CN104841018B - A kind of multi-layer biological composite and preparation method thereof - Google Patents
A kind of multi-layer biological composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of multi-layer biological composite and preparation method thereof, belong to bio-medical material preparation field.Biocomposite material of the present invention is using titanium alloy as matrix, and titanium alloy+hydroxyapatite is intermediate layer, and hydroxyapatite is biological ceramic surface；Processing step is as follows：It will be dried after titanium, niobium, zirconium powder mechanical alloying ball milling, obtain matrix mixed-powder；After titanium, niobium, zirconium powder mechanical alloying, addition hydroxyapatite ball milling is mixed dries after powder, obtains intermediate layer mixed-powder.Matrix mixed-powder, intermediate layer mixed-powder and hydroxyapatite powder are respectively charged into lower floor, middle level and the upper strata of graphite jig, then using plasma discharging stove sintering, furnace cooling produces multi-layer biological composite.Not only there is with mechanical property that people's bone photo is worked as but also substantially increase the bioactivity of material using the multilayer materials prepared by the present invention；Present invention process is clean, simple, with low cost, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to a kind of multi-layer biological composite and preparation method thereof, belong to bio-medical material preparation field.
Background technology
Multi-layer biological composite is the bio-medical material being composited by two or more different biomaterials, and it leads
It is used for the manufacture of the reparation, replacement and artificial organs of tissue.Conventional medical titanium alloy material mechanical property is higher, is moved
Easily stress shielding is produced after plant with surrounding tissue and causes transplanting to fail, in addition, titanium alloy material is bio-inert material, is difficult
In inducing peripheral tissue cell growth, so that with reference to insecure, by the shadow of physiological environment in physiological environment or after implanting
Ring, cause metal ion or monomer to discharge, cause the harmful effect to body.Although and hydroxyapatite is with good chemistry
Stability and compatibility, high intensity and wear-resisting, corrosion resistance, but the bending strength of material is low, fragility big, in physiological environment
Fatigue is not high with breakdown strength, and under conditions of no reinforcement measure, it can be only applied to be not subject to load or is subjected only to pure pressure
The situation of mechanical load.
Therefore homogenous material can not meet the requirement of clinical practice well, utilize Material cladding of different nature
Bio-medical composition has been achieved for certain research effect, wherein bioceramic is mixed into metallic matrix, using mixed
Biocomposite material prepared by the techniques such as conjunction, sintering, ceramics are difficult for drop-off, and the mixing of ceramics and metal is added each other
Wellability, so as to be conducive to the raising of material compactness and mechanical property.Patent publication No. is CN 101125244A, titanium/hydroxyl
A kind of titanium/hydroxyapatite powder is disclosed in apatite biological composite and preparation method thereof and passes through 3 ~ 6 hours ball millings,
0 ~ 100MP sintering pressures, 1000 DEG C of -1200 DEG C of sintering prepare Biocomposite material, and the volume of titanium accounts for the 60-69% of composite,
The modulus of elasticity of prepared Biocomposite material is matrix because of pure titanium（Pure titanium 100GPa）It can cause and people's bone performance (springform
Amount is in 10-30GPa) mismatch, so as to cause " stress shielding " phenomenon.Document（Park, S.-H., K.-D. Woo, et
al. Mechanical properties and bio-compatibility of Ti-Nb-Zr-HA biomaterial
fabricated by rapid sintering using HEMM powders. Korean Journal of Materials
Research, 2011,21（7）: 384-390.）Report 10-2Torr vacuums, 70MPa axial compressive forces, 1000 DEG C of sintering
Ti-35%Nb-7%Zr-10HA Biocomposite materials tissue and hardness.According to another document（Zhang Yumei, titanium-based hydroxylapatite biology
The preparation of composite, Master's thesis, 2007）Report, by high-energy ball milling 4 hours（Ratio of grinding media to material 5:1）, sintering pressure 5-
30MPa, 1000 DEG C -1200 DEG C of sintering temperature is risen to 20 DEG C/min, and insulation 10min is prepared for Ti13Nb13Zr-44vol%HA
With Ti15Mo-30vol%HA, show by simulated body fluid immersion test, composite material surface easily forms the hole of class people's bone structure
Gap, but its modulus of elasticity is in 44.8-66.3GPa, caused by the matrix elastic modulus of alloy are higher because selected by, from without good
Good mechanical compatibility.In addition, above-mentioned Biocomposite material has preferable bioactivity due to the addition of bioceramic, but
It is that HA additions are limited, the raising for bioactivity is unfavorable.
