CN108103546B - A kind of controlled degradation magnesium-based functionally graded material and preparation method thereof - Google Patents

A kind of controlled degradation magnesium-based functionally graded material and preparation method thereof Download PDF

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CN108103546B
CN108103546B CN201810035416.5A CN201810035416A CN108103546B CN 108103546 B CN108103546 B CN 108103546B CN 201810035416 A CN201810035416 A CN 201810035416A CN 108103546 B CN108103546 B CN 108103546B
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base
magnesium
magnesium alloy
functionally graded
tcp
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CN108103546A (en
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朱世杰
雷少倩
关绍康
刘明明
徐雪雪
王利国
王剑锋
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Zhengzhou University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on light metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Abstract

The present invention discloses a kind of preparation method of controlled degradation magnesium-based functionally graded material: 1) making annealing treatment to magnesium alloy, 2) it drills to the magnesium alloy after annealing: 3) to magnesium alloy drilling after the completion of carry out the loading of HA or β-TCP；4) friction processing is stirred to the magnesium alloy for having loaded hydroxyapatite or tricalcium phosphate: in rotation speed 300-1700r/min, feeding rate 10-50mm/min, under conditions of volume under pressure 0.5-3mm, agitating friction 2-6 passage obtains Mg base/HA layers or Mg base/β-TCP layers of thick 0.5-3mm；5) using Mg base/HA or Mg base/β-TCP layer as base material, through surface polishing, cleaning, drying, electro-deposition is carried out then to obtain thick 1-12 μm of hydroxyapatite coating layer in substrate material surface to get controlled degradation magnesium-based functionally graded material.The magnesium-based functionally graded material has good biocompatibility, osteoinductive, corrosion resistance and controlled degradation, realizes timing degradation and controlled degradation of the magnesium alloy as bone implant material.

Description

A kind of controlled degradation magnesium-based functionally graded material and preparation method thereof
Technical field
The invention belongs to biomedical material technologies, and in particular to a kind of controlled degradation magnesium-based functionally graded material and Preparation method.
Background technique
Clinically widely used bone implant material is mainly titanium alloy and stainless steel, but it implants and cannot be inhaled Receive, degradation, when the injury of the bone healing after need second operation to take out, increase sufferer physiology pain and financial burden, therefore with give birth to Object medical degradable material replaces conventional medical metal material to get more and more attention.Magnesium alloy has good biodegradability And biocompatibility, it can gradually be degraded in human body by corrosion, be expected to become novel bone implant material, but as implantation material The magnesium base alloy mechanical property of material is insufficient, corrosion resistance is poor, and controlled degradation difference becomes it and is applied to clinical obstacle.Therefore, Urgently research and development have the medical function material of more preferable controlled degradation and biocompatibility, to meet medicine needs.
Summary of the invention
Present invention aims to overcome that prior art defect, provides a kind of controlled degradation magnesium-based functionally graded material, the material Material has preferable controlled degradation, biocompatibility and osteoinductive.
The present invention also provides the preparation methods of above-mentioned controlled degradation magnesium-based functionally graded material.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of controlled degradation magnesium-based functionally graded material comprising following steps:
(1) magnesium alloy is made annealing treatment, annealing treating process parameter: 200-500 DEG C of temperature, soaking time 12- 120h；
(2) it drills to the magnesium alloy after annealing:
(3) loading of hydroxyapatite (HA) or tricalcium phosphate (β-TCP) is carried out to the magnesium alloy after the completion of drilling；
(4) friction processing is stirred to the magnesium alloy for having loaded hydroxyapatite or tricalcium phosphate:
Under conditions of rotation speed 300-1700r/min, feeding rate 10-50mm/min, volume under pressure 0.5-3mm, Friction processing is stirred to the magnesium alloy for having loaded hydroxyapatite or tricalcium phosphate, agitating friction 2-6 passage obtains thickness The Mg base of 0.5-3mm/HA layers or Mg base/β-TCP layers；HA particle or β-TCP particle are evenly distributed on magnesium alloy (i.e. magnesium matrix) In；
(5) it using Mg base/HA or Mg base/β-TCP layer as base material, through surface polishing, cleaning, dries (it is required that substrate material Material surface there is no oxidation film), then carry out electro-deposition with substrate material surface obtain thick 1-12 μm (degradable nano lack Calcium type) hydroxyapatite coating layer is to get controlled degradation magnesium-based functionally graded material.
In step (5), electrodeposition technology can refer to Chinese invention patent " pure magnesium or Mg alloy surface hydroxyapatite coating layer Pulse electrodeposition preparation method (patent No.: ZL200910065998.2) " carry out.Hydroxyapatite coating layer and basis material Bond strength is greater than 25MPa, and degradation rate is controllable.
According to the flow behavior of processing district metal material during the additive amount and mixing yoghurt of HA or β-TCP, To design the quantity and distribution situation in hole.It is further preferred that pore size distribution is designed as 2-6 row, row and row when step (2) drills Between distance be 0.5-3mm, same row's mesoporous at a distance from hole be 1-18mm, aperture 0.5-4mm, hole depth 0.5-4mm.
The present invention also provides the controlled degradation magnesium-based functionally graded material being prepared using the above method.
In the method for the present invention, mixing yoghurt technology can be such that alloy grain refines, and the second phase constitution becomes uniformly, and Hydroxyapatite (HA) and tricalcium phosphate (β-TCP) are the main components of skeleton, and there is good bioactivity and bone to lure Function is led, but brittleness is larger, so preparing Mg base/HA or Mg base/β-using mixing yoghurt technology and electro-deposition techniques TCP functionally gradient material (FGM).The advantage of magnesium base alloy and HA/ β-TCP is combined first, magnesium base alloy both can be improved and planted as bone Enter the mechanical property of material, and the osteoinductive effect of HA/ β-TCP can be played, so as to improve magnesium base alloy as bone implant The mechanical property and Biofunctional of material；Further by process for modifying surface, in Mg base/HA material or Mg base/β-TCP material Expect that surface prepares degradable calcium deficiency type HA or the β-TCP coating of one layer of even compact by bidirectional pulse electrodeposition process, obtains A kind of biomedical degradation-controllable Mg base functionally graded material, on the one hand greatly improves the corrosion resistance of magnesium alloy, another party Face makes magnesium alloy as the degradation of bone implant material realization timing.And with the electrodeposited coating phase directly on metallic matrix Than Mg base/HA layers or Mg base/β-TCP layers are as base material, HA(β-TCP therein) have to the HA coating that electro-deposition is formed Play the role of inducing its growth, greatly improves the bond strength of coating and base material.The present invention is added using agitating friction Work and electro-deposition techniques prepare controlled degradation magnesium-based functionally graded material there is not yet report.
Compared to the prior art, beneficial effects of the present invention:
Controlled degradation magnesium-based functionally graded material its good biocompatibility being prepared using the method for the present invention, coating with Substrate bond strength is high (being greater than 25MPa), has the function of the induced growth of bone and controlled degradation；Preparation method of the invention is suitable Answer the magnesium such as AZ and ZK series alloy, WE43 alloy, Mg-Zn-Ca alloy, Mg-Zn-Y-Nd alloy and Mg-Zn-Y-Nd-Zr alloy Alloy.
