CN103044699A - Method for preparing medical high polymer material by adopting ion implantation technology - Google Patents
Method for preparing medical high polymer material by adopting ion implantation technology Download PDFInfo
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- CN103044699A CN103044699A CN2011103070750A CN201110307075A CN103044699A CN 103044699 A CN103044699 A CN 103044699A CN 2011103070750 A CN2011103070750 A CN 2011103070750A CN 201110307075 A CN201110307075 A CN 201110307075A CN 103044699 A CN103044699 A CN 103044699A
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- ion implantation
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- 238000005468 ion implantation Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 86
- 238000005516 engineering process Methods 0.000 title abstract description 4
- 239000002861 polymer material Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 91
- 230000002924 anti-infective effect Effects 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- -1 polyoxyethylene Polymers 0.000 claims description 36
- 229910052786 argon Inorganic materials 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000004332 silver Substances 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 22
- 230000001133 acceleration Effects 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
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- 239000010949 copper Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000126 substance Substances 0.000 abstract description 5
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- 239000010410 layer Substances 0.000 description 6
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 5
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- 101100230376 Acetivibrio thermocellus (strain ATCC 27405 / DSM 1237 / JCM 9322 / NBRC 103400 / NCIMB 10682 / NRRL B-4536 / VPI 7372) celI gene Proteins 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 241000699802 Cricetulus griseus Species 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 210000001672 ovary Anatomy 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
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- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 210000004409 osteocyte Anatomy 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000011667 zinc carbonate Substances 0.000 description 3
- 235000004416 zinc carbonate Nutrition 0.000 description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
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- 210000004978 chinese hamster ovary cell Anatomy 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000003709 heart valve Anatomy 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
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- 241000222122 Candida albicans Species 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000588748 Klebsiella Species 0.000 description 1
- 241000193998 Streptococcus pneumoniae Species 0.000 description 1
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- Materials For Medical Uses (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a method for preparing medical polymer material by adopting ion implantation technology; the method comprises the steps of fixing or moving a medical high polymer material through a treatment table of ion implantation equipment, vacuumizing, introducing gas, starting a power supply of an ion implantation machine, and treating to obtain the medical high polymer material with surface anti-infection and biocompatibility; the method is simple to operate, does not influence the physical and chemical structure of the material body, and the treated high molecular material has a stable surface structure, long-acting and broad-spectrum anti-infection performance, and the cell compatibility is not lower than the inherent biocompatibility of the material.
Description
Technical field
The present invention relates to a kind for the treatment of process of medical macromolecular materials, especially relate to a kind of method that adopts ion implantation technique to prepare the medical macromolecular materials with high anti-infection property and biocompatibility.
Background technology
The medical macromolecular materials such as the wound dressings that uses now, burn dressing, bandage dressing, operation dress, Operating sheet, garment for patient, medical polymer Interventional instrument all are to be developed by polymkeric substance such as polyester polymkeric substance, polyolefin polymers, polysaccharide polymer, polyamine esters, cellulose families.In actual use, these materials contact with wound, scalded skin, in-vivo tissue, but usually because they do not have anti-infective performance and relatively poor biocompatibility causes wound or tissue to occur to infect or inflammatory phenomena, further cause the regeneration difficulty of wound healing and tissue.For example; the wound pad pasting is polylactic acid electrospinning silk non-woven fabrics; be not subjected to ectocine except its protection wound of needs in the use procedure; also need it can kill or suppress near the bacterial infection of wound; and have excellent biocompatibility, create a good regeneration microenvironment to give the wound cell or tissue.
Ion implantation technique is the method on a kind of modified macromolecule material surface, it can be injected into required element the upper layer of material, unlike magnetron sputtering technique element deposition at material surface, so the polymer surface difficult drop-off that obtains of ion implantation technique, have persistence.
