CN104616836A - Method for quickly preparing conducting polymer film polyurethane/gold - Google Patents
Method for quickly preparing conducting polymer film polyurethane/gold Download PDFInfo
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- CN104616836A CN104616836A CN201510053379.7A CN201510053379A CN104616836A CN 104616836 A CN104616836 A CN 104616836A CN 201510053379 A CN201510053379 A CN 201510053379A CN 104616836 A CN104616836 A CN 104616836A
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Abstract
The invention discloses a method for quickly preparing conducting polymer film polyurethane/gold. The method for quickly preparing the conducting polymer film polyurethane/gold includes that using a home-made spraying device to directly assemble polyurethane and gold nano-particles layer by layer, the film surface is uniform based on keeping the electric conductivity of a conducting film, and the Au nano-particle dispersion is uniform. The method for quickly preparing the conducting polymer film polyurethane/gold overcomes many disadvantages of a traditional method, and moreover, the device is simple, the conditions are moderate, the technique is simple, the cost is low, and electric conductivity of the prepared conducting polymer film is higher than that of the conducting polymer film prepared by a traditional method.
Description
Technical field
The invention belongs to field of material technology, particularly a kind of method preparing conducting polymer thin film polyurethane/gold fast.
Background technology
Along with the development of science and technology and improving constantly of living standards of the people, high-resolution, large scale flat-panel screens, solar cell, energy-saving infrared reflectance coating, the extensive uses such as electrochromic are more and more large to the demand of conductive film.The conductivity that transparent conductive film not only requires, also will have excellent visible light transmission.From physical angle, the light transmission of material and conductivity are a pair basic contradictions.In order to make material, there is usually described conductivity, just must make the misalignment momentum space initial point of its Fermi sphere, that is, according to band theory Fermi sphere and near energy level distribution very intensive, be there is not energy gap by between the energy level of electrons occupy and unoccupied level.Like this when there being incident light to enter, be easy to produce internal photoelectric effect, light is decayed because excitation electron loses energy.So, do not wish to produce internal photoelectric effect from the angle of light transmission, just require that energy gap must be greater than photon energy.Broadband transparent conductive oxide semiconductor, keep good visible light transmission, and its plasma frequency is just less than visible frequency, and certain conductivity be kept just to need certain carrier concentration, and plasma frequency and carrier concentration proportional.The exploitation of nesa coating is exactly based on how making the two better organic unity.
A.J.Heeger, A.G.M acD iarm id in 1977 and Hideki Shirakawa (H.Shirakawa) find, polyacetylene film is through electron acceptor (I, AsF5 etc.) conductivity adds 9 orders of magnitude after doping, is increased to 103S/cm (they for this reason jointly obtain 2000 annual Nobel chemistry Prizes) from 10-6S/cm.The traditional concept that organic polymer is all insulator has been broken in this discovery, has started the research field of conducting polymer, has induced the research boom of conducting polymer in world wide.
Self-assembling technique be a kind of from bottom to top, by little and large manufacture method, namely from atom or molecular level, intactly construct device.It is defined as basic structural unit (molecule, nano material, the material of micron or more large scale) the spontaneous a kind of technology being formed with sequence structure.So in the process of self assembly, basic structural unit spontaneous tissue or gathering under based on the interaction of non-covalent bond are a structure stablizing, have certain regular geometric outward appearance.This process is not the simple superposition of weak force between a large amount of atom, ion, molecule, but a kind of entirety, complicated synergy.
At present, the method preparing conductive film both at home and abroad generally adopts LBL self-assembly, conductive effect is not in post synthesis too desirable, main cause is: the experiment restriction of (1) LBL self-assembly itself, the size of conducting polymer thin film generally only has 3cm × 3cm, and the cycle needed for the conducting polymer thin film of preparation multilayer is longer; (2) in building-up process, easily cause Au nano particle to be gathered in certain region on PU surface, thus affect conductance.So these reasons all limit the application of PU/Au conductive film in industrial production; (3) in preparation process, obtain conducting polymer thin film in a solution of hydrofluoric acid by soaking, this causes secondary pollution to a certain extent.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of method preparing conducting polymer thin film polyurethane/gold fast, adopt LBL self-assembly and spray the method combined, by to the analysis and characterization of synthesized conductive film PU/Au and conductance, the test of tensile property, this synthetic method not only improves the degree of scatter of Au nano particle on polymer P U surface effectively, solve the Thin film conductive rate that conventional synthesis conductive film PU/Au method causes not high, film surface is uneven first-class not enough, and than using the conductive film of conventional method synthesis to have higher conductance and tensile property.
To achieve these goals, the technical solution used in the present invention is:
Prepare a method for conducting polymer thin film polyurethane/gold fast, comprise the steps:
Step 1, the matrix using Teflon paper as assembling film material;
Step 2, is dissolved in deionized water by quantitative polyurethane (PU), stirs and makes PU dissolving obtain PU solution;
Step 3, is dissolved in gold chloride in deionized water, adds thermal agitation, add trisodium citrate afterwards, continues stirring and obtains wine-colored gold particle solution, by this solution suction filtration, concentrates, obtains solution of gold nanoparticles;
Step 4, is added to plastic solvent bottle respectively by PU solution and nano Au particle solution, and utilize spraying apparatus by the two alternating spray on matrix, prepared by the self assembly carrying out conducting polymer thin film;
Step 5, by the baking oven inner drying 24 hour of the sample of self assembly preparation synthesis at 70 DEG C.
In described PU solution, the quality proportioning of PU and deionized water is 3:7.
In described step 3,0.15g gold chloride is dissolved in 800mL deionized water, adds thermal agitation 30 minutes at 60 DEG C, add the trisodium citrate of 0.01mol afterwards, continue stirring and obtain wine-colored solution of gold nanoparticles in 20 minutes.
In described step 4, first to matrix spraying PU solution, be deposited on after matrix surface until PU, spray nano Au particle solution again, under electrostatic interaction, on matrix surface, self assembly forms thin film, and then sprays PU solution and nano Au particle solution successively, alternating spray like this, the final self assembly preparation realizing the conducting polymer thin film of the required number of plies.
In described step 4, spraying apparatus comprises spray gun, spray cup and matrix platform, and spray gun and spray cup all have 2 at least, are respectively used to spraying and store PU solution and nano Au particle solution, the nozzle distance matrix 1.6cm of spray gun during spraying.
Described matrix, before spraying, first carries out preliminary treatment with wipe oil, takes out and spray after its drying again in volume ratio is the concentrated sulfuric acid of 1:3 and hydrogen peroxide mixed liquor.
Compared with prior art, the method that the present invention is combined with spraying by top-down LBL self-assembly, Au nano particle is chemisorbed on PU surface better, improve its conductance, Au nanoparticle dispersion is even simultaneously, thus form nano level Au on PU surface, make the uniform surface of film; Experiment shows that the film that the conductance of this conducting polymer thin film is prepared than conventional method is significantly improved; Select Teflon paper as the matrix of assembling film material simultaneously, replacing conventional method uses glass as basis material, the film obtained is without the need to the immersion through hydrofluoric acid HF, both overcome the limitation can only preparing small size film to a certain extent, it also avoid the secondary harm and secondary pollution that use glass basis to use hydrofluoric acid to bring.The present invention can prepare the film of 20cm × more than 20cm size, and this overcomes the limitation that conventional method can only prepare small size film to a certain extent, also improves the operating efficiency preparing film simultaneously.
Accompanying drawing explanation
Fig. 1 is the SEM figure of conducting polymer thin film PU/Au.
Fig. 2 is the SEM figure of conducting polymer thin film PU/Au.
Fig. 3 is the load-deformation curve of conducting polymer thin film PU/Au.
Embodiment
Embodiments of the present invention are described in detail below in conjunction with drawings and Examples.
Prepare a method for conducting polymer thin film polyurethane/gold fast, comprise the steps:
Step 1, the matrix using Teflon paper as assembling film material;
Step 2 is 3:7 according to quality proportioning, is dissolved in deionized water by quantitative polyurethane (PU), stirs and makes PU dissolving obtain PU solution;
Step 3, is dissolved in 0.15g gold chloride in 800mL deionized water, adds thermal agitation 30 minutes at 60 DEG C, add the trisodium citrate of 0.01mol afterwards, continue stirring and within 20 minutes, obtain wine-colored gold particle solution, by this solution suction filtration, concentrate, obtain nano Au particle solution;
Step 4, PU solution and nano Au particle solution are added to plastic solvent bottle respectively, utilize spraying apparatus by the two alternating spray on matrix, spraying apparatus comprises spray gun, spray cup and matrix platform, spray gun and spray cup all have 2 at least, be respectively used to spraying and store PU solution and nano Au particle solution, the nozzle distance matrix 1.6cm of spray gun during spraying.Matrix is before spraying, and first in volume ratio is the concentrated sulfuric acid of 1:3 and hydrogen peroxide mixed liquor, carry out preliminary treatment with wipe oil, take out and spray after its drying again, pre-treatment is bad, causes film easily to come off, the phenomenons such as bubbling.During spraying, first to matrix spraying PU solution, be deposited on after matrix surface until PU, spray nano Au particle solution again, under electrostatic interaction, on matrix surface, self assembly forms thin film, and then sprays PU solution and nano Au particle solution successively, alternating spray like this, the final self assembly preparation realizing the conducting polymer thin film of the required number of plies.
In this step, spraying rate and coating cycles number of times carry out control realization by computer software such as Mach 3 software, and this is that conventional Industry Control can reach, and does not repeat them here.Generally, can use two or four nozzles, setting speed, low speed is generally 0.05cm/s-0.5cm/s, and middling speed is generally 0.5cm/s-1.5cm/s, is 1.5cm/s-3cm/s at a high speed.The track of nozzle according to space coordinates XYZ to carrying out three-dimensional motion, and can utilize G code Programming.
PU macromolecule sprays after nozzle atomization, and the particulate be atomized is sprayed onto basis material Teflon paper.Because polyurethane (PU) is positively charged, be more easily deposited on matrix surface, due to suitable concentration, can effectively increase its surface charge density.Pass through the flushing of distilled water and air afterwards, the PU molecule that chemical reaction does not occur is rinsed out.When then positively charged band Au nano-particle solution being sprayed to matrix surface, under electrostatic interaction, LBL self-assembly can be there is form uniform conducting film on matrix surface.The last flushing again using distilled water and air, rinses out not there is the Au molecule that electrostatic attracts each other.Under such one-period, can think and define thin film.Repeat this process, can form the conducting polymer thin film of the required number of plies, synthesis technologic parameter is in table 1.
The synthesis technologic parameter (selection one-period is example) of table 1 PU/Au
| Material | Spraying rate | The nozzle quantity used | Cycle-index |
| Polyurethane solutions | 35 | 1 | 1 |
| Distilled water | 20 | 1 | 2 |
| Air | 10 | 2 | 2 |
| Solution of gold nanoparticles | 35 | 1 | 1 |
| Distilled water | 20 | 1 | 2 |
| Air | 10 | 2 | 2 |
Step 5, by the baking oven inner drying 24 hour of the sample of self assembly preparation synthesis at 70 DEG C.
Four electrode method is utilized to test its resistivity, to determine its conductance conducting polymer thin film polyurethane/gold (PU/Au) that this method is synthesized.Meanwhile, stretching-machine is utilized to test its tensile property.(1), conducting polymer thin film is cut into the rectangular slat of 2cm × 10cm; (2), utilize stretching-machine and four electrode method to test its tensile property and conductance, and make comparisons with the conducting polymer thin film using conventional method to synthesize.
Utilize the analytical technology such as ESEM, transmission electron microscope, result shows: utilize the method for spraying to prepare conducting polymer thin film Au nano particle and be chemisorbed on PU surface well, and film surface is smooth, homogeneous.
Shown by conductivity test, golden nanometer particle is loaded in polyether polyols with reduced unsaturation (PU), polymer can be converted to an electric conductor, than the conducting polymer thin film of conventional method synthesis, there is better conductance.Meanwhile, in polymer, golden nanometer particle (Au) is when being stretched, and can form conductive path.Conductivity does not also still weaken after the stretch, in table 1.
The structural parameters of table 2 PU/Au
| Numbering | The number of plies | Conductance (× 10 4，S/cm) | Film thickness (μm) |
| 1 | 300 | 1.56 | 10.45 |
| 2 | 400 | 1.62 | 15.19 |
| 3 | 500 | 1.66 | 20.65 |
| 4 | 600 | 1.69 | 26.07 |
Fig. 1 is the SEM figure of conducting polymer thin film PU/Au cross section, and the film number of plies is 300 layers.As can be seen from the figure PU layer and Au layer cover matrix surface equably, and there is obviously boundary between layers.The method utilizing spraying is described, synergy can construct stable structure system, is self-assembled into conductive film.
The SEM figure on Fig. 2 conducting polymer thin film PU/Au surface, the film number of plies is 300 layers.As can be seen from the figure this conductive film surface is very even, and this can ensure that this self-assembly system energy is lower, thus guarantees the stability of whole system.
The tensile stress curve of Fig. 3 conducting polymer thin film PU/Au, the film number of plies is 300 layers, and as can be seen from the figure this material has good tensile property.Meanwhile, conductive path is formed in the process stretched.Conductivity does not also still weaken after the stretch.
Claims (6)
1. prepare a method for conducting polymer thin film polyurethane/gold fast, it is characterized in that, comprise the steps:
Step 1, the matrix using Teflon paper as assembling film material;
Step 2, is dissolved in deionized water by quantitative polyurethane (PU), stirs and makes PU dissolving obtain PU solution;
Step 3, is dissolved in gold chloride in deionized water, adds thermal agitation, add trisodium citrate afterwards, continues stirring and obtains wine-colored gold particle solution, by this solution suction filtration, concentrates, obtains solution of gold nanoparticles;
Step 4, is added to plastic solvent bottle respectively by PU solution and nano Au particle solution, and utilize spraying apparatus by the two alternating spray on matrix, prepared by the self assembly carrying out conducting polymer thin film;
Step 5, by the baking oven inner drying 24 hour of the sample of self assembly preparation synthesis at 70 DEG C.
2. prepare the method for conducting polymer thin film polyurethane/gold according to claim 1 fast, it is characterized in that, in described PU solution, the quality proportioning of PU and deionized water is 3:7.
3. prepare the method for conducting polymer thin film polyurethane/gold according to claim 1 fast, it is characterized in that, in described step 3,0.15g gold chloride is dissolved in 800mL deionized water, thermal agitation is added 30 minutes at 60 DEG C, add the trisodium citrate of 0.01mol afterwards, continue stirring and obtain wine-colored solution of gold nanoparticles in 20 minutes.
4. prepare the method for conducting polymer thin film polyurethane/gold according to claim 1 fast, it is characterized in that, in described step 4, first to matrix spraying PU solution, be deposited on after matrix surface until PU, spray nano Au particle solution again, under electrostatic interaction, on matrix surface, self assembly forms thin film, and then sprays PU solution and nano Au particle solution successively, alternating spray like this, the final self assembly preparation realizing the conducting polymer thin film of the required number of plies.
5. according to claim 1 or 4, prepare the method for conducting polymer thin film polyurethane/gold fast, it is characterized in that, in described step 4, spraying apparatus comprises spray gun, spray cup and matrix platform, spray gun and spray cup all have 2 at least, be respectively used to spraying and store PU solution and nano Au particle solution, the nozzle distance matrix 1.6cm of spray gun during spraying.
6. according to claim 1 or 4, prepare the method for conducting polymer thin film polyurethane/gold fast, it is characterized in that, described matrix, before spraying, first carries out preliminary treatment with wipe oil, takes out and spray after its drying again in volume ratio is the concentrated sulfuric acid of 1:3 and hydrogen peroxide mixed liquor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105291512A (en) * | 2015-11-25 | 2016-02-03 | 哈尔滨工业大学 | Preparation method of high-strength polyurethane-based composite film |
| CN110548636A (en) * | 2019-09-05 | 2019-12-10 | 大连理工大学 | Automatic spraying device for preparing film material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474897A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Grapheme-organic material layered assembling film and preparation method thereof |
| US20110147337A1 (en) * | 2009-12-18 | 2011-06-23 | Korea University Research And Business Foundation | Use of block copolymers for preparing conductive nanostructures |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474897A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Grapheme-organic material layered assembling film and preparation method thereof |
| US20110147337A1 (en) * | 2009-12-18 | 2011-06-23 | Korea University Research And Business Foundation | Use of block copolymers for preparing conductive nanostructures |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105291512A (en) * | 2015-11-25 | 2016-02-03 | 哈尔滨工业大学 | Preparation method of high-strength polyurethane-based composite film |
| CN110548636A (en) * | 2019-09-05 | 2019-12-10 | 大连理工大学 | Automatic spraying device for preparing film material |
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