CN103933607B - The preparation method of the organic strontium coating of TC4 titanium alloy surface - Google Patents
The preparation method of the organic strontium coating of TC4 titanium alloy surface Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 57
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910001427 strontium ion Inorganic materials 0.000 claims abstract description 16
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 16
- 150000003438 strontium compounds Chemical class 0.000 abstract description 11
- 210000000988 bone and bone Anatomy 0.000 abstract description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000007943 implant Substances 0.000 abstract description 6
- 230000002138 osteoinductive effect Effects 0.000 abstract description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 abstract description 5
- 230000006698 induction Effects 0.000 abstract description 4
- 108090000723 Insulin-Like Growth Factor I Proteins 0.000 abstract description 2
- 102000013275 Somatomedins Human genes 0.000 abstract description 2
- 229910000883 Ti6Al4V Inorganic materials 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 235000013619 trace mineral Nutrition 0.000 abstract description 2
- 239000011573 trace mineral Substances 0.000 abstract description 2
- 241001597008 Nomeidae Species 0.000 abstract 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 238000001727 in vivo Methods 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229960003638 dopamine Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical class CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000024279 bone resorption Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010883 osseointegration Methods 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses the preparation method of the organic strontium coating of a kind of TC4 titanium alloy surface; With medical TC4 titanium alloy (Ti-6Al-4V) for matrix, in the method for the organic strontium coating of its surface construction degradable, object is the quick reparation of induction bone.Based on the distinctive osteoinductive of trace element strontium, strontium ion is carried on titanium alloy surface by the derivant of carboxymethyl cellulose, prepares the organic strontium compound of degradation-type.By strontium ion degraded release in vivo, reach the object that cambium is repaired fast at implant surface growth, promotion bone.The present invention can solve in the past that coating osteoinductive is poor, the limitation that somatomedin costliness, easy in inactivation, action time are short, is conducive to developing cheap, efficient, stable bone induction material.
Description
Technical field
The present invention relates to a kind of novel method of repairing fast with organic strontium modification TC4 titanium alloy (Ti-6Al-4V) material surface induction bone, be mainly used in the fields such as biological and medicine, medical equipment.
Background technology
Strontium (Strontium, Sr) is a kind of trace element, and it is of the same clan with calcium in the periodic table of elements.In recent years, strontium is found to have the non-couple of the uniqueness improving osteogenic activity and suppress broken bone resorption, and it has huge potential using value at orthopaedics.Titanium alloy, because excellent in mechanical performance, corrosion resistance are strong and the advantage such as good biocompatibility, is widely used as the material of main part of orthopaedics implant.But titanium alloy is biologically inert, itself and implant site osseointegration property are poor, are easily separated with surrounding host tissue and cause loosening, therefore, titanium alloy surface modified, promotes the repair ability of implant site osseous tissue, shorten the research focus that healing time becomes medical titanium alloy.There is the limitation such as fragility is large, residual stress is high, osteoinductive is poor in existing inorganic coating; Organic polymer is the development trend that titanium alloy surface is modified, but it is without osteoinductive.To sum up consider, the present invention proposes to synthesize organic strontium compound to modify titanium alloy surface, and promotes the quick reparation of implant site osseous tissue by the release of the degraded and strontium ion that control material.This, for the surgical effect promoting titanium alloy apparatus, improves quality of life of patients, saves social medical resource and have significant effect.
Summary of the invention
The object of the invention is to propose a kind of effectively can improve titanium alloy osteoinductive, promote that implant and bone are integrated fast, and can be used for clinical key technology.
By regulation and control reactant CMC-Na and DOPAHCl mol ratio 1:1, utilize 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides (EDC)/N-hydroxysuccinimide (NHS) to activate the carboxymethyl of CMC, preparation has the organic compound (DOPA-CMC) of strontium ion binding site.Namely strontium ion is obtained organic strontium compound (DOPA-CMC-Sr) by the carboxyl chelating in above-mentioned Organic substance.
DOPA-CMC-Sr technology of preparing route
The preparation method of the organic strontium coating of TC4 titanium alloy surface of the present invention, step is as follows:
(1) Homogeneous phase mixing under the effect of coupling agent by the sodium carboxymethyl cellulose solution of equimolar amounts and the tris solution of dopamine hydrochloride;
(2) six water strontium chloride aqueous solutions are added in above-mentioned steps (1) gained solution, Homogeneous phase mixing;
(3) be soaked in by titanium alloy sheet in step (2) gained solution, lucifuge is reacted, and spends the night, dry after taking out, and obtains the organic strontium coating of TC4 titanium alloy surface; As shown in Figure 1.
Selected TC4 titanium alloy sheet, as coated substrate, first can carry out pretreatment, by it after liquid honing cleans up, through nitric acid and NaOH pretreatment first, and drying for standby.
