Morphology Distribution in Injection Molded Parts.

A more sustainable use of plastic parts makes it necessary to replace current plastic parts with recyclable components, also allowing the modulation of the part properties through the process. Injection molding is one of the most widely used technologies for obtaining rigid plastic parts, so it is crucial to understand how to tailor properties by adopting the correct processing conditions. One way is to perform annealing steps directly inside the mold: in-mold annealing improves the structural integrity and durability of the material, reduces defects, increases the resistance of parts against certain chemicals, reduces wear and tear, increases ductility, and lowers brittleness. In this work, several in-mold annealing steps were conducted, changing the mold temperature and annealing duration selected on the basis of the half crystallization time of the adopted isotactic polypropylene. The typical molded part morphology, composed of oriented layers at the surface, transition zones, and spherulitic core, is strongly affected by in-mold annealing. In particular, the thickness of the oriented layer, which forms in the early phase of the process, decreases, and the spherulites increase in size. Concerning mechanical behavior, the orientation degree mostly determines the elastic modulus value close to the surface, whereas the conditions under which crystallization occurs determine the modulus in the core.

Modulating poly(lactic acid) degradation rate for environmentally sustainable applications.

The huge amount of plastics generated by the massive use of packaging makes it difficult to manage waste safely. Introducing biodegradable polymers, such as poly(lactic acid) (PLA), can at least partially reduce the environmental pollution from plastic waste. Biodegradable polymers must have a degradation rate appropriate for the intended use to replace durable plastics. This work aims to introduce PLA fillers that can modulate the degradation rate during hydrolysis and composting. For this purpose, fumaric acid and magnesium hydroxide have been proposed. The experimental findings demonstrated that magnesium oxide makes hydrolysis faster than fumaric acid. A model describing the hydrolysis reaction, which also considers the effect of crystallinity, is proposed. The model can capture the filler effect on the kinetic constants related to the autocatalytic part of the hydrolysis reaction. Degradation of the PLA and compounds was also conducted in a composting medium. The compound with fumaric acid shows faster degradation than the compound with magnesium oxide; this behavior is opposite to what is observed during hydrolysis. Degradation in a composting medium is favored in a narrow pH window corresponding to the optimum environment for microorganism growth. Magnesium oxide leads to a pH increase above the optimum level, making the environment less favorable to microorganism growth. Vice-versa, fumaric acid maintains the pH level in the optimum range: it represents an additional carbon source for microorganism growth.

Analysis of Weld Lines in Micro-Injection Molding.

Micro-injection molding (µIM) is a widespread process for the production of plastic parts with at least one dimension, or feature, in the microscale (conventionally below 500 µm). Despite injection molding being recognized as a robust process for obtaining parts with high geometry accuracy, one last occurrence remains a challenge in micro-injection molding, especially when junctions are present on the parts: the so-called weld lines. As weld lines are crucial in determining mechanical part performances, it is mandatory to clarify weld line position and characteristics, especially at the industrial scale during mold design, to limit failure causes. Many works deal with weld lines and their dependence on processing parameters for conventional injection molding, but only a few works focus on the weld line in µIM. This work examines the influence of mold temperature on the weld line position and strength by both experimental and simulation approaches in µIM. At mold temperatures below 100 °C, only short shots were obtained in the chosen cavity. At increased mold temperatures, weld lines show up to a 40% decrease in the whole length, and the overall tensile modulus doubles. This finding can be attributed to the reduction of the orientation at the weld line location favored by high mold temperatures. Moldflow simulations consistently reproduce the main features of the process, weld line position and length. The discrepancy between experimental and simulated results was attributed to the fact that crystallization in flow conditions was not accounted for in the model.

Hybrid Hemp Particles as Functional Fillers for the Manufacturing of Hydrophobic and Anti-icing Epoxy Composite Coatings.

The development of hydrophobic composite coatings is of great interest for several applications in the aerospace industry. Functionalized microparticles can be obtained from waste fabrics and employed as fillers to prepare sustainable hydrophobic epoxy-based coatings. Following a waste-to-wealth approach, a novel hydrophobic epoxy-based composite including hemp microparticles (HMPs) functionalized with waterglass solution, 3-aminopropyl triethoxysilane, polypropylene-graft-maleic anhydride, and either hexadecyltrimethoxysilane or 1H,1H,2H,2H-perfluorooctyltriethoxysilane is presented. The resulting epoxy coatings based on hydrophobic HMPs were cast on aeronautical carbon fiber-reinforced panels to improve their anti-icing performance. Wettability and anti-icing behavior of the prepared composites were investigated at 25 °C and -30 °C (complete icing time), respectively. Samples cast with the composite coating can achieve up to 30 °C higher water contact angle and doubled icing time than aeronautical panels treated with unfilled epoxy resin. A low content (2 wt %) of tailored HMPs causes an increase of ∼26% in the glass transition temperature of the coatings compared to pristine resin, confirming the good interaction between the hemp filler and epoxy matrix at the interphase. Finally, atomic force microscopy reveals that the HMPs can induce the formation of a hierarchical structure on the surface of casted panels. This rough morphology, combined with the silane activity, allows the preparation of aeronautical substrates with enhanced hydrophobicity, anti-icing capability, and thermal stability.

