CN103802411A - Electrospun aramid 1313 nanofiber/polylactic acid composite material and preparation method for same - Google Patents
Electrospun aramid 1313 nanofiber/polylactic acid composite material and preparation method for same Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000747 poly(lactic acid) Polymers 0.000 title abstract description 26
- 239000004626 polylactic acid Substances 0.000 title abstract description 25
- 239000004760 aramid Substances 0.000 title abstract description 9
- 229920003235 aromatic polyamide Polymers 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001523 electrospinning Methods 0.000 claims abstract description 3
- 238000009987 spinning Methods 0.000 claims description 79
- 229920006231 aramid fiber Polymers 0.000 claims description 74
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 58
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 44
- 239000000835 fiber Substances 0.000 claims description 35
- 230000003068 static effect Effects 0.000 claims description 33
- 239000004310 lactic acid Substances 0.000 claims description 29
- 235000014655 lactic acid Nutrition 0.000 claims description 29
- 238000004090 dissolution Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical group CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
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- 230000001276 controlling effect Effects 0.000 abstract 1
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 7
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 238000001746 injection moulding Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an electrospun aramid 1313 nanofiber/polylactic acid composite material and a preparation method for the same. The preparation method specifically comprises the following steps of preparing oriented arranged aramid 1313 nanofibers by using an electrospinning method, and performing impregnation and hot-pressing to prepare an electrospun aramid 1313 nanofiber-reinforced polylactic acid composite material by using the electrospun nanofibers as reinforcement bodies. According to the composite material and the preparation method for the same, the preparation method for the electrospun aramid 1313 nanofiber-reinforced polylactic acid composite material is realized by systematically optimizing a preparation process; the bearing capacity of the composite material subjected to external force in different directions is regulated by controlling the arrangement direction of a highly-oriented aramid 1313 nanofiber layer, so that the obtained electrospun aramid 1313 nanofiber-reinforced polylactic acid composite material has longitudinal and transverse isotropic and anisotropic tensile mechanical properties, and is expected to be applied to the field of lightweight components.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material and preparation method thereof.
Background technology
Electrostatic spinning is a kind of novel spining technology of preparing nano-scale fiber, under the effect of high-voltage electrostatic field, polymer solution (or melt) can be spun into the fiber of diameter from tens nanometer to hundreds of nanometers.Because the method has the advantages such as equipment is simple, with low cost, since the Formhals invention Static Spinning technology of the U.S. in 1934, just constantly there is researcher to carry out the research of this respect; After the nineties in 20th century, along with the development of nanometer technology, the preparation of electrostatic spinning nano fiber and application thereof have become one of study hotspot of field of nanometer material technology.At present, existing hundreds of natural material and high molecular polymers is successfully spun into electrostatic spinning nano fiber.The fibrofelt that prepared product has also been random alignment state by initial fiber develops into can be controlled fiber and be the fibrofelt aligning.
Aramid fiber 1313 is to spin by poly (PMIA) a kind of tencel material obtaining.The heat resistance of this fiber is outstanding especially, at 260 ℃, use continuously after 1000h, still can keep 65% of original intensity, at 300 ℃, use a week, keep former intensity 50%, there are in addition good anti-flammability, electrical insulating property, chemical stability, radiation resistance and mechanical performance etc., thereby be widely used in special protecting clothing, high-temperature-resistant filtering material, electrically insulating material, reinforcing material and honeycomb revetment material etc.Current development and the performance study that the research of aramid fiber 1313 is mainly concentrated on to its composite, and few to the research of Static Spinning aramid fiber 1313 nanofiber aspect.
Chinese invention patent application CN101838888A discloses a kind of preparation method of electrospun meta-aramid nano-fiber; Chinese invention patent application CN102704028A discloses a kind of preparation method of meta-aramid nanometer spider web tunica fibrosa.The form that said method obtains product is the fibrofelt of random packing of fibers, and this felt material exists fiber assembly structural disorder and secondary operations wayward, product is restricted, can only be with defects such as single form are used.
In addition, PLA (PLA) is that a kind of lactic acid being obtained by fermentation by renewable material is again through the synthetic biodegradable plastic being prepared from.PLA belongs to thermoplastic, stable performance under normal temperature, and glass transition temperature is about 60 ℃, and fusing point is about 175 ℃.PLA is nontoxic, good biocompatibility, and plasticity is good, is suitable for blowing, extrudes, the multiple processing mode such as injection moulding.It is exactly biodegradability that PLA also has a feature, and it can be degradable under certain conditions by natural microorganism, finally generates carbon dioxide and water, can not cause any pollution to environment.But PLA quality is hard, property is crisp, easy to crack, extension at break is very little, poor impact resistance, conventionally can set it as matrix and prepare polymer/fiber composite to obtain better mechanical performance, expands its application.
At present, there is not yet about strengthening polylactic acid polymer with Static Spinning aramid fiber 1313 nanofiber, prepare the report of composite.
Summary of the invention
The object of this invention is to provide a kind of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material and preparation method thereof.
To achieve the above object of the invention, the technical solution used in the present invention is:
A preparation method for Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material, comprises the following steps:
(1) in polar solvent, add anhydrous Lithium chloride, form the dissolution system of chloride containing lithium, aramid fiber 1313 is joined in dissolution system, dissolve and obtain the spinning solution that contains aramid fiber 1313; In spinning solution, in mass, the content of aramid fiber 1313 is 8～16%, and the content of lithium chloride is 5～8%;
(2) adopt electrospinning process, obtain fiber and be the aramid fiber 1313 nanofiber mats aligning;
(3) PLA is dissolved in carrene, obtains mass concentration and be 2～6% PLA solution;
(4) the aramid fiber 1313 nanofiber mats two steps (2) being obtained is superimposed, then impregnated in the PLA solution that step (3) obtains, after the solvent in the aramid fiber 1313 nanofiber mats after to be impregnated volatilizees naturally, obtain aramid fiber 1313 nanofiber mats/PLA prepreg;
(5) by the Static Spinning aramid fiber 1313 nanofiber mats/lactic acid composite material described in hot-forming the obtaining of aramid fiber 1313 nanofiber mats/PLA prepreg process; Described pressure when hot-forming is 600～3000MPa, and temperature is 170～190 ℃, and the time is 20～35 minutes.
In preferred technical scheme, in described step (1), anhydrous Lithium chloride is vacuum drying 2～5h under 100～120 ℃ of conditions first, then joins in polar solvent, forms the dissolution system of chloride containing lithium.
In technique scheme, in described step (1), polar solvent is dimethylacetylamide.
In technique scheme, in described step (1), the temperature while dissolving aramid fiber 1313 is 80～130 ℃.
In technique scheme, in described step (2), electrostatic spinning condition is, spinning voltage 20～30KV, spinning head is internal diameter 0.35～0.85mm, spinning solution flow 0.1～0.6ml/h, collecting drum rotating speed 4～9m/min, spinning head transverse shifting speed 10～26cm/min, spinning distance 8～15cm.
In technique scheme, in described step (4), the superimposed mode of two aramid fiber 1313 nanofiber mats for following any one: the fiber in two fibrofelts is that single direction is arranged, fiber in two fibrofelts be 45 ° be staggered, fiber in two fibrofelts is 90 ° and is staggered.
In technique scheme, in described step (5), prepreg, after hot-forming, keeps pressure constant, cooling under room temperature after, obtaining described Static Spinning aramid fiber 1313 nanofiber mats/lactic acid composite material through finishing.
The invention also discloses the Static Spinning aramid fiber 1313 nanofiber mats/lactic acid composite material preparing according to said method.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
1. the present invention is combined Static Spinning aramid fiber 1313 nanofiber first with PLA, has obtained through hot pressing the fiber reinforced polymer composites that quality is light, mechanical property is excellent;
2. the present invention adopts the technique of optimization to prepare the aramid fiber 1313 nanofiber mats of height-oriented arrangement, has overcome the defect of random packing of fibers in prior art; The Static Spinning aramid fiber 1313 nanofiber that has obtained having again various mechanical characteristics by controlling superimposed mode between each layer of nanofiber mats strengthens lactic acid composite material, the bearing capacity while can be used to regulate composite to be subject to different directions External Force Acting;
3. preparation method's Raw disclosed by the invention is easy to get, reaction condition gentleness, and the reaction time is short, and equipment requirement is low, and cost of manufacture is few, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the superimposed mode schematic diagram of two aramid fiber 1313 nanofiber mats in embodiment, wherein A be two fibers in fibrofelt be 90 ° be staggered, B be two fibers in fibrofelt be 45 ° be staggered, C be two fibers in fibrofelt be single direction arrange;
Fig. 2 is the scanning electron microscope (SEM) photograph of Static Spinning aramid fiber 1313 nanofiber mats in embodiment bis-;
Fig. 3 is the photo that in embodiment bis-, Static Spinning aramid fiber 1313 nanofiber mats strengthens lactic acid composite material.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described:
Embodiment mono-
Take a certain amount of anhydrous LiCl, 120 ℃ of vacuum drying 2h, then join and in DMAc, form LiCl/DMAc dissolution system, take a certain amount of aramid fiber 1313, join in LiCl/DMAc dissolution system, under 120 ℃ of conditions, stirring and dissolving becomes clear solution, and the mass fraction that wherein mass fraction of aramid fiber 1313 is 11%, LiCl is 7%;
At spinning voltage 26kv, spinning head is internal diameter 0.85mm, spinning solution flow 0.45ml/h, collecting drum rotating speed 9m/min, spinning head transverse shifting speed 16cm/min, spinning, apart from 15cm, is carried out spinning under the condition that the spinning time is 18h, prepare the aramid fiber 1313 nanofiber mats that fiber alignment is arranged;
Referring to accompanying drawing 1A, fiber in two orientations aramid fiber 1313 nano fibrous membranes of above-mentioned spinning is staggered by 90 °, then impregnated in the dichloromethane solution of PLA, in solution, PLA mass fraction is 7%, then make at normal temperatures solvent evaporates complete, obtain prepreg;
Prepreg is placed between two smooth glass plates, exerts pressure as 2200MPa, heat treatment 30min in the baking oven of 190 ℃, then keep pressure constant, at room temperature cooling, then it is repaired, Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material obtained.
Embodiment bis-
Take a certain amount of anhydrous LiCl, 120 ℃ of vacuum drying 3h, then join and in DMAc, form LiCl/DMAc dissolution system, take a certain amount of aramid fiber 1313, join in LiCl/DMAc dissolution system, under 100 ℃ of conditions, stirring and dissolving becomes clear solution, and the mass fraction that wherein mass fraction of aramid fiber 1313 is 14%, LiCl is 5%;
At spinning voltage 24kv, spinning head is internal diameter 0.85mm, spinning solution flow 0.3ml/h, collecting drum rotating speed 8m/min, spinning head transverse shifting speed 20cm/min, spinning, apart from 13cm, is carried out spinning under the condition that the spinning time is 14h, prepare the aramid fiber 1313 nanofiber mats that fiber alignment is arranged;
Referring to accompanying drawing 1B, fiber in two orientations aramid fiber 1313 nano fibrous membranes of above-mentioned spinning is staggered by 45 °, then impregnated in the dichloromethane solution of PLA, in solution, PLA mass fraction is 3%, then make at normal temperatures solvent evaporates complete, obtain prepreg;
Prepreg is placed between two smooth glass plates, exerts pressure as 1400MPa, heat treatment 20min in the baking oven of 180 ℃, then keep pressure constant, at room temperature cooling, then it is repaired, Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material obtained.
The scanning electron microscope (SEM) photograph of the aramid fiber 1313 nanofiber mats that accompanying drawing 2 is above-mentioned preparation, can find out that nanofiber form is even, and orientations degree is good, is very beneficial for as directed reinforcing fiber materials.
The photo of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material that accompanying drawing 3 is above-mentioned preparation, can find out that composite material forming is good, and surface is more smooth, and without obvious crackle, between fiber and matrix, caking property is good.
Embodiment tri-
Take a certain amount of anhydrous LiCl, 110 ℃ of vacuum drying 4h, then join and in DMAc, form LiCl/DMAc dissolution system, take a certain amount of aramid fiber 1313, join in LiCl/DMAc dissolution system, under 110 ℃ of conditions, stirring and dissolving becomes clear solution, and the mass fraction that wherein mass fraction of aramid fiber 1313 is 10%, LiCl is 7%;
At spinning voltage 25kv, spinning head is internal diameter 0.85mm, spinning solution flow 0.35ml/h, collecting drum rotating speed 7m/min, spinning head transverse shifting speed 18cm/min, spinning, apart from 13cm, is carried out spinning under the condition that the spinning time is 16h, prepare the aramid fiber 1313 nanofiber mats that fiber alignment is arranged;
Referring to accompanying drawing 1B, fiber in two orientations aramid fiber 1313 nano fibrous membranes of above-mentioned spinning is staggered by 45 °, then impregnated in the dichloromethane solution of PLA, in solution, PLA mass fraction is 5%, then make at normal temperatures solvent evaporates complete, obtain prepreg;
Prepreg is placed between two smooth glass plates, exerts pressure as 1800MPa, heat treatment 25min in the baking oven of 185 ℃, then keep pressure constant, at room temperature cooling, then it is repaired, Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material obtained.
