CN105063420B - A kind of preparation method of the medical titanium alloy bar of strong antibacterial - Google Patents
A kind of preparation method of the medical titanium alloy bar of strong antibacterial Download PDFInfo
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- CN105063420B CN105063420B CN201510476578.9A CN201510476578A CN105063420B CN 105063420 B CN105063420 B CN 105063420B CN 201510476578 A CN201510476578 A CN 201510476578A CN 105063420 B CN105063420 B CN 105063420B
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 8
- 238000005242 forging Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000005507 spraying Methods 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical class [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 230000007547 defect Effects 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 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
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 235000021110 pickles Nutrition 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000010456 wollastonite Substances 0.000 claims description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims description 5
- 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 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
- 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
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 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 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 2
- 230000000415 inactivating effect Effects 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 210000000988 bone and bone Anatomy 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 230000017423 tissue regeneration Effects 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 208000035985 Body Odor Diseases 0.000 description 3
- 206010055000 Bromhidrosis Diseases 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- -1 alkyl Imidazoline quaternary ammonium salt Chemical class 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 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
- 235000013312 flour Nutrition 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Forging (AREA)
- Materials For Medical Uses (AREA)
Abstract
A kind of preparation method of the medical titanium alloy bar of strong antibacterial, comprises the following steps：Ingot blank prepares the steps such as forging molding heat treatment surface pretreating surface coating spraying, the present invention passes through design of alloy, forging technology, heat treatment, spraying coating process optimization, technique refinement cooperation, the preparation process making medical titanium alloy bar more refines, ensure that quality, 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.
Description
Technical field
The present invention relates to a kind of preparation method of the medical titanium alloy bar of strong antibacterial, belong to medical artificial bone system
Standby technical field.
Background technology
Titanium or titanium alloy is because density is low, intensity is high, elastic modelling quantity is low, fine corrosion resistance and good biocompatibility
The advantages of and be widely used in biologic medical field, be the desirable material producing complicated surgical implant.Early stage surgery is planted
The titanium alloy entering is mainly pure titanium and Ti6Al4V alloy, but going deep into application, the deficiency of pure titanium and Ti6Al4V alloy is also
It is found, pure titanium intensity is too low, be unfit to do supporting part implantation human body, although Ti6Al4V alloy intensity is higher, the V containing
Element is harmful.Therefore, the medical titanium alloy Ti6Al7Nb substituting V with Nb is developed, and is used for the productive manpower
Joint.
Metal, pottery and macromolecular material are current three medical greatly joint prosthesis's materials, and three kinds of materials respectively have it excellent scarce
Point：Metal and pottery are widely used in negative load medical field, but metal is easy to wear and corrodes, and pottery is then
Fragility is big：Macromolecular material pliability is good but wearability and hardness are poor.Titanium alloy is due to having high intensity, toughness and corrosion-resistant
Characteristic thus become a new generation joint prosthesis's material.But simply a kind of embedding even property of machinery is integrated between titanium alloy and bone,
In vivo after long service, the abrasive dust that friction produces can affect its biologically inert to implant, thus causing local organization inflammation, contracting
Its service life short.Therefore surface modification is carried out to improve the attention that its biocompatibility causes researcher to titanium alloy.Table
Face is modified to be typically all to pass through to prepare wear-resistant bio-compatible using various face coats or thin film technique in metal base surface
Coating is used for improving mar proof, corrosion resistance and the biocompatibility of joint prosthesis, and modified surface typically has good
Good biological activity.
The present invention is directed to the limitation of existing medical joint prosthesis, in the compound painting of titanium alloy artificial boney joint surfaces preparation
Layer, improves case hardness and the bond strength of coating, and strengthens biocompatibility, promote sending out further of joint prosthesis's technology
Exhibition.
Content of the invention
The present invention is directed to the problems referred to above and proposes a kind of technique refinement, medical titanium alloy bar of good performance.
A kind of preparation method of the medical titanium alloy bar of strong antibacterial, comprises the 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%, balance of titanium
By alloying component mass percent dispensing, melting in fine vacuum arc heating furnace, it is sufficiently stirred for, is cast into ingot
Base, by ingot blank, in vacuum drying oven plus Ar gas shielded carries out heat treatment, and ingot blank is warming up to 920-940 with 200-250 DEG C/h
DEG C, it is incubated 6-10 hour, then cools to 550-580 DEG C with 120-150 DEG C/h, be incubated 2-6 hour, then with 80-90
DEG C/h cool to 280-320 DEG C, be incubated 2-5 hour, continue to cool to 180-190 DEG C with 50-65 DEG C/h, be incubated 2-5
Hour, then furnace cooling is to room temperature；
(2) forging molding
Surface-coated：Coat oxidation when one layer of coating with boron nitride as main component prevents high temperature process in surface of ingot blank
And increase lubrication；
With 1000 tons of hydraulic presses, step ingot blank is incubated 1-2 hour at 900-1000 DEG C, using open die forging, final forging temperature
660-720 DEG C, repeated multiple times after be swaged into the length of side be 200-300mm square billet；
The square billet for 200-300mm for the length of side is cooled to room temperature, the blank heating after thinning surface defect to 900-950
DEG C jumping-up and pulling deformation 3-6 time, final forging temperature 770-810 DEG C, pass deformation 20-45%, total deformation adds up 90-
130%；
Then forging stock is cooled to room temperature, after thinning surface defect, is heated to 700-740 DEG C of jumping-up and pulling is forged 3-6 time,
Pass deformation 15-30%, accumulative total deformation 90-110%；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, is heated to 680-720 DEG C of jumping-up and pulling
Forging 2-3 time, pass deformation 40-50%；And the last time pulling forging when chamfered edge, round as a ball；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, is heated to 730-740 DEG C of chamfered edge, rolling
Circle, pulling are swaged to the bar of a diameter of Ф 40- Ф 80mm；
(3) heat treatment
Bar is carried out in chamber type electric resistance furnace solution treatment, solid solubility temperature is 860-900 DEG C, solution time is 15-
45min, carries out water quenching after solid solution, then carry out interrupted aging process：Bar after water quenching is added in vacuum drying oven Ar gas shielded
It is heated to 450-480 DEG C, be incubated 2-3h, then furnace cooling to 280-310 DEG C, insulation 3-4h, then furnace cooling is to 180-
220 DEG C, it is incubated 5-6h, is then water-cooled；
(4) surface preparation：Washing：By the titanium alloy rod bar elder generation after heat treatment in temperature in 90-100 DEG C of hot water
It is carried out, be then carried out with the flowing cool water of room temperature；Sandblasting：Dry up titanium alloy rod bar with compressed air, then blow and spray
Quartz sand, removal machine adds vestige, increases roughness；Alkali cleaning：Titanium alloy rod bar be impregnated in the alkali fusion that temperature is at 350-550 DEG C
In liquid, dip time be 30-60min, described alkali fusion liquid by percentage by weight be 70～80% sodium hydroxide and 20～30%
Sodium nitrate mixing composition；Pickling：Pickling processes are carried out to Surface of Rod Bar, being immersed in temperature is 15- in 40-50 DEG C of pickle
45min, wherein：Pickle consists of（Weight）：Take 98% concentrated sulphuric acid 20-30 part, 36.5% HCl 6-8 part, double alkyl
Imidazoline quaternary ammonium salt 1-2 part, ethylenediamine 1-3 part, water 30-60 part；Passivation Treatment：Titanium alloy rod bar after pickling be impregnated in temperature
At 90～150 DEG C, concentration is the sodium nitrate of 150～200g/l to degree, in the aqueous solution of the sodium fluoride of 15-45g/l, controls in solution
Fe3+Concentration ＜ 20g/l, dip time is 15-20min；
(5) surface coating injection：Coating spraying raw material is (weight portion)：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.After above-mentioned powder is mixed
Using atmospheric plasma spraying technique, it is sprayed on titanium alloy rod bar, plasma spray process parameter is arc plasma
The flow of bromhidrosis body Ar is 15-30 standard liter/min, arc-plasma gas H2Flow 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, spray
Painting electric current is 450-600A, and coating thickness is 0.5-3mm；After spraying, by titanium alloy rod bar, in vacuum drying oven plus Ar gas shielded is carried out
Heat treatment, first, is heated to 550-650 DEG C, is incubated 1-2 hour, then furnace cooling to 150-200 DEG C, is incubated 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%, balance of titanium.
Further, coating spraying raw material consists of (weight portion)：Titanium oxide powder：70 parts, silver powder：0.35 part；Silicon
Limestone flour：18 parts；Oxidation argentum powder：0.2 part；Titanium boride powder：3 parts；Magnesia powder：5.6 part.
Further, pickle consists of（Weight）：Take 25 parts of 98% concentrated sulphuric acid, 7 parts of 36.5% HCl, double alkane
1.5 parts of base imidazoline quaternary ammonium salt, 1.4 parts of ethylenediamine, 45 parts of water；Inactivating treatment liquid is：Concentration is the sodium nitrate of 160g/l, 22g/
The aqueous solution of the sodium fluoride of l.
Effect of the invention is that：To titanium alloy component, deformation, surface treatment, heat treating regime is optimized so that titanium
The performance of alloy bar material is more excellent；Such technique refinement coordinates so that the preparation process of medical titanium alloy bar more refines,
Ensure that quality, 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.
Specific embodiment
Embodiment 1
A kind of preparation method of the medical titanium alloy bar of strong antibacterial, 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%, balance of titanium；
By alloying component mass percent dispensing, melting in fine vacuum arc heating furnace, it is sufficiently stirred for, is cast into ingot
Base, by ingot blank, in vacuum drying oven plus Ar gas shielded carries out heat treatment, and ingot blank is warming up to 930 DEG C with 230 DEG C/h, and insulation 8 is little
When, 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, insulation 5 is little
When, 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：Coat oxidation when one layer of coating with boron nitride as main component prevents high temperature process in surface of ingot blank
And increase lubrication；
With 1000 tons of hydraulic presses, step ingot blank is incubated 1.4 hours at 965 DEG C, using open die forging, 685 DEG C of final forging temperature,
It is swaged into the square billet that the length of side is 260mm after repeated multiple times；
The square billet for 260mm for the length of side is cooled to room temperature, the blank heating after thinning surface defect to 930 DEG C of jumping-ups and
Pulling deformation 4 times, 775 DEG C of final forging temperature, pass deformation 30%；
Then forging stock is cooled to room temperature, after thinning surface defect, is heated to 720 DEG C of jumping-ups and pulling is forged 4 times, passage becomes
Shape amount 25%；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, is heated to 695 DEG C of jumping-ups and pulling forging
3 times, pass deformation 45%；And the last time pulling forging when chamfered edge, round as a ball；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, be heated to 735 DEG C of chamfered edges, round as a ball, pull out
Length is swaged to the bar of a diameter of Ф 45mm；
(3) heat treatment
Bar is carried out in chamber type electric resistance furnace solution treatment, solid solubility temperature is 880 DEG C, solution time is 20min, solid solution
After carry out water quenching, then carry out interrupted aging process：By the bar after water quenching, in vacuum drying oven plus Ar gas shielded is heated to 460
DEG C, it is incubated 2.5h, then furnace cooling to 290 DEG C, be incubated 3h, then furnace cooling to 185 DEG C, be incubated 5.5h, then use water
Cooling；
(4) surface preparation：Washing：By the titanium alloy rod bar after heat treatment first temperature be 90 DEG C hot water in carry out clear
Wash, be then carried out with the flowing pure water of room temperature；Sandblasting：Dry up titanium alloy rod bar with compressed air, then blow and spray quartz
Sand, removal machine adds vestige, increases roughness；Alkali cleaning：Titanium alloy rod bar be impregnated in temperature in 420 DEG C of alkali fusion liquid, leaching
The stain time is 35min, and described alkali fusion liquid is 75% sodium hydroxide by percentage by weight and 25% sodium nitrate mixing forms；Acid
