A kind of flexible display material based on bacteria cellulose
Technical field
The invention belongs to biomaterial, macromolecular material and photovaltaic material technical field, be specifically related to flexible display material based on bacteria cellulose and preparation method thereof.
Background technology
Bacteria cellulose is by mikrobe synthetic Mierocrystalline cellulose.Bacteria cellulose fibre has the character of many uniquenesses.Except that the cardinal trait with high purity, high-crystallinity, high-polymerization degree, it still is the meticulousst nanofiber of occurring in nature, has been combined to form the hyperfine network structure of the prosperity that is interweaved by multi-level primitive fiber; " nano effect " but make it have high-hydroscopicity, high-moisture-retention, high permeability, high wet strength, characteristic such as original position machine-shaping under hygrometric state especially to liquids and gases.The excellent comprehensive performance makes bacteria cellulose fibre be widely used in special dimension.Bacteria cellulose aquagel has high mechanical strength, high light transmission and low thermal expansivity, can be used as good optoelectronic thin film material.
Be accompanied by the high speed development of digitizing technique, various both pictures and texts are excellent, look the information major part that sound merges transmits and exchanges through electronic medium, and this is stimulating the market demand high quality, and is light, and portable electron device supplies the human consumer to use.So the rise of flexible display has been satisfied people to light, the requirement of could carry electrons device.Flexible display is frivolous, firm, flexible and impact-resistant characteristic, has not only eliminated the development dead angle of display viewing angles problem in the past, can reach better visual effect, and further represent the applied imagination that has a bright future.It is applicable to mobile telephone, PDA(Personal Digital Assistant), notebook, fascia, the PDA product with camber display screen, electronic poster, RF identification system, transmitter etc.Have the report U.S. to develop the flexible display technology based on active matrix OLED, this technology will be used for the wrist protection type communication equipment of integrated multiple ability to communicate, watch video and graphical information in real time, be mainly used in the military communication equipment a few days ago.Predicted 2013 according to U.S. iSuppli company, flexible display market will reach 2,800,000,000 dollars market scale, and will be not less than 7 times of speed with annual growth and increase rapidly.And for the technological improvement and popularization of following flexible display, it also will be deep in the life of ordinary consumer.
A kind of flexible display material based on bacteria cellulose, it is with high purity, high-crystallinity, high-polymerization degree, and the bacteria cellulose of the nanofiber that occurring in nature is the meticulousst is a flexible substrates; Through infiltrating through transparency and the electroconductibility that silk fibroin and conductive ion liquid improve bacteria cellulose respectively; With the electrochromic material is pigment, carries out the reversible color transition of material.Based on the flexible display material of bacteria cellulose, not only have the performance of quick color reversible transition, kept the pliable and tough bendable folding endurance of material after the processing, can be used as the material of flexible display device, for example can be used as the material of Electronic Paper, flexible display screen.Bacteria cellulose is a kind of biocompatibility and environmental friendliness type material simultaneously, can be used as biosensor etc.
Because this technology is original achievement, therefore do not retrieve domestic as yet about patented claim and mandate.Nowadays, domestic bacteria cellulose industry is just risen, and the carrying out just like a raging fire with application to the various properties of bacteria cellulose do not relate to the correlative study achievement of bacteria cellulose as flexible display material so far.From external patent situation, this respect also is the external advanced subject of research energetically.
Summary of the invention
The object of the present invention is to provide a kind of flexible display material based on bacteria cellulose and preparation method thereof.
Realize that technical scheme of the present invention is:
This flexible display material provided by the invention based on bacteria cellulose; Be to leave standstill the cellulosic bacterium of cultivation product in the liquid medium within to obtain the bacteria cellulose film; Soak the bacteria cellulose film with silk fibroin protein solution; Obtain the bacteria cellulose film that is compounded with silk fibroin that transparency improves; Soak the bacteria cellulose film that is compounded with silk fibroin with conductive ion liquid, obtain the bacteria cellulose film that high conductivity is compounded with silk fibroin, make the electrochromic material polymerization with electrochemical method again and be deposited on high conductivity to be compounded with the flexible display material that obtains on the bacteria cellulose film of silk fibroin.Wherein said with silk fibroin protein solution immersion bacteria cellulose film; The concrete grammar that obtains the high bacteria cellulose film that is compounded with silk fibroin of transparency is: the bacteria cellulose film is immersed in the silk fibroin protein solution that concentration is 1%-5%; 4 ℃ were stirred 48 hours down, obtain the high bacteria cellulose film that is compounded with silk fibroin of transparency; The wherein said bacteria cellulose film that is compounded with silk fibroin that soaks with conductive ion liquid; Obtaining the concrete grammar that high conductivity is compounded with the bacteria cellulose film of silk fibroin is: the bacteria cellulose film that will be compounded with silk fibroin is immersed in the conductive ion liquid that concentration is 10%-20%; 4 ℃ were stirred 48 hours down, obtain the bacteria cellulose film that high conductivity is compounded with silk fibroin; Wherein said make the electrochromic material polymerization and be deposited on the concrete grammar that high conductivity is compounded with on the bacteria cellulose film of silk fibroin with electrochemical method be: the bacteria cellulose film that high conductivity is compounded with silk fibroin places on the electro-conductive material; Drying at room temperature also is fixed on the electro-conductive material; The bacteria cellulose film that is compounded with silk fibroin with the high conductivity that is fixed on the electro-conductive material is as working electrode; Platinum is as supporting electrode; Ag/AgCl is as reference electrode; The monomer of electrochromic material is as electrolytic solution, and the continuous current effect makes the electrochromic material polymerization generate and be deposited on high conductivity and is compounded with on the bacteria cellulose film of silk fibroin.
A kind of preparation method of the flexible display material based on bacteria cellulose may further comprise the steps:
(1) will produce to leave standstill in the cellulosic bacterium liquid medium within and cultivate produce film, and place the 1wt% sodium hydroxide solution to boil 30 minutes the cellulosefilm of producing, be washed with distilled water to neutrality then, obtain the bacteria cellulose film;
(2) the bacteria cellulose film is immersed in the silk fibroin protein solution that concentration is 1%-5%, 4 ℃ were stirred 48 hours down, obtain the high bacteria cellulose film that is compounded with silk fibroin of transparency;
The bacteria cellulose film that (3) will be compounded with silk fibroin is immersed in the conductive ion liquid that concentration is 10%-20%, and 4 ℃ were stirred 48 hours down, obtain the bacteria cellulose film that high conductivity is compounded with silk fibroin;
(4) utilize electrochemical method; The bacteria cellulose film that high conductivity is compounded with silk fibroin places on the electro-conductive material; Drying at room temperature also is fixed on the electro-conductive material, and the bacteria cellulose film that is compounded with silk fibroin with the high conductivity that is fixed on the electro-conductive material is as working electrode, and platinum is as supporting electrode; Ag/AgCl is as reference electrode; The monomer of electrochromic material is as electrolytic solution, and the continuous current effect makes the electrochromic material polymerization generate and be deposited on high conductivity and is compounded with on the bacteria cellulose film of silk fibroin, obtains the flexible display material based on bacteria cellulose.
The bacteria culture of the product bacteria cellulose described in the above-mentioned steps (1) can be the glucose acetobacter xylinum, produce a kind of in acetobacter, acetify bacillus, Acetobacter pasteurianus, Agrobacterium, root nodule bacterium, the sarcina or more than two kinds; Liquid nutrient medium described in the step (1) is a Production by Bacteria film substratum, specifically can be LB substratum or S-H substratum.
Silk fibroin protein solution described in the above-mentioned steps (2) is the silk cocoon that shreds to be placed 0.5% Na
2CO
3Boil in the solution and come unstuck, then at CaCl
2: CH
3CH
2OH: H
2O=1: the ternary component solution of 2: 8 (mol ratio) dissolves in 70 ℃ of water-baths, cools off under the room temperature, and using molecular weight cut-off is that 7000 dialysis tubing dialysis obtains.
The described conductive ion liquid of above-mentioned steps (3) is selected from two (trifluoromethyl sulfonyl) imides of 1-butyl-1-methylpyrrole pyridine, and 1,2-dimethyl--3-propyl imidazole salt compounded of iodine, a kind of in two (trifluoromethyl sulfonyl) imide li ionic liquid or more than two kinds.
Electrochemical method described in the above-mentioned steps (4) is the interaction that utilizes electricity and chemistry, utilizes the effect of electrode high pressure electrostatic discharge, is the method for electrochromic material with the conversion of monomer of the electrochromic material in the electrolyte solution; Electro-conductive material described in the step (4) is that the surface is covered with SnO
2: the conductive glass of F or conductive tinsel; Electrochromic material described in the step (4) can or constitute more than two kinds by polyaniline, polypyrrole, Polythiophene, a kind of in Prussian blue.
The invention discloses a kind of flexible display material based on bacteria cellulose and preparation method thereof, through biotechnology, the compound combination with modification and electrochemical techniques of polymer.Leave standstill the cellulosic bacterium of cultivation product in the liquid medium within and obtain the bacteria cellulose film; Soak the bacteria cellulose film with silk fibroin protein solution; Obtain the high bacteria cellulose film that is compounded with silk fibroin of transparency; Soak the bacteria cellulose film that is compounded with silk fibroin with conductive ion liquid; Obtain the bacteria cellulose film that high conductivity is compounded with silk fibroin, make the electrochromic material polymerization with electrochemical method again and be deposited on high conductivity to be compounded with the flexible display material that obtains on the bacteria cellulose film of silk fibroin.Because electrochromic material is depressed in different electric reversible color transition can be taken place, so, make to be compounded in the electrochromic material color generation reversible tautomerization in the cellulosefilm through applying appropriate voltage.Still kept the high-flexibility of bacteria cellulose after a series of courses of processing, made it can be used as flexible display material.Adopting the inventive method can make with the bacteria cellulose is the electrochromic display device of flexible substrates.
Description of drawings
Fig. 1 systems produce schema of the present invention;
Fig. 2 is based on the structural representation of the flexible display material of bacteria cellulose;
is conductive ion liquid positive ion among the figure;
is conductive ion liquid negative ion;
is electrochromic material, and
is silk fibroin;
Bacteria cellulose film and the bacteria cellulose film clarity test result that is compounded with silk fibroin among Fig. 3 embodiment 1;
Fig. 4 embodiment 1 neutral line voltammetry scanning high conductivity is compounded with the result of the bacteria cellulose film of silk fibroin;
Electrochromic material galvanic deposit result among Fig. 5 embodiment 1, a is that polyaniline is deposited on the result on the conductive glass through electrochemical method among the figure; B is fixed on the bacteria cellulose film that high conductivity on the conductive glass is compounded with silk fibroin among the figure; C is compounded with the result on the bacteria cellulose film of silk fibroin for the polyaniline electrochemical method is deposited on high conductivity among the figure.Can know that by experimental result picture polyaniline successfully has been deposited on conductive glass and high conductivity is compounded with on the bacteria cellulose film of silk fibroin, has obtained the flexible display material based on bacteria cellulose;
The electrochromic reversible color change result of polyaniline among Fig. 6 embodiment 1.When a was a voltage-0.2V among the figure, the color of display material was shown in green; When b was a voltage-1.0V among the figure, the color of display material was shown as yellow; When c was a voltage+1.2V among the figure, the color of display material was shown as blueness; When d was a voltage+0.2V among the figure, the color of display material was shown in green.Reversible tautomerization takes place based on the flexible display material color of bacteria cellulose in the experimental result picture explanation between green, yellow, blueness.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration.
Embodiment 1
(1) utilizes glucose acetobacter xylinum bacterial classification ATCC53582, be seeded in (medium component is: contain 20 gram glucose, 5 gram yeast powders, 5 gram peptones, 1.5 gram Hydrocerol As, 2.7 gram Sodium phosphate, dibasics in the 1L water) in the S-H substratum.Leave standstill under 26 ℃ and cultivated 6 days, obtain the bacterial cellulose gel film.Place zero(ppm) water to soak two days the bacteria cellulose film, with boiling in the 1wt% sodium hydroxide solution 30 minutes, take out and be washed till neutrality then, obtain purified bacteria cellulose film, preserve subsequent use down in 4 ℃ with zero(ppm) water;
(2) place 0.5% Na through the silk cocoon that shreds
2CO
3Boil in the solution and come unstuck, then at CaCl
2: CH
3CH
2OH: H
2O=1: the ternary component solution of 2: 8 (mol ratio) dissolves in 70 ℃ of water-baths, cools off under the room temperature, and using molecular weight cut-off is that 7000 dialysis tubing dialysis obtains silk fibroin protein solution.The bacteria cellulose film is immersed in the silk fibroin protein solution that concentration is 1%-5%, and 4 ℃ were stirred 48 hours down, obtain the high bacteria cellulose film that is compounded with silk fibroin of transparency.
The clarity test result is as shown in Figure 3, and bacteria cellulose film and the bacteria cellulose film that is compounded with silk fibroin is simultaneously dry under the room temperature, with the transparency of measurement of ultraviolet-visible spectrophotometer sample.The test wavelength is from 200nm to 700nm; Exsiccant bacteria cellulose transparency is in 700nm wavelength transparency only 3%; Exsiccant is compounded with the bacteria cellulose film of silk fibroin and has brought up to 50% in 700nm wavelength transparency; Can know that by experimental result the bacteria cellulose film clarity that is compounded with silk fibroin is greatly improved.
