WO1997043468A1 - Polymeric strands with high surface area and methods for making same - Google Patents
Polymeric strands with high surface area and methods for making same Download PDFInfo
- Publication number
- WO1997043468A1 WO1997043468A1 PCT/US1997/007112 US9707112W WO9743468A1 WO 1997043468 A1 WO1997043468 A1 WO 1997043468A1 US 9707112 W US9707112 W US 9707112W WO 9743468 A1 WO9743468 A1 WO 9743468A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- melt
- component
- strand
- liquid
- pressurized
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- 238000001125 extrusion Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 33
- 239000003921 oil Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 139
- -1 viricides Substances 0.000 claims description 75
- 239000000835 fiber Substances 0.000 claims description 19
- 229920001169 thermoplastic Polymers 0.000 claims description 17
- 235000019198 oils Nutrition 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical class OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 239000004166 Lanolin Substances 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 239000003899 bactericide agent Substances 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000003974 emollient agent Substances 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 239000000417 fungicide Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000002917 insecticide Substances 0.000 claims description 4
- 229940039717 lanolin Drugs 0.000 claims description 4
- 235000019388 lanolin Nutrition 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 239000001993 wax Substances 0.000 claims description 4
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000846 In alloy Inorganic materials 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000000704 physical effect Effects 0.000 abstract description 13
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 230000001720 vestibular Effects 0.000 description 4
- 230000002238 attenuated effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 238000006677 Appel reaction Methods 0.000 description 2
- MJBPUQUGJNAPAZ-AWEZNQCLSA-N Butin Natural products C1([C@@H]2CC(=O)C3=CC=C(C=C3O2)O)=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-AWEZNQCLSA-N 0.000 description 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000009960 carding Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229920001780 ECTFE Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002863 poly(1,4-phenylene oxide) polymer Polymers 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
-
- 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
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2978—Surface characteristic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31—Surface property or characteristic of web, sheet or block
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
Definitions
- This invention relates to polymeric strands made by melt-extruding an emulsion comprising a melt-extrudable polymer as a continuous phase and an immiscible component as a discontinuous phase for altering the physical properties of the strand.
- the melt-extrusion of liquids such as, for example, thermoplastic polymers
- the melt-extrusion of liquids generally involves forcing a molten polymer through a plurality of orifices to form a plurality of molten threadlines, contacting the molten threadlines with a fluid, usually air, directed so as to form strands (filaments or fibers) and attenuate them.
- the attenuated strands then are randomly deposited on a surface to form a nonwoven web.
- Meltblowing references include, by way of example, U.S. Patent Nos. 3,016,599 to Perry, Jr., 3,704,198 to Prentice, 3,755,527 to Keller et al., 3,849,241 to Butin et al., 3,978,185 to Butin et al., and 4,663,220 to Wisneski et al. See, also, V. A. Wente, "Superfine Thermoplastic Fibers", Industrial and Engineering Chemistry, Vol. 48, No. 8, pp. 1342-1346 (1956); V. A.
- Coforming references i.e., references disclosing a meltblowing process in which fibers or particles are commingled with the meltblown fibers as they are formed
- spunbonding references include, among others, U.S. Patent Nos. 3,341 ,394 to Kinney, 3,655,862 to Dorschner et al., 3,692,618 to Dorschner et al., 3,705,068 to Dobo et al., 3,802,817 to Matsuki et al., 3,853,651 to Porte, 4,064,605 to Akiyama et al., 4,091 ,140 to Harmon, 4,100,319 to Schwartz, 4,340,563 to Appel and Mo ⁇ rnan, 4,405,297 to Appel and Morman, 4,434,204 to Hartman et al., 4,627,811 to Greiser and Wagner, and 4,644,045 to Fowells.
- Nonwoven webs have many uses including cleaning products such as towels and industrial wipes, personal care items such as incontinence products, infant care products, and absorbent feminine care products, and garments such as medical apparel. These applications require polymeric strands with a wide variety of physical properties. The physical properties of melt-extruded polymeric strands are limited, however, and must often be engineered or surface treated for use in certain applications. For example, many thermoplastic materials used to make polymeric strands and nonwoven materials are hydrophobic and do not attract or wick water very well. To make some thermoplastic strands and resulting nonwoven materials hydrophilic, they must be treated with a material such as a surfactant which is often applied by spraying or dipping the product.
- melt-extruded polymeric strands and nonwoven materials made therewith there remains a need for a wider variety of physical properties and more economical and effective ways of altering the physical properties of melt-extruded strands and nonwovens.
- This invention addresses some of the needs described above by providing a melt-extruded polymeric strand comprising a melt-extrudable polymer and having a plurality of fissures in the surface of the strand.
- the strand has a B.E.T. surface area within a range from about 0.10 to about 0.18 m 2 g.
- This invention also encompasses a method for making such a strand by extruding an emulsion while applying ultrasonic energy to form the emulsion.
- This invention further encompasses a nonwoven web and a method for making a nonwoven web comprising such a melt-extruded polymeric strand.
- the melt-extruded polymeric strand of this invention having the plurality of surface fissures also has a mean diameter within the range from about 1 to about 200 micrometers and the fissures are desirably present in an amount from about 1x10 ⁇ to about 1x10 10 per m 2 .
- the B.E.T. surface area of such a strand is 2 to 6 times the B.E.T. surface are of an otherwise identical strand lacking the plurality of fissures.
- Such a high surface polymeric strand more effectively wicks liquid such as water than an otherwise identical strand lacking the plurality of fissures.
- a nonwoven web made with a strand of this invention having the enhanced surface area.
- the melt-extruded polymeric strand having the plurality of surface fissures may also include an immiscible component which is present at the surface of the strand at the fissures.
- the immiscible component is immiscible with the melt-extrudable polymer when the melt-extrudable polymer and the immiscible component are at a temperature suitable for melt-extrusion of the polymer.
- the immiscible component desirably performs a function at the surface of the strand not performed by the melt-extrudable polymer.
- the immiscible component can comprise a hydrophilic polymer while the melt-extrudable polymer is hydrophobic.
- Other exemplary immiscible components include surfactants, odorants and starches.
- the polymeric strand of this invention having the plurality of fissures in the strand surface is made by applying ultrasonic energy to a portion of a multicomponent liquid to form an emulsion and extruding the emulsion. More particularly, the method includes extruding a multi-component pressurized liquid through a die assembly, applying ultrasonic energy to a portion of the multi-component liquid, and attenuating the extruded multi-component liquid to form a strand.
- the die assembly includes a die housing and a device for applying ultrasonic energy to the multi-component liquid.
- the die housing comprises a chamber adapted to receive the pressurized multi-component liquid, an inlet adapted to supply the chamber with the pressurized multi-component liquid, and an exit orifice defined by the walls of a die tip.
- the exit orifice is adapted to receive the pressurized multi-component liquid from the chamber and pass the multi-component liquid out of the die housing.
- the multi-component pressurized liquid comprises a melt-extrudable polymer and an immiscible component which is immiscible in the melt-extrudable polymer when the multi-component pressurized liquid is at a temperature suitable for melt-extrusion and is capable of forming an expanding gas after the multi-component pressurized liquid is passed out of the die housing through the exit orifice.
- the ultrasonic energy is applied to a portion of the pressurized multi-component liquid within the chamber and without applying ultrasonic energy to the die tip, while the exit orifice receives the pressurized multi-component liquid from the die housing chamber. Consequently, the pressurized multi-component liquid passes out of the exit orifice in the die tip as an emulsion.
- the melt-extrudable polymer forms a continuous phase of the emulsion and the immiscible component forms a disperse phase of the emulsion.
- the immiscible component forms an expanding gas which explodes through the surface of the strand and forms the plurality of fissures in the strand surface.
- the immiscible component includes water which forms steam during extrusion of the polymer and explodes through the surface of the strand to form the fissures.
- the immiscible component may also include a functional ingredient such as a hydrophilic polymer, a surfactant, an odorant, or the like, as described above with regard to the melt-extruded polymeric strand.
- this invention further comprehends a melt-extruded polymeric strand comprising a continuous phase which is the melt-extrudable polymer and a disperse phase comprising an amendment for altering the physical properties of the strand.
- the amendment is immiscible with the continuous phase when the continuous phase and the disperse phase are at a temperature suitable for melt-extrusion of the polymeric strand.
- the melt-extruded polymeric strand of this invention described immediately hereinbefore has a dispersed phase which comprises discreet pockets of material separated by the continuous phase.
- the disperse phase desirably includes an ingredient which performs a function not performed by the melt-extrudable polymer.
- the disperse phase may include lubricating oils, skin emollients, tinting oils, waxes, polishing oils, silicones, vegetable oils, glycerines, lanolin, flame retardants, tackifiers, degradation triggers, insecticides, fungicides, bactericides, viricides, colloids, and suspensions.
- the disperse phase can comprise a gas such as air, or an electroluminescent gas such as neon or argon.
- the disperse phase can comprise a low melting point metal or alloy such as bismuth alloys, indium alloys, tin, or gallium. Such metals should be molten at temperatures suitable for melt-extrusion of the polymeric strand.
- the foregoing amendments which form the disperse phase of the polymeric strand impart a variety of physical properties to the polymeric strand and allow the polymeric strands to be useful for a variety of end uses.
- This invention encompasses a method for making a polymeric strand including the amendments described immediately hereinbefore.
- the method is very similar to the method described hereinabove with regard to the strand having the plurality of fissures except that the immiscible component of the multi-component liquid does not necessarily include a component for forming an expanding gas.
- Nonwoven webs made with the above-described polymeric strands are made by depositing the polymeric strands onto a collecting surface such as in meltblowing, coforming, or spunbonding techniques.
- FIG. 1 is a cross-sectional elevation view of an apparatus for making an embodiment of the present invention.
- FIG. 2 is a photomicrograph of a strand made according to an embodiment of this invention with fissures in the surface of the strand.
- FIG. 3 is a photomicrograph of another strand made according to an embodiment of this invention with a plurality of fissures in the surface of the strand.
- FIG. 4 is a photomicrograph of an undrawn strand made according to an embodiment of this invention.
- the strand has been insulted on the left side with tap water.
- FIG. 5 is a photomicrograph showing the severed end of a slightly drawn strand made according to an embodiment of this invention and having a plurality of fissures on its surface. The strand has been insulted on the right end with tap water.
- FIG. 6 is a photomicrograph of an air drawn strand made according to an embodiment of this invention with the insult water wicking left to right.
- this invention encompasses melt-extruded polymeric strands with altered physical properties, nonwoven webs made with such strands and methods for making the foregoing.
- an apparatus for use in making strands in accordance with an embodiment of this invention is described, followed by a description of methods for using the apparatus and particular examples of polymeric strands made with the apparatus.
- strand refers to an elongated extrudate formed by passing a polymer through a forming orifice such as a die. Strands include fibers, which are discontinuous strands having a definite length, and filaments, which are continuous strands of material.
- nonwoven web means a web of material which has been formed without use of weaving processes which produce a structure of individual strands which are interwoven in an identifiable repeating manner.
- Nonwoven webs may be formed by a variety of processes such as meltblowing processes, spunbonding processes, film aperturing processes, coforming processes, and staple fiber carding processes.
- liquid refers to an amorphous (noncrystalline) form of matter intermediate between gases and solids, in which the molecules are much more highly concentrated than in gases, but much less concentrated than in solids.
- a liquid may have a single component or may be made of multiple components. The components may be other liquids, solids and/or gases.
- characteristic of liquids is their ability to flow as a result of an applied force. Liquids that flow immediately upon application of force and for which the rate of flow is directly proportional to the force applied are generally referred to as Newtonian liquids. Some liquids have abnormal flow response when force is applied and exhibit non-Newtonian flow properties.
- thermoplastic polymer and “thermoplastic material” refer to a high polymer that softens when exposed to heat and returns to its original condition when cooled to room temperature.
- the terms are meant to include any thermoplastic polymer which is capable of being melt-extruded.
- the term also is meant to include blends of two or more polymers and alternating, random, and block copolymers.
- thermoplastic polymers include, by way of illustration only, end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), and the like; fluorocarbon polymers, such as poty(tetrafluoroethylene), perfluorinated ethylene-propylene copolymers, ethylene-tetrafluoroethylene copolymers, poly(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like; polyamides, such as poly(6-aminocaproic acid) or poly(
- thermoplastic polymer may be a polyolefin, examples of which are listed above.
- thermoplastic polymer may be a polyolefin which contains only hydrogen and carbon atoms and which is prepared by the addition polymerization of one or more unsaturated monomers.
- polystyrene examples include, among others, polyethylene, polypropylene, poly(1 -butene), poly(2-butene), poly(1 -pentene), poly(2-pentene), poly (3-methy 1-1 -pentene), poly(4-methyl-1 -pentene), 1 ,2-poly-1 ,3-butadiene, 1 ,4-poly-1 ,3-butadiene, polyisoprene, polystyrene, and the like, as well as blends of two or more such polyolefins and alternating, random, and block copolymers prepared from two or more different unsaturated monomers.
- hydrophilic when describing polymers, means a polymer having a surface energy at 20°C within the range of about 55 to about 75 dynes/cm 2 .
- hydrophobic with regard to polymers, means a polymer having a surface energy of 20°C within the range of about 20 dynes/cm 2 to about 50 dynes/cm 2
- emulsion refers to a relatively stable mixture of two or more immiscible liquids that, in some cases, may be held in suspension by small percentages of substances called emulsifiers or stabilizers. Emulsions may also be held in suspension or stabilized by the continuous phase being extremely viscous, or by the solidification of the continuous phase after the formation of the emulsion. Emulsions are composed of a continuous phase and a disperse phase. For example, in an oil in water emulsion, water is the continuous phase and oil is the disperse phase.
- node means the point on the longitudinal excitation axis of the ultrasonic horn at which no longitudinal motion of the horn occurs upon excitation by ultrasonic energy.
- the node sometimes is referred to in the art, as well as in this specification, as the nodal point.
- close proximity is used herein in a qualitative sense only. That is, the term is used to mean that the means for applying ultrasonic energy is sufficiently close to the exit orifice (e.g., extrusion orifice) to apply the ultrasonic energy primarily to the liquid (e.g., multi-component liquid) passing into the exit orifice (e.g., extrusion orifice).
- the term is not used in the sense of defining specific distances from the extrusion orifice.
- the apparatus of the present invention includes a die housing and a means for applying ultrasonic energy to a portion of a pressurized multi-component liquid such as a molten thermoplastic polymer and water.
- the die housing defines a chamber adapted to receive the pressurized multi-component liquid, an inlet (e.g., inlet orifice) adapted to supply the chamber with the pressurized multi-component liquid, and an exit orifice (e.g., extrusion orifice) adapted to receive the pressurized liquid from the chamber and pass the liquid out of the exit orifice of the die housing so that the multi-component liquid is emulsified.
- the means for applying ultrasonic energy is located within the chamber.
- the means for applying ultrasonic energy can be located partially within the chamber or the means for applying ultrasonic energy can be located entirely within the chamber.
- the apparatus 100 includes a die housing 102 which defines a chamber 104 adapted to receive a pressurized multi-component liquid such as molten thermoplastic polymer.
- the die housing 102 has a first end 106 and a second end 108.
- the die housing 102 also has an inlet 110 (e.g., inlet orifice) adapted to supply the chamber 104 with the pressurized multi-component liquid.
- An exit orifice 112 (which may also be referred to as an extrusion orifice) is located in the first end 106 of the die housing 102; it is adapted to receive the pressurized multi-component liquid from the chamber 104 and pass the multi-component liquid out of the die housing 102 along a first axis 114.
- An ultrasonic hom 116 is located in the second end 108 of the die housing 102. The ultrasonic hom has a first end 118 and a second end 120.
- the horn 116 is located in the second end 108 of the die housing 102 in a manner such that the first end 118 of the hom 116 is located outside of the die housing 102 and the second end 120 of the hom 116 is located inside the die housing 102, within the chamber 104, and is in close proximity to the exit orifice 112.
- the hom 116 is adapted, upon excitation by ultrasonic energy, to have a nodal point 122 and a longitudinal mechanical excitation axis 124.
- the first axis 114 and the mechanical excitation axis 124 will be substantially parallel. More desirably, the first axis 114 and the mechanical excitation axis 124 will substantially coincide, as shown in FIG. 1.
- the size and shape of the apparatus of the present invention can vary widely, depending, at least in part, on the number and arrangement of exit orifices (e.g., extrusion orifices) and the operating frequency of the means for applying ultrasonic energy.
- the die housing may be cylindrical, rectangular, or any other shape.
- the die housing may have a single exit orifice or a plurality of exit orifices.
- a plurality of exit orifices may be arranged in a pattern, including but not limited to, a linear or a circular pattern.
- the means for applying ultrasonic energy is located within the chamber, typically at least partially surrounded by the pressurized liquid. Such means is adapted to apply the ultrasonic energy to the pressurized liquid as it passes into the exit orifice. Stated differently, such means is adapted to apply ultrasonic energy to a portion of the pressurized liquid in the vicinity of each exit orifice. Such means may be located completely or partially within the chamber.
- the hom When the means for applying ultrasonic energy is an ultrasonic horn, the hom conveniently extends through the die housing, such as through the first end of the housing as identified in FIG. 1.
- the present invention comprehends other configurations.
- the hom may extend through a wall of the die housing, rather than through an end.
- neither the first axis nor the longitudinal excitation axis of the hom need to be vertical.
- the longitudinal mechanical excitation axis of the hom may be at an angle to the first axis.
- the longitudinal mechanical excitation axis of the ultrasonic hom desirably will be substantially parallel with the first axis. More desirably, the longitudinal mechanical excitation axis of the ultrasonic hom desirably and the first axis will substantially coincide, as shown in FIG. 1.
- more than one means for applying ultrasonic energy may be located within the chamber defined by the die housing. Moreover, a single means may apply ultrasonic energy to the portion of the pressurized liquid which is in the vicinity of one or more exit orifices.
- the ultrasonic horn may be composed of a magnetostrictive material.
- the hom may be surrounded by a coil (which may be immersed in the liquid) capable of inducing a signal into the magnetostrictive material causing it to vibrate at ultrasonic frequencies.
- the ultrasonic horn can simultaneously be the transducer and the means for applying ultrasonic energy to the multi-component liquid.
- the application of ultrasonic energy to a plurality of exit orifices may be accomplished by a variety of methods.
- the second end of the hom may have a cross-sectional area which is sufficiently large so as to apply ultrasonic energy to the portion of the pressurized multi-component liquid which is in the vicinity of all of the exit orifices in the die housing.
- the second end of the ultrasonic hom desirably will have a cross-sectional area approximately the same as or greater than a minimum area which encompasses all exit orifices in the die housing (i.e., a minimum area which is the same as or greater than the sum of the areas of the exit orifices in the die housing originating in the same chamber).
- the second end of the horn may have a plurality of protrusions, or tips, equal in number to the number of exit orifices.
- the cross-sectional area of each protrusion or tip desirably will be approximately the same as or less than the cross-sectional area of the exit orifice with which the protrusion or tip is in close proximity.
- planar relationship between the second end of the ultrasonic hom and an array of exit orifices may also be shaped (e.g., parabolically, hemispherically, or provided with a shallow curvature) to provide or correct for certain spray patterns.
- the term "close proximity" is used herein to mean that the means for applying ultrasonic energy is sufficiently close to the exit orifice to apply the ultrasonic energy primarily to the pressurized multi-component liquid passing into the exit orifice.
- the actual distance of the means for applying ultrasonic energy from the exit orifice in any given situation will depend upon a number of factors, some of which are the flow rate of the pressurized multi-component liquid (e.g., the flow rate, rheological characteristics or the viscosity of a liquid), the cross-sectional area of the end of the means for applying the ultrasonic energy relative to the cross-sectional area of the exit orifice, the frequency of the ultrasonic energy, the gain of the means for applying the ultrasonic energy (e.g., the magnitude of the longitudinal mechanical excitation of the means for applying ultrasonic energy), the temperature of the pressurized multi-component liquid, the particular emulsification properties of the liquids, the rheological characteristics of the emulsion, and the
- the distance of the means for applying ultrasonic energy from the exit orifice in a given situation may be determined readily by one having ordinary skill in the art without undue experimentation. In practice, such distance will be in the range of from about 0.002 inch (about 0.05 mm) to about 1.3 inches (about 33 mm), although greater distances can be employed. Such distance determines the extent to which ultrasonic energy is applied to the pressurized multi-component liquid other than that which is about to enter the exit orifice; i.e., the greater the distance, the greater the amount of pressurized liquid which is subjected to ultrasonic energy.
- the means for applying ultrasonic energy is an immersed ultrasonic hom having a longitudinal mechanical excitation axis and in which the end of the hom located in the die housing nearest the orifice is in close proximity to the exit orifice but does not apply ultrasonic energy directly to the exit orifice.
- the exit orifice is adapted to be self-cleaning when the means for applying ultrasonic energy is excited with ultrasonic energy (without applying ultrasonic energy directly to the orifice) while the exit orifice receives pressurized multi-component liquid from the chamber and passes the multi-component liquid out of the die housing to form an emulsion.
- melt-extruded polymeric strands are formed with the extruder apparatus 100 illustrated in FIG. 1 by introducing a pressurized multi-component liquid into the chamber 104 of the die housing 102 through the inlet 110 and exciting the ultrasonic hom 116 as the pressurized multi-component liquid is extruded through the exit orifice 112.
- the multi-component pressurized liquid comprises a melt-extrudable polymer and an immiscible component which is immiscible in the melt-extrudable polymer when the multi-component pressurized liquid is at a temperature suitable for melt-extrusion.
- the ultrasonic energy applied by the ultrasonic hom 116 applies ultrasonic energy to a portion of the pressurized multi-component liquid within the chamber and without applying ultrasonic energy to the die tip, while the multi-component liquid is received and extruded through the exit orifice 112.
- the ultrasonic energy emulsifies the multi-component liquid so that the melt-extrudable polymer forms a continuous phase of the emulsion and the immiscible component forms a disperse phase of the emulsion.
- the extruded multi-component liquid is attenuated to form a strand.
- the attenuation of the extruded multi-component liquid can be accomplished mechanically or by entraining the fiber in a fluid such as in a meltblowing or spunbonding process.
- a fluid such as in a meltblowing or spunbonding process.
- the strand is randomly deposited on a collecting surface.
- Nonwoven webs can also be prepared by extruding the multi-component liquid and forming a strand, cutting the strand into staple fibers, and carding the staple fibers into a nonwoven web which can be subsequently bonded by known means.
- melt-extruded polymeric strand The physical properties of the resulting melt-extruded polymeric strand depend largely on the melt-extruded polymer which forms a continuous phase and the amendment or immiscible component which forms the disperse phase.
