Biaxially oriented polypropylene film in power capacitors

The use of polymer dielectrics, particularly biaxially oriented polypropylene (BOPP), has revolutionized power distribution around the world. BOPP film of sub mil thickness has displaced impregnated Kraft paper because of superior dielectric performance, lower cost, and small volume. The polypropylene molecule has a unique set of properties which combine stable dielectric properties in the operating temperature and frequency range along with an adequate dielectric constant. High levels of orientation and a small unbalance of orientation are required to produce films of high dielectric strength over large areas of film. Control of thickness uniformities to approximately ± 5 percent are critical to the reliable operation of the capacitor under load and to control of capacitance in the product. A special fibrillated surface is required which promotes complete impregnation by the dielectric fluid. This surface is acquired by the development of a specific crystal morphology at one surface of the film. No additives are used to promote this crystalline structure since most additives effect dissipation factor and generate unwanted heat. Similarly, control of contamination (ppm and ppb) is a key factor in the manufacture of film power capacitors.     

Relationship between biaxial orientation and oxygen permeability of polypropylene film

Biaxially oriented polypropylene (BOPP) films were produced by simultaneous and sequential biaxial stretching to various balanced and unbalanced draw ratios. The BOPP films were characterized in terms of density, crystallinity, refractive index, oxygen permeability and dynamic mechanical relaxation behavior. It was found that the density and crystallinity of BOPP films decreased as the area draw ratio increased. Sequential stretching led to a slightly lower density than simultaneous stretching to the same draw ratio. Moreover, sequential stretching produced lower orientation in the first stretch direction and higher orientation in the second stretch direction compared to simultaneous stretching. The study confirmed the generality of a one-to-one correlation between the oxygen permeability of BOPP films and the mobility of amorphous tie chains as measured by the intensity of the dynamic mechanical β-relaxation. Moreover, the study established the correlation for commercially important sequentially drawn BOPP films with an unbalanced draw ratio. Finally, the chain mobility in the stretch direction was found to depend on the final stress during stretching.     

Comparative study on development of structural hierarchy in constrained annealed simultaneous and sequential biaxially stretched polylactic acid films

Structural evolution during constrained annealing of PLA films biaxially stretched in simultaneous and sequential biaxial stretching was compared. Annealing of simultaneous biaxially stretched films yields films with in-plane isotropy with (100) crystallographic planes parallel to the surface. The first stage of sequential stretching where the films are stretched in Uniaxial constrained mode was found to yield films exhibiting transverse isotropy. The transverse stretching of these films lead to formation of a distinct second population of chains primarily oriented in transverse direction, generating bimodal orientation texture. When the extent of stretching in two directions are balanced, constrained annealed samples were found to exhibit uniplanar axial (100)[001] texture with the primary chain axial direction now switched to transverse direction. Two new superstructures, along [110] and [100] respectively were discovered in annealed PLA films.     

Preparation and characterization of biaxially oriented polypropylene film with high molecular orientation in the machine direction by sequential biaxial stretching

Novel approach of applying the ternary polymer blend of long‐chain branched polypropylene (LCB‐PP), conventional polypropylene (PP), and hydrogenated polydicyclopentadiene (hDCPD) has been employed to tensilize biaxially oriented polypropylene (BOPP) film in the machine direction (MD) by successive sequential biaxial stretching method. It is found that the addition of LCB‐PP improves the MD stretchability of the BOPP film of PP/hDCPD blend. Depending on the content of LCB‐PP, LCB‐PP/PP/hDCPD ternary blend could be biaxially stretched up to the MD stretching ratio (MDX) of 12 without film breakage whereas that of PP (conventional BOPP film) resulted in the MDX up to 6. This excellent MD stretchability enabled to tensilize the BOPP film in the MD, where Young's modulus in the MD could be increased up to 4.9 GPa, twice higher than that of conventional BOPP film. The orientation of total molecular chains and that of crystalline molecular chains were evaluated by in‐plane distribution of refractive indices and wide‐angle X‐ray diffraction, respectively. The results are discussed from the viewpoint of deformation behavior during stretching process. Moreover, the resultant film had a dimensional stability substantially equivalent to that of conventional one, in spite of the higher stretching ratio, and an improved moisture barrier property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Development of orientation and mechanical properties of extrusion cast polyamide 11 films in biaxial stretching process

The development of orientation of extrusion cast polyamide 11 films in the biaxial stretching process was studied with birefringence and wide angle X‐ray diffraction (WAXD) pole figures. White‐Spruiell biaxial orientation factors of the crystalline phase were calculated with the pole figure data. Both biaxially stretched films were developed. Planarity of hydrogen bonding planes with respect to the film surface was observed from WAXD pole figures. Mechanical properties of the films were studied. Tensile strength and elongation at break were successfully correlated with the out‐of‐plane birefringences.     

Orientation distribution in the noncrystalline regions of biaxially drawn poly(ethylene terephthalate) film: A chain-intrinsic fluorescence study

We have studied development of the in-plane distribution of “amorphous orientation” during sequential and simultaneous biaxial drawing of poly(ethylene terephthalate) film, using polarized intrinsic fluorescence. The machine direction (MD) draw ratio was always fixed at 3.5, and the transverse direction (TD) draw ratio was varied. The rate of increase in the proportion of TD-oriented chains with increasing TD draw ratio is almost identical in the sequential and simultaneous processes up to a draw ratio of 2.7. At this point, sequential drawing starts to involve transverse realignment of MD-oriented chains, which accelerates redistribution of orientation from the MD to the TD. Consequently, in sequential drawing, a “balanced” biaxial orientation distribution is achieved at a TD draw ratio significantly below the MD draw ratio, whereas at the same TD draw ratio in the simultaneous process, MD orientation remains dominant. At equal MD and TD draw ratios, the non-crystalline chains in sequentially drawn film are predominantly oriented along the TD, but their orientation distribution is isotropic in simultaneously drawn film. High-temperature annealing at fixed dimensions diminishes the proportion of TD-oriented chains in films with transverse draw ratios < 2.5. We attribute this to a more highly developed crystallite network in the MD, which constrains orientational relaxation along the MD. A balanced distribution of amorphous orientation is directly responsible for achieving balanced tensile strength and balanced extensibility. © 1993 John Wiley & Sons, Inc.     

Polymer Crystallization Induced by Biaxial Stretching During Film Manufacture

Abstract

In the manufacture of semicrystalline polymer films, orientation is commonly introduced. This orientation may be uniaxial, unbalanced biaxial, or balanced biaxial. Machine-direction and transverse stretching may be concurrent or sequential; each orienting process is characterized by a trajectory on the biaxial stress plane and the biaxial extension plane. The presence of uniaxial or biaxial tensile stress strongly affects the process of polymer crystallization, influencing the crystal-amorphous equilibrium, crystallization kinetics, and the resulting polymer morphology. Post-solidification alterations in morphology can be imposed by drawing or heat-setting under biaxial tension, below the crystalline melting point.

The machine-direction and transverse properties of a semicrystalline polymer film depend strongly on the crystalline morphology, and hence on the processing history. The dependence of film properties on processing conditions are well recognized and widely exploited; but the morphology of biaxially oriented films and the structure-property relationships involved are only partly understood.     

Preparation of biaxially oriented polyamide 6/polyketone/graphene oxide films with enhanced barrier and mechanical behaviors

In this study, biaxially oriented polyamide 6/polyketone/graphene oxide (PA6/PK/GO) films were prepared by melt blending then simultaneously biaxially stretched process, with the aim of obtaining high barrier properties films and improvements in their mechanical properties. The oxygen transmission rate of biaxially oriented PA6/PK/GO film significantly decreased with addition of polyketone and GO. It is surprising that the biaxially oriented process can excellently improve the barrier properties of biaxially oriented PA6/PK/GO film. For example, there was 94.7% OTR reduction of the film containing 20 wt% PK and 0.08 wt% GO compared with PA6 film at a stretching ratio of 3.3 × 3.3. It is due to more tortuous permeation path of oxygen molecule owing to molecular orientation during biaxially stretching, and higher relative crystallinity with addition of GO. The tensile strength of film was remarkablly improved by stretching orientation and increase GO concentration. However, the elongation at break of film was considerably reduced by increase of stretching ratio. Although addition of GO may slightly improve the elongation at break of film at low stretching ratio, there was dramatic decline of elongation at break with increasing the content of GO at a stretching ratio of 3.3 × 3.3.     

