Classifications

• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
  • D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness
• • 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
  • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
• • 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
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
• • 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
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
• • 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
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
  • D01F6/64—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters from polycarbonates
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
  • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
  • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
  • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
  • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
  • D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
  • D04H3/153—Mixed yarns or filaments
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
  • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
  • B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
  • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
  • B01D2239/0258—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanoparticles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D39/00—Filtering material for liquid or gaseous fluids
  • B01D39/14—Other self-supporting filtering material ; Other filtering material
  • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
  • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
  • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
• • 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
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties

Definitions

• the invention concerns the morphologically optimized nonwoven textiles on the basis of nanofibres that can be produced by electrospinning and that embody an increased quality factor of filtration nanofibre nonwoven textiles (nNT).
• nNT filtration nanofibre nonwoven textiles
• nanofibre structures will find application particularly in the area of microfiltration (i.e. for removing particles sized from 100 nm to 15 ⁇ ) and ultrafiltration (for particles from 5 to 100 nm).
• microfiltration i.e. for removing particles sized from 100 nm to 15 ⁇
• ultrafiltration for particles from 5 to 100 nm
• the presence of drop-like defects in the PU structures may be also very effectively eliminated by an addition of surface active compounds, e.g. ionic liquids (Figs. 3 and 4).
• surface active compounds e.g. ionic liquids (Figs. 3 and 4).
• the change has been achieved by adding 1 wt. % (related to solid of the polymer) l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide of the IoLiTec Ionic Liquids Technologies company, FRG.
• the largest changes in the planar nanofibre structures may be achieved at the electrostatic fibre formatting process by the change of processed solution properties (polymer concentration and, hence, solution viscosity, polymer molar weight, solution conductivity, polymer permittivity%) and of the process parameters themselves (applied voltage, kind and distance of electrodes, quality and electric conductivity of the collecting substrate). It is by addition of various additives, solvents, modifying polymers and by a suitable combination of process variables not substantially changing the process intensity that nanofibre nonwoven textile (nNT) with high homogeneity, with required nanofibre diameter and organized space arrangement may be prepared in a continual process.
• nNT nanofibre nonwoven textile
• the morphologically optimized nonwoven textiles on the basis of nanofibres in accordance with the invention that show in particular an increased filtration effect contribute to removal of the above mentioned deficiency of the existing technology status.
• the invention principle consists of the fact that these nonwoven textiles include nanofibre structure with the morphologically separated nanofibres, as:
• nanofibre structure with nanofibres physically separated by drop-like spacers and/or nanoparticles dispersed within the nanostructure that form regular structures with drop-like spacers and/or nanoparticles dispersed within the nanostructure
• a morphologically optimized nonwoven textile containing nanofibre structure with nanofibres physically separated by drop-like spacers that form regular structures with droplike spacers cumulated in columns interconnected by nanofibres into regular morphological arrangements similar to honey combs is with an advantage polycarbonate nanofibre structure that may be prepared by the electrospinning technology from a spinning solution of polycarbonate in tetrachlorethane containing an addition of chloroform and borax.
• the organized space structures with spacers arranged into structures of honey combs may be prepared also from the polyurethane spinning solution in mixture of solvents dimethylformamide and tetracholorethane.
• the enhanced filtration features in comparison with planar structures show also organized space structures with spacers without honey combs morphology (as for example on Fig. 3).
• the elegant method of formation of structure with polymer distance spacers consists in combination of two polyurethane types with different average molar weight, where the one of them (with a lower M) under given electrospinning conditions forms globular microspheres and the other the nanofibres. It is possible to use also one of rigid polyurethane with a content of hard segments at least 20 wt. %.
• nanoparticles may be with advantage used as distance spheres (e.g. titanium dioxide, silver, phtalocyanine agglomerates, clay (refer to structure on Fig. 8) or jet milled clay (refer to structure on Fig. 9) that may be surface modified e.g. by chlorhexidine or zinc dioxide) dispersed in the nanofibre structure.
• materials may be prepared with additional added value, e.g. antibacterial properties.
• the incorporation of the nanoparticles into the fibrous composites during electrospinning under optimum conditions is very efficient (ca. 95%).
• the compared nanostructures (Table 1, Fig. 10) that show the same pressure drop at filtration of ultrafine particles are formed by fibres with a comparable average diameters and distribution of pores in the nanostructure (D n , D w ) but theysubstantially differ in area mass, thickness and filter effective area, which is the reason of enhancement of the filtration efficiency of the space nanostructure, and hence, of the filter quality factor.
• the space nanostructure has approximately 15 times larger area mass and 11 times larger thickness.
• the space arrangement results in physical separation of nanofibre layers increase of the distance between the nanofibres and angles, under which they are embedded in the nanostructures. Such morphology results in the enhancement of the nanostructures filtration properties.
• the fibres with a diameter in units of micrometres can also provide the function of distance spacers that form the space structure.
• Such arrangements that provide thickness and volume increase of the filtration material and that are created by fibres with a broad distribution of their diameters show also enhanced filtration properties.
• the rigid polymers with high modulus of elasticity as e.g. polymehtylmetacrylate (PMMA), styrene - acrylonitrile copolymer (SAN) as well as polyurethane with a high contents of hard segments, have tendency to form such arrangements - ref. to Figs. 13 through 15.
• the space arrangements originate in both the area of nanofibres (Fig. 13, magnification 5 OOOx) as well as the area of microfibers with fibre diameters of units of ⁇ (Fig. 14, magnification 1 500x) and/or diameters of tens of ⁇ (Fig. 15, magnification only 500x).
• the compared materials differ in distribution of fibre diameters (Fig. 17) and distribution of pore sizes (Fig. 18).
• the more voluminous structures are in the area of ultrafine particles capturing more effective maintaining the same pressure drop.
• Morphologically optimized nonwoven textiles may also contain structure with bimodal distribution of fibre diameters on the basis of combination of polymeric microfibers and nanofibres that form voluminous morphological arrangements.
• the Fig. 19 shows a structure with the bimodal distribution of fibre diameters containing polymethylmetacrylate microfibers and of polyurethane nanofibers.
• Fig. 2 polyurethane nanostructure with eliminated drop-like defects by addition of Na 2 B 4 0 7 .
• Fig. 5 polycarbonate nanostructure prior to the optimization process, magnification 1 500x.
• Fig. 6 polycarbonate nanostructure after the optimization - regular structures of drop-like spacers, magnification 1 500x
• Fig. 7 polyurethane nanostructure with regular structures of drop-like distance spheres prepared from the mixture of solvents dimethylformamide/tetrachlorethane, magnification 1 500x
• Fig. 8 composite nanostructure based on copolymer of ethylenvinylacetate (EVA)
• Fig. 9 composite nanostructure based on copolymer of ethylenvinylacetate (EVA)
• Fig. 10 comparison of filtration efficiency of planar and space nanostructure (ref. Table 1); pressure drop of compared nanostructures -90 Pa
• Fig. 1 1 comparison of distributions of fibre diameters of the planar and space nanostructures
• Fig. 14 combined space nanostructure based on polymethylmetacrylate fibres with a broad distribution of diameters, magnification 1 500x
• Fig. 15 combined space structure based on fibres of copolymer styrene- acrylonitrile with a broad distribution of diameters, magnification 1 500x
• Fig. 16 comparison of filtration efficiencies of the planar nanostructure and structure based on polymethylmetacrylate combaining microfibres and nanofibres, pressure drop of the compared materials -45 Pa
• Fig. 18 comparison of pores distribution of planar and pace nanostructure (ref. Table 2)
• Fig. 19 combined nanostructure based on polymethylmetacrylate microfibers and polyurethane nanofibres - bimodal distribution of fibre diameters, magnification
• electrospinning equipment Nanospider Elmarco, Liberec, Czech Republic
• rotating electrode with three cotton cords in accordance with PCT/CZ2010/000042
• the voltage in solution bath U 25 - 75 kV
• distance of electrodes D 15 - 25 cm
