CN100436529C - Interface modifier of organic polymer and iron inorganic composite materials and its preparation - Google Patents
Interface modifier of organic polymer and iron inorganic composite materials and its preparation Download PDFInfo
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- CN100436529C CN100436529C CNB200510018192XA CN200510018192A CN100436529C CN 100436529 C CN100436529 C CN 100436529C CN B200510018192X A CNB200510018192X A CN B200510018192XA CN 200510018192 A CN200510018192 A CN 200510018192A CN 100436529 C CN100436529 C CN 100436529C
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Abstract
The present invention relates to an interface modifying agent for organic polymers and iron inorganic composite materials and a preparation method. Inorganic nanometer particles in composite materials are used as an inorganophilic phase by the interface modifying agent, and a polymer phase in the composite materials is used as composite master particles of an organic phase. The interface modifying agent can be applied to the composite materials of piezoelectric ceramics and polymers, and the composite materials of piezoelectric ceramics, polymers and rare earth alloy. The preparation method comprises an in-situ composite method and an ultrasonic dispersion method, wherein a temperature is increased and acetylacetone or glacial acetic acid is added after acetate is added to polymer solution and is uniformly mixed in the in-situ composite method, solution obtained by the reaction after the polymer solution, the acetate, the acetylacetone or the glacial acetic acid are uniformly mixed and titanate is added is directly distilled or poured into solvent which is insoluble to the used polymers for sedimentation so as to obtain sol, and the interface modifying agent is obtained after the sol is dried and is ground into fine powder; in the ultrasonic dispersion method, the prepared inorganic nanometer particles are put into the polymer solution after sintered, a film is spilt on glass base materials after ultrasonic dispersion, and the film is pulverized into powder after being dried so that the interface modifying agent is obtained. The problem of low performance of piezoelectricity and magnetoelectricity caused by a poorer interface combination is solved by the interface modifying agent.
Description
Technical field:
The present invention relates to the interface modifier and the preparation of organic polymer and iron inorganic composite materials.Its interface modifier can be applied to piezoelectric ceramics and polymer composites, piezoelectric ceramics and polymkeric substance and rare earth alloy matrix material.
Background technology:
Utilizing polymer materials excellent mechanical property, film-forming properties and stupalith good electrical properties to carry out compound is a new way that is worth exploration.Synthetic gained matrix material has overcome the fragility of stupalith self and the temperature limitation of polymer materials, has improved the material electrical property greatly.The recombining process of existing such matrix material of preparation mainly contains the hydrostomia method, pressure sintering and spin-coating method.All there is the problem in conjunction with difference of interface between polymkeric substance and the piezoelectric ceramics in these complex methods, thereby have influenced the raising of composite property.
When matrix materials such as preparation polymkeric substance and piezoelectric ceramics, piezoelectric ceramics and polymkeric substance and rare earth alloy, the method for often using coupling agent that the piezoelectric ceramics surface is handled is improved the interphase interface combination, to obtain high performance matrix material at present.But mostly used coupling agent is to increase the nonpolar of inorganic particulate surface usually, and for polar polymer, be difficult to improve the biphase bonding strength with coupling agent modified piezoelectric ceramics is compound, particularly when the recombining process that has shearing force to exist, coupling agent is difficult to play a role.Therefore the desired matrix material of difficult acquisition.
Sol-gel method is the main synthesis method of preparation nano material, and it has plurality of advantages such as goods purity and uniformity coefficient height, good moldability, is subjected to domestic and international material domain expert scholar's generally attention in recent years.But do not see the report that utilizes sol-gel method to prepare piezoelectric ceramics and polymer nanocomposite master batch as yet.
Summary of the invention:
The objective of the invention is to solve piezoelectric ceramics and polymer composites, piezoelectric ceramics and polymkeric substance and rare earth alloy matrix material are because the interface is in conjunction with relatively poor piezoelectric property that causes and the not high problem of magnetic electricity performance.Utilize inorganic nano-particle to be easy to the characteristics of adsorbing, reuniting, interface modifier is close inorganic phase with inorganic nano-particle, with the polymer phase in the matrix material as organic phase, the interface modifier and the preparation method of a kind of organic polymer and iron inorganic composite materials are provided, this interface modifier can be applied to piezoelectric ceramics and polymer composites, piezoelectric ceramics and polymkeric substance and rare earth alloy matrix material.This kind interface modifier is different from coupling agent.
The interface modifier of organic polymer of the present invention and iron inorganic composite materials, it is to be close inorganic phase with inorganic nano-particle in the matrix material, with the composite master batch of the polymer phase in the matrix material as organic phase, described polymkeric substance is the thermoplastic polymer polyethylene, or polyvinylidene difluoride (PVDF), or vinylidene-trifluoro-ethylene copolymer, or vinylidene-TFE copolymer, or polyvinyl acetal, or polyvinyl chloride, described inorganic nano ceramic particle is Pb-based lanthanumdoped zirconate titanates or lead titanate, or barium titanate, or adds Pb (Mg in the Pb-based lanthanumdoped zirconate titanates
1/3Nb
2/3) O
3. or add Pb (Mn in the Pb-based lanthanumdoped zirconate titanates
1/3Sb
2/3) O
3, or the terbium dysprosium ferrum nanoparticle.
The preparation of interface modifier of the present invention has two kinds of methods:
1, in-situ compositing
The steps include:
1st, adding acetate in polymers soln mixes, be warming up to 60 ℃～120 ℃ after mixing and add methyl ethyl diketone or Glacial acetic acid, after stirring, the stoichiometry of pressing the metal ion generation titanate in the acetate drips titanic acid ester, reacts the nano ceramics colloidal sol that obtained containing polymkeric substance in 1～4 hour;
2nd, the resulting nano ceramics colloidal sol of step 1 is directly distilled under 120 ℃～170 ℃ or pour into and carry out sedimentation in the solvent that is insoluble to used polymkeric substance;
3rd, with the resulting sediment drying of step 2 1～10 day, behind the complete drying mixture is ground into fine powder, promptly gets piezoelectric ceramics and polymer in situ composite master batch;
Wherein said polymers soln is the polyvinyl chloride tetrahydrofuran solution, or polyvinylidene difluoride (PVDF) N, the N dimethyl formamide solution, or the acetone soln of polyvinyl acetal, or vinylidene-trifluoro-ethylene copolymer aqueous liquid dispersion, or the polyethylene xylene solution, described acetate is plumbic acetate, barium acetate perhaps adds zirconium nitrate when adding acetate, the add-on of described methyl ethyl diketone or Glacial acetic acid is 3～7% of a titanic acid ester add-on.
This composite master batch can be used as the interface modifier of piezoelectric ceramics and polymer composites, piezoelectric ceramics and polymkeric substance and rare earth alloy matrix material.
2. ultrasonic dispersion
The steps include:
1st, prepare the inorganic nano ceramic particle with sol-gel method;
2nd, with the resulting inorganic nano ceramic particle of step 1 at 500～700 ℃ of following sintering, obtain nano ceramic powder;
3rd, resulting nano ceramics particle behind step 2 sintering is put into polymers soln, carry out ultra-sonic dispersion under 15～50 ℃, back bold and vigorous film on glass baseplate is uniformly dispersed, in 70～100 ℃ vacuum drying oven, be ground into powder after the film forming drying, promptly get piezoelectric ceramics and polymkeric substance composite master batch;
Wherein said inorganic nano ceramic particle is a Pb-based lanthanumdoped zirconate titanates, or lead titanate, or barium titanate, or adds Pb (Mg in the Pb-based lanthanumdoped zirconate titanates
1/3Nb
2/3) O
3, or add Pb (Mn in the Pb-based lanthanumdoped zirconate titanates
1/3Sb
2/3) O
3, or the terbium dysprosium ferrum nanoparticle; Described polymers soln is the polyvinyl chloride tetrahydrofuran solution, or polyvinylidene difluoride (PVDF) N, N dimethyl formamide solution, or vinylidene-trifluoro-ethylene copolymer aqueous liquid dispersion, the acetone soln of polyvinyl acetal, or polyethylene xylene solution; Described ultra-sonic dispersion frequency is 30～60HZ, and the time is 10～30 minutes.
This powder can be used as the interface modifier of piezoelectric ceramics and polymer composites, piezoelectric ceramics and polymkeric substance and rare earth alloy matrix material.
Description of drawings:
Fig. 1 a, 1b are respectively the microscopic pattern photo that adds interface modifier front and back matrix material
Fig. 2. be (dE/dH) that adds interface modifier front and back PZT/PVDF/Terfenol-D (terbium dysprosium ferrum) matrix material
33max-H curve
Add the preceding BaTiO of interface modifier as seen from Figure 1
3The interface of/PVDF matrix material is in conjunction with very poor, and behind the adding interface modifier, obviously improve at the interface.
Add as seen from Figure 2 after the interface modifier, the saturation magnetic field intensity of matrix material increases, and the seepage flow threshold value brings up to 0.07 from 0.05, and the magnetic electricity performance of PZT/PVDF/Terfenol-D matrix material increases substantially.(dE/dH) of PZT/PVDF/Terfenol-D/ matrix material
33maxIncrease to 78mV/cmOe by 52mV/cm Oe.
Embodiment:
Embodiment 1: at the N of polyvinylidene difluoride (PVDF) (PVDF), adding barium acetate in N dimethyl formamide (DMF) solution mixes, be warming up to 60 ℃～120 ℃ adding Glacial acetic acid after mixing, after stirring, drip titanic acid ester by generating the barium titanate stoichiometry, react the nano barium phthalate colloidal sol that obtained containing polymkeric substance in 1～4 hour.Directly in 120 ℃～170 ℃ distillations down, dry 7～10 days, behind the complete drying mixture is ground into fine powder and promptly gets nano-BaTiO then
3/ PVDF original position composite master batch.
Take by weighing PVDF, BaTiO
3And nano-BaTiO
3/ PVDF, volume ratio is: PVDF15～50%, nano-BaTiO
3/ PVDF is 1～5%, and all the other are BaTiO
3Pour into after mixing in the mould,, obtain the BaTiO of interface modification after the cooling at 160～200 ℃ of following mold pressing 15～30min
3/ PVDF matrix material, the SEM figure of matrix material sees Fig. 1.
Embodiment 2: add plumbic acetate and mix in methyl alcohol, be warming up to 60 ℃～120 ℃ after mixing and add methyl ethyl diketone, after stirring, drip titanic acid ester, react the nano barium titanate alucol that obtained containing polymkeric substance in 1～4 hour by generating the lead titanate stoichiometry.Directly in 120 ℃～170 ℃ distillations down, dry 7～10 days, behind the complete drying mixture is ground into fine powder and promptly gets nano-PbTiO then
3Under 500～600 ℃ to nano-PbTiO
3Carry out sintering, obtain the plumbous ceramic powder of nano barium titanate.Nano barium titanate lead behind the sintering is put in DMF (N, the N dimethyl formamide) solution of PVDF, carried out ultra-sonic dispersion under the normal temperature, film is sprinkled in the back that is uniformly dispersed on glass baseplate, be ground into powder after the film forming drying in 70～100 ℃ vacuum drying oven.
Take by weighing PVDF, Pb-based lanthanumdoped zirconate titanates (PZT), terbium dysprosium ferrum (Terfenol-D) and nano-PbTiO
3/ PVDF, volume ratio is: PVDF15～50%, nano-PbTiO
3/ PVDF is 3～10%, and Terfenol-D is 1～12%, and all the other are PZT.Pour in the mould after mixing, at 160～200 ℃ of following mold pressing 15～30min, obtain the PZT/PVDF/Terfenol-D matrix material of interface modification after the cooling, add interface modifier PVDF/nano-PT, the magnetic electricity performance of PZT/PVDF/Terfenol-D matrix material increases substantially, as shown in Figure 2.
Embodiment 3: at the N of polyvinylidene difluoride (PVDF) (PVDF), adding plumbic acetate in N dimethyl formamide (DMF) solution mixes, mix the back and add zirconium nitrate, be warming up to 60 ℃～120 ℃ and add methyl ethyl diketone, after stirring, drip titanic acid ester by generating the Pb-based lanthanumdoped zirconate titanates stoichiometry, react the nano barium titanate alucol that obtained containing polymkeric substance in 1～4 hour.Directly in 120 ℃～170 ℃ distillations down, dry 7～10 days, behind the complete drying mixture is ground into fine powder and promptly gets PVDF/nano-PZT then.
Take by weighing PVDF, Pb-based lanthanumdoped zirconate titanates (PZT), terbium dysprosium ferrum (Terfenol-D) and PVDF/nano-PZT, volume ratio is: PVDF15～50%, PVDF/nano-PZT are 3～10%, and Terfenol-D is 1～12%, and all the other are PZT.Pour in the mould after mixing, at 160～200 ℃ of following mold pressing 15～30min, obtain the PZT/PVDF/Terfenol-D matrix material of interface modification after the cooling, add interface modifier PVDF/nano-PT, the piezoelectric property of PZT/PVDF/Terfenol-D matrix material is brought up to 76pC/N from 60pC/N.
Claims (1)
1, the preparation method of the interface modifier of a kind of organic polymer and iron inorganic composite materials is characterized in that ultrasonic dispersion, the steps include:
1st, prepare the inorganic nano ceramic particle with sol-gel method;
2nd, with the resulting inorganic nano ceramic particle of step 1 at 500～700 ℃ of following sintering, obtain the inorganic nano ceramic powder;
3rd, resulting inorganic nano ceramic powder behind step 2 sintering is put into the solution of polymkeric substance, under 15～50 ℃, carry out ultra-sonic dispersion, back bold and vigorous film on glass baseplate is uniformly dispersed, film forming crushed after being dried powdered in 70～100 ℃ vacuum drying oven then, promptly get piezoelectric ceramics and polymkeric substance composite master batch, i.e. interface modifier;
Wherein, described inorganic nano ceramic particle is a Pb-based lanthanumdoped zirconate titanates, or barium titanate, or adds Pb (Mg in the Pb-based lanthanumdoped zirconate titanates
1/3Nb
2/3) O
3, or add Pb (Mn in the Pb-based lanthanumdoped zirconate titanates
1/3Sb
2/3) O
3, or the terbium dysprosium ferrum nanoparticle; The solution of described polymkeric substance is the polyvinyl chloride tetrahydrofuran solution, or polyvinylidene difluoride (PVDF) N, N dimethyl formamide solution, or the acetone soln of polyvinyl acetal, or vinylidene-trifluoro-ethylene copolymer aqueous liquid dispersion, or polyethylene xylene solution; Described ultra-sonic dispersion frequency is 30～60Hz, and the time is 10～30 minutes.
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| CN100497469C (en) * | 2007-09-24 | 2009-06-10 | 林玉珠 | Environment-friendly type macromolecule surfacant |
| EP2234807B1 (en) * | 2007-12-18 | 2011-06-15 | Kuraray Co., Ltd. | Interlayer film for laminated glass, method for manufacturing the same, and laminated glass containing the same |
| CN101661991B (en) * | 2009-09-16 | 2011-04-13 | 四川大学 | Lead-free piezoceramic-polyvinyl alcohol (PVA) piezoelectric composite material and preparation method thereof |
| CN104098859B (en) * | 2013-04-09 | 2018-01-26 | 合肥杰事杰新材料股份有限公司 | A kind of poly meta fluoroethylene piezoelectric film and preparation method thereof |
| CN109499496B (en) * | 2018-12-29 | 2021-07-02 | 电子科技大学 | Flexible PZT/PVDF composite piezoelectric aerogel material and preparation method thereof |
| WO2020144578A1 (en) * | 2019-01-07 | 2020-07-16 | Sabic Global Technologies B.V. | Piezoelectric compositions and uses thereof |
| CN112239327A (en) * | 2020-10-14 | 2021-01-19 | 北京化工大学 | Piezoelectric intelligent material for active control of structural vibration |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1395325A (en) * | 2002-07-12 | 2003-02-05 | 清华大学 | Three-component compound magnetoelectric material using organic polymer as adhesive and its preparation method |
| CN1462761A (en) * | 2003-05-30 | 2003-12-24 | 武汉理工大学 | New method for preparing composite material of piezodielectric ceramics/polymer |
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| CN1395325A (en) * | 2002-07-12 | 2003-02-05 | 清华大学 | Three-component compound magnetoelectric material using organic polymer as adhesive and its preparation method |
| CN1462761A (en) * | 2003-05-30 | 2003-12-24 | 武汉理工大学 | New method for preparing composite material of piezodielectric ceramics/polymer |
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