WO2009158046A1 - Formulations de composites polymères à base de poly(fluorure de vinylidène) (pvdf) et de cyanoacrylates (ca) et procédés pour leur utilisation dans des applications à grande échelle - Google Patents

Formulations de composites polymères à base de poly(fluorure de vinylidène) (pvdf) et de cyanoacrylates (ca) et procédés pour leur utilisation dans des applications à grande échelle Download PDF

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WO2009158046A1
WO2009158046A1 PCT/US2009/036203 US2009036203W WO2009158046A1 WO 2009158046 A1 WO2009158046 A1 WO 2009158046A1 US 2009036203 W US2009036203 W US 2009036203W WO 2009158046 A1 WO2009158046 A1 WO 2009158046A1
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pvdf
composition
polymer
zno
coating
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PCT/US2009/036203
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Constantine M. Megaridis
Ilker S. Bayer
Manish K. Tiwari
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The Board Of Trustees Of The University Of Illinois
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • 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
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • VDF VINYLIDINE FLUORIDE
  • CA CYANO ACRYLATES
  • This invention is related to the area of polymer composites including poly(vinylidine fluoride) (PVDF).
  • PVDF poly(vinylidine fluoride)
  • CA cyanoacrylates
  • PVDF Poly(vinylidine fluoride)
  • PVDF is a polymer with exceptional chemical resistance, thermal stability and outstanding dielectric and piezoelectric properties, which justify its widespread use in many industries, for example as ultrafiltration and microf ⁇ ltration membrane materials, in lithium ion batteries, and in developing organic/inorganic or all- organic electro-mechanical composite materials.
  • PVDF is characterized by having a repeating monomer of the following structure: -[CH 2 -CF 2 ]-
  • PVDF has been used to prepare, for instance, special bioactive surfaces facilitating cellular proliferation and adhesion in human osteogenesis, in soft tissue applications, and as a suture material.
  • surface adhesion is critical
  • use of PVDF poses a severe challenge due to its inherent hydrophobicity and chemical inertness against functionalization.
  • dispersion of functional fillers, such as nanoparticles is poor.
  • polymer blending in solution is an easy and cost-effective technique, insolubility of PVDF in many common solvents hinders its potential use in polymer composites.
  • PVDF polymethylmethacrylate
  • PVDF+PMMA polymethylmethacrylate
  • PMMA polymethylmethacrylate
  • PVDF+PMMA polymethylmethacrylate
  • CA cyanoacrylates
  • C ⁇ N cyanoacrylates
  • cyanoacrylates display superior adhesion strength compared to other acrylics and they cure rapidly in biomedically favorable moist environments.
  • CAs are becoming increasingly important materials as tissue adhesives and sealants for various surgical procedures.
  • DMF Dimethyl formamide
  • An embodiment of the invention is a polymeric composition comprising a blend of poly(vinylidine fluoride) and at least one cyanoacrylate (CA). Rosin may be included in the composition to inhibit polymerization of the cyanoacrylate.
  • Another aspect of the invention is a polymeric composition
  • a polymeric composition comprising a blend of poly(vinylidine fluoride) and at least one starting cyanoacrylate monomer.
  • the CA monomer may be an ethyl 2-cyanoacrylate.
  • the monomer can be polymerized in a controlled fashion in solution in the presence of DMF.
  • a further aspect of the invention is a use of a polymeric composition comprising a blend of poly(vinylidine fluoride) and at least one cyanoacrylate (CA), comprising coating the composition onto a substrate and curing the composition to form a film on the substrate.
  • the substrate may be a rigid or flexible material (metal, plastic, etc.).
  • Another aspect of the invention is the incorporation of functional filler micro/nanoparticles.
  • Both surface functionalized and non-functionalized fillers can be added to the blends of poly(vinylidine fluoride) and at least one cyanoacrylate (CA) to provide coatings with controllable surface energy (wettability), morphology and other useful properties, such as chemical inertness, enhanced environmental stability, thermal stability, improved electrical characteristics and many others.
  • CA cyanoacrylate
  • Fig. l(a) illustrates aluminum foil coated with a CA/rosin dispersion containing zinc oxide particles but no PVDF.
  • Fig. l(b) illustrates aluminum foil coated with a PVD F/C A/rosin dispersion containing zinc oxide particles.
  • Fig. l(c) is a graph that illustrates the change in elastic modulus and peel strength of nanocomposite coating over a range of PVDF/CA blend weight ratios and with varying amounts of zinc oxide.
  • Fig. 2(b) is a SEM micrograph of a glass fiber covered with ZnO nanopowder-filled PVDF/CA/rosin coating.
  • Fig. 2(c) is a SEM micrograph of a bundle of glass fibers with a microporous PVDF/CA/rosin coating.
  • Fig. 3(a) is a graph of water contact angle variation as a function of applied tensile stress on woven fiberglass cloths coated with PVDF/CA/rosin/ZnO, containing unmodified ZnO nanopowder.
  • Fig. 3(b) is a graph of water contact angle variation as a function of applied tensile stress on woven fiberglass cloths coated with PVDF/CA/rosin/ZnO, containing functionalized ZnO.
  • Fig. 4(a) is a SEM micrograph of an edge portion of a drop-cast PVDF/polyCA film.
  • Fig. 4(b) is a SEM micrograph of a portion very near the edge of a drop-cast PVDF/polyCA film.
  • Fig. 4(c) is a SEM micrograph of a middle portion of a drop-cast PVDF/polyCA film.
  • Fig. 4(d) is a SEM micrograph of the center portion of a drop cast PVDF/polyCA film.
  • Fig. 5 shows a schematic of a drop cast PVDF/polyCA film to illustrate the locations of the film portions shown in the micrographs of Fig 4(a) - Fig. 4(d).
  • Fig. 6 is an x-ray diffraction plot of PVDF/polyCA films.
  • Fig. 7(a) is a graph of water droplet contact line diameter versus time for PVDF/polyCA films in the droplet spreading stages.
  • Fig. 7(b) is a graph of water droplet contact line diameter versus time for PVDF/polyCA films in the droplet receding stages.
  • Fig. 8(a) is a graph of water droplet contact line diameter versus time for PVDF/polyCA films in the droplet spreading stages.
  • Fig. 8(b) is a graph of water droplet contact line diameter versus time for PVDF/polyCA films in the droplet receding stages.
  • Fig. 9 is a graph of the dynamic contact angle of water droplets impacting rigid PVDF/polyCA films.
  • Fig. 10 is a graph of estimated surface energy of PVDF/polyCA films.
  • Figs. 11 (a) - l l(d) are SEM micrographs of a ZnO nanoparticle-laden PVDF/polyCA film, at different magnifications.
  • Figs. 12(a) - 12(d) are SEM micrographs of a ZnO nanoparticle-laden PVDF/polyCA film modified with rosin and layered silicate particles, at different magnifications.
  • Fig. 13 illustrates a water droplet impact and bounce back on a ZnO-in-PVDF/polyCA nanocomposite surface.
  • Fig. 14 is a graph of the change in water and water + IPA mixture contact angle with content of ZnO nanoparticles in the coating
  • Fig. 15 is a graph of the change in water and water + IPA mixture contact angle with content of PTFE microparticles in the coating.
  • Fig. 16 is a graph of the change in water and water + IPA mixture contact angle with content of ZnO microparticles in the coating.
  • Fig. 17 is a graph of the change in water and water + IPA mixture contact angle with content of PTFE microparticles and ZnO nanoparticles in the coating.
  • Fig. 18 is a graph of the change in water and water + IPA mixture contact angle with content of ZnO microparticles and ZnO nanoparticles in the coating.
  • cyanoacrylates cyanoacrylates
  • CAs 2-cyanoacrylic acid
  • Dermabond a commonly used wound adhesive
  • Other higher molecular weight CAs can also be used. These CAs can be obtained by altering the alkoxycarbonyl (-COOR) group of the molecule to obtain CA compounds of different chain lengths.
  • a strong adhesive bond is achieved at room temperature, without use of catalysts or pressure, within a short time period, ranging from several seconds to several minutes.
  • the adhesive action is the result of exothermal anionic polymerization, initiated by adsorbed moisture on the surface.
  • many polar and environmentally friendly solvents react with CAs through nucleophilic polymerization. As such, the instant polymerization of CAs hinders their applications in solution-based polymer composites.
  • CAs Another drawback of CAs is their inability to disperse nanoparticles that are comprised mostly of metal or metal oxide, due to the existence of naturally adsorbed moisture on the surface of these particles.
  • CA pastes containing a number of inorganic fillers were developed particularly for dental applications, and some instant polymerization inhibitors, such as weak acids, have been suggested to enable particle dispersion in such CA compositions.
  • use of surfactants in CA systems is again nearly impossible due to instant reaction of CAs with various ionic and anionic surfactants in solution.
  • DMF Dimethylformamide
  • the CA monomer for instance ethylcyanoacrylate
  • polyCA polymer having a high degree of polymerization
  • the ethylcyanoacrylate monomer may be partially polymerized in DMF in the presence of an appropriate co- solvent prior to mixing, for instance methyl ethyl ketone (MEK) or acetone, thus blends of PVDF and polymerized CA are made possible, and are referred to herein as "PVDF- polyCA” or "PVDF/polyCA.”
  • Suitable co-solvents are ketones and acetates. These are generally used to disperse cyanoacrylates. Ideal PVDF to polyCA weight ratios would be 60:40 or 70:30, much like commercial PVDF/PMMA coating formulations.
  • an alternative co-solvent based technique to control the polymerization reaction of cyanoacrylates is provided.
  • This technique eliminates the need for cooling, which is typically used to remove the heat generated by exothermic polymerization of CA in the presence of DMF.
  • boiled linseed oil (BLO) a common drying oil frequently used in woodworking as a water and oil resistant coating, is incorporated in the solvent blend. It is known that the presence of weak carboxylic acids in solution hinders rapid exothermic polymerization of CAs in solution.
  • Linseed oil is a natural fatty acid, with typical fatty acid content by weight as follows: Palmitic acid 6.0; Stearic acid 2.5; Arachidic acid 0.5; Oleic acid 19; Linoleic acid 24.1; Linolenic acid 47.4.
  • a CA monomer solution in either methyl ethyl ketone (MEK) or acetone may be prepared, then drops of BLO are added to the solution and stirred. The solution will become visibly thicker, indicating that the CA is polymerizing.
  • This polyCA solution may then be blended with a solution of PVDF in DMF to form a PVDF-polyCA composite.
  • solvent-processed fabrication of coatings comprising PVDF and CA blends form a polymer matrix with tunable microstructure and hydrophobicity.
  • Application-specific variations in surface wettability and microstructure are achieved by adding functional micro and nano-structured fillers into the polymer blend.
  • the PVDF-CA and PVDF-polyCA blends can be filled with various microf ⁇ llers and/or nanofillers, for example and without limitation, particles of ZnO, TiO 2 , Indium Tin Oxide (ITO), SiO 2 , single or multi-walled carbon nanotubes (SWCNT or MWCNT), carbon black (CB), hydroxyapatite, clay or various other polymer powder fillers, such as Teflon or polyetheretherketone (PEEK) or polyethylene (PE), for additional functionality (e.g., tuning the surface energy of films from partially hydrophilic to super hydrophobic) and enhanced high temperature resistance.
  • a coating of a PVDF/CA or PVDF/polyCA blend comprising fillers may exhibit superhydrophobicity.
  • the characteristic "superhydrophobic" may be applied to a material having a static water contact angle greater than 150°.
  • the polymeric composite coatings described herein achieve such high static water contact angles by the presence of a hierarchical roughness structure spanning from micro to nano-scale sizes, along with the presence of the hydrophobic polymer PVDF.
  • Superhydrophobic surfaces over which water contact angles exceed 150° are also considered self-cleaning. Surfaces over which water contact angles are as high as 120° (Teflon, for example) are considered hydrophobic.
  • PVDF-CA and PVDF-polyCA composites can be used as functional and biocompatible coatings in numerous industries, for example and without limitation in microelectronics, fluid power, construction, and medical technology applications.
  • the polymer composites according to embodiments of the invention may be applied as a coating to a substrate in an open-air well ventilated environment, for example, by low-cost methods, such as drop casting, spin coating and spray casting. Any suitable casting equipment may be employed to coat the composite onto a substrate, for example an industrial grade internal mix airbrush atomizer (ANEST IWATA, USA Inc., Westchester, OH). Further, any substrate that is sufficiently clean to allow good adhesion of the coating may be used.
  • a notable advantage of this coating technique is that it may be performed by a regular spraying process, which is uniquely suited to large area coating applications. In general, this is one of the primary limitations in commercializing technologies for making superhydrophobic surfaces for large area applications.
  • plasma processing appeared to be the only technique of superhydrophobic surface preparation with potential for large area applications.
  • plasma processing is limited by the size of the plasma reactor.
  • recently some works have demonstrated the use of scalable spray techniques for making superhydrophobic surfaces, our technique remains unique because the drying stage in our methods occurs at moderate temperatures (i.e., below 130 0 C), with drying times on the order of minutes. Even temperatures below 100 0 C can be used when the drying times are extended.
  • most of our superhydrophobic coatings are prepared from biocompatible components, which make them uniquely suited for biological applications. These characteristics make the processes very attractive for wide range of industrial applications.
