Pressure-Driven Piezoelectric Sensors and Energy Harvesting in Biaxially Oriented Polyethylene Terephthalate Film.

This study reports the possibility of using biaxially oriented polyethylene terephthalate (BOPET) plastic packaging to convert mechanical energy into electrical energy. Electricity is generated due to the piezoelectricity of BOPET. Electricity generation depends on the mechanical deformation of the processing aids (inorganic crystals), which were found and identified by SEM and EDAX analyses as SiO2. BOPET, as an electron source, was assembled and tested as an energy conversion and self-powered mechanical stimuli sensor using potential applications in wearable electronics. When a pressure pulse after pendulum impact with a maximum stress of 926 kPa and an impact velocity of 2.1 m/s was applied, a voltage of 60 V was generated with short-circuit current and charge densities of 15 µAcm-2 and 138 nCm-2, respectively. Due to the orientation and stress-induced crystallization of polymer chains, BOPET films acquire very good mechanical properties, which are not lost during their primary usage as packaging materials and are beneficial for the durability of the sensors. The signals detected using BOPET sensors derived from pendulum impact and sieve analyses were also harvested for up to 80 cycles and up to 40 s with short-circuit voltages of 107 V and 95 V, respectively. In addition to their low price, the advantage of sensors made from BOPET plastic packaging waste lies in their chemical resistance and stability under exposure to oxygen, ultraviolet light, and moisture.

Effect of Chain Extending Cross-Linkers on the Disintegration Behavior of Composted PBAT/PLA Blown Films.

A biodegradable blend of PBAT-poly(butylene adipate-co-terephthalate)-and PLA-poly(lactic acid)-for blown film extrusion was modified with four multi-functional chain extending cross-linkers (CECL). The anisotropic morphology introduced during film blowing affects the degradation processes. Given that two CECL increased the melt flow rate (MFR) of tris(2,4-di-tert-butylphenyl)phosphite (V1) and 1,3-phenylenebisoxazoline (V2) and the other two reduced it (aromatic polycarbodiimide (V3) and poly(4,4-dicyclohexylmethanecarbodiimide) (V4)), their compost (bio-)disintegration behavior was investigated. It was significantly altered with respect to the unmodified reference blend (REF). The disintegration behavior at 30 and 60 °C was investigated by determining changes in mass, Young's moduli, tensile strengths, elongations at break and thermal properties. In order to quantify the disintegration behavior, the hole areas of blown films were evaluated after compost storage at 60 °C to calculate the kinetics of the time dependent degrees of disintegration. The kinetic model of disintegration provides two parameters: initiation time and disintegration time. They quantify the effects of the CECL on the disintegration behavior of the PBAT/PLA compound. Differential scanning calorimetry (DSC) revealed a pronounced annealing effect during storage in compost at 30 °C, as well as the occurrence of an additional step-like increase in the heat flow at 75 °C after storage at 60 °C. The disintegration consists of processes which affect amorphous and crystalline phase of PBAT in different manner that cannot be understood by a hydrolytic chain degradation only. Furthermore, gel permeation chromatography (GPC) revealed molecular degradation only at 60 °C for the REF and V1 after 7 days of compost storage. The observed losses of mass and cross-sectional area seem to be attributed more to mechanical decay than to molecular degradation for the given compost storage times.

Modeling of Creep Behavior of Particulate Composites with Focus on Interfacial Adhesion Effect.

Evaluation of creep compliance of particulate composites using empirical models always provides parameters depending on initial stress and material composition. The effort spent to connect model parameters with physical properties has not resulted in success yet. Further, during the creep, delamination between matrix and filler may occur depending on time and initial stress, reducing an interface adhesion and load transfer to filler particles. In this paper, the creep compliance curves of glass beads reinforced poly(butylene terephthalate) composites were fitted with Burgers and Findley models providing different sets of time-dependent model parameters for each initial stress. Despite the finding that the Findley model performs well in a primary creep, the Burgers model is more suitable if secondary creep comes into play; they allow only for a qualitative prediction of creep behavior because the interface adhesion and its time dependency is an implicit, hidden parameter. As Young's modulus is a parameter of these models (and the majority of other creep models), it was selected to be introduced as a filler content-dependent parameter with the help of the cube in cube elementary volume approach of Paul. The analysis led to the time-dependent creep compliance that depends only on the time-dependent creep of the matrix and the normalized particle distance (or the filler volume content), and it allowed accounting for the adhesion effect. Comparison with the experimental data confirmed that the elementary volume-based creep compliance function can be used to predict the realistic creep behavior of particulate composites.

Electrical Detection of Vibrations of Electrospun PVDF Membranes.

We prepared electroactive PVDF membranes, which were subjected to mechanical as well as dual electro-mechanical signals and their responses were detected by the evoked electrical pulses. The aim was to obtain primarily electric energy that could be used for light signalling, sensing of the membrane properties and membrane motion detection. The obtained data showed the unique as well as usable properties of PVDF membranes. From this point of view, the gain and analysis of the electrical responses to combined electro-mechanical loads of PVDF membranes have been important in terms of identifying the mechanism. The detected electrical response of the PVDF membrane to their electro-mechanical pulses also indicated the possibility of using this phenomenon. Among others, it suggests monitoring of membrane fouling and use for a self-cleaning mechanism.

Qualitative Beam Profiling of Light Curing Units for Resin Based Composites.

This study investigates two technically simple methods to determine the irradiance distribution of light curing units that governs the performance of a visible-light curing resin-based composites. Insufficient light irradiation leads to under-cured composites with poor mechanical properties and elution of residual monomers. The unknown irradiance distribution and its effect on the final restoration are the main critical issues requiring highly sophisticated experimental equipment. The study shows that irradiance distributions of LCUs can easily be determined qualitatively with generally available equipment. This significantly helps dentists in practices to be informed about the homogeneity of the curing lights.

Polyolefin backbone substitution in binders for low temperature powder injection moulding feedstocks.

This paper reports the substitution of polyolefin backbone binder components with low melting temperature carnauba wax for powder injection moulding applications. The effect of various binder compositions of Al2O3 feedstock on thermal degradation parameters is investigated by thermogravimetric analysis. Within the experimental framework 29 original feedstock compositions were prepared and the superiority of carnauba wax over the polyethylene binder backbone was demonstrated in compositions containing polyethylene glycol as the initial opening agent and governing the proper mechanism of the degradation process. Moreover, the replacement of synthetic polymer by the natural wax contributes to an increase of environmental sustainability of modern industrial technologies.

Effect of Particle Size and Shape on Wall Slip of Highly Filled Powder Feedstocks for Material Extrusion and Powder Injection Molding.

A necessity to distinguish between the influence of powder shape and size (particle size distribution) is especially demanding for highly filled metal powder feedstocks employed in additive manufacturing and powder injection molding. As their processability is evaluated through rheological behavior, the study focuses on the effect of powder size/shape on a wall slip, which is a typical phenomenon determining flow performance of these materials. Water and gas atomized 17-4PH stainless steel powders with D 50 of about 3 and 20 µm are admixed into a binder containing low-density polyethylene, ethylene vinyl acetate, and paraffin wax. Mooney analysis to intercept the slip velocity of 55 vol. % filled compounds reveals that wall slip effect appears to vary significantly with size and shape of metal powders-round shaped and large particles are the most prone to the wall slip. However, the evaluation is affected by the type of the flow streams resulting from the geometry of the dies-conical dies reduce the slip up to 60% in case of fine and round particles.

Tensile Properties of Four Types of ABS Lattice Structures-A Comparative Study.

This article aims to compare the behaviour of four types of lattice structures named Cartesian, Rhomboid, Octagonal, and Starlit under tensile stress loading. The structures were made of Acrylonitrile Butadiene Styrene (ABS) material using the Fused Filament Fabrication (FFF) technique with three different specific volumes (24, 42, and 60%). Five samples of each type were produced, and a total of 60 samples were tested. Experimental testing was performed according to EN ISO 527-1:2012 and EN ISO 527-2:2012. The obtained data were statistically processed, while no outliers were identified. The experimental results pointed out that the specimens' topology, together with the specific volume, very significantly affected the resultant ABS properties of the tested samples made of the same material. The comparative study showed that in terms of ultimate strength, yield strength, and Young's modulus, the Cartesian structure appeared to be the most suitable for tensile stress, and the least suitable structure was the Rhomboid structure. On the other hand, the Rhomboid-type of the structure showed not only the highest amount of absorbed energy but also the highest toughness among the investigated lattice structures, so in the near future, its behaviour under an impact test should be studied.

Introduction of an adhesion factor to cube in cube models and its effect on calculated moduli of particulate composites.

The cube in cube approach was used by Paul and Ishai-Cohen to model and derive formulas for filler content dependent Young's moduli of particle filled composites assuming perfect filler matrix adhesion. Their formulas were chosen because of their simplicity, and recalculated using an elementary volume approach which transforms spherical inclusions to cubic inclusions. The EV approach led to expression of the composites moduli that allows introducing an adhesion factor kadh ranging from 0 and 1 to take into account reduced filler matrix adhesion. This adhesion factor scales the edge length of the cubic inclusions, thus reducing the stress transfer area between matrix and filler. Fitting the experimental data with the modified Paul model provides reasonable kadh for PA66, PBT, PP, PE-LD and BR which are in line with their surface energies. Further analysis showed that stiffening only occurs if kadh exceeds [Formula: see text] and depends on the ratio of matrix modulus and filler modulus. The modified model allows for a quick calculation of any particle filled composites for known matrix modulus EM, filler modulus EF, filler volume content vF and adhesion factor kadh. Thus, finite element analysis (FEA) simulations of any particle filled polymer parts as well as materials selection are significantly eased. FEA of cubic and hexagonal EV arrangements show that stress distributions within the EV exhibit more shear stresses if one deviates from the cubic arrangement. At high filler contents the assumption that the property of the EV is representative for the whole composite, holds only for filler volume contents up to 15 or 20% (corresponding to 30 to 40 weight %). Thus, for vast majority of commercially available particulate composites, the modified model can be applied. Furthermore, this indicates that the cube in cube approach reaches two limits: (i) the occurrence of increasing shear stresses at filler contents above 20% due to deviations of EV arrangements or spatial filler distribution from cubic arrangements (singular), and (ii) increasing interaction between particles with the formation of particle network within the matrix violating the EV assumption of their homogeneous dispersion.

Process-Induced Morphology of Poly(Butylene Adipate Terephthalate)/Poly(Lactic Acid) Blown Extrusion Films Modified with Chain-Extending Cross-Linkers.

Process-induced changes in the morphology of biodegradable polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) blends modified with various multifunctional chain-extending cross-linkers (CECLs) are presented. The morphology of unmodified and modified films produced with blown film extrusion is examined in an extrusion direction (ED) and a transverse direction (TD). While FTIR analysis showed only small peak shifts indicating that the CECLs modify the molecular weight of the PBAT/PLA blend, SEM investigations of the fracture surfaces of blown extrusion films revealed their significant effect on the morphology formed during the processing. Due to the combined shear and elongation deformation during blown film extrusion, rather spherical PLA islands were partly transformed into long fibrils, which tended to decay to chains of elliptical islands if cooled slowly. The CECL introduction into the blend changed the thickness of the PLA fibrils, modified the interface adhesion, and altered the deformation behavior of the PBAT matrix from brittle to ductile. The results proved that CECLs react selectively with PBAT, PLA, and their interface. Furthermore, the reactions of CECLs with PBAT/PLA induced by the processing depended on the deformation directions (ED and TD), thus resulting in further non-uniformities of blown extrusion films.

The Effects of Chain-Extending Cross-Linkers on the Mechanical and Thermal Properties of Poly(butylene adipate terephthalate)/Poly(lactic acid) Blown Films.

