CN114274567A - Phenolic filling aramid fiber honeycomb structure and preparation method and application thereof - Google Patents
Phenolic filling aramid fiber honeycomb structure and preparation method and application thereof Download PDFInfo
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- CN114274567A CN114274567A CN202111667128.XA CN202111667128A CN114274567A CN 114274567 A CN114274567 A CN 114274567A CN 202111667128 A CN202111667128 A CN 202111667128A CN 114274567 A CN114274567 A CN 114274567A
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- aramid fiber
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 81
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000011049 filling Methods 0.000 title claims description 19
- 241000264877 Hippospongia communis Species 0.000 claims abstract description 125
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000005011 phenolic resin Substances 0.000 claims abstract description 63
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 63
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 36
- 239000002313 adhesive film Substances 0.000 claims abstract description 29
- 238000005187 foaming Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000011825 aerospace material Substances 0.000 claims abstract description 3
- 239000004760 aramid Substances 0.000 claims description 33
- 229920003235 aromatic polyamide Polymers 0.000 claims description 33
- 238000001723 curing Methods 0.000 claims description 33
- 239000003292 glue Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000007731 hot pressing Methods 0.000 claims description 11
- 239000002356 single layer Substances 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000004026 adhesive bonding Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000013530 defoamer Substances 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000009413 insulation Methods 0.000 abstract description 7
- 238000004321 preservation Methods 0.000 abstract description 7
- 238000002679 ablation Methods 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract description 4
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 229920000784 Nomex Polymers 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000004763 nomex Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ISNKSXRJJVWFIL-UHFFFAOYSA-N (sulfonylamino)amine Chemical class NN=S(=O)=O ISNKSXRJJVWFIL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
The invention relates to a phenolic aldehyde filled aramid fiber honeycomb structure and a preparation method and application thereof, wherein the phenolic aldehyde filled aramid fiber honeycomb structure takes aramid fiber honeycombs as a framework, phenolic resin is filled in cells of the aramid fiber honeycombs, then a phenolic resin adhesive film with the thickness of 0.5-3 mm is loaded, and the phenolic aldehyde filled aramid fiber honeycomb structure is obtained after foaming and curing; the phenolic resin adhesive film is prepared from the following raw materials: 80-120 parts of phenolic resin, 10-60 parts of foaming agent, 2-15 parts of curing agent and 5-30 parts of filler. The foamed phenolic filled aramid fiber honeycomb provided by the invention has the characteristics of light weight, high bending resistance, high compression resistance, shear resistance, heat preservation, heat insulation, flame retardance and ablation resistance; in the limited use space, the material is endowed with multiple functions, and the design space of the material is saved. Can be widely applied to aerospace materials.
Description
Technical Field
The invention relates to an aramid honeycomb, in particular to a phenolic aldehyde filled aramid honeycomb structure and a preparation method and application thereof.
Background
As a mature resin system, the phenolic resin is widely applied to the fields of composite materials, heat preservation and bonding due to the advantages of various molding processes, low cost, mature technology, high fire safety and the like. The foamed phenolic aldehyde not only has light weight and high strength, but also has the characteristic of intrinsic flame retardance, and is an ideal heat-insulating material. Due to excellent compression resistance, bending resistance and flame retardance, the aramid fiber honeycomb is widely used as a secondary load-bearing structure and applied to the fields of aviation, aerospace and military. With the technical progress in the field of aerospace military equipment, higher requirements are put forward on the performance of composite materials, and the materials are required to have higher specific strength, safer flame retardance, better heat insulation and the like. The aramid fiber honeycomb filled with the foamed phenolic aldehyde provides a new material design idea, the material can maintain higher specific strength, can also play the functions of flame retardance, heat insulation and heat preservation, and is a typical new material integrating structural functions.
In the existing foaming phenolic aldehyde technology, phenolic resin is made into a closed-cell low-density foaming material, and the prepared foaming phenolic aldehyde has poor mechanical property, poor toughness and poor impact resistance, cannot be used as a bearing structure and only can be used as a covering piece to play a role in heat preservation. Aramid fiber honeycomb is a widely used secondary load-bearing structure, and the heat insulation performance is poor.
Disclosure of Invention
The invention provides a phenolic aldehyde filled aramid fiber honeycomb structure, which takes an aramid fiber honeycomb as a framework, wherein phenolic resin is filled in cells of the aramid fiber honeycomb, then a phenolic resin adhesive film with the thickness of 0.5-3 mm is loaded, and the phenolic aldehyde filled aramid fiber honeycomb structure is obtained after foaming and curing;
the phenolic resin adhesive film is prepared from the following raw materials: 80-120 parts of phenolic resin, 10-60 parts of foaming agent, 2-15 parts of curing agent and 5-30 parts of filler.
Wherein the phenolic resin is water-soluble phenolic resin.
Specifically, the method comprises the following steps: firstly, soaking aramid fiber honeycombs in phenolic resin, and filling phenolic resin into the pores of the aramid fiber honeycombs; then compounding with a phenolic resin adhesive film with the thickness of 0.5-3 mm (the compounding process comprises curing and foaming); further loading and filling of the cells allows the cells to be completely filled.
The phenolic aldehyde filled aramid fiber honeycomb structure provided by the invention is filled in aramid fiber honeycomb by impregnation, and foaming phenolic resin is filled in honeycomb cells; the foamed phenolic resin is pre-prepared into a glue film in advance, the glue film and the honeycomb are compounded and hot-pressed, and the foaming, curing and filling of the honeycomb are synchronously completed.
Honeycomb filling technology refers to the filling of a material into the cell structure of a honeycomb such that the filled honeycomb has some functionality. The foamed phenolic aldehyde is filled into the aramid fiber honeycomb, so that the defect of poor mechanical property of the phenolic aldehyde is overcome, the heat preservation and heat insulation performance of the aramid fiber honeycomb can be improved, the foamed phenolic aldehyde has the advantages of high compression resistance, bending resistance, shearing resistance, flame retardance, heat preservation, heat insulation, ablation resistance and the like, the design space of the material can be saved, and the foamed phenolic aldehyde is a typical structure function integrated material and has wide application in the fields of aerospace, military and the like.
The invention further provides that the addition of the foaming agent mainly ensures the foaming effect, but different components, the foaming effect, the density and the performance of the final product have larger differences.
The foaming agent is one or more of azo compounds and sulfonyl hydrazine compounds;
the curing agent is one or more of oxalic acid, benzenesulfonic acid, citric acid and p-toluenesulfonic acid;
the filler is one or more of white carbon black, glass beads and alumina.
The invention further provides a composition which also comprises 0.5-2 parts of defoaming agent and 0.5-2 parts of flatting agent; preferably, the defoaming agent is vinyl silicone oil; the leveling agent is polyurethane.
The phenolic resin adhesive film is preferably prepared from the following raw materials: 80-120 parts of phenolic resin, 20-30 parts of foaming agent, 2-5 parts of curing agent and 5-8 parts of filler;
wherein the foaming agent is azobisisobutyronitrile.
The invention further provides a phenolic aldehyde filled aramid fiber honeycomb structure, wherein the aramid fiber honeycomb is made of aramid fiber paper, and the length of the side of each cell of the aramid fiber honeycomb is 1.8-4.5 mm; preferably 3.5-4.5 mm;
preferably meta-aramid paper, such as DuPont's Nomex, which has excellent flame retardancy, low toxicity and excellent mechanical and fatigue resistance properties.
Preferably, the thickness of the aramid honeycomb is 8-12 mm;
more preferably, the aramid fiber honeycomb is prepared by the following method: and (3) subjecting aramid paper to gluing, laminating, cold pressing and hot pressing, and then stretching and shaping to obtain the aramid honeycomb.
The invention further provides that the thickness of the phenolic resin adhesive film is 0.5-2mm, and the foaming ratio of the adhesive film is 12-20 times; preferably 0.8 to 1.2 mm.
The thickness of the foamed phenolic resin adhesive film is different from 0.5-2mm according to the foaming multiplying power of the foamed phenolic resin and the height of the honeycomb core.
