Monolayer Grafting of Organo-Silica Nanoparticles on Poly(ethylene naphthalate) Films

Wall, Jason; Hu, Bin; Siddiqui, and J. A.; Ottenbrite, Raphael M.

doi:10.1021/la0105073

Cited by 11 publications

(7 citation statements)

References 9 publications

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“…Prior work to control interfacial compatibility can be divided into three categories: (1) modifying the filler surface chemistry via the use of coupling agents such as silane coupling agents to covalently bond these two phases, − (2) surface-initiated polymerization with preformed particles, − (3) in situ synthesis of particles within prefabricated polymer matrixes. − Use of coupling agents is usually limited to a specific polymer/filler pair because the selection of coupling agents depends on the detailed chemical structure of the polymeric matrix. The latter two methods have offered possibilities to improve interfacial contact; however, a generally applicable approach involving the blending of premade particles into a presynthesized polymer is most attractive.…”

Section: Introductionmentioning

confidence: 99%

A General Strategy for Adhesion Enhancement in Polymeric Composites by Formation of Nanostructured Particle Surfaces

2006

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In this work we present a general methodology to enhance the interfacial adhesion in polymeric composites by creating nanoscale morphologies on the surfaces of particles. The surface morphology, which appears as inorganic whiskers, is achieved by treating silicate particles (zeolites 4A) with thionyl chloride, followed by subsequent reaction with methylmagnesium bromide (Grignard reagent). Poly(vinyl acetate) and Ultem composites containing this type of modified particles exhibit defect-free interfaces. Dynamic mechanical analysis testing reveals that such composites have higher moduli as compared to those embedded with nontreated fillers with the same loadings. Furthermore, gas permeation measurements demonstrate that these materials also show impressive enhancements in gas separation efficiency. The dramatic increase in the topological roughness (physical heterogeneity) on the sieve surfaces is proposed to provide improved interaction at the interface via thermodynamically induced adsorption and physical interlocking of polymer chains in the nanoscopic inorganic whisker structure. The presented strategy need not be tailored to a specific polymer/filler pair and therefore has potential to be extended to many other polymeric composites for a variety of applications, where tailoring polymer/solid interface compatibility is important.

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Section: Introductionmentioning

confidence: 99%

A General Strategy for Adhesion Enhancement in Polymeric Composites by Formation of Nanostructured Particle Surfaces

2006

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“…9 Adhesion between the additive and the matrix has previously been achieved using interfacial agents, modied particle surfaces, and ionic liquids. 6,10,11 We recently reported 9 that physical aging could be addressed through a strong interaction of the carbonaceous pores of PAF-1 12 with polymer side-chains.…”

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confidence: 99%

AIMs: a new strategy to control physical aging and gas transport in mixed-matrix membranes

et al. 2015

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“…Several strategies for controlling the interface properties have been reported, such as surface-initiated polymerization, , modification of the inorganic particle surfaces via silane-based covalent attachment to the polymer, , in situ polymerization of the polymer on the inorganic particle, , or the deposition of roughened inorganic nanostructures on the particle surface. ,, The use of inorganic nanostructures to roughen molecular sieve particle surfaces has recently allowed enhancements in the properties of MMMs in gas separations. ,, In particular, MgO x H y (1 ≤ x ≤ 2, 0 ≤ y ≤ 2) nanostructures have been grown on the surface of zeolites such as pure-silica MFI and aluminosilicate LTA through four techniques, namely Grignard decomposition reactions, , solvothermal and modified solvothermal depositions, , and ion exchange induced surface crystallization . The roughened surfaces provide a high surface area for noncovalent interactions and also allow for entanglement of the polymer chains leading to enhanced adhesion. ,,, …”

Section: Introductionmentioning

confidence: 99%

“…Several strategies for controlling the interface properties have been reported, such as surface-initiated polymerization, 14,15 modification of the inorganic particle surfaces via silane-based covalent attachment to the polymer, 2,16 in situ polymerization of the polymer on the inorganic particle, 14,15 or the deposition of roughened inorganic nanostructures on the particle surface. 5,7,17 The use of inorganic nanostructures to roughen molecular sieve particle surfaces has recently allowed enhancements in the properties of MMMs in gas separations.…”

Section: ■ Introductionmentioning

confidence: 99%

Structure–Property Relationships of Inorganically Surface-Modified Zeolite Molecular Sieves for Nanocomposite Membrane Fabrication

et al. 2012

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A multiscale experimental study of the structural, compositional, and morphological characteristics of aluminosilicate (LTA) and pure-silica (MFI) zeolite materials surface-modified with MgO x H y nanostructures is presented. These characteristics are correlated with the suitability of such materials in the fabrication of LTA/ Matrimid mixed-matrix membranes (MMMs) for CO 2 /CH 4 separations. The four functionalization methods studied in this work produce surface nanostructures that may appear superficially similar under SEM observation but in fact differ considerably in shape, size, surface coverage, surface area/ roughness, degree of attachment to the zeolite surface, and degree of zeolite pore blocking. The evaluation of these characteristics by a combination of TEM, HRTEM, N 2 physisorption, multiscale compositional analysis (XPS, EDX, and ICP-AES elemental analysis), and diffraction (ED and XRD) allows improved understanding of the origin of disparate gas permeation properties observed in MMMs made with four types of surface-modified zeolite LTA materials, as well as a rational selection of the method expected to result in the best enhancement of the desired properties (in the present case, CO 2 /CH 4 selectivity increase without sacrificing permeability). A method based on ion exchange of the LTA with Mg 2+ , followed by base-induced precipitation and growth of MgO x H y nanostructures, deemed "ion exchange functionalization" here, offers modified particles with the best overall characteristics resulting in the most effective MMMs. LTA/ Matrimid MMMs containing ion exchange functionalized particles had a considerably higher CO 2 /CH 4 selectivity (∼40) than could be obtained with the other functionalization techniques (∼30), while maintaining a CO 2 permeability of ∼10 barrers. A parallel study on pure silica MFI surface nanostructures is also presented to compare and contrast with the zeolite LTA case.

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Monolayer Grafting of Organo-Silica Nanoparticles on Poly(ethylene naphthalate) Films

Cited by 11 publications

References 9 publications

A General Strategy for Adhesion Enhancement in Polymeric Composites by Formation of Nanostructured Particle Surfaces

A General Strategy for Adhesion Enhancement in Polymeric Composites by Formation of Nanostructured Particle Surfaces

AIMs: a new strategy to control physical aging and gas transport in mixed-matrix membranes

Structure–Property Relationships of Inorganically Surface-Modified Zeolite Molecular Sieves for Nanocomposite Membrane Fabrication

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