CN102019695B - Preparation method of chopped carbon fiber reinforced phenolic resin base composite material - Google Patents
Preparation method of chopped carbon fiber reinforced phenolic resin base composite material Download PDFInfo
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- CN102019695B CN102019695B CN2010105202389A CN201010520238A CN102019695B CN 102019695 B CN102019695 B CN 102019695B CN 2010105202389 A CN2010105202389 A CN 2010105202389A CN 201010520238 A CN201010520238 A CN 201010520238A CN 102019695 B CN102019695 B CN 102019695B
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Abstract
The invention provides a preparation method of a chopped carbon fiber reinforced phenolic resin base composite material, which comprises the following steps: dissolving chopped carbon fibers after dispersion, which are used as the reinforcing material, in anhydrous alcohol; meanwhile, adding phenolic resin, and evenly mixing; and carrying out die pressing to obtain the chopped carbon fiber reinforced phenolic resin base composite material. The chopped carbon fibers in the material have a three-dimensional network structure, the three-dimensional network structure converts the combination of fibers and resin matrix from two-dimensional connection to three-dimensional connection with spatial effect; when being subjected to shear action, work needs to be applied to overcome the binding force between the matrix and the fibers, so that the expansion of the cracks consumes more energy, thereby enhancing the interlaminar shear strength, avoiding the generation of aggregation and requiring low cost.
Description
Technical field
The present invention relates to a kind of preparation method of composite, particularly a kind of chopped carbon fiber strengthens the preparation method of phenolic resin-base composite.
Background technology
The Short Carbon Fiber Reinforced PF Resin based composites is widely used in many high performance civilian structures such as Aeronautics and Astronautics, automobile, boats and ships with characteristics such as its high-strength light, high temperature resistant, anticorrosive, antifatigues.Yet the interlaminar shear strength that carbon fiber enhancement resin base composite material is lower is a weak link during it is used.
The structure of rationalization's fibre reinforcement is one of the effective ways that improve the interlaminar shear strength of composite.For example, adopt carbon fiber 3 D weaving body or whole felt can improve the interlayer performance of composite greatly, but that 3 D weaving implements difficulty is big, cost is high.Again for example, the preparation method that China invention bulletin patent discloses a kind of carbon fiber enhancement resin base composite material ZL200510096438.5 number, this method have improved the interlaminar shear strength of composite through adding whisker in the Composite Preparation process.Yet the adding of inorganic crystal whisker has not only increased material cost, and is difficult to avoid the reunion of whisker in resin.
Summary of the invention
Topic provides the preparation method that a kind of chopped carbon fiber strengthens phenolic resin-base composite between technology to be solved by this invention; This method is carried out pre-dispersed processing back with chopped carbon fiber and is added in the resin, strengthens phenolic resin composite through having prepared chopped carbon fiber after dispersion, oven dry, the compression molding; This preparation method can effectively improve the distribution of carbon fiber in the composite, and fiber is space network in composite, reaches the purpose that improves composite interlayer shear strength.
For realizing above-mentioned purpose, the invention provides the preparation method that a kind of chopped carbon fiber strengthens phenolic resin-base composite, may further comprise the steps:
Step 1: chopped carbon fiber is heat-treated,, in ultrasonic wave, cleans to surperficial no glue with acetone then, cleaned then in baking oven, to dry by the fire to acetone and volatilized fully to remove surface metal ion and impurity;
Step 2: the chopped carbon fiber after step 1 handled soaks 10～25 hours in dispersant solution after, clean the oven dry of clean back with distilled water;
Step 3: get chopped carbon fiber 10～40g that step 2 obtains, place the 200ml absolute ethyl alcohol, fully stir, dissolve in 100g phenolic resins simultaneously, fully mix, promptly get the batch mixing of resin matrix and chopped carbon fiber;
Step 4: the batch mixing that step 3 is obtained is after room temperature leaves standstill 5h, 30～45 ℃ of oven dry;
Step 5: the compound that obtains after step 4 oven dry is put in the mould compression molding in vulcanizer;
Step 6: at last behind 210 ℃ of oven dry 6h, naturally cool to normal temperature after, mould unloading promptly get chopped carbon fiber enhancing phenolic resin-base composite.
As a kind of preferred version of the present invention, said phenolic resins is selected from phenol formaldehyde resin, cresols formaldehyde resin, xylenol-formaldehyde resin, p tert butylphenol formaldehyde resin or their mixture;
As another kind of preferred version of the present invention, said chopped carbon fiber is selected from common carbon fiber T300, T400H, T700, T800 or high modulus carbon fiber M40, M40J, M55J, M60J;
As another kind of preferred version of the present invention, said dispersant solution is selected from a kind of in methocel solution, Gonak and the Sodium Polyacrylate;
As another kind of preferred version of the present invention, the weight percent concentration of said dispersant is 0.1～0.7%;
As another kind of preferred version of the present invention, the condition that said chopped carbon fiber is heat-treated is: in 1200～1800 ℃ argon gas atmosphere, carry out;
As another kind of preferred version of the present invention, said moulding process is: be under the condition of 2～5MPa at pressure, behind 120 ℃ of insulation 20min, respectively at 130 ℃, 140 ℃, 150 ℃ insulations 30 minutes, mold pressing naturally cooled to normal temperature after finishing.
The preparation method that chopped carbon fiber of the present invention strengthens phenolic resin-base composite has the following advantages at least: the present invention with dispersion treatment after carbon fiber be reinforcing material; Carbon fiber has the non-directional spatial arrangements and overlaps each other; Place absolute ethyl alcohol to add phenolic resins simultaneously on carbon fiber and evenly mix, make chopped carbon fiber through mold pressing and strengthen phenolic resin-base composite.Short carbon fiber has space network in this material, and this space network makes the combination between fiber and the resin matrix become the three-dimensional connection with three-dimensional effect from original two dimension, when receiving shear action; Need overcome the bonding between matrix and the fiber and do work; Make crackle when expansion, consume more energy, thereby improve the interlaminar shear strength of fiber-reinforced resin matrix compound material, compare with chopped carbon fiber without dispersion treatment; Its interlaminar shear strength has improved 5～20%; And preparation method's technology of the present invention is simple, has avoided the generation of agglomeration, and with low cost.
Description of drawings
Fig. 1 is the fracture apperance that is strengthened phenolic resin composite by the carbon fiber of the present invention's preparation;
Fig. 2 is the bridging that carbon fiber of the present invention strengthens fiber when crackle is expanded in the phenolic resin composite.
The specific embodiment
Embodiment 1:
Step 1: get chopped carbon fiber, surface metal ion and impurity are removed in heat treatment in 1200 ℃ of argon gas atmosphere stoves; Then, the chopped carbon fiber after the heat treatment is cleaned the no glue to the surface with acetone in ultrasonic wave, cleaned afterwards in baking oven, to dry to acetone and volatilized fully, subsequent use;
Step 2: take by weighing the chopped carbon fiber 25g after step 1 is handled, placing weight percent concentration is that 0.1% dispersant solution soaks 10h, and said dispersant is selected from methocel solution, cleans the oven dry of clean back with distilled water then, and is subsequent use;
Step 3: take by weighing the material 10g that step 2 obtains, place the 200ml absolute ethyl alcohol then, fully stir, dissolve in the 100g phenol formaldehyde resin simultaneously, after fully mixing, promptly get the batch mixing of resin matrix and chopped carbon fiber with agitator;
Step 4: the batch mixing that step 3 is obtained leaves standstill 5h in room temperature, again it is dried 4h in 30 ℃;
Step 5: the compound after the step 4 oven dry processing is passed in the mould; Compression molding on vulcanizer, wherein, pressing process is: be under the condition of 2MPa at pressure; At 120 ℃ of insulation 20min; Respectively at 130 ℃, 140 ℃, 150 ℃ insulations 30 minutes, mold pressing naturally cooled to normal temperature after finishing then;
Step 6: after the moulding, with the material that forms in baking oven behind 210 ℃ of oven dry 6h, naturally cool to normal temperature, mould unloading promptly get chopped carbon fiber enhancing phenolic resin-base composite.
The interlaminar shear strength of the composite that is obtained by this method is 60MPa, compares with the contrast material without the carbon fiber of dispersion treatment, and interlaminar shear strength has improved about 5%.
Embodiment 2:
Step 1: get chopped carbon fiber; Surface metal ion and impurity are removed in heat treatment in 1400 ℃ argon gas atmosphere stove, and the carbon fiber after the heat treatment cleans the no glue to the surface with acetone in ultrasonic wave; Cleaned the back and in baking oven, dried to acetone and volatilize fully, subsequent use;
Step 2: take by weighing the chopped carbon fiber 35g after step 1 is handled, placing weight percent concentration is that 0.3% dispersant solution soaks 15h, and said dispersant solution is selected from Gonak, cleans the oven dry of clean back with distilled water then, and is subsequent use;
Step 3: take by weighing the material that 20g step 2 obtains, place the 200ml absolute ethyl alcohol, fully stir, dissolve in 100g cresols formaldehyde resin simultaneously, mix, obtain the batch mixing of resin matrix and chopped carbon fiber with agitator;
Step 4: the batch mixing room temperature that step 3 is obtained leaves standstill 5h, again in 35 ℃ of oven dry 6h;
Step 5: the compound that obtains after step 4 oven dry is passed in the mould; Compression molding on vulcanizer; Pressing process is: be under the condition of 3MPa at pressure, at 120 ℃ of insulation 20min, then respectively at 130 ℃, 140 ℃, 150 ℃ insulations 30 minutes; Mold pressing naturally cools to normal temperature after finishing;
Step 6: after the moulding, with the material of moulding in baking oven in 210 ℃ of oven dry 6h, naturally cool to normal temperature after, mould unloading promptly get chopped carbon fiber enhancing phenolic resin-base composite.
The interlaminar shear strength of the composite that is obtained by this method is 70MPa, compares with the contrast material without the carbon fiber of dispersion treatment, and interlaminar shear strength has improved about 10%.
Embodiment 3:
Step 1: get chopped carbon fiber; Surface metal ion and impurity are removed in heat treatment in 1600 ℃ argon gas atmosphere stove, and the carbon fiber after the heat treatment cleans the no glue to the surface with acetone in ultrasonic wave; Cleaned the back and in baking oven, dried to acetone and volatilize fully, subsequent use;
Step 2: take by weighing the chopped carbon fiber 45g after step 1 is handled, placing weight percent concentration is that 0.5% dispersant solution soaks 20h, and said dispersant solution is selected from sodium polyacrylate solution, cleans the oven dry of clean back with distilled water then, and is subsequent use;
Step 3: take by weighing the material that 30g step 2 obtains, place the 200ml absolute ethyl alcohol, fully stir, dissolve in the 100g xylenol-formaldehyde resin simultaneously, stir, obtain the batch mixing of resin matrix and chopped carbon fiber with agitator;
Step 4: the batch mixing room temperature that obtains after step 3 oven dry is left standstill 5h, again in 40 ℃ of oven dry 8h;
Step 5: the compound that obtains after step 4 oven dry is passed in the mould; Compression molding on vulcanizer, wherein, pressing process is: be under the condition of 4MPa at pressure; Keep 20min at 120 ℃; Respectively at 130 ℃, 140 ℃, 150 ℃ insulations 30 minutes, mold pressing naturally cooled to normal temperature after finishing then;
Step 6: after the moulding, the material of moulding is kept 6h in 210 ℃ in baking oven, naturally cool to normal temperature after, mould unloading promptly get chopped carbon fiber enhancing phenolic resin-base composite.
The interlaminar shear strength of the composite that is obtained by this method is 80MPa, compares with the contrast material without the carbon fiber of dispersion treatment, and interlaminar shear strength has improved about 15%.
Embodiment 4:
Step 1: get chopped carbon fiber; Surface metal ion and impurity are removed in heat treatment in 1800 ℃ argon gas atmosphere stove, and the carbon fiber after the heat treatment cleans the no glue to the surface with acetone in ultrasonic wave; Cleaned the back and in baking oven, dried to acetone and volatilize fully, subsequent use;
Step 2: take by weighing the chopped carbon fiber 55g after step 1 is handled, placing weight percent concentration is that 0.7% dispersant solution soaks 25h, and said dispersant solution is selected from sodium polyacrylate solution, cleans the oven dry of clean back with distilled water then, and is subsequent use;
Step 3: take by weighing the material that 40g step 2 obtains, place the 200ml absolute ethyl alcohol, fully stir, dissolve in the 100g p tert butylphenol formaldehyde resin simultaneously, stir, obtain the batch mixing of resin matrix and chopped carbon fiber with agitator;
Step 4: the batch mixing that step 3 is obtained leaves standstill 5h in room temperature, again in 45 ℃ of oven dry 10h;
Step 5: the compound that obtains after step 4 oven dry is passed in the mould; Compression molding on vulcanizer, wherein, pressing process is: be under the condition of 5MPa at pressure; At 120 ℃ of insulation 20min; Respectively at 130 ℃, 140 ℃, 150 ℃ insulation 30min, mold pressing naturally cools to normal temperature after finishing then;
Step 6: the material after the moulding in baking oven in 210 ℃ of oven dry 6h, naturally cool to normal temperature after, mould unloading promptly get chopped carbon fiber enhancing phenolic resin-base composite.
The interlaminar shear strength of the composite that is obtained by this method is 90MPa, compares with the contrast material without the carbon fiber of dispersion treatment, and interlaminar shear strength has improved about 20%.
The fracture apperance figure of the composite that is made by the inventive method is as shown in Figure 1, from figure, can find out that carbon fiber is evenly distributed in composite, and not have tangible fiber agglomeration.
Fig. 2 is the bridging of the carbon fiber that made by the inventive method fiber when strengthening crackle expansion in the phenolic resin composite; Therefrom can find out: short carbon fiber has space network in the composite; Has the bridging effect; The expansion of obstruction crackle, thereby the interlaminar shear strength of raising fiber-reinforced resin matrix compound material.
The above is merely one embodiment of the present invention; It or not whole or unique embodiment; The conversion of any equivalence that those of ordinary skills take technical scheme of the present invention through reading specification of the present invention is claim of the present invention and contains.
Claims (7)
1. a chopped carbon fiber strengthens the preparation method of phenolic resin-base composite, it is characterized in that: may further comprise the steps:
Step 1: chopped carbon fiber is heat-treated,, in ultrasonic wave, cleans to surperficial no glue with acetone then, cleaned then in baking oven, to dry by the fire to acetone and volatilized fully to remove surface metal ion and impurity;
Step 2: the chopped carbon fiber after step 1 handled soaks 10～25 hours in dispersant solution after, clean the oven dry of clean back with distilled water;
Step 3: get chopped carbon fiber 10～40g that step 2 obtains, place the 200ml absolute ethyl alcohol, fully stir, dissolve in 100g phenolic resins simultaneously, fully mix, promptly get the batch mixing of resin matrix and chopped carbon fiber;
Step 4: the batch mixing that step 3 is obtained is after room temperature leaves standstill 5h, 30～45 ℃ of oven dry;
Step 5: the compound that obtains after step 4 oven dry is put in the mould compression molding in vulcanizer;
Step 6: at last behind 210 ℃ of oven dry 6h, naturally cool to normal temperature after, mould unloading promptly get chopped carbon fiber enhancing phenolic resin-base composite.
2. chopped carbon fiber as claimed in claim 1 strengthens the preparation method of phenolic resin-base composite, and it is characterized in that: said phenolic resins is selected from phenol formaldehyde resin, cresols formaldehyde resin, xylenol-formaldehyde resin, p tert butylphenol formaldehyde resin or their mixture.
3. according to claim 1 or claim 2 chopped carbon fiber strengthens the preparation method of phenolic resin-base composite, and it is characterized in that: said chopped carbon fiber is selected from common carbon fiber T300, T400H, T700, T800 or high modulus carbon fiber M40, M40J, M55J, M60J.
4. chopped carbon fiber as claimed in claim 1 strengthens the preparation method of phenolic resin-base composite, it is characterized in that: said dispersant solution is selected from a kind of in methocel solution, Gonak and the Sodium Polyacrylate.
5. chopped carbon fiber as claimed in claim 4 strengthens the preparation method of phenolic resin-base composite, and it is characterized in that: the weight percent concentration of said dispersant is 0.1～0.7%.
6. chopped carbon fiber as claimed in claim 1 strengthens the preparation method of phenolic resin-base composite, and it is characterized in that: the condition that said chopped carbon fiber is heat-treated is: in 1200～1800 ℃ argon gas atmosphere, carry out.
7. chopped carbon fiber as claimed in claim 1 strengthens the preparation method of phenolic resin-base composite; It is characterized in that: said moulding process is: be under the condition of 2～5MPa at pressure; Behind 120 ℃ of insulation 20min; Respectively at 130 ℃, 140 ℃, 150 ℃ insulations 30 minutes, mold pressing naturally cooled to normal temperature after finishing.
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| CN102303411B (en) * | 2011-09-09 | 2013-11-27 | 陕西科技大学 | Preparation method of carbon fiber paper-reinforced phenolic resin matrix composite material |
| CN103541266B (en) * | 2013-10-12 | 2016-02-10 | 陕西科技大学 | A kind of preparation method of the paper friction material based on suction filtration |
| CN103589184B (en) * | 2013-11-22 | 2014-09-17 | 成都市永益泵业有限公司 | Fiber-contained silicon carbide/resin composite material and method thereof for producing pump parts |
| CN104177111B (en) * | 2014-08-18 | 2015-11-25 | 中国科学院上海应用物理研究所 | A kind of slip casting prepares the method for carbon/carbon composite profiles |
| CN105038099B (en) * | 2015-06-10 | 2018-06-05 | 苏州宏恒化工有限公司 | Fishing rod phenolic resin-base composite and preparation method thereof |
| CN105238072B (en) * | 2015-10-30 | 2018-02-16 | 陕西科技大学 | A kind of preparation method of inorganic powder enhancing carbon cloth/resin composite materials |
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| CN109940908A (en) * | 2017-12-21 | 2019-06-28 | 宜兴市宜泰碳纤维织造有限公司 | A kind of moulding process of carbon fiber and phenolic resin composite |
| CN109251332B (en) * | 2018-08-20 | 2021-07-20 | 浙江亚太机电股份有限公司 | Chopped carbon fiber reinforced phenolic resin matrix composite material and preparation method thereof |
| CN111408343B (en) * | 2019-01-08 | 2022-01-28 | 湖南农业大学 | Preparation method of three-dimensional biochar and application of three-dimensional biochar in heavy metal adsorption |
| CN115385707B (en) * | 2021-05-20 | 2023-08-08 | 中国科学院上海硅酸盐研究所 | Preparation method of high volume fraction carbon-bonded chopped carbon fiber composite material |
| CN115368706B (en) * | 2021-05-20 | 2024-02-06 | 中国科学院上海硅酸盐研究所 | Preparation method of bubble dispersed chopped carbon fiber reinforced phenolic resin matrix composite material |
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| CN1065251C (en) * | 1997-06-18 | 2001-05-02 | 中国石油化工总公司 | Friction material for braking control system |
| US20060118992A1 (en) * | 2004-12-03 | 2006-06-08 | Geng-Wen Chang | Process of maniudacturing dual-layered thermal insulation composite panel |
| US7758779B2 (en) * | 2005-12-29 | 2010-07-20 | Graftech International Holdings Inc. | Reinforced resin-derived carbon foam |
| US20070172617A1 (en) * | 2006-01-25 | 2007-07-26 | Burrowes Thomas G | Curing sleeve reinforced with chopped carbon fibers |
| CN101628816B (en) * | 2008-07-17 | 2013-03-13 | 鞍山塞诺达碳纤维有限公司 | Method for manufacturing high-density rigid carbon-fiber heat-insulation material |
| CN101798774B (en) * | 2010-04-01 | 2011-10-05 | 东华大学 | Carbon fiber paper and preparation method thereof |
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