CN105056297A - Medical titanium alloy bar material with strong antibiosis capability - Google Patents
Medical titanium alloy bar material with strong antibiosis capability Download PDFInfo
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- CN105056297A CN105056297A CN201510476615.6A CN201510476615A CN105056297A CN 105056297 A CN105056297 A CN 105056297A CN 201510476615 A CN201510476615 A CN 201510476615A CN 105056297 A CN105056297 A CN 105056297A
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title abstract description 14
- 230000003115 biocidal effect Effects 0.000 title abstract 2
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010955 niobium Substances 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 9
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 9
- 239000010456 wollastonite Substances 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 3
- 238000005242 forging Methods 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000007547 defect Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 14
- 230000000844 anti-bacterial effect Effects 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 235000021110 pickles Nutrition 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 230000004927 fusion Effects 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000005461 lubrication Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 4
- 238000007750 plasma spraying Methods 0.000 claims description 4
- 238000005488 sandblasting Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000000415 inactivating effect Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 210000000988 bone and bone Anatomy 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract 1
- 210000001519 tissue Anatomy 0.000 abstract 1
- 210000004746 tooth root Anatomy 0.000 abstract 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000007943 implant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a medical titanium alloy bar material with strong antibiosis capability, which comprises a titanium alloy bar material body and an externally-coated coating, the titanium alloy bar material comprises the following components: 7-10% of zirconium, 1.5-2.5% of iron, 0.5-0.8% of chromium, 0.5-0.9% of gallium, 0.25-0.75% of tin, 0.02-0.07% of hafnium, 1-2% of tantalum, 1-2% of aluminium, 0.25-0.45% of vanadium, 0.1-0.18% of boron, 0.12-0.18% of cerium, 4-15% of niobium, 9-13% of molybdenum, 0.001-0.005% of silver and the balance of titanium; the externally-coated coating comprises the following components: 60-80 parts of titanium oxide, 0.1-1 part of metal silver, 15-20 parts of wollastonite, 0.1-0.5 parts of silver oxide, 2-4 parts of titanium boride and 4-8 parts of magnesium oxide powder. The quality of the medical titanium alloy bar material is excellent, mechanical property of the alloy is excellent, and the medical titanium alloy bar material can be used as a substitution material for hard tissues restoration as bone, joint and artificial dental root.
Description
Technical field
The present invention relates to the medical titanium alloy bar that a kind of antibacterial ability is strong, belong to medical artificial bone field.
Background technology
Titanium or titanium alloy because density is low, intensity is high, elastic modelling quantity is low, the advantage such as fine corrosion resistance and good biocompatibility and be widely used in biologic medical field, be the desirable material producing complicated surgical implant.The titanium alloy of early stage Srgery grafting is mainly pure titanium and Ti6Al4V alloy, but going deep into along with application, the deficiency of pure titanium and Ti6Al4V alloy is also found, pure titanium intensity is too low, be unfit to do supporting part implant into body, although Ti6Al4V alloy intensity is higher, the V element contained is harmful.Therefore, the medical titanium alloy Ti6Al7Nb substituting V with Nb is developed, and is used to productive manpower joint.
Metal, pottery and macromolecular material are current three large medical joint prosthesis's materials, three kinds of materials respectively have its pluses and minuses: metal and pottery are widely used at negative load medical field, but metal is easy to wear and corrosion, and pottery then fragility is large: the good but wearability of macromolecular material pliability and hardness poor.Titanium alloy is owing to having high strength, toughness and corrosion resistant characteristic thus becoming joint prosthesis's material of new generation.But just the embedding property that connects of a kind of machinery is integrated between titanium alloy and bone, implant is in vivo after long service, and fricative abrasive dust can affect its biologically inert, thus causes local organization inflammation, shortens its service life.Therefore surface modification is carried out to improve the attention that its biocompatibility causes researcher to titanium alloy.Surface modification is all generally that modified surface generally has good biological activity by adopting various face coat or thin film technique to resistance to wear biocompatible coating for improving the mar proof of joint prosthesis, corrosion resistance and biocompatibility in metal base surface preparation.