In order to improve the bioactivity of metal material surface, the research of top layer activated metal is more and more, mainly uses
The modes such as plasma spraying, laser melting coating, differential arc oxidation prepare surface ceramic coat.Patent CN1451444 discloses a species
Osteolith artificial joint with bio-active gradient coating material and preparation method thereof, this method is using plasma spraying technology in gold
It is 60~80 μm of bioactivity coatings that category matrix surface, which prepares the change of composition continuous gradient, thickness, then in bioactivity ladder
The bionical thickness of preparing of degree coating surface is 5~15 μm of bone like apatite layer.The bio-active gradient coating of this method（Quality hundred
Divide content）Main component is 30~60% hydroxyapatites, 20~50% bioactivity glass and 10~30% titanium oxide.Specially
Sharp CN102031518A discloses a kind of preparation method of titanium alloy surface laser-clad composite bioceramic coating material, this side
Method uses laser melting and coating process, by the low calcium salt composite powder of good fluidity, water content in the case of not adding additives it is prefabricated
Coating, then cladding is in titanium alloy substrate surface, and prepared composite material surface even tissue, crystallinity are good, coating with
Matrix forms enhanced primary treatment, it is possible to resolve bioceramic delamination is the problem of human body easily comes off, but its coating layer thickness is most
Greatly 2mm.Patent CN012560595A discloses a kind of medical surface of metal titanium and prepares hydroxyapatite and poriferous titanium dioxide
Pure titanium or titanium alloy are placed in the stainless steel trough body containing alkaline electrolyte by the method for composite coating, this invention, using bipolar
The pulse power, forms one layer of porous silica titanium coating, then using hydro-thermal method porous by differential arc oxidation in metal surface
Titanium dioxide surface growth in situ hydroxyapatite coating layer, coating layer thickness is up to 3-20 μm.Patent CN101537208A is disclosed
A kind of titanium or titanium alloy surface bioactivity coatings and method, the method are combined using anodic oxidation and alkali process and prepare surface life
Thing coating, inside and outside three layers prepared of coating point, internal layer is titanium oxide layer, and thickness is 0.5-10 μm, and centre is sodium titanate
Gel thicknesses of layers is 0.1-10 μm, and outer layer is hydroxyapatite layer, and thickness is 1-15 μm.Patent CN102631704A is disclosed
A kind of titanium aluminium base hydroxyapatite coating layer and preparation method, this invention use synthesis of hydroxyapatite by deposition method powder and glycerine
Mixture, is then brushed on the titanium-aluminium alloy surface Jing Guo corrosion treatment, made by high temperature sintering formation biological coating
Standby coating layer thickness is 0.1-3.0mm.Bio-ceramic coating in foregoing invention enhances the bioactivity of metal, is easy to induction
Cell growth.But because ceramic coating is relatively thin and easily taken off because of the difference of coating and metallic matrix property in transplant
Fall, so as to have impact on its application.
Based on this, using HA as bioceramic top layer in the present invention, Ti-Nb-Zr alloys/hydroxyapatite is centre
Layer, the Ti-Nb-Zr alloys of low elastic modulus are matrix, by improving preparation technology, successfully prepare a kind of and people's bone performance
With multi-layer biological composite preferable and with preferable bioactivity.
The content of the invention
The technical problem to be solved in the present invention is：For current face coat Biocomposite material and it is mixed with biology
The problem of composite, the titanium alloy of low elastic modulus is used for matrix, titanium alloy/ceramics are transition zone, ceramic layer is biology
Active layer, can solve the problems, such as to influence interface cohesion because difference of thermal expansion coefficients is larger between ceramics and metal, maintain again good
Good mechanical property, can more increase substantially the bioactivity of composite.
It is an object of the invention to provide a kind of multi-layer biological composite, the multi-layer biological composite is with titanium alloy
For matrix, titanium alloy-titanium/hydroxyl apatite biological composite material is intermediate layer, and hydroxyapatite is biological ceramic surface；Titanium alloy
The mass percent that the mass percent that Ti mass percent is 60 ~ 73%, Nb in matrix is 25 ~ 34%, Zr is 2 ~ 6%, middle
The mass percent that the mass percent that Ti mass percent is 35 ~ 42%, Nb in layer is 25 ~ 34%, Zr is 2 ~ 6%, HA's
Mass percent is 25 ~ 30%, and bioceramic top layer is HA.