Mechano Chemical Compatibilization of Polyethylene with Graphite by Means of a Suitable Ester.

An effective non-covalent compatibilization method for graphite and low-density polyethylene is reported. To obtain this result, pyren-1-yl-stearate (P1S) was synthesized, characterized and mixed with graphite to provide a better dispersion in polyethylene matrix. The P1S improves the dispersion of carbon filler in polyethylene through non-covalent compatibilization: the pyrenyl group gives π-π stacking interactions with graphite and the stearyl chain provides van der Waals interaction with the polymer chain (specifically London dispersion forces). In this study, different P1S/graphite fillers were prepared with a ratio by weight of 90/10 and 50/50, respectively, by using manual and ball-milling mixing. Their stability, interaction and morphology were evaluated through TGA, RX, and SEM. Thermogravimetric analyses showed that ball-milling mixing is more effective than manual mixing in promoting π-π stacking interactions of molecules such as P1S ester containing an alkyl chain and aromatic rings. The role of ball milling is confirmed by X-ray diffraction measurements since it was possible to observe both exfoliation and intercalation phenomena when this technique was used to mix the P1S ester with graphite. SEM analyses of polyethylene containing 1% of the carbon fillers again highlighted the importance of ball milling to promote the interaction of the ester with graphite and, simultaneously, the importance of the alkyl chain in order to achieve polyethylene-graphite compatibilization.

Nanometric Mechanical Behavior of Electrospun Membranes Loaded with Magnetic Nanoparticles.

This work analyzes on nanoscale spatial domains the mechanical features of electrospun membranes of Polycaprolactone (PCL) loaded with Functionalized Magnetite Nanoparticles (FMNs) produced via an electrospinning process. Thermal and structural analyses demonstrate that FMNs affect the PCL crystallinity and its melting temperature. HarmoniX-Atomic Force Microscopy (H-AFM), a modality suitable to map the elastic modulus on nanometric domains of the sample surface, evidences that the FMNs affect the local mechanical properties of the membranes. The mechanical modulus increases when the tip reveals the magnetite nanoparticles. That allows accurate mapping of the FMNs distribution along the nanofibers mat through the analysis of a mechanical parameter. Local mechanical modulus values are also affected by the crystallinity degree of PCL influenced by the filler content. The crystallinity increases for a low filler percentage (<5 wt.%), while, higher magnetite amounts tend to hinder the crystallization of the polymer, which manifests a lower crystallinity. H-AFM analysis confirms this trend, showing that the distribution of local mechanical values is a function of the filler amount and crystallinity of the fibers hosting the filler. The bulk mechanical properties of the membranes, evaluated through tensile tests, are strictly related to the nanometric features of the complex nanocomposite system.

Role of MWCNTs Loading in Designing Self-Sensing and Self-Heating Structural Elements.

This work proposes nanocomposites with carbon nanotubes characterized by self-sensing and self-heating properties. Recently, a growing interest in these two properties has been found in many industrial sectors, especially in the aerospace and automotive fields. While the self-sensing function allows diagnosing the presence of micro-damage in the material thanks to the detection of residual resistance, the self-heating function is exploited to properly tune the heating performance in terms of the heating rate and final temperature values. An electrical percolation value of around 0.5% by weight of carbon nanotubes was found by electrical characterization. The AC conductivity of the nanocomposites, in the range of 100 Hz to 1 MHz, evidences that beyond a CNTs amount of 0.5% wt/wt, they are characterized by a purely resistive behavior. The self-sensing analysis displayed a gauge factor value of 4.1. The solid thermal stability up to 300 °C makes the material suitable as a heating element at high temperatures. SEM investigations and temperature maps evidence a good dispersion of the conductive filler in the epoxy matrix and, consequently, good isotropy in heat distribution. As regards the trend of electrical resistance by varying the temperature, the electro-thermal investigation has shown the presence of both Positive Temperature Coefficient (PTC) and Negative Temperature Coefficient (NTC) behaviors with a predominance of NTC as soon as the temperature becomes closer to the glass transition temperature of the epoxy resin.

Modeling and Analysis of Morphology of Injection Molding Polypropylene Parts Induced by In-Mold Annealing.

It is generally recognized that high-temperature treatments, namely annealing, influence the microstructure and the morphology, which, in turn, determine the mechanical properties of polymeric parts. Therefore, annealing can be adopted to control the mechanical performance of the molded parts. This work aims to assess the effect of annealing on the morphology developed in isotactic polypropylene (iPP) injection-molded parts. In particular, a two-step annealing is adopted: the polymer is injected in a mold at a high temperature (413 or 433 K), which is kept for 5 min (first annealing step); afterward, the mold temperature is cooled down at 403 K and held at that temperature for a time compatible with the crystallization half-time at that temperature (second annealing step). The characterization of morphology is carried out by optical and electronic scanning microscopy. The temperature of the first annealing step does not influence the thickness of the fibrillar skin layer; however, such a layer is thinner than that found in the molded parts obtained without any annealing steps. The second annealing step does not influence the thickness of the fibrillar skin layer. The dimension of spherulites found in the core is strongly influenced by both annealing steps: the spherulite dimensions enlarge by the effect of annealing steps. A model that considers spherulite and fibril evolutions is adopted to describe the effect of molding conditions on the final morphology distribution along the part thickness. The model, which adopts as input the thermo-mechanical histories calculated by commercial software for injection molding simulation, consistently predicts the main effects of the molding conditions on the morphology distributions.

Production of Mesoglycan/PCL Based Composites through Supercritical Impregnation.

The development of targeted therapies for wound repair is knowing a growing interest due to the increasing aging of the population and the incidence of chronic pathologies, mainly pressure ulcers. Among molecules recruiting cell populations and promoting the formation of new vital tissue, sodium mesoglycan (MSG) has been proven to be effective in wound healing. In this work, MSG impregnation of polymer matrices has been attempted by a supercritical carbon dioxide-based process. Polymeric matrices are composed of polycaprolactone blends, where water-soluble polymers, polyethylene glycol, polyvinyl pyrrolidone, gelatin, and thermoplastic starch, have been employed to modulate the MSG release, making the devices potentially suitable for topical administrations. Two different techniques have been used to obtain the films: the first one is compression molding, producing compact and continuous structures, and the second one is electrospinning, producing membrane-like designs. A higher amount of MSG can be loaded into the polymeric matrix in the membrane-like structures since, in these films, the impregnation process is faster than in the case of compression molded films, where the carbon dioxide has firstly diffused and then released the active molecule. The type of water-soluble polymer influences the drug release rate: the blend polycaprolactone-gelatin gives a prolonged release potentially suitable for topical administration.

Multi-Scale Simulation of Injection Molding Process with Micro-Features Replication: Relevance of Rheological Behaviour and Crystallization.

The possibility of tailoring key surface properties through the injection molding process makes it intriguing from the perspective of sustainability enhancement. The surface properties depend on the replication accuracy of micro and nanostructures on moldings; such an accuracy is enhanced with cavity temperature. The simulation of the injection molding process is very challenging in the presence of micro and nanostructures on the cavity surface; this does not allow for the neglect of phenomena generally considered not to influence the overall process. In this paper, a multiscale approach was proposed: in the first step, the simulation of the overall process was conducted without considering the presence of the microstructure; in the second step the outputs of the first step were used as an input to simulate the replication of the microfeature. To this purpose, a lubrication approximation was adopted, and the contribution of the trapped air, which slows down the polymer advancement, was accounted for. A modification of the viscosity equation was also proposed to describe the rheological behavior of isotactic polypropylene at very low temperatures. Concerning the microcavity filling simulation, the modification of the viscosity description at low temperatures consistently describes the process, in terms of polymer solidification. Concerning the replication accuracy, it increases with the cavity surface temperature, consistently with the experimental observations.

Polycaprolactone/polyethylene-glycol capsules made by injection molding: A drug release modeling.

