Interdiffusion of Low Molecular Weight Deuterated Polystyrene and Poly(methyl methacrylate)

Shearmur, T.E.; Clough, A.S.; Drew, D.W.; Grinten, M. G. D. van der; Jones, R. C.

doi:10.1021/ma960458e

Cited by 28 publications

(25 citation statements)

References 49 publications

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“…For high molecular weight polymers, characteristic diffusion distances that define the interfacial structure are in the range of tens to hundreds of nanometers. Several techniques which high‐spatial resolution (<100 nm) have been employed to investigate the topic, such as Forward Recoil Spectrometry, Nuclear Reaction Analysis or Fluorescence Resonance Energy Transfer, along with many others recently developed . With these techniques, diffusion coefficients below 10 −14 cm 2 /s have been typically measured.…”

Section: Introductionmentioning

confidence: 99%

Tracking high molecular weight polymer interdiffusion on a SERS‐based platform

Mana

Tomba

2016

J Raman Spectroscopy

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We describe the implementation of an experimental setup based on Surface Enhanced Raman Spectroscopy (SERS) to investigate polymer interdiffusion. Ultra‐thin bilayer films of deuterated polystyrene (dPS) and polystyrene (PS) are placed in contact onto SERS‐active gold substrates with inverted square‐base pyramidal geometry and subsequently annealed. Initially, the Raman spectrum shows only spectral features of the polymer adjacent to the substrate. Upon annealing, Raman bands of the polymer located far from the substrate start to emerge, an indication of chain diffusion into the substrate hotspot and mixing between polymer layers. The kinetics of the process is consistent with transport of polymer chains in nanometer scale, with diffusion coefficients in the range 10−13 – 10−15 cm2/s. The temperature response of the process is characterized by an activation energy of 48.93 ± 1.5 kcal/mol, in excellent agreement with earlier experiments. SERS experiments provide a powerful and reliable experimental platform to characterize polymer interdiffusion without the need of chemical labeling, with several prospective applications to the study of chain dynamics in advanced polymer‐based nanocomposite materials. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

Tracking high molecular weight polymer interdiffusion on a SERS‐based platform

Mana

Tomba

2016

J Raman Spectroscopy

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“…The process that is dominant in this technique is the segregation of the copolymer from a blend to a biphasic interface. Many studies have investigated the surface and interfacial properties of polymer blend thin films, including wetting phenomena, surface and interfacial segregation, and phase separation 17–39. In the case of surface segregation, small differences in the surface energy between the components can drive the segregation process of the lower surface energy component of a polymer blend to an interface.…”

Section: Introductionmentioning

confidence: 99%

Using neutron reflectivity to determine the dynamic properties of a copolymer in a homopolymer matrix

Arlen

Dadmun

Hamilton

2004

J Polym Sci B Polym Phys

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A protocol for using neutron reflectivity to monitor the dynamic properties of a copolymer in a homopolymer matrix is described. This technique may be used to monitor a broad range of systems, as long as the copolymer and homopolymer form a miscible blend at low copolymer concentrations. Moreover, with knowledge of the Flory-Huggins interaction parameter between the copolymer and homopolymer, the molecular dynamic parameters of the copolymer, such as the tracer diffusion coefficient, segmental friction factor, and longest relaxation time, can be quantitatively determined. This technique is demonstrated by the determination of these parameters for a series of styrene/methyl methacrylate alternating copolymers dispersed in a matrix of deuterated poly(methyl methacrylate). Interestingly, the segmental friction factor of these alternating copolymers is significantly different from that of similar diblock copolymers.

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“…These studies have m ade possible the benchtesting of diffusion models and have contributed to the elucidation of the physical mechanisms that operate in polymer diffusion processes. [2][3][4][5][6][7][8][9][10][11][13][14][15][16] Details of the measured composition pro les can be used to test physical models and to calculate diffusion param eters such as front advancing rates, pro le slopes, and corner shapes. These parameters play a m ain role in tting experimental data to m odels, and therefore, instrumental resolution and accuracy are crucial.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11] Nuclear reaction analysis (NRA) has the same high intrinsic resolution, but only recently has it been applied to polymer studies. [12][13][14] This group of techniques is based on hitting the sample surface with charged He nuclei (He 21 for FRES or RBS, He 31 for NRA), and they require a heavier tracer element to be linked to the diffusing species. Collisions between He nuclei and the heavier element can produce a recoiling of the heavier element (in the case of FRES), backscattering of He 21 nuclei (in the case of RBS), or a nuclear reaction that produces He 41 ions (in the case of NRA).…”

Section: Introductionmentioning

confidence: 99%

“…In the case of FRES, RBS, and NRA, the broadening in the energy values recorded by the detector has been reported as the most important. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] As the energy of the detected nuclei is a function of the depth into the polymer sample, it leads to a broadening in the diffusion coordinate scale. M any authors have used these techniques to study diffusion processes such as transport of small m olecules into glassy polymer m atrices and interpenetration of polymers with different physical properties.…”

Section: Introductionmentioning

confidence: 99%

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True Chemical Composition Profiles at Polymer Interphases: Recovery from Measurements Distorted by Instrumental Broadening

Tomba

Eliçabe

2003

Appl Spectrosc

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The determination of chemical composition profiles at polymer interphases is an important issue at the moment of elucidating the physical mechanisms that operate in polymer diffusion processes and for calculating diffusion parameters. Several techniques are available to measure these profiles, the most common being forward recoil spectroscopy, Rutherford backscattering spectrometry, nuclear reaction analysis, confocal Raman microspectroscopy (CRM), and scanning infrared microscopy. However, all these techniques are affected by the limited resolution of the experimental setup, which in practice produces a rounding effect on the sharp corners of the composition profile; this may lead to incorrect conclusions regarding the measurements. In this work an inverse technique is proposed to correct this undesirable effect in the profiles. The inversion is performed on a model of the measuring process, which includes the instrumental broadening function, a quantitative representation of the limited resolution. The proposed methodology was tested using numerically generated experiments and genuine experimental runs obtained from CRM measurements at interphases of polymer bilayers. In all cases, the recovered profiles were close to the expected ones. In the truly experimental results diffusion tails are observed behind and ahead of the diffusion front before the numerical treatment of the data. These tails may be caused by a genuine mass diffusion or by an artifact. After the numerical treatment the tails disappear and a sharp interphase is recovered, a result one expects for the polymer pairs under study.

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Interdiffusion of Low Molecular Weight Deuterated Polystyrene and Poly(methyl methacrylate)

Cited by 28 publications

References 49 publications

Tracking high molecular weight polymer interdiffusion on a SERS‐based platform

Tracking high molecular weight polymer interdiffusion on a SERS‐based platform

Using neutron reflectivity to determine the dynamic properties of a copolymer in a homopolymer matrix

True Chemical Composition Profiles at Polymer Interphases: Recovery from Measurements Distorted by Instrumental Broadening

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