CN101269238A - 316L toughening HA group biological function gradient material and preparation method thereof - Google Patents
316L toughening HA group biological function gradient material and preparation method thereof Download PDFInfo
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- CN101269238A CN101269238A CNA2008100311306A CN200810031130A CN101269238A CN 101269238 A CN101269238 A CN 101269238A CN A2008100311306 A CNA2008100311306 A CN A2008100311306A CN 200810031130 A CN200810031130 A CN 200810031130A CN 101269238 A CN101269238 A CN 101269238A
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Abstract
The invention discloses a 316L toughened HA-radical biology functionally gradient material and a preparation method thereof, which is to mix HA powder and 316L fiber or 316 powder by gradient ratio, the volume percentage content of the 316 fiber varies between 0 and 60 percent in a gradient way, the volume percentage content of the 316 powder varies between 0 and 100 percent in a gradient way, and the volume percentage content of the HA varies between 0 and 100 percent in a gradient way. The gradient mixed materials are evenly spread in a hot-pressing die in turn by 1-2 mm per layer, and are hot-pressed under 20-30 MPas of inert atmosphere. The biology functionally gradient material solves the problems that the two phases thermal stress of HA/316L do not match with each other, and combines with the respective advantages of 316 material and HA biological ceramic; a kind of 316L toughened HA-radical FGM which possesses fine biocompatibility and bioactivity as well as good mechanical properties is produced.
Description
Technical field
The invention belongs to FGM (Functionally Gradient Materials is called for short FGM) field, particularly HA base FGM.
Background technology
Hydroxyapatite (HA) has good biocompatibility and biological activity, is extensively paid attention in recent years.Yet hydroxyapatite is as bioceramic, also has the toughness deficiency, easily the shortcoming of brittle failure takes place, and can not be used for the reparation of load-bearing bone.316L rustless steel (316L) is with its superior mechanical property and biocompatibility and be widely used in clinical medicine, but its biological activity is then relatively poor relatively.So bond material and bioceramic advantage separately design and make a class and both had good biocompatibility and biological activity, having preferably again, the research of the Biocomposite material of mechanical property has become the research focus.But because both thermal coefficient of expansions differ bigger, cause the thermal stress of these two kinds of material combination interfaces bigger, thereby make composite or coating shedding, be full of cracks and lost efficacy.
FGM is meant by factors such as the structure that changes continuously two kinds of materials, composition, density (or quasi-continuous), its internal interface is reduced and even disappears, can be corresponding to forming and the variation of structure and the heterogeneous body composite of performance gradual change thereby obtain.FGM introduces transition zone between the material of two kinds of different in kinds, by the regulation and control of two kinds of components, make the thermal coefficient of expansion in the transition zone be slow successive variation, thereby reach the effect that relaxes thermal stress.
The preparation method of FGM comprises: vapour deposition process, plasma spraying method, self propagating high temperature synthetic method, laser cladding and powder metallurgic method etc.The vapour deposition process shortcoming is that aggregate velocity is slow, generally can not prepare the big gradient film of thickness, and to the equipment requirements height.There is the mutual interferential problem between plasma jet in plasma spraying method for the xenogenesis particle that makes independent spraying being evenly distributed of each zone in coating.Self propagating high temperature synthetic method process is simple, be swift in response, product purity height and less energy consumption, but variant owing to caloric value between the different component, the sintering degree different and the difficult density that influences material of controlling.Laser cladding is a kind of technology very fast, but needs special equipment.Comparatively speaking, powder metallurgic method has that equipment is simple, easy operating and low cost and other advantages, controls but need carry out strictness to holding temperature, temperature retention time and cooldown rate.
Summary of the invention
The objective of the invention is to solve the unmatched problem of the biphase thermal stress of HA/316L, a kind of method for preparing the toughness reinforcing HA biological function gradient material of 316L (FGM) with powder metallurgy process is proposed, in conjunction with 316L material and HA bioceramic advantage separately, produce a kind of both had good biocompatibility and biological activity, the 316L toughening HA group biological function gradient material that has better mechanical property again.