Detailed description of the invention
Fig. 1 is the schematic diagram of controlled degradation magnesium-based functionally graded material of the present invention；
Fig. 2 is the mixing yoghurt schematic diagram in the method for the present invention；
Fig. 3 is the pore size distribution figure in the method for the present invention on magnesium alloy plate；
Fig. 4 is Mg base/HA layers of (a), Mg base/β-TCP layer in Mg base/HA functionally graded material obtained by prepared by embodiment 1 (b) microscopic structure；
Fig. 5 is the SEM for the degradable hydroxyapatite coating that embodiment 1 is prepared in gained Mg base/HA functionally graded material Microscopic appearance (a) and EDS map (b)；
Fig. 6 is that embodiment 1 prepares gained Mg base/HA functionally graded material material phase analysis result；
Fig. 7 is that embodiment 1 prepares gained Mg base/HA functionally graded material Cross Section Morphology and Elemental redistribution；
Fig. 8 is that embodiment 1 prepares gained Mg base/HA functionally graded material and Mg base/HA layers of base material in simulated body fluid Middle polarization curve；
Fig. 9 is that embodiment 4 prepares gained Mg base/β-TCP functionally graded material Cross Section Morphology and Elemental redistribution；
Figure 10 is that embodiment 4 prepares gained Mg base/β-TCP functionally graded material polarization curve in simulated body fluid；
Figure 11 is the microscopic appearance and energy that embodiment 3 prepares Mg base in gained Mg base/HA functionally graded material/HA layers Spectrum；
Figure 12 be embodiment 5 prepare in gained Mg base/β-TCP functionally graded material Mg base/β-TCP layer microscopic appearance and Power spectrum；
Figure 13 is that HA makees the induced growth of coating in Mg base/HA functionally graded material matrix obtained by prepared by embodiment 3 With；
Figure 14 is that embodiment 5 prepares induction life of the β-TCP to coating in gained Mg base/β-TCP functionally graded material matrix Long effect；
Figure 15 is that embodiment 1 prepares gained Mg base/HA functionally graded material degradation rate curve；
Figure 16 is that embodiment 4 prepares gained Mg base/β-TCP functionally graded material degradation rate curve.
Specific embodiment
Below with reference to embodiment, the invention will be further described, and listed embodiment is to be with technical solution of the present invention Under the premise of implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to down The embodiment stated.
In the present invention, magnesium alloy can purchase ordinary commercial products, or be prepared using this field routine techniques.Following realities It applies in example, the present invention is described in detail by taking as cast condition Mg-Zn-Y-Nd as an example.Each ingredient hundred of as cast condition Mg-Zn-Y-Nd(used Point than composition are as follows: Zn 1 ~ 3%, Y 0.23 ~ 0.69%, Nd 0.5 ~ 1%, surplus Mg) plate can voluntarily melting or consignable company into Semicontinuous ingot casting is obtained after row magnesium alloy smelting, ingot casting is prepared into plate through wire cutting, this uses this field routine techniques, And the place of non-present invention innovation, so it will not be repeated.
Embodiment 1:
A kind of preparation method of controlled degradation magnesium-based functionally graded material comprising following steps:
1) as cast condition Mg-Zn-Y-Nd board dimension is 200mm × 50mm × 8mm, carries out homogenizing annealing processing to it, moves back 500 DEG C of fiery temperature soaking time 120 hours, the magnesium alloy plate after annealing is taken out in heat-treatment furnace, naturally cold at room temperature But；
2) its surface is polishing to light, is punched with the drill bit that diameter is 4mm, pore size distribution is designed as 3 rows, row and row Between distance be 2.5mm, same round is 16.6mm, aperture 4mm, hole depth 4mm at a distance from hole, the distribution in hole and quantity with Mixing needle is that the loading of hydroxyapatite (HA) is carried out after the completion of drilling referring to (being detailed in Fig. 3)；
3) by the magnesium alloy plate for having loaded HA be fixed on mixing yoghurt workbench carry out mixing yoghurt (see Fig. 2), processing passage is 6 passages, and Rotating speed 1700r/min, feeding rate 50mm/min, volume under pressure is 3mm obtains the Mg base with a thickness of 1mm/HA layers.The microstructure of Mg base/HA layers is shown in Fig. 4 (a)；
4) step 3) products obtained therefrom is subjected to wire wire cutting, 10mm × 10mm × 8mm sample is cut into, with Mg base/HA Layer is the base material of electro-deposition, uses 200#, 400#, 600# respectively, 800#SiC abrasive paper for metallograph successively beat by its surface by machinery Mill is put into dehydrated alcohol after the completion of polishing and impregnates 3s, and natural air drying (it is required that its surface does not have oxidation film), spare after taking-up；
5) electro-deposition: electrolyte is configured, wherein CaNO3·4H2O concentration 10.5mol/L, NH4H2PO4Concentration is 6.5mol/ L, NaNO3Concentration is 2.4mol/L；Using the resulting Mg base of step 4)/HA layers of base material as cathode, graphite is anode, is being electrolysed When being heated to 90 DEG C of constant temperature in liquid, cathode and anode are put into the electrolyte for being heated to 90 DEG C simultaneously, wherein two pole span of yin-yang From for 5cm；Using bidirectional pulse electro-deposition method, wherein positive peak current density 40mA/cm2, direct impulse frequency 600HZ, positive duty ratio 10%, positive peak current density 80mA/cm2, reverse impulse frequency 3000HZ, reversed duty ratio 60%；
6) after 70min electro-deposition, sample is taken out, is rinsed well with deionized water, it is dry, be in substrate material surface One layer of good degradable hydroxyapatite coating (see figure 1) in connection is formed to get controlled degradation magnesium-based functionally gradient material Expect (Mg base/HA functionally graded material).The bond strength of hydroxyapatite coating layer and base material is 30MPa, hydroxyapatite Coating layer thickness is 10 μm.
Analysis to the progress microscopic structure of the Mg base obtained after mixing yoghurt /HA layers, as shown in Figure 4, it can be seen that HA is evenly distributed in crystal grain, and obtained crystal grain is tiny equiax crystal, effectively raises the mechanical property of magnesium alloy.
Mg base/HA layer surface pulse electrodeposition HA coating SEM spectrum as shown in Fig. 5 (a), it can be seen that the painting in figure Layer is mainly flake, approximately perpendicular to the growth of matrix direction, and in addition there are also superfine spicules, it may be possible in electrodeposition process just The HA of formation.According to the analysis data of Fig. 5 (b) EDS: calcium-phosphorus ratio in coating is 1.5, deducibility electrochemistry under this condition Depositing coating is degradable hydroxyapatite (the Ca/P molar ratio in degradable HA is 1.33-1.65), wherein containing on a small quantity Mg2+、Na+、CO3 2-It is similar with the composition of natural bone.
The XRD spectrum of the preparation gained controlled degradation magnesium-based functionally graded material of embodiment 1 in figure as shown in fig. 6, can be seen that The HA coating of well-crystallized is obtained in Mg alloy surface using above-mentioned bidirectional pulse electrodeposition technology.
The preparation of embodiment 1 gained controlled degradation magnesium-based functionally graded material Cross Section Morphology and Elemental redistribution are shown in Fig. 7.By Fig. 7 It can be seen that the Elemental redistribution of controlled degradation magnesium-based functionally graded material changes in gradient, from coating to magnesium alloy substrate, calcium with Phosphorus element content is successively reduced until not having, and change of gradient is presented.
Corrosive nature of the magnesium alloy sample in simulated body fluid is shown in Fig. 8 before and after test pulse electro-deposition, the results showed that coating Magnesium alloy can be made, which to improve 100mV, corrosion electric current density in the corrosion potential of simulated body fluid, reduces an order of magnitude, corrosion rate by 10mm·y-1 It is reduced to 3.1 mmy-1, illustrate that coating can effectively slow down the corrosion rate of magnesium alloy, i.e. raising magnesium alloy Corrosion resistance.
Figure 15 is the degradation rate curve that embodiment 1 prepares gained controlled degradation magnesium-based functionally graded material.From corrosion speed For rate it can be seen that at immersion test initial stage, corrosion rate is slower, and with the extension of soaking time, coating is gradually degraded, to sample Protective effect weaken, corrosion rate increases rapidly, and corrosion rate when impregnating 72h is 0.057 mg cm-2•h-1, rotten later Rate is lost to increase slowly, this is because simulated body fluid erodes to stirring and processing layer by hole, the HA induction in stirring and processing layer Calcium microcosmic salt deposition blocks the erosion of simulated body fluid, and stirring and processing layer crystal grain is tiny, has certain corrosion resisting property, when soaking Between when extending to 336h, corrosion rate increases, and illustrates that sample has been corroded to magnesium alloy substrate.
Embodiment 2:
A kind of preparation method of controlled degradation magnesium-based functionally graded material comprising following steps:
1) as cast condition Mg-Zn-Y-Nd board dimension is 200mm × 50mm × 8mm, carries out homogenizing annealing processing to it, moves back Fiery temperature is 450 DEG C, keeps the temperature 80 hours, the magnesium alloy plate after annealing is taken out in heat-treatment furnace, at room temperature natural cooling；
2) light is polishing to its surface, is punched with the drill bit that diameter is 2mm, pore size distribution is designed as 4 rows, row and row Between distance be 1mm, same row's mesoporous at a distance from hole be 3mm, aperture 2mm, hole depth 2mm, drilling after the completion of carry out hydroxyl phosphorus The loading of lime stone (HA)；
3) magnesium alloy plate for having loaded HA is fixed on mixing yoghurt workbench and carries out mixing yoghurt, added Work passage is 3 passages, and Rotating speed 1000r/min, feeding rate 20mm/min, volume under pressure 1.5mm obtains With a thickness of 0.5mm Mg base/HA layers；
4) step 3) products obtained therefrom is subjected to wire wire cutting, 10mm × 10mm × 8mm sample is cut into, with Mg base/HA Layer is the base material of electro-deposition, uses 200#, 400#, 600# respectively, 800#SiC abrasive paper for metallograph successively beat by its surface by machinery Mill is put into dehydrated alcohol after the completion of polishing and impregnates 3s, and natural air drying (it is required that its surface does not have oxidation film), spare after taking-up；
5) electro-deposition: electrolyte is configured, wherein CaNO3·4H2O concentration is 9.0mol/L, NH4H2PO4Concentration is 6.0mol/ L, NaNO3Concentration is 0.2mol/L.Using the resulting Mg base of step 4)/HA layers of base material as cathode, graphite is anode, is being electrolysed When liquid is heated to 75 DEG C of constant temperature, cathode and anode are put into the electrolyte for being heated to 75 DEG C simultaneously, wherein yin-yang the two poles of the earth distance For 1cm.Using bidirectional pulse electro-deposition method, wherein positive peak current density 15mA/cm2, direct impulse frequency 30HZ, just To duty ratio 8%, positive peak current density 20mA/cm2, reverse impulse frequency 450HZ, reversed duty ratio 55%；
6) after 40min is deposited, sample is taken out, is rinsed well with deionized water, it is dry, in substrate material surface, that is, shape At one layer of good degradable hydroxyapatite coating in connection to get controlled degradation magnesium-based functionally graded material.Hydroxyl phosphorus The bond strength of lime stone coating and base material is 28MPa, and hydroxyapatite coating layer is with a thickness of 12 μm.
Embodiment 3:
A kind of preparation method of controlled degradation magnesium-based functionally graded material comprising following steps:
1) as cast condition Mg-Zn-Y-Nd board dimension is 200mm × 50mm × 8mm, carries out homogenizing annealing processing to it, moves back 200 DEG C of fiery temperature, soaking time 12 hours.Magnesium alloy plate after annealing is taken out in heat-treatment furnace, it is naturally cold at room temperature But；
2) light is polishing to its surface, is punched with the drill bit that diameter is 0.5mm, pore size distribution is designed as 6 rows, row with Distance is 3mm between row, and same row's mesoporous is 1mm, aperture 0.5mm, hole depth 1mm at a distance from hole.Hydroxyl is carried out after the completion of drilling The loading of base apatite (HA)；
3) magnesium alloy plate for having loaded HA is fixed on mixing yoghurt workbench and carries out mixing yoghurt, added Work passage is 6 passages, and Rotating speed 300r/min, feeding rate 10mm/min, volume under pressure 0.5mm obtains With a thickness of 0.5mm Mg base/HA layers；
4) step 3) products obtained therefrom is subjected to wire wire cutting, 10mm × 10mm × 8mm sample is cut into, with Mg base/HA Layer is the base material of electro-deposition, uses 200#, 400#, 600# respectively, 800#SiC abrasive paper for metallograph successively beat by its surface by machinery Mill is put into dehydrated alcohol after the completion of polishing and impregnates 3s, and natural air drying (it is required that its surface does not have oxidation film), spare after taking-up；
5) electro-deposition: electrolyte is configured, wherein CaNO3·4H2O concentration is 5mol/L, NH4H2PO4Concentration is 4mol/L, NaNO3Concentration is 0.1mol/L.Using the resulting Mg base of step 4)/HA layers of base material as cathode, graphite is anode, in electrolyte When being heated to 40 DEG C of constant temperature, cathode and anode are put into the electrolyte for being heated to 40 DEG C simultaneously, wherein yin-yang the two poles of the earth distance is 1cm.Using bidirectional pulse electro-deposition method, wherein positive peak current density 5mA/cm2, direct impulse frequency 20HZ, forward direction Duty ratio 5%, positive peak current density 10mA/cm2, reverse impulse frequency 300HZ, reversed duty ratio 50%；
6) after 1min is deposited, sample is taken out, is rinsed well with deionized water, it is dry, in substrate material surface, that is, shape At one layer of good degradable hydroxyapatite coating in connection to get controlled degradation magnesium-based functionally graded material (Mg base/HA Functionally graded material).The bond strength of hydroxyapatite coating layer and base material is 28MPa, and hydroxyapatite coating layer is with a thickness of 2 μm。
Figure 11 be embodiment 3 prepare gained magnesium-based functionally graded material Mg base/HA layers microscopic appearance (left side) and power spectrum (right side).From power spectrum: segregation is distributed in white particle HA, HA in magnesium matrix.Figure 13 is magnesium-based functionally graded material HA acts on the induced growth of coating in matrix.As seen from Figure 13: the microscopic appearance of HA coating is foliaceous, is sprawled uniformly, Know that Ca, P element, and calcium, phosphorus atoms ratio are all contained less than 1.67 in 1,2 regions by power spectrum, is biodegradable coating, but 1 region Calcium phosphorus element content is higher than 2 regions, i.e., HA coatings growth is very fast at 1, and HA particle is hexagonal crystal system, and degradable HA coating is also Hexagonal crystal system, matrix and the basal plane structure for being critically depend on crystal and matrix for applying interlayer bonding, if in molecule or atomic level Upper two alternate complementary structures simultaneously arrange unanimously, can promote crystal face preference forming core on matrix.Again by Figure 11 (left side) Known to: the distribution of HA particle in the base, therefore 1 region HA coatings growth is faster the reason is that the HA particle in matrix is to HA coating Growth has inducing action.
Embodiment 4:
A kind of preparation method of controlled degradation magnesium-based functionally graded material comprising following steps:
1) as cast condition Mg-Zn-Y-Nd board dimension is 200mm × 50mm × 8mm, carries out homogenizing annealing processing to it, moves back 400 DEG C of fiery temperature keeps the temperature 48 hours.Magnesium alloy plate after annealing is taken out in heat-treatment furnace, at room temperature natural cooling；
2) light is polishing to its surface, is punched with the drill bit that diameter is 1mm, pore size distribution is designed as 3 rows, row and row Between distance be 2mm, same row's mesoporous at a distance from hole be 5mm, aperture 1mm, hole depth 3mm.Tricresyl phosphate is carried out after the completion of drilling The loading of calcium (β-TCP)；
3) magnesium alloy plate for having loaded β-TCP progress agitating friction on mixing yoghurt workbench is fixed on to add Work, processing passage are 5 passages, and Rotating speed 1200r/min, feeding rate 40mm/min, volume under pressure is 1.5mm obtains Mg base/β-TCP layer with a thickness of 1.5mm；
4) step 3) products obtained therefrom is subjected to wire wire cutting, 10mm × 10mm × 8mm sample is cut into, with Mg base/β- TCP layer is the base material of electro-deposition, uses 200#, 400#, 600# respectively, 800#SiC abrasive paper for metallograph is successively by its surface machinery Polishing is put into dehydrated alcohol after the completion of polishing and impregnates 3s, and natural air drying (it is required that its surface does not have oxidation film), standby after taking-up With；
5) electro-deposition: electrolyte is configured, wherein CaNO3·4H2O concentration is 8.5mol/L, NH4H2PO4Concentration is 6.1mol/ L, NaNO3Concentration is 0.3mol/L.Using the resulting Mg base/β-TCP layer base material of step 4) as cathode, graphite is anode, When electrolyte is heated to 78 DEG C of constant temperature, cathode and anode are put into the electrolyte for being heated to 78 DEG C simultaneously, wherein yin-yang the two poles of the earth Distance is 5cm.Using bidirectional pulse electro-deposition method, wherein positive peak current density 15mA/cm2, direct impulse frequency 100HZ, positive duty ratio 11%, positive peak current density 30mA/cm2, reverse impulse frequency 200HZ, reversed duty ratio 60%；
6) after 35min is deposited, sample is taken out, is rinsed well with deionized water, it is dry, in substrate material surface, that is, shape At one layer of good degradable hydroxyapatite coating in connection to get controlled degradation magnesium-based functionally graded material (Mg base/β- TCP functionally graded material).The bond strength of hydroxyapatite coating layer (HA coating) and base material is 32MPa, hydroxyapatite Coating layer thickness is 10 μm.
Fig. 9 is that embodiment 4 prepares gained Mg base/β-TCP functionally graded material Cross Section Morphology (left side) and Elemental redistribution (right side).As seen from Figure 9: Mg base/β-TCP functionally graded material Elemental redistribution changes in gradient, from coating to magnesium alloy Matrix, calcium are successively reduced with phosphorus element content until not having, and change of gradient is presented.
Figure 10 is that embodiment 4 prepares gained Mg base/β-TCP functionally graded material polarization curve in simulated body fluid.By scheming Known to: its corrosion electric current density is 1.267 × 10-5And the same quantity of Mg base/HA functionally graded material corrosion electric current density Grade, illustrates that its corrosion resisting property is good.
Figure 16 is that embodiment 4 prepares gained Mg base/β-TCP functionally graded material degradation rate curve.From corrosion rate It can be seen that corrosion rate is slower at immersion test initial stage, as soaking time extends, coating is gradually degraded, to the guarantor of sample Declines are protected, corrosion rate increases rapidly, and corrosion rate when impregnating 72h is 0.055 mg cm-2•h-1, post-etching speed Rate increases slowly, this is because simulated body fluid erodes to stirring and processing layer by hole, the β-TCP in stirring and processing layer induces calcium Microcosmic salt deposition blocks the erosion of simulated body fluid, and stirring and processing layer crystal grain is tiny, there is certain corrosion resisting property, when the soaking time When extending to 336h, corrosion rate increases, and illustrates that sample has been corroded to magnesium alloy substrate.
Embodiment 5:
A kind of preparation method of controlled degradation magnesium-based functionally graded material comprising following steps:
1) as cast condition Mg-Zn-Y-Nd board dimension is 200mm × 50mm × 8mm, carries out homogenizing annealing processing to it, adds 400 DEG C of hot temperature, soaking time 48 hours.Magnesium alloy plate after annealing is taken out in heat-treatment furnace, it is naturally cold at room temperature But；
2) light is polishing to its surface, is punched with the drill bit that diameter is 1mm, pore size distribution is designed as 3 rows, row and row Between distance be 2mm, same row's mesoporous at a distance from hole be 5mm, aperture 1mm, hole depth 3mm.Tricresyl phosphate is carried out after the completion of drilling The loading of calcium (β-TCP)；
3) magnesium alloy plate for having loaded β-TCP progress agitating friction on mixing yoghurt workbench is fixed on to add Work, processing passage are 5 passages, and Rotating speed 1200r/min, feeding rate 40mm/min, volume under pressure is 1.5mm obtains Mg base β-TCP layer with a thickness of 1.5mm；
4) step 3) products obtained therefrom is subjected to wire wire cutting, 10mm × 10mm × 8mm sample is cut into, with Mg base/β- TCP layer is the base material of electro-deposition, uses 200#, 400#, 600# respectively, 800#SiC abrasive paper for metallograph is successively by its surface machinery Polishing is put into dehydrated alcohol after the completion of polishing and impregnates 3s, and natural air drying (it is required that its surface does not have oxidation film), standby after taking-up With；
5) electro-deposition: electrolyte is configured, wherein CaNO3·4H2O concentration is 8.5mol/L, NH4H2PO4Concentration is 6.1mol/ L, NaNO3Concentration is 0.3mol/L.Using the resulting Mg base/β-TCP layer base material of step 4) as cathode, graphite is anode, When electrolyte is heated to 78 DEG C of constant temperature, cathode and anode are put into the electrolyte for being heated to 78 DEG C simultaneously, wherein yin-yang the two poles of the earth Distance is 5cm.Using bidirectional pulse electro-deposition method, wherein positive peak current density 5mA/cm2, direct impulse frequency 100HZ, positive duty ratio 11%, positive peak current density 10mA/cm2, reverse impulse frequency 200HZ, reversed duty ratio 60%；
6) after 1min is deposited, sample is taken out, is rinsed well with deionized water, it is dry, in substrate material surface, that is, shape At one layer of good degradable hydroxyapatite coating in connection to get controlled degradation magnesium-based functionally graded material (Mg base/β- TCP functionally graded material).The bond strength of hydroxyapatite coating layer (HA coating) and base material is 30MPa, hydroxyapatite Coating layer thickness is 1 μm.
Figure 12 is the Mg base/β-TCP layer microscopic appearance (left side) and energy in 5 Mg base of embodiment/β-TCP functionally graded material It composes on (right side).As seen from the figure: white particle is β-TCP, and segregation is distributed in β-TCP in magnesium matrix.
Figure 14 is that embodiment 5 prepares induction of the β-TCP to coating in gained Mg base/β-TCP functionally graded material matrix Growth.As seen from Figure 14: the microscopic appearance of HA coating is foliaceous, is sprawled uniformly.Know that 3,4 regions are all contained by power spectrum Ca, P element, and calcium, phosphorus atoms ratio are biodegradable coating less than 1.67, but the calcium phosphorus element content in 3 regions is higher than 4 regions, HA coatings growth is very fast at i.e. 3, and β-TCP particle is hexagonal crystal system, and degradable HA coating is also hexagonal crystal system, matrix and coating Between bonding the basal plane structure for being critically depend on crystal and matrix, if two alternate complementary structures are simultaneously on molecule or atomic level Arrangement is consistent, can promote crystal face preference forming core on matrix.Point of β-TCP particle in the base is known by Figure 12 again Cloth, therefore 3 region HA coatings growths are faster the reason is that β-TCP the particle in matrix has inducing action to HA coatings growth.
In summary it can be seen: the present invention prepares resulting magnesium-based functionally graded material with good biocompatibility, bone Inductivity, corrosion resistance and controlled degradation realize timing degradation and controlled degradation of the magnesium alloy as bone implant material.

Claims (2)

1. a kind of preparation method of controlled degradation magnesium-based functionally graded material, which comprises the following steps:
(1) magnesium alloy is made annealing treatment, annealing treating process parameter: 200-500 DEG C of temperature, soaking time 12-120h；
(2) it drills to the magnesium alloy after annealing:
(3) loading of hydroxyapatite or tricalcium phosphate is carried out to the magnesium alloy after the completion of drilling；
(4) friction processing is stirred to the magnesium alloy for having loaded hydroxyapatite or tricalcium phosphate:
Under conditions of rotation speed 300-1700r/min, feeding rate 10-50mm/min, volume under pressure 0.5-3mm, to dress The magnesium alloy for having carried hydroxyapatite or tricalcium phosphate is stirred friction processing, and agitating friction 2-6 passage obtains thick 0.5- The Mg base of 3mm/HA layers or Mg base/β-TCP layers；
(5) using Mg base/HA or Mg base/β-TCP layer as base material, through surface polishing, cleaning, drying, electro-deposition is then carried out Thick 1-12 μm of hydroxyapatite coating layer is obtained in substrate material surface to get controlled degradation magnesium-based functionally graded material；
When step (2) drills, pore size distribution is designed as 3-6 row, and distance is 0.5-3mm, same row's mesoporous and hole between row and row Distance be 1-18mm, aperture 0.5-4mm, hole depth 0.5-4mm.
2. the controlled degradation magnesium-based functionally graded material being prepared using claim 1 the method.
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