The present invention is directed to the limitation of existing medical joint prosthesis, prepare composite coating at titanium alloy artificial boney joint surfaces, improve case hardness and the bond strength of coating, and strengthen biocompatibility, promote further developing of joint prosthesis's technology.
Summary of the invention
The present invention is directed to the problems referred to above and propose a kind of technique refinement, medical titanium alloy bar that antibacterial ability of good performance is strong.
The medical titanium alloy bar that a kind of antibacterial ability is strong, described titanium alloy rod bar comprises the coating of titanium alloy rod bar body and its outside, the chemical composition of described titanium alloy rod bar body is: zirconium 7-10%, ferrum: 1.5-2.5%, chromium: 0.5-0.8%, gallium: 0.5-0.9%, stannum: 0.25-0.75%, hafnium 0.02-0.07%, tantalum 1-2%, aluminum: 1-2%, vanadium: 0.25-0.45%, boron: 0.1-0.18%, cerium: 0.12-0.18%, niobium 4-15%, molybdenum: 9-13%, silver: 0.001-0.005%, surplus is titanium; Consisting of of described outside coating: titanium oxide: 60-80 part, argent: 0.1-1 part; Wollastonite: 15-20 part; Silver oxide: 0.1-0.5 part; Titanium boride: 2-4 part; Magnesia powder: 4-8 part.
Further, described titanium alloy rod bar is obtained by following steps:
(1) ingot blank preparation: the chemical composition of described ingot blank is: zirconium 7-10%, ferrum: 1.5-2.5%, chromium: 0.5-0.8%, gallium: 0.5-0.9%, stannum: 0.25-0.75%, hafnium 0.02-0.07%, tantalum 1-2%, aluminum: 1-2%, vanadium: 0.25-0.45%, boron: 0.1-0.18%, cerium: 0.12-0.18%, niobium 4-15%, molybdenum: 9-13%, silver: 0.001-0.005%, surplus is titanium;
Prepare burden by alloying component mass percent, melting in fine vacuum arc heating furnace, abundant stirring, be cast into ingot blank, ingot blank is added in vacuum drying oven Ar gas shielded to heat-treat, ingot blank is warming up to 920-940 DEG C with 200-250 DEG C/h, insulation 6-10 hour, then cool to 550-580 DEG C with 120-150 DEG C/h, insulation 2-6 hour, then cools to 280-320 DEG C with 80-90 DEG C/h, insulation 2-5 hour, continue to cool to 180-190 DEG C with 50-65 DEG C/h, insulation 2-5 hour, then furnace cooling is to room temperature;
(2) forging molding
Surface-coated: applying one deck at surface of ingot blank is that the coating of main component prevents from being oxidized during high temperature process and increasing lubrication with boron nitride;
With 1000 tons of hydraulic presses, step ingot blank is incubated 1-2 hour at 900-1000 DEG C,
adoptwith open die forging, final forging temperature 660-720 DEG C, is swaged into the square billet that the length of side is 200-300mm after repeated multiple times;
Be the square billet cool to room temperature of 200-300mm by the length of side, the blank heating after thinning surface defect is out of shape 3-6 time to 900-950 DEG C of jumping-up and pulling, final forging temperature 770-810 DEG C, pass deformation 20-45%, and total deformation adds up 70-130%;
Then forging stock cool to room temperature, after thinning surface defect, is heated to 700-740 DEG C of jumping-up and pulls out forging 3-6 time, pass deformation 15-30%, accumulative total deformation 55-110%;
By the forging stock cool to room temperature that upsetting pull is forged, after thinning surface defect, then be heated to 680-720 DEG C of jumping-up and pull out forging 2-3 time, pass deformation 40-50%; And the last time pulling forging time chamfered edge, round as a ball;
By upsetting pull forge forging stock cool to room temperature, after thinning surface defect, then be heated to 730-740 DEG C of chamfered edge, round as a ball, pulling be swaged to the bar that diameter is Ф 40-Ф 80mm;
(3) heat treatment
Bar is carried out solution treatment in chamber type electric resistance furnace, solid solubility temperature is 860-900 DEG C, solution time is 15-45min, carries out shrend after solid solution, then carries out interrupted aging process: the bar after shrend is added Ar gas shielded in vacuum drying oven and is heated to 450-480 DEG C, insulation 2-3h, then furnace cooling is to 280-310 DEG C, insulation 3-4h, and then furnace cooling is to 180-220 DEG C, insulation 5-6h, then uses water cooling;
Further, the coating of its outside is obtained by following steps: the bar that step (3) is obtained then carries out following steps,
(4) surface preparation: washing: be first clean in the hot water of 90-100 DEG C in temperature by the titanium alloy rod bar after heat treatment, then cleans with the flowing cool water of room temperature; Sandblasting: dry up titanium alloy rod bar with compressed air, then blows and sprays quartz sand, and removal machine adds vestige, increases roughness; Alkali cleaning: titanium alloy rod bar be impregnated in temperature in the alkali fusion liquid of 350-550 DEG C, dip time is 30-60min, described alkali fusion liquid is that 70 ~ 80% sodium hydroxide and 20 ~ 30% Chile saltpeters mix and form by percentage by weight; Pickling: pickling processes is carried out to Surface of Rod Bar, being immersed in temperature is 15-45min in 40-50 DEG C of pickle, wherein: pickle consists of (weight): take 98% concentrated sulphuric acid 20-30 part, HCl 6-8 part of 36.5%, di-alkyl-imidazole hyamine 1-2 part, ethylenediamine 1-3 part, water 30-60 part; Passivation Treatment: the titanium alloy rod bar after pickling be impregnated in temperature at 90 ~ 150 DEG C, concentration is the Chile saltpeter of 150 ~ 200g/l, in the aqueous solution of the sodium fluoride of 15-45g/l, controls Fe in solution
3+concentration < 20g/l, dip time is 15-20min;
(5) surface coating injection: coating spraying raw material is (weight portion): titanium oxide powder: 60-80 part, silver powder: 0.1-1 part; Wollastonite in powder: 15-20 part; Oxidation argentum powder: 0.1-0.5 part; Titanium boride powder: 2-4 part; Magnesia powder: 4-8 part; Adopt atmospheric plasma spraying technique by after above-mentioned powder mixing, be sprayed on titanium alloy rod bar, plasma spray process parameter is the flow of arc-plasma gas Ar is 15-30 standard liter/min, arc-plasma gas H
2flow be 15-20 standard liter/min, the flow of powder carrier gas Ar is 0.5-2.5 standard liter/min, and spray distance is 40-60mm, and powder feeding rate is 5-10g/min, and spraying current is 450-600A, and coating thickness is 0.5-3mm; After spraying, titanium alloy rod bar is added in vacuum drying oven Ar gas shielded to heat-treat, first, be heated 550-650 DEG C, insulation 1-2 hour, then furnace cooling is to 150-200 DEG C, insulation 24-48 hour, then furnace cooling.
Further, the chemical composition of described ingot blank is: zirconium 8%, niobium 4.8%, ferrum: 2%, chromium: 0.75%, gallium: 0.65%, stannum: 0.34%, hafnium: 0.04%, tantalum: 1.56%, aluminum: 1.45%, vanadium: 0.33%, boron: 0.16%, cerium: 0.14%, molybdenum: 10.2%, silver: 0.0015%, surplus is titanium.
Further, coating spraying raw material consists of (weight portion): titanium oxide powder: 70 parts, silver powder: 0.35 part; Wollastonite in powder: 18 parts; Oxidation argentum powder: 0.2 part; Titanium boride powder: 3 parts; Magnesia powder: 5.6 parts.
Further, pickle consists of (weight): take 98% concentrated sulphuric acid 25 parts, the HCl of 36.5% 7 parts, di-alkyl-imidazole hyamine 1.5 parts, ethylenediamine 1.4 parts, 45 parts, water; Inactivating treatment liquid is: concentration is the aqueous solution of the Chile saltpeter of 160g/l, the sodium fluoride of 22g/l.
Effect of the present invention is: be optimized titanium alloy component, distortion, surface treatment, heat treating regime, makes the performance of titanium alloy rod bar more excellent; Such technique refinement coordinates, and the preparation process refinement more of the medical titanium alloy bar making antibacterial ability strong, ensure that quality, and alloy mechanical property is excellent, can be used as the substitution material of the hard tissue repair such as bone, joint and artificial tooth root.
Detailed description of the invention
Embodiment 1
The medical titanium alloy bar that antibacterial ability is strong, its preparation method, comprises the following steps:
(1) ingot blank preparation: the chemical composition of described ingot blank is: zirconium 6.5%, niobium 6.8%, ferrum: 1.95%, chromium: 0.68%, gallium: 0.72%, stannum: 0.38%, hafnium 0.05%, tantalum 1.66%, aluminum: 1.59%, vanadium: 0.28%, boron: 0.165%, cerium: 0.17%, molybdenum: 10.43%, silver: 0.0025%, surplus is titanium;
By alloying component mass percent batching, melting in fine vacuum arc heating furnace, fully stirs, be cast into ingot blank, ingot blank added in vacuum drying oven Ar gas shielded and heat-treat, ingot blank is warming up to 930 DEG C with 230 DEG C/h, be incubated 8 hours, then cool to 560 DEG C with 135 DEG C/h, be incubated 4 hours, then cool to 285 DEG C with 85 DEG C/h, be incubated 5 hours, continue to cool to 186 DEG C with 58 DEG C/h, be incubated 2.5 hours, then furnace cooling is to room temperature;
(2) forging molding
Surface-coated: applying one deck at surface of ingot blank is that the coating of main component prevents from being oxidized during high temperature process and increasing lubrication with boron nitride;
With 1000 tons of hydraulic presses, step ingot blank is incubated 1.4 hours at 965 DEG C,
adoptwith open die forging, final forging temperature 685 DEG C, is swaged into the square billet that the length of side is 260mm after repeated multiple times;
Be the square billet cool to room temperature of 260mm by the length of side, the blank heating after thinning surface defect is to 930 DEG C of jumping-ups and pull out distortion 4 times, final forging temperature 775 DEG C, pass deformation 30%;
Then forging stock cool to room temperature, after thinning surface defect, is heated to 720 DEG C of jumping-ups and pulls out forging 4 times, pass deformation 25%;
By the forging stock cool to room temperature that upsetting pull is forged, after thinning surface defect, then be heated to 695 DEG C of jumping-ups and pull out forging 3 times, pass deformation 45%; And the last time pulling forging time chamfered edge, round as a ball;
By upsetting pull forge forging stock cool to room temperature, after thinning surface defect, then be heated to 735 DEG C of chamfered edges, round as a ball, pulling be swaged to the bar that diameter is Ф 45mm;
(3) heat treatment
Bar is carried out solution treatment in chamber type electric resistance furnace, solid solubility temperature is 880 DEG C, solution time is 20min, carries out shrend after solid solution, then carries out interrupted aging process: the bar after shrend is added Ar gas shielded in vacuum drying oven and is heated to 460 DEG C, insulation 2.5h, then furnace cooling is to 290 DEG C, insulation 3h, and then furnace cooling is to 185 DEG C, insulation 5.5h, then uses water cooling;
