CN107033544B - A kind of nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material and preparation method thereof - Google Patents
A kind of nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing materials and preparation method thereof, first will be dried except the nano-absorbent after glue treated silicon carbide fibre cloth and acidification；Silicon carbide fibre cloth after drying is attached on conductive plate, is then attached to the anode of electrophoretic deposition instrument, another piece of conductive plate is as cathode；In organic solvent by the nano-absorbent dispersion after drying, electrophoretic deposition is carried out, nano-absorbent-silicon carbide fibre multi-scale reinforcing body is obtained；Using fire resistant resin as matrix, nano-absorbent-silicon carbide fibre multi-scale reinforcing body is absorber, and wherein matrix accounts for the 30~50% of matrix and absorber gross mass, and nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material is made.Material of the present invention has both good mechanical property and absorbing property simultaneously, and material structure integrality is good, and impact resistance is strong, is not easy to be layered.
Description
Technical field
The invention belongs to absorbing material fields, and in particular to a kind of nano-absorbent-silicon carbide fibre multi-scale reinforcing body
Reinforced resin based structures absorbing material and preparation method thereof.
Background technique
Compared with resin base microwave absorbing coating, resin-based structural absorbing material has high specific strength and specific stiffness, designability
By force, the advantages that structure size stability is good has become one of the direction of absorbing material most research potential.With stealth technology
Development, develop has the resin-based structural absorbing materials of the excellent performances such as broadband, high-selenium corn, high intensity with important simultaneously
Realistic meaning.Matrix is concentrated mainly on to the research of resin-based structural absorbing material absorbing property at present to be electrically adjustable,
It is largely focused on the research of glass fibre/epoxy resin-base composite material, technological approaches is usually in epoxy resin-base
The middle various conductive fillers of addition, such as carbon black (CB), carbon nanotube (CNTs), graphene, carbon nano-fiber, chopped carbon fiber, ZnO
Etc., but get both absorbing property and mechanical property are tended not to only by the structural wave-absorbing material for adjusting the preparation of matrix electrical property
Can, this is because the volume fraction high (50%-65%) and conductivity of glass fibre are low in structural wave-absorbing material, need high-content
Nano-absorbent improve its absorbing property, and the addition of high-content nano-absorbent can be such that the viscosity of resin system increases, and make
At absorbent, dispersing uniformity is reduced inside structural wave-absorbing material, to compromise the mechanical property of structural wave-absorbing material.
Patent CN 102218868A discloses a kind of absorbing material of silicon carbide fibre reinforced resin base sandwich structure, should
Absorbing material includes first medium layer, absorbed layer, second dielectric layer and the Multifunctional layered in reflecting layer superimposed type structure, serves as each function
The continuous carbofrax fibre of reinforcing material has different resistivity in ergosphere, and the composite material process planning is simple, but not
Dielectric design difficulty with structure sheaf is big, and the thickness of different medium layer can also generate apparent influence to absorbing property.Specially
Sharp CN 102181153A discloses the preparation method of a kind of carbon nanotube and functional fiber enhancing composite polyimide material,
By carbon nanotube after carboxyl-functional, diamine or polyamine are introduced on the carbon nanotubes, will obtain amidized carbon
Nanotube is reacted with the carbon fiber of carboxylated, obtains the carbon fiber of the carbon nanotube of surface grafting, will finally obtain functionalization
Carbon nanotube and carbon fiber are applied in the preparation of composite polyimide material, and intensity and the toughness that can use carbon nanotube are strong
Change toughening carbon fiber, improves the adhesive property of carbon fiber and resin matrix, improve the interface binding intensity of composite material, but simultaneously
Not to its study of radar absorbing property, and due to the characteristic of the high conductivity of carbon fiber, which will not have good
Absorbing property.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, it is fine to provide a kind of nano-absorbent-silicon carbide
Multi-scale reinforcing body reinforced resin based structures absorbing material and preparation method thereof is tieed up, by electrophoretic deposition, is made and has both well
Mechanical property and absorbing property resin-based structural absorbing material.
In order to achieve the above object, the present invention adopts the following technical scheme:
The following steps are included:
(1) it takes silicon carbide fibre cloth handle except glue, nano-absorbent is taken to carry out acidification, it will be except treated for glue
Nano-absorbent after silicon carbide fibre cloth and acidification is dried；
(2) the silicon carbide fibre cloth of step (1) after dry is attached on conductive plate, is then attached to electrophoretic deposition instrument
Anode, another piece of conductive plate is as cathode；The nano-absorbent dispersion of step (1) after dry in organic solvent, is subjected to electricity
Swimming deposition, obtains nano-absorbent-silicon carbide fibre multi-scale reinforcing body, wherein nano-absorbent is in nano-absorbent-carbonization
Mass fraction in silica fibre multi-scale reinforcing body is 0.5%~9.5%；
(3) using fire resistant resin as matrix, nano-absorbent-silicon carbide fibre multi-scale reinforcing body is absorber, wherein
Matrix accounts for the 30~50% of matrix and absorber gross mass, and using polymer matrix composites moulding process, nano-absorbent-is made
Silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material.
Further, comprising the concrete steps that except glue processing in step (1), silicon carbide fibre cloth is put into acetone, 80
It is cleaned 1~12 hour in the ultrasonic wave of~100W.
Further, acidification is that nano-absorbent is put into concentrated nitric acid in step (1), at 50 DEG C~90 DEG C
Reason 5h~for 24 hours, wherein the quality of concentrated nitric acid is 8~30 times of quality of nano-absorbent.
Further, in silicon carbide fibre cloth the conductivity of silicon carbide fibre in 1~1.6S/cm or conductivity 10-6~
10-4S/cm。
Further, nano-absorbent uses the carbon nanotube that caliber is 2~15um for 5~100nm and length, or
The graphene for being 0.2~0.6um with a thickness of 0.8~1nm and particle size.
Further, the drying in step (1) is dried at 50~100 DEG C.
Further, organic solvent is acetone, N-N dimethyl acetamide or ethyl alcohol in step (2)；Nanometer in step (2)
The mass fraction of absorbent in organic solvent is 1%~10%.
Further, in step (2) voltage of electrophoretic deposition in 20V~100V, time of electrophoretic deposition 1~for 24 hours.
Further, in step (3), fire resistant resin is epoxy resin or silicone resin, and polymer matrix composites
Moulding process is manual pasting forming process；Or fire resistant resin is polyimide resin or polybenzoxazoles resin, resin base is multiple
The moulding process of condensation material is die press technology for forming.
It is a kind of to utilize nano-absorbent made from preparation method as described above-silicon carbide fibre multi-scale reinforcing body enhancing tree
Aliphatic radical structural wave-absorbing material.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention puts forward a kind of preparation method of silicon carbide fibre reinforced resin based structures absorbing material, by using electricity
The surface that nano-absorbent deposits to silicon carbide fibre is obtained nano-absorbent-silicon carbide fibre multi-scale enhancement by swimming sedimentation
Body is absorber preparation using nano-absorbent-silicon carbide fibre multi-scale reinforcing body then again using fire resistant resin as matrix
Structural wave-absorbing material makes it while having both good mechanical property and absorbing property, it is hidden to radar wave to meet weapon medium temperature position
The requirement of body and bearing capacity can also be applied to the fields such as anti-electromagnetic radiation, solve conventional multilayer structure absorbing material dielectric
Design difficulty is big, and preparation process is complicated, the relatively low problem of mechanical property.
The bending strength of material of the present invention is 3.5 in bandwidth of the 8-18GHz reflectivity lower than -8dB in 235~594MPa
~7.6GHz, product structure integrality is good, and impact resistance is strong, is not easy to be layered.
Detailed description of the invention
Fig. 1 is that nano-absorbent-silicon carbide fibre multi-scale reinforcing body of 2 hand paste process of embodiment preparation enhances high temperature resistant
The pictorial diagram of resin structure absorbing material.
Fig. 2 is nano-absorbent-silicon carbide fibre multi-scale reinforcing body fire resistant resin of 4 mould pressing process of embodiment preparation
The reflectance curve figure of structural wave-absorbing material.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawing.
Reinforcement is two-dimentional silicon carbide fiber cloth in silicon carbide fibre reinforced resin base wave-absorbing material in the present invention, and matrix is
Fire resistant resin.The conductivity of silicon carbide fibre is in 1~1.6S/cm or conductivity 10-6~10-4S/cm。
Nano-absorbent of the present invention use carbon nanotube or graphene, wherein the optimum tube diameter of carbon nanotube be 5~
100nm, length are 2~15um；For graphene with a thickness of 0.8~1nm, particle size is 0.2~0.6um.
Preparation method of the present invention, comprises the following steps that:
The nano-absorbent of step 1, two-dimentional the silicon carbide fiber cloth and varying particle size of the different conductivity of selection.
Step 2, above-mentioned silicon carbide fibre cloth is put into acetone carry out except glue handle, in ultrasonic wave clean 1~12
It is put into baking oven and dries after hour；Ultrasonic power is 80~100W.Above-mentioned nano-absorbent, which is put into mass fraction, is about
Acidification is carried out in 65% concentrated nitric acid, wherein the quality of concentrated nitric acid is 8~30 times of nano-absorbent, acidification temperature
It is 50 DEG C~90 DEG C, the processing time is 5h~for 24 hours, receiving after carrying out except glue treated silicon carbide fibre cloth and acidification
Rice absorbent, which is put into vacuum oven, dries；Drying temperature is 50~100 DEG C.
The silicon carbide fibre cloth that step 2 obtains is attached to and is then attached to electrophoretic deposition instrument in metal copper plate by step 3
Anode, for another piece of metal copper plate as cathode, the nano-absorbent after step 2 to be obtained to acidification is dispersed in organic solvent
In, in acetone, N-N dimethyl acetamide, ethyl alcohol, wherein the mass fraction of nano-absorbent in organic solvent 1%~
10%.Size 20V~100V of voltage in regulation electrophoretic deposition process, the electrophoretic deposition time 1~for 24 hours, it obtains different nanometers and inhales
Nano-absorbent-silicon carbide fibre multi-scale reinforcing body preparation of agent deposition content is received, wherein nano-absorbent is inhaled in nanometer
Receiving the mass fraction in agent-silicon carbide fibre multi-scale reinforcing body is 0.5%~9.5%.Metal copper plate can be substituted for other
Plate with good electrical conductive properties, such as electrically conductive graphite plate.
Step 4, using fire resistant resin as matrix, nano-absorbent-silicon carbide fibre multi-scale reinforcing body be absorber, adopt
With polymer matrix composites moulding process, nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures are prepared
Absorbing material.Wherein, matrix accounts for the 30~50% of matrix and absorber gross mass, cannot be too low or too high, otherwise obtained
The mechanical property of absorbing material is relatively low.
Wherein, polymer matrix composites moulding process is according to different resins, using its applicable curing process；When resistance to height
Warm resin refers to epoxy resin, organic siliconresin, and the moulding process of polymer matrix composites is manual pasting forming process；Work as high temperature resistant
Resin refers to polyimide resin, polybenzoxazoles resin, and the moulding process of polymer matrix composites is die press technology for forming.
For the present invention using fire resistant resin as matrix, nano-absorbent-silicon carbide fibre multi-scale reinforcing body is to absorb system
Standby absorbing material, makes the absorbing material have certain mechanical property and absorbing property.It is characteristic of the invention that the resistance to height selected
Warm resin such as epoxy resin, organic siliconresin etc. can be used simple hand paste process and be prepared；Such as polyimide resin, polyphenyl
And die press technology for forming can be used in oxazole resin etc..It is an advantage of the invention that easy to operate, structure of title compound integrality is good, resists
Impact is strong, is not easy to be layered.And resin matrix used is all excellent combination property, the good resin of temperature tolerance, this makes this
The use scope for inventing the composite material of preparation greatly expands.
The present invention is described in further details below by specific embodiment.
Embodiment 1
The present embodiment is a kind of structural wave-absorbing material, nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin
Based structures absorbing material, using epoxy resin as matrix, carbon nanotube-silicon carbide fibre multi-scale reinforcing body is reinforcement.Its
Reinforcement used in middle carbon nanotube-silicon carbide fibre multi-scale reinforcing body is two-dimentional silicon carbide fiber cloth, silicon carbide fibre
Woven cloth conductivity is 1S/cm, and mass fraction of the carbon nanotube in carbon nanotube-silicon carbide fibre multi-scale reinforcing body is
0.5%.The content of multi-scale reinforcing body is 70wt% in composite material, and the content of epoxy resin-base is 30wt%.
The present embodiment, which also proposed, a kind of prepares carbon nanotube-silicon carbide fibre multi-scale reinforcing body reinforced epoxy base
The method of absorbing material, detailed process are:
The two-dimentional silicon carbide fibre knitting cloth and caliber that step 1, the above-mentioned conductivity of selection are 1S/cm are 5nm, and length is
The carbon nanotube of 15um.
Step 2, to cut out above-mentioned silicon carbide fibre cloth be 6, and every specification is 45mm*45mm.The carbon that will be cut
SiClx fiber cloth, which is put into acetone, carries out ultrasound except glue processing, 1 hour ultrasonic in ultrasonic wave, ultrasonic power 80W.It will be upper
It states carbon nanotube and is put into concentrated nitric acid and carry out acidification, wherein the quality of concentrated nitric acid is 8 times of carbon nanotube, acidification
Temperature is 50 DEG C, and the processing time is 5h, will remove the carbon nanotube after glue treated silicon carbide fibre cloth and acidification
It is put into vacuum oven and dries；Drying temperature is 50 DEG C.
The silicon carbide fibre cloth that step 2 obtains is attached on copper sheet and is being then attached to electrophoretic deposition instrument just by step 3
Pole, for another piece of metal copper plate as cathode, the carbon nanotube after step 2 to be obtained to acidification is dispersed in organic solvent-acetone
In, wherein the mass fraction of carbon nanotube in organic solvent is 1%.Regulate and control the size 20V of voltage in electrophoretic deposition process, electricity
Swim sedimentation time 1h, obtains carbon nanotube-silicon carbide fibre multi-scale reinforcing body, wherein carbon nanotube is in carbon nanotube-carbonization
Mass fraction in silica fibre multi-scale reinforcing body is 0.5%.
Step 4, with 6 layers of carbon nanotube of electronic analytical balance precise-silicon carbide fibre multi-scale reinforcing body quality,
Using epoxy resin as resin matrix, polyamide is curing agent, and the two quality proportioning is 4:1, with electronic analytical balance precise
The quality of epoxy resin and curing agent, wherein the quality and carbon nanotube-silicon carbide fibre of epoxy resin and curing agent are multiple dimensioned
The ratio of reinforcement quality is 3:7.
Step 5 prepares composite material using hand paste process method, by after evenly mixing epoxy resin and curing agent slurry use
Brush is uniformly brushed on 6 layers of carbon nanotube-silicon carbide fibre multi-scale reinforcing body, and then proper alignment is at precast body, in advance
Body processed is put into baking oven after placing 2 hours at room temperature, is warming up to 120 DEG C with the heating rate of 3 DEG C/min and is kept the temperature 1h, is completed
The curing molding of precast body obtains carbon nanotube-silicon carbide fibre multi-scale reinforcing body reinforced epoxy base wave-absorbing material.It should
The bending strength of composite material can achieve 398MPa, be 3.5GHz in bandwidth of the 8-18GHz reflectivity lower than -8dB.
Embodiment 2
The present embodiment is a kind of structural wave-absorbing material, nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin
Based structures absorbing material, using organic siliconresin as matrix, carbon nanotube-silicon carbide fibre multi-scale reinforcing body is reinforcement.
Wherein reinforcement used in carbon nanotube-silicon carbide fibre multi-scale reinforcing body is two-dimentional silicon carbide fiber cloth, and silicon carbide is fine
Dimension woven cloth is 1.6S/cm, quality of the carbon nanotube in carbon nanotube-silicon carbide fibre multi-scale reinforcing body point with conductivity
Number is 3.5%.The content of multi-scale reinforcing body is 60wt% in composite material, and the content of organic siliconresin matrix is 40wt%.
The present embodiment, which also proposed, a kind of prepares carbon nanotube-silicon carbide fibre multi-scale reinforcing body enhancing organic siliconresin
The method of base wave-absorbing material, detailed process are:
The two-dimentional silicon carbide fibre knitting cloth and caliber that step 1, the above-mentioned conductivity of selection are 1.6S/cm are 20nm, length
For the carbon nanotube of 10um.
Step 2, to cut out above-mentioned silicon carbide fibre cloth be 6, and every specification is 45mm*45mm.The carbon that will be cut
SiClx fiber cloth, which is put into acetone, handle except glue, is cleaned 6 hours in ultrasonic wave, ultrasonic power 100W.It will be above-mentioned
Carbon nanotube, which is put into concentrated nitric acid, carries out acidification, and wherein the quality of concentrated nitric acid is 16 times of carbon nanotube, acidification
Temperature is 70 DEG C, and the processing time is 10h, will remove the carbon nanotube after glue treated silicon carbide fibre cloth and acidification
It is put into vacuum oven and dries；Drying temperature is 80 DEG C.
The silicon carbide fibre cloth that step 2 obtains is attached on copper sheet and is being then attached to electrophoretic deposition instrument just by step 3
Pole, for another piece of metal copper plate as cathode, the carbon nanotube after step 2 to be obtained to acidification is dispersed in organic solvent ethyl alcohol
In, wherein the mass fraction of carbon nanotube in organic solvent is 3.5%.Regulate and control the size 40V of voltage in electrophoretic deposition process,
Electrophoretic deposition time 6h obtains carbon nanotube-silicon carbide fibre multi-scale reinforcing body, and wherein carbon nanotube is in carbon nanotube-carbon
Mass fraction in SiClx fiber multi-dimension reinforcement body is 3.5%.
Step 4, with 6 layers of carbon nanotube of electronic analytical balance precise-silicon carbide fibre multi-scale reinforcing body quality,
Using organic siliconresin as resin matrix, the wherein quality of organic siliconresin and carbon nanotube-silicon carbide fibre multi-scale reinforcing body
The ratio of quality is 4:6.
