WO2008060294A2 - Polymer matrix composites with nano-scale reinforcements - Google Patents

Polymer matrix composites with nano-scale reinforcements Download PDF

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Publication number
WO2008060294A2
WO2008060294A2 PCT/US2006/047483 US2006047483W WO2008060294A2 WO 2008060294 A2 WO2008060294 A2 WO 2008060294A2 US 2006047483 W US2006047483 W US 2006047483W WO 2008060294 A2 WO2008060294 A2 WO 2008060294A2
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Prior art keywords
matrix
reinforcement
approximately
composite material
nanoparticles
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PCT/US2006/047483
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French (fr)
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WO2008060294A3 (en
Inventor
Mohammad Naghi Ghasemi Nejhad
Vinod P. Veedu
Andrea Yuen
Davood Askari
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University Of Hawaii
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Publication of WO2008060294A3 publication Critical patent/WO2008060294A3/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/044Suspensions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25Silicon; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00Manicure or pedicure preparations
    • A61Q3/02Nail coatings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52Stabilizers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00Nanotechnology
    • Y10S977/902Specified use of nanostructure
    • Y10S977/904Specified use of nanostructure for medical, immunological, body treatment, or diagnosis
    • Y10S977/926Topical chemical, e.g. cosmetic or sunscreen

Definitions

  • Certain embodiments of the present invention relate generally to composite materials and, in particular, relate to systems and methods for reinforcement of polymer matrices with low concentrations of uniformly dispersed nanomaterials.
  • Composite materials have been developed to meet increasing demands for materials possessing a broad array of desirable properties.
  • Composites are material systems which combine two or more distinct materials, each with its own distinctive, desirable properties, to create a new material with properties that may not be present, or to the same extent, in the components alone.
  • Composite materials broadly, possess at least two phases - a reinforcement and a matrix.
  • the reinforcement is a material which is embedded within the matrix.
  • the reinforcing material and the matrix material may comprise any combination of metals, ceramics, or polymers.
  • polymer matrix composites combine strong reinforcing fibers within a polymer matrix.
  • PMCs possess relatively high strength, low weight, and corrosion resistance, which has spurred their development for applications in aerospace, sporting goods, automotive, and other industries where environmental and weight concerns play a key role in design considerations.
  • these materials may be fabricated at relatively low costs, further increasing their desirability.
  • Nano-scale materials possess great promise as composite reinforcements.
  • the greater the surface to volume ratio of a reinforcement the greater the effectiveness of a material as a reinforcement, and nano-scale materials have a high surface to volume ratio owing to their small size.
  • One embodiment of the present invention provides a composite material, comprising a matrix material and a reinforcement material.
  • the reinforcement material preferably has at least one dimension of approximately 100 nm or less and is dispersed substantially uniformly within the matrix material.
  • the reinforcement material is present in a concentration between approximately 0.01% to less than about 1% on the basis of the weight of the composite material.
  • the matrix is reinforced with nanoparticles in a concentration of between about 0.1 % and 0.5% by weight.
  • the nanoparticles are provided in the range of approximately 0.2 to less than 0.5 wt %.
  • the nanoparticles are provided in the range of approximately 0.2 to 0.4 wt %.
  • the nanoparticles are provided in the range of approximately 0.2 to less than 0.4 wt %.
  • the matrix is reinforced with nanotubes in a concentration of between about 0.01% and 0.1% by weight.
  • the SiC-reinforced composite comprises a matrix material such as epoxy and SiC nanoparticles.
  • the SiC nanoparticles have a diameter of about 100 nm or less and are present in a concentration of between approximately 0.1 to less than about 1%, more preferably less than about 0.9%, and even more preferably between about 0.2 to 0.5% or about 0.2 to 0.4%, on the basis of the weight of the composite material.
  • a composite material is provided with titanium dioxide nanoparticle reinforcement.
  • the composite may comprise a polyester resin and about 0.1 wt% to 0.4 wt%, more preferably about 0.2 wt% titanium dioxide nanoparticles.
  • a composite material is provided with carbon nanotube reinforcement.
  • the composite may comprise an epoxy resin and a very low weight percentage of carbon nanotubes, e.g., about 0.01% to 0.1% by weight.
  • the nanotubes may have a width or diameter of about 100 nm or less.
  • any suitable nano-material loading that causes an increase in ultimate strength of about 10% or more, more preferably about 25% or more, and/or an increase in strain to failure of about 50% or more may be utilized.
  • any suitable nano-material loading that causes about a two fold or more rise in G ⁇ c, and/or about a 20% or more rise in Kic may be utilized.
  • a method of manufacturing a nanocomposite such as a polymer nanocomposite, is provided.
  • the method comprises providing a reinforcement material having at least one dimension of approximately 100 nm or less and in a concentration between approximately 0.01 wt % to less than about 1 wt % on the basis of the weight of the composite material.
  • the method further comprises providing a matrix material.
  • the method additionally comprises dispersing the reinforcement material within the matrix material using a magnetic mixing system.
  • a curing agent may be added to the reinforcement-matrix mixture, and the dispersed reinforcement-matrix mixture may be placed within a mold.
  • the method further comprises curing the matrix material.
  • the reinforcement material comprises carbon nanotubes (CNTs), which are first added to a substantially volatile solvent such as ethyl alcohol (EtOH). A sonication technique is then utilized to disperse the CNT's within the solvent. The dispersed solution is then mixed with the resin using the magnetic mixing technique described above. A further sonication technique may be utilized to disperse the CNTs within the resin.
  • a substantially volatile solvent such as ethyl alcohol (EtOH).
  • EtOH ethyl alcohol
  • a sonication technique is then utilized to disperse the CNT's within the solvent.
  • the dispersed solution is then mixed with the resin using the magnetic mixing technique described above.
  • a further sonication technique may be utilized to disperse the CNTs within the resin.
  • a nanomaterial-reinforced nail polish is provided.
  • the nail polish may be a composite comprising one or more nail polish coatings and a nanomaterial reinforcement material in one or more of the coatings.
  • the nanomaterial reinforcement is provided in a concentration of about 0.2 to 0.4 wt % on the basis of the weight of the composite.
  • FIGS IA-B are schematic illustrations of embodiments of nanocomposites having substantially uniformly distributed nanomaterials: (IA) Nanoparticles; (IB) Carbon Nanotubes;
  • Figures 2 A and 2B are embodiments of methods for manufacture of the nanocomposites having substantially uniformly distributed nanoparticles (Figure 2A) and carbon nanotubes ( Figure 2B);
  • Figures 2C-E illustrate embodiments of nanocomposites containing a SiC nanoparticle reinforcement at loadings of 0.2% (2C), 1% (2D), and 1.5% (2E);
  • Figures 3A-3B are schematic illustrations of test specimens for measurement of tensile and fracture properties of the nanocomposites of Figures IA-B;
  • Figures 4A-B are micrographs of as-processed neat matrix and SiC reinforced nanocomposites
  • Figures 5 A-E are micrographs of embodiments of an as-processed neat matrix and SiC nanocomposites at loadings of approximately 0.2, 0.5, 1, and 1.5%, respectively;
  • Figures 6A-D present measured the tensile properties for embodiments of SiC nanocomposites and the corresponding neat matrix: (6A) Tensile stress-strain response; (6B) Young's Modulus as a function of SiC loading; (6C) Ultimate tensile strength as a function of SiC loading; (6D) Strain to failure as a function of SiC wt %;
  • Figures 7A-B present the measured fracture properties for SiC nanocomposites and the corresponding neat matrix: (7A) Gic as a function of SiC loading; (6B) K ⁇ c as a function of SiC loading;
  • Figures 8A-C are micrographs of SENB fracture surfaces of embodiments of a neat matrix (Figure 8A) and SiC reinforced nanocomposites having loading fractions of 0.2% (Figure 8B) and 1% (Figure 8C);
  • Figures 9A-B are micrographs of embodiments of an as-processed neat matrix and a 0.2% TiO 2 -reinforced nanocomposite;
  • Figures lOA-C present measured tensile properties for embodiments of a TiO 2 nanocomposites and the corresponding neat matrix: (10A) Stress-strain response; (10B) Strain to failure as a function of TiO 2 loading; (10C) Ultimate tensile strength as a function of TiO 2 wt %;
  • Figures HA-B present measured fracture properties for embodiments of a TiO 2 nanocomposites and the corresponding neat matrix; (HA) Gic as a function of TiO 2 loading; (HB) K ⁇ c as a function of TiO 2 loading;
  • Figures 12A-B are photographs of embodiments of an as-processed neat matrix and an approximately 0.02 wt% nanotube-reinforced nanocomposite;
  • Figures 13A-C present measured tensile properties for embodiments of CNT nanocomposites and the corresponding neat matrix: (13A) Stress-strain response; (13B) Strain to failure as a function of CNT loading; (13C) Ultimate tensile strength as a function of CNT wt %;
  • Figures 14A-B present measured fracture properties for embodiments of CNT nanocomposites and the corresponding neat matrix: (14A) Kic as a function of CNT loading; (14B) Gic as a function of CNT loading and;
  • Figures 15 A-B present micrographs of artificial nails painted with a single coating of nail polish; (15A) Unreinforced; (15B) Reinforced with TiO 2 nanoparticles.
  • nano-scale reinforcing materials such as nanoparticles and carbon nanotubes
  • polymer matrices may be mechanically dispersed during fabrication of polymer nanocomposites to provide nanocomposites which are substantially free of agglomerates.
  • nano-scale reinforcing materials according to certain embodiments have at least one dimension of about 100 nm or less. More preferably, the nano-scale reinforcing materials have two dimensions of about 100 nm or less. It will be appreciated, however, that other embodiments of the invention may not be limited to these particular dimensions.
  • the nano-scale reinforcement may comprise nanoparticles having a diameter of approximately 100 nm or less. Such nanoparticles may be elemental, oxide or non-oxide ceramics, metallic alloys and intermetallics, or combinations thereof. More preferably, certain embodiments described herein are directed to ceramic or elemental nanoparticle reinforcements.
  • the nano-scale reinforcement may comprise carbon nanotubes having a diameter of approximately less than 100 nm.
  • polymer nanocomposites so fabricated possess significantly enhanced fracture toughness while concurrently preserving or improving their tensile properties, such as tensile strength, elastic modulus, and strain to failure, over comparable un-reinforced polymers.
  • Figures IA-B present embodiments of a nanocomposite 100 having substantially uniformly distributed nano-scale reinforcements 102 possessing substantially low levels of agglomerates, designed for improved fracture toughness and strain to failure.
  • the nanocomposite 100 comprises a polymer matrix 104 reinforced with nanoparticles 102A ( Figure IA) or carbon nanotubes 102B ( Figure IB), which are substantially uniformly distributed within the matrix 104 during processing.
  • the weight fraction of the nano-scale reinforcement 102, or loading is relatively low, on the order of approximately 0.02% to 1.5%.
  • the loading is in the range of approximately 0.02% to less than approximately 1 wt %.
  • nano-reinforcement 102 is substantially dispersed using a magnetic mixing process, as discussed below. So fabricated, i.e., using low loading percentages and mixing as disclosed above here and with proper mixing technique as employed here, embodiments of the nanocomposites 100 possess less substantially no agglomerated nano- scale reinforcements 102 (as shown in Figures 2C-E below), where the agglomerates comprise a plurality of individual nano-scale reinforcements 102 in contact with one another, on the basis of the total amount of reinforcing material 102 added.
  • the matrix 104 may comprise a polymer.
  • the polymer may comprise a high temperature epoxy based on diglycidyl ether of bisphenol A (DGEBPA) and alkylglycidyl ether (AE), or DGEBPA-AE.
  • DGEBPA diglycidyl ether of bisphenol A
  • AE alkylglycidyl ether
  • the polymer matrix may comprise a polyester.
  • the matrix may comprise other polymers or polymer precursors such as pre-ceramic polymers.
  • a pre- ceramic polymer comprises KiON CERASET .
  • the nano-scale reinforcements 102 may comprise nanoparticles 102A of elements, oxide and non-oxide ceramics, metallic alloys and intermetallics, or combinations thereof.
  • the nanoparticles 102A may comprise Titanium Dioxide (TiO 2 ), Yttrium Oxide (Y 2 O 3 ), Zinc Oxide (ZnO), Silicon Carbide (SiC), and Carbon (C) or combinations thereof.
  • TiO 2 Titanium Dioxide
  • Y 2 O 3 Yttrium Oxide
  • ZnO Zinc Oxide
  • SiC Silicon Carbide
  • C Carbon
  • a single nanoparticle species is utilized as a reinforcement.
  • the nanoparticles 102A may further range in size from approximately 15 run to 45 nm and are provided in a relatively low weight fraction with respect to the total weight of the nanocomposite.
  • the nanoparticles 102 A are provided in the range of approximately 0.2 to 1.5 wt %, more preferably less than about 1 wt %. In an alternative embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to 0.5 wt %. In a further embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to less than 0.5 wt %. In another embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to 0.4 wt %. In an additional embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to less than 0.4 wt %.
  • the nano-scale reinforcement 102 may comprise carbon nanotubes 102B.
  • Carbon nanotubes 102B are a relatively new configuration of carbon which exhibit a variety of superior mechanical properties. Progress made in the production and purification of nanotubes in recent years has made it practical to consider nanotubes 102B as reinforcements in composite materials. With respect to their mechanical properties, nanotubes 102B exhibit extraordinary strength, on the order of tens of GPa, and elastic moduli on the order of about ITPa. Additionally, nanotubes 102B may undergo plastic deformation at elevated tensile stresses, allowing for some degree of permanent deformation. This deformation begins at strains of approximately 5% and can increase the maximum strain the tube undergoes before fracture.
  • CNTs 102B excellent candidates as reinforcing materials.
  • carbon nanotubes 102B possess a relatively low density for a solid, approximately 1.3-1.4 g/cm 3 . This provides CNTs 102B a specific strength which is very high, also making them very attractive for use in composite materials, which are often utilized in applications where weight is a key design consideration.
  • the CNTs 102B may comprise single walled carbon nanotubes (SWNTs) and/or multiple walled carbon nanotubes, MWNTs.
  • SWNTs can be conceptualized as wrapping a one-atom-thick layer of graphite called graphene into a seamless cylinder, while MWNTs are multiple layers of graphite rolled upon themselves to form a tube shape.
  • CNTs 102B possess diameters on the order of about 1 nm with tube lengths that can be many thousands of times larger.
  • the CNTs 102B comprise SWNTs having lengths in the range of approximately 1 to 500 micrometers.
  • the SWNTs are provided at loadings of approximately 0.02 to 0.1 wt %.
  • the use of substantially uniformly dispersed nanoparticles or CNTs 102B as reinforcements for nanocomposites 100 provides improved fracture toughness while concurrently preserving or improving the tensile properties of the nanocomposite 100, such as tensile strength and strain to failure, compared to un-reinforced neat matrices.
  • the carbon nanotubes 102B are provided in the range of approximately 0.01 to 0.1 wt %.
  • the loading fraction of the nano-scale materials may be adjusted within this range as generally understood by one of skill in the art so as to provide nanocomposites 100 having combinations of mechanical properties which are elevated above those of the un-reinforced matrix.
  • FIG. 2A One embodiment of a method 200 by which nanocomposites having substantially uniformly distributed nanoparticles may be fabricated is illustrated in Figure 2A.
  • a predetermined, low weight loading of nanoparticles is added to a matrix material which is contained within a beaker or other vessel.
  • the nanoparticle material, size, and loading fraction may be varied, as discussed above.
  • the ' matrix material will be referred to as a polymer resin, however, as discussed above, the matrix is not limited to polymer materials.
  • the nanoparticle-resin mixture is mechanically mixed using a magnetic mixing system.
  • the magnetic mixing system comprises a magnetic stirring device and a magnetic stirring bar.
  • the magnetic stirring bar is added to the beaker and the beaker is placed upon the magnetic stirring device.
  • Activation of the stirring device causes the stirring bar to rotate using non-contact magnetic torque, providing mechanical mixing of the nanoparticle-matrix mixture.
  • the magnetic mixer is operated according to a predetermined schedule of mixing time and rpm, based on the matrix and nanoparticle materials. In one embodiment, approximate values for magnetic mixing times and speeds which may provide a substantially uniform distribution of nanoparticles within the matrix are provided as illustrated below in Table I and discussed in greater detail below with respect to the examples.
  • the magnetic mixing speed and time may be increased or decreased as necessary
  • a curing agent such as a hardener is added to the resin-nanoparticle mixture.
  • the resin to hardener ratio is provided in accordance with the manufacturer's instruction.
  • a resin to hardener ratio of approximately 3:1 may be used with DGEBPA-AE epoxy, while a ratio of approximately 30 mL to 10 drops may be used with polyester resins.
  • the ratio of hardener to resin may be increased or decreased as necessary to cure the nanocomposite.
  • a fourth step 210 of the method 200 the nanoparticle-resin mixture is subjected to a manual mixing procedure for a predetermined time.
  • the mixture is stirred with a stirring rod or other device or implement generally known in the art for hand mixing.
  • the mixing is performed at a linear speed of approximately 1 cm/sec to avoid foaming of the mixture.
  • the manual mixing is conducted over the time range of approximately 5 to 30 minutes, as illustrated in Table I above. In alternative embodiments, the manual mixing time and linear speed may be increased or decreased.
  • the nanoparticle-resin mixture is poured into a polished aluminum mold or other mold and allowed to cure in air.
  • Cure times and temperatures are, in one embodiment, provided in accordance with the resin manufacturer's instructions.
  • the nanocomposite is cured at approximately room temperature for times ranging between approximately 3 hours to 4 hours.
  • the cure time and temperature may be increased or decreased.
  • the cured nanocomposite may be subjected to a sixth step 214 comprising a post-cure at elevated temperature.
  • the post-cure schedule comprises heat treatment at approximately 120 0 C for approximately one hour.
  • a method 216 of manufacture of CNT reinforced nanocomposites builds upon the framework of the first method 200 described above ( Figure 2A), using additional steps.
  • the second method 216 utilizes these additional steps in order to disperse the CNTs, as a high degree of adhesion is present between CNTs which can make SWNTs difficult to separate into single units from aggregates and clusters within the viscous polymer matrix during processing.
  • a predetermined, low weight loading of nanotubes is added to a substantially volatile solvent which is contained within a beaker or other vessel.
  • ethyl alcohol EtOH
  • other volatile solvents such as, in non-limiting embodiments, other alcohols and acetone.
  • the size, and loading fraction of the nanotubes may be varied, as discussed above.
  • a second step of the method 222 the beaker is subsequently placed in a sonication water bath which utilizes sound waves to cause vibrations within the water which are transferred to the CNT-EtOH solution.
  • sonication is performed for approximately five hours at room temperature to generate a substantially uniform distribution of CNTs within the EtOH.
  • the dispersed EtOH-CNT solution is mixed with the resin using the magnetic mixing technique discussed above.
  • the resin comprises DGEBPA-AE.
  • the magnetic stirring bar rotates at approximately 700 RPM at approximately room temperature for approximately 15 hours At the end of the mixing period, further stirring is performed at approximately the same speed at about 80 0 C for approximately 45 minutes. In this manner, the volatile EtOH or other CNT dispersion solvent is substantially removed from the resin-CNT mixture.
  • sonication is performed a second time as in order to ensure substantially uniform dispersion of the CNTs within the resin prior to curing.
  • the resin- CNT mixture is sonicated for approximately 25 minutes.
  • a fifth step 230 of the second method 216 the hardener is added to the resin-CNT mixture.
  • a resin to hardener ratio of approximately 3:1 is used with DGEBPA-AE epoxy.
  • the ratio of hardener to resin may be increased or decreased.
  • a sixth step 232 of the second method 216 the mixture is subjected to a manual mixing procedure for a predetermined time.
  • the mixture is stirred with a stirring rod or other device generally known in the art for mixing by hand.
  • the mixing is performed at a linear speed of approximately 1 cm/sec to avoid foaming of the mixture.
  • the manual mixing is conducted for approximately 20-30 minutes.
  • the manual mixing time and linear speed may be increased or decreased, as necessary to ensure substantially uniform distribution of the CNTs within the resin.
  • a seventh step 234 following mixing, the mixture is poured into a polished aluminum mold or other mold and allowed to cure in air. Cure times and temperatures are, in one embodiment, provided in accordance with the polymer manufacturer's instructions. In one embodiment, the nanocomposite is cured at approximately room temperature for approximately 5 hours. In alternative embodiments, the cure time and temperature may be increased or decreased.
  • the nanocomposite may be optionally subjected to a post-cure treatment.
  • the post-cure comprises heat treatment at approximately 120°C for approximately one hour.
  • Nanocomposites fabricated according to the methods 200, 216 may possess substantially low levels of agglomerates.
  • Figure 2C-E present embodiments of SiC-reinforced nanocomposites at loading fractions of 0.2, 1, and 1.5 wt %, respectively. It is observed that at 0.2 wt%, the nano-scale reinforcements 102 are substantially uniformly distributed and unagglomerated 240. In contrast, at loadings of 1 and 1.5 wt%, relatively large agglomerates 242 of the nano-scale materials are observed, with the size of the agglomerates 242 increasing with increasing loading.
  • testing is performed on nanocomposites reinforced using nanoparticles and carbon nanotubes and their corresponding neat matrices in order to illustrate the property improvements which may be achieved in these composites over comparable un-reinforced polymer materials.
  • the nanocomposites tested are formed as described above, using two commonly available nanoparticles, SiC and TiO 2; and SWNTs with matrices of DGEBPA-AE and polyester.
  • these polymers are representative of those commonly used in present composites manufacturing, room temperature cure polymers and high temperature cure epoxies, and thus provide results which are relevant to present applications.
  • neat matrices were formed without the reinforcements.
  • mechanical characterization focuses on evaluation of the tensile and fracture properties of embodiments of the nanocomposite and corresponding neat matrix.
  • Tensile properties of the neat matrices and nanocomposites are measured according to ASTM D638, Standard Test Method for Tensile Properties of Plastics.
  • Dogboned uniaxial tensile specimens 300 of each material are provided having dimensions consistent with the standard ( Figure 3A). Tests are conducted using an Instron type 4200 universal testing machine and the load (P) and displacement (d) are recorded. Strain along the loading axis of the composite is also measured and recorded using strain gauges 302 bonded to the specimen 300. From the stress-strain data, the elastic modulus, yield stress, ultimate stress, and strain to failure are determined in accordance with the standard. For each material condition, at least four specimens were tested.
  • Kic and Gic are material properties which provide a measure of the resistance of a material to crack propagation in the presence of a sharp crack in a Mode I, or tensile mode. Kic scales with the load at which crack propagation begins, while Gic scales with the fracture work.
  • the SENB test specimen 304 is illustrated in Figure 3B.
  • the SENB specimen 304 comprises a generally rectangular beam having a length L, a width, W, a thickness B.
  • a notch 306 of length, a is introduced into the SENB specimen 304, approximately centered on the length, extending in the width direction.
  • the SENB specimen 304 is loaded in flexure at a rate of approximately 0.25 mm/min, approximately opposite the notch 306, and supported at positions flanking the notch 306, separated by a span length S, and centered approximately on the notch 306. So configured, the SENB specimen 304 is loaded in compression, with monotonically increasing load, P, causing the specimen 304 to bend downwards. Load and displacement of the specimen 304 at the load line are measured and the notch 306 is monitored to identify the load at which crack propagation initiates at the notch 306.
  • Kic is calculated according to the standard ASTM D5045. The validity of the plain strain Kic value so calculated is verified using Equation (1):
  • Gic is calculated using the load-displacement response of the SENB specimen 306 according to ASTM D5045. A corrected displacement is obtained from an indentation test outlined in the standard. Gic is then determined from the energy given by the area under the load-displacement curve using Equation (2):
  • fracture surfaces of the SENB specimens 306 are also examined using a Hitachi S-4800 Field Emission Scanning Electron Microscope (SEM). Fracture surfaces are covered with a thin layer of sputtered gold and imaged in the SEM using an acceleration voltage of approximately 1 kV.
  • SEM Field Emission Scanning Electron Microscope
  • SiC nanoparticle reinforced nanocomposites [0067] Investigations below illustrate the effect of inclusion of low loadings of SiC nanoparticles on the tensile and fracture properties of embodiments of the nanocomposites and comparable un-reinforced neat matrices.
  • An epoxy based on DGEBPA-AE is mixed with SiC nanoparticles (Accumet Materials Co.).
  • the SiC nanoparticles possess a density of about 3.22 g/cm 3 , a surface area of 70-90 m 2 /g, and a size n ranging between about 45 to 55 nm.
  • Four weight fractions of SiC nanoparticles are investigated: 0.2, 0.5, 1 , and 1.5%.
  • the SiC nanoparticles are added to the epoxy resin and the mixture is stirred using the magnetic mixing device for approximately 10 hours at about 1200 rpm in order to disperse the nanoparticles within the matrix resin.
  • the hardener is added to the homogeneous mixture in an epoxy to hardener ratio of approximately 3:1.
  • the mixture is stirred manually for approximately 20-30 minutes at a rate of approximately 1 cm/sec.
  • the mixture is poured into a polished aluminum mold and allowed to cure in air at room temperature for approximately 3 hours.
  • the cured composites are post-cured for approximately lhr at about 12O 0 C in air.
  • an epoxy panel without SiC nanoparticles is also manufactured using the same procedure.
  • Figures 4A-B illustrates the appearance of the as-processed neat matrix and SiC-reinforced nanocomposite of approximately 0.2% to 0.4% SiC by weight. It is apparent from the micrographs of Figure 4A-B, the SiC reinforced nanocomposites (4B) present an ash-colored appearance, while the neat matrix (4A) is approximately transparent. In one aspect, this result demonstrates that even small loadings of nanoparticles are sufficient to change the optical properties of the nanocomposite from those of the neat matrix from transparent to opaque. In another aspect, this result indicates that the mixing procedure described above provides substantially homogeneous dispersion of the nanoparticles within the resin, as the appearance of the nanocomposite is approximately uniform.
  • FIG. 5A-E The appearance of an as-processed neat matrix and SiC nanocomposites at loadings of approximately 0.2, 0.5, 1, and 1.5% are provided in Figures 5A-E. Examining the appearance of the nanocomposites, it is apparent that poorer dispersion of the SiC nanoparticles takes place at the higher loading fractions of 1 and 1.5% ( Figures 5D and 5E), even though each material condition has undergone the same processing method and nanoparticle distribution procedure. Examining the micrographs of Figures 5A-E in order of increasing loading fraction, from left to right, the appearance of the 0.2 and 0.5 wt % nanocomposites ( Figures 5B and 5C) appear approximately uniform, indicating homogeneous dispersion of the SiC nanoparticles.
  • Figures 6B-D compare the ultimate strength, strain to failure, and elastic modulus of the SiC reinforced nanocomposite compared to the baseline neat matrix, illustrating that the ultimate strength and strain to failure of the nanocomposites increase significantly with low nanoparticle loadings.
  • the ultimate strength rises from about 35 MPa in the neat matrix to about 57-60 MPa in the range of 0.2-0.5% loadings, an increase of more than about 70% over the un-reinforced matrix.
  • the ultimate strength may increase by about 70% or more compared to the un-reinforced matrix.
  • any suitable nanoparticle loading that causes an increase in ultimate strength of about 10% or more, more preferably about 25% or more, and even more preferably about 50% or more, may be utilized.
  • the strain to failure is also found to benefit over this range of nanoparticle loadings, increasing to about 0.024 at 0.5% loading from about 0.011 in the neat matrix, an increase of more than 200% over the un- reinforced matrix, an increase of over 150%.
  • any suitable nanoparticle loading that causes an increase in strain to failure of about 50% or more may be utilized.
  • the elastic modulus remains approximately constant with the increase in nanoparticles, decreasing only slightly, approximately 14%, when initially added to the polymer matrix.
  • low loadings of SiC nanoparticles for example between about 0.2-0.5%, and even between about 0.2 and 0.4%, significantly improve the tensile properties of polymer nanocomposites.
  • FIG. 3B An exemplifying SENB fracture specimen 304 is illustrated in Figure 3B.
  • the fracture specimen 304 has a nominal width of about 25.4 mm, a span length of about 1 12 mm, and an average thickness of approximately 6.4 mm.
  • a notch 306 of approximately 12 mm in length and 1.5 mm in width is cut using a milling cutter and sharpened using a razor blade tapped into the notch.
  • the SENB specimens 304 so provided have a nominal crack length to specimen width ratio a/W, of approximately 0.5, satisfying the ASTM standard's requirement for a valid SENB test. At least four such specimens were tested for each material condition.
  • Kic, and Gic values for the nanocomposites and neat matrix as a function of nanoparticle loading are presented in Figures 7A-B.
  • improvements in both Kic, and Gic values are observed with nanoparticle loadings up to 0.2%.
  • Kic rises from approximately 0.8 MPa m l/2 in the neat matrix to approximately 1.5 MPa m 1/2 in the 0.2%-SiC nanocomposite, a nearly two-fold rise.
  • Gic increases from approximately 200 J/m 2 to 750 J/m 2 , over the same range, a nearly four-fold rise. Beyond approximately 0.2% nanoparticle inclusion, both Kic and Gic are found to fall back to approximately the value of the neat matrix.
  • any suitable nanoparticle loading that causes about a two fold or more rise in Gic, and/or about a 20% or more rise in Kic, may be utilized.
  • TiO 2 loadings of 0.2% are investigated in relation to neat polyester matrix only materials. It will be appreciated that other TiO 2 loadings may also be utilized, such as in the range of approximately 0.1 % to 0.5%.
  • the TiO 2 nanoparticles are added to the polyester resin and the mixture stirred using the magnetic mixer approximately 15 hours at 700 rpm in order to disperse the nanoparticles within the matrix resin.
  • the hardener is added to the homogeneous mixture, in an amount so as to provide an epoxy to hardener ratio of approximately 3OmL to 10 drops. Following addition of the hardener, the mixture is stirred manually for approximately 5 minutes at a linear speed of about 1 cm/sec. Following mixing, the mixture is poured into a polished aluminum mold and allowed to cure in air at room temperature for approximately 4 hours.
  • a polyester panel without nanoparticles is also manufactured using the same procedure.
  • Figures 9A-B illustrate the appearance of an as-processed neat matrix (9A) and a 0.2% TiO 2 -reinforced nanocomposite (9B). It is apparent from the micrographs that the nanocomposite presents a white, opaque appearance, while the neat matrix is approximately transparent. In one aspect, this result demonstrates that even small loadings of nanoparticles are sufficient to change the optical properties of the nanocomposite from those of the neat matrix. In another aspect, this result indicates that the mixing procedure described above provides substantially homogeneous dispersion of the nanoparticles within the resin, as the appearance of the nanocomposite is approximately uniform.
  • Figures lOB-C presents the ultimate strength and strain to failure of the TiO 2 -polyester nanocomposites containing 0.2% TiO 2 compared to the baseline neat polyester matrix as well as the relative percentage change in the nanocomposite properties with respect to the baseline.
  • the ultimate strength and strain to failure of the nanocomposites are substantially higher than that obtained in the neat matrix.
  • the ultimate strength of the nanocomposite is approximately 25% higher than the neat matrix, approximately 47.43 ⁇ 3.2 MPa, compared to approximately 38 ⁇ 0.05 MPa.
  • the failure strain is almost doubled, from about 0.014 ⁇ 0.001 in the neat matrix to approximately 0.028 ⁇ 0.004 in the 0.02-TiO 2 nanocomposite.
  • any suitable nanoparticle loading that causes an increase in ultimate strength of about 10% or more, or an increase in strain to failure of about 50% or more, may be utilized. Addition of nanoparticles to the neat matrix is found to not significantly affect the Young's modulus of the nanocomposite (about 10% reduction), with the modulus of the neat matrix determined to be approximately 3.15 ⁇ 0.02 GPa to the 2.83 ⁇ 0.4 GPa measured in the nanocomposite.
  • SENB fracture specimens 304 of TiO 2 reinforced nanocomposites are provided as schematically illustrated in Figure 3B.
  • the fracture specimen 304 has a nominal width of about 12.5 mm, a span length of about 56 mm, and an average thickness of approximately 3.2 mm.
  • a notch 306 of approximately 6 mm in length and 1.5 mm in width is cut using a milling cutter and sharpened using a razor blade tapped into the notch.
  • the SENB specimens 304 so provided have a nominal crack length to specimen width ratio a/W, of approximately 0.5, satisfying the ASTM standard's requirement for a valid SENB test. At least four such specimens were tested for each material condition
  • Figures HA-B illustrate the results of SENB fracture tests of an embodiment of a 0.2% TiO 2 -polyester nanocomposites and comparable neat polyester matrix.
  • Kic of the nanocomposite increases from about 0.7 MPa m 1/2 to about 1.17 MPa m 1/2 , a roughly 65% increase and more than about a 50% increase over the neat matrix.
  • Gic of the nanocomposite increases more than three fold, from approximately 129 J/m 2 for the neat matrix to approximately 546 J/m 2 for the nanocomposite.
  • any suitable nanoparticle loading that causes about a two fold or more rise in Gic, and/or about a 20% or more rise in Kic, may be utilized.
  • SWNTs are difficult to separate into single units from aggregates and clusters within epoxy, as epoxy possesses a high viscosity.
  • SWNTs are first dispersed within ethyl alcohol (EtOH).
  • EtOH ethyl alcohol
  • the nanotubes are added to EtOH and subjected to a sonication treatment for approximately 5 hours at room temperature.
  • the dispersed EtOH-SWNT solution is mixed at room temperature with the resin using a magnetic hot plate stirrer at approximately 700 rpm for about 15 hours. Further stirring at approximately the same speed is continued, in addition to heating at a constant temperature of about " 80°C, for about 45 minutes in order to evaporate the highly volatile EtOH from resin.
  • the mixture is subsequently subjected to a second sonication treatment for approximately 25 min.
  • the hardener is then added to the nanotube-epoxy mixture in an approximately 3 : 1 ratio of epoxy-to-hardener.
  • the nanotube- epoxy-hardener mixture is subjected to slow manual stirring for about 20-30 minutes at a linear speed of approximately 1 cm/sec.
  • This mixing process provides a substantially homogeneously dispersed mixture of SWNT and resin.
  • the mixture is poured into a polished aluminum mold and allowed to cure in air at room temperature for approximately 5 hours. Subsequently, the cured composites are post-cured at approximately 12O 0 C for 1 hour in air.
  • FIGs 12A-B illustrate the appearance of the as-processed neat matrix and an approximately 0.02% nanotube-reinforced nanocomposite. It is apparent from the micrographs of Figure 12B, the nanocomposite is colored in appearance, while the neat matrix is approximately transparent, Figure 12A. In one aspect, this result demonstrates that even small loadings of nanoparticles are sufficient to change the optical properties of the nanocomposite from those of the neat matrix to translucent or opaque. In another aspect, this result indicates that the mixing procedure described above provides substantially homogeneous dispersion of the nanoparticles within the resin, as the appearance of the nanocomposite is approximately uniform.
  • Figures 13B-C presents the ultimate strength and strain to failure of embodiments of the CNT-DGEBPA-AE nanocomposites containing about 0.02%-0.1% CNTs compared to the baseline neat matrix as well as the relative percentage change in the nanocomposite properties with respect to the baseline.
  • the neat matrix exhibits a brittle elastic response, with the stress-strain response rising approximately linearly to failure.
  • the nanotube-reinforced nanocomposites illustrate yielding prior to failure.
  • the ultimate strength and strain to failure of the nanocomposites are higher than that obtained in the neat matrix: ultimate strength of the nanocomposite is approximately 15% higher than the neat matrix, approximately 40.72 ⁇ 4.5 MPa, compared to 35.9 ⁇ 1.05 MPa.
  • the failure strain also illustrates improvement, rising approximately 150% higher to 2.77%, compared to 1.09%.
  • any suitable nanotube loading that causes an increase in ultimate strength of about 10% or more, and/or an increase in strain to failure of about 50% or more, may be utilized.
  • the Young's modulus of the nanocomposite is found to be reduced approximately 45%, with the modulus of the neat matrix measured to be approximately 3.5 GPa to the 2.04 GPa measured in the nanocomposite.
  • SENB fracture specimens 304 of CNT reinforced nanocomposites are provided as schematically illustrated in Figure 3B.
  • the SENB specimens 304 tested possess a width of approximately 12.5 mm, a span length of approximately 56 mm, and an average thickness of approximately 3.2 mm.
  • a notch 306 of approximately 6 mm in length and 1.5 mm width is cut into the specimens using a milling cutter and sharpened using a razor blade tapped into the notch. So configured, the crack length to width ratio, a/W, is approximately 0.5, satisfying the ASTM requirements for a valid SENB fracture test.
  • Figure 14A-B illustrates the results of SENB fracture tests of embodiments of nanotube-epoxy nanocomposites and the neat matrix.
  • Kic of the nanocomposite With introduction of the 0.02-0.1% nanotubes, Kic of the nanocomposite more than doubled, exhibiting a roughly three fold increase, from about 0.7 MPa m l/2 in the neat matrix, to about 2.2 MPa m 1/2 in the nanocomposite. Further, Gic of the nanocomposite increases by more than a factor of 8 and almost ten fold over the neat matrix, from approximately 200 J/m 2 for the neat matrix to approximately 1900 J/m 2 for the nanocomposite.
  • testing is also performed on polymer coatings reinforced using nanoparticles and their corresponding un-reinforced counterparts in order to illustrate the property improvements which may be achieved in these coatings over un- reinforced coatings.
  • polymer coatings comprising nail polish are investigated.
  • chemical resistance and mechanical resistance to wear and chipping are examined.
  • nail polishes reinforced with TiO 2 nanoparticles it may be understood that other nanoparticles which include, but are not limited to SiC, ZnO, Y 2 O 3 , and C, as well as CNTs may be utilized in alternative embodiments of the invention.
  • a single nanoparticles or nanotubes species is provided as a reinforcement.
  • a base coating which is applied directly upon the nail
  • a main color coating which is applied upon the base coating
  • a top coating which is applied upon the main color.
  • representative, commercially available nail polish products are employed.
  • base and top coatings comprising REVLON FIRMA NAIL and main color coatings comprising REVLON ® COLOR ILLUSION, having a metallic red color, are examined.
  • REVLON ® FIRMA NAIL comprises combinations of the following compounds: Isopropanol, Acetyl tributyl citrate, Citric acid, Butyl acetate, Sucrose acetate isobutyrate, Ethyl acetate, Heptane, Etocrylene, Malic acid, Bismuth oxychloride, Nitrocellulose, Sucrose benzoate, 2-Propenoic acid, polymer with N-( 1,1 -dimethyl ethyl)-2-propenamide and ethyl 2- propenoate, Stearalkonium hectorite, and Stearalkonium bentonite.
  • REVLON ® COLOR ILLUSION is a nail enamel, generally comprising film forming agents (e.g. Nitrocellulose), resins and plasticizers, solvents, and coloring agents. Further details regarding the formulation of nail polish utilized in embodiments of the invention discussed above may be found in U.S. Patent Application Publication 2005/0220730 to Malnou, et al., the entirety of which is hereby incorporated by reference.
  • TiO 2 nanoparticles are added to each nail polish coating separately and dispersed using the magnetic stirring technique discussed above.
  • the TiO 2 nanoparticles possess a particle size of approximately 15 nm, a density in the range of about 0.04-0.06 g/cm 3 , and a surface area of approximately 190-290 m Ig.
  • the nanoparticles may be provided in a quantity as described above, for example about 0.1 wt% to 0.4 wt%, more preferably about 0.2 wt%.
  • an octagonal stirring bar having a length of approximately 1/2 inch and a diameter of approximately 1/8 inch is used for magnetic stirring. Stirring is performed in a closed container at a speed in the range of about 220-280 r.p.m. for approximately 15 hours.
  • the main color is substantially unchanged by the nanoparticle reinforcement.
  • the color of the base and top coatings exhibited modest whitening. It is further noted, however, that the change in color of the base and top coatings did not substantially alter the appearance of the final nail polish color when the three coatings were layered upon one another.
  • nanoparticle reinforcements of nail polishes have previously been performed, such as in U.S. Patent Application Number 2005/0220730, the influence of the reinforcement on the color of the resulting polish has not previously been appreciated.
  • the loading fraction of the nanomaterial reinforcement is selected so as to not substantially influence the color of the resulting polish. It is additionally noted that the nanoparticle reinforcement had substantially no influence on the consistency of the nail polish or ease of application.
  • the prepared coatings are applied to artificial finger nails for testing.
  • a commercially available artificial nail, Fing'rs ® is employed. These artificial nails possess a length of approximately 19 mm and a curvature of about 6.5 mm.
  • the coatings are applied to the nails using appropriate nail polish brushes in two different configurations. In the first configuration, a layer of either the base coating/top coating or the main coating is applied to the nail. Four sets of nails are coated in this manner for testing, with two sets using nail polish reinforced with nanoparticles and two sets using unreinforced nail polish. Each set possessed three nails.
  • one layer of base coating, two layers of main color coating, and one layer of top coating are applied, while the layers which possess the nanoparticle reinforcement are varied.
  • a drying time of approximately 10 minutes is employed after each coating layer is applied.
  • each coating is without nanoparticle reinforcement.
  • the base layer possesses the nanoparticle reinforcement.
  • the base coating and the two main color coating layers possess the nanoparticle reinforcement.
  • the nanoparticle reinforcement is present within all the coating layers. Nails prepared in this manner are observed to demonstrate substantially no difference in appearance, despite the variation in nanoparticle reinforcement..
  • the coated nails are glued to aluminum bars having diameters and curvatures approximately equal to that of the nails. Approximately 2/3 of the length of each nail, about 12.5mm, is affixed to the aluminum bars, leaving about 1/3 of the nail length, or approximately 6.5 mm, extending past the end of the bars.
  • the daily exposure time is used to estimate the total exposure time over the life cycle of the nail polish. Taking the life cycle of the nails to be approximately four weeks, the daily exposure time is multiplied by 28 days to yield approximate values for the total exposure time over the life cycle of the nails. These values are taken to be, respectively, 22.5, 7.5, 6, 3, and 0.75 hours for dish washing liquid, liquid hand soap, hair shampoo, hair conditioner, and makeup remover.
  • Accelerated testing is performed to simulate these total exposure times.
  • the total exposure time for each chemical and mechanical activity is divided into 9 testing cycles.
  • the nails are successively soaked in dish washing liquid, liquid hand soap, hair shampoo, hair conditioner, and makeup remover, for approximately 150, 50, 40, 20, and 5 minutes, respectively. Between each exposure, the nails are allowed to dry for approximately 2 hours. Nails are wiped and dried after each chemical exposure using paper towels for the last five testing cycles. Following each chemical exposure cycle, the nails are used to type continuously for approximately one hour, cyclically bringing the nails in and out of contact with a keyboard in order to simulate a typing action on a computer keyboard. Upon completion of all the testing cycles, the appearance of the nails is examined.
  • FIG. 15A-B illustrates artificial nails 1500 having a single layer of main color coating which are unreinforced (Figure 15A) and reinforced with the TiO 2 nanoparticles ( Figure 15B). It is observed that the unreinforced nail polish exhibits scratches 1502 on the surface of the nail after testing, as well as chipping 1504 at the tip of the nail. In contrast, nails painted with nanoparticle reinforced nail polish appear substantially free of such scratching or chipping. These results, therefore, demonstrate that the nanoparticle reinforcement enhances the durability, and thus the useful lifetime, of single nail polish coatings.
  • certain embodiments of the present invention provide systems and methods of fabricating nanocomposites having low weight fractions of nanoparticles and nanotubes which are substantially uniformly distributed.
  • the disclosed mixing technique including a magnetic mixing step, provide a substantially uniform distribution of the nanotubes and nanoparticles which can provide significantly enhanced tensile strength, strain to failure, and fracture toughness over neat matrices alone.

Abstract

Embodiments of the present invention provide polymer matrix nanocomposites reinforced with nano-scale materials such as nanoparticles and carbon nanotubes and methods of fabricating. The nanomaterials are provided within relatively low weight fractions, for example in the range of approximately 0.01 to about 0.4% by weight and distributed within the matrix by a magnetic mixing procedure to provide substantially uniform reinforcement of the nanocomposites. Advantageously, these nanocomposites provide significantly enhanced tensile strength, strain to failure, and fracture toughness over corresponding neat matrices.

Description

POLYMER MATRIX COMPOSITES WITH NANO-SCALE REINFORCEMENTS
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority under 35 U. S. C. § 1 19(e) to U.S. Provisional Application Number 60/753,006 filed on December 12, 2005, entitled TOUGHENING OF EPOXY USING SIC NANOP ARTICLES, U.S. Provisional Application Number 60/753,155 filed on December 20, 2005, entitled TOUGHENING OF POLYESTER RESIN USING TIO2 NANOP ARTICLES, and U.S. Provisional Application Number 60/753,496 filed on December 22, 2005 entitled SUPER PERFORMING CNT/EPOXY RESIN, the entirety of each of which is incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED R&D [0002] This invention was made with Government support under Contract Number N00014-05-1 -05086 awarded by ONR (Office of Naval Research). The Government has certain rights in this invention.
BACKGROUND OF THE INVENTION Field of the Invention
[0003] Certain embodiments of the present invention relate generally to composite materials and, in particular, relate to systems and methods for reinforcement of polymer matrices with low concentrations of uniformly dispersed nanomaterials.
Description of the Related Art
[0004] Composite materials have been developed to meet increasing demands for materials possessing a broad array of desirable properties. Composites are material systems which combine two or more distinct materials, each with its own distinctive, desirable properties, to create a new material with properties that may not be present, or to the same extent, in the components alone. Composite materials, broadly, possess at least two phases - a reinforcement and a matrix. The reinforcement is a material which is embedded within the matrix. In general, the reinforcing material and the matrix material may comprise any combination of metals, ceramics, or polymers.
[0005] In one example polymer matrix composites (PMCs) combine strong reinforcing fibers within a polymer matrix. Advantageously, PMCs possess relatively high strength, low weight, and corrosion resistance, which has spurred their development for applications in aerospace, sporting goods, automotive, and other industries where environmental and weight concerns play a key role in design considerations. Furthermore, these materials may be fabricated at relatively low costs, further increasing their desirability.
[0006] The use of polymers as matrix materials in composites demands excellent mechanical performance over a large range of temperatures. A limiting factor in the use of polymer matrices, however, is their relative brittleness and tendency to exhibit microcracking at low levels of strain. These microcracks may coalesce under load, forming macrocracks, and due to the relative brittleness of the polymer matrices, result in catastrophic failure with little warning. And while design strains can be kept to low levels to prevent microcracking and catastrophic failure, additional composite material is required to bear the applied load, increasing the total weight of the composite structures.
[0007] To mitigate the brittleness and microcracking of polymer matrices, researchers have experimented with the addition of nano-scale materials to polymer matrices in order to improve their strain to failure and fracture toughness. Nano-scale materials possess great promise as composite reinforcements. In general, the greater the surface to volume ratio of a reinforcement, the greater the effectiveness of a material as a reinforcement, and nano-scale materials have a high surface to volume ratio owing to their small size.
[0008] Agglomeration, however, has been a significant obstacle to the use of nano-scale materials as reinforcements. Small particles, those having a diameter less than approximately 1 μm, have a strong tendency to agglomerate, or group together, under the influence of Van der Waals forces. In the case of submicron particles, these forces are stronger than gravitational forces and gives rise to spontaneous agglomeration. Agglomerated particles contain small voids which are difficult for the reinforcing matrix to enter by capillary action during processing of the composite. Thus, a reinforced composite formed with agglomerates possesses voids which can act as flaws that, instead of benefiting the composite, are detrimental to its mechanical properties. In particular, a number of studies have observed that the addition of nano-scale materials may improve some mechanical properties, such as fracture toughness or stiffness, while other mechanical properties, such as strength, are detrimentally affected to the point where properties of the composite are less than that of the matrix alone.
[0009] Thus, there is need for an improved systems and methods of manufacturing composites reinforced with nano-scale materials and, in particular, polymer matrix composites which have improved fracture properties without incurring substantially detrimental impact upon other mechanical properties.
SUMMARY OF THE INVENTION
[0010] One embodiment of the present invention provides a composite material, comprising a matrix material and a reinforcement material. The reinforcement material preferably has at least one dimension of approximately 100 nm or less and is dispersed substantially uniformly within the matrix material. In one embodiment, the reinforcement material is present in a concentration between approximately 0.01% to less than about 1% on the basis of the weight of the composite material. In one embodiment, the matrix is reinforced with nanoparticles in a concentration of between about 0.1 % and 0.5% by weight. In a further embodiment, the nanoparticles are provided in the range of approximately 0.2 to less than 0.5 wt %. In another embodiment, the nanoparticles are provided in the range of approximately 0.2 to 0.4 wt %. In an additional embodiment, the nanoparticles are provided in the range of approximately 0.2 to less than 0.4 wt %. In another embodiment, the matrix is reinforced with nanotubes in a concentration of between about 0.01% and 0.1% by weight.
[0011] Another embodiment of the present invention provides a SiC- reinforced composite material. The SiC-reinforced composite comprises a matrix material such as epoxy and SiC nanoparticles. The SiC nanoparticles have a diameter of about 100 nm or less and are present in a concentration of between approximately 0.1 to less than about 1%, more preferably less than about 0.9%, and even more preferably between about 0.2 to 0.5% or about 0.2 to 0.4%, on the basis of the weight of the composite material.
[0012] In another embodiment, a composite material is provided with titanium dioxide nanoparticle reinforcement. For example, the composite may comprise a polyester resin and about 0.1 wt% to 0.4 wt%, more preferably about 0.2 wt% titanium dioxide nanoparticles.
[0013] In another embodiment, a composite material is provided with carbon nanotube reinforcement. For example, the composite may comprise an epoxy resin and a very low weight percentage of carbon nanotubes, e.g., about 0.01% to 0.1% by weight. The nanotubes may have a width or diameter of about 100 nm or less.
[0014] In other embodiments, any suitable nano-material loading that causes an increase in ultimate strength of about 10% or more, more preferably about 25% or more, and/or an increase in strain to failure of about 50% or more, may be utilized. In other embodiments, any suitable nano-material loading that causes about a two fold or more rise in Gιc, and/or about a 20% or more rise in Kic, may be utilized.
[0015] In another embodiment of the present invention, a method of manufacturing a nanocomposite, such as a polymer nanocomposite, is provided. The method comprises providing a reinforcement material having at least one dimension of approximately 100 nm or less and in a concentration between approximately 0.01 wt % to less than about 1 wt % on the basis of the weight of the composite material. The method further comprises providing a matrix material. The method additionally comprises dispersing the reinforcement material within the matrix material using a magnetic mixing system. A curing agent may be added to the reinforcement-matrix mixture, and the dispersed reinforcement-matrix mixture may be placed within a mold. The method further comprises curing the matrix material.
[0016] In a further embodiment, the reinforcement material comprises carbon nanotubes (CNTs), which are first added to a substantially volatile solvent such as ethyl alcohol (EtOH). A sonication technique is then utilized to disperse the CNT's within the solvent. The dispersed solution is then mixed with the resin using the magnetic mixing technique described above. A further sonication technique may be utilized to disperse the CNTs within the resin.
[0017] In another embodiment, a nanomaterial-reinforced nail polish is provided. The nail polish may be a composite comprising one or more nail polish coatings and a nanomaterial reinforcement material in one or more of the coatings. In one embodiment, the nanomaterial reinforcement is provided in a concentration of about 0.2 to 0.4 wt % on the basis of the weight of the composite. [0018] These and other objects and advantages of preferred embodiments of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figures IA-B are schematic illustrations of embodiments of nanocomposites having substantially uniformly distributed nanomaterials: (IA) Nanoparticles; (IB) Carbon Nanotubes;
[0020] Figures 2 A and 2B are embodiments of methods for manufacture of the nanocomposites having substantially uniformly distributed nanoparticles (Figure 2A) and carbon nanotubes (Figure 2B);
[0021] Figures 2C-E illustrate embodiments of nanocomposites containing a SiC nanoparticle reinforcement at loadings of 0.2% (2C), 1% (2D), and 1.5% (2E);
[0022] Figures 3A-3B are schematic illustrations of test specimens for measurement of tensile and fracture properties of the nanocomposites of Figures IA-B;
[0023] Figures 4A-B are micrographs of as-processed neat matrix and SiC reinforced nanocomposites;
[0024] Figures 5 A-E are micrographs of embodiments of an as-processed neat matrix and SiC nanocomposites at loadings of approximately 0.2, 0.5, 1, and 1.5%, respectively;
[0025] Figures 6A-D present measured the tensile properties for embodiments of SiC nanocomposites and the corresponding neat matrix: (6A) Tensile stress-strain response; (6B) Young's Modulus as a function of SiC loading; (6C) Ultimate tensile strength as a function of SiC loading; (6D) Strain to failure as a function of SiC wt %;
[0026] Figures 7A-B present the measured fracture properties for SiC nanocomposites and the corresponding neat matrix: (7A) Gic as a function of SiC loading; (6B) Kιc as a function of SiC loading;
[0027] Figures 8A-C are micrographs of SENB fracture surfaces of embodiments of a neat matrix (Figure 8A) and SiC reinforced nanocomposites having loading fractions of 0.2% (Figure 8B) and 1% (Figure 8C);
[0028] Figures 9A-B are micrographs of embodiments of an as-processed neat matrix and a 0.2% TiO2-reinforced nanocomposite; [0029] Figures lOA-C present measured tensile properties for embodiments of a TiO2 nanocomposites and the corresponding neat matrix: (10A) Stress-strain response; (10B) Strain to failure as a function of TiO2 loading; (10C) Ultimate tensile strength as a function of TiO2 wt %;
[0030] Figures HA-B present measured fracture properties for embodiments of a TiO2 nanocomposites and the corresponding neat matrix; (HA) Gic as a function of TiO2 loading; (HB) Kιc as a function of TiO2 loading;
[0031] Figures 12A-B are photographs of embodiments of an as-processed neat matrix and an approximately 0.02 wt% nanotube-reinforced nanocomposite;
[0032] Figures 13A-C present measured tensile properties for embodiments of CNT nanocomposites and the corresponding neat matrix: (13A) Stress-strain response; (13B) Strain to failure as a function of CNT loading; (13C) Ultimate tensile strength as a function of CNT wt %;
[0033] Figures 14A-B present measured fracture properties for embodiments of CNT nanocomposites and the corresponding neat matrix: (14A) Kic as a function of CNT loading; (14B) Gic as a function of CNT loading and;
[0034] Figures 15 A-B present micrographs of artificial nails painted with a single coating of nail polish; (15A) Unreinforced; (15B) Reinforced with TiO2 nanoparticles.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0035] Reference will now be made to the drawings wherein like numerals refer to like parts throughout. Throughout the disclosure, reference to loadings of nano- scale reinforcing materials are provided as wt % on the basis of the total weight of the nanocomposite.
[0036] It has been discovered that low weight percentage loadings of nano- scale reinforcing materials, such as nanoparticles and carbon nanotubes, to polymer matrices may be mechanically dispersed during fabrication of polymer nanocomposites to provide nanocomposites which are substantially free of agglomerates. As described herein, nano-scale reinforcing materials according to certain embodiments have at least one dimension of about 100 nm or less. More preferably, the nano-scale reinforcing materials have two dimensions of about 100 nm or less. It will be appreciated, however, that other embodiments of the invention may not be limited to these particular dimensions.
[0037] In one non-limiting embodiment, the nano-scale reinforcement may comprise nanoparticles having a diameter of approximately 100 nm or less. Such nanoparticles may be elemental, oxide or non-oxide ceramics, metallic alloys and intermetallics, or combinations thereof. More preferably, certain embodiments described herein are directed to ceramic or elemental nanoparticle reinforcements. In a further non- limiting embodiment, the nano-scale reinforcement may comprise carbon nanotubes having a diameter of approximately less than 100 nm. Advantageously, polymer nanocomposites so fabricated possess significantly enhanced fracture toughness while concurrently preserving or improving their tensile properties, such as tensile strength, elastic modulus, and strain to failure, over comparable un-reinforced polymers.
[0038] Figures IA-B present embodiments of a nanocomposite 100 having substantially uniformly distributed nano-scale reinforcements 102 possessing substantially low levels of agglomerates, designed for improved fracture toughness and strain to failure. In certain embodiments, the nanocomposite 100 comprises a polymer matrix 104 reinforced with nanoparticles 102A (Figure IA) or carbon nanotubes 102B (Figure IB), which are substantially uniformly distributed within the matrix 104 during processing. In one embodiment, the weight fraction of the nano-scale reinforcement 102, or loading, is relatively low, on the order of approximately 0.02% to 1.5%. In a preferred embodiment, the loading is in the range of approximately 0.02% to less than approximately 1 wt %. Higher loadings may be used, as necessary, depending on factors such as the nano-scale reinforcement 102 and the ability to disperse the reinforcement within the matrix 104. In further embodiments, nano-reinforcement 102 is substantially dispersed using a magnetic mixing process, as discussed below. So fabricated, i.e., using low loading percentages and mixing as disclosed above here and with proper mixing technique as employed here, embodiments of the nanocomposites 100 possess less substantially no agglomerated nano- scale reinforcements 102 (as shown in Figures 2C-E below), where the agglomerates comprise a plurality of individual nano-scale reinforcements 102 in contact with one another, on the basis of the total amount of reinforcing material 102 added. Advantageously, nanocomposites 100 within these loading ranges may concurrently demonstrate significantly improved tensile strength, strain to failure, and fracture toughness over comparable, un-reinforced neat matrices, as discussed in detail below. [0039] In a non-limiting embodiment, the matrix 104 may comprise a polymer. In a preferred embodiment, the polymer may comprise a high temperature epoxy based on diglycidyl ether of bisphenol A (DGEBPA) and alkylglycidyl ether (AE), or DGEBPA-AE. In an alternative embodiment, the polymer matrix may comprise a polyester. In further alternative embodiments, the matrix may comprise other polymers or polymer precursors such as pre-ceramic polymers. One preferred embodiment of a pre- ceramic polymer comprises KiON CERASET .
[0040] In non-limiting embodiments, the nano-scale reinforcements 102 may comprise nanoparticles 102A of elements, oxide and non-oxide ceramics, metallic alloys and intermetallics, or combinations thereof. In preferred embodiments, the nanoparticles 102A may comprise Titanium Dioxide (TiO2), Yttrium Oxide (Y2O3), Zinc Oxide (ZnO), Silicon Carbide (SiC), and Carbon (C) or combinations thereof. In one particularly preferred embodiment, a single nanoparticle species is utilized as a reinforcement. The nanoparticles 102A may further range in size from approximately 15 run to 45 nm and are provided in a relatively low weight fraction with respect to the total weight of the nanocomposite. In one embodiment, the nanoparticles 102 A are provided in the range of approximately 0.2 to 1.5 wt %, more preferably less than about 1 wt %. In an alternative embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to 0.5 wt %. In a further embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to less than 0.5 wt %. In another embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to 0.4 wt %. In an additional embodiment, the nanoparticles 102A are provided in the range of approximately 0.2 to less than 0.4 wt %.
[0041] In a further non-limiting embodiment, the nano-scale reinforcement 102 may comprise carbon nanotubes 102B. Carbon nanotubes 102B are a relatively new configuration of carbon which exhibit a variety of superior mechanical properties. Progress made in the production and purification of nanotubes in recent years has made it practical to consider nanotubes 102B as reinforcements in composite materials. With respect to their mechanical properties, nanotubes 102B exhibit extraordinary strength, on the order of tens of GPa, and elastic moduli on the order of about ITPa. Additionally, nanotubes 102B may undergo plastic deformation at elevated tensile stresses, allowing for some degree of permanent deformation. This deformation begins at strains of approximately 5% and can increase the maximum strain the tube undergoes before fracture. These mechanical properties make CNTs 102B excellent candidates as reinforcing materials. Further, carbon nanotubes 102B possess a relatively low density for a solid, approximately 1.3-1.4 g/cm3. This provides CNTs 102B a specific strength which is very high, also making them very attractive for use in composite materials, which are often utilized in applications where weight is a key design consideration.
[0042] In one embodiment, the CNTs 102B may comprise single walled carbon nanotubes (SWNTs) and/or multiple walled carbon nanotubes, MWNTs. SWNTs can be conceptualized as wrapping a one-atom-thick layer of graphite called graphene into a seamless cylinder, while MWNTs are multiple layers of graphite rolled upon themselves to form a tube shape. CNTs 102B possess diameters on the order of about 1 nm with tube lengths that can be many thousands of times larger. In one preferred embodiment, the CNTs 102B comprise SWNTs having lengths in the range of approximately 1 to 500 micrometers. In further embodiments, the SWNTs are provided at loadings of approximately 0.02 to 0.1 wt %.
[0043] As discussed in greater detail with respect to the examples below, the use of substantially uniformly dispersed nanoparticles or CNTs 102B as reinforcements for nanocomposites 100 provides improved fracture toughness while concurrently preserving or improving the tensile properties of the nanocomposite 100, such as tensile strength and strain to failure, compared to un-reinforced neat matrices. . In one embodiment, the carbon nanotubes 102B are provided in the range of approximately 0.01 to 0.1 wt %. In further alternative embodiments, the loading fraction of the nano-scale materials may be adjusted within this range as generally understood by one of skill in the art so as to provide nanocomposites 100 having combinations of mechanical properties which are elevated above those of the un-reinforced matrix.
[0044] One embodiment of a method 200 by which nanocomposites having substantially uniformly distributed nanoparticles may be fabricated is illustrated in Figure 2A. In a first step 202, a predetermined, low weight loading of nanoparticles is added to a matrix material which is contained within a beaker or other vessel. The nanoparticle material, size, and loading fraction may be varied, as discussed above. In a non-limiting example of the method, the ' matrix material will be referred to as a polymer resin, however, as discussed above, the matrix is not limited to polymer materials.
[0045] In a second step 204, the nanoparticle-resin mixture is mechanically mixed using a magnetic mixing system. In one embodiment, the magnetic mixing system comprises a magnetic stirring device and a magnetic stirring bar. The magnetic stirring bar is added to the beaker and the beaker is placed upon the magnetic stirring device. Activation of the stirring device causes the stirring bar to rotate using non-contact magnetic torque, providing mechanical mixing of the nanoparticle-matrix mixture. The magnetic mixer is operated according to a predetermined schedule of mixing time and rpm, based on the matrix and nanoparticle materials. In one embodiment, approximate values for magnetic mixing times and speeds which may provide a substantially uniform distribution of nanoparticles within the matrix are provided as illustrated below in Table I and discussed in greater detail below with respect to the examples.
Figure imgf000012_0001
In alternative embodiments, the magnetic mixing speed and time may be increased or decreased as necessary
[0046] In a third step 206, a curing agent such as a hardener is added to the resin-nanoparticle mixture. In one embodiment, the resin to hardener ratio is provided in accordance with the manufacturer's instruction. In a non-limiting example, a resin to hardener ratio of approximately 3:1 may be used with DGEBPA-AE epoxy, while a ratio of approximately 30 mL to 10 drops may be used with polyester resins. In alternative embodiments, the ratio of hardener to resin may be increased or decreased as necessary to cure the nanocomposite.
[0047] In a fourth step 210 of the method 200, the nanoparticle-resin mixture is subjected to a manual mixing procedure for a predetermined time. The mixture is stirred with a stirring rod or other device or implement generally known in the art for hand mixing. The mixing is performed at a linear speed of approximately 1 cm/sec to avoid foaming of the mixture. In one embodiment, the manual mixing is conducted over the time range of approximately 5 to 30 minutes, as illustrated in Table I above. In alternative embodiments, the manual mixing time and linear speed may be increased or decreased. [0048] In a fifth step 212, following mixing, the nanoparticle-resin mixture is poured into a polished aluminum mold or other mold and allowed to cure in air. Cure times and temperatures are, in one embodiment, provided in accordance with the resin manufacturer's instructions. In one embodiment, the nanocomposite is cured at approximately room temperature for times ranging between approximately 3 hours to 4 hours. In alternative embodiments, the cure time and temperature may be increased or decreased.
[0049] In alternative embodiments, the cured nanocomposite may be subjected to a sixth step 214 comprising a post-cure at elevated temperature. In one embodiment, the post-cure schedule comprises heat treatment at approximately 1200C for approximately one hour.
[0050] In one embodiment, a method 216 of manufacture of CNT reinforced nanocomposites (Figure 2A) builds upon the framework of the first method 200 described above (Figure 2A), using additional steps. The second method 216 utilizes these additional steps in order to disperse the CNTs, as a high degree of adhesion is present between CNTs which can make SWNTs difficult to separate into single units from aggregates and clusters within the viscous polymer matrix during processing.
[0051] In a first step 220 of the second method 216, a predetermined, low weight loading of nanotubes is added to a substantially volatile solvent which is contained within a beaker or other vessel. In one embodiment, ethyl alcohol (EtOH) is a used as the volatile solvent, owing to its relatively high volatility and its low viscosity compared to the polymer resin. However, in alternative embodiments, other volatile solvents may be used, such as, in non-limiting embodiments, other alcohols and acetone. The size, and loading fraction of the nanotubes, may be varied, as discussed above.
[0052] In a second step of the method 222, the beaker is subsequently placed in a sonication water bath which utilizes sound waves to cause vibrations within the water which are transferred to the CNT-EtOH solution. In one embodiment, sonication is performed for approximately five hours at room temperature to generate a substantially uniform distribution of CNTs within the EtOH.
[0053] Subsequently, in a third step 224 of the method 216, the dispersed EtOH-CNT solution is mixed with the resin using the magnetic mixing technique discussed above. In one embodiment, the resin comprises DGEBPA-AE. In a further embodiment, the magnetic stirring bar rotates at approximately 700 RPM at approximately room temperature for approximately 15 hours At the end of the mixing period, further stirring is performed at approximately the same speed at about 800C for approximately 45 minutes. In this manner, the volatile EtOH or other CNT dispersion solvent is substantially removed from the resin-CNT mixture.
[0054] In a fourth step 226 of the second method 216, sonication is performed a second time as in order to ensure substantially uniform dispersion of the CNTs within the resin prior to curing. In one embodiment, the resin- CNT mixture is sonicated for approximately 25 minutes.
[0055] In a fifth step 230 of the second method 216, the hardener is added to the resin-CNT mixture. In a non-limiting example, a resin to hardener ratio of approximately 3:1 is used with DGEBPA-AE epoxy. In alternative embodiments, the ratio of hardener to resin may be increased or decreased.
[0056] In a sixth step 232 of the second method 216, the mixture is subjected to a manual mixing procedure for a predetermined time. The mixture is stirred with a stirring rod or other device generally known in the art for mixing by hand. The mixing is performed at a linear speed of approximately 1 cm/sec to avoid foaming of the mixture. In one embodiment, the manual mixing is conducted for approximately 20-30 minutes. In alternative embodiments, the manual mixing time and linear speed may be increased or decreased, as necessary to ensure substantially uniform distribution of the CNTs within the resin.
[0057] In a seventh step 234, following mixing, the mixture is poured into a polished aluminum mold or other mold and allowed to cure in air. Cure times and temperatures are, in one embodiment, provided in accordance with the polymer manufacturer's instructions. In one embodiment, the nanocomposite is cured at approximately room temperature for approximately 5 hours. In alternative embodiments, the cure time and temperature may be increased or decreased.
[0058] In an eighth step 236 of the method 216, the nanocomposite may be optionally subjected to a post-cure treatment. In one embodiment, the post-cure comprises heat treatment at approximately 120°C for approximately one hour.
[0059] Nanocomposites fabricated according to the methods 200, 216 may possess substantially low levels of agglomerates. Figure 2C-E present embodiments of SiC-reinforced nanocomposites at loading fractions of 0.2, 1, and 1.5 wt %, respectively. It is observed that at 0.2 wt%, the nano-scale reinforcements 102 are substantially uniformly distributed and unagglomerated 240. In contrast, at loadings of 1 and 1.5 wt%, relatively large agglomerates 242 of the nano-scale materials are observed, with the size of the agglomerates 242 increasing with increasing loading.
EXAMPLES: Bulk Nanocomposites
[0060] In the following examples, testing is performed on nanocomposites reinforced using nanoparticles and carbon nanotubes and their corresponding neat matrices in order to illustrate the property improvements which may be achieved in these composites over comparable un-reinforced polymer materials. In particular, the tensile and fracture properties are examined. The nanocomposites tested are formed as described above, using two commonly available nanoparticles, SiC and TiO2; and SWNTs with matrices of DGEBPA-AE and polyester. Advantageously, these polymers are representative of those commonly used in present composites manufacturing, room temperature cure polymers and high temperature cure epoxies, and thus provide results which are relevant to present applications. To assess the influence of the nano-scale reinforcements on the performance of the nanocomposites, neat matrices were formed without the reinforcements.
Bulk Nanocomposites: Mechanical Testing
[0061] In the examples, mechanical characterization focuses on evaluation of the tensile and fracture properties of embodiments of the nanocomposite and corresponding neat matrix. Tensile properties of the neat matrices and nanocomposites are measured according to ASTM D638, Standard Test Method for Tensile Properties of Plastics. Dogboned uniaxial tensile specimens 300 of each material are provided having dimensions consistent with the standard (Figure 3A). Tests are conducted using an Instron type 4200 universal testing machine and the load (P) and displacement (d) are recorded. Strain along the loading axis of the composite is also measured and recorded using strain gauges 302 bonded to the specimen 300. From the stress-strain data, the elastic modulus, yield stress, ultimate stress, and strain to failure are determined in accordance with the standard. For each material condition, at least four specimens were tested.
[0062] The fracture properties of the nanocomposites and neat matrices are quantified by measurement of the critical stress intensity factor, Kic, and the critical strain energy release rate, Gic, through single edge notch bend tests (SENB) performed according to ASTM D5045, "Standard Test Method for Plane-Strain Fracture Toughness and Strain Energy Release Rate of Plastic Materials." Kic and Gic are material properties which provide a measure of the resistance of a material to crack propagation in the presence of a sharp crack in a Mode I, or tensile mode. Kic scales with the load at which crack propagation begins, while Gic scales with the fracture work.
[0063] The SENB test specimen 304 is illustrated in Figure 3B. The SENB specimen 304 comprises a generally rectangular beam having a length L, a width, W, a thickness B. A notch 306 of length, a, is introduced into the SENB specimen 304, approximately centered on the length, extending in the width direction. The SENB specimen 304 is loaded in flexure at a rate of approximately 0.25 mm/min, approximately opposite the notch 306, and supported at positions flanking the notch 306, separated by a span length S, and centered approximately on the notch 306. So configured, the SENB specimen 304 is loaded in compression, with monotonically increasing load, P, causing the specimen 304 to bend downwards. Load and displacement of the specimen 304 at the load line are measured and the notch 306 is monitored to identify the load at which crack propagation initiates at the notch 306.
[0064] Kic is calculated according to the standard ASTM D5045. The validity of the plain strain Kic value so calculated is verified using Equation (1):
B,a,and (W - a) > 0)
Figure imgf000016_0001
where σy is the yield stress, calculated from a 0.2% offset applied to the tensile stress- strain curve.
[0065] Gic is calculated using the load-displacement response of the SENB specimen 306 according to ASTM D5045. A corrected displacement is obtained from an indentation test outlined in the standard. Gic is then determined from the energy given by the area under the load-displacement curve using Equation (2):
G,c = -^- (2) IC BWφ
where U is the corrected energy and φ is an energy calibration factor. [0066] In some cases, fracture surfaces of the SENB specimens 306 are also examined using a Hitachi S-4800 Field Emission Scanning Electron Microscope (SEM). Fracture surfaces are covered with a thin layer of sputtered gold and imaged in the SEM using an acceleration voltage of approximately 1 kV.
Bulk nanocomposites: SiC nanoparticle reinforced nanocomposites [0067] Investigations below illustrate the effect of inclusion of low loadings of SiC nanoparticles on the tensile and fracture properties of embodiments of the nanocomposites and comparable un-reinforced neat matrices. An epoxy based on DGEBPA-AE is mixed with SiC nanoparticles (Accumet Materials Co.). The SiC nanoparticles possess a density of about 3.22 g/cm3, a surface area of 70-90 m2/g, and a size n ranging between about 45 to 55 nm. Four weight fractions of SiC nanoparticles are investigated: 0.2, 0.5, 1 , and 1.5%. The SiC nanoparticles are added to the epoxy resin and the mixture is stirred using the magnetic mixing device for approximately 10 hours at about 1200 rpm in order to disperse the nanoparticles within the matrix resin. Subsequently, the hardener is added to the homogeneous mixture in an epoxy to hardener ratio of approximately 3:1. Following addition of the hardener, the mixture is stirred manually for approximately 20-30 minutes at a rate of approximately 1 cm/sec. Following mixing, the mixture is poured into a polished aluminum mold and allowed to cure in air at room temperature for approximately 3 hours. Subsequently, the cured composites are post-cured for approximately lhr at about 12O0C in air. To quantify the effect of low SiC nanoparticle loading on the performance of the composite, an epoxy panel without SiC nanoparticles is also manufactured using the same procedure.
[0068] Figures 4A-B illustrates the appearance of the as-processed neat matrix and SiC-reinforced nanocomposite of approximately 0.2% to 0.4% SiC by weight. It is apparent from the micrographs of Figure 4A-B, the SiC reinforced nanocomposites (4B) present an ash-colored appearance, while the neat matrix (4A) is approximately transparent. In one aspect, this result demonstrates that even small loadings of nanoparticles are sufficient to change the optical properties of the nanocomposite from those of the neat matrix from transparent to opaque. In another aspect, this result indicates that the mixing procedure described above provides substantially homogeneous dispersion of the nanoparticles within the resin, as the appearance of the nanocomposite is approximately uniform.
[0069] The appearance of an as-processed neat matrix and SiC nanocomposites at loadings of approximately 0.2, 0.5, 1, and 1.5% are provided in Figures 5A-E. Examining the appearance of the nanocomposites, it is apparent that poorer dispersion of the SiC nanoparticles takes place at the higher loading fractions of 1 and 1.5% (Figures 5D and 5E), even though each material condition has undergone the same processing method and nanoparticle distribution procedure. Examining the micrographs of Figures 5A-E in order of increasing loading fraction, from left to right, the appearance of the 0.2 and 0.5 wt % nanocomposites (Figures 5B and 5C) appear approximately uniform, indicating homogeneous dispersion of the SiC nanoparticles. Even better uniformity is found in the 0.2 wt% sample, indicating that loadings of less than 0.5 wt% may be particularly advantageous. With loadings of 1 and 1.5% SiC, however, the nanocomposites exhibit dark and light areas, indicating that agglomeration occurs in these higher loading nanocomposites. This inhomogenaeity may negatively affect the composite properties, as illustrated below.
[0070] Dogboned tensile specimens were employed for measurement of the tensile properties of the two materials using ASTM D638. At least four specimens were tested for each material condition. Figures 6A-D below present the tensile properties of embodiments of the SiC-DGEBPA-AE nanocomposites and corresponding neat matrix.
[0071] Examining representative stress-strain curves for the nanocomposite with weight fraction of approximately 0.2% to 1.5% SiC as well as the neat matrix, Figure 6A, the un-reinforced neat matrix is observed to fail in a brittle manner, with the stress- strain curve rising linearly to failure. In contrast, nanocomposites containing 0.2-0.4% SiC nanoparticles exhibit yielding prior to failure, as illustrated by the non-linear portion of the curves at elevated values of stress. Nanocomposites containing 1% and 1.5% exhibit brittle failure, similar to the neat matrix.
[0072] Figures 6B-D compare the ultimate strength, strain to failure, and elastic modulus of the SiC reinforced nanocomposite compared to the baseline neat matrix, illustrating that the ultimate strength and strain to failure of the nanocomposites increase significantly with low nanoparticle loadings. In the range of nanoparticle loadings from 0.2-0.5%, the ultimate strength rises from about 35 MPa in the neat matrix to about 57-60 MPa in the range of 0.2-0.5% loadings, an increase of more than about 70% over the un-reinforced matrix. Thus, generally for a loading of about 0.4 wt%, the ultimate strength may increase by about 70% or more compared to the un-reinforced matrix. In other embodiments, any suitable nanoparticle loading that causes an increase in ultimate strength of about 10% or more, more preferably about 25% or more, and even more preferably about 50% or more, may be utilized. The strain to failure is also found to benefit over this range of nanoparticle loadings, increasing to about 0.024 at 0.5% loading from about 0.011 in the neat matrix, an increase of more than 200% over the un- reinforced matrix, an increase of over 150%. In other embodiments, any suitable nanoparticle loading that causes an increase in strain to failure of about 50% or more may be utilized.
[0073] Beyond approximately 0.5% loadings, both strength and failure strain are found to diminish with increased SiC loading, falling below the values of the neat matrix at a loading of 1.5%. In fact, the predicted curves shown in Figures 6C and 6D indicate that even at about 0.5% loading, strength and strain to failure may begin to decrease; thus, loadings less than about 0.5% wt%, e.g.,, up to about 0.4 wt%, may be advantageous. For example, at about 1% SiC loading Figures 6C and 6D show approximately no change in strength and strain to failure, and at about 1.5% SiC loading there is about a -55% and -50% drop in strength and strain-to-failure, respectively, compared to the neat matrix. Further, over the range of SiC loadings investigated, the elastic modulus remains approximately constant with the increase in nanoparticles, decreasing only slightly, approximately 14%, when initially added to the polymer matrix. Thus, low loadings of SiC nanoparticles, for example between about 0.2-0.5%, and even between about 0.2 and 0.4%, significantly improve the tensile properties of polymer nanocomposites.
[0074] An exemplifying SENB fracture specimen 304 is illustrated in Figure 3B. In one embodiment, the fracture specimen 304 has a nominal width of about 25.4 mm, a span length of about 1 12 mm, and an average thickness of approximately 6.4 mm. A notch 306 of approximately 12 mm in length and 1.5 mm in width is cut using a milling cutter and sharpened using a razor blade tapped into the notch. The SENB specimens 304 so provided have a nominal crack length to specimen width ratio a/W, of approximately 0.5, satisfying the ASTM standard's requirement for a valid SENB test. At least four such specimens were tested for each material condition. [0075] Kic, and Gic values for the nanocomposites and neat matrix as a function of nanoparticle loading are presented in Figures 7A-B. In general, improvements in both Kic, and Gic values are observed with nanoparticle loadings up to 0.2%. Kic rises from approximately 0.8 MPa ml/2 in the neat matrix to approximately 1.5 MPa m1/2 in the 0.2%-SiC nanocomposite, a nearly two-fold rise. Similarly, Gic increases from approximately 200 J/m2 to 750 J/m2, over the same range, a nearly four-fold rise. Beyond approximately 0.2% nanoparticle inclusion, both Kic and Gic are found to fall back to approximately the value of the neat matrix. Fracture tests, therefore, demonstrate that significant improvements in the fracture toughness and critical strain energy release rate of epoxy can be obtained with low loadings of nanoparticles, particularly less than approximately 0.2%. In one embodiment, any suitable nanoparticle loading that causes about a two fold or more rise in Gic, and/or about a 20% or more rise in Kic, may be utilized.
[0076] These mechanical measurements are further supported by SEM micrographs of the fracture surfaces of the two composites, Figures 8A-C. The micrograph of the neat epoxy surface (Figure 8A) shows a very shiny or glossy surface suggesting that brittle, fast propagation of fracture has taken place. The fracture surface of 0.2% SiC reinforced specimen, Figure 8B) in contrast, is duller. Taken with the mechanical measurements, particularly the stress-strain curves demonstrating plastic yielding, this result illustrates that a more ductile or damage tolerant failure process has occurred in this nanocomposite than in the neat matrix. Furthermore, the fracture surface possesses a very uniform appearance, indicating a lack of agglomerated nanoparticles which would otherwise act as failure initiation sites. Examining the fracture surface of the nanocomposite containing 1% SiC nanoparticles, Figure 8C, the surface appears nonuniform, with dark, generally circular irregularities of agglomerated SiC particles 242. The micrograph further illustrates striations 802 in the fracture surface, consistent with what would be expected from brittle fracture. Thus at increased nanoparticle concentrations, nanoparticle dispersion becomes more difficult to achieve, resulting in agglomerates 242 which act as defects and striations 802 or stress concentration sites which promote crack propagation and give rise to brittle fracture of nanocomposites.
[0077] These mechanical testing and microscopy results demonstrate that low loading fractions of SiC nanoparticles provide composites with substantially dispersed reinforcement having improved toughness, tensile strength, and strain to failure. Bulk nanocomposites: TiO? nanoparticle reinforced nanocomposites [0078] Investigations below illustrate the effects of low loadings of TiO2 nanoparticles on the tensile and fracture properties of nanocomposites and comparable un- reinforced neat matrices. Polyester resin is mixed with TiO2 nanoparticles (Accumet Materials Co.). The TiO2 nanoparticles possess a density of about 0.04-0.06 g/cm3, a surface area of 190-290 m2/g, and a size of approximately 15 nm. TiO2 loadings of 0.2% are investigated in relation to neat polyester matrix only materials. It will be appreciated that other TiO2 loadings may also be utilized, such as in the range of approximately 0.1 % to 0.5%. The TiO2 nanoparticles are added to the polyester resin and the mixture stirred using the magnetic mixer approximately 15 hours at 700 rpm in order to disperse the nanoparticles within the matrix resin. Subsequently, the hardener is added to the homogeneous mixture, in an amount so as to provide an epoxy to hardener ratio of approximately 3OmL to 10 drops. Following addition of the hardener, the mixture is stirred manually for approximately 5 minutes at a linear speed of about 1 cm/sec. Following mixing, the mixture is poured into a polished aluminum mold and allowed to cure in air at room temperature for approximately 4 hours. To quantify the effect of the nanoparticles loading on the performance of the composite, a polyester panel without nanoparticles is also manufactured using the same procedure.
[0079] Figures 9A-B illustrate the appearance of an as-processed neat matrix (9A) and a 0.2% TiO2-reinforced nanocomposite (9B). It is apparent from the micrographs that the nanocomposite presents a white, opaque appearance, while the neat matrix is approximately transparent. In one aspect, this result demonstrates that even small loadings of nanoparticles are sufficient to change the optical properties of the nanocomposite from those of the neat matrix. In another aspect, this result indicates that the mixing procedure described above provides substantially homogeneous dispersion of the nanoparticles within the resin, as the appearance of the nanocomposite is approximately uniform.
[0080] Dogboned tensile specimens were employed for measurement of the tensile properties of the two materials using ASTM D638. At least four specimens were tested for each material condition. Figures 1 OA-C below present the tensile properties of embodiments of the TiO2-Polyester nanocomposites and corresponding neat matrix. [0081] Examining representative stress-strain curves for the nanocomposite, as well as the neat matrix, Figure 1OA, the un-reinforced neat matrix is observed to fail in a brittle manner, with the stress-strain curve rising linearly to failure. In contrast, nanocomposites containing 0.2% TiO2 nanoparticles exhibit yielding prior to failure, as illustrated by the non-linear portion of the curves at elevated values of stress.
[0082] Figures lOB-C presents the ultimate strength and strain to failure of the TiO2-polyester nanocomposites containing 0.2% TiO2 compared to the baseline neat polyester matrix as well as the relative percentage change in the nanocomposite properties with respect to the baseline. In general, the ultimate strength and strain to failure of the nanocomposites are substantially higher than that obtained in the neat matrix. Specifically, the ultimate strength of the nanocomposite is approximately 25% higher than the neat matrix, approximately 47.43 ± 3.2 MPa, compared to approximately 38 ± 0.05 MPa. Furthermore, the failure strain is almost doubled, from about 0.014 ± 0.001 in the neat matrix to approximately 0.028 ± 0.004 in the 0.02-TiO2 nanocomposite. In other embodiments, any suitable nanoparticle loading that causes an increase in ultimate strength of about 10% or more, or an increase in strain to failure of about 50% or more, may be utilized. Addition of nanoparticles to the neat matrix is found to not significantly affect the Young's modulus of the nanocomposite (about 10% reduction), with the modulus of the neat matrix determined to be approximately 3.15 ± 0.02 GPa to the 2.83 ± 0.4 GPa measured in the nanocomposite.
[0083] SENB fracture specimens 304 of TiO2 reinforced nanocomposites are provided as schematically illustrated in Figure 3B. In one embodiment, the fracture specimen 304 has a nominal width of about 12.5 mm, a span length of about 56 mm, and an average thickness of approximately 3.2 mm. A notch 306 of approximately 6 mm in length and 1.5 mm in width is cut using a milling cutter and sharpened using a razor blade tapped into the notch. The SENB specimens 304 so provided have a nominal crack length to specimen width ratio a/W, of approximately 0.5, satisfying the ASTM standard's requirement for a valid SENB test. At least four such specimens were tested for each material condition
[0084] Figures HA-B illustrate the results of SENB fracture tests of an embodiment of a 0.2% TiO2-polyester nanocomposites and comparable neat polyester matrix. With introduction of the 0.2% TiO2, Kic of the nanocomposite increases from about 0.7 MPa m1/2 to about 1.17 MPa m1/2, a roughly 65% increase and more than about a 50% increase over the neat matrix. Further, Gic of the nanocomposite increases more than three fold, from approximately 129 J/m2 for the neat matrix to approximately 546 J/m2 for the nanocomposite. In other embodiments, any suitable nanoparticle loading that causes about a two fold or more rise in Gic, and/or about a 20% or more rise in Kic, may be utilized.
Bulk nanocomposites: CNT reinforced nanocomposites
[0085] Investigations below illustrate the effect of inclusion of low loadings of SWNTs on the tensile and fracture properties of nanocomposites and comparable un- reinforced neat polymers. An epoxy based on DGEPBA-AE is mixed with single walled CNTs (SWNTs) (CarboLex Corporation). These carbon nanotubes have an average diameter of approximately 1.4 ran and are found in "ropes" which are typically about 20nm in diameter or approximately 50 tubes per rope with lengths of 2 - 5 microns. Two weight fractions of CNTs are investigated: 0.02, and 0.1 wt%. Owing to the high degree of adhesion between nanotubes, SWNTs are difficult to separate into single units from aggregates and clusters within epoxy, as epoxy possesses a high viscosity. To circumvent this difficulty, SWNTs are first dispersed within ethyl alcohol (EtOH). The nanotubes are added to EtOH and subjected to a sonication treatment for approximately 5 hours at room temperature. The dispersed EtOH-SWNT solution is mixed at room temperature with the resin using a magnetic hot plate stirrer at approximately 700 rpm for about 15 hours. Further stirring at approximately the same speed is continued, in addition to heating at a constant temperature of about"80°C, for about 45 minutes in order to evaporate the highly volatile EtOH from resin. The mixture is subsequently subjected to a second sonication treatment for approximately 25 min. The hardener is then added to the nanotube-epoxy mixture in an approximately 3 : 1 ratio of epoxy-to-hardener. Subsequently, the nanotube- epoxy-hardener mixture is subjected to slow manual stirring for about 20-30 minutes at a linear speed of approximately 1 cm/sec. This mixing process provides a substantially homogeneously dispersed mixture of SWNT and resin. Following mixing, the mixture is poured into a polished aluminum mold and allowed to cure in air at room temperature for approximately 5 hours. Subsequently, the cured composites are post-cured at approximately 12O0C for 1 hour in air. To quantify the effect of nanotube loading on the performance of the composite, an epoxy panel without nanotubes is also manufactured using the same procedure. [0086] Figures 12A-B illustrate the appearance of the as-processed neat matrix and an approximately 0.02% nanotube-reinforced nanocomposite. It is apparent from the micrographs of Figure 12B, the nanocomposite is colored in appearance, while the neat matrix is approximately transparent, Figure 12A. In one aspect, this result demonstrates that even small loadings of nanoparticles are sufficient to change the optical properties of the nanocomposite from those of the neat matrix to translucent or opaque. In another aspect, this result indicates that the mixing procedure described above provides substantially homogeneous dispersion of the nanoparticles within the resin, as the appearance of the nanocomposite is approximately uniform.
[0087] Dogboned tensile specimens were employed for measurement of the tensile properties of the two materials using ASTM D638. At least four specimens were tested for each material condition. Figures 13A-C below present the tensile properties of the CNT-DGEBPA-AE nanocomposites and corresponding neat matrix.
[0088] Examining representative stress-strain curves for the nanocomposite, as well as the neat matrix, Figure 13 A, the un-reinforced neat matrix is observed to fail in a brittle manner, with the stress-strain curve rising linearly to failure. In contrast, nanocomposites containing 0.2% CNTs nanoparticles exhibit yielding prior to failure, as illustrated by the non-linear portion of the curves at elevated values of stress
[0089] Figures 13B-C presents the ultimate strength and strain to failure of embodiments of the CNT-DGEBPA-AE nanocomposites containing about 0.02%-0.1% CNTs compared to the baseline neat matrix as well as the relative percentage change in the nanocomposite properties with respect to the baseline.
[0090] As illustrated in Figures 13B-C, the neat matrix exhibits a brittle elastic response, with the stress-strain response rising approximately linearly to failure. In contrast, the nanotube-reinforced nanocomposites illustrate yielding prior to failure. Furthermore, the ultimate strength and strain to failure of the nanocomposites are higher than that obtained in the neat matrix: ultimate strength of the nanocomposite is approximately 15% higher than the neat matrix, approximately 40.72 ± 4.5 MPa, compared to 35.9 ± 1.05 MPa. The failure strain also illustrates improvement, rising approximately 150% higher to 2.77%, compared to 1.09%. In other embodiments, any suitable nanotube loading that causes an increase in ultimate strength of about 10% or more, and/or an increase in strain to failure of about 50% or more, may be utilized. The Young's modulus of the nanocomposite is found to be reduced approximately 45%, with the modulus of the neat matrix measured to be approximately 3.5 GPa to the 2.04 GPa measured in the nanocomposite.
[0091] SENB fracture specimens 304 of CNT reinforced nanocomposites are provided as schematically illustrated in Figure 3B. The SENB specimens 304 tested possess a width of approximately 12.5 mm, a span length of approximately 56 mm, and an average thickness of approximately 3.2 mm. A notch 306 of approximately 6 mm in length and 1.5 mm width is cut into the specimens using a milling cutter and sharpened using a razor blade tapped into the notch. So configured, the crack length to width ratio, a/W, is approximately 0.5, satisfying the ASTM requirements for a valid SENB fracture test.
[0092] Figure 14A-B illustrates the results of SENB fracture tests of embodiments of nanotube-epoxy nanocomposites and the neat matrix. With introduction of the 0.02-0.1% nanotubes, Kic of the nanocomposite more than doubled, exhibiting a roughly three fold increase, from about 0.7 MPa ml/2 in the neat matrix, to about 2.2 MPa m1/2 in the nanocomposite. Further, Gic of the nanocomposite increases by more than a factor of 8 and almost ten fold over the neat matrix, from approximately 200 J/m2 for the neat matrix to approximately 1900 J/m2 for the nanocomposite.
EXAMPLES: Nanocomposite Coatings
[0093] In further examples, testing is also performed on polymer coatings reinforced using nanoparticles and their corresponding un-reinforced counterparts in order to illustrate the property improvements which may be achieved in these coatings over un- reinforced coatings. In the examples below, polymer coatings comprising nail polish are investigated. In particular, chemical resistance and mechanical resistance to wear and chipping are examined. While the examples below illustrate nail polishes reinforced with TiO2 nanoparticles, it may be understood that other nanoparticles which include, but are not limited to SiC, ZnO, Y2O3, and C, as well as CNTs may be utilized in alternative embodiments of the invention. In preferred embodiments of the invention, a single nanoparticles or nanotubes species is provided as a reinforcement.
[0094] In general, when applying nail polish, three coatings are employed, a base coating which is applied directly upon the nail, a main color coating which is applied upon the base coating, and a top coating which is applied upon the main color. To test the influence of nanoparticle reinforcements on nail polish coatings, representative, commercially available nail polish products are employed. For example, base and top coatings comprising REVLON FIRMA NAIL and main color coatings comprising REVLON® COLOR ILLUSION, having a metallic red color, are examined. REVLON® FIRMA NAIL comprises combinations of the following compounds: Isopropanol, Acetyl tributyl citrate, Citric acid, Butyl acetate, Sucrose acetate isobutyrate, Ethyl acetate, Heptane, Etocrylene, Malic acid, Bismuth oxychloride, Nitrocellulose, Sucrose benzoate, 2-Propenoic acid, polymer with N-( 1,1 -dimethyl ethyl)-2-propenamide and ethyl 2- propenoate, Stearalkonium hectorite, and Stearalkonium bentonite. REVLON® COLOR ILLUSION, is a nail enamel, generally comprising film forming agents (e.g. Nitrocellulose), resins and plasticizers, solvents, and coloring agents. Further details regarding the formulation of nail polish utilized in embodiments of the invention discussed above may be found in U.S. Patent Application Publication 2005/0220730 to Malnou, et al., the entirety of which is hereby incorporated by reference.
Sample Preparation: Nanocomposite Coatings
[0095] TiO2 nanoparticles are added to each nail polish coating separately and dispersed using the magnetic stirring technique discussed above. The TiO2 nanoparticles possess a particle size of approximately 15 nm, a density in the range of about 0.04-0.06 g/cm3, and a surface area of approximately 190-290 m Ig. Preferably, the nanoparticles may be provided in a quantity as described above, for example about 0.1 wt% to 0.4 wt%, more preferably about 0.2 wt%. To distribute the nanoparticles uniformly within the coatings, an octagonal stirring bar having a length of approximately 1/2 inch and a diameter of approximately 1/8 inch is used for magnetic stirring. Stirring is performed in a closed container at a speed in the range of about 220-280 r.p.m. for approximately 15 hours.
[0096] Examining the as-mixed coatings, several observations were noted. In one aspect, after mixing, it is observed that the main color is substantially unchanged by the nanoparticle reinforcement. In another aspect, the color of the base and top coatings exhibited modest whitening. It is further noted, however, that the change in color of the base and top coatings did not substantially alter the appearance of the final nail polish color when the three coatings were layered upon one another. While nanoparticle reinforcements of nail polishes have previously been performed, such as in U.S. Patent Application Number 2005/0220730, the influence of the reinforcement on the color of the resulting polish has not previously been appreciated. In embodiments of the present invention, the loading fraction of the nanomaterial reinforcement is selected so as to not substantially influence the color of the resulting polish. It is additionally noted that the nanoparticle reinforcement had substantially no influence on the consistency of the nail polish or ease of application.
[0097] The prepared coatings are applied to artificial finger nails for testing. A commercially available artificial nail, Fing'rs® is employed. These artificial nails possess a length of approximately 19 mm and a curvature of about 6.5 mm. The coatings are applied to the nails using appropriate nail polish brushes in two different configurations. In the first configuration, a layer of either the base coating/top coating or the main coating is applied to the nail. Four sets of nails are coated in this manner for testing, with two sets using nail polish reinforced with nanoparticles and two sets using unreinforced nail polish. Each set possessed three nails.
[0098] In the second configuration, one layer of base coating, two layers of main color coating, and one layer of top coating are applied, while the layers which possess the nanoparticle reinforcement are varied. A drying time of approximately 10 minutes is employed after each coating layer is applied. In a first sample set, each coating is without nanoparticle reinforcement. In a second sample set, only the base layer possesses the nanoparticle reinforcement. In a third sample set, the base coating and the two main color coating layers possess the nanoparticle reinforcement. In a fourth sample set, the nanoparticle reinforcement is present within all the coating layers. Nails prepared in this manner are observed to demonstrate substantially no difference in appearance, despite the variation in nanoparticle reinforcement..
[0099] In preparation for testing, the coated nails are glued to aluminum bars having diameters and curvatures approximately equal to that of the nails. Approximately 2/3 of the length of each nail, about 12.5mm, is affixed to the aluminum bars, leaving about 1/3 of the nail length, or approximately 6.5 mm, extending past the end of the bars.
Chemical and Mechanical Testing: Nanocomposite Coatings
[0100] To examine the performance of nanoparticle reinforced nail polish, chemical and mechanical tests are performed to simulate environments and activities that human nails are commonly exposed to and engaged in. Chemical tests are performed by soaking the prepared nails in common household chemicals. A concentration of approximately 50 wt % is used for all chemicals in order to provide a relatively conservative simulation of chemical exposure. Mechanical testing is performed by simulating a typing action. The aluminum bars are used as fingers to cyclically press the nail tips into and out of contact with a computer keyboard. The testing times are illustrated in Table II below.
Table II - Testing Matrix
Figure imgf000028_0001
Chemical and mechanical tests to evaluate the performance of nanoparticle reinforced nail polish are conducted on the polished nails based upon an estimation of a daily exposure time for each chemical or mechanical activity (typing). Respectively, the daily exposure times are taken to be approximately 48, 16, 13, 6.5, and 1.5 minutes for dish washing liquid, liquid hand soap, hair shampoo, hair conditioner, and makeup remover. Similarly, the daily time spent typing is taken to be approximately 19 minutes.
[0101] The daily exposure time is used to estimate the total exposure time over the life cycle of the nail polish. Taking the life cycle of the nails to be approximately four weeks, the daily exposure time is multiplied by 28 days to yield approximate values for the total exposure time over the life cycle of the nails. These values are taken to be, respectively, 22.5, 7.5, 6, 3, and 0.75 hours for dish washing liquid, liquid hand soap, hair shampoo, hair conditioner, and makeup remover.
[0102] Accelerated testing is performed to simulate these total exposure times. The total exposure time for each chemical and mechanical activity is divided into 9 testing cycles. In a cycle, the nails are successively soaked in dish washing liquid, liquid hand soap, hair shampoo, hair conditioner, and makeup remover, for approximately 150, 50, 40, 20, and 5 minutes, respectively. Between each exposure, the nails are allowed to dry for approximately 2 hours. Nails are wiped and dried after each chemical exposure using paper towels for the last five testing cycles. Following each chemical exposure cycle, the nails are used to type continuously for approximately one hour, cyclically bringing the nails in and out of contact with a keyboard in order to simulate a typing action on a computer keyboard. Upon completion of all the testing cycles, the appearance of the nails is examined.
[0103] Examination and comparison of the nails having single layer nanocomposite coatings, multiple layer nanocomposite coatings, and their unreinforced counterparts revealed that nail polishes with nanoparticle reinforcements often exhibit superior performance to unreinforced nail polishes. Figure 15A-B illustrates artificial nails 1500 having a single layer of main color coating which are unreinforced (Figure 15A) and reinforced with the TiO2 nanoparticles (Figure 15B). It is observed that the unreinforced nail polish exhibits scratches 1502 on the surface of the nail after testing, as well as chipping 1504 at the tip of the nail. In contrast, nails painted with nanoparticle reinforced nail polish appear substantially free of such scratching or chipping. These results, therefore, demonstrate that the nanoparticle reinforcement enhances the durability, and thus the useful lifetime, of single nail polish coatings.
[0104] And while the single layer main color coatings tested using the techniques, setup, and durations discussed above showed clear differences in terms of scratches and chipping with and without nanoparticles, the multiple layer nail polish coatings with and without nanoparticles did not illustrate such differences. Further testing may be required to clearly identify improvements.
[0105] These findings demonstrate the substantial gains which can be achieved in strength and strain to failure, as well as in toughening upon low percentage reinforcement of bulk polymer matrices with homogenously distributed nanoparticles and nanotubes. The results further show that nail polish applications may benefit from the use of low loading fractions of reinforcing nanoparticles. It should be noted that U. S Patent Application Publication 2005/0220730 fails to appreciate the advantages and features which may be obtained in nail polishes and other polymer systems reinforced with nanomaterials in the quantities and to obtain the properties as discussed above, and for example in the loading range of approximately 0.01 to 0.4 wt %. In particular, the benefits to the strength and toughness of nanocomposites so reinforced have not previously been recognized.
[0106] Thus, certain embodiments of the present invention provide systems and methods of fabricating nanocomposites having low weight fractions of nanoparticles and nanotubes which are substantially uniformly distributed. Advantageously, the disclosed mixing technique, including a magnetic mixing step, provide a substantially uniform distribution of the nanotubes and nanoparticles which can provide significantly enhanced tensile strength, strain to failure, and fracture toughness over neat matrices alone.
[0107] Although the foregoing description has shown, described, and pointed out the fundamental novel features of the present teachings, it will be understood that various omissions, substitutions, and changes in the form of the detail of the apparatus as illustrated, as well as the uses thereof, may be made by those skilled in the art, without departing from the scope of the present teachings. Consequently, the scope of the present teachings should not be limited to the foregoing discussion, but should be defined by the appended claims.

Claims

WHAT IS CLAIMED IS:
1. A composite material, comprising: a matrix material; and a reinforcement material having at least one dimension of about 100 nm or less dispersed within the matrix material, wherein the reinforcement is present in a concentration between approximately 0.01% and 0.4% on the basis of the weight of the composite material so as to improve at least one of strength and toughness of the composite.
2. The composite material of Claim 1 , wherein the reinforcement material comprises at least one of nanoparticles selected from the group consisting of TiO2, ZnO, SiC, Y2O3, C and carbon nanotubes.
3. The composite material of Claim 2, wherein the nanoparticles are present in a concentration between approximately 0.1% to 0.4% on the basis of weight of the composite material.
4. The composite material of Claim 1 , wherein the matrix material comprises an epoxy and the reinforcement material comprises SiC.
5. The composite material of Claim 4, wherein the SiC reinforcement material is provided in a concentration between about 0.2% and 0.4% on the basis of the weight of the composite material.
6. The composite material of Claim 1 , wherein the matrix material comprises a polyester resin and the reinforcement material comprises TiO2.
7. The composite material of Claim 6, wherein the TiO2 reinforcement material is provided in a concentration of about 0.2% on the basis of the weight of the composite material.
8. The composite material of Claim 1, wherein the reinforcement material comprises carbon nanotubes in a concentration of about 0.01% to 0.1 % on the basis of the weight of the composite material.
9. The composite material of Claim 1, wherein the matrix comprises a high temperature epoxy based on diglycidyl ether of bisphenol A and alkylglycidyl ether, a ceramic based on KiON CERACET™, or polyester.
10. The composite material of Claim 1, wherein the reinforcement causes an increase in ultimate strength of the composite of about 10% or more compared to an unreinforced matrix.
1 1. The composite material of Claim 1 , wherein the reinforcement causes an increase in strain to failure of the composite of about 50% or more compared to an unreinforced matrix.
12. The composite material of Claim 1, wherein the reinforcement causes an increase in Gic of about two-fold or more compared to an unreinforced matrix.
13. The composite material of Claim 1, wherein the reinforcement causes an increase in K|C of about 20% or more compared to an unreinforced matrix.
14. The composite material of Claim 1, wherein the matrix material comprises a nail polish and the reinforcement material comprises TiO2.
15. The composite material of Claim 14, wherein the TiO2 reinforcement material is provided in a concentration of about 0.2% on the basis of the weight of the composite material.
16. A method of manufacturing a nanocomposite, comprising: providing a reinforcement material having dimensions of less than about 100 nm or less in a concentration between about 0.02% to less than about 1% on the basis of the weight of the composite material; providing a matrix material; dispersing the reinforcement material within the matrix material using a magnetic mixing system; adding a curing agent to the reinforcement-matrix mixture; placing the dispersed reinforcement-matrix mixture within a mold; and curing the matrix material.
17. The method of Claim 16, wherein the magnetic mixing system comprises a magnetic stirring device and a magnetic stirring bar.
18. The method of Claim 16, further comprising manual mixing of the matrix material-reinforcement mixture prior to addition of the curing agent.
19. The method of Claim 16, wherein the matrix material is a polymer.
20. The method of Claim 16, wherein the reinforcement material comprises SiC.
21. The method of Claim 16, wherein the reinforcement material comprises TiO2.
22. The method of Claim 16, wherein the reinforcement material comprises carbon nanotubes and wherein the method further comprises: adding the carbon nanotubes to a substantially volatile solvent and subjecting the solvent-nanotube mixture to a sonication treatment prior to addition of the nanoparticles to the matrix material; and adding the solvent-nanotube mixture to the matrix material.
23. A nanomaterial-reinforced nail polish, comprising between approximately 0.2 to 0.4 wt % nanomaterials.
24. The nail polish of Claim 23, wherein color of the nail polish is substantially unchanged by the presence of the nanomaterials.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2474594C2 (en) * 2011-05-10 2013-02-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" Polymer nanocomposites and method for production thereof
CN104693683A (en) * 2015-03-06 2015-06-10 天津鹰麟节能科技发展有限公司 Ceramic anticorrosive material and application method thereof
AU2011230532B2 (en) * 2010-03-26 2015-06-25 University Of Hawaii Nanomaterial-reinforced resins and related materials
EP2955193A1 (en) * 2009-09-03 2015-12-16 Fulcrum S.P. Materials Ltd Multi-site modified sp1 polypeptides and uses thereof
USRE45911E1 (en) 2005-12-20 2016-03-01 University Of Hawaii Polymer matrix composites with nano-scale reinforcements

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007038673A1 (en) * 2005-09-28 2007-04-05 Entrotech Composites, Llc Linerless prepregs, composite articles therefrom, and related methods
DE112007001930A5 (en) * 2006-08-25 2010-02-18 Institut Für Verbundwerkstoffe Gmbh Titanium dioxide-containing composite
US7666327B1 (en) * 2007-05-22 2010-02-23 Oceanit Laboratories, Inc. Multifunctional cementitious nanocomposite material and methods of making the same
EP2176348B1 (en) * 2007-08-02 2017-01-18 Dow Global Technologies LLC Amphiphilic block copolymers and inorganic nanofillers to enhance performance of thermosetting polymers
US7713448B1 (en) * 2007-08-21 2010-05-11 Oceanit Laboratories, Inc. Carbon nanomaterial dispersion and stabilization
US7763187B1 (en) * 2007-08-23 2010-07-27 Oceanit Laboratories, Inc. Carbon nanotubes-reinforced conductive silver ink
JP5034992B2 (en) * 2008-02-06 2012-09-26 住友大阪セメント株式会社 Sintered body and manufacturing method thereof
GB0811357D0 (en) * 2008-06-20 2008-07-30 Q Flo Ltd A mtheod of making carbon nanotube dispensions for the enhancement of fluids
US9023175B2 (en) * 2008-08-04 2015-05-05 Lockheed Martin Corporation Carbon/carbon film adhesive
US8545167B2 (en) * 2009-08-26 2013-10-01 Pratt & Whitney Canada Corp. Composite casing for rotating blades
US8062563B2 (en) * 2009-12-14 2011-11-22 Bowas AG für Industrieplanung Method of manufacturing explosives
US9051216B1 (en) 2010-04-20 2015-06-09 Oceanit Laboratories, Inc. Highly durable composite and manufacturing thereof
US20120251807A1 (en) * 2011-03-31 2012-10-04 University Of Hawaii Nanoparticulate-enhanced coatings
JP5454623B2 (en) * 2012-06-11 2014-03-26 住友大阪セメント株式会社 Sintered body and manufacturing method thereof
US20140175338A1 (en) * 2012-12-21 2014-06-26 Polyone Corporation Electrically conductive polyphenylene sulfide compounds
US10408078B2 (en) 2013-01-29 2019-09-10 United Technologies Corporation Blade rub material
WO2014120117A1 (en) 2013-01-29 2014-08-07 United Technologies Corporation Blade rub material
US10539036B2 (en) * 2014-01-14 2020-01-21 United Technologies Corporation Abradable seal having nanolayer material
RU2612284C1 (en) * 2015-09-09 2017-03-06 Федеральное Государственное Автономное Образовательное Учреждение Высшего Профессионального Образования "Дальневосточный Федеральный Университет" (Двфу) Composite reinforcement
US11391297B2 (en) 2017-11-09 2022-07-19 Pratt & Whitney Canada Corp. Composite fan case with nanoparticles
RU180464U1 (en) * 2018-01-17 2018-06-14 Общество с ограниченной ответственностью "ПолиКомпозит" COMPOSITE FITTINGS MADE FROM GLASS AND EPOXY BINDING
WO2020176560A1 (en) * 2019-02-28 2020-09-03 Cochran Brianna Storm Soluble 3d printed custom artificial nails designed through a mobile application
RU2755343C1 (en) * 2021-03-17 2021-09-15 Сергей Валентинович Белкин Method for obtaining polymer-composite material and composite reinforcement

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020226A2 (en) * 2001-08-31 2003-03-13 L'oreal S.A. Cosmetic compositions comprising nanoparticles and processes for using the same
US20050220730A1 (en) * 2004-04-01 2005-10-06 Alain Malnou Nail polish compositions comprised of nanoscale particles free of reactive groups
US20050228099A1 (en) * 2004-04-13 2005-10-13 Eastman Kodak Company Composition of matter comprising polymer and derivatized nanoparticles

Family Cites Families (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040202603A1 (en) * 1994-12-08 2004-10-14 Hyperion Catalysis International, Inc. Functionalized nanotubes
US6203814B1 (en) * 1994-12-08 2001-03-20 Hyperion Catalysis International, Inc. Method of making functionalized nanotubes
ATE241576T1 (en) * 1995-03-31 2003-06-15 Hyperion Catalysis Int CARBIDE NANOFIGLASSES AND METHOD FOR PRODUCING THE SAME
US6683783B1 (en) * 1997-03-07 2004-01-27 William Marsh Rice University Carbon fibers formed from single-wall carbon nanotubes
US6855202B2 (en) * 2001-11-30 2005-02-15 The Regents Of The University Of California Shaped nanocrystal particles and methods for making the same
DE69923359T2 (en) * 1999-10-28 2005-12-22 3M Innovative Properties Co., Saint Paul COMPOSITIONS AND OBJECTS MANUFACTURED THEREFROM
US6730156B1 (en) * 1999-10-28 2004-05-04 3M Innovative Properties Company Clustered particle dental fillers
AU3505400A (en) * 1999-10-28 2001-05-08 3M Innovative Properties Company Dental materials with nano-sized silica particles
US6653356B2 (en) * 1999-12-13 2003-11-25 Jonathan Sherman Nanoparticulate titanium dioxide coatings, and processes for the production and use thereof
JP5535418B2 (en) * 2000-03-24 2014-07-02 ハイブリッド・プラスチックス・インコーポレイテッド Nanostructured chemicals as alloying agents in polymers
DE10128356A1 (en) * 2000-06-14 2003-01-02 Thueringisches Inst Textil Process for the production of nano-reinforced, thermoplastic polymers
US6495258B1 (en) * 2000-09-20 2002-12-17 Auburn University Structures with high number density of carbon nanotubes and 3-dimensional distribution
US6927301B2 (en) * 2000-10-27 2005-08-09 The Regents Of The University Of Michigan Well-defined nanosized building blocks for organic/inorganic nanocomposites
US7241835B2 (en) * 2001-05-16 2007-07-10 General Electric Company Cosmetic compositions comprising silicone gels
US7001556B1 (en) * 2001-08-16 2006-02-21 The Board Of Regents University Of Oklahoma Nanotube/matrix composites and methods of production and use
US20030148042A1 (en) * 2001-12-28 2003-08-07 Zhikai Wang Ultrasonic method for the production of inorganic/organic hybrid nanocomposite
US6734262B2 (en) * 2002-01-07 2004-05-11 General Electric Company Methods of forming conductive thermoplastic polyetherimide polyester compositions and articles formed thereby
JP3453377B2 (en) * 2002-01-08 2003-10-06 科学技術振興事業団 Carbon nanotube / carbon nanohorn composite and method for producing the same
US6911260B2 (en) * 2002-01-11 2005-06-28 Trustees Of Boston College Reinforced carbon nanotubes
US20040029706A1 (en) * 2002-02-14 2004-02-12 Barrera Enrique V. Fabrication of reinforced composite material comprising carbon nanotubes, fullerenes, and vapor-grown carbon fibers for thermal barrier materials, structural ceramics, and multifunctional nanocomposite ceramics
EP1338361B1 (en) * 2002-02-18 2005-12-14 Fuji Photo Film Co., Ltd. Method of producing nanoparticle
EP1370489B1 (en) * 2002-03-14 2014-03-12 Samsung Electronics Co., Ltd. Composite materials comprising polycarbonate and single-wall carbon nanotubes
EP3656802A1 (en) * 2002-07-22 2020-05-27 Aspen Aerogels Inc. Polyimide aerogels, carbon aerogels, and metal carbide aerogels and methods of making same
US20040127621A1 (en) * 2002-09-12 2004-07-01 Board Of Trustees Of Michigan State University Expanded graphite and products produced therefrom
US7153452B2 (en) * 2002-09-12 2006-12-26 Clemson University Mesophase pitch-based carbon fibers with carbon nanotube reinforcements
CN1225515C (en) * 2002-09-30 2005-11-02 罗姆和哈斯公司 Damage resistant coating, thin film and products containing cross-linked nano-particles
JP3735651B2 (en) * 2002-10-08 2006-01-18 独立行政法人 宇宙航空研究開発機構 Carbon nanofiber dispersed resin fiber reinforced composite material
US6798127B2 (en) * 2002-10-09 2004-09-28 Nano-Proprietary, Inc. Enhanced field emission from carbon nanotubes mixed with particles
CA2504283A1 (en) * 2002-10-31 2004-05-21 Umd, Inc. Therapeutic compositions for drug delivery to and through covering epithelia
US20040101822A1 (en) * 2002-11-26 2004-05-27 Ulrich Wiesner Fluorescent silica-based nanoparticles
US7585349B2 (en) * 2002-12-09 2009-09-08 The University Of Washington Methods of nanostructure formation and shape selection
JP4345308B2 (en) * 2003-01-15 2009-10-14 富士ゼロックス株式会社 Polymer composite and method for producing the same
US7632481B2 (en) * 2003-06-16 2009-12-15 William Marsh Rice University Sidewall functionalization of nanotubes with hydroxyl terminated moieties
US20080112909A1 (en) * 2003-06-24 2008-05-15 Ppg Industries Ohio, Inc. Compositions for providing color to animate objects and related methods
JP2005041835A (en) * 2003-07-24 2005-02-17 Fuji Xerox Co Ltd Carbon nanotube structure, method for producing the same, carbon nanotube transfer and solution
EP1650264A1 (en) * 2003-07-25 2006-04-26 Kaneka Corporation Resin composition containing ultrafine particles
JP2005072209A (en) * 2003-08-22 2005-03-17 Fuji Xerox Co Ltd Resistive element, its manufacturing method, and thermistor
US20050119371A1 (en) * 2003-10-15 2005-06-02 Board Of Trustees Of Michigan State University Bio-based epoxy, their nanocomposites and methods for making those
JP4412052B2 (en) * 2003-10-28 2010-02-10 富士ゼロックス株式会社 Composite material and method for producing the same
JP2005131492A (en) * 2003-10-29 2005-05-26 Fuji Photo Film Co Ltd Gas-liquid separation method and gas-liquid separator
US20060029537A1 (en) * 2003-11-20 2006-02-09 Xiefei Zhang High tensile strength carbon nanotube film and process for making the same
US7074302B2 (en) * 2003-12-05 2006-07-11 Sonoco Development, Inc. Apparatus and process for forming three-dimensional fibrous panels
JP4515798B2 (en) * 2004-03-24 2010-08-04 本田技研工業株式会社 Method for producing carbon nanotube reinforced composite material
US7547361B2 (en) * 2004-03-31 2009-06-16 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Method and apparatus for fabrication of polymer-coated fibers
US7862624B2 (en) * 2004-04-06 2011-01-04 Bao Tran Nano-particles on fabric or textile
US20050257715A1 (en) * 2004-04-08 2005-11-24 Christophe Dumousseaux Compositions for application to the skin, to the lips, to the nails, and/or to hair
JP5254608B2 (en) * 2004-04-13 2013-08-07 ザイベックス パフォーマンス マテリアルズ、インク. Method for synthesizing modular poly (phenylene ethylenin) and method for fine-tuning its electronic properties to functionalize nanomaterials
ATE517202T1 (en) * 2004-10-22 2011-08-15 Dow Global Technologies Llc IMPROVED POLYOLEFINIC MATERIALS FOR PLASTIC COMPOSITIONS
US20060111501A1 (en) * 2004-11-19 2006-05-25 General Electric Company Thermoplastic wear resistant compositions, methods of manufacture thereof and articles containing the same
SG123727A1 (en) * 2004-12-15 2006-07-26 Univ Singapore Nanofiber construct and method of preparing thereof
JP2008527119A (en) * 2005-01-13 2008-07-24 シンベンション アーゲー Composite materials containing carbon nanoparticles
US20070292459A1 (en) * 2005-07-18 2007-12-20 Cooper Sarah M Halloysite microtubule processes, structures, and compositions
US7893148B2 (en) * 2005-08-24 2011-02-22 University Of Houston Nanocomposites of polymers with dispersed nanotubes
US8148276B2 (en) * 2005-11-28 2012-04-03 University Of Hawaii Three-dimensionally reinforced multifunctional nanocomposites
US7658870B2 (en) * 2005-12-20 2010-02-09 University Of Hawaii Polymer matrix composites with nano-scale reinforcements
US7623340B1 (en) * 2006-08-07 2009-11-24 Nanotek Instruments, Inc. Nano-scaled graphene plate nanocomposites for supercapacitor electrodes
US8349067B2 (en) * 2006-11-09 2013-01-08 Sun Chemical Corp. Multi-colored lustrous pearlescent pigments
US7850775B2 (en) * 2006-11-09 2010-12-14 Sun Chemical Corporation Multi-colored lustrous pearlescent pigments
US8211224B2 (en) * 2006-11-09 2012-07-03 Sun Chemical Corp. Multi-colored lustrous pearlescent pigments and process for making
US7666327B1 (en) * 2007-05-22 2010-02-23 Oceanit Laboratories, Inc. Multifunctional cementitious nanocomposite material and methods of making the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020226A2 (en) * 2001-08-31 2003-03-13 L'oreal S.A. Cosmetic compositions comprising nanoparticles and processes for using the same
US20050220730A1 (en) * 2004-04-01 2005-10-06 Alain Malnou Nail polish compositions comprised of nanoscale particles free of reactive groups
US20050228099A1 (en) * 2004-04-13 2005-10-13 Eastman Kodak Company Composition of matter comprising polymer and derivatized nanoparticles

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE45911E1 (en) 2005-12-20 2016-03-01 University Of Hawaii Polymer matrix composites with nano-scale reinforcements
EP2955193A1 (en) * 2009-09-03 2015-12-16 Fulcrum S.P. Materials Ltd Multi-site modified sp1 polypeptides and uses thereof
US9982181B2 (en) 2009-09-03 2018-05-29 Sp Nano Ltd. Multi-site modified SP1 polypeptides and uses thereof
AU2011230532B2 (en) * 2010-03-26 2015-06-25 University Of Hawaii Nanomaterial-reinforced resins and related materials
US9120908B2 (en) 2010-03-26 2015-09-01 University Of Hawaii Nanomaterial-reinforced resins and related materials
RU2474594C2 (en) * 2011-05-10 2013-02-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" Polymer nanocomposites and method for production thereof
CN104693683A (en) * 2015-03-06 2015-06-10 天津鹰麟节能科技发展有限公司 Ceramic anticorrosive material and application method thereof

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