WO2013173335A1 - Fibre de carbone broyée - Google Patents

Fibre de carbone broyée Download PDF

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Publication number
WO2013173335A1
WO2013173335A1 PCT/US2013/040946 US2013040946W WO2013173335A1 WO 2013173335 A1 WO2013173335 A1 WO 2013173335A1 US 2013040946 W US2013040946 W US 2013040946W WO 2013173335 A1 WO2013173335 A1 WO 2013173335A1
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WIPO (PCT)
Prior art keywords
carbon fiber
sizing
resin
weight
heat resistant
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PCT/US2013/040946
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English (en)
Inventor
Satoshi Seike
Makoto Kibayashi
Anand Valliyur Rau
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Toray Carbon Fibers America, Inc.
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Priority to EP13790250.8A priority Critical patent/EP2850123A1/fr
Publication of WO2013173335A1 publication Critical patent/WO2013173335A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • 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
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]

Definitions

  • the present invention relates to a milled carbon fiber with a sizing capable of achieving good mechanical properties and high resistance against thermal degradation.
  • Milled carbon fiber can be easily mixed with matrix resin, resulting in Carbon fiber reinforced plastics (CFRP) , and improve the mechanical properties, conductivity, corrosion and abrasion resistance.
  • CFRP Carbon fiber reinforced plastics
  • CFRP Carbon Fiber Reinforced Plastics
  • polymer matrix composite materials tend to show reduced strength and modulus under high temperature conditions.
  • heat resistant matrix resins are
  • Such heat resistant matrix resins include a thermosetting polyimide resin, a urea
  • polyamideimide resin a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyetheretherketone resin, a polyetherketoneketone resin, a polyamide, and a
  • CFRP with heat resistant matrix resins are molded under high temperature conditions, so a sizing must withstand thermal degradation. If the sizing undergoes thermal degradation, voids and some other problems occur inside a composite, resulting in undesired composite mechanical
  • a heat resistant sizing is an essential part of CFRP for better handleability, superior interfacial adhesive capability, controlling fuzz development, etc .
  • reinforced polymer having desirable mechanical and physical properties, including good friction and wear characteristics, as well as low outgassing has disclosed.
  • a sizing and a sized fiber used for heat resistant applications, and the sizing amount on a carbon fiber have not been described.
  • An object of the present invention is to provide a milled carbon fiber with a thermally stable sizing that enables enhanced adhesion to the thermoplastic matrix, good resin impregnation, and a lower propensity for generation of voids and harmful volatiles during processing owing to the inherent thermal stability as compared with less stable sizings.
  • milled carbon fiber is made of a carbon fiber coated with a sizing at an amount X between 0.05 and 0.30 weight%.
  • the sizing is formed of a heat resistant polymer or a precursor of the heat resistant polymer.
  • the amount X of the sizing is expressed with the following
  • Fig. 1 is a graph showing a relationship between strand tensile strength and sizing amount (KAPTON type polyimide, T800SC-24K, KAPTON is a registered trademark of E. I. du Pont de Nemours and Company) ;
  • Fig. 2 is a graph showing a relationship between drape value and sizing amount (KAPTON type polyimide, T800SC-24K)
  • Fig. 3 is a graph showing a relationship between rubbing fuzz and sizing amount (KAPTON type polyimide, T800SC-24K) ;
  • Fig. 4 is a graph showing a relationship between ILSS and sizing amount (KAPTON type polyimide, T800SC-24K) ;
  • Fig. 5 is a graph showing a TGA measurement result of T800S type fiber coated with KAPTON type polyimide
  • Fig. 6 is a graph showing a TGA measurement result of
  • Fig. 7 is a graph showing a relationship between strand tensile strength and sizing amount (ULTEM type polyetherimide, T800SC-24K, ULTEM is a registered trademark of Saudi Basic Industries Corporation) ;
  • Fig. 8 is a graph showing a relationship between drape value and sizing amount (ULTEM type polyetherimide, T800SC- 24K) ;
  • Fig. 9 is a graph showing a relationship between rubbing fuzz and sizing amount (ULTEM type polyetherimide, T800SC- 24K) ;
  • Fig. 10 is a graph showing a relationship between ILSS and sizing amount (ULTEM type polyetherimide, T800SC-24K) ;
  • Fig. 11 is a graph showing a TGA measurement result of T800S type fiber coated with ULTEM type polyetherimide
  • Fig. 12 is a graph showing a TGA measurement result of ULTEM type polyetherimide
  • Fig. 13 is a graph showing a relationship between strand tensile strength and sizing amount (ULTEM type polyetherimide, T700SC-12K) ;
  • Fig. 14 is a graph showing a relationship between drape value and sizing amount (ULTEM type polyetherimide, T700SC- 12K) ;
  • Fig. 15 is a graph showing a relationship between rubbing fuzz and sizing amount (ULTEM type polyetherimide, T700SC- 12K) ;
  • Fig. 16 is a graph showing a relationship between ILSS and sizing amount (ULTEM type polyetherimide, T700SC-12K) ;
  • Fig. 17 is a graph showing a relationship between strand tensile strength and sizing amount (Methylated melamine- formaldehyde, T700SC-12K) ;
  • Fig. 18 is a graph showing a relationship between drape value and sizing amount (Methylated melamine-formaldehyde,
  • Fig. 19 is a graph showing a relationship between rubbing fuzz and sizing amount (Methylated melamine-formaldehyde, T700SC-12K) ;
  • Fig. 20 is a graph showing a relationship between ILSS and sizing amount (Methylated melamine-formaldehyde, T700SC- 12K) ;
  • Fig. 21 is a graph showing a TGA measurement result of T700S type fiber coated with methylated melamine-formaldehyde ;
  • Fig. 22 is a graph showing a TGA measurement result of methylated melamine-formaldehyde ;
  • Fig. 23 is a graph showing a relationship between strand tensile strength and sizing amount (Epoxy cresol novolac, T700SC-12K) ;
  • Fig. 24 is a graph showing a relationship between drape value and sizing amount (Epoxy cresol novolac, T700SC-12K) ;
  • Fig. 25 is a graph showing a relationship between rubbing fuzz and sizing amount (Epoxy cresol novolac, T700SC-12K)
  • Fig. 26 is a graph showing a relationship between ILSS and sizing amount (Epoxy cresol novolac, T700SC-12K) ;
  • Fig. 27 is a graph showing a TGA measurement result of T700S type fiber coated with epoxy cresol novolac
  • Fig. 28 is a graph showing a TGA measurement result of epoxy cresol novolac
  • Fig. 29 is a schematic view showing a measurement
  • Fig. 30 is a schematic view showing a measurement
  • Fig. 31 is geometry of a dumbbell shaped specimen for Single Fiber Fragmentation Test
  • Table 1 shows a relationship between strand tensile strength and sizing amount (KAPTON type polyimide, T800SC- 24K) ;
  • Table 2 shows a relationship between drape value and sizing amount (KAPTON type polyimide, T800SC-24K) ;
  • Table 3 shows a relationship between rubbing fuzz and sizing amount (KAPTON type polyimide, T800SC-24K) ;
  • Table 4 shows a relationship between ILSS and sizing amount (KAPTON type polyimide, T800SC-24K) ;
  • Table 5 shows a relationship between strand tensile strength and sizing amount (ULTEM type polyetherimide, T800SC- 24K) ;
  • Table 6 shows a relationship between drape value and sizing amount (ULTEM type polyetherimide, T800SC-24K) ;
  • Table 7 shows a relationship between rubbing fuzz and sizing amount (ULTEM type polyetherimide, T800SC-24K) ;
  • Table 8 shows a relationship between ILSS and sizing amount (ULTEM type polyetherimide, T800SC-24K) ;
  • Table 9 shows a relationship between strand tensile strength and sizing amount (ULTEM type polyetherimide, T700SC- 12K) ;
