Differential Scanning Calorimetry Tests Research Articles

An improved linear systems model of hydrothermal isometric tension testing to aid in assessing bone collagen quality: Effects of ribation and type-2 diabetes.

This study sought to further develop and validate a previously proposed physics-based model that maps denaturation kinetics from differential scanning calorimetry (DSC) to the isometric tension generated during hydrothermal isometric tension (HIT) testing of collagenous tissues. The primary objectives of this study were to verify and validate two physics-based model parameters: α, which indicates the amount of instantaneous isometric tension developed per unit of collagen denaturation, and β, which captures the proportionality between temperature and the generated isometric tension post denaturation initiation. These parameters were used as measures of bone collagen quality, employing data from HIT and DSC testing of human bone collagen from two previous studies. Additionally, given the physical basis of the model, the study aimed to further validate Max.Slope, the rate of change in isometric tensile stress with change in temperature, as an independent measure of collagen network connectivity. Max.Slope has previously been positively correlated with measures of cortical bone fracture resistance. Towards this verification and validation, the hypotheses were a) that α would correlate strongly with HIT denaturation temperature, Td, and the enthalpy of melting (ΔH) from DSC, and b) that β would correlate positively and strongly with Max.Slope.The model was employed in the analysis of HIT-DSC data from the testing of demineralized bone collagen isolated from cadaveric human femurs in two prior studies. In one study, data were collected from HIT-DSC testing of cortical bone collagen from 74 donors. Among them, 38 had a history of type 2 diabetes +/− chronic kidney disease, while the remaining 36 had no history of T2D again with or without CKD. Cortical bone specimens were extracted from the lateral mid-shaft. The second study involved 15 donor femora, with four cortical bone specimens extracted from each. Of these four, two specimens underwent a 4-week incubation in 0.1 M ribose at 37 °C to induce non-enzymatic ribation and advanced glycation endproducts, while the other two served as non-ribated controls.The examination involved investigating correlations between the model parameters α and β and various measures, such as Max.Slope, Td, ΔH, age, and duration of type 2 diabetes. The results revealed positive correlations between the model parameter β and Max.Slope (r = 0.55–0.58). The parameter α was found to be associated with Td, but also sensitive to the shape of the HIT curve around Td resulting in difficulties with variability and interpretation. As a result, while both hypotheses are confirmed, Max.Slope and β are better indicators of bone collagen quality because they are measures of the connectivity or, more generally, the integrity of the bone collagen network.

A coherent engineering assessment of ABS/biochar biocomposites in MEX 3D additive manufacturing

Acrylonitrile butadiene styrene (ABS) composites were prepared in filament form compatible with the material extrusion (MEX) 3D printing method, using biochar as a filler at various loadings of up to 10.0 wt %. Samples were fabricated to experimentally investigate their mechanical performance. The ABS/biochar composites were characterized using thermogravimetric analysis, differential scanning calorimetry, Raman spectroscopy, and rheological tests. The electrical properties of the composites were investigated using broadband dielectric spectroscopy. Scanning electron microscopy was utilized to analyze the morphological features of the fabricated specimens by examining their side and fracture surfaces. The results indicate that the composite with 4.0 wt % biochar content compared to pure ABS showed the highest mechanical response between the prepared composites (24.9 % and 21 % higher than the pure ABS tensile and flexural strength respectively). The composites retained their insulating behavior. These findings contribute to expanding the utilization of the material extrusion (MEX) 3D printing method while also unlocking prospects for potential applications in microelectronics, apart from mechanical reinforcement.

