Classifications

• • 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
  • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues

Definitions

• This invention relates to a spin size and thermosetting aid for pitch fibers.
• the present invention provides a method of treating a multifilament bundle of pitch fibers, such as yarn or tow, to prepare such multifilament bundle for further processing which comprises applying to the fibers thereof an aqueous finishing composition comprising a dispersion of graphite or carbon black in water in which is dissolved a water-soluble oxidizing agent and a water-soluble surfactant.
• the aqueous dispersion employed to treat a multifilament bundle of pitch fibers according to the present invention serves as both a size for the bundle and as an effective thermosetting aid during the infusibilization step which must be conducted before the fibers can be carbonized to produce the desired product. Because the graphite or carbon black particles are applied as a finely-divided dispersion, more effective penetration of these particles between the filaments of the bundle is achieved. As a result of this increased penetration of the particles, greater lubricity is provided between the filaments which helps prevent physical damage to the fiber surfaces during subsequent processing.
• the separation of the fiber bundle caused by the infiltration of these minute particles between the filaments allows improved penetration of the oxidizing gas into the bundle during thermosetting, which helps reduce oxidation time and the exothermic excursion and filament fusion which ordinarily occurs at that time. As noted previously, such fusion reduces the flexibility and tensile strength of the yarn or tow.
• Either finely-divided graphite or carbon black can be employed in the dispersions employed in the present invention.
• Materials such as activated carbon and coal are undesirable because they are abrasive and contain a high amount of inorganic impurities (usually several percent) which is known to cause pitting of the fiber surfaces during oxidation and a concomitant loss of fiber strength.
• inorganic impurities usually several percent
• the graphite or carbon black should contain less than 0.5 percent by weight of inorganic impurities. This inorganic impurity content is usually measured by determining the ash content of such materials.
• any form of carbon black e.g. gas blacks, furnace combustion blacks, furnace thermal blacks, lampblacks, may be employed in the dispersions of the present invention.
• any form of graphite either natural or synthetic, can be employed.
• they should be no greater than 15 microns in size.
• they Preferably, they have a size of from 0.3 micron to 5 microns. Because of the small size of these particles they readily infiltrate the fiber bundle and uniformly coat the filaments. When the fiber bundle is further processed, these soft and slippery particles readily slide over each other and over the filaments so that the fibers are less subject to breakage and damage.
• the separation of the fiber bundle caused by the infiltration of these minute particles between the filaments facilitates permeation of the oxidizing gas into the bundle during thermosetting.
• This increased permeation of oxygen into the fiber bundle reduces the oxidation time and allows the fibers to be processed at greatly increased speeds.
• an exotherm excursion occurs during oxidation which causes fusion of the filaments to occur.
• the filament surfaces are brought into contact with the oxidizing gas to a greater content during oxidation and such heat excursion is prevented.
• the dispersion contains from about 0.1 part by weight to about 10 parts by weight of graphite or carbon black per 100 parts by weight of mixture, preferably from 1 part by weight to 6 parts by weight of graphite or carbon black per 100 parts by weight of mixture..
• thermosetting aid in the aqueous dispersions employed in the present invention, provided such compound does not cause the suspension to flocculate. Because the compounds employed are water soluble, their physical presence on the fiber surfaces during thermosetting is assured. Oxidation and infusibilization of the fibers is thereby enhanced during thermosetting, allowing the fibers to be processed at greatly increased speeds.
• Suitable oxidizing agents include peroxygenated compounds, for example, peroxides, persulfates, pyrosulfates, and perchlorates.
• Sulfates, sulfites, bisulfites sulfamater. and nitrates are alse suitable, including, for example, sodium sulfate, potassium sulfate, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium sulfamate, potassium sulfamate, sodium nitrate, and potassium nitrate.
• sodium sulfate, potassium sulfate, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium sulfamate, potassium sulfamate, sodium nitrate, and potassium nitrate are particularly useful, because such salts leave residues on the fiber
• Any water soluble surfactant can be employed in the aqueous dispersions employed in the present invention, provided such surfactant does not cause the suspension to flocculate.
• Anionic and nonionic surfactants are preferred for this reason.
• Such surfactants serve to increase wetting of the fibers by the dispersion by reducing the surface tension of the water, thereby promoting the distribution of the graphite or carbon black throughout the fiber bundle. As a result, oxidation and infusibilization of the fibers during thermosetting is enhanced and the fibers can be processed at greatly increased speeds.
• Suitable surfactants include tetramethyl sodium oleate, tetramethyl sodium laurate, sodium laurate, and the like. However, because such salts leave residues on the fibers and may cause pitting of the fiber surfaces during oxidation, it is preferred to use the corresponding ammonium salts.
• an amount of surfactant is employed which will impart a sirface tension of less than about 50 dynes/cm. to the dispersion, preferably less than about 40 dynes/cm.
• the amount of oxidizing agent employed should not exceed an amount of which will destroy the stability of such dispersion.
• from about 0.1 part by weight to about 2.0 parts by weight, preferably from about 0.2 part by weight to about 0.8 part by weight, per 100 parts by weight of mixture are satisfactory.
• a suitable dispersing agent may be employed to facilitate dispersion of the graphite or carbon black in the water and maintenance of the dispersion. Suitable stabilizers, film formers, etc. may also be employed if desired.
• a water-soluble surfactant which is also capable of functioning as an oxidizing agent at the temperature at which thermosetting is effected can be employed in the aqueous dispersions employed in the present invention, provided such oxidation agent-surfactant does not cause the suspension to flocculate.
• Anionic surfactants are preferred for this reason.
• Such oxidizing agent-surfactants serve both to increase wetting of the fibers by the dispersion and as a thermosetting aid during the subsequent infusibilization step. By reducing the surface tension of the water they promote the distribution of the graphite or carbon black throughout the fiber bundle and their own presence on the fiber surfaces, thereby further enhancing the oxidation and infusibilization of the fibers during thermosetting and allowing them to be processed at greatly increased speeds.
• Suitable oxidizing agent-surfactants include alkali metal hydrocarbyl sulfates, for example, alkali metal aryl sulfates and alkali metal alkyl sulfates.
• alkali metal hydrocarbyl sulfates for example, alkali metal aryl sulfates and alkali metal alkyl sulfates.
• the compounds which can be employed are sodium 2-ethylhexyl sulfate, sodium heptadecyl sulfate, and sodium tetradecyl sulfate. These compounds are sold commercially under the trademark "Tergitol" * .
• Tegitol because such salts leave residues on the fibers and may cause pitting of the fiber surfaces during oxidation, it is preferred to use the corresponding ammonium salts.
• oxiding agent/surfactant per 100 parts by weight of mixture
• a suitable dispersing agent may be employed to facilitate dispersion of the graphite or carbon black in the water and maintenance of the dispersion.
• oxidizing agents and wetting agents over and above the oxidizing agent/ surfactant employed may be added to the dispersion to facilitate oxidation or wetting of the fibers, although they are unnecessary.
• Suitable stabilizers, film formers, etc. may also be employed if desired.
• the dispersion After the dispersion has been formed, it is applied to the fipers by any convenient means, such as by spraying, brushing, rolling, or simply by immersing the fibers in the dispersion-.
• a convenient means of applying the dispersion to the fibers is to pass the fibers over a sizing wheel which rotates in a bath of the dispersion and is coated with the dispersion. This, preferably, is done as the fibers emerge from the spinnerette. By controlling the size and speed of the wheel it is possible to control the amount of the dispersion which is applied to the fibers. In any event, the fibers should be allowed to absorb a sufficient amount of the suspension to provide from about 0.1 gram of the dispersion to about 1.5 grams of the dispersion per gram of fiber.
• thermosetting in a conventional manner by heating in an oxygen-containing atmosphere, such as pure oxygen or air. Drying of the fibers is not necessary and the fibers can be thermoset while still wet if desired.
• Such thermosetting must be carried out at a temperature below the temperature at which the fibers soften or distort. Because the thermosetting action of the oxidizing agent employed usually commences at a temperature below 200°C. where the rate of oxidation is ordinarily quite slow, infusibilization can usually be effected at lower temperatures than are normally required, or in shorter periods of time than are normally required.
• time re ⁇ quired to oxidize the fibers to the desired degree will vary with such factors as the particular oxidizing atmosphere, the temperature employed, the diameter of the fibers, and the particular pitch from which the fibers were prepared, at any given temperature such time is usually less than two-thirds of the time required when the fibers are not treated with the dispersions of the present invention.
• thermoset fibers may then be carbonized in a conventional manner by heating them in an inert atmosphere to a temperature sufficiently elevated to remove hydrogen and other carbonizable by-products and produce a substantially all-carbon fiber.
• Fibers having a carbon content greater than about 98 percent by weight can generally be produced by heating to a temperature in excess of about 1000°C., and at temperatures in excess of about 1500°C. the fibers are completely carbonized. Generally, carbonization times of from about 2 seconds to about 1 minute are sufficient.
• the carbonized fibers may be further heated in an inert atmosphere to a graphitization temperature, e.g. from about 2500°C. to about 3300°C.
• Pitch fibers suitable for use in the present invention can be prepared in accordance with well-known techniques.
• the fibers employed are prepared from mesophase pitch as described in U.S. Pat. No. 4,005,183.
• Tensile strength was determined on an Instron testing machine at a cross-head speed of 0.02 cm/min. All measurements were made on 10-inch length unidirectional fiber-epoxy composites.
• Pull strength was determined on Mechanical Force Gage Model D-20-T, manufactured by Hunter Spring Co., Hatfield, Pa., a division of Ametak Inc.
• the filament or filament bundle to be tested is passed over a pulley which is attached by means of a spring to a gauge designed to record the force in pounds exerted on the pulley.
• Both ends of the filament or filament bundle are then wrapped around a mandrel which is suspended from the pulley by means of the filament or filament bundle.
• a distance of from about 3 to 12 inches is provided between the pulley and the mandrel.
• Tension is then exerted on the filament or filament bundle by pulling down on the mandrel until the yarn breaks.
• the total force in pounds required to break the filament or filament bundle is recorded on the gauge. This force is designated as the pull strength of the filament or filament bundle.
• Continuous pitch filaments were spun through two 1000 hole hot melt spinnerettcs from a 322°C. softening point mesophase pitch having a mesophase content of 77 percent.
• the capillary holes of the spinnerette were 4 mils in diameter and 8 mils in length.
• the fibers were spread over the slowly rotating wheel as they were brought into contact with it and were thoroughly wetted by and uniformly coated with the suspension by this procedure.
• the coated fibers were then collimated into a yarn by means of a gathering wheel having a "V" slot, and subsequently drawn down to a diameter of about 14 microns by means of two godet wheels.
• the suspension employed to coat the fibers contained 3.6 parts by weight of carbon black, 0.8 part by weight of ammonium persulfate, and 0.4 part by weight of ammonium laurate per 100 parts by weight of mixture.
• the carbon black particles present in the suspension had an average size of 0.5 micron.
• the composition was prepared by admixing (a) 3.2 parts by weight of an aqueous solution containing 25 parts by weight of ammonium persulfate in 75 parts by weight of water with (b) 20 parts by weight of an aqueous solution containing 2 parts by weight of ammonium laurate in 98 parts by weight of water, and (c) 6.4 parts by weight of "Dylon” * DS insulating carbon coating (a commercially available suspension of 56 parts by weight of amorphous carbon in 44 parts by weight of water), and then adjusting the pH of the mixture to 10 by means of ammonium hydroxide to give 100 parts of mixture.
• thermoset fibers treated in this manner were then thermoset by transporting them through a 40-foot long forced air convec- * "Dylon" is a registered trademark of Dylon Industries. tion furnace at a speed of 6 inches per minute. The furnace contained eight zones, each 5 feet in length, and the fibers were gradually heated from 175°C. in the first or entrance zone to 380°C. in the eighth or exit zone while air was passed through the furnace at a velocity of 4 feet/minute. Total rcsidence time in the furnace was 80 minutes. The fibers produced in this manner were totally infusible. A 3- inch length of the thermoset fibers had a pull strength of 5.1 lbs. and a 12-inch length had a pull strength of 3.1 lbs. (By 3-inch and 12-inch lengths is meant the distance between the pulley and the mandrel of the Mechanical Force Gage employed in the determination.)
• thermoset fibers c then wound on a roller and carbonized by heating them in a nitrogen atmosphere at a temperature of about 2200°C. for 3 seconds. After carbonization, the fibers had a strand tensile strength of 302,000 psi.
• Example 1 The procedure of Example 1 was repeated employing a colloidal suspension of graphite flour in an aqueous solution of ammonium persulfate and ammonium laurate.
• the suspension contained 3.6 parts by weight of graphite, 0.8 part by weight of ammonium persulfate, and 0.4 part by weight of ammonium laurate per 100 parts by weight of mixture.
• the graphite particles present had an average size of 1 micron.
• This composition was prepared by admixing (a) 3.2 parts by weight of an aqueous solution containing 25 parts by weight of ammonium persulfate in 75 parts by weight of water with (b) 20 parts by weight of an aqueous solution containing 2 parts by weight of ammonium laurate in 98 parts by weight of water, and (c) 16.4 parts by weight of "Aquadag” * micro-graphite colloid in aqueous suspension (a commercially available col- * "Aquadag” is a registered trademark of Acheson Colloids Company loidal suspension of 22 parts by weight of graphite in 78 parts by weight of water), and then adjusting the pH of the mixture to 9.7 by means of ammonium hydroxide to give 100 parts of mixture.
• a 3-inch length of the fibers had a pull strength of 4.7 lbs. and a 12-inch length had a pull strength of 3.8 lbs.
• thermoset fibers When the procedure was repeated eliminating the ammonium persulfate from the colloidal suspension employed to treat the fibers, a 3-inch length of the thermoset fibers had a pull strength of 2.4 lbs. and a 12-inch length had a pull strength of 1.8 lbs.
• Continuous pitch filaments were spun through two 1000 hole hot melt spinnerettes from a 322°C scftening point mesophase pitch having a mesophase content of 77 percent.
• the capillary holes of the spinnerette were 4 mils in diameter and 8 mils in length.
• the fibers were spread over the slowly rotating wheel as they were brought into contact with it and were thoroughly wetted by and uniformly coated with the suspension by this procedure.
• the coated fibers were then collimated into a yarn by means of a gathering wheel having a "V" slot, and subsequently drawn down to a diameter of about 14 microns by means of two godet wheels.
• the colloidal suspension employed to coat the fibers contained 3.6 parts by weight of graphite and 2.7 parts by weight of ammonium 2-ethylhexyl sulfate per 100 parts by weight of mixture.
• the graphite particles present had an average size of 1 micron.
• This composition was prepared by admixing 8.7 parts by weight of an aqueous solution containing 31 parts by weight of ammonium 2-cthylhcxyl sulfate in 69 parts by weight of water with 16.4 parts by weight of "Aquadag”* micro-graphite colloid in aqueous suspension (a commercially available colloidal suspension of 22 parts by weight of graphite in 78 parts by weight of water), and then adjusting the pH of the mixture to 10 by means of ammonium hydroxide to give 100 parts of mixture.
• thermoset fibers treated in this manner were then thermoset by transporting them through a 40-foot long forced air convection furnace at a speed of 6 inches per minute.
• the oven contained eight zones, each 5 feet in length, and the fibers were gradually heated from 175°C. in the first or entrance zone to 380 0 C. in the eighth or exit zone while air was passed through the furnace at a velocity of 4 feet/minute. Total residence time in the furnace was 80 minutes.
• the fibers produced in this manner were totally infusible.
• a 3- inch length of the thermoset fibers had a pull strength of 4.9 lbs. and a 12-inch length had a pull strength of 4.6 lbs. (By 3-inch and 12-inch lengths is meant the distance between the pulley and the mandrel of the Mechanical Force Gage employed in the determination.)
• thermoset fibers were then wound on a roller and carbonized by heating them in a nitrogen atmosphere at a temperature of about 2200°C. for 3 seconds. After carbonization, the fibers had a strand tensile strength of 247,000 psi.
• thermoset fibers When the procedure was again repeated substituting 0.4 part by weight of ammonium laurate for ammonium 2-ethylhexyl sulfate in the colloidal suspension employed to treat the fibers, a 3-inch length of the thermoset fibers had a pull strength of 2.4 lbs. and a 12-inch length had a pull strength of 1.8 lbs. These fibers were stiff, brittle, and too fused and weak to be wound on a roller and carbonized.
• thermoset fibers When the fibers were treated in like manner with suspensions containing from 1 part by weight to 3 parts by weight of colloidal graphite and from 0.08 part by weight to 0.39 part by weight of tetramethyl ammonium oleate per 100 parts by weight of mixture, 12-inch lengths of the thermoset fibers had pull strengths of from 0.3 lbs. to 2.6 lbs. These fibers were stiff, brittle, and too fused and weak to be wound on a roller and carbonized.
• Example 3 The procedure of Example 3 was repeated employing a suspension of carbon black flour in an aqueous solution of sodium 2-ethylhexyl sulfate.
• the suspension contained 3.6 parts by weight of carbon black and 2.7 parts by weight of sodium 2-ethylhexyl sulfate per 100 parts by weight of mixture.
• the carbon black particles present in the suspension had an average size of 0.5 micron.
• the composition was prepared by admixing 6.8 parts by weight of an aqueous solution containing 40 parts by weight of sodium 2-ethylhexyl sulfate in 60 parts by weight of water with 6.4 parts by weight of "Dylon” * DS insulating carbon coating (a commercially avail- * "Dylon” is a registered trademark of Dylon Industries. able suspension of 56 parts by weight of amorphous carbon in 44 parts by weight of water), and then adjusting the pH of the mixture to 10 by means of ammonium hydroxide to give 100 parts of mixture.
• thermosetting After thermosetting, a 12-inch length of fibers had a pull strength of 7.5 lbs. The carbonized fibers had a strand tensile strength of 307,000 psi.
• thermoset fibers When the procedure was repeated eliminating the sodium 2-ethylhexyl sulfate from the suspension employed to treat the fibers, 12-inch lengths of the thermoset fibers had a pull strength of 0.8 lbs. These fibers were stiff, brittle, and too fused and weak to be wound on a rcller and carbonised.
• thermoset fibers had a pull strength of 5.4 lbs and a 12-inch length had a pull strength of 3.1 lbs.
• the carbonized fibers had a strand tensile strength of 297,000 psi.
• thermoset fibers When 0.4 part by weight of ammonium laurate was substituted for sodium 2-ethylhexyl sulfate in the suspension, a 3-inch length of the thermoset fibers had a pull strength of 1.7 lbs and a 12-inch length had a pull strength of 1.6 lbs. These fibers were stiff, brittle, and too fused and weak to be wound on a roller and carbonized.
• thermoset fibers When 0.02 part by weight and 0.07 part by weight of tetramethyl ammonium oleate was substituted for sodium 2-ethylhexyl sulfate in the suspension, 12-inch lengths of the thermoset fibers had pull strengths of 0.6 lbs. and 1.1 lbs., respectively. Once again, the fibers were stiff, brittle, and too fused and weak to be wound on a roller and carbonized.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Inorganic Fibers (AREA)

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• 1980
  • 1980-01-28 EP EP19800400136 patent/EP0014161B1/de not_active Expired
  • 1980-01-28 DE DE8080400136T patent/DE3062488D1/de not_active Expired

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