Mixed-conducting perovskite-type Sr_xBi_(1-X)FeO_(3-δ)oxygen-permeating membranes

SrxBi1-xFeO3- (SBF) series mixed conductors were synthesized using Standard ceramic method. The properties of such materials were characterized by XRD, O2-TPD techniques. Ab-normal crystal phenomena were found and explained and correlated with the oxygen permeation results. By analysis of the critical radius (rc), the degree of openness of the lattice (Fv) and the average metal-oxygen bonding energy of the perovskite lattice (ABE), it was proposed that the oxygen permeation flux is determined mainly by the oxygen diffusion rate in bulk when 1-x≤0.5, and by the concentration of oxygen vacancy when 1-x≥ 0.5. The stability of Sr0.5Bi0.5FeO3- was also investigated, and the high stability of it was attributed to the stable BO6 octahedra.     

SOLID STATE CHEMISTRY OF La_(1-x)Li_(x)MnO_3 AND RELATED COMPOUND

A series of perovskite type oxides La_(1-x)A_(x)MnO_3(x=0.1 for A=Li,Na,K;x=0.1～0.5 for A=Li)have been prepared by impregnation.Experimental results showed that the substitution of La~(3 ) by Li~ inLaMnO_(3 ?) greatly increased the selectivity to ethane and ethylene for theoxidative coupling of methane.Temperature-programmed desorption of oxygenproved the presence of oxygen vacancies in the oxide lattice.The higher Mn~(4 )/Mn_t ratio in oxide made the formation of oxygen vacancies easier on the oxidesurface.The general formula of the oxides is La_(1-x)Li_(x)Mn＇V＇_(y)O_(3-y),V=vacancy.     

PREPARATION OF NANOCRYSTALLINE MATERIALS OF PEROVSKITE-TYPE La_(1-x)Sr_xFeO_3 bY USINO GEL OF POLYVINYL ALCOHOL

Precursors of La_(1-x)Sr_xFeO_3(x=0.0,0.1,0.4 and 0.6)nanocrystalline materialswere prepared by the mixed salts dissolved in an aqueous solution ofpolyvinyl alcohol(PVA).XRD,DTA and TEM were used to characterize the samples.Well-nanocrystalline perovskite-type La_(1_x)Sr_xFeO_3 could be synthesized at thetemperatures as low as 400～550℃ for 2h by the calcination of these amorphousprecursors,and the calcination of wet LaFeO_3 gel was investigated at 300℃ forlh and 700℃ for 0.5h.     

DEFECTS IN PEROVSKITE-TYPE CATALYSTS Ca_xLa_(1-x)MnO_(3 λ) AND THEIR ROLE IN AMMONIA OXIDATION

The crystal structure of perovskite-type catalysts, Ca_xLa_(1-x)MnO_(3 λ), remains unchangedwhen x varies from 0 to 1 as identified by X-ray analysis. Both non-stoichiometric amountof oxygen (denoted by λ) and Mn~(4 ) content are functions of x. ESR analysis showed thatvarying the substitution value x in A, the oxidation state of B could simultaneously be adjust-ed, this permits one to change the oxygen chemisorpting ability of these catalysts and toraise their catalytic activity. Based upon the experimental results and from the point ofview of solid defect chemistry, a theoretical analysis for the possible formation of defecttypes is made, and the assumption that the formation of the active species O_2~- or O~- isthrough the reaction of oxygen anion defect with molecular oxygen in gas phase is proposed.This idea is supported by the data obtained by XPS investigation. The reaction mechanism ofpcrovskite-type catalyst for ammonia oxidation is discussed accordingly.     

STUDIES OF MULTICOMPONENT COMPLEX OXIDE CATALYSTS FOR THE OXIDATIVE COUPLING OF METHANE Ⅳ CATALYSTS LiLa_(1-x)Mn_xO(2-λ)(X=0-1)

A series of catalysts LiLa_(1-x)Mn_xO_(2-λ)(x=0—1)were examined for the oxidative couplingof methane.A high C_2 yield of 22％ was obtained.The structures and physico-chemical properties ofsamples have been studied by means of XRD,IR,XPS and SEM.It was found that some complex ox-ides could be formed as X value changed,among them the K_2NiF_4-type oxide La_2Mn_(1-y)Li_yO_(4-λ)was theactive phase for methane coupling,while the Li_2MnO_3 and LiMn_2O_4 were the active phases for completeoxidation of re.ethane.The increase of catalytic activity for methane coupling was attributed to theincrease of the amount of active site,namely,oxygen vacancy in oxide La_2Mn_(1-y)Li_yO_(4-λ)     

THE ROLE OF LATTICE AND GASEOUS OXYGEN ON THE OXIDATIVE COUPLING OF METHANE STUDIED BY A PULSE REACTION TECHNIQUE

A comparative study of the role of lattice and gaseous oxygen in theoxidative coupling of methane over Na~ /Cao and Ca_xSr_(1-x)TiO_3 perovskiteoxide catalysts was performed by using a pulse reaction technique with CH_4,O_2 and mixtures of CH_4and O_2.It was found that there is an oxygen species onthe Surface of Cao which is active only for the total oxidation of methane at thereaction temperature.These oxygen species.once reacted with methane andconsumed,can be regenerated by the adsorption of oxygen molecules from thegas phase or by the migration of the lattice oxysen from the bulk onto thesurface.In contrast,no such oxygen species and no reaction can be detected bymethane pulsed over Ca_xSr_(1-x)TiO_3perovskite oxide catalysts.Na~ can heavilysuppress the non-selective oxygen species on the surface,and When 5mol%Na~ was incorporated onto the surface of Cao,the sample showed no reactivityto methane.When oxygen exists in the gas phase,or the pulse containsmethane and oxygen,the reaction over(Cao is mai     

SURFACE REARRANGEMENTS OF OXYGEN PLASMA TREATED POLYSTYRENE： SURFACE DYNAMICS AND HUMIDITY EFFECT

The time evolution of oxygen plasma treated polystyrene(PS)surfaces was investigated upon storing them in theair under controlled humidity conditions.The methods of water contact angle,X-ray photoelectron spectroscopy(XPS),sumfrequency generation(SFG)vibrational spectroscopy,and atomic force microscopy(AFM)were used to infer the surfaceproperties and structure.Chemical groups containing oxygen were formed on the PS surface with the plasma treatment,demonstrated by water contact angle and XPS.The surface polarity decayed markedly on time,as assessed by steady increasein the water contact angle as a function of storage time,from zero to around 60°.The observed decay is interpreted as arisingfrom surface rearrangement processes to burying polar groups away from the uppermost layer of the surfaces,which is incontact with air.On the other hand,XPS results show that the chemical composition in the first 3 nm surface layer isunaffected by the surface aging,and the depth profile of oxygen is essentially the same with time.A possible change of PSsurface roughness was examined by AFM,and it showed that the increase of water contact angle during surface aging couldnot be attributed to surface roughness.Thus,it is concluded that surface aging is attributable to surface reorganization andthe motion of oxygen containing groups is confined within the XPS probing depth.SFG spectroscopy,which is intrinsicallyinterface-specific,was used to detect the chemical structure of PS surface at the molecular level after various aging times.The results are interpreted as follows.During the aging of the plasma treated PS surfaces,the oxygen containing groupsundergo reorientation processes toward the polymer bulk and/or parallel to the surface,while the CH_2 moiety stands up onthe PS surface.Our results indicate that the surface configuration changes do not require large length scale segmentalmotions or migration of macromolecules.Motions that are responsible for surface configuration changes could be relativelysmall rotational motions.The aging behaviors under different relative humidity conditions were shown to be similar from18% to 91%,whereas the kinetics of surface polarity decays were faster in higher relative humidity.Here,the surfacerearrangement of polystyrene films that were previously treated by oxygen plasma and aged,and was investigated in terms ofcontact angle after the water immersion.The contact angles of the water-immersed samples were found to change andapproach the initial values before the immersion asymptotically.     

Synthesis and adsorptivity of acryloylmorpholine resin to various fission product elements in nitric acid media

A novel silica-supported resin with a cyclic monoamide of polymerized 4-acryloylmorpholine(Silica-AM) was synthesized, and adsorptivity to metal ions of major fission products(FP) was examined in HNO3 and HCl solutions. Silica-AM has a carbonyl oxygen atom outside of the 6-membered morpholine ring, and a cyclic structure that is different than other cyclic monoamide resins we have studied. These include polyvinylpolypyrrolidone(PVPP) and poly-N-vinyl-ε-caprolactam(VEC), both of which have coordinative carbonyl groups included in the ring. Silica-AM was similar to a cyclic monoamide we have reported because it exhibited adsorption to Pd(Ⅱ) and Re(VⅡ) in HNO3 of a particularly low concentration range. Silica-AM has an ether oxygen atom included in the ring as well. Considering the difference in the chemical structures of Silica-AM and other cyclic monoamide resins, it was suggested that oxygen atoms in the carbonyl group and in ether may be main contributors to Silica-AM's respective adsorptions to Pd(Ⅱ) and Re(VⅡ), and Mo(VI) and Zr(IV). Our results imply that the contribution of the two types of oxygen atoms to adsorption is more observable in an HCl system. The contribution of the ether oxygen atom to the adsorption of Pd(Ⅱ) was also suggested from our study on crystal prepared from 4-acetylmorpholine and palladium nitrate.     

STUDIES OF MULTICOMPONENT COMPLEX OXIDE CATALYSTS FOR THE OXIDATIVE COVPLING OF METHANE V.CATALYSTS LiLa_(1-x)Ti_xO_(2+λ)(x=0.0～1.0)

The composition and structure of trinary mixed oxidesLita_(1-x)Ti_xO_2as well as catalytic behavior in the methane oxidative coupling(MOC) have been studied by means of XRD,IR,SEM,XPS and so on.Itwas found that in the series of oxides LiLa_(1-x)Ti_xO_2, as the x value changed,thephases of La_2O_3,LaTi_(1-y)Li_yO_(3-λ),Li_2TiO_3,La_(0.66)TiO_(2.993) and Li_(1.33)Ti(1.66)O_4 wereformed.Among them the complex oxide LaTi_(1-y)Li_yO_(3-λ) was the active phasefor methane oxidative coupling,resulted from the formation of active site Li~+-O~--Ti~(3+) in this phase,and La_(0.66)-TiO_(2.993) and Li_2TiO_3 were active for deep oxi-dation,while Li_(1.33)Ti_(l.66)O_4 was not active for both methane oxidative couplingand deep oxidation.     

THE DOUBLE MELTING PEAKS OF POLY(ETHYLENE TEREPHTHALATE)

Three sets of PET samples, comprising original (undrawn), uniaxially drawn and biaxially ones, after annealed at 230°, 240°and 250℃respectively, were subjected to DSC thermal analysis, X-ray diffraction analysis and IR analysis. The results indicate that the phenomenon of double melting peaks during DSC analysis is due to the partial melting and recrystallization of the crystallite at the moment of thermal scanning. The lower temperature peak, which varies slightly according to annealing condition, corresponds to the melting of imperfect crystallite, and the higher temperature peak corresponds to the melting of better organized crystallite. In the course of temperature scanning, the unit cell parameters of PET remains unchanged while the crystals turn to better crystal lattice, greater crystal size and more regular folding.We also found that there is a slight reduction in crystal size between the two melting peaks, and an explanation is suggested for this phenomenon.     

INQUIRY OF PHOTOSENSITIZATION MECHANISM OF YANGZHOU HEMATOPORPHYRIN DERIVATIVE(YHPD)

By the use of the advanced ESR technique and through comparing with BHPD, the characteristic of YHPD photosensitization is discussed in this paper in the respect of the primary process of photosensitization. The experiment results showed: (ⅰ) not only ~1O_2, but also free radicals(O_2· OH and YHPD)can be formed by the aid of YHPD; and (ⅱ) as to the ability of producing ~1O_2, YHPDBHPD. Two points are indicated: first, the photosensitized damage of YHPD is interrelated to not only ~1O_2, but also free radicals (O_2. OH and YHPD); second, although the photosensitized damage of YHPD is stronger than that of BHPD, yet the photosensitized damage is negatively correlated to the yield of ~1O_2 but positively correlated to those of O_2 and OH. Based on these two points, it is suggested that activated oxygen free radicals(O_2 and. OH) instead of ~1O_2 play the main role as instantaneously activated material in the photosensitized damage of YHPD.     

MESOMORPHIC BEHAVIOR AND MULTIPLE MELTING TRANSITION OF AROMATIC POLYESTER FRACTIONS

Fractions of an aromatic polyester have been studied by DSC, polarizing microscopy, SALS and WAXS techniques. The intrinsic viscosity of the samples in tetrachloroethane is ranging from 0.197 to 0.591dl / g. All the samples exhibit enantiotropic liquid crystal behavior, and the thermal stability of mesophase decrease withlowering the molecular weight of the fractions. The glass transition temperature keeps almost constant for allthe samples, however its value for supercooled mesophase is about 20~C lower than that for amorphous phase.Multiple melting phenomenon was also found for samples crystallized from their mesophases and was similarto that observed for nonliquid crystal forming polymers.     

Activation in the initial stage of oxygen permeation in SrCo0.9Ta0.1O3-δ

Mixed conducting perovskite oxide SrCo_0.9Ta_0.1O_3-δ（SCT） is synthesized by solid-state reaction method.The activation in the initial stage of oxygen permeation through the SCT membrane is investigated.The results show that the activation in the initial stage of oxygen permeation has activate-memory,the first activation can only help to reduce active time of the next cycles,but it is helpless to increase the final oxygen permeation flux.XRD characterization shows that the imperfect perovskite phase structure is gradually improved and the crystal lattice has made some self-adjustment under the permeation conditions,therefore,the oxygen permeation flux of SCT disk membrane increases gradually and till it reaches a steady state.     

Influence of Fe203 Impurity on the Crystalline Structure of Cordierite Synthesized from Waste Aluminum Slag

The influence of Fe203 impurity on the crystalline structure of cordierite synthesized from waste aluminum slag is discussed. XRD and SEM techniques were employed to characterize the crystalline structure and microstructure of each specimen. Philips X‘pert plus software was used to determine the lattice parameters of each specimen. The results show that the Fe2O3 content of 0.8-1.6wt% is beneficial to the formation of cordierite, with the cordierite amount reaching 90wt%. So 0.8-1.6wt% is considered as the allowable Fe2O3 content in the specimens and 0.8wt% is determined to be the best after overall analysis. Plus software analysis shows that the cordierite in each specimen has the same symmetrical hexagonal structure as the single crystal, and the lattice parameters as well as the lattice dimensions change slightly.     

Role of Microstructure and Spectrum Features on the Catalysis Effect of Ce_(1-x)(Nd_(0.5)Eu_(0.5))_xO_(2-δ) Solid Solutions

Nanosized Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) solid solutions(x = 0.00~0.20) were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg_2Ni and Ni powders for 20 h to get the Mg_2Ni–Ni–5 mol% Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) composites.The structures and spectrum characteristics of the Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) solid solutions catalysts were analyzed systemically.XRD results showed that the doped samples exhibited single phase of CeO_2 fluorite structure.The cell parameters and cell volumes were increased with increasing the doped content.Raman spectrum revealed that the peak position of F_(2g) mode shift to higher wavenumbers and the peak corresponding to oxygen vacancies were observed distinctly for the doped samples.UV-Vis technique indicated that the absorption peaks of Eu~(3+) and Nd~(3+) ions appeared; the bandgap energy was decreased linearly.The electrochemical and kinetic properties of the Mg_2Ni–Ni–5 mol% Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) composites were measured.The maximum discharge capacity was increased from 722.3 mA h/g for x = 0.00 to 819.7 mA h/g for x = 0.16,and the cycle stability S_(20) increased from 25.0%(x = 0.00) to 42.2%(x = 0.20).The kinetic measurement proved that the catalytic activity of composite surfaces and the hydrogen diffusion rate were improved for the composites with doped catalysts,especially for the composites with x = 0.16 and x = 0.20.The catalysis mechanism was analyzed from the point of microstructure and spectrum features of the Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) solid solutions.     

Growth Defects in Cubic KTa1-xNbxO3 Crystal

Potassium tantalate niobate （KTa1-xNbxO3, KTN） crystals with different dimensions and quality situations were grown by Czochralski method. Crystal growth process and morphology properties of KTN are presented in this paper. It was found that some defects, such as bubble, inclusion, crack, dislocation etc., can all appear if the crystal is grown in an improper condition. The character and formation mechanism of such defects in macro growth are discussed. We consider that the CO2, which was not released absolutely during the sintering process and dissolved in the melt, led to bubbles. The composition of the inclusion caused by high pulling and rotation rates is KTN polycrystalline. The crack and dislocation in KTN crystal mainly come from improper temperature field. Etching and high-resolution X-ray diffraction （HRXRD） experiment results indicate that the central area is the defects concentrated.     

STUDY ON OXYGEN ADSORPTION AND CATALYTIC PROPERTIES OF TiO_2-BASED CATALYSTS

The active oxygen species and active sites for MOC(methane ox-idative coupling)over TiO_2-based catalysts are studied by ESR method.Oxy-gen chemisorption on TiO_2,La/TiO_2 and Li/TiO_2 was measured by dynamicESR technique from 295 K to 105 K.The process of oxygen adsorption onTiO_2 is discussed.The spectra show that O_2~- ions exist largely on TiO_2 but lit-tle on Li/TiO_2 due to the decrease of surface density of electrons caused bythe substitution of Li~+ for lattice Ti~(4+) in Li/TiO_2.O~- was not detected on allsamples.Both O_2~- and O~- are not likely to be the active species in MOC reac-tion.Two triplet peaks in ESR spectra of Li/TiO_2 are attributed to Ti~(3+)(Ⅱ)and Ti~(3+)(Ⅲ)of low coordination numbers,which are active in the presenceof oxygen.Sites of low coordinated Ti~(3+) or Ti~(4+) are suggested to be responsi-ble for the formation of active oxygen species.     

A STUDY OF METHANE OXIDATIVE COUPLING OVER La-Th-O MIXED OXIDE CATALYSTS

The compositions and structures of La-Th-O mixed oxides as well astheir catalytic activity for methane oxidative coupling have been studied bymeans of XRD,XPS and IR.The results indicated that the solid solution ofLa_xTh_(1-x)O_(2-&)with the fluorite structure was formed in the range of 0≤x≤0.6and it was the main active phase for oxidative coupling of methane(OCM).     

Inhibitory effect of H_(3 + x)PMo_(12－x)V_xO_(40)-Ton the self-polymerization of methyl methacrylate

In this work,a series of molybdovanadophosphoric heteropoly acid quaternary ammonium salts H_(3+x)PMo_(12 -x)V_xO40-T were synthesized and employed as a reaction inhibitor in the selfpolymerization of methyl methacrylate(MMA).The polymerization inhibition effect of H_(3+x)PMoPMo_(12 -x)V_xO40-T)with different number of vanadium atoms and reaction dosages was investigated using differential scanning calorimetry(DSC).It shows that the inhibitory effect was improved with the increasing dosages of H_(3+x)PMoPMo_(12 -x)V_xO40-T),and the polymerization inhibition was also affected by the number of vanadium atoms in the H_(3+x)PMo_(12 -x)V_xO40-T .Furthermore,cyclic voltammograms(CV)was used to probe the mechanism of the inhibition reaction with H3+xPMo12xVxO40-T.The result of CV indicates that the inhibition reaction is an oxidation–reduction reaction.H_(3+x)PMo_(12 -x)V_xO40-T can react directly with the MMA monomer radicals,which eliminated the MMA monomers,and therefore the self-polymerization of the MMA can be effectively inhibited by H_(3+x)PMo_(12 -x)V_xO40-T.     

Approach to lattice-related/content-specific spectral ranges of near-infrared diffuse reflectance spectroscopy of cefazolin sodium and the construction of a quantitative model for the determination of cefazolin sodium content in different crystal forms

Cefazolin sodium can form both - and -form crystals. It also can form dehydrated crystalline and amorphous products through different production processes. Because different polymorphic medicines usually have different physical and chemical properties, it is critical to emphasize the crystallization control of polymorphic medicines. Near-infrared (NIR) analysis, which incorporates a combination of NIR spectroscopic techniques and multivariate chemometric methods, is considered a powerful tool for the determination of the crystallinity of polymorphic drugs. The selection of optimal spectral ranges that correlate with the lattice specificity and content specificity is crucial to obtaining a specific NIR model. In the present work, near-infrared (NIR) spectra of cefazolin sodium with different crystal forms created through different processes were studied. The results suggest that wavelengths within the range of 9102.7-8597.5 cm-1 is related to the specificity of the cefazolin sodium crystal lattice and that the range of 6001.6-5496.4 cm-1 is associated with the quantitative content of cefazolin sodium. The two ab- sorptions are caused by the second overtone of the C-H stretching band (3υC-H) and the first overtone of C-H stretching band (2υC-H), respectively. Using these results, we established a suitable method of constructing a universal quantitative model by using mixed samples in different crystal forms as a calibration set, selecting a content-specific range (6001.6-5496.4 cm-1 ), and adding lattice-related spectral ranges where appropriate. This may provide a framework for the construction of prediction models for polymorphic medicines.