2022 Books

DUAL-PHASE DEPOLARIZATION ANALYSIS.

INTERACTIVE COUPLING IN THE AMORPHOUS STATE OF POLYMERS

DE GRUYTER Publisher Berlin/Boston

Part. I. 384 p. 240 Figs. 28 Tables

Part. II 305 p. 212 Figs. 19 Tables

Part I and II published in one single volume

675 References

-Describes Thermal Stimulated Depolarization techniques of polymer characterization (TSD, TWD) to decouple the relaxation modes collectively interacting (interactive coupling) to form the cohesion of the amorphous phase of amorphous and semi-crystalline polymers.

- Understands the results of depolarization in terms of the new physics of polymer interactions: the Dual-Phase model of dipoles-space charge dynamics.

- Provides practical examples of application of the TSD and TWD characterization techniques to describe coupled molecular motions in resins, medical tissues, wood, blends and block copolymers interfaces, rubbers, can coatings, internal stress in molded parts, etc.

Keywords

Polymer Characterization, Thermal Analysis, amorphous phase characterization, Thermal Stimulated Depolarization (TSD), Thermal-Windowing Deconvolution(TWD), Interactive coupling between dipoles, Dipoles interactions, Dipole polarization, Dipole depolarization, Debye relaxation, relaxation mode, Arrhenius mode of relaxation, WLF mode of relaxation, Relaxation map, Arrhenius plane, Eyring plane, DG plane, T_g transition, T_LL transition, glass transition, liquid-liquid transition, space charges, free volume, T_gr peak, compensation, compensation line, super-compensation, compensation point, enthalpy of activation, Entropy of activation, Degree of Disorder (DOD), Dual-Phase model and Cross-Dual-Phase model of Polymer Interactions, Dissipative Interactions (Temperature and Voltage Field), Interactions, Horizontal Structuring, Vertical Structuring, Dissipative Function, Open dissipative systems, Polymer Physics.

Prof. Dr. Jean Pierre IBAR

ABD-PhD MIT, PhD UPV/EHU

ENSCP Paristech

Ikerbasque Fellow

Director New School Polymer Physics

PREFACE

This book is a totally revised edition of a manual of instructions I once wrote (in 1993) which had the purpose to second the sales of the TSC/RMA Spectrometers, in the Thermal Instrumentation division of Solomat Enterprises Corp, (Stamford, CT, USA). When I left this start-up in 1994, we had sold a few dozen instruments and had approximately twice as many orders of these instruments to deliver. This showed the strong interest in this new technology. I moved on to new polymer horizons, especially in the area of the flow enhancement of melts by processing them under vibration conditions (Rheomolding and Rheo-Fluidification): this was another particular application requiring the understanding of how the interactive coupling between molecular motions controlled the properties, in particular their processing easiness.

In Ch. 6 of the 1993 manuel, I disclosed that the relaxation map of the interactive relaxation modes of the dipoles of a series of Rheomolded PS samples structured as a network of compensation lines, themselves compensating into a super-compensation macro-structure. The pattern of the macro-structure was a function of the Rheomolding thermal mechanical history. This was, and still is, an extraordinary and astonishing discovery: how could we explain such a high level of relaxation order across Tg for a pure amorphous polymer?

This discovery, that no current theory can explain, was buried in the middle of a book dedicated to the sale of a commercial instrument!

There are two reasons to resurrect the subject of thermal stimulated activation and depolarization of dipoles in polymers: one is theoretical and the other one practical. This new edition has two specific volumes: Volume I deals with the physics of interactions under a voltage field excitation; Volume II is filled with case studies teaching how to apply the characterization techniques of Thermal Stimulated Depolarization (TSD) and Thermal Windowing Deconvolution (TWD) to understand the behavior of polymers.

I am currently writing a series of books dedicated to the dissemination of a new understanding of the interactions in polymers. I have designated this research and the teaching of its principles and objectives under the name “New School Polymer Physics”. The new edition of the 1993 book fits in: not only because it is rewritten to remove all the references to the commercial aspect that were part of the 1^st publication, but also, and mainly, because the new physics of polymer interactions is the reason for the manifestation of compensations of the Arrhenius relaxation modes in a relaxation map and of the super network of compensation structures found for the Rheomolded PS samples.

Part I is dedicated to the fundamentals of this powerful sophisticated dielectric characterization technique: the origin of the dipoles formation, induced or permanent dipoles, the origin of the Wagner space charges, of the Tg,r transition, of the TLL manifestation; the origin of the Debye elementary relaxations of the relaxation map and of their compensation, the origin of their super-compensations.

Part II provides a multitude of practical examples of use of Thermal Stimulated Depolarization and Thermal Windowing Deconvolution to characterize samples that other thermal analysis techniques (DSC, DMA, DEA) have a hard time characterize to help the engineers and researchers of the industry find answers : the characterization of interfaces in blends, two phases copolymers, coated films, wood samples, paints, etc.

With the proliferation of fully automated TSD instruments in the labs of the universities and of the industry for the last 30 years, the field of thermal stimulation current depolarization has advanced a great deal, as evidenced by the large increase of the number of publications in this area of thermal analysis.

This new edition in no way represents a review of the field of thermal stimulated current depolarization; it is a reflection of my own interpretation of the interactions in polymers, what I call “interactive coupling” applied to Thermal Stimulated Depolarization (TSD) and Thermal-Windowing Deconvolution (TWD) results. These characterization methods provide the best way to study local and cooperative relaxations in the amorphous state of matter that are, in my opinion, essential to understand the glass transition, molecular motions in the rubbery and molten states and even the processes leading to crystallization. The last Chapter of Volume I and the Appendix address the fundamental nature of the local and collective aspects of the interactions, proposing an explanation of compensations and multi-compensations based on the new advances I have made on the dual-phase and cross-dual phase models. This was my main interest in completing and rewriting the work of 1993.