Tribological behavior of UHMWPE in water lubrication: the effect of molding temperature

Purpose Ultra-high molecular weight polyethylene (UHMWPE) is adopted in water-lubricated bearings for its excellent performance. This paper aims to investigate the tribological properties of UHMWPE with a molecular weight of 10.2 million (g mol‐1) under different molding temperatures. Design/methodology/approach The UHMWPE samples were prepared by mold pressing under constant pressure and different molding temperatures (140°C, 160°C, 180°C, 200°C, 220°C). The friction and wear tests in water were conducted at the RTEC tribo-tester. Findings The friction coefficient and wear loss decreased first and rose later with the increasing molding temperature. The minimums of the friction coefficient and wear loss were found at the molding temperatures of 200°C. At low melting temperatures, the UHMWPE molecular chains could not unwrap thoroughly, leading to greater abrasive wear. On the other hand, high melting temperatures will cause the UHMWPE molecular chains to break up and decompose. The optimal molding temperatures for UHMWPE were found to be 200°C. Originality/value Findings are of great significance for the design of water-lubricated UHMWPE bearings.

Machine Learning-Based Enzyme Engineering of PETase for Improved Efficiency in Degrading Non-Biodegradable Plastic

Globally, nearly a million plastic bottles are produced every minute (1). These non-biodegradