CN104673184A - Electromagnetic wave absorber as well as preparation method and application thereof - Google Patents
Electromagnetic wave absorber as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104673184A CN104673184A CN201310642548.1A CN201310642548A CN104673184A CN 104673184 A CN104673184 A CN 104673184A CN 201310642548 A CN201310642548 A CN 201310642548A CN 104673184 A CN104673184 A CN 104673184A
- Authority
- CN
- China
- Prior art keywords
- carbonyl iron
- carbonyl
- iron dust
- solution
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a method of preparing an electromagnetic wave absorber. The method comprises the following steps: carrying out a ball milling technology carbonyl iron powder; carrying out surface treatment on the ball-milled carbonyl iron powder by using strong base; treating the carbonyl iron powder by virtue of a titanium-containing compound to obtain carbonyl iron-TiO2 core-shell-structured microparticles; and magnetizing the carbonyl iron-TiO2 core-shell-structured microparticles. The electromagnetic wave absorber is prepared from the following components in percentage by weight: 10-60 percent of modified carbonyl iron powder and 40-90 percent of a coating material. The electromagnetic wave absorber prepared by virtue of the method is capable of effectively showing good electromagnetic wave absorption capability in multiple frequency bands; compared with the prior art, the electromagnetic wave absorber is wide in electromagnetic wave absorption frequency band.
Description
Technical field
The present invention relates to Material Field, in particular to a kind of wave absorbing agent, preparation method and application thereof.。
Background technology
At the society of fast development, due to the generally application of various electron device, create a large amount of hertzian wave to our living environment, " these hertzian wave not only have interference each other, and also have hazardness to human body to cause the electromagnetic pollution in space.Therefore microwave absorbing material comes into people's livelihood field from Military Application.Along with the development of absorbing material, the concern that electromagnetic wave absorbing material is subject to is more and more higher.Micro-powder of metals has that Curie temperature is high, temperature stability good, in magneticsubstance, the specific magnetising moment is the highest, microwave magnetic permeability is comparatively large, specific inductivity comparatively advantages of higher, is therefore used widely in absorbing material field.
Information society requires that the speed of transferring content wants fast, and quality wants high, and this makes the electromagnetic frequency of application transport more and more higher.So, the operating frequency for eliminating the microwave absorbing material of these Electromagnetic Interference also will improve accordingly.The preparation method of carbonyl iron dust of the prior art comprises: at room temperature carry out ball-milling technology to carbonyl iron dust; Use the carbonyl iron dust 3 times after the first ball milling of ethanol purge and flash baking; Again ball-milling technology is implemented to dried carbonyl iron dust; After ball grinder cooling, namely iron powder and steel ball sieving separating are obtained flaky carbonyl iron powder sample.But the wave-sucking performance of traditional oxo iron powder wave absorbing agent poor and inhale wave width narrower.Therefore need to develop and a kind ofly there is better wave-absorbing effect and inhale the wider material of ripple frequency band.
Summary of the invention
Poor and inhale the narrower problem of ripple frequency range for the wave-sucking performance of carbonyl iron dust in prior art, one aspect of the present invention proposes a kind of method preparing wave absorbing agent, comprising:
Ball-milling technology is implemented to carbonyl iron dust;
Highly basic is used to carry out surface treatment to the carbonyl iron dust after ball milling;
Use titanium-containing compound process carbonyl iron dust, obtain iron carbonyl-TiO
2nucleocapsid structure particulate; And
Magnetization iron carbonyl-TiO
2nucleocapsid structure particulate.
In certain embodiments, in ball grinder, step carbonyl iron dust being implemented to ball-milling technology is implemented.
In certain embodiments, ball grinder comprises pellet, and wherein, the weight ratio of pellet and carbonyl iron dust is between 20:1 and 30:1.
In certain embodiments, the weight ratio of pellet and carbonyl iron dust is 25:1.
In certain embodiments, the step of carbonyl iron dust enforcement ball-milling technology is implemented in organic solvent.
In certain embodiments, organic solvent is selected from a kind of in ethanol, acetone, Virahol, normal hexane and octane or their combination.
In certain embodiments, the rotating speed of ball grinder is 300 ~ 650r/min.
In certain embodiments, the rotating speed of ball grinder is 500r/min.
In certain embodiments, to carbonyl iron dust implement ball-milling technology step continue 5 ~ 9 hours.
In certain embodiments, to carbonyl iron dust implement ball-milling technology step continue 8 hours.
In certain embodiments, carry out surface-treated step at use highly basic to the carbonyl iron dust after ball milling to comprise further:
Carbonyl iron dust after ball milling is put into strong base solution and forms the first mixture;
Supersound process is carried out to the first mixture;
From the first mixture after supersound process, take out carbonyl iron dust, and clean carbonyl iron dust; And
Dry carbonyl iron dust.
In certain embodiments, strong base solution is a kind of in sodium hydroxide solution and potassium hydroxide solution or their combination.
In certain embodiments, the pH value of strong base solution is 10 ~ 13.
In certain embodiments, the pH value of strong base solution is 11.
In certain embodiments, under the power of 180 watts, the step of the first mixture being carried out to supersound process is implemented.
In certain embodiments, to the first mixture carry out supersound process step continue 10 minutes to 40 minutes.
In certain embodiments, to the first mixture carry out supersound process step continue 20 minutes.
In certain embodiments, the step of cleaning carbonyl iron dust is with an organic solvent implemented.
In certain embodiments, organic solvent comprises dehydrated alcohol.
In certain embodiments, the step of 3-5 cleaning carbonyl iron dust is repeated.
In certain embodiments, in air dry oven, the step of drying carbonyl iron dust is implemented.