In the application process, aramid honeycomb cells of the invention need to be filled with foaming phenolic aldehyde; in order to ensure the effect, sufficient foaming agent needs to be added into the preparation components of the foaming adhesive film to ensure the full foaming, but different addition amounts of the foaming agent and other components can directly influence the density and other properties of the final product. In addition, the correlation between different preparation conditions and the formula has a great influence on the performance of the final product. In order to ensure that the phenolic aldehyde filled aramid fiber honeycomb structure has better performance and is light enough; the invention further provides a preparation method of the phenolic aldehyde filled aramid fiber honeycomb structure,
the method comprises the following steps:
1) after the aramid fiber paper is subjected to gluing, laminating, cold pressing and hot pressing, the aramid fiber paper is stretched and shaped into an aramid fiber honeycomb shape;
2) soaking the aramid fiber honeycomb in an alcohol-soluble phenolic resin solution, and airing until ethanol is volatilized completely; repeating the steps of dipping and airing for multiple times until the density of the phenolic resin filled aramid fiber honeycomb is 50-65 kg/m3, and drying and curing; slicing and cutting into single-layer aramid fiber honeycombs;
3) mixing phenolic resin, a foaming agent, a filler, a defoaming agent and a flatting agent, and grinding the mixture into uniform colloid; adding a curing agent, and continuously grinding to obtain uniform glue solution; then spreading the glue solution into a phenolic resin glue film with the thickness of 0.5-3 mm; preferably 0.5-2mm, more preferably 0.8-1.2 mm;
4) loading the phenolic resin adhesive film on the single-layer aramid honeycomb obtained in the step 2), and curing for 0.4-0.7 hour under the conditions that the temperature is 120-180 ℃ and the pressure is 0.4-0.5 Mpa, so as to obtain the phenolic filling aramid honeycomb structure.
Preferably, the foaming ratio of the phenolic resin adhesive film is 12-25 times; more preferably 20 to 25 times.
The invention provides a preferable scheme, and the preparation method comprises the following steps:
1) after the aramid fiber paper is subjected to gluing, laminating, cold pressing and hot pressing, the aramid fiber paper is stretched and shaped into an aramid fiber honeycomb shape with the side length of 3.5-4.5 mm;
2) soaking the aramid fiber honeycomb in an alcohol-soluble phenolic resin solution, and airing until ethanol is volatilized completely; repeating the steps of dipping and airing for multiple times until the density of the phenolic resin filled aramid fiber honeycomb is 50-65 kg/m3, and drying and curing; slicing and cutting the aramid fiber honeycombs with the thickness of 8-12 mm into single layers;
3) mixing 80-120 parts of phenolic resin, 20-30 parts of foaming agent, 5-8 parts of filler, 0.5-2 parts of defoaming agent and 0.5-2 parts of flatting agent, and grinding into uniform colloid; adding 2-5 parts of curing agent, and continuously grinding to obtain uniform glue solution; then spreading the glue solution into a phenolic resin glue film with the thickness of 0.8-1.2 mm;
4) loading the phenolic resin adhesive film on the single-layer aramid honeycomb obtained in the step 2), and curing for 0.4-0.7 hour under the conditions that the temperature is 120-180 ℃ and the pressure is 0.4-0.5 Mpa, so as to obtain the phenolic filling aramid honeycomb structure.
The foamed phenolic filled aramid fiber honeycomb provided by the invention has the characteristics of light weight, high bending resistance, high compression resistance, shear resistance, heat preservation, heat insulation, flame retardance and ablation resistance; in the limited use space, the material is endowed with multiple functions, and the design space of the material is saved. Can be widely applied to aerospace materials.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The preparation method of the phenolic aldehyde filled aramid fiber honeycomb structure comprises the following specific steps:
1) after the aramid fiber paper is subjected to gluing, laminating, cold pressing and hot pressing, the aramid fiber paper is stretched and shaped into an aramid fiber honeycomb shape with the side length of 3.5-4.5 mm;
2) soaking the aramid fiber honeycomb in an alcohol-soluble phenolic resin solution, and airing until ethanol is volatilized completely; repeating the steps of dipping and airing for multiple times until the density of the phenolic resin filled aramid fiber honeycomb is 50-65 kg/m3, and drying and curing; slicing and cutting the aramid fiber honeycombs with the thickness of 8-12 mm into single layers;
3) mixing 80-120 parts of aqueous solution phenolic resin, 20-30 parts of azodiisobutyronitrile, 5-8 parts of filler, 0.5-2 parts of vinyl silicone oil and 0.5-2 parts of polyurethane, and grinding the mixture to form uniform colloid; adding 2-5 parts of benzenesulfonic acid, and continuously grinding to obtain a uniform glue solution; then spreading the glue solution into a phenolic resin glue film with the thickness of 0.8-1.2 mm;
wherein the filler is white carbon black or glass beads;
4) loading the phenolic resin adhesive film on the single-layer aramid honeycomb obtained in the step 2), and curing for 0.4-0.7 hour under the conditions that the temperature is 120-180 ℃ and the pressure is 0.4-0.5 Mpa, so as to obtain the phenolic filling aramid honeycomb structure.
Example 1
The embodiment provides a phenolic aldehyde filled aramid fiber honeycomb structure, which is prepared by adopting the following method:
preparation of 1 aramid honeycomb
Preparing aramid fiber honeycombs: coating DuPont Nomex aramid fiber paper with the thickness of 0.04mm, dispensing, laminating, cold pressing, hot pressing at 150 ℃ for 2 hours, curing the node glue, stretching on a stretching machine to form a honeycomb structure, then shaping at the high temperature of 120 ℃ for 1 hour, immersing the shaped honeycomb into alcohol-soluble phenolic resin solution tanks with different concentrations, taking out and drying until ethanol volatilizes, soaking and drying for multiple times, repeating the previous steps until the designed density is reached, putting the honeycomb impregnated with the phenolic resin into an oven for 1 hour at 180 ℃ for curing, and finally obtaining the honeycomb with the side length of 3.8mm and the density of 54kg/m3The hexagonal Nomex aramid paper honeycomb is marked as NRH-3.8-54.
And cutting the NRH-3.8-54 into honeycomb sheets with the thickness of 10mm on a honeycomb sheet cutting machine for later use.
2 preparation of phenolic foam adhesive film for filling
Weighing 100 parts of water-soluble phenolic resin, 20 parts of foaming agent azodiisobutyronitrile, 5 parts of white carbon black, 2 parts of defoaming agent vinyl silicone oil, 1 part of flatting agent polyurethane, grinding into uniform colloid on a three-roller grinder, adding 3 parts of benzenesulfonic acid curing agent, grinding for 5 minutes, adjusting the roller spacing, extruding the mixed colloid into a film with the thickness of 1mm, placing a PET release film at the lower part of the film, rolling and placing into a refrigeration house at the temperature of-17 ℃ for later use. The expansion ratio of this foam was 12 times.
3 honeycomb filling
Firstly, taking out the adhesive film, unfreezing, cutting into a proper size, then taking out NRH-3.8-54 with the thickness of 10mm, placing the adhesive film above, setting the temperature at 150 ℃, the pressure at 0.5MPa and the time at 0.5 hour to obtain the aramid fiber honeycomb filled with the foamed phenolic aldehyde. The method for preparing the honeycomb filled with the foamed phenolic aldehyde has the advantages of high efficiency, simple operation, continuity and standard operation. In the hot pressing process, the foaming process and the curing process of the foaming phenolic aldehyde for filling are synchronously finished.
Performance comparison
It can be seen that the foamed phenolic filled NRH-3.8-54 honeycomb has better mechanical properties, the thermal conductivity coefficient of the honeycomb is reduced to one twentieth of that of the unfilled honeycomb, and the honeycomb has ablation resistance functionality and stronger toughness.
Example 2
The embodiment provides a phenolic aldehyde filled aramid fiber honeycomb structure, which is prepared by adopting the following method:
preparation of 1 aramid honeycomb
Preparing aramid fiber honeycombs: coating DuPont Nomex aramid fiber paper with the thickness of 0.05mm, dispensing, laminating, cold pressing, hot pressing at 150 ℃ for 2 hours, curing the node adhesive, stretching on a stretcher, forming a honeycomb structure, and then shaping at the high temperature of 120 ℃ for 1 hourSoaking the shaped honeycomb into alcohol-soluble phenolic resin solution tanks with different concentrations, taking out and airing until ethanol is volatilized, soaking and airing for multiple times, repeating the previous steps until the designed density is reached, placing the honeycomb soaked with the phenolic resin into an oven for curing at 180 ℃ for 1 hour to finally obtain the honeycomb with the side length of 4.2mm and the density of 64kg/m3The hexagonal Nomex aramid paper honeycomb is marked as NRH-4.2-64.
The NRH-4.2-54 was sliced into 12mm thick honeycomb pieces on a honeycomb slicer for use.
2 preparation of phenolic foam adhesive film for filling
Weighing 100 parts of water-soluble phenolic resin, 30 parts of foaming agent azodiisobutyronitrile, 5 parts of glass beads, 1 part of defoaming agent vinyl silicone oil, 0.5 part of flatting agent polyurethane, grinding the mixture into uniform colloid on a three-roll grinder, adding 3 parts of benzenesulfonic acid curing agent, grinding for 5 minutes, adjusting the roll spacing, extruding the mixed glue solution into a film with the thickness of 0.6mm, placing a PET release film below the film, and rolling the film into a refrigeration house at the temperature of-17 ℃ for later use. The expansion ratio of this foam was 20 times.
3 honeycomb filling
Firstly, taking out the adhesive film, unfreezing, cutting into a proper size, then taking out NRH-4.2-64 with the thickness of 12mm, placing the adhesive film above, setting the temperature at 150 ℃, the pressure at 0.5MPa and the time at 0.5 hour to obtain the aramid fiber honeycomb filled with the foamed phenolic aldehyde. The method for preparing the honeycomb filled with the foamed phenolic aldehyde has the advantages of high efficiency, simplicity in operation and convenience in standardized operation. In the hot pressing process, the foaming process and the curing process of the foaming phenolic aldehyde for filling are synchronously finished.
Performance comparison
It can be seen that the NRH-4.2-64 honeycomb filled with the foamed phenolic aldehyde has better mechanical property, the heat conductivity coefficient is obviously reduced, and the honeycomb has ablation resistance functionality; in addition, the toughness is excellent.
Example 3
This example provides a phenolic-filled aramid honeycomb structure, differing from example 2 only in that the blowing agent azobisisobutyronitrile was 15 parts; the foaming ratio of the prepared foaming adhesive is 10 times.
The heat conductivity coefficient is about 0.1W/mK, but the density is obviously increased.
Example 4
The embodiment provides a phenolic aldehyde filled aramid fiber honeycomb structure, which is different from the embodiment 2 only in that 6 parts of a benzene sulfonic acid curing agent is used;
the strength of the prepared phenolic aldehyde filled aramid fiber honeycomb structure is improved to some extent, but the toughness is obviously reduced.
Comparative example 1
This comparative example provides a phenolic-filled aramid honeycomb structure, differing from example 2 only in step 1), the aramid honeycomb does not include a step of impregnation;
the overall performance of the obtained phenolic aldehyde filled aramid fiber honeycomb structure is obviously reduced.
Comparative example 2
This comparative example provides a foam filled aramid honeycomb, differing from example 2 in that foamed polyurethane is used instead of phenolic resin;
the final product does not have the ablation resistance function, and the overall performance is poor.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The phenolic aldehyde filled aramid fiber honeycomb structure is characterized in that aramid fiber honeycombs are used as frameworks, phenolic resin is filled in cells of the aramid fiber honeycombs, then a phenolic resin adhesive film with the thickness of 0.5-3 mm is loaded, and foaming and curing are carried out to obtain the phenolic aldehyde filled aramid fiber honeycomb structure;
the phenolic resin adhesive film is prepared from the following raw materials: 80-120 parts of phenolic resin, 10-60 parts of foaming agent, 2-15 parts of curing agent and 5-30 parts of filler.
2. The phenolic-filled aramid honeycomb structure of claim 1, wherein the blowing agent is one or more of an azo compound and a sulfonyl hydrazide compound;
and/or the curing agent is one or more of oxalic acid, benzenesulfonic acid, citric acid and p-toluenesulfonic acid;
and/or the filler is one or more of white carbon black, glass beads and alumina.
3. The phenolic-filled aramid honeycomb structure of claim 2, wherein the phenolic resin adhesive film is prepared from raw materials comprising: 80-120 parts of phenolic resin, 20-30 parts of foaming agent, 2-5 parts of curing agent and 5-8 parts of filler;
wherein the foaming agent is azobisisobutyronitrile.
4. The phenolic filling aramid fiber honeycomb structure of any one of claims 1 to 3, wherein the aramid fiber honeycomb is made of aramid fiber paper, and the length of the cell side of the aramid fiber honeycomb is 1.8-4.5 mm; preferably 3.5-4.5 mm;
preferably, the thickness of the aramid honeycomb is 8-12 mm;
more preferably, the aramid fiber honeycomb is prepared by the following method: and (3) subjecting aramid paper to gluing, laminating, cold pressing and hot pressing, and then stretching and shaping to obtain the aramid honeycomb.
5. The phenolic-filled aramid honeycomb structure of any one of claims 1 to 4, wherein the composition further comprises 0.5 to 2 parts of a defoamer and 0.5 to 2 parts of a leveling agent; preferably, the defoaming agent is vinyl silicone oil; the leveling agent is polyurethane.
6. The phenolic-filled aramid honeycomb structure as claimed in any one of claims 1 to 5, wherein the thickness of the phenolic resin adhesive film is 0.5 to 2mm, and the foaming ratio of the adhesive film is 12 to 20 times; preferably 0.8-1.2 mm, and the foaming ratio of the adhesive film is 12-20 times.
7. The preparation method of the phenolic aldehyde filled aramid fiber honeycomb structure as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
1) after the aramid fiber paper is subjected to gluing, laminating, cold pressing and hot pressing, the aramid fiber paper is stretched and shaped into an aramid fiber honeycomb shape;
2) soaking the aramid fiber honeycomb in an alcohol-soluble phenolic resin solution, and airing until ethanol is volatilized completely; repeating the steps of dipping and airing for multiple times until the density of the phenolic resin filled aramid fiber honeycomb is 50-65 kg/m3Then drying and curing; slicing and cutting into single-layer aramid fiber honeycombs;
3) mixing phenolic resin, a foaming agent, a filler, a defoaming agent and a flatting agent, and grinding the mixture into uniform colloid; adding a curing agent, and continuously grinding to obtain uniform glue solution; then spreading the glue solution into a phenolic resin glue film with the thickness of 0.5-3 mm; preferably 0.5-2mm, more preferably 0.8-1.2 mm;
4) loading the phenolic resin adhesive film on the single-layer aramid honeycomb obtained in the step 2), and curing for 0.4-0.7 hour under the conditions that the temperature is 120-180 ℃ and the pressure is 0.4-0.5 Mpa, so as to obtain the phenolic filling aramid honeycomb structure.
8. The preparation method according to claim 7, wherein the foaming ratio of the phenolic resin adhesive film is 12-25 times; preferably 20 to 25 times.
9. The method of claim 7, comprising the steps of:
1) after the aramid fiber paper is subjected to gluing, laminating, cold pressing and hot pressing, the aramid fiber paper is stretched and shaped into an aramid fiber honeycomb shape with the side length of 3.5-4.5 mm;
2) soaking the aramid fiber honeycomb in an alcohol-soluble phenolic resin solution, and airing until ethanol is volatilized completely; repeating the steps of dipping and airing for multiple times until the density of the phenolic resin filled aramid fiber honeycomb is 50-65 kg/m3Then drying and curing; slicing and cutting the aramid fiber honeycombs with the thickness of 8-12 mm into single layers;
3) mixing 80-120 parts of phenolic resin, 20-30 parts of foaming agent, 5-8 parts of filler, 0.5-2 parts of defoaming agent and 0.5-2 parts of flatting agent, and grinding into uniform colloid; adding 2-5 parts of curing agent, and continuously grinding to obtain uniform glue solution; then spreading the glue solution into a phenolic resin glue film with the thickness of 0.8-1.2 mm;
4) loading the phenolic resin adhesive film on the single-layer aramid honeycomb obtained in the step 2), and curing for 0.4-0.7 hour under the conditions that the temperature is 120-180 ℃ and the pressure is 0.4-0.5 Mpa, so as to obtain the phenolic filling aramid honeycomb structure.
10. Use of a phenolic filled aramid honeycomb structure as claimed in any one of claims 1 to 6 in an aerospace material.
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| CN116100907A (en) * | 2022-09-29 | 2023-05-12 | 北京玻钢院复合材料有限公司 | Preparation method of aircraft cargo compartment floor and aircraft cargo compartment floor |
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