Glass Transition Distribution in Miscible Polymer Blends: From Calorimetry to Rheology

At their glass transition, simple liquids and polymers exhibit a broad spectrum of relaxation—with a width of more than 4 decades in time. Blends of miscible polymers exhibit an even broader relaxation spectrum. Here, we assume that a blend can be considered as an ensemble of domains of various local glass transition temperatures. Using calorimetric data, with or without aging, we probe the distribution of glass transition temperature (Tg) of miscible polymer blends of polybutadiene (PB) and styrene butadiene rubber (SBR). Using the self-consistent averaging method inspired by the Olroyd–Palierne model, we predict quantitatively, with no adjustable parameter, the viscoelastic spectrum of our blends from the Tg distribution obtained by calorimetry. This quantitative prediction confirms thus the assumption that mechanically a blend can be considered as an ensemble of domains, each of which have a different glass transition temperature.

[1]  S. Arrese-Igor,et al.  Comparison of calorimetric and dielectric single component glass transitions in PtBS−PI blends , 2010 .

[2]  Nicolas Charalambakis,et al.  Homogenization Techniques and Micromechanics. A Survey and Perspectives , 2010 .

[3]  Lian Yu,et al.  Two DSC Glass Transitions in Miscible Blends of Polyisoprene/ Poly(4-tert-butylstyrene) , 2009 .

[4]  O. Urakawa,et al.  Component dynamics in miscible polymer blends: A review of recent findings , 2009 .

[5]  G. McKenna Glass dynamics: Diverging views on glass transition , 2008 .

[6]  Wei Zheng,et al.  The glass transition in athermal poly(α‐methyl styrene)/oligomer blends , 2008 .

[7]  F. Lequeux,et al.  Revealing the respective effect of aging and cyclic deformation through the memory effect in glassy polymers , 2008 .

[8]  J. Colmenero,et al.  Segmental dynamics in miscible polymer blends: recent results and open questions. , 2007, Soft matter.

[9]  R. Colby,et al.  Dynamics of Miscible Polymer Blends: Role of Concentration Fluctuations on Characteristic Segmental Relaxation Times , 2007 .

[10]  R. Kant,et al.  Dynamics of Miscible Polymer Blends: Predicting the Dielectric Response , 2007 .

[11]  S. Havriliak,et al.  A complex plane analysis of α‐dispersions in some polymer systems , 2007 .

[12]  R. Colby,et al.  Modeling the Segmental Relaxation Time Distribution of Miscible Polymer Blends: Polyisoprene/Poly(vinylethylene) , 2005 .

[13]  R. Kant,et al.  What Length Scales Control the Dynamics of Miscible Polymer Blends , 2003 .

[14]  Á. Alegría,et al.  Segmental Dynamics in Miscible Polymer Blends: Modeling the Combined Effects of Chain Connectivity and Concentration Fluctuations , 2003 .

[15]  T. Vu-khanh,et al.  Effects of time and temperature on physical aging of polycarbonate , 2003 .

[16]  S. Ciliberto,et al.  Advanced memory effects in the aging of a polymer glass , 2002, cond-mat/0201268.

[17]  Sindee L. Simon,et al.  Volume and enthalpy recovery of polystyrene , 2001 .

[18]  A. Ajdari,et al.  Averaging rheological quantities in descriptions of soft glassy materials. , 2000, Physical review. E, Statistical, nonlinear, and soft matter physics.

[19]  T. Lodge,et al.  Self-Concentrations and Effective Glass Transition Temperatures in Polymer Blends , 2000 .

[20]  S. Ciliberto,et al.  Memory in the aging of a polymer glass , 1999, cond-mat/9906162.

[21]  G. Floudas,et al.  Segmental dynamics of miscible polymer blends: Comparison of the predictions of a concentration fluctuation model to experiment , 1999 .

[22]  R. Colby,et al.  Rheology of Miscible Blends: SAN and PMMA† , 1998 .

[23]  J. Colmenero,et al.  DYNAMICS OF GLASS-FORMING POLYMERS : HOMOGENEOUS VERSUS HETEROGENEOUS SCENARIO , 1998 .

[24]  F. Kremer,et al.  INFLUENCE OF CONCENTRATION FLUCTUATIONS ON THE DIELECTRIC ALPHA-RELAXATION IN HOMOGENEOUS POLYMER MIXTURES , 1995 .

[25]  J. Hutchinson,et al.  Physical aging of polymers , 1995 .

[26]  Á. Alegría,et al.  Observation of the component dynamics in a miscible polymer blend by dielectric and mechanical spectroscopies , 1994 .

[27]  Frick,et al.  Dynamics of the alpha relaxation of a glass-forming polymeric system: Dielectric, mechanical, nuclear-magnetic-resonance, and neutron-scattering studies. , 1991, Physical review. B, Condensed matter.

[28]  J. Palierne Linear rheology of viscoelastic emulsions with interfacial tension , 1990 .