CN109369932A - The method for improving carbon fiber reinforced epoxy resin-based composite interfacial bond property based on curing agent modified sizing agent - Google Patents
The method for improving carbon fiber reinforced epoxy resin-based composite interfacial bond property based on curing agent modified sizing agent Download PDFInfo
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- CN109369932A CN109369932A CN201811227914.6A CN201811227914A CN109369932A CN 109369932 A CN109369932 A CN 109369932A CN 201811227914 A CN201811227914 A CN 201811227914A CN 109369932 A CN109369932 A CN 109369932A
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
A method of carbon fiber reinforced epoxy resin-based composite interfacial bond property is improved based on curing agent modified sizing agent.Curing agent, epoxy resin and organic solvent are uniformly mixed, sizing agent is made；Agent is carried out to carbon fiber to handle；It is dry using infusion process by carbon fiber by the slurry tank equipped with sizing agent；The carbon fiber of starching is subjected to Temperature Treatment afterwards, then prepares carbon fiber reinforced epoxy resin-based composite with epoxy resin-matrix bluk recombination.The present invention can be under the premise of not losing carbon fiber mechanical property, the interface area of crosslink density gradient variation is formed between fiber and resin, increase the Degree of interaction of sizing agent and fiber surface activity group, promote uniformly transferring for composite inner stress, improves the interfacial bond property of composite material.Method of the invention has many advantages, such as that simple and easy, favorable repeatability, low cost, are suitble to industrialized production at high efficiency.
Description
Technical field
The invention belongs to the surfaces of material and interface modification applied technical field, and in particular to one kind is based on curing agent modified
The method of sizing agent raising carbon fiber reinforced epoxy resin-based composite interfacial bond property.
Background technique
Carbon fiber enhancement resin base composite material is because of property such as its excellent specific strength, specific modulus, corrosion-resistant and conductive and heat-conductives
Can feature and be widely used in the fields such as aerospace, the energy, electronics, civil engineering, high-end Leisure Sport articles, and with complete
The consumption of ball energy resources and environmental pollution increasingly, carbon fiber enhancement resin base composite material can be by reducing weight, mentioning
High fuel efficiency solves the above problems with carbon emission is reduced and is highly expected.However, carbon fibre surface energy is low, hydrophily
The feature of difference keeps it poor with the wellability of resin matrix, and interface cohesion is weak, influences effective biography of the load between resin and fiber
It passs and disperses, the mechanical performance of composite material is made to reach theoretical value far away.Therefore, optimized based on Properties of Carbon Fiber Surface, occurred
A series of process for modifying surface, including oxidation, corona treatment, radiation modification, chemical graft, self assembly etc..These sides
Although the interfacial bond property of carbon fiber enhancement resin base composite material can be improved in method, but at the same time often along with complexity
Process process, the time is long, and acutely, process is toxic to human body and environment, is not suitable for industrialized production, not only wastes for reaction
The a large amount of energy and resource, and often will cause the reduction of carbon fiber strength.Therefore, fine in protection based on starching processing
While dimension, raising convergence, sizing agent processing has the characteristics that easy and is easy to large-scale production, closes it extensively
Note.Good sizing agent can be further improved the binding force between fiber and resin.Therefore, seek a kind of changing based on sizing agent
Property optimization method improve carbon fiber resin matrix composite boundary strength have important practical significance and application value.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation process is simple, the time is short and suitable industrialized production based on solidification
The method that the modified sizing agent of agent improves carbon fiber reinforced epoxy resin-based composite interfacial bond property.
To achieve the above object, the technical solution adopted by the present invention is that:
1) preparation of curing agent modified sizing agent
0.5~2% epoxy resin and 98%~99.5% organic solvent is taken to be uniformly mixed to obtain ring by mass percentage
Oxygen starching agent solution；
Then curing agent mixing is added into epoxy sizing agent solution by the 15%~60% of epoxy resin chemistry metering ratio
It is uniform to obtain curing agent modified starching agent solution；
2) carbon fiber surface goes agent
It is using soxhlet extraction method that carbon fiber is dry after 70 DEG C~80 DEG C 24~48h of condensing reflux using acetone as solvent；
Or carbon fiber is impregnated to drying after 24~72h in the solution of acetone or petroleum ether；
3) carbon fiber surface starching is handled
Carbon fiber after step 2) to be gone to agent using infusion process is by dry after the slurry tank equipped with starching agent solution, i.e., complete
It is handled at the surface size of carbon fiber used in carbon fiber reinforced epoxy resin-based composite；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 25 DEG C or T~T+20 DEG C 1~2h of processing, wherein T is the precuring temperature of epoxy resin
Degree；
5) carbon fiber of step 4) and epoxy resin-matrix bluk recombination are obtained into carbon fiber reinforced epoxy resin-based composite.
The epoxy resin of the step 1) is thermosetting epoxy resin.
The organic solvent of the step 1) is acetone, dimethylformamide, tetrahydrofuran or methylene chloride.
The curing agent of the step 1) is amine, anhydride or imidazole curing agent.
The mixing of the step 1) uses mechanical stirring, magnetic agitation or ultrasonic disperse.
Dip time of the step 3) carbon fiber in slurry tank is 10~30s.
The step 2,3) drying are in 60 DEG C~80 DEG C dry 2~3h.
The epoxy resin-base of the step 5) is thermosetting epoxy resin.
The invention has the following advantages that
1) present invention can form the interface area of crosslink density gradient variation between carbon fiber and resin, promote composite material
Internal stress uniformly transfers, and improves the interfacial bond property of composite material.
2) carbon fiber through the curing agent modified sizing agent coating of Temperature Treatment can increase sizing agent and carbon fiber surface is living
The Degree of interaction of property group, improves the interfacial bond property of composite material.
3) method of the invention is simple and easy, favorable repeatability, at low cost, high-efficient, be suitble to industrialized production, has good
Good economic benefit and prospects for commercial application.
4) present invention is not limited only to a certain specific carbon fiber resin matrix composite system, has universal adaptability and good
Good development prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrum of the epoxy sizing agent containing 15% stoichiometric ratio curing agent prepared by the embodiment of the present invention 1.
Fig. 2 is the carbon fiber of the epoxy sizing agent coating containing 15% stoichiometric ratio curing agent prepared by the embodiment of the present invention 1
Tie up surface topography map.
Fig. 3 is carbon fiber/epoxy interface shear strength histogram, and 1 is non-starching Treatment of Carbon and epoxy resin in Fig. 3
The interface shear strength of the composite material of compound preparation, 2 carbon fibers and epoxy resin coated for the sizing agent not containing curing agent
The interface shear strength of the composite material of compound preparation, the 3 epoxy starching to contain 15% stoichiometric ratio curing agent in embodiment 1
The interface shear strength of the composite material of the carbon fiber and compound preparation of epoxy resin of agent coating.
Fig. 4 is the carbon fiber of the epoxy sizing agent coating containing 15% stoichiometric ratio curing agent prepared by the embodiment of the present invention 2
Tie up the surface topography map after handling 2h at 150 DEG C.
Fig. 5 is carbon fiber/epoxy interface shear strength histogram, and 1 is non-starching Treatment of Carbon and epoxy resin in Fig. 5
The interface shear strength of the composite material of compound preparation, 2 carbon fibers and epoxy resin coated for the sizing agent not containing curing agent
The interface shear strength of the composite material of compound preparation, the 3 epoxy starching to contain 15% stoichiometric ratio curing agent in embodiment 2
Interface shear strength of the carbon fiber of agent coating after 150 DEG C of processing 2h with the composite material of the compound preparation of epoxy resin.
Fig. 6 is the carbon fiber of the epoxy sizing agent coating containing 30% stoichiometric ratio curing agent prepared by the embodiment of the present invention 3
Tie up surface topography map.
