Effect of cellulose nanofiber-montmorillonite hybrid filler on the melt blending of thermoplastic starch composites.

This study investigated the impact of cellulose nanofibers (CNFs) on montmorillonites (MMTs) exfoliation within thermoplastic starch (TPS) nanocomposites during the melt blending process. TPS nanocomposite films were manufactured using an internal mixer with a controlled ratio of CNFs and MMTs to evaluate the effect of individual and hybrid fillers on the material interactions and characteristics of the TPS composites. The incorporation of hybrid fillers resulted in notable enhancements in torque values and rheological properties, suggesting interactions between the starch, CNFs, and MMTs. The degree of MMT intercalation, obtained via X-ray diffraction analysis, decreased with the addition of CNFs, indicating that CNFs positively impacted MMT exfoliation. Scanning electron microscopy (SEM) images of cryo- and tensile-fractured samples highlighted the effectiveness of CNFs in facilitating MMT exfoliation and reinforcing interactions between the MMTs and TPS matrix. These interactions enhanced the tensile strength and Young's modulus by up to 95.8 % and 278.2 %, respectively, with a 1:1 weight ratio of CNFs to MMTs. Additionally, well-dispersed MMTs within the TPS matrix caused passivation and created tortuous paths, improving the water contact angle and decreasing the water vapor sorption. These synergistic effects of the hybrid filler, achieved through a melt blending process, indicate the potential use of TPS nanocomposites as an eco-friendly packaging material.

Fabrication and Characterization of Hydrophobic Cellulose Nanofibrils/Silica Nanocomposites with Hexadecyltrimethoxysilane.

Cellulose nanofibrils (CNFs) have attracted much attention because of their renewability and potential biocompatibility. However, CNFs are extremely hydrophilic due to the presence of a large number of hydroxyl groups, limiting their use as a water-resistant material. In this work, we controlled the adsorption behavior of silica nanoparticles on the surface of CNFs by adjusting the synthesis conditions. The silica nanoparticle size and packing efficiency on the CNF surface could be controlled by varying the ammonium hydroxide and water concentrations. In addition, hexadecyltrimethoxysilane (HDTMS) was successfully grafted onto CNF or CNF/silica nanocomposite surfaces, and the quantitative content of organic/inorganic substances in HDTMS was analyzed through XPS and TGA. The HDTMS-modified CNF/silica nanocomposites were more advantageous in terms of hydrophobicity than the HDTMS-modified CNF composites. This is because the silica nanoparticles were adsorbed on the surface of the CNFs, increasing the surface roughness and simultaneously increasing the amount of HDTMS. As a result, the HDTMS-modified CNFs showed a water contact angle (WCA) of ~80°, whereas HDTMS-modified CNF/silica nanocomposites obtained superhydrophobicity, with a WCA of up to ~159°. This study can provide a reference for the expansion of recyclable eco-friendly coating materials via the adsorption of silica nanoparticles and hydrophobic modification of CNF materials.

A Study on the Oxygen Permeability Behavior of Nanoclay in a Polypropylene/Nanoclay Nanocomposite by Biaxial Stretching.

Polypropylene (PP) has poor oxygen barrier properties, therefore it is manufactured in a multi-layer structure with other plastics and metals, and has been widely used as a packaging material in various industries from food and beverage to pharmaceuticals. However, multi-layered packaging materials are generally low in recyclability and cause serious environmental pollution, therefore we have faced the challenge of improving the oxygen barrier performance as a uni-material. In this work, PP/nanoclay nanocomposites were prepared at nanoclay contents ranging from 0.8 to 6.4 wt% by the biaxial stretching method, performed through a sequential stretching method. It was observed that, as the draw ratio increased, the behavior of the agglomerates of the nanoclay located in the PP matrix changed and the nanoclay was dispersed along the second stretching direction. Oxygen barrier properties of PP/nanoclay nanocomposites are clearly improved due to this dispersion effect. As the biaxial stretching ratio and the content of nanoclay increased, the oxygen permeability value of the PP/nanoclay nanocomposite decreased to 43.5 cc·mm/m2·day·atm, which was reduced by about 64% compared to PP. Moreover, even when the relative humidity was increased from 0% to 90%, the oxygen permeability values remained almost the same without quality deterioration. Besides these properties, we also found that the mechanical and thermal properties were also improved. The biaxially-stretched PP/nanoclay nanocomposite fabricated in this study is a potential candidate for the replacement of the multi-layered packaging material used in the packaging fields.

Effect of PMMA/Silica Hybrid Particles on Interfacial Adhesion and Crystallization Properties of Poly(lactic acid)/Block Acrylic Elastomer Composites.

Poly(lactic acid) (PLA) is a relatively brittle polymer, and its low melt strength, ductility, and thermal stability limit its use in various industrial applications. This study aimed to investigate the effect of poly(methyl methacrylate) (PMMA) and PMMA/silica hybrid particles on the mechanical properties, interfacial adhesion, and crystallization behavior of PLA/block acrylic elastomer. PLA/block acrylic elastomer blends exhibit improved flexibility; however, phase separation occurs between PLA and block acrylic elastomer domains. Valid time-temperature superposition (TTS) measurements of viscoelastic behavior were obtained and exhibited interfacial adhesion with the addition of PMMA or PMMA/silica in PLA/block acrylic elastomer blends. In particular, the phase separation temperature was increased by the incorporation of PMMA/silica hybrid particles, which suggests a potential role for these particles in improving the phase stability. In addition, PMMA inhibits crystallization, while PMMA/silica acts as a nucleating agent, thus increasing the crystallization rate and crystallinity degree.

Synergistic Effect of Cellulose Nanofiber and Nanoclay as Distributed Phase in a Polypropylene Based Nanocomposite System.

Since the plastic-based multilayer films applied to food packaging are not recyclable, it is necessary to develop easily recyclable single materials. Herein, polypropylene (PP)-based cellulose nanofiber (CNF)/nanoclay nanocomposites were prepared by melt-mixing using a fixed CNF content of 1 wt %, while the nanoclay content varied from 1 to 5 wt %. The optimum nanoclay content in the PP matrix was found to be 3 wt % (PCN3), while they exhibited synergistic effects as a nucleating agent. PCN3 exhibited the best mechanical properties, and the tensile and flexural moduli were improved by 51% and 26%, respectively, compared to PP. In addition, the oxygen permeability was reduced by 28%, while maintaining the excellent water vapor permeability of PP. The improvement in the mechanical and barrier properties of PP through the production of PP/CNF/nanoclay hybrid nanocomposites suggested their possible application in the field of food packaging.

Graphene oxide and laponite composite films with high oxygen-barrier properties.

The design and fabrication of oxygen barrier films is important for both fundamental and industrial applications. We prepared three different thin films composed of graphene oxide (GO) and laponite (LN), a typical low cost inorganic clay, with the GO/LN volume ratios of 1.9/0.1, 1.7/0.3 and 1.5/0.5 together with a double layer film of the GO and LN. We found that the films with GO/LN = 1.9/0.1 and the double layers exhibited high oxygen barrier and oxygen transmission rate values that reached 0.55 and 0.37 cm(3) per m(2) per atm per day, respectively, which were much lower than those of the films prepared from the pure GO, only LN and GO/LN = 1.7/0.3 and 1.5/0.5. This study is important for the design and fabrication of a film from GO-based all inorganic nanomaterials for applications in gas-barrier membranes.

Direct electrospray deposition of graphene onto paper and effect of binder on its surface resistance.

The electrospray-deposited patterns of graphene onto filter paper were characterized to study the effect of cellulose acetate phthalate (CAP) binder on the surface resistance of the resulting paper. The amount of CAP determines the extent of penetration of graphene into the heterogeneous networks, because graphene gets anchored and crowded into the network with CAP. A graphene-dispersed ink was prepared in water using sodium dodecylbenzenesulfonate, and this ink was used to fabricate graphene-coated paper (GCP) by electrospray deposition technique. The SEM images of the GCP revealed the impregnation of graphene into the filter paper. The mechanical properties and surface resistance of the GCP were studied using a universal testing machine (UTM) and indigenous four-probe meter, respectively. The low-cost GCP prepared in this study showed relatively low surface resistance (96.2 omega/sq) owing to the effective electro-conducting pathway provided by the crowded and impregnated deposition of grapheme onto the filter paper. Consequently, CAP improved the electrical and mechanical characteristics of GCP, even though only a small amount of graphene was used during deposition.

Cellulosic binder-assisted formation of graphene-paper electrode with flat surface and porous internal structure.

We have reported the fabrication of flexible graphene-paper electrode (GPE) with a flat surface, whose internal structure has been formed with gradient porous build-up (from the surface to the 2-hydroxyethyl cellulose (HC)-coated paper). HC solution was used as a binder to form the gradient porous graphene layer, enabling it to create an anchoring force between the porous graphene layer and the filter paper. The morphology of GPE was investigated using a scanning electron microscope, and the surface resistance of the GPE as a function of graphene content was determined using four-probe method. The electrochemical performance of the GPE was evaluated using a three-electrode test cell by cyclic voltammetry. The gravimetric capacitance of GPE was found to be 120 F per gram of graphene, and the capacitance retention was within ca. 96% for over 500 cycles. This could be attributed to both the low surface resistance resulting from the flat surface and the high electrochemical activity caused by the gradient porous structure. This unique structure not only offers an enhanced conductivity and good electrical contact between the electrode and electrolyte but also helps GPE to maintain good cyclic stability, proving its potential for use in various rechargeable and portable energy-storage devices.

Formulation of emulsion adhesives with removal properties by using alkali soluble resins.

This study was aimed at developing environmental friendly adhesion materials using alkali soluble resins (ASRs). Water-borne emulsion pressure-sensitive adhesives show good compatibility with different polymer emulsions, high solid contents, and good working property, thereby allowing adjustment of the extensive viscosity. On the other hand, it is not easily recyclable and its adhesion and water-resistance properties are not optimal. Herein, ASR was used as the polymeric surfactant. ASR presents good emulsion stabilization, high molecular weight, and solubility in alkali solutions. ASR contains both hydrophobic and hydrophilic groups, thereby reducing the surface tension of the aqueous phase stabilizing monomer droplet or polymer particles. Additionally, it can form aggregates as a result of inter- and intramolecular hydrophobic interactions. The large number of carboxyl groups of this resin stabilizes polymer particles by an electrostatic effect. The recycling and adhesion properties of this resin were assessed by using UTM, a weight method. Further properties of the resin were determined by DSC, GPC, and ETC.

Fabrication of polymer-silica core-shell particles using copolymeric spheres prepared via precipitation polymerization.

Silica-coated polymeric particles were synthesized based on cationic colloidal particles which were prepared by precipitation polymerization of divinylbenzene in the presence of a cationic monomer, N-[3-(dimethylamino)propyl]methacrylamide. Negatively charged silica precursors were interacted with the cationic charged dimethylamine groups in colloidal particles. The resulting polymer/silica core/shell particles were characterized by scanning electron microscopy (SEM). Moreover, omniphobic particles were achieved by coupling reaction of the core/shell particles with nonafluorohexyl-triethoxysilane. Their water/oil static contact angles were investigated.

Use of polymer nanoparticles as functional nano-absorbents for low-molecular weight hydrophobic pollutants.

To use amphiphilic polymer nanoparticles as a new nano-absorbent for improving environmental process, urethane acrylate nonionomer (UAN) chain having hydrophobic polypropylene oxide-based segment and hydrophilic polyethylene oxide-based segment at the same backbone was synthesized and dispersed as nanoparticles at water phase without using a surfactant or dispersion agent. These UAN nanoparticles were converted to crosslinked amphiphilic polymer (CAP) nanoparticles through soap-free emulsion polymerization and suspension agent-free suspension polymerization process. Emulsion polymerization process exhibited higher conversion of polymerization compared to suspension polymerization process. CAP nanoparticles showed interfacial activity and solubilize hydrophobic pollutants (phenanthrene and toluene) like surfactant micelles. This result indicates possible application of CAP nanoparticles as nano-absorbent for improving efficiency of soil washing and micellar-enhanced ultrafiltration (MEUF) process.

Comparison of amphiphilic polyurethane nanoparticles to nonionic surfactants for flushing phenanthrene from soil.

Amphiphilic polyurethane (APU) nanoparticles were synthesized through crosslinking polymerization of nano-aggregates of urethane acrylate nonionomer (UAN). The efficiency of in situ extraction of sorbed phenanthrene from aquifer material was tested using soil columns and compared with that of surfactants such as Triton X-100, Brij 30, and Tween 80. The extraction efficiency of those washing materials strongly depended on their concentration, flow rate, and the degree of sorption within soil column. That is, the extraction efficiency increased with the decrease of flow rate and the degree of sorption and the increase of the concentration. Even though the surfactants are superior to APU nanoparticles at solubilizing phenanthrene, at the same flow rate (0.02 mL/min) and concentration (4000 mg/L), the effectiveness of in situ soil washing of APU nanoparticles was about two times higher than those of surfactants. This is because, at the lower flow rates, the degree of sorption of APU nanoparticles was lower than that of surfactants, owing to the chemically crosslinked nature of APU nanoparticles.

Effect of amphiphilic polyurethane nanoparticles on sorption-desorption of phenanthrene in aquifer material.

Micelle-like amphiphilic nano-sized polyurethane (APU) nanoparticles were synthesized via chemical cross-linking reaction of nano-aggregates of urethane acrylate nonionomer (UAN) chain and were tested for extraction efficiency of sorbed phenanthrene from aquifer material. Even though the solubilizing performance and interfacial activity of APU nanoparticles were inferior to that of Triton X-100, in the low concentration region, APU nanoparticles could effectively reduce phenanthrene sorption on the aquifer material and extracted sorbed phenanthrene from the aquifer material, whereas Triton X-100 could not extract sorbed phenanthrene and rather increased phenanthrene sorption onto the aquifer materials. At higher concentrations, APU nanoparticles and Triton X-100 had almost the same soil washing effectiveness. This interesting result is mainly due to a lower degree of sorption of APU nanoparticles onto the aquifer material. The sorption of APU nanoparticles onto aquifer sand is largely hindered by their chemically cross-linked nature, resulting in better soil-washing performance of APU nanoparticles than Triton X-100.