CN105506744B - A kind of preparation method of metal material surface from growth whisker fibre - Google Patents
A kind of preparation method of metal material surface from growth whisker fibre Download PDFInfo
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- CN105506744B CN105506744B CN201410503191.3A CN201410503191A CN105506744B CN 105506744 B CN105506744 B CN 105506744B CN 201410503191 A CN201410503191 A CN 201410503191A CN 105506744 B CN105506744 B CN 105506744B
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- 239000000835 fiber Substances 0.000 title claims abstract description 32
- 239000007769 metal material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 44
- 239000011777 magnesium Substances 0.000 claims abstract description 44
- 238000005260 corrosion Methods 0.000 claims abstract description 30
- 230000007797 corrosion Effects 0.000 claims abstract description 30
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- -1 phosphate radical salt Chemical class 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000007836 KH2PO4 Substances 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 239000012876 carrier material Substances 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 150000001804 chlorine Chemical class 0.000 claims 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 13
- 239000007857 degradation product Substances 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 108010022355 Fibroins Proteins 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Materials For Medical Uses (AREA)
Abstract
A kind of preparation method it is an object of the invention to provide metal material surface from growth whisker fibre, it is characterised in that：Simple metal magnesium reacts in the mixed solution containing villaumite and phosphate radical salt through corrosion degradation, from one layer of whisker fibre of growth on simple metal magnesium surface.This method technique is simple, cost is low, thus it is possible to vary material surface form, increases its specific surface area, so as to meet metal material application under particular surroundings.
Description
Technical field
The present invention relates to the technology of preparing in metal material surface modification field, it is spontaneous especially to provide a kind of metal material surface
The preparation method of long whisker fibre.
Background technology
Bulk metal material surface modification, is the hot spot in Recent study Material Field.Either in aerospace, vapour
The industries such as turner industry, chemical industry, building industry, medicine and biomaterial, it is desirable to which metal material surface modification technique is more and more
It is high.With coating technology, the continuous development of membrane technology, electroplating technology, metal material surface modification technique becomes dynamic, note
More new intensions are entered.Metal surface modification be in order to improve the application of material, preferably with the environments match of surrounding.
In recent years by the method for special modification, make application of the material under certain particular surroundings quite varied.Such as：Hu Jia
[Materials Science and Engineering .2001,19 (3) such as mountain：79-83] carbon fiber and former silk are made after organic reagent is surface-treated
The fiber and hydroxyapatite mix that length is 2mm or so, and it is compressing with 10MPa pressure.[the fibre reinforceds such as Zhao Junliang
The preparation of Hydroxyapatite/Epoxy Composite and mechanical property, Materials Science and Engineering journal, 2003,21 (5)：
640-643] it is compound using epoxy resin, carbon fiber and hydroxyapatite, the toughness and intensity for making hydroxylapatite ceramic improve,
The purpose is to make material possess certain function, the application requirement under particular surroundings is complied with.
Chinese patent application " cranial bone implant of hydroxyapatite " (publication number CN1370507A) discloses one kind in silk
Layering adds the technology that cranial bone implant is made in hydroxylapatite powder between net, hollow nylon wire；A kind of " fibroin hydroxyapatite
Composite material and preparation method thereof " (publication number CN1736492A) is disclosed using hydroxyapatite, fibroin albumen as matrix, is used
Solution blending-freezing gel method, is made the composite porous technology of fibroin hydroxyapatite.These patent applications are all logical
Surface, the special modification of aspect progress of material are crossed, to reach the requirement under certain environmental requirement." magnesium powder surface in situ is given birth to
The long method for preparing magnesia crystal whisker/magnesium composite powder " (103008652 A of publication number CN) is disclosed in magnesium powder surface in situ
The method that growth prepares magnesia crystal whisker, prefabricated mixed-powder is obtained using boric acid and magnesium powder, then mixed-powder is laid in stone
Calcined in Britain side's boat under argon gas protection and magnesia crystal whisker is made.
However, document report is had not yet to see from the technical solution for growing whisker in magnesium metal block materials surface in situ.
The content of the invention
It is an object of the invention to provide a kind of metal material surface from the preparation method for growing whisker fibre, directly by gold
Belong to material immersion in the solution, change through a series of materializations, obtain the self-growing whisker fibre of metal material surface, this method can
In the form of changing material surface, increase its specific surface area, so as to meet its application requirement in particular circumstances.
The present invention specifically provides a kind of metal material surface from the preparation method for growing whisker fibre, it is characterised in that：
Simple metal magnesium (preferably pure content of magnesium >=99.9%) is immersed in the mixed solution containing villaumite and phosphate radical salt, is dropped through corrosion
Solution reaction, from one layer of whisker fibre of growth on simple metal magnesium surface.The metal material is block materials, such as metal bar, gold
Belong to plate (or piece), metal derby, wire etc., but can not be for metal dust, rolling, extruding, drawing form can be used to prepare.
Wherein described villaumite is NaCl, KCl, CaCl2、MgCl2、FeCl2、FeCl3、CuCl、CuCl2、ZnCl2, one kind
Or it is a variety of, phosphate radical salt is Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、KH2PO4、Ca3(PO4)2、CaHPO4、Ca
(H2PO4)2One or more.
When preparing solution, villaumite and phosphate radical salt (including phosphate radical salt, hydrogen phosphate salt and dihydrogen phosphate salt)
Mass ratio is 60-2:1, or require Chlorine in Solution ion and phosphate anion (including phosphate anion, one hydrogen radical ion of phosphoric acid
And dihydrogen phosphate ions) molar ratio be 150-5:1, it can also contain MgSO in mixed solution4And/or NaHCO3, this is mixed
Chemical stability requirements should be met by closing solution.
Preparation method of the metal material surface of the present invention from growth whisker fibre, it is characterised in that：Prepare whisker fibre
Environment temperature during dimension is between room temperature -80 DEG C, when preparation time is >=3 small.
The metallic magnesium surface being prepared using the method for the invention has one layer of tiny whisker fibre, convenient in metal
Magnesium surface coat high molecular material and it is not easily to fall off, can be as new biological medical degradable carrier material.
Pure magnesium material can be made on pure magnesium surface from one layer of tiny whisker fibre is grown using the method for the invention
Material specific surface area significantly increases, so as to greatly increase its cell adsorption capacity.Pure MAG block body material surface grows whisker certainly at the same time
Fiber condition, also allows for carrying out secondary modification, by adsorbing other materials, such as polyphosphazene polymer lactic acid gas chromatography and medicine
Mixing, so that it may become new degradable carrier material.And the method for the invention possesses technological process simplicity, equipment requirement is not
The features such as height, manufacturing cost is cheap.
Brief description of the drawings
1 magnesium rod 7h shape appearance figures of Fig. 1 embodiments；
1 magnesium rod 24h shape appearance figures of Fig. 2 embodiments；
2 magnesium rod 7h shape appearance figures of Fig. 3 embodiments；
2 magnesium rod 24h shape appearance figures of Fig. 4 embodiments；
3 magnesium silk 7h shape appearance figures of Fig. 5 embodiments；
3 magnesium silk 24h shape appearance figures of Fig. 6 embodiments；
4 magnesium rod 3h shape appearance figures of Fig. 7 embodiments；
4 magnesium rod 7h shape appearance figures of Fig. 8 embodiments；
5 magnesium rod 3h shape appearance figures of Fig. 9 embodiments；
5 magnesium rod 7h shape appearance figures of Figure 10 embodiments.
Embodiment
Embodiment 1
Pure magnesium rolling stock, pure content of magnesium >=99.9%, if with linear cutter into the bar of diameter 1mmx20mm shapes
Dry root, polishes by sand paper, removes oxide layer during cutting, puts it into vial, places into a certain amount of absolute ethyl alcohol,
Submerged.Then carry out ultrasonic cleaning, the time every time at 15 minutes or so, untill cleaning up.After taking out drying,
It is put into spare in clean bottle.
Prepare solution chemistry component；9.5 grams of NaCl, 0.3 gram of KCl, 0.8 gram of Na2HPO4, add distilled water 200mL, corruption be made
Degraded solutions 200mL is lost, is fitted into spare in clean bottle.
5 ready pure magnesium rods are taken to be respectively put into the test tube that 5 volumes are 20mL cleanings, then with pipette, extract
Prepared solution 15mL, is added dropwise to and is respectively provided with the test tube of 1 magnesium rod, this test tube is put into the insulating box of temperature-controllable
In, the temperature controlling range of insulating box is room temperature -200 DEG C scope, after setting reaction temperature as 50 DEG C, waits corrosion degradation production
The generation of thing.From the corrosion degradation time, 3 it is small when after, just have in solution corrosion degradation product generation.Continuous observation corrodes
Degraded situation, observes pure magnesium corrosion degradation product in different reaction time points respectively, and the time is set in 7h, 24h and is observed.
And take out the magnesium rod for the degraded that is corroded, cleaned, be put into after dry in the preferable bottle of seal, in case scanning electron microscope with distilled water
Carry out surface topography observation.Electronic Speculum morphology observation is scanned through, finds there is a substratum whisker fibre in pure MAG block body material surface
Growth, scanning electron microscope (SEM) photograph are shown in Fig. 1,2.
Embodiment 2
Pure magnesium extrded material, pure content of magnesium >=99.9%, if with linear cutter into the bar of diameter 1mmx20mm shapes
Dry root, polishes by sand paper, removes oxide layer during cutting, puts it into vial, places into a certain amount of absolute ethyl alcohol,
Submerged.Then carry out ultrasonic cleaning, the time every time at 15 minutes or so, untill cleaning up.Taking-up is dried
After machine drying, it is put into spare in clean bottle.
Prepare solution chemistry component：9.5 grams of NaCl, 0.3 gram of KCl, 1.25 grams of Na2HPO4, 0.5 gram of KH2PO4, add distilled water
200mL, is made corrosion degradation solution 200mL, is fitted into spare in clean bottle.
5 ready pure magnesium rods are taken to be respectively put into the test tube that 5 volumes are 20mL cleanings, then with pipette, extract
Prepared solution 15mL, is added dropwise to and is respectively provided with the test tube of 1 magnesium rod, this test tube is put into the insulating box of temperature-controllable
In, after setting reaction temperature as 80 DEG C, wait the generation of corrosion degradation product.From the corrosion degradation time, 3 it is small when after,
Just there is the generation of corrosion degradation product in solution.Continuous observation corrosion degradation situation, it is pure in different reaction time point observations respectively
Magnesium corrosion degradation product, time are set in 7h, 24h and are observed.And take out the magnesium rod for the degraded that is corroded, it is clear with distilled water
Wash, be put into after dry in the preferable bottle of seal, be scanned through Electronic Speculum morphology observation, find there is one in pure MAG block body material surface
Substratum whisker fibre is grown, and scanning electron microscope (SEM) photograph is shown in Fig. 3,4.
Embodiment 3
Pure magnesium drawable material, pure content of magnesium >=99.9%, is processed into some of the silk material of diameter 1mmx10mm shapes, passes through
Sand paper is polished, and is removed oxide layer during cutting, is put it into vial, places into a certain amount of absolute ethyl alcohol, submerged.
Then carry out ultrasonic cleaning, the time every time at 15 minutes or so, untill cleaning up.After taking out drying, cleaning is put into
It is spare in bottle.
Prepare solution chemistry component；5.5 grams of NaCl, 0.3 gram of KCl, 2.5 grams of Na2HPO4, add distilled water 200mL, corruption be made
Degraded solutions 200mL is lost, is fitted into spare in clean bottle.
5 ready pure magnesium silks are taken to be respectively put into the test tube that 5 volumes are 20mL cleanings, then with pipette, extract
Prepared solution 15mL, is added dropwise to and is respectively provided with the test tube of 1 magnesium silk, this test tube is put into the insulating box of temperature-controllable
In, after setting reaction temperature as 30 DEG C, wait the generation of corrosion degradation product.From the corrosion degradation time, 3 it is small when after,
Just there is the generation of corrosion degradation product in solution.Continuous observation corrosion degradation situation, it is pure in different reaction time point observations respectively
Magnesium corrosion degradation product, time are set in 7h, 24h and are observed.And take out the magnesium silk for the degraded that is corroded, it is clear with distilled water
Wash, be put into after dry in the preferable bottle of seal, be scanned through Electronic Speculum morphology observation, find to have on pure magnesium wire material surface one small
Layer crystal palpus fiber growth, scanning electron microscope (SEM) photograph are shown in Fig. 5,6.
Embodiment 4
Pure magnesium drawable material, pure content of magnesium >=99.9%, is processed into some of the silk material of diameter 1mmx10mm shapes, passes through
Sand paper is polished, and is removed oxide layer during cutting, is put it into vial, places into a certain amount of absolute ethyl alcohol, submerged.
Then carry out ultrasonic cleaning, the time every time at 15 minutes or so, untill cleaning up.After taking out drying, cleaning is put into
It is spare in bottle.
Prepare solution chemistry component；5.5 grams of NaCl, 0.3 gram of KCl, 2.5 grams of Na2HPO4, 0.2 gram of CaCl2, 0.1 gram
MgSO4, 2.2 grams of NaHCO3, add distilled water 200mL, corrosion degradation solution 200mL be made, be fitted into spare in clean bottle.
5 ready pure magnesium silks are taken to be respectively put into the test tube that 5 volumes are 20mL cleanings, then with pipette, extract
Prepared solution 15mL, is added dropwise to and is respectively provided with the test tube of 1 magnesium silk, this test tube is put into the insulating box of temperature-controllable
In, after setting reaction temperature as 40 DEG C, wait the generation of corrosion degradation product.From the corrosion degradation time, 3 it is small when after,
Just there is the generation of corrosion degradation product in solution.Continuous observation corrosion degradation situation, it is pure in different reaction time point observations respectively
Magnesium corrosion degradation product, time are set in 3h, 7h and are observed.The magnesium silk for the degraded that is corroded is taken out, is cleaned with distilled water, is done
It is put into after dry in the preferable bottle of seal, is scanned through Electronic Speculum morphology observation, finds there is a small layer crystal on pure magnesium wire material surface
Palpus fiber growth, scanning electron microscope (SEM) photograph are shown in Fig. 7,8.