  • a further significant advantage of the polymeric composites of the present invention is that they are robust.
  • coatings formed from the composites can withstand mechanical stress and still remain adhered to a substrate and maintain their hydrophobic or superhydrophobic characteristics.
  • the materials involved in the coatings described herein are fairly inexpensive, making the process scalable and economically feasible. Therefore, these techniques can be developed into versatile, industrially feasible, low cost methods to produce coatings with different surface energies for a broad range of applications.
  • PVDF/CA solution blends may be prepared in the presence of rosin.
  • CA monomer (2-ethylcyanoacrylate, Sigma-Aldrich, USA) dissolved in MEK was directly blended with rosin (Sigma-Aldrich, USA) stock solution consisting of a 60 wt. % rosin dispersion in isopropyl alcohol/castor oil (7/1 wt.) solvent.
  • rosin Sigma-Aldrich, USA
  • the blends were adjusted such that a PVD F/C A/rosin wt. ratio of 6/3/1 was maintained in solution to ascertain hydrophobic coatings.
  • MEK was added to further dilute the multi-component polymer dispersion and make it suitable for spray coating.
  • the polymer mixtures prepared in this manner were used to obtain different filler dispersions by adding either dry zinc oxide (ZnO) microparticles ( ⁇ 5 ⁇ m in diameter, Sigma-Aldrich, USA) or dry (ZnO) nano-powder ( ⁇ 70 nm in diameter, Alfa Aesar, Ward Hill, MA) or a commercial surface functionalized ZnO nano-dispersion (NanoTek 50 wt. %, 70 nm, Alfa Aesar, Ward Hill, MA). Surface functionalization of ZnO was achieved by encapsulating the particles with hydrophilic polyhydroxylated macromolecules (i.e., long-chain glycols).
  • Coatings were spray cast onto substrates using an industrial grade internal mix airbrush atomizer (ANEST IWATA, USA Inc., Westchester, OH). Polished aluminum foil and a highly hydrophilic 2-D yarn fiberglass cloth (BGF Industries, Greensboro, NC) were used as substrates. As discussed further below, the surface functionality of the nanoparticles prior to blending had a profound effect on the wettability and adhesion strength of the resulting coatings.
  • Figs. l(a) to l(c) a piece of aluminum foil coated with a film containing 7 wt. % functionalized ZnO nanoparticles dispersed in a CA/rosin (3/1 wt.) solution and without any PVDF is shown in Fig. l(a).
  • the coating was cured at a temperature of ⁇ 85 0 C in open air for 30 minutes, and the coating caused the initially flat foil to coil up.
  • the contraction of the film is believed to be caused by rapid cross-linking of the CA monomer upon thermosetting.
  • the cohesive cross-linking strength of acrylic matrices upon curing can reach ⁇ 10 MPa, which may cause the aluminum foil to coil up.
  • CA polymerization cohesive strength is even higher, i.e., ⁇ 25 MPa, thus causing the film to be stiff and brittle.
  • the change in modulus of elasticity was measured as a function of PVDF/CA blend weight ratio, while the rosin content was ⁇ 12 wt. % in all cases.
  • An Instron 5540 tensile tester (Instron, Norwood, MA) was used with 400 ⁇ m thick cast film specimens.
  • Curves (1), (2), (3) in Fig. l(c) show the elastic modulus of the nanocomposite coatings to increase with concentration of functionalized ZnO nanoparticles in the range 2 to 8 wt. %.
  • Pure CA/ZnO composites (0% PVDF/CA ratio) were very stiff; as PVDF was added and its concentration increased, the modulus of elasticity of the coatings declined by more than 50%. This suggested more flexible composites in the presence of PVDF.
  • Ultra-high molecular weight polyethylene which is widely used as a load- bearing orthopedic implant, has a modulus of elasticity of - 1000 MPa.
  • the PVDF/CA based composites produced here appear to match or exceed the elastic properties of UHMWPE, in addition to being easily solution processable.
  • Figure l(c) also shows the estimated peel strengths of the composite coatings on a polished smooth aluminum surface in curves (V), (T) and (3'). Two separate regions of peel strength are apparent, namely a regime of low sensitivity to PVDF concentration (up to 60 wt. %), and above 60 wt. % a regime of higher sensitivity.
  • Estimated peel strength values of the present composites with less than 60 wt. % PVDF match or exceed commercial aluminum composite panels containing modified polyester/PVDF blends ( ⁇ 400 N/m) or PVDF surfaces modified by plasma enhanced graft co-polymerization techniques.