(4) surface preparation: washing: be first clean in the hot water of 90 DEG C in temperature by the titanium alloy rod bar after heat treatment, then cleans with the flowing pure water of room temperature; Sandblasting: dry up titanium alloy rod bar with compressed air, then blows and sprays quartz sand, and removal machine adds vestige, increases roughness; Alkali cleaning: titanium alloy rod bar be impregnated in temperature in the alkali fusion liquid of 420 DEG C, dip time is 35min, described alkali fusion liquid is that 75% sodium hydroxide and 25% Chile saltpeter mix and form by percentage by weight; Pickling: pickling processes is carried out to Surface of Rod Bar, being immersed in temperature is 18min in 45 DEG C of pickles, wherein: pickle consists of (weight): take 98% concentrated sulphuric acid 28 parts, the HCl of 36.5% 7 parts, di-alkyl-imidazole hyamine 1.6 parts, ethylenediamine 2.3 parts, 35 parts, water; Passivation Treatment: the titanium alloy rod bar after pickling be impregnated in temperature at 95 DEG C, concentration is the Chile saltpeter of 170g/l, in the aqueous solution of the sodium fluoride of 22g/l, controls Fe in solution
3+concentration < 20g/l, dip time is 16min;
(5) surface coating injection: coating spraying raw material is (weight portion): titanium oxide powder: 65 parts, silver powder: 0.18 part; Wollastonite in powder: 18 parts; Oxidation argentum powder: 0.22 part; Titanium boride powder: 2.8 parts; Magnesia powder: 4.7 parts; Adopt atmospheric plasma spraying technique by after above-mentioned powder mixing, be sprayed on titanium alloy rod bar, plasma spray process parameter is the flow of arc-plasma gas Ar is 23 standard liter/min, arc-plasma gas H
2flow be 17 standard liter/min, the flow of powder carrier gas Ar is 1.6 standard liter/min, and spray distance is 45mm, and powder feeding rate is 8g/min, and spraying current is 460A, and coating thickness is 1.2mm; After spraying, titanium alloy rod bar is added in vacuum drying oven Ar gas shielded to heat-treat, first, be heated 580 DEG C, be incubated 1.3 hours, then furnace cooling is to 180 DEG C, is incubated 29 hours, then furnace cooling.
Embodiment 2
The medical titanium alloy bar that antibacterial ability is strong, its preparation method, comprises the following steps:
(1) ingot blank preparation: the chemical composition of described ingot blank is: zirconium 9.5%, niobium 8.25%, ferrum: 1.58%, chromium: 0.72%, gallium: 0.88%, stannum: 0.28%, hafnium 0.06%, tantalum 1.6%, aluminum: 1.3%, vanadium: 0.27%, boron: 0.145%, cerium: 0.166%, molybdenum: 11.3%, silver: 0.0035% surplus is titanium;
By alloying component mass percent batching, melting in fine vacuum arc heating furnace, fully stirs, be cast into ingot blank, ingot blank added in vacuum drying oven Ar gas shielded and heat-treat, ingot blank is warming up to 930 DEG C with 230 DEG C/h, be incubated 7 hours, then cool to 570 DEG C with 130 DEG C/h, be incubated 4.5 hours, then cool to 295 DEG C with 84 DEG C/h, be incubated 3.5 hours, continue to cool to 185 DEG C with 58 DEG C/h, be incubated 3.5 hours, then furnace cooling is to room temperature;
(2) forging molding
Surface-coated: applying one deck at surface of ingot blank is that the coating of main component prevents from being oxidized during high temperature process and increasing lubrication with boron nitride;
With 1000 tons of hydraulic presses, step ingot blank is incubated 1.8 hours at 940 DEG C,
adoptwith open die forging, final forging temperature 690 DEG C, is swaged into the square billet that the length of side is 260mm after repeated multiple times;
Be the square billet cool to room temperature of 260mm by the length of side, the blank heating after thinning surface defect is to 930 DEG C of jumping-ups and pull out distortion 4 times, final forging temperature 780 DEG C, pass deformation 35%;
Then forging stock cool to room temperature, after thinning surface defect, is heated to 720 DEG C of jumping-ups and pulls out forging 4 times, pass deformation 25%;
By the forging stock cool to room temperature that upsetting pull is forged, after thinning surface defect, then be heated to 700 DEG C of jumping-ups and pull out forging 2 times, pass deformation 45%; And the last time pulling forging time chamfered edge, round as a ball;
By upsetting pull forge forging stock cool to room temperature, after thinning surface defect, then be heated to 732 DEG C of chamfered edges, round as a ball, pulling be swaged to the bar that diameter is Ф 55mm;
(3) heat treatment
Bar is carried out solution treatment in chamber type electric resistance furnace, solid solubility temperature is 870 DEG C, solution time is 40min, carries out shrend after solid solution, then carries out interrupted aging process: the bar after shrend is added Ar gas shielded in vacuum drying oven and is heated to 460 DEG C, insulation 2.5h, then furnace cooling is to 290 DEG C, insulation 3.5h, and then furnace cooling is to 195 DEG C, insulation 5h, then uses water cooling;
(4) surface preparation: washing: be first clean in the hot water of 95 DEG C in temperature by the titanium alloy rod bar after heat treatment, then cleans with the flowing cool water of room temperature; Sandblasting: dry up titanium alloy rod bar with compressed air, then blows and sprays quartz sand, and removal machine adds vestige, increases roughness; Alkali cleaning: titanium alloy rod bar be impregnated in temperature in the alkali fusion liquid of 395 DEG C, dip time is 45min, described alkali fusion liquid is that 72% sodium hydroxide and 28% Chile saltpeter mix and form by percentage by weight; Pickling: pickling processes is carried out to Surface of Rod Bar, being immersed in temperature is 18min in 48 DEG C of pickles, wherein: pickle consists of (weight): take 98% concentrated sulphuric acid 26 parts, the HCl of 36.5% 6.7 parts, di-alkyl-imidazole hyamine 1.88 parts, ethylenediamine 1.35 parts, 40 parts, water; Passivation Treatment: the titanium alloy rod bar after pickling be impregnated in temperature at 110 DEG C, concentration is the Chile saltpeter of 175g/l, in the aqueous solution of the sodium fluoride of 26g/l, controls Fe in solution
3+concentration < 20g/l, dip time is 17min;
(5) surface coating injection: coating spraying raw material is (weight portion): titanium oxide powder: 68 parts, silver powder: 0.35 part; Wollastonite in powder: 17 parts; Oxidation argentum powder: 0.33 part; Titanium boride powder: 3.6 parts; Magnesia powder: 7.2 parts; Adopt atmospheric plasma spraying technique by after above-mentioned powder mixing, be sprayed on titanium alloy rod bar, plasma spray process parameter is the flow of arc-plasma gas Ar is 18 standard liter/min, arc-plasma gas H
2flow be 17 standard liter/min, the flow of powder carrier gas Ar is 1.25 standard liter/min, and spray distance is 43mm, and powder feeding rate is 7.8g/min, and spraying current is 510A, and coating thickness is 0.9mm; After spraying, titanium alloy rod bar is added in vacuum drying oven Ar gas shielded to heat-treat, first, be heated 590 DEG C, be incubated 1.6 hours, then furnace cooling is to 175 DEG C, is incubated 38 hours, then furnace cooling.
