CN109778160A - Medical magnesium alloy implant inorganic agent and its application method - Google Patents
Medical magnesium alloy implant inorganic agent and its application method Download PDFInfo
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- CN109778160A CN109778160A CN201711124377.8A CN201711124377A CN109778160A CN 109778160 A CN109778160 A CN 109778160A CN 201711124377 A CN201711124377 A CN 201711124377A CN 109778160 A CN109778160 A CN 109778160A
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Abstract
The invention discloses a kind of medical magnesium alloy implant inorganic agents, contain: the gallium ion of 0.01~0.5 mol/L；The phosphate anion of 0.005~0.5 mol/L；The pH value of the medical magnesium alloy implant inorganic agent is adjusted into the buffer to 1.0~5.0；Wherein the molar ratio of gallium ion and phosphate anion is 1:(0.6~1.2).In addition, the invention also discloses a kind of application methods of medical magnesium alloy implant inorganic agent, comprising steps of 1) carrying out surface preparation to medical magnesium alloy implant；2) by a period of time in the medical magnesium alloy implant merging medical magnesium alloy implant inorganic agent Jing Guo surface preparation；3) medical magnesium alloy implant is taken out, it is dry after washing.In addition, the invention also discloses a kind of medical magnesium alloy implant, it is processed according to above-mentioned application method.The medical magnesium alloy implant has good biocompatibility and bactericidal effect with inorganic agent.
Description
Technical field
The present invention relates to the inorganic agent of a kind of inorganic agent and its application method more particularly to a kind of bio-medical material and its
Application method.
Background technique
In medical Bone Defect Repari and bone implant material, stainless steel, cobalt-chromium-molybdenum alloy and titanium, titanium alloy are because its is excellent
Mechanical property, biocompatibility and corrosion resistance become widely used clinical application biomaterial.But above-mentioned three kinds normal
The main mechanical properties of metal based biomaterial, such as elasticity modulus are advised, is not matched that with skeleton, easily generation " stress
Shielding " effect in turn results in the bone tissue contacted with implant and generates atrophy or even loose symptom, and it is de- to eventually lead to implant
It falls and fails.Required subsequent prosthesis necessarily brings the financial burden and pain for being difficult to bear to patient.Meanwhile normal
Advise (such as bone nail, the bone plate prepared based on stainless steel material of nondegradable metal implant used in repair of fractured bones
Deng), after the recovery from illness of affected part, subsequent procedures taking-up is generally required, also will increase rehabilitation course after treatment cost and lengthening.It can drop
The object material that depolymerizes can partially meet above-mentioned requirements, but its too low mechanical performance is difficult the load-bearing replaced required for supporting
The daily stress demand of bony site.
At present magnesium alloy be it is emerging, can most light structural metallic materials in practical applications.Because its excellent high ratio is strong
Degree and specific stiffness, excellent electromagnetic shielding performance, to be easy to machining, weldability, impact resistance, easy castability, size steady
It is fixed, be easily recycled and the advantages that natural rich reserves, have and be widely used in the system such as space flight, aviation, electronics, communication, automobile
The prospect for making industry is known as " green engineering material of 21 century ".However, even if comparing (normal electrode with pure magnesium metal material
Point -2.372VSHE), magnesium alloy also has the shortcomings that corrosion resistance is poor.In corrosive environment, especially contain Cl-From
In the solution of son, it is easy to generate heavy corrosion.Therefore, limitation magnesium alloy is widely used is faced in various engineer applications
One of principal element, be how effectively to improve the corrosion resistance of magnesium alloy.
However the low corrosion resistance of magnesium and magnesium alloy is but that research and development are opened using degradable medical Bone Defect Repari and bone implant material
New possibility.Firstly, reserves very abundant of the magnesium in the earth's crust.Magnesium is the inorganic elements of the 4th high-content in human body simultaneously,
It is that body metabolism synthesizes indispensable important nutrient, and plays an active part in energy transportation, storage and utilization.And because of its human body
Interior catabolite, harm to the human body is minimum, can be excreted by human normal metabolism.Secondly, the intensity of magnesium alloy,
The critical mechanicals such as elasticity modulus performance indicator and skeleton are very close, can be to avoid the various of existing medical metal material
Problem.It is similar with people's bone finally, the mass density of magnesium alloy is well below stainless steel, vitallium and titanium alloy, it can be with
Reduce the burden generated after implantation human body to patient's daily life.
