Fabrication of composite films with poly(methyl methacrylate) and incompletely condensed cage‐silsesquioxane fillers

Polyhedral oligomeric silsesquioxane (POSS) is a promising nanofiller for tuning properties of optically transparent polymer materials. On the other hand, traditional completely condensed POSS (CC‐POSS) has a fundamental problem for fabricating optically transparent composite films; CC‐POSS has high crystallinity due to its symmetrical structure, resulting in aggregation in the polymer matrices. In this work, we have demonstrated that incompletely‐condensed POSS (IC‐POSS), which has an open‐cage structure, can be well dispersed in a poly(methyl methacrylate) (PMMA) matrix. IC‐POSS with various substituents were readily synthesized, and their composite films of PMMA were fabricated by solution‐casting method. High transparency was achieved with up to 30 wt % of the IC‐POSS fillers, while the CC‐POSS analogues caused phase separation with 10 wt % loading. Addition of the IC‐POSS fillers can improve thermal stability and control glass transition temperature by the substituent structure. Additionally, refractive index was tuned from 1.485 to 1.513. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46033.     

The preparation of Al2O3 based organic/inorganic composite films and the application in agricultural greenhouse

The work presented herein focuses on developing the Al₂O₃ based organic/inorganic multifunctional composite films via an internal addition method in the presence of dripping agent, antifogging agent, light stabilizer and insulation barrier agent. The resulting composite films were systematically characterized using scanning electron microscope, FTIR, differential scanning calorimetry, UV, and tensile testing machine. The morphology changed obviously after introducing the inorganic fillers. In addition, the results indicated that the contact angle of the activated Al₂O₃–10 film had the best stability and the film with ultrafine Al₂O₃ possessed the best anti-dripping performance. The time of the first water drop of the film containing 10 g activated Al₂O₃ (the activated Al₂O₃–10) was 7 min and 18 s, and the time of each ten-drops was less than 120 s. The simulated anti-aging period of the films with anti-aging agent was up to 423 days, which is superior to many other reported organic/inorganic composite films and can be applied to those extreme climate areas (such as Xinjiang, China).     

Ferroelectric nanodot formation from spin‐coated poly(vinylidene fluoride‐co‐trifluoroethylene) films and their application to organic solar cells

We demonstrated a facile route to the preparation of self‐assembled poly(vinylidene fluoride‐co‐trifluoroethylene) [P(VDF‐TrFE)] nanodots from spin‐coated thin films. We found that the initial film thickness would play an important role in the formation of such P(VDF‐TrFE) nanodots. Interestingly, the electric dipoles of such nanodots were self‐aligned toward the bottom electrode and their ferroelectric properties were determined by using piezoresponse force microscopy. In addition, the self‐polarized ferroelectric nanostructures were introduced to small molecular organic photovoltaic devices and allowed for enhancing the short circuit current density (J_sc) from 9.4 mA/cm² to 10.2 mA/cm² and the power conversion efficiency from 2.37% to 2.65%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41230.     

Fabrication of amido group functionalized carbon quantum dots and its transparent luminescent epoxy matrix composites

Functional amido groups are modified onto the surface of carbon quantum dots (CQDs) in order to provide reactive groups. The modified CQDs are subsequently added into amine cured epoxy resin system. After curing reaction, transparent and luminescent composites are obtained. The modified CQDs are denoted as CQDs@NH₂, and composites studied in this article are denoted as CQDs@NH₂/epoxy. It is found that the dispersion of CQDs@NH₂ in epoxy matrix is effectively improved with the bridge of covalent bonding interface. As a result, the homogenously dispersed CQDs@NH₂ reduce light scattering. And more than double increased transparency and eightfold enhanced luminescence of CQDs@NH₂/epoxy are obtained compared with original CQDs@COONa/epoxy composites. This composite has potential for encapsulating materials in white light‐emitting diodes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42667.     

Effect of clay type on dispersion and barrier properties of hydrophobically modified poly(vinyl alcohol)–bentonite nanocomposites

The oxygen and water vapor permeability at high relative humidity was studied for composite films formed by incorporation of three different bentonites (MMT) into an ethylene‐modified, water‐soluble poly(vinyl alcohol), EPVOH. The oxygen permeability decreased linearly with an increased addition of hydrophilic MMTs. X‐ray diffraction and Fourier transform infrared spectroscopy suggested a homogeneous distribution in the thickness direction with disordered and probably exfoliated structures for hydrophilic MMTs. In contrast, organophilic modified clay showed an intercalated structure with the clay preferentially located at the lower film surface, a combination which was however efficient in reducing the water vapor‐ and oxygen permeabilities at low addition levels. Composite films of EPVOH and Na⁺‐exchanged MMT resulted in high resistance to dissolution in water, which was ascribed to strong interactions between the components resulting from matching polarities. Annealing the films at 120°C resulted in enhanced resistance to water dissolution and a further reduction in oxygen permeability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42229.     

Hydrogen-bonding assembly of heteropolyacid and poly(vinyl alcohol) for strong,flexible, and transparent UV-protective films

Although many preparation approaches have been developed, it remains a huge challenge to achieve ultraviolet (UV)-protection films that combine high transparency, excellent UV-shielding, and mechanical properties. Herein, we demonstrate a facile and eco-friendly process for fabricating strong, flexible, and transparent UV-protective poly(vinyl alcohol) (PVA) films by exploiting silicomolybdic acid (SiMoA) as UV absorber and reinforcing phase. Fourier-transform infrared analysis confirms the formation of strong hydrogen-bonding interactions between PVA and SiMoA. The glass-transition temperature, mechanical properties, and UV-shielding stability of the UV-protective PVA composite films obviously increase with increasing the content of SiMoA. By incorporation of only 2 wt % SiMoA, the UV-protective PVA composite film can block more than 90% of UV light in the entire UV regions and retain high visible light transparency (up to 95%). Simultaneously, the UV-protective PVA composite film presents excellent mechanical properties with a tensile strength of 65.2 MPa and an elongation at break of 172.6%, which are 72.0 and 69.5% higher than that of pristine PVA films. This work provides a simple but effective approach for creating strong, flexible, and transparent UV-blocking polymeric materials via hydrogen-bonding assembly, which are expected to have wide application prospects in UV-protection field. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48813.     

Formation of nanoporous poly(methyl silsesquioxane) thin films using adamantane for low‐k application

Nanoporous poly(methyl silsesquioxane) PMSSQ thin films for low‐k application have been prepared using chemically attached adamantylphenols as pore generating materials (porogen). To obtain the mechanically stable porous structure, multifunctional 1,2‐bistrimethoxysilylethane (BTMSE) was employed in addition to methyltrimethoxysilane as a main matrix material. From the decomposition of porogen, confirmed by FTIR and TGA, the nanoporous thin films containing pores less than 5 nm, which are characterized using sorption analysis, were successfully achieved. The dielectric constant was significantly decreased to 1.9, while maintaining the stable mechanical properties with the elastic modulus of 3.7 GPa measured by a nanoindenter. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fabrication and surface characterization of electrosprayed poly(L‐lactide) microspheres

Electrospraying is a one‐step technique for fabricating polymeric microspheres/nanospheres, and the surface characterization of polymeric microspheres fabricated under high voltage is different from an emulsion method. In this study, biodegradable poly(l ‐lactide) (PLLA) microspheres were successfully fabricated by electrospraying, and electrospraying parameters were used to investigate the size and ζ potential of the electrosprayed PLLA microspheres. The results demonstrate that electrospraying was a one‐step method for fabricating monodispersed PLLA microspheres with a size of 1.92 ± 0.35 μm and that the enrichment of methyl groups on the surface of the microspheres contributed to the strong hydrophobicity of electrosprayed PLLA microspheres. Of all the electrospraying parameters investigated, the size and ζ potential of the PLLA microspheres increased with increasing solution concentration and flow rate and decreased with increasing injection voltage and collecting distance. The results provide a theoretical basis for preparing electrosprayed polymeric microspheres as drug carriers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Performances of novel poly(diaryloxyphosphazene) based heat shielding materials with various fibrous reinforcements

Elastomeric heat shielding materials (EHSMs) are necessary to protect combustion chambers of solid rocket motors during their working. Poly(diaryloxyphosphazene) (PDPP) elastomers own inherent thermal stability and flame retardancy because the backbone of alternating phosphorus and nitrogen atoms can be a novel promising polymer matrix toward EHSMs. The present study deals with the development of a novel PDPP based EHSMs with several different fibrous reinforcements, including Kevlar, polyimide, and carbon short fibers. It is found that PDPP/Kevlar composites show outstanding tensile strength and ablation resistance because of their strong interfacial bonding between matrix and fibers which benefits from the possible network of intermolecular hydrogen bonds. PDPP/carbon composites produce a compact charred layer due to their high char yields of carbon fibers. These results improve the understanding of the role of polyphosphazenes with different kinds of fibers on ablation mechanisms, which enable the possibility to exploit intrinsic properties of polyphosphazenes.     

Preparation of aromatic poly(1,3,4‐oxadiazoles) pulps and their paper properties

To improve the paper properties of the poly(1,3,4‐oxadiazoles) (POD), the POD pulps were prepared by prechemical and mechanical methods to increase their polarity, contact area, and interaction. The fibrillated degree of the staple fibers was evaluated by the Canadian Standard Freeness and the specific surface area, while the surface free energy was calculated by the Micro–wilhelmy method. Meanwhile, the functional groups and compositions on the surface of the POD fibers were confirmed by the FTIR–ATR and the X‐ray photoelectron spectroscopy, and the surface morphological structure and the crystalline structure of the POD fibers were observed by the fiber analyzer, scanning electron microscope, and Wide‐angle X‐ray diffraction, respectively. It was found that the pronounced abrasive and distinctive grooves were formed on the surface of the POD fibers after prechemical and mechanical treatment. The surface free energy of POD fibers increased 8.41%, and the polar part increased by 32.10% after treatment. It was confirmed that the polar functional groups and fibril were formed after chemical and mechanical treatment, so the interaction of the POD fibers was highly enhanced, and as a result the apparent density, tensile strength, fold endurance, and tear strength of the paper formed by those treated fibers were all improved apparently. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39818.     

Preparation and properties of UV‐curable fluorinated polyurethane acrylates

A series of UV‐curable polyurethane acrylates (PUA0, FPUA3, FPUA6, FPUA 9 FPUA12, FPUA15, where the numbers indicate the wt % of perfluoroalkyl acrylate), were prepared from a reactive oligomer [4,4 ?‐dicyclohexymethanediisocyanate(H12MDI)/ poly(tetramethylene glycol)(PTMG)/2‐hydroxyethyl methacrylate (HEMA): 2/1/2 molar ratio, prepolymer:40 wt %] and diluents [methyl methacrylate (MMA, 20 wt %)/ isobornyl acrylate (IBOA, 40–25 wt %)/heptadecafluorodecyl methacrylate (PFA, 0–15 wt), total diluents: 60 wt %]. This study examined the effect of PFA/IBOA weight ratio on the properties of the UV‐curable polyurethane acrylates for antifouling coating materials. The as‐prepared UV‐curable coating material containing a 15 wt % PFA content in diluents (MMA/IBOA/PFA) form a heterogeneous mixture, indicating that a PFA content of approximately 15 wt % was beyond the limit of the dilution capacity of diluents for the oligomer. In the wavelength range of 400–800 nm, the UV‐cured PUA0 film sample was quite transparent (transmittance%: near 100%). On the other hand, the transmittance% of the FPUA film sample decreased markedly with increasing PFA content. XPS showed that the film‐air surface of the UV‐cured polyurethane acrylate film had a higher fluorine content than the film‐glass dish interface. As the PFA content increased from 0 to 12 wt %, the surface tension of the UV‐cured urethane acrylates decreased from 26.8 to 15.6 mN/m, whereas the water/methylene iodide contact angles of the film–air surface increased from 90.1/63.6° to 120.9/87.1°. These results suggest that the UV‐curable polyurethane acrylates containing a PFA content up to 12 wt % have strong potential as fouling‐release coating materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40603.     

Preparation and properties of β‐phase graphene oxide/PVDF composite films

We report preparation of graphene oxide (GO) from expanded graphite (EG) via a modified Hummers method. GO/PVDF composites films were obtained using solvent N, N‐Dimethylformamide (DMF) and cosolvent comprising deionized water/DMF combination. X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses revealed that the main crystal structure of the composite films is β‐phase, and use cosolvent method tends to favor the formation of β‐phase. Scanning electron microscopy (SEM) was used to investigate the microstructure of composite films. Storage modulus and loss modulus were measured by Dynamic mechanical analysis (DMA). Broadband dielectric spectrum tests showed an increase in the dielectric constant of the GO/PVDF composite films with the rising content of GO, and by cosolvent method could improve the dielectric constant while reducing the dielectric loss. Our method that uses GO as an additive and deionized water/DMF as the cosolvent provides a promising and low‐cost pathway to obtain high dielectric materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41577.     

Surface modification of microcrystalline cellulose (MCC) and its application in LDPE‐based composites

Microcrystalline cellulose (MCC) was modified by grafting onto its surface ferulic acid, methacryloyl chloride and oleoyl chloride. The efficacy of the chemical modification was confirmed by X‐ray photoelectron spectroscopy. In addition, the size distribution of the cellulosic particles was investigated by optical microscopy and laser granulometry and its hydrophobicity was evaluated using a contact angle method. Finally, to investigate the affinity of modified MCC with a nonpolar polymer and to assess its potential as a biobased reinforcing filler, the modified MCC was compounded into low‐density polyethylene. An organic peroxide, dicumyl peroxide, was added at selected formulations to see if it could further enhance mechanical bonding between the polymer and the particulates. The dispersion was assessed by scanning electron microscopy. Mechanical properties were investigated through tensile testing while the melt rheology of the composites was monitored by small angle oscillatory shear rheology. The acylation modification of the MCC improved the dispersion within LDPE and enhanced the mechanical properties of the composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44348.     

Antibacterial poly{(4‐vinyl phenylboronic acid)‐co‐[2‐(dimethylamino)ethyl methacrylate]} copolymers and their application in water‐based paints

Herein, we report the synthesis of poly(4‐vinylphenylboronic acid) (PVPBA) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) homopolymers, copolymers, and their methyl, pentyl, and octyl quaternized forms as dopant in water‐based permanent antibacterial paints. Both quaternized and nonquaternized forms of P(VPBA‐co‐DMAEMA) copolymers have reflected higher MIC values relative to PDMAEMA homopolymers. High molecular weight copolymers were more active against Escherichia coli ATCC 25922, contrarily, lower molecular weight copolymers showed higher antibacterial activity against Staphylococcus aureus ATCC 25923. The paint films prepared with quaternized PDMAEMA homopolymers with a weight of 10% showed better antibacterial activity in water and airborne tests than the copolymers. However, it has been shown that the inadequate anti‐biofilm properties of homopolymer‐containing paint films are overcome with the VPBA content of the copolymer structure and the most effective antibacterial and anti‐biofilm properties have been obtained with paint films containing P(VPBA‐co‐5QDMAEMA) copolymers. These paint films, which can maintain antibacterial and anti‐biofilm properties for at least 1 year, have the potential to be an alternative to Ag/Cl based solid surfaces which require the active substance to be regenerated. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46245.     

Hybrid polyaniline–TiO2 nanocomposite Langmuir–Blodgett thin films: Self‐assembly and their characterization

Polyaniline (PANi)–titanium dioxide (TiO₂) nanocomposite materials were prepared by chemical polymerization of aniline doped with TiO₂ nanoparticles. Surface pressure–area (π‐A) isotherms of these nanocomposites show phase transformations in the monolayer during compression process. Multiple isotherms indicate that the monolayer of the nanocomposite material can retain its configuration during compression‐expansion cycles. Langmuir–Blodgett thin films of PANi–TiO₂ nanocomposite were deposited on the quartz and indium tin oxide coated conducting glass substrates. Fourier transfer infrared spectroscopy and UV–visible spectroscopy study indicates the presence of TiO₂ in PANi, whereas X‐ray Diffraction study confirmed the anatase phase of TiO₂ and particle size (～nm) of PANi–TiO₂. The morphology of Langmuir–Blodgett films of these nanocomposites was also characterized by atomic force microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41386.     

Surface modification of halloysite nanotubes with l‐lactic acid: An effective route to high‐performance poly(l‐lactide) composites

To improve the interfacial bonding between halloysite nanotubes (HNTs) and poly(l ‐lactide) (PLLA), a simple surface modification of HNTs with l ‐lactic acid via direct condensation polymerization has been developed. Two modified HNTs were obtained: HNTs grafting with l ‐lactic acid (l‐HNTs) and HNTs grafting with poly(l ‐lactide) (p‐HNTs). The structures and properties of l‐HNTs and p‐HNTs were investigated. Then, a series of HNTs/PLLA, l‐HNTs/PLLA and p‐HNTs/PLLA composites were prepared using a solution casting method and were characterized by polarized optical microscopy (POM), field scanning electron microscopy, and tensile testing. Results showed that l ‐lactic acid and PLLA could be easily grafted onto the surface of HNTs by forming an Al carboxylate bond and following with condensation polymerization, and the amounts of the l ‐lactic acid and PLLA grafted on the surface of the HNTs were 5.08 and 14.47%, respectively. The surface‐grafted l ‐lactic acid and PLLA played the important role in improving the interfacial bonding between the nanotubes and matrix. The l‐HNTs and p‐HNTs can disperse more uniformly in and show better compatibility with the PLLA matrix than untreated HNTs. As a result, the l‐HNTs/PLLA and p‐HNTs/PLLA composites had better tensile properties than that of the HNTs/PLLA composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41451.     

High loading boron nitride chemically bonded with silicone rubber to enhance thermal neutron shielding and flexibility of polymer nanocomposites

Flexible materials with excellent radiation shielding and flexibility are essential to the personal protective equipments (PPEs) for protecting workers from nuclear radiations. However, it is an enormous challenge to obtain the desired materials since high loading filler in polymer nanocomposites usually promotes radiation shielding while restrains its flexibility. Here, a facile “thiol-ene click” means is applied to chemically bond high loading boron nitride (BN) nanoparticles with silicone rubber (SR) in SR/BN nanocomposites for thermal neutron shielding. Uniform dispersion of BN nanoparticles and good compatibility of interfaces in the nanocomposites with high loading filler lead to increased flexibility instead of decrease. In particular, the nanocomposite with 40 wt% BN displays 911% of elongation at break that is about 50% enhancement to that of neat SR. Furthermore, higher loading BN in the nanocomposites means better thermal neutron shielding. Namely, enhanced thermal neutron shielding and flexibility is achieved at SR/BN nanocomposite with 40 wt% BN. The present work provides a facile strategy towards superior integrated performance of flexible materials for radiation shielding, such as wearable devices.     

Low-frequency ferroelectric switching studies in PVDF thin films across Cu or (Ag/Cu)/PVDF/Cu capacitor structures

Ferroelectric switching dynamics of polyvinylidene fluoride (PVDF) thin films in Cu or (Ag/Cu)/PVDF/Cu capacitors are explored by varying PVDF film thickness, applied electric field amplitude (4.35–87.5 MV/m) and frequency (100 mHz–200 Hz). Comprehending spontaneous polarization and its dependence upon interfaces, an electric field is critical for organic ferroelectric memory devices. In this article, quasi-static current–voltage, and polarization–electric field measurements are used to explain the relationship between the coercive field, signal amplitude, and frequency. The observed coercivity enhancement at lower PVDF film thicknesses and with rising frequencies of the applied signal is discussed with Kolmogorov-Avrami-Ishibashi domain nucleation and growth model. The relation between domain growth and the top electrode layer is further discussed from the exponent parameters.     

Fabrication of large‐scale superhydrophobic composite films with enhanced tensile properties by multinozzle conveyor belt electrospinning

Large‐scale superhydrophobic composite films with enhanced tensile properties were prepared by multinozzle conveyor belt electrospinning. First, a strategy of conveyor belt electrospinning was introduced for large‐scale fabrication since the conveyor belt can expand the electrospinning area unlimitedly. During the electrospinning (or electrospraying) process, certain kinds of fibers are combined on the conveyor belt in one electrospinning (or electrospraying) step. The superhydrophobicity of electrospun film can be achieved by the presence of PS beads and bead‐on‐string PVDF fibers, while submicron PAN fibers are responsible for the improvement of mechanical properties. The result shows that CA value of the surface comprising of PS beads and bead‐on‐string PVDF fibers could reach up to 155.0°. As the submicron PAN fibers increased, the value of CA decreased, changing from 155.0° to 140.0°, meanwhile the tensile strength of composite film was enhanced from 1.14 to 4.12 MPa correspondingly which is beneficial to putting the films into practice. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39735.     

Employment of ultrasonic waves for the preparation of PVA/TiO2‐BSA nanocomposites: Mechanical,thermal, and optical properties

The goal of this project is to obtain poly(vinyl alcohol) (PVA)/TiO₂‐bovine serum albumin (BSA) nanocomposite (NC) films in different weight percentages of modified TiO₂. For this purpose, to prevent the accumulation of nanoparticles (NPs) in the PVA matrix, the surface of the TiO₂ NPs was treated with the BSA molecules. To achieve this aim, ultrasonic waves were used as an environmentally friendly and green process that decrease the time of reactions, help better spreading of TiO₂ NPs and maintain dimensions of TiO₂ NPs in the nanoscale range. In the end, the features of the PVA/TiO₂‐BSA NC films were considered with a variety of techniques. The Fourier transform infrared spectroscopy, energy dispersive X‐ray, and X‐ray diffraction showed that the BSA was well placed on the surface of TiO₂ NPs. The thermal gravimetric analysis and UV‐visible results demonstrated that all the PVA/TiO₂‐BSA NC films have better thermal and optical properties than the pure PVA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46558.