- Suitable melt-extrudable polymers are described above and a wide variety of amendments can be combined with the melt-extrudable polymer.
- a high surface area strand can be produced by combining water, as the immiscible component, with a non-water soluble, melt-extrudable polymer as the continuous phase.
- the melt-extrudable polymer forms the continuous phase of the emulsion and the water forms the disperse phase of the emulsion.
- the melt-extrudable polymer/water emulsion is extruded and attenuated to form a strand, the water forms steam which expands and explodes through the surface of the strand and forms a plurality of fissures in the strand surface. These fissures increase the surface area of the strand and cause the strand to be more effective in wicking liquid such as water.
- the polymeric strand formed with the melt-extrudable polymer and water can have a plurality of fissures in the surface of the strand such that the strand has a B.E.T. surface area which is 2 to 6 times the B.E.T. surface area of an otherwise identical strand lacking the plurality of fissures. More particularly, the fissures can create a B.E.T. surface area within a range from about 0.10 to about 0.18 m 2 /g. In a desirable embodiment, such a melt-extruded high surface area polymeric strand has a mean diameter within the range from about 1 to about 200 micrometers and has fissures present in an amount from about 1x10 ⁇ to about 1x10 10 per m 2 .
- the melt-extruded polymeric strand is formed with an aqueous solution containing water and a component which performs a function at the surface of the strand not performed by the melt-extrudable polymer.
- the melt-extrudable polymer can be a hydrophobic polymer such as polyproylene and the immiscible component can comprise an aqueous solution of a hydrophilic polymer such as polyvinyl alcohol.
- the resulting polymeric strand has a plurality of fissures in the surface of the strand and polyvinyl alcohol is present at the surface of the strand at the fissures.
- the hydrophilic polyvinyl alcohol improves the wettability of the polymeric strand and the ability of the strand to wick fluid such as water.
- Suitable aqueous solutions for use as the immiscible component or disperse phase in making polymeric strands of this invention include other aqueous polymers, surfactants, odorants, starches, anti-fouling agents, salts, and other functional chemical compounds.
- the immiscible component or disperse phase of the multi-component liquid can include a low melting point metal or alloy.
- low melting it is meant that the metal or alloy is molten at melt-extrusion temperatures for the multi-component liquid.
- Suitable low melting point metals and alloys include tin, gallium, bismuth alloys, and indium alloys.
- the immiscible component or disperse phase of the multi-component liquid can include a variety of oils, oil based materials, and other non-phase change liquids such as lubricating oils, skin emollients, tinting oils, including fluorescent and luminescent oils, waxes, polishing oils, silicones, vegetable oils, glycerin, lanolin, flame retardants, tackifiers, degradation triggers such as time, photo, or chemical environment sensitive degradation triggers, insecticides, fungicides, bactericides, viricides, colloids and suspensions, and emulsion reaction catalysts.
- oils oil based materials
- other non-phase change liquids such as lubricating oils, skin emollients, tinting oils, including fluorescent and luminescent oils, waxes, polishing oils, silicones, vegetable oils, glycerin, lanolin, flame retardants, tackifiers, degradation triggers such as time, photo, or chemical environment sensitive degradation triggers, insecticides, fung
- the immiscible component or disperse phase of the multi-component liquid can include gases such as air or electroluminescent gases such as neon and argon.
- gases such as air or electroluminescent gases such as neon and argon.
- the resulting strands can have relatively light density, opacity, increase surface area, or electroluminescence.
- the immiscible component or disperse phase of the multi-component liquid includes a substance which forms an expanding gas upon extrusion of the multi-component liquid
- the immiscible component is initially entrapped in the melt-extrudable polymer during melt-extrusion and then explodes through the surface of the strand to form fissures in the strand.
- the immiscible component or the disperse phase of the multi-component liquid does not include a substance that forms such an expanding gas
- the disperse phase forms pockets of the immiscible component and the resulting strand includes the pockets of this disperse phase entrapped in the continuous melt-extrudable polymer phase.
- the die housing 102 of the apparatus was a cylinder having an outer diameter of 1.375 inches (about 34.9 mm), an inner diameter of 0.875 inch (about 22.2 mm), and a length of 3.086 inches (about 78.4 mm).
- the outer 0.312-inch (about 7.9-mm) portion of the second end 108 of the die housing was threaded with 16-pitch threads.
- the inside of the second end had a beveled edge 126, or chamfer, extending from the face 128 of the second end toward the first end 106 a distance of 0.125 inch (about 3.2 mm). The chamfer reduced the inner diameter of the die housing at the face of the second end to 0.75 inch (about 19.0 mm).
- An inlet 110 (also called an inlet orifice) was drilled in the die housing, the center of which was 0.688 inch (about 17.5 mm) from the first end, and tapped.
- the inner wall of the die housing consisted of a cylindrical portion 130 and a conical frustrum portion 132.
- the cylindrical portion extended from the chamfer at the second end toward the first end to within 0.992 inch (about 25.2 mm) from the face of the first end.
- the conical frustrum portion extended from the cylindrical portion a distance of 0.625 inch (about 15.9 mm), terminating at a threaded opening 134 in the first end.
- the diameter of the threaded opening was 0.375 inch (about 9.5 mm); such opening was 0.367 inch (about 9.3 mm) in length.
- a die tip 136 was located in the threaded opening of the first end.
- the die tip consisted of a threaded cylinder 138 having a circular shoulder portion 140.
- the shoulder portion was 0.125 inch (about 3.2 mm) thick and had two parallel faces (not shown) 0.5 inch (about 12.7 mm) apart.
- An exit orifice 112 also called an extrusion orifice was drilled in the shoulder portion and extended toward the threaded portion a distance of 0.087 inch (about 2.2 mm).
- the diameter of the extrusion orifice was 0.0145 inch (about 0.37 mm).
- the extrusion orifice terminated within the die tip at a vestibular portion 142 having a diameter of 0.125 inch (about 3.2 mm) and a conical frustrum portion 144 which joined the vestibular portion with the extrusion orifice.
- the wall of the conical frustrum portion was at an angle of 30° from the vertical.
- the vestibular portion extended from the extrusion orifice to the end of the threaded portion of the die tip, thereby connecting the chamber defined by the die housing with the extrusion orifice.
- the means for applying ultrasonic energy was a cylindrical ultrasonic hom 116.
- the horn was machined to resonate at a frequency of 20 kHz.
- the hom had a length of 5.198 inches (about 132.0 mm), which was equal to one-half of the resonating wavelength, and a diameter of 0.75 inch (about 19.0 mm).
- the face 146 of the first end 118 of the horn was drilled and tapped for a 3/8-inch (about 9.5-mm) stud (not shown).
- the horn was machined with a collar 148 at the nodal point 122.
- the collar was 0.094-inch (about 2.4-mm) wide and extended outwardly from the cylindrical surface of the hom 0.062 inch (about 1.6 mm).
- the diameter of the horn at the collar was 0.875 inch (about 22.2 mm).
- the second end 120 of the horn terminated in a small cylindrical tip 150 0.125 inch (about 3.2 mm) long and 0.125 inch (about 3.2 mm) in diameter.
- Such tip was separated from the cylindrical body of the hom by a parabolic frustrum portion 152 approximately 0.5 inch (about 13 mm) in length. That is, the curve of this frustrum portion as seen in cross-section was parabolic in shape.
- the face of the small cylindrical tip was normal to the cylindrical wall of the hom and was located about 0.4 inch (about 10 mm) from the extrusion orifice.
- the face of the tip of the hom i.e., the second end of the hom, was located immediately above the vestibular opening in the threaded end of the die tip.
