CN101302638A - Preparation of nano-HAP coating/magnesium alloy composite biological material - Google Patents
Preparation of nano-HAP coating/magnesium alloy composite biological material Download PDFInfo
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- CN101302638A CN101302638A CNA2008100490236A CN200810049023A CN101302638A CN 101302638 A CN101302638 A CN 101302638A CN A2008100490236 A CNA2008100490236 A CN A2008100490236A CN 200810049023 A CN200810049023 A CN 200810049023A CN 101302638 A CN101302638 A CN 101302638A
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Abstract
The invention provides a method for making a nano HAP coating/magnesium alloy composite biomaterial. The method is as follows: the method takes a magnesium alloy as a cathode and graphite as an anode; the magnesium alloy and the graphite are placed in electrolyte containing NH4H2PO4, NaHO3 and Ca(OH3)2.4H2O so as to carry out stepped electrodeposition at a temperature of between 60 and 95 DEG C and a voltage of between minus 5 V to minus 1 V and 0 V, thereby effectively improving the interface bonding between a coating and a matrix and reducing hydrogen evolution during electrodeposition; meanwhile, the increase of magnesium ions at an interface can realize in-situ doping of magnesium ions and hydroxyapatite so as to generate a magnesium phosphate transition layer on the surface of the magnesium alloy and to increase bonding strength; thus, a degradable nano acicular hydroxyapatite/magnesium alloy coating composite biomaterial with excellent mechanical property, biocompatibility and corrosion resistance can be obtained. Meanwhile, the method also has the advantages of low cost of raw materials and simple technological operation, etc.
Description
Technical field
The invention belongs to magnesium alloy biomaterial preparing technical field, be specifically related to the preparation method of a kind of nano-HAP (HAP is a hydroxyapatite) coating/magnesium alloy composite biological material.
Background technology
The life medical material relates to the raising of human beings'health and quality of life, is the hi tech and new material of a class new development, is just developing into a pillar industry of 21 century economy.In the Artificial bone material implant into body, must satisfy two primary conditions: (1) embedded material should have excellent biological compatibility and high biological activity; (2) embedded material should have suitable mechanical property and certain chemical stability.The most frequently used internal fixing metallic substance mainly contains stainless steel, Co-Cr alloy, titanium and alloy at present, and than pottery and polymkeric substance, they have higher mechanical property, are more suitable for as bone implant material.But their shortcoming also displays gradually, as stress shielding, electrolytic corrosion, second operation etc.
Degradable biomaterial is classified as 21 century by many developed countries and is given priority to object.Magnesium and magnesium alloy are a kind of metallic substance of environment degradable in vivo, as biomaterial, can avoid above-mentioned untoward reaction effectively, and have mechanical property and the excellent biological compatibility near with people's bone photo: (1) tissue toughness is better than ceramic biomaterial; In addition Young's modulus and ultimate compression strength also than other metal implant materials more near people's bone, the stress shielding phenomenon that can avoid the Young's modulus with metal implant into body internal cause material not match and produce.(2) density of magnesium and magnesium alloy is about 1.7g/cm
3, minimum in all structured materials, with the density 1.75g/cm of human body dense bone
3The most approaching, far below the density 4.47g/cm of Ti6Al4V
3(3) magnesium alloy has degradable in vivo, does not need to carry out second operation.(4) magnesium elements itself is exactly the necessary element of human body, and content is only second to potassium in vivo, and it participates in a series of metabolism in the body, comprises the formation of accelerated bone cell, the healing of osteocyte etc.Magnesium elements is also in close relations with nerve, muscle and heart.So with the magnesium implant into body, not only need not consider the toxicity of trace metal ion, and the trace of magnesium ion discharges also to the human body beneficial in the embedded material to human body cell.
