CN103834984B - A kind of preparation method with classification nanostructure marmem - Google Patents
A kind of preparation method with classification nanostructure marmem Download PDFInfo
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- CN103834984B CN103834984B CN201410076918.4A CN201410076918A CN103834984B CN 103834984 B CN103834984 B CN 103834984B CN 201410076918 A CN201410076918 A CN 201410076918A CN 103834984 B CN103834984 B CN 103834984B
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- nitinol
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Abstract
A kind of preparation method with classification nanostructure marmem. The object of this invention is to provide a kind of easy and simple to handle, do not changing under original Nitinol premium properties condition, making its surface there is better biocompatibility and can carry other materials in the above to make it obtain the preparation method of the niti-shaped memorial alloy with classification nanostructure of different biological function.
Description
Technical field
The present invention relates to niti-shaped memorial alloy surface modification field, particularly relate to surface and there is classifying nanoThe preparation method of the niti-shaped memorial alloy of architectural feature.
Background technology
Biomaterial (Biomaterials) refers to the material using in physiological environment, to bioactivatorBeing fixed, diagnoses, treats and replace the tissue of damage, the material of organ to organism. It is to grindStudy carefully the basis of artificial organs and medicine equipment, along with aging population, and industry, traffic, physical culture etc. causeWound increase, people are also increasing to the demand of biological and medicinal implant material and goods thereof. Wherein medical nickelTitanium shape memory alloy has special SME, super-elasticity, higher fatigue limit, good because of itWearability and good biocompatibility, obtain a wide range of applications at medical domain, as abnormal tooth silk, painstaking effortEnlargement of pipe support, repair of fractured bones material etc. But because Nitinol is metal material, metal implant corrosion andBiocompatibility issues receives much concern, and the surface nature of these problems and implant is closely related.
Although niti-shaped memorial alloy has many clinical advantages, itself can discharge a large amount of nickel, weKnow that a certain amount of nickel is needed in human body, but just there is very strong cytotoxicity and carcinogenic work after how measuringWith, so a kind of material implant into body, is harmful. Therefore do not changing alloy substrate shape effectAnswer under prerequisite, to improve biocompatibility and reduce cytotoxicity and be very important. For these problems, peopleDeveloped niti-shaped memorial alloy, surface modification becomes a focus of this area research for many years.
Utilize the classifying nano material of preparing after Nitinol removal alloying, its surface is with a kind of hierarchy,Surface has nano-scale hole, is a kind of special co-continuous loose structure, this nano level aperture sizeMake it have higher specific area and other special physics, chemistry and mechanical property. And prepare thisClassifying nano material mainly contains two kinds of methods: template and removal alloying method. Template be with the aluminium oxide of porous,Liquid crystalline phase or nano particle are template, obtain final nano-porous structure by copying the structure of template. Go to closeAurification uses selective chemical or electrochemical corrosion principle, and between alloy constituent element, electrode potential differs larger feelingsUnder condition, allow the element that electrochemical properties is more active in alloy optionally dissolve and to enter electricity under electrolytical effectSeparate liquid and leave electrochemical properties compared with stable element, the metallic atom of remaining comparatively inertia is final through the growth of reunitingForm the nano-porous structure of co-continuous. Different from template, go alloyage can be by corrosion process andThe adjustment of follow-up heat treatment process realizes the dynamic control to bore hole size and spatial arrangement. Nowadays NiTi shapeThere is following some deficiency in memorial alloy surface treatment: the one, and operating process complexity; The 2nd, changing bio-compatibleAfter property, other performances of alloy also can change.
Summary of the invention
The object of the invention is to prepare two not enough aspects of classification nanostructure Nitinol for removal alloying,Provide a kind of easy and simple to handle, not changing under original Nitinol premium properties condition, make it have better lifeThing compatibility and can carry that other materials make that it obtains difference in functionality in the above there is classification nanostructureThe preparation method of niti-shaped memorial alloy.
Object of the present invention is achieved through the following technical solutions.
There is a preparation method for classification nanostructure marmem, it is characterized in that comprising as followsStep:
Step 1,
Sample pretreatment, by Nitinol polishing, is placed in the about 30min of acetone ultrasonic cleaning, subsequently go fromIn sub-water, the about 20min of ultrasonic cleaning, for subsequent use.
Step 2,
Compound concentration scope is the HF acid of 0.25%-1%, adds the dipotassium hydrogen phosphate solution of equivalent 60g/L to be configured toElectrolyte, for subsequent use.
Step 3,
Self-control rubber form, described template has 15 holes, and three of every rows, below template in six holesWelding copper wire wire, is coated with and seals its hole with epoxide-resin glue, outside not exposed to copper wire. Not being coated with in sealing of hole holeWhether the Nitinol described in installation steps one, with conducting electricity between universal meter test copper sheet and alloy surface, testCheng Hou, is coated with alloy in sealing of hole hole with normal temperature cure silicon rubber and does not fill up region, only exposes question response alloy surface,Finally test it with universal meter again and whether conduct electricity, conduction can be carried out following step.
Step 4,
Be anode by prepared step 3 template, graphite (purity is 99.99%), as reference electrode, is put inBe equipped with in the beaker of electrolyte of step 2 configuration, the Nitinol that participates in reaction is placed in below liquid level of electrolyte,Described beaker is placed on magnetic stirring apparatus, constantly stirs, electromotive force increases from open circuit potential under 0.1V/s conditionBe added to 10V, and under 10V, keep reaction 2h.
Step 5,
Nitinol is taken out, by washed with de-ionized water, the dry classification nanostructure marmem that both obtained.
2, a kind of preparation method with classification nanostructure marmem according to claim 1,The Nitinol that it is characterized in that described step 1 is marmem.
3, a kind of preparation method with classification nanostructure marmem according to claim 1,It is characterized in that used for electrolyte in described step 2 is that the volumetric concentration of HF acid is selected from: 0.25%, 0.5% orPerson 1%.
4, a kind of preparation side with classification nanostructure marmem according to claim 1Method, is characterized in that in described step 4, reaction temperature is normal temperature.
Beneficial effect:
(1) the prepared Nitinol with hierarchy, can effectively remove nickel ion, surfaceHierarchy can effectively stop the stripping of nickel, strengthens its biologically active, is more conducive to enter thin after human bodyBorn of the same parents' suction-operated;
(2) at titania nanotube surface deposition noble metal, can provide its photoelectric activity, antibacterialAbility, with respect to other noble metals, the price of silver is relatively cheap, toxicity is little and effect is also fine.
Brief description of the drawings
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
Fig. 1 is from pallet schematic diagram;
Fig. 2 is the Nitinol surface sweeping Electronic Speculum of the classification nanostructure of embodiment 1 use 0.25%HF acid preparationFigure;
Fig. 3 is the Nitinol surface sweeping Electronic Speculum figure of the classification nanostructure of embodiment 2 use 0.5%HF acid preparations;
Fig. 4 is the Nitinol surface sweeping Electronic Speculum figure of the classification nanostructure of embodiment 3 use 1%HF acid preparations.
Detailed description of the invention
Below in conjunction with specific embodiment, further set forth the present invention.
For a better understanding of the present invention, the present invention is done detailed further below in conjunction with drawings and ExamplesExplanation.
Embodiment 1
The Nitinol of the classification nanostructure of 0.25%HF acid preparation:
(1) sample pretreatment, by Nitinol polishing, is placed in the about 30min of acetone ultrasonic cleaning, exists subsequentlyDeionized water for ultrasonic is cleaned about 20min, for subsequent use.
(2) prepare 0.25% HF acid, add the dipotassium hydrogen phosphate of 60g/L to be configured to electrolyte.
(3) original mold plate (seeing accompanying drawing 1) is put in self-control, below template, in six holes, welds copper wire wire, usesEpoxide-resin glue is coated with other holes of envelope, outside not exposed to copper sheet. In hole, install Nitinol not encapsulating,With whether conducting electricity between universal meter test copper sheet and alloy surface, after having tested, be coated with and seal with normal temperature cure silicon rubberIn hole, alloy does not fill up region, only exposes question response alloy surface, finally again with universal meter test its conduction withNo, conduction can be carried out following step.
(4), taking above-mentioned Ti-Ni alloy template as anode, graphite, as reference electrode, is put in step 2 electricity is housedSeparate in the beaker of liquid, the Nitinol that participates in reaction is placed in below liquid level of electrolyte, and described beaker is placed in to magnetic forceOn agitator, constantly stir, electromotive force is increased to 10V from open circuit potential under 0.1V/s condition in addition, andUnder 10V, keep 2h.
(5) sample is taken out, by washed with de-ionized water, dry. Testing result: the classification that has making is receivedThe island of skewness not of uniform size on the Nitinol surface of rice structure, are formed, as shown in Figure 2.
Embodiment 2
The Nitinol of the classification nanostructure of 0.5%HF acid preparation:
(1) (3) (4) (5) step is with embodiment 1.
(2) mixed electrolytic solution consists of 0.5% HF acid, the dipotassium hydrogen phosphate solution of appropriate 60g/L.
Testing result: the Nitinol surface with classification nanostructure making has formed more island, and moreCome more intensive, as shown in Figure 3.
Embodiment 3
The Nitinol of the classification nanostructure of 1%HF acid preparation:
(1) (3) (4) (5) step is with embodiment 1.
(2) mixed electrolytic solution consists of 1% HF acid, the dipotassium hydrogen phosphate solution of appropriate 60g/L.
Testing result: more encrypt on the inert atom island that the Nitinol surface with classification nanostructure making formsCollect and be interconnected, these island are also by being interconnected to form, as shown in Figure 4 by little island. ICan be at inner other materials that add of these holes as macromolecule, the situation that this alloy is improved in compatibilityUnder can also meet the otherwise needs of human body.
Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described. In addition shouldUnderstand, after having read the content of the present invention's instruction, those skilled in the art can do various changing to the present inventionMove or amendment, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (4)
1. there is a preparation method for classification nanostructure marmem, it is characterized in that comprising the steps:
Step 1,
Sample pretreatment, by Nitinol polishing, is placed in acetone ultrasonic cleaning 30min, cleans 20min subsequently in deionized water for ultrasonic, for subsequent use;
Step 2,
Compound concentration scope is the HF acid of 0.25%-1%, adds the dipotassium hydrogen phosphate solution of equivalent 60g/L to be configured to electrolyte, for subsequent use;
Step 3,
Self-control rubber form, described template has 15 holes, and three of every rows weld copper wire wire in six holes below template, are coated with and seal its hole with epoxide-resin glue, outside not exposed to copper wire; Nitinol is installed not being coated with in sealing of hole hole, with whether conducting electricity between universal meter test copper sheet and alloy surface, after having tested, be coated with alloy in sealing of hole hole with normal temperature cure silicon rubber and do not fill up region, only expose question response alloy surface, finally test it with universal meter again and whether conduct electricity, conduction can be carried out following step;
Step 4,
Be anode by prepared step 3 template, purity is that 99.99% graphite is as reference electrode, be put in the beaker of the electrolyte that step 2 configuration is housed, the Nitinol that participates in reaction is placed in below liquid level of electrolyte, described beaker is placed on magnetic stirring apparatus, constantly stir, electromotive force is increased to 10V from open circuit potential under 0.1V/s condition, and under 10V, keeps reaction 2h;
Step 5,
Sample is taken out, by washed with de-ionized water, be drying to obtain classification nanostructure marmem.
2. a kind of preparation method with classification nanostructure marmem according to claim 1, the Nitinol that it is characterized in that described step 1 is marmem.
3. a kind of preparation method with classification nanostructure marmem according to claim 1, is characterized in that the volumetric concentration of the HF acid used for electrolyte in described step 2 is selected from: 0.25%, 0.5% or 1%.
4. a kind of preparation method with classification nanostructure marmem according to claim 1, is characterized in that in described step 4, reaction temperature is normal temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101437467A (en) * | 2004-08-13 | 2009-05-20 | 斯特根有限公司 | Medical devices having porous layers and methods for making the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101437467A (en) * | 2004-08-13 | 2009-05-20 | 斯特根有限公司 | Medical devices having porous layers and methods for making the same |
Non-Patent Citations (1)
| Title |
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| Fabrication of Nanoporous Surface on Biomedical NiTi Alloy by Surface Dealloying of Ni;Yunchang Xin;《3rd International Nanoelectronics Conference》;20100131;第1页 * |
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