm, thickness is 50~200nm.
It is preferred that the thickness of the super-hydrophobic coat is at 1~5 μm.
It is preferred that the element composition of the super-hydrophobic coat is C：20~25wt%, O：40~60wt%, Mg：20~
30wt%, Al：2~6wt%.
The application also provides the preparation method of above-mentioned super-hydrophobic magnesium or magnesium alloy materials, including：
In the alkaline solution that magnesium or magnesium alloy are placed in containing a source of aluminum and enuatrol, hydro-thermal process obtains described at 100~150 DEG C
Super-hydrophobic magnesium or magnesium alloy materials.
The preparation method prepares above-mentioned super-hydrophobic magnesium or magnesium alloy materials, the letter of its technique by hydro-thermal process one-step method
Single, without special installation, required reagent also all environmental sound is conducive to large-scale industrialized production.In magnesium or magnesium alloy table
Face, super-drainage structure is built by hydro-thermal process one-step method, while improving the corrosion resistance and cell compatibility of material.
It is preferred that the pH value of the alkaline solution of the containing a source of aluminum and enuatrol is 10~13.
It is preferred that source of aluminium is aluminum soluble salt, preferably at least one of aluminum nitrate, aluminum sulfate, aluminum acetate,
In the alkaline solution, aluminium ion concentration is 0.02~0.06M.
It is preferred that in the alkaline solution, the concentration of the enuatrol is 20 μM~600 μM.
It is preferred that hydrothermal conditions are 10~24 hours.
The application also provides the application of above-mentioned super-hydrophobic magnesium or magnesium alloy materials in bio-medical apparatus is prepared.
Present invention gives the good corrosion resistance of magnesium or magnesium alloy and biocompatibility, can be widely used in magnesium or
The surface of magnesium alloy medicine equipment is modified.
Brief description of the drawings
Fig. 1 is the Sample Scan electron microscope and contact angle figure and water droplet obtained after being handled through embodiment 1 (a) and 2 (b)
The material of (d) is reversed (at embodiment 2 material (sample obtained after being handled through the embodiment 2) surface of vertical (c) and 180 °
The sample obtained after reason) surface adhesion situation；
The XRD spectrum of sample after Fig. 2 is pure magnesium and handled through Examples 1 and 2；
Fig. 3 is enuatrol powder (a), and the FTIR of sample surfaces powder schemes after being handled through embodiment 1 (b) and 2 (c)；
Fig. 4 is the cross-sectional view of sample after being handled through embodiment 1 (a) and 2 (b)；
Fig. 5 be pure magnesium and handled through Examples 1 and 2 after corrosion potential figure of the sample in 37 DEG C of phosphate buffered saline solution；
Fig. 6 be Human umbilical vein endothelial cells in pure magnesium and after handling through Examples 1 and 2 the adhesion on surface sprawl test result；
Toxicity of the leaching liquor of sample to cell after Fig. 7 is pure magnesium and handled through Examples 1 and 2；
Multiplication rate after Fig. 8 is endothelial cell in pure magnesium and handled through Examples 1 and 2 after sample surfaces culture one day.
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, is not intended to limit the present invention.
Characteristic of the invention in order to solve existing medical magnesium or magnesium alloy materials corrosion resistance difference and cell compatibility difference,
The super-hydrophobic magnesium or magnesium alloy materials with good corrosion resistance and cell compatibility being modified there is provided a kind of surface.
In an embodiment of the present invention, there is modified coating (super-hydrophobic coat) on the surface of magnesium or magnesium alloy materials, should
Modified coating has the magnesium hydroxide and magnalium laminar double-metal hydroxide mixed phase of nano-sheet, and in magnesium hydroxide and magnesium
The surface scion grafting of the aluminium layered double hydroxide mixed phase enuatrol of low-surface-energy.Enuatrol mainly leads to magnesium hydroxide
Van der Waals force is crossed together with Hydrogenbond, enuatrol mainly passes through the oleic acid base of negative electricity with magnalium laminar double-metal hydroxide
Electrostatic attraction between group and the metallic hydrogen oxide layer of positive electricity is combined together.On this coarse Nanosurface and low surface certainly
Under the collective effect of the enuatrol of energy, modified magnesium or magnesium alloy materials has super-hydrophobic property, for example its contact angle
Up to more than 151 °, also with super adhesion, material is reversed into water droplet after 180 ° and also not fallen out.This super-hydrophobic property has
Improve to effect the corrosion resistance of material.Meanwhile, the high-adhesiveness under half wet face state does not interfere with cell in material surface yet
Adhesion.In addition, magnesium hydroxide, magnalium laminar double-metal hydroxide and the most oleic acid of the no biotoxicity of top layer scion grafting
Sodium etc. is all the fabulous material of biocompatibility so that material has good cell compatibility.It is an advantage of the current invention that
Under coarse Nanosurface (micro-nano structure) and the synergy of the enuatrol of low surface free energy, by it is super-hydrophobic raising magnesium or
After the corrosion resistance of magnesium alloy, because liquid and material surface are the contact conditions of half infiltration, cell can't be influenceed in material
The adhesion on surface.
