CN108164843A - A kind of high machine-photoelectric transformation efficiency native rubber composite material and preparation method thereof - Google Patents
A kind of high machine-photoelectric transformation efficiency native rubber composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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Abstract
The present invention relates to a kind of high electromechanical conversion efficiency native rubber composite materials and preparation method thereof.The composite material contains rubber matrix：100 parts, vulcanizing agent：25 parts, inorganic filler：10 50 parts, plasticizer：10 50 parts.The preparation method is filled into using the inorganic filler and plasticizer of high-k in natural rubber matrix, the dielectric elastomer composite material for taking into account high-k and low elastic modulus is obtained, this composite material has big draw ratio, high-electric breakdown strength, high electromechanical conversion efficiency and high-energy density.Natural rubber dielectric elastomer composite material provides the preparation method and thinking of a kind of new material for dielectric elastomer electrical generator fields.
Description
Technical field：
The invention belongs to materials processing technology fields, are related to high machine-photoelectric transformation efficiency natural rubber dielectric elastomeric bluk recombination
Material and preparation method thereof.More particularly to prepared using high dielectric ceramic filler and plasticizer have high machine-photoelectric transformation efficiency and
The dielectric elastomer generator native rubber composite material of high-energy density.
Background technology：
Dielectric elastomer generator (DEG) is by elastomer thin film and is coated on the compliant electrodes of lower surface and forms, energy
A variety of mechanical energy in natural environment are changed into electric energy, it is expected to as a kind of renewable sources of energy new paragon.Electromagnetism more traditional DEG
Formula, piezoelectric generator are compared, and have many advantages, such as light weight, energy density height, high conversion efficiency, at low cost.Dielectric elastomer
With flexibility is good, deformation quantity is big, energy density is high, the response time is fast, dielectric loss and viscoelastic hysteresis loss are small, processing cost
Low, the advantages that mass producing, be the good selection for preparing DEG materials.
In recent years, applied to the most of acrylic acid from Minnesota Mining and Manufacturing Company of dielectric material on dielectric elastomer generator
Ester VHB4910 adhesive tapes.But VHB4910 dielectric constants relatively low (4.8), glutinous to play hysteresis loss big, seriously restricts its machine-electricity and converts
The raising of efficiency.Therefore, it designs and prepares with high-k, low-dielectric loss, low elastic modulus, big draw ratio, high strike
The dielectric elastomer material for wearing intensity is the key factor for developing high machine-photoelectric transformation efficiency DEG.Such as, Dongrui Wang etc.,
“Dielectric elastomer generator withimproved energy density andconversion
efficiency based onpolyurethane composites”(《ACS Applied Materials&
Interfaces》2017,9：5237-5243) in a text, describe in detail with polyurethane (PU) as basis material, pass through filling
Barium titanate (BT) ceramic packing and dibutyl phthalate (DBP) plasticizer, prepare dielectric elastomer composite material.It compares
Compared with pure polyurethane material, this compound polyurethane material is by energy density from 0.1mJ/cm3It is increased to 1.6mJ/cm3, simultaneously
Machine-photoelectric transformation efficiency is increased to 0.7% from 0.1%.Although the work proposes a kind of preparation method of new material, but composite wood
The raising of machine-photoelectric transformation efficiency of material is very limited.
Invention content
It is an object of the present invention to provide a kind of high machine-photoelectric transformation efficiency native rubber composite materials and preparation method thereof.
The present invention is that the dielectric ceramic filler of high-k is added into natural rubber dielectric elastomer matrix to improve
The dielectric constant of elastomer, while elasticity modulus is further reduced by filling small molecule plasticizer, take into account Gao Jie so as to prepare
The dielectric elastomer composite material of electric constant and big draw ratio, so as to obtain high machine-photoelectric transformation efficiency and high-energy density, to be situated between
Electric elastic body electric generating field provides a kind of preparation method of new material.
Native rubber composite material of the present invention, including following components and mass fraction：The rubber of 100 mass parts
Matrix, 2-5 mass parts vulcanizing agent, 10-50 mass parts high dielectric inorganic filler, the plasticizer of 10-50 mass parts.
Above-mentioned elastomer matrix is：Natural rubber, the natural rubber have excellent electrical insulating property, big draw ratio, good
Good tear resistance, wearability and drought tolerance；Above-mentioned high dielectric inorganic filler is：Barium titanate, titanium dioxide, aluminium oxide, niobium magnesium
Lead zirconate titanate, copper lead titanate ceramics filler；Above-mentioned plasticizer is：Dioctyl phthalate (DOP), aromatic oil, paraffin oil or
Naphthenic oil.The grain size of the semiconductor fills is 30nm-200nm.
Above-mentioned high machine-photoelectric transformation efficiency native rubber composite material preparation method is：
(1) by 100 mass parts of brombutyl and 2-5 mass parts vulcanizing system, the inorganic filler of 10-50 mass parts and
10-50 mass parts plasticizer is kneaded uniform slice at 20-60 DEG C,
(2) after step (1) resulting sheet being parked 7-9h, vulcanize on vulcanizing press, mixture is in 140-150 DEG C of mould
Natural rubber dielectric elastomer composite material is made in pressure vulcanization.
Natural rubber dielectric elastomer composite material obtained above at 1 khz dielectric constant be 3.45-12.32, Young
Modulus is 0.05-0.36MPa, and machine-photoelectric transformation efficiency is 4.5-14.7%.
The present invention choose natural rubber be matrix the reason of be, natural rubber have excellent electrical insulating property, big draw ratio,
Good tear resistance, wearability and drought tolerance.
Dielectric Coefficient：Dielectric properties are tested using German NovochtrolAlpha-A impedances instrument at room temperature, are tested
Frequency range is：1-106Hz。
Machine-photoelectric transformation efficiency is measured and is calculated：Composite material upper and lower surface is sprayed into self-control flexible electrode, is positioned over air blast
Then dry 2h in baking oven is sticked to the side of material upper and lower surface with aluminium foil respectively, aluminium foil here will be straight as electrode of extending
The positive and negative anodes of stream high voltage power supply ride over flexible electrode two surfaces up and down.It is answered first by force-extension natural rubber dielectric elastomer
Condensation material film, increases membrane area, and film is thinning, and high voltage power supply is to its charging a period of time at this time.Cancel mechanical energy, dielectric bullet
Property body thin film free shrink, membrane capacitance reduces, and film surface voltage becomes larger, and dielectric elastomer storage energy increases, increased electric energy
For force-extension dielectric elastomeric body thin film work done.Increased electric energy and the ratio of mechanical work are dielectric elastomeric body thin film
Machine-photoelectric transformation efficiency.
The beneficial effects of the invention are as follows unlike conventional thought：Natural rubber is chosen as matrix, adds in high dielectric
Filler prepares to reach raising dielectric constant, while add in plasticizer reduction elasticity modulus and takes into account high-k and stretch greatly
The dielectric elastomer composite material of ratio.This composite material has high machine-photoelectric transformation efficiency and high-energy density, is dielectric elastomeric
Body power field provides the preparation method and thinking of a kind of new material.
Specific embodiment
Below by embodiment, the present invention will be further described, but not as to the limitation in the scope of the present invention.
Embodiment 1
Using natural rubber as matrix, using nano barium phthalate, concrete operation step is for filler：(1) by 100 mass parts
Natural rubber on a mill practice by room temperature modeling, is gradually added into the nano barium phthalate of 10 mass parts grain size 30nm, is then gradually added into 2
Mass parts sulphur cutter is kneaded, and beats triangle bag, is allowed to be kneaded uniformly, then be gradually poured into the DOP of 10 mass parts, is kneaded uniformly, goes out
Piece.(2) it is kneaded after parking 7-16h, pressure 15Mpa on vulcanizing press is set, vulcanizes 40min at 150 DEG C.(3) moral is used
State NovochtrolAlpha-A impedances instrument tests dielectric elastomer at room temperature, 1-106Dielectric constant in Hz frequency ranges.
The dielectric constant for obtaining brominated butyl dielectric elastomer composite material is shown in Table 1.(4) according to national standard GB/T 528-2009, using type
Number for U.S. Instron 3366 microcomputer controlled electronic universal tester sample stress-strain diagram.From ess-strain song
Elasticity modulus is calculated in line.The elasticity modulus data for obtaining dielectric elastomer composite material are shown in Table 1.
Embodiment 2
The preparation method is the same as that of Example 1, the difference is that the number of barium titanate is 50 mass parts.Test result is shown in Table 1.
Embodiment 3
The preparation method is the same as that of Example 1, the difference is that the number of DOP is 50 mass parts.Test result is shown in Table 1.
Embodiment 4
The preparation method is the same as that of Example 1, the difference is that the number of sulphur is 5 mass parts.Test result is shown in Table 1.
Embodiment 5
The preparation method is the same as that of Example 1, the difference is that particle is the TiO 2 particles of 60nm, mass parts are 10 parts, plasticising
Agent is aromatic oil, and mass parts are 10 parts, and test result is shown in Table 1.
Embodiment 6
Preparation method is with embodiment 5, the difference is that titanium dioxide number is 50 mass parts.Test result is shown in Table 1.
Embodiment 7
Preparation method is with embodiment 5, the difference is that aromatic oil number is 50 mass parts.Test result is shown in Table 1.
Embodiment 8
The preparation method is the same as that of Example 1, the difference is that particle is 200nm aluminium oxide particles, mass parts are 10 parts, and plasticizer is
Paraffin oil, mass parts are 10 parts, and test result is shown in Table 1.
Embodiment 9
Preparation method is with embodiment 8, the difference is that aluminium oxide particles mass parts are 50 mass parts.Test result is shown in Table 1.
Embodiment 10
Preparation method is with embodiment 8, the difference is that paraffin oil mass parts are 50 mass parts.Test result is shown in Table 1.
Embodiment 11
The preparation method is the same as that of Example 1, the difference is that particle is 30nm magnesium niobium lead zirconate titanate particles, mass parts are 10 parts, are increased
Modeling agent is naphthenic oil, and mass parts are 10 parts, and test result is shown in Table 1.
Embodiment 12
The preparation method is the same as that of Example 11, unlike magnesium niobium lead zirconate titanate particle number be 50 mass parts.Test result is shown in
Table 1.
Embodiment 13
The preparation method is the same as that of Example 11, unlike naphthenic oil number be 50 mass parts.Test result is shown in Table 1.
Embodiment 14
The preparation method is the same as that of Example 1, the difference is that particle is 30nm copper lead titanates particles, mass parts are 10 parts, plasticizer
For DOP, mass parts are 10 parts, and test result is shown in Table 1.
Embodiment 15
The preparation method is the same as that of Example 14, unlike copper lead titanates particle number be 50 mass parts.Test result is shown in Table 1.
Embodiment 16
The preparation method is the same as that of Example 14, unlike DOP numbers be 50 mass parts.Test result is shown in Table 1.Comparative example 1
The preparation method is the same as that of Example 1, the difference is that rubber matrix selection polyurethane, adds in receiving for 50 mass parts grain size 30nm
Rice barium titanate particles, 50 mass parts DOP.Test result is shown in Table 1.
Table 1
The present invention using natural rubber prepare dielectric elastomer composite material have smaller elasticity modulus (0.05MPa) and
Higher energy density (3.03mJ/cm3) and high machine-photoelectric transformation efficiency (14.7%).
Technical scheme of the present invention is described in detail in above-described embodiment.It is apparent that the present invention is not limited it is retouched
The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint
What is equal with the present invention or similar variation shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of high machine-photoelectric transformation efficiency native rubber composite material, which is characterized in that including following components and mass fraction：
Rubber matrix：100 parts
Vulcanizing agent：2-5 parts
Inorganic filler：10-50 parts
Plasticizer：10-50 parts
The rubber matrix is natural rubber；The vulcanizing agent is sulphur, and the inorganic filler is barium titanate, titanium dioxide
Titanium, aluminium oxide, magnesium niobium lead zirconate titanate or copper lead titanates；The plasticizer is dioctyl phthalate, aromatic oil, paraffin oil
Or naphthenic oil.
2. composite material according to claim 1, which is characterized in that the grain size of the semiconductor fills is 30nm-
200nm。
3. composite material according to claim 1, which is characterized in that dielectric constant is the composite material at 1 khz
3.45-12.32, Young's modulus 0.05-0.36MPa, machine-photoelectric transformation efficiency are 4.5-14.7%.
4. the preparation method of high machine-photoelectric transformation efficiency native rubber composite material described in claim 1, which is characterized in that including
Following steps：
(1) 100 mass parts of natural rubber, 2-5 mass parts vulcanizing agent, the inorganic filler of 10-50 mass parts, 10-50 mass parts are increased
It moulds agent and is kneaded slice；
(2) step (1) resulting sheet is vulcanized, required composite material is made.
5. preparation method according to claim 4, which is characterized in that the natural rubber is brombutyl.
6. preparation method according to claim 4, which is characterized in that the melting temperature is 20-60 DEG C.
7. preparation method according to claim 4, which is characterized in that park 7-9h before the sheet material vulcanization.
8. preparation method according to claim 4, which is characterized in that the temperature of the sheet material vulcanization is 140-150 DEG C.
9. preparation method according to claim 4, which is characterized in that the equipment of the sheet material vulcanization is vulcanizing press.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265983A (en) * | 2018-08-17 | 2019-01-25 | 北京旭阳科技有限公司 | Dielectric polyamide elastomer composition and preparation method thereof |
| CN114316364A (en) * | 2020-10-09 | 2022-04-12 | 北京化工大学 | Montmorillonite ceramic filler composite modified dielectric elastomer and preparation method and application thereof |
| CN115368725A (en) * | 2021-05-18 | 2022-11-22 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer composite material with high dielectric constant and low dielectric loss and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265983A (en) * | 2018-08-17 | 2019-01-25 | 北京旭阳科技有限公司 | Dielectric polyamide elastomer composition and preparation method thereof |
| CN114316364A (en) * | 2020-10-09 | 2022-04-12 | 北京化工大学 | Montmorillonite ceramic filler composite modified dielectric elastomer and preparation method and application thereof |
| CN114316364B (en) * | 2020-10-09 | 2023-06-27 | 北京化工大学 | Montmorillonite ceramic filler composite modified dielectric elastomer and preparation method and application thereof |
| CN115368725A (en) * | 2021-05-18 | 2022-11-22 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer composite material with high dielectric constant and low dielectric loss and preparation method thereof |
| CN115368725B (en) * | 2021-05-18 | 2023-08-11 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer composite material with high dielectric constant and low dielectric loss and preparation method thereof |
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