Stop-and-return DSC method to study fat crystallization

Differential scanning calorimeters have frequently been used to study the isothermal crystallization kinetics of fats and oils. In some circumstances (e.g. start of crystallization during cooling to the crystallization temperature, crystallization in emulsion) this straightforward approach is not applicable. This paper describes an indirect DSC method for determination of the crystallization kinetics under these ‘difficult’ circumstances. The principle is to stop the crystallization at different moments during the isothermal crystallization and raise the sample temperature. The amount of heat released is then used as a measure for the amount of crystallization and plotted as function of time. Combination of the stop-and-return method with the direct method may sometimes be used to save on measurement time. Stop-and-return experiments can furthermore be used to gain more insight in the crystallization mechanism based on the fact that different polymorphic forms and fractions have different melting temperatures.     

DSC and DMA study of chestnut shell tannins for their application as wood adhesives without formaldehyde emission

The use of chestnut (Castanea sativa) shell tannin extracts for the formulation of wood adhesives has been studied. The interest was centred not only on the formulation of adhesives from a renewable resource but also on the possibility of completely removing formaldehyde from the adhesive formulations. Tris(hydroxymethyl)nitromethane (TRIS), glyoxal (GLY) and hexamine (HEX) were used as hardeners and the results were compared with those obtained with the traditional hardener, paraformaldehyde (PAR). Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to study the chemical and mechanical cure of the formulated adhesives and the influence of the type of hardener on the curing properties. DSC curves were obtained at three heating rates and using an isoconversional method, chemical conversion vs. time at a given temperature was obtained. The curing enthalpy for the adhesive with hexamine as hardener was the highest and decreased in the order HEX ~ TRIS ≫ GLY > PAR. The highest rate of chemical cure was achieved using PAR as hardener followed by GLY > HEX > TRIS, that required higher curing temperatures to achieve complete chemical cure. Mechanical cure was analyzed from isothermal DMA experiments. The rate of mechanical curing decreased in the order TRIS > HEX > GLY, however, the rigidity after completion of curing increased in the same order. Alternative hardeners increased significantly adhesive pot-life compared to paraformaldehyde, especially tris(hydroxymethyl)nitromethane.     

Fast DSC applied to the crystallization of polypropylene

In an effort to find the limit of crystallization of polypropylene, a series of quantitative and semiquantitative DSC experiments at rates up to 10,000 deg/min are described. Even at these fast rates polypropylene crystallized on cooling between 350±15 K and 280±6 K. No fully amorphous polypropylene was produced. No initial stage crystallization to the condis state could be proven by quenching after partial crystallization.

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Zusammenfassung Eine Reihe von quantitativen und semiquentitativen DSC-Versuchen mit Aufheizgeschwindigkeiten bis 10000 K/min wurden ausgeführt, um die Grenze der Kristallisation von Polypropylen festzustellen. Sogar bei diesen schnellen Aufheizgeschwindigkeiten kristallisiert Polypropylen beim Abkühlen zwischen 350±15 K und 280±6 K. Kein völlig amorphes Polypropylen wurde erhalten.

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, 10 000 /. 350±15 280±6 . « » . .

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This work was supported in part by a grant of Hercules, Inc. to the ATHAS effort and in part by the Polymers Program of the National Science Foundation (Grant number DMR 8317097). The experimentation was helped by an instrument gift by the Celanese Company.     

Use of sub-ambient DSC to complement conventional DSC and TG

Several drug substances or excipients are hygroscopic. The uptake or loss of water of such substances is generally difficult to control during processing or storage of drug products. DSC instruments with sub-ambient temperature equipment allow the determination of the amount of freezable water by measuring the corresponding melting enthalpy.The determination of freezable water adds valuable information complementary to TG analysis for understanding the processing and storage of raw materials and drug products. Several substances were tested as is, without treatment, after storage at 92% r.h. and after equilibration with water. The results of these experiments showed that it was possible to demonstrate defined hydrate formation, to determine the upper level of binding of water in amorphous substances and to confirm reversible hydrate formations demonstrated by temperature resolved X-ray diffraction.     

Polyurethanes for potential use in transparent armour investigated using DSC and DMA

A material combination that may be applied as transparent armour is glass-clad polyurethane. These are comprised of a relatively thin glass strike face and a relatively thick (transparent) polyurethane backing layer. Three transparent polyurethane samples were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The DSC results identified the glass transitions and in some cases the melting and crystallisation processes. The DMA experiments were only performed on heating around the glass transition region to further investigate this transition. The experiments were performed at three different frequencies (1, 10 and 100 Hz); the shift of the glass transition with the frequency was clearly observed. The method of time–temperature superposition was used to extrapolate the results to higher frequencies as the magnitude of the strain-rate occurring within ballistic applications is in the order of 1000 s⁻¹ or higher. Polyurethane with a rubbery behaviour at normal (low) strain rates can be stiff and brittle when used as an armour component (temperature below its dynamic T _g value).     

Determination of physical and structural parameters by DMA and DSC application to an epoxidic formulation

Mechanical behaviour play an important role in the election of an epoxidic formulation of well determined properties as it has a marked influence on both structural and external factors. Temperature and time strongly act on polymers properties owing to their viscoelastic nature. Knowledge of the dynamic moduli and properties of polymeric materials is indispensable for the design of this materials. At the same time, the influence of the temperature on polymers behaviour may be studied once the activation energy is known. In this paper the different dynamic moduli and activation energy are measured using a Perkin Elmer DMA 7. The relationships between the dynamic mechanical properties and the molecular weight of the polymers make possible the calculation of the molecular weight. Results reasonably agree with literature values.     

A DSC study of the crystallization behaviour of polylactic acid and its nanocomposites

The isothermal crystallization behaviour of polylactic acid (PLA) and a clay nanocomposite of have been examined using differential scanning calorimetry. The data obtained clearly indicates that the presence of the nanocomposite particles in the composite material influences the crystallization kinetics of the PLA when crystallized both from the solid amorphous state as well as from the melt. When crystallized from the melt the presence of the clay nano-particles appears to be influencing the nucleation and crystal growth rate of the PLA such that the crystallization rate is enhanced by a factor of about 15 to 20. This result is of tremendous significance in identifying the processing window for the production of foamed nanocomposites from PLA. In addition the effect of thermal exposure at 200°C on the crystallization behaviour of these materials has been investigated, with the results suggesting that holding these materials at 200°C for periods of time up to 60 min in an inert atmosphere only has a marginal effect.     

Nanoconfinement as a tool to study early stages of polymer crystallization

This article promotes the idea that crystallization experiments under confinement can be an interesting tool to learn more about the early stages of polymer crystallization in bulk systems. Based on various results from the recent literature, it is demonstrated that crystalline forms that are metastable, transient, or inaccessible in bulk samples can be easily obtained and studied in nanoscopic compartments. This is interesting in the light of the recent discussion about thermodynamic reasons for the temporary occurrence of a mesophase at the growth front of crystals in bulk polymers, in particular, about a hexagonally packed mesophase in polyethylene. The experimental findings for nanoconfined methylene sequences seem to support indirectly thermodynamic approaches explaining the occurrence of a mesophase based on the small thickness of the crystal at the growth front. A first estimate for the critical crystal thickness d_mc defining the transition from hexagonal to orthorhombic packing in case of confined methylene sequences is provided based on results for side chain polymers. Further perspectives of crystallization experiments on confined systems are discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1556–1561, 2008     

Coaxial-electrospinning as a new method to study confined crystallization of polymer

Coaxial-electrospinning (ES) was used as a new method to fabricate one-dimensional (1D) confinements for studying confined crystallization of poly(ethylene glycol) (PEG). A series of core–sheath ultrafine fibers with PEG as the core and cellulose acetate as the sheath were obtained by coaxial ES. It was found that the uniform core–sheath ultrafine fibers could be fabricated and a (1D) confinement environment, a nanotube with a diameter from 68 to 860 nm, could be obtained by coaxial-ES. When the confinement dimension decreased to be smaller than 120 nm in diameter, the melt temperature (T_m), the crystallization temperature (T_c), the crystallinity (X_m), and the crystal sizes of the PEG were much smaller than those of bulk PEG and when the nanotube was larger than 200 nm in diameter, the T_m, T_c, X_m, and the crystallite sizes of the PEG were close to those of bulk PEG, which suggested that the crystallization of the PEG was influenced by the confinement dimension. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Elastic Moduli and Activation Energies for an Epoxy/m-XDA System by DMA and DSC

The influence of the resin/diamine ratio on the properties of the system diglycidyl ether of bisphenol A (BADGE n=0/m-xylylenediamine) (m-XDA) was studied. Variation of this ratio resulted in significant effects on the cure kinetics and final dynamic mechanical properties of the product material. The study was made in terms of storage modulus (E′), vss modulus (E″) and molecular mass between cross-links (M_c) at different ratios. Two geometries (cylindrical and rectangular) were considered. The influence of temperature was studied through the activation energy (E_a>), which depends on the epoxy/amine ratio and the geometry of the samples. Glass transition temperatures (T_g>) and glass transition temperatures for thermosets with null degree of conversion (T_go>) were determined by DSC. T_g> decreases when amounts of curing agent greatly in excess of the stoichiometric composition were used. This revised version was published online in July 2006 with corrections to the Cover Date.     

TG and DSC kinetics of thermal decomposition and crystallization processes

The simplen ^th order model equation combined with the Arrhenius approach of the temperature dependency of the reaction rate constant is widely used in thermal analysis. The new Mettler software package for thermal analysis, GraphWare TA72 allows to access a full model comprising the power law and the crystallization kinetics (AvramiErofe'ev). The kinetics of the following reactions are studied to illustrate some applications:

thermal decomposition of dissolved dibenzoylperoxide, (dynamic and isothermal DSC measurement)

crystallization of polyethylene terephthalate (PET) (isothermal DSC measurements).

The kinetic model applied and the accuracy of the kinetic data obtained are discussed by means of a comparison of a predicted behaviour with the kinetic data measured isothermally.     

DSC and X-ray studies on side-chain crystallization of comb-like polymers

Thermal properties of acrylate and methacrylate monomers containing long-fluorocarbon chains (H(CF₂)_nCH₂OCOCH=CH₂, (F_nA) and H(CF₂)_nCH₂OCOC(CH₃)=CH₂, (F_nMA), wheren=6, 8, 10) and their comb-like polymers have been investigated by differential scanning calorimeter (DSC) and X-ray diffraction. The comb-like polymers (PF₁₀A and PF₁₀MA) with sufficiently long-fluorocarbon chains showed a simple melting and crystallizing behavior. For the fusion of PF₁₀A in 1st heating, enthalpy change H _f was 18 kJ mol^–1 and entropy change S _f was 45 J K^–1 mol^–1, while for PF₁₀MA the values H _f and S_f were 5.3 kJ mol^–1 and 14 J K^–1 mol^–1, respectively. Melted PF₈A crystallized slowly, whereas PF₈MA with same fluorocarbon chain and also both of PF₆A and PF₆MA with shorter fluorocarbon chains can hardly crystallize by the aggregation of side-chains. Effects of the length of side-chain and the flexibility of main chain on the side-chain crystallization of comb-like polymers are clear. Crystallization process of the methacrylate monomers was sensitively affected by the scanning rate of DSC measurement and the length of fluorocarbon chains.     

A study of the crystallization kinetics of PVF2 by DSC and dilatometry

Poly(vinylidene fluoride) was crystallized isothermally from the melt at several temperatures. Crystallization rates have been measured using dilatometry and differential scanning calorimetry. The results were analysed in terms of the Avrami equation. The different methods yielded similar values for the kinetic parameters. The surface free energy of the lamellar crystallites has been determined.     

Physical Aging of a Tetrafunctional/phenol Novolac Epoxy Mixture Cured with Diamine. DSC and DMA measurements

The physical aging of a system containing tetraglycidyl-4-4′-diaminodiphenylmethane (TGDDM), with a multifunctional novolac glycidyl ether resin hardened by 4,4′-diaminodiphenylsulphone (DDS) has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Samples fully cured were aged at temperatures between 200 and 250°C, during periods of time from 1 to a maximum of 336 h. Furthermore, the dynamic mechanical relaxation behaviour annealed at temperature of 220°C, was studied, aging during 24 and 168 h. The effect of the enthalpy relaxation during DSC heating scan is shown by the presence of an endothermic peak whose position and intensity depends on the aging conditions, both temperature and time. DSC studies suggest that enthalpy relaxation increases gradually with aging time to a limiting value for each temperature where structural equilibrium is reached. DMA results show that the effect of aging is to cause chain stiffening and a decrease in the height of the peak value of the loss factor. This revised version was published online in August 2006 with corrections to the Cover Date.     

Modulated DSC as a tool for polyethylene structure characterization

The Modulated Differential Scanning Calorimeter (MDSC) technique, using TA Q1000 instrument, has been applied as a tool to study the reversible and non-reversible heat flow characteristics of a wide range of polyethylenes. It was found that the heat flow characteristic is dependent upon the heating rates and modulation period used in the test. By using a set of standard test conditions, MDSC was found to be useful in studying the effect of previous thermal processing conditions, additive effects, and also the density, MI, type of comonomer, and molecular architecture.     

丁基橡胶阻尼材料相容性的DSC与DMA研究

高聚物力学阻尼材料是一种能消除振动和噪声以聚合物为基质的功能材料。当聚合物处于玻璃化转变温度(Tg)区域时,其链段运动不能完全跟上振动的速度而产生分子链内摩擦,吸收一部分振动能,再以“热”的形式而耗散,这样就起到减少振幅或降低振幅的作用。     

Kinetics of crystallization of metallic glasses studied by non-isothermal and isothermal DSC

A method for describing the lengths of induction periods at linear-heating measurements, is employed for the study of induction periods in the crystallisation of metallic glasses. For Fe₇₅Si₁₅B₁₀ glass, close values of the related kinetic parameters were obtained from isothermal and nonisothermal measurements. On the basis of the results obtained, the absence of induction period in the first crystallisation step of Al₉₀Fe₇Nb₃ glass in the isothermal DSC measurement has been elucidated.     

Use of subambient DSC for liquid and semi solid dosage forms

Examples of the use of subambient DSC for characterizing excipients which have the melting range within ambient or subambient temperatures as well as liquid and semiliquid dosage forms are presented in the following paper.Influences of the quality, polymorphism, storage of excipients used for dosage forms and changes in the composition on the melting behaviour and quality of dosage forms were investigated.Changes of the melting behaviour of dosage forms determined with subambient DSC have shown to correlate with the quality of the dosage form, the quality of excipients used or structural changes (due to various influences) in the dosage form. DSC for use in the range of subambient and ambient temperatures represents an alternative analytical method for development and quality assurance in pharmaceutical industry for liquid and semiliquid preparations.