• rotating speed of the electrode 7 - 14 rpm
• Example 2 All the conditions have been the same as in Example 1, only the experimental equipment manufactured by SPUR a.s. is equipped with spinning nozzles instead of rotating cotton cord electrode.
• Organized space nanostructures based on nanofibres and globular spacers have been prepared from highly elastic polyurethanes as well - combination of two or more polyurethanes with different distribution of molar weight, when at least one of them forms fine fibres and, at least one of them forms rather spheres or drop-like spacers under given electrospinning conditions.
• the polyurethane solution contains dimethylformamide as solvent.
• the prepared mixtures with solid content of 10,5 - 19 wt. % and viscosity of 0,35 - 2,7 Pa.s has generated (under electrospinning conditions from Example 1) required organized space structures. These materials have shown the same filtration efficiency as nanostructures without globular distance spacers but substantially lower pressure drop.
• Another space structure has been prepared by electrospinning using PU 918, synthesized in accordance with Example 3 and solved in a mixture of solvents dimethylformamide and tetrachlorethane in ratio of 98,5:1,5 by weight.
• Such space arrangement has shown an increase of filtration efficiency in the area of ultrafme particles from 90,4% to 97,8% for MPPS 70 nm keeping the same pressure drop of 100 Pa in comparison with a planar arrangement.
• Space structure has been prepared by ellecrtospinning at conditions of Example 1.
• the solution of PU 918 in dimethylformamide containing 1,5 wt. % of jet milled nanoclay has been used.
• the space one shows an increase in quality factor of the filtration material to more than doubled values at the same pressure drop of 80 Pa (measured by Lorenz equipment, adjusted in accordance with EN 143).
• Example 6 Conditions of Example 6 have been the same as of Example 5 but instead of polyurethane solution the solution of copolymer ethylene-vinylacetate (EVA) in the solvents mixture toluene/tetrachlorethane in ratio 3:1 by weight has been used.
• EVA copolymer ethylene-vinylacetate
• Example 5 All the conditions have been the same as in Example 5 but instead of nanoclay nanoparticles of titanium dioxide with an average diameter of 60 nm have been used.
• Example 5 All the conditions have been the same as in Example 5 but instead of nanoclay nanoparticles of silver with an average diameter of 45 nm have been used.
• Example 10 All the conditions have been the same as in Example 5 but instead of nanoclay agglomerates of zinc phtalocyanine (COC, Rybitvi, Czech Republic) with an average diameter of 180 nm have been used.
• COC zinc phtalocyanine
• the concentration of polymer solution was 20 wt. % , viscosity 0,1 1 Pa.s and conductivity 1,3 ⁇ ⁇ "1 .
• the filtration properties of the materials with such space structure and a broad distribution of fibre diameters outperform the potency of the planar nanofibre materials as well.
• Another space structure based on fibres with a broad distribution of diameters of rigid polymers with high moduli of elasticity has been prepared from 20% solution of polyethersulphone in dimethylformamide (Ultrason, BASF, Germany) with viscosity of 0,84 Pa.s, and electric conductivity of 159 ⁇ 8 ⁇ "1 using SPUR' s jet electrostatic spinning equipment.
• PVDF polyvinylidenfluoride
• the space structure with a broad distribution of fibre diameters on the base of bicomponent fibre has been prepared from copolymer styrene-acrylonitrile (SAN- Luran) and PU 918 in a solvent system dimethylformamide/toluene.
• the prepared nanostructure has shown, in addition to the required filtration properties, also substantially better mechanical properties due to the use of elastic polyurethane.
• the space structure formed by combination of microfibres and nanofibres has been prepared using the SPUR's electrospinning equipment with four rows of nozzles.
• the solution of polymethylmetacrylate in mixture of solvents dimethylformamide/toluene in the ratio of 1 : 1 generating microfibers has been dosed into the first and third rows of nozzles.
• the solution of polyurethane in dimethylformamide generating nanofibres has been dosed in the second and fourth rows of nozzles.
• the electric conductivity of PU solution has been adjusted by borax and citric acid to the value about 150 ⁇ 8. ⁇ "1 .
• PVDF polyvinylidenfluoride
• Example 22 All the conditions have been the same as in Example 6, only the polyurethane with a high content of hard segments which is able under given electrospinning conditions produce microfibers has been used instead of polymethylmetacrylate.
• Example 22

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Dispersion Chemistry (AREA)
• Mechanical Engineering (AREA)
• Nonwoven Fabrics (AREA)
• Artificial Filaments (AREA)
• Filtering Materials (AREA)

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• 2011
  • 2011-07-19 CZ CZ2011-439A patent/CZ306779B6/cs not_active IP Right Cessation
• 2012
  • 2012-07-13 WO PCT/CZ2012/000065 patent/WO2013010517A2/en active Application Filing

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