CN102719824A - Dopamine-nanosilver composite coating and preparation method thereof - Google Patents
Dopamine-nanosilver composite coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 239000011248 coating agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title abstract description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 45
- 229960003638 dopamine Drugs 0.000 claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 30
- 239000002071 nanotube Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract 3
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims 16
- 229940100890 silver compound Drugs 0.000 claims 10
- 150000003379 silver compounds Chemical class 0.000 claims 10
- 238000007654 immersion Methods 0.000 claims 4
- 238000006424 Flood reaction Methods 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 49
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 14
- 238000003491 array Methods 0.000 abstract description 14
- 239000007853 buffer solution Substances 0.000 abstract description 3
- 239000007943 implant Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 239000007983 Tris buffer Substances 0.000 description 14
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
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- 239000000523 sample Substances 0.000 description 7
- 101710134784 Agnoprotein Proteins 0.000 description 6
- 238000007743 anodising Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 229910001093 Zr alloy Inorganic materials 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 208000035143 Bacterial infection Diseases 0.000 description 1
- 208000037408 Device failure Diseases 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
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- -1 silver ions Chemical class 0.000 description 1
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- 238000001356 surgical procedure Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明涉及金属材料表面改性领域，更具体地说，涉及金属钛(Ti)及钛合金表面与金属银的复合及其制备方法。The invention relates to the field of surface modification of metal materials, and more specifically relates to the composite of metal titanium (Ti) and titanium alloy surface with metal silver and a preparation method thereof.
背景技术 Background technique
众所周知，银(Ag)自古以来广泛用在抗菌材料上，纳米银具有优异的抗菌性能，纳米银粒子比表面积大，其抗菌作用与银离子(Ag+)有关。钛(Ti)及钛合金以其优异的物理、化学性能及良好的生物相容性，成为目前应用最广泛的组织修复与替代材料，但是由于其本身不具有生物活性，因此需要对其进行表面处理，如在合金表面生长二氧化钛(TiO2)纳米管薄膜来提高其生物活性。同时，在植入手术中，细菌感染也是导致植入材料失效的另一重要原因。As we all know, silver (Ag) has been widely used in antibacterial materials since ancient times, nano-silver has excellent antibacterial performance, nano-silver particles have a large specific surface area, and its antibacterial effect is related to silver ions (Ag + ). Titanium (Ti) and titanium alloys have become the most widely used tissue repair and replacement materials due to their excellent physical and chemical properties and good biocompatibility. Treatment, such as growing titanium dioxide (TiO 2 ) nanotube films on the surface of the alloy to improve its biological activity. At the same time, in implant surgery, bacterial infection is also another important reason for the failure of implant materials.
发明内容 Contents of the invention
本发明的目的在于克服现有技术的不足，提出利用多巴胺与金属离子的螯合特性及自聚合过程中的还原性，在钛合金表面制备纳米银涂层来提高材料的抗菌性能，这对于开发新型功能性金属植入材料具有重要的应用价值和指导意义。The purpose of the present invention is to overcome the deficiencies in the prior art, propose to utilize the chelating characteristic of dopamine and metal ion and the reducibility in self-polymerization process, prepare nano-silver coating on titanium alloy surface and improve the antibacterial performance of material, this is very important for development New functional metal implant materials have important application value and guiding significance.
本发明的目的通过下述技术方案予以实现：The purpose of the present invention is achieved through the following technical solutions:
多巴胺-纳米银复合涂层及其制备方法，按照下述步骤进行：Dopamine-nano-silver composite coating and preparation method thereof are carried out according to the following steps:
首先，即步骤1，将金属基底材料纯钛或表面生长二氧化钛纳米管阵列的钛合金放入多巴胺的缓冲溶液(即Tris溶液)中浸渍，以得到负载有多巴胺的金属基底材料First, step 1, the metal substrate material pure titanium or the titanium alloy with titanium dioxide nanotube arrays grown on the surface is immersed in a buffer solution of dopamine (ie Tris solution) to obtain a metal substrate material loaded with dopamine
其中所述多巴胺的浓度为0.1-0.3mg/ml；Wherein the concentration of said dopamine is 0.1-0.3mg/ml;
所述金属基底材料为纯钛、钛合金、表面生长二氧化钛纳米管阵列的钛合金或者表面生长二氧化钛纳米管阵列的纯钛，其中钛合金的选择和表面生长二氧化钛纳米管的制备可根据利用现有技术“一种在二氧化钛纳米管中掺杂纳米银颗粒的方法”的记载(申请号为201010278615.2、申请日为2010年9月11日、公开日为2010年12月22日)进行实施，选择Ti-Zr合金(Ti和Zr的原子摩尔比为(7-9)∶(3-1)，优选Ti和Zr的原子摩尔比为7∶3、8∶2或者9∶1)、Ti-Zr-Nb合金(Ti、Zr和Nb的原子摩尔比为(73-74)∶(2-4)∶(22-25)，优选Ti、Zr和Nb的原子摩尔比为74∶4∶22或者73∶2∶25)、或者Ti-Zr-Nb-Sn合金(Ti、Zr、Nb和Sn的原子摩尔比为72∶4∶22∶2)，利用阳极氧化法制备表面二氧化钛纳米管；The metal substrate material is pure titanium, titanium alloy, titanium alloy with titanium dioxide nanotube arrays grown on the surface or pure titanium with titanium dioxide nanotube arrays grown on the surface, wherein the selection of titanium alloy and the preparation of titanium dioxide nanotubes grown on the surface can be based on the existing Technology "A method of doping nano-silver particles in titanium dioxide nanotubes" (application number 201010278615.2, application date is September 11, 2010, publication date is December 22, 2010) for implementation, and Ti -Zr alloy (the atomic molar ratio of Ti and Zr is (7-9):(3-1), preferably the atomic molar ratio of Ti and Zr is 7:3, 8:2 or 9:1), Ti-Zr- Nb alloy (the atomic molar ratio of Ti, Zr and Nb is (73-74):(2-4):(22-25), preferably the atomic molar ratio of Ti, Zr and Nb is 74:4:22 or 73: 2:25), or a Ti-Zr-Nb-Sn alloy (the atomic molar ratio of Ti, Zr, Nb and Sn is 72:4:22:2), and anodic oxidation method is used to prepare titanium dioxide nanotubes on the surface;
所述浸渍温度为20-25℃；The dipping temperature is 20-25°C;
所述浸渍时间为20-24小时；The soaking time is 20-24 hours;
所述缓冲溶液的pH为8-8.5；The pH of the buffer solution is 8-8.5;
然后，即步骤2，将负载有多巴胺的金属基底材料置于硝酸银溶液中浸渍，同时光照还原得到纳米银颗粒，其中：Then, step 2, the dopamine-loaded metal base material is immersed in a silver nitrate solution, and simultaneously photoreduced to obtain silver nanoparticles, wherein:
所述硝酸银溶液为硝酸银的水溶液，浓度为0.01-0.05mol/LDescribed silver nitrate solution is the aqueous solution of silver nitrate, and concentration is 0.01-0.05mol/L
所述浸渍温度为20-25℃；The dipping temperature is 20-25°C;
所述浸渍时间为10-15min；The soaking time is 10-15min;
所述光照的工艺参数为光源采用氙灯光源、光强为150mw/cm2 The technical parameters of the illumination are that the light source adopts a xenon lamp light source, and the light intensity is 150mw/cm 2
本发明的技术方案以钛合金为基体，利用多巴胺的螯合及还原特性制备纳米银抗菌涂层的方法，目的是将纳米银颗粒均匀分布在钛合金表面，并与多巴胺形成复合，如附图2所示。经过表面成份的能谱分析和拉曼光谱分析(附图3和4)，金属基底的表面最终形成纳米银。由以上方法得到的抗菌涂层与钛合金基底结合力强，且纳米银颗粒大小可控、分布均匀。本发明实施费用低、操作简便、耗时短，能广泛用于金属医疗器械的表面抗菌涂层的制备。The technical scheme of the present invention uses titanium alloy as the substrate, and uses the chelating and reducing properties of dopamine to prepare nano-silver antibacterial coating. The purpose is to evenly distribute nano-silver particles on the surface of titanium alloy and form a composite with dopamine, as shown in the accompanying drawing 2. After energy spectrum analysis and Raman spectrum analysis of the surface composition (accompanying drawings 3 and 4), the surface of the metal substrate finally forms nano-silver. The antibacterial coating obtained by the above method has a strong binding force with the titanium alloy substrate, and the size of the nano-silver particles is controllable and evenly distributed. The invention has the advantages of low implementation cost, simple operation and short time consumption, and can be widely used in the preparation of surface antibacterial coatings of metal medical instruments.
附图说明 Description of drawings
图1本发明技术方案的示意图The schematic diagram of Fig. 1 technical scheme of the present invention
图2扫描电镜表征负载纳米银前后的形貌照片，其中(a)负载多巴胺后的形貌；(b)直接沉积纳米银后的形貌；(c)经多巴胺还原生成的纳米银颗粒的形貌Figure 2 Scanning Electron Microscope Characterizes the morphology photos before and after loading nano-silver, in which (a) the morphology after loading dopamine; (b) the morphology after direct deposition of nano-silver; (c) the morphology of nano-silver particles generated by dopamine reduction appearance
图3表面成份的能谱分析结果示意图Figure 3 Schematic diagram of energy spectrum analysis results of surface components
图4经多巴胺还原生成的纳米银涂层的拉曼光谱Figure 4 Raman spectrum of nano-silver coating generated by dopamine reduction
具体实施方式 Detailed ways
下面结合具体实施例进一步说明本发明的技术方案。其中硝酸银溶液选择其水溶液；温度选择为25摄氏度下进行浸渍；所述光源采用氙灯光源、光强为150mw/cm2；所述Tris溶液的pH值为8.5。扫描电镜为S4800；Hitachi，Japan。拉曼光谱选用英国雷尼绍公司的inVia reflex，RENISHAW激光拉曼光谱仪；能谱选用美国EDAX公司的Apollo XV型能谱探头。The technical solutions of the present invention will be further described below in conjunction with specific embodiments. Among them, the silver nitrate solution is selected as its aqueous solution; the temperature is selected to be impregnated at 25 degrees Celsius; the light source is a xenon lamp light source with a light intensity of 150mw/cm 2 ; the pH value of the Tris solution is 8.5. The scanning electron microscope was S4800; Hitachi, Japan. The Raman spectrum uses inVia reflex and RENISHAW laser Raman spectrometer from Renishaw Company in the United Kingdom; the energy spectrum uses the Apollo XV energy spectrum probe from EDAX Company in the United States.
实施例1Example 1
以纯钛为基体，制备纳米银抗菌涂层，利用多巴胺的螯合及还原特性制备纳米银颗粒。所说的以纯钛为基体，是尺寸为10*10*6mm的纯钛板，将Ti片用去离子水清洗干净，无水乙醇超声5分钟后干燥备用。Nano-silver antibacterial coating is prepared with pure titanium as the substrate, and nano-silver particles are prepared by using the chelating and reducing properties of dopamine. The said pure titanium as the substrate is a pure titanium plate with a size of 10*10*6mm. The Ti sheet is cleaned with deionized water, and dried with absolute ethanol for 5 minutes before being used.
所说的纳米银颗粒是利用多巴胺还原法制备得到，将Ti片置于多巴胺Tris溶液中反应24小时，再将其置于硝酸银(AgNO3)溶液中经光照反应制得，将样品取出，用无水乙醇超声清洗，即在Ti表面得到均匀分布的纳米银颗粒。Said nano-silver particles are prepared by dopamine reduction method, the Ti sheet is placed in the dopamine Tris solution to react for 24 hours, then it is placed in the silver nitrate (AgNO 3 ) solution and prepared by light reaction, the sample is taken out, Ultrasonic cleaning with absolute ethanol resulted in evenly distributed nano-silver particles on the Ti surface.
制备纳米银的工艺参数为：The process parameters for preparing nano-silver are:
Tris浓度：0.3mg/mlTris concentration: 0.3mg/ml
多巴胺浓度：0.1mg/mlDopamine concentration: 0.1mg/ml
硝酸银溶液浓度：0.01mol/LSilver nitrate solution concentration: 0.01mol/L
光照时间：10minLighting time: 10min
实施例2Example 2
以纯钛为基体，制备纳米银抗菌涂层，利用多巴胺的螯合及还原特性制备纳米银颗粒。所说的以纯钛为基体，是尺寸为10*10*6mm的纯钛板，将Ti片用去离子水清洗干净，无水乙醇超声5分钟后干燥备用。Using pure titanium as the substrate, prepare nano-silver antibacterial coating, and use the chelating and reducing properties of dopamine to prepare nano-silver particles. The said pure titanium as the substrate is a pure titanium plate with a size of 10*10*6mm. The Ti sheet is cleaned with deionized water, and dried with absolute ethanol for 5 minutes before being used.
所说的纳米银颗粒是利用多巴胺还原法制备得到，将Ti片置于多巴胺Tris溶液中反应24小时，再将其置于硝酸银(AgNO3)溶液中经光照反应制得，将样品取出，用无水乙醇超声清洗，即在Ti表面得到均匀分布的纳米银颗粒。Said nano-silver particles are prepared by dopamine reduction method, the Ti sheet is placed in the dopamine Tris solution to react for 24 hours, then it is placed in the silver nitrate (AgNO 3 ) solution and prepared by light reaction, the sample is taken out, Ultrasonic cleaning with absolute ethanol resulted in evenly distributed nano-silver particles on the Ti surface.
制备纳米银的工艺参数为：The process parameters for preparing nano-silver are:
Tris浓度：0.3mg/mlTris concentration: 0.3mg/ml
多巴胺浓度：0.2mg/mlDopamine concentration: 0.2mg/ml
硝酸银溶液浓度：0.01mol/LSilver nitrate solution concentration: 0.01mol/L
光照时间：10minLighting time: 10min
实施例3Example 3
以纯钛为基体，制备纳米银抗菌涂层，利用多巴胺的螯合及还原特性制备纳米银颗粒。所说的以纯钛为基体，是尺寸为10*10*6mm的纯钛板，将Ti片用去离子水清洗干净，无水乙醇超声5分钟后干燥备用。Nano-silver antibacterial coating is prepared with pure titanium as the substrate, and nano-silver particles are prepared by using the chelating and reducing properties of dopamine. The said pure titanium as the substrate is a pure titanium plate with a size of 10*10*6mm. The Ti sheet is cleaned with deionized water, and dried with absolute ethanol for 5 minutes before being used.
所说的纳米银颗粒是利用多巴胺还原法制备得到，将Ti片置于多巴胺Tris溶液中反应24小时，再将其置于硝酸银(AgNO3)溶液中经光照反应制得，将样品取出，用无水乙醇超声清洗，即在Ti表面得到均匀分布的纳米银颗粒。Said nano-silver particles are prepared by dopamine reduction method, the Ti sheet is placed in the dopamine Tris solution to react for 24 hours, then it is placed in the silver nitrate (AgNO 3 ) solution and prepared by light reaction, the sample is taken out, Ultrasonic cleaning with absolute ethanol resulted in evenly distributed nano-silver particles on the Ti surface.
制备纳米银的工艺参数为：The process parameters for preparing nano-silver are:
Tris浓度：0.3mg/mlTris concentration: 0.3mg/ml
多巴胺浓度：0.3mg/mlDopamine concentration: 0.3mg/ml
硝酸银溶液浓度：0.01mol/LSilver nitrate solution concentration: 0.01mol/L
光照时间：10minLighting time: 10min
实施例4Example 4
以表面生长二氧化钛纳米管阵列的钛合金或者金属钛为基体，制备纳米银抗菌涂层，利用多巴胺的螯合及还原特性制备纳米银颗粒。The nano-silver antibacterial coating is prepared on the basis of titanium alloy or metal titanium with titanium dioxide nanotube arrays grown on the surface, and nano-silver particles are prepared by using the chelating and reducing properties of dopamine.
所说的表面生长二氧化钛纳米管阵列的钛合金是利用现有技术“一种在二氧化钛纳米管中掺杂纳米银颗粒的方法”的记载(申请号为201010278615.2、申请日为2010年9月11日、公开日为2010年12月22日)进行制备，利用阳极氧化法，以Ti-Zr合金(Ti和Zr的原子摩尔比为7∶3)为基底，将表面分别用800、1000和2000目砂纸打磨至光滑，后用去离子水清洗干净，无水乙醇超声5分钟后干燥备用。采用两电极系统在NH4F-甘油/水混合溶液中反应制得。将样品取出，用无水乙醇超声清洗后干燥待用。Said titanium alloy with titanium dioxide nanotube arrays grown on the surface is the record of "a method of doping nano-silver particles in titanium dioxide nanotubes" using the prior art (application number is 201010278615.2, application date is September 11, 2010 , date of publication is December 22, 2010) for preparation, using the anodic oxidation method, using Ti-Zr alloy (the atomic molar ratio of Ti and Zr is 7:3) as the substrate, and the surface is respectively coated with 800, 1000 and 2000 mesh Grind it with sandpaper until it is smooth, then clean it with deionized water, ultrasonically dry it for 5 minutes with anhydrous ethanol, and set it aside. It is prepared by reacting in NH 4 F-glycerin/water mixed solution by using two-electrode system. The samples were taken out, cleaned ultrasonically with absolute ethanol, and dried for use.
阳极氧化构成中采用的工艺参数为：The process parameters used in the formation of anodic oxidation are:
阳极氧化电压：30VAnodizing voltage: 30V
阳极氧化时间：3hAnodizing time: 3h
电解液浓度：甘油∶水的体积比为1∶1，加入0.3MNH4FElectrolyte concentration: the volume ratio of glycerol: water is 1:1, add 0.3MNH 4 F
所说的纳米银颗粒是利用多巴胺还原法制备得到，将表面生长二氧化钛纳米管阵列的钛合金置于多巴胺Tris溶液中反应24小时，再将其置于硝酸银(AgNO3)溶液中经光照反应制得，将样品取出，用无水乙醇超声清洗，即在TiO2纳米管表面得到均匀分布的纳米银颗粒。The nano-silver particles are prepared by dopamine reduction method. The titanium alloy with titanium dioxide nanotube arrays grown on the surface is placed in a dopamine Tris solution for 24 hours, and then placed in a silver nitrate (AgNO 3 ) solution for light reaction. prepared, the sample was taken out, and ultrasonically cleaned with absolute ethanol, that is, evenly distributed nano-silver particles were obtained on the surface of the TiO 2 nanotube.
制备纳米银的工艺参数为：The process parameters for preparing nano-silver are:
Tris浓度：0.3mg/mlTris concentration: 0.3mg/ml
多巴胺浓度：0.1mg/mlDopamine concentration: 0.1mg/ml
硝酸银溶液浓度：0.01mol/LSilver nitrate solution concentration: 0.01mol/L
光照时间：10minLighting time: 10min
实施例5Example 5
以表面生长二氧化钛纳米管阵列的钛合金或者金属钛为基体，制备纳米银抗菌涂层，利用多巴胺的螯合及还原特性制备纳米银颗粒。The nano-silver antibacterial coating is prepared on the basis of titanium alloy or metal titanium with titanium dioxide nanotube arrays grown on the surface, and nano-silver particles are prepared by using the chelating and reducing properties of dopamine.
所说的表面生长二氧化钛纳米管阵列的钛合金是利用现有技术“一种在二氧化钛纳米管中掺杂纳米银颗粒的方法”的记载(申请号为201010278615.2、申请日为2010年9月11日、公开日为2010年12月22日)进行制备，利用阳极氧化法，以Ti-Zr合金(Ti和Zr的原子摩尔比为7∶3)为基底，将表面分别用800、1000和2000目砂纸打磨至光滑，后用去离子水清洗干净，无水乙醇超声5分钟后干燥备用。采用两电极系统在NH4F-甘油/水混合溶液中反应制得。将样品取出，用无水乙醇超声清洗后干燥待用。采用两电极系统在NH4F-甘油/水混合溶液中反应制得。Said titanium alloy with titanium dioxide nanotube arrays grown on the surface is the record of "a method of doping nano-silver particles in titanium dioxide nanotubes" using the prior art (application number is 201010278615.2, application date is September 11, 2010 , date of publication is December 22, 2010) for preparation, using the anodic oxidation method, using Ti-Zr alloy (the atomic molar ratio of Ti and Zr is 7:3) as the substrate, and the surface is respectively coated with 800, 1000 and 2000 mesh Grind it with sandpaper until it is smooth, then clean it with deionized water, ultrasonically dry it for 5 minutes with anhydrous ethanol, and set it aside. It is prepared by reacting in NH 4 F-glycerin/water mixed solution by using two-electrode system. The samples were taken out, cleaned ultrasonically with absolute ethanol, and dried for use. It is prepared by reacting in NH 4 F-glycerin/water mixed solution by using two-electrode system.
阳极氧化构成中采用的工艺参数为：The process parameters used in the formation of anodic oxidation are:
阳极氧化电压：30VAnodizing voltage: 30V
阳极氧化时间：3hAnodizing time: 3h
电解液浓度：甘油∶水的体积比为1∶1，加入0.3MNH4FElectrolyte concentration: the volume ratio of glycerol: water is 1:1, add 0.3MNH 4 F
所说的纳米银颗粒是利用多巴胺还原法制备得到，将表面生长二氧化钛纳米管阵列的钛合金置于多巴胺Tris溶液中反应24小时，再将其置于硝酸银(AgNO3)溶液中经光照反应制得，将样品取出，用无水乙醇超声清洗，即在TiO2纳米管表面得到均匀分布的纳米银颗粒。制备纳米银的工艺参数为：The nano-silver particles are prepared by dopamine reduction method. The titanium alloy with titanium dioxide nanotube arrays grown on the surface is placed in a dopamine Tris solution for 24 hours, and then placed in a silver nitrate (AgNO 3 ) solution for light reaction. prepared, the sample was taken out, and ultrasonically cleaned with absolute ethanol, that is, evenly distributed nano-silver particles were obtained on the surface of the TiO 2 nanotube. The process parameters for preparing nano-silver are:
Tris浓度：0.3mg/mlTris concentration: 0.3mg/ml
多巴胺浓度：0.2mg/mlDopamine concentration: 0.2mg/ml
硝酸银溶液浓度：0.01mol/LSilver nitrate solution concentration: 0.01mol/L
光照时间：10minLighting time: 10min
实施例6Example 6
以表面生长二氧化钛纳米管阵列的钛合金或者金属钛为基体，制备纳米银抗菌涂层，利用多巴胺的螯合及还原特性制备纳米银颗粒。The nano-silver antibacterial coating is prepared on the basis of titanium alloy or metal titanium with titanium dioxide nanotube arrays grown on the surface, and nano-silver particles are prepared by using the chelating and reducing properties of dopamine.
所说的表面生长二氧化钛纳米管阵列的钛合金是利用现有技术“一种在二氧化钛纳米管中掺杂纳米银颗粒的方法”的记载(申请号为201010278615.2、申请日为2010年9月11日、公开日为2010年12月22日)进行制备，利用阳极氧化法，以Ti-Zr合金(Ti和Zr的原子摩尔比为7∶3)为基底，将表面分别用800、1000和2000目砂纸打磨至光滑，后用去离子水清洗干净，无水乙醇超声5分钟后干燥备用。采用两电极系统在NH4F-甘油/水混合溶液中反应制得。将样品取出，用无水乙醇超声清洗后干燥待用。采用两电极系统在NH4F-甘油/水混合溶液中反应制得。Said titanium alloy with titanium dioxide nanotube arrays grown on the surface is the record of "a method of doping nano-silver particles in titanium dioxide nanotubes" using the prior art (application number is 201010278615.2, application date is September 11, 2010 , date of publication is December 22, 2010) for preparation, using the anodic oxidation method, using Ti-Zr alloy (the atomic molar ratio of Ti and Zr is 7:3) as the substrate, and the surface is respectively coated with 800, 1000 and 2000 mesh Grind it with sandpaper until it is smooth, then clean it with deionized water, ultrasonically dry it for 5 minutes with anhydrous ethanol, and set it aside. It is prepared by reacting in NH 4 F-glycerin/water mixed solution by using two-electrode system. The samples were taken out, cleaned ultrasonically with absolute ethanol, and dried for use. It is prepared by reacting in NH 4 F-glycerin/water mixed solution by using two-electrode system.
阳极氧化构成中采用的工艺参数为：The process parameters used in the formation of anodic oxidation are:
阳极氧化电压：30VAnodizing voltage: 30V
阳极氧化时间：3hAnodizing time: 3h
电解液浓度：甘油∶水的体积比为1∶1，加入0.3MNH4FElectrolyte concentration: the volume ratio of glycerol: water is 1:1, add 0.3MNH 4 F
所说的纳米银颗粒是利用多巴胺还原法制备得到，将表面生长二氧化钛纳米管阵列的钛合金置于多巴胺Tris溶液中反应24小时，再将其置于硝酸银(AgNO3)溶液中经光照反应制得，将样品取出，用无水乙醇超声清洗，即在TiO2纳米管表面得到均匀分布的纳米银颗粒。制备纳米银的工艺参数为：The nano-silver particles are prepared by dopamine reduction method. The titanium alloy with titanium dioxide nanotube arrays grown on the surface is placed in a dopamine Tris solution for 24 hours, and then placed in a silver nitrate (AgNO 3 ) solution for light reaction. prepared, the sample was taken out, and ultrasonically cleaned with absolute ethanol, that is, evenly distributed nano-silver particles were obtained on the surface of the TiO 2 nanotube. The process parameters for preparing nano-silver are:
Tris浓度：0.3mg/mlTris concentration: 0.3mg/ml
多巴胺浓度：0.3mg/mlDopamine concentration: 0.3mg/ml
硝酸银溶液浓度：0.01mol/LSilver nitrate solution concentration: 0.01mol/L
光照时间：10minLighting time: 10min
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。The present invention has been described as an example above, and it should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be made by those skilled in the art without creative labor all fall within the scope of this invention. protection scope of the invention.
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