Wash：Pickling processes are carried out to Surface of Rod Bar, being immersed in temperature is 18min in 45 DEG C of pickles, wherein：Pickle consists of（Weight
Amount）：Take 28 parts of 98% concentrated sulphuric acid, 7 parts of 36.5% HCl, 1.6 parts of di-alkyl-imidazole hyamine, 2.3 parts of ethylenediamine,
35 parts of water；Passivation Treatment：Titanium alloy rod bar after pickling be impregnated in temperature at 95 DEG C, concentration is the sodium nitrate of 170g/l,
In the aqueous solution of the sodium fluoride of 22g/l, control Fe in solution3+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 part；Magnesia powder：4.7 part；After above-mentioned powder is mixed
Using atmospheric plasma spraying technique, it is sprayed on titanium alloy rod bar, plasma spray process parameter is arc plasma
The flow of bromhidrosis body Ar is 23 standard liter/min, arc-plasma gas H2Flow be 17 standard liter/min, powder carry
The flow of 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, spray
Painting thickness is 1.2mm；After spraying, by titanium alloy rod bar, in vacuum drying oven plus Ar gas shielded carries out heat treatment, first, is heated
To 580 DEG C, it is incubated 1.3 hours, then furnace cooling to 180 DEG C, it is incubated 29 hours, then furnace cooling.
Embodiment 2
A kind of preparation method of the medical titanium alloy bar of strong antibacterial, 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% balance of titanium；
By alloying component mass percent dispensing, melting in fine vacuum arc heating furnace, it is sufficiently stirred for, is cast into ingot
Base, by ingot blank, in vacuum drying oven plus Ar gas shielded carries out heat treatment, and ingot blank is warming up to 930 DEG C with 230 DEG C/h, and insulation 7 is little
When, 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
Hour, 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：Coat oxidation when one layer of coating with boron nitride as main component prevents high temperature process in surface of ingot blank
And increase lubrication；
With 1000 tons of hydraulic presses, step ingot blank is incubated 1.8 hours at 940 DEG C, using open die forging, 690 DEG C of final forging temperature,
It is swaged into the square billet that the length of side is 260mm after repeated multiple times；
The square billet for 260mm for the length of side is cooled to room temperature, the blank heating after thinning surface defect to 930 DEG C of jumping-ups and
Pulling deformation 4 times, 780 DEG C of final forging temperature, pass deformation 35%；
Then forging stock is cooled to room temperature, after thinning surface defect, is heated to 720 DEG C of jumping-ups and pulling is forged 4 times, passage becomes
Shape amount 25%；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, is heated to 700 DEG C of jumping-ups and pulling forging
2 times, pass deformation 45%；And the last time pulling forging when chamfered edge, round as a ball；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, be heated to 732 DEG C of chamfered edges, round as a ball, pull out
Length is swaged to the bar of a diameter of Ф 55mm；
(3) heat treatment
Bar is carried out in chamber type electric resistance furnace solution treatment, solid solubility temperature is 870 DEG C, solution time is 40min, solid solution
After carry out water quenching, then carry out interrupted aging process：By the bar after water quenching, in vacuum drying oven plus Ar gas shielded is heated to 460
DEG C, it is incubated 2.5h, then furnace cooling to 290 DEG C, be incubated 3.5h, then furnace cooling to 195 DEG C, be incubated 5h, then use water
Cooling；
(4) surface preparation：Washing：By the titanium alloy rod bar after heat treatment first temperature be 95 DEG C hot water in carry out
Cleaning, is then carried out with the flowing cool water of room temperature；Sandblasting：Dry up titanium alloy rod bar with compressed air, then blow and spray quartz