In certain embodiments, the step of titanium-containing compound process carbonyl iron dust is used to comprise further:
Titanium-containing compound is dissolved in organic solvent, forms the first solution;
Carbonyl iron dust is mixed with organic solvent, forms the second solution;
Deionized water is mixed with organic solvent, forms the 3rd solution;
First solution is added drop-wise in the second solution, and carries out the first stirring supersound process, form the 4th solution;
3rd solution is added drop-wise in the 4th solution, and carries out the second stirring supersound process;
Filter the 4th solution, and with an organic solvent clean the solid product leached; And
Dry solid product.
In certain embodiments, titanium-containing compound is tetrabutyl titanate.
In certain embodiments, organic solvent is ethanol.
In certain embodiments, in the first solution, the volume ratio of titanium-containing compound and organic solvent is between 1:4 to 1:2.
In certain embodiments, in the first solution, the volume ratio of titanium-containing compound and organic solvent is 1:4.
In certain embodiments, in the 3rd solution, the volume ratio of deionized water and organic solvent is 1:1.
In certain embodiments, the time of the first ultrasonic agitation process is between 10 minutes to 40 minutes.
In certain embodiments, the first time of stirring supersound process was 10 minutes.
In certain embodiments, the second time of stirring supersound process was 4 hours.
In certain embodiments, iron carbonyl-TiO is magnetized
2the step of nucleocapsid structure particulate comprises further:
By iron carbonyl-TiO
2nucleocapsid structure particulate and coating material put into mould simultaneously;
Heating mould is until coating material melts; And
Mould is put into magnetic field, and rotating mold is until room temperature is down to by coating material.
In certain embodiments, by iron carbonyl-TiO
2the step of mould put into by nucleocapsid structure particulate and coating material simultaneously, iron carbonyl-TiO
2the weight ratio of nucleocapsid structure particulate and coating material is between 1:9 to 2:3.
In certain embodiments, in the step that heating mould to coating material melts, Heating temperature is between 80 DEG C to 90 DEG C.
In certain embodiments, coating material comprises paraffin, polyethylene, polypropylene, polystyrene, epoxy resin or resol.
In certain embodiments, 2-10 the described iron carbonyl of described magnetization-TiO is repeated
2the step of nucleocapsid structure particulate.
In certain embodiments, before step carbonyl iron dust being implemented to ball-milling technology, comprise further:
Oxidation carbonyl iron dust.
In certain embodiments, the step being oxidized carbonyl iron dust comprises further:
Carbonyl iron dust is put into the mixing solutions of hydrogen peroxide and organic solvent;
Supersound process is implemented to mixing solutions; And
Filter mixing solutions, and with an organic solvent solid product after cleaning and filtering; And
Dry solid product after filtering.
In certain embodiments, carbonyl iron dust is being put into the step of mixing solutions of hydrogen peroxide and organic solvent, the volume ratio of hydrogen peroxide and organic solvent is between 1:19 to 2:3.
In certain embodiments, under the power of 900 watts, carry out step mixing solutions being implemented to supersound process, and the time of supersound process is 120 minutes.
In certain embodiments, organic solvent is dehydrated alcohol.
According to another aspect of the present invention, provide a kind of wave absorbing agent, comprising:
Modified carbonyl iron powder 10% ~ 60%(weight); And coating material 40% ~ 90%(weight).
In certain embodiments, modified carbonyl iron powder comprises iron carbonyl-TiO
2nucleocapsid structure particulate.
In certain embodiments, described coating material comprises paraffin, polyethylene, polypropylene, polystyrene, epoxy resin or resol.
A kind of suction ripple substrate being filled with above-mentioned wave absorbing agent is also comprised in other aspects of the present invention; And a kind of prepreg being filled with above-mentioned wave absorbing agent.
The absorbing property being improved wave absorbing agent by means such as the oxidation to carbonyl iron dust, ball milling, surface treatment, surface growth, coated and rotatingfield orientations of the present invention.The wave absorbing agent prepared by method of the present invention is overcome wave absorbing agent wave-sucking performance of the prior art difference and inhales the narrow problem of ripple frequency band.Wave absorbing agent of the present invention can all show good wave-sucking performance effectively in multiple frequency range, and it is wider compared with prior art to inhale ripple frequency band.According to experiment of the present invention, wave absorbing agent of the present invention all has outstanding wave-sucking performance in the range of frequency from 3.0GHz to 8.7GHz, and when-5dB, it inhales ripple frequency range can reach 10.7GHz; When-10dB, it inhales frequency range also can reach 4.8GHz.
Accompanying drawing explanation
Fig. 1 is the intermediate steps of the method for the preparation of absorbing material of the present invention according to some embodiments.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain, all belongs to the scope of protection of the invention.
The preparation method of absorbing material
As shown in the step S101 of Fig. 1, oxide treatment is implemented to carbonyl iron dust.Hydrogen peroxide and organic solvent are mixed into mixing solutions, and carbonyl iron dust is mixed into wherein.Carry out supersound process to the mixing solutions being mixed with carbonyl iron dust can fully contact with hydrogen peroxide to make carbonyl iron dust and be oxidized.In certain embodiments, the volume ratio of hydrogen peroxide and organic solvent is between about 1:19 to about between 2:3, and wherein, organic solvent is ethanol.According to some embodiments, under the power of 900 watts, implement supersound process, and the treatment time is 120 minutes.After supersound process, the carbonyl iron dust after oxidation is taken out from mixing solutions, use ethanol to clean, and dry carbonyl iron dust.In the process of supersound process, can adjust the volume ratio of ultrasonic power, hydrogen peroxide and organic solvent and treatment time, thus control the degree of oxidation of carbonyl iron dust.To in the oxidising process of carbonyl iron dust, the specific inductivity of material should be reduced, do not reduce magnetic permeability as much as possible again.
As shown in the S103 in Fig. 1, ball-milling processing is implemented to carbonyl iron dust.In certain embodiments, carbonyl iron dust is put into ball grinder (comprising pellet), and the ball milling solution in ball grinder is organic solution.Under the rotating speed of 300 ~ 650r/min, carbonyl iron dust processes 5 ~ 9 hours in ball grinder.In the present embodiment, the weight ratio of pellet and carbonyl iron dust in the scope of about 20:1 to about 30:1, preferably 25:1; And ball milling solution is selected from a kind of in ethanol, acetone, Virahol, normal hexane and octane or their combination.In certain embodiments, the rotating speed of ball grinder is preferably 500r/min, and the time length of ball-milling technology is preferably 8 hours.Although in the above-described embodiments, the carbonyl iron dust used is the carbonyl iron dust without oxide treatment, in some embodiment, also can be the carbonyl iron dust after oxidation.After ball-milling technology, carbonyl iron dust becomes sheet.
As shown in the S105 of Fig. 1, surface treatment is carried out to carbonyl iron dust.Carbonyl iron dust after ball milling is put into strong base solution.Then the strong base solution comprising carbonyl iron dust is carried out supersound process under the power of 180 watts, the time length was between about 10 minutes to about 40 minutes.Carbonyl iron dust after surface treatment is taken out from strong base solution, with an organic solvent repeatedly cleans 3-5 time, and dry in air dry oven.In certain embodiments, sodium hydroxide, potassium hydroxide and ammonium hydroxide etc. can be comprised for surface-treated highly basic.The pH value of strong base solution can in the scope of 10 to 13, and preferable ph is 11.The time of preferred supersound process is 20 minutes in certain embodiments.According to some embodiments, be dehydrated alcohol at the organic solvent carrying out using in surface-treated step.Use highly basic to carry out surface treatment to carbonyl iron dust and can adhere to one deck hydroxyl (-OH) on the surface of carbonyl iron dust, this process is referred to as hydroxylation.Hydroxylation procedures contributes to surface growth TiO in technological process subsequently
2.
As shown in the S107 of Fig. 1, surface growth is implemented to carbonyl iron dust.Titanium-containing compound is dissolved in organic solvent and forms the first solution.In the first solution, the volume ratio of titanium-containing compound and organic solvent is between 1:4 to 1:2, and preferably, this volume ratio is 1:4.In certain embodiments, titanium-containing compound can be tetrabutyl titanate.Carbonyl iron dust and organic solvent are mixed to form the second solution.Deionized water and organic solvent are mixed to form the 3rd solution.In the 3rd solution, the volume ratio of deionized water and organic solvent is 1:1.Then, the first solution is added drop-wise in the second solution gradually, and carries out stirring supersound process formation the 4th solution, stir ultrasonic time remaining 10 minutes to 40 minutes.Subsequently, by the 3rd solution gradually drop be added in the 4th solution, and carry out stirring supersound process, stir ultrasonic time remaining 4 hours.4th solution is filtered, with an organic solvent repeatedly cleans the solid product leached, and dry described solid product.In the above-described embodiments, the organic solvent used is ethanol.Iron carbonyl-TiO is formed by the above-mentioned surface growth technique to carbonyl iron dust
2nucleocapsid structure particulate.
As shown in the S109 of Fig. 1, to iron carbonyl-TiO
2magnetization treatment implemented by nucleocapsid structure particulate.By iron carbonyl-TiO
2nucleocapsid structure particulate and coating material put into mould simultaneously, wherein, and iron carbonyl-TiO
2the weight ratio of nucleocapsid structure particulate and coating material is in the scope of about 1:9 to 2:3.Iron carbonyl-TiO will be comprised
2the mould of nucleocapsid structure particulate and coating material heats, Heating temperature within the scope of about 80 DEG C to about 90 DEG C, until the coating material in mould is in molten state completely.Then, mould is put into magnetic field, until mold cools down is to room temperature.Due to iron carbonyl-TiO
2nucleocapsid structure particulate is sheet, and therefore it has anisotropy.In magnetic field, iron carbonyl-TiO
2the usual level of magnetic moment of nucleocapsid structure particulate in flaky particles, under the effect of therefore outside magnetic field, iron carbonyl-TiO
2nucleocapsid structure particulate can be followed magnetic field and rotate.Repeat aforesaid operations 2-10 time, thus complete the preparation of modification wave absorbing agent.To iron carbonyl-TiO
2nucleocapsid structure particulate is implemented operable coating material in the operation of magnetization treatment and is comprised paraffin, polyethylene, polypropylene, polystyrene, epoxy resin or resol.Should be appreciated that, although only use paraffin to be described as the example of coating material hereinafter, above-mentioned other coating materials exemplified also can realize object of the present invention.
Embodiment 1
5ml hydrogen peroxide is mixed with 95ml ethanol, and 2g carbonyl iron dust is added wherein.Then the above-mentioned mixing solutions of supersound process 120 minutes under the power of 900 watts.After supersound process, the carbonyl iron dust after oxidation is taken out from mixing solutions, use ethanol to clean, and dry the carbonyl iron dust after oxidation.
Carbonyl iron dust after being oxidized by 2.6g puts into ball grinder, and the weight ratio of pellet and the carbonyl iron dust after being oxidized is 25:1, and ball milling solution is anhydrous ethene.Under the rotating speed of 500r/min, implement ball-milling technology 8 hours.
