Synthesis of novel block copolymers containing polyhedral oligomeric silsesquioxane (POSS) pendent groups via ring-opening metathesis polymerization (ROMP)

Ring-opening metathesis copolymerization of norbornene ethyl polyhedral oligomeric silsesquioxane monomer (NBEPOSS) and 2-endo-3-exo-5-norbornene-2,3-dicaboxylic acid trimethyl ester (NBETMS) was performed using a Ru-based catalyst, RuCl₂(CHPh)(PCy₃)₂. The block copolymers poly(NBETMS-b-NBEPOSS) were then converted to poly(NBECOOH-b-NBEPOSS) by hydrolysis and precipitation. The polymers were characterized by NMR and GPC and the actual NBEPOSS contents were found in good correspondence with the theoretical values. A linear dependence of M_n on conversion and a linear dependence of ln([M₀]/[M]) on reaction time observed in the polymerization of NBETMS suggest that chain breaking reactions such as termination and chain transfer are minimal. Low PDI values and smooth GPC peak shifts during polymerization after addition of a second batch of the same monomer or a NBEPOSS monomer also reflect a living process.     

Characterization of polyurethane foam prepared by using starch as polyol

Polyurethane foams were prepared using starch as a main component of polyols and their structural, mechanical, and absorbing properties for organic solvents were investigated. Fourier transform infrared spectra showed that urethane linkage was formed by the reactions between ? NCO of diisocyanates and ? OH of polyols. When polyurethane foams were prepared at high molar ratio of ? NCO/? OH, the unreacted ? NCO groups were detected. Also, urea linkage was formed by the reaction between diisocyanate and water, which was used as the foaming agent. The micrographs showed that the polyurethane foams had closed‐cell structure, of which the cell size increased with ? NCO/? OH molar ratio. The density of polyurethane foams increased with molecular weight of polyethylene glycol. The compressive moduli of polyurethane foams increased with ? NCO/? OH molar ratio. Polyurethane foams prepared using toluene‐2,4‐diisocyanate as diisocyanate had the highest modulus, while those prepared using hexamethylene diisocyanate had the lowest modulus. In case of the absorbency for the organic solvents, the polyurethane foams prepared at ? NCO/? OH molar ratio of 0.8 had the maximum absorbency. Among several organic solvents, the absorbency for dimethyl sulfoxide was the highest, while the absorbency for tetrahydrofuran was the lowest. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1544–1553, 2007     

Preparation of hydroxyapatite/poly(vinyl alcohol) composite film with uniformly dispersed hydroxyapatite particles using citric acid

Biocompatible hydroxyapatite (HA)/poly(vinyl alcohol) (PVA) composites and their transparent films were prepared by the coprecipitation and solvent casting method. The formation of HA in PVA composite powder was confirmed by the characteristic phosphate bands at 1100–1032 and 565 cm^?1 at FT‐IR spectra, and the weight ratio of HA to PVA was 50/50 examined by TGA. The crystal melting temperature of HA/PVA decreased compared with that of pure PVA. HA/PVA (50/50) composite powder and pure PVA were dissolved in dimethyl sulfoxide to obtain a film with HA/PVA weight ratio of 10/90. To improve HA particles' dispersity, which is one of the major factors affecting the mechanical properties of composite materials, various contents of citric acid were used for the preparation of HA/PVA films. At a citric acid concentration of 5 wt %, HA/PVA film with good dispersity of HA particles was obtained. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Application of essential work of fracture concept to toughness characterization of high‐density polyethylene

Deformation and fracture toughness of high‐density polyethylene (HDPE) in plane‐stress tension was studied using the concept of essential work of fracture (EWF). Strain range for necking was determined from uniaxial tensile test, and was used to explain the deformation transition for 2‐staged crack growth in double‐edge‐notched tensile test. Through work‐partitioning, EWF values for HDPE were determined for each stage of the crack growth. Appropriateness of these EWF values to represent the material toughness is discussed. The study concludes that the EWF values for ductile polymers like HDPE may not be constant, but vary with the deformation behaviour involved in the crack growth process. POLYM. ENG. SCI., 47:1327–1337, 2007. © 2007 Society of Plastics Engineers     

Estimation of the saw-tooth shock wave using a lead shock programmer

Structure durability under shock load is evaluated by performing a shock resistance test. Saw-tooth shock wave is generated in a specific environment and transmitted to the structure. The saw-tooth shock wave is generated using a specific impact test system. In general, the impact test system is generally composed of three types: Drop, lateral and rotational. Each type of impact test system has different detail parts. This study applies the drop-type impact test system. A test table, a fixed table, and a shock programmer compose comprise the drop-type impact test system. The drop-type impact test system uses the initial height of the test table, where the specimen is mounted on. The impact velocity in the drop-type impact test is determined by the initial height of the test table. The shock programmer generates the shock wave transmitted to the specimen mounted on the test table, which is then. The shock wave transmitted to the specimen is then generated by the shock programmer material. Parameter research of the parameter testing on the shock programmer has to be performed using the drop-type impact test system to generate the saw-tooth shock wave with non-linear characteristics. This study generates the saw-tooth shock wave by designing and simulating the lead shock programmer. Lead is considered as the shock programmer material. The accuracy of the simulation program (i.e., LS-Dyna) is verified by performing the drop shock test of theon the three types of lead shock programmer with three types. The results of the time history on the test table acceleration between the simulation and the test are compared with those of the shock test and the simulation. The shock test and simulation results are plotted using the tolerance range of the saw-tooth shock wave presented in MIL-STD-810G. The saw-tooth shock wave generated using the lead shock programmer with conical and truncated conical shape is estimated using the verified simulation program. The aspect ratio of the conical and truncated conical lead shock programmer is presented to generate the saw-tooth shock wave is also presented.

     

Living cationic polymerization of isobutyl vinyl ether (II): Photoinduced living cationic polymerization in a mixed solvent of toluene and diethyl ether

A new method of preparation of living cationic polymer of isobutyl vinyl ether via photoinduced polymerization in the presence of diphenyliodonium iodide (DPII, initiator) and zinc iodide in a mixed solvent of toluene/diethyl ether, which was irradiated at ?78°C for short period, was completed within 15 min. The reaction was allowed for further reaction in the dark until monomer was fully consumed. It was found that increase in the conversion of monomer to polymer during the irradiation is very limited. Confirmation of the linear dependence of number‐average molar mass of resulting polymer on % conversion together with the fact that polymerization proceeds until monomer consumption, and controllability of number‐average molar mass of resulting polymer, depending on the molar ratio of monomer and initiator, strongly suggests the living nature of this polymerization, unless reaction temperature becomes higher than 0°C, i.e., the absence of chain breaking process. The narrow molar mass distribution, whose polydispersity index values are less than 1.2, reveals that the rate of initiation where irradiation is usually completed within 15 min is much faster than that of propagation in cationic nature in this system. Effect of some major factors, such as solvent polarity and temperature, on the living nature of the polymerization was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3581–3586, 2006     

Preparation and barrier property of poly(ethylene terephthalate)/clay nanocomposite using clay‐supported catalyst

Poly(ethylene terephthalate) (PET)/clay nanocomposite was prepared by the direct polymerization with clay‐supported catalyst. The reaction degree of catalyst against the cation exchange capacity of clay was 8 wt %. The intercalation of PET chains into the silicate layers was revealed by X‐ray diffraction studies. SEM morphology of the nanocomposite showed a good dispersion of clay‐supported catalyst, ranging from 30 to 100 nm. The intercalated and exfoliated clay‐supported catalyst in PET matrix was also observed by TEM. The improvement of O₂ permeability for PET/clay‐supported catalyst composite films over the pure PET is approximately factors of 11.3–15.6. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4875–4879, 2006     

Encapsulation mechanism of N2 molecules into the central hollow of carbon nitride multiwalled nanofibers

Nitrogen molecules have been encapsulated into the central hollows of vertically aligned carbon nitride (CN) multiwalled nanofibers by dc plasma-enhanced chemical vapor deposition with C₂H₂, NH₃, and N₂ gases on a Ni/TiN/Si(1 0 0) substrate at 650 °C. X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectra showed the existence of nitrogen molecules in CN nanofibers. Elemental mapping images with electron energy loss spectroscopy of the CN nanofiber and catalyst metal, and optical emission spectroscopy spectra of the plasma showed the distribution of nitrogen atoms and molecules in the CN nanofiber, catalyst metal, and gaseous precursor, respectively. These studies showed that atomic nitrogen diffused into the catalytic metal particle because of the concentration gradient and then saturated at the bottom of the particle. Saturated nitrogen atom participated in the formation of the CN nanofiber wall but most of nitrogen was trapped in the central hollow of the nanofiber as molecules.     

Enhanced surface morphologies of screen-printed carbon nanotube films by heat treatment and their field-emission properties

A heating process for obtaining free-standing carbon nanotube emitters is presented with the aim of improving field-emission properties from the screen-printed multiwalled carbon nanotube (MWCNT) films. Using an atmosphere with an optimum combination of nitrogen and air for heat treatment of CNT films, the CNT emitters can be made to protrude from the surface. This allows for a high emission current and the formation of very uniform emission sites without special surface treatment. The morphological change of the CNT film by this technique has eliminated additional processing steps, such as surface treatment which may result in secondary contamination and damage to the film. Despite its simplicity the process provides a high reproducibility in emission current density which makes the films suitable for practical applications.     

Novel blue‐light‐emitting polymers based on a diphenylanthracene moiety

New luminescent copolyethers with diphenylanthracene‐emitting segments and electron‐transporting benzoxazole phenyl were successfully synthesized by aromatic nucleophilic substitution. The polymers, characterized by NMR and IR spectroscopy, were obtained in high yields, showed good solubility in various organic solvents, and had high thermal stability with high glass‐transition temperatures (125–129). The number‐average molecular weights of the polymers were 10,000–20,000, and they had polydispersity indices of 1.2–1.4. The optical and electrochemical properties of the polymers were also investigated. The pure blue emission for the polymers (maximum wavelength = 430–440 nm) was obtained with high photoluminescence quantum efficiency (76–78%) in a chloroform solution. The blue electroluminescence for the poly(TDPB) (maximum wavelength = 440 nm) was obtained with a turn‐on voltage of 15–20 V when simple light‐emitting diodes (indium tin oxide/polymer/Al) were fabricated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2151–2157, 2006