Step 5 prepares composite material using hand paste process method, and organic siliconresin is uniformly brushed to 6 layers of carbon with brush
On nanotube-silicon carbide fibre multi-scale reinforcing body, then proper alignment at precast body, place 2 hours at room temperature by precast body
After be put into baking oven.The cured temperature of precast body is change of gradient, specifically, from room temperature with the heating rate of 3 DEG C/min to 150
DEG C and keep the temperature 30min.After heat preservation, baking oven is warming up to 180 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 1h, then will be dried
Case is warming up to 280 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 40min；So far it completes solidification and obtains carbon nanotube-silicon carbide fibre
Tieing up multi-scale reinforcing body enhances organic siliconresin structural wave-absorbing material.Absorbing material obtained is as shown in Figure 1, structural intergrity
Good, the bending strength of the composite material can achieve 440MPa, and impact resistance is strong, be not easy to be layered；It is low in 8-18GHz reflectivity
In the bandwidth of -8dB be 4.7GHz.
Embodiment 3
The present embodiment is a kind of structural wave-absorbing material, nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin
Based structures absorbing material, using polybenzoxazoles resin as matrix, carbon nanotube-silicon carbide fibre multi-scale reinforcing body is enhancing
Body.Wherein reinforcement used in carbon nanotube-silicon carbide fibre multi-scale reinforcing body is two-dimentional silicon carbide fiber cloth, silicon carbide
Fibre knitting cloth conductivity is 10-6S/cm, quality of the carbon nanotube in carbon nanotube-silicon carbide fibre multi-scale reinforcing body
Score is 9.5%.The content of multi-scale reinforcing body is 50wt% in composite material, and the content of polybenzoxazoles resin matrix is
50wt%.
The present embodiment, which also proposed, a kind of prepares carbon nanotube-silicon carbide fibre multi-scale reinforcing body enhancing polybenzoxazoles
The method of resin base wave-absorbing material, detailed process are:
Step 1, the above-mentioned conductivity of selection are 10-6The two-dimentional silicon carbide fibre knitting cloth and caliber of S/cm is 100nm, length
For the carbon nanotube of 2um.
Step 2, to cut out above-mentioned silicon carbide fibre cloth be 6, and every specification is 45mm*45mm.The carbon that will be cut
SiClx fiber cloth, which is put into acetone, handle except glue, is cleaned 1 hour in ultrasonic wave, ultrasonic power 100W.It will be above-mentioned
Carbon nanotube, which is put into concentrated nitric acid, carries out acidification, and wherein the quality of concentrated nitric acid is 30 times of carbon nanotube, acidification
Temperature is 90 DEG C, and the processing time is that for 24 hours, will carry out except the carbon nanotube after glue treated silicon carbide fibre cloth and acidification
It is put into vacuum oven and dries；Drying temperature is 100 DEG C.
The silicon carbide fibre cloth that step 2 obtains is attached on copper sheet and is being then attached to electrophoretic deposition instrument just by step 3
Pole, for another piece of metal copper plate as cathode, the carbon nanotube after step 2 to be obtained to acidification is dispersed in organic solvent N-N bis-
In methylacetamide, wherein the mass fraction of carbon nanotube in organic solvent is 10%.Regulate and control voltage in electrophoretic deposition process
Size 80V, the electrophoretic deposition time for 24 hours, obtains carbon nanotube-silicon carbide fibre multi-scale reinforcing body, wherein carbon nanotube exists
Mass fraction in carbon nanotube-silicon carbide fibre multi-scale reinforcing body is 9.5%.
Step 4, with 6 layers of carbon nanotube of electronic analytical balance precise-silicon carbide fibre multi-scale reinforcing body quality,
Using polybenzoxazoles resin as resin matrix, with the quality of electronic analytical balance precise polybenzoxazoles resin, wherein gathering
The quality and carbon nanotube of benzoxazoles resin-silicon carbide fibre multi-scale enhancement weight ratio are 5:5.
Step 5, using mould pressing process forming composite, polybenzoxazoles is uniformly brushed to 6 layers of carbon nanotube-carbon
It is prepared into prefabricated component on SiClx fiber multi-dimension reinforcement body, prefabricated component is put into vacuum drying oven, is vacuumized to exclude in prefabricated component
Bubble, vacuum degree be 0.08MPa under conditions of keep 30min, then restore to normal pressure state.
