Incorporation of postconsumer polyurethane foam into a polymer/clay aerogel matrix

The feasibility of incorporating ground recycled polyurethane (PU) foam into clay/polymer aerogels was demonstrated, and a range of compositions were prepared and characterized to determine the effect of variation in the formulations on density and mechanical properties of the resulting materials. This study followed a modified combinatorial approach. Initially, experiments were performed in water using either sodium exchanged montmorillonite or laponite clay, poly(vinyl alcohol) (PVOH) solution as the polymer binder, and the recycled PU foam. Freezing and freeze‐drying the aqueous gels produced aerogels, which were characterized through density and mechanical testing, scanning electron microscopy, and thermal gravimetric analysis. The study was expanded by exploring alternative binder chemistries, including the use of an alginate polymer in place of the PVOH or adding a polyisocyanate as a crosslinking agent for PVOH. The effect of recycled PU foam content, clay type and level, and binder type and level on the mechanical properties of the aerogels were determined and will be discussed herein. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42586.     

FTIR-ATR studies of the sorption and diffusion of acetone:water mixtures in poly(vinyl alcohol)-clay nanocomposites

The simultaneous ingress of acetone and water into dried PVOH-clay nanocomposites containing 2.5 wt% or 5 wt% of well dispersed Na-Cloisite, using FTIR-ATR, has been compared with that into pure PVOH films. The rate at which water and acetone moved through the PVOH films is significantly reduced (i) at high acetone concentrations and (ii) when clay is incorporated in the PVOH film. For example, it takes 9 min and 17 min for water and acetone, respectively, to saturate a 25 ± 5 μm PVOH film containing 2.5 wt% of well dispersed clay when the acetone:water ratio is 90:10 v/v compared with ca. 1 min for a pure PVOH film when the acetone:water ratio is 70:30 v/v. The presence of significant quantities of water in the PVOH (nanocomposite) films was necessary before acetone began to permeate the film. The acetone entering the evanescent field was always highly hydrated even if the water content of the reservoir in contact with the film was low. There was no substantial evidence that the presence of clay altered the way in which the PVOH interacted with the acetone:water mixtures. The clay only acted to increase the tortuosity of the path through the film to the ATR prism.     

Separation of toluene–methanol mixtures by pervaporation using crosslink IPN membranes

Polyvinyl alcohol (PVOH) has been chemically modified by crosslink copolymerization of acrylic acid (AA) and hydroxyethylmethacrylate (HEMA) in aqueous solution of PVOH and finally crosslinking PVOH to produce a full interpenetrating network (IPN) membrane termed as PVAH. Accordingly, three such full crosslink IPNs membranes, i.e. PVAHI, PVAHII and PVAHIII containing varied weight ratio of PVOH and copolymer have been synthesized and used for pervaporative separation of methanol from its mixtures with toluene. For comparison, a conventional PVOH membrane crosslinked with glutaraldehyde has also been used for the same pervaporation study. The flux and selectivity of these IPN membranes were found to be much higher than the conventional glutaraldehyde crosslinked PVOH membrane. Among the three membranes, PVAHII with 50 wt% polyAH incorporation showed optimum performance in terms of flux and methanol selectivity.     

Competitive adsorption of water-soluble polymers on attapulgite clay

The individual, competitive, and displacement adsorption of polyvinyl alcohol (PVOH), hydroxyethyl cellulose (HEC), and hydroxypropylmethyl cellulose (HPMC) in aqueous solution onto an attapulgite clay has been systematically studied. For the individual adsorption experiments, the amount of polymer adsorbed at equilibrium decreased in the order PVOH, HEC, HPMC. In the competitive adsorption experiments, the adsorption level of each polymer is diminished by the presence of a competing polymeric species. Binary mixtures of a cellulosic polymer (HEC or HPMC) with PVOH result in a substantial reduction in the amount of cellulosic polymer adsorbed. In the displacement adsorption studies, the sequential addition of HEC or HPMC is not able to displace previously adsorbed PVOH molecules to any appreciable extent. However, the addition of PVOH to previously equilibrated HEC/clay or HPMC/clay suspensions results in a large amount of the adsorbed cellulosic polymer being displaced by PVOH, especially under conditions of high surface coverage. These results indicate that PVOH is preferentially adsorbed on the clay surface and the strength of attachment to the surface is greater for PVOH than for either cellulosic polymer.     

HES-HEMA nanocomposite polymer hydrogels: swelling behavior and characterization

Organophilic sodium montmorillonite (Na-MMT) and Laponite-RD clays were incorporated into photopolymerizable hydroxyethyl starch (HES) modified with 2-hydroxyethyl methacrylate (HEMA). Swelling, mechanical properties and thermal stability of obtained crosslinked nanocomposite polymers were evaluated. A camphorquinone-amine system was used as photoinitiating system in visible light. The interaction between nano-sized filler particles and polymer hydrogel was evaluated by FT-IR spectroscopy and the platelet distribution was investigated by SEM. An increased thermal stability of nanocomposite polymers upon addition of clay was observed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicating interaction between the clay platelets and the polymer chains. The crosslinking density for HES-HEMA/MMT nanocomposite hydrogels as investigated by swelling measurements increases with increasing the organo-clay content. The mechanical properties of virgin hydrogels were improved by the introduction of organo-clay as evidenced by oscillation rheology measurements. Whereas, the increase in crosslink density and storage modulus with clay content for laponite was found to be increasing for all concentrations investigated, for MMT there is an optimum content of ca. 1.5 wt%.     

Crosslinked glutinous rice starch filled polyvinyl alcohol films

The influence of glutinous rice starch (GRS) content and sodium hexametaphosphate (SHMP) in polyvinyl alcohol (PVOH) films were studied. The increase of GRS content (0–40 wt%) reduced the tensile strength (from 14.3 to 4.3 MPa) and elongation at break (from 183 to 52.5) of PVOH/GRS films. Nevertheless, the modulus of elasticity of PVOH/GRS films increased with GRS content, from 20.3 to 132.83 MPa. SHMP was used as a crosslinking agent, which improved more than 30% of tensile strength and modulus of elasticity of PVOH/GRS films. However, the elongation at break reduced after crosslinking process of the films. The crosslinked film showed better interaction between GRS and PVOH, as demonstrated by scanning electron microscopy. Conversely, the crosslinked films exhibited a lower swelling degree, but a higher gel content compared to uncrosslinked films. J. VINYL ADDIT. TECHNOL., 25:359–365, 2019. © 2019 Society of Plastics Engineers     

Influence of the nanofiber dimensions on the properties of nanocellulose/poly(vinyl alcohol) aerogels

The investigation of aerogels made from cellulose nanofibers and poly(vinyl alcohol) (PVOH) as a polymeric binder is reported. Aerogels based on different nanocellulose types were studied to investigate the influence of the nanocellulose dimensions and their rigidity on the morphology and mechanical properties of the resulting aerogels. Thus, cellulose nanocrystals (CNCs) with low (10), medium (25), and high (80) aspect ratios, isolated from cotton, banana plants, and tunicates, respectively, microfibrillated cellulose (MFC) and microcrystalline cellulose (MCC) were dispersed in aqueous PVOH solutions and aerogels were prepared by freeze‐drying. In addition to the cellulose type, the PVOH‐ and the CNC‐concentration as well as the freeze‐drying conditions were varied, and the materials were optionally cross‐linked by an annealing step or the use of a chemical cross‐linker. The data reveal that at low PVOH content, rigid, high‐aspect ratio CNCs isolated from tunicates afford aerogels that show the least amount of shrinking upon freeze‐drying and display the best mechanical properties. However, with increasing concentration of PVOH or upon introduction of a chemical cross‐linker the differences between materials made from different nanocellulose types decrease. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41740.     

Flame retardancy and thermal stability of ethylene-vinyl acetate copolymer nanocomposites with alumina trihydrate and montmorillonite

The development of fire retardant for wire and cable sheathing materials has oriented toward low smoke and halogen-free flame retardant technology to achieve better safety for electrical equipment and devices and to satisfy standards. However, many polymer flame resistance materials require a very high proportion of metal hydrate filler within the polymer matrix (60 wt%) to achieve a suitable level of flame resistance, which may lead to inflexibility, poor mechanical properties and problems during compounding and processing. In this study, the alumina trihydrate (ATH) was added to montmorillonite (MMT) as the halogen-free flame retardant of ethylene-vinyl acetate (EVA) copolymer, with various ratios of EVA/ATH/MMT. The prepared nanocomposites were characterized through various techniques of XRD, tensile test, DSC analysis, TGA, LOI evaluation, and FE-SEM to explore the effects of organic modified clay (OMMT) and the layer distance on the mechanical, thermal, and flame resistance properties. In the XRD examinations, the layer-distance of MMT increased from 1.27 to 1.96 nm when polymer was added to the octadecylamine modified MMT. The best tensile strength was obtained at 3 wt% MMT. In addition, the halogen-free flame resistance grade of EVA containing 3 wt% OMMT and 47 wt% ATH revealed the best elongation and fire resistance (LOI = 28). The tensile and flame resistance properties of the nanocomposites were also significantly improved.     

Nanoindentation on hybrid organic/inorganic silica aerogels

The hybrid organic/inorganic silica aerogels experiment a drastic mechanical change into rubber behaviour in relation with the pure inorganic silica aerogel as a brittle material. Aerogels were prepared by sol–gel process and drying by venting off the supercritical ethanol, no degradation of the organic polymer was detected. TEOS (tetraethoxysiloxane) and PDMS (polydimethylsiloxane) were used as inorganic and organic precursors, respectively. Depth sensing nanoindentator was used to study the mechanical properties, which is extremely sensitive to small loads (1 mN) and penetration depths (10 nm). The TEOS inorganic clusters and the polymer crosslinking degree influence the microstructure of the hybrid aerogels. Surface indentations maps reveal the different heterogeneities such as the tough silica matrix, the softness of the elastic polymer chains and the plastic microcracks in pores. The values obtained are compatible with the macroscopic ones resulting from uniaxial compression. Creep tests confirm that the compliance parameter increases with the polymer content and results can be theoretically modeled by the Burger model.     

Rheological study of the gelation of cross-linking polyhedral oligomeric silsesquioxanes (POSS)/PU composites

The gelation process of N-Phenylaminomethyl-POSS/PU (polyurethane) nanocomposites during curing and at the stable state after curing was investigated by rheology. An increase in dynamic shear moduli, G′ and G″, was observed during the dynamic temperature ramps of the sample. In time-resolved mechanical spectroscopy (TRMS), G′ and G″ increased with curing time at constant curing temperatures over a wide of frequencies. The gelation time of the composites decreased with the rise of curing temperature or with the increase of POSS concentration. The relaxation exponent n at the critical gel was around 0.73. The gel stiffness S decreased as curing temperature increased or as POSS concentration increased. After the completion of the curing reaction, the critical concentration of POSS beyond which the gelation of POSS/PU composites would happen was found around 2.5 wt%. The viscoelastic properties of crosslinking POSS/PU fitted time–temperature-superposition well which implied the incorporation of multifunctional POSS into PU increased the homogeneity of crosslinking POSS/PU composites. Surprisingly, the modulus of the fully cured materials between 2.7 wt% and 6 wt% could also be supposed onto a master curve at high temperature, which implied self-similarity of network near the critical gel. The similar microstructure of POSS/PU at stable state was also confirmed by TEM. The network formation mechanism and the fine structure of the crosslinking POSS/PU were firstly investigated which would provide technical and theoretical basis for other hybrid crosslinking systems.     

Foam‐like polymer/clay aerogels which incorporate air bubbles

The structure/property relationships of polymer/clay aerogels interfused with uniformly distributed air bubbles were examined. Through the incorporation of a polyelectrolyte in a montmorillonite(MMT) clay solution, the viscosity was systematically changed by the addition of ions with different charges. The bubbles were achieved via high speed mixing and were stabilized through the use of the surfactant sodium dodecyl sulfate (SDS). As the charge of the ion increased from +1 (Na⁺ ions) to +2 (Ca²⁺ ions) to finally +3 (Al³⁺ ions), the modulus of the resultant aerogels increased. The foamed polymer/clay aerogels showed a reduction in thermal conductivity while retaining similar mechanical properties to unfoamed polymer/clay aerogels. The most promising composition was one which contained 5% MMT clay/5% poly(vinyl alcohol)/0.5% xanthum gum/0.5% SDS/0.2% Al₂(SO₄)₃·6(H₂O) possessing a density of 0.083 g/cm³, an average modulus of 3.0 MPa, and a thermal conductivity of 41 W/m·K. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39546.     

Highly compressible ceramic/polymer aerogel-based piezoelectric nanogenerators with enhanced mechanical energy harvesting property

Ceramic piezoelectric materials have orders of magnitude higher piezoelectric coefficients compared to polymers. However, their brittleness precludes imposition of large strains in mechanical energy harvesting applications. We report here that ice templating affords low bulk modulus lead-free aerogel piezoelectric nanogenerators (PENG) with unprecedented combination of flexibility and high piezoelectric response (voltage and power density). A modified ice templating protocol was used to fabricate piezoelectric nanocomposites of surface modified BaTiO₃ (BTO) nanoparticles in crosslinked polyethylene imine. This protocol allowed incorporating a significantly high fraction of BTO particles (up to 83 wt %) in the aerogel, while retaining remarkably high compressibility and elastic recovery up to 80% strain. The output voltage, at an applied compressive force of 20 N (100 kPa), increased with BTO loading and a maximum output voltage of 11.6 V and power density of 7.22 μW/cm² (49.79 μW/cm³) was obtained for PENG aerogels containing 83 wt% BTO, which is orders of magnitude higher than previously reported values for foam-based piezoelectric energy harvesters. The BTO/PEI PENGs also showed cyclic stability over 900 cycles of deformation. PENGs with higher porosity showed better elastic recovery and piezoelectric properties than lower porosity and higher BTO content aerogels. To the best of our knowledge, this is the first report to demonstrate the piezoelectric properties of high ceramic content aerogels having very high compressibility and elastic recovery.     

Polymer/clay aerogel‐based glass fabric laminates

Laminates of polymer/clay aerogels and glass fabric sheets were prepared with varying epoxy adhesion application levels. A poly(amide‐imide) and an epoxy (1,4‐butanediol diglycidyl ether/2,6‐diaminopyridine) were chosen as the two “foam core” polymers; both single‐layered and double‐layered glass fiber laminates were investigated. The adhesion between polymer clay aerogels and glass fibers was quantified using the T‐peel method. The peel strength properties were found to increase as adhesive loading increased up to an optimal value, after which peel strength declines. Flexural and compressive testing of the laminates was also performed as a way of measuring mechanical strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of nitrogen-doped graphene-based binary composite aerogels for ultralightweight and broadband electromagnetic absorption

The development of ultralightweight and broadband electromagnetic wave (EMW) absorbing materials remains a big challenge. In this work, porous magnesium ferrite microspheres decorated nitrogen-doped reduced graphene oxide (NRGO/MgFe₂O₄) composite aerogels were prepared by a two-step route of solvothermal synthesis and hydrothermal self-assembly. Results of microscopic morphology characterization showed that NRGO/MgFe₂O₄ composite aerogels had a unique hierarchical porous structure. Moreover, the influence of additive amounts of graphene oxide on the electromagnetic parameters and EMW absorption properties of NRGO/MgFe₂O₄ composite aerogels was explored. Remarkably, the attained binary composite aerogel with the content of NRGO of 70.21 wt% exhibited the best EMW absorption performance. The minimum reflection loss reached up to −55.7 dB, and the corresponding effective absorption bandwidth was as large as 5.36 GHz at a thin matching thickness of 1.98 mm. Furthermore, when the matching thickness was slightly increased to 2.29 mm, the widest effective absorption bandwidth was enlarged to 7.1 GHz, covering the entire Ku-band. The magnetodielectric synergy and unique hierarchical porous structure in NRGO/MgFe₂O₄ composite aerogels not only improved the impedance matching, but also greatly enhanced the EMW absorption capacity. It was believed that the results of this work could be helpful for the preparation of graphene-based magnetic composites as broadband and efficient EMW absorbers.     

Study on properties of nanocomposites based on HDPE,LDPE, PP,PVC, wood and clay

Wood polymer nanocomposite (WPC) was prepared by solution blending of high density polyethylene, low density polyethylene, polypropylene and polyvinyl chloride (1:1:1:0.5) with wood flour and nanoclay. Xylene and tetrahydrofuran were used as solvent and the ratio was optimized at 70:30. TEM study revealed better dispersion of silicate layers in WPC loaded with 3 wt% of clay. WPC loaded with 3 wt% nanoclay exhibited higher thermal stability compared to WPC loaded with 1 and 5 wt% clay. The storage and loss modulus were found to enhance on incorporation of clay to WPC. The damping peak was found to be lowered by the addition of clay to WPC. Limiting oxygen index value increased due to incorporation of nanoclay. WPCs were subjected to exposure to cellulase producing Bacillus sp. and it showed the growth of bacteria as revealed by SEM study. Mechanical properties of WPC decreased due to degradation by bacteria. Water vapour uptake of WPC decreased due to addition of nanoclay.     

Enhanced bioactivity and low temperature degradation resistance of yttria stabilized zirconia/clay composites for dental applications

Yttria stabilized zirconia (YSZ)/clay composites were produced to improve osseointegration and undesired tetragonal-to-monoclinic phase transformation (low temperature degradation, LTD) of YSZ ceramics so that long-term clinical success of YSZ implants is achieved. Various amounts (0.5,1,2, and 4 wt%) of clay was incorporated to YSZ. Predetermined amounts of clay and YSZ were mixed and pressed uniaxially at 15 MPa into compacts that were subsequently pressureless sintered at 1450 °C. Density, compressive strength, hardness and indentation crack resistance of 4 wt% clay incorporated YSZ/clay composite were 5.77 ± 0.01 g/cm³, 1188 ± 121 MPa, 1223 ± 9 HV, and 4.4 ± 0.1 MPa√m, respectively. Additionally, biological properties of YSZ/clay composites were assessed in vitro using bone cells. Incorporation of 4 wt% clay significantly enhanced bone cell proliferation, spreading, and functions. Moreover, a significant increase in the LTD resistance of YSZ was achieved upon 4 wt% clay incorporation. The findings collectively suggest that YSZ/clay composites have a potential to be used as an alternative material for dental applications.     

Structure and properties of clay ceramics for thermal energy storage

In this paper, the structure‐property relationships of a clay ceramic with organic additives (biomass and biochar) are investigated to develop an alternative material for thermal energy storage. The firing transformations were elucidated using X‐ray pair distribution function analysis, differential scanning calorimetry, and scanning electron microscopy. It was found that the biomass increased the porosity, which resulted in a decrease of the specific heat capacity. On the other hand, the biochar remained in the clay ceramic without any interaction with the clay matrix up to 950°C. The specific heat capacity of the clay ceramic increased from 1.20 to 1.49 kJ/kg·K for a 30 wt% addition of biochar. The clay ceramic with a 30 wt% addition of biochar also conserved a high flexural strength of 11.1 MPa compared to that of the clay ceramic without organic additives (i.e., 18.9 MPa). Furthermore, the flexural strength only decreased by 23% after 100 thermal cycles. The crack growth associated with the thermal fatigue was limited by crack bridging and crack trapping. Hence, the current results suggest that clay/biochar ceramics can be as efficient as molten salts in thermal energy storage with the added benefit of an ease of use in the physical form of bricks.     

Synthesis, characterization, and crosslinking of soluble cyano-containing poly(arylene ether)s bearing phthalazinone moiety

A novel series of phthalazinone-based poly(arylene ether nitrile)s bearing terminal cyano groups via N-C linkages (PPEN-DCs) were synthesized by a simple solution polycondensation of 4-(4-hydroxylphenyl)(2H)-phthalazin-1-one (HPPZ) with calculated 2,6-difluorobenzonitrile (DFBN), followed by the termination of 4-chlorobenzonitrile (CBN). The M_ns of oligomeric PPEN-DCs, which are in the range of 1600-6200, can be well-controlled by adjusting reactant ratio. The incorporation of phthalazinone into the polymer chain results in an improvement in the solubility and glass transition temperatures (T_gs). The amorphous PPEN-DCs were thermally crosslinked to afford insoluble products in the presence of terephthalonitrile and zinc chloride. The pendant cyano groups in the polymer chain hardly undergo any crosslinking or cyclization, while the terminal cyano groups with nitrogen-bridged phthalazinone in the para-substitution are much more reactive in s-triazine forming reaction and effectively promote certain crosslinking under normal pressure. T_gs of the oligomers, which range from 245 to 269 °C, could be further increased at least by 94 °C upon thermal curing. The crosslinked samples exhibit excellent thermal stability and absorb less than 2.7 wt% water after exposure to an aqueous environment for extended periods. This kind of cyano-terminated poly(arylene ether nitrile)s may be a good candidate as matrix resins for high-performance polymeric materials.     

Improved strength and toughness of polyketone composites using extremely small amount of polyamide 6 grafted graphene oxides

Polyketone (PK) composites were prepared by a solution casting method using 1,1,1,3,3,3-hexafluoro-2-propanol as a solvent and polyamide 6 grafted graphene oxides (PA 6-GOs) as filler materials. PA 6-GOs were obtained by in situ polymerization of ε-caprolactam using GOs having different amounts of oxygen functional groups. The PK composites containing only an extremely small amount of the PA 6-GOs (0.01 wt%) showed much improved mechanical properties compared to PK. This could be ascribed to the homogeneous dispersion of the graphene-based filler materials in the polymer and specific interactions such as dipole–dipole interactions and/or the hydrogen bonds between the fillers and the polymer matrix. For example, when 0.01 wt% of PA 6-GO having less oxygen functional groups was used as a filler for the composite, the tensile strength, Young’s modulus, and elongation at break of the composite increased by 35%, 26%, and 76%, respectively. When 0.01 wt% of PA 6-GO having larger content of oxygen functional groups and PA 6 was used, Young’s modulus decreased, while the tensile strength increased by 37%, and the elongation at break increased tremendously by 100 times, indicating that very tough polymeric materials could be prepared using a very small amount of the graphene-based fillers.     

Improving the mechanical properties of clay/polymer aerogels by a simple dip‐coating procedure

Clay aerogels have many advantages as one of the lowest density family of materials current technology can provide; they possess very low thermal conductivities, high porosities, and high surface areas. Although the mechanical properties of native clay aerogels are rather low, incorporating water‐dispersible polymers into the clay gel before they are processed into aerogel forms can easily produce more robust, low‐density composites. Various processing modifications and additives can be employed to strengthen the aerogel material, but currently, the materials have some notable weaknesses in abrasion resistance, water absorption, and flexural properties. In this study, we employed a low‐cost rubber coating material to quickly and efficiently address all three of these problems. After coating, the aerogels gained significant mechanical reinforcement, a 20‐fold increase in flexural modulus and a 15‐fold increase in yield stress, while exhibiting an increase of only 8% in the thermal conductivity. Improvements such as these can improve the commercial applicability of clay/polymer aerogels as thermal insulation materials. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012