Analysis of Selected Properties of Injection Moulded Sustainable Biocomposites from Poly(butylene succinate) and Wheat Bran

The paper presents a procedure of the manufacturing and complex analysis of the properties of injection mouldings made of polymeric composites based on the poly(butylene succinate) (PBS) matrix with the addition of a natural filler in the form of wheat bran (WB). The scope of the research included measurements of processing shrinkage and density, analysis of the chemical structure, measurements of the thermal and thermo-mechanical properties (Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TG), Heat Deflection Temperature (HDT), and Vicat Softening Temperature (VST)), and measurements of the mechanical properties (hardness, impact strength, and static tensile test). The measurements were performed using design of experiment (DOE) methods, which made it possible to determine the investigated relationships in the form of polynomials and response surfaces. The mass content of the filler and the extruder screw speed during the production of the biocomposite granulate, which was used for the injection moulding of the test samples, constituted the variable factors adopted in the DOE. The study showed significant differences in the processing, thermal, and mechanical properties studied for individual systems of the DOE.     

Modern Biodegradable Plastics—Processing and Properties Part II

Four different plastics were tested: potato starch based plastic (TPS-P)–BIOPLAST GF 106/02; corn starch based plastic (TPS-C)–BioComp BF 01HP; polylactic acid (polylactide) plastic (PLA)—BioComp BF 7210 and low density polyethylene, trade name Malen E FABS 23-D022; as a petrochemical reference sample. Using the blown film extrusion method and various screw rotational speeds, films were obtained and tested, as a result of which the following were determined: breaking stress, strain at break, static and dynamic friction coefficient of film in longitudinal and transverse direction, puncture resistance and strain at break, color, brightness and gloss of film, surface roughness, barrier properties and microstructure. The biodegradable plastics tested are characterized by comparable or even better mechanical strength than petrochemical polyethylene for the range of film blowing processing parameters used here. The effect of the screw rotational speed on the mechanical characteristics of the films obtained was also demonstrated. With the increase in the screw rotational speed, the decrease of barrier properties was also observed. No correlation between roughness and permeability of gases and water vapor was shown. It was indicated that biodegradable plastics might be competitive for conventional petrochemical materials used in film blowing niche applications where cost, recyclability, optical and water vapor barrier properties are not critical.     

Artificial Ageing,Chemical Resistance,and Biodegradation of Biocomposites from Poly(Butylene Succinate) and Wheat Bran

The results of comprehensive studies on accelerated (artificial) ageing and biodegradation of polymer biocomposites on PBS matrix filled with raw wheat bran (WB) are presented in this paper. These polymer biocomposites are intended for the manufacture of goods, in particular disposable packaging and disposable utensils, which decompose naturally under the influence of biological agents. The effects of wheat bran content within the range of 10–50 wt.% and extruder screw speed of 50–200 min⁻¹ during the production of biocomposite pellets on the resistance of the products to physical, chemical, and biological factors were evaluated. The research included the determination of the effect of artificial ageing on the changes of structural and thermal properties by infrared spectra (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TG). They showed structural changes—disruption of chains within the ester bond, which occurred in the composition with 50% bran content as early as after 250 h of accelerated ageing. An increase in the degree of crystallinity with ageing was also found to be as high as 48% in the composition with 10% bran content. The temperature taken at the beginning of weight loss of the compositions studied was also lowered, even by 30 °C at the highest bran content. The changes of mechanical properties of biocomposite samples were also investigated. These include: hardness, surface roughness, transverse shrinkage, weight loss, and optical properties: colour and gloss. The ageing hardness of the biocomposite increased by up to 12%, and the surface roughness (R_a) increased by as much as 2.4 µm at the highest bran content. It was also found that ageing causes significant colour changes of the biocomposition (ΔE = 7.8 already at 10% bran content), and that the ageing-induced weight loss of the biocomposition of 0.31–0.59% is lower than that of the samples produced from PBS alone (1.06%). On the other hand, the transverse shrinkage of moldings as a result of ageing turned out to be relatively small, at 0.05%–0.35%. The chemical resistance of biocomposites to NaOH and HCl as well as absorption of polar and non-polar liquids (oil and water) were also determined. Biodegradation studies were carried out under controlled conditions in compost and weight loss of the tested compositions was determined. The weight of samples made from PBS alone after 70 days of composting decreased only by 4.5%, while the biocomposition with 10% bran content decreased by 15.1%, and with 50% bran, by as much as 68.3%. The measurements carried out showed a significant influence of the content of the applied lignocellulosic fillers (LCF) in the form of raw wheat bran (WB) on the examined properties of the biocompositions and the course of their artificial ageing and biodegradation. Within the range under study, the screw speed of the extruder during the production of biocomposite pellets did not show any significant influence on most of the studied properties of the injection mouldings produced from it.     

Development of Toughened Flax Fiber Reinforced Composites. Modification of Poly(lactic acid)/Poly(butylene adipate-co-terephthalate) Blends by Reactive Extrusion Process

The presented study focuses on the development of flax fiber (FF) reinforced composites prepared with the use of poly(lactic acid)/poly(butylene adipate-co-terephthalate)—PLA/PBAT blend system. This type of modification was aimed to increase impact properties of PLA-based composites, which are usually characterized by high brittleness. The PLA/PBAT blends preparation was carried out using melt blending technique, while part of the samples was prepared by reactive extrusion process with the addition of chain extender (CE) in the form of epoxy-functionalized oligomer. The properties of unreinforced blends was evaluated using injection molded samples. The composite samples were prepared by compression molding technique, while flax fibers reinforcement was in the form of plain fabric. The properties of the laminated sheets were investigated during mechanical test measurements (tensile, flexural, impact). Differential scanning calorimetry (DSC) analysis was used to determine the thermal properties, while dynamic mechanical thermal analysis (DMTA) and heat deflection temperature (HDT) measurements were conducted in order to measure the thermomechanical properties. Research procedure was supplemented with structure evaluation using scanning electron microscopy (SEM) analysis. The comparative study reveals that the properties of PLA/PBAT-based composites were more favorable, especially in the context of impact resistance improvement. However, for CE modified samples also the modulus and strength was improved. Structural observations after the impact tests confirmed the presence of the plastic deformation of PLA/PBAT matrix, which confirmed the favorable properties of the developed materials. The use of PBAT phase as the impact modifier strongly reduced the PLA brittleness, while the reactive extrusion process improves the fiber-matrix interactions leading to higher stiffness and strength.     

Optimization of Polymer Processing: A Review (Part II-Molding Technologies)

The application of optimization techniques to improve the performance of polymer processing technologies is of great practical consequence, since it may result in significant savings of materials and energy resources, assist recycling schemes and generate products with better properties. The present review aims at identifying and discussing the most important characteristics of polymer processing optimization problems in terms of the nature of the objective function, optimization algorithm, and process modelling approach that is used to evaluate the solutions and the parameters to optimize. Taking into account the research efforts developed so far, it is shown that several optimization methodologies can be applied to polymer processing with good results, without demanding important computational requirements. Furthermore, within the field of artificial intelligence, several approaches can reach significant success. The first part of this review demonstrated the advantages of the optimization approach in polymer processing, discussed some concepts on multi-objective optimization and reported the application of optimization methodologies to single and twin screw extruders, extrusion dies and calibrators. This second part focuses on injection molding, blow molding and thermoforming technologies.     

Material Extrusion of Structural Polymer–Aluminum Joints—Examining Shear Strength,Wetting, Polymer Melt Rheology and Aging

Generating polymer–metal structures by means of additive manufacturing offers huge potential for customized, sustainable and lightweight solutions. However, challenges exist, primarily with regard to reliability and reproducibility of the additively generated joints. In this study, the polymers ABS, PETG and PLA, which are common in material extrusion, were joined to grit-blasted aluminum substrates. Temperature dependence of polymer melt rheology, wetting and tensile single-lap-shear strength were examined in order to obtain appropriate thermal processing conditions. Joints with high adhesive strength in the fresh state were aged for up to 100 days in two different moderate environments. For the given conditions, PETG was most suitable for generating structural joints. Contrary to PETG, ABS–aluminum joints in the fresh state as well as PLA–aluminum joints in the aged state did not meet the demands of a structural joint. For the considered polymers and processing conditions, this study implies that the suitability of a polymer and a thermal processing condition to form a polymer–aluminum joint by material extrusion can be evaluated based on the polymer’s rheological properties. Moreover, wetting experiments improved estimation of the resulting tensile single-lap-shear strength.     

Morphology,Thermo-Mechanical Properties and Biodegradibility of PCL/PLA Blends Reactively Compatibilized by Different Organic Peroxides

Reactive blending is a promising approach for the sustainable development of bio-based polymer blends and composites, which currently is gaining more and more attention. In this paper, biodegradable blends based on poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared via reactive blending performed in an internal mixer. The PCL and PLA content varied in a ratio of 70/30 and 55/45. Reactive modification of PCL/PLA via liquid organic peroxides (OP) including 0.5 wt.% of tert-butyl cumyl peroxide (BU), 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane (HX), and tert-butyl peroxybenzoate (PB) is reported. The materials were characterized by rotational rheometer, atomic force microscopy (AFM), thermogravimetry (TGA), differential scanning calorimetry (DSC), tensile tests and biodegradability tests. It was found that the application of peroxides improves the miscibility between PCL and PLA resulted in enhanced mechanical properties and more uniform morphology. Moreover, it was observed that the biodegradation rate of PCL/PLA blends reactively compatibilized was lower comparing to unmodified samples and strongly dependent on the blend ratio and peroxide structure. The presented results confirmed that reactive blending supported by organic peroxide is a promising approach for tailoring novel biodegradable polymeric systems with controllable biodegradation rates.     

A Combined Experimental and Modeling Study for Pellet-Fed Extrusion-Based Additive Manufacturing to Evaluate the Impact of the Melting Efficiency

To improve the product quality of polymeric parts realized through extrusion-based additive manufacturing (EAM) utilizing pellets, a good control of the melting is required. In the present work, we demonstrate the strength of a previously developed melt removal using a drag framework to support such improvement. This model, downscaled from conventional extrusion, is successfully validated for pellet-based EAM—hence, micro-extrusion—employing three material types with different measured rheological behavior, i.e., acrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA) and styrene-ethylene-butylene-styrene polymer (SEBS). The model’s validation is made possible by conducting for the first time dedicated EAM screw-freezing experiments combined with appropriate image/data analysis and inputting rheological data. It is showcased that the (overall) processing temperature is crucial to enable similar melting efficiencies. The melting mechanism can vary with the material type. For ABS, an initially large contribution of viscous heat dissipation is observed, while for PLA and SEBS thermal conduction is always more relevant. It is highlighted based on scanning electron microscopy (SEM) analysis that upon properly tuning the finalization of the melting point within the envisaged melting zone, better final material properties are achieved. The model can be further used to find an optimal balance between processing time (e.g., by variation of the screw frequency) and material product performance (e.g., strength of the printed polymeric part).     

Solution Blow Spinning of Polycaprolactone—Rheological Determination of Spinnability and the Effect of Processing Conditions on Fiber Diameter and Alignment

The growing popularity of solution blow spinning as a method for the production of fibrous tissue engineering scaffolds and the vast range of polymer–solvent systems available for the method raises the need to study the effect of processing conditions on fiber morphology and develop a method for its qualitative assessment. Rheological approaches to determine polymer solution spinnability and image analysis approaches to describe fiber diameter and alignment have been previously proposed, although in a separate manner and mostly for the widely known, well-researched electrospinning method. In this study, a series of methods is presented to determine the processing conditions for the development of submicron fibrous scaffolds. Rheological methods are completed with extensive image analysis to determine the spinnability window for a polymer–solvent system and qualitatively establish the influence of polymer solution concentration and collector rotational speed on fiber morphology, diameter, and alignment. Process parameter selection for a tissue engineering scaffold target application is discussed, considering the varying structural properties of the native extracellular matrix of the tissue of interest.     

Evaluation of the Mechanical and Biocidal Properties of Lapacho from Tabebuia Plant as a Biocomposite Material

The aim of this article is to discuss in detail the physicochemical properties of polylactide (PLA) reinforced by cortex fibers, which may cause bacterial mortality and increased biodegradation rates. PLA biocomposites containing cortex Lapacho fibers from Tabebuia (1–10 wt%) were prepared by extrusion and injection moulding processes. The effects of Lapacho on the mechanical and biocidal properties of the biocomposites were studied using tensile and impact tests, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetry (TG), and the method of evaluating the antibacterial activity of antibacterial treated according to the standard ISO 22196:2011. It also presented the effects of Lapacho on the structural properties and biodegradation rates of biocomposites. This research study provides very important results complementing the current state of knowledge about the biocidal properties of Lapacho from Tabebuia plants and about cortex-reinforced biocomposites.     

Theoretical Studies of the Interaction between Screw Surface and Material in the Mixer

Mixing is one of the most commonly used processes in food, animal feed, chemical, cosmetic, etc., industries. It is supposed to provide high-quality homogenous, nutritious mixtures. To provide appropriate mixing of materials while maintaining the process high efficiency and low energy consumption it is crucial to explore and describe the material flow caused by the movement of mixing elements and the contact between particles. The process of mixing is also affected by structural features of the machine components and the mixing chamber, speed of mixing, and properties of the mixed materials, such as the size of particles, moisture, friction coefficients. Thus, modeling of the phenomena that accompany the process of mixing using the above-listed parameters is indispensable for appropriate implementation of the process. The paper provides theoretical power calculations that take into account the material speed change, the impact of the material friction coefficient on the screw steel surface and the impact of the friction coefficient on the material, taking into account the loading height of the mixing chamber and the chamber loading value. Dependencies between the mixer power and the product degree of fineness, rotational speed of screw friction coefficients, the number of windings per length unit, and width of the screw tape have been presented on the basis of a developed model. It has been found that power increases along with an increase in the value of these parameters. Verification of the theoretical model indicated consistence of the predicted power demand with the power demand determined in tests performed on a real object for values of the assumed, effective loading, which was 65–75%.     

Tribology of Polymer Blends PBT + PTFE

This paper presents results on tribological characteristics for polymer blends made of polybutylene terephthalate (PBT) and polytetrafluoroethylene (PTFE). This blend is relatively new in research as PBT has restricted processability because of its processing temperature near the degradation one. Tests were done block-on-ring tribotester, in dry regime, the variables being the PTFE concentration (0%, 5%, 10% and 15% wt) and the sliding regime parameters (load: 1, 2.5 and 5 N, the sliding speed: 0.25, 0.5 and 0.75 m/s, and the sliding distance: 2500, 5000 and 7500 m). Results are encouraging as PBT as neat polymer has very good tribological characteristics in terms of friction coefficient and wear rate. SEM investigation reveals a quite uniform dispersion of PTFE drops in the PBT matrix. Either considered a composite or a blend, the mixture PBT + 15% PTFE exhibits a very good tribological behavior, the resulting material gathering both stable and low friction coefficient and a linear wear rate lower than each component when tested under the same conditions.     

Thermal and mechanical behavior of biocomposites using additive manufacturing

Research on additive manufacturing (AM) has gained significant attention in recent years. In this study, two different matrices of polypropylene and polylactic acid materials filled with three different percentages of wood flour were employed; namely 10, 20, and 30%. Biocomposite filaments (developed by twin screw extrusion) were further used in AM by fused deposition modeling (FDM) to obtain testing samples for the characterization of the tensile and flexural properties through mechanical testing. Tensile and flexural mechanical properties of the composite material obtained by AM-FDM were compared against those obtained by injection molding. Experimental results showed that samples obtained with a percentage of 20% of wood flour showed lower mechanical properties, while those obtained at 30% testing samples turned very brittle. Mechanical properties like flexural stiffness were higher in the testing samples obtained by injection molding compared to those by AM-FDM. To understand the thermal behavior of the composites, specimens were subjected to TGA experimentation. Experimental results show an analysis of the optimum temperatures for processing the composites through AM, and provide evidence that these composites could potentially be applied in the design of auto parts due to their biodegradability and mechanical strength.     

Study of Thermal,Mechanical and Barrier Properties of Biodegradable PLA/PBAT Films with Highly Oriented MMT

In order to improve the properties of biodegradable polylactide (PLA), mixtures with polybutylene adipate-co-terephthalate (PBAT) were prepared. PLA is a bio-based and renewable biodegradable material, made from starch. PBAT is a biodegradable polyester for compostable film. In order to improve the composite properties, two types of additives were implemented via melt mixing, a chain extender (CE) and montmorillonite (MMT). CE was used as an interfacial modifier to enhance the adhesion between components. Montmorillonite is a widely studied clay added to polymer nanocomposites. Due to the lamellar structure, it improves the barrier properties of materials. PLA/PBAT films were oriented in the extrusion process and the amounts of filler introduced into the PLA/PBAT nanocomposites were 1.0, 3.0, and 5.0%. The improvement in the PLA barrier properties by the addition of PBAT and 5% of MMT was confirmed as the oxygen permeability decreased almost by a factor of 3. The addition of the biodegradable polymer, chain extender, montmorillonite, and the implemented orientation process resulted in a decrease in composite viscosity and an increase in the PLA crystallinity percentage (up to 25%), and the wettability tests confirmed the synergic behavior of the selected polymer blend.     

Design of Shape Memory Thermoplastic Material Systems for FDM-Type Additive Manufacturing

The work presented here describes a paradigm for the design of materials for additive manufacturing platforms based on taking advantage of unique physical properties imparted upon the material by the fabrication process. We sought to further investigate past work with binary shape memory polymer blends, which indicated that phase texturization caused by the fused filament fabrication (FFF) process enhanced shape memory properties. In this work, two multi-constituent shape memory polymer systems were developed where the miscibility parameter was the guide in material selection. A comparison with injection molded specimens was also carried out to further investigate the ability of the FFF process to enable enhanced shape memory characteristics as compared to other manufacturing methods. It was found that blend combinations with more closely matching miscibility parameters were more apt at yielding reliable shape memory polymer systems. However, when miscibility parameters differed, a pathway towards the creation of shape memory polymer systems capable of maintaining more than one temporary shape at a time was potentially realized. Additional aspects related to impact modifying of rigid thermoplastics as well as thermomechanical processing on induced crystallinity are also explored. Overall, this work serves as another example in the advancement of additive manufacturing via materials development.     

Effect of Secondary Carbon Nanofillers on the Electrical,Thermal, and Mechanical Properties of Conductive Hybrid Composites Based on Epoxy Resin and Graphite

In this work, we present a comparative study of the impact of secondary carbon nanofillers on the electrical and thermal conductivity, thermal stability, and mechanical properties of hybrid conductive polymer composites (CPC) based on high loadings of synthetic graphite and epoxy resin. Two different carbon nanofillers were chosen for the investigation—low-cost multi-layered graphene nanoplatelets (GN) and carbon black (CB), which were aimed at improving the overall performance of composites. The samples were obtained by a simple, inexpensive, and effective compression molding technique, and were investigated by the means of, i.a., scanning electron microscopy, Raman spectroscopy, electrical conductivity measurements, laser flash analysis, and thermogravimetry. The tests performed revealed that, due to the exceptional electronic transport properties of GN, its relatively low specific surface area, good aspect ratio, and nanometric sizes of particles, a notable improvement in the overall characteristics of the composites (best results for 4 wt % of GN; σ = 266.7 S cm⁻¹; λ = 40.6 W mK⁻¹; fl. strength = 40.1 MPa). In turn, the addition of CB resulted in a limited improvement in mechanical properties, and a deterioration in electrical and thermal properties, mainly due to the too high specific surface area of this nanofiller. The results obtained were compared with US Department of Energy recommendations regarding properties of materials for bipolar plates in fuel cells. As shown, the materials developed significantly exceed the recommended values of the majority of the most important parameters, indicating high potential application of the composites obtained.     

Friction Stir Processing Influence on Microstructure,Mechanical, and Corrosion Behavior of Steels: A Review

Friction stir processing (FSP) technology has received reasonable attention in the past two decades to process a wide range of materials such as aluminum, magnesium, titanium, steel, and superalloys. Due to its thermomechanical processing nature, FSP is used to alter grain structure and enhance mechanical and corrosion behavior in a wide range of steels. The refinement in grains and phase transformations achieved in steel after FSP affects hardness, tensile properties, fracture toughness, fatigue crack propagation rate, wear resistance, and corrosion resistance. A number of review papers are available on friction stir welding (FSW) or FSP of nonferrous alloys. In this article, a comprehensive literature review on the FSP/FSW of different types of steels is summarized. Specifically, the influence of friction stir processing parameters such as advancing speed, rotational speed, tool material, etc., on steels’ performance is discussed along with assessment methodologies and recommendations.     

