CO2-induced Crystallization of Isotactic Polypropylene by Annealing Near Its Melting Temperature

CO₂-induced crystallization of isotactic polypropylene (iPP) by annealing had been studied using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). The iPP before annealed was in α-form and amorphous states. At lower temperatures by CO₂ isothermal treatments, iPP chains crystallized from the amorphous phase and only one crystal form, i.e., α-form, was observed. At higher temperatures by CO₂ isothermal treatments, both crystallization from the amorphous phase and thickening of existing crystal lamellae were observed. Moreover, light γ-form crystal appeared in the treated iPP. The crystalline lamellar thickness of iPP annealed at different CO₂ pressures had been determined. Using the Gibbs–Thomson plot method, the equilibrium melting temperature was found to be 187.6°C.     

Effect of Temperature and Comonomer Content on Thermal Behavior and Crystallization Property of the Propylene–Ethylene Random Copolymers

The effects of ethylene units content and crystallization temperature on the conformations, and the thermal and crystallization behavior were investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). The characterization of FTIR spectroscopy proves that the longer helical conformation sequences of the propylene–ethylene random (PER) samples decrease, whereas the shorter helical conformation sequences increase with the increase in ethylene units content. The increase of the shorter helical conformation sequences is favorable for the formation of the γ-phase in the crystals. A group of broad endothermic peaks can be seen clearly in the DSC curves of PER copolymers, which may be associated with the melting of mixtures of the α- and γ-forms in the crystals. The melting point, crystallization temperature, and crystallinity degree of the PER copolymers decrease with the increase in ethylene units contents. Three typical melting peaks of the PER copolymers crystallized isothermally between 80°C and 130°C were observed. The two higher melting peaks result from melting of the α- and γ-phase in the crystals, whereas the materials crystallized on quenching give the lowest peak. The WAXD results confirm that the PER copolymers crystallize from the melt, as mixtures of α and γ forms, in a wide temperature range. The critical number ζ_lim of the crystallizable units for the α-form increases with the increase in crystallization temperature for PER copolymers, which is favorable for the formation of the γ phases. The amount of γ-form increases with the increase in crystallization temperature at the expense of its α component, then reaches a maximum value at the crystallization temperature of 115°C, and finally decreases with further increase in the crystallization temperature.     

Studies on crystalline forms of Nylon 6. III. Crystallization from the glassy state

The relative amounts of the α- and γ-crystalline forms of nylon 6 obtained from the glassy state under different crystallization conditions have been studied by the X-ray diffraction procedure described in the previous paper. The weight fraction of the γ-form decreases with increasing crystallization temperature above 160°C and that of the α-form increases. Growth of the γ-form is predominant in crystallization at 100°C and of the α-form at 200°C. Differential scanning calorimetry and density data are presented. A large amount of a thermally unstable form is included in the γ-form crystallized from the glassy state at lower crystallization temperatures and is transformed into the a-form with annealing at 200γC. Thermal stability of the γ-form obtained from the glassy state was quantitatively investigated and discussed.     

Isothermal Crystallization and Melting Behavior of Composites Composed of Poly(L-lactic Acid) and Poly(glycolic Acid) Fibers

Several composites of poly (L-lactic acid) (PLLA) with poly (glycolic acid) (PGA) fibers were prepared. The isothermal crystallization kinetics and melting behavior of PLLA and all of the composites were characterized by using differential scanning calorimetry. The experimental data were processed by using the Avrami equation. The relative parameters, such as the Avrami exponent and half-time crystallization, revealed that PGA fibers had positive effects on the crystallization of PLLA, but these effects had only a minimal dependence on the PGA fiber content. Moreover, at low isothermal crystallization temperatures (85°C～110°C), recrystallization during the heating scan was observed, which could lower the melting point of the samples to a certain extent.     

Melting behavior of the oriented β-phase polypropylene texture crystallized by the temperature slope method

Isotactic polypropylene consisting of uniaxially oriented P-phase lamellae was crystallized in a temperature gradient. The β → α transition was investigated by simultaneous measurements with differential scanning calorimetry (DSC) and X-ray diffraction using synchrotron radiation (SR). To compare the transition mechanism, the β-phase sample was deformed by rolling it along the direction of the crystallization. During rolling, the β-crystal is deformed by interlamellar and interchain slip, which induces c-axis-oriented molecules along the rolling direction. The melting behavior is changed by the rolling deformation. For the as-grown β-crystal, the DSC thermogram has three peaks: the β-melting endotherm at 150°C, an exotherm by recrystallization into the °-form, and the endotherm at 167°C caused by melting of the recrystallized α-form. After the rolling deformation, the β-endotherm is extinguished by the successive exotherm. Simultaneous X-ray measurements reveal that the β → α transition is shifted to a lower temperature and that the recrystallized α-form has a c-axis-orientation caused by the rolling deformation. In the process of the β→ α transition, higher-order lamellar structure is developed earlier than formation of the crystalline structure. In this study, the heating phenomena, such as the β α transition and thickening of the β- and α-lamellae, are consistently explained by a mechanism involving melting and subsequent recrystallization.     

Hydrolysis etching of crystalline and amorphous poly(ethylene terephthalate): Influence of molecular weight and microstructure

The degradation of samples of amorphous and semicrystalline PET with different molecular weights by means of hydrolysis at 180°C has been investigated by measuring the weight loss and the x-ray crystallinity as a function of etching time. It is shown that during the first hours of etching, a concurrent crystallization of the amorphous samples takes place. It is found that weight loss values of amorphous samples after long etching times are higher than the weight loss of the crystallized materials. Results also indicate that weight loss depends to some extent on the initial degree of crystallinity of the material. It is emphasized that the lateral size of the crystallites is a major parameter in determining the total amount of etched material. Analysis of results further confirms that mainly the amorphous regions lying outside of the lamellar stacks are removed by hydrolysis. However, the crystals formed during annealing of the amorphous samples at 180°C are less perfect and the lamellar stacks in these samples are more affected by the hydrolysis attack than in the previously crystallized PET samples.     

Thermal Performance of a Blend System Based on Poly(l-lactic acid) and an Aliphatic Multiamide Derivative of 1H-Benzotriazole

An aliphatic multiamide derivative derived from 1H-benzotriazole, N, N'-bis(1H-benzotriazole) sebacic acid acethydrazide (SA), was synthesized to evaluate its effect on the thermal performance, including non-isothermal crystallization and melting behavior as well as thermal stability, of poly(l-lactic acid) (PLLA). The comparative study, by means of DSC measurements, showed that the incorporation of SA caused a non-isothermal crystallization peak to appear and become sharp, showing its advanced crystallization promoting effect for PLLA. The non-isothermal crystallization results further indicated that 2 wt% SA was the saturation concentration for PLLA crystallization, and that the cooling rate was also a crucial determinant for PLLA crystallization. Considering the melting behavior, the difference between the virgin PLLA and PLLA/2%SA further confirmed the crystallization accelerative effect of SA for PLLA, with the increase of crystallization temperature in the temperature zone from 90 to 130°C being beneficial to the crystallization of PLLA during processing. Compared to the virgin PLLA, the trends of thermal decomposition curves were similar, suggesting that the introduction of SA of 0.5–3 wt% did not significantly change the thermal decomposition behavior of PLLA.     

Effect of annealing on the structure of quenched isotactic polypropylene

Smectic isotactic polypropylene films were annealed at different temperatures for different times. Density, wide-angle x-ray scattering (WAXS), differential scanning calorimetry, and the transport properties of methylene chloride vapor were used to follow the transformation of the smectic phase into the monoclinic phase. The results of WAXS diffractograms indicate different saturation levels of crystallization with the maximum order attained progressively more quickly at higher temperatures. Density measurements, however, show that, after a first saturation level, a further increase of this parameter occurs after long annealing times; and this second step is lower, the higher the temperature. Sorption and diffusion, analyzed to investigate the amorphous component, show that annealing the smectic phase at 50°C results in a decrease of amorphous fraction without transformation of the smectic phase. The transition from smectic to monoclinic phase occurs at temperatures higher than 60°C. During the annealing at 80°C there is first a decrease of amorphous fraction corresponding to the first saturation level of the density, and then a further decrease of amorphouse phase corresponding to the final increase of density after 24 hr of annealing.     

Effect of annealing on the structure and morphology of nylon 6 fibers

Changes in the structure of nylon 6 fibers annealed in dry and wet atmospheres were studied by small-and wide-angle x-ray diffraction. In the presence of water or saturated steam, fibers can be annealed to the same strucutral state at temperatures 70°C lower than in dry atmosphere. This is due to the enhanced mobility of the molecular segments in the amorphous region, a mechanism which is also known to lower the T_g by the same amount. Upon annealing under unconstrained conditions, lamellar spacing, crystallite size in the equatorial plane, crystalline as well as fiber density, and the chain-axis repeat increase with annealing-temperature; whereas crystalline orientation and the Van der Waals separation of the hydrogen-bonded sheets decrease. The monoclinic angle 8 remains constant at 66.7° (σ = 0.3°) and might depend on the starting fiber rather than on the treatment of the fiber. Most of these changes occur above a critical temperature of 170°C if dry, or 100°C if wet; rate of crystallization is also the highest under these conditions in nylon. The effect of these changes on such fiber properties as dyeing and the role of micro voids in dye diffusion and in dye uptake are discussed. Surface premelting and the accompanying changes in the surface structure of the lamellae, selective melting, and more importantly, the longitudinal motion of the nylon 6 chains and the resulting folding of interfibrillar extended amorphous chains are invoked to explain the shrinkage of the fiber, disorientation of the crystallites, increase in crystalline perfection, and the increase in lamellar spacing.     

Recoilless fraction, structural, magnetic and thermal properties of Fe73.5Cu1Nb3Si13.5B9 alloy

Differential scanning calorimetry, X-ray diffraction and room temperature Mössbauer spectrum measurements of Fe_73.5Cu₁Nb₃Si_13.5B₉ (Finemet) alloy have been carried out in order to study its structural and magnetic properties as a function of annealing temperature. The DSC profile of as-quenched Finemet showed two exothermic peaks at 530 and 702 °C, corresponding to two crystallization processes. The Finemet alloy remains amorphous at 450 °C with one broad peak in XRD pattern and one broad sextet in Mössbauer spectrum. When the Finemet alloy was annealed at 550 °C, only well indexed body-center-cubic phase was detected. After being annealed at 650 and 750 °C, the XRD patterns showed the coexistence of α-Fe(Si) and Fe-B intermetallic phases with the increase in XRD peak intensities, indicating the growth of crystallites and the decomposition of Fe_73.5Cu₁Nb₃Si_13.5B₉ alloy at elevated temperatures. The Mössbauer spectra of annealed Finemet alloy could be fitted with 4 or 5 sextets and one doublet at higher annealing temperatures, revealing the appearance of different crystalline phases corresponding to the different Fe sites above the crystallization temperature. The appearance of the nanocrystalline phases at different annealing temperatures was further confirmed by the recoilless fraction measurements.     

Correlation Between Structural and Dynamic‐Mechanical Transitions of Different Syndiotactic Polypropylene Polymorphs

Abstract

We prepared several well‐characterized syndiotactic polypropylene (sPP) polymorphs so as to correlate their thermal and dynamic‐mechanical behaviors. A sample was crystallized in pure form I at 100°C; a second sample containing only the trans‐planar mesophase was prepared by directly drawing a quenched sample at 0°C; a third sample, drawn at room temperature, contained both the trans‐planar mesophase and a fraction of the helical form II. By annealing this sample at increasing temperatures, we obtained a series of samples containing either trans‐planar mesophase, or form II and form I crystallinities.

In the dynamic‐mechanical analysis, the sample containing form I crystallinity showed only the amorphous glass transition, at 19°C, before melting at a high temperature. The trans‐planar mesophase transformed, at temperatures higher than 50°C, into the helical forms, and this transition was completed at 80°C. The dynamic mechanical curve of the sample containing only the mesophase showed a peak, centered at 50°C, which could be clearly associated to this transition. The sample containing the trans‐planar mesophase and the helical form II, showed in the dynamic‐mechanical curve a third peak that can be associated with the melting recrystallization of form II into the most stable form I. These results are important, because it was possible to directly correlate the structural transitions of the sPP polymorphs to the dynamic‐mechanical behavior. Moreover, a dynamic‐mechanical analysis could help recognize the presence of the trans‐planar mesophase or of the helical form II in more complex structural organizations.     

Influence of Degradation of Poly-L-lactide on Mass Loss,Mechanical Properties,and Crystallinity in Phosphate-Buffered Solution

A bulk degradation of poly-L-lactide (PLLA) rectangular bars was studied by incubating them in phosphate-buffered solution at 37°C for different periods. The characteristics of the mass, water uptake, mechanical properties, thermal behavior, and crystallinity of the PLLA samples were investigated. The results indicate that mass loss and water uptake of PLLA increase with increasing time; however, pH value and mechanical strength decrease. The melting temperature, melting enthalpy, and crystallinity of PLLA firstly increase and then decrease with increasing degradation time. There is no new diffraction peak formed with increasing degradation time, which indicates that the degradation could occur in the amorphous regions firstly and then in the crystalline regions.     

Photoinduced darkening, crystallization and reversible emission in ZnTe thin films

Laser-induced darkening and crystallization of ZnTe-based thin films is reported. ZnTe thin films of 1500-nm thickness were deposited on bare and Zn buffer layered borosilicate glass substrates. The as-deposited films were subjected to laser irradiation at 532 nm. The as-deposited films were amorphous but transformed to the crystalline state under influence of the laser treatment. The X-ray diffraction patterns revealed that the ZnTe crystallized in the zinc blende structure. In addition, presence of peaks from Te was observed, signifying the dissociation of ZnTe. The spectral transmission of the films decreased by more than 15 % under the influence of the laser irradiation and this was accompanied by a red shift in the band gap. These results clearly point to the occurrence of laser-induced darkening and crystallization of the films. To understand the mechanisms of darkening and crystallization, all the films were annealed at 500 °C for 60 min. Similar to the laser-irradiated samples, the thermally annealed films showed an amorphous–crystalline transition, presence of Te in the X-ray diffraction patterns as well as a large decrease in spectral transmission (>70 %). Photoinduced emission analysis carried out as a function of laser intensities indicated a strong red shift of about 51 meV in emission energy with increase in laser intensity due to the photodarkening. The peak position of the emission spectrum can be tuned by increasing the laser intensity and is completely reversible with decrease in laser intensity. It is proposed that laser-induced darkening occurs due to the dissociation of ZnTe into ZnTe and Te and that crystallization is a consequence of laser annealing.     

Thermal annealing of a-Si:H/a-SiNx:H multilayers

The crystallinity of Si/SiN_x multilayers annealed by a rapid thermal process and furnace annealing is investigated by a Raman-scattering technique and transmission electron microscopy. It is found that the crystallization temperature varies from 900 °C to 1000 °C when the thickness of a-Si:H decreases from 4.0 nm to 2.0 nm. Raman measurements imply that the high crystallization temperature for the a-Si:H sublayers originates from the confinement modulated by the interfaces between a-Si:H and a-SiN_x:H. In addition to the annealing temperature, the thermal process also plays an important role in crystallization of a-Si sublayers. The a-Si:H sublayers thinner than 4.0 nm can not be crystallized by furnace annealing for 30 min, even when the annealing temperature is as high as 1000 °C. In contrast, rapid thermal annealing is advantageous for nucleation and crystallization. The origin of process-dependent crystallization in constrained a-Si:H is briefly discussed. Received: 11 April 2001 / Accepted: 20 June 2001 / Published online: 30 August 2001     

The Effect of Crystallization on the Solid State Polycondensation of Poly(L‐lactic Acid)

Melt solid polycondensation is an approach to increase the molecular weight of poly (L‐lactic acid) (PLLA). For this report, the effect of crystallization time of PLLA prepolymer on the molecular weight of the biomaterial was studied. In this process, PLLA prepolymer with a molecular weight of 18,000 was first prepared by the ordinary melt‐polycondensation process. The prepolymer was crystallized at 105°C for various times, and then heated at 135°C for 15–50 h for further solid state polycondensation (SSP). The differential scanning calorimetry (DSC) and viscosity measurements were used to characterize the crystalline properties and molecular weight of the resulting PLLA polymers, respectively. The results showed that the molecular weight of PLLA reached a maximum value under the condition of a crystallization time of 30 min and SSP of 35 h.     

Structural characterisation and thermal stability of SnSe\GaSb stacked films

We have investigated the effect of thermal annealing on the structure of single and stacked phase change memory films based on SnSe and GaSb. Samples were prepared by pulsed laser deposition and investigated by X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) methods. Electrical resistance versus temperature investigations showed crystallisation temperatures of 292°C and 198°C for SnSe and GaSb single films, respectively. Above the transition temperature, GaSb crystallises into a face-centered cubic structure, whereas SnSe has an orthorhombic arrangement. Annealing at three temperatures (160°C, 250°C and 350°C) of the SnSe\GaSb stacked films promotes bond breaking, atom diffusion between the two layers and formation of new phases. At 160°C, GaSb films crystallise partially and no effect is observed on the crystallinity of SnSe films. After 250°C, rhombohedral SnSb emerges in addition to GaSb complete crystallisation. A major, completely new, body-centered orthorhombic unindexed quaternary Ga-Sn-Sb-Se phase formation was observed in the samples annealed at 350°C. The GaSb crystallites are fully dissolved and we have observed the formation of a minor hexagonal SnSe₂ phase. The analysis of EXAFS data, measured at Se and Ga K-edges, revealed changes in the local atomic environment as a function of the annealing temperature. A tetrahedral configuration is obtained for the Ga atoms in both as-deposited and annealed samples, whereas Se is mostly bivalent in the amorphous samples and has an octahedral arrangement in crystalline SnSe. Our results show that inter-layer diffusion should always be considered and evaluated when designing memory cells composed of stacked phase change chalcogenide films.     

非晶La80Al20晶化相的超导电性

 本文把非晶La₈₀Al₂₀在真空中、不同温度及其时间条件下进行退火，以及在6 GPa不同温度退火40 min，并对退火样品的相结构及超导性进行了研究。发现真空中，250 ℃退火的样品晶化成了T>4.2 K、不超导的单相四方La₄Al；300 ℃及450 ℃退火的样品晶化成La₃Al、α-La、β-La及一些未知杂相，这些多相混合物的T_C<6.0 K。在6 GPa 300 ℃及以下温度退火的样品，晶化成单相六角La₄Al，其晶格常数与六角La₃Al的完全相同，这些样品的T_C>5.1 K；6 GPa、350 ℃及以上温度退火的样品，晶化成La₃Al相及新未知相H，新相H的T_C约为6.3 K。     

Melting Point Elevation of Isotactic Polypropylene

The melting point of a conventional isotactic polypropylene (PP) was enhanced by a rapid annealing procedure of an extruded sheet composed of β trigonal form crystals having thick lamellae, which was prepared by T-die processing with a specific β-nucleating agent, N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide. Although the melting point of PP with α monoclinic form, prepared by a conventional processing method, is known to be located around at 165°C, the sample obtained by the present technique showed a higher melting point, 170°C. The phase transformation from β-to α-form crystals, retaining the lamellar thickness, was responsible for the melting point elevation.     

Surface properties of Fe76Mo8Cu1B15 alloy after annealing

NANOPERM-type alloy Fe₇₆Mo₈Cu₁B₁₅ is investigated in amorphous and in partially crystallized state. Samples were prepared by 1 h isothermal annealing in vacuum at temperatures ranging from 330°C up to 700°C. Bulk and surface microstructural characteristics were studied using transmission and conversion electron Mössbauer effect techniques, respectively. Surface features were checked by the help of atomic force microscopy. Presence of nanocrystalline bcc-Fe phase was detected during the first crystallization stage. The crystallization process starts at 450°C and it is more pronounced in surface regions than in the bulk. With progressing crystallization, hyperfine parameters especially of the amorphous residual phase are altered. Distinctions in surface morphology are revealed between wheel and air side of the ribbon-shaped samples.     

The annealing of damage in ion implanted gallium arsenide

Photoluminescence measurements at 77°K and Rutherford scattering of 450 keV protons were used to study radiation damage and annealing in ion implanted GaAs. The characteristic band edge luminescence (8225 Å) in GaAs is completely quenched by ion implantation. Photoluminescence measurements on samples which were isochronally annealed show a single annealing stage at 600°C. A luminescence peak at 9140 Å is introduced into the spectra of all implanted and annealed samples. This peak is attributed to an acceptor level created by As vacancies. The intensity of the peak is greatly reduced by protecting the surface of implanted layers with SiO₂ during annealing. Rutherford scattering measurements on isochronally annealed samples reveal two annealing stages. A 300°C annealing stage is observed on samples which have an initial aligned yield less than random while a 650°C stage is observed on samples which have an initial aligned yield equal to random.