CN103170643B - Preparing method of long-range order micron silver tubes - Google Patents
Preparing method of long-range order micron silver tubes Download PDFInfo
- Publication number
- CN103170643B CN103170643B CN201310101281.5A CN201310101281A CN103170643B CN 103170643 B CN103170643 B CN 103170643B CN 201310101281 A CN201310101281 A CN 201310101281A CN 103170643 B CN103170643 B CN 103170643B
- Authority
- CN
- China
- Prior art keywords
- optical fibers
- solution
- microstructured optical
- preparation
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a preparing method of long-range order micron silver tubes. Polymer micro structure optical fibers serve as a mould plate, a multi-hole cellulose acetate film is laid in the mould plate, inner channels of the micro structure optical fibers are washed through reducing agent of stannous chloride solution, mixture solution of glucose solution and absolute ethyl alcohol is mixed with silver ammonia solution of definite concentration according to a certain ratio after ice-bath, the mixed solution is pressed into the micro structure optical fibers through high pressure, the polymer micro structure optical fibers and cellulose acetate are removed through solvent in a dissolved mode after reaction, and at last, the micron silver tubes arranged orderly are obtained. Hundreds of arrayed micron silver tubes can be prepared once through the method, the lengths and diameters of the prepared silver tubes can be regulated according to requirements, and the method is flexible. The long-range order micron silver tubes have the wide application prospect in Raman spectrum analysis and other fields.
Description
Technical field
The present invention relates to the preparation method of a kind of micron of silver-colored pipe, particularly relate to the preparation method of a kind of long-range order micron silver pipe.
Background technology
Because one-dimensional micron tubulose (diameter is little 1 ~ 100 μm) and nanotube-shaped material have peculiar character, become the focus of research in recent years.Cause the very big concern of scientist.The hollow tubular structure of this uniqueness, makes it in catalysis, sensing, fuel cell, spectrum analysis, electronics, medical science and technology, and there is potential extensive use in the fields such as bio-separation and biomedicine.Such as, metal micro-tubes has higher intensity, is added in coating, can be used for the electroactive functional material of development of new.If be prepared into silver metal micro pipe, due to the special nature of silver, it can also be applied in the spectrum analyses such as SERS.In current research, less to the research of the preparation method of micron silver pipe.And often concentrate on silver powder and these silver-colored samples easily prepared of silver-colored line.The preparation method of the silver-colored pipe of micron is mainly template and method of electrostatic spinning.But the micron of these methods or preparation silver length of tube is limited, or the micron silver pipe of preparation is deposited in together in a jumble, which limits the range of application of micron silver pipe.
As " Qingdao University of Science and Technology's journal " the 28th volume the 3rd phase the 227th page describes using spider silk as template in the article " Templated Synthesis of Metallic Micro-tubes via Electroless Plating " delivered in June, 2007, by coated, go the process such as template, reduction, prepared metal micro-tubes.But due to the randomness of spider silk, the metal tube prepared by this method can only be rambling existence.Method of electrostatic spinning is utilized to prepare micron tube as " J.Mater.Sci.Technol. " the 20th volume the 5th phase the 613rd page describes in the article " Preparation of a Novel Micro/nano Tubes via Electrospun Fiber as a Template " to deliver for 2004.But because the randomness of electrostatic spinning, it is stacking that prepared micron tube also remains randomness.
And domestic what often prepare is all sheet, dendroid or tubulose silver powder.As publication number is: the Introduction To Cn Patent of CN101569935A, CN101811196A and CN101254539A preparation method of silver powder, but all the micron silver pipe of long-range order not to be studied.
In known microstructured optical fibers field, microstructured optical fibers has the characteristics such as endless single mode characteristic, dispersion-tunable.Be widely used in Dispersion managed, the field such as nonlinear optics and Fibre Optical Sensor.As shown in Figure 1, microstructured optical fibers is made up of polymethyl methacrylate (PMMA), and single microstructured optical fibers just has hundreds of microchannels 1.All on the books in the articles such as the article " case study in microstructured optical fibers preparation " that the structure of microstructured optical fibers is delivered " optical communication technique " o. 11th in 2006 55 pages and " laser and optoelectronics progress " the 2nd phase in 2008 the 43rd page of article delivered " status quo and development of photonic crystal fiber ".
Summary of the invention
The object of this invention is to provide the preparation method of a kind of long-range order micron silver pipe, using the polymer micro-structural optical fiber in hundreds of hole as template, silver-plated after the Adsorption on Surface CAM in duct therein, can the micron silver pipe of one time to produce hundreds of.Can adjust length and the diameter of the silver-colored pipe of preparation as required, method is flexible.The micron silver pipe of this long-range order has a wide range of applications in Raman spectrum analysis etc.
