CN1762686A - Self-reinforced interlayer shearing intensity resin base fiber reinforced composite material preparation method - Google Patents
Self-reinforced interlayer shearing intensity resin base fiber reinforced composite material preparation method Download PDFInfo
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- CN1762686A CN1762686A CN 200510061548 CN200510061548A CN1762686A CN 1762686 A CN1762686 A CN 1762686A CN 200510061548 CN200510061548 CN 200510061548 CN 200510061548 A CN200510061548 A CN 200510061548A CN 1762686 A CN1762686 A CN 1762686A
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Abstract
The invention discloses a resin fiber composite material making method of self-reinforced interlayer shearing strength, which is characterized by the following: weighing 5-100 liquid crystal resin; preparing prepreg according to wet method or melting method; or adapting liquid phase modeling craft to form composite material without preparing prepreg according to the conventional composite material moulding method; paving prepreg layer; forcing static magnetic field or variable pulse magnetic field with 2-20 T magnetic strength in the moulding course; orienting the solid liquid crystal at the given direction; cooling the moulded mold to atmospheric temperature naturally then demoulding; or doing after-treatment again to demould after cooled to atmospheric temperature naturally. The invention improves the shearing strength and, which reduces cost.
Description
Technical field
The present invention relates to a kind of preparation method of self-reinforced interlayer shearing intensity resin base fiber reinforced composite material.
Background technology
Advanced polymer matrix composites with its outstanding lightweight, high heat-resisting, height ratio strong, the characteristics of height ratio mould and playing the part of indispensable key player in modern industry, the research and development level of composite has been considered to estimate the important indicator of a national comprehensive strength.The performance that material is higher, better manufacturability, suitable cost are the targets that people pursue always.Yet general, the interlayer shear performance of composite is lower, and impact is very sensitive, especially when suffering low velocity impact.And be the advanced composite material of representative with the carbon fiber, this problem is more outstanding, seriously restricts it than the more application under the exacting terms of work on hand environment.
The method of the interlaminar shear strength of raising composite is more, roughly can consider, promptly obtain the composite of high interlaminar shear strength by the interfacial adhesion strength between the body intensity, fiber and the matrix that improve polymer, the structure (as two dimension, 3 D weaving etc.) of rationalization's fibre reinforcement from resin matrix, fortifying fibre, three aspects, interface.These methods are all comparatively effective and obtained application, but also have certain problem, can make the bigger potentiality of existing resin system performance as braiding structure, still be method itself no matter from resin system, all help reducing cost, still, this method is difficult to be used in labyrinth.In addition, braiding structure causes the bending of fiber inevitably, thereby reduces the mechanical property of composite.Moreover the cost of braiding is higher.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of self-reinforced interlayer shearing intensity resin base fiber reinforced composite material.
The technical solution adopted for the present invention to solve the technical problems is: the step of this method is as follows:
1) liquid crystal hot solids weight resin percentage composition is 5～100% in the matrix resin, and the aathermoset resin system weight percentage is 95～0%;
2) prepare the fiber prepreg by wet method or fusion method; Or adopt liquid phase moulding process forming composite, then need not prepare prepreg;
3) with prepreg overlay, put into mould, composite material forming method forming composite routinely, in forming process, apply magnetostatic field or variable pulse magnetic field that magnetic field intensity is 2-20T simultaneously, the liquid crystal hot solids is orientated at direction initialization, after mold pressing finishes, naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites; Or carry out post processing again, naturally cool to normal temperature after, mould unloading promptly gets the advanced polymer matrix composites of self-reinforced interlayer shearing intensity.
Described liquid crystal hot solids resin system is a kind of and any combination in epoxy resin by using liquid crystal system, liquid crystal bismaleimide resin system, liquid crystalline acrylate ester resin system or the liquid crystal unsaturated polyester resin system.
Described aathermoset resin system is a kind of and any combination in epoxy-resin systems, bismaleimide resin system, unsaturated polyester resin system, properties of diallyl isophathalate resin, cyanate ester resin system or the phenolic resin system.
Described liquid phase moulding process is meant resin transfer moulding and resin infiltration process.
Described conventional forming composite method is compression molding, laminated into type, autoclave moulding, vacuum bag is molded, contact is molded or long filament is Wrapping formed.
The present invention compares the beneficial effect that has with background technology: the present invention is a matrix with the resin that contains the aligned liquid-crystal hot solids, utilizing electromagnetic field effect is liquid crystal molecular orientation, thereby improve the fracture strength of material by the development that molecularly oriented effectively hinders crazing, obtain self-reinforced material.Secondly, effectively reduce thermal coefficient of expansion (CTE), it is poor because of CTE differs the shrinkage stress difference and the interfacial stress that cause too greatly to reduce matrix and interlaminar resin.The 3rd, make the differently-oriented directivity of mesomorphic unit and the radially quadrature of fiber, forming " pinning " effect makes the contact between fiber and the resin matrix become the three-dimensional connection with three-dimensional effect from original simple bonding interface (two dimension), thereby increase substantially the interlaminar shear strength of goods, effectively solve the interlayer cracking problem that is prone to after the laminar composite goods are hit.
The specific embodiment
Embodiment 1:
1) the 23.66g P-aminobenzene-sulfonamide is put into 100g 4 in 155-160 ℃, in 4 '-two (2, the 3-glycidoxy)-Alpha-Methyl talan, stir 20min after, the epoxy resin by using liquid crystal that obtains mixing;
2) at 100-110 ℃ the 10g epoxy resin by using liquid crystal is joined among the 100g commodity modified bismaleimide resin 4501A, stir.Add 200ml acetone again, stir, obtain the acetone soln of resin matrix;
3) wet method prepares the continuous glass fibre prepreg routinely, gel content 40% (percentage by weight);
4) with the unidirectional shop of prepreg layer, put into mould, carry out compression molding.Adopt magnetostatic field, magnetic direction is parallel to thickness direction, and field intensity is 9T.The solidification temperature control program is 150 ℃/4h+180 ℃/1h+200 ℃/4h; After mold pressing finishes, naturally cool to normal temperature after, mould unloading;
5) in baking oven, carry out post processing (220 ℃/6h), naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites.Performance sees Table 1.
The comparative example of embodiment 1
Be equipped with glass fiber compound material by embodiment 1 legal system, difference is that the matrix composition only is bimaleimide resin 4501A resin, and no liquid crystal is formed, and does not have magnetic field during moulding.Performance sees Table 1.
Embodiment 2
1) the 23.66g P-aminobenzene-sulfonamide is put into 100g 4 in 155-160 ℃, in 4 '-two (2, the 3-glycidoxy)-Alpha-Methyl talan, stir 20min after, the epoxy resin by using liquid crystal that obtains mixing;
2) at 100-110 ℃ the 10g epoxy resin by using liquid crystal is joined among the 100g commodity modified bismaleimide resin 4501A, stir.Add 200ml acetone again, stir, obtain the acetone soln of resin matrix;
3) prepare the continuous carbon fibre prepreg by conventional wet, gel content 40%;
4) with prepreg overlay, put into mould, carry out compression molding.Adopting variable pulse magnetic field (magnetic direction is parallel to thickness direction, and field intensity is from 2-20T), solidification temperature control program is 150 ℃/4h+175 ℃/1h+200 ℃/4h; After mold pressing finishes, naturally cool to normal temperature after, mould unloading;
5) in baking oven, carry out post processing (220 ℃/6h), naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites.Performance sees Table 1.
The comparative example of embodiment 2
Be equipped with carbon fibre composite by embodiment 2 legal systems, difference is that the matrix composition only is bimaleimide resin 4501A resin, and no liquid crystal is formed, and does not have magnetic field during moulding.Performance sees Table 1.
Embodiment 3:
1) the 23.66g P-aminobenzene-sulfonamide is put into 100g 4 in 155-160 ℃, in 4 '-two (2, the 3-glycidoxy)-Alpha-Methyl talan, stir 20min after, the epoxy resin by using liquid crystal that obtains mixing;
2) be that the 23g short glass fiber of 3mm is put into epoxy resin by using liquid crystal at 100-110 ℃ with length, mix, obtain prepreg;
4) with the prepreg lay in mould, carry out compression molding.Adopting magnetostatic field (magnetic direction and thickness direction are at 45, field intensity 12T), solidification temperature control program is 150 ℃/4h+175 ℃/1h+200 ℃/4h; After mold pressing finishes, naturally cool to normal temperature after, mould unloading promptly get self-reinforced interlayer shearing intensity advanced person polymer matrix composites.Performance sees Table 1.
Embodiment 4
1) the 23.66g P-aminobenzene-sulfonamide is put into 100g 4 in 155-160 ℃, in 4 '-two (2, the 3-glycidoxy)-Alpha-Methyl talan, stir 20min after, the epoxy resin by using liquid crystal that obtains mixing;
2) at 100-110 ℃ the 5g epoxy resin by using liquid crystal is joined in 95g resin transfer moulding (or being called for short die casting, the RTM) resin-4503 (by BMI and epoxy resin compositional system), stir;
3) press glass fibre preformation base, put into mould, the normal temperature resin injection;
4) after resin injection is finished, be cured.Moulding process is: magnetostatic field (magnetic direction is parallel to thickness direction, and field intensity is 12T), and 150 ℃ of program curings/2h+170 ℃/2h+200 ℃/2h is cured;
5) after the RTM moulding finishes, naturally cool to normal temperature after, mould unloading; In baking oven, carry out post processing (220 ℃/5h), naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites.Performance sees Table 1.
Embodiment 5
1) the 23.66g P-aminobenzene-sulfonamide is put into 100g 4 in 155-160 ℃, in 4 '-two (2, the 3-glycidoxy)-Alpha-Methyl talan, stir 20min after, the epoxy resin by using liquid crystal that obtains mixing;
2) at 100-110 ℃ the 15g epoxy resin by using liquid crystal is joined 100g RTM (resin transfer moulding, or title die casting) resin--in BMI (4503) resin system, stir;
3) press glass fibre preformation base, put into mould, the normal temperature resin injection;
4) after resin injection is finished, be cured.Moulding process is: magnetostatic field (magnetic direction and thickness direction are at 45, and field intensity is 12T), 150 ℃ of program curings/2h+170 ℃/2h+200 ℃/2h;
5) after the RTM moulding finishes, naturally cool to normal temperature after, mould unloading; In baking oven, carry out post processing (220 ℃/5h), naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites.Performance sees Table 1.
Embodiment 6
1) DAIP is mixed with dimethyl benzene formyl DCP (1%),, be cooled to room temperature, discharging, obtain the DAIP performed polymer at 110 ℃ of reaction 1h.
2) 100g DAIP performed polymer, 15g 4 (3-methacryloxy-2-hydroxyl propoxyl group) benzoic acid 4 '-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl ester liquid crystalline resin mix, be heated to 80 ℃, under the effect of stirring, make it transparent, be cooled to 60 ℃, add benzoyl peroxide BPO (2%), mix, obtain resin matrix;
3) prepare the continuous glass fibre prepreg by conventional wet, gel content 50%;
4) with the unidirectional shop of prepreg layer, put into mould, it is molded to carry out vacuum bag.Adopt magnetostatic field, (magnetic direction and thickness direction are at 45, and field intensity is 9T, and the solidification temperature control program is 60 ℃/2h+80 ℃/2h+100 ℃/2h+120 ℃/2h+140 ℃/2h+170 ℃/2h;
5) after mold pressing finishes, naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites.Performance sees Table 1.
The comparative example of embodiment 6
Be equipped with composite by embodiment 6 legal systems, difference is that the matrix composition only is the DAIP resin, and no liquid crystal is formed, and does not have magnetic field during moulding.Performance sees Table 1.
Embodiment 7
1) DAIP is mixed with DCP (1%),, be cooled to room temperature, discharging, obtain the DAIP performed polymer at 110 ℃ of reaction 1h.
2) the 11.83g P-aminobenzene-sulfonamide is put into 50g 4 in 155-160 ℃, in 4 '-two (2, the 3-glycidoxy)-Alpha-Methyl talan, stir 20min after, the epoxy resin by using liquid crystal that obtains mixing;
3) 100g DAIP performed polymer, 15g 4 (3-methacryloxy-2-hydroxyl propoxyl group) benzoic acid 4 '-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl ester liquid crystalline resin, 10g epoxy resin by using liquid crystal mix, be heated to 80 ℃, under the effect of stirring, make it transparent, be cooled to 60 ℃, add benzoyl peroxide BPO (1%), mix, obtain resin matrix;
4) wet method prepares the continuous glass fibre prepreg routinely, gel content 50%;
5) with quadrature shop layer in the prepreg plane, put into mould, carry out the autoclave moulding.(magnetic direction becomes 30 ° with thickness direction, field intensity is 9T, and the solidification temperature control program is 60 ℃/2h+80 ℃/2h+100 ℃/2h+120 ℃/2h+140 ℃/2h+170 ℃/2h to adopt magnetostatic field;
6) after the autoclave moulding finishes, naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites.Performance sees Table 1.
Table 1 composite interlayer shear strength and impact flexibility
| Interlaminar shear strength (MPa) | |
| Embodiment 1 | 48.0 |
| The comparative example of embodiment 1 | 43.5 |
| Embodiment 2 | 42.3 |
| The comparative example of embodiment 2 | 38.9 |
| Embodiment 3 | 46.2 |
| Embodiment 4 | 41.9 |
| Embodiment 5 | 47.6 |
| Embodiment 6 | 29.2 |
| The comparative example of embodiment 6 | 25.4 |
| Embodiment 7 | 32.1 |
Claims (5)
1, the preparation method of self-reinforced interlayer shearing intensity resin base fiber reinforced composite material is characterized in that the step of this method is as follows:
1) liquid crystal hot solids weight resin percentage composition is 5～100% in the matrix resin, and the aathermoset resin system weight percentage is 95～0%;
2) prepare the fiber prepreg by wet method or fusion method; Or adopt liquid phase moulding process forming composite, then need not prepare prepreg;
3) with prepreg overlay, put into mould, composite material forming method forming composite routinely, in forming process, apply magnetostatic field or variable pulse magnetic field that magnetic field intensity is 2-20T simultaneously, the liquid crystal hot solids is orientated at direction initialization, after mold pressing finishes, naturally cool to normal temperature after, mould unloading promptly gets the self-reinforced interlayer shearing intensity polymer matrix composites; Or carry out post processing again, naturally cool to normal temperature after, mould unloading promptly gets the advanced polymer matrix composites of self-reinforced interlayer shearing intensity.
2, the preparation method of self-reinforced interlayer shearing intensity resin base fiber reinforced composite material according to claim 1 is characterized in that: described liquid crystal hot solids resin system is a kind of and any combination in epoxy resin by using liquid crystal system, liquid crystal bismaleimide resin system, liquid crystalline acrylate ester resin system or the liquid crystal unsaturated polyester resin system.
3, the preparation method of self-reinforced interlayer shearing intensity resin base fiber reinforced composite material according to claim 1 is characterized in that: described aathermoset resin system is a kind of and any combination in epoxy-resin systems, bismaleimide resin system, unsaturated polyester resin system, properties of diallyl isophathalate resin, cyanate ester resin system or the phenolic resin system.
4, the preparation method of self-reinforced interlayer shearing intensity resin base fiber reinforced composite material according to claim 1 is characterized in that: described liquid phase moulding process is meant resin transfer moulding and resin infiltration process.
5, the preparation method of self-reinforced interlayer shearing intensity resin base fiber reinforced composite material according to claim 1 is characterized in that: described conventional forming composite method is compression molding, laminated into type, autoclave moulding, vacuum bag is molded, contact is molded or long filament is Wrapping formed.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101870176B (en) * | 2009-04-24 | 2012-11-07 | 昆山同寅兴业机电制造有限公司 | Processing techniques of carbon fiber products and glass fiber products |
| CN104761742A (en) * | 2014-01-06 | 2015-07-08 | 财团法人工业技术研究院 | Prepreg and method for forming the same |
| WO2019208242A1 (en) * | 2018-04-27 | 2019-10-31 | 東レ株式会社 | Prepreg and carbon-fiber-reinforced composite material |
| CN112629324A (en) * | 2020-11-12 | 2021-04-09 | 湖南欧亚碳纤维复合材料有限公司 | Carbon fiber composite bulletproof plate and preparation process thereof |
| CN113186657A (en) * | 2021-04-29 | 2021-07-30 | 西安建筑科技大学 | Metal-wrapped short fiber cloth forming device and using method thereof |
| CN114633493A (en) * | 2022-01-21 | 2022-06-17 | 南京航空航天大学 | Novel magnetic-guidance interlayer particle-reinforced composite material and preparation method thereof |
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| JP3456301B2 (en) * | 1995-03-30 | 2003-10-14 | チッソ株式会社 | Fiber-reinforced thermoplastic composite containing fibers and specific carbon black uniformly |
| JP2003158883A (en) * | 2001-11-16 | 2003-05-30 | Makoto Morishita | Functional element, and flow-variable valve using the same |
| JP4220805B2 (en) * | 2003-03-03 | 2009-02-04 | 本田技研工業株式会社 | Manufacturing method for vehicle hood made of fiber reinforced composite material |
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- 2005-11-14 CN CNB2005100615488A patent/CN100358708C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870176B (en) * | 2009-04-24 | 2012-11-07 | 昆山同寅兴业机电制造有限公司 | Processing techniques of carbon fiber products and glass fiber products |
| CN104761742A (en) * | 2014-01-06 | 2015-07-08 | 财团法人工业技术研究院 | Prepreg and method for forming the same |
| WO2019208242A1 (en) * | 2018-04-27 | 2019-10-31 | 東レ株式会社 | Prepreg and carbon-fiber-reinforced composite material |
| CN112041380A (en) * | 2018-04-27 | 2020-12-04 | 东丽株式会社 | Prepreg and carbon fiber-reinforced composite material |
| JPWO2019208242A1 (en) * | 2018-04-27 | 2021-03-25 | 東レ株式会社 | Prepreg and carbon fiber reinforced composites |
| JP7264050B2 (en) | 2018-04-27 | 2023-04-25 | 東レ株式会社 | Prepregs and carbon fiber reinforced composites |
| CN112629324A (en) * | 2020-11-12 | 2021-04-09 | 湖南欧亚碳纤维复合材料有限公司 | Carbon fiber composite bulletproof plate and preparation process thereof |
| CN113186657A (en) * | 2021-04-29 | 2021-07-30 | 西安建筑科技大学 | Metal-wrapped short fiber cloth forming device and using method thereof |
| CN114633493A (en) * | 2022-01-21 | 2022-06-17 | 南京航空航天大学 | Novel magnetic-guidance interlayer particle-reinforced composite material and preparation method thereof |
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