  • Table 10 shows a relationship between drape value and sizing amount (ULTEM type polyetherimide, T700SC-12K) ;
  • Table 11 shows a relationship between rubbing fuzz and sizing amount (ULTEM type polyetherimide, T700SC-12K) ;
  • Table 12 shows a relationship between ILSS and sizing amount (ULTEM type polyetherimide, T700SC-12K) ;
  • Table 13 shows a relationship between strand tensile strength and sizing amount (Methylated melamine-formaldehyde, T700SC-12K) ;
  • Table 14 shows a relationship between drape value and sizing amount (Methylated melamine-formaldehyde, T700SC-12K) ;
  • Table 15 shows a relationship between rubbing fuzz and sizing amount (Methylated melamine-formaldehyde, T700SC-12K) ;
  • Table 16 shows a relationship between ILSS and sizing amount (Methylated melamine-formaldehyde, T700SC-12K) ;
  • Table 17 shows a relationship between strand tensile strength and sizing amount (Epoxy cresol novolac, T700SC-12K) ;
  • Table 18 shows a relationship between drape value and sizing amount (Epoxy cresol novolac, T700SC-12K) ;
  • Table 19 shows a relationship between rubbing fuzz and sizing amount (Epoxy cresol novolac, T700SC-12K) ;
  • Table 20 shows a relationship between ILSS and sizing amount (Epoxy cresol novolac, T700SC-12K) ;
  • Table 21 shows adhesion strength between a T800S type fiber and polyetherimide resin
  • Table 22 shows adhesion strength between a T700S type fiber and polyetherimide resin.
  • a pitch type carbon fiber a rayon type carbon fiber, or a PAN (polyacrylonitrile) type carbon fiber is used.
  • the PAN type carbon fibers that have high tensile strength are the most desirable for the invention.
  • the carbon fibers there are a twisted carbon fiber, an untwisted carbon fiber and a never twisted carbon fiber.
  • the carbon fibers have preferably a yield of 0.06 to 4.0 g/m and a filament number of 1,000 to 48,000.
  • the single filament diameter should be within 3 ym to 20 ym, more ideally, 4 ym to 10 ym.
  • Strand strength is desirably 3.0 GPa or above. 4.5 GPa or above is more desirable. 5.5 GPa or above is even more desirable.
  • Tensile modulus is desirably 200 GPa or above.
  • 220 GPa or above is more desirable.
  • 240 GPa or above is even more desirable. If the strand strength and modulus of the carbon fiber are below 3.0 GPa and 200 GPa, respectively, it is difficult to obtain the desirable mechanical property when the carbon fiber is made into composite materials.
  • the desirable sizing amount on carbon fiber is between 0.05 and 0.30 weight%. Between 0.05 and 0.25 weight ⁇ 6 is more desirable. Between 0.05 and 0.20 weight% is even more
  • the sizing amount is less than 0.05 weight%, when carbon fiber is produced, fuzz generation makes the smooth production more difficult. If on the other hand, the sizing amount is above 0.30 weight%, the carbon fiber is almost completely coated by the heat resistant polymer, resulting in low density of a carbon fiber strand, and poor spreadability . When this occurs, even resins with relatively low viscosity have undergone reduced impregnation; thereby leading to low mechanical properties. In addition from an environmental standpoint, if the sizing amount is above 0.30 weight%, the possibility that harmful volatiles are generated becomes higher during the sizing application process.
  • the good way to make the above milled carbon fiber is mechanical crush methods such as a hammer mill, a roll mill, an orient mill, or an impeller mill.
  • a fiber can be milled many times with one method or with different ones.
  • the length of the milled fiber in this invention is preferably 3 ⁇ or above. 50 ⁇ or above is more desirable. 100 ⁇ or above is even more desirable. 2 mm or below is desirable. 1 mm or below is more desirable. 500 ⁇ or below is even more desirable.
  • the desirable relation B/A is greater than 1.05, and more desirable relation B/A is greater than 1.1, where A is the Interfacial Shear Strength (IFSS) of unsized fiber and B is IFSS of sized fiber in the present invention whose surface treatment must be same as the unsized fiber.
  • IFSS can be measured by the Single Fiber Fragmentation Test (SFFT) , and unsized fiber could be de-sized fiber. A SFFT procedure and a de-sizing method will be described later.
  • Either carbonization, carbon fiber surface treatment, sizing application, winding or carbonization, carbon fiber surface treatment, sizing application, milling are preferably in continuous process. Sizing application process as a part of carbon fiber manufacturing is preferable. Post application or "oversizing" of carbon fiber can be also used.
  • a drape value (measured by the procedures described below) of the continuous fiber before milled should be less than 15 cm, 12 cm or less is better, 10 cm or less is even more desirable, 8 cm or less is most desirable.
  • thermosetting As to the matrix resin, either thermosetting or
  • thermoplastic resins could be used.
  • the invention is not limited to any particular resins, and a thermosetting polyimide resin, an epoxy resin, a polyester resin, a polyurethane resin, a urea resin, a phenol resin, a melamine resin, a cyanate ester resin, and a
  • bismaleimide resin may be used.
  • thermoplastic resin resins, mostly heat resistant resins, that contain oligomer could be used.
  • the invention is not limited to any particular heat resistant thermoplastic resins, and a
  • thermoplastic polyimide resin a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyetheretherketone resin, a polyetherketoneketone resin, a polyamide, and a polyphenylenesulfide resin may be used .
  • a heat resistant polymer is a desirable sizing agent to be used for coating a carbon fiber.
  • the sizing agents are preferably a phenol resin, a urea resin, a melamine resin, a polyimide resin, a polyetherimide resin, or others, which can be an aqueous solution, an aqueous dispersion or an aqueous emulsion. These polymers can be also dissolved with organic solvent and applied to a carbon fiber. And organic solvent based sizing agents such as a polysulfone resin, a
  • polyethersulfone resin a polyetheretherketone resin, a polyetherketoneketone resin, a polyphenylenesulfide resin, a polyamide resin, or others can be also used.
  • water could be generated as a condensation product.
  • An example of a heat resistant polymer will be shown as below.
  • a polyimide is made by heat reaction or chemical reaction of polyamic acid. During the imidization process, water is generated; therefore, it is important to complete imidization before composite fabrication.
  • a water generation ratio W based on a carbon fiber during a composite fabrication process is preferably 0.05 weight% or less. 0.03 weight% or less is desirable. Ideally, 0.01 weight% or less is optimal.
  • the water generation ratio W can be defined by the following equation:
  • weight A of a sized fiber is measured after holding 2 hours at 110 degrees Celsius and the weight difference B between 130 degrees Celsius and 415 degrees Celsius of a sized fiber is measured under air atmosphere with TGA (holding 110 degrees Celsius for 2 hours, then heating up to 450 degrees Celsius at 10 degrees Celsius/min) .
  • An imidization ratio X of 80% or higher is acceptable, and 90% or higher is desirable. Ideally, 95% or higher is optimal.
  • the imidization ratio X is defined by the following equation :
  • weight loss ratio C of a polyamic acid without being imidized and the weight loss ratio D of a polyimide are measured between 130 degrees Celsius and 415 degrees Celsius under air atmosphere with TGA (holding 110 degrees Celsius for 2 hours, then heating up to 450 degrees Celsius at 10 degrees Celsius/minute) .
  • the heat resistant polymer is preferably used in a form of an organic solvent solution, an aqueous solution, an aqueous dispersion or an aqueous emulsion of the polymer itself or a polymer precursor.
  • a polyamic acid which is the precursor to a polyimide is enabled to be water soluble by neutralization with alkali. It is preferred for the alkali to be water soluble.
  • Chemicals such as ammonia, a monoalkyl amine, a dialkyl amine, a trialkyl amine, and
  • tetraalkylammonium hydroxide could be used.
  • Organic solvents such as DMF (dimethylformamide) , DMAc (dimethylacetamide) , DMSO (dimethylsulfoxide) , NMP (N- methylpyrrolidone) , THF ( tetrahydrofuran) , etc. could be used.
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethylsulfoxide
  • NMP N- methylpyrrolidone
  • THF tetrahydrofuran
  • the sizing has a glass transition temperature above 100 degrees Celsius. Above 150 degrees Celsius is better. Even more preferably the glass transition temperature shall be above 200 degrees Celsius.
  • a glass transition temperature is measured according to ASTM E1640 Standard Test Method for "Assignment of the Glass Transition Temperature by Dynamic Mechanical Analysis” using a Differential Scanning Calorimetry (DSC) .
  • a thermal degradation onset temperature of a sized fiber is preferably above 300 degrees Celsius. 370 degrees Celsius or higher is more desirable, 450 degrees Celsius or higher is more desirable, and 500 degrees Celsius or higher is most desirable.
  • a thermal degradation onset temperature is measured, first, a sample with a weight of about 5 mg is dried in an oven at 110 degrees Celsius for 2 hours, and cooled down to room temperature. Then it is weighed and placed on a thermogravimetric analyzer (TGA) under air atmosphere. Then, the sample is analyzed under an air flow of 60 ml/minute at a heating ratio of 10 degrees Celsius/minute. A weight change is measured between room temperature and 600 degrees Celsius.
  • TGA thermogravimetric analyzer
  • the degradation onset temperature of a sized fiber is defined as a temperature at which an onset of a major weight loss occurs. From the TGA experimental data, the sample weight, expressed as a percentage of the initial weight, is plotted as a function of the temperature (abscissa) . By drawing tangents on a curve, the thermal degradation onset temperature is defined as an intersection point where tangent at a steepest weight loss crosses a tangent at minimum gradient weight loss adjacent to the steepest weight loss on a lower temperature side .
  • thermal degradation onset temperature applies to the state of a carbon fiber after the chemical reaction but before a resin impregnation.
  • the heat resistant property is imparted to the sized fiber by a chemical reaction affected before fiber is impregnated with resin.
  • the sizing can be used in place of a sized fiber.
  • a 30% weight reduction temperature of a sizing is
  • thermogravimetric analyzer TGA
  • temperature of the sizing is defined as a temperature at which the weight of the sizing reduces by 30% with reference to the weight of the said sizing at 130 degrees Celsius.
  • a sizing agent application method includes a roller sizing method, a submerged roller sizing method and/or a spray sizing method.
  • the submerged roller sizing method is
  • the carbon fiber goes through the drying treatment process in which water and/or organic solvent will be dried, which are solvent or dispersion media. Normally an air dryer is used and the dryer is run for 6 seconds to 15 minutes.
  • the dry temperature should be set at 200 degrees Celsius to 450 degrees Celsius, 240 degrees Celsius to 410 degrees Celsius would be more ideal, 260 degrees Celsius to 370 degrees Celsius would be even more ideal, and 280 degrees Celsius to 330 degrees Celsius would be most desirable.
  • thermoplastic dispersion it is desirable that it should be dried at over the formed or softened temperature. This could also serve a purpose of reacting to the desired polymer characteristics.
  • the atmosphere to be used for the drying treatment should be air; however, when an organic solvent is used in the process, an inert atmosphere involving elements such as nitrogen could be used.
  • the carbon fiber tow then, is wound onto a bobbin.
  • the carbon fiber produced as described above is evenly sized.
  • Sizing amount in this invention is defined as the higher of the values obtained by the following two methods outlined below, and is considered to represent a reasonably true estimate of the actual amount of sizing on the fiber.
  • Sizing amount (weight%) is measured by the following method .
  • the de-sized sample is rinsed with enough water and placed in an oven for 1 hour at 110 degrees Celsius.
  • the sizing amount (weight%) is calculated by the
  • the sizing amount (weight%) is measured by the following method .
  • a carbon fiber tow is cut from the bobbin to a length of about 50 cm without applying any tension.
  • a weight is
  • the weight is 30 g for 12,000 filaments and 60 g for 24,000 filaments, so that 1 g tension is applied per 400 filaments.
  • the specimen is then hung in a vertical position for 30 minutes with the weighted end hanging freely. After the weight is released from the specimen, the specimen is placed on a rectangular table such that a portion of the specimen is extended by 25 cm from an edge of the table having 90 degrees angle as shown in Fig. 29.
  • the specimen on the table is fixed with an adhesive tape without breaking so that the portion hangs down from the edge of the table.
  • a distance D (refer to Fig. 29) between a tip of the specimen and a side of the table is defined as the drape value.
  • a carbon fiber tow is slid against four pins with a diameter of 10 mm (material: chromium steel, surface roughness: 1 to 1.5 ym RMS) at a speed of 3
  • the initial tension to a carbon fiber is 500 g for the 12,000 filament strand and 650 g for 24,000 filament strand.
  • the carbon fiber is slid against the pins by an angle of 120 degrees.
  • the four pins are placed (horizontal distance) 25 mm, 50 mm and 25 mm apart (refer to Fig. 30) .
  • fuzz blocks light incident on a photo electric tube from above, so that a fuzz counter counts the fuzz count.
  • ILSS Interlaminar Shear Strength
  • ILSS of the composites consisting of the polymer coated carbon fiber and an epoxy resin matrix is measured according to ASTM D2344 Standard Test Method for "Short-Beam Strength of Polymer Matrix Composite Materials and Their Laminates". ⁇ Single Fiber Fragmentation Test (SFFT)>
  • Specimens are prepared with the following procedure.
  • the filament is fixed at the both sides with a KAPTON tape to be kept straight.
  • the filament (filaments) is overlapped with another ULTEM type polyetherimide resin sheet (length: 90 ⁇ width: 150 ⁇ thickness: 0.26 (mm)), and KAPTON film (thickness: 0.1 (mm)) coated with a mold release agent is overlapped on it.
  • Spacers are set between two aluminum plates .
  • the aluminum plates including a sample are set on the pressing machine at 290 degrees Celsius.
  • a dumbbell shaped specimen where a single filament is embedded in the center along the loading direction, has the center length 20 mm, the center width 5 mm and the thickness 0.5 mm as shown in Fig. 31.
  • SFFT is performed at an instantaneous strain rate of approximately 4 %/minute counting the fragmented fiber number in the center 20 mm of the specimen at every 0.64% strain with a polarized microscope until the saturation of fragmented fiber number.
  • the preferable number of specimens is more than 2 and Interfacial Shear Strength (IFSS) is obtained from the average length of the fragmented fibers at the saturation point of fragmented fiber number.
  • IFSS Interfacial Shear Strength
  • De-sized fiber may be used for SFFT in place of unsized fiber.
  • De-sizing process is as follows.
  • Sized fiber is placed in a furnace of nitrogen atmosphere at 500 degrees Celsius, where the oxygen concentration is less than 7 weight%.
  • KAPTON type polyimide coated milled carbon fiber can be obtained by milling the following carbon fiber. Unsized 24K high tensile strength, intermediate modulus carbon fiber
  • Torayca T800SC (Registered trademark by Toray Industries; strand strength 5.9 GPa, strand modulus 294 GPa) was used.
  • the carbon fiber was continuously submerged in the sizing bath containing polyamic acid ammonium salt of 0.1 to 1.0 weight% .
  • the polyamic acid is formed from the monomers pyromellitic dianyhydride and 4 , 4 ' -oxydiphenylene . After the submerging process, it was dried at 300 degrees Celsius for 1 minute in order to have poly (4, 4 ' -oxydiphenylene-pyromellitimide)
  • the sizing amount was measured with an alkaline method.
  • Thermogravimetric analysis was conducted under air atmosphere.
  • Example 5 The heat degradation onset temperature of the same carbon fiber as the above is 510 degrees Celsius as shown in Fig. 5.
  • the heat degradation onset temperature of the sizing of the sizing is 585 degrees Celsius and the 30% weight reduction temperature is 620 degrees Celsius as shown in Fig. 6, confirming the heat resistance is in excess of 500 degrees Celsius.
  • ULTEM type polyetherimide coated milled carbon fiber can obtained by milling the following carbon fiber. Unsized 24K high tensile strength, intermediate modulus carbon fiber
  • Torayca T800SC (Registered trademark by Toray Industries; strand strength 5.9 GPa, strand modulus 294 GPa) was used.
  • the carbon fiber was continuously submerged in the sizing bath containing polyamic acid dimethylaminoethanol salt of 0.1 to 2.0 weight%.
  • the polyamic acid is formed from the monomers 2, 2 ' -Bis (4- (3, 4-dicarboxyphenol) phenyl) propane dianhydride and meta-phenylene diamine.
  • Thermogravimetric analysis was conducted under air atmosphere. (Example 10) The heat degradation onset
  • the temperature of the same carbon fiber as the above is over 550 degrees Celsius as shown in Fig. 11.
  • the heat degradation onset temperature of the sizing was 548 degrees Celsius and the 30% weight reduction temperature is 540 degrees Celsius as shown in Fig. 12, confirming the heat resistance is in excess of 500 degrees Celsius.
  • ULTEM type polyetherimide coated milled carbon fiber can be obtained by milling the following carbon fiber.
  • Unsized 12K high tensile strength, standard modulus carbon fiber "Torayca” T700SC (Registered trademark by Toray Industries - strand strength 4.9 GPa, strand modulus 230 GPa) was used.
  • the carbon fiber was continuously submerged in the sizing bath containing polyamic acid dimethylaminoethanol salt of 0.1 to 2.0 weight%.
  • the polyamic acid is formed from the monomers 2, 2' -Bis (4- (3, 4-dicarboxyphenol) phenyl) propane dianhydride and meta-phenylene diamine.
  • Methylated melamine-formaldehyde coated milled carbon fiber can be obtained by milling the following carbon fiber.
  • melamine-formaldehyde resin After the submerging process, it was dried at 220 degrees Celsius for 1 minute. The sizing amount was measured with a burn off method.
  • Thermogravimetric analysis was conducted under air atmosphere. (Example 19) The heat degradation onset
  • the temperature of the same carbon fiber as the above is 390 degrees Celsius as shown in Fig. 21.
  • the heat degradation onset temperature of the sizing is 375 degrees Celsius and the 30% weight reduction temperature is 380 degrees Celsius as shown in Fig. 22, confirming the heat resistance is in excess of 350 degrees Celsius.
  • Epoxy cresol novolac coated milled carbon fiber can be obtained by milling the following carbon fiber. Unsized 12K high tensile strength, standard modulus carbon fiber "Torayca" T700SC (Registered trademark by Toray Industries - strand strength 4.9 GPa, strand modulus 230 GPa) was used. The carbon fiber was continuously submerged in the sizing bath containing 0.1 to 2.0 weight% of epoxy cresol novolac resin. After the submerging process, it was dried at 220 degrees Celsius for 1 minute. The sizing amount was measured with a burn off method.
  • Thermogravimetric analysis was conducted under air atmosphere. (Example 24) The heat degradation onset
  • the temperature of the same carbon fiber as the above is 423 degrees Celsius as shown in Fig. 27.
  • the heat degradation onset temperature of the sizing is 335 degrees Celsius and the 30% weight reduction temperature is 420 degrees Celsius as shown in Fig. 28, confirming the heat resistance is in excess of 300 degrees Celsius.
  • Fig. 29 and Table 21 show the results of SFFT using polyetherimide resin. From the results, it can be shown the IFSS of Examples 25 and 26 - ⁇ ⁇ 5"6 higher than that of Comparative Example 21. Examples 27, 28, 29, Comparative Example 22:
  • the carbon fiber with about 0.2 weight% heat resistant sizing (Examples 27, 28, 29) and Unsized fiber T700SC-12K (Comparative Example 22) were used .
  • Fig. 30 and Table 22 show the results of SFFT using polyetherimide resin. It can be shown the IFSS of Examples 27 through 29 - ⁇ ⁇ 5"6 higher than that of Comparative Example 22 and the IFSS of Examples 27 and 29 are over 10% higher than that of Comparative Example 22.

Abstract

La présente invention concerne une fibre de carbone broyée réalisée à partir d'une fibre de carbone, qui est revêtue d'un produit d'encollage en une quantité X comprise entre 0,05 et 0,29 % en poids. Le produit d'encollage est formé d'un polymère résistant à la chaleur ou d'un précurseur du polymère résistant à la chaleur. La quantité X du produit d'encollage est exprimée par la formule suivante : X= (W0-W1)/W0 x 100%, dans laquelle W0 est le poids de la fibre de carbone avec le produit d'encollage, et W1 est le poids de la fibre de carbone sans le produit d'encollage.
PCT/US2013/040946 2012-05-15 2013-05-14 Fibre de carbone broyée WO2013173335A1 (fr)

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US20160075876A1 (en) * 2013-05-08 2016-03-17 Solvay Specialty Polymers Usa, Llc Polyarylene ether sulfone (PAES) compositions
CN107337808B (zh) * 2017-07-31 2019-05-10 中国科学院长春应用化学研究所 一种碳纤维用界面增强乳液型上浆剂及其制备方法
CN112351966A (zh) * 2018-07-02 2021-02-09 巴斯夫欧洲公司 制备包含至少一种增强纤维的烧结粉末颗粒(sp)的方法
CN114729185B (zh) * 2022-02-23 2023-09-26 浙大宁波理工学院 阻燃碳纤维增强聚酰胺复合材料及其制备方法、表面接枝碳纤维的制备方法

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US20100120972A1 (en) * 2008-11-11 2010-05-13 E. I. Du Pont De Nemours And Company Composite compositions including semi-aromatic polyamides and carbon fiber, and articles thereof
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US20110003955A1 (en) * 2008-02-07 2011-01-06 Daiwa Can Company Imide Oligomer And Polyimide Resin Obtained By Thermal Curing Thereof
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US3837904A (en) * 1970-03-09 1974-09-24 Great Lakes Carbon Corp A method of sizing carbon fibers
US5230956A (en) * 1982-05-28 1993-07-27 Amoco Corporation Polyamide-imide sized fibers
US5239046A (en) * 1987-09-03 1993-08-24 The Boeing Company Amideimide sizing for carbon fiber
US5093155A (en) * 1988-11-29 1992-03-03 Tonen Corporation Process for sizing reinforcing fiber by applying sulfone compounds containing sulfonyl groups and sized reinforcing fibers obtained thereby
US5106680A (en) * 1990-05-08 1992-04-21 Hoechst Celanese Corporation Adhesion between carbon fibers and thermoplastic matrix materials in carbon fiber composites by using multifunctional amine and azo compounds as bridging agents
WO1997035715A1 (fr) * 1996-03-27 1997-10-02 Virginia Tech Intellectual Properties, Inc. Composites de resines thermodurcissables et de fibres de carbone presentant des encollages comprenant un polyamide aliphatique
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US20020050574A1 (en) * 1999-04-07 2002-05-02 Board Of Trustrees Operating Michigan State University Process for the treatment of a fiber
US20040109991A1 (en) * 2000-07-13 2004-06-10 Jean Guevel Unidirectional web made of composite material
US20090062426A1 (en) * 2005-03-25 2009-03-05 Teijin Techno Products Limited Carbon Fiber Strand for Reinforcing Thermoplastic Resins and Method of Producing the Same
US7754323B2 (en) * 2006-02-24 2010-07-13 Toray Industries, Inc. Fiber-reinforced thermoplastic resin molded article, molding material, and method for production of the molded article
US20110003955A1 (en) * 2008-02-07 2011-01-06 Daiwa Can Company Imide Oligomer And Polyimide Resin Obtained By Thermal Curing Thereof
US20110217228A1 (en) * 2008-11-10 2011-09-08 Toray Industries ,Inc. Fiber bundle with pieced part, process for producing same, and process for producing carbon fiber
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US20110294943A1 (en) * 2009-02-05 2011-12-01 Arkema Inc. Fibers sized with polyetherketoneketones

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