CN106566226B - A kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application - Google Patents
A kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application Download PDFInfo
- Publication number
- CN106566226B CN106566226B CN201610919480.0A CN201610919480A CN106566226B CN 106566226 B CN106566226 B CN 106566226B CN 201610919480 A CN201610919480 A CN 201610919480A CN 106566226 B CN106566226 B CN 106566226B
- Authority
- CN
- China
- Prior art keywords
- graphene
- thermoplastic polyurethane
- foamed material
- thermoplastic
- gradient
- 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.)
- Active
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/22—All layers being foamed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
- B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0207—Materials belonging to B32B25/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention discloses a kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application, the thermoplastic polyurethane/graphene foamed material has strong electromagnetic shield effectiveness and high absorbing property；This method prepares thermoplastic polyurethane/graphene fretting map film of single layer first with phase separation method, then with glue by the different monolayer thermoplastic's polyurethane of graphene content/graphene fretting map film being bonded to one material, to realize gradient dispersion of the graphene in thermoplastic polyurethane/graphene foamed material.Gradient-structure can assign thermoplastic polyurethane/good shield effectiveness of graphene foamed material, its absorbing property can also be greatly improved simultaneously, thermoplastic polyurethane/graphene foamed material of prepared lightweight has a good application prospect in electromagnetic shielding and absorbing material field.
Description
Technical field
The invention belongs to polymer matrix electromagnetic shielding material field, in particular to a kind of thermoplastic polyurethane/graphene hair
Foam material and its preparation method and application.
Background technique
Electromagnetic Interference refers to that harmful electromagnetic wave makes the normal function of electronic device be interfered or cause showing for obstacle
As, abbreviation EMI (electromagnetic interference), refer to radio wave, magnetic wave, light wave, sunspot and its
Its some natural disturbance from space.With the fast development of modern electronics industry, various wireless communication systems and high-frequency electrical
Sub- number of devices sharply increases, and it is outstanding day by day with electromagnetic pollution problem to result in increasing for electromagnetic interference phenomenon.On the one hand,
Electromagnetic radiation can cause severe jamming to the electronic equipment of surrounding, their working procedure is made to get muddled, and generate mistake
Movement；Also, electromagenetic wave radiation will cause information leakage, make the information security of the instruments such as computer by serious influence.It is existing
Not only there is interference to electronic device in discovery electromagnetic radiation, harm can also be generated to human body.The disease incidences such as cancer, leukaemia
Raising and the increase of electromagnetic radiation have certain relationship.Currently, how international organization and national governments, scientific research circle etc. are to preventing
Electromagnetic Interference gives great attention, and has formulated stringent regulation and carried out trapped electromagnetic wave radiation capacity.Therefore, it explores efficient
Electromagnetic shielding material prevents electromagnetic radiation pollution to protect environmental and human health impacts, it has also become problem in the urgent need to address.
Preventing and treating the most frequently used effective method of electromagnetic radiation is that harmful electromagnetic wave is shielded using electromagnetic shielding material
It covers.Therefore exploitation High Performance Shielding material is of great significance.The definition of material electromagnet shield effect is incident electromagnetic wave
Intensity and transmitted electromagnetic wave intensity rate logarithm, unit dB.Electromagnet shield effect numerical value is higher to mean fewer electricity
Magnetic wave can penetrate shielding material.For example, the minimum electromagnet shield effect that business application requires is 20dB, it is meant that only 1%
Electromagnetic wave can penetrate shielding material.
Traditional Metal Substrate shielding material the disadvantages of there are perishable, density is high, difficult processing, graphene is a kind of novel
Two-dimensional nano-carbon material, has good conductive, thermally conductive and electromagnetic shielding performance, it can be prepared with mixed with polymers soft
Tough composite material of good performance is expected to the substitute as metal material.Foaming structure is introduced in polymer composites
The density and processing cost of such material can be further decreased.Meanwhile porous structure can also induce electromagnetic wave in material
Portion carries out multipath reflection and scattering, increases its absorption to electromagnetic wave.So being commonly used for radar absorbing and shielded anechoic chamber etc.
Field.
In fact, material mainly includes two kinds of reflection and absorption to shielding electromagnetic waves mechanism.However, most of at present
Mainly by adding the conductive filler of high-content, to reach industrialized standard, (shield effectiveness is not less than polymeric barrier material
20dB), such as document: Adv.Funct.Mater., 2016,26,303-310；Carbon,2016,96,768-777；
Adv.Mater.2005,17,1999-2003.As a result, excessively high conductive filler enhances it substantially the reflection of electromagnetic wave, draw
Send out the secondary pollution to environment.In order to improve this situation, foaming structure is combined preparation with gradient-structure and provided by the present invention
There is lightweight thermoplastic polyurethane/graphene composite material of good flexibility, excellent electromagnetic shield effectiveness and high absorbing property.
Summary of the invention
Technical purpose of the invention is to provide a kind of thermoplastic polyurethane/graphene foamed material and preparation method thereof and answers
With the thermoplastic polyurethane/graphene foamed material has excellent electromagnetic shield effectiveness and high absorbing property, can using this method
To realize the large scale preparation of polymer matrix composite, there is good market application prospect.
A kind of preparation method of thermoplastic polyurethane/graphene foamed material, comprising:
(1) it disperses graphene in organic solvent, must be mixed after addition thermoplastic polyurethane elastomer stirring and dissolving molten
Mixed solution is poured into and carries out precipitating in coagulating bath by liquid, and rear powder is dried in thermoplastic polyurethane/graphene mixture of precipitation
It is broken；
(2) thermoplastic polyurethane obtained in step (1)/graphene mixture is dissolved in organic solvent, is mixed
Alloying film liquid carries out film with scraper and is mutually separated, and is done after obtaining thermoplastic polyurethane/graphene fretting map film
It is dry；
(3) thermoplastic polyurethane obtained in step (2)/graphene fretting map film is subjected to multiple-layer stacked, layer and layer
Between bonded with glue, form integrated thermoplastic polyurethane/graphene foamed material.
In step (1), the thermoplastic polyurethane elastomer is polyester-type or polyether-type.
In step (1), the organic solvent is N, N'- dimethylformamide (DMF), N, N'- dimethyl acetamide
(DMAc), one of acetone, cyclohexanone and butanone or a variety of.
In step (1), the coagulating bath is at least one of water or ethyl alcohol.
In the mixed solution of step (1), the mass ratio of the graphene, thermoplastic polyurethane elastomer and organic solvent is
1~30:70~99:1000~2500.
In step (2), phase separation include: by mixed solution pour into scraper carry out film and be exposed to temperature be 0~
50 DEG C and relative humidity carry out in the environment of being 50~99%, and the time of the phase separation is 0.1~for 24 hours.
In step (2), it is described mixing casting solution with a thickness of 0.001~5mm.
In step (2), the thermoplastic polyurethane/graphene fretting map film pore size is 1~15 μm, with a thickness of
100~400 μm.
In step (2), the drying temperature is 20~80 DEG C.
In step (3), the glue is one or more of PU glue, epoxy glue and UV glue.
In step (3), the thermoplastic polyurethane/graphene foamed material is by 2~100 layers of the poly- ammonia of monolayer thermoplastic
Ester/graphene fretting map film is formed by stacking.
Further preferably, in step (3), the thermoplastic polyurethane/graphene foamed material is by 2~100 layers of single layer
Thermoplastic polyurethane/graphene fretting map film by graphene in matrix content it is incremented by successively, be first incremented by and successively decrease afterwards or first pass
The constant rule successively decreased again is overlapped after increasing, forms gradient-structure.According to impedance matching principle, when electromagnetic wave is from air incidence
When to polymer composites surface, the variation of inner conductive packing density gradient advantageously reduces electromagnetic wave on the surface of the material
Reflection, increase it in the absorption of material internal.
The present invention also provides a kind of thermoplastic polyurethane/graphene foamed material, the thermoplastic polyurethane/graphene
Foamed material is prepared by the above method.
The present invention also provides above-mentioned thermoplastic polyurethane/application of the graphene foamed material in electromagnetic shielding field.
The present invention also provides above-mentioned thermoplastic polyurethane/application of the graphene foamed material in absorbing material field.
Compared with prior art, the invention has the following beneficial effects:
(1) there is thermoplastic polyurethane/graphene fretting map film of high graphene content using phase separation method preparation, gram
Conventional physical foaming (fast pressure relief and the method that is rapidly heated) has been taken to be difficult to prepare the difficulty of the foamed material of high filler content；
(2) foaming structure is combined with gradient-structure, not only significantly reduces the weight and cost of shielding material, also mentions
Its high absorption loss to electromagnetic wave；
(3) using phase separation method can realize monolayer thermoplastic's polyurethane/graphene fretting map film continuous production and
Large scale preparation is had good using integrated thermoplastic polyurethane/graphene foamed material itself prepared by layer stackup addition
Good flexibility and tack, may be used as the sealing element market application prospect with higher in electromagnetic shielding device.
Detailed description of the invention
Fig. 1 is that thermoplastic polyurethane/graphene that the graphene content that the embodiment of the present invention 1 is prepared is 4wt.% is micro-
The scanning electron microscope (SEM) photograph of foamed thin sheet；
Fig. 2 is double-deck thermoplastic polyurethane/graphene prepared by the embodiment of the present invention 1 with graphene concentration gradient
The shield effectiveness of composite material prepared by foamed material and comparative example 1 in Ku wave band (12~18GHz)；
Fig. 3 is double-deck thermoplastic polyurethane/graphene prepared by the embodiment of the present invention 1 with graphene concentration gradient
Composite material prepared by foamed material and comparative example 1 is in Ku wave band to the comparison diagram of electromagnetic wave absorptivity and reflectivity；
Fig. 4 is three layers of thermoplastic polyurethane/graphene prepared by the embodiment of the present invention 4 with graphene concentration gradient
The shield effectiveness of composite material prepared by foamed material and comparative example 4 in Ku wave band；
Fig. 5 is three layers of thermoplastic polyurethane/graphene prepared by the embodiment of the present invention 4 with graphene concentration gradient
Composite material prepared by foamed material and comparative example 4 is in Ku wave band to the comparison diagram of electromagnetic wave absorptivity and reflectivity.
Specific embodiment
The present invention is specifically described with reference to the accompanying drawings and examples.
Embodiment 1
(1) graphene of 0.83g is added in the DMF of 300mL, ultrasonic disperse 10 minutes, obtains black suspension.It is outstanding at this
20g thermoplastic polyurethane elastomer particle is added in supernatant liquid, oil bath high speed stirring and dissolving 5 hours of 60 DEG C, then by gained
To mixed solution pour into precipitating in distilled water.Finally, the thermoplastic polyurethane of precipitation/graphene mixture is placed in 60 DEG C
Dry 48h, crushes spare after taking-up in vacuum drying oven；
(2) thermoplastic polyurethane in step (1)/graphene mixture is re-dissolved in the DMF of 100mL and is mixed
Casting solution is poured into the slot scraping of scraper and carries out film on clean glass plate, and blade thickness is set as 4mm.It completes
Afterwards, it is placed in 3h in the air that relative humidity is 80% under room temperature, then takes out to be placed in 30 DEG C of vacuum drying oven and do
It is dry to obtain thermoplastic polyurethane/graphene fretting map film that graphene content is 4wt.% for 24 hours, it is labeled as PUG4, scanning
Electron microscope is as shown in Figure 1.
Thermoplastic polyurethane/graphene that graphene content is 8,12,16,20wt.% is prepared by the same method
Fretting map film, and it is respectively labeled as PUG8, PUG12, PUG16, PUG20.All thermoplastic polyurethanes prepared by this method/
Graphene fretting map film all has similar density (0.42g/cm3) and thickness (2mm).
(3) the two kinds of materials of PUG12 and PUG20 prepared in selecting step (2) press the sequence of graphene content from small to large
It is bonded with PU glue, forms the double-deck thermoplastic polyurethane/graphene foamed material with graphene concentration gradient.
Comparative example 1
Two layers of the PUG16 prepared in embodiment 1 is bonded.
Since the monolayer material of composition multilayer materials is different, there is more permutation and combination in different monolayer materials again
Mode.So the electromagnetic shielding test process of multilayer materials is typically more complicated.In view of above-mentioned reason.The present invention is first
To with gradient-structure two layers of thermoplastic polyurethane/graphene composite material shielding properties and absorbing property expansion research,
And then it spreads to three layers of thermoplastic polyurethane/graphene composite material.
Because thermoplastic polyurethane/grapheme foam similar density, facilitates MULTILAYER COMPOSITE prepared by phase separation method
The design of gradient-structure and homogeneous texture in the process.By taking PUG12, PUG16, PUG20 in embodiment 1 as an example, single layer PUG12 and
The content of graphene and two layers of single layer PUG16 compound material in the compound obtained double-layer composite material (embodiment 1) of PUG20
(comparative example 1) is equal.Therefore, graphene is in gradient in the compound obtained double layer material of PUG12 and PUG20 in embodiment 1
Dispersion, graphene is evenly dispersed in the compound obtained material of bilayer PUG16 in comparative example 1.Similar structure design
Theory is equally applicable in embodiment and comparative example below.
