CN110305429A - A kind of flexibility absorbing material and preparation method thereof - Google Patents
A kind of flexibility absorbing material and preparation method thereof Download PDFInfo
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- CN110305429A CN110305429A CN201910635376.2A CN201910635376A CN110305429A CN 110305429 A CN110305429 A CN 110305429A CN 201910635376 A CN201910635376 A CN 201910635376A CN 110305429 A CN110305429 A CN 110305429A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The present invention relates to a kind of flexible absorbing materials and preparation method thereof, the technical problem which solve thermal stability existing for existing absorbing material is poor, density is big, corrosion resistance is weak comprising polymeric matrix Kynoar and inorganic functional fillers zinc ferrite silica redox graphene.Invention also provides preparation methods.It invention can be widely used in the preparation field of flexible absorbing material.
Description
Technical field
The present invention relates to a kind of absorbing material, specifically a kind of flexible absorbing material and preparation method thereof.
Background technique
With the high speed development of electronic information technology and popularizing for various electronic products, electromagenetic wave radiation has become one kind
New environmental pollution.Studies have shown that excessive electromagenetic wave radiation can cause nervous system, immune system, reproductive system and blood to follow
The lesion of loop system, in some instances it may even be possible to induce the serious disease including various cancers.Equally, electromagnetic interference caused by electromagnetic wave
Also the normal operation that will affect broadcast, TV, communication, precision instrument, Medical Devices, navigation equipment etc., after may cause seriously
Fruit.For example, since Electromagnetic Interference causes the electronic instrument of delayed flight, hospital can not work normally, the communication such as mobile phone, computer
The electromagnetic wave radiated in tool use process interferes other signals while being also possible to leak state secrets and a information.
Absorbing material is the incident electromagnetic wave that can absorb and decay, and its electromagnetic energy is fallen or made for other forms energy dissipation
A kind of functional material that electromagnetic wave disappears by interference, therefore, research and develop have excellent properties absorbing material, control and
Electromagnetic environment is purified, there is huge meaning and value for military field and civil field.
In a variety of different electromagnetic wave absorbent materials, ferrite is because of its abundant raw materials, at low cost, good dispersion and electricity
Superior magnetic property is always scientists focus of attention.But there is also one as radio-radar absorber for simple Ferrite Material
Fixed limitation, thermal stability is poor, density is big, corrosion resistance is weak etc., and it is very fast in the ferritic disaccommodation of high band, it leads
Absorbing property is caused to reduce.Carbon and its compound have the characteristics that light weight, absorption band are wide as absorbing material, in electromagnetism wave screen
The field of covering possesses broad application prospect, and typical example is exactly graphene and its compound.Graphene is introduced not in wave absorbing agent
The density that compound can only be reduced, can also improve its electromagnetic wave absorption performance.But simple inorganic absorbent generally cannot
It directly uses, needs to be cooperated with matrix.Major part document report is by Inorganic Fillers Filled into paraffin, only at present
In order to meet sample test requirement, practical application is not considered.In consideration of it, how further by inorganic suction wave filler and matrix
Combine, play the synergistic effect between each component, needs what is solved to ask with higher application value, and at present
Topic.
Summary of the invention
The present invention is exactly to solve the technology that thermal stability existing for existing absorbing material is poor, density is big, corrosion resistance is weak
Problem provides a kind of flexible absorbing material with excellent absorbing property.
For this purpose, the present invention provides a kind of flexible absorbing material comprising polymeric matrix, the polymeric matrix are poly- inclined
Vinyl fluoride；Further include inorganic functional fillers, the inorganic functional fillers be zinc ferrite@silica@redox graphene without
Machine functional stuffing.
Preferably, the loading of the inorganic functional fillers in a polymer matrix is 5-30wt%.
Present invention simultaneously provides a kind of preparation methods of flexible absorbing material comprising following steps:
(1) solvent structure nanometer zinc ferrite is used, silica is obtained by teos hydrolysis, forms ferrous acid
Zinc@silicon dixoide nucleocapsid structure；(2) the zinc ferrite silica core shell particles that the step (1) obtains are dispersed in anhydrous second
In alcohol, graphene oxide dispersion is first mixed with cetyl trimethylammonium bromide ultrasound, then mixes with zinc ferrite@silica,
Ultrasonic agitation obtains zinc ferrite@silica@graphene oxide after then using mechanical stirring；It is dry after being separated using magnet
Processing, obtains zinc ferrite@silica@redox graphene ternary functional stuffing；It (3) will be obtained in the step (2)
Zinc ferrite@silica@redox graphene functional stuffing, ultrasonic disperse add poly- in n,N-Dimethylformamide
Vinylidene powder, mechanical stirring, re-ultrasonic dispersion obtain flexible absorbing material after dry.
Preferably, in step (2), the ratio of zinc ferrite@silica and dehydrated alcohol are as follows: 1g:(100-300) ml, oxygen
Graphite alkene dispersion liquid and cetyl trimethylammonium bromide ratio are (10-30) ml:1g.
Preferably, in step (2), after separating using magnet, drying, drying temperature 60-80 are placed in vacuum drying oven
, drying time 12-24h.
Preferably, in step (3), graphene oxide obtains redox graphene in retort after high-temperature process,
Condition is 600-800, keep the temperature 3-5h, heating rate 2-5, nitrogen or argon atmosphere.
The present invention selects Ferrite Material zinc ferrite, and electromagnetic wave transparent material silica and graphene material devise ternary
Complex function filler, and flexible absorbing material is prepared in conjunction with high molecular material Kynoar, give full play to each component
Performance advantage and composite effect, the magnetic loss generated using zinc ferrite magnetic particle, dielectric loss includes zinc ferrite and titanium dioxide
Interfacial polarization effect between silicon, silica and graphene and graphene and Kynoar and graphene and gather inclined fluorine
The dipole polarization effect that ethylene generates, realizes the synergistic effect of dielectric loss and magnetic loss, effectively improves absorbing property.
The flexible absorbing material that the present invention is prepared has superior absorbing property compared to common inorganic wave absorbing agent.It is poly-
Vinylidene has good dielectric properties, excellent chemical corrosion resistance, low-density, good flexibility and filming performance, with
Impedance matching between inorganic filler is good, and the composite material of composition has excellent absorbing property.
Detailed description of the invention
Fig. 1 is that loading of the functional stuffing of the present invention in Kynoar matrix is respectively 5wt%, 10wt%,
The dielectric loss figure of composite material when 15wt%.
Fig. 2 is that loading of the functional stuffing of the present invention in Kynoar matrix is respectively 5wt%, 10wt%,
The magnetic loss figure of composite material when 15wt%.
Fig. 3 is the absorbing property figure that loading of the functional stuffing of the present invention in Kynoar matrix is 10wt%.
Fig. 4 is that loading of the functional stuffing of the present invention in Kynoar matrix is respectively 5wt%, 10wt%,
The absorbing property comparison diagram of material when 15wt%.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without this hair described in claims should will not be limited
It is bright.The clad structure of "@" symbology composite material herein, such as " zinc ferrite@silica " represent coated with silica and exist
Ferrous acid zinc surface.
Embodiment 1
The preparation of ternary structural zinc ferrite@silica@redox graphene: using ethylene glycol as solvent, six hydrations three
The molar ratio of iron chloride and zinc chloride is 2:1, and trisodium citrate and sodium acetate is added, using solvent structure nanometer ferrous acid
Then the zinc ferrite being prepared is dispersed in the in the mixed solvent of water and dehydrated alcohol, the ratio of zinc ferrite and solvent by zinc bead
Example is 1g:300ml, the volume ratio 1:3 of water and dehydrated alcohol, and 0.5ml ammonium hydroxide is added, while ethyl orthosilicate being dispersed in anhydrous
In ethyl alcohol, ethyl orthosilicate dispersion liquid is added dropwise to zinc ferrite dispersion liquid using separatory funnel later by volume ratio 1:40
In, core-shell structure zinc ferrite@silica is obtained, then divides the zinc ferrite@silica being prepared in dehydrated alcohol
It dissipates, ratio 1g:100ml, cetyl trimethylammonium bromide is added to graphene oxide dispersion, ratio 1g:10ml,
Ultrasonic 2h mixes ultrasound 1h with zinc ferrite@silica dispersions afterwards, and stirring at normal temperature 8h, drying temperature is 60 after magnet separation
DEG C, drying time 12h, then restore to obtain zinc ferrite@silica@redox graphene using 600 DEG C of high temperature cabonizations, it rises
Warm rate is 2 DEG C/min, soaking time 3h, nitrogen atmosphere.
Polyvinylidene fluoride flexibility absorbing material preparation method: the zinc ferrite@silica@reduction-oxidation that will be prepared
Graphene ultrasonic disperse is in n,N-Dimethylformamide, ultrasonic 1h, and Kynoar powder, zinc ferrite@dioxy is then added
SiClx redox graphene accounts for the 5% of Kynoar substrate quality, room temperature mechanical stirring 1h, then ultrasound 1h, pours into culture
Ware is placed into vacuum oven, and 60 DEG C of drying temperature, drying time 12h, it is that the flexible of 5wt% is inhaled that loading, which can be obtained,
Wave material.
Embodiment 2
Compared with Example 1, the part that embodiment 2 changes is the ratio that zinc ferrite@silica disperses in dehydrated alcohol
Example is 1g:200ml, and cetyl trimethylammonium bromide is added to graphene oxide dispersion, ratio 1g:20ml, ultrasound
3h mixes ultrasound 2h with zinc ferrite@silica dispersions afterwards, and stirring at normal temperature 10h, drying temperature is 70 DEG C after magnet separation,
Drying time is 18h, then restores to obtain zinc ferrite@silica@redox graphene using 700 DEG C of high temperature cabonizations, is heated up
Rate is 3 DEG C/min, soaking time 4h, argon atmosphere.
Polyvinylidene fluoride flexibility absorbing material preparation method: the zinc ferrite@silica@reduction-oxidation that will be prepared
Graphene ultrasonic disperse is in n,N-Dimethylformamide, ultrasonic 1.5h, and Kynoar powder, zinc ferrite@bis- is then added
Silica redox graphene accounts for the 15% of Kynoar substrate quality, room temperature mechanical stirring 2h, then ultrasound 1.5h,
Enter culture dish, be placed into vacuum oven, 70 DEG C of drying temperature, drying time 18h, it is 15wt%'s that loading, which can be obtained,
Flexible absorbing material.Remaining operation and explanation are the same as embodiment 1.
Embodiment 3
Compared with Example 1, the part that embodiment 2 changes is the ratio that zinc ferrite@silica disperses in dehydrated alcohol
Example is 1g:300ml, and cetyl trimethylammonium bromide is added to graphene oxide dispersion, ratio 1g:30ml, ultrasound
5h mixes ultrasound 3h with zinc ferrite@silica dispersions afterwards, and stirring at normal temperature 12h, drying temperature is 80 DEG C after magnet separation,
Drying time is for 24 hours, then to restore to obtain zinc ferrite@silica@redox graphene using 800 DEG C of high temperature cabonizations, is heated up
Rate is 5 DEG C/min, soaking time 5h.
Polyvinylidene fluoride flexibility absorbing material preparation method: the zinc ferrite@silica@reduction-oxidation that will be prepared
Graphene ultrasonic disperse is in n,N-Dimethylformamide, ultrasonic 2h, and Kynoar powder, zinc ferrite@dioxy is then added
SiClx@redox graphene accounts for the 30% of Kynoar quality, and room temperature machinery stirs 3h, then ultrasound 2h, pours into culture dish, puts
It is placed in vacuum oven, 80 DEG C of drying temperature, drying time, it was that the flexible of 30wt% inhales wave material that loading, which can be obtained, for 24 hours
Material.Remaining operation and explanation are the same as embodiment 1.
The absorbing material of each embodiment is cut into after the rectangle of 22.9*10.2mm and carries out suction wave using vector network analyzer
Performance test, test wave band are X-band, the experimental results showed that, Absorbing Materials are excellent, and reason is to have given full play to ferrous acid
Zinc@silica@redox graphene and the mutual synergistic effect of Kynoar, silicon dioxide layer enhance material
Wave transparent performance, so that electromagnetic wave enters material internal as much as possible, the introducing of redox graphene reduces the density of material,
Impedance matching is enhanced, the reflection of electromagnetic wave is effectively reduced, is gone back by zinc ferrite and silica, silica and oxidation
The interfacial polarization effect generated between former graphene, redox graphene and Kynoar, the magnetic loss that magnetic core zinc ferrite generates
The dipole polarization that consumption, redox graphene and Kynoar generate acts on, and realizes the collaboration of dielectric loss and magnetic loss
Effect, and then obtain excellent absorbing property.
It can be seen that the composite material dielectric loss and magnetic loss from Fig. 1, Fig. 2 and play synergistic effect, it can be with by Fig. 3
Find out, when zinc ferrite silica redox graphene in Kynoar matrix loading be 10wt%, material it is thick
When degree is 1.57mm, reflection loss is minimum to reach nearly -50dB, can absorb nearly 99.99% electromagnetic wave, better performances.Fig. 4 can be with
Find out, when loading is 5wt%, reflection loss is close to zero, and material is substantially without wave effect is inhaled, when loading is increased by 10wt%
When being added to 15wt%, for reflection loss only up to -10dB or so, performance is poor, so loading appropriate is to material property shadow
Sound is very big.
Claims (6)
1. a kind of flexibility absorbing material comprising polymeric matrix, characterized in that the polymeric matrix is Kynoar；
It further include inorganic functional fillers, the inorganic functional fillers are that zinc ferrite@silica@redox graphene inorganic functional is filled out
Material.
2. flexibility absorbing material according to claim 1, which is characterized in that the inorganic functional fillers are in Kynoar
Loading in matrix is 5-30wt%.
3. the preparation method of flexibility absorbing material as described in claim 1, it is characterized in that including the following steps:
(1) solvent structure nanometer zinc ferrite is used, silica is obtained by teos hydrolysis, forms zinc ferrite@
Silicon dixoide nucleocapsid structure；
(2) the zinc ferrite@silica that the step (1) obtains is dispersed in dehydrated alcohol, graphene oxide dispersion is first
It with cetyl trimethylammonium bromide ultrasonic mixing, then mixes with zinc ferrite@silica, is stirred by ultrasonic, then using machinery
Zinc ferrite@silica@graphene oxide is obtained after stirring；After being separated using magnet, it is dried, obtains zinc ferrite@dioxy
SiClx@redox graphene ternary functional stuffing；
(3) zinc ferrite@silica@redox graphene functional stuffing, ultrasonic disperse obtained in the step (2) are existed
In n,N-Dimethylformamide, Kynoar powder, mechanical stirring are added, re-ultrasonic dispersion obtains flexible suction after dry
Wave material.
4. the preparation method of flexibility absorbing material according to claim 3, which is characterized in that in the step (2), ferrous acid
The ratio of zinc@silica and dehydrated alcohol are as follows: 1g:(100-300) ml, graphene oxide dispersion and cetyl trimethyl
Ammonium bromide ratio is (10-30) ml:1g.
5. the preparation method of flexibility absorbing material according to claim 3, which is characterized in that in the step (2), use
After magnet separation, it is placed in vacuum drying oven drying, drying temperature is 60-80 DEG C, drying time 12-24h.
6. the preparation method of flexibility absorbing material according to claim 3, which is characterized in that in the step (3), oxidation
Graphene obtains redox graphene in retort after high-temperature process, and condition is 600-800 DEG C, keeps the temperature 3-5h, heating
Rate is 2-5 DEG C/min, nitrogen or argon atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835447A (en) * | 2019-12-02 | 2020-02-25 | 西安交通大学 | Ku waveband composite wave-absorbing material and preparation method thereof |
| CN115246994A (en) * | 2021-12-31 | 2022-10-28 | 浙江师范大学 | Heat conduction-wave absorption integrated flexible material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951916A (en) * | 2014-04-29 | 2014-07-30 | 南昌航空大学 | RGO (Reduced Graphene oxide)/ferric oxide-filled polyvinylidene fluoride composite wave-absorbing material and preparation method thereof |
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2019
- 2019-07-15 CN CN201910635376.2A patent/CN110305429A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951916A (en) * | 2014-04-29 | 2014-07-30 | 南昌航空大学 | RGO (Reduced Graphene oxide)/ferric oxide-filled polyvinylidene fluoride composite wave-absorbing material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIANTAO FENG, ET AL.: "Synthesis of Hierarchical ZnFe2O4@SiO2@GRO Core-Shell Microspheres for Enhanced Electromagnetic Wave Absorption", 《APPL. MATER. INTERFACES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835447A (en) * | 2019-12-02 | 2020-02-25 | 西安交通大学 | Ku waveband composite wave-absorbing material and preparation method thereof |
| CN115246994A (en) * | 2021-12-31 | 2022-10-28 | 浙江师范大学 | Heat conduction-wave absorption integrated flexible material and preparation method and application thereof |
| CN115246994B (en) * | 2021-12-31 | 2024-04-05 | 浙江师范大学 | Heat conduction-wave absorption integrated flexible material and preparation method and application thereof |
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Application publication date: 20191008 |