EP0189134A2 - Kettwirkgewebe mit aktiviertem Kohlenstoffgarn als Schusseintrag - Google Patents

Kettwirkgewebe mit aktiviertem Kohlenstoffgarn als Schusseintrag Download PDF

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Publication number
EP0189134A2
EP0189134A2 EP86100570A EP86100570A EP0189134A2 EP 0189134 A2 EP0189134 A2 EP 0189134A2 EP 86100570 A EP86100570 A EP 86100570A EP 86100570 A EP86100570 A EP 86100570A EP 0189134 A2 EP0189134 A2 EP 0189134A2
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EP
European Patent Office
Prior art keywords
yarn
activated carbon
fold
yarns
fabric
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP86100570A
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English (en)
French (fr)
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EP0189134A3 (de
Inventor
Robert Domenico Giglia
Ward Charles Stevens
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Wyeth Holdings LLC
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American Cyanamid Co
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Publication date
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Publication of EP0189134A2 publication Critical patent/EP0189134A2/de
Publication of EP0189134A3 publication Critical patent/EP0189134A3/de
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/32—Apparatus therefor
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles

Definitions

  • This invention relates to activated carbon yarns (multi-fold activated carbon yarns).
  • activated carbon for sorption of toxic chemical vapors or gases is well-known.
  • the use of activated carbon in the form of activated carbon yarns for sorption of toxic substances is also known.
  • U.S. 4,285,831 relates to a process for producing activated carbon fibers reportedly having high adsorption capacity.
  • This patent discloses that by adjusting the amount of bonded oxygen in the oxidized fiber to a certain amount of oxygen, and by controlling the shrinkage of the fiber during the oxidation to a limited value an activated carbon fiber reportedly having excellent adsorption capacity and excellent mechanical properties can be obtained.
  • the oxidized fiber is activated by heating in a gas selected from C0 2 , NH 3 , steam or a mixture thereof, at a temperature of about 200 o C to about 1000°C for 10 minutes to 3 hours while the fiber is allowed to shrink freely.
  • the activated carbon fiber produced has a specific surface area of from 300 m 2 /g to 2,000 m 2 (B.E.T. method using nitrogen gas adsorption isotherm at 25°C).
  • the activated carbon fiber also has a tensile strength of about 20 to about 80 kg/mm 2 , a tensile elongation of about 0.5 to 3% and a tensile modulus of about 1,500 to about 5,000 kg/mm 2 .
  • U.S. 4,412,937 relates to a method for manufacturing activated carbon fiber reportedly having high strength, high adsorbing ability and high processability.
  • the method disclosed comprises preoxidation and activation steps. Before preoxidation, a treating agent, selected from phosphorus and borax compounds, is incorporated with an acrylic fiber. The acrylic fiber is then preoxidized in an oxidizing atmosphere. The concentration of the phosphorous and/or borax in the oxidized fiber is adjusted and then the oxidized fiber is activated. The temperature of activation is in the range of 900 0 C to 1,300°C.
  • U.S. 4,362,646 discloses that the use of an acrylonitrile-based fiber containing an iron compound prevents the coalescence of fibers at the oxidation step, markedly shortens the oxidation time and provides a fibrous activated carbon reportedly having excellent performance in high yields.
  • the patent discloses that the activation processing can be accomplished by physical activation or a method comprising impregnating the fiber with an activating agent used in chemical activation and then applying physical activation. The activation is generally carried out at a temperature of from about 600°C to 1,300°C, preferably about 800°C to about 1,300 0 C for from about 6 seconds to 2 hours.
  • U.S. 4,256,607 relates to a process for producing. an activated carbon fiber reportedly having excellent adsorption capacities and sufficient mechanical strength.
  • the patent discloses a process whereby an acrylonitrile based fiber is subjected to sufficient oxidation in an oxidizing atmosphere at a temperature of about 200 o C to about 300°C while applying a tension until the amount of bonded oxygen reaches about 50% to about 90% of the saturated amount of bonded oxygen.
  • the fiber so obtained is then subject to activation.
  • the activation can be carried out by known methods.
  • the activation is generally carried out at a temperature of about 700 0 to about 1,000° for about 10 minutes to about 3 hours.
  • U.S. patent 4,401,588 relates to making activated carbon fabric by heating an aramid fabric of poly-(benzimidazole) or poly(p-phenylene terephthalamide) under a gaseous stream containing a mixture of inert gas, preferably nitrogen and about 20% by volume steam at a temperature in the range of 850-950 o C for at least 10 minutes.
  • a translation of Japanese Applicantion No. 123784 filed July 17, 1982 and laid-open (published) as No 59-015531-A on January 20, 1984 discloses an active carbon fiber spun yarn which is composed of single fibers whose twist coefficient is 30 to 60.
  • the activated carbon fiber yarn is spun yarn of single yarn or at least two folded yarn.
  • that twist coefficient is of the yarn itself.
  • the twist coefficient is of the primary twist or first twist. If the twist coefficient surpasses 60, the tenacity of the yarn becomes high but snarls will form easily and the processability will become bad; when less than 30, not only will the tenacity of the yarn drop to the extreme but clogging of yarn scraps toward the yarn guide will occur frequently.
  • non-carbon-containing precursor yarns can be intertwined together to form a plied yarn having improved elasticity over the component yarns.
  • these type of plied yarns are not activated carbon yarns they do not have and therefore do not solve the problem associated with activated carbon yarns.
  • This invention provides an activated carbon yarn comprising a plurality of carbon containing precursor yarns, intertwined together to produce a multi-fold yarn and then subjected to an activation process.
  • Another embodiment of this invention provides an activated carbon yarn comprising a plurality of carbon containing precursor yarns, intertwined together to produce a multi-fold yarn and then subjected to an activation process, said activated yarn having a tenacity of greater than about 0.1 gram/denier (g/d) with about 1.0 g/d to about 4 g/d being preferred and a carbon tetrachloride (CC1 4 ) sorptivity of greater than about 25% by weight, based on the weight of activated carbon yarn, with about 25% to about 140% being preferred.
  • g/d 0.1 gram/denier
  • CC1 4 carbon tetrachloride
  • an activated carbon yarn comprising a plurality of oxidized yarns, intertwined together to produce a multi-fold yarn and then subjected to an activation process, said activated carbon yarn having a tenacity greater than about 1 g/d and a CC1 4 sorptivity of greater than about 60% by weight based on the weight of activated carbon yarn.
  • the oxidized yarn is an oxidized acrylic yarn.
  • Yet another embodiment of this invention provides articles of manufacture made from the activated carbon yarns of this invention, in particular articles of manufacture which are fabrics and the objects made therefrom --e.g. garments (clothing), tents, masks, and the like.
  • activated carbon material can be treated with an aqueous dispersion of polymeric fluorocarbon resin particles to provide an activated carbon material coated with a polymeric fluorocarbon.
  • the polymeric fluorocarbon coating provides the activated carbon material with increased abrasion resistance without decreasing CC1 4 sorptivity. This is surprising and unexpected because one skilled in the art would expect that a coating placed on the activated carbon material would occlude the activation sites causing decreased sorptivity. However, contrary to expectations, activated carbon materials do not exhibit a decreased sorptivity when coated with polymeric fluorocarbons.
  • this invention in another embodiment provides an activated carbon material coated with a polymeric fluorocarbon and having increased abrasion resistance comprising an activated carbon material treated with an aqueous dispersion of polymeric fluorocarbon resin particles.
  • this invention provides an activated carbon yarn comprising a plurality of carbon containing precursor yarns, intertwined together to produce a multi-fols yarn, and then subjected to an activation process, and then treated with an aqueous dispersion of polymeric fluorocarbon resin particles.
  • this invention provides a process for making an abrasion resistant activated carbon material comprising immersing or dipping an activated carbon materia in, or spraying an activated carbon material with, an aqueous dispersion of polymeric fluorocarbon resin particles and then drying said material.
  • this invention provides an improved warp knitted activated carbon fabric comprising a weft of a multi-fold activated carbon yarn and a warp of a hydrophobic, monofilament yarn.
  • a hydrophilic layer is incorporated on one side of the above described warp knitted activated carbon fabric.
  • the fabrics of this invention may be used in clothing or fabric enclosures -- e.g., tents, window covers, and the like -- to protect individuals from toxic chemical vapors.
  • the invention may also be used as air filters and in water treatment as well as other applications requiring the filtration of toxic chemical vapors, gases and liquids.
  • the carbon containing precursors in the above embodiments are oxidized acrylic yarns.
  • the multi-fold activated carbon yarns of this invention can be activated to a higher CC1 4 sorptivity on a weight for weight basis than a single ply yarn (of which the multi-fold yarn is composed of) and still maintain high levels of tenacity.
  • This is unexpected because it appears that the multi-fold yarn.has less fiber surface exposed to the activating gas stream due to the intertwining of the single plies.
  • the reduced surface area would result in reduced activation of the yarn resulting in reduced sorptivity capabilities.
  • the multi-fold activated carbon yarns of this invention also have greater ability to deform or distort in response to an applied force (such as that encountered during a commercial weaving process). This ability to deform or distort is due to increased elasticity resulting from intertwining the plies of yarn together before the activation process.
  • char yield means that a carbon residue remains after the yarn has been pyrolyzed (usually at 1000°C).
  • twist coefficient refers to the primary yarn and as used herein means the:
  • twist ratio means the ratio of the twist (final twist) of the activated carbon yarn to the twist of the primary yarns.
  • primary yarn refers to the individual plies or the multi-fold yarn.
  • Carbon containing yarns comprising one of the following precursors may prove useful in producing the activated carbon yarns of this invention: phenolic, poly(benzimidazole), poly(p-phenyleneterephthalamide), polyacrylonitrile, pitch (petroleum or coal tar), and the like.
  • Examples of commercially available yarns are: KYNOL, a produce designation for a phenolic-aldehyde yarn available from American Kynol, Inc.; KEVLAR O 49, brand of aramid yarn from E. I. du Pont de Nemburs & Co., Inc.; PYRON O brand of oxidized polyacrylonitrile yarn from Stackpole Fibers Co., Inc.; CELIOX O brand of oxidized polyacrylonitrile yarn from Celanese Corporation, Celion Fiber Division; GRAFIL '0', a product designation for an oxidized polyacrylonitrile yarn from Hysol Grafil Limited; FORTAFIL® OPF brand of oxidized polyacrylonitrile yarn from Great Lakes Carbon Corp.
  • oxidized acrylic yarns are widely used with acrylonitrile oxidized yarns being preferred.
  • a preferred oxidized acrylonitrile based acrylic yarn is available from Celanese Corporation, Celion Carbon Fiber Division under the trademark CELIOX®.
  • Yarns made from fibers of acrylonitrile homopolymers and acrylonitrile copolymers and then oxidized are suitable for use in this invention.
  • copolymers may include copolymers containing not less than about 60% by weight, preferably not less than 85% by weight, acrylonitrile.
  • Copolymers containing less than about 60% by weight acrylonitrile may be used in admixture with acrylonitrile polymers to produce the fiber, if the amount of acrylonitrile in the ultimate fiber exceeds 60% by weight.
  • Comonomers which may be introduced into the above copolymers include addition-polymerizable vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl bromide, acrylic acid, methacrylic acid, itaconic acid; the salts (e.g., the sodium salts) of these acids; derivatives of these acids, e.g., acrylic acid esters (e.g., alkyl esters containing 1 to 4 carbon atoms in the alkyl moiety such as methyl acrylate, butyl acrylate, and the like), methacrylic acid esters (e.g., alkyl esters containing 1 to 4 carbon atoms in the alkyl moiety such as methyl methacrylate, and the like); acrylamide, N-methylolacrylamide; allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and the salts (e.g., the sodium salts) of these acids; vinyl acetate; 2-hydroxyeth
  • the degree of polymerization of these polymers or polymer mixtures will be sufficient if a fiber can be formed, and it is generally about 500 to about 3,000, preferably 1,000 to 2,000.
  • acrylonitrile based polymers can be produced using hitherto known methods, for example, suspension polymerization or emulsion polymerization in an aqueous system, or solution polymerization in a solvent. These methods are described in, for example, U.S. 3,208,962, U.S. 3,287,307 and U.S. 3,479,312.
  • Spinning of the acrylonitrile based polymer can be carried out by hitherto known methods.
  • spinning solvents which can be used include inorganic solvents such as a concentrated solution of zinc chloride in water, concentrated nitric acid and the like, and organic solvents such as dimethylformamide, dimethyl- acramide, dimethyl sulfoxide, and the like.
  • spinning methods which can be used are dry spinning and wet spinning. In wet spinning, in general, steps such as coagulation, waterwashing, stretching, shrinking, drying and the like are suitably combined. These spinning methods are described in U.S. 3,135,812 and U.S. 3,097,053.
  • This stretching is carried out to the same extent as in a usual acrylonitrile based fiber, and a suitable degree of stretching is generally about 5 to about 30 times the original length.
  • the conditions by which the yarn is oxidized effect the physical properties of the resulting oxidized yarn.
  • the resulting oxidized yarn will vary in physical properties--e.g., stability.
  • stability it is meant that the fiber structure is heat resistant and will not melt, nor will neighboring fibers coalesce in the temperature range 200°C to 1000 o C.
  • the physical properties and the polymeric makeup of the oxidized yarn effect the activation conditions under which the activated carbon yarns of this invention having optimum properties can be obtained.
  • optimum properties it is meant a tenacity of at least about 1 g/d and a CC1 4 sorptivity of greater than about 60% by weight, based on the weight of the activated carbon yarn. Therefore, those skilled in the art can appreciate that oxidized yarns, differing in polymeric makeup and/or method of oxidation, may have to be activated under conditions-- e.g., temperature, gas flow rate, and through-put rate--which vary from yarn to yarn in order to obtain activated carbon yarns having optimum properties. However, such conditions may be determined by those skilled in the art without undue experimentation.
  • a plurality of carbon containing precusor yarns preferably oxidized acrylic yarns, or a combination of different carbon containing precusor yarns are brought together and arranged spatially by intertwining to form a multi-fold yarn structure.
  • Intertwining is defined as including any method for making yarns including the art recognized methods for making yarns from staple or continuous filaments--e.g., twisting or braiding. Methods for making yarns and the configurations by which yarns are made--e.g., braided or twisted--are well known in the art.
  • the multi-fold yarn for the activation process is made by longitudinally twisting or braiding together a plurality of carbon containing precusor yarns.
  • the carbon containing precuror yarns generally have a twist coefficient greater than about 65 and usually within the range of from about'65 to about 150.
  • the multi-fold yarn made by twisting generally has from about 0.5 to about 10 turns per inch.
  • the twist ratio is generally within the range of about 0.1 to about 0.5.
  • the multi-fold yarn is generally made from about 2 to about 20 carbon containing yarns, preferably oxidized acrylic yarns, with about 3 to about 10 being preferred.
  • the yarns can be intertwined together at one time or a given number of yarns can be intertwined together to form a unit and then a given number of units can be intertwined together to form the multi-fold yarn for activation.
  • 2 oxidized acrylic yarns can be intertwined to form a pair and then 3 pairs can be intertwined to form the multi-fold yarn for activation.
  • the denier of the individual plies and consequently the denier of the plied yarn are generally chosen to meet specific requirements of the end product.
  • 6 oxidized acrylic spun yarns of 10 worsted count (797 denier) were plied and activated to yield a plied yarn of from about 20 to 6 worsted count (400 to 1300 denier).
  • the multi-fold yarn is then subjected to an activation process.
  • a continuous activation process can be utilized.
  • the multi-fold yarn is continuously pulled or fed through at least one hot zone (furnace) while passing an activating gas through the hot zone.
  • the gas for example, can be passed through the hot zone counter current to the direction of the multi-fold yarn.
  • Multiple hot zones for example 2, can be utilized--see for example FIG. I--to supply the energy requirements of the process.
  • the conditions of the temperature, gas flow rate, through-put rate and the tension the yarn is held at during the process are such that an activated carbon yarn is produced having a tenacity greater than about 0.1 g/d and a CC1 4 sorptivity of greater than about 25% by weight, based on the weight of the activated carbon yarn.
  • the activated carbon yarn produced preferably has a tenacity of about 0.1 g/d to about 4 g/d with about 1 to about 4 g/d being most preferred and greater than about 2 g/d being even more preferred.
  • the yarn produced has a CC1 4 sorptivity of about 25% to about 140% by weight, based on the weight of activated carbon yarn, with greater than about 60% being most preferable and greater than about 75% being even more preferable.
  • the physical properties of the activated carbon yarn obtained will have some variation based upon the denier of the precursor yarn and, as discussed above, the denier is generally chosen for specific applications.
  • activation conditions for a continuous process are as follows: the temperature range of the furnace(s) is high enough to allow activation to occur under the conditions of operation, but not so high as to cause unnecessary degradation of the multi-fold yarn; thus the temperature is generally from about 700 to about 1300°C with about 900 to about 1150 being preferred.
  • the gas flow rate, yarn through-put rate, and yarn tension can vary because they are dependent on the precursor, the precursor's denier, and hot zone lengths, and these parameters are interactive with each other. Thus, as indicated, some experimentation may be required to determine the ranges for these parameters that will yield optimum physical properties of the yarn.
  • the gases which are suitable for use in the activation process are well known in the art.
  • the amount of allowable oxygen is such that the fiber does not burn, and the concentration is generally not more than 3 vol %.
  • One or more inert gases such as N 2 , Ar or He may be contained in an activation gas in an amount of up to about 50 vol % of--e.g., C0 2 and N 2 , and the like.
  • C0 2 which is bubbled through a gas washing bottle containing H 2 0 imparting a H 2 0 vapor content to the C0 2 is utilized.
  • FIG. 1 A diagram showing an example of a continuous activation process scheme for the production of an activated carbon yarn utilizing two furnaces is shown in FIG. 1.
  • a precursor spool (1) contains the carbon containing yarn (2).
  • Tension is applied to the yarn with a spring tension device (12) with the tension being monitored by a tension meter (3).
  • the yarn is pulled longitudinally, entering into a quartz reaction tube (4a) which is heated in a furnace (5a), for example, a Lindberg furnace.
  • the yarn exits the quartz reaction tube (4a') and enters the second quartz reaction tube (4b) which is in a furnace, (5b), for example, a Lindberg furnace.
  • a digital thermometer monitors the temperature of entering gas.
  • the equipment in processing unit 14 is equivalent to the equipment in processing unit 13. If only one furnace is used in the activation process then either unit 13 or unit 14 would be eliminated. If more than two furnaces are utilized, other units equivalent to units 13 and 14 would be added.
  • Precursor yarns of this invention may be activated in furnace at 900 0- 1300 0 C containing a flowing activating gas. The residence time would determine the degree of activation.
  • FIG. 2 is a schematic of the yarn feed-through entrance (4a and 4b of FIG. 1).
  • FIG. 3 is a schematic of the yarn feed-through exit (4a' and 4b' of FIG. 1).
  • the yarn enters through 15 (FIG. 2) and exits through 17 (FIG. 3).
  • the activating gas enters through 18 (FIG. 3).
  • the yarn feed-througbs are connected to pyrex and caps, which in turn are connected to the quartz reaction rube by ground glass joints, for example 24/40 around glass joints, (16 and 19, FIG. 2 and 3, respectively).
  • the present invention provides new and improved activated carbon fiber yarns and cloths provided with a polyfluorocarbon coating which are characterized by imprpoved abrasion resistance and weav- ability of the fibers, without adversely affecting their toxic chemical sorbitivity.
  • polymeric fluorocarbon resins utilized in this aspect of the invention are those capable of being made into an aqueous dispersion and are well known to those skilled in the art.
  • Such polymeric fluorocarbons include for example: polytetraflurooethylene and fluorinated ehtylenepropylene polymers, and the like. Polyhexa- fluoropropylene may also prove useful.
  • These polymeric fluorocarbon resins are available, for example, from E. I. duPont de Nemours & Co., Inc. under the trademark TEFLON@.
  • An example of such a resin is TEFLON® 30B TFE.
  • the polymeric fluorocarbon resin coating imrpoits the abrasion resistance of activated carbon fibers, reduces the release of carbon fiber particulates, i.e., fly, produced by abrasion, and creates a hydrophobic surface without reducing the chemical sorptivity'of the cloth.
  • the activated carbon material can be immersed or dipped in an aqueous dispersion of the fluorocarbon resin particles or can be sprayed with an aqueous dispersion of the fluorocarbon resin particles.
  • An example of such a resin is TEFLON O 30B TFE which is a tetrafluoroethylene resin.
  • any commercially available aqueous dispersion of fluorocarbon resin particles can be used, such as those available under the trademark TEFLON®.
  • a suspension having particles ranging in size from about 0.05 microns to about 0.5 microns can be used.
  • the coated activated material is then dryed to remove the water at ambient temperatures or with the application of heat, such as in an oven at a temperature of about 90 to about 250°C.
  • the concentration of the aqueous dispersion can vary depending on the amount of coating desired on the activated carbon material. In general, the amount of coating placed on the activated carbon material will not effect sorptivity, but will effect the weight of the activated carbon material. Thus, considerations of the desired weight of the coated activated carbon material will basically determine the amount of coating placed on the material. Therefore, any concentration of % solids of fluorocarbon resin in an aqueous dispersion sufficient to coat the activated carbon material can be used. For example, among the aqueous dispersions that can be used are those containing about 0.01% to about 10% solids (e.g., 0.01%, 0.1%, 0.5%, 1%, 5%, and 10% solids).
  • this coating should allow activated fibers or yarns to be processed with conventional textile equipment that would destroy or greatly reduce the properties of uncoated fibers or yarns. Thus activated yarns or fibers may be woven or knit into useful articles.
  • the life of the garment, made from coated fibers or coated subsequent to manufacture, should increase as a result of improved abrasion resistance. Less fly is produced, which decreases safety hazards, when materials are coated.
  • the coating also creates a hydrophobic surface and repels water and chemical agents that might be contained within an aqueous media.
  • any activated carbon material can be increased by coating with the fluorocarbon resin as described herein.
  • the invention provides and improved warp knitted activated carbon fabric comprising a weft of a multi-fold activated carbon yarn and a warp of a hydrophobic polymeric monofilament yarn wherein every course of said activated yarn is inserted across the full width of said fabric with said monofilament being in the wales and courses of said fabric.
  • the activated carbon fabrics of this invention can be produced by a variety of knitting designs known in the art e.g., tricot or raschel knit fabric design.
  • a tricot knit fabric of this invention has a design pattern represented by the bar movement pattern:
  • the leakage encountered with prior art fabrics is at least partially due to a "wicking effect.” Since the protective yarn is, for example, wrapped or braided along the entire length of the activated carbon yarn a leakage path is established from outside to inside by a "wicking effect" when, for example, the fabric gets wet. This wicking effect is overcome by the use in this invention of a hydrophobic monofilament yarn as the warp.
  • the monofilament yarns suitable for use include for example: polyesters such as DENIER 20/1 SEMIDOLL MONOFIL available from Hanover Mills Inc., NY, NY.
  • the monofilament generally has a denier of about 10 to about 100, with about 10 to about 30 being preferred and about 15. to about 20 being most preferred.
  • the warp knit fabrics of this invention have monofilament yarn in the warp while activated carbon yarn is weft inserted a selected number of courses per inch- i.e., from about 20 to about 60 courses per inch with about 24 to about 50 being preferred and about 30 to about 40 being most preferred--to provide a warp knit fabric which is flexible and has high sorptive capacity for toxic chemical vapors and gases and liquids, is reasonably strong, and has sufficiently good abrasion resistance to retain a large amount of sorptivity for toxic chemical vapors even after being subjected to considerable abrasion.
  • the warp knit fabrics may be produced on tricot type or raschel type warp knitting machines modified so as to insert the unprotected activated carbon yarn as weft while the monofilament yarn is being warp knitted.
  • Such apparatuses and methods are exemplified by U.S. Patent No. 3,364,701 and U.S. Patent No. 3,495,423.
  • the activated carbon yarn utilized has excellent tenacity, flexibility and abrasion resistance, during experimental testing in a commercial weaving process, it occasionally snags and is subject to a minimal amount of breakage around sharp angle bends in the commercial weaving equipment. It is to be noted that the breakage which occurs with these multi-fold activated carbon yarns is much less than that which occurs with other activated carbon yarns.
  • the knitting equipment may be modified, for example, by placing plastic sleeves at sharp angle bends to guide the yarn through.
  • the warp knit fabric contain at least 2 oz/yd 2 of the activated carbon yarn with about 3 oz/yd 2 to about 7 oz/yd 2 being most preferred. It is also preferred that the warp knit fabric have an ai" permeability of at least 50 cubic feet/minute/square foot of fabric wiht about 200 ft 3 /min/ft 2 to about 1000 ft 3 /min/ft 2 being most preferred.
  • Clothing constructed of warp knit fabric having the above-stated-preferred characteristics will be effective for protecting the wearer of such clothing against toxic chemical vapors or gasses for a reasonable length of time, depending on the concentration of such vapors or gases in the atmosphere, and may be worn without experiencing undue heat stress since the fabric breathes while sorbing the toxic chemical vapors or gases and is relatively light weight due to the absence of multilayers and excessive support yarns to protect the activated carbon yarn.
  • a layer of hydrophilic fiber is incorporated on to one side of the warp knit fabric described above.
  • This can be done by known knitting methods as for example, in the manner described in FIG. 9 by, for example, the addition of a third beam to a knitting machine of the Karl Mayer type.
  • the added layer When the added layer is placed toward the skin of the wearer it improves abrasion resistance, protects the wearer against carbon fiber cut ends and serves to spread perspiration for easy release through to the outside of the fabric Since this added layer is on one side only and does not penetrate the activated carbon yarn layer, it does not produce a leakage path for toxic liquid agents.
  • Hydrophilic fibers or yarns which are useful include but are not limited to: 50/50 polyester/cotton (polycotton), 100% cotton, 100% polyester, rayon, wool, and linen.
  • the hydrophilic yarns have a denier of about 100 to about 300 with about 150 to about 250 being preferred and about 175 to about 190 being most preferred. It is anticipated that the addition of the second layer will add only about 1 to about 1.5 oz/yd 2 to weight of the warp knitted fabric described above.
  • the tenacity of the activated carbon yarns was determined by measuring the load required to break the multi-fold yarn. These loads were measured with a tensile testing machine manufactured by Testing Machines, Inc. of New York. Six-inch yarn lengths were gripped by two pairs of one-inch square rubber-faced jaws, three inches apart. The loads were measured to the nearest 0.01 pound. Tenacities were then calculated by dividing that load, in grams, by the denier of the yarn tested. Yarn deniers (yarn weight per 9000 meters of yarn) were determined by weighing 20 cm. lengths of yarn.
  • An oxidized acrylic yarn was activated in the system own in FIG 1.
  • CELIOX O brand of oxidized acrylic yarn available from Celanese Corporation, was pulled through two 5.4 cm (ID) by 120 cm long quartz reaction tubes. Each tube was placed within a Lindberg Model 54352 tube furnace. The speed of the yarn through the system was controlled by take-up rolls and tension in the yarn was monitored with a Tensilon tension meter. Yarns entered and exited the reaction tube through pyrex end caps and feed throughs. Flowing countercurrent to the fiber line was a stream of humidified carbon dioxide. Humidificaticn was achieved by bubbling the gas through heated gas washing bottles. The temperature of the gas was measured just prior to entering the furnace. A Tylan mass flow controller was used to control and monitor the flow of carbon dioxide into each washing bottle.
  • the sample of activity carbon yarn for determining tenacity and CC1 4 sorptivated was taken from the end of about a 200 yard length of the activated carbon yarn-- i.e., after about 200 yards of yarn had been subjected to the activation process, a sampling was taken from the end of that length for testing.
  • Table 1 reports the results for the 19 samples from which the average tenacity and average CC1 4 sorptivity was determined.
  • Examples 7-23 lists the % CC1 4 sorptivity and the tenacity (Example 12 only) for activated carbon yarns made from CELIOX O brand of oxidized acrylic yarn. Following the procedure of Examples 3-6, six oxidized yarns each having a worsted count of 10 were intertwined by twisting to form a single plied yarn (multi-fold yarn). The multi-fold yarn was activated in a single furnace at the conditions listed in Table 3, using carbon dioxide as the oxidizing gas. One multi-fold yarn was activated at a time and line tensions are approximate.
  • Examples 24-26 lists the % CC1 4 sorptivity and the tenacity for activated carbon yarns made from CELIOX® brand of oxidized acrylic yarn.
  • multi-fold yarn Following the procedure of Example 1, six oxidized yarns each having a worsted count of 10 were intertwined by twisting to form a single plied yarn (multi-fold yarn).
  • the multi-fold yarn was activated using two furnaces at the conditions listed in Table 4 using carbon dioxide as the oxidizing gas.
  • One multi-fold yarn was activated at a time and gas temperature and line tensions are approximate.
  • Examples 27-34 lists the % CC1 4 sorptivity and the tenacity for activated carbon yarns made from CELIOX O brand of oxidized acrylic yarns.
  • multi-fold yarn Following the procedure of Example 1, six oxidized yarns each having a worsted count of 10, were intertwined together by twisting to form a single plied yarn (multi-fold yarn).
  • the multi-fold yarn was activated using two furnaces at the conditions listed in Table 5. Nitrogen gas was used in the first furnace and carbon dioxide gas was used in the second furnace. One multi-fold yarn was activated at a time and gas temperatures are approximate.
  • Examples 50-59 lists the results of experiments which provided yarns with less than optimum properties.
  • the procedure and oxidized yarns used were the same as in Examples 1 and 24-26.
  • the multi-fold yarn was activated at the conditions listed in Table 7 using carbon dioxide as the oxidizing gas and gas temperatures and line tesions are approximate.
  • Examples 60-68 lists the results of experiments which provided yarns with less than optimum properties.
  • the procedures and oxidized yarns used were the same as in Examples 27-34.
  • the multi-fold "arn was activated at the conditions listed in Table 8 using carbon dioxide as the oxidizing gas. The gas temperatures are approximate.
  • the yarns were then laid on aluminum foil and were dried at 115 0 C for 1 hour. To determine the percentage weight gain of TEFLON O 30B TFE resin, the yarns were evacuated for 1 hour, backfilled with nitrogen and reweighed. Each yarn was then tested to determine CC1 4 sorptivity. The results are shown in Table 9.
  • the same concentrations of solids in suspensions were used to continuously coat the same activated carbon yarns for mechanical testing.
  • the activated carbon yarn contained on a spool (1) was pulled through a dip tank containing the suspension (2) and then through an 18 inch hot zone (3), at about 170°C, with take-off rolls (4) at a speed of about 20 inches/minute.
  • FIG. 6 represents how the abrasion resistance of the yarn was tested by drawing a weighted yarn over a yarn hook/guide (1) from a Karl Meyer Weftamatic Warp Knit Machine. The yarn was pulled down one inch and released up one inch (2) with a 50 gm weight (3) attached to the other end of the yarn. This down-up motion comprised one cycle. This was repeated until the yarn broke. The number of cycles to failure was noted and are listed in Table 9.
  • a TEFLON® 30B TFE suspension containing about 1% solids was used to dip and spray coat activated carbon fiber yarns described in Example 69.
  • a glass atomizer similar to Kontes Model Number 42250 Thin Layer Chromatography Sprayer was used to spray the suspension. Samples were dried at about 135 0 C for about 0.5 hours.
  • the yarns were tested for CCL 4 sorptivity and abrasion resistance as described in Example 69. CC1 4 sorptivities are based on the yarn plus coating weight. The results are shown in Table 10.
  • Activated carbon yarn in the form of continuous untwisted tow, was dipped into a TEFLON® 30B TFE suspension containing about 1% solids. The tow was then dried at 135°C for about 0.5 hours. The coating weight was found to be about 2% based on the weight of the uncoated fiber.
  • CC1 4 sorptivity and abrasion resistance were determined as in Example 69 and the.results are shown in Table 11.
  • One sheet was dipped into a suspension containing about 1% of TEFLON® 30B TFE solids and was dried at 135 0 C to yield a coating weight of about 15% based on the initial fabric weight.
  • a plain weave fabric of Kuractive activated carbon fiber cloth (available from Kuraray Chemical Co., Ltd., Japan) was dipped into a suspension containing about 1% of TEFLON® 30B TFE solids and was dried at 135 0 C.
  • the coating weight was determined to be about 6% based on the initial fabric weight. Water was found to bead up on the TEFLON® 30B TFE coated Kuractive woven cloth whereas water was quickly absorbed into the uncoated cloth.
  • the analyzer was tuned to the 12.6 micron absorbance band of CC1 4 . Calibration of the analyzer was achieved prior to the run by injecting known amounts of CC1 4 into a recirculating air pump. At a flow of one 1/min, as establizhed by a rotometer (10), the breakthrough concentration of CC1 4 downstream from the filler was set at 0.5 mg/l as specified in MIL-C-43558. Excess gas was vented through (11). Apparatus (2), (3), (4), and (7) were maintained at a constant temperature of 32.5 ⁇ 1°C in an oven (12). The dynamic CC1 4 adsorption was calculated as follows: where t b is the breakthrough time in minutes. The military specification for chemical protective clothing is 1.8 mg/cm 2 . The results of these tests are shown in Table 12.
  • a six-ply CELIOX O oxidized stabilized yarn having a worsted count of 6/10 was activated using the single furnace technique described in copending Application Serial No. (Case 29,733), filed (herewith).
  • the multi-fold yarn had a twist coefficient of about 87.5 and a twist ratio of about 0.2.
  • the activated carbon yarn has a tenacity of 1.3 g/d, weight 1300 denier and static sorption to CC1 4 greater than 80% by weight, based on the weight of the activated carbon yarn.
  • the yarn was knitted into fabric using a Karl Mayer Weftamatic Warp Knit Machine and a 2 bar chain stitch plus tricot. Monofilament polyester of 20 denier was machine fed in the warp while-the activated carbon yarn was fed in the weft. Testing yielded the following characteristics:
  • MIL-C-43858 (GL) lists the following requirements:

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Fibers (AREA)
  • Woven Fabrics (AREA)
  • Knitting Of Fabric (AREA)
EP86100570A 1985-01-18 1986-01-17 Kettwirkgewebe mit aktiviertem Kohlenstoffgarn als Schusseintrag Ceased EP0189134A3 (de)

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US69295985A 1985-01-18 1985-01-18
US69296085A 1985-01-18 1985-01-18
US69296185A 1985-01-18 1985-01-18
US692961 1985-01-18
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753087A1 (de) * 1994-03-28 1997-01-15 Hitco Technologies Inc. Verfahren zur herstellung von biegsamen kohlenstoffgarnen und kohlenstoffgegenstände damit zubereitet
US20160265144A1 (en) * 2013-10-29 2016-09-15 Kolon Industries, Inc. Activated carbon fiber and preparation method therefor
CN113735122A (zh) * 2021-08-17 2021-12-03 山东利特纳米技术有限公司 一种疏水活性炭的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1290039A (fr) * 1961-05-26 1962-04-06 Du Pont Tissus enduits d'un polymère pour paliers auto-graisseurs
JPS5641818A (en) * 1979-09-10 1981-04-18 Mitsubishi Rayon Co Ltd Nonwoven fabriclike activated carbon fiber and its manufacture
US4351816A (en) * 1980-12-17 1982-09-28 Union Carbide Corporation Method for producing a mesophase pitch derived carbon yarn and fiber

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1290039A (fr) * 1961-05-26 1962-04-06 Du Pont Tissus enduits d'un polymère pour paliers auto-graisseurs
JPS5641818A (en) * 1979-09-10 1981-04-18 Mitsubishi Rayon Co Ltd Nonwoven fabriclike activated carbon fiber and its manufacture
US4351816A (en) * 1980-12-17 1982-09-28 Union Carbide Corporation Method for producing a mesophase pitch derived carbon yarn and fiber

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 95, no. 8, August 1981, page 67, abstract no. 63615m, Columbus, Ohio, US; & JP-A-81 41 818 (MITSUBISHI RAYON CO., LTD) 18-04-1981 *
TEXTILE CHEMIST AND COLORIST, vol. 4, no. 2, February 1972, pages 33-36; J.H. ROSS: "A chemical finish system to enhance weaving of carbon and graphite yarns" *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753087A1 (de) * 1994-03-28 1997-01-15 Hitco Technologies Inc. Verfahren zur herstellung von biegsamen kohlenstoffgarnen und kohlenstoffgegenstände damit zubereitet
EP0753087A4 (de) * 1994-03-28 1997-06-18 Hitco Technologies Inc Verfahren zur herstellung von biegsamen kohlenstoffgarnen und kohlenstoffgegenstände damit zubereitet
US6248443B1 (en) 1994-03-28 2001-06-19 Hitco Carbon Composites, Inc. Process for the preparation of flexible carbon yarn and carbon products therefrom
US20160265144A1 (en) * 2013-10-29 2016-09-15 Kolon Industries, Inc. Activated carbon fiber and preparation method therefor
CN113735122A (zh) * 2021-08-17 2021-12-03 山东利特纳米技术有限公司 一种疏水活性炭的制备方法

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