Tri-alpha-naphthylbenzene as a crystalline or glassy matrix for matrix-assisted laser desorption/ionization: a model system for the study of effects of dispersion of polymer samples at a molecular level

Tri-alpha-naphthylbenzene (TalphaNB) can exist as either a crystalline or glassy solid at ambient temperatures, making it a unique matrix in matrix-assisted laser desorption/ionization (MALDI) spectroscopy. Electrosprayed TalphaNB is crystalline and has a melting point of 180 +/- 2 degrees C, as measured by differential scanning calorimetry (DSC). A glass of TalphaNB is obtained upon heating above the crystalline melting point with a glass transition temperature of 68 +/- 2 degrees C having no remaining crystallinity. MALDI samples containing mass fraction 1% polystyrene (PS) are run in both the crystalline and amorphous states. In the crystalline state, there is a strong spectrum typical of PS, but upon melting and quenching to the glassy state, the MALDI signal disappears. If the transparent, amorphous sample is treated with 1-butanol, it becomes white, and the MALDI signal returns. DSC shows that the 1-butanol treatment leads to the return of some of the crystallinity. Small angle neutron scattering (SANS) shows that the crystalline state has large aggregations of PS while the amorphous state has molecularly dispersed PS molecules. MALDI gives strong signals only when there are large aggregations of polymer molecules, with individually dispersed molecules producing no signal.     

Porous membranes of PLLA-PCL blend for tissue engineering applications

Porous membranes of polycaprolactone-poly(l-lactic acid) blends were prepared by a freeze-extraction process. This procedure was able to disperse homogeneously both components despite their amorphous phases being immiscible (as proven by the fact that the glass transition temperature of PCL in the blend is independent of blend composition) and both polymers crystallize. Thus, the porous membrane consists of amorphous and crystalline phases of both components. DSC and AFM were used to characterize the microstructure of the blends, whereas SEM and gravimetric methods enabled the porosity (around 70%) and pore architecture to be determined. Compression stress-strain experiments show the characteristic behaviour of porous materials with a yield stress that rapidly drops when the PCL content increases - whereas the deformation plateau zone enlarges.     

Phase and state transition effects on dielectric, mechanical, and thermal properties of polyols

The present study investigated the glass transition, crystallisation and melting behaviour of erythritol, xylitol, and glucitol (sorbitol) using dielectric analysis (DEA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). Sorbitol and xylitol were plasticised by water and their glass transition temperatures decreased when water content was increased. Erythritol crystallised rapidly, and its water plasticisation behaviour could not be determined. Melting of the crystalline polyols occurred at their specific melting temperatures. Melts of erythritol and xylitol crystallised on recooling and no glass transition was apparent on reheating. Quench cooled sorbitol melt remained amorphous and showed a glass transition on reheating. Glass transition and crystallisation were apparent in the DSC thermogram and the dielectric and the dynamic mechanical spectra of mixtures of amorphous and crystalline xylitol.     

Revisiting the Optimal Nano‐Morphology: Towards Amorphous Organic Photovoltaics

Organic photovoltaic cells commonly use an active layer with a polycrystalline bulk heterojunction. However, for simplifying the fabrication process, it may be worthwhile to use an amorphous active layer to lessen the burden on processing to achieve optimal performance. While polymers can adopt amorphous phases, molecular glasses, small molecules that can readily form glassy phases and do not crystallize over time, offer an appealing alternative, being monodisperse species. Our group has developed a series of reactive molecular glasses that can be covalently bonded to chromophores to form glass‐forming adducts, and this strategy has been used to synthesize glass‐forming donor and acceptor materials. Herein, the results of devices incorporating these materials in either partially or fully amorphous active layers are summarized. Additionally, these molecular glasses can be used as ternary components in crystalline systems to enhance efficiency without perturbing the morphology.     

Mechanism of amorphisation in Cu–Ru,a binary alloy with a positive heat of mixing

Cu–Ru has a positive heat of formation and does not form equilibrium alloys. Nevertheless, amorphous alloys have been obtained by He (Phys. Rev. B 75, 045431 (2007)) by ion mixing of multilayers. Analysis of the free energies of the competing phases (the glass and the crystalline solid solutions based on Cu and Ru) leads us to propose that formation of glasses occurs as a result of kinetic frustration between the hcp and fcc solid solutions. These two have lower free energies than the glass, but those free energies are very similar, so a strong driving force for the formation of a particular crystalline phase does not exist. In addition, formation and growth of hcp and the fcc phases appears equally difficult from a kinetic point of view. Very small embryos can form but their growth will be frustrated by the presence of embryos of the other phase.     

不同结晶度的乙二醇及其水溶液玻璃化转变与焓松弛

为了考察晶体成分对无定形成分玻璃化转变和结构松弛行为的影响,利用差示扫描量热法(DSC),结合低温显微技术,研究了乙二醇(EG)及其50％水溶液在不同结晶度时的玻璃化转变和焓松弛行为.采用等温结晶方法控制骤冷的部分结晶玻璃体中的晶体份额.DSC结果表明,对于部分结晶的EG,只有单一的玻璃化转变过程,而对于50％EG,当结晶度不同时,不同程度地表现出两次玻璃化转变（无定形相Ⅰ和无定形相Ⅱ）.相Ⅰ的玻璃化转变温度和完全无定形态的含水EG的玻璃化转变温度相一致;相Ⅱ的玻璃化转变温度要比此温度约高6 ℃.低温显微观察结果印证了DSC实验结果.DSC等温退火的实验和KWW(Kohlrausch-Williams-Watts)衰变函数分析结果表明,EG无定形和50％EG中的两种无定形有不同的焓松弛行为.     

The mechanism and stability of thermal transitions in hair keratin

Differential Scanning Calorimetry (DSC) has been applied to study the interactions between components of human hair keratin. Keratin is a biopolymeric composite made of several proteins forming basically two phases: amorphous matrix and crystalline microfibrillar phase. Water, the content of which depends on atmospheric humidity, is also an integral part of keratin structure. The following processes are apparent from the DSC: removal of loosely bound water (ca. 70°C), a transition in the amorphous phase (155°C) and melting/denaturation of the -crystalline phase (233°C). The process occurring in keratin at ca. 155°C has an opposite character to a glass transition; we refer to this process as the toughening transition. The area of the -keratin peak increases significantly upon annealing at temperatures from 80°C to 150°C and decreases for higher annealing temperatures. Water affects both the crystalline and amorphous phases of keratin. The process similar in nature to annealing — induced recrystallization in synthetic polymers is strictly correlated with removal of strongly bound fraction of water in keratin.     

Structural arrangement of crystalline/amorphous phases of polyethylene‐block‐polystyrene copolymer as induced by orientation techniques

A polyethylene‐block‐polystyrene copolymer film having a bicontinuous crystalline/amorphous phases was tensile‐drawn under various conditions for the structural arrangement of these phases. The prepared film could be drawn below the melting temperature of the polyethylene component, with the highest drawability obtained at 60°C. However, the initial bicontinuous structure was gradually destroyed with increasing strain because the drawing temperature was lower than the glass‐transition temperature of the polystyrene component. Correspondingly, a necking phenomenon was clearly recognizable when samples were drawn. In contrast, drawing near the melting temperature of the polyethylene component produced less orientation of both the crystalline and amorphous phases, resulting in homogeneous deformation with lower drawing stress. These results indicated that the modification of the lower ductility of the polystyrene component was key to the effective structural arrangement of both phases by tensile drawing. Here, a solvent‐swelling technique was applied to improve polystyrene deformability even below its glass‐transition temperature. Tensile drawing after such a treatment successfully induced the orientation of both the crystalline and amorphous phases while retaining their initial continuities. A change in the deformation type from necking to homogeneous deformation was also confirmed for the stress–strain behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1731–1737, 2006     

Characterization of crystalline and amorphous content in pharmaceutical solids by dielectric thermal analysis

Morphological and thermodynamic transitions in drugs as well as their amorphous and crystalline content in the solid state have been distinguished by thermal analytical techniques, which include dielectric analysis (DEA), differential scanning calorimetry (DSC), and macro-photomicrography. These techniques were used successfully to establish a structure versus property relationship with the United States Pharmacopeia standard set of active pharmaceutical ingredient (API) drugs. A distinguishing method is the DSC determination of the amorphous and crystalline content which is based on the fusion properties of the specific drug and its recrystallization. The DSC technique to determine the crystalline and amorphous content is based on a series of heat and cool cycles to evaluate the drugs ability to recrystallize. To enhance the amorphous portion, the API is heated above its melting temperature and cooled with liquid nitrogen to ?120 °C (153 K). Alternatively a sample is program heated and cooled by DSC at a rate of 10 °C min^?1. DEA measures the crystalline solid and amorphous liquid API electrical ionic conductivity. The DEA ionic conductivity is repeatable and differentiates the solid crystalline drug with a low conductivity level (10^?2 pS cm^?1) and a high conductivity level associated with the amorphous liquid (10⁶ pS cm^?1). The DSC sets the analytical transition temperature range from melting to recrystallization. However, analysis of the DEA ionic conductivity cycle establishes the quantitative amorphous and crystalline content in the solid state at frequencies of 0.10–1.00 Hz and to greater than 30 °C below the melting transition as the peak melting temperature. This describes the “activation energy method.” An Arrhenius plot, log ionic conductivity versus reciprocal temperature (K^?1), of the pre-melt DEA transition yields frequency dependent activation energy (E _a, J mol^?1) for the complex charging in the solid state. The amorphous content is inversely proportional to the E _a where the E _a for the crystalline form is higher and lower for the amorphous form with a standard deviation of ±2%. There was a good agreement between the DSC crystalline melting, recrystallization, and the solid state DEA conductivity method with relevant microscopic evaluation. An alternate technique to determine amorphous and crystalline content has been established for the drugs of interest based on an obvious amorphous and crystalline state identified by macro-photomicrography and compared to the conductivity variations. This second “empirical method” correlates well with the “activation energy” method.     

Quantification of amorphous content in maltitol by

A method was developed for the quantification of low levels of amorphous content in maltitol with StepScan DSC. The method was based on the fact that the change of specific heat at the glass transition is linearly proportional to the amorphous content. The influence of different measurement parameters of StepScan DSC was evaluated and two different calibration heating rates were tested. Synthetic mixtures with various proportions of crystalline and amorphous maltitol were prepared. Two different measurement methods were compared and the linear regression between ΔC_p and amorphous content was obtained. The limit of detection (LOD) and the limit of quantification (LOQ) values were for the fictive temperature 0.24% (amorphous content) and 0.81% and for the half point temperature 0.27 and 0.92%, respectively, (method 1) and for the fictive temperature 0.18 (amorphous content) and 0.61% and for the half point temperature 0.16 and 0.52%, respectively (method 2). Very low determination limits for the quantification of amorphous content could be attained with the StepScan DSC method. However, the realistic limit of quantification was somewhat higher (about 3%) because of noise in the StepScan measurement. The main advantage of the StepScan DSC method for quantification of amorphous content was that the glass transition and relaxation peaks are separated into different curves and the interpretation becomes easier.     

Avrami exponent of crystallization in tellurite glasses

Nucleation process and crystal growth for three samples of the (20-x)Li₂O–80TeO₂–xWO₃ glass system were studied using X-ray diffraction and differential scanning calorimetry techniques. X-ray diffraction data confirmed the amorphous characteristic of the as-quenched samples and indicated the growth of crystalline phases formed due to the thermal treatment for annealed samples. These results reveal the presence of three distinct γ-TeO₂, α-TeO₂ and α-Li₂Te₂O₅ crystalline phases in the TL sample, and two distinct α-TeO₂ and γ-TeO₂ crystalline phases in the TLW5 and TLW10 samples. The activation energy and the Avrami exponent were determined from DSC measurements. The activation energy values X-ray diffraction data of the TLW10 glass sample suggest that γ-TeO₂ phase occur before the α-TeO₂. The results obtained for the Avrami exponent point to that the nucleation process is volumetric and that the crystal growth is two or three-dimensional.     

The effect of copolymerization on transition temperatures of polymeric materials

The relationship between transition temperatures and copolymer composition was studied by DSC. Three types of copolymers were studied: styrene-acrylonitrile (SAN), vinyl chloride-vinyl acetate (VC-VA), and ethylene vinyl acetate (EVA). SAN's and VC-VA's are amorphous copolymers, whereas EVA's are semi-crystalline copolymers. The variation of the glass transitions and the crystalline melting are discussed in this study.     

Direct crystallization of silicate–phosphate glasses of NaCaPO4–SiO2 system

The subject of the study was silicate–phosphate glasses of NaCaPO₄–SiO₂ system which are precursors of glass–crystalline materials. Glass–crystalline materials of NaCaPO₄–SiO₂ system obtained via crystallization of glasses belong to a group of the so-called bioactive materials. In order to obtain glass–crystalline materials with pre-established parameters, it is necessary to conduct crystallization of glasses at specific conditions. In order to design direct crystallization process properly, it is necessary to know the structure and microstructure of the glassy precursor. Microscopic investigation showed that liquation takes place in all the studied glasses. Based on DSC examinations, it has been found out that crystallization of the glasses of NaCaPO₄–SiO₂ system is a multistep process. The presence of several clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the separated phase with the matrix remaining amorphous or vice versa. Conducted detailed X-ray and spectroscopic studies of the materials obtained by heating in a gradient furnace (in the temperature specified on the basis of DSC) showed that separated phase and matrix crystallizes separately. Therefore, bioactive glass–crystalline materials can be obtained due to the existence of the phase separation phenomenon and pre-established sizes of the crystalline phase.     

Glass transition and enthalpy relaxation of ethylene glycol and its aqueous solution

Differential scanning calorimetry (DSC) and cryomicroscopy were employed to investigate the glass transition and enthalpy relaxation behaviors of ethylene glycol (EG) and its aqueous solution (50% EG) with different crystallization percent. Isothermal crystallization method was used in devitrification region to get different crystallinity after samples quenched below glass transition temperature. The DSC thermograms upon warming showed that the pure EG has a single glass transition, while the 50% EG solution has two if the solution crystallized partially. It is believed that the lower temperature transition represents the glass transition of bulk amorphous phase of EG aqueous solution glass state, while the higher one is related to ice inclusions, whose mobility is restricted by ice crystal. Cryomicroscopic observation indicated that the EG crystal has regular shape while the ice crystal in 50% EG aqueous solution glass matrix has no regular surface. Isothermal annealing experiments at temperatures lower than T_g were also conducted on these amorphous samples in DSC, and the results showed that both the two amorphous phases presented in 50% EG experience enthalpy relaxation. The relaxation process of restricted amorphous phase is more sensitive to annealing temperature.     

A study of crystalline transitions in a thermoplastic polyimide

A new polyimide derived from 4,4′-isophthaloyldiphthalic anhydride (IDPA) and 1,3-bis(4-aminophenoxy-4′-benzoyl)benzene (1,3-BABB) having semicrystalline behavior was prepared at NASA Langley Research Center in 1987. The crystalline transitions of this thermoplastic polyimide have been studied. The differential scanning calorimetry (DSC) pattern of partially imidized film exhibited two distinct crystalline melt endotherms. For this study each crystalline phase was isolated and enhanced by controlled thermal treatment. A film containing approximately 50% of both phases and an amorphous film were also prepared. Evaluations of these films were performed by DSC, wide-angle x-ray scattering (WAXS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Three distinct crystalline morphologies; ellipsoid, cubic, and needlelike embedded in an amorphous matrix were observed as a function of various cure conditions by SEM.     

共聚聚醚酯酰胺的多重转变及其相态结构

Segmented polyesteramides have been synthesized from N,N'-bis（p-carbomethoxybenzoy）butanediamine（T4T）as crystalline segments and mixture of poly（tetramethylene oxide）with the average molecular weight 1000（PTMO1000）and 1,5-pentanediol（PDO）as soft segments. The polymerization was carried out in the melt at 250℃ for 1-2 h while vacuum was applied. The chemical composition of the copolymer was measured by H1-NMR. The melting behavior of the copolymers was studied by the differential scanning calorimeter. The dynamic mechanical properties were investigated on injection moulded bars by means of dynamic mechanical analysis. It was found that the copolymers with more than 40% molar ratio PDO showed two glass transition temperatures and two melting temperatures. The glass transition temperatures are independent of composition,and thus two fully phaseseparated amorphous phases are present. The melting temperatures change with PDO content. The amount of PDO has an effect on both TmA and TmB . TmA is attributed to the lamella consisting of extended T4T segments,while TmB results from the much thicker lamella consisting of both extended T4T and PDO segments. It is also possible that some PDO is present in the interphase as adjacent re-entry groups. So the resultant copolymer shows that a complex system,two crystalline phases,two amorphous phases and an interphase are involved in the copolymer. The undercooling for these copolymers is small,which means that these segmented copolymers crystallize fast.     

Influence of modifiers and glass-forming ions on the crystallization of glasses of the NaCaPO4–SiO2 system

Silicate?Cphosphate glasses of the XYPO₄?CSiO₂ and XYPO₄?CSiO₂?CAlPO₄ (where X?=?Na⁺ and/or K⁺ and Y?=?Ca²⁺ and/or Mg²⁺) systems have been the subject of the presented investigations. Bioactive glasses from these systems are the base for obtaining glass-crystalline biomaterials through a direct crystallization. However, growth of crystalline phases very adversely affects the bioactivity of the glasses. Uncontrolled growth of crystalline phases can be reduced by means of a glass phase separation phenomenon in the silicate?Cphosphate glasses because boundaries of inclusion-matrix phase may be a barrier limiting the growth of crystalline phases. Microscopic and EDX investigations which have been carried out have shown that glass phase separation occurs in glasses belonging to XYPO₄?CSiO₂ and XYPO₄?CSiO₂?CAlPO₄ systems. Introduction of aluminum ions into the glass structure leads to a rapid homogenization of its texture. Based on DSC examinations it has been found out that crystallization of the glasses of XYPO₄?CSiO₂ systems is a multistep process. The presence of several (the number depends on the type of modifiers and glass-forming ions) clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the inclusions with the matrix remaining amorphous or vice versa. It has been shown that, crystallization of glasses of XYPO₄?CSiO₂?CAlPO₄ system is single-stage process, which is the consequence of the homogenizing effect of aluminum ions on their texture.     

Thermal behavior and evolution of the mineral phases of Brazilian red mud

This article studied the thermal behavior and the evolution of the crystalline phases with temperature of the red mud (bauxite tailing) from an aluminum industry at Maranhão, North-Northwestern Brazil. The experiments were carried out by Field Emission Scanning Electron Microscopy (FE-SEM), Simultaneous Thermal Analysis (TG–DSC), Optical Dilatometry up to 1623 K, and X-ray diffraction (XRD) of previously heated samples between 523 and 1523 K. The crystalline phases and the amorphous contents were quantified on raw and heated samples (at 1523 K) according to the Rietveld Quantitative Analysis (RQA) method. The data obtained showed that the raw red mud is composed by a mixture of seven different phases (hematite, goethite, sodalite, anatase, gibbsite, calcite, and amorphous). Finally in the interval of 1023–1523 K the following crystalline phases: hematite, nepheline, sodalite, anatase, perovskite, and pseudobrookite have been observed.     

Solid-state relaxations in linear low-density (1-octene comonomer), low-density,and high-density polyethylene blends

Extensive thermal and relaxational behavior in the blends of linear low-density polyethylene (LLDPE) (1-octene comonomer) with low-density polyethylene (LDPE) and high-density polyethylene (HDPE) have been investigated to elucidate miscibility and molecular relaxations in the crystalline and amorphous phases by using a differential scanning calorimeter (DSC) and a dynamic mechanical thermal analyzer (DMTA). In the LLDPE/LDPE blends, two distinct endotherms during melting and crystallization by DSC were observed supporting the belief that LLDPE and LDPE exclude one another during crystallization. However, the dynamic mechanical β and γ relaxations of the blends indicate that the two constituents are miscible in the amorphous phase, while LLDPE dominates α relaxation. In the LLDPE/HDPE system, there was a single composition-dependent peak during melting and crystallization, and the heat of fusion varied linearly with composition supporting the incorporation of HDPE into the LLDPE crystals. The dynamic mechanical α, β, and γ relaxations of the blends display an intermediate behavior that indicates miscibility in both the crystalline and amorphous phases. In the LDPE/HDPE blend, the melting or crystallization peaks of LDPE were strongly influenced by HDPE. The behavior of the α relaxation was dominated by HDPE, while those of β and γ relaxations were intermediate of the constituents, which were similar to those of the LLDPE/HDPE blends. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1633–1642, 1997