Carbonyl iron dust after 2g ball milling is put into the sodium hydroxide solution of 100ml pH=11, then under the power of 180 watts ultrasonic 20 minutes.Take out the carbonyl iron dust after surface treatment, clean 3-5 time in dehydrated alcohol, and room temperature is dried.
5ml tetrabutyl titanate (TBT) is dissolved in 20ml ethanol and forms the first solution; 2g carbonyl iron dust after surface treatment is put into 30ml ethanol and forms the second solution; 15ml deionized water and 15ml ethanol are mixed to form the 3rd solution.First solution is added drop-wise in the second solution, and stirs ultrasonic 10 minutes, then the 3rd solution is added drop-wise in the mixing solutions of first and second solution, and stir ultrasonic 4 hours.Filter final mixing solutions afterwards, get solid much filtrate, use ethanol purge and dry, obtaining iron carbonyl-TiO
2nucleocapsid structure particulate.
By 2g iron carbonyl-TiO
2nucleocapsid structure particulate and 2g paraffin put into mould, by mold heated to 80 DEG C.Then mould is transferred in magnetic field, until the temperature of mould is down to room temperature.Repeat the operation of twice above-mentioned heating and cooling.Final formation modification wave absorbing agent.In the finished product modification wave absorbing agent formed by the technique of the present embodiment, iron carbonyl-TiO
2the weight percent of nucleocapsid structure particulate is 50%, and the weight percent of paraffin is 50%.
Embodiment 2
40ml hydrogen peroxide is mixed with 60ml ethanol, and 5g carbonyl iron dust is added wherein.Then the above-mentioned mixing solutions of supersound process 120 minutes under the power of 900 watts.After supersound process, the carbonyl iron dust after oxidation is taken out from mixing solutions, use ethanol to clean, and dry the carbonyl iron dust after oxidation.
Carbonyl iron dust after being oxidized by 5g puts into ball grinder, and the weight ratio of pellet and the carbonyl iron dust after being oxidized is 20:1, and ball milling solution is anhydrous ethene.Under the rotating speed of 300r/min, implement ball-milling technology 9 hours.
Carbonyl iron dust after 2g ball milling is put into the sodium hydroxide solution of 100ml pH=10, then under the power of 180 watts ultrasonic 10 minutes.Take out the carbonyl iron dust after surface treatment, clean 3-5 time in dehydrated alcohol, and room temperature is dried.
5ml tetrabutyl titanate (TBT) is dissolved in 10ml ethanol and forms the first solution; 5g carbonyl iron dust after surface treatment is put into 30ml ethanol and forms the second solution; 15ml deionized water and 15ml ethanol are mixed to form the 3rd solution.First solution is added drop-wise in the second solution, and stirs ultrasonic 20 minutes, then the 3rd solution is added drop-wise in the mixing solutions of first and second solution, and stir ultrasonic 4 hours.Filter final mixing solutions afterwards, get solid much filtrate, use ethanol purge and dry, obtaining iron carbonyl-TiO
2nucleocapsid structure particulate.
By 5g iron carbonyl-TiO
2nucleocapsid structure particulate and 7.5g paraffin put into mould, by mold heated to 85 DEG C.Then mould is transferred in magnetic field, until the temperature of mould is down to room temperature.Repeat the operation of twice above-mentioned heating and cooling.Final formation modification wave absorbing agent.In the finished product modification wave absorbing agent formed by the technique of the present embodiment, iron carbonyl-TiO
2the weight percent of nucleocapsid structure particulate is 40%, and the weight percent of paraffin is 60%.
Embodiment 3
10ml hydrogen peroxide is mixed with 90ml ethanol, and 10g carbonyl iron dust is added wherein.Then the above-mentioned mixing solutions of supersound process 120 minutes under the power of 900 watts.After supersound process, the carbonyl iron dust after oxidation is taken out from mixing solutions, use ethanol to clean, and dry the carbonyl iron dust after oxidation.
Carbonyl iron dust after being oxidized by 10g puts into ball grinder, and the weight ratio of pellet and the carbonyl iron dust after being oxidized is 20:1, and ball milling solution is anhydrous ethene.Under the rotating speed of 650r/min, implement ball-milling technology 7 hours.
Carbonyl iron dust after 10g ball milling is put into the sodium hydroxide solution of 100ml pH=13, then under the power of 180 watts ultrasonic 10 minutes.Take out the carbonyl iron dust after surface treatment, clean 3-5 time in dehydrated alcohol, and room temperature is dried.
5ml tetrabutyl titanate (TBT) is dissolved in 13ml ethanol and forms the first solution; 2g carbonyl iron dust after surface treatment is put into 30ml ethanol and forms the second solution; 15ml deionized water and 15ml ethanol are mixed to form the 3rd solution.First solution is added drop-wise in the second solution, and stirs ultrasonic 20 minutes, then the 3rd solution is added drop-wise in the mixing solutions of first and second solution, and stir ultrasonic 2 hours.Filter final mixing solutions afterwards, get solid much filtrate, use ethanol purge and dry, obtaining iron carbonyl-TiO
2nucleocapsid structure particulate.
By 10g iron carbonyl-TiO
2nucleocapsid structure particulate and 6.7g paraffin put into mould, by mold heated to 85 DEG C.Then mould is transferred in magnetic field, until the temperature of mould is down to room temperature.Repeat the operation of twice above-mentioned heating and cooling.Final formation modification wave absorbing agent.In the finished product modification wave absorbing agent formed by the technique of the present embodiment, iron carbonyl-TiO
2the weight percent of nucleocapsid structure particulate is 60%, and the weight percent of paraffin is 40%.
Embodiment 4
5g is put into ball grinder without the carbonyl iron dust of oxide treatment, and the weight ratio of pellet and the carbonyl iron dust after being oxidized is 30:1, and ball milling solution is anhydrous ethene.Under the rotating speed of 600r/min, implement ball-milling technology 5 hours.
Carbonyl iron dust after 5g ball milling is put into the sodium hydroxide solution of 100ml pH=10, then under the power of 180 watts ultrasonic 30 minutes.Take out the carbonyl iron dust after surface treatment, clean 3-5 time in dehydrated alcohol, and room temperature is dried.
5ml tetrabutyl titanate (TBT) is dissolved in 15ml ethanol and forms the first solution; 5g carbonyl iron dust after surface treatment is put into 30ml ethanol and forms the second solution; 15ml deionized water and 15ml ethanol are mixed to form the 3rd solution.First solution is added drop-wise in the second solution, and stirs ultrasonic 30 minutes, then the 3rd solution is added drop-wise in the mixing solutions of first and second solution, and stir ultrasonic 2 hours.Filter final mixing solutions afterwards, get solid much filtrate, use ethanol purge and dry, obtaining iron carbonyl-TiO
2nucleocapsid structure particulate.
By 5g iron carbonyl-TiO
2nucleocapsid structure particulate and 20g paraffin put into mould, by mold heated to 90 DEG C.Then mould is transferred in magnetic field, until the temperature of mould is down to room temperature.Repeat the operation of twice above-mentioned heating and cooling.Final formation modification wave absorbing agent.In the finished product modification wave absorbing agent formed by the technique of the present embodiment, iron carbonyl-TiO
2the weight percent of nucleocapsid structure particulate is 20%, and the weight percent of paraffin is 80%.
Embodiment 5
10g is put into ball grinder without the carbonyl iron dust of oxide treatment, and the weight ratio of pellet and the carbonyl iron dust after being oxidized is 25:1, and ball milling solution is anhydrous ethene.Under the rotating speed of 400r/min, implement ball-milling technology 6 hours.
Carbonyl iron dust after 10g ball milling is put into the sodium hydroxide solution of 100ml pH=12, then under the power of 180 watts ultrasonic 40 minutes.Take out the carbonyl iron dust after surface treatment, clean 3-5 time in dehydrated alcohol, and room temperature is dried.
5ml tetrabutyl titanate (TBT) is dissolved in 17.5ml ethanol and forms the first solution; 10g carbonyl iron dust after surface treatment is put into 30ml ethanol and forms the second solution; 15ml deionized water and 15ml ethanol are mixed to form the 3rd solution.First solution is added drop-wise in the second solution, and stirs ultrasonic 40 minutes, then the 3rd solution is added drop-wise in the mixing solutions of first and second solution, and stir ultrasonic 2 hours.Filter final mixing solutions afterwards, get solid much filtrate, use ethanol purge and dry, obtaining iron carbonyl-TiO
2nucleocapsid structure particulate.
By 10g iron carbonyl-TiO
2nucleocapsid structure particulate and 23.3g paraffin put into mould, by mold heated to 80 DEG C.Then mould is transferred in magnetic field, until the temperature of mould is down to room temperature.Repeat the operation of twice above-mentioned heating and cooling.Final formation modification wave absorbing agent.In the finished product modification wave absorbing agent formed by the technique of the present embodiment, iron carbonyl-TiO
2the weight percent of nucleocapsid structure particulate is 30%, and the weight percent of paraffin is 70%.
Test 1 wave-sucking performance test
The sample of the modification wave absorbing agent made in Example 1 to embodiment 5 is respectively according to GJB2038-94(radar absorbing reflectivity test method) in described experimental technique, carry out wave-sucking performance test.
| Embodiment | Fm/GHz | RLmin/dB | Δw（-5dB）/GHz | Δw（-10dB）/GHz |
| 1 | 3.0 | -17.9 | 4.1（1.6-5.7） | 1.6（2.2-3.8） |
| 2 | 4.8 | -25.6 | 6.3（2.9-9.2） | 2.4（4.1-6.5） |
| 3 | 2.1 | -16.8 | 2.6（1.3-3.9） | 1.2（2.1-3.3） |
| 4 | 9.4 | -34.5 | 10.7（4.1-14.8） | 4.1（5.6-10.7） |
| 5 | 8.7 | -23.1 | 10.5（4.6-15.1） | 4.8（6.8-11.6） |
Table 1 wave-sucking performance test result
In upper table, Fm/GHz carries out wave-sucking performance test under corresponding frequency.Some series datas of Δ w represent the frequency range of wave-sucking performance, such as, 4.1(1.6-5.7) represent the wave-absorbing effect that all can reach-5dB in the scope of 1.6GHz to 5.7GHz, and frequency range is 4.1GHz.
Experimental result shows, the wave absorbing agent obtained by method of the present invention all has good wave-sucking performance in multiple different suction ripple frequency range.As shown in table 1, the wave absorbing agent prepared by method of the present invention all has outstanding wave-sucking performance in the range of frequency from 3.0GHz to 8.7GHz, and when-5dB, it inhales ripple frequency range can reach 10.7GHz; When-10dB, it inhales frequency range also can reach 4.8GHz.
The preparation of embodiment 6 prepreg
Use stirrer to be mixed by any one finished product modification wave absorbing agent manufactured in resin and embodiment 1-5, after mixing completely, form the mixture of resin and wave absorbing agent.Use adhesive applicator to be coated on by said mixture in separate-type paper and form resin glued membrane.Smoking ripple prepreg will be formed in the impregnation to fiber of above-mentioned resin glued membrane.
Embodiment 7 prepreg shaping
The suction ripple prepreg formed in embodiment 6 is added in predetermined mould.Before prepreg is joined mould, brushing external release agent in mould.After preheating and precharge are carried out to prepreg, prepreg is put into molding apparatus.In molding apparatus, the dwell time, forming pressure was in the scope of 15MPa to 29MPa, and mold temperature is in the scope of 150 DEG C to 180 DEG C, and soaking time is in the scope of 3 minutes to 5 minutes in the scope of 20 minutes to 120 minutes.In certain embodiments, the moulding process used can be vacuum-bag process or autoclave molding etc.Formed after mould pressing process and inhale ripple substrate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (37)
1. prepare a method for wave absorbing agent, it is characterized in that, comprising:
Ball-milling technology is implemented to carbonyl iron dust;
Highly basic is used to carry out surface treatment to the described carbonyl iron dust after ball milling;
Use carbonyl iron dust described in titanium-containing compound process, obtain iron carbonyl-TiO
2nucleocapsid structure particulate; And
Magnetize described iron carbonyl-TiO
2nucleocapsid structure particulate.
2. method according to claim 1, is characterized in that, implements step carbonyl iron dust being implemented to ball-milling technology in ball grinder.
3. method according to claim 2, is characterized in that, described ball grinder comprises pellet, and wherein, the weight ratio of described pellet and described carbonyl iron dust is between 20:1 and 30:1.
4. method according to claim 2, is characterized in that, step carbonyl iron dust being implemented to ball-milling technology is implemented in organic solvent.
5. method according to claim 4, is characterized in that, described organic solvent is selected from a kind of in ethanol, acetone, Virahol, normal hexane and octane or their combination.
6. method according to claim 2, is characterized in that, the rotating speed of described ball grinder is 300 ~ 650r/min.
7. method according to claim 2, is characterized in that, step carbonyl iron dust being implemented to ball-milling technology continues 5 ~ 9 hours.
8. method according to claim 1, is characterized in that, uses highly basic to carry out surface-treated step to the described carbonyl iron dust after ball milling and comprises further:
Described carbonyl iron dust after ball milling is put into strong base solution and forms the first mixture;
Supersound process is carried out to described first mixture;
From described first mixture after supersound process, take out described carbonyl iron dust, and clean described carbonyl iron dust; And
Dry described carbonyl iron dust.
9. method according to claim 8, is characterized in that, described strong base solution is a kind of in sodium hydroxide solution and potassium hydroxide solution or their combination.
10. method according to claim 8, is characterized in that, the pH value of described strong base solution is 10 ~ 13.
11. methods according to claim 8, is characterized in that, implement the step of the first mixture being carried out to supersound process under the power of 180 watts.
12. methods according to claim 8, is characterized in that, the step of the first mixture being carried out to supersound process continues 10 minutes to 40 minutes.
13. methods according to claim 8, is characterized in that, with an organic solvent implement the step of cleaning carbonyl iron dust.
14. methods according to claim 13, is characterized in that, described organic solvent comprises dehydrated alcohol.
15. methods according to claim 8, is characterized in that, repeat the step of 3-5 the described carbonyl iron dust of cleaning.
16. methods according to claim 8, is characterized in that, implement the step of drying described carbonyl iron dust in air dry oven.
17. methods according to claim 1, is characterized in that, use the step of carbonyl iron dust described in titanium-containing compound process to comprise further:
Titanium-containing compound is dissolved in organic solvent, forms the first solution;
Described carbonyl iron dust is mixed with organic solvent, forms the second solution;
Deionized water is mixed with organic solvent, forms the 3rd solution;
Described first solution is added drop-wise in described second solution, and carries out the first stirring supersound process, form the 4th solution;
Described 3rd solution is added drop-wise in described 4th solution, and carries out the second stirring supersound process;
Filter described 4th solution, and with an organic solvent clean the solid product leached; And
Dry described solid product.
18. methods according to claim 17, is characterized in that, described titanium-containing compound is tetrabutyl titanate.
19. methods according to claim 17, is characterized in that, described organic solvent is ethanol.
20. methods according to claim 17, is characterized in that, in described first solution, the volume ratio of described titanium-containing compound and described organic solvent is between 1:4 to 1:2.
21. methods according to claim 20, is characterized in that, in described first solution, the volume ratio of described titanium-containing compound and described organic solvent is 1:4.
22. methods according to claim 17, is characterized in that, in described 3rd solution, the volume ratio of described deionized water and described organic solvent is 1:1.
23. methods according to claim 17, is characterized in that, the time of described first ultrasonic agitation process is between 10 minutes to 40 minutes.
24. methods according to claim 1, is characterized in that, magnetize described iron carbonyl-TiO
2the step of nucleocapsid structure particulate comprises further:
By described iron carbonyl-TiO
2nucleocapsid structure particulate and coating material put into mould simultaneously;
Heat described mould until described coating material melts; And
Described mould is put into magnetic field, and rotates described mould until room temperature is down to by described coating material.
25. methods according to claim 24, is characterized in that, by described iron carbonyl-TiO
2the step of mould put into by nucleocapsid structure particulate and coating material simultaneously, described iron carbonyl-TiO
2the weight ratio of nucleocapsid structure particulate and described coating material is between 1:9 to 2:3.
26. methods according to claim 24, is characterized in that, at heating mould until in the step of described coating material thawing, Heating temperature is between 80 DEG C to 90 DEG C.
27. methods according to claim 24, is characterized in that, described coating material comprises paraffin, polyethylene, polypropylene, polystyrene, epoxy resin or resol.
28. methods according to claim 24, is characterized in that, repeat 2-10 the described iron carbonyl of described magnetization-TiO
2the step of nucleocapsid structure particulate.
29. methods according to claim 1, is characterized in that, before the step described carbonyl iron dust being implemented to ball-milling technology, comprise further:
Oxidation carbonyl iron dust.
30. methods according to claim 29, is characterized in that, the step of oxidation carbonyl iron dust comprises further:
Carbonyl iron dust is put into the mixing solutions of hydrogen peroxide and organic solvent;
Supersound process is implemented to described mixing solutions; And
Filter described mixing solutions, and with an organic solvent solid product after cleaning and filtering; And
Dry solid product after described filtration.
31. methods according to claim 30, is characterized in that, carbonyl iron dust is being put into the step of mixing solutions of hydrogen peroxide and organic solvent, the volume ratio of described hydrogen peroxide and described organic solvent is between 1:19 to 2:3.
32. methods according to claim 30, described organic solvent is dehydrated alcohol.
33. 1 kinds of wave absorbing agents, is characterized in that, comprising:
Modified carbonyl iron powder 10% ~ 60%(weight); And coating material 40% ~ 90%(weight).
34. wave absorbing agents according to claim 33, is characterized in that, described modified carbonyl iron powder comprises iron carbonyl-TiO
2nucleocapsid structure particulate.
35. wave absorbing agents according to claim 33, is characterized in that, described coating material comprises paraffin, polyethylene, polypropylene, polystyrene, epoxy resin or resol.
36. 1 kinds of prepregs being filled with the wave absorbing agent according to any one of claim 33-35.
37. 1 kinds of suction ripple substrates being filled with the wave absorbing agent according to any one of claim 33-35.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310642548.1A CN104673184B (en) | 2013-12-03 | 2013-12-03 | A kind of wave absorbing agent, preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310642548.1A CN104673184B (en) | 2013-12-03 | 2013-12-03 | A kind of wave absorbing agent, preparation method and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104673184A true CN104673184A (en) | 2015-06-03 |
| CN104673184B CN104673184B (en) | 2016-09-07 |
Family
ID=53308789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310642548.1A Active CN104673184B (en) | 2013-12-03 | 2013-12-03 | A kind of wave absorbing agent, preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104673184B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163500A (en) * | 2017-07-18 | 2017-09-15 | 陈剑桃 | A kind of composite wave-suction material of multi-layer hollow structure |
| CN107415336A (en) * | 2017-07-28 | 2017-12-01 | 韦德永 | A kind of multilayer high temperature resistant absorbent structure based on honeycomb |
| CN109219335A (en) * | 2018-11-22 | 2019-01-15 | 昆山市中迪新材料技术有限公司 | Wide-band and wave-absorbing piece and preparation method thereof |
| CN109207123A (en) * | 2018-09-10 | 2019-01-15 | 中南大学 | A kind of double shell structurre carbonyl iron composite absorbers and preparation method |
| CN109957376A (en) * | 2017-12-26 | 2019-07-02 | 洛阳尖端技术研究院 | A kind of wave absorbing agent and preparation method thereof |
| CN109957375A (en) * | 2017-12-22 | 2019-07-02 | 深圳光启尖端技术有限责任公司 | A kind of oxidation wave absorbing agent and preparation method thereof |
| WO2020114089A1 (en) * | 2018-12-06 | 2020-06-11 | 洛阳尖端技术研究院 | Low-frequency wave absorbing material and preparation method therefor |
| CN112071618A (en) * | 2020-08-28 | 2020-12-11 | 南京大学 | Preparation method of iron-silicon-aluminum sheet magnetic powder with surface insulated and coated with titanium dioxide |
| CN112409653A (en) * | 2019-08-23 | 2021-02-26 | 洛阳尖端技术研究院 | Wave absorbing agent, preparation method and application thereof |
| CN112744870A (en) * | 2019-10-30 | 2021-05-04 | 洛阳尖端技术研究院 | Aluminum oxide-carbonyl iron microsphere wave absorbing agent and preparation method thereof |
| CN114684863A (en) * | 2020-12-31 | 2022-07-01 | 洛阳尖端技术研究院 | Sheet carbonyl iron/silver wave-absorbing material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235206A (en) * | 2008-01-29 | 2008-08-06 | 东华理工大学 | Core-shell type lightweight broad-band composite wave-absorbing material and preparation method thereof |
| CN102815754A (en) * | 2012-08-14 | 2012-12-12 | 南京航空航天大学 | Preparation method for flaky carbonyl iron powder with high magnetic permeability |
| CN103008674A (en) * | 2013-01-08 | 2013-04-03 | 安徽工业大学 | Nickel/copper oxide composite nanometer wave absorbing material and preparation method thereof |
| CN103396762A (en) * | 2013-08-05 | 2013-11-20 | 中国科学院合肥物质科学研究院 | Wave-absorbing material and preparation method thereof |
-
2013
- 2013-12-03 CN CN201310642548.1A patent/CN104673184B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235206A (en) * | 2008-01-29 | 2008-08-06 | 东华理工大学 | Core-shell type lightweight broad-band composite wave-absorbing material and preparation method thereof |
| CN102815754A (en) * | 2012-08-14 | 2012-12-12 | 南京航空航天大学 | Preparation method for flaky carbonyl iron powder with high magnetic permeability |
| CN103008674A (en) * | 2013-01-08 | 2013-04-03 | 安徽工业大学 | Nickel/copper oxide composite nanometer wave absorbing material and preparation method thereof |
| CN103396762A (en) * | 2013-08-05 | 2013-11-20 | 中国科学院合肥物质科学研究院 | Wave-absorbing material and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163500A (en) * | 2017-07-18 | 2017-09-15 | 陈剑桃 | A kind of composite wave-suction material of multi-layer hollow structure |
| CN107415336A (en) * | 2017-07-28 | 2017-12-01 | 韦德永 | A kind of multilayer high temperature resistant absorbent structure based on honeycomb |
