Cintica de cristalizacin por Anlisis Trmico

Anlisis Trmico

Todos aquellos mtodos de medida basados en el cambio, con la temperatura (o en funcin del tiempo a temperatura constante), de una propiedad fsica o mecnica de un material, mientras se le somete a un programa de temperaturas controlado. Conjunto de tcnicas mediante las cuales el cambio de una propiedad fsica o qumica de un material es medida en funcin del tiempo controlando la temperatura

Tcnicas de anlisis
Tcnica Termogravimetra (TG) Propiedad medida Masa Determine: Kinetic parameters (of the process) Method: Coats and Redfem Madhysudanan et al. Tang et al. Wajun et al.

Anlisis Trmico Diferencial (DTA) Calorimetra diferencial de barrido (DSC)

Temperatura Entalpa

Dominant crystallization mechanism (in glass) The kind of nucleation (homogeneous or heterogeneous), and the growth geometry (one, two or three dimensional growth)

Avrami Kissinger Ozawa Takhor Augis and Bernet Gao and Wang Approximation Free

Termooptometra Anlisis Electrotrmico Otros

Propiedad ptica Conductividad Elctrica ---

Termogravimetra (TG, DTG)

Anlisis Termogravimtrico Registro, de manera continua, de la masa de una muestra (en atmsfera controlada), o bien en funcin de la temperatura, o bien en funcin del tiempo a T = cte. Anlisis Termogravimtrico diferencial Medida del gradiente en la variacin de masa con T t (T = cte). Termograma Representacin de la masa o porcentaje de cambio en funcin de T t.

Termogravimetra (TG, DTG)

Termograma Tpico: a) Curva primaria (TGA); b) curva derivada (DTGA) Sistema de gas de purga: Gases de purga (N2, Ar, O2: depende del anlisis)

Termogravimetra (TG, DTG)

Aplicaciones: Causas del cambio de peso:
Reaccin de descomposicin Reaccin de oxidacin Vaporizacin Sublimacin Desorcin

Aplicaciones del anlisis termogravimtrico:

Control de calidad. Efecto de aditivos Estabilidad trmica en atmsfera inerte Oxidacin en aire o atmsfera rica en oxgeno Degradacin trmica de polmeros Estudios de cintica de degradacin y anlisis de los productos Identificacin de materiales

Termogravimetra (TG, DTG)

Termograma de descomposicin del CaC2O4 H2O a 5 C/min Anlisis cuantitativo de una mezcla de iones Ca, Sr, Ba, precipitados como oxalatos monohidratados

Termogravimetra (TGA, DTGA)

Year Title / Author / Source Abstract A kinetic and microscopic investigation of the thermal dehydration of dl lithium potassium tartrate monohydrate is reported and the reaction mechanism discussed. This work forms part of a more comprehensive study concerned with the influence of reactant structure on the reactivity and the mechanism of chemical change. The other hydrated reactants with which this salt will be compared contain the d and meso forms of the tartrate anion and crystallize with different structures. dl lithium potassium tartrate monohydrate lost the single molecule of water of crystallization in one predominantly deceleratory process that was studied between 350-460 K. Reaction was accompanied by melting to yield a residual glassy anhydrous product that was amorphous to X-ray diffraction. An initial, relatively rapid release of water (6%) was followed by a deceleratory process that led to a zero-order reaction (that, in crystals, extended between 18% and 80%) before completion by an approximately first-order stage. Dehydrations of crushed powder reactant samples differed from single crystals in being relatively more rapid (an eight-fold increase); the deceleratory process was THE KINETICS AND MECHANISM OF WATER EVOLUTION FROM long and the zero-order process shorter (50-85%). The activation energy for dehydrations of crystal MOLTEN DL LITHIUM POTASSIUM TARTRATE MONOHYDRATE and of powder was 330 $\pm $ 30 kJ mol$^{-1}$. This pattern of kinetic behaviour was not in Sreelekha D. Bhattamisra, Genevieve M. Laverty, Nikolai A. Baranov, Vladimir 1992 accordance with expectation for a homogeneous reaction, the rate was not directly related to reactant B. Okhotnikov and Andrew K. Galwey concentration terms. Alternative analyses of the obedience of data to rate expressions applicable to Published 15 December 1992 doi:10.1098/rsta.1992.0112Phil. Trans. R. Soc. solid state reactions were equally unsuccessful. Our mechanistic interpretation of the rate data, Lond. A 15 December 1992 vol. 341 no. 1662 479-498 therefore, considered a priori the factors expected to participate in the control of water evolution from the melt. It is concluded that the vitreous or molten phase is not homogeneous and, therefore, behaviour is different from reactions in an isotropic fluid or in a solid. Two models are proposed to explain our observations. In the two phase equilibrium mechanism it is assumed that the reactant particles are composed of two phases, zones of hydrate are embedded in dehydrated material that retains a constant but small proportion of water. (These phases participate in an equilibrium analogous to that of liquid/vapour.) The surface boundary layer model envisages the initial development of a peripheral barrier zone through which the constant rate of water diffusion is rate controlling. This class of reaction, proceeding in a fluid but the absence of added solvent, has received relatively little attention. The present discussion is intended to identify the characteristic behaviour and draw attention to the necessity to consider such mechanisms in discussions of reactions of solids where there is the possibility of melt participation.

THERMAL STABILITY OF LIXCOO2, LIXNIO2 AND -MNO2 AND CONSEQUENCES FOR THE SAFETY OF LI-ION CELLS 1994 J DAHN, E FULLER, M OBROVAC, U VONSACKEN Journal: Solid State Ionics , vol. 69, no. 3-4, pp. 265-270, 1994 DOI: 10.1016/0167-2738(94)90415-4

LiCoO2, LiNiO2 and LiMn2O4 are all stable in air to high temperature. By contrast, LixCoO2, LixNiO2 and LixMn2O4 (x<1) are metastable and liberate oxygen when they are heated in air or in inert gas. The temperature at which oxygen evolution occurs depends on x and on the material. Using thermal gravimetric analysis and mass spectrometry, we have studied the thermal decomposition of these materials in inert gas. We find that the nickel materials are least stable, the manganese compounds are most stable, and that the cobalt compounds show intermediate behaviour. These results have important consequences for the safety of Li-ion cells, and suggest that cells using LiMn2O4 as the cathode should be safer than those using LiNiO2or LiCoO2.

Termogravimetra (TGA, DTGA)

Year Title / Author / Source Title: THERMAL BEHAVIOR OF LI1-YNIO2 AND THE DECOMPOSITION MECHANISM Author(s): Arai, H; Okada, S; Sakurai, Y; et al. 1998 Source: SOLID STATE IONICS Volume: 109 Issue: 3-4 Pages: 295-302 DOI: 10.1016/S0167-2738(98)00075-7 Published: JUN 1998 Times Cited: 129 (from Web of Science) Abstract We report the thermal behavior of Li1-yNiO2 up to 300 degrees C which we investigated using thermogravimetry (TG) and differential scanning calorimetry (DSC). The decomposition mechanism was studied using the X-ray diffraction data obtained for the thermally decomposed products. At about 200 degrees C Li1-yNiO2 turned into Li(1-y/(2-y))Ni1/(2-y)O which has a rock-salt structure. This was accompanied by oxygen evolution. A significant exothermic process was observed for compounds with y greater than or equal to 0.7 and this resulted in products with disordered rock-salt structures. Using these results, we propose a mechanism in which the exothermic behavior is caused by random cation mixing. Stearic acid in tetramethylammonium hydroxide is used to co-precipitate lithium and manganese in stoichiometric proportions from aqueous solutions of manganese and lithium salts. Calcination of the precipitate in air produces uniformly sized, fine particles of spinel LiMn2O4 as the end product. The effect of heat treatment on the spinel formation reaction is followed by thermogravimetry and powder X-ray diffraction measurements. The electrochemical performance of the spinel is evaluated in test cells using the spinel as the positive electrode material, and lithium metal as the negative electrode. The chargedischarge data indicate that the spinel has a specific capacity of about 119 mAh g1. The material shows good rate capability in the range of 0.5 3 mA cm2.

Tittle: PREPARATION OF SPINEL LITHIUM MANGANESE OXIDE BY AQUEOUS CO-PRECIPITATION 2000 Author(s): Naghash, AR; Lee, JY Source: JOURNAL OF POWER SOURCES Volume: 85 Issue: 2 Pages: 284293 DOI: 10.1016/S0378-7753(99)00347-X Published: FEB 2000

THERMAL BEHAVIOR AND THE DECOMPOSITION MECHANISM OF Thermal behavior of Li1xNiO2 ( or C2/m) up to 400 C was studied using thermogravimetry (TG), ELECTROCHEMICALLY DELITHIATED LI1XNIO2 differential scanning calorimetry (DSC), and high-temperature X-ray diffraction measurements and its Kyung-Keun Leea, , , Won-Sub Yoona, Kwang-Bum Kima, Ki-Young Leeb, decomposition mechanism was proposed. Delithiated Li1xNiO2 was thermally decomposed to Seung-Tae Hong LiNi2O4spinel (Fd3m) at the temperature range of 180 250C. For x0.5, Li1xNiO2 was Division of Materials Science and Engineering, Yonsei University, 134 Shinchon- decomposed to LiNiO2 and LiNi2O4 and the fraction of the spinel in the decomposed product increased 2001 dong, Seodaemun-gu, Seoul, South Korea almost linearly with x. For 0.5<x0.8, Li1xNiO2 was converted into LiNi2O4 spinel and this reaction Battery Research Institute, LG Chemical Ltd., Research Park, Taejon 305-380, was accompanied by oxygen evolution. Li1xNiO2 of all compositions turned into a rock -salt phase South Korea (Fm3m) with oxygen liberation at temperatures above 270C. The temperature for the decomposition Journal of Power Sources of Li1xNiO2 to a spinel or a rock-salt phase decreased with x in Li1xNiO2. The thermal behavior of Volumes 9798, July 2001, Pages 321325 Li1xNiO2 could be interpreted as an overlap of the exothermic rearrangement of cations (nickel and Proceedings of the 10th International Meeting on Lithium Batteries lithium ions) to form a spinel or a rock-salt phase and the endothermic oxygen evolution reaction. The kinetic behavior of LiNH2 decomposition by ammonia release was quantified using thermogravimetric analysis (TGA). While not itself a hydrogen storage material, LiNH2 is a primary component of the hydrided state in Li NH storage materials based on Li3N or Li2NH. Its decomposition by ammonia release, and consequent degradation of the hydrogen storage capacity, has important implications for the durability of Li NH storage systems. LiNH2 from two commercial lots and one batch prepared at GM R&D were ball milled for 10 or 20 min to obtain fine LiNH2 powders. Kinetic parameters were extracted from sets of TGA weight loss curves taken at different heating rates. The activation energy for the decomposition reaction was determined to be about 128 kJ/mole, virtually independent of the source and purity of the LiNH2, its stoichiometry, ball milling time, and TGA sample size. The reaction rate was found to depend on the sample size as a consequence of the very low NH3LiNH2 equilibrium vapor pressure at temperatures below 300 C. Larger samples produce a local concentration of NH3 high enough to inhibit further reaction. Direct isothermal measurements of the initial reaction rates at temperatures between 200 and 300 C agree well with the values calculated from the heating rate-derived kinetic parameters. The durability of Li NH for hydrogen storage was estimated from the measured kinetic parameters by calculating the time required to decompose 20% of the initial LiNH2, as a function of the operating temperature. The predicted lifetime falls below 105 min for operating temperatures in excess of 160 C.

DECOMPOSITION KINETICS OF LITHIUM AMIDE FOR HYDROGEN STORAGE MATERIALS F.E. Pinkerton , Materials and Processes Laboratory, MC 480-106-224, General Motors 2005 Research and Development Center, 30500 Mound Road, Warren, MI 480909055, USA Journal of Alloys and Compounds Volume 400, Issues 12, 1 September 2005, Pages 7682

Termogravimetra (TGA, DTGA)

Year Title / Author / Source Abstract A lithium-ion battery cathode material, Li(Ni1/3Co1/3Mn1/3)O-2, with excellent electrochemical properties was prepared via two-step isothermal sintering, using eutectic lithium salts (0.38LiOH center dot H2O-0.62LiNO(3)) mixed with Co, Ni, or Mn hydroxides. Based on analysis using X-ray diffraction (XRD), scanning electron microscopy (SEM), a thermogravimetric-differential scanning calorimetric (TGTitle: THE SYNTHESIS OF LI(NI1/3CO1/3MN1/3)O-2 USING EUTECTIC DSC) analyzer, and Fourier-transform Infrared (FT-IR), this synthetic process consists of procedures MIXED LITHIUM SALT LINO3-LIOH including lithium salt melting, permeation, reaction, crystalline transformation, and crystallization. Due Author(s): Chang, Zhaorong; Chen, Zhongjun; Wu, Feng; et al. 2009 to the lower melting point of the eutectic molten salts compared with that of the single lithium salt, a Source: ELECTROCHIMICA ACTA Volume: 54 Issue: 26 Pages: 6529-6535 relatively mild synthetic condition (low temperature) is needed, and the product can be highly DOI: 10.1016/j.electacta.2009.06.013 Published: NOV 1 2009 crystallized with low cation mixing, which facilitates maintenance of the precursor morphology. The Times Cited: 9 (from Web of Science) electrochemical properties of the product were investigated by constant current discharge-charge and cyclic voltammetry. The results show that the initial discharge capacity is 160 mhA g(-1), with excellent cycling stability even after 50 cycles. We conclude that this novel eutectic molten salt method is a promising and practical approach for synthesizing cathode materials for lithium-ion batteries. Title: NANO-CRYSTALLINE LIMNPO4 PREPARED BY A NEW PHOSPHATE-FORMATE PRECURSOR METHOD Author(s): Koleva, V.; Stoyanova, R.; Zhecheva, E. 2010 Source: MATERIALS CHEMISTRY AND PHYSICS Volume: 121 Issue: 1-2 Pages: 370-377 DOI: 10.1016/j.matchemphys.2010.01.043 Published: MAY 15 2010 The preparation of homogeneous phosphate-formate precursors by freeze-drying of solutions containing lithium, Mn(II), phosphate and formate ions ensures production of stoichiometric, well crystallized, defectless and nano-sized LiMnPO4 powders at temperatures above 400 degrees C. A systematic study of the influence of the synthesis conditions on the structure and morphology of LiMnPO4 is performed. It is established that the concentration of the solutions subjected to freeze-drying and the annealing temperature strongly affect the structure, particle dimensions and morphology of LiMnPO4. LiMnPO4 with low extent of Li-to-Mn disorder (below 1%) are formed between 500 and 600 degrees C. Uniform and regular particles with close sizes distribution in the 60-120 nin range are prepared from diluted freeze-dried solutions and at relatively low annealing temperature. In a previous work, the synthesis and structural-microstructural characterization of different nanocrystalline lithium metasilicate (Li2SiO3) samples were performed. Then, in this work, initially, a textural analysis was performed over the same samples. Li2SiO3 samples prepared with a non-ionic surfactant (TRITON X-114) presented the best textural properties. Therefore, this sample was selected to evaluate its water vapor (H2O) and carbon dioxide (CO2) sorption properties. Sorption experiments were performed at low temperatures (3080 C) in presence of water vapor using N2 or CO2 as carrier gases. Results clearly evidenced that CO2sorption on these materials is highly improved by H2O vapor, and of course, textural properties enhanced the H2OCO2 sorption efficiency, in comparison with the solid-state reference sample. To reduce the reaction time, electrical energy consumption, and cost, LiFePO4/C/graphene has been synthesized by a rapid, one-pot, microwave-assisted hydrothermal method within 15 min at a temperature of 200 C, followed by sintering at 600 C for 2 h under a H2/Ar (5 : 95, v/v) atmosphere. The microstructure and morphology of the LiFePO4/C/graphene products were characterized by means of X-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy. The carbon coated LiFePO4/C nanoparticles, around 200 nm in size, are thoroughly wrapped by crumpled micrometer-size graphene sheets. In this kind of structure, the bridging graphene nanosheets can form an effective conducting network and provide interconnected open pores that favor electrolyte absorption and reduce the diffusion path of the lithium ions. The cyclic voltammograms, charge/discharge profiles, and AC impedance measurements indicated that the kinetics of the LiFePO4/C/graphene was better than that of LiFePO4/C. The LiFePO4/C/graphene composite exhibited a discharge capacity of 165 mA h g1 at 0.1 C and 88 mA h g1 at 10 C, respectively. Therefore, the LiFePO4/C/graphene composite is a promising candidate for the development of high-performance, cost-effective lithium batteries for the hybrid vehicle and electric vehicle markets.

SURFACTANT-ASSISTED HYDROTHERMAL CRYSTALLIZATION OF NANOSTRUCTURED LITHIUM METASILICATE (LI2SIO3) HOLLOW SPHERES: IITEXTURAL ANALYSIS AND CO2H2O SORPTION EVALUATION 2011 Jos Ortiz-Landerosb, Carlos Gmez-Yezb, Heriberto Pfeiffera, , Instituto de Investigaciones en Materiales, Universidad Nacional Autnoma de Mxico. Journal of Solid State Chemistry, Volume 184, Issue 8, August 2011, Pages 22572262

Title: GRAPHENE WRAPPED LIFEPO4/C COMPOSITES AS CATHODE MATERIALS FOR LI-ION BATTERIES WITH ENHANCED RATE CAPABILITY 2012 Author(s): Shi, Yi; Chou, Shu-Lei; Wang, Jia-Zhao; et al. Source: JOURNAL OF MATERIALS CHEMISTRY Volume: 22 Issue: 32 Pages: 16465-16470 DOI: 10.1039/c2jm32649c Published: 2012

Anlisis Trmico Diferencial (DTA)

Mide la diferencia de temperatura entre la muestra y un material inerte de referencia mientras son sometidos al mismo programa de temperaturas.

Anlisis Trmico Diferencial (DTA)

Aplicaciones ATD
Determinacin de cambios de fase:
Fusin Cristalizacin Sublimacin Cristal A Cristal B

Reacciones qumicas Desorcin

Anlisis Trmico Diferencial (DTA)

Termograma tpico para un material que sufre una transicin. El ATD es un anlisis cualitativo. No se conoce la variacin de la conductividad trmica de la muestra durante la transicin.

Anlisis Trmico Diferencial (DTA)

Year Title / Author / Source Abstract The LiPO(3) glass crytallization have been investigated according to isothermal and non-isothermal approaches by using various techniques such as thermal analysis, helium pycnometry, scanning electronic microcospy and X-ray powder diffraction. Different experimental procedures have been developed to determine the crystallized volume fraction. The different results are a good agreement and leadto a better Title: MACROSCOPIC AND MICRO-STRUCTURAL ASPECTS OF THE comprehension at a "macroscopic" scale of this first order transition. In addition, from "ex-situ" X-ray powder LITHIUM METAPHOSPHATE GLASS CRYSTALLIZATION diffraction experiments, the understanding of the diffraction line intensities as a function of the annealing Author(s): Rocherulle, Jean; Chenu, Sebastien; Benard-Rocherulle, Patricia 2010 time, at a fixed temperature, has revealed a new metastable crystalline form of LiPO(3) (named alpha) stable Source: JOURNAL OF NON-CRYSTALLINE SOLIDS Volume: 356 Issue: 52-54 over a short time range. Attempts for indexing led to a possible monoclinic system close to that reported in Special Issue: SI Pages: 2969-2976 DOI: 10.1016/j.jnoncrysol.2010.03.049 literature for the thermodynamical stable variety (named beta). The micro-structure of annealed samples has Published: DEC 2010 been discussed in terms of crystallite sizes and lattice micro-distorsions at a nanometer scale. This study based on diffraction line broadening analysis was carried out with the integral breadth method. Finally, from "in-situ" X-ray powder diffraction experiments, evidence was shown that the LiPO(3) glass matrix crystallizes first in a metastable LiPO(3)-alpha form which, in turn, transforms into the beta form. (DTA) (XRD). Single crystals of Li6Y(BO3)(3) have been grown by both the Bridgman and Czochralski methods. It was found that the complex nature of the melt solidifications affects the efficiency of the crystallization process and the composition of the grown crystals. High supercooling favored melt dissociation and the formation of thermodynamically unstable phases Li3Y(BO3)(2) and Li3Y2(BO3)(3). Applying X-ray phase analysis for airquenched ceramic samples it was shown that the room temperature stability region of the off-stoichiometric Li6Y(BO3)(3) phase is extended towards the B2O3 rich, Y2O3 deficient compositions. Mixed phosphate-formate precursors, LiFePO4Hx(HCOO)xyH2O (x 1, 1 < y < 1.3 and x < y), were prepared by freeze-drying of solutions containing Li+, Fe2+, PO43 and HCOO in a ratio of 1:1:1:2. Fe(HCOO)22H2O was used as an iron source. The concentration of the freeze -dried solutions allows affecting the morphology of phosphate-formate precursors. Powder XRD, IR spectroscopy, DTA, BET measurements, SEM and XPS analyses were used for the characterization of the precursors and LiFePO4. IR spectroscopic study of the precursors shows that the deprotonated phosphate and formate ions are coordinated around the metal ions. The thermal heating of the lithium-iron phosphate-formate precursors at 350 C for a short period yields stoichiometric defectless LiFePO4 having a high-specific surface area of about 35 m2/g, a mesoporous structure and containing up to 1.5 mass% carbon. By variation of the solutions concentration subjected to freeze-drying, the morphology of LiFePO4 and the carbon content are changed. The morphology of target LiFePO4 comprises micrometric aggregates, which are composed of nanometric particles with close particle size distribution in the range of 60 140 nm. The nanometric particles are interconnected in a way to form mesoporous network. This method is suitable for the preparation of LiFePO4 as cathode material for lithium-ion batteries since it allows affecting both the particle dimensions and carbon content.

Title: SYNTHESIS AND CRYSTALLIZATION OF LITHIUM-YTTRIUM ORTHOBORATE LI6Y(BO3)(3) PHASE 2012 Author(s): Peter, A.; Polgar, K.; Toth, M. Source: JOURNAL OF CRYSTAL GROWTH Volume: 346 Issue: 1 Pages: 6974 DOI: 10.1016/j.jcrysgro.2012.02.034 Published: MAY 1 2012

Title: A NEW PHOSPHATE-FORMATE PRECURSOR METHOD FOR THE PREPARATION OF CARBON COATED NANO-CRYSTALLINE LIFEPO4 Author(s): Koleva, V.; Zhecheva, E.; Stoyanova, R. 2009 Source: JOURNAL OF ALLOYS AND COMPOUNDS Volume: 476 Issue: 1-2 Pages: 950-957 DOI: 10.1016/j.jallcom.2008.09.144 Published: MAY 12 2009

Anlisis Trmico Diferencial (DTA)

Year Title / Author / Source Abstract Thermal kinetic parameters of Cr2O3 doped lithium-aluminum-silicate (LAS) photonic glass are calculated using differential thermal analysis (DTA). The dependence of kinetic parameters together with the glass forming ability of the investigated glass on the Cr2O3 doping level showed an anomalous behavior around 0.4 g. Correlation between the obtained thermal properties and the materials electronegativity and band gap is given. An energy band diagram is proposed explaining the density of energy states of Cr3+ and its transformation to Cr6+. The non-bridging oxygen bonds generated by Cr2O3 produce a deep donor level responsible for the red shift of the absorption edge. The local order structure is studied for the LAS glass network using the radial distribution function of XRD. The atomic pairs of Si-O, Li-O and Si-Si are clearly revealed in both short range (SRO) and medium range (MRO) orders, respectively. The addition of Cr2O3 into the glass network has changed appreciably both the atomic pair distances and the coordination numbers in the MRO due to the multivalent nature of Cr ions. The observed decrease in the fourth shell coordination number, N-4, reflects the atomic size decrease in the given glass network which means an increase in glass compactness. Title: Glass transition kinetics and radial distribution function to investigate the role of Cr2O3 on the structure of Li2O-Al2O3-SiO2 photonic glass 2012 Author(s): Abdel-Wahab, F. A.; Abou Shama, Ali; Abdel-Baki, Manal; et al. Source: JOURNAL OF ALLOYS AND COMPOUNDS Volume: 513 Pages: 172179 DOI: 10.1016/j.jallcom.2011.10.014 Published: FEB 5 2012

Title: Preparation of nanocrystalline LiMnPO4 via a simple and novel method and its isothermal kinetics of crystallization 2011 Author(s): Liu, Chen; Wu, Xuehang; Wu, Wenwei; et al. Source: JOURNAL OF MATERIALS SCIENCE Volume: 46 Issue: 8 Pages: 2474-2478 DOI: 10.1007/s10853-010-5094-z Published: APR 2011

The precursor of nanocrystalline LiMnPO4 was obtained by solid-state reaction at low heat using Li2SO4 center dot H2O, MnSO4 center dot H2O, and Na3PO4 center dot 12H(2)O as raw materials, maintaining the mixture at 333 K for 4 h, and then washing the mixture with deionized water to remove soluble inorganic salts, and at last drying at 373 K. The nanocrystalline LiMnPO4 was obtained by calcining the precursor. The precursor and its calcined products were characterized using TG/DTA, FT-IR, and XRD. The data showed that the precursor dried at 373 K for 3 h was a compound with amorphous structure. However, when the precursor was calcined at 973 K for 2 h, highly crystallization LiMnPO4 with orthorhombic structure [space group Pmnb (62)] was obtained with a crystallite size of 38 nm. The mechanism and kinetics of the crystallization process of LiMnPO4 were studied using XRD technique, the results showed that activation energy of the crystallization process of LiMnPO4 was 103.30 kJ/mol, and the mechanism of crystallization process of LiMnPO4 is the random nucleation and growth of nuclei reaction.

The effects of K2O content on sintering and crystallization of glass powder compacts in the Li2O-K2O-Al2O3SiO2 system were investigated. Glasses featuring SiO2/Li2O molar ratios of 2.69-3.13, far beyond the lithium disilicate (LD-Li2Si2O5) stoichiometry, were produced by conventional melt-quenching technique. The Title: The role of K2O on sintering and crystallization of glass powder sintering and crystallization behaviour of glass powders was explored using hot stage microscopy (HSM), compacts in the Li2O-K2O-Al2O3-SiO2 system scanning electron microscopy (SEM), differential thermal (DTA) and X-ray diffraction (XRD) analyses. Author(s): Fernandes, Hugo R.; Tulyaganov, Dilshat U.; Pascual, Maria J.; et al. 2012 Increasing K2O content at the expense of SiO2 was shown to lower the temperature of maximum shrinkage, Source: JOURNAL OF THE EUROPEAN CERAMIC SOCIETY Volume: 32 Issue: eventually resulting in early densification of the glass-powder compacts. Lithium metasilicate was the main 10 Pages: 2283-2292 DOI: 10.1016/j.jeurceramsoc.2012.02.003 crystalline phase formed upon heat treating the glass powders with higher amounts of K2O. In contrast, Published: AUG 2012 lithium disilicate predominantly crystallized from the compositions with lower K2O contents resulting in strong glass ceramics with high chemical and electrical resistance. The total content of K2O should be kept below 4.63 mol% for obtaining LD-based glass ceramics.

Anlisis Trmico Diferencial (DTA)

Year Title / Author / Source Abstract Two glasses based on lithium disilicate (LS2), with and without fluorapatite (FA), were synthesised in the Li2O-SiO2-CaO-P2O5-CaF2 system with P2O5: CaO : CaF2 ratios corresponding to fluorapatite. Glassceramics have then been prepared by thermal treatment. The mechanism and kinetics of crystallization as functions of grain size and rate of heating were investigated using thermal analysis methods. The smaller Title: Mechanism and kinetics of glass-ceramics formation in the LiO2particles crystallize preferentially by surface crystallization, which is replaced by volume crystallization at SiO2-CaO-P2O5-CaF2 system larger particle sizes. Inclusion of FA in the LS2 favours crystallization through the surface mechanism. The 2009 Author(s): Palou, Martin; Kuzielova, Eva; Vitkovic, Martin; et al. onset limit for volume crystallization replacing the surface mechanism is at about 0.3 mm for pure LS2 glass Source: CENTRAL EUROPEAN JOURNAL OF CHEMISTRY Volume: 7 Issue: 2 and 0.9 mm for glass containing FA. The calculated activation energies of the glasses (299 +/- 1 kJ mol(-1) Pages: 228-233 DOI: 10.2478/s11532-009-0002-6 Published: JUN 2009 for pure LS2 glass and 288 +/- 7 kJ mol(-1) for glass containing FA according to Kissinger, or 313 +/- 1 kJ mol(-1) for pure LS2 glass and 303 +/- 8 kJ mol(-1) for glass containing FA according to Ozawa) indicate that the tendency of the glasses to crystallize is supported by the FA presence. Bioactivity of all samples has been proved in vitro by the formation of new layers of apatite-like phases after soaking in SBF. In this study, the high-temperature phase transformation of a multicomponent lithium disilicate glass was investigated by in situ and real-time synchrotron X-ray diffraction in the SiO2Li2OP2O5Al2O3ZrO2 glass system. Quantitative phase analysis via the Rietveld method was performed on the high-resolution data aiming to reveal the crystallization sequence, crystallization kinetics, and the role of P2O5 on nucleation. It is found that the nucleation of lithium metasilicate (LS) and lithium disilicate (LS2) in this complex glass is triggered by the steep compositional gradients associated with the disordered lithium phosphate (LP) precursors in the glass matrix. The LS2 crystals grow at the expense of the LS, cristobalite, and quartz phases in the glass during the isothermal crystallization process at 770 C. The nucleation kinetics is temperature dependent, and the induction period of nucleation is longer at a lower temperature. Single crystals of Li6Y(BO3)(3) have been grown by both the Bridgman and Czochralski methods. It was found that the complex nature of the melt solidifications affects the efficiency of the crystallization process and the composition of the grown crystals. High supercooling favored melt dissociation and the formation of thermodynamically unstable phases Li3Y(BO3)(2) and Li3Y2(BO3)(3). Applying X-ray phase analysis for airquenched ceramic samples it was shown that the room temperature stability region of the off-stoichiometric Li6Y(BO3)(3) phase is extended towards the B2O3 rich, Y2O3 deficient compositions.

Title: Nucleation and Crystallization Kinetics of a Multicomponent Lithium Disilicate Glass by in Situ and Real-Time Synchrotron X-ray Diffraction 2013 Saifang Huang , Peng Cao *, Ying Li , Zhaohui Huang , and Wei Gao Department of Chemical and Materials Engineering, Cryst. Growth Des., 2013, 13 (9), pp 40314038 DOI: 10.1021/cg400835n. Publication Date (Web): July 31, 2013

Title: Synthesis and crystallization of lithium-yttrium orthoborate Li6Y(BO3)(3) phase 2012 Author(s): Peter, A.; Polgar, K.; Toth, M. Source: JOURNAL OF CRYSTAL GROWTH Volume: 346 Issue: 1 Pages: 6974 DOI: 10.1016/j.jcrysgro.2012.02.034 Published: MAY 1 2012

The single phase -LiZnPO4H2O was directly synthesized via solid-state reaction at room temperature using LiH2PO4H2O, ZnSO47H2O, and Na2CO3 as raw materials. XRD analysis showed that LiZnPO4H2O was a compound with orthorhombic structure. The thermal process of -LiZnPO4H2O experienced two steps, which involved the dehydration of one crystal water molecule at first, and then the crystallization of LiZnPO4. The DTA curve had the one endothermic peak and one exothermic peak, Title: Preparation of LiZnPO4 H2O via a novel modified method and its respectively, corresponding to dehydration of -LiZnPO4H2O and crystallization of LiZnPO4. Based on the non-isothermal kinetics and thermodynamics of thermal iterative iso-conversional procedure, the average values of the activation energies associated with the 2012 decomposition thermal dehydration of -LiZnPO4H2O, was determined to be 86.59 kJ mol1. Dehydration of the crystal Author: Chen, Zhipeng, Qian Chai, Sen Liao, Yu He, Wenwei Wu, and Bin Li. water molecule of -LiZnPO4H2O is single-step reaction mechanism. A method of multiple rate isoJournal of thermal analysis and calorimetry 108, no. 3 (2012): 1235-1242. temperature was used to define the most probable mechanism g() of the dehydration step. The dehydration step is contracting cylinder model (g() = 1(1)1/2) and is controlled by phase boundary reaction mechanism. The pre-exponential factor A was obtained on the basis of E a and g(). Besides, the thermodynamic parameters (S , H , and G ) of the dehydration reaction of -LiZnPO4H2O were determined.

Calorimetra diferencial de Barrido (DSC)

Mide el flujo de calor que tiene lugar en la muestra y en la referencia, de forma independiente.

Se basa en el principio de Balance nulo de Temperatura

DSC es una tcnica cuantitativa. El rea de debajo de la curva del termograma puede relacionarse con la entalpa de la transicin.

Calorimetra diferencial de Barrido (DSC)

Factores que afectan las curvas de DTA y DSC
De tipo instrumental
Velocidad de calentamiento Geometra de las clulas Tipo de sensor de temperatura Tipo de registro del termograma

De la muestra
Tamao de la muestra Grado de divisin de la muestra

Empaquetamiento
Control atmsfera ambiente Tratamiento previo

Material de referencia

Calorimetra diferencial de Barrido (DSC)

Aplicaciones comunes de DSC
Calor especfico y propiedades en las que vara el calor especfico como la temperatura de transicin vtrea o la transicin de Curie. Transiciones de fase Polimorfismos

Determinacin de puntos de fusin

Determinacin de parte amorfa y cristalina Cinticas de reaccin Tiempo e induccin a la oxidacin

Descomposicin

Calorimetra diferencial de Barrido (DSC)

Transiciones Trmicas: Las transiciones trmicas no ocurren a temperaturas fijas. Eventos que pueden observarse en una curva DSC

Calorimetra diferencial de Barrido (DSC)

Fusin
Temperatura de fusin = mximo del pico de fusin Entalpa de fusin = rea del pico Factores que afectan a la fusin:
Tamao de muestra Velocidad de calentamiento Sobrecalentamiento de la muestra Reorganizacin de molculas durante el sobrecalentamiento Tamao de cristales y perfeccin Distribucin de pesos moleculares Annealing (recocido)

Calorimetra diferencial de Barrido (DSC)

Cristalizacin La forma de cristalizacin afecta al grado de cristalinidad y a su naturaleza y, por tanto, a las distintas propiedades (del polmero).

Calorimetra diferencial de Barrido (DSC)

Year Title / Author / Source Title: KINETIC-ANALYSIS OF THE NONISOTHERMAL DEHYDRATION OF LITHIUM-SULFATE MONOHYDRATE 1991 Author(s): KOGA, N; TANAKA, H Source: THERMOCHIMICA ACTA Volume: 185 Issue: 1 Pages: 135-140 DOI: 10.1016/0040-6031(91)80124-2 Published: AUG 12 1991 Abstract Kinetic data of the title dehydration obtained from simultaneous TG-DSC measurements were compared between the single crystals and crushed crystal material. The kinetics were interpreted in relation to the reaction geometry observed by polarizing microscopy. The kinetic compensation effect established for the Arrhenius parameters evaluated by the Ozawa method was discussed in terms of the temperature interval analyzed.

Title: Crystallization kinetics of a lithium zinc silicate glass studied by DTA and DSC 2004 Author(s): Donald, IW Source: JOURNAL OF NON-CRYSTALLINE SOLIDS Volume: 345 Pages: 120126 DOI: 10.1016/j.jnoncrysol.2004.08.007 Published: OCT 15 2004

The crystallization kinetics of a lithium zinc silicate glass have been determined using isothermal and nonisothermal DSC and non-isothermal DTA. Values for the kinetic parameters for as-quenched and nucleated samples are reported and discussed. Particular reference is given to the similarities and differences noted between isothermally and non-isothermally derived data.

Layered lithium nickel-rich oxides, Li[Ni1-xMx]O2 (M=metal), have attracted significant interest as the cathode material for rechargeable lithium batteries owing to their high capacity, excellent rate capability and low cost. However, their low thermal-abuse tolerance and poor cycle life, especially at elevated temperature, prohibit their use in practical batteries. Here, we report on a concentration-gradient cathode material for HIGH-ENERGY CATHODE MATERIAL FOR LONG-LIFE AND SAFE LITHIUM rechargeable lithium batteries based on a layered lithium nickel cobalt manganese oxide. In this material, BATTERIES each particle has a central bulk that is rich in Ni and a Mn-rich outer layer with decreasing Ni concentration Yang-Kook Sun, Seung-Taek Myung, Byung-Chun Park, Jai Prakash, Ilias and increasing Mn and Co concentrations as the surface is approached. The former provides high capacity, 2009 Belharouak, Khalil Amine whereas the latter improves the thermal stability. A half cell using our concentration-gradient cathode Journal: Nature Materials - NAT MATER , vol. 8, no. 4, pp. 320-324, 2009 material achieved a high capacity of 209mAhg-1 and retained 96% of this capacity after 50 charge-discharge DOI: 10.1038/nmat2418 cycles under an aggressive test profile (55oC between 3.0 and 4.4V). Our concentration-gradient material also showed superior performance in thermal-abuse tests compared with the bulk composition Li[Ni0.8Co0.1Mn0.1]O2 used as reference. These results suggest that our cathode material could enable production of batteries that meet the demanding performance and safety requirements of plug-in hybrid electric vehicles.

The ionic conductivity of mol% 50Li(2)O-50P(2)O(5) melt quenched glass shows an anomalous increase after its glass transition temperature (T-g) around 590 K. On further increasing the temperature gradually, the conductivity decreases owing to the devitrification of Li2O-P2O5 glass. The evolution of devitrified crystallites was evidenced by XRD patterns. To understand the devitrification process, isothermal and non-isothermal Title: Crystallization kinetics and phase transformation in superionic DSC studies have been carried out on mol% 50Li(2)O-50P(2)O(5) glass. T-g as well as T-c values are found lithium metaphosphate (Li2O-P2O5) glass system to increase monotonically with increasing heating rates. Variation of T-g as a function of heating rates has Author(s): Money, Benson K.; Hariharan, K. been investigated to evaluate the lower limiting temperature of T-g and the activation energy for structural 2009 Source: JOURNAL OF PHYSICS-CONDENSED MATTER Volume: 21 Issue: 11 relaxation. Results of the DSC studies indicate (i) single-stage bulk crystallization of the glass, with DSC Article Number: 115102 DOI: 10.1088/0953-8984/21/11/115102 Published: traces exhibiting a single amorphous double right arrow crystalline (T-c) transition, (ii) an order parameter MAR 18 2009 (Avrami constant) of 2.8 +/- 0.1, suggesting internal (bulk) crystallization of the glass, (iii) an activation energy for crystallization equal to 121.7 kJ mol (1) and (iv) the activation energy for structural relaxation, Eg, to be 558.8 kJ mol(-1). The crystallization mechanism is closely associated with the JMA model and the experimental dataset have been fitted to a non-isothermal Avrami expression and the obtained parameters confirm the experimental results.

Calorimetra diferencial de Barrido (DSC)

Year 2011 Title / Author / Source SYNTHESIS OF NANO-LIMNPO4 FROM MNPO4H2O PREPARED BY MECHANOCHEMISTRY Li Wang, Wenting Sun, Xiangming He*, Jianjun Li, Changyin Jiang Beijing Key Lab of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, PR China *E-mail: hexm@tsinghua.edu.cn; Received: 8 April 2011 / Accepted: 15 May 2011 / Published: 1 June 2011 Int. J. Electrochem. Sci., 6 (2011) 2022 - 2030 Abstract Synthesis of nano-LiMnPO4 from MnPO4H2O prepared by mechanochemistry is attempted. SEM, TEM, XRD and TG/DSC are performed to characterize the products. The results show that the primary particles are loosely aggregated with an average particle size of 40-50 nm. The morphology and particle size distribution of nano-LiMnPO4 preserves those of MnPO4H2O. This paves a promising way of high efficiency, easy accessibility and speediness to prepare nano-LiMnPO4.

2011

In the present work, tellurite 20Li(2)O-80TeO(2) glasses were prepared with identical nominal composition under different glassforming histories to produce a stressed and stress-free samples. X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC) techniques were used to study the effects of the glass-forming histories on the thermal and structural properties of these glasses. The Title: Effects of glass-forming histories on the crystallization kinetic gamma-TeO2 (metastable), alpha-TeO2 and alpha-Li2Te2O5 phases were identified during the controlled devitrification in these of the 20Li(2)O-80TeO(2) glass glasses. The mestastable character of the gamma-TeO2 phase was clearly observed in the glass under stress but this effect is not so Author(s): Araujo, E. B.; Idalgo, E. clear in the stress-free glass. The gamma-TeO2 and alpha-TeO2 phases crystallizes during the initial stages of crystallization in both Source: OPTICAL MATERIALS Volume: 33 Issue: 12 Special Issue: SI studied glasses while the alpha-Li2Te2O5 phase crystallize in the final stages of the crystallization. The activation energies and Pages: 1847-1852 DOI: 10.1016/j.optmat.2011.02.044 Published: OCT Avrami exponent were calculated for both studied glasses with different particle size leading to E-3 > E-2 > E-1 for stressed glass and 2011 E-3 > E-2 approximate to E-1 for stress-free glass, where E-1, E-2 and E-3 were associated to the gamma-TeO2, alpha-TeO2 and alpha-Li2Te2O5 phases, respectively. The observed distinct (n) over bar (1) < <(n)over bar>(2) < <(n)over bar>(3) in both glasses is an indicative that nucleation and growth takes place by more than one mechanism in the early stages of the crystallization. According to a hypothesis by Russel and coworkers, the absence of Ostwald ripening during isothermal crystallization of lithium aluminosilicate (LAS) and other glass ceramics indicates the existence of a kinetic hindrance of atomic reorganization in the interstitial spaces between the crystals. Methods of Thermal Analysis (Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA)) which are sensitive to the local atomic rearrangements in the interstitial spaces (including viscous flow) are applied to find support for the idea of kinetic hindrance and the formation of a core shell structure acting as diffusion barrier. Both the DSC-measured calorimetric glass transition and the DMA-measured viscoelastic properties indicate an increase in the time constants of atomic rearrangements and diffusion by at least two orders of magnitude during ceramization. This fits to the above idea. We collect and critically analyze extensive literature data, including our own, on three important kinetic processes viscous flow, crystal nucleation, and growthin lithium disilicate (Li2O2SiO2) over a wide temperature range, from above T m to 0.98T g where T g 727 K is the calorimetric glass transition temperature and T m = 1307 K, which is the melting point. We found that crysta l growth mediated by screw dislocations is the most likely growth mechanism in this system. We then calculated the diffusion coefficients controlling crystal growth,DUeff, and completed the analyses by looking at the ionic diffusion coefficients of Li+1, O2, and Si4+estimated from experiments and molecular dynamic simulations. These values were then employed to estimate the effective volume diffusion coefficients, DVeff, resulting from their combination within a hypothetical Li2Si2O5 molecule. The similarity of the temperature dependencies of 1/, where is shear viscosity, and DVeff corroborates the validity of the Stokes-Einstein/Eyring equation (SEE) at high temperatures around T m . Using the equality of DVeff and Deff, we estimated the jump distance 2.70 from the SEE equation and showed that the values of DUeff have the same temperature dependence but exceed Deff by about eightfold. The difference between Deff and DUeff indicates that the former determines the process of mass transport in the bulk whereas the latter relates to the mobility of the structural units on the crystal/liquid interface. We then employed the values of (T) reduced by eightfold to calculate the growth rates U(T). The resultant U(T) curve is consistent with experimental data until the temperature decreases to a decoupling temperature TUd1.11.2Tg, when Deff begins decrease with decreasing temperature faster than DUeff. A similar decoupling occurs between Deff and Deff (estimated from nucleation time-lags) but at a lower temperatureTdTg. For T > T g the values of Deff exceed Deff only by twofold. The different behaviors of Deff(T) and DUeff(T) are likely caused by differences in the mechanisms of critical nuclei formation. Therefore, we have shown that at low undercoolings, viscosity data can be employed for quantitative analyses of crystal growth rates, but in the deeply supercooled liquid state, mass transport for crystal nucleation and growth are not controlled by viscosity. The origin of decoupling is assigned to spatially dynamic heterogeneity in glass-forming melts.

2011

Thermal analyses to assess diffusion kinetics in the nano-sized interspaces between the growing crystals of a glass ceramics Author(s): Fotheringham, Ulrich; Wurth, Roman; Ruessel, Christian Source: THERMOCHIMICA ACTA Volume: 522 Issue: 1-2 Special Issue: SI Pages: 144-150 DOI: 10.1016/j.tca.2011.03.023 Published: AUG 10 2011

2011

Title: Dynamic processes in a silicate liquid from above melting to below the glass transition Author(s): Ferreira Nascimento, Marcio Luis; Fokin, Vladimir Mihailovich; Zanotto, Edgar Dutra; et al. Source: JOURNAL OF CHEMICAL PHYSICS Volume: 135 Issue: 19 Article Number: 194703 DOI: 10.1063/1.3656696 Published: NOV 21 2011

Calorimetra diferencial de Barrido (DSC)

Year Title / Author / Source 2011 Abstract Differential scanning calorimetry (DSC) measurements were used to study crystallization in the Se(70)Te(30) glass under non-isothermal conditions. The crystallization kinetics was described in terms of the nucleation-growth Johnson-Mehl-Avrami and autocatalytic Sestak-Berggren models. An extensive discussion of all aspects of a full-scale kinetic study for a complex crystallization process was performed. Number of suggestions regarding the experimental part (sample and glass preparation, temperature programs, data Title: Interpretation of crystallization kinetics results provided by DSC acquisition, etc.) was introduced to maximize precision and reproducibility of the experimental data. Complexity of the Author(s): Svoboda, Roman; Malek, Jiri crystallization process was in this particularly described case represented by very closely overlapping consecutive competing Source: THERMOCHIMICA ACTA Volume: 526 Issue: 1-2 Pages: 237-251 DOI: surface and bulk nucleation-growth mechanisms. Mutual interactions of both mechanisms as well as all other observed 10.1016/j.tca.2011.10.005 Published: NOV 10 2011 effects were explained in terms of thermal gradients, surface crystallization centres arising from the sample preparation treatments and changing amount of volume nuclei originating from the combination of pre-nucleation period and the very glass preparation phase. Advanced error analysis was performed for each step of the kinetic study. Objective of the presented study was to demonstrate extensity of information the differential scanning calorimetry is able to provide and, furthermore, to show how a thorough kinetic analysis may lead to reliable, valid and detailed description of complex processes as well as to interpretations of any observable trend occurring in experimental data. Crystallization kinetic studies of Li+ ion conducting mol% 60Li(2)O-40P(2)O(5) glass indicate a 2-dimensional crystal growth mechanism as compared to the 3-dimensional growth mechanism for LiPO3 glass (mol% 50Li(2)O-50P(2)O(5)). Title: Lithium rich phosphate glass: Crystallization kinetics, structural and Spectroscopic studies reveal that the structures of these two glass compositions differ considerably resulting in different conduction characteristics mechanisms for crystal growth. Isothermal ionic conductivity studies further support 2-dimensional crystallization in mol% Author(s): Dabas, Prashant; Hariharan, K. 60Li(2)O-40P(2)O(5) glass. Above the glass transition temperature the ionic conductivity deviates from the usual Arrhenian Source: JOURNAL OF NON-CRYSTALLINE SOLIDS Volume: 358 Issue: 2 Pages: temperature dependence due to the additional effect of the movement of the phosphate polymeric chains in the glass 252-260 DOI: 10.1016/j.jnoncrysol.2011.09.024 Published: JAN 15 2012 network. The ionic conductivity of the glass ceramic corresponding to the mol% 60Li(2)O-40P(2)O(5) glass behaves in an Arrhenian fashion with an activation energy of 1.21 eV, much higher than that of 0.77 eV for the glass. Further, it is established using canonical scaling that the mechanism for ionic conduction is temperature independent. Title: Effect of Simultaneous Nucleation and Crystal Growth on DSC Crystallization Peaks of Glasses Author(s): Rodrigues, Alisson M.; Costa, Alberth M. C.; Cabral, Aluisio A. Source: JOURNAL OF THE AMERICAN CERAMIC SOCIETY Volume: 95 Issue: 9 Special Issue: SI Pages: 2885-2890 DOI: 10.1111/j.1551-2916.2012.05333.x Published: SEP 2012 In this study, the change of the height of the crystallization peak, (delta T)p, and the reciprocal of the crystallization peak temperature, 1/Tp, were investigated as a function of nucleation heat-treatment time for two silicate glasses: (2BaO center dot TiO2 center dot 2SiO2B2TS2) and lithium disilicate (Li2O center dot 2SiO2LS2). Then, monolithic pieces were heattreated in a differential scanning calorimetry furnace. The results demonstrated that these glasses behave similarly with respect to peak crystallization temperature, i.e., 1/Tp decreases with the heating rate for nucleation (phi n). However, the results with B2TS2 samples demonstrated that (delta T)p increases with rising heating rates for nucleation (shorter nucleation heat treatment times), fn, whereas (delta T)p was found to decrease with phi n in the LS2 specimens. This unexpected behavior is attributed to the extensive overlapping of the I(T) and U(T) curves shown by fresnoite glass.

2012

2012

2012

2013

The crystallization kinetics of a commercial lithium-aluminum silicate (LAS) glass were characterized by differential scanning calorimetry (DSC) under non-isothermal conditions, by in-situ X-ray diffraction, and by three point beam bending Title: Study of the crystallization kinetics of LAS glass by differential viscosimeter (BBV). Non-isothermal DSC experiments were conducted at different heating rates. Results show that the scanning calorimetry, X-ray diffraction, and beam bending viscometry crystal growth is controlled by a thermally activated process of the Arrhenius type. The activation energies obtained from Author(s): Ovono, D. Ovono; Berre, S.; Pradeau, P.; et al. isoconversional analysis are close to that extracted using the Johnson-Mehl-Avrami equation. While X-ray diffraction volume Source: THERMOCHIMICA ACTA Volume: 527 Pages: 158-164 DOI: fraction data confirm the DSC analysis, it also shows that the crystallite size changes only at the end of the heat treatment 10.1016/j.tca.2011.10.021 Published: JAN 10 2012 protocol, during a hold at temperatures as high as 1000 degrees C. In this latter case, the crystal growth follows the Ostwald ripening mechanism. Finally, the viscosity measured in the crystallization region by BBV provides the activation energy for viscous flow, and it is slightly higher than the values obtained by DSC The initial stages of the crystallization kinetics of lithium metasilicate (LS) in glasses of the Li2O center dot SiO2-CaO center Title: NONSTOICHIOMETRIC CRYSTALLIZATION OF LITHIUM dot SiO2 join - which has a simple eutectic - was investigated at high undercoolings, somewhat above the glass transition METASILICATE-CALCIUM METASILICATE GLASSES. PART 1-CRYSTAL temperatures. Calcium metasilicate crystals precipitate and grow only in the advanced stages of crystallization. The variation NUCLEATION AND GROWTH RATES of glass composition from the eutectic (26.5 mol% Li2O) towards lithium metasilicate (50 mol% Li2O) results in a sharp Author(s): Fokin, Vladimir M.; Reis, Raphael M. C. V.; Abyzov, Alexander S.; et al. increase of the internal nucleation rate of LS crystals, whereas the growth rates increase only weakly. This strong increase of Source: JOURNAL OF NON-CRYSTALLINE SOLIDS Volume: 362 Pages: 56-64 the nucleation rate is primarily caused by a decrease of the thermodynamic barrier for nucleation - due to an increase of the DOI: 10.1016/j.jnoncrysol.2012.11.020 Published: FEB 15 2013 thermodynamic driving force for crystallization and a decrease of the nucleus/liquid interfacial energy - as the glass composition approaches the crystal composition.

Calorimetra diferencial de Barrido (DSC)

Year Title / Author / Source Abstract Non-isothermal kinetics of lithium ion phosphate synthesis via carbothermal reduction method with raw materials Li2CO3, FePO4 center dot 2H(2)O and C6H12O6 center dot 2H(2)O is studied by thermogravimetry-differential scanning calorimetry (TG-DSC) technology. The results indicate the synthesis process can be divided into two stages: dehydration and LiFePO4 formation. The apparent activation energy and natural logarithm frequency factor (In A-value) for dehydration reaction is respectively 83.4 +/- 4.7 kJ mol(-1) and 22.1 +/- 1.5 s(-1), and that for LiFePO4 formation reaction is in turn 184.2 +/- 10.4 kJ mol(-1) and 28.3 +/- 1.9 s(-1). Additionally, the mechanism for dehydration and LiFePO4 formation stages is Avrami's A(1.5) and A(4), respectively. Furthermore, the dehydration process is diffusion controlled, and the crystallization of LiFePO4 formation is controlled by nuclei being formed randomly and growing in three-dimensions, and the kinetic equations for each stage are shown as follows: Dehydration stage : [-ln(1 - a)](2/3) = 3.96 x 10(9) exp (-8.34 x 10(4)/RT) t; LiFePO4 formation stage : [-ln(1 - a)](1/4) = 1.95 x 10(12) exp (-1.84 x 10(5)/RT) t; where a is the fractional conversion, T the calcination temperature (K), t the calcination time (s), R the gas constant (8.314J mol(-1) K-1). 66.7Li(2)O-33.3P(2)O(5) mol% glass prepared by twin-roller rapid quenching has been chosen to investigate the nucleation and crystallization kinetics using differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and high temperature X-ray diffraction (XRD) as the experimental tools. Such studies assume importance in designing materials for solid state ionic devices. The glass exhibits a nucleation rate of 3.1 x 10(18) M-3 s(-1) at a typical temperature of 583 K and crystal growth rate of 2.1 x 10(-2) nm s(-1) at 643 K. Non-isothermal DSC studies reveal that the glass undergoes bulk crystallization with an activation energy of 114 kJ mol(-1). The crystallized phase is identified as lithium pyrophosphate (Li4P2O7). Crystallization kinetic studies reveal that Li4P2O7 crystallizes three dimensionally with increasing number of nuclei. Interestingly, lithium metaphosphate (LiPO3) appears as a secondary phase in the glass matrix, however, the final glass ceramic product obtained after prolonged heat treatment of the glass is single phase Li4P2O7. The secondary phase also grows three dimensionally with an activation energy of 365 kJ mol(-1), but with constant number of nuclei in contrast to Li4P2O7. The high nucleation and growth rate with lower activation energy for crystallization of Li4P2O7 underscore that the glass is extremely prone to nucleation and crystallization. Modification in the crystallization kinetics behaviour of the polymer poly(ethylene oxide) due to the incorporation of an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate; BMIMPF6) has been studied. The PEO + x wt% BMIMPF6 polymer films were prepared by a solution casting technique. Crystallization kinetic parameters, such as relative crystallinity (X-t), crystallization half time (t(1/2)), crystallization rate constant (K), crystallization rate (G) and Avrami exponents (n), have been determined by both isothermal and non-isothermal techniques using DSC. The experimental results based on both non-isothermal and isothermal methods show that the melt crystallization of PEO slows down significantly with the incorporation of BMIMPF6 in the membranes. The growth of crystallized spherulites has also been monitored by polarizing optical microscope (POM), which confirms that the growth rate of crystallized spherulites slows down on the addition of BMIMPF6 in the polymeric membranes. It is well known that the variation in the crystallized fraction, x(t), can be determined directly by optical microscopy (OM) or indirectly by differential scanning calorimetry (DSC) under isothermal conditions. In this work, the kinetic crystallization parameters E (activation energy) and n (Avrami index) of a quasi-stoichiometric lithium disilicate glass (Li2O2SiO2LS2) were studied. First, bulk samples were heat treated in a vertical tube furnace between 500C and 530C for different periods of time, and were carefully prepared. Furthermore, the same samples were then heated in a calorimeter from room temperature to 850C at 10C/min. The following E andn values were obtained: (i) OM: 462.2 1.23 kJ/mol and 4; and (ii) DSC: 187.5 0.45 kJ/mol and 2.4. The results indicated that the activation energy was reduced due to the formation of new crystals and growing of the preexisting crystals during the DSC experiments, and that the predominant crystallization mechanism in the samples changed according to the chosen thermal history. 2013 Title: Non-isothermal kinetics study on synthesis of LiFePO4 via carbothermal reduction method Author(s): He, Lihua; Liu, Xuheng; Zhao, Zhongwei Source: THERMOCHIMICA ACTA Volume: 566 Pages: 298-304 DOI: 10.1016/j.tca.2013.06.014 Published: AUG 20 2013

2013

Title: Nucleation and crystallization kinetics of rapidly quenched lithium pyrophosphate glass Author(s): Dabas, Prashant; Hariharan, K. Source: SOLID STATE IONICS Volume: 243 Pages: 42-49 DOI: 10.1016/j.ssi.2013.04.017 Published: JUL 15 2013 Times Cited: 0 (from Web of Science) Title: Nucleation and crystallization kinetics of rapidly quenched lithium pyrophosphate glass Author(s): Dabas, Prashant; Hariharan, K. Source: SOLID STATE IONICS Volume: 243 Pages: 42-49 DOI: 10.1016/j.ssi.2013.04.017 Published: JUL 15 2013

2013

Title: Effect of ionic liquid on the crystallization kinetics behaviour of polymer poly(ethylene oxide) Author(s): Chaurasia, S. K.; Singh, R. K.; Chandra, S. Source: CRYSTENGCOMM Volume: 15 Issue: 30 Pages: 6022-6034 DOI: 10.1039/c3ce40576a Published: 2013

2013

Determining the Kinetic Parameters for Isothermal Crystallization in a Lithium Disilicate (Ls2) Glass by OM and DSC Leyliane S. Everton1, Aluisio A. Cabral1,2,* Article first published online: 28 NOV 2013 DOI: 10.1111/jace.12638 2013 The American Ceramic Society. Journal of the American Ceramic Society

Cintica de Cristalizacin
La nucleacin y cristalizacin pueden definirse como los procesos trmicos y cinticos en virtud de los cuales, a partir de una fase estructuralmente desordenada, se forma una fase slida estable con una ordenacin geomtrica regular. Este proceso de ordenacin, es consecuencia de una disminucin de la energa libre del sistema cuando un fundido es enfriado por debajo de su temperatura de liquidus (TL = Temperatura de fusin).

Metodologa
Preparacin y/u obtencin por otros medios

Preparada por Reaccin qumica

Precursor

Seleccin y caracterizacin de las muestras

Muestra a partir de Fusin por arco

Molienda y homogenizacin

Fusin

Recocido Muestras

Muestras

Anlisis Qumico y caracterizacin

Cintica de Cristalizacin
Proceso Petrrgico. Cristalizacin primaria de un vdrio: obtencin del vidrio y tratamientos trmicos posteriores se incluyen dentro de un nico proceso de enfriamiento Proceso Vitrocermico. Cristalizacin secundaria de un vdrio: aplicacin de ciclos trmicos posteriores y diferentes al de la obtencin del vidrio.

Cintica de Cristalizacin
Enfriamientos bruscos (quenching) a las temperaturas elegidas (picos exotrmicos ATD. Enfriamientos lentos, va petrrgica, en el intervalo Temperatura de Fusin (TL) 800C.