This study investigates the effects of four multifunctional chain-extending cross-linkers (CECL) on the processability, mechanical performance, and structure of polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) blends produced using film blowing technology. The newly developed reference compound (M·VERA® B5029) and the CECL modified blends are characterized with respect to the initial properties and the corresponding properties after aging at 50 °C for 1 and 2 months. The tensile strength, seal strength, and melt volume rate (MVR) are markedly changed after thermal aging, whereas the storage modulus, elongation at the break, and tear resistance remain constant. The degradation of the polymer chains and crosslinking with increased and decreased MVR, respectively, is examined thoroughly with differential scanning calorimetry (DSC), with the results indicating that the CECL-modified blends do not generally endure thermo-oxidation over time. Further, DSC measurements of 25 µm and 100 µm films reveal that film blowing pronouncedly changes the structures of the compounds. These findings are also confirmed by dynamic mechanical analysis, with the conclusion that tris(2,4-di-tert-butylphenyl)phosphite barely affects the glass transition temperature, while with the other changes in CECL are seen. Cross-linking is found for aromatic polycarbodiimide and poly(4,4-dicyclohexylmethanecarbodiimide) CECL after melting of granules and films, although overall the most synergetic effect of the CECL is shown by 1,3-phenylenebisoxazoline.

Environmentally Efficient 316L Stainless Steel Feedstocks for Powder Injection Molding.

In this study, environmentally convenient highly metal powder filled feedstocks intended for powder injection molding is presented. The composition of 60 vol % 316L stainless steel gas atomized powder feedstocks containing semicrystalline waxes: acrawax or carnauba wax and paraffin wax, combined with polyethylene glycol and modifier, was optimized to provide defect-free parts. Rheological as well as thermogravimetric analyses supported with scanning electron microscopy and metallography were employed to set up optimum conditions for molding, debinding and sintering. The performance of the novel feedstock was compared with currently available polyolefines-based materials, and results showed an efficiency enhancement due to the substantially lower (about 100 °C) mixing and molding temperatures as well as a reduction of debinding and sintering times at the simultaneous achievement of better mechanical properties in terms of elongation and tensile strength, in comparison to the mass production feedstock.

Online Rheometry Investigation of Flow/Slip Behavior of Powder Injection Molding Feedstocks.

Wall slip in the flow of powder injection molding (PIM) compounds can be the cause of unrealistically low viscosity values, and can lead to a failure of flow simulation approaches. Regardless of its importance, it has been considered only scarcely in the rheological models applied to PIM materials. In this paper, an online extrusion rheometer equipped with rectangular slit dies was used to evaluate the slip velocity of commercial as well as in-house-prepared PIM feedstocks based on metallic and ceramic powders at close-to-processing conditions. The tested slit dies varied in their dimensions and surface roughness. The wall-slip effect was quantified using the Mooney analysis of slip velocities. The smaller gap height (1 mm) supported the wall-slip effect. It was shown that both the binder composition and the powder characteristic affect slip velocity. Slip velocity can be reduced by tailoring a powder particle size distribution towards smaller particle fractions. The thickness of the polymer layer formed at the channel wall is higher for water-soluble feedstocks, while in the case of the catalytic polyacetal feedstocks the effect of surface roughness was manifested through lower viscosity at smooth surfaces.

Development of an Advanced Dynamic Microindentation System to Determine Local Viscoelastic Properties of Polymers.

This study presents a microindentation system which allows spatially resolved local as well as bulk viscoelastic material information to be obtained within one instrument. The microindentation method was merged with dynamic mechanical analysis (DMA) for a tungsten cone indenter. Three tungsten cone indenters were investigated: tungsten electrode, tungsten electrode + 2% lanthanum, and tungsten electrode + rare earth elements. Only the tungsten electrode + 2% lanthanum indenter showed the sinusoidal response, and its geometry remained unaffected by the repeated indentations. Complex moduli obtained from dynamic microindentation for high-density polyethylene, polybutylene terephthalate, polycarbonate, and thermoplastic polyurethane are in agreement with the literature. Additionally, by implementing a specially developed x-y-stage, this study showed that dynamic microindentation with a tungsten cone indenter was an adequate method to determine spatially resolved local viscoelastic surface properties.

Correlation of shear and dielectric ion viscosity of dental resins - Influence of composition, temperature and filler content.

OBJECTIVE: Shear viscosity and ion viscosity of uncured visible light-curing (VLC) resins and resin based composites (RBC) are correlated with respect to the resin composition, temperature and filler content to check where Dielectric Analysis (DEA) investigations of VLC RBC generate similar results as viscosity measurements. METHODS: Mixtures of bisphenol A glycidyl methacrylate (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA) as well as the pure resins were investigated and compared with two commercial VLC dental resins and RBCs (VOCO, Arabesk Top and Grandio). Shear viscosity data was obtained using a Haake Mars III, Thermo Scientific. Ion viscosity measurements performed by a dielectric cure analyzer (DEA 231/1 Epsilon with Mini IDEX-Sensor, Netzsch-Gerätebau). RESULTS: Shear viscosity depends reciprocally on the mobility of molecules, whereas the ion viscosity also depends on the ion concentration as it is affected by both ion concentration and mixture viscosity. Except of pure TEGDMA, shear and ion viscosities depend on the resin composition qualitatively in a similar manner. Furthermore, shear and ion viscosities of the commercial VLC dental resins and composites exhibited the same temperature dependency regardless of filler content. Application of typical rheological models (Kitano and Quemada) revealed that ion viscosity measurements can be described with respect to filler contents of up to 30vol.%. SIGNIFICANCE: Rheological behavior of a VLC RBC can be characterized by DEA under the condition that the ion concentration is kept constant. Both methods address the same physical phenomenon - motion of molecules. The proposed relations allows for calculating the viscosity of any Bis-GMA-TEGDMA mixture on the base of the viscosities of the pure components. This study demonstrated the applicability of DEA investigations of VLC RBCs with respect to quality assurance purposes.

Effect of the irradiance distribution from light curing units on the local micro-hardness of the surface of dental resins.

OBJECTIVE: An inhomogeneous irradiance distribution from a light-curing unit (LCU) can locally cause inhomogeneous curing with locally inadequately cured and/or over-cured areas causing e.g. monomer elution or internal shrinkage stresses, and thus reduce the lifetime of dental resin based composite (RBC) restorations. The aim of the study is to determine both the irradiance distribution of two light curing units (LCUs) and its influence on the local mechanical properties of a RBC. METHODS: Specimens of Arabesk TOP OA2 were irradiated for 5, 20, and 80s using a Bluephase® 20i LCU in the Low mode (666mW/cm(2)), in the Turbo mode (2222mW/cm(2)) and a Celalux® 2 (1264mW/cm(2)). The degree of conversion (DC) was determined with an ATR-FTIR. The Knoop micro-hardness (average of five specimens) was measured on the specimen surface after 24h of dark and dry storage at room temperature. RESULTS: The irradiance distribution affected the hardness distribution across the surface of the specimens. The hardness distribution corresponded well to the inhomogeneous irradiance distributions of the LCU. The highest reaction rates occurred after approximately 2s light exposure. A DC of 40% was reached after 3.6 or 5.7s, depending on the LCU. The inhomogeneous hardness distribution was still evident after 80s of light exposure. SIGNIFICANCE: The irradiance distribution from a LCU is reflected in the hardness distribution across the surface. Irradiance level of the LCU and light exposure time do not affect the pattern of the hardness distribution--only the hardness level. In areas of low irradiation this may result in inadequate resin polymerization, poor physical properties, and hence premature failure of the restorations as they are usually much smaller than the investigated specimens. It has to be stressed that inhomogeneous does not necessarily mean poor if in all areas of the restoration enough light intensity is introduced to achieve a high degree of cure.

Examining exposure reciprocity in a resin based composite using high irradiance levels and real-time degree of conversion values.

OBJECTIVE: Exposure reciprocity suggests that, as long as the same radiant exposure is delivered, different combinations of irradiance and exposure time will achieve the same degree of resin polymerization. This study examined the validity of exposure reciprocity using real time degree of conversion results from one commercial flowable dental resin. Additionally a new fitting function to describe the polymerization kinetics is proposed. METHODS: A Plasma Arc Light Curing Unit (LCU) was used to deliver 0.75, 1.2, 1.5, 3.7 or 7.5 W/cm(2) to 2mm thick samples of Tetric EvoFlow (Ivoclar Vivadent). The irradiances and radiant exposures received by the resin were determined using an integrating sphere connected to a fiber-optic spectrometer. The degree of conversion (DC) was recorded at a rate of 8.5 measurements a second at the bottom of the resin using attenuated total reflectance Fourier Transform mid-infrared spectroscopy (FT-MIR). Five specimens were exposed at each irradiance level. The DC reached after 170s and after 5, 10 and 15 J/cm(2) had been delivered was compared using analysis of variance and Fisher's PLSD post hoc multiple comparison tests (alpha=0.05). RESULTS: The same DC values were not reached after the same radiant exposures of 5, 10 and 15 J/cm(2) had been delivered at an irradiance of 3.7 and 7.5 W/cm(2). Thus exposure reciprocity was not supported for Tetric EvoFlow (p<0.05). SIGNIFICANCE: For Tetric EvoFlow, there was no significant difference in the DC when 5, 10 and 15J/cm(2) were delivered at irradiance levels of 0.75, 1.2 and 1.5 W/cm(2). The optimum combination of irradiance and exposure time for this commercial dental resin may be close to 1.5 W/cm(2) for 12s.

Dielectric analysis of depth dependent curing behavior of dental resin composites.

OBJECTIVES: The aim of this study is to investigate depth dependent changes of polymerization process and kinetics of visible light-curing (VLC) dental composites in real-time. The measured quantity - "ion viscosity" determined by dielectric analysis (DEA) - provides the depth dependent reaction rate which is correlated to the light intensity available in the corresponding depths derived from light transmission measurements. METHODS: The ion viscosity curves of two composites (VOCO Arabesk Top and Grandio) were determined during irradiation of 40s with a light-curing unit (LCU) in specimen depths of 0.5/0.75/1.0/1.25/1.5/1.75 and 2.0mm using a dielectric cure analyzer (NETZSCH DEA 231 with Mini IDEX sensors). The thickness dependent light transmission was measured by irradiation composite specimens of various thicknesses on top of a radiometer setup. RESULTS: The shape of the ion viscosity curves depends strongly on the specimen thickness above the sensor. All curves exhibit a range of linear time dependency of the ion viscosity after a certain initiation time. The determined initiation times, the slopes of the linear part of the curves, and the ion viscosities at the end of the irradiation differ significantly with depth within the specimen. The slopes of the ion viscosity curves as well as the light intensity values decrease with depth and fit to the Lambert-Beer law. The corresponding attenuation coefficients are determined for Arabesk Top OA2 to 1.39mm(-1) and 1.48mm(-1), respectively, and for Grandio OA2 with 1.17 and 1.39mm(-1), respectively. For thicknesses exceeding 1.5mm a change in polymerization behavior is observed as the ion viscosity increases subsequent to the linear range indicating some kind of reaction acceleration. SIGNIFICANCE: The two VLC composites and different specimen thicknesses discriminate significantly in their ion viscosity evolution allowing for a precise characterization of the curing process even with respect to the polymerization mechanism.

Curing kinetics of visible light curing dental resin composites investigated by dielectric analysis (DEA).

During the curing process of light curing dental composites the mobility of molecules and molecule segments is reduced leading to a significant increase of the viscosity as well as the ion viscosity. Thus, the kinetics of the curing behavior of 6 different composites was derived from dielectric analysis (DEA) using especially redesigned flat sensors with interdigit comb electrodes allowing for irradiation at the top side and measuring the ion viscosity at the bottom side. As the ion viscosities of dental composites change 1-3 orders of magnitude during the curing process, DEA provides a sensitive approach to evaluate their curing behavior, especially in the phase of undisturbed chain growth. In order to determine quantitative kinetic parameters a kinetic model is presented and examined for the evaluation of the ion viscosity curves. From the obtained results it is seen that DEA might be employed in the investigation of the primary curing process, the quality assurance of ingredients as well as the control of processing stability of the light curing dental composites.