Biaxial orientation of poly(vinyl chloride) compounds: Interaction between drawing,structure, and properties

Rigid poly(vinyl chloride) (PVC) sheets were stretched uniaxially (at constant width), equally biaxially, and unequally biaxially to various draw ratios. Tensile properties, density, and birefringence of the stretched sheets were measured, and their wide angle X-ray diffraction traces recorded. Comparison of results showed the highest crystallite and overall orientation and density in the uniaxial samples, and lowest values for the equal biaxial samples. Drawing resulted in the alignment of some existing crystallites in the plane of the film, together with the formation of new mesomorphous structures. Changes in tensile strength were attributed to overall orientation.     

Preparation and characterization of biaxially oriented films from polybutylene terephthalate based thermoplastic elastomer block copolymers

Film casting and biaxial stretching of a series of polyester thermoplastic elastomers (TPEs) were studied. Biaxial orientation in the stretched films was characterized by wide‐angle X‐ray diffraction and birefringence measurements. Biaxial orientation factors were determined. The X‐ray diffraction and birefringence clearly indicated the development of planar biaxial orientation in the stretched films with biaxial stretching. The phenyl groups in the stretched PBT and TPE films gradually became more parallel to the film surfaces with increasing biaxial orientation. The lower the PBT content in the stretched TPE films, the lower the planar biaxial orientation achieved. The β form of crystalline PBT was found only in the stretched PBT films, but not in the TPE films.     

Enhanced dielectric properties of sandwich-structured biaxially oriented polypropylene by grafting hyper-branched aromatic polyamide as surface layers

This work represents multilayer films with sandwich structure by grafting hyper-branched aromatic polyamide (HBP) on both sides of biaxially oriented polypropylene (BOPP) (HBP BOPP HBP). BOPP serves as the middle layer to offer high breakdown strength and HBP acts as surface layers to boost the dielectric constant. As a result, the dielectric constant increases significantly from 2.2 of control BOPP to 5.5 (almost increased 1.5 times) after grafting 2.06 μm HBP surface layers, while the dielectric loss still remains at a very low level (<0.03). In addition, all HBP BOPP HBP sandwich-structured films show higher charge energy density than that of unmodified BOPP. For instance, the discharge energy density of HBP BOPP HBP (1-20-1) film is up to 2.38 J/cm³ at an applied electric field of 400 kV/mm, which increases about 36% over that of pure BOPP (i.e., 1.75 J/cm³). Meanwhile, charge–discharge efficiency retains about 90%. This work offers a simple strategy to fabricate polymer-based high performance dielectric composites.     

Influence of incorporation of ZnO nanoparticles and biaxial orientation on mechanical and oxygen barrier properties of polypropylene films for food packaging applications

In this work, the effect of zinc oxide (ZnO) concentration and shape on processing and properties of new biaxially oriented polypropylene (BOPP)‐ZnO nanocomposites was studied. The use of spherical nanoparticles and nanorods was expected to differently influence the properties of the final material. Films of isotactic polypropylene prepared with different ZnO incorporation were biaxially oriented under conditions of temperature and strain rate that were similar to those encountered in a commercial film process. Scanning electron microscopy analysis was performed to visualize the dispersion degree of the ZnO nanoparticles in the polymer matrix and to observe the surface and the orientation of the elongated nanoparticles. Furthermore, the prepared ZnO‐BOPP nanocomposites were evaluated for both mechanical and oxygen barrier property enhancement. A good combination of mechanical and oxygen barrier properties was obtained for the ZnO‐BOPP films. This result makes the ZnO‐BOPP nanocomposite a proper material for applications such as food packaging. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The relationship between microstructure and toughness of biaxially oriented semicrystalline polyester films

The relationship between microstructure and toughness of biaxially stretched semicrystalline polyester films was investigated. Optically transparent films were prepared by simultaneous biaxial stretching of melt-cast sheets near the glass transition temperature. Copolyesters of polyethylene terephthalate (PET) with different compositions of two diols: ethylene glycol (EG) and cyclohexane dimethanol (CHDM), and stoichiometrically matched terephthalic acid were used to produce films with different degrees of crystallinity. In addition, the PET films with different crystalline morphologies were produced by constrained high temperature annealing of biaxially oriented films. The toughness, degree of crystallinity and crystalline morphology/molecular ordering were studied using mechanical testing, synchrotron small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD) techniques, and differential scanning calorimetry (DSC). The results indicate that the toughness of a semicrystalline polymeric film is determined by the interconnectivity of the crystalline phase within the amorphous phase and is greatly influenced by the degree of crystallinity and the underlying crystalline morphology.     

