US20110049769A1 - Method for production of inorganic nanofibres through electrostatic spinning - Google Patents
Method for production of inorganic nanofibres through electrostatic spinning Download PDFInfo
- Publication number
- US20110049769A1 US20110049769A1 US12/991,000 US99100009A US2011049769A1 US 20110049769 A1 US20110049769 A1 US 20110049769A1 US 99100009 A US99100009 A US 99100009A US 2011049769 A1 US2011049769 A1 US 2011049769A1
- Authority
- US
- United States
- Prior art keywords
- solution
- spinning
- alkoxide
- vinylpyrrolidone
- nanofibres
- 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.)
- Abandoned
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
Definitions
- the invention relates to a method for production of inorganic nanofibres through electrostatic spinning of solution, which contains alkoxide of metal or of semi-metal or of non-metal dissolved in a solvent system on basis of alcohol.
- Inorganic materials feature a number of properties, thanks to which they are suitable for usage in many technical fields, e.g. in electrotechnics, medicine, industry, etc.
- TiO 2 , SiO 2 , Al 2 O 3 , ZrO 2 and B 2 O 3 belong to the important inorganic substances.
- Nanoparticles from inorganic material which may be produced through the above mentioned or other suitable method, could also be incorporated into a structure of nanofibres, which may be realised e.g. by adding the nanoparticles into polymer solution and consequent production of nanofibres from this solution. Presence of inorganic nanoparticles in polymer nanofibres renders specific properties to these nanofibres. Nevertheless the substantial portion of these nanoparticles is formed of polymer component.
- the pure inorganic nanofibres are produced by discontinual methods of electrostatic spinning at usage of nozzle or needle spinning electrode, into which the solution is supplied, which may be represented by a precursor of given inorganic elements, or the polymer solution containing alkoxide of respective metal or non-metal as a source of inorganic basis of fibres.
- the goal of the invention is to develop a continual production method of inorganic nanofibres through electrostatic spinning, which would remove disadvantages of the background art.
- the goal of the invention has been achieved through a method for production of inorganic nanofibres according to the invention, whose principle consists in that, the alkoxide solution of metal or of semi-metal or non-metal is in a solvent system on basis of alcohol stabilised by chelating agent, which prevents hydrolysis of alkoxide, and after homogenizing is mixed with solution of poly(vinylpyrrolidone) in alcohol, after then the resultant solution is brought into electrostatic field, in which continually on long-term basis the electrostatic spinning is running, the result of which is production of organic-inorganic nanofibres, which are outside the spinning device calcinated after then in the air atmosphere at the temperature from 500° C. to 1300° C.
- a concentrated acid which is according to the claim 3 preferably selected from the group of hydrochloric acid, nitric acid, phosphoric acid.
- the chelating agent is composed of ⁇ -diketone, while the most suitable ⁇ -diketone seems to be acetylacetone, at whose usage the stabilisation of solution is permanent.
- Alcohol in solution of poly(vinylpyrrolidone) is selected from the group of ethanol, 1-propanol, 2-propanol or their mixtures.
- the poly(vinylpyrrolidone) has an average molecular weight within 1000000-1500000 g/mol and its weight concentration in solution is within the range from 4 to 9%, while the most preferred seems to be the poly(vinylpyrrolidone) having average molecular weight of 1300000 g/mol.
- Alkoxide of metal is preferably selected from the group of titanium tetrabutoxide, titanium tetraisopropoxide, aluminium tri-sec-butoxide, aluminiumtriisopropoxide or zirconium tetraisopropoxide.
- Alkoxide of semi-metal is preferably tetraethoxysilane or borium triethoxide.
- the ratio of alkoxide and chelating agent in solution is within 1:0.8 to 1:2.2.
- the alkoxide solution in electrostatic field is to be found on surface of active zone of the spinning mean of a spinning electrode.
- the alkoxide solution is into electrostatic field for spinning transported by surface of the spinning electrode, which is preferably formed of rotating spinning electrode of an oblong shape, which extends by a section of its circumference into the solution being subjected to spinning.
- the drawing represents in the FIG. 1 produced TiO 2 nanofibres, and in the FIG. 2 their XRD spectrum, the FIG. 3 represents Al 2 O 3 nanofibres and the FIG. 4 their XRD spectrum, the FIG. 5 represents B 2 O 3 nanofibres and the FIG. 6 their XRD spectrum, the FIG. 7 represents ZrO 2 nanofibres and the FIG. 8 their XRD spectrum.
- Spinning solution for production of inorganic nanofibres contains as a source of inorganic basis an alkoxide of respective metal, semi-metal or non-metal, which is dissolved in a suitable solvent, e.g. in ethanol, 1 -propanol or 2-propanol.
- a suitable solvent e.g. in ethanol, 1 -propanol or 2-propanol.
- chelating agent is necessary to stabilise the solution of alkoxide, especially to prevent its hydrolysis.
- the most suitable chelating agent is 6-diketone, e.g. acetylaceton.
- Molecular ratio between alkoxide and chelating agent should be within the range from 1:0.8 to 1:2.2.
- poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol or viscosity number K-90, while its weight concentration towards a total weight of solution is from 4 to 9% by weight.
- the process of electrostatic spinning depends on concentration, or more precisely on viscosity, surface tension and other parameters of alkoxide solution.
- the exact composition of alkoxide solution depends on temperature and humidity of environment and parameters of electrostatic spinning, such as rotation and type of electrode, distance between electrodes and applied voltage.
- the resultant solution of tetraethoxysilane was used for production of SiO 2 nanofibres by means of electrostatic spinning.
- a device for electrostatic spinning of polymer solutions comprising a spinning electrode and against it arranged collecting electrode, while the spinning electrode comprised rotatably mounted spinning mean extending by a section of its circumference into a solution of tetraethoxysilane being present in a reservoir.
- the rotating spinning mean thanks to its rotation, carried out the solution of tetraethoxysilane into a electrostatic field induced between the spinning electrode and the collecting electrode, while a portion of surface of rotating spinning mean being positioned against the collecting electrode represents an active spinning zone of the spinning mean.
- the nanofibrous organic-inorganic layer was consequently calcinated in a furnace in air atmosphere at temperature from 600 to 800° C. at production of pure amorphous SiO 2 nanofibres.
- TiO 2 nanofibres for preparation of solution the mixture of 250 g of ethanol and 29.4 g of acetylacetone was used, in which 100 g of titanium tetrabutoxide was dissolved. After homogenisation the obtained solution was carefully mixed with solution of 35.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 758.8 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous organic-inorganic layer was calcinated in furnace in air atmosphere at the temperature of 500° C. The crystallic form (structure) of resultant TiO 2 of inorganic nanofibres was purely of anatase.
- the mixture of 150 g ethanol and 29.4 g of acetylacetone was used, in which 100 g of titanium tetrabutoxide was dissolved.
- the obtained solution was mixed with solution of 35.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 272.1 g of ethanol, and after then acidified with concentrated hydrochloric acid.
- the resultant solution was subject to spinning through electrostatic spinning.
- the nanofibrous layer was calcinated at the temperature of 500° C. Crystallic form of resultant TiO 2 nanofibres was purely of anatase.
- B 2 O 3 nanofibres For production of B 2 O 3 nanofibres the mixture of 500 g of ethanol and 68.6 g of acetylacetone was used, in which 100 g of borium triethoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 71.5 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 1644.3 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning.
- the nanofibrous layer was calcinated at the temperature of 500° C.
- the resultant inorganic fibres showed B 2 O 3 crystallic structure with amorphous addition, which is witnessed by the picture represented in the FIG. 5 and XRD spectrum represented in the FIG. 6 .
- Production of nanofibres from the above mentioned solutions of alkoxides is not limited only to the described electrostatic spinning device with rotating spinning electrode, but it is possible to use also other types of spinning electrodes, at which the solution of alkoxide in electrostatic field for spinning is to be found on surface of active spinning zone of a spinning mean of a spinning electrode.
- Spinning of alkoxide solution runs successfully also on wire spinning electrodes according to the CZ PV 2007-485, at which the active spinning zone of the wire has during the spinning process a stable position towards the collecting electrode and alkoxide solution is to the active spinning zone of the wire supplied either by applying or by movement of the wire in direction of its length.
- the solution of alkoxide in electrostatic field for spinning is to be found on surface of active zone of the wire of spinning mean.
- the described solutions of alkoxides can of course be used also for discontinuous production of nanofibres at usage of nozzle or needle as a spinning electrode.
- the mentioned method for production of nanofibres ensures a sufficient stability of the solution being subject to spinning for entire period of spinning, and it is a key aspect for continuous production of inorganic nanofibres.
- Application of layers of inorganic nanofibres is important in many technical fields and industry, e.g. for production of composite materials, catalysts and electrochemical active elements.
Abstract
The present disclosure relates to the production method of inorganic nanofibres through electrostatic spinning of solution, which comprises alkoxide of metal or of semi-metal or of non-metal dissolved in a solvent system on basis of alcohol. The solution is stabilised by chelating agent, which prevents hydrolysis of alkoxide, and after homogenisation it is mixed with solution of poly(vinylpyrrolidone) in alcohol, after then the resultant solution is brought into electrostatic field, in which the electrostatic spinning is running continually, the result of which is production of organic-inorganic nanofibres, which are after then calcinated outside the spinning device in the air atmosphere at the temperature from 500° C. to 1300° C.
Description
- The invention relates to a method for production of inorganic nanofibres through electrostatic spinning of solution, which contains alkoxide of metal or of semi-metal or of non-metal dissolved in a solvent system on basis of alcohol.
- Inorganic materials feature a number of properties, thanks to which they are suitable for usage in many technical fields, e.g. in electrotechnics, medicine, industry, etc. For example, TiO2, SiO2, Al2O3, ZrO2 and B2O3 belong to the important inorganic substances. At inorganic nanofibres there are combined properties of nanofibrous materials, like an organised one-dimensional structure with properties of nanomaterials, especially with high specific surface, and with physical-chemical properties of inorganic substances as hardness, thermal resistance and structure of electron stripes. Therefore the resultant nanofibres are suitable for production of composite materials, catalysts, electrochemical elements, etc.
- At present, there are known various methods for production of nanoparticles from inorganic materials. Production of inorganic nanoparticles, namely from SiO2 and Al2O3, is disclosed in WO2007/079841.
- Nanoparticles from inorganic material, which may be produced through the above mentioned or other suitable method, could also be incorporated into a structure of nanofibres, which may be realised e.g. by adding the nanoparticles into polymer solution and consequent production of nanofibres from this solution. Presence of inorganic nanoparticles in polymer nanofibres renders specific properties to these nanofibres. Nevertheless the substantial portion of these nanoparticles is formed of polymer component.
- At present the pure inorganic nanofibres are produced by discontinual methods of electrostatic spinning at usage of nozzle or needle spinning electrode, into which the solution is supplied, which may be represented by a precursor of given inorganic elements, or the polymer solution containing alkoxide of respective metal or non-metal as a source of inorganic basis of fibres.
- The known solutions used for production of anorganic nanofibres through electrostatic spinning from nozzles cannot be used for continual production of nanofibres, because alkoxides are time-unsteady and are easily subject to degradation of alkoxide through hydrolysis, this even through action of air humidity, which occurs still before their spinning. To date for electrostatic spinning there was not used any solution of alkoxide, that would be stable enough and could be used for continual production of inorganic nanofibres.
- The goal of the invention is to develop a continual production method of inorganic nanofibres through electrostatic spinning, which would remove disadvantages of the background art.
- The goal of the invention has been achieved through a method for production of inorganic nanofibres according to the invention, whose principle consists in that, the alkoxide solution of metal or of semi-metal or non-metal is in a solvent system on basis of alcohol stabilised by chelating agent, which prevents hydrolysis of alkoxide, and after homogenizing is mixed with solution of poly(vinylpyrrolidone) in alcohol, after then the resultant solution is brought into electrostatic field, in which continually on long-term basis the electrostatic spinning is running, the result of which is production of organic-inorganic nanofibres, which are outside the spinning device calcinated after then in the air atmosphere at the temperature from 500° C. to 1300° C.
- By stabilisation of solution the hydrolysis of alkoxides by action of air humidity and other impacts of working environment is prevented, so that the process of electrostatic spinning runs continually and in the long-term. In the published works, in case of nozzle electro-spinning, they use the solutions of alkoxide of metal in alcohol in combination with poly(vinylpyrrolidone). Alkoxide is stabilised by additive of acetic acid (see Journal of America Ceramic Society 89[6]1861-1869(2006), Science and Technology of Advanced Materials 6(2005)240-245). Usage of this solution in case of electrostatic spinning from opened surface is possible in laboratory scale, nevertheless at the process lasting longer than half an hour the degradation of solution and hydrolysis of alkoxide occurs. This effect prevents industrial utilization of in literature described compositions of solutions for production of ceramic nanofibres through the method of electrostatic spinning from opened surface.
- For the purpose to increase the electrical conductivity of solution and to increase efficiency of production process, it is possible to add into the solution a concentrated acid, which is according to the claim 3 preferably selected from the group of hydrochloric acid, nitric acid, phosphoric acid.
- In preferred embodiment of the method the chelating agent is composed of β-diketone, while the most suitable β-diketone seems to be acetylacetone, at whose usage the stabilisation of solution is permanent.
- Alcohol in solution of poly(vinylpyrrolidone) is selected from the group of ethanol, 1-propanol, 2-propanol or their mixtures.
- In advantageous embodiment the poly(vinylpyrrolidone) has an average molecular weight within 1000000-1500000 g/mol and its weight concentration in solution is within the range from 4 to 9%, while the most preferred seems to be the poly(vinylpyrrolidone) having average molecular weight of 1300000 g/mol.
- Alkoxide of metal is preferably selected from the group of titanium tetrabutoxide, titanium tetraisopropoxide, aluminium tri-sec-butoxide, aluminiumtriisopropoxide or zirconium tetraisopropoxide.
- Alkoxide of semi-metal is preferably tetraethoxysilane or borium triethoxide.
- To achieve a good stabilisation of alkoxide solution it is preferred if the ratio of alkoxide and chelating agent in solution is within 1:0.8 to 1:2.2.
- For the electrostatic spinning itself, the alkoxide solution in electrostatic field is to be found on surface of active zone of the spinning mean of a spinning electrode.
- At the same time it is preferred, if the alkoxide solution is into electrostatic field for spinning transported by surface of the spinning electrode, which is preferably formed of rotating spinning electrode of an oblong shape, which extends by a section of its circumference into the solution being subjected to spinning.
- The drawing represents in the
FIG. 1 produced TiO2 nanofibres, and in theFIG. 2 their XRD spectrum, theFIG. 3 represents Al2O3 nanofibres and theFIG. 4 their XRD spectrum, theFIG. 5 represents B2O3 nanofibres and theFIG. 6 their XRD spectrum, theFIG. 7 represents ZrO2 nanofibres and theFIG. 8 their XRD spectrum. - Spinning solution for production of inorganic nanofibres, especially of TiO2, SiO2, Al2O3, ZrO2 and B2O3, by means of electrostatic spinning contains as a source of inorganic basis an alkoxide of respective metal, semi-metal or non-metal, which is dissolved in a suitable solvent, e.g. in ethanol, 1-propanol or 2-propanol. To stabilise the solution of alkoxide, especially to prevent its hydrolysis, an addition of chelating agent as stabiliser is necessary. The most suitable chelating agent is 6-diketone, e.g. acetylaceton. Molecular ratio between alkoxide and chelating agent should be within the range from 1:0.8 to 1:2.2. To improve the spinning ability of the solution also supporting polymer is added into it, which may be represented by e.g. poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol or viscosity number K-90, while its weight concentration towards a total weight of solution is from 4 to 9% by weight.
- The process of electrostatic spinning depends on concentration, or more precisely on viscosity, surface tension and other parameters of alkoxide solution. The exact composition of alkoxide solution depends on temperature and humidity of environment and parameters of electrostatic spinning, such as rotation and type of electrode, distance between electrodes and applied voltage.
- In particular example of embodiment for production of SiO2 nanofibres for production of solution a mixture of 250 g of ethanol and 39 g of acetylacetone was used, in which there was carefully dissolved 100 g of tetraethoxysilane. After homogenisation the obtained solution was carefully mixed with solution of 35.2 g poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 747.9 g of ethanol. After following homogenisation the resultant solution was acidified with concentrated hydrochloric acid.
- The resultant solution of tetraethoxysilane was used for production of SiO2 nanofibres by means of electrostatic spinning. There was used a device for electrostatic spinning of polymer solutions comprising a spinning electrode and against it arranged collecting electrode, while the spinning electrode comprised rotatably mounted spinning mean extending by a section of its circumference into a solution of tetraethoxysilane being present in a reservoir. The rotating spinning mean, thanks to its rotation, carried out the solution of tetraethoxysilane into a electrostatic field induced between the spinning electrode and the collecting electrode, while a portion of surface of rotating spinning mean being positioned against the collecting electrode represents an active spinning zone of the spinning mean. During spinning the solution of tetraethoxysilane was present in electrostatic field on surface of active spinning zone of the spinning mean of the spinning electrode. Rotating spinning mean may be construed e.g. according to the CZ patent 294274 or according to the CZ PV 2006-545 or CZ PV 2007-485. At concrete spinning of solution of tetraethoxysilane described above a portion of solution, about 125 ml, was poured into storing vessel and this was equipped with a spinning rotating cylindrical electrode. The vessel with the electrode was positioned into a device for production of nanofibres through electrostatic spinning. As a substrate material any fabric, foil, etc., may be used. The obtained organic-inorganic nanofibrous layer comprised the nanofibres having thickness of 30-1000 nm.
- The nanofibrous organic-inorganic layer was consequently calcinated in a furnace in air atmosphere at temperature from 600 to 800° C. at production of pure amorphous SiO2 nanofibres.
- Similarly, the following solutions of alkoxides were subject to electrostatic spinning.
- For production of TiO2 nanofibres for preparation of solution the mixture of 250 g of ethanol and 29.4 g of acetylacetone was used, in which 100 g of titanium tetrabutoxide was dissolved. After homogenisation the obtained solution was carefully mixed with solution of 35.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 758.8 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous organic-inorganic layer was calcinated in furnace in air atmosphere at the temperature of 500° C. The crystallic form (structure) of resultant TiO2 of inorganic nanofibres was purely of anatase.
- In further example of embodiment for production of Li4Ti5O12 nanofibres for preparation of solution the mixture of 250 g of ethanol and 29.4 g of acetylacetone was used, in which 100 g of titanium tetrabutoxide was dissolved. After homogenisation the obtained solution was carefully mixed with solution of 35.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol and 24 g of dihydrate of lithium acetate in 758.8 g of ethanol. The resultant solution was subject to electrostatic spinning. The nanofibrous organic-inorganic layer was calcinated in furnace in air atmosphere at the temperature of 750° C. The resultant inorganic fibres showed the phase of Li4Ti5O12 with addition of anatase and rutile less than 5%.
- In another example of embodiment for production of solution of TiO2 nanofibres the mixture of 250 g of 2-propanol and 29.4 g of acetylacetone was used, in which 100 g of titanium tetrabutoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 35.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 758.8 g of ethanol, and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 700° C. Crystallic form of resultant nanofibres was partially of anatase and partially of rutile, that is witnessed by the picture represented in the
FIG. 1 and XRD spectrum of nanofibres represented in theFIG. 2 . - In further exemplary embodiment for production of solution for production of TiO2 nanofibres the mixture of 250 g of 1-propanol and 29.4 g of acetylacetone acidified with 0.3 g of phosphoric acid was used. In the given mixture 100 g of titanium tetrabutoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 35.2 g poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 758.8 g of ethanol. The resultant Solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 500° C. Crystallic form of resultant inorganic TiO2 nanofibres was purely of anatase.
- At further example of embodiment for production of solution for production of TiO2 nanofibres the mixture of 250 g of ethanol and 58.8 g of acetylacetone was used, in which 100 g of titanium tetrabutoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 35.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 729.4 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 700° C. Crystallic form of resultant TiO2 nanofibres was partially of anatase and partially of rutile.
- For production of solution for production of TiO2 nanofibres according to further example of embodiment the mixture of 150 g ethanol and 29.4 g of acetylacetone was used, in which 100 g of titanium tetrabutoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 35.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 272.1 g of ethanol, and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 500° C. Crystallic form of resultant TiO2 nanofibres was purely of anatase.
- In another embodiment for production of solution for production of TiO2 nanofibres the mixture of 250 g ethanol and 35.2 g of acetylacetone was used, in which 100 g of titanium tetraisopropoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 42.2 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 977.7 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 500° C. Crystallic form of resultant TiO2 nanofibres was purely of anatase.
- For production of Al2O3 nanofibres the mixture of 500 g of 2-propanol and of 40.7 g of acetylacetone was used, in which 100 g of aluminium tri-sec-butoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 62.1 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 1366.9 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 700° C. The resultant inorganic fibres showed a pure □-Al2O3 crystallic structure, which is witnessed by the picture represented in the
FIG. 3 and XRD spectrum represented in theFIG. 4 . - In another embodiment for production of solution for production of Al2O3 nanofibres the mixture of 350 g of 2-propanol and 40.7 g of acetylacetone was used, in which 100 g of aluminium tri-sec-butoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 62.1 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 827 g of ethanol and after then acidified with concentrated hydrochloric acid. The nanofibrous layer was calcinated at the temperature of 800° C. The resultant inorganic fibres showed a pure □-Al2O3 crystallic structure.
- In another embodiment for production of solution for production of Al2O3 nanofibres the mixture of 500 g of 2-propanol and 49 g of acetylacetone was used, in which 100 g of aluminium triisopropoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 74.9 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 1772.2 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 700° C. The resultant inorganic fibres showed a pure □-Al2O3 crystallic structure.
- For production of B2O3 nanofibres the mixture of 500 g of ethanol and 68.6 g of acetylacetone was used, in which 100 g of borium triethoxide was dissolved. After homogenisation the obtained solution was mixed with solution of 71.5 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 1644.3 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning.
- The nanofibrous layer was calcinated at the temperature of 500° C. The resultant inorganic fibres showed B2O3 crystallic structure with amorphous addition, which is witnessed by the picture represented in the
FIG. 5 and XRD spectrum represented in theFIG. 6 . - For production of ZrO2 nanofibres the mixture of 500 g of ethanol and 30.6 g of acetylacetone was used, into which the solution of 142.9 g of zirconium tetraisopropoxide in 1-propanol was added. After homogenisation the obtained solution was mixed with solution of 56.4 g of poly(vinylpyrrolidone) having molecular weight of 1300000 g/mol in 1193.8 g of ethanol and after then acidified with concentrated hydrochloric acid. The resultant solution was subject to spinning through electrostatic spinning. The nanofibrous layer was calcinated at the temperature of 700° C. The resultant inorganic fibres showed ZrO2 mixture of monoclinic and tetragonal crystallic structure, which is witnessed by the picture represented in the
FIG. 7 and XRD spectrum represented in theFIG. 8 . - In all cases the long-term continual spinning process was achieved and thickness of produced nanofibres was from 30 to 1000 nm.
- Production of nanofibres from the above mentioned solutions of alkoxides is not limited only to the described electrostatic spinning device with rotating spinning electrode, but it is possible to use also other types of spinning electrodes, at which the solution of alkoxide in electrostatic field for spinning is to be found on surface of active spinning zone of a spinning mean of a spinning electrode. Spinning of alkoxide solution runs successfully also on wire spinning electrodes according to the CZ PV 2007-485, at which the active spinning zone of the wire has during the spinning process a stable position towards the collecting electrode and alkoxide solution is to the active spinning zone of the wire supplied either by applying or by movement of the wire in direction of its length. In this case, the solution of alkoxide in electrostatic field for spinning is to be found on surface of active zone of the wire of spinning mean. The described solutions of alkoxides can of course be used also for discontinuous production of nanofibres at usage of nozzle or needle as a spinning electrode.
- The mentioned method for production of nanofibres ensures a sufficient stability of the solution being subject to spinning for entire period of spinning, and it is a key aspect for continuous production of inorganic nanofibres. Application of layers of inorganic nanofibres is important in many technical fields and industry, e.g. for production of composite materials, catalysts and electrochemical active elements.
Claims (15)
1. A method for production of inorganic nanofibres through electrostatic spinning of solution, which comprises alkoxide of metal or of semi-metal or of non-metal dissolved in a solvent system on basis of alcohol, wherein the solution is stabilised by acethylacetone, which prevents hydrolysis of alkoxide, and after homogenisation it is mixed with solution of poly(vinylpyrrolidone) in an alcohol, after then the resultant solution is brought into electrostatic field, in which the electrostatic spinning is running continually, the result of which is production of organic-inorganic nanofibres, which are after then calcinated outside the spinning device in air atmosphere at the temperature from 500 ° C. to 1300° C.
2. The method according to claim 1 , wherein, to increase the electrical conductivity of the solution, a concentrated acid is added into the solution.
3. The method according to claim 2 , the wherein the acid is selected from the group of hydrochloric acid, nitric acid, phosphoric acid.
4. (canceled)
5. The method according to claim 1 , wherein the alcohol in solution of poly(vinylpyrrolidone) is selected from the group of ethanol, 1-propanol, 2-propanol or their mixtures.
6. The method according to claim 1 , wherein the poly(vinylpyrrolidone) has an average molecular weight within the range of 1000000-1500000 g/mol and its weight concentration in the solution is within the range from 4 to 9%.
7. The method according to claim 6 , wherein the poly(vinylpyrrolidone) has average molecular weight of 1300000 g/mol.
8. The method according to claim 1 , wherein the poly(vinylpyrrolidone) has viscosity number K within the range from K-70 to K-95 and its concentration in solution is in the range from 4 to 9%.
9. The method according to claim 8 , wherein the poly(vinylpyrrolidone) has viscosity number K-90.
10. The method according to claim 1 , wherein the alkoxide of metal is selected from the group of titanium tetrabutoxide, titanium tetraisopropoxide, aluminium tri-sec-butoxide, aluminium triisopropoxide, zirconium tetraisopropoxide.
11. The method according to claim 1 , wherein the alkoxide of semi-metal is selected from the group of tetraethoxysilane, borium triethoxide.
12. The method according to claim 1 , wherein the molecular ratio of alkoxide and chelating agent in solution is from 1:0.8 to 1:2.2.
13. The method according to claim 1 , wherein the alkoxide solution in electrostatic field for spinning is to be found on surface of active spinning zone of the spinning mean of the spinning electrode.
14. The method according to claim 12 , wherein the solution of alkoxide is transported into electrostatic field for spinning by surface of the spinning electrode.
15. The method according to claim 12 , wherein the spinning electrode is formed of rotating spinning electrode of an oblong shape, which extends by a section of its circumference into the spinning solution.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CZ20080277A CZ2008277A3 (en) | 2008-05-06 | 2008-05-06 | Process for preparing inorganic nanofibers by electrostatic spinning |
CZPV2008-277 | 2008-05-06 | ||
PCT/CZ2009/000065 WO2009135448A2 (en) | 2008-05-06 | 2009-05-05 | A method for production of inorganic nanofibres through electrostatic spinning |
Publications (1)
Publication Number | Publication Date |
---|---|
US20110049769A1 true US20110049769A1 (en) | 2011-03-03 |
Family
ID=41258174
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/991,000 Abandoned US20110049769A1 (en) | 2008-05-06 | 2009-05-05 | Method for production of inorganic nanofibres through electrostatic spinning |
Country Status (12)
Country | Link |
---|---|
US (1) | US20110049769A1 (en) |
EP (1) | EP2276880A2 (en) |
JP (1) | JP2011520045A (en) |
KR (1) | KR20100135975A (en) |
CN (1) | CN102084044A (en) |
AU (1) | AU2009243816A1 (en) |
BR (1) | BRPI0912221A2 (en) |
CA (1) | CA2723471A1 (en) |
CZ (1) | CZ2008277A3 (en) |
IL (1) | IL209135A0 (en) |
RU (1) | RU2010147892A (en) |
WO (1) | WO2009135448A2 (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080311815A1 (en) * | 2003-06-19 | 2008-12-18 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
US20100269995A1 (en) * | 2009-04-24 | 2010-10-28 | Eastman Chemical Company | Sulfopolyesters for paper strength and process |
US20110089595A1 (en) * | 2003-06-19 | 2011-04-21 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8216953B2 (en) | 2003-06-19 | 2012-07-10 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8840757B2 (en) | 2012-01-31 | 2014-09-23 | Eastman Chemical Company | Processes to produce short cut microfibers |
US9273417B2 (en) | 2010-10-21 | 2016-03-01 | Eastman Chemical Company | Wet-Laid process to produce a bound nonwoven article |
US9303357B2 (en) | 2013-04-19 | 2016-04-05 | Eastman Chemical Company | Paper and nonwoven articles comprising synthetic microfiber binders |
CN106207149A (en) * | 2015-04-30 | 2016-12-07 | 中国电力科学研究院 | A kind of method preparing submicron order lithium titanate material |
US9598802B2 (en) | 2013-12-17 | 2017-03-21 | Eastman Chemical Company | Ultrafiltration process for producing a sulfopolyester concentrate |
US9605126B2 (en) | 2013-12-17 | 2017-03-28 | Eastman Chemical Company | Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion |
WO2017186201A1 (en) | 2016-04-26 | 2017-11-02 | Pardam, S.R.O. | Precursor fibers intended for preparation of silica fibers, method of manufacture thereof, method of modification thereof, use of silica fibers |
CN110004519A (en) * | 2019-04-16 | 2019-07-12 | 天津工业大学 | One kind can produce the electrostatic spinning liquid of the multiple dimensioned alumina fibre of " caterpillar " shape |
EP3604640A4 (en) * | 2017-03-30 | 2021-01-13 | JNC Corporation | Method for producing metal titanate fibers |
CN113151933A (en) * | 2021-05-21 | 2021-07-23 | 北京邮电大学 | Method for preparing alumina nano-fiber by utilizing electrostatic spinning |
US11141506B2 (en) * | 2018-04-03 | 2021-10-12 | Peking University School And Hospital Of Stomatology | Electrified composite membrane with extracellular matrix electrical topology characteristics, and preparation method thereof |
CN114149024A (en) * | 2021-11-30 | 2022-03-08 | 陕西科技大学 | Boron-doped porous titanium dioxide/carbon fiber negative electrode material and preparation method thereof |
CN114920552A (en) * | 2022-05-20 | 2022-08-19 | 湘潭大学 | Preparation process of two-dimensional nanosheet |
WO2022247346A1 (en) * | 2021-05-26 | 2022-12-01 | 山东大学 | Method for preparing oxide high-entropy ceramic fibers |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2204480B1 (en) * | 2008-12-25 | 2013-03-20 | Shinshu University | Process of manufacturing inorganic nanofibers |
CZ2009152A3 (en) | 2009-03-10 | 2010-11-10 | Elmarco S.R.O. | Layered filtration material and device for purification of gaseous medium |
AT509504A1 (en) * | 2010-02-19 | 2011-09-15 | Rubacek Lukas | METHOD FOR PRODUCING LITHIUM TITANATE |
KR101113311B1 (en) * | 2010-03-31 | 2012-03-13 | 광주과학기술원 | Method for fabricating hybrid catalyst with metal oxide nanowire, electrode and fuel cell containing hybrid catalyst fabricated by the same |
CN101922060B (en) * | 2010-09-01 | 2012-07-04 | 青岛大学 | Method for preparing rare earth fluorescence micro/nano fibers |
CZ2011540A3 (en) | 2011-08-30 | 2012-10-31 | Vysoká Škola Bánská -Technická Univerzita Ostrava | Process for preparing fibrous and lamellar microstructures and nanostructures by controlled vacuum freeze drying of nanoparticle liquid dispersion |
JP2015514876A (en) * | 2011-10-03 | 2015-05-21 | エヌディーエスユー リサーチ ファウンデーション | Liquid silane composition and processing method |
JP2015523473A (en) * | 2012-05-16 | 2015-08-13 | ノースカロライナ ステート ユニヴァーシティNorth Carolina State University | Apparatus and method for making nanofibers from solution sheared under continuous flow |
CN103752848B (en) * | 2014-02-10 | 2016-02-03 | 南昌欧菲光科技有限公司 | A kind of preparation method of nano-silver thread |
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 |
CZ306773B6 (en) * | 2016-04-26 | 2017-06-28 | Pardam, S.R.O. | Precursor fibre intended for the preparation of silicon fibres, the method of its manufacture, the method of its modification and its use |
KR102248182B1 (en) * | 2018-01-26 | 2021-05-04 | (주)엘지하우시스 | Fine dust filter for windows and method for manufacturing the same |
CN109095894A (en) * | 2018-06-22 | 2018-12-28 | 西安工程大学 | The preparation method of flexible metal oxide nanofiber phosphorylation peptide gathering material |
CN109082769A (en) * | 2018-06-22 | 2018-12-25 | 西安工程大学 | A kind of preparation method of flexibility TiOx nano fiber phosphorylation peptide gathering material |
CN111187424A (en) * | 2020-02-14 | 2020-05-22 | 山东大学 | Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, and preparation method and application thereof |
CN111995393B (en) * | 2020-09-10 | 2022-04-29 | 山东大学 | Method for preparing aluminum titanate ceramic fiber from titanium-aluminum polymer precursor |
CN112899889B (en) * | 2021-01-22 | 2022-06-21 | 清华大学深圳国际研究生院 | Preparation method of titanate fiber membrane |
CN114560709B (en) * | 2021-11-19 | 2023-05-02 | 东华大学 | Ceramic nanofiber aerogel with hinged structure and preparation method thereof |
WO2024070017A1 (en) * | 2022-09-27 | 2024-04-04 | Jnc株式会社 | Spinning solution for producing silica fibers |
WO2024070018A1 (en) * | 2022-09-27 | 2024-04-04 | Jnc株式会社 | Silica fibers, and manufacturing method for same |
JP2024051672A (en) * | 2022-09-30 | 2024-04-11 | Jnc株式会社 | Metal oxide porous fiber |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4584365A (en) * | 1985-02-15 | 1986-04-22 | Manville Sales Corporation | Production of polymer from metal alkoxide and reaction mixture of carboxylic acid and hydroxy compound |
US20090082501A1 (en) * | 2005-05-31 | 2009-03-26 | Shinichi Tamura | Polymer made from organosilane compound and boron compound |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR910000294B1 (en) * | 1988-07-20 | 1991-01-24 | 한국과학기술원 | Process for synthesis of alumina-gol |
JPH04263615A (en) * | 1991-02-18 | 1992-09-18 | Colloid Res:Kk | Production of viscous aluminosilicate sol |
JP3963439B2 (en) * | 2001-06-08 | 2007-08-22 | 日本バイリーン株式会社 | Inorganic structure manufacturing method and inorganic structure |
US7575707B2 (en) * | 2005-03-29 | 2009-08-18 | University Of Washington | Electrospinning of fine hollow fibers |
WO2006129844A1 (en) * | 2005-05-31 | 2006-12-07 | Teijin Limited | Ceramic fiber and process for producing the same |
US9267220B2 (en) * | 2006-03-31 | 2016-02-23 | Cornell University | Nanofibers, nanotubes and nanofiber mats comprising crystaline metal oxides and methods of making the same |
-
2008
- 2008-05-06 CZ CZ20080277A patent/CZ2008277A3/en unknown
-
2009
- 2009-05-05 RU RU2010147892/05A patent/RU2010147892A/en not_active Application Discontinuation
- 2009-05-05 KR KR1020107027149A patent/KR20100135975A/en not_active Application Discontinuation
- 2009-05-05 US US12/991,000 patent/US20110049769A1/en not_active Abandoned
- 2009-05-05 WO PCT/CZ2009/000065 patent/WO2009135448A2/en active Application Filing
- 2009-05-05 BR BRPI0912221A patent/BRPI0912221A2/en not_active IP Right Cessation
- 2009-05-05 CA CA2723471A patent/CA2723471A1/en not_active Abandoned
- 2009-05-05 AU AU2009243816A patent/AU2009243816A1/en not_active Abandoned
- 2009-05-05 CN CN2009801262333A patent/CN102084044A/en active Pending
- 2009-05-05 JP JP2011507784A patent/JP2011520045A/en active Pending
- 2009-05-05 EP EP09741722A patent/EP2276880A2/en not_active Withdrawn
-
2010
- 2010-11-04 IL IL209135A patent/IL209135A0/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4584365A (en) * | 1985-02-15 | 1986-04-22 | Manville Sales Corporation | Production of polymer from metal alkoxide and reaction mixture of carboxylic acid and hydroxy compound |
US20090082501A1 (en) * | 2005-05-31 | 2009-03-26 | Shinichi Tamura | Polymer made from organosilane compound and boron compound |
Non-Patent Citations (4)
Title |
---|
Li, Dan et al, "Electrospinning: A simple and Versatile Technique for Producing Ceramic Nanofibers and Nanotubes" J. of the Amer Ceram Soc., Vol 89, No 6, April 2006, pages 1861-1869 * |
Li, Dan et al. "Electrospinning of polymeric and Ceramic Nanofibers as Uniaxially Aligned Arrays" Nanoletters, Vol 3, No 8, August 2003, pages 1167-1171 * |
Li, Dan et al. "Fabrication of Titania Nanofibers by Electrospinning" Nanoletters, Vol 3, No 4, March 2003, pages 555-560 * |
Madhugiri et al., "Electrospun mesoporous titanium dioxide fibers", Microporous and Mesoporous Materials, Volume 69, Issues 1-2, 8 April 2004, Pages 77-83 * |
Cited By (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8444896B2 (en) | 2003-06-19 | 2013-05-21 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US20110089601A1 (en) * | 2003-06-19 | 2011-04-21 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US20080311815A1 (en) * | 2003-06-19 | 2008-12-18 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
US20110089600A1 (en) * | 2003-06-19 | 2011-04-21 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8691130B2 (en) | 2003-06-19 | 2014-04-08 | Eastman Chemical Company | Process of making water-dispersible multicomponent fibers from sulfopolyesters |
US20110105975A1 (en) * | 2003-06-19 | 2011-05-05 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US20110168625A1 (en) * | 2003-06-19 | 2011-07-14 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
US8148278B2 (en) | 2003-06-19 | 2012-04-03 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8158244B2 (en) | 2003-06-19 | 2012-04-17 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8163385B2 (en) | 2003-06-19 | 2012-04-24 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8178199B2 (en) | 2003-06-19 | 2012-05-15 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
US8216953B2 (en) | 2003-06-19 | 2012-07-10 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8227362B2 (en) | 2003-06-19 | 2012-07-24 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8236713B2 (en) | 2003-06-19 | 2012-08-07 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8247335B2 (en) | 2003-06-19 | 2012-08-21 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8513147B2 (en) | 2003-06-19 | 2013-08-20 | Eastman Chemical Company | Nonwovens produced from multicomponent fibers |
US8262958B2 (en) | 2003-06-19 | 2012-09-11 | Eastman Chemical Company | Process of making woven articles comprising water-dispersible multicomponent fibers |
US8273451B2 (en) | 2003-06-19 | 2012-09-25 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8277706B2 (en) | 2003-06-19 | 2012-10-02 | Eastman Chemical Company | Process of making water-dispersible multicomponent fibers from sulfopolyesters |
US8314041B2 (en) | 2003-06-19 | 2012-11-20 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8388877B2 (en) | 2003-06-19 | 2013-03-05 | Eastman Chemical Company | Process of making water-dispersible multicomponent fibers from sulfopolyesters |
US8398907B2 (en) | 2003-06-19 | 2013-03-19 | Eastman Chemical Company | Process of making water-dispersible multicomponent fibers from sulfopolyesters |
US8435908B2 (en) | 2003-06-19 | 2013-05-07 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8444895B2 (en) | 2003-06-19 | 2013-05-21 | Eastman Chemical Company | Processes for making water-dispersible and multicomponent fibers from sulfopolyesters |
US20110089595A1 (en) * | 2003-06-19 | 2011-04-21 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US8623247B2 (en) | 2003-06-19 | 2014-01-07 | Eastman Chemical Company | Process of making water-dispersible multicomponent fibers from sulfopolyesters |
US8257628B2 (en) | 2003-06-19 | 2012-09-04 | Eastman Chemical Company | Process of making water-dispersible multicomponent fibers from sulfopolyesters |
US8557374B2 (en) | 2003-06-19 | 2013-10-15 | Eastman Chemical Company | Water-dispersible and multicomponent fibers from sulfopolyesters |
US20100269995A1 (en) * | 2009-04-24 | 2010-10-28 | Eastman Chemical Company | Sulfopolyesters for paper strength and process |
US8512519B2 (en) | 2009-04-24 | 2013-08-20 | Eastman Chemical Company | Sulfopolyesters for paper strength and process |
US9273417B2 (en) | 2010-10-21 | 2016-03-01 | Eastman Chemical Company | Wet-Laid process to produce a bound nonwoven article |
US8840757B2 (en) | 2012-01-31 | 2014-09-23 | Eastman Chemical Company | Processes to produce short cut microfibers |
US8840758B2 (en) | 2012-01-31 | 2014-09-23 | Eastman Chemical Company | Processes to produce short cut microfibers |
US8871052B2 (en) | 2012-01-31 | 2014-10-28 | Eastman Chemical Company | Processes to produce short cut microfibers |
US8882963B2 (en) | 2012-01-31 | 2014-11-11 | Eastman Chemical Company | Processes to produce short cut microfibers |
US8906200B2 (en) | 2012-01-31 | 2014-12-09 | Eastman Chemical Company | Processes to produce short cut microfibers |
US9175440B2 (en) | 2012-01-31 | 2015-11-03 | Eastman Chemical Company | Processes to produce short-cut microfibers |
US9303357B2 (en) | 2013-04-19 | 2016-04-05 | Eastman Chemical Company | Paper and nonwoven articles comprising synthetic microfiber binders |
US9617685B2 (en) | 2013-04-19 | 2017-04-11 | Eastman Chemical Company | Process for making paper and nonwoven articles comprising synthetic microfiber binders |
US9598802B2 (en) | 2013-12-17 | 2017-03-21 | Eastman Chemical Company | Ultrafiltration process for producing a sulfopolyester concentrate |
US9605126B2 (en) | 2013-12-17 | 2017-03-28 | Eastman Chemical Company | Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion |
CN106207149A (en) * | 2015-04-30 | 2016-12-07 | 中国电力科学研究院 | A kind of method preparing submicron order lithium titanate material |
WO2017186201A1 (en) | 2016-04-26 | 2017-11-02 | Pardam, S.R.O. | Precursor fibers intended for preparation of silica fibers, method of manufacture thereof, method of modification thereof, use of silica fibers |
EP3604640A4 (en) * | 2017-03-30 | 2021-01-13 | JNC Corporation | Method for producing metal titanate fibers |
US11141506B2 (en) * | 2018-04-03 | 2021-10-12 | Peking University School And Hospital Of Stomatology | Electrified composite membrane with extracellular matrix electrical topology characteristics, and preparation method thereof |
CN110004519A (en) * | 2019-04-16 | 2019-07-12 | 天津工业大学 | One kind can produce the electrostatic spinning liquid of the multiple dimensioned alumina fibre of " caterpillar " shape |
CN113151933A (en) * | 2021-05-21 | 2021-07-23 | 北京邮电大学 | Method for preparing alumina nano-fiber by utilizing electrostatic spinning |
WO2022247346A1 (en) * | 2021-05-26 | 2022-12-01 | 山东大学 | Method for preparing oxide high-entropy ceramic fibers |
CN114149024A (en) * | 2021-11-30 | 2022-03-08 | 陕西科技大学 | Boron-doped porous titanium dioxide/carbon fiber negative electrode material and preparation method thereof |
CN114920552A (en) * | 2022-05-20 | 2022-08-19 | 湘潭大学 | Preparation process of two-dimensional nanosheet |
Also Published As
Publication number | Publication date |
---|---|
AU2009243816A1 (en) | 2009-11-12 |
EP2276880A2 (en) | 2011-01-26 |
WO2009135448A3 (en) | 2010-01-21 |
RU2010147892A (en) | 2012-06-20 |
IL209135A0 (en) | 2011-01-31 |
CA2723471A1 (en) | 2009-11-12 |
KR20100135975A (en) | 2010-12-27 |
BRPI0912221A2 (en) | 2015-10-06 |
CZ2008277A3 (en) | 2009-11-18 |
CN102084044A (en) | 2011-06-01 |
WO2009135448A2 (en) | 2009-11-12 |
JP2011520045A (en) | 2011-07-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20110049769A1 (en) | Method for production of inorganic nanofibres through electrostatic spinning | |
Shao et al. | A novel method for making ZrO2 nanofibres via an electrospinning technique | |
Ding et al. | Morphology and crystalline phase study of electrospun TiO2–SiO2 nanofibres | |
Lee et al. | Preparation of SiO2/TiO2 composite fibers by sol–gel reaction and electrospinning | |
Lotus et al. | Characterization of TiO2–Al2O3 composite fibers formed by electrospinning a sol–gel and polymer mixture | |
KR101596786B1 (en) | Method for manufacturing inorganic nano-fiber | |
Mirmohammad Sadeghi et al. | Morphology enhancement of TiO2/PVP composite nanofibers based on solution viscosity and processing parameters of electrospinning method | |
Koo et al. | Controlling the diameter of electrospun Yttria‐stabilized zirconia nanofibers | |
Castkova et al. | Electrospinning and thermal treatment of yttria doped zirconia fibres | |
Nataraj et al. | Effect of added nickel nitrate on the physical, thermal and morphological characteristics of polyacrylonitrile-based carbon nanofibers | |
Cui et al. | Fabrication of zirconium carbide (ZrC) ultra-thin fibers by electrospinning | |
Memarian et al. | Innovative method for electrospinning of continuous TiO2 nanofiber yarns: Importance of auxiliary polymer and solvent selection | |
CZ2008278A3 (en) | Method for production of inorganic nanofibers and/or nanofibrous structures comprising TiN, inorganic nanofibers and/or nanofibrous structures comprising TiN and use of such nanofibrous structures | |
Cho et al. | Properties of PVA/HfO2 hybrid electrospun fibers and calcined inorganic HfO2 fibers | |
KR20150028529A (en) | Nb-TiO2 CATALYST SUPPORTS AND METHOD FOR SYNTHESIS OF THE SAME USING ELECTROSPINNING | |
Tsotetsi et al. | Sol-gel derived mesoporous TiO2: Effects of non-ionic co-polymers on the pore size, morphology, specific surface area and optical properties analysis | |
Frontera et al. | A new approach to the synthesis of titania nano-powders enriched with very high contents of carbon nanotubes by electro-spinning | |
EP2103722A1 (en) | Ceramic fiber and method for production of ceramic fiber | |
Shepa et al. | Influence of the polymer precursor blend composition on the morphology of the electrospun oxide ceramic fibers | |
Gonzalez et al. | Nanocomposite building blocks of TiO2–MWCNTf and ZrO2–MWCNTf | |
Kim et al. | Enhancement of mechanical properties of TiO2 nanofibers by reinforcement with polysulfone fibers | |
Tunç et al. | Preparation of gadolina stabilized bismuth oxide doped with boron via electrospinning technique | |
KR101227087B1 (en) | Morphology control method of nano-structured material | |
Singh et al. | Electrospun ZrO2 fibers obtained from polyvinyl alcohol/zirconium n-propoxide composite fibers processed through halide free sol–gel route using acetic acid as a stabilizer | |
Mudra et al. | Preparation and characterization of ceramic nanofibers based on lanthanum tantalates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |