Surface morphology and crystalline orientation of uniaxially drawn polytetrafluoroethylene films

For polytetrafluoroethylene (PTFE) films drawn uniaxially at 100, 150, 250, and 350°C, the morphology and degree of crystalline orientation were investigated by electron scanning microscopy and wide-angle X-ray diffraction, respectively. On the surface of the PTFE films which were heat-treated at 350°C for 2 h before the drawing, granules with a diameter of about 2 μm and bands with a width of about 0.3 μm were observed. By the drawing below the melting point, the bands are transformed into fibrils and a porous structure is formed by the drawing above the draw ratio (λ) of about 1.3. By drawing above the melting point, striations appear perpendicularly to the draw direction, and the collapse of the granules is observed. The orientation of the crystallites increases rapidly with increasing the draw ratio and approaches a plateau at λ ≈ 1.5 for the films drawn above the melting point and at λ ≈ 2.0 for that below it.     

Effects of orientation on mechanical properties of uniaxially oriented polystyrene films

Oriented samples of polystyrene have been produced by drawing at temperatures just above the glass transition range. Birefringence measurements have been used to characterise the degree of orientation. Mechanical measurements of elastic modulus and tensile yield stress have been made in the direction of drawing and it has been established that the birefringence value does not uniquely determine the mechanical properties—samples drawn to a high draw ratio at high temperatures have a higher modulus and yield stress than samples drawn at lower temperatures and lower draw-ratios to the same birefringence. The results are explained qualitatively by the convective constraint release theory of McLeish et al.     

聚乳酸的热降解性能研究

研究了聚乳酸(PLA)在10-40 min和170-200℃的条件下热降解后的特性粘数和端羧基含量的变化。结果表明,在一定温度下,PLA熔体特性粘数随熔融时间的延长而下降,在一定时间下,随熔融温度升高而下降,端羧基含量随熔融温度升高而增大,在PLA成型加工中,应严格控制加工温度。     

Ultrasonic and impulse welding of polylactic acid films

The weldability of polylactic acid (PLA) is examined in this article. Biaxially oriented PLA films of various thicknesses were joined with impulse and ultrasonic welding techniques. Relatively high weld strengths were achieved with impulse welding over a wide range of welding parameters. Ultrasonic welding produced high weld strengths with relatively short cycle times. In detail, ultrasonic welded samples had a weld factor (weld strength/base material strength) of 1 at cycle times of 0.25 sec. The weld factor was significantly lower at shorter weld times and weld times above 0.35 sec. In contrast, 100‐μm thick samples joined by impulse welding for 2–3 sec had a weld factor of 1 and a standard deviation of only ±5%. The peak temperature during the impulse welding was measured to determine the fusion temperatures of the films. Mechanical, thermal, and optical analysis was used to examine the properties of the PLA at various welding and annealing conditions. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Properties and weldability of plasticized polylactic acid films

The objectives of the presented work were to investigate films based on polylactic acid (PLA) and polyethylene glycol (PEG) in order to improve ductility and weldability of PLA films. The effect of plasticizer amount on the thermal, rheological, and mechanical properties of PLA plasticized films was investigated. The PEG content does affect the glass transition and the cold crystallization temperature of PLA in blends, while the melting temperature was not affected by the addition of PEG. The complex viscosity of the neat PLA granules and of plasticized films showed strong temperature and angular velocity dependence. The Young's modulus and tensile strength of plasticized films were improved with increasing plasticizer concentration, while the elongation at break stays rather constant. Plasticized PLA films were furthermore heat welded. These investigations showed that plasticized PLA films can be welded by heat welding. The obtained weld strength is strongly depending on the PEG amount as well as on selected welding parameters. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40394.     

