Polymer Science and Innovative Applications: Materials, Techniques, and Future Developments

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Chapter 1

Polymers to improve the world and lifestyle: physical, mechanical, and chemical needs

Mariam Al Ali AlMaadeed¹, Deepalekshmi Ponnamma² and Ali Alaa El-Samak³,    ¹Qatar University, Doha, Qatar,    ²Center for Advanced Materials, Qatar University, Doha, Qatar,    ³Materials Science & Technology Program (MATS), College of Arts & Sciences, Qatar University, Doha, Qatar

Abstract

The wide-ranging applications of polymers are due to their important advantages that involve their relatively low cost, low density, resistance to corrosion, resistance to most chemicals, and easier manufacturing designs. Their lightweight and flexible designs are crucial in applying polymers in the majority of industrial and technological applications such as aircraft engineering, space studies, packaging, and smart biomaterials. The properties of the polymers highly depend on the monomer units present within them, the connection points or nodes, their conformation, and the chemical and physical attributes of the monomers. Though polymers cover a large area ranging from elastomers to thermosets, their elasticity, insulating behavior, ductility, optical, and conducting properties sometimes necessitates additional reinforcements. Polymers can be transferred to different types of composites, and find extensive applications in environmental technologies, energy generation, storage devices, solar cells, and biomedical engineering. This chapter discusses the increase in production rate and cost of polymers during the past century up to the present date. It also provides the basic concepts of the physical, chemical, and mechanical strategies of polymers that can make them applicable in improving global lifestyles.

Keywords

Technology; polymeric; lifestyle; smart materials

1.1 Introduction

The role of polymers in biological processes is significant as they are the molecular basis of life [1–5]. The relationship of polymers with biorelated fields start from macromolecular deoxyribonucleic acid to medicines and biomedical devices. Proteins, carbohydrates such as polysaccharides, enzymes, and tissues are arranged in the form of repeating structural units similar to that of polymer skeletons [6,7]. As living tissues are composed of polymers, these macromolecules are considered as natural allies of medicines. Many polymers like polyamides, polyesters, polyurethanes, polyethylene, silicones, polycarbonate, fluorocarbons, and so forth are used in medical fields [8]. However, biocompatibility, toxicity, biodegradability, among others, are major concerns when applying synthetic polymers in medical sectors. Biomimetic synthetic phospholipid membranes for coatings, cellophanes for kidney-related applications, hydroxyapatites for dental applications, etc. are examples of the numerous applicabilities of polymers in biomedical areas [3].

While polymers can be synthesized in many different ways using polymerization techniques, their final application including mechanical, structural, and functional properties highly depends on the conformation of the monomer units, molecular size and weight, monomer type and distribution, or polydispersity index. Based on the mode of synthesis, polymers vary as homopolymers and heteropolymers, whereas based on their origin they vary as natural and synthetic [9]. There are numerous classification strategies for polymers and studies have revealed specific shapes at atomic and nanometer resolutions. In the case of industrial applications, their chain flexibility and mobility are highly desirable qualities that can be achieved by the selection of polymers with small side chains, less polarity, and noncrystallizing under deformation [10]. Crosslinking is another important area, as in the case of elastomers such as natural rubber, the process of crosslinking helps the molecules to strengthen the molecular skeleton [11]. As far as industrial applications are considered, energy efficiency is also significant. Lower energy loss, high toughness, and appreciable mechanical strength are necessary parameters in addition to lightweight and stretchability.

Numerous studies have been performed on various polymers over the past few decades. Reinforcements such as macro-, micro-, and nanoparticles were also handled by several research groups [12–14]. Though this vast topic of polymer science is much investigated, there is a huge demand from technology on exploring the complete exploitation of polymeric properties. This chapter will discuss the significance of polymers to satisfy the global demand. Other than explaining the history of polymers and their classifications, the role of polymers and composites in regulating global requirements, and utilization of the chemical, mechanical, and physical properties for specific demands needed in the society are explained in this chapter.

1.2 Industrial revolutions and polymer applications

Polymers represent an advanced class of materials, consisting of multiple repeating building blocks known as monomers that are linked together to form a much longer chain. The importance of polymers is due to their wide application range, as they resemble industrial, economical, medical, and academic interests and goods that enhance our lives on a daily basis [1].

Polymers were utilized in daily life and in industry for a long time, yet the true appearance of their importance and use was discovered in the late 20th century. Natural polymers such as cellulose were produced in 1838 from natural plants. It is composed of repeated units of glucose. The natural polymer industry started in 1818 with the production of natural rubber for different daily life commodity items such as shoes and gloves. Artificial polymers (e.g., plastic, fiberglass, nylon, and many other products) impacted the society and changed it for the better, providing a class of synthetic polymers formed to satisfy niche applications. Synthetic and natural polymers play a major role in facilitating a comfortable lifestyle due to their integration in many aspects of modern society, including transportation, medicine, communication, and fashion [2].

The first industrial revolution started in the 18th century with an emphasis on the utilization and improvement of metals (mainly steel) through steam engines. The industrial revolutions continued through other stages of electrical energy and mass production (second revolution), electronics and automation (third revolution), and now we are in the fourth revolution, which includes cyber–physical systems. Future technologies will depend on the previous revolutions and combined technologies between digital and physical sectors. The new modified technologies can improve operations and be more productive. New businesses and industries can be driven by the new technologies. Polymers, as will be seen later in this chapter, are leading many sectors in the fourth industrial revolution.

