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We investigated the effects of hydrogen separation using high-temperature anhydrous proton-exchange membrane fuel-cell technology. Various acid-doped para-polybenzimidazole (p-PBI)-chain end-tethered amine-polyhedral oligomeric silsesquioxane (NH2-POSS) membranes were prepared via a unique sol–gel transition method termed as the poly(phosphoric acid) process. The resulting NH2-POSS-capped p-PBI membranes exhibited a higher phosphoric acid-doping level (128–223.5%) and proton conductivity (0.23–0.29 S cm−1 at 160 °C and 0% relative humidity) than the parent p-PBI membrane. The chemical chain end-termination of p-PBI with cage-like NH2-POSS significantly enhanced the electrochemical H2/CO2 and H2/CO separation at 160 °C. The hydrogen separation of the NH2-POSS-capped p-PBI system required a relatively small amount of energy, and the system exhibited a good dynamic response. The favorable interfacial interaction between the NH2-POSS and the p-PBI host, high thermomechanical stability, and good fuel-cell and hydrogen-separation performance at high temperatures up to 160 °C indicate the applicability of the NH2-POSS-capped p-PBI membranes to electrochemical power generation and hydrogen pumps for practical industrial applications in harsh and extreme environments.

Here, highly stretchable and transparent UV curable poly(urethane-acry-late) elastomer has been synthesized by reacting urethane acrylate oligomer and two reactive diluents monomers. The synthesized elastomers can be stretched up to 600% and have high transparency of over 90% transmittance. The synthesized elastomers have been applied to several applications. Simple 3D model was printed with a 3D printer on the market. Stretchable ionic conductors were fabricated by a facile method of adding salt with ionic conductivity. Similarly, the resin with β-cyclodextrin, a cage-structured molecule, was cured and foam was generated simultaneously under the UV radiation. This research paves a new way for further development in applications of UV curable transparent elastomer and 3D printable elastomeric material.

The main challenge to developing future display substrates is to synthesize flexible substrate materials that also have excellent optical and thermal properties, and low thermal expansion number. In this study, a novel trifluoromethylated asymmetric aromatic diamine, 4-[[4-(4-amino-2-trifluoromethylphenoxy)phenyl]sulfonyl-3-(trifluoromethyl)]benzenamine (AFPSFB), was synthesized through nucleophilic substitution. Conventional two-step polycondensation of AFPSFB with commercially available tetracarboxylic dianhydrides enabled the fabrication of fully or semi-aromatic polyimides (PIs). The resulting PIs were highly soluble in polar aprotic solvents with good optical and thermal properties. Next, polyhedral oligomeric silsesquioxane containing an amine group (NH2-POSS) was reacted with the resulting soluble PI. All the PI-POSS nanohybrids displayed excellent optical properties, including high transparency (>91% at 400 nm), low refractive index (

We report herein on thermally stable polyimide (PI) hybrid optical imaging sensors based on chalcogenide element-blocks that can be advantageously used in light-weight optical materials, especially in infrared (IR) applications. A change in the length of chalcogenide element-blocks, which formed the building block backbone of PI, induced a difference in overall transmittance in the visible and near IR range of frequencies. The PI hybrids covalently bonded with zirconia displayed tunable refractive indices up to 1.79 at 532 nm along with an unprecedented transmission from the visible to the IR spectral region. The amine-functionalized zirconia nanofillers can also significantly improve the thermomechanical properties of the host PI due to the favorable interaction with the PI matrix. In particular, we demonstrate that PI hybrids can accomplish high-quality IR thermographic imaging of human subjects, and even visualize details of elaborate micropatterns. Consequently, the PI hybrids can be used to manufacture thermally robust and transparent optical lenses that are cost-competitive compared to the conventionally used inorganic types, thus offering advantages of improved processability, flexibility, reduced volume, and light-weight characteristics.

Crosslinked metal oxide containing nanocomposite membranes, in which the filler also acts as crosslinker, were prepared by blending polybenzimidazole (PBI-OO) and phenylsulfonated TiO2 particles (s-TiO2). Thermal curing changes the ionically crosslinked system into a covalently crosslinked system. The synthesized s-TiO2 nanoparticles were analyzed by thermal gravimetric analysis and scanning electron microscopy. The covalently crosslinked nanocomposite membranes (c-sTiO2-PBI-OO) were doped with phosphoric acid (PA) for high temperature proton exchange membrane fuel cell (HT-PEMFC) application. The membrane properties, such as PA uptake, dimensional change, gel content, proton conductivity, mechanical property, and single cell performance were evaluated and compared with the properties of acid-doped c-PBI-OO. PA doped 6-c-sTiO2-PBI-OO (6 wt% sTiO2) showed the highest uptake of 392 wt%, and a proton conductivity at 160 °C of 98 mS cm−1. In the fuel cell, a peak power density of 356 mW cm−2 was obtained, which is 76% higher than that of a c-PBI-OO based system (202 mW cm−2). To evaluate the stability of the membrane performance over time, the best performing membrane was tested for over 700 h.

A method to improve the optical properties of transparent poly(amide-imide) (PAI) by incorporating a new flexible diamine is demonstrated. The new diamine-incorporated PAI films show a lower glass transition temperature, yellow index, residual stress than neat PAIs irrespective of their structure. The DSC results show that the new diamine increases the flexibility of the polymer matrix indicating the poor packing of the matrix. However, the light transmittance reduces from 89.73 to 88.58%. This discrepancy can be clarified by measuring the residual stress of the PAI films. The results confirm that PAI has high elasticity and flexibility at low and high temperatures. Thus, flexible diamines can be added to PAI films for transparent materials owing to their good optical properties such as a transmittance of over 87%, yellow index lower than 2.8 and low residual stress

A new diamine was designed and synthesized to improve the flexibility of colorless polyimides by reducing residual stress. Four variations of colorless polyimides with the same dianhydride (4,4′-(hexafluoroisopropylidene)-diphthalic) and four different diamines (bis[4-(3-aminophenoxy)-phenyl] sulfone, bis(3-aminophenyl) sulfone, 2,2′-bis(trifluoromethyl)benzidine, and 2,2-bis(4-aminophenyl)-hexafluoropropane) were used. A series of colorless polyimides were prepared by adding the new diamine. The carbon and ether bonds between the benzene rings of the new diamine affected the flexibility and optical properties of colorless polyimide. The synthesis of the new diamine was confirmed by NMR measurements. Furthermore, the decrease in residual stress at room temperature and the glass transition temperature was confirmed. The effect of the new diamine was most evident for polyimide with a bulky and rigid structure. Though a slight yellow color appears because of the broken charge transfer complex balance, controlling the content of the new diamine will allow application of polyimides in flexible display.

Nanocomposite polymer electrolyte membranes comprising a crosslinked polymer blend of poly(vinyl alcohol)/poly(styrene sulfonic acid-co-maleic acid) (PVA/PSSA-co-MA) and fumed silica nanoparticles were prepared for direct methanol fuel cell (DMFC) applications. Silica nanoparticles could be incorporated well uniformly in the completely miscible system, which can form a three-dimensional network structure to achieve the enhancement of mechanical properties as well as the additional reduction of methanol permeability. The optimized proton conductivities and methanol permeability of the PVA/PSSA-co-MA membrane with silica nanoparticles of 10 wt.% were 0.0482 S cm-1 at room temperature and 5.78 × 10-7 cm2 s-1 at the methanol concentration of 40% (w/w), respectively.

The development of tannic‐acid‐based textile materials is a good candidate that enables both flame retardancy and antibacterial properties. When nanocarbon materials are used together, it is possible to not only realize complex functions but also increase physical properties, thereby expanding the potential range of application of the materials.

In this study, transparent thin films for coating material are synthesized by adding bulky CF3 and hydroxyl groups intro into poly(amide-imide)s. As expected, these poly(amide-imide)s show higher shear adhesion and higher glass transition temperatures than the neat poly(amide-imide) due to hydrogen bonding of the hydroxyl groups. In addition, the modification to the poly(amide-imide) structure leads to only slight decreases in transmittance and yellow index. Consequently, the successful synthesis of poly(amide-imide)s with wide applications as transparent coating materials due to their optical properties and high adhesion is demonstrated. Transparent flexible display and coating products can be manufactured with poly(amide-imide)s having high reliability and a low chance of cracking due to their favorable thermal properties.

We report a facile method to enhance mechanical properties of polymer nanocomposites using three-dimensional (3D) network structures of functionalized graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs) in a polymer matrix. The GO and MWCNTs were functionalized using Fisher indole and diazonium-salt reactions to produce pyridine (Py) moiety on the GO and MWCNTs. The functionalized GO (Py-RGO) and MWCNT (Py-MWCNT) nanocomposites exhibited hydrogen-bond assisted 3D network structures in a polyimide (PI) matrix. By incorporating 1 wt% of carbon materials (0.9 wt% Py-RGO and 0.1 wt% Py-MWCNTs) in a PI, the tensile strength and modulus of the ternary nanocomposites reached 581 MPa and 31 GPa, respectively, which was an enhancement of 221% and 312% compared with pristine PI. The fracture energy of the PI/Py-RGO/Py-MWCNT nanocomposites improved 200% and approached 29.7 MJ m−3. The formation of the 3D network structure of the functionalized carbon nanomaterials is considered to significantly affect load transfer of nanofillers in the polymer matrix, and produce high performance polymer nanocomposites.

The decomposition of formic acid (HCOOH) over ZrO2 catalysts synthesized by precipitation method was investigated and their catalytic activity based on unit mass of catalyst was compared by varying the calcination temperature in the 500–1000 °C range. The calcined ZrO2 samples were characterized using temperature-programed desorption (TPD) of iso-propanol (IPA), H2O, and HCOOH as well as X-ray diffraction (XRD), pyridine-adsorbed infrared spectroscopy (Py-IR) and N2 sorption. The catalytic activity as a function of the calcination temperature of ZrO2 showed a volcano-type curve with a maximum at 900 °C. The catalytic activity of ZrO2 in the decomposition of HCOOH well correlated with Bronsted acid site density, and it was influenced by the crystalline phase of ZrO2. Furthermore, the evolution of the Bronsted acid site density measured by Py-IR as a function of the calcination temperature was in good accordance with the desorption temperature determined by IPA- and HCOOH-TPD experiments. When H2O vapor was added, the conversion of HCOOH slightly decreased, while the CO selectivity remained almost constant. However, when CO was supplied, the conversion of HCOOH decreased continuously, and the selectivity to H2 gradually increased, indicating that the formation of zirconium suboxides with characteristics approaching those of metals was successful using CO as a reductant.

New diamines for high-performance poly(ester imide)s (PEsIs) containing dimethyl groups at the ortho-position of amino groups and ester derivatives have been developed to improve optical transparency and glass transition temperature (Tg) while maintaining a low coefficient of thermal expansion (CTE). Four kinds of PEsIs derived from bis(4-amino-3,5-dimethylphenyl) terephthalate (BADMT) and aromatic dianhydrides such as 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 4,4’-oxydiphthalic anhydride (ODPA), and 4,4'-(hexafluoroisopropylidene)diphthalic (6FDA) were synthesized via a two-step polycondensation. All PEsIs exhibited outstanding properties, such as light color, a good transmittance of >90% at 550 nm, high Tg above 289 °C and 5% weight loss temperature (483–511 °C), and low CTE (11–68 ppm/°C). The effect of the substituent on molecular packing and properties, including optical and thermomechanical properties for the resulting PEsIs were examined in detail. The temperature-dependent CTE of the PEsIs was determined using molecular dynamics (MD) simulation. The molecular orbital (MO) calculation models support the discussions on the electronic substituent effect of the PEsI main chains. Our molecular architecture and systematic property studies with MD and MO promote a better understanding of the polyimides.

A facile one-step method for synthesis of a porous monolithic polyimide aerogel was successfully developed. The specific thermal curing, slow desiccating process and swelling method were used in synthesizing monolithic polyimide aerogel without any additional chemical reaction to create a connected structure among the polyimide-based spherical aerogel microparticles. Using this method, the monolithic polyimide aerogel can be easily fabricated whilst using no additional chemicals for crosslinking. This type of polyimide aerogel was produced homogeneously by the polyimidization of pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA). The synthesized porous monolithic polyimide aerogel has many good properties which could be used in various industries, as it maintained a high thermal decomposition temperature (10% weight decomposition temperature: T d10% ) of approximately 577 °C and a glass transition temperature (T g ) of 432 °C, with bulk density of 490.7 kg/m 3 , porosity of approximately 45% and average pore size of 4 nm (by nitrogen adsorption test) of polymer and 157 nm (by mercury intrusion method) of space observed in FE-SEM image. Also, the monolithic polyimide aerogel had an excellent oil-adsorbing capacity of 150%, and the adsorbed oil could be separated easily using a simple drying process. The dried monolithic polyimide aerogel showed significant recoverability and reusability of adsorbed oil. In addition, the monolithic polyimide aerogel exhibited high mechanical resistance such that the structure can withstand a high pressure greater than 122.3 kPa, under which the monolithic polyimide aerogel (MPA) was compressed but did not break. This type of MPA shows excellent thermal, mechanical properties and great processability, and could be the new candidate for high performance materials in various industries, especially catalyst field.

Supercritical methanol is a popular fluid as a supercritical medium for decrosslinking reaction of crosslinked polyethylene. However, due to its toxicity, a safe alternative medium is much to be desired. In this work, various sub- and supercritical fluids with different polarity characters were investigated to find a safe alternative medium for continuous decrosslinking of silane-crosslinked polyethylene (S-XLPE). Like methanol, all examined fluids, including ethanol, propanol, and water, exhibited first-order reaction kinetics regarding the gel content in the continuous decrosslinking process. The reaction rate constant values were observed as 2.806, 2.569, 2.383, and 2.130 min −1 in supercritical methanol, supercritical ethanol, supercritical 2-propanol, and subcritical water at 380 °C, respectively. As a non-toxic fluid with reaction kinetics very comparable to that of methanol, ethanol was found to be the best alternative medium for the continuous decrosslinking reaction of S-XLPE.

For the first time, a kinetic study on the supercritical decrosslinking reaction of silane-crosslinked polyethylene (S-XLPE) in a continuous process was conducted. The decrosslinking reaction in a continuous process was corresponding to the first-order reaction model in which the reaction rate was linearly proportional to the gel content. The residual gel content exponentially decreased with reaction time. Reaction constant was observed exponentially related to the reaction temperature. The continuous decrosslinking reaction revealed kinetic constants of 1.355 ± 0.103, 2.715 ± 0.177, and 4.348 ± 0.218 min −1 at 360, 380 and 390 °C, respectively and activation energy of 132.36 kJ mol −1 .

In this study, poly(amide-imide)s are synthesized for electronic materials by adding amide groups into polyimide. As it is expected, poly(amide-imide) shows an amorphous structure with a lower glass transition temperature and residual stress than the neat polyimide due to the high steric hindrance of the amide group. Also, the modification to the polyimide structure leads to higher transmittance and enhances colorless properties. Consequently, successful synthesis of poly(amide-imide)s is demonstrated which has wide applicability in the electronic industries due to their low glass transition temperature. It is expected that semiconductor and integrated circuit products can be manufactured utilizing poly(amide-imide)s with high reliability and a low chance of cracking due to their lower residual stress. Furthermore, it envisioned that the improved optical properties of poly(amide-imide) materials will allow for their applications in transparent displays and coating products.

Graphene nanoparticles coated with tannic acid were synthesized as non-halogen flame retardants; further, these nanoparticles were electrospun with polyurethane to produce multifunctional composite nanofibers. The composite nanofibers showed improved flame retardant, antimicrobial, and mechanical properties with increasing amounts of bio-based, non-halogen flame retardant. For instance, at 5 wt% of flame retardant, the peak heat release rate was reduced from 340.75 to 235.23 W/g along with 500% and 135% improvement in the antimicrobial activity and Young's modulus, respectively, compared to neat polyurethane fibers. These multifunctional composite nanofibers have potential applications in various fields, such as automobile, construction, and biomedical device.

Simple self-healing behavior of polymers that respond to multiple physicochemical stimuli are highly desirable for industrial applications. In this study, under various external environmental stimulating factors, we focus on the self-healing kinetics of polymer bilayer films (PBFs) comprising a colorless polyimide (CPI) bottom-substrate layer and linseed oil loaded microcapsule (LOMC)-embedded polydimethylsiloxane (PDMS) upper-healing layer. The experimental results showed clear correlation between stimulating factors and the healing time. Although the crack-healing behavior of PBF with 5 wt% microcapsule under air atmosphere is fairly slow, it has an improved healing effect at the artificial crack interface heating to 70 °C; moreover, gradual healing is observed by moisture absorption in environments with relative humidity of 70%. Remarkably, we found that ultraviolet (UV)-light irradiation through the 5 wt% LOMC-filled PDMS layer triggers a noticeable kinematic advantage for the drying reaction that initiates interfacial self-healing. Short-time (20 min) UV-irradiated PBF 5 wt% exhibits a low water vapor permeability of 35.4 g m−2 day−1 and excellent healability with ~91% recovery by single capsule-type photochemical-induced self-healing. The proposed approach advances the extrinsic healing of colorless polymers in a kinetically effective way without compromising their chemical composition.

We herein report an effective way to fabricate high-performance polybenzimidazole (PBI) nanocomposite membranes using sulfophenylated titanium oxide (s-TiO2) nanoparticles for application in high temperature polymer electrolyte membrane fuel cell (HT-PEMFC). The s-TiO2, multifunctional inorganic proton conductors that can improve proton conductivity and cell performance of PBI, was obtained through the surface modification. The PBI nanocomposite membranes were doped with phosphoric acid (PA) for performance evaluation. Properties such as PA doping level, proton conductivity, PA retention and cell performance were evaluated and compared to neat PBI. PA doped PBI-sTP2 (2 wt% TiO2) showed the highest doping of 12.1 and proton conductivity of 0.096 S/cm at 150 °C. In the cell test, peak power density of 621 mW/cm2 was obtained, roughly 30% better performance compared to neat PBI (471 mW/cm2).

Polyurethane acrylate/surface-modified colloidal calcium carbonate (PUA/SCaCO3) nanocomposite coatings were successfully prepared via a UV-curing technology. The structural and morphological features of the PUA/SCaCO3 nanocomposites were characterized by Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), and wide angle X-ray diffraction (XRD). The physical properties were strongly dependent upon chemical and morphological structures that originated from differences in SCaCO3 loading. A critical SCaCO3 concentration was observed for the evolution of both the structure and physical properties of the PUA/SCaCO3 nanocomposites as a function of SCaCO3 content. The thermal stability was measured by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively, and displayed some enhancement with the incorporation of SCaCO3 into PUA. Although the nanomechanical properties increased up to 3 wt% SCaCO3 content, they decreased due to lack of interfacial interaction with high SCaCO3 loading. Most importantly, the water uptake and water vapor transmission rate (WVTR) varied from 5.51 to 1.78 wt% and 28.9 to 19.9 g/m2 day, respectively, exhibiting significant enhancement in water resistance. The results clearly reveal that the performance of UV-curable PUA/SCaCO3 nanocomposites is strongly dependent on organically-modified colloidal SCaCO3 nanoparticles.

The effects of norbornene (NE) crosslinking and diamine bridge linkages (ether, sulfone, and trifluoromethyl) on polyimide films were investigated. The purpose of this study was to study the behavior of the NE endcapped polyimide with different diamine bridge linkage structure at elevated temperatures on residual stress and modulus change. 5-Norbornene-2,3-dicarboxylic acid was introduced as the end-capping agent in order to increase the ratio of crosslinking in the structure through reverse Diels-Alder reaction. Wide angle X-ray diffraction (WAXD) was measured to study the relation of d-spacing and structure change of the bridge linkage of polymers through NE crosslinking. Coefficient of thermal expansion (CTE) and residual stress were measured to confirm the loaded stress between the substrate and polymer film through a thin film stress analyzer (TFSA). Storage (e′) and loss modulus (e″) were studied at elevated temperatures to study the relation of bridge linkage mobility of the polyimide at elevated temperature.

To enhance the thermal stability and barrier properties of pure poly(vinyl alcohol) (PVA), five different cross-linked poly(vinyl alcohol)/boric acid (PVA/BA) hybrid films were prepared via a solution blending method, and their properties including barrier properties, thermal stability, transparency, and mechanical properties were investigated as a function of the BA content. The physical properties of the PVA/BA hybrid films were strongly dependent upon the chemical structure and morphology of the films originating from the amount of BA and change in degree of cross-linking. With increasing BA content, the size and amount of PVA crystallites decreased, whereas the cross-linking density increased, resulting in more compact packing of the molecules and lower free volume in the amorphous regions. The glass transition temperature and thermal stability were highly enhanced with increasing BA content. The oxygen transmission rate (OTR) of pure PVA decreased from 5.96 to 0.15 cc/m 2 day with increasing BA content and were greatly suppressed by 22.8% for 1% BA, 7.7% for 3% BA, and 2.5% for 3% BA, respectively, relative to pure PVA film. With increasing BA content, their water-resistant pressure and tensile strength increased with BA loading. All the hybrid films showed good transparency. These properties of the cross-linked PVA/BA hybrid films make them potential candidates for versatile applications as coatings, films, and packaging materials.

Cuprous oxide (Cu2O) has received much attention as a photocatalyst due to its direct band gap structure, small band gap energy, non-toxicity, and abundance. However, Cu2O usually suffers from poor stability because the oxidation state of copper is easily changed. In this work, Cu2O particles of three different shapes were prepared with distinct surface structures: cubes with (100) facets, octahedra with (111) facets, and rhombic dodecahedra with (110) facets. Their shape stability was estimated in deionized water with or without light irradiation. The Cu2O(100) facets were selectively deformed under dark conditions, as expected from density functional theory calculations. The rhombic dodecahedra showed the most violent degradation under light irradiation, with many large thorns appearing on the surface. When water splitting was attempted using the shaped Cu2O particles, the rhombic dodecahedra produced the most hydrogen, whereas the cubes produced none. Oxygen was not measured because the holes generated upon light absorption were used to oxidize the Cu2O surface to CuO. A conformal TiIrOx overlayer was successfully formed on the rhombic dodecahedral Cu2O particles, and the coated particles presented overall water splitting producing both hydrogen and oxygen. They also showed significantly improved stability over repeated water splitting reactions relative to bare Cu2O particles or TiOx-coated Cu2O particles.

A series of polyimide (PI) was prepared by reacting 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) as the anhydride and bis(3-aminophenyl) sulfone (APS), bis(4-(3-aminophenoxy)-phenyl) sulfone (BAPS), 2,2- bis(4-aminophenyl)-hexafluoropropane (6FPD), 2,2-bis(4-(4-aminophenoxy)-phenyl)hexafluoropropane (6FBAPP), 2,2'- bis(trifluoromethyl)benzidine (TFDB), or 1,4-phenylenediamine (PDA) as the diamine. Residual stress behaviors were detected in-situ during thermal imidization of the polyimide precursors using a thin film stress analyzer (TFSA), and inter- preted with respect to their morphology. According to the molecular orientation and packing order, the residual stress var- ied from 23.1 to 12.5 MPa, decreased with increasing chain rigidity. The thermal properties of the PI films were investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and thermomechanical analysis (TMA). Their optical properties were measured by ultraviolet-visible spectrophotometer (UV-vis), and spec- trophotometry. The properties of PI films were found to be strongly dependent upon the morphological structure. How- ever, trade-offs between residual stress and optical properties were identified.

A series of poly(urethane acrylate)/Cloisite 15A (PUA/C15A) nanocomposite films were successfully prepared via a UV-curing system, and their physical and barrier properties were investigated as a function of clay content. The physical properties were strongly dependent upon the chemical and morphological structures originating from differences in Cloisite 15A content. With high clay content, the PUA/C15A nanocomposite films displayed an intercalation/exfoliation combined structure. However, no strong interfacial interactions occurred between the PUA and clay, possibly leading to poor dispersion with relatively high clay content. The thermal stability displayed some enhancement with the introduction of clay into PUA, while the gas and moisture barrier properties showed significant enhancement. The oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) decreased with increasing contents of Cloisite 15A, and varied within the range of 714.0–71.1 cm3/m2 day and 29.9–13.9 g/m2 day, respectively. Thus the enhanced gas and moisture barrier properties of PUA/C15A nanocomposite films make them promising candidates for food and pharmaceutical packaging applications. However, further studies will be performed to increase the compatibility and dispersion of clay particles in the PUA polymer matrix.

A series of poly(vinyl alcohol)/sodium montmorillonite (PVA/NaMMT) nanocomposite films were prepared via a solution method, and their water sorption and water-resistant properties were investigated as a function of clay content. The water sorption and water resistance properties were strongly dependent on the chemical structure and film morphology originating from the NaMMT content. The water diffusion coefficient and water uptake of the PVA/NaMMT nanocomposite films were obtained by best fits to a Fickian diffusion model. The diffusion coefficient and water uptake in the PVA/NaMMT nanocomposite films varied between 8.16 × 10−10 and 3.60 × 10−10 cm2 s−1 and 35.6 and 29.9 wt%, respectively. Both the diffusion coefficient and water uptake decreased as the content of NaMMT in pure PVA was increased. Additionally, the water resistance pressure (mm) of the PVA/NaMMT nanocomposite films increased with increasing NaMMT content. Contact angle analyses showed that the chemical affinity to water and the surface energy of the nanocomposite films decreased with increasing NaMMT content. Furthermore, the well-dispersed and exfoliated structure in the nanocomposite films not only induced an increased tortuous path for water molecules to pass through, but also increased the molecular order. However, to enhance the water sorption properties and water resistance of hydrophilic PVA, further studies to increase the dispersion of clay particles and ensure desired morphological qualities such as crystallinity and molecular packing order in the PVA/clay nanocomposite films are required. POLYM. COMPOS., 36:660–667, 2015. © 2014 Society of Plastics Engineers

In this study, the swelling method for controlling the pore size of the polyimide aerogel is demonstrated. The swelling method allows the pore size to be increased by changing the spherulitic formation. This newly developed method is simple and hardly affects original polymer chain and thus can be applied to a variety of precursor polymers without hindering the synthesis process. Unlike other methods, no foreign additives such as additional chemicals or crosslinkers are required to enlarge the pores of the aerogel, which contributes to higher homogeneity of the material. In order to test its effectiveness in pore size control and observe its behavior with different polyimides, various monomers—pyromellitic dianhydride, 3,3′,4,4′-benzophenonete-trac-arboxylic dianhydride, and 4,4′-oxydiphthalic anhydride—were tested to verify the potential of the proposed method. Depending on different polymer backbone, each aerogel showed a similar slope but different increase rate of the pore size. The retained thermal and structural properties of the synthesized aerogels were confirmed by thermogravimetric analysis, differential scanning calorimetry, and Fourier-transform infrared spectroscopy. This newly proposed simple method showed its effectiveness in increasing the pore sizes, enlarging the mesopore size from 4 nm to 20 nm and total pore volume from 1.29 cm 3 / g to 2.06 cm 3 / g for swollen aerogel when pyromellitic dianhydride was used. Also, the surface area increased from 54 m 2 / g to 88 m 2 / g , and the porosity increased from 58% to 73%.

Polybenzimidazole hybrid membranes (H1–H3) were prepared by incorporating different amounts (wt.%) of inorganic hetero poly acids (IHA-Si) into polybenzimidazole (PBI) matrix. Structural, morphological and thermal characteristics of all the hybrid membranes were studied by FT-IR, XRD, SEM and TGA and further investigated functional relationships between the materials structure and metal ion uptake using Hg(II), Pb(II), Y(III), and Cd(II). It was found that H3 was most selective toward Hg(II) as compared to H1 and H2 and further uptake capacity of H1–H3 was strongly dependent on mesoporous silica. The hybrid membranes with high mesoporous silica (H3) exhibited high thermal stability and high uptake capacity toward Hg(II) which was experimentally determined to be 2.48 mg g−1. Desorption study for the regeneration of adsorbent was also achieved using ethylenediaminetetraacetic acid solution. Ultimately, the proposed method provided reasonable results for the determination of Hg(II) in environmental water samples.

친환경 소재인 폴리프로필렌카보네이트(PPC)를 포장소재로서 응용하기 위하여 가로세로비가 큰 박리흑연 EFG (exfoliated graphite)를 이용하여 함량을 달리한 6종류의 PPC/EFG 나노복합필름을 제조하였다. 제조한 나노복합필름의 수분흡수 거동을 gravimetric method를 이용하여 측정하였으며, 나노복합필름의 수분에 대한 화학적 친화성(chemical affinity)과 모폴로지(morphology) 변화를 이용하여 해석하였다. 필름 내로의 수분확산 거동은 박막의 불균일성에도 불 구하고 Fickian diffusion model에 잘 부합하였으며, EFG의 함량이 증가할수록 수분 확산계수와 수분 흡수량은 12.5 × 10 -10 cm 2 sec -1 에서 7.2 × 10 -10 cm 2 sec -1 , 8.9 wt%에서 4.2 wt%로 각각 감소하였다. 이는 수분에 대한 PPC의 차단특성이 EFG의 도입에 따라 향상되는 것을 의미한다. 높은 가로세로비를 가진 EFG를 PPC에 도입함으로써 PPC/EFG 나노복합 필름의 수분에 대한 우수한 차단성 특성 발현은 패키징분야를 포함한 차단성이 요구되는 분야로의 친환경 PPC 응용 성이 클 것으로 기대된다. 한편, EFG의 도입효과를 극대화하기 위한 추가적인 EFG의 분산성 향상연구가 필요하다.

Relatively high aspect ratio exfoliated graphite (EFG) particles with an average size of 7.4 mu m and a nanometer sized thickness of 30-50 nm were successfully prepared by thermal treatment at 1050 degrees C and subsequent ultrasonication for application as a filler to improve the physical properties of eco-friendly poly(propylene carbonate) (PPC). A series of poly(propylenecarbonate)/exfoliated graphite (PPC/EFG) nanocomposite films with different EFG contents were prepared via a solution blending method. The physical properties were strongly dependent upon the chemical and morphological structures originating from the differences in EFG composition. The morphological structures, thermal properties, mechanical properties and barrier properties of the nanocomposite films were investigated as a function of the EFG content. While all of the PPC/EFG nanocomposite films exhibited good dispersion of EFG to some extent, Fourier transform infrared and SEM results revealed that solution blending did not lead to strong interactions between PPC and EFG. As a result, poor dispersion occurred in composite films with a high EFG content. By loading EFG particles, the oxygen permeabilities, moisture permeabilities and water uptake at equilibrium decreased as the EFG content increased. Compared with pure PPC, PPC/EFG nanocomposite films have enhanced molecular ordering. Specifically, the 2% PPC/EFG composite film shows greater molecular ordering than the other composite films, which results in the highest mechanical strength. In future work, the compatibility and dispersion of the PPC matrix polymer and EFG filler particles should be increased by modifying the EFG surface or introducing additives

The current paper describes enhanced electrochemical capacitive performance of chemically grown Cobalt hydroxide (Co(OH)2) nanorods (NRs) decorated porous three dimensional graphitic carbon foam (Co(OH)2/3D GCF) as a supercapacitor electrode. Freestanding 3D porous GCF is prepared by carbonizing, high internal phase emulsion (HIPE) polymerized styrene and divinylbenzene. The PolyHIPE was sulfonated and carbonized at temperature up to 850 °C to obtain graphitic 3D carbon foam with high surface area (389 m2 g−1) having open voids (14 μm) interconnected by windows (4 μm) in monolithic form. Moreover, entangled Co(OH)2 NRs are anchored on 3D GCF electrodes by using a facile chemical bath deposition (CBD) method. The wide porous structure with high specific surface area (520 m2 g−1) access offered by the interconnected 3D GCF along with Co(OH)2 NRs morphology, displays ultrahigh specific capacitance, specific energy and power. The Co(OH)2/3D GCF electrode exhibits maximum specific capacitance about ~1235 F g−1 at ~1 A g−1 charge-discharge current density, in 1 M aqueous KOH solution. These results endorse potential applicability of Co(OH)2/3D GCF electrode in supercapacitors and signifies that, the porous GCF is a proficient 3D freestanding framework for loading pseudocapacitive nanostructured materials.

A novel hyper-branched polybenzimidazole (HB-PBI) has been synthesized and efficiently utilized as a conducting polymer for the fabrication of an efficient high temperature fuel cell. The developed fuel cell showed outstanding proton conductivity (0.168 Scm(-1) at 150 A degrees C) along with excellent single cell performance, displaying a maximum power density of 0.346 Wcm(-2). The HB-PBI has been synthesized by polymerization of bibenzimidazole diterephthalic acid (BBIDTA) and 3,3'-diaminobenzene in the presence of poly phosphoric acid while the BBIDTA was synthesized by treating trimellitic anhydride with 3,3'-diaminobenzene. Both HB-PBI and BBIDTA were structurally characterized by nuclear magnetic resonance (H-1 and C-13 NMR). HB-PBI showed high thermal stability and mechanical properties, findings that were corroborated by thermogravimetric analysis and use of a universal testing machine. Additionally, proton conduction and the thermal and mechanical properties of HB-PBI were compared with polybenzene imidazole (m-PBI), and found that HB-PBI has higher proton conducting, thermal and mechanical properties.

A series of polyurethane acrylate (PUA)/ZnO nanocomposite films with different ZnO contents were prepared via a UV-curing system. To ensure good dispersion in the PUA matrix, ZnO nanoparticles were modified with a silane coupling agent and confirmed by FT-IR analysis. The morphological structures, thermal properties, mechanical properties and water transfer properties of the prepared films were investigated as a function of their ZnO concentration. WAXD and SEM analyses showed that the surface-modified ZnO nanoparticles were homogeneously dispersed in the PUA matrix and the molecular ordering increased with increasing ZnO content. Compared with neat PUA, the hardness and elastic modulus in films increased from 0.03 to 0.056 GPa and from 2.75 to 3.55 GPa, respectively. Additionally, the water uptake and WVTR in the PUA/ZnO nanocomposite films decreased as the ZnO content nanoparticles increased, which may come from enhanced molecular ordering and hydrophobicity in films. UV light below approximately 450 nm can be efficiently absorbed by incorporating ZnO nanoparticles into a PUA matrix, indicating that these composite films exhibit good weather ability and UV-shielding effects. The enhanced physical properties achieved by incorporating modified ZnO nanoparticles can be advantageous in various applications, whereas the thermal stability of the composite films should be increased.

Organic-inorganic nanohybrids, 3,4-dihydroxycinnamic acid/layered double hydroxide (CA/LDH), 4-hydroxy-3,5-dimethoxycinnamic acid/layered double hydroxide (SA/LDH), and 3-amino-5-triflouromethylbenzoic acid/layered double hydroxide (FBA/LDH) have been synthesized by co-precipitation reaction of organic ultraviolet (UV) ray absorbents such as 3,4-dihydroxycinnamic acid, 4-hydroxy-3,5-dimethoxycinnamic acid, 3-amino-5-triflouromethylbenzoic and Zn2Al layered double hydroxide (LDH). Detailed structural and absorption properties of the nanohybrids were studied by using X-ray diffraction (XRD), FT-IR and UV-Vis transmittance spectra which revealed that organic UV absorbents have been intercalated into the interlayer spaces of LDH and all nanohybrids showed excellent UV ray absorption. All the nanohybrids showed a lower catalytic activity as compared to the net organic UV ray absorbents by applying air oxidation to castor oil.

The thermal cationic latent initiators, N-benzyl-3-methylimidazolium hexafluoroantimonate (BMH1) and N-butyl-3-methylimidazolium hexafluoroantimonate (BMH2) were synthesized and applied to the thermal cationic polymerization of diglycidyl ether of bisphenol A (DGEBA). The performance of BMH1 and BMH2 was examined by differential scanning calorimetry (DSC), which showed good thermal latent properties and excelled epoxy resin curing behavior. The morphology, thermal, mechanical, and water sorption properties of DGEBA resin cured by 1 wt% of BMH1 and BMH2 were measured by X-ray diffraction (XRD), scaming electron microscopy (SEM), thermogravimetric analysis (TGA), nanoindentation, and thin film diffusion analysis. The cured DGEBA/BMH1 system showed relatively higher thermal stability than the DGEBA/BMH2 system. The diffusion coefficient and water uptake were 14.2×10−9 cm2/s and 1.15 wt% for the DGEBA/BMH1 system and 11.5×10−9 cm2/s and 1.07 wt% for the DGEBA/BMH2 system, respectively. Therefore, DGEBA/BMH2 showed higher resistance to water sorption than DGEBA/BMH1. On the other hand, hardness and elastic modulus of DGEBA/BMH2 were higher than those of DGEBA/BMH1. This can be attributed to the difference in the end group of initiators as well as the degree of crosslinking in the cured resin network. Open image in new window

Organic-inorganic hybrid membranes (HM1-HM4) were synthesized by incorporating 3 wt% (HM1), 5 wt% (HM2), 10 wt% (HM3), and 20 wt% (HM4) of silica precursors into UV-curable polyurethane acrylate (PU) matrix using sol-gel technique. PU, which was prepared by reacting polycaprolactone triol (PCLT) and isophorone diisocyanate (IPDI), was used as the starting organic polymer whereas tetraethoxysilane (TEOS) was used as a precursor for the development of the inorganic phase. The completion of the polymerization reaction of PU and the synthesis of hybrid membranes were confirmed by Fourier transform infrared spectroscopy (FTIR) whereas the morphology was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The thermal, mechanical, and anti-water sorption properties of the hybrid membranes were examined by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), nanoindentator and thin film diffusion analysis, which revealed that HM2 has the highest thermal, mechanical, and anti-water sorption properties. TGA demonstrated that the thermal decomposition temperature (T d10%) of HM2 increased significantly, being 30 °C higher than that of pure PU, whereas DSC indicated that the introduction of 5 wt% of TEOS increased the glass transition temperature from 93.8 to 103 °C. Accordingly, the mechanical and water sorption properties were also enhanced greatly as evidenced by nanoindentation analysis and anti-water sorption data, in which HM2 shows the highest elastic modulus (8.354 GPa), hardness (0.262 GPa), and lowest water sorption capacity. These thermal, mechanical, and anti-water sorption improvements are important for the practical process and applications of PU.

A series of polypropylene carbonate (PPC)/ZnO nanocomposite films with different ZnO contents were prepared via a solution blending method. The morphological structures, thermal properties, oxygen permeability, water sorption, and antibacterial properties of the films were investigated as a function of ZnO concentration. While all of the composite films with less than 5 wt % ZnO exhibited good dispersion of ZnO in the PPC matrix, FTIR and SEM results revealed that solution blending did not lead to a strong interaction between PPC and unmodified ZnO. As such, poor dispersion was induced in the composite films with a high ZnO content. By incorporating inorganic ZnO filler nanoparticles, the diffusion coefficient, water uptake in equilibrium, and oxygen permeability decreased as the content of ZnO increased. The PPC/ZnO nanocomposite films also displayed a good inhibitory effect on the growth of bacteria in the antimicrobial analysis. The enhancement in the physical properties achieved by incorporating ZnO is advantageous in packaging applications, where antimicrobial and environmental-friendly properties, as well as good water and oxygen barrier characteristics are required. Furthermore, UV light below ∼ 350 nm can be efficiently absorbed by incorporating ZnO nanoparticles into a PPC matrix. ZnO nanoparticles can also improve the weatherability of a PPC film. In future research, the compatibility and dispersion of the PPC matrix polymer and the inorganic ZnO filler nanoparticles should be increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.

UV-cured poly(urethane acrylate- co -acrylic acid) (PU- co -AA) films with five different compositions were prepared by reacting isophorone diisocyanate (IPDI), polycaprolactone triol (PCLT), 2-hydroxyethyl acrylate (HEA), and different weight ratios of trimethylolpropane triacrylate (TMPTA) and acrylic acid (AA) as diluents. Their synthesis and physical properties including gel content, adhesion properties, morphological structure, thermal properties, and mechanical hardness were investigated as a function of the AA content. It was found that the physical properties of the PU- co -AA films are strongly dependent upon the AA content. Crosscut tests showed that PU- co -AA films with lower AA content showed 0% adhesion (0B), and the adhesion of films increased dramatically as the AA content increased to 40–50%. The pull-off measurements showed that the adhesion force of the PU- co -AA films to stainless steel substrates varied from 6 to 31 kg f /cm 2 and increased linearly with increasing AA content. PU- co -AA films with higher AA content can be good candidates for UV-curable coating of metal substrates such as stainless steel. However, the thermal stabilities and mechanical hardness decreased with increasing AA content, which results from the relatively linear and flexible structure of AA.

Nanohybrids based on UV-curable polyurethane acrylate (PU) and cloisite 20B (C-20B) have been synthesized by solution blending method using different loading levels of C-20B. The structures of PU/C-20B nanohybrids were confirmed by Fourier transform infrared spectroscopy (FTIR) while X-ray diffraction and transmission electron microscopy (TEM) showed the intercalation of PU into layer silicates. The thermal properties of PU and PU/C-20B nanohybrids were investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetric (DSC). TGA tests revealed that the thermal decomposition temperature ( T d10% ) of the nanohybrid containing 5 wt% of C-20B increased significantly, being 61 °C higher than that of pure PU while DSC measurements indicated that the introduction of 5 wt% of clay increased the glass transition temperature from 89.7 to 101 °C. Accordingly, the mechanical and anti-water absorption properties proved also to be enhanced greatly as evidenced by nanoindentation anylsis and water absorptions data in which the nanohybrid containing 5 wt% of clay have highest elastic modulus (4.508 GPa), hardness (0.230 GPa) and lowest water absorption capacity. Thus the formations of nanohybrids manifests through the enhancement of thermal, mechanical and anti-water absorption properties as compared with neat PU due to the nanometer-sized dispersion of layered silicate in polymer matrix.

본 연구에서는 스테인레스 스틸(stainless steel)의 표면 코팅용 광경화 필름 개발을 위하여 isophorone diisocyanate(IPDI), polycaprolactone triol(PCLT), 2-hydroxyethyl acrylate(HEA), 그리고, 희석제로서 trimethylolpropane triacrylate(TMPTA)와 acrylic acid(AA)의 첨가비율을 달리한 광경화형 poly(urethane acrylate-co-acrylic acid)(PU-co-AA) 필름을성공적으로 제조하였으며, 제조한 PU-co-AA 필름의 모폴로지, 접착특성, 기계적 특성, 전기적 특성 등에 대한 AA 첨가량의 영향을 조사하였다. 모든 PU-co-AA 필름은 비정형 구조를 나타내었으나, AA의 함량이 증가할수록 분자 규칙및 패킹밀도는 감소하였다. 접착특성은 AA 함량 50% 이상에서는 접착력 5B 수준으로 스테인레스 스틸에 대한 우수한 접착특성을 나타내었으며, AA 함유량이 0%에서 66%까지 증가함에 따라 Pull-off strength법 접착력은 6~31 kg

Page 1115, the Acknowledgments should be corrected as follows: This work was supported by the KIST Institutional Program (Project No. 2E26600-16-041) and National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2017R1D1A1B03033332).

In this study, a biomimetic template was prepared and applied for growing calcium carbonate (CaCO 3 ) nanorods whose shape and polymorphism were controlled. A biomimetic template was prepared by adsorbing catalytic dipeptides into the pores of an anodic aluminum oxide (AAO) membrane. Using this peptide-adsorbed template, mineralization and aggregation of CaCO 3 was carried out to form large nanorods in the pores. The nanorods were aragonite and had a structure similar to nanoneedle assembly. This aragonite nanorod formation was driven by both the AAO template and catalytic function of dipeptides. The AAO membrane pores promoted generation of aragonite polymorph and guided nanorod formation by guiding the nanorod growth. The catalytic dipeptides promoted the aggregation and further dehydration of calcium species to form large nanorods. Functions of the AAO template and catalytic dipeptides were verified through several control experiments. This biomimetic approach makes possible the production of functional inorganic materials with controlled shapes and crystalline structures.

Four different structure polyimide thin films based on 1,4-phenylene diamine (PDA) and 4,4′-oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X-ray diffraction patterns and refractive indices. The residual stress was in the range of −5 to 38 MPa and increased in the following order: PMDA-PDA < BPDA-PDA < PMDA-ODA < BPDA-ODA. The hardness of the polyimide films increased in the following order: PMDA-ODA < BPDA-ODA < PMDA-PDA < BPDA-PDA. The PDA-based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA-based polyimide films. The in-plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA-ODA < BPDA-ODA < BPDA-PDA ∼ PMDA-PDA. The PDA-based polyimides, having a rigid structure, showed relatively better-developed morphological structure than the corresponding ODA-based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Two series of semi-interpenetrating polymer network (semi-IPN) composite films, PEI/bismaleimide (UTBM) and PEI/fluorinated BMI (UTFBM) were prepared using a thermoplastic PEI and two different crosslinkable imide moieties. The effects of chemical structure and content of crosslinkable imide moieties on thermal stability, dielectric properties, and water sorption have been investigated. Glass transition temperature and weight loss temperatures increased with increase in the content of crosslinkable imide moieties, indicating the enhanced thermal stability of the semi-IPN composite films. The refractive indices of the semi-IPN composite systems increased with increasing crosslinkable imide moieties due to the higher polarizabilities of atoms. The water sorption of the semi-IPN composite films was significantly decreased by the incorporation of crosslinkable imide moieties, which are interpreted by morphological structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Ferrocenophane-containing (Fcph) Schiff's bases p-C 12 H 25 O-(C 6 H 4 )CH=N(C 6 H 4 )Fcph (L A H) and p-C 12 H 25 O(C 6 H 4 )COO-(C 6 H 4 )CH=N(C 6 H 4 )Fcph (L B H) react with palladium(II) acetate to form μ-acetato- and chloro-bridged dimeric organopalladium complexes. By exchanging acetato-groups with the chloride anions, μ-chloro-bridged heteropolynuclear dimers are obtained that show thermotropic smectic A phases over a temperature range of 198 to 260 °C. The complexes [PdCIL A ] 2 and [PdCΙL B ] 2 can be transformed into a variety of mixed-ligand Pd ΙΙ complexes by treatment with salicyl-aldimine p-C 12 H 25 O(C 6 H 4 )COO(C6H3)(OH)CH=N(C6H4)-Fcph (L C H) and β-aminovinyl ketone p-C 12 H 25 O(C 6 H 4 )-COCH=CHNH(C 6 H 4 )Fcph (L D H). The obtained mixed-ligand heterometallic complexes [PdL A L C ], [PdL B L C ], [PdL A L D ] and [PdL B L D ] exhibit enantiotropic, thermotropic nematic phases over a broad temperature range from 71 to 205 °C. The structures of the synthesized compounds were characterized by means of 1 H NMR, IR and UV spectroscopy, as well as elemental analysis. The liquid crystalline properties were studied by polarising optical microscopy and DSC.

A simple method to synthesize silver or silver sulfide nanoparticle-decorated nanotubes without additional templating molecules or thermal treatment is reported in this study. Silver precursor ions were transferred to organic phase using phase-transfer agent from the aqueous precursor and organic solvent mixture, and then reduced to form nanoparticle-decorated nanotubes under the guidance of the self-assembled alkylthiol molecules at room temperature without additional templates. During the reduction of the precursor metal ions, the alkylthiol molecules formed cylindrical template as well as capped silver and silver sulfide nanoparticles, simultaneously. Through this multifunctional role of alkylthiol molecules, one-step preparation of nanoparticle-decorated nanotubes or nanorods was achieved. A series of control experiments were carried out in order to survey the effect of thiol amount on the nanotube formation. The concentration of alkylthiol was turned out to be a key factor determining the final morphology of the product. In addition, the nanotube formation is governed by the type of metal precursor ion used. These results will provide an advanced synthesis method on the alkylthiol-based nanotubes decorated with functional nanoparticles.