The present invention adopts following technical proposals:
A preparation method for long-range order micron silver pipe, concrete preparation comprises the following steps:
1) first with the acetum of cellulose acetate under high pressure fast press-in have in the microstructured optical fibers internal gutter in hundreds of hole, in microstructured optical fibers duct, be covered with one deck CAM.Then by this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.Wash inner passage secondary again.
2) rinse microstructured optical fibers internal gutter once with reducing agent stannous chloride solution, then clean once by secondary deionized water.
3) prepare ice bath after certain density silver ammino solution, then the glucose solution of 35% and absolute ethyl alcohol are pressed ice bath after certain volume mixing;
4) after the silver ammino solution in step 3) and glucose solution being mixed by certain volume ratio with the mixed liquor of absolute ethyl alcohol, high pressure is pressed in microstructured optical fibers internal gutter.Microstructured optical fibers is placed in 45-60 degree isoperibol, reaction 0.2-1.5 hour.Microstructured optical fibers is inner will form the micron silver pipe of array.
5) by above-mentioned steps 4) in silver-plated microstructured optical fibers soak 1-2 hour with chloroform respectively after filter, three times so repeatedly.
6) by above-mentioned steps 5) in product soak 3-5 hour with acetic acid after filter, three times so repeatedly, the micron silver pipe that final acquisition arranges in certain sequence.
The acetum of the cellulose acetate of step (1) is by cellulose acetate 0.2580g, acetic acid 10-15mL, and 65 degree of backflow 4-5 hour, are prepared into cellulose acetate solution.
The stannous chloride solution of step (2) is by stannous chloride 0.2256g, adds concentrated hydrochloric acid 1.0-2.0g, then adds deionized water 20-25g and be prepared from.
The silver ammino solution of step (3) gets the liquor argenti nitratis ophthalmicus that concentration is 2% to 15%, add the potassium hydroxide solution of 3% until there is a small amount of precipitation, then adding the ammoniacal liquor of 28% to precipitating disappearance, again instilling the liquor argenti nitratis ophthalmicus of 6% to variable color, then the ammoniacal liquor instilling 6% is to just becoming clear.
In step (3), the volume ratio of glucose solution and absolute ethyl alcohol is 2:1 ~ 4:1.
The volume ratio of the silver ammino solution of step (4) and mixed liquor (glucose solution and absolute ethyl alcohol) is 1:1 ~ 2:1.
Step (5) is dissolved by the PMMA of microstructured optical fibers, and to remove microstructured optical fibers, step (6) is dissolved by the CAM of microstructured optical fibers inside, and to remove cellulose acetate, cleaning process is tried not, and vibration micron is silver-colored manages.
In preparation process, because the inwall of polymer micro-structural optical fiber is more smooth, bad to the adsorptivity of silver, so the CAM of first wall layer overlay porous within it.The length of the microstructured optical fibers adopted and the diameter in single hole can select different optical fiber as required.
Adopting microstructured optical fibers to be Template preparation micron silver pipe, there are following three outstanding substantive distinguishing features and significant progressive: one is by choosing suitable microstructured optical fibers, almost can prepare the micron silver pipe of random length and diameter; Two is disposablely can prepare up to a hundred microns silver pipe; Three is that prepared micron silver pipe arranges in sequence.
Accompanying drawing explanation
Fig. 1 is the end face partial schematic diagram of microstructured optical fibers;
Fig. 2 is the microstructured optical fibers end face partial schematic diagram being modified with array porous membrane;
Fig. 3 is preparation method's schematic diagram of micron silver pipe;
Fig. 4 is the microstructured optical fibers end face partial schematic diagram being modified with array micron silver pipe;
Detailed description of the invention
Below in conjunction with accompanying drawing and instantiation, the present invention will be further described, but the present invention is not limited to this.
Embodiment 1
1) prepare 2% liquor argenti nitratis ophthalmicus for subsequent use; The liquor argenti nitratis ophthalmicus of preparation 6% is for subsequent use; The potassium hydroxide solution of preparation 3% is for subsequent use; The glucose solution of preparation 35% is for subsequent use.
2) get stannous chloride 0.2256g, add concentrated hydrochloric acid 1.0-2.0g, then add deionized water 20-25g, make solution A.
3) get cellulose acetate 0.2580g, acetic acid 10-15mL, 65 degree of backflow 4-5 hour, are prepared into cellulose acetate solution.
4) see Fig. 2, a small amount of cellulose acetate is under high pressure pressed in microstructured optical fibers 1 fast, in microstructured optical fibers, is covered with one deck CAM 3.Then by this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.
