Internal stress,lattice deformation,and modulus of polymers

The relationships among internal stress, lattice deformation, and the moduli of polymers, such as poly(ethylene terephthalate) (PET), polypropylene (PP), polyethylene (PE), polyacryonitrile (PAN), and poly(p-phenylene terephthalamide) (PPTA), have been studied systematically. Compared to small molecule crystals, polymer crystals have many more defects and their parameters of the crystal unit cells and the density of the crystalline region are easy to vary to a certain extent. During the processing, external stresses were put on the polymer fibers and polymer molecules were drastically deformed, which induced polymer crystallization and preferred orientation. After processing, there are many macromolecules frozen in the nonequilibrium status, which is the cause of internal stress. Heat treatment could give energy to the macromolecules to release the internal stress and to approach thermodynamic equilibrium. For polymer crystals, the higher the annealing temperature, the shorter the lengths of the unit cell axes, the more integral and regular the crystal lattice, and the smaller the unit cell volume. Crystalline modulus changes not only with different kinds of polymer materials, but also with measurement temperature and processing history. Polymer processing, mainly drawing, causes orientation and internal stress which causes lattice deformation and raises tensile modulus of polymer materials.     

Epitaxial crystallization of nylon 6 cast from solution on the surface of poly(p-phenylene terephthalamide) filament

Poly(p-phenylene terephthalamide) (PPTA) fiber has the characteristics of high modulus and strength, and has been employed as the reinforcement in composite materials. The interfacial interaction between the PPTA filament and nylon 6 matrix has been investigated to make use of these characteristics of PPTA in fiber-reinforced composite systems. In the case of composites composed of the PPTA filament and nylon 6, two types of expitaxial crystallization have been observed depending on the concentration of a formic acid solution. From concentrated solution, nylon 6 forms a columnar cystal around the PPTA filament. A two-dimensional spherulite model, (i.e., a disk shape) is proposed for the aggregated structure of nylon 6 chains on the basis of wide-angles x-ray diffraction, small-angle x-ray scattering studies, and scanning electron microscopic ebservation. The a*-axis of the nylon 6 crystal is directed radially in its columnar crystal. In the inner portion, close to the interface, the be-plane is in contact with the surface of the PPTA filament, also, the directions of the b- and c-axes are paral el and perpendicular to the PPTA filament axis, respectively. On the other hand, their axes rotate about the a*-axis in the outer portion, far from the interface region. Furthermore, a different type of epitaxy was observed in the case of crystallization from a dilute solution of nylon 6 in formic acid. These two types of crystal growth were investigated from the view of crystallization condition and crystallographic lattice matching at the interface region between the PPTA filament a nylon 6. It is concluded that the hydrogen bonding between PPTA and nylon 6 molecules at the interface plays an important role for epitaxial crystallization, in addition to lattice matching.     

Electron diffraction and molecular modelling investigation of the crystal structure of poly (para-phenylene terephthalamide) form II

Microsingle crystals of poly(para-phenylene terephthalamide), abbreviated PPTA, were obtained by water-vapor induced precipitation of PPTA rigid-flexible copolymers in sulfuric acid solution. Electron diffraction was performed and yielded hk0 patterns. The crystal structure of a model compound, N, N′ para (4-methoxycarbonyl) phenylene dibenzamide, abbreviated 3ARB-COOMe, is also reported. Its structure is compatible with that of the polymer, in which aromatic rings are all coplanar and form a 30° angle with amide groups. A reinvestigation of form II, based on electron diffraction data and molecular modeling simulations, is reported. The proposed space group is P112, and corresponds to a parallel chain arrangement, with terephthaloyl groups facing one another, and carbonyl groups pointing in opposite directions along the b-axis in adjacent hydrogen-bonded sheets. Chain conformation is the same as in form I, as previously established. The 3ARB-COOMe conformation is suggested as a possible polymorph or as defects in the crystal phase.     

Enthalpic and entropic origins of nucleation barriers during polymer crystallization: the Hoffman-Lauritzen theory and beyond

In the search for a greater understanding of polymer crystallization, numerous experimental observations with regards to microscopic structures and macroscopic properties have been reported in the past half-century. There are generally two types of experimental results to provide information about the mechanisms of polymer crystal growth, i.e. molecular dynamic/scattering and structural/morphological. Since we cannot follow the trajectory of individual chain molecules when they undergo the transition from liquid to solid state during the crystallization process, structural/morphological analysis of polymer crystals reveal information recorded during this process. Namely, the final structure and morphology of polymer crystals have atomic, stem and global chain conformation information embedded in them during crystallization which provides evidence which can be used to deduce molecular aspects of the polymer crystallization process. It is commonly understood that polymer crystallization, from the thermodynamic perspective, is a first-order transition involving the relaxation of a metastable undercooled melt towards the equilibrium state which is rarely reached in polymer crystals. This process is controlled by a free energy barrier. A molecular model is required to describe the landscape of the free energy barriers and to provide an analytical explanation concerning and predictions about polymer crystallization. The Hoffman-Lauritzen (HL) theory, which was put forward more than 40 years ago, was one of the first analytical theories to illustrate how polymers crystallize. Since then, modifications to the HL theory and suggestions for new approaches have been reported, but the core physical picture of the HL theory has largely remained intact. This article consists of four major parts: (1) we will compare the crystallization of small molecules and long chain molecules, and the relationship between crystallization and crystal habits. The diversity of crystalline structures and morphologies of semi-crystalline polymers must be taken into account when studying the crystallization mechanism of polymers (2) this article also serves as a brief review of the HL theory and its importance in our understanding of polymer crystallization (3) we have tried to answer the question: what is the nucleation barrier? Specifically, we will illustrate that the nucleation barrier in polymer crystallization consists of both enthalpic and entropic components as deduced from experimental results. This barrier, from our perspective, consists of selection processes taking place in different length- and time-scales (4) finally, there is a brief discussion on what issues remain, in particular, in the areas of undercooled liquid structures and the initial stages of crystallization.     

Miscibility in poly-p-phenylene terephthalamide/nylon 6 and nylon 66 molecular composites

Miscibility and crystallization of poly-p-phenylene terephthalamide (PPTA)/nylon 6 and nylon 66 composites prepared by coagulation of isotropic ternary sulfuric acid solutions were studied. The apparent crystallinity of nylon 6 and nylon 66 in molecular composites was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy. The solvation of nylon 6 crystals in PPTA matrix was observed when the PPTA content exceeds 70 wt%. Cross-hydrogen bonding seems to be responsible for the virtual disappearance of nylon 6 crystals. Specific interaction between PPTA and nylon 6 macromolecules and phase separation during thermal treatment has been discussed.     

Miscibility and toughness improvement of poly(lactic acid)/poly(3-Hydroxybutyrate) blends using a melt-induced degradation approach

Biodegradable polymer blends of high-molecular-weight poly(3-hydroxybutyrate) (PHB) and poly(lactic acid) (PLA) are not miscible in general. Yet, by decreasing the molecular weight of PHB, the low-molecular-weight PHB could have improved miscibility with the PLA. In this study, a melt-induced degradation process of PLA/PHB blends was therefore implemented, termed the in-situ self-compatibilization approach, to produce low-molecular-weight PHB during melt blending process. The solution blends of PLA and oligomer PHB (PLA/OPHB) were also prepared as a basis to understand the role of low-molecular-weight PHB to improve its miscibility with PLA in PLA/PHB blends. Only one single glass transition temperature (T_g) was found for the resulting PLA/PHB blends at compositions of 95/05 to 80/20, proving that the miscibility was greatly improved by decreasing molecular weight of PHB. Because the degraded PHB had a relatively lower T_g, it thus provided plasticization effect to the PLA and resulted in the decreased crystallization temperature. Moreover, with increasing PHB content to 20% in the blend, the elongation at break increased significantly from 7.2% to 227%, more than 30-fold. The extensive shear yielding and necking behavior were observed during tensile testing for the blend of 80/20. The localized plasticization within PLA/PHB matrix with the reduction of local yield stress and the well-dispersed PHB crystallites were the major contributing factors to trigger shear yielding phenomenon. Moreover, initial modulus decreased only 20%, from 1.68 to 1.35 GPa. A common problem of severely reduced stiffness from the added plasticizer encountered in the plasticized PLA blends was therefore not perceived here.     

废弃芳纶粉末环氧化改性及其固化物性能

针对国内对位芳纶（PPTA）在实际生产中产生的低分子量PPTA粉末,探讨了一种有效回收再利用的方法。本文以低分子量PPTA为原料、环氧氯丙烷为改性剂,采用金属化/取代反应,制备了环氧氯丙烷（ECH）修饰的PPTA（PPTAGE）,并通过单因素实验优化了PPTAGE合成条件。结果表明：合成条件为m(ECH）∶m(PPTA)=3∶1、NaH用量（与总投料量质量之比）0.4%、反应温度80℃、反应时间4.5h时,PPTAGE接触角最小,纤维表面能最佳。将改性前后的芳纶分别作为环氧树脂的填料,得到固化物样条,研究了PPTAGE对环氧树脂复合材料力学性能的影响。固化物力学性能研究表明,PPTAGE可以在一定程度上提高与环氧树脂基体的黏合,在添加量为1%时,复合材料的力学性能达到最佳;热重（TGA）分析表明,固化物热稳定性较PPTA/E-51有所提高;扫描电镜（SEM）测试表明,PPTAGE/E-51冲击断裂面为韧性断裂。     

超高相对分子质量PPTA树脂及其高模量芳纶的研究

对高相对分子质量聚对苯二甲酰对苯二胺(PPTA)树脂进行了表征,开展了添加超高相对分子质量PPTA树脂与普通相对分子质量PPTA树脂共混进行液晶纺丝得到高强度和高模量芳纶的结构表征与性能试验,同时对芳纶的力学性能与其PPTA树脂相对分子质量的关系进行了研究。结果表明,芳纶的力学性能与其PPTA聚合体的相对分子质量紧密相关,如果PPTA树脂的相对分子质量不够高,加上液晶纺丝和高模量热处理过程分子链的进一步降解,高模量芳纶的制备就无法实现。在系统研究PPTA聚合反应规律,特别是聚合诱导相互转变规律及其影响因素研究基础上,通过调控连续聚合的反应条件,在1 000 t/a连续聚合生产线上制备出比浓对数粘度高达9.2 dl/g的超高相对分子质量PPTA树脂;用超高相对分子质量PPTA树脂与通用级PPTA树脂(比浓对数粘度6.8 dl/g)混合进行纺丝,制备出高强度的芳纶,并进一步热处理得到高强度和高模量的芳纶。     

Molecular composites via in situ polymerization: Poly(phenylene terephthalamide)–nylon 3

All-polyamide molecular level composites composed of rigid rod and flexible coil polymers were prepared using an in situ polymerization process in which the anion of the rigid rod poly-(phenylene terephthalamide) (PPTA) was used as the initiator for the anionic polymerization of acrvlamide to form the nylon 3 matrix. The rigid aramid component then serves as the reinforcing agent. This polymerization resulted in both graft and homo-nylon 3 formation. Composite films prepared using in situ processing showed greatly improved strength and modulus over unmodified nylon 3 with no loss of flexibility. The composites showed aggregation and phase separation of PPTA fibrils at PPTA weight fractions of > 30% as indicated by wide angle X-ray scattering and electron microscopic analysis. The structure of the PPTA formed is that produced from swelled liquid crystalline solutions, indicating that the in situ process involves polymerization in the liquid crystalline state.     

Morphology of nascent polyethylene prepared with the catalyst VOCl3/(C2H5)2AlCl

The catalyst VOCI₃/(C₂H₅)₂AICI was used to prepare polyethylene under various conditions of polymerization. The nascent polymer samples were examined by optical and electron microscopy, fuming nitric acid oxidation and differential scanning calorimetry. It was observed that the samples consisted of lamellar as well as fibrillar crystals. Examination of catalyst preparations by light-scattering photometry revealed the presence of a colloidal dispersion besides the soluble catalyst complex. It is proposed that the lamellar and fibrillar crystals have different origins. The lamellar crystals are formed by intramolecular crystallization of polymer chains generated from the soluble catalyst complex, whereas the fibrils are the product of intermolecular crystallization of polymer chains growing from adjacent active sites residing on the surface of the colloidal particles. The degree of chain extension in the fibrillar crystals is dependent on the conditions of polymerization.     

