CN102657896A - Method for preparing biological gradient coating on surface of titanium alloy - Google Patents
Method for preparing biological gradient coating on surface of titanium alloy Download PDFInfo
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- CN102657896A CN102657896A CN2012101804862A CN201210180486A CN102657896A CN 102657896 A CN102657896 A CN 102657896A CN 2012101804862 A CN2012101804862 A CN 2012101804862A CN 201210180486 A CN201210180486 A CN 201210180486A CN 102657896 A CN102657896 A CN 102657896A
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- 238000000576 coating method Methods 0.000 title claims abstract description 75
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 55
- 238000000498 ball milling Methods 0.000 claims abstract description 42
- 239000010936 titanium Substances 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 33
- 239000011159 matrix material Substances 0.000 claims description 28
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 25
- 238000005507 spraying Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 230000007423 decrease Effects 0.000 claims description 18
- 239000011812 mixed powder Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 13
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 229960004756 ethanol Drugs 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 230000002159 abnormal effect Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 230000035943 smell Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 abstract description 43
- 239000000463 material Substances 0.000 abstract description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 5
- 208000037656 Respiratory Sounds Diseases 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 230000009772 tissue formation Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a method for preparing a biological gradient coating on surface of a titanium alloy. The structure of the coating is Ti-yttria stabilized zirconia (YSZ)-fluor-hydroxyapatite (FHA). YSZ and FHA powder which is evenly mixed is prepared by ball-milling mixed material by virtue of a roller; Ti-YSZ-FHA compound powder with different ingredient ratio of Ti to YSZ and FHA by high-efficient ball-milling (planetary ball-milling); and the biological gradient coating is prepared on the surface of Ti-25Nb-10Ta-1Zr-0.2Fe titanium alloy by a slurry spraying-sintering method. The thickness of the gradient coating is controlled by changing the concentration of slurry and the coating and the basal body has excellent comprehensive mechanical property after sintering.
Description
Technical field
The invention belongs to medical titanium alloy face coat preparing technical field, what relate to is that titanium alloy surface prepares Ti-YSZ-FHA biological gradient coating and preparation method thereof, specifically is at Ti with slip spraying-sintering process
6Al
4V alloy surface preparation Ti-YSZ-FHA biological gradient active coating.
Background technology
(Hydroxyapatite, HA) molecular formula is Ca to hydroxyapatite
10(PO
4)
6(OH)
2, be the basic inorganic constituents of human body hard tissue, have excellent biological compatibility and biological activity, the dissolving of HA coating has stimulated the combination of osseous tissue, can combine closely with the soft tissue formation of human body at short notice behind its implant into body.But HA fragility is big, intensity is low, rupture strength and fracture toughness are poor, has limited its application at human body heavy burden position.And pass through coating technology at strong basis body (pure titanium or titanium alloy) surface-coated HA active coating; The composite construction implantation body that forms can change virgin metal implant surface form; The hole that formation is communicated with each other is prominent; The tissue that generates is growth in the hole is prominent, has strengthened the frame for movement of implantation body and bone and has guided osteogenesis, becomes one of focus of present research.But clinical practice finds that the degradation speed of HA in human body is fast, causes peeling off of coating, so that implantation body lost efficacy in human body fast.The fluorine-containing HA that adopts fluorine part substituted hydroxy to form, i.e. FHA, the biological activity of existing HA has lower dissolubility simultaneously, and degradation speed in vivo is low, and longer RT is arranged; And FHA has good antibacterial action.
The slip spraying is for be widely used in preparing various functional metal/ceramic composite in recent years; Have that deposition velocity is fast, deposit thickness, The Nomenclature Composition and Structure of Complexes are controlled, equipment and technical process is simple, low cost and other advantages, use the FHA coating that the slip spraying method prepares HA and modification and more and more get more and more people's extensive concerning.The coating material of slip spraying preparation needs a follow-up heat treatment so that the further densification of sedimentary deposit.
