Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/40—Organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C03C25/36—Epoxy resins

Definitions

• the present invention relates to glass fibers and more particularly it relates to sizing compositions for glass fibers. Even more particularly, the invention relates to size compositions for continuous glass fibers useful for the reinforcement of plastics.
• glass fibers which are intended for use as reinforcements usually require a size. This size is applied during the fiber forming process. That is, the glass fibers are sized with a protective material substantially immediately after they are formed. The sized glass fibers then are gathered into a bundle and the bundles are wound onto a forming package. The continuous glass fibers then are used in various processes such as pultrusion or filament winding.
• Sizing compositions need to provide a lubricating quality to the individual filaments to provide them with abrasion resistance.
• the sizing composition must provide the fibers with an outer film which is compatible with the resin they will reinforce.
• Filament winding is a process in which continuous filaments are impregnated with a resin, wound onto a mandrel to build the desired shape and thickness, and cured.
• mandrel is meant a tool used in filament winding on which bands of fibers are deposited into filamentary patterns to form layers. Upon curing of the resin, the composite so shaped is removed from the mandrel and applied to its intended use.
• the pultrusion process generally consists of pulling continuous filaments through a resin bath or impregnator and then into preforming fixtures (dies) in which a section of continuous filament impregnated with resin is partially shaped and excess resin and/or air are removed. Then the section is pulled through in heated dies in which it is cured.
• the industry continues to want the composites to have a longer working life, i.e., improved fatigue life such as cyclic fatigue in which the composites are subjected to repetitive loading cycles. These composites also need to sustain high working pressures, i.e., increased pressures at which the composite fail.
• the bis silanes we use are represented by the formula: (R) 3 Si - R 1 - Si(R) 3 wherein R is an alkyl or alkoxy radical having 1 to 10 carbon atoms and R 1 is an alkylene radical having 1 to 10 carbon atoms.
• R is an alkyl or alkoxy radical having 1 to 5 carbon atoms and R 1 is an alkylene radical having 1 to 5 carbon atoms.
• the preferred bis silane is 1 -(triethoxy silyl)-2-(methyldiethoxy silyDethane represented by the formula:
• each R radical may be different.
• the size composition also contains epoxy (film forming epoxies), other silanes, lubricants, wetting agents and the like.
• film forming epoxy is a diglycidyl ether of bisphenol A.
• the term also includes suitable surfactants or emulsifiers. It is best, to employ commercially available film forming epoxy materials, and to also first form these epoxy materials into an emulsion for subsequent combination with the other ingredients of the size composition.
• the epoxy materials used in the size composition are diglycidyl ethers of bisphenol A, and are commercially available under such trade designations as AD 502 and NEOXIL 962. Such diglycidyl ethers have terminal unreacted epoxy groups and are generally of the formula:
• Preferred ethers are low molecular weight materials in which n is value between about 0.2 to about 0.34. These epoxy materials typically have epoxide equivalent weights of less than about 600 and suitably about 540 to about 170. In the preferred embodiment of this invention, we employ two epoxy emulsions.
• methylacryloxysilane While any methylacryloxysilane may be employed, the preferred material is gamma-methacryloxypropyltrimethoxysilane such as that commercially available under the trade designation A-174.
• the wetting agent, an acid and water make up the balance of the size composition.
• the preferred acid for pH adjustment is acetic acid.
• the above ingredients will constitute about 5 to about 10 percent by weight of the final applied size emulsion, with the balance being the acid and water.
• At least one continuous filament is coated with a resin.
• the resin is selected from the group consisting of an unsaturated polyester, a vinyl ester, and mixtures thereof with vinyl ester being preferred.
• Vinyl ester resins which we employ are well known and are disclosed in U.S. Patent Nos. 3,367,992; 3,066,1 12; 3,179,623; 4,673,706 and 5,015,701 .
• the backbone component of vinyl ester resin can be derived from a variety of well known resins such as, for example, an epoxide resin, polyester resin, or a urethane resin. Those based on epoxide resins are widely used commercially and, hence, are especially preferred in the process of the present invention.
• Vinyl ester resins employed in the process of the present invention are well known and are generally prepared by reacting at least equivalent proportions of a polyepoxide resin and an unsaturated monocarboxylic acid wherein