Polyethylene/carbon nanotube nano hybrid shish-kebab obtained by solvent evaporation and thin-film crystallization

Crystallization of polymers on carbon nanotubes (CNTs) has resulted in a novel nano hybrid shish kebab (NHSK) structure, within which CNTs serve as the nucleation sites (shish) and polymer lamellar crystals form the kebabs. Previously reported NHSK structures were obtained by solution crystallization, bulk crystallization and physical vapor deposition methods. Herein we report a simple, rapid, yet effective approach to produce NHSK materials using solvent evaporation and thin film crystallization. Polyethylene (PE) was used as the model polymer. PE solution was drop cast on CNT-coated carbon films, and upon solvent evaporation, PE crystallized onto/near CNTs, following the template of the latter and NHSK structure was then formed. The final morphology was found to result from the competition between heterogeneous nucleation and homogeneous nucleation of PE. The formation of NHSK also strongly depends on the structure of CNTs as well as the molecular weight of PE. This work shows a facile method to form NHSK and to study CNT-induced crystallization under nonequilibrium conditions.     

Molecular weight determinations on polymers by electron microscopy

A technique has been developed by which molecular weight averages and distributions may be obtained for polymer fractions of high molecular weight. For glassy amorphous polymers, very dilute solutions in solvent-precipitant mixtures are atomised on to a thin carbon substrate, shadowed with platinum-carbon mixture and examined in the electron microscope. A solvent is chosen which is more volatile than the precipitant, so that on the path from the atomiser system to the substrate, and on the substrate itself, preferential evaporation of the solvent takes place. Contacts between polymer segments become more favourable than polymer-solvent contacts, resulting in the progressive contraction of the molecular coils, and the deposition of single spherical self-supporting molecules, the diameters of which can be determined from the lengths of the shadows cast by them. Molecules of polymers having glass transition temperatures below room temperature, or even slightly above, show varying degrees of collapse when prepared at room temperature. A device has been constructed which allows such polymer molecules to be deposited and shadowed at temperatures down to ?100°, at which temperature molecular collapse is not apparent. Molecular diameters may then be measured as for glassy polymers. An atomiser-separator system was constructed, which produced small droplets containing, essentially, one or zero polymer molecules, when a fraction of high molecular weight was used. All the solvent was evaporated from the droplets on the path to the cooled substrate, allowing the deposition of solvent-free molecules. Molecular weight averages and distributions are presented for a series of high-molecular-weight polymer fractions, in the glass transition temperature range from 100° to —73°. The high precision of the results from this technique is demonstrated, together with the close agreement between molecular weight averages obtained by electron microscopy, and those obtained by light-scattering and viscometry.     

Effects of hydrocarbon tackifiers on the adhesive properties of contact adhesives based on polychloroprene - III. The effect of the molecular weight of the tackifier

Aromatic hydrocarbon resins with different molecular weights (M_w = 1300-50400 daltons) were added to a solvent-based polychloroprene adhesive. The hydrocarbon resins were characterized using infra-red (IR) and differential scanning calorimetry (DSC) measurements. The properties and compatibility of the polychloroprene/resin blends were studied using mechanical tests, DSC measurements, scanning electron microscopy (SEM), and stress-controlled rheology. Tack measurements were also carried out and the adhesion strength was obtained from T-peel tests on roughened styrene-butadiene rubber/polychloroprene adhesive joints. The addition of low-molecular-weight tackifiers produced a compatible polychloroprene/tackifier system (only one T_g was found in DSC measurements), while the addition of a high-molecular-weight (and broad molecular weight distribution) tackifier produced a partially incompatible system (two Tg's were found in DSC measurements). The compatibility of polychloroprene/tackifier blends was also assessed with stress-controlled rheology and SEM. An increase in the T-peel strength and tack were produced when the molecular weight of the tackifier increased, although the addition of a hydrocarbon resin with a M_w higher than about 50 000 reduced the tack. A broad molecular weight distribution in the tackifier favoured incompatibility with the polychloroprene, resulting in a reduction in the tack and rheological properties.     

直接成纤法芳纶－Ⅱ短纤维形态和性能的研究

利用聚对苯二甲酰对苯二胺（芳纶－Ⅱ树脂）的聚合物凝胶,在聚合的环境下就地直接成纤的方法制备了芳纶－Ⅱ短纤维。研究了在直接成纤法中,芳纶－Ⅱ树脂的对数比浓粘度（η＿（ｉｎｂ））与所制备的短纤维的长度和长径比之间的关系;建立了用短纤维一环氧树脂复合材料的性能表征短纤维性能的方法。在此基础上进一步研究了短纤维的长度和长径比对其性能的影响．结果表明,利用直接成纤法,由η＿（ｉｎｈ）≥３．５ｄＬ／ｇ的聚合物凝胶可以制备性能较好、适用于复合材料应用的芳纶－Ⅱ短纤维。     

Crystallization behavior of nylon 6 nanocomposites

The crystallization behavior of nylon 6 nanocomposites formed by melt processing was investigated. Nanocomposites were produced by extruding mixtures of organically modified montmorillonite and molten nylon 6 using a twin screw extruder. Isothermal and non-isothermal crystallization studies involving differential scanning calorimetry (DSC) were conducted on samples to understand how organoclay concentration and degree of clay platelet exfoliation influence the kinetics of polyamide crystallization. Very low levels of clay result in dramatic increases in crystallization kinetics relative to extruded pure polyamide. However, increasing the concentration of clay beyond these levels retards the rate of crystallization. For the pure nylon 6, the rate of crystallization decreases with increasing the molecular weight as expected; however, the largest enhancement in crystallization rate was observed for nanocomposites based on high molecular weight polyamides; this is believed to stem from a higher degree of platelet exfoliation in these nanocomposites. Wide angle X-ray diffraction (WAXD) and DSC were further used to characterize the polymer crystalline morphology of injection molded nanocomposites. The outer or skin layer of molded specimens was found to contain only γ-crystals; whereas, the central or core region contains both the α and γ-forms. The presence of clay enhanced the γ-structure in the skin; however, the clay has little effect on crystal structure in the core. Interestingly, higher levels of crystallinity were observed in the skin than in the core for the nanocomposites, while the opposite was true for the pure polyamides. In general, increasing the polymer matrix molecular weight resulted in a lower degree of crystallinity in molded samples as might be expected.     

Static and dynamic light scattering studies of the crystallization of poly(ethylene oxide) from dilute solutions

We have monitored in situ the self-seeded crystallization of poly(ethylene oxide) from dilute toluene solutions by dynamic light scattering. In supercooled dilute solution, the radii (R) of the crystals grow linearly with time. the rate constant obtained from the slope of the plot R versus time depends on the temperature and the molecular weight of the polymer, both of which determine the degree of the supercooling. The maximum crystal size obtained from solutions of fixed concentration also depends on the temperature and the polymer molecular weight. It appears that crystal growth is limited because of molecular weight fractionation. Static light scattering from suspensions of stable crystals provides information on the crystal morphology. A comparison of experimental and theoretical particle scattering functions suggests that the crystals form short cylinders and that the crystal growth from the seeds is primarily two-dimensional. Some comparisons to melt crystallization are possible. The preparation and use of tiny seed crystals is critical to the success of these studies.     

Crystallization of polyamides under elevated pressure: 5.Pressure-induced crystallization from the melt and annealing of folded-chain crystals of nylon-11, poly(aminoundecaneamide) under pressure

