Microstructural development of a vitrified hindered phenol compound during thermal annealing

Structural changes in vitrified 3,9-bis{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5,5]-undecane (AO-80) during the annealing process were studied by DSC, WAXD and FT-IR. The initial AO-80 is highly crystalline, whereas AO-80 obtained by cooling from its melting state is an amorphous material. Annealing treatments below the melting point of AO-80 resulted in structural development. In addition, the modification of the crystal formed by annealing treatment depended on the annealing conditions. The IR spectra of various crystal modifications were different. Analysis of the microstructures of the crystals that formed indicated that the crystal formed by annealing at 100 °C is a smectic crystal, whereas the crystal formed by annealing at 80 °C is a nematic crystal. The AO-80 crystal formed within the chlorinated polyethylene (CPE) matrix during annealing at 100 °C is also a nematic crystal. Though the CPE matrix decreased regularity of AO-80 crystals, it raised the growth rate of AO-80 crystals.     

Polycarbonate/liquid crystalline polymer blend: Crystallization of polycarbonate

The enhanced crystallization of polycarbonate in the blend of liquid crystalline polymer/polycarbonate/(ethylene-methyl acrylate-glycidyl methacrylate) copolymer (LCP/PC/E-MA-GMA) was studied by wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The LCP/PC/E-MA-GMA 5/95/5 blends annealed at 200 °C, for 2, 4, 6, and 10 h, present an obvious crystalline structure corresponding to PC crystallization. The PC crystal obtained shows two melting temperature, T_m1 of about 214 °C and T_m2 of about 231 °C, with a total heat of fusion of 29 J/g (annealing time = 10 h). The preliminary results indicate that amorphous PC can be induced to crystallization by the synergistic action of LCP dispersed phase and reactive compatibilizer.     

Effects of silicalite-1 nanoparticles on rheological and physical properties of HDPE

The addition of silicalite-1 nanoparticles (0.2-20 wt%) increased slightly the crystallization temperature of HDPE with silicalite-1 content, at 20 wt% loading by ca. 2.5 °C, but it had little effect on the melting temperature. The nanocomposites displayed a little higher onset degradation temperature than pure polymer by 7-11 °C. The WAXD profiles showed that the intensity of diffraction peaks for HDPE was decreased with increasing silicalite-1 content from 5 wt% but that the peak position of every crystal plane did not shift in the presence of silicalite-1 nanoparticles. The incorporation of the nanoparticles increased the melt viscosity of HDPE with silicalite-1 content. It also increased both storage (G′) and loss modulus (G″). In the so-called Cole-Cole plot, pure HDPE showed a single master curve whose slope was 1.37, while the nanocomposites with 10 and 20 wt% silicalite-1 exhibited the inflection in the low frequency range before which the slopes were 1.22 and 1.02, respectively. Much more accelerated crystallization behavior under shear was observed with silicalite-1 content at the isothermal crystallization temperature of 125 °C than at 120 °C.     

Thermal, spectroscopy, and morphological studies on polymorphic crystals in poly(heptamethylene terephthalate)

Polymorphism and its influential factors in poly(heptamethylene terephthalate) (PHepT) were probed using differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide angle X-ray diffraction (WAXD). PHepT exhibits two crystal types (α and β) upon crystallization at various isothermal melt-crystallization temperatures (T_cs) by quenching from different T_maxs (maximum temperature above T_m for melting the original crystals). Melt-crystallized PHepT with either initial α- or β-crystal by quenching from T_max lower than 110 °C leads to higher fractions of α-crystal, but crystallization from T_max higher than 140 °C leads to higher fractions of β-crystal. In addition to T_max, polymorphism in PHepT is also influenced by crystallization temperature (T_c = 25-75 °C). When PHepT is melt-crystallized from a high T_max = 150 °C (completely isotropic melt), it shows solely β crystal for higher T_c, and solely the α-crystal for T_c < 25 °C; in-between T_c = 25 and 35 °C, mixed fractions of both α- and β-crystals. However, by contrast, when PHepT is melt-crystallized from a lower T_max = 110 °C, it shows α-crystal only at all T_cs, high or low.     

A unique crystallization and double melting behavior of a polyimide derived from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and 1,4-bis(3-aminopropyl)piperazine

A unique crystallization and melting behavior of a novel semicrystalline polyimide derived from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and 1,4-bis(3-aminopropyl)piperazine were studied by differential scanning calorimetry (DSC) with and without temperature modulation and wide-angle X-ray diffraction (WAXD). Polymer samples isolated from a chloroform solution showed melting transitions in the DSC. However, WAXD traces showed crystallinity only after annealing above the glass transition, for about 2 h. For samples crystallized from the melt, crystallization could be achieved only in a narrow crystallization range of 200-220 °C, after 10 h. A maximum crystallinity of this polyimide was found to be 30%. Two distinct melting transitions were observed by DSC, which could be explained using a partial disordering—reorganization—final melting model.     

Confined crystallization phenomena in immiscible polymer blends with dispersed micro-and nanometer sized PA6 droplets part 4: polymorphous structure and (meta)-stability of PA6 crystals formed in different temperature regions

The genesis and stability of different PA6 crystalline polymorphs, dispersed as micro- and submicrometer sized droplets inside an amorphous polymer matrix, are discussed over a very broad temperature range. Different PA6 droplet sizes lead to different PA6 crystallization events in a 100 °C wide temperature window that extends down to 85 °C. Static WAXD and DSC experiments on micrometer sized PA6 droplets indicate the formation of a stable γ-crystal phase in the region between 175 and 130 °C. Sub-micrometer sized PA6 droplets only crystallize at 85 °C in the β-phase. Upon heating above the PA6 glass transition, these crystals progressively increase their perfection and ultimately transform into the α-phase around 170 °C.     

Orientation-induced crystallization of poly(ethylene terephthalate) fibers with controlled microstructure

Orientation-induced crystallization of PET fibers was studied by the in-situ wide-angle X-ray diffraction (WAXD) utilizing synchrotron radiation source combined with thermomechanical analysis. The noncrystalline as-spun fiber spun was heat-treated at 150, 165, 180 and 195 °C for 0.1 s under constrained condition. The heat-treatment allowed the fibers to have various amount of isotropic amorphous (IA), oriented noncrystalline (ON), and crystalline (Cr) phase. The structure evolution accompanying the crystallization of the fibers was then examined upon elevating temperature while the fiber length was held constant. The X-ray results clearly showed that the crystallization takes place first by ON phase (extended-chain crystallization) and then followed by the crystallization of IA phase (folded-chain crystallization). The on-set of extended-chain crystallization was dependent on the amount and degree of orientation of ON phase in the fiber that was derived from the various heat-treatment temperatures. It is also noted that the IA phase transforms into not only the CR phase but also the ON phase. The crystallization on the surface of preformed extended-chain crystals appeared to induce the spontaneous orientation of the chains. The thermomechanical data indicated that a stress emerges rapidly on fiber above glass transition temperature (T_g), which is associated with the entropic relaxation of the ON phase. The stress emerged on fiber then dropped drastically as the temperatures of fibers reached the temperatures of extended-chain crystallization, indicating that the stress drop is closely related with the extended-chain crystallization. The fibers heat-treated at the highest temperature showed the highest initial crystallinity but showed the slowest crystallization rate, resulting in the lowest final crystallinity among the fibers.     

Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)

Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-T_m component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-T_m component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.     

Carbon nanotubes induced crystallization of poly(ethylene terephthalate)

We have investigated the crystallization characteristics of melt compounded nanocomposites of poly(ethylene terephthalate) (PET) and single walled carbon nanotubes (SWNTs). Differential scanning calorimetry studies showed that SWNTs at weight fractions as low as 0.03 wt% enhance the rate of crystallization in PET, as the cooling nanocomposite melt crystallizes at a temperature 10 °C higher as compared to neat PET. Isothermal crystallization studies also revealed that SWNTs significantly accelerate the crystallization process. WAXD showed oriented crystallization of PET induced by oriented SWNTs in a randomized PET melt, indicating the role of SWNTs as nucleating sites.     

Thermal analysis, X-ray and electron diffraction studies on crystalline phase transitions in solvent-treated poly(hexamethylene terephthalate)

The crystal polymorphism, transformation, and morphologies in chloroform solvent-cast poly(hexamethylene terephthalate) (PHT) were examined by using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and temperature in situ transmission electron microscopy (TEM). Solvent-induced crystallization of PHT at room temperature yielded an initial crystal of γ-form, as confirmed by WAXD. Upon DSC scanning, the original γ-form in PHT exhibited three endothermic peaks, whose origins and association were carefully analyzed. The first peak, much smaller than the other two, is in the temperature range of ca. 100-120 °C. It was found that the solvent-induced γ-form was transformed to β-form at 125 °C via a solid-to-solid transformation mechanism. In addition, WAXD showed that γ- and β-forms co-existed in the temperature range of 100-125 °C. These mixed crystal forms were further identified using TEM, and the selected-area electron diffraction (ED) patterns revealed that both γ- and β-form crystals co-existed and were packed within the same spherulite. Solid-solid transformation from the solvent-induced γ-form to β-form in PHT upon heat scanning was presented with evidence and discussed.     

Melting and crystallization behavior of poly(trimethylene 2,6-naphthalate)

The melting and crystallization behavior of poly(trimethylene 2,6-naphthalate) (PTN) are investigated by using the conventional DSC, the temperature-modulated DSC (TMDSC), wide angle X-ray diffraction (WAXD) and polarized light microscopy. It is observed that PTN has two polymorphs (α- and β-form) depending upon the crystallization temperature. The α-form crystals develop at the crystallization temperature below 140 °C while β-form crystals develop above 160 °C. Both α- and β-form crystals coexist in the samples crystallized isothermally at the temperature between 140 and 160 °C. When complex multiple melting peaks of PTN are analyzed using the conventional DSC, TMDSC and WAXD, it is found that those arise from the combined mechanism of the existence of different crystal structures, the dual lamellar population, and melting-recrystallization-remelting. The equilibrium melting temperatures of PTN α- and β-form crystals determined by the Hoffman-Weeks method are 197 and 223 °C, respectively. When the spherulitic growth kinetics is analyzed using the Lauritzen-Hoffmann theory of secondary crystallization, the transition temperature of melt crystallization between regime II and III for the β-form crystals is observed at 178 °C. Another transition is observed at 154 °C, where the crystal transformation from α- to β-form occurs.     

Acceleration or retardation to crystallization if liquid-liquid phase separation occurs: Studies on a polyolefin blend by SAXS/WAXD, DSC and TEM

Blends of statistical copolymers containing ethylene/hexene (PEH) and ethylene/butene (PEB) exhibited the behavior of upper critical solution temperature (UCST). The interplay between the early and intermediate stage liquid-liquid phase separation (LLPS) and crystallization of the PEH/PEB 50/50 blend was studied by time-resolved simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. Samples were treated by two different quench procedures: in single quench, the sample was directly quenched from 160 °C to isothermal crystallization temperature of 114 °C; while in double quench, the sample was firstly quenched to 130 °C for 20 min annealing, where LLPS occurred, and then to 114 °C. It was found that in the early stage of crystallization, the integrated values of Iq² and crystallinity, X_c, in the double quench procedure were consistently higher than those in the single quench procedure, which could be attributed to accelerated nucleation induced by enhanced concentration fluctuations and interfacial tension. In the late stage of crystallization, some morphological parameters were found to crossover and then reverse, which could be explained by retardation of lamellar growth due to phase separation formed during the double quench procedure. This phenomenon was also confirmed by DSC measurements in blends of different compositions at varying isothermal crystallization temperatures. The crystal lamellar thickness determined by SAXS showed a good agreement with TEM observation. Results indicated that the early stage LLPS in the PEH/PEB blend prior to crystallization indeed dictated the resulting lamellar structures, including the average size of lamellar stack and the stack distribution. There seemed to be little variation of lamellar thickness and long period between the two quenching procedures (i.e., single quench versus double quench).     

Isothermal crystallization of isotactic polypropylene blended with low molecular weight atactic polypropylene. Part I. Thermal properties and morphology development

The thermal properties and morphology development of isotactic polypropylene (iPP) homopolymer and blended with low molecules weigh atactic polypropylene (aPP) at different isothermal crystallization temperature were studied with differential scanning calorimeter and wide-angle X-ray scattering. The results of DSC show that aPP is local miscible with iPP in the amorphous region and presented a phase transition temperature at T_c=120 °C. However, below this transition temperature, imperfect α-form crystal were obtained and leading to two endotherms. While, above this transition temperature, more perfect α- and γ-form crystals were formed which only a single endotherm was observed. In addition, the results of WAXD indicate that the contents of the γ-form of iPP remarkably depend both on the aPP content and isothermal crystallization temperature. Pure iPP crystallized was characterized by the appearance of α- and γ-forms coexisting. Moreover, the highest intensity of second peak, i.e. the (0 0 8) of γ-form coexisting with (0 4 0) of α-form, and crystallinity were obtained for blended with 20% of aPP, the γ-form content almost disappeared for iPP/aPP blended with 50% aPP content. Therefore, detailed analysis of the WAXD patterns indicates that at small amount aPP lead to increasing the crystallinity of iPP blend, at larger amount aPP, while decreases crystallinity of iPP blends with increasing aPP content. On the other hand, the normalized crystallinity of iPP molecules increases with increasing aPP content. These results describe that the diluent aPP molecular promotes growth rate of iPP because the diluent aPP molecular increases the mobility of iPP and reduces the entanglement between iPP molecules during crystallization.     

Phase transitions and structural parameters of HIQ-40 liquid crystalline co-polyester

We describe the impact of thermal treatment on the structure and phase transitions of the liquid crystalline aromatic co-polyester, HIQ-40, comprising 40 mol% p-hydroxybenzoic acid (H), 30 mol% isophthalic acid (I), and 30 mol% p-hydroquinone (Q). Simultaneous, real-time wide and small angle X-ray scattering (WAXS, SAXS), differential scanning calorimetry, and optical ellipsometry were used to study initially isotropic, amorphous films of HIQ-40. Films were annealed above the glass transition temperature, T_g, at temperatures, T_a, from 130 to 290 °C. Depending upon T_a, thermal treatment results in formation of regions of nematic order and/or crystalline order in a disordered matrix. As T_a increases, molecular mobility in the amorphous phase increases resulting in a reduction in T_g. Two or three endothermic events are seen in all samples by thermal analysis. The lowest temperature endotherm is associated with melting of crystals formed either at T_a or during the thermal scan. The two higher temperature endotherm features result from transformation of crystal melt-to-nematic, and formation of more mobile nematic domains from constrained liquid, respectively, and are relatively insensitive to T_a.A strong Bragg scattering peak is seen for corresponding to formation of two-phase structure comprising crystals and disordered phase. At higher temperatures, very strong scattered intensity in the SAXS pattern re-emerges, even after all WAXS crystal reflections have disappeared. Results suggest that a two-phase structure, of ordered nematic domains co-existing with less ordered regions, may be forming continuously above the crystal melting point.     

Synthesis and characterization of poly(ester amide)s containing crystallizable amide segments

High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of 1,4-butanediol, dimethyl adipate and a preformed bisamide-diol based on 1,4-diaminobutane and ε-caprolactone. By varying the ratio of the bisamide-diol and 1,4-butanediol, a series of polymers was obtained with a hard segment content between 10 and 85 mol%. FT-IR and WAXD analysis revealed that the poly(ester amide)s crystallize in an α-type phase similar to the α-phase of even-even nylons. These polymers all have a micro-phase separated structure with an amide-rich hard phase and an ester-rich flexible soft phase. The polymers have a low and a high melt transition, corresponding with the melting of crystals comprising single ester amide sequences and two or more ester amide sequences, respectively. The low melt transition is between 58 and 70 °C and is independent of polymer composition. By increasing the hard segment content from 10 to 85 mol% the high melt transition increased from 83 to 140 °C while the glass transition temperature increased from −45 to −5 °C. Likewise, the elastic modulus increased from 70 to 524 MPa, the stress at break increased from 8 to 28 MPa while the strain at break decreased from 820 to 370%. Thermal and mechanical properties can thus be tuned for specific applications by varying the hard segment content in these segmented polymers.     

Effects of crystallization temperature on the polymorphic behavior of syndiotactic polystyrene

The influence of crystallization temperature on formation of the α- and β-form crystals of syndiotactic polystyrene (sPS) was investigated by X-ray diffraction and non-isothermal differential scanning calorimetry analysis. For sPS samples without any thermal history, the crystallization temperature must be the intrinsic factor controlling the formation the α and β-form crystals. Being crystallized at different cooling rate from the melt, sPS forms the β-form crystal until the temperature cooled down to about 230 °C, and α-form crystal can only be obtained when the temperature was below about 230 °C.     

Fast isothermal calorimetry of modified polypropylene clay nanocomposites

Calorimetric experiments at cooling rates comparable to those during injection molding, as an example, are needed to study phase transitions under conditions relevant for processing. Ultra fast scanning calorimetry is a technique which provides a means to analyze the materials of interest under rapid cooling conditions and it is a promising technique by which the crystallization behavior of composite systems based on fast crystallizing polymers like isotactic polypropylene (iPP) can be studied. By combining conventional DSC and ultra fast chip calorimetry isothermal crystallization experiments were performed in the whole temperature range between glass transition and melting temperature of iPP. Because of the very small time constant of the calorimeter, isothermal crystallization processes with peak times down to 100 ms were investigated after cooling the sample from the melt at 2000 K/s. iPP grafted with maleic anhydride (PPgMA) - montmorillonite clay nanocomposites were studied. The influence of various clay loadings on the crystallization behavior of PPgMA at different temperatures was followed by ultra fast isothermal calorimetry. PPgMA clay nanocomposites showed a variation in crystallization peak times with different clay loadings at crystallization temperatures between 70 °C and 100 °C. No influence of clay loading was observed at lower crystallization temperatures. At these temperatures, where the mesophase is formed and homogeneous nucleation is expected, the contribution of the clay as a nucleating agent is negligible. For crystallization at about 80 °C, where the α-phase is formed, the nucleating effect of the clay is observed yielding complex crystallization kinetics. In the temperature range 75-85 °C in some nanocomposites a double peak during isothermal crystallization was observed corresponding to a fast and a slow crystallization processes occurring simultaneously. At higher temperatures, above 120 °C, the clay slightly retards the crystallization process.     

Incorporation of different crystallizable amide blocks in segmented poly(ester amide)s

High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of dimethyl adipate, 1,4-butanediol and a symmetrical bisamide-diol based on ε-caprolactone and 1,2-diaminoethane or 1,4-diaminobutane. FT-IR and WAXD analysis revealed that segmented poly(ester amide)s based on the 1,4-diaminobutane (PEA(4)) give an α-type crystalline phase whereas polymers based on the 1,2-diaminoethane (PEA(2)) give a mixture of α- and γ-type crystalline phases with the latter being similar to γ-crystals present in odd-even nylons. PEA(2) and PEA(4) polymers with a hard segment content of 25 or 50 mol% have a micro-phase separated structure with an amide-rich hard phase and an ester-rich flexible soft phase. All polymers have a glass transition temperature below room temperature and melt transitions are present at 62-70 °C (T_m,1) and at 75-130 °C (T_m,2) with the latter being highest at higher hard segment content. The two melt transitions are ascribed to melting of crystals comprising single ester amide sequences and two or more ester amide sequences, respectively. These polymers have an elastic modulus in the range of 159-359 MPa, a stress at break in the range of 15-25 MPa combined with a high strain at break (590-810%). The thermal and mechanical properties are not influenced by the different crystalline structures of the polymers, only by the amount of crystallizable hard segment present.     

Conformation transition and crystalline phase variation of long chain branched isotactic polypropylenes (LCB-iPP)

The changes of conformation and crystalline structure of long chain branched isotactic polypropylene (LCB-iPP) under different crystallization temperatures and the effects of their special molecular architecture on the crystallization behavior were investigated by a combination of Fourier transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). In these polymers, long chain branching was introduced via in situ polymerization of polypropylene and an asymmetric diene monomer using the metallocene catalyst technology. Through the characterization of the specific IR band variation, it was proved that the conformational orders of helical sequences of LCB-iPP show great changes in different crystallization temperature ranges. In lower crystallization temperature range (100-130 °C), the intensities of all regular helical conformation bands of LCB-iPP increase with the increasing crystallization temperature and the regular helical conformation bands with more monomer units increase faster than that with less monomer units. In higher crystallization temperature range (130-150 °C), the intensities of all regular helical conformation bands of LCB-iPP decrease with the increasing crystallization temperature and the regular helical conformation bands with more monomer units decrease faster than that with less monomer units. The results of WAXD and DSC showed that LCB-iPP crystallizes from the melt as a mixture of α and γ forms. The content of the γ form increases with the increasing crystallization temperature, reaches a maximum value at 130 °C, and then decreases with a further increase of the temperature. At the same time, the crystallization of γ form is favored by the presence of the LCB structure of iPP. Moreover, the transitional temperatures of different helical conformations and crystallization structures of LCB-iPP show obvious correlations.     

Crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) studied by 2D IR correlation spectroscopy

Crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx)) (HHx=12 mol%) was studied by means of two-dimensional infrared (2D IR) correlation spectroscopy. Three types of crystallization; the gradual cooling from the melt, the isothermal crystallization of the supercooled melt, and the isothermal crystallization of the solution-cast film were investigated. The order of crystal growth steps taking place during the three different types of crystallization processes was analyzed in detail. It was revealed by the asynchronous 2D correlation spectra generated from the dynamic IR spectra in the CO stretching band region that the development of the highly ordered crystals occurs prior to that of the less ordered crystals for the gradual cooling crystallization. On the other hand, for the supercooled melt and solution-cast film crystallization, the formation of the less ordered crystals takes place before that of the highly ordered crystals. The transition from the amorphous phase to the less ordered crystals is a simultaneous process for all three types of crystallization.