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Review

Polymer Nanocomposites

by
Masami Okamoto
Advanced Polymeric Nanostructured Materials Engineering, Graduate School of Engineering, Toyota Technological Institute, 2-12-1 Hisakata, Tempaku, Nagoya 468 8511, Japan
Eng 2023, 4(1), 457-479; https://doi.org/10.3390/eng4010028
Submission received: 30 November 2022 / Revised: 11 January 2023 / Accepted: 26 January 2023 / Published: 1 February 2023
(This article belongs to the Special Issue REPER Recent Materials Engineering Performances)
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Abstract

:
In the last 20 years, there has been a strong emphasis on the development of polymer nanocomposites, where at least one of the dimensions of the filler material is of the order of a nanometer. Polymer nanocomposites are fundamentally different from traditional filled polymers because of the immense internal interfacial area and the nanoscopic nature of the nanomaterials. The new multifunctional properties derived from the nano-structure of nanocomposites provide an opportunity to circumvent the traditional properties associated with traditional composites. Numerous examples can be found in the literature that show significant improvements in multifunctional properties of the nanocomposites and this new class materials now being introduced in structural applications, such as gas barrier film, flame retardant product, and other load-bearing applications. This review offers a comprehensive review on the basic concept, technology and application for polymer nanocomposites.

Graphical Abstract

1. Introduction

For the past five decades, we have devoted ourselves to macrocomposites, such as filler reinforced polymer matrix composites, in which the length scale of the filler or the fiber diameters is in micrometers (Figure 1). Polymer composites are manufactured commercially for many diverse applications, such as automobiles, sporting goods, aerospace components, and so on. Over the last 20 years, we have been discovering polymer nanocomposites [1], where the length scale of the reinforcement (nanomaterials) is on the nanometer scale, as shown in Figure 1. Polymer nanocomposites have the potential to significantly impact growth at every level of the world economy in the 21st century. This surge in the field of polymer composites has been greatly facilitated by the advent of scanning tunneling microscopy and scanning probe microscopy in the early 1980s.
The nano-filler (nanomaterials) in the polymer nanocomposites have ultra-large interfacial area per unit volume, and distances between the filler and filler components (correlation length ξ) are close to polymer random coil/chain size with 20 nm in diameter [2]. In addition, the nano-fillers are on the same order of magnitude as the polymer coil. At the same time, the correlation length between filler particles ξ is smaller than the average value of the particle diameter D (ξ ≤ D) with increasing filler content, indicating the formation of the highly geometric constraints. That is, the spatial-linked-like structure of the dispersed filler particles is formed [3]. Low concentrations necessary to influence in a matrix polymer have generated much interest in the field of the polymer nanocomposites. As a result, very unusual material properties are induced by molecular interaction between polymer coils/chains and nano-fillers. This is not possessed in the conventional macrocomposites. Furthermore, we can fabricate and process many polymeric nanocomposites via a similar way of conventional polymer-based macrocomposites, indicating them to be particularly attractive from a manufacturing point of view [1].

2. Nanomaterials

In the case of particles, platelets, or fibers, the surface area per unit volume is inversely proportional to the material’s diameter D. The surface/volume ratio R is 6/D. The smaller the diameter, the larger the surface area per unit volume. Figure 2 shows common particle geometries and their value of R [4]. For the fiber and layered (platelet) materials, the first term in the equation is dominant, but second term (2/l and 4/l) has very small effect as compared with the first term. Therefore, a change in D from the micrometer to nanometer range affects the value of R by three orders of magnitude [4].
Typical nano-fillers under investigation include, nanoparticles, nanotubes, nanofibers, fullerenes, and nanowires, where are classified into three classes by their geometries, such as one-, two-, or three-dimensional nanoscale materials, as shown in Figure 2 [5,6]. Figure 3 shows the schematic illustration of several nano-fillers with dimensions. Silica, nano-silicon carbide (n-SiC), carbon black, fullerens, polyhedral oligomeric sislesquioxanes (POSS), allophane nanoball are classified as nanoparticle reinforcing agents. Carbon nanofibers, carbon nanotubes and nanofibers (halloysite, nickel nanostrand: NiNs) are fibrous materials. In the case of the filler having a nanometer thickness and a high aspect ratio (50–1000) platelet structure, it is classified as a layered nanomaterial, such as an organically modified layered silicate (Figure 3) [1,3,5].
Eng 04 00028 g002 550
Figure 2. Common particle reinforcements/geometries and their respective surface area-to-volume ratios R. Source: Reproduced with permission from [6]. © 2005, Elsevier Ltd.
Figure 2. Common particle reinforcements/geometries and their respective surface area-to-volume ratios R. Source: Reproduced with permission from [6]. © 2005, Elsevier Ltd.
Eng 04 00028 g002

3. Multifunctional Properties

Polymer nanocomposites have interphases that dominate the composite properties due to the very small size of the nano-filler component. For nano-fillers, at least one dimension is on the nanometer scale, as shown in Figure 2 and Figure 3. The polymers are thermoplastic, thermoset, or rubber and elastomer. The polymer–nano-filler interface is the dominant factor for the nanocomposite properties. The interaction between the polymer molecule is entirely a molecular-level interaction. The surface chemistry and bulk mixing dynamics have affected the incorporation of nanoparticles into the polymer matrix. Since the invention of polymer nanocomposite in 1993 [7], polymer nanocomposites have become an important class of materials that offer superior properties as compared with those of conventional macrocomposites. A new property is the multifunctional properties that extend their scope of application to new areas.
This new class of materials is now being introduced in structural applications, such as gas barrier film, flame retardant product, and other load-bearing applications (Figure 4). The polymer nanocomposites exhibit other property enhancement such as thermal (stability and conductivity) ablation, electrical, optical, tribological, chemical resistance. These multifunctional properties of polymer nanocomposites are discussed in detail in the literature [8,9,10,11,12,13,14,15,16,17,18]. It is a very complex matter to understand the reason why the property enhancement takes place in polymer nanocomposites. Table 1 summarizes the advantages/disadvantages to illustrate this point in new material.
The researchers of Toyota Central Research & Development (TCRD) reported work based on Nylon-6-clay nanocomposites [7]. The resulting composite with a loading of only 4.2 wt% organically modified layered silicate possessed a double modulus, a 50% enhanced strength, and an increase in heat distortion temperature of 80 °C, as compared with the neat Nylon-6 [19]. In recent years, for nanocomposite fabrication, organically modified layered silicate (organoclay) has been used in various polymer systems including epoxy, polyurethanes, and so on [1].
The US Army research laboratory investigated the ballistic impact strength of polycarbonate-layered silicate nanocomposites [6,20]. Nanocomposites showed an important role in longer-range missiles. Koo and colleague investigated the nanocomposites for high-temperature application by cyanate ester, epoxy, phenolic, nylon-11, etc., and the feasibility of using these materials for fire retardant coating, rocket production insulation, rocket nozzle ablative materials, damage tolerant performance [21]. Nanoclay plays an important role in reducing the flammability of coating system for solid rocket exhaust plumes (3600 °C) at very high velocity. Flammability enhancement by organoclay is an important issue for many applications as compared to pure polymer systems [1].
NASA Langley Center developed transparent nanocomposites with organically modified layered silicate. Those are lightweight and durable and suitable for aerospace applications [6,22]. Using nanoclays in carbon fiber/epoxy reinforced composites cryogenic storage system has been developed [23]. Both mechanical and thermal expansion characteristics were improved to avoid micro cracking and thermal cycling because of the temperature range from –196 to 125 °C for space application.

4. Structure and Characterization Techniques for Nanocomposites

Nanomaterials provide reinforcing efficiency with their high aspect ratio. The properties of a nanocomposite are greatly affected by the size scale of the component phases and the degree of mixing between the two phases. Depending on the nature of the components used (layered silicate or nanofiber) and the method of preparation, the obtained properties may be different [1].
Of particular interest has been recently developed nanocomposites consisting of a polymer and layered silicate because they often exhibit remarkably improved mechanical and various other properties [1,3,5,8], as compared with pure polymer or conventional macrocomposites. Layered silicates have a layer thickness in the order of 1 nm and very high aspect ratio (e.g., 10–1000). Therefore, a few weight percent of layered silicate properly dispersed throughout the polymer matrix provides a much larger surface area for polymer/filler interaction than conventional composites. Depending on the strength of interfacial interaction between polymer matrix and layered silicate (modified or not), three different types of polymer-layered silicate (PLS) nanocomposites are thermodynamically achievable (Figure 4).
(1) Intercalated nanocomposites: in an intercalated nanocomposite, the insertion of polymer matrix into the layered silicate structure occurs in a crystallographically regular fashion, regardless of the silicate layer (clay) to polymer ratio. Properties of the composites typically resemble those of ceramic materials.
(2) Flocculated nanocomposites: conceptually this is same with intercalated nanocomposites; however, silicate layers are sometimes flocculated due to hydroxylated edge–edge interaction of the silicate layers. The length of the oriented collections in the range of 300–800 nm is far larger than the original silicate layer (mean diameter 150 nm) [24]. Such flocculation presumably is governed by an interfacial energy between polymer matrix and organoclays and controlled by ammonium cation-matrix polymer interaction. The polarity of the matrix polymer is of fundamental importance in controlling the nanoscale structure.
(3) Exfoliated nanocomposites: in exfoliated nanocomposites, the individual silicate layers are separated in a continuous polymer matrix by an average distance that is entirely dependent on the layered silicate loading. Usually, the clay content of an exfoliated nanocomposite is much lower than that of intercalated nanocomposites.
The preparative methods are broadly classified into three main categories.
(1)
Intercalation of polymer or pre-polymer from solution
This is based on a solvent system in which polymer or pre-polymer is soluble and the silicate layers are swellable. The layered silicate is first swollen in a solvent, such as water, chloroform or toluene, etc. When the polymer and layered silicate solutions are mixed, the polymer chains intercalate and displace the solvent within the interlayer of the silicate. Upon solvent removal, the intercalated structure remains, resulting in polymer-layered silicate (PLS) nanocomposites.
(2)
In situ intercalative polymerization method
In this method, the organically modified layered silicate is swollen within the liquid monomer or a monomer solution so as the polymer formation can occur in between the intercalated sheets. Polymerization can be initiated either by heat or radiation, by the diffusion of a suitable initiator or by an organic initiator or catalyst fixed through cation exchange inside the interlayer before the swelling step by the monomer.
(3)
Melt intercalation method
This method involves annealing, statically or under shear, a mixture of the polymer and organically modified layered silicate above the softening point of the polymer. This method has great advantages over either in situ intercalative polymerization or polymer solution intercalation. Firstly, this method is environmentally benign due to the absence of organic solvents. Secondly, it is compatible with current industrial processes, such as extrusion and injection molding. Melt intercalation method allows the use of polymers which were previously not suitable for in situ polymerization or solution intercalation method. Other possibilities are exfoliation adsorption, and template synthesis [1,13]. Nowadays, this solvent-free method is much preferred for practical industrial material production by its high efficiency and possibility of avoiding environmental hazards.
Analogously, in fibrous or particle-reinforced polymer nanocomposites, dispersion of the nanoparticle and adhesion at the particle–matrix interface play pivotal roles in determining the mechanical properties of the nanocomposite. Without proper dispersion, the nanomaterial will not offer improved mechanical properties over that of conventional composites, in fact, a poorly dispersed nanomaterial may degrade the mechanical properties [1]. Graphite and graphene platelets have a similar geometry (layered sheet structure) with clay; therefore, a clay polymer reinforcement concept is also applicable. Additionally, optimizing the interfacial bond between the particle and the matrix, one can tailor the properties of the overall composite, similar to what is performed on macrocomposites. For example, good adhesion at the interface will improve properties such as interlaminar shear strength, delamination resistance, fatigue, and corrosion resistance.
Various techniques for nanocomposite characterization have been employed. The structure of the nanocomposites has typically been established using a Wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) analysis, scanning electron microscopy (SEM), and transmission electron microscope (TEM) observation [1,16]. The structure of the PLS nanocomposites has typically been established using WAXD analysis and TEM observation. Due to its easiness and availability WAXD is most commonly used to probe the PLS nanocomposite structure and sometimes to study the kinetics of the polymer melt intercalation [1,16]. By monitoring the position, shape, and intensity of the basal reflections from the distributed silicate layers, the nanocomposite structure either intercalated or exfoliated may be identified. For example, in case of exfoliated nanocomposites, the extensive layer separation associated with the delamination of the original silicate layers in the polymer matrix results in the eventual disappearance of any coherent X-ray diffraction from the distributed silicate layers.
On the other hand, for intercalated nanocomposites, the finite layer expansion associated with the polymer intercalation results in the appearance of a new basal reflection corresponding to the larger gallery height. Although, WAXD offers a convenient method to determine the interlayer spacing of the silicate layers in the original layered silicates and in the intercalated nanocomposites (within 1–4 nm); however, little can be said about the spatial distribution of the silicate layers or any structural in-homogeneities in the PLS nanocomposites.
Additionally, some layered silicates initially do not exhibit well-defined basal reflection. Thus, peak broadening and intensity decreases are very difficult to study systematically. Therefore, conclusions concerning the mechanism of nanocomposites formation and their structure based solely on WAXD patterns are only tentative. On the other hand, TEM allows a qualitative understanding of the internal structure, spatial distribution of the various phases, and defect structure through direct visualization. However, special care must be exercised to guarantee a representative cross section of the sample.
With SEM, we can obtain images of surface features associated with a sample. In addition, two other microscopies, scanning probe microscopy (SPM) and scanning tunneling microscopy (STM) are useful to analyze nanotube research [16]. The SPM uses the interaction between a sharp tip and a surface to obtain an image. For STM, a sharp conducting tip is held sufficiently close to a surface (typically ~0.5 nm), such that electrons can ‘tunnel’ across the gap [16]. This method provides surface structural and electronic information at atomic level. The invention of the STM inspired the development of other ‘scanning probe’ microscopes, such as atomic force microscope (AFM) [16]. The AFM uses a sharp tip to scan the entire sample. Raman spectroscopy has also proven to be a useful probe for carbon-based material properties [16].

5. Types of Polymers so far Used for Polymer–Layered Silicate (PLS) Nanocomposites

Before describing commercial examples of polymer nanocomposites, we summarize the large variety of polymer systems that have so far been used in nanocomposites preparation with layered silicate can be conventionally classified as below (Table 2, Table 3, Table 4, Table 5 and Table 6).
Several technologically important polycondensates and rubbers have also been used in the nanocomposite preparation with layered silicate (Table 3).
Polyolefines such as polypropylene (PP) and polyethylene (PE) have been used and are shown in Table 4.
In addition to the above-mentioned conventional polymers, several interesting developments have also taken place in the preparation of PLS nanocomposites with some specialty polymers (Table 5).
Today, tremendous amounts and varieties of plastics, notably polyolefin, polystyrene and poly (vinyl chloride), are currently produced mostly from fossil fuels, consumed and discarded into the environment, ending up as spontaneously undegradable wastes. Their disposal by incineration always produces large amounts of CO2 and contributes to global warming, and some but not all of them even release toxic gases and again makes global pollution. For these reasons, there is an urgent need for the development of “green polymeric materials” that would not involve the use of toxic or noxious components in their manufacture and could allow to be composted to naturally occurring degradation products. Accordingly, polylactide (PLA) is of increasing commercial interest because it is made from renewable sources and readily biodegradable.
Okamoto and colleagues [24] have started the preparation, characterization and materials properties of various kinds of biodegradable polymers/layered silicate nanocomposites having properties suitable for a wide-range of applications (Table 6).

6. Commercial Market Opportunities

The first commercial example of polymer nanocomposites in automotive applications was nylon-6–clay nanocomposites used for making timing belt covers (the Toyota Motor Company, 1991) [352]. More significantly, these nanocomposites were used in under the hood application in the Toyota Camry [20]. Related to the early successful development, General Motors Corporation (GMC) developed a step assist component for 2002 GMC Safari and Chevrolet Astro vans, which are made of thermoplastic polyolefin–clay nanocomposite. This nanocomposite showed lighter and stiffer, more robust at low temperatures, and easily recyclable. GMC also tried to use these nanocomposites in the lateral protection wire of the 2004 Cherolet Impala and 2005 Hummer H2 cargo because they are 7% lighter in weight and present a better surface appearance (Figure 5a,c,d).
Putsch and Sud-Chemie jointly prepared Elan XP, a compound of polypropylene and polystyrene compatibilized by clay, which is used as an interior air vent for the Audi A4 and a Volkswagen van (Figure 5f).
InMat Inc. has developed several applications for their nanocomposite coatings. The nanocomposite coating of the Wilson tennis balls maintains the internal pressure for an extended period of time (Figure 5h). The Wilson tennis balls have a double core, which is coated by a polymer–clay nanocomposite which acts as a gas barrier, doubling the ball’s shelf life. This technology was extended to the rubber industry and was incorporated into soccer balls or into bicycle tires.
The barrier properties of polymer nanocomposite have also been extended to liquid or molecule, such as water, since these liquids are responsible for polymer deterioration in some instances. Ube Industries reveal significant reduction in fuel transmission via polyamide-6/66 polymers by incorporation of nano-clay particles, resulting in reduced fuel emission for fuel tank and fuel line components (Figure 5b).
Improvement in barrier resistance in nanocomposites plays an important role in beverage applications. When the layers are delaminated, it increases the effective path length for molecular diffusion and the path becomes highly tortuous to reduce the effect of gas and moisture transmission through the film [1]. Based on the barrier properties, nanocomposite packaging films made in PET have been studied as replacements for conventional polymer films [24]. Coor Inc. developed commercial PET–clay nanocomposite product for beer bottles (Figure 5i). Unitika Ltd. developed PLA–clay nanocomposite for bottle applications [24].
Thermal stability and fire retardancy have been investigated for commodity polymers. Due to the good flame retardancy of polymer–clay nanocomposite materials, Nexans’ introduced cable jacketing nanocomposite, the first such product for plenum cable used in office buildings (Figure 5g).
In some cases, the value of polymer nanocomposites technology relates to value-added performance of medical and agricultural applications not present in neat polymer but occurs via the low-volume introduction of organically modified clay nanoparticles. For example, Geoflow’s linear low-density polyethylene–clay nanocomposite drip emitter for irrigation tubing ensures timed release of herbicide from the plastic (Figure 5e).

7. Future Outlook

The potential of nanocomposites in various sectors of research and application is promising in many parts of the world. With only moderate success in the last two decades, researchers need to continue exploring strategies for optimization. Until now, there are some niche applications where nanotechnology is in the market, but the main impact is at least 10 years away [354].
Biodegradable polymer-based nanocomposites have a great deal of future promise for potential applications as high-performance biodegradable materials. These are entirely new types of materials based on plant and nature materials (organoclay). When disposed of in compost, these are safely decomposed into CO2, water, and humus through the activity of microorganisms. The CO2 and water will become corn or sugarcane again through plant photosynthesis. Undoubtedly, their unique properties originating from the controlled nanostructure paves the way for a much broader range of applications (already commercially available through Unitika Ltd., Japan), and opens a new dimension for plastics and composites [24].
Sustainability needs to be further enhanced based on the Life Cycle Assessment (LCA) presented in the study on biodegradable polymer-based nanocomposites. On the other hand, to enable complete recycling, society must also require manufacturers to present LCA and assessment results comparable to research efforts on all environmental impacts of nanocomposite materials.

Funding

This work was supported by the TTI Grant (Special Research Project: FY2021).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The raw/processed data required to reproduce these findings cannot be shared at this time as the data also forms part of an ongoing study.

Conflicts of Interest

The author has declared that no competing interests exist.