In addition, existing during the test for double-deck thermoplastic polyurethane/grapheme foam in embodiment 1
Two kinds of situations: (1) by the incidence of the face PUG12, across the injection of the face PUG20, (situation is known as positive gradient to electromagnetic wave, in figure 2 and figure 3
Labeled as 12-20)；(2) electromagnetic wave is by the incidence of the face PUG20, pass through the face PUG12 project (situation is known as negative gradient, in Fig. 2 and
Label is in Fig. 3).Since form double-deck thermoplastic polyurethane/graphene composite material in comparative example 1 is two layers of phase
Therefore same PUG16 only exists a kind of situation during the test, i.e., the face PUG16 is incident and projects through the face PUG16, should
Situation is labeled as 16-16 in figure 2 and figure 3.Finally, to two kinds of composite materials prepared in above-described embodiment 1 and comparative example 1
Three kinds of situations using vector network analyzer carry out electromagnetic shielding performance test.Their screens in Ku wave band (12~18GHz)
Efficiency is covered as shown in Fig. 2, corresponding electromagnetic wave absorptivity and reflectivity comparison diagram is as shown in Figure 3.
The result shows that: (1) gradient-structure have no significant effect the shield effectiveness of multilayer materials, has positive gradient (right
Answer the 12-20 in embodiment 1) and negative gradient (20-12 in corresponding embodiment 1) structure two kinds of thermoplastic polyurethane/graphite
The electromagnet shield effect curve of alkene double-layer composite material essentially coincide (~23-31dB) and compared with comparative example 1 it is slightly higher~2dB；(2) terraced
Degree structure has larger impact to the absorbing property of multilayer materials, and positive gradient structure is compared with negative gradient structure to incoming electromagnetic wave energy
The high 10-15% of the absorptivity of amount, the low 10-15% of reflectivity；(3) for compared with comparative example 1, positive gradient structure is to incoming electromagnetic wave energy
The absorptivity of amount improves 6~10%, and reflectivity reduces 6~10%；In contrast, with the double-deck thermoplastic of negative gradient structure
For property polyurethane/graphene foamed material absorbing property compared with comparative example 1 low 6~7%, reflectivity is high by 6~7%.
In view of positive gradient structure in multilayer materials stronger absorbing property, just to have positive ladder in following embodiment
The multilayer materials for spending structure test their electromagnetic shielding and absorbing property as a kind of preference.
Embodiment 2
Material therefor in the present embodiment is PUG8 and PUG16 prepared in embodiment 1, they are pressed graphene content
Sequence from small to large is bonded with PU glue, forms the double-deck thermoplastic polyurethane/graphite with graphene concentration gradient
Alkene foamed material.
Comparative example 2
Two layers of the PUG12 prepared in embodiment 1 is bonded.
The two kinds of composite materials prepared to embodiment 2 and comparative example 2 carry out electromagnetic wave shielding using vector network analyzer
It can test.The result shows that: (1) two kind composite materials shield effectiveness Ku wave band in be 23~24dB, and gradient-structure is to more
The shield effectiveness of layer composite material has no significant effect；(2) with thermoplastic polyurethane/graphene foamed material of positive gradient structure
10~12% is improved compared with comparative example 2 to the absorptivity of incoming electromagnetic wave energy in Ku wave band, reflectivity reduces 10~
12%.
Embodiment 3
Material therefor in the present embodiment is PUG4 and PUG12 prepared in embodiment 1, they are pressed graphene content
Sequence from small to large is bonded with PU glue, forms the double-deck thermoplastic polyurethane/graphite with graphene concentration gradient
Alkene foamed material.
Comparative example 3
Two layers of the PUG8 prepared in embodiment 1 is bonded.
The two kinds of composite materials prepared to embodiment 3 and comparative example 3 carry out electromagnetic wave shielding using vector network analyzer
It can test.The result shows that: (1) two kind composite materials shield effectiveness Ku wave band in be 15~18dB, and gradient-structure is to more
The shield effectiveness of layer composite material has no significant effect；(2) the double-deck thermoplastic polyurethane with positive gradient structure/graphene foaming
Material improves 5~20% compared with comparative example 4 to the absorptivity of incoming electromagnetic wave energy in Ku wave band, and reflectivity reduces 5~
20%.
Embodiment 4
Material therefor in the present embodiment is PUG4, PUG8 and PUG12 prepared in embodiment 1, they are pressed PUG4 │
PUG8 │ PUG12 and PUG4 │ PUG12 │ PUG8 sequence is bonded with PU glue, and forming two kinds has graphene concentration gradient
Three layers of thermoplastic polyurethane/graphene composite foam material.
Comparative example 4
Prepare in embodiment 1 three layers of PUG8 are bonded.
Finally, three kinds of situations to three kinds of composite materials prepared in above-described embodiment 4 and comparative example 4 use vector net
Network analyzer carries out electromagnetic shielding performance test.It is main for three layers of thermoplastic polyurethane/grapheme foam in embodiment 4
Test two kinds of situations: (1) electromagnetic wave passes through PUG8 by PUG4 incidence, projects (the positive ladder in corresponding diagram 4 and Fig. 5 from PUG12
Degree is labeled as 4-8-12)；(2) electromagnetic wave passes through PUG12 by PUG4 incidence, projects from PUG8 (double in corresponding diagram 4 and Fig. 5
Gradient is labeled as 4-12-8).Since the sample in comparative example 4 is three layers of PUG8 composite material, only exist during the test
A kind of situation is labeled as 8-8-8 in figures 4 and 5.Finally, they Ku wave band shield effectiveness as shown in figure 4, corresponding
Electromagnetic wave absorptivity and reflectivity comparison diagram it is as shown in Figure 5.
The result shows that: (1) three kind composite materials shield effectiveness Ku wave band in be 18~26dB, and gradient-structure is to more
The shield effectiveness of layer composite material has no significant effect；(2) gradient-structure is affected to the absorbing property of multilayer materials,
Three layers of thermoplastic polyurethane with double gradient-structures/suction of the graphene foamed material in Ku wave band to incoming electromagnetic wave energy
Yield improves 15~20% compared with comparative example 4, and reflectivity reduces 15~20%；(3) with three layers of thermoplastic of positive gradient structure
Property polyurethane/graphene foamed material improves 5 compared with comparative example 4 to the absorptivity of incoming electromagnetic wave energy in Ku wave band~
10%, reflectivity reduces 5~10%.In view of double gradients and positive gradient structure in terms of improving multilayer materials absorbing property
Advantage, the present invention just using they as two kinds of preferred structures be applied to following embodiment in.
Embodiment 5
Material therefor in the present embodiment is PUG8, PUG12 and PUG16 prepared in embodiment 1, they are pressed PUG8
The sequence of │ PUG12 │ PUG16 (positive gradient structure) and PUG8 │ PUG16 │ PUG12 (double gradient-structures) are bonded with PU glue,
Form the three layers of thermoplastic polyurethane/graphene foamed material with graphene concentration gradient.
Comparative example 5
Prepare in embodiment 1 three layers of PUG12 are bonded.
The three kinds of composite materials prepared to embodiment 5 and comparative example 5 carry out electromagnetic wave shielding using vector network analyzer
It can test.The result shows that: (1) three kind composite materials shield effectiveness Ku wave band in be 28~37dB, and gradient-structure is to more
The shield effectiveness of layer composite material has no significant effect；(2) there is three layers of thermoplastic polyurethane/graphene foaming of double gradient-structures
Material improves 17~20% compared with comparative example 5 to the absorptivity of incoming electromagnetic wave energy in Ku wave band, and reflectivity reduces 17
~20%；(3) three layers of thermoplastic polyurethane/graphene foamed material with positive gradient structure is in Ku wave band to incoming electromagnetic
The absorptivity of wave energy improves 12~20% compared with comparative example 5, and reflectivity reduces 12~20%.
Embodiment 6
Material therefor in the present embodiment is PUG12, PUG16 and PUG20 prepared in embodiment 1, they are pressed
The sequence of PUG12 │ PUG16 │ PUG20 (positive gradient structure) and PUG12 │ PUG20 │ PUG16 (double gradient-structures) with PU glue into
Row bonding forms two kinds of three layers of thermoplastic polyurethane/graphene foamed materials with graphene concentration gradient.
Comparative example 6
Prepare in embodiment 1 three layers of PUG16 are bonded.
The three kinds of composite materials prepared to embodiment 6 and comparative example 6 carry out electromagnetic wave shielding using vector network analyzer
It can test.The result shows that: (1) three kind composite materials shield effectiveness Ku wave band in be 32~45dB, and gradient-structure is to more
The shield effectiveness of layer composite material has no significant effect；(2) there is three layers of thermoplastic polyurethane/graphene foaming of double gradient-structures
Material improves 15~22% compared with comparative example 6 to the absorptivity of incoming electromagnetic wave energy in Ku wave band, and reflectivity reduces 15
~22%；(3) three layers of thermoplastic polyurethane/graphene foamed material with positive gradient structure is in Ku wave band to incoming electromagnetic
The absorptivity of wave energy improves 12~20% compared with comparative example 6, and reflectivity reduces 12~20%.
Claims (8)
1. a kind of thermoplastic polyurethane/graphene foamed material preparation method characterized by comprising
(1) it disperses graphene in organic solvent, obtains mixed solution after thermoplastic polyurethane elastomer stirring and dissolving is added, it will
Mixed solution pours into and carries out precipitating in coagulating bath, and thermoplastic polyurethane/graphene mixture of precipitation crushes after being dried；
(2) thermoplastic polyurethane obtained in step (1)/graphene mixture is dissolved in organic solvent, obtains mixing casting
Film liquid carries out film with scraper and is mutually separated, and is dried after obtaining thermoplastic polyurethane/graphene fretting map film；
(3) thermoplastic polyurethane obtained in step (2)/graphene fretting map film is subjected to multiple-layer stacked, between layers
It is bonded with glue, forms integrated thermoplastic polyurethane/graphene foamed material；
In step (3), the thermoplastic polyurethane/graphene foamed material is by 3~100 layers of monolayer thermoplastic's polyurethane/stone
Black alkene fretting map film is first incremented by by the content of graphene in matrix successively decreases afterwards or is first incremented by the rear constant rule progress successively decreased again
Superposition.
2. thermoplastic polyurethane according to claim 1/graphene foamed material preparation method, which is characterized in that step
Suddenly in the mixed solution of (1), the mass ratio of the graphene, thermoplastic polyurethane elastomer and organic solvent be 1~30:70~
99:1000~2500.
3. thermoplastic polyurethane according to claim 1/graphene foamed material preparation method, which is characterized in that step
Suddenly in (2), phase separation includes: that mixed solution is poured into scraper to carry out film and be exposed to temperature to be 0~50 DEG C and opposite
Humidity carries out in the environment of being 50~99%, and the time of phase separation is 0.1~for 24 hours；The drying temperature is 20~80
℃。
4. thermoplastic polyurethane according to claim 1/graphene foamed material preparation method, which is characterized in that step
Suddenly in (2), it is described mixing casting solution with a thickness of 0.001~5mm.
5. thermoplastic polyurethane according to claim 1/graphene foamed material preparation method, which is characterized in that step
Suddenly in (2), the thermoplastic polyurethane/graphene fretting map film pore size is 1~15 μm, with a thickness of 100~400 μ
m。
6. a kind of thermoplastic polyurethane/graphene foamed material, which is characterized in that the thermoplastic polyurethane/graphene foaming
According to claim 1 ,~5 described in any item methods are prepared material.
7. a kind of application of thermoplastic polyurethane according to claim 6/graphene foamed material, which is characterized in that institute
State thermoplastic polyurethane/application of the graphene foamed material in electromagnetic shielding field.
8. a kind of application of thermoplastic polyurethane according to claim 6/graphene foamed material, which is characterized in that institute
State thermoplastic polyurethane/application of the graphene foamed material in absorbing material field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610919480.0A CN106566226B (en) | 2016-10-21 | 2016-10-21 | A kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610919480.0A CN106566226B (en) | 2016-10-21 | 2016-10-21 | A kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106566226A CN106566226A (en) | 2017-04-19 |
| CN106566226B true CN106566226B (en) | 2019-04-02 |
Family
ID=58534034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610919480.0A Active CN106566226B (en) | 2016-10-21 | 2016-10-21 | A kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106566226B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774390B (en) * | 2018-06-22 | 2021-03-16 | 四川大学 | Layered foam wave-absorbing material and preparation method thereof |
| CN108770327B (en) * | 2018-06-22 | 2020-05-12 | 四川大学 | Gradient layered foamed wave-absorbing material and preparation method thereof |
| CN109438988A (en) * | 2018-11-06 | 2019-03-08 | 四川大学 | A kind of composite elastic body foamed material and preparation method thereof |
| CN110526239A (en) * | 2019-09-20 | 2019-12-03 | 黄淮学院 | A kind of graphene fine-celled foam and its preparation method and application |
| CN113086977B (en) * | 2020-01-08 | 2022-08-02 | 广东墨睿科技有限公司 | Preparation method of double-layer graphene oxide film |
| CN112969356A (en) * | 2021-01-19 | 2021-06-15 | 西安理工大学 | Preparation method of polyurethane/graphene nanosheet/sponge composite material |
| CN113121982B (en) * | 2021-04-20 | 2022-05-31 | 浙江优可丽新材料有限公司 | Absorption loss type gradient structure composite electromagnetic shielding material and preparation method thereof |
| CN114621497B (en) * | 2022-04-22 | 2023-01-10 | 福州大学 | Preparation method of gradient macroporous conductive composite hydrogel for flexible strain sensor |
| CN115500067B (en) * | 2022-09-02 | 2023-08-29 | 苏州申赛新材料有限公司 | Electromagnetic shielding composite material with low-reflection magneto-electric dual-functional gradient structure |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11261288A (en) * | 1998-03-11 | 1999-09-24 | Sumitomo Bakelite Co Ltd | Electromagnetic wave shielding transparent member |
| JP2010065123A (en) * | 2008-09-10 | 2010-03-25 | Teijin Ltd | Heat-conductive molding |
| CN102702562A (en) * | 2012-05-24 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method for thermoplastic polyimide foaming particle and formed body thereof |
| CN104151521A (en) * | 2014-07-30 | 2014-11-19 | 北京市射线应用研究中心 | Polyurethane imide-graphene/nanometer carbon fiber blending wave-absorbing foam material and preparation method thereof |
| CN104497263A (en) * | 2014-11-28 | 2015-04-08 | 瀚寅(苏州)新材料科技有限公司 | Nano-modified polyurethane packaging material and preparation method thereof |
| CN104592477A (en) * | 2015-02-16 | 2015-05-06 | 中北大学 | Preparation method of high-performance magnetic polyurethane elastomer composites |
| CN105555112A (en) * | 2016-01-22 | 2016-05-04 | 武汉理工大学 | Electromagnetic shielding composite material |
| CN105694427A (en) * | 2014-11-26 | 2016-06-22 | 中国科学院金属研究所 | Application of graphene composite material electromagnetic shielding material |
| KR20160108747A (en) * | 2015-03-06 | 2016-09-20 | 주식회사 미래텍 | Polyurethane foam for vehicle interior having electric wave preventing function and manufacturing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITRM20120495A1 (en) * | 2012-10-16 | 2014-04-17 | Univ Roma | "GNP POLYMERIC NANOCOMPOSITES FOR THE REDUCTION OF ELECTROMAGNETIC INTERFERENCES" |
| US9731456B2 (en) * | 2013-03-14 | 2017-08-15 | Sabic Global Technologies B.V. | Method of manufacturing a functionally graded article |
-
2016
- 2016-10-21 CN CN201610919480.0A patent/CN106566226B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11261288A (en) * | 1998-03-11 | 1999-09-24 | Sumitomo Bakelite Co Ltd | Electromagnetic wave shielding transparent member |
| JP2010065123A (en) * | 2008-09-10 | 2010-03-25 | Teijin Ltd | Heat-conductive molding |
| CN102702562A (en) * | 2012-05-24 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method for thermoplastic polyimide foaming particle and formed body thereof |
| CN104151521A (en) * | 2014-07-30 | 2014-11-19 | 北京市射线应用研究中心 | Polyurethane imide-graphene/nanometer carbon fiber blending wave-absorbing foam material and preparation method thereof |
| CN105694427A (en) * | 2014-11-26 | 2016-06-22 | 中国科学院金属研究所 | Application of graphene composite material electromagnetic shielding material |
| CN104497263A (en) * | 2014-11-28 | 2015-04-08 | 瀚寅(苏州)新材料科技有限公司 | Nano-modified polyurethane packaging material and preparation method thereof |
| CN104592477A (en) * | 2015-02-16 | 2015-05-06 | 中北大学 | Preparation method of high-performance magnetic polyurethane elastomer composites |
| KR20160108747A (en) * | 2015-03-06 | 2016-09-20 | 주식회사 미래텍 | Polyurethane foam for vehicle interior having electric wave preventing function and manufacturing the same |
| CN105555112A (en) * | 2016-01-22 | 2016-05-04 | 武汉理工大学 | Electromagnetic shielding composite material |
Non-Patent Citations (9)
| Title |
|---|
| "Flexible graphene/polymer composite films in sandwich structures for effective electromagnetic interference shielding";Wei-Li Song，等;《ScienceDirect》;20141231;第66卷(第1期);第65-76页 * |
| "Gradient multilayer structural design of CNTs/SiO composites for improving microwave absorbing properties";Mingxia Chen，等;《Materials and Design》;20110114;第32卷(第5期);第3013-3016页 * |
