Detailed I.R. Study of the Phase Transition in the System AgNO3-Fe(NO3)3

A complete infrared study of the mixed crystal system of AgNO₃ and Fe(NO₃)₃ is carried out in the region 400–4000 cm^?1. The study includes internal fundamental normal vibrations of the NO₃^? ion in the ordered and disordered phases of AgNO₃ at different values of the ferric concentration, I.R. spectra, spectral band shape intensities, and frequencies of the internal modes as functions of the ferric ion concentration. Special attention is paid to bending mode, combination mode, asymmetric stretching mode, and over-tone. The rotational energy barrier is determined at different concentration of the ferric ions in the system of AgNO₃-Fe(NO₃)₃.     

Structural behaviour of AgNO3 at low temperatures by neutron diffraction

Structural behaviour of silver nitrate (AgNO₃) at low temperatures has been investigated by neutron powder diffraction and differential scanning calorimetry (DSC). Analysis showed abnormal changes in the rotations of nitrate (NO₃) anions and thermal displacement parameters of the atoms near 220 K and 125 K. However, the basic lattice is compatible with the orthorhombic symmetry (space group Pbca) till 12 K. The fine, small-scale structural anomalies probably originate from freezing of reorientation of NO₃ ions from high-temperature disordered phase.      

Comparitive study of structure changes with temperature in univalent and divalent ionic nitrate crystals

The temperature dependence of the d.c. resistivity and dielectric constant of polycrystalline samples of Pb(NO₃)₂, Ba(NO₃)₂ and Sr(NO₃)₂ were found to show anomalies in the high temperature region. In addition, sharp peaks were obtained in both differential thermal analysis (DTA) and thermomechanical analysis (TMA) curves in the same temperature range. The observed anomalies were attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for the first time. A comparison is made between the role of NO₃^?ions in both the divalent and univalent nitrates, taking NaNO₃ as representative. The TMA curve for Sr(NO₃)₂ showed a pronounced peak at 325°C. This peak was related to a sudden increase in the expansion coefficient associated with the rotation of the NO₃^? group leading to a solid state phase transformation. Energy diagrams describing the conduction mechanism and showing a fractionization of energy barriers in the case of divalent nitrates are introduced.     

A Study of the Thermal Hysteresis in AgNO3

The reversible phase transformation of AgNO₃ is studied. Dielectric constant, d.c. resistivity, differential thermal analysis (DTA) and dilatometric measurements show the occurrence of a reversible phase transition II→I at 160°C with heat of transformation H = 0.78 kcal/mol. The thermal hysteresis in this reversible transformation is examined, the magnitude of the temperature hysteresis does not exceed 12°C. An acceptable agreement is observed between the measured values of the transition temperature obtained by three different experimental techniques. The dilatometric analysis shows that this transition is accompanied by thermal shrinkage with relative shrinkage coefficient 8 × 10^?4. Thermal analysis are also used to get thermodynamic and kinetic data of this phase transition. The temperature dependence of the dielectric constant and d.c. resistivity for single crystals as well as polycrystalline samples of AgNO₃ have clearly located and confirm the phase transitions II→I→II with a strong support to its thermal hysteresis character. The conduction mechanism is found to be activated by energy 0.12 eV for phase I and 0.36 eV for phase II. The observed thermal behaviour of the various measured parameters is attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for first time in AgNO₃.     

Proton magnetic resonance study of the low-temperature phase transition in a LiNH4SO4 single crystal

The proton NMR line width and spin-lattice relaxation times for LiNH₄SO₄ single crystal were studied at low temperature range of 6 and 280 K. The changes in the proton relaxation behavior near the phase transition temperature indicates a change in the state of internal motion at the transition. The molecular motions obtained by the spin-lattice relaxation processes were found to be determined by molecular reorientation of the NH₄ ions in phases III, IV, and V. We also confirmed that the phase transitions occur at 26 and 133 K.     

Characterization of LaMnAl11O19 by FT-IR spectroscopy of adsorbed NO and NO/O2

The nature of the NO_x species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on LaMnAl₁₁O₁₉ sample with magnetoplumbite structure obtained by a sol-gel process has been investigated by means of in situ FT-IR spectroscopy. The adsorption of NO leads to formation of anionic nitrosyls and/or cis-hyponitrite ions and reveals the presence of coordinatively unsaturated Mn³⁺ ions. Upon NO/O₂ adsorption at room temperature various nitro-nitrato structures are observed. The nitro-nitrato species produced with the participation of electrophilic oxygen species decompose at 350 °C directly to N₂ and O₂. No NO decomposition is observed in absence of molecular oxygen. The adsorbed nitro-nitrato species are inert towards the interaction with methane and block the active sites (Mn³⁺ ions) for its oxidation. Noticeable oxidation of the methane on the NOx⁻-precovered sample is observed at temperatures higher than 350 °C due to the liberation of the active sites as a result of decomposition of the surface nitro-nitrato species. Mechanism explaining the promoting effect of the molecular oxygen in the NO decomposition is proposed.     

A Study of the Phase Transition in the System [Ag1−x(Na)x]NO3 by Infrared Spectroscopy

A complete infrared study of the mixed crystal system of AgNO₃ and NaNO₃ is carried out in the region 400–4000 cm^?1. The study includes internal fundamental normal vibrations of the NO^?₃ ion in the ordered and disordered phases of AgNO₃ at different values of the sodium concentration, the I.R. spectra, spectral band shape intensities, and frequencies of the internal modes as functions of the sodium ion concentration. Special attention is paid to bending mode, combination mode, asymmetric stretching mode, and over-tone. The rotational energy barrier is determined at different concentrations of the sodium ions in the system.     

Frequency-dependent specific heat near the glass transition measured with the photoacoustic effect

For the supercooled salt melt 0.4 Ca(NO₃)₂–0.6 KNO₃ the photoacoustic amplitude and phase shift are measured in the glass transition region. The transition temperature is defined by the maximum in the phase angle. It is shifted to lower temperatures for lower frequencies. A frequency-dependent specific heat can be calculated from the data in the dispersion region. The frequency dependence of the transition temperature can be fitted by a power law with exponent =8.8±1.This work is part of a Ph. D. thesis at the Technische Universität München     

Raman scattering study of the low temperature phase of ammonium nitrate

Raman spectra of NH₄NO₃ and ND₄NO₃ have been recorded from room temperature down to 11K. A sluggish transition from phase IV to phase V was clearly observed but no evidence was found for another low temperature phase. Large splitting of the ν₃ mode indicates that the interionic interaction between NH⁺₄ and NO^-₃ is rather strong in both phases. A possible mechanism for the transition involving coupled modes is discussed.     

Electron spin resonance studies at the phase transition in YbInCu4

In the intermetallic compound YbInCu₄ the Gd³⁺-ESR and the static susceptibility were measured in the temperature range 1.5K–300 K, i.e. both below and above the valence phase transition which occurs in this material at T_ph≈50 K. The Gd³⁺ resonance is mainly determined by exchange interaction of Gd³⁺ ions with fluctuating Yb³⁺ ions via conduction electrons (RKKY coupling) both below and above this transition. Arguments are presented that at low temperature YbInCu₄ is a dense Kondo system (mixed valent state).     

Phase coexistence in annealed CaMn7O12

The structural phase transition in annealed CaMn₇O₁₂ has been investigated by using high resolution synchrotron radiation powder diffraction. There is a phase coexistence phenomenon: two different crystallographic phases coexist in the material between 410 and 458 K. The first one is trigonal and it has a charge ordering (CO) of the Mn³⁺ and Mn⁴⁺ ions, while the second one is cubic and charge delocalized (CD). The volume fraction of the CD phase increases with temperature from 22% at 418 K up to 100% at 468 K. Both phases have domains of at least 150 nm at each temperature. The annealing of CaMn₇O₁₂ relaxed a part of the strains in the lattice, but did not influence the phase coexistence phenomenon.     

Role of Mn doping for obtaining of hexagonal phase in Ba0.98Zn0.02TiO3 ceramics

This paper reports the observation of hexagonal phase of barium titanate by Mn doping and its effect on dielectric and magnetic properties. Ceramic samples of Ba_0.98Zn_0.02Ti_1−xMn_xO₃ (where, x= 0.04, 0.06 and 0.08) were prepared by traditional solid-state reaction route. The hexagonal phase is stabilized in the composition Ba_0.98Zn_0.02Ti_0.92Mn_0.08O₃ and a very feeble M–H loop is also observed in that composition. This induced magnetism is expected due to the exchange interactions between magnetic polarons formed by oxygen vacancies with Mn ions. The dielectric constant as well as the ferroelectric to paraelectric transition temperature is systematically decreased with increasing of Mn doping concentration. Further to that, the temperature dependent dielectric constant curve is also broadened at transition temperature with increasing of Mn concentration. However, the ferroelectric to paraelectric transition temperature is well above room temperature.     

SERS observation of the effects of pressure and water on the absorbed state of nitrogen dioxide on a silver powder surface

The effects of pressure and water on the adsorbed state of nitrogen dioxide on silver powder produced from an aqueous solution of AgNO₃ were studied by SERS. NO₂ of 10² Pa was added to the silver powder in the sample chamber and then pressure was raised up to ∼10⁵ Pa with dry Ar, N₂ or O₂. The observed surface species are NO₃⁻ and NO₂⁻ ions under atmospheric pressure. When the total pressure decreases, NO₂⁻ is transformed into NO₃⁻ and NO⁺. This reaction is reversible with the total pressure variation of dry gases regardless of kind. Once the silver powder adsorbing nitrogen oxides is exposed to moistened gas or air of ∼10⁵ Pa, the reversible variation was interrupted, and NO₃⁻ and NO₂⁻ ions are observed on the silver surface.     

Pressure and temperature induced high spin–low spin phase transition: Macroscopic and microscopic consideration

The behavior under pressure of the high spin–low spin phase transition in the coordination compounds containing 3d ions is analyzed using thermodynamic and microscopic approaches. For thermodynamic approach the mean field model with interactions between spin-crossover molecules is considered. Microscopic model takes into account the interaction of d electrons of the transition metal ions with full symmetric distortions of the ligands. The relationship of the thermodynamic interaction parameters with microscopic ones is installed and shown how the quantum–mechanical interactions form the cooperativity of the system. Within the microscopic model the temperature and pressure dependences of the high spin fraction in 2-D compounds {Fe(3-Fpy)₂[M(CN)₄]} (M=Pd, Pt) are simulated and microscopic parameters are evaluated. It is concluded that different experimental behaviors of the temperature and pressure induced spin transitions are determined by different variations of the inelastic and elastic energies under pressure, and vibrational component of the free energy drives the ST equally with electronic part.     

外加热型金刚石对顶压砧高压装置及高温下的压力测量

 本文报导了一种外加热型金刚石对顶压砧装置的高温高压技术，装置的压力可达20 GPa，温度可达350 ℃。采用本装置对六角结构的α-LiIO₃进行了高温高压X射线衍射实验，获得的四方结构高压相与用淬火卸压所得的ε相结构一致；建立了高温下的红宝石测试技术。发现可以根据由此法测定的Δγ_p-T曲线初步判别样品是否存在伴随有体积变化的结构相变，并可估计出该相变的压力、温度范围及相变造成的压力下降值。     

Study of the optically diffused reflectance and thermal-microstructure for the phase transformation of AgNO3

Optical, microstructural, and thermal properties of the investigated silver nitrate samples were characterized by various techniques, such as X-ray analysis, scanning electron microscopy, UV–Vis–NIR absorption and differential scanning calorimetry (DSC). The presence of structural phase transition [orthorhombic structure (phase II) to rhombohedral structure (phase I)] was checked by DSC and X-ray analysis measurements. The thermal energy required for such transformation is found to be 11.6 J/g. The optical band gaps of AgNO₃ are 1.4 and 2.02 eV for phase II and phase I, respectively, at the low-energy region. But at high-energy region, the optical band gaps are 3.41 and 3.43 eV for phase II and phase I, respectively. Characteristic peaks for AgNO₃ corresponding to (2 1 1), (0 0 4) and (3 5 1) for phase II and (0 0 4), (3 1 1) and (0 2 4) for phase I have been observed. The average crystalline size for AgNO₃ samples and the values of dislocation density δ and the strain ε for the planes of two phases II and I are calculated and also the texture coefficient is determined. Such information can considerably aid in understanding the process of phase transformations in AgNO₃.     

Magnetic properties of disordered ferrite and ilmenite-hematite thin films

We have synthesized thin films of disordered zinc ferrite (ZnFe₂O₄) and ilmenite-hematite (FeTiO₃-Fe₂O₃) solid solution, the former and the latter of which are interesting from the viewpoints of magnetooptics and spintronics, respectively, by utilizing sputtering and pulsed laser deposition methods, and have explored their magnetic, magnetooptical, and electrical properties. Although ZnFe₂O₄ possesses a normal spinel structure as its stable phase, some of the Fe³⁺ ions occupy the tetrahedral as well as the octahedral sites in ZnFe₂O₄ of which the sputtered thin film is composed. Consequently, the as-deposited thin film manifests large magnetization even at room temperature although the magnetic phase transition temperature of the stable phase of ZnFe₂O₄ is as low as 10 K. Also, the thin film exhibits a cluster spin glass transition at a temperature as high as 325 K. Furthermore, the ZnFe₂O₄ thin films exhibit large Faraday effects at a wavelength of 400 nm or so. The ilmenite-hematite solid solution is one of the ferrimagnetic semiconductors. Most of the compositions possess Curie temperatures higher than room temperature, and the type of carrier can be tuned only by changing the composition. We have succeeded in synthesizing solid-solution thin films of various compositions grown epitaxially on sapphire substrates with a (0 0 0 1) plane, and have shown that the thin films are ferrimagnetic semiconductors.     

Ca-doping effects on N-type ferrimagnetism of NdVO3

Ca²⁺-doping effects were studied on the N-type ferrimagnet of NdVO₃. The chemical pressures by Ca²⁺-doping induced lowering of ferrimagnetic transition temperature T_c and compensation temperature θ_c, resulting in the phase transition from N- to P-type ferrimagnetic phase. In the N-phase, spontaneous magnetization M_sp becomes zero at finite temperature θ_c and in the P-phase, M_sp is positive in whole temperature range. It was revealed that NdVO₃ and Ca_0.1Nd_0.9VO₃ located in the N-phase and Ca_0.2Nd_0.8VO₃ in the P-phase. This N→P transition by the chemical pressure was discussed by the intra- and inter-sublattice exchange integrals estimated from the molecular field approximation.     

Rotational and vibrational relaxation of the NO3 - ion in molten binary systems (M,Ag)NO3 (M = Li,Na and K) by Raman spectroscopy

Polarized and depolarized Raman scattering spectra for the totally symmetric stretching υ₁ mode of nitrate ions (D_3h symmetry) in the molten binary systems (M1,Ag)NO₃(M1= Li, Na, and K) have been measured. Vibrational and rotational autocorrelation³ functions, C_v(t) and C_r(t), respectively, have been evaluated from Fourier transformation of the spectra. The shifts in the peak frequencies are deeply correlated with the polarizability of silver in these mixtures. The vibrational relaxation rate increases with increasing mole fraction of silver nitrate in (K,Ag)NO₃, but does not vary so much in (Li,Ag)NO₃ and (Na,Ag)NO₃. The vibrational relaxation time negatively deviates from additivity on the order of (Na,Ag)NO₃< (Li,Ag)NO₃< (K,Ag)NO₃. In the systems (Na,Ag)NO₃ and (K,Ag)NO₃ rotational relaxation time becomes slower with increasing concentration of AgNO₃. The Ag⁺ coordinating to several nitrate ions in these mixtures appreciably restricts the rotational motion of the nitrate ions. On the other hand, rotational motion becomes easier in the mixture system (Li,Ag)NO₃ mainly because the different preferential sites of the two cations coordinating to an NO₃ ^-ion, and partly because the exchange rates of these cations around the NO_-3 ^-ion are high.     

Study of the orientation of HNO3 molecules intercalated in graphite using nuclear techniques

Nuclear resonance scattering of photons from ¹⁵N has been used to study the orientation of the HNO₃ intercalant molecule with respect to the graphite planes. In the second-stage compound C₁₀(HNO₃) and the temperature range T = 15°K ? 300°, no orientational phase transition was observed and the NO₃ molecular plane was found to be oriented at an angle θ ∽ 82 ± 8° with respect to the graphite planes.