CN105506586A - Method for preparing degradable magnesium cage implant with antibacterial and anti-corrosion graphene/apatite composite coating - Google Patents

Method for preparing degradable magnesium cage implant with antibacterial and anti-corrosion graphene/apatite composite coating Download PDF

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CN105506586A
CN105506586A CN201511028119.0A CN201511028119A CN105506586A CN 105506586 A CN105506586 A CN 105506586A CN 201511028119 A CN201511028119 A CN 201511028119A CN 105506586 A CN105506586 A CN 105506586A
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magnesium
implant
composite coating
graphene
cage implant
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CN105506586B (en
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王亚明
吴云峰
郭立新
贾德昌
周玉
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Harbin Institute of Technology
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract

The invention provides a method for preparing a degradable magnesium cage implant with an antibacterial and anti-corrosion graphene/apatite composite coating and relates to a degradable magnesium cage implant, aiming to solve the problems that magnesium in the prior art has low corrosion potential, high corrosion rate in the body fluid environment and excessively fast mechanical integrity loss, and apatite has the defects of poor film-substrate bonding strength and easiness in wear. The method is achieved by the following steps: I, processing magnesium into a cage and removing oil, thus obtaining a cage implant; II, adding the cage implant to a reaction kettle to undergo hydrothermal reaction for surface modification, thus obtaining a hydrothermal composite coating containing graphene and apatite; and III, washing the hydrothermal composite coating by using deionized water and drying the hydrothermal composite coating, thus obtaining the degradable magnesium cage implant with the antibacterial and anti-corrosion graphene/apatite composite coating. The method is applied to the field of degradable magnesium cage implants.

Description

A kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating
Technical field
The present invention relates to degradable magnesium cage implant, particularly a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.
Background technology
Cranial defect is common clinical, causes the reason of Cranial defect may have the excision of bone wound, infection of bone sequestrum, the excision of bone tumor section etc.Bone defect healing technology mainly contains Ilizarow technology, fibular autograft, allogeneic bone-specific drug etc.Adopt implant device assisting therapy to be common method for the treatment of, it has fixing-stable, and the advantage such as reset accurate.The existing implant device for repairing bone defect is generally to be selected to adopt titanium, zirconium, zirconium white, platinum, rhodium, niobium, surgery stainless steel, cobalt chromium-steel, tantalum etc. not to degrade or difficult degradation alloy, as the caged implant of bone stabilizer equipment (CN104602629A), intervertebral implant (CN101938957A).Select above-mentioned not degrade or the caged implant of difficult degradation alloy material has stronger mechanical property, can implant for a long time in human body.But in the long-term process implanted, due to human bone and the larger mechanics difference of above-mentioned materials and the stress shielding caused, surrounding bone is organized easily fracture, long-term accumulated wearing and tearing implant chip piles up and be difficult to hidden danger such as excreting in human body, still need above-mentioned implant device taking-up after bone tissue restoration for some time.In addition, after being implanted by surgical operation, although employ antibiotic etc, the bacteriological infection case of implant site still often occurs.
Biodegradable magnesium alloy material and skeleton have close mechanical property.Caged implant prepared by magnesium alloy is applied to the reparation of Cranial defect, there is reduction stress shielding, enough mechanics supports are provided at the implantation initial stage, and progressively at people's vivo degradation after completing Bone Defect Repari, to be absorbed by the body or metabolism excretes, avoid by advantages such as second operation taking-ups, thus in medical implant field, there is potential using value.And hinder magnesium cage material to be that magnesium corrosion of metal current potential is low as the biggest factor that implant is applied, under fluid environment, have very high erosion rate, mechanical integrity loss is too fast.Deposit apatite coating by hydrothermal method at Mg alloy surface, not only can improve the erosion resistance of magnesium alloy, its biological activity is also had some improvement simultaneously.But the shortcoming such as phosphatic rock has film substrate bond strength difference, easy to wear.
Summary of the invention
The object of the invention is to solve prior art magnesium corrosion of metal current potential low, there is very high erosion rate under fluid environment, too fast and the phosphatic rock of mechanical integrity loss has film substrate bond strength difference, the problem of shortcoming easy to wear, and a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating proposed.
