CN106543608A - The manufacture method of modified carbon fiber reinforced resin based composites - Google Patents
The manufacture method of modified carbon fiber reinforced resin based composites Download PDFInfo
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- CN106543608A CN106543608A CN201611131358.3A CN201611131358A CN106543608A CN 106543608 A CN106543608 A CN 106543608A CN 201611131358 A CN201611131358 A CN 201611131358A CN 106543608 A CN106543608 A CN 106543608A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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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
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- 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
- C08J2327/00—Characterised by the use of 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 a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses the manufacture method of modified carbon fiber reinforced resin based composites, comprises the following steps：1) carbon fiber is soaked in hypophosphites solution, adds peroxide, 2～4h is processed at 85～100 DEG C, is filtered, drying obtains the carbon fiber of surface phosphinic acid；2) carbon fiber of surface hypophosphorous acid and politef powder are carried out into mechanical blending, by mixed powder extrusion forming, sinters, obtain final product.The present invention by after carbon fiber modified process can with politef formed strong mechanical interlock and chemical bond and, substantially improve the interfacial adhesion of carbon fiber and matrix material so that carbon fiber high-performance is given full play to.
Description
Technical field
The present invention relates to a kind of carbon fibre composite, and in particular to a kind of modified carbon fiber reinforced resin based composites
Manufacture method.
Background technology
Carbon fiber is the fibrous polymer carbon changed by organic fiber Jing solid state reactions, is a kind of high performance elder generation
Enter nonmetallic materials.Not only density is low, specific strength is high for carbon fiber, modulus is big, also with good thermostability and chemical stability.
Some functions of performance although carbon fiber can be used alone, it is belonged to fragile material, only it is firmly combined with matrix material
When together, its excellent mechanical property could be effectively played.Therefore, carbon fiber is mainly used as the enhancing phase in composite.
At present, purposes is most widely carbon fiber enhancement resin base composite material.In carbon fiber enhancement resin base composite material, carbon is fine
Dimension is main carrying constituent element, and matrix is then for carbon fiber is adhesively fixed, and transfers loads to every fiber.Composite
Interface be the bridge connected between carbon fiber and matrix, and the transmitter of stress.The property at interface directly determines composite wood
Every mechanical property of material.When interfacial adhesion is preferable, plus load major part can be delivered to fiber, play fiber
Effect potentiation, and it is improved the bulk strength of composite.When interfacial adhesion is bad or even there is gap or hole
During hole, stress effectively can not be transmitted, and the stress concentration that hole is produced under plus load can also accelerate sprouting for crackle
Raw and extension, so as to cause composite to be easily layered, have impact on the heat resistance and mechanical property of composite.Carbon fiber exists
During preparation will in high temperature inert gas carbonization treatment, with the effusion and the enrichment of carbon of non-carbon element, carbon fiber surface is lived
Property number of functional groups reduce, be deteriorated with the wellability of matrix resin.Additionally, in order to the tensile strength for improving carbon fiber subtracts as far as possible
Few surface defect, thus results in carbon fiber specific surface area less.So smooth surface is poor with the Anchoring Effect of matrix, causes
Carbon fibre composite boundary strength is reduced, and also limit the high performance performance of carbon fiber.Therefore, in order to improve carbon fiber with
The bonding interface of matrix material, and give full play to the characteristic of carbon fiber high-strength degree and high-moduluss, it is necessary to by the surface of carbon fiber
It is modified to improve its wellability and cementability with matrix, so as to improve the interfacial combined function of composite.
The content of the invention
The technical problem to be solved is to provide a kind of making of modified carbon fiber reinforced resin based composites
Method, the method is by increasing the mechanical interlock and chemical bond of composite material interface and substantially increasing the boundary of composite
Face binding ability.
The technical scheme that the present invention is provided is the manufacture method of modified carbon fiber reinforced resin based composites, including following
Step：
1) carbon fiber is soaked in hypophosphites solution, adds peroxide, 2～4h, mistake are processed at 85～100 DEG C
Filter, drying, obtains the carbon fiber of surface phosphinic acid；
2) carbon fiber of surface hypophosphorous acid and politef powder are carried out into mechanical blending, mixed powder is pressurizeed into
Type, sintering, obtains final product.
Step 1) in, carbon fiber being soaked in into phosphinates solution, and adds peroxide, peroxide is affine with carbon
Effect causes the carbon key of carbon fiber surface to relax, and increases the activity of carbon fiber surface so that hypophosphorous acid group just smoothly can be introduced
To carbon fiber surface, so as to complete the phosphinic acid base of carbon fiber.
Step 2) in, Jing after phosphinic acid process, the corrasion of hypophosphites and peroxide causes carbon fine to carbon fiber
Dimension table face defines micropore of a large amount of diameters more than 10nm, and the presence of these micropores expands the surface area of carbon fiber, and poly- four
The molecular weight of fluorothene is 106～107, the micropore that molecular dimension is produced with corrasion is suitable, therefore, politef molecule
Chain forms mechanical interlock in can extending into the micropore of carbon fiber surface, increased the bonding at carbon fiber and politef interface
Intensity.
In addition, carbon fiber is Jing after phosphinic acid process, phosphinic acid base is introduced on carbon fiber surface, and the basic body of phosphinic acid has
There are non-centrosymmetrical construction featuress, a kind of tetrahedral configuration can be regarded as, P atoms are located at tetrahedral center, 4 summits
Respectively occupied by 2 C atoms and 2 O atoms so that the oxygen atom in phosphinic acid group has very strong coordination ability, can
To form hydrogen bond action with the F atom on politef, and hydrogen atom is in the center of O atom and F atom line, its bond distance
Shorter than common hydrogen bond, bond energy is far longer than common hydrogen bond, can reach 140～170KJ/mol so that politef and Jing phosphorus
Strong interface cohesion is formed between the carbon fiber of acidification.
Preferably, the concentration of the hypophosphites solution is 1～2mol/L.The feed liquid of carbon fiber and hypophosphites solution
Than for 1：8～15g/ml.
The consumption of peroxide for carbon fiber weight 1～3%.The peroxide is sodium peroxide or potassium peroxide.
The consumption of the carbon fiber of surface hypophosphorous acid for mixed powder volume 15～25%.
The extrusion forming is 3～6min of process under 30～40MPa.
Compared with prior art, the invention has the advantages that：
1) carbon fiber surface Jing hypophosphorous acidization process, increase carbon fiber surface area and generate it is substantial amounts of with diameter greater than
The micropore of 10nm so that politef molecule can be embedded in the hole of carbon fiber surface and form mechanical cohesive bond, considerably increase
The interfacial adhesion strength of composite.
2) Jing after phosphinic acid process, the O atom on phosphinic acid base passes through hydrogen with the F atom on politef to carbon fiber
Bond is closed, and H atom is placed exactly on the midpoint of O atom and F atom on line so that the bond distance of the hydrogen bond is shorter, and bond energy is up to
140～170KJ/mol, significantly larger than 20～40KJ/mol of conventional hydrogen bond, so as to greatly strengthen carbon fiber and politef
The adhesive strength at interface.
Specific embodiment
The present invention is further elaborated for specific examples below, but not as a limitation of the invention.
Embodiment 1
1) carbon fiber is pressed into solid-liquid ratio for 1：8g/ml is soaked in the hypophosphites solution of 1mol/L, adds carbon fiber
The sodium peroxide of the 1% of weight, processes 2h at 85 DEG C, filters, and drying obtains the carbon fiber of surface phosphinic acid；
2) carbon fiber of surface hypophosphorous acid and politef powder are carried out into mechanical blending, obtains mixed powder, its
In, the consumption of the carbon fiber of surface hypophosphorous acid is the 15～25% of mixed powder volume；Mixed powder is pressurizeed under 30MPa
Molding 3min, compressing blank is taken out, is put in Muffle furnace, is sintered 10h at 400 DEG C, obtain final product modified carbon fiber tree
Resin-based composite.
Comparative example 1
1) carbon fiber is put in batch-type furnace, is warming up to 450 DEG C, and is incubated 40min, take out standby after furnace cooling, obtain
To the carbon fiber of airoxidation；
2) carbon fiber of airoxidation and politef powder are carried out into mechanical blending, obtains mixed powder, its
In, the consumption of the carbon fiber after airoxidation is the 15～25% of mixed powder volume；Mixed powder is added under 30MPa
Molded 3min, compressing blank is taken out, is put in Muffle furnace, is sintered 10h, obtain final product carbon fibre resin at 400 DEG C
Based composites.
Comparative example 2
Carbon fiber is carried out into mechanical blending with poly- four ethylene powder, mixed powder is obtained, wherein, the consumption of carbon fiber is mixed
Close the 15～25% of powder volume；By mixed powder under 30MPa extrusion forming 3min, compressing blank is taken out, is put
Enter in Muffle furnace, 10h is sintered at 400 DEG C, obtain final product carbon fiber resin matrix composite.
Embodiment 2
1) carbon fiber is pressed into solid-liquid ratio for 1：15g/ml is soaked in the hypophosphites solution of 2mol/L, adds carbon fiber
The potassium peroxide of the 3% of weight, processes 4h at 100 DEG C, filters, and drying obtains the carbon fiber of surface phosphinic acid；
2) carbon fiber of surface hypophosphorous acid and politef powder are carried out into mechanical blending, obtains mixed powder, its
In, the consumption of the carbon fiber of surface hypophosphorous acid is the 25% of mixed powder volume；By mixed powder extrusion forming under 40MPa
6min, compressing blank is taken out, is put in Muffle furnace, is sintered 10h at 400 DEG C, obtain final product modified carbon fiber resin base
Composite.
Embodiment 3
1) carbon fiber is pressed into solid-liquid ratio for 1：10g/ml is soaked in the hypophosphites solution of 1.5mol/L, adds carbon fine
The sodium peroxide of the 2% of dimension weight, processes 3h at 95 DEG C, filters, and drying obtains the carbon fiber of surface phosphinic acid；
2) carbon fiber of surface hypophosphorous acid and politef powder are carried out into mechanical blending, obtains mixed powder, its
In, the consumption of the carbon fiber of surface hypophosphorous acid is the 20% of mixed powder volume；By mixed powder extrusion forming under 35MPa
5min, compressing blank is taken out, is put in Muffle furnace, is sintered 10h at 400 DEG C, obtain final product modified carbon fiber resin base
Composite.
Embodiment 4
1) carbon fiber is pressed into solid-liquid ratio for 1：8g/ml is soaked in the hypophosphites solution of 2mol/L, adds carbon fiber
The potassium peroxide of the 1% of weight, processes 2h at 100 DEG C, filters, and drying obtains the carbon fiber of surface phosphinic acid；
2) carbon fiber of surface hypophosphorous acid and politef powder are carried out into mechanical blending, obtains mixed powder, its
In, the consumption of the carbon fiber of surface hypophosphorous acid is the 25% of mixed powder volume；By mixed powder extrusion forming under 30MPa
6min, compressing blank is taken out, is put in Muffle furnace, is sintered 10h at 400 DEG C, obtain final product modified carbon fiber resin base
Composite.
The composite of embodiment 1～4 and comparative example 1～2 is carried out into tensile property and bending property test, is as a result seen
Following table：
| Group | Tensile strength MPa | Elongation at break % | Stretch moduluses GPa | Bending strength MPa |
| Embodiment 1 | 26.67 | 321.8 | 0.246 | 5.94 |
| Embodiment 2 | 26.45 | 316.7 | 0.253 | 6.03 |
| Embodiment 3 | 27.33 | 329.0 | 0.249 | 5.94 |
| Embodiment 4 | 28.72 | 310.4 | 0.253 | 5.99 |
| Comparative example 1 | 17.43 | 157.1 | 0.179 | 5.02 |
| Comparative example 2 | 16.45 | 148.2 | 0.055 | 4.92 |
Claims (7)
1. the manufacture method of modified carbon fiber reinforced resin based composites, it is characterised in that：Comprise the following steps：
1) carbon fiber is soaked in hypophosphites solution, adds peroxide, 2～4h is processed at 85～100 DEG C, is filtered,
Drying, obtains the carbon fiber of surface phosphinic acid；
2) carbon fiber of surface hypophosphorous acid and politef powder are carried out into mechanical blending, by mixed powder extrusion forming,
Sintering, obtains final product.
2. the manufacture method of modified carbon fiber reinforced resin based composites according to claim 1, it is characterised in that：Institute
The concentration for stating hypophosphites solution is 1～2mol/L.
3. the preparation method of modified carbon fiber reinforced resin based composites according to claim 2, it is characterised in that：Carbon
Fiber is 1 with the solid-liquid ratio of hypophosphites solution：8～15g/ml.
4. the manufacture method of modified carbon fiber reinforced resin based composites according to claim 1, it is characterised in that：Cross
The consumption of oxide for carbon fiber weight 1～3%.
5. the manufacture method of modified carbon fiber reinforced resin based composites according to claim 4, it is characterised in that：Institute
Peroxide is stated for sodium peroxide or potassium peroxide.
6. the manufacture method of modified carbon fiber reinforced resin based composites according to claim 1, it is characterised in that：Table
The consumption of the carbon fiber of face hypophosphorous acid for mixed powder volume 15～25%.
7. the manufacture method of modified carbon fiber reinforced resin based composites according to claim 1, it is characterised in that：Institute
It is 3～6min of process under 30～40MPa to state extrusion forming.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383788A (en) * | 2017-08-29 | 2017-11-24 | 张艳雪 | A kind of method that photocuring quickly prepares fiber-reinforced resin matrix compound material |
| CN111574811A (en) * | 2020-05-22 | 2020-08-25 | 陕西科技大学 | Preparation method of multilayer reticular zirconia fiber reinforced resin-based material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383788A (en) * | 2017-08-29 | 2017-11-24 | 张艳雪 | A kind of method that photocuring quickly prepares fiber-reinforced resin matrix compound material |
| CN111574811A (en) * | 2020-05-22 | 2020-08-25 | 陕西科技大学 | Preparation method of multilayer reticular zirconia fiber reinforced resin-based material |
| CN111574811B (en) * | 2020-05-22 | 2022-11-04 | 陕西科技大学 | Preparation method of multilayer reticular zirconia fiber reinforced resin-based material |
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Application publication date: 20170329 |