Electret properties and chemical modification of cellular polypropylene films

The electret properties of virginal cellular polypropylene (PP) films and chemically modified cellular PP films by extraction from CH₂Cl₂ solution, oxidation in a mixture solution of H₂SO₄, CrO₃ and H₂O and fluorination in a hydrofluoric acid (HF) solution, were systematically studied by measuring the open-circuit thermally stimulated discharge (TSD) current spectra, charge TSD spectra and isothermal charge decay. The results point out that there are more deep traps than shallow traps in the surface region while the contrary case occurs in the bulk region. The thermal stability of charge storage of the chemically modified cellular PP film is significantly improved in comparison with that of the virginal one. Light irradiation or reacting at elevated temperature has remarkable promotion effect on the reaction of HF with the extracted and oxidized film. Moreover, a method for investigating the dynamic changes of mean charge depth relative to its initial value during heating was proposed.     

Modification of surface properties of polypropylene (PP) film using DC glow discharge air plasma

The industrial use of polypropylene (PP) films is limited because of undesirable properties such as poor adhesion and printability. In the present study, a DC glow discharge plasma has been used to improve the surface properties of PP films and make it useful for technical applications. The change in hydrophilicity of modified PP film surface was investigated by contact angle (CA) and surface energy measurements as a function of exposure time. In addition, plasma-treated PP films have been subjected to an ageing process to determine the durability of the plasma treatment. Changes in morphological and chemical composition of PP films were analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The improvement in adhesion was studied by measuring T-peel and lap shear strength. The results show that the surface hydrophilicity has been improved due to the increase in the roughness and the introduction of oxygen-containing polar groups. The AFM observation on PP film shows that the roughness of the surface increased due to plasma treatment. Analysis of chemical binding states and surface chemical composition by XPS showed an increase in the formation of polar functional groups and the concentration of oxygen content on the plasma-processed PP film surfaces. T-peel and lap shear test for adhesion strength measurement showed that the adhesion strength of the plasma-modified PP films increased compared with untreated films surface.     

Improved piezoelectric properties of cellular polypropylene ferroelectrets by chemical modification

To improve the thermal stability of piezoelectricity of polypropylene (PP) ferroelectrets, chemical modification of the cellular PP film was performed via chromic acid oxidation and then hydrofluoric acid treatment. Deep chemical modification is achieved as indicated by the energy-dispersive X-ray analyses on the cross-section of the modified cellular PP film. The results of the isothermal decay for piezoelectric d ₃₃-coefficient at 70°C indicate the improved thermal stability of piezoelectricity and the enhanced piezoelectric activity of the modified PP ferroelectrets. The former is attributed to the improvement of thermal stability of the charges trapped in the internal void surface layers as indicated by the thermally stimulated discharge measurements, while the latter results not only from the improved thermal stability of the charges but also from the reduction in Young’s modulus of the PP ferroelectrets due to the chemical modification as revealed by the dielectric resonance analyses.     

Surface modification of polypropylene non-woven fabric using atmospheric nitrogen dielectric barrier discharge plasma

In this paper, a dielectric barrier discharge operating in nitrogen at atmospheric pressure has been used to improve the surface hydrophilic property of polypropylene (PP) non-woven fabric. The changes in the hydrophilic property of the modified PP samples are investigated by the contact angle measurements and the variation of water contact angle is obtained as a function of the energy density; micrographs of the PP before and after plasma treatment are observed by scanning electron microscopy (SEM) and the chemical composition of the PP surface before and after plasma treatment is also analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that the surface hydrophilic property of the PP samples is greatly improved with plasma treatment for a few seconds, as evidenced by the fact that the contact angle of the treated PP samples significantly decreases after plasma treatment. The analysis of SEM shows that the surface roughness of the treated PP samples increases due to bonding and etching in plasma processing. The analyses of FTIR and the C1s peak in the high-resolution XPS indicate that oxygen-containing and nitrogen-containing polar functional groups are introduced into PP surface in plasma processing. It can be concluded that the surface hydrophilic property of the modified PP samples has been obviously improved due to the introduction of oxygen-containing and nitrogen-containing polar groups and the increase of the surface roughness on the PP surface.     

