Dynamic relaxation characteristics of crosslinked poly(ethylene oxide) copolymer networks: Influence of short chain pendant groups

Borns, Matthew A.; Kalakkunnath, Sumod; Kalika, Douglass S.; Kusuma, Victor A.; Freeman, Benny D.

doi:10.1016/j.polymer.2007.10.020

Cited by 16 publications

(14 citation statements)

References 41 publications

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“…6, and demonstrate the influence of increasing co-monomer content on the glass-rubber relaxation. Similar data for the PEGDA/DEGEEA series were presented earlier [32]. With increasing PEGPEA comonomer, the glass transition temperature shifts to higher values consistent with the calorimetric results; the associated peak temperatures (T˛, based on peak in tan ı at 1 Hz) are reported in Table 3.…”

Section: Fractional Free Volume and Chain Mobilitysupporting

confidence: 85%

“…Dielectric studies on crystalline PEO and the XLPEGDA homopolymer indicate two local sub-glass relaxations (ˇ1 andˇ2), as well as the glass-rubber relaxation (˛) with increasing temperature [34]; the influence of co-monomer content on the dielectric dispersion characteristics of various PEGDA copolymers has been reported in detail [32,35]. An Arrhenius plot (f MAX vs. 1000/T) for the PEGDA/PEGPEA copolymers studied here is shown in Fig.…”

Section: Fractional Free Volume and Chain Mobilitymentioning

confidence: 64%

“…(7)), such correlations are not necessarily universal across various copolymer series. Both the length of the co-monomer side chains and the nature of the side chain terminal groups can significantly affect the glass transition temperature and free volume characteristics of the resulting networks [8,9,16,32]. FFV-T g correlations for the copolymers considered in this study are shown in Fig.…”

Section: Fractional Free Volume and Chain Mobilitymentioning

confidence: 99%

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Influence of phenoxy-terminated short-chain pendant groups on gas transport properties of cross-linked poly(ethylene oxide) copolymers

Kusuma

Matteucci

Freeman

et al. 2009

Journal of Membrane Science

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Section: Fractional Free Volume and Chain Mobilitysupporting

confidence: 85%

Section: Fractional Free Volume and Chain Mobilitymentioning

confidence: 64%

Section: Fractional Free Volume and Chain Mobilitymentioning

confidence: 99%

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Influence of phenoxy-terminated short-chain pendant groups on gas transport properties of cross-linked poly(ethylene oxide) copolymers

Kusuma

Matteucci

Freeman

et al. 2009

Journal of Membrane Science

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“…As a result, the relationship between network structure, chain dynamics and bulk properties of cross-linked polymers has been widely studied in the literature using different techniques for a wide range of material systems. [8][9][10][11][12][13] In particular, the dielectric relaxation spectroscopy (DRS) is where  * is the  relaxation time, i.e.  *   and KWW parameter is the stretch exponent that lies in the range 0-1 and quantifies the extent of deviation from pure exponentially, i.e.…”

Section: Effect Of Cross-linking On the Molecular Dynamics Of The Segmentioning

confidence: 99%

The effect of cross-linking on the molecular dynamics of the segmental and β Johari–Goldstein processes in polyvinylpyrrolidone-based copolymers

et al. 2015

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Royal Society of ChemistryRedondo Foj, MB.; Sanchis Sánchez, MJ.; Ortiz Serna, MP.; Carsí Rosique, M.; García, JM.; García, FC. (2015). The effect of cross-linking on the molecular dynamics of the segmental and Johari-Goldstein processes in polyvinylpyrrolidone-based copolymers. Soft Matter. 11:7171-7180. doi:10.1039/c5sm00714c. The effect of the cross-link density on the molecular dynamics of copolymers composed of vinylpyrrolidone (VP) and butyl acrylate (BA) was studied using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). A single glass transition was detected by DSC measurements, showing good copolymer miscibility. The dielectric spectra exhibit conductive processes and three dipolar relaxations labeled as ,  and  in decreasing order of decreasing temperatures. The cross-linker content affects both  and  processes, but the fastest  process is relatively unaffected. An increase of the cross-linking produces a typical effect on the  process dynamics: (i) the glass transition temperature is increased, (ii) the dispersion is broadened (iii) its strength is decreased and (iv) the relaxation times are increased. However, the  process, which is a Johari-Goldstein relaxation possesses typical features of pure Johari-Goldstein relaxation, unexpectedly loses the intermolecular character for the highest cross-linker content. . The basis of the CM is the existence of a temperature-insensitive crossover time, tc, which is about 2 ps for small molecules and polymeric glass formers 32,33 . At times shorter than t , there are basic molecular units that relax independently of each other, whose relaxation function can be described by a simple exponential decay: Effect of cross-linking on the molecular dynamics of the segmental and  Johari-Goldstein processes in Polyvinylpyrrolidone-based copolymersBelénBA (PBA) is hydrophobic and has a glass transition of 219K, while the PVP is an extremely hydrophilic polymer(uncross-linked PVP is water soluble), with glass transition of 448 K. Thus, copolymers comprised of VP and BA can be presented as tractable materials with moderate hydrophilicity and good mechanical and thermal properties. In addition to the copolymers, it is also highly interesting the study of cross-linked polymer networks. The dynamics of cross-linked polymers is influenced by the network composition and the polymer chain architecture. As it is well-known, both the glass-rubber and the subHowever, at times longer than tc, the intermolecular interactions (i.e. cooperativity 34 , which is associated with the dynamic heterogeneity) slow the relaxation. Thus, there is a coupling between the motions of the different basic molecular units. Therefore, the relaxation function assumes the Kohlrausch-Williams-Watts (KWW) equationglass transitions are highly sensitive to changes in the backbone structure, the cross-link density, and the introduction of pendant groups or branches. As a result, the relationship between network structure, chain dynamics and bulk properties of cross-l...

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“…As it is well-known, both the glass-rubber and the sub-glass transitions are highly sensitive to changes in the backbone structure, the cross-link density, and the introduction of pendant groups or branches. As a result, the relationship between network structure, chain dynamics and bulk properties of cross-linked polymers has been widely studied in the literature using different techniques for a wide range of material systems (Borns, et al, 2007;Qazvini, et al, 2005;Cook, et al, 2004;Viciosa, et al, 2007;Jobish, et al, 2012;Bekin, et al, 2014). In particular, the dielectric relaxation spectroscopy (DRS) is presented as one of the most powerful techniques to study the chain dynamics of solid polymers with temperature and frequency.…”

Section: Introductionmentioning

confidence: 99%

A contribution to the study of the molecular mobility in polymeric materials by Thermal and Dielectric Analysis

Foj¹,

Belén²

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T h e s i s S u p e r v i s o r : P R O F . D r . M a r í a J e s ú s S a n c h i s S á n c h e z t o o b t a i n t h e d e g r e e o f D o c t o r o f P h i l o s o p h y a t t h e U n i v e r s i t a t P o l i t è c n i c a d e V a l è n c i a Prof. Dr. María Jesús Sanchis SánchezThe work presented in this thesis was carried out at the Universitat Politècnica de València and was financially supported by the Spanish Ministry of Economy and Competitiveness (Projects Nos. MAT2008-06725-C03-03 and MAT2012-33483)."Cuando quieres algo, todo el Universo conspira para que ACKNOWLEDGEMENTSTras estos años de trabajo, llega el momento de mostrar mi agradecimiento a todas las personas que me han acompañado y apoyado durante el desarrollo de mi tesis doctoral.En primer lugar, me gustaría expresar mi gratitud a mi directora de tesis María J.Sanchis por su inestimable ayuda durante todos estos años. Muchas gracias por confiar en mí, por darme esta oportunidad y por las incalculables horas invertidas tanto para el desarrollo de esta tesis como al mío propio.También me gustaría agradecer a mis estimadas compañeras Marta Carsí y Pilar Ortiz su ayuda y amistad en este largo recorrido que suponer realizar una tesis doctoral. He aprendido mucho de vosotras tanto científica como personalmente. En este punto, no puedo olvidarme de mi querida Aurora Alonso, que pese a no formar parte de nuestro grupo de investigación, me ha apoyado, aconsejado y dado su amistad durante todos estos años.Quiero mostrar mi agradecimiento a los profesores José M. García y Félix C. García ABSTRACTThe development of new and more complex polymeric materials involves challenging problems to basic sciences. The relationship between structure and molecular dynamics assumes great importance for the future development of novel technologies based on such polymers. Thus, the understanding of how small changes in the chemical structure affect the properties of the material is essential to progress in the technological and scientific area. An in-depth analysis of the molecular mobility leads to establish the structure-properties relationships. On this basis, the main aim of the present work is to study the molecular mobility of two different families of polymeric materials. For this purpose, the experimental techniques mainly used were Differential Scanning Calorimetry (DSC) and Dielectric Relaxation Spectroscopy (DRS) (Chapter 3).The first family of polymers characterized was a series of chemically cross-linked copolymers composed by Vinylpyrrolidone (VP) and Butyl Acrylate (BA) monomers. The study was divided in two parts, which are collected in Chapter 4 and 5.In the first place, Chapter 4 contains the influence of the monomer molar ratio (XVP/YBA) on the copolymer properties. Thus, a Fourier Transform Infrared Spectroscopy (FTIR) analysis verified dipole-dipole interactions between amide groups. The influence of these interactions on several parameters related to the molecular mobility was evidenced by the DSC, DRS and Dynamic Mechanical Analysis (DMA) techni...

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Dynamic relaxation characteristics of crosslinked poly(ethylene oxide) copolymer networks: Influence of short chain pendant groups

Cited by 16 publications

References 41 publications

Influence of phenoxy-terminated short-chain pendant groups on gas transport properties of cross-linked poly(ethylene oxide) copolymers

Influence of phenoxy-terminated short-chain pendant groups on gas transport properties of cross-linked poly(ethylene oxide) copolymers

The effect of cross-linking on the molecular dynamics of the segmental and β Johari–Goldstein processes in polyvinylpyrrolidone-based copolymers

A contribution to the study of the molecular mobility in polymeric materials by Thermal and Dielectric Analysis

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