Thin Polypropylene Films Research Articles

Adsorption isotherm and kinetics of diffusion of water accumulated between polypropylene thin film and Si substrate: Neutron reflectivity investigation

Isotactic polypropylene (PP) thin films deposited on Si substrates were subjected to neutron reflectivity (NR) measurements under various humidity conditions to evaluate the isothermal adsorption of water accumulated between the PP layer and Si substrate, with focus on the temperature-dependence of the adsorption isotherm. The adsorption of accumulated water followed a single type II isotherm according to the Brunauer-Emmett-Teller (BET) classification, regardless of temperature. This can be attributed to the weak interactions between the PP layer and Si substrate, and between the PP layer and water molecules. Hydrophobic PP does not significantly interact with water molecules and the hydrophilic Si surface. Therefore, the interfacial water molecules are simply adsorbed on the native oxide layer on Si via simple interaction between the water molecules and the silicon oxide surface without being affected by the PP layer. Consequently, the adsorption isotherm of the accumulated water follows the single type II adsorption isotherm regardless of temperature, similar to the adsorption isotherm of water simply adsorbed on exposed silica surfaces. These weak interactions of the PP layer with the Si surface and water molecules also lead to fast diffusion kinetics for the accumulated water along the interface.

Process-induced residual stress in a single carbon fiber semicrystalline polypropylene thin film

During the processing of semicrystalline thermoplastic composites, various models for the prediction of residual stress have been proposed but experimental validation is limited. In this study, a modeling framework is developed to predict the evolution of residual stress in a single carbon fiber embedded in a semicrystalline polypropylene thin film subjected to non-isothermal cooling. Validation is based on in-situ measurement of axial fiber strain after processing using micro-Raman Spectroscopy. A material model for polypropylene (50% equilibrium crystallinity) is presented that incorporates the effects of non-isothermal cooling on crystallinity-dependent resin shrinkage and crystallinity-dependent resin modulus from the amorphous polymer melt to room temperature. The evolution of residual stress is calculated using a finite element (FE) model with a user-developed subroutine incorporating the resin material models. Single-fiber polypropylene films are fabricated using a range of fiber pretension levels to prevent fiber waviness during cooling and to induce a wide range of axial strain levels in the fiber for model validation. The fiber axial strain was measured over the length of the fiber, from the free edge into the bulk, capturing the ineffective length region where strain builds up and plateaus. A good correlation has been obtained between the model results and the in-situ measurements of axial compression strain in the fiber. A key finding was the importance of including temperature-dependent resin modulus and that the contribution of crystallinity shrinkage to residual strain in the carbon fiber is relatively low. The model developed in this study is also compared to residual stress models in the literature which shows the importance of including the effects of crystallization and cooling rate on temperature and crystallinity-dependent modulus and resin shrinkage for accurate predictions.

Nanoscale thinning of metal-coated polypropylene films by Helium-ion irradiation

Polypropylene (PP) films have a wide range of applications, e.g. as dielectric materials for metallized film capacitors. In this article, we present a method for thickness reduction of PP films by ion irradiation, which has a direct effect on device capacitance. We show that the thickness of PP layers can be reduced by irradiation with He+ ions and controlled on the nanometer scale by the irradiation dose. The effect of different thin metal film coatings on PP surface was also investigated. The metal coatings were used for two reasons: they function as one of the metal electrodes in the capacitor structure, and they minimize sample charging during ion irradiation. Three different metallization materials were investigated: 5 nm Pt60Pd40, 5 nm Au, and 15 nm Al. We studied two technologically relevant PP films: the thinnest commercially available biaxially oriented polypropylene (BOPP) and spin-coated polypropylene (SC-PP) thin films. The irradiation was done with a focused Helium-ion beam (He-FIB) in a Zeiss Orion NanoFab Microscope at a landing energy of 30 keV with doses in a range of 5.4 × 10–5 nC/μm2 to 8.1 × 10–3 nC/μm2. An atomic force microscope (AFM) was used to analyze the details of surface modification: the surface height of the irradiated regions and surface morphology changes caused by the irradiation. For all applied doses, the Al-coated samples demonstrated smaller surface-height reduction compared to the Pt60Pd40 and Au-coated samples. We speculate that the possible factors responsible for this effect include differences in the thickness and the crystalline-grain orientation (texture) of the metallization films. Both BOPP and spin-coated PP presented surface ridges at the borders between the irradiated and non-irradiated regions. It can be attributed to the mechanical strain induced by the material modification.

Determining the maximum melting temperature of polymer crystals from a change in morphology of dewetting rims

Dewetting experiments on molten spherulites, previously grown at Tc = 120 °C in thin films of isotactic polypropylene (iPP), revealed two kinds of instabilities of the dewetting rims, namely a fingering instability and a fracture instability for dewetting temperatures Ts above and below ca. 165 °C, respectively. For Ts ≥ 165 °C, the dynamics of growing dewetting holes on slippery substrates was governed by viscous dissipation, causing undulations leading to a fingering instability of the rims. However, for 160 °C < Ts < 165 °C, the dewetting rims exhibited a fracture instability, which was related to the release of elastic energy stored in the rim. From the dewetting dynamics of the molten polymers, we derived the non-equilibrium viscosity ηnon-equ(Ts) and equilibrated viscosity ηequ(Ts) as a function of Ts. The values of ηnon-equ(Ts) were significantly larger than ηequ(Ts), with differences decreasing for increasing Ts. Interestingly, extrapolation of ηnon-equ(Ts) to the cross-over point ηnon-equ = ηequ yielded Ts,cross ≈ 166 °C. We relate Ts,cross with the maximum melting temperature of crystalline domains which existed within iPP spherulites. Below Ts,cross, not all crystallites were molten and the melt contained crystalline seeds. Above Ts,cross, the melt was homogeneous and free of any seeds. Our approach opens up a new possibility for determining the maximum melting temperature of polymer crystals.

Synthesis of silylamine and siloxyamine compounds: A novel approach to flame retardancy of polypropylene and Epoxy resins

A series of innovative flame retardants containing N-Si and N-O-Si bonds have been synthesized. Their chemical structures were verified by nuclear magnetic resonance (NMR) spectroscopy and thermal stabilities determined by thermogravimetric analysis (TGA). The results indicate that their thermal and hydrolytic stabilities could be adjusted by fine tuning their silylamine (N-Si) and siloxyamine (N-O-Si) skeletons. Thus, the substituents bonded to the phthalimides, such as diphenylmethylsilyl, dimethylphenylsilyl, diphenyl‑tert-butylsilyl, triisopropylsilyl or diphenylmethylsiloxy; whichever was attached to the imide played a significant role on its thermal and hydrolytic properties. Upon thermal dissociation, the N-Si and N-O-Si compounds were shown to yield aminyl, silyl and oxygen-centered radicals that provided fire proofing effect in polypropylene (PP) films alone and a synergistic effect in combination with conventional phosphorous flame retardant in PP, linear low-density polyethylene (LLDPE) and epoxy resins (EP). Their efficacy as flame retardants alone in thin PP films were evaluated according to the DIN4102-B2 test. Both N-Si and N-O-Si significantly slowed down the burning of PP films. Moreover, their potential as adjuvants with a conventional phosphorous based flame retardant, i.e., spirocyclic phosphonate (AFLAMMIT® PCO 900) in PP and EP resins was evaluated according to the UL-94 V fire standard. A synergistic effect was observed when the phosphorous flame retardant was combined with either N-Si or N-O-SI containing compounds, since none of the flame retardants by themselves could provide V-0 rating in the UL94-V test in PP, LLDPE or EP resins even at much higher loadings. The thermogravimetric analysis carried out under inert atmosphere revealed enhanced and earlier onset of decomposition and thermal activation of phosphorous based flame retardant in the presence of N-Si or N-O-Si in comparison to spirocyclic phosphonate, N-Si or N-O-Si used alone, respectively. The interaction of the phosphorus flame retardant with N-Si was verified by 31P NMR.