Step 6 starts to warm up the prefabricated component of step 5 from room temperature, 5 DEG C/min of heating rate, is warming up to 120 DEG C of heat preservations
30min, while applying pressure 5MPa, pressure is shed after heat preservation, completes the production processing of structure Wave suction composite material.This is multiple
The bending strength of condensation material can achieve 235MPa, be 5.6GHz in bandwidth of the 8-18GHz reflectivity lower than -8dB.
Embodiment 4
The present embodiment is a kind of structural wave-absorbing material, nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin
Based structures absorbing material, using polyimide resin as matrix, graphene-silicon carbide fibre multi-scale reinforcing body is reinforcement.
Wherein reinforcement used in graphene-silicon carbide fibre multi-scale reinforcing body is two-dimentional silicon carbide fiber cloth, silicon carbide fibre
Woven cloth conductivity is 10-4S/cm, mass fraction of the carbon nanotube in carbon nanotube-silicon carbide fibre multi-scale reinforcing body
It is 7.5%.The content of multi-scale reinforcing body is 60wt% in composite material, and the content of polyimide resin matrix is 40wt%.
The present embodiment, which also proposed, a kind of prepares graphene-silicon carbide fibre multi-scale reinforcing body enhancing polyimide resin
The method of base wave-absorbing material, detailed process are:
Step 1, the above-mentioned conductivity of selection are 10-4The two-dimentional silicon carbide fibre knitting cloth of S/cm and with a thickness of 0.8nm, particle
Graphene having a size of 0.6um.
Step 2, to cut out above-mentioned silicon carbide fibre cloth be 6, and every specification is 45mm*45mm.The carbon that will be cut
SiClx fiber cloth, which is put into acetone, handle except glue, is cleaned 10 hours in ultrasonic wave, ultrasonic power 90W.It will be above-mentioned
Carbon nanotube, which is put into concentrated nitric acid, carries out acidification, and wherein the quality of concentrated nitric acid is 24 times of carbon nanotube, acidification
Temperature is 70 DEG C, and the processing time is 8h, will remove the carbon nanotube after glue treated silicon carbide fibre cloth and acidification
It is put into vacuum oven and dries；Drying temperature is 80 DEG C.
The silicon carbide fibre cloth that step 2 obtains is attached on copper sheet and is being then attached to electrophoretic deposition instrument just by step 3
Pole, for another piece of metal copper plate as cathode, the carbon nanotube after step 2 to be obtained to acidification is dispersed in organic solvent-acetone
In, wherein the mass fraction of carbon nanotube in organic solvent is 8.5%.Regulate and control the size of voltage in electrophoretic deposition process
100V, electrophoretic deposition time 12h obtain carbon nanotube-silicon carbide fibre multi-scale reinforcing body, and wherein carbon nanotube is in carbon nanometer
Mass fraction in pipe-silicon carbide fibre multi-scale reinforcing body is 7.5%.
Step 4, with 6 layers of carbon nanotube of electronic analytical balance precise-silicon carbide fibre multi-scale reinforcing body quality,
Using polyimide resin as resin matrix, with the quality of electronic analytical balance precise polyimide precursor polyamic acid,
It is that 40%, the wherein quality of polyamic acid and graphene-silicon carbide are fine that wherein polyamic acid, which is converted into the conversion ratio of polyimides,
The ratio for tieing up multi-scale enhancement weight is 10:6.
Step 5, using mould pressing process forming composite, polyamic acid solution is uniformly brushed to graphene-carbonization
Prefabricated component is prepared on silica fibre multi-scale reinforcing body.Prefabricated component after brushing is put into vacuum drying oven, is vacuumized prefabricated to exclude
Bubble in part keeps 10min under conditions of vacuum degree is 0.08MPa, then restores to normal pressure state.By prefabricated component from room
Temperature starts to warm up, 5 DEG C/min of heating rate, is warming up to 240 DEG C and keeps the temperature 2 hours.
Prefabricated component after step 5 processing is placed in mold by step 6, is pressurizeed on a hydraulic press.With the heating of 3 DEG C/min
Rate is warming up to 300 DEG C, starts to apply pressure 15MPa and keeps the temperature 30min, then proceedes to heat up with the heating rate of 3 DEG C/min
To 370 DEG C, 1 hour is kept the temperature, pressure is shed after heat preservation, completes the production processing of structure Wave suction composite material.Such as Fig. 2 institute
Show, the bending strength of the composite material can achieve 594MPa, be 7.6GHz in bandwidth of the 8-18GHz reflectivity lower than -8dB.
Embodiment 5
The present embodiment is a kind of structural wave-absorbing material, nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin
Based structures absorbing material, using polyimide resin as matrix, graphene-silicon carbide fibre multi-scale reinforcing body is reinforcement.
Wherein reinforcement used in graphene-silicon carbide fibre multi-scale reinforcing body is two-dimentional silicon carbide fiber cloth, silicon carbide fibre
Woven cloth conductivity is 10-4S/cm, mass fraction of the carbon nanotube in carbon nanotube-silicon carbide fibre multi-scale reinforcing body
It is 6%.The content of multi-scale reinforcing body is 60wt% in composite material, and the content of polyimide resin matrix is 40wt%.
The present embodiment, which also proposed, a kind of prepares graphene-silicon carbide fibre multi-scale reinforcing body enhancing polyimide resin
The method of base wave-absorbing material, detailed process are:
Step 1, the above-mentioned conductivity of selection are 10-4The two-dimentional silicon carbide fibre knitting cloth of S/cm and with a thickness of 1nm, particle ruler
The very little graphene for 0.2um.
Step 2, to cut out above-mentioned silicon carbide fibre cloth be 6, and every specification is 45mm*45mm.The carbon that will be cut
SiClx fiber cloth, which is put into acetone, handle except glue, is cleaned 12 hours in ultrasonic wave, ultrasonic power 100W.It will be above-mentioned
Graphene, which is put into concentrated nitric acid, carries out acidification, and wherein the quality of concentrated nitric acid is 30 times of graphene, acidification temperature
It is 80 DEG C, the processing time is 18h, will carry out being put into very except the graphene after glue treated silicon carbide fibre cloth and acidification
It is dried in empty drying box；Drying temperature is 90 DEG C.
The silicon carbide fibre cloth that step 2 obtains is attached on copper sheet and is being then attached to electrophoretic deposition instrument just by step 3
Pole, another piece of metal copper plate as cathode, the graphene dispersion after step 2 to be obtained to acidification in organic solvent ethyl alcohol,
Wherein the mass fraction of graphene in organic solvent is 8%.Regulate and control the size 70V of voltage in electrophoretic deposition process, electrophoresis is heavy
Product time 10h, obtains graphene-silicon carbide fibre multi-scale reinforcing body, wherein graphene is in the more rulers of graphene-silicon carbide fibre
The mass fraction spent in reinforcement is 6%.
Step 4, with 6 layers of carbon nanotube of electronic analytical balance precise-silicon carbide fibre multi-scale reinforcing body quality,
Using polyimide resin as resin matrix, with the quality of electronic analytical balance precise polyimide precursor polyamic acid,
It is that 40%, the wherein quality of polyamic acid and graphene-silicon carbide are fine that wherein polyamic acid, which is converted into the conversion ratio of polyimides,
The ratio for tieing up multi-scale enhancement weight is 10:6.
Step 5, using mould pressing process forming composite, polyamic acid solution is uniformly brushed to graphene-carbonization
Prefabricated component is prepared on silica fibre multi-scale reinforcing body, the prefabricated component after brushing is put into vacuum drying oven, is vacuumized prefabricated to exclude
Bubble in part keeps 10min under conditions of vacuum degree is 0.08MPa, then restores to normal pressure state.By prefabricated component from room
Temperature starts to warm up, 5 DEG C/min of heating rate, is warming up to 240 DEG C and keeps the temperature 2 hours.
Prefabricated component after step 5 processing is placed in mold by step 6, is pressurizeed on a hydraulic press.With the heating of 3 DEG C/min
Rate is warming up to 300 DEG C, starts to apply pressure 15MPa and keeps the temperature 30min, then proceedes to heat up with the heating rate of 3 DEG C/min
To 370 DEG C, 1 hour is kept the temperature, pressure is shed after heat preservation, completes the production processing of structure Wave suction composite material.The composite wood
The bending strength of material can achieve 594MPa, be 6.1GHz in bandwidth of the 8-18GHz reflectivity lower than -8dB.
Silicon carbide fibre cloth reinforced resin structural wave-absorbing material produced by the present invention, which integrates, inhales wave and bearing function, easily
In molding, structure is simple.
Nano-absorbent of the present invention-silicon carbide fibre multi-scale reinforcing body is to be inhaled above-mentioned nanometer by electrophoretic deposition
Receive agent and deposit to two-dimentional silicon carbide fiber cloth, by the regulation time of electrophoretic deposition, the voltage of electrophoretic deposition, solution concentration etc. because
Element realizes nano-absorbent-silicon carbide fibre multi-scale reinforcing body preparation of different nano-absorbent deposition contents, wherein adjusting
The time of control electrophoretic deposition is longer, electrophoretic deposition voltage is bigger, solution concentration is higher, and nano-absorbent is in nano-absorbent-
Mass fraction in silicon carbide fibre multi-scale reinforcing body is higher, generally 0.5%-9.5%.
Good absorbing property and mechanical property may be implemented in composite material prepared by the present invention, is absorbed by deposition nanometer
The preparation of different conductivity nano-absorbent-silicon carbide fibre multi-scale reinforcing bodies may be implemented in the regulation of agent content, reaches pair
Composite material dielectric properties are adjusted, and then adjust the purpose of absorbing property, and composite material is made to have good mechanics
Performance meets the light-weighted requirement of composite material component.
Claims (10)
1. a kind of nano-absorbent-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures absorbing material preparation method,
It is characterized by comprising following steps:
(1) take silicon carbide fibre cloth carry out except glue handle, take nano-absorbent carry out acidification, will except glue treated carbonization
Nano-absorbent after silica fibre cloth and acidification is dried；
(2) the silicon carbide fibre cloth of step (1) after dry is attached on conductive plate, is being then attached to electrophoretic deposition instrument just
Pole, another piece of conductive plate is as cathode；The nano-absorbent dispersion of step (1) after dry in organic solvent, is subjected to electrophoresis
Deposition, obtains nano-absorbent-silicon carbide fibre multi-scale reinforcing body, wherein nano-absorbent is in nano-absorbent-silicon carbide
Mass fraction in fiber multi-dimension reinforcement body is 0.5%~9.5%；
(3) using fire resistant resin as matrix, nano-absorbent-silicon carbide fibre multi-scale reinforcing body is absorber, wherein matrix
The 30~50% of matrix and absorber gross mass are accounted for, using polymer matrix composites moulding process, nano-absorbent-carbonization is made
Silica fibre multi-scale reinforcing body reinforced resin based structures absorbing material；
In step (3), fire resistant resin is epoxy resin or silicone resin；Or fire resistant resin be polyimide resin or
Polybenzoxazoles resin.
2. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: comprising the concrete steps that except glue processing in step (1) lays silicon carbide fibre
Enter in acetone, is cleaned 1~12 hour in the ultrasonic wave of 80~100W.
3. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: acidification is that nano-absorbent is put into concentrated nitric acid in step (1),
In 50 DEG C~90 DEG C processing 5h~for 24 hours, wherein the quality of concentrated nitric acid is 8~30 times of quality of nano-absorbent.
4. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: in silicon carbide fibre cloth the conductivity of silicon carbide fibre in 1~1.6S/cm or
Conductivity is 10-6~10-4S/cm。
5. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: it for 5~100nm and length is 2~15 μm that nano-absorbent, which uses caliber,
Carbon nanotube, or the graphene for being 0.2~0.6 μm with a thickness of 0.8~1nm and particle size.
6. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: the drying in step (1) is dried at 50~100 DEG C.
7. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: organic solvent is acetone, N-N dimethyl acetamide or ethyl alcohol in step (2)；
The mass fraction of nano-absorbent in organic solvent is 1%~10% in step (2).
8. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: in step (2) voltage of electrophoretic deposition in 20V~100V, electrophoretic deposition when
Between 1~for 24 hours.
9. a kind of nano-absorbent according to claim 1-silicon carbide fibre multi-scale reinforcing body reinforced resin based structures
The preparation method of absorbing material, it is characterised in that: in step (3), when fire resistant resin is epoxy resin or silicone resin, tree
Resin-based composite moulding process is manual pasting forming process；Or fire resistant resin is polyimide resin or polybenzoxazoles tree
When rouge, the moulding process of polymer matrix composites is die press technology for forming.
10. a kind of increased using nano-absorbent made from preparation method described in claim 1-silicon carbide fibre multi-scale reinforcing body
Strong resin-based structural absorbing material.
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| CN108252114B (en) * | 2018-02-09 | 2020-12-29 | 青海大学 | Silicon carbide fiber cloth reinforced polyimide resin-based structural wave-absorbing material and preparation method thereof |
| CN108437579A (en) * | 2018-05-16 | 2018-08-24 | 山东天磁新材料科技有限公司 | A kind of high temperature resistant Wave suction composite material and preparation method thereof |
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| CN102628214A (en) * | 2012-04-09 | 2012-08-08 | 天津大学 | Carbon fiber composite material with ZnO layer electrolytically deposited on surface as well as preparation method and application thereof |
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| CN102628214A (en) * | 2012-04-09 | 2012-08-08 | 天津大学 | Carbon fiber composite material with ZnO layer electrolytically deposited on surface as well as preparation method and application thereof |
| CN103408899A (en) * | 2013-07-16 | 2013-11-27 | 同济大学 | Tree-like structure micro-nano wave absorption agent/epoxy resin composite wave absorption material preparation method |
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