Thermal Stability and Dynamic Mechanical Properties of Poly(ε-caprolactone)/Chitosan Composite Membranes

Poly (ε-caprolactone) (PCL) and chitosan (CS) are widely used as biodegradable and biocompatible polymers with desirable properties for tissue engineering applications. Composite membranes (CS–PCL) with various blend ratios (CS:PCL, w/w) of 0:100, 5:95, 10:90, 15:85, 20:80, and 100:0 were successfully prepared by lyophilization. The thermal stabilities of the CS–PCL membranes were systematically characterized by thermogravimetric analysis (TG), dynamic thermogravimetry (DTG), and differential scanning calorimetry (DSC). It was shown that the blend ratio of PCL and CS had a significant effect on the thermal stability, hydrophilicity, and dynamic mechanical viscoelasticity of the CS–PCL membranes. All the samples in the experimental range exhibited high elasticity at low temperature and high viscosity at high temperatures by dynamic mechanical thermal analysis (DMTA). The performances of the CS–PCL membranes were at optimum levels when the blend ratio (w/w) was 10:90. The glass transition temperature of the CS–PCL membranes increased from 64.8 °C to 76.6 °C compared to that of the pure PCL, and the initial thermal decomposition temperature reached 86.7 °C. The crystallinity and porosity went up to 29.97% and 85.61%, respectively, while the tensile strength and elongation at the breakage were 20.036 MPa and 198.72%, respectively. Therefore, the 10:90 (w/w) blend ratio of CS/PCL is recommended to prepare CS–PCL membranes for tissue engineering applications.     

Influence of Strain Route Changes on the Microstructure and Mechanical Properties of CuZn36 Alloy during Cross Channel Extrusion CCE

This study evaluates the impact of changing the deformation routes of the extrusion process in a cross-shaped die (CCE) on the structure and properties of a CuZn36 alloy (% at.). Samples with dimensions of Ø8 × 36 mm were subjected to extrusion at room temperature according to two variants: straight extrusion in the A route (2-, 4-, 8- and 12-pass) and extrusion with interoperative rotation by 90° in the B_C route (2- and 4-pass). The improvement of strength properties was obtained as a result of grain fragmentation in the CCE process. Changes in the microstructure were observed using a light microscope, and mechanical properties were measured in the microhardness test and a static tensile test. The obtained results showed that the mechanical properties of the alloy depend on the number of passes and the material deformation route. This observation was related to the fragmentation of its structure and strengthening, which resulted in changes in its properties. The highest strength was characterized by the material pressed four times with the rotation of 90° (B_C route), whose properties were comparable and even slightly better than the material squeezed twelve times without rotation (A route).     

The Influence of Alkoxy Substitutions on the Properties of Diketopyrrolopyrrole-Phenyl Copolymers for Solar Cells

A previously reported diketopyrrolopyrrole (DPP)-phenyl copolymer is modified by adding methoxy or octyloxy side chains on the phenyl spacer. The influence of these alkoxy substitutions on the physical, opto-electronic properties, and photovoltaic performance were investigated. It was found that the altered physical properties correlated with an increase in chain flexibility. Well-defined oligomers were synthesized to verify the observed structure-property relationship. Surprisingly, methoxy substitution on the benzene spacer resulted in higher melting and crystallization temperatures in the synthesized oligomers. This trend is not observed in the polymers, where the improved interactions are most likely counteracted by the larger conformational possibilities in the polymer chain upon alkoxy substitution. The best photovoltaic performance was obtained for the parent polymer: fullerene blends whereas the modifications on the other two polymers result in reduced open-circuit voltage and varying current densities under similar processing conditions. The current densities could be related to different polymer: fullerene blend morphologies. These results show that supposed small structural alterations such as methoxy substitution already significantly altered the physical properties of the parent polymer and also that oligomers and polymers respond divergent to structural alterations made on a parent structure.