CN102886071A - Medicinal silver-loaded metal bioactive coating as well as preparation method and application thereof - Google Patents

Medicinal silver-loaded metal bioactive coating as well as preparation method and application thereof Download PDF

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CN102886071A
CN102886071A CN2011102041591A CN201110204159A CN102886071A CN 102886071 A CN102886071 A CN 102886071A CN 2011102041591 A CN2011102041591 A CN 2011102041591A CN 201110204159 A CN201110204159 A CN 201110204159A CN 102886071 A CN102886071 A CN 102886071A
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silver
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medical metal
bioactivity coatings
metal
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王美艳
姜来新
何丹农
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Abstract

A preparation method of a medicinal silver-loaded metal bioactive coating, which is characterized by adopting a magnetron sputtering process, and comprises the following steps of: (1) processing a metallic matrix; (2) processing the metallic matrix before sputtering; (3) preparing the medicinal silver-loaded metal bioactive coating through the magnetron sputtering process, and obtaining the medicinal silver-loaded metal bioactive coating by controlling the precipitating time under the following conditions: a cathode is a high-purity silver target, a working gas is argon, the vacuum of a substrate in a vacuum chamber is 2.0*10<-3>Pa, the power of the target is 40 to 80 W, the frequency is 13.0 to 15.6MHz, and the flow is 30 SCCM. The medicinal silver-loaded metal bioactive coating provided by the invention is stable in property, free from biological toxicity and good in biocompatibility, and realizes antibiosis.

Description

Carrying silver-colored medical metal bioactivity coatings and preparation method thereof uses
Technical field
The present invention relates to a kind of preparation method and application thereof of medical metal bioactivity coatings, particularly relate to preparation method and the application thereof of a kind of year silver-colored medical metal bioactivity coatings.
Background technology
Human autopsy tissues is often because wound, disease, functional deterioration or birth defect etc. are former thereby reduce even lose its original function, and the applying biological medical material is repaired or alternative tissue and function are effective medicinal approaches clinically.Titanium alloys etc. are a kind ofly not only to have good shape memory effect, and have the novel intelligent material of phase transformation pseudoelasticity.Because it has good biocompatibility, nontoxic, not carcinogenic, not teratogenesis, do not bring out allergy, with body tissue good affinity is arranged, be widely used at biomedical engineering field at present.For open fracture and the serious damaged treatment of bone, it is the insoluble problem of medical circle always.Difficulty is if do not perform the operation in early days the bone grafting repairing bone defect, may cause fracture delayed union, be difficult to form the problem of connection: as fracture end blood fortune is interfered, increase the damage of soft tissue; Absorption sclerosis, osteoporosis and bone and the soft tissue atrophy of epiphysis also can appear, and with ankylosis.And there be possibility that occur to infect in the operation bone grafting, and if the appearance that infection also has complication occurs.So conventional solution is at the large segmental bone defect wound healing that the infection after the fracture, chronic osteomyelitis the are left over bone grafting of just performing the operation after at least ten months, however, bone usually transplants also because the recurrence of infecting and failure.
Prior art adopts the antibiotics of gentamycin, cephalo-type usually when bone-grafting material is loaded with the processing of antibacterials.The problem that causes is: one, many pathogenic bacterium can develop immunity to drugs fast to antibiotics; Two, because the wound site blood circulation is destroyed, be difficult to reach effective antibiotic concentration, can cause the whole body toxic and side effects and increase medication raising blood drug level.Therefore, the traditional treatment pattern not only the course for the treatment of long, and disability rate is high.Silver be used for antibacterial therapy have nontoxic, without irritated, without anti-, without plurality of advantages such as intersection interfering effects of drugs.Nanometer silver has higher specific surface area, higher active face, thereby bactericidal activity is also stronger, consumption reduces, and saves cost.In order to address these problems, we adopt nanometer silver as antibacterial improvement to be modified on the medical metal surface.
The method of the metal base surface deposition of having developed at present has sol-gel (Sol-G el), plasma spraying, hydro-thermal method, pulsed laser deposition, electrochemical deposition method, coating-sintering process, spray pyrolysis and sputter etc.Magnetron sputtering is a kind of " the high-speed low temperature sputtering technology " that development in recent years is got up.The principle of this technology is that electronics accelerates to fly under the effect of electric field in the process of substrate and bumps with ar atmo, ionizes out a large amount of argon ions and electronics, and electronics flies to substrate.Argon ion accelerates the bombardment target under the effect of electric field, sputter a large amount of target atom, is neutral target atom (or molecule) and is deposited on film forming on the substrate.This technology has that the matrix temperature rise is low, film forming speed is fast, film component is even, film performance is stable, thin-film body adhesive strength advantages of higher.Present this technology is used for the preparation of glass-film mostly, and the preparation of sedimentary organism active coating is also than lacking on metallic matrix.V.NeLea etc. prepare hydroxyapatite (HA) coating by contrast magnetron sputtering and two kinds of technology of pulse laser, the result shows that the HA coating of two kinds of method preparations all is crystalline state, and has good mechanical property, but compare with the pulse laser method, the coating surface that magnetron sputtering makes is more smooth.Reported that the implantation technology that adopts high energy, mental retardation to combine prepares the method for silver-enriched antibacterial film RESEARCH OF PYROCARBON.But also there is not magnetron sputtering technique to prepare the report of the antibacterial medical metal bioactivity coatings of carrying nano silver granule at present.
Summary of the invention
The object of the present invention is to provide a kind of deposition of silver to the lip-deep technology of preparing of medical metal, prepared the antibiotic bioactive coating of stable performance, antibiotic, inanimate object toxicity, good biocompatibility on the medical material surface.
For achieving the above object, the invention provides the preparation method of a kind of year silver-colored medical metal bioactivity coatings: it is characterized in that adopting magnetron sputtering method, may further comprise the steps:
(1) processing of metallic matrix;
(2) processing of metallic matrix before the sputter;
(3) silver-colored medical metal bioactivity coatings is carried in the magnetron sputtering method preparation, and negative electrode is the high purity silver target, and working gas is argon, and vacuum chamber substrate vacuum is lower than 2.0x10 -3Pa, the power of target are 40-80W, and frequency is 13.0-15.6MHz, and flow is 30SCCM, and the control sedimentation time obtains carrying silver-colored medical metal bioactivity coatings.
Being treated to of described metallic matrix, metal substrate place first the deionized water oscillation cleaning, put into the acetone soln oscillation cleaning again, then use washed with de-ionized water.
Metal substrate is treated to the metal substrate nitrogen sputter clean after step (1) is processed before the described sputter.
The purity of described high purity silver target is 99.99%.
Described sedimentation time is 1-2 minute.
Described medical metal is medical titanium, or titanium alloy, or medical stainless steel.
The invention provides a kind of year silver-colored medical metal bioactivity coatings.
The invention provides the application of silver-colored medical metal bioactivity coatings aspect the hard tissue substituting material of implant into body in a kind of year.
The concrete technology parameter is as shown in table 1.
Table 1
Figure BDA0000077193500000021
Among the present invention, carry the antibacterial medical metal bioactivity coatings pattern of silver-colored granule by scanning electron microscopic observation, find that its face coat is even, the XRD figure analysis of spectrum shows that the main phase of nanometer silver antimicrobial bioactivity coatings for preparing by magnetron sputtering is Ag.
The antibacterial medical metal bioactivity coatings of the carrying nano silver granule of the present invention's preparation, its antibiotic rate is up to more than 99%.
The present invention also provides the application of the antibacterial medical metal bioactivity coatings of year silver-colored granule, and the antibacterial medical metal biological coating that is about to the carrying nano silver granule is used for the biotic influence of preosteoblast MC3T3-E1.The preosteoblast MC3T3-E1 of exponential phase is joined on the carrying nano silver antibacterial medical metal biological coating, cultivated 24 hours, detect it to the propagation situation of preosteoblast MC3T3-E1 with MTT, find that it has the ability that promotes preosteoblast propagation.