- the first end 108 of the die housing was sealed by a threaded cap 154 which also served to hold the ultrasonic hom in place.
- the threads extended upwardly toward the top of the cap a distance of 0.312 inch (about 7.9 mm).
- the outside diameter of the cap was 2.00 inches (about 50.8 mm) and the length or thickness of the cap was 0.531 inch (about 13.5 mm).
- the opening in the cap was sized to accommodate the horn; that is, the opening had a diameter of 0.75 inch (about 19.0 mm).
- the edge of the opening in the cap was a chamfer 156 which was the mirror image of the chamfer at the second end of the die housing.
- the thickness of the cap at the chamfer was 0.125 inch (about 3.2 mm), which left a space between the end of the threads and the bottom of the chamfer of 0.094 inch (about 2.4 mm), which space was the same as the length of the collar on the horn.
- the diameter of such space was 1.104 inch (about 28.0 mm).
- the top 158 of the cap had drilled in it four 1/4-inch diameter x 1/4-inch deep holes (not shown) at 90° intervals to accommodate a pin spanner.
- the collar of the hom was compressed between the two chamfers upon tightening the cap, thereby sealing the chamber defined by the die housing.
- a Branson elongated aluminum waveguide having an inputoutput mechanical excitation ratio of 1 :1.5 was coupled to the ultrasonic hom by means of a 3/8-inch (about 9.5-mm) stud.
- a Branson Model 502 Converter To the elongated waveguide was coupled a piezoelectric transducer, a Branson Model 502 Converter, which was powered by a Branson Model 1120 Power Supply operating at 20 kHz (Branson Sonic Power Company, Danbury, Connecticut). Power consumption was monitored with a Branson Model A410A Wattmeter.
- This example illustrates the present invention as it relates to the emulsification of a molten thermoplastic polymer and water.
- the device has the capability to process up to 25 pounds of polymer per hour (about 11 kilograms per hour), and has an integral variable speed gear pump with a displacement of 1.752 cc/revolution.
- Temperature of the melt is regulated in two zones, premelt and main melt. Pressure is limited and regulated by an internal variable by-pass valve, and indicated by digital readout resolved to increments of 10 psi.
- Pump drive speed is controlled by a panel mounted potentiometer.
- the Grid Melter was used to melt and pressurize a thermoplastic polymer.
- the polymer used was Himont HH-441 (Himont HH-441 , Himont Company, Wilmington, Delaware), a polypropylene having no melt processing additives and a melt flow rate of 400 grams per 10 minutes, or g/10 min.
- the melt flow rate is expressed in units of mass divided by time (i.e., grams/10 minutes).
- the melt flow rate was determined by measuring the mass of molten thermoplastic polymer under a 2.160 kg load that flowed through an orifice diameter of 2.0995 + 0.0051 mm during a specified time period such as, for example, 10 minutes at a specified temperature such as, for example, 180°C as determined in accordance with ASTM Test Method D 1238-82, "Standard Test Method for Flow Rates of Thermoplastic By Extrusion Plastometer," using a Model VE 4-78 Extrusion Plastometer (Tinius Olsen Testing Machine Co., Willow Grove, Pennsylvania).
- Water was injected into the molten polymer upstream of the ultrasonic apparatus (i.e., before the polymer and water entered the ultrasonic apparatus) utilizing a High Pressure Injector Pump; 90 V DC parallel shaft drive gear motor from W.W. Grainger, Inc., Alpharetta, Georgia, speed range of 0 - 21 rpm; Dayton DC Speed Controller Model 6X165 from W. W. Grainger, Inc., Alpharetta, Georgia. A 9/16" piston was used to inject water into the polymer stream.
- the high pressure side stream injector pump was fitted with the 9/16 inch diameter piston and was filled with distilled water.
- the fibers wound on the drum were cold drawn by hand to about 7-10 times their original length.
- the cold drawn fibers were examined by scanning electron microscopy.
- FIG. 2 is a photomicrograph (800X linear magnification) of the fiber produced at an extrusion temperature of 340° F and a pressure of 250 psi.
- FIG. 3 is a photomicrograph (503X linear magnification) of the fiber produced at an extrusion temperature of 330° F and a pressure of
- FIGS. 2 and 3 were made with a Cambridge Stereoscan 200 scanning electron microscope (SEM) and show that the fibers are covered with elongate fissures that are formed from ruptured steam bubbles near the surface of the fiber.
- the number of fissures in the strands range from about 1x10 ⁇ to about 1x10 10 fissures per m 2 and is determined by visually counting the fissures in a square area of the strand surface using a scanning electron microscope.
- Example 1 To further characterize the effect of the ultrasonic emulsion on the polymeric strand produced in Example 1 , a quantity (1 gram) of the drum wound strand of Example 1 formed at 340°F and 250 psi was hand-drawn, and 15 random measurements of diameter were taken, the mean diameter being 75.1 micrometers. This sample is referred to as Sample 1. A 1 gram quantity of the same strand, undrawn, was likewise measured for diameter, the mean diameter being 211.5 micrometers. This sample is referred to as Sample 2. Both Sample 1 and Sample 2 were analyzed for surface area by using the B.E.T. krypton adsorbate method in accordance with ASTM D4780-88. The surface area was measured by Micromeritics® of Norcross, Georgia.
- the B.E.T. surface area of Sample 1 was 0.1518 m 2 /g.
- the surface area of a solid polypropylene fiber having a density of 0.9, and the same diameter as Sample 1 was 0.05918 m 2 /g.
- the B.E.T. surface area of Sample 2 was 0.1233 m 2 /g.
- the surface area of a solid polypropylene strand having a density of 0.9, and the same diameter as Sample 2 was 0.0210 m 2 /g.
- a polymeric strand was made in accordance with the procedure of Example 1 except that the grid melter and piping temperature was 370°F and the extrusion apparatus temperature was 380°F, the water was replaced with a solution of water and 20% polyvinyl alcohol (No. 125, Lot No. 04031512 available from Air Products and Chemicals, Inc. of Allentown, Pennsylvania), the pressure of the grid melter was adjusted to 500 psi, the polymer flow rate, with the ultrasonic power setting at 30% and drawing about 50 watts, was 1.8 to 2.0 grams per minute, and the water injection pump was started at a setting of 20. The onset of the polyvinyl alcohol solution in the polymer extrudate was indicated by a change in the opacity of the extruded strand from translucent to milky white.
- FIG. 4 is a photomicrograph (51 x linear magnification) of the undrawn strand from Example 2 having been insulted on the left side with tap water.
- FIG. 5 is a photomicrograph (51x linear magnification) showing a severed end of a slightly drawn strand from Example 2. The striations from lower right to upper left are the elongated microbubbles formed by the water component flashing in the seam. The sample was insulted at the lower right with tap water. The short lines that are approximately normal to the long striations are the fronts of water streams as they wicked through the strand from right to left.
- FIG. 4 is a photomicrograph (51 x linear magnification) of the undrawn strand from Example 2 having been insulted on the left side with tap water.
- FIG. 5 is a photomicrograph (51x linear magnification) showing a severed end of a slightly drawn strand from Example 2. The striations from lower right to upper left are the elongated microbubbles
- FIGS. 4-6 are photomicrograph (128x linear magnification) showing an air drawn strand from Example 2 with the insult water wicking from left to right.
- FIGS. 4-6 were made with an Olympus BH-2 stereo microscope coupled to a Hitachi VK-C350 video camera.
- the method of this invention permits the formation of extruded products with constituent materials and properties different from those produced by conventional extrusion methods.
- the method of this invention accommodates the addition of amendments currently used in normal extrusions methods.