Claims (6)
1. the medical titanium alloy bar that an antibacterial ability is strong, it is characterized in that: described titanium alloy rod bar comprises the coating of titanium alloy rod bar body and its outside, the chemical composition of described titanium alloy rod bar body is: zirconium 7-10%, ferrum: 1.5-2.5%, chromium: 0.5-0.8%, gallium: 0.5-0.9%, stannum: 0.25-0.75%, hafnium 0.02-0.07%, tantalum 1-2%, aluminum: 1-2%, vanadium: 0.25-0.45%, boron: 0.1-0.18%, cerium: 0.12-0.18%, niobium 4-15%, molybdenum: 9-13%, silver: 0.001-0.005%, surplus is titanium; Consisting of of described outside coating: titanium oxide: 60-80 part, argent: 0.1-1 part; Wollastonite: 15-20 part; Silver oxide: 0.1-0.5 part; Titanium boride: 2-4 part, magnesia powder: 4-8 part.
2. the medical titanium alloy bar that antibacterial ability as claimed in claim 1 is strong, is characterized in that: described titanium alloy rod bar is obtained by following steps:
(1) ingot blank preparation: the chemical composition of described ingot blank is: zirconium 7-10%, ferrum: 1.5-2.5%, chromium: 0.5-0.8%, gallium: 0.5-0.9%, stannum: 0.25-0.75%, hafnium 0.02-0.07%, tantalum 1-2%, aluminum: 1-2%, vanadium: 0.25-0.45%, boron: 0.1-0.18%, cerium: 0.12-0.18%, niobium 4-15%, molybdenum: 9-13%, silver: 0.001-0.005%, surplus is titanium;
Prepare burden by alloying component mass percent, melting in fine vacuum arc heating furnace, abundant stirring, be cast into ingot blank, ingot blank is added in vacuum drying oven Ar gas shielded to heat-treat, ingot blank is warming up to 920-940 DEG C with 200-250 DEG C/h, insulation 6-10 hour, then cool to 550-580 DEG C with 120-150 DEG C/h, insulation 2-6 hour, then cools to 280-320 DEG C with 80-90 DEG C/h, insulation 2-5 hour, continue to cool to 180-190 DEG C with 50-65 DEG C/h, insulation 2-5 hour, then furnace cooling is to room temperature;
(2) forging molding
Surface-coated: applying one deck at surface of ingot blank is that the coating of main component prevents from being oxidized during high temperature process and increasing lubrication with boron nitride;
With 1000 tons of hydraulic presses, step ingot blank is incubated 1-2 hour at 900-1000 DEG C,
adoptwith open die forging, final forging temperature 660-720 DEG C, is swaged into the square billet that the length of side is 200-300mm after repeated multiple times;
Be the square billet cool to room temperature of 200-300mm by the length of side, the blank heating after thinning surface defect is out of shape 3-6 time to 900-950 DEG C of jumping-up and pulling, final forging temperature 770-810 DEG C, pass deformation 20-45%, and total deformation adds up 70-130%;
Then forging stock cool to room temperature, after thinning surface defect, is heated to 700-740 DEG C of jumping-up and pulls out forging 3-6 time, pass deformation 15-30%, accumulative total deformation 55-110%;
By the forging stock cool to room temperature that upsetting pull is forged, after thinning surface defect, then be heated to 680-720 DEG C of jumping-up and pull out forging 2-3 time, pass deformation 40-50%; And the last time pulling forging time chamfered edge, round as a ball;
By upsetting pull forge forging stock cool to room temperature, after thinning surface defect, then be heated to 730-740 DEG C of chamfered edge, round as a ball, pulling be swaged to the bar that diameter is Ф 40-Ф 80mm;
(3) heat treatment
Bar is carried out solution treatment in chamber type electric resistance furnace; solid solubility temperature is 860-900 DEG C; solution time is 15-45min, carries out shrend after solid solution, then carries out interrupted aging process: the bar after shrend is added Ar gas shielded in vacuum drying oven and is heated to 450-480 DEG C; insulation 2-3h; then furnace cooling is to 280-310 DEG C, insulation 3-4h, and then furnace cooling is to 180-220 DEG C; insulation 5-6h, then uses water cooling.
