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Modification of Polymer Properties
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Commencer à lireLongueur: 655 pages10 heures
- Éditeur:
- Elsevier Science
- Sortie:
- Sep 14, 2016
- ISBN:
- 9780323443982
- Format:
- Livre
Description
Modification of Polymer Properties provides, for the first time, in one title, the latest information on gradient IPNs and gradient copolymers. The book covers the broad range of polymer modification routes in a fresh, current view representing a timely addition to the technical literature of this important area. Historically, blends, copolymers, or filled polymers have been developed to meet specific properties, or to optimize the cost/properties relationship.
Using the gradient structure approach with conventional radical polymerization, it has been shown that it is possible to optimize properties if appropriate gradients in the composition of copolymer chains are obtained. An overview of the gradient structure approach for designing polymers has not appeared in the recent literature and this title covers the different methods used to modify properties, offering the whole range of ways to modify polymers in just one volume and making this an attractive option for a wide audience of practitioners.
The approach for each chapter is to explain the fundamental principles of preparation, cover properties modification, describe future research and applications as examples of materials that may be prepared for specific applications, or that are already in use, in present day applications. The book is for readers that have a basic background in polymer science, as well as those interested in the different ways to combine or modify polymer properties.
Provides an integrated view on how to modify polymer properties Presents the entire panorama of polymer properties modification in one reference, covering the essential information in each topic Includes the optimization of properties using gradients in polymers composition or structureInformations sur le livre
Modification of Polymer Properties
Longueur: 655 pages10 heures
Description
Modification of Polymer Properties provides, for the first time, in one title, the latest information on gradient IPNs and gradient copolymers. The book covers the broad range of polymer modification routes in a fresh, current view representing a timely addition to the technical literature of this important area. Historically, blends, copolymers, or filled polymers have been developed to meet specific properties, or to optimize the cost/properties relationship.
Using the gradient structure approach with conventional radical polymerization, it has been shown that it is possible to optimize properties if appropriate gradients in the composition of copolymer chains are obtained. An overview of the gradient structure approach for designing polymers has not appeared in the recent literature and this title covers the different methods used to modify properties, offering the whole range of ways to modify polymers in just one volume and making this an attractive option for a wide audience of practitioners.
The approach for each chapter is to explain the fundamental principles of preparation, cover properties modification, describe future research and applications as examples of materials that may be prepared for specific applications, or that are already in use, in present day applications. The book is for readers that have a basic background in polymer science, as well as those interested in the different ways to combine or modify polymer properties.
Provides an integrated view on how to modify polymer properties Presents the entire panorama of polymer properties modification in one reference, covering the essential information in each topic Includes the optimization of properties using gradients in polymers composition or structure- Éditeur:
- Elsevier Science
- Sortie:
- Sep 14, 2016
- ISBN:
- 9780323443982
- Format:
- Livre
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Aperçu du livre
Modification of Polymer Properties
(Argentina).
Preface
Historically, polymer composites, blends, and copolymers have been developed to combine component properties, or to optimize the cost/properties relationship. Nowadays, the specific needs for polymeric materials are constantly changing and their applications keep growing and growing. Under such circumstances it is important to gather in one book the different methods that can be used to modify polymer properties and accomplish the application requirements, which are necessary to design polymers with tailormade properties.
The approach for each topic included in this book is to explain the fundamental principles of preparation, to cover properties’ modification, and to describe applications as examples of materials that may be prepared or are already in use for specific applications. The book is for readers that have a basic background in polymer science, and are interested in the different ways to combine or modify polymer properties.
For those reasons, in the introduction chapter of this book, among other topics, the parameters of polymer size and structure, production processes, and different types of classifications are presented; the book continues with the preparation of polymer composites (see chapter: Filled Polymer Composites) and nanocomposites (see chapter: Nanofillers in Polymers), which are treated in a separate chapter due to their increasing importance and different ways of preparation. For additives (see chapter: Additives in Polymers), the content is focused on those that are used to modify bulk properties, while in Chapter 5, Surface Modification of Polymers: Chemical, Physical, and Biological Routes, the techniques and reactions that are used to modify surface polymer properties are included. Smart polymers that change in behavior when they receive a stimulus are reported in Chapter 6, Smart Polymers, and the principles and phase behavior of blends and alloys are shown in Chapter 7, Blends and Alloys. To complete the panorama on the modification of polymer properties, the book closes with Chapter 8, Gradients in Homopolymers, Blends, and Copolymers, reporting the methods to form gradients in structures that may be used to design the properties of composites, blends, or copolymers. This comprehensive coverage on gradient polymeric materials is a novelty for a book.
The relevance of this work for the reader relies on the visualization that can be attained of the panorama on how to modify polymer properties in just one book. This in turn may facilitate the conception to expand polymer applications, or the preparation of new products.
The book content may be useful for people studying or working on polymers and engineering research in areas such as plastics, rubbers, paints and coats, or adhesives.
The editors are grateful to Elsevier for the invitation to work on a book related to tailormade polymers.
1
Introduction
Modifiable Characteristics and Applications
C.F. Jasso-Gastinel, J.F.A. Soltero-Martínez and E. Mendizábal, University of Guadalajara, Guadalajara, Jalisco, México
Abstract
For the introductory chapter, an overview of the science and technology panorama of polymers is presented, focusing on the elements that have an influence on their properties. In that way, it starts by highlighting the importance of primary and secondary bonds on the structure and properties of polymers, and continues with some classifications of polymers that allow the understanding of the parameters that are related to their properties, including type and number of components, chemical and spatial structure, as well as polymer response to temperature after a polymer is formed; the different types of applications are also included before polymer morphology is explained and the relevance of polymer molecular weight is examined. Polymer recyclability and degradability are also discussed along with the relationship between chemical structure and properties, as well as the theoretical estimation of polymer properties with respect to structure, and finally the factors to be considered for polymer selection are presented.
Keywords
Bonds; classifications; molecular weight; structure-properties; morphology; properties estimation; polymer selection
1.1 Development of Polymers
The development of humankind since the first half of the 20th century has been closely related to the application of polymers from natural or synthetic origin. The studies to understand the relationship between structure and properties of those polymers have contributed significantly to the advancement in the field. From there, considerable research has also been done to expand the available properties by the combination or modification of polymers to make products.
The word polymer
(from Greek roots) stands for a molecule that contains many (poly) parts (mers); i.e., it has a high number of equal parts or units (e.g., 1000–5000 for hydrocarbons), and with that size it acquires properties that are useful for different applications in solution, dispersion, or as a solid material. If the number of units is small (around 12–20), the molecule is known as an oligomer (a few units); those molecules find their use in the oil field (Wu, 1989), in electronics (Murphy and Fréchet, 2007), etc., while smaller molecules like telomers (2–5 units) have no practical use as materials. The reactant to make a polymer consists of a single molecule (monomer) that can react and rapidly grow unit by unit as a chain; alternatively, two molecules containing different functional groups may react (comers) to form polymer chains by means of stepwise reactions (Odian, 2004a).
Monomers and comers are commonly simple small (gaseous or liquid) molecules. For small molecules, chemical structure, molecular weight (MW), and isomerism play an essential role in their behavior at environmental conditions. For instance, in Table 1.1, it can be observed that sulfhydric acid is a gas, while water is a liquid at room temperature, even though the former has higher MW than the latter. In that case, the main difference between them relies on their chemical structure, because of the high forces of attraction that occur between water molecules. In the same table, it can be seen that hydrocarbons like methane or butene are gases at room temperature, while decane is a liquid, and as the MW of hydrocarbons increases, they convert into brittle or hard solids at room temperature. It is clear that in this case, the main difference between those molecules is the MW rather than the chemical structure. Additionally, in Table 1.1, pentane isomers show different boiling points due to their different spatial configuration. The parameters that affect small molecules also affect the behavior of big molecules, including natural macromolecules like proteins and cellulose or synthetic polymers.
Table 1.1
Properties of Some Common Substances
In addition to the above-mentioned parameters that affect polymer behavior, the technological potential of polymeric materials broadens because they can be synthesized with more than one monomer in a reactor, be mixed with additives and/or blended with other polymers, and even be modified after they are formed (Carraher and Moore, 1983; Swift et al., 1997). Moreover, since the properties of a polymer article also depend on the processing method and the article geometry, plenty of methods to prepare polymers and processes to make products have been developed and applied with success since decades ago (Cheremisinoff, 1998; Lenz and Ciardelli, 1979; Matyjaszewski and Davis, 2002), and processing equipment is also in constant development.
To visualize the advances and potential of the polymer field, some classifications and schemes are presented in Section 1.3. Detailed nomenclature and basic definitions can be seen in the compendium prepared by the IUPAC (Jones et al., 2008).
1.2 Bonding in Polymers
The electrostatic forces that hold together or attract atoms and molecules apply also to polymers. Depending on the force magnitude, they have been classified as primary and secondary bonds. Primary bonds (ionic, covalent, coordinated covalent, and metallic) vary approximately from 35 kcal/mol to 213 kcal/mol depending on the electronegativity of the atoms involved. The force of primary bonds is big enough to hold together the atoms to form a molecule (e.g., O2, H2O, C2H4, polyethylene, etc.). The most common bond of this type in polymer structure is the covalent bond, while the coordinated covalent appears seldom. Ionic bonds are present in polymer with ionic charge, and the metallic bond became of interest in this field with the appearance of conductive polymers (Wudl et al., 1980).
The dissociation of primary bonds can only happen by chemical reaction. That is, the spatial configuration formed with such bonds during a synthesis reaction is fixed, giving the capability to obtain stable isomers (e.g., cis, trans, or isotactic polymers). As a consequence, primary bonds are responsible for the thermal and photochemical stability of polymers. Secondary bonds (dispersion, polar, induced polar, and hydrogen bond) that stand for forces of attraction between molecules are much weaker than primary bonds, normally ranging from 3 kcal/mol to 7 kcal/mol, and can be dissociated by the application of energy that promotes physical changes with no modification in chemical structure. That is, they are related to physical properties like fusion, evaporation, dissolution, flow, elastic deformation, etc. The dispersion forces which are present in all compounds are the weakest forces of attraction between molecules; the presence of polarity in molecules causes an increase in molecular cohesion, promoting an increase in their mechanical and thermal resistance. A stronger force of attraction appears if a bridge or link between a hydrogen atom and one of oxygen, nitrogen, or fluorine is formed (hydrogen bond); that kind of attraction may occur inter- or intramolecularly contributing to cohesion and chain alignment, magnifying mechanical and solvent resistance in polymers. The importance of hydrogen bonding is so great that water is a liquid at ambient conditions due to the bridges generated between the oxygen and hydrogen of different molecules. In polymeric materials it is of great importance for processing conditions and the final properties of polymers like polyamides, polyesters, polyurethanes, polyureas, etc.
The alignment of individual polymer molecules leads to ordered regions in the polymer bulk; such regions allow the formation of geometric arrangements known as crystals (see Section 1.4) that contribute to the final physical properties of the polymer product.
Secondary forces of attraction have to take place in polymer blends to reach miscibility; in Table 1.2, some of the different possibilities of interactions are shown with examples of polymer blends that show a certain type of interaction (Coleman et al., 1991).
Table 1.2
Interactions Involved in Some Polymer Blends
Adapted with permission from Coleman M.M., Graf J.F., Painter P.C., 1991. Specific Interactions and the Miscibility of Polymer Blends. Technomic Publishing Company, Inc., Lancaster, PA, pp. 59–156.
1.3 Classifications of Polymers With Respect to Origin, Structure, and Applications
1.3.1 Source of Origin
Polymers can be of natural, modified natural, or synthetic origin. Cotton and wool to make clothes represent ancestral applications of natural macromolecules, while regenerated cellulose or rayon are examples of macromolecules’ modification which led to the expansion of textiles, as well as to the industrialization of rubber by the vulcanization reaction of natural rubber with sulfur, or allowed the start of film making with nitrocellulose at the end of the 19th century. The synthetic polymer industry developed after the preparation of the phenol-formaldehyde resin (bakelite), at the start of the 20th century. A chronology of polymer science and technology development can be seen elsewhere (Rodríguez et al., 2015).
1.3.2 Chemical Elements or Groups in Polymers
Polymers can be of organic or inorganic character; the chemical structure of most commercial polymers is carbon based (organic type), and a few elements are commonly used to vary properties considerably. In addition to carbon and hydrogen as the main elements, oxygen, nitrogen, and halogens (mainly chlorine and fluorine) allow the formation of a vast number of polymers, and as in low MW molecules, chemical groups or types of compounds that give name to particular families are also used in high MW molecules, following the prefix poly
to describe different types of polymers (e.g., polyacids, polyamides, polyesters, polyurethanes, polyolefins, etc.). The characteristic group essentially determines the specific chemical properties of a polymer. Inorganic polymers, which were basically silicon based for many years, are able to form very flexible chains with –Si–O– linkages (Manners, 1996), which require less energy than the –C–C– linkages for rotation in space.
1.3.3 Number of Monomers in Polymers
Polymers can be made with one (homopolymer), two (copolymer), three (terpolymer), or more monomers. The production of copolymers or terpolymers is pursued when the combination of properties of specific elements or groups is desired within the polymer molecules. Different ways have been used to make useful copolymers and terpolymers; however, if two monomers are charged in a batch reactor, to predetermine the expected composition within the chains in that copolymer, the relative affinities of the reacting monomers (relative reactivities, Odian, 2004b) have to have been previously determined. Alternatively, to avoid the relative reactivities problem, different types of reactions and processes have been developed to try to control the composition of multicomponent polymer chains (Jasso-Gastinel et al., 2006; Matyjaszewski and Davis, 2002).
In the copolymers of Fig. 1.1, for equivalent A/B global compositions, the expected properties of a material will vary depending on the number of A and B units in sequence within the molecules; the bulk of alternate or statistical copolymer chains (Fig. 1.1A and B respectively) will usually present one phase, and the expected performance will approximate the average properties of the respective global composition, provided that the relative reactivities are not too different in the statistical copolymers (i.e., do not have the tendency to form blocks). Block and graft copolymers (Fig. 1.1C and D respectively) will commonly show two phases with domains of each component (see Section 1.4), and the material will show the tendency to combine the properties of each component as homopolymer (if the blocks or grafts are big enough, as it will be explained in Section 1.5), depending on the domains interaction (e.g., three block chains offer better component interaction than two block chains). For the block copolymers case, the blocks may be readily formed in the polymer bulk by alternating the monomer to feed, while graft copolymers are usually made by grafting units of monomer B
into polymer A.
In this case, if grafting of B is done at the surface of A, polymer properties at the surface are modified for specific applications (see chapter: Surface Modification of Polymers: Chemical, Physical, and Biological Routes). Gradient copolymers (Fig. 1.1E) will present one or more phases depending on the sequence size of A and/or B units, hypothetically falling between statistical and block copolymer performance depending on the size sequence of the components within the chains, although they offer better component interaction than block copolymers (see chapter: Gradients in Homopolymers, Blends, and Copolymers).
Figure 1.1 Types of copolymers. (A) Alternate. (B) Statistical. (C) Block. (D) Graft. (E) Gradient.
A third component in a reaction system may be considered if it is able to contribute with an additional property to a two component system. In the most commercial terpolymer, acrylonitrile (A) imparts chemical resistance, butadiene (B) contributes to impact resistance, and styrene (S) provides rigidity. Such a terpolymer (ABS) has been widely used for decades in automotive parts, electronic products, etc.
1.3.4 Number of Space Dimensions in Polymers
Depending on the monomer or comer functionality, polymer chains can be linear, branched, or cross-linked (one, two, and three dimensions respectively). In Fig. 1.2, it can be seen that in linear (Fig. 1.2A) and branched polymers (Fig. 1.2B), the molecules are separated and can usually be dissolved with appropriate solvents, or can be melted under the application of heat. Branching arrangements have given rise to configurations such as comb, ladder, star, dendritic, etc. (Fréchet and Tomalia, 2001). A covalent link between atoms of different polymer molecules will provide a cross-link to form a third dimension. If a polymer is properly cross-linked, the polymer bulk is essentially one molecule with loose ends; for that reason, cross-linked polymers (Fig. 1.2C and D) cannot be dissolved nor able to flow, unless covalent links break under the application of shear at high temperature (e.g., sulfur cross-links in rubber products; Banyopadhyay et al., 2008; Sayer, 2014). Lightly cross-linked polymers (Fig. 1.2C) can swell with an appropriate solvent, while in tightly cross-linked polymers (Fig. 1.2D), solvent molecules are not able to swell the polymer bulk, and such a type of molecule would suffer combustion under heating before covalent bonds could break.
Figure 1.2 Polymer arrangements in space. (A) Linear. (B) Branched. (C) Lightly cross-linked. (D) Tightly cross-linked.
1.3.5 Type of Components in Polymers
To combine properties, two component polymers can be prepared as copolymers (see Section 1.3.3), or polymer blends. Furthermore, reinforcement of homopolymers or two component polymers can be used to prepare polymer composites. Each one of these types of polymeric materials is of great technological importance; they were expanded upon in the second half of the 20th century, and they are in constant development. See Chapters 2, Filled Polymer Composites, 3, Nanofillers in Polymers, 7, Blends and Alloys, and 8, Gradients in Homopolymers, Blends, and Copolymers, where composites, nanocomposites, blends, and gradients in polymers are respectively presented.
1.3.6 Reaction of Polymers to Temperature
After the polymers are formed and processed to make articles, if the polymer chains are linear or branched, in most cases they can be melted and flow again under the application of temperature and pressure; i.e., they are thermoplastic polymers that may be used to make new articles. On the contrary, since cross-linked polymer chains cannot be dissolved or melted, the cross-linking reaction to prepare thermoset polymers has to be performed in the final article production stage (i.e., during article fabrication). In Fig. 1.3 diagrams showing the parameters which affect the properties of a polymer article are presented for thermoplastic (Fig. 1.3A) and thermoset (Fig. 1.3B) polymer products. As it can be seen in Fig. 1.3, the final properties of a polymer article will be a combination of the properties of the material itself depending on the type of synthesis (intrinsic), the additives used, and type of processing and conditions used, as well as the design and geometry of the product.
Figure 1.3 Parameters that influence the final properties of thermoplastic (A) and thermoset (B) products.
1.3.7 Applications of Polymers
In order of industrial importance, polymers are essentially applied in five areas: plastics, rubbers, fibers, paints and coatings, and adhesives. The final structure and article geometry determine the area of application of a polymeric material, although some polymers can be applied in more than one area (e.g., some polyamides, polyesters, and polyolefins may be formulated for plastic or fiber products), mainly by changing the method of processing. Chemically pure polymers may be used for some applications, but in most cases, additives are included in commercial production for ease of processing, to lower costs, to look for special properties, etc. (see chapter: Additives in Polymers). Due to the diversity of properties that the polymers may offer, plastics are commonly used to replace materials like glass, wood, metal, or paper. Synthetic rubbers not only complement or replace natural rubber due to availability or cost; they can also offer a better option in cases where extremely low temperature or chemical resistance is important (e.g., nitrile rubber is used for special industrial hoses, gaskets, etc.; Hayashi, 2001). Besides the importance of additives in rubbers, the possible variation in cross-linking (e.g., structure in Fig. 1.2C varying slightly the weight percent of cross-linker in the formulation) allows for a variation in elasticity, diversifying rubber applications (e.g., rubber bands, tires for different road types, etc.). If cross-linking is high (Fig. 1.2D), the polymer behavior changes from elastic to semirigid or rigid plastic depending on the number of atoms between cross-links.
The use of synthetic fibers, which started to grow on the 1940s, has surpassed the use of natural fibers since the 1970s; for different applications, fibers can be textured, crimped, or may be treated to avoid static electricity or staining. To obtain high resistance in one axis, prior to fiber formation, polymer filaments obtained in continuous form are drawn at specific conditions to increase packing order of molecules in that axis. Paints and coatings are used to decorate, protect, or even add a certain property to a surface. Polymer film formation can be accomplished by several methods; in Table 1.3, it can be noticed that polymer molecules can be dispersed in solution, suspension, or emulsion to be applied as paints over a surface. For the thin film formation process, polymer molecules are gathered together by solvent or water evaporation, or oil drying, repeating the operation to obtain thick films. In the same table, it can be seen that coats may be formed with plasticized polymers, as well as by electrodeposition of polymers containing a functional group (e.g., a carboxylic or amino group, or polymerizing an oligomer in situ over a surface). Variations on each type of paint or coat have widened the list of products and the ways of application.
Table 1.3
Typical Paints and Coatings
Natural adhesives like starch, casein from milk, or collagen-based have been used since ancestral times. For adhesion, the electric nature of the adherend and the adhesive interact by primary covalent and/or secondary bonding, and even by mechanical interlocking. For adherence to surfaces that are difficult to bond (e.g., polyethylene, polytetrafluoroethylene, etc.), polar sites have to be formed there by chemical treatment. The inner strength of the polymer structure leads to high shear strength or heat resistant bonding, provided that full intimate contact is reached between the adherend surface and the flowing adhesive before it solidifies. In Table 1.4, different ways to obtain solid adhered films with synthetic polymers are presented. Linear or branched adhesives are sensitive to their solvents or temperature, while cross-linked adhesives cannot be dissolved and are heat resistant. Commonly, additives are essential to plasticize, increase wetting, tack, adhesion, or cross-link (see chapter: Additives in Polymers).
Table 1.4
Adhesives Classification
1.4 Morphology
1.4.1 Polymer Morphology
The physical and thermal properties of polymer materials are a result of the shape and the way in which molecules are organized in the solid state: their morphology. The morphology is a consequence of the molecular interactions which control the self-assembling of the molecules to form a solid phase. The molecular structure, conformation, and orientation of polymers are important for the parameters which produce major effects on the macroscopic properties of the material. Polymer researchers have, for many years, sought to establish structure–property relationships that predict various physical properties from the information about the chemical structure of the polymer, i.e., tacticity, ramification, cross-links, etc. The general concept of self-assembly enters into the organization of molecules on the micro- and macroscopic scale when polymers aggregate to form more ordered structures. The physical properties of a material are caused by its ability to self-assemble in order to form crystalline phases. It is necessary to distinguish between crystalline and amorphous phases in polymeric materials and then to show how these phases can coexist in polymeric materials. Regarding the comparison between glass that is an amorphous material and sodium chloride that is a crystalline material, regardless of their common appearance as hard and clear materials and capable of being melted, a difference is revealed when they are observed between crossed polarizers. The highly ordered crystalline structure of sodium chloride changes the properties of the polarized light, and the sodium chloride appears bright, but glass, lacking that highly ordered structure, appears dark. The amorphous morphology of glass leads to very different properties when compared with those of crystalline solids. This can be illustrated by the heating process where the application of heat to glass turns it gradually from a hard and fragile solid-like material at ambient temperature to a viscous liquid, whose viscosity decreases with temperature. In contrast, the application of heat to sodium chloride turns it from solid to liquid at a single melting point. Crystalline melting produces changes in optical properties during the melting process. Both glass and sodium chloride appear dark when they are observed between crossed polarizers while melting. The reasons for the different behaviors are due mainly to the solids’ structures. In crystalline materials their molecules are arranged in repeating patterns. Table salt has one of the simplest atomic structures with its component atoms (Na+ and Cl−) arranged in alternating rows and the spatial structure is formed as a small cube. Many common materials like salt, sugar, ice, quartz, and metals are crystalline materials. As such, they all tend to have highly ordered and regular structures.
Polymeric materials, in contrast, show random molecular arrangements and their long chains are twisted and curved around one another, making large regions of highly disordered structure. The morphology of most polymers is semicrystalline. That is, they are mixtures of small crystals and amorphous material and crystals or the bulk melt over a range of temperature rather than at a single melting point. The crystalline part shows a high degree of order formed by folding and stacking of the polymer chains. The amorphous or glass-like structure shows no long-range order, and the chains are entangled, as illustrated in Fig. 1.4.
Figure 1.4 Scheme of the polymer chain orientation in a lamellar crystalline region (A) and the amorphous phase (B).
There are some polymers that are completely amorphous (e.g., atactic PS or PMMA), but most are a combination of entangled and disordered regions that surround the crystalline lamellar-type zone regions. Such a combination is depicted in Fig. 1.5.
Figure 1.5 Scheme of a semicrystalline polymer.
The crystallization of a polymer can be performed by cooling it in solution or in melted form. In both cases, polymer molecules are either like an isotropic fluid or partially ordered in a liquid crystalline mesophase. Crystallization can also be produced during the polymerization process. The most common crystals that a polymer can form are faceted single lamellas, nonfaceted lamellas, branched structures (dendritic), sheaf-like arrays of lamellar ribbons (axialites, hedrites), spherulitic arrays of lamellar ribbons (spherulites), fibrous structures, and epitaxial lamellar overgrowth on microfibrils (Chanzy et al., 1971; Keller, 1958).
Amorphous polymer regions are formed when parts of the chains are unoriented throughout the bulk polymer. During the crystallization process, it has been observed that relatively short chains self-assemble into crystalline structures more readily than longer molecules. Therefore, the degree of polymerization (DP) is an important factor that determines the crystallinity of a polymer. Polymers with a high DP have difficulty to get organized into layers because they tend to become entangled. Polymers with low MW (short chains) are generally weaker in strength. If they are crystalline, only weak secondary forces hold the lattice together. This permits the crystalline layers to slip past each other causing a disruption in the material; crystallinity promotes an increase in density and strength. Higher DP (amorphous) molecules have great strength because the molecules become entangled between layers. In the case of fibers, tensile forces originate a deformation of the polymer about three or more times their original length, while in a semicrystalline state they produce increased chain alignment, crystallinity, and strength. Two parameters that also influence the polymer morphology are the size and shape of the substituent groups in the repeating unit. If the units are large and atactic, it is difficult for the polymer chains to self-assemble in an ordered manner, resulting in a more amorphous solid. Likewise, smaller unit chains that have a very regular structure (e.g., rod-like) will form more crystalline polymers. The regularity of the polymer backbone is a key factor to get order in polymer chains (e.g., isotactic polypropylene crystallizes forming a rigid stable solid), whereas atactic polypropylene does not crystallize and forms a rubbery elastic solid. Atactic polymers may crystallize when the substituent X group in (–CH2CHX–)n is very small, allowing regular packing of the chains regardless of whether the different pendant groups are randomly placed; e.g., poly(vinyl alcohol) has a small hydroxyl X and hydrogen bonding helps for molecular packing. Besides, if the X group forms a longer regular side chain, crystallization may occur provided that the pendant groups have sufficient length—usually greater than about six repeating repeat units (Pethrick, 2007; Woodward,
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