CN1300049C - Copolymerized nylon and piezo-electric ceramic composite material and preparation - Google Patents

Copolymerized nylon and piezo-electric ceramic composite material and preparation Download PDF

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Publication number
CN1300049C
CN1300049C CNB2005100194351A CN200510019435A CN1300049C CN 1300049 C CN1300049 C CN 1300049C CN B2005100194351 A CNB2005100194351 A CN B2005100194351A CN 200510019435 A CN200510019435 A CN 200510019435A CN 1300049 C CN1300049 C CN 1300049C
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piezoelectric ceramics
composite materials
nylon
poly
copolymerization
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CN1765823A (en
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董丽杰
熊传溪
权红英
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The present invention relates to piezoelectric ceramic and copolymerized nylon composite material and preparation thereof. The composite material is composed of 10% to 50% copolymerized nylon and 90% to 50% of piezoelectric ceramic according to volume proportion, wherein the copolymerized nylon is PA1010/PA6, or PA1010/ PA66, or PA66/ PA6, or PA66/PA610, or PA1010/PA66/PA610, or PA1010/PA610/PA66/PA6; the piezoelectric ceramic is titanium lead zirconate, or lead titanate, or titanium lead zirconate added with Pb (Mg1/3Nb2/3) O3, or titanium lead zirconate added with Pb (Mn1/3Sb2/3) O3, or (LixK1-x-yNay) NbO3, (wherein 0.01</=x</=0.06, and 0.4</=y</=0.5). the preparation method is the same with the preparation method of the piezoelectric ceramic and the polymer composite material, when the copolymerized nylon and the piezoelectric ceramic are compounded, the crystallographic structure of the copolymerized nylon is turned into fibrous crystal or extended chain crystal by a spherulite structure, the modulus is increased, the force-electricity coupling of the composite material is improved, and the stress dissipation is reduced. Thereby, the piezoelectric property of the composite material is higher than that of PVDF and piezoelectric ceramic composite material.

Description

Copolymer nylon and piezo-electric ceramic composite material and preparation
Technical field:
The present invention relates to a kind of polarity crystalline polymer and piezo-electric ceramic composite material and preparation, particularly copolymer nylon and piezo-electric ceramic composite material and preparation.
Technical background:
Polymer phase in piezoelectric ceramics and the polymer composites has excellent cohesiveness and good processibility, and polymkeric substance commonly used at present comprises non-polar high polymer and polarity polymer.Polyethylene (PE), polypropylene (PP) etc. belong to non-polar high polymer, by ought to there not being piezoelectricity, but owing to have asymmetrically distributed impurity charge in the material or also can make this class material have piezoelectricity because of the injection effect of electrode, but in general, non-polar polymer is that the piezoelectric property of piezo-electric ceramic composite material of matrix is less.Polyvinylidene difluoride (PVDF) (PVDF), fluorinated ethylene propylene, polyvinyl chloride (PVC), polycarbonate (PC), nylon etc. are the polarity polymers, with piezoelectric ceramics compound after, the polarization of piezo-electricity composite material can be promoted by the polarity of self, the piezoelectric property of matrix material can be improved.
The polymer phase that is used to prepare polymkeric substance and piezo-electric ceramic composite material at present mainly contains fluorinated polymkeric substance, Resins, epoxy and nylon etc.Wherein shortcoming makes the mechanical property of piezo-electricity composite material of preparation very poor to Resins, epoxy because matter is crisp etc., has therefore limited its application; Fluorinated polymkeric substance as the piezo-electricity composite material polymer phase mainly contains polyvinylidene difluoride (PVDF), vinylidene-trifluoro-ethylene copolymer P (VDF-TrFE), vinylidene-TFE copolymer P (VDF-TeFE) etc., prepared piezo-electricity composite material mechanical property is good, piezoelectric constant is higher, caused polymer phase to bond at the interface of extreme difference mutually but the weakness of the maximum of fluorinated polymkeric substance is the existence of fluorine atom, so piezoelectric property is also undesirable with piezoelectric ceramics; Nylon is because its polar structure and crystal property, the research of some trial property is arranged aspect compound with piezoelectric ceramics, but because the fusing point of nylon usually more than 200 ℃, thereby has limited its application in some field.
Copolymer nylon (co-Nylon) is a kind of polarity, crystalline polymer (polar crystal), amide group wherein has bigger moment of dipole, it can be the multipolymer (PA1010/PA6) of poly-sebacic acid decamethylene diamine and polycaprolactam, the multipolymer (PA1010/PA66) of poly-sebacic acid decamethylene diamine and PA 66, the multipolymer of PA 66 and polycaprolactam (PA66/PA6), the multipolymer (PA66/PA610) of PA 66 and poly-hexanodioic acid decamethylene diamine, the multipolymer (PA1010/PA66/PA610) of poly-sebacic acid decamethylene diamine and PA 66 and poly-hexanodioic acid decamethylene diamine, the multipolymer (PA1010/PA610/PA66/PA6) of poly-sebacic acid decamethylene diamine and poly-hexanodioic acid decamethylene diamine and PA 66 and polycaprolactam etc.Copolymer nylon is compared with general nylon, has low-crystallinity, low melting point, advantage such as transparent, has excellent comprehensive performances, can be widely used in the application in fields such as automobile decoration material hot melt adhesive and apparel binding fibre.
Summary of the invention
The purpose of this invention is to provide higher piezo-electricity composite material of a kind of piezoelectric property and preparation, i.e. piezoelectric ceramics and copolymerization nylon composite materials and preparation.
Realize the piezoelectric ceramics and the copolymerization nylon composite materials of the object of the invention, by volume percent is that 10%～50% copolymer nylon and 90%～50% piezoelectric ceramics are formed, described copolymer nylon is the multipolymer of sebacic acid decamethylene diamine and polycaprolactam, the multipolymer of poly-sebacic acid decamethylene diamine and PA 66, the multipolymer of PA 66 and polycaprolactam, the multipolymer of PA 66 and poly-hexanodioic acid decamethylene diamine, the multipolymer of poly-sebacic acid decamethylene diamine and PA 66 and poly-hexanodioic acid decamethylene diamine, perhaps be the multipolymer of poly-sebacic acid decamethylene diamine and poly-hexanodioic acid decamethylene diamine and PA 66 and polycaprolactam, described piezoelectric ceramics is lead titanate-zirconate (PZT), lead titanate (PT), the ternary system piezoelectric ceramics lead titanate-zirconate adds Pb (Mg 1/3Nb 2/3) O 3(PCM), lead titanate-zirconate adds Pb (Mn 1/3Sb 2/3) O 3And leadless piezoelectric ceramic lithium sodium kalium niobate (Li (PMS), xK 1-x-yNa y) NbO 3, 0.01≤x≤0.06,0.4≤y≤0.05 wherein.
The preparation method of piezoelectric ceramics of the present invention and copolymerization nylon composite materials is suitable for the general method for preparing piezoelectric ceramics and polymer composites, copolymer nylon and piezoelectric ceramics carry out compound, the crystalline texture of the copolymer nylon in the matrix material can change, be transformed into fibrous crystal or extended-chain crystal by original spherulitic crystal structure, because the copolymer nylon modulus increase that has the fibrous crystal structure or stretch the chain crystalline structure, improved the power-electric coupling in the matrix material, reduced the stress loss, so the piezoelectric property of piezoelectric ceramics and copolymerization nylon composite materials improves.The piezoelectric constant of copolymer nylon and piezo-electric ceramic composite material can replace PVDF to use than the piezoelectric constant height of PVDF and piezo-electric ceramic composite material.