3. the medical titanium alloy bar that the antibacterial ability as described in claim 1-2 is strong, is characterized in that: the coating of its outside is obtained by following steps: the bar that step (3) is obtained then carries out following steps,
(4) surface preparation: washing: be first clean in the hot water of 90-100 DEG C in temperature by the titanium alloy rod bar after heat treatment, then cleans with the flowing cool water of room temperature; Sandblasting: dry up titanium alloy rod bar with compressed air, then blows and sprays quartz sand, and removal machine adds vestige, increases roughness; Alkali cleaning: titanium alloy rod bar be impregnated in temperature in the alkali fusion liquid of 350-550 DEG C, dip time is 30-60min, described alkali fusion liquid is that 70 ~ 80% sodium hydroxide and 20 ~ 30% Chile saltpeters mix and form by percentage by weight; Pickling: pickling processes is carried out to Surface of Rod Bar, being immersed in temperature is 15-45min in 40-50 DEG C of pickle, wherein: pickle consists of (weight): take 98% concentrated sulphuric acid 20-30 part, HCl 6-8 part of 36.5%, di-alkyl-imidazole hyamine 1-2 part, ethylenediamine 1-3 part, water 30-60 part; Passivation Treatment: the titanium alloy rod bar after pickling be impregnated in temperature at 90 ~ 150 DEG C, concentration is the Chile saltpeter of 150 ~ 200g/l, in the aqueous solution of the sodium fluoride of 15-45g/l, controls Fe in solution
3+concentration < 20g/l, dip time is 15-20min;
(5) surface coating injection: coating spraying raw material is (weight portion): titanium oxide powder: 60-80 part, silver powder: 0.1-1 part; Wollastonite in powder: 15-20 part; Oxidation argentum powder: 0.1-0.5 part; Titanium boride powder: 2-4 part; Magnesia powder: 4-8 part; Adopt atmospheric plasma spraying technique by after above-mentioned powder mixing, be sprayed on titanium alloy rod bar, plasma spray process parameter is the flow of arc-plasma gas Ar is 15-30 standard liter/min, arc-plasma gas H
2flow be 15-20 standard liter/min, the flow of powder carrier gas Ar is 0.5-2.5 standard liter/min, and spray distance is 40-60mm, and powder feeding rate is 5-10g/min, and spraying current is 450-600A, and coating thickness is 0.5-3mm; After spraying, titanium alloy rod bar is added in vacuum drying oven Ar gas shielded to heat-treat, first, be heated 550-650 DEG C, insulation 1-2 hour, then furnace cooling is to 150-200 DEG C, insulation 24-48 hour, then furnace cooling.
4. the medical titanium alloy bar that antibacterial ability as claimed in claim 1 is strong, is characterized in that: the chemical composition of described ingot blank is: zirconium 8%, niobium 4.8%, ferrum: 2%, chromium: 0.75%, gallium: 0.65%, stannum: 0.34%, hafnium: 0.04%, tantalum: 1.56%, aluminum: 1.45%, vanadium: 0.33%, boron: 0.16%, cerium: 0.14%, molybdenum: 10.2%, silver: 0.0015%, surplus is titanium.
5. the medical titanium alloy bar that antibacterial ability as claimed in claim 1 is strong, is characterized in that: coating spraying raw material consists of (weight portion): titanium oxide powder: 70 parts, silver powder: 0.35 part; Wollastonite in powder: 18 parts; Oxidation argentum powder: 0.2 part; Titanium boride powder: 3 parts; Magnesia powder: 5.6 parts.
6. the medical titanium alloy bar that antibacterial ability as claimed in claim 3 is strong, it is characterized in that: pickle consists of (weight): take 98% concentrated sulphuric acid 25 parts, the HCl of 36.5% 7 parts, di-alkyl-imidazole hyamine 1.5 parts, ethylenediamine 1.4 parts, 45 parts, water; Inactivating treatment liquid is: concentration is the aqueous solution of the Chile saltpeter of 160g/l, the sodium fluoride of 22g/l.
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