The development of FGM (FGM) the particularly proposition of functionally gradient coating (FGC) provides a kind of new thinking for the unmatched problem of mechanical property between solution coating and the matrix.The component of (FGM) of FGM is divided cloth in gradient, and material property is changed continuously, thereby has brought into play group member's material advantage separately.FGM group member composition variation continuously weakens even has eliminated the macroscopic interface in the material, makes the stress in the coating obtain relaxing even eliminating.
Zirconium oxide (ZrO
2), particularly (yttria stabilized zirconia YSZ) has good toughness to the partially stabilized zirconium oxide of yittrium oxide; Higher modulus of elasticity, the existence of YSZ make the difference of the thermal coefficient of expansion between coating and the matrix that the one slow interval that changes arranged, and help reducing the internal stress between coating and matrix; Strengthen the bond strength at interface; Research shows that behind the adding YSZ, the thermal stability of coating improves greatly in hydroxyapatite coating layer; The mechanical property of coating has all obtained tangible improvement like bond strength, elastic modelling quantity, fracture toughness etc.
Therefore the advantage of various preparation coatings more than the present invention has combined; With Ti-25Nb-10Ta-1Zr-0.2Fe is matrix; YSZ is the reinforcing and toughening phase, and the combination of coating and matrix has been strengthened in the adding of Ti powder, reduces gradually to coating Ti content from matrix; FHA content increases gradually, and the method for first Application slip spraying at home and abroad and subsequent heat treatment has prepared Ti-YSZ-FHA compound bio gradient coating material.The coatings prepared material mechanical performance is good.
Summary of the invention
The objective of the invention is to the prior art defective, use slip spraying-sintering process at titanium alloy surface and prepare Ti-YSZ-FHA biological function gradient coating and concrete method for preparing thereof.
The objective of the invention is to realize in the following manner:
A kind of biological gradient active coating of titanium alloy surface is in the titanium alloy surface electro-deposition Ti-YSZ-FHA biological gradient active coating to be arranged; The order that said coating reduces with the mass ratio of Ti and YSZ+FHA respectively gradually successively in each solution electro-deposition obtain; The described mass ratio that successively decreases is by 51 to 15; Mass ratio 1:5 ~ 1:2 of YSZ and FHA, said FHA are Ca
10(PO
4)
6[(OH)
1-xF
x]
2, 0<x≤1, the YSZ powder is by 6-8 wt%Y
2O
3And 92-94wt%ZrO
2Form, described titanium alloy is the Ti-25Nb-10Ta-1Zr-0.2Fe alloy.
The method that a kind of titanium alloy surface prepares the biological gradient active coating may further comprise the steps:
(1) preparation of slip dusty spray
A, preparation FHA powder
A. solution preparation: prepare Ca (NO respectively
3)
24H
2O and (NH
4)
2HPO
4Solution, the mol ratio of control Ca and P is 1.67 1, according to chemical formula Ca
10(PO
4)
6[(OH)
1-xF
x]
2, 0<the NH of corresponding x value in x≤1
4F joins (NH
4)
2HPO
4In the solution, stir, the solid in each solution is fully dissolved, strong aqua ammonia is splashed in each solution, making each solution pH value is 11;
B. titration: with aforementioned (NH
4)
2HPO
4Solution dropwise joins Ca (NO slowly
3)
24H
2In the O solution, titrating while vigorous stirring keeps the pH value of mixed liquor to be not less than 10.5 with ammonia, and the back mixed liquor that reacts completely places and continues to stir 2 ~ 24h under the room temperature;
C. the mixed liquor ageing after-filtration after will stirring, drying and grinding is crossed 200 orders ~ 325 mesh sieves and is obtained the FHA powder
B, prepare the Ti-YSZ-FHA composite powder with planetary ball mill
YSZ and the FHA powder of mass ratio 1:5 ~ 1:2 are placed the ball grinder ball mill mixing; Again the Ti powder is placed the ball grinder planetary ball mill by the different gradient mass ratioes of mass ratio 1:5 ~ 5:1 respectively with mixed uniformly YSZ+FHA powder, obtain the composite powder of heterogeneity proportioning
(2) titanium alloy surface is through polishing, oil removing and sour pretreatment
(3) the order obtain solution that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively, the described mass ratio that successively decreases is by 51 to 15, the mass concentration of total soluble matters is 10g/L ~ 120g/L, being matrix through pretreated titanium alloy sheet
(4) adopt the inert gas shielding heat treatment technics that coating is sprayed the after heat sintering processes.
Ageing process is described in the c step: mixed liquor is left standstill 24h ~ 72h, pour out the supernatant, residual mixed liquor is placed be heated to boiling on the heating furnace, until no obvious ammonia abnormal smells from the patient; Said filter process is: residual mixed liquor is distilled washing, is 7 until pH value, carries out filtering filter cake with dehydrated alcohol at last; Said dry run is: the gained filter cake places drying baker in 60 ℃ ~ 80 ℃ dry 24h ~ 72h; Said grinding, the process of sieving is: dry products therefrom is ground in grinding alms bowl, use 200 orders ~ 325 mesh to sieve then and finally obtain the FHA powder.
B places zirconium oxide ball milling jar ball mill mixing with YSZ and FHA powder by mass ratio 1:5 ~ 1:2 in the step, and dehydrated alcohol is a medium, roller ball grinding machine rotating speed 100 rpm ~ 150rpm, ball milling time 1 ~ 5h; Ball milling is placed in the drying baker dry, 60 ℃ ~ 80 ℃ of baking temperatures, time 24h ~ 72h; The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively places the ball grinder planetary ball mill, and the described mass ratio that successively decreases is by 51 to 15, and dehydrated alcohol is a medium, and drum's speed of rotation is 200 ~ 300rpm, ball milling time 5h ~ 10h; Ball milling is placed in the drying baker dry, 60 ℃ ~ 80 ℃ of baking temperatures, time 24h ~ 72h.
(2) preprocessing process of titanium alloy is in the step: the titanium alloy sheet places the mixed solution ultrasonic cleaning 15min ~ 30min oil removing of ethanol and acetone, and the dose volume mark is 10% ~ 30% HNO
3Mixed solution with 1% ~ 4% HF soaks 1 ~ 2min with the titanium alloy test piece in solution, distilled water ultrasonic cleaning 15min ~ 30min, oven dry.
The detailed process of described step (3) does; The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively, the described mass ratio that successively decreases is by 51 to 15, mixed-powder is scattered in the dehydrated alcohol; Obtain the mixed liquor of heterogeneity proportioning; The concentration of mixed liquor is 10g/L ~ 120g/L, to be matrix through pretreated titanium sheet, carries out the slip spraying; Control coating thickness 10 μ m ~ 120 μ m, oven dry.
Heat treatment protection gas is argon in the described step (4), and programming rate is 3 ℃/min ~ 7 ℃/min, and heat treatment temperature is 500 ℃ ~ 1000 ℃, and temperature retention time is 2h ~ 5h, and cooling rate is 1 ℃/min ~ 5 ℃/min.
The sub-size of Ti powder of preparation coating is 30 μ m ~ 50 μ m in the described step (1), and the YSZ powder is by the Y of 6-8wt%
2O
3ZrO with 92-94wt%
2, particle size is 0.5 μ m ~ 5 μ m), the sub-size of FHA powder is 20 μ m ~ 40 μ m.
FHA of the present invention is Ca
10(PO
4)
6[(OH)
1-xF
x]
2, 0<x≤1, FHA makes coating have good heat stability and biocompatibility.Ti has strengthened the combination between coating and the matrix, and YSZ has improved the mechanical property of coating.Adopt slip spraying-sintering technology, make coating have excellent mechanical property through adjustment slip spray voltage and sintering temperature, concrete steps are following:
(1) preparation of slip dusty spray prepares the Ti-YSZ-FHA composite powder with planetary ball mill;
(2) substrate pretreated;
(3) dehydrated alcohol+dilute hydrochloric acid system is adopted in slip spraying, and control deposition voltage and slip are sprayed on the time of carrying out in the mixed liquor of heterogeneity proportioning, the structure and the thickness of control gradient coating;
(4) heat treatment adopts the inert gas shielding heat treatment technics that coating is sprayed subsequent treatment.
Described step (1), specifically:
The raw material that the present invention is used: pure Ti powder (30 μ m ~ 50 μ m), YSZ powder (6-8wt%Y
2O
3, 92-94wt%ZrO
2, 0.5 μ m ~ 5 μ m), FHA powder (20 μ m ~ 40 μ m).
1. prepare mixed uniformly YSZ+FHA powder
(mass ratio 1:5 ~ 1:2) place zirconium oxide ball milling jar ball mill mixing, dehydrated alcohol is a medium, roller ball grinding machine rotating speed 100rpm ~ 150rpm, ball milling time 1 ~ 5h with YSZ and FHA powder.Ball milling is placed in the drying baker dry, 60 ℃ ~ 80 ℃ of baking temperatures, time 24h ~ 72h.
2. the preparation of Ti+YSZ+FHA composite powder
The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively places the ball grinder planetary ball mill, and the described mass ratio that successively decreases is by 51 to 15, and dehydrated alcohol is a medium, and drum's speed of rotation is 200 ~ 300rpm, ball milling time 5h ~ 10h.Ball milling is placed in the drying baker dry, 60 ℃ ~ 80 ℃ of baking temperatures, time 24h ~ 72h.
Described step (2), specifically:
(the 0# sand papering is used in 10mm * 10mm * 2 ~ 3mm) to the Ti-25Nb-10Ta-1Zr-0.2Fe alloy sheet, places the mixed solution ultrasonic cleaning 15min ~ 30min oil removing of ethanol and acetone, and the dose volume mark is 10% ~ 30% HNO
3Mixed solution with 1% ~ 4% HF soaks 1 ~ 2min with the titanium alloy test piece in solution, distilled water ultrasonic cleaning 15min ~ 30min, oven dry.
Described step (3), specifically:
The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively; The described mass ratio that successively decreases is by 51 to 15; Mixed-powder is scattered in the dehydrated alcohol, obtains the mixed liquor of heterogeneity proportioning, and the concentration of mixed liquor is 10g/L ~ 120g/L; To be matrix, carry out the slip spraying through pretreated titanium sheet; Reduce gradually to coating surface Ti content from matrix, FHA content increases gradually, forms gradient coating, oven dry.Control coating thickness 10 μ m ~ 120 μ m.
Described step (4), specifically:
With being coated with to be placed in the tube furnace and under argon shield, heat-treating of slip spraying, programming rate is 3 ℃/min ~ 7 ℃/min, and heat treatment temperature is 500 ℃ ~ 1000 ℃, and temperature retention time is 2h ~ 5h, and cooling rate is 1 ℃/min ~ 5 ℃/min.
The present invention has tangible technological progress; The present invention is matrix with Ti-25Nb-10Ta-1Zr-0.2Fe; YSZ is the reinforcing and toughening phase; Reduce gradually to coating Ti content from matrix, FHA content increases gradually, and the method for first Application slip spraying at home and abroad and subsequent heat treatment has prepared Ti-YSZ-FHA compound bio gradient coating material.The coatings prepared material not only can be realized graded on composition; Improve matrix and the hot rerum natura of coating can with the matching of mechanical property; Thereby improve the adhesion (can reach 26.8MPa) of coating and matrix; And adopt the slip spraying also have simple to operate, convenient regulation and control, applicable to the matrix of complicated shape, have very strong industrialization prospect.
The specific embodiment
Below in conjunction with instance the present invention is done further description.
Embodiment 1
Ca (the NO of preparation 1mol/L
3)
24H
2O and 1mol/L (NH
4)
2HPO
4Solution, corresponding corresponding Ca
10(PO
4)
6(OH) NH of F value
4F joins (NH
4)
2HPO
4In the solution, the mol ratio of control Ca and P is 1.67:1, stirs, and the solid in the solution is fully dissolved, and strong aqua ammonia is splashed in each solution, and making each solution pH value is 11.
