Filled SA phases in binary liquid crystalline systems of terminal-nonpolar compounds (III). The role of the molecule length of the rod-like component

The phase diagrams of 8 binary systems of liquid crystals are presented whereby one component is a “biswallow tailed” compound and the second component is a member of the homologous series of 4,4′-bis-n-alkyloxy-azoxybenzenes. In all phase diagrams studied induced smectic A phases occur. X-ray investigations give evidence that in the binary systems of short-chain homologues the layer spacing d of the smectic A phase is clearly greater than the average molecular length L̄, whereas in the systems of long-chain homologoues d is found to be somewhat smaller than L̄. The results are interpreted on the basis of a simple packing model.     

Filled SA phases in binary systems of terminal-nonpolar compounds (IV). Mixtures of biswallow-tailed compounds and nematogenic twin compounds

The phase diagrams of three binary systems of liquid crystals are presented whereby one component is a biswallow-tailed compound and the second component is a member of homologous twin compounds. The most important feature of the diagrams is the occurrence of induced S_A phases and reentrant nematic phases. The existence of the induced S_A phase can be interpreted by the special molecular structure of the mixing components.     

Laser produced amorphous phases in NbSi and VSi thin films

The binary systems NbSi and VSi are investigated by laser induced melting and quenching of vapor deposited thin films. Glassy phases of various compositions are produced. The established compositional glass forming ranges support that the equilibrium compounds Nb₄Si is stable only at high temperature. Thermal decomposition of the amorphous NbSi films proceeds via several intermediate stages. In particular, the AuCu₃-type configuration of Nb₃Si was found to be formed. In addition, amorphous NbSi films around 20 at.% si show the formation of an undentified metastable compounds upon post-irradiation annealing. Amorphous VSi films proved to be stable up to at least 500°C. Above this temperature they decompose directly into their respective equilibrium phases.     

Formation of nanocrystalline and amorphous phases in Cu80P20, Ni82P18 and Cu87Ni13 mechanically alloyed systems

Variations in the crystallite size and stored strain caused by mechanical milling of binary alloy systems of copper, nickel and phosphor were compared. During mechanical alloying process, an amorphous phase is partially produced in CuP and NiP alloy systems and only a nanoscale crystalline phase in CuNi alloy system. The CuP alloy system first forms a Cu₃P intermetallic compound and then the partial amorphous phase by the reaction of primary copper phase and Cu₃P intermetallic compound, while the NiP alloy system directly forms a partial amorphous phase by the reaction of primary nickel and phosphor phases. When the crystallite sizes of primary copper and nickel phases become of the order of a few nanometers in the CuP and NiP alloy systems, they are in an almost strain-free state.     

The influence of silicon on the crystallographic phases of the niobium-gallium system studied by x-ray diffraction methods

The influence of silicon on the crystallographic phases of the binary niobium-gallium system is studied by X-ray diffraction methods. The samples were prepared by rapid quenching. Silicon substituted gallium in all phases of the binary system. It exists a complete pseudobinary solid solution Nb₅Ga₃-Nb₅Si₃. The maximum degree of substitution in the A 15 phase Nb₃Ga_1–xSi_x is x = 0.5. The presence of two A 15 phases with different cell parameters indicates the existence of a miscibility gap. Contrary to the expections the supercondusting transition temperatures decreases with an increasing degree of substitution.     

Induced SA phases in binary systems with EDA complexing

The phase diagrams of 13 binary systems are presented in which electron donor-acceptor (EDA) complexing is clearly detectable. In all binary systems studied the same electron donor compound was used whereas the electron acceptor compounds were members of two homologous series. It was found that the induction of smectic A phases increases with increasing length of the alkyl chain of the acceptor compound and with increasing stability of the complexes.     

System of hydrogen bonds in high-pressure phases of CsHSO4 crystals

The system of hydrogen bonds in the high-pressure phases of CsHSO₄ crystals has been constructed on the basis of the group-theoretical analysis of the systems of hydrogen bonds in the CsHSO₄ phases with the known symmetry.     

X-ray quantitative determination of the phases in a batch for the synthesis of poly- and monocrystal yttriumaluminium garnet

For the synthesis of ceramics and single crystals of yttriumaluminium garnet, a batch consisting of Y₂O₃ and Al₂O₃ is first treated thermally in order to obtain the garnet phase Y₃Al₅O₁₂. It is possible to make a choice of the optimum technological parameters of the batch if the amounts of all oxide phases, present during the synthesis, are well known. A combined X-ray quantitative method is suggested for this purpose. The initial oxides and a garnet phase are determined by the method with external standard. The rest two impurity oxide phases are determined as binary system. The specific diffraction characteristics of the present compounds were taken into account. The amounts of all phases in the batch, treated thermally from 1373 to 2075 K at every 100 K are shown.     

Studies on induced smectic phases (III). Fourier transform infrared and laser-raman spectral differences between isotropic and induced smectic phase of binary mixtures of nematogens with contrasting dielectric anisotropies

The S_E, S_B, S_A induced phase sequence was detected in binary mixtures of two nematogens, 4,4′-di-n-heptyl azobenzene (7AB) with 4-n-pentyl-4′-cyano biphenyl (5CB). The mixtures as well as the single components were studied by Fourier transform IR and laser-Raman spectroscopy at different temperatures. Charge redistribution of 5CB is demonstrated by the spectral differences found by the ratio-recorded IR spectra and also by integrating the intensities of some Raman lines. The spectra of the different phases of the 7AB—5CB mixture, built up from components of different length, indicate a population increase of the gauche conformers of 7AB in the smectic A phase.     

Stabilization and destabilization of the SA phase in mixtures of 4-nitrobenzyl-2,5-bis(4-n-alkyloxybenzoyloxy)benzoates

4-Nitrobenzyl-2,5-bis(4-n-alkyloxybenzoyloxy)benzoates exhibit S_A phases which are characterized by an antiparallel packing of the molecules and a partial intercalation of the terminal alkyl chains. In binary systems of selected rod-like components the S_A mixed phase can be stabilized or destabilized depending on the molecular length of the rod-like molecules. This unusual behaviour is mainly due to steric interaction and can be interpreted by a simple packing model.     

On the bindings in the crystal phases of Mn

The heterotypism of Mn may be interpreted energetically when a temperature dependent valence electron concentration is supposed which takes on values between 2.2 and 0.6 electrons per atom. The room temperature phase Mn.r (= αMn) belongs to a series of structural types: Cr₃Si, U.h₁ (= βU), Mn.r, which occur in alloy systems such as MoRe_M (M = undetermined mole number) at certain values of the averaged group number (AGN) of the perodic system of chemical elements (rule of Raub). An interpretation of the series by means of the plural-correlations model becomes possible when instead of the (Ekmanian) AGN count another (non-Ekmanian) electron count is used. The phase Mo₃Re (Cr₃Si-type) yields a simple bonding type (binding) which undergoes moderate transformations to form the phases Mo₂Re₃(U.h₁) and MoRe₃(Mn.r) and the binding of MoRe₃ may be taken to be valid also for Mn.r; it corresponds to the valence electron concentration N′^A_b = 2.16. For the high temperature phases Mn.h₁ (= βMn) and Mn.h₂ (= γMn) the values N′^A_b = 1.6 and 1.0 are probable and allow the brass-like structures Mn.h₁ (C20) and Cu(Fl). The binding of Mn.h₂, incidentally, explains the occurrence of the tetragonal metastable phase Mn.m. finally Mn.h₃ (= δMn) crystallizing in the W-type is isodesmic to Fe.h₂ (= δFe), i.e. of the same binding.     

Solid phases in cycloheptanol: Dynamic disorder and glass transitions

The stable solid polymorphism of cycloheptanol (C₇H₁₄O, for short C₇–OH) is revised in the present paper. Four solid stable phases, denoted on cooling from the liquid as phases I, II, III and IV are identified from X-ray diffraction measurements. Lattice symmetry of phase III has been unambiguously stated as orthorhombic. Diffraction patterns corresponding to phase IV have been also indexed as orthorhombic, but only in a tentative way. A detailed broadband dielectric spectroscopy study devoted to these phases has been made. Such an experimental technique has no revealed differences between phases III and IV and from specific-heat measurements, the III–IV phase transition has not been observed yet. Dielectric results seem to evidence that the dynamic disorder of phase III and/or IV should be intra-molecular attributed to changes between the possible distinguishable molecular conformations along with possible hydroxyl group rotations. The possibility of C₇–OH as conformational glass-forming material is discussed.     

Identification of phases in thin amorphous films of zinc phosphides

Analysis of the experimental atomic radial distribution functions for thin amorphous films of zinc phosphides obtained by explosive laser sputtering has been performed within a fragmentary model. The experiment was carried out with an EMP-100A electron diffractometer in transmitted light at accelerating voltages of 50 and 75 kV. The films obtained by sputtering of β-ZnP₂ single crystals contained nanoparticles of this phase. The films based on Zn₃P₂ turned out to be two-phase and consisted of dispersed Zn₃P₂ and β-ZnP₂ nanoparticles. The composition of the film obtained on the basis of α-ZnP₂ corresponded neither to any one of the known phases in the Zn-P system nor to any mixture of these phases. Crystallization of films in a divergent electron beam confirmed the results of the phase analysis performed using the model atomic radial distribution functions.     

Dielectric relaxation in nematic,smectic A and C phases in the MHz region

The dielectric properties of four 4-n-alkyloxyphenyl 4-n-alkyloxybenzoates with nematic, smectic C and partly additional S_A phases were investigated. In 2 substances for ϵ′ reproducible values also in the smectic phases resulted allowing to conclude on a good orientation in the samples. In all 4 substances the dielectric relaxation in the MHz region was measured and the respective activation energies were determined. The molecular mobility in the S_C phases is higher than in the S_A phases, however comparable with that of the nematic phases. In all 3 phase types a single relaxation mechanism exists, which is explained as rotation of the molecules around a short axis.     

Structural investigation of bismuth borate glasses and crystalline phases

Glasses of the system: xBi₂O₃-(100−x)B₂O₃ (x = 20 to 66 mol%) were prepared and characterized by density, DSC, UV-visible absorption and ¹¹B MAS-NMR spectroscopy. Glass molar volume increases while the glass transition temperature decreases with Bi₂O₃ concentration. Densities of some bismuth borate glasses are found to be greater or very close to those of single crystal phases with equal composition. B¹¹ MAS-NMR studies determined that the fraction of tetrahedrally coordinated borons (N₄) is maximum at 42 mol% of Bi₂O₃ and that there is a local maxima in N₄ at Bi₂O₃ concentration of 50 mol%. Glasses containing Bi₂O₃ concentration of 33 mol% and higher show an unusual, intense absorption band just below the optical band gap. Two crystalline phases: Bi₃B₅O₁₂ and Bi₄B₂O₉ were prepared by devitrification of glasses and characterized by X-ray diffraction, FTIR and ¹¹B MAS-NMR studies. Both crystalline phases contained significantly lower N₄ than glasses with equal composition.     

Characterization of the Hexatic B and Crystal B phases by Optical Microscopy

Recent investigations concerning the structure of the B Phase have unearthed a variety of packing arrangements of the molecular layers for this semctic modification. Two general structures have been discovered; one in which the B Phase has three-dimensional crystalline order (crystal B), and one that is characterized by short-range in-plane positional ordering of the constituent molecules, and long-range bond orientational order, both within and between the layers (heatic B). In this present study n-hexyl 4′-n-pentyloxybiphenyl-4-carboxylated (650BC) has been synthesized and its smectic phases charaterized. Typically, this ester exhibits an A, B,E, phase sequence, with the B Phase being of the hexactic type. The Synthesis, microscopic textures, and miscibility studise ar reported here. The results show that while the two types of B phase appear co-miscibly by conventional optical mehtods, in fact X-ray diffraction studies show that a transition occurs between the two phases in certain binary mixtures. Thus, the hexactic B and crystal B modification are thermodynamically distint phasaes.     

