932 resultados para phase change


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A series of solid electrolytes Ce1-xSmxO2-y (x=0similar to0.6) were prepared by sol-gel method. XRD measurement showed that single-phase solid solution was formed in all investigated ranges at 160 degreesC, which is a significantly lower synthesis temperature compared to traditional solid state reaction. High temperature X-ray, ESR, and Raman scattering were used to characterize the samples. ESR measurement showed that ESR with sample irradiated by high-energy particle is an effective way to study the defect structure. These changes in the Raman spectrum are attributed to O vacancies, which are introduced into the lattice when tetravalent Ce4+ is substituted by trivalent Sm3+.

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Phase behavior of the extraction system, Cyanex 923-heptane/Ce4+-H2SO4 has been studied and compared with Cyanex 923-heptane/H2SO4 System. Cerium(IV) is mainly extracted into the third phase, and its concentration in the third phase first increases with the increasing aqueous acid concentration, reaches maximum and then decreases. At higher acidity, cerium(IV) is hardly extracted in the third phase. The phase behavior and change of the contents of acid and water are similar to those in the acid system. The acid concentration increases with increase of the aqueous acid in the whole extraction region while the water content first decreases with it and then increases after the third phase formation. The third phase has a characteristic lamellar structure formed by the aggregates of Cyanex 923 (.) (H2SO4)(2) (.) H2O as those in the case of acid system. The third phase loaded Ce(IV) has been used to prepare ultrafine CeO2 powder conveniently by precipitation with oxalic acid, and powders with size mostly smaller than 100 nm can be obtained.

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The behavior of electrical conductivity for excimer laser irradiated polyimide films in the vicinity of the critical number of laser shots was described by three-dimensional percolative phase transition model. It is: found that electrical conductivity changed more rapidly than that predicted by the percolation model. Thus, the change in microstructure with increasing number of laser shots was analyzed by FT-IR Raman spectrometry and laser desorption time-of-flight mass spectrometry. It is demonstrated that not only the number but also the average size of graphite particles on the irradiated polyimide film surfaces increased with increasing number of laser shots. These results were helpful to better understand the critical change in electrical conductivity on the irradiated polyimide film surfaces. (C) 2001 Elsevier Science B.V. All rights reserved.

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A poly(methyloctadecylsilane) oligomer was synthesized by a typical Wurtz coupling reaction. Upon cooling, three transitions were observed at temperatures of 39.9, 37.5 and 33.9 degreesC at a rate of 2.5 degreesC/min in differential scanning calorimetry (DSC). The first transition, with enthalpy change of 0.47 kT/mol and supercooling of 0.2 degreesC, was characteristic of the conformational change in the Si-Si backbone into an all-trans conformation, which was detected by temperature-dependent Fourier transform infrared (FT-FR) spectroscopy. The second and the third transitions with large supercooling were identified as the formation of two-dimensional hexagonal crystal packing and three-dimensional two-chain orthorhombic crystal packing, respectively. The crystal structure was determined by the combination of WAXD and transmission electron microscopy (TEM) experiments. (C) 2000 Elsevier Science Ltd. All rights reserved.

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A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

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Valence stability and change of Eu(II) in oxides have been studied by luminescence spect a. The results show that the valence stability and change of Eu(II)in oxides is closely related to the radius and electric charge of positive ions substituted by Eu(II) and crystal structure of the host such as Al2O3 which can form alpha-Al2O3 single phase and alpha-Al2O3 and gamma-Al2O3 mixed phases under different reaction temperatures. A, fairly good explanation is made by the proposed relation between energy coefficient and crystal structure for the first time to the observed experiment results. if the energy coefficients of substitution ions is more than that of Eu(II), the lattice substitution of Eu(II)for these ions is not occured generally and valence stare of Eu(II)is not stable and be easily changed into Eu(III). The lattice of gamma-Al2O3 can stablize the valence state of Eu(II)within certain coped concentration and in alpha-Al2O3 crystal lattice Eu(II)can be easily changed into Eu(III).

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The change of Eu3+-surroundings with the Al/B ratio varying from 4.5 to 2 and Eu/(Al + B) = 0.02, was investigated through X-ray diffraction, infrared spectra, excitation and emission spectra, and phonon sideband. The results show coexistence of the crystal phase Al18B4O33 and the amorphous phase and Eu3+ ions of the samples with the Al/B ratio from 3 to 2 are incorporated into the amorphous phase. It was also found that electron-phonon coupling strength decreases with the Al/B ratio from 3 to 2, non-radiative decay rate decreases, resulting in an increase of the Eu3+-emission intensity. (C) 1999 Elsevier Science Ltd. All rights reserved.

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In this paper, phase transition temperatures of side chain liquid crystal polymer were predicted by molecular dynamics simulation. We analyzed the change of energy and the degree of similarity(S) with the temperature varying. The simulated phase transition temperatures agree with the experimental values in a proper deviation.

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Square-wave voltommetry is used to study the oxidation of polypyrrole doped with dodecylsulfate. The net current curve in this experiment shows why the oxidation current does not display the capacitive-like shape common in cyclic voltammetry. In cyclic voltammetry, the redox behavior of polypyrrole is attributed to the size of dodecylsulfate, irreversible incorporation and the complete consumption of dodecylsulfate. After the polypyrrole film was scanned in aqueous NaCl solution, square wave voltammetric measurements show different results, indicating the change of the polymer nature with regard to the charge transport. This is explained by anion replacement, exclusion and the change of the charge transport mechanism.

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The solid-solid phase transition of [n-C11H23NH3]2ZnCl4 Complex have been studied by Raman spectroscopy. The results show that the occurence of the structural phase transitions mainly related to the change of packing structure and molecular conformation o

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The solid-solid phase transitions in the perovskite-type layer compound [n- C16H33NH3]2CoCl4 have been studied by infrared spectroscopy. A new phase transition at 340 K was found by comparison with differential scanning calorimetry results. A temperature dependence study of the infrared spectra provides evidence of the occurrence of structural phase transitions related to the dynamics of the alkylammonium ions and hydrogen bonds. The main transition at 374 K corresponds to the conformational order-disorder change in the chain, which probably couples with reorientational motions of the NH3 polar heads. GTG or GTG' defects appear in the high temperature disordered phase.

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The aim of this study was to determine the maximum tolerated dose (MTD), dose-limiting toxicities (DLT), and potential activity of combined gemcitabine and continuous infusion 5-fluorouracil (5-FU) in metastatic breast cancer (MBC) patients that are resistant to anthracyclines or have been pretreated with both anthracyclines and taxanes. 15 patients with MBC were studied at three European Organization for Research and Treatment of Cancer centres. 13 patients had received both anthracylines and taxanes. Gemcitabine was given intravenously (i.v.) on days 1 and 8, and 5-FU as a continuous i.v. infusion on days 1 through to 14, both drugs given in a 21-day schedule at four different dose levels. Both were given at doses commonly used for the single agents for the last dose level (dose level 4). One of 6 patients at level 4 (gemcitabine 1200 mg/m2 and 5-FU 250 mg/m2/day) had a DLT, a grade 3 stomatitis and skin toxicity. One DLT, a grade 3 transaminase rise and thrombosis, occurred in a patient at level 2 (gemcitabine 1000 mg/m2 and 5-FU 200 mg/m2/day). Thus, the MTD was not reached. One partial response and four disease stabilisations were observed. Only 1 patient withdrew from the treatment due to toxicity. The MTD was not reached in the phase I study. The combination of gemcitabine and 5-FU is well tolerated at doses up to 1200 mg/m2 given on days 1 and 8 and 250 mg/m2/day given on days 1 through to 14, respectively, every 21 days. The clinical benefit rate (responses plus no change of at least 6 months) was 33% with one partial response, suggesting that MBC patients with prior anthracycline and taxane therapy may derive significant benefit from this combination with minimal toxicity.

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BACKGROUND: To our knowledge, the antiviral activity of pegylated interferon alfa-2a has not been studied in participants with untreated human immunodeficiency virus type 1 (HIV-1) infection but without chronic hepatitis C virus (HCV) infection. METHODS: Untreated HIV-1-infected volunteers without HCV infection received 180 microg of pegylated interferon alfa-2a weekly for 12 weeks. Changes in plasma HIV-1 RNA load, CD4(+) T cell counts, pharmacokinetics, pharmacodynamic measurements of 2',5'-oligoadenylate synthetase (OAS) activity, and induction levels of interferon-inducible genes (IFIGs) were measured. Nonparametric statistical analysis was performed. RESULTS: Eleven participants completed 12 weeks of therapy. The median plasma viral load decrease and change in CD4(+) T cell counts at week 12 were 0.61 log(10) copies/mL (90% confidence interval [CI], 0.20-1.18 log(10) copies/mL) and -44 cells/microL (90% CI, -95 to 85 cells/microL), respectively. There was no correlation between plasma viral load decreases and concurrent pegylated interferon plasma concentrations. However, participants with larger increases in OAS level exhibited greater decreases in plasma viral load at weeks 1 and 2 (r = -0.75 [90% CI, -0.93 to -0.28] and r = -0.61 [90% CI, -0.87 to -0.09], respectively; estimated Spearman rank correlation). Participants with higher baseline IFIG levels had smaller week 12 decreases in plasma viral load (0.66 log(10) copies/mL [90% CI, 0.06-0.91 log(10) copies/mL]), whereas those with larger IFIG induction levels exhibited larger decreases in plasma viral load (-0.74 log(10) copies/mL [90% CI, -0.93 to -0.21 log(10) copies/mL]). CONCLUSION: Pegylated interferon alfa-2a was well tolerated and exhibited statistically significant anti-HIV-1 activity in HIV-1-monoinfected patients. The anti-HIV-1 effect correlated with OAS protein levels (weeks 1 and 2) and IFIG induction levels (week 12) but not with pegylated interferon concentrations.

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In the summers of 1998 and 1999, the Archaeology in Annapolis project carried out archaeological investigation at the eighteenth century Dr. Upton Scott House site (18AP18)located at 4 Shipwright Street in the historic district of Annapolis, Anne Arundel County, Maryland. The Upton Scott House is significant as one of only a few Georgian houses with remnants of its original plantation-inspired landscape still visible (Graham 1998:147). Investigation was completed in agreement with the owners of the historic property, Mr. and Mrs. Paul Christian, who were interested in determining the condition and arrangement of Dr. Upton Scott’s well-documented pleasure gardens. Betty Cosans’ 1972 Archaeological Feasibility Report, the first real archaeological study of the Upton Scott House site, guided the research design and recovery efforts. Cosans determined that testing and survey in the back and side yards of the Scott property would yield important information on the use and history of the property, including that of Scott’s famous gardens. Excavation units and trenches were placed within three separate areas of backyard activity on the site which included Area One: extant brick stables in the southwest of the property; Area Two: the brick foundations of a small outbuilding located in the northwest area of the site; and Area Three: the area of Scott’s formal gardens. The research design included an interest in recovering evidence of African-American spiritual practice and domestic life at the site. Also of significant importance was an analysis of Scott’s garden beds, concerning the order and layout. Also sought was an understanding of the change in perception and use of the backyard by the various owners of the property.

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Intensive archaeological investigation was undertaken on an urban backlot in Annapolis, Maryland. Fieldwork was conducted on behalf of Historic Annapolis Foundation for the property's owners, King and Cornwall, Inc. Supplemental documentary research, an evaluation of existing conditions on the property, and below-ground excavation of a 35 X 70 ft. urban backlot were conducted. While the project was not a Section 106 compliance effort, the field methods and rationale for the site's investigation are comparable to those of standard Phase II site evaluations. Historical documentation attested to the fact that the 22 West Street Backlot, located along the western most edge of the Historic District of Annapolis, Maryland, had seen development and occupation since the first quarter of the eighteenth century. A substantial brick structure was known to have occupied the property in a series of altered forms for much of that period. This structure served a variety of purposes over time: a private residence in the eighteenth century, a boarding house in the nineteenth century (known as the National Hotel), a duplex in the early twentieth century, half of which remained in use until the structure was entirely razed in the 1970s after destruction by fire. Recovery and analysis of site formation processes (i.e., both cultural and natural transformations of the buried remains) indicated that sections of the site were disturbed to a depth of six feet. In contrast to what initially seemed a poor prognosis for site integrity, other areas of the backlot revealed numerous intact historical features and deposits. Structural remains from the dwelling and its associated outbuildings, additions, and attendant trash deposits were recovered. What was initiated as a program of limited testing evolved into a larger-scale undertaking that made use of largely hand-excavated units in conjunction with machine-assisted stripping of areas demonstrated to contain from four to six-foot deep sterile layers of fill. The current investigations provided a window into a portion of the city and period in its history not documented archaeologically. Moreover, this project provided valuable insight into the archaeology of the homelot within a lightly industrialized, urban context. Evidence was recovered of shifts in the layout and arrangement of the houselot as well as changing relations between individuals and the workplace--all within an urban context--an issue defined elsewhere in the archaeological literature as a significant one. No further investigations are recommended for the site, however, further analysis and interpretation of materials recovered are ongoing. In the event that the site were to undergo development, monitoring of any construction activity is recommended.