Surface electric charge decay behavior of Polypropylene (PP) films treated by atmospheric air dielectric barrier discharge

Atmospheric air dielectric barrier discharge (DBD) is one of the most effective physical techniques for the cold plasma source. It is a promising technique used to modify the surface properties of polymers. This modification leads to improving wetting and adhesion properties, a change in surface roughness and other significant technological features. In recent studies, researchers have showed that DBD plasma exposure can modify the electric properties of insulating materials. In this study, we focused our attention on the influence of DBD plasma treatment on the surface electric charge behavior in polypropylene (PP) thin films. The effect of DBD plasma has been studied as a function of treatment time for two values of applied discharge voltages; 7 and 12 kV. After being exposed to DBD plasma, the samples were charged for 5 seconds in ambient air using a negative triode corona electrode system. The influence of DBD plasma treatment on the surface electric charge behaviour in PP thin films was investigated. The surface characterization of the untreated and treated PP films is performed using surface electric charge decay measurements, for identical charging conditions.

Neutron Reflectivity Study on the Suppression of Interfacial Water Accumulation between a Polypropylene Thin Film and Si Substrate Using a Silane-Coupling Agent.

We measured the neutron reflectivity (NR) of isotactic polypropylene (PP) thin films deposited on Si substrates modified by hexamethyldisilazane (HMDS) at the saturated vapor pressure of deuterated water at 25 °C and 60 °C/85% RH to investigate the effect of HMDS on the interfacial water accumulation in PP-based polymer/inorganic filler nanocomposites and metal/resin bonding materials. We found that the amount of water accumulated at the PP/Si interface decreased with increasing immersion time of the Si substrate in a solution of HMDS in hexane prior to PP film deposition. During the immersion of the Si substrate, the HMDS molecules were deposited on the Si substrate as a monolayer without aggregation. Furthermore, the coverage of the HMDS monolayer on the Si substrate increased with increasing immersion time. At 60 ° C and 85% RH, only a slight amount of interfacial water was detected after HMDS treatment for 1200 min. As a result, the maximum concentration of interfacial water was reduced to 0.1 from 0.3, where the latter corresponds to the PP film deposited on the untreated substrate.

Dynamic conductivity of multilayer graphene during pulsed mechanical activation of a composite (polypropylene - graphene nanoplatelets)

Polymer composite films of polypropylene and graphene nanoplatelets were subjected to mechanical activation . Electrical current pulses are observed during this process. Fourier transforms of the signals are fitted to Havriliak-Negami model and the Kubo model for multilayer graphene. The calculated frequency dependences of conductivity are in good agreement with the experimental results. Relaxation processes and changes in the local geometry of graphene sheets under the influence of elastic waves are responsible for the effects. • Thin films of polypropylene and graphene nanoplatelets are subjected to mechanical activation. • Electrical current pulses are observed. • Fourier transforms of the signals are described by the Kubo model for multilayer graphene.

Confined crystallization and polymorphism in iPP thin films

The morphological and structural evolution of isotactic polypropylene (iPP) in thin and ultrathin films casted by hot-solution spin coating is investigated by means of atomic force microscopy (AFM) and grazing incidence wide angle X-ray scattering (GIWAXS). When reducing the film thickness from 300 nm to 15 nm, changes from a 3D to a quasi-2D morphology are observed. The quasi-2D confined morphology is found in the 220-40 nm thickness range and is characterized by a predominant edge-on orientation (EO) of the lamellae. A transition to the flat-on (FO) orientation paired to a drastic decrease of the sample roughness is observed for thicknesses below 30 nm. Surprisingly, a mixed morphology where orthorhombic γ-phase branches develop from FO α-phase lamellae is observed at the lowest prepared thickness of 15 nm. The unexpected appearance of the γ-phase for the iPP grade used here is due to the favourable flat-on lamellar orientation at the lowest film thickness. Thanks to a quantitative analysis of the GIWAXS patterns, the relative amount between edge-on and flat-on oriented lamellae (χ EO /χ FO ) is calculated, providing useful insights on the real morphological composition of the iPP thin films, a task that is very challenging to achieve with microscopy techniques. • Isotactic polypropylene thin film prepared by hot-solution spin coating present confined crystallization behaviour. • Morphology evolution is investigated via AFM, nanostructural composition and lamellar orientation is studied by means of GIWAXS. • Lamellae maintain a mixed morphological structure, preferential orientation changes from edge-on to flat-on on the substrate. • Formation of the orthorhombic γ-phase is induced by increasing the degree of confinement ( i.e. : decreasing film thickness).

A novel poly (4-methyl-1-pentene)/polypropylene (PMP/PP) thin film composite (TFC) artificial lung membrane for enhanced gas transport and excellent hemo-compatibility.

Extracorporeal membrane oxygenation is a technique that provides short-term supports to the heart and lungs. It removes CO2 from the blood and provides enough oxygen, which is a huge help in the fight against COVID-19. As the key component, the artificial lung membranes have evolved in three generations including silicon, polypropylene and poly (4-methyl-1-pentene). Herein, we for the first time design and fabricate a novel poly (4-methyl-1-pentene)/polypropylene (PMP/PP) thin film composite (TFC) membrane with the anticoagulant coating composed of poly (sodium 4-styrenesulfonate) and cross-linked poly (vinyl alcohol). Poly (sodium 4-styrenesulfonate) provides sulfonic acid groups to inhibit the coagulant factors (FVIII and FXII), and cross-linked poly (vinyl alcohol) increase the stability of the anticoagulant coating and further improve the hydrophilicity via abundant hydroxyl groups to depress the protein adsorption. Long-term anticoagulant property was demonstrated by whole human blood for 28 days. Blood compatibility was evaluated by hemolysis rate, anticoagulation activity (APTT, TT and PT), complement activation, platelet activation and contact activation. Pure CO2, O2 and N2 permeation rates were determined to evaluate the mass transfer properties of PMP/PP TFC membranes. Gas permeation results revealed that gas permeation flux increased in the TFC membranes because of the decrease of crystallinity. Overall, the so prepared PMP/PP membrane shows good CO2/O2 selectivity and blood compatibility as novel TFC artificial lung membrane.

Morphological study of isotactic polypropylene thin films on different substrates using grazing incidence wide-angle X-ray diffraction

Isotactic polypropylene (iPP) is one of the most commonly used polymers owing to its excellent mechanical properties and well-balanced physical properties. These properties can be achieved and controlled through a better understanding of its hierarchical structures. The crystal structures of iPP thin films of ∼120 nm thickness formed on graphite and silicon substrates were investigated via grazing incidence wide-angle X-ray diffraction (GIWAXD) with hard and tender X-rays along with grazing incidence small-angle X-ray scattering, atomic force microscopy, and transmission electron microscopy. The lamellae were found to be edge-on-oriented on the graphite substrate due to epitaxial iPP crystal growth and flat-on-oriented on the silicon substrate due to iPP crystal growth along the thermodynamically dominant orientation. GIWAXD results obtained with tender X-rays revealed that the orientation of the crystal lamellae did not change along the thickness direction and that the degree of crystallinity at the surface was lower than that in the interior of the iPP thin films for each substrate. These results indicate that crystallization at the substrate-film interface played a significant role in the formation of the crystal structure of the iPP thin film, that is, the crystals grew throughout the thin films along the substrate-induced orientation even in the case of edge-on orientation, where the growth axes of the crosshatched lamellae were not parallel to the thickness direction. The relationship between the growth axes of lamella and the growth of surface-induced orientation along the normal direction of the substrates was successfully clarified for the first time using the thin film systems. The obtained results can be extended to interface-induced crystallization inside bulk composite materials.

A methodology for predicting processing induced thermal residual stress in thermoplastic composite at the microscale

A computational finite element (FE) model of thermal residual stress was developed for carbon fiber/thermoplastic composites at the microscale and implemented via user material subroutine (UMAT) in ABAQUS. This model accounts for cooling-rate effects on crystallinity and stress-free temperature, temperature-dependent elastic modulus, temperature-dependent coefficient of thermal expansion (CTE) of the matrix, and the temperature-independent transversely isotropic properties of the carbon fiber. Results are generated for a model composite, consisting of a single carbon fiber embedded in a polypropylene thin film. Single filaments are pre-tensioned in the polymer melt to induce different levels of residual axial strain as well as maintain straight fibers during cool-down. Three different preload conditions (1g, 4g, and 8g) were experimentally fabricated and modeled. The residual strain along the length of the fiber is quantified and validated including the shear lag region that develops at the free edge of the sample. Experimentally measured residual strain shows a good correlation with the FE predictions for the applied fiber preloading conditions.

Investigation of Interfacial Water Accumulation between Polypropylene Thin Film and Si Substrate by Neutron Reflectivity.

We performed neutron reflectivity (NR) measurements of isotactic polypropylene (PP) thin films deposited on a Si substrate at the saturated vapor pressure of deuterated water to investigate interfacial water accumulation between the PP and metal surfaces in PP-based polymer/inorganic filler nanocomposites and metal/resin bonding materials. The PP thin films prepared on a Si substrate by a spin-coating technique were adequate as a model system for the PP/metal interface in these materials. A water-rich layer with a maximum water concentration of 0.5, which was considerably higher than those reported in previous studies of organic/inorganic interfaces, was observed within a width of approximately 3 nm at the interface under saturated vapor conditions. This could be attributed to the weak interaction between the PP thin film and the Si substrate. The pathway of moisture transport to the interfacial region was along the interface rather than through the PP film because the hydrophobic PP thin film does not entirely swell with water vapor.

Comparison of angular-selective metasurfaces as tools for sub-THz single-frequency sensing

We demonstrate and numerically characterize a set of single-layer metasurfaces based on capacitively-coupled bent metal strips deposited on a thin polypropylene film operating as band-stop filters at 139.1 GHz. Due to a high inter-digital coupling capacitance between neighboring inclusions formed by the strips, the resonance of the metasurface becomes highly sensitive to the incidence angle of a plane wave. At the same time, a narrow-band resonance is achieved by reducing the conductor length along the vertical polarization direction of the incident wave. We propose to use both properties for designing a sensor, which analyses the thickness of a thin slab of a known substance deposited over the structure by tracking the angle at which the minimum of transmission can be measured at a single frequency. We compare three versions of the proposed geometry by numerical calculation of the transmission coefficient depending on both the incidence angle and analyte slab’s thickness. We select the most suitable structure for sensing.

Local orientation of chains at crystal/amorphous interfaces buried in isotactic polypropylene thin films.

A better understanding of the aggregation states of polymer chains in thin films is of pivotal importance for developing thin film polymer devices in addition to its inherent scientific interest. Here we report the preferential orientation of the crystalline lamellae for isotactic polypropylene (iPP) in spin-coated films by grazing incidence of wide-angle X-ray diffraction in conjunction with sum frequency generation vibrational spectroscopy, which provides information on the local conformation of chains at crystal/amorphous interfaces buried in a thin film. The crystalline orientation of iPP, which formed cross-hatched lamellae induced by lamellar branching, altered from a mixture of edge-on and face-on mother lamellae to preferential face-on mother lamellae with decreasing thickness. The orientation of methyl groups at the crystal/amorphous interfaces in the interior region of the iPP films changed, accompanied by a change in the lamellar orientation.

Improving the repetitive washing and abrasion resistance properties of fabrics produced with metallized yarns

Metallized yarns have become an integral part of fashion because they give extra sheen to garments and an inimitable appearance to fabrics, making them special yarns. However, because of repetitive washing and abrasions, the metallic part of the yarn in the fabric is removed and the fabric loses its brightness and becomes transparent. This study aims to solve this issue by searching for high-quality metallized yarn production methods to eliminate problems during usage. In the experimental part of the study, eight different types of metallized films were produced using the lamination technique with two kinds of adhesives. Non-laminated metallized polyester films were used as a reference to understand the effectiveness of the lamination process. Metallized yarns were produced from laminated metallized films by using standard production parameters. After producing nine different types of metallized yarns, monotype knitted fabrics were then from these yarns. Yarn’s basic properties and fabric’s mechanical properties were then measured to compare the effect of the thin film type, lamination process and adhesive type effect on these properties. The test results showed that the lamination technique significantly improves the resistance of the repetitive washing process and the abrasion property of fabrics. The best results were obtained with polypropylene thin films. However, they had a higher friction coefficient and a harder handle property than polyester films. When using a thinner polypropylene film, this problem could be eliminated, and the yarns could be an important alternative choice for commercially producing metallized yarns in the future.

Impulse and DC breakdown strength of polypropylene thin film

Impulse and DC breakdown strength of polypropylene thin film

Direct High-Temperature Form I Crystallization of Isotactic Poly(1-butene) Assisted by Oriented Isotactic Polypropylene

The crystallization behavior of isotactic poly(1-butene) (iPBu) from melt on the surface of melt-drawn oriented isotactic polypropylene (iPP) thin films and in the melt-drawn oriented iPBu/iPP blen...

Frequency-Controllable Polarization Rotation of THz Waves With an SCMS

In this article, we theoretically and experimentally study the conversion from a circularly polarized (CP) plane electromagnetic wave into a linearly polarized (LP) transmitted one using anisotropic self-complementary metasurfaces. For this purpose, a metasurface design operable at sub-terahertz frequencies is proposed and investigated in the range of 230-540 GHz. The metasurface is composed of alternating complementary rectangular patches and apertures patterned in an aluminum layer deposited on a thin polypropylene film. Our study shows that the translational symmetry of the metasurface results in unusual and useful electromagnetic properties under illumination with CP radiation beams. In particular, alongside with broadband circular-to-linear conversion, the transmitted wave exhibits a frequency-independent magnitude, while its polarization angle gradually changes with frequency that paves the way for new beam-splitting applications.

Graphene Aerogel Broken to Fragments for a Piezoresistive Pressure Sensor with a Higher Sensitivity.

The porous and elastic reduced graphene aerogel (rGA) is a promising active material for piezoresistive pressure sensors (PRSs) to realize an electronic skin. Due to the specific working mechanism and the limitation of the rGA's monolithic conductive network, the PRSs based on rGA suffer from a limited change of resistance with mechanical deformation, so they show poor sensitivity and cannot detect low pressures. Here we aim to improve the sensitivity of the PRS and make it suitable for a low-pressure system (0.5-8 kPa) through an effective method. The monolithic rGA is broken into small pieces by cutting (named as CGA). The sensitivity of the PRS based on CGA can be improved by 10 times that of the uncut rGA (named as UCGA). The resistance variation ratio of CGA (0.96) is 1.45 times of the resistance variation ratio of the UCGA (0.66). By using a package of elastic polypropylene thin films (PP), the cycle stability performance of CGA remains stable after 4200 cycles. The CGA can detect the pulse of a human being with sensitivity higher than the UCGA and the ordinary sensors. This method is simple, effective, and universal to improve the sensitivity of PRS based on porous and elastic materials.