Mechanism of adhesion between protein-based hydrogels and plasma treated polypropylene backing

We studied the mechanism of adhesion between N₂ plasma treated polypropylene (PP/N₂) backing and a hybrid hydrogel (HG) produced by chemical crosslinking between poly(ethylene glycol) and soy albumin. The work of adhesion, measured by peel testing, was found to be 25 times higher for PP/N₂ compared to untreated PP (≈5.0 J/m² versus ≈0.2 J/m²). In order to understand the adhesion mechanism, we performed a detailed analysis of the surface chemical composition of PP and PP/N₂ using X-ray photoelectron spectroscopy (XPS), chemical derivatization and attenuated total reflectance infra-red (ATR-IR) measurements. The results confirm incorporation of different nitrogen- (amine, amide,…) and oxygen- (hydroxyl, carboxyl,…) containing chemical groups on the PP/N₂ surface. The derivatized functions were primary amine, hydroxyl, carboxyl and carbonyl groups. Chemical derivatization reactions validated the XPS results (except for carbonyl groups), and they clearly underlined the essential role of primary amine groups in the adhesion process. In fact, after derivatization of the amine functions, the work of adhesion was found to be 0.41 ± 0.12 J/m². Participation of amine groups in the formation of covalent bonds at the interface between PP/N₂ and HG was directly confirmed by ATR-IR measurements.     

Biocompatibility of polypropylene non-woven fabric membrane via UV-induced graft polymerization of 2-acrylamido-2-methylpropane sulfonic acid

This work described the graft polymerization of a sulfonic acid terminated monomer, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), onto the surface of polypropylene non-woven (NWF PP) membrane by O₂ plasma pretreatment and UV-induced photografting method. The chemical structure and composition of the modified surfaces were analyzed by FTIR-ATR and XPS, respectively. The wettability was investigated by water contact angle and equilibrium water adsorption. And the biocompatibility of the modified NWF PP membranes was evaluated by protein adsorption and platelet adhesion. It was found that the graft density increased with prolonging UV irradiation time and increasing AMPS concentration; the water contact angles of the membranes decreased from 124° to 26° with the increasing grafting density of poly(AMPS) from 0 to 884.2 μg cm⁻², while the equilibrium water adsorption raised from 5 wt% to 75 wt%; the protein absorption was effectively suppressed with the introduction of poly(AMPS) even at the low grafting density (132.4 μg cm⁻²); the number of platelets adhering to the modified membrane was dramatically reduced when compared with that on its virgin surface. These results indicated that surface modification of NWF PP membrane with AMPS was a facile approach to construct biocompatible surface.     

Effect of the external medium on the spectral characteristics of polypropylene films doped with Eu(fod)<Subscript>3</Subscript> molecules

We have studied the effect of external factors (humidity, pressure, temperature) on the stability of the organometallic compound Eu(fod)3 (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione) impregnated into polypropylene (PP) using supercritical CO₂. We have established that under the influence of external conditions, there is a decrease in the integrated intensity of the absorption band for the Eu(fod)₃ molecule and the photoluminescence (PL) of Eu³⁺ ions as a function of the properties of the medium, and in the presence of water molecules the shape of the bands for these spectra changes. We propose a physical model explaining the behavior of the absorption and photoluminescence spectra when the polypropylene films are stored under different conditions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 42–47, January–February, 2007.     

Mechanical,Thermal, and Surface Properties of Ultrahigh Molecular Weight Polyethylene/Polypropylene Blends

Various compositions of ultrahigh molecular weight polyethylene/polypropylene (UHMWPE/PP) blends were prepared in decalin, with the rheological, mechanical, thermal, and surface properties of the blends being determined using the solution cast film. Viscosity and mechanical properties of the blends decreased below the additivity value with increasing PP content implying that PP molecules disturb the entanglement of UHMWPE. Contact angle of the blend films with a water drop increased with increasing content of PP. The atomic force microscope (AFM) images showed that the surface of cast UHMWPE was very smooth whereas that of cast PP was very uneven. For blends, the surface became rough and uneven with increasing content of PP. The melting temperature of PP (T _mP) decreased in the blends with increasing UHMWPE content while that of UHMWPE (T _mU) remained almost constant in blends.     

Synthesis and enrichment of a macromolecular surface modifier PP-b-PVP for polypropylene

Polypropylene-block-poly(vinylpyrrolidone) copolymer was synthesized through the esterification of dicarboxyl-terminated polypropylene with monohydroxyl-terminated poly(vinylpyrrolidone) and used as a macromolecular surface modifier to improve the surface hydrophilicity of PP. The results of ATR-FTIR and contact angles measurements indicated that PP-b-PVP could diffuse preferably onto the surface by the inducement of high energy interface and lower the water contact angle of polypropylene. Lower loading and lower molecular weight of PP and PVP segment would result in higher surface selective enrichment.     

Significantly improved charge stability of cellular polypropylene films by fluorination and subsequent annealing

An extremely effective and practical approach is proposed and used for improving charge stability of cellular polypropylene (PP) films. The approach is composed of fluorination and subsequent annealing of the PP films. Surface charge stability is significantly improved by the approach, as revealed by the measurements of open-circuit thermally stimulated discharge (TSD) current, charge TSD and isothermal charge decay at 90 °C. As an example, after 7 h at 90 °C, the amount of surface charge of the treated PP film by the approach still remains about 72% of its initial value, while the corresponding value is only 27% for the virgin PP film. The improvement of charge stability is attributed to chemical composition change and structure modification of the PP films due to the fluorination and annealing treatments, as indicated by attenuated total reflection infrared analyses and wide angle X-ray diffraction measurements. The treatments eliminate the shallow charge traps almost completely and produce much deeper ones.     

Deodorisation effect of diamond-like carbon/titanium dioxide multilayer thin films deposited onto polypropylene

Many types of plastic containers have been used for the storage of food. In the present study, diamond-like carbon (DLC)/titanium oxide (TiO₂) multilayer thin films were deposited on polypropylene (PP) to prevent flavour retention and to remove flavour in plastic containers.For the flavour removal test, two types of multilayer films were prepared, DLC/TiO₂ films and DLC/TiO₂/DLC films. The residual gas concentration of acetaldehyde, ethylene, and turmeric compounds in bottle including the DLC/TiO₂-coated and the DLC/TiO₂/DLC-coated PP plates were measured after UV radiation, and the amount of adsorbed compounds to the plates was determined. The percentages of residual gas for acetaldehyde, ethylene, and turmeric with the DLC/TiO₂ coated plates were 0.8%, 65.2% and 75.0% after 40 h of UV radiation, respectively. For the DLC/TiO₂/DLC film, the percentages of residual gas for acetaldehyde, ethylene and turmeric decreased to 34.9%, 76.0% and 85.3% after 40 h of UV radiation, respectively. The DLC/TiO₂/DLC film had a photocatalytic effect even though the TiO₂ film was covered with the DLC film.     

Laser cutting of polymeric materials: An experimental investigation

The CO₂ laser cutting of three polymeric materials namely polypropylene (PP), polycarbonate (PC) and polymethyl methacrylate (PMMA) is investigated with the aim of evaluating the effect of the main input laser cutting parameters (laser power, cutting speed and compressed air pressure) on laser cutting quality of the different polymers and developing model equations relating input process parameters with the output. The output quality characteristics examined were heat affected zone (HAZ), surface roughness and dimensional accuracy. Twelve sets of tests were carried out for each of the polymer based on the central composite design. Predictive models have been developed by response surface methodology (RSM). First-order response models for HAZ and surface roughness were presented and their adequacy was tested by analysis of variance (ANOVA). It was found that the response is well modeled by a linear function of the input parameters. Response surface contours of HAZ and surface roughness were generated. Mathematical model equations have been presented that estimate HAZ and surface roughness for various input laser cutting parameters. Dimensional accuracies of laser cutting on polymers were examined by dimensional deviation of the actual value from the nominal value. From the analysis, it has been observed that PMMA has less HAZ, followed by PC and PP. For surface roughness, PMMA has better cut edge surface quality than PP and PC. The response models developed can be used for practical purposes by the manufacturing industry. However, all three polymeric materials showed similar diameter errors tendency in spite of different material properties.     

