Variations in the Thermomechanical and Structural Properties during the Cooling of Shape-Memory R-PETG.

One of the useful features of 3D-printed specimens of recycled polyethylene terephthalate glycol (R-PETG) is the ability to repetitively develop free recovery as well as the work-generating, shape-memory effect. This behavior is enabled by the R-PETG's capacity to stiffen during cooling, thus allowing for a new temporary shape to be induced. Aiming to devise an explanation for the polymer's stiffening, in this study, the variation in some of the R-PETG's parameters during cooling are emphasized and discussed. The evolution of an R-PETG filament's shape was monitored during room-temperature-bending heating-cooling cycles. Straight-shape recovery and the complete loss of stiffness were observed at the start and the end of heating, respectively, followed by the forced straightening of the filament, performed by the operator, around 40 °C, during cooling. The tests performed by dynamic mechanical analysis disclosed the rise of the storage modulus (E') after 100 °C heating followed by either liquid-nitrogen- or air-cooling to room temperature, in such a way that E' was always larger after cooling than initially. Static tests emphasized a peculiar stress variation during a heating-cooling cycle applied in air, within the heating chamber of the tensile testing machine. Tensile-failure tests were performed at -10 °C at a rate of 100 mm/min, with specimens printed at various deposition directions between 10 and 40° to the transversal direction. The specimens printed at 40°, which had the largest ultimate strains, were broken with tensile rates between 100 and 500 mm/min. Deformation rate increase favored the shift from crazing to delamination failure modes. The correlation between the structural changes, the sharp E' increase on heating, and the stiffening induced by cooling represents a novel approach that enables the use of 3D-printed R-PETG for the fabrication of the active parts of low-priced lightweight resettable actuators.

Analysis of Degradation Products of Biodegradable ZnMgY Alloy.

Biodegradable metallic materials are increasingly gaining ground in medical applications. Zn-based alloys show a degradation rate between those recorded for Mg-based materials with the fastest degradation rate and Fe-based materials with the slowest degradation rate. From the perspective of medical complications, it is essential to understand the size and nature of the degradation products developed from biodegradable materials, as well as the stage at which these residues are eliminated from the body. This paper presents investigations conducted on the corrosion/degradation products of an experimental material (ZnMgY alloy in cast and homogenized state) after immersion tests in three physiological solutions (Dulbecco's, Ringer's and simulated body fluid (SBF)). Scanning electron microscopy (SEM) was used to highlight the macroscopic and microscopic aspects of corrosion products and their effects on the surface. An X-ray energy dispersive detector (EDS), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) provided general information about the compounds based on their non-metallic character. The pH of the electrolyte solution was recorded for 72 h during immersion. The pH variation of the solution confirmed the main reactions proposed for the corrosion of ZnMg. The agglomerations of corrosion products were on the micrometer scale, mainly oxides, hydroxides and carbonates or phosphates. The corrosion effects on the surface were homogeneously spread, with a tendency to connect and form cracks or larger corrosion zones, transforming the pitting corrosion pattern into a generalized one. It was noticed that the alloy's microstructure strongly influences the corrosion characteristics.

On the Thermomechanical Behavior of 3D-Printed Specimens of Shape Memory R-PETG.

From commercial pellets of recycled polyethylene terephthalate glycol (R-PETG), 1.75 mm diameter filaments for 3D printing were produced. By varying the filament's deposition direction between 10° and 40° to the transversal axis, parallelepiped specimens were fabricated by additive manufacturing. When bent at room temperature (RT), both the filaments and the 3D-printed specimens recovered their shape during heating, either without any constraint or while lifting a load over a certain distance. In this way, free-recovery and work-generating shape memory effects (SMEs) were developed. The former could be repeated without any visible fatigue marks for as much as 20 heating (to 90 °C)-RT cooling-bending cycles, while the latter enabled the lifting of loads over 50 times heavier than the active specimens. Tensile static failure tests revealed the superiority of the specimens printed at larger angles over those printed at 10°, since the specimens printed at 40° had tensile failure stresses and strains over 35 MPa and 8.5%, respectively. Scanning electron microscopy (SEM) fractographs displayed the structure of the successively deposited layers and a shredding tendency enhanced by the increase in the deposition angle. Differential scanning calorimetry (DSC) analysis enabled the identification of the glass transition between 67.5 and 77.3 °C, which might explain the occurrence of SMEs in both the filament and 3D-printed specimens. Dynamic mechanical analysis (DMA) emphasized a local increase in storage modulus of 0.87-1.66 GPa that occurred during heating, which might explain the development of work-generating SME in both filament and 3D-printed specimens. These properties recommend 3D-printed parts made of R-PETG as active elements in low-price lightweight actuators operating between RT and 63 °C.

Heat Treatment and Dynamic Mechanical Analysis Strain Sweep Effects on the Phase Structure and Morphology of an Fe-28Mn-6Si-5Cr Shape Memory Alloy.

Fe-Mn-Si-based shape memory alloys (SMAs) have been extensively investigated since 1982 for various useful properties that enhance the development of different applications such as anti-seismic dampers for very tall buildings, pipe joints, or rail fasteners. In particular, the Fe-28Mn-6Si-5Cr (mass. %) alloy has been mainly used in vibration mitigation or self-adjustable axial displacement applications. Dynamic mechanical analysis (DMA), performed by strain sweeps (SS), enables the monitoring of the evolution of storage modulus and internal friction variations with increasing strain amplitudes at different constant frequencies and temperatures. Thus, applying dynamic bending with various frequencies and amplitudes that actually represents an isothermal mechanical treatment. In the present paper, an Fe-28Mn-6 Si-5Cr (mass. %) SMA was cast by ingot metallurgy, hot-rolled, and water quenched in order to obtain thermally induced martensite and avoid the occurrence of cooling cracks. The influence of the holding time, between 2 and 10 h, at 1050 °C and the effects of DMA-SS performed at three different frequencies were analyzed by a differential scanning calorimetry, an X-ray diffraction, and a scanning electron and atomic force microscopy. The effects of the holding time and mechanical treatment on the structure and morphology of martensite plates were corroborated with the results of the thermal analysis.

Influence of Dynamic Strain Sweep on the Degradation Behavior of FeMnSi-Ag Shape Memory Alloys.

Iron-based SMAs can be used in the medical field for both their shape memory effect (SME) and biodegradability after a specific period, solving complicated chirurgical problems that are partially now addressed with shape-memory polymers or biodegradable polymers. Iron-based materials with (28-32 wt %) Mn and (4-6 wt %) Si with the addition of 1 and 2 wt % Ag were obtained using levitation induction melting equipment. Addition of silver to the FeMnSi alloy was proposed in order to enhance its antiseptic property. Structural and chemical composition analyses of the newly obtained alloys were performed by X-ray diffraction (confirming the presence of ε phase), scanning electron microscopy (SEM) and energy-dispersive spectroscopy. The corrosion resistance was evaluated through immersion tests and electrolyte pH solution variation. Dynamic mechanical solicitations were performed with amplitude sweep performed on the FeMnSi-1Ag and FeMnSi-2Ag samples, including five deformation cycles at 40 °C, with a frequency of 1 Hz, 5 Hz and 20 Hz. These experiments were meant to simulate the usual behavior of some metallic implants subjected to repetitive mechanical loading. Atomic force microscopy was used to analyze the surface roughness before and after the dynamic mechanical analysis test followed by the characterization of the surface profile change by varying dynamic mechanical stress. Differential scanning calorimetry was performed in order to analyze the thermal behavior of the material in the range of -50-+200 °C. X-ray diffraction and Fourier transform infrared spectroscopy (FTIR) along with Neaspec nano-FTIR experiments were performed to identify and confirm the corrosion compounds (oxides, hydroxides or carbonates) formed on the surface.

DMA Investigation of the Factors Influencing the Glass Transition in 3D Printed Specimens of Shape Memory Recycled PET.

Polyethylene terephthalate (PET) is used worldwide for packing, and for this reason, it is the main material in plastic waste. The paper uses granules of recycled PET (R-PET) as raw material for producing filaments for 3D printing, subsequently used for printing the test specimens in different ways: longitudinally and at angles between 10° and 40° in this direction. Both the filaments and the printed specimens experience thermally driven shape memory effect (SME) since they have been able to recover their straight shape during heating, after being bent to a certain angle, at room temperature (RT). SME could be reproduced three times, in the case of printed specimens, and was investigated by cinematographic analysis. Then, differential scanning calorimetry (DSC) was used, in R-PET granules, filaments and 3D printed specimens, to emphasize the existence of glass transition, which represents the governing mechanism of SME occurrence in thermoplastic polymers, as well as a recrystallization reaction. Subsequently, the paper investigated the 3D printed specimens by dynamic mechanical analysis (DMA) using a dual cantilever specimen holder. Temperature (DMA-TS) and isothermal scans (DMA-Izo) were performed, with the aim to discuss the variations of storage modulus and loss modulus with temperature and time, respectively.

Structural-Functional Changes in a Ti50Ni45Cu5 Alloy Caused by Training Procedures Based on Free-Recovery and Work-Generating Shape Memory Effect.

Active elements made of Ti50Ni45Cu5 shape memory alloy (SMA) were martensitic at room temperature (RT) after hot rolling with instant water quenching. These pristine specimens were subjected to two thermomechanical training procedures consisting of (i) free recovery shape memory effect (FR-SME) and (ii) work generating shape memory effect (WG-SME) under constant stress as well as dynamic bending and RT static tensile testing (TENS). The structural-functional changes, caused by the two training procedures as well as TENS were investigated by various experimental techniques, including differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray diffraction (XRD), and atomic force microscopy (AFM). Fragments cut from the active regions of trained specimens or from the elongated gauges of TENS specimens were analyzed by DSC, XRD, and AFM. The DSC thermograms revealed the shift in critical transformation temperatures and a diminution in specific absorbed enthalpy as an effect of training cycles. The DMA thermograms of pristine specimens emphasized a change of storage modulus variation during heating after the application of isothermal dynamical bending at RT. The XRD patterns and AMF micrographs disclosed the different evolution of martensite plate variants as an effect of FR-SME cycling and of being elongated upon convex surfaces or compressed upon concave surfaces of bent specimens. For illustrative reasons, the evolution of unit cell parameters of B19' martensite, as a function of the number of cycles of FR-SME training, upon concave regions was discussed. AFM micrographs emphasized wider and shallower martensite plates on the convex region as compared to the concave one. With increasing the number of FR-SME training cycles, plates' heights decreased by 84-87%. The results suggest that FR-SME training caused marked decreases in martensite plate dimensions, which engendered a decrease in specific absorbed enthalpy during martensite reversion.

In-Vitro Analysis of FeMn-Si Smart Biodegradable Alloy.

Special materials are required in many applications to fulfill specific medical or industrial necessities. Biodegradable metallic materials present many attractive properties, especially mechanical ones correlated with good biocompatibility with vivant bodies. A biodegradable iron-based material was realized through electric arc-melting and induction furnace homogenization. The new chemical composition obtained presented a special property named SME (shape memory effect) based on the martensite transformation. Preliminary results about this special biodegradable material with a new chemical composition were realized for the chemical composition and structural and thermal characterization. Corrosion resistance was evaluated in Ringer's solution through immersion tests for 1, 3, and 7 days, the solution pH was measured in time for 3 days with values for each minute, and electro-corrosion was measured using a potentiostat and a three electrode cell. The mass loss of the samples during immersion and electro-corrosion was evaluated and the surface condition was studied by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). SME was highlighted with differential scanning calorimetry (DSC). The results confirm the possibility of a memory effect of the materials in the wrought case and a generalized corrosion (Tafel and cyclic potentiometry and EIS) with the formation of iron oxides and a corrosion rate favorable for applications that require a longer implantation period.

Nanocomposite Biopolymer Arboblend V2 Nature AgNPs.

Due to the pressing problems of today's world, regarding both the finding of new, environmentally friendly materials which have the potential to replace classic ones, and the need to limit the accelerated spread of bacteria in hospitals, offices and other types of spaces, many researchers have chosen to develop their work in this field. Thus, biopolymeric materials have evolved so much that they are gradually becoming able to remove fossil-based plastics from major industries, which are harmful to the environment and implicitly to human health. The biopolymer employed in the present study, Arboblend V2 Nature with silver nanoparticle content (AgNP) meets both aspects mentioned above. The main purpose of the paper is to replace several parts and products in operation which exhibit antibacterial action, preventing the colonization and proliferation of bacteria (Streptococcus pyogenes and Staphylococcus aureus, by using the submerged cultivation method), but also the possibility of degradation in different environments. The biopolymer characterization followed the thermal behavior of the samples, their structure and morphology through specific analyses, such as TGA (thermogravimetric analysis), DSC (differential scanning calorimetry), SEM (scanning electron microscopy) and XRD (X-ray diffraction). The obtained results offer the possibility of use of said biocomposite material in the medical field because of its antibacterial characteristics that have proved to be positive, and, therefore, suitable for such applications. The thermal degradation and the structure of the material highlighted the possibility of employing it in good conditions at temperatures up to 200 °C. Two types of samples were used for thermal analysis: first, in the form of granules coated with silver nanoparticles, and second, test specimen cut from the sample obtained by injection molding from the coated granules with silver nanoparticles.

Tribological and Dynamical Mechanical Behavior of Prototyped PLA-Based Polymers.

It is essential to combine current state-of-the-art technologies such as additive manufacturing with current ecological needs. Due to the increasing demand for non-toxic biodegradable materials and products, human society has been searching for new materials. Consequently, it is compulsory to identify the qualities of these materials and their behavior when subjected to various external factors, to find their optimal solutions for application in various fields. This paper refers to the biodegradable Polylactic acid (PLA)-based filament (commercially known as Extrudr BDP (Biodegradable Plastic) Flax) compared with the biodegradable composite material PLA-lignin filament whose constituent's trade name is Arboblend V2 Nature as a lignin base material and reinforcement with Extrudr BDP Pearl, a PLA based polymer, 3D printed by Fused Deposition Modeling technology. Certain mechanical properties (tensile strength, bending strength and DMA-Dynamic Mechanical Analysis) were also determined. The tribology behavior (friction coefficient and wear), the structure and the chemical composition of the biodegradable materials were investigated by SEM-Scanning Electron Microscopy, EDX-Energy Dispersive X-Ray Analysis, XRD-X-Ray Diffraction Analysis, FTIR-Fourier Transform Infrared Spectrometer and TGA-Thermogravimetric Analysis. The paper also refers to the influence of technological parameters on the 3D printed filaments made of Extrudr BDP Flax and the optimization those of technological parameters. The thermal behavior during the heating of the sample was analyzed by Differential scanning calorimetry (DSC). As a result of the carried-out research, we intend to recommend these biodegradable materials as possible substituents for plastics in as many fields of activity as possible.