- a significant advantage to the method of this invention is that the amendments or immiscible components are added at the point of extrusion, and are not a consideration in upstream portions of the processes such as blending, feeding, melting, pressurizing, filtering, and metering.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2249324 CA2249324C (en) | 1996-05-10 | 1997-04-28 | Polymeric strands with high surface area and methods for making same |
AU28164/97A AU2816497A (en) | 1996-05-10 | 1997-04-28 | Polymeric strands with high surface area and methods for making same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/644,511 | 1996-05-10 | ||
US08/644,511 US5801106A (en) | 1996-05-10 | 1996-05-10 | Polymeric strands with high surface area or altered surface properties |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997043468A1 true WO1997043468A1 (en) | 1997-11-20 |
Family
ID=24585222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/007112 WO1997043468A1 (en) | 1996-05-10 | 1997-04-28 | Polymeric strands with high surface area and methods for making same |
Country Status (4)
Country | Link |
---|---|
US (1) | US5801106A (en) |
AU (1) | AU2816497A (en) |
CA (1) | CA2249324C (en) |
WO (1) | WO1997043468A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005016194A1 (en) * | 2005-04-08 | 2006-10-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the preparation of polymer moldings from polymers which are immiscible or poorly miscible with one another |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6010592A (en) | 1994-06-23 | 2000-01-04 | Kimberly-Clark Corporation | Method and apparatus for increasing the flow rate of a liquid through an orifice |
ZA969680B (en) | 1995-12-21 | 1997-06-12 | Kimberly Clark Co | Ultrasonic liquid fuel injection on apparatus and method |
US6053424A (en) | 1995-12-21 | 2000-04-25 | Kimberly-Clark Worldwide, Inc. | Apparatus and method for ultrasonically producing a spray of liquid |
US6663027B2 (en) | 2000-12-11 | 2003-12-16 | Kimberly-Clark Worldwide, Inc. | Unitized injector modified for ultrasonically stimulated operation |
US6543700B2 (en) | 2000-12-11 | 2003-04-08 | Kimberly-Clark Worldwide, Inc. | Ultrasonic unitized fuel injector with ceramic valve body |
US6528554B1 (en) | 2001-02-15 | 2003-03-04 | The University Of Akron | Ultrasound assisted continuous process for making polymer blends and copolymers |
US8501232B2 (en) * | 2002-04-23 | 2013-08-06 | Nanotherapeutics, Inc. | Process of forming and modifying particles and compositions produced thereby |
ES2390183T3 (en) * | 2006-10-11 | 2012-11-07 | Crititech, Inc. | Method of precipitation of small particles of medicine in use container |
CA2692638C (en) * | 2010-02-25 | 2011-05-10 | The Procter & Gamble Company | Absorbent article with improved garment-like character |
WO2017010451A1 (en) * | 2015-07-16 | 2017-01-19 | 大川原化工機株式会社 | Wet disperser |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB865707A (en) * | 1956-04-28 | 1961-04-19 | Rasmussen O B | Method of manufacturing artificial fibres |
US4239720A (en) * | 1978-03-03 | 1980-12-16 | Akzona Incorporated | Fiber structures of split multicomponent fibers and process therefor |
EP0644280A1 (en) * | 1993-09-17 | 1995-03-22 | PETOCA, Ltd | Milled carbon fiber and process for producing the same |
WO1996000318A2 (en) * | 1994-06-23 | 1996-01-04 | Kimberly-Clark Corporation | Method and apparatus for increasing the flow rate of a liquid through an orifice |
Family Cites Families (107)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE134052C (en) * | ||||
DE177045C (en) * | ||||
US2484012A (en) * | 1946-07-01 | 1949-10-11 | American Viscose Corp | Manufacture of fibers |
US2484014A (en) * | 1947-01-24 | 1949-10-11 | American Viscose Corp | Production of artificial fibers |
US2745136A (en) * | 1951-03-14 | 1956-05-15 | Deboutteville Marcel Delamare | Apparatus and method for making wool-like artificial fibres |
US3016599A (en) * | 1954-06-01 | 1962-01-16 | Du Pont | Microfiber and staple fiber batt |
US3071809A (en) * | 1960-05-09 | 1963-01-08 | Western Electric Co | Methods of and apparatus for extruding plastic materials |
NL267323A (en) * | 1960-08-05 | |||
US3203215A (en) * | 1961-06-05 | 1965-08-31 | Aeroprojects Inc | Ultrasonic extrusion apparatus |
US3194855A (en) * | 1961-10-02 | 1965-07-13 | Aeroprojects Inc | Method of vibratorily extruding graphite |
US3233012A (en) * | 1963-04-23 | 1966-02-01 | Jr Albert G Bodine | Method and apparatus for forming plastic materials |
US3285442A (en) * | 1964-05-18 | 1966-11-15 | Dow Chemical Co | Method for the extrusion of plastics |
US3341394A (en) * | 1966-12-21 | 1967-09-12 | Du Pont | Sheets of randomly distributed continuous filaments |
US3463321A (en) * | 1967-02-24 | 1969-08-26 | Eastman Kodak Co | Ultrasonic in-line filter system |
US3542615A (en) * | 1967-06-16 | 1970-11-24 | Monsanto Co | Process for producing a nylon non-woven fabric |
DE1785158C3 (en) * | 1968-08-17 | 1979-05-17 | Metallgesellschaft Ag, 6000 Frankfurt | Round nozzle for pulling off and depositing threads to form a thread fleece |
US3978185A (en) * | 1968-12-23 | 1976-08-31 | Exxon Research And Engineering Company | Melt blowing process |
US3849241A (en) * | 1968-12-23 | 1974-11-19 | Exxon Research Engineering Co | Non-woven mats by melt blowing |
US3619429A (en) * | 1969-06-04 | 1971-11-09 | Yawata Welding Electrode Co | Method for the uniform extrusion coating of welding flux compositions |
DE2048006B2 (en) * | 1969-10-01 | 1980-10-30 | Asahi Kasei Kogyo K.K., Osaka (Japan) | Method and device for producing a wide nonwoven web |
DE1950669C3 (en) * | 1969-10-08 | 1982-05-13 | Metallgesellschaft Ag, 6000 Frankfurt | Process for the manufacture of nonwovens |
US3755527A (en) * | 1969-10-09 | 1973-08-28 | Exxon Research Engineering Co | Process for producing melt blown nonwoven synthetic polymer mat having high tear resistance |
US3704198A (en) * | 1969-10-09 | 1972-11-28 | Exxon Research Engineering Co | Nonwoven polypropylene mats of increased strip tensile strength |
GB1344635A (en) | 1970-05-14 | 1974-01-23 | Plessey Co Ltd | Transducers |
GB1355190A (en) * | 1970-09-26 | 1974-06-05 | Secr Defence | Seals |
GB1382828A (en) | 1971-04-02 | 1975-02-05 | Plessey Co Ltd | Liquidspraying devices having a nozzle subjected to high-frequency vibrations |
SU468948A1 (en) | 1971-10-12 | 1975-04-30 | Киевский Ордена Тудовог Красного Знаени Институт Инженеров Гражданской Авиации | "Device for flooding of liquid fuels |
BE793649A (en) * | 1972-01-04 | 1973-07-03 | Rhone Poulenc Textile | DEVICE FOR THE MANUFACTURE OF NONWOVEN CONTINUOUS FILAMENT TABLECLOTH |
US3884417A (en) * | 1972-02-01 | 1975-05-20 | Plessey Handel Investment Ag | Nozzles for the injection of liquid fuel into gaseous media |
GB1471916A (en) * | 1974-03-14 | 1977-04-27 | Plessey Co Ltd | Fuel injection arrangements having vibrating fuel injection nozzles |
GB1481707A (en) * | 1974-07-16 | 1977-08-03 | Plessey Co Ltd | Fuel injection nozzle arrangement |
SU386977A1 (en) | 1972-05-25 | 1973-06-21 | Государственное конструкторское бюро коксохимического машиностроени | JOESSING> &: 6I5L1-1O ' |
US3819116A (en) * | 1972-07-26 | 1974-06-25 | Plessey Handel Investment Ag | Swirl passage fuel injection devices |
GB1415539A (en) | 1972-12-19 | 1975-11-26 | Plessey Co Ltd | Liquid injection system |
GB1432760A (en) | 1972-12-19 | 1976-04-22 | Plessey Co Ltd | Fuel injection systems for engines |
US4038348A (en) * | 1973-03-26 | 1977-07-26 | Kompanek Harry W | Ultrasonic system for improved combustion, emission control and fuel economy on internal combustion engines |
US4100324A (en) * | 1974-03-26 | 1978-07-11 | Kimberly-Clark Corporation | Nonwoven fabric and method of producing same |
JPS5326605B2 (en) * | 1974-07-03 | 1978-08-03 | ||
FR2293988A1 (en) * | 1974-12-11 | 1976-07-09 | Plessey Handel Investment Ag | Fuel injection regulator system - has piezoelectric crystal to vibrate ball valve in jet nozzle |
US4100319A (en) * | 1975-07-14 | 1978-07-11 | Kimberly-Clark Corporation | Stabilized nonwoven web |
GB1552419A (en) * | 1975-08-20 | 1979-09-12 | Plessey Co Ltd | Fuel injection system |
US4064605A (en) * | 1975-08-28 | 1977-12-27 | Toyobo Co., Ltd. | Method for producing non-woven webs |
US4127624A (en) * | 1975-09-09 | 1978-11-28 | Hughes Aircraft Company | Process for producing novel polymeric fibers and fiber masses |
US4198461A (en) * | 1975-09-09 | 1980-04-15 | Hughes Aircraft Company | Polymeric fiber masses, fibers therefrom, and processes for producing the same |
GB1555766A (en) | 1975-09-19 | 1979-11-14 | Plessley Co Ltd | fuel injection systems |
GB1556163A (en) * | 1975-09-19 | 1979-11-21 | Plessey Co Ltd | Fuel injection systems |
JPS6011224B2 (en) * | 1975-11-04 | 1985-03-23 | 株式会社豊田中央研究所 | Ultrasonic fuel injection supply device |
SU532529A1 (en) | 1975-11-05 | 1976-10-25 | Московский Институт Химического Машиностроения | Ultrasonic processing method of polymeric materials |
GB1568832A (en) * | 1976-01-14 | 1980-06-04 | Plessey Co Ltd | Apparatus for metering fuel for an engine |
US4091140A (en) * | 1976-05-10 | 1978-05-23 | Johnson & Johnson | Continuous filament nonwoven fabric and method of manufacturing the same |
DE2622117B1 (en) * | 1976-05-18 | 1977-09-15 | Siemens Ag | FLOW METER |
CA1073648A (en) * | 1976-08-02 | 1980-03-18 | Edward R. Hauser | Web of blended microfibers and crimped bulking fibers |
AU1691276A (en) * | 1976-08-03 | 1978-02-23 | Plessey Handel Investment Ag | A vibratory atomizer |
US4134931A (en) * | 1978-03-16 | 1979-01-16 | Gulf Oil Corporation | Process for treatment of olefin polymer fibrils |
SU706250A1 (en) | 1978-07-27 | 1979-12-30 | Предприятие П/Я Р-6594 | Method of making corrugated tubular articles from thermoplastic materials |
US4372491A (en) * | 1979-02-26 | 1983-02-08 | Fishgal Semyon I | Fuel-feed system |
DE3008618A1 (en) * | 1980-03-06 | 1981-09-10 | Robert Bosch Gmbh, 7000 Stuttgart | FUEL SUPPLY SYSTEM |
DE3010985A1 (en) * | 1980-03-21 | 1981-10-01 | Siemens AG, 1000 Berlin und 8000 München | FUEL INJECTION NOZZLE WITH ADDITIONAL FUEL SPRAYING |
US4340563A (en) * | 1980-05-05 | 1982-07-20 | Kimberly-Clark Corporation | Method for forming nonwoven webs |
US4405297A (en) * | 1980-05-05 | 1983-09-20 | Kimberly-Clark Corporation | Apparatus for forming nonwoven webs |
GB2077351B (en) | 1980-06-06 | 1984-06-20 | Rockwell International Corp | Diesel engine with ultrasonic atomization of fuel injected |
FR2488655A2 (en) * | 1980-08-18 | 1982-02-19 | Rockwell International Corp | FUEL INJECTOR EQUIPPED WITH A ULTRA-SOUND VIBRATION RETENTION CHECK, IN PARTICULAR FOR A DIESEL ENGINE |
DE3124854C2 (en) * | 1981-06-24 | 1985-03-14 | Reinhard 8057 Eching Mühlbauer | High pressure injection system with ultrasonic atomization |
DE3151294C2 (en) * | 1981-12-24 | 1986-01-23 | Fa. Carl Freudenberg, 6940 Weinheim | Spunbonded polypropylene fabric with a low coefficient of fall |
US4496101A (en) * | 1982-06-11 | 1985-01-29 | Eaton Corporation | Ultrasonic metering device and housing assembly |
FR2530183B1 (en) * | 1982-07-13 | 1988-01-22 | Legrand Sa | VIBRATORY ASSISTANCE DEVICE FOR MOLDING INSTALLATION, PARTICULARLY FOR SYNTHETIC MATERIAL |
US4526733A (en) * | 1982-11-17 | 1985-07-02 | Kimberly-Clark Corporation | Meltblown die and method |
JPS59162972A (en) * | 1983-03-07 | 1984-09-13 | Hitachi Ltd | Atomizer |
JPS60104757A (en) * | 1983-11-10 | 1985-06-10 | Hitachi Ltd | Multi-cylinder fuel atomizer for car |
DE3401639A1 (en) * | 1984-01-19 | 1985-07-25 | Hoechst Ag, 6230 Frankfurt | DEVICE FOR PRODUCING A SPINNING FLEECE |
EP0156371B1 (en) * | 1984-03-28 | 1990-05-30 | Hitachi, Ltd. | Fuel dispenser for internal combustion engine |
JPS6198957A (en) * | 1984-10-19 | 1986-05-17 | Hitachi Ltd | Fuel supply device of automobile |
US4726523A (en) * | 1984-12-11 | 1988-02-23 | Toa Nenryo Kogyo Kabushiki Kaisha | Ultrasonic injection nozzle |
JPS61138558A (en) * | 1984-12-11 | 1986-06-26 | Toa Nenryo Kogyo Kk | Oscillator for ultrasonic wave injection nozzle |
JPH0646018B2 (en) * | 1985-01-23 | 1994-06-15 | 株式会社日立製作所 | Fuel atomizer |
JPS61226555A (en) * | 1985-03-29 | 1986-10-08 | Hitachi Ltd | Fuel injector/feeder associated with atomizer |
JPS61259784A (en) * | 1985-05-13 | 1986-11-18 | Toa Nenryo Kogyo Kk | Vibrator for ultrasonic injection |
JPS61259781A (en) * | 1985-05-13 | 1986-11-18 | Toa Nenryo Kogyo Kk | Vibrator for ultrasonic pulverization having curved multistage edge part |
JPS61259782A (en) * | 1985-05-13 | 1986-11-18 | Toa Nenryo Kogyo Kk | Vibrator for ultrasonic atomization having multistage edge part |
JPS61259780A (en) * | 1985-05-13 | 1986-11-18 | Toa Nenryo Kogyo Kk | Vibrator for ultrasonic atomization |
US4663220A (en) * | 1985-07-30 | 1987-05-05 | Kimberly-Clark Corporation | Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers |
JPH065060B2 (en) * | 1985-12-25 | 1994-01-19 | 株式会社日立製作所 | Drive circuit for ultrasonic fuel atomizer for internal combustion engine |
JPH0620528B2 (en) * | 1986-02-06 | 1994-03-23 | 鐘淵化学工業株式会社 | Method of forming uniform droplets |
US4644045A (en) * | 1986-03-14 | 1987-02-17 | Crown Zellerbach Corporation | Method of making spunbonded webs from linear low density polyethylene |
SU1479464A1 (en) | 1986-06-24 | 1989-05-15 | Московский химико-технологический институт им.Д.И.Менделеева | Method of producing articles of polyolephines |
JPS636074U (en) * | 1986-06-27 | 1988-01-16 | ||
DE3713253A1 (en) * | 1986-07-23 | 1988-02-04 | Bosch Gmbh Robert | ULTRASONIC SPRAYER |
DE3724545A1 (en) * | 1987-07-24 | 1989-02-02 | Bosch Gmbh Robert | FUEL INJECTION NOZZLE FOR INTERNAL COMBUSTION ENGINES |
US4793954A (en) * | 1987-08-17 | 1988-12-27 | The B. F. Goodrich Company | Shear processing thermoplastics in the presence of ultrasonic vibration |
DE3912524A1 (en) | 1988-04-20 | 1989-11-02 | Deutsche Forsch Luft Raumfahrt | Device for periodically producing drops of the smallest dimensions |
US4974780A (en) * | 1988-06-22 | 1990-12-04 | Toa Nenryo Kogyo K.K. | Ultrasonic fuel injection nozzle |
US5017311A (en) * | 1988-07-21 | 1991-05-21 | Idemitsu Kosan Co., Ltd. | Method for injection molding into a resonating mold |
JPH069845B2 (en) * | 1988-11-24 | 1994-02-09 | 出光興産株式会社 | Extrusion molding method and apparatus |
US4986248A (en) * | 1989-03-30 | 1991-01-22 | Tonen Corporation | Fuel supply system for internal combustion engine using an ultrasonic atomizer |
US5160746A (en) * | 1989-06-07 | 1992-11-03 | Kimberly-Clark Corporation | Apparatus for forming a nonwoven web |
DE3918663A1 (en) * | 1989-06-08 | 1990-12-13 | Eberspaecher J | FUEL PREHEATING ARRANGEMENT FOR AN ULTRASONIC SPRAYER FOR HEATER |
US5179923A (en) * | 1989-06-30 | 1993-01-19 | Tonen Corporation | Fuel supply control method and ultrasonic atomizer |
US4995367A (en) * | 1990-06-29 | 1991-02-26 | Hitachi America, Ltd. | System and method of control of internal combustion engine using methane fuel mixture |
JPH0486367A (en) * | 1990-07-30 | 1992-03-18 | Aisin Seiki Co Ltd | Fuel injection valve |
DE4101303A1 (en) * | 1991-01-17 | 1992-07-30 | Guenter Poeschl | ARRANGEMENT FOR SPRAYING PRESSURE FROM LIQUID FUEL AND METHOD THEREFOR |
US5226364A (en) * | 1991-03-27 | 1993-07-13 | Rockwell International Corporation | Ultrasonic ink metering for variable input control in lithographic printing |
US5114633A (en) * | 1991-05-16 | 1992-05-19 | Shell Oil Company | Method for the resin-impregnation of fibers |
US5112206A (en) * | 1991-05-16 | 1992-05-12 | Shell Oil Company | Apparatus for the resin-impregnation of fibers |
US5269981A (en) * | 1991-09-30 | 1993-12-14 | Kimberly-Clark Corporation | Process for hydrosonically microaperturing |
US5330100A (en) * | 1992-01-27 | 1994-07-19 | Igor Malinowski | Ultrasonic fuel injector |
US5382400A (en) * | 1992-08-21 | 1995-01-17 | Kimberly-Clark Corporation | Nonwoven multicomponent polymeric fabric and method for making same |
GB2274877A (en) | 1993-02-03 | 1994-08-10 | Ford Motor Co | Fuel injected i.c. engine. |
-
1996
- 1996-05-10 US US08/644,511 patent/US5801106A/en not_active Expired - Lifetime
-
1997
- 1997-04-28 AU AU28164/97A patent/AU2816497A/en not_active Abandoned
- 1997-04-28 WO PCT/US1997/007112 patent/WO1997043468A1/en active Application Filing
- 1997-04-28 CA CA 2249324 patent/CA2249324C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB865707A (en) * | 1956-04-28 | 1961-04-19 | Rasmussen O B | Method of manufacturing artificial fibres |
US4239720A (en) * | 1978-03-03 | 1980-12-16 | Akzona Incorporated | Fiber structures of split multicomponent fibers and process therefor |
EP0644280A1 (en) * | 1993-09-17 | 1995-03-22 | PETOCA, Ltd | Milled carbon fiber and process for producing the same |
WO1996000318A2 (en) * | 1994-06-23 | 1996-01-04 | Kimberly-Clark Corporation | Method and apparatus for increasing the flow rate of a liquid through an orifice |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005016194A1 (en) * | 2005-04-08 | 2006-10-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the preparation of polymer moldings from polymers which are immiscible or poorly miscible with one another |
EP1710065A3 (en) * | 2005-04-08 | 2007-07-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing molded polymers based on non other poorly mixable polymers |
DE102005016194B4 (en) * | 2005-04-08 | 2009-06-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the preparation of polymer moldings from polymers which are immiscible or poorly miscible with one another |
Also Published As
Publication number | Publication date |
---|---|
CA2249324C (en) | 2005-08-23 |
US5801106A (en) | 1998-09-01 |
CA2249324A1 (en) | 1997-11-20 |
AU2816497A (en) | 1997-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6020277A (en) | Polymeric strands with enhanced tensile strength, nonwoven webs including such strands, and methods for making same | |
CA2193724C (en) | Method and apparatus for increasing the flow rate of a liquid through an orifice | |
US5801106A (en) | Polymeric strands with high surface area or altered surface properties | |
US9457538B2 (en) | Absorbent non-woven fibrous mats and process for preparing same | |
EP1639159B1 (en) | Coated nanofiber webs | |
US5652048A (en) | High bulk nonwoven sorbent | |
JP4393513B2 (en) | Fine particles in nanofiber web | |
EP1638496B1 (en) | Articles containing nanofibers produced from a low energy process | |
KR100249638B1 (en) | Method of preparing a nonwoven web of poly(vinyl alcohol) fibers and a disposable absorbent product which includes the nonwoven web | |
US9663883B2 (en) | Methods of producing fibers, nonwovens and articles containing nanofibers from broad molecular weight distribution polymers | |
US20060163152A1 (en) | Porous composite materials comprising a plurality of bonded fiber component structures | |
US8395016B2 (en) | Articles containing nanofibers produced from low melt flow rate polymers | |
CA2605101A1 (en) | Process and apparatus for producing sub-micron fibers, and nonwovens and articles containing same | |
EP4055220A1 (en) | Co-mingling of particulate material and co-axial-meltblown fibers | |
CA2249333A1 (en) | Polymeric strands with enhanced tensile strength, nonwoven webs including such strands, and methods for making same | |
MXPA00000768A (en) | Coform material having improved fluid handling and method for producing |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 2249324 Country of ref document: CA Ref document number: 2249324 Country of ref document: CA Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/A/1998/009387 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref document number: 97540885 Country of ref document: JP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
122 | Ep: pct application non-entry in european phase |