Search

Cationic photo-initiated and polymerized epoxies are characterized by good adhesion, high modulus, zero volatiles, low shrinkage and living polymerization characteristics. Radiation—cured acrylate resins are characterized by rapid initial curing with increased initial strength. The combination of radiation-cured acrylates and epoxies may present advantageous attributes. Thus, the system investigated is a hybrid epoxy/methyl acrylate and three different initiators for cationic polymerization of epoxies, the radical reaction of acrylates and the thermal initiator. When incorporating additives like opaque WS2 nanoparticles (NPs), absorption of the photo radiation takes place, which may lead to low photo activity. Curing kinetics measurements revealed that the absorbing/masking effect of WS2 was insignificant, and surprisingly, the level of curing was enhanced when the WS2 NPs were incorporated. FTIR results demonstrated that covalent bonds were formed between the inorganic fullerenes (IF-WS2) and the crosslinked matrix. Viscosity measurements showed a surprising reduction of five to ten times in the low-shear viscosity upon NPs incorporation compared to neat resins. It was concluded that the decrease of viscosity by the inorganic NPs, in addition to the enhanced level of conversion, has profound advantages for structural adhesives and 3D printing resins. To the best of our knowledge, this investigation is the first to report on a radiation-induced curing system containing opaque WS2 NPs that leads to an enhanced degree of curing and reduced shear viscosity.

The effect of particle loading on the wetting properties of coatings was investigated by modifying a coating formulation based on hydrophilic silica nanoparticles and poly (acrylic acid) (PAA). Water contact angle (WCA) measurements were conducted for all coatings to characterize the surface wetting properties. Wettability was improved with an increase in particle loading. The resulting coatings showed superhydrophilic (SH) behavior when the particle loading was above 53 vol. %. No new peaks were detected by attenuated total reflection (ATR-FTIR). The surface topography of the coatings was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The presence of hydrophilic functional groups and nano-scale roughness were found to be responsible for superhydrophilic behavior. The surface chemistry was found to be a primary factor determining the wetting properties of the coatings. Adhesion of the coatings to the substrate was tested by tape test and found to be durable. The antifogging properties of the coatings were evaluated by exposing the films under different environmental conditions. The SH coatings showed anti-fogging behavior. The transparency of the coatings was significantly improved with the increase in particle loading. The coatings showed good transparency (>85% transmission) when the particle loading was above 84 vol. %.

This article describes the study of the topography effect of superhydrophobic surfaces on the corrosion protection performance of steel through the air plastron behavior when subjected to an underwater environment. A random superhydrophobic surface was fabricated using spray coating and characterized for morphology and wettability by scanning electron microscopy (SEM) and goniometer measurements, respectively. By comparing the coated surfaces both with and without air plastron, it was found that superhydrophobicity postponed the corrosion of the coated steel specimens. This increase in corrosion protection of the superhydrophobic surface was due to the air plastron created by the superhydrophobicity in underwater immersion. Since different areas showed differing air plastron lifetimes (wetting behavior), it was assumed that the underlying topography of the superhydrophobic coating controlled the air plastron lifetime. To investigate this behavior, the micron scale topography of the different areas was studied using the technique of laser confocal microscopy over the specific areas and correlating with air plastron lifetime. Using the theoretical analysis based on superhydrophobic robustness and assuming the solid fraction is the same for different locations, it was demonstrated that the feature size [extracted by roughness analysis as root-mean-square (RMS)] correlated with the air plastron lifetime. It was confirmed from the plot of RMS and air plastron lifetime that smaller feature sizes could extend the air plastron lifetime and provide better anticorrosion performance.

The composition–processing–property relationship of imine containing reversible covalent bond containing polymers (RCBPs) was studied using an innovative (regarding this type of polymer) combination of characterization methods. This combination led, for the first time, to a classification of the various chemical reactions occurring during the processing of imine based RCBP, affecting their final chemical structure and properties. RCBPs, based on PIs (polyimines), were synthesized from polyethyleneimine (PEI) and terephthalaldehyde (TPA) in the presence of ethanol. The chemical composition and derived thermal and mechanical properties were investigated. Material characterization using ATR-IR, 13C-solid state NMR, swell tests, and a novel illustrative model based on the Flory–Rehner equation led to the conclusion that at least 80% of the secondary amine groups reacted to form a cross-linking network, along with 100% of the primary amines, and that during 20 min compression molding at 220 °C under 2.7 MPa, a post-curing reaction occurs. 13C-SSNMR and ATR-IR indicated that the chemical structure is determined not only by the reactants but also by the elevated temperature processing conditions. During heating, three mechanisms affect the final composition–transimination, reduction (back into amine groups) and oxidation (to oxaziridine and amide groups which are almost negligible). The reduction/oxidation processes were found to dominate the mechanical properties. The vitrification temperature (Tv), which is characteristic of RCBPs, is dependent on the thermal history, with a higher Tv resulting from longer compression molding times. The mechanical properties are affected by the processing temperatures, changing from high-performance to very low strength. Under specific processing conditions, the imine cross-linking bonds are reduced/oxidized, which causes the formation of more polar but lower energy bond cross-linking, resulting in lower tensile strength and a change in the hydrophobicity of the polymer, which may be used in future applications.

In this work the drag reduction performance of superhydrophobic composite coatings was investigated. The drag reduction behavior for both short-term and long-term use was studied using a parallel p...

The mechanical properties of braided carbon nanotube yarns (CNTYs) on an elastomeric core to produce stretchable conductive materials were modeled and studied under tension. The elastomeric core served as the stretchable spring and the CNTYs braiding, with shape changing capabilities, as the conductive shell. The model predicts the stress-strain behavior of the composite as a function of the initial braiding angle and the number of pitches. The innovative aspect was included in the model related to the friction between the braid and the core. Results indicated good agreement between the theoretical model and the experimental results. Since the rate of the diameter decrease of the CNTYs braid was higher than that of the elastomeric core diameter, squeezing out of the core through the braid inter yarn space occurred. This limited the maximum potential extension of the braid. Thus, a critical strain was defined where the braid came into contact with the core. The addition of the friction stresses made a significant contribution to the overall stresses and the accuracy of the model and its agreement with the experimental results. An apparent friction coefficient was proposed to account for the effect of the elastomer core/braid interactive restriction and squeezing out of the elastomer through the braiding, as observed in experimental results. As the CNTYs are conductive, a stretchable conductive composite was obtained having a resistivity of 9.05x10-4 Ohm*cm, which remained constant throughout the tensile loading until failure and under cyclic loading.

Superhydrophilic coatings based on a hydrophilic silica nanoparticle suspension and Poly (acrylic acid) (PAA) were prepared by dip coating. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) were used to examine the morphology of the coating. The effect of surface morphology on the dynamic wetting behavior of the superhydrophilic coatings was studied by changing the silica suspension concentration from 0.5% wt. to 3.2% wt. while keeping the silica concentration in the dry coating constant. The droplet base diameter and dynamic contact angle with respect to time were measured using a high-speed camera. A power law was found to describe the relationship between the droplet diameter and time. A significantly low experimental power law index was obtained for all the coatings. Both roughness and volume loss during spreading were suggested to be responsible for the low index values. The water adsorption of the coatings was found to be the reason for the volume loss during spreading. The coatings exhibited good adherence to the substrates and retention of hydrophilic properties under mild abrasion.

The radiation curing paradigm of opaque WS2 nanoparticle (NP)-based epoxy/acrylate nanocomposites was studied and found to exhibit both a reduction in viscosity and an enhanced degree of curing when incorporating WS2 NPs. The objective of this study was to investigate the mechanical, thermal, and physical properties of a radiation-induced and cured epoxy/acrylate blend containing 0.3 to 1.0 wt.% WS2 NPs. Experimental results indicate that the tensile toughness increased by 22% upon optimizing the NP content compared to that of WS2-free formulations. Tensile fractured surfaces with different WS2 NP contents were analyzed with a scanning electron microscope and an atomic force microscope and showed distinctive morphology depending on the WS2 NP content, supporting the results of the tensile test. The energy required to break shear adhesion specimens demonstrated an increase of up to 60% compared to that of the neat resin. The glass transition temperature determined by dynamic mechanical analysis presented similar or higher values upon WS2 NP incorporation. Furthermore, up to 80% improvement in impact strength was demonstrated when WS2 NPs were dispersed in the epoxy/acrylate blend. It was concluded that the surface chemistry and dispersion level of the WS2 NPs are the major variables affecting the macro properties of cationically radiation-cured resins and their adhesion properties. This study is the first to demonstrate the possibility for radiation-induced curing of opaque NPs based on WS2 that serve as both a reinforcement nanoparticle at low concentrations and an enhancement of the degree of curing.

Hybrid sol–gel superhydrophobic coatings based on alkyl silane-modified nanosilica were synthesized and studied. The hybrid coatings were synthesized using the classic Stöber process for producing hydrophilic silica nanoparticles (NPs) modified by the in-situ addition of long-chain alkyl silanes co-precursors in addition to the common tetraethyl orthosilicate (TEOS). It was demonstrated that the long-chain alkyl substituent silane induced a steric hindrance effect, slowing the alkylsilane self-condensation and allowing for the condensation of the TEOS to produce the silica NPs. Hence, following the formation of the silica NPs the alkylsilane reacted with the silica’s hydroxyls to yield hybrid alkyl-modified silica NPs having superhydrophobic (SH) attributes. The resulting SH coatings were characterized by contact angle goniometry, demonstrating a more than 150° water contact angle, a water sliding angle of less than 5°, and a transmittance of more than 90%. Confocal microscopy was used to analyze the micro random surface morphology of the SH surface and to indicate the parameters related to superhydrophobicity. It was found that a SH coating could be obtained when the alkyl length exceeded ten carbons, exhibiting a raspberry-like hierarchical morphology.

The wettability of poly (dimethylsiloxane) (PDMS) coating on plasma-treated glass was studied at room temperature using polar and non-polar liquids. The wettability was investigated regarding the liquids&rsquo, surface tensions (STs), dielectric constants (DCs) and solubility parameters (SPs). For polar liquids, the contact angle (CA) and contact angle hysteresis (CAH) are controlled by the DCs and non-polar liquids by the liquids&rsquo, STs. Solubility parameter difference between the PDMS and the liquids demonstrated that non-polar liquids possessed lower CAH. An empirical model that integrates the interfacial properties of liquid/PDMS has been composed. Accordingly, the difference between the SPs of PDMS and the liquid is the decisive factor affecting CAH, followed by the differences in DCs and STs. Moreover, the interaction between the DCs and the SPs is of importance to minimize CAH. It has been concluded that CAH, and not CA, is the decisive attribute for liquid repellency of PDMS coating.

Antiviral polymers are part of a major campaign led by the scientific community in recent years. Facing this most demanding of campaigns, two main approaches have been undertaken by scientists. First, the classic approach involves the development of relatively small molecules having antiviral properties to serve as drugs. The other approach involves searching for polymers with antiviral properties to be used as prescription medications or viral spread prevention measures. This second approach took two distinct directions. The first, using polymers as antiviral drug-delivery systems, taking advantage of their biodegradable properties. The second, using polymers with antiviral properties for on-contact virus elimination, which will be the focus of this review. Anti-viral polymers are obtained by either the addition of small antiviral molecules (such as metal ions) to obtain ion-containing polymers with antiviral properties or the use of polymers composed of an organic backbone and electrically charged moieties like polyanions, such as carboxylate containing polymers, or polycations such as quaternary ammonium containing polymers. Other approaches include moieties hybridized by sulphates, carboxylic acids, or amines and/or combining repeating units with a similar chemical structure to common antiviral drugs. Furthermore, elevated temperatures appear to increase the anti-viral effect of ions and other functional moieties.

Tehila Nahum,1 Hanna Dodiuk,2 Samuel Kenig,2 Artee Panwar,1 Carol Barry,1 Joey Mead,1 1Department of Plastics Engineering, University of Massachusetts Lowell, Lowell, MA, USA; 2Department of Polymers and Plastics Engineering, Shenkar College of Engineering Design and Art, Ramat Gan, Israel Abstract: Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders’ concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings. Keywords: superhydrophobic coating, durability, thermodynamics, silica nanoparticles, morphology

Carbon nanotube yarns (CNTYs) possess low density, high conductivity, high strength, and moderate flexibility. These intrinsic properties allow them to be a preferred choice for use as conductive elements in high-performance composites. To fully exploit their potential as conductive reinforcing elements, further improvement in their electrical conductivity is needed. This study demonstrates that tensile cyclic loading under ambient conditions improves the electrical conductivity of two types of CNTYs. The results showed that the electrical resistance of untreated CNTYs was reduced by 80% using cyclic loading, reaching the resistance value of the drawn acid-treated CNTYs. Scanning electron microscopy showed that cyclic loading caused orientation and compaction of the CNT bundles that make up the CNTYs, resulting in significantly improved electrical conductivity of the CNTYs. Furthermore, the elastic modulus was increased by 20% while preserving the tensile strength. This approach has the potential to replace the environmentally unfriendly acid treatment currently used to enhance the conductivity of CNTYs.

This paper focuses on the effect of composite interface morphology on the wetting behavior of a nanocomposite coating based on an organosilane binder. Experimental results supported by modeling demonstrated that a sharp change in contact angle hysteresis occurred at air fractions in the range of 40–60%, as controlled by particle loading. The air-liquid interface evolution with particle loading was visualized using the fluorescent dye staining method. A correlation between topography and this air-liquid-solid interface was done by overlapping the optical images and fluorescence dye stained images of the stained superhydrophobic surface, which allowed the visualization of microscale features. The results showed the structures supporting solid-liquid contacts were 20 to 40 μm in size and had an edge-to-edge spacing that decreased with increasing particle loading. In this system a critical spacing to transition from the Wenzel to the Cassie-Baxter state was found to be approximately five times the average width of these microscale structures. Identification of critical surface topography can aid in the development of coatings that provide anti-corrosive and/or anti-icing features for marine vessels, bridges, and buildings.

The electrical percolation threshold of different polyethylene/carbon nanotube nanocomposites was studied as a function of chain structure, matrix viscosity, and the effect of compatibilizer. The lower the viscosity of the matrix the lower is the percolation threshold, regardless of the chain architecture and degree of crystallization. To improve dispersion a series of acrylic acid copolymer are introduced into the system. The highest concentration of acid co-monomer that maintain miscibility with the polyethylene matrix is 5 wt.%. The compatibilizer in its pristine form does not have a significant effect on dispersion and on volume resistivity. When the acidic copolymer was modified with aminomethylpyridine, in order to facilitate π–π interaction with the nanotubes, a 4-decade reduction was recorder for the high viscosity matrices at 10 wt.% compatibilizer loading. Copyright © 2014 John Wiley & Sons, Ltd.

This work focuses on the use of silica nanoparticles for producing durable, transparent, and super-hydrophilic coatings on painted surfaces. Two methods were studied in detail: bottom-up approach u...

Poly(methyl methacrylate-co-methacrylic acid) was modified with 4-aminomethyl pyridine, in order to facilitate π–π interactions with carbon nanotubes. The π–π * transitions of both the carbon nanotubes and the pyridine modified copolymer were observed by X-ray photoelectron and UV–vis spectroscopy, respectively. The π-interactions themselves were evident by UV–vis absorbance quenching and red shift and also by fluorescence emission quenching and blue-shift. Those spectroscopic evidences suggested that the nanotubes were wrapped by the modified copolymer through π–π interactions. Introducing the pyridine modified copolymer as a compatibilizer in polymethyl methacrylate composites enabled improved nanotube dispersion, which led to reductions in volume resistivity and increases in composite storage modulus. Those results indicated that this novel compatibilizer could be suitable for a variety of carbon nanotube/poly(methyl methacrylate) composite based applications, where improved nanotube dispersion is desirable without damaging the nanotubes inherent properties.

An hierarchical structure, composed of a ternary cocontinuous polymer blend, where carbon nanotubes are mostly localized in one of the phases through π–π interactions, is fabricated by direct melt mixing of polyamide 12 and polypropylene, as the two major components of the ternary blend, together with pyridine-modified poly(ethylene-co-methacrylic acid) as the minor component that can form strong interactions with the CNTs via π–π interactions and confined the percolated network at the polyamide/polypropylene interface. The hierarchical structure was designed by means of surface energies, and the obtained morphology was verified using electron microscopy. This ternary structure has lower electrical resistivity as compared to cocontinuous binary composites. Different polymer viscosities were used in this study in order to emphasize the importance of kinetics during cocontinuous morphology formation.

It is now possible to synthesize inorganic nanotubes (INT) of WS2 in a pure phase and substantial amounts. Due to their crystalline perfection, they are characterized by excellent mechanical behavior. This study is dedicated to the investigation of the effect of INT-WS2 on the mechanical, thermal, adhesion and tribological properties of epoxy based nanocomposites. Various concentrations up to 1.0 wt% of the INT were added to the epoxy matrix. First a method was developed to mix the nanotubes in the epoxy resin matrix. A combination of both magnetic stirring and ultrasonic mixing was used. The adhesion, fracture toughness and strain energy release rate were studied. The INT-WS2 were found to significantly improve all these properties. The wear of the nanotubes-reinforced epoxy was eight-times lower than that of pure epoxy. These results suggest numerous applications.

In this paper we evaluated the effect of embedding inorganic nanotubes (INT) of tungsten disulfide (WS2) in an epoxy matrix, on the mechanical, thermal and adhesion properties of the resulting nanocomposites. The nanotube content spanned a range of values (0, 0.1, 0.3, 0.5 and 1.0 wt%), and the nanotube incorporation process consisted of a combination of both distributive (magnetic stirring) and dispersive (ultrasonic mixing) methods. The adhesion of the nanocomposites to an aluminum substrate was characterized by both a single lap shear and a T-peel test. The fracture toughness (K IC) of the nanocomposites was characterized by a standard compact tension (CT) plane-strain fracture test. The thermal properties of the nanocomposites were determined by dynamic mechanical thermal analysis (DMTA). Overall, the addition of INT-WS2 was found to improve the shear strength and peel properties of the nanocomposite, and to significantly improve its fracture toughness and glass transition temperature. The extent and ...

In this work the effect of inorganic fullerene-like (closed cages) nanoparticles of tungsten disulfide (IF-WS2) on the mechanical properties and especially on the toughness of epoxy resins, was studied. The epoxy resin used was the well-known DGEBA (di-glycidyl ether of bis-phenol A) cured with polyamidoamine. The epoxy/IF-WS2 nanocomposites were prepared by applying a high shear mixing to obtain a uniform dispersion and homogeneous distribution of the IF nanoparticles in the epoxy matrix. Two mixing procedures were used — a low shear of short duration and high shear with a long mixing time. The resulting epoxy nanocomposites were first characterized for their shear and peel strength using appropriate bonded joints. The experimental results demonstrate that enhanced shear strengths and shear moduli were achieved, together with a significant increase in the peel strengths at low concentrations of the IF-WS2 nanoparticles (more than 100% increase at 0.5 wt% IF-WS2). Above the threshold value of 0.5% IF-WS2 ...

Nanomodification of poly-hydroxy-butyrate (PHB), with hyperbranched polymers (HBP), was studied. Solid-hyperbranched polyesters of different generations were incorporated into a biobased and biodegradable, thermoplastic, polyester. Thermal, rheological, and molecular weight measurements had indicated that due to the interactions between the hydroxyl groups and the polar esters in PHB, the rate of recrystallization was significantly increased. Furthermore, the degree of crystallinity and nonisothermal crystallization temperature were also increased. Molecular weight measurements did not indicate a reduction or retention when HBPs were incorporated. These results are of great significance for the processing of biodegradable polymers and specifically for PHB, where improved processability and enhanced crystallization are of importance. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers

Organically modified montmorillonite clays were incorporated at a 5% loading level into film grade of poly-L-lactic acid (PLLA) using a variety of masterbatches based on either semi-crystalline or amorphous poly-(lactic acid), as well as biodegradable aromatic aliphatic polyester. The PLLA masterbatches and compounded formulations were prepared using a twin screw compounding extruder, while the films were prepared using a single screw cast film extruder. The thermal and mechanical properties of the films were examined in order to determine the effect of the clay and different carriers on the polymer–clay interactions. In the optimal case, when a PLLA-based masterbatch was used, the tensile modulus increased by 30%, elongation increased by 40%, and the cold crystallization temperature decreased by 15 °C, compared to neat PLLA. The properties improvement of PLLA films containing nano clays demonstrated the possibility to extend the range of biodegradable film applications, especially in the field of packaging.

The effect of pigments having different chemical composition on the crystallization process of polypropylene, PP, was studied by means of differential scanning calorimeter in isothermal mode. Analysis of the experimental results was carried out using Avrami's equation to obtain the crystallization parameters. Furthermore, Lipatov's approach was applied for evaluation of the thickness and content of the transition layers formed as a result of the interaction between the PP and the various pigments. Results have shown that depending on their composition the pigments act like nucleating agents affecting the degree of crystallinity, the structure of the amorphous phase and the interphase between the PP and the different pigments. The resultant morphology has been associated with the mechanical properties of the various pigmented PP compositions.

This study focused on the effect of Multi Wall Carbon Nanotubes (MWCNT) content and its surface treatment on thermo-mechanical properties of epoxy nanocomposites. MWCNTs were surface treated and incorporated into two epoxy systems. MWCNT's surface treatments were based on: (a) Titania coating obtained by sol-gel process and (b) a nonionic surfactant. Thermo-mechanical properties improvement was obtained following incorporation of treated MWCNT. It was noticed that small amounts of titania coated MWCNT (0.05 wt %) led to an increase in the glass transition temperature and stiffness. The best performance was achieved adding 0.3 wt % titania coated MWCNT where an increase of 10 °C in the glass transition temperature and 30% in storage modulus were obtained.

Conventional short-fiber thermoplastic compounds (fiber length usually

Voids in polymer composites may arise from various sources such as entrapped air within compounded pelletized material, moisture, volatiles evolved during cure, or residual solvents. Voids, or bubbles, are formed in short-fiber thermoplastic composites because of entrapment of air in the compounding and melt flow processing steps and as a result of uneven shrinkage due to temperature gradients involved in the solidification step by cooling. This article reviews theoretical and experimental studies dealing with void formation during melt flow compounding and processing of fiber-reinforced thermoplastic composites. The mechanism of void formation during processing under various flow conditions and the methods used for the determination of void content in composites were reviewed. The mechanism of bubble formation in molten polymer is that of nucleation and growth by expansion in a viscous medium. Voids nucleate at fiber ends, and their content depends on the processing method and processing conditions, on fiber concentration, and on fiber length. Keywords: voids; short fibers; mechanical properties; thermoplastic; composites

Blends containing two, wholly aromatic, naphthalene-based liquid crystalline polymers (LCPs) are studied. Experimental results show that the viscosities of the resulting blends are lower than the parent LCPs over the entire shear-rate range investigated. The orientation development following capillary flow demonstrates, that over a defined blend composition range, some blends have higher orientability than the constituent polymers. This is further manifested in the tensile and flexural properties of injection-molded specimens. A detailed analysis indicates that in the composition range where synergistic effects are observed in orientation development as well as in mechanical properties, only one glass transition temperature is detected. This suggests that “miscibility” is desirable for obtaining maximum properties in these blend systems.