Polymers were mostly applied as insulators and packaging materials due to their economic manufacturing benefits, long-term stability, significant toughness, good dielectric properties, and durable mechanical strength [15]. For example, polyethylene is one of the major polymers used particularly for the cable industry, with certain functional modified versions for special applications such as less flammability [16]. Over the past two decades, polymers were explored for their electrical and energy-related properties such as applications in energy harvesting devices, solar cells, piezoelectric nanogenerators, fuel cells, optical switches, and lithography [17,18]. They are now used in many other applications like 3D printing, aerospace, water purification, and smart textiles.

1.3 Polymers: general classification and production

As explained shortly in the introduction, polymers are materials that consist of many simple structural units (monomers) joined together to form giant molecules. The art of modifying and manipulating the high number of molecules in polymers allowed modern society to fabricate different types of polymers in the form of fibers, films, and adhesives. There are two main sources of polymers, natural and synthesized. (1) Natural polymers are found in nature. Examples include proteins, rubber, cellulose, and starch. Plants and trees are made of cellulose, which make it the most common polymer on Earth. Chitin is another common polymer available in the shells of shrimp, crabs, and lobsters. It has a combination of attractive properties of hardness, insolubility, and flexibility. (2) Synthesized polymers are produced from fossil fuels. They are arranged with longer chains compared to natural polymers [8,9].

Synthesized polymers are mainly derived from its low cost and highly abundant predecessor, petroleum, with highly efficient processing methods, allowing for the use of less than 5% of an oil barrel to contribute to the production of large amounts of polymer, therefore crowning petroleum as the most effective and main source of polymers for the near future. Additionally, the polymer industry experienced rapid expansion when synthetic polymers were first discovered in the 19th century, allowing them to compete and sometimes overtake older, more-established industries, such as the steel, aluminum, and copper industries. The value of produced polymers depends on the processing method, properties, and specifications of these materials. Polymer properties are heavily influenced by the molecular composition, such as molecular size and branching. The processing method such as the set up and flow time can add to the expenses of the produced polymer.

The cost of polymers depends on the manufacturing procedures. For instance, polyolefins (e.g., polyethylene and polypropylene) cost less because they are derived directly from crackers streams (the plant in which saturated hydrocarbons are broken down to unsaturated smaller hydrocarbons). Treatment and modification of polymers increase the cost, but at the same time utilize the polymers for different and new applications. In 2016 the global plastic compounding market size was estimated to be 26.73 million tons. Replacement of metallic parts with polymers owing to their lightweight and flexible nature influences the production rate, cost, and consumption patterns of typical polymers. Various factors such as demand for versatile materials, availability of feedstocks, sociopolitical events, manufacturing processes, and so forth affect the global polymer production. Reports have detailed the progressive increase in the US plastic compounding market revenue for the time period 2014–26 [3]. The market for polypropylene and polyethylene is expected to increase as these materials are highly needed in packaging, automotive, and construction applications. The production of polyvinyl chloride and polyethylene terephthalate (PET) is also increasing due to technological innovations. The environmental challenges necessitate the production of biodegradable materials, therefore biobased polymers are also receiving increasing and significant attention.

It is well-known that the supply and demand of polymer production depend on the applications of the polymer. These applications will be discussed in-depth later on in this chapter, but here we would like to bring it up to view its correlation with the price rate and production percentage. Polymers that are used for structural purposes had a production rate of 32.2 billion kilograms in 1992 in the United States alone, split into plastic production of 26.1 billion kilograms, fiber production of 4.1 billion kilograms, and rubber production of 1.9 billion kilograms [4]. With rough estimates, we can conclude that the production rate has tripled since the start of the 21st century. Structural polymers are usually sold in the range of US$0.50 and upwards per pound, while the price of its raw material (crude oil) is only US$0.132 per kilogram. Therefore structural polymers represent a large turnover for the manufacturer.

Another important application of polymers can be derived from thermoplastics that acquire outstanding packaging ability [19]. And since these polymers can be recycled on demand, their production and importance will only increase in the future due to advancement in recycling technology and the shift in the global demand from single-use polymers to recyclable polymers.

It is essential to review the case study of ethylene production to understand the drastic increase in polymers’ supply and demand. Starting in the early 1940s, England was producing the simplest form of thermoplastic, polyethylene [20]. Polyethylene backbone consists of four hydrogen and two carbon monomer blocks that are constantly repeated. Moving to the 1980s, the discovery of different processing methods allowed the production of different grades and types of polyethylene such as low-density and high-density polyethylene. Increasing the production of linear low-density polyethylene alone, it reached approximately 2.2×10⁹ kilograms per year. Furthermore, synthetic rubber had high importance due to its significant use, with production numbers estimated to be 1.9 billion kilograms produced in 1992 in the United States alone. Synthetic fiber production is estimated to be 4 billion kilograms yearly in the United States (Fig. 1.1).

Figure 1.1 US production of thermoplastics by type in the year 1990.

Mass production of plastics increased from 50 million tons in 1977 to 322 million tons in 2015 [21], which is a 544% increase in production. This increase is mostly in polyolefin production, which accounts for more than 55% of the plastics industry. China is the leading country in plastic production, with about 49% of the global market [22]. Alternating polymer properties made them one of the most functional materials during the past few years. Up to 2015, about 8300 million metric tons (Mt) of virgin plastics were produced, and 6300 Mt of plastic waste was generated up to 2015 as shown in Table 1.1 [23]. This huge amount of waste causes severe land and water pollution, negatively affecting the environment. For example, microplastic is currently a global concern due to its high presence in fish, mussels, salt, and water.