(Zreiqat H such as Zreiqat, Howlett CR, Zannettino A, et al.Mechanisms ofmagnesium stimulated adhesion of osteoblastic cells to commonly usedorthopaedic implantsJ.J Biomed Mater Res.2002,622:175-184.), (Yamasaki Y such as Yamasak, Yoshida Y, Okazaki M, et al.Synthesis of functionally gradedMgCO
3Apatite accelerating osteoblast adhesionJ.J Biomed Mater Res, 2002,621:99-105.) show that by experiment the bioceramic implant that contains magnesium ion, the surperficial scleroblast of collagen stick increase, integrate plain expression and signal conductive protein genetic expression and increase, the bone integration ability strengthens.Employing experimentation on animalies such as Chang Xiaofeng think that early stage Mg supplementation can be accelerated the speed of poroma distraction osteogenesis, promote the maturation of sclerotin and the performance of function.(Sul YT such as Sul, Johansson C, Albrektsson T.Whichsurface properties enhance bone response to implants Comparison of oxidizedmagnesium, Tiunite and Osseotite implant surfaces J.Int J Prosthodont.2006,19) show by experimentation on animals, contain the magnesium ion ceramic membrane in the plating of titanium or magnesium implant surface and can improve the bone integration ability, and early stage functional burdening can be provided.(Witte F such as Witte, Kaese V, Haferkamp H, et al.In vivo corrosionoffour magnesium alloys and the associated bone responseJ.Biomaterials, 2005,26 17:3557-3563.) the magnesium base planting body that experimental results show that has more calcium phosphates to form than the poly(lactic acid) surface, and the surrounding bone amount increases, and the magnesium ion of prompting high density can improve osteoblastic activity; Magnesium can promote the calcium phosphate deposition in external environment, increases osteogenesis, improves the original position solidity to corrosion simultaneously.
In sum, magnesium and magnesium alloy have enough intensity, and excellent biological compatibility and degradable in vivo are expected to become novel bone implant material.But because osseous tissue is repaired fully and is needed 12-18 week, and be that the degradation speed of pure magnesium in the body fluid environment of 7.4-7.6 is very fast in the pH value, bone tissue restoration such as also do not have fully just to be degraded fully, limited the application of magnesium and magnesium alloy as bone reparation and bone implant material.Therefore, make magnesium replace the prior biological embedded material to become possibility, just must carry out alloying or surface modification provides corrosive nature and biocompatibility MAGNESIUM METAL.
Surface modification is a kind of effective control mg-based material degradation rate, improves the approach of biocompatibility.The HAP coating is stable under body fluid PH=7.4 environment, corrosion resistance nature to magnesium alloy improves, it possesses excellent biological compatibility simultaneously, can form chemical bond with osseous tissue, osseous tissue is deposited positive inducing action at Mg alloy surface, promote the growth of bone and shorten healing time.But the mechanical property of HAP material is relatively poor, and folding strength and fracture toughness property index all are lower than the human body dense bone, thereby has limited the application on human body hard tissue.Therefore, adopt the HAP coating that magnesium alloy is carried out surface modification and make material both have the intensity and the toughness of metal, the HAP excellent biological compatibility is arranged again, also possess the degradability that body is implanted into simultaneously, be very suitable for the application of embedded material on the clinical medicine.
The preparation method of HAP coating is a lot, and the fusing point of magnesium alloy is low and solidity to corrosion is poor, and as the magnesium base degradable material, the selection of its coating production is most important.Except high temperature preparation methods such as plasma spraying, laser cladding can cause the overheated and coating high-temp phase transformation of matrix, cause mechanical properties decrease, biological activity to reduce; Sol-gel method usually is accompanied by high-temperature heat treatment, also is not suitable for magnesium alloy; For the biomimetic growth method,, also form local corrosion easily and affect the mechanical properties because magnesium alloy corrodes in bionical solution comparatively fast.Adopt electrochemical process, by pre-treatment to magnesium alloy substrate, coating preparation process parameter control with, can realize the low temperature preparation of coating, avoid the overheated and coating phase transformation of matrix.By processing parameter control, can prepare the Ca/P atomic ratio and present non-stoichiometric.