In the present invention, magnesium or magnesium alloy refer to magnesium metal or the alloy of other elements composition are added by matrix of magnesium.Institute
State other elements and include but is not limited to aluminium, zinc, zirconium etc..Because present invention is generally directed to the magnesium clinically used or the anti-corruption of magnesium alloy
Magnesium or magnesium alloy are preferably medical magnesium or magnesium alloy, including but not limited to model in the problem of corrosion is poor, therefore the present invention
Any one in ZK60, JDBM, AZ31, AZ61, AZ91 magnesium or magnesium alloy.
In the present invention, magnalium laminar double-metal hydroxide be by positively charged magnalium hydroxide layer and it is electronegative it is cloudy from
The hydrotalcite-like compound of sublayer composition.The magnalium laminar double-metal hydroxide may also function as anticorrosive effect in itself, it is specific and
Speech, in the high corrosive liquid of chlorine ion concentration, due to the moon such as nitrate anion, the borates of magnalium laminar double-metal hydroxide interlayer
Ion can be swapped with chlorion, so as to reduce the concentration of alloy surface chlorion, it is suppressed that the hydrogen-oxygen of chlorion pair
Change the corrosion of magnesium layer, so as to completely cut off the contact between corrosive liquid and substrate magnesium or magnesium alloy, realize the guarantor to magnesium or magnesium alloy
Shield.
Magnesium hydroxide and the radial dimension of magnalium laminar double-metal hydroxide mixed phase nanometer sheet can be 400~600nm,
Thickness can be 50~200nm.Each nanometer sheet forms fine and close and coarse surface texture in magnesium or the random arrangement of Mg alloy surface
(micro-nano structure).The thickness of whole super-hydrophobic coat can be 1~5 μm.
In an embodiment of the present invention, magnesium or Mg alloy surface element composition be C (20~25wt%), O (40~
60wt%), Mg (20~30wt%), Al (2~6wt%).
In an embodiment of the present invention, super-drainage structure is built in magnesium or Mg alloy surface using hydro-thermal process one-step method.
In one example, magnesium or magnesium alloy are placed in hydro-thermal liquid and carry out hydro-thermal process.Hydro-thermal liquid can be to contain silicon source and enuatrol
Alkaline aqueous solution.
The pH value of hydro-thermal liquid can be 10~13, preferably 12~13, more preferably 12.Usable alkali such as sodium hydroxide or
Hydro-thermal liquid pH value is adjusted to 10~13 by potassium hydroxide.
Silicon source can be aluminum soluble salt, preferably at least one of aluminum nitrate, aluminum sulfate, aluminum acetate.Aluminium in hydro-thermal liquid
The concentration of ion can be 0.02~0.06M.The concentration of enuatrol can be 20 μM~600 μM in hydro-thermal liquid.Aluminium ion and enuatrol
Molar concentration rate can be 1：(0.01~0.04).By adjusting the ratio of the two, can adjust ultimately form it is super-hydrophobic in
Magnesium hydroxide and magnalium laminar double-metal hydroxide mixed phase and the ratio of enuatrol.
Hydro-thermal reaction equipment can be electric drying oven with forced convection and reactor.Hydro-thermal process temperature can be 100~150 DEG C.Water
Heat treatment time can be 10~24h.
Magnesium or magnesium alloy can be also machined and cleaning step before hydro-thermal process.For example by magnesium or magnesium alloy plate according to
It is secondary to be polished flat with 600# and 1000#SiC sand paper, then with the clean simultaneously drying at room temperature of absolute ethyl alcohol ultrasound.
Magnesium or Mg alloy surface after hydro-thermal can be cleaned and done after hydro-thermal process by magnesium or magnesium alloy with a large amount of deionized waters
Only.The present invention is prepared by one-step method, and raw material, technique are all very simple.