Modification and extrusion coating of polylactic acid films

Polyethylene (PE) extrusion coating on paper substrates are the traditional packing material for coffee cups and take‐out food containers. It is difficult to recycle the PE/paper laminates and the thin polymer films remain in landfills after the decomposition of their paper substrates. Disposal of plastic materials is causing serious effects on our environment and wildlife. Demand for compostable or biodegradable plastic packaging products is increasing because of consumer pressure and legislation. Biodegradable polylactic acid (PLA) is regarded as one of the most promising biopolymers with a large market potential, but its applications are limited by poor thermal stability, mechanical properties and processibility. We utilize modified gelatin as additives to improve PLA's performance without compromizing the biomass origin and compostable properties of the material. Extrusion coating, or extrusion casting, of polylactic acid (PLA) films onto paper substrates to form PLA/paper laminates was achieved by modification of the polymer with a plant or animal gelatin. Various paper substrates with thin PLA coatings were prepared using a conventional extrusion coating equipment for the fabrication of take‐out food containers and coffee cups. Melt rheology of PLA and adhesion of the resulting thin film were greatly improved in the presence of a small amount of gelatin in the polymer matrices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42472.     

Effect of orientation on the biodegradability of uniaxially stretched aliphatic copolyester films

The effects of uniaxial drawing conditions on the orientation of aliphatic copolyester films were investigated by using both Fourier transform infrared-attenuated total reflection (FTIR-ATR) dichroism and wide angle X-ray diffraction (WAXD) methods. The results showed that orientation in uniaxially drawn films was determined by the drawing rate and drawing temperature. At higher drawing rates and higher drawing temperatures, higher orientation was obtained due to a large deformation of spherulites. The WAXD patterns of drawn films exhibited the preferential orientation of lamellar crystallites. The results of microbial degradation indicated that development of crystalline orientation evidently depressed biodegradability of samples. Video microscopy observations revealed that the degree of orientation played a dominant role in determining the rate of surface erosion. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1999–2006, 1997     

Mechanical,thermal, and structural properties of uniaxially drawn polylactic acid/halloysite nanocomposites

The effect of solid-state drawing at different conditions including drawing ratio (DR), drawing temperature (DT), and drawing speed (DS) on mechanical, thermal, and structural properties of polylactic acid (PLA)/halloysite nanotubes (HNTs) composites were studied. PLA/HNTs composite films were prepared by melt mixing process followed by compression molding. Subsequently, drawing was performed using a tensile testing machine. Field emission scanning electron microscopy confirmed alignment and orientation of polymer chains and HNTs after stretching. Thermal and mechanical analysis of the drawn films revealed that glass transition temperature, crystallinity, ultimate tensile strength, and Young's modulus were enhanced by increasing DR, DT, and DS. However, toughness was decreased by increasing DR and DS and increased by increasing DT. In addition, the drawn nanocomposites showed superior mechanical and thermal properties compared to the drawn neat PLA films indicating the high efficiency of solid-state drawing and positive effect of HNTs. Therefore, this study could be helpful to introduce an approach to enhance the properties of biopolymers and renewable polymers by uniaxial drawing.     

Morphology and glass transition of thin polylactic acid films

The aim of this study is to highlight the effect of the morphology of polylactic acid (PLA) thin films on the glass transition in this confined geometry. For that purpose, poly(L ‐lactic acid) and poly(D ‐lactic acid) polymer films were prepared on different surfaces such as mica and silicon surfaces by using two different solvents. The films exhibit different morphologies starting from individual macromolecular chains at very low concentration to homogeneous films at higher concentrations. Globular to elongated rodlike structures of the PLA macromolecules were observed according to the polarity of the surface and the solvent. The T_g of PLA enantiomeric film, determined by adhesion force using atomic force microscopy (AFM) as a function of temperature, was confirmed by ellipsometric measurements. Surprisingly, this value is independent of the morphology of thin enantiomeric film. A balance between the attractive surface effects and a decrease of the crystallinity of PLA on the mobility in the amorphous region will be discussed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Crystal structure and orientation of uniaxially and biaxially oriented PLA and PP nanoclay composite films

Cast films of poly(lactic acid) (PLA) and polypropylene (PP) with 2.5 and 5 wt % organo modified nanoclay were prepared and then uniaxially and biaxially hot drawn at T = 90 and 155°C, respectively, using a biaxial stretcher. The orientation of PLA and PP crystal unit cells, alignment of clay platelets, as well as the extent of intercalation and exfoliation were studied using wide angle X‐ray diffraction (WAXD). The measurement of d‐spacing of the 001 plane (normal to platelets plane) of the clay tactoids indicated the intercalation of the silicate layers for the PLA nanocomposite films, whereas the PP nanofilled films showed only dispersion of the nanoparticles (i.e., neither intercalation nor exfoliation were observed). The intercalation level of the clay platelets in PLA was almost identical for the uniaxially and biaxially drawn films. Our finding showed that the crystallite unit cell alignments are appreciably dependent on uniaxial and biaxial stretching. Moreover, the incorporation of clay to some extent influenced the orientation of the crystal unit cell axes (a, b, and c) of the oriented films. The silicate layers revealed a much higher orientation into the flow direction in the uniaxially stretched films compared to the biaxially drawn samples. In addition, the orientation of the 001 plane of nanoclays was significantly greater in the PLA compared to the PP nanoclay composite films probably due to a better intercalation and stress transfer in the former. Morphological pictograms illustrating the effects of uniaxial and biaxial stretching on the clay orientation are proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of annealing and orientation on microstructures and mechanical properties of polylactic acid

Two types of polylactic acid (PLA) films (one amorphous and one semi‐crystalline) were produced by sheet extrusion. Talc was used as a nucleation agent for the semi‐crystalline PLA. The films were annealed above their T_g or were uniaxially orientated in two ways: (1) via a drawing system in front of the extruder and die or (2) via a three‐roller stretching system. The slower crystallization rate and lower melting stress of the PLA resulted in amorphous film using the drawing system. Annealing above T_g increased crystallinity and polymer chain relaxation, which resulted in increases in both strength and toughness. Stretching above T_g also produced simultaneous crystallization and chain relaxation, which resulted in increases in both modulus and toughness. Both modulus and tensile strength in the stretching direction were higher than in the crosswise direction. Talc acted not only as a rigid filler to reinforce the PLA, but also as a nucleation agent for the PLA, especially during annealing. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Morphology and rheological behavior of polylactic acid/clay nanocomposites

The investigated rheological properties of polylactic acid (PLA)/clay nanocomposite are important to understand the effect of organically modified layered silicates (OMLS) (clay) on processing as well as the change in viscoelastic properties due to polymer filler interaction. The time sweep result revealed that the thermal stability improved with addition of nanoclay due to the formation of percolating network structure. It was also supported by multi wave ramp test. The frequency sweep analysis showed that the dynamic moduli increased with addition of nanoclay. Viscoelastic spectra (DMTA) showed an increase of the storage and loss moduli with the increase in the clay content. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) were used to determine the degree of intercalation, or exfoliation and nanostructure level of clay dispersion on PLA nanocomposites. XRD data demonstrated complete exfoliation at lower nanoclay content. On increasing the nanoclay content, exfoliated and partially intercalated structures were obtained. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Properties of uniaxially stretched polypropylene films

Polypropylene (PP) films have been prepared through two different cast extrusion processes: one using a machine direction orientation (MDO) unit and the other stretching the films at the die under high cooling conditions (lab unit). Films for two PP resins different in molecular structure have been prepared using both processing techniques. The effect of the resin structure and the processing conditions on the film properties has been examined. It was found that the MDO unit generated a highly oriented fibrillar crystalline structure with a distribution of elongated thick fibrils while extrusion under high cooling conditions generated an oriented row nucleated lamellar structure. The films showed distinctive tensile responses in stretching, with a strong solid‐elastic response for the oriented MDO films and a steady strain hardening after yielding for the sample obtained from lab unit cast extrusion. It was found that the strength in the transverse direction (TD) was particularly very low for the oriented MDO films made of the bimodal PP. The oxygen permeability was reduced with increasing draw ratio (DR) for the MDO films. The haze property for the MDO samples reduced to a plateau for DR up to 5 while clarity improved continuously with DR.     

Influence of biaxial stretching mode on the crystalline texture in polylactic acid films

Structural evolution during simultaneous (SB) and sequential rubbery state biaxial stretching (SEQ) of polylactic acid (PLA) films from cast amorphous precursors was investigated. Simultaneous biaxial stretching always leads to films with in-plane isotropy and poor crystalline order. In the first stage of sequential biaxial stretching, oriented crystallization gradually develops while transverse isotropy is maintained. Application of transverse stretching to these films possessing semicrystalline structure gradually destroys the crystalline structure oriented in MD during this realignment while establishing a second population of oriented but poorly ordered crystallites in TD. This destruction is caused primarily by splaying action under transverse stretching as evidenced by the decrease of crystallite sizes in MD.     

The role of nanofillers on the degradation behavior of polylactic acid

This study examines the effect of type and content of various nanofillers on the aging behavior of polylactic acid (PLA)/nanocomposites compared with that of pristine PLA, under specific environmental conditions, namely 80% relative humidity, 40°C temperature, and exposure time up to 6 months. Two different types of nanosized fillers (silica and montmorillonite, MMT) at three different weight fractions as well their mixtures were used for this purpose. The role of the various nanofillers on the aging of pristine PLA and its nanocomposites was investigated in terms of several experimental techniques including Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and tensile testing. All studied samples, except those of PLA/MMT/Si nanocomposites, exhibited the same trend in properties during aging. In particular, no significant changes are noted after 1 month of aging. The materials after 3 months of aging experienced a dramatic lowering of the stress–strain curve, whereas at 6 months a reverse effect was observed. Comparing the effect of nanofiller types on the degradation, one could conclude that PLA/MMT nanocomposites exhibit a more homogeneous degradation effect, having a higher impact on yield stress in comparison with silica. In contrast, silica has a greater effect in Young's modulus and strain at break, compared with MMT. The peculiar behavior of the PLA/MMT/Si nanocomposites during aging is explained by the hindering action of the mixture of the two nanofillers on the molecular reordering of the PLA chains in the amorphous region. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Electrospinning of porous polylactic acid fibers during nonsolvent induced phase separation

In this study, porous micron‐sized fibers of polylactic acid (PLA) are fabricated via electrospinning of PLA‐dichloromethane (DCM)‐hexane systems with no post treatment involved. Several compositions from the liquid‐liquid phase separated region of the phase diagram of this ternary system are selected and their electrospinnability are investigated throughout their phase separation process before gelation. We show that under constant processing and ambient parameters, there is a phase separation shelf time for each composition wherein the viscoelasticity of the systems is optimum to produce long, uniform porous fibers. For the first time, we investigate the effect of aging time during phase separation on the morphology of the electrospun fibers using scanning electron microscopy (SEM). Based on our results, certain phase separated systems provide a range of viscosity allowing for the production of porous spherical micro beads or fibers via electrospraying and electrospinning, respectively. It is also shown that obtaining long, uniform fibers from electrospinning of highly phase separated systems, e.g., a gel, is not feasible due to the high degree of crystallinity of their polymer‐rich domains and the solid‐like yielding behavior. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44862.     

Production of porous polylactic acid monoliths via nonsolvent induced phase separation

Polylactic acid (PLA) is one of the most promising polymers for use as the matrix of a bone scaffold. In this work, porous PLA monoliths are fabricated via nonsolvent induced phase separation using dichloromethane as a solvent and hexane as a nonsolvent. The PLA-dichloromethane-hexane compositions which undergo liquid–liquid phase separation followed by gelation are shown to allow for the production of high quality foams. Solvent exchange with methanol after aging the gel is found to substantially reduce shrinkage during drying. Using this simple, versatile and template-free method we produced PLA foams with porosities as high as ∼90.8%, specific surface area up to 54.14 m²/g, crystallinity up to 62.6% and compressive modulus ranging from 1.8 to 57 MPa. Depending on ternary mixture concentration and standing temperature a range of mesoporous and combined meso/macroporous morphologies suitable for use as a bone scaffold are produced.     

Influence of pearlescent pigments on mechanical properties and crystallization behavior of polylactic acid

Polylactic acid (PLA)/pearlescent pigments (PEPs) composites were fabricated by melt blending method and their properties were studied using a rotational rheometry, field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). Because PEP could disperse uniformly in PLA matrix and would form PEP networks, there were improvements made in the flexural strength, tensile strength and impact strength of PLA composites. Interestingly, the viscosity of PLA composites reduced significantly as compared with neat PLA, indicating an improvement in processing properties. The rheological tests confirmed that the storage modulus of PLA composites decreased as PEP content increased at a given frequency. Also, there was a plateau at low frequency range, which was a sign of PEP networks formation. The DMA tests showed that the storage modulus of PLA composite increased with PEP content, suggesting the enhancement of rigidity. According to the XRD results, no change was observed in the crystal structure of PLA in the presence of PEP. The addition of PEP did not change melting temperature, but the glass transition temperature increased a little, and the cold crystallization temperature of PLA decreased largely. The DSC results also showed that nucleation ability of PLA was enhanced by addition of PEP at low cooling rates, but the whole crystallization process of PLA in composite was inhibited at higher cooling rates. This conclusion was also confirmed by the results of crystallization kinetics.     

Dynamic viscoelasticity and molecular orientation in uniaxially drawn PC/PET blends

The dependence of dynamic viscoelasticity on molecular orientation of the hot-drawn polycarbonate (PC)/poly(ethylene terephthalate) blends was studied experimentally. The oriented states of samples were investigated by wide-angle X-ray diffraction and quantified by Hermans' factor. The viscoelasticity was probed by dynamic mechanical analysis. For the fitting curves of dynamic modulus versus orientation, the PC-rich blends with different compositions had an opposite concavity and convexity compared with the neat PC. The difference revealed the influence of molecular mobility on orientation and viscoelasticity. The assumption on the phase morphological change from sea-island to local sandwich-like structure in blends was proposed and used to interpret the variation of slope of fitting curves. The relationship between orientation and viscoelasticity was observed in PC-rich blends, which can help understand the mechanism of molecular orientation and develop the constitutive relations for simulation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47514.     

Crystallization behavior and morphology of polylactic acid (PLA) with aromatic sulfonate derivative

This article provides a detailed investigation of crystallization behavior and morphology of polylactic acid (PLA) in the presence of a nucleating agent: potassium salt of 5‐dimethyl sulfoisothalate, an aromatic sulfonate derivative (Lak‐301). Isothermal crystallization kinetics of PLA melt mixed with Lak at concentrations of 0.25–1 wt % was investigated at a range of crystallization temperature, 140–150 °C. To gain further insight on the effect of Lak, nonisothermal differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized optical microscope (POM), heat deflection temperature (HDT), and rheology were also performed. At 0.25 wt % Lak, crystallinity of PLA increased from 10% to 45%, and in 1 wt % Lak, maximum crystallinity of 50% was achieved. With 1 wt % Lak, crystallization half time reduced to 1.8 min from 61 min for neat PLA at 140 °C. The isothermal crystallization kinetics was analyzed using Avrami model. Values of the Avrami exponent for PLA with Lak were mainly in the range of 3 indicating a three dimensional crystal growth is favored. Crystallization rate was found to increase with increase in Lak content. Observation from POM confirmed that the presence of Lak in the PLA matrix significantly increased the nucleation density. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43673.