| CN109957375A (en) * | 2017-12-22 | 2019-07-02 | 深圳光启尖端技术有限责任公司 | A kind of oxidation wave absorbing agent and preparation method thereof |
| CN109957376A (en) * | 2017-12-26 | 2019-07-02 | 洛阳尖端技术研究院 | A kind of wave absorbing agent and preparation method thereof |
| CN109207123B (en) * | 2018-09-10 | 2021-06-22 | 中南大学 | Carbonyl iron powder composite wave-absorbing material with double-shell structure and preparation method thereof |
| CN109207123A (en) * | 2018-09-10 | 2019-01-15 | 中南大学 | A kind of double shell structurre carbonyl iron composite absorbers and preparation method |
| CN109219335A (en) * | 2018-11-22 | 2019-01-15 | 昆山市中迪新材料技术有限公司 | Wide-band and wave-absorbing piece and preparation method thereof |
| CN109219335B (en) * | 2018-11-22 | 2024-04-30 | 江苏中迪新材料技术有限公司 | Broadband wave absorbing plate and manufacturing method thereof |
| WO2020114089A1 (en) * | 2018-12-06 | 2020-06-11 | 洛阳尖端技术研究院 | Low-frequency wave absorbing material and preparation method therefor |
| CN111285671A (en) * | 2018-12-06 | 2020-06-16 | 洛阳尖端技术研究院 | Low-frequency wave-absorbing material and preparation method thereof |
| CN112409653A (en) * | 2019-08-23 | 2021-02-26 | 洛阳尖端技术研究院 | Wave absorbing agent, preparation method and application thereof |
| CN112744870A (en) * | 2019-10-30 | 2021-05-04 | 洛阳尖端技术研究院 | Aluminum oxide-carbonyl iron microsphere wave absorbing agent and preparation method thereof |
| CN112071618A (en) * | 2020-08-28 | 2020-12-11 | 南京大学 | Preparation method of iron-silicon-aluminum sheet magnetic powder with surface insulated and coated with titanium dioxide |
| CN114684863A (en) * | 2020-12-31 | 2022-07-01 | 洛阳尖端技术研究院 | Sheet carbonyl iron/silver wave-absorbing material and preparation method thereof |
| CN114684863B (en) * | 2020-12-31 | 2024-08-27 | 洛阳尖端技术研究院 | Sheet carbonyl iron/silver wave-absorbing material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104673184B (en) | 2016-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104673184A (en) | Electromagnetic wave absorber as well as preparation method and application thereof | |
| CN105297530B (en) | One kind inhales ripple honeycomb and preparation method thereof | |
| CN107734950B (en) | Zinc ferrite@manganese dioxide@graphene composite wave-suction material and preparation method thereof | |
| CN108587159B (en) | Graphene-like carbon nitride/ferroferric oxide/polyaniline nano composite wave-absorbing material and preparation method thereof | |
| CN108795379A (en) | A kind of preparation method of three-dimensional netted multi-walled carbon nanotube/Ni ferrite composite wave-suction material | |
| CN108010649A (en) | A kind of in-situ preparation method of multi-layer core-shell nanostructured and its application in electromagnetic wave absorbent material is prepared | |
| CN109310038A (en) | One kind is using copper MOFs as porous C o/Cu/C composite wave-suction material and preparation method thereof made from presoma | |
| CN109943018B (en) | Wave absorbing agent, wave absorbing material and respective preparation method | |
| CN108675765B (en) | Preparation method of microwave absorbing material based on coal gangue | |
| CN112430451A (en) | Nitrogen-doped graphene/cobalt-zinc ferrite composite aerogel wave-absorbing material and preparation method thereof | |
| CN108546547A (en) | A kind of preparation method of multiple spectra composite wave-absorbing agent | |
| CN107286907A (en) | The molybdenum disulfide of a kind of core shell structure/carbonyl iron composite microwave absorbent and preparation method thereof | |
| CN106986991A (en) | The preparation method of polyaniline/expanded perlite/barium ferrite magnetoelectric composites | |
| CN115650286A (en) | rGO/MXene/TiO 2 /Fe 2 Preparation method of C multi-stage heterostructure porous microsphere wave-absorbing material | |
| CN104439273B (en) | Preparation method for FeCo/ZnO composite wave-absorbing material | |
| CN102129904A (en) | Floating bead-based barium ferrite magnetic composite material and preparation method thereof | |
| CN106521312A (en) | Method for preparing FeSiAl-series alloy micro powder electromagnetic absorbent | |
| CN103224595B (en) | A kind of polymer-based nano absorbing material | |
| CN112226203A (en) | Hollow microsphere core-shell structure wave-absorbing material and preparation method and application thereof | |
| CN106947256A (en) | Composite wave-suction material for medical apparatus | |
| CN107445627B (en) | A kind of preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder | |
| CN114496544B (en) | Manufacturing method of low-power consumption iron-nickel-molybdenum magnetic powder core | |
| CN113277784B (en) | Pumice concrete with electromagnetic wave absorption function | |
| CN105462178A (en) | Preparing method for microwave-absorption compound epoxy resin doped with nanometer iron oxide | |
| CN105419250B (en) | One kind inhales ripple insulating coating material formula and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210415 Address after: 2 / F, software building, No.9, Gaoxin Zhongyi Road, Nanshan District, Shenzhen City, Guangdong Province Patentee after: KUANG-CHI INSTITUTE OF ADVANCED TECHNOLOGY Address before: 18B, building a, CIC international business center, 1061 Xiangmei Road, Futian District, Shenzhen, Guangdong 518034 Patentee before: KUANG-CHI INNOVATIVE TECHNOLOGY Ltd. |