CN104773707A - Micro/nanotube array type nickel biomimetic material and preparation method thereof - Google Patents
Micro/nanotube array type nickel biomimetic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a micro/nanotube array type nickel biomimetic material and a preparation method thereof. The micro/nanotube array type nickel biomimetic material is characterized in that the biomimetic material is based on a micro/nanotube array of fibrilia bundle templates, and the pipe wall of the micro/nanotube array consists of a nickel nanofilm. The preparation method of the biomimetic material comprises the following steps: firstly, processing fibrilia bundles with a diluted alkali solution or a sodium chlorite and sodium hydroxide aqueous solution to obtain the fibrilia bundle templates of different aggregation morphologies; then, carrying out surface grafting processing on the templates by using amino saline, and putting the templates in a nickel bath for chemical nickel plating; finally, processing the fibrilia plated with a nickel nanofilm by using an NMMO (N-methylmorpholine Oxide) aqueous solution, and removing a fiber matrix to obtain the micro/nanotube array type biomimetic materials of two aggregation morphologies. According to the method disclosed by the invention, the defects that the energy consumption is high and the material structure is easy to control when a biomimetic material is prepared at high temperature are overcome, and the metal nickel biomimetic material which is controllable in morphology can be prepared and has a potential application value in the fields of microreactors, chemical and photoelectric catalysis and the like.
Description
Technical field
The invention belongs to field of new, particularly a kind of micro-nano mitron array nickel biomimetic material and preparation method thereof.
Background technology
The material of nanoscale has excellent physical and chemical performance, but the problem of the reunion occurred in its preparations and applicatio process and random alignment can reduce effect and the availability thereof of material.The materials such as nano particle, nano wire, nanotube and nano thin-film being carried out ordering assembling is improve the performance of nano material, action and efficacy and using value, expedite product process and the very important step that should take.In the product development of micro-nano device, nanometer and micrometer tube array are a kind of excellent structures, effectively can be played effect of material, and be easy to make device by this structure assemble nanometer material.Therefore, the micro-nano pipe array preparing different shape has important using value.
Template is the important method obtaining micro-nano pipe array, and existing more report successfully uses porous silicon, aluminium oxide, titanium oxide etc. to carry out the preparation of tube array as template.Such as: China Patent Publication No.: CN102651279, publication date is on August 29th, 2012, disclose the preparation method of high energy storage polymer nanotube array of capacitors, this invention take aluminum oxide film as the polymer nanotube array of capacitors of Template preparation different size.China Patent Publication No.: CN102191555A, publication date is on September 21st, 2011, disclose the preparation method of copper-indium-selenium nanotube array film, this invention prepares multiaperture pellumina by the method for electrolytic etching, then carries out gold-plated to it and immerses containing CuCl
2, InCl
2and H
2seO
3mixed solution, eventually pass the CIS nano-tube array with yellow copper structure that annealing in process obtains dimension adjustable.China Patent Publication No.: CN102728405A, publication date is on October 17th, 2012, disclose polyoxometallate one-dimensional nano-array and the preparation method of functional direction, this invention with pellumina and polycarbonate film for template, prepared the one-dimensional nano-array of polymer and polyoxometallate MULTILAYER COMPOSITE by the method for suction filtration repeatedly, the light degradation for catalysis rhodamine B molecule is reacted.More than there is the problem that fragility is large and wellability is poor in citing display inorganic template, need in the application to carry out more complicated pretreatment, and the form of template is more single.