The molecular weight of described sodium carboxymethyl cellulose is preferably 100kDa ~ 250kDa.(kDa is the molecular mass unit of protein in biology).
The concentration range of described dopamine hydrochloride is preferably 1mg/ml ~ 5mg/ml.
The coupling agent of described step (1) is 1-ethyl-3-(3-dimethyl aminopropyl)-carbodiimides (EDC)/N-hydroxysuccinimide (NHS).
In described step (2) gained mixed solution, the concentration of strontium ion is 5mg/ml ~ 15mg/ml.
By above method, modify with organic strontium compound the quick reparation that titanium alloy surface can promote bone.The limitation that the present invention can solve in the past that coating osteoinductive is poor, somatomedin is expensive, easy in inactivation, action time are short, is conducive to developing cheap, efficient, stable bone induction material.
Accompanying drawing explanation
The structure process chart of the organic strontium coating in the titanium alloy-based surface of Fig. 1 TC4;
Infrared spectrum (FT-IR) figure of Fig. 2 DOPA-CMC and DOPA-CMC-Sr;
Fig. 3 a TC4 titanium alloy scanning electron microscope after acid-alkali treatment (SEM) spectrogram;
X-ray energy spectrum analysis (EDS) figure of Fig. 3 b TC4 titanium alloy after acid-alkali treatment;
Scanning electron microscope (SEM) spectrogram of organic strontium coating on Fig. 4 a TC4 titanium alloy;
X-ray energy spectrum analysis (EDS) figure of organic strontium coating on Fig. 4 b TC4 titanium alloy;
X-ray photoelectron power spectrum (XPS) figure of Fig. 5 a TC4 titanium alloy after acid-alkali treatment;
X-ray photoelectron power spectrum (XPS) figure not containing strontium organic coating on Fig. 5 b TC4 titanium alloy;
X-ray photoelectron power spectrum (XPS) figure of organic strontium coating on Fig. 5 c TC4 titanium alloy;
X-ray photoelectron power spectrum (XPS) figure of strontium element in organic strontium coating on Fig. 5 d TC4 titanium alloy.
Detailed description of the invention
Illustrate technology of the present invention and concrete implementation column below:
Embodiment 1:
With TC4 titanium alloy for matrix, prepare the method for organic strontium coating, utilize the characteristic of strontium ion and carboxyl chelating to prepare organic strontium compound, the characteristic utilizing the o-phenol functional group of dopamine and substrate to combine closely is by immobilized in titanium alloy surface for this organic strontium compound.
Described with TC4 titanium alloy for matrix, be of a size of 10*10*2mm
3tC4 titanium alloy sheet
The technological parameter of the organic strontium coating of preparation TC4 titanium alloy surface is:
HNO
3concentration and etching time: 40%, 40min
NaOH concentration and temperature retention time: 5mol/L, 5h
DOPAHCl concentration: 1mg/ml
SrCl
26H
2o concentration: 5mg/ml
Preparation method and the step thereof of above-mentioned coating are as follows:
(1) linear cutter is utilized to become 10 × 10 × 2mm on sample
3, use 600# respectively, 800#, 2500# sand paper is polished, dehydrated alcohol ultrasonic cleaning, dry.
(2) acid, oxygenation pretreatment are carried out in the surface of said sample, successively 40% HNO
3corrode 40min in solution, be incubated 5h in the NaOH solution of 5mol/L at 90 DEG C, washed with de-ionized water is clean, and dehydrated alcohol is drying for standby after ultrasonic 15 minutes.
(3) configure the CMC aqueous solution of 1%, in solution, add the EDC of equimolar amounts, stir 15min under magnetic stirring apparatus after, add the NHS of equimolar amounts, reaction 40min.
(4) the Tris solution of the DOPAHCl of 1mg/ml is configured, pH=8.5, makes it fully dissolve under light protected environment.
(5) add in the solution of step (3) by the solution of step (4), under magnetic stirring apparatus, stirring 1h to solution is uniform solution.
(6) SrCl is configured
26H
2o solution, uses the filter of 0.22um to be filtered in step (5) gained solution, fully dissolves, make the concentration of strontium ion in mixed solution be 5mg/ml.
(7) sample that step (1) prepares is put into step (6) gained solution and soak 24h, keep in Dark Place.Leave standstill to the solution in titanium sheet dry after sample is taken out, with washed with de-ionized water several, put into 56 DEG C of drying baker dry, obtain organic strontium coating of TC4 titanium alloy surface.
Embodiment 2:
With TC4 titanium alloy for matrix, prepare the method for organic strontium coating, it is characterized in that: utilize the characteristic of strontium ion and carboxyl chelating to prepare organic strontium compound, the characteristic utilizing the o-phenol functional group of dopamine and substrate to combine closely is by immobilized in titanium alloy surface for this organic strontium compound.
Described with TC4 titanium alloy for matrix, be of a size of 10*10*2mm
3tC4 titanium alloy sheet
The technological parameter of the organic strontium coating of preparation TC4 titanium alloy surface is:
HNO
3concentration and etching time: 50%, 1h
NaOH concentration and temperature retention time: 5mol/L, 7h
DOPAHCl concentration: 5mg/ml
SrCl
26H
2o concentration: 10mg/ml
Preparation method and the step thereof of coating described above are as follows:
(1) linear cutter is utilized to become 10 × 10 × 2mm on sample
3, use 600# respectively, 800#, 2500# sand paper is polished, dehydrated alcohol ultrasonic cleaning, dry.
(2) acid, oxygenation pretreatment are carried out in the surface of said sample, successively 50% HNO
3corrode 1h in solution, be incubated 7h in the NaOH solution of 5mol/L at 90 DEG C, washed with de-ionized water is clean, and dehydrated alcohol is drying for standby after ultrasonic 15 minutes.(3) configure the CMC aqueous solution of 1%, in solution, add the EDC of equimolar amounts, stir 15min under magnetic stirring apparatus after, add the NHS of equimolar amounts, reaction 40min.
(4) configure the Tris solution of the DOPAHCl of 5mg/ml, pH=8.5, makes it fully dissolve under light protected environment.
(5) add in the solution of step (3) by the solution of step (4), under magnetic stirring apparatus, stirring 1h to solution is uniform solution.
(6) SrCl is configured
26H
2o solution, uses the filter of 0.22um to be filtered in step (5) gained solution, fully dissolves, make the concentration of strontium ion in mixed solution be 10mg/ml.
(7) sample that step (1) prepares is put into step (6) gained solution and soak 24h, keep in Dark Place.Leave standstill to the solution in titanium sheet dry after sample is taken out, with washed with de-ionized water several, put into 56 DEG C of drying baker dry, obtain organic strontium coating of TC4 titanium alloy surface.
Embodiment 3:
With TC4 titanium alloy for matrix, prepare the method for organic strontium coating, it is characterized in that: utilize the characteristic of strontium ion and carboxyl chelating to prepare organic strontium compound, the characteristic utilizing the o-phenol functional group of dopamine and substrate to combine closely is by immobilized in titanium alloy surface for this organic strontium compound.
Described with TC4 titanium alloy for matrix, be of a size of 10*10*2mm
3tC4 titanium alloy sheet
The technological parameter of the organic strontium coating of preparation TC4 titanium alloy surface is:
HNO
3concentration and etching time: 60%, 2h
NaOH concentration and temperature retention time: 5mol/L, 5h
DOPAHCl concentration: 5mg/ml
SrCl
26H
2o concentration: 15mg/ml
Preparation method and the step thereof of coating described above are as follows:
(1) linear cutter is utilized to become 10 × 10 × 2mm on sample
3, use 600# respectively, 800#, 2500# sand paper is polished, dehydrated alcohol ultrasonic cleaning, dry.
(2) acid, oxygenation pretreatment are carried out in the surface of said sample, successively 60% HNO
3corrode 2h in solution, be incubated 5h in the NaOH solution of 5mol/L at 90 DEG C, washed with de-ionized water is clean, and dehydrated alcohol is drying for standby after ultrasonic 15 minutes.
(3) configure the CMC aqueous solution of 1%, in solution, add the EDC of equimolar amounts, stir 15min under magnetic stirring apparatus after, add the NHS of equimolar amounts, reaction 40min.
(4) configure the Tris solution of the DOPAHCl of 5mg/ml, make it fully dissolve under light protected environment.
(5) add in the solution of step (3) by the solution of step (4), under magnetic stirring apparatus, stirring 1h to solution is uniform solution.
(6) SrCl is configured
26H
2o solution, uses the filter of 0.22um to be filtered in step (5) gained solution, fully dissolves, make the concentration of strontium ion in mixed solution be 15mg/ml.
(7) sample that step (1) prepares is put into step (6) gained solution and soak 24h, keep in Dark Place.Leave standstill to the solution in titanium sheet dry after sample is taken out, with washed with de-ionized water several, put into 56 DEG C of drying baker dry, obtain organic strontium coating of TC4 titanium alloy surface.