Described Ti, Zr, Nb powder purity is 99. 5%, 99.95% and 99%, 25 μm ~ 44 μm of particle mean size；Hydroxyl phosphorus
The purity 97% of lime stone, particle mean size is 20nm ~ 10 μm；
The intermediate layer thickness of the composite is 1 ~ 5mm, and bioceramic top layer is maximum up to 8mm.
Another object of the present invention is to provide the preparation method of the multi-layer biological composite, concrete technology step is such as
Under：
（1）Titanium alloy substrate powder is weighed by composition proportion, the metal dust in intermediate layer is put into ball grinder, sealed with alcohol
It is evacuated to ball milling after 20 ~ 30Pa；Wherein titanium alloy substrate powder dried after 10 ~ 12h of mechanical alloying ball milling, obtains base
Body mixed-powder；After the 6 ~ 8h of metal dust mechanical alloying in intermediate layer, then add after 1 ~ 2h of the mixed powder of hydroxyapatite ball milling
Drying, obtains intermediate layer mixed-powder, wherein（Ball-milling medium is stainless steel ball in mechanical milling process, and ratio of grinding media to material is 3:1~4:1）；
（2）By step（1）Matrix mixed-powder, intermediate layer mixed-powder and the hydroxyapatite powder of gained are filled respectively
Enter lower floor, middle level and the upper strata of graphite jig, be subsequently placed in plasma discharging stove sintering, discharge plasma sintering is inserted after compacting
In stove, under the conditions of 45 ~ 60MPa of axial compressive force, 2 ~ 10Pa of vacuum, first 900 DEG C are risen to 100 DEG C/min heating rates, then with
25 ~ 50 DEG C/min programming rate is heated to 1050 ~ 1200 DEG C of sintering temperature, is incubated 10 ~ 15min, then proceedes to keep vacuum
Until being cooled to room temperature obtains multi-layer biological composite.
Beneficial effects of the present invention：
（1）Matrix uses mechanical alloying ball milling with intermediate layer in ball-milling technology, and wherein intermediate layer is in mechanical alloying
After add ceramic powders, reduce the inhibition of the opposite β phase in version of α, be conducive to keeping titanium alloy substrate and intermediate layer
Alloy in low elastic modulus β phases be principal phase, reduce the content of high elastic modulus α phases, thus keep in composite matrix with
And the low elastic modulus in intermediate layer.
（2）It can be reduced because of hydroxyapatite and alloy powder expansion coefficient difference by segmented heating in sintering process
Larger and produce the defects such as loose, shrinkage cavity, higher axial compressive force is also beneficial to improve the consistency of material in sintering process, from
And reduce defect.
（3）Preparing multi-layer biological composite using the inventive method has composition and even tissue, interface cohesion good
The features such as.This material bioceramic does active layer, is conducive to improving bioactivity；The titanium alloy of low elastic modulus is matrix, is had
Beneficial to holding with people's bone compared with the mechanical property matched；Titanium alloy/hydroxyapatite is intermediate layer, is easy to improve Biocomposite material
Interface bond strength, and keep good bioactivity.
（4）The present invention makes full use of discharge plasma sintering to heat up, and controllable, sintering time is short, consistency is high, preparation process
Clean the advantages of, improve the microstructure and property of alloy, it is easy to accomplish industrialized production.
Brief description of the drawings
The prepared composite structure schematic diagram of Fig. 1 present invention；
Multi-layer biological matrices of composite material that Fig. 2 embodiments 1 are prepared and intermediate layer SEM patterns (a) and intermediate layer with
Bioceramic interface SEM patterns (b)；
The multi-layer biological composite intermediate layer that Fig. 3 embodiments 1 are prepared and bioceramic top layer interface (a) and line
Scan (b).
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
（1）Titanium alloy substrate presses Ti60%, Nb 34%, Zr 6.0% mass percent（wt%）It is 99. to weigh purity respectively
5%th, 99.95% and 99%, particle mean size is 45 μm of Ti, Nb, Zr metal dusts；Press Ti35%, Nb 34%, Zr in intermediate layer
6.0%, HA25% mass percent（wt%）It is 99. 5%, 99.95% and 99% to weigh purity, Ti, the Nb that 45 μm of particle mean size,
Zr metal dusts and purity are the hydroxyapatite powder that 97%, particle mean size is 100nm, and its quality is 3.4g；Bioceramic
Top layer is that 97%, granularity is that 100nm weighs HA powder 4g by purity.
（2）Step (1) is weighed into titanium alloy substrate powder, the metal dust in intermediate layer is respectively put into ball grinder, uses wine
Precision envelope is evacuated to 20Pa, and ratio of grinding media to material is 4:1；Wherein titanium alloy substrate powder is after mechanical alloying ball milling 12h, true
Drying obtains matrix mixed-powder under the conditions of 40 DEG C in empty drying box；After metallic intermediate layer Mechanical Alloying ball milling 8h, then
Add hydroxyapatite powder and mix powder 2h, then drying obtains intermediate layer mixed-powder under the conditions of 40 DEG C in vacuum drying chamber.
（3）By step（2）Matrix mixed-powder, intermediate layer mixed-powder and the hydroxyapatite powder of gained are filled respectively
Enter lower floor, middle level and the upper strata of graphite jig, inserted after compacting in discharge plasma sintering stove, in axial compressive force 45MPa, vacuum
Under the conditions of 10Pa, 900 DEG C first are risen to 100 DEG C/min heating rates, then sintering temperature is warming up to 25 DEG C/min programming rate
1050 DEG C of degree, is incubated 12min, then proceedes to keep vacuum until being cooled to room temperature sampling.The intermediate layer thickness of composite is
2mm, ceramic layer thickness reaches 4mm.
SEM patterns such as Fig. 2 of prepared multi-layer biological matrices of composite material and interlayer interface in the present embodiment（a）Institute
Show, matrix and intermediate layer are well combined as seen from the figure, and interface is in metallurgical binding, this is conducive to the boundary in matrix and intermediate layer
The raising of face bond strength；
The intermediate layer of the present embodiment multi-layer biological composite and the interface SEM patterns such as Fig. 2 on bioceramic top layer（b）Institute
Show, intermediate layer and bioceramic top layer interface cohesion are good as seen from the figure, in metallurgical binding；Bioceramic textura epidermoidea causes
It is close uniform, without obvious crackle under high power.
Biocomposite material intermediate layer manufactured in the present embodiment-bioceramic top layer interface, from intermediate layer to ceramic layer
In the line of Ti and Ca elements scan（Such as Fig. 3（b））As can be seen that in interface（Near 25 μm of distance）Occur in that Ti and Ca compared with
High peak, illustrates that element has certain diffusion in interface, and this is conducive to the raising of intermediate layer-ceramic layer interface bond strength.
To sum up, the present invention has the advantage that：One is using Ti-34Nb-6Zr as matrix（Modulus of elasticity is after tested
46GPa）It ensure that the low elastic modulus of composite；The HA that two Ti-34Nb-6Zr-25HA are incorporation 25wt% in intermediate layer has
Beneficial to the transition of ceramic layer and metallic matrix, so as to improve interface cohesion；Two be to add a certain amount of Ti in HA to contribute to pottery
The metallurgical binding of enamel coating and transition zone；Therefore, using the multilayer materials of titanium alloy-titanium alloy/ceramic to ceramic, by putting
Electric plasma agglomeration, by modified technique, is entirely capable of preparing the particulate metal matrix composites of low elastic modulus.Both improved compound
The mechanical compatibility of material, also substantially increases its bioactivity.
Embodiment 2
（1）Ti73%, Nb 25%, Zr 2% mass percent are pressed in titanium alloy substrate（wt%）Weighing purity respectively is
99. the 5%th, 99.95% and 99%, particle mean size is 25 μm of Ti, Nb, Zr metal dusts；Press Ti39%, Nb 25%, Zr in intermediate layer
6.0%, HA30% mass percent（wt%）Purity is weighed respectively for 99. 5%, 99.95% and 99%, the Ti that 25 μm of particle mean size,
Nb, Zr metal dust and purity are the hydroxyapatite powder that 97%, particle mean size is 10 μm, and its quality is 1.6g；Biology pottery
Porcelain top layer is that 97%, granularity is 10 μm and weighs HA powder 2g by purity.
（2）Step (1) is weighed into titanium alloy substrate powder, the metal dust in intermediate layer is respectively put into ball grinder, uses wine
Precision envelope is evacuated to 30Pa, and ratio of grinding media to material is 3:1, wherein titanium alloy substrate powder is after mechanical alloying ball milling 10h, true
Drying obtains matrix mixed-powder under the conditions of 40 DEG C in empty drying box；After metallic intermediate layer Mechanical Alloying ball milling 7h, then
Add hydroxyapatite powder and mix powder 1.5h, then drying obtains intermediate layer mixed powder under the conditions of 40 DEG C in vacuum drying chamber
End.
（3）By step（2）Matrix mixed-powder, intermediate layer mixed-powder and the hydroxyapatite powder of gained are filled respectively
Enter lower floor, middle level and the upper strata of graphite jig, inserted after compacting in discharge plasma sintering stove, in axial compressive force 50MPa, vacuum
Under the conditions of 2Pa, 900 DEG C first are risen to 100 DEG C/min heating rates, then 1100 DEG C of sintering temperature is warming up to 40 DEG C/min,
15min is incubated, then proceedes to keep vacuum until being cooled to room temperature sampling.The intermediate layer thickness of composite is 1mm, ceramic layer
Thickness 2mm.
Embodiment 3
（1）Ti65%, Nb 30%, Zr 5% mass percent are pressed in titanium alloy substrate（wt%）Weighing purity respectively is
99. the 5%th, 99.95% and 99%, particle mean size is 30 μm of Ti, Nb, Zr metal dusts；Press Ti38%, Nb 30%, Zr in intermediate layer
5%, HA27% mass percent（wt%）Purity is weighed respectively for 99. 5%, 99.95% and 99%, the Ti that 30 μm of particle mean size,
Nb, Zr metal dust and purity are the hydroxyapatite powder that 97%, particle mean size is 20nm, and its quality is 6.6g；Biology pottery
Porcelain top layer is that 97%, granularity is that 20nm weighs HA powder 8g by purity.
（2）Step (1) is weighed into titanium alloy substrate powder, the metal dust in intermediate layer is respectively put into ball grinder, uses wine
Precision envelope is evacuated to 25Pa, and ratio of grinding media to material is 4:1, wherein titanium alloy substrate powder is after mechanical alloying ball milling 10h, true
Drying obtains matrix mixed-powder under the conditions of 40 DEG C in empty drying box；After metallic intermediate layer Mechanical Alloying ball milling 8h, then
Add hydroxyapatite powder and mix powder 1h, then drying obtains intermediate layer mixed-powder under the conditions of 40 DEG C in vacuum drying chamber.
（3）By step（2）Matrix mixed-powder, intermediate layer mixed-powder and the hydroxyapatite powder of gained are filled respectively
Enter lower floor, middle level and the upper strata of graphite jig, inserted after compacting in discharge plasma sintering stove, in axial compressive force 60MPa, vacuum
Under the conditions of 2Pa, 900 DEG C first are risen to 100 DEG C/min heating rates, then sintering temperature is warming up to 50 DEG C/min programming rate
1200 DEG C, 10min is incubated, then proceedes to keep vacuum until being cooled to room temperature sampling.The intermediate layer thickness of composite is
4mm, ceramic layer thickness 8mm.
Embodiment 4
（1）Ti67%, Nb29%, Zr 4% mass percent is pressed in titanium alloy substrate（wt%）Weighing purity respectively is
99. the 5%th, 99.95% and 99%, particle mean size is 25 μm of Ti, Nb, Zr metal dusts；Press Ti42%, Nb 29%, Zr in intermediate layer
4%, HA25% mass percent（wt%）Purity is weighed respectively for 99. 5%, 99.95% and 99%, the Ti that 25 μm of particle mean size,
Nb, Zr metal dust and purity are the hydroxyapatite powder that 97%, particle mean size is 100nm, and its quality is 5.1g；It is biological
Ceramic surface is that 97%, granularity is that 100nm weighs HA powder 6g by purity.
（2）Step (1) is weighed into titanium alloy substrate powder, the metal dust in intermediate layer is respectively put into ball grinder, uses wine
Precision envelope is evacuated to 25Pa, and ratio of grinding media to material is 3:1.Wherein titanium alloy substrate powder is after mechanical alloying ball milling 11h, true
Drying obtains matrix mixed-powder under the conditions of 40 DEG C in empty drying box；After metallic intermediate layer Mechanical Alloying ball milling 6h, then
Add hydroxyapatite powder and mix powder 1.5h, then drying obtains intermediate layer mixed powder under the conditions of 40 DEG C in vacuum drying chamber
End.