Through retrieval, (publication number is: CN1385142A) to adopt at present ion injection method modification medical material sufacing to have the people such as Liu Xianghuai, Wang Xi to improve the method for artificial cardiac valve material blood compatibility and safety in utilization, with the ion implantation heart valve leaflet surface of making to RESEARCH OF PYROCARBON of N+, the method has only improved the blood compatibility of material, do not solve material surface anti-infective performance and and the tissue between biocompatibility issues; (publication number is the surface modifying method of the clear medical grade silicon rubber of the human hair such as Zhang Yiming, Chen Yu: CN101880402A), the method is injected into silastic surface with carbon ion, reach tissue compatible by improving its surface hydrophilicity, also do not solve the silastic surface infection problems; For another example, the people such as Zhao Jie, Liu Qianxiang have reported and have prepared the method for silver-enriched antibacterial film at medical RESEARCH OF PYROCARBON and TiN film (publication number is: 1827840), the method is only silver ions to be injected on RESEARCH OF PYROCARBON and the TiN film to reach antibacterial effect.This shows, at present the patent about ion implantation of report is less, and they for base material be mainly metal alloy and carbon material, rather than medical macromolecular materials; And all only pay close attention to the performance in a certain respect that improves material and the otherwise performance requriements of having ignored material.
The anti-infection property of macromolecular material and biocompatibility are very important in the application of field of medicaments.Therefore, need to provide a kind of method that can process fast, easily macromolecular material, process the existing higher anti-infective performance of macromolecular material that obtains, preferably biocompatibility is arranged again.
Summary of the invention
The technical problem to be solved in the present invention provides the method that adopts ion implantation technique to prepare medical macromolecular materials; The method is by the treatment bench in the vacuum chamber of medical macromolecular materials being fixed or moved through ion implantation device, vacuumize, pass into gas, open the power supply of ion implanter, process material, obtain having the medical macromolecular materials of surface anti infection and biocompatibility; Present method is simple to operate, does not affect the physical chemistry structure of material body, and the polymer surface Stability Analysis of Structures that obtains after the processing have anti-infective performance long-acting, wide spectrum, and cell compatibility is not less than the intrinsic biocompatibility of material itself.
For solving the problems of the technologies described above, the invention provides a kind of method that adopts ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
1) medical macromolecular materials is fixed or is moved through treatment bench in the vacuum chamber of ion implantation device;
2) sealed vacuum chamber is evacuated down to the base vacuum degree;
3) pass into gas;
4) power supply of unlatching ion implanter, control accelerating power source and ion implantation dosage after processing finishes, obtain having the medical macromolecular materials of high anti-infection property and biocompatibility.
Further, described step 4) comprise that also the power supply of opening plasma source processed material 0.001～5 hour.
Described plasma source comprises Hall plasma source, radio frequency plasma body source.
The frequency of described plasma source is 1～50MHz, and power is 0.001～3000W.
Further, described medical macromolecular materials are the macromolecular materials that are applied to medicine equipment, medical facilities, medical auxiliary tool, artificial organ; Comprise one or more blends in polyester, polyolefine, urethane, polymeric amide, the Mierocrystalline cellulose; Preferably, comprise one or more blends in tetrafluoroethylene, Mierocrystalline cellulose, polyether-ether-ketone, chitosan, methyl methacrylate, polyvinyl alcohol, polyoxyethylene glycol, Polyvinylpyrolidone (PVP), polyglycolic acid, polyethylene, polystyrene, polypropylene, poly(lactic acid), polymeric amide-66, the polymeric amide-6.
Described medical macromolecular materials move be with medical macromolecular materials take rate travel as 0.01～10 cel through the treatment bench in the vacuum chamber of ion implantation device.
Further, described gas is argon gas.
Preferably, described gas also comprises one or more gaseous mixture in nitrogen, ammonia, oxygen, hydrogen, methane, acetylene, alcohol gas, water vapor, tetrachloromethane gas, acetic gas, the vinylformic acid gas.
The described gas that passes into can pass into various gases simultaneously, and also successively different time or intermittent type pass into various gases.
The vacuum tightness that passes in the described vacuum chamber behind the gas maintains 1.0 * 10
1～1.0 * 10
-4Pa.
Further, described ion implanter is equipped with electrode; Described electrode comprises one or more mixtures in silver, aluminium, zinc, titanium, copper, carbon, phosphorus, calcium, graphite and their compound.When ion implanter has one or more electrode, can open simultaneously the power supply of all electrodes, also can the interval in succession open the power supply of each electrode in 0～5 hour.
" their compound " refers to contain the material of silver, aluminium, zinc, titanium, copper, phosphorus or calcium constituent in the literary composition.Such as silver chloride, silver suboxide, aluminium hydroxide, zinc oxide, zinc chloride, zinc sulfate, titanium oxide, copper carbonate, zinc carbonate, oxidation two phosphorus, calcium sulfate, calcium carbonate etc.
The power supply of described plasma source and ion implanter can be opened simultaneously, also can successively open.
Described ion implanter, the control acceleration voltage is 2～50KV, ion implantation dosage is 1 * 10
10～1 * 10
18Ions/cm
2
The medical macromolecular materials surface portion that described anti-infection property refers to adopt the ion implantation technique preparation reaches more than 90% the anti-infective rate of bacterium; Bacterial species comprises intestinal bacteria, streptococcus aureus, staphylococcus epidermidis, Pseudomonas aeruginosa, Candida albicans, streptococcus pneumoniae, klebsiella, blackish green coccus.
Described biocompatibility refers to that the medical macromolecular materials surface of adopting ion implantation technique to prepare is conducive to the growth and breeding of cell and tissue, the biocompatibility of material before the biocompatibility of material surface is not less than and processes after processing.
The present invention has following beneficial effect:
1, after the present invention opened the power supply of ion implanter, ionization occured and produces ion in gas, with the material effect, has changed the surface tissue of material.
2, the present invention adds top electrode in ion implanter, by making alive on the electrode, generates electrode ion, under the action of a magnetic field that acceleration voltage forms, the acceleration injecting material is surperficial, has improved the anti-infective performance of medical macromolecular materials, has ensured simultaneously the biocompatibility of material surface.
3, the present invention utilizes ion implanter to process medical macromolecular materials, and anti-infective element is injected into the medical macromolecular materials surface, and the material of producing has persistence, difficult drop-off more.
4, the present invention utilizes the chemical structure on Plasma-Modified medical macromolecular materials surface, makes it not only be conducive to cell and tissue growth breeding, and the effect that has prolonged antibacterial effect.Simultaneously, by ion implanter anti-infective element (such as silver, zinc, copper etc.) is injected into the medical macromolecular materials surface, the chemical structure that generates with plasma body produces interaction, stablized anti-infective element in chemistry and the physical condition on medical polymer surface, both mutual coordinative roles, not only improve the anti-infective performance of medical macromolecular materials, and ensured the biocompatibility of material surface.
5, the present invention is simple to operate, does not affect the physical chemistry structure of material body.
6, the polymer surface that obtains after the present invention's processing, form the modified surface layer of certain depth, modified layer can reach 50-500nm usually, and be not only to be deposited on material surface, Stability Analysis of Structures, have anti-infective performance long-acting, wide spectrum, and cell compatibility is not less than the intrinsic biocompatibility of material itself.
Description of drawings
Fig. 1 is the schematic diagram of the treating processes of embodiment 1.
Fig. 2 is the variation diagram of the content of carbon in the XPS test process, silver, nitrogen element with the argon ion sputtering time.
Fig. 3 is the polyethylene film upper layer TEM figure that embodiment 1 makes.
Fig. 4 is embodiment 1 polyethylene film that makes and the fibroblastic growth and breeding situation map of material surface of processing without the inventive method.
Fig. 5 is the growth and breeding situation map of embodiment 2 the PLA film that makes and the material surface Chinese hamster ovary cell of processing without the inventive method.