5) by above-mentioned steps 4) after the microstructured optical fibers high-pressure solution A that obtains rinses one time, then with secondary deionized water cleaning once, for subsequent use.
6) get the liquor argenti nitratis ophthalmicus of 50mL2%, add the potassium hydroxide solution of 3% wherein until there is a small amount of precipitation, then add the ammoniacal liquor of 28%, until precipitation disappears, again instill the liquor argenti nitratis ophthalmicus of 6% to variable color, then the ammoniacal liquor instilling 6% is to just becoming clear.Obtain silver ammino solution B ice bath for subsequent use.
7) using after the 2:1 mixing by volume of the glucose solution of 35% and absolute ethyl alcohol as solution C, and ice bath;
8) after getting the solution C 2:1 mixing by volume of the solution B after step 6) ice bath and step 7), ice bath is for subsequent use.
9) see Fig. 3, by above-mentioned steps 8) obtained mixed liquor high pressure press-in microstructured optical fibers under condition of ice bath, liquid is slowly flowed in microstructured optical fibers, and microstructured optical fibers is placed in 45-60 degree isoperibol, reaction 0.2-1.5 hour.See Fig. 4, microstructured optical fibers inside will form micron silver pipe 4.
10) by above-mentioned steps 9) the microstructured optical fibers chloroform being coated with silver-colored pipe that obtains soaks after 1-2 hour and filters, dissolved by PMMA, leave Solid Silver pipe, three times so repeatedly.
11) by above-mentioned steps 11) in solid product soak 3-5 hour with acetic acid after filter, cellulose acetate dissolves is removed, leaves solid matter, three times so repeatedly.The micron silver pipe of the length-adjustable ordering of final acquisition.
Embodiment 2
1) prepare 10% liquor argenti nitratis ophthalmicus for subsequent use; The liquor argenti nitratis ophthalmicus of preparation 6% is for subsequent use; The potassium hydroxide solution of preparation 3% is for subsequent use; The glucose solution of preparation 35% is for subsequent use.
2) get stannous chloride 0.2256g, add concentrated hydrochloric acid 1.0-2.0g, then add deionized water 20-25g, make solution A.
3) get cellulose acetate 0.2580g, acetic acid 10-15mL, 65 degree of backflow 4-5 hour, are prepared into cellulose acetate solution.
4) see Fig. 2, a small amount of cellulose acetate is under high pressure pressed in microstructured optical fibers 1 fast, in microstructured optical fibers, is covered with one deck CAM 3.Then by this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.
5) by above-mentioned steps 4) after the microstructured optical fibers high-pressure solution A that obtains rinses one time, then with secondary deionized water cleaning once, for subsequent use.
6) get the liquor argenti nitratis ophthalmicus of 50 milliliter 10%, add the potassium hydroxide solution of 3% wherein until there is a small amount of precipitation, then add the ammoniacal liquor of 28%, until precipitation disappears, again instill the liquor argenti nitratis ophthalmicus of 6%, to variable color, then the ammoniacal liquor instilling 6% is to becoming clear.Obtain silver ammino solution B ice bath for subsequent use.
7) using after the 3:1 mixing by volume of the glucose solution of 35% and absolute ethyl alcohol as solution C, and ice bath.
8) after getting the solution C 3:2 mixing by volume of the solution B after step 6) ice bath and step 7), ice bath is for subsequent use.
9) see Fig. 3, by above-mentioned steps 8) obtained mixed liquor high pressure press-in microstructured optical fibers under condition of ice bath, liquid is slowly flowed in microstructured optical fibers, and microstructured optical fibers is placed in 45-60 degree isoperibol, reaction 0.2-1.5 hour.See Fig. 4, microstructured optical fibers inside will form micron silver pipe 4.
10) by above-mentioned steps 9) the microstructured optical fibers chloroform being coated with silver-colored pipe that obtains soaks after 1-2 hour and filters, dissolved by PMMA, leave Solid Silver pipe, three times so repeatedly.
11) by above-mentioned steps 11) in solid product soak 3-5 hour with acetic acid after filter, cellulose acetate dissolves is removed, leaves solid matter, three times so repeatedly.The micron silver pipe of the length-adjustable ordering of final acquisition.
Embodiment 3
1) prepare 15% liquor argenti nitratis ophthalmicus for subsequent use; The liquor argenti nitratis ophthalmicus of preparation 6% is for subsequent use; The potassium hydroxide solution of preparation 3% is for subsequent use; The glucose solution of preparation 35% is for subsequent use.
