CN105506744A - Preparation method for self-growing whisker fiber on surface of metal material - Google Patents
Preparation method for self-growing whisker fiber on surface of metal material Download PDFInfo
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- CN105506744A CN105506744A CN201410503191.3A CN201410503191A CN105506744A CN 105506744 A CN105506744 A CN 105506744A CN 201410503191 A CN201410503191 A CN 201410503191A CN 105506744 A CN105506744 A CN 105506744A
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Abstract
The objective of the invention is to provide a preparation method for a self-growing whisker fiber on the surface of a metal material. The preparation method is characterized by comprising a step of allowing pure magnesium metal to undergo a corrosion and degradation reaction in a mixed solution containing chlorine salt and phosphate salt so as to realize self-growing of a layer of a whisker fiber on the surface of the pure magnesium metal. The preparation method is simple, has low cost and can change the surface morphology of the material and increase the specific surface area of the material, thereby meeting requirements of application of the metal material in special environments.
Description
Technical field
The present invention relates to the technology of preparing that metal material surface modifies field, provide a kind of metal material surface from the preparation method of growth whisker fibre especially.
Background technology
Bulk metal material finishing is the focus in Recent study Material Field.No matter be in industries such as aerospace, automotive industry, chemical industry, building industry, medicine and biomaterials, require that metal material surface modification technique is more and more high.Along with the development of coating technology, membrane technique, electroplating technology, metal material surface modification technique becomes dynamic, is filled with how new intension.It is applicability in order to improve material that metallic surface is modified, better and the environments match of surrounding.
In recent years by the method for special modification, make the application of material under certain particular surroundings very extensive.As: carbon fiber and former silk are made the fiber and hydroxyapatite mix that length is about 2mm by Hu Jiashan etc. [Materials Science and Engineering .2001,19 (3): 79-83] after organic reagent surface treatment, and with the compression moulding of 10MPa pressure.[preparation of carbon fibre reinforced hydroxylapatite/epoxy resin composite material and the mechanical property such as Zhao Junliang, Materials Science and Engineering journal, 2003,21 (5): 640-643] epoxy resin, carbon fiber and hydroxyapatite compound is adopted, the toughness of hydroxylapatite ceramic and intensity are improved, its objective is and make material possess certain function, the application requiring under making it meet particular surroundings.
Chinese patent application " cranial bone implant of hydroxyapatite " (publication number CN1370507A) disclose a kind of between silk net, hollow nylon wire layering add the technology that hydroxylapatite powder makes cranial bone implant; " a kind of fibroin hydroxyapatite composite material and preparation method thereof " (publication number CN1736492A) discloses with hydroxyapatite, silk fibroin as matrix, adopt solution blending-freezing gel method, the technology that obtained fibroin hydroxyapatite is composite porous.These patent applications are all carry out special modification, to reach the service requirements under certain environmental requirement by the surface of material, aspect." method of magnesia crystal whisker/magnesium composite powder is prepared in the growth of magnesium powder surface in situ " (publication number CN103008652A) discloses the method preparing magnesia crystal whisker in the growth of magnesium powder surface in situ; adopt boric acid and magnesium powder to obtain prefabricated mixed powder, then mixed powder to be laid in quartzy Noah's ark calcining under argon shield and to obtain magnesia crystal whisker.
But, have not yet to see bibliographical information at MAGNESIUM METAL block materials surface in situ from the technical scheme of growth whisker.
Summary of the invention
The object of the present invention is to provide a kind of metal material surface from the preparation method of growth whisker fibre, directly metallic substance is soaked in the solution, change through a series of materialization, obtain the self-growing whisker fibre of metal material surface, the method can change material surface form, increase its specific surface area, thus meet its application requiring in particular circumstances.
The present invention specifically provides the preparation method of a kind of metal material surface from growth whisker fibre, it is characterized in that: pure metal magnesium (preferred pure Mg content >=99.9%) is immersed in the mixing solutions containing villaumite and phosphate radical salt, through corrosion degradation reaction, from growth one deck whisker fibre on pure metal magnesium surface.Described metallic substance is block materials, as metal bar, metal sheet (or sheet), metal block, wire etc., but can not think metal-powder, can adopt rolling, extruding, the preparation of drawing form.