Although domestic and foreign scholars have widely carried out the research and development of Medical magnesium alloy material, clinical medical example pole
It is limited.Main challenge is to find effectively control magnesium alloy in the intracorporal method that is orderly, slowly degrading of people.Too fast drop
Solution preocess can bring series of negative to influence especially at implantation initial stage, directly or indirectly restrict the clinical table of magnesium alloy
It is existing.For example, magnesium alloy can subcutaneously generate a large amount of hydrogen, hydroxide ion and various degradations in the intracorporal fast degradation of people
Product.Its presence can inhibit wound healing, inflammation infection, bubble hydrogen largely subcutaneously to assemble, and then implant surgery is caused to be failed.It crosses
Fast degradation process can greatly damage the mechanical strength of magnesium alloy implant, it is made to lose its support before the healing of fracture affected part
Fixed effect eventually leads to operation failure.Therefore, be badly in need of find one kind efficiently control magnesium alloy implant especially after surgery just
The degradation scheme of phase, it is ensured that its orderly, slow, harmless progress.
Process for modifying surface is by the Surface Creation one in magnesium and its alloy as a kind of important corrosion protection method
Passivating film is planted magnesium alloy and corrosive environment is isolated, and then improves their corrosion resistances during service, extends it
Service life.The method for improving corrosion resistance of magnesium alloy energy by surface modification technologies, mainly there is chemical composition coating, inertia
Metal plating coating, differential arc oxidation, anodic oxidation, hybrid material, organic coating etc..Wherein, chemical conversion membrane technology has
Have the advantages that it is simple and easy, do not need special installation, be suitable for structure is complicated and large scale workpiece, can be greatly reduced and be produced into
This, thus be widely adopted.
At this stage, many chemically transformed film techniques have been exploited for improving the corrosion resistance of magnesium alloy materials.Its
Basic principle is to be in contact, chemically reacted with film forming solution by magnesium alloy, forms one layer of attachment in metallic substrate surface
Power is good, stability is high, the passivation compound film layer of slightly solubility, is influenced to protect basis material not by corrosive environment.However,
Existing diversity chemically transformed film technique, for example, chromate, fluoride, alum salts, stannate, rare earth metal salt, ionic liquid
Body and hot melt salt, but because of their intrinsic, higher bio-toxicity disadvantages, and it is raw to be effectively implanted body medical equipment
Production is used.Chemical composition coating based on calcium phosphate has lower production costs, excellent biocompatibility and to environment shadow
Lesser advantage is rung, therefore is compared by industrial welcome.However, synthos chemical composition coating can only provide magnesium alloy
Limited defencive function, and can only keep stablizing in the section that a pH value changes very little, thus greatly limit this change
Learn practical application of the conversion membrane technology in field of engineering technology.
Implant replacement is postoperative to be easily inflamed and the complication such as infected wound, plays post-operative recovery or even implant
Its expectation function all generates immeasurable negative effect.Although implant device can all undergo a system before being placed in human body
Column disinfection and sterilization process, but still can not effectively avoid infected wound.
The process for treating surface such as a variety of representative use chemical composition coatings have been developed at present in Biological magnesium alloy table
Wheat flour is for the protection membrane process based on calcium phosphate (mainly hydroxyapatite).Such as: Publication No. CN105420789A, it is open
Day is on March 23rd, 2016, entitled " pure magnesium or the hydrophobic composite biological coatings of Mg alloy surface and preparation method thereof "
Chinese patent literature discloses a kind of pure magnesium or the hydrophobic composite biological coatings of Mg alloy surface and preparation method thereof, the patent
Technical solution disclosed in document use pure magnesium and MgCa, MgZnCa, MgSr, MgZnZr or MgZn Mg alloy surface according to
It is secondary to protect hydrophobic hydroxyapatite composite biologically active coating using the preparation of the methods of differential arc oxidation, electro-deposition and hydrophobic treatment
Technique.Although the hydrophobic composite biological coatings have good corrosion resistance, paint film adhesion, biocompatibility and bone
Inducibility, but its technique is relative complex, and maximum response time is up to 4.5 hours, thus carries out industrialization production to its technique
Extreme difficulties are caused, in addition, the patent document is not directed to any anti-microbial property.
Publication No. CN105420796A, publication date are on March 23rd, 2016, entitled " magnesium-based surface carbon nanotubes-
The Chinese patent literature of the modified coating and preparation method of hydroxyapatite " discloses a kind of magnesium-based surface carbon nanotubes-hydroxyl
The modified coating and preparation method thereof of base apatite, technical solution disclosed in the patent document use on magnesium-base metal material
(including pure magnesium, MgZn, MgMn, MgCa, MgSr or MgAl alloy) contains carbon nanotube by differential arc oxidation-electrophoretic deposition preparation
Modified hydroxyapatite coating layer preparation process.Its technical characterstic is that can effectively seal the hole of differential arc oxidation coating, and pass through
Introducing high-strength light carbon nanotube and being formed has high-intensitive, obdurability and wearability hydroxyapatite bioactive coating.So
And technique involved in the patent document still needs to longer preparation time (no less than one hour) and is not directed to sterilizing function.