3D printing of shape memory Alloys for complex architectures of smart structures

Shape Memory Alloys (SMA) are materials used to design smart structures with intrinsic functional properties and improved efficiency. This is a key aspect of aerospace industry and makes SMA good candidates in this field. One of the most widespread SMA is the equiatomic NiTi alloy which, however, has the strong limitation of poor machinability, so only simple shapes can be obtained. Additive Manufacturing processes allow to overcome this limit and to design complex shapes. Compared to other metallic materials, the optimization of the process for NiTi alloy is complicated because, beside mechanical properties and presence of defects, considerable attention needs to be dedicated to the material functionality. The high temperatures involved in the additive process significantly affect the material properties due to possible evaporation of Ni and formation of precipitates that enable a shift of the phase transformation temperatures. This paper is focused on the optimization of the process parameters of the NiTi alloy printed through the Laser Powder Bed Fusion (L-PBF) to ensure optimal pseudo-elastic behaviour, which is essential for the design of structural dampers. This was accomplished starting from simple structures and then designing a damper that couples the pseudoelasticity of NiTi with load support capacity.The L-PBF is a powder-bed technique that selectively melts layers of micrometric metal powder. A pseudoelastic NiTi powder with 50.8 at. % of Ni content was selected and characterized through scanning electron microscope (SEM) and observations connected to an Energy Dispersive X-ray Spectroscopy (EDX) probe. After that, some cubic samples were manufactured, with the dimension of 3 × 3 × 15 mm3. A set of different laser powers and scanning speeds were used to find the set of process parameters that optimize the functional properties of the printed parts. Near fully dense specimens with density higher than 99.5 % were selected for further investigations. Differential scanning calorimetry (DSC) and mechanical tests were performed on as-built and heat-treated samples.Quasi-static mechanical tests were accomplished in compression mode, at different strains, up to 8 %. It was observed that the residual strain for cyclic loading at 4 % is lower than 1 %, so good recovery of the deformation was shown. Moreover, numerical analyses that mimic the pseudoelastic behaviour in compression tests were implemented.Finally, the best set of parameters was selected on the basis of the material's ability to recover deformations and its loss factor.

Non‐isocyanate polyurethane‐acrylate as UV‐ and thermo‐responsive plasticizer for thermoplastic elastomer

AbstractA UV‐ and thermo‐responsive polyurethane‐acrylate prepolymer was synthesized from palm olein (POo) via a non‐isocyanate route. The process included epoxidation of POo, carbonation of epoxidized palm olein (EPOo) into polycyclic carbonate in a solvent‐free and mild condition (100°C, 1 atm), followed by reacting with ethylene diamine and acrylic acid. The chemical structure of the non‐isocyanate polyurethane‐acrylate (NIPUA) prepolymer was elucidated by 1H and 13C nuclear magnetic resonance (NMR) and Fourier transform‐infrared spectroscopy (FTIR), while weight average molecular weight of NIPUA was determined by gel permeation chromatography (GPC). The NIPUA (0–20 wt%) was incorporated with thermoplastic elastomer (TPE) as a plasticizer and cured under UV light and thermal stimulations. The cured NIPUA/TPE films were characterized by FTIR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile strength test. Under UV and thermal stimulations, the NIPUA/TPE demonstrated enhanced tensile properties (elongation at break >1280%, Young's modulus ~25 MPa), thermal properties (lower Tg), lower water contact angle, and shortened curing time as compared with the blank TPE. The 20 wt% NIPUA/TPE films exhibited susceptibility to enzymatic biodegradation and noncytotoxic to HEK 293 cells in vitro, demonstrated it's potential as a UV‐ and thermo‐responsive plasticizer for TPE in manufacturing of medical devices.

Expanding the Frontiers of nail product evaluation: Novel application of differential scanning calorimetry (DSC) for assessing crosslinking density and predicting nail brittleness and flexibility.

While modern industry advancements have expanded nail beautification options, scientific literature primarily focuses on nail biology and medicine, with limited attention on cosmetic treatments. This study aimed to investigate human nail denaturation properties, including gender impact, blending nails to enlarge the sample pool, nail sensitization through bleaching, and active effectiveness testing. The objective was to understand the DSC and bending fatigue relationship, and define the consumer relevance of the DSC test. Nail clippings were collected from adult female and male volunteers. The wet DSC was employed to validate sample preparation, explore the effects of gender, and assess the potential of using blended nails for claims substantiation testing. Nails were sensitized through bleaching using hydrogen peroxide. The effects were confirmed through DSC and nail flexure tests. Furthermore, the ability of actives to address concerns related to nail softness and brittleness was assessed using these techniques. The results confirmed the viability of equilibrating nails in water for up to 14 h as a standardized testing method. The denaturation temperature results were independent of gender and suitable for claims substantiation testing. Blending nails from different sources did not yield significant variations in denaturation properties. A preliminary study suggested that cadaver nails should be used with caution because they exhibited differences in denaturation temperature, influenced by the sampling location. Bending fatigue tests highlighted the significance of humidity, with higher humidity conditions (80%) enhancing nail flexibility and providing better resolution for claims substantiation. Sensitizing the nails with hydrogen peroxide induced alterations in both DSC and bending fatigue results. Proof-of-principle studies demonstrated an elevation in denaturation temperature and a decrease in the number of cycles to break, indicating a nail-hardening effect when formaldehyde was applied. The use of a nail softener led to an enhancement in nail fatigue resistance due to a notable reduction in nail crosslinking density. The measurement of crosslinking density proved to be a sensitive tool for assessing the effects of cosmetic treatments on nails, particularly in predicting outcomes related to nail brittleness and flexibility.