Embodiment tetra-
Take a certain amount of anhydrous LiCl, 100 ℃ of vacuum drying 2h, then join and in DMAc, form LiCl/DMAc dissolution system, take a certain amount of aramid fiber 1313, join in LiCl/DMAc dissolution system, under 100 ℃ of conditions, stirring and dissolving becomes clear solution, and the mass fraction that wherein mass fraction of aramid fiber 1313 is 12%, LiCl is 6%;
At spinning voltage 23kv, spinning head is internal diameter 0.85mm, spinning solution flow 0.26ml/h, collecting drum rotating speed 6m/min, spinning head transverse shifting speed 14cm/min, spinning, apart from 11cm, is carried out spinning under the condition that the spinning time is 12h, prepare the aramid fiber 1313 nanofiber mats that fiber alignment is arranged;
Referring to accompanying drawing 1C, fiber in two orientations aramid fiber 1313 nano fibrous membranes of above-mentioned spinning is pressed to single direction and arrange, then impregnated in the dichloromethane solution of PLA, in solution, PLA mass fraction is 3%, then make at normal temperatures solvent evaporates complete, obtain prepreg;
Prepreg is placed between two smooth glass plates, exerts pressure as 1000MPa, heat treatment 30min in the baking oven of 185 ℃, then keep pressure constant, at room temperature cooling, then it is repaired, Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material obtained.
Performance test
Respectively along the vertical and horizontal direction of fiber in the Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material of above-mentioned preparation, prepare dumbbell shaped batten, under standard atmosphere condition, after balance 24h, on Instron 5967 electronics strength testers, carry out stretching mechanical property testing.The concrete data of tensile property that obtain are in table 1.
The mechanical property of table 1 composite characterizes
| ? | Fiber quality mark/% | Longitudinal stretching fracture strength/MPa | Cross directional stretch fracture strength/MPa |
| Embodiment mono- | 18.96 | 9.72 | 9.45 |
| Embodiment bis- | 45.63 | 10.62 | 6.87 |
| Embodiment tri- | 27.17 | 12.33 | 7.26 |
| Embodiment tetra- | 39.61 | 18.65 | 6.51 |
Can find the arrangement mode difference of fiber between laminated fibrofelt, the load difference can bear on longitudinal and transverse draw direction from the experimental data recording.Fortifying fibre layer is 90 ° of staggered Static Spinning aramid fiber 1313 nanofiber/lactic acid composite materials (embodiment mono-), and the peak load can bear when longitudinal stretching is similar during to cross directional stretch, has the feature of the same sex in length and breadth; 45 ° of staggered Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material of fortifying fibre layer (embodiment bis-, three), when longitudinal stretching, the peak load that composite can bear is also greater than cross directional stretch, also there is in length and breadth the feature of the opposite sex, but difference is between the two less than fortifying fibre while being single arrangement direction; Fortifying fibre is Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material (embodiment tetra-) that single direction is arranged, the peak load that longitudinal stretching can bear much larger than with cross directional stretch, the former is the more than 2 times of the latter, has significantly different in nature feature in length and breadth.As can be seen here, adopt method of the present invention, can be according to the stress characteristic in composite use procedure, by control the orientation of aramid fiber 1313 nanofiber layer of height-oriented arrangement regulate composite be subject to different directions External Force Acting time bearing capacity.
Claims (8)
1. a preparation method for Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material, is characterized in that, comprises the following steps:
(1) in polar solvent, add anhydrous Lithium chloride, form the dissolution system of chloride containing lithium, aramid fiber 1313 is joined in dissolution system, dissolve and obtain the spinning solution that contains aramid fiber 1313; In spinning solution, in mass, the content of aramid fiber 1313 is 8～16%, and the content of lithium chloride is 5～8%;
(2) adopt electrospinning process, obtain fiber and be the aramid fiber 1313 nanofiber mats aligning;
(3) PLA is dissolved in carrene, obtains mass concentration and be 2～6% PLA solution;
(4) the aramid fiber 1313 nanofiber mats two steps (2) being obtained is superimposed, then impregnated in the PLA solution that step (3) obtains, after the solvent in the aramid fiber 1313 nanofiber mats after to be impregnated volatilizees naturally, obtain aramid fiber 1313 nanofiber mats/PLA prepreg;
(5) by the Static Spinning aramid fiber 1313 nanofiber mats/lactic acid composite material described in hot-forming the obtaining of aramid fiber 1313 nanofiber mats/PLA prepreg process; Described pressure when hot-forming is 600～3000MPa, and temperature is 170～190 ℃, and the time is 20～35 minutes.
2. the preparation method of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material according to claim 1, it is characterized in that: in step (1), anhydrous Lithium chloride is vacuum drying 2～5h under 100～120 ℃ of conditions first, then joins in polar solvent, forms the dissolution system of chloride containing lithium.
3. the preparation method of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material according to claim 1, is characterized in that: in step (1), polar solvent is dimethylacetylamide.
4. the preparation method of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material according to claim 1, is characterized in that: in step (1), the temperature while dissolving aramid fiber 1313 is 80～130 ℃.
5. the preparation method of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material according to claim 1, it is characterized in that: in step (2), electrostatic spinning condition is, spinning voltage 20～30KV, spinning head is internal diameter 0.35～0.85mm, spinning solution flow 0.1～0.6ml/h, collecting drum rotating speed 4～9m/min, spinning head transverse shifting speed 10～26cm/min, spinning distance 8～15cm.
6. the preparation method of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material according to claim 1, it is characterized in that: in step (4), the superimposed mode of two aramid fiber 1313 nanofiber mats for following any one: the fiber in two fibrofelts is that single direction is arranged, fiber in two fibrofelts be 45 ° be staggered, fiber in two fibrofelts is 90 ° and is staggered.
7. the preparation method of Static Spinning aramid fiber 1313 nanofiber/lactic acid composite material according to claim 1, it is characterized in that: in step (5), prepreg is after hot-forming, keep pressure constant, after cooling under room temperature, obtain described Static Spinning aramid fiber 1313 nanofiber mats/lactic acid composite material through finishing.
8. the Static Spinning aramid fiber 1313 nanofiber mats/lactic acid composite material preparing according to any one method in claim 1～7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017116598A1 (en) * | 2015-12-30 | 2017-07-06 | The Regents Of The University Of Michigan | Gels and nanocomposites containing aramid nanofibers |
| CN108624016A (en) * | 2018-04-24 | 2018-10-09 | 上海交通大学 | Aramid fiber modified carbon fiber enhances polylactic acid thermoplastic composite and preparation method |
| CN115198567A (en) * | 2022-06-28 | 2022-10-18 | 陈克复 | High-performance aramid laminated board and preparation method and application thereof |
| CN115217000A (en) * | 2022-06-28 | 2022-10-21 | 陈克复 | High-performance aramid fiber paperboard and preparation method and application thereof |
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| WO2017116598A1 (en) * | 2015-12-30 | 2017-07-06 | The Regents Of The University Of Michigan | Gels and nanocomposites containing aramid nanofibers |
| CN108699259A (en) * | 2015-12-30 | 2018-10-23 | 密执安州立大学董事会 | Gel containing ANF and nanocomposite |
| US11111343B2 (en) | 2015-12-30 | 2021-09-07 | The Regents Of The University Of Michigan | Gels and nanocomposites containing ANFS |
| CN108624016A (en) * | 2018-04-24 | 2018-10-09 | 上海交通大学 | Aramid fiber modified carbon fiber enhances polylactic acid thermoplastic composite and preparation method |
| CN115198567A (en) * | 2022-06-28 | 2022-10-18 | 陈克复 | High-performance aramid laminated board and preparation method and application thereof |
| CN115217000A (en) * | 2022-06-28 | 2022-10-21 | 陈克复 | High-performance aramid fiber paperboard and preparation method and application thereof |
| CN115198567B (en) * | 2022-06-28 | 2023-10-13 | 陈克复 | High-performance aramid laminate and preparation method and application thereof |
| CN115217000B (en) * | 2022-06-28 | 2023-11-07 | 陈克复 | High-performance aramid fiber paperboard and preparation method and application thereof |
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