Table 1.1

Fig. 1.2A shows the estimated mass of mismanaged plastics waste in 2010 [22], according to which the maximum contribution is from China. Unfortunately, oceans are considered the ideal places to dispose plastic waste, where the currents make plastic waste virtually irretrievable. Many studies demonstrated that rivers carry a large amount of plastic waste, finally depositing it into the sea. Microplastics of 1–1000 μm size are generated by such processes. Several reports show the presence of microplastics in seafood products, salt, and even in animals’ bodies. Karami et al. addressed the issue of microplastics by investigating 17 types of salt produced in eight countries over four continents. As represented in Fig. 1.2B, the chemical composition of the extracted materials was studied. The group found that in a given sample, 41.6% were plastic polymers, 23.6% pigments, 29.1% unidentified, and 5.5% nonplastics. The major polymers were polypropylene, polyethylene, PET, polyisoprene/polystyrene, polyacrylonitrile, and nylon-6 [23]. Though the study did not find direct health hazards by salt consumption, possibilities of gradual accumulation of microplastics in human bodies in the future can have negative results.

Figure 1.2 (A) Estimated mass of mismanaged plastic waste 2010, in metric tonnes; (B) chemical composition of the isolated particles from salt. (a) Pie chart of the chemical composition of the isolated particles from all salt samples and the corresponding proportion of different (b) plastic polymers and (c) pigments [24].

The Middle East region contributes to about 7.3% of the global plastic production. The developed economy, huge population, and large coastal area in this region promote the generation of microplastics. Fig. 1.3 shows the microplastics isolated from the north eastern coast of Qatar’s Exclusive Economic Zone by Castillo et al. [25]. Granular particles in the size range of 125 μm–1.82 mm and fibrous particles of 150 μm–15.98 mm were obtained. Anthropogenic activities such as oil-rig installations and shipping operations in this region cause the presence of many microplastics.

Figure 1.3 Microplastic particles isolated from seawater samples in the north eastern marine waters of the Qatar’s Exclusive Economic Zone [25].

1.3.1 Fabrication methods

There are many techniques for polymer fabrication technology. Listed below is a summary of the common technologies:

1. Casting: The polymer in this case is solidified in a mold by chemical or physical procedures.

2. Molding: In this technology, heat and pressure are used to change the shape of the polymer using different types of molds. Examples include:

• compression molding,

• injection molding,

• blow molding, and

• other molding techniques such as rotational molding and reaction-injection molding.

3. Extrusion: In this technology, a screw (or more) is used to process the polymer with heat and pressure. The extruder can be divided to different chambers. Examples include:

• coextrusion,

• film extrusion,

• blow film extrusion, and

• over jacketing extrusion.

4. Electrospinning: This is the most used technique for polymer fiber production. Starting with polymers as a suspension in a suitable solvent, and by regulating the concentration of the solution and applied voltage, fibers of various dimensions can be fabricated.

Other techniques of polymer fabrication include, calendaring, coating, and foaming. After specific processing, the produced polymer systems and composites can be tailored according the required final application and shape.

Polymer systems can include:

• Immiscible or miscible polymer blends.

• Polymers composites.

• Since polymers possess certain limitations that make them functionally unstable for specific areas, or fields of applications, reinforcing them with other stable particles is often necessary. Here the significance of micro- and nanoparticles come to the fore as they are largely applied to improve polymer properties and to design the polymer composites and nanocomposites. Polymer nanocomposites can be designed based on clay nanolayers, carbon nanotubes, ZnO nanoparticles, graphene, etc. [14,26]. However, the particle dispersion is rather difficult due to less compatibility of the filler–polymer chemical environments, usage of surfactants, chemical reagents, etc., which can modify the filler surfaces and thus strengthen the polymer–filler interfaces. This pointed out significant enhancements in nanocomposite properties such as electrical, dielectrical, mechanical, and gas permeability properties. Different types of additives can be added to improve the properties of the polymers. This can include additives that advance the mechanical properties, antifouling additives, flame retardants, plasticizers, self-healing agents, and antioxidants. One way of modifying the polymer properties is changing it into nanosized materials. In this case they will have large surface area to volume ratio. They can also be more flexible in surface functionalities and other mechanical properties.

These processing techniques can be used to tailor polymers, change them into smart materials, and improve their properties. Other techniques that can be used to change the properties include chemical modifications of the structure and physical modifications (e.g., gamma irradiation).

1.3.2 Classification of polymers

Polymers can be classified into two main classes, (1) thermoplastics and (2) thermosets. The main differences are shown in Table 1.2.

Table 1.2

1.3.2.1 Thermoplastics

This class of polymers can be shaped through several heating and cooling steps. The materials flow through specific molds to have the required shape when it is hot. Then a cooling procedure is arranged to solidify the polymer to the required shape. This special feature allows thermoplastics to be recyclable and allows them to be considered environmentally safe and friendly. Furthermore, thermoplastics can be produced through different techniques, such as extrusion or molding. Major types of thermoplastics include styrene, propylene, and ethylene, which resemble between 80% and 90% of the overall thermoplastic monomers produced. This class of polymers is heavily used as a source for packaging bags. Another application of thermoplastics includes high heat and mechanical resistivity. Modified thermoplastics are known as engineering thermoplastics, which cost more to produce in comparison to low-quality thermoplastics, with their application consisting of structural support in transportation, such as for automobiles and aircrafts. Thermoplastics are also viable for niche markets as they can be blended with different materials to increase toughness and chemical stability, and to obtain special forms of structures. Fig. 1.4 shows some of the classical applications of thermoplastics.

Figure 1.4 Categories of uses for thermoplastics in the United States, 1990.

1.3.2.2 Thermosets

Thermosets are specific class of polymers that form well-defined, irreversible, chemical networks that tend to grow in three dimensional directions through the process of curing, which can either occur due to heating or through the addition of a curing agent [29], therefore causing a crosslinking formation between its chemical components, and giving the thermoset a strong and rigid structure that can be added to other materials to increase strength. Further applications of thermosets include coating and epoxy adhesives. Around 69% of the application of thermosets present in the construction and building industry, other uses of thermosets are in transportation, adhesives, and electrical equipment. Thermosets are also highly used in advanced applications, especially in the aerospace and military industries due to the multiple composites that can be produced with the presence of thermosets, including reinforced carbon fibers and glass.

1.3.2.3 Elastomers (rubbers)

Elastomers are typically amorphous with a low amount of crosslinkage, while also being soft and flexible, and can usually withstand a large amount of force that would normally lead to deformation, therefore are capable of attaining their original form. Synthetic elastomers were first produced in the United States due to the shortage of natural rubber supply during World War II. Elastomers have wide applications in many industrial products, such as electrical insulators and tyres. In addition, they are found in many consumer products including sporting goods and casual wear. The interest of industries in thermosets is due to their high strength, resilience, and durability.

1.4 Current lifestyle and the need of polymers

The possibility of modifying polymers for specific applications through functionalization made them available around us in everyday life. The common use of polymers in the modern world is mainly due to their lightweight, easy manufacturing, and the possible tailoring procedures that suit the needs of consumers. It is well-known that polymers have improved the lifestyle of humanity significantly. Industries and governments have their own requirements for these materials, including standards, compliances, and certifications. The use of polymers depends on their physical and mechanical properties. It is important that the used material has its own failure analysis tests, have no design faults, and have relatively low costs.

One important advantage of polymers is the possibility of altering their properties [30–33], to meet specific requirements and applications, such as increases their conductivity, mechanical strength, piezoelectricity, and stability. This modification opened new markets in electronics and communications. Over the past century, polymers were used mostly as insulators and packaging materials. They are mostly synthesized materials and are not biodegradable or recyclable. They are now used in cables due to their good mechanical properties and excellent dielectric behavior. Major applications of polymers include aerospace, electronics, medical, packaging, and the automotive and building industries. Another emerging field of sensors is currently using new modified polymers. New advanced techniques in improving polymers and polymer composites led to an increase in sensors sensitivity, selectivity, and response time. Other parameters in these polymers can be utilized such as their permeability, durability, and thermal and electrical properties.

Polymers are widely used in other applications as structural adhesives and protective coating [34], such as epoxies. New techniques for self-healing coatings are under study and expected to be available in the market soon.

In packaging application, there are many used materials with different sources. The most common packaging material is low-density polyethylene. Most packaging materials are synthesized materials and are not biodegradable or recyclable.

One major disadvantage of polymers is their long-life stability, which may affect the environment. Recycling is a common procedure to reduce this negative effect. In the case of polymers, the waste should be separated to different categories and then recycled. Another way to reduce polymer waste is incineration and direct combustion. The energy required to burn plastics exceeds 40 MJ/kg. This is slightly less than natural gas (48 MJ/kg) and approximately similar to oil combustion [35]. Landfills are also used in many countries. To reduce the negative effect on the environment, biodegradable polymers are now used in many applications to reduce waste. The most common applications for biodegradable polymers are in packaging, drug delivery, and agriculture.

Biodegradable plastic: Petroleum-based plastic continues to affect the environment and cause habitat destruction. There is an increased search for biodegradable alternatives, and an excellent example of this is polyhydroxyalkonates, biodegradable plastics that are synthesized by microbial polyesters [36]. The reason behind the importance of these polymers to the world is that the biodegradable plastic is produced from renewable materials that involves producing the biopolymer through using waste as the primary reactant under anaerobic digestion and composting. Furthermore, these polymers are excellent for their low cost, renewability, and biodegradability.

Biomedical application: Another advanced usage of polymers is present in the form of biodegradable hydrophobic polymers, which are plastics (mainly polyethylene glycol) that possess biocompatibility and high mechanical strength. Additionally, these polymers can be fused with a hydrogel network that allows them to interact and obtain cell-like interaction [37]. This interaction allows for higher water absorption that is crucial in multiple biomedical devices.

There are many other applications of polymers that will be covered in more details in this book. For example, in the medical field polymers are used in controlled drug released orthopedic implants, artificial, organs, dressing, and bandages. Biocompatibility of polymers with tissues is one of the main challenges in this field. Another important application of polymers is self-healing.

Self-healing: New techniques are produced to improve the protective coatings by introducing self-healing functions [34]. These polymers can save costs with regards to machinery and production, and is usually a property only possessed by plants and animals. This advanced technology is currently utilized in different industries to reduce the corrosion cost especially when using low cost and green healing materials.

Current classes of polymers such as dynamic polymers and polymer composites loaded with healing agents are capable of providing self-healing properties [38]. Hence the polymer can be used as a storage device in order to contain the healing agent, and if the mechanical damage was sufficient enough to break the storage device (microcapsule), the healing agent would diffuse through the mechanical slip and polymerize, therefore minimizing the mechanical damage (Fig. 1.5).

Figure 1.5 An example of self-healing polymers: immersed coatings in 10 wt.% NaCl solution: control epoxy coating on (A) first day, (B) second day, and (C) fourth day; EP/7.5 HNT coating on (D) first day, (E) second day, and (F) fourth day [39].

1.5 Polymers to composites

Since polymers possess certain limitations, which make them functionally unstable for specific areas or fields of applications, reinforcing them with other stable particles is necessary. Here comes the significance of micro- or nanoparticles that are largely applied to improve polymer properties and to design polymer composites and nanocomposites. Our group has significant experience in designing polymer nanocomposites based on clay nanolayers, carbon nanotubes, ZnO nanoparticles, graphene, and so forth [32,40–42]. However, particle dispersion is rather difficult due to less compatibility of the filler–polymer chemical environments. Different procedures can be applied to modify the filler surfaces such as usage of surfactants and chemical reagents. These procedures can strengthen the polymer–filler interfaces. This pointed out significant enhancements in the nanocomposite properties such as electrical, dielectrical, mechanical, and gas permeability.

1.6 Specific requirements of polymers using physical, mechanical, and chemical methods

Many of the desirable properties for particular polymer applications are well-known, however achieving those qualities are really challenging. Polymers in general are made of multifunctional monomer units connected through nodes in the form of a network. The physical, chemical, and mechanical properties of a polymer network depend highly on the density and functionality of these connecting nodes. The properties can be modulated by varying the monomer molecular weight, functionality of the units, and the multifunctional monomer ratio. However, these processes can induce variations in network chemistry and can create defects and loops that directly affect the mechanical strength of the final products [43]. The significance of such primary defects and loops on the mechanical strength and elastic modulus of a typical polymeric system was the subject of study by Chan et al. [43], where they have synthesized elastomeric polymers following selective and rapid thiol-ene click chemistry.

The physical properties of a polymer highly depend on the nature and arrangement of monomer units. For instance, high-density polyethylene (HDPE) is a rigid translucent solid that can withstand up to 100°C heating, but low-density polyethylene (LDPE) is soft and deforms after 75°C of heating. The large molecular chains of polymers generally pack in a nonuniform way, with ordered crystalline regions mixed up with disordered amorphous regions. Depending on this packing, the polymers can be semicrystalline and completely amorphous. The factors that determine the crystalline nature of a polymer include the chain length, branching, and interchain bonding. A few examples of crystalline polymers include LDPE, HDPE, cellulose etc. However, elastomers like natural rubber are fully amorphous in nature. In those cases, crosslinking with sulfur results in achieving desirable properties especially at 2%–3% crosslinking, whereas 25%–35% crosslinking causes rigid and hard rubber formation. The crystallinity of the polymer regulates many properties such as piezoelectric performances (for polymers such as polyvinylidene fluoride), mechanical strength, and thermal stability.

The emerging area of responsive biointerfaces that are capable of mimicking natural surfaces are based on synthetic polymers, where the function and structure of these materials vary with environmental changes. A stimuli-responsive macromolecule undergoes chemical and conformational changes when its environment (such as temperature, magnetic/electrical/optical field, chemical composition or mechanical field) changes. Various dimensional stimuli-responsive polymer systems are represented in Fig. 1.6 [44]. Stimuli-responsive polymers are highly useful for satisfying various functional needs that society demands.

Figure 1.6 Galaxy of nanostructured stimuli-responsive polymer materials [44].

1.7 Internet of Things and smart materials

The polymer industry is a key factor in the Internet of Things (IoT) era. In this vision, one network will be connecting all materials in a wireless and sustainable way. The base technology of IoT is the need for flexible electronics, sensors, devices, and power sources. These smart polymers change their properties and/or shape according to the environment and external effects. These external stimuli have different characteristics such as thermal, electrical, mechanical, or magnetic effect. 3D printing of polymers is developing rapidly due to high-speed production, flexibility, low cost, and specific application customization. Utilization of polymers and polymer composites in traditional applications will be reflected in future applications of new smart cities where there are interactions between users and devices due to the developments in information and communications technology [45]. Application domains of IoT are shown in Fig. 1.7 where classic polymer applications play a major role.

Figure 1.7 Smart cities in the application domain of IoT [45].

Piezoelectric polymers with self-powered capability are common smart materials used in control systems and wireless sensors. Another smart material application entails printing them on specific sources to increase the information related to these materials. This is used in different industries such as active packaging in the food industry to maintain the quality of the food and inform the buyers of their contents. Smart biomaterials are widely used to improve the healthcare system, such as smart wound monitoring systems with bandages that control the drug release in a smart system [46]. Other applications of polymers in IoT include monitoring systems, the energy sector, and storage systems. Collaboration between scientists from different disciplines can lead to more progress in this field.

1.8 Conclusions

To conclude, polymers are an essential part of our day-to-day activities as they are involved directly or indirectly to the majority of commodity items that are being handled. Studying their significance, properties, and modification possibilities can further improve their applications. Polymers are modified by the inclusion of various fillers to develop themselves to composites, and that opens up numerous electronic, mechanical, and biomedical applications in industry and technology. This chapter provides a glimpse into this information and a short note on the fundamental aspects of the whole book.

Acknowledgments

This chapter was made possible by NPRP grant 10-0127-170269 from the Qatar National Research Fund (a member of Qatar Foundation). The statements made herein are solely the responsibility of the authors.

The author Ali Alaa El-Samak would like to acknowledge Qatar University for the support granted through the Graduate Research Assistantship Program (GRA).

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Chapter 2

Morphology analysis

Anton Popelka, Sifani Zavahir and Salma Habib,    Center for Advanced Materials, Qatar University, Doha, Qatar

Abstract

This chapter is dedicated to the surface morphology and topography analyses of various types of polymers in terms of their structural conformations and resulting material structures. The morphology of polymers includes their overall polymeric structure such as branching, molecular weight, crosslinking, and crystallinity. The morphology analyses of crystalline polymers, amorphous polymers, and polymer blends prepared in different forms such as foils, fibers, or foams, are described in this chapter. Moreover, the analysis and effect of surface modifications on the resulting surface morphology and topography of polymers is reviewed as well. This chapter includes techniques and methods regularly applied to investigate the morphology and topography of polymer materials. These techniques include optical microscopy and electron microscopy, scanning probe techniques, X-ray diffraction, differential scanning calorimetry, and dynamic mechanical analyses. A combination of these multidisciplinary techniques can enable the analysis of polymer morphology from a complex point of view.

Keywords

Polymer; structure; morphology; topography; characterization

2.1 Introduction

Surface morphology and topography represent important properties of polymeric materials (from the nano- to the macroscale), and originate from their chemical nature/structure and production processes. Polymeric materials are characterized by specific aspects of their surface morphology, which affect their final surface properties such as wettability and adhesiveness and applicability to printing, dying, lamination, water repellency, and biocompatible processes. Therefore information about the surface morphology and topography of polymers is crucial for their use in various industry sectors such as automotive, aerospace, building, textile, medical, and packaging. Different types of polymers have different natures and structural conformations that are responsible for their resulting morphologies and topographies. The overall polymeric structure such as molecular weight, crystallinity, branching, and crosslinking, affects the final morphology. An overview of the internal morphology analysis of amorphous, crystalline, and polymer blends is discussed in this chapter. Moreover, the external surface morphology/topography of the resulting polymers in the form of foils, fibers, and foams is described in this chapter as well. Last but not least, the effects of various surface modifications that affect the surface morphology in 2D and 3D (roughness) are also reviewed. This chapter also includes a description of techniques and methods commonly applied to analyze the surface morphology/topography of polymeric materials. These techniques include various scanning probe and optical/electron microscopies. The implementation of these techniques and their combination is necessary for multidisciplinary study of polymer morphology/topography.

2.2 Polymer morphology

The characterization of polymers contains many aspects; this study is concerned with morphology measurements that use developed techniques. Studying the morphology of a polymer surface gives a clear identification of the changes and modifications that have occurred. The measurement of polymer morphology is an interesting field of study as it refers to the functional properties, modification, and applications of polymers. Over the past four decades, many different techniques have been developed to obtain a quick, clear, and accurate morphology measurement of polymers. In the case of composition studies, photon radiation such as X-ray and infrared radiation have been efficiently used to characterize the chemical composition of materials quickly. The measurements started with the study of 1D wired detectors [1,2] and expanded to 2D structures [3–5] with the ability to sense position once the orientation of beamlines was detected [6–9]. Another significant breakthrough in the first decade of the 2000s included a morphological development from the melt state that can be analyzed by atomic force microscopy (AFM) allowing images with a high resolution to be obtained [10–12]. AFM was developed as a quick method for obtaining topographical images [13–17]. AFM is a nondestructive technique; the same area can be scanned many times without any negative impact on it. Studying multiple sites on the surface of a polymer only provides information about the morphology changes for a few micrometers of material based on the applied treatments or modifications.

2.2.1 Crystalline polymers

Crystalline polymers are defined by their strict composition and perfect order or translation of atoms or molecules. A perfect translation gives the shape of the lattice defining each crystal type. Although some dislocations have a limited impact, their general translation symmetry preserves the overall shape of the polymer [18]. As the chain is well defined and oriented in one direction of the lattice, the crystals form a polymer crystal [19]. The growth rate of the crystal with a certain folding affects the stability of the folding [20]. Each type of polymer crystal has a specific order and melting temperature in accordance with the entropy of the conformation of the chain folding [21,22], which is not the case for small molecules that have a precise melting point (no chain folding effect) [23]. In small molecules, the crystallization step provides the same change in entropy with the same molecule repetition. This is not the case in polymers because the molecule differs based on each unit built causing variety in the entropy (each unit causes a certain type of entropy while folding) [24].

Despite being in a metastable state, single crystals in polymeric materials have the same orientation. This is caused by the nucleation process, and polymers are integrated based on the same parameters of the unit cell [20]. Polymer chains are able to crystallize into various metastable states (different chain folding degrees) [23,25,26]. The crystallization of polymeric chains represents a difficult process in comparison to that of small molecules [27]. If all accessible sites are already occupied in a crystal, some of the chain blocks will be excluded and are responsible for the formation of lamellar bounds [21]. Further ordering can also occur after additional reorganization in the crystalline state [28–31]. It has been reported that crystallization and heterogeneous nucleation of polymeric melts in comparison with metals (high surface free energy surfaces) lead to noticeable changes in the surface morphology. Moreover, transcrystallinity can be incurred in polypropylene (PP) or polyethylene (PE) polymers with low surface free energy (wettability) after melts contact copper or aluminum. On the contrary, surfaces with low surface free energy (Teflon, Mylar) in a combination with nitrogen gas have no nucleating activity with a spherulitic morphology [32].

2.2.2 Amorphous polymers

Amorphous homopolymers such as polycarbonate, poly(methyl methacrylate) (PMMA), or polystyrene (PS) are defined by the absence of crystalline structures and may only have weak supramolecular structures [33,34]. They are associated with the idealistic model of an amorphous solid. The strong interpenetration of a great number of macromolecular segments induces the formation of a large number of topological (physical) links, and entanglements keep the macromolecules compact, which provides toughness and strength to polymeric materials. A second contribution comes from the Van der Waals forces within macromolecule segments with an entangled molecular network. Coiled macromolecules have lower packing densities in comparison with that of parallel arranged conformations of molecules, which are typical of semicrystalline polymers. Therefore the density of amorphous polymers is usually lower than that of semicrystalline polymers (with the exception of existing heavier elements in the chains as in polyvinyl chloride). The volume that is not filled by molecules, that is, the unoccupied volume between the molecular segments, is expressed by the term free volume, and affects the thermal and mechanical properties of polymeric materials. The macromolecules are entangled in the interlamellar (amorphous) regions or form linked lamellae, the so-called tie molecules [35].

2.2.3 Semicrystalline polymers

Semicrystalline polymers are based on a parallel arrangement of neighboring molecular segments, possibly by folding or bundle formation (Fig. 2.1) [36]. Macromolecules are partly included in crystals and, therefore, also have reduced mobility of neighboring segments. Thus the formation of new crystals is hindered, preventing the total crystallization (as in atomic structures) of macromolecules and yielding semicrystalline structures. The characteristic elements of semicrystalline polymers are represented by the crystalline lamellae, interlamellar amorphous regions, and lamellae interfaces. Often, chain ends, short branches, or defects in the crystals inside the lamellae between crystalline blocks are responsible for the formation of defected layers. The lamella interface (lamella surface layer) contains folds, branches, and chain ends, and is often visible in electron micrographs because of its strong staining as a separate structure. The macromolecules are entangled in the amorphous regions (interlamellar) as in amorphous polymers or they can form lamellae links, so-called tie molecules. The typical thicknesses of lamellae lie in the range of 10–30 nm (but can reach thicknesses of more than 1 µm in high-pressure crystallized ultrahigh molecular weight PE) with lengths up to 1 µm. Different types of crystalline lamellae can be produced such as sheaf-like structures, parallel arrangements in stacks or bundles, spherulites with a radial arrangement of lamellae, which are typical for high-density PE or PP, and twisted lamellae that are arranged in concentric rings of banded spherulites as is typical for low-density PE (LDPE). Depending on the polymer and thermal treatment, the spherulites can reach up to hundreds of microns in diameter [35,37,38].

Figure 2.1 Scheme of spherulite with a birefringent structure consisting of crystalline lamellae with amorphous interlamellar joins [36]. Copyright 2019. Reproduced with permission from Elsevier.

2.2.4 Polymer blends

Mixtures of two or more polymeric materials in polymer blends represent another combination of different macromolecules. Various polymeric materials are normally incompatible, resulting in a phase separation between the dispersed phase (minor component) and the matrix (major component). Networks or interpenetrating structures are usually formed with an equal composition of both components (50:50). This phase separation corresponds to microphase separation in block copolymers due to the absence of covalent bonds between the components with coarser structures. Several methods can be utilized to improve the compatibility of polymers including mixing with compatibilizers, reactive blending, or grafting. Compatibilizers (block copolymers or graft polymers) are responsible for particle size reduction of the minor component. Between the components, separate interfaces (thin boundaries) and interphases (thicker layers often with their own structures) exist. The fine morphologies of polymers with similar chemical compositions having relatively good miscibility can be formed [39]. For example, the network morphology of a cryogenic fractured PE/PS blend is shown in Fig. 2.2 and was obtained by scanning electron microscopy (SEM). These blends were prepared by a reactive compatibilization using a Friedel–Crafts reaction. The homogeneity and shape of the dispersed PS phase was investigated. The homogeneous distribution of PS particles within the PE matrix can be clearly seen [40].

Figure 2.2 Network morphology of a PE/PS (80:20) blend with a PE matrix containing embedded PS: (A) linear LDPE type 6200 (Mw: 52,000 g/mol) and (B) linear LDPE type 6600 (Mw: 40,000 g/mol) [40]. Copyright 2019. Reproduced with permission from Elsevier.

There are different classifications of polymer blends based on the type of polymers blended together. A homogeneous blend is a blend of two miscible polymers that have only one phase. This happens when the total free energy of the blend is negative. This leads to one glass transition temperature (Tg), making it a homogeneous material. In contrast, blends that have positive free energy are not immiscible, but compatible, and have more than one phase in the material structure; the Tg is then separate for each phase. The initial information about the morphology can be obtained by a simple visual checking. The blending of two colorless (transparent) amorphous polymeric materials with different refractive indexes results in an opaque material and the size of the phases usually surpasses the visible light wavelength (>500 nm). The difference in the refractive indexes has to be larger than 0.003 to have opacity [41,42]. In the case of crystalline polymers, this rule is even more complicated. These polymeric materials are often opaque due to differences in the refractive indexes of the crystalline and amorphous phases. Moreover, the spherulites are large (>500 nm) too [43,44]. Therefore the visual inspection can be performed for semicrystalline polymeric materials, which are heated above melting temperature of crystalline component.

Nowadays, polymer blends and composites comprise over 80% of all plastic materials. Market pressures force manufacturers of resins to develop economically improved materials with superior properties. This is rather to replace traditional polymers than steel or wood. Therefore the scale production of multiphase/multicomponent materials, and the establishment of new processing methods has increased.

Morphology represents a decisive factor, which controls various practical properties such as transparency or impact strength in multicomponent polymeric materials [45]. Cocontinuous structures, which are formed by polymeric materials, have been of interest to material oriented scientists due to their ascendancy over those with a random structural morphology [46,47]. Although many techniques for producing polymer materials with cocontinuous structures were developed such as the violent freezing of the spinoidal structures of polymer blends [48–51], an effective technique to control their regularity is missing. A technique based on periodic photocrosslinking was demonstrated allowing for the distribution of the length-scale of the spinoidal structures in binary polymer blends to be controlled. The distribution period of the resulting cocontinuous structures is narrow when it is forced. Additionally, a particular irradiation frequency is present where the periodic structures exhibit a minimum, confirming the presence of an ordering process that is driven by the modulation frequency (external). These findings led to the discovery of an effective and easy way to produce polymeric materials that are promising for applications related to biological separation (hemodialysis) and useful for optical applications as well as [52].

2.2.5 Polymer composites

Composites represent those materials that consist of two or more constituents and contain some reinforced components (fibers or particles) in a polymeric matrix. Reinforced materials are distributed and arranged in the polymeric matrix in a specific pattern to achieve unique properties for specific applications. The reinforced materials are held by the matrix to sustain a relative position. Simple commodity plastics based on polymer composites are commonly used in a broad range of products such as food packaging, bottles, cups, aerospace/aviation structures, electromagnetic shielding coatings, and biomedical coatings. Understanding the morphology of polymer composites is necessary to tailor the functional properties since a hierarchical morphology is usually implemented during processing, especially in polymer-containing particles [53,54]. These properties extend from the nanometer scale (nanoparticles, crystalline lamella) to the micrometer scale (homogeneity, domains) to the macroscale (surface and mechanical properties) and are essential for the development of novel materials and the enhancement of processing conditions [55].

Based on the reinforcing material, there are two main categories of polymers, namely particle-reinforced and fiber-reinforced polymer composites. The particles are used as reinforcing agents in particle-reinforced polymer composites. The particles, which are dispersed in the polymer matrix as a reinforcing agent, include glasses, ceramics, metals as well as organics. The size of the dispersing particles in these composites may vary from a few micrometers to several tens of micrometers; the size range in nanocomposites ranges from hundreds of nanometers to 10 nm. A large particle distribution is enabled by the high filler contents because of the small space between the large particles [35]. A small particle diameter, in the range of 10–100 nm, is used for the dispersant strengthening of composites. The shape of the particles vary with application and can be layered, spherical, or irregular [56]. The particles used in these composites can have a variety of geometries, but the dimensions of all the sides should be approximately the same (equiaxed). To achieve effective reinforcement, the particles should be small is size and evenly distributed in the matrix. Mineral-based particles are usually utilized for the improvement of surface hardness, matrix modulus, and abrasion and wear resistance; for the improvement of performance at increased temperatures; and for a reduction of friction, shrinkage, and the permeability of the matrix. Metallic particles are predominantly used for the improvement of the electrical conductivities of insulating matrices of polymeric materials. Carbon nanotube (CNT)-reinforced polymers are used in numerous applications such as actuators, textiles, microfluidic devices, biomedical implants, and lightweight structures [57–61]. CNTs incorporated in polymeric composites cause improvements in thermal, electrical, and mechanical properties [60,61].

2.3 Characterization methods

This section is focused on characterization methods of polymer morphologies. The methods and techniques can be divided into two main groups depending on the way the polymer morphology is observed, namely indirect (structural, nonstructural) and direct methods. For the structural analysis of polymer morphology, small angle X-ray scattering (SAXS), X-ray diffraction (XRD), or angle light scattering (SALS) can be used. Kinetic dynamic mechanical analyses (DMA) or thermodynamic differential scanning calorimetry (DSC) represent methods for the nonstructural direct observation of polymer morphology. In contrast, most microscopic techniques can be used for the direct observation of polymer morphology or topography, for example, optical microscopy (OM), SEM, TEM, scanning tunneling microscopy (STM), or AFM.

2.3.1 Indirect observation methods

Some methods can be categorized as indirect testing methods because they are not visualizing tools in which the polymer morphology is imaged by some means. Rather, these techniques provide information on the polymer morphology indirectly. For instance, the shape of an XRD [62,63] peak gives an indication of the phase, whether it is amorphous, crystalline, or semicrystalline. Similarly, in DSC, the appearance of a crystallizing point/temperature (Tc) reveals that the given polymer has amorphous fragments that are crystallizable. This is extremely useful information when studying blends because some polymers do not crystallize in certain polymer matrices. Techniques such as XRD, SALS [64], and SAXS [65–67] are referred to as structural techniques, while DSC [68,69] and DMA [70,71] provide nonstructural details of polymer materials. DSC is employed when the thermodynamics of the polymerization of neat polymers, copolymers, or polymer blends is studied. These techniques are described and discussed in detail here.

2.3.1.1 X-ray diffraction

XRD is a nondestructive technique, which means that the sample is not destroyed during analysis. During XRD, a monochromatic X-ray beam strikes a sample at different angles, usually starting from a θ value equal to 2.5–50 degrees (or 2θ equal to 5–100 degrees). This results in either constructive or destructive interference. Constructive interference between an atom in a particular lattice plane with the incident monochromatic radiation leads to a diffracted X-ray (Fig. 2.3). This diffracted X-ray is detected and processed, and the data are recorded and displayed via data acquisition software. Constructive interference occurs when the X-ray beam is incident on a specific set of crystallographic planes with a particular lattice spacing and forms a peak in the diffractogram. The appropriate relationship among these parameters is given by Bragg’s law (Eq. (2.1)).

(2.1)

where ƛ is the wavelength of the X-ray, d is the interlayer spacing, and θ is the incident angle.

Figure 2.3 Scheme of (A) diffractometer apparatus and (B) diffraction by particles (atoms) in parallel lattice planes.

Each different lattice plane produces a constructive interference at a certain angle and technically displays a separate peak for every single plane of a crystalline sample. XRD provides an initial indication of crystallinity and also details whether it is a neat polymer or a composite blend of two phases such as polymer–polymer [72], polymer–wax, or polymer–metal/metal oxide [73–75]. The crystallinity of a polymer is different from that of a metal or metal oxide lattice material. By definition, a crystalline material maintains a regular arrangement and orientation. XRD is indicative of the unit cell type, and for a polymer, a unit cell is a repeating segment of polymer chain. Polymer chains may consist of several tens or even hundreds of carbon atoms in a single