Influence of Carboxymethyl Cellulose as a Thickening Agent for Glauber's Salt-Based Low Temperature PCM.

This work is focused on a novel, promising low temperature phase change material (PCM), based on the eutectic Glauber's salt composition. To allow phase transition within the refrigeration range of temperatures of +5 °C to +12 °C, combined with a high repeatability of melting-freezing processes, and minimized subcooling, the application of three variants of sodium carboxymethyl cellulose (Na-CMC) with distinct molecular weights (700,000, 250,000, and 90,000) is considered. The primary objective is to optimize the stabilization of this eutectic PCM formulation, while maintaining the desired enthalpy level. Preparation methods are refined to ensure repeatability in mixing components, thereby optimizing performance and stability. Additionally, the influence of Na-CMC molecular weight on stabilization is examined through differential scanning calorimetry (DSC), T-history, and rheology tests. The PCM formulation of interest builds upon prior research in which borax, ammonium chloride, and potassium chloride were used as additives to sodium sulfate decahydrate (Glauber's salt), prioritizing environmentally responsible materials. The results reveal that CMC with molecular weights of 250 kg/mol and 90 kg/mol effectively stabilize the PCM without phase separation issues, slowing crystallization kinetics. Conversely, CMC of 700 kg/mol proved ineffective due to the disruption of gel formation at its low gel point, hindering higher concentrations. Calculations of ionic concentration indicate higher Na ion content in PCM stabilized with 90 kg/mol CMC, suggesting increased ionic interactions and gel strength. A tradeoff is discovered between the faster crystallization in lower molecular weight CMC and the higher concentration required, which increases the amount of inert material that does not participate in the phase transition. After thermal cycling, the best formulation had a latent heat of 130 J/g with no supercooling, demonstrating excellent performance. This work advances PCM's reliability as a thermal energy storage solution for diverse applications and highlights the complex relationship between Na-CMC molecular weight and PCM stabilization.

Low temperature effect on cyclic behavior of shape memory alloy U-shaped dampers

Although Nickel-Titanium (NiTi) shape memory alloys (SMAs) have been widely studied as seismic response mitigation devices in civil structures, their temperature sensitivity due to the coupled thermo-mechanical behavior prevents their practical implementation in cold temperature environments. This paper investigated the effects of varying ambient temperatures (particularly low ambient temperature) on the hysteretic behavior and self-centering (SC) ability of shape memory alloy U-shaped dampers (SMAUDs) that were made of NiTi showing superelasticity (SE) at room temperature. Thermo-mechanical properties of SMAUDs were identified through differential scanning calorimetry (DSC) tests. Cyclic loading experiments on SMAUDs were conducted at a wide ambient temperature range from −40 °C to 20 °C. The variations in the hysteretic characteristics of the SMAUDs, including partial superelasticity (SE), strength, stiffness, SC, and energy dissipation capabilities, at different ambient temperatures were investigated. In general, the decreasing ambient temperature leads to the degradation of the SC ability. At ambient temperatures below the phase transformation temperature, the SMAUDs lose the SE but still maintain certain levels of strength and energy dissipation, which is different from common axial-type SMA elements. Meanwhile, the SMAUDs can restore their SC ability and strength after the recovery from low temperatures to room temperature, making them suitable for use in a cold environment.

Effects of freeze-drying bovine pericardium using a combination of polyethylene glycol and trehalose

The freeze-drying is a technology that preserves biological samples in a dry state, which is beneficial for storage, transportation, and cost saving. In this study, the bovine pericardium was treated with a freeze-drying protectant composed of polyethylene glycol (PEG) and trehalose (Tre), and then freeze-dried. The results demonstrated that the mechanical properties of the pericardium treated with PEG + 10% w/v Tre were superior to those of the pericardium fixed with glutaraldehyde (GA). The wet state water content of the rehydrated pericardium, determined using the Karl Fischer method, was (74.81 ± 1.44)%, which was comparable to that of the GA-fixed pericardium. The dry state water content was significantly reduced to (8.64 ± 1.52)%, indicating effective dehydration during the freeze-drying process. Differential scanning calorimetry (DSC) testing revealed that the thermal shrinkage temperature of the pericardium was (84.96 ± 0.49) ℃, higher than that of the GA-fixed pericardium (83.14 ± 0.11) ℃, indicating greater thermal stability. Fourier transform infrared spectroscopy (FTIR) results showed no damage to the protein structure during freeze-drying. Hematoxylin and eosin (HE) staining demonstrated that the freeze-drying process reduced pore formation, prevented ice crystal growth, and resulted in a tighter arrangement of tissue fibers. The frozen-dried bovine pericardium was subjected to tests for cell viability and hemolysis rate. The results revealed a cell proliferation rate of (77.87 ± 0.49)%, corresponding to a toxicity grade of 1. Additionally, the hemolysis rate was (0.17 ± 0.02)%, which is below the standard of 5%. These findings indicated that the frozen-dried bovine pericardium exhibited satisfactory performance in terms of cytotoxicity and hemolysis, thus meeting the relevant standards. In summary, the performance of the bovine pericardium treated with PEG + 10% w/v Tre and subjected to freeze-drying could meet the required standards.

Pseudo-Eutectic of Isodimorphism to Design Biaxially-Oriented Bio-Based PA56/512 with High Strength, Toughness and Barrier Performances.

The biaxially-oriented PA56/512 has excellent mechanical strength, extensibility and water-oxygen barrier properties and has broad application prospects in green packaging, lithium battery diaphragm and medical equipment materials. The correlation between the aggregation structure evolution and macroscopic comprehensive properties of copolymer PA56/512 under biaxial stretching has been demonstrated in this work. The structure of the random copolymerization sequence was characterized by 13C Nuclear magnetic resonance (NMR). The typical isodimorphism behavior of the co-crystallization system of PA56/512 and its BOPA-56/512 films was revealed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) tests. And the aggregation structure, including the hydrogen bond arrangement, crystal structure and crystal morphology of PA56/512 before and after biaxial stretching, was investigated by XRD, Fourier-transform infrared spectroscopy (FTIR) and polarized optical microscopy (POM) tests. Furthermore, the effect of the biaxially-oriented stretching process on the mechanical properties of PA56/512 has been demonstrated. In addition, a deep insight into the influence of the structure on the crystallization process and physical-mechanical performance has been presented. The lowest melting point at a 512 content of 60 mol% is regarded as a "eutectic" point of the isodimorphism system. Due to the high disorder of the structural units in the polymer chain, the transition degree of the folded chain (gauche conformation) is relatively lowest when it is straightened to form an extended chain (trans conformation) during biaxially-oriented stretching, and part of the folded chain can be retained. This explains why biaxially stretched PA56/512 has high strength, outstanding toughness and excellent barrier properties at the pseudo-eutectic point. In this study, using the unique multi-scale aggregation structure characteristics of a heterohomodymite polyamide at the pseudo-eutectic point, combined with the new material design scheme and the idea of biaxial-stretching processing, a new idea for customized design of high-performance multifunctional polyamide synthetic materials is provided.