（3）By step（2）Matrix mixed-powder, intermediate layer mixed-powder and the hydroxyapatite powder of gained are filled respectively
Enter lower floor, middle level and the upper strata of graphite jig, inserted after compacting in discharge plasma sintering stove, in axial compressive force 55MPa, vacuum
Under the conditions of 5Pa, 900 DEG C first are risen to 100 DEG C/min heating rates, then sintering temperature is warming up to 30 DEG C/min programming rate
1150 DEG C, 13min is incubated, then proceedes to keep vacuum until being cooled to room temperature sampling.The intermediate layer thickness of composite is
3mm, ceramic layer thickness is maximum up to 6mm.
Claims (4)
1. a kind of preparation method of multi-layer biological composite, it is characterised in that concrete technology step is as follows：
（1）The powder for weighing titanium alloy substrate and Ti, Nb, the Zr in intermediate layer by composition proportion is respectively put into ball grinder, uses wine
Precision envelope is evacuated to ball milling after 20 ~ 30Pa；Wherein the powder of titanium alloy substrate dried after 10 ~ 12h of mechanical alloying ball milling
It is dry, obtain matrix mixed-powder；After the 6 ~ 8h of metal dust mechanical alloying in intermediate layer, then add hydroxyapatite ball milling mix
Dried after 1 ~ 2h of powder, obtain intermediate layer mixed-powder；
（2）By step（1）In matrix mixed-powder, intermediate layer mixed-powder and hydroxyapatite powder be respectively charged into graphite
Lower floor, middle level and the upper strata of mould, are inserted after compacting in discharge plasma sintering stove, in 45 ~ 60MPa of axial compressive force, vacuum 2
Under the conditions of ~ 10Pa, 1050 ~ 1200 DEG C of sintering temperature is heated to by segmented heating, 10 ~ 15min is incubated, then proceed to keep
Vacuum produces multi-layer biological composite until being cooled to room temperature；
The multi-layer biological composite, using titanium alloy as matrix, titanium alloy-titanium/hydroxyl apatite biological composite material is centre
Layer, hydroxyapatite is biological ceramic surface；Ti mass percent is 60 ~ 73%, Nb mass percent in titanium alloy substrate
The mass percent for being Ti in 2 ~ 6%, intermediate layer for 25 ~ 34%, Zr mass percent is 35 ~ 42%, Nb mass percent
The mass percent for being 2 ~ 6%, HA for 25 ~ 34%, Zr mass percent is 25 ~ 30%, and bioceramic top layer is HA；
Step（3）The segmented heating is first to rise to 900 DEG C with 100 DEG C/min heating rates, then with 25 ~ 50 DEG C/min liter
Warm speed is warming up to sintering temperature.
2. the preparation method of multi-layer biological composite according to claim 1, it is characterised in that：Described Ti, Nb, Zr's
Powder purity is 99. 5%, 99.95% and 99%, 25 μm ~ 45 μm of particle mean size, the purity 97% of hydroxyapatite, and particle mean size is
20nm~10μm。
3. the preparation method of multi-layer biological composite according to claim 1, it is characterised in that：Step（1）Middle ball milling mistake
Ball-milling medium is stainless steel ball in journey, and ratio of grinding media to material is 3:1~4:1.
4. the preparation method of multi-layer biological composite according to claim 1, it is characterised in that：The multi-layer biological is combined
The intermediate layer thickness of material is 1 ~ 5mm, and biological ceramic layer is up to 8mm.
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| CN105367078A (en) * | 2015-12-02 | 2016-03-02 | 上海大学 | Preparation method for HA/binder/ZrO2 laminar composite biological ceramic material |
| US10926480B2 (en) * | 2017-09-05 | 2021-02-23 | The Boeing Company | Methods for manufacturing components having spatially graded properties |
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| CN108863341A (en) * | 2018-08-24 | 2018-11-23 | 山东建筑大学 | Titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic preparation method |
| CN109330744B (en) * | 2018-09-27 | 2020-08-25 | 山东建筑大学 | 3D printing artificial finger bone of customized degradable multi-element multi-layer nano composite |
| CN110560695B (en) * | 2019-09-03 | 2021-10-22 | 西安建筑科技大学 | Titanium-based functional gradient material with porous surface and preparation method thereof |
| CN111590080A (en) * | 2020-05-21 | 2020-08-28 | 南京航空航天大学 | Method for rapidly preparing titanium-plated diamond copper composite material by SPS |
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