CN100436529C - Interface modifier of organic polymer and iron inorganic composite materials and its preparation - Google Patents

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

A method for improving the performance of organic polymer and ferroinorganic composite material

Technical field:

The invention relates to an interface modifier of an organic polymer and a ferroinorganic composite material and its preparation. The interface modifier can be applied to composite materials of piezoelectric ceramics and polymers, composite materials of piezoelectric ceramics, polymers and rare earth alloys.

Background technique:

Combining the excellent mechanical properties and film-forming properties of polymer materials with the good electrical properties of ceramic materials is a new way worth exploring. The synthesized composite material overcomes the brittleness of the ceramic material itself and the temperature limitation of the polymer material, and greatly improves the electrical properties of the material. Existing composite processes for preparing such composite materials mainly include salivation method, hot pressing method and spin coating method. These composite methods all have the problem of poor interfacial bonding between the polymer and the piezoelectric ceramic, which affects the improvement of the performance of the composite material.

At present, when preparing composite materials such as polymers and piezoelectric ceramics, piezoelectric ceramics and polymers, and rare earth alloys, coupling agents are often used to treat the surface of piezoelectric ceramics to improve interphase bonding to obtain high-performance composite materials. Material. However, most of the coupling agents used are to increase the non-polarity of the surface of inorganic particles, and for polar polymers, it is difficult to improve the bonding strength of the two phases when combined with piezoelectric ceramics modified by coupling agents, especially in the presence of shear. When the composite process exists in the presence of force, it is difficult for the coupling agent to play a role. It is therefore difficult to obtain the desired composite material.

The sol-gel method is the main synthesis method for the preparation of nanomaterials. It has many advantages such as high product purity and uniformity, and good formability. In recent years, it has been widely valued by experts and scholars in the field of materials at home and abroad. However, there is no report on the preparation of piezoelectric ceramics and polymer nano-masterbatches by sol-gel method.

Invention content:

The purpose of the present invention is to solve the problem of low piezoelectric performance and magnetoelectric performance caused by poor interface bonding of piezoelectric ceramics and polymer composite materials, piezoelectric ceramics and polymers and rare earth alloy composite materials. Utilizing the characteristics of easy adsorption and agglomeration of inorganic nanoparticles, the interface modifier uses inorganic nanoparticles as the inorganic phase and the polymer phase in the composite material as the organic phase to provide an interface between the organic polymer and the ferro-inorganic composite material Modifier and preparation method, the interfacial modifier can be applied to composite materials of piezoelectric ceramics and polymers, composite materials of piezoelectric ceramics, polymers and rare earth alloys. Such interfacial modifiers are different from coupling agents.

The interface modifying agent of organic polymer and ferroinorganic composite material of the present invention, it is the composite masterbatch that uses inorganic nano particle in composite material as inorganic phase, polymer phase in composite material as organic phase, described The polymer is the thermoplastic polymer polyethylene, or polyvinylidene fluoride, or vinylidene fluoride-trifluoroethylene copolymer, or vinylidene fluoride-tetrafluoroethylene copolymer, or polyvinyl acetal, or polyvinyl chloride, The inorganic nano ceramic particles are lead zirconate titanate, or lead titanate, or barium titanate, or lead zirconate titanate with Pb(Mg _1/3 Nb _2/3 )O ₃ . or lead zirconate titanate Add Pb(Mn _1/3 Sb _2/3 )O ₃ , or terbium dysprosium iron nanoparticles.

The preparation of interfacial modifier of the present invention has two kinds of methods:

1. In situ composite method

The steps are:

1. Add acetate to the polymer solution and stir to mix. After mixing evenly, heat up to 60°C~120°C and add acetylacetone or glacial acetic acid. After stirring evenly, produce titanate according to the metal ion in acetate Measure and drop titanate, and react for 1 to 4 hours to obtain nano-ceramic sol containing polymer;

2. Distill the nano-ceramic sol obtained in step 1 directly at 120°C to 170°C or pour it into a solvent insoluble in the polymer used for sedimentation;

3. Dry the sediment obtained in step 2 for 1 to 10 days, and grind the mixture into fine powder after complete drying to obtain the in-situ composite masterbatch of piezoelectric ceramics and polymers;

Wherein said polymer solution is polyvinyl chloride tetrahydrofuran solution, or polyvinylidene fluoride N,N dimethylformamide solution, or polyvinyl acetal acetone solution, or vinylidene fluoride-trifluoroethylene copolymer aqueous Dispersion, or polyvinyl xylene solution, the acetate is lead acetate, barium acetate, or zirconium nitrate is added while acetate is added, the amount of acetylacetone or glacial acetic acid added is titanate 3-7% of the amount.

The composite masterbatch can be used as an interface modifier of piezoelectric ceramics and polymer composite materials, piezoelectric ceramics and polymers, and rare earth alloy composite materials.

2. Ultrasonic dispersion method

The steps are:

1. Prepare inorganic nano-ceramic particles by sol-gel method;

2. Sintering the inorganic nano-ceramic particles obtained in step 1 at 500-700° C. to obtain nano-ceramic powder;

3. Put the nano-ceramic particles obtained after sintering in step 2 into the polymer solution, ultrasonically disperse them at 15-50°C, spread the film on the glass substrate after the dispersion is uniform, and put them in a vacuum drying oven at 70-100°C After the film is dried in the medium, it is crushed into powder to obtain the composite masterbatch of piezoelectric ceramics and polymers;

The inorganic nano ceramic particles are lead zirconate titanate, or lead zirconate titanate, or barium titanate, or Pb(Mg _1/3 Nb _2/3 )O ₃ added to lead zirconate titanate, or lead zirconate titanate Add Pb(Mn _1/3 Sb _2/3 )O ₃ , or terbium dysprosium iron nanoparticles; the polymer solution is polyvinyl chloride tetrahydrofuran solution, or polyvinylidene fluoride N,N dimethylformamide solution , or vinylidene fluoride-trifluoroethylene copolymer aqueous dispersion, polyvinyl acetal in acetone solution, or polyethylene xylene solution; the ultrasonic dispersion frequency is 30-60HZ, and the time is 10-30 minutes.

The powder can be used as an interface modifier of piezoelectric ceramics and polymer composite materials, piezoelectric ceramics and polymers, and rare earth alloy composite materials.

Description of drawings:

Figures 1a and 1b are the microscopic morphology photos of the composites before and after adding interface modifiers

Figure 2. It is the (dE/dH) _33max -H curve of the PZT/PVDF/Terfenol-D (terbium dysprosium iron) composite before and after adding the interface modifier

It can be seen from Figure 1 that the interface bonding of BaTiO ₃ /PVDF composites is very poor before adding the interface modifier, and the interface is obviously improved after adding the interface modifier.

It can be seen from Figure 2 that after adding the interface modifier, the saturation magnetic field strength of the composite material increases, the percolation threshold value increases from 0.05 to 0.07, and the magnetoelectric properties of the PZT/PVDF/Terfenol-D composite material are greatly improved. The (dE/dH) _33max of PZT/PVDF/Terfenol-D/composite increased from 52mV/cm Oe to 78mV/cmOe.

Detailed ways:

Example 1: Add barium acetate to the N, N dimethylformamide (DMF) solution of polyvinylidene fluoride (PVDF) and stir to mix. After mixing evenly, heat up to 60°C to 120°C and add glacial acetic acid. After stirring evenly, The titanate is added dropwise according to the stoichiometric amount to form barium titanate, and reacted for 1 to 4 hours to obtain a polymer-containing nano barium titanate sol. Then directly distill at 120°C-170°C, dry for 7-10 days, grind the mixture into fine powder after complete drying to obtain nano-BaTiO ₃ /PVDF in-situ composite masterbatch.

Weigh PVDF, BaTiO ₃ and nano-BaTiO ₃ /PVDF, the volume ratio is: PVDF 15-50%, nano-BaTiO ₃ /PVDF 1-5%, and the rest is BaTiO ₃ . After mixing evenly, pour it into a mold, press at 160-200°C for 15-30 minutes, and obtain an interface-modified BaTiO ₃ /PVDF composite material after cooling. The SEM image of the composite material is shown in Figure 1.

Example 2: Add lead acetate to methanol and stir to mix. After mixing evenly, heat up to 60°C-120°C and add acetylacetone. After stirring evenly, titanate is added dropwise according to the stoichiometric amount of lead titanate, and react for 1-4 hours to obtain Polymer nano lead titanate sol. Then directly distill at 120°C-170°C, dry for 7-10 days, grind the mixture into fine powder after complete drying to obtain nano-PbTiO ₃ . The nano-PbTiO ₃ is sintered at 500-600°C to obtain nano-lead titanate ceramic powder. Put the sintered nano-lead titanate into the DMF (N, N dimethylformamide) solution of PVDF, carry out ultrasonic dispersion at room temperature, spread the film on the glass substrate after the dispersion is uniform, and put it in a vacuum of 70 ~ 100 ℃ After the film is dried in a drying oven, it is pulverized into powder.

Weigh PVDF, lead zirconate titanate (PZT), terfenol-D and nano-PbTiO ₃ /PVDF, the volume ratio is: PVDF15～50%, nano-PbTiO ₃ /PVDF is 3～10%, Terfenol -D is 1 to 12%, and the rest is PZT. After mixing evenly, pour it into a mold, press at 160-200°C for 15-30 minutes, and obtain an interface-modified PZT/PVDF/Terfenol-D composite material after cooling, add interface modifiers PVDF/nano-PT, PZT/PVDF /Terfenol-D composite material greatly improves the magnetoelectric properties, as shown in Figure 2.

Example 3: Add lead acetate to the N, N dimethylformamide (DMF) solution of polyvinylidene fluoride (PVDF) and stir to mix. After mixing evenly, add zirconium nitrate, heat up to 60°C to 120°C, add acetylacetone, and stir After uniformity, titanate is added dropwise according to the stoichiometric amount of lead zirconate titanate, and reacted for 1 to 4 hours to obtain a polymer-containing nano lead titanate sol. Then directly distill at 120°C-170°C, dry for 7-10 days, and grind the mixture into fine powder after complete drying to obtain PVDF/nano-PZT.

Weigh PVDF, lead zirconate titanate (PZT), terbium dysprosium iron (Terfenol-D) and PVDF/nano-PZT, the volume ratio is: PVDF15～50%, PVDF/nano-PZT is 3～10%, Terfenol-D 1 to 12%, and the rest is PZT. After mixing evenly, pour it into a mold, press at 160-200°C for 15-30 minutes, and obtain an interface-modified PZT/PVDF/Terfenol-D composite material after cooling, add interface modifiers PVDF/nano-PT, PZT/PVDF The piezoelectric performance of the /Terfenol-D composite was improved from 60pC/N to 76pC/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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