Structure of polyurethane elastomers. X-ray diffraction and conformational analysis of MDI-propandiol and MDI-ethylene glycol hard segments

X-ray diffraction and conformational analysis have been used to investigate the structure of polyurethane hard segments prepared from diphenylmethane 4,4′-diisocyanate (MDI) with propandiol (PDO) and ethylene glycol (EDO) as chain extenders. The results are compared with those obtained previously for MDI-butandiol (BDO) hard segments. In the latter system, the poly(MDI-BDO) chains are fully extended with an all-trans conformation for the O(CH₂)₄O unit, and a monomer repeat of 18.95 Å. The unit cell is triclinic with a tilted base plane such that adjacent chains are staggered along the fibre axis. In contrast both poly(MDI-PDO) and poly(MDI-EDO) adopt unstaggered structures, i.e. the chains are in register and the unit cell base planes are perpendicular to the chain axis. The monomer repeats of 16.2 Å for poly(MDI-PDO) and 15.0 Å for poly(MDI-EDO) are shorter than the predicted repeats for fully-extended chains, indicating that these polymers have contracted conformations containing some gauche CH₂ groups. Conformational analysis shows that the 16.2 Å repeat for poly(MDI-PDO) can be achieved with the O(CH₂)₃O unit in the trans-gauche⁺-gauche⁺-trans or gauche⁺-trans-trans-gauche⁺ conformations. Similarly the 15.0 Å repeat for poly(MDI-EDO) is predicted for the gauche⁺-trans-gauche^? conformation for the O(CH₂)₂O unit. These conformations are of higher energy than the all-trans fully-extended chains. This may explain the higher crystalline perfection of the poly(MDI-BDO) hard segments, for which crystallization in the all-trans form will probably provide a greater driving force for phase separation.     

Comparative effects of cobalt carboxylates on the thermo‐oxidative degradation of LDPE films

This article reports the effect of three cobalt carboxylates—cobalt stearate (CoSt₃), cobalt palmitate (CoPal₃), and cobalt laurate (CoLau₃)—on the thermo‐oxidative degradation of low‐density polyethylene (LDPE) films prepared by sheeting process. The carboxylates were blended with LDPE in the concentration range of 0.05–0.2% (w/w). The degradation was monitored by techniques such as FTIR spectroscopy, change in the mechanical properties (tensile strength and elongation at break), viscometry, surface electron microscopy, melt flow index measurements, and apparent density measurements. Studies indicate that films containing these additives are highly susceptible to thermo‐oxidative degradation. Oxygen containing functionalities such as carbonyl and vinyl species are generated on the surface of polyethylene because of thermo‐oxidation, as indicated by FTIR studies. This oxidative process is accelerated in the presence of cobalt carboxylates. The degradation of LDPE was found to increase proportionally with concentration as well as with increasing chain length of the cobalt carboxylate, and follow the order CoSt₃ > CoPal₃ > CoLau₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3758–3765, 2007     

Conformational analysis of poly(MDI-butandiol) hard segment in polyurethane elastomers

As part of our study of the structure of the hard segments of polyurethane elastomers, we have used conformational analysis to predict the conformation of the polyurethane chain formed from diphenylmethane 4,4′-diisocyanate (MDI), with butandiol as the chain extender. X-ray diffraction indicates the chain conformation is highly extended in the solid state, with a monomer repeat of 18.95 Å. The chain conformation can be predicted from the interaction between the large contiguous groups. Semiempirical and CNDO/2 molecular orbital calculations have been used to investigate the phenyl-phenyl, phenyl-urethane, and urethane-butandiol interactions. Minimum energy for the diphenyl-methane section occurs for a CCH₂C bridge angle of θ = 110°. However, the more likely conformation in the polymer is probably that at the subsidiary minimum at θ = 118°, in which the phenyl rings are mutually perpendicular, which is comparable to the conformation seen for model compounds. For the phenyl-urethane interactions the energy minimum is at $\text{ч = ±90°}$, with the combination $\text{(ч}{}_1\text{, ч}{}_2\text{) = (?90°, +90°)}$ leading to the necessary extended conformation. Calculations for the butandiol segment favour an all-trans conformation which is coplanar with the urethane groups. The predicted conformation of the polymer chain has a fibre repeat which matches the observed value, and this cannot be attained if the butandiol unit contains any gauche bonds. Model compounds show large variations for the phenyl-urethane conformation from the predicted minimum at $\text{ч = ±90°}$, indicating the importance of intermolecular stacking forces in determining the polymer conformation. However, provided the adjacent butandiol and urethane groups are coplanar, the fibre repeat is relatively insensitive to variations of ч.     

A two‐station embossing process for rapid fabrication of surface microstructures on thermoplastic polymers

An embossing strategy involving a hot station and a cold station for sequentially heating and cooling the embossing tool was investigated to reduce cycle times in hot embossing polymer microstructures. Experimental studies showed that aluminum stamps with a thickness of 1.4 mm can be rapidly heated from room temperature to 200°C in 3 s using contact heating against a hot station at 250°C. Microchannels and microlenses were successfully embossed onto high‐density polyethylene and acrylonitrile–butadiene–styrene substrates using a heating time less than 3 s and a total cycle time around 10 s. The two‐station embossing process for the microlens was also numerically studied. The simulated filling behavior agreed with the experimental observation and the predicted thermal and deformation history of the polymer offered a good explanation on the experimentally observed process characteristics. POLYM. ENG. SCI., 47:530–539, 2007. © 2007 Society of Plastics Engineers.     

Corrosion of nickel-base and iron-base alloys in a simulated fluidized-bed coal-combustion environment

The modes of initiation and propagation of corrosion attack on a series of high-temperature alloys were studied in synthetic gas mixtures at 900°C. The gas mixtures were intended to simulate the oxygen and sulfur partial pressures experienced in reducing zones in a coal-fired fluidized-bed combustor and comprised mixtures of CO, CO₂, and SO₂. The alloys studied were candidates for in-bed heat exchanger tubing for an air-heater cycle operating at 843°C and 300–500 psig and so ranged from type 300-series stainless steels to nickel-base alloys. With the exception of two FeCrAlY alloys and types 304 and 347 stainless steels, it was found that sulfidation corrosion could be initiated on all the alloys within 0.25 hr; the rate of propagation of the corrosive attack depended on the flux of SO₂ in the environment and on the nickel content of the alloys. The presence of iron in the alloys appeared to slow the initiation of sulfidation, by forming a continuous iron oxide layer. The effects of various alloying additions are discussed, and a schematic model for the initiation of sulfidation is proposed.     

Improving the performance of speaker and language identification tasks using unique characteristics of a class

In classification tasks, the error rate is proportional to the commonality among classes. In conventional GMM-based modeling technique, since the model parameters of a class are estimated without considering other classes in the system, features that are common across various classes may also be captured, along with unique features. This paper proposes to use unique characteristics of a class at the feature-level and at the phoneme-level, separately, to improve the classification accuracy. At the feature-level, the performance of a classifier has been analyzed by capturing the unique features while modeling, and removing common feature vectors during classification. Experiments were conducted on speaker identification task, using speech data of 40 female speakers from NTIMIT corpus, and on a language identification task, using speech data of two languages (English and French) from OGI_MLTS corpus. At the phoneme-level, performance of a classifier has been analyzed by identifying a subset of phonemes, which are unique to a speaker with respect to his/her closely resembling speaker, in the acoustic sense, on a speaker identification task. In both the cases (feature-level and phoneme-level) considerable improvement in classification accuracy is observed over conventional GMM-based classifiers in the above mentioned tasks. Among the three experimental setup, speaker identification task using unique phonemes shows as high as 9.56 % performance improvement over conventional GMM-based classifier.     

Equivalence of classicality and separability based on P phase–space representation of symmetric multiqubit states

Classical and quantum world views differ in peculiar ways. Understanding decisive quantum features—for which no classical explanation exist—and their interrelations is of foundational interest. Moreover, recognizing non-classical features carries practical significance in information processing tasks as it offers insights as to why quantum protocols work better than their classical counterparts. We focus here on two celebrated notions of non-classicality viz., negativity of P phase–space representation and entanglement in symmetric multiqubit systems. We prove that they imply each other.     

Fully developed flow of granular materials down a heated inclined plane

Summary The mechanics of flowing granular materials such as coal, sand, metal ores, etc., and their flow characteristics have received considerable attention in recent years as it has relevance to several important technological problems. In a number of instances, these materials are also heated prior to processing, or cooled after processing. The governing equations for the flow of granular materials, taking into account the heat transfer mechanism by conduction, are derived using a continuum model (cf. Goodman and Cowin [1], [2], Rajagopal and Massoudi [3]). For a fully developed flow of these materials down an inclined plane, the equations reduce to a system of coupled non-linear ordinary differential equations. The resulting boundary value problem is solved numerically and the results are presented for cases where the viscosity and thermal conductivity are assumed to be functions of the volume fraction. It is shown that the equations admit multiple solutions for certain values of the parameters.List of symbols D Symmetric part of the velocity gradient - K thermal conductivity - L velocity gradient - T Cauchy stress tensor - b body force - h characteristic height - q heat flux - r radiating heat - u velocity vector - angle of inclination of the inclined plane with the horizontal - specific internal energy - distributed mass density - temperature - volume fraction - bulk mass density     

Design of high-speed data transfer turbo code for body channel communication transceivers

In this work, a digital differential transmitter based on low-power wireless compensation transceiver for body channel communication (BCC) is proposed. Further, the proposed transceiver is composed of Touch Status Detection Unit (TSDU), Wireless Status Compensation Unit (WSCU), and a reconfigurable preamplifier. Initially, the human body channel environment for wireless communication is investigated based on properties from 1 to 100 MHz. Further, the turbo code-based encoding scheme is used to encode the data before transferring the data on the transmitter side. Also, the proposed error-correcting parallel turbo decoder using a modified step-by-step algorithm is presented. The turbo code-based decoding scheme is used to recover the error-free transmitted data at the receiver side. Results demonstrate that the proposed BCC transceiver is designed using 90 nm CMOS technology and it is observed that the proposed BCC transceiver has utilized an area of 600mm². Also, the maximum data rate achieved by a proposed BCC transceiver was 100 Mbps, and the overall transceiver power consumption is 0.42 mW, and energy for communication is 0.02 nj/b.