CN106279872B - Polymer/carbon fiber hollow composite material and preparation method thereof - Google Patents

Polymer/carbon fiber hollow composite material and preparation method thereof Download PDF

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CN106279872B
CN106279872B CN201610645285.3A CN201610645285A CN106279872B CN 106279872 B CN106279872 B CN 106279872B CN 201610645285 A CN201610645285 A CN 201610645285A CN 106279872 B CN106279872 B CN 106279872B
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polymer
carbon fiber
composite material
hollow composite
grafted
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CN106279872A (en
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杨鸣波
夏小超
刘正英
杨伟
谢丹丹
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Sichuan University
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    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/46—Means for plasticising or homogenising the moulding material or forcing it into the mould
    • B29C45/57—Exerting after-pressure on the moulding material
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to technical field of polymer materials, and in particular to a kind of high-performance polymer/carbon fiber hollow composite material and preparation method thereof.The present invention provides a kind of polymer/carbon fiber hollow composite material, and in the hollow composite material, carbon fiber is evenly dispersed in polymer, and polymer molecule forms the shish-kebab structure of orientation in carbon fiber surface crystallization of growing nonparasitically upon another plant；Wherein, it is 1%~20wt% that carbon fiber, which accounts for polymer/carbon fiber hollow composite material mass ratio,.The most significant advantage of hollow composite material of the method for the present invention preparation is: the polymer molecular chain (a) being grafted in the polymer molecular chain and matrix of carbon fiber surface is mutually interspersed to be piled up to form platelet, can enhance the interface binding power between carbon fiber and polymeric matrix；(b) polymer molecule forms highly oriented hybrid structure and makes hollow composite material that may show the strong and unyielding mechanical property taken into account in carbon fiber surface crystallization of growing nonparasitically upon another plant.

Description

Polymer/carbon fiber hollow composite material and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of high-performance polymer/carbon fiber is hollow compound Material and preparation method thereof.
Background technique
Carbon fiber is a kind of source and uses very extensive reinforcing filler, its main feature is that cheap easy acquisition, has High mechanical property.But with carbon fiber reinforced polymer composite material due to high ratio modulus, high specific strength, it is corrosion-resistant, A series of excellent performances such as high temperature resistant, it is each to have been widely used for guided missile, aviation, automobile, stationery sports goods and medical equipment etc. Field.But untreated carbon fiber surface lacks active function groups, and surface inertness is big, makes it difficult in a polymer matrix It is uniformly dispersed, and its interface performance between matrix resin is poor.
For these defects, a series of chemical surface modification often is carried out to filler in the prior art or to filler Shape carry out special designing and (such as Carbon 1997,35 (10), the 1581-1585.) (Carbon 2004,42 that achieves the goal (10), 1923-1929), for another example patent application CN103469534A describes carbon fiber surface chemical graft hexa Improve its interface performance between resin；Patent application CN103806274A, which is described, utilizes Ce4+Cause in carbon fiber surface Chemical grafting polymerization object improves the surface-active of carbon fiber, and then improves its interface quality between resin.There are also a large amount of A variety of methods of document report enhancing carbon fiber and resin base interface binding power, it is main including carbon fiber surface activation method and table The method of face grafting.
But these methods exist or react fierce uncontrollable or excessively high to the more demanding or cost of equipment, Or the defects of complex process, it can not heavy industrialization so as to cause these methods.
Air-auxiliary injection forming (GAIM) be regular injection form (CIM) on the basis of develop one kind it is novel Method for processing forming, have short molding cycle, save raw material, reduce clamp force, reduce residual stress and product size it is steady The advantages that qualitative good, has received widespread attention (Advances in Polymer Technology, 1995,14 (1): 1- 13).In Gas-assisted Injection Molding, a certain amount of polymer melt is injected in mold cavity first, secondly by high pressure inert gas Body (usually N2) injection mold cavity, polymer melt is penetrated and pushes, until melt is full of entire mold cavity, Zhi Hou Melt gradually cools and solidifies under the pressure maintaining effect of high pressure gas, finally be discharged gas and be opened take out product (Polymer, 2007, 48(19):5486-5492).Currently, the forming technique has been applied to prepare automobile component, electronic device, household electrical appliances, office automatically Change in the field of plastic products such as equipment, construction material (Macromolecular materials and engineering, 2000,284(1):76-80)。
But in the prior art, polymer/carbon fiber composite is prepared using air-auxiliary injection forming method without related The relevant report of material.
Summary of the invention
The purpose of the present invention is to provide a kind of polymer/carbon fiber hollow composite material, in gained composite material, polymerization A part of object is grafted to carbon fiber surface, and the polymer molecular chain for being grafted on carbon fiber surface polymerize with non-grafted part Object strand is mutually interspersed to be piled up to form platelet, is a large amount of highly oriented structure inside gained hollow composite material, to improve Interface binding power between carbon fiber and polymer, so that hollow composite material possesses high mechanical property.
Technical solution of the present invention:
The invention solves first technical problem be to provide a kind of polymer/carbon fiber hollow composite material, it is described In hollow composite material, carbon fiber is evenly dispersed in polymer, and polymer molecule grows nonparasitically upon another plant to crystallize in carbon fiber surface to be formed The shish-kebab structure of orientation；Wherein, it is 1%~20wt% that carbon fiber, which accounts for polymer/carbon fiber hollow composite material mass ratio,.
Further, in the polymer/carbon fiber hollow composite material, a part of strand of polymer is grafted to carbon fiber Dimension table face, the polymer molecular chain for being grafted on carbon fiber surface mutually interts with non-grafted part polymer molecular chain to be piled up Form platelet.
Further, in polymer/carbon fiber hollow composite material, the polymer is semi-crystalline polymer, is selected from isotactic At least one of polypropylene, nylon, polyethylene or polytetrafluoroethylene (PTFE)；Further, the weight average molecular weight of the polymer exists Between 10~600,000.
Further, the diameter of the carbon fiber is 80nm~5 μm.
The invention solves second technical problem there is provided above-mentioned polymer/carbon fiber hollow composite material systems Preparation Method includes the following steps:
(1) polymer/carbon fiber (Polymer/ first is made in carbon fiber (CF) and polymer (Polymer) melt blending CF) mixture；
(2) mixture of step (1) preparation is made to a part of polymer using electron irradiation method or plasma method Strand is grafted to carbon fiber surface, is prepared into polymer/polymer grafting carbon fiber (Polymer/Polymer-g-CF) altogether Mixed object；Wherein, the grafting rate of carbon fiber is 1%~30wt%；
(3) the polymer/polymer grafted carbon fiber blends by step (2) preparation use air-auxiliary injection forming system It is standby to obtain polymer/carbon fiber hollow composite material.
Further, the forming process of step (3) is as follows: first the polymer/polymer by step (2) preparation is grafted carbon fiber Blend plasticizing, then is penetrated through melt is short, and then high pressure gas penetrates melt and pushes melt full of entire type chamber, last pressure maintaining, Cooling, demoulding, is made polymer/carbon fiber hollow composite material.
Further, in step (2), when using electron irradiation method, irradiation dose is 1~40KGy.
Further, in step (3), the technological parameter of air-auxiliary injection forming is arranged are as follows: plasticization temperature is 175~220 DEG C, the short amount of penetrating 60~80%, 6.0~15.0Mpa of air pressure, 0~25s of gas cooling time, 10~30 DEG C of mold temperature.
In the present invention, polymer/carbon fiber is made in carbon fiber (CF) and polymer (Polymer) melt blending in step 1 (Polymer/CF) mixture is prepared using existing melt blending such as twin-screw basis comminution granulation, so that carbon fiber is equal Even dispersion is in the polymer.
The invention solves third technical problem be to provide interface cohesion between a kind of improvement carbon fiber and polymer The method of power: first carbon fiber is blended with polymer melting, polymer/carbon fiber mixture is made；Again by mixture through electronics Irradiation method or plasma method make carbon fiber surface be grafted a part of polymer polymer/polymer grafted carbon fiber blend Object；Polymer/carbon fiber hollow composite material finally is prepared using air-auxiliary injection forming method in blend；To rise The effect for improving interface binding power between carbon fiber and polymer is arrived.
Further, a kind of to improve between carbon fiber and polymer in the method for interface binding power, the gas assisted injection Forming method is as follows: polymer/polymer grafted carbon fiber blends being plasticized, then penetrates through melt is short, then high pressure gas is worn Root penetration body simultaneously pushes melt full of entire type chamber, and the hollow composite wood of polymer/carbon fiber is made in last pressure maintaining, cooling, demoulding Material.
Further, the technological parameter setting of air-auxiliary injection forming are as follows: plasticization temperature is 175~220 DEG C, the short amount of penetrating 60 ~80%, 6.0~15.0Mpa of air pressure, 0~25s of gas cooling time, 10~30 DEG C of mold temperature.
Beneficial effects of the present invention:
(1) the most significant advantage of hollow composite material of this method preparation is:
(a) polymer molecular chain being grafted in the polymer molecular chain and matrix of carbon fiber surface is mutually interspersed to pile up shape At platelet, the interface binding power between carbon fiber and polymeric matrix can be enhanced；(b) polymer molecule is in carbon fiber surface Crystallization of growing nonparasitically upon another plant forms highly oriented hybrid structure and makes hollow composite material that may show the strong and unyielding mechanical property taken into account；
(2) hollow composite material is using injection moulding preparation, and method is simple and efficient, at low cost, is advantageously implemented work Industry metaplasia produces；
(3) polymer and CF selected by are technical grade product, and raw material is easy to get.
Detailed description of the invention
High density polyethylene (HDPE)/carbon nano-fiber after Fig. 1 predose after high density polyethylene (HDPE) (HDPE) and predose (HDPE/CNF) infrared spectrogram；IR mark passes through electron irradiation in figure；
Fig. 2 gas-assistance injection molding high density polyethylene (HDPE)/grafted polyethylene carbon nano-fiber (GAIM HDPE/HDPE-g- CNF) the cross-section morphology figure of hollow composite material: (a) 40000 ×；(b)80000×；
The crystalline morphology structures figure of Fig. 3 GAIM HDPE/HDPE-g-CNF hollow composite material: (a) 100nm；(b) 300nm；(c)600nm；(d)1000nm；(e)1400nm；Vertical direction is shear flow direction.
Fig. 4 gas assisted molding high density polyethylene (HDPE) (GAIM HDPE) hollow material and GIAM HDPE/HDPE-g-CNF are hollow Composite material and normal injection form high density polyethylene (HDPE)/grafted polyethylene carbon nano-fiber (CIM HDPE/HDPE-g- CNF) the stress-strain diagram of composite material.
Specific embodiment
The present invention provides a kind of polymer/carbon fiber hollow composite material, and in the hollow composite material, carbon fiber is uniform Ground disperses in the polymer, and polymer molecule is in carbon fiber surface (growth pattern are as follows: if polymer molecule is perpendicular to carbon fiber surface Face is grown nonparasitically upon another plant growth) crystallization of growing nonparasitically upon another plant forms the hydridization shish-kebab structure of orientation；Wherein, it is hollow compound to account for polymer/carbon fiber for carbon fiber Quality of materials ratio is 1%~20wt%.
In the present invention, the polymer is industrial products grade semi-crystalline polymer；The CF is common commercialization Enhance carbon fiber.
The present invention also provides a kind of carbon fiber hollow composite material of high-performance polymer/graft polymers and its preparations Method.Make polymer molecular chain using the method for electron irradiation than melt blending by certain mass using carbon fiber and polymer It is grafted to carbon fiber surface, finally by air-auxiliary injection forming, is prepared in polymer/graft polymers carbon fiber Empty composite material.The most significant feature of hollow composite material of this method preparation is: (1) polymer molecule is attached in carbon fiber surface Raw crystallization forms highly oriented hybrid structure；(2) polymer being grafted in the polymer molecular chain and matrix of carbon fiber surface Strand is mutually interspersed to form platelet, can enhance the interface binding power between carbon fiber and polymeric matrix；(3) hollow compound Material shows the strong and unyielding mechanical property taken into account；(4) hollow composite material is using injection moulding preparation, and method is simply high Effect is expected to realize industrialized production.
Inventive polymers/carbon fiber hollow composite material preparation method, can be used following specific embodiment:
(1) carbon fiber (CF) and polymer (Polymer) is first utilized into double-screw extruding pelletizing, it is ensured that CF is in the polymer It is uniformly dispersed, to prepare Polymer/CF composite granule；Wherein, extruder temperature is arranged are as follows: 170-220 DEG C；
(2) the further electron irradiation of pellet for preparing (1), makes partial polymer strand be grafted to carbon fiber surface Face, to prepare Polymer/Polymer-g-CF composite granule, grafting rate is 3%~15% percent；Wherein, irradiation dose For 1~40KGy；
(3) polymer/carbon fiber hollow composite material is prepared using air-auxiliary injection forming, forming process is as follows:
By the Polymer/Polymer-g-CF plasticizing of (2) preparation, melt is short penetrates for experience first, and then high pressure gas penetrates Melt simultaneously pushes a melt to be full of entire type chamber, and last pressure maintaining, cooling, demoulding prepare Polymer/Polymer-g- CF hollow composite material；Wherein, the technological parameter setting of air-auxiliary injection forming: 175-220 DEG C, the short amount of penetrating 60~80%, 6.0~15.0MPa of air pressure, 0~25s of gas cooling time, 0~30 DEG C of mold temperature.
In the present invention, irradiation dose is 1~40KGy；Irradiation dose refers to the radiation energy that per unit material mass is received Amount, referred to as dosage；International unit is defined as gray(Gy) (Gy), and 1 gray(Gy) indicates 1 kilogram of (Kg) material absorbing erg-ten (J) energy, 1Gy =1J/Kg；Traditionally commonly using draws special (rad) to indicate, 1 drawing is special to indicate 1 gram of 100 erg of (g) material absorbing (erg) energy, 1rad =100erg/g；So 1Gy=100rad.Kilogray (KGy) and million is commonly used in RADIATION PROCESSING draws special (Mrad) to indicate absorbent Amount: 10KGy=1Mrad.
Example given below is to specific descriptions of the invention, it is necessary to which indicated herein is that following embodiment is only used In the present invention is described further, it should not be understood as limiting the scope of the invention, field person skilled in the art Some nonessential modifications and adaptations are made to the present invention according to aforementioned present invention content, still fall within protection scope of the present invention.
Embodiment
14 ten thousand) and Nano carbon fibers (HDPE, 2911, Lanzhou Petrochemical, the weight average molecular weight of HDPE is to linear high-density polyethylene (CNF) (PR-19-XT-PS, Pyrograf-III, the diameter of carbon fiber are 100nm, length 200um) is tieed up according to mass ratio 90:10, which is added twin-screw extrude, to be blended, and is distributed to CNF uniformly in HDPE matrix and is obtained mixing pellet；Then By the electron irradiation of 30KGy, the blend of HDPE/HDPE-g-CNF is obtained；Finally prepared using air-auxiliary injection forming HDPE/HDPE-g-CNF hollow composite material, specific forming process are as follows:
The HDPE/HDPE-g-CNF blend of preparation is plasticized, melt is short penetrates for experience, and then high pressure gas penetrates primary molten Body simultaneously pushes a melt to be full of entire type chamber, and last pressure maintaining, cooling, demoulding prepare the hollow composite wood of HDPE/HDPE-g-CNF Material；Wherein, the technological parameter setting of air-auxiliary injection forming: 175 DEG C of plasticization temperature, the short amount of penetrating 80%, air pressure 10.4MPa, Gas cooling time 10s, 30 DEG C of mold temperature.
In addition, the present invention uses the method with embodiment 1, CNF is not dosed only, it only need to be by electron irradiation processing (no Pass through air-auxiliary injection forming), obtain irradiation HDPE sample.Also using the method with embodiment 1, (raw material and proportion are the same as implementation Example 1), but be not required to by electron irradiation processing and air-auxiliary injection forming, the HDPE/CNF sample not irradiated.
It is the preparation method difference of the pure HDPE product and common injecting forming material in Fig. 4 in Mechanics Performance Testing Are as follows:
Pure HDPE: using the method with embodiment 1, CNF is not added only, without irradiation, using gas assisted injection Molding；
Common injecting forming material: using the method with embodiment 1, by irradiation, but gas auxiliary note is not used Molding is penetrated, but normal injection is used to form, molding technological condition: 175 DEG C, 30 DEG C of mold temperature.
Performance test:
The infrared spectroscopy of sample after predose, the section and crystallization shape of hollow composite material, the power of hollow composite material Performance is learned to be tested as follows:
After being irradiated using 6700 infrared spectrometer of the Nicolet difference testing example 1 of Nicolet instrument company, the U.S. HDPE/CNF sample (IR-CNF/HDPE), irradiation HDPE sample (IR-HDPE) and the HDPE/CNF sample, pure not irradiated HDPE sample, the wave-number range of record are 400-4000cm-1, as a result as shown in Figure 1.As shown in Figure 1, HDPE/CNF sample after irradiation Product are in 840 and 1147cm-1There is new wave crest, 1100 and 1459cm in place-1Blue shift has occurred in the wave number at place, and irradiate HDPE and The HDPE/CNF sample not irradiated illustrates that polyethylene molecular chain has been grafted to carbon nano-fiber table there is no variation described above Face.
GAIM HDPE/HDPE-g-CNF hollow composite material is impregnated into 45min in liquid nitrogen, then along flow direction Carry out brittle failure.The hollow composite material brittle failure face GAIM HDPE/HDPE-g-CNF is in concentrated nitric acid, the concentrated sulfuric acid and liquor potassic permanganate Middle etching 5h.The processing of vacuum metal spraying is carried out in sample brittle failure face and etching surface, then uses the Inspect F type of FEI Co. Scanning electron microscope observes sample section pattern, the knot of analysis CNF dispersity in the base and hollow composite material The pattern of crystal structure, acceleration voltage 10kV, hollow composite material is as shown in Figures 2 and 3.It is can be found that from 40,000 times of Fig. 2 (a) Carbon nano-fiber is uniformly dispersed in polyethylene ontology, is uniformly dispersed in from 80,000 times of discovery carbon nano-fibers of Fig. 2 (b) poly- In ethylene ontology, base polyethylene is significantly coated on carbon nano-fiber surface, table between carbon nano-fiber and base polyethylene Reveal good interface cohesion.From Fig. 3 (a) it can be found that carbon nano-fiber along shear flow direction arranged in parallel, polyethylene The vertical carbon nano-fiber surface of strand is grown nonparasitically upon another plant growth, and highly oriented hydridization shish-kebab structure is formed, from Fig. 3 (b, c, d and e) can be with It was found that all foring this highly oriented structure in other regions of product, that is to say, that this highly oriented structure is in hollow composite wood Material all areas are formed on a large scale.
The mechanical property of three groups of hollow composite materials is tested using the omnipotent test machine of 5567Instron, rate of extension is 50mm/min, as a result as shown in Figure 4.From Fig. 4 it can be found that 1 gained hollow composite material (GAIM HDPE/HDPE- of embodiment G-CNF mechanical property) is apparently higher than pure HDPE product (GAIM HDPE) and the molding hollow composite material of normal injection (CIM HDPE/HDPE-g-CNF), it is molding hollow with pure HDPE (GIAM HDPE) product (21.5MPa) and normal injection The yield strength of composite material (CIM HDPE/HDPE-g-CNF) product (24.0MPa) compares, GAIM HDPE/HDPE-g- 85.1% and 65.8% has been respectively increased in the yield strength of CNF hollow composite material (39.8MPa).In terms of modulus: with GIAM HDPE product (990MPa) compares with the modulus of CIM HDPE/HDPE-g-CNF product material (1480MPa), GAIM HDPE/ 98.0% and 32.4% has been respectively increased in the yield strength of HDPE-g-CNF hollow composite material (1960MPa).With GIAM HDPE Product is compared, and the elongation at break of GAIM HDPE/HDPE-g-CNF hollow composite material is substantially reduced, but still is that toughness is disconnected It splits, can satisfy the use needs of certain materials.

Claims (11)

1. polymer/carbon fiber hollow composite material, which is characterized in that in the hollow composite material, carbon fiber equably divides It dissipates in the polymer, polymer molecule is grown nonparasitically upon another plant in carbon fiber surface crystallizes the shish-kebab structure for forming orientation；Wherein, carbon fiber accounts for poly- Conjunction object/carbon fiber hollow composite material mass ratio is 1wt%~20wt%；The polymer is semi-crystalline polymer；And: In the polymer/carbon fiber hollow composite material, a part of strand of polymer is grafted to carbon fiber surface, is grafted on carbon The polymer molecular chain and non-grafted polymers strand of fiber surface are mutually interspersed to be piled up to form platelet；
The polymer/carbon fiber hollow composite material is made using following preparation methods:
(1) first carbon fiber is blended with polymer melting and polymer/carbon fiber mixture is made；
(2) polymer/carbon fiber mixture by step (1) preparation makes polymer using electron irradiation method or plasma method A part of strand be grafted to carbon fiber surface, polymer/polymer grafted carbon fiber blends are prepared；Wherein, carbon The grafting rate of fiber is 1%~30wt%；
(3) polymer/polymer grafted carbon fiber blends prepared by step (2) are prepared into using air-auxiliary injection forming To polymer/carbon fiber hollow composite material.
2. polymer/carbon fiber hollow composite material according to claim 1, which is characterized in that the semi-crystalline polymer Selected from least one of isotactic polypropylene, nylon, polyethylene or polytetrafluoroethylene (PTFE).
3. polymer/carbon fiber hollow composite material according to claim 2, which is characterized in that the weight of the polymer is equal Molecular weight is between 100,000~600,000.
4. polymer according to claim 1 or claim 2/carbon fiber hollow composite material, which is characterized in that the carbon fiber it is straight Diameter is 80nm~5 μm.
5. any one of Claims 1 to 4 polymer/carbon fiber hollow composite material preparation method, which is characterized in that institute Preparation method is stated to include the following steps:
(1) first carbon fiber is blended with polymer melting and polymer/carbon fiber mixture is made；
(2) polymer/carbon fiber mixture by step (1) preparation makes polymer using electron irradiation method or plasma method A part of strand be grafted to carbon fiber surface, polymer/polymer grafted carbon fiber blends are prepared；Wherein, carbon The grafting rate of fiber is 1%~30wt%；
(3) polymer/polymer grafted carbon fiber blends prepared by step (2) are prepared into using air-auxiliary injection forming To polymer/carbon fiber hollow composite material.
6. polymer/carbon fiber hollow composite material preparation method according to claim 5, which is characterized in that step (3) Air-auxiliary injection forming process it is as follows: first by step (2) preparation polymer/polymer grafted carbon fiber blends mould Change, then penetrated through melt is short, then high pressure gas penetrates melt and pushes melt full of entire type chamber, and last pressure maintaining, takes off cooling Polymer/carbon fiber hollow composite material is made in mould.
7. according to the polymer of claim 5 or 6/carbon fiber hollow composite material preparation method, which is characterized in that step (2) in, when using electron irradiation method, irradiation dose is 1~40KGy.
8. according to the polymer of claim 5 or 6/carbon fiber hollow composite material preparation method, which is characterized in that gas The technological parameter of assisted injection molding is arranged are as follows: and plasticization temperature is 175~220 DEG C, the short amount of penetrating 60~80%, air pressure 6.0~ 15.0Mpa, 10~25s of gas cooling time, 10~30 DEG C of mold temperature.
9. a kind of method for improving interface binding power between carbon fiber and polymer, which is characterized in that first by carbon fiber with polymerize Polymer/carbon fiber mixture is made in object melt blending；Mixture is made into carbon fiber through electron irradiation method or plasma method again A part of polymer polymer/polymer grafted carbon fiber blends of surface grafting；Last blend is assisted using gas Polymer/carbon fiber hollow composite material is prepared in injection moulding；Improve between carbon fiber and polymer to play The effect of interface binding power；Wherein, the polymer is semi-crystalline polymer.
10. the method according to claim 9 for improving interface binding power between carbon fiber and polymer, which is characterized in that The semi-crystalline polymer is selected from least one of isotactic polypropylene, nylon, polyethylene or polytetrafluoroethylene (PTFE).
11. according to a kind of method for improving interface binding power between carbon fiber and polymer of claim 9 or 10, feature It is, the process of air-auxiliary injection forming is as follows: is first plasticized polymer/polymer grafted carbon fiber blends, then through molten Body is short to be penetrated, and then high pressure gas penetrates melt and pushes melt full of entire type chamber, and polymerization is made in last pressure maintaining, cooling, demoulding Object/carbon fiber hollow composite material.
CN201610645285.3A 2016-08-09 2016-08-09 Polymer/carbon fiber hollow composite material and preparation method thereof Expired - Fee Related CN106279872B (en)

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聚乙烯/碳纤维熔体在二次流动过程中碳纤维直径对杂化串晶形成的影响;夏小超，杨鸣波;《2015年全国高分子学术论文报告会》;20151017;摘要部分

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