Sand, removal machine adds vestige, increases roughness；Alkali cleaning：Titanium alloy rod bar be impregnated in temperature in 395 DEG C of alkali fusion liquid, leaching
The stain time is 45min, and described alkali fusion liquid is 72% sodium hydroxide by percentage by weight and 28% sodium nitrate mixing forms；Acid
Wash：Pickling processes are carried out to Surface of Rod Bar, being immersed in temperature is 18min in 48 DEG C of pickles, wherein：Pickle consists of（Weight
Amount）：Take 26 parts of 98% concentrated sulphuric acid, 6.7 parts of 36.5% HCl, 1.88 parts of di-alkyl-imidazole hyamine, ethylenediamine 1.35
Part, 40 parts of water；Passivation Treatment：Titanium alloy rod bar after pickling be impregnated in temperature at 110 DEG C, concentration is the nitric acid of 175g/l
Sodium, in the aqueous solution of the sodium fluoride of 26g/l, controls Fe in solution3+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 part；Magnesia powder：7.2 part；After above-mentioned powder is mixed
Using atmospheric plasma spraying technique, it is sprayed on titanium alloy rod bar, plasma spray process parameter is arc plasma
The flow of bromhidrosis body Ar is 18 standard liter/min, arc-plasma gas H2Flow be 17 standard liter/min, powder carry
The flow of 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,
Coating thickness is 0.9mm；After spraying by titanium alloy rod bar in vacuum drying oven plus Ar gas shielded carry out heat treatment, first, by itself plus
Heat, to 590 DEG C, is incubated 1.6 hours, and then furnace cooling to 175 DEG C is incubated 38 hours, then furnace cooling.
Claims (4)
1. a kind of medical titanium alloy bar of strong antibacterial preparation method it is characterised in that：Comprise the 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%, balance of titanium；
By alloying component mass percent dispensing, melting in fine vacuum arc heating furnace, it is sufficiently stirred for, be cast into ingot blank, will
In vacuum drying oven plus Ar gas shielded carries out heat treatment to ingot blank, ingot blank is warming up to 920-940 DEG C with 200-250 DEG C/h, insulation
6-10 hour, then cools to 550-580 DEG C with 120-150 DEG C/h, is incubated 2-6 hour, is then dropped with 80-90 DEG C/h
Temperature arrives 280-320 DEG C, is incubated 2-5 hour, continues to cool to 180-190 DEG C with 50-65 DEG C/h, is incubated 2-5 hour, then
Furnace cooling is to room temperature；
(2) forging molding
Surface-coated：Coat when one layer of coating with boron nitride as main component prevents high temperature process in surface of ingot blank and aoxidize and increase
Plus lubrication；
With 1000 tons of hydraulic presses, the ingot blank that step (1) is obtained is incubated 1-2 hour at 900-1000 DEG C, using open die forging, finish-forging
Temperature 660-720 DEG C, repeated multiple times after be swaged into the length of side be 200-300mm square billet；
The square billet for 200-300mm for the length of side is cooled to room temperature, the blank heating after thinning surface defect is to 900-950 DEG C of upsetting
Thick and pulling deforms 3-6 time, final forging temperature 770-810 DEG C, pass deformation 20-45%, and total deformation adds up 70-130%；
Then forging stock is cooled to room temperature, after thinning surface defect, is heated to 700-740 DEG C of jumping-up and pulling is forged 3-6 time, passage
Deflection 15-30%, accumulative total deformation 55-110%；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, is heated to 680-720 DEG C of jumping-up and pulling forging
2-3 time, pass deformation 40-50%；And the last time pulling forging when chamfered edge, round as a ball；
The forging stock that upsetting pull is forged is cooled to room temperature, after thinning surface defect, is heated to 730-740 DEG C of chamfered edge, round as a ball, pulling
It is swaged to the bar of a diameter of Ф 40- Ф 80mm；
(3) heat treatment
Bar is carried out in chamber type electric resistance furnace solution treatment, solid solubility temperature is 860-900 DEG C, solution time is 15-45min,
