CN108589267A - A kind of industrial method of carbon fiber surface continuous modification - Google Patents
A kind of industrial method of carbon fiber surface continuous modification Download PDFInfo
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- CN108589267A CN108589267A CN201810460689.4A CN201810460689A CN108589267A CN 108589267 A CN108589267 A CN 108589267A CN 201810460689 A CN201810460689 A CN 201810460689A CN 108589267 A CN108589267 A CN 108589267A
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
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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
- 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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- 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
The present invention relates to a kind of industrial methods of carbon fiber surface continuous modification, solves existing the technical issues of using carbonitride modified carbon fiber research and development application technical field blank, the present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:(1) pre-treatment of carbon fiber:The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A, is then dried, pretreatment carbon fiber is obtained;Component A is made of one or more of cyanamide, dicyandiamide, melamine, urea or thiocarbamide;(2) carbon fiber surface in-situ preparation carbonitride reinforcement:The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation carbonitride reinforcement;Component B is made of one or more of melamine, urea or thiocarbamide, the composite can be widely applied to high-performance composite materials preparation field.
Description
Technical field
The present invention relates to high-performance composite materials preparation fields, and in particular to a kind of industry of carbon fiber surface continuous modification
Change method.
Background technology
Carbon fiber (Carbon Fiber) be a kind of phosphorus content 95% or more high intensity, high-modulus fibrous material,
Its many excellent performance with elemental carbon:As proportion is small, heat-resist, coefficient of thermal expansion is small, thermal coefficient is big, corrosion resistance
It is good etc. with electric conductivity.Meanwhile and with the flexibility as fiber, braiding processing and Wrapping formed can be carried out.Carbon fiber is optimal
Good performance is that specific strength height and specific modulus are high, is the ideal reinforcement of polymer matrix composites.Carbon-fibre reinforced epoxy resin
Based composites are widely used in aerospace, national defence weapon equipment, athletic sports appliance and traffic and transport field, can be notable
Mitigate weight, improve payload, improve overall performance, is excellent structural material.But carbon fiber also has inherent defect:Table
Face is smooth and lacks reaction active groups, causes it poor with epoxy resin wellability, and interface binding power is weak between the two, serious to limit
Further the applying of carbon fiber reinforced epoxy resin-based composite.
To solve the technical problem of interface cohesion difference between carbon fiber and epoxy resin-base, the scientific research work in interface engineering field
Author develops a variety of carbon fiber surface modification technologies, including:Surface cladding process (CN102312377A), wet chemical oxidation method
(CN102021678A), vapour deposition process (CN104532548A), corona treatment (CN103696228A), chemical graft process
(CN105063999A), electrochemicial oxidation (CN104178790A), high-energy ray radiation treatment (CN105887463A) and
Particle grafted modified method (CN105690802A) of nano surface etc..Wherein, the particle grafted modified method of nano surface can pass through increase
The sealed area of machinery and chemical bonding effect, the interface cohesion between reinforcing fiber and matrix between carbon fiber and epoxy resin are shown
It writes and improves composite material overall performance.Common carbon fiber surface nanoreinforcement material has silica, titanium dioxide, zinc oxide
Deng also being found no at present about the relevant report for using carbonitride modified carbon fiber, the present invention has been filled up to be changed using carbonitride
The blank of property carbon fiber research and development application technical field.
Invention content
The purpose of the present invention is exactly in order to overcome the above-mentioned deficiencies of the prior art, to provide a kind of carbon fiber surface continuous modification
Industrial method, by carbon fiber surface in-situ preparation carbonitride reinforcement improve Interface Properties of Carbon Fibers Reinforced Composites.
The technical proposal for solving the technical problem of the invention is:The present invention provides a kind of carbon fiber surface continuous modification
Industrial method comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A, then dries, is pre-processed
Carbon fiber;Component A is made of one or more of cyanamide, dicyandiamide, melamine, urea or thiocarbamide;
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement;Component B is made of one or more of melamine, urea or thiocarbamide.
Preferably, the cyanamide mass concentration in step (1) is 0~775g/L;Dicyandiamide mass concentration is 0~60g/L;
Melamine mass concentration is 0~10g/L;A concentration of 0~1100g/L of urea quality, thiocarbamide mass concentration are 0~150g/L.
Preferably, the aqueous solution in step (1) is the saturated aqueous solution of component A.
Preferably, the aqueous temperature in step (1) is 20~50 DEG C.
Preferably, the drying temperature in step (1) is 300~1000 DEG C.
Preferably, the aqueous solution dip time in step (1) is 10~90s.
Preferably, the melamine mass concentration in step (2) is 0~1g/cm3;A concentration of 0~1.1g/ of urea quality
cm3;Thiocarbamide mass concentration is 0~1.2g/cm3。
Preferably, temperature is 450~650 DEG C in the fluid bed in step (2).
Preferably, the pretreatment carbon fiber in step (2) is 30~120s in the vulcanization bed internal stops time.
Preferably, the carbon fibre precursor by uncoated sizing agent in step (1) is immersed in the aqueous solution containing component A and surpasses
Sonication is then dried, and pretreatment carbon fiber is obtained.
Beneficial effects of the present invention:The present invention provides a kind of industrial method of carbon fiber surface continuous modification, in carbon fiber
Dimension table face is formed in situ carbonitride reinforcement, realize structure-controllable, be evenly distributed, load capacity it is controllable, increase carbon fiber surface
Product and surface active groups quantity, regulate and control and optimize carbon fiber specific surface area and surface reaction activity, improve itself and epoxy resin
Between wellability and interface cohesion, solve in carbon-fibre reinforced epoxy resin composite material between carbon fiber and epoxy resin-base
Interface cohesion difference technical problem, improve carbon-fibre reinforced epoxy resin composite material overall performance, filled up use nitrogen
Change the blank of carbon modified carbon fiber technical research applied technical field.
Description of the drawings
Fig. 1 is the structural schematic diagram of carbon fiber surface in-situ preparation carbonitride;
Fig. 2 is the reaction mechanism figure of carbon fiber surface in-situ preparation carbonitride;
Fig. 3 is the industrial continuous flow diagram of carbon fiber surface in-situ preparation carbonitride.
Label declaration:1. carbon fiber;2. pre-treatment of carbon fiber pond;3. tube type drying stove;4. fluid bed;5. deflector roll.
Specific implementation mode
The invention will be further described in the following with reference to the drawings and specific embodiments, to help present disclosure is understood.
Method used in the present invention is conventional method unless otherwise required;Used raw material and device, such as without special rule
It is fixed, it is conventional commercial product.
Embodiment 1
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is cyanamide, is 775g/L in the mass concentration of aqueous solution;Aqueous temperature is 20
℃;Drying temperature is 300 DEG C, drying time 65s;Aqueous solution dip time is 20s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is melamine, mass concentration 1g/cm3;Temperature is 650 DEG C in fluid bed;Pre- place
It is 30s that carbon fiber, which is managed, in the vulcanization bed internal stops time.
After testing, embodiment 1 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
71.2MPa, interlaminar shear strength 84.9MPa, interface shear strength increase rate are 80.25%, meet product requirement.
Embodiment 2
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is dicyandiamide, is 60g/L in the mass concentration of aqueous solution;Aqueous temperature is 40
℃;Drying temperature is 700 DEG C, drying time 30s;Aqueous solution dip time is 30s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is urea, mass concentration 1.1g/cm3;Temperature is 475 DEG C in fluid bed;Pretreatment
Carbon fiber is 110s in the vulcanization bed internal stops time.
After testing, embodiment 2 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
78.7MPa, interlaminar shear strength 87.5MPa, interface shear strength increase rate are 99.20%, meet product requirement.
Embodiment 3
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is melamine, is 10g/L in the mass concentration of aqueous solution;Aqueous temperature is
35℃;Drying temperature is 500 DEG C, drying time 40s;Aqueous solution dip time is 60s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is thiocarbamide, mass concentration 1.2g/cm3;Temperature is 550 DEG C in fluid bed;Pretreatment
Carbon fiber is 100s in the vulcanization bed internal stops time.
After testing, embodiment 3 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
69.3MPa, interlaminar shear strength 85.1MPa, interface shear strength increase rate are 75.44%, meet product requirement.
Embodiment 4
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is urea, is 1100g/L in the mass concentration of aqueous solution;Aqueous temperature is 25
℃;Drying temperature is 1000 DEG C, drying time 10s;Aqueous solution dip time is 10s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is melamine and urea, and the mass concentration of melamine is 0.6g/cm3, the matter of urea
Measure a concentration of 0.4g/cm3;Temperature is 450 DEG C in fluid bed;It is 120s that carbon fiber, which is pre-processed, in the vulcanization bed internal stops time.
After testing, embodiment 4 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
83.1MPa, interlaminar shear strength 86.4MPa, interface shear strength increase rate are 110.27%, meet product requirement.
Embodiment 5
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is thiocarbamide, is 150g/L in the mass concentration of aqueous solution;Aqueous temperature is 50
℃;Drying temperature is 400 DEG C, drying time 50s;Aqueous solution dip time is 90s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is melamine and thiocarbamide, and the mass concentration of melamine is 0.4g/cm3, the matter of thiocarbamide
Measure a concentration of 0.8g/cm3;Temperature is 525 DEG C in fluid bed;It is 90s that carbon fiber, which is pre-processed, in the vulcanization bed internal stops time.
After testing, embodiment 5 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
77.5MPa, interlaminar shear strength 87.1MPa, interface shear strength increase rate are 96.20%, meet product requirement.
Embodiment 6
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is cyanamide and dicyandiamide, and cyanamide is 500g/L in the mass concentration of aqueous solution, double
Cyanogen ammonia is 60g/L in the mass concentration of aqueous solution;Aqueous temperature is 30 DEG C;Drying temperature is 350 DEG C, drying time 60s;Water
Solution dip time is 80s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is urea and thiocarbamide, and the mass concentration of urea is 0.9g/cm3, the mass concentration of thiocarbamide is
0.2g/cm3;Temperature is 480 DEG C in fluid bed;It is 60s that carbon fiber, which is pre-processed, in the vulcanization bed internal stops time.
After testing, embodiment 6 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
66.2MPa, interlaminar shear strength 76.3MPa, interface shear strength increase rate are 67.59%, meet product requirement.
Embodiment 7
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is melamine and urea, and melamine is 10g/L in the mass concentration of aqueous solution,
Urea is 900g/L in the mass concentration of aqueous solution;Aqueous temperature is 45 DEG C;Drying temperature is 800 DEG C, drying time 35s;
Aqueous solution dip time is 40s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is melamine, urea and thiocarbamide, and the mass concentration of melamine is 0.2g/cm3, urine
The mass concentration of element is 0.6g/cm3, the mass concentration of thiocarbamide is 0.3g/cm3;Temperature is 500 DEG C in fluid bed;Pre-process carbon fiber
Dimension is 80s in the vulcanization bed internal stops time.
After testing, embodiment 7 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
64.3MPa, interlaminar shear strength 77.5MPa, interface shear strength increase rate are 62.78%, meet product requirement.
Embodiment 8
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is cyanamide, dicyandiamide and thiocarbamide, and cyanamide is in the mass concentration of aqueous solution
400g/L, dicyandiamide are 30g/L in the mass concentration of aqueous solution, and thiocarbamide is 150g/L in the mass concentration of aqueous solution;Aqueous solution
Temperature is 25 DEG C;Drying temperature is 450 DEG C, drying time 50s;Aqueous solution dip time is 55s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is urea, and the mass concentration of urea is 1.0g/cm3;Temperature is 625 DEG C in fluid bed;In advance
Treatment of Carbon is 50s in the vulcanization bed internal stops time.
After testing, embodiment 8 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
76.8MPa, interlaminar shear strength 88.2MPa, interface shear strength increase rate are 94.43%, meet product requirement.
Embodiment 9
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is cyanamide, dicyandiamide, melamine and urea, quality of the cyanamide in aqueous solution
A concentration of 400g/L, dicyandiamide are 10g/L in the mass concentration of aqueous solution, and melamine is 8g/ in the mass concentration of aqueous solution
L, urea are 1000g/L in the mass concentration of aqueous solution;Aqueous temperature is 35 DEG C;Drying temperature is 600 DEG C, drying time
35s;Aqueous solution dip time is 50s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is melamine and urea, and the mass concentration of melamine is 0.4g/cm3, the matter of urea
Measure a concentration of 0.7g/cm3;Temperature is 580 DEG C in fluid bed;It is 70s that carbon fiber, which is pre-processed, in the vulcanization bed internal stops time.
After testing, embodiment 9 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
86.2MPa, interlaminar shear strength 102.9MPa, interface shear strength increase rate are 118.22%, meet product requirement.
Embodiment 10
The present invention provides a kind of industrial method of carbon fiber surface continuous modification comprising following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A to be ultrasonically treated, then dries, obtains
To pretreatment carbon fiber.Wherein, component A is cyanamide, dicyandiamide, melamine, urea and thiocarbamide, and cyanamide is in aqueous solution
Mass concentration is 200g/L, and dicyandiamide is 20g/L in the mass concentration of aqueous solution, and melamine is in the mass concentration of aqueous solution
6g/L, urea are 700g/L in the mass concentration of aqueous solution, and thiocarbamide is 100g/L in the mass concentration of aqueous solution;Aqueous temperature
It is 40 DEG C;Drying temperature is 900 DEG C, drying time 15s;Aqueous solution dip time is 70s.
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement.Wherein, component B is melamine and thiocarbamide, and the mass concentration of melamine is 0.5g/cm3, the matter of thiocarbamide
Measure a concentration of 0.7g/cm3;Temperature is 600 DEG C in fluid bed;It is 40s that carbon fiber, which is pre-processed, in the vulcanization bed internal stops time.
After testing, embodiment 10 is in the generated in-situ carbonitride reinforcement of carbon fiber surface, interface shear strength
79.7MPa, interlaminar shear strength 94.6MPa, interface shear strength increase rate are 101.77%, meet product requirement.
Shown in Fig. 1, Fig. 2, the present invention provides a kind of industrial method of carbon fiber surface continuous modification, in carbon fiber surface
Face in-situ polymerization generates carbonitride reinforcement, and carbon fiber specific surface area increases, and the amino-functional group for nitrogenizing carbon surface enhances
Carbon fiber surface reactivity substantially improves its wellability with interlaminar resin, increases the machine between carbon fiber and epoxy resin
Tool is sealed, while amino group can react between epoxy molecule, forms chemical bonding effect at interface, greatly changes
It has been apt to the interface bond strength of composite material, has improved the interface performance of composite material.Currently, also finding no about using nitrogen
Change the relevant report of carbon modified carbon fiber, the present invention, which discloses, to still belong to the first time, and has filled up the blank of this technology.Aforementioned present invention is real
It applies in 1~embodiment of example 10, carbon fiber surface in-situ preparation carbonitride reinforcement interface shear strength is 64.3~86.2MPa,
Interlaminar shear strength is 76.3~102.9MPa, and wherein interface shear strength increase rate is 62.78%~118.22%, and it is investigated that
Pertinent literature is read, the interface shear strength after current nano-material modified carbon fiber improves degree and is generally 30~100%, can
See, the present invention uses new carbon fiber surface modification method, equally significantly improves the interface bond strength of composite material, reaches
To the good result for the interface performance for improving composite material, meet product requirement.
The present invention provides a kind of industrial method of carbon fiber surface continuous modification, 1~embodiment of above-described embodiment 10,
Flow is as shown in Figure 3:Pre-treatment of carbon fiber pond 2 and tube type drying stove 3 are pre-processed for carbon fiber 1, wherein pre-treatment of carbon fiber
Hold the aqueous solution containing component A in pond 2, component A by cyanamide, dicyandiamide, melamine, urea or thiocarbamide one kind or
Several compositions, 1 precursor of carbon fiber for uncoated sizing agent impregnate, and further use aqueous solution and are ultrasonically treated, are water-soluble
Liquid temperature setting is 20~50 DEG C and the aqueous solution of component A is set as supersaturated solution increase concentration, may advantageously facilitate carbon fiber
Tie up the rapid impregnation of 1 precursor;Tube type drying stove 3 is drying unit, and drying temperature is 300~1000 DEG C, may advantageously facilitate carbon fiber
The flash baking after 1 precursor dipping is tieed up, component A is made firmly to be adsorbed on 1 surface of carbon fiber.Fluid bed 4 is used for 1 surface of carbon fiber
In-situ preparation carbonitride reinforcement, interior to contain component B, component B is by one or more of melamine, urea or thiocarbamide group
At wherein temperature is set as 450~650 DEG C in fluid bed 4, is conducive to 1 surface in situ of carbon fiber and generates carbonitride reinforcement.Carbon fiber
In dimension pretreatment pool 2, tube type drying stove 3 and fluid bed 4 and its between joining place be equipped with deflector roll 5, for being sent carbon fiber
1, continuous production is formed, working efficiency is improved.In pre-treatment of carbon fiber pond 2 the impregnated carbon fiber time of unit length be 10~
90s, 3 drying time of tube type drying stove be 10~65s, pretreatment carbon fiber 1 the 4 internal stops time of vulcanization bed be 30~
120s, therefore, the industrialized production of 1 surface continuous modification of unit length carbon fiber of the present invention need 50~275s.Existing carbon
Fiber surface nano particle grafting is modified fado and uses intermittent treatment process, tedious process, and low production efficiency, generally requires
Even more than ten hour several hours, carbon fibre composite industrialization development process is seriously affected, and in contrast, this hair
Bright process is simple, and production efficiency is high, strong to push carbon fibre composite industrialization development process.
The only above person, only specific embodiments of the present invention, it is all when cannot be limited the scope of implementation of the present invention with this
The equivalent changes and modifications done according to scope of the present invention patent should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of industrial method of carbon fiber surface continuous modification, which is characterized in that it includes the following steps:
(1) pre-treatment of carbon fiber
The carbon fibre precursor of uncoated sizing agent is immersed in the aqueous solution containing component A, is then dried, pretreatment carbon fiber is obtained
Dimension;The component A is made of one or more of cyanamide, dicyandiamide, melamine, urea or thiocarbamide;
(2) carbon fiber surface in-situ preparation carbonitride reinforcement
The pretreatment carbon fiber that the step (1) is obtained is by the fluid bed containing component B, in carbon fiber surface in-situ preparation
Carbonitride reinforcement;The component B is made of one or more of melamine, urea or thiocarbamide.
2. a kind of industrial method of carbon fiber surface continuous modification according to claim 1, which is characterized in that the step
Suddenly the cyanamide mass concentration in (1) is 0~775g/L;The dicyandiamide mass concentration is 0~60g/L;The trimerization
Cyanamide mass concentration is 0~10g/L;A concentration of 0~the 1100g/L of urea quality, the thiocarbamide mass concentration be 0~
150g/L。
3. a kind of industrial method of carbon fiber surface continuous modification according to claim 2, which is characterized in that the step
Suddenly the aqueous solution in (1) is the saturated aqueous solution of the component A.
4. a kind of industrial method of carbon fiber surface continuous modification according to claim 3, which is characterized in that the step
Suddenly the aqueous temperature in (1) is 20~50 DEG C.
5. a kind of industrial method of carbon fiber surface continuous modification according to claim 4, which is characterized in that the step
Suddenly the drying temperature in (1) is 300~1000 DEG C.
6. a kind of industrial method of carbon fiber surface continuous modification according to claim 5, which is characterized in that the step
Suddenly the aqueous solution dip time in (1) is 10~90s.
7. a kind of industrial method of carbon fiber surface continuous modification according to claim 1, which is characterized in that the step
Suddenly the melamine mass concentration in (2) is 0~1g/cm3;A concentration of 0~1.1g/cm of urea quality3;Thiocarbamide mass concentration is 0
~1.2g/cm3。
8. a kind of industrial method of carbon fiber surface continuous modification according to claim 7, which is characterized in that the step
Suddenly temperature is 450~650 DEG C in the fluid bed in (2).
9. a kind of industrial method of carbon fiber surface continuous modification according to claim 8, which is characterized in that the step
Suddenly the pretreatment carbon fiber in (2) is 30~120s in the vulcanization bed internal stops time.
10. a kind of industrial method of carbon fiber surface continuous modification according to claim 1, which is characterized in that described
The carbon fibre precursor by uncoated sizing agent in step (1) is immersed in the supersound process of the aqueous solution containing component A, then dries
It is dry, obtain pretreatment carbon fiber.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN109809106A (en) * | 2018-11-28 | 2019-05-28 | 青岛环球输送带有限公司 | A kind of dedicated heat resistance conveyor belt of large junk and its preparation process |
CN112979334A (en) * | 2021-02-25 | 2021-06-18 | 攀枝花容则钒钛有限公司 | Preparation method of carbon fiber reinforced pantograph carbon slide plate based on 3D printing |
CN113308879A (en) * | 2021-05-26 | 2021-08-27 | 河南工业大学 | By using g-C3N4Preparation method of modified carbon fiber immobilized carrier |
CN115430396A (en) * | 2021-06-01 | 2022-12-06 | 中国石油天然气集团有限公司 | Modified activated carbon fiber loaded TiO 2 Composite material and preparation method and application thereof |
CN113386349A (en) * | 2021-06-16 | 2021-09-14 | 西南交通大学 | 3D printing method of carbon fiber reinforced resin-based plate |
CN113386349B (en) * | 2021-06-16 | 2022-07-12 | 西南交通大学 | 3D printing method of carbon fiber reinforced resin-based plate |
CN114645376A (en) * | 2022-05-13 | 2022-06-21 | 浙江星辉新材料科技有限公司 | Preparation method of low-density carbon fiber hard heat-preservation felt |
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