Compare inorganic template, biological template has various profile, and the structural form of environment optimization and more simple pretreatment process are the desirable templates preparing material structure, such as: timber, bone, silk, DNA, diatom and collagen etc.Timber is used maximum templates in biological template, has the loose structure aligned.Its derived material has potential application in micro-reaction carriers, catalytic carrier, electro-magnetic wave absorption and drug delivery etc.Such as: China Patent Publication No.: CN101838148A; publication date is on September 22nd, 2010; disclose the preparation method of corn-cob structure morph-genetic ceramic-based composite material; this invention take corncob as template; by resin-dipping under protective atmosphere and presoma dipping, and the mode of subsequent high temperature vacuum-thermal reduction obtains bionic ceramic.China Patent Publication No.: CN101838146A; publication date is on September 22nd, 2010; disclose the preparation method of hemp fabric construction morph-genetic ceramic composite material; this invention with hemp fabric structure for template; ceramic composite is obtained, the arrangement mode of heredity rayon and arrangement by carburizing under vacuum or protective atmosphere or nitriding reaction.China Patent Publication No.: CN102028972A, publication date is on April 27th, 2011, discloses a kind of honeycomb polymer-based bionic porous scaffold material and preparation method thereof etc.In addition, the both positive and negative template (.Cellulose, 2007,14:269-279) of Yongsoon Shin by regulating the acid-base value of solution to prepare the wood tissue of SiC ceramic; Atul SDeshpande obtains directed square tube array, stable chemical nature have the Ce of high-crystallinity by nanoparticle penetration dragon spruce tissue
0.5zr
0.5o
2ceramic material (Small, 2006,2:994-998), above citing gained biomimetic material is all the pottery of silica-based, carbide or oxide, there is the problem of fragility, wellability and poorly conductive, limits the range of application of formwork structure.
For above problem, in the recent period, Tang etc. are by secondary template method, the ZnO prepared by the first step receives micro tube array, synthesize electrically conductive polyaniline micrometer tube array (the Journal of Material Chemistry with fir institutional framework, 2011,21:12927-12934), but its mechanical property is low.The mode that Sandhage etc. are removed by chemical plating and presoma has prepared imitative diatom institutional framework (the Advanced Functional Materials of gold, 2012,22:2550-2559), but the hydrofluoric acid that normal temperature removes template used makes preparation process have larger potential safety hazard, the cultivation of diatom and the employing of gold also both increase manufacturing cycle and cost.
Adopt simple and effective method prepares the imitative plant tissue integrating excellent conductive and mechanical property metal material rarely has report so far; Secondly, plant tissue template is overall structure, and the distribution of array structure, size and coherent condition are difficult to regulate; And pyroreaction energy consumption is high, the grain growth of course of reaction is difficult to control, and formwork structure easily deformation occurs under thermal stress effect, will directly affect structure and the performance of material.
Summary of the invention
For above-mentioned existing problems, the object of the present invention is to provide a kind of micro-nano mitron array nickel biomimetic material and preparation method thereof, the method overcome high temperature and prepare the high and uppity shortcoming of material structure of biomimetic material energy consumption, the nickel biomimetic material that form is controlled can be prepared.
In order to reach above object, technical solution of the present invention is as follows: a kind of micro-nano mitron array nickel biomimetic material, it is characterized in that: this biomimetic material is the micro-nano mitron array based on flaxen fiber bundle template, have the accumulation shape of bundle-shaped array or single tubular array, the tube wall of micro-nano mitron array is made up of nano nickel film.
Described flaxen fiber is the one in abaca, sisal hemp, ramie, hemp, jute, mestha or flax fiber.
The thickness of described nickel film is 10nm ~ 1000nm.
Described micro-nano mitron array is made up of micro-nano mitron, and the diameter of micro-nano mitron is 5 ~ 20 μm, and length is 1mm ~ 10mm.
Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm.
A preparation method for micro-nano mitron array nickel biomimetic material, is characterized in that comprising the steps:
1) flaxen fiber bundle is cut into the sample of 1-10mm length, then adopts one of following two kinds of methods:
A () is under 30 ~ 50 DEG C of conditions, sample is immersed the sodium hydrate aqueous solution process 0.5 ~ 6 hour that mass fraction is 1 ~ 5%, use deionized water rinsing 1-5 time, then dry 12 ~ 16 hours at 60 DEG C, obtain bundle-shaped flaxen fiber bundle template sample;
B () is at 60 DEG C, sample is immersed successively 75 DEG C, pH=4.5 (adopting mass fraction to be that 10% acetic acid aqueous solution regulates), mass fraction be 5 ~ 10% sodium chlorite aqueous solution 120min and 20 DEG C, the mass fraction sodium hydrate aqueous solution 120min that is 10 ~ 18%, then the cleaning respectively 1-5 time of deionized water and absolute ethyl alcohol is carried out at normal temperatures, then dry 12 ~ 16 hours at 60 DEG C, obtain single tubular flaxen fiber bundle template sample;
2) above-mentioned bundle-shaped flaxen fiber bundle template sample or single tubular flaxen fiber bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse respectively by ethanol and deionized water, dry 60min at 30 DEG C-110 DEG C, obtains the flaxen fiber bundle template after surface graft modification;
3) NiSO of the 1mmol/L flaxen fiber bundle template (sample) after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 20 ~ 30 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 30 ~ 40 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the flaxen fiber bundle template after surface active;
4) by the flaxen fiber bundle template after above-mentioned surface active, be placed in nickel bath, at 82 ~ 86 DEG C, react 60s, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C, drying 1 ~ 4 hour, obtains the flaxen fiber that inside and outside wall deposits nano nickel film;
5) flaxen fiber immersion temperature inside and outside wall being deposited nano nickel film is 85 ~ 95 DEG C, mass fraction (concentration) is in the NMMO solution of 85 ~ 90%, dissolve after 24 hours solvent clean is clean, (described nickel film thickness is 10nm ~ 1000nm to obtain micro-nano mitron array nickel biomimetic material; Described micro-nano mitron diameter is 5 ~ 20 μm, and length is 1mm ~ 10mm; Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm).
NiSO containing 20g/L in described nickel bath
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3the triton x-100 of COONa, 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.3 ~ 4.9.
Biomimetic material of the present invention take flaxen fiber as template, and obtained by the method for omnidistance liquid phase synthesis, have the accumulation shape of bundle-shaped array or single tubular array, tube wall is nickel nano thin-film.The preparation process of this biomimetic material is: first, to flaxen fiber Shu Jinhang dilute alkaline soln or sodium chlorite+sodium hydrate aqueous solution, obtains the flaxen fiber bundle template of different accumulation shape; Then, this template is carried out the process of amino silane surface grafting, and be placed in nickel bath carry out chemical nickel plating; Finally, adopt the aqueous solution of NMMO to process the flaxen fiber being coated with nickel nano thin-film, remove the micro-nano mitron array nickel biomimetic material that fibrous matrix finally obtains bundle-shaped or single tubular two kinds of different accumulation shapes.The method overcome high temperature and prepare the high and uppity shortcoming of material structure of biomimetic material energy consumption, the metallic nickel biomimetic material that form is controlled can be prepared.This biomimetic material has that chemical stability is good, mechanics and the excellent feature of electric conductivity, and in microreactor, chemistry and photoelectrocatalysis etc., have potential application, also can be used as template prepared by other materials, is the material that a kind of structural behaviour is excellent.
Owing to have employed above technical scheme, the invention has the beneficial effects as follows (there is following innovative point):
1) flaxen fiber belongs to high strength string, have content of cellulose high, draw ratio is large, the feature that porosity is high, the accumulation shape of flaxen fiber bundle template can be regulated by solution-treated, thus prepared the nickel biomimetic features of single tube array and tube bundle array two kinds of accumulation shapes.
2) preparation process of this biomimetic material is the method for omnidistance liquid phase synthesis, and be easy to the growth controlling nickel film, thickness and the density of film are variable, and can adulterate as alloying elements such as P and B.Overcome conventional high temperature and prepare the high and uppity shortcoming of structure of biomimetic material energy consumption, solve the difficult problem that conventional method is difficult to prepare metal biomimetic material simultaneously.
3) this biomimetic material adopts elemental nickel to be basic composition material, has the advantages that chemical stability is good, mechanics, electric conductivity are excellent.Can be applicable to the fields such as microreactor, chemistry and photoelectrocatalysis, also can be used as mould material prepared by other materials.
Accompanying drawing explanation
Fig. 1 is bundle-shaped flaxen fiber bundle Prototype drawing of the present invention.
Fig. 2 is single tubular flaxen fiber bundle Prototype drawing of the present invention.
Fig. 3 is the side view of bundle-shaped micro-nano mitron array nickel biomimetic material structure of the present invention.
Fig. 4 is the side view of single tubular micro-nano mitron array nickel biomimetic material structure of the present invention.
Fig. 5 is the stereogram of bundle-shaped micro-nano mitron array nickel biomimetic material structure of the present invention.
Fig. 6 is the stereogram of single tubular micro-nano mitron array nickel biomimetic material structure of the present invention.
In figure, 1,2 and 3 represent lumen, cell membrane and nickel nano thin-film respectively.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
A preparation method for micro-nano mitron array nickel biomimetic material, comprises the steps:
1) biologic slice machine is used abaca fibre bundle (flaxen fiber bundle) to be cut into the sample of 1mm length, then under 30 DEG C of conditions, sample is immersed the sodium hydrate aqueous solution process 0.5 hour that mass fraction is 1%, use deionized water rinsing 1-5 time, then dry 16 hours at 60 DEG C, obtain the bundle-shaped abaca fibre bundle template sample (bundle-shaped flaxen fiber bundle template) shown in Fig. 1;
2) above-mentioned bundle-shaped abaca fibre bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse respectively by ethanol and deionized water, dry 60min at 110 DEG C, obtains the abaca fibre bundle template after surface graft modification;
3) NiSO of the 1mmol/L abaca fibre bundle template (sample) after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 20 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 40 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the bundle-shaped abaca fibre bundle template after surface active;
4) by the bundle-shaped abaca fibre bundle template after above-mentioned surface active, the nickel bath (NiSO containing 20g/L is placed in
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3cOONa, the triton x-100 of 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.5) in, 60s is reacted at 83 DEG C, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C dry 4 hours, obtain the abaca fibre that inside and outside wall deposits nano nickel film;
5) abaca fibre immersion temperature inside and outside wall being deposited nano nickel film is 86 DEG C, mass fraction (concentration) is in the NMMO solution of 86%, dissolve after 24 hours solvent clean is clean, obtain the bundle-shaped micro-nano mitron array nickel biomimetic material shown in Fig. 3 or Fig. 5.
Described nickel film thickness is 10nm ~ 1000nm.Described micro-nano mitron diameter is 5 ~ 20 μm, and length is 1mm ~ 10mm.Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm, as Fig. 5.
Embodiment 2:
A preparation method for micro-nano mitron array nickel biomimetic material, comprises the steps:
1) biologic slice machine is used abaca fibre bundle (flaxen fiber bundle) to be cut into the sample of 4mm length, then at 60 DEG C, sample is immersed 75 DEG C successively, pH=4.5 (adopting mass fraction to be that 10% acetic acid aqueous solution regulates) mass fraction is the sodium chlorite aqueous solution 120min and 20 DEG C of 5 ~ 10%, mass fraction is the sodium hydrate aqueous solution 120min of 18%, then the cleaning respectively 1-5 time of deionized water and absolute ethyl alcohol is carried out at normal temperatures, dry (drying 16 hours at 60 DEG C), obtain the single tubular abaca fibre bundle template sample (single tubular flaxen fiber bundle template) shown in Fig. 2,
2) above-mentioned single tubular abaca fibre bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse respectively by ethanol and deionized water, dry 60min at 110 DEG C, obtains the abaca fibre bundle template after surface graft modification;
3) NiSO of the 1mmol/L abaca fibre bundle template (sample) after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 20 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 40 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the abaca fibre bundle template after surface active;
4) by the abaca fibre bundle template after above-mentioned surface active, the nickel bath (NiSO containing 20g/L is placed in
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3cOONa, the triton x-100 of 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.5) in, 60s is reacted at 83 DEG C, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C dry 4 hours, obtain the abaca fibre that inside and outside wall deposits nano nickel film;
5) abaca fibre immersion temperature inside and outside wall being deposited nano nickel film is 86 DEG C, mass fraction (concentration) is in the NMMO solution of 85 ~ 90%, dissolve after 24 hours solvent clean is clean, obtain the micro-nano mitron array nickel biomimetic material shown in Fig. 4 or Fig. 6.
Described nickel film thickness is 10nm ~ 1000nm; Described micro-nano mitron diameter is 5 ~ 20 μm, and length is 1mm ~ 10mm; Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm.
Embodiment 3:
A preparation method for micro-nano mitron array nickel biomimetic material, comprises the steps:
1) sisal fiber bundle (flaxen fiber bundle) is cut into the sample of 10mm length, then under 30 DEG C of conditions, sample is immersed the sodium hydrate aqueous solution process 1 hour that mass fraction is 1%, use deionized water rinsing 1-5 time, then dry 12 hours at 60 DEG C, obtain bundle-shaped sisal fiber bundle template sample;
2) above-mentioned bundle-shaped sisal fiber bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse 1-5 time respectively by ethanol and deionized water, dry 60min at 110 DEG C, obtains the sisal fiber bundle template after surface graft modification;
3) NiSO of the 1mmol/L sisal fiber bundle template (sample) after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 20 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 40 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the sisal fiber bundle template after surface active;
4) by the sisal fiber bundle template after above-mentioned surface active, the nickel bath (NiSO of nickel bath containing 20g/L is placed in
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3cOONa, the triton x-100 of 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.3 ~ 4.9), 60s is reacted at 83 DEG C, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C dry 4 hours, obtain the sisal fiber that inside and outside wall deposits nano nickel film;
5) sisal fiber immersion temperature inside and outside wall being deposited nano nickel film is 86 DEG C, mass fraction (concentration) is in the NMMO solution of 85 ~ 90%, dissolve after 24 hours solvent clean is clean, (described nickel film thickness is 10nm ~ 1000nm to obtain micro-nano mitron array nickel biomimetic material; Described micro-nano mitron diameter is 5 ~ 20 μm, and length is 1mm ~ 10mm; Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm).
Embodiment 4:
A preparation method for micro-nano mitron array nickel biomimetic material, comprises the steps:
1) sisal fiber bundle (flaxen fiber bundle) is cut into the sample of 2mm length, then at 60 DEG C, sample is immersed successively 75 DEG C, pH=4.5 (adopting mass fraction to be that 10% acetic acid aqueous solution regulates), mass fraction be 10% sodium chlorite aqueous solution 120min and 20 DEG C, the mass fraction sodium hydrate aqueous solution 120min that is 18%, then the cleaning respectively 1-5 time of deionized water and absolute ethyl alcohol is carried out at normal temperatures, then dry 12 hours at 60 DEG C, obtain single tubular sisal fiber bundle template sample;
2) above-mentioned single tubular sisal fiber bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse respectively by ethanol and deionized water, dry 60min at 30 DEG C, obtains the sisal fiber bundle template after surface graft modification;
3) NiSO of the 1mmol/L sisal fiber bundle template (sample) after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 20 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 40 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the sisal fiber bundle template after surface active;
4) by the sisal fiber bundle template after above-mentioned surface active, the nickel bath (NiSO of nickel bath containing 20g/L is placed in
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3cOONa, the triton x-100 of 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.3 ~ 4.9), 60s is reacted at 83 DEG C, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C dry 4 hours, obtain the sisal fiber that inside and outside wall deposits nano nickel film;
5) sisal fiber immersion temperature inside and outside wall being deposited nano nickel film is 86 DEG C, mass fraction (concentration) is in the NMMO solution of 85 ~ 90%, dissolve after 24 hours solvent clean is clean, (described nickel film thickness is 10nm ~ 1000nm to obtain micro-nano mitron array nickel biomimetic material; Described micro-nano mitron diameter is 5 ~ 20 μm, and length is 1mm ~ 10mm; Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm).
