CN1296413C - Crystalline modified method for transfering phase polymer in magnetic-force-electro-coupling effect - Google Patents
Crystalline modified method for transfering phase polymer in magnetic-force-electro-coupling effect Download PDFInfo
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- CN1296413C CN1296413C CNB2005100182072A CN200510018207A CN1296413C CN 1296413 C CN1296413 C CN 1296413C CN B2005100182072 A CNB2005100182072 A CN B2005100182072A CN 200510018207 A CN200510018207 A CN 200510018207A CN 1296413 C CN1296413 C CN 1296413C
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Abstract
The present invention relates to a method for increasing the piezoelectric property and the magnetoelectricity of a composite material of piezoelectric ceramics, a polymer and a ferromagnetic material, and a composite material of the piezoelectric ceramics and the polymer. The present invention is characterized in that polymer crystals in the composite material are modified. The method comprises the steps that firstly, a nucleating agent solution of a noncrystalline polymer is prepared from solvents, noncrystalline polymer powder is sprayed and dried by the solution, and the noncrystalline polymer powder is hot treated for 2 to 6 hours at 0.85Tm (+/-) 20 DEG C to obtain crystalline polymer miropowder which is pulverized into powder by an airflow mill. The obtained polymer powder or polyethylene, polypropylene, polyvinylidene fluoride or nylon crystalline polymers, the piezoelectric ceramic powder and the ferromagnetic material are mixed, cold pressed and formed according to the following volume ratio of 15 to 30% of polymer, 0 to 50% of ferromagnetic material and piezoelectric ceramic powder as the rest; then, the polymer is hot pressed and formed at Tf (+/-) 5 to 10 DEG C, and the hot pressed and formed composite material is annealed at 0.85Tm(+/-)15 DEG C at maintained pressure to obtain the composite material with high piezoelectric property and magnetoelectricity.
Description
Technical field:
The present invention relates to a kind of by changing the structure of transmitting the gathering compound in the magnetic-force-electric coupling effect, reduce stress loss in the magnetic-force-electric coupling effect, thereby improve piezoelectric ceramics and polymkeric substance and ferromagnetic material matrix material, piezoelectric ceramics transmits the method that influences the matrix material functional issues as inertia mutually with piezoelectric property and magnetic electricity performance, the solution of polymer composites.
Background technology:
Ferroelectric and ferromagnetic and polymer composites not only possesses the piezoelectric effect of ferroelectric material, the magnetic stretching effect of ferromagnetic material, and has magnetic electricity performance by ferroelectric phase with ferromagnetic magnetic-Li-electric coupling mutually.Because ferroelectric material and ferromagnetic material are difficult to be combined with each other, therefore need carry out compound realization magnetic-Li-electric coupling by the bonding of polymkeric substance has magnetic electricity performance.But because the influence of modulus can produce bigger stress loss in magnetic-Li-electric coupling, therefore can reduce ferroelectric and piezoelectric property and magnetic electricity performance ferromagnetic composite material greatly as the polymkeric substance that transmits phase.Therefore change the intensity and the rigidity of polymkeric substance, make the polymer phase structurizing, can reduce the stress loss in the magnetic-force-electric coupling effect, improve the functional of matrix material.
In polymkeric substance and piezo-electric ceramic composite material, piezoelectric ceramics Pb-based lanthanumdoped zirconate titanates (PZT), lead titanate (PT), barium titanate (BT), PMNT, various PZT doping modified ceramic and ternary ceramics have higher piezoelectric property, as the piezoelectric constant d of PZT
33Can reach 400～500pC/N, PT can reach 100pC/N, but because self fragility is bigger, and is normal and polymkeric substance is compound, utilizes the snappiness of polymkeric substance to prepare the processing characteristics that piezo-electricity composite material improves piezoelectric ceramics.From existing document as can be seen, the preparation piezo-electricity composite material, selectable polymkeric substance has: polymethylmethacrylate (PMMA), Resins, epoxy, silicon rubber, polyethylene (PE), polypropylene (PP), polyvinylidene difluoride (PVDF) (PVDF), vinylidene and trifluoro-ethylene copolymer (P (VDF-TrFE)) and nylon etc., but the introducing of polymkeric substance, the piezoelectric property of matrix material reduces significantly.Piezoelectric constant d as comparatively desirable, operable PZT and PVDF matrix material
33Maximum can reach 60pC/N, is significantly less than the piezoelectric constant of the piezoelectric ceramics in the matrix material, and this mainly is because the stress loss of PVDF has influenced the power-fax in the matrix material and passed.In ferroelectric and ferromagnetic and polymer composites, there is such problem equally, the stress loss of polymkeric substance has influenced the piezoelectric property of matrix material, has also influenced the magnetic electricity performance of matrix material then.
Crystallization, orientation and crosslinked be the main method that improves polymer strength, rigidity.The crystalline texture of polymkeric substance, crystal type, degree of crystallinity can change the rigidity and the intensity of polymkeric substance significantly.Under different ambient conditions, polymkeric substance can form platelet, spherocrystal, extended-chain crystal, shish-kebab, fibrous crystal etc.; The mutual conversion of crystal formation can take place in crystalline texture along with the difference of ambient conditions; Degree of crystallinity affects polymer properties greatly.
Summary of the invention:
The present invention mainly solves existing piezoelectric ceramics and polymkeric substance and ferromagnetic material matrix material, piezoelectric ceramics and polymer composites are because piezoelectric property and the lower problem of magnetic electricity performance that the stress loss of polymkeric substance causes, a kind of crystalline modified piezoelectric ceramics and polymkeric substance and ferromagnetic material matrix material, the piezoelectric property of piezoelectric ceramics and polymer composites and magnetic electricity performance of improving by polymkeric substance is provided.
Realize that technical scheme of the present invention is:
A kind of raising piezoelectric ceramics and polymkeric substance and ferromagnetic material matrix material, the piezoelectric property of piezoelectric ceramics and polymer composites and the method for magnetic electricity performance, polymkeric substance is non-crystalline polymer or crystalline polymer, and non-crystalline polymer is polyvinyl butyral acetal, polymethylmethacrylate or polyvinyl chloride; Crystalline polymer is polyethylene (PE), polypropylene (PP), polyvinylidene difluoride (PVDF) (PVDF) or nylon, and employing is carried out crystalline modified to polymkeric substance in the matrix material, and its method steps is:
1st, with the nucleator solution of solvent preparation amorphism polymkeric substance, with this solution the non-crystalline polymer powder is carried out hydrojet, drying, ℃ thermal treatment 2～6h obtains the crystalline polymer micro mist in 0.85Tm ± 20;
2nd, by airflow milling the resulting crystalline polymer micro mist of step 1 is pulverized, obtained nanocrystalline polymer powder;
3rd, with the resulting nanocrystalline polymer powder of step 2 or polyethylene, polypropylene, polyvinylidene difluoride (PVDF) or nylon crystalline polymer and ceramic powder, ferromagnetic material by volume per-cent be that polymkeric substance is 15～30%, ferromagnetic material is 0～50%, all the other for ceramic powder mix, at the flow temperature T of used polymkeric substance
f± 5～10 ℃, pressure is hot-forming under 10～20MPa, molding time 15～30min;
4th, step 3 is hot-forming matrix material is heat-treated, and method is under pressurize 10～20MPa situation, at 0.85T
m± 15 ℃ of temperature ranges are annealed, and promptly obtain the high matrix material of piezoelectric property and magnetic electricity performance;
The nucleator solution of wherein said amorphism polymkeric substance is the cyclohexanone solution of polyvinyl chloride, the acetone soln of polyvinyl butyral acetal, the acetone soln of polymethylmethacrylate; Described piezoelectric ceramics is Pb-based lanthanumdoped zirconate titanates (PZT), lead titanate (PT), barium titanate (BT), PMNT, Pb-based lanthanumdoped zirconate titanates doping modified ceramic or ternary ceramics, and described ferromagnetic material is terbium dysprosium ferrum (Terfenol-D).
Description of drawings:
Fig. 1 is crystallization PVC and PZT matrix material and common PVC and PZT matrix material piezoelectric constant d
33With polymer volume fractional relation curve;
Fig. 2 is the DSC curve of PZT/PVDF matrix material under the Different Heat Treatment Conditions;
From Fig. 1 curve as can be seen the piezoelectric property of crystalline poly(vinyl chloride) and Pb-based lanthanumdoped zirconate titanates (PVC and PZT) matrix material far above the piezoelectric property of common PVC and PZT matrix material.
Under the different as can be seen heat-treat condition of Fig. 2 curve, the degree of crystallinity difference of PVDF is respectively 21% and 27% in the matrix material.
Embodiment
Embodiment 1:
With isotactic PVC dissolving, the common PVC powder is carried out the hydrojet drying with cyclohexanone solvent,, obtain crystallization PVC micro mist at 100 ℃ of thermal treatment 4h with this solution.By airflow milling crystallization PVC is pulverized, make the nanocrystalline PVC micro mist of 5～20 μ m, the crystal grain in the wherein nanocrystalline PVC micro mist is less than 100nm, after crystallization PVC and PZT mixed in 15: 85 by volume, 130 ℃ hot-forming, the hot-forming time is 25min, pressure is 10MPa.The piezoelectric constant d of crystallization PVC and PZT matrix material and common PVC and PZT matrix material
33See Fig. 1 with polymer volume fractional relation curve.The piezoelectric property of crystallization PVC and PZT matrix material is higher than common PVC and PZT matrix material as seen from the figure.
Embodiment 2:
With isotactic PVC dissolving, the common PVC powder is carried out the hydrojet drying with cyclohexanone solvent,, obtain crystallization PVC micro mist at 120 ℃ of thermal treatment 2h with this solution.By airflow milling crystallization PVC is pulverized, make the nanocrystalline PVC micro mist of 5～20 μ m, the crystal grain in the wherein nanocrystalline PVC micro mist is less than 100nm, obtains degree of crystallinity at 15～30% crystallization PVC.With crystallization PVC and PZT and terbium dysprosium ferrum (Terfenol-D) by 30: 64: 6 volume ratios 155 ℃ hot-forming, molding time is 10min, pressure is 20MPa, the magnetoelectricity gain factor α E of matrix material
33Be 60mV/cm Oe, common PVC and PZT and Terfenol-D compound composite material test are less than magnetic electricity performance.
Embodiment 3: with PVDF and PZT by 30: 70 volume ratios 170 ℃ hot-forming, time 30min, pressure 10MPa, be divided into two parts after the moulding, a matrix material quenches, and the degree of crystallinity of PVDF is 21% in PZT and the PVDF matrix material, see Fig. 2, the piezoelectric constant d of matrix material
33Be 40pC/N; Another part matrix material was 120 ℃ of pressurize 10MPa annealing 6 hours, and the degree of crystallinity of PVDF is 27% in gained PZT and the PVDF matrix material, sees Fig. 2, the piezoelectric constant d of matrix material
33Be 75pC/N.
Embodiment 4: PP and PZT taken by weighing by 30: 70 volume ratios, and a mixing in Banbury mixer under 160 ℃, compression molding on vulcanizing press, polymkeric substance is a spherulitic crystal structure in the gained matrix material, the piezoelectric constant d of matrix material
33Be 45pC/N; Another part 190 ℃ of moulding in mill, speed range is 10～30r/min, and the drawing force of the shearing force by mill when mixing makes matrix material in blocks, and polymkeric substance is a fibrous crystal in the gained matrix material, the piezoelectric constant d of matrix material
33Be 57pC/N.
Embodiment 5: the copolymer nylon of selecting two kinds of different crystallinities for use, the fusing point of copolymer nylon 1 is 120 ℃, the fusing point of copolymer nylon 2 is 160 ℃, hot-forming at 120 ℃ with PZT, Terfenol-D by 30: 65: 5 volume ratios, time 20min, pressure 15MPa, the magnetoelectricity gain factor α E of copolymer nylon 1 matrix material
33Be 60mV/cm Oe, the magnetoelectricity gain factor α E of copolymer nylon 2 matrix materials
33Be 72mV/cm Oe.
Claims (1)
1, a kind of piezoelectric ceramics and polymkeric substance and the piezoelectric property of ferromagnetic material matrix material and piezoelectric ceramics and polymer composites and method of magnetic electricity performance of improving, polymkeric substance is non-crystalline polymer or crystalline polymer, and non-crystalline polymer is polyvinyl butyral acetal, polymethylmethacrylate or polyvinyl chloride; Crystalline polymer is polyethylene, polypropylene, polyvinylidene difluoride (PVDF) or nylon, it is characterized in that to the polymer crystallization modification, its method steps is:
1st, with the nucleator solution of solvent preparation amorphism polymkeric substance, with this solution the non-crystalline polymer powder is carried out hydrojet, drying, ℃ thermal treatment 2～6h obtains the crystalline polymer micro mist in 0.85Tm ± 20;
2nd, by airflow milling the resulting crystalline polymer micro mist of step 1 is pulverized, obtained nanocrystalline polymer powder;
3rd, with the resulting nanocrystalline polymer powder of step 2 or polyethylene, polypropylene, polyvinylidene difluoride (PVDF) or nylon crystalline polymer and ceramic powder, ferromagnetic material by volume per-cent be that polymkeric substance is 15～30%, ferromagnetic material is 0～50%, all the other mix for ceramic powder, at the flow temperature T of used polymkeric substance
f± 5～10 ℃, pressure is hot-forming under 10～20MPa, molding time 15～30min;
4th, step 3 is hot-forming matrix material is heat-treated, and method is under pressurize 10～20MPa situation, at 0.85T
m± 15 ℃ of temperature ranges are annealed, and promptly obtain the high matrix material of piezoelectric property and magnetic electricity performance;
The nucleator solution of wherein said amorphism polymkeric substance is the pimelinketone solution of polyvinyl chloride, the acetone soln of polyvinyl butyral acetal, the acetone soln of polymethylmethacrylate; Described piezoelectric ceramics is Pb-based lanthanumdoped zirconate titanates, lead titanate, barium titanate, PMNT, Pb-based lanthanumdoped zirconate titanates doping modified ceramic or ternary ceramics, and described ferromagnetic material is a terbium dysprosium ferrum.
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| CN102061091B (en) * | 2010-12-16 | 2012-02-08 | 郑州大学 | Method for preparing nylon nano-fiber/polyolefin hybrid shish-kebab |
| CN103146101B (en) * | 2013-02-26 | 2014-12-17 | 华中科技大学 | Preparation method of high-crystallinity polyvinylidene fluoride (PVDF) |
| CN104927254B (en) * | 2015-07-07 | 2017-09-22 | 北京工业大学 | A kind of ferrotitanium niobium/Kynoar high-dielectric composite material and preparation method thereof |
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| CN1462765A (en) * | 2003-05-30 | 2003-12-24 | 武汉理工大学 | Nano crystal PVC material utilized in construction and its preparing method |
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