Polycaprolactone (PCL)/Polyethylene-glycol (PEG) capsules are prepared by injection molding with the aim of producing Colon-specific Drug Delivery Systems (CDDS). PCL, being a gastroresistant polymer, is suitable for this kind of delivery; however, the release from PCL devices is too slow. For this reason, in this paper, different percentages of PEG (10, 20 and 30 w/w %) have been added to obtain blends able to modulate the release from PCL-based capsules. The drug release rate from PCL/PEG capsules increases with the PEG percentage; using PCL/PEG 70/30 w/w capsules, the drug release is suitable for CDDS. The experimental data have been modelled, accounting for three steps: the penetration of the release medium into the capsule, the drug dissolution in the release medium, and the drug migration from the capsule to the medium. The model accurately describes the data, showing a mass transfer coefficient strongly dependent on the PEG percentage.

Comparison of Degradation Behavior of Newly Developed Encapsulation Materials for Photovoltaic Applications under Different Artificial Ageing Tests.

The main focus of this work is to investigate the degradation behavior of two newly developed encapsulants for photovoltaic applications (thermoplastic polyolefin (TPO) and polyolefin elastomer (POE)), compared to the most widely used Ethylene Vinyl Acetate (EVA) upon exposure to two different artificial ageing tests (with and without ultraviolet (UV) irradiation). Additive composition, optical and thermal properties and chemical structure (investigated by means of Thermal Desorption Gas Chromatography coupled to Mass Spectrometry, UV-Visible-Near Infrared spectroscopy, Differential Scanning Calorimetry, Thermogravimetric Analysis and Fourier Transform-Infrared spectroscopy, respectively) of the analyzed polymers were monitored throughout the exposure to artificial ageing tests. Relevant signs of photo-oxidation were detectable for TPO after the UV test, as well as a depletion of material's stabilizers. Signs of degradation for EVA and POE were detected when the UV dose applied was equal to 200 kW h m-2. A novel approach is presented to derive information of oxidation induction time/dose from thermogravimetric measurements that correlate well with results obtained by using oxidation indices.

Fused Filament Deposition of PLA: The Role of Interlayer Adhesion in the Mechanical Performances.

A set of criteria to enhance mechanical performances of standard specimens (Type V, ANSI D368) made of polylactic acid (PLA) were proposed. Fused PLA deposition was conducted with nozzle temperature ranging from 180 to 230 °C and deposition plate temperature ranging from 70 to 110 °C. Optical microscopy, elastic modulus analysis and density measurement allowed emphasizing the effect of temperature field, also measured during the process, on the morphology and the mechanical characteristics of the specimen. Atomic force microscopy revealed a morphology typical of amorphous samples with globular structures. Poor interlayer adhesion was detected in the part of the specimen located at larger distance from the deposition plate, showing an elastic modulus lower than those measured in the central part (220 MPa vs. 500 MPa). The specimen crystallinity degree was below 3%. The molecular weight between entanglements was adopted as a measure of the interlayer molecular diffusion. A successful diffusion and re-entanglement of the polymer melt at the interface was the key to improving mechanical performance. A mathematical model describing the transient heat transfer during the fused PLA deposition and accounting for solidification and the nonisothermal crystallization kinetics was introduced. Simulated temperature evolutions were consistent with the experimental ones. They were related to the mechanical performances, the morphology, and the molecular weight between entanglements of the parts.

Reinforced Smart Foams Produced with Time-Profiled Magnetic Fields.

Polymeric smart foams are lightweight and multifunctional porous materials that are sensitive to the magnetic field due to the presence of magnetic particles embedded in the matrix. Recently, a constant magnetic field has been exploited to align the particles along the magnetic field lines during the formation of the porous structure. In this paper, a new field-structuring process was developed that makes use of a time-profiled magnetic field during the foaming process to control the geometrical features of the particles aggregates. The effects of magnetic field strength as well as the switch-on and switch-off times on the magnetoelastic behavior of the smart foams were investigated. It was proven that the alignment of the particles results in both a strong relative sensitivity to the magnetic field and a positive stress change, whose extent depends on the geometrical features of the developed aggregates.

State-of-the-Art Polymer Science and Technology in Italy.

The history of polymers in Italy certainly begins with Giulio Natta and the discovery of isotactic polypropylene [...].

Low-Voltage Icing Protection Film for Automotive and Aeronautical Industries.

High-performance heater films are here proposed. They manifest great applicative potentiality in the de-icing technology of aircraft and motor vehicles. The films are suitable to be integrated into composite structures for the de/anti-icing function, which can be activated if the need arises. The heating is based on the joule effect of the current flowing through the electrically conductive films. Voltage and current parameters have been set based on the generators' capacities on-board an aircraft and a car, as well as on the energy consumption during the operating conditions and the autonomy in the time. Green processes have been employed through all preparative steps of the films, which are composed of expanded graphite (60% wt/wt) and polyvinyl alcohol (PVA) (40% wt/wt). The results reveal a very significant influence of the aspect ratio of the filler on the heating and de-icing performance and suggest how to enhance the de-icing efficiency saving energy and adapting the current on-board aircraft/car generators for de-icing operations.

