CN103170643A - Preparing method of long-range order micron silver tubes - Google Patents
Preparing method of long-range order micron silver tubes Download PDFInfo
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- CN103170643A CN103170643A CN2013101012815A CN201310101281A CN103170643A CN 103170643 A CN103170643 A CN 103170643A CN 2013101012815 A CN2013101012815 A CN 2013101012815A CN 201310101281 A CN201310101281 A CN 201310101281A CN 103170643 A CN103170643 A CN 103170643A
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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 silver-colored pipe, relate in particular to a kind of preparation method of long-range order micron silver pipe.
Background technology
Because one-dimensional micron tubulose (little 1～100 μ m of diameter) and nanotube-shaped material have peculiar character, become the focus of research in recent years.Caused scientist's very big concern.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.For example, 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 micron tube, due to the special nature of silver, it can also be applied in the spectrum analyses such as SERS.In present research, less to the preparation method's of micron silver pipe research.And often concentrate on these easy silver-colored samples of preparation of silver powder and silver-colored line.The preparation method of the silver-colored pipe of micron is mainly template and method of electrostatic spinning.But the silver-colored length of tube of micron of these methods or preparation is limited, or the micron silver pipe of preparation is deposited in together in a jumble, and this has just limited the range of application of the silver-colored pipe of micron.
Introduced with spider silk as template in the article " Templated Synthesis of Metallic Micro-tubes via Electroless Plating " of delivering in June, 2007 as the 227th page of " Qingdao University of Science and Technology's journal " the 28th the 3rd phase of volume, by coating, going the processing such as template, reduction, prepared metal micro-tubes.But due to the randomness of spider silk, the prepared metal tube of this method can only be rambling existence.Having introduced in the article " Preparation of a Novel Micro/nano Tubes via Electrospun Fiber as a Template " of delivering in 2004 as the 613rd page of " J.Mater.Sci.Technol. " the 20th the 5th phase of volume utilizes method of electrostatic spinning to prepare micron tube.But because the randomness of electrostatic spinning, it is stacking that prepared micron tube also remains randomness.
And domestic often preparation is all sheet, dendroid or tubulose silver powder.As publication number be: the Introduction To Cn Patent of CN101569935A, CN101811196A and CN101254539A the preparation method of silver powder, but all to long-range order the micron a silver-colored pipe do not study.
In known microstructured optical fibers field, microstructured optical fibers has the characteristics such as endless single mode characteristic, dispersion is adjustable.Be widely used in dispersion and control, the fields such as nonlinear optics and Fibre Optical Sensor.As shown in Figure 1, microstructured optical fibers is made by polymethyl methacrylate (PMMA), and single microstructured optical fibers just has hundreds of microchannels 1.The structure of microstructured optical fibers is all on the books in the articles such as 55 pages of articles of delivering of " optical communication technique " o. 11th in 2006 " microstructured optical fibers preparation in case study " and " laser and optoelectronics progress " 2008 the 2nd phase the 43rd page of article of delivering " present situation of photonic crystal fiber and development ".
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of long-range order micron silver pipe, as template, silver-plated after the Adsorption on Surface CAM in section duct within it with the polymer micro-structural optical fiber in hundreds of holes, but the micron silver pipe of hundreds of of one time to produces.Can adjust as required length and the diameter of the silver-colored pipe of preparation, method is flexible.The silver-colored pipe of micron of this long-range order has a wide range of applications at aspects such as Raman spectrum analyses.
The present invention adopts following technical proposals:
A kind of preparation method of long-range order micron silver pipe, concrete preparation comprises the following steps:
1) first under high pressure be pressed into fast in the microstructured optical fibers with hundreds of holes inner duct with the acetum of cellulose acetate, be covered with one deck CAM in the microstructured optical fibers duct.Then with this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.Wash again the inner passage secondary.
2) rinse microstructured optical fibers internal holes pipeline in one step with the reducing agent stannous chloride solution, then clean once with secondary deionized water.
3) ice bath after the certain density silver ammino solution of preparation, then 35% glucose solution and absolute ethyl alcohol are pressed the rear ice bath of certain volume mixing;
4) silver ammino solution in step 3) and glucose solution and high pressure after the mixed liquor of absolute ethyl alcohol mixes by certain volume ratio are pressed in microstructured optical fibers inner duct.Microstructured optical fibers is placed in 45-60 degree isoperibol, reacts 0.2-1.5 hour.Microstructured optical fibers inside will form the micron silver pipe of array.
5) with above-mentioned steps 4) in silver-plated microstructured optical fibers soak with chloroform respectively and filter after 1-2 hour, three times so repeatedly.
6) with above-mentioned steps 5) in product soak with acetic acid and filter after 3-5 hour, three times so repeatedly, the final micron silver pipe that obtains to arrange in certain sequence.
The acetum of the cellulose acetate of step (1) is with cellulose acetate 0.2580g, acetic acid 10-15mL, and 65 degree backflows 4-5 hour are prepared into cellulose acetate solution.
The stannous chloride solution of step (2) is with stannous chloride 0.2256g, adds concentrated hydrochloric acid 1.0-2.0g, then adds deionized water 20-25g to be prepared from.
The silver ammino solution of step (3) is that to get concentration be 2% to 15% liquor argenti nitratis ophthalmicus, add 3% potassium hydroxide solution until a small amount of precipitation occurs, then add 28% ammoniacal liquor to precipitation to disappear, again splash into 6% liquor argenti nitratis ophthalmicus to variable color, then splash into 6% ammoniacal liquor 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 the PMMA dissolving with microstructured optical fibers, and to remove microstructured optical fibers, step (6) is the CAM dissolving with microstructured optical fibers inside, and to remove cellulose acetate, cleaning process tries not to vibrate micron silver pipe.
In preparation process, bad to the adsorptivity of silver because the inwall of polymer micro-structural optical fiber is more smooth, so the first CAM of wall layer overlay porous within it.The length of the microstructured optical fibers that adopts and the diameter in single hole can be selected different optical fiber as required.
Adopting microstructured optical fibers is template preparation micron silver pipe, has following three outstanding substantive distinguishing features and significant progressive: the one, by choosing suitable microstructured optical fibers, almost can prepare the micron silver pipe of random length and diameter; The 2nd, disposablely can prepare up to a hundred microns silver pipe; The 3rd, prepared micron silver pipe is arranged in sequence.
Description of drawings
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 that is modified with the array porous membrane;
Fig. 3 is preparation method's schematic diagram of the silver-colored pipe of micron;
Fig. 4 is the microstructured optical fibers end face partial schematic diagram that is modified with array micron silver pipe;
The specific embodiment
The present invention will be further described below in conjunction with accompanying drawing and instantiation, but the present invention is not limited to this.
1) liquor argenti nitratis ophthalmicus of preparation 2% is standby; The liquor argenti nitratis ophthalmicus of preparation 6% is standby; The potassium hydroxide solution of preparation 3% is standby; The glucose solution of preparation 35% is standby.
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 backflows 4-5 hour are prepared into cellulose acetate solution.
4) referring to Fig. 2, a small amount of cellulose acetate under high pressure is pressed in microstructured optical fibers 1 fast, be covered with one deck CAM 3 and get final product in microstructured optical fibers.Then with this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.
5) with above-mentioned steps 4) after resulting microstructured optical fibers rinses one time with high-pressure solution A, then clean once with secondary deionized water, standby.
6) get the liquor argenti nitratis ophthalmicus of 50mL2%, add wherein 3% potassium hydroxide solution until a small amount of precipitation occurs, then add 28% ammoniacal liquor, until precipitation disappears, again splash into 6% liquor argenti nitratis ophthalmicus to variable color, then splash into 6% ammoniacal liquor to just becoming clear.Obtain silver ammino solution B ice bath standby.
7) 35% glucose solution and absolute ethyl alcohol 2:1 mixing by volume is rear as solution C, and ice bath;
8) get the solution C of solution B after the step 6) ice bath and step 7) 2:1 mix by volume after ice bath standby.
9) referring to Fig. 3, with above-mentioned steps 8) mixed liquor high pressure under condition of ice bath of making is pressed into microstructured optical fibers, and liquid is slowly flowed in microstructured optical fibers, and microstructured optical fibers is placed in 45-60 degree isoperibol, reacts 0.2-1.5 hour.Referring to Fig. 4, microstructured optical fibers inside will form micron silver pipe 4.
10) with above-mentioned steps 9) microstructured optical fibers that is coated with silver-colored pipe that obtains soaks with chloroform and filters after 1-2 hour, with the PMMA dissolving, stays the Solid Silver pipe, three times so repeatedly.
11) with above-mentioned steps 11) in solid product soak with acetic acid and filter after 3-5 hour, the cellulose acetate dissolving is removed, stay solid matter, three times so repeatedly.The final micron silver pipe that obtains length-adjustable ordering.
1) liquor argenti nitratis ophthalmicus of preparation 10% is standby; The liquor argenti nitratis ophthalmicus of preparation 6% is standby; The potassium hydroxide solution of preparation 3% is standby; The glucose solution of preparation 35% is standby.
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 backflows 4-5 hour are prepared into cellulose acetate solution.
4) referring to Fig. 2, a small amount of cellulose acetate under high pressure is pressed in microstructured optical fibers 1 fast, be covered with one deck CAM 3 and get final product in microstructured optical fibers.Then with this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.
5) with above-mentioned steps 4) after resulting microstructured optical fibers rinses one time with high-pressure solution A, then clean once with secondary deionized water, standby.
6) get the liquor argenti nitratis ophthalmicus of 50 milliliter 10%, add wherein 3% potassium hydroxide solution until a small amount of precipitation occurs, then add 28% ammoniacal liquor, until precipitation disappears, again splash into 6% liquor argenti nitratis ophthalmicus, to variable color, then splash into 6% ammoniacal liquor to becoming clear.Obtain silver ammino solution B ice bath standby.
7) 35% glucose solution and absolute ethyl alcohol 3:1 mixing by volume is rear as solution C, and ice bath.
8) get the solution C of solution B after the step 6) ice bath and step 7) 3:2 mix by volume after ice bath standby.
9) referring to Fig. 3, with above-mentioned steps 8) mixed liquor high pressure under condition of ice bath of making is pressed into microstructured optical fibers, and liquid is slowly flowed in microstructured optical fibers, and microstructured optical fibers is placed in 45-60 degree isoperibol, reacts 0.2-1.5 hour.Referring to Fig. 4, microstructured optical fibers inside will form micron silver pipe 4.
10) with above-mentioned steps 9) microstructured optical fibers that is coated with silver-colored pipe that obtains soaks with chloroform and filters after 1-2 hour, with the PMMA dissolving, stays the Solid Silver pipe, three times so repeatedly.
11) with above-mentioned steps 11) in solid product soak with acetic acid and filter after 3-5 hour, the cellulose acetate dissolving is removed, stay solid matter, three times so repeatedly.The final micron silver pipe that obtains length-adjustable ordering.
1) liquor argenti nitratis ophthalmicus of preparation 15% is standby; The liquor argenti nitratis ophthalmicus of preparation 6% is standby; The potassium hydroxide solution of preparation 3% is standby; The glucose solution of preparation 35% is standby.
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 backflows 4-5 hour are prepared into cellulose acetate solution.
4) referring to Fig. 2, a small amount of cellulose acetate under high pressure is pressed in microstructured optical fibers 1 fast, be covered with one deck CAM 3 and get final product in microstructured optical fibers.Then with this microstructured optical fibers under 45-60 degree condition dry 3-5 hour.
5) with above-mentioned steps 4) after resulting microstructured optical fibers rinses one time with high-pressure solution A, then clean once with secondary deionized water, standby.
6) get the liquor argenti nitratis ophthalmicus of 50mL15%, add wherein 3% potassium hydroxide solution until a small amount of precipitation occurs, then add 28% ammoniacal liquor, until precipitation disappears, again splash into 6% liquor argenti nitratis ophthalmicus to variable color, then splash into 6% ammoniacal liquor to just becoming clear, obtain silver ammino solution B ice bath standby.
7) 35% glucose solution and absolute ethyl alcohol 4:1 mixing by volume is rear as solution C, and ice bath.
8) get the solution C of solution B after the step 6) ice bath and step 7) 1:1 mix by volume after ice bath standby.
9) referring to Fig. 3, with above-mentioned steps 8) mixed liquor high pressure under condition of ice bath of making is pressed into microstructured optical fibers, and liquid is slowly flowed in microstructured optical fibers, and microstructured optical fibers is placed in 45-60 degree isoperibol, reacts 0.2-1.5 hour.Referring to Fig. 4, microstructured optical fibers inside will form micron silver pipe 4.
10) with above-mentioned steps 9) microstructured optical fibers that is coated with silver-colored pipe that obtains soaks with chloroform and filters after 1-2 hour, with the PMMA dissolving, stays the Solid Silver pipe, three times so repeatedly.
11) with above-mentioned steps 11) in solid product soak with acetic acid and filter after 3-5 hour, the cellulose acetate dissolving is removed, stay solid matter, three times so repeatedly.The final micron silver pipe that obtains length-adjustable ordering.
Claims (7)
1. the preparation method of a long-range order micron silver pipe, is characterized in that, it comprises the following steps:
1) first under high pressure be pressed into fast in microstructured optical fibers inner duct with the acetum of cellulose acetate, be covered with one deck CAM in the microstructured optical fibers duct, microstructured optical fibers under 45-60 degree condition dry 3-5 hour.Washing inner passage secondary.
2) rinse microstructured optical fibers internal holes pipeline in one step with the reducing agent stannous chloride solution, then clean once with secondary deionized water.
3) ice bath after the certain density silver ammino solution of preparation, then 35% glucose solution and absolute ethyl alcohol are pressed the rear ice bath of certain volume mixing;
4) silver ammino solution in step 3) and glucose solution and high pressure after the mixed liquor of absolute ethyl alcohol mixes by certain volume ratio are pressed in microstructured optical fibers inner duct, mixed liquor is slowly flowed in the optical fiber duct, microstructured optical fibers is placed in 45-60 degree isoperibol, reacted 0.2-1.5 hour, microstructured optical fibers inside will form the micron silver pipe of array.
5) with above-mentioned steps 4) in microstructured optical fibers soak with chloroform respectively and filter after 1-2 hour, three times so repeatedly.
6) with above-mentioned steps 5) in product soak with acetic acid and filter after 3-5 hour, three times so repeatedly, the final micron silver pipe that obtains to arrange 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 is to get cellulose acetate 0.2580g, acetic acid 10-15mL, and 65 degree backflows 4-5 hour are prepared into cellulose acetate solution.
4. preparation method according to claim 1, is characterized in that, stannous chloride solution is with stannous chloride 0.2256g, adds concentrated hydrochloric acid 1.0-2.0g, then add deionized water 20-25g to be prepared from.
5. preparation method according to claim 1, it is characterized in that, the method for preparing silver ammino solution is that to get concentration be 2% to 15% liquor argenti nitratis ophthalmicus, add 3% potassium hydroxide solution until a small amount of precipitation occurs, then add 28% ammoniacal liquor to precipitation to disappear, again splash into 6% liquor argenti nitratis ophthalmicus to variable color, then splash into 6% ammoniacal liquor to just becoming clear.
6. preparation method according to claim 1, is characterized in that, 35% glucose solution and absolute ethyl alcohol be 2:1～4:1 by volume.
7. preparation method according to claim 1, is characterized in that, the volume ratio of silver ammino solution and mixed liquor (glucose solution and absolute ethyl alcohol) is 1:1～2:1.
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| 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 |
| CN102198510A (en) * | 2011-04-27 | 2011-09-28 | 黑龙江大学 | Method for preparing nano copper/carbon nano tube composite powder by liquid phase method |
| CN102277622A (en) * | 2011-07-22 | 2011-12-14 | 北京化工大学 | Copper-platinum superlattice alloy nano-tube and preparation method thereof |
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Patent Citations (6)
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|---|---|---|---|---|
| US6346136B1 (en) * | 2000-03-31 | 2002-02-12 | Ping Chen | Process for forming metal nanoparticles and fibers |
| CN1460634A (en) * | 2003-06-03 | 2003-12-10 | 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 |
| CN102198510A (en) * | 2011-04-27 | 2011-09-28 | 黑龙江大学 | Method for preparing nano copper/carbon nano tube composite powder by liquid phase method |
| CN102277622A (en) * | 2011-07-22 | 2011-12-14 | 北京化工大学 | Copper-platinum superlattice alloy nano-tube and preparation method thereof |
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