2) get stannous chloride 0.2256g, add concentrated hydrochloric acid 1.0-2.0g, then add deionized water 20-25g, make solution A.
3) get cellulose acetate 0.2580g, acetic acid 10-15mL, 65 degree of backflow 4-5 hour, are prepared into cellulose acetate solution.
4) see Fig. 2, a small amount of cellulose acetate is under high pressure pressed in microstructured optical fibers 1 fast, in microstructured optical fibers, is covered with one deck CAM 3.Then by this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.
5) by above-mentioned steps 4) after the microstructured optical fibers high-pressure solution A that obtains rinses one time, then with secondary deionized water cleaning once, for subsequent use.
6) get the liquor argenti nitratis ophthalmicus of 50mL15%, add the potassium hydroxide solution of 3% wherein until there is a small amount of precipitation, then add the ammoniacal liquor of 28%, until precipitation disappears, again instill the liquor argenti nitratis ophthalmicus of 6% to variable color, then the ammoniacal liquor instilling 6% is to just becoming clear, obtains silver ammino solution B ice bath for subsequent use.
7) using after the 4:1 mixing by volume of the glucose solution of 35% and absolute ethyl alcohol as solution C, and ice bath.
8) after getting the solution C 1:1 mixing by volume of the solution B after step 6) ice bath and step 7), ice bath is for subsequent use.
9) see Fig. 3, by above-mentioned steps 8) obtained mixed liquor high pressure press-in microstructured optical fibers under condition of ice bath, liquid is slowly flowed in microstructured optical fibers, and microstructured optical fibers is placed in 45-60 degree isoperibol, reaction 0.2-1.5 hour.See Fig. 4, microstructured optical fibers inside will form micron silver pipe 4.
10) by above-mentioned steps 9) the microstructured optical fibers chloroform being coated with silver-colored pipe that obtains soaks after 1-2 hour and filters, dissolved by PMMA, leave Solid Silver pipe, three times so repeatedly.
11) by above-mentioned steps 11) in solid product soak 3-5 hour with acetic acid after filter, cellulose acetate dissolves is removed, leaves solid matter, three times so repeatedly.The micron silver pipe of the length-adjustable ordering of final acquisition.
Claims (7)
1. a preparation method for long-range order micron silver pipe, it is characterized in that, it comprises the following steps:
1) be first under high pressure pressed into fast in microstructured optical fibers internal gutter with the acetum of cellulose acetate, one deck CAM is covered with in microstructured optical fibers duct, individual hour of microstructured optical fibers dry 3-5 under 45 DEG C of-60 DEG C of conditions, washing inner passage secondary;
2) rinse microstructured optical fibers internal gutter once with reducing agent stannous chloride solution, then clean once by secondary deionized water;
3) prepare ice bath after certain density silver ammino solution, then the glucose solution of 35% and absolute ethyl alcohol are pressed ice bath after certain volume mixing;
4) by step 3) in silver ammino solution and the mixed liquor of glucose solution and absolute ethyl alcohol mix by certain volume ratio after high pressure be pressed in microstructured optical fibers internal gutter, mixed liquor is slowly flowed in optical fiber duct, microstructured optical fibers is placed in 45 DEG C of-60 DEG C of isoperibols, reaction 0.2-1.5 hour, microstructured optical fibers is inner will form the micron silver pipe of array;
5) by above-mentioned steps 4) in microstructured optical fibers soak 1-2 hour with chloroform after filter, three times so repeatedly;
6) by above-mentioned steps 5) in product soak 3-5 hour with acetic acid after filter, three times so repeatedly, the micron silver pipe that final acquisition arranges in certain sequence.
2. preparation method according to claim 1, is characterized in that, optical fiber used is polymer micro-structural optical fiber.
3. preparation method according to claim 1, is characterized in that, the acetum of cellulose acetate gets cellulose acetate 0.2580g, acetic acid 10-15mL, and 65 DEG C of backflow 4-5 hour, are prepared into cellulose acetate solution.
4. preparation method according to claim 1, is characterized in that, stannous chloride solution is by stannous chloride 0.2256g, adds concentrated hydrochloric acid 1.0-2.0g, then adds deionized water 20-25g and be prepared from.
5. preparation method according to claim 1, it is characterized in that, the method preparing silver ammino solution gets the liquor argenti nitratis ophthalmicus that concentration is 2% to 15%, add the potassium hydroxide solution of 3% until there is a small amount of precipitation, then the ammoniacal liquor of 28% is added to precipitating disappearance, again instill the liquor argenti nitratis ophthalmicus of 6% to variable color, then the ammoniacal liquor instilling 6% is to just becoming clear.
6. preparation method according to claim 1, is characterized in that, the glucose solution of 35% and absolute ethyl alcohol 2:1 ~ 4:1 by volume.
7. preparation method according to claim 1, is characterized in that, the volume ratio of the mixed liquor of silver ammino solution and glucose solution and absolute ethyl alcohol is 1:1 ~ 2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101281.5A CN103170643B (en) | 2013-03-26 | 2013-03-26 | Preparing method of long-range order micron silver tubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101281.5A CN103170643B (en) | 2013-03-26 | 2013-03-26 | Preparing method of long-range order micron silver tubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103170643A CN103170643A (en) | 2013-06-26 |
| CN103170643B true CN103170643B (en) | 2014-12-17 |
Family
ID=48631073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310101281.5A Active CN103170643B (en) | 2013-03-26 | 2013-03-26 | Preparing method of long-range order micron silver tubes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103170643B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6346136B1 (en) * | 2000-03-31 | 2002-02-12 | Ping Chen | Process for forming metal nanoparticles and fibers |
| CN1199846C (en) * | 2003-06-03 | 2005-05-04 | 清华大学 | Pure siler nano tube array and its preparation method |
| US20080083299A1 (en) * | 2006-10-06 | 2008-04-10 | General Electric Company | Composition and associated method |
| CN102122016A (en) * | 2010-10-13 | 2011-07-13 | 成都亨通光通信有限公司 | Method for preparing polymer photonic crystal fiber |
| CN102198510B (en) * | 2011-04-27 | 2012-09-12 | 黑龙江大学 | Method for preparing nano copper/carbon nano tube composite powder by liquid phase method |
| CN102277622B (en) * | 2011-07-22 | 2013-03-13 | 北京化工大学 | Copper-platinum superlattice alloy nano-tube and preparation method thereof |
-
2013
- 2013-03-26 CN CN201310101281.5A patent/CN103170643B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103170643A (en) | 2013-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Bioinspired helical microfibers from microfluidics | |
| McCann et al. | Electrospinning of nanofibers with core-sheath, hollow, or porous structures | |
| Park et al. | Electrolyte‐assisted electrospinning for a self‐assembled, free‐standing nanofiber membrane on a curved surface | |
| Lee et al. | New electrospinning nozzle to reduce jet instability and its application to manufacture of multi-layered nanofibers | |
| Liu et al. | Formation of helical alginate microfibers using different G/M ratios of sodium alginate based on microfluidics | |
| CN103100239A (en) | Separation net membrane with super-hydrophilicity/underwater super-lipophobicity as well as preparation method and application thereof | |
| CN104436760A (en) | Magnetic response type high-efficiency oil-water separation fiber membrane and preparation method thereof | |
| CN102260963A (en) | Method for preparing micro-nano-scale patterned electrospun fiber membrane | |
| CN101387018B (en) | Visualization preparation method of electro spinning hollow TiO2 fiber | |
| CN102704028A (en) | Preparation method of meta-aramid nano-nets fiber membrane | |
| CN105297286B (en) | A kind of preparation method of functional polyalkylene methyl methacrylate, cyclodextrin and carbon nano tube composite nanofiber membrane | |
| CN103386257A (en) | Nano-fiber composite ultrafiltration membrane preparation method based on electrostatic spinning technology | |
| CN108755111B (en) | A method of deposition silver nano-grain processability stablizes antibacterial superhydrophobic fabric | |
| CN101474105A (en) | Parallel type electrostatic filature blood vessel support collector | |
| Jalaja et al. | Effective SERS detection using a flexible wiping substrate based on electrospun polystyrene nanofibers | |
| CN105300955B (en) | The micro-fluidic SERS chip-detecting apparatus of integrated liquid core light guide and nano metal | |
| CN103170643B (en) | Preparing method of long-range order micron silver tubes | |
| CN110215914A (en) | A kind of solid-phase micro-extraction fibre and the preparation method and application thereof based on zeolite imidazole skeleton material ZIF-8 | |
| WO2020248473A1 (en) | Method for preparing microfluidic chip-based nano-microcrystalline cellulose | |
| CN101788478B (en) | Optical fibre localization plasma resonance sensing device and system thereof | |
| CN110006873A (en) | Environmental pollutant detection method based on three-dimensional micro-nano structure enhancing Raman spectrum | |
| Song et al. | Cactus-inspired Janus membrane with a conical array of wettability gradient for efficient fog collection | |
| KR20120041661A (en) | Cellulose microfibers and synthesis thereof | |
| He et al. | Adhesion of perfume-filled microcapsules to model fabric surfaces | |
| CN106310719A (en) | High efficiency and continuous oil-water separation device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |