KR102619125B1 - Piezoelectric paint composition containing reduced graphene oxides and manufacturing method thereof - Google Patents
Piezoelectric paint composition containing reduced graphene oxides and manufacturing method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 239000003973 paint Substances 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 50
- 239000011737 fluorine Substances 0.000 claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000003607 modifier Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229940113088 dimethylacetamide Drugs 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000006057 reforming reaction Methods 0.000 claims 1
- 239000008199 coating composition Substances 0.000 abstract description 16
- 239000010408 film Substances 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000003306 harvesting Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 4
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- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- WXJFKAZDSQLPBX-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)F WXJFKAZDSQLPBX-UHFFFAOYSA-N 0.000 description 1
- QROUUECTKRZFHF-UHFFFAOYSA-N 4,4,5,5,5-pentafluoropentan-1-ol Chemical compound OCCCC(F)(F)C(F)(F)F QROUUECTKRZFHF-UHFFFAOYSA-N 0.000 description 1
- VQBQAYXQUOKRAE-UHFFFAOYSA-N FC(CCCO)(C(F)(F)F)F.FC(CCCO)(C(F)(F)F)F Chemical compound FC(CCCO)(C(F)(F)F)F.FC(CCCO)(C(F)(F)F)F VQBQAYXQUOKRAE-UHFFFAOYSA-N 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- -1 fluoro-tert-butyl Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
Abstract
본 발명에 의한 압전 도료 조성물은 불소계 고분자, 알코올 표면개질제로 표면개질된 환원 그래핀 및 용매를 포함하며, 상기 알코올 표면개질제는 불소계 알코올을 포함하고, 상기 표면 개질된 환원 그래핀은 상기 불소계 고분자와 대비하여 0.0005 내지 0.002 중량% 포함되는 것을 특징으로 한다.The piezoelectric coating composition according to the present invention includes a fluorine-based polymer, reduced graphene surface-modified with an alcohol surface modifier, and a solvent, the alcohol surface modifier includes a fluorine-based alcohol, and the surface-modified reduced graphene is combined with the fluorine-based polymer. It is characterized in that it contains 0.0005 to 0.002% by weight.
Description
본 발명은 환원 그래핀을 포함하는 압전 도료 조성물 및 이의 제조방법에 관한 것이다. The present invention relates to a piezoelectric paint composition containing reduced graphene and a method for manufacturing the same.
에너지 하베스팅(Energy harvesting)이란 태양광, 진동, 열, 풍력 등과 같은 자연적인 에너지원으로부터 발생하는 에너지를 전기 에너지로 전환시켜 수확하는 기술을 의미한다. Energy harvesting refers to a technology that harvests energy generated from natural energy sources such as sunlight, vibration, heat, and wind power by converting it into electrical energy.
이 중에서도 압전 효과를 바탕으로 제안된 압전기반의 에너지 하베스터는 바람 및 태양 등과 같은 통상의 신재생 에너지원이 존재하지 않는 상황에서도, 미세한움직임에 의해 발생되는 진동, 굽힘 및 하중 등의 기계적 에너지를 전기적 에너지로 변환할 수 있는 기술로, 차세대 에너지 생산기술로 주목받고 있다. Among these, the piezoelectric-based energy harvester proposed based on the piezoelectric effect collects mechanical energy such as vibration, bending, and load generated by microscopic movements into electrical energy even in situations where ordinary renewable energy sources such as wind and sun do not exist. It is a technology that can be converted into energy, and is attracting attention as a next-generation energy production technology.
특히, 도로에 압전 기반의 에너지 하베스터를 설치하는 경우 안정적인 에너지원을 확보할 수 있는 장점이 있어, 이에 관련한 연구가 활발히 수행되고 있다. In particular, installing piezoelectric-based energy harvesters on roads has the advantage of securing a stable energy source, and related research is being actively conducted.
그러나, 통상의 압전 기반 에너지 하베스터의 경우 이를 제조한 뒤, 이를 기존 도로의 아스팔트면을 제거하고 매설하는 방법으로 설치가 가능하며, 이 과정에서 많은 시간 및 비용이 소요되는 문제점이 있다. However, in the case of a typical piezoelectric-based energy harvester, it can be manufactured and then installed by removing the asphalt surface of the existing road and burying it, but this process has the problem of taking a lot of time and money.
아울러, 종래 압전 물질을 포함하는 조성물을 도포하여 압전층을 형성하는 경우, 조성물을 도포하여 필름을 형성한 뒤 열처리 및 코로나 폴링 처리 등의 처리를 추가적으로 거쳐야 유의미한 수준의 압전 성능이 나타나는 한계가 있다. 그러나 이러한 코로나 폴링 처리는 대면적 처리가 극히 어려우며, 주변 설비들을 필요로 하여 도로 등의 구조물에서는 처리가 불가능한 한계가 있다.In addition, when forming a piezoelectric layer by applying a composition containing a conventional piezoelectric material, there is a limit to achieving a significant level of piezoelectric performance only after applying the composition to form a film and then undergoing additional treatments such as heat treatment and corona poling treatment. However, this corona polling treatment is extremely difficult to treat large areas, and requires surrounding facilities, so it has limitations that make it impossible to process on structures such as roads.
이에, 코로나 폴링 등을 필요로 하지 않으면서도 간단한 방법으로 에너지 하베스팅이 가능한 압전 도료 조성물의 개발이 필요한 실정이다. Accordingly, there is a need to develop a piezoelectric paint composition that allows energy harvesting in a simple manner without requiring corona poling.
본 발명의 목적은 간단한 방법으로 에너지 하베스팅이 가능한 압전 도료 조성물을 제공하는 것이다. The purpose of the present invention is to provide a piezoelectric paint composition capable of energy harvesting in a simple method.
본 발명의 다른 목적은 기존 도로를 훼손하는 공사과정 없이 압전 도료 조성물을 도포하여 압전 필름을 제조할 수 있는 압전 도료 조성물을 제공하는 것이다. Another object of the present invention is to provide a piezoelectric paint composition that can produce a piezoelectric film by applying the piezoelectric paint composition without a construction process that damages existing roads.
본 발명의 또 다른 목적은 코로나 폴링 처리 없이도 에너지 하베스팅 효율이 우수한 압전 도료 조성물을 제공하는 것이다.Another object of the present invention is to provide a piezoelectric paint composition with excellent energy harvesting efficiency even without corona poling treatment.
본 발명에 의한 압전 도료 조성물은 불소계 고분자, 알코올 표면개질제로 표면개질된 환원 그래핀 및 용매를 포함하며, The piezoelectric coating composition according to the present invention includes a fluorine-based polymer, reduced graphene surface-modified with an alcohol surface modifier, and a solvent.
상기 알코올 표면개질제는 불소계 알코올을 포함하고,The alcohol surface modifier includes a fluorinated alcohol,
상기 표면 개질된 환원 그래핀은 상기 불소계 고분자와 대비하여 0.0005 내지 0.002 중량% 포함되는 것을 특징으로 한다.The surface-modified reduced graphene is characterized in that it is contained in an amount of 0.0005 to 0.002% by weight compared to the fluorine-based polymer.
본 발명의 일 실시예에 의한 압전 도료 조성물에서 상기 불소계 고분자는 불화비닐리덴 작용기를 포함하는 것을 특징으로 할 수 있다. In the piezoelectric paint composition according to an embodiment of the present invention, the fluorine-based polymer may be characterized as including a vinylidene fluoride functional group.
본 발명의 일 실시예에 의한 압전 도료 조성물에서 상기 불소계 고분자는 폴리비닐리덴-트리플루오로에틸렌 공중합체인 것을 특징으로 할 수 있다. In the piezoelectric paint composition according to an embodiment of the present invention, the fluorine-based polymer may be a polyvinylidene-trifluoroethylene copolymer.
본 발명의 일 실시예에 의한 압전 도료 조성물에서 상기 폴리비닐리덴-트리플루오로에틸렌 공중합체는 트리플루오로에틸렌 작용기를 10 내지 40 몰% 포함하는 것을 특징으로 할 수 있다. In the piezoelectric paint composition according to an embodiment of the present invention, the polyvinylidene-trifluoroethylene copolymer may be characterized as containing 10 to 40 mol% of a trifluoroethylene functional group.
본 발명의 일 실시예에 의한 압전 도료 조성물에서 상기 용매는 메틸에틸케톤, 디메틸포름아마이드, 디메틸아세트아마이드, 트리에틸포스페이트 및 N-메틸-2-피롤리돈에서 선택되는 하나 또는 둘 이상을 포함하는 것을 특징으로 할 수 있다. In the piezoelectric coating composition according to an embodiment of the present invention, the solvent includes one or two or more selected from methyl ethyl ketone, dimethyl formamide, dimethyl acetamide, triethyl phosphate, and N-methyl-2-pyrrolidone. It can be characterized as:
본 발명의 일 실시예에 의한 압전 도료 조성물에서 상기 불소계 알코올은 말단에 -CF3 작용기를 포함하는 것을 특징으로 할 수 있다. In the piezoelectric paint composition according to an embodiment of the present invention, the fluorine-based alcohol may be characterized as including a -CF 3 functional group at the terminal.
본 발명의 일 실시예에 의한 압전 도료 조성물에서 상기 불소계 알코올은 분자량이 250 g/mol 이하인 것을 특징으로 할 수 있다. In the piezoelectric paint composition according to an embodiment of the present invention, the fluorine-based alcohol may have a molecular weight of 250 g/mol or less.
본 발명의 일 실시예에 의한 압전 도료 조성물에서 상기 압전 도료 조성물은 용매 100 중량부 대비 10 내지 30 중량부의 불소계 고분자를 포함하는 것을 특징으로 할 수 있다. In the piezoelectric paint composition according to an embodiment of the present invention, the piezoelectric paint composition may be characterized as containing 10 to 30 parts by weight of a fluorine-based polymer based on 100 parts by weight of the solvent.
본 발명은 또한 압전 도료 조성물 제조방법을 제공하며, 본 발명에 의한 압전 도료 조성물 제조방법은 산화 그래핀과 알코올 개질제를 혼합하여 개질 환원 그래핀을 제조하는 제 1단계; The present invention also provides a method for producing a piezoelectric coating composition, which includes a first step of producing modified reduced graphene by mixing graphene oxide and an alcohol modifier;
상기 개질 산화그래핀을 열처리로 환원하여 환원 그래핀을 제조하는 제 2단계; 및A second step of producing reduced graphene by reducing the modified graphene oxide through heat treatment; and
상기 환원 그래핀을 불소계 고분자에 투입한 뒤, 용매를 혼합하는 제 3단계;를 포함하며, A third step of adding the reduced graphene to the fluorine-based polymer and mixing a solvent,
상기 알코올 개질제는 불소계 알코올을 포함한다.The alcohol modifier includes fluorine-based alcohol.
본 발명의 일 실시예에 의한 압전 도료 조성물 제조방법에서 상기 알코올 개질제는 불소계 알코올을 25 내지 55 부피%로 포함하는 것을 특징으로 할 수 있다. In the method for manufacturing a piezoelectric coating composition according to an embodiment of the present invention, the alcohol modifier may be characterized in that it contains 25 to 55% by volume of fluorine-based alcohol.
본 발명의 일 실시예에 의한 압전 도료 조성물 제조방법에서 상기 제 1단계의 개질 반응 시 산을 투입하는 단계를 더 포함하는 것을 특징으로 할 수 있다.The method for manufacturing a piezoelectric paint composition according to an embodiment of the present invention may further include adding acid during the modification reaction in the first step.
본 발명에 의한 압전 도료 조성물은 불소계 고분자, 알코올 표면개질제로 표면개질된 환원 그래핀 및 용매를 포함하며, 상기 알코올 표면개질제는 불소계 알코올을 포함하고, 상기 표면 개질된 환원 그래핀은 상기 불소계 고분자와 대비하여 0.0005 내지 0.002 중량% 포함하여 도료의 도포만으로 에너지 하베스팅이 가능한 장점이 있으며, 도로에 시공 시 기존 도로의 훼손 없이 신속하게 시공이 가능한 장점이 있다.The piezoelectric coating composition according to the present invention includes a fluorine-based polymer, reduced graphene surface-modified with an alcohol surface modifier, and a solvent, the alcohol surface modifier includes a fluorine-based alcohol, and the surface-modified reduced graphene is combined with the fluorine-based polymer. In comparison, it has the advantage of enabling energy harvesting just by applying paint containing 0.0005 to 0.002% by weight, and has the advantage of being able to be constructed quickly without damaging the existing road when constructed on a road.
도 1 및 2는 본 발명의 제조예에 의해 제조된 도료 조성물을 도포 후 표면을 SEM(Scanning Electron Microscope)으로 관찰하고 이를 도시한 것이다.
도 3 및 4는 표면개질된 산화 그래핀의 환원 전후 FT-IR 측정 결과를 도시한 것이다. Figures 1 and 2 illustrate the surface observed with a SEM (Scanning Electron Microscope) after applying the coating composition prepared according to the preparation example of the present invention.
Figures 3 and 4 show FT-IR measurement results before and after reduction of surface-modified graphene oxide.
본 발명의 실시예들에 대한 이점 및 특징, 그리고 그것들을 달성하는 방법은 첨부되는 도면과 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해질 것이다. 그러나 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있으며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하고, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다. 명세서 전체에 걸쳐 동일 참조 부호는 동일 구성 요소를 지칭한다.Advantages and features of the embodiments of the present invention and methods for achieving them will become clear by referring to the embodiments described in detail below along with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and may be implemented in various different forms. The present embodiments are merely provided to ensure that the disclosure of the present invention is complete and to be understood by those skilled in the art. It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.
본 발명의 실시예들을 설명함에 있어서 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략할 것이다. 그리고 후술되는 용어들은 본 발명의 실시예에서의 기능을 고려하여 정의된 용어들로서 이는 사용자, 운용자의 의도 또는 관례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다.In describing embodiments of the present invention, if a detailed description of a known function or configuration is judged to unnecessarily obscure the gist of the present invention, the detailed description will be omitted. The terms described below are terms defined in consideration of functions in the embodiments of the present invention, and may vary depending on the intention or custom of the user or operator. Therefore, the definition should be made based on the contents throughout this specification.
본 발명에 의한 압전 도료 조성물은 불소계 고분자, 알코올 표면개질제로 표면개질된 환원 그래핀 및 용매를 포함하며, The piezoelectric coating composition according to the present invention includes a fluorine-based polymer, reduced graphene surface-modified with an alcohol surface modifier, and a solvent.
상기 알코올 표면개질제는 불소계 알코올을 포함하고,The alcohol surface modifier includes a fluorinated alcohol,
상기 표면 개질된 환원 그래핀은 상기 불소계 고분자와 대비하여 0.0005 내지 0.002 중량% 포함되는 것을 특징으로 한다. The surface-modified reduced graphene is characterized in that it is contained in an amount of 0.0005 to 0.002% by weight compared to the fluorine-based polymer.
본 발명에 의한 압전 도료 조성물은 도료를 도포하는 간단한 방법으로 압전 소자를 제조할 수 있는 장점이 있으며, 도로에 적용하고자 하는 경우 기존 도로를 훼손하지 않고 도포하는 방법으로 에너지 하베스팅이 가능한 장점이 있다. The piezoelectric paint composition according to the present invention has the advantage of being able to manufacture piezoelectric elements by a simple method of applying paint, and when applying it to roads, it has the advantage of being able to harvest energy by applying it without damaging the existing road. .
본 발명에서, 환원 그래핀이라 함은 산화 그래핀을 환원하여 제조된 것을 의미한다. In the present invention, reduced graphene means manufactured by reducing graphene oxide.
좋게는 상기 표면개질된 환원 그래핀은 상기 불소계 고분자와 대비하여 0.0007 내지 0.0015 중량% 포함될 수 있으며, 이러한 범위에서 환원 그래핀이 다수 포함되어 압전 네트워크에 영향을 주는 문제를 예방하고, 충분한 압전 성능 향상 효과를 나타낼 수 있는 장점이 있다. Preferably, the surface-modified reduced graphene may contain 0.0007 to 0.0015% by weight compared to the fluorine-based polymer. In this range, a large number of reduced graphene is included to prevent problems affecting the piezoelectric network and sufficiently improve piezoelectric performance. It has the advantage of being effective.
본 발명에 의한 압전 도료 조성물은 불소계 알코올을 포함하는 알코올 표면개질제로 표면개질된 환원 그래핀을 포함함으로써, 환원 그래핀의 분산성이 현저히 높아져 도막 내에 균일하게 분산되는 장점이 있으며, 이에 따라 환원 그래핀 첨가에 따른 압전 효율이 상승하여 출력 전압이 높아지며, 환원 전 산화 그래핀을 첨가한 경우와 대비하여도 높은 압전 효율을 나타내는 특징이 있다. The piezoelectric coating composition according to the present invention contains reduced graphene surface-modified with an alcohol surface modifier containing a fluorine-based alcohol, so that the dispersibility of the reduced graphene is significantly increased and has the advantage of being uniformly dispersed within the coating film. As a result, the reduced graphene is dispersed uniformly in the coating film. The piezoelectric efficiency increases with the addition of pins, resulting in a higher output voltage, and it has the characteristic of showing higher piezoelectric efficiency compared to the case where graphene oxide was added before reduction.
구체적으로, 상기 불소계 알코올은 말단에 -CF3기를 포함하는 알코올을 이용할 수 있으며, 좋게는 상기 불소계 알코올은 분자량이 250 g/mol 이하인 것을 이용할 수 있다. 구체적인 일예로 상기 불소계 알코올은 4,4,5,5,5-펜타플루오로-1-펜탄올, 2,2,3,3,4,4,4,-헵타플루오로-1-부탄올, 노나플루오로-터트-부틸 알코올 및 1,1,1,3,3,3,-헥사플루오로-2-프로판올에서 선택되는 하나 또는 둘 이상을 포함할 수 있다. Specifically, the fluorine-based alcohol may be an alcohol containing a -CF 3 group at the terminal, and preferably, the fluorine-based alcohol may have a molecular weight of 250 g/mol or less. As a specific example, the fluorine-based alcohol is 4,4,5,5,5-pentafluoro-1-pentanol, 2,2,3,3,4,4,4,-heptafluoro-1-butanol, nona It may include one or two or more selected from fluoro-tert-butyl alcohol and 1,1,1,3,3,3,-hexafluoro-2-propanol.
상기 알코올 표면개질제는 불소계 알코올과 저분자량 알코올을 포함할 수 있으며, 상기 저분자량 알코올은 구체적으로 메탄올, 에탄올 및 이소프로판올에서 선택되는 하나 또는 둘 이상을 포함할 수 있다. The alcohol surface modifier may include a fluorine-based alcohol and a low molecular weight alcohol, and the low molecular weight alcohol may specifically include one or two or more selected from methanol, ethanol, and isopropanol.
상기 알코올 표면개질제는 상기 불소계 알코올을 25 내지 55 부피%, 좋게는 30 내지 45 부피% 포함할 수 있으며, 잔부의 저분자량 알코올을 포함할 수 있으며, 불소계 알코올을 상술한 범위로 포함함으로써, 압전 도료 조성물로 생성되는 도막이 높은 납전 효율을 나타냄과 동시에 우수한 기계강도를 나타내는 특징이 있다. The alcohol surface modifier may contain 25 to 55% by volume of the fluorine-based alcohol, preferably 30 to 45% by volume, and may include the balance of low molecular weight alcohol. By including the fluorine-based alcohol in the above-mentioned range, the piezoelectric paint The coating film produced from the composition has the characteristic of exhibiting high soldering efficiency and excellent mechanical strength at the same time.
상기 불소계 고분자는 좋게는 불화비닐리덴 작용기를 포함하는 고분자를 이용할 수 있으며, 더욱 좋게는 상기 불소계 고분자는 폴리비닐리덴-트리플루오로에틸렌 공중합체일 수 있다. The fluorine-based polymer may preferably be a polymer containing a vinylidene fluoride functional group, and more preferably, the fluorine-based polymer may be a polyvinylidene-trifluoroethylene copolymer.
구체적인 일예로 상기 폴리비닐리덴-트리플루오로에틸렌 공중합체는 트리플루오로에틸렌 작용기를 10 내지 40 몰%, 좋게는 15 내지 35 몰% 포함할 수 있으며, 이러한 범위에서 상기 표면개질된 환원 그래핀과의 상용성을 극대화하고 높은 압전 효율을 확보할 수 있다. As a specific example, the polyvinylidene-trifluoroethylene copolymer may contain 10 to 40 mol%, preferably 15 to 35 mol%, of trifluoroethylene functional groups, and within this range, the surface-modified reduced graphene and It is possible to maximize compatibility and secure high piezoelectric efficiency.
상기 압전도료는 용매 100 중량부 대비 10 내지 30 중량부, 좋게는 12 내지 20 중량부, 더욱 좋게는 13 내지 19 중량부의 불소계 고분자를 포함할 수 있으며, 불소계 고분자를 소량 포함하는 경우 충분한 도막 두께 및 압전 효과를 확보하기 어려울 수 있으며, 불소계 고분자를 다량 포함하는 경우 작업성이 저하되고 균일한 두께의 도막을 형성하기 어려운 한계가 있다. The piezoelectric paint may contain 10 to 30 parts by weight, preferably 12 to 20 parts by weight, and more preferably 13 to 19 parts by weight of a fluorine-based polymer based on 100 parts by weight of the solvent. When it contains a small amount of the fluorine-based polymer, it has a sufficient film thickness and It may be difficult to secure the piezoelectric effect, and if a large amount of fluorine-based polymer is included, workability is reduced and there are limitations in forming a coating film of uniform thickness.
상기 용매는 상기 불소계 고분자를 용해시킬 수 있는 유기용매를 이용할 수 있으며, 좋게는 상기 용매는 메틸에틸케톤, 디메틸포름아마이드, 디메틸아세트아마이드, 트리에틸포스페이트 및 N-메틸-2-피롤리돈에서 선택되는 하나 또는 둘 이상을 이용할 수 있다. The solvent may be an organic solvent capable of dissolving the fluorine-based polymer. Preferably, the solvent is selected from methyl ethyl ketone, dimethyl formamide, dimethyl acetamide, triethyl phosphate, and N-methyl-2-pyrrolidone. You can use one or more than two.
본 발명은 또한 압전 도료 조성물 제조방법을 제공하며, 산화 그래핀과 알코올 개질제를 혼합하여 개질 환원 그래핀을 제조하는 제 1단계; The present invention also provides a method for producing a piezoelectric coating composition, comprising: a first step of producing modified reduced graphene by mixing graphene oxide and an alcohol modifier;
상기 개질 산화그래핀을 열처리로 환원하여 환원 그래핀을 제조하는 제 2단계; 및A second step of producing reduced graphene by reducing the modified graphene oxide through heat treatment; and
상기 환원 그래핀을 불소계 고분자에 투입한 뒤, 용매를 혼합하는 제 3단계;를 포함하며, A third step of adding the reduced graphene to the fluorine-based polymer and mixing a solvent,
상기 알코올 개질제는 불소계 알코올을 포함하는 것을 특징으로 한다. The alcohol modifier is characterized in that it contains a fluorine-based alcohol.
본 발명에 의한 압전 도료 조성물 제조방법은 상술한 단계를 포함하여 압전 도료 조성물을 제조할 수 있으며, 제조된 압전 도료 조성물을 단순히 도포하는 것으로 압전 효과를 나타내는 장점이 있다. The method for producing a piezoelectric paint composition according to the present invention can produce a piezoelectric paint composition including the steps described above, and has the advantage of exhibiting a piezoelectric effect by simply applying the prepared piezoelectric paint composition.
상기 제 1단계는 알코올 개질제 1L 당 산화 그래핀 1 내지 7 g을 투입하여 개질하는 단계일 수 있으며, 좋게는 상기 알코올 개질제 1L 당 산 수용액 20 내지 50 ㎖을 투입할 수 있고, 상기 산 수용액은 농도가 30 중량% 이상인 것을 이용할 수 있다. 아울러 상기 산화 그래핀은 통상의 Hummer’s method 등을 통해 제조된 것을 이용할 수 있으나, 본 발명이 이에 제한되는 것은 아니다. The first step may be a step of modifying by adding 1 to 7 g of graphene oxide per 1 L of the alcohol modifier. Preferably, 20 to 50 ml of an acid aqueous solution may be added per 1 L of the alcohol modifier, and the acid aqueous solution has a concentration of It can be used in an amount of 30% by weight or more. In addition, the graphene oxide may be manufactured using a conventional Hummer's method, etc., but the present invention is not limited thereto.
상기 제 2단계의 열처리는 비활성 기체 분위기에서 200 내지 300 ℃에서 3 내지 10시간 동안 수행될 수 있으며, 열처리 시간이 짧거나 온도가 낮은 경우 산화 그래핀의 환원이 충분히 이루어지지 않을 수 있으며, 열처리 시간이 길거나 온도가 높은 경우 산화 그래핀의 환원 효율은 높아지지 않으면서 알코올 개질에 의한 효과가 저하되고 환원 산화그래핀 생산에 불필요하게 많은 에너지가 소모될 수 있다. The second stage heat treatment may be performed at 200 to 300° C. for 3 to 10 hours in an inert gas atmosphere. If the heat treatment time is short or the temperature is low, the reduction of graphene oxide may not be sufficient, and the heat treatment time If this is long or the temperature is high, the reduction efficiency of graphene oxide does not increase, but the effect of alcohol modification decreases, and a lot of energy may be consumed unnecessarily in the production of reduced graphene oxide.
상기 제 2단계를 거쳐 환원된 산화그래핀을 불소계 고분자 및 용매와 혼합하여 압전 도료 조성물을 제조할 수 있으며, 불소계 고분자 및 용매는 앞서 설명한 것과 동일하며 중복기재를 피하기 위하여 상세한 설명은 생략한다. A piezoelectric paint composition can be prepared by mixing the graphene oxide reduced through the second step with a fluorine-based polymer and a solvent. The fluorine-based polymer and solvent are the same as those described above, and detailed descriptions are omitted to avoid redundant description.
본 발명은 또한 상기 압전 도료 조성물로 제조된 압전 필름을 포함한다. 상기 압전 필름은 압전 도료 조성물로 형성된 도막; 및 상기 도막의 일면 또는 양면에 형성된 전극을 포함할 수 있다. 이때 전극은 도막에서 압전 효과에 의해 생성된 전력을 전력을 필요로 하는 장치 또는 전력 저장장치에 전달하기 위한 것으로, 크게는 박막형 전극 및 전극용 도료 조성물로 형성한 전극 도막으로 구분할 수 있다. The present invention also includes a piezoelectric film made from the above piezoelectric coating composition. The piezoelectric film is a coating film formed of a piezoelectric coating composition; And it may include electrodes formed on one or both sides of the coating film. At this time, the electrode is used to transmit the power generated by the piezoelectric effect in the coating film to a device requiring power or a power storage device, and can be broadly divided into a thin film electrode and an electrode coating formed from a coating composition for electrodes.
상기 박막형 전극은 통상적으로 당업계에서 이용되는 것인 경우 제한없이 이용이 가능하며, 구체적으로 금, 은, 백금, 구리 및 알루미늄 등에서 선택되는 하나 또는 둘 이상을 포함하는 박막을 이용할 수 있다. The thin film electrode can be used without limitation as long as it is commonly used in the industry. Specifically, a thin film containing one or two or more selected from gold, silver, platinum, copper, and aluminum can be used.
상기 전극용 도료 조성물로 형성한 전극 도막은 전도성 필러 및 고분자 바인더를 포함하는 도료 조성물을 도포하여 전극 도막을 형성할 수 있다. 이때 전도성 필러는 탄소나노튜브, 그래핀, 환원 그래핀 및 환원된 환원 그래핀 등에서 선택되는 하나 또는 둘 이상의 탄소계 필러 또는 금, 은, 백금, 구리 및 알루미늄 등에서 선택되는 금속 필러를 포함할 수 있다. The electrode coating film formed from the electrode coating composition can be formed by applying a coating composition containing a conductive filler and a polymer binder. At this time, the conductive filler may include one or more carbon-based fillers selected from carbon nanotubes, graphene, reduced graphene, and reduced reduced graphene, or metal fillers selected from gold, silver, platinum, copper, and aluminum. .
또한 고분자 바인더는 통상적으로 이용되는 바인더인 경우 제한없이 이용이 가능하며, 좋게는 아크릴-우레탄 공중합체를 이용할 수 있으나 본 발명이 이에 제한되는 것은 아니다. In addition, the polymer binder can be used without limitation as long as it is a commonly used binder, preferably an acrylic-urethane copolymer, but the present invention is not limited thereto.
또한, 박막형 전극을 이용하는 경우, 상기 박막형 전극과 압전 도료 조성물을 경화하여 형성된 도막 사이에 접착을 위한 접착층을 더 포함할 수 있으며, 이러한 접착층 또한 상술한 탄소계 필러 또는 금속 필러를 포함하여 전도성을 확보하며, 압전 도막 및 박막형 전극을 접착할 수 있는 것인 경우 제한없이 이용이 가능하다. In addition, when using a thin film electrode, an adhesive layer for adhesion between the thin film electrode and a coating film formed by curing the piezoelectric paint composition may be further included, and this adhesive layer also includes the carbon-based filler or metal filler described above to ensure conductivity. It can be used without limitation as long as it can adhere piezoelectric coatings and thin film electrodes.
이하, 본 발명을 실시예 및 비교예에 의해 구체적으로 설명한다. 아래 실시예는 본 발명의 이해를 돕기 위한 것일 뿐이며, 본 발명의 범위가 아래 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples and comparative examples. The examples below are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the examples below.
[제조예 1][Production Example 1]
1. 표면개질된 산화 그래핀의 제조 1. Preparation of surface-modified graphene oxide
환원 그래핀 입자 3 g을 알코올 개질제 1L에 분산시키고, 90분간 초음파를 인가하여 분산한 뒤, 35 중량% 농도의 진한 염산 수용액을 35 ㎖ 혼합하고, 55 ℃에서 3시간 교반하여 개질반응을 수행하였다. 이후, 탄산수소나트륨을 pH가 6.5 내지 7이 될 때까지 투입하였으며, 고형분을 분리하고 상온에서 완전히 건조하여 개질 환원 그래핀을 제조하였다. 3 g of reduced graphene particles were dispersed in 1 L of alcohol modifier, and ultrasonic waves were applied for 90 minutes to disperse, then mixed with 35 ml of concentrated hydrochloric acid aqueous solution with a concentration of 35% by weight, and stirred at 55°C for 3 hours to perform a modification reaction. . Afterwards, sodium bicarbonate was added until the pH reached 6.5 to 7, and the solid content was separated and completely dried at room temperature to prepare reduced modified graphene.
이때 알코올 개질제는 메탄올 : 불소계 알코올을 6:4의 부피비로 혼합한 것을 이용하였으며, 불소계 알코올은 4,4,5,5,5-펜타플루오로-1-펜탄올(4,4,5,5,5-Pentafluoro-1-pentanol)을 이용하였다. At this time, the alcohol modifier was used as a mixture of methanol and fluorinated alcohol at a volume ratio of 6:4, and the fluorinated alcohol was 4,4,5,5,5-pentafluoro-1-pentanol (4,4,5,5 ,5-Pentafluoro-1-pentanol) was used.
2. 압전 도료 조성물의 제조2. Preparation of piezoelectric coating composition
제조된 표면개질된 환원 그래핀을 메틸에틸 케톤 용매 85 g에 투입한 뒤, 초음파를 조사하여 환원 그래핀을 분산시켰다. 이후, 15 g의 불소계 수지를 투입하고 교반하여 압전 도료 조성물을 제조하였다. 이때, 불소계 수지는 불화비닐리덴/트리플루오로에틸렌 공중합체(P(VDF-co-TrFE)로, VDF/TrFE 몰비가 70/30인 수지를 이용하였으며, 표면개질된 환원 그래핀은 상기 불소계 수지와 대비하여 0.001 중량%가 되도록 투입하였다. The prepared surface-modified reduced graphene was added to 85 g of methyl ethyl ketone solvent, and ultrasonic waves were applied to disperse the reduced graphene. Afterwards, 15 g of fluorine-based resin was added and stirred to prepare a piezoelectric paint composition. At this time, the fluorine-based resin was vinylidene fluoride/trifluoroethylene copolymer (P(VDF-co-TrFE), and a resin with a VDF/TrFE molar ratio of 70/30 was used, and the surface-modified reduced graphene was the fluorine-based resin. It was added to be 0.001% by weight compared to .
3. 압전 필름의 제조3. Preparation of piezoelectric film
하부 전극으로 백금 전극을 준비하였으며, 준비된 백금 전극에 전도성 접착제를 도포한 뒤, 여기에 압전 도료 조성물을 도포한 뒤 완전히 건조시켰다. 이후, 전도성 접착제를 다시 한번 도포하고, 상부 백금 전극을 접착한 뒤 완전히 건조하여 압전 필름을 제조하였다. A platinum electrode was prepared as the lower electrode, a conductive adhesive was applied to the prepared platinum electrode, a piezoelectric paint composition was applied thereto, and it was completely dried. Afterwards, the conductive adhesive was applied once again, the upper platinum electrode was attached, and then completely dried to prepare a piezoelectric film.
이때 전도성 접착제는 NMP(N-메틸-2-피롤리돈) 용매에 폴리아닐린을 10 중량% 농도로 용해한 뒤, 폴리아닐린 100 중량부 대비 백금 나노입자 80 중량부를 혼합하여 제조한 것을 이용하였다. At this time, the conductive adhesive was prepared by dissolving polyaniline in NMP (N-methyl-2-pyrrolidone) solvent at a concentration of 10% by weight and then mixing 80 parts by weight of platinum nanoparticles with 100 parts by weight of polyaniline.
[제조예 2][Production Example 2]
제조예 1과 같은 방법으로 제조하되, 상기 불소계 수지와 대비하여 환원 그래핀의 함량이 0.002 중량%가 되도록 혼합한 뒤, 이를 이용하여 압전 도료 및 압전 필름을 제조하였다. It was prepared in the same manner as Preparation Example 1, but mixed so that the content of reduced graphene was 0.002% by weight compared to the fluorine-based resin, and then used to prepare a piezoelectric paint and a piezoelectric film.
[비교예 1][Comparative Example 1]
메틸에틸케톤 용매에 15 중량%의 불화비닐리덴/트리플루오로에틸렌 공중합체(P(VDF-co-TrFE), VDF/TrFE = 70/30 몰비, 이하 수지라 함)을 혼합하여 압전 도료 조성물을 제조하였으며, 제조된 압전 도료 조성물을 이용하여 제조예 1과 같은 방법으로 압전 필름 또한 제조하였다. A piezoelectric paint composition was prepared by mixing 15% by weight of vinylidene fluoride/trifluoroethylene copolymer (P(VDF-co-TrFE), VDF/TrFE = 70/30 molar ratio, hereinafter referred to as resin) in methyl ethyl ketone solvent. A piezoelectric film was also manufactured in the same manner as Preparation Example 1 using the prepared piezoelectric paint composition.
[비교예 2][Comparative Example 2]
실시예 1과 같은 방법으로 제조하되, 환원 그래핀에 아무런 처리도 하지 않고 혼합하여 압전 도료 조성물 및 압전 필름을 제조하였다. A piezoelectric paint composition and a piezoelectric film were prepared in the same manner as in Example 1, but mixed with reduced graphene without any treatment.
산화 그래핀 함량 및 첨가 유무에 따른 압전 효과 확인Confirmation of piezoelectric effect depending on graphene oxide content and presence or absence of addition
제조예 1, 2 및 비교예 1, 2에서 제조된 압전 필름을 압전 미터(PiezoMeter)를 이용하여 d33 값을 측정하였으며, 1㎠ 당 50 N의 압력을 가하여 나타나는 출력 전압을 측정하고 그 결과를 하기 표 1로 나타내었다. The d33 value of the piezoelectric films prepared in Preparation Examples 1 and 2 and Comparative Examples 1 and 2 was measured using a PiezoMeter, and the output voltage appeared by applying a pressure of 50 N per 1 cm 2 was measured and the results are shown below. It is shown in Table 1.
표 1을 참고하면, 산화 그래핀을 전혀 포함하지 않은 비교예 1의 경우 d33값 및 출력 전압이 가장 낮은 것을 확인할 수 있다. 아무런 처리도 하지 않은 산화 그래핀을 포함하는 비교예 2의 경우 비교예 1과 대비하여 d33 값이 소폭 상승했으며, 출력전압이 현저히 상승한 것을 확인할 수 있다. 아울러, 불소계 알코올로 표면개질한 제조예 1 및 2의 경우 비교예 1 및 비교예 2와 대비하여 높은 d33값 및 출력 전압을 나타내는 것을 확인할 수 있으며, 이들 중에서도 제조예 1의 d33값 및 출력 전압이 가장 높은 것을 확인할 수 있다. Referring to Table 1, it can be seen that Comparative Example 1, which does not contain any graphene oxide, has the lowest d33 value and output voltage. In the case of Comparative Example 2 including graphene oxide without any treatment, it can be seen that the d33 value slightly increased and the output voltage increased significantly compared to Comparative Example 1. In addition, it can be seen that Preparation Examples 1 and 2, surface modified with fluorine alcohol, exhibit higher d33 values and output voltages compared to Comparative Examples 1 and 2. Among these, the d33 value and output voltage of Preparation Example 1 are You can check the highest one.
아울러, 제조예 1 및 제조예 2에서 제조된 압전층의 표면을 SEM으로 관찰하고 그 결과를 도 1 및 2로 나타내었다, 도 1 및 2를 참고하면, 도 1은 균일한 압전층을 나타냄을 확인할 수 있으나, 도 2의 경우 검은색의 결함이 발생함을 확인할 수 있으며, 이러한 결함에 의하여 표 1에 나타난 바와 같이 낮은 압전 성능을 나타내는 것으로 볼 수 있다. In addition, the surface of the piezoelectric layer manufactured in Preparation Example 1 and Preparation Example 2 was observed with SEM, and the results are shown in Figures 1 and 2. Referring to Figures 1 and 2, Figure 1 shows a uniform piezoelectric layer. However, in the case of Figure 2, it can be confirmed that black defects occur, and these defects can be seen as showing low piezoelectric performance as shown in Table 1.
[제조예 3] 환원에 의한 효과 확인[Preparation Example 3] Confirmation of effect by reduction
상기 제조예 1에서 제조된 표면 개질된 산화 그래핀을 아르곤 분위기에서 250 ℃로 4시간 동안 가열하여 산화 그래핀을 열환원하였으며, 최종적으로 표면개질된 환원 그래핀을 제조하였다. 제조된 환원 그래핀을 제조예 1과 같은 방법으로 혼합하여 압전 도료 조성물을 제조하고 이를 이용하여 압전 필름을 제조하였다. The surface-modified graphene oxide prepared in Preparation Example 1 was heated at 250° C. for 4 hours in an argon atmosphere to thermally reduce the graphene oxide, and finally, surface-modified reduced graphene was produced. The prepared reduced graphene was mixed in the same manner as in Preparation Example 1 to prepare a piezoelectric paint composition, and a piezoelectric film was manufactured using the same.
도 3 및 4는 표면개질된 산화 그래핀의 환원 전(도 3) 및 환원 후(도 4) FT-IR 측정 결과를 도시한 것으로, 도 3 및 4를 비교하면 환원에 의하여 3000 cm-1 부근의 피크가 작아져 산소가 제거된 것을 확인할 수 있다. Figures 3 and 4 show the FT-IR measurement results before reduction (Figure 3) and after reduction (Figure 4) of surface-modified graphene oxide. Comparing Figures 3 and 4, the reduction is around 3000 cm -1 due to reduction. The peak becomes smaller, confirming that oxygen has been removed.
아울러, 제조예 1의 압전 필름과 제조예 3의 압전 필름의 압전 효과를 측정하고 그 결과를 하기 표 2로 나타내었다. In addition, the piezoelectric effect of the piezoelectric film of Preparation Example 1 and the piezoelectric film of Preparation Example 3 was measured, and the results are shown in Table 2 below.
표 2를 참고하면, 산화 그래핀을 환원함으로써 d33값이 증가하고, 출력 전압 또한 높아지는 것을 확인할 수 있으며, 산화 그래핀을 환원하여 첨가함으로써 압전 효과에 긍정적인 영향을 미침을 확인할 수 있다.Referring to Table 2, it can be seen that the d33 value increases and the output voltage also increases by reducing graphene oxide, and that adding reduced graphene oxide has a positive effect on the piezoelectric effect.
Claims (14)
상기 알코올 표면개질제는 불소계 알코올 및 저분자량 알코올을 포함하고,
상기 불소계 알코올은 말단에 -CF3 작용기를 포함하며,
상기 알코올 표면개질제는 상기 불소계 알코올을 25 내지 55 부피%, 잔부의 저분자량 알코올을 포함하고,
상기 표면 개질된 환원 그래핀은 상기 불소계 고분자와 대비하여 0.0005 내지 0.002 중량% 포함되는 것을 특징으로 하는 압전 도료 조성물.
Contains reduced graphene surface-modified with a fluorine-based polymer and an alcohol surface modifier, and a solvent.
The alcohol surface modifier includes fluorine-based alcohol and low molecular weight alcohol,
The fluorinated alcohol contains a -CF 3 functional group at the end,
The alcohol surface modifier contains 25 to 55% by volume of the fluorinated alcohol and the balance is a low molecular weight alcohol,
A piezoelectric paint composition, characterized in that the surface-modified reduced graphene is contained in an amount of 0.0005 to 0.002% by weight compared to the fluorine-based polymer.
상기 불소계 고분자는 불화비닐리덴 작용기를 포함하는 것을 특징으로 하는 압전 도료 조성물.
According to clause 1,
A piezoelectric paint composition characterized in that the fluorine-based polymer contains a vinylidene fluoride functional group.
상기 불소계 고분자는 폴리비닐리덴-트리플루오로에틸렌 공중합체인 것을 특징으로 하는 압전 도료 조성물.
According to clause 2,
A piezoelectric paint composition, wherein the fluorine-based polymer is polyvinylidene-trifluoroethylene copolymer.
상기 폴리비닐리덴-트리플루오로에틸렌 공중합체는 트리플루오로에틸렌 작용기를 10 내지 40 몰% 포함하는 것을 특징으로 하는 압전 도료 조성물.
According to clause 3,
A piezoelectric paint composition, wherein the polyvinylidene-trifluoroethylene copolymer contains 10 to 40 mol% of a trifluoroethylene functional group.
상기 용매는 메틸에틸케톤, 디메틸포름아마이드, 디메틸아세트아마이드, 트리에틸포스페이트 및 N-메틸-2-피롤리돈에서 선택되는 하나 또는 둘 이상을 포함하는 것을 특징으로 하는 압전 도료 조성물.
According to clause 1,
A piezoelectric paint composition characterized in that the solvent includes one or two or more selected from methyl ethyl ketone, dimethyl formamide, dimethyl acetamide, triethyl phosphate, and N-methyl-2-pyrrolidone.
상기 불소계 알코올은 분자량이 250 g/mol 이하인 것을 특징으로 하는 압전 도료 조성물.
According to clause 1,
A piezoelectric paint composition, characterized in that the fluorine-based alcohol has a molecular weight of 250 g/mol or less.
상기 압전 도료 조성물은 용매 100 중량부 대비 10 내지 30 중량부의 불소계 고분자를 포함하는 것을 특징으로 하는 압전 도료 조성물.
According to clause 1,
The piezoelectric paint composition is characterized in that it contains 10 to 30 parts by weight of a fluorine-based polymer based on 100 parts by weight of the solvent.
상기 환원 그래핀은 열환원된 것을 특징으로 하는 압전 도료 조성물.
According to clause 1,
A piezoelectric paint composition, wherein the reduced graphene is thermally reduced.
상기 개질 산화 그래핀을 열처리로 환원하여 환원 그래핀을 제조하는 제 2단계; 및
상기 환원 그래핀을 불소계 고분자에 투입한 뒤, 용매를 혼합하는 제 3단계;를 포함하며,
상기 알코올 개질제는 불소계 알코올 및 저분자량 알코올을 포함하고,
상기 불소계 알코올은 말단에 -CF3 작용기를 포함하며,
상기 알코올 개질제는 상기 불소계 알코올을 25 내지 55 부피%, 잔부의 저분자량 알코올을 포함하는 것을 특징으로 하는 압전 도료 조성물 제조방법.
A first step of producing modified graphene oxide by mixing graphene oxide and an alcohol modifier;
A second step of producing reduced graphene by reducing the modified graphene oxide through heat treatment; and
A third step of adding the reduced graphene to the fluorine-based polymer and mixing a solvent,
The alcohol modifier includes fluorinated alcohol and low molecular weight alcohol,
The fluorinated alcohol contains a -CF 3 functional group at the end,
The alcohol modifier is a method of producing a piezoelectric paint composition, characterized in that it contains 25 to 55% by volume of the fluorine-based alcohol and the balance is a low molecular weight alcohol.
상기 제 1단계의 개질 반응 시 산을 투입하는 단계를 더 포함하는 것을 특징으로 하는 압전 도료 조성물 제조방법.
According to clause 10,
A method for manufacturing a piezoelectric paint composition, further comprising adding acid during the reforming reaction in the first step.
상기 제 2단계는 비활성기체 분위기 하에서 수행되는 것을 특징으로 하는 압전 도료 조성물 제조방법.
According to clause 10,
A method for manufacturing a piezoelectric paint composition, characterized in that the second step is performed under an inert gas atmosphere.
상기 제 2단계는 200 내지 300 ℃에서 수행되는 것을 특징으로 하는 압전 도료 조성물 제조방법.According to clause 10,
The second step is a method for producing a piezoelectric paint composition, characterized in that performed at 200 to 300 ° C.
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