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    Polymeric Foams Structure-Property-Performance: A Design Guide
    Polymeric Foams Structure-Property-Performance: A Design Guide
    Polymeric Foams Structure-Property-Performance: A Design Guide
    Ebook1,133 pages11 hours

    Polymeric Foams Structure-Property-Performance: A Design Guide

    By Bernard Obi

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    Polymeric Foams Structure–Property–Performance: A Design Guide is a response to the design challenges faced by engineers in a growing market with evolving standards, new regulations, and an ever-increasing variety of application types for polymeric foam. Bernard Obi, an author with wide experience in testing, characterizing, and applying polymer foams, approaches this emerging complexity with a practical design methodology that focuses on understanding the relationship between structure–properties of polymeric foams and their performance attributes. The book not only introduces the fundamentals of polymer and foam science and engineering, but also goes more in-depth, covering foam processing, properties, and uses for a variety of applications.

    By connecting the diverse technologies of polymer science to those from foam science, and by linking both micro- and macrostructure–property relationships to key performance attributes, the book gives engineers the information required to solve pressing design problems involving the use of polymeric foams and to optimize foam performance. With a focus on applications in the automotive and transportation industries, as well as uses of foams in structural composites for lightweight applications, the author provides numerous case studies and design examples of real-life industrial problems from various industries and their solutions.

    • Provides the science and engineering fundamentals relevant for solving polymer foam application problems
    • Offers an exceptionally practical methodology to tackle the increasing complexity of real-world design challenges faced by engineers working with foams
    • Discusses numerous case studies and design examples, with a focus on automotive and transportation
    • Utilizes a practical design methodology focused on understanding the relationship between structure-properties of polymeric foams and their performance attributes
    LanguageEnglish
    PublisherElsevier Science
    Release dateDec 7, 2017
    ISBN9781455777563
    Polymeric Foams Structure-Property-Performance: A Design Guide
    Author

    Bernard Obi

    Dr. Bernard E. Obi began his career in 1985 at The Dow Chemical Company and retired after 30 years of service. He worked as senior research scientist in various capacities in research and development throughout his years of service with Dow. He obtained degrees in chemistry and chemical engineering. He received his Ph.D. in chemical engineering from Michigan State University.

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      Polymeric Foams Structure-Property-Performance - Bernard Obi

      Polymeric Foams Structure–Property–Performance

      A Design Guide

      Bernard E. Obi, PhD

      Senior Research Scientist, The Dow Chemical Company, Retired July 31, 2015

      Table of Contents

      Cover image

      Title page

      Copyright

      Dedication

      About the Author

      Preface

      Acknowledgments

      Part I: Introduction

      1. Overview of Applications of Polymeric Foams

      Abstract

      1.1 Introduction

      1.2 Structure–Property–Performance Relationships in Polymeric Foams

      1.3 Applications of Polymeric Foams

      References

      Part II: Polymer Science and Engineering

      2. Polymer Chemistry and Synthesis

      Abstract

      2.1 Polymer Chemistry

      2.2 Polymer Synthesis

      References

      3. Characterization of Polymeric Solids

      Abstract

      3.1 Introduction

      References

      Further Reading

      4. Structure–Property Relationships of Polymeric Solids

      Abstract

      4.1 Overview

      4.2 Random Copolymers

      4.3 Block Copolymers

      4.4 Role of Plasticizers

      References

      Part III: Science and Engineering of Polymeric Foams

      5. Fundamentals of Polymeric Foams and Classification of Foam Types

      Abstract

      5.1 Classification of Foam Types

      5.2 Fundamentals of Foam Overview

      References

      6. Foaming Processes

      Abstract

      6.1 Introduction

      6.2 Thermosetting Polymeric Foams

      References

      7. Structure–Property Relationships of Polymeric Foams

      Abstract

      7.1 Structure–Property Relationships of Polymeric Foams

      References

      Part IV: Design and Uses of Polymeric Foams

      8. Fundamentals of Structure–Property Relationships of Polyurethane Foams

      Abstract

      8.1 Defining Applications Key Performance Attributes

      8.2 Fundamentals of Structure–Property Relationships of Polyurethane Foams

      References

      9. Structural Foams

      Abstract

      9.1 Structural Foams in a Range of Applications

      9.2 Building and Construction

      9.3 Transportation, Tanks, Pipes, and Flotation

      9.4 Furniture and Architectural Decorations

      9.5 Packaging, Food, and Drinks Containers

      References

      10. Flexible Foams

      Abstract

      10.1 Overview

      References

      11. Biomedical Applications of Polymeric Foams

      Abstract

      11.1 Bones and Cartilage

      11.2 Lightweight Cast and Orthopedic Equipment

      11.3 Tissue Engineering and Synthetic Organs

      11.4 Specialized Case Study in Use of Shape Memory Foams for Treatment of Aneurysms

      References

      12. Applications of Polymeric Foams in Automobiles and Transportation

      Abstract

      12.1 Overview of Key Applications Areas of Polymeric Foams in Automobiles and Transportation

      12.2 Design for Comfort Seating

      12.3 Design for NVH

      12.4 Structural Foam Design for Body Cavity Filling

      12.5 Design for Insulation

      12.6 Design for Interior Components in Automobiles

      References

      13. Other Specialized and Emerging Applications

      Abstract

      13.1 Space Applications

      13.2 Filtration Applications

      13.3 Carrier of Inks, Dyes, and Lubricants

      13.4 Water-Repellant Membranes

      13.5 Artificial Skin Applications

      13.6 High Coefficient of Friction—Nonslip Surface Applications

      13.7 High Damping Capacity—Sound Absorption Applications

      13.8 Electrical Properties—Dielectric Loss

      References

      14. Correlating Structure–Properties to Performance Attributes

      Abstract

      14.1 Influence of Polymer Structure–Property to Performance

      14.2 Influence of Foam Cellular Structure–Property on Performance

      References

      15. Composites and Sandwich Structures

      Abstract

      15.1 Overview of Composites and Sandwich Structures

      15.2 Optimization of Sandwich Composites

      References

      Index

      Copyright

      William Andrew is an imprint of Elsevier

      The Boulevard, Langford Lane, Kidlington, Oxford, OX5 1GB, United Kingdom

      50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

      Copyright © 2018 Elsevier Inc. All rights reserved.

      No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.

      This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

      Notices

      Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

      Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

      To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

      British Library Cataloguing-in-Publication Data

      A catalogue record for this book is available from the British Library

      Library of Congress Cataloging-in-Publication Data

      A catalog record for this book is available from the Library of Congress

      ISBN: 978-1-4557-7755-6

      For Information on all William Andrew publications visit our website at https://www.elsevier.com/books-and-journals

      Publisher: Matthew Deans

      Acquisition Editor: Edward Payne

      Editorial Project Manager: Katie Chan

      Production Project Manager: Anusha Sambamoorthy

      Cover Designer: Mark Rogers

      Typeset by MPS Limited, Chennai, India

      Dedication

      This work is dedicated to my extended family, beginning with my parents Ignatius A. and Fidelia E. Obi-ahuba. I am immensely grateful for my upbringing where education and knowledge was highly emphasized. Next to my spouse Dr. Ify E. Obi, my gratitude for agreeing to share her life with me and always supporting my endeavors. And finally to my children for my motivation to always keep learning and working hard to show them that it takes hard work and perseverance to succeed in life.

      About the Author

      Dr. Bernard E. Obi began his career in 1985 at The Dow Chemical Company and retired after 30 years of service. He worked as senior research scientist in various capacities in research and development throughout his years of service with Dow. He obtained degrees in chemistry and chemical engineering. He received his Ph.D. in chemical engineering from Michigan State University.

      He started his Dow career through a rotational program designed to introduce new researchers with the various businesses and technology areas of the company. He later joined the R&D organization of the then Saran™ and converted products business where he led significant novel research projects in the suspension polymerization processes which resulted in several patented technologies.

      Ten years later, he joined the polyurethanes business. His initial efforts focused on the optimization of the processes for producing MDI used in the development of polyurethane products. His work here was based on applying fundamental and first principles model based approaches culminating in the development of a new process for MDI production that maximized product yield and purity. That work was leveraged in his design of a more efficient new MDA production plant which he validated through Aspen simulations and pilot plant tests.

      In 2000, he shifted his focus to polyurethane foam technologies. His first area of focus was on the development of optimal polyurethane rigid foams for the appliance and construction markets. That work covered fundamental technology developments in all aspects of rigid PU foaming, including cell nucleation, growth and stabilization. The work also involved developing understanding of cell morphology control including cell size, cell shape and closed cell content optimization. This necessitated understanding of the roles of surfactants, catalysts and other foaming aids used in the control of the foam development for rigid polyurethane foams.

      This initial work on rigid polyurethane technology development was later leveraged into breakthrough development of various polyurethane flexible foams technologies; particularly in the area of memory or viscoelastic (shape contouring) foams. Here, a deep understanding of polymer physics and material science was utilized to develop significant fundamental understanding of viscoelastic properties of polymeric materials and how that influenced the final performance attributes of the various flexible foams including high resilience (HR), conventional flexible slab-stock and viscoelastic or memory foams. These various innovative technologies were useful in the development of a host of patented technologies for The Dow Chemical Company in both the rigid and flexible polyurethane foams platforms.

      In 2008 he moved to the corporate R&D organization as a senior scientist, where his expertise in engineering, polymer and material science was now significantly leveraged in both trouble shooting and technology development across Dow businesses. He led technology developments efforts in a number of areas including films technologies for both barrier and packaging applications; EPDM foams for automotive sealing, water filtration technology, thermoplastics foaming and processing; in addition to his continuing guidance of the polyurethanes technologies platforms. By way of methodology, a lot of work done by Dr. Obi over the years was accomplished by judicial application of strategic model exploration and optimization using both first principles, semiempirical and data driving modeling; leveraging his vast engineering and applied polymer physics background in identifying, defining and solving problems involving areas of reaction kinetics, interfacial science, transport phenomena, thermodynamics, and phase equilibria.

      He initiated the ongoing efforts toward the development of a foams technology expertise center within the corporate R&D organization. He worked extensively with Dow Automotive business in product development and optimization, particularly in the development of optimal foams for seating application in automotive.

      Preface

      Bernard E. Obi, PhD

      There are numerous polymeric foam products in use today fulfilling a variety of functions in diverse applications and industries. Many of these products were developed by iterative formulations work. As demands for new innovative products are dictated by regulations, customers changing habits, and evolving standards, efficiently meeting these new challenges requires problem-solving methodology involving understanding of the fundamental relationships between structure–properties of polymeric foams and their performance attributes.

      There are many excellent books on polymer science and engineering providing various degrees of fundamental theoretical and practical treatments of the subjects of polymeric materials, their design, properties, and uses. Similarly, there are equally a good number of books dealing with the fundamental science and practical aspects of foams, their processing, properties, and uses.

      While these sources provide the scientists, engineers, and polymer technicians a wealth of information to draw from their activities, significant effort has to be spent to bring all the relevant but disparate information together in order to solve real-life design problems involving polymeric foams applications.

      The main objective of this book is to attempt to bridge the relevant but diverse technologies from polymer science and engineering, to those from foam science and engineering required to solve many design problems involving the use of polymeric foams. The hope is that in a single source, researchers, engineers, polymeric foam technicians, and other practitioners will readily be able to leverage pertinent information and problem-solving methodology and expertise to enable solutions to their technical problems. This problem-solving methodology involves beginning with critical analysis to define key elements of the problem, followed by sound hypotheses development based on key facts and relevant fundamental science, and finally development of a solution space to the problem by connecting both micro- and macro-structure–property relationships to performance attributes.

      There are four main parts to the book. Part I consisting of Chapter 1, provides an overview of the applications of polymeric foams. Part II comprising Chapters 2–4 provides a review of polymer science and engineering, including polymer chemistry and synthesis, characterization of polymeric solids, and structure–property relationships of polymeric solids. Part III comprising Chapters 5–7 covers the science and engineering of polymeric foams, including classification of foam types and the fundamentals of polymeric foams, foaming processes, and structure–property relationships of polymeric foams. Finally Part IV comprising Chapters 8–15 delves into the design and use of polymeric foams; starting with review of the fundamentals of structure–property relationships of polyurethane foams, followed by discussions on structural (rigid) and flexible foams, foams in biomedical applications, use of foams in automotive and transportation and other specialized and emerging applications areas. Chapter 14 summarizes by correlating structure–property to performance attributes. Finally Chapter 15 gives a brief overview of the use of polymeric foams in composites and sandwich structures.

      May 2017

      Acknowledgments

      There are a host of individuals whom I wish to express my sincere gratitude to for my entire career spanning my education through my work at the Dow Chemical Company. I begin by thanking Professor Eric Grulke who was my PhD adviser at Michigan State University. At Dow there are a good number of excellent managers who enabled me to be the best that I could be. My most memorable managers include Gary Krook, Kerry Kelly, and Dr. Cora Leibig. Colleagues whose interactions provided the best of teaching and learning include Dr. Don Kirkpatrick, Dr. L.J. Chen, Dr. Ike Latham, Dr. Venkat Minikanti, and most importantly Dr. Anteneh Worku who provided tremendous guidance during the preparation of this book. I could not name all the incredible technical staff who provided invaluable support during my 30 years career at Dow. However, a few were most helpful and they include Roy Gamboa and Eddie Leyva. To all these individuals I say many thanks for all that we shared together teaching and learning from each other throughout my career.

      Part I

      Introduction

      Outline

      1 Overview of Applications of Polymeric Foams

      1

      Overview of Applications of Polymeric Foams

      Abstract

      It is hard to look around our modern world without encountering various types of polymeric materials, since they are used in such a wide variety of applications and functions. A closer examination reveals that many of these polymers are used as foamed articles. Their wide range of cellular morphological and functional characteristics allows them to be used in numerous applications where their lightweight and many other attributes can follow from the cellular nature of these foams. A potential classification and potential end-use applications of polymeric foams include structural foams, flexible foams, and specialty foams.

      Keywords

      Polymeric foams; blowing agents; structure–property–performance relationship; structural foams; insulation foams; flexible foams; bedding and seating foams; specialty foams; water-repellent membranes

      1.1 Introduction

      1.1.1 Background

      It is hard to look around our modern world without encountering various types of polymeric materials, since they are used in such a wide variety of applications and functions. A closer examination reveals that many of these polymers are used as foamed articles. Their wide range of cellular morphological and functional characteristics allows them to be used in numerous applications where their lightweight and many other attributes can follow from the cellular nature of these foams. A potential classification and potential end-use applications of polymeric foams include:

      1. Structural foams: appliances, building and construction, transportation, marine, tanks, pipes and floatation, furniture, packaging, food and drink containers.

      2. Flexible foams: bedding and furniture, packaging, carpet underlay, absorbents, footwear and sports applications, toys and novelties, transportation, and textiles.

      3. Specialty foams:

      a. Biomedical applications: bones and cartilage, lightweight casts, orthopedic equipment, tissue engineering, and synthetic organs.

      b. Space application: insulation, coatings, advanced sensors and actuators, structural components, space suits, and expanded structures.

      The major foamed products by polymer types used in the various applications described earlier include polyurethane (PU) foams, polyolefin (PO) foams, polystyrene (PS) foams, and polyvinyl chloride (PVC) foams. More specialty polymeric foams include phenolic foams and fluoropolymer foams.

      Polymeric foams comprise a small proportion of the total global plastic market [1]. It was estimated to be about 7% of the total polymer consumption in 2007. The foam industry is expected to witness steady growth, since cellular materials offer unique advantages over traditional materials. High-density cellular plastics are widely used in furniture, transportation, and building products, while low-density foams find use in shock absorption, insulation, and rigid packaging. The global polymeric foams market is projected to reach 30 million metric tons by 2020, at an average compounded annual growth rate (CAGR) of more than 3.5% [1]. The Asia-Pacific region is by far the largest and the fastest growing foam market which is projected to exceed 10 million tons by 2020, at a CAGR of more than 4.5% [1]. Although there has been a subdued demand in the recent past, future growth is expected due to various initiatives in polyurethane foams, as well as new and evolving applications, e.g., using foamed PVC for windows, doors, and house sidings; use of cross-linked polyolefin foams in sports and leisure goods [1,2]. It is expected that the resurgence in the polymeric foams market would be sustained from the emerging and continued demand from particularly the Asian-Pacific economies, as well as the Latin American regions [1,2]. Also the construction industry’s renewed focus on sustainable and green construction products particularly in Europe as well as in other developed geographies will continue to drive growth in polymeric foams in the future. The US foamed plastics industry is valued at US$22.5 billion, and demand was expected to reach 10.5 billion pounds in 2015 as key construction and motor vehicle markets recover [1–3]. Foamed urethane will remain the largest segment, while foamed low-density polyethylene (LDPE) will grow the fastest [1–3]. Construction will provide the best opportunities based on growth in insulation and carpet underlay applications [1–3].

      The global polymer foam industry has shown steady progress in the past few years due to innovations in technology and applications. The inherent foam characteristics include insulation, energy conservation, sound attenuation and absorption, shock absorption, and light-weighting resulting in material savings. Cellular materials can offer a wide range of properties. Foam technology covers a wide range of techniques including those useful for microcellular foaming. These techniques include injection molding and extrusion foaming, bead foaming, and cross-linked polyolefin foaming. These techniques continue to evolve as new designs of screw, mold, die, and blowing agent (BAs) continue to improve. As a result, uniform fine-celled polymeric foam products have been produced to meet demanding performance requirements. Protective packaging is a large, constantly developing market for foams. Nova Chemicals Corporation has manufactured food grade microwaveable foams from styrene maleic anhydride (SMA) copolymers [4]. Huntsman has new expanded polystyrene technology with 0.4–1.6 mm beads developed with a low rate of pentane BA inclusion (3%–7%) [5]. Molders expand the beads for applications ranging from packaging to roofing insulation. All industries are concerned with reducing environmental impact. Efforts are being made to reduce volatile organic compound (VOC) emissions in foaming. Alternatively there are environmentally friendly BAs such as those newly developed by Adeka Palmarole for food packaging, and many types of foam are now water-blown. Foams have been produced using the latest polymeric materials including nano-composites, wood composites, and biodegradable polymers such as polylactic acid (PLA).

      1.1.1.1 Polymeric Foaming Systems and Processes

      Polymeric foams represent a class of composites in which a gas phase is dispersed in a solid polymer matrix. The polymeric foam is typically achieved by processes that combine the two phases in such a way to lock in the metastable gas dispersion in a polymer liquid matrix via solidification during the foam expansion process. Solidification can be achieved in two types of foaming systems, namely (1) reactive foaming systems and (2) nonreactive foaming systems. In reactive foaming systems, solidification is predominantly achieved by a sol-gel process due to cross-linking network reactions involving multifunctional reactive low viscosity monomeric or prepolymer species. In nonreactive foaming systems, foaming involves fully polymerized species which is heated to a liquid state, and then mixed with the blowing gases prior to the expansion process. In the nonreactive foaming processes, solidification can be accomplished by either vitrification, as in glassy polymers or by crystallization as in semicrystalline polymers.

      In both foaming processes, both physical blowing agents (PBAs) and chemical blowing agents (CBAs) may be used, either individually or in combination. PBAs are typically gases or low boiling liquids that are not generated by reaction but are released either by depressurization or increasing temperatures due to active heating or exothermic heat released during the reactive foaming process. On the other hand, CBAs typically release gases via a decomposition reaction during the foaming process. The decomposition reaction is typically thermally activated by active heating or exothermic heat released during the reactive foaming process.

      In reactive foaming processes, both PBAs and CBAs may be used. However, PBAs are predominantly used in reactive foaming systems. In reactive foaming involving simultaneous polymerization and foaming processes, the polymerization of monomeric species is usually exothermic, providing a large heat release required for boiling the liquid blowing agent and expanding the gases during the blowing or foam expansion process. CBAs may be used in reactive foaming as well, in as much as the heat released during the polymerization reaction will cause the decomposition of the CBAs, releasing the gas for foam expansion.

      In nonreactive foaming processes, the predominant practice is the equilibrium saturation/dissolution of gaseous and/or liquid BAs in the polymer melt under high temperature and pressure in the processing equipment. Exiting the processing equipment is normally accompanied by large pressure drops which drive the gas expansion foaming process. The gas expansion process creates cooling effect which leads to solidification by either vitrification at temperatures below the glass transition temperature (Tg) for amorphous polymers or by crystallization below the crystallization temperatures (Tc) for semicrystalline polymers. In nonreactive foaming processes, both PBAs and CBAs are used, either individually or in combination to achieve the product design and performance objectives.

      The resulting foam has a polymer matrix with either encapsulated gas/air bubbles or air tunnels incorporated in it. When the foam is a composite of polymer matrix encapsulating gas/air bubbles, the foam is described as closed cell foam structure. On the other hand, when the foam is a composite of polymer matrix with air tunnels running through it, the foam is described as open celled foam structure. Closed cell foams are generally more rigid, while open celled foams are usually more flexible.

      Polymeric foams are produced in a number of different ways [6–13]. Examples are through slab-stock foams formed by pouring, extrusion, and different forms of molding. Polymeric foams can be divided into either thermoplastics or thermosets, which are further divided into rigid or flexible foams. Thermoplastics-based foams can usually be broken down and recycled, while thermosets-based foams are harder to recycle because they are usually highly cross-linked.

      1.2 Structure–Property–Performance Relationships in Polymeric Foams

      The thrust of this book is a guide to designing optimally performing polymeric foam articles, parts, and systems based on as thorough an understanding as possible of the relationships between the structure of the foam and its properties, as well as the relationships between the properties of the foam and the performance attributes being sought.

      Fig. 1.1 shows the various attributes of the structure–property–performance relationships found in polymeric foams that need to be understood in other to design foams and foaming systems for optimal performance.

      Figure 1.1 Overview of structure–properties–performance relationships in polymeric foams.

      The design philosophy begins with defining the performance attributes desired in the finish foamed article. The performance attributes derives from the specific applications that the foamed articles are designed for, as well as the economic considerations for the intended applications. It can be seen in Fig. 1.1 in the performance bucket that a drill-down process starts with classification of application types for flexible foams, structural foams, foams for biomedical applications, etc., followed by further classifications within the application types as in flexible foams for packaging, bedding, furniture, etc. or as in structural foams for building and construction, appliances, even packaging, etc. to name just a few.

      The next step after identification of the performance attributes is to move into the properties bucket and identify which foam properties would yield the desired performance attributes. For example, we will use a flexible foam for a bedding application to illustrate this concept. We can refine further the performance attributes for bedding application to require a soft feel with body contouring, while still providing great support and cool and comfortable feel during sleep. This set of performance attributes then drive the foam properties attributes. The desired foam properties will include: (1) High airflow for the dissipation of body heat during sleep, low modulus for soft feel, and high density for support. (2) The foam should be highly viscoelastic, which enables high damping characteristics that are necessary for body contouring. High body contouring results in uniform pressure distribution on the body. (3) Finally the foam should show very low creep to meet the long lifetime performance expectations in bedding applications.

      Following identification of the key foam properties required for the desired optimal performance for the bedding application, we can now go into the structural attributes bucket for design and process conditions necessary to meet these specifications.

      One of the most important property attributes for this application is the requirement for very low creep. The topic of creep will be discussed more fully in Part II on polymer science and engineering. For now it is enough to know that creep results in permanent dimensional changes to the formed part undergoing creep under load. Thus for the bedding mattress application, creep under load in the polymeric foam will result in permanent depression of the foam resulting in densification and hardness in the deformed section. This will cause the bed to lose its overall comfort appeal. To minimize creep in the polymeric foam for bedding applications, the polymer of choice will preferably be a thermoset with optimally designed cross-link density and minimal network imperfection. The polymer microphase morphology should be designed to minimize the interference of inclusions such as the urea hard phase for polyurethane foams, or the crystalline phase for semicrystalline polymers, with the polymer’s cross-linked rubber phase from undergoing the desired highly elastic deformations during the loading and unloading cycles encountered in use. More detailed discussions on the viscoelastic foam design for bedding applications will be offered in Part IV on the design and use of polymeric foams.

      Next it is desirable that the bed offers cool comfort during sleep by conducting body heat away from the bed. This requires the foam to have an open cell structure. The open cell structure means that the foam macro-morphology has tunnels running through the entire foam matrix all the way to the surface. Since by their nature foams are good insulators, this open cell architecture greatly enables heat dissipation by convection through these tunnels. If there is a significant amount of closed cell content, heat dissipation by conduction will be very poor on account of the insulating power of foams leading to uncomfortable hot and sweaty feeling during sleep.

      The luxurious feel of comfort in viscoelastic foam bedding comes from two properties of the foam. Relatively low modulus (softness) and high level of damping or viscoelastic property in the end-use temperature range, both lead to uniform load distribution throughout the body minimizing pressure points and resulting in the sensation of lying on a "cloud of air." Low modulus is obtained by use of highly flexible polymer backbone with very low glass transition temperature, coupled with the right level of cross-link density. Further adjustment of the modulus is obtained by reinforcement using high glass transition temperature (Tg) copolymer blocks such as urea for polyurethane systems. The level of urea and the microphase morphology in the polyurethane composite polymer determines the glass transition temperature of the resulting polymer. Design in composition and phase morphology put the glass transition temperature in the room temperature (RT) range of 10–30°C with a large loss tangent (tan δ) value which leads to high levels of damping. To avoid bottoming due to the softness of these foams, a high density is necessary to provide the support required to keep the occupant from bottoming out during sleep or rolling on to the bed.

      In this example of comfort viscoelastic foam for bedding applications, we have shown that starting with the determination of performance requirements, enable the determination of the properties requirements of the foamed product; which then drives the structural design considerations. As shown in Fig. 1.1, performance drives property which drives structure; with structure resulting in a set of properties which in turn results in the desired performance. This concept will be used throughout this book to evaluate the design of various polymeric foams for optimal performance in their various applications.

      1.3 Applications of Polymeric Foams

      As part of the overview of applications of polymeric foams, this section introduces applications of polymeric foams and highlights how performance requirements are used to design the appropriate polymer micro and macrostructures of the cellular morphology. While in this section, a general overview is offered for the various applications. Part IV will describe the design and processing of the various varieties of polymeric foams used for the various applications highlighted here in great detail. Table 1.1 lists applications and functions for numerous varieties of polymeric foams, the key markets served, attributes that drive the performance of these foams, and the polymers of choice for the various foams used for these various applications.

      Table 1.1

      Overview of Applications of Foamed Polymers [14]

      1.3.1 Structural (Rigid) Foams

      Structural foams are used in a variety of situations where they are required to provide structural support among other functions. These foams are used in appliances, building and construction, transportation, marine, tanks, pipes, and floatation, as well as furniture, packaging, food and drink containers. The main differentiating features of structural foams when compared to flexible foams are that structural foams have a higher modulus (higher stiffness or rigidity), and in many instances are designed to be close-celled foams as in the case of thermal insulation applications. We will use the application of structural foams in energy management via thermal insulation in both building and construction and appliances to illustrate the design philosophy espoused earlier.

      Polymeric foams play an indispensable role in global energy conservation and management. They are used to provide insulation against heat losses for heating applications on the one hand, or against heat gain for cooling and refrigeration applications on the other. Thermal insulation is the reduction of heat transfer between two objects in contact or within range of radiative influence of each other, when a temperature gradient exists between the two objects.

      Heat flow occurs between two objects of differing temperatures. Thermal insulation provides a region in which thermal conduction is reduced or in which thermal radiation is reflected instead of absorbed by the object at the lower temperature. The insulating capacity of a material is measured by its thermal conductivity (K-factor or lambda λ). Low thermal conductivity corresponds to high insulating capacity, also described as R-value. So for thermal insulation applications, optimal performance requires minimization of thermal conductivity (lowest K-factor) of the insulating material. The thermal conductivity, λ, of insulating foams is made up of three contributing thermal conductivities and can be described by Eq. (1.1) [15].

      (1.1)

      The thermal conductivity of the entrapped gas λgas, the thermal conductivity of the solid polymer λsolid, and the radiative conductivity λradiative due to black body radiation all make up the overall thermal conductivity λfoam of the insulating foam. Minimization of the various contributing components λi will therefore be required for optimal insulating performance of insulating foams. It follows that the insulating foam should have the following structures and properties:

      1. Closed foam structure in order to trap the low thermal conductivity gas mixtures used to produce the foam in order to minimize the gas contribution.

      2. Polymer with the lowest thermal conductivity possible to minimize solid contribution.

      3. The lowest foam density possible while maximizing the closed cell content and maintaining the smallest cell size possible in order to minimize the solid contribution.

      4. The smallest cell size possible to minimize the radiative contribution.

      In addition to minimizing the thermal conductivity of the foam, it is often required to provide structural support to the fabricated article. For example, in building and construction, it is common practice to use spray rigid polyurethane foams for roof and wall insulation in home construction. The foam provides both thermal as well as other categories of insulation; in addition to providing structural reinforcement to the building walls and roofing. Another example of the use of structural foams with thermal insulation properties is found in refrigeration. The refrigerator walls are made of thin outer metal sheets and inner plastic liners. The rigid polyurethane foam is used to provide thermal insulation and also provide overall structural support to the refrigerator via a composite property effect of a sandwich structure of metal-polymeric foam-plastic liner.

      1.3.2 Flexible Foams

      Flexible foams find application in a range of functions where they are required to provide cushioning support and comfort, energy absorption, as well as many other uses. These foams find applications in bedding, furniture, packaging, carpet underlay, absorbents, sports applications, toys and novelties, transportation, and textile. The main differentiating features of flexible foams when compared to structural foams discussed earlier are that flexible foams have a lower modulus (relatively soft), and in many instances are designed to be open-celled foams such as in bedding and furniture where cushioning is essential for comfort. The use of flexible viscoelastic foams for bedding application was discussed in Section 1.2 to illustrate the structure–property–performance relationships. It was shown in Section 1.2 that these foams are open celled and the polymer is designed to provide softness and viscoelastic behavior, necessary for cushioning and comfort.

      We will use the application of flexible foams in packaging to further illustrate the design philosophy discussed in Section 1.1. The purpose of flexible polyurethane foam in packaging is to act as a shock absorber, protecting a moving packaged object from damage as it meets resistance, slows and finally comes to rest. Whether you need to protect a moderately heavy piece of equipment or a delicate electronic component, the physical performance of polyurethane foam can be fine-tuned to meet most packaging needs. Industry sources suggest that a flexible polyurethane foam that can absorb impacts efficiently and recover its physical shape quickly, and repeatedly, is appropriate for packaging fragile items within a wide range of weights and sizes [16]. In addition, flexible foam can be cut and shaped easily for bracing, supporting, and wrapping objects.

      Two basic properties of flexible polyurethane foams namely firmness (expressed numerically as IFD) and density are key to packaging performance. IFD (indentation force deflection) is a measure of foam firmness at 25% deflection. For most packaging applications, IFD is a good indicator of the foam’s surface flexibility. High IFD values indicate a firm surface that will be less conforming to surface details. A lower IFD value, indicating foam with a more conforming facial texture, may be more appropriate for use in protecting delicate surface configurations such as found in many assembled electronic components and fragile glass and ceramic pieces. Density is the weight of a unit volume of foam and is an indication of the amount of material available to absorb energy. Density is independent of firmness. In addition to lower IFD, higher density foams will be better able to stand up to repeated impacts without its cushioning characteristics being affected. High-density foams with high energy absorption capability can be specified to have a very soft and conforming surface, or it can be produced to be very firm and not so conforming. Density adds an important aspect to foam specification. Foam thickness is not the only energy absorbing consideration. For heavier objects or with shipping conditions where great shock is anticipated, higher density and/or thicker polyurethane foam materials may be appropriate. Since higher density flexible foam absorbs energy more efficiently, there may be opportunities to optimize packaging space and reduce overall shipping size [16]. Detailed discussions and analysis will be provided in Part IV.

      1.3.3 Biomedical Application

      Many biomedical applications utilize foams with a range of macro- and micro-polymeric and cellular properties adapted to function and performance. Key areas of biomedical applications include tissue engineering, bones and cartilage, synthetic organs, lightweight casts, and orthopedic equipment.

      We will discuss these applications in more detail in subsequent sections, but as in the preceding sections of this introductory chapter, we will illustrate the case of foam design that may find use in a number of applications alluded to earlier. Viscoelastic foams, also called memory foams, can be designed for use as shape memory devices in biomedical applications. The most important controllable parameter that lends the foam its shape memory function is the design and location of the polymer’s glass transition temperature (Tg). The human body temperature is approximately 37°C or 98.6°F. Design of polymeric foams with a Tg above 37°C would mean that at temperatures below 37°C, the foam will be in the glassy state and rigid, maintaining the given shape. However, at temperatures above 37°C, the foam will be elastomeric with a high degree of flexibility.

      In a hypothetical design for biomedical application, the polymeric foam could be designed to have a Tg of 30°C. The transition should be relatively very sharp, such that the loss tangent (tan δ) at 37°C is less than 0.01, which is an indicative of high elastic properties. Detailed discussions on glass transition temperature and loss tangent will be offered in Part II, Polymer Science and Engineering, on the section on mechanical properties. With polymeric foam of this characteristic design, biomedical devices can be produced and shaped for application at ambient temperature—approximately 25°C. This might entail producing the devices in the glassy state (RT), followed by raising the temperature to above the Tg to shape the device for application. This will invariably entail miniaturization for insertion into the body for in vivo applications. Following miniaturization and shaping above Tg, the device is cooled below its Tg to RT to maintain the predeployment configuration in the rigid state. When the device is deployed in vivo or even if the device is used in vitro, as it warms up to the body temperature, it undergoes the transformation from rigid to highly flexible elastomeric materials recovering their original shape and dimensions.

      The other major considerations in the design of these types of foams for biomedical applications include the cellular structure encompassing the open cell content, porosity, cell size, and cell size distribution. Additionally and most importantly, the polymeric material must show excellent biocompatibility.

      Current areas of application cited in the literature include wound care, restraining bleeding, for closing a wound, preventing tissue adhesion, and/or for supporting tissue regeneration, in the form of a plug or a tampon. Other application areas include use as porous absorbent material suitable for packing an antrum or other cavity of a human or animal body. Potential vascular uses include removal of blood clot (thrombus) from arterial network [17–20].

      1.3.4 Space Application

      By virtue of their lightweight, polymeric foams provide opportunities for space applications where weight reduction is a premium. Polymeric foams could be used for structural components, space suits, expandable structures, advanced sensors and actuators, coatings and insulation in space applications.

      An example of a foam suitable for space applications is a polyimide-based foam. Evonik Industries produces polyimide foams, named SOLIMIDE, which find uses in various space applications. These polyimide SOLIMIDE aircraft foam products are the ideal insulation to meet the stringent requirements of the aircraft/aerospace industries. They provide excellent acoustic and thermal insulation at extremely low weight. Their superior fire resistance meets FAR25.856(a) Radiant Panel Flame Propagation Rule; toxic gas, smoke generation, and off-gassing are virtually nonexistent. SOLIMIDE foams can be found in Airbus, Boeing, Canadair, Embraer, business jets, military aircraft, and helicopters, as well as in demanding aerospace applications, including the International Space Station, Mars rover, solar shields, and cryogenic fuel tanks [21].

      The properties that make these polyimide foams ideal for aerospace applications include lightweight, superior fire resistance, virtually no smoke or toxic gas production, outstanding thermal and acoustic insulation, environmentally friendly, proven durability, ease of installation, and wide operating temperature range. These foams remain flexible over a very wide temperature range from cryogenic conditions at −196°C to oven temperatures as hot as 300°C [21]. These set of properties constitute critical to quality (CTQ) for a highly safety conscious aerospace application space.

      1.3.5 Other Applications of Polymeric Foams

      1.3.5.1 Filters

      Polymeric foams can be used in various filtration operations by virtue of its cellular nature. Foams that are used in filtration applications will have very high open cell content. In addition, such foams will be designed with predetermined cell sizes to target filtrates rejection effectiveness. The foams will also be designed to meet a targeted stiffness (modulus) to effectively provide structural integrity in the required applications depending on the flow through induced stress requirements. Thus, cell size, cell size distribution (normally narrow for these applications), high open cell content, and targeted modulus are CTQs for polymeric foams that are used in filtration applications. The production of such foams will be discussed in Parts III and IV of this book.

      A polymeric foam in a filtration application is produced by ATI Industries. This company produces washable reusable foam filters for Heating, ventilation, and air-conditioning (HVAC) applications including room air conditioners, fan coil units, unit ventilators, built-up filter banks, and air handling units [22]. The polymeric foam filter media can be cleaned for reuse by vacuuming, flushing, washing in warm water with detergents, and even steaming. The resulting foam filters can be designed for applications across a wide range of temperature, i.e., from −50°F to 200°F.

      Reticulated polyurethane foams find applications in various filtration applications. The reticulation process assures the most open cell content. These foams have large amounts of surface area for beneficial biological capacity.

      1.3.5.2 Carriers of Inks, Dyes, and Lubricants

      The text on cellular solids by Gibson and Ashby [23] discusses the potential uses of foam sheets as carriers for inks, dyes, and lubricants, as well as for enzymes in chemical processing. The cells are saturated with the given fluid, which can be either leached out in a controlled release or expelled when the sheet is squeezed.

      The design of the polymeric foams must take into account the desired performance. For these types of applications, the foams must be open celled to facilitate uptake and release of the fluids. It could be imagined that for those applications requiring slow release, the cellular structure may likely constitute relatively small cells. Small cells are those that fall into the fine-celled (~10⁹ cell density) and microcellular (~10¹² cell density) foams categories. The classifications of cellular foams in terms of size will be fully discussed in Part III. In addition to being small-celled, the foams for slow release by leaching may also be designed to be relatively rigid (high modulus). Such a design would prevent stress induced mass discharge of the fluids during foam handling.

      On the other hand, for applications where the fluids are desired to be readily discharged by squeezing stresses, the foams may have slightly larger cell size structure that may be in the conventional foam cell size domain (~10³–10⁶ cell density). The selection of cell size design will be as a function of discharge rates desired and the rheological properties of the fluid. High viscosity fluids may require larger cells while low viscosity fluids may require smaller cells. The foams must be designed by flexible (low modulus) and highly elastomeric to perform the function of uptake and release.

      1.3.5.3 Water-Repellent Membranes

      Foams made from highly hydrophobic polymers like polytetrafluoroethylene (PTFE) have special advantages as water-repellant membranes while allowing free passage of air. PTFE open-celled microporous foams are used as hydrophobic barrier in high-quality sporting and leisure wear, providing a fabric which breathes, yet excludes water [24]. A more cost-effective alternative to PTFE foams maybe foams made from general-purpose polymers that are later functionalized with penetrating water-repellent chemicals like reactive silanes and siloxane resins with cross-linkable side chains [25]. These materials have smaller molecular structures, which enable them to penetrate deeply into the substrate, where they chemically bond with it. Such functionalized polymeric foamed materials would equally provide water-repellant properties.

      Dow Corning provided a descriptive mechanism for the water-repellant properties of its silicone-based chemistry for hydrophobicity as shown in Fig. 1.2 [25].

      Figure 1.2 The mechanics of waterproofing [25].

      Silicones have low surface tension, which enables them to spread and soak easily into a substrate’s pores. Their highly flexible and mobile siloxane backbone enables the water-repelling methyl groups to orient themselves toward the surface, creating a waterproof umbrella. What makes this umbrella unique is its ability to breathe. Because silicones have a very open molecular structure, water vapor trapped in the substrate can easily slip through. Water molecules, however, are too large to enter [25].

      More recently, researchers have developed extreme water-repellent graphene foams. Researchers have shown that it is possible to use graphene sheets to create a super-hydrophobic coating material that shows stable super-hydrophobicity under both static and dynamic (droplet impact) conditions. They demonstrated a novel macroscopic graphene structure composed of an integrated foam-like network of graphene sheets with well-controlled microscale porosity and roughness. The novel idea here was to grow graphene over a sacrificial nickel foam template and then leech away the nickel, leaving behind a graphene foam with few-layered graphene sheets that comprise the walls of the foam. The foam is then coated with a 200-nm layer of Teflon [26]. If this graphene technology could be applied to polymeric foams, e.g., in PTFE foams, then the water-repellant properties of such polymeric foam material can go from hydrophobic to super-hydrophobic performance.

      1.3.5.4 Artificial Skin

      The same material properties which provide water-repellant and breathability behaviors in polymeric foam membranes used for water-repellant applications can be employed for developing artificial skin technology. The artificial skin would provide protection to burn victims, while still allowing for free access to air due to its breathability.

      Recently, 3M developed a foam dressing that was redesigned to allow it to be more responsive to the degree of moisture present in the wound. The new dressing (Tegaderm) differs from its predecessor and other marketed foam dressings in that it incorporates a new moisture control layer that modulates moisture vapor permeability through the backing under varying wound conditions [27].

      1.3.5.5 Nonslip Surface Applications

      Open-celled foams have a relatively rough surface compared to the base polymeric solid from which they are produced. This roughness gives foams a high coefficient of friction. The high coefficient of friction enables foams to be used for nonslip applications, such as surfaces of trays, tables, floors, and even cloth hangers. They are designed for use with hangers as self-adhesive foams strips on a roll with readily peeled off backing for affixing to the hanger. They can be added to any existing hanger [28].

      Nonslips are designed for use with garments that are prone to slippage on a traditional hanger without them, like knitwear and lingerie. A foam strip with self-adhesive backing is applied to each end of the dress hanger arm.

      1.3.5.6 High Damping Capacity—Sound Absorption

      Sound waves are reflected by hard smooth surfaces. One method of attenuating sound wave is by absorption. Polymeric cellular foams are porous materials which act as sound absorbing sponge by converting the sound energy into heat within the material. To be effective, these foams must have open cell architecture. The mechanism of sound absorption by showing the attenuation of sound waves from a noise source as it travels through the semi-open cell acoustic foam is explained in [29]. In this particular design further noise reduction is achieved by coupling the open cell foam with a very high-density acoustic barrier mass [29].

      A more detailed treatment of the application of polymeric foams in sound absorption will be offered in Parts IV and V detailing important design considerations and the structure–property implications of the design of these foams for the sound management systems.

      1.3.5.7 Electrical Properties—Dielectric Loss

      The absorption of electrical energy by a dielectric material that is subjected to an alternating electric field is termed dielectric loss. The dielectric must be a good electric insulator so as to minimize any DC current leakage through a capacitor. The presence of the dielectric decreases the electric field produced by a given charge density. Fig. 1.3 shows the influence of the dielectric in reducing the electric field for a given charge per unit area [30]. The factor k by which the effective field is decreased by the polarization of the dielectric is called the dielectric constant of the material. Eq. (1.2) relates the effective electric field relative to the hypothetical field in free space.

      (1.2)

      where the terms E, Eeffective, Epolarization, σ, ε0 are defined in Fig. 1.3.

      Figure 1.3 Schematic showing electric field reduction in a dielectric medium [30].

      The dielectric constant of free space (vacuum) is set to 1.0, that of air at STP is approximately 1.0006 (practically taken as 1.0), that of fluoropolymers are typically 2.1, for polyolefin’s and for most nonpolar polymers, k is in the range of 2.2–2.8. For polar polymers, k is greater than 3 and for water at STP k is 80. It follows from Eq. (1.2) that the higher the dielectric constant the lower the effective electric field, the higher the absorption of electric energy and consequently the higher the dielectric loss resulting into heating for a given charge density.

      Water will therefore result in the highest dielectric loss for the example materials listed earlier, while air would result in the lowest dielectric loss. It follows then that voids containing air can have a dielectric constant of nearly 1, thus the dielectric constant of the porous material may be reduced by increasing the porosity of the material. Converting a polymeric solid with low dielectric constant to a cellular material presents a way of further reducing the dielectric constant of the final polymeric article via a gas–solid composite behavior.

      1.3.5.8 Structure and Properties of Solid Food Foams

      Many foods are produced as foams. Their cellular structures are often deliberately designed to impart many desirable attributes from esthetics to feel during consumption. The cellular structure of many solid foods generally makes it easier to bite, chew, and digest. Fig. 1.4 shows the cellular nature of bread as a foamed structure [31].

      Figure 1.4 Image of sliced bread showing the cellular nature of some solid foods [31].

      References

      1. Smartech Global Solutions Ltd. <www.plastemart.com>, 2003 (accessed 03.02.17).

      2. Global Polymeric Foams Market, Global Industry Analysts, Inc., <http://www.strategyr.com/MarketResearch/Polymeric_Foams_Market_Trends.asp>, 2016.

      3. PlasticsEurope, Association of Plastics Manufacturers. <www.plasticseurope.org>, 2015.

      4. Robert DR, Kwok JC. Styrene–maleic anhydride copolymer foam for heat resistant packaging. J Cell Plast. 2007;43:135–143 (accessed 03.02.17).

      5. Huntsman International LLC., News Source: Chemical Online, June 12, 2006. <https://www.chemicalonline.com/doc/chemicals-manufacturer-huntsman-new-expandabl-0001>.

      6. Herrington R, Hock K. Flexible Polyurethane Foams Midland, MI: The Dow Chemical Company; 1997.

      7. Ashida K. Polyurethane and Related Foams United Kingdom: Taylor and Francis; 2007.

      8. Klempner D, Sendijarevic V. Polymeric Foams and Foam Technology 2nd.ed. Cincinnati, OH: Hanser Gardner Publications, Inc. 2004.

      9. Lee S-T, Park CB, Ramesh NS. Polymer Foams Boca Raton, FL: Taylor and Francis; 2007.

      10. Khemani KC. Polymeric Foams Orlando, FL: American Chemical Society; 1996.

      11. Throne J. Thermoplastic Foam Extrusion Washington, DC: Hanser Gardner Publications, Inc. 2004.

      12. Gendron R. Thermoplastic Foam Processing Boca Raton, FL: CRC Press; 2005.

      13. Uhlig K. Discovering Polyurethanes Hanser Gardner Publications, Inc. 1999.

      14. Foams Tutorial 2008, Thermoplastic Materials & Foams Division and Carolinas Section, SPE, September 8–9, 2008.

      15. Jarfelt U, Ramnäs O. Thermal conductivity of polyurethane foam best performance—10th International Symposium on District Heating and Cooling Göteborg/Sweden: Chalmers University of Technology; 2006.

      16. In Touch™, Flexible Polyurethane Foams, Publication of Polyurethane Foam Association (PFA), vol. 5, No. 2, 1996.

      17. Stasis foam for battlefield wounds shows promise—Stripes. <https://www.stripes.com/stasis-foam-for-battlefield-wounds-shows-promise-1.216687> April 21, 2013.

      18. M. Dowling, I. MacIntire, J.White, M. Narayan, M. Duggan, D. King, ACDS Biomaterials Science & Engineering, Sprayable Foams Based on an Amphiphilic Biopolymer for Control of Hemorrhage Without Compression, 2015.

      19. Treating Brain Aneurysms With Polymer Foam. <www.medicaldesignbriefs.com/component/content/article/mdb/tech-briefs/21830>, 2015.

      20. Texas A&M-led Research Aimed at Treating Brain Aneurysms Receives $2.5 Million NIH Grant. <https://today.tamu.edu/.../texas-am-led-research-aimed-at-treating-brain-aneurysms>, 2015.

      21. Evonik Industries. <www.evonikfoams.com> (accessed 03.02.17).

      22. ATI Airguard Foam Filter Media, Total Filtration Services, Inc. A CLARCOR Company <http://catalog.tfsi1.com/AdvancedWebPage.aspx>.

      23. Gibson LJ, Ashby MF. Cellular Solids Structure & Properties Pergamon Press 1988.

      24. Types of waterproof-breathable membranes. <http://www.nemoequipment.com/pdfs/classroom/wbtechnologies_6-12-12.pdf>.

      25. The mechanics of waterproofing, Dow Corning Literature, ©2000–2013 Dow Corning Corporation.

      26. http://www.nanowerk.com/index.php (accessed February 2017).

      27. 3M™ Tegaderm™ High Performance Foam Dressing, In Vitro and Health Human Studies, 3M Skin & Wound Care, 2011.

      28. Foam hanger strips. <www.saddlebackdisplay.com> (accessed March 3017).

      29. Acoustic Composite Sound Absorption Properties, <www.acoustiproducts.com> (accessed March 2017).

      30. Parallel Plate with Dielectric. <hyperphysics.phy-astr.gsu.edu> (accessed March 2017).

      31. Donna Currie, Ask the Food Lab: On Hot Chocolate and Whole Wheat|Serious Eats <www.seriouseats.com> (accessed March 2017).

      Part II

      Polymer Science and Engineering

      Outline

      2 Polymer Chemistry and Synthesis

      3 Characterization of Polymeric Solids

      4 Structure–Property Relationships of Polymeric Solids

      2

      Polymer Chemistry and Synthesis

      Abstract

      Polymer or macromolecular chemistry is a multidisciplinary science that deals with the chemical synthesis and chemical properties of polymers or macromolecules. IUPAC defines macromolecules as individual molecular chains and this is the domain of chemistry. The bulk properties of polymeric materials belong to the field of polymer physics which is a subfield of physics.

      Keywords

      Polymer chemistry; types of polymers; urethane chemistry; polymer synthesis; step growth polymerization; copolymer

      2.1 Polymer Chemistry

      Polymer or macromolecular chemistry is a multidisciplinary science that deals with the chemical synthesis and chemical properties of polymers or macromolecules [1]. IUPAC defines macromolecules as individual molecular chains and this is the domain of chemistry [2,3]. The bulk properties of polymeric materials belong to the field of polymer physics which is a subfield of physics.

      Polymer chemistry is that branch of chemistry which deals with the study of the synthesis and properties of macromolecules. Polymers are formed by the polymerization of monomers. A polymer is chemically described by its degree of polymerization, molar mass distribution, tacticity, copolymer distribution, the degree of branching, by its end groups, cross-links, crystallinity, and thermal properties such as its glass transition temperature and melting temperature. Polymers in solution have special characteristics with respect to solubility, viscosity, and gelation. There are extensive open literatures on polymer chemistry [4–7].

      2.1.1 Classification and Types of Polymers

      Because of the diversity of function and structure found in the field of macromolecules, it is advantageous to construct some scheme which groups these materials under convenient headings. Fig. 2.1 is one such way of classifying polymers.

      Figure 2.1 Classification of polymers.

      Naturally occurring polymers usually have more complex structures than their synthetic counterparts. Elastomers or rubbers can be either natural or synthetic (man-made). While all polymeric materials, both natural and synthetic, can be produced in a cellular form, the majority of polymeric foam products are derived from synthetic polymers and elastomers. The structure–property–performance relationships will be addressed for all classes of polymeric materials required for specific applications depending on the application and class of polymeric material utilized. However, the emphasis of this book will be on polymeric foams produced from synthetic elastomers, thermoplastic, and thermosetting polymers, by virtue of their overwhelmingly high volume compared to natural polymers.

      A polymer is a large molecule produced from many smaller units called monomers. The monomers are usually covalently bonded to each other in many conceivable patterns. In some polymerization processes, atoms are eliminated from the monomeric unit. In such instances the macromolecule is said to be made up of monomeric residues. The essential requirement for a small molecule to qualify as a monomer is the possession of two or more bonding sites, through which each can be linked to other monomers to form the polymer chain. The number of bonding sites is referred to as the functionality, f, of the monomer.

      Examples of monomeric species and their reaction can be shown by considering monomers such as a hydroxyacid (HO–R–COOH) or vinyl chloride (CH2=CHCl), which are both bifunctional monomers. The hydroxyacid will undergo condensation reaction with other hydroxyacid molecules through the –OH and –COOH groups to form a linear polymer. The polymerization reaction in this case consists of a series of simple condensation–elimination reactions in which water is eliminated as a by-product of the polymerization. The condensation polymerization is a reversible reaction and is shown in the following scheme:

      In the case of vinyl chloride, the double bond is also bifunctional. It is typically activated by a free radical or an ion to form polymer by addition reaction without the elimination of any part of the monomer as in the case of condensation polymerization. The vinyl polymerization is also known as addition polymerization. Addition polymerization is not a reversible reaction and is shown in the following scheme.

      Bifunctional monomers form linear macromolecules. However, if the monomers have more than two functional groups, they are known as polyfunctional monomers. An example of a polyfunctional monomer is glycerol (CH2OH–CHOH–CH2OH) which is trifunctional and has three reactive OH groups. When polyfunctional monomers are polymerized, branched macromolecules can be produced. In many cases polyfunctional monomers are used to produce large three-dimensional networks containing both branches and cross-links.

      When only one species of monomer is used to produce a macromolecule, the product is called a homopolymer, and normally referred to as a polymer. However, when two types of monomer species are used to produce the macromolecule, the material is referred to as a copolymer. When three different monomers are incorporated in one macromolecule, the resulting material is referred to as a terpolymer.

      Further classifications involving copolymers produced from bifunctional monomers result in four main categories [1]:

      1. Statistical copolymers are those where the distribution of the two monomers in the copolymer backbone is essentially random, dictated by the reactivities of the individual monomers. Example of an A–B random copolymer:

      2. Alternating copolymers are those where there is a regular placement of the two different monomers along the copolymer backbone. Example of an A–B alternating copolymer:

      3. Block copolymers are those where there are substantial sequences or blocks of each monomer in the copolymer backbone. Example of an A–B block copolymer:

      4. Graft copolymers are those where the blocks of one monomer are grafted on to the backbone of the other monomer as branches. Example of an A–B graft copolymer:

      2.1.2 Polymers Used Extensively in Foams

      As was mentioned in the preceding section, synthetic (man-made) polymers are predominantly used to produce foamed products. While almost all synthetic polymers could be transformed into cellular materials, there are a handful of polymers that find widespread applications in various foamed products. These polymers in order of their global volumetric consumption into foamed products are polyurethanes (PU), polystyrene (PS), polyolefin (PO), and polyvinyl chloride (PVC). These polymers are mostly transformed into foamed materials for major applications, in the order of usage volumes: cushioning, insulation, packaging, others, and structural and décor.

      Figs. 2.2 and 2.3 illustrate the types of polymers used extensively in foamed materials and major application areas of the foamed products from various sources [8–10]. By far the polymer used most abundantly in foaming applications is polyurethane, followed by polystyrene at a distant second. Polyolefin, polyvinyl chloride, and a variety of other polymers all together constitute only about 20% of the foamed polymeric materials.

      Figure 2.2 Relative demands for the major foamed polymers [8–10].

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