Induced super hydrophilicity due to surface modification of polypropylene membrane treated by O2 plasma

Radio frequency (RF) plasma offers a unique route for the surface modification of polymer. The influence of the plasma treatment on the basic properties of the porous membranes such as effective void volume and the flow rate were investigated. It was shown that the polymer ablation significantly alters the hydrophilicity leading to the enhancement of the water flux. Here, the polypropylene membrane was tested by O₂ plasma to emphasize that the contact angle nonlinearly decreases with the treatment time. The XPS surface sensitive technique was applied to confirm the drastic skin change of the oxygen content showing that membrane becomes super hydrophilic due to the significant O₂ implant.     

Polymer-filler interaction and control of structure in barium sulphate-filled blends of polypropylene

The structure of barium sulphate-filled immiscible blends with a polypropylene (PP) matrix can be controlled with respect to the occlusion of the filler with the aid of maleic anhydride-grafted polypropylene (PP-g-MAH) through the formation of an interlayer around the filler particles. Here we analyze the interlayer and the mechanism of interlayer formation in a blend with a poly(methylmethacrylate) (PMMA) dispersed phase and compare the results with previous studies, which concerned PP blends with polystyrene (PS) and poly(styrene-co-acrylonitrile) (SAN) minority phases. The main analytical tools were scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) and Fourier Transform Infrared Spectroscopy (FTIR). The filler is occluded in the PMMA polymer in the PP/PMMA/BaSO₄ (60/20/20 vol.%) blend, but is occluded in the PP phase at the addition of a sufficient amount of PPg-MAH. The reason for the formation of the latter structure is a PP-g-MAH layer surrounding the filler particles, and the most likely mechanism behind this phenomenon is judged to be specific weak interactions between carbonyl groups in the graft copolymer and Ba²⁺ ions at the filler surface.     

AC corona-discharge treatment of polypropylene foils effects of gaseous atmosphere

The AC corona-discharge treatment of PP foils has been studied in air, N₂, CO₂ gases at a pressure of 93·6 kPa and at ambient temperatures. The highest increase in surface energy _S of PP foil, by about 100% of initial value, was observed after treatment in CO₂. The best durability of induced enhancement of surface energy was also achieved after the treatment in carbon dioxide. The enhancement of polar component _S ^P and unsubstantial reduction of dispersion component _S ^D , and the results of other experiments indicate that the role of charged particles, namely the role of electrons in treatment process of PP is very important.Authors are much obliged to Mrs. L. Izoldova of Technical University, Bratislava, for technical assistance.     

Influence of High-Density Polyethylene and Nano-Calcium Carbonate of Various Content Ratios on the Crystallization of Polypropylene

The influence of high-density polyethylene (HDPE) and nano-CaCO₃ of various content ratios on the crystallization of polypropylene (PP) was investigated by differential scanning calorimetry, dynamic rheology, wide angle X-ray diffraction (WAXD), and Izod impact strength measurements. The results showed that HDPE and PP were phase separated in their blends and the additive CaCO₃ filler mainly dispersed in the PP phase, acting as a nucleation agent to promote the crystallization of PP. For the samples HDPE/ nano-CaCO₃ 30/0 and 25/5, the β crystals content was much higher than the other samples. The reason is that the viscosity difference between HDPE and PP led to a velocity difference, which could induce shear stress at the interfaces of HDPE and PP during injection molding. The intensive shear stress at their phase interfaces is advantageous for orientation of the chains, inducing the formation of β crystals. However, with the increment of CaCO₃ content, there were dual effects of CaCO₃ on the crystallization of PP: at low CaCO₃ content, it would hamper the orientation of PP chains, thus leading to a decrease of β crystals; at high CaCO₃ content, it would induce β crystals by itself.     

Femtosecond laser ablation of polypropylene for breathable film

A polypropylene (PP) film was ablated using a femtosecond laser with a center wavelength of 785 nm, a pulse width of 184 fs and a repetition rate of 1 kHz. Increments of both the pulse energy and the shot number of pulses lead to co-occurrence of photochemical and thermal effect, demonstrated by the spatial expansion of rim on the surface of PP. The shapes of the laser-ablated PP films were imaged by a scanning electron microscope (SEM) and measured by a 3D optical measurement system (NanoFocus). And, the gas and water vapor transmission rate, mechanical properties of PP film micropatterned by fs laser pulses was characterized. Our results demonstrate that a femtosecond pulsed laser is an efficient tool for breathable packaging films in modifying the flow of air and gas, where the micropatterns are specifically tailored in size, location and number of which is easily controlled by laser processing conditions.     

Composites from Brazilian natural fibers with polypropylene: mechanical and thermal properties

Brazil has a well established ethanol production program based on sugarcane. Sugarcane bagasse and straw are the main by-products that may be used as reinforcement in natural fiber composites. Current work evaluated the influence of fiber insertion within a polypropylene (PP) matrix by tensile, TGA and DSC measurements. Thus, the mechanical properties, weight loss, degradation, melting and crystallization temperatures, heat of melting and crystallization and percentage of crystallinity were attained. Fiber insertion in the matrix improved the tensile modulus and changed the thermal stability of composites (intermediary between neat fibers and PP). The incorporation of natural fibers in PP promoted also apparent T _c and ΔH _c increases. As a conclusion, the fibers added to polypropylene increased the nucleating ability, accelerating the crystallization process, improving the mechanical properties and consequently the fiber/matrix interaction.     

Plasma-induced graft-polymerization of polyethylene glycol acrylate on polypropylene substrates

A detailed study of argon plasma-induced graft-polymerization of polyethylene glycol acrylate (PEGA) on polypropylene (PP) substrates (membranes and films) is presented. The process consists of four steps: (a) plasma pre-activation of the PP substrates; (b) immersion in a PEGA solution; (c) argon plasma-induced graft-polymerization; (d) washing and drying of the samples. Influence of the solution and plasma parameters on the process efficiency evaluated in terms of amount of grafted polymer, coverage uniformity and substrates wettability, are investigated. The plasma-induced graft-polymerization of PEGA is then followed by sample weighting, water droplet adsorption time and contact angle measurements, attenuated total reflection infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) analyses. The stability of the obtained thin films was evaluated in water and in phosphate buffer saline (PBS) at 37 °C. Results clearly indicates that plasma-induced graft-polymerization of PEGA is a practical methodology for anti-fouling surface modification of materials.     

Polypropylene modified with 2-hydroxyethyl acrylate-g-2-methacryloyloxyethyl phosphorycholine and its hemocompatibility

Polypropylene (PP) was modified with 2-hydroxyethyl acrylate (HEA) by solution radical grafting to introduce active hydroxyl groups on polypropylene backbone (PP-g-HEA). Then the biomimic monomer, 2-methacryloyloxyethyl phosphorycholine (MPC), was grafted onto the surface of PP-g-HEA film (PP-g-HEA-g-MPC) by redox graft polymerizations with ceric(IV) ammonium nitrate as an initiator. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) showed that the HEA and MPC were introduced onto PP molecular chains and the copolymer, PP-g-HEA-g-MPC were formed. The water contact angle measurements demonstrated that the final modified PP film exhibited a better hydrophilic surface compared to the neat PP film. The platelets adhesion on the neat PP, PP-g-HEA and PP-g-HEA-g-MPC film was examined by scanning electron microscopy (SEM). It was found that a large number of platelets were adhered and activated on the surface of neat PP and PP-g-HEA films, while the number of platelets on PP-g-HEA-g-MPC surface was decreased remarkably. The result revealed that the introduction of poly(MPC) onto the PP surface improved the hemocompatibility of PP substantially.