  • FIG. 1 shows a SEM image of an uncoated glass fiber having a diameter of about ⁇ 10 ⁇ m diameter, separated from a hydrophilic fiberglass cloth.
  • the inset in Fig. 2(a) shows a coated fiberglass cloth sample.
  • FIG. 2(b) shows the morphology of the dry ZnO nanopowder-filled PVDF/C A/rosin (wt. ratio of 6/3/1) coating on a glass fiber separated from the yarn.
  • the coating was spray cast on the fiberglass textile and cured at 100 0 C for 30 minutes. As illustrated, the coating introduced both micro and nano-scale roughness on the fiberglass substrate, thus rendering the fiber hydrophobic. The detail of the roughness is magnified in the inset of Fig. 2(b).
  • the contact angles appear to stay nearly constant for applied stresses up to 3 kN/m 2 for all samples.
  • the amount of stress experienced by joints in a human body during normal movement is approximately 1 kN/m 2 , whereas athletes may apply up to about 3 kN/m 2 of stress on their joints. Consequently, the polymeric composite coatings containing ZnO filler particles remain hydrophobic even under substantial mechanical stress.
  • Figure 3(b) shows the results for fiberglass cloths coated with PVDF/CA/rosin (wt. ratio of 6/3/1) composite containing functionalized ZnO nanoparticles. Wetting of the coated surfaces remained nearly unchanged for stress values up to 15 kN/m 2 even for 10 wt. % particle loading. This indicates that the coatings withstood higher stress rates without peeling off from the substrate. It is possible that better dispersion of the functionalized nanoparticles within the polymer matrix, as compared to unmodified ZnO, enables efficient polymer chain mobility, hence improving strain resistance.
  • nanoparticle dispersion within the polymer matrix can transform large PVDF spherulites into thin fiber-like crystallites, thus causing better energy dissipation within the polymer matrix.
  • Better dispersed functionalized nanoparticles decreased coating hydrophobicity, as evidenced by the contact angles in Fig. 3b when compared to those in Fig. 3a, possibly by diminishing hierarchical surface roughness.
  • CA ethyl 2-cyanoacrylate (CA) monomer
  • MEK reagent grade MEK
  • DMF acts as a catalyst in rapid anionic polymerization of CA, however, in a co- solvent system in which the relative amount of DMF in solution is adjusted, the anionic polymerization reaction of CA progresses more slowly. Through such slow polymerization, a polymer having a high degree of polymerization (polyCA) is obtained, resulting in lower residual strain and elevated flexibility in comparison with polymers obtained by rapid polymerization.
  • polyCA polymer having a high degree of polymerization
  • the fillers were added directly and stirred using a vortex mixer without using additional dispersants or surfactants.
  • the resulting dispersions were very stable for the time scale of subsequent coating/casting experiments.
  • FIG. 4(a)-(d) the change in morphology is shown for a PVDF/polyCA film with a weight blend ratio of 0.25:1 PVDF:polyCA as a function of distance from the edge (i.e., contact line) of the film. Similar variations in the morphology were found for other concentrations as well.
  • the pictures shown in Fig. 4 are SEM images. The image at the film center, Fig. 4(d), reveals a membrane with pore sizes of 2-5 ⁇ m in diameter. The micro-porosity of the film decreases from its center to the edge, and ultimately vanishes at the film edge, as shown in Fig. 4(a). Without wishing to be bound by theory, it is believed that this morphological change is related to the change in the film thickness from center to edge, and can be explained using the schematic shown in Fig. 5, as follows.
  • FIGs. 7 and 8 the results of water droplet impact on the PVDF/polyCA drop cast composite films are presented.
  • the impact Weber numbers, (“We") were 11 and 14, respectively.
  • the two values of the We are in the range that should produce droplet spreading/receding on the partially wettable to non-wettable surfaces that are considered here.
  • the drop impact for each Weber number was performed on three different films with different blend ratios of PVDF to polyCA (0.25:1 by wt., represented by stars, 0.5:1 by wt., represented by circles, and 1 :1 by wt., represented by triangles, in Figs. 7 and 8).
  • Fig. 9 the temporal change in apparent dynamic contact angle for water droplet impact on the PVDF/polyCA films is presented. Only impacts with We ⁇ 11 on each of two films (blend wt. ratios 0.25:1, represented by stars, and 0.5:1, represented by squares) are shown; the measurements for other We were similar due to close We values.
  • the equilibrium contact angles of 60° and 70° for the two tests in Fig. 9 suggest that these films are partially wettable in nature.
  • the dynamic contact angle variation shown in Fig. 9 is typical of partially wettable surfaces except in the receding phase of the contact line motion for t ⁇ 1 to 5.
  • the receding phase is marked by more rapid changes in the dynamic contact angle, which reflects a competition between the capillary forces and contact line friction, which is enhanced by the surface heterogeneity, especially for the second film, which has a blend wt. ratio of 0.5:1 PVDF to polyCA.
  • Figure 10 presents the change in surface energy of the PVDF/polyCA composite films as function of the blend ratio of the two polymers.
  • the surface energy was estimated using the acid-base method, as described in connection with different polymeric surfaces in the following publication: Bayer, I. S., CM. Megarids, J. Zhang, D. Gamota, and A. Biswas, "Analysis and surface energy estimation of various model polymeric surfaces using contact angle hysteresis," Journal of Adhesion Science and Technology, 21(15): p. 1439-1467, 2007.
  • the surface energy of a surface is a measure of its adhesion, and the higher the surface energy, the better is its adhesion quality.
  • the surface energy of the PVDF/polyCA films decreases with increasing concentration of the PVDF in the blends.
  • the second technique involved blending a commercial ZnO acetate-based colloidal dispersion (Alfa Aesar, Ward Hill, MA) with the PVDF/polyCA polymer solution.
  • the multi- component slurries were then spray coated on aluminum substrates.
  • a tackifying resin i.e., gum rosin
  • a tackifying resin was introduced as a powder to the polymer blends in solution.
  • the best dispersion was achieved when rosin was also present.
  • TiO 2 particles were introduced from a separate colloidal dispersion prepared according to the method disclosed in the following publication: Conley, R.F., Practical dispersion, New York: Wiley- VCH, p.201, 1996.
  • the dispersion formulation was adjusted with the help of surfactants and plasticizers in such a way that it could form high-solid content conformal coatings.
  • Table I shows the compositional details of the solvent-based TiO 2 suspension.
  • Table I Compositional details of the solvent-based TiO 2 suspension.
  • TiO 2 42 Filler Ti-Pure ® R-902+ rutile, DuPont, Edge Moor, DE
  • the colloidal dispersion was miscible with the PVDF/polyCA solution at any proportion.
  • the level of hydrophobicity of the surfaces of the resulting film coated and cured on a substrate as a function of nano-particle inclusion was characterized by means of static contact angle measurements, and the morphologies of these coatings were investigated by SEM.
  • SEM images are provided of spray coatings of PVDF/polyCA blends containing ZnO nanoparticle filler.
  • the coatings possesses the hierarchical roughness structure that changes from micro-roughness to nano-roughness, as is evident from the images in Fig. 11, which were taken at increasingly higher magnifications from 11 (a) to l l(d).
  • the two-polymer blend on its own i.e., in the absence of any filler
  • the presence of nanoparticle fillers at high concentration such as about ⁇ 9 wt.
  • % provides nucleation sites for the polymer phases coming out of the solution due to solvent removal. This nucleation phenomenon results in the formation of a nanocomposite, as illustrated by Fig. l l(d).
  • the static contact angle of a sessile water droplet on this coating was measured to be about 155°.
  • This superhydrophobicity of the sprayed coating can be explained by the presence of a hierarchical roughness structure spanning from micro to nano-scales, along with the presence of the hydrophobic polymer PVDF. The presence of polyCA improves the adhesion property of these coatings.
  • Figure 12 shows surface morphology of clay- and ZnO-f ⁇ lled PVDF/PolyCA nano- porous composite surfaces including the gum rosin tackifier.
  • ZnO in the composite was introduced from a commercial colloidal dispersion. Similar to Fig. 11, the SEM images of Figs. 12(a) to 12(d) were taken at increasingly higher magnifications.
  • Fig. 12 shows that both clay and ZnO fillers are well dispersed within the multi-component polymer matrix.
  • nanocomposite surfaces fabricated using the pre-dispersed ZnO suspension were not highly water repellent (not shown).
  • the degree of dispersion of the nanoparticles has a direct influence on surface morphology.
  • formation of hierarchical hydrophobic surface morphology a necessary condition for water repellency, was obtained by introducing ZnO nanoparticles directly rather than in pre-dispersed form.
  • a uniform surface porosity was formed more readily when ZnO was added from a solution-based colloidal dispersion. Therefore, by appropriately choosing the type of nanofillers and their concentrations, the coating properties may be tailored towards specific industrial applications.
  • Functional filler particles could also be dispersed in the polymer blend for obtaining coatings with tunable hydrophobicity and adhesion strength.
  • the prepared multi- component mixtures were spray cast on various substrates and cured at 130 0 C for 30 minutes to form nanocomposite coatings. These coatings displayed superior substrate adhesion compared to coatings obtained using direct DMF catalyzed CA/PVDF blends.
  • This technique may be employed with fillers such as microparticles or nanoparticles of ZnO, TiO 2 , Indium Tin Oxide (ITO), SiO 2 , single or multi-walled carbon nanotubes (SWCNT or MWCNT), carbon black (CB), hydroxyapatite, clay or various other polymer powder fillers, such as Teflon or polyetheretherketone (PEEK) or polyethylene (PE).
  • fillers such as microparticles or nanoparticles of ZnO, TiO 2 , Indium Tin Oxide (ITO), SiO 2 , single or multi-walled carbon nanotubes (SWCNT or MWCNT), carbon black (CB), hydroxyapatite, clay or various other polymer powder fillers, such as Teflon or polyetheretherketone (PEEK) or polyethylene (PE).
  • the spraying was performed using a Paasche VL siphon feed airbrush (Paasche Airbrush Company, Chicago, IL).
  • the coated foils were heated at 125°C for 45 minutes to cure the coatings and remove any solvents.
  • All dispersions comprised PVDF and PECA in 60:40 weight ratio to ensure proper particle dispersion and good adhesion of the resulting coatings.
  • concentrations of the polymers were kept constant.
  • 18 grams of polymer/filler/solvents mixture (dispersion) was used to spray a 10-inch x 10-inch square of aluminum foil; the relative weight of the different components in the standard dispersion is shown in Table 2 below.
  • Table 2 Composition of the standard dispersion used to make coatings
  • PTFE poly(tetrafluoroethylene)
  • ZnO microparticles ⁇ 5 ⁇ m in diameter
  • ZnO nanoparticles ⁇ 40-100 nm in diameter
  • the wettability of the coatings was tested using sessile droplet contact angle measurements for water and also water + isopropyl alcohol (IPA, 2-Propanol) mixtures in a 90:10 weight ratio.
  • IPA isopropyl alcohol
  • This latter mixture should have a surface tension of 40.42 mN/m and serves as a measure to determine the alcohol repellency of the present coatings.
  • the requirement of water repellency is of great importance for large area coating of medical fabrics, for instance.
  • repellency of such a low surface tension liquid is a more severe test for the surface energy of coatings and, in general, very challenging to achieve for large area coating applications. It should be mentioned here that these coatings consist of biocompatible components, which combined with their alcohol repellency could be especially well suited for medical applications.
  • the addition of particles is expected to influence the wettability of the resulting coatings by two different mechanisms. On one hand, it should influence the surface roughness of the coatings, which can change the contact angle of liquid drops present on the surface (the Wenzel effect), and on the other hand, it can influence surface energy of the coating depending on the surface energy of the particles (i.e., hydrophilic or hydrophobic). For each type of filler particles used here, particle amounts were added ranging from the low to the maximum possible limit to obtain the entire range of wettability obtainable by adding these fillers to PVDF/PECA blends.
  • Roll-over angle can be measured by letting a liquid droplet roll over a pre-inclined coated surface or by increasingly inclining a coated surface with a sessile droplet sitting on top of it. The measurements described herein were performed with the latter technique.
  • the coated aluminum foil pieces were cut and pasted on a tilt stage, having angle measure accuracy (graduation) of 1 degree. After a sessile droplet was gently placed on the coated foil, the stage was inclined steadily until the droplet rolled over.
  • WSA water sliding angle
  • WISA water + IPA sliding angle
  • Table 3 Sliding angles for liquid droplets on coatings containing PTFE filler particles. Two sliding angle measurements were performed for each liquid. The error column represents the error originating from angular graduation on the tilt stage used in this study.
  • Table 4 Sliding angles for liquid droplets on coatings containing ZnO filler microparticles. Two sliding angle measurements were performed for each liquid. The error column represents the error originating from angular graduation on the tilt stage used in this study. ⁇ ZnO WSAl WSA2 Avg. Err. WISAl WISA2 Avg. Err.
  • Table 6 Sliding angles for liquid droplets on coatings containing both micro and nanoparticles of ZnO as fillers. The two types of particles were added in 50:50 wt. ratio and their combined weight was used to calculate the percentage of filler content listed in the first column. Two sliding angle measurements were performed for each liquid. The error column represents the error originating from angular graduation on the tilt stage used in this study.
  • Figure 16 shows the WCA and WICA variation with addition of hydrophilic ZnO microparticles ( ⁇ 5 ⁇ m in diameter). Addition of hydrophilic microparticles should increase the surface roughness of the coatings, but increase the overall surface energy of the coating. These two effects are in competition with each other. Therefore, although there is a rise in contact angle for both liquids with addition of ZnO microparticles, the rise in contact angle slows down from 6% and higher particle concentrations (see, especially WICA variation in Fig. 16).
  • Table 4 shows sliding angle for water and water + IPA drops on these coatings. The water + IPA drops never slide no matter what the particle content. The water droplets do slide for intermediate ZnO microparticle content because the surface roughness effects dominate over surface energy, however, they remain stuck at 10% particle content where the surface energy effect starts to dominate.
  • FIG. 17-18 the results showing the effect of adding both micro and nanoparticles are presented. This should result in hierarchical micro/nanoscale surface roughness morphology, which is essential to obtain superhydrophobic surfaces.
  • Fig. 17 the change in WCA and WICA with addition of PTFE micro ( ⁇ 1 ⁇ m in diameter) and ZnO nanoparticles ( ⁇ 40-100 nm in diameter) is shown. The two types of particles are used in 50:50 wt. ratio with respect to each other and their overall content in dispersion is plotted along the abscissa of Fig. 17.
  • Figure 18 shows the contact angle variation for coatings containing both micro ( ⁇ 5 ⁇ m in diameter) and nanoparticles ( ⁇ 40-100 nm in diameter) of ZnO.
  • the trends appear to be very similar to those of Fig. 14.
  • a key difference appears in sliding angle measurements shown in Table 6. Water drops do slide at high particle contents (10 and 12%), whereas the water + IPA drops never slide. Note that for these fillers 12% was the highest particle amount that could be dispersed in PVDF/PECA blends prepared here.
  • the coatings disclosed herein may be used in combination with other materials to provide multiple benefits, such as by providing one layer of a multilayer coating.
  • a coating comprising PVDF, PECA and nanoparticles was applied over a layer of a thermoplastic polymer (i.e., polyethylene) adhered to the aluminum.
  • the application of the PVDF-based coating can be performed with any suitable method, such as a capillary bridge based printing method, and any number of thin films of the coating may be applied to provide a total PVDF-based coating thickness between about 20 microns and several hundred microns.
  • the PVDF-based nanocomposite coating was allowed to dry at 50 0 C for one hour.
  • the PVDF-based nanocomposite coating provides a durable, chemically-inert and mechanically strong exterior surface to protect the polyethylene and acetonitrile from environmental and weather conditions such as UV radiation, rain, wind, abrasion, etc.
  • the two-layer coating exhibits a negligible water vapor transmittance due to the superhydrophobic nature of the PVDF- based coating. Consequently, the PVDF-based coating may be used as part of a multilayer coating in contact with liquids and effective to seal liquids within containers.

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  • Wood Science & Technology (AREA)
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Abstract

La composition polymère ci-décrite comprend un mélange de poly(fluorure de vinylidène) et d'au moins un cyanoacrylate (CA) qui donne un composite polymère alliant les caractéristiques utiles des deux matériaux. Une colophane et/ou une huile de lin portée à ébullition peuvent être incluses dans la composition, de manière à inhiber la polymérisation du cyanoacrylate. En variante, le cyanoacrylate peut être préparé sous la forme d'une solution contenant un polymère CA (par exemple, polymère de 2-cyanoacrylate d'éthyle). Plusieurs co-solvants différents peuvent être utilisés pour contrôler la polymérisation du CA. De plus, des charges telles que des microparticules/nanoparticules ou des combinaisons de celles-ci peuvent être ajoutées pour pouvoir affiner l'hydrophobie du composite et/ou d'autres caractéristiques. La composition polymère, comprenant un mélange de PVDF et d'au moins un CA, peut en outre être revêtue sur un substrat et durcie pour former un film adhérant au substrat.
PCT/US2009/036203 2008-06-27 2009-03-05 Formulations de composites polymères à base de poly(fluorure de vinylidène) (pvdf) et de cyanoacrylates (ca) et procédés pour leur utilisation dans des applications à grande échelle WO2009158046A1 (fr)

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ITTO20101040A1 (it) * 2010-12-22 2012-06-23 Fond Istituto Italiano Di T Ecnologia Procedimento di trattamento di materiali fibrosi per ottenere proprieta' idrorepellenti, materiali fibrosi idrofobici ed articoli che li comprendono cosi' ottenuti
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