Effect of substitution of divalent ions on the electrical andmagnetic properties of Ni-Zn-Me ferrites

The effect of Cu²⁺, Cd²⁺, Co²⁺, Ca²⁺, Mn²⁺, and Mg²⁺ ions on the physical properties of stoichiometric Ni_0.5Zn_0.5Fe ₂O₄ ferrite is investigated. The specimen is prepared by the conventional manufacturing method without atmosphere control. The divalent ions replace one-half the Ni²⁺ ion molar content. We found that the magnetic and electrical properties of Ni-Zn ferrite changes considerably with the substituent species. Copper ions play an important role in lowering the sintering temperature and increasing density. Manganese and cobalt ions increase electrical resistivity by about two orders of magnitude, while the Ca and Mn ions improve thermal stability of the initial permeability. We also discuss our investigation of the physical properties of the Ni-Zn-Me ferrites on the basis of site occupation of the cation species in the spinel structure     

Study on monolayer behavior of C60 using BAM and π–A isotherms

The influence of the experimental conditions (concentration, subphase, volume, waiting time, compressing speed and compression–expansion cycle, etc.) and UV-light irradiation on the monolayer behavior of C₆₀ was studied in details by using pressure–area (π–A) isotherms and Brewster angle microscopy (BAM) images. The concentration of spreading solution and the subphase were the most important factors in the formation of relatively homogenous C₆₀ monolayers and Langmuir–Blodgett (LB) films. A concentration of 10⁻⁵ M and the phenol subphase were preferred.     

Investigation of dioctadecyl bilirubinamide in monolayers and Langmuir–Blodgett films

A new amphiphilic ligand, dioctadecyl bilirubinamide [B(CONHR)₂, R=C₁₈H₃₇] form stable monolayers at the air–water interface on neutral, acidic and basic subphases as well as on subphases containing metal ions. Changes in the pH of the subphase do not produce remarkable effects on monomolecular films. The interactions between metal ions and B(CONHR)₂ molecules were investigated by means of various techniques in monolayers and Langmuir–Blodgett (LB) films. B(CONHR)₂ with its complexing head group in contact with the aqueous phase can form metal complexes with many metal ions present in the aqueous phase. The formation of B(CONHR)₂–metal complexes leads to large changes in the area per B(CONHR)₂ molecule. LB films transferred from pure water and metal ions containing subphases were characterized by XPS and low-angle X-ray diffraction.     

A novel highly conducting phosphonium tetracyanoquinodimethane Langmuir-Blodgett film

We describe the properties of pristine and iodine-doped Langmuir-Blodgett films built up from a new semi-amphiphilic tetracyanoquinodimethane (TCNQ) salt, namely trimethyloctadecylphosphonium TCNQ. The films are transferred from a water subphase to a solid substrate. After exposure to diluted iodine vapour, the films become conducting. This behaviour is checked by the IR absorption spectrum. The conductivity estimated from the energy of the maximum of the charge transfer absorption band is about 20–50 Ω^-1 cm^-1.     

One pot synthesis of monodispersed L-glutathione stabilized gold nanoparticles for the detection of Pb2+ ions

Direct mixture of Au³⁺ with glutathione (GSH), which act as both reduction agents and stabilizers, in aqueous solution gave rise to production of gold nanoparticles (Au NPs) with uniform sizes of around 21 nm. The GSH stabilizer Au NPs in solution show immediate aggregation after addition of 1 mol/L NaCl aqueous solution containing Pb²⁺ ions. The Pb²⁺-induced aggregation in Au NP solution is monitored by both colorimetric response and UV-vis spectroscopy. A rather broad linear range (from 0.1 to 30 μmol/L) and low detection limit (0.1 μmol/L) are explored for Au NP sensors used for detection of Pb²⁺ ions. Furthermore, the response of GSH-stabilized Au NPs toward Pb²⁺ ions is specific compared with other possible interferants (Hg²⁺, Mg²⁺, Zn²⁺, Ni²⁺, Cu²⁺, Co²⁺, Ca²⁺, Mn²⁺, Cd²⁺, and Ba²⁺).     

Aggregation of cyanine dyes at Langmuir-Blodgett monolayers

Cyanine dyes are adsorbed from aqueous solution to Langmuir-Blodgett (LB) films, forming monolayers of Scheibe or J aggregates, whereas the dye in solution is in monomeric state. As well as J aggregates other types of aggregates (H, H^* aggregates, oligomers, dimers) can form and interchange at the LB interface depending on conditions and the structures of the dyes and amphiphiles. Reflection spectroscopy proved to be a useful method for studying aggregates and kinetic processes at the air-water interface as the bulk subphase is not recorded by this method.

Aggregation of dyes seems to be controlled by Coulomb interactions and the surface structure of the interacting monolayers. Cationic cyanine dyes are adsorbed only at negatively charged monolayers (e.g. fatty acids) whereas cyanine dyes with negative net charge form aggregates only at positively charged monolayers (e.g. amphiphilic ammonium salts).

Aggregation of cyanine dyes has also been found at LB monolayers of amphiphilic nucleic acids which have been synthesized for the first time. Aggregates of adsorbed cyanine dyes can be transferred to solid substrates by the LB method and investigated by other spectroscopic methods or microscopy.

Adsorption of cyanine dyes at vesicle bilayers has been reported; this was studied by absorption spectroscopy of vesicular dye solutions. Comparison of these spectra with reflection spectra of corresponding LB films reveals significant differences between the effects in LB monolayers and those in vesicular bilayers.     

CuO nanocrystallites obtained by oxidation of copper arachidate LB multilayers

Copper arachidate (CuA) Langmuir–Blodgett (LB) multilayers were transferred in the subphase pH range 4.6–5.7. FTIR studies of multilayers show a gradual increase in CuA content as subphase pH is increased. X-ray reflection patterns of multilayers show presence of a single layered structure in all the multilayers transferred at different subphase pH. A continuous decrease in bilayer period from 52.5 Å to 47 Å is seen with decrease in CuA content of the multilayers. These observations suggest mixing of CuA and arachidic acid molecules at the molecular level. The precursor CuA multilayers were oxidized at 300 °C–700 °C. The formation of CuO is confirmed by UV–Visible spectroscopy. Atomic force micrographs show the formation of CuO nanocrystallites and their clusters, with the average size, size distribution, height and density of nanocrystallites depending strongly on subphase pH, number of monolayers and oxidation temperature. Typically, 7–11 monolayers CuA transferred at subphase pH of 4.6 and oxidized at 700 °C resulted in isolated and nearly mono-disperse nanocrystallites of size 20–30 nm and height ∼ 1 nm. Crystallites of size 2–10 nm along with few clusters were obtained by oxidation of a 3 monolayer CuA.     

Ordered Langmuir-Blodgett films of a substituted lutetium bisphthalocyanine

High-quality LB multilayers have been prepared from the Lu(III) sandwich complex of 2,3,9,10,16,17,23,24-octa (n-butoxy)phthalocyanine (LuPc₂(OBu)₁₆). Surface pressure-area isotherms were characterized and indicate that a stable monolayer is formed corresponding to an area per molecule of 2.4 nm² at 30 mN m⁻¹. The LB films were highly birefringent, and polarized spectra gave dichroic ratios of 3.3 for the 670 nm absorption band and between 0.5 and 2.8 for infrared absorptions. The results indicate that the phthalocyanine rings were highly oriented perpendicular to the dipping direction but somewhat tilted from the substrate normal. The order was shown to be absent when (i) unsubstituted LuPc₂ was used for LB films, or (ii) the horizontal lifting method of film deposition was used, or (iii) the surface pressure was increased to 50 mN m⁻¹, causing a molecular rearrangement. The ordering was improved at 100 °C and finally lost at 280 °C by annealing on a hot stage. The d.c. electrical conductivity of LB films of LuPc₂(OBu)₁₆ was low (σ ≈ 2 × 10⁻⁷ Ω⁻¹ m⁻¹), in contrast with unsubstituted LuPc₂ (σ ≈ 10⁻¹ Ω⁻¹ m⁻¹) and showed no evidence for anisotropy. The findings are in broad agreement with related studies and illustrate some of the many factors involved in improving the structure of phthalocyanine LB films for possible applications.     

焙烧温度对Cu-Mn/γ-Al2O3催化剂催化氧化甲苯性能的影响

采用浸渍法合成了Cu-Mn/γ-Al₂O₃催化剂, 通过XRD、BET、H₂-TPR和XPS等方法对经不同温度(300~600℃)焙烧的催化剂进行表征, 采用固定床管式反应装置考察了焙烧温度对催化剂催化氧化甲苯的影响, 并讨论活性组分、表面Cu⁺/(Cu⁺+Cu²⁺)和Mn⁴⁺/(Mn⁴⁺+Mn³⁺)摩尔比值与催化剂活性的关系。结果发现, 550℃焙烧温度的催化剂活性最好, 氧化能力最强, 其转化率为95%时对应的反应温度T₉₅(286 ℃)最低, CO₂的选择性达100%。在550℃焙烧时生成的Cu_1.4Mn_1.6O₄新相以及催化剂表面中相对含量更高的Cu⁺和Mn⁴⁺是催化剂具有高活性的主要原因。     

铋膜电极阳极溶出伏安法检测痕量Cd金属

镉氧化产生的溶出电流与样品中Cd²⁺的浓度有关。本研究通过方波阳极溶出伏安法(SWASV)在活化铋膜电极(Activated BFE)上对低浓度μg/L水平的Cd(II)进行测定。通过电化学方法对电极进行初步改性, 然后电沉积制备铋膜再次对电极进行改进, 从而增强了对痕量目标Cd²⁺的敏感性。对改性前后的玻碳电极(GCE)表面进行SEM、CV、EIS和SWV的表征。为了将这种伏安法传感器应用于含有低浓度Cd²⁺的实际样品中, 对检测Cd²⁺的实验参数进行了研究。使用选定的条件, 在10 min的预富集条件下Cd²⁺的检测限为1 μg/L。     

Stability of dimethyldioctadecylammonium bromide Langmuir-Blodgett films on mica in aqueous salt solutions—implications for surface force measurements

Langmuir-Blodgett (LB) monolayer films of dimethyldioctadecylammonium bromide (DDOA) on muscovite mica have been studied using Wilhelmy plate type wetting measurements, surface force measurements, atomic force microscopy (AFM), and Brewster angle microscopy (BAM) on insoluble monolayers of DDOA before deposition. In particular, the effect of exposure to aqueous KBr salt solutions was investigated. BAM shows a heterogeneous monolayer with small condensed domains of dendritic shape under conditions normally used for deposition. A stick-jump behaviour of the meniscus is seen during deposition, leading to a large-scale heterogeneity measurable in wetting studies. These also show breakdown and hydrophilization of the LB film at the three-phase contact line (meniscus) and when exposed to salt solutions of approximately 10⁻² M concentration. The advancing contact angle against water is approximately 105°. Surface force measurements show long-range attraction in water, but also a surface charge which depends on salt concentration, and breakdown when surfaces are brought into contact in high salt concentrations. AFM images of untreated films show small holes, and breakdown when exposed to salt solution, especially at the three-phase line. The LB film is judged to be less suitable as a model hydrophobic surface owing to its heterogeneity and instability in salt solution.     

SO_4~（2-）对Mn掺杂硫磷酸盐玻璃结构和发光性能的影响

采用高温熔融法制备了Mn掺杂P_2O_5-ZnO-ZnSO_4-Na_2O硫磷酸盐玻璃,研究了不同SO_4~（2-）含量下玻璃结构的变化以及Mn离子的发光性能。结果表明：在409 nm光激发下,MN离子掺杂硫磷酸盐玻璃可产生500 nm到750 nm的宽带发射,SO_4~（2-）的引入改变了Mn~（2＋）周围的配位场,...     

Langmuir-Blodgett films from dioctadecylamine picrate

Langmuir-Blodgett (LB) films prepared from picrate of dioctadecylamine(PDODA) and dioctadecylamine (DODA) were studied for the high picrate dipole moment, potentially effective in pyroelectricity. Stable condensed monolayers were obtained on pure water at pH from 5 to 8. About 90% of the PDODA in the films was hydrolysed to DODA. Moderate repulsion between ionized polar heads in the films promoted the desirable X- or Z-type deposition on solid supports, but it prevented a successive deposition of more than five monolayers. At pH below 5 the content of CdCl₂ or picric acid in the subphase decreased the PDODA hydrolysis. Strong repulsion under these conditions caused an expansion of the films and prevented the deposition of more than a single monolayer.     

Sol–gel deposition and characterization of Mn-doped silicate phosphor films

Mn²⁺-doped Zn₂SiO₄ and Mg₂Gd₈(SiO₄)₆O₂ phosphor films were deposited on silicon and quartz glass substrates by sol–gel process (dip-coating). The variations of sol viscosity with time and film thickness with the number of layers were investigated in Zn₂SiO₄: Mn system. The results of XRD and IR showed that the Zn₂SiO₄: Mn films remained amorphous below 700°C and crystallized completely around 1000°C. From AFM studies, it was observed that the grains with 0.5–0.8 μm size packed closely in Zn₂SiO₄: Mn films, which were uniform and crack free. The luminescence properties of Zn₂SiO₄: Mn films were characterized by absorption, excitation and emission spectra as well as luminescence decay. These properties were discussed in detail by a comparison with those of Mn²⁺ (and Pb²⁺)-doped Mg₂Gd₈(SiO₄)₆O₂ phosphor films.     

C60/PVK/CdS纳米粒子功能复合 LB 膜研究

目的 尝试用Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ（ＬＢ）技术组装Ｃ６０技术组装Ｃ６０功能复合体系的新方法。方法 采用（ＬＢ）技术制备Ｃ６０／ＰＶＫ／ＣｄＳ花生酸混合ＬＢ膜并利用界面化学反应技术将混合膜与硫化氢气体反应制得Ｃ６０／ＰＶＫ／ＣｄＳ纳米粒子功能复合ＬＢ膜并进行紫外光谱表征。结果 含不同比例Ｃ６０的Ｃ６０ＰＶＫ／ＡＡ体系可以在辐亚相上形成稳定的单层膜并转移到固体基片上得到了ＬＢ多层膜,ＬＢ混     

调控Al2O3晶型控制MgAl2O4:Mn4+荧光粉中Mn价态研究

Mn⁴⁺激活红光荧光粉是白光半导体发光二极管(wLEDs)领域当前研究热点之一。Mn⁴⁺离子²E→⁴A₂跃迁在铝酸盐中的最短发光波长是在MgAl₂O₄中实现的651 nm发光, 由于其结构中含有形成四面体或八面体配位的两种阳离子格位(Mg²⁺/Al³⁺), 易造成所掺杂锰元素存在多种价态(+2/+4/+3等)。本研究通过改变起始原料中Al₂O₃的晶型(γ/α比例)及退火处理来调控锰离子在MgAl₂O₄晶格中的占据格位, 对其主要存在价态实现调控。采用荧光光谱和紫外-可见-近红外漫反射光谱技术来表征所合成荧光粉中Mn离子的价态及其演变。研究发现, 高α/(α+γ)比铝源促进Mn²⁺形成, 而低α/(α+γ)比铝源促进Mn⁴⁺形成。通过使用高活性纳米γ-Al₂O₃为铝源, 有效抑制了锰离子在MgAl₂O₄中Mg²⁺格位的占据及Mn²⁺离子的形成, 经空气中1550 ℃保温5 h的一次高温热处理即可制备出在可见光区只有Mn⁴⁺红光发光的高纯高亮度MgAl₂O₄:Mn⁴⁺荧光粉。氧化铝晶型影响锰离子掺杂格位和掺杂价态的本质规律是: 氧化铝活性决定实际固溶掺杂反应步骤, 进而影响锰离子掺杂格位和价态。本研究提出的反应步骤调控作为反应气氛、电荷补偿剂、反应温度三种调控方法外的一种新方法, 为Mn⁴⁺激活铝酸盐荧光粉中锰离子掺杂价态调控提供了新思路。     

Static energy transfer for Mn : Pr system in Phosphate glasses

The process of energy transfer from divalent manganese to trivalent praseodymium ions is studied with the help of Forster–Dexter theory. Some of the important energy transfer parameters such as transfer probability (P_SA), quantum yield of energy transfer (μ), critical radius (R₀) and critical concentration of the acceptor (C_A) are evaluated for the energy transfer pairs Mn²⁺ : Pr³⁺, Pr³⁺ : Pr³⁺ in phosphate glasses. The transfer of energy from Mn²⁺ to Pr³⁺ was confirmed by recording the fluorescence decay curves of Mn²⁺ emission corresponding to various activator concentrations which show a non-exponential behaviour. Large values of transfer probabilities and transfer efficiencies suggest that Mn²⁺ ion can act as a good sensitizer to Pr³⁺ ion in phosphate glass.     

One-step synthesis of poly(2-hexadecyloxyaniline)/selenium nanocomposite Langmuir–Blogett film by in situ redox reaction

Poly(2-hexadecyloxyaniline)/selenium (Se) nanocomposite monolayer was successfully prepared by spreading 2-hexadecyloxyaniline (2-C₁₆OAn) on selenious acid aqueous solution without additional oxidant and reductant. The formation of Se nanoparticles and the polymerization of 2-C₁₆OAn in the monolayer occurred simultaneously. The results showed that the limiting area per repeat unit on selenious acid subphase was larger than that on pure water, which indicated the formation of poly(2-hexadecyloxyaniline)/Se nanocomposite monolayer at air/water interface. The amorphous spherical Se nanoparticles and triangular single-crystal ones in the Langmuir–Blogett (LB) films were formed at 20 ± 1 °C and 35 ± 1 °C, respectively. Poly(2-hexadecyloxyaniline)/Se nanocomposite LB films with excellent quality could be obtained on different substrates, indicating that the transfer ratio of monolayer was close to unity. Furthermore, poly(2-hexadecyloxyaniline)/Se nanocomposite LB films possessed high conductivity with the current of 10⁻⁵ A cm⁻¹.     

Mn,Cu掺杂对ZnS∶Mn,Cu电致发光材料亮度的影响

采用水热法制备了ZnS∶Mn,Cu电致发光材料,利用透射电镜对发光材料的结构和形貌进行表征,并且探讨了Cu2+、Mn2+掺杂量和反应温度对ZnS∶Mn,Cu发光材料亮度的影响。结果显示,随着Cu2+、Mn2+掺杂量的增加,发光材料的亮度也随之增加,但对于Cu2+、Mn2+掺杂都存在最佳值,当Cu2+掺杂量0.2%,Mn2+掺杂量4%,温度150℃时,得到的电致发光材料亮度较高,粒径约10nm左右。     

Highly conducting Langmuir-Blodgett films of the TMTTF-CnTCNQ system

Highly conducting Langmuir-Blodgett (LB) films of the tetramethyltetrathia-fulvalene- alkyltetracyanoquinodimethane (TMTTF-C_n TCNQ, where C_n represents C_nH_2n+1) system are reported. The electron affinities of the acceptors C_nTCNQ (n=14, 18 or 22) in solution are almost the same and lie between those of TCNQ and dimethylTCNQ. These TCNQ derivatives form solid charge transfer complexes with TMTTF. The limiting areas of the complexes, normalized to the number of TCNQ derivatives at the air-water interface, are almost the same irrespective of the donor-to-acceptor ratio and of the length of the alkyl chain, indicating that the areas are governed by the TCNQ moiety. The monolayers of TMTTF-C_n TCNQ (n=14 or 18) are transferred onto solid substrates as LB films. Polarized UV-visible absorption spectra indicate that the long axis of TCNQ is parallel to the film surface. These LB films exhibit lateral conductivities as high as 0.4 S cm^-1 and 0.1 S cm^-1 when n=14 and n=18 respectively.