It is 10% conductive ion liquid 1 that the bacteria cellulose film that (3) will be compounded with silk fibroin is immersed in concentration, and in 2-dimethyl--3-propyl imidazole salt compounded of iodine, 4 ℃ were stirred 48 hours down, obtain the bacteria cellulose film that high conductivity is compounded with silk fibroin.
The electrical performance test result is as shown in Figure 4, and the bacteria cellulose film that bacteria cellulose and high conductivity is compounded with silk fibroin is fixed in two conductive glass drying at room temperature.Sample is measured its conductivity with linear voltammetry, and TV is from-4 volts to+4 volts, and the bacteria cellulose film current density, J that high conductivity is compounded with silk fibroin is from-0.10mA/cm
2To+0.08mA/cm
2, and bacteria cellulose film current density, J is 10
-8Scope, electroconductibility has improved 10
6Doubly.The electroconductibility that high conductivity is compounded with the bacteria cellulose film of silk fibroin is greatly improved.
(4) the bacteria cellulose film that high conductivity is compounded with silk fibroin places on the conductive glass, and drying at room temperature also is fixed on the conductive glass, and the bacteria cellulose film that is compounded with silk fibroin with the high conductivity that is fixed on the conductive glass is as working electrode; Platinum is as supporting electrode; Ag/AgCl is as reference electrode, and electrolytic solution is 0.2mol/l aniline, the 0.04mol/l tween 80; 1.2mol/l the mixed solution of hydrochloric acid is 0.15mA/cm in constant current density
2Electropolymerization forms polyaniline in the three-electrode system, and the polyaniline that aggregates into is deposited on high conductivity and is compounded with on the bacteria cellulose film of silk fibroin.Obtained flexible display material based on bacteria cellulose.
Result after the galvanic deposit is as shown in Figure 5, and figure a is that polyaniline is deposited on the result on the conductive glass through electrochemical method; Figure b is fixed on the bacteria cellulose film that high conductivity on the conductive glass is compounded with silk fibroin; Figure c is compounded with the result on the bacteria cellulose film of silk fibroin for the polyaniline electrochemical method is deposited on high conductivity.Can know that by experimental result picture polyaniline successfully has been deposited on conductive glass and high conductivity is compounded with on the bacteria cellulose film of silk fibroin.Obtained flexible display material based on bacteria cellulose.
(5) will be based on the flexible display material of bacteria cellulose as working electrode, platinized platinum is as counter electrode, and electrolytic solution is the Klorvess Liquid of 1mol/L.Utilize cyclic voltammetry, the voltage change scope is-2 volts to 2 volts, and frequency is 50mv/s.Reversible tautomerization takes place in the flexible display material color of observing based on bacteria cellulose between green, yellow, blueness.
The variable color process is as shown in Figure 6, and when figure a was a voltage-0.2V, the color of display material was shown in green; When figure b was a voltage-1.0V, the color of display material was shown as yellow; When figure c was a voltage+1.2V, the color of display material was shown as blueness; When figure d was a voltage+0.2V, the color of display material was shown in green.Reversible tautomerization takes place based on the flexible display material color of bacteria cellulose in the experimental result picture explanation between green, yellow, blueness.
(6) will take off from conductive glass based on the flexible display material of bacteria cellulose, the two sides adds tin electrode, and in addition scope is-2 volts to+2 volts voltage, through changing voltage, can make color reversible tautomerization between green, yellow, blueness of film.
Embodiment 2
(1) cultivation of bacteria cellulose: utilize glucose acetobacter xylinum bacterial classification ATCC53582, be seeded in (medium component is: contain 20 gram glucose, 5 gram yeast powders, 5 gram peptones, 1.5 gram Hydrocerol As, 2.7 gram Sodium phosphate, dibasics in the 1L water) in the S-H substratum.Leave standstill under 26 ℃ and cultivated 6 days, obtain the bacterial cellulose gel film.Place zero(ppm) water to soak two days the bacteria cellulose film, with boiling in the 1wt% sodium hydroxide solution 30 minutes, take out and be washed till neutrality then, preserve subsequent use down for 4 ℃ with zero(ppm) water.
(2) the bacteria cellulose film being immersed in concentration is in two (trifluoromethyl sulfonyl) imides of conductive ion liquid 1-butyl-1-methylpyrrole pyridine of 10%, and 4 ℃ were stirred 48 hours down, obtain the bacteria cellulose film of high conductivity.
(3) place 0.5% Na through the silk cocoon that shreds
2CO
3Boil in the solution and come unstuck, then at CaCl
2: CH
3CH
2OH: H
2O=1: the ternary component solution of 2: 8 (mol ratio) dissolves in 70 ℃ of water-baths, cools off under the room temperature, and using molecular weight cut-off is that 7000 dialysis tubing dialysis obtains silk fibroin protein solution.It is that 4 ℃ were stirred 48 hours down, obtain the bacteria cellulose film that is compounded with silk fibroin of high conductivity in 2% the silk fibroin protein solution that the bacteria cellulose film of high conductivity is immersed in concentration.
(4) the bacteria cellulose film that high conductivity is compounded with silk fibroin places on the conductive glass, and drying at room temperature also is fixed on the conductive glass, and the bacteria cellulose film that is compounded with silk fibroin with the high conductivity that is fixed on the conductive glass is as the working electrode working electrode; Platinum is as supporting electrode; Ag/AgCl is as reference electrode, and electrolytic solution is 0.2mol/l aniline, the 0.04mol/l tween 80; 1.2mol/l the mixed solution of hydrochloric acid is 0.15mA/cm in constant current density
2Electropolymerization forms polyaniline in the three-electrode system, and the polyaniline that aggregates into is deposited on high conductivity and is compounded with on the bacteria cellulose film of silk fibroin.Obtained flexible display material based on bacteria cellulose.
(5) will take off from conductive glass based on the flexible display material of bacteria cellulose, the two sides adds tin electrode, and in addition scope is-4 volts to+4 volts voltage, through changing voltage, can make color reversible tautomerization between green, yellow, blueness of film.
Embodiment 3
(1) cultivation of bacteria cellulose: utilize glucose acetobacter xylinum bacterial classification ATCC53582, be seeded in (medium component is: contain 20 gram glucose, 5 gram yeast powders, 5 gram peptones, 1.5 gram Hydrocerol As, 2.7 gram Sodium phosphate, dibasics in the 1L water) in the S-H substratum.Leave standstill under 26 ℃ and cultivated 6 days, obtain the bacterial cellulose gel film.Place zero(ppm) water to soak two days the bacteria cellulose film, with boiling in the 1wt% sodium hydroxide solution 30 minutes, take out and be washed till neutrality then, preserve subsequent use down for 4 ℃ with zero(ppm) water.
(2) place 0.5% Na through the silk cocoon that shreds
2CO
3Boil in the solution and come unstuck, then at CaCl
2: CH
3CH
2OH: H
2O=1: the ternary component solution of 2: 8 (mol ratio) dissolves in 70 ℃ of water-baths, cools off under the room temperature, and using molecular weight cut-off is that 7000 dialysis tubing dialysis obtains silk fibroin protein solution.It is in 2% the silk fibroin protein solution that the bacteria cellulose film is immersed in concentration, and 4 ℃ were stirred 48 hours down, obtain the high bacteria cellulose film that is compounded with silk fibroin of transparency.
It is in two (trifluoromethyl sulfonyl) imides of conductive ion liquid 1-butyl-1-methylpyrrole pyridine of 10% that the bacteria cellulose film that (3) will be compounded with silk fibroin is immersed in concentration; 4 ℃ were stirred 48 hours down, obtain the bacteria cellulose film that high conductivity is compounded with silk fibroin.
(4) the bacteria cellulose film that high conductivity is compounded with silk fibroin places on the conductive glass; Drying at room temperature also is fixed on the conductive glass; Be fixed on be compounded with silk fibroin as the high conductivity on the conductive material of electrodes the bacteria cellulose film as the working electrode working electrode; Platinum is as supporting electrode, and Ag/AgCl is as reference electrode, and electrolytic solution is 0.1mol/L K
3[Fe (CN)
6], 0.1mol/LFeCl
3, 0.1mol/l HCL mixing solutions is 0.1mA/cm in constant current density
2Electropolymerization forms polyaniline in the three-electrode system, and what aggregate into Prussian bluely is deposited on the bacteria cellulose film that high conductivity is compounded with silk fibroin.
(5) will be covered with Prussian blue composite package and take off from conductive glass, the two sides adds tin electrode, and in addition-1 volt to+1 volt voltage through changing voltage, can make the color reversible tautomerization of film.