139 Advances in Polymer Science

E d i t o r i a l Boa rd :

A. A b e - A.-C. A l b e r t s s o n • H.-]. C a n t o w • K. D u ~ e k S. E d w a r d s . H. H 6 c k e r • ]. E ] o a n n y • H. -H. K a u s c h T. K o b a y a s h i • K.-S. L e e . ]. E. M c G r a t h L. M o n n e r i e - S. I. S t u p p • U. W. Su te r E. L. T h o m a s . G. W e g n e r • R. ]. Young

Springer Berlin Heidelberg New York Barcelona Hong Kong London Milan Paris Singapore Tokyo

Mineral Fillers in Thermoplastics I Raw Materials and Processing

Volume Editor: J. Jancar

With contributions by E. Fekete, P.R. Hornsby, J. Jancar, B. Puk~inszky, R.N. Rothon

~,~~ Springer

This series presents critical reviews of the present and future trends in polymer and biopolymer science including chemistry, physical chemistry, physics and materials science. It is addressed to all scientists at universities and in industry who wish to keep abreast of advances in the topics covered.

As a rule, contributions are specially commissioned. The editors and publish- ers will, however, always be pleased to receive suggestions and supplementary information. Papers are accepted for ,,Advances in Polymer Science" in English.

In references Advances in Polymer Science is abbreviated Adv. Polym. Sci. and is cited as a journal.

Springer WWW home page: http://www.springer.de

ISSN OO65-3195 ISBN 3-540-64621-3 Springer-Verlag Berlin Heidelberg New York

Library of Congress Catalog Card Number 61642

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Volume Editor

Prof. losef Jancar School of Chemistry Technical University Brno Purkynova 118 61200 Brno Czech Republic E-maih jancar@fch, vutbr.cz

Editorial Board

Prof. Akihiro Abe Department of Industrial Chemistry Tokyo Institute of Polytechnics 1583 liyama, Atsugi-shi 243-02, Japan E-mail'. aabe@chem.t-kougei.ac.jp

Prof. Ann-Christine Albertson Department of Polymer Technology The Royal Institute of Technolgy S-10044 Stockholm, Sweden E-maih aila@polymer.kth.se

Prof. Hans-Joachim Cantow Freiburger Materialforschungszent rum Stefan Meier-Str. 21 D-79104 Freiburg i. Br., FRG E-maih cantow@fmf uni-freiburg.de

Profi Karel Du~ek Institute of Macromolecular Chemistry, Czech Academy of Sciences of the Czech Republic Heyrovsk~ Sq. 2 16206 Prague 6, Czech Republic E-maih office@imc.cas.cz

Prof. Sam Edwards Department of Physics Cavendish Laboratory University of Cambridge Madingley Road Cambridge CB30HE, UK E-maih sfel 1 @phy.cam.ac. uk

Prof. Hartwig HiScker Lehrstuhl ffir Textilchemie und Makromolekulare Chemie RWTH Aachen Veltmanplatz 8 D-52062 Aachen, FRG E-maih lO0732.1557@compuserve.com

Prof. Jean-Francois Joanny Institute Charles Sadron 6, rue Boussingault F-67083 Strasbourg Cedex, France E-maih joanny@europe, u-strasbg.fr

Prof. Hans-Henning Kausch Laboratoire de Polym6res I~cole Polytechnique F~d~rale de Lausanne, MX-C Ecublens CH- 1015 Lausanne, Switzerland E-maih hans-henning.kausch@lp.dmx.epfl.ch

Prof. Takashi Kobayashi Institute for Chemical Research Kyoto University Uji, Kyoto 611, Japan E-maih kobayash@eels.kuicr.kyoto-u.ac.jp

Prof. Kwang-Sup Lee Department of Macromolecular Science Hannam University Teajon 300-791, Korea E-mail kslee@eve.hannam.ac.kr

VI Editorial Board

Prof. ]ames E. McGrath Polymer Materials and Interfaces Laboratories Virginia Polytechnic and State University 2111 Hahn Hall Blacksbourg Virginia 24061-0344, USA E-mail: jmcgrath@chemserver.chem.vt.edu

Prof. Lucien Monnerie t~cole Sup4rieure de Physique et de Chimie Industrielles Laboratoire de Physico-Chimie Structurale et Macromol4culaire 10, rue Vauquelin 75231 Paris Cedex 05, France E-maih lucien.monnerie@espci.fr

Prof. Samuel I. Stupp Department of Materials Science and Engineering University of Illinois at Urbana-Champaign 1304 West Green Street Urbana, IL 61801, USA E-mail: s-stupp@uiuc.edu

Prof. Ulrich W. Suter Department of Materials Institute of Polymers ETZ,CNB E92 CH-8092 Ziirich, Switzerland E-maih suter@ifp.mat.ethz.ch

Prof. Edwin L. Thomas Room 13-5094 Materials Science and Enginering Massachusetts Institute of Technology Cambridge, MA 02139, USA E-mail. thomas@uzi.mit.edu

Prof. Gerhard Wegner Max-Planck-Institut fiir Polymerforschung Ackermannweg 10 Postfach 3148 D-55128 Mainz, FRG E-mail'. wegner@mpip-mainz, mpg.de

Prof. Robert J. Young Manchester Materials Science Centre University of Manchester and UMIST Grosvenor Street Manchester M1 7HS, UK E-mail: robert.young@umist.ac, uk

Preface

In recent years, a growing number of engineering applications of light-weight and energy efficient plastics can be found in high-quality parts vital to the func- tioning of entire equipments and structures. Improved mechanical properties, especially balance of stiffness and toughness, are among the most frequently desired features of the new materials. In addition, reduced flammability is con- sidered the single most important requirement for further expansion of plastics into large volume and demanding markets such as construction and mass trans- port. Production of power cables also requires flame retardant cable jacketing plastics to replace or at least to reduce consumption of environmentally unsound PVC.

The two principal ways to achieve the goals mentioned above include the development of completely new thermoplastic polymers and various modifica- tions of the existing ones. Development and commercialization of a new ther- moplastic require mobilization of large human and financial resources, the lat- ter being within the range from $100 million to $10 billion, in comparison to $100 thousand to $10 million needed to develop and commercialize polymeric mate- rial with prescribed end-use properties using physical or chemical modification of an existing plastic. In addition, the various markets utilizing thermoplastics demand large flexibility in material properties with only moderate volumes, at the best. Hence, while the majority of both commodity and engineering ther- moplastics were introduced during the 18 years between 1954 and 1972, only PEEK and liquid crystalline polymers have reached the market in the last 20 years (Table 1). On the other hand, more than 4000 blends and compounds entered the marketplace between 1980 and 1997, while only very few in the years before [1].

From the arguments put forward above, one can draw the conclusion that the physical modification of the existing polymers, i.e. their compounding with sol- id fillers or blending with other polymers, has been the primary approach used in the development of polymeric materials ,,tailored" for the majority of new engineering applications. Development and production of completely new ther- moplastics with desired properties appear to be a long term, very expensive and risky alternative to the engineering of thermoplastic materials using com- pounding with fillers, elastomers and blending with other thermoplastics.

In addition to purely consumption related reasons, the trend towards exten- sion of the product range by physical modifications of existing plastics is sup-

VIII Preface

Table 1. Commercialization dates for selected thermoplastics used as matrices in com- pounding [ 11 Year Polymer Producer Abbreviation 1927 polyvinylchloride B.E Goodrich PVC 1936 polyamide 6,6 DuPont PA6,6 1938 polystyrene Dow PS 1939 low density polyethylene ICI LDPE 1954 polyurethanes Bayer/DuPont PUR 1954 high density polyethylene Hoechst HDPE 1954 polyethyleneterephthalate ICI PET 1956 polyamide 6 Allied PA6 1957 polypropylene Phillips Petroleum PP 1958 polycarbonate GEC/Bayer PC 1959 linear low density polyethylene DuPont LLDPE 1965 polysulfone Union Carbide/3M PSO 1969 polybutyleneterephthalate Celanese PBT 1972 polyphenylene sulfide Philips Petroleum PPS

ported by the effort of the plastics industry to reduce the variety of produced thermoplastics and to supply the various markets with polymeric materials based on, in an ideal case, one polymer. In addition, this ,,unification" also appears reasonable for greatly improving ease of recycling, as it would lead to a reduction in the need for sorting of various plastics especially in recycling of cars and durable goods (refrigerators, computer cases, batteries, etc). Due to the large variety of plastics and rubbers used in current consumer and durable goods, recy- cling into reusable materials has been expensive with very little commercial suc- cess. Since the advent of metallocene catalyst technology, capable of producing polyolefins with properties ranging from elastomers to hard polymers in a sin- gle process, polypropylene has been among the most frequently cited candidates to fulfil this role.

Commodity thermoplastics (polypropylene, polyethylene, polyvinylchloride, etc.) and some engineering thermoplastics (nylons, PBT, etc.) have become attractive candidates for many engineering applications replacing traditional materials and substituting for more expensive resins [2]. Relatively low price, excellent chemical resistance, good processability, potential for part consolida- tion and assembly simplification due to part consolidation and the possibility of modifying mechanical properties in a wide range by adding fillers and elas- tomers has contributed to the growing application range of filled polyolefins, especially polypropylene (PP) and polyethylene (PE). This has been made pos- sible by creating a solid database of experimental, theoretical and empirical knowledge gathered by researchers and compounders over the last 20 years. Part of the knowledge has been published, part remains with the companies as a por- tion of their ,,know-how".

This book aims to assemble this somewhat fragmented information, which is dispersed in a large body of literature, in a unified, coherent manner emphasiz- ing both quantitative and qualitative relationships between structural variables

Preface IX

and mechanical properties. The book is divided into two volumes, the first of which deals with raw materials and compounding technology. The second vol- ume focuses on the relationships between structural variables and mechanical and physicochemical properties of p articulate-filled thermoplastics. This volume deals with the current state-of-the-art in thermoplastic matrices, particulate fillers, surface modifications of fillers and with compounding and processing technologies. Despite the fact that this volume has been edited from contri- butions by scientists from three countries, effort has been devoted to orchestrate the individual contributions in a manner equal to monographs written by a single author.

Brno, July 1998 Josef Jancar

References

1. Gruenwald G (1992) Plastics, how structure determines properties. Hanser, Munich 2. Rubin II (ed) (1990) Handbook of plastic materials and technology. J Wiley Interscience,

New York

Contents

Structure-Property Relationships in Thermoplas t ic Matrices ]. ]ancar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Mineral Fillers in Thermoplast ics : Filler Manufacture and Character isat ion R.N. Rothon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

Adhesion and Surface Modif icat ion B. Puk~inszky, E. Fekete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

Rheology, Compound ing and Processing of Filled Thermoplas t ics P.R. Hornsby . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155

Author Index Volumes 101 - 139 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229