The preparation method that the present invention proposes mainly has the following advantages:
1) high sedimentation rate is arranged;
2) defective is low in the film;
3) the film internal stress is low, and is strong with basal body binding force;
4) film component is even;
5) plasma ion energy is low, and is very little to the damage of substrate;
6) film-forming temperature is low, even might synthesize at low temperatures the metastable state thin film.
Description of drawings
Fig. 1 deposits 1 minute carrying nano silver medical metal biological coating surface topography map.
Fig. 2 deposits 1 minute carrying nano silver medical metal biological coating scanning electron microscope thickness chart.
Fig. 3 deposits 2 minutes carrying nano silver medical metal biological coating scanning electron microscope thickness chart.
Fig. 4 carrying nano silver medical metal biological coating XRD figure spectrum (abscissa represents the angle of diffraction 2 (theta), and vertical coordinate represents diffracted intensity).
The antibiotic bacterium colony figure of Fig. 5 carrying nano silver medical metal biological coating.
Fig. 6 carrying nano silver medical metal biological coating is to the vegetative map of preosteoblast MC3T3-E1.
(1) blank titanium sheet; (2) carry nanometer medical metal gold biological coating 1; (3) carrying nano silver medical metal biological coating 2; (4) carrying nano silver medical metal biological coating 3.
The specific embodiment
Following examples are implemented under take the invention technical scheme as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to following embodiment.
The preparation that embodiment 1 different-thickness carries silver-colored titanium alloy bioactivity coatings
(1) processing of metallic matrix:
This method is base materials employed for being of a size of the circular titanium sheet of Φ 12mm * 1.5mm.Polish step by step with 800,1000 and No. 1200 abrasive paper for metallograph, until surfacing is smooth.The titanium sheet is placed deionized water oscillation cleaning 15min, put into again acetone soln oscillation cleaning 20min after, then use washed with de-ionized water, for subsequent use.
(2) preparation of different-thickness carrying nano silver medical metal bioactivity coatings
First vacuum chamber substrate vacuum is evacuated to and is lower than 2.0x10 -3Pa passes into argon metal base surface is carried out pre-sputter clean, and the time is 5min.During thin film deposition, argon is passed in the vacuum chamber with the certain flow ratio.Shielding power supply adopts dc source, and power setting is 40W, and frequency is 13.56MHz, and argon flow amount is 40SCCM.The reactive sputtering under this parameter is adopted in this work, and obtain the carrying nano silver medical metal bioactivity coatings of different-thickness by the change sputtering time: sputtering time is 1min respectively, 2min.
Observed the carrying nano silver medical metal bioactivity coatings even (Fig. 1) that shows by the magnetron sputtering method preparation by field emission scanning electron microscope, increase along with sputtering time, its thickness increases, be respectively 9.5 ± 1.51 μ m, 19.0 ± 0.57 μ m, energy spectrum analysis shows the increase along with the time, and the content of nanometer silver (table 2) XRD figure analysis of spectrum that also is multiplied shows that the main phase of nanometer silver medical metal bioactivity coatings for preparing by magnetron sputtering is Ag.
Table 2
Figure BDA0000077193500000041
The preparation of embodiment 2 different-grain diameter nanometer silver medical metal thing active coatings
(1) processing of metallic matrix:
This method is base materials employed for being of a size of the circular titanium sheet of Φ 12mm * 1.5mm.Polish step by step with 800,1000 and No. 1200 abrasive paper for metallograph, until surfacing is smooth.The titanium sheet is placed deionized water oscillation cleaning 15min, put into again acetone soln oscillation cleaning 20min after, then use washed with de-ionized water, for subsequent use.
(2) preparation of different-grain diameter nanometer silver medical metal bioactivity coatings:
First vacuum chamber substrate vacuum is evacuated to and is lower than 2.0x10 -3Pa passes into argon metal base surface is carried out pre-sputter clean, and the time is 5min.During thin film deposition, argon is passed in the vacuum chamber with the certain flow ratio.Shielding power supply adopts dc source, and frequency setting is 13.56MHz, and argon flow amount is 40SCCM, and sputtering time is 1min.The reactive sputtering under this parameter is adopted in this work, and obtain the nanometer silver medical metal bioactivity coatings of different-grain diameter size by the variance power size: power is set as respectively 40W, 80W.
Observe the carrying nano silver medical metal bioactivity coatings that shows by the magnetron sputtering method preparation by field emission scanning electron microscope even, increase along with power, its nanometer silver particle diameter increases, be respectively 20nm, 40nm, energy spectrum analysis shows that under the certain condition of sedimentation time along with the increase of power, the content of nanometer silver also is multiplied.
The anti-microbial property of embodiment 3 carrying nano silver medical metal bioactivity coatings
According to JC/T 897-2002 antibacterial ceramic products anti-microbial property detection method, adopt plate culture to carry out antibacterial test.We are to gram-negative, positive bacteria: escherichia coli and staphylococcus aureus are tested, and antibiotic rate=(matched group-antibiotic group)/matched group * 100% the results are shown in Table 3.The clump count of carrying nano silver medical metal bioactivity coatings in culture dish, as shown in Figure 4.These results show that carrying nano silver titanium alloy bioactivity coatings all has obvious anti-microbial property.
Table 3
Sample number into spectrum To colibacillary antibiotic rate Antibiotic rate to staphylococcus aureus
1 100% 100%
2 100% 100%
3 100% 99%
Embodiment 4 carrying nano silver medical metal bioactivity coatings are on the impact of preosteoblast MC3T3-E1
(1) cultivation of cell:
The used preosteoblast MC3T3-E1 of the present invention is available from Shanghai Chinese Academy of Sciences cell bank, and used culture fluid is to contain the α that volume fraction is the penicillin-streptomycin of 10% hyclone and 1%-MEM culture fluid.Used cell is 5%CO at 37 ℃ in volume fraction 2The saturated humidity incubator in cultivate, the exponential phase cell is selected in experiment.
(2) MTT detects cell proliferation:
Collect the exponential phase cell, adjust concentration of cell suspension, making cell density is 5 * 10 3-1 * 10 4/ hole; The carrying nano silver bioactivity coatings is put into 24 orifice plates, and every hole adds 700ul cell suspension; 5%C0 2, hatched 24 hours for 37 ℃; Suck culture fluid, every hole adds 70ul MTT solution (5mg/ml, i.e. 0.5%MTT), continues to cultivate 4h; Every hole adds 700ul dimethyl sulfoxide (DMSO), puts low-speed oscillation 10min on the shaking table, and crystal is fully dissolved; Then it is sucked in 96 orifice plates, at enzyme-linked immunosorbent assay instrument OD 490nmThe light absorption value in each hole is measured at the place.
The cell proliferation rate of carrying nano silver medical metal bioactivity coatings is greater than matched group as shown in Figure 6, and this result shows that carrying nano silver medical metal bioactivity coatings has facilitation to the growth of preosteoblast, and this will more be conducive to clinical application.

Claims (8)

1. preparation method of carrying silver-colored medical metal bioactivity coatings: it is characterized in that adopting magnetron sputtering method, may further comprise the steps:
(1) processing of metallic matrix;
(2) processing of metallic matrix before the sputter;
(3) silver-colored medical metal bioactivity coatings is carried in the magnetron sputtering method preparation, and negative electrode is the high purity silver target, and working gas is argon, and vacuum chamber substrate vacuum is lower than 2.0x10 -3Pa, the power of target are 40-80W, and frequency is 13.0-15.6MHz, and flow is 30SCCM, and the control sedimentation time obtains carrying silver-colored medical metal bioactivity coatings.
2. the preparation method of according to claim 1 year silver-colored medical metal bioactivity coatings, it is characterized in that being, being treated to of described metallic matrix, metal substrate places first the deionized water oscillation cleaning, put into again the acetone soln oscillation cleaning, then use washed with de-ionized water.
3. the preparation method of according to claim 1 year silver-colored medical metal bioactivity coatings is characterized in that being, metal substrate is treated to the metal substrate nitrogen sputter clean after step (1) is processed before the described sputter.
4. the preparation method of according to claim 1 year silver-colored medical metal bioactivity coatings is characterized in that being, the purity of described high purity silver target is 99.99%.
5. the preparation method of according to claim 1 year silver-colored medical metal bioactivity coatings is characterized in that being, described sedimentation time is 1-2 minute.
6. the preparation method of according to claim 1 year silver-colored medical metal bioactivity coatings is characterized in that being, described medical metal is medical titanium, or titanium alloy, or medical stainless steel.
7. year silver-colored medical metal bioactivity coatings that is obtained by the described method of one of claim 1-6.
By claimed in claim 7 year silver-colored medical metal bioactivity coatings in the application aspect the hard tissue substituting material of implant into body.
CN2011102041591A 2011-07-20 2011-07-20 Medicinal silver-loaded metal bioactive coating as well as preparation method and application thereof Pending CN102886071A (en)

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Cited By (11)

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CN103816569A (en) * 2014-02-28 2014-05-28 宋凤麒 Method for treating medical implant material with gas-phase Ag nano-particles
CN104225679A (en) * 2014-09-30 2014-12-24 广西中医药大学 Modification method of titanium metal with antibacterial properties and capable of promoting growth of osteoblasts
CN104353109A (en) * 2014-09-30 2015-02-18 广西中医药大学 Method for modifying titanium with antibacterial property and effect of promoting growth of osteoblasts
CN104353114A (en) * 2014-09-30 2015-02-18 广西中医药大学 Medical titanium with osteoblast growth promotion function and surface modification method of medical titanium
CN104372301A (en) * 2014-11-21 2015-02-25 国家纳米科学中心 Method for preparing monodisperse size-controllable nanosilver particles by using radio frequency magnetron sputtering method
CN108295312A (en) * 2018-04-19 2018-07-20 四川理工学院 Mix titanium or titanium alloy of silver and preparation method thereof in surface
CN108354681A (en) * 2018-03-08 2018-08-03 南京医科大学附属口腔医院 Maintenance, the integrated gutta-percha point of tip of a root closing in a kind of argentiferous titanium alloy root pipe
CN111821506A (en) * 2020-06-16 2020-10-27 温州医科大学附属口腔医院 Preparation of strontium/silver nano-coating modified bone bionic titanium implant
RU2760453C1 (en) * 2021-05-05 2021-11-25 Федеральное государственное автономное образовательное учреждение высшего образования "Московский политехнический университет" (Московский Политех) Method for forming a silver-containing biocompatible coating on titanium alloy implants
CN114369808A (en) * 2021-12-20 2022-04-19 中国兵器科学研究院宁波分院 Method for preparing antibacterial coating on surface of magnesium and magnesium alloy
CN115581800A (en) * 2022-10-24 2023-01-10 杭州明康捷医疗科技有限公司 Titanium-based silver-coated implantable antibacterial medical device and preparation method thereof

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CN103816569B (en) * 2014-02-28 2016-05-11 丹阳纳瑞康纳米科技有限公司 The method of the implant medical material of a kind of gas phase Ag nano particle processing
CN103816569A (en) * 2014-02-28 2014-05-28 宋凤麒 Method for treating medical implant material with gas-phase Ag nano-particles
CN104225679A (en) * 2014-09-30 2014-12-24 广西中医药大学 Modification method of titanium metal with antibacterial properties and capable of promoting growth of osteoblasts
CN104353109A (en) * 2014-09-30 2015-02-18 广西中医药大学 Method for modifying titanium with antibacterial property and effect of promoting growth of osteoblasts
CN104353114A (en) * 2014-09-30 2015-02-18 广西中医药大学 Medical titanium with osteoblast growth promotion function and surface modification method of medical titanium
CN104372301A (en) * 2014-11-21 2015-02-25 国家纳米科学中心 Method for preparing monodisperse size-controllable nanosilver particles by using radio frequency magnetron sputtering method
CN108354681A (en) * 2018-03-08 2018-08-03 南京医科大学附属口腔医院 Maintenance, the integrated gutta-percha point of tip of a root closing in a kind of argentiferous titanium alloy root pipe
CN108295312A (en) * 2018-04-19 2018-07-20 四川理工学院 Mix titanium or titanium alloy of silver and preparation method thereof in surface
CN111821506A (en) * 2020-06-16 2020-10-27 温州医科大学附属口腔医院 Preparation of strontium/silver nano-coating modified bone bionic titanium implant
RU2760453C1 (en) * 2021-05-05 2021-11-25 Федеральное государственное автономное образовательное учреждение высшего образования "Московский политехнический университет" (Московский Политех) Method for forming a silver-containing biocompatible coating on titanium alloy implants
CN114369808A (en) * 2021-12-20 2022-04-19 中国兵器科学研究院宁波分院 Method for preparing antibacterial coating on surface of magnesium and magnesium alloy
CN114369808B (en) * 2021-12-20 2024-02-06 中国兵器科学研究院宁波分院 Method for preparing antibacterial coating on surface of magnesium and magnesium alloy
CN115581800A (en) * 2022-10-24 2023-01-10 杭州明康捷医疗科技有限公司 Titanium-based silver-coated implantable antibacterial medical device and preparation method thereof
CN115581800B (en) * 2022-10-24 2023-08-18 杭州明康捷医疗科技有限公司 Titanium-based silver-coated implanted antibacterial medical instrument and preparation method thereof

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