| "Polyimide/Graphene Composite Foam Sheets with Ultrahigh Thermostability for Electromagnetic Interference Shielding";Yang Li，等;《RSC Advances》;20151231;第5卷(第31期);第24342-24351页 * |
| "单层和多层蜂窝结构吸波材料";华家宝，等;《宇航材料工艺》;19891231(第4-5期);第65-70页 * |
| "微孔发泡聚酰亚胺电磁屏蔽复合材料的制备与表征";凌建强;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140815(第08期);第B014-273页 * |
| "结构型吸波复合材料的研究进展";李俊燕，等;《纤维复合材料》;20120630(第2期);第11-14页 * |
| "聚氨酯功能梯度材料的研究现状与展望";周成飞;《化工技术与开发》;20130531;第42卷(第5期);第9-13页 * |
| Yang Li，等."Polyimide/Graphene Composite Foam Sheets with Ultrahigh Thermostability for Electromagnetic Interference Shielding".《RSC Advances》.2015,第5卷(第31期),第24342-24351页. * |
| 凌建强."微孔发泡聚酰亚胺电磁屏蔽复合材料的制备与表征".《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2014,(第08期),第B014-273页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106566226A (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106566226B (en) | A kind of thermoplastic polyurethane/graphene foamed material and its preparation method and application | |
| Zhu et al. | Ultralight, compressible, and anisotropic MXene@ Wood nanocomposite aerogel with excellent electromagnetic wave shielding and absorbing properties at different directions | |
| Wang et al. | Review on shielding mechanism and structural design of electromagnetic interference shielding composites | |
| Bora et al. | Electromagnetic interference shielding efficiency of MnO2 nanorod doped polyaniline film | |
| CN106183136B (en) | A kind of electromagnetic shielding composite material material and its preparation and application | |
| CN106564227A (en) | Polymer/graphene foamed material with electromagnetic shielding performance, and preparation method and application thereof | |
| Naghdi et al. | Graphene family, and their hybrid structures for electromagnetic interference shielding applications: Recent trends and prospects | |
| Chen et al. | Enhanced electromagnetic interference shielding properties of carbon fiber veil/Fe3O4 nanoparticles/epoxy multiscale composites | |
| Vasconcelos da Silva et al. | Glass fiber/carbon nanotubes/epoxy three‐component composites as radar absorbing materials | |
| CN108003364A (en) | A kind of Flexible graphene group compound film and preparation method thereof and the application as electromagnetic shielding material | |
| Karim et al. | Future advances and challenges of nanomaterial-based technologies for electromagnetic interference-based technologies: A review | |
| CN105670560A (en) | Preparation method of nano-cobalt oxide/graphene composite wave-absorbing coating | |
| Antony Vincent et al. | Fabrication and characterization of hybrid natural fibre-reinforced sandwich composite radar wave absorbing structure for stealth radomes | |
| He et al. | Preparation and microwave absorption properties of metal magnetic micropowder-coated honeycomb sandwich structures | |
| CN109573988A (en) | A kind of graphene composite aerogel absorbing material and its preparation method and application | |
| Salem et al. | Electrospun PVDF/Barium hexaferrite fiber composites for enhanced electromagnetic shielding in the X-band range | |
| Zhan et al. | Simple approach to fabricate MXene/cellulose paper for electromagnetic interference shielding applications | |
| Zachariah et al. | From waste to wealth: A critical review on advanced materials for EMI shielding | |
| Yeswanth et al. | Recent developments in RAM based MWCNT composite materials: a short review | |
| Verma et al. | A review on efficient electromagnetic interference shielding materials by recycling waste—A trio of land to lab to land concept | |
| CN110054182A (en) | A kind of magnetic graphite alkenyl inhales wave cellular material and preparation method thereof | |
| CN114150496A (en) | Flexible nanofiber membrane with electromagnetic shielding and piezoresistive sensing performances and preparation method thereof | |
| Huang et al. | A graphene-based compatible flexible film with ultra-wideband microwave absorption and low infrared emissivity | |
| CN109971300A (en) | A kind of microwave absorbing coating and preparation method thereof | |
| Silveira et al. | Microwave absorbing properties of glass fiber/epoxy resin composites tailored with frequency selective surface based on nonwoven of carbon fibers metalized with nickel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |