CN103435849B - A kind of cellulose base matrix material for ammonia detection and preparation method thereof - Google Patents
A kind of cellulose base matrix material for ammonia detection and preparation method thereof Download PDFInfo
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- CN103435849B CN103435849B CN201310372901.9A CN201310372901A CN103435849B CN 103435849 B CN103435849 B CN 103435849B CN 201310372901 A CN201310372901 A CN 201310372901A CN 103435849 B CN103435849 B CN 103435849B
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Abstract
The present invention relates to a kind of cellulose base matrix material for ammonia detection and preparation method thereof, this matrix material contains natural cellulose matrix and powdered conductive filler; The present invention adopts cotton fibre to be matrix, and matrix macromolecular chain has a large amount of hydroxyls, is easy to form hydrogen bonded with the ammonia gas of polarity, thus matrix material of the present invention is had the comparatively strong gas-sensitive property responded of ammonia performance.Matrix material of the present invention utilizes native cellulose fibre for matrix, is composited with electroconductive stuffing, and when running into ammonia, the resistance of matrix material can change rapidly.The finished product of this matrix material are nonpoisonous and tasteless, do not pollute the environment.Matrix material of the present invention also has high stability and reusability, can be the gas sensitive element device manufacturing detection ammonia and provides base material.
Description
Technical field
The present invention relates to conductive polymer composite technical field, be specifically related to a kind of cellulose base matrix material for ammonia detection and preparation method thereof.
Background technology
With electroconductive stuffing (as carbon nanotube etc.) fiberfill fibers element matrix the gas sensitive conductive polymer composite that formed, there is conductivity adjustable in a big way, be easy to forming process, cost is low and to ammonia responsive high.Its principle of work is: matrix material is placed in ammonia gas, gas enters material internal very soon, hydrogen bonded can be formed with Mierocrystalline cellulose, the hydrogen bond between Mierocrystalline cellulose and carbon nanotube is caused to be destroyed, the substitute is Mierocrystalline cellulose and ammonia forms intermolecular hydrogen bonding, thus carbon nanotube and cellulosic interaction are weakened greatly, the effect of carbon nanotube aggregation of particles strengthens, thus the conductivity of material is increased.When in air, ammonia is to external diffusion, and Mierocrystalline cellulose and carbon nanotube recombine, resistance increases rapidly.Be that the gas sensitive of matrix has lower excess effusion value with synthetic polymer, thus have good electroconductibility, its mechanical property is better, and is that the gas sensitive conductive composite material of matrix rarely has report with natural cellulose.In addition, by conductive filler material modifying function, add the hydrogen bonded between conductive filler material and matrix, thus improve stability and the circulation ratio of material.
The organism material of filled-type gas sensitive conductive polymer composite is nonpolar body substantially, usually only to substrate macromolecule material solvent gas that is swelling or that dissolve can be made to present strong air-sensitive response.According to negative steam coefficient effect, polar gas is tended to form hydrogen bonded with cellulosic matrix, and nonpolar gas then tends to swelling or dissolves non-polar high polymer matrix.So, adopt Mierocrystalline cellulose only to have larger response performance to polar gas (as ammonia) as the matrix material of matrix gained, and very little to the response of nonpolar gas.
Summary of the invention
The object of this invention is to provide a kind of cellulose base matrix material detecting ammonia and preparation method thereof, it is low that this matrix material has excess effusion value, and good stability, the characteristic such as highly sensitive, repeat performance is excellent, concrete technical scheme is as follows.
For the cellulose base matrix material that ammonia detects, it contains natural cellulose matrix A and powdered conductive filler B; The mass ratio of natural cellulose matrix A and powdered conductive filler B is: 16.7-66.7:1.
The above-mentioned preparation method stating cellulose base matrix material, it comprises the steps:
1. powdered conductive filler is put into moisture eliminator after concentrated nitric acid process, sodium laurylsulfonate process for subsequent use;
2. add in a reservoir and be equivalent to electroconductive stuffing quality 1.67 × 10
3ionic liquid doubly, pass into nitrogen and in oil bath pan heated and stirred, temperature is 90-105 DEG C, adds cellulosic matrix afterwards;
3. after above-mentioned substance (cellulosic matrix) dissolves completely, add the powdered conductive filler after 1. step processes by calculated amount, continue logical nitrogen gas stirring 8-10min and obtain viscous material;
4. gained viscous material is applied on vitreous electricity pole plate, washes away ionic liquid with deionized water, vacuumize dry 9-10min in 70-80 DEG C, obtain the Cellulose-base gas-sensitive conductive composite i.e. described cellulose base matrix material detected for ammonia.
Further, described ionic liquid is 1-butyl-3-Methylimidazole villaumite ([BMIM] Cl), 1-butyl-3-Methylimidazole acetate ([BMIM] Ac), 1-ethyl-3-methylimidazole villaumite ([EMIM] Cl) or 1-ethyl-3-methylimidazole acetate ([EMIM] Ac).
Further, the electrode of described vitreous electricity pole plate be two copper wire wound in parallel on the sheet glass of long 2cm, wide 1cm, now resistance R=∞.
Further, described powdered conductive filler is carbon nanotube, has typical one-dimentional structure and larger specific surface area, and its diameter < 2nm, length is 5-15 μm, specific surface area 500-700m
2/ g, conductive powder purity is greater than 95%.
Further, described cellulosic matrix is cotton fibre.
The present invention is to cellulosic matrix without particular restriction, and main raw material is cotton fibre.Electroconductive stuffing of the present invention is generally Powdered, as carbon nanotube.Need through modification before using.
The fact of synthesis polymer or metal oxide semiconductor is for filled-type gas sensitive conductive polymer composite overwhelming majority matrix, the present invention adopts cotton fibre to be matrix, matrix macromolecular chain has a large amount of hydroxyls, be easy to form hydrogen bonded with ammonia, thus matrix material of the present invention is had the comparatively strong gas-sensitive property responded of ammonia performance.
The present invention adopts conductive filler material modification, increase the method for hydroxyl, conductive filler particles can be scattered in the middle of cellulosic matrix more uniformly, thus effectively reduce the excess effusion value of matrix material, under the condition that matrix material be can't harm in matrix mechanical property, obtain excellent conductivity.
Compared with prior art, tool of the present invention has the following advantages and technique effect:
Do not need to add other auxiliary agent in whole process for making of the present invention, and matrix is Mierocrystalline cellulose, resulting materials is nonpoisonous and tasteless, can not work the mischief to environment.
The present invention adopts the cellulosic method of ion liquid dissolving, dissolving cellulos, material is made to have higher specific conductivity, by carbon nano-tube modification, add the hydroxyl on its surface, fully mix with Mierocrystalline cellulose, thus add the consistency between filler and matrix, improve the interaction between electroconductive stuffing and cellulosic matrix, finally reach the object improving matrix material air-sensitive response sensitivity and stability.
Matrix material of the present invention shows comparatively high sensitivity to ammonia, and has high stability and reusability.
Below by way of example, the invention will be further described.
Accompanying drawing explanation
Fig. 1 a ~ Fig. 1 d is respectively matrix material (embodiment 1-4) response curve in ammonia of different cellulose base content, wherein relative resistance (transient resistance R/ initial resistance R
0) characterize matrix material air-sensitive response performance, probe temperature is 30 DEG C.
Embodiment
Below in conjunction with example and accompanying drawing, enforcement of the present invention is described further, but enforcement of the present invention and protection are not limited thereto.
The proportioning of embodiment 1 ~ 4 is as table 1, and its preparation method concrete steps are as follows:
1. by carbon nanotube (diameter 2nm, length 15 μm, specific surface area 700m
2/ g, purity is 95%) through concentrated nitric acid at 120 DEG C of reflux 4h, to be placed in sodium laurylsulfonate-ethanol (sodium laurylsulfonate massfraction is 4%) solution heated and stirred 90min at 70 DEG C again, to put into moisture eliminator after being finally washed with distilled water to neutrality for subsequent use;
2. 1g ionic liquid is placed in test tube, adds the cotton fibre (get 1/10 at every turn, add in batches) of 0.02g by calculated amount, pass into nitrogen and in oil bath pan heated and stirred, temperature is 100 DEG C;
3. dissolve until above-mentioned cotton fibre the electroconductive stuffing adding 0.0006g after (about 1h) and 1. processed through step completely, continue logical nitrogen gas stirring 10min;
4. gained viscous material is applied on vitreous electricity pole plate, washes away ionic liquid with deionized water, vacuumize dry 10min in 80 DEG C, obtain matrix material.
Make 4 groups of these matrix materials altogether by above-mentioned steps, wherein the quality (multiple relative to electroconductive stuffing quality) of cotton fibre is respectively 16.7,33.3,50.0,66.7.
Table 2 is matrix material (embodiment 1-4) air-sensitive response-recovery time in ammonia gas, and Fig. 1 a ~ Fig. 1 d is respectively the response performance of matrix material (embodiment 1-4) in ammonia of different content of cellulose, and probe temperature is 30 DEG C.
Table 1 cellulose base matrix material compositing formula *
* in this table embodiment, matrix fiber element A is raw materials used is cotton fibre (polymerization degree is 4050), and conductive filler material B is carbon nanotube (purity > 95%)
Table 2 compares * containing the response-recovery time of matrix material (embodiment 1-4) in ammonia of different Mierocrystalline cellulose quality
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Response recovery time (s) | 235 | 200 | 248 | 230 |
* the response-recovery time stablizes time sum used for this material its resistance in ammonia and air reaches respectively herein.
From above-mentioned example, be the cellulose base matrix material that solvent has successfully prepared for detecting ammonia with ionic liquid [BMIm] Cl.When content of carbon nanotubes is near percolation threshold, this matrix material shows good susceptibility and repeat performance to ammonia, and when content of cellulose is 33.3 times of carbon nanotube, response recovery time is the shortest, and other embodiment time phase differences are little.Be different from non-polar polymer base gas sensitive conductive composite material, cellulose/carbon nano matrix material shows typical negative vapor coefficient to ammonia.The finished product of this matrix material are nonpoisonous and tasteless, do not pollute the environment.Matrix material of the present invention shows very strong susceptibility to ammonia, and has high stability and reusability, can be the gas sensitive element device manufacturing detection ammonia and provides base material.
Claims (5)
1. prepare a method for cellulose base matrix material, it is characterized in that comprising the steps:
1. powdered conductive filler is put into moisture eliminator after concentrated nitric acid process, sodium laurylsulfonate process for subsequent use; Described powdered conductive filler is carbon nanotube, has typical one-dimentional structure and larger specific surface area, and its diameter < 2nm, length is 5-15 μm, specific surface area 500-700m
2/ g, powdered conductive filler purity is greater than 95%;
2. add in a reservoir and be equivalent to electroconductive stuffing quality 1.67 × 10
3ionic liquid doubly, pass into nitrogen and in oil bath pan heated and stirred, temperature is 90-105 DEG C, adds natural cellulose matrix afterwards; The mass ratio of natural cellulose matrix and powdered conductive filler is: 16.7-66.7:1;
3. after natural cellulose matrix dissolves completely, add the powdered conductive filler after 1. step processes by calculated amount, continue logical nitrogen gas stirring 8-10min and obtain viscous material;
4. gained viscous material is applied on vitreous electricity pole plate, washes away ionic liquid with deionized water, vacuumize dry 9-10min in 70-80 DEG C, obtain Cellulose-base gas-sensitive conductive composite namely for the cellulose base matrix material of ammonia detection.
2. preparation method according to claim 1, is characterized in that described ionic liquid is 1-butyl-3-Methylimidazole villaumite ([BMIM] Cl), 1-butyl-3-Methylimidazole acetate ([BMIM] Ac), 1-ethyl-3-methylimidazole villaumite ([EMIM] Cl) or 1-ethyl-3-methylimidazole acetate ([EMIM] Ac).
3. preparation method according to claim 1, it is characterized in that the electrode of described vitreous electricity pole plate be two copper wire wound in parallel on the sheet glass of long 2cm, wide 1cm, now resistance R=∞.
4. preparation method according to claim 1, it is characterized in that step 1. the described condition through concentrated nitric acid process be: 100-120 DEG C of heating-condensing backflow 3.5-4h, nitric acid massfraction is 60%; The described condition through sodium laurylsulfonate process is: temperature 60-70 DEG C, pH=7, and the time is 90-100min, and sodium laurylsulfonate massfraction is 4%.
5. a kind of cellulose base matrix material detected for ammonia obtained by method described in claim 1, is characterized in that containing natural cellulose matrix and powdered conductive filler; The mass ratio of natural cellulose matrix and powdered conductive filler is: 16.7-66.7:1.
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| EP4365589A3 (en) * | 2016-06-17 | 2024-06-12 | Massachusetts Institute of Technology | Chemiresistor with ionic liquid carbon nanotube composite for wireless chemical sensing |
| CN113788900B (en) * | 2021-09-13 | 2022-08-09 | 桂林理工大学 | Modified cellulose nanocrystal with high thermal stability and preparation method thereof |
| CN114670507B (en) * | 2022-03-31 | 2023-12-22 | 湖北中烟工业有限责任公司 | Cotton fiber filter disc for flue gas detection, preparation method of cotton fiber filter disc and flue gas detection method |
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| US7801687B1 (en) * | 2005-07-08 | 2010-09-21 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Chemical sensors using coated or doped carbon nanotube networks |
| CN101973713A (en) * | 2010-09-25 | 2011-02-16 | 东华大学 | Manufacturing method of polyaniline composite nano fiber membrane optical sensor and detection method thereof |
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| WO2013109135A1 (en) * | 2012-01-16 | 2013-07-25 | Mimos Berhad | A sensor for dissolved ammonia and a process of preparation thereof |
| CN103374146A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Cellulose-base gas-sensitive conductive composite material and preparation method thereof |
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| US7801687B1 (en) * | 2005-07-08 | 2010-09-21 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Chemical sensors using coated or doped carbon nanotube networks |
| GB2483158A (en) * | 2010-08-25 | 2012-02-29 | Inst Chemii Fizycznej Polskiej Akademii Nauk | Method to prepare a carbon nanotubes incorporated cellulose nanocomposites and a carbon nanotubes incorporated cellulose nanocomposite |
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