CN103709565A - Composite fiber and polymer based flexible composite film and preparation method thereof - Google Patents
Composite fiber and polymer based flexible composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite fiber and polymer based flexible composite film and a preparation method thereof. The composite fiber and polymer based flexible composite film comprises a composite fiber and a polymer matrix, wherein the volume percentage of the composite fiber is 1-30%; the composite fiber is composed of an oxide fiber and ceramic particles and/or metal particles embedded in the oxide fiber; the polymer matrix is at least one out of polyvinylidene fluoride, epoxy resin, polyvinylidene fluoride-trifluoroethene, polypropylene, polyethylene terephthalate and polyimide. According to the composite fiber and polymer based flexible composite film disclosed by the invention, the composite fiber and the polymer matrix are compounded, and since additional polarization is introduced into the composite fiber, the polymer based flexible composite film can get a higher dielectric constant under a condition of small adding dosage so as to meet the dielectric performance requirements of the composite material and maintain original related properties of the polymer film, such as mechanical flexibility, to the maximum extent at the same time.
Description
Technical field
The present invention relates to a kind of conjugated fibre and polymer-based carbon flexible composite film and preparation method thereof, belong to electron recombination technical field of material.
Background technology
As important base electronic element, electrical condenser has occupied the 40% above share in electronic component market, the electronic component output value in the whole world in 2011 has surpassed 15,000,000,000 dollars, in dielectric substance field, along with making rapid progress of electronics development in recent years, widely used electrical condenser is to high energy storage, miniaturization and environmentally friendly future development.Traditional high dielectric constant dielectric material is inorganic ceramic material, although ceramic dielectric material has very excellent dielectric properties, but it needs high temperature sintering in preparation process, cannot be applied on organic substrate or printed circuit board (PCB) (PCB), exist the drawbacks such as fragility is large, processing temperature is higher, loss is large, in the face of miniaturization, the lightness development trend of product, independent inorganic ceramic high capacitance dielectric materials has been difficult to meet the demands.Polymer materials due to be easy to processing, flexible, lightweight, with organic substrate and printed circuit board (PCB) consistency good, can make the advantages such as large-area film, be widely used in dielectric substance.The high-k polymer matrix composite with advantages such as lightweight, easily processing, low cost and good mechanical properties is just being subject to the world and is paying close attention to widely.They both can be used as the dielectric material of high density capacitors in electric works field, also can be used as the stress cone material of high-tension cable homogenizing electric field.Particularly its snappiness and and the feature of the consistency of organic circuit board, the good application aspect embedded encapsulation technology and corresponding embedded circuit board of polymer-based carbon laminated film.And except as electronic component in the application aspect embedded encapsulation, in recent years, along with the development of national intelligent grid and the promotion of new energy field, to the demand of superpower, jumbo electrical condenser also in continuous increase, at new energy fields such as generation of electricity by new energy, power transmission, there is a large amount of demands, and polymer-based carbon laminated film is due to its higher breaking down field strength, the feature that can use in hyperbaric environment also becomes the important use material of high-power components.And be directed to polymkeric substance itself, it has good mechanical flexibility and high breaking down field strength, but the specific inductivity too low (being generally 2～3) of itself, all restricted to the raising of the microminiaturization of element itself and energy storage density, to adding high dielectric ceramic nanoparticle in polymeric matrix or conductive component can be that specific inductivity is effectively promoted, but a large amount of introducings due to inorganic component, can damage again mechanical property and the breaking down field strength of polymkeric substance, therefore how under the prerequisite that does not change the original flexibility of polymkeric substance itself and breakdown performance, to improve research emphasis and the focus that its specific inductivity becomes polymer matrix composite as far as possible.
Aspect polymer matrix composite research work, have at present a large amount of progress, the people such as Liang are by BaTiO
3particle carries out compound with bis-phenol, find under the condition of 1MHz, 298K, along with BaTiO
3content increase, the specific inductivity of matrix material increases, BaTiO
3content while reaching 60%, the specific inductivity of matrix material reaches 15.The people BaTiO such as xie
3to carry out with polyimide compoundly, under 10KHz, room temperature, under condition, work as BaTiO
3when content reaches 50%, the specific inductivity that obtains matrix material is 35.The people such as Song Yu are by BaTiO
3nanofiber with polyvinylidene difluoride (PVDF), carry out compoundly can 12%, reaching 30% in the volume fraction of inorganic interpolation.Except above-mentioned employing high dielectric ceramic and polymkeric substance compound outside, it is compound that the people such as Dang Zhimin adopt the conductive components such as carbon fiber, metal Ni particle and polyvinylidene difluoride (PVDF) (PVDF) matrix to carry out, and utilizes the seep effect of conductive particle in insulating body to improve significantly the specific inductivity of matrix material.From current some, study, for ceramic particle with the compound specific inductivity that can improve polymkeric substance of polymkeric substance, but need higher inorganic addition just can obtain the specific inductivity (general volume fraction is greater than 50%) obviously promoting, causing like this mechanical flexibility of polymkeric substance greatly to reduce, can be also that breaking down field strength reduces greatly because inorganic component adds the defect too much causing.And for adding conductive component, can under less addition, obtain higher specific inductivity, but conductive component can produce too high dielectric loss, once and conductive component content surpass percolation threshold, will make matrix material become conductor from isolator.
Summary of the invention
The object of this invention is to provide a kind of conjugated fibre and polymer-based carbon flexible composite film and preparation method thereof, the present invention realizes under lower inorganic addition obtaining and has the polymer matrix composite of high dielectric constant by add conjugated fibre in polymeric matrix, thereby makes the correlated performance of polymkeric substance itself not be subject to the interpolation of ceramic particle and the impact that produces.
A kind of conjugated fibre provided by the present invention and polymer-based carbon flexible composite film, it comprises conjugated fibre and polymeric matrix, the volumn concentration of described conjugated fibre is 1%～30%;
Described conjugated fibre is comprised of oxide fibre and the ceramic particle and/or the metallic particles that are embedded in oxide fibre;
Described polymeric matrix can be polyvinylidene difluoride (PVDF) (PVDF), epoxy resin (Epoxy, EP), polyvinylidene difluoride (PVDF)-trifluoro-ethylene (P(VDF_TRFE)), in polypropylene (PP), polyethylene terephthalate (PET) and polyimide (PI) at least one.
In described flexible composite film, described oxide fibre can be titania fiber, silicon oxide fibre or sapphire whisker;
Described ceramic particle can be BaTiO
3or Ba
xsr
1-xtiO
3, wherein, x can be the number between 0.1～0.8;
Described metallic particles can be Al particle or Ag particle.
In described flexible composite film, in described conjugated fibre, the volumn concentration of described ceramic particle and/or described metallic particles can be 1%～70%, specifically can be 33.3%～50%, 33.3% or 50%;
The particle diameter of described ceramic particle and/or described metallic particles can be 10nm～100nm, as 50nm.
In described flexible composite film, the diameter of described conjugated fibre can be 100nm～1 μ m, and as 400nm～500nm, 400nm or 500nm, the length of described conjugated fibre can be 1 μ m～1mm, as 100 μ m;
The thickness of described flexible composite film can be 1 μ m～100 μ m, as 16 μ m.
In described flexible composite film, the surface of described conjugated fibre is also coated with Dopamine HCL rete;
The thickness of described Dopamine HCL rete can be 1～10nm, as 3nm.
In described flexible composite film, the volumn concentration of described conjugated fibre specifically can be 1.3%～11.4%, 1.3%, 3%, 4.1%, 7.4% or 11.4%.
The present invention also provides the preparation method of described flexible composite film, comprises the steps:
(1) tetrabutyl titanate, tetraethyl orthosilicate or aluminic acid three isopropyl esters are dissolved in organic solvent I and obtain colloidal sol; Described ceramic particle and/or described metallic particles are added in described colloidal sol, obtain spinning precursor sol;
(2) described spinning precursor sol is carried out to electrostatic spinning, obtain the presoma of conjugated fibre;
(3) presoma of described conjugated fibre is calcined under the condition of 450～550 ℃, obtained described conjugated fibre;
(4) described conjugated fibre is scattered in organic solvent II and obtains suspension, in described suspension, add described polymeric matrix to obtain mixed solution; Described mixed solution, through tape-casting, obtains described flexible composite film.
In described preparation method, described organic solvent I can be at least one in ethanol, DMF, ethylene glycol monomethyl ether, Skellysolve A and dimethylbenzene;
Described organic solvent II can be at least one in DMF, Skellysolve A, ethylene glycol monomethyl ether and dimethylbenzene.
In described preparation method, in step (1), described method also comprises to the step that adds polyvinylpyrrolidone in described spinning precursor sol, the addition of described polyvinylpyrrolidone is spinning precursor sol described in 0.02～0.08g/ml, as described in the addition of polyvinylpyrrolidone be spinning precursor sol as described in 0.04g/ml.
In described preparation method, in step (2), described electrostatic spinning can carry out under the electric field of 0.5-2kV/cm, as carried out under the electric field of 1.3kV/cm.
In described preparation method, in step (3), the time of described calcining can be 1 hour～and 3 hours, as 2 hours; The temperature of described calcining specifically can be 450 ℃ or 500 ℃.
In described preparation method, afterwards, described method is also included under the condition of 40～80 ℃ carries out dry step to described flexible composite film to step (4).
In described preparation method, step (4) before, described method is also included in the step of the coated described Dopamine HCL rete in surface of described compounding fiber: described conjugated fibre is scattered in the Dopamine HCL aqueous solution, at 60 ℃, stir 10h, after centrifugal again with after deionized water and washing with alcohol and get final product; The volumetric molar concentration of the described Dopamine HCL aqueous solution can be 0.001mol/L～0.01mol/L, as 0.01mol/L.
Flexible composite film prepared by the present invention is that specific inductivity under 1V, the frequency condition that is 100Hz can reach 12～45 in test voltage.
The present invention is embedded in the middle of the relatively low oxide compound of specific inductivity by some being had to the ceramic particle of high dielectric constant, ceramic nano particle in the oxide fibre of nanometer owing to having formed the interface topological framework of UNICOM, thereby can make specific inductivity be greatly enhanced, can realize and under the condition of lower inorganic addition, make the specific inductivity of polymeric matrix be significantly improved.Owing to having introduced extra interfacial polarization in filler inside, so can obtain higher specific inductivity under the condition of identical volume addition, thereby be greatly reduced to, meet the requirement of matrix material specific inductivity and needed inorganic interpolation content, thereby substantially can not exert an influence to the mechanical flexibility of polymeric matrix and breaking down field strength.BaTiO as prepared in the present invention
3nano particle/TiO
2nanofiber conjugated fibre and polyvinylidene difluoride (PVDF) laminated film specific inductivity when conjugated fibre volume content is 10% can reach 41, on the basis of script PVDF, promoted nearly 300%, obviously exceed the performance of matrix material at present prepared under equal conditions, therefore laminated film of the present invention has excellent dielectric properties and mechanical property.
The present invention has following effectively effect:
The present invention is limited in ceramic nano particle in composite nano fiber, thereby in fiber, between particle and particle, can form the inner boundary of UNICOM, for space charge provides mobile passage, thereby produces stronger interfacial polarization, and specific inductivity is increased.Like this by conjugated fibre and polymeric matrix carry out compound, due to the extra polarization in the inner introducing of conjugated fibre, can be in the situation that lower addition make polymer-based carbon laminated film obtain higher specific inductivity, thus the correlated performances such as the original mechanical flexibility of polymeric film maintained to greatest extent meeting when matrix material dielectric properties require.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope picture of the conjugated fibre prepared by method of electrostatic spinning in embodiment 1.
Fig. 2 is the scanning electron microscope picture of the conjugated fibre prepared by method of electrostatic spinning in embodiment 2.
Fig. 3 is coated the Dopamine HCL rete high resolution projection Electronic Speculum picture of conjugated fibre afterwards in embodiment 3.
Fig. 4 be in embodiment 3 PVDF and conjugated fibre mix after the surface sweeping Electronic Speculum picture of the film surface prepared of curtain coating.
Fig. 5 is that the specific inductivity of embodiment 3,4,5,6 and 75 kinds of laminated films preparing is with the variation relation (test voltage is 1V) of frequency.
Fig. 6 is that the dielectric loss of embodiment 3,4,5,6 and 75 kinds of laminated films preparing is with the variation relation (test voltage is 1V) of frequency.
Fig. 7 is that the dielectric of 5 kinds of laminated films of embodiment 3,4,5,6 and 7 preparations is damaged constant with the variation relation (test voltage is 1V, and frequency is 100Hz) of the volume fraction of conjugated fibre interpolation.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
In following embodiment, charging capacity is to add by massfraction, and then obtains respectively polymkeric substance and the shared volume of conjugated fibre according to the density of polymkeric substance in laminated film and conjugated fibre, then obtains the volume fraction of conjugated fibre.
Take and measure 2ml tetrabutyl titanate and 4ml methyl ethyl diketone is added dropwise in 4ml ethanol in order, and be stirred to uniform and stable state, then add 1g barium titanate (BaTiO
3) particle (particle diameter is 50nm) continues to be stirred to uniform and stable state, then adding 0.4g PVP(addition is 0.04g/ml colloidal sol, be used for regulating the viscosity of colloidal sol to the viscosity number that is applicable to spinning), stir 2h and form stable colloidal sol, colloidal sol is transferred to and in syringe, carried out electrostatic spinning, electrostatic spinning carries out under the electric field of 1.3kV/cm, and the mode of collecting by cylinder obtains the fiber of electrostatic spinning and calcine 2h at 500 ℃, and (density is 5g/cm to obtain conjugated fibre
3).
As shown in Figure 1, wherein, the scale in Fig. 1 (a) is 2 μ m to the scanning electron microscope (SEM) photograph of the conjugated fibre pattern that the present embodiment obtains, scale in Fig. 1 (b) is 1 μ m, by this figure, can be learnt, the diameter of conjugated fibre prepared by the present embodiment is 500nm, and length is 100 μ m.
In the conjugated fibre that the present embodiment obtains, BaTiO
3the volumn concentration of particle is 50%.
Take and measure 2ml tetrabutyl titanate and 4ml methyl ethyl diketone is added dropwise in 4ml ethanol in order, and be stirred to uniform and stable state, then add 0.5g barium titanate (BaTiO
3) particle (particle diameter is 50nm) continues to be stirred to uniform and stable state, then adding 0.4g PVP(addition is 0.04g/ml colloidal sol) stir 2h and form stable colloidal sol, colloidal sol is transferred to and in syringe, carried out electrostatic spinning, electrostatic spinning carries out under the electric field of 1.3kV/cm, the mode of collecting by cylinder obtains the fiber of electrostatic spinning and calcine 2h at 450 ℃, obtains conjugated fibre.
As shown in Figure 2, wherein, the scale in Fig. 2 (a) is 2 μ m to the scanning electron microscope (SEM) photograph of the conjugated fibre pattern that the present embodiment obtains, scale in Fig. 2 (b) is 1 μ m, by this figure, can be learnt, the diameter of conjugated fibre prepared by the present embodiment is 400nm, and length is 100 μ m.
In the conjugated fibre that the present embodiment obtains, BaTiO
3the volumn concentration of particle is 33.3%.
The conjugated fibre 0.2g that gets embodiment 1 preparation is placed in the 0.01mol/L Dopamine HCL aqueous solution of 50ml, at 60 ℃, stirs 10h, through centrifugal, is dried 5h after washing with alcohol at 60 ℃.Measure 3.5mlDMF solvent, add 0.018g through the conjugated fibre of above-mentioned processing, ultrasonic 30min, then to add the PVDF(density of 0.332g be 1.2g/cm
3), stir 5h to uniform and stable state, then mixed solution is carried out to curtain coating, after dry 2h, can obtain film at 50 ℃.
In the present embodiment, as shown in Figure 3, as seen from the figure, the thickness of coated Dopamine HCL rete is 3nm to the high-resolution electron microscopy picture of the conjugated fibre after Dopamine HCL is coated with.
The surface scan Electronic Speculum picture of laminated film prepared by the present embodiment as shown in Figure 4, can be learnt by figure, and the thickness of laminated film is 16 μ m.
In laminated film prepared by the present embodiment, the volumn concentration of conjugated fibre is 1.3%.
As shown in Figure 5, the relation of dielectric loss and frequency as shown in Figure 6 for the specific inductivity of laminated film prepared by the present embodiment and the relation of frequency.
Embodiment 4, prepare flexible composite film
The conjugated fibre 0.2g that gets embodiment 1 preparation is placed in the 0.01mol/L Dopamine HCL aqueous solution of 50ml, at 60 ℃, stirs 10h, and through centrifugal, washing with alcohol is carried out drying treatment.Measure 3.5mlDMF solvent, add 0.039g through the conjugated fibre of above-mentioned processing, ultrasonic 30min, then add the PVDF of 0.311g, stirs 5h to uniform and stable state, then mixed solution is carried out to curtain coating, after dry 2h, can obtain laminated film at 50 ℃.
The thickness of laminated film prepared by the present embodiment is 16 μ m.
In laminated film prepared by the present embodiment, the volumn concentration of conjugated fibre is 3%.
As shown in Figure 5, the relation of dielectric loss and frequency as shown in Figure 6 for the specific inductivity of laminated film prepared by the present embodiment and the relation of frequency.
The conjugated fibre 0.2g that gets embodiment 1 preparation is placed in the 0.01mol/L Dopamine HCL aqueous solution of 50ml, at 60 ℃, stirs 10h, and through centrifugal, washing with alcohol is carried out drying treatment.Measure 3.5mlDMF solvent, add 0.053g through the conjugated fibre of above-mentioned processing, ultrasonic 30min, then add the PVDF of 0.297g, stirs 5h to uniform and stable state, then mixed solution is carried out to curtain coating, after dry 2h, can obtain laminated film at 50 ℃.
The thickness of laminated film prepared by the present embodiment is 16 μ m.
In laminated film prepared by the present embodiment, the volumn concentration of conjugated fibre is 4.1%.
As shown in Figure 5, the relation of dielectric loss and frequency as shown in Figure 6 for the specific inductivity of laminated film prepared by the present embodiment and the relation of frequency.
Embodiment 6, prepare flexible composite film
The conjugated fibre 0.2g that gets embodiment 1 preparation is placed in the 0.01mol/L Dopamine HCL aqueous solution of 50ml, at 60 ℃, stirs 10h, and through centrifugal, washing with alcohol is carried out drying treatment.Measure 3.5mlDMF solvent, add 0.087g through the conjugated fibre of above-mentioned processing, ultrasonic 30min, then add the PVDF of 0.263g, stirs 5h to uniform and stable state, then mixed solution is carried out to curtain coating, after dry 2h, can obtain laminated film at 50 ℃.
The thickness of laminated film prepared by the present embodiment is 16 μ m.
In laminated film prepared by the present embodiment, the volumn concentration of conjugated fibre is 7.4%.
As shown in Figure 5, the relation of dielectric loss and frequency as shown in Figure 6 for the specific inductivity of laminated film prepared by the present embodiment and the relation of frequency.
Embodiment 7, prepare flexible composite film
The conjugated fibre 0.2g that gets embodiment 1 preparation is placed in the 0.01mol/L Dopamine HCL aqueous solution of 50ml, at 60 ℃, stirs 10h, and through centrifugal, washing with alcohol is carried out drying treatment.Measure 3.5mlDMF solvent, add 0.122g through the conjugated fibre of above-mentioned processing, ultrasonic 30min, then add the PVDF of 0228g, stirs 5h to uniform and stable state, then mixed solution is left a message, and after dry 2h, can obtain laminated film at 50 ℃.
The thickness of laminated film prepared by the present embodiment is 16 μ m.
In laminated film prepared by the present embodiment, the volumn concentration of conjugated fibre is 11.4%%.
As shown in Figure 5, the relation of dielectric loss and frequency as shown in Figure 6 for the specific inductivity of laminated film prepared by the present embodiment and the relation of frequency.
As seen from Figure 5, by add BaTiO in PVDF matrix
3and TiO
2conjugated fibre can significantly promote the specific inductivity of matrix under lower addition, when the volume addition of conjugated fibre reaches 11.4%, can make the specific inductivity of matrix promote over 300%.
As seen from Figure 6, in laminated film, although specific inductivity has larger lifting, dielectric loss still maintains lower level.
Fig. 7 is that the dielectric of 5 kinds of laminated films of embodiment 3,4,5,6 and 7 preparations is damaged the variation relation of the volume fraction that constant adds with conjugated fibre (test voltage is 1V, frequency is 100Hz), as seen from the figure, the specific inductivity of laminated film promotes along with the increase of the volume addition of conjugated fibre, and pulling speed is very fast.
Claims (10)
1. conjugated fibre and a polymer-based carbon flexible composite film, is characterized in that: described flexible composite film comprises conjugated fibre and polymeric matrix, and the volumn concentration of described conjugated fibre is 1%～30%;
Described conjugated fibre is comprised of oxide fibre and the ceramic particle and/or the metallic particles that are embedded in oxide fibre;
Described polymeric matrix is at least one in polyvinylidene difluoride (PVDF), epoxy resin, polyvinylidene difluoride (PVDF)-trifluoro-ethylene, polypropylene, polyethylene terephthalate and polyimide.
2. flexible composite film according to claim 1, is characterized in that: described oxide fibre is titania fiber, silicon oxide fibre or sapphire whisker;
Described ceramic particle is BaTiO
3or Ba
xsr
1-xtiO
3, wherein, x is the number between 0.1～0.8;
Described metallic particles is Al particle or Ag particle.
3. flexible composite film according to claim 1 and 2, is characterized in that: in described conjugated fibre, the volumn concentration of described ceramic particle and/or described metallic particles is 1%～70%;
The particle diameter of described ceramic particle and/or described metallic particles is 10nm～100nm.
4. according to the flexible composite film described in any one in claim 1-3, it is characterized in that: the diameter of described conjugated fibre is 100nm～1 μ m, the length of described conjugated fibre is 1 μ m～1mm;
The thickness of described flexible composite film is 1 μ m～100 μ m.
5. according to the flexible composite film described in any one in claim 1-4, it is characterized in that: the surface of described conjugated fibre is also coated with Dopamine HCL rete;
The thickness of described Dopamine HCL rete is 1nm～10nm.
6. the preparation method of flexible composite film described in any one in claim 1-5, comprises the steps:
(1) tetrabutyl titanate, tetraethyl orthosilicate or aluminic acid three isopropyl esters are dissolved in organic solvent I and obtain colloidal sol; Described ceramic particle and/or described metallic particles are added in described colloidal sol, obtain spinning precursor sol;
(2) described spinning precursor sol is carried out to electrostatic spinning, obtain the presoma of conjugated fibre;
(3) presoma of described conjugated fibre is calcined under the condition of 450～550 ℃, obtained described conjugated fibre;
(4) described conjugated fibre is scattered in organic solvent II and obtains suspension, in described suspension, add described polymeric matrix to obtain mixed solution; Described mixed solution, through tape-casting, obtains described flexible composite film.
7. preparation method according to claim 6, is characterized in that: described organic solvent I is at least one in ethanol, DMF, ethylene glycol monomethyl ether, Skellysolve A and dimethylbenzene;
Described organic solvent II is at least one in dimethyl formamide, ethylene glycol monomethyl ether, Skellysolve A and dimethylbenzene.
8. according to the preparation method described in claim 6 or 7, it is characterized in that: in step (2), described electrostatic spinning carries out under the electric field of 0.5～2kV/cm;
In step (3), the time of described calcining is 1 hour～3 hours.
9. according to the preparation method described in any one in claim 6-8, it is characterized in that: afterwards, described method is also included under the condition of 40～80 ℃ carries out dry step to described flexible composite film to step (4).
10. according to the preparation method described in any one in claim 6-9, it is characterized in that: step (4) before, described method is also included in the step of the coated described Dopamine HCL rete in surface of described compounding fiber: described conjugated fibre is scattered in the Dopamine HCL aqueous solution, stirs by centrifugal and get final product.
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