(Shirkhanzadeh M.J.Mater Sci Let such as Shirkhanzadeh, 1993, be negative electrode with medical titanium alloy Ti6Al4V at first 12:16) with electrodip process, platinized platinum is an anode, obtain very uniformly, by the calcium phosphate coating that the omnidirectional crystal of the sheet that is of a size of 15～20 μ m is formed, the Ca/P ratio is 1.63.Royer etc. (Royer P, Pey C.Surface and Coating Technology, 1991,45:171 is 7.8 in the pH value, 20～70 ℃ of deposit fluid temperature, under the condition of voltage-3V, in the surface deposition of titanium the calcium phosphate bioactive pottery.) (Hideki M.J Ceram Soc Jap such as Hidexi, 1993,101:737) reported, changed the electrodeposition technology condition, can obtain the phosphorite crystal coating of ellipse, needle-like or fine particle shape with the technology of electrodip process at stainless steel surface deposition calcium deficiency phosphatic rock.
The patent application (application number is 200710189682.5) of " kind bone HAP/ magnesium alloy coating biomaterial and preparation method thereof " disclosed a kind of electrochemical process that adopts constant current can be on the Mg alloy surface deposition method of good hydroxyapatite coating layer, its electrodeposition step is, the electrolytic solution of heating in the body material (negative electrode) putting into graphite (anode) and handle well, according to current density and the long-pending deposition current (electric current=current density * surface-area) of calculating of specimen surface, current density is made as 1.0～2.5mA/cm
2, opening power deposits when regulating the electric current postscript, and the time is made as 0.5～2h, uses rinsed with deionized water, dry getting final product.But comparatively serious hydrogen evolution phenomenon can appear in specimen surface when sedimentation potential is higher in electrodeposition process, this has influenced phosphatic nucleation greatly, it is not very fine and close making coating, and bonding strength is lower, and the OH that evolving hydrogen reaction produces is that the formation hydroxyapatite crystal is essential.
Summary of the invention
The object of the present invention is to provide a kind of HAP surface deposition that both helped, significantly reduce evolving hydrogen reaction in the deposition process again, can prepare the method for coating densification and well behaved nano-HAP coating/magnesium alloy composite biological material.
To achieve these goals, the technical solution used in the present invention is as follows.
Prepare the method for nano-HAP coating/magnesium alloy composite biological material, may further comprise the steps:
(1) preparation of coating electrolytic solution
Each composition of electrolytic solution is as follows, and electrolytic solution is formulated by ammonium di-hydrogen phosphate (99.5%), SODIUMNITRATE (99%) and four water-calcium nitrate (99%), and the calcium phosphorus atom is than by 1.6～2.5 preparations in the electrolytic solution, and the content of each composition is in every liter of solution: NH
4H
2PO
40.54g～5.4g, NaNO
33.2g～9.6g, Ca (NO
3)
24H
2O1.86g～18.6g uses HNO
3Or (CH
2OH)
3CNH
2Regulator solution pH value is 3.0～7.0, stirs, and is standby;
(2) pre-treatment of body material
Select for use the magnesium alloy substrate to make body material,, wash with deionized water earlier with 100～1000SiC abrasive paper for metallograph sanding and polishing successively; Volume ratio configuration acetone, alcohol mixing solutions by 0.5～1: 1 place this mixing solutions ultrasonic cleaning 5～25min oil removing with body material, and be at room temperature dry; And at room temperature put into 20%～40% hydrofluoric acid solution activation treatment, 5～30min, wash seasoning then with deionized water;
(3) galvanic deposit
The coating electrolytic solution of above-mentioned configuration is heated to 60 ℃～95 ℃ in water-bath, put into electrolytic solution with graphite (anode) and through the body material (negative electrode) that step (2) is handled well, earlier constant potential-5V～-the 1V condition under preplating 5～30min, the pre-plating layer that is obtained is cleaned with redistilled water, drying is placed in the NaOH alkaline solution of 0.1～1mol/L and handles 2～3h at 60～95 ℃, makes the galvanic deposit precursor change the HAP sample into; Sample is cleaned with redistilled water, dries naturally, adopts continuous bipotential step to carry out prepared by electrodeposition HAP coating then, earlier from open circuit potential E
1=0V step is to E
2For-5V～-1V, stop the certain hour note and make t
1Be 5～60s; Step is returned E again
1=0V keeps for some time, and note is made t
2Be 5～60s, successive cycle step so repeatedly, electrodeposition time is controlled at 0.5～3h, takes out after the time and use rinsed with deionized water, and at room temperature drying makes sample;
(4) alkaline purification
Alkali lye is handled the NaOH solution that adopts 0.1～1mol/L, be heated to 60-95 ℃, the sample of step (3) preparation put into take out after NaOH solution soaks 2～8h, with rinsed with deionized water for several times, clean up until its surperficial alkali lye, the loft drier of putting into 60～120 ℃ then dries by the fire 4～24h taking-up, promptly makes nano-HAP/magnesium alloy coating matrix material.
