Morphology and melting behavior of semicrystalline poly(ethylene terephthalate). II. Annealed PET

Annealing of poly(ethylene terephthalate) samples crystallized under isothermal conditions above the crystallization temperature has a marked influence on their morphology and results in increased thermal stability of the crystalline structure as indicated by the melting point increase of the samples. The morphological transformation processes induced by annealing are very complex and depend on the thermal history of the samples, i.e., crystallization temperature and heating procedure. Depending on the nature of the processes occurring during annealing, various parameters characterizing the semicrystalline state of the samples can be affected such as the degree of crystallinity, the long spacing, the thickness of amorphous and crystalline layers, the crystal perfection, the fold-surface structure, and the mosaic structure of the crystalline lamellae. Annealing involves a solid-state transformation of the original crystalline structure including crystal perfection without thickening or a melting followed by recrystallization with crystal perfection and crystal thickening. The combination of differential scanning calorimetric (DSC) measurements and small-angle x-ray scattering is a powerful analytical tool to detect morphological changes and helps in deciding on the processes which are involved in the transformation of the microstructure upon annealing.     

Multiphase structure of segmented polyurethanes: Its relation with spherulite structure

Small-angle light-scattering (SALS), Polarized light microscopy (PLM), differntial scanning calorimetry (DSC), and small-angle x-ray scattering (SAXS) were used to study morphological changes in segmented polyurethanes with 4,4′-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) as the hard segment. It was found. for the first time, that spherulites could form from the melt by quenching the polyurethanes in the melt state to annealing temperatures between 120°C and T_h, the highest annealing temperature for spherulite formation. T_h ranged from 140°C to ca. 170°C and depended upon the hard-and soft-segment compatibility. Within the range 120°C to T_h, the radius of the spherulite increased with increasing hard-segment content at each fixed annealing temperature. Annealing at 135–140°C gave rise to the largest spherulites. SAXS was used to investigate the phase-separated structures corresponding to the spherulite formation. The interdomain spacing increased with increasing hard-segment content and with increasing annealing temperature.The degree of phase separation first increased with increasing annealing temperature from room temperatures (ca. 25°C), reached a maximum at ca. 107°C, and then decreased with further increase in the annealing temperature. On the basis of these observations, the mechanisms of phase separation, crystallization, and spherulite formation are discussed. © 1993 John Wiley & Sons, Inc.     

Solution grown isotactic polystyrene crystals. II. Kinetics of thermal changes by x-ray diffraction

The present paper is a study of the annealing, melting, and recrystallization behavior of solution grown isotactic polystyrene crystals in order to elucidate changes both in total lamellar thickness and in the thickness of the crystalline “core” as a function of temperature. The lamellar thickness was obtained from x-ray long spacings and the core thickness from the broadening of appropriate reflections, both assessed by a high sensitivity x-ray detector system able to produce records within a few minutes during time dependent processes. The x-ray results were correlated with differential scanning calorimetry (DSC) measurements. On heating, first the usual annealing effects with little net melting were observed, but on increasing the temperature large changes in long spacing, which were reversible with temperature, were seen accompanied by only small changes in crystal core thickness. The second effect was found to be associated with a substantial degree of melting. Even after heating above the temperature where complete melting was indicated by DSC, the recrystallization rate was found to decrease as the melt temperature was increased and to be much faster than on cooling from the usual melts. Strikingly, this recrystallization was accompanied by a decrease in long period with time even under isothermal conditions. It is inferred that the memory of the preceding crystalline stack is preserved throughout the melting range and even beyond this, far into the molten state. This “seeding” effect is intrinsic to the polymer even if its nature cannot be specified. The principal effects in question can then be explained by envisaging that randomly placed lamellas gradually disappear within the stack on melting and successively reappear on crystallization during cooling. These ideas agree well with previous work on reversible long spacing changes in polyethylene (see ref. 9) and are likely to be of wider generality for melting and recrystallization phenomena in systems having stacked lamellar morphologies.     

聚(1,3-二氧环庚烷)二醇类聚氨酯的相态结构——软段链结构对聚氨酯相态结构的影响

用ＦＴＩＲ和ＤＳＣ对聚（１，３－二氧环庚烷）二醇为软段的聚氨酯的相态结构进行了分析．结果表明：与聚四氢呋喃二元醇类聚氨酯相比，主链中引入甲氧基后，软段相的结晶能力和硬段相中有序区的均匀程度下降．探讨了软段链结构对聚氨酯相态结构的影响     

Kinetics of fiber heat treatment. III Poly(butylene terephthalate) fibers

Small- and wide-angle X-ray scattering (SAXS and WAXS), shrinkage, and density experiments were performed on poly(butylene terephthalate) fibers which had been isothermally crystallized at different temperatures, and at constant tension, for times ranging from 100 to 1050 ms. A consistent correlation among WAXS, SAXS, and the kinetic results is demonstrated. Shrinkage results show that the crystallization process prevails over the chain-re-coiling process. Density measurements show that the rate of crystallization increases with temperature. Pinhole X-ray photos show that the orientation of the chains within the crystals remains constant with time and temperature. WAXS diffractometer scans show the development of wide-angle Bragg peaks. SAXS shows the development of small-angle Bragg peaks, as the annealing time is increased. The two-lobe arced pattern is the characteristic pattern. The value for long spacing ranged from 100 to 120 Å, increasing with temperature.     

冻干保护剂溶液低温退火特性的研究

利用差示扫描量热仪(DSC)研究了10%叔丁醇/10%蔗糖/水溶液的冻结特性, 退火温度及退火时间, 分析了溶液的退火行为. 实验结果表明, 溶液降温时, 蔗糖的存在阻碍了叔丁醇析出, 最大冻结浓缩溶液玻璃化转变温度Tg′由－32.5 ℃降低到－42.0 ℃, 升温时在－30 ℃叔丁醇发生反玻璃化. 在反玻璃化峰附近的温度进行退火可使叔丁醇充分析出, Tg′由－42.0 ℃上升到－34.9 ℃. 所需的退火时间与退火温度有关, 退火温度越接近Tg′, 所需的退火时间越长. 在－37 ℃时, 退火20 min可完全消除反玻璃化.     

偏氟乙烯/三氟氯乙烯无规共聚物的结晶

用示差扫描量热法(DSC)、广角X射线衍射(WAXD)和傅里叶红外光谱(FTIR)研究了偏氟乙烯/三氟氯乙烯单体摩尔比为1:4的无规共聚物的结晶与晶体结构.结果表明,该无规共聚物属于半结晶型聚合物.在333～353K温度范围内退火,片晶逐渐完善、增厚,熔点和结晶度均随着退火时间的延长而升高.于353K退火时,由DSC结果计算得到片晶厚度约4.68nm.在333K退火时得到共聚物的最大结晶度约为14%.WAXD测试结果表明,沿晶粒(101)晶面的面间距为0.55nm,垂直于(101)衍射晶面方向上的晶粒平均尺寸为5.86nm.     

Segmental orientation studies of polyether polyurethane block copolymers with different hard segment lengths and distributions

The orientation behavior of two series of segmented polyether polyurethanes containing different hard segment length distributions has been studied as a function of the average hard segment length which was varied from one to five methylene bis (p-phenyl isocyanate) (MDI) units. The orientation behavior of the soft segments, isolated hard segments, and of hard segments aggregated in hard domains was determined from the dichroic behavior of representative infrared bands. As the hard segment length increases, a transition in orientation behavior is observed which corresponds to a change in sample morphology.The effects of annealing and hard segment length distribution were also studied and were shown to affect the orientation response through their influence on sample morphology. Orientation hysteresis studies were performed to probe the mechanism of the transverse orientation and orientation inversion which occurred in polyurethanes with the longer, more crystallizable hard segment lengths.     

Small-angle x-ray scattering studies of thermally-induced morphological changes in segmented polyurethane elastomers

The effect of temperature on the morphology of a series of polyether and polyester polyurethanes has been studied using small-angle x-ray scattering. Scattering curves were obtained in situ at high temperature (90 and 150°C) and also later at room temperature to study the effects of thermal history on the materials. In general, annealing improves the degree of phase separation and increases the hard domain size in the materials studied. Annealing improves the degree of phase separation in more compatible systems to a greater degree than in less compatible systems. Increased interfacial mixing is apparent in the materials studied in situ at high temperatures. Thicker interfacial regions are also present in the annealed material relative to the control.     

Annealing effects on the thermal properties of liquid crystalline polyurethanes

This work is a continuation of our earlier investigations of liquid crystalline polyurethanes prepared from 4,4′-bis(2-hydroxyethoxy) biphenyl (BHBP), 2,4-tolylene diisocyanate (TDI), and poly (oxytetramethylene) diols (PTMO). The annealing effects on the thermal properties of the investigation polyurethanes are presented for three samples with the same BHBP content, different flexible spacer length, and different molecular weight of the polyurethanes. The annealed polyurethanes were investigated by means of DSC, and polarizing microscopy. The results of the thermal analysis show that the temperatures of phase transitions depend on the annealing temperature and time. These dependences are different for different molecular weights. © 1994 John Wiley & Sons, Inc.     

具有热致形状记忆功能的热塑性多嵌段聚氨酯

以ＰＣＬ为软段、ＴＤＩ－ＢＤＯ为硬段，采用溶液聚合的方法合成了具有形状记忆功能的线性多嵌段聚氨酯．利用ＤＳＣ、ＤＭＴＡ、ＷＡＸＤ等测试手段对体系的结晶性、微相分离行为进行了研究．结果发现：聚氨酯中硬段的存在对软段的结晶有着很大的影响，当软段序列的平均分子量达到３０００以上时，软段才可以很好地结晶；并且，硬段含量也必须高于一定值才能形成较为完善的物理交联点．符合这些条件的试样能显示很好的形状记忆特征．此外还就拉伸比、多次形变以及组成等对材料的形状回复性能的影响进行了详细的研究．     

Micro‐phase‐separation behavior of amphiphilic polyurethanes involving poly(ethylene oxide) and poly(tetramethylene oxide)

The temperature dependence of thermal, morphological, and rheological properties of amphiphilic polyurethanes was examined with differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS), rheological measurements, and Fourier transform infrared spectroscopy. Multiblock (MPU) and triblock (TPU) polyurethanes were synthesized with two crystallizable segments—poly(ethylene oxide) (PEO) as a hydrophilic block and poly(tetramethylene oxide) (PTMO) as a hydrophobic block. DSC and WAXS measurements demonstrated that the microphase of MPUs in the solid state is dominantly affected by the PEO crystalline phase. However, high‐order peaks were not observed in the SAXS measurements because the crystallization of the PEO segments in MPUs was retarded by poor sequence regularity. The microphase in the melt state was induced by the hydrogen bonding between the N? H group of hexamethylene diisocyanate linkers and the ether oxygen of PEO or PTMO blocks. As the temperature increased, the smaller micro‐phase‐separated domains were merged into the larger domains, and the liquidlike ordering was eventually disrupted because of the weakening hydrogen bonding. However, the fully homogeneous state of an MPU with a molar ratio of 5/5 PEO/PTMO (MPU55) was not confirmed even at much higher temperatures with both SAXS and rheological measurements. However, the SAXS patterns of TPU showed weak but broad second‐order peaks below the melting temperature of the PEO block. Compared with MPU55, the ordering of the TPU crystalline lamellar stacks was enhanced because of the high sequence regularity and the low hydrogen‐bonding density. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2365–2374, 2003     

The effect of thermal annealing on the thermal properties and molecular weight of a segmented polyurethane copolymer

The influence of thermal annealing on molecular weight, microphase mixing, and multiple melting behavior of a segmented block copolyurethane is reported. The material studied contained 55% of hard segment consisting of 4,4'-diphenylmethane diisocyanate and butanediol, and a poly (propylene oxide) diol of molecular weight 2000 as the soft segment. The thermal stability of the materials was influenced greatly by the order-disorder transition, estimated to occur at ca. 191°C. Upon annealing above this temperature, molecular weight increased rapidly as a result of chain branching reactions. Microphase separation increased under these conditions, while the degree of hard segment crystallinity decreased. Annealing below the order-disorder transition temperature resulted in relatively small molecular weight increases for short annealing times, but large increases for annealing times greater than one hour. Glass transition temperature data for these thermal treatments was consistent with upper critical solution temperature behavior and selective solubility by hard segment sequence length according to the Koberstein-Stein hard microdomain model. The critical hard segment sequence for segregation was estimated (for 30 min annealing) to contain ca. 5 diisocyanate residues at 80°C, ca. 8 residues at 185°C, and increased slowly with annealing time. © 1994 John Wiley & Sons, Inc.     

Microstructure and properties of polyurethanes derived from castor oil

The goal of this work was the synthesis of novel segmented polyurethanes with a high percentage of components derived from renewable sources. The soft segment was a polyol derived from castor oil and the hard segment structure was varied by means of different chain extenders, petrochemical-based 1,4-butanediol (BD) and corn sugar-based 1,3-propanediol (PD). The synthesis was carried out in bulk and without catalyst via a two-step polymerization varying hard segment ratio. Physico-chemical, mechanical and morphological characterization was performed by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), atomic force microscopy (AFM), mechanical testing and termogravimetric analysis (TGA). Properties have been discussed from the viewpoint of hard/soft microdomain phase separation and also the hard segment nature and formed structure. An increase in hard segment content was accompanied by an increase in hard domain order, crystallinity, and stiffness. The hard segment structures, in addition to the elastic nature of soft segment, provide enough physical crosslink sites to impart properties ranging from elastomeric to rigid behaviour with the increase of hard segment content. Polyurethanes synthesized from bio-based chain extender showed a slightly lower crystallinity in the hard segment structure than that synthesized from BD as the chain extender. This lower crystallinity avoids strength concentrations at the soft/crystalline hard segment interface, thus improving the mechanical properties at high hard segment content. The slightly higher thermal stability observed for BD based polyurethanes is related with their more packed structures and crystallinity observed in the hard segment structure.     

Thermal properties of poly(urethane-ester-siloxane)s based on hyperbranched polyester

Novel polyurethanes (PUs) were synthesized using hydroxy-terminated hyperbranched polyester (BH-20) and 4,4′-methylenediphenyl diisocyanate (MDI) as hard segments and hydroxy-terminated ethylene oxide-poly(dimethylsiloxane)-ethylene oxide triblock copolymer (PDMS-EO) as soft segment, with soft segment content ranging from 30 to 60 wt %. The PUs were synthesized by two-step solution polymerization method. The influence of the soft segment content on the structure, swelling behavior and thermal properties of PUs was investigated. According to the results obtained by swelling measurements, the increase of the hard segment content resulted in the increase of the crosslinking density of synthesized samples. DSC results showed that the glass transition temperatures increase from 36 to 65°C with increasing hard segment content. It was demonstrated using thermogravimetric analysis (TGA) that thermal stability of investigated PUs increases with increase of the soft PDMS-EO content. This was concluded from the temperatures corresponding to the 10 wt % loss, which represents the beginning of thermal degradation of samples.     

Effect of Chain Extender on Hydrogen Bond and Microphase Structure of Biodegradable Thermoplastic Polyurethanes

Thermomechanical properties of polyurethanes (PUs) strongly depend on the molecular interactions and microphase structure.In this work,two chain extenders with different ratios,flexile 1,4-butanediol (BDO) and branched trimethylolpropane mono allyl ether (TMPAE),are used to tune the molecular interactions and microphase structures of a series of biodegradable thermoplastic polyurethanes (TPUs).In TPUs,the biodegradable polycaprolactone (PCL,Mn of 2000) is used as soft segment while 1,6-diisocyanatohexane (HDI) and chain extenders are used as hard segment.Fourier transform infrared spectroscopy (FTIR),proton nuclear magnetic resonance spectroscppy (1H-NMR),gel permeation chromatography (GPC),differential scanning calorimetry (DSC),dynamic mechanical analysis (DMA) and mechanical tests were performed to characterize the bulk structure and properties of TPUs.Compared with BDO,the steric bulk of TMPAE is larger.The increment of TMPAE can help to increase the hydrogen bond content,microphase separation,and the elastic modulus ratio (R),which would strongly affect the thermomechanical property of the TPUs.The results of this work verify the importance of the structure of chain extender on the properties of TPUs.It provides valuable information for further understanding the structure-property relationships of these polyurethanes.     

Polyisobutylene‐based polyurethanes: VII. structure/property investigations for medical applications

The outstanding hydrolytic and oxidative stabilities of polyisobutylene‐based polyurethanes (PIB‐based PUs) were reported earlier. Herein, we summarize recent investigations aimed at further enhancing hydrolytic‐oxidative stabilities (in terms of resistance to aqueous buffer, nitric acid and CoCl₂/H₂O₂) together with excellent mechanical properties. The purity and dryness of ingredients together with precise NCO/OH stoichiometry (～1.05) are essential to obtain PIB‐based PUs with improved properties. Static and dynamic mechanical properties were optimized by analyzing stress–strain traces, thermal (TGA, DSC) responses, self‐organization (XRD) profiles, and rheological (DMA, creep) information. According to microstructure and surface analyses (AFM, contact angle) annealing increases the segregation of individual segments and increases surface hydrophobicity, which in turn enhances the shielding of hydrolytically oxidatively vulnerable carbamate bonds by inert PIB barriers, and thus significantly improves hydrolytic‐oxidative stability. Annealing does not much affect bulk properties, such as static and dynamic mechanical and thermal properties; however, it increases damping over a wide temperature range. Annealed PIB‐based PU containing 72.5% PIB exhibits outstanding hydrolytic‐oxidative stability together with ～26 MPa tensile strength, ～500% elongation, and ～77 Microshore hardness. PIB‐based PUs are significantly more resistant to hydrolytic and oxidative degradation than ElastEon? E2A, a commercially available PDMS‐based PU, widely used for medical applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 532–543     

Development of the morphology and crystalline state due to hybridization of reinforced toughened nylon containing a liquid‐crystalline polymer

A hybrid composite consisting of rubber‐toughened nylon‐6,6, short glass fibers, and a thermotropic liquid‐crystalline polymers (LCP) was investigated by the LCP content being varied. The thermal behavior, morphology, and crystallization behavior due to hybridization were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and wide‐angle X‐ray scattering (WAXS). DSC results indicated that the crystallinity of the glass‐fiber‐reinforced toughened nylon‐6,6 was reduced by LCP addition, particularly 5–10 wt % LCP. DMA data showed that the miscibility between the blended components was maximum at the 5 wt % LCP composition, and the miscibility decreased with increasing LCP content. SEM photomicrographs revealed information consistent with the thermal behavior on miscibility. It was also observed that the 10 wt % LCP composition showed predominantly an amorphous character with FTIR and WAXS. WAXS results indicated that LCP hybridization increased the interplanar spacing of the hydrogen‐bonded sheets of the nylon crystals rather than the spacing between the hydrogen‐bonded chains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 549–559, 2003     

Synthesis and characterization of novel environmentally friendly shape memory polyurethanes based on poly(epsilon-caprolactone) diol/castor oil mixtures

A new category of polyurethane plastics (PUs) was obtained from poly (ε-caprolactone) diol/castor oil mixture as a dual-component of their soft segment and hexamethylene diisocyanate (HDI) as the hard segment. The main aim of this study was to explore the effect of castor oil on content chemical structure, dynamic and mechanical properties and low temperature heat induced shape memory of the obtained polyurethane system. The chemical structure of samples was confirmed by Fourier transforms infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Differential scanning calorimetry (DSC) was carried out to study thermal transitions of synthesized polyurethanes. At 50 mol % of oil, the polyurethane showed the highest enhancement in tensile strength (54%) and Young’s modulus (23%) compared to PU-0. The PU containing 50 mol % of oil was nearly recovered by 99%.     

SIMULTANEOUS SAXS／WAXS／DSC STUDIES ON MICROSTRUCTURE OF CONVENTIONAL AND METALLOCENE-BASED ETHYLENE-BUTENE COPOLYMERS

The fractions of one metallocene-based (mPE) and one conventional (znPE) ethylene-butene copolymer eluted at 80-82℃ from temperature rising elution fractionation were selected for DSC and time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) characterization. The DSC and WAXS results show that two crystal structures exist in both mPE and znPE: structure A with higher melting temperature and structure B with lower melting temperature. It was found that original znPE (s-znPE) contains more highly ordered structure A than original mPE (s-mPE) in spite of the higher comonomer content of znPE. Another structure C is also identified because of higher crystallinity measured by WAXS than by DSC and is attributed to the interfacial region. The SAXS data were analyzed with correlation function and two maxima were observed in s-mPE and s-znPE, in agreement with the conclusion of two crystal populations drawn from DSC and WAXS results. These two crystal populatiorts have close long periods in s-mPE, but very different long periods in s-znPE. In contrast, freshly crystallized mPE and znPE (f-mPE and f-znPE) contain only a single crystal population with a broader distribution of long period