The Development of a 3D-Printed Compliant System for the Orientation of Payloads on Small Satellites: Material Characterization and Finite Element Analysis of 3D-Printed Polyetherketoneketone (PEKK)

This article focuses on the development of a 3D-printed 2-degree-of-freedom (DOF) joint for the payloads’ orientation on small satellites. This system is a compliant mechanism, meaning that this monolithic system composed of cross-axis flexural pivots (CAFPs) produces complex movements through the elastic deformation of its structure. Using fused filament fabrication (FFF), a demonstrator made of Polyetherketoneketone (PEKK) is printed to determine its potential compatibility with space conditions. Focusing on a segment of the joint, the CAFP, this study aims for an enhancement of its mechanical behavior through the study of its printing direction and the creation of an accurate finite element model of this compliant mechanism. First, material characterization of 3D-printed PEKK is achieved through differential scanning calorimetry tests of the filament and flexural and tensile tests of specimens printed in different printing directions. Then, these data are used to perform a finite element analysis of different CAFP designs and compare their mechanical response of their 3D-printed twin using digital image correlation software. Finally, the CAFP structures were observed by X-ray tomography. The results show that printing direction greatly influences both flexural and tensile strength. Voids induced by the FFF process could impact the mechanical behavior of 3D-printed parts as the simple CAFP design has a better test/model correlation than complex ones. This could influence its resistance to space environment.

Poly(ether‐ester)s synthesized from furandicarboxylic acid and ethylene glycol using an acidic binary catalyst

AbstractPoly(ethylene 2,5‐furandicarboxylate) (PEF) is an important biobased polyester with better thermal, mechanical, and gas barrier properties than poly(ethylene terephthalate). In PEF synthesis, diethylene glycol furandicarboxylate (DF) is inevitably formed via etherification side reaction. Taking advantage of the side reaction, poly(ethylene‐co‐diethylene furandicarboxylate) (PEDF) poly(ether‐ester)s were synthesized only from 2,5‐furandicarboxylic acid (FDCA) and ethylene glycol (EG), using a cheap binary propanedisulfonic acid/dibutyltin oxide (PSA/DBTO) catalyst. The polymers were characterized by 1H NMR, intrinsic viscosity, solubility, differential scanning calorimetry, thermogravimetric analysis, tensile, and gas barrier test. Due to strong acidity of PSA, not only major DF but also minor oligoethylene glycol furandicarboxylate ether‐containing units were formed. Their total content can be adjusted up to 78 mol% by simply increasing the dosage of PSA from 0 to 0.4 wt%. The effect of ether‐containing units on the solubility, thermal transition, mechanical, and oxygen barrier properties of the poly(ether‐ester)s were examined and compared with the poly(ether‐ester)s synthesized via copolycondensation.

Optimizing ageing conditions for commercial NiTi archwires: Insights from thermal phase transformation and tensile deformation analysis

Superelastic nickel-titanium (NiTi) archwires are now commonly used as the standard archwire during the orthodontic alignment and levelling stage. They are preferred due to their ability to apply minimal force on teeth while allowing for a wide range of tooth movements. During orthodontic treatment, the orthodontist assesses the dimension and shape of the NiTi archwire to determine the amount and direction of force required to align misaligned teeth. The main contribution of this study is the parametric analysis and establishment of a set of optimal ageing temperatures and duration for the investigation of functionally graded nickel-titanium archwire using differential scanning calorimetry (DSC) and tensile deformation testing. The mechanical and thermal phase transformation behavior after ageing at six temperatures for duration of 15 minutes have been investigated using tensile deformation test and differential scanning calorimetry (DSC) test in this paper. Experimental results reveal that in thermal analysis as the ageing temperatures increase from 400 °C to 490 °C, the austenite finish temperature rises to a value between 9.53 °C and 35.48 °C, and subsequently decreases to 520 °C. The archwire specimen aged for temperature of 490 °C exhibited the austenite finish temperature of around 35.48 °C, and it is highest among the aged wire specimens closest to oral temperature. In tensile deformation, the ideal ageing temperature for orthodontic applications was determined to be 490 °C for 15 minutes, resulting in relatively low plateau slope 13.73 GPa with high superelatic ratio 12.04, and maximum plateau strain of 7 %.

Comparative study on interactions of phillyrin and phillygenol with lysozyme: Spectroscopy, differential scanning calorimetry and molecular modeling approaches

Phillyrin (PR) and its derivative phillygenol (PG) are major active extracts of the Chinese medicine Forsythiae Fructus. Lysozyme, an important carrier protein, has a variety of physiological along with pharmaceutical functions. Herein, the interactions of PR and PG with hen egg white lysozyme (HEWL) are investigated in details by spectroscopic analyses, differential scanning calorimetry (DSC) tests, and molecular modeling approaches. Fluorescence measurement and UV–visible absorption difference spectroscopy reveal that an “untypical static quenching” takes place pointing towards the formation of ground state complex. The binding constants of HEWL-PG are greater than that of HEWL-PR. Moreover, the major driving force for the binding process is elucidated as hydrophobic interactions for both cases. Circular dichroism spectroscopy and three-dimensional fluorescence indicate that PR and PG decrease the helical structure of the HEWL and hydrophobicity surrounding Trp and Tyr residues. The thermal stability of HEWL decreases in the presence of PR and PG by DSC. Docking study infers that both PR and PG could bind to the hydrophobic cavity of HEWL and supports the higher binding of PG than PR. Molecular dynamics study illustrates that PR has higher relative position change, which may attribute to its lower binding ability. In terms of the radius of gyration (Rg), PG causes the protein structure to swell even more. The average hydrogen bonds number of HEWL-PG is less than that of HEWL-PR and more changes of the residual fluctuation are observed in HEWL-PG system. Furthermore, MM-PBSA analysis exhibits that HEWL-PG has lower binding energy. Collectively, these results support that both PR and PG could bind to HEWL, but PG possesses higher affinity which leads to stronger secondary structural changes of HEWL than PR. These findings are beneficial to comprehensively understand the binding characteristic of PR and PG with HEWL, providing experimental basis for pharmacokenitics of PR and PG.

Characterization of eco‐friendly composites for automotive applications prepared by the compression molding method

AbstractThe need to comply with environmental regulations and provisions set by the government for sustainability and environmental awareness has caused the use of natural fiber‐reinforced composites in the automotive industry to increase. Furthermore, there has been a lack of extensive research on the production of eco‐friendly composites for automotive applications utilizing epoxy resin, rice husk, Al2O3, and Fe2O3 by the compression molding technique. Therefore, the objective of this study is to determine the influence of compression molding pressure on the properties of eco‐friendly composites for automotive applications. The specimens consisted of epoxy resin, rice husk, Al2O3, and Fe2O3, in that order by weight percentages of 50%, 20%, 15%, and 15%, respectively. Compression molding with pressures of 10, 20, and 30 MPa and a holding time of 20 min at room temperature was utilized in this study. To evaluate the properties of the obtained specimens, density, hardness, flexural, wear, TGA (thermal gravimetric analysis), and DSC (differential scanning calorimetry) tests were conducted. The research findings show that composite specimens' physical and mechanical properties decrease while the friction coefficient increases with increasing pressure during compression molding. In contrast, the pressure increase did not significantly alter the thermal characteristics of the composite specimens. The BP_10 specimen, fabricated at a molding pressure of 10 MPa, exhibited superior properties compared to other specimens. Density, hardness, flexural strength, coefficient of friction, total residue, Tmax, Tg, and Tc in specimen BP_10 was 1.881 g/cm3, 80.5 shore D, 35.84 MPa, 0.262, 58.67%, 354.87, 285.53, and 497.7°C, respectively.Highlights The demand for natural fiber‐reinforced composites is increasing because more vehicles are on the road. The properties of natural fiber‐reinforced composites are strongly influenced by the pressure applied during compression molding. Results show that compression molding pressure strongly influenced the hardness, density, flexural strength, friction coefficient, and thermal stability of natural fiber‐reinforced composites. The natural fiber‐reinforced composites developed in this research can contribute to several Sustainable Development Goals (SDGs).

