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

[1] ON TEMPERATURE DEPENDENCE OF COOPERATIVE RELAXATION PROPERTIES IN GLASS-FORMING LIQUIDS [J].

ADAM, G ;

GIBBS, JH .

JOURNAL OF CHEMICAL PHYSICS, 1965, 43 (01) :139-&

[2] Molecular dynamics studies of heterogeneous dynamics and dynamic crossover in supercooled atomic liquids [J].

Andersen, HC .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2005, 102 (19) :6686-6691

[3] SPECTROSCOPY SIMULATION AND SCATTERING, AND THE MEDIUM RANGE ORDER PROBLEM IN GLASS [J].

ANGELL, CA .

JOURNAL OF NON-CRYSTALLINE SOLIDS, 1985, 73 (1-3) :1-17

[4] Study of the cooperativity at the glass transition temperature in PC/PMMA multilayered films: Influence of thickness reduction from macro- to nanoscale [J].

Arabeche, Khadidja ;

Delbreilh, Laurent ;

Adhikari, Rameshwar ;

Michler, Goerg H. ;

Hiltner, Anne ;

Baer, Eric ;

Saiter, Jean-Marc .

POLYMER, 2012, 53 (06) :1355-1361

[5] Reducing the Gap between the Activation Energy Measured in the Liquid and the Glassy States by Adding a Plasticizer to Polylactide [J].

Araujo, Steven ;

Delpouve, Nicolas ;

Dhotel, Alexandre ;

Domenek, Sandra ;

Guinault, Alain ;

Delbreilh, Laurent ;

Dargent, Eric .

ACS OMEGA, 2018, 3 (12) :17092-17099

[6] A structural interpretation of the two components governing the kinetic fragility from the example of interpenetrated polymer networks [J].

Araujo, Steven ;

Batteux, Florian ;

Li, Wenlong ;

Butterfield, Lena ;

Delpouve, Nicolas ;

Esposito, Antonella ;

Tan, Li ;

Saiter, Jean-Marc ;

Negahban, Mehrdad .

JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS, 2018, 56 (20) :1393-1403

[7] Thermal and mechanical properties of plasticized poly(L-lactic acid) [J].

Baiardo, M ;

Frisoni, G ;

Scandola, M ;

Rimelen, M ;

Lips, D ;

Ruffieux, K ;

Wintermantel, E .

JOURNAL OF APPLIED POLYMER SCIENCE, 2003, 90 (07) :1731-1738

[8] On the mutual relationships between spin probe mobility, free volume and relaxation dynamics in organic glass-formers: Glycerol [J].

Bartos, J. ;

Svajdlenkova, H. .

CHEMICAL PHYSICS LETTERS, 2017, 670 :58-63

[9] Positron annihilation and broadband dielectric spectroscopy: A series of propylene glycols [J].

Bartos, J. ;

Sausa, O. ;

Koehler, M. ;

Svajdlenkova, H. ;

Lunkenheimer, P. ;

Kristiak, J. ;

Loidl, A. .

JOURNAL OF NON-CRYSTALLINE SOLIDS, 2011, 357 (02) :376-384

[10] Cooperativity and the Freezing of Molecular Motion at the Glass Transition [J].

Bauer, Th. ;

Lunkenheimer, P. ;

Loidl, A. .

PHYSICAL REVIEW LETTERS, 2013, 111 (22)

← 1 2 3 4 5 6 7 →