Comparison of the Structural Evolution of β Polypropylene during the Sequential and Simultaneous Biaxial Stretching Process

In this work, the lamellar structural evolution and microvoids variations of β polypropylene(β-PP) during the processing of two different stretching methods, sequential biaxial stretching and simultaneous biaxial stretching, were investigated in detail. It was found that different stretching methods led to significantly different lamellae deformation modes, and the microporous membranes obtained from the simultaneous biaxial stretching exhibited better mechanical properties. For the sequential biaxial stretching, abundant coarse fibers originated from the tight accumulation of the lamellae parallel to the longitudinal stretching direction, whereas the lamellae perpendicular to the stretching direction were easily deformed and separated. Those coarse fibers were difficult to be separated to form micropores during the subsequent transverse stretching process, resulting in a poor micropores distribution. However, for the simultaneous biaxial stretching, the β crystal had the same deformation mode, that is, the lamellae distributed in different directions were all destroyed, forming abundant microvoids and little coarse fibers.     

Orientation effects in biaxially stretched linear polyethylene

The literature on polymer morphology contains many studies of structural and orientation changes occurring upon uniaxial stretching of films and fibers, but it has only an occasional reference to such studies on biaxially stretched film. This paper presents data on a structural change due to simultaneous biaxial stretching up to 6 × 6 stretch ratio of quenched linear polyethylene slightly below the melting temperature. At low stretch ratios the b axis of the orthorhombic unit cell orients predominantly in the biaxial plane of stretching or film plane. At higher than 4 × 4 stretch ratio, a second crystal orientation appears which is a (110) orientation in the film plane. Differential scanning calorimetry scans show two melting peaks occurring concurrently with diffraction effects of two crystal orientations. The evidence for two populations of crystals differing in orientation are discussed in the light of current concepts of folded-chain lamellae and their fragmentation with elongation.     

泡压-滤速法研究聚丙烯微孔膜的孔径及其分布

膜科学与膜技术作为新兴的材料科学分支之一,在国民经济中发挥着越来越重要的作用．近年来,高分子微孔膜的研究与应用正引起人们日益增长的关注．采用双轴拉伸方法制备的聚丙烯微孔膜同时具备了良好的力学性能和透过性能［１］,克服了单轴拉伸方法各向异性的缺点,是一...     

Influence of solid-state biaxial orientation on the adhesion between poly(ethylene terephthalate)/tie layer/isotactic polypropylene multilayer films

Current state-of-the-art packaging films typically consist of solid-state stretched multilayer polymer systems, in which each of the polymer layers provides a specific property. Often these polymer film layers are incompatible and need to be glued together by so-called “tie layers.” In this article, we apply a novel biaxial orientation technique to examine the effect of solid-state biaxial stretching on the adhesive behavior of a model multilayer system consisting of poly(ethylene terephthalate) and isotactic polypropylene, as an example of two typical incompatible base layers, glued together by a common tie layer. Two main factors affecting the adhesion, the temperature at which the biaxial stretching is performed and the thickness of the tie layer, are discussed in detail. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 446–454     

单向和双向拉伸聚酯(PET)薄膜取向的光学评价

<正> 通常人们采用X-射线法和红外二向色性法等获得有关高聚物材料的晶区取向和分子链上某些特定基团的取向状况,但存在着设备要求高且操作复杂的弊端。Schael和Samuels等发展了利用改装型阿贝折射仪,可以方便地同时获得高聚物薄膜样品(聚烯烃和羟基丙基纤维素等)三个轴向上的折射率。有关聚酯(PET)的报道则不多见。本工作主要研究了不同拉伸条件(拉伸方式和拉伸速率等)对PET薄膜取向状况(折射率和     

Influence of the stretching in the crystallinity of biaxially oriented polypropylene (BOPP) films

Summary The production of biaxially oriented polypropylene (BOPP) films, by tenter-frame technology in its different steps, was studied to find the crystalline morphology of these films. DMA, DSC, and WAXD measurements and tensile tests were carried out for the cast film, the MDO film (the produced film in the machine direction orienter unit) and BOPP film. The obtained results suggest that the stretchings lead to a strong alignment of the crystals, producing fibers oriented in the stretching direction. This fact can be proved by WAXD, DMA, and tensile tests, moreover the DSC technique is not sensitive to detect these changes.     

Crystallinity and dimensional stability of biaxial oriented poly(lactic acid) films

Transparent biaxial oriented poly(lactic acid) (BOPLA) films with improved dimensional stability were successfully prepared by controlling the crystallization of poly(lactic acid) (PLA). The crystalline morphology of PLA films can be manipulated by changing certain processing parameters, such as stretch ratio, heat setting temperatures, and heat setting time. Optical and mechanical properties as well as dimensional stability of the resulting polymer films are governed by their crystallinity and crystalline morphology. Crystallization behavior and kinetics of PLA, therefore, were investigated using wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC) techniques. Mechanical properties and the dimensional stability of the biaxial oriented PLA films were obtained and correlated with their processing conditions. Poly(lactic acid) films prepared by melt extrusion methods have great potential for food packaging, shrink labeling and protective film applications. However, shrinkage at elevated processing temperature should be minimized to avoid puckering of the polymer film. Shrinkage of less than 2% was achieved for a BOPLA film stretched 300% in both directions at 75 °C and then annealed at 160 °C for 30 s. Fabrication, properties, and potential applications of a series of biodegradable films will be described.     

A novel polypropylene microporous film

The structure and properties of a polypropylene microporous film prepared by biaxial stretching of non-porous polypropylene film of high β-crystal content were investigated. The porosity of these films can be as high as 30–40%, and the average pore size was around 0.05 μm. The films were found to have the structure of a two-phase interpenetrating network; both the polypropylene and the pore regions were three-dimensionally continuous. The advantages of the biaxially stretched microporous films are the combination of high permeability to fluids with good mechanical properties and almost circular pore shape with narrow pore size distribution. The application of this microporous film for battery separators, filtration membranes and substrates of functional polymer composites is discussed.     

Effects of chain extender and uniaxial stretching on the properties of PLA/PPC/mica composites

Poly(lactic acid) (PLA)/poly(propylene carbonate) (PPC)/mica composites with different amount of chain extender (CE) were melt compounded and then processed via two routes (compression molding and uniaxial stretching) into sheets and films. The tensile, thermal, and oxygen barrier properties of all the samples were investigated. Tensile test showed that the tensile strength and elongation at break of all films were much higher than that of all sheets, especially for PLA/PPC/mica with 0.9‐wt% CE composite (CM₃(CE)_0.9) film. The crystallinity of all films increased significantly after uniaxial stretching of sheet samples. The Fourier transform infrared spectroscopy (FTIR) results proved the chemical reactions occurred between PLA/PPC and CE. Scanning electron microscope (SEM) analysis revealed that compatibility and interfacial adhesion of all samples were improved after adding mica and CE, and they were further enhanced after uniaxial stretching. The addition of CE was not favorable to improve the oxygen barrier performance of PLA/PPC/mica sheet samples. However, the oxygen barrier performance of film samples was significantly improved after uniaxial stretching. In particular, the CM₃(CE)_0.9 film had the lowest oxygen permeability coefficient (1.4 × 10^?15 cm³·cm/(cm²·s·Pa)), and this was the best oxygen barrier properties reported in the literature for PLA‐based composites, which was comparable with PA film. This study demonstrated the high efficiency of uniaxial stretching on improvement of properties of composites, which would promote the application of biodegradable polymers in oxygen sensitive food packaging.     

Effect of biaxial orientation on dielectric and breakdown properties of poly(ethylene terephthalate)/poly(vinylidene fluoride‐co‐tetrafluoroethylene) multilayer films

Polymer films with enhanced dielectric and breakdown properties are essential for the production of high energy density polymer film capacitors. By capitalizing on the synergistic effects of forced assembly nanolayer coextrusion and biaxial orientation, polymer multilayer films using poly(ethylene terephthalate) (PET) and a poly(vinylidene fluoride‐co‐tetrafluoroethylene) [P(VDF‐TFE)] copolymer were produced. These films exhibited breakdown fields, under a divergent field using needle/plane electrodes, as high as 1000 kV mm^?1. The energy densities of these same materials, under a uniform electric field measured using plane/plane electrodes, were as high as 16 J cm^?3. The confined morphologies of both PET and P(VDF‐TFE) were correlated to the observed breakdown properties and damage zones. On‐edge P(VDF‐TFE) crystals induced from solid‐state biaxial stretching enhanced the effective P(VDF‐TFE) layer dielectric constant and therefore increased the dielectric contrast between the PET and P(VDF‐TFE) layers. This resulted in additional charge buildup at the layer interface producing larger tree diameters and branches and ultimately increasing the breakdown and energy storage properties. In addition to energy storage and breakdown properties, the hysteresis behavior of these materials was also evaluated. By varying the morphology of the P(VDF‐TFE) layer, the low‐field dielectric loss (or ion migration behavior) could be manipulated, which in turn also changed the observed hysteresis behavior. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 882–896     

聚对苯二甲酸乙二酯非晶态膜片单轴热——拉伸中的结晶与松弛

用动态力学损耗温度谱作为测试手段,研究了非晶态PET膜片在78—112℃温度范围内的单轴拉伸。实验结果说明,在较低温度下所得结晶的拉伸试样,完全由于应变诱发结晶,发生在应力-应变曲线的屈服后应力开始上升的阶段。在较高温度下(90℃或更高)拉伸可得非晶态而且光学各向同性的试样,是由于分子链的小尺度取向在拉伸过程中已完全热松弛所致,而分子链的大尺度取向要通过高弹态流动而松弛,其速率较慢,用拉伸后试样两端固定时的应力松弛进行了观察。在较低温度下应力松弛后仍为非晶态,在较高温度下应力松弛到起始应力的1O％下才开始结晶。FTIR研究表明在这种状态下的结晶有一结晶诱导期,其时间尺度与应力松弛阶段相当。     

Partly Imidized Polyamic Acid and Its UniaxialStretched Polyimide Films

Partly imidized polyamic acid(PAA) has been used to prepare high performance polyimide films. The behaviors of two polyamic acids derived from pyromellitic dianhydride(PMDA)/4,4′-oxydianiline(ODA) and 3,3′,4,4′-biphenyltetracarboxylic diahhydride(BPDA)/paraphenylenediamine(PPD) containing dehydrating agents composed of acetic anhydride and a tertiary amine as the catalyst were investigated. The gel point was dependent on imidization degree in despite of temperature and the molar ratio of catalyst to acetic acid. Imdization content was about 35% for PMDA/ODA and about 22% for BPDA/PPD. The effect of catalyst on imidization possessed an order of triethylamine>3-methylpyridine>pyridine>isoquinoline>2-methylpyridine. The stretching of the films greatly reduced the coefficient of linear thermal expansion(CTE) either in the longitudinal direction or transversal direction. Compared to the film from polyamic acid, the partly imidized film had greater stretching ratio, so that the uniaxial stretched polyimide film from partly imidized PAA had higher tensile strength and tensile modulus, but lower elongation in the stretching direction.     

An x-ray pole figure analysis on biaxially deformed polyethylene film

The orientational states induced upon two-step biaxially stretching low-density polyethylene at 25°C have been investigated. A pole figure analysis of the (200), (020), and (002) crystalline planes has been employed to elucidate the evolution of the molecular crystalline orientation as a function of biaxial stretching. The initial uniaxial-like orientation induced along the extrusion direction of the films was gradually lost upon transverse stretching and, consequently, replaced by a biaxial orientation as suggested by the orientation functions. In these cases, the a crystallographic axis was observed to be strongly oriented along the film normal, thus confining the c and b axes to the film plane. The pole figures clearly indicate that the c and b axes are preferentially aligned 45° with respect to the stretching directions. This unique orientational state of the orthorhombic unit cell of polyethylene has been termed a biaxial-double orientation. Birefringence measurements on the biaxial samples indicated that the amorphous and crystalline regions are simultaneously biaxially oriented. The evolution of the crystalline orientation as a function of stretching was conveniently followed on a White/Spruiell orientation triangle. Quantification was hindered, however, by the presence of different crystal populations in the biaxially stretched samples. © 1994 John Wiley & Sons, Inc.     

Thermal and Dynamic-Mechanical Characterization of Uni- and Biaxially Oriented Polypropylene Films

The effect of uni- and biaxial orientation in the morphology of polypropylene films has been investigated by thermal, dynamic-mechanical, X-ray pole figure and diffraction patterns. In uniaxial oriented films the level of damping is roughly three times higher in the MD direction than it is in the TD direction. The stretching always produces crystals of the form independently of the starting type. Fast DSC scans show two melting peaks indicative of two crystalline species. The Fujiyama et al. model for the crystalline structure can be also applied to the uniaxially stretched films. Upon biaxially orienting, the folded lamellae crystals (kebabs) are the ones to support all the force applied, and when their maximum level of stress slippage is reached they deform following the Peterlin's model, forming a new shish structure. These new shishes are aligned to the TD direction and by linking the original shishes in the MD direction produce a planar orthogonal net of linked shish structures. The space among the shishes is filled with small and imperfect folded lamellae with c-axis in the film plane and preferentially oriented in the MD and TD directions, keeping constant crystallinity density throughout.This revised version was published online in November 2005 with corrections to the Cover Date.     

Biaxial orientation of polyamide films: processability and properties

The production of biaxially oriented films can be performed with two techniques: the tenter frame and the double bubble process. The most important difference between the two processes is that in tubular orientation the MD and TD stretching are simultaneous. This event is very important specially in the case of biaxially oriented polyamide films to avoid hydrogen bonding which occur during the first stretching stage of tenter frame process and cause resistance to subsequent transverse direction orientation (1-4). Double bubble process consists in the stretching of a tubular film where the stretching ratios in the machine and transverse directions are determined by inside bubble pressure and the difference in roll speeds between the two sets of nips rolls that contain the bubble. The work presented here reports some results about double bubble polyamide films realised with a laboratory scale system. The study concerns the processability (5-6) of two different polyamides: a nylon 6 (PA6) and a copolymer of the nylon 6 with isophthalic acid and isophorondiamine (PA6 - IPA.IPD) at 5% w/w of comonomer. Two main process arrangements where adopted differing for first bubble cooling technique: a water cooling and a air cooling. The films produced in both conditions were then characterised with a particular regard to mechanical and barrier performances. Morphological analyses were also carried out in order to correlate the process conditions to structure and properties of films.     

Mechanical behavior of films of miscible polyamide 6/polyamide 6I‐6T blends

The deformation behavior of miscible PA6/aPA blends films under uniaxial and biaxial tensile drawing has been investigated in relation to blend composition. Whatever be the composition, the initial crystalline structure is ill‐ordered and no evidence of spherulitic morphology was shown. At temperatures beyond the activation of the viscoelastic α relaxation, a ductility improvement upon addition of aPA has been revealed in both uniaxial and biaxial stretching. The decrease in the yield stress with increasing aPA content mainly originates from the reduction in crystal fraction. Regarding the observed evolution in ultimate drawability and strain hardening upon addition of aPA, the latter component of the blend is considered to act as a diluent of the macromolecular network, and the experimental data are fairly well accounted for according to Graessley's theory. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1690–1701, 2006     

Characterization of PVA and Chitosan/PVA Blends Prepared from Aqueous Solutions of Various Na2SO4 Concentrations

Uniplaner orientation of a particular crystal plane along the surface of a film was investigated for poly (vinyl alcohol) (PVA) film prepared by a coagulation bath with concentrated aqueous solution containing 100 ∼ 300g of Na₂SO₄ against 1 ℓ of water. The orientation distribution functions of the three crystallographic principal axes of the dried films were obtained by the X-ray diffraction technique. The same treatment was carried out for the films prepared by stretching biaxially of the fresh gel and then by drying the resultant fresh gel. The very high preferential orientation of the crystal chain axes and amorphous chain segments could be realized by the biaxially elongation. Accordingly, the techniques were applied to the biaxially stretching of chitosan and PVA blend films with high Young's modulus. The planer orientation of the chain axes of chitosan and PVA crystallites could be confirmed. The morphology of the film surface was estimated by measurements of contact angle and electron spectroscopy for chemical analysis. The results suggested that the admixture of chitosan decreases wet ability of the specimen and this tendency was slightly enhanced by the biaxially elongation.     

On the distribution of dye molecules in stretched poly(vinyl alcohol)

The symmetry of the orientational distribution function of dye molecules in stretched PVA films is studied using polarized fluorescence. The different symmetries are monitored by a simple experimental technique in which angle-resolved fluorescence depolarization ratios are measured. A uniaxial distribution of rhodamine 6G molecules is obtained on stretching the film at temperatures above 60°C. In contrast a biaxial distribution of trypaflavine molecules is found for stretch temperatures in the 50–115°C range. It is suggested that the hydrogen bonding between the PVA chains, and between the dye molecules and the PVA chains, influences the symmetry of the distribution upon stretching.     

Refractive index measurements of films with biaxial symmetry. 1. Determination of complex refractive indices using polarized reflectance/transmittance ratio

A new method to extract complex refractive indices of films with biaxial symmetry from polarized transmission and reflection spectra is described. Theoretical analysis demonstrates that the reflectance/transmittance ratio (R/T ratio) of two films of different thicknesses but with the same optical anisotropy is a simple function of the refractive index (n) and extinction coefficient (k). For films with biaxial symmetry, components of n and k on symmetric axes can be extracted from either s- or p-polarized R/T ratios if the film thickness values are known. The R/T ratio method can generate n and k spectra within a particular wavelength range without assuming a specific relationship among n, k, and wavelength, which is an advantage over many currently available techniques. The R/T ratio method is used to extract the anisotropic complex refractive indices of a polyimide film with known uniaxial symmetry. The resultant n and k spectra compare well with simulations based on known n and k values. The accuracy of n and k spectra is affected mostly by data error in reflection and transmission spectra collection, thickness variation across sample films, and error in sample alignment.     

Evaluation of poly(4‐methyl‐1‐pentene) as a dielectric capacitor film for high‐temperature energy storage applications

Poly(4‐methyl‐1‐pentene) (P4MP) was characterized to evaluate its viability as a high‐temperature dielectric film for capacitors. Detailed investigation of thermal, mechanical, rheological, and dielectric properties was carried out to assess its high‐temperature performance and processability. P4MP was melt‐processable below 270 °C without degradation and application temperatures as high as 160–190 °C can be achieved. The dielectric constant and loss of melt‐processed P4MP films was comparable to biaxially oriented polypropylene (BOPP) capacitor films, although the dielectric strength was lower. Enhancements in dielectric strength up to 250–300% were achieved via solution‐processing P4MP films, which could be easily scaled up on a roll‐to‐roll platform to yield isotropic, free‐standing films as thin as 3–5 μm. The influence of crystal structure, crystallinity, and surface morphology of these films on the dielectric properties was examined. The dielectric strength was further increased by 450% through biaxial stretching of solution‐cast films, and a Weibull breakdown field of 514 V/μm was obtained. The dielectric constant was very stable as a function of frequency and temperature and the dielectric loss was restricted to <1–2%. Overall, these results suggest that BOP4MP is a promising candidate to obtain similar energy density as a BOPP capacitor film but at much higher operating temperatures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1497–1515