Wherein, magnesium alloy is that matrix is the basic alloy of Mg-(Zn, Al, Mn, Ca); Coating is a nano-HAP, and its grain-size is the 10-100 nanometer.The nano-HAP coating/magnesium alloy composite biological material that makes with aforesaid method can be used in the implantation and reparation of human body bone.
Compared with prior art, the invention has the advantages that:
Magnesium alloy matrix surface successfully prepared bonding strength better, the nano-HAP coating of top coat even compact.This coating phase free from foreign meter, degree of crystallinity height (more than 95%), crystallization crystal grain are nano level needle-like HAP, and ratio of calcium and phosphorus is higher adjustable between 1.6～1.67; Coating possesses good biological activity.
2. utilize electrochemical process and low-temperature alkaline to handle and combine, realize the low temperature preparation of coating, avoid the overheated and coating phase transformation of matrix.
3. adopted the cyclical operation of multiple bipotential step, can change evolving hydrogen reaction and give the sedimentary destruction of coating, can make HAP at Mg alloy surface crystallization better, stable growth, the dense coating that obtained performance is good.Can realize simultaneously magnesium ion in-situ doped to hydroxyapatite, generate the phosphoric acid salt transition layer of magnesium, increase bonding strength at Mg alloy surface.
Description of drawings
Fig. 1 is the E-t graphic representation of the bipotential step method of nano-HAP coating/magnesium alloy composite biological material preparation.
Fig. 2 is for optimizing the nano-HAP coating/magnesium alloy composite biological material SEM figure that obtains under the technology.
Among Fig. 1, adopt the cycling of multiple bipotential step to deposit HAP at Mg alloy surface, E2 is set at-5V～-1V about, the potential setting of E1 is 0V, establishes t1＝t
2, the party Method is improved the hydrogen evolution phenomenon of deposition process, can prepare the fine and close and well behaved HAP coating of coating. Simultaneously can realize magnesium ion to the doping of hydroxyapatite, generate the phosphate mistake of magnesium at Mg alloy surface Cross layer, increase bond strength.
Among Fig. 2, nano-HAP coating is petal-shaped to external radiation, and crystal grain is tiny needle-like and is fully given birth to Long and on needle-like, can see more tiny acicular crystal growth; This needle-like pattern and osteolith Crystal characteristic more similar, and form the porous network structure of commissure at matrix surface, can provide more Big surface area, thus more be conducive to the deposition of sclerotin in the body, have better biocompatibility.
Specific implementation method
Below in conjunction with embodiment the present invention is further described, but is not limited to the following example.
Embodiment 1:
As body material, its alloying constituent (wt%) is: Al 3.13% with the AZ31 magnesium alloy, and Zn 1.21%, and Mn 0.47%, and Si 0.04%, the Mg surplus.
(1) preparation coating electrolytic solution: take by weighing NH
4H
2PO
4(99.5%) 0.54g, NaNO
3(99%) 6.38g, Ca (NO
3)
2.4H
2O (99%) 1.89g is configured to dilute solution 750ml, and promptly adjusting calcium phosphorus atom ratio is 1.67, stirs with glass stick; Use HNO
3Or (CH
2OH)
3CNH
2The pH value of regulator solution is 5.0, stirs, and obtains stand-by electrolytic solution.
(2) body material pre-treatment: the rectangular block that AZ31 magnesium alloy plate line cuts into, with 100-1000 abrasive paper for metallograph sanding and polishing successively, after washing with deionized water, configuration acetone, alcohol mixing solutions, its volume ratio is 1: 1, body material is placed this mixing solutions ultrasonic cleaning 10min oil removing, at room temperature dry; And at room temperature put into 40% hydrofluoric acid solution activation treatment 10min, and wash with deionized water then, measure matrix length 2.5cm, width 1.0cm, height 0.7cm, redundance covers with silicon rubber, seasoning.
(3) galvanic deposit: the coating electrolytic solution of preparation is heated to 80 ℃ in water-bath, graphite (anode) and the body material (negative electrode) handled well are placed in the electrolytic solution, the preplating 20min under constant potential-3V condition of elder generation, the pre-plating layer that is obtained is cleaned with redistilled water, drying is placed in the NaOH alkaline solution of 0.5mol/L and handles 2h at 80 ℃, makes the galvanic deposit precursor change the HAP sample into; Sample is cleaned with redistilled water, dries naturally.Adopt continuous bipotential step method to carry out galvanic deposit HAP coating then, earlier from open circuit potential E
1=0V step is to E
2For-3.2V, stop 20s (t
1), step is returned E again
1=0V keeps 20s (t
2), so take out behind the cycle step 1h and use rinsed with deionized water, dry under the room temperature.
(4) alkaline purification: alkali lye is handled the NaOH solution that adopts 0.5mol/L, be heated to 80 ℃, the sample of preparation put into take out after solution soaks 5h, with rinsed with deionized water for several times, wash the alkali lye on surface, the loft drier baking 10h that puts into 80 ℃ then takes out, and promptly makes nano-HAP/magnesium alloy coating matrix material.
Embodiment 2:
As body material, its alloying constituent (wt%) is: Zn 5.83% with the ZK60 magnesium alloy, and Zr 0.45%, and Mn 0.04%, and Ca 0.02%, the Mg surplus.
(1) configuration of electrolytic solution: take by weighing NH
4H
2PO
4(99.5%) 2.7g, NaNO
3(99%) 3.2g, Ca (NO
3)
2.4H
2O (99%) 9.45g is configured to dilute solution 750ml, and promptly adjusting calcium phosphorus atom ratio is 1.67, stirs with glass stick, uses HNO
3Or (CH
2OH)
3CNH
2The pH value of regulator solution is 6.0, stirs, and obtains stand-by electrolytic solution.
(2) pre-treatment of body material: the rectangular block that AZ31 magnesium alloy plate line cuts into, with 100-1000 abrasive paper for metallograph sanding and polishing successively, after washing with deionized water, configuration acetone: the alcohol volume ratio is 0.8: 1 a mixing solutions, body material is placed this mixing solutions ultrasonic cleaning 5min oil removing, at room temperature dry; And at room temperature put into 30% hydrofluoric acid solution activation treatment 20min, wash with deionized water then; Measure matrix length 2.5cm, width 1.0cm, height 0.7cm, redundance covers with silicon rubber, seasoning.
(3) galvanic deposit: the coating electrolytic solution of preparation is heated to 95 ℃ in water-bath, graphite (anode) and the body material (negative electrode) handled well are placed in the electrolytic solution, the preplating 10min under constant potential-5V condition of elder generation, the pre-plating layer that is obtained is cleaned with redistilled water, drying is placed in the NaOH alkaline solution of 0.8mol/L and handles 2h at 90 ℃, makes the galvanic deposit precursor change HAP into; Sample is cleaned with redistilled water, dries naturally; Adopt continuous bipotential step method to carry out galvanic deposit HAP coating then, earlier from open circuit potential E
1=0V step is to E
2For-3.8V, stop 10s (t
1); Step is returned E again
1=0V keeps 10s (t
2), like this cycle step, the time is controlled at 0.5h, takes out after the time and use rinsed with deionized water, drying under the room temperature.
(4) alkaline purification: alkali lye is handled the NaOH solution that adopts 0.25mol/L, is heated to 90 ℃, and the sample of preparation is put into taken out after solution soaks 8h, with rinsed with deionized water for several times, the alkali lye of clean surface.Sample is put into 120 ℃ loft drier baking 20h taking-up, promptly makes nano-HAP/magnesium alloy coating matrix material.
Embodiment 3:
With the AZ80 magnesium alloy is body material, and its alloying constituent (wt%) is, Al 7.98%, and Zn 0.32%, and Mn 0.23%, the Mg surplus.
(1) configuration of electrolytic solution: take by weighing NH
4H
2PO
4(99.5%) 0.54g, NaNO
3(99%) 9.6g, Ca (NO
3)
2.4H
2O (99%) 2.26g is configured to dilute solution 750ml, and promptly adjusting calcium phosphorus atom ratio is 2.0, stirs with glass stick, uses HNO
3Or (CH
2OH)
3CNH
2The pH value of regulator solution is 4.2, stirs, and obtains stand-by electrolytic solution.
(2) pre-treatment of body material: the rectangular block that AZ31 magnesium alloy plate line cuts into, with 100-1000 abrasive paper for metallograph sanding and polishing successively, after washing with deionized water, configuration acetone: the alcohol volume ratio is 0.5: 1 a mixing solutions, body material is placed this mixing solutions ultrasonic cleaning 15min oil removing, at room temperature dry; And at room temperature put into 40% hydrofluoric acid solution activation treatment 20min, wash with deionized water then; Measure matrix length 2.5cm, width 1.0cm, height 0.7cm, redundance covers with silicon rubber, seasoning.
(3) galvanic deposit: the coating electrolytic solution of preparation is heated to 90 ℃ in water-bath, graphite (anode) and the body material (negative electrode) handled well are placed in the electrolytic solution, the preplating 30min under constant potential-1V condition of elder generation, the pre-plating layer that is obtained is cleaned with redistilled water, drying is placed in the NaOH alkaline solution of 1mol/L and handles 2h at 95 ℃, makes the galvanic deposit precursor change HAP into; Sample is cleaned with redistilled water, dries naturally; Adopt continuous bipotential step method to carry out the heavy HAP coating of electricity then, earlier from open circuit potential E
1=0V step is to E
2For-1.2V, stop the certain hour note and make t
1Be 60s; Step is returned E again
1=0V keeps for some time, and note is made t
2Be 60s, like this cycle step, the time is controlled to be 3h, takes out after the time and use rinsed with deionized water, drying under the room temperature.
(4) alkaline purification: alkali lye is handled the NaOH solution that adopts 1mol/L, is heated to 70 ℃, and the sample of preparation is put into taken out after solution soaks 2h, with rinsed with deionized water for several times, the alkali lye of clean surface.Sample is put into 60 ℃ loft drier baking 24h taking-up, promptly makes nano-HAP/magnesium alloy coating matrix material.
Embodiment 4:
With the AM60 magnesium alloy is body material, and its alloying constituent (wt%) is, Al 6.08%, and Mn 0.13%, the Mg surplus.
(1) preparation of coating electrolytic solution: take by weighing NH
4H
2PO
4(99.5%) 2.7g, NaNO
3(99%) 6.38g, Ca (NO
3)
2.4H
2O (99%) 11.3g is configured to dilute solution 750ml, and promptly adjusting calcium phosphorus atom ratio is 2.0, stirs with glass stick; Use HNO
3Or (CH
2OH)
3CNH
2The pH value of regulator solution is 3.0, stirs, and obtains stand-by electrolytic solution.
(2) pre-treatment of body material: the rectangular block that AZ31 magnesium alloy plate line cuts into, with 100-1000 abrasive paper for metallograph sanding and polishing successively, after washing with deionized water, configuration acetone, alcohol mixing solutions, its volume ratio is 1: 1, body material is placed this mixing solutions ultrasonic cleaning 5min oil removing, at room temperature dry; And at room temperature put into 25% hydrofluoric acid solution activation treatment 16min, and wash with deionized water then, measure matrix length 2.5cm, width 1.0cm, height 0.7cm, redundance covers with silicon rubber, seasoning.
(3) galvanic deposit: the coating electrolytic solution of preparation is heated to 65 ℃ in water-bath, graphite (anode) and the body material (negative electrode) handled well are placed in the electrolytic solution, the preplating 15min under constant potential-2V condition of elder generation, the pre-plating layer that is obtained is cleaned with redistilled water, drying is placed in the NaOH alkaline solution of 0.8mol/L and handles 2.5h at 70 ℃, makes the galvanic deposit precursor change HAP into; Sample is cleaned with redistilled water, dries naturally; Adopt continuous bipotential step method to carry out the heavy HAP coating of electricity then, earlier from open circuit potential E
1=0V step is to E
2For-4.5V, stop the certain hour note and make t
1Be 15s; Step is returned E again
1=0V keeps for some time, and note is made t
2Be 15s, so cycle step.Time is made as 2h, takes out after the time and use rinsed with deionized water, drying under the room temperature.
(4) alkaline purification: alkali lye is handled the NaOH solution that adopts 0.5mol/L, is heated to 85 ℃, and the sample of preparation is put into taken out after solution soaks 7h, with rinsed with deionized water for several times, the alkali lye of clean surface.Sample is put into 110 ℃ loft drier baking 8h taking-up, promptly makes nano-HAP/magnesium alloy coating matrix material.
Embodiment 5:
With the AZ91 magnesium alloy is body material, and its alloying constituent (wt%) is: Al 9.06%, and Zn 1.05%, and Mn 0.18%, and Si 0.01%, the Mg surplus.
(1) preparation of coating electrolytic solution: take by weighing NH
4H
2PO
4(99.5%) 1.08g, NaNO
3(99%) 5.60g, Ca (NO
3)
2.4H
2O (99%) 5.66g is configured to dilute solution 750ml, and promptly adjusting calcium phosphorus atom ratio is 2.5, stirs with glass stick; Use HNO
3Or (CH
2OH)
3CNH
2The pH value of regulator solution is 5.0, stirs, and obtains stand-by electrolytic solution.
(2) pre-treatment of body material: the rectangular block that AZ31 magnesium alloy plate line cuts into, with 100-1000 abrasive paper for metallograph sanding and polishing successively, after washing with deionized water, configuration acetone, alcohol mixing solutions, its volume ratio is 0.9: 1, body material is placed this mixing solutions ultrasonic cleaning 20min oil removing, at room temperature dry; And at room temperature put into 35% hydrofluoric acid solution activation treatment 25min, and wash with deionized water then, measure matrix length 2.5cm, width 1.0cm, height 0.7cm, redundance covers with silicon rubber, seasoning.
(3) galvanic deposit: the coating electrolytic solution of preparation is heated to 75 ℃ in water-bath, graphite (anode) and the body material (negative electrode) handled well are placed in the electrolytic solution, the preplating 25min under constant potential-3.8V condition of elder generation, the pre-plating layer that is obtained is cleaned with redistilled water, drying is placed in the NaOH alkaline solution of 0.3mol/L and handles 2.8h at 90 ℃, makes the galvanic deposit precursor change HAP into; Sample is cleaned with redistilled water, dries naturally; Adopt continuous bipotential step method to carry out the heavy HAP coating of electricity then, earlier from open circuit potential E
1=0V step is to E
2For-3.8V, stop the certain hour note and make t
1Be 25s; Step is returned E again
1=0V keeps for some time, and note is made t
2Be 25s, so cycle step.Time is made as 1.5h, takes out after the time and use rinsed with deionized water, drying under the room temperature.
(4) alkaline purification: alkali lye is handled the NaOH solution that adopts 0.75mol/L, is heated to 95 ℃, and the sample of preparation is put into taken out after solution soaks 5h, with rinsed with deionized water for several times, the alkali lye of clean surface; Sample is put into 95 ℃ loft drier baking 15h taking-up, promptly makes nano-HAP/magnesium alloy coating matrix material.