Carry out water quenching after solid solution, then carry out interrupted aging process：By the bar after water quenching, in vacuum drying oven plus Ar gas shielded is heated to
450-480 DEG C, insulation 2-3h, then furnace cooling to 280-310 DEG C, insulation 3-4h, then furnace cooling to 180-220 DEG C,
Insulation 5-6h, is then water-cooled；
(4) surface preparation：Washing：Titanium alloy rod bar after heat treatment is first carried out in temperature is for 90-100 DEG C of hot water clear
Wash, be then carried out with the flowing cool water of room temperature；Sandblasting：Dry up titanium alloy rod bar with compressed air, then blow and spray quartz sand,
Removal machine adds vestige, increases roughness；Alkali cleaning：Titanium alloy rod bar be impregnated in temperature in 350-550 DEG C of alkali fusion liquid, leaching
The stain time is 30-60min, and described alkali fusion liquid is 70～80% sodium hydroxide by percentage by weight and 20～30% sodium nitrates mix
It is combined into；Pickling：Pickling processes are carried out to Surface of Rod Bar, being immersed in temperature is 15-45min in 40-50 DEG C of pickle, wherein：
Pickle composition is calculated as by weight：Take 98% concentrated sulphuric acid 20-30 part, 36.5% HCl 6-8 part, di-alkyl-imidazole quinoline season
Ammonium salt 1-2 part, ethylenediamine 1-3 part, water 30-60 part；Passivation Treatment：By the titanium alloy rod bar after pickling impregnated in temperature 90～
150 DEG C, concentration is the sodium nitrate of 150～200g/L, in the aqueous solution of the sodium fluoride of 15-45g/L, controls Fe in solution3+Concentration
＜ 20g/L, dip time is 15-20min；
(5) surface coating injection：Coating spraying raw material is calculated as by weight：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；By above-mentioned powder
Adopt atmospheric plasma spraying technique after the mixing of end, be sprayed on titanium alloy rod bar, plasma spray process parameter is electricity
The flow of arc plasma gas Ar is 15-30 standard liter/min, arc-plasma gas H2 H2Flow be 15-20 mark
Accurate 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, 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 carries out heat treatment, first, is heated to 550-650 DEG C, is incubated 1-2 hour, and then furnace cooling is to 150-200
DEG C, it is incubated 24-48 hour, then furnace cooling.
2. the method for claim 1 it is characterised 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%, balance of titanium.
3. method as claimed in claim 1 or 2 it is characterised in that：Coating spraying raw material composition is calculated as by weight：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 part.
4. method as claimed in claim 3 it is characterised in that：Pickle composition is calculated as by weight：Take 98% concentrated sulphuric acid
25 parts, 36.5% HCl7 part, 1.5 parts of di-alkyl-imidazole hyamine, 1.4 parts of ethylenediamine, 45 parts of water；Inactivating treatment liquid is：
Concentration is the sodium nitrate of 160g/L, the aqueous solution of the sodium fluoride of 22g/L.
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| CN108950353A (en) * | 2018-08-01 | 2018-12-07 | 钛格斯医疗设备（重庆）有限公司 | The medical titanium alloy processing method that a kind of grain size is small and material property is high |
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| CN110846535A (en) * | 2019-11-25 | 2020-02-28 | 江苏威拉里新材料科技有限公司 | Titanium alloy powder |
| CN112048641A (en) * | 2020-09-10 | 2020-12-08 | 沈阳中核舰航特材科技有限公司 | Manufacturing method of novel medical titanium alloy ingot |
| CN113693696A (en) * | 2021-08-03 | 2021-11-26 | 西北有色金属研究院 | Medical titanium alloy bone fixing clamp and manufacturing method thereof |
| CN114247893B (en) * | 2022-02-24 | 2022-05-17 | 西南医科大学附属医院 | Application of metal powder in field of medical materials |
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| CN103100114B (en) * | 2013-01-23 | 2014-05-21 | 西南交通大学 | Preparation method of medical metal surface slow-released growth factor coating |
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