TG-DTA properties of new nonlinear optical materials: K(2)Ln(NO3)(5)center dot 2H(2)O (Ln = La, Ce, Pr, Nd, Sm)

Single crystals of K(2)Ln(NO3)(5). 2H(2)O (KLnN) (Ln = La, Ce, Pr, Nd, Sm) were grown from aqueous solution. The thermogravimetric analysis and differential thermal analysis curves of KLnN demonstrate that the processes of dehydration, melting, irreversible phase transformation and decomposition of NO3- take place in sequence in the heating processes (except KCN). There are three stages in the decomposition of NO3- in KLnN (Ln = La, Nd, Sm) while two in KLnN (Ln = Ce, Pr). K(2)Ln(NO3)(5) is formed at about 225 degrees C by the reaction of KNO3 and Ln(NO3)(3). nH(2)O (Ln = La, Ce, Pr, Nd). (C) 2000 Elsevier Science Ltd. All rights reserved.

Crystal growth and TG-DTA properties of K(2)Ln(NO3)(5).2H(2)O (Ln = La, Ce, Pr, Nd, Sm)

Single crystals of KLnN(Ln=La, Ce, Pr, Nd, Sm) can be grown in water solution with pH approximate to 1 similar to 2 at about 40 degrees C. Crystals of KLnN (Ln=La, Ce, Pr, Nd) are orthorhombic with space group Fdd2. KPrN crystal was grwon and its crystal structure was determined for the first time. The KPrN crystal parameters obtained by the direct method are as follows: a=21.411(3) Angstrom, b=11.2210(10)Angstrom, c=12.208(2) Angstrom, Z=6, R=0.0240. The TG-DTA curves of KLnN(Ln=La,Ce, Pr, Nd, Sm) demonstrate that the processes of dehydration, melt, irreversible phase transition and decomposition of NO3- take place in sequence with the temperature increasing(except KCN). There are three steps in the decomposition of NO3- in KLnN(Ln=La, Nd, Sm) while two steps in KLnN (Ln=Ce, Pr). K(2)Ln(NO3)(5). 2H(2)O are formed at about 225 degrees C by the reaction of the starting materials of KNO3 and Ln(NO3)(3). nH(2)O.

高压差热分析方法（HP-DTA）研究钙蒙脱石-氯化钙-水体系中的脱水作用

在开放（P_水DTA）在压力达800巴的范围内对钙蒙脱石-氯化钙-水体系的脱水作用共进行了三百多次实验研究。实验所需的钙蒙脱石是用1N浓度的CaCl_2溶液对初始样品怀俄明富钠蒙脱石（SWy-1）进行离子交换后产生。通过本次论文的工作深刻地认识到蒙脱石族矿物的脱水作用是受水的逸度所控制，这是一新的认识，而且相当重要，因为清楚了蒙脱石矿物脱水作用的控制因数对于我们了解许多浅部地球化学过程具有重要的意义。在CaSWy-H_2O和CaSWy体系中，蒙脱石的脱水作用是分两级进行的，其脱水温度随压力的增加而向高温区移动，尤其是在<100巴的范围内，其递增速率相当快。在相同压力下，钙蒙脱石的两级脱水温度分别高于水的蒸发温度50℃和110℃，在压力大于水的临界点时，钙蒙脱石的脱水温度增加的趋势相当缓慢。两级脱水反应的吸热谷形态随着压力的增加而发生变化。这些特点被理解为钙蒙脱石层间水的密度大于自由水的密度，其层间水具有两种不同的水组态，其组态形式随着压力的增加而发生变化，但组态之间的能量间距却不随压力的变化而变化。应用实验数据，在论文中给出了一种新的在一大气压下计算钙蒙脱石层间吸附力焓值大小的办法，共值为：ΔH_(iw),湿~I = 7.74KJ/mol, ΔH_(iw), 干~I = 8.13KJ/mol; ΔH_(iw),湿~I = 20.74KJ/mol, H_(iw), 干~I = 21.28KJ/mol。这些值也表明了使用干体系或者湿体系来研究钙蒙脱石的脱水作用基本上没有什么区别。同时也指出在常压DTA实验技术中常论及的影响DTA峰（谷）值大小和峰（谷）的形态的样品因数实质上是由于这些因数引起了围绕在样品颗粒之间的水逸度的变化所致，这是一种对样品影响因数的新认识。把CaSWy同已知重量比为0.9、1.8、5、10、20和30wt.%的氯化钙均匀混合，在实验过程中分别产生浓度为0.5M、1.8M、2.82M、5.63M、11.26和16.9M的CaCl_2-H_2O流体。同CaSWy体系相比，在CaSWy-CaCl_2体系中，由于盐的加入，使体系中水的逸度降低，在相同压力下降低了钙蒙脱石的脱水温度，其降低的量同盐的浓度成正比。在0-11.26M浓度之间钙蒙脱石的脱水温度降低速度较快，但当浓度大于或等于11.26.时盐水流体的浓度不再能降低钙蒙脱石的脱水温度，而且在较高压力下其效应更加明显。在体系中CaCl_2-H_2O流体的浓度为5.63M、11.26M和16.9M时，在一大气下钙蒙脱石脱水温度可低于水的蒸发温度。因此，在具有一定盐浓度的岩层中存在蒙脱石脱水作用会对岩层中孔隙水的水压产生缓冲作用，出现超压现象。利用实验数据，计算出了各种浓度的盐体系脱水作用的van't Hoff线方程：0%: 1np= 15.008 - 7.237 * (1000/T) (0.5M) 0.9%: 1np=14.634-6.781* (1000/T) (1M) 1.8%: 1np = 15.347-7.130 * (1000/T) (2.82M) 5%: 1np = 14.717 - 6.381 * (1000/T) (5.63M) 10%: 1np = 14.270-5.806 * (1000/T) (11.26M) 20%: 1np = 14.580 - 5.831 * (1000/T) (16.9M) 30%: 1np = 14.412 - 5.519 * (1000/T)根据这些等式求出了在不同压力、温度下各种浓度的CaCl_2-H_2O流体的水逸度系数（￡）。由于至目前为止在文献中还没有这方面的实验研究报道，因而无法评价这一新方法所获得的数据的准确性。利用求得的￡值，在本篇论文中建立起了不同浓度的CaCl_2-H_2O流体影响钙蒙脱石脱水温度的热力学模式：TD' = [T_1*T_D*(ΔH_(tw) + ΔH_(sv)~盐）/[T_1*(ΔG + ΔH_(dn)~水）-T_D~* (ΔH_(av)~水-ΔH_(sv)~盐）在0-1M浓度范围内，可以认为ΔH_(dh)~水≈H_(dh)~盐，等式变为：TD' = (TD*ΔH_(dh))/(ΔG + ΔH_(dh)）根据这个模式，能推导出在实验浓度范围内，钙蒙脱石在盐水体系中的脱水温度。通过本次论文的实验研究知道在一般沉积盆地的埋芷条件下，钙蒙脱石矿物不会发生简单的脱水作用。在缺乏K~+和低盐度的环境中，含水相蒙脱石可稳定地存在在一定深度的地壳中因而不可忽略蒙脱石在海洋化学和俯冲带水来源中的作用。在选择处理簇射性废料的回填料（backfill）时，如其它条件相同，则应优先选择钙蒙脱石，而不是蛭石。在石油采矿和勘探工程中，因压力释放所造成的蒙脱石的脱水作用可能是使钻井变大和塌方的可能性原因之一。

Comparing whole-link travel time models used in DTA

In a model commonly used in dynamic traffic assignment the link travel time for a vehicle entering a link at time t is taken as a function of the number of vehicles on the link at time t. In an alternative recently introduced model, the travel time for a vehicle entering a link at time t is taken as a function of an estimate of the flow in the immediate neighbourhood of the vehicle, averaged over the time the vehicle is traversing the link. Here we compare the solutions obtained from these two models when applied to various inflow profiles. We also divide the link into segments, apply each model sequentially to the segments and again compare the results. As the number of segments is increased, the discretisation refined to the continuous limit, the solutions from the two models converge to the same solution, which is the solution of the Lighthill, Whitham, Richards (LWR) model for traffic flow. We illustrate the results for different travel time functions and patterns of inflows to the link. In the numerical examples the solutions from the second of the two models are closer to the limit solutions. We also show that the models converge even when the link segments are not homogeneous, and introduce a correction scheme in the second model to compensate for an approximation error, hence improving the approximation to the LWR model.

