Development of thermoplastic starch (TPS) including leather waste fragments

A thermoplastic starch (TPS) material is developed, based on corn starch plasticized with glycerol and citric acid in a 9:3:1 ratio and further bonded with isinglass and mono-and diglycerides of fatty acids (E471). In TPS, leather fragments, in the amount of 7.5 15 or 22.5 g/100 g of dry matter, were also introduced. The mixture was heated at a maximum temperature of 80 °C, then cast in an open mold to obtain films with thickness in the range 300 ± 50 microns. The leather fragments used were based on collagen obtained from production waste from shoemaking and tanned with tannins obtained from smoketree (Rhus cotinus), therefore free from chromium. Thermogravimetric (TGA) tests suggested that material degradation started at a temperature around 285 °C, revealing that the presence of leather fragments did not influence the occurrence of this process in TPS. Tensile tests indicated an increase in tensile properties (strength and Young's modulus) with increasing leather content, albeit coupled, especially at 22.5 wt%, with a more pronounced brittle behavior. Leather waste provided a sound interface with the bulk of the composite, as observed under scanning electron microscopy. The production process indicated a very limited degradation of the material after exposure to UV radiation for eight days, as demonstrated by the slight attenuation of amide I (collagen) and polysaccharide FTIR peaks. Reheating at 80 °C resulted in a weight loss not exceeding 3%

Hybrid metal/polymer filaments for fused filament fabrication (FFF) to print metal parts

The exploitation of mechanical properties and customization possibilities of 3D printed metal parts usually come at the cost of complex and expensive equipment. To address this issue, hybrid metal/polymer composite filaments have been studied allowing the printing of metal parts by using the standard Fused Filament Fabrication (FFF) approach. The resulting hybrid metal/polymer part, the so called “green”, can then be transformed into a dense metal part using debinding and sintering cycles. In this work, we investigated the manufacturing and characterization of green and sintered parts obtained by FFF of two commercial hybrid metal/polymer filaments, i.e., the Ultrafuse 316L by BASF and the 17-4 PH by Markforged. The Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS) analyses of the mesostructure highlighted incomplete raster bonding and voids like those observed in conventional FFF-printed polymeric structures despite the sintering cycle. A significant role in the tensile properties was played by the building orientation, with samples printed flatwise featuring the highest mechanical properties, though lower than those achievable with standard metal additive manufacturing techniques

3D Printing of Low-Filled Basalt PA12 and PP Filaments for Automotive Components

Fused Deposition Modeling (FDM) enables many advantages compared to traditional manufacturing techniques, but the lower mechanical performance due to the higher porosity still hinders its industrial spread in key sectors like the automotive industry. PP and PA12 filaments filled with low amounts of basalt fibers were produced in the present work to improve the poor mechanical properties inherited from the additive manufacturing technique. For both matrices, the introduction of 5 wt.% of basalt fibers allows us to achieve stiffness values comparable to injection molding ones without modifying the final weight of the manufactured components. The increased filament density compared with the neat polymers, upon the introduction of basalt fibers, is counterbalanced by the intrinsic porosity of the manufacturing technique. In particular, the final components are characterized by a 0.88 g/cm3 density for PP and 1.01 g/cm3 for PA12 basalt-filled composites, which are comparable to the 0.91 g/cm3 and 1.01 g/cm3, respectively, of the related neat matrix used in injection molding. Some efforts are still needed to fill the gap of 15–28% for PP and of 26.5% for PA12 in tensile strength compared to injection-molded counterparts, but the improvement of the fiber/matrix interface by fiber surface modification or coupling agent employment could be a feasible solution

Hybrid cellulose–Basalt polypropylene composites with enhanced compatibility. The role of coupling agent

This study deals with the development and optimization of hybrid composites integrating microcrystalline cellulose and short basalt fibers in a polypropylene (PP) matrix to maximize the mechanical properties of resulting composites. To this aim, the effects of two different coupling agents, endowed with maleic anhydride (MA-g(grafted)-PP) and acrylic acid (AA-g-PP) functionalities, on the composite properties were investigated as a function of their amount. Tensile, flexural, impact and heat deflection temperature tests highlighted the lower reactivity and effectiveness of AA-g-PP, regardless of reinforcement type. Hybrid formulations with basalt/cellulose (15/15) and with 5 wt. % of MA-g-PP displayed remarkable increases in tensile strength and modulus, flexural strength and modulus, and notched Charpy impact strength, of 45% and 284%, 97% and 263%, and 13%, in comparison with neat PP, respectively. At the same time, the thermo-mechanical stability was enhanced by 65% compared to neat PP. The results of this study, if compared with the ones available in the literature, reveal the ability of such a combination of reinforcements to provide materials suitable for automotive applications with environmental benefits

Polylactic acid as biobased binder for the production of 3D printing filaments for Ti6Al4V alloy manufacturing via bound metal deposition

In this paper, a biobased binder mainly composed of polylactic acid (PLA) was developed for the production of Ti6Al4V feedstock suitable for 3D printing via material extrusion. 3D printed samples were debound via solvent and thermal treatments and successfully sintered in reducing atmosphere obtaining dense metallic components. The designed and produced bio-binder is completely eliminated during the debinding processes leading to sintered samples showing a high densification (93–94%), with a microstructure composed of primary alpha phase with segregated beta phase at grain boundaries and having average grain size of 70 μm. 3D printed sintered samples show good mechanical properties (yield strength (σy) = 662 MPa, ultimate tensilte strength (UTS) = 743 MPa, elongation at break (εmax) = 12%, hardness = 5.15 GPa) influenced by the sintering parameters and the presence of some degree of micro-porosity in the final structure

Assessment of agglomerated corks and PVC foams cores crashworthiness under multiple-impact events in different loading conditions

Thanks to the unique flexural properties, sandwich composites are considered as irreplaceable structures in many industrial fields, but their susceptibility to impact events is still a considerable drawback that undermines their structural integrity determining a reduction of their load-bearing capabilities. Considering that the core material plays the major role to distance the skins, the knowledge of its multiple-impacts response becomes a key design parameter in order to ensure a long-term stability to the structure. In view of this, the present work addresses the multiple-impacts behavior in dynamic compression and puncture impact conditions of bio-based agglomerated cork cores taking into account the effect of density and providing a meaningful comparison with more traditional petroleum-based foams. Despite the inherently higher mechanical properties of the PVC (polyvinyl chloride) foams, agglomerated cork demonstrated to provide a higher dimensional stability to the structure after repeated impacts thanks to its unique microstructure. With a reduction lower than 25% of its initial height after 10 impacts, agglomerated cork NL25 proved to be an exceptional alternative to the common HP130 foam, which undergoes a halving of its initial height after only 3 impacts, to obtain a more eco-friendly and performing sandwich composite

Experimental characterization and numerical modelling of the impact behavior of PVC foams

Background Polyvinyl chloride (PVC) foams are widely used in crashworthiness and energy absorption applications due to their low density and the capability of crushing up to large deformations with limited loads. This property is due to their particular constitutive behavior: the stress-strain curve is characterized, after an initial yield or peak stress, by a relevant plateau region followed by a steep increase due to foam densification. Furthermore, the mechanical response of PVC foam is strongly strain rate dependent. Objective This work aims to characterize the mechanical behavior of PVC foams and to develop a complete constitutive model for impact and energy absorption applications. Methods Compressive tests are carried out at different speeds on PVC foam samples having different relative densities. Quasi-static and intermediate strain rate tests are performed by a pneumatic machine, while high strain rate tests are conducted by means of a Split Hopkinson Pressure Bar. The uniaxial stress-strain curves are used to calibrate the visco-elastic and visco-plastic constitutive model. In particular, the material behavior is divided into two parallel branches: the former describes the elasto-plastic behavior, while the latter accounts for the visco-elastic one; the plastic branch also includes a multiplicative term accounting for the strain rate sensitivity of the base material. Results The tests highlight a strong compressibility of the foam with negligible lateral expansion. The energy absorption efficiency, as well as the densification strain, is evaluated. The material model is also implemented in Finite Element (FE) simulations of puncture impact tests, validating the results of the calibration procedure. Conclusions The calibration of the visco-elasto-plastic material model offers a physically consistent identification of the constitutive response of the PVC foams, showing an effective characterization of the impact behavior of the material

Surface modification of basalt fibres with ZnO nanorods and its effect on thermal and mechanical properties of pla-based composites

The composites based on basalt fibres and poly(lactic acid) (PLA) show promising applications in biomedical and automotive fields, but their mechanical performance is still largely hindered by poor interfacial properties. Zinc oxide nanorods have been successfully used to tune the PLA/basalt fibre interface by growing them on commercially available basalt fabrics. The hierarchical fibres significantly enhanced the mechanical properties of PLA-based composites, especially their flexural strength and stiffness. These values are 26% and 22% higher than those of unmodified basalt/PLA composites, and 24% and 34% higher than those of glass/PLA composites used as a baseline. The increase in tensile and flexural properties hinges on the mechanical interlocking action promoted by ZnO nanorods and on the creation of a compact transcrystallinity structure. A degradation of PLA matrix was detected but it was positively counteracted by the better interfacial stress transfer. This study offers a novel approach for modifying the fibre–matrix interface of biocomposites intended for high-performance applications

Chemical regeneration of thermally conditioned basalt fibres

The disposal of fibre reinforced composite materials is a problem widely debated in the literature. This work explores the ability to restore the mechanical properties of thermally conditioned basalt fibres through chemical treatments. Inorganic acid (HF) and alkaline (NaOH) treatments proved to be effective in regenerating the mechanical strength of recycled basalt fibres, with up to 94% recovery of the strength on treatment with NaOH. In particular, HF treatment proved to be less effective compared to NaOH, therefore pointing towards a more environmentally sustainable approach considering the disposal issues linked to the use of HF. Moreover, the strength regeneration was found to be dependent on the level of temperature experienced during the thermal treatment process, with decreasing effectiveness as a function of increasing temperature. SEM analysis of the fibres' lateral surfaces suggests that surface defects removal induced by the etching reaction is the mechanism controlling recovery of fibre mechanical properties. In addition, studies on the fracture toughness of the regenerated single fibres were carried out, using focussed ion beam (FIB) milling technique, to investigate whether any structural change in the bulk fibre occurred after thermal exposure and chemical regeneration. A significant increase in the fracture toughness for the regenerated fibres, in comparison with the as-received and heat-treated basalt ones, was measured

Surface modification of flax yarns by enzymatic treatment and their interfacial adhesion with thermoset matrices

The aim of this study was to assess the effects of commercially available and relatively inexpensive enzyme preparations based on endo 1,4-β-xylanase, pectinase and xyloglucanase on the thermal (TGA), morphological (SEM), chemical (FT-IR) and mechanical (single yarn tensile tests) properties of flax yarns. The preparation based on pectinase and xyloglucanase provided the best results, resulting in the effective removal of hydrophilic components such as hemicellulose and pectin, the individualization of yarns and increased thermal stability at the expense of a reduction in mechanical properties, depending on the treatment parameters. Single yarn fragmentation tests pointed out an improved interfacial adhesion after enzymatic treatment, with reduced debonding length values of 18% for an epoxy matrix and up to 36% for a vinylester resin compared to untreated flax yarns