Piezoelectric ceramics of the present invention and copolymerization nylon composite materials prepare with following several method:
A kind of preparation method is, by volume per-cent is with 10%～50% copolymer nylon and 90%～50% ceramic powder, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 15～30min under 120～190 ℃ of temperature, pressure 10～25MPa, 0-3 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.
A kind of preparation method is, by volume per-cent is with 10%～50% copolymer nylon and 90%～50% ceramic powder, the difference cold pressing plate, alternately be placed in the mould again, then on vulcanizing press, mold pressing 15～30min under 120～190 ℃ of temperature, pressure 10～25MPa, the pressurize cooling promptly makes 2-2 type piezoelectric ceramics and copolymerization nylon composite materials again
A kind of preparation method is, by volume per-cent is with 10%～50% copolymer nylon and 90%～50% piezoelectric ceramic fibers, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 15～30min under 120～150 ℃ of temperature, pressure 10～25MPa, the pressurize cooling promptly makes 1-3 type piezoelectric ceramics and copolymerization nylon composite materials again.
A kind of preparation method is, in 90%～50% piezoelectric ceramic fibers of directed sintering preparation, inject 10%～50% copolymer nylon solution, the solvent of copolymer nylon is 40～70 ℃ a phenol, after the removal of solvents drying, on vulcanizing press, mold pressing 15～30min under 120～150 ℃ of temperature, pressure 5～10MPa, the pressurize cooling promptly makes 1-3 type piezoelectric ceramics and copolymerization nylon composite materials again.
Piezoelectric ceramics of the present invention and copolymerization nylon composite materials:
The 0-3 type is meant that granular piezoelectric ceramics is dispersed in the copolymer nylon matrix;
The 1-3 type is meant that fibrous piezoelectric ceramics is dispersed in the copolymer nylon matrix;
The 2-2 type is meant that piezoelectric ceramics and copolymer nylon stratiform are compound.
Description of drawings
The SEM microstructure pattern of Fig. 1 copolymer nylon/lead titanate-zirconate two-phase composite material section.
The piezoelectric constant of Fig. 2 copolymer nylon/lead titanate-zirconate two-phase composite material and copolymerization nylon body amass the fractional relation curve.
As can be seen from Figure 1 polymkeric substance is wrapped in inorganic piezoelectric ceramic particle, and inorganic piezoelectric ceramic particle is evenly distributed in the matrix material.Copolymer nylon has formed the fibrous crystal structure on the lead titanate-zirconate surface.
The piezoelectric constant of matrix material all is higher than 30pC/N as can be seen from Figure 2, and maximum reaches 75pC/N.
Embodiment
The piezoelectric ceramics of following embodiment and copolymerization nylon composite materials, it is made up of piezoelectric ceramics and copolymer nylon, and piezoelectric ceramics selects for use lead titanate-zirconate (PZT), lead titanate (PT), ternary system piezoelectric ceramics PCM (to add Pb (Mg among the PZT 1/3Nb 2/3) O 3), (PZT adds Pb (Mn to PMS 1/3Sb 2/3) O 3), and leadless piezoelectric ceramic lithium sodium kalium niobate (Li xK 1-x-yNa y) NbO 3, 0.01≤x≤0.06,0.4≤y≤0.5; Copolymer nylon is selected PA1010/PA6, PA1010/PA66, PA66/PA6 for use, any among PA66/PA610, PA1010/PA66/PA610 and the PA1010/PA610/PA66/PA6.
Embodiment 1
By volume with 10% copolymer nylon PA1010/PA6 and 90% lead titanate-zirconate powder, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 30min under 135 ± 15 ℃ of temperature, pressure 10MPa, 0-3 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 60～80pC/N.
Embodiment 2
By volume with 50% copolymer nylon PA1010/PA66 and 50% lead titanate powder, the difference cold pressing plate, be placed in the mould in a certain order, on vulcanizing press, under mold pressing 15min under 155 ± 30 ℃ of temperature, the pressure 25MPa, 2-2 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 50～80pC/N.
Embodiment 3
By volume with 40% copolymer nylon PA66/PA6 and 60% piezoelectric ceramic fibers PCM, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 20min under 135 ± 15 ℃ of temperature, pressure 20MPa, 1-3 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 60～100pC/N.
Embodiment 4
By volume with 50% copolymer nylon PA66/PA610 and 50% lead titanate powder, the difference cold pressing plate, be placed in the mould in a certain order, on vulcanizing press, under mold pressing 30min under 160 ± 30 ℃ of temperature, the pressure 15MPa, 2-2 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 30～60pC/N.
Embodiment 5
By volume with 10% copolymer nylon PA1010/PA66/PA610 and 90% leadless piezoelectric ceramics Li 0.04K 0.56Na 0.4NbO 3Powder, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 30min under 135 ± 15 ℃ of temperature, pressure 10MPa, 0-3 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 50～80pC/N.
Embodiment 6
In 70% piezoelectric ceramic fibers PMS of directed sintering preparation, inject 30% copolymer nylon PA1010/PA610/PA66/PA6 solution, solvent is 50 ℃ a phenol, after the drying, on vulcanizing press, mold pressing 30min under 135 ± 15 ℃ of temperature, the pressure 5MPa, 1-3 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 70～100pC/N.
Embodiment 7
By volume with 20% copolymer nylon PA1010/PA66 and 80% lead titanate-zirconate ceramic fiber, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 30min under 160 ± 30 ℃ of temperature, pressure 15MPa, 1-3 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 80～110pC/N.
Embodiment 8
In 85% piezoelectric ceramics lead titanate-zirconate fiber of directed sintering preparation, inject 15% copolymer nylon PA1010/PA66 solution, solvent is that 60 ℃ phenol, dry back are on vulcanizing press, mold pressing 20min under 145 ± 25 ℃ of temperature, pressure 20MPa, 1-3 type piezoelectric ceramics and copolymerization nylon composite materials are promptly prepared in the pressurize cooling again.The piezoelectric property of matrix material reaches 80～120pC/N.

Claims (5)

1, a kind of piezoelectric ceramics and copolymerization nylon composite materials, it is characterized in that by volume percent being that 10%～50% copolymer nylon and 90%～50% piezoelectric ceramics are formed, described copolymer nylon is the multipolymer of poly-sebacic acid decamethylene diamine and polycaprolactam, the multipolymer of poly-sebacic acid decamethylene diamine and PA 66, the multipolymer of PA 66 and polycaprolactam, the multipolymer of PA 66 and poly-hexanodioic acid decamethylene diamine, the multipolymer of poly-sebacic acid decamethylene diamine and PA 66 and poly-hexanodioic acid decamethylene diamine, perhaps be the multipolymer of poly-sebacic acid decamethylene diamine and poly-hexanodioic acid decamethylene diamine and PA 66 and polycaprolactam, described piezoelectric ceramics is a lead titanate-zirconate, lead titanate, the ternary system piezoelectric ceramics lead titanate-zirconate adds Pb (Mg 1/3Nb 2/3) O 3, lead titanate-zirconate adds Pb (Mn 1/3Sb 2/3) O 3, perhaps be leadless piezoelectric ceramics (Li xK 1-x-yNa y) NbO 3, 0.01≤x≤0.06,0.4≤y≤0.5 wherein.
2, a kind of method for preparing described piezoelectric ceramics of claim 1 and copolymerization nylon composite materials, it is characterized in that by volume per-cent is with 10%～50% copolymer nylon and 90%～50% ceramic powder, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 15～30min under 120～190 ℃ of temperature, pressure 10～25MPa, the pressurize cooling promptly makes 0-3 type piezoelectric ceramics and copolymerization nylon composite materials again.
3, a kind of method for preparing described piezoelectric ceramics of claim 1 and copolymerization nylon composite materials, it is characterized in that by volume per-cent is with 10%～50% copolymer nylon and 90%～50% ceramic powder, the difference cold pressing plate, alternately be placed in the mould again, on vulcanizing press, mold pressing 15～30min under 120～190 ℃ of temperature, pressure 10～25MPa, the pressurize cooling promptly makes 2-2 type piezoelectric ceramics and copolymerization nylon composite materials again.
4, a kind of method for preparing described piezoelectric ceramics of claim 1 and copolymerization nylon composite materials, it is characterized in that by volume per-cent is with 10%～50% copolymer nylon and 90%～50% piezoelectric ceramic fibers, thorough mixing is even in mixing machine, on vulcanizing press, mold pressing 15～30min under 120～150 ℃ of temperature, pressure 10～25MPa, the pressurize cooling promptly makes 1-3 type piezoelectric ceramics and copolymerization nylon composite materials again.
5, a kind of method for preparing described piezoelectric ceramics of claim 1 and copolymerization nylon composite materials, it is characterized in that in 90%～50% piezoelectric ceramic fibers of directed sintering preparation, injecting 10%～50% copolymer nylon solution, the solvent of copolymer nylon is 40～70 ℃ a phenol, after the removal of solvents drying, on vulcanizing press, mold pressing 15～30min under 120～150 ℃ of temperature, pressure 5～10MPa, the pressurize cooling promptly makes 1-3 type piezoelectric ceramics and copolymerization nylon composite materials again.
CNB2005100194351A 2005-09-15 2005-09-15 Copolymerized nylon and piezo-electric ceramic composite material and preparation Expired - Fee Related CN1300049C (en)

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Publication number Priority date Publication date Assignee Title
CN100432019C (en) * 2007-04-11 2008-11-12 华中科技大学 Manufacture method for nylon tectorial membrane ceramics powder material
CN102432998B (en) * 2011-11-01 2013-05-22 芜湖精塑实业有限公司 Master bathes of polyamide heat insulating strip
CN103788631A (en) * 2013-11-19 2014-05-14 中北大学 Method for testing high dielectric property of novel composite generated from polyamide 11/lead zirconate titanate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002294069A (en) * 2001-03-30 2002-10-09 Asahi Kasei Corp Polyamide resin composition
CN1454934A (en) * 2002-04-29 2003-11-12 中国科学院化学研究所 Polyamide 66 composite material and preparing method thereof
CN1546425A (en) * 2003-12-02 2004-11-17 天津大学 Graphite, phenolic resin, (Ba1-x-y, Srx, Pby) TiO3 based PTC thermistor and method for preparing the same
CN1587206A (en) * 2004-08-04 2005-03-02 武汉理工大学 Process for preparing piezoelectric ceramic and polymer piezoelectric composite material
JP2005145752A (en) * 2003-11-14 2005-06-09 Tdk Corp Ceramic green sheet for manufacturing laminated chip electronic component, and method of manufacturing ceramic green sheet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002294069A (en) * 2001-03-30 2002-10-09 Asahi Kasei Corp Polyamide resin composition
CN1454934A (en) * 2002-04-29 2003-11-12 中国科学院化学研究所 Polyamide 66 composite material and preparing method thereof
JP2005145752A (en) * 2003-11-14 2005-06-09 Tdk Corp Ceramic green sheet for manufacturing laminated chip electronic component, and method of manufacturing ceramic green sheet
CN1546425A (en) * 2003-12-02 2004-11-17 天津大学 Graphite, phenolic resin, (Ba1-x-y, Srx, Pby) TiO3 based PTC thermistor and method for preparing the same
CN1587206A (en) * 2004-08-04 2005-03-02 武汉理工大学 Process for preparing piezoelectric ceramic and polymer piezoelectric composite material

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