Polymer/layered silicate nanocomposites: a review from preparation to processing

This review aims at reporting on very recent developments in syntheses, properties and (future) applications of polymer-layered silicate nanocomposites. This new type of materials, based on smectite clays usually rendered hydrophobic through ionic exchange of the sodium interlayer cation with an onium cation, may be prepared via various synthetic routes comprising exfoliation adsorption, in situ intercalative polymerization and melt intercalation. The whole range of polymer matrices is covered, i.e. thermoplastics, thermosets and elastomers. Two types of structure may be obtained, namely intercalated nanocomposites where the polymer chains are sandwiched in between silicate layers and exfoliated nanocomposites where the separated, individual silicate layers are more or less uniformly dispersed in the polymer matrix. This new family of materials exhibits enhanced properties at very low filler level, usually inferior to 5 wt.%, such as increased Young’s modulus and storage modulus, increase in thermal stability and gas barrier properties and good flame retardancy.

Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials

Polymer nanocomposites with layered silicates as the inorganic phase (reinforcement) are discussed. The materials design and synthesis rely on the ability of layered silicates to intercalate in the galleries between their layers a wide range of monomers and polymers. Special emphasis is placed on a new, versatile and environmentally benign synthesis approach by polymer melt intercalation. In contrast to in-situ polymerization and solution intercalation, melt intercalation involves mixing the layered silicate with the polymer and heating the mixture above the softening point of the polymer. Compatibility with various polymers is accomplished by derivatizing the silicates with alkyl ammonium cations via an ion exchange reaction. By fine-tuning the surface characteristics nanodispersion (i. e. intercalation or delamination) can be accomplished. The resulting polymer layered silicate (PLS) nanocomposites exhibit properties dramatically different from their more conventional counterparts. For example, PLS nanocomposites can attain a particular degree of stiffness, strength and barrier properties with far less inorganic content than comparable glass- or mineral reinforced polymers and, therefore, they are far lighter in weight. In addition, PLS nanocomposites exhibit significant increase in thermal stability as well as self-extinguishing characteristics. The combination of improved properties, convenient processing and low cost has already led to a few commercial applications with more currently under development.

Polymer Layered Silicate Nanocomposites

https://cyberleninka.org/article/n/1018032.pdf

Polymer nanotechnology: Nanocomposites

http://staff.ulsu.ru/moliver/ref/polymers/pott11.pdf

Graphene-based polymer nanocomposites

Various nylon 6-clay hybrids, such as molecular composites of nylon 6 and silicate layers of montmorillonite and saponite, NCH's and NCHP's, respectively, have been synthesized. To estimate the mechanical properties of these hybrids, tensile, flexural, impact, and heat distortion tests were carried out. NCH was found superior in strength and modulus and comparable in impact strength to nylon 6. The heat distortion temperature (HDT) of NCH (montmorillonite: 4.7 wt. %) was 152 °C, which was 87 °C higher than that of nylon 6. In NCHP, saponite had a smaller effect on the increase of these mechanical properties. The modulus and HDT of NCH and NCHP increased with an increase in the amount of clay minerals. It was found that these properties were well described by the contribution of the constrained region calculated from the storage and loss modulus at the glass transition temperature. According to the mixing law on elastic modulus, the following expression was obtained between the modulus E at 120 °C and the fraction of the constrained region C, En = Ecn = C, where the values of n and Ec (modulus of the constrained region) were 0.685 and 1.02 GPa, respectively.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400020537

Mechanical properties of nylon 6-clay hybrid

It was found that montmorillonite cation exchanged for 12-aminolauric acid (12-montmorillonite) was swollen by ∊-caprolactam to form a new intercalated compound. Caprolactam was polymerized in the interlayer of montmorillonite, a layer silicate, yielding a nylon 6-clay hybrid (NCH). The silicate layers of montmorillonite were uniformly dispersed in nylon 6. The carboxyl end groups of 12-aminolauric acid in 12-montmorillonite initiated polymerization of ∊-caprolactam, and as 12-montmorillonite content became larger, the molecular weight of nylon was reduced. From the result of end-group analysis, carboxyl end groups were more than amino end groups. The difference between the carboxyl and the amino end groups was attributed to ammonium cations (-NH3+) of nylon molecules, because the difference agreed with the anion site concentration of the montmorillonite in NCH. It is suggested that the ammonium cations in nylon 6 interact with the anions in montmorillonite.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400020525

Synthesis of nylon 6-clay hybrid

A polyimide hybrid with montmorillonite clay mineral has been synthesized from a dimethylacetamide (DMAC) solution of poly(amic acid) and a DMAC dispersion of montmorillonite intercalated with an ammonium salt of dodecylamine. Montmorillonite consists of stacked silicate sheets about 2000 A in length, 10 A in thickness. In this hybrid, montmorillonite is dispersed homogeneously into the polyimide matrix and oriented parallel to the film surface. Thanks to this special structure, this hybrid showed excellent gas barrier properties. Only 2 wt % addition of montmorillonite brought permeability coefficients of various gases to values less than half of those of ordinary polyimide. Furthermore, this hybrid had low thermal expansion coefficient. © 1993 John Wiley & Sons, Inc.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.1993.080311009

Synthesis and properties of polyimide–clay hybrid

Natural Na-montmorillonite was cation exchanged for the ammonium cations of various ω-amino acids [H3N+(CH2)n−1 COOH, n = 2, 3, 4, 5, 6, 8, 11, 12, and 18]. X-ray diffraction (XRD) results suggested that the chain axes of ω-amino acids with a carbon number of eight or less were parallel to the silicate layers, and that the chain axes of those with a carbon number of 11 or more were slanted to the layers. The cation-exchanged montmorillonites form intercalated compounds with ∊-caprolactam at 25 °C. The montmorillonites intercalated with both ω-amino acid and ∊-caprolactam were studied by XRD measurement at room temperature and 100 °C. We propose a model where amino acid molecules were arranged perpendicular to silicate layers and ∊-caprolactam molecules filled the space between them. When the ∊-caprolactam was melted at 100 °C, the basal spacing for the montmorillonite increased, in which the carbon number exceeds 11. This phenomenon will be applicable to obtaining the nylon 6-clay hybrid, a molecular composite of nylon 6 and montmorillonite.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400020513

Swelling behavior of montmorillonite cation exchanged for ω-amino acids by ∊-caprolactam

It was found that montmorillonite was intercalated with ϵ-caprolactam. X-ray diffraction revealed that the chain axes of the ϵ-caprolactam were parallel to the montmorillonite plates. The intercalated montmorillonite was swollen by molten ϵ-caprolactam at 200°C. ϵ-Caprolactam and 6-aminocaproic acid (accelerator) were polymerized with the intercalated montmorillonite at 260°C for 6 h, yielding a nylon 6-clay hybrid. X-ray diffraction and transmission electron micrography revealed that the silicate layers of the hybrid were uniformly dispersed in the nylon 6 matrix. Mechanical properties of the hybrid were improved. The strength and the modulus of the hybrid increased compared with the previously reported nylon 6 clay-hybrid (NCH) synthesized by montmorillonite intercalated with 12-aminolauric acid. The heat distortion temperature (HDT) of the hybrid was 164°C, which was 12°C higher than that of NCH. © 1993 John Wiley & Sons, Inc.

Osami Kamigaito

Papers

Mechanical properties of nylon 6-clay hybrid

Synthesis of nylon 6-clay hybrid

Synthesis and properties of polyimide–clay hybrid

Swelling behavior of montmorillonite cation exchanged for ω-amino acids by ∊-caprolactam

Synthesis of nylon 6-clay hybrid by montmorillonite intercalated with ε-caprolactam