With (NH
4)
2HPO
4Solution dropwise joins Ca (NO slowly
3)
24H
2In the O solution, titrating while vigorous stirring keeps the pH value of mixed liquor to be not less than 10.5 with ammonia, and the back mixed liquor that reacts completely places and continues to stir 4h under the room temperature.Mixed liquor is left standstill 24h, pour out the supernatant, residual mixed liquor is placed be heated to boiling on the heating furnace, until no obvious ammonia abnormal smells from the patient.Residual mixed liquor is distilled washing, is 7 until pH value, filters with dehydrated alcohol at last.The gained filter cake places drying baker in 60 ℃ of dry 48h.Products therefrom is ground in grinding alms bowl, and sieving with 325 mesh then finally obtains the FHA powder.
Y with 8wt%
2O
3And 92wt%ZrO
2Be mixed with the YSZ powder, YSZ and FHA powder quality are placed zirconium oxide ball milling jar ball mill mixing than 1:5, dehydrated alcohol is a medium, roller ball grinding machine rotating speed 100rpm, ball milling time 1h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, time 24h.
Ti powder and mixed uniformly YSZ+FHA powder quality ratio are respectively 1:5, and 1:1,5:1 place zirconium oxide ball milling jar planetary ball mill, and dehydrated alcohol is a medium, and drum's speed of rotation is 200rpm, ball milling time 5h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, times 24 h.
(the dose volume mark is 10% HNO to the Ti-25Nb-10Ta-1Zr-0.2Fe alloy sheet for 10mm * 10mm * 2mm) use the 0# sand papering, the mixed solution ultrasonic cleaning 15min oil removing that places ethanol and acetone
3Mixed solution with 1% HF soaks 1min with the titanium alloy test piece in solution, distilled water ultrasonic cleaning 30min, oven dry.
The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively; The described mass ratio that successively decreases is by 51 to 15; Mixed-powder is scattered in the dehydrated alcohol, obtains the mixed liquor of heterogeneity proportioning, and the concentration of mixed liquor is 10g/L; To be matrix, carry out the slip spraying through pretreated titanium sheet; Reduce gradually to coating surface Ti content from matrix, FHA content increases gradually, forms gradient coating, oven dry.Control coating thickness 10 μ m.
With being coated with to be placed in the tube furnace and under argon shield, heat-treating of slip spraying, programming rate is 3 ℃/min, and heat treatment temperature is 500 ℃, and temperature retention time is 2h, and cooling rate is 1 ℃/min.
Coating layer thickness is about 10 μ m; Coating has a little crackle, and the adhesion of coating and matrix is 12.5MPa.
Embodiment 2
FHA powder and YSZ powder preparation method are with embodiment 1.YSZ and FHA powder quality are placed zirconium oxide ball milling jar ball mill mixing than 1:3, and dehydrated alcohol is a medium, roller ball grinding machine rotating speed 100rpm, ball milling time 1h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, time 24h.
Ti powder and mixed uniformly YSZ+FHA powder quality ratio are respectively 1:5, and 1:3,1:1,3:1,5:1 place zirconium oxide ball milling jar planetary ball mill, and dehydrated alcohol is a medium, and drum's speed of rotation is 250rpm, ball milling time 5h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, time 24h.
The titanium alloy sheet places the mixed solution ultrasonic cleaning 20min oil removing of ethanol and acetone, and the dose volume mark is 15% HNO
3Mixed solution with 2% HF soaks 1min with the titanium alloy test piece in solution, distilled water ultrasonic cleaning 20min, oven dry.
The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively; The described mass ratio that successively decreases is by 51 to 15; Mixed-powder is scattered in the dehydrated alcohol, obtains the mixed liquor of heterogeneity proportioning, and the concentration of mixed liquor is 50g/L; To be matrix, carry out the slip spraying through pretreated titanium sheet; Control coating thickness 50 μ m, oven dry.
With being coated with to be placed in the tube furnace and under argon shield, heat-treating of slip spraying, programming rate is 3 ℃/min, and heat treatment temperature is 700 ℃, and temperature retention time is 2h, and cooling rate is 1 ℃/min.
Coating layer thickness is about 50 μ m; Coating and matrix bond are fine and close, do not have obvious crackle, and the adhesion of coating and matrix is 26.8MPa.