Control of well‐defined crater structures on the surface of biaxially oriented polypropylene film by adding nucleators

While it is common to add anti‐blocking agents to biaxially oriented polypropylene (BOPP) films for general use in order to prevent blocking against each other, the technology of crater‐like film surface roughness formed on the BOPP films without any additives is well known in the industrial BOPP film areas. Numerous studies have been reported on the crater‐like film surface roughness on the BOPP films since the 1980s, but its formation mechanism and the controlling method of the crater‐like film surface roughness are yet to be clarified. In our previous reports, we presented a new hypothesis of crater formation mechanism from a new point of view on sheet morphology and crater shape on the BOPP film surface. It was strongly influenced by the crystal grain shape in the surface layer of PP sheet. In this report, it was clarified that a nucleator has a big influence on the formation of the crystal grains in the surface layer of PP sheets and on the formation of craters. In addition, craters did not form on the BOPP films stretched from the sheet of which the skin layer with crystal grain was shaved, even though β crystal still remained. It was clarified that the crystal grain is trans‐crystal from the observation using TEM. Therefore, it is concluded that the existence of β crystals in the surface layer of PP sheets is not essential in order to produce craters on BOPP films, but trans‐crystals are necessary to form the craters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3555–3564, 2013     

Effects of the biaxial orientation on the mechanical and optical properties and shrinkage of polyamide 6-66–montmorillonite–nanosilica nanocomposite films

Polyamide 6–66 (PA6-66)–montmorillonite (MMT)–nanosilica (NS) nanocomposite films were fabricated through a cast film process and then biaxially stretched on a laboratory stretcher. Uniaxial or biaxial stretching induced the elongated conformation of MMT and NS. The b axis of the α crystals and the amorphous phase were revealed to align along the machine direction (MD) after stretching, with the uniaxial orientation playing a more significant role. Furthermore, the crystallinity of PA6-66 stretching increased with the stretching ratio. Uniaxial stretching gave rise to a significantly enhanced tensile strength along the MD, whereas it slightly decreased the mechanical properties along the transverse direction (TD). In contrast, the films subjected to biaxial stretching exhibited more balanced mechanical properties. Uniaxial and biaxial stretching led to decreased transmittance and increased haze in the PA6-66–MMT–NS films; this could have been due to the elongated nanostructure of the two nanofillers, which inhibited the transmission and facilitated the scattering of visible light. The thermal shrinkage of the films increased with increasing stretching ratio, and the biaxially oriented films presented nearly equal shrinkage in the MD and TD. The addition of nanofillers decreased the shrinkage attributed to the mobility inhibition of the polymer chains during heating. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47504.     

Nanoindentation and nanoscratch testing of uniaxially and biaxially drawn poly(ethylene terephthalate) film

Nanoindentation and nanoscratch testing have revealed large differences in nanomechanical behaviour on uniaxially and biaxially drawn poly(ethylene terephthalate) films. Differences can be ascribed to the processing history of the film. The biaxial material exhibited significantly higher hardness and elastic modulus than the uniaxial film, presumably due to increased crystallinity from the second draw. The biaxially drawn material was also less susceptible to creep deformation. The plasticity index, the ratio of the dissipated energy to the total indentation energy, was greater on the uniaxial film, indicating that it exhibits less plastic deformation than the biaxially stretched film. The differences in processing also affected the resistance of the films to nanoscratching wear. The wear resistance of the films correlated with the ratio of the hardness to the modulus.     

Effect of molecular orientation on the dielectric properties of spin-coated polyimide films

The effect of molecular orientation on the dielectric properties of spin-coated polymide films has been studied in Situ for pyromellitic dianhydride with 4,4′-oxydianiline (PMDA/ODA) and biphenyldianhydride with p-phenylendiamine (BPDA/PPD). The degree of molecular orientation is characterized by the optical anisotropy between the in-plane and the through-plane, refractive indices. The through-plane dielectric properties are measured by fabricating parallel-plate capacitors directly onto the silicon substrate. Both the birefringence and the dielectric constant of PMDA/ODA polyimide vary with film thickness; however, these properties are independent of film thickness for BPDA/PPD films. To confirm that the measured dielectric constant obtained from the parallel-plate structures is free from a significant edge effect, finite element modeling of the electrstatic potential within the dielectric edge effect, finite element modeling of the electrostatic potential within the dielectric is performed. Models for both isotropic and anisotropic dielectric properties indicated that the fringing effects are indeed negligible for the film thicknesses examined. Thus, the changes observed in the measured dielectric constant are attributed to the variations in the molecular orientation. The optical anisotropy observed for the polyimides suggests a corresponding dielectric anisotropy in the films. An estimation using the Maxwell relation indicates that the dielectric anisotropy at 10⁵ Hz is 0.31 for PMDA/ODA and 0.85 for BPDA/PPD. © John Wiley & Sons, Inc.     

A new method for achieving nanoscale reinforcement of biaxially oriented polypropylene film

Nanolayers of poly(ethylene oxide) (PEO) produced by layer-multiplying coextrusion crystallize as single, high aspect ratio lamellae that resemble large single crystals. The confined crystallization habit imparts two orders of magnitude reduction in the gas permeability. We now demonstrate how the highly oriented lamellar nanolayers can be obtained with biaxial stretching. For this purpose, we chose biaxially oriented polypropylene (BOPP) film for modification and incorporated PEO nanolayers under conditions that mimicked the typical fabrication process. Sheet that contained a center core with 33 alternating layers of polypropylene (PP) and PEO was coextruded and subsequently biaxially oriented at 145 °C. Biaxial stretching reduced the PEO layer thickness from the spherulitic microscale to nanolayers of highly oriented PEO single lamellae. The nanolayers improved the oxygen barrier by an order of magnitude without sacrificing the high clarity and good tear resistance of BOPP film.     

Morphology-property relationships in oriented PET films: A role of in-plane crystalline orientation distribution on the film properties

The role of in-plane crystalline, amorphous, and overall molecular orientation on various properties in the plane of the films was investigated using a variety of techniques. It is shown that for a fixed value of crystallinity the in-plane crystalline orientation and the nature of the constraint imposed by the crystallites on the molecules play an important role in obtaining isotropic in-plane expansion or shrinkage properties. Achievement of in-plane isotropic tensile strength and elongation at the break are found to depend entirely upon an isotropic distribution of the amorphous orientation; the orientation of crystallites plays no detectable role. Furthermore, the deformation mechanisms of sequential and simultaneous biaxial stretching processes have been investigated and compared. The simulteneous stretching process is considered to be a more controlled film-fabricating method compared to sequential stretching in achieving balanced, in-plane film properties. © 1993 John Wiley & Sons, Inc.     

Biaxially oriented poly(ethylene terephthalate) bottles: Effects of resin molecular weight on parison stretching behavior

Uni- and biaxial stretching of poly(ethylene terephthalate) (PET) specimens of appropriate geometry at temperatures near the glass-rubber transition may lead to non-uniform deformation unless the draw ratio exceeds a critical value, the natural draw ratio, characteristic of the onset of strain hardening due to stress-induced crystallization. Experimental results obtained in the present investigation show that natural draw ratios in uni- and biaxial stretching decrease with increasing resin molecular weight and with decreasing temperature. Undesirable uneven wall thickness distribution in biaxially stretched cylindrical parisons can only be prevented if draw ratios in both orthogonal principal stretching directions exceed the corresponding natural values. The minimum thickness reduction required for uniform biaxial stretching of a cylindrical parison at 95°C may vary between 12 and 5 depending on the resin's molecular weight or viscosity and this will affect the optimum design of parison geometry. The degree of unbalanced biaxial molecular orientation in the wall of cylindrical parisons stretched up to or beyond the natural draw ratios also depends on the resin molecular weight. Unbalanced biaxial orientation has been investigated by means of wide angle X-ray diffraction and birefringence measurements as well as its effect on various properties: rigidity, yield stress, creep compliance, and dimensional stability.