Embodiment 5
Pure magnesium drawable material, pure content of magnesium >=99.9%, is processed into some of the silk material of diameter 1mmx10mm shapes, passes through
Sand paper is polished, and is removed oxide layer during cutting, is put it into vial, places into a certain amount of absolute ethyl alcohol, submerged.
Then carry out ultrasonic cleaning, the time every time at 15 minutes or so, untill cleaning up.After taking out drying, cleaning is put into
It is spare in bottle.
Prepare solution chemistry component；8 grams of NaCl, 0.4 gram of KCl, 0.09 gram of Na2HPO4, 0.2 gram of CaCl2, 0.1 gram of MgSO4、
2.2 grams of NaHCO3, 0.06 gram of KH2PO4Add distilled water 200mL, corrosion degradation solution 200mL is made, be fitted into spare in clean bottle.
5 ready pure magnesium silks are taken to be respectively put into the test tube that 5 volumes are 20mL cleanings, then with pipette, extract
Prepared solution 15mL, is added dropwise to and is respectively provided with the test tube of 1 magnesium silk, this test tube is put into the insulating box of temperature-controllable
In, after setting reaction temperature as 40 DEG C, wait the generation of corrosion degradation product.From the corrosion degradation time, 3 it is small when after,
Just there is the generation of corrosion degradation product in solution.Continuous observation corrosion degradation situation, it is pure in different reaction time points, observation respectively
Magnesium corrosion degradation product, time are set in 3h, 7h and are observed.And take out the magnesium silk for the degraded that is corroded, cleaned with distilled water,
It is put into after drying in the preferable bottle of seal, is scanned through Electronic Speculum morphology observation, finds there is a substratum on pure magnesium wire material surface
Whisker fibre is grown, and scanning electron microscope (SEM) photograph is shown in Fig. 9,10.
Inspection result according to embodiment 1-5 scanning electron microscope shape appearance figures carries out phenetic analysis, determines by of the present invention
Technology of preparing, can obtain a kind of bulk metal material surface self-grown whisker fibre.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of metal material surface grows the preparation method of whisker fibre certainly, it is characterised in that：Simple metal magnesium is containing villaumite
In the mixed solution of phosphate radical salt, reacted through corrosion degradation, grow one layer of whisker fibre certainly in simple metal magnesium surface；It is described mixed
The molar ratio for closing Chlorine in Solution ion and phosphate anion is 150-5:1.
2. grow the preparation method of whisker fibre certainly according to metal material surface described in claim 1, it is characterised in that：The chlorine
Salt is NaCl, KCl, CaCl2、MgCl2、FeCl2、FeCl3、CuCl、CuCl2、ZnCl2One or more, phosphate radical salt is
Na3PO4、Na2HPO4、NaH2PO4、K3PO4、K2HPO4、KH2PO4、Ca3(PO4)2、CaHPO4、Ca(H2PO4)2One or more.
3. grow the preparation method of whisker fibre certainly according to the metal material surface of claim 1 or 2, it is characterised in that：It is mixed
Close in solution and also contain MgSO4And/or NaHCO3。
4. grow the preparation method of whisker fibre certainly according to the metal material surface of claim 1 or 2, it is characterised in that：Institute
State the mixed solution containing villaumite and phosphate radical salt and meet chemical stability requirements.
5. grow the preparation method of whisker fibre certainly according to the metal material surface of claim 1 or 2, it is characterised in that：System
Environment temperature during standby whisker fibre is between room temperature -80 DEG C, when preparation time is >=3 small.
6. grow the preparation method of whisker fibre certainly according to metal material surface described in claim 1, it is characterised in that：It is described pure
Pure content of magnesium >=99.9% in magnesium metal.
7. the metal material of surface self-grown whisker fibre prepared by preparation method described in a kind of claim 1.
8. the metal material of surface self-grown whisker fibre is as biological medical degradable carrier material described in a kind of claim 7
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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 |
-
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 |
|---|
| AZ63 镁合金在氯化钠溶液中的孔蚀及缓蚀研究;陈琳等;《表面技术》;20131031;第24-28页 * |
| Comparative study of different environmentally friendly (Chromium-free) methods for surface modification of pure magnesium;A.A. Zuleta等;《Surface & Coatings Technology》;20110606;第5254-5259页 * |
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