Embodiment 3
FHA powder and YSZ powder preparation method are with embodiment 1.YSZ and FHA powder quality are placed zirconium oxide ball milling jar ball mill mixing than 1:3, and dehydrated alcohol is a medium, roller ball grinding machine rotating speed 150rpm, ball milling time 1h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, time 24h.
Ti powder and mixed uniformly YSZ+FHA powder quality ratio are respectively 1:5, and 1:3,1:1,3:1,5:1 place zirconium oxide ball milling jar planetary ball mill, and dehydrated alcohol is a medium, and drum's speed of rotation is 300rpm, ball milling time 5h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, time 24h.
The titanium alloy sheet places the mixed solution ultrasonic cleaning 25min oil removing of ethanol and acetone, and the dose volume mark is 25% HNO
3Mixed solution with 3% HF soaks 2min with the titanium alloy test piece in solution, distilled water ultrasonic cleaning 25min, oven dry.
The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively; The described mass ratio that successively decreases is by 51 to 15; Mixed-powder is scattered in the dehydrated alcohol, obtains the mixed liquor of heterogeneity proportioning, and the concentration of mixed liquor is 70g/L; To be matrix, carry out the slip spraying through pretreated titanium sheet; Control coating thickness 70 μ m, oven dry.
With being coated with to be placed in the tube furnace and under argon shield, heat-treating of slip spraying, programming rate is 3 ℃/min, and heat treatment temperature is 900 ℃, and temperature retention time is 2h, and cooling rate is 1 ℃/min.
Coating layer thickness is about 70 μ m; Coating and matrix bond are fine and close, do not have obvious crackle, and the adhesion of coating and matrix is 20.1MPa.
Embodiment 4
FHA powder and YSZ powder preparation method are with embodiment 1.YSZ and FHA powder quality are placed zirconium oxide ball milling jar ball mill mixing than 1:4, and dehydrated alcohol is a medium, roller ball grinding machine rotating speed 100rpm, ball milling time 1h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, time 24h.
With mixed uniformly YSZ+FHA powder quality is than placing zirconium oxide ball milling jar planetary ball mill for 5:1, dehydrated alcohol is a medium with the Ti powder, and drum's speed of rotation is 250rpm, ball milling time 5h.Ball milling is placed in the drying baker dry, 60 ℃ of baking temperatures, time 24h.
The titanium alloy sheet places the mixed solution ultrasonic cleaning 30min oil removing of ethanol and acetone, and the dose volume mark is 30% HNO
3Mixed solution with 4% HF soaks 1min with the titanium alloy test piece in solution, distilled water ultrasonic cleaning 30min, oven dry.
The order mixed-powder that reduces gradually according to the mass ratio of Ti and YSZ+FHA respectively; The described mass ratio that successively decreases is by 51 to 15; Mixed-powder is scattered in the dehydrated alcohol, obtains the mixed liquor of heterogeneity proportioning, and the concentration of mixed liquor is 120g/L; To be matrix, carry out the slip spraying through pretreated titanium sheet; Control coating thickness 120 μ m, oven dry.
With being coated with to be placed in the tube furnace and under argon shield, heat-treating of slip spraying, programming rate is 3 ℃/min, and heat treatment temperature is 1000 ℃, and temperature retention time is 5h, and cooling rate is 1 ℃/min.
Coating layer thickness is about 120 μ m; Have tangible crackle to produce, the adhesion of coating and matrix is 8.6Mpa.
Claims (8)
1. the biological gradient active coating of a titanium alloy surface; It is characterized in that; At described titanium alloy surface slip spraying Ti-YSZ-FHA biological gradient active coating, said coating sprays acquisition with the order that the mass ratio of Ti and YSZ+FHA successively decreases respectively successively, and the described mass ratio that successively decreases is by 51 to 15; Mass ratio 1:5 ~ 1:2 of YSZ and FHA, said FHA are Ca
10(PO
4)
6[(OH)
1-xF
x]
2, 0<x≤1, the YSZ powder is by the Y of 6-8wt%
2O
3With 92-94wt% ZrO
2Form, described titanium alloy is the Ti-25Nb-10Ta-1Zr-0.2Fe alloy.
2. the method for preparing of a titanium alloy surface biological gradient active coating is characterized in that, may further comprise the steps:
(1) preparation of slip dusty spray:
A, preparation FHA powder
A. solution preparation: prepare Ca (NO respectively
3)
24H
2O and (NH
4)
2HPO
4Solution, the mol ratio of control Ca and P is 1.67 1, according to chemical formula Ca
10(PO
4)
6[(OH)
1-xF
x]
2, 0<the NH of corresponding x value in x≤1
4F joins (NH
4)
2HPO
4Stir in the solution, the solid in each solution is fully dissolved, strong aqua ammonia is splashed in each solution, making each solution pH value is 11;
B. titration: with aforementioned (NH
4)
2HPO
4Solution dropwise joins Ca (NO slowly
3)
24H
2In the O solution, titrating while vigorous stirring keeps the pH value of mixed liquor to be not less than 10.5 with ammonia, and the back mixed liquor that reacts completely places and continues to stir 2 ~ 24h under the room temperature;
C. the mixed liquor ageing after-filtration after will stirring, drying and grinding is crossed 200 orders ~ 325 mesh sieves and is obtained the FHA powder
B, prepare the Ti-YSZ-FHA composite powder with planetary ball mill
YSZ and the FHA powder of mass ratio 1:5 ~ 1:2 are placed the ball grinder ball mill mixing, again the Ti powder is placed the ball grinder planetary ball mill by the different gradient mass ratioes of mass ratio 1:5 ~ 5:1 respectively with mixed uniformly YSZ+FHA powder;
(2) titanium alloy surface is through polishing, oil removing and sour pretreatment;
(3) the order preparation slip that successively decreases according to the mass ratio of Ti and YSZ+FHA respectively, the described mass ratio that successively decreases is by 51 to 15, the mass concentration of total soluble matters is 10g/L ~ 120g/L, being matrix through pretreated titanium alloy sheet;
(4) adopt the inert gas shielding heat treatment technics that coating is sprayed the after heat sintering processes.
3. titanium alloy surface according to claim 2 prepares the method for biological gradient coating; It is characterized in that ageing process is described in the c step: mixed liquor is left standstill 24h ~ 72h, pour out the supernatant; Residual mixed liquor placed be heated to boiling on the heating furnace, until no obvious ammonia abnormal smells from the patient; Said filter process is: residual mixed liquor is distilled washing, is 7 until pH value, carries out filtering filter cake with dehydrated alcohol at last; Said dry run is: the gained filter cake places drying baker in 60 ℃ ~ 80 ℃ dry 24h ~ 72h; Said grinding, the process of sieving is: dry products therefrom is ground in grinding alms bowl, use 200 orders ~ 325 mesh to sieve then and finally obtain the FHA powder.
4. titanium alloy surface according to claim 2 prepares the method for biological gradient coating; It is characterized in that; B places zirconium oxide ball milling jar ball mill mixing with YSZ and FHA powder by mass ratio 1:5 ~ 1:2 in the step; Dehydrated alcohol is a medium, roller ball grinding machine rotating speed 100rpm ~ 150rpm, ball milling time 1 ~ 5h; Ball milling is placed in the drying baker dry, 60 ℃ ~ 80 ℃ of baking temperatures, time 24h ~ 72h; The order mixed-powder that successively decreases according to the mass ratio of Ti and YSZ+FHA respectively places the ball grinder planetary ball mill, and the described mass ratio that successively decreases is by 51 to 15, and dehydrated alcohol is a medium, and drum's speed of rotation is 200 ~ 300rpm, ball milling time 5h ~ 10h; Ball milling is placed in the drying baker dry, 60 ℃ ~ 80 ℃ of baking temperatures, time 24h ~ 72h.
5. titanium alloy surface according to claim 2 prepares the method for biological gradient coating; It is characterized in that; (2) preprocessing process of titanium alloy is in the step: the titanium alloy sheet is used the 0# sand papering; Place the mixed solution ultrasonic cleaning 15min ~ 30min oil removing of ethanol and acetone, the dose volume mark is 10% ~ 30% HNO
3Mixed solution with 1% ~ 4% HF soaks 1 ~ 2min with the titanium alloy test piece in solution, distilled water ultrasonic cleaning 15min ~ 30min, oven dry.
6. titanium alloy surface according to claim 2 prepares the method for biological gradient coating, it is characterized in that, the detailed process of described step (3) does; The order mixed-powder that successively decreases according to the mass ratio of Ti and YSZ+FHA respectively, the described mass ratio that successively decreases is by 51 to 15, mixed-powder is scattered in the dehydrated alcohol; Obtain the mixed liquor of heterogeneity proportioning, the concentration of mixed liquor is 10g/L ~ 120g/L, carries out the slip spraying; Control coating thickness 10 μ m ~ 120 μ m, oven dry.
7. titanium alloy surface according to claim 2 prepares the method for biological gradient coating; It is characterized in that; Heat treatment protection gas is argon in the described step (4), and programming rate is 3 ℃/min ~ 7 ℃/min, and heat treatment temperature is 500 ℃ ~ 1000 ℃; Temperature retention time is 2h ~ 5h, and cooling rate is 1 ℃/min ~ 5 ℃/min.
8. titanium alloy surface according to claim 2 prepares the method for biological gradient coating, it is characterized in that, the sub-size of Ti powder of preparation coating is 30 μ m ~ 50 μ m in the described step (1), and the YSZ powder is by the Y of 6-8wt%
2O
3ZrO with 92-94wt%
2, particle size is 0.5 μ m ~ 5 μ m), the sub-size of FHA powder is 20 μ m ~ 40 μ m.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103463681A (en) * | 2013-09-16 | 2013-12-25 | 同济大学 | Method for preparing biodegradable magnesium alloy surface modification fluoridated hydroxyapatite coating |
| CN108014368A (en) * | 2017-11-21 | 2018-05-11 | 西安理工大学 | A kind of Mg alloy surface graded composite piezoelectric biological coating and preparation method thereof |
| CN112662986A (en) * | 2020-12-16 | 2021-04-16 | 苏州热工研究院有限公司 | Large-scale shaft surface gradient coating and preparation method thereof |
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| CN101455860A (en) * | 2008-12-19 | 2009-06-17 | 中南大学 | Titanium alloy surface TiO2-FHA biological gradient active coating and preparation method thereof |
| CN101455859A (en) * | 2008-12-19 | 2009-06-17 | 中南大学 | Titanium alloy surface Ti-YSZ-FHA biological gradient active coatings and preparation method thereof |
| CN102167586A (en) * | 2011-01-20 | 2011-08-31 | 中南大学 | Low-temperature activated sintered 8YSZ-based ceramic and preparation method thereof |
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| CN101455860A (en) * | 2008-12-19 | 2009-06-17 | 中南大学 | Titanium alloy surface TiO2-FHA biological gradient active coating and preparation method thereof |
| CN101455859A (en) * | 2008-12-19 | 2009-06-17 | 中南大学 | Titanium alloy surface Ti-YSZ-FHA biological gradient active coatings and preparation method thereof |
| CN102167586A (en) * | 2011-01-20 | 2011-08-31 | 中南大学 | Low-temperature activated sintered 8YSZ-based ceramic and preparation method thereof |
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| CN103463681A (en) * | 2013-09-16 | 2013-12-25 | 同济大学 | Method for preparing biodegradable magnesium alloy surface modification fluoridated hydroxyapatite coating |
| CN103463681B (en) * | 2013-09-16 | 2015-01-14 | 同济大学 | Method for preparing biodegradable magnesium alloy surface modification fluoridated hydroxyapatite coating |
| CN108014368A (en) * | 2017-11-21 | 2018-05-11 | 西安理工大学 | A kind of Mg alloy surface graded composite piezoelectric biological coating and preparation method thereof |
| CN112662986A (en) * | 2020-12-16 | 2021-04-16 | 苏州热工研究院有限公司 | Large-scale shaft surface gradient coating and preparation method thereof |
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