Test check and analysis to product show:
1. adopt the bipotential step can obtain the nano-HAP coating of needle-like densification, low-temperature alkaline is handled can promote that presoma transforms to HAP, can improve calcium phosphorus atom ratio and be up to 1.67, is the calcium phosphorus atom ratio of natural bone;
2. corrosion electrochemistry system testing result shows that the HAP coating can improve the corrosion potential 200mV of magnesium alloy in simulated body fluid (SBF), illustrates that coating can the better protecting matrix;
3. the bonding stretching method has been measured the bonding strength of HAP/ magnesium alloy coating material, has shown that the bonding properties of coating that the technology optimized makes and matrix is good, can reach 20.8MPa, satisfies the basic demand that body is implanted into;
4. the simulated body fluid soak test shows, its corrosion of cated sample presents trend from slow to fast, and soaking preceding 2 all cated samples all has obvious weightening finish, and weightlessness and weightening finish just are tending towards relaxing after one month.At the immersion initial stage, deposition plays a leading role, and the later stage corrosion plays a leading role.
Claims (2)
1. the preparation method of a nano hydroxyapatite coating/magnesium alloy composite biological material is characterized in that comprising following steps:
(1) preparation of coating electrolytic solution: each composition of electrolytic solution is as follows, and electrolytic solution is formulated by ammonium di-hydrogen phosphate, SODIUMNITRATE and four water-calcium nitrate, and the calcium phosphorus atom is than by 1.6～2.5 preparations in the electrolytic solution, and the content of each composition is in every liter of solution: NH
4H
2PO
40.54g～5.4g, NaNO
33.2g～9.6g, Ca (NO
3)
24H
2O1.86g～18.6g uses HNO
3Or (CH
2OH)
3CNH
2Regulator solution pH value is 3.0～7.0, stirs, and is standby;
(2) pre-treatment of body material: select for use magnesium alloy plate to make body material, earlier with 100～1000SiC abrasive paper for metallograph sanding and polishing successively, the deionization washing, put into acetone, alcohol mixing solutions ultrasonic cleaning 5～25min oil removing then, dry under the room temperature, at room temperature put into 20%～40% hydrofluoric acid solution activation treatment, 5～30min, wash seasoning again with deionized water; Wherein the volume ratio of acetone, alcohol mixing solutions is 0.5～1: 1;
(3) galvanic deposit: the coating electrolytic solution of step (1) configuration is heated to 60 ℃～95 ℃, put into electrolytic solution with graphite and through the body material that step (2) is handled well, earlier constant potential-5V～-the 1V condition under preplating 5～30min, the pre-plating layer that is obtained is cleaned with redistilled water, drying is placed in the NaOH alkaline solution of 0.1～1mol/L and handles 2～3h at 60～95 ℃, makes the galvanic deposit precursor change the HAP sample into; Sample is cleaned with redistilled water, dries naturally; Adopt continuous bipotential step method to carry out prepared by electrodeposition HAP coating then; Earlier from open circuit potential E
1=0V step is to E
2For-5V～-1V, stop 5～60s, step is returned E again
1=0V keeps 5～60s, successive cycle step so repeatedly, and electrodeposition time is controlled at 0.5～3h, takes out after the time and use rinsed with deionized water, at room temperature drying;
(4) alkaline purification: alkali lye is handled the NaOH solution that adopts 0.1～1mol/L, be heated to 60-95 ℃, the sample of step (3) preparation put into take out after NaOH solution soaks 2～8h, with rinsed with deionized water for several times, the alkali lye of clean surface, the loft drier of putting into 60～120 ℃ then dries by the fire 4～24h taking-up, promptly gets product.
2. according to the preparation method of the described nano hydroxyapatite coating/magnesium alloy composite biological material of claim 1, it is characterized in that: the magnesium alloy as body material is the basic alloy of Mg-(Zn, Al, Mn, Ca).
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