CN106319488B - Beading FeNi alloy-coated CNTs/PDMS flexible composite films and preparation method - Google Patents
Beading FeNi alloy-coated CNTs/PDMS flexible composite films and preparation method Download PDFInfo
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- CN106319488B CN106319488B CN201610810943.XA CN201610810943A CN106319488B CN 106319488 B CN106319488 B CN 106319488B CN 201610810943 A CN201610810943 A CN 201610810943A CN 106319488 B CN106319488 B CN 106319488B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- B22F1/17—Metallic particles coated with metal
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
Abstract
The present invention relates to beading FeNi alloy-coated CNTs/PDMS flexible composite films and preparation methods；The carbon nano-tube film prepared using chemical vapour deposition technique is restrained surface in carbon as matrix, by chemical plating and coats iron-nickel alloy coating to improve its capability of electromagnetic shielding：Carbon nanotube is sensitized using stannous chloride, palladium bichloride activates carbon nanotube, under divalent tin ion effect one layer of palladium chtalyst active site of external sediment is restrained in carbon nanotube, centered on this catalytic activity point, iron nickel particle is with global deposition and is coated in carbon nanotube tube bank, one layer of continuous, fine and close alloy layer is formed, the microstructure of the continuous enveloped carbon nanometer tube tube bank of spherical alloy particle " beading " is obtained.Prepare this iron nickel@carbon nano-tube/poly dimethyl siloxane flexible composite film.It can be applied to electronic equipment, electronics industry, information technology, aerospace, the electromagnetic wave shielding field in national defense and military.
Description
Technical field
The present invention relates to one kind " beading " FeNi@CNTs/PDMS flexible electromagnetic shielding laminated films and preparation method thereof,
Belong to high band electromagnetic screen film material field, can be applied to the information technology fields such as electronic equipment, electronics industry, army
The ELECTROMAGNETIC RADIATION SHIELDING in the fields such as thing.
Background technology
Carbon nanotube (CNTs) can regard graphite flake as and be curled into seamless tubular shaped nanofiber, have good conductive property and
Higher dielectric constant, prodigious draw ratio and great specific surface area, it is a kind of new that these properties all so that CNTs has been used as
The nano electromagnetic of type shields (EMI SE) material obturator, is added in the high molecular materials such as epoxy resin, polyurethane, can make
It is standby go out high performance electromagnetic shielding material.Studies have shown that novel C NTs/ polymer composites have under relatively low bias-voltage
Tuneable dielectric properties, and there is excellent electromagnetic performance in high-frequency region (2~18GHz).Therefore, CNTs is as conductive
Filling mutually receives significant attention in electromagnetic shielding material field, has been applied to electronics industry.It is led in military security equipment
There is important application prospect in domain.However, since CNTs surface defects and microstructure directly affect the electromagnetic wave shielding of CNTs
Can, CNTs and highly conductive and high magnetic permeability metal composite are become into the active material in terms of current electromagnetic shielding research.It is domestic
Outer researcher has utilized the magnetic metal nano particle by high magnetic permeability such as electrochemical deposition method, electroless plating method, galvanoplastic
The surfaces CNTs are deposited on, the composite material of CNTs/ metals is prepared.Since metal is a kind of good conductor, and magnetic metal iron
(Fe), cobalt (Co), nickel (Ni) have high magnetic permeability, have a clear superiority in terms of electromagnetic wave absorption, therefore in CNTs/ metals now
In the research of composite electromagnetic shield materials, the selection of metal is concentrated mainly on the magnetic connection metal such as iron, cobalt, nickel.It is as high
Frequency screen can obtain maximum absorption loss and reflection loss, and CNTs has great specific surface area can be further
Reflection loss is improved, therefore the more simple CNTs of this kind of composite material or metal material have more excellent capability of electromagnetic shielding.And
And compared with, rigidity height big with weight, perishable conventional metals, this composite material has lightweight, more excellent chemistry resistance to
The performances such as corrosivity, stability, high frequency dispersion.
In addition, as the electromagnetic shielding material used in the fields such as electronics industry, military affairs is to requirements such as plasticity, frivolous property
It improves year by year, the research of flexible electromagnetic shielding material increasingly obtains extensive favor.And development trend gradually from powder type coating preparation to
Film-like material direction changes.Since CNTs also has stronger advantage in mechanical property, CNTs is gradually used for flexible material
The correlative study of the preparation of material, CNT flexible electromagnetic shielding materials is also gradually developed.Simultaneously as PDMS has producing high-molecular
The outstanding obdurability of object, strong moulding is closed, therefore it can be utilized to enhance toughness, the plasticity of laminated film.Due to complex process etc.
Reason, the in recent years research of flexible electromagnetic shielding material just start, also in the preliminary stage, and most of research work
Have focused largely on diaphragm type CNTs/ polymer composites.The method of generally use dispersion is by CNTs powder and high score flexible
Subbase body (such as polystyrene) carries out compound.Due to having strong Van der Waals force between CNTs, easily reunites, lead to the dispersion of CNTs
Property is poor, and the conductive network for being hardly formed in macromolecule matrix connection directly affects to affect the electric conductivity of material
Its capability of electromagnetic shielding.
Invention content
Carbon nano-tube film is preparing flexible electromagnetic shielding material side's rice with advantage outstanding, this is because carbon nano-tube film
The effects that middle carbon nanotube passes through Van der Waals force connects into three-dimensional network, can be used as carrier directly with metal, high molecular material
It etc. compound, and can be very good in recombination process to keep this three-dimensional network, to improve the electric conductivity of material.And it uses
Carbon nano-tube film replaces carbon nanotube powder that can effectively solve the scattering problem of carbon nanotube in the base.Therefore, in conjunction with existing
Modern information technology field is to the demand and electromagnetic shielding material current situation of high band electromagnetic wave high-performance electromagnetic shielding material, profit
Preparation advantage in terms of carbon nano-tube film, a kind of Armco magnetic iron nickel alloy nanoparticles of this project proposition and carbon nano tube flexible
The design of film composite material innovatively proposes a kind of continuous enveloped carbon nanometer tube tube bank of spherical alloy particle " beading "
Microstructure, it is compound after flexible material integrally have lightweight, ultra-thin, strong plasticity, high electromagnet shield effect etc. multinomial superior
Performance can replace conventional metals shielding material, adapt to the huge of modern military information war, stealth aircraft, privacy device etc.
Big demand.
The carbon nano-tube film of the present invention and the compound flexible electromagnetic shielding thin-film material of ferromagnetic metal alloy.Microstructure is
The continuous enveloped carbon nanometer tube tube bank of spherical alloy particle " beading ".This laminated film have lightweight, ultra-thin, strong plasticity,
The multinomial superior function such as high electromagnet shield effect, can be applied to the electricity of the information technology fields such as electronic equipment and electronics industry
Magnetic radiation shields.
The flexible electromagnetic shielding film of the present invention is the carbon nano-tube film that is prepared using chemical vapour deposition technique as matrix, is passed through
Chemical plating coats iron-nickel alloy coating to improve its capability of electromagnetic shielding on carbon tube bank surface：Using stannous chloride to carbon nanotube
It is sensitized, palladium bichloride activates carbon nanotube, and one layer of external sediment is restrained in carbon nanotube under divalent tin ion effect
Palladium chtalyst active site, centered on this catalytic activity point, iron nickel particle is with global deposition and is coated in carbon nanotube tube bank, shape
At one layer of continuous, fine and close alloy layer, the microcosmic of the continuous enveloped carbon nanometer tube tube bank of spherical alloy particle " beading " is obtained
Structure.Through being filtered, washed, drying, impregnate dimethyl silicone polymer, standing and drying, this iron nickel carbon nano-tube/poly is prepared
Dimethyl siloxane flexible composite film.
" beading " iron nickel@carbon nanotube three-dimensional pilotaxitic textures of the flexible electromagnetic shielding film of the present invention are as shown in Figure 8.
Technical scheme is as follows：
The beading iron-nickel alloy enveloped carbon nanometer tube film of the present invention；Microstructure is that spherical alloy particle beading is continuous
Enveloped carbon nanometer tube is restrained.
The preparation method of the beading iron-nickel alloy enveloped carbon nanometer tube film of the present invention；
1) carbon nanotube sensitization, activation process：Using stannous chloride as sensitizer, using palladium bichloride as activator, will pass through pure
The carbon nanotube for changing processing is immersed in ultrasonic disperse progress sensitized treatment in stannous chloride solution, then is immersed in palladium chloride solution
Ultrasonic disperse carries out activation process；
2) chemical plating fluid is configured：Using nickel sulfate and iron ammonium sulfate as source metal, using sodium hypophosphite as reducing agent, with wine
Stone acid potassium sodium is complexing agent, adjusts pH=9~11 using ammonium sulfate as buffer, with ammonium hydroxide, configures chemical plating fluid；
3) reducing agent replenisher is configured：Ammonium sulfate is added in ortho phosphorous acid sodium solution, ammonium hydroxide is added dropwise and adjusts pH=9
~11, configure reducing agent replenisher；
4) chemical plating fluid that carbon nano-tube film is immersed to step 1) carries out the stirring of first time constant temperature magnetic, ultrasonic disperse successively,
The stirring of second constant temperature magnetic, a dropping step 2 while second of constant temperature magnetic stirs) the reducing agent replenisher for preparing；Iron is made
Nickel@carbon nano-tube compound films；
5) iron nickel@carbon nano-tube compound films are soaked into the dimethyl silicone polymer added with curing agent, wait for that outer layer wraps completely
It is put into curing oven after wrapping up in a strata dimethyl siloxane, it is thin to obtain iron nickel@carbon nano-tube/poly dimethyl siloxane flexible compounds
Film.
Carbon nano-tube film can carry out purifying pretreatment：By carbon nano-tube film made from chemical vapour deposition technique through too strong
The impurity such as the metallic catalyst of alkali, the purifying removal amorphous carbon of strong acid and remaining, then washed and dried.
Optimum condition is as follows：
A concentration of 0.08~0.12mol/L of stannous chloride solution, activation process are 20~30min of ultrasonic disperse.
A concentration of 0.66~3.15mmol/L of palladium chloride solution, activation process are 20~30min of ultrasonic disperse.
Concentration of nickel sulfate is 0.08~0.09mol/L, the nickel sulfate of addition and the solute molality ratio of iron ammonium sulfate
It is 3~4:1.
The solute molality of sodium hypophosphite and nickel sulfate ratio is 0.5~2.5:1.
A concentration of 0.15~0.2mol/L of complexing agent potassium sodium tartrate solution.
A concentration of 0.1~0.15mol/L of buffer ammonium sulfate
The solute molality ratio of nickel sulfate is 2 in sodium hypophosphite and plating solution in reducing agent replenisher:1, reducing agent is mended
Filling liquid and plating solution total volume ratio are 1:1.
It purifies in preprocessing process, a concentration of 0.3mol of strong base solution NaOH solution, 40 DEG C of water-bath 1h；In mixed acid solution
Dense H2SO4With dense HNO3Volume ratio is 2:5, impregnate 10h；
The present invention provides it is a kind of prepare iron nickel@carbon nano-tube/polies dimethyl siloxane flexible electromagnetic shielding film and its
Preparation method, for developing the development significant application value of high band electromagnetic shielding material.The laminated film is different from common
Using carbon nanotube powder as the carbon nanotube@macromolecule composite shielding materials of filler.The technical characteristic of the present invention is received with carbon
Mitron film is matrix, and by regulating and controlling the content and ratio of iron, nickel, reducing agent in plating solution, iron-nickel alloy is realized using electroless plating method
Particle obtains the continuous enveloped carbon nanometer tube tube bank of spherical alloy particle " beading " to the continuous cladding of the densification of carbon nano-tube bundle
Microstructure.By the way of wrapping dimethyl silicone polymer in iron nickel@carbon nano-tube compound film outer layers, further enhance compound
The flexibility and mechanical strength of film.
The electromagnetic shielding of iron nickel@carbon nano-tube/poly dimethyl siloxane flexible electromagnetic shielding films prepared by the above method
Performance carries out shielding properties test at 8~12GHz, and shielding properties reaches nearly 20dB at 10~11GHz.Therefore the present invention can answer
Electromagnetic wave shielding field in electronic equipment, electronics industry, information technology, aerospace, national defense and military.
Description of the drawings
Fig. 1：The optical photograph of FeNi@CNTs composite membranes prepared by the embodiment of the present invention 2.
Fig. 2：The electron scanning micrograph of 1CNTs films of the embodiment of the present invention.
Fig. 3：The electron scanning micrograph of FeNi@CNTs composite membranes prepared by the embodiment of the present invention 1.
Fig. 4：The capability of electromagnetic shielding curve of FeNi@CNTs/PDMS composite membranes prepared by the embodiment of the present invention 1.
Fig. 5：The electron scanning micrograph of FeNi@CNTs composite materials prepared by the embodiment of the present invention 3.
Fig. 6：The electron scanning micrograph of FeNi@CNTs composite materials prepared by the embodiment of the present invention 5.
Fig. 7：The electron scanning micrograph of FeNi@CNTs composite materials prepared by the embodiment of the present invention 7.
Fig. 8：" beading " iron nickel carbon nanotube three-dimensional single fisherman's knot composition of flexible electromagnetic shielding film.
Specific implementation mode
The preparation method of the flexible composite film of the present invention, CNTs films made from chemical vapour deposition technique (CVD) are carried out
Purifying, stannous chloride (SnCl2·2H2O it) is sensitized, palladium bichloride (PdCl2) activated；Electroless plating method is recycled, with sulfuric acid
Nickel (NiSO4.6H2O), iron ammonium sulfate ((NH4)2Fe(SO4)2.6H2O it is) source metal, with sodium hypophosphite (NaH2PO2.H2O)
It carries out redox reaction and deposits iron nickel (FeNi) alloy layer in CNTs tube banks；Obtained iron nickel@carbon nanotubes (FeNi@
CNTs) composite membrane is soaked into dimethyl silicone polymer (PDMS) to enhance its overall flexibility and mechanical strength, obtains iron nickel@carbon and receives
Mitron/dimethyl silicone polymer (FeNi@CNTs/PDMS) flexible composite film.
Above-mentioned electromagnetic shielding FeNi@CNTs/PDMS flexible composite films；It is characterized in that using CNTs films as matrix,
CNTs restrains outer cladding spherical shape FeNi alloy nanoparticles, forms fine and close, continuous " beading " coating structure, outermost layer package
PDMS flexible, with excellent corrosion protection and heat-resisting quantity.
The preparation method of above-mentioned FeNi@CNTs/PDMS flexible composite films, it is characterized in that using the method for chemical plating,
Detailed process includes：1. the pretreatment of CNTs films：CNTs films are by highly basic, the gold of purifying the removal amorphous carbon and remaining of strong acid
The impurity such as metal catalyst are immersed in SnCl after washed and dry2In solution, ultrasonic disperse carries out sensitized treatment, then is immersed in
PdCl2In solution, ultrasonic disperse carries out activation process, then washed, suction filtration, drying for standby；2. configuring chemical plating fluid：With
NiSO4·6H2O is the sources Ni, (NH4)2Fe(SO4)2·6H2O is the sources Fe, sodium potassium tartrate tetrahydrate (C4H4KNaO6·4H2Be O) complexing agent,
NaH2PO2For reducing agent, ammonium sulfate [(NH4)2SO4] it is buffer, pH=9~11 are adjusted with ammonium hydroxide, configure chemical plating fluid；3. matching
Set reducing agent replenisher：In NaH2PO2(NH is added in solution4)2SO4Solution is added dropwise ammonium hydroxide and adjusts pH=9~11, configuration reduction
Agent replenisher；4. chemically plating is for FeNi@CNTs composite membranes：CNTs films immersion chemical plating fluid carries out first time constant temperature magnetic and stirs successively
It mixes, ultrasonic disperse, second of constant temperature magnetic stir, dropwise addition reducing agent replenisher while second of constant temperature magnetic stirs, by upper
It states redox reaction and deposits FeNi Nanoparticulate alloy layers on the tube bank surface of carbon nanotube, then be washed with distilled water to
Neutrality, through being dried to obtain FeNi@CNTs composite membranes；5. compound with PDMS：FeNi@CNTs composite membranes are soaked into and are added with quality
In the PDMS of 10% curing agent, it is put into curing oven after the fully wrapped around one layer of PDMS of outer layer, obtains FeNi@CNTs/PDMS
Flexible composite film.
Above-mentioned preparation method, it is characterized in that NaH2PO2/NiSO4Molar ratio and PdCl2Dosage to obtain beading
FeNi particles are most important, NaH2PO2/NiSO4Molar ratio controls FeNi granular sizes, PdCl2Dosage control FeNi particle balls
Shape degree and continuity degree.
Above-mentioned preparation method, it is characterized in that SnCl2A concentration of 0.08~the 0.12mol/L, PdCl of solution2It is a concentration of
0.66~3.15mmol/L
Above-mentioned preparation method, it is characterized in that NiSO in chemical plating fluid4A concentration of 0.08~0.09mol/L, addition
NiSO4·6H2O and (NH4)2Fe(SO4)2·6H2Ni the and Fe atomic molar ratios of O are 3:1~4:1.
Above-mentioned preparation method, it is characterized in that reducing agent NaH in chemical plating fluid2PO2With NiSO4Solute molar ratio be
0.5:1~2.5:1.
Above-mentioned preparation method, it is characterized in that chemical plating fluid complexing agent C4H4KNaO6·4H2O is 0.15~0.2mol/
L, buffer (NH4)2SO4For 0.1~0.15mol/L
Above-mentioned pretreated CNTs films are immersed in by above-mentioned preparation method it is characterized in that after the completion of plating solution configures
It in plating solution and is fixed in the middle part of liquid, deposits FeNi nano particles on CNTs tube banks surface under stirring, that is, realize the anti-of chemical plating
Answer process.Reducing agent replenisher is added dropwise while stirring.
The configuration method of above-mentioned reducing agent replenisher, it is characterized in that in NaH2PO2(NH is added in solution4)2SO4Solution,
Ammonium hydroxide is added dropwise later and carries out pH adjustings, until reducing agent replenisher pH value reaches in 9~11 ranges；Reducing agent replenisher is characterized in
NaH2PO2With NiSO in plating solution4Solute molality ratio be 2:1, reducing agent replenisher and plating solution total volume ratio are 1:1.
Embodiment 1：The purification process of original CNTs films is carried out in such a way that highly basic, nitration mixture impregnate successively.It will be original
CNTs films (0.06g) are immersed in NaOH solution (0.5g, 0.3mol), and it is (dense to be immersed in mixed acid solution after washing by 40 DEG C of water-bath 1h
H2SO4With dense HNO3Volume ratio is 2:5) 10h in；Take out washing, drying for standby.Scanning electron microscope (SEM) proves CNTs films
By above-mentioned alkali, acid processing, CNTs is interbank and tube bank on, the pipe clean by processing such as the irregular shape impurity particle that adheres to
Beam clearly it is exposed outside, and be interleaved with each other and to form network structure.Fig. 1 is the SEM photograph of original CNTs films
SnCl is carried out successively to the above-mentioned CNTs films after alkali, sour purification process2Sensitized treatment and PdCl2Activation
Processing.The CNTs films obtained in embodiment 1 will be immersed in SnCl2·2H2In O solution (0.36g, 0.10mol/L) and it is fixed on
In the middle part of liquid, ultrasonic disperse 30min carries out sensitized treatment；Above-mentioned CNTs films are immersed in PdCl in time after sensitization2Solution
In (1.8mmg, 0.66mmol/L) and fixed, ultrasonic disperse 30min carries out activation process；After the above pretreatment, film is carried out
Washing, suction filtration, drying for standby.
To above-mentioned the compound of FeNi alloys is carried out through CNTs films sensitization plays, after activation process.Plating solution is configured first and is gone back
Former agent replenisher：NiSO is respectively configured4·6H2O solution (1.1705g, 0.089mol/L), (NH4)2Fe(SO4)2·6H2O solution
(0.4935g, 0.025mol/L), potassium sodium tartrate solution (2.5000g, 0.177mol/L), NaH2PO2Solution (0.4907g,
0.089mol/L)、(NH4)2SO4Solution (0.8328g, 0.126mol/L), is added sequentially to 100ml beakers in the order described above
In, it is carried out at the same time and is stirred continuously in mixing, ammonium hydroxide is added dropwise until bath pH value reaches in 9~11 ranges；Wherein NiSO4With
(NH4)2Fe(SO4)2Solute molar ratio be 3.56:1, wherein NaH2PO2And NiSO4Solute molar ratio be 1:1.
Secondly configuration reducing agent replenisher：In NaH2PO2(NH is added in solution (0.5g, 0.094mol/L)4)2SO4Solution
Ammonium hydroxide is added dropwise until reducing agent replenisher pH value reaches in 9~11 ranges in (0.8328g, 0.126mol/L).Reducing agent replenisher
It is characterized in NaH2PO2With NiSO in plating solution4Solute molality ratio be 2:1, reducing agent replenisher and plating solution total volume ratio are
1:1。
Thirdly carry out plating process：Pretreated CNTs films prepared by embodiment 1 are completely soaked into plating solution simultaneously
It is fixed in the middle part of liquid, carries out first time constant temperature magnetic stirring 15min, ultrasonic disperse 30min, second of constant temperature magnetic stirring successively
30min, wherein magnetic whipping process are maintained under the conditions of 50 DEG C of waters bath with thermostatic control, and keep reducing agent to mend while second of magnetic stirring
The at the uniform velocity dropwise addition of filling liquid supplements.Obtain FeNi@CNTs composite membranes.
The compound of PDMS is carried out to the above-mentioned FeNi@CNTs composite membranes after plating process：By plating process
The FeNi@CNTs composite membranes obtained after redox reaction take out, and washing to neutrality is soaked into after dry added with matter
It in PDMS of the amount for 10% curing agent, is put into 50 DEG C of baking oven after the fully wrapped around one layer of PDMS of outer layer, until being taken after solidification
Go out.Obtain FeNi@CNTs/PDMS composite membranes.
Capability of electromagnetic shielding test is carried out to sample using vector network analyzer (Agilent N5242A), Fig. 4 is electricity
Magnetic shield performance test curve.As can be seen from the figure composite films at 10.36GHz shielding properties up to 17.6dB.
Figure of description 2 show the electron scanning micrograph of the original CNTs films used in the present embodiment 1, by Fig. 2
As it can be seen that tube bank is upper in CNTs films and surrounding impurities are more, tube bank has the network-like connection of intersection to each other.
Figure of description 3 show the SEM photograph of the FeNi@CNTs composite membranes of the present embodiment 1.As seen from Figure 3, CNTs tables
It is FeNi alloys that, which there are a large amount of, apparent deposit, deposit in face, and deposit graininess spherical in shape is coated in CNTs tube banks, ball
For shape particle size in~200nm, deposit is in dense packing.The region of partially visible carbon pipe shows that deposit is in " beading "
It is through on carbon tube bank.Therefore, spherical alloy particle " beading " microstructure that continuously cladding CNTs is restrained is obtained.
Explanation is the capability of electromagnetic shielding test knot for the FeNi@CNTs/PDMS composite membranes that attached drawing 4 show the present embodiment 1
Fruit.By electromagnetic shielding test result as it can be seen that the properties of product highest is close to 18dB (10.36GHz), and>The regions 10dB
Absorption band wider range.
Embodiment 2：Using 1 identical method of embodiment, reducing agent NaH in plating solution is changed2PO2With NiSO4Solute mole
Than being 0.5:1, other conditions are constant.Pretreated CNTs is completely soaked into plating solution and is fixed in the middle part of liquid, successively into
Row magnetic stirs 15min, ultrasonic disperse 30min, magnetic and stirs 30min, and wherein magnetic whipping process is maintained at 50 DEG C of water bath with thermostatic control conditions
Under, and keep the at the uniform velocity dropwise addition of reducing agent replenisher to supplement while second of magnetic stirring.After reaction by this FeNi@CNTs
Composite membrane takes out, washing to neutrality, dry.
Figure of description 1 show the optical photograph of the FeNi@CNTs composite membranes of the present embodiment 2.As seen from Figure 1, CNTs
Film is in reducing agent NaH2PO2Without apparent color change, plating effect unobvious when content is relatively low.
Embodiment 3：Using 2 identical method of embodiment, PdCl is changed2Quality (1.9mmg, 0.704mmol/L), other
Condition is constant.Pretreated CNTs is completely soaked into plating solution and is fixed in the middle part of liquid, carry out successively magnetic stirring 15min,
Ultrasonic disperse 30min, magnetic stir 30min, and wherein magnetic whipping process is maintained under the conditions of 50 DEG C of waters bath with thermostatic control, and second of magnetic stirs
The at the uniform velocity dropwise addition supplement of reducing agent replenisher is kept while mixing.This FeNi@CNTs composite material is taken out after reaction, is washed
It washs to neutrality, it is dry.
Figure of description 5 show the electron scanning micrograph of the FeNi@CNTs composite materials of the present embodiment 3.By
Fig. 5 is as it can be seen that change PdCl in smaller range2Dosage, but reducing agent NaH in plating solution2PO2When still very low, deposition is without obviously changing
Kind, FeNi alloying pellets still deposit seldom in CNTs tube banks.
Embodiment 4：Using 3 identical method of embodiment, reducing agent NaH in plating solution is changed2PO2With NiSO4Solute mole
Than being 2.0:1, other conditions are constant.Pretreated CNTs is completely soaked into plating solution and is fixed in the middle part of liquid, successively into
Row magnetic stirs 15min, ultrasonic disperse 30min, magnetic and stirs 30min, and wherein magnetic whipping process is maintained at 50 DEG C of water bath with thermostatic control conditions
Under, and keep the at the uniform velocity dropwise addition of reducing agent replenisher to supplement while second of magnetic stirring.After reaction by this FeNi@CNTs
Composite material takes out, washing to neutrality, dry.
The experimental results showed that in PdCl2Dosage does not change, but reducing agent NaH in plating solution2PO2When content increases 4 times, deposition
Improvement with obvious effects.FeNi alloying pellet sizes are obviously grown up, deposition showed increased, and spheric granules is relatively uniformly dispersed throughout
In CNTs.
Embodiment 5：Using 3 identical method of embodiment, reducing agent NaH in plating solution is changed2PO2With NiSO4Solute mole
Than being 2.5:1, other conditions are constant.Pretreated CNTs is completely soaked into plating solution and is fixed in the middle part of liquid, successively into
Row magnetic stirs 15min, ultrasonic disperse 30min, magnetic and stirs 30min, and wherein magnetic whipping process is maintained at 50 DEG C of water bath with thermostatic control conditions
Under, and keep the at the uniform velocity dropwise addition of reducing agent replenisher to supplement while second of magnetic stirring.After reaction by this FeNi@CNTs
Composite material takes out, washing to neutrality, dry.
Figure of description 6 show the electron scanning micrograph of the FeNi@CNTs composite materials of the present embodiment 5.By
Fig. 6 and Fig. 5 comparisons are as it can be seen that in PdCl2Dosage does not change, but reducing agent NaH in plating solution2PO2When content continues to increase to 5 times, sink
Product improvement with obvious effects.FeNi alloying pellet sizes continue to grow up, and deposition continues to increase, and spheric granules has formed fine and close connect
Continuous coating is coated in CNTs tube banks.CNTs bundle diameters are about 22nm, and spherical alloy particle " beading " continuously tie by cladding
Structure becomes continuous fine and close " column " coating package tube bank, overall diameter about 82.2nm
Embodiment 6：Using 5 identical method of embodiment, PdCl when changing activation process2Quality, other conditions are constant.
CNTs is subjected to alkali, sour purification process, SnCl2After sensitized treatment, it is immersed in PdCl in time2(8.5mmg, 3.15mmol/L)
In solution and fixed, ultrasonic disperse 30min carries out activation process；Pretreated CNTs is completely soaked into plating solution and is fixed on
In the middle part of liquid, magnetic stirring 15min, ultrasonic disperse 30min, magnetic are carried out successively and stirs 30min, wherein magnetic whipping process is maintained at 50
The at the uniform velocity dropwise addition supplement of reducing agent replenisher is kept under the conditions of DEG C water bath with thermostatic control, and while second of magnetic stirring.Reaction terminates
This FeNi@CNTs composite material is taken out afterwards, washing to neutrality is dry.
As long as the experimental results showed that being activated by Pd, deposit FeNi alloys are spheric granules, are coated in " beading ",
Surface has nanometer Filamentous or tablet.And Pd dosages are more, shape is more regular.There is subregion when Pd is fewer in the form of sheets
Deposition
Embodiment 7：Using 5 identical method of embodiment, removal sensitization, activation process step (no SnCl2、PdCl2Place
Reason), other conditions are constant.CNTs is subjected to alkali, sour purification process and is washed to neutrality, is completely soaked into plating solution and is fixed on
In the middle part of liquid, magnetic stirring 15min, ultrasonic disperse 30min, magnetic are carried out successively and stirs 30min, wherein magnetic whipping process is maintained at 50
The at the uniform velocity dropwise addition supplement of reducing agent replenisher is kept under the conditions of DEG C water bath with thermostatic control, and while second of magnetic stirring.Reaction terminates
This FeNi@CNTs composite material is taken out afterwards, washing to neutrality is dry.
Figure of description 7 show the electron scanning micrograph of the FeNi@CNTs composite materials of the present embodiment 7.By
Fig. 7 and above-mentioned Fig. 3,6 comparisons have Pd activations as it can be seen that the activation of Pd influences the pattern of deposit FeNi alloy depositions
Lower deposit graininess spherical in shape, no Pd are in big sheet.
Embodiment 8：Using 5 identical method of embodiment, SnCl in plating solution is changed2Solution concentration (0.2880g,
0.08mol/L), NiSO4Solution concentration (1.0521g, 0.08mol/L), (NH4)2Fe(SO4)2·6H2O solution (0.3948g,
0.02mol/L), potassium sodium tartrate solution (2.1186g, 0.15mol/L), (NH4)2SO4Solution (0.6610g, 0.1mol/L)；
Wherein NiSO4(NH4)2Fe(SO4)2Solute molar ratio be 4:1.It is sensitized, activates each ultrasonic disperse 20min, other conditions are not
Become.Pretreated CNTs is completely soaked into plating solution and is fixed in the middle part of liquid, carries out magnetic stirring 15min, ultrasound point successively
30min, magnetic stirring 30min are dissipated, wherein magnetic whipping process is maintained under the conditions of 50 DEG C of waters bath with thermostatic control, and second of magnetic stirring is same
When keep reducing agent replenisher at the uniform velocity dropwise addition supplement.This FeNi@CNTs composite membrane is taken out after reaction, is washed into
Property, it is dry.
Embodiment 9：Using 5 identical method of embodiment, SnCl in plating solution is changed2Solution concentration (0.4320g,
0.12mol/L), NiSO4Solution concentration (1.1837g, 0.09mol/L), (NH4)2Fe(SO4)2·6H2O solution (0.5922g,
0.03mol/L), potassium sodium tartrate solution (2.8248g, 0.2mol/L), (NH4)2SO4Solution (0.9914g, 0.15mol/L)；
Wherein NiSO4(NH4)2Fe(SO4)2Solute molar ratio be 3:1.It is sensitized, activates each ultrasonic disperse 25min, other conditions are not
Become.Pretreated CNTs is completely soaked into plating solution and is fixed in the middle part of liquid, carries out magnetic stirring 15min, ultrasound point successively
30min, magnetic stirring 30min are dissipated, wherein magnetic whipping process is maintained under the conditions of 50 DEG C of waters bath with thermostatic control, and second of magnetic stirring is same
When keep reducing agent replenisher at the uniform velocity dropwise addition supplement.This FeNi@CNTs composite membrane is taken out after reaction, is washed into
Property, it is dry.
Claims (9)
1. the preparation method of beading iron-nickel alloy enveloped carbon nanometer tube/dimethyl silicone polymer flexible composite film；Its feature
It is the tube bank that microstructure is the continuous enveloped carbon nanometer tube of spherical alloy particle beading；Steps are as follows：
1) sensitization of carbon nano-tube film, activation process：Using stannous chloride as sensitizer, using palladium bichloride as activator, will pass through pure
The carbon nano-tube film for changing processing is immersed in ultrasonic disperse progress sensitized treatment in stannous chloride solution, then is immersed in palladium chloride solution
Middle ultrasonic disperse carries out activation process；
2) chemical plating fluid is prepared：Using nickel sulfate and iron ammonium sulfate as source metal, using sodium hypophosphite as reducing agent, with tartaric acid
Potassium sodium is complexing agent, adjusts pH=9~11 using ammonium sulfate as buffer, with ammonium hydroxide, prepares chemical plating fluid；
3) reducing agent replenisher is prepared：Be added ammonium sulfate in ortho phosphorous acid sodium solution, be added dropwise ammonium hydroxide adjust pH=9~
11, prepare reducing agent replenisher；
4) chemical plating fluid that carbon nano-tube film is immersed to step 2) carries out the stirring of first time constant temperature magnetic, ultrasonic disperse successively, then drips
Reducing agent replenisher prepared by step 3) is added to carry out second of constant temperature magnetic stirring；It is compound that iron-nickel alloy enveloped carbon nanometer tube is made
Film；
5) iron-nickel alloy enveloped carbon nanometer tube composite membrane is soaked into the dimethyl silicone polymer added with curing agent, waits for that outer layer is complete
It is put into curing oven after wrapping up a strata dimethyl siloxane, obtains iron-nickel alloy enveloped carbon nanometer tube/dimethyl silicone polymer
Flexible composite film.
2. the method as described in claim 1, it is characterized in that the carbon nano-tube film carries out purifying pretreatment：By chemical gaseous phase
Carbon nano-tube film made from sedimentation is miscellaneous by the metallic catalyst of highly basic, the purifying removal amorphous carbon of strong acid and remaining etc.
Matter, then washed and dried.
3. the method as described in claim 1, it is characterized in that a concentration of 0.08~0.12mol/ of the stannous chloride solution
L, activation process are 20~30min of ultrasonic disperse.
4. the method as described in claim 1, it is characterized in that a concentration of 0.66~3.15mmol/L of the palladium chloride solution,
Activation process is 20~30min of ultrasonic disperse.
5. the method as described in claim 1, it is characterized in that the concentration of nickel sulfate is 0.08~0.09mol/L, addition
The solute molality of nickel sulfate and iron ammonium sulfate ratio is 3~4:1.
6. the method as described in claim 1, it is characterized in that the solute molality ratio of the sodium hypophosphite and nickel sulfate
It is 0.5~2.5:1.
7. the method as described in claim 1, it is characterized in that a concentration of the 0.15 of the complexing agent potassium sodium tartrate solution~
0.2mol/L。
8. the method as described in claim 1, it is characterized in that a concentration of 0.1~0.15mol/L of the buffer ammonium sulfate.
9. the method as described in claim 1, it is characterized in that sulphur in sodium hypophosphite and plating solution in the reducing agent replenisher
The solute molality ratio of sour nickel is 2:1, reducing agent replenisher and plating solution total volume ratio are 1:1.
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