CN104928517B - Porous magnesium based hydroxylapatite composite material and preparation method thereof and resulting materials thereof - Google Patents
Porous magnesium based hydroxylapatite composite material and preparation method thereof and resulting materials thereof Download PDFInfo
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Abstract
The invention provides a kind of porous magnesium based hydroxylapatite composite material and preparation method thereof and resulting materials thereof, wherein preparation method, comprise the following steps: 1) paraffin core is connected in outer die casing, the space between outer die casing and core is filled magnesium powder, obtains outer die casing matrix；2) to carrying out vacuum-sintering after outer die casing matrix extrusion forming, remove outer die casing and obtain porous magnesium matrix；3) by electrophoretic deposition at porous magnesium matrix surface formation of deposits hydroxyapatite layer, porous magnesium based hydroxylapatite composite is obtained.After using the composite that the present invention provides, the healing rate of experimental mouse brings up to 280 days.
Description
Technical field
The present invention relates to field of medical materials, especially, relate to a kind of porous magnesium based hydroxylapatite composite material and preparation method thereof
And resulting materials.
Background technology
Magnesium as can in human body the material of ira situ degradation, metallic orthopaedic implant material nondegradable with tradition (as titanium alloy,
Rustless steel etc.) compare that to have specific strength high, elastic modelling quantity is more close with natural bone (3～30Gpa), and high elastic modulus can be avoided golden
Belong to the stress capture-effect caused.When especially magnesium is as body support's materials'use, can degrade at human internal environment's situ, keep away
Exempt from second operation this advantage of injury to human body so that it is by the extensive concern of researcher.But when magnesium uses as backing material,
In human internal environment, corrode decomposition rate be far longer than the speed of growth of human bone cell, cause implanting the magnesium fid in human body
Material, the mechanics task that support organization of human body is had not been completed has been decomposed complete.Have impact on the recovery of patient.
Hydroxyapatite is similar to the composition of biological bone, has good biocompatibility with human body new life sclerotin, and has bone biography
The property led and osteoinductive, can improve the resume speed of human body.But this material mechanical performance is poor, fragility is big, can not load-bearing,
Therefore cannot function as artificial bone backing material in human body, it is achieved to the support suffering from body.
CN201310031015.X such as discloses a kind of magnesium or magnesium alloy porous hydroxyapatite composite and preparation thereof
Method, wherein magnesium or magnesium alloy are only capable of penetrating in hydroxyapatite, form the multiple micro hole accommodating hydroxyapatite in matrix
Hole, pore space structure and position are difficult to fixing, it is difficult to ensure that the position of gained hole meets human bone cell growth tendency and direction,
The limited space provided of growing up for new osteocyte.After human body, the regeneration of sclerotin is slow, extends the human body recovery phase.
Summary of the invention
The present invention provides a kind of porous magnesium based hydroxylapatite composite material and preparation method thereof and resulting materials thereof, to solve existing skill
Art lacks growing space due to new bone, thus causes reducing new bone growth speed, reduce the technical problem of human body recovery time.
According to an aspect of the invention, it is provided the preparation method of a kind of porous magnesium based hydroxylapatite composite, including
Following steps: 1) paraffin core is connected in outer die casing, the space between outer die casing and core is filled magnesium powder, outside obtaining
Die sleeve matrix；2) to carrying out vacuum-sintering after outer die casing matrix extrusion forming, remove outer die casing and obtain porous magnesium matrix；3) logical
Cross electrophoretic deposition at porous magnesium matrix surface formation of deposits hydroxyapatite layer, obtain porous magnesium based hydroxylapatite composite；
The condition of extrusion forming step is the power that outer die casing matrix applies 25KN, pressurize 5 minutes.
Further, magnesium powder by purity be 99.8% granularity be magnesium powder material and the purity of 100 mesh be the dehydrated alcohol of 99.5%, by magnesium
Powder is that 6:1 is mixed to get with the mass ratio of dehydrated alcohol.
Further, with porous magnesium matrix as negative electrode in electrophoretic deposition, using stereotype as anode, comprise the following steps: anode is put down
Row is arranged in negative electrode, and anode is 10mm with the spacing of negative electrode, and constant voltage 60V deposits 60 minutes, with hydroxyapatite solution is
Suspension, is the hydroxyapatite layer of 2mm at porous magnesium matrix surface deposit thickness.