La nutrition des personnes âgées en stades précoces de la démence du type Alzheimer (DTA) : exploration du rôle du proche aidant et des répercussions sur sa santé

Contexte : La détérioration de l’état nutritionnel liée à la perte d’autonomie qui accompagne l’évolution de la démence du type Alzheimer (DTA) peut être limitée par un proche aidant efficace. À long terme, le rôle soignant du proche aidant peut affecter sa propre santé physique et psychologique. Objectifs : (1) décrire les caractéristiques sociodémographiques des patients et de leurs proches aidants; (2) examiner l’évolution de la maladie et des variables à l’étude au cours de la période de suivi; (3) explorer la relation possible entre le fardeau perçu du proche aidant, l’état nutritionnel des patients et la stabilité du poids corporel du proche aidant. Hypothèses : L’absence du fardeau chez l’aidant est associée à un meilleur état nutritionnel chez le patient; la détérioration de la fonction cognitive chez le patient s’accompagne d’une augmentation du fardeau perçu par l’aidant; la dégradation du fardeau chez l’aidant conduit à sa perte de poids. Méthode : Les données analysées proviennent de l’étude « Nutrition-mémoire » menée entre 2003 et 2006 dans les trois cliniques de cognition situées dans des hôpitaux universitaires à Montréal. Quarante-deux patients avec une DTA probable vivant dans la communauté et leurs aidants ont été suivis en dyades pendant une période de dix-huit mois. Les analyses ont porté sur les données colligées du recrutement à douze mois plus tard en raison du nombre restreint des patients interviewés à la dernière mesure. La relation entre le fardeau de l’aidant et les variables caractérisant l’état nutritionnel chez les patients a été évaluée à l’aide des analyses de corrélations, du test khi-carré ou du test de Fisher. L’état cognitif des patients était évalué à l’aide du score au Mini-Mental State Examination, le fardeau de l’aidant était estimé par le score au « Zarit Burden Interview », l’état nutritionnel des patients était défini par la suffisance en énergie et en protéines, le score à l’outil de dépistage nutritionnel des aînés, le poids et l’indice de masse corporelle des patients. Résultats : Le fardeau perçu des aidants était associé à la suffisance en énergie chez les patients. Le nombre de patients ayant des apports insuffisants en énergie était plus important chez les dyades où les aidants percevaient un fardeau plus élevé. Toutefois, aucune association n’a été observée entre le fardeau des aidants et le risque nutritionnel ou la suffisance en protéines chez les patients. La détérioration de la fonction cognitive des patients ne semble pas avoir provoqué une augmentation du fardeau chez leurs aidants. De plus, l’augmentation du fardeau de l’aidant n’était pas accompagnée d’une perte de son poids corporel. Par ailleurs, un fardeau plus important a été observé chez les aidants des patients obèses ou présentant un embonpoint. Conclusion : La réduction du fardeau perçu des aidants permettrait d’améliorer les apports alimentaires des patients et ainsi de limiter ou minimiser le risque de détérioration de leur état nutritionnel et de perte de poids.

DTA : discriminador de tráfego ATM

As redes ATM têm se constituído na solução tecnológica ideal para o desenvolvimento da RDSI-FL. O ATM foi desenvolvido para dar suporte, com altas velocidades e com garantia de qualidade, a uma ampla variedade de serviços. A demanda por serviços de comunicação de dados, em velocidades maiores do que as redes de pacotes atuais são capazes de oferecer, tem crescido rapidamente, estimulando o desenvolvimento da tecnologia ATM, que tem sido muito promissora, devida a sua flexibilidade e eficiência. Para dar suporte à comunicação de dados em redes ATM, foram desenvolvidas soluções, como a emulação de redes locais (LANE), a interconexão de redes locais (LAN) e metropolitanas (MAN), e o protocolo IP sobre ATM. O ATM utiliza multiplexação estatística (assíncrona) para inserir os dados nos canais de comunicação de forma otimizada. Esta técnica, permite atender uma quantidade maior de fontes heterogêneas sob num único canal, porém, pode causar congestionamento na rede. O uso da multiplexação estatística, aliada à necessidade de garantir níveis de qualidade diferentes, para cada tipo de serviço, torna necessária a adoção de uma combinação de técnicas de controle de tráfego e congestionamento. Com este propósito, foram desenvolvidos diversas funções e mecanismos, como, por exemplo, controle de acesso (CAC), controle dos parâmetros de uso (UPC), descarte seletivo de células e conformação de tráfego (TS), os quais necessitam conhecer as características do tráfego emitido pela fonte. Por esta razão, toda e qualquer conexão ATM está associada a um contrato de tráfego, que especifica as exigências do usuário, quanto à qualidade de serviço (QoS) a ser oferecida pela rede, através de um descritor de tráfego. O trabalho apresentado nesta dissertação, tem por objetivo propor uma metodologia capaz de discriminar um fluxo de células ATM arbitrário, visando a obter os parâmetros descritores de UPC do mesmo. A discriminação de tráfego é relevante à medida que todos os usuários de redes ATM necessitam, de alguma forma, determinar os parâmetros que caracterizam seu fluxo, para poder negociar o contrato de trafego. Infelizmente, a maioria das aplicações ATM, não tem condições prévias de fornecer dados sobre o comportamento do fluxo que geram. Para estas situações, estamos propondo um Discriminador de Tráfego ATM (DTA), que infere a partir de uma amostra inicial do fluxo um conjunto mais provável de parâmetros, os quais constituirão o descritor de tráfego da fonte (STD).

Caracterização térmica (TG/DTG, DTA, DSC, DSC-fotovisual) de Hormônios bioidênticos (estriol estradiol)

Bioidentical hormones are defined as compounds that have exactly the same chemical and molecular structure as hormones that are produced in the human body. It is believed that the use of hormones may be safer and more effective than the non-bioidentical hormones, because binding to receptors in the organism would be similar to the endogenous hormone. Bioidentical estrogens have been used in menopausal women, as an alternative to traditional hormone replacement therapy. Thermal data of these hormones are scarce in literature. Thermal analysis comprises a group of techniques that allows evaluating the physical-chemistry properties of a drug, while the drug is subjected to a controlled temperature programming. The thermal techniques are used in pharmaceutical studies for characterization of drugs, purity determination, polymorphism identification, compatibility and evaluation of stability. This study aims to characterize the bioidentical hormones estradiol and estriol through thermal techniques TG/DTG, DTA, DSC, DSC-photovisual. By the TG curves analysis was possible to calculated kinetic parameters for the samples. The kinetic data showed that there is good correlation in the different models used. For both estradiol and estriol, was found zero order reaction, which enabled the construction of the vapor pressure curves. Data from DTA and DSC curves of melting point and purity are the same of literature, showed relation with DSC-photovisual results. The analysis DTA curves showed the fusion event had the best linearity for both hormones. In the evaluation of possible degradation products, the analysis of the infrared shows no degradation products in the solid state

Contribuições sobre estudos térmicos (TG/DTG, DTA, DSC e DSC-Fotovisual) da rifampicina e seus principais produtos de degradação

Since its synthesis over 48 years rifampicin has been extensively studied. The literature reports the characterization of thermal events for rifampicin in nitrogen atmosphere, however, no characterization in synthetic air atmosphere. This paper aims to contribute to the thermal study of rifampicin through thermal (TG / DTG, DTA, DSC and DSC - FOTOVISUAL ) and non-thermal (HPLC, XRPD , IR - FTIR , PCA) and its main degradation products ( rifampicin quinone , rifampicin N-oxide 3- formylrifamicin). Rifampicin study was characterized as polymorph form II from techniques DSC, IR and XRPD. TG curves for rifampicin in synthetic air atmosphere showed higher thermal stability than those in N2, when analyzed Ti and Ea. There was characterized as overlapping events melting and recrystallization under N2 with weight loss in the TG curve, suggesting concomitant decomposition. Images DSCFotovisual showed no fusion event and showed darkening of the sample during analysis. The DTA curve in synthetic air atmosphere was visually different from DTA and DSC curves under N2, suggesting the absence of recrystallization and melting or presence only decomposition. The IV - FTIR analysis along with PCA analysis and HPLC and thermal data suggest that rifampicin for their fusion is concomitant decomposition of the sample in N2 and fusion events and recrystallization do not occur in synthetic air atmosphere. Decomposition products studied in an air atmosphere showed no melting event and presented simultaneously to the decomposition initiation of heating after process loss of water and / or solvent, varying the Ti initiating events. The Coats - Redfern , Madsudhanan , Van Krevelen and Herwitz - Mertzger kinetic parameters for samples , through the methods of OZAWA , in an atmosphere of synthetic air and / or N2 rifampicin proved more stable than its degradation products . The kinetic data showed good correlation between the different models employed. In this way we contribute to obtaining information that may assist studies of pharmaceutical compatibility and stability of substances

Estudo da estabilidade térmica de óleos e gorduras vegetais por TG/DTG e DTA

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)