It is double golden by the magnesium hydroxide and magnalium laminar of coarse nano-sheet by the modified obtained material surface of the present invention
Belong to hydroxide mixing phase composition, and the enuatrol of low-surface-energy is combined on the surface of mixed phase.Corrosion resistance result shows
Super-hydrophobic magnesium or magnesium alloy have more preferable corrosion resistance.For example, the super-hydrophobic magnesium of the present invention or the corrosion potential of magnesium alloy can
For more than -1.45V, corrosion current can be 0.982 μ A/cm2Hereinafter, polarization resistance can be 1.16 × 106Ω·cm-2More than.Carefully
Born of the same parents' experiment shows, compared with hydrophilic modified surface, and super hydrophobic surface can't influence cell adherence, modified material extraction
Liquid is substantially reduced to the toxicity of cell, and cell is bred also faster in material surface.This shows modified magnesium or magnesium alloy
Corrosion resistance and cell compatibility have significant raising.Present invention gives the good corrosion resistance of magnesium or magnesium alloy and
Biocompatibility, the surface that can be widely used in magnesium or magnesium alloy medicine equipment is modified.
Embodiment is enumerated further below to describe the present invention in detail.It should be understood that following examples are served only for the present invention
It is further described, and it is not intended that limiting the scope of the invention, those skilled in the art is according to the present invention
Some nonessential modifications and adaptations for making of the above belong to protection scope of the present invention.Following specific works of example
Skill parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done suitably by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
It is 2mm by thickness, length and width are all 10mm pure magnesium sheet, remove surface oxidation with 600# and 1000# SiC sand paper successively
Layer, then it is clean with alcohol ultrasound.Hydro-thermal process is carried out afterwards, and hydro-thermal liquid is 50ml 0.02M aluminum nitrate solution, and uses hydrogen
Its pH value is transferred to 12.8 by sodium oxide molybdena or potassium hydroxide, and reaction temperature is 120 DEG C, and the reaction time is 12h.Gained sample is labeled as
LDH。
(a) in Fig. 1 is scanning electron microscope (SEM) photograph and the contact of the magnesium material surface topography obtained through the present embodiment modification
Angle is tested.It can be seen that surface is the structure of one layer of fine and close nano-sheet after processing, its contact angle is about 66.1 °
Left and right.Fig. 2 (LDH) gives handled through the present embodiment after sample surfaces XRD, it can be seen that after treatment
The structure of material surface is the mixed phase of magnesium hydroxide and magnalium laminar double-metal hydroxide.(b) in Fig. 3 is given from warp
The infrared spectrogram for the powder that sample surfaces after the present embodiment processing are scraped off, wherein 3442cm-1Corresponding peak represents structure
In some hydrones and hydroxyl vibration peak, 1635cm-1Locate the hydrone that corresponding peak represents Mg-Al LDH interlayers.In Fig. 4
(a) give handled through the present embodiment after sample cross-sectional view, it can be seen that the thickness of coating be 3.48 ±
0.34μm.Table 1 gives handled through the present embodiment after sample surfaces element composition be C：7.90 ± 1.28wt%, O：60.33
± 1.35wt%, Mg：28.58 ± 2.34wt%, Al：3.19 ± 0.42wt%.
Embodiment 2
It is 2mm by thickness, length and width are all 10mm pure magnesium sheet, remove surface oxidation with 600# and 1000# SiC sand paper successively
Layer, then it is clean with alcohol ultrasound.Hydro-thermal process is carried out afterwards, and hydro-thermal liquid is 50ml 0.02M aluminum nitrate solution, and adds
400 μM of enuatrol, and its pH value is transferred to 12.8 using sodium hydroxide or potassium hydroxide, reaction temperature is 120 DEG C, during reaction
Between be 12h.Gained sample is labeled as LDHSO.
