WO2013099436A1 - 複合材料 - Google Patents
複合材料 Download PDFInfo
- Publication number
- WO2013099436A1 WO2013099436A1 PCT/JP2012/078276 JP2012078276W WO2013099436A1 WO 2013099436 A1 WO2013099436 A1 WO 2013099436A1 JP 2012078276 W JP2012078276 W JP 2012078276W WO 2013099436 A1 WO2013099436 A1 WO 2013099436A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- glass
- composite material
- oxide glass
- rubber
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 86
- 239000011347 resin Substances 0.000 claims abstract description 86
- 239000000075 oxide glass Substances 0.000 claims abstract description 27
- 229920001971 elastomer Polymers 0.000 claims abstract description 21
- 239000005060 rubber Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims description 66
- 239000003365 glass fiber Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 7
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229930182556 Polyacetal Natural products 0.000 claims description 2
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 229920001230 polyarylate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920001290 polyvinyl ester Polymers 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 229920001748 polybutylene Polymers 0.000 claims 1
- 238000010248 power generation Methods 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000004455 differential thermal analysis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 238000009730 filament winding Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920005560 fluorosilicone rubber Polymers 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- 238000001721 transfer moulding Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- 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
- C03C13/00—Fibre or filament compositions
-
- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/06—Polystyrene
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
- F03D—WIND MOTORS
- F03D1/00—Wind motors with rotation axis substantially parallel to the air flow entering the rotor
- F03D1/06—Rotors
- F03D1/065—Rotors characterised by their construction elements
- F03D1/0675—Rotors characterised by their construction elements of the blades
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
Definitions
- the present invention relates to a composite material in which glass and resin or rubber are mixed.
- Resins and rubbers are lightweight and easy to be molded at a relatively low temperature as compared with other materials, but they have disadvantages such as severe deterioration due to ultraviolet light and low mechanical strength and gas barrier properties.
- glass is excellent in chemical stability as compared with resin and rubber, and has high mechanical strength and gas barrier properties, but has a drawback that it is easily fragile and heavy.
- GFRP glass fiber reinforced plastic
- Patent Document 1 discloses that a bundling agent containing a silane coupling agent and a resin is applied to the surface of a glass fiber.
- the object of the present invention is to increase the mechanical strength of the composite material in a simple process.
- the present invention is a composite material comprising a resin or rubber and an oxide glass, wherein the resin or rubber is dispersed in the oxide glass, or the oxide glass is the resin or It disperse
- the mechanical strength of the composite material can be increased by a simple process.
- the present invention is a composite material composed of a resin or rubber (hereinafter referred to as a resin or the like) and an oxide glass, and the resin or the like is dispersed in the glass, or the glass is dispersed in the resin or the like.
- a resin or the like a resin or rubber
- the glass softens and melts (melts) at or below the thermal decomposition temperature of a resin or the like. Since the interface between the glass and the resin once melted is smooth, the adhesion between the resin and the glass is higher than that in which the glass particles are simply dispersed in the resin.
- the thermal decomposition temperature is a temperature at which weight reduction starts by heating and is thermogravimetrically measured (TG).
- the oxide glass forming the composite material of the present invention contains Ag and two or more of Te, P, and V, so that it has a softening point even without using elements harmful to the environment such as Pb and Bi. Can be lowered. Since the softening point of this glass can be made equal to or lower than the temperature at which the resin etc. decomposes, it softens and flows the glass without much decomposition of the resin of the composite material in which the glass and the resin are mixed, and integrates with the resin. be able to. Therefore, the adhesion of the interface between the glass and the resin can be enhanced, and the mechanical strength of the composite material can be enhanced. Moreover, the composite material of the present invention can be produced by a simple process of mixing and heating glass particles and a resin. Furthermore, the weather resistance and the mechanical strength are enhanced as compared with the resin only material, and the weight can be reduced as compared with the glass only material.
- the oxide glass at least containing the Ag 2 O and V 2 O 5 and TeO 2, the total content of Ag 2 O and V 2 O 5 and TeO 2 may If it is 75 mass% or more.
- Ag 2 O and TeO 2 are components that contribute to lowering the softening point, and the softening point of the glass of the present invention roughly corresponds to the content of Ag 2 O and TeO 2 .
- V 2 O 5 suppresses the precipitation of metal Ag from Ag 2 O in glass and contributes to the improvement of the thermal stability of the glass. With such a composition range, the softening point of the glass (the peak temperature of the second endothermic peak in the temperature raising process in DTA) can be lowered to 320 ° C. or lower, and sufficient thermal stability is ensured. be able to.
- the oxide glass it is preferable to contain 10 to 60% by mass of Ag 2 O, 5 to 65% by mass of V 2 O 5 and 15 to 50% by mass of TeO 2 .
- 10 to 60% by mass it indicates 10% by mass or more and 60% by mass or less. Since the deposition of the metal Ag from Ag 2 O is suppressed by the addition of V 2 O 5, with a softening point makes it possible to increase the Ag 2 O is more temperature reduction, chemical stability of the glass (e.g. , Moisture resistance) is improved. By setting it as such a composition range, moisture resistance better than the conventional low melting-point lead-free glass is securable.
- the Ag 2 O content is more than 2.6 times the V 2 O 5 content, the softening point Ts does not become so low in temperature even if Ag 2 O is added, and the glass is easily crystallized. Therefore, the Ag 2 O content is preferably 2.6 times or less of the V 2 O 5 content.
- the oxide glass contains 10 to 60% by mass of Ag 2 O, 5 to 65% by mass of V 2 O 5 and 15 to 50% by mass of TeO 2, and Ag 2 O and V 2 O
- the total content rate of 5 and TeO 2 is 75% by mass or more, and the moisture resistance is excellent even when the sum of the Ag 2 O content rate and the V 2 O 5 content rate is 40 to 80% by mass.
- glasses having various compositions were produced, and the softening point and moisture resistance of the glasses were investigated.
- Each starting material powder was mixed in the mass ratio shown in Table 1 and placed in a platinum crucible.
- the ratio of Ag 2 O in the raw material using alumina crucible in the case of more than 40 wt%.
- mixing in consideration of avoiding excessive moisture absorption to the raw material powder, mixing was performed in a crucible using a metal spoon.
- the crucible containing the raw material mixed powder was placed in a glass melting furnace, and was heated and melted. The temperature was raised at a temperature rising rate of 10 ° C./min, and the molten glass was maintained at a set temperature (700 to 900 ° C.) for 1 hour while stirring. Thereafter, the crucible was taken out of the glass melting furnace, and the glass was cast into a graphite mold which had been preheated to 150 ° C. Next, the casted glass was transferred to a strain removing furnace which had been previously heated to a strain removing temperature, and after holding strain for 1 hour, the strain was removed and cooled to room temperature at a rate of 1 ° C./min. The glass cooled to room temperature was crushed to prepare a glass powder having the composition shown in the table.
- the softening point Ts was measured by differential thermal analysis (DTA) for each of the glass powders obtained above.
- the DTA measurement was carried out at a temperature rising rate of 5 ° C./min in the atmosphere with the mass of the reference sample ( ⁇ -alumina) and the measurement sample of 650 mg respectively, and the peak temperature of the second endothermic peak was determined as the softening point Ts 1).
- the results are shown in Table 1.
- FIG. 2 is a schematic view of a cross-sectional SEM image of the composite material.
- the black contrast part is the glass 21, and the white contrast part is the resin 22.
- the glass powder is heated and softened and flows, and the molten glasses are connected to each other to be coarsened. Since the glass particles tend to stick to other nearby glass particles when softening, the possible shapes of the glass 21 after softening differ depending on how the glass powder is heated in a dispersed state in the resin. . Therefore, although the glass 21 is illustrated as being elongated and elongated in a rod-like shape in FIG. 2, it can take various shapes such as a near spherical shape, a meandering shape, and a mesh shape.
- glass is dispersed in the resin, but if the amount of glass is increased relative to the resin, a composite material in which the resin is dispersed in the glass can be manufactured in the same manner.
- the resin may be crystalline or amorphous, and polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyvinyl acetate, ABS resin, AS resin, acrylic resin, polyacetal resin, polyimide, polycarbonate, modified polyphenylene ether (PPE) ), Polybutylene terephthalate (PBT), polyarylate, polysulfone, polyphenylene sulfide, polyether ether ketone, polyimide resin, fluorine resin, polyamide imide, polyether ether ketone, epoxy resin, phenol resin, polyester, polyvinyl ester, etc. .
- the conditions for compounding are that the glass softens and flows below the thermal decomposition temperature of the resin or the like, and the difference between the glass transition point of the glass and the glass transition point of the amorphous resin (melting point of the crystalline resin) is Preferably, the temperature is within 100 ° C. This is because if the temperature difference exceeds 100 ° C., the thermal strain due to the difference in the thermal expansion coefficient of the two becomes large, the crack is easily generated at the interface of the two, and the good adhesion between the two can not be secured. .
- the composite material is produced by mixing and heating glass particles and flakes such as resin, so that when the mixing ratio of resin etc is high, the glass is softened to fuse the flakes together. It is necessary not to make the temperature difference between the point and the glass transition point (melting point in the case of crystalline resin) of resin etc. too large (within about 100 ° C.).
- thermoplastic resins can be softened and flowed by heating even after producing the composite material, so that breakages and defects of the composite material can be repaired. .
- the molded body produced has a certain degree of conductivity, and can therefore be used as a package for various electronic devices having an antistatic function.
- the oxygen permeability and water vapor permeability of the resulting composite material were evaluated.
- the measurement of oxygen permeability is carried out under the condition of temperature 30 ° C. and humidity 90% RH using an oxygen permeability measurement device (OX-TRAN (R) 2/20) manufactured by US MOCON Co., Ltd. It was performed under the condition of 0.1 MPa.
- the measurement limit of the device is 0.01 cc / m 2 / day.
- the water vapor transmission rate was measured at a temperature of 30 ° C. and a humidity of 90% RH using a moisture permeability measuring device (PERMATRAN (R) 2/20) manufactured by US MOCON Co., Ltd. under a pressure difference of 0.1 MPa. Made under the conditions of The measurement limit of the device is 0.01 g / m 2 / day.
- PERMATRAN (R) 2/20 moisture permeability measuring device manufactured by US MOCON Co., Ltd.
- the oxygen permeability and the water vapor permeability of the composite material of the present invention were below the measurement limit of the device.
- composite with rubber can be used, and as rubber, fluoro rubber, silicone rubber and acrylic rubber are suitable.
- FIG. 3 is a cross-sectional view of the fiber-reinforced resin windmill blade structure in a direction perpendicular to the longitudinal axis of the blade.
- the blade comprises an outer skin called an upper skin 33 and a lower skin 34 connecting the front edge 31 and the rear edge 32.
- the inside surrounded by the outer panel is a space for weight reduction.
- a box-shaped girder called a spar 35 having a layered structure is inserted and reinforced in the longitudinal direction of the blade.
- the spar 35 is composed of a flange portion 36 in contact with the inner skin of the upper skin 33 and the lower skin 34, and a web portion 37 connecting upper and lower flange portions of the blade.
- the spar 35 may be C-shaped, I-shaped, or plate-like in addition to box-like.
- the upper skin 33 and the lower skin 34 are preferably made of fiber reinforced resin (FRP) for weight reduction and corrosion resistance, and in the present embodiment, a glass fiber reinforced resin (glass fiber impregnated with a matrix resin) GFRP was used.
- the glass fiber is a fibrous glass mainly composed of silicon dioxide (SiO 2 ) and has a fiber diameter of about 5 to 20 ⁇ m.
- FIG. 4 is a partial cross-sectional view of the upper flange 36 (flange 50) of FIG.
- the composite layer 44 is integrally configured by the carbon fiber layer 42, the glass fiber layer 45, and the adhesive layer 43 laminated alternately.
- the adhesive layer 43 is adhered to the upper skin (not shown).
- the glass fiber layer 45 is obtained by impregnating the glass fiber 46 with the matrix resin 47.
- the carbon fiber layer 42 is obtained by impregnating a carbon fiber 49 with a resin.
- thermosetting resins such as an epoxy resin, vinyl ester resin, unsaturated polyester resin
- the composite material of this embodiment is used for the upper skin 33 and the lower skin 34 and the matrix resin 47 of the glass fiber layer 45. Since the glass fiber 46 contains SiO 2 as a main component, it does not soften at the temperature at which the glass in the matrix resin 47 softens, and maintains the function as a reinforcing material. The glass in the matrix resin 47 is in partial contact with the glass fiber 46.
- the glass in the matrix resin 47 is softened and adhered to the glass fiber 46, whereby high adhesion between the glass in the matrix resin 47 and the glass fiber 46 is achieved, and the interface between the glass fiber 46 and the matrix resin 47 Bonding strength is greatly improved as compared with the case of a normal resin matrix. Further, when the composite material of this embodiment is used also for the matrix resin 48 of the carbon fiber layer 42, both the glass in the matrix resin 47 and the glass in the matrix resin 48 are softened and adhered. High adhesion with the carbon fiber layer 42 can also be achieved.
- the glass of the present embodiment is a semiconductor
- the upper skin 33 and the lower skin 34 have a certain degree of conductivity, so that damage due to current flow due to lightning strike or the like is reduced, which is advantageous for safety.
- any known forming techniques such as a prepreg method, a resin transfer molding (RTM) method, a drawing method, a filament winding method, a hand layup method and the like can be used.
- the glass powder, the resin binder, and the solvent were mixed, and the slurry (coating material) for spray spraying was produced.
- Nitrocellulose was used as the resin binder and butyl carbitol acetate was used as the solvent.
- the slurry is applied to the surface of the blade by spray spraying, and the protective film can be formed by heating and holding the temperature above the softening point temperature of the glass.
- the weather resistance of the blade can be improved, and conductivity can be imparted.
Abstract
Description
本発明は樹脂またはゴム(以下、樹脂等と称する)と酸化物ガラスから構成される複合材料であって、樹脂等がガラス中に分散しているか、ガラスが樹脂等中に分散している。この複合材料を加熱することで、ガラスが、樹脂等の熱分解温度かそれよりも低い温度で軟化流動(溶融)する。一度溶けたガラスと樹脂との界面は滑らかであるため、単に樹脂中にガラス粒子が分散しているものと比較して、樹脂とガラスとの密着性は高くなる。なお、熱分解温度は、加熱により重量減少が始まる温度であり、熱重量測定(TG)する。
表1に示す組成を有するガラス(SPL-01~25)を作製した。表中の組成は、各成分の酸化物換算における質量比率で表示してある。出発原料としては、(株)高純度化学研究所製の酸化物粉末(純度99.9%)を用いた。一部の試料においては、Ba源およびP源としてBa(PO3)2(リン酸バリウム、ラサ工業(株)製)を用いた。
上記で得られた各ガラス粉末に対して、示差熱分析(DTA)により軟化点Tsを測定した。DTA測定は、参照試料(α-アルミナ)および測定試料の質量をそれぞれ650mgとし、大気中5℃/minの昇温速度で行い、第2吸熱ピークのピーク温度を軟化点Tsとして求めた(図1参照)。結果を表1に併記する。
表1に記載のSPL-21ガラス粉末(粒子径:3μm)と、フレーク状のポリスチレン樹脂とを体積比で1:1になるように配合し、2軸混錬機により複合化した。混練機の加熱保持温度を250℃、スクリューの回転速度を40rpm/minとした。
酸素透過度の測定は、温度30℃、湿度90%RHの条件で、米国モコン(MOCON)株式会社製の酸素透過度測定装置(OX-TRAN(R)2/20)を使用し、圧力差0.1MPaの条件で行われた。装置の測定限界は0.01cc/m2/dayである。
22 樹脂
31 前縁部
32 後縁部
33 上スキン
34 下スキン
35 スパー
36、50 フランジ部
37 ウエブ部
42 炭素繊維層
43 接着層
44 複合層
45 ガラス繊維層
46 ガラス繊維
47、48 マトリクス樹脂
49 炭素繊維
Claims (13)
- 樹脂またはゴムと、酸化物ガラスを備えた複合材料において、前記樹脂またはゴムが前記酸化物ガラス中に分散、あるいは、前記酸化物ガラスが前記樹脂またはゴム中に分散し、加熱により、前記酸化物ガラスが、前記樹脂またはゴムの熱分解温度以下で軟化流動することを特徴とする複合材料。
- 樹脂またはゴムと、酸化物ガラスを備えた複合材料において、前記樹脂またはゴムが前記酸化物ガラス中に分散、あるいは、前記酸化物ガラスが前記樹脂またはゴム中に分散し、前記酸化物ガラスが、Te、P、Vの少なくとも2種とAgを含有することを特徴とする複合材料。
- 請求項1において、前記酸化物ガラスが、Te、P、Vの少なくとも2種とAgを含有することを特徴とする複合材料。
- 請求項3において、前記酸化物ガラスが、Te、V、Agを含有することを特徴とする複合材料。
- 請求項4において、前記酸化物ガラスが、Ag2O、V2O5、TeO2を含有し、Ag2OとV2O5とTeO2との合計含有率が75質量%以上であることを特徴とする複合材料。
- 請求項5において、前記酸化物ガラスが、10~60質量%のAg2Oと、5~65質量%のV2O5と、15~50質量%のTeO2とを含有することを特徴とする複合材料。
- 請求項6において、前記酸化物ガラスのAg2O含有率がV2O5含有率の2.6倍以下であることを特徴とする複合材料。
- 請求項7において、前記酸化物ガラスのAg2O含有率とV2O5含有率との和が40~80質量%であることを特徴とする複合材料。
- 請求項1または2において、前記樹脂が、ポリエチレン、ポリ塩化ビニル、ポリプロピレン、ポリスチレン、ポリ酢酸ビニル、ABS樹脂、AS樹脂、アクリル樹脂、ポリアセタール樹脂、ポリイミド、ポリカーボネート、変性ポリフェニレンエーテル(PPE)、ポリブチレンテレフタレート(PBT)、ポリアリレート、ポリサルホン、ポリフェニレンスルフィド、ポリエーテルエーテルケトン、ポリイミド樹脂、フッ素樹脂、ポリアミドイミド、ポリエーテルエーテルケトン、エポキシ樹脂、フェノール樹脂、ポリエステル、ポリビニルエステルのいずれかであることを特徴とする複合材料。
- 請求項1または2の複合材料と有機溶剤とを含むことを特徴とする塗料。
- 請求項1または2の複合材料とガラス繊維とが複合化されたことを特徴とするガラス繊維強化型樹脂。
- 請求項1または2の複合材料から構成されることを特徴とする導電性パッケージ。
- 請求項11のガラス繊維強化型樹脂を備えることを特徴とする風力発電用ブレード。
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KR102323875B1 (ko) * | 2021-06-25 | 2021-11-09 | 일성 주식회사 | 교면 방수제 제조방법 및 시공방법 |
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TW201335250A (zh) | 2013-09-01 |
CN103987791B (zh) | 2016-05-11 |
JP5712123B2 (ja) | 2015-05-07 |
CN103987791A (zh) | 2014-08-13 |
US9708460B2 (en) | 2017-07-18 |
JP2013133342A (ja) | 2013-07-08 |
US20140334937A1 (en) | 2014-11-13 |
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