High pressure dilatometry, differential scanning calorimetry, electron microscopy, X-ray diffraction, and infra-red spectroscopy to study how the crystallization of nylon-11 from the melt, as well as annealing of the folded-chain crystals, are affected by pressure in the range from 1 to 10 kbar (1 kbar = 100 MN/m²) and temperature in the range from 200° to 320°C. Pressures exceeding 3 kbar and temperatures higher than 230°C are sufficient for growth of the chain-extended crystals of nylon-11 either by pressure-induced crystallization from the melt or by annealing of the folded-chain crystals. Crystallization from the melt or annealing at 320°C or higher, and 10 kbar, resulted in crosslinking of the polymer. The highest melting temperature and heat of melting found for the chain-extended crystals of nylon-11 were 226°C and 35 cal/g respectively, as compared to 190°C and 13.6 cal/g for the folded-chain material. The texture of the chain-extended crystals of nylon-11 was found to be spherulitic with well developed striations forming circle patterns, and polymer chains passing through several lamellae. No sharp boundaries were found between the chain-extended lamellae. The alpha-crystalline modification, found for the folded-chain crystals of nylon-11, was preserved in the high pressure crystallization and annealing experiments. Infra-red absorption bands at 1420 and 1225 cm^?1 seem to be associated with the presence of folds in the nylon-11 crystals. It is suggested that, during the initial stage of crystallization under pressure, folded-chain crystals are formed, with a crystalline order and long spacing larger than that of the starting nylon-11.     

Insight into how molecular structures of thiophene-based conjugated polymers affect crystallization behaviors

Combining the structural characterization of solution crystals fabricated from thiophene-based conjugated polymers with different molecular structures and a theoretical investigation of the polymer conformational transformability leads to an interesting discovery of the relationship between the molecular structures and their crystallization behaviors. The chain folding or nonfolding behavior of thiophene-based conjugated polymers in crystallization, an important factor to shape polymer crystals, is determined by their molecular structures, and can be estimated by the inter-ring rotation energy barriers of the polymer backbones. A quantitative theoretical calculation is proposed to evaluate the inter-ring rotation energy barriers, and the values are correlated with the experimentally observed chain folding or nonfolding behavior. The higher percentage of type I inter-ring σ bond (CH₃ and H are at 3 and 3′ position of adjacent aromatic rings, respectively) or the lower average rotation barrier in polymer backbones creates higher capability of polymer conformational transformation and higher tendency of chain folding. Our study provides a valid prediction of the crystallization behavior of thiophene-based conjugated polymers through a theoretical evaluation of conjugated polymer molecular structures, and offers an essential understand of the structure-property relationship of conjugated polymers.     

Polymer composite of rigid and flexible molecules: Blend systems of poly(p-phenylene terephthalamide) and ABS resin

Homogeneous coagulant of poly(p-phenylene terephthalamide) (PPTA) and ABS resin was obtained by pouring the dimethylsulfoxide solution of N-sodium PPTA and ABS into acidic water. Transmission electron microscopic observation proved that PPTA was dispersed in the matrix in a form of microfibril with a diameter of 10–30 nm. The T_g of the resin component in ABS shifted to higher temperatures with increasing fraction of PPTA. Stress-strain behavior of the polymer composite showed increased tensile modulus and strength with addition of PPTA. The transition temperature from brittle to ductile fracture, however, shifted to higher temperature resulting in lower extensibility. Incorporation of the block copolymer of PPTA and polybutadiene into ABS improved the ultimate extensibility, i.e., increased toughness was provided compared with the simple composite systems of ABS and PPTA microfibrils. Scanning electron microscopic observation showed that the polymer composite made with the block copolymer generated many crazes upon deformation, while the composite with PPTA homopolymer fractured without remarkable craze formation. Thus, a new type of thermoplastic with improved mechanical properties was obtained by use of PPTA block copolymer as compatibilizer.     

溶剂与杂质对11α羟基-16α,17α-环氧黄体酮晶习的影响

The effects of solvent and impurity on the crystal habit of 11α-hydroxy-16α, 17α-epoxyprogesterone (HEP) grown from solution were studied by scanning electron microscope. Long prismatic crystals were produced when HEP was crystallized from pure acetone and N,N-dimethylformamide, while blocky crystals were produced from pure chloroform by cooling crystallization. One kind of isomorphic impurity, 16α, 17α-epoxyprogesterone (EP)was selected to examine its effect on the HEP crystal habit. When the content of EP in the mother liquor is very high (55.45%, solvent free basis), the habit of produced HEP crystals was greatly modified from prismatic to octahedral. The differential scanning calorimetry and X-ray powder diffraction analyses showed that the change of crystal habit was originated from the crystal structure modification.