Embodiment 5:
A preparation method for micro-nano mitron array nickel biomimetic material, comprises the steps:
1) ramee bundle (flaxen fiber bundle) is cut into the sample of 1mm length, then under 50 DEG C of conditions, sample is immersed the sodium hydrate aqueous solution process 6 hours that mass fraction is 5%, use deionized water rinsing 1-5 time, then dry 16 hours at 60 DEG C, obtain bundle-shaped ramee bundle template sample;
2) above-mentioned bundle-shaped ramee bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse respectively by ethanol and deionized water, dry 60min at 30 DEG C, obtains the ramee bundle template after surface graft modification;
3) NiSO of the 1mmol/L ramee bundle template (sample) after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 30 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 30 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the ramee bundle template after surface active;
4) by the ramee bundle template after above-mentioned surface active, the nickel bath (NiSO of nickel bath containing 20g/L is placed in
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3cOONa, the triton x-100 of 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.3 ~ 4.9), 60s is reacted at 82 DEG C, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C dry 1 hour, obtain the ramee that inside and outside wall deposits nano nickel film;
5) ramee immersion temperature inside and outside wall being deposited nano nickel film is 85 DEG C, mass fraction (concentration) is in the NMMO solution of 85%, dissolve after 24 hours solvent clean is clean, (described nickel film thickness is 10nm ~ 1000nm to obtain micro-nano mitron array nickel biomimetic material; Described micro-nano mitron diameter is 5 ~ 20 μm, and length is 1mm ~ 10mm; Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm).
Embodiment 6:
A preparation method for micro-nano mitron array nickel biomimetic material, comprises the steps:
1) hemp bundle (flaxen fiber bundle) is cut into the sample of 5mm length, at 60 DEG C, sample is immersed successively 75 DEG C, pH=4.5 (adopting mass fraction to be that 10% acetic acid aqueous solution regulates), mass fraction be 10% sodium chlorite aqueous solution 120min and 20 DEG C, the mass fraction sodium hydrate aqueous solution 120min that is 10%, then the cleaning respectively 1-5 time of deionized water and absolute ethyl alcohol is carried out at normal temperatures, then dry 12 hours at 60 DEG C, obtain single tubular hemp bundle template sample;
2) above-mentioned single tubular hemp bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse respectively by ethanol and deionized water, dry 60min at 50 DEG C, obtains the hemp bundle template after surface graft modification;
3) NiSO of the 1mmol/L hemp bundle template (sample) after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 25 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 35 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the hemp bundle template after surface active;
4) by the hemp bundle template after above-mentioned surface active, the nickel bath (NiSO of nickel bath containing 20g/L is placed in
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3cOONa, the triton x-100 of 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.3 ~ 4.9), 60s is reacted at 86 DEG C, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C dry 4 hours, obtain the hemp that inside and outside wall deposits nano nickel film;
5) hemp immersion temperature inside and outside wall being deposited nano nickel film is 95 DEG C, mass fraction (concentration) is in the NMMO solution of 90%, dissolve after 24 hours solvent clean is clean, (described nickel film thickness is 10nm ~ 1000nm to obtain micro-nano mitron array nickel biomimetic material; Described micro-nano mitron diameter is 5 ~ 20 μm, and length is 1mm ~ 10mm; Described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm).
