CN104178928A - Flexible tin oxide nanofiber membrane and preparation method thereof - Google Patents
Flexible tin oxide nanofiber membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flexible tin oxide nanofiber membrane and a preparation method thereof. The preparation method comprises steps as follows: firstly, dissolving a tin source and a non-tin metal salt in a solvent, and sequentially adding and evenly mixing a coupling agent and a surfactant to prepare a uniform and stable precursor solution, wherein the precursor solution contains molecular chains adopting interpenetrating three-dimensional network structures; then preparing the precursor solution into a precursor fiber membrane with an electrostatic spinning technology; calcining the precursor fiber membrane at the air atmosphere to obtain the flexible tin oxide nanofiber membrane. The preparation technology is simple, the cost is low, and the obtained tin oxide nanofiber membrane has good flexibility and has potential application values in numerous technical fields of electro-conductive films, sensors, liquid crystal displays, solar cells and the like.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of flexible tin oxide nano tunica fibrosa and preparation method thereof, particularly relate to and a kind ofly there is the precursor solution of IPN tridimensional network strand as the preparation method of the flexible tin oxide nano tunica fibrosa of spinning solution.
Background technology
Tin oxide, as a kind of good semi-conducting material, because it has high conductivity, high-transmission rate and good chemistry and heat endurance, makes it be widely used in numerous technical fields such as conductive film, sensor, liquid crystal display, solar cells.Electrostatic spinning, as a kind of preparation method of novel nano-material, because its preparation technology is simple, spinning is with low cost, can spin the advantages such as of a great variety, has caused people's common concern.Utilize at present electrostatic spinning technique to prepare more than 50 kind of inorganic oxide nano fibrous membrane.But method of electrostatic spinning is prepared the large problem of inorganic oxide nano fibrous membrane ubiquity fragility, thereby limit its practical application.
Chinese patent CN201310492460.6 discloses the preparation side of a kind of tin oxide fibre presoma and tin oxide crystal fibre, but this method all needs the aging long period preparing in precursor solution process, and the fibre diameter uniformity preparing is poor, easy fracture, cannot obtains and there is flexible tin oxide nano fiber.
NPG Asia Materials (2014) 6 has reported and has utilized electrostatic spinning technique to prepare flexible tin oxide nano fiber, these methods have added high molecular polymer in the time preparing tin oxide nano fiber, make hybridized fiber film ceramic composition content low, cause inorfil productive rate extremely low, in addition too much organic matter easily causes hybridized fiber film in calcination process, to shrink seriously, thereby makes tunica fibrosa mechanical performance variation.
Summary of the invention
The object of this invention is to provide a kind of flexible tin oxide nano tunica fibrosa and preparation method thereof, particularly provide a kind of precursor solution of IPN tridimensional network strand to prepare the method for flexible tin oxide nano tunica fibrosa as spinning solution.
The preparation method of a kind of flexible tin oxide nano tunica fibrosa of the present invention, concrete steps are:
The first step: Xi Yuan and a kind of non-tin metal salt are dissolved in solvent successively, first stir a period of time, make that hydrolysis condensation reaction occurs between Xi Yuan and solvent in whipping process or chelation forms the strand with tridimensional network, the object that adds a kind of non-tin metal salt is in calcination process, to suppress grain growth by ion doping, makes the crystal defect of generation less, add coupling agent, continue again to stir a period of time, on coupling agent, there are two kinds of groups, comprise the group of close inorganic molecule and the group of close organic molecule, wherein close inorganic molecule group forms hydroxyl by there is part hydrolysis in solution, afterwards again with above-mentioned tridimensional network strand on part of hydroxyl generation condensation reaction, coupling agent is connected with covalent bond with the strand of tridimensional network, then add surfactant, mix the precursor solution of making stable homogeneous, in described precursor solution, there is the strand of IPN tridimensional network, now the close organic molecule group on coupling agent is connected by chemical reaction occurring or producing hydrogen bond action with the hydrophilic radical on surfactant, along with the increase of coupling agent hydrolysis degree, hydroxyl generation condensation reaction on hydroxyl continuation and above-mentioned tridimensional network strand on coupling agent, close organic molecule group on coupling agent and the hydrophilic radical on surfactant continue to occur chemical reaction or form hydrogen bond simultaneously, hydrophobic group on surfactant aligns by hydrogen bond, tridimensional network strand constantly interts and tangles, and between strand in tridimensional network-coupling agent-surfactant, produce " bridging ", thereby form the tridimensional network of IPN, the viscosity of precursor solution is increased, spinnability strengthens.
Second step: under the condition of 20-28 DEG C and relative humidity 30-60%, above-mentioned precursor solution is carried out to electrostatic spinning, under electric field action, charged drop overcomes surface tension, slenderizing fibroblast in air, finally be deposited on and receive on substrate, obtain precursor fibre film, prepared precursor fibre has the characteristics such as fibre diameter is little, fiber continuity is good;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, obtained flexible tin oxide nano tunica fibrosa.In the precursor solution of preparing due to the present invention, strand is IPN tridimensional network, in precursor fibre, inorganic component content is higher simultaneously, therefore the skeleton structure that filament is complete in calcination process can not be damaged because of the spinodal decomposition of a large amount of organic components, makes the last tin oxide nano tunica fibrosa obtaining have good flexibility.
As preferred technical scheme:
The preparation method of a kind of flexible tin oxide nano tunica fibrosa as above, in the described first step, Xi Yuan and non-tin metal salt mol ratio are 100:1-10; The ratio of Xi Yuan and solvent is 10g:50-150mL; It is described that first to stir a period of time be 60-120min; The mol ratio of Xi Yuan and coupling agent is 1:0.05-0.25; It is 15-30min that a period of time is stirred in described continuation again; The mol ratio of Xi Yuan and surfactant is 1:0.05-0.2; The dynamic viscosity of described precursor solution is that 0.1-5Pas, electrical conductivity are 10-50mS/m.
The preparation method of a kind of flexible tin oxide nano tunica fibrosa as above, described Xi Yuan is more than one in butter of tin, stannous chloride, stannous sulfate, stannous oxalate.
Described non-tin metal salt is the one in magnesium salts, aluminium salt, calcium salt, chromic salts, manganese salt, molysite, cobalt salt, nickel salt, mantoquita, zinc salt, yttrium salt, zirconates, antimonic salt, cadmium salt, titanium salt, barium salt;
Magnesium salts is Magnesium dichloride hexahydrate, magnesium nitrate hexahydrate or magnesium sulfate;
Aluminium salt is ANN aluminium nitrate nonahydrate, Aluminium chloride hexahydrate or aluminium isopropoxide;
Calcium salt is calcium sulfate, calcium nitrate tetrahydrate or calcium chloride;
Chromic salts is chromium acetate, chromium trichloride or chromic nitrate;
Manganese salt is four hydration manganese chlorides, four hydration manganese acetate or Manganous sulfate monohydrates;
Molysite is Fe(NO3)39H2O, Iron(III) chloride hexahydrate or ferric sulfate;
Cobalt salt is cobalt acetate, cabaltous nitrate hexahydrate or Cobalt monosulfate heptahydrate;
Nickel salt is single nickel salts, Nickelous nitrate hexahydrate or Nickel dichloride hexahydrate;
Mantoquita is Copper dichloride dihydrate, Salzburg vitriol or Gerhardite;
Zinc salt is zinc chloride, Zinc vitriol or zinc nitrate hexahydrate;
Yttrium salt is six nitric hydrate yttriums or six hydration yttrium chlorides;
Zirconates is zirconium chloride or zirconium acetate;
Antimonic salt is Antimony pentachloride, trichloride antimony or antimony acetate;
Cadmium salt is caddy or four nitric hydrate cadmiums;
Titanium salt is titanium tetrachloride, isopropyl titanate or butyl titanate;
Barium salt is barium chloride dihydrate or barium nitrate.
The preparation method of a kind of flexible tin oxide nano tunica fibrosa as above, described solvent corresponds to respectively according to Xi Yuan:
Butter of tin: water, ethanol, toluene, carbon tetrachloride or acetone;
Stannous chloride: water, ethanol, isobutanol or acetone;
Stannous sulfate: water or sulfuric acid;
Stannous oxalate: hydrochloric acid.
The preparation method of a kind of flexible tin oxide nano tunica fibrosa as above, described coupling agent is the one in gamma-aminopropyl-triethoxy-silane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, MTMS, vinyltrimethoxy silane or γ-(methacryloxypropyl) propyl group methyl dimethoxysilane.
The preparation method of a kind of flexible tin oxide nano tunica fibrosa as above, described surfactant is dodecyl benzyl dimethyl ammonium chloride, neopelex, DDAO, dodecyl-dimethyl amine second lactone, N, the one in N-bis-(2-ethoxy) laurylamide or glycerin polyoxyethylene ether.
The preparation method of a kind of flexible tin oxide nano tunica fibrosa as above, described electrospinning process refers to that described precursor solution is input to the flow velocity of 1-5mL/h on the spinning head of electrospinning device, the high voltage source that simultaneously spinning head is connected to 10-30kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 10-30cm.
The preparation method of a kind of flexible tin oxide nano tunica fibrosa as above, described calcining refers to that calcining heat progressively rises to 500-800 DEG C from room temperature, programming rate is 1-10 DEG C/min, and keeps 10-240min under the highest calcining heat.The fibrous inside crystallite dimension obtaining in the present invention is 5-100nm.
The present invention also propose to prepare by preparation method described above the flexible tin oxide nano tunica fibrosa of one, the average fibre diameter of described flexible tin oxide nano tunica fibrosa is 10-500nm, and relative standard deviation is 1-5%; The pliability of described flexible tin oxide nano tunica fibrosa is 10-100mN, (fibrous material prepared of electrostatic spinning is textile-like to have good flexibility, can use for reference test paper pliability method and characterize its flexibility, flexible standard: pliability 0-80mN is flexible outstanding; Pliability 80-160mN is flexible good, referring to the mensuration of QB3529-1999 the People's Republic of China light industry standard-tissue, GB/T8942-2002 National Standard of the People's Republic of China-paper pliability), the fibrous inside crystallite dimension of acquisition is 5-100nm.
First the present invention is dissolved in Xi Yuan and a kind of non-tin metal salt in solvent successively, and add successively coupling agent and surfactant to mix, make the precursor solution of stable homogeneous by the chemical reaction between active group or hydrogen bond action, in described precursor solution, there is the strand of IPN tridimensional network; Through calcining organic component spinodal decomposition in precursor fibre, inorganic component is retained, due in fiber taking inorganic component as main body, therefore the skeleton structure that filament is complete in calcination process can not be damaged because of the spinodal decomposition of a large amount of organic components, makes the last tin oxide nano tunica fibrosa obtaining have good flexibility.
Beneficial effect:
The preparation method of a kind of flexible tin oxide nano tunica fibrosa of the present invention, without adding polymer or aging, and in spinning solution, tin oxide content is higher, and tin oxide nano fiber yield is high, and preparation technology is simple, with low cost.A kind of flexible tin oxide nano tunica fibrosa of the present invention has good flexibility.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
A preparation method for flexible tin oxide nano tunica fibrosa, concrete steps are:
The first step: tin source butter of tin and non-tin metal salt Magnesium dichloride hexahydrate are dissolved in water successively, after stirring 60min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 15min, add surfactant dodecyl benzyl dimethyl ammonium chloride, wherein butter of tin and Magnesium dichloride hexahydrate mol ratio are 100:1, the ratio of butter of tin and water is 10g:50mL, the mol ratio of butter of tin and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.05, the mol ratio of butter of tin and surfactant dodecyl benzyl dimethyl ammonium chloride is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 3Pas, electrical conductivity are 50mS/m, has the strand of IPN tridimensional network in described precursor solution, and its structural formula is as follows:
Second step: above-mentioned precursor solution is made to precursor fibre film by electrospinning process; Electrostatic spinning process parameter: spinning temperature is 20 DEG C, relative humidity is 30%, and rate of flooding is 3mL/h, and receiving range is 10cm, and spinning voltage is 10kV;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 500 DEG C from room temperature, programming rate is 1 DEG C/min, and under the highest calcining heat, keep 240min, obtain flexible tin oxide nano tunica fibrosa, described flexible tin oxide nano tunica fibrosa average fibre diameter is 280nm, and relative standard deviation is 1%, described fibrous inside crystallite dimension is 5nm, the densification of described flexible tin oxide nano fibre structure, described flexible tin oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T8942-2002 National Standard of the People's Republic of China-paper pliability, recording tunica fibrosa pliability is 10mN.
Embodiment 2
A preparation method for flexible tin oxide nano tunica fibrosa, concrete steps are:
The first step: tin source butter of tin and non-tin metal salt Aluminium chloride hexahydrate are dissolved in the mixed solvent of water/ethanol successively, after stirring 120min, add coupling agent MTMS, after continuing again to stir 30min, add surfactant DDAO, wherein butter of tin and Aluminium chloride hexahydrate mol ratio are 100:10, the ratio of butter of tin and water/ethanol is 10g:150mL, the volume ratio of water and ethanol is 2:1, the mol ratio of butter of tin and coupling agent MTMS is 1:0.25, the mol ratio of butter of tin and surfactant DDAO is 1:0.2, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 1Pas, electrical conductivity are 30mS/m, has the strand of the IPN tridimensional network similar with embodiment 1 in described precursor solution,
Second step: above-mentioned precursor solution is made to precursor fibre film by electrospinning process; Electrostatic spinning process parameter: spinning temperature is 20 DEG C, relative humidity is 30%, and rate of flooding is 1mL/h, and receiving range is 30cm, and spinning voltage is 30kV;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 800 DEG C from room temperature, programming rate is 10 DEG C/min, and under the highest calcining heat, keep 240min, obtain flexible tin oxide nano tunica fibrosa, described flexible tin oxide nano tunica fibrosa average fibre diameter is 500nm, and relative standard deviation is 5%, described fibrous inside crystallite dimension is 100nm, the densification of described flexible tin oxide nano fibre structure, described flexible tin oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T8942-2002 National Standard of the People's Republic of China-paper pliability, recording tunica fibrosa pliability is 100mN.
Embodiment 3
A preparation method for flexible tin oxide nano tunica fibrosa, concrete steps are:
The first step: tin source stannous chloride and non-tin metal salt calcium chloride are dissolved in the mixed solvent of water/ethanol/acetone successively, after stirring 100min, add coupling agent vinyltrimethoxy silane, after continuing again to stir 20min, add surfactant neopelex, wherein the mol ratio of stannous chloride and calcium chloride is 100:3, the ratio of stannous chloride and water/ethanol/acetone is 10g:90mL, water, ethanol, the volume ratio of acetone is 1:1:1, the mol ratio of stannous chloride and coupling agent vinyltrimethoxy silane is 1:0.15, the mol ratio of stannous chloride and surfactant neopelex is 1:0.1, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 2Pas, electrical conductivity are 15mS/m, has the strand of the IPN tridimensional network similar with embodiment 1 in described precursor solution,
Second step: above-mentioned precursor solution is made to precursor fibre film by electrospinning process; Electrostatic spinning process parameter: spinning temperature is 25 DEG C, relative humidity is 50%, and rate of flooding is 2mL/h, and receiving range is 20cm, and spinning voltage is 25kV;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, programming rate is 5 DEG C/min, and under the highest calcining heat, keep 120min, obtain flexible tin oxide nano tunica fibrosa, described flexible tin oxide nano tunica fibrosa average fibre diameter is that 300nm and relative standard deviation are 2%, described fibrous inside crystallite dimension is 30nm, the densification of described flexible tin oxide nano fibre structure, described flexible tin oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T8942-2002 National Standard of the People's Republic of China-paper pliability, recording tunica fibrosa pliability is 50mN.
