Cooperativity Scaling and Free Volume in Plasticized Polylactide

被引：20

作者：

Araujo, Steven ^{[1
,2
]}

Delpouve, Nicolas ^{[1
]}

Domenek, Sandra ^{[3
]}

Guinault, Alain ^{[4
]}

Golovchak, Roman ^{[5
]}

Szatanik, Roman ^{[6
]}

Ingram, Adam ^{[7
]}

Fauchard, Cyrille ^{[2
]}

Delbreilh, Laurent ^{[1
]}

Dargent, Eric ^{[1
]}

机构：

[1] Normandie Univ, UNIROUEN Normandie, INSA Rouen, CNRS,Grp Phys Mat, F-76000 Rouen, France

[2] CEREMA, Direct Terr Normandie Ctr, F-76120 Grand Quevilly, France

[3] Univ Saclay, INRA, AgroParisTech, UMR Ingn Proc Aliments, 1 Ave Olympiades, F-91744 Massy, France

[4] Cnam, CNRS, Ensam, Lab PIMM, 151 Blvd Hop, F-75013 Paris, France

[5] Austin Peay State Univ, Dept Phys & Astron, Clarksville, TN 37044 USA

[6] Opole Univ, Inst Phys, PL-45052 Opole, Poland

[7] Opole Univ Technol, Fac Phys, PL-45370 Opole, Poland

来源：

MACROMOLECULES | 2019年 / 52卷 / 16期

基金：

美国国家科学基金会;

关键词：

MISCIBLE POLYMER BLENDS; GLASS-TRANSITION; DYNAMIC HETEROGENEITY; TEMPERATURE-DEPENDENCE; CONCENTRATION FLUCTUATIONS; POSITRON-ANNIHILATION; CHARACTERISTIC LENGTH; RELAXATION DYNAMICS; MOLECULAR-DYNAMICS; FRAGILITY;

D O I：

10.1021/acs.macromol.9b00464

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The experimental evidence of the increase of activation energy associated with the super Arrhenius behavior governing amorphous polylactide by free volume variations has been obtained through a combination of calorimetric, dielectric, and positron annihilation lifetime measurements. The amount of free volume in polylactide was controlled by the amount of acetyltributylcitrate plasticizer in the composition. Plasticization is shown to decrease both the fragility index and the scale of cooperative motions at the glass transition. The calculations of volume and energetic components of kinetic fragility reveal that the fragility drop is governed by the change in the size of cooperative rearranging region. As a result, direct correlation has been established between cooperativity and activation energy for the entire plasticized polylactide series. It is also shown that cooperativity variations with both temperature and plasticizer content can be simplified as a master curve with free volume.

引用

页码：6107 / 6115

页数：9

共 70 条

[31] On possible deviations of experimental PALS data from positronium pick-off model estimates [J].

Goworek, T ;

Jasinska, B ;

Wawryszczuk, J ;

Zaleski, R ;

Suzuki, T .

CHEMICAL PHYSICS, 2002, 280 (03) :295-307

[32] Nanoscale cooperativity on a series of statistical methacrylates copolymers with electron donor-acceptor pendant groups [J].

Grigoras, Cristian Vasile ;

Grigoras, Anca Giorgiana .

JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 2011, 103 (02) :661-668

[33]

HAVRILIAK S, 1966, J POLYM SCI POL SYM, P99

[34] Little evidence for dynamic divergences in ultraviscous molecular liquids [J].

Hecksher, Tina ;

Nielsen, Albena I. ;

Olsen, Niels Boye ;

Dyre, Jeppe C. .

NATURE PHYSICS, 2008, 4 (09) :737-741

[35] Is there a connection between fragility of glass forming systems and dynamic heterogeneity/cooperativity? [J].

Hong, L. ;

Novikov, V. N. ;

Sokolov, A. P. .

JOURNAL OF NON-CRYSTALLINE SOLIDS, 2011, 357 (02) :351-356

[36] Dynamic heterogeneity in miscible polymer blends with stiffness disparity: Computer simulations using the bond fluctuation model [J].

Kamath, S ;

Colby, RH ;

Kumar, SK .

MACROMOLECULES, 2003, 36 (22) :8567-8573

[37] Microcomputer program for analysis of positron annihilation lifetime spectra [J].

Kansy, J .

NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION A-ACCELERATORS SPECTROMETERS DETECTORS AND ASSOCIATED EQUIPMENT, 1996, 374 (02) :235-244

[38] STABLE AND METASTABLE STATES IN MEAN-FIELD POTTS AND STRUCTURAL GLASSES [J].

KIRKPATRICK, TR ;

WOLYNES, PG .

PHYSICAL REVIEW B, 1987, 36 (16) :8552-8564

[39] In search of a theory of supercooled liquids [J].

Kivelson, Steven A. ;

Tarjus, Gilles .

NATURE MATERIALS, 2008, 7 (11) :831-833

[40] Concentration fluctuation induced dynamic heterogeneities in polymer blends [J].

Kumar, SK ;

Colby, RH ;

Anastasiadis, SH ;

Fytas, G .

JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (09) :3777-3788

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