Further, the compound method of hydroxyapatite solution: hydroxy apatite powder is joined dispersion in dehydrated alcohol and obtains
Concentration is the suspension of 0.02kg/L, instill in suspension suspension cumulative volume 1～3% salpeter solution as electrolyte, use ammonia
Suspension pH value is adjusted to 4～5 by water, stirs 60 minutes through ultrasonic echography, and after boiling 2 hours, ageing obtains hydroxyl in 10 days
Apatite solution.
Further, also include porous magnesium based hydroxylapatite composite is carried out coating densification, coating densification
It is processed as in 400 DEG C of argon gas atmosphere insulation 10 hours.
Further, outer die casing includes removable sleeve and multiple pipe collar, removable sleeve is provided with along its bus and takes seam apart, and pipe collar divides
It is not installed on the two ends of removable sleeve.
Further, vacuum-sintering step comprises the following steps: be 2Mpa in vacuum, sintering temperature 550～600 DEG C, insulation
40～60 minutes, after taking out cooling after having sintered 4 hours, remove outer die casing.
Further, for the vacuum protection set of outer die casing matrix evacuation is included for accommodating outer die casing in vacuum-sintering step
The vacuum cylinder of matrix and for the cover plate sealing vacuum cylinder, cover plate offers exhaust tube, and one end of exhaust tube is installed on
It is connected on cover plate and with vacuum cylinder, the other end of exhaust tube is installed the mounting flange of bleeding for being connected with air extractor.
Additionally provide a kind of porous magnesium based hydroxylapatite composite, porous magnesio hydroxyl according to a further aspect in the invention
Apatite composite material is that method described above prepares；Porous magnesium based hydroxylapatite composite includes magnesium matrix and sets
It is placed in the hydroxyapatite layer on magnesium matrix surface, be connected with each other logical multiple radial holes and multiple axial hole is set in magnesium matrix,
Radial hole is arranged in magnesium matrix along extending radially through of magnesium matrix；Axial hole is arranged in magnesium matrix along axially penetrating through of magnesium matrix；
Axial hole is 5mm with the diameter of radial hole, and the centre-to-centre spacing in axial hole is 7mm two-by-two；The centre-to-centre spacing of radial hole is 7mm two-by-two；
After the internal surface of hole deposited hydroxyl apatite layer in radial hole and axial hole, all leave the centre bore of a diameter of 1mm.
The method have the advantages that
The composite inner that the present invention provides is provided with a plurality of skeletonization passage perpendicular to one another, is formed at material internal and has especially big sky
Between loose structure, control the aperture of institute formation loose structure simultaneously, thus on the one hand reduce the elastic modelling quantity of magnesium matrix so that it is
Biomechanical property is closer to natural bone, and on the other hand the osteoblastic growth that exists for of the skeletonization passage of hole formation provides
Convenient.Form hydroxyapatite also by electrophoretic deposition on skeletonization channel surface within magnesium matrix, utilize hydroxyapatite to be had
Having good biocompatibility, bone conductibility and osteoinductive, for osteocyte in skeletonization passage, oriented growth provides nutrition to become
Point, thus reach to promote the purpose of bone healing.After using this material, the healing rate of experimental mouse brings up to 280 days.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.Below
Will be with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing of the part constituting the application is used for providing a further understanding of the present invention, the illustrative examples of the present invention and
Its explanation is used for explaining the present invention, is not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the schematic perspective view of the magnesium matrix of the preferred embodiment of the present invention；
Fig. 2 is the three-dimensional partial schematic sectional view of the magnesium matrix of the preferred embodiment of the present invention；
Fig. 3 is the porous magnesium based hydroxylapatite composite schematic perspective view of the preferred embodiment of the present invention；
Fig. 4 is the electrophoretic deposition process schematic diagram of the preferred embodiment of the present invention；
Fig. 5 is the outer die casing schematic top plan view of the preferred embodiment of the present invention；
Fig. 6 is the outer die casing schematic front view of the preferred embodiment of the present invention；
Fig. 7 is the core schematic perspective view of the preferred embodiment of the present invention；
Fig. 8 is that the vacuum protection set of the preferred embodiment of the present invention is main regarding cross-sectional schematic；
Fig. 9 is that the tissue slice result of the Implantation Time of preferred embodiment of the present invention porous magnesium based hydroxylapatite composite is shown
It is intended to (× 100): a. matched group tissue slice；The most postoperative 2 weeks tissue slices；The most postoperative 3 weeks tissue slices；The most postoperative 4 weeks groups
Knit section (× 40).
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail, but the present invention can be defined by the claims and cover
Multitude of different ways implement.
If not specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art.
The percentage sign " % " arrived referred to herein, if not specified, refers to mass percent；But the percentage ratio of solution, except another
Have outside regulation, refer in solution 100m1 containing some grams of solute；Percentage ratio between liquid, refers to the ratio of capacity when 20 DEG C
Example.
The porous magnesium based hydroxylapatite composite material and preparation method thereof that the present invention provides, comprises the following steps:
1) paraffin core is connected in outer die casing, the space between outer die casing and core is filled magnesium powder, obtains outer die casing base
Body；
2) to carrying out vacuum-sintering after outer die casing matrix extrusion forming, remove outer die casing and obtain porous magnesium matrix；
3) by electrophoretic deposition at porous magnesium matrix surface formation of deposits hydroxyapatite layer, porous magnesium based hydroxylapatite is obtained
Composite；The condition of extrusion forming step is the power that described outer die casing matrix applies 25KN, pressurize 5 minutes.
It is prepared by this condition, and controls carry out pressurize under this condition and apply pressure, hydroxy-apatite in resulting materials can be made
Rock layers penetrates in the miniature hole of magnesium matrix, thus reaches to extend the effect of magnesium matrix supporting time comprehensively.Can make again simultaneously
Space is left in hydroxyapatite layer in magnesium matrix hole.Make various types of cells liquid and grow into osteocyte desired substance entrance magnesium
In matrix, form new skeletal tissue wherein, make full use of hydroxyapatite therein and grow.Thus be effectively increased
The rehabilitation speed of patient, shortens rehabilitation duration.
The condition of preferably extrusion forming step is the power that outer die casing matrix applies 25KN, pressurize 5 minutes.Carry out by this condition,
The consistency of gained magnesium matrix 100 can be effectively improved.The support effect making magnesium matrix 100 is more preferable and lasting.
Preferably, magnesium powder by purity be 99.8% granularity be magnesium powder material and the purity of 100 mesh be the dehydrated alcohol of 99.5%, by magnesium powder with
Dehydrated alcohol mass ratio is that 6:1 is mixed to get.It is filled with as magnesium powder after using the material mixing of this purity and granularity, permissible
It is effectively improved the intermiscibility of magnesium powder and hydroxyapatite.Extend the thickness of the penetrating layer that magnesium matrix 100 is formed with hydroxyapatite,
Slow down the speed of magnesium matrix 100 corrosion.Can be in this ratio mixing space filling between outer die casing and core of gained magnesium powder
Excellent, improve the quality of gained composite.
Preferably, with porous magnesium matrix as negative electrode in electrophoretic deposition, using stereotype as anode, comprise the following steps: anode is parallel to
Negative electrode is arranged, and anode is 10mm with the spacing of negative electrode, and constant voltage 60V deposits 60 minutes, with hydroxyapatite solution for suspending
Liquid, is the hydroxyapatite layer of 2mm at porous magnesium matrix surface deposit thickness.The setting of each electrode such as figure in electrophoretic deposition step
Shown in 4, tiselius apparatus is poured suspension 240 into.Again the first stereotype 210 and the second stereotype 220 are arranged near electrophoresis pool wall.
The magnesium matrix 100 with radial hole 120 and axial hole 110 is positioned over the first stereotype 210 and the second stereotype as negative electrode 240
Between 220.Lead flake a size of 40mm × 40mm × 2mm used.Negative and positive the two poles of the earth keeping parallelism, spacing is adjusted to 10mm, perpendicular
Straight cutting enters in suspension, in order to the coating making magnesium matrix 100 axial hole 110 hole inner surface is more uniform, by axial hole 110
Two opposing end surfaces towards the first stereotype 210 and the second stereotype 220.60V constant voltage mode is used to carry out electrophoretic deposition, during deposition
Between be 60 minutes.Obtaining face coat thickness is 2mm.Carry out electrophoresis by this condition, gained composite can be effectively improved and use
After human body, the rehabilitation efficiency of human body, shortens rehabilitation duration.Making in this material, hydroxyapatite can effectively stretch into magnesium matrix
In 100, form transition region, improve the resistance to corrosion of magnesium matrix 100.
The compound method of hydroxyapatite solution the most used: hydroxy apatite powder is joined in dehydrated alcohol and disperses
Be the suspension of 0.02kg/L to concentration, instill in suspension suspension cumulative volume 1～3% salpeter solution as electrolyte, use
Suspension pH value is adjusted to 4～5 by ammonia, stirs 60 minutes through ultrasonic echography, and after boiling 2 hours, ageing obtains hydroxyl in 10 days
Base apatite solution.Configure by this, the ionization of hydroxyapatite in electrophoresis process can be effectively improved and to magnesium matrix 100
Adhesive ability, the amount of bringing into of impurity is down to minimum.Thus extend gained composite service life in human body, improve
The acceptable degree of human body.
Preferably, also include porous magnesium based hydroxylapatite composite is carried out coating densification, coating densification
For being incubated 10 hours in 400 DEG C of argon gas atmosphere.Process by this condition, gained hydroxyapatite coating layer can be effectively improved
Compactness extent, improve the osteoblast utilization rate to hydroxyapatite coating layer, extend hydroxyapatite coating layer to osteoblast layer
Inducing action timeliness, improve Oesteoblast growth speed.
Preferably outer die casing includes removable sleeve 330 and multiple pipe collar 320, removable sleeve is provided with along its bus and takes seam 340 apart, pipe
Hoop 320 is respectively arranged in the two ends of removable sleeve 330.Seeing Fig. 5～6, the removable sleeve 330 in outer die casing used can use
Steel pipe is made.After steel pipe 330 is rived along its bus, being formed and take seam 340 apart, after molding completes, outer die casing can be along taking seam apart
340 are divided into two, thus realize the dismounting of magnesium matrix 100.Avoid magnesium matrix 100 is damaged by demolishing process.In order to anti-
Only in removable sleeve 330, the magnesium powder of filling leaks in compacting process, and two opposite ends of removable sleeve 330 are provided with pipe collar 320.
Pipe collar 320 is strained by screw 310.Using this respective outer side edges core 400 as shown in Figure 7, core 400 is made for paraffin.
Profile one big cylinder of approximation of core 400, this big cylinder is by some axial cylindrical 410 of a diameter of 5mm and radially cylinder 420
Composition.Axial cylindrical 410 along big cylinder axis to setting.Radially cylinder 420 is radially arranged along big cylinder.Axial cylindrical 410 He
Radially the arrangement mode of cylinder 420 and axial hole 110 and radial hole 120 is identical.Axial cylindrical 410 and radially cylinder 420
Diameter be 5mm.Centre-to-centre spacing between axial cylindrical 410 is 7mm two-by-two.Centre-to-centre spacing between radial direction cylinder 420 two-by-two
For 7mm.Core 400 first passes through three-dimensional modeling, then uses 3D wax spray printer to print.The core 400 printed
It is stored in the place less than 25 DEG C, prevents deformation.Use paraffin as core 400, can melt during follow-up sintering,
Can effectively reduce the structural failure of gained magnesium matrix 100.
Preferably, vacuum-sintering step comprises the following steps: be 2Mpa in vacuum, sintering temperature 550～600 DEG C, is incubated 40～60
Minute, remove outer die casing after taking out cooling after having sintered 4 hours.Magnesium matrix 100 is put into vacuum protection together with outer die casing
In set, vacuum protection being overlapped evacuation, vacuum keeps 2MPa.Vacuum protection set is put in Muffle furnace sintering, sets sintering
Temperature is 550 DEG C～600 DEG C, and temperature retention time is 40～60 minutes.In sintering process, the gasification of paraffin core disappears, and forms magnesium
Intrinsic silicon hole.Take out vacuum protection after having sintered and be placed on room temperature cooling 4 hours, take out magnesium matrix together with external mold, pine
Over mould trip bolt, spiral pipe collar is taken off, separately external mold, take out porous magnesium matrix 100.It is sintered place by this condition
Reason can be effectively improved the compactness in gained magnesium matrix 100 between magnesium molecule, reduces human internal environment to its corrosion rate.Prolong
The long gained composite supporting role time to human body, the beneficially recovery of human body.
See Fig. 8, for including the vacuum protection set of outer die casing matrix evacuation for accommodating outer die casing base in vacuum-sintering step
The vacuum cylinder 1 of body and for the cover plate 5 sealing vacuum cylinder 1, cover plate 5 offers exhaust tube 7, the one of exhaust tube 7
End is installed on cover plate 5 and is connected with vacuum cylinder 1, and the other end of exhaust tube 7 is installed for being connected with air extractor
Mounting flange 8 of bleeding.
Vacuum protection set can realize the highest 2MPa vacuum, and its function is that protection is put under the sintering temperature of 550 DEG C～600 DEG C
The magnesium matrix entering it interior is not oxidized, and vacuum cylinder 1 is cylinder, can accommodate the prepattern magnesium matrix 100 being coated with by outer die casing.Lid
Plate 5 seals with vacuum cylinder 1.Vacuum cylinder 1 opening end is provided with mounting flange 4 on lateral wall.Mounting flange 4 and cover plate 5
On installing hole be connected.In order to ensure sealing, cover plate 5 and vacuum cylinder 1 joint arrange sealing ring 6, and pass through bolt
3 fixing connections.Cover plate 5 center offers exhaust tube 7.In order to air extractor being fixed on one end of exhaust tube 7, exhaust tube
Mounting flange 8 of bleeding it is additionally provided with on the outer wall of 7.Air extractor can be vacuum pump.Can also can be with the device of evacuation for other.
Vacuum pump is fixed on mounting flange 8 of bleeding and vacuum cylinder 1 is carried out evacuation.
Preferably, the pipeline that air extractor is connected is additionally provided with stop valve 9, it is achieved the guarantor of vacuum protection set vacuum with exhaust tube 7
Hold.During use, turn on bolt 3, cover plate 5 is unloaded, sample is loaded in vacuum cylinder 1, loads onto cover plate 5, tight a bolt
3, vacuum pump is fixedly installed in by the installing hole of mounting flange 8 of bleeding and bleeds on mounting flange 8, open stop valve 9, take out
Vacuum, after vacuum reaches predetermined value, closes stop valve, unloads vacuum pump.Vacuum protection set can realize vacuum protection to sample.
Preferably gained magnesium matrix 100 also needs just to carry out electrophoretic deposition step through pretreatment.Pretreatment includes with 320～No. 800
The outer surface of SiC liquid honing magnesium matrix 100, the most sequentially carries out ultrasonic cleaning each in acetone, dehydrated alcohol and distilled water
10 minutes, after completing, take out natural drying.So carry out pretreatment, it is possible to reduce the impact on gained composite of the various impurity.
Improve the outer surface of magnesium matrix 100 and the intermiscibility of hydroxyapatite, improve the steadiness of hydroxyapatite, thus realize shortening
The effect of Oesteoblast growth time.
Another aspect of the present invention additionally provides a kind of porous magnesium based hydroxylapatite composite prepared as stated above.
Seeing Fig. 1～3, arrange be connected with each other logical multiple radial holes 120 and multiple axial hole 110 in magnesium matrix, radial hole 120 is along magnesium
Being radially disposed in magnesium matrix 100 of matrix 100；Axial hole 110 axially penetrates through magnesium matrix 100 along magnesium matrix 100；Axially
Hole 110 is 5mm with the diameter of radial hole 120, and the centre-to-centre spacing in axial hole 110 is 7mm two-by-two；Radial hole 120 two-by-two
Centre-to-centre spacing is；After the internal surface of hole deposited hydroxyl apatite layer 130 in radial hole 120 and axial hole 110, all leave a diameter of 1mm
Centre bore 140.Axial hole 110 along magnesium matrix 100 axially through magnesium matrix 100.Radial hole 120 two ends are submerged in magnesium matrix
In 100.
Gained composite outer surface is cylindrical, similar with skeleton structure, can play a supporting role in human body.Matrix
Hydroxyapatite layer 130 it is also equipped with on 100 outer surfaces.Improve the osteoblast speed of growth at composite material surface.Thus promote
Enter human body to recover.Hydroxyapatite layer 130 hydroxyapatite layer that formation of deposits is thicker in radial hole 120 and axial hole 110
130.And on the centre bore 140 in each hole, offer the centre bore 140 of a diameter of 1mm.Centre bore 140 is respectively arranged at radially
In hole 120 and axial hole 110.The centre bore 140 being arranged in radial hole 120 and the dead in line of radial hole 120.It is arranged at
Centre bore 140 in axial hole 110 and the dead in line in axial hole 110.Centre bore 140 radially hole 120 axially through footpath
Arrange to hole 120.Arranging axially through axial hole of centre bore 140 hole 110 vertically.The centre bore 140 of this diameter is set
Osteoblast can be made to be more easy to go deep into fast-growth in radial hole 120 and axial hole 110, be internally formed at magnesium matrix 100 and hand in length and breadth
Wrong dictyonalia structure, is conducive to being initially formed the network structure with supporting role inside magnesium matrix 100.Axial hole 110
It is 5mm with the diameter of radial hole 120.By this size, the radial hole 120 in composite and axial hole 110 and skeleton are set
In hone lamella arrangement architecture similar with size, osteoblast obtains after the nourishing of hydroxyapatite layer 130 first at radial hole 120
Form osteocyte with growth in axial hole 110, and further growth forms hone lamella, thus improve the resume speed of human body, shorten health
The multiple time.
The centre-to-centre spacing in axial hole 110 is 7mm two-by-two.The centre-to-centre spacing of radial hole 120 is 7mm two-by-two..By this, centre bore is set,
The elastic modelling quantity that can make magnesium matrix 100 reaches optimum, can realize the supporting role to human body so that it is supporting role is more nearly
In skeleton, this supporting role can be kept before forming hone lamella in axial hole 110 with radial hole 120 simultaneously.And can be
Hone lamella gradually melts with the growth of skeleton after being formed in time.
Embodiment
In following example, material used and instrument are commercially available.
Embodiment 1
1) core is fixed in outer die casing.
2) by 600 grams of magnesium powder (purity is 99.8%, and granularity is 100 mesh) and 100 grams of dehydrated alcohol (purity is 99.5%)
It is sufficiently mixed, stirs.Then magnesium powder is filled uniformly with in the core hole with outer die casing, make magnesium powder and outer die casing top
Face is concordant.
3) populated model is put on hydraulic press, applies the pressure of 25KN, pressurize 5 minutes, unloading, porous magnesium
Matrix molding.
4) together with outer die casing, magnesium matrix being put into vacuum protection set, vacuum protection is overlapped evacuation, vacuum keeps 2MPa.
Vacuum protection set being put in Muffle furnace sintering, sets sintering temperature as 550 DEG C, temperature retention time is 40 minutes.In sintering process
In, the gasification of paraffin core disappears, and forms magnesium matrix inner void.Take out vacuum protection after having sintered and be placed on room temperature cooling 4
Hour, taking-up magnesium matrix, together with outer die casing, unclamps outer die casing trip bolt, is taken off by spiral pipe collar, separately outer die casing, takes out
Porous magnesium matrix.
5) pretreatment of magnesium matrix material: by porous magnesium outer surface of matrix after No. 320 SiC liquid honings respectively acetone,
Dehydrated alcohol and ultrasonic cleaning in distilled water 10 minutes, take out natural drying after completing.
6) preparation of hydroxyapatite suspensions: hydroxy apatite powder joins configuration concentration in dehydrated alcohol disperse medium is
The suspension of 0.02kg/L, instills a little (about suspension cumulative volume 2%) salpeter solution and adjusts as electrolyte, addition proper ammonia
Joint suspension pH value 4.Stir 60 minutes through ultrasonic echography, boil 2 hours, and be aged 10 days.
7) electrophoretic deposition: the porous magnesium matrix previously prepared is made negative electrode, anode made by lead flake (40mm × 40mm × 2mm)；
Negative and positive the two poles of the earth keeping parallelism, spacing is adjusted to 10mm, is inserted vertically in suspension, in order to make the coating of magnesium matrix hole inner surface more
Add uniformly, the through hole on porous magnesium matrix two opposite end is arranged towards two anodes.60V constant voltage mode is used to carry out electrophoretic deposition,
Sedimentation time is 60 minutes.Obtaining face coat thickness is 2mm.
8) subsequent treatment of coating: at ambient temperature coating is dried process.In order to make coating densification, at 400 DEG C
Argon gas atmosphere is incubated 10 hours.Obtain porous magnesium based hydroxylapatite composite.
Embodiment 2
1) core is fixed in outer die casing.
2) by 600 grams of magnesium powder (purity is 99.8%, and granularity is 100 mesh) and 100 grams of dehydrated alcohol (purity is 99.5%)
It is sufficiently mixed, stirs.Then magnesium powder is filled uniformly with in the core hole with outer die casing, make magnesium powder and outer die casing top
Face is concordant.
3) populated model is put on hydraulic press, applies the pressure of 25KN, pressurize 5 minutes, unloading, porous magnesium
Matrix molding.
4) together with outer die casing, magnesium matrix being put into vacuum protection set, vacuum protection is overlapped evacuation, vacuum keeps 2MPa.
Vacuum protection set being put in Muffle furnace sintering, sets sintering temperature as 600 DEG C, temperature retention time is 60 minutes.In sintering process
In, the gasification of paraffin core disappears, and forms magnesium matrix inner void.Take out vacuum protection after having sintered and be placed on room temperature cooling 4
Hour, taking-up magnesium matrix, together with outer die casing, unclamps outer die casing trip bolt, is taken off by spiral pipe collar, separately outer die casing, takes out
Porous magnesium matrix.
5) pretreatment of magnesium matrix material: by porous magnesium outer surface of matrix after No. 800 SiC liquid honings respectively acetone,
Dehydrated alcohol and ultrasonic cleaning in distilled water 10 minutes, take out natural drying after completing.
6) preparation of hydroxyapatite suspensions: hydroxy apatite powder joins configuration concentration in dehydrated alcohol disperse medium is
The suspension of 0.02kg/L, instills a little (about suspension cumulative volume 2%) salpeter solution and adjusts as electrolyte, addition proper ammonia
Joint suspension pH value 5.Stir 60 minutes through ultrasonic echography, boil 2 hours, and be aged 10 days.
7) electrophoretic deposition: the porous magnesium matrix previously prepared is made negative electrode, anode made by lead flake (40mm × 40mm × 2mm)；
Negative and positive the two poles of the earth keeping parallelism, spacing is adjusted to 10mm, is inserted vertically in suspension, in order to make the coating of magnesium matrix hole inner surface more
Add uniformly, the through hole on porous magnesium matrix two opposite end is arranged towards two anodes.60V constant voltage mode is used to carry out electrophoretic deposition,
Sedimentation time is 60 minutes.Obtaining face coat thickness is 2mm.
8) subsequent treatment of coating: at ambient temperature coating is dried process.In order to make coating densification, at 400 DEG C
Argon gas atmosphere is incubated 10 hours.Obtain porous magnesium based hydroxylapatite composite.
Zoopery:
In order to verify the biocompatibility of porous magnesium based hydroxylapatite composite, biological activity, we utilize embodiment 2
Middle resulting materials has done zoopery and has tested with SBF (simulated body fluid) solution soaking.
1) zoopery object: SD rat 40, derives from University Of Nanhua's animal experimental center.It is divided into 4 groups, blank
The combination of group i.e. blank, experiment 1, experiment 2 and experiment 3 groups, often group mouse 10.By gained experiment material in embodiment 1
Material, is implanted in experimental mouse body respectively by operation.Perusal experimental mouse postoperative wound, it is seen that mild redness, without infiltration, greatly
Wound healing after about two weeks.
A, zoopery one are using in embodiment 1, gained porous magnesium based hydroxylapatite composite is as experiment material, by it
Implanting in Rat muscle tissue, this muscular tissue is near skeleton.Put to death experimental rat respectively at postoperative 2 weeks, 3 weeks and 4 weeks in batches,
After dissection, treating excess syndrome tests the tissue of surrounding materials, carries out tissue slice and carries out HE dyeing, uses biological microscope perusal muscle
Tissue topography.
One of which does not implants this material as blank group.In a) figure that blank group acquired results is listed in Fig. 9.Real
Test the group b that is listed in Fig. 9 of acquired results) figure, c) figure and d) in figure, b) figure is that experiment material implants mouse body 2 weeks
Rear tissue slice result figure.C) figure is that experiment material implants mouse body tissue slice result figure after 3 weeks.D) figure is that experiment material is planted
Enter the mouse body tissue slice result figure of 4 weeks.
From the b of Fig. 9) figure, c) figure and d) figure, experiment material surrounding soft tissue all without significantly hyperemia, hydrops, degeneration,
Downright bad and suppuration etc. shows.Compare matched group figure tissue slice, the b in Fig. 9) figure has the shape of connective tissue proliferation and new vessels
Becoming, there are the infiltration of the inflammatory cells such as a small amount of lymphocyte, megalokaryocyte in connective tissue and surrounding soft tissue；C in Fig. 9) figure with
B in Fig. 9) figure compares, and connective tissue proliferation is more, but the inflammatory cell such as lymphocyte, megalokaryocyte is the most less；Fig. 9
In d) have no the infiltration of the inflammatory cells such as a large amount of multinucleated giant cell and neutrophilic granulocyte around experiment material, and have substantial amounts of fiber to tie
Forming hamartoplasia, fibrous connective tissue parcel implant forms fibrous capsule.The experiment material taken out is carried out perusal and weighs
Measuring, the experiment material after taking off does not occurs degraded and weight to have almost no change, the hydroxyl phosphorus on this explanation experiment material surface
Lime stone coating can hinder the corrosion of slow magnesium alloy substrate.In sum, porous magnesium based hydroxylapatite experiment material has good
Biocompatibility.
B, zoopery two, in experimental group 2～3 and blank group, implant experiment material in experimental mouse fracture site.Experiment
After starting 1 month to experimental group 2～3 and the experimental mouse of blank group do X-ray detection respectively, detect one the most week about
Secondary experimental group 2～3 and the experimental mouse snap of blank group.
Find after testing, the averagely healing in 280 days after implanting experiment material of the mouse snap of experimental group 2～3.Blank
Experimental group in group terminates to experiment, and the skeleton of snap heals not yet.
2) SBF solution soaking experiment.Porous magnesium based hydroxylapatite composite is soaked in SBF solution, with analogue body
Interior environment.After 4 weeks, composite material surface is not the most corroded, and its coating layer thickness increases on the contrary, has one layer of white covering to sink
Amass in coating surface.Through XRD analysis, this covering has apatite crystalline phase, apatite contained in the coating after immersion
XRD diffraction peak intensity increases, and magnesium alloy XRD diffraction peak intensity reduces, and shows that the composite after soaking is containing bone-like apatite
Stone composition increases.Calcium ion concentration in SBF solution before and after soaking is carried out atomic absorption spectroscopy, before comparing immersion, leaching
In SBF solution after bubble composite, calcium ion concentration reduces, by original Ca2+Concentration is that 105.23mg/L is reduced to Ca2+Concentration
For 67.35mg/L.Therefore, the composite that the present invention provides can induce the formation of osteoid apatite, has good biology and lives
Property.
From the foregoing, it will be observed that the zoopery that the present invention provides proves, this material can be effectively improved effective in human body of backing material
The support time, moreover it is possible to play the effect of induced tissue growth, thus play the effect shortening the Rehabilitation time.
These are only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art,
The present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made, equivalent,
Improve, should be included within the scope of the present invention.
Claims (1)
1. a porous magnesium based hydroxylapatite composite, it is characterised in that
Described porous magnesium based hydroxylapatite composite includes magnesium matrix and the hydroxyl being arranged on described magnesium matrix surface
Apatite layer, arranges be connected with each other logical multiple radial holes and multiple axial hole in described magnesium matrix, described radial hole is along institute
State extending radially through of magnesium matrix to be arranged in described magnesium matrix；
Described axial hole is arranged in described magnesium matrix along axially penetrating through of described magnesium matrix；
Described axial hole is 5mm with the diameter of described radial hole, and the centre-to-centre spacing in the most described axial hole is 7mm；Two-by-two
The centre-to-centre spacing of radial hole is 7mm；After the internal surface of hole in described radial hole and described axial hole deposits described hydroxyapatite layer,
All leave the centre bore of a diameter of 1mm.
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| CN109172050A (en) * | 2018-09-21 | 2019-01-11 | 广州市健齿生物科技有限公司 | The titanium plate and preparation method thereof of compound can be filled in a kind of Bioexperiment inside |
| CN114086011B (en) * | 2021-10-25 | 2022-07-08 | 江苏理工学院 | Preparation method of component gradient magnesium-based implant material with controllable degradation |
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