CN104264484A - Emulsion type carbon fiber sizing agent and preparation method and application thereof - Google Patents
Emulsion type carbon fiber sizing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an emulsion type carbon fiber sizing agent and a preparation method and application thereof. The sizing agent comprises main size, an emulsifier, graphene oxide, a diluent and water, wherein the amount of the emulsifier is 0.5-6 weight percent of that of the main size; and the amount of graphene oxide is 0.1-2 weight percent of that of the main size. The preparation method comprises the following steps: mixing the main size, the diluent and the emulsifier, stirring and premixing; and slowly adding an aqueous solution of graphene oxide for performing phase inversion emulsification to form Pickering emulsion in which graphene oxide and the emulsifier are stable, thereby obtaining the sizing agent. The preparation method disclosed by the invention is easy to operate, the stability of the sizing agent is improved by adopting the synergistic effect of graphene oxide and the emulsifier, the amount of the emulsifier is reduced, the environmental pollution is alleviated, the defects that the sizing agent with a single stable emulsifier is low in stability and the amount of the emulsifier is extremely large are overcome, the selection range of the main size is widened, the performances of carbon fibers can be improved after sizing, an interface bonding effect of a carbon fiber composite material is enhanced, and the mechanical strength of the carbon fiber composite material is improved.
Description
Technical field
The present invention relates to a kind of emulsion type carbon fiber sizing agent and its preparation method and application, particularly a kind of take graphene oxide as Pickering emulsion type carbon fiber sizing agent of stabilizing agent and its preparation method and application.
Background technology
Carbon fiber and composite thereof have a lot of excellent properties, have been widely used in military domain and civil area.But carbon fiber has certain fragility, and carbon fiber can produce the phenomenon such as single wire fracture, lousiness in process of production, so must carry out starching process to carbon fiber.Carbon fiber sizing agent has solvent-borne type and emulsion-type, and relatively more conventional is emulsion-type.Emulsion-type sizing agent is take resin as main component, by adding the sizing agent that a certain amount of emulsifying agent and auxiliary agent etc. are made, it take water as dispersant, cheap, pollution-free, generally can not on deflector roll cull, therefore, this kind of sizing agent is the inexorable trend of research and development.
The emulsion type carbon fiber sizing agent of current use, generally with resin for main slurry, utilize the surfactant of some routines as emulsifying agent, adopt phase conversion emulsifying preparation.The emulsifying agent used is sub-thermodynamic instability state, and the emulsion of preparation easily produces the phenomenon such as layering, precipitation by the impact of the external factor such as temperature and pH value, very unfavorable to application.Because resin viscosity is large, is not easy emulsification, generally needs to add a large amount of emulsifying agents, emulsifying agent is relatively costly, and cost is high, and has certain toxicity, a large amount of emulsifying agent also can remain in resistance to water, the heat resistance that fiber surface affects fiber, thus affects the performance of fibre reinforced composites.
Pickering emulsion, also known as solids stable emulsion, is utilize solids to substitute the thermodynamically stable emulsion of one of conventional surfactant as emulsifying agent.Because of the performance that it is good, Pickering emulsion is subject to the extensive concern of domestic and international researcher, has good application at secondary oil recovery, paint, food, medicine, cosmetic field.But the application of current Pickering emulsion in carbon fiber sizing agent has no relevant report.In Pickering emulsion, the selection of solids is very important, and not every solid particle can as the stabilizing agent of Pickering emulsion, and the solids selected by different system also exist larger difference, and conventional is Nano-meter SiO_2 at present
2.
Patent CN 1632217A discloses a kind of Nano-meter SiO_2
2the preparation method of modified carbon fiber emulsion pasting agent, by epoxy resin and nano silicon high-speed stirred, carries out modification to epoxy resin; Then adding emulsifying agent joins in the epoxy resin of modification, obtains sizing agent by Phase inversion emulsification.This sizing agent can improve interface performance and the intensity of carbon fiber, and emulsion can also be made more stable, high temperature resistant.SiO in this patent
2just as modifier, do not play the effect of stabilizing agent, sizing agent emulsion is not Pickering emulsion, does not reduce the consumption of emulsifying agent.And preparation method is that epoxy resin directly mixes with nano silicon, and in mixed process, nano silicon is easily reunited.
There is the technology added in carbon fiber sizing agent by Graphene open at present, such as patent CN102206919A discloses a kind of Graphene modified carbon fiber emulsion pasting agent and preparation method, the sizing agent of the method is made up of organic resin, emulsifying agent, lubricant, Graphene, organic solvent and deionized water, first adopt phase conversion emulsifying to form stable emulsion organic resin, emulsifying agent etc. during preparation, then Graphene is added in this emulsion form final sizing agent.Adding Graphene in this sizing agent is interface performance in order to improve carbon fiber and macro property, does not mention the effect that Graphene is improved emulsion-stabilizing.
Also graphene oxide is not added in sizing agent the relevant report improving sizing agent stability at present, if replaced by graphene oxide partial emulsifier to prepare sizing agent emulsion, greatly will improve the stability of sizing agent, the impact of emulsifying agent on carbon fiber performance can also be reduced, there is very large researching value.
Summary of the invention
The object of this invention is to provide a kind of emulsion type carbon fiber sizing agent, this sizing agent emulsifying agent use amount is few, and environmental pollution is little, can also improve the interface performance of carbon fibre composite, effective.
Another object of the present invention is to provide the preparation method of this sizing agent, and the method is simple to operate, easy to implement, gained sizing agent good stability.
Present invention also offers and use this sizing agent to the method for carbon fiber starching, after employing sizing agent of the present invention, carbon fiber performance is well improved.
The present invention is directed to the problem that existing emulsion type carbon fiber sizing agent emulsifier is large, replace partial emulsifier with graphene oxide, both improve the stability of sizing agent, the performance of carbon fiber can be improved again.Under the guidance of this thinking, through large quantifier elimination and experiment, by the selection of emulsifying agent, the selection of graphene oxide, emulsifier, the optimization of diluent, water and the adjustment of preparation method, finally obtain the emulsion type carbon fiber sizing agent that performance is good.Concrete technical scheme is as follows:
Emulsion type carbon fiber sizing agent of the present invention (is called for short carbon fiber sizing agent or sizing agent, lower same), comprise main slurry, emulsifying agent, graphene oxide, diluent and water, the consumption of emulsifying agent is 0.5 ~ 6wt% of main slurry, and the consumption of graphene oxide is 0.1 ~ 2wt% of main slurry.
Selective oxidation Graphene of the present invention but not Graphene replaces partial emulsifier, containing a large amount of hydroxyls and carboxyl in graphene oxide, by force water-soluble, good peptizaiton can be played in emulsion, and graphenic surface is not through preliminary treatment, water insoluble, there is no this peptizaiton.
The present invention replaces partial emulsifier with graphene oxide, decreases the consumption of emulsifying agent, improves the dispersiveness of main slurry in sizing agent, improves the stability of sizing agent.The consumption of graphene oxide is preferably the 0.2-0.6wt% of main slurry.After adding graphene oxide, the consumption of emulsifying agent can drop to below 6wt%, such as, can reduce 0.5-5wt%, 0.5-1.8wt%, 3-5wt%.
The present invention's graphene oxide used can take crystalline flake graphite as raw material, is obtained, also directly can buy commercially available prod by the Hummers method improved.The performance parameter of graphene oxide and self-characteristic are: thickness 0.9 ~ 1.5nm, lamella diameter 2 ~ 5 μm, number of plies 1-2.Only have and meet these requirements, the dispersion effect of main slurry just can be made good, otherwise the stabilizing agent of sizing agent can reduce.
The pH of sizing agent system of the present invention should about 6.0.
The consumption of diluent of the present invention is 10 ~ 50wt% of main slurry.
In sizing agent, the consumption flexibility of water is comparatively large, can control the consumption of water according to the concentration requirement of required sizing agent.General, in order to reduce the cost of sizing agent in transportation, preferably using less water when preparing sizing agent, adding extra water when starching again and being diluted to required concentration.In a preferred embodiment of the invention, the mass ratio of water and main slurry is 4:1.
What emulsifying agent of the present invention was selected is blended emulsifier, mass ratio is the mixture of the octyl phenol polyoxyethylene ether (OP-10) of 5 ~ 25:50 ~ 70:10 ~ 35, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS), and preferred mass is than being 10:65:25.Blended emulsifier is more effective than single emulsifier, and namely the selection of emulsifying agent of the present invention decreases the consumption of emulsifying agent, also improves the performance of sizing agent.
The main slurry that current sizing agent is selected is all the epoxy resin such as E-51, E-55 that viscosity is less, so easy emulsification, but these resin non-refractories, high-temperature resistant composite material system cannot be used for, and although AG80 epoxy resin can overcome this shortcoming, but be difficult to emulsification because viscosity is large, need the consumption strengthening emulsifying agent, be unfavorable for the use of carbon fiber.The present invention is by the adjustment to sizing agent formula, the high viscosity resins such as AG80 can be made when lower emulsifier content well to be disperseed and emulsification, widened the range of choice of main slurry, gained sizing agent good stability, also can not reduce the performance of carbon fiber, performance is high.In embodiments of the present invention, main slurry used is E-51, E-55 or AG80 epoxy resin.
The present invention's diluent used is non-activated thinner or reactive diluent, is preferably reactive diluent.Wherein, non-activated thinner is acetone, and reactive diluent is neopentylglycol diglycidyl ether (trade name 678).
Sizing agent of the present invention formula is unique, by working in coordination with of graphene oxide and emulsifying agent, and the acting in conjunction of other compositions, make sizing agent stable in properties, effect is good.Sizing agent preparation method of the present invention is also unique, in the preparation, by the selection to graphene oxide addition sequence and emulsification condition, makes sizing agent performance better.
The present invention adopts graphene oxide and emulsifying agent to work in coordination with stable method and has prepared Pickering emulsion-type sizing agent, decrease the consumption of emulsifying agent in emulsion, and graphene oxide is incorporated in sizing agent, improve the mechanical strength of carbon fibre composite.For this reason, must be significant to Industry of Carbon Fiber according to the carbon fiber sizing agent emulsion containing graphene oxide of Pickering emulsion emulsifiers principle exploitation.
The preparation method of emulsion type carbon fiber sizing agent of the present invention, comprising: main slurry, diluent are mixed with emulsifying agent, carries out stirring premix, and then slowly adds graphene oxide water solution and carry out Phase inversion emulsification, obtains sizing agent.Such hybrid mode can give full play to the dispersion and emulsion effect of emulsifying agent and graphene oxide, controls to minimum by the amount of emulsifying agent and graphene oxide.
In preparation method of the present invention, graphene oxide be join in form of an aqueous solutions comprise main slurry mixture in.Water required in water in graphene oxide water solution and sizing agent.In addition, the pH adjusting the aqueous solution is 6.0.
In preparation method of the present invention, graphene oxide water solution preferably joins in main slurry with the form dripped, and rate of addition is 0.1-5 mL/min, preferred 1mL/min.
In preparation method of the present invention, during premix, the mixture comprising main slurry stirs 20 min under the rotating speed of 2000 rpm.
In preparation method of the present invention, add graphene oxide when stirring the mixture comprising main slurry, mixing speed is 6500-10500 r/min; After adding graphene oxide, mixture is continued to stir 20min under this rotating speed, completes Phase inversion emulsification.
After method of the present invention, the sizing agent stability of gained is better.
Carbon fiber sizing agent of the present invention to the method for carbon fiber starching is: be 0.5-3.0wt% by above-mentioned emulsion type carbon fiber sizing agent thin up to solid content, then adopts infusion process to be invested on carbon fiber by the emulsion type carbon fiber sizing agent after dilution.The method is simple to operate, easy to implement.
In the above-mentioned method to carbon fiber starching, the dip time of carbon fiber in emulsion type carbon fiber sizing agent is 30s, by carbon fiber dry 10min at 100 DEG C after dipping.
The present invention has the following advantages:
1. the present invention adopts graphene oxide and emulsifying agent to work in coordination with the stability improving sizing agent, decrease the consumption of emulsifying agent, alleviate environmental pollution, overcome sizing agent poor stability stable by emulsifying agent merely and the too much defect of emulsifier, and the high-temperature-resistant epoxy resin being difficult to emulsification can be used as main slurry, stabilizing power is stronger, has also widened the range of choice of main slurry.
2, sizing agent even particle size distribution of the present invention, there is good heat resistance and bin stability, carbon fiber performance can be improved after starching, strengthen the effect of carbon fibre composite interface cohesion, improve the mechanical strength of carbon fibre composite.
3. preparation method of the present invention is simple to operate, easy to implement, and the preparation for carbon fiber sizing agent provides wide research and apply prospect.
Detailed description of the invention
Sizing agent of the present invention specifically comprises following preparation process:
First, get graphene oxide, use water-soluble solution; The pH value regulating the aqueous solution is 6.0, and ultrasonic disperse is even, is put in constant voltage dropper, stand-by.
Secondly, by main slurry, diluent, emulsifying agent mixing, mixture is uniformly mixed under 30 DEG C of water-baths, makes viscosity; Then mixture is taken out, stir 20 min with high-shearing dispersion emulsifying machine with the rotating speed of 2000 rpm, complete premix.
3rd, graphene oxide water solution is added drop-wise in the mixture after premix, regulate the rotating speed of high-shearing dispersion emulsifying machine to 6500 ~ 10500 r/min in dropping process, under this rotating speed, stirring 20 min is continued after adding, complete Phase inversion emulsification, namely obtain carbon fiber sizing agent of the present invention after cooling, survey its solid content stand-by.
In following embodiment, carbon fiber used is the model that toray Co., Ltd produces is the carbon fiber of T700SC, carries out slurry process before starching.Slurry is gone to adopt soxhlet extraction: to be wound around wherein uniformly by the carbon fiber bundle of suitable length on stainless steel rectangular framework, and to be put in apparatus,Soxhlet's.Assembling Soxhlet extraction device, add the acetone of appropriate volume, by controlling electric jacket voltage, regulating apparatus,Soxhlet's siphon 4 times per hour.After 36 h, adopt deionized water repeatedly to rinse carbon fiber, be then placed in 100 DEG C of thermostatic drying chambers dry, after 4 h, it is for subsequent use that cooling is placed in drier.
Graphene oxide used is that laboratory utilizes the Hummers method preparation improved, and detailed process prepared by graphene oxide is:
A., under room temperature, 0.5 weight portion sodium nitrate, 1 parts by weight of graphite powder and the 46 weight portion 98wt% concentrated sulfuric acids are mixed under condition of ice bath, stirs 30 min, and then slowly add 3 weight portion potassium permanganate, stir 30 min;
B. the reaction system in step a is heated to 35 DEG C, stirs 2 ~ 48 h, obtain brown suspension; In suspension, add 50 parts by weight of deionized water lentamente, stir, be warming up to 98 DEG C and continue reaction 5 ~ 10min, be cooled to room temperature;
C. the reactant liquor of step b is poured in 167 parts by weight of deionized water while stirring, add 5 weight portion 30wt% hydrogen peroxide, leave standstill 24h;
D. lower sediment is got, with deionized water centrifuge washing three times under 8000 r/min conditions, each 5min; Precipitate with deionized water is dialysed, until BaCl
2detect without SO
4 2-, add in deionized water by thick liquid after dialysis, ultrasonic process 1h, then by solution centrifugal 5min under the condition of 4000r/min, gained supernatant liquid is graphene oxide water solution.
E. the graphene oxide water solution obtained is diluted to 2 mg/mL, after ultrasonic 30 min, be placed in centrifuge tube, centrifugal 10min under 5000 rpm rotating speeds, gets upper solution and is placed in centrifuge tube, centrifugal 10min under 8000 rpm rotating speeds, get upper solution and be placed in centrifuge tube, centrifugal 10min under 11000 rpm rotating speeds, gets lower sediment, be dissolved in water to obtain graphene oxide water solution, graphene oxide water solution utilized freeze-drying to obtain graphene oxide powder.
The correlation performance parameters of graphene oxide is thickness 0.9 ~ 1.5nm, lamella diameter 2 ~ 5 μm, number of plies 1-2 layer.
Enumerate several preferred example of the present invention below, to be further elaborated the present invention, if no special instructions, in following embodiment, each constituent content of sizing agent is weight portion.
embodiment 1
Sizing agent consists of: main slurry epoxy resin (AG80) 100 parts, graphene oxide 0.1 part, emulsifying agent 6 parts, diluent neopentylglycol diglycidyl ether 15 parts, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is: first, adds in beaker, add main slurry AG80 epoxy resin neopentylglycol diglycidyl ether, emulsifying agent, mixture is uniformly mixed under 30 DEG C of water-baths, makes viscosity; Then mixture is taken out, stir 20 min with high-shearing dispersion emulsifying machine with the rotating speed of 2000 rpm.Secondly, get graphene oxide, soluble in water, the pH value regulating graphene oxide water solution with ammoniacal liquor is 6, ultrasonic 20 min, solution is put in constant voltage dropper, be added drop-wise in mixture with the speed of 5mL/min, and regulate the rotating speed of high-shearing dispersion emulsifying machine to 6500 r/min, add rear continuation stirring 20 min, namely obtain sizing agent after cooling, survey its solid content stand-by.
embodiment 2
Sizing agent consists of: main slurry epoxy resin (E-51) 100 parts, graphene oxide 0.3 part, emulsifying agent 5 parts, diluent neopentylglycol diglycidyl ether 10 parts, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Span-80) and neopelex (SDBS).
Sizing agent preparation method is: first, adds in beaker, add main slurry epoxy resin (E-51) neopentylglycol diglycidyl ether, emulsifying agent, mixture is uniformly mixed under 30 DEG C of water-baths, makes viscosity; Then mixture is taken out, stir 20 min with high-shearing dispersion emulsifying machine with the rotating speed of 2000 rpm.Secondly, get graphene oxide, be dissolved in water; The pH value regulating graphene oxide water solution with ammoniacal liquor is 6, ultrasonic 20 min, be put in constant voltage dropper, be added drop-wise in mixture with the speed of 1mL/min, and regulate the rotating speed of high-shearing dispersion emulsifying machine to 8500 r/min, add rear continuation stirring 20 min, namely obtain sizing agent after cooling, survey its solid content stand-by.
embodiment 3
Sizing agent consists of: main slurry epoxy resin (E-55) 100 parts, graphene oxide 2 parts, emulsifying agent 0.5 part, 50 parts, diluent acetone, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is: first, adds in beaker, add main slurry epoxy resin (E-55) acetone, mixture is uniformly mixed under 30 DEG C of water-baths, makes viscosity; Then, mixture is taken out, stirs 20 min with high-shearing dispersion emulsifying machine with the rotating speed of 2000 rpm.Secondly, get graphene oxide, be dissolved in water; The pH value regulating graphene oxide water solution with ammoniacal liquor is 6, ultrasonic 20 min, be put in constant voltage dropper, be added drop-wise in mixture with the speed of 0.1mL/min, and regulate the rotating speed of high-shearing dispersion emulsifying machine to 10500 r/min, add rear continuation stirring 20 min, namely obtain sizing agent after cooling, survey its solid content stand-by.
embodiment 4
Sizing agent consists of: main slurry epoxy resin (AG80) 100 parts, graphene oxide 0.5 part, emulsifying agent 6 parts, 30 parts, diluent acetone, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is: first, adds in beaker, add main slurry epoxy resin (AG80) acetone, emulsifying agent, mixture is uniformly mixed under 30 DEG C of water-baths, makes viscosity; Then, mixture is taken out, stirs 20 min with high-shearing dispersion emulsifying machine with the rotating speed of 2000 rpm.Secondly, get graphene oxide, be dissolved in water; The pH value regulating graphene oxide water solution with ammoniacal liquor is 6, ultrasonic 20 min, be put in constant voltage dropper, be added drop-wise in mixture with the speed of 1mL/min, and regulate the rotating speed of high-shearing dispersion emulsifying machine to 9500 r/min, add rear continuation stirring 20 min, namely obtain sizing agent after cooling, survey its solid content stand-by.