316L toughening HA group biological function gradient material of the present invention be by HA powder and 316L fiber or 316 powder by the gradient proportioning, with the thickness layering laying of every layer of 1～2mm, hot pressing gets; The 316L fibre diameter is 40～50 μ m, and length is 1～3mm; 316L powder mean diameter is 2～80 μ m; The mean diameter of HA is 5～20 μ m; 316 fiber volume percentage compositions graded between 0～60%, 316 powder volume percentage compositions graded between 0～100%, HA volumn concentration graded between 0～100%.
For FGM of the present invention, each gradient layer can be axially symmetric, also can be axially asymmetrical.The purpose of asymmetric FGM is in order to relax the preparation residual thermal stress, the biological activity of more efficient use HA and the high-strength tenacity of 316L; The purpose of symmetry FGM is to utilize the difference of the thermal coefficient of expansion of intermediate layer and symmetric both side surface layer, introduces residual compressive stress at surface layer, thereby improves the fracture toughness and the elastic modelling quantity of FGM.
The preparation method of 316L toughening HA group biological function gradient material of the present invention is: add respective amount 316L fiber or 316L powder respectively by the gradient proportioning in HA, mix, obtain the compound of each gradient layer of 316L toughening HA group biological FGM; By every layer of 1～2mm with the gradient compound successively evenly laying in hot-die, under 20～30MPa inert atmosphere, carry out hot pressing then, hot pressing temperature is 1050～1100 ℃, is incubated 1～1.5h after the hot pressing.
In order to make forming effect better, can also in the HA/316L compound, add mass percent and be 0.5～1% stearic acid as plasticizer.
Among the present invention, the process of HA and respective amount 316L fiber or 316L powder mixes can adopt ball milling method to carry out, and the time is preferably 4～8h.
For preventing in the hot pressing mould and sample generation chemical reaction and being convenient to the demoulding, can apply BN at the graphite jig inside and outside wall in advance.
The present invention utilizes PM technique to make mechanical property and biocompatibility has both and the significant 316L fiber of thermal stress alleviation effects (powder) toughening HA group biological FGM.Promptly adopt the intensified-sintered technology of hot pressing, make powder be heated to normal sintering temperature or lower in pressurization, the process short period sinters densification into and uniform goods.Hot-pressing technique will be suppressed and two operations of sintering are finished in the lump, can obtain high-compactness rapidly under lower pressure, and can reduce forming pressure greatly and shorten sintering time, thus capable of reducing energy consumption.
The present invention is matrix with HA, with 316L fiber or 316L powder is wild phase, with powder metallurgy hot-pressing technique and lay-up method is manufacture method, and at HA pottery and the unmatched present situation of 316L metal thermal stress, the selection function functionally gradient material (FGM) is for realizing the demulcent approach of thermal stress.Finally by fiber extract toughness reinforcing, the interlayer crack deflection is toughness reinforcing and the crackle bridging is toughness reinforcing has realized the preparation of symmetry with asymmetric 316L fiber or 316L powder toughening HA group biological FGM.On the FGM macroscopic view bulk deformation does not take place, the also non-microcracked existence in surface then shows composition and changes continuously on the microcosmic.Along with HA content increases, the fracture toughness and the elastic modelling quantity of each gradient layer of FGM reduce gradually, have reached that biological activity relaxes the purpose that designs with mechanical property among the FGM.The mechanical property of HA matrix successively relaxes improvement.Material of the present invention has superior biocompatibility and mechanical property concurrently, and the fracture toughness of prepared each gradient layer of material all is higher than fracture toughness (0.6～1MPam of HA
1/2), and with the close (2～12MPam of fracture toughness of human body bone
1/2), will have broad clinical application prospect aspect load-bearing bone reparation and the reconstruction.
Description of drawings
Fig. 1 is the vertical section SEM figure of the biological FGM of the fiber reinforced HA base of embodiment 1 asymmetric 316L;
Fig. 2 is the two-phase interface micro-structure diagram of the FGM of embodiment 1;
Fig. 3 is the vertical section SEM figure of the biological FGM of the fiber reinforced HA base of the symmetrical 316L of embodiment 2;
Fig. 4 is the SEM figure of the asymmetric 316L powder toughening HA group biological FGM of embodiment 3;
Fig. 5 is the bending strength of embodiment 3 each gradient layer and the graph of relation between the 316L content of powder;
Fig. 6 is the SEM figure of the symmetrical 316L powder toughening HA group biological FGM that makes of embodiment 4.
The specific embodiment
Embodiment 1
Prepare the biological FGM of the fiber reinforced HA base of asymmetric 316L.Each gradient layer prescription consists of A:316L fiber 5vol%, HA95vol%; B:316L fiber 10vol%, HA90vol%; C:316L fiber 15vol%, HA85vol%; D:316L fiber 20vol%, HA80vol%.316L fibre diameter 40 μ m, length 1mm; The mean diameter 10 μ m of HA.Add respective amount 316L fiber respectively by proportioning, and add the 0.5wt% stearic acid, add zirconia ball ball milling 8h simultaneously, promptly get the compound of biological each gradient layer of FGM of the fiber reinforced HA base of asymmetric 316L as plasticizer.The biological FGM sample of the fiber reinforced HA base of asymmetric 316L adopts the laminated type composition gradient, calculate each gradient layer quality according to every layer of 1mm of theoretical height of specimen, the powder of heterogeneity proportioning is pressed the even successively laying of A → B → C → D in Φ 50mm high-strength graphite hot-die.Carry out hot pressing then under the 20MPa argon gas atmosphere, hot pressing temperature is 1080 ℃, insulation 1.5h.
Each gradient layer of the biological FGM of the fiber reinforced HA base of obtained asymmetric 316L is made fracture toughness and elasticity modulus test, and the result is as shown in table 1.Fig. 1 is the vertical section SEM figure of gained material, and Fig. 2 is the two-phase interface micro-structure diagram.
The fracture toughness and the elastic modelling quantity of each gradient layer of FGM that table 1 embodiment 1 makes
From table 1, the fracture toughness (4.84～5.98MPam of each gradient layer of material that the present invention is prepared
1/2) all be higher than fracture toughness (0.6～1MPam of HA
1/2), and with the close (2～12MPam of fracture toughness of human body bone
1/2), for FGM provides good mechanical property guarantee.Along with the increase of HA content, fracture of composite materials toughness reduces gradually, embodies the mitigation design of each gradient layer mechanical property among the FGM.Elastic modelling quantity increases successively along HS5 → HS10 → HS15 → HS20, the stress that also embodies each gradient layer among the FGM relaxes design, the elastic modelling quantity of FGM surface layer HS5 is 107.7GPa simultaneously, though (7～25GPa) want high, than inert bioceramic ZrO than human body flexible bone modulus
2(210GPa) and Al
2O
3(380GPa) much lower, cause the human body osteanabrosis problem that " stress shielding " causes because of elastic modelling quantity is too high thereby reduce greatly.
Bulk deformation does not take place in the biological FGM of the fiber reinforced HA base of asymmetric 316L, the also non-microcracked existence in surface, and can obviously see the asymmetric Gradient distribution of 316L fiber vertically, show under these process conditions, successfully to prepare the biological FGM of the fiber reinforced HA base of asymmetric 316L.The 316L fiber is in FGM unordered, uniform distribution state, and integral body is not seen obvious crackle or hole (referring to Fig. 1).The biological FGM hole of the fiber reinforced HA base of asymmetric 316L obviously reduces, and internal flaw is eliminated in a large number, and the material microstructure obtains obviously to improve, and interface bonding state is strengthened (referring to Fig. 2) greatly.
Embodiment 2
Prepare the biological FGM of the fiber reinforced HA base of symmetrical 316L.Each gradient layer prescription consists of A:316L fiber 0vol%, HA100vol%; B:316L fiber 10vol%, HA90vol%; C:316L fiber 20vol%, HA80vol%.316L fibre diameter 50 μ m, length 3mm; The mean diameter 12 μ m of HA.Add respective amount 316L fiber respectively by proportioning, and add percetage by weight be the stearic acid of 1wt% as plasticizer, add zirconia ball ball milling 8h simultaneously, promptly get the compound of basic biological each gradient layer of FGM of the fiber reinforced HA of symmetrical 316L.The biological FGM sample of the fiber reinforced HA base of symmetry 316L adopts the laminated type composition gradient, calculate each gradient layer quality according to every layer of 1.5mm of theoretical height of specimen, the powder of heterogeneity proportioning is pressed the even successively laying of C → B → A → B → C in Φ 50mm high-strength graphite hot-die.Carry out hot pressing then under the 20MPa argon gas atmosphere, hot pressing temperature is 1050 ℃, insulation 1.5h.
Bulk deformation does not take place in the biological FGM of the fiber reinforced HA base of symmetry 316L, the also non-microcracked existence in surface, and can see obviously that vertically the symmetric gradient of 316L fiber distributes, show under these process conditions, successfully to prepare the biological FGM of the fiber reinforced HA base of symmetrical 316L.The interface is fuzzy between each gradient layer, does not have tangible macroscopic interface, in gradient layer and gradient layer at the interface, the 316L fiber evenly and being distributed in the HA matrix of disperse, both interfaces are in conjunction with good (referring to Fig. 3).
The fracture toughness of gained material HS10, HS20 is respectively 5.13MPam
1/2And 5.98MPam
1/2, all be higher than the fracture toughness of HA, close with the fracture toughness of human body bone.Reduce along with the elder generation of HA content increases afterwards, increase gradually again after material fracture toughness reduces earlier gradually, elastic modelling quantity reduces the back successively along HS20 → HS10 → HS0 → HS10 → HS20 and increases, and the axial symmetry that embodies each gradient layer mechanical property among the FGM relaxes design.
Embodiment 3
Prepare asymmetric 316L powder toughening HA group biological FGM.Each gradient layer prescription consists of A:316L powder 100vol%, HA0vol%; B:316L powder 80vol%, HA20vol%; C:316L powder 60vol%, HA40vol%; D:316L powder 40vol%, HA60vol%; E:316L powder 20vol%, HA80vol%; F:316L powder 0vol%, HA100vol%.316L powder mean diameter 78 μ m; The mean diameter 18 μ m of HA.According to said ratio 316L powder and HA mixed-powder are put into polyethylene bottle respectively, add zirconia ball ball milling mixing 4h, obtain each gradient layer composition.Adopt the laminated type composition gradient, at first according to each gradient layer quality of THICKNESS CALCULATION of every layer of 1.5mm of theoretical sample, again the order of the powder of heterogeneity proportioning being pressed A → B → C → D → E → F according to institute's expense successively equably laying in Φ 50mm high-strength graphite hot-die, every shop one deck gently precompressed once, smooth to guarantee the interface.Carry out hot pressing then under the 30MPa nitrogen atmosphere, hot pressing temperature is 1050 ℃, insulation 1h.
Can be clear that the Gradient distribution of HA pottery and two kinds of compositions of 316L powder among the asymmetric 316L powder toughening HA group biological FGM, each gradient layer interface is straight, biphase being evenly distributed in gradient layer, and do not have crackle or big hole (referring to Fig. 4) to occur.Each gradient layer of material is made elastic modelling quantity and bending strength test.Each gradient layer elastic modelling quantity test result sees Table 2.Each gradient layer and the 316L powder content between relation referring to Fig. 5.
The elastic modelling quantity of each gradient layer in the table 2 embodiment 2 gained materials
Embodiment 4
Prepare symmetrical 316L powder toughening HA group biological FGM.Each gradient layer prescription consists of A:316L powder 60vol%, HA40vol%; B:316L powder 80vol%, HA20vol%; C:316L powder 100vol%, HA0vol%.316L powder mean diameter 2 μ m; The mean diameter 5 μ m of HA.According to said ratio 316L powder and HA mixed-powder are put into polyethylene bottle respectively, add zirconia ball ball milling mixing 4h and obtain each gradient layer composition.Asymmetric 316L powder toughening HA group biological FGM adopts the laminated type composition gradient, at first according to each gradient layer quality of THICKNESS CALCULATION of every layer of 2mm of theoretical sample, again the order of the powder of heterogeneity proportioning being pressed A → B → C → B → A according to institute's expense successively equably laying in Φ 50mm high-strength graphite hot-die, every shop one deck gently precompressed once, smooth to guarantee the interface.Carry out hot pressing then under the 20MPa nitrogen atmosphere, hot pressing temperature is 1020 ℃, insulation 1h.
Symmetry 316L powder toughening HA group biological FGM does not deform, the also non-microcracked existence in surface, and can see obviously that the symmetric gradient of 316L powder distributes (referring to Fig. 6), show under the heat pressing process condition, successfully to prepare HA/316L powder symmetry FGM.
Claims (9)
1. 316L toughening HA group biological function gradient material is characterized in that: described material be by HA powder and 316L fiber or 316 powder by the gradient proportioning, with the thickness layering laying of every layer of 1～2mm, hot pressing gets; Described 316L fibre diameter is 40～50 μ m, and length is 1～3mm; Described 316L powder mean diameter is 2～80 μ m; The mean diameter of described HA is 5～20 μ m; 316 fiber volume percentage compositions graded between 0～60%, 316 powder volume percentage compositions graded between 0～100%, HA volumn concentration graded between 0～100%.
2. biological function gradient material according to claim 1 is characterized in that: the graded of the volume content proportioning of HA and 316L is axially symmetric in each gradient layer.
3. biological function gradient material according to claim 1 is characterized in that: the graded of the volume content proportioning of HA and 316L axially is axially asymmetrical in each gradient layer.
4. biological function gradient material according to claim 1 is characterized in that: described hot pressed process conditions are: carry out hot pressing under 20～30MPa inert atmosphere, hot pressing temperature is 1050～1100 ℃.
5. the preparation method of biological function gradient material as claimed in claim 1 adds respective amount 316L fiber or 316L powder mixes respectively by the gradient proportioning in HA, obtains the compound of each gradient layer of 316L toughening HA group biological FGM; By every layer of 1～2mm with the gradient compound successively evenly laying in hot-die, under 20～30MPa inert atmosphere, carry out hot pressing then, hot pressing temperature is 1050～1100 ℃, is incubated 1～1.5h after the hot pressing.
6. preparation method according to claim 5 is characterized in that: the interpolation mass percent is 0.5～1% stearic acid in described HA/316L compound.
7. preparation method according to claim 5 is characterized in that: the process of described HA and 316L fiber or 316L powder mixes adopts ball milling method to carry out, and the time is 4～8h.
8. preparation method according to claim 5 is characterized in that: apply BN at the hot pressing die inwall in advance before the hot pressing.
9. preparation method according to claim 5 is characterized in that: described inert atmosphere is argon gas atmosphere or nitrogen atmosphere.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549175B (en) * | 2009-05-15 | 2012-07-04 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
| WO2017152541A1 (en) * | 2016-03-11 | 2017-09-14 | 安徽拓宝增材制造科技有限公司 | Composite biomedical implant material and preparation method therefor |
| CN114683460A (en) * | 2022-04-21 | 2022-07-01 | 中国人民解放军军事科学院国防工程研究院 | Preparation method of functionally gradient polyolefin sheet material |
-
2008
- 2008-04-24 CN CNA2008100311306A patent/CN101269238A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549175B (en) * | 2009-05-15 | 2012-07-04 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
| WO2017152541A1 (en) * | 2016-03-11 | 2017-09-14 | 安徽拓宝增材制造科技有限公司 | Composite biomedical implant material and preparation method therefor |
| CN114683460A (en) * | 2022-04-21 | 2022-07-01 | 中国人民解放军军事科学院国防工程研究院 | Preparation method of functionally gradient polyolefin sheet material |
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Open date: 20080924 |