Structural change in the Brill transition of Nylon m/n (1) Nylon 10/10 and its model compounds

Structural changes in the Brill transitions of Nylon 10/10 and its model compounds have been investigated by carrying out the temperature-dependent measurements of X-ray diffraction and infrared spectra along with the DSC measurement. The crystal structure at room temperature was found to be the so-called α form with the all-trans zigzag methylene segments. When the samples were heated, the infrared progression bands of the methylene segments, which are sensitive to the length of all-trans segmental parts, were found to change their spectral patterns in the transition temperature region: the progression bands decreased in intensity and disappeared above the transition region. At the same time several new bands were observed to appear, which were found to correspond to the progression bands of (CH₂)₇-(CH₂)₅trans-zigzag segments. These spectral changes indicate that the methylene segments were conformationally disordered by an invasion of some gauche bonds and as a result the effective length of trans-zigzag segments became shorter. This conformational disordering was found to occur more remarkably in the methylene segment of NH-(CH₂)₁₀-NH part than the CO-(CH₂)₈-CO part. At the same time the infrared bands of amide groups, in particular the bands sensitive to the twisting angles about the CH₂-amide bonds were found to show the remarkable change, indicating the local conformational change from planar-zigzag to twisted form in the CH₂-amide moiety. The frequency shift of amide A band (NH stretching mode) indicated a weakening of intermolecular hydrogen bonds, which however, did not disappear up to the melting region. From these data combined with the X-ray diffraction data, the structural disordering in the Brill transition phenomena was deduced concretely.     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.     

Robust digital control of a DC–DC buck converter with low frequency samplings

A robust DC?CDC converter which can covers extensive load change and also input voltage changes with one controller is needed. Then the demand to suppress output voltage change becomes still severer. We propose an approximate 2-degree-of-freedom (2DOF) digital controller which realized start-up response and dynamic load response independently. The controller makes a control bandwidth wider, and at the same time makes variations of the output voltage small at sudden changes of a load and an input voltage. In this paper, a new approximate 2DOF digital control system with additional zeros is proposed. Using the additional zeros, the second-order differential transfer characteristics between equivalent disturbances and a output voltage are realized. Therefore, the new controller makes variations of the output voltage smaller and the sudden changes of the load and the input voltage. This controller is actually implement on a DSP and is connected to the DC?CDC converter. Experimental results demonstrate that this type of digital controller can satisfy given severe specifications with low frequency sampling.     

GemstoneFire: adaptive dispersive ray tracing of polyhedrons

Synthesizing realistic images of gemstones requires techniques beyond the scope of normal ray tracing. The fire of such highly refractive objects is what makes gemstones attractive, and also imposes very high computational overhead to perform time consuming dispersive ray tracing. Gemstones are usually cut in polyhdrons as for example, a brillant cut. After a detailed analysis of the nature of dispersive ray tracing of polyhedral objects, we propose here a new method of using three simple rays adaptively to model the ray spreading caused by dispersive refraction. It is shown that the proposed method reduces the computational complexity to an order close to that of normal ray tracing.     

Residual Stress in Siliceous Glass Between Mullite Crystals

A birefringence of siliceous glass, which is coexisting with mullite crystals, was studied by an optical polarizing microscope. The cause of the birefringence was assumed to be the residual stress induced by a large contraction difference between the mullite and glass on cooling. The stress has been evaluated to be as high as—0.3 GPa, and to correspond to the elastic one which began to develop at the glass transition point.     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Abnormal metabolism of polyunsaturated fatty acids and phospholipids in diabetic glomeruli

Studies were done on changes in phospholipid content and fatty acid composition of phospholipids and on the role of the acylation pathway in synthesis of phospholipids in the development of abnormal fatty acid composition in the glomeruli of rats 2 and 10 mo after induction of diabetes with streptozotocin. The proportions of individual phospholipids in the glomeruli of rats were not changed 2 mo after induction of diabetes, but the proportion of phosphatidylethanolamine (PE) decreased and that of sphingomyelin increased 10 mo after induction of diabetes. In contrast, in liver the proportion of PE was increased and that of phosphatidylcholine was decreased. These results showed that changes of individual phospholipids in glomeruli were time-dependent and tissue-specific. Two mo after induction of diabetes, the main change in the phospholipid fatty acid composition of diabetic glomeruli was a decrease in arachidonic acid (AA); the main change in serum free fatty acids (FFA) was an increase in linoleic acid (LA) and a decrease in AA. Ten mo after induction of diabetes, the main changes in the phospholipid fatty acid composition of glomeruli were an increase in LA and a decrease in AA; the main change of the serum FFA composition was a decrease in AA. Thus, the fatty acid composition of glomerular phospholipids was not directly correlated to that of the serum in diabetic rats. Acyl-CoA synthetase and acyltransferase activities increased in diabetic glomeruli with either AA or LA as substrate, but activity toward LA increased more at 2 mo after induction of diabetes. Acyl-CoA synthetase activity increased in diabetic glomeruli with LA as substrate, but that did not change with AA as substrate at 10 mo after induction of diabetes. Furthermore, acyltransferase activity decreased in diabetic glomeruli with AA as substrate, although that did not change with LA as substrate at 10 mo after induction of diabetes.     

Conformational disorder in the Brill transition of uniaxially-oriented nylon 10/10 sample investigated through the temperature-dependent measurement of X-ray fiber diagram

X-ray fiber diagram of uniaxially-oriented nylon 10/10 sample has been measured at the various temperatures. The 11th layer line originating from the methylene zigzag sequences became diffuse above the Brill transition region (140-170 °C), while the layer reflections corresponding mainly to the original repeating period of the parent nylon chains were kept almost unchanged. This observation makes us confirm that in the Brill transition region, the conformational disordering occurs in the methylene sequential parts with keeping the repeating period of the whole skeletal chain by still forming the intermolecular hydrogen bonds between the amide groups of the neighboring chains. This conclusion is consistent with the already-reported infrared spectral data. The characteristic X-ray diffraction patterns observed at the various temperatures were reproduced well by a computer simulation technique utilizing the previously-reported molecular dynamics calculation results.     

Antioxidizing component,musizin, inrumex japonicus houtt

A substance with antioxidant properties was obtained from the hexane extract of roots ofRumex japonicus Houtt. The active component of the hexane extract was isolated and characterized as 2-acetyl-1,8-dihydroxy-3-methyl naphthalene, trivially named musizin (MUS). The antioxidant activities of MUS in six types of fats and oils were higher than that of butyl hydroxyanisole (BHA) and δ-tocopherol (δ-TOC). Together, TOC and MUS have a synergistic effect, because comparable amounts of either had lower antioxidant activity than various combinations of the two antioxidants. When we studied the antioxidant properties of a mixture of MUS and δ-TOC with methyl linoleate (MeLH), we found that the rates of destruction of the two antioxidants were comparable, but that their destruction occurred sequentially, with MUS first followed by δ-TOC, after which the oxidation of MeLH quickly occurred. Comparison of the antioxidant activity of MUS and its analogs suggests that only one of the two hydroxyl groups in MUS is involved in its antioxidant activit. Intermolecular hydrogen bonding may be involved.     

The eta phases and mechanical properties of TIG welded joints of WC-Co cemented carbide and steel

The tungsten-inert-gas (TIG) arc welding experiments of cemented carbide YG30 and steel 45 were carried out using the Ni-Fe-C filling alloys. The eta phases and mechanical properties of welded joints were analyzed by means of scanning electronic microscope (SEM) , transmission electronic microscope (TEM) coupled with selected diffraction, electronic probe microanalysis and bending strength method. The experimental results show that the chemical composition of the filling alloys affects eta phase formation. When the carbon and nickel contents in filling alloys are O. 61 wt% and 55. 29 wt% ,respectively, no eta phases form. And the joint bending strength is the highest to 1. 352 GPa. But if they are O. 01wt% and 55.38wt%, the eta phases are formed at the boundaries of the cemented carbide and the weld, and the thickness of eta phase layer is about 110 micrometers. And the joint bending strength is low. Usually, these eta phases are anomalously granular,and easy to accumulate at the boundaries between cemented carbides and the weld. They are multiple M6C rich in tungsten and iron.