CN107498941A - Carbon fibre reinforced composite, Preparation method and use - Google Patents

Carbon fibre reinforced composite, Preparation method and use Download PDF

Info

Publication number
CN107498941A
CN107498941A CN201710628915.0A CN201710628915A CN107498941A CN 107498941 A CN107498941 A CN 107498941A CN 201710628915 A CN201710628915 A CN 201710628915A CN 107498941 A CN107498941 A CN 107498941A
Authority
CN
China
Prior art keywords
composite
carbon fiber
carbon
cloth
metakaolin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710628915.0A
Other languages
Chinese (zh)
Other versions
CN107498941B (en
Inventor
张雪梅
李松
高龙飞
于坤
肖沅谕
董可心
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing FRP Research and Design Institute Composite Co Ltd
Original Assignee
Beijing FRP Research and Design Institute Composite Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing FRP Research and Design Institute Composite Co Ltd filed Critical Beijing FRP Research and Design Institute Composite Co Ltd
Priority to CN201710628915.0A priority Critical patent/CN107498941B/en
Publication of CN107498941A publication Critical patent/CN107498941A/en
Application granted granted Critical
Publication of CN107498941B publication Critical patent/CN107498941B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5292—Flakes, platelets or plates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9684—Oxidation resistance

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a kind of carbon fibre reinforced composite, Preparation method and use.The composite is using carbon fiber as reinforcement, using the mixture comprising KP1, metakaolin, alkali metal hydroxide and water as original gelatin, is prepared using condensation of aluminum phosphate and/or aluminium triphosphate as the curing agent of original gelatin.Well and without flue dust and toxic gas release, it may be used as thermally protective materials for the composite machinery intensity and toughness.

Description

Carbon fibre reinforced composite, Preparation method and use
Technical field
A kind of carbon fibre reinforced composite of the present invention, Preparation method and use, especially a kind of carbon fiber reinforced inorganic Polymer composites and its production and use.
Background technology
Aluminosilicate-type inorganic polymer has good heat resistance, thus be widely used in aviation, naval vessel, traffic, National defence etc..Aluminosilicate-type inorganic polymer has the characteristic of similar resin, can use the system of conventional resins based composites Standby mode (such as hot pressing, winding, air pressure tank) is molded, thus technique is simple and convenient, easily fabricated large-size ceramic base composite wood Expect part.Such inorganic polymer low-temperature setting can be molded below 300 DEG C, it is not necessary to large-scale ceramic post sintering equipment.With it Its ceramic matric composite is compared, and aluminosilicate-type inorganic polymer can substantially reduce manufacturing cost.Especially led in thermal protection Domain, compared to traditional tree aliphatic radical thermally protective materials, aluminosilicate-type inorganic polymer has the advantages that heatproof temperature is high.But its machine Tool performance, flue dust and toxicity release performance are still up for improving.
On the one hand, prior art generally use carbon fiber is mixed to form ceramic composite with Multiple components.For example, CN106191715A discloses a kind of ceramic composite, and it is prepared from the following raw materials in parts by weight：Aluminum oxide ceramic 15~24 parts of particle, 10~17 parts of silicon carbide ceramics particle, 4~9 parts of magnesium hydroxide, 2~6 parts of cumyl peroxide, carbon are fine 3~7 parts of dimension, 6~10 parts of frog stone, 5~9 parts of sodium silicate binder, 7~10 parts of zinc stearate, 5~9 parts of copper powder, silicon nitride 7~ 12 parts, 3~6 parts of calcium oxide, 7~10 parts of aluminum silicofluoride, 6~11 parts of short glass fiber, 5~8 parts of barium titanate, 3~5 parts of nickel, 8~14 parts of kaolin.Such combination can not avoid the generation of flue dust and toxic gas.
On the other hand, KP1 is commonly used for preparing fire resisting binder materials, binding agent etc. with carbon fiber, has not been used to Prepare ceramic composite.For example, CN106116391A discloses a kind of refractory concrete, including granulated blast-furnace slag 100~ 120 parts, 8~12 parts of KP1,4~6 parts of sodium hydroxide, 80~100 parts of portland cement, 30~70 parts of flyash, river sand 100~150 parts, 200~250 parts of stone, 2~5 parts of modified carbon fiber cloth, 8~15 parts of expanded perlite, silicon rubber rubber powder 2~4 Part, 600010~15 parts of modified poly (ethylene glycol), 2~3 parts of epoxy resin latex, 1~2 part of di-2-ethylhexylphosphine oxide naphthalene sulfonic acids disodium are wooden Plain 0.5~1.5 part of sodium sulfonate, 65~75 parts of water.And for example, CN104129969A discloses a kind of ground polymers base carbon fibre cloth and bonded Agent, carbon cloth binding agent is prepared by raw material of KP1, slag, metakaolin, flyash, retarder and water, wherein with Industrial solid castoff slag, the flyash of abundance are primary raw material, using KP1 as exciting agent, add dibastic sodium phosphate Or sodium acid carbonate class compound is retarder, the carbon cloth binding agent of preparation, when temperature reaches 170 DEG C, caking property is not still Subtract.
The content of the invention
The defects of in order to overcome prior art, present inventor have made intensive studies, and find using carbon fiber as increasing Qiang Ti, using a kind of specific aluminosilicate-type inorganic polymer ceramics as matrix, the suitable curing agent of addition, can obtain mechanical strong The carbon fiber reinforced inorganic polymer ceramic matric composite that degree and toughness well and without flue dust and toxic gas discharge.
It is an object of the present invention to provide a kind of carbon fibre reinforced composite, mechanical strength and toughness it is good and It there is no flue dust and toxic gas release.
It is another object of the present invention to provide a kind of preparation method of carbon fibre reinforced composite, the letter of its technique Singly and can be with low temperature moulding.
It is yet a further object of the present invention to provide a kind of purposes of carbon fibre reinforced composite, its be used as aircraft or The thermally protective materials of automobile, it there is no flue dust and toxic gas release.
The present invention provides a kind of carbon fibre reinforced composite, the composite using carbon fiber as reinforcement, with comprising KP1, metakaolin, the mixture of alkali metal hydroxide and water are as original gelatin, with condensation of aluminum phosphate and/or trimerization Aluminum phosphate is prepared as the curing agent of original gelatin.The carbon fibre reinforced composite of the present invention can be that a kind of carbon fiber increases Strong inorganic polymer ceramic matric composite.The present invention uses specific original gelatin and curing agent, the machinery of gained composite Intensity and toughness are good, and without the release of flue dust and poison gas.For example, do not contained in the mixture of the present invention any in high temperature The material of flue dust and poison gas can be discharged down.Described high temperature can be 200~1300 DEG C, preferably 800~1000 DEG C.
According to the composite of the present invention, it is preferable that the mixture is by KP1, metakaolin, alkali metal hydrogen-oxygen Compound and water composition.It so can further avoid carrying flue dust and toxic gas release composition in raw material secretly, avoid at high temperature Produce flue dust and toxic gas.
Carbon fiber is high intensity, the new fiber materials of high modulus fibre of a kind of phosphorus content more than 95%.Carbon fiber It can be divided mainly into polyacrylonitrile (PAN) base, asphaltic base, viscose glue base three types.The carbon fiber of the present invention is preferably polyacrylonitrile Base carbon fibre, it can so avoid producing flue dust and toxic gas at high temperature.The carbon fiber example that the present invention uses include but It is not limited to T300, T700, T800 carbon fiber of toray company production.Preferably, the carbon fiber of the present invention is selected from Japan The T300 carbon fibers of Toray production.The tow of the carbon fiber of the present invention can be 1~12k root monofilament, preferably 3~6k roots Monofilament (1k is equivalent to 1000).According to an embodiment of the invention, carbon fiber of the invention uses tow as 3k's T300 carbon fibers.The carbon fiber of the present invention is used in the form of carbon cloth, can use plain weave carbon cloth.
In the present invention, the molecular formula of KP1 is K2O·nSiO2, its main component is K2O and nSiO2.The present invention KP1 Baume degrees Be (20 DEG C) can be 35~45, preferably 40~45.Metakaolin is with kaolin (Al2O3· 2SiO2·2H2O it is) raw material, is dehydrated the anhydrous aluminium silicate (Al of formation at moderate temperatures2O3·2SiO2).It is a discovery of the invention that potassium The combination of waterglass and metakaolin is advantageous to improve the mechanical performance of composite, and does not cause the production of flue dust or poison gas It is raw.
Prior art is typically using retarder of the phosphoric acid species as KP1 such as dibastic sodium phosphates.It is of the invention then send out Existing, condensation of aluminum phosphate, aluminium triphosphate are highly suitable as the curing agent for promoting composite to be solidified.Although mechanism is still not It is clear, but it is presumed that mechanism be：Condensation of aluminum phosphate, aluminium triphosphate slowly hydrolyze in aqueous, discharge hydrogen ion Promote the colloidization of KP1, so as to separate out silicon dioxide colloid；With the evaporation of moisture, silicon dioxide colloid is condensed into silicon Oxygen network structure.It is a discovery of the invention that condensation of aluminum phosphate, aluminium triphosphate be very beneficial for improve composite mechanical performance and Toughness, and do not cause the generation of flue dust or poison gas.
According to the composite of the present invention, it is preferable that KP1, metakaolin, the weight of alkali metal hydroxide and water Amount is than being 100: 101~108: 16~22: 6~16.Preferably, KP1, metakaolin, alkali metal hydroxide and water Weight ratio be 100: 105~108: 19~22: 11~16.By said components control in above range, be advantageous to improve compound The tensile strength and bending strength of material, linear ablative rate is reduced, improve specific heat capacity.
According to the composite of the present invention, it is preferable that the mass ratio of the mixture and the carbon fiber is 3~6: 1；And The mass ratio of the mixture and the curing agent is 100: 0.2~0.4.It is described mixed according to an embodiment of the invention The mass ratio of compound and the carbon fiber is 4~6: 1；And the mass ratio of the mixture and the curing agent for 100: 0.28~ 0.4.Said components are controlled to the mechanical performance in above range, being advantageous to improve composite, reduce linear ablative rate and raising Specific heat capacity.
According to the composite of the present invention, it is preferable that the K in the KP12O content is 9~18wt% and SiO2 Content is 22~31wt%；And described alkali metal hydroxide is potassium hydroxide.Preferably, in the KP1 K2O content is 15~17.5wt% and SiO2Content is 28~31wt%.Using said components, the machine of composite can be improved Tool performance, and reduce flue dust.
According to the present invention composite, it is preferable that by thickness be 12mm composite sample in 1000 DEG C of ablations Composite quality retention rate >=98% after 600s.It is the compound of 12mm by thickness according to an embodiment of the invention Composite quality retention rate >=99% of the material sample after 1000 DEG C of ablation 600s.
According to the composite of the present invention, it is preferable that using GJB 323A-1996 in heat flow density 4309.1Kw/m2With Setting-out line ablating rate is 0.05~0.1mm/s under ablation time 20s；Using GJB 330A-2000 to a diameter of 11mm and height It is 1.1~1.4kJ/kg DEG C to spend the specific heat capacity determined for 32mm cylinder sample at a temperature of room temperature~800 DEG C；Using GB/T 1447-2005 are 117 to the tensile strength for the Specimen Determination that size is 250 × 25 × 4mm (length × width × height)~ 163MPa；With use GB/T 1449-2005 strong for the bending of 80 × 15 × 5mm (length × width × height) Specimen Determination to size Spend for 109~134MPa.
The present invention also provides a kind of preparation method of above-mentioned composite, comprises the following steps：
(1) original gelatin is prepared：KP1, metakaolin, alkali metal hydroxide and water are mixed to get mixture, made For original gelatin；
(2) glue is prepared：Curing agent and original gelatin are mixed to get glue；
(3) carbon fiber is handled：10~30min is cleaned by ultrasonic to the carbon cloth of carbon fiber-containing using organic solvent, dried standby；
(4) prepreg cloth is made：Glue obtained by step (2) is coated in obtained by step (3) on carbon cloth, and hangs and is presoaked Cloth；
(5) blank plate is made：Prepreg cloth obtained by step (4) is cut, and is superimposed, is pressed into blank plate；
(6) solidify：Blank plate obtained by step (5) is handled 6~12 hours at 80~200 DEG C, then cooling obtains institute State composite.
In the preparation process in accordance with the present invention, the species of carbon fiber, curing agent, KP1, metakaolin, alkali metal hydrogen-oxygen The quality of species and its weight ratio of compound and water, the mass ratio of mixture (original gelatin) and carbon fiber, mixture and curing agent Than as it was previously stated, repeating no more here.
In steps (1), KP1, metakaolin, alkali metal hydroxide and water are mixed, then stirred, So as to obtain mixture as original gelatin.For example, metakaolin, alkali metal hydroxide and water are added in KP1, so After stir, so as to obtain mixture as original gelatin.Specifically, metakaolin, potassium hydroxide and distilled water are added into potassium In waterglass, then stir, so as to obtain mixture as original gelatin.In step (2), curing agent and original gelatin are mixed Conjunction obtains glue.For example, curing agent is added into original gelatin, then stir, so as to obtain glue.
Preparation in accordance with the present invention, it is preferable that in step (3), the organic solvent is selected from acetone or alcohol, institute The carbon cloth for stating carbon fiber-containing is plain weave carbon cloth；In step (4), open assembly time is 1~2h；In step (5), the thickness of blank plate Spend for 5~30mm；With in step (6), described is cooled to furnace cooling.In the step (5) of the present invention, prepreg cloth is cut out Cut required size and be superimposed, be subsequently placed in and the blank plate for requiring thickness is pressed on press.The thickness of blank plate is excellent Elect 10~15mm as.According to an embodiment of the invention, after compressing blank plate is pressed from both sides into upper steel plate locking up and down, put It is placed in baking oven and solidifies.
The present invention also provides the purposes of above-mentioned composite, and the composite is used as aircraft or automobile thermal protection material Material.The carbon fibre reinforced composite of the present invention has high temperature resistant, anti-yaw damper, mechanical strength and good-toughness, can manufacture big face Product component, can meet the heat shield member in the fields such as aircraft, automobile to material performance requirement.
The present invention carbon fibre reinforced composite using carbon fiber as reinforcement, with specific aluminosilicate-type inorganic polymer Ceramics is matrixes and add specific curing agent, are lacked so as to solve the intrinsic fragility of inorganic polymer, low mechanical strength etc. Point, and do not produce flue dust and toxic gas substantially at high temperature.The preparation technology of the present invention is carried out at a lower temperature, Gu It is relatively low to change temperature, is suitable for industrialized production.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to This.
The method of testing used in example below is described as follows：
Composite quality retention rate：By thickness be 12mm composite sample after 1000 DEG C of ablation 600s, measure The weight of ablation, composite quality retention rate is calculated.
Linear ablative rate：Using GJB 323A-1996 in heat flow density 4309.1Kw/m2Surveyed with ablation time 20s It is fixed.
Specific heat capacity：It is 32mm cylinder sample in room temperature~800 to a diameter of 11mm and height to use GJB 330A-2000 It is measured at a temperature of DEG C.
Tensile strength：GB/T 1447-2005 are used to be measured size for 250 × 25 × 4mm sample.
Bending strength：GB/T 1449-2005 are used to be measured size for 80 × 15 × 5mm sample.
Embodiment 1
(1) original gelatin is prepared：In KP1: metakaolin: KOH: distilled water=100: 101: 16: 6 ratios are prepared 3278g original gelatins, and stir.
(2) glue is prepared：6.56g condensation of aluminum phosphate is added in the original gelatin that step (1) is prepared, obtained after stirring Glue.
(3) carbon fiber is handled：One piece of 1000 × 4100mm of breadth 3k T300 plain weave carbon cloth is determined, after weighing, is used EtOH Sonicate handles 10min, dries standby.
(4) prepreg cloth is made：The 3284.56g of step (2) glue is uniformly brushed and on carbon cloth, dried in the air obtained by step (3) Put 1h.
(5) blank plate is made：The prepreg cloth of step (4) is cut into 50 220 × 310mm prepreg cloth, is then superimposed Together, 40 DEG C of baking 1h, are subsequently placed on press, are pressed into thickness as blank plate thick 15mm.
(6) solidify：The blank plate suppressed is pressed from both sides and goes up lower plate, after lock screw, is positioned in baking oven, 150 DEG C solid Change 8 hours, product is made after the demoulding.The linear ablative rate of gained composite is 0.0965mm/s, specific heat capacity 1.21kJ/kg DEG C, tensile strength 117MPa, bending strength 109MPa.
Embodiment 2
(1) original gelatin is prepared, in KP1: metakaolin: KOH: distilled water=100: 105: 19: 11 ratios are prepared 4578g original gelatins, and stir.
(2) glue is prepared：13.73g condensation of aluminum phosphate is added in the original gelatin that step (1) is prepared, after stirring To glue.
(3) carbon fiber is handled：One piece of 1000 × 4100mm of breadth 3k T300 plain weave carbon cloth is determined, after weighing, is used EtOH Sonicate handles 10min, dries standby.
(4) prepreg cloth is made：The 4591.73g of step (2) glue is uniformly brushed and on carbon cloth, dried in the air obtained by step (3) Put 1h.
(5) blank plate is made：The prepreg cloth of step (4) is cut into 50 220 × 310mm prepreg cloth, is then superimposed Together, 40 DEG C of baking 1h, are subsequently placed on press, are pressed into thickness as blank plate thick 15mm.
(6) solidify：The blank plate suppressed is pressed from both sides and goes up lower plate, after lock screw, is positioned in baking oven 150 DEG C, Gu Change 8 hours, product is made after the demoulding.The linear ablative rate of gained composite is 0.0570mm/s, specific heat capacity 1.31kJ/kg DEG C, tensile strength 163MPa, bending strength 134MPa.
Embodiment 3
(1) original gelatin is prepared：In KP1: metakaolin: KOH: distilled water=100: 108: 22: 16 ratios are prepared 4900g original gelatins, and stir.
(2) glue is prepared：19.6g aluminium triphosphates are added in the original gelatin of step (1), glue is obtained after stirring Liquid.
(3) carbon fiber is handled：One piece of 1000 × 4100mm of breadth 3k T300 plain weave carbon cloth is determined, after weighing, is used Acetone is ultrasonically treated 20min, dries standby.
(4) prepreg cloth is made：The 4919.6g of step (2) glue is uniformly brushed and on carbon cloth, dried in the air obtained by step (3) Put 1h.
(5) blank plate is made：The prepreg cloth of step (4) is cut into 50 220 × 310mm prepreg cloth, is then superimposed Together, 40 DEG C of baking 1h, are subsequently placed on press, are pressed into thickness as blank plate thick 15mm.
(6) solidify：The blank plate suppressed is pressed from both sides and goes up lower plate, after lock screw, is positioned in baking oven 150 DEG C, Gu Change 8 hours, product is made after the demoulding.The linear ablative rate of gained composite is 0.0780mm/s, specific heat capacity 1.33kJ/kg DEG C, tensile strength 153MPa, bending strength 121MPa.
In addition, the composite of embodiment 1~3 is compared with high silicone/phenolic resin based composites, test specimen is thick Spend for 12mm, 1000 DEG C of ablation 600s of static state.Composite quality retention rate >=98% of embodiment 1~3, and high silica/phenol The quality retention rate of aldehyde radical composite is less than 90%.Meanwhile the composite of embodiment 1~3 do not have in ablation flue dust and Poison gas discharges；High silicone/phenolic resin based composites then discharge volume of smoke and poison gas in ablation.
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the substantive content of the present invention, this area skill Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.

Claims (10)

1. a kind of carbon fibre reinforced composite, it is characterised in that the composite is using carbon fiber as reinforcement, to include potassium Waterglass, metakaolin, the mixture of alkali metal hydroxide and water are as original gelatin, with condensation of aluminum phosphate and/or trimerization phosphorus Sour aluminium is prepared as the curing agent of original gelatin.
2. composite according to claim 1, it is characterised in that the mixture is by KP1, metakaolin, alkali Metal hydroxides and water composition.
3. composite according to claim 1 or 2, it is characterised in that KP1, metakaolin, alkali metal hydrogen-oxygen Compound and the weight of water ratio are 100: 101~108: 16~22: 6~16.
4. composite according to claim 3, it is characterised in that the mass ratio of the mixture and the carbon fiber is 3~6: 1；And the mass ratio of the mixture and the curing agent is 100: 0.2~0.4.
5. composite according to claim 4, it is characterised in that the K in the KP12O content be 9~ 18wt% and SiO2Content is 22~31wt%；And described alkali metal hydroxide is potassium hydroxide.
6. composite according to claim 1 or 2, it is characterised in that the composite sample that thickness is 12mm exists Composite quality retention rate >=98% after 1000 DEG C of ablation 600s.
7. composite according to claim 6, it is characterised in that：
Using GJB 323A-1996 in heat flow density 4309.1Kw/m2It is 0.05 with setting-out line ablating rate under ablation time 20s ~0.1mm/s；
It is 32mm cylinder sample at a temperature of room temperature~800 DEG C to a diameter of 11mm and height to use GJB 330A-2000 The specific heat capacity of measure is 1.1~1.4kJ/kg DEG C；
It is 117~163MPa for the tensile strength of 250 × 25 × 4mm Specimen Determination to size to use GB/T 1447-2005； With
It is 109~134MPa for the bending strength of 80 × 15 × 5mm Specimen Determination to size to use GB/T 1449-2005.
8. the preparation method of the composite according to any one of claim 1~7, it is characterised in that comprise the following steps：
(1) original gelatin is prepared：KP1, metakaolin, alkali metal hydroxide and water are mixed to get mixture, as original Glue；
(2) glue is prepared：Curing agent and original gelatin are mixed to get glue；
(3) carbon fiber is handled：10~30min is cleaned by ultrasonic to the carbon cloth of carbon fiber-containing using organic solvent, dried standby；
(4) prepreg cloth is made：Glue obtained by step (2) is coated in obtained by step (3) on carbon cloth, and hangs to obtain prepreg cloth；
(5) blank plate is made：Prepreg cloth obtained by step (4) is cut, and is superimposed, is pressed into blank plate；
(6) solidify：Blank plate obtained by step (5) is handled 6~12 hours at 80~200 DEG C, then cooling obtains described multiple Condensation material.
9. preparation method according to claim 8, it is characterised in that：
In step (3), the organic solvent is selected from acetone or alcohol, and the carbon cloth of the carbon fiber-containing is plain weave carbon cloth；
In step (4), open assembly time is 1~2h；
In step (5), the thickness of blank plate is 5~30mm；With
In step (6), described is cooled to furnace cooling.
10. the purposes of the composite according to any one of claim 1~7, it is characterised in that the composite is used as The thermally protective materials of aircraft or automobile.
CN201710628915.0A 2017-07-28 2017-07-28 Carbon fibre reinforced composite, Preparation method and use Active CN107498941B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710628915.0A CN107498941B (en) 2017-07-28 2017-07-28 Carbon fibre reinforced composite, Preparation method and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710628915.0A CN107498941B (en) 2017-07-28 2017-07-28 Carbon fibre reinforced composite, Preparation method and use

Publications (2)

Publication Number Publication Date
CN107498941A true CN107498941A (en) 2017-12-22
CN107498941B CN107498941B (en) 2019-08-30

Family

ID=60690243

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710628915.0A Active CN107498941B (en) 2017-07-28 2017-07-28 Carbon fibre reinforced composite, Preparation method and use

Country Status (1)

Country Link
CN (1) CN107498941B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108621038A (en) * 2018-05-03 2018-10-09 威海南海碳材料有限公司 A kind of resin wheel of fibre reinforced and preparation method thereof
CN110128095A (en) * 2019-05-13 2019-08-16 武汉理工大学 A kind of particulate fibrous hybrid buildup aluminosilicate polymer composite material and preparation method thereof
CN111718180A (en) * 2020-07-01 2020-09-29 北京玻钢院复合材料有限公司 Chopped carbon fiber reinforced aluminum silicate ceramic matrix composite and preparation method thereof
CN113800837A (en) * 2021-09-30 2021-12-17 湖南工业大学 Continuous carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102010157A (en) * 2010-09-30 2011-04-13 华南理工大学 Bi-component environment-friendly inorganic polymer coating material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102010157A (en) * 2010-09-30 2011-04-13 华南理工大学 Bi-component environment-friendly inorganic polymer coating material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
RICHARD E. LYON, USMAN SORATHIA: "Fire resistant aluminosilicate composites", 《FIRE AND MATERIALS》 *
李克亮: "《地聚合物材料及其重金属固化处理》", 31 December 2014, 中国水利水电出版社 *
谢岁岁、饶曦、张芳等: "增强型地质聚合物的制备", 《武汉工程大学学报》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108621038A (en) * 2018-05-03 2018-10-09 威海南海碳材料有限公司 A kind of resin wheel of fibre reinforced and preparation method thereof
CN110128095A (en) * 2019-05-13 2019-08-16 武汉理工大学 A kind of particulate fibrous hybrid buildup aluminosilicate polymer composite material and preparation method thereof
CN111718180A (en) * 2020-07-01 2020-09-29 北京玻钢院复合材料有限公司 Chopped carbon fiber reinforced aluminum silicate ceramic matrix composite and preparation method thereof
CN113800837A (en) * 2021-09-30 2021-12-17 湖南工业大学 Continuous carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof
CN113800837B (en) * 2021-09-30 2022-11-25 湖南工业大学 Continuous carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof

Also Published As

Publication number Publication date
CN107498941B (en) 2019-08-30

Similar Documents

Publication Publication Date Title
CN107498941B (en) Carbon fibre reinforced composite, Preparation method and use
US6899837B2 (en) Inorganic matrix compositions, composites and process of making the same
Ribeiro et al. A review of particle-and fiber-reinforced metakaolin-based geopolymer composites
Villaquirán-Caicedo et al. A novel MK-based geopolymer composite activated with rice husk ash and KOH: performance at high temperature
Alomayri et al. Mechanical properties of cotton fabric reinforced geopolymer composites at 200–1000 C
AU2001292841A1 (en) Inorganic matrix compositions, composites and process of making the same
CN102731050B (en) Fireproof heat-insulated board with inorganic light aggregates and preparation method thereof
EP1328489A2 (en) Inorganic matrix compositions and composites incorporating the matrix composition
CN102936150A (en) Thermal insulation plate made of composite materials
Hong et al. Development of Cr-free aluminum phosphate binders and their composite applications
Lahoti et al. Influence of mix design parameters on geopolymer mechanical properties and microstructure
Adesanya et al. Thermal behaviour of ladle slag mortars containing ferrochrome slag aggregates
Gajiwala et al. Hybridized resin matrix approach applied for development of carbon/carbon composites—I
CN107188505B (en) A kind of fiber reinforcement inorganic composite heat-preserving plate and preparation method thereof
GB2245899A (en) Composite materials
CN107324697A (en) A kind of heat insulating material and preparation method thereof
Azmi et al. Crumb rubber geopolymer mortar at elevated temperature exposure
CN110627520A (en) Method for preparing composite heat-insulating material from waste inorganic heat-insulating material
Mandal et al. Effect of Na2O content on performance of fly ash geopolymers at elevated temperature
CN102127453A (en) Chemical sand fixing agent and preparation method thereof
JP7449701B2 (en) Geopolymer-like cured body
CN114213019A (en) Preparation method of sodium-calcium geopolymer glass ceramic filled with phosphate glass
Niu et al. Self-reinforced aluminum phosphate framework/bismaleimide composites with double cross-linking hybrid structures
CN111909484B (en) In-situ nano modified phenolic resin building thermal insulation material and preparation method thereof
CZ2009733A3 (en) Liquid geopolymeric resin suitable for the production of volume-stable reinforced composites and process for preparing thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant