The present disclosure generally relates to a nanocomposite composition.
Gas transport through a polymer may be modeled according to a solution-diffusion mechanism, and may be expressed as a permeability of the polymer, i.e., a rate at which gas passes through the polymer. For example, during gas transport through the polymer, a gas molecule may dissolve into the polymer from a region of relatively high pressure, diffuse through a thickness of the polymer, and desorb from a surface of the polymer to a region of comparatively low pressure. Permeability may therefore be affected by the diffusivity of the gas molecule within the polymer.
Such diffusivity may be expressed as a diffusivity coefficient, i.e., a measure of a mobility of the gas molecule within the polymer. As the diffusivity coefficient decreases, permeation of the gas molecule through the polymer also decreases, and gas transport through the polymer is slowed.
A nanocomposite composition includes a polymer and a barrier component sufficiently dispersed within the polymer so as to define a tortuous path within the polymer. The barrier component includes a nano-constituent including a plurality of layers and a macro-constituent including a plurality of particles. Each of the plurality of layers has a first average thickness, and each of the plurality of particles has a second average thickness that is greater than the first average thickness.
A nanocomposite system includes a substrate and a coating disposed on the substrate. The coating is formed from the nanocomposite composition.
The above features and advantages and other features and advantages of the present disclosure are readily apparent from the following detailed description of the best modes for carrying out the disclosure when taken in connection with the accompanying drawings.
Referring to the Figures, wherein like reference numerals refer to like elements, a schematic illustration of a magnified portion of a nanocomposite composition 10 is shown generally in
As used herein, the terminology “nanocomposite composition” refers to a material in which at least one constituent has one or more dimensions, such as length, width, or first average thickness 12 (
Referring again to
As described with continued reference to
Referring again to
As shown in
In one variation, the nano-constituent 24 (
In another variation, the nano-constituent 24 may include a carbon-based platelet-type nanoparticle. For example, the nano-constituent 24 may include grapheme. The nano-constituent 24 may have a first average thickness 12 (
The nano-constituent 24 may be present in an amount of from about 0.1 parts by weight to about 100 parts by weight based on 100 parts of the polymer 14. In one example, the nano-constituent 24 may be present in an amount of from about 20 parts by weight to about 40 parts by weight based on 100 parts by weight of the polymer 14. At amounts less than about 0.1 parts by weight, the barrier component 16 may not effectively impede gas permeation in the polymer 14, and at amounts greater than about 100 parts by weight, the barrier component 16 may not sufficiently disperse within the polymer 14. A suitable nano-constituent 24 is commercially available from Nanocor Inc. of Arlington Heights, Ill., under the trade name Nanomer®.
In one variation, the nano-constituent 24 may be chemically modified. Chemical modification of the nano-constituent 24 may improve the dispersion and/or the adhesion of the nano-constituent 24 within the polymer 14. That is, chemical modification of the nano-constituent 24 may improve compatibility with the polymer 14 (
In one example, the nano-constituent 24 may be chemically modified via an ion-exchange reaction to replace a hydrated cation on a surface of the layers 18 of the nano-constituent 24. For example, the layers 18 of the nano-constituent 24 may be modified by a surfactant, a monomer group, and/or combinations thereof. A suitable surfactant includes alkylamonium. Suitable monomer groups include ammonium salt, octadecylamine, hydrogenated tallow-bis(2-hydroxyethyl) methyl ammonium salt, methyl-tallow-bis(2-hydroxyethyl) quaternary ammonium salt, octadecyltrimethyl ammonium salt, dimethyl hydrogenated tallow 2-ethylhexyl quaternary ammonium salt, and combinations thereof.
Referring again to
As shown in
Referring to
In one variation, the macro-constituent 28 may be chemically modified. Chemical modification of the macro-constituent 28 may improve compatibility with the nano-constituent 24 and/or the polymer 14. The macro-constituent 28 may be chemically modified with a silane such as, but not limited to, an organosilane. Suitable silanes include methyltrimethoxysilane, aminopropyltriethoxysilane, diaminosilane, triaminosilane, and combinations thereof. However, the macro-constituent 28 may be substantially free from chemical modification by an alkyl ammonium salt so as not to interfere with compatibility of the nano-constituent 24 and the polymer 14.
Without intending to be limited by theory, the macro-constituent 28 may exfoliate the nano-constituent 24 of the barrier component 16. As used herein, the terminology “exfoliate” or “exfoliated” refers to individual layers 18 of the nano-constituent 24 dispersed throughout a carrier material, e.g., the polymer 14. Generally, “exfoliated” denotes a highest degree of separation of layers 18 of the nano-constituent 24 and is contrasted with intercalated layers 18 as defined below. Likewise, the terminology “exfoliation” refers to a process for forming an exfoliated nano-constituent 24 from an intercalated or otherwise less-dispersed state of separation of the layers 18 of the nano-constituent 24. In contrast, the terminology “intercalate” or “intercalated” refers to a layered constituent having merely increased interlayer spacing between adjacent layers 18, i.e., interlayer spacing that is less than the interlayer spacing of the exfoliated nano-constituent 24. Stated differently, exfoliated nano-constituent 24 represents the highest level of dispersion of the individual layers 18 of nano-constituent 24 within the polymer 14.
Referring again to
Further, the nano-constituent 24 may be uniformly dispersed within the polymer 14. That is, although an orientation of the individual layers 18 of the nano-constituent 24 may differ in two separate regions of the nanocomposite composition 10 as shown in
Likewise, the macro-constituent 28 may be uniformly dispersed within the polymer 14. That is, two separate regions of the nanocomposite composition 10 may include an equal amount of the macro-constituent 28. Alternatively, the macro-constituent 28 may be randomly dispersed within the polymer 14. That is, two separate regions of the nanocomposite composition 10 may include differing amounts or concentrations of the macro-constituent 28.
As best shown in
More specifically, as described with reference to
In addition, the macro-constituent 28 (
The nanocomposite composition 10 (
Referring now to
The coating 46 may be applied to the substrate 44 via any suitable process and/or device. For example, the coating 46 may be sprayed or roll-coated onto the substrate 44. In addition, the coating 46 may have a thickness 48 of from about 5 microns to about 1,000 microns. Further, the substrate 44 may be any suitable material configured for supporting the coating 46. The substrate 44 may be selected from the group including elastomers, e.g., rubber, fabric, e.g., woven para-aramid synthetic fiber, and combinations thereof.
Referring again to
The polymer 14 and the barrier component 16 may be mixed by any suitable process and/or apparatus. By way of non-limiting examples, mixing may include processes selected from the group including melt mixing, extruding, shear mixing, pulverizing, solution casting, compounding, and combinations thereof. That is, mixing may sufficiently interdisperse the nano-constituent 24 and the macro-constituent 28 within the polymer 14 so that the macro-constituent 28 may shear and/or exfoliate the nano-constituent 24 to thereby define the tortuous path 36 (
The method may further include chemically modifying each of the plurality of layers 18. For example, the individual layers 18 may be chemically modified to improve the dispersion, adhesion, and/or compatibility of the nano-constituent 24 (
In one example, the nano-constituent 24 (
The method may further include chemically modifying each of the plurality of particles 30 (
The method may also include combining the blend and one or more additives and/or curing agents. Suitable additives include, but are not limited to, fillers, dyes, plasticizers, antioxidants, activators, and combinations thereof. Suitable curing agents include vulcanizing agents, crosslinking agents, organic peroxides, and combinations thereof.
The nanocomposite composition 10 and system 42 exhibit decreased gas permeability. In particular, the nano-constituent 24 and the macro-constituent 28 interact to impede gas transport through the polymer 14. As such, the nanocomposite composition 10 and system 42 are useful for applications requiring materials having decreased gas permeability, and excellent elongation at break, tensile strength, and modulus of elasticity.
The following examples are meant to illustrate the disclosure and are not to be viewed in any way as limiting to the scope of the disclosure.
To prepare the nanocomposite compositions of Examples 1 and 2 and Comparative Examples 3-5, components A-G are combined in the amounts listed in Table 1. Specifically, the nanocomposite compositions of each of Examples 1 and 2 and Comparative Examples 4 and 5 are prepared by compounding component B and/or component C in component A with Additives D and E in a Banbury Mixer BR 1600 at a rotor speed of 55 revolutions per minute for 5 minutes to prepare respective homogeneous blends. Additive F and Curing AgenteG are combined with each of the homogeneous blends and mixed for an additional 2 minutes to form the respective nanocomposite compositions of Examples 1 and 2 and Comparative Examples 4 and 5. Each of the resulting nanocomposite compositions is mixed on a roll mill to form a sheet, and cured to form plaques for evaluation according to the test methods set forth below. The amounts of components B-G listed in Table 1 refer to parts by weight based on 100 parts by weight of component A.
Component A is hydrogenated acrylonitrile-butadiene rubber commercially available from Zeon Chemicals L.P. of Louisville, Ky., under the trade name Zetpol®.
Component B is 2:1 layered phyllosilicate and includes a plurality of layers each having a first average thickness of 1 nm. Component B is commercially available from Nanocor Inc. of Arlington Heights, Ill., under the trade name Nanomer®.
Component C is hydrated magnesium silicate, i.e., talc, and includes a plurality of particles each having a second average thickness of 50 microns. Component C is commercially available from Luzenac Inc. of Greenwood Village, Colo., under the trade name Mistron® Vapor R talc.
Additive D is carbon black. Component D is commercially available from Columbian Chemicals Company of Marietta, Ga.
Additive E is 4,4′-bis dimethylbenzyl diphenylamine. Component E is commercially available from Chemtura Corporation of Middlebury, Conn.
Additive F is a combination of zinc oxide, commercially available under the trade name Kadox® 911 from Horsehead Corporation of Monaca, Pa., and stearic acid, commercially available under the trade name INDUSTRENE® R from Akrochem Corporation of Akron, Ohio.
Curing Agent G is 1,1′-bis(t-butylperoxy)-diisopropylbenzene. Curing Agent G is commercially available from GEO® Specialty Chemicals of Gibbstown, N.J., under the trade name Vul-Cup® 40KE.
After compounding, the resulting nanocomposite compositions of Example 1, Comparative Example 4, and Comparative Example 5 have a thickness of 500 microns.
In contrast, the nanocomposite composition of Example 2 is roll-coated onto a natural rubber substrate to form a nanocomposite system including a coating disposed on the substrate. The resulting coating formed from the nanocomposite composition of Example 2 has a thickness of 750 microns, and the natural rubber substrate has a thickness of 2 cm.
Each of the nanocomposite compositions of Examples 1 and 2 and Comparative Examples 3-5 is evaluated according to the test procedures set forth below.
Each of the nanocomposite compositions of Examples 1 and 2 and Comparative Examples 3-5 is evaluated to determine an interlayer spacing between the plurality of layers of component B on a Scintag XDS2000 diffractometer in a Bragg-Brentano geometry. Each nanocomposite composition is scanned in a continuous symmetric scan with a step size of 0.02° at a scan rate of 0.5°/min. The scan range in 20 is from 1° to 10°. The tube and director fixed slits are 0.3°, 0.5° and 1°, 0.2°, respectively. The x-ray radiation is a CuKα1, λ=1.5418 Å. Patterns and data are processed with MDI JADE 9+ software.
Referring to
By comparison, described with continued reference to
The nanocomposite compositions of each of Examples 1 and 2 and Comparative Examples 4 and 5 are evaluated for gas permeability at 23° C. and 80° C. according to test method ASTM D 1434-82. Control 6, a hydrogenated acrylonitrile-butadiene rubber, is also evaluated for gas permeability according to the aforementioned test method and compared to the nanocomposite compositions of each of Example 1 and 2 and Comparative Examples 4 and 5. The results of the gas permeability testing are illustrated in
The nanocomposite compositions of Examples 1 and 2, which include both phyllosilicate (component B) and talc (component C), have a lower gas permeability than the rubber of Control 6. In comparison, the nanocomposite compositions of each of Comparative Examples 4 and 5 have higher gas permeability than the nanocomposite compositions of Examples 1 and 2 for the same loading of phyllosilicate (component B). As such, the nanocomposite compositions of Examples 1 and 2 exhibit improved gas permeability as compared to the nanocomposite compositions of Comparative Examples 4 and 5.
The nanocomposite compositions of each of Examples 1 and 2 and Comparative Examples 4 and 5 are evaluated for tensile strength according to test method ASTM D 412. Control 6, a hydrogenated acrylonitrile-butadiene rubber, is also evaluated for tensile strength according to the aforementioned test method and compared to the nanocomposite compositions of each of Examples 1 and 2 and Comparative Examples 4 and 5. The results of the tensile strength testing are listed in Table 2.
The nanocomposite compositions of Examples 1 and 2, which include both phyllosilicate (component B) and talc (component C), have a comparable tensile strength to the rubber of Control 6. The addition of component B and component C does not significantly decrease the tensile strength of the nanocomposite compositions of Examples 1 and 2 as compared to the rubber of Control 6.
The nanocomposite compositions of each of Examples 1 and 2 and Comparative Examples 4 and 5 are evaluated for elongation at break according to test method ASTM D 412. Control 6, a hydrogenated acrylonitrile-butadiene rubber, is also evaluated for elongation at break according to the aforementioned test method and compared to the nanocomposite compositions of each of Examples 1 and 2 and Comparative Examples 4 and 5. The results of the elongation at break testing are listed in Table 3.
The nanocomposite compositions of Examples 1 and 2, which include both phyllosilicate (component B) and talc (component C), and Comparative Examples 4 and 5 have an acceptable elongation at break when compared to the rubber of Control 6. As such, the inclusion of both phyllosilicate (component B) and talc (component C) in the nanocomposite composition of Example 1 does not unacceptably decrease elongation at break.
The nanocomposite compositions of each of Examples 1 and 2 and Comparative Examples 4 and 5 are evaluated for modulus of elasticity at 50% strain according to test method ASTM D 412. Control 6, a hydrogenated acrylonitrile-butadiene rubber, is also evaluated for modulus of elasticity at 50% strain according to the aforementioned test method and compared to the nanocomposite compositions of each of Example 1 and Comparative Examples 4 and 5. The results of the modulus of elasticity testing are listed in Table 4.
The nanocomposite compositions of Examples 1 and 2, which include both phyllosilicate (component B) and talc (component C), have a higher modulus of elasticity than the rubber of Control 6. As such, the nanocomposite compositions of Examples 1 and 2 exhibit a greater modulus of elasticity than the nanocomposite compositions of Comparative Examples 4 and 5 for the same loading of component B.
While the best modes for carrying out the disclosure have been described in detail, those familiar with the art to which this disclosure relates will recognize various alternative designs and embodiments for practicing the disclosure within the scope of the appended claims.
This application claims the benefit of U.S. Provisional Patent Application No. 61/245,776, filed Sep. 25, 2009, which is hereby incorporated by reference in its entirety.
Number | Date | Country | |
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61245776 | Sep 2009 | US |