Embodiment 4
A preparation method for flexible tin oxide nano tunica fibrosa, concrete steps are:
The first step: by tin source butter of tin, stannous chloride and non-tin metal salt chromium trichloride are dissolved in water, after stirring 80min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 20min, add surfactant dodecyl benzyl dimethyl ammonium chloride, wherein butter of tin, the mass ratio of stannous chloride is 1:1, butter of tin, the mol ratio of stannous chloride and chromium trichloride is 100:1, butter of tin, the ratio of stannous chloride and water is 10g:60mL, butter of tin, the mol ratio of stannous chloride and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.05, butter of tin, the mol ratio of stannous chloride and surfactant dodecyl benzyl dimethyl ammonium chloride is 1:0.1, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 1Pas, electrical conductivity are 35mS/m, has the strand of the IPN tridimensional network similar with embodiment 1 in described precursor solution,
Second step: above-mentioned precursor solution is made to precursor fibre film by electrospinning process; Electrostatic spinning process parameter: spinning temperature is 28 DEG C, relative humidity is 45%, and rate of flooding is 1mL/h, and receiving range is 25cm, and spinning voltage is 25kV;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 700 DEG C from room temperature, programming rate is 5 DEG C/min, and under the highest calcining heat, keep 120min, obtain flexible tin oxide nano tunica fibrosa, described flexible tin oxide nano tunica fibrosa average fibre diameter is 350nm, and relative standard deviation is 3%, described fibrous inside crystallite dimension is 60nm, the densification of described flexible tin oxide nano fibre structure, described flexible tin oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T8942-2002 National Standard of the People's Republic of China-paper pliability, recording tunica fibrosa pliability is 80mN.
Embodiment 5
A preparation method for flexible tin oxide nano tunica fibrosa, concrete steps are:
The first step: by tin source butter of tin, stannous chloride and non-tin metal salt four hydration manganese chlorides are dissolved in water/ethanol, after stirring 70min, add coupling agent MTMS, after continuing again to stir 30min, add surfactant N, N-bis-(2-ethoxy) laurylamide, wherein butter of tin, the mass ratio of stannous chloride is 2:1, butter of tin, the mol ratio of stannous chloride and four hydration manganese chlorides is 100:9, butter of tin, the ratio of stannous chloride and water/ethanol is 10g:80mL, the volume ratio of water and ethanol is 3:1, butter of tin, the mol ratio of stannous chloride and coupling agent MTMS is 1:0.25, butter of tin, stannous chloride and surfactant N, the mol ratio of N-bis-(2-ethoxy) laurylamide is 1:0.1, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas, electrical conductivity are 22mS/m, has the strand of the IPN tridimensional network similar with embodiment 1 in described precursor solution,
Second step: above-mentioned precursor solution is made to precursor fibre film by electrospinning process; Electrostatic spinning process parameter: spinning temperature is 25 DEG C, relative humidity is 55%, and rate of flooding is 5mL/h, and receiving range is 25cm, and spinning voltage is 30kV;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 550 DEG C from room temperature, programming rate is 2 DEG C/min, and under the highest calcining heat, keep 120min, obtain flexible tin oxide nano tunica fibrosa, described flexible tin oxide nano tunica fibrosa average fibre diameter is 320nm, and relative standard deviation is 3%, described fibrous inside crystallite dimension is 58nm, the densification of described flexible tin oxide nano fibre structure, described flexible tin oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T8942-2002 National Standard of the People's Republic of China-paper pliability, recording tunica fibrosa pliability is 55mN.
Embodiment 6
A preparation method for flexible tin oxide nano tunica fibrosa, concrete steps are:
The first step: by tin source butter of tin, stannous chloride and non-tin metal salt Iron(III) chloride hexahydrate are dissolved in water/ethanol/acetone, after stirring 120min, add coupling agent vinyltrimethoxy silane, after continuing again to stir 30min, add surfactant glycerin polyoxyethylene ether, wherein butter of tin, the mass ratio of stannous chloride is 1:2, butter of tin, the mol ratio of stannous chloride and Iron(III) chloride hexahydrate is 100:5, butter of tin, the ratio of stannous chloride and water/ethanol/acetone is 10g:60mL, water, ethanol, the volume ratio of acetone is 1:1:1, butter of tin, the mol ratio of stannous chloride and coupling agent vinyltrimethoxy silane is 1:0.1, butter of tin, the mol ratio of stannous chloride and surfactant glycerin polyoxyethylene ether is 1:0.1, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 2Pas, electrical conductivity are 20mS/m, has the strand of the IPN tridimensional network similar with embodiment 1 in described precursor solution,
Second step: above-mentioned precursor solution is made to precursor fibre film by electrospinning process; Electrostatic spinning process parameter: spinning temperature is 25 DEG C, relative humidity is 45%, and rate of flooding is 3mL/h, and receiving range is 15cm, and spinning voltage is 30kV;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 550 DEG C from room temperature, programming rate is 1 DEG C/min, and under the highest calcining heat, keep 60min, obtain flexible tin oxide nano tunica fibrosa, described flexible tin oxide nano tunica fibrosa filament average diameter is that 400nm and relative standard deviation are 3%, described fibrous inside crystallite dimension is 45nm, the densification of described flexible tin oxide nano fibre structure, described flexible tin oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T8942-2002 National Standard of the People's Republic of China-paper pliability, recording tunica fibrosa pliability is 78mN.
Embodiment 7
A preparation method for flexible tin oxide nano tunica fibrosa, concrete steps are:
The first step: by tin source butter of tin, stannous chloride, stannous sulfate and non-tin metal salt cobalt acetate are dissolved in water, after stirring 120min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 15min, add surfactant neopelex, wherein butter of tin, stannous chloride, the mass ratio of stannous sulfate is 1:1:1, butter of tin, stannous chloride, the mol ratio of stannous sulfate and cobalt acetate is 100:1, butter of tin, stannous chloride, the ratio of stannous sulfate and water is 10g:50mL, butter of tin, stannous chloride, the mol ratio of stannous sulfate and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.15, butter of tin, stannous chloride, the mol ratio of stannous sulfate and surfactant neopelex is 1:0.2, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 5Pas, electrical conductivity are 25mS/m, has the strand of the IPN tridimensional network similar with embodiment 1 in described precursor solution,
Second step: above-mentioned precursor solution is made to precursor fibre film by electrospinning process; Electrostatic spinning process parameter: spinning temperature is 24 DEG C, relative humidity is 45%, and rate of flooding is 1mL/h, and receiving range is 15cm, and spinning voltage is 30kV;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 650 DEG C from room temperature, programming rate is 2 DEG C/min, and under the highest calcining heat, keep 180min, obtain flexible tin oxide nano tunica fibrosa, described flexible tin oxide nano tunica fibrosa average fibre diameter is 420nm, and relative standard deviation is 5%, described fibrous inside crystallite dimension is 38nm, the densification of described flexible tin oxide nano fibre structure, described flexible tin oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T8942-2002 National Standard of the People's Republic of China-paper pliability, recording tunica fibrosa pliability is 65mN.
Embodiment 8-42
Embodiment 8-42 preparation process is with embodiment 1, wherein (note: mixing time 1-Jiang Xiyuan is dissolved in solvent, adds coupling agent after stirring 60-120min as table for precursor solution configuration parameter, electrostatic spinning parameter and flexible tin oxide nano tunica fibrosa performance parameter; Mixing time 2-continue to add surfactant after stirring 15-30min)
Claims (9)
1. a preparation method for flexible tin oxide nano tunica fibrosa, is characterized in that, concrete steps are:
The first step: Xi Yuan and a kind of non-tin metal salt are dissolved in solvent, first stir a period of time, add coupling agent, continue again to stir a period of time, then add surfactant, mix the precursor solution of making stable homogeneous, in described precursor solution, there is the strand of IPN tridimensional network;
Second step: under the condition of 20-28 DEG C and relative humidity 30-60%, above-mentioned precursor solution is made to precursor fibre film by electrospinning process;
The 3rd step: above-mentioned precursor tunica fibrosa is calcined under air atmosphere, obtained flexible tin oxide nano tunica fibrosa.
2. the preparation method of a kind of flexible tin oxide nano tunica fibrosa according to claim 1, is characterized in that, in the described first step, Xi Yuan and non-tin metal salt mol ratio are 100:1-10; The ratio of Xi Yuan and solvent is 10g:50-150mL; It is described that first to stir a period of time be 60-120min; The mol ratio of Xi Yuan and coupling agent is 1:0.05-0.25; It is 15-30min that a period of time is stirred in described continuation again; The mol ratio of Xi Yuan and surfactant is 1:0.05-0.2; The dynamic viscosity of described precursor solution is that 0.1-5Pas, electrical conductivity are 10-50mS/m.
3. the preparation method of a kind of flexible tin oxide nano tunica fibrosa according to claim 1 and 2, is characterized in that, described Xi Yuan is more than one in butter of tin, stannous chloride, stannous sulfate, stannous oxalate;
Described non-tin metal salt is the one in magnesium salts, aluminium salt, calcium salt, chromic salts, manganese salt, molysite, cobalt salt, nickel salt, mantoquita, zinc salt, yttrium salt, zirconates, antimonic salt, cadmium salt, titanium salt, barium salt;
Magnesium salts is Magnesium dichloride hexahydrate, magnesium nitrate hexahydrate or magnesium sulfate;
Aluminium salt is ANN aluminium nitrate nonahydrate, Aluminium chloride hexahydrate or aluminium isopropoxide;
Calcium salt is calcium sulfate, calcium nitrate tetrahydrate or calcium chloride;
Chromic salts is chromium acetate, chromium trichloride or chromic nitrate;
Manganese salt is four hydration manganese chlorides, four hydration manganese acetate or Manganous sulfate monohydrates;
Molysite is Fe(NO3)39H2O, Iron(III) chloride hexahydrate or ferric sulfate;
Cobalt salt is cobalt acetate, cabaltous nitrate hexahydrate or Cobalt monosulfate heptahydrate;
Nickel salt is single nickel salts, Nickelous nitrate hexahydrate or Nickel dichloride hexahydrate;
Mantoquita is Copper dichloride dihydrate, Salzburg vitriol or Gerhardite;
Zinc salt is zinc chloride, Zinc vitriol or zinc nitrate hexahydrate;
Yttrium salt is six nitric hydrate yttriums or six hydration yttrium chlorides;
Zirconates is zirconium chloride or zirconium acetate;
Antimonic salt is Antimony pentachloride, trichloride antimony or antimony acetate;
Cadmium salt is caddy or four nitric hydrate cadmiums;
Titanium salt is titanium tetrachloride, isopropyl titanate or butyl titanate;
Barium salt is barium chloride dihydrate or barium nitrate.
4. the preparation method of a kind of flexible tin oxide nano tunica fibrosa according to claim 1 and 2, is characterized in that, described solvent corresponds to respectively according to Xi Yuan:
Butter of tin: water, ethanol, toluene, carbon tetrachloride or acetone;
Stannous chloride: water, ethanol, isobutanol or acetone;
Stannous sulfate: water or sulfuric acid;
Stannous oxalate: hydrochloric acid.
5. the preparation method of a kind of flexible tin oxide nano tunica fibrosa according to claim 1 and 2, it is characterized in that, described coupling agent is the one in gamma-aminopropyl-triethoxy-silane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, MTMS, vinyltrimethoxy silane or γ-(methacryloxypropyl) propyl group methyl dimethoxysilane.
6. the preparation method of a kind of flexible tin oxide nano tunica fibrosa according to claim 1 and 2, it is characterized in that, described surfactant is dodecyl benzyl dimethyl ammonium chloride, neopelex, DDAO, dodecyl-dimethyl amine second lactone, N, the one in N-bis-(2-ethoxy) laurylamide or glycerin polyoxyethylene ether.
7. the preparation method of a kind of flexible tin oxide nano tunica fibrosa according to claim 1, it is characterized in that, described electrospinning process refers to that described precursor solution is input to the flow velocity of 1-5mL/h on the spinning head of electrospinning device, the high voltage source that simultaneously spinning head is connected to 10-30kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 10-30cm.
8. the preparation method of a kind of flexible tin oxide nano tunica fibrosa according to claim 1, it is characterized in that, in the 3rd described step, described calcining refers to that calcining heat progressively rises to 500-800 DEG C from room temperature, programming rate is 1-10 DEG C/min, and keeps 10-240min under the highest calcining heat.
9. the flexible tin oxide nano tunica fibrosa of preparing according to method described in any one in claim 1～8, it is characterized in that, the average fibre diameter of described flexible tin oxide nano tunica fibrosa is 10-500nm, and relative standard deviation is 1-5%; The pliability of described flexible tin oxide nano tunica fibrosa is 10-100mN, and the fibrous inside crystallite dimension of acquisition is 5-100nm.
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