Comparing investigation of the smectic C and A phases of the di-n-alkyl 4,4′-azoxycinnamates (II) X-ray studies

The paper continues the investigation of the smectic C and A phases of the title compounds which has been done in Part I by DSC calorimetry. Here the layer spacings in the S_C and S_A phases are presented which exhibit a remarkable different temperature dependence in the S_C phases within the homologous series. A tendency of a change from a second order S_C/S_A transition to a first order transition has been found. The layer spacings of the S_A phase show a chain length dependent difference to the lengths of the molecules which may be explained by an increasing amount of gauche conformations in the higher homologues.     

Structural Studies on Ni75(SnSi)25 and Ni75(SnBi)25 Alloys

Ternary alloys on the quasi-binary system Ni₃Sn(r) in equilibrium condition. It has been observed that these phases undergo transformations at high temperatures but upto 500 °C room temperature modifications are stable. The two phases do not have any appreciable solid solubility in either of them. The phase Ni₃Si(r) crystallizes in to Cu₃Au (Li₂) structure where as Ni₃Sn(r) is based on c.p.h. structure with a = 5.305 A°, c = 4.254 A°. No new ternary phase has been detected in Ni₃Sn Ni₃Si section. The investigated alloys of the Ni Sn Bi system contain 75 at.% Ni. All the ternary alloys show simultaneous occurrence of three phases, namely Ni₃Sn(r), NiBi and Ni(Sn) in equilibrium state. The phase NiBi has NiAs(B8) type of structure. Due to non-existence of isostructural phases in the two binary systems (Ni Sn and Ni Bi), single solid solution phases are not formed. Widely differing atomic sizes of nickel and bismuth atoms restrict the formation of solid solution of bismuth in nickel in contrast to Ni(Sn) where atomic size factor is favourable.     

Thermodynamic assessment of the Cu‐Mg‐Si system in its copper‐rich region

A thermodynamic assessment of the ternary Cu‐Mg‐Si system was made in its copper‐rich region in relation with the development of a thermodynamic database for Cu‐Mg alloys. The adjustable parameters of the binary end‐systems (Cu‐Mg, Cu‐Si and Mg‐Si) were taken from the literature and those of the Cu‐Mg‐Si system were optimized using experimental thermodynamic and topological data. For the sake of simplicity, the solution phases were described with the substitutional solution model and the intermetallic compounds were treated as plain semi‐stoichiometric phases ((A,B)_pC_q‐type). The assessment developed is applicable for magnesium contents up to 20 wt% (i.e. magnesium mole fractions ≈0.4) and silicon contents up to 16 wt% (i.e. silicon mole fractions ≈0.3). (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ionic conductivity of the phases of five types formed in the BaF2-GdF3 system

The ionic conductivity has been measured in ceramic phases of five structure types found in the BaF₂-GdF₃ system: the fluorite type (CaF₂), its trigonal and tetragonal distortions, the tysonite type (LaF₃), and the orthorhombic ??-YF₃ modification. The phases have been obtained by solid-phase synthesis from BaF₂ and GdF₃ mixtures in hermetic nickel containers at 925, 964, and 1067°C for 108?C360 h in a fluorine atmosphere. Their conductivity ?? is compared in correlation with the composition and structure type. The highest conductivity values are found for the tysonite Gd_{1 ? y} Ba _y F_{3 ? y} phase (0.10 ?? y ?? 0.25): (1?2) × 10^?3 S/cm at 683 K. The ordered Ba_0.60Gd_0.40F_2.40 and Ba_0.57Gd_0.43F_2.43 phases with fluorite-derived structures and different degrees of order are characterized by the lowest conductivities: i(1.5?3.5 × 10^?5) S/cm.