Embodiment
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
With thickness be the polyethylene film of 1 μ m with the treatment bench in 1 m/min of vacuum chamber that moves through ion implantation device, silver electrode is contained on the ion implanter sealing equipment vacuum chamber then, and be evacuated down to 1 * 10
-5During Pa, pass into the nitrogen of 10.0SCCM and the argon gas of 10.0SCCM, finally make the working vacuum degree maintain 1 * 10
-2About Pa, open the Hall plasma source, power is 300W, opens simultaneously ion implantation electromechanical source, and acceleration voltage is 15KV, and ion implantation dosage is 1 * 10
15～1 * 10
17Ions/cm
2, after processing finishes, turn off the power supply of ion implanter and Hall plasma source, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, namely obtain the polyethylene film of required anti-infective and biocompatibility.
Fig. 1 has provided the schematic diagram of polyethylene film treating processes.
The polyethylene film that embodiment 1 makes is tested.The polyethylene film that embodiment 1 makes is 1 * 10 to concentration
4The colibacillary antibiotic rate of CFU/ml is 99.9%.
Fig. 2 is the variation diagram of the content of carbon, silver, nitrogen element with the argon ion sputtering time.This figure is by adopting argon ion source that the polyethylene film that embodiment 1 makes is carried out ion beam sputtering, utilizing ionic fluid to peel off certain thickness upper layer, and then use the XPS analysis surface composition.Adopt argon ion sputtering herein.Owing to the speed of the peeling rate of material is that the speed of relative Ar is decided, and and do not know the peeling rate that it is definite, therefore adopting the time of Ar sputter is X-coordinate.And the argon sputtering time is longer, represents that namely the case depth of material is darker.As can be seen from the figure, in the argon sputter procedure, have silver and nitrogen element, namely showing has silver element and nitrogen element in the surface of material certain depth always.
Fig. 3 is the polyethylene film surface transmission electron microscope SEM figure that embodiment 1 makes.As can be seen from the figure, Ag is distributed in the polyethylene surface layer, and the modification degree of depth can reach 300nm.
From Fig. 2 and Fig. 3, can find, silver element and nitrogen element are injected into the upper layer of polyethylene film, and be not only to rest on outside surface, the physical chemistry structure that generates forms transition layer, it is conducive to the stable of element, further be conducive to process the lasting anti-infection property of rear sample, be specially adapted to improve biocompatibility and the anti-infective performance of the biomaterial surface of motor tissue.
Fig. 4 is the polyethylene film that makes of the present invention (being: process sample) surface among the figure, can find out, inoblast is better than untreated samples in the growth and breeding speed of processing sample surfaces.
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
Be that the PLA film of 0.5 μ m is fixed on the treatment bench in the vacuum chamber of ion implantation device with thickness, silver electrode and zinc electrode are contained on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 5 * 10
-6During Pa, pass into the argon gas of ammonia, 5.0SCCM acetic gas and the 10.0SCCM of 5.0SCCM, finally make the working vacuum degree maintain 5 * 10
-3About Pa, open the radio frequency plasma body source, power is 500W, processes after 5 minutes, opens the power supply of ion implanter again, and acceleration voltage is 30KV, and ion implantation dosage is 1 * 10
16～5 * 10
16Ions/cm
2, processed for 5 seconds after, turn off the power supply of ion implanter and rf plasma source, and under this condition, kept 60 minutes, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain the medical PLA film of required anti-infective and biocompatibility.
After tested, the PLA film of ion implantation modification is 1 * 10 to concentration
4The anti-infective performance of the streptococcus aureus of CFU/ml, antibiotic rate is greater than 95%.The Growth of Cells situation of the Chinese hamster ovary celI (Chinese hamster ovary cell) that Fig. 5 has provided equal amts after the PLA of ion implantation modification film surface and unmodified PLA film surface are cultivated 2 days, can obviously find out, in the quantity of the Chinese hamster ovary celI of the PLA of ion implantation modification film surface (A) far away more than the quantity of the Chinese hamster ovary celI of unmodified PLA film surface (B), the breeding growth of the Chinese hamster ovary celI that the PLA film surface (A) that ion implantation modification is described more is conducive to than unmodified PLA film surface (B).
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
With supporter between polymeric amide-66 artificial vertebral body with the treatment bench in 2 m/mins of vacuum chambers that move through ion implantation device, each electrode of silver electrode, Graphite Electrodes and phosphorus electrode is contained on the ion implanter, then sealing equipment vacuum chamber, and be evacuated down to 5 * 10
-4During Pa, pass into the argon gas of nitrogen, 5.0SCCM acetylene gas and the 5.0SCCM of 10.0SCCM, finally make the working vacuum degree maintain 1 * 10
-4About Pa, open the Hall plasma source, power is 800W, processes after 10 minutes, opens the power supply of ion implanter, and acceleration voltage is 30KV, and ion implantation dosage is 1 * 10
17～5 * 10
17Ions/cm
2After processing finishes, the power supply of turning off ion implanter, and after keeping 5 minutes under this condition, turn off the power supply of Hall plasma source, kept again 2 hours, pass into subsequently atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain supporter between medical polymeric amide-66 artificial vertebral body of required anti-infective and biocompatibility.
After tested, supporter is 1 * 10 to concentration between the polymeric amide of ion implantation modification-66 artificial vertebral body
4The anti-infective performance of the streptococcus aureus of CFU/ml, antibiotic rate is greater than 90%; Osteocyte (MC3T3-EI) supporting body surface growth and breeding speed between polymeric amide-66 artificial vertebral body of ion implantation modification is better than the growth and breeding speed of supporting body surface between unmodified polymeric amide-66 artificial vertebral body.
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
The PEEK spinal fusion device is fixed on the treatment bench in the vacuum chamber of ion implantation device, calcium electrode, silver electrode and phosphorus electrode are contained on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 2 * 10
-5During Pa, pass into the argon gas of oxygen, 5.0SCCM nitrogen and the 5.0SCCM of 1.0SCCM, finally make the working vacuum degree maintain 5x10
-2About Pa, open the power supply of radio frequency plasma body source, power is 1000W again, opens simultaneously the power supply of ion implanter, and acceleration voltage is 50KV, and ion implantation dosage is 1 * 10
15～5 * 10
15Ions/cm
2, process after 5 minutes, turn off the power supply of ion implanter, turn off oxygen, pass into the H of 50.0SCCM
2O gas, and after keeping 10 minutes under this condition, turn off the power supply of radio frequency plasma body source, kept again 2 hours, pass into subsequently atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain the PEEK spinal fusion device of required anti-infective and biocompatibility.
After tested, the PEEK spinal fusion device of ion implantation modification is 1x10 to concentration
4The colibacillary anti-infective performance of CFU/ml, antibiotic rate is greater than 95%; The growth and breeding speed of osteocyte (MC3T3-EI) on the PEEK of ion implantation modification spinal fusion device surface is better than the growth and breeding speed on unmodified PEEK spinal fusion device surface.
Embodiment 5
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
With natural cellulose and polypropylene mixed goods with 1 m/min speed through the treatment bench in the vacuum chamber of ion implantation device, silver electrode, zinc electrode are packed on the ion implanter sealing equipment vacuum chamber then, and be evacuated down to 1 * 10
-4During Pa, pass into the ammonia of 10.0SCCM and the argon gas of 5.0SCCM, finally make the working vacuum degree maintain 1 * 10
-3About Pa, open the power supply of Hall plasma source, power is 200W, opens the power supply of ion implanter, and acceleration voltage is 5KV, and ion implantation dosage is 1 * 10
14～9 * 10
14Ions/cm
2After handling continuously natural cellulose and polypropylene fabric, turn off the power supply of Hall plasma source and ion implanter, turn off all gas, and pass into atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain natural cellulose and the polypropylene mixed goods of required anti-infective and biocompatibility.
After tested, the natural cellulose of ion implantation modification and polypropylene mixed goods are 1 * 10 to concentration
4The Pseudomonas aeruginosa of CFU/ml and the antibiotic rate of staphylococcus epidermidis are greater than 92%; The growth and breeding speed of inoblast on the natural cellulose of ion implantation modification and polypropylene mixed goods surface is not less than the growth and breeding speed on unmodified natural cellulose and polypropylene mixed goods surface.
Embodiment 6
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
Polyglycolic acid, polyvinyl alcohol and chitosan blend thing film are fixed on the treatment bench in the vacuum chamber of ion implantation device, titanium electrode and zinc electrode are contained on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 1 * 10
-5During Pa, pass into the nitrogen of 10.0SCCM and the argon gas of 2.0SCCM, finally make the working vacuum degree maintain 1 * 10
-1About Pa, open the Hall plasma source, power is 300W, and the acceleration voltage of opening simultaneously ion implanter is 5KV, and ion implantation dosage is 1 * 10
15～1 * 10
16Ions/cm
2, turn off the power supply of Hall plasma source and ion implanter, turn off nitrogen and argon gas, and pass into 20.0SCCMH
2O gas 1 hour passes into subsequently atmosphere and makes vacuum chamber be returned to normal atmosphere, namely obtains polyglycolic acid, polyvinyl alcohol and the chitosan blend thing film of required anti-infective and biocompatibility.
After tested, the polyglycolic acid of ion implantation modification, polyvinyl alcohol and chitosan blend thing film are 1x10 to concentration
4The Pseudomonas aeruginosa of CFU/ml and the antibiotic rate of staphylococcus epidermidis are greater than 90%; Inoblast and osteocyte are better than the growth and breeding speed on unmodified polyglycolic acid, polyvinyl alcohol and chitosan film surface in the growth and breeding speed of polyglycolic acid, polyvinyl alcohol and the chitosan film of ion implantation modification.
Embodiment 7
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
Poly tetrafluoroethylene is fixed on the treatment bench in the vacuum chamber of radio frequency ion implantation device, carbon dioxide process carbon electrode and titanium electrode are contained on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 1 * 10
-5During Pa, pass into the argon gas of 30.0SCCM, the working vacuum degree is maintained about 1.0Pa, open the radio frequency plasma body source, frequency is 1MHz, and power is 3000W, opens simultaneously the power supply of ion implanter, and acceleration voltage is 30KV, and ion implantation dosage is 1 * 10
10～1 * 10
12Ions/cm
2, processed for 10 seconds after, turn off the power supply of radio frequency plasma body source and ion implanter, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, namely obtain the poly tetrafluoroethylene of required anti-infective and biocompatibility.
Embodiment 8
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
The methyl methacrylate film with the treatment bench in 6 m/mins of vacuum chambers that move through ion implantation device, is contained in aluminium electrode and zinc electrode on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 1 * 10
-5During Pa, pass into the alcohol gas of 0.1SCCM, the methane gas of 100.0SCCM and the argon gas of 10.0SCCM, finally make the working vacuum degree maintain 1 * 10
-4About Pa, open the power supply of Hall plasma source, frequency is 1MHz, and power is 3000W, and opens the power supply of ion implanter, and acceleration voltage is 30KV, and ion implantation dosage is 1 * 10
12～1 * 10
13Ions/cm
2, processed 5 hours, turn off the power supply of Hall plasma source and ion implanter, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, namely obtain the methyl methacrylate film of required anti-infective and biocompatibility.
Embodiment 9
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
Polyvinylpyrolidone (PVP) and polyethylene glycol blending thing film with the treatment bench in 0.5 m/min of vacuum chamber that moves through ion implantation device, are contained in carbon dioxide process carbon electrode and copper electrode on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 1 * 10
-2During Pa, pass into the tetrachloromethane of 200.0SCCM and the argon gas of 0.1SCCM, finally make the working vacuum degree maintain 1 * 10
-2About Pa, open the power supply of Hall plasma source, frequency is 50MHz, and power is 0.001W, and opens the power supply of ion implanter, and acceleration voltage is 50KV, and ion implantation dosage is 1 * 10
17～1 * 10
18Ions/cm
2, process after 2 hours, turn off the power supply of Hall plasma source and ion implanter, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, namely obtain required Polyvinylpyrolidone (PVP) and polyethylene glycol blending thing film.
Embodiment 10
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
Polymeric amide-6 is fixed on the treatment bench in the vacuum chamber of ion implantation device, copper carbonate electrode and zinc carbonate electrode electrode are contained on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 2 * 10
-5During Pa, pass into the argon gas of 10.0SCCM, the working vacuum degree is maintained about 5Pa, open the power supply of ion implanter, acceleration voltage is 50KV, and ion implantation dosage is 1 * 10
10～1 * 10
11Ions/cm
2, process after 20 minutes, turn off the power supply of ion implanter, turn off argon gas, kept again 2 hours, pass into subsequently atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain the polymeric amide-6 of required anti-infective and biocompatibility.
Embodiment 11
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
With thickness be the polystyrene film of 0.1 μ m with the treatment bench in 10 m/mins of vacuum chambers that move through ion implantation device, silver chloride electrode and each electrode of aluminium hydroxide are contained on the ion implanter sealing equipment vacuum chamber then, and be evacuated down to 5 * 10
-4During Pa, pass into the hydrogen of 10.0SCCM and the argon gas of 20.0SCCM, the working vacuum degree is maintained about 10Pa, open the Hall plasma source, power is 500W, opens the power supply of ion implanter, and acceleration voltage is 2KV, and ion implantation dosage is 1 * 10
17～1 * 10
18Ions/cm
2, after processing finishes, turn off the power supply of ion implanter and Hall plasma source, and under this condition, kept 60 minutes, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain the polystyrene film of required anti-infective and biocompatibility.
Embodiment 12
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
The methyl methacrylate film with the treatment bench in 60 m/mins of vacuum chambers that move through ion implantation device, is contained in phosphorus electrode and silver oxide electrode on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 1 * 10
-5During Pa, pass into the alcohol gas of 0.1SCCM and the argon gas of 10.0SCCM, finally make the working vacuum degree maintain 1 * 10
2About Pa, open the power supply of Hall plasma source, frequency is 1MHz, and power is 3000W, and opens the power supply of ion implanter, and acceleration voltage is 35KV, and ion implantation dosage is 5 * 10
15～1 * 10
16Ions/cm
2, after processing finishes, turn off the power supply of Hall plasma source and ion implanter, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, namely obtain the methyl methacrylate film of required anti-infective and biocompatibility.
Embodiment 13
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps:
Polymeric amide-6 is fixed on the treatment bench in the vacuum chamber of ion implantation device, titanium electrode and Vanadium Pentoxide in FLAKES electrode are contained on the ion implanter, sealing equipment vacuum chamber then, and be evacuated down to 2 * 10
-5During Pa, pass into the argon gas of 10.0SCCM, finally make the working vacuum degree maintain 1.0x10
-4About Pa, open the power supply of ion implanter, acceleration voltage is 45KV, and ion implantation dosage is 1 * 10
16～5 * 10
16Ions/cm
2, process after 15 minutes, turn off the power supply of ion implanter, turn off argon gas, kept again 2 hours, pass into subsequently atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain the polymeric amide-6 of required anti-infective and biocompatibility.
Embodiment 14
Adopt ion implantation technique to prepare medical macromolecular materials, may further comprise the steps: be that the PLA film of 0.5 μ m is with the treatment bench in 0.06 m/min of vacuum chamber that moves through ion implantation machine equipment with thickness, calcium sulfate electrode and silver electrode are contained on the ion implanter, then sealing equipment vacuum chamber, and be evacuated down to 5 * 10
-4During Pa, pass into the vinylformic acid gas of 10.0SCCM and the argon gas of 20.0SCCM, the working vacuum degree is maintained about 10Pa, open the Hall plasma source, power is 500W, opens the power supply of ion implanter, acceleration voltage is 40KV, and ion implantation dosage is 1 * 10
13～5 * 10
14Ions/cm
2, process after 1.5 hours, turn off the power supply of ion implanter and Hall plasma source, and under this condition, kept 60 minutes, pass into atmosphere and make vacuum chamber be returned to normal atmosphere, can obtain the medical PLA film of required anti-infective and biocompatibility.
Embodiment 15
With embodiment 14, unique variation is to change respectively calcium sulfate electrode and silver electrode into silver chloride electrode and silver oxide electrode.
Embodiment 16
With embodiment 14, unique variation is to change respectively calcium sulfate electrode and silver electrode into aluminium hydroxide electrode and zinc oxide electrode.
Embodiment 17
With embodiment 14, unique variation is to change respectively calcium sulfate electrode and silver electrode into zinc chloride electrode and zinc sulfate electrode.
Embodiment 18
With embodiment 14, unique variation is to change respectively calcium sulfate electrode and silver electrode into Titanium oxide electrode and copper carbonate electrode.
Embodiment 19
With embodiment 14, unique variation is to change respectively calcium sulfate electrode and silver electrode into zinc carbonate electrode and titanium dioxide phosphorus electrode.
With embodiment 14, unique variation is to change respectively calcium sulfate electrode and silver electrode into calcium sulfate electrode and calcium carbonate electrode.
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give all embodiments exhaustive.Everyly belong to the row that apparent variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (10)
1. adopt ion implantation technique to prepare the method for medical macromolecular materials, it is characterized in that, may further comprise the steps:
1) medical macromolecular materials is fixed or is moved through treatment bench in the vacuum chamber of ion implantation device;
2) sealed vacuum chamber is evacuated down to the base vacuum degree;
3) pass into gas;
4) power supply of unlatching ion implanter, control accelerating power source and ion implantation dosage after processing finishes, obtain having the medical macromolecular materials of high anti-infection property and biocompatibility.
2. employing ion implantation technique according to claim 1 prepares the method for medical macromolecular materials, it is characterized in that described step 4) comprise that also the power supply of opening plasma source processed material 0.001～5 hour.
3. employing ion implantation technique according to claim 1 and 2 prepares the method for medical macromolecular materials, it is characterized in that, described medical macromolecular materials comprise one or more blends in polyester, polyolefine, urethane, polymeric amide, the Mierocrystalline cellulose.
4. employing ion implantation technique according to claim 3 prepares the method for medical macromolecular materials, it is characterized in that, described medical macromolecular materials comprise one or more blends in tetrafluoroethylene, Mierocrystalline cellulose, polyether-ether-ketone, chitosan, methyl methacrylate, polyvinyl alcohol, polyoxyethylene glycol, Polyvinylpyrolidone (PVP), polyglycolic acid, polyethylene, polystyrene, polypropylene, poly(lactic acid), polymeric amide-66, the polymeric amide-6.
5. employing ion implantation technique according to claim 1 and 2 prepares the method for medical macromolecular materials, it is characterized in that, described gas is argon gas, and the vacuum tightness that passes in the described vacuum chamber behind the gas maintains 1.0 * 10
1～1.0 * 10
-4Pa.
6. employing ion implantation technique according to claim 5 prepares the method for medical macromolecular materials, it is characterized in that, described gas also comprises the mixture of one or more gases in nitrogen, ammonia, oxygen, hydrogen, methane, acetylene, alcohol gas, water vapor, tetrachloromethane gas, acetic gas, the vinylformic acid gas.
7. employing ion implantation technique according to claim 1 and 2 prepares the method for medical macromolecular materials, it is characterized in that, described ion implanter is equipped with electrode; Described electrode comprises one or more mixtures in silver, aluminium, zinc, titanium, copper, carbon, phosphorus, calcium, graphite and their compound.
8. employing ion implantation technique according to claim 2 prepares the method for medical macromolecular materials, it is characterized in that, described plasma source comprises Hall plasma source, radio frequency plasma body source; The frequency of described plasma source is 1～50MHz, and power is 0.001～3000W.
9. employing ion implantation technique according to claim 1 prepares the method for medical macromolecular materials, it is characterized in that, described ion implanter control acceleration voltage is 2～50KV, and ion implantation dosage is 1 * 10
10～1 * 10
18Ions/cm
2
10. employing ion implantation technique according to claim 1 and 2 prepares the method for medical macromolecular materials, it is characterized in that, described medical macromolecular materials move be with medical macromolecular materials take rate travel as 0.01～10 cel through the treatment bench in the vacuum chamber of ion implantation device.
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