Publication No. CN101461964, publication date are on June 24th, 2009, a kind of entitled " biological medical degradable magnesium
The Chinese patent literature of the bioactivity surface modification method of alloy " discloses a kind of biology of biological medical degradable magnesium alloy
Active surface method of modifying, technical solution disclosed in the patent document use on magnesium-base metal material (including pure magnesium and
A series of commercialization magnesium alloys) technique for preparing chemical composition coating middle layer and outer layer bioactive ceramic layer.Its technical characterstic is
Intermediate chemical composition coating can control simultaneously the degradation rate of magnesium alloy base material and improve the system of outer layer bioactive ceramic layer
The binding force of standby performance and matrix.However technique involved in the patent document still needs to multistep reaction process, preparation process is more multiple
Miscellaneous, reaction condition influences the property of final coating product huge.
Based on this, it is expected that obtaining a kind of medical magnesium alloy implant inorganic agent, agent obtains medical magnesium through this process
Alloy implant forms a kind of new chemical conversion membrane coat, and the coating have good biocompatibility, it is excellent can
Control degradation and postoperative bactericidal effect early period.
Summary of the invention
One of the objects of the present invention is to provide a kind of medical magnesium alloy implant inorganic agent, medical magnesium alloy implantation
Body inorganic agent environmental sound, without the ingredient that is harmful to the human body, and cheap, good corrosion resistance, good anti-bacterial effect, operation side
Just, it can be applied to large-scale industrial production.
In order to achieve the purpose that foregoing invention, the present invention provides a kind of medical magnesium alloy implant inorganic agents, contain
Have:
The gallium ion of 0.01~0.5 mol/L；
The phosphate anion of 0.005~0.5 mol/L；
The pH value of the medical magnesium alloy implant inorganic agent is adjusted into the buffer to 1.0~5.0；
Wherein the molar ratio of gallium ion and phosphate anion is 1:(0.6~1.2).
In technical solutions according to the invention, effective component is phosphoric acid gallium, by gallium ion in conjunction with phosphate anion
It arrives, after the medical magnesium alloy implant is coated with inorganic agent, so that Mg alloy surface covers to form chemical composition coating, it should
Chemical composition coating is a kind of crystalline compounds conversion film, including magnesia, magnesium hydroxide, magnesium phosphate and phosphoric acid gallium, is compared
There is characteristic stable in more extensive pH value region in the conversion film based on phosphate of the prior art.This is because oxygen
The crystalline compounds for changing magnesium, magnesium hydroxide and phosphoric acid gallium have extremely low solubility.Therefore, as magnesium alloy implant
The medical magnesium alloy implant inorganic agent chemical composition coating obtained of the present invention of anti-sheath is in strong acid/alkalinity ring
It is also not readily dissolved under border.It can thus be seen that the medical magnesium alloy implant stabilization with super strength with the chemical composition coating
Property.
It should be noted that phosphoric acid gallium can be mixed with by the aqueous solution and phosphate solution of gallium salt
At, it can also be by hybrid solid shape gallium salt particle and phosphate solid particle, then be placed in stirring and dissolving in water and mix
Proportion is that required molar ratio prepares, and can also be obtained by the way that gallium salt particle to be blended in phosphatic aqueous solution
It obtains or is obtained by the way that phosphate solid particle to be blended in the aqueous solution of gallium salt.
In above scheme, it can contain in medical magnesium alloy implant inorganic agent of the present invention and effective component
Do not conflict, influence ion or compound that effective component acts on.
In addition, medical magnesium alloy implant of the present invention is to stablize chemical conversion using buffer with inorganic agent
The pH value of membrane reagent, and then obtain the stable conversion film product of quality.By the medical magnesium alloy implant inorganic agent
It is magnesium and magnesium alloy because under conditions of lower buffering pH value (such as less than pH5.0) that pH value, which is adjusted to 1.0~5.0,
The reaction of the chemical composition coating on surface can generally be carried out with faster rate.If the medical magnesium alloy after buffering enters body processing
The pH value of agent is too low (such as less than pH1.0), and the reaction process of conversion film can become unstable, while generating and largely need not
The impurity wanted.
In addition, control gallium and phosphorus acid ion concentration are under conditions of a certain range, there are the pH values of certain buffering
Section to sterilize corrosion resistance chemical composition coating, and there is relatively reliable and stable forming process (and can avoid to greatest extent
The generation of impurity).The reaction rate of chemical composition coating in inorganic agent gallium ion with phosphorus acid ion concentration raising and add
Fastly.However, gallium ion can also reduce the control for producing the pH value for stablizing chemical composition coating with the raising of phosphorus acid ion concentration
Section processed, and then improve the difficulty of production.Therefore, comprehensively consider the quality and throughput rate of the product finally obtained, the present invention
The technical solution controls gallium ion concentration, phosphorus acid ion concentration and inorganic agent pH value: 0.01~0.5 rubs
You/liter gallium ion；The phosphate anion of 0.005~0.5 mol/L；By the medical magnesium alloy implant inorganic agent
PH value is adjusted to 1.0~5.0.
Furthermore another object of the present invention is to provide a kind of medical magnesium alloy implant inorganic agent, which is closed
Golden implant inorganic agent environmental sound without the ingredient that is harmful to the human body, cheap, good corrosion resistance, antibacterial, and operates
It is convenient, it can be applied to large-scale industrial production.
In order to achieve the purpose that foregoing invention, the present invention provides a kind of medical magnesium alloy implant inorganic agent, by
Gallium ion salt and phosphate anion salt is soluble in water obtains solution, then adjusted the pH value of solution to 1.0~5.0 using buffer
It is made, the molar ratio of gallium ion and phosphate anion is 1:(0.6~1.2 in the solution).
Further, in medical magnesium alloy implant inorganic agent of the present invention, the gallium ion is from nitre
At least one of sour gallium, gallium chloride, acetic acid gallium, boric acid gallium and acid iodide gallium.
Further, in medical magnesium alloy implant inorganic agent of the present invention, the gallium ion is from nitre
Sour gallium.This is because: gallium nitrate has solubility in high water, that is to say, that available to have by using gallium nitrate
The solution of higher gallium ion concentration, and then the preparation time of chemical composition coating can be shortened.Meanwhile it can be greatly reduced and finally make
The impurity of undissolved gallium nitrate salt is generated in standby chemical composition coating to improve product purity and quality.
Further, in medical magnesium alloy implant inorganic agent of the present invention, the phosphate anion is come from
In at least one of ammonium dihydrogen phosphate, sodium phosphate, sodium dihydrogen phosphate, potassium phosphate and potassium dihydrogen phosphate.
When phosphate is dissolved in water, and solution is made, according to solution acid alkalinity value, positive phosphorus acid ion (PO4 3-)
The equilibrium state coexisted can be generated with the phosphate anion of other various forms of acidifications, including phosphoric acid molecules (H3PO4), phosphorus
Acid dihydride radical ion (H2PO4 -) and one hydrogen radical ion (HPO of phosphoric acid4 2-)。
Further, in medical magnesium alloy implant inorganic agent of the present invention, the phosphate anion is come from
In ammonium dihydrogen phosphate.This is because: ammonium ion volume size is larger, solubility is larger in water, is not likely to produce precipitating, thus
Into in final conversion film product without introduce objectionable impurities.Therefore, in technical solutions according to the invention, phosphorus can be used
Source of the acid dihydride ammonium as phosphate anion.
Further, in medical magnesium alloy implant inorganic agent of the present invention, gallium ion and phosphate anion
Molar ratio be 1:1.
By the control of the molar ratio of gallium ion and phosphate anion in 1:1, be to provide for gallium ion with phosphate anion it
Between coordination balance, with match finally Mg alloy surface generate phosphoric acid gallium (GaPO4) based on chemical composition coating in gallium
With the molar ratio of phosphate radical.Meanwhile the control of the molar ratio of gallium ion and phosphate anion can also be reduced in 1:1 and turned in chemistry
Change film preparation and generates unnecessary impurity in the process.
Further, in medical magnesium alloy implant inorganic agent of the present invention, the buffer is by nitric acid, salt
At least one composition of acid, sulfuric acid, acid iodide and organic acid.
In some preferred embodiments, buffer can use nitric acid, this is because the organic acid with weak acid is compared,
The highly acid of nitric acid can effectively adjust reagent in the pH value in acid section.In addition, nitric acid has opposite hydrochloric acid and sulphur
Acid is compared, and has relatively high stability, and can control reaction process.
In addition, another object of the present invention is to provide a kind of use of above-mentioned medical magnesium alloy implant inorganic agent
Method, medical magnesium alloy implant can be made to be formed in magnesium alloy substrate surface using the application method has excellent corrosion resistant
Erosion and antibiotic property film layer, the application method have simple process, and used inorganic agent is free from environmental pollution.
In order to achieve the purpose that foregoing invention, the present invention provides a kind of above-mentioned medical magnesium alloy implant inorganic agents
Application method, comprising steps of
1) surface preparation is carried out to medical magnesium alloy implant；
It 2) will be one in the medical magnesium alloy implant merging medical magnesium alloy implant inorganic agent Jing Guo surface preparation
The section time；
3) medical magnesium alloy implant is taken out, it is dry after washing.
In application method of the present invention, by sending out magnesium alloy substrates with inorganic agent with medical magnesium alloy implant
Raw reaction, especially reacts with the effective component (i.e. phosphoric acid gallium) in inorganic agent, thus in metal surface or close to surface
Place forms chemical conversion membrane coat, a kind of chemical conversion membrane coat high, good, the highly crystalline state of stability chemistry with compactness
Conversion film, the ingredient of chemical conversion membrane coat mainly include metal magnesium cation, alloying component metal cation, hydroxyl yin from
Son, oxygen anion, phosphate radical anion and gallium cation.
In addition, in technical solutions according to the invention, surface preparation includes pickling, alkali cleaning, deoil, decontamination or other
The pretreating process that those skilled in that art are contemplated that, such as: use milling tools paper by magnesium alloy sample machine
Tool polishing, respectively in alcohol and acetone, room temperature ultrasonic is cleaned 5~15 minutes.It is activated 20~50 seconds in phosphoric acid solution,
It is placed in citric acid and cleans 5~15 seconds again.Then, in sodium hydroxide solution under 80~150 DEG C of hydrothermal condition reaction 5~
15 minutes.Finally, at room temperature, with citric acid cleaning 5~15 seconds.Then again respectively in alcohol and acetone, room temperature is super
Sound wave cleans 5~15 minutes.
Medical magnesium alloy implant after surface preparation is used as agents for film forming treatment with inorganic agent, contains metal gallium ion
The medical magnesium alloy implant of source and phosphate ion sources is contacted with inorganic agent with magnesium metal or magnesium alloy, it may occur that following anti-
It answers:
(1) magnesium from magnesium alloy substrate is dissolved in membrane-forming agent, discharges a large amount of metal magnesium ion (Mg2+), hydrogen
(H2) and hydroxide radical anion, and it is increased sharply the pH value of the solution near metal surface region simultaneously, what is be related to is anti-
Answer equation as follows:
Mg+2H2O→Mg2++H2+2OH-
(2) it results in phosphoric acid gallium in the raising of the pH value of near metal surface region solution to generate, and phosphoric acid gallium is heavy
For product in metallic substrate surface, the reaction equation being related to is as follows:
Ga3++PO4 3-→GaPO4
The main function of agents for film forming treatment ingredient be contacted with magnesium alloy substrate and produce containing gallium cation and
Phosphate radical anion chemical conversion membrane coat as main component.The chemical conversion membrane coat can in magnesium alloy substrate surface or
It is grown close at surface.Chemical conversion membrane coat is with the compound of gallium, phosphate radical phosphoric acid gallium as main component, this theca externa
Magnesium phosphate (Mg can be contained3(PO4)2), magnesium hydroxide (Mg (OH)2) and magnesium monohydrogen phosphate (MgHPO4) at least one.
Further, in application method of the present invention, in step 2), medical magnesium alloy implant use is controlled
The temperature for managing agent is room temperature~90 DEG C, and controlling described a period of time is 30 seconds~15 minutes.Medical magnesium alloy implant is controlled to use
The temperature of inorganic agent is room temperature~90 DEG C, is in order to enable reaction temperature is lower than the boiling temperature that normal atmosphere (An) is lauched
In addition, a further object of the present invention is to provide a kind of medical magnesium alloy implant, the medical magnesium alloy implant
Surface forms a kind of new chemical conversion membrane coat, so that the medical magnesium alloy implant has good biocompatibility, excellent
Different controlled degradation and postoperative bactericidal effect early period.
In order to achieve the above object of the invention, the present invention also provides a kind of medical magnesium alloy implants, rise using above-mentioned
Application method is processed.
Medical magnesium alloy implant inorganic agent strong applicability of the present invention is suitable for pure magnesium and magnesium alloy materials
(such as traditional commercial AZ31 and novel Mg (Zn) Ca system alloy)
It can be in magnesium alloy substrate table using the application method of medical magnesium alloy implant inorganic agent of the present invention
The film layer that face is formed, the film growth in situ formed at high temperature under high pressure, binding force is excellent, even film layer, densification, ultra-thin, anti-corrosion
It has excellent performance, the corrosion potential of chemical composition coating improves 150~350mV compared with matrixSCELeft and right, corrosion electric current density is compared with its base
The corrosion electric current density of body improves 1~2 order of magnitude, reaches the international leading level.
In addition, compared with the treatment process such as traditional chromate, phosphate, application method treatment process of the present invention
The reagent preparation simply, used is low harmful toxic matter (or trace reagent adjusting pH value), chemical composition coating coating binding force is high,
Corrosion resistance is strong, and production cost can be greatly reduced, be easy to industrial application.
Also, the antibiotic property of medical magnesium alloy implant of the present invention is with corresponding bare metal material (i.e. without this
Invention medical magnesium alloy enters the metal material that body is handled with inorganic agent) it compares, improve the 2-3 order of magnitude.
Detailed description of the invention
Fig. 1 illustrates the change of the sample surfaces obtained after the medical magnesium alloy implant inorganic agent processing using embodiment 1
Learn conversion film pattern.
Fig. 2 illustrates the change of the sample surfaces obtained after the medical magnesium alloy implant inorganic agent processing using embodiment 2
Learn conversion film pattern.
Fig. 3 illustrates the change of the sample surfaces obtained after the medical magnesium alloy implant inorganic agent processing using embodiment 4
Learn conversion film pattern.
Fig. 4 is that the chemistry of the sample surfaces obtained after being handled using the medical magnesium alloy implant inorganic agent of embodiment 4 is turned
Change film energy spectrum diagram.
Fig. 5 is that the chemistry of the sample surfaces obtained after being handled using the medical magnesium alloy implant inorganic agent of embodiment 4 is turned
Change film energy spectrum diagram, which show in chemical composition coating the case where Mg element.
Fig. 6 is that the chemistry of the sample surfaces obtained after being handled using the medical magnesium alloy implant inorganic agent of embodiment 4 is turned
Change film energy spectrum diagram, which show in chemical composition coating the case where Ga element.
Fig. 7 is that the chemistry of the sample surfaces obtained after being handled using the medical magnesium alloy implant inorganic agent of embodiment 4 is turned
Change film energy spectrum diagram, which show in chemical composition coating the case where O element.
Fig. 8 is that the chemistry of the sample surfaces obtained after being handled using the medical magnesium alloy implant inorganic agent of embodiment 4 is turned
Change film energy spectrum diagram, which show in chemical composition coating the case where P element.
Fig. 9 is comparative example 1 and must obtain after handling using the medical magnesium alloy implant inorganic agent of embodiment 1-5
The dynamic potential polarization curve figure of the surface chemical conversion film of sample.
Figure 10 illustrates comparative example 1 and obtains after handling using the medical magnesium alloy implant inorganic agent of embodiment 1-3
The antibacterial situation of the sample of acquisition.
Specific embodiment
It below will according to specific embodiment and Figure of description handles medical magnesium alloy implant of the present invention
Agent and its application method are described further, but the explanation does not constitute the improper restriction to technical solution of the present invention.
Embodiment 1-5
Table 1 lists the component proportion in the medical magnesium alloy implant inorganic agent of embodiment 1-5.
Table 1.
The salting liquid containing gallium ion can be used when it should be noted that preparing medical magnesium alloy implant inorganic agent
Agent solution is handled needed for obtaining with the salting liquid mixing and water adding constant volume containing phosphate ion, can also be used ion salt and phosphoric acid
Radical ion salt is soluble in water to obtain required solution, adds water after salt containing gallium ion can also be dissolved in the salting liquid containing phosphate ion
Solution needed for constant volume obtains, furthermore it is also possible to add water constant volume to obtain after phosphate anion salt is dissolved in the salting liquid containing gallium ion
Solution needed for obtaining.
By the medical magnesium alloy implant of embodiment 1-5 with inorganic agent to medical implant carry out using, comprising steps of
1) surface preparation is carried out to medical magnesium alloy implant；
It 2) will be one in the medical magnesium alloy implant merging medical magnesium alloy implant inorganic agent Jing Guo surface preparation
The temperature of section time, control medical magnesium alloy implant inorganic agent are room temperature~90 DEG C, and controlling described a period of time is 30 seconds
~15 minutes；
3) medical magnesium alloy implant is taken out, it is dry after washing.
Table 2 lists the ginseng of the concrete technology in the application method of the medical magnesium alloy implant inorganic agent of embodiment 1-5
Number.
Table 2.
Note: in table 2, pretreating scheme 1 are as follows: using carborundum paper polishing medical magnesium alloy implant surfaces, and
Successively respectively in 95% alcohol and acetone, each 15 minutes of ultrasonic cleaning at room temperature；
Pretreating scheme 2 are as follows: using carborundum paper polishing medical magnesium alloy implant surfaces, successively respectively in 95% wine
In essence and acetone, each 15 minutes of ultrasonic cleaning at room temperature, then the dilution of the concentrated phosphoric acid of 85wt% (dilution by
Every 200 milliliters of concentrated phosphoric acids, which are adopted, to be diluted with water to 1 liter and is made) in activation 30 seconds, then be placed in the citric acid of 20 grams per liters and clean
It 5 seconds, is then reacted 15 minutes under 150 DEG C of hydrothermal condition in the sodium hydroxide solution of 20 grams per liters, subsequently, in room temperature
Under, with citric acid cleaning 5 seconds of 20 grams per liters, finally under conditions of ultrasonic wave, with 95% ethanol solution and acetone soln point
It Qing Xi not be 10 and 5 minutes；
Pretreating scheme 3 are as follows: using carborundum paper polishing medical magnesium alloy implant surfaces, successively respectively in 95% wine
In essence and acetone, each 15 minutes of ultrasonic cleaning at room temperature, the subsequent dilution (dilution in the concentrated phosphoric acid of 85wt%
Adopted by every 200 milliliters of concentrated phosphoric acids and be diluted with water to 1 liter and be made) in activation 50 seconds, then be placed in the citric acid of 20 grams per liters clear
It washes 15 seconds, is then reacted 5 minutes under 100 DEG C of hydrothermal condition in the sodium hydroxide solution of 20 grams per liters, subsequently, in room
Under the conditions of temperature, with citric acid cleaning 15 seconds of 20 grams per liters, finally under conditions of ultrasonic wave, with 95% ethanol solution and third
Each cleaning of ketone solution difference 15 minutes.
By the medical magnesium alloy implant of treated embodiment 1-5 with as a comparison case 1 without the pure of any processing
Sample is made in magnesium material, carries out properties test experiments, and it is described that test result is as follows:
Firstly, can see by visually intuitively observing, each embodiment surface is all covered with the change of golden yellow metallic luster
Learn conversion membrane coat.Fig. 1 illustrates the sample surfaces obtained after the medical magnesium alloy implant inorganic agent processing using embodiment 1
Chemical composition coating pattern.Fig. 2 illustrates the sample obtained after the medical magnesium alloy implant inorganic agent processing using embodiment 2
The chemical composition coating pattern on surface.Fig. 3 is obtained after illustrating the medical magnesium alloy implant inorganic agent processing using embodiment 4
The chemical composition coating pattern of sample surfaces.And can be seen that each embodiment surface microscopic tissue in conjunction with Fig. 1 to Fig. 3 has rule
The crystal grain of the phosphoric acid gallium of lamellar then is fine and close, and is completely covered by surface, and be firmly combined with metal material matrix.
Fig. 4 is that the chemistry of the sample surfaces obtained after being handled using the medical magnesium alloy implant inorganic agent of embodiment 4 is turned
Change film energy spectrum diagram.Fig. 5 shows the sample surfaces obtained after the medical magnesium alloy implant inorganic agent processing using embodiment 4
In chemical composition coating the case where Mg element.Fig. 6 is obtained after showing the medical magnesium alloy implant inorganic agent processing using embodiment 4
In the chemical composition coating of the sample surfaces obtained the case where Ga element.Fig. 7 shows the medical magnesium alloy implant using embodiment 4
In the chemical composition coating of the sample surfaces obtained after inorganic agent processing the case where O element.Fig. 8 shows the doctor using embodiment 4
In the chemical composition coating of the sample surfaces obtained after being handled with magnesium alloy implant inorganic agent the case where P element.
Can be seen that the chemical composition coating on the sample surfaces in embodiment 4 in conjunction with reference Fig. 4 to Fig. 8 includes hydroxide
Magnesium, magnesia, magnesium phosphate and phosphoric acid gallium.
Fig. 9 is comparative example 1 and must obtain after handling using the medical magnesium alloy implant inorganic agent of embodiment 1-5
The dynamic potential polarization curve figure of the surface chemical conversion film of sample.Horizontal axis i in figurecorrRefer to corrosion current value, log, which refers to, to be taken pair
Numerical value, longitudinal axis EcorrRefer to corrosion potential value, Mg refers to the song that the numerical value measured according to the sample of comparative example 1 is drawn in legend
Line, legend 1 refer to the curve drawn according to the numerical value that the sample of embodiment 1 measures, and legend 2 refers to be surveyed according to the sample of embodiment 2
The curve that the numerical value obtained is drawn, legend 3 refer to the curve drawn according to the numerical value that the sample of embodiment 3 measures, and legend 4 refers to root
According to the curve that the numerical value that the sample of embodiment 4 measures is drawn, the finger of legend 5 is drawn according to the numerical value that the sample of embodiment 5 measures
The curve of system.
