EP2496740A1 - Process for producing nanofibres - Google Patents
Process for producing nanofibresInfo
- Publication number
- EP2496740A1 EP2496740A1 EP10771101A EP10771101A EP2496740A1 EP 2496740 A1 EP2496740 A1 EP 2496740A1 EP 10771101 A EP10771101 A EP 10771101A EP 10771101 A EP10771101 A EP 10771101A EP 2496740 A1 EP2496740 A1 EP 2496740A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- solution
- process step
- solvent
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5296—Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9661—Colour
Definitions
- the present invention relates to a process for the preparation of metal oxide nanofibers using a sol-gel precursor.
- the "green fibers" produced by the process according to the invention consisting of a polymer component, an inorganic fraction and, if appropriate, solvent residues, are distinguished by an increased proportion of inorganic components compared with the prior art.
- the metal oxide nanofibers according to the invention are produced by calcining, the thermal removal of the polymer component and transformation of the inorganic moiety into the desired metal oxide. Nanofibers are becoming increasingly important in textile production, optics, electronics, biotechnology, pharmacy, medicine and plastics engineering, e.g. as filtration and separation media.
- nanofibers refers to fiber structures whose diameter is in a range of about 0.1 to 999 nm (also referred to as nano-scale).
- nanostructures such as nanowires and nanotubes, both of which have a nanoscale cross-section.
- the currently common method for the production of nanofibers is the so-called electrospinning.
- a polymer solution or a polymer melt containing a metal compound, for example a metal salt, and optionally further additives brought by means of two electrodes in a strong electric field.
- Electrostatic charge creates local instabilities in the solution, which are first formed into conical structures and then into fibers.
- the fibers move towards an electrode most of the solvent evaporates and the fibers are additionally stretched.
- the transformation of the metal compound into the corresponding metal oxide takes place.
- oxidic nanofibers are obtained with a diameter of ⁇ 1 ⁇ .
- filtration applications as part of gas sensors, as well as in catalyst applications.
- nanofibers in particular of ZnO nanofibers
- Siddheswaran et al. Preparation and characterization of ZnO nanofibers by electrospinning", Cryst. Rest. Technol. 2006, 41, 447-449.
- Siddheswaran et al. initially provide a precursor solution consisting of poly- vinyl alcohol, zinc acetate and water, which is transformed at elevated temperature to a viscous gel. Subsequently, this precursor solution is spun with a syringe-based electrospinning apparatus ("needle electrospinning") into nanofibers. These nanofibers are then calcined to ZnO fibers.
- the ZnO nanofibers produced by this process have a very irregular surface structure and varying diameters and are fused together at the contact points, which also results in a low aspect ratio.
- a process for producing Sn0 2 nanofibers is described by Zhang et al. described ("fabrication and ethanol-sensing properties of micro gas sensor based on electrospun Sn0 2 nanofibers", Sensors and Actuators B 2008, 67-73).
- Zhang et al. prepare a precursor solution consisting of polyvinyl alcohol, tin (IV) chloride and water and spin them into nanofibers with an electrospinning machine. These nanofibers are then calcined to Sn0 2 nanofibers.
- the Sn0 2 nanofibers produced by this process have varying diameters and are also fused together at the contact points, resulting in a low aspect ratio and also an unsatisfactory metal loading.
- the object of the present invention is to provide an improved process for the preparation of metal oxide nanofibers with a diameter in the range of 0.1 to 999 nm. Furthermore, it is an object of the invention to provide a process for the preparation of metal oxide fibers, by means of which first green fibers with high inorganic content can be produced, which are subsequently calcined.
- This object is achieved by a method for producing metal oxide fibers having a diameter in the range of 0.1 to 999 nm comprising the steps
- the "green fibers" produced in process step (f) have an increased inorganic content compared to green fibers known from the prior art.
- the solution prepared for the electrospinning step has high hydrolytic stability - it can be stored in air over a period of about 12 months. This is particularly advantageous, because thus the loss of mass in the removal of the polymer in process step (g), for example, the calcination is lower.
- the fibers obtained in process step (g) have a lower porosity and roughness.
- the metal compound or a plurality of metal compounds in a solvent selected from the group consisting of water, ethanol, isopropanol, n-propanol, tetrahydrofuran (THF) and dimethylformamide or dissolved in a mixture of two, three or more of the abovementioned solvents.
- the amount of the metal compound which is dissolved in the solvent can vary over wide ranges.
- the metal ion contained in the metal compound or the metal ions in the solution has a concentration in the range of 0.1 to 7 mol / l, preferably in the range of 0.2 to 1 mol / l.
- metal compound in the context of the present invention means a compound in which the metal is bound anionically or covalently with organic or inorganic ligands.
- At least one Metal compounds are, for example, inorganic or organic compounds or salts of one or more metal (s) selected from the group Cu, Ag, Au, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn , Re, Fe, Ru, Ni, Pd, Co, Rh, Ir, Sb, Sn, In, Al, Ga, Er and Zn.
- the metal of the metal compound is selected from the group Sb, Sn, In, Al, Ga and Zn According to a particularly preferred embodiment, it is a mixture containing compounds of the metals Sn, Sb or In or to a mixture containing compounds of the metals Sn and Sb.
- Inorganic compounds in the sense of the present invention For example, chlorides, sulfates and nitrates, if these combinations of organic anions and the respective metal cations exist.
- Organic compounds in the context of the present invention are salts of carboxylic acids, for example formates, acetates, citrates and acetylacetonates with the corresponding metals, if combinations of organic anions and the respective metal cation are present.
- an alkaline precipitation of the at least one metal ion in the form of its hydroxide is carried out in process step (b).
- the alkaline precipitation of the at least one metal or metal ion is carried out by adding at least one ammonium compound and / or at least one alkali metal hydroxide.
- the compounds that can be used for alkaline precipitation are generally selected from the group NR 4 OH, wherein R is independently H or C 1 to C 4 alkyl, NH 4 OH, NH 3 , NaOH, KOH, NH 4 HC0 3 and (NH 4 ) 2 C0 3 , NH 4 F, NaF, KF and LiF or a mixture of two, three or more of the aforementioned compounds.
- R is independently H or C 1 to C 4 alkyl
- the amount of ammonium compound or alkali hydroxide necessary for carrying out the alkaline precipitation can vary over wide ranges.
- the person skilled in the art uses an appropriate amount so that the pH value is in the range specified above and the metal ions precipitate out of the solution in the form of their hydroxides.
- at least one stabilizer selected from the group of the amino acids, such as alanine, phenylalanine, valine, leucine, and ⁇ -caprolactam before carrying out the alkaline precipitation in process step (b) of the solution, at least one stabilizer selected from the group of the amino acids, such as alanine, phenylalanine, valine, leucine, and ⁇ -caprolactam.
- the proportion of this stabilizer can be wider are varied and is generally 0.5 to 10 wt .-%, preferably 1 to 5 wt .-%, based on the provided in step (a) solution.
- This suspension can likewise be added to a mixture prepared in process step (e) in a proportion of from 1 to 99% by weight.
- this intermediate step the preparation of the dispersion of metal oxide precursors, in the presence of a stabilizer selected from the group alanine, phenylalanine, valine, leucine and ⁇ -caprolactam is performed.
- the precipitated hydroxides are separated in the subsequent process step (c).
- the separation of the hydroxides from the mother liquor by means of filtration, decantation and / or centrifugation. Methods for separating a precipitated solid from a mother liquor are known in the art and are not further detailed at this point.
- the metal hydroxides separated in process step (c) or the metal hydroxide separated off in process step (c) are washed.
- a solvent selected from the group consisting of water, methanol, ethanol, i-propanol and n-propanol or a mixture thereof is generally used.
- ammonium ions, alkali ions or chloride ions are removed from the metal hydroxide.
- the washing process can be repeated several times.
- the solvent or solvent mixture used for washing has a pH which corresponds to the pH at which the alkaline precipitation was carried out in process step (b).
- the precipitate or the metal hydroxide is dissolved in an amine, or preferably in a solvent-amine mixture.
- the solvent in the solvent-amine mixture is according to a preferred Embodiment of the invention selected from the group consisting of water, methanol, ethanol, i-propanol, n-propanol, tetrahydrofuran (THF) and dimethylformamide or a mixture thereof, particularly preferably the solvent is water.
- the amine contained in the solvent-amine mixture is generally a primary, secondary or tertiary amine according to general formula NR 3 , where R independently of one another is H, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 6, preferably 2 to 4, more preferably 2, represents carbon atoms.
- Alkyl group means a saturated aliphatic hydrocarbon group which may be straight chain or branched and may have from 1 to 6 carbon atoms in the chain. Branched means that a lower alkyl group such as methyl, ethyl or propyl is attached to a linear alkyl chain.
- the alkyl group is, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert.
- the amine is diethylamine.
- the weight ratio of solvent to amine can be varied over wide ranges and is generally in the range of 5 to 10 to 1 to 5, preferably in the range of 7 to 8 to 3 to 2.
- the concentration of the metal hydroxide or metal hydroxides is generally in the range from 5 to 30 wt .-%, preferably in the range of 10 to 20 wt .-%, more preferably the proportion is 15 wt .-%, based on the total mass of the solution or dispersion prepared in process step (d).
- the mixture prepared in process step (d), also called sol-gel precursor, is miscible over both concentration ranges with conventional solvents used in the production of metal oxide nanofibers.
- the presence of several hydroxides in the precursor leads to a thorough mixing of the hydroxides, which leads to a very homogeneous metal distribution in the subsequently produced nanofibers.
- the use of the so-called sol-gel precursor in the context of the method according to the invention is advantageous since the electrospinning delivers approximately always equal amounts of green fibers.
- a solution containing one or more polymers, one or more solvents and the mixture prepared in process step (d), the sol-gel precursor are prepared from which the metal oxide nanofibers are subsequently produced.
- the solvent or solvent mixture is selected so that both the one or more polymers and the sol-gel precursor are soluble in it.
- Soluble is understood to mean that the polymer and the sol-gel precursor have a solubility of at least in each case 1% by weight in the corresponding solvent or solvent mixture.
- the person skilled in the art is aware that for this purpose he has to coordinate the polarities of the polymer, the sol-gel precursor and the solvent. He can do this with the help of his general knowledge.
- the solvent used in process step (e) is selected from the group consisting of water, methanol, ethanol, ethanediol, n-propanol, 2-propanol, n-butanol, isobutanol, tert-butanol, cyclohexanol, formic acid, acetic acid, trifluoroacetic acid, diethylamine , Diisopropylamine, phenylethylamine, acetone, acetylacetone, acetonitrile, diethylene glycol, formamide, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene, dimethylacetamide, N-methylpyrrolidone (NMP) and tetrahydrofuran or a mixture of two or more of the aforementioned solvents.
- the solvent used to prepare the solution in step (e) is one or more selected from water, methanol, ethanol, ethane
- the polymer used in the preparation of the solution in process step (e) is generally selected from the group consisting of polyethers, polyethylene oxides, polyvinyl alcohols, polyvinyl acetates, polyvinylpyrolidones, polyacrylic acids, polyurethanes, polylactides, polyglycosides, polyvinylformamides, polyvinylamines, polyvinylimines and polyacrylonitriles or mixtures of two or more of the aforementioned polymers.
- polyvinyl alcohols, polyvinyl acetates, polyvinylpyrolidones have been found.
- copolymers of the abovementioned polymers such as polyvinyl alcohol-polyvinyl acetate copolymers or mixtures of copolymers have been found.
- the one or more polymers in the sense of the present invention are thermal, chemical, radiochemical, physical, biological with plasma, ultrasound or by extraction with a solvent degradable polymeric material.
- the proportion of the polymer in the solution prepared in process step (e) can vary over further ranges. In general, the proportion of the polymer is in the range of 1 to 20 wt .-%, preferably in the range of 5 to 15 Wt .-% and particularly preferably in the range of 6 to 10 wt .-%, based on the solution prepared in step (e) solution.
- the proportion of the sol-gel precursor, based on the solution prepared in process step (e), is generally in the range of 1 to 20 wt .-%, preferably in the range of 5 to 10 wt .-% and particularly preferably in the range of 6 to 10 wt .-%.
- the remaining constituent of the solution prepared in process step (e) forms the solvent or form the solvent and further optional additives.
- crystalline and / or amorphous metal oxide nanoparticles which usually have an average particle size in the range from 1 to 100 nm, are added to the solution prepared in process step (e).
- the proportion of the added particles is in the range of 1 to 99 wt .-%, preferably in the range of 1 to 40 wt .-%, particularly preferably in the range of 1 to 20 wt .-%, based on the process step (e) prepared solution or suspension.
- the crystalline metal oxide nanoparticles are ATO particles (antimony-doped tin oxide particles) and / or ITO particles (tin-doped indium oxide particles).
- crystalline and / or amorphous metal nanoparticles which usually have an average particle size in the range from 1 to 100 nm, are added to the solution prepared in process step (e).
- the proportion of added particles is in the range from 1 to 99% by weight, based on the solution prepared in process step (e).
- the nanoparticles are particles of silver, gold, copper or aluminum.
- the preparation of the nanofibers - consisting of one or more polymer (s), one or more metal oxide precursors from the solution prepared in process step (e) takes place by means of electrospinning from this solution.
- Electrospinning processes are known to the person skilled in the art. Electrospinning can be carried out, for example, with an electrospinning device whose structure is similar to or similar to the electrospinning devices described in the literature (Xia et al., Advanced Materials 2004, 16, 151). The electrospinning can also be carried out with an electrospinning device, which is described for example in WO 2006/131081 A1 or in WO 2007/137530 A2.
- the removal of the polymer or polymers in process step (g) of the process according to the invention is generally carried out thermally, chemically, radically, physically, biologically with plasma, ultrasound or by extraction with a solvent.
- the removal of the polymer preferably takes place thermally by means of calcining.
- the calcining is generally carried out over a period of 1 to 24 hours, preferably over a period of 3 to 6 hours at a temperature in the range of 250 to 900 ° C, preferably at a temperature in the range of 300 to 800 ° C, more preferably at a temperature in the range of 400 to 700 ° C.
- the atmosphere may be generally air atmosphere, but also a nitrogen atmosphere, which may additionally contain oxygen or hydrogen.
- the metal oxide fibers obtained after calcination have a diameter in the range of 0.1 nm to 999 nm, preferably in the range of 10 nm to 300 nm, preferably in the range of 50 nm to 200 nm.
- the aspect ratio is in the range of 10 to 1000, preferably in the range of 100 to 500.
- the nanofibers are dried after electrospinning and before calcination. The drying of the nanofibers is usually carried out at a temperature in the range of 80 to 180 ° C, preferably at a temperature in the range of 100 to 150 ° C in ambient atmosphere, in air or in vacuo.
- a process for the production of metal fibers in which the metal oxide fibers produced in process step (g) are reduced to the corresponding metal fibers.
- Suitable reducing agents are hydrogen, carbon monoxide, gaseous hydrocarbons, carbon, furthermore metals which are less noble, ie have a negative standard potential than the metal to be reduced, furthermore sodium borohydride, lithium aluminum hydride, alcohols and aldehydes.
- the metal oxide fibers can be electrochemically reduced or reduced. The person skilled in the art can use these reduction methods with the aid of his general knowledge and thereby obtains the corresponding metal fibers with a diameter of ⁇ 1 ⁇ m.
- the nanofibers can also be used for the electrochemical deposition of metal oxides and metals.
- a further subject of the invention is the use of the metal oxide fibers according to the invention as additives for plastics, for mechanical reinforcement, for antistatic / electrically conductive equipment, for flame retardancy, for improving the thermal conductivity of plastics; and as part of filters and filter parts for gas and liquid filtration, especially for high temperature filtration, as a component of a catalyst; as a component of Li-ion batteries, solar cells, fuel cells and other electronic components / elements.
- Example 1 Synthesis of ATO (antimony tin oxide) nanofibers
- the sol-gel precursor solution containing 6.7 wt.% PVP (Kollidon 92F from BASF SE), 6.7 wt.% ATO precursor, 26.4 wt % Water, 48.9 wt% ethanol and 1.1-3 wt% diethylamine was prepared as follows:
- Electrospinning of this solution was performed using the Nanospider apparatus (NS Lab 500S, Elmarco, Czech Republic). Electrode type: 6 wire electrode; Electrode spacing 25 cm; Voltage: 82 kV.
- the resulting fibers (also called green fibers) were calcined under an air atmosphere. To this was heated at a heating rate of 5 ° C per minute to 550 ° C and held this temperature of 550 ° C for two hours to obtain the ATO nanofibers in the form of light blue solid.
- the mean diameter of the fibers ranged from 100 to 130 nm
- the sol-gel precursor solution containing 6.7 wt .-% PVP (Kollidon 92F from BASF SE), 6.7 wt .-% ATO precursor, 26.4 wt .-% water, 48.9 wt Ethanol and 1, 3 wt .-% diethylamine was prepared as follows: With vigorous stirring, a solution of 66 g of stannic chloride and 5.8 g of antimony (III) chloride and 2.24 g ⁇ -caprolactam prepared in 560 g of water. The solution was warmed to 50 ° C and at this temperature 142 g of a 25 wt% aqueous ammonium hydroxide solution was added.
- the resulting suspension was stirred at 50 ° C for 10 hours.
- the formed precipitate was separated by a centrifuge and washed 4 times with pH 10 water (adjusted with ammonia solution), each being redispersed with an Ultraturrax.
- the resulting precipitate was dissolved in a mixture of water and diethylamine 7: 3 to obtain a 15 wt% (in terms of metal oxide content) ATO precursor solution.
- 200 g of the ATO precursor solution described above were dissolved in 200 g of 15% strength PVP solution in ethanol and then added to 50 ml of ethanol.
- the resulting solution had the following characteristics:
- Electrospinning was performed using the Nanospider apparatus (NS Lab 500S, Elmarco, Czech Republic). Electrode type: 6-wire electrode; Electrode spacing 25 cm; Voltage: 82 kV.
- the obtained fibers (also called green fibers) were calcined under air atmosphere. To this was heated at a heating rate of 5 ° C per minute to 550 ° C and held this temperature of 550 ° C for two hours to obtain the ATO nanofibers in the form of light blue solid.
- the sol-gel precursor solution containing 6.7 wt .-% PVP (Kollidon 92F from BASF SE), 6.7 wt .-% ATO precursor, 26.4 wt .-% water, 48.9 wt % Ethanol and 11.3% diethylamine was prepared as follows:
- the obtained precipitate was dissolved in a mixture of water and diethylamine 7: 3 to obtain a 15 wt% (in terms of metal oxide content) ATO precursor solution.
- 200 g of the ATO precursor solution described above were dissolved in 200 g of 15% strength PVP solution in ethanol and then added to 50 ml of ethanol.
- Electrospinning was performed using a Nanospider apparatus (NS Lab 500S, Elmarco, Czech Republic). Electrode type: 6-wire electrode; Electrode spacing 25 cm; Voltage: 82 kV.
- the obtained fibers (also called green fibers) were calcined under air atmosphere. To this was heated at a heating rate of 5 ° C per minute to 550 ° C and held this temperature of 550 ° C for two hours to obtain the ATO nanofibers in the form of light blue solid.
- Example 4 Synthesis of ATO (antimony tin oxide) nanofibers
- the sol-gel precursor solution containing 6.7 wt .-% PVP (Kollidon 92F from BASF SE), 6.7 wt .-% ATO precursor, 26.4 wt .-% water, 48.9 wt Ethanol and 1, 3 wt .-% diethylamine was prepared as follows: With vigorous stirring, a solution of 66 g of stannic chloride and 5.8 g of antimony (III) chloride and 2.24 g ⁇ -caprolactam prepared in 560 g of water.
- the solution was warmed to 50 ° C and at this temperature 142 g of a 25 wt% aqueous ammonium hydroxide solution was added.
- the resulting suspension was stirred at 50 ° C for 10 hours.
- the resulting suspension was then placed in an autoclave and heated to 150 ° C for 3.5 hours.
- the precipitate was separated by means of a centrifuge and washed 4 times with water, each redispersed with an Ultraturrax.
- the obtained precipitate was dissolved in a mixture of water and diethylamine 7: 3 to obtain a 15 wt% (in terms of metal oxide content) ATO precursor solution.
- 200 g of the ATO precursor solution described above were dissolved in 200 g of 15% strength PVP solution in ethanol and then added to 50 ml of ethanol.
- Electrospinning was performed using the Nanospider apparatus (NS Lab 500S, Elmarco, Czech Republic). Electrode type: 6-wire electrode; Electrode spacing 25 cm; Voltage: 82 kV.
- the obtained fibers (also called green fibers) were calcined under air atmosphere. This was heated at a heating rate of 5 ° C per minute to 550 ° C and held this temperature of 550 ° C for two hours.
- Example 5 Synthesis of ATO (antimony tin oxide) nanofibers
- PVP Sigma-Aldirch, MW 1, 300,000
- ATO precursor a sol-gel precursor solution containing 4.8% by weight of PVP (Sigma-Aldirch, MW 1, 300,000), 11.5% by weight of ATO precursor, 25.7 %
- water 10% by weight of ethanol, 35.2% by weight of methanol and 12.8% by weight of diethylamine were prepared as follows:
- ATO precursor solution 200 g of a 25% by weight aqueous ammonium hydroxide solution was placed in a glass flask. With vigorous stirring, a solution of 78.4 g of stannic chloride and 5.2 g of antimony (III) chloride in 960 g of ethanol and 16 g of concentrated HCl was added. The formed precipitate was separated by a centrifuge and washed 4 times with pH 10 water (adjusted with ammonia solution), each being redispersed with an Ultraturrax. The resulting precipitate was in a mixture of water and diethylamine 2: 1 dissolved to obtain a 23 wt .-% (based on the metal oxide content) ATO precursor solution. 200 g of the above-described ATO precursor solution were dissolved in methanol with 160 g of 12% strength by weight PVP solution and then 40 g of ethanol were added.
- Electrospinning of this solution was spun into nanofibers with a needle spinning apparatus, i.e., a syringe pump in combination with a high voltage device.
- the feed of the syringe pump was set to 0.5 ml / h, the electrode gap was 8 cm at a voltage of 7 kV.
- the obtained fibers (also called green fibers) were calcined under air atmosphere. To this was heated at a heating rate of 5 ° C per minute to 550 ° C and held this temperature of 550 ° C for two hours to obtain the ATO nanofibers in the form of light blue solid.
Abstract
Description
Claims
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KR101723700B1 (en) | 2009-06-30 | 2017-04-18 | 바스프 에스이 | Polyamide fibers comprising stainable particles and method for the production thereof |
US8623945B2 (en) | 2011-03-18 | 2014-01-07 | Basf Se | Use of oligomeric carbodiimides as stabilizers |
JP6266519B2 (en) | 2011-08-30 | 2018-01-24 | コーネル・ユニバーシティーCornell University | Metal and ceramic nanofibers |
JP5946180B2 (en) * | 2012-09-12 | 2016-07-05 | 花王株式会社 | Method for producing nanofiber |
JP6058969B2 (en) * | 2012-10-16 | 2017-01-11 | 日本バイリーン株式会社 | Method for producing metal oxide fiber |
CZ308566B6 (en) * | 2014-06-27 | 2020-12-09 | Ústav fyzikální chemie J. Heyrovského AV ČR, v. v. i. | Preparing inorganic nanofibres, in particular for use as heterogeneous catalysts, and inorganic nanofibres |
US20170362740A1 (en) * | 2016-06-16 | 2017-12-21 | Eurekite Holding BV | Flexible ceramic fibers and polymer composite and method of making the same |
CN107974731A (en) * | 2016-10-21 | 2018-05-01 | 苏州今道创业投资有限公司 | A kind of preparation method of erbium nitrate doped zinc oxide nano fiber |
CN109306550A (en) * | 2017-07-27 | 2019-02-05 | Tcl集团股份有限公司 | A kind of inorganic, metal oxide and preparation method thereof |
CN107663717B (en) * | 2017-11-09 | 2020-07-03 | 苏州大学 | Polyvinylidene fluoride nanofiber membrane and preparation method thereof |
CN109096585B (en) * | 2018-08-25 | 2021-06-01 | 深圳市金升彩包装材料有限公司 | Preparation method of hollow nanofiber reinforced composite packaging material |
US11566328B2 (en) * | 2019-06-17 | 2023-01-31 | Oregon State University | Amorphous thin films and method of making |
KR102345591B1 (en) * | 2020-11-17 | 2022-01-03 | 주식회사 위드엠텍 | Electrospinning Solution for Fabricating Titania Nanofibers and Method for preparing Titania Nanofibers Using the Same |
CN115896981A (en) * | 2022-12-01 | 2023-04-04 | 中自环保科技股份有限公司 | ATO (antimony tin oxide) nano-fiber and preparation method thereof |
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JP2004107181A (en) * | 2002-09-20 | 2004-04-08 | Canon Inc | Composition for forming piezoelectric element, method of manufacturing piezoelectric film, piezoelectric element and inkjet recording head |
JP4314362B2 (en) * | 2003-02-28 | 2009-08-12 | 独立行政法人理化学研究所 | Metal oxide nanofiber, method for producing the same, and nanocomposite material using the nanofiber |
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WO2005118925A2 (en) * | 2004-06-01 | 2005-12-15 | Massachusetts Institute Of Technology | Field-responsive superparamagnetic composite nanofibers and methods of use thereof |
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CZ299537B6 (en) | 2005-06-07 | 2008-08-27 | Elmarco, S. R. O. | Method of and apparatus for producing nanofibers from polymeric solution using electrostatic spinning |
DE102005040422A1 (en) * | 2005-08-25 | 2007-03-01 | TransMIT Gesellschaft für Technologietransfer mbH | Production of metal nanofibres and mesofibers |
US7618580B2 (en) * | 2005-10-03 | 2009-11-17 | The United States Of America As Represented By The Secretary Of The Navy | Method for fabrication of a polymeric, conductive optical transparency |
CZ2006359A3 (en) | 2006-06-01 | 2007-12-12 | Elmarco, S. R. O. | Device for producing nanofibers by electrostatic spinning of polymeric solutions |
WO2008111960A2 (en) * | 2006-09-29 | 2008-09-18 | University Of Akron | Metal oxide fibers and nanofibers, method for making same, and uses thereof |
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- 2010-10-26 US US13/508,268 patent/US20120217681A1/en not_active Abandoned
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- 2010-10-26 WO PCT/EP2010/066173 patent/WO2011054701A1/en active Application Filing
- 2010-10-26 KR KR1020127014221A patent/KR20130004564A/en not_active Application Discontinuation
- 2010-10-26 EP EP10771101A patent/EP2496740A1/en not_active Withdrawn
- 2010-10-26 JP JP2012537343A patent/JP2013510244A/en not_active Withdrawn
- 2010-10-26 CN CN201080060429XA patent/CN102695824A/en active Pending
Non-Patent Citations (1)
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Also Published As
Publication number | Publication date |
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JP2013510244A (en) | 2013-03-21 |
AU2010314191A1 (en) | 2012-05-31 |
WO2011054701A1 (en) | 2011-05-12 |
CA2779661A1 (en) | 2011-05-12 |
US20120217681A1 (en) | 2012-08-30 |
CN102695824A (en) | 2012-09-26 |
KR20130004564A (en) | 2013-01-11 |
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