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Figure 1. Typical particle reinforcements/geometries in nano- and macro-composites. The correlation length between filler particles ξ is smaller than average value of the particle diameter D (ξ ≤ D) with increasing filler content. In general, the ξ value (≅30 nm) corresponds to the random coil size of polymer. The root-mean-square radius of gyration <S2>1/2 is around 10 nm, which is calculated by <S2>1/2 = 4.0 × 10−2 Mw1/2 [2]. The polymeric chain mobility presumably is decreased in translational motion. The morphological difference comes from the loading amount of filler particles.
Figure 1. Typical particle reinforcements/geometries in nano- and macro-composites. The correlation length between filler particles ξ is smaller than average value of the particle diameter D (ξ ≤ D) with increasing filler content. In general, the ξ value (≅30 nm) corresponds to the random coil size of polymer. The root-mean-square radius of gyration <S2>1/2 is around 10 nm, which is calculated by <S2>1/2 = 4.0 × 10−2 Mw1/2 [2]. The polymeric chain mobility presumably is decreased in translational motion. The morphological difference comes from the loading amount of filler particles.
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Figure 3. Schematic illustration of several nano-fillers (nanomaterials) with dimension. Polyhedral oligomeric sislesquioxanes (POSS), carbon nanotubes (single-wall nanotube (SWNT) and multi-wall nanotube (MWNT)), nanofiber (halloysite), nanoneedle (sepiolite), nanoballs (fullerens, allophane), layered nanomaterials (layered silicate, layered titanate), and silicon carbide (SiC).
Figure 3. Schematic illustration of several nano-fillers (nanomaterials) with dimension. Polyhedral oligomeric sislesquioxanes (POSS), carbon nanotubes (single-wall nanotube (SWNT) and multi-wall nanotube (MWNT)), nanofiber (halloysite), nanoneedle (sepiolite), nanoballs (fullerens, allophane), layered nanomaterials (layered silicate, layered titanate), and silicon carbide (SiC).
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Figure 4. Schematic illustration of three different types of thermodynamically achievable polymer–layered silicate nanocomposites. Reproduced with permission from [1]. © 2003, Elsevier Ltd.
Figure 4. Schematic illustration of three different types of thermodynamically achievable polymer–layered silicate nanocomposites. Reproduced with permission from [1]. © 2003, Elsevier Ltd.
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Figure 5. (a) Toyota and Mitsubishi engine covers and (b) gasoline tank injection-molded from polyamide-6/clay nanocomposites. (c) GMC’s Chevrolet Impala 2004: nanocomposite application and (d) Polypropylene/EPDM-based nanocomposite: GMC’s 2005 Hummer H2 cargo bed uses ~7 lb, Trough the courtesy of M. Verbrugge, General Motors Corporation (GMC). (e) Geoflow’s linear low-density polyethylene/clay nanocomposite drip emitter for irrigation tubing ensures timed release of herbicide from the plastic. (f) Putsch and Sud-Chemie jointly prepared Elan XP, a compound of polypropylene and polystyrene compatibilized by clay, which is used as an interior air vent for the Audi A4 and a Volkswagen van. (g) Due to the good flame retardancy of polymer/clay materials, Nexans’ introduced cable jacketing nanocomposite, the first such product for plenum cable used in office buildings. (h) Wilson’s double-core tennis balls uses. (i) Coor’s beer bottles. (j) Low O2 gas permeability poly(L-lactic acid) bottles from Unitika Ltd. [353].
Figure 5. (a) Toyota and Mitsubishi engine covers and (b) gasoline tank injection-molded from polyamide-6/clay nanocomposites. (c) GMC’s Chevrolet Impala 2004: nanocomposite application and (d) Polypropylene/EPDM-based nanocomposite: GMC’s 2005 Hummer H2 cargo bed uses ~7 lb, Trough the courtesy of M. Verbrugge, General Motors Corporation (GMC). (e) Geoflow’s linear low-density polyethylene/clay nanocomposite drip emitter for irrigation tubing ensures timed release of herbicide from the plastic. (f) Putsch and Sud-Chemie jointly prepared Elan XP, a compound of polypropylene and polystyrene compatibilized by clay, which is used as an interior air vent for the Audi A4 and a Volkswagen van. (g) Due to the good flame retardancy of polymer/clay materials, Nexans’ introduced cable jacketing nanocomposite, the first such product for plenum cable used in office buildings. (h) Wilson’s double-core tennis balls uses. (i) Coor’s beer bottles. (j) Low O2 gas permeability poly(L-lactic acid) bottles from Unitika Ltd. [353].
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Table
Table 1. Advantages/disadvantages of polymer nanocomposites.
Table 1. Advantages/disadvantages of polymer nanocomposites.
Improved PropertiesDisadvantages
Mechanical properties (tensile strength, Melt viscosity increase
stiffness, toughness) Dispersion difficulties of nano-fillers
Gas permeabilityHaze properties
Free volume reduction in matrix polymerSedimentation
Heat resistanceColor issues
Flame retardant Cost of creating nano-fillers
Dimensional stabilitySafety of nano-fillers
Thermal expansion
Electrical conductivity
Proton conductivity
Field emission
Ablation resistance
Chemical resistance
Optical properties
Biodegradability
Crystallization control
Rheological properties
Processability
Table
Table 2. Vinyl polymer classification.
Table 2. Vinyl polymer classification.
Vinyl Polymer SystemsReferences
methyl methacrylate (MMA)[25,26,27,28,29,30,31,32,33,34,35,36,37,38]
MMA copolymers[39,40,41,42]
polyacrylates[43,44,45]
polyacrylic acid[46,47]
polyacrylonitrile (AN)[48,49,50,51]
polystyrene (S)[52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69,70,71,72,73,74,75,76,77]
4-vinylpyridine[78]
polyacrylamide[79,80,81]
polytetrafluoro ethylene[82]
poly(vinyl alcohol)[83,84,85,86]
poly(N-vinyl pyrrolidone)[87,88,89,90,91]
poly(vinyl pyrrolidinone)[92,93]
poly(vinyl pyridine)[94]
poly(ethylene glycol)[95]
poly(ethylene vinyl alcohol)[96]
poly(vinylidene fluoride)[97]
poly(p-phenylenevinylene)[98]
polybenzoxazole[99]
poly(S-co-AN)[100]
ethyl vinyl alcohol copolymer[101]
PS-polyisoprene diblock copolymer[102,103]
other[104]
Table
Table 3. Condensation polymers and rubbers classification.
Table 3. Condensation polymers and rubbers classification.
Condensation Polymer SystemsReferences
Nylon-6[6,18,105,106,107,108,109,110,111,112,113,114,115,116,117,118,119,120,121,122,123,124,125,126,127]
Other polyamides[128,129,130,131,132,133,134]
poly(ε-caprolactone) (PCL)[135,136,137,138,139,140,141,142,143,144,145,146]
Poly(ethylene terephtalate) (PET)[147,148,149,150,151,152,153]
poly (trimethylene terephthalate)[154,155]
poly(butylene terephthalate)[156]
polycarbonate[157,158]
Polyethylene oxide[159,160,161,162,163,164,165,166,167,168,169,170,171,172,173,174,175,176,177,178,179]
polyethylene oxide copolymers[180,181]
poly (ethylene imine)[182]
poly (dimethyl siloxane)[183,184,185,186,187,188]
polybutadiene[189]
polybutadiene copolymers[190,191,192]
epoxidized natural rubber[193,194]
epoxy polymer resins[195,196,197,198,199,200,201,202,203,204,205,206,207,208,209,210,211,212,213,214,215,216]
phenolic resins[217,218]
polyurethanes[219,220,221,222,223]
polyurethane uera[224]
polyimides[225,226,227,228,229,230,231,232,233,234,235,236,237,238,239,240]
poly(amic acid)[241,242]
polysulphone[243]
polyetherimide[244,245]
fluoropoly(ether-imide)[246]
Table
Table 4. Polyolefines classification.
Table 4. Polyolefines classification.
PolyolefinesReferences
PP[247,248,249,250,251,252,253,254,255,256,257,258,259,260,261,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280,281,282,283,284]
PE[285,286,287,288,289,290,291,292,293,294]
PE oligomers[295]
poly(ethylene-co-vinyl acetate) [296]
ethylene propylene diene methylene linkage[297]
poly(1-butene)[298]
Table
Table 5. Specialty polymers.
Table 5. Specialty polymers.
Specialty PolymersReferences
polypyrrole[299,300,301,302,303,304]
poly (N-vinylcarbazole)[305,306]
polyaniline[307,308,309,310,311,312,313,314,315,316,317,318,319,320]
poly(p-phenylene vinylene)[321]
liquid crystalline polymers[322,323,324,325,326]
hyper branch polymers[327]
cyanate ester[328]
Nafion®[329]
Aryl-ethany-terminated imide oligomer[330]
Table
Table 6. Biodegradable polymers.
Table 6. Biodegradable polymers.
Biodegradable PolymersReferences
Polylactide (PLA)[24,331,332,333,334,335,336,337,338,339,340]
poly (butylene succinate)[341,342,343]
PCL[135,136,137,138,139,140,141,142,143,144,145,146]
unsaturated polyester[344]
polyhydroxy butyrate[345,346,347]
aliphatic polyester[348,349,350,351]
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Okamoto, M. Polymer Nanocomposites. Eng 2023, 4, 457-479. https://doi.org/10.3390/eng4010028

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Okamoto M. Polymer Nanocomposites. Eng. 2023; 4(1):457-479. https://doi.org/10.3390/eng4010028

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Okamoto, Masami. 2023. "Polymer Nanocomposites" Eng 4, no. 1: 457-479. https://doi.org/10.3390/eng4010028

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