Molecular Dynamics in Poly(N-vinylpyrrolidone)-Poly(ethylene glycol) Blends Investigated by the Pulsed-Field Gradient NMR Method: Effects of Aging, Hydration and PEG Chain Length

Vartapetian, R. Sh.; Khozina, E. V.; Kärger, Jörg; Geschke, D.; Rittig, Frank; Feldstein, Michail M.; Chalykh, A.Ye.

doi:10.1002/1521-3935(20010801)202:12<2648::aid-macp2648>3.0.co;2-l

Cited by 16 publications

(14 citation statements)

References 7 publications

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“…46,51,52 Interdiffusion and PVP-PEG miscibility have been characterized using optical microinterference techniques, 35,37,53 while self diffusion of polymer components and absorbed water has been studied using pulsed field gradient (PFG) nuclear magnetic resonance (NMR). 54,55 Rheological (mechanical) properties have also been characterized in detail. 56,57 Relaxation properties of model PVP-PEG PSAs have been studied on withdrawal of bonding pressure.…”

Section: Model Psa System Designed To Elicit Molecular Structures Resmentioning

confidence: 99%

“…54,55 In PFG-NMR experiments, the incoherent intermediate structure function, S inc (q, t), of protons in a system, given by spin echo attenuation, is measured as a function of the generalized scattering vector, q ¼ c Â d Â g, where c is the gyromagnetic ratio of the proton, d is pulse width, and g is the magnitude of the PFG. Spin echo attenuation curves are fitted to a biexponential expression,…”

Section: Diffusion Coefficientsmentioning

confidence: 99%

“…Over the following 32 days, however, diffusion decay evolved into a biexponential behavior with a slower self diffusion coefficient of 1.5 Â 10 À9 cm 2 /s and p ¼ 0.87. 55 After this time, the diffusion properties of the system were unchanged. Such an aging process is typical for self assembling supramolecular structures involving hydrogen bonding and stoichiometric complex formation.…”

Section: Diffusion Coefficientsmentioning

confidence: 99%

“…The observed character of PEG motion agrees well with the effect of PEG immobilization in PVP-PEG blends that has been established by PFG-NMR. 55 Thus, the effect of hydrogen bonding of terminal hydroxyl groups in short chain PEG to the repeat units in PVP macromolecules is responsible not only for miscibility of the system, but also for the character of PEG diffusion in the blends. Clearly, H-bonding of PEG to PVP macromolecules results in constrained PEG motion.…”

Section: Reviewmentioning

confidence: 99%

“…Clearly, H-bonding of PEG to PVP macromolecules results in constrained PEG motion. 37 Figure 21 23 compares peel adhesion (P) of the PVP-PEG model adhesives with their diffusion behaviors expressed in terms of the self diffusion coefficient of the slowly diffusing component, 54,55 and the partial diffusion coefficient of PEG-400 in blends with PVP (D PEG ). As follows from the data presented in Figure 21, the self diffusion coefficient of PEG-400 within the H-bonded PVP-PEG network at 36% PEG concentration in the blend is D PEG ¼ 1.3 Â 10 À9 cm 2 /s.…”

Section: Reviewmentioning

confidence: 99%

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Molecular and nanoscale factors governing pressure‐sensitive adhesion strength of viscoelastic polymers

Feldstein

Siegel

2012

J Polym Sci B Polym Phys

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Pressure‐sensitive adhesives (PSAs) are finding increasing applications in various areas of industry and medicine. PSAs are a special class of viscoelastic polymers that form strong adhesive joints with substrates of varying chemical nature under application of light external bonding pressures (1–10 Pa) over short periods of time (1–5 s). To be a PSA, a polymer should possess both high fluidity under applied bonding pressure, to form good adhesive contact, and high cohesive strength and elasticity, which are necessary for resistance to debonding stresses and for dissipation of mechanical energy at the stage of adhesive bond failure under detaching force. For rational design of novel PSAs, molecular insight into mechanisms of their adhesive behavior is necessary. As shown in this review, strength of PSA adhesive joints is controlled by a combination of diffusion, viscoelastic, and relaxation mechanisms. At the molecular level, strong adhesion is the result of a narrow balance between two generally conflicting properties: high cohesive strength and large free volume. These conflicting properties are difficult to combine in a single polymer material. Individually, high cohesive interaction energy and large free volume are necessary but insufficient prerequisites for PSA strength. Evident correlations are observed between the adhesive bond strengths of different PSAs, and their relaxation behaviors are described by longer relaxation times. Innovative PSAs with tailored properties can be produced by physical mixing of nonadhesive long‐ and short‐chain linear parent polymers, with groups at the two ends of the short chains complementary to the functional groups in the recurring units of the long chains. Although chemical composition and molecular structure of such innovative adhesives are unrelated to those of conventional PSAs, their mechanical properties and adhesive behaviors obey the same general laws, such as the Dahlquist's criterion of tack. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

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Section: Model Psa System Designed To Elicit Molecular Structures Resmentioning

confidence: 99%

Section: Diffusion Coefficientsmentioning

confidence: 99%

Section: Diffusion Coefficientsmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

See 3 more Smart Citations

Molecular and nanoscale factors governing pressure‐sensitive adhesion strength of viscoelastic polymers

Feldstein

Siegel

2012

J Polym Sci B Polym Phys

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Competitive hydrogen bonding mechanisms underlying phase behavior of triple poly(N‐vinyl pyrrolidone)–poly(ethylene glycol)–poly(methacrylic acid‐co‐ethylacrylate) blends

Kireeva

Shandryuk

Kostina

et al. 2007

J of Applied Polymer Sci

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Differential scanning calorimetry (DSC) of triple blends of high molecular weight poly(N‐vinyl pyrrolidone) (PVP) with oligomeric poly(ethylene glycol) (PEG) of molecular weight 400 g/mol and copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA) demonstrates partial miscibility of polymer components, which is due to formation of interpolymer hydrogen bonds (reversible crosslinking). Because both PVP and PMAA‐co‐EA are amorphous polymers and PEG exhibits crystalline phase, the DSC examination is informative on the phase state of PEG in the triple blends and reveals a strong competition between PEG and PMAA‐co‐EA for interaction with PVP. The hydrogen bonding in the triple PVP–PEG–PMAA‐co‐EA blends has been established with FTIR Spectroscopy. To evaluate the relative strengths of hydrogen bonded complexes in PVP–PEG–PMAA‐co‐EA blends, quantum‐chemical calculations were performed. According to this analysis, the energy of H‐bonding has been found to diminish in the order: PVP–PMAA‐co‐EA–PEG(OH) > PVP–(OH)PEG(OH)–PVP > PVP–H2O > PVP–PEG(OH) > PMAA‐co‐EA–PEG(O) > PVP–PMAA‐co‐EA > PMAA‐co‐EA–PEG(OH). Thus, most stable complexes are the triple PVP–PMAA‐co‐EA–PEG(OH) complex and the complex wherein comparatively short PEG chains form simultaneously two hydrogen bonds to PVP carbonyl groups through both terminal OH‐groups, acting as H‐bonding crosslinks between longer PVP backbones. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

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Free volume, adhesion, and viscoelastic properties of model nanostructured pressure‐sensitive adhesive based on stoichiometric complex of poly(N‐vinyl pyrrolidone) and poly(ethylene glycol) of disparate chain lengths

Feldstein

Bermesheva

Jean

et al. 2010

J of Applied Polymer Sci

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Positron annihilation lifetime spectroscopy was used to characterize the size and content of subnanoscopic free volume in a model pressure-sensitive adhesive based on a stoichiometric hydrogen-bonded network complex of poly(N-vinyl pyrrolidone) (PVP) and oligomeric poly(ethylene glycol) (PEG). Adhesive properties were examined with peel and probe tack tests, and mechanical properties were studied with tensile test. Nonequimolar stoichiometry and the structure of PVP-PEG model pressure-sensitive adhesive blends were found to be determined by the length of PEG short chains. The size and number density of free volume domains in the PVP-PEG blends were determined as functions of blend composition and relative humidity of the surrounding atmosphere, which controls the amount of absorbed water. Correlating the free volume, adhesion behaviors, and tensile properties of the blends, the range of free volume favoring pressure-sensitive adhesion in examined compositions was established.

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Molecular Dynamics in Poly(N-vinylpyrrolidone)-Poly(ethylene glycol) Blends Investigated by the Pulsed-Field Gradient NMR Method: Effects of Aging, Hydration and PEG Chain Length

Cited by 16 publications

References 7 publications

Molecular and nanoscale factors governing pressure‐sensitive adhesion strength of viscoelastic polymers

Molecular and nanoscale factors governing pressure‐sensitive adhesion strength of viscoelastic polymers

Competitive hydrogen bonding mechanisms underlying phase behavior of triple poly(N‐vinyl pyrrolidone)–poly(ethylene glycol)–poly(methacrylic acid‐co‐ethylacrylate) blends

Free volume, adhesion, and viscoelastic properties of model nanostructured pressure‐sensitive adhesive based on stoichiometric complex of poly(N‐vinyl pyrrolidone) and poly(ethylene glycol) of disparate chain lengths

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