Wherein said villaumite is NaCl, KCl, CaCl
2, MgCl
2, FeCl
2, FeCl
3, CuCl, CuCl
2, ZnCl
2, one or more, phosphate radical salt is Na
3pO
4, Na
2hPO
4, NaH
2pO
4, K
3pO
4, K
2hPO
4, KH
2pO
4, Ca
3(PO
4)
2, CaHPO
4, Ca (H
2pO
4)
2one or more.
During obtain solution, the mass ratio of villaumite and phosphate radical salt (comprising phosphate radical salt, hydrogen phosphate salt and dihydrogen phosphate salt) is 60-2:1, or the mol ratio requiring Chlorine in Solution ion and phosphate anion (comprising phosphate anion, phosphoric acid one hydrogen radical ion and dihydrogen phosphate ions) is 150-5:1, also can contain MgSO in mixing solutions
4and/or NaHCO
3, this mixing solutions should meet chemical stability requirements.
Metal material surface of the present invention, from the preparation method of growth whisker fibre, is characterized in that: envrionment temperature when preparing whisker fibre is between normal temperature-80 DEG C, and preparation time is >=3 hours.
The whisker fibre that the metallic magnesium surface adopting the method for the invention to prepare has one deck tiny, conveniently the difficult drop-off at metallic magnesium surface coating macromolecular material, can be used as new biological medical degradable solid support material.
Adopt the method for the invention from growing the tiny whisker fibre of one deck on pure magnesium surface, pure magnesium material specific surface area obviously can be increased, thus greatly increase its cell adsorption ability.Pure MAG block body material surface is from growth whisker fibre state simultaneously, being also convenient to carry out secondary modification, by adsorbing other material, as gas chromatography and medicament mixed such as polyphosphazene polymer lactic acid, just becoming new degradable solid support material.And the method for the invention to possess technical process easy, the features such as equipment requirements is not high, and preparation cost is cheap.
Accompanying drawing explanation
Fig. 1 embodiment 1 magnesium rod 7h shape appearance figure;
Fig. 2 embodiment 1 magnesium rod 24h shape appearance figure;
Fig. 3 embodiment 2 magnesium rod 7h shape appearance figure;
Fig. 4 embodiment 2 magnesium rod 24h shape appearance figure;
Fig. 5 embodiment 3 magnesium silk 7h shape appearance figure;
Fig. 6 embodiment 3 magnesium silk 24h shape appearance figure;
Fig. 7 embodiment 4 magnesium rod 3h shape appearance figure;
Fig. 8 embodiment 4 magnesium rod 7h shape appearance figure;
Fig. 9 embodiment 5 magnesium rod 3h shape appearance figure;
Figure 10 embodiment 5 magnesium rod 7h shape appearance figure.
Embodiment
Embodiment 1
Pure magnesium rolling stock, pure Mg content >=99.9%, becomes the bar some of diameter 1mmx20mm shape with linear cutter, through sand papering, remove zone of oxidation during cutting, put it in vial, then put into a certain amount of dehydrated alcohol, by its submergence.Then carry out ultrasonic cleaning, the time at every turn at about 15 minutes, until clean up.After taking-up dries up, put into clean bottle for subsequent use.
Obtain solution chemical composition; 9.5 grams of NaCl, 0.3 gram of KCl, 0.8 gram of Na
2hPO
4, adding distil water 200mL, obtained corrosion degradation solution 200mL, loads in clean bottle for subsequent use.
Get 5 ready pure magnesium rods and put into the test tube that 5 volumes are 20mL cleaning respectively, again with the solution 15mL that pipette, extract has prepared, be added dropwise in the test tube that 1 magnesium rod is housed respectively, this test tube is put into the thermostat container of temperature-controllable, the temperature controlling range of thermostat container is normal temperature-200 DEG C scopes, setting temperature of reaction is after 50 DEG C, waits for the generation of corrosion degradation product.Observe from the corrosion degradation time, after 3 hours, in solution, just have corrosion degradation product to generate.Continuous observation corrosion degradation situation, observe pure magnesium corrosion degradation product at point of different reaction times respectively, the time is set in 7h, 24h and observes.And the magnesium rod of the degraded that is corroded is taken out, with distilled water cleaning, put into the good bottle of stopping property after drying, carry out surface topography observation in order to scanning electron microscope.Through scanning electron microscope morphology observation, find there is a substratum whisker fibre growth at pure MAG block body material surface, scanning electron microscope (SEM) photograph is shown in Fig. 1,2.
Embodiment 2
Pure magnesium extruded material, pure Mg content >=99.9%, becomes the bar some of diameter 1mmx20mm shape with linear cutter, through sand papering, remove zone of oxidation during cutting, put it in vial, then put into a certain amount of dehydrated alcohol, by its submergence.Then carry out ultrasonic cleaning, the time at every turn at about 15 minutes, until clean up.After taking-up blower dries up, put into clean bottle for subsequent use.
Obtain solution chemical composition: 9.5 grams of NaCl, 0.3 gram of KCl, 1.25 grams of Na
2hPO
4, 0.5 gram of KH
2pO
4, adding distil water 200mL, obtained corrosion degradation solution 200mL, loads in clean bottle for subsequent use.
Get 5 ready pure magnesium rods and put into the test tube that 5 volumes are 20mL cleaning respectively, again with the solution 15mL that pipette, extract has prepared, be added dropwise in the test tube that 1 magnesium rod is housed respectively, this test tube is put into the thermostat container of temperature-controllable, setting temperature of reaction is after 80 DEG C, waits for the generation of corrosion degradation product.Observe from the corrosion degradation time, after 3 hours, in solution, just have corrosion degradation product to generate.Continuous observation corrosion degradation situation, observe pure magnesium corrosion degradation product at point of different reaction times respectively, the time is set in 7h, 24h and observes.And the magnesium rod of the degraded that is corroded is taken out, with distilled water cleaning, put into the good bottle of stopping property after drying, through scanning electron microscope morphology observation, find there is a substratum whisker fibre growth at pure MAG block body material surface, scanning electron microscope (SEM) photograph is shown in Fig. 3,4.
Embodiment 3
Pure magnesium drawable material, pure Mg content >=99.9%, is processed into the silk material some of diameter 1mmx10mm shape, through sand papering, removes zone of oxidation during cutting, puts it in vial, then put into a certain amount of dehydrated alcohol, by its submergence.Then carry out ultrasonic cleaning, the time at every turn at about 15 minutes, until clean up.After taking-up dries up, put into clean bottle for subsequent use.
Obtain solution chemical composition; 5.5 grams of NaCl, 0.3 gram of KCl, 2.5 grams of Na
2hPO
4, adding distil water 200mL, obtained corrosion degradation solution 200mL, loads in clean bottle for subsequent use.
Get 5 ready pure magnesium silks and put into the test tube that 5 volumes are 20mL cleaning respectively, again with the solution 15mL that pipette, extract has prepared, be added dropwise in the test tube that 1 magnesium silk is housed respectively, this test tube is put into the thermostat container of temperature-controllable, setting temperature of reaction is after 30 DEG C, waits for the generation of corrosion degradation product.Observe from the corrosion degradation time, after 3 hours, in solution, just have corrosion degradation product to generate.Continuous observation corrosion degradation situation, observe pure magnesium corrosion degradation product at point of different reaction times respectively, the time is set in 7h, 24h and observes.And the magnesium silk of the degraded that is corroded is taken out, with distilled water cleaning, put into the good bottle of stopping property after drying, through scanning electron microscope morphology observation, find there is a substratum whisker fibre growth on pure magnesium wire material surface, scanning electron microscope (SEM) photograph is shown in Fig. 5,6.
Embodiment 4
Pure magnesium drawable material, pure Mg content >=99.9%, is processed into the silk material some of diameter 1mmx10mm shape, through sand papering, removes zone of oxidation during cutting, puts it in vial, then put into a certain amount of dehydrated alcohol, by its submergence.Then carry out ultrasonic cleaning, the time at every turn at about 15 minutes, until clean up.After taking-up dries up, put into clean bottle for subsequent use.
Obtain solution chemical composition; 5.5 grams of NaCl, 0.3 gram of KCl, 2.5 grams of Na
2hPO
4, 0.2 gram of CaCl
2, 0.1 gram of MgSO
4, 2.2 grams of NaHCO
3, adding distil water 200mL, obtained corrosion degradation solution 200mL, loads in clean bottle for subsequent use.
Get 5 ready pure magnesium silks and put into the test tube that 5 volumes are 20mL cleaning respectively, again with the solution 15mL that pipette, extract has prepared, be added dropwise in the test tube that 1 magnesium silk is housed respectively, this test tube is put into the thermostat container of temperature-controllable, setting temperature of reaction is after 40 DEG C, waits for the generation of corrosion degradation product.Observe from the corrosion degradation time, after 3 hours, in solution, just have corrosion degradation product to generate.Continuous observation corrosion degradation situation, observe pure magnesium corrosion degradation product at point of different reaction times respectively, the time is set in 3h, 7h and observes.Taken out by the magnesium silk of the degraded that is corroded, with distilled water cleaning, put into the good bottle of stopping property after drying, through scanning electron microscope morphology observation, find there is a substratum whisker fibre growth on pure magnesium wire material surface, scanning electron microscope (SEM) photograph is shown in Fig. 7,8.
Embodiment 5
Pure magnesium drawable material, pure Mg content >=99.9%, is processed into the silk material some of diameter 1mmx10mm shape, through sand papering, removes zone of oxidation during cutting, puts it in vial, then put into a certain amount of dehydrated alcohol, by its submergence.Then carry out ultrasonic cleaning, the time at every turn at about 15 minutes, until clean up.After taking-up dries up, put into clean bottle for subsequent use.
Obtain solution chemical composition; 8 grams of NaCl, 0.4 gram of KCl, 0.09 gram of Na
2hPO
4, 0.2 gram of CaCl
2, 0.1 gram of MgSO
4, 2.2 grams of NaHCO
3, 0.06 gram of KH
2pO
4adding distil water 200mL, obtained corrosion degradation solution 200mL, loads in clean bottle for subsequent use.
Get 5 ready pure magnesium silks and put into the test tube that 5 volumes are 20mL cleaning respectively, again with the solution 15mL that pipette, extract has prepared, be added dropwise in the test tube that 1 magnesium silk is housed respectively, this test tube is put into the thermostat container of temperature-controllable, setting temperature of reaction is after 40 DEG C, waits for the generation of corrosion degradation product.Observe from the corrosion degradation time, after 3 hours, in solution, just have corrosion degradation product to generate.Continuous observation corrosion degradation situation, respectively at point of different reaction times, observe pure magnesium corrosion degradation product, the time is set in 3h, 7h and observes.And the magnesium silk of the degraded that is corroded is taken out, with distilled water cleaning, put into the good bottle of stopping property after drying, through scanning electron microscope morphology observation, find there is a substratum whisker fibre growth on pure magnesium wire material surface, scanning electron microscope (SEM) photograph is shown in Fig. 9,10.
Assay according to embodiment 1-5 scanning electron microscope shape appearance figure carries out phenetic analysis, determines by technology of preparing of the present invention, can obtain a kind of bulk metal material surface self-grown whisker fibre.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (9)
1. metal material surface is from a preparation method for growth whisker fibre, it is characterized in that: pure metal magnesium, in the mixing solutions containing villaumite and phosphate radical salt, through corrosion degradation reaction, grows one deck whisker fibre at pure metal magnesium surface certainly.
2., according to the preparation method of metal material surface described in claim 1 from growth whisker fibre, it is characterized in that: described villaumite is NaCl, KCl, CaCl
2, MgCl
2, FeCl
2, FeCl
3, CuCl, CuCl
2, ZnCl
2one or more, phosphate radical salt is Na
3pO
4, Na
2hPO
4, NaH
2pO
4, K
3pO
4, K
2hPO
4, KH
2pO
4, Ca
3(PO
4)
2, CaHPO
4, Ca (H
2pO
4)
2one or more.
3., according to the preparation method of metal material surface described in claim 1 from growth whisker fibre, it is characterized in that: the mol ratio of described chlorion and phosphate anion is 150-5:1.
4. according to the preparation method of metal material surface described in claim 1,2 or 3 from growth whisker fibre, it is characterized in that: also containing MgSO in mixing solutions
4and/or NaHCO
3.
5. according to the preparation method of metal material surface described in claim 1,2 or 3 from growth whisker fibre, it is characterized in that: the described mixing solutions containing villaumite and phosphate radical salt meets chemical stability requirements.
6. according to the preparation method of metal material surface described in claim 1,2 or 3 from growth whisker fibre, it is characterized in that: envrionment temperature when preparing whisker fibre is between normal temperature-80 DEG C, and preparation time is >=3 hours.
7., according to the preparation method of metal material surface described in claim 1 from growth whisker fibre, it is characterized in that: pure Mg content >=99.9% in described pure metal magnesium.
8. the metallic substance of surface self-grown whisker fibre prepared by preparation method described in a claim 1.
9. the metallic substance of surface self-grown whisker fibre described in a claim 8 is as the application of biological medical degradable solid support material.
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|---|---|---|---|---|
| JPH01308899A (en) * | 1988-06-08 | 1989-12-13 | Mitsubishi Mining & Cement Co Ltd | Production of magnesia whisker |
| US6117251A (en) * | 1999-03-24 | 2000-09-12 | Bulk Chemicals, Inc. | No rinse zinc phosphate treatment for prepaint application |
| CN1919361A (en) * | 2005-08-26 | 2007-02-28 | 中国科学院金属研究所 | Biomedical degradation-absorption-controllable macromolecule metal composite implantation material and use thereof |
| CN101935872A (en) * | 2009-07-02 | 2011-01-05 | 中国科学院金属研究所 | Method for preparing Sn crystal whiskers |
| CN103328015A (en) * | 2011-01-24 | 2013-09-25 | 奥林巴斯株式会社 | Biodegradable implant material and method for producing same |
| CN105502325A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院金属研究所 | Whisker fiber material, and preparation and application thereof |
-
2014
- 2014-09-26 CN CN201410503191.3A patent/CN105506744B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308899A (en) * | 1988-06-08 | 1989-12-13 | Mitsubishi Mining & Cement Co Ltd | Production of magnesia whisker |
| US6117251A (en) * | 1999-03-24 | 2000-09-12 | Bulk Chemicals, Inc. | No rinse zinc phosphate treatment for prepaint application |
| CN1919361A (en) * | 2005-08-26 | 2007-02-28 | 中国科学院金属研究所 | Biomedical degradation-absorption-controllable macromolecule metal composite implantation material and use thereof |
| CN101935872A (en) * | 2009-07-02 | 2011-01-05 | 中国科学院金属研究所 | Method for preparing Sn crystal whiskers |
| CN103328015A (en) * | 2011-01-24 | 2013-09-25 | 奥林巴斯株式会社 | Biodegradable implant material and method for producing same |
| CN105502325A (en) * | 2014-09-26 | 2016-04-20 | 中国科学院金属研究所 | Whisker fiber material, and preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| A.A. ZULETA等: "Comparative study of different environmentally friendly (Chromium-free) methods for surface modification of pure magnesium", 《SURFACE & COATINGS TECHNOLOGY》 * |
| 陈琳等: "AZ63 镁合金在氯化钠溶液中的孔蚀及缓蚀研究", 《表面技术》 * |
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