Characterizing method and effect as follows:
(1) infrared spectrum (FT-IR) figure is utilized to characterize above-mentioned Organic substance, as shown in Figure 2.Correspondence C=O(1700cm can be found out in feature spectrogram
-1), N-H(1490cm
-1) characteristic peak, prove the generation of amido link in polymer.In addition, also can find from the Comparative result before and after chelating strontium, infrared spectrum variation tendency is similar, proves that the chelating of strontium does not change the backbone structure of polymer.In order to prove that strontium ion to be chelated in polymer and the strontium element that is chelated of quantitative analysis, after micro-wave digestion, ICP-MS test is carried out to organic strontium compound.In test result show sample, Sr constituent content is: 70.099mg/g.
(2) for improving the bond strength of coating and matrix, dopamine and titanium alloy substrate is adopted to combine.The organic strontium in the titanium alloy-based surface of TC4 is coated with the technological process of layer building as shown in Figure 1, utilize the characteristic that o-phenol functional group and substrate are combined closely, the DOPA-CMC of above-mentioned preparation being combined with titanium alloy substrate, forming organic strontium coating finally by being sequestered in its surface with strontium ion.The surface topography before and after the organic strontium coating of matrix load is observed, as shown in Fig. 3 a, Fig. 4 a with scanning electron microscope (SEM).Fig. 3 a represents the surface topography of matrix before the organic strontium coating of load, and matrix surface presents cellular.Fig. 4 a represents the surface topography after the organic strontium coating of load, can find out that the pattern of titanium alloy surface before and after load coating has obvious difference by the contrast of two width figure, the latter can find out has the uniform load of material of one deck similar gels shape at matrix surface.Composition and the structure of titanium alloy substrate Surface Creation product is characterized, as shown in Fig. 3 b, Fig. 4 b and Fig. 5 with X-ray energy spectrum, x-ray photoelectron power spectrum etc.Discovery can be contrasted from X-ray energy spectrum Fig. 3 b and Fig. 4 b, compared to the matrix (Fig. 3 b) before the organic strontium coating of load, after load organic strontium coating there is the peak that Sr is corresponding in matrix surface, and the peak value that Ti element is corresponding weakens, illustrate that matrix covers by organic strontium coating, as shown in Figure 4 b.In addition, carry out x-ray photoelectron power spectrum (XPS) to the composition before and after the organic strontium coating of matrix surface load to characterize, compared to the XPS spectrum figure before load coating (Fig. 5 a), can find from Fig. 5 b/5c, the peak that after load coating, the Ti of titanium alloy surface is corresponding weakens gradually or disappears, after chelating strontium element, there is the peak corresponding to Sr in fig. 5 c, and be in the 3d track (shown in Fig. 5 d) that combination can be 133.919 places, also again can verify that organic strontium coating can be uniformly distributed in titanium alloy-based surface in polymer form by above result.
(3) the external degradation performance of test compound material in simulated body fluid, with the release behavior of atomic absorption spectrum monitoring strontium ion; By above sign, sum up contacting between organic strontium structure and degradation characteristic, optimize organic constitution further.
Claims (3)
1. a preparation method for the organic strontium coating of TC4 titanium alloy surface, is characterized in that step is as follows:
(1) configure sodium carboxymethyl cellulose solution, in solution, add the EDC of equimolar amounts, stir 15min under magnetic stirring apparatus after, add the NHS of equimolar amounts, reaction 40min;
(2) configure the tris solution of the dopamine hydrochloride of 1mg/ml ~ 5mg/ml, pH=8.5, makes it fully dissolve under light protected environment;
(3) added in the solution of step (1) by the solution of step (2), make the mol ratio of sodium carboxymethyl cellulose and dopamine hydrochloride be 1:1, under magnetic stirring apparatus, be stirred to solution is uniform solution;
(4) SrCl is configured
26H
2o solution, use the filter of 0.22 μm to be filtered in step (3) gained solution, fully dissolve, in mixed solution, the concentration of strontium ion is 5mg/ml ~ 15mg/ml;
(5) TC4 titanium alloy sheet is put into step (4) gained solution and soak 24h, keep in Dark Place; Leave standstill to the solution in titanium sheet dry after sample is taken out, with washed with de-ionized water several, put into 56 DEG C of drying baker dry, obtain organic strontium coating of TC4 titanium alloy surface.
2. the method for claim 1, is characterized in that: TC4 titanium alloy sheet, as coated substrate, first carries out pretreatment, by it after liquid honing cleans up, through nitric acid and NaOH pretreatment first, dry.
3. the method for claim 1, is characterized in that: the molecular weight of described sodium carboxymethyl cellulose is 100kDa ~ 250kDa.
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| US7087085B2 (en) * | 2000-07-26 | 2006-08-08 | Straumann Holding Ag | Surface-modified implants |
| CN101829357A (en) * | 2010-03-30 | 2010-09-15 | 浙江大学 | Implant surface biomimetic coating material for promoting sacralization and preparation method thereof |
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