WO2015155040A1 - Peinture et enduits gélifiés à haute teneur en nanotubes de carbone - Google Patents

Peinture et enduits gélifiés à haute teneur en nanotubes de carbone Download PDF

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Publication number
WO2015155040A1
WO2015155040A1 PCT/EP2015/056773 EP2015056773W WO2015155040A1 WO 2015155040 A1 WO2015155040 A1 WO 2015155040A1 EP 2015056773 W EP2015056773 W EP 2015056773W WO 2015155040 A1 WO2015155040 A1 WO 2015155040A1
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WO
WIPO (PCT)
Prior art keywords
cnt
coating
epoxy
water
solvent
Prior art date
Application number
PCT/EP2015/056773
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English (en)
Inventor
Mikael Johannes NORDENG
Paal A. SKYBAK
Stein Dietrichson
Joachim KARTHÄUSER
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Re-Turn As
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Publication of WO2015155040A1 publication Critical patent/WO2015155040A1/fr

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Classifications

    • 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
    • C09D5/32—Radiation-absorbing paints
    • 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
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K3/041—Carbon nanotubes

Definitions

  • This invention relates to paint and gelcoat production
  • RAM radiation-absorbing materials
  • the invention describes a method to produce paints and gelcoats with high loads, such as higher than 5% or even higher than 10% by weight, of fillers, especially fillers which after dispersion cause a significant increase of
  • CNT viscosity, in particular CNT whereby CNT should be understood as carbon nano tubes, single wall and multi-wall,
  • metallized CNT such as metallized CNT or any similar carbon based material including grafene, fullerene and certain carbon black materials and other materials essentially
  • the production method includes dispersion of CNT in a liquid medium, preferably water or benign organic solvents such as lactates and acetates, by ultrasound or rapid
  • Additives include water- soluble polymers, hyperbranched polymers, dispersants, foam controllers and the like, see under embodiments.
  • the products thus obtained are applied by spraying or as gelcoat.
  • Separate A- and Ef ⁇ fractions containing CNT A and B standing for epoxy and curing agents, respectively) can also be sprayed together whereby the A- and B-stream are mixed prior to entry into the spray nozzle.
  • Gelcoats can show viscosities up to several thousand cps.
  • Gelcoats are usually applied by roll-up. It is important that sagging of paint is avoided. This is achieved by optimizing the paint thickness, adhesion to substrate, evaporation speed of solvent and hardening time. Equally, excessive porosity of paints is usually not desired. According to the invention, a system is provided which
  • the invention describes useful embodiments for coating of wind turbines, aircrafts, civil engineering objects and off-shore constructions.
  • Epoxy paint or gelcoat the following raw materials were used:
  • CNT are provided in dispersed form, starting from a water- dispersable masterbatch a.o. containing CNT and CMC (carboxy- methylcellulose) , available from e.g. Arkema under the trade name "Graphistrength CW2-45", alternatively by dispersing pure CNT and CMC by conventional means, e.g. ultrasound.
  • Water- bourne epoxy e.g.
  • Examples Epilink 360, 701, Anquamine 401, Anquawhite 100 or as available from Momentive (examples Epicure Curing agents 6870-W-53, 8290-Y-60, 8535-W-50, 8536-MY-60, 8537-WY-60, 8538- Y-68) .
  • Optional additives are impact modifiers such as
  • thickening agents such as micro- or nano-silica, such as
  • Aerosil TM or Cab-O-SilTM are added in concentrations of about 1-3% by weight.
  • PU paint or gelcoat the procedure is very similar to the one useful for epoxy formulation.
  • a range of water-dispersable candidates are available from companies such as Bayer, BASF and others.
  • two different epoxy or PU systems are used whereby the first system is curing rapidly, and the second system less rapidly.
  • the purpose is to achieve a viscosity increase quickly in order to prevent sagging of paint and gelcoat layers.
  • Useful raw materials are e.g.
  • Bayhydol A 2542 / Desmophen 3900 It is also generally useful to add metal articles, such as aluminium flakes.
  • formulation containing a very high CNT content which in addition can be applied outside of a factory and under adverse climatic conditions, e.g. during rainy periods.
  • the following general composition has been developed, based on a medium molecular weight epoxy (i.e. molecular weight 700-2500) diluted in xylene with typical
  • Typical trade names are Epikote 1001x75, Araldite GZ 601x75
  • the curing agent in the formulation is preferably a medium to low viscosity, reactive polyamide-based resin solution with typical values:
  • a concentrate of CNT with an epoxy carrier- Graphistrength CSl-25, typically 25% CNT is mixed with the epoxy solvent cut and a combination of ketones, MIBK, MEK under high shear mixing until the CNT is evenly dispersed.
  • the amount of solvents may vary from 100 to 500% calculated on the epoxy resin .
  • a concentrate of CNT with a CMC carrier Graphistrength CW 2- 45, typically 45% CNT is mixed with the polyamide based curing agent and a combination of Xylene, MIBK and MEK under high shear mixing until the CNT concentrate is evenly dispersed.
  • the amount of solvent may vary from 100 to 500% calculated on the polyamide curing agent.
  • the dissolving process may be followed by
  • the amount of CNT concentrate will be 10% CNT concentrate calculated on epoxy resin, combined with a curing agent with a content of 100% CNT concentrate calculated on polyaminoamide .
  • the amount of CNT concentrate will be 200% parts CNT concentrate calculated on epoxy resin, combined with a curing agent with a content of 75% CNT concentrate calculated on polyaminoamide.
  • Added solvent may also contain CNT in dispersed form,
  • Useful solvents are e.g. xylene, MIBK, MEK, acetone, i.e. solvents of aromatic, ester, ketone, paraffin or (capped) glycol nature, or mixtures of those.
  • Water is useful as additive as the CNT/cellulose complexes are especially water-dispersable .
  • Wind power blade deicing coating It was found that 500 micrometer of such a coating containing 11% CNT effectively absorb >90% of the microwave radiation emitted inside a wing. Deicing of a 1 m composite pipe used in cooled laboratory conditions (at minus 20 °C) could be achieved within 15 minutes, using ⁇ 0,1 kWh / m2. Higher or lower CNT
  • a very rough coating may be preferred facing the outside of the wing to minimise radar interference, see also arguments below.
  • a top coating is used which levels out the surface roughness of the CNT-containing coating.
  • a high quality top coating results in erosion stability and allows freedom to apply light colours to the final product.
  • metal as surface e.g. in the case of airplane wings, is acceptable.
  • Wind power blades are preferably used as coatings beneath the top coat of wind power blades, and preferably above a thermally insulating coating on the composite material, to avoid unnecessary heat loss. It is not necessary for blade producers to repeat the stability calculations for blades as the invention provides a method to apply a light-weight coating (e.g. 50 kg coating for a 60 m blade weighing some 15 000 kg) . Production processes do not have to be changed, as opposed to a heatable material (Ohmic or resistance heating) integrated into the current base composite. It also turned out that the coating is partly absorbing and partly reflecting microwave radiation. The ratio of absorption / reflection depends on the conductivity of the coating whereby higher CNT content results in higher
  • the coating can be embossed or structured, there are further technical options to control absorption and reflection. This can be done both at the surface facing the inside of the wing as well as the outside of the wing.
  • Radar absorbing and EMI shielding coatings Based on the chemistries described above, radar absorbing and EMI shielding coatings can be formulated whereby it is desired that the coating shows minimum reflectivity. An optimum combination of high CNT- concentration, low conductivity and low layer thickness is chosen.
  • the surface facing a radar source is preferably not smooth, but rather structured, e.g. embossed, such that radiation is reflected in an irregular manner. It can be suitable to apply a multilayer coating with increasing CNT concentration towards the inside of the object (and reverse in the case of EMI shielding coatings) . The task of the layer (s) with lower CNT concentration is to weaken incident and reflected radiation.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un nouveau procédé de production de peintures ou d'enduits gélifiés hautement chargés en charge, en particulier en nanotubes de carbone (CNT) qui peuvent être pulvérisés ou qui peuvent être appliqués par des brosses roulantes. La partie centrale de l'invention est d'employer un solvant tel que l'eau ou un solvant organique pour la dispersion des nanotubes de carbone (CNT). Ensuite, des composants de matériaux thermodurcissables tels que de l'époxy ou du polyuréthane (PU) sont ajoutés et intégrés dans la dispersion de nanotubes de carbone (CNT) jusqu'à ce qu'une viscosité appropriée soit atteinte de telle sorte que le produit peut être utilisée par pulvérisation (= peinture) ou par application roulante (= enduit gélifié). Le temps de durcissement et la vitesse d'évaporation du solvant, de préférence l'eau, sont ajustés de sorte que la production de pores, l'affaissement de la peinture, etc. sont réduits au minimum. Les produits sont utiles pour des revêtements antiradar (RAM = absorption des rayonnements), des revêtements de dégivrage, par exemple servant au chauffage par micro-ondes, blindages généraux contre les rayonnements électromagnétiques, les zones où la conductivité électrique de plus grandes surfaces sont nécessaires, tels que des revêtements antistatiques, et autres. Des modes de réalisation préférés sont décrits en détail.
PCT/EP2015/056773 2014-04-09 2015-03-27 Peinture et enduits gélifiés à haute teneur en nanotubes de carbone WO2015155040A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE1400194 2014-04-09
SE1400194-5 2014-04-09

Publications (1)

Publication Number Publication Date
WO2015155040A1 true WO2015155040A1 (fr) 2015-10-15

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108192493A (zh) * 2018-01-03 2018-06-22 深圳市碳能科技有限公司 一种石墨烯、碳纳米管增强防腐防弹涂料的制备方法
CN109332705A (zh) * 2018-10-29 2019-02-15 南京工程学院 石墨烯改性铜-钼-铜复合材料及其制备方法
CN109535865A (zh) * 2018-11-13 2019-03-29 云浮华云创新设计有限公司 一种纳米复合石材防护剂及其制备方法
CN109575783A (zh) * 2018-12-14 2019-04-05 合众（佛山）化工有限公司 一种抗静电防辐射新型环保涂料
CN111393988A (zh) * 2020-04-28 2020-07-10 西安钧盛新材料科技有限公司 一种基于石墨烯超黑消光涂层及其制备方法
CN112080168A (zh) * 2020-09-29 2020-12-15 衡阳凌云特种材料有限公司 一种环保防辐射复合涂料及制备方法
CN112411178A (zh) * 2020-10-16 2021-02-26 温州大学 一种碳纳米管-聚氨酯复合纤维的制备方法
CN115627119A (zh) * 2022-10-11 2023-01-20 航天特种材料及工艺技术研究所 轻质耐温隔热隐身涂料、涂层及其制备方法
CN117736626A (zh) * 2023-12-19 2024-03-22 扬州市鑫源电气股份有限公司 一种金属封闭式绝缘电线及其生产工艺
CN118460069A (zh) * 2024-07-11 2024-08-09 中国电建集团华东勘测设计研究院有限公司 一种压力交变工况的深海装备用涂层及其制备方法和应用

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WO2004106420A2 (fr) * 2003-05-22 2004-12-09 Zyvex Corporation Nanocomposites et procedes
US20100270069A1 (en) * 2009-04-24 2010-10-28 Lockheed Martin Corporation Cnt-infused emi shielding composite and coating
WO2011117530A1 (fr) * 2010-03-23 2011-09-29 Arkema France Melange-maitre de charges conductrices carbonees pour les formulations liquides, notamment dans les batteries li-ion
US20110281034A1 (en) * 2010-05-12 2011-11-17 Lee James L Layer-by-layer fabrication method of sprayed nanopaper
WO2012118434A1 (fr) * 2011-03-01 2012-09-07 Karthaeuser Joachim Procédés pour fabriquer des nanoparticules de carbone métallisées
WO2013172762A1 (fr) * 2012-05-16 2013-11-21 Jka Kemi Ab Dégivrage d'une surface de structures en général telles que des pales d'aérogénérateurs, des ailes d'aéronefs à l'aide de l'induction ou du rayonnement

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004106420A2 (fr) * 2003-05-22 2004-12-09 Zyvex Corporation Nanocomposites et procedes
US20100270069A1 (en) * 2009-04-24 2010-10-28 Lockheed Martin Corporation Cnt-infused emi shielding composite and coating
WO2011117530A1 (fr) * 2010-03-23 2011-09-29 Arkema France Melange-maitre de charges conductrices carbonees pour les formulations liquides, notamment dans les batteries li-ion
US20110281034A1 (en) * 2010-05-12 2011-11-17 Lee James L Layer-by-layer fabrication method of sprayed nanopaper
WO2012118434A1 (fr) * 2011-03-01 2012-09-07 Karthaeuser Joachim Procédés pour fabriquer des nanoparticules de carbone métallisées
WO2013172762A1 (fr) * 2012-05-16 2013-11-21 Jka Kemi Ab Dégivrage d'une surface de structures en général telles que des pales d'aérogénérateurs, des ailes d'aéronefs à l'aide de l'induction ou du rayonnement

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108192493A (zh) * 2018-01-03 2018-06-22 深圳市碳能科技有限公司 一种石墨烯、碳纳米管增强防腐防弹涂料的制备方法
CN108192493B (zh) * 2018-01-03 2020-03-17 深圳市碳能科技有限公司 一种石墨烯、碳纳米管增强防腐防弹涂料的制备方法
CN109332705A (zh) * 2018-10-29 2019-02-15 南京工程学院 石墨烯改性铜-钼-铜复合材料及其制备方法
CN109332705B (zh) * 2018-10-29 2021-01-12 南京工程学院 石墨烯改性铜-钼-铜复合材料及其制备方法
CN109535865A (zh) * 2018-11-13 2019-03-29 云浮华云创新设计有限公司 一种纳米复合石材防护剂及其制备方法
CN109575783A (zh) * 2018-12-14 2019-04-05 合众（佛山）化工有限公司 一种抗静电防辐射新型环保涂料
CN111393988A (zh) * 2020-04-28 2020-07-10 西安钧盛新材料科技有限公司 一种基于石墨烯超黑消光涂层及其制备方法
CN112080168A (zh) * 2020-09-29 2020-12-15 衡阳凌云特种材料有限公司 一种环保防辐射复合涂料及制备方法
CN112411178A (zh) * 2020-10-16 2021-02-26 温州大学 一种碳纳米管-聚氨酯复合纤维的制备方法
CN115627119A (zh) * 2022-10-11 2023-01-20 航天特种材料及工艺技术研究所 轻质耐温隔热隐身涂料、涂层及其制备方法
CN117736626A (zh) * 2023-12-19 2024-03-22 扬州市鑫源电气股份有限公司 一种金属封闭式绝缘电线及其生产工艺
CN118460069A (zh) * 2024-07-11 2024-08-09 中国电建集团华东勘测设计研究院有限公司 一种压力交变工况的深海装备用涂层及其制备方法和应用

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