(b) in Fig. 1 is scanning electron microscope (SEM) photograph and the contact of the magnesium material surface topography obtained through the present embodiment modification
Angle is tested.It can be seen that surface is the structure of one layer of fine and close nano-sheet after processing, the radial dimension of nanometer sheet is
400~600nm, thickness is 50~200nm, and its contact angle is about 151.9 ° or so.(c) and (d) in Fig. 1 is water droplet vertical
Material surface and 180 ° of reversings material surface adhesion situation, as can be seen from Fig. material water droplet is shown superpower viscous
Attached power.Its strong adhesion derives from the negative pressure that the air sealed up for safekeeping under half wet face state is produced, and wetted part, solid liquid interface
Van der Waals force.Fig. 2 (LDH) gives handled through the present embodiment after sample surfaces XRD, it can be seen that by
The structure of material surface is the mixed phase of magnesium hydroxide and magnalium laminar double-metal hydroxide after reason.The crystallinity of enuatrol is not
Reach, therefore XRD has no and detects its diffraction maximum.(c) in Fig. 3 gives the sample surfaces after being handled through the present embodiment and scraped
The infrared spectrogram of the powder come, wherein 3442cm-1Corresponding peak represents some hydrones and hydroxyl vibration peak in structure,
1635cm-1Locate the hydrone that corresponding peak represents Mg-Al LDH interlayers.From unlike (b) in Fig. 3, in 2921cm-1With
2852cm-1Place has also detected that peak, corresponds to that C-H in oily sulfonate groups is symmetrical and nonsymmetrical vibration peak respectively.Illustrate material list
Contain oily sulfonate groups in face.(b) in Fig. 4 gives handled through the present embodiment after sample cross-sectional view, can from figure
Go out, the thickness of coating is 2.05 ± 0.09 μm.Table 1 gives handled through the present embodiment after sample surfaces element composition be C：
23.43 ± 0.86wt%, O：48.53 ± 0.53wt%, Mg：25.73 ± 0.23wt%, Al：2.32 ± 0.11wt%.From table
In it can be seen that the surface of embodiment 2 C element content be far above embodiment 1, further illustrate the surface scion grafting of embodiment 2 oil
Sulfonate groups；
Table 1：The Elemental redistribution mass percent of sample surfaces after what X-ray energy spectrometer (EDS) was measured handled through Examples 1 and 2
Embodiment 3
The sample obtained to unmodified sample and above-described embodiment 1,2 carries out electro-chemical test.Corrosive liquid used is slow for phosphate
Electuary (PBS), test temperature is 37 DEG C.Instrument is electrochemical workstation (Shanghai Chen Hua CHI760C).Test sample is
It is reference electrode to electrode, calomel electrode that working electrode, graphite rod, which are,.
Fig. 5 be pure magnesium and handled through Examples 1 and 2 after corrosion potential of the sample in 37 DEG C of phosphate buffered saline solution
Figure.For the purer magnesium of sample obtained as we can see from the figure after implementing 1 and the processing of embodiment 2, corrosion potential is all positive
Move, and corrosion current is all reduced, and illustrates that the corrosion resistance of modified sample is obviously improved.And further by tower
The polarization resistance that Fei Er calculation by extrapolation comes out is respectively 5.80 × 104(pure magnesium), 3.46 × 104(LDH)、1.16×106
(LDHSO).The corrosion resistance that the sample being modified through embodiment 2 can significantly be found out is best.
Embodiment 4
Using Human umbilical vein endothelial cells HUVEC in vitro cultures and fluorescent staining experimental evaluation above-described embodiment 1 and 2 modifications
The influence that gained magnesium material is sprawled to cell adherence.Specific method is as follows：
1) it will be put into by the sample of 12h ultraviolet sterilizations in 24 well culture plates, it is 5 × 10 that 1mL density is added dropwise per hole4cell/mL
Cell suspension；
2) Tissue Culture Plate is put into 5%CO236.5 DEG C of hatchings in the cell culture incubator of saturated humidity；
3) culture 1, after 4 and 24 hours, cell is dyed with FITC and DAPI, and use laser confocal microscope
(CLSM) observe.
Test result is sprawled in the adhesion on surface after Fig. 6 is HUVEC in pure magnesium and handled through Examples 1 and 2.Can from Fig. 6
To see whether 1 hour, 4 hours or 24 hours, cell through the modified material surface of embodiment 2 sprawl situation with
Embodiment 1 is much the same, illustrates the magnesium material surface of ultra-hydrophobic high sticking prepared through embodiment 2, is improving the anti-corruption of coating
While corrosion, cell can't be influenceed in the adhesion of material surface.
Embodiment 5
Using Human umbilical vein endothelial cells (HUVEC) in vitro culture experimental evaluation above-described embodiment 1,2 and unmodified magnesium material
The toxicity of leaching liquor.Specific method is as follows：
1) it will be put into by the sample of 12h ultraviolet sterilizations in 24 well culture plates, per hole 2mL culture mediums；Dripped simultaneously in 96 orifice plates
Plus 200 μ L density be 5 × 104cell/mL cell suspensions；
2) two pieces of growth plates are put into 36.5 DEG C of cell culture incubators of 5%CO2 saturated humidities；
3) nutrient solution that will be placed with the Tissue Culture Plate of sample takes out, and the concentration of the initial leaching liquor of gained is defined as 100%, then uses
Culture medium dilutes the leaching liquor for obtaining 60% and 30% concentration.The cell culture fluid in 96 orifice plates is sucked afterwards, and added per hole
Enter the leaching liquor of 200 each gradients of μ L；
4) after cultivating 1 day, original fluid is sucked, the new culture containing blue (AlamarBlueTM) dye liquor of 10% ALMA is added
Liquid, culture plate is placed in incubator and cultivated after 4h, from every hole 100 μ L nutrient solutions of taking-up are put into 96 orifice plates；
5) each hole is measured in the case where wavelength is 530nm exciting light using ELIASA (BIO-TEK, ELX800), the transmitting at 590nm
Luminous intensity.Its light intensity is proportionate with cell quantity.
Toxicity of the leaching liquor of sample to cell after Fig. 7 is pure magnesium and handled through Examples 1 and 2.As can be seen from the figure
Unmodified magnesium material extraction is very big to the toxicity of cell, and cytoactive only has 20%, and passes through the leaching of the modified material of embodiment 1
The toxicity of extract is significantly reduced, and cytoactive is lifted to 60%, and the toxicity by the modified material of embodiment 2 is minimum, culture
Cytoactive is close to 90% after one day.
Embodiment 6
Using Human umbilical vein endothelial cells (HUVEC) in vitro culture experimental evaluation above-described embodiment 1,2 and unmodified magnesium material pair
The influence of normal cell activity.It is thin using blue (AlamarBlueTM, AbD serotec Ltd, UK) kit detection of ALMA
Proliferative conditions of the born of the same parents in material surface.Method is as follows：
1) it will be put into by the sample of 12h ultraviolet sterilizations in 24 well culture plates, it is 5 × 104cell/mL that 1mL density is added dropwise per hole
Cell suspension；
2) Tissue Culture Plate is put into 36.5 DEG C of hatchings in the cell culture incubator of 5%CO2 saturated humidities；
3) after cell culture 1 day, original fluid is sucked, the culture plate renewed, and add blue containing 10% ALMA
(AlamarBlueTM) the new nutrient solution of dye liquor, culture plate is placed in incubator and cultivated after 4h, and 100 μ L trainings are taken out from every hole
Nutrient solution is put into 96 orifice plates；
5) each hole is measured in the case where wavelength is 530nm exciting light using ELIASA (BIO-TEK, ELX800), the transmitting at 590nm
Luminous intensity.Its light intensity is proportionate with cell quantity.
Multiplication rate after Fig. 8 is endothelial cell in pure magnesium and handled through Examples 1 and 2 after sample surfaces culture one day.
As can be seen from the figure after the culture of one day, cell is minimum in unmodified magnesium material number of surfaces, is modified through embodiment 1
Afterwards, cell is obviously improved in the quantity of material surface, and modified by embodiment 2, and the cell quantity of material surface is most
It is many.
The result of integrated embodiment 4 and embodiment 5, it can be seen that by the cell phase of the modified magnesium material of embodiment 2
Capacitive is best.
Claims (10)
1. a kind of super-hydrophobic magnesium or magnesium alloy materials with good corrosion resistance and cell compatibility, it is characterised in that including：
Magnesium or magnesium alloy and the super-hydrophobic coat for being formed at the magnesium or Mg alloy surface, the super-hydrophobic coat include nanometer sheet
The magnesium hydroxide and magnalium laminar double-metal hydroxide mixed phase of shape and the oleic acid of the surface scion grafting in the mixed phase
Sodium.
2. super-hydrophobic magnesium according to claim 1 or magnesium alloy materials, it is characterised in that the footpath of the flaky nanometer structure
It is 400~600nm to size, thickness is 50~200nm.
3. super-hydrophobic magnesium according to claim 1 or 2 or magnesium alloy materials, it is characterised in that the super-hydrophobic coat
Thickness is at 1~5 μm.
4. super-hydrophobic magnesium according to any one of claim 1 to 3 or magnesium alloy materials, it is characterised in that described super thin
The element composition of water coating is C：20~25wt%, O：40~60wt%, Mg：20~30wt%, Al：2~6wt%.
5. a kind of preparation method of the super-hydrophobic magnesium or magnesium alloy materials any one of Claims 1-4, its feature exists
In, including：
In the alkaline solution that magnesium or magnesium alloy are placed in containing a source of aluminum and enuatrol, hydro-thermal process obtains described at 100~150 DEG C
Super-hydrophobic magnesium or magnesium alloy materials.
6. preparation method according to claim 5, it is characterised in that the pH of the alkaline solution of the containing a source of aluminum and enuatrol
It is worth for 10~13.
7. the preparation method according to claim 5 or 6, it is characterised in that source of aluminium is aluminum soluble salt, preferably nitre
At least one of sour aluminium, aluminum sulfate, aluminum acetate, in the alkaline solution, aluminium ion concentration is 0.02~0.06M.
8. the preparation method according to any one of claim 5 to 7, it is characterised in that described in the alkaline solution
The concentration of enuatrol is 20 μM~600 μM.
9. the preparation method according to any one of claim 5 to 8, it is characterised in that hydrothermal conditions are 10~24
Hour.
10. the super-hydrophobic magnesium or magnesium alloy materials any one of a kind of Claims 1-4 are in bio-medical apparatus is prepared
Application.
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Cited By (3)
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|---|---|---|---|---|
| CN109338451A (en) * | 2018-12-03 | 2019-02-15 | 中国科学院海洋研究所 | A kind of aluminium base is anticorrosive, antimicrobial attachment super-hydrophobic film and preparation method thereof |
| CN112549224A (en) * | 2020-11-28 | 2021-03-26 | 浙江农林大学 | Method for manufacturing colored super-hydrophobic bamboo wood |
| CN115613103A (en) * | 2022-11-07 | 2023-01-17 | 南京工程学院 | Micro-arc magnesium oxide alloy surface hydrophobic Mg-Al hydrotalcite film and one-step preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113012A (en) * | 2006-07-28 | 2008-01-30 | 北京化工大学 | Highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite film and method for preparing same |
| CN101538019A (en) * | 2009-04-24 | 2009-09-23 | 山东慧科助剂股份有限公司 | Method for preparing hydrophobic nanometer hydrotalcite |
| CN103241752A (en) * | 2013-05-29 | 2013-08-14 | 肇庆学院 | Preparation method of surface-modified hydrotalcite |
| CN104561999A (en) * | 2014-12-19 | 2015-04-29 | 北京科技大学 | Method for preparing superhydrophobic film on magnesium alloy surface |
| CN106283017A (en) * | 2016-09-07 | 2017-01-04 | 南京工程学院 | Magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg Sn houghite composite membrane and preparation method thereof |
-
2017
- 2017-04-11 CN CN201710232076.0A patent/CN107190255B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113012A (en) * | 2006-07-28 | 2008-01-30 | 北京化工大学 | Highly-adherent super-hydrophobic double-functional intercalation configuration type hydrotalcite film and method for preparing same |
| CN101538019A (en) * | 2009-04-24 | 2009-09-23 | 山东慧科助剂股份有限公司 | Method for preparing hydrophobic nanometer hydrotalcite |
| CN103241752A (en) * | 2013-05-29 | 2013-08-14 | 肇庆学院 | Preparation method of surface-modified hydrotalcite |
| CN104561999A (en) * | 2014-12-19 | 2015-04-29 | 北京科技大学 | Method for preparing superhydrophobic film on magnesium alloy surface |
| CN106283017A (en) * | 2016-09-07 | 2017-01-04 | 南京工程学院 | Magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg Sn houghite composite membrane and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FENG PENG ET AL.: ""Enhanced Corrosion Resistance and Biocompatibility of Magnesium Alloy by Mg−Al-Layered Double Hydroxide"", 《APPLIED MATERIALS & INTERFACES》 * |
| 赵丽丽: ""类水滑石薄膜的制备及其耐腐蚀性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109338451A (en) * | 2018-12-03 | 2019-02-15 | 中国科学院海洋研究所 | A kind of aluminium base is anticorrosive, antimicrobial attachment super-hydrophobic film and preparation method thereof |
| CN112549224A (en) * | 2020-11-28 | 2021-03-26 | 浙江农林大学 | Method for manufacturing colored super-hydrophobic bamboo wood |
| CN112549224B (en) * | 2020-11-28 | 2022-03-04 | 浙江农林大学 | Method for manufacturing colored super-hydrophobic bamboo wood |
| CN115613103A (en) * | 2022-11-07 | 2023-01-17 | 南京工程学院 | Micro-arc magnesium oxide alloy surface hydrophobic Mg-Al hydrotalcite film and one-step preparation method and application thereof |
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