Evolution of NaNO<Subscript>2</Subscript> in porous matrices

NMR and dielectric studies of NaNO₂ loaded into an SBA-15 mesoporous matrix are reported. The spin-lattice relaxation rate and the ²³Na NMR line shift, as well as the permittivity, were measured within a broad temperature interval including the ferroelectric phase transition in NaNO₂. The phase transition temperature of sodium nitrite in as-prepared samples was shown to differ substantially from that characteristic of a bulk crystal. The permittivity grows strongly in the vicinity of the phase transition. Heating a sample causes the properties of NaNO₂ embedded in pores to gradually approach those of bulk crystals.     

Study of commensurate and incommensurate phases in NaNO2 by 23Na NMR

The temperature dependence was determined of the ²³Na NMR spectrum of NaNO₂ with special emphasis on the small incommensurate phase and the surroundings of the phase transition points. Whereas far away from the transitions satellite lines of Gaussian shape with the natural line widths are observed near the transitions broad line distributions are detected showing distinct edge singularities. The results are related to the sinusoidally modulated and homogeneous order parameters of the incommensurate and ferroelectric phases.     

Dielectric properties of porous aluminum and silicon oxides with inclusions of triglycine sulfate and its modified analogs

This paper reports on an investigation of the temperature dependences of the capacitance and conductance of composite materials prepared by incorporating the ferroelectric TGS and its analogs—TGS with addition of L,α-alanine and chromium—into porous Al₂O₃ and SiO₂ matrices. It has been established that conduction of the structures under study involves charge transport predominantly through the ferroelectric embedded in the porous matrix. A mechanism is proposed to account for the displacement of the phase transition temperature of the ferroelectric inclusion under “restricted geometry” conditions, which is driven by the difference between the thermal expansion coefficients of the porous matrix and the embedded ferroelectric.     

Thermal effects in the vicinity of phase transition temperatures in matrix-isolated sodium nitrite NaNO<Subscript>2</Subscript>

Thermal effects in some nanoporous silicate matrices (with different pore sizes) loaded with ferroelectric NaNO₂ from both a saturated solution and from a melt have been studied in a wide temperature range including the phase transition temperatures. All the samples reliably demonstrate maxima of the heat capacity, corresponding to first-order ferroelectric phase transitions. The characteristics of the maxima (intensity, half-width, phase transition temperature, etc.) have been determined. A more complex situation is the observation of an incommensurable phase (sinusoidal antiferroelectric), in particular, in the case of pore sizes comparable to the period of an “incommensurable” wave, the manifestation of which can be explained by the appearance of a corresponding orientation of sodium nitrite nanocrystals in pores of these matrices. It is found that the characteristics of above noted effects depend on the prehistory of the samples under study.     

Observation of87Rb NMR satellite transitions in the commensurate and incommensurate phases of Rb2ZnCl4

It is shown that the first order quadrupole split NMR satellite transition frequencies of the⁸⁷Rb nucleus can be detected in the paraelectric, incommensurate and ferroelectric phases of Rb₂ZnCl₄. From rotation patterns the electric field gradient tensor at the Rb sites is determined for the paraelectric phase. The data demonstrate a considerable influence of the structural changes in the incommensurate and ferroelectric phases on the observed NMR transition frequencies. For some crystal orientations the satellite transitions are followed through the incommensurate into the ferroelectric phase. Whereas in the former typical quasi continuous spectra are observed in the latter several sharp lines appear. The results are discussed in relation to the structural changes at the phase transitions.     

Nuclear magnetic resonance study of potassium dihydrophosphate

A powder sample of potassium dihydrophosphate KH₂PO₄ has been studied by the ³¹P NMR method in a wide temperature range covering the ferroelectric phase transition. Changes in the position and shape of the resonance line at the transition to the ferroelectric phase have been revealed. The parameters of the chemical shift tensor of ³¹P (isotropic shift, anisotropy, and asymmetry) in the ferroelectric phase have been calculated from the experimental data. A sharp increase in the anisotropy of the tensor at the phase transition has been demonstrated. Dielectric measurements have also been carried out to verify the transition temperature.     

NMR of23Na in small particles of ferroelectric NaNO2

Pulse and wide line NMR spectroscopy were applied to small ferroelectric NaNO₂ particles, produced from aqueous solution and embedded loosely in silicagel. Mean particle diameters as determined by SEM and TEM were between 0.2 and 5.0 µm. From the cw-experiments it followed, that the particles had the crystalline structure of the bulk. It is shown that the spectrum of critical fluctuations and the phase transition temperature in the particles proved to be independent of the size. If there is a dead layer at the particle surfaces its thickness does not exceed 1×10^–2µm.     

High-resolution 31P nuclear magnetic resonance study of phase transitions in TlH2PO4

High-resolution ³¹P nuclear magnetic resonance (NMR) techniques were employed to study a KH₂PO₄-type ferroelectric system, TlH₂PO₄. A marked temperature dependence of the isotropic chemical shift below the ferroelastic phase transition temperature is indicative of an electronic instability. The NMR linewidth showed a discontinuity at the ferroelastic phase transition, and the anisotropy was measured to increase rapidly below the antiferroelectric phase transition. Thus, the changes in the microscopic environments associated with the phase transitions were sensitively reflected in a characteristic manner.     

典型高分子材料的固体核磁共振研究

本论文通过固体核磁共振（NMR）谱及动力学参量的测量,并结合X-射线衍射技术和DSC测量等研究了两种典型高分子材料的相结构、链的运动以及相与相之间的关系.  乙烯-醋酸乙烯共聚物( EVA) 是最主要的乙烯共聚物之一. 研究发现,EVA的相组成非常复杂,共有5个不同的组分. 除了PE中所观察到的常规单斜晶相和刚性的正交晶相外,我们发现还存在第三个晶相分量－运动性较强的晶相（SOCP,可能是转动相）. 它不仅拥有自己的熔点,而且它的化学位移和分子运动性不同于刚性正交晶相（LOCP）. 另一方面,非晶相也由两种不同的分量组成：运动受限的各相异性的非晶界面相和高度可动的橡胶型的非晶相. 我们进一步详细研究了EVA中的晶区链动力学和非晶区的低温冻结行为. 实验发现,在正交晶相中,高分子链以180° flip-flop方式运动,同时伴随沿链方向的平移型跳跃运动,并引起正交晶相和非晶相之间的长程链扩散,通过NOE的测量证实了这种相间链扩散的存在,并进一步通过实验证实这种相间链扩散是一种受限扩散而不是自由扩散. 同时非晶相的两个组分具有不同的低温冻结行为：当温度低于-弛豫转变温度时,橡胶型的非晶相中的长程分子运动被冻结,但仍存在分子的局域运动;而界面非晶在低温时冻结成一种有序取向结构,并用质子自旋扩散实验证实该有序结构与正交晶相相邻近.  少量纳米级片层状粘土分散在聚合物中就可赋予材料许多优异的性能,我们用固体NMR技术对EVA/REC复合材料的结构和其中粘土的分散性质进行研究,发现上述复合材料中所形成的晶体类型不仅依赖于各组分的性质还依赖于所形成的复合材料的类型.  偏氟乙烯/三氟乙烯共聚物（P（VDF-TrFE））是最主要的铁电高聚物之一. 我们利用变温固体¹⁹F MAS NMR 谱及弛豫数据的测量详细研究了电子辐照对P(VDF-TrFE)共聚物的分子结构、构型、运动性以及相变等的影响. 发现,电子辐照不仅改变了分子链段的构型和运动性,同时也改变了局部分子化学结构. 电子辐照促使铁电相向顺电相(或者非晶相)转变,与此同时诱发了富含VDF和含-TrFE链段从全反式的构型到混合的反式-旁式构型的转变. 电子辐照加剧顺电区域中的分子运动而在高温熔融态中(>100 ℃）,分子的运动反而受限.     

23Na nuclear magnetic resonance study of the phase transition in ammonium rochelle salt,NaNH4C4H4O6 • 4H2O

The satellite NMR spectrum of ²³Na in ammonium Rochelle salt (NaNH₄C₄H₄O₆ ? 4H₂O) is investigated near the transition temperature. Each line in the paraelectric phase splits discontinuously into four lines at the transition temperature; this fact is compatible with the first-order phase transition and reveals the existence of the superstructure in the ferroelectric phase.     

On the dielectric and thermal behaviour of the ferroelectric NaNO2

The temperature dependence of the spontaneous polarization of the uniaxial ferroelectric NaNO₂ is measured. The results are discussed in connection with the known behaviour of the dielectric constant and of the specific heat. They can be represented by a Landau expansion of the thermodynamic potential describing a phase transition of the first order. The coefficients of this expansion could be uniquely determined from the data of the ferroelectric phase.     

An EPR study of local fluctuations in the vicinity of the ferroelectric phase transition in Li2Ge7O15

EPR spectra of Mn²⁺ ions have been studied in the temperature interval containing the ferroelectric transition in crystalline lithium heptagermanate Li₂Ge₇O₁₅. The EPR linewidth and shape were measured as functions of temperature and orientation. It is shown that the critical resonance-line broadening observed to occur in the vicinity of the phase transition is due to fluctuations in the local order parameter with frequencies below 10⁷ Hz.     

EPR study of the ferroelectric phase transition in chromium-doped DMAAS

X-band electron paramagnetic resonance (EPR) investigations of single crystals of Cr³⁺-doped dimethylammonium aluminium sulphate hexahydrate are presented from 100 K to room temperature. The crystal undergoes a phase transition at 152 K from the ferroelastic to the ferroelectric phase. The spin-Hamiltonian parameters have been determined for both phases. The spin-Hamiltonian parameters in the ferroelectric phase are:g=1.980±0.003,b ₂ ⁰ =(1140±15)·10^?4 cm^?1,b ₂ ² =(214±10)·10^?4 cm^?1. Remarkable EPR line width changes confirm the order-disorder character of the ferroelectric phase transition on a microscopic level and demonstrate that the dimethylammonium reorientation freezing-out is the prime reason for this transition.     

87Rb NMR study of the temperature and electric field dependence of the soliton density near the lock-in transition of incommensurate Rb2ZnCl4

The frequency distribution of the⁸⁷Rb NMR 1/2–1/2 central transition is measured in a detailed manner as a function of the temperature and the crystal orientation in the normal (N), incommensurate (IC), and commensurate (C) phases of high quality single crystals of Rb₂ZnCl₄ (RZC). Special emphasis is laid upon the region around the lock-in transition atT _c . While in the N and C phases discrete lines are observed, in the IC phase a continuous distribution of frequencies is detected. In a temperature interval not exceeding 15 K aboveT _c some centers of intensity termed C lines can be observed in the frequency distribution. They reflect the fact that in the IC phase close toT _c several nuclei feel a local surrounding very similar to that of the low temperature C phase. For the first time in the region aroundT _c the influence could be studied which an electric field favouring the ferroelectric C phase has on the NMR spectra. The experimental results are related to the temperature and electric field dependence of the soliton density near the lock-in transition. A general definition of the soliton density is developed whose validity is not limited to the very narrow soliton limit. The meaning of this definition is also discussed in terms of well known phenomenological theories of the three phases of RZC. The experimental NMR data can be well described by this general definition.Dedicated to Prof. Dr. H.E. Müser on the occasion of his 60th birthday     

High-pressure dielectric studies of a novel hydrogen-bonded ferroelectric (NH4)2H2P2O6

The hydrostatic pressure effect on the dielectric properties of (NH₄)₂H₂P₂O₆ ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dT_c/dp=?5.16×10^?2 K MPa^?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C₊) and ferroelectric (C_?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.     

Second harmonic generation in layered TunS2 in the vicinity of the low-temperature phase transitions

Second-harmonic generation in the ternary layered semiconductor TlInS₂ excited with the wavelength λ = 1.06 μm of YAG: Nd^{3 +} laser is investigated in the temperature range corresponding to the low-temperature phase transitions. It is shown that the intensity of the second-harmonic signal corresponding to the non-linear coefficients d_eff, d₂₁, d₂₂ reveals peculiarities close to the commensurate-incommensurate phase transitions. The temperature hysteresis of the second-harmonic signal in the low-temperature region (below and close to T_i2 = 206K) is explained assuming that an incomplete lock-in transition in TlInS₂ takes place at T_c1 =204K within the temperature range between a ferroelectric (T_c2 = 201K) and an incommensurate (T_i2 = 206 K) phases. It is shown that the monoclinic point group symmetry C₂ is preserved also at temperatures lower than the phase transition temperature Tc4 = 79K to a weak ferroelectric state.     

Nuclear magnetic resonance study of the smectic-cholesteric phase transition in a dimesogenic liquid crystal

Nuclear magnetic resonance (NMR) spectroscopy has provided a unique opportunity to study the characteristic smectic-A to chiral nematic phase transition in a dimesogenic liquid crystal (“KI-5S”). The order parameters in the liquid crystalline phases were obtained from the ²H NMR quadrupole splitting and ¹³C NMR chemical shift measurements, manifesting a first-order smectic-nematic phase transition.     

Origin of the structural local transition in the molecular impurity ion MnO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack> in the K<Subscript>3</Subscript>Na(CrO<Subscript>4</Subscript>)<Subscript>2</Subscript> ferroelastic

A new model is proposed for a local transition in a Jahn-Teller impurity center in a crystal with a ferroelastic (ferroelectric) phase transition. This model is based on direct interaction of the order parameter of the phase transition in the matrix with the Jahn-Teller impurity degrees of freedom. It is shown that, under these conditions, the order parameter field can induce lifting of degeneracy of the electronic states active in the Jahn-Teller effect, which is accompanied by a transition from the Jahn-Teller effect to the pseudo-Jahn-Teller effect with its subsequent suppression. As a result, a decrease in temperature gives rise to a structural local transition in the region of the low-symmetry ferroelastic (ferroelectric) matrix phase from the many-well local adiabatic to a single-well potential. The model proposed allows interpretation of experimental data obtained in an EPR study of the molecular impurity ion MnO ₄ ^2? in the K₃Na(CrO₄)₂ ferroelastic.     

Photoluminescence investigations on the nanoscale phase transition in Pb(Mg1/3Nb2/3)O3

The temperature dependence of the photoluminescence spectra of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃ has been reported. The temperature behaviours of the 1.57, 1.67 and 1.73 eV bands indicate a phase transition at 110 K. This is attributed to a structural phase transition in the charged nanoshell. Analysis of the temperature dependence of 1.67 eV band intensity with a thermal quenching model indicated the existence of a phonon mode at 1153 cm⁻¹. This mode is identified in the Raman spectra measurement. The intensity of the 1.73 eV band showing an anomalous behaviour at 210 K is attributed to a transition from a crystalline phase to an amorphous phase in the charged nanoshell.     

The thermodynamic functions of ferroelectric and paraelectric SbSI

A first-principle method is used to calculate phonon density of states, Helmholtz free energy, internal energy, and entropy for ferroelectric and paraelectric SbSI. Theoretical phase transition temperature was obtained using the difference of the Helmholtz free energy, internal energy, and entropy term between ferroelectric and paraelectric phases on temperature. The obtained value is in reasonable agreement with the experimental second-order phase transition temperature T_c2 = 233 K.