A data-driven analysis of HDPE post-consumer recyclate for sustainable bottle packaging

The packaging industry faces mounting demand to integrate post-consumer recyclate (PCR). However, the complex structure-property relationships of PCRs often obscure their performance compared to virgin equivalents, posing challenges in selecting suitable PCRs for applications. Focused on extrusion blow moulding grade high-density polyethylene (HDPE), this study presents the most extensive characterisation of HDPE PCR to date, encompassing 23 resins (3 virgin, 20 PCR). Employing Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), rheology, colour analysis, and mechanical testing, we established a feature-rich dataset with 56 distinctive characteristics. Utilising a data science approach based on principal component analysis, with the virgin samples as a benchmark, we identified that combining FTIR, TGA and mechanical testing provided effective identification of PCRs that closely match the properties of virgin HDPE. The pipeline created can be utilised for new PCRs to determine suitability as a replacement for virgin plastic in a desired application.

Closing the loop in space 3D printing: Effect of vacuum, recycling, and UV aging on high performance thermoplastics produced via filament extrusion additive manufacturing

The outlook for space exploration, and the long-term sustainable presence of humans in space, rely upon the advancement of in-situ manufacturing capabilities. In-space additive manufacturing (AM) has gained significant attention due to its potential to produce spare parts in-situ and facilitate repairs for extending space missions. However, to date, there is no AM system capable of processing high-performance engineering thermoplastic polymers within uncontrolled space conditions (i.e., reduced gravity, vacuum, and radiation environment). Additionally, the effect of ultra-violet (UV) radiation on printed parts has remained unexplored. In this work, a custom-built filament extrusion AM breadboard has been developed and tested enabling the fabrication of engineering thermoplastic polymers, whereby the machine was placed inside a vacuum chamber to partly mimic the harsh space environment. Mechanical (tensile and flexural) and thermal (thermogravimetric analysis, differential scanning calorimetry and dynamic mechanical analysis) tests were conducted on the printed specimens before and after exposure to UV aging. Moreover, the printed geometries underwent a recycling process involved the shredding of the pristine 3D-printed polymeric samples, the drying of the obtained granulates and finally the extrusion of 3D-printable filaments. The polymeric recycled 3D-printed specimens were then subjected to further mechanical and thermal testing, offering valuable insights into the feasibility of in-space AM and the potential to augment the circularity of the printed parts. The results of the mechanical and thermal tests, together with the effect of vacuum printing, UV aging, and recycling, are provided within the manuscript. This work cements the basic building blocks to sustainably advance on-orbit and in-space infrastructure, and paves the way for long-term human space missions.

Preparation and Characterization of Guaiacol-Furfuramine Benzoxazine and Its Modification of Bisphenol A-Aniline Oxazine Resin.

A new type of benzoxazine resin has been synthesized using a natural phenol source, guaiacol, and a biomass amines, furfuramine. The synthesis conditions were optimized; when the reaction molar ratio of guaiacol, furfuramine, and polyformaldehyde was 1:1:4, the highest synthetic yield was reached. The product was characterized via testing using transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), mass spectrogram (MS), and nuclear magnetic resonance (1H-NMR) to confirm its molecular structure. A differential scanning calorimetry (DSC) test was conducted to analyze the thermodynamic properties of the product, and the results showed that the product decomposed and evaporated at around 180 °C, making it impossible to achieve self-curing. However, the prepared guaiacol-furfuramine benzoxazine resin (GFZ) can be blended and cured in certain proportions with bisphenol A-aniline oxazine resin (BAZ) as a GFZ/BAZ binary system (5:95, 10:90, 20:80, and 40:60). Dynamic mechanical analysis (DMA) test results showed that when the content of GFZ was 10%, the storage modulus of the copolymer resin was greatly improved. After conducting impact strength tests on the copolymer resin, it was found that the toughness of the copolymer resin had improved, and the maximum impact strength had increased by nearly three times. This indicates that the flexible long-chain structure in GFZ can effectively improve the toughness of the cured copolymer system. The reaction of active groups on benzoxazine molecules with other resins can not only improve the mechanical properties of their cured products, but also has important significance in the preparation of low-cost and environmentally friendly sustainable composite materials with excellent comprehensive performance.