Correction: Speranza, V. et al. Hierarchical Structure of iPP During Injection Molding Process with Fast Mold Temperature Evolution. Materials 2019, 12, 424.

The correction reported in the following has to be applied to the paper [...].

Effect of Rapid Mold Heating on the Structure and Performance of Injection-Molded Polypropylene.

The tailoring by the process of the properties developed in the plastic objects is the more effective way to improve the sustainability of the plastic objects. The possibility to tailor to the final use the properties developed within the molded object requires further understanding of the relationship between the properties of the plastic objects and the process conduction. One of the main process parameters that allow adjusting the properties of molded objects is the mold temperature. In this work, a thin electrical heater was located below the cavity surface in order to obtain rapid and localized surface heating/cooling cycles during the injection molding process. An isotactic polypropylene was adopted for the molding tests, during which surface temperature was modulated in terms of values and heating times. The modulation of the cavity temperature was found able to control the distribution of relevant morphological characteristics, thus, properties along the sample thickness. In particular, lamellar thickness, crystallinity distribution, and orientation were analyzed by synchrotron X-ray experiments, and the morphology and elastic modulus were characterized by atomic force microscopy acquisitions carried out with a tool for the simultaneous nanomechanical characterization. The crystalline degree slightly increased with the cavity temperature, and this induced an increase in the elastic modulus when high temperatures were adopted for the cavity surface. The cavity temperature strongly influenced the orientation distribution that, on its turn, determined the highest values of the elastic modulus found in the shear layer. Furthermore, although the sample core, not experiencing a strong flow field, was not characterized by high levels of orientation, it might show high values of the elastic modulus if temperature and time during crystallization were sufficient. In particular, if the macromolecules spent adequate time at temperatures close to the crystallization temperature, they could achieve high levels of structuring and, thus, high values of elastic modulus.

PCL/Mesoglycan Devices Obtained by Supercritical Foaming and Impregnation.

In this work, a one-shot process for the simultaneous foaming of polycaprolactone (PCL) and impregnation of mesoglycan (MSG) into the porous structure was successfully attempted. Supercritical carbon dioxide plays the role of the foaming agent with respect to PCL and of the solvent with respect to MSG. The main objective is to produce an innovative topical device for application on skin lesions, promoting prolonged pro-resolving effects. The obtained device offers a protective barrier to ensure a favorable and sterilized environment for the wound healing process. The impregnation kinetics revealed that a pressure of 17 MPa, a temperature of 35 °C, and a time of impregnation of 24 h assured a proper foaming of PCL in addition to the impregnation of the maximum amount of MSG; i.e., 0.22 mgMSG/mgPCL. After a preliminary study conducted on PCL granules used as brought, the MSG impregnation was performed at the optimized process conditions also on a PCL film, produced by compression molding, with the final goal of producing medical patches. Comparing the dissolution profiles in phosphate buffered saline solution (PBS) of pure MSG and MSG impregnated on foamed PCL, it was demonstrated that the release of MSG was significantly prolonged up to 70 times. Next, we performed functional assays of in vitro wound healing, cell invasion, and angiogenesis to evaluate the biological effects of the PCL-derived MSG. Interestingly, we found the ability of this composite system to promote the activation of human keratinocytes, fibroblasts, and endothelial cells, as the main actors of tissue regeneration, confirming what we previously showed for the MSG alone.

Lightweight High-Performance Polymer Composite for Automotive Applications.

The automotive industry needs to produce plastic products with high dimensional accuracy and reduced weight, and this need drives the research toward less conventional industrial processes. The material that was adopted in this work is a glass-fiber-reinforced polyamide 66 (PA66), a material of great interest for the automotive industry because of its excellent properties, although being limited in application because of its relatively high cost. In order to reduce the cost of the produced parts, still preserving the main properties of the material, the possibility of applying microcellular injection molding process was explored in this work. In particular, the influence of the main processing parameters on morphology and performance of PA66 + 30% glass-fiber foamed parts was investigated. An analysis of variance (ANOVA) was employed to identify the significant factors that influence the morphology of the molded parts. According to ANOVA results, in order to obtain homogeneous foamed parts with good mechanical properties, an injection temperature of 300 °C, a high gas injection pressure, and a large thickness of the parts should be adopted.