Assessment of damage in old parchments by DSC and SEM</o:p>

Summary Environmental impact on parchment was investigated by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Parchments subjected to accelerated ageing and old parchments were compared to evaluate quality and extent of deterioration. Stability of fibrillar collagen within parchment was determined from the changes in thermodynamic parameters associated with thermal denaturation. Parchment surface was characterised, and specific morphological criteria were selected for damage assessment. The thermodynamic and morphological changes of collagen induced by deterioration are discussed, and their correlations are proposed as a means of ranking damage in old parchments.</o:p>     

表面修饰TiO2、ZrO2纳米微粒的DSC、TGA表征

采用ＤＳＣ及ＴＧＡ技术对制备的表面为硬脂酸修饰的二氧化钛及二氧化锆纳米微粒的热性能进行了研究，结合透射电的分析表征，结果表明，我们所得的ＴｉＯ２，ＺｒＯ２纳米微粒表面确为硬脂民修饰，由于其纳米微粒核的存在使其表面修饰层的熔点温度高；此外表面修饰纳米闰由于其大的比表面积和不稳定的晶体结构使其分别在７１０Ｋ左右产生粘着和型变。     

几种含有酰胺基团超滤膜吸水情况的FTIR,TGA和DSC研究

对几种超滤膜的TGA、DSC及FTIR研究表明,室温下含酰胺基的干燥膜体仍以氢键的形式结合一定数量的单分子水,同时也含有微量的二聚水和多聚水。当温度上升到40℃左右,水与膜体形成的氢键几乎完全断裂。每个酰胺基吸附水量的顺序为:聚砜酰胺>聚苯并咪唑酮>芳香聚酰胺;每种膜吸附水的绝对量顺序为芳香聚酰胺>聚砜酰胺>聚苯并咪唑酮。     

Chaotic parameters and their role in quantifying noise in the output signals from UV, TGA and DSC apparatus

Two fractal dimensions and the Liapunov exponent (LE) have been applied to detect noisy output signals from UV spectrophotometer (UV), thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC) apparatus of 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid ([emim][EtSO₄]). The data collected from these three pieces of equipment were classified before calculating LE, regularization (RD) and box dimensions (BD). The RD and LE are able individually to detect and quantify noisy output signals with a mean error value less than 5% in all cases tested. Given that the LE can be calculated using a really simple method, this chaotic parameter has been selected as the most suitable to detect noise of signals from these apparatus.     

Application of DSC Method for Thermal Stability and Flammability Assessment of Modified Polyurethanes

Differential scanning calorimetry (DSC) was applied to investigate the thermal behaviour of a series of segmented polyurethanes based on diphenylmethane-4,4'-diisocyanate (MDI), polyoxypropylenediol (POPD) and 3-chloro-1,2-propanediol (CPD)/1,2-propanediol (PD).It has been found that the heat of thermal transition in the range of 250–300°C increases with the amount of CPD, which also causes a decrease of polyurethanes' flammability, characterised by its Limited Oxygen Index (LOI) value. On the basis of obtained results it can be concluded that DSC may be applied for flammability evaluation of segmented polyurethanes.This revised version was published online in November 2005 with corrections to the Cover Date.     

取代度和金属平衡离子对羧甲基纤维素热行为的影响

低取代度(DS<0.8)的NaCMC具有纤维素(Ⅱ)型的晶型结构,随DS增加结晶度迅速下降,DS>1时为无定形结构。其T_(?)随DS增加而降低,但DS=1.55的CMC的T_(?)则稍有提高。其起始分解温度(T_(?))随DS增加而增加,而分解活化能则与DS没有规律性的关系。CMC链上的平衡离子H~+、Na~+、Mg~+、Ca~+和Al~(3+)等对其结晶形态的破坏能力不同,对相同价数的离子,随离子半径增大,破坏力增强,而对半径相近的离子,高价的比低价的破坏作用明显。NaCMC的分解活化能E=251～293 kJ/mol,而高价平衡离子的CMC的E=105 kJ/mol左右。     

Thermal analysis of Moroccan phosphates 'Youssoufia' in an oxidative atmosphere by TG and DSC

A non-isothermal experimental study using thermogravimetry (TG) and differential scanning calorimetry (DSC) was conducted for investigation the oxidation reactivity of natural phosphate and its demineralised products. The analyses were carried out in oxygen atmosphere and at different heating rate (5, 10, 20, 30, 50, 60°C min-1) up to 1000°C. The results indicated that the material washed with HCl from the original phosphate, mainly apatite and carbonates of calcium and magnesium, as well as with HCl/HF, silicates minreals, had an inhibition effect during oxidation reactions of organic material. The increase of the heating rate shifted the reactions to higher temperatures. In addition, kinetic parameters were determined by assuming a single first-order kinetic model, using the Coats-Redfern method. The influences of demineralization process of natural phosphate and the heating rate were examined and discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal analysis techniques for characterization of polymer materials

Routine DSC and TGA techniques, used to characterise polymer thermal stability, have been further used for assessment of comparative thermal stability of various polymer materials and for prediction of material lifetimes. The following materials were investigated: (1) commercial and experimental polymer materials - results for poly(vinyl chloride) (PVC) and bisphenol A polycarbonate (PC) are presented; (2) a polydimethylsiloxane-polytetrafluoroethylene (SIL-PTFE) coating system; and (3) commercially available linear low density polyethylene (PE-LLD), unmodified and modified chemically and physically. The plot of reciprocal temperature of initial decomposition 1/T_di vs log heating rate β has been recommended for assessment of comparative thermal stability. The lifetime of polymer materials was calculated from the plots of log time-to-failure, log t_f, vs reciprocal temperature 1/T, where t_f values were obtained using T_di from TGA measurements or directly from the oxidation induction time (OIT) data as criteria for initial deterioration of polymer thermal stability. The following sequences of increasing thermal stability were found for investigated materials:

(1)

PVC ? PC;

(2)

SIL < SIL-PTFE 20% < SIL-PTFE 50% ? PTFE;

(3)

(B) PE-LLD, grafted < (A) PE-LLD, unmodified < (C) PE-LLD, filled.

The lifetime of polymer materials predicted from the plots of log t_f vs 1/T are in reasonable agreement with experimental data and users' observations, e.g. approximately 1 year for PC and unmodified PE-LLD both at 373 K (100 °C) and for PVC at temperature of outdoor conditions about 298 K (25 °C).     

Thermal decomposition of two synthetic glycosides by TG,DSC and simultaneous Py-GC-MS analysis

To develop thermal stable flavor, two glycosidic bound flavor precursors, geranyl-tetraacetyl-β-D-glucopyranoside (GLY-A) and geranyl-β-D-glucopyranoside (GLY-B) were synthesized by the modified Koenigs–Knorr reaction. The thermal decomposition process and pyrolysis products of the two glycosides were extensively investigated by thermogravimetry (TG), differential scanning calorimeter (DSC) and on-line pyrolysis-gas chromatography mass spectroscopy (Py-GC-MS). TG showed the T _p of GLY-A and GLY-B were 254.6 and 275.7°C. The T _peak of GLY-A and GLY-B measured by DSC were 254.8 and 262.1°C respectively. Py-GC-MS was used for the simply qualitative analysis of the pyrolysis products at 300 and 400°C. The results indicated that: 1) A large amount of geraniol and few by-products were produced at 300°C, the by-products were significantly increased at 400°C; 2) The characteristic pyrolysis product was geraniol; 3) The primary decomposition reaction was the cleavage of O-glycosidic bound of the two glycosides flavor precursors. The study on the thermal behavior and pyrolysis products of the two glycosides showed that this kind of flavor precursors could be used for providing the foodstuff with specific flavor during heating process.     

Metrologically based procedures for the temperature, heat and heat flow rate calibration of DSC

Metrologically based measuring procedures and evaluation methods are recommended as guidance for practical temperature, heat and heat flow rate calibration of DSC instruments which are largely independent of instrumental, test and sample parameters. The relevant terms are defined, the measuring procedures and evaluation methods described, calibration materials and their characteristic data stated and guidance for the sample handling provided. Reference is made to three extended papers on calibration. The recommendations were developed by the working group Calibration of Scanning Calorimeters of the German Society of Thermal Analysis (GEFTA).Recommendation of the working group Calibration of scanning calorimeters of the Gesellschaft für Thermische Analyse e.V. (GEFTA)     

New aspects of thermal analysis,Part I. Resolution of DSC and means for its optimization

The definitions of the temperature resolution, the so-called resolution of DSC instruments given in literature are discussed. A new definition of the resolution for DSC instruments is presented and outlined. The main characteristic introduced in this new definition is a minimum between two caloric events as a prerequisite of an existing resolution. Possible candidates of test substances have been evaluated. The oligomer n-hexatriacontane is revealing an interesting phenomenon, namely a lambda transition which is in the peak temperature only 2 K lower than the melting temperature of 76°C. The substance was selected as an ideal test substance for the quantification of the resolution of DSC instruments. The lambda transition is a second order process which may reach under certain conditions the saturation of the occurring molecular dislocation within 0.2 K, and after saturation the heat flow rate drops sharply down. Investigations concerning the main characteristics of n-hexatriacontane in respect to the temperatures of transition (lambda transition and melting), to the involved enthalpies, and to the resolution factors were performed as functions of the sample mass and the heating rate. The importance of relevant evaluation procedures increasing the resolution factors of DSC curves are discussed and these procedures are integrated into the testing of the resolution. The necessity for widening the experimental scope from instruments to evaluation procedures is forced by the existence of instruments with built-in signal treatments based on electronic devices and software procedures. A comparison with literature data is outlined for all of the mentioned characteristic values of n-hexatriacontane. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nanocalorimeter fabrication procedure and data analysis for investigations on implantation damage annealing

Nanocalorimetry operates on similar principles as conventional differential thermal analysis, but the thinness of the system provides a mass addenda small enough to observe thermal processes in thin films or at surface, involving energies in the order of the nanojoules. The fabrication procedure of nanocalorimeters used to measure the heat released by damage after low-energy (30 keV) ion implantation in polycrystalline silicon (poly-Si) is described. Nanocalorimeters are fabricated from low-stress Si₃N_x membranes (100 nm) on which a Pt strip (25 nm) is deposited which serves both as a heater and thermometer. Using Pt allows us to carry out the metallization step prior to Si anisotropic chemical etching releasing the rectangular Si₃N_x membrane, so the success yield nearly reaches 100%. A 140 nm Si layer is deposited on the nanocalorimeters. Large-grain (∼75 nm) poly-Si is obtained by annealing at 900 °C for 100 s. The calculation method used to obtain heat rate curves is described, including the corrections necessary to take into account the dissimilarity between sample and reference calorimeters (baseline), and the increased heating rate and associated losses. Examples of heat release after 30 keV Si implantations are presented, showing that the total amount of heat release is characterized by a saturation above a fluence of 1 Si⁻/nm². The similarity observed in the signal shape between low and high fluence measurements also suggests that each impacting ion produces a high damage zone similar to the damage generated by high fluence irradiation. This conclusion is compatible with the annealing of damage zones proposed by molecular dynamic studies. It is also shown that the measured signal is not affected significantly by temperature non-uniformity.     

Sample encapsulation on glass transition of methylmetacrylate copolymers: TMDSC and DSC studies

The use of modulated temperature differential scanning calorimetry (TMDSC) and differential scanning calorimetry (DSC) in the measurement of the glass transition temperature (T _g) in polymer-water systems presents several important problems. These include the presence of water evaporation endotherms, partial water evaporation during scanning, changes in pan integrity due to vapour pressure developing in the pan headspace during analysis, and possible interaction between water and polymer at high temperatures. As a result, in most of the cases, only apparent T_g values can be obtained. In this study, TMDSC and DSC were used to determinate the thermal behaviour of methylmethacrylate copolymer-water systems. The samples were previously equilibrated at different relative humidities (RH) from 0 to 97% RH. Three different pan arrangements were used. In addition, thermogravimetric analysis (TG) was carried out to determine the initial amount of water in the sample. None of the pan arrangements was entirely suitable for the study of these systems. When sealed pans were used, the plastification effect of water was observed. Some evidence of degradation was also observed in which water and methylmethacrylate appeared to play roles.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effects of high electrolyte concentration on DPPC-multilayers: an ESR and DSC investigation

The effects of salinity on the lateral headgroup interactions of dipalmitoylphosphatidylcholine (DPPC) molecules in fully hydrated multilayers have been investigated by spin label electron spin resonance (ESR) spectroscopy and differential scanning calorimetry (DSC).By increasing the NaCl concentration from 0 to 3 M in the multilayers' dispersion medium, the ESR measurements performed with the 5-stearic acid spin label and di-tert-butyl-nitroxide show an increase in the orientational degree of order of the lipid molecules, mainly in the gel phase, and a decrease of the membrane permeability. An upward shift from 31.5° to 36.5°C and from 40.5° to 41.9°C of the pre- and main DPPC phase transition temperatures, respectively, is observed with 5-SASL, while slightly higher values are detected with DTBN. Small effects are evident on the properties of the liquid crystalline phase of the DPPC multilayers.The DSC measurements also reveal an upward shift of the pre- and main transition temperatures. The shifts, however, are more marked if compared to the ones observed with the ESR technique.The findings suggest an increase in the packing density of the DPPC molecules in the multilayers in presence of high salt concentration. Dehydration of the DPPC interfacial region with a variation of the lateral electrostatic interactions between phospholipid polar heads trigger the phenomena observed.     

Solid state interaction of steroids with calixarenes. I. A preliminary FTIR and DSC study on 4-en-3-keto-steroids

Both DSC and FTIR studies indicate that co-grinding and co-precipitation cause steroids to interact with calixarenes. This interaction leads to breaking of the crystal lattice of the steroids, dispersion of the steroidal carbonyls in a hydrophobic environment and formation of hydrogen bonds between steroidal and calixarene hydroxyls. This interaction seems to be specific, depending on the structure of the calixarene and of the steroid involved. It is reasonable to assume that inclusion complexes are formed.     

Morphology of homogeneous copolymers of ethene and 1-octene. I. Influence of thermal history on morphology

The morphology of homogeneous copolymers of ethene and 1-octene synthesized using a V-based Ziegler-Natta catalyst was studied as a function of the short chain branching content (SCBC) and the molar mass. Linear polyethylenes (LPE) were used as reference material. For the linear samples an increase in molar mass results in an increase of the long period and the crystalline lamella thickness. A decrease of cooling rate results in an increase of the melting temperature, the long period and the crystalline lamella thickness and an evolution from spherulitic structures to perfectly stacked lamellae. For the branched samples, increasing the SCBC results in a decrease of the melting and the crystallization temperature, crystallinity, spherulite radius, the long period, and the crystalline lamella thickness. The two latter tend to a limiting value on reaching a SCBC of 20CH₃/1000C. On the other hand, an increase of the a axis and to a lesser extent the b axis of the unit cell is observed. Decreasing the cooling rate affects only the crystallinity of the least branched samples. Furthermore decreasing the cooling rate results in smaller spherulites, has a minor influence on the lamellar parameters and reduces the dimensions of the basal plane of the unit cell. Increasing the molar mass of the branched samples results in a drop of the crystallinity, a deterioration of the superstructure, enlarges the amorphous layer thickness and the dimensions of the basal plane. All these observations can be accounted for by the different crystallization regimes being applicable when different molar masses, SCBC and cooling rates are used. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2689–2713, 1997     

Effect of a bioactive curcumin derivative on DPPC membrane: A DSC and Raman spectroscopy study

Interactions of dimethoxycurcumin (1) a lipophilic bioactive curcumin derivative with dipalmitoyl phosphatidylcholine (DPPC) were investigated. The thermodynamic changes caused by (1) and its location into DPPC lipid bilayers were monitored by differential scanning calorimetry and Raman spectroscopy. The results reveal that (1) influences the thermotropic properties of DPPC lipid membrane causing abolition of the pretransition and broadening of the phase-transition profile and slightly decreases the T_m at increasing concentrations. The Raman height intensity ratios of the peaks I_2935/2880, I_2844/2880 and I_1090/1130 are representative of the interaction of (1) with the alkyl chains and furnish information about the ratio between disorder and order that exists in the conformation of the alkyl chain. The intensity changes of the peak at 715 cm⁻¹ indicates interaction between the choline head group and (1). The Raman spectroscopy results are in agreement with the thermal analysis results. Biologically active lipophilic molecules such as (1) should be studied in terms of their interaction with lipid bilayers prior to the development of advanced lipid carrier systems such as liposomes. The results of these studies provide information on the membrane integrity and physicochemical properties that are essential for the rational design lipidic drug delivery systems.     

Thermal stability and viscoelastic properties of MF/PVAc hybrid resins on the adhesion for engineered flooring in under heating system; ONDOL

The thermal properties of blends of melamine-formaldehyde (MF) resin and poly(vinyl acetate) (PVAc) for engineered flooring used on the Korean traditional ONDOL house floor heating system were investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The viscoelastic properties of the blends were also studied. Because MF resin is a thermosetting adhesive, the effect of MF rein was shown across all thermal behaviors. The addition of PVAc reduced the curing temperature. The TGA results showed that the DTG_max temperature and thermal stability of the blends increased with increasing PVAc content. The blends were examined in non-isothermal DSC experiments at a heating rate of 10 °C/min. There was an exothermic peak in all the heating scanning curves, with each blend displaying a single curing peak temperature (T_p), intermediate between those of the two pure components and varying with the blend composition. The DMTA thermogram of MF resin showed that the storage modulus (E′) increased as the temperature was further increased as a result of the cross-linking induced by the curing reaction of the resin. E′ of MF resin increased both as a function of increasing temperature and with increasing heating rate.