Pressure-Assisted Freezing and Thawing of Foods: A Review of Recent Studies

Phase transition phenomena take place in aqueous solutions, model foods and cellular tissues subjected to combined high pressure and low (subzero) temperature. The kinetics and mechanisms of pressure-shift ice nucleation, of type III, V or VI ice crystal formation, or of pressure-thawing are still poorly documented. Physical and chemical factors affect the ice crystal size distribution throughout sample depth. These phase transition phenomena, as well as the pressure level, influence both chemical constituents (proteins, enzymes) and structural elements (gels, emulsions, cellular tissues, micro-organisms). Recent studies indicate that: (1) in pressure-shift freezing of muscle foods, the aggregation of myofibrillar proteins and the resulting toughness due to high pressure exposition appear to offset the benefit of small ice crystal formation; (2) the cell and tissue structure of some fruits or vegetables is less disrupted by pressure-shift than air-blast freezing, but it is doubtful whether this brings improved appearance, texture or water retention; (3) high pressure-low temperature inactivation of enzymes is not sufficient to replace thermal blanching; (4) high pressure microbial inactivation is enhanced below 0 °C, but probably not enough for practical applications; (5) the benefits of pressure-thawing in terms of enhanced rate and hygiene may not compensate for increased equipment and packaging costs; (6) progress is made in modelling pressure-freezing and thawing, and in assessing the extent of pressure-shift nucleation.     

Fourier Self-Deconvolution Analysis of β-Sheet Contents in the Amide I Region of Hemoglobin Aqueous Solutions under Exposure to 900 MHz Microwaves and Bioprotective Effectiveness of Sugar and Salt Solutions

Spectroscopic Fourier self-deconvolution analysis was used to investigate β-sheet features in the secondary structure of hemoglobin under mobile phone microwaves at 900 MHz. To this end, four samples of hemoglobin in bidistilled water, sucrose, trehalose, and sodium chloride aqueous solutions were exposed for up to 4 hr to 900 MHz microwaves at an average H-field intensity of 42 mA/m. Quantitative spectral analyses highlighted significant increases in β-sheet contents in the Amide I region of hemoglobin samples in bidistilled water solution, but no appreciable change was observed in hemoglobin samples in sucrose, trehalose, and sodium chloride solutions. These results led us to conclude that mobile phone microwaves can denaturate hemoglobin in bidistilled water solution whereas sucrose, trehalose, and sodium chloride solutions produce a protective effect against microwaves, preserving the protein from unfolding.     

Thermoluminescence in gallium sulfide crystals: an unusual heating rate dependence

Trap centres in gallium sulfide single crystals have been investigated by thermoluminescence measurements in the temperature range of 10–230 K. A curve-fitting method was utilized to evaluate the activation energies (52, 200 and 304 meV) of the revealed three trap centres. The heating rate dependence and trap distribution of the peaks have been studied using experimental techniques based on various heating rates and various illumination temperatures, respectively. An anomalous heating rate dependence of the high-temperature peak was found by carrying out TL measurements with various heating rates between 0.2 and 1.0 K/s. This behaviour was explained on the basis of a semi-localized transition model. Whereas normal heating rate dependence was established for low-temperature peak, that is, the TL intensity of the glow curve decreases and the peak maximum temperature shifts to higher values with increasing the heating rate. Moreover, a quasi-continuous trap distribution with the increase of activation energies from 52 to 90 meV, from 200 to 268 meV and from 304 to 469 meV for the observed three different traps was established employing the various illumination temperatures method.     

Stabilisation of Ce-Cu-Fe amorphous alloys by addition of Al

The present work describes the formation of amorphous alloys in the (Al_1?xCe_x)₆₂Cu₂₅Fe₁₃ quaternary system (0 ≤ x ≤ 1). When the amount of Ce falls in the range 0.67 ≤ x ≤ 0.83, the alloys obtained exhibit a completely amorphous structure confirmed by powder X-ray diffraction. Otherwise, at compositions x = 0.5, 0.58, 0.92 and 1, a primary crystalline phase forms together with an amorphous matrix. The crystallisation temperature (T_x) decreases with increasing Ce content, varying from 593 K for x = 0.5–383 K for x = 1. Composition x = 0.75 is considered as the best glass former, exhibiting a large supercooled liquid region of 40 K width that precedes crystallisation. In order to form bulk amorphous alloys, ribbons with this later composition were consolidated into few millimetre thick discs using pulsed electric current sintering at different temperatures, yet preserving the amorphous structure. Meanwhile, increasing temperature above 483 K triggers crystallisation of a primary phase isostructural to AlCe₃. Further increase in the temperature up to 573 K yields a higher fraction of the crystalline phase. Testing mechanical properties, using nanoindentation, revealed that both elastic modulus (E) and hardness (H) depend on the Al content, ranging from E = 85.6 ± 3.7 GPa and H = 6.2 ± 0.7 GPa for x = 0.5 down to E = 39.8 ± 1.0 GPa and H = 3.1 ± 0.2 GPa for x = 0.92.     

Pressure-induced phase transition of ice in aqueous LiOH solution

I have examined the changes in in situ Raman spectra of ice in aqueous LiOH solution as a function of pressure at liquid nitrogen temperature (77 K). Here, I have shown the possibility that ice in aqueous LiOH solution transforms to a high-density amorphous like phase at around 0.9 GPa. I have mentioned that the results show differences strongly depending on the salts dissolved in the aqueous solutions.     

Shock compression of preheated molybdenum

A set of shock adiabats of molybdenum is constructed at various initial temperatures. It is shown that the dependence between shock velocity and particle velocity for Mo is nonlinear at high initial temperatures in a range of particle velocities 0.2<u<0.7 km/s. In a range of particle velocities 0.2 < u < 1.4 km/s the initial heating of molybdenum to 1000 K changes its shock adiabat approximately by 4%.     

Fixed-grid method for the modelling of unsteady partial oxidation of a spherical coal particle

The main goal of this work is the development of a fixed-grid method to model unsteady partial oxidation of a solid with implicit tracking of the interface. As a first step diffusive oxidation of a spherical coal particle is considered. The energy and species conservation equations formulated in spherical coordinates are discretised using the finite-volume approach. The boundary conditions for the temperature and species mass fractions at the solid–gas interface are modelled via special source terms activated in the interface cells. The numerical model was validated against analytic one- and two-film models for coal combustion in a dry-air atmosphere. Very good agreement was obtained. Based on the model developed a numerical study was carried out on the influence of water vapour on the partial oxidation of a spherical coal particle. Numerous numerical simulations were performed for particle diameters in the range 200×10^?6 m to 2×10^?2 m. The ambient temperature was varied in the range between 700 and 3000 K. The analysis of results showed that the addition of H₂O has an influence on the solution convergence due to the catalytic effect of water in the coal monoxide oxidation reaction making the whole system stiffer. However, at the same time, it was found that if the ambient mass fraction of water vapour is below 1×10^?3, its influence on combustion rates is minimal. The results of numerical simulations obtained for higher H₂O concentration (>1×10^?3) are discussed.     

Structural,magnetic, and physical properties of La(1–x)MnO3±δ nano-manganite

A detailed structural, magnetic and physics properties of La_1?xMnO_3±δ (LMO) nanomanganites were investigated to find out the role of cationic vacancies (La vacancy with Mn³⁺/Mn⁴⁺) in grain size modulation. Crystal structure and phase analysis of all samples were carried out by Rietveld refinement of high-resolution XRD and neutron diffraction data. We report here, the oxygen content in studied LMO compound decreases with increase in La vacancies in parent site and a parasitic Mn₃O₄ phase has been evolved in the range of 0.9 ≥ La/Mn ≥ 0.7. Para to ferro magnetic transition temperature (T_C) of all nanometric samples (La/Mn < 0.9) was found at high temperature side (≥260 K) whereas, the same for bulk one (La/Mn ≥ 0.9) was around 160 K. The enhancement of T_C (~70 K) with size reduction is attributed to broadening of bandwidth due to compaction of MnO₆ octahedra in system unit cell. In bulk sample, a secondary cluster/spin glassy phase is found below 50 K, whereas the glassy phase has been suppressed in nanoscale. Field-dependent magneto-resistance measurements are also carried out for all samples at different temperatures to get a profound insight of magneto-transport dynamics of the present system.     

Metamagnetic effects in epitaxial BaFe<Subscript>1.8</Subscript>Cr<Subscript>0.2</Subscript>As<Subscript>2</Subscript> thin films

Epitaxial BaFe_1.8Cr_0.2As₂ thin films with the tetragonal c-axis perpendicular to the thin film surface were grown on (LaAlO₃)_0.3(Sr₂AlTaO₆)_0.7 (LSAT) single crystalline substrates using pulsed laser deposition (PLD). Resistive measurements indicate the existence of two transitions at temperatures of about 80 K and 40 K. The transition at 80 K is attributed to the structural transition from the high temperature tetragonal phase to the low temperature orthorhombic phase accompanied with the magnetic transition from a paramagnetic to an antiferromagnetic state as known for doped bulk systems. Below T ≈ 40 K the magnetization curves measured perpendicularly to the orthorhombic c-axis in fields up to 9 Tesla show two inflexion points indicating metamagnetic transitions.     

Incommensurate Phases of the MgSiF6·6H2O Crystals: EPR and Group-Theoretical Studies

The group-theoretical study of the structural phase transition to incommensurate state of MgSiF₆·6H₂O crystals, revealed by the electron paramagnetic resonance (EPR) method, as well as analysis of the EPR results, are presented. The consideration of temperature dependences of Mn²⁺ admixture ion EPR spectrum symmetry and parameters leads to the conclusion that at T _i1 = 370 ± 0.3 K they undergo second-order structural phase transition to incommensurately modulated state, the order parameter of this transition may be the angle of [Mg(H₂O)₆]²⁺ octahedra rotation around crystal C ₃ axis. At temperature decreasing below T _i1 the gradual transformation of plane-wave modulation of lattice displacements into soliton mode occurs, which is interrupted by the first-order phase transition at T _i2 = 343 ± 0.3 K accompanied by abrupt decrease in modulation amplitude. At T _c = 298.5 ± 0.3 K the first-order improper ferroelastic phase transition into monoclinic phase occurs. The group-theoretical analysis of the phase transition at T _i1 in the investigated crystals, carried out for the first time, has shown that the existence of the incommensurately modulated phase is conditioned by the fundamental reasons (presence of Lifshitz invariant). The conclusions of this analysis on the nature of order parameter, the structural motifs of incommensurate phase and the possible character of temperature evolution of the structure are in agreement with the EPR investigation data.     

Evidence of magnetic broadening in Mössbauer spectra of superconducting FeTe 0.8 S 0.2

Magnetic properties of the FeTe_0.8S_0.2 superconductor were studied by Mössbauer spectroscopy. Low-velocity Mössbauer spectra that were recorded in the temperature range from 5.7 K up to 300 K show a paramagnetic doublet with a broadening at temperatures below 77 K. The broadening can be explained by the appearance of a distribution of hyperfine magnetic fields due to the magnetic ordering of a part of the sample. The magnetically ordered fraction starts to decrease at temperatures below 20 K indicating a possible competition with the onsetting superconductive state.     

X-band EPR study on benzo[c]cinnoline single crystals

The benzo[c]cinnoline compound has been crystallized in ethanol solution. These crystals have been irradiated with ⁶⁰Coγ-rays at room temperature. The crystals have been investigated by an X-band electron spin resonance (ESR) spectrometer two days after irradiation. Very strong ESR peaks have been observed at the temperatures between 130 and 430 K. However, a line broadening has been observed at 130 K. Also analyses found that EPR specra are temperature-dependent and show anisotropic behaviour.     

Broad-band dielectric response of 0.5Ba(Ti0.8Zr0.2)O3–0.5(Ba0.7Ca0.3)TiO3 piezoceramics: soft and central mode behaviour

ABSTRACT

Dielectric properties of 0.5Ba(Ti_0.8Zr_0.2)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ ceramics were probed in the frequency range from 10 Hz to 100 THz in a broad temperature range (10–900 K). Polar soft phonon observed in infrared spectra softens with cooling; however, below 500 K, its frequency becomes temperature independent. Simultaneously, a central mode activates in terahertz and microwave spectra; and it actually drives the ferroelectric phase transitions. Consequently, the phase transitions strongly resemble a crossover between the displacive and order–disorder type. The central mode vanishes below 200 K. The dielectric relaxation in the radiofrequency and microwave range anomalously broadens on cooling below T_C1, resulting in the nearly frequency independent dielectric loss below 200 K. This broadening comes from a broad frequency distribution of ferroelectric domain wall vibrations. Raman spectra reveal new phonons below 400 K, i.e. already 15 K above T_C1. Several weak modes are detected in the paraelectric phase up to 500 K in Raman spectra. Activation of these modes is ascribed to the presence of polar nanoclusters in the material.     

A Comparison of the Effects of Calcium Glutarate and Pimelate on the Formation of β Crystalline Form in Isotactic Poly(propylene)

The effect of calcium glutarate (Cagt) and calcium pimelate (Capt) on the formation of β crystalline form in isotactic poly(propylene) in the crystallization temperature range of 110–130°C has been investigated. The content of β phase crystals increase with the addition of calcium glutarate. K (relative content of β crystalline form in the iPP sample) attains its maximum value for iPP doped with 0.3 wt.% Cagt isothermally crystallized at 110°C (26.71%) or 120°C (30.27%), and for iPP doped with 0.2 wt.% Cagt isothermally crystallized at 130°C (31.97%), respectively. Compared with the K values of iPP doped with 0.1 wt.% Capt (78.33–94.76%), the β nucleation ability of Cagt is inferior to that of Capt. The spherulite size of iPP doped with Capt is smaller than that of iPP doped with Cagt. The difference in the β nucleation ability between Cagt and Capt is explained by the difference between their crystal structure parameters and those of β‐iPP.     

Effect of strontium substitution on the structural and magnetic properties of La1.8Sr0.2MMnO6 (M = Ni,Co)-layered manganites

Sr-substituted perovskites, La_1.8Sr_0.2MMnO₆ (M = Ni, Co), were synthesized using the solid-state reaction technique to present a systematic study on their morphological, structural and magnetic properties. The average grain size of the as-prepared La_1.8Sr_0.2NiMnO₆ samples are in the range of 0.2–0.7 µm and those for La_1.8Sr_0.2CoMnO₆ manganites are 0.1–2.8 μm, which is significantly less than that of unsubstituted La₂NiMnO₆ (LNMO) and La₂CoMnO₆ (LCMO) manganites. The XPS analysis enlightened about phase purity, binding energy and oxygen vacancy of La_1.8Sr_0.2MMnO₆ manganites. The Sr-substituted LNMO has revealed a sharp ferromagnetic to paramagnetic phase transition at 160 ± 2 K, which is about 120 K less than that of parent LNMO. The Sr-substituted LCMO exhibited such a transition at 220 ± 2 K, which is 8 K less than that of parent LCMO. The temperature-dependent magnetization measurements suggest that the effect of Sr on the transition temperature in LNMO is more significant than that of LCMO.     

Induced absorption in yttrium aluminium perovskite crystals irradiated by 12C and 235U ions

The present work is devoted to investigation of optical absorption in pure and neodymium-doped YAlO₃ (YAP) single crystals in the spectral range 0.2–1.1 μm induced by the influence of ¹²C ions irradiation with energy 4.50 MeV/u (MeV per nucleon) and a fluence 2 × 10⁹ cm^?2 or of ²³⁵U ion irradiation with energy 9.35 MeV/u and a fluence 5 × 10¹¹ cm^?2. The induced absorption in the case of ¹²C ions irradiation is caused by recharging of point growth defects and impurities under the radiation influence. After irradiation by ²³⁵U ions with fluence 5 × 10¹¹ cm^?2 the strong absorption rise is probably caused by contribution of the lattice destruction as a result of heavy ion bombardment.     

Thermal analysis, Raman spectroscopy and complex impedance analysis of Cu2+-doped KDP

Raman spectroscopy and differential thermal analysis (DTA) and thermogravimetric analysis have been carried out on Cu-doped KH₂PO₄ (Cu-KDP). X-ray diffraction powder data reveal that the structure of the KDP crystal does not change with the additive Cu²⁺ ion. DTA analysis and Raman study of Cu-KDP as a function of temperature reveal that this compound undergoes two phase transitions at about Ttr =453 and 473 K. The electrical conductivity measurements on polycrystalline pellet of Cu-KDP (5) are performed from room temperature (RT) up to 495 K. Only one phase transition is observed at 470 K. The activation energy in the migration is 0.42 eV in the temperature range from RT to 470 K. For temperature above 470 K, the activation energy of the superprotonic phase is 1.87 eV.     

Phase transition in Cu2+-doped RbH2 PO4 as observed by EPR

The electron paramagnetic resonance (EPR) spectra of Cu²⁺-doped RbH₂ PO₄ at elevated temperatures indicate a phase transition at 358 K. The EPR-silent state at this temperature is attributed to a so-called polymeric phase transition. After the transition when the temperature is lowered to 293 K, the EPR signal does not appear; therefore, the transition is irreversible. This result seems to be in agreement with the other observations. The EPR spectra for the sample indicate the presence of two sites for Cu²⁺, and the values of EPR parameters are in accord with the literature on Cu²⁺-doped single crystals. Any other phase transitions could not to be observed at low temperatures down to 113 K.     

Thermoluminescence and photoluminescence studies on gamma irradiated CsI: Pb2+ crystals

Pure and Pb²⁺-doped CsI crystals have been grown by the Bridgemann technique. Optical absorption, thermoluminescence (TL) and photoluminescence (PL) measurements have been performed. In undoped and Pb²⁺-doped cesium iodide crystals, F-centers and V-centers have been produced at 770 nm and 350 nm, respectively. In Pb²⁺-doped crystals, additional centers at 373 nm, 290 nm and 258 nm bands have been produced. In undoped samples, only two glow peaks at 343 K and 373 K have been produced, and in Pb²⁺-doped samples additional glow peaks at 383 K and 423 K have been produced. For all the samples, TL emission, PL and excitation measurements have been performed.     

Orientational and positional disorder of ions and its freezing in the CsNO2-TlNO2 system2

The heat capacities of Cs_0.695Tl_0.305NO₂ (Specimen I) and Cs_0.385Tl_0.615NO₂ (Specimen II) have been measured between 14 and 350 K. Specimen I underwent a phase transition at (197.7 ± 0.1) K, with ΔS = (19.2 ± 1.5) JK^?mol^?, and specimen II at (214.5 ± 0.2) K, with ΔS = (5.4 ± 1.0) JK^?1mol^?1, respectively. Above the phase transition, an exothermic temperature drift due to phase separation was observed. Annealing of the sample at 203 K for 300 hr brought about complete phase separation. The solid solution system annealed at 203 K gave two heat capacity peaks at (203.3 ± 0.1) K, with ΔS = (13.8 ± 0.8) JK^?1 mol^?1, and (242.4 ± 0.2) K, with ΔS = (10.6 ± 1.3) JK^?1 for Specimen I, and at (203.0 ± 0.1) K with ΔS = (6.7 ± 0.5) JK^?1 mol^?1, and (257.5 ± 0.2) K with ΔS = (17.9 ± 1.7) JK^?1 mol^?1 for Specimen II. The phase diagram of the CsNO₂-TlNO₂ binary system was constructed on the basis of DTA, heat capacity and dielectric measurements. In the metastable phase, the existence of a residual entropy due to the freezing of a random distribution of Cs⁺₁ and Tl⁺ cations in addition to the orientational disorder of the NO₂^?1 ion was confirmed by a comparison of entropies of the stable and the metastable phases.