embodiment 5
Sizing agent consists of: main slurry epoxy resin (AG80) 100 parts, graphene oxide 0.6 part, emulsifying agent 1.8 parts, diluent neopentylglycol diglycidyl ether 40 parts, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is with embodiment 2.
embodiment 6
Sizing agent consists of: main slurry epoxy resin (AG80) 100 parts, graphene oxide 0.5 part, emulsifying agent 3 parts, diluent neopentylglycol diglycidyl ether 50 parts, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is with embodiment 2.
embodiment 7
The composition of sizing agent and preparation method with embodiment 2, unlike the mixture of the octyl phenol polyoxyethylene ether (OP-10) of: emulsifying agent to be mass ratio be 5:70:10, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is with embodiment 2.
embodiment 8
The composition of sizing agent and preparation method with embodiment 2, unlike the mixture of the octyl phenol polyoxyethylene ether (OP-10) of: emulsifying agent to be mass ratio be 25:50:35, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is with embodiment 2.
comparative example 1
Sizing agent consists of: main slurry epoxy resin (AG80) 100 parts, emulsifying agent 5 parts, diluent neopentylglycol diglycidyl ether 10 parts, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Sizing agent preparation method is with embodiment 2.
comparative example 2
Sizing agent composition is with embodiment 5, as follows: main slurry epoxy resin (AG80) 100 parts, graphene oxide 0.6 part, emulsifying agent 1.8 parts, diluent neopentylglycol diglycidyl ether 40 parts, 400 parts, water.The wherein mixture of the octyl phenol polyoxyethylene ether (OP-10) of emulsifying agent to be mass ratio be 10:65:25, anhydrous sorbitol list olein (Arlacel-80) and neopelex (SDBS).
Preparation method adopts the method with patent CN102206919A, graphene oxide is added again after forming emulsion, as follows: first, main slurry epoxy resin (AG80) is added in beaker, add neopentylglycol diglycidyl ether, emulsifying agent, mixture is uniformly mixed under 30 DEG C of water-baths, makes viscosity; Then, mixture is taken out, stirs 20 min with high-shearing dispersion emulsifying machine with the rotating speed of 2000 rpm.Secondly, according to the ratio of main slurry and water 1:4, mix up pH value be 6 deionized water be put in constant voltage dropper, be added drop-wise in mixture with the speed of 1mL/min, and regulate the rotating speed of high-shearing dispersion emulsifying machine to 8500 r/min, add rear continuation stirring 20 min, after cooling, form emulsion; Finally, graphene oxide is slowly added in this emulsion, stirs, obtain graphene oxide modification sizing agent.Finally add at this graphene oxide, do not play Phase inversion emulsification.
comparative example 3
Sizing agent composition and preparation method with embodiment 2, unlike: emulsifying agent is only OP-10.
The interlaminar shear strength (ILSS) of the stability of each sizing agent of above-mentioned preparation, the rate of sizing of starching carbon fiber, stiffness, lousiness amount, abrasion resistance and carbon-fibre reinforced epoxy resin is measured under room temperature.
The method for sizing of each sizing agent is: each sizing agent being diluted to solid content is 1.5wt %, and be attached on carbon fiber by infusion process by sizing agent, the impregnation time is 30 s, carbon fiber dry 10min at 100 DEG C after starching.
Test and evaluation method as follows:
1. sizing agent stability
Adopt centrifuge at room temperature to measure the dewatering ability of sizing agent, dewatering ability classification is as follows:
I grade: in 1500 r/min × 20min lower leafs;
II grade: in 2000 r/min × 20min lower leafs;
III grade: not stratified under 2500 r/min × 20min;
IV grade: not stratified under 3000 r/min × 20min;
V grade: not stratified under 3500 r/min × 20min.
2. sizing agent average grain diameter
With deionized water, sizing agent emulsion is diluted to measurement category, then adopts LS-13320 type laser particle size analyzer to carry out analyzing the granularmetric analysis of emulsion.
3. stiffness
Performance when research carbon fiber is subject to flecition is very important, because carbon fiber is in the process of braiding, be subject to bending stress repeatedly, especially when weaving multidimensional fabric, the angle of bank of carbon fiber on loom is very large, the flecition be subject to is very large, can produce flexural deformation, therefore requires that carbon fiber has the pliability of appropriateness.Before and after starching, the stiffness of carbon fiber can reflect the pliability of carbon fiber to a certain extent, and stiffness is larger, and pliability is lower.
The mensuration of stiffness adopts the fiber of fixed length to put the principle hanging up certain angle of dangling wherein.First unwinding to be carried out to carbon fiber.By carbon fiber through the twizzle of unwinding device, and walk around three stainless steel wheels, be wrapped on bobbins that rotating speed is about 10mm/s, starter motor reels.
Fiber after unwinding carries out the test of stiffness.Testing arrangement by radius be the stainless steel hook of 10mm as hitch point, under hitch point, there is a slide scale at 60mm place, and the carbon fiber measured after 500mm unwinding is suspended on hook, and the length that sample is stretched out from both sides is equal, leaves standstill the distance measuring two ends after 30s.
4. lousiness amount
Carbon fiber bundle wipes at two polyurethane sponges that to be of a size of 40mm(long) × 10mm(is wide) × 5mm(is thick) and clamping under, whole polyurethane sponge wipes load-carrying 200g.Carbon fiber bundle by minor face with the speed of 1m/min, is attached to the weight of lousiness on sponge, is the friction lousiness amount of carbon fiber bundle after surveying 10min.
5. ABRASION RESISTANCE
In wear-resistant device, godet roller diameter is 10mm, and stainless steel roller diameter is 15mm, and the angle of two godet rollers and stainless steel rider is 120 degree.Load-carrying is 300g/12000 root, and carbon fiber bundle with the speed of 120 times per minute at the uniform velocity reciprocating motion, and rubs repeatedly with stainless steel rider, number of times when record fiber rubs.
6. shear strength (ILSS) between carbon fiber composite layer
The interlaminar shear strength of carbon fibre composite is according to JC/T773-1996(GB3357-82) measure gained.
The parameter of the Unidirectional fiber reinforced epoxy resin sample of preparation is: sample size is thick 3mm × wide 6mm × long 25mm, and span and Thickness Ratio are 5, and loading velocity is 1mm/min.
Tested according to the method described above sizing agent prepared by each embodiment or comparative example, contrast with unsized carbon fiber, result is as shown in table 1 below simultaneously.
Claims (10)
1. an emulsion type carbon fiber sizing agent, is characterized in that: comprise main slurry, emulsifying agent, graphene oxide, diluent and water, and the consumption of emulsifying agent is 0.5 ~ 6wt% of main slurry, and the consumption of graphene oxide is 0.1 ~ 2wt% of main slurry.
2. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: the consumption of graphene oxide is the 0.2-0.6wt% of main slurry.
3. emulsion type carbon fiber sizing agent according to claim 1 and 2, is characterized in that: the thickness of graphene oxide is 0.9 ~ 1.5nm, and lamella diameter is 2 ~ 5 μm, number of plies 1-2 layer.
4. emulsion type carbon fiber sizing agent according to claim 1, it is characterized in that: the mixture of the octyl phenol polyoxyethylene ether of described emulsifying agent to be mass ratio be 5 ~ 25:50 ~ 70:10 ~ 35, anhydrous sorbitol list olein and neopelex, is preferably the mixture of octyl phenol polyoxyethylene ether, anhydrous sorbitol list olein and the neopelex that mass ratio is 10:65:25.
5. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: the consumption of diluent is 10 ~ 50wt% of main slurry; The mass ratio of deionized water and main slurry is 4:1.
6. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described main slurry is epoxy resin, comprises E-51, E-55, AG80 epoxy resin; Described diluent is non-activated thinner, such as acetone, or is reactive diluent, such as neopentylglycol diglycidyl ether.
7. a preparation method for emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: main slurry, diluent are mixed with emulsifying agent, carries out stirring premix, and then slowly adds graphene oxide water solution and carry out Phase inversion emulsification, obtains sizing agent.
8. preparation method according to claim 1, is characterized in that: graphene aqueous solution is added drop-wise in main slurry, and rate of addition is 0.1-5 mL/min, preferred 1mL/min.
9. preparation method according to claim 1, is characterized in that: the mixture of main slurry, diluent and emulsifying agent is stirred 20 min under the rotating speed of 2000 rpm, realizes premix; Graphene oxide water solution adds under the mixing speed of 6500-10500 r/min, continues to stir 20min after adding under this rotating speed, completes Phase inversion emulsification.
10. a method for carbon fiber starching, is characterized in that: be 0.5 ~ 3.0 wt% by emulsion type carbon fiber sizing agent thin up according to claim 1 to solid content, then adopts infusion process to be invested on carbon fiber by the emulsion type carbon fiber sizing agent after dilution.
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| CN105176008A (en) * | 2015-10-29 | 2015-12-23 | 济南大学 | Formula and preparing method of carbon fiber sizing agent for reinforcing polypropylene |
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| WO2017089825A1 (en) * | 2015-11-27 | 2017-06-01 | Thomas Swan & Co.Ltd | A process for the continuous production of sub-micron two-dimensional materials such as graphene |
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| CN105862428A (en) * | 2016-05-05 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method and product of graphene-modified carbon fiber sizing agent |
| CN105862428B (en) * | 2016-05-05 | 2018-01-23 | 中国科学院宁波材料技术与工程研究所 | Preparation method of carbon fiber sizing agent that a kind of graphene is modified and products thereof |
| CN107043475A (en) * | 2017-04-21 | 2017-08-15 | 厦门正新橡胶工业有限公司 | Graphene pickering emulsion optimization rubber composition and preparation method thereof |
| CN108360263A (en) * | 2018-02-07 | 2018-08-03 | 航天材料及工艺研究所 | The compound 3D printing composite material high activity Interface enhancer of quick in situ and preparation method |
| JP2021519870A (en) * | 2018-03-28 | 2021-08-12 | ゾルテック コーポレイション | Conductive sizing for carbon fiber |
| US11566369B2 (en) * | 2018-03-28 | 2023-01-31 | Zoltek Corporation | Electrically conductive sizing for carbon fibers |
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| CN110079993A (en) * | 2019-04-28 | 2019-08-02 | 陕西科技大学 | A kind of method of zirconium dioxide/surface of graphene oxide modified carbon fiber |
| CN110079993B (en) * | 2019-04-28 | 2021-09-17 | 陕西科技大学 | Method for surface modification of carbon fiber by zirconium dioxide/graphene oxide |
| CN110273209A (en) * | 2019-07-03 | 2019-09-24 | 江苏先诺新材料科技有限公司 | A kind of high-strength fire-retarding high temperature resistant type polyimides yarn and preparation method thereof |
| CN110273209B (en) * | 2019-07-03 | 2021-01-01 | 江苏先诺新材料科技有限公司 | High-strength flame-retardant high-temperature-resistant polyimide yarn and preparation method thereof |
| CN110468591A (en) * | 2019-08-09 | 2019-11-19 | 浙江理工大学 | A kind of graphene fiber sizing agent and preparation method thereof |
| CN110468591B (en) * | 2019-08-09 | 2022-04-19 | 浙江理工大学 | Sizing agent for graphene fibers and preparation method thereof |
| CN110714332A (en) * | 2019-11-20 | 2020-01-21 | 长春工业大学 | Water-based polyether sulfone sizing agent for carbon fibers and preparation method thereof |
| CN110714332B (en) * | 2019-11-20 | 2022-06-21 | 长春工业大学 | Water-based polyether sulfone sizing agent for carbon fibers and preparation method thereof |
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