Fig. 7 is carbon fiber/epoxy interface shear strength histogram, and 1 is non-starching Treatment of Carbon and epoxy resin in Fig. 7
The interface shear strength of the composite material of compound preparation, 2 carbon fibers and epoxy resin coated for the sizing agent not containing curing agent
The interface shear strength of the composite material of compound preparation, the 3 epoxy starching to contain 30% stoichiometric ratio curing agent in embodiment 3
The interface shear strength of the composite material of the carbon fiber and compound preparation of epoxy resin of agent coating.
Fig. 8 is the carbon fiber of the epoxy sizing agent coating containing 30% stoichiometric ratio curing agent prepared by the embodiment of the present invention 4
Tie up the surface topography map after handling 2h at 130 DEG C.
Fig. 9 is carbon fiber/epoxy interface shear strength histogram, and 1 is non-starching Treatment of Carbon and epoxy resin in Fig. 9
The interface shear strength of the composite material of compound preparation, 2 carbon fibers and epoxy resin coated for the sizing agent not containing curing agent
The interface shear strength of the composite material of compound preparation, the 3 epoxy starching to contain 30% stoichiometric ratio curing agent in embodiment 4
Interface shear strength of the carbon fiber of agent coating after 130 DEG C of processing 2h with the composite material of the compound preparation of epoxy resin.
Figure 10 is the carbon fiber of the epoxy sizing agent coating containing 60% stoichiometric ratio curing agent prepared by the embodiment of the present invention 5
Tie up surface topography map.
Figure 11 is carbon fiber/epoxy interface shear strength histogram, and 1 is non-starching Treatment of Carbon and asphalt mixtures modified by epoxy resin in Figure 11
The interface shear strength of the composite material of the compound preparation of rouge, 2 carbon fibers and asphalt mixtures modified by epoxy resin coated for the sizing agent not containing curing agent
The interface shear strength of the composite material of the compound preparation of rouge, 3 is on the epoxies in embodiment 5 containing 60% stoichiometric ratio curing agent
Starch the interface shear strength of the carbon fiber of agent coating and the composite material of the compound preparation of epoxy resin.
Figure 12 is the carbon fiber of the epoxy sizing agent coating containing 60% stoichiometric ratio curing agent prepared by the embodiment of the present invention 6
Tie up the surface topography map after handling 1h at 140 DEG C.
Figure 13 is carbon fiber/epoxy interface shear strength histogram, and 1 is non-starching Treatment of Carbon and asphalt mixtures modified by epoxy resin in Figure 13
The interface shear strength of the composite material of the compound preparation of rouge, 2 carbon fibers and asphalt mixtures modified by epoxy resin coated for the sizing agent not containing curing agent
The interface shear strength of the composite material of the compound preparation of rouge, 3 is on the epoxies in embodiment 6 containing 60% stoichiometric ratio curing agent
Starch interface shear strength of the carbon fiber of agent coating after 140 DEG C of processing 1h with the composite material of the compound preparation of epoxy resin.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and embodiments.
Embodiment 1:
1) preparation of curing agent modified sizing agent
1% thermosetting epoxy resin and 99% organic solvent-acetone magnetic agitation 10min is taken to obtain by mass percentage
Epoxy sizing agent solution；
Then amine curing agent magnetic force is added into epoxy sizing agent solution by the 15% of epoxy resin chemistry metering ratio to stir
It mixes 20min and obtains curing agent modified starching agent solution；
2) carbon fiber surface goes agent
Using acetone as solvent, in 60 DEG C of dry 3h after carbon fiber is condensed back for 24 hours at 80 DEG C using soxhlet extraction method；
3) carbon fiber surface starching is handled
After carbon fiber after step 2) to be gone to agent using infusion process is by impregnating 20s in the slurry tank equipped with starching agent solution
In 60 DEG C of dry 3h, i.e. the surface size processing of carbon fiber used in completion carbon fiber reinforced epoxy resin-based composite；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 25 DEG C of processing 2h；
5) by the carbon fiber of step 4) and thermosetting epoxy resin matrix it is compound obtain it is carbon fiber reinforced epoxy resin-based multiple
Condensation material.Wherein the curing process temperature of epoxy resin-base is first 130 DEG C of precuring 1h, rear 180 DEG C of solidifications 2h, last 190
Solidify 3h after DEG C.
Infrared spectrum before and after the modified sizing agent of amine curing agent is located at as shown in Figure 1, amine curing agent is modified
3509cm-1Hydroxyl vibration peak be moved to 3440cm to lower wave number-1, and in 3377cm-1And 3248cm-1Appearance-NH2Function
The vibration of group and bending peak.
Fig. 2 is the carbon fiber surface shape appearance figure that the prepared epoxy sizing agent containing 15% stoichiometric ratio curing agent coats,
Sizing agent is uniformly coated in fiber surface, and fiber surface roughness reduces.
As shown in figure 3, the carbon fiber and epoxy of the sizing agent coating compared to non-starching Treatment of Carbon and not containing curing agent
The composite material of resin compounded preparation, the interface of the composite material of carbon fiber and the compound preparation of epoxy resin prepared by embodiment 1
57.3% and 26.7% has been respectively increased in adhesion strength.
Embodiment 2:
1) preparation of curing agent modified sizing agent
1% thermosetting epoxy resin and 99% organic solvent-acetone magnetic agitation 10min is taken to obtain by mass percentage
Epoxy sizing agent solution；
Then amine curing agent magnetic force is added into epoxy sizing agent solution by the 15% of epoxy resin chemistry metering ratio to stir
It mixes 20min and obtains curing agent modified starching agent solution；
2) carbon fiber surface goes agent
Using acetone as solvent, in 60 DEG C of dry 3h after carbon fiber is condensed back for 24 hours at 80 DEG C using soxhlet extraction method；
3) carbon fiber surface starching is handled
After carbon fiber after step 2) to be gone to agent using infusion process is by impregnating 20s in the slurry tank equipped with starching agent solution
In 60 DEG C of dry 3h, i.e. the surface size processing of carbon fiber used in completion carbon fiber reinforced epoxy resin-based composite；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 150 DEG C of processing 2h；
5) by the carbon fiber of step 4) and thermosetting epoxy resin matrix it is compound obtain it is carbon fiber reinforced epoxy resin-based multiple
Condensation material.Wherein the curing process temperature of epoxy resin-base is first 130 DEG C of precuring 1h, rear 180 DEG C of solidifications 2h, last 190
Solidify 3h after DEG C.
Fig. 4 is that the carbon fiber that the prepared epoxy sizing agent containing 15% stoichiometric ratio curing agent coats is handled at 150 DEG C
Surface topography map after 2h, sizing agent are uniformly coated in fiber surface, and fiber surface roughness reduces.
As shown in figure 5, the carbon fiber and epoxy of the sizing agent coating compared to non-starching Treatment of Carbon and not containing curing agent
The composite material of resin compounded preparation, the interface of the composite material of carbon fiber and the compound preparation of epoxy resin prepared by embodiment 2
33.8% and 7.8% has been respectively increased in adhesion strength.
Embodiment 3:
1) preparation of curing agent modified sizing agent
0.5% thermosetting epoxy resin and 99.5% organic solvent tetrahydrofuran mechanical stirring are taken by mass percentage
8min obtains epoxy sizing agent solution；
Then acid anhydride type curing agent machinery is added into epoxy sizing agent solution by the 30% of epoxy resin chemistry metering ratio
Stirring 10min obtains curing agent modified starching agent solution；
2) carbon fiber surface goes agent
Using acetone as solvent, using soxhlet extraction method by carbon fiber after 70 DEG C of condensing reflux 48h in 80 DEG C of dry 2h；
3) carbon fiber surface starching is handled
After carbon fiber after step 2) to be gone to agent using infusion process is by impregnating 30s in the slurry tank equipped with starching agent solution
In 70 DEG C of dry 3h, i.e. the surface size processing of carbon fiber used in completion carbon fiber reinforced epoxy resin-based composite；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 25 DEG C of processing 2h；
5) by the carbon fiber of step 4) and thermosetting epoxy resin matrix it is compound obtain it is carbon fiber reinforced epoxy resin-based multiple
Condensation material.Wherein the curing process temperature of epoxy resin-base is first 130 DEG C of precuring 1h, rear 180 DEG C of solidifications 2h, last 190
Solidify 3h after DEG C.
Fig. 6 is the carbon fiber surface shape appearance figure that the prepared epoxy sizing agent containing 30% stoichiometric ratio curing agent coats,
Sizing agent is uniformly coated in fiber surface, and fiber surface roughness reduces.
As shown in fig. 7, the carbon fiber and epoxy of the sizing agent coating compared to non-starching Treatment of Carbon and not containing curing agent
The composite material of resin compounded preparation, the interface of the composite material of carbon fiber and the compound preparation of epoxy resin prepared by embodiment 3
33.8% and 7.8% has been respectively increased in adhesion strength.
Embodiment 4:
1) preparation of curing agent modified sizing agent
0.5% thermosetting epoxy resin and 99.5% organic solvent tetrahydrofuran mechanical stirring are taken by mass percentage
8min obtains epoxy sizing agent solution；
Then acid anhydride type curing agent machinery is added into epoxy sizing agent solution by the 30% of epoxy resin chemistry metering ratio
Stirring 10min obtains curing agent modified starching agent solution；
2) carbon fiber surface goes agent
In 80 DEG C of dry 2h after carbon fiber is impregnated for 24 hours in the solution of acetone or petroleum ether；
3) carbon fiber surface starching is handled
After carbon fiber after step 2) to be gone to agent using infusion process is by impregnating 30s in the slurry tank equipped with starching agent solution
In 70 DEG C of dry 3h, i.e. the surface size processing of carbon fiber used in completion carbon fiber reinforced epoxy resin-based composite；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 130 DEG C of processing 2h；
5) by the carbon fiber of step 4) and thermosetting epoxy resin matrix it is compound obtain it is carbon fiber reinforced epoxy resin-based multiple
Condensation material.Wherein the curing process temperature of epoxy resin-base is first 130 DEG C of precuring 1h, rear 180 DEG C of solidifications 2h, last 190
Solidify 3h after DEG C.
Fig. 8 is that the carbon fiber that the prepared epoxy sizing agent containing 30% stoichiometric ratio curing agent coats is handled at 130 DEG C
Surface topography map after 2h, sizing agent is more uniform in fiber surface coating, sheet protrusion occurs, and fiber surface roughness increases.
As shown in figure 9, the carbon fiber and epoxy of the sizing agent coating compared to non-starching Treatment of Carbon and not containing curing agent
The composite material of resin compounded preparation, the interface of the composite material of carbon fiber and the compound preparation of epoxy resin prepared by embodiment 4
49.6% and 20.5% has been respectively increased in adhesion strength.
Embodiment 5:
1) preparation of curing agent modified sizing agent
2% thermosetting epoxy resin and 98% organic solvent dichloromethane ultrasonic disperse 5min are taken by mass percentage
Obtain epoxy sizing agent solution；
Then imidazole curing agent ultrasound is added into epoxy sizing agent solution by the 60% of epoxy resin chemistry metering ratio
Dispersion 30min obtains curing agent modified starching agent solution；
2) carbon fiber surface goes agent
Carbon fiber is impregnated in the solution of acetone or petroleum ether after 72h in 60 DEG C of dry 3h；
3) carbon fiber surface starching is handled
After carbon fiber after step 2) to be gone to agent using infusion process is by impregnating 10s in the slurry tank equipped with starching agent solution
In 80 DEG C of dry 2h, i.e. the surface size processing of carbon fiber used in completion carbon fiber reinforced epoxy resin-based composite；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 25 DEG C of processing 1h；
5) by the carbon fiber of step 4) and thermosetting epoxy resin matrix it is compound obtain it is carbon fiber reinforced epoxy resin-based multiple
Condensation material.Wherein the curing process temperature of epoxy resin-base is first 130 DEG C of precuring 1h, rear 180 DEG C of solidifications 2h, last 190
Solidify 3h after DEG C.
Figure 10 is the carbon fiber surface shape appearance figure that the prepared epoxy sizing agent containing 60% stoichiometric ratio curing agent coats,
Sizing agent is uniformly coated in fiber surface, and fiber surface roughness reduces.
As shown in figure 11, compared to the composite material of non-starching Treatment of Carbon and the compound preparation of epoxy resin, embodiment 5 is made
The interface binding intensity of the composite material of standby carbon fiber and the compound preparation of epoxy resin improves 14.0%；But compared to not containing solid
The carbon fiber of the sizing agent coating of agent and the composite material of the compound preparation of epoxy resin, carbon fiber and ring prepared by embodiment 5
The interface binding intensity of the composite material of oxygen resin compounded preparation reduces 8.1%.
Embodiment 6:
1) preparation of curing agent modified sizing agent
2% thermosetting epoxy resin and 98% organic solvent dichloromethane ultrasonic disperse 5min are taken by mass percentage
Obtain epoxy sizing agent solution；
Then imidazole curing agent ultrasound is added into epoxy sizing agent solution by the 60% of epoxy resin chemistry metering ratio
Dispersion 30min obtains curing agent modified starching agent solution；
2) carbon fiber surface goes agent
Using acetone as solvent, using soxhlet extraction method by carbon fiber after 80 DEG C of condensing reflux 48h in 70 DEG C of dry 3h；
3) carbon fiber surface starching is handled
After carbon fiber after step 2) to be gone to agent using infusion process is by impregnating 10s in the slurry tank equipped with starching agent solution
In 80 DEG C of dry 2h, i.e. the surface size processing of carbon fiber used in completion carbon fiber reinforced epoxy resin-based composite；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 140 DEG C of processing 1h；
5) by the carbon fiber of step 4) and thermosetting epoxy resin matrix it is compound obtain it is carbon fiber reinforced epoxy resin-based multiple
Condensation material.Wherein the curing process temperature of epoxy resin-base is first 130 DEG C of precuring 1h, rear 180 DEG C of solidifications 2h, last 190
Solidify 3h after DEG C.
Figure 12 is that the carbon fiber that the prepared epoxy sizing agent containing 60% stoichiometric ratio curing agent coats is handled at 140 DEG C
Surface topography map sizing agent after 1h is more uniform in fiber surface coating, sheet protrusion occurs, and fiber surface roughness increases.
As shown in figure 13, compared to the composite material of non-starching Treatment of Carbon and the compound preparation of epoxy resin, embodiment 6 is made
The interface binding intensity of the composite material of standby carbon fiber and the compound preparation of epoxy resin improves 19.4%；But compared to not containing solid
The carbon fiber of the sizing agent coating of agent and the composite material of the compound preparation of epoxy resin, carbon fiber and ring prepared by embodiment 6
The interface binding intensity of the composite material of oxygen resin compounded preparation reduces 3.8%.
Claims (8)
1. a kind of improve carbon fiber reinforced epoxy resin-based composite interfacial bond property based on curing agent modified sizing agent
Method, it is characterised in that:
1) preparation of curing agent modified sizing agent
Take by mass percentage 0.5~2% epoxy resin and 98%~99.5% organic solvent be uniformly mixed on epoxy
Starch agent solution；
Then curing agent is added into epoxy sizing agent solution by the 15%~60% of epoxy resin chemistry metering ratio to be uniformly mixed
Obtain curing agent modified starching agent solution；
2) carbon fiber surface goes agent
It is using soxhlet extraction method that carbon fiber is dry after 70 DEG C~80 DEG C 24~48h of condensing reflux using acetone as solvent；
Or carbon fiber is impregnated to drying after 24~72h in the solution of acetone or petroleum ether；
3) carbon fiber surface starching is handled
The carbon fiber after agent is gone to pass through drying after the slurry tank equipped with starching agent solution, i.e. completion carbon step 2) using infusion process
The surface size of carbon fiber used in fiber reinforced epoxy resin based composites is handled；
4) carbon fiber surface Temperature Treatment
By the carbon fiber after starching in 25 DEG C or T~T+20 DEG C 1~2h of processing, wherein T is the precuring temperature of epoxy resin；
5) carbon fiber of step 4) and epoxy resin-matrix bluk recombination are obtained into carbon fiber reinforced epoxy resin-based composite.
2. according to claim 1 improve carbon fiber reinforced epoxy resin-based composite based on curing agent modified sizing agent
The method of interfacial bond property, it is characterised in that: the epoxy resin of the step 1) is thermosetting epoxy resin.
3. according to claim 1 improve carbon fiber reinforced epoxy resin-based composite based on curing agent modified sizing agent
The method of interfacial bond property, it is characterised in that: the organic solvent of the step 1) is acetone, dimethylformamide, tetrahydro furan
It mutters or methylene chloride.
4. according to claim 1 improve carbon fiber reinforced epoxy resin-based composite based on curing agent modified sizing agent
The method of interfacial bond property, it is characterised in that: the curing agent of the step 1) is amine, anhydride or imidazole curing agent.
5. according to claim 1 improve carbon fiber reinforced epoxy resin-based composite based on curing agent modified sizing agent
The method of interfacial bond property, it is characterised in that: the mixing of the step 1) is using mechanical stirring, magnetic agitation or ultrasound point
It dissipates.
6. according to claim 1 improve carbon fiber reinforced epoxy resin-based composite based on curing agent modified sizing agent
The method of interfacial bond property, it is characterised in that: dip time of the step 3) carbon fiber in slurry tank is 10~30s.
7. according to claim 1 improve carbon fiber reinforced epoxy resin-based composite based on curing agent modified sizing agent
The method of interfacial bond property, it is characterised in that: the step 2,3) drying are in 60 DEG C~80 DEG C dry 2~3h.
8. according to claim 1 improve carbon fiber reinforced epoxy resin-based composite based on curing agent modified sizing agent
The method of interfacial bond property, it is characterised in that: the epoxy resin-base of the step 5) is thermosetting epoxy resin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113278173A (en) * | 2021-07-07 | 2021-08-20 | 中科英华长春高技术有限公司 | Application of lignin-based sizing agent in epoxy acrylate composite material |
| CN113737528A (en) * | 2021-09-16 | 2021-12-03 | 泰山体育产业集团有限公司 | Degradable resin carbon fiber sizing agent |
| CN115012216A (en) * | 2022-05-30 | 2022-09-06 | 哈尔滨工程大学 | Modified PEEK-based sizing agent, preparation thereof and application thereof in preparation of carbon fiber/epoxy resin composite material |
| CN115262230A (en) * | 2022-08-30 | 2022-11-01 | 北京航空航天大学 | Fiber pretreatment method, sizing agent obtaining method and composite material fiber |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113278173A (en) * | 2021-07-07 | 2021-08-20 | 中科英华长春高技术有限公司 | Application of lignin-based sizing agent in epoxy acrylate composite material |
| CN113737528A (en) * | 2021-09-16 | 2021-12-03 | 泰山体育产业集团有限公司 | Degradable resin carbon fiber sizing agent |
| CN115012216A (en) * | 2022-05-30 | 2022-09-06 | 哈尔滨工程大学 | Modified PEEK-based sizing agent, preparation thereof and application thereof in preparation of carbon fiber/epoxy resin composite material |
| CN115012216B (en) * | 2022-05-30 | 2023-06-23 | 哈尔滨工程大学 | Modified PEEK-based sizing agent, preparation thereof and application thereof in preparation of carbon fiber/epoxy resin composite material |
| CN115262230A (en) * | 2022-08-30 | 2022-11-01 | 北京航空航天大学 | Fiber pretreatment method, sizing agent obtaining method and composite material fiber |
| CN115262230B (en) * | 2022-08-30 | 2023-06-16 | 北京航空航天大学 | Fiber pretreatment method, sizing agent obtaining method and composite fiber |
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