• Suitable vinyl ester resins include, for example, 8303 from Interplastics Corporation (Vadnais Heights, Minnesota) and Hetron ® 925 from Ashland Chemical Co. (Ashland, OH).
• polyester resins which can be employed are well known in the art.
• polyester resins are prepared by condensing an ethylenically unsaturated dicarboxylic acid or anhydride or mixtures thereof with a dihydric alcohol or mixtures of dihydric alcohols.
• Filament means a single filament or fiber, and a multiplicity of fibers is known as a strand.
• the preferred glass fiber composition is selected from the group consisting of E-type, S-type, A-type and C-type. Most preferably the glass fiber is E- or S-type.
• the glass fiber used in this invention preferably have tensile strengths of approximately 2.9 to 4.4 GPa and Young's modulus of approximately 70 to 87 GPa. Glass fiber for use in the present invention is available as roving in yields from 675 to
• Glass fibers are conventionally manufactured by discharging a plurality of molten glass streams from a heated bushing, attenuating the plurality of glass streams into a plurality of fibers and passing the fibers through an applicator to apply the aqueous based size to the fibers. Afterwards the fibers are gathered into a strand at a gathering shoe and wound on a collet to produce a glass fiber package. The package is dried to evaporate the water from the aqueous-based size.
• the in-line drying process of U.S. Patent No. 5,055, 1 19 is an energy efficient process for forming glass fiber packages which are free of migration.
• air from around the fiber forming bushing passes beneath the bushing whereby it is heated by bushing heat and the heated air is then drawn into a chamber through which the glass fibers pass in heat transfer contact with the heated air.
• the heat transfer causes the water or solvent in the applied size to be evaporated and results in a migration free glass fiber package.
• the amount of each ingredient in the size is not critical. Typically, the size contains standard amounts of each ingredient on a percent by weight basis. Usually, these amounts are:
• these amounts are: Ingredient Percent bv Weight as Received
• This size is an aqueous based size containing up to 10% solids with the balance being water.
• NEOXIL 962 epoxy emulsion 2.00
• the size was an aqueous based size containing about 95% water and about 5% solids. We applied the size to E glass fiber strands. The strands were prepared according to the method described in Example I of U.S. Patent No. 5,055,1 19.
• test samples were the same except for the size employed.
• the sample contained about 70% glass and about 30% vinyl ester resin.
• the filament wound pipes were fabricated by passing the glass fiber strand through a resin bath containing a thermosetting resin, styrene and a strain relieving polymer in amounts designated in the tables. Fibers so impregnated were wound onto a mandrel to form a tube or pipe and placed in an oven at room temperature. The oven was heated to 82.2°C (180°F) in 6 minutes. The temperature of the oven was then raised to 148.9°C (300°F) in about 15 minutes and the mandrels with pipe were heated at that temperature for 15 minutes. The oven was allowed to cool to room temperature before the pipes were removed from the oven and separated from the mandrel. After the pipe was dislodged from the mandrel, it was cut into 61 cm segments each having a diameter of 57 mm. The wall thickness was measured for each pipe, and it was approximately 1.27 mm thick.
• the number of cycles for water to penetrate to the outer wall of the pipe was measured by each detector. After all the detectors failed, an average number of cycles was taken for each pipe section. Pipe sections were tested at different pressures. The pipe section's minimum wall thickness was determined according to ASTM D-2992.
• the hoop stress is defined as the tensile stress in the wall of the piping product in the circumferential direction due to internal pressure.
• the linear regression of the logarithm of the hoop stress versus the logarithm of number of cycles was used to calculate the number of cycles to weep at a hoop stress of 131 MPa (19,000 psi), a commonly accepted method for reporting fatigue life in the art of continuous fiber reinforced pipe.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Reinforced Plastic Materials (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1993
  • 1993-11-08 JP JP6512281A patent/JPH07503229A/ja active Pending
  • 1993-11-08 EP EP94901342A patent/EP0620805A1/en not_active Withdrawn
  • 1993-11-08 KR KR1019940702311A patent/KR940703788A/ko not_active Ceased
  • 1993-11-08 WO PCT/US1993/010788 patent/WO1994011318A1/en not_active Application Discontinuation
  • 1993-11-09 TW TW082109397A patent/TW249811B/zh active
  • 1993-11-10 CN CN93112943A patent/CN1088231A/zh active Pending

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