Each raw material (as jute, mestha or flax fiber) cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of technological parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (7)
1. a micro-nano mitron array nickel biomimetic material, is characterized in that: this biomimetic material is the micro-nano mitron array based on flaxen fiber bundle template, has the accumulation shape of bundle-shaped array or single tubular array, and the tube wall of micro-nano mitron array is made up of nano nickel film.
2. a kind of micro-nano mitron array nickel biomimetic material according to claim 1, is characterized in that: described flaxen fiber is the one in abaca, sisal hemp, ramie, hemp, jute, mestha or flax fiber.
3. a kind of micro-nano mitron array nickel biomimetic material according to claim 1, is characterized in that: the thickness of described nickel film is 10nm ~ 1000nm.
4. a kind of micro-nano mitron array nickel biomimetic material according to claim 1, it is characterized in that: described micro-nano mitron array is made up of micro-nano mitron, the diameter of micro-nano mitron is 5 ~ 20 μm, and length is 1mm ~ 10mm.
5. a kind of micro-nano mitron array nickel biomimetic material according to claim 1, is characterized in that: described micro-nano mitron array diameter is 100 ~ 300 μm, and length is 1mm ~ 10mm.
6. the preparation method of a kind of micro-nano mitron array nickel biomimetic material as claimed in claim 1, is characterized in that comprising the steps:
1) flaxen fiber bundle is cut into the sample of 1-10mm length, then adopts one of following two kinds of methods:
A () is under 30 ~ 50 DEG C of conditions, sample is immersed the sodium hydrate aqueous solution process 0.5 ~ 6 hour that mass fraction is 1 ~ 5%, use deionized water rinsing 1-5 time, then dry 12 ~ 16 hours at 60 DEG C, obtain bundle-shaped flaxen fiber bundle template sample;
B () is at 60 DEG C, sample is immersed successively 75 DEG C, pH=4.5 mass fraction be 5 ~ 10% sodium chlorite aqueous solution 120min and 20 DEG C, the mass fraction sodium hydrate aqueous solution 120min that is 10 ~ 18%, then the cleaning respectively 1-5 time of deionized water and absolute ethyl alcohol is carried out at normal temperatures, then dry 12 ~ 16 hours at 60 DEG C, obtain single tubular flaxen fiber bundle template sample;
2) above-mentioned bundle-shaped flaxen fiber bundle template sample or single tubular flaxen fiber bundle template sample being immersed mass fraction is in the ethanolic solution of the aminopropyl trimethoxysilane (APTMS) of 0.05% 24 hours, then rinse respectively by ethanol and deionized water, dry 60min at 30 DEG C-110 DEG C, obtains the flaxen fiber bundle template after surface graft modification;
3) NiSO of the 1mmol/L flaxen fiber bundle template after above-mentioned surface graft modification immersed
4or AgNO
3the aqueous solution in, adsorb 30min at 20 ~ 30 DEG C after, take out carry out deionized water rinsing, and then sample is immersed in the sodium borohydride solution of 0.1mol/L, under the condition of 30 ~ 40 DEG C, react 20min, then use washed with de-ionized water 1-5 time, obtain the flaxen fiber bundle template after surface active;
4) by the flaxen fiber bundle template after above-mentioned surface active, be placed in nickel bath, at 82 ~ 86 DEG C, react 60s, take out rear deionized water and ethanol rinses 1-5 time respectively, in the baking oven of 50 DEG C, drying 1 ~ 4 hour, obtains the flaxen fiber that inside and outside wall deposits nano nickel film;
5) flaxen fiber immersion temperature inside and outside wall being deposited nano nickel film is 85 ~ 95 DEG C, and mass fraction is in the NMMO solution of 85 ~ 90%, dissolves after 24 hours solvent clean is clean, obtains micro-nano mitron array nickel biomimetic material.
7. the preparation method of a kind of micro-nano mitron array nickel biomimetic material according to claim 6, is characterized in that the NiSO containing 20g/L in described nickel bath
46H
2the NaH of O, 25g/L
2pO
2h
2the CH of O, 15g/L
3the triton x-100 of COONa, 5mg/L, the lactic acid of 12g/L and the natrium citricum of 8g/L, adjust pH=4.3 ~ 4.9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105935772A (en) * | 2016-07-14 | 2016-09-14 | 四川天塬增材制造材料有限公司 | Metal 3D printing preparing method for achieving bionic surface structure |
| CN107385891A (en) * | 2017-07-11 | 2017-11-24 | 复旦大学 | A kind of preparation method of ternary alloy three-partalloy anti-corrosion electric conducting fabric |
| CN108914150A (en) * | 2018-06-11 | 2018-11-30 | 江苏科技大学 | A kind of preparation method of the ultra-thin Ni-P combination electrode material of orderly micro-nano hole array structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101660125A (en) * | 2009-09-18 | 2010-03-03 | 邵楠 | Technology for plating nano-metal on fiber |
| CN101976594A (en) * | 2010-08-31 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite conductor application of carbon nano tube fiber and preparation method thereof |
| CN102154818A (en) * | 2011-05-16 | 2011-08-17 | 东北林业大学 | Method for preparing nickel coating on surface of cotton fabric or linen fabric |
| US20120277091A1 (en) * | 2011-04-29 | 2012-11-01 | Korea Institute Of Energy Research | Method of Preparing Catalyst Using Alkali Metal or Alkaline Earth Metal in Natural Cellulose Fibers as Co-Catalyst and Dispersant |
| CN103132059A (en) * | 2013-01-29 | 2013-06-05 | 上海工程技术大学 | Fabric chemical plating method using HBP-NH2/ Ag+ coordination compound as activate fluid |
-
2015
- 2015-04-14 CN CN201510176328.3A patent/CN104773707B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101660125A (en) * | 2009-09-18 | 2010-03-03 | 邵楠 | Technology for plating nano-metal on fiber |
| CN101976594A (en) * | 2010-08-31 | 2011-02-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite conductor application of carbon nano tube fiber and preparation method thereof |
| US20120277091A1 (en) * | 2011-04-29 | 2012-11-01 | Korea Institute Of Energy Research | Method of Preparing Catalyst Using Alkali Metal or Alkaline Earth Metal in Natural Cellulose Fibers as Co-Catalyst and Dispersant |
| CN102154818A (en) * | 2011-05-16 | 2011-08-17 | 东北林业大学 | Method for preparing nickel coating on surface of cotton fabric or linen fabric |
| CN103132059A (en) * | 2013-01-29 | 2013-06-05 | 上海工程技术大学 | Fabric chemical plating method using HBP-NH2/ Ag+ coordination compound as activate fluid |
Non-Patent Citations (3)
| Title |
|---|
| HOUFANG LU ET AL.: "Fabrication of micro-Ni arrays by electroless and electrochemical depositions with etched porous aluminum template", 《BULLETIN OF MATERIALS SCIENCE》 * |
| 崔培英: "麻纤维表面化学镀镍", 《化学世界》 * |
| 鲁博等: "《天然纤维复合材料》", 31 October 2005 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105935772A (en) * | 2016-07-14 | 2016-09-14 | 四川天塬增材制造材料有限公司 | Metal 3D printing preparing method for achieving bionic surface structure |
| CN107385891A (en) * | 2017-07-11 | 2017-11-24 | 复旦大学 | A kind of preparation method of ternary alloy three-partalloy anti-corrosion electric conducting fabric |
| CN108914150A (en) * | 2018-06-11 | 2018-11-30 | 江苏科技大学 | A kind of preparation method of the ultra-thin Ni-P combination electrode material of orderly micro-nano hole array structure |
| CN108914150B (en) * | 2018-06-11 | 2020-01-10 | 江苏科技大学 | Preparation method of ultrathin Ni-P composite electrode material with ordered micro-nano-pore array structure |
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