Above-mentioned goal of the invention is achieved through the following technical solutions:
Step one, magnesium intermetallic composite coating is become caged implant, at room temperature, utilize 20 ~ 100ml acetone, dehydrated alcohol ultrasonic cleaning caged implant 5 ~ 20min at 15 ~ 25 DEG C successively;
Step 2, utilize deionized water to clean dehydrated alcohol ultrasonic cleaning under temperature 15 ~ 25 DEG C of conditions after caged implant 3 ~ 5min after, under temperature 20 ~ 50 DEG C of conditions dry 10 ~ 20min, obtain pretreated magnesium metallic substance;
Step 3, hydrothermal treatment consists is carried out to magnesium metallic substance pretreated in step 2, obtain the magnesium metal cage implant of surperficial graphene-containing/phosphatic rock hydro-thermal compound coating modification;
Described to the detailed process that magnesium metallic substance pretreated in step 2 carries out hydrothermal treatment consists is:
Pretreated magnesium metallic substance is placed on Ca (NO 3) 2-K 2hPO 4in-GO hydro-thermal reaction solution, adopt HNO 3and NH 3h 2o regulates Ca (NO 3) 2-K 2hPO 4-GO hydro-thermal reaction solution is 1.5 ~ 3.5 to pH, and hydrothermal temperature is 100 ~ 200 DEG C, and the reaction times is 1 ~ 3h.
Wherein, Ca (NO 3) 2-K 2hPO 4ca (NO in-GO hydro-thermal reaction solution 3) 2be 0.1 ~ 0.3mol/L, K 2hPO 4be 0.1 ~ 0.4mol/L and GO be 0.1 ~ 0.5mg/mL;
Step 4, at room temperature, after the magnesium metal cage implant supersound process 5 ~ 10min of the hydrothermal treatment consists rear surface modification utilizing deionized water step 3 to be obtained, drying and processing 20 ~ 40min at 40 DEG C, namely obtains a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.
Invention effect
The invention provides and a kind ofly prepare method with the degradable magnesium cage implant of Antibacterial Graphene/apatite composite coating and preparation method.Coating magnesium cage has anti-corrosion antibacterial, can contain collagen, particulate cancellous bone and the active slowly-releasing factor etc., to reach the quick reparation of Cranial defect, reduces and infects probability.Magnesium metal carrying is for enough mechanics supports during one's term of military service, and magnesium alloy progressively degraded and absorbed after Bone Defect Repari completes, without the need to the object of second operation.
Graphene has perfect two dimensional crystal structure, and in apatite coating, doped graphene material can significantly improve the strength and toughness of rete.Adopt hydrothermal method to build containing the apatite composite coating of Graphene at magnesium based metal, this coating has compared to aspects such as simple apatite coating film substrate bond strength, erosion resistances and significantly improves.Meanwhile, Graphene/apatite coating has good antibacterial effect, is applied to Medical implant material, due to the antibacterial effect that implant itself has, thus effectively can reduce growing and the probability infected of bacterium.
The present invention is based on conventional metals implant not easily to degrade, large with human bone mechanical property gap; After surgical operation implant devices, operative site easy infection; Corrosion stability of magnesium alloy can be poor, too fast and easily lose mechanical integrity at people's vivo degradation; The problems such as apatite coating film substrate bond strength is poor, easy to wear, in conjunction with the advantageous property that Graphene has, invent a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.And further, autologous or allosome particulate cancellous bone can be added in magnesium cage implant, promote bone to merge or the antibacterial sustained-release activity factor etc. thus reach and improve bone and merge speed, reduce the healing cycle of Cranial defect, reduce effects such as infecting probability.
Magnesium metal cage implant material of the present invention completes by foundry engieering, laser 3D printing technique, laser cutting or laser fusion technology, and can make needles of various sizes and shape needed for implant site.
The present invention adds particulate cancellous bone and Cranial defect can be made to repair sooner in magnesium metal cage implant, wherein can add the active slowly-releasing factor and merge to improve bone, bacteria growing inhibiting.Hole on caged beyond the region of objective existence wall can promote planting body endoparticle bone and external exchange of substance.The present invention carries out hydrothermal surface modification to magnesium metal cage implant, be specially in hydrothermal reaction process, graphene sheet layer and phosphatic rock alternately grow at magnesium based metal, the apatite deposition that the composite structure of formation is more simple is finer and close, the solidity to corrosion of coating and film substrate bond strength are obviously strengthened, and makes coating be provided with certain germ resistance by Graphene to bacterial cell membrane structural damage.Adopt streptococcus aureus and colon bacillus to carry out germ resistance test, the antibiotic rate of coating reaches 93.5%, and 95.6%.
The present invention has the following advantages: one, adopt magnesium metal as planting body material, reduce stress shielding, can slowly degrade after completing reparation, avoid 2 operations; Two, in magnesium metal implants body, add particulate cancellous bone, promote knitting, add the active slowly-releasing factor, improve bone and merge speed, reduce and infect probability; Three, machining small on the external wall of magnesium metal implants, promotes exchange of substance inside and outside planting body; Four, on magnesium metal implants body, adopt hydrothermal method surface modification, improve its corrosion resistance, for magnesium metal provided enough mechanics supports before knitting reparation; Five, in hydro-thermal coating, add Graphene, the film substrate bond strength of coating is increased, further enhances corrosion resistance, make coating have certain germ resistance simultaneously; Six, magnesium metal implants body can be designed to true form as required, and hydro-thermal immerseable surface modification is not by the restriction of magnesium cage body material shape.
Magnesium metal cage implant model prepared by the present invention as shown in Fig. 1 (a) He (b), in coating graphene-doped in contrast to uncorporated film substrate bond strength test as shown in Fig. 2 (a) ~ (d).The film substrate bond strength of Fig. 2 (a) ~ (d) for adopting GMW14829 standard to carry out testing coating, the evaluation and test of apatite coating is 5 grades and comes off serious, and Graphene/apatite composite coating is 2 grades and comes off lighter.
The present invention adopts magnesium metal as planting body material, reduces stress shielding, can slowly degrade after completing reparation, avoids 2 operations.In magnesium metal implants body, add particulate cancellous bone, promote knitting, add the active slowly-releasing factor, improve bone and merge speed, reduce and infect probability.Machining small on the external wall of magnesium metal implants, promotes exchange of substance inside and outside planting body.Magnesium metal implants body adopts hydrothermal method surface modification, improves its corrosion resistance, for magnesium metal provided enough mechanics supports before knitting reparation.In hydro-thermal coating, add Graphene, the film substrate bond strength of coating is increased, further enhances corrosion resistance, make coating have certain germ resistance simultaneously.Magnesium metal implants body can be designed to true form as required, and hydrothermal surface is modified as different shape and provides support.
The method prepared with the degradable magnesium cage implant of Antibacterial Graphene/apatite composite coating has the multiple advantages such as antibacterial, anti-corrosion, degradable, film rheobase are high, is mainly used in the reparation of Cranial defect, as interbody bone, and bones of extremities etc.The present invention is a kind of prepares the preparation of the method for the degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating, and method is simple, and repeatability is strong, can realize batch production.
Accompanying drawing explanation
The magnesium metal cage implant model schematic that Fig. 1 (a) proposes for embodiment one;
The magnesium cage implant schematic diagram of the coating that Fig. 1 (b) proposes for embodiment one;
The coating macrograph not adding Graphene that Fig. 2 (a) proposes for embodiment one;
The coated membrane film-substrate binding strength test schematic diagram not adding Graphene that Fig. 2 (b) proposes for embodiment one;
The graphene-doped coating schematic diagram that Fig. 2 (c) proposes for embodiment one;
The graphene-doped coated membrane film-substrate binding strength test schematic diagram that Fig. 2 (d) proposes for embodiment one.
Embodiment
Embodiment one: present embodiment a kind of prepares the method for the degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating, specifically prepares according to following steps:
Step one, magnesium intermetallic composite coating is become caged implant, at room temperature (room temperature is 15 ~ 25 DEG C), after utilizing 20 ~ 100ml acetone to clean caged implant 5 ~ 20min, utilize 20 ~ 100ml dehydrated alcohol ultrasonic cleaning caged implant 5 ~ 20min at 15 ~ 25 DEG C;
Step 2, utilize deionized water to clean dehydrated alcohol ultrasonic cleaning under temperature 15 ~ 25 DEG C of conditions after caged implant 3 ~ 5min after, under temperature 20 ~ 50 DEG C of conditions dry 10 ~ 20min, obtain pretreated magnesium metallic substance; (this deionized water is that International Standards Organization ISO/TC specifies)
Step 3, hydrothermal treatment consists is carried out to magnesium metallic substance pretreated in step 2, obtain the magnesium metal cage implant of surperficial graphene-containing/phosphatic rock hydro-thermal compound coating modification as Fig. 1 (b);
Described to the detailed process that magnesium metallic substance pretreated in step 2 carries out hydrothermal treatment consists is:
Pretreated magnesium metallic substance is placed on Ca (NO 3) 2-K 2hPO 4in-GO hydro-thermal reaction solution, adopt HNO 3and NH 3h 2o regulates Ca (NO 3) 2-K 2hPO 4-GO hydro-thermal reaction solution is 1.5 ~ 3.5 to pH, and hydrothermal temperature is 100 ~ 200 DEG C, and the reaction times is 1 ~ 3h.
Wherein, Ca (NO 3) 2-K 2hPO 4ca (NO in-GO hydro-thermal reaction solution 3) 2be 0.1 ~ 0.3mol/L, K 2hPO 4be 0.1 ~ 0.4mol/L and GO be 0.1 ~ 0.5mg/mL;
Step 4, at room temperature, after the magnesium metal cage implant supersound process 5 ~ 10min of the hydrothermal treatment consists rear surface modification utilizing deionized water step 3 to be obtained, drying and processing 20 ~ 40min at 40 DEG C, namely obtains a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.
Present embodiment effect:
Present embodiments provide for and a kind ofly prepare method with the degradable magnesium cage implant of Antibacterial Graphene/apatite composite coating and preparation method.Coating magnesium cage has anti-corrosion antibacterial, can contain collagen, particulate cancellous bone and the active slowly-releasing factor etc., to reach the quick reparation of Cranial defect, reduces and infects probability.Magnesium metal carrying is for enough mechanics supports during one's term of military service, and magnesium alloy progressively degraded and absorbed after Bone Defect Repari completes, without the need to the object of second operation.
Graphene has perfect two dimensional crystal structure, and in apatite coating, doped graphene material can significantly improve the strength and toughness of rete.Adopt hydrothermal method to build containing the apatite composite coating of Graphene at magnesium based metal, this coating has compared to aspects such as simple apatite coating film substrate bond strength, erosion resistances and significantly improves.Meanwhile, Graphene/apatite coating has good antibacterial effect, is applied to Medical implant material, due to the antibacterial effect that implant itself has, thus effectively can reduce growing and the probability infected of bacterium.
Present embodiment is not easily degraded based on conventional metals implant, large with human bone mechanical property gap; After surgical operation implant devices, operative site easy infection; Corrosion stability of magnesium alloy can be poor, too fast and easily lose mechanical integrity at people's vivo degradation; The problems such as apatite coating film substrate bond strength is poor, easy to wear, in conjunction with the advantageous property that Graphene has, invent a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.And further, autologous or allosome particulate cancellous bone can be added in magnesium cage implant, promote bone to merge or the antibacterial sustained-release activity factor etc. thus reach and improve bone and merge speed, reduce the healing cycle of Cranial defect, reduce effects such as infecting probability.
Present embodiment magnesium metal cage implant material completes by foundry engieering, laser 3D printing technique, laser cutting or laser fusion technology, and can make needles of various sizes and shape needed for implant site.
Present embodiment adds particulate cancellous bone and Cranial defect can be made to repair sooner in magnesium metal cage implant, wherein can add the active slowly-releasing factor and merge to improve bone, bacteria growing inhibiting.Hole on caged beyond the region of objective existence wall can promote planting body endoparticle bone and external exchange of substance.Present embodiment carries out hydrothermal surface modification to magnesium metal cage implant, be specially in hydrothermal reaction process, graphene sheet layer and phosphatic rock alternately grow at magnesium based metal, the apatite deposition that the composite structure of formation is more simple is finer and close, the solidity to corrosion of coating and film substrate bond strength are obviously strengthened, and makes coating be provided with certain germ resistance by Graphene to bacterial cell membrane structural damage.Adopt streptococcus aureus and colon bacillus to carry out germ resistance test, the antibiotic rate of coating reaches 93.5%, and 95.6%.
Present embodiment has the following advantages: one, adopt magnesium metal as planting body material, reduce stress shielding, can slowly degrade after completing reparation, avoid 2 operations; Two, in magnesium metal implants body, add particulate cancellous bone, promote knitting, add the active slowly-releasing factor, improve bone and merge speed, reduce and infect probability; Three, machining small on the external wall of magnesium metal implants, promotes exchange of substance inside and outside planting body; Four, on magnesium metal implants body, adopt hydrothermal method surface modification, improve its corrosion resistance, for magnesium metal provided enough mechanics supports before knitting reparation; Five, in hydro-thermal coating, add Graphene, the film substrate bond strength of coating is increased, further enhances corrosion resistance, make coating have certain germ resistance simultaneously; Six, magnesium metal implants body can be designed to true form as required, and hydro-thermal immerseable surface modification is not by the restriction of magnesium cage body material shape.
Magnesium metal cage implant model prepared by present embodiment as shown in Fig. 1 (a) He (b), in coating graphene-doped in contrast to uncorporated film substrate bond strength test as shown in Fig. 2 (a) ~ (d).The film substrate bond strength of Fig. 2 (a) ~ (d) for adopting GMW14829 standard to carry out testing coating, the evaluation and test of apatite coating is 5 grades and comes off serious, and Graphene/apatite composite coating is 2 grades and comes off lighter.
Present embodiment adopts magnesium metal as planting body material, reduces stress shielding, can slowly degrade after completing reparation, avoid 2 operations.In magnesium metal implants body, add particulate cancellous bone, promote knitting, add the active slowly-releasing factor, improve bone and merge speed, reduce and infect probability.Machining small on the external wall of magnesium metal implants, promotes exchange of substance inside and outside planting body.Magnesium metal implants body adopts hydrothermal method surface modification, improves its corrosion resistance, for magnesium metal provided enough mechanics supports before knitting reparation.In hydro-thermal coating, add Graphene, the film substrate bond strength of coating is increased, further enhances corrosion resistance, make coating have certain germ resistance simultaneously.Magnesium metal implants body can be designed to true form as required, and hydrothermal surface is modified as different shape and provides support.
The method prepared with the degradable magnesium cage implant of Antibacterial Graphene/apatite composite coating has the multiple advantages such as antibacterial, anti-corrosion, degradable, film rheobase are high, is mainly used in the reparation of Cranial defect, as interbody bone, and bones of extremities etc.Present embodiment a kind of prepares the preparation of the method for the degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating, and method is simple, and repeatability is strong, can realize batch production.
Embodiment two: present embodiment and embodiment one unlike: the magnesium metal described in step one is pure magnesium, magnalium, magnesium-zinc alloy, Mg-Zr alloys, magnesium-rare earth or magnesium calcium alloy.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two fill collagen, autogenous particulate bone, allosome particulate cancellous bone unlike: the implant of caged described in step one inside, it is one or more to promote in the bone fusion-activity factor or the antimicrobial sustained-release factor.Other step and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the magnesium alloy caged implant described in step one is the hollow cylindrical body structure of wall thickness 0.3 ~ 3mm, hollow cylindrical body internal diameter is 2 ~ 6mm, wall is provided with the aperture that can make exchange of substance inside and outside caged thing, hole diameter is 0.3 ~ 2mm, is distributed as 1 ~ 5 aperture/mm 2; Further, after scanning modeling is carried out to implant position, corresponding matching Design is carried out to implant shape and structure.
Described caged implant is that ((as Fig. 1 (a)), caged implant can carry out adjustment caged implant size needed for implantation cervical vertebra, lumbar vertebrae, thoracic vertebrae, radius, ulna, shin bone, fibula and mandibular bone position for hollow rule or erratic composition.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the magnesium metal cage implant that step 3 obtains surperficial graphene-containing/phosphatic rock hydro-thermal compound coating modification is applied to the reparation of cervical vertebra, lumbar vertebrae, thoracic vertebrae, radius, ulna, shin bone, fibula and mandibular bone Cranial defect.Other step and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: in step 3, GO is 0.2 ~ 0.4mg/mL.Other step and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are unlike Ca (NO in step 3 3) 2for 0.2mol/L.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven are unlike K in step 3 2hPO 4be 0.2 ~ 0.3mol/L.Other step and parameter identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: the hydro-thermal compound coating thickness described in step 3 is 5 ~ 100 μm.Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the hydro-thermal compound coating described in step 3 is phosphatic rock and Graphene compound coating.Other step and parameter identical with one of embodiment one to nine.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
The present embodiment is a kind of prepares the method for the degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating, specifically prepares according to following steps:
One, magnesium intermetallic composite coating is become caged implant shape, at room temperature use acetone, dehydrated alcohol ultrasonic cleaning 20min successively, use washed with de-ionized water, oven dry afterwards, obtain pretreated magnesium metallic substance;
Two, carry out hydrothermal treatment consists to the magnesium metallic substance after step one processing treatment, wherein hydrothermal temperature is 100 DEG C, and the reaction times is 2h, and hydro-thermal reaction solution is Ca (NO 3) 2-K 2hPO 4-GO mixing solutions, Ca (NO in solution 3) 2for 0.1mol/L, K 2hPO 4for 0.1mol/L, GO are 0.1mg/mL, and adopt HNO 3and NH 3h 2the pH of O regulator solution is 1.5, obtains the magnesium metal cage implant of hydrothermal treatment consists rear surface modification;
Three, use deionized water at room temperature supersound process 5min, drying and processing 20min at 40 DEG C, both obtain a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.
In this test, magnesium metallic substance is Mg-Zn-Ca alloy.The specimen shape of this test processing is cylinder shape hollow cage implant, is specifically of a size of internal diameter 8mm, wall thickness 1mm, height 15mm.Stochastic distribution hole diameter 1mm on outer wall, little pore distribution every square centimeter 2 ~ 4.Coat-thickness is 50 μm, and coating outer surface visual inspection is black.Tested by stretching bonding strength, the film substrate bond strength of coating is 25.3MPa, and for the apatite coating not adding Graphene and prepare, film substrate bond strength is 5.0MPa.Adopt streptococcus aureus and colon bacillus to carry out germ resistance test, the antibiotic rate of coating reaches 92.3%, and 94.5%.
Embodiment two:
One, magnesium intermetallic composite coating is become caged implant shape, at room temperature use acetone, dehydrated alcohol ultrasonic cleaning 20min successively, use washed with de-ionized water, oven dry afterwards, obtain pretreated magnesium metallic substance;
Two, carry out hydrothermal treatment consists to the magnesium metallic substance after step one processing treatment, wherein hydrothermal temperature is 120 DEG C, and the reaction times is 3h, and hydro-thermal reaction solution is Ca (NO 3) 2-K 2hPO 4-GO mixing solutions, Ca (NO in solution 3) 2for 0.15mol/L, K 2hPO 4for 0.1mol/L, GO are 0.2mg/mL, and adopt HNO 3and NH 3h 2the pH of O regulator solution is 2.0, obtains the magnesium metal cage implant of hydrothermal treatment consists rear surface modification;
Three, use deionized water at room temperature supersound process 5min, drying and processing 20min at 40 DEG C, both obtain a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.
In this test, magnesium metallic substance is AZ31 magnesium alloy.The specimen shape of this test processing is cylinder shape hollow cage implant, is specifically of a size of internal diameter 10mm, wall thickness 1mm, height 20mm.Stochastic distribution hole diameter 1mm on outer wall, little pore distribution every square centimeter 2 ~ 4.Coat-thickness is 60 μm, and coating outer surface visual inspection is black.Learn test by stretching, the film substrate bond strength of coating is 22.5MPa.Adopt streptococcus aureus and colon bacillus to carry out germ resistance test, the antibiotic rate of coating reaches 88.9%, and 92.1%.
Embodiment three:
One, magnesium intermetallic composite coating is become caged implant shape, at room temperature use acetone, dehydrated alcohol ultrasonic cleaning 20min successively, use washed with de-ionized water, oven dry afterwards, obtain pretreated magnesium metallic substance;
Two, carry out hydrothermal treatment consists to the magnesium metallic substance after step one processing treatment, wherein hydrothermal temperature is 150 DEG C, and the reaction times is 3h, and hydro-thermal reaction solution is Ca (NO 3) 2-K 2hPO 4-GO mixing solutions, Ca (NO in solution 3) 2for 0.2mol/L, K 2hPO 4for 0.15mol/L, GO are 0.1mg/mL, and adopt HNO 3and NH 3h 2the pH of O regulator solution is 3.0, obtains the magnesium metal cage implant of hydrothermal treatment consists rear surface modification;
Three, use deionized water at room temperature supersound process 10min, drying and processing 20min at 40 DEG C, both obtain a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.
In this test, magnesium metallic substance is AM50 magnesium alloy.The specimen shape of this test processing is cylinder shape hollow cage implant, is specifically of a size of internal diameter 12mm, wall thickness 1mm, height 15mm.Stochastic distribution hole diameter 1mm on outer wall, little pore distribution every square centimeter 3 ~ 5.Coat-thickness is 80 μm, and coating outer surface visual inspection is black.Learn test by stretching, the film substrate bond strength of coating is 26.2MPa.Adopt streptococcus aureus and colon bacillus to carry out germ resistance test, the antibiotic rate of coating reaches 93.5%, and 95.6%.
The present invention also can have other various embodiments; when not deviating from the present invention's spirit and essence thereof; those skilled in the art are when making various corresponding change and distortion according to the present invention, but these change accordingly and are out of shape the protection domain that all should belong to the claim appended by the present invention.

Claims (10)

1. prepare a method for the degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating, it is characterized in that what a kind of method prepared with the degradable magnesium cage implant of Antibacterial Graphene/apatite composite coating was specifically carried out according to following steps:
Step one, magnesium intermetallic composite coating is become caged implant, at room temperature, utilize 20 ~ 100ml acetone, dehydrated alcohol ultrasonic cleaning caged implant 5 ~ 20min at 15 ~ 25 DEG C successively;
Step 2, utilize deionized water to clean dehydrated alcohol ultrasonic cleaning under temperature 15 ~ 25 DEG C of conditions after caged implant 3 ~ 5min after, under temperature 20 ~ 50 DEG C of conditions dry 10 ~ 20min, obtain pretreated magnesium metallic substance;
Step 3, hydrothermal treatment consists is carried out to magnesium metallic substance pretreated in step 2, obtain the magnesium metal cage implant of surperficial graphene-containing/phosphatic rock hydro-thermal compound coating modification;
Described to the detailed process that magnesium metallic substance pretreated in step 2 carries out hydrothermal treatment consists is:
Pretreated magnesium metallic substance is placed on Ca (NO 3) 2-K 2hPO 4in-GO hydro-thermal reaction solution, adopt HNO 3and NH 3h 2o regulates Ca (NO 3) 2-K 2hPO 4-GO hydro-thermal reaction solution is 1.5 ~ 3.5 to pH, and hydrothermal temperature is 100 ~ 200 DEG C, and the reaction times is 1 ~ 3h;
Wherein, Ca (NO 3) 2-K 2hPO 4ca (NO in-GO hydro-thermal reaction solution 3) 2be 0.1 ~ 0.3mol/L, K 2hPO 4be 0.1 ~ 0.4mol/L and GO be 0.1 ~ 0.5mg/mL;
Step 4, at room temperature, after the magnesium metal cage implant supersound process 5 ~ 10min of the hydrothermal treatment consists rear surface modification utilizing deionized water step 3 to be obtained, drying and processing 20 ~ 40min at 40 DEG C, namely obtains a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating.
2. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 1, is characterized in that: the magnesium metal described in step one is pure magnesium, magnalium, magnesium-zinc alloy, Mg-Zr alloys, magnesium-rare earth or magnesium calcium alloy.
3. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 2, is characterized in that: the implant of caged described in step one inside fills collagen, autogenous particulate bone, allosome particulate cancellous bone, it is one or more to promote in the bone fusion-activity factor or the antimicrobial sustained-release factor.
4. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 3, it is characterized in that: the magnesium alloy caged implant described in step one is the hollow cylindrical body structure of wall thickness 0.3 ~ 3mm, hollow cylindrical body internal diameter is 2 ~ 6mm, wall is provided with aperture, hole diameter is 0.3 ~ 2mm, is distributed as 1 ~ 5 aperture/mm 2.
5. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 4, is characterized in that: the magnesium metal cage implant of the hydrothermal treatment consists rear surface modification that step 3 obtains is applied to the reparation of cervical vertebra, lumbar vertebrae, thoracic vertebrae, radius, ulna, shin bone, fibula and mandibular bone Cranial defect.
6. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 5, is characterized in that: in step 3, GO is 0.2 ~ 0.4mg/mL.
7. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 6, is characterized in that: Ca (NO in step 3 3) 2for 0.2mol/L.
8. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 7, is characterized in that: K in step 3 2hPO 4be 0.2 ~ 0.3mol/L.
9. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 8, is characterized in that: the hydro-thermal compound coating thickness described in step 3 is 5 ~ 100 μm.
10. a kind of method preparing degradable magnesium cage implant with Antibacterial Graphene/apatite composite coating according to claim 9, is characterized in that: the hydro-thermal compound coating described in step 3 is phosphatic rock and Graphene compound coating.
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CN106567062A (en) * 2016-10-20 2017-04-19 中国科学院上海硅酸盐研究所 Surface modified magnesium alloy material with good corrosion resistance and biocompatibility and preparation method and application thereof
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