Introducing Ni-N-C ternary nanocomposite as an active material to enhance the hydrogen storage properties of MgH2

The use of Mg-based materials as solid-state hydrogen storage materials can provide a viable solution to the bottleneck hindering the development of hydrogen energy. However, it is necessary to address their excessively stable thermodynamic properties and sluggish kinetic performances. In this study, we prepared a Ni-N-C ternary nanocomposite (designated as Ni@NC) catalyst using Ni-based metal-organic frameworks (Ni-MOFs) as a precursor for catalytic MgH2 hydrogen storage properties. The Ni@NC catalyst exhibited excellent promotion effects on the hydrogen absorption and desorption kinetics and the cycling stability of the Mg-based materials. Notably, the composite exhibited room-temperature hydrogen absorption initiation and an onset dehydrogenation temperature of 188 °C, with complete hydrogenation achieved after holding at 100 °C for 60 min. After undergoing 100 cycles of absorption/dehydrogenation, the capacity retention rate was 99.5 %. The differential scanning calorimetry (DSC) test results indicated that the re-hydrogenated MgH2-Ni@NC composites consist of Mg2NiH4 and MgH2, with corresponding dehydrogenation activation energies of 75.2 and 82.9 kJ mol−1 respectively. The mechanism analysis revealed that Ni@NC was uniformly distributed on the MgH2 surface. During dehydrogenation/rehydrogenation, Mg2NiH4/Mg2Ni “hydrogen pumping” by Ni and MgH2/Mg occurred in situ, the presence of N-C effectively inhibited the expansion of MgH2/Mg, and the enhanced charge transfer effect was facilitated by N in the Ni@NC composite, synergistically enhancing the kinetic performance and cycling stability of MgH2.

Enhancing polyamide 6: Acid hydrolysis for functionalization and amino group quantification

In this study, our primary aim was to increase the presence of amine groups in polyamide 6 fibers. To achieve this, we employed a functionalization process that mainly depended on increasing the number of reactive sites via acid-catalyzed hydrolysis. The effects of several acids were rigorously examined, including hydrochloric acid (HCl), sulfuric acid (H2SO4), and formic acid (HCOOH). Following this comprehensive acid-based treatment, the method that demonstrated the most significant increase in amine groups was selected for further evaluation in dyeing experiments and full characterization. The quantification of amino groups was performed using potentiometry, evaluating the equilibrium state of acid removal from the fibers. To corroborate these results, the acid dye Levaset Blue 2R was employed, which measured the amount of dye bound to the fibers during the dyeing process. Characterization of the polyamide 6 fiber structural changes was conducted using multiple techniques, including tensile tests, Fourier transform infrared (FTIR) spectroscopy, and differential scanning calorimetry (DSC). Among the acid treatments, the 11% HCl treatment exhibited the most significant increase in amine groups, amounting to an approximately 110% increase as measured by potentiometry and an approximately 150% increase using the dyeing method. During the dyeing process, the 11% HCl-treated fibers absorbed 91% of the dye from the dye bath, indicating enhanced color intensity and K/S value, thus affirming the efficacy of the amine group increasing. Tensile testing revealed a decrease in the strength of the functionalized fiber. In the FTIR spectra, there was a notable increase in the intensity of bands associated with the fiber's crystalline regions and hydrogen bonds. DSC tests validated the FTIR results, demonstrating a 9% increase in crystallinity. Furthermore, SEM micrographs depicted surface alterations induced by the hydrolysis process. These results collectively highlight the effectiveness of hydrolysis in introducing functional groups, enhancing color intensity during dyeing with acid dyes, and reducing dye content in the bath. Additionally, the potentiometric method for quantifying amine group demonstrated practicality and accuracy, serving as a valuable contribution to the field.

Influence of modified phosphogypsum content on the properties of HDPE/phosphogypsum composites

Phosphogypsum has received increasing attention for solid waste with high production and environmental pollution. This study treated phosphogypsum with the silane coupling agent 3-(methacryloyloxy) propyltrimethoxysilane (KH570) to create modified HDPE/phosphogypsum composites. The modified phosphogypsum was then melted and blended with high-density polyethylene (HDPE). Thermal weight loss (TG), differential scanning calorimetry (DSC), and rheological and mechanical property testing were used to study the impact of the changed phosphogypsum content on the properties of the composites. The outcomes demonstrate that even at low filling levels, the modified phosphogypsum may be evenly distributed throughout the matrix. Furthermore, the addition of increased phosphogypsum filling enhances the mechanical characteristics of the HDPE matrix.