As shown in figure 9, the film growth in situ that each embodiment of this case is formed at high temperature under high pressure, binding force is excellent, film layer
Uniformly, fine and close, ultra-thin, excellent corrosion-proof performance, the corrosion potential of chemical composition coating improve 150~350mV compared with matrixSCELeft and right,
Corrosion electric current density improves 1~2 order of magnitude compared with the corrosion electric current density of its matrix.
Figure 10 illustrates comparative example 1 and obtains after handling using the medical magnesium alloy implant inorganic agent of embodiment 1-3
The antibacterial situation of the sample of acquisition.
As shown in Figure 10, after comparative example 1 and embodiment 1-3 sample impregnate 24 hours in Escherichia coli culture dish, by meat
Eye directly observation can see, and at A, comparative example 1 does not have apparent inhibiting effect to surrounding Escherichia coli, and in B-D
Locate, there is no E. coli clones around each embodiment of this case, illustrates that each embodiment of this case has good bacteriostasis.
It should be noted that prior art part is not limited to given by present specification in protection scope of the present invention
Embodiment, all prior arts not contradicted with the solution of the present invention, including but not limited to first patent document, formerly
Public publication, formerly openly use etc., it can all be included in protection scope of the present invention.
In addition, in this case in the combination of each technical characteristic and unlimited this case claim documented combination or
It is combination documented by specific embodiment, all technical characteristics that this case is recorded can be freely combined in any way
Or combine, unless generating contradiction between each other.
It is also to be noted that embodiment enumerated above is only specific embodiments of the present invention.The obvious present invention is not
Above embodiments are confined to, the similar variation or deformation made therewith are that those skilled in the art can be from present disclosure
It immediately arrives at or is easy to just to associate, be within the scope of protection of the invention.
Claims (11)
1. a kind of medical magnesium alloy implant inorganic agent, which is characterized in that it contains:
The gallium ion of 0.01~0.5 mol/L；
The phosphate anion of 0.005~0.5 mol/L；
The pH value of the medical magnesium alloy implant inorganic agent is adjusted into the buffer to 1.0~5.0；
Wherein the molar ratio of gallium ion and phosphate anion is 1:(0.6~1.2).
2. a kind of medical magnesium alloy implant inorganic agent, which is characterized in that it is dissolved in by gallium ion salt and phosphate anion salt
Solution is obtained in water, then the pH value of solution is adjusted to 1.0~5.0 using buffer and is made, gallium ion and phosphorus in the solution
The molar ratio of acid ion is 1:(0.6~1.2).
3. medical magnesium alloy implant inorganic agent as claimed in claim 1 or 2, which is characterized in that the gallium ion comes from
In at least one of gallium nitrate, gallium chloride, acetic acid gallium, boric acid gallium and acid iodide gallium.
4. medical magnesium alloy implant inorganic agent as claimed in claim 3, which is characterized in that the gallium ion is from nitre
Sour gallium.
5. medical magnesium alloy implant inorganic agent as claimed in claim 1 or 2, which is characterized in that the phosphate anion
From at least one of ammonium dihydrogen phosphate, sodium phosphate, sodium dihydrogen phosphate, potassium phosphate and potassium dihydrogen phosphate.
6. medical magnesium alloy implant inorganic agent as claimed in claim 5, which is characterized in that the phosphate anion comes from
In ammonium dihydrogen phosphate.
7. medical magnesium alloy implant inorganic agent as claimed in claim 1 or 2, which is characterized in that gallium ion and phosphate radical
The molar ratio of ion is 1:1.
8. medical magnesium alloy implant inorganic agent as claimed in claim 1 or 2, which is characterized in that the buffer is by nitre
At least one composition of acid, hydrochloric acid, sulfuric acid, acid iodide and organic acid.
9. the application method of the medical magnesium alloy implant inorganic agent as described in any one of claim 1-8, feature
It is, comprising steps of
1) surface preparation is carried out to medical magnesium alloy implant；
2) when by one section in the medical magnesium alloy implant merging medical magnesium alloy implant inorganic agent Jing Guo surface preparation
Between；
3) medical magnesium alloy implant is taken out, it is dry after washing.
10. application method as claimed in claim 9, which is characterized in that in step 2), control medical magnesium alloy implant is used
The temperature of inorganic agent is room temperature~90 DEG C, and controlling described a period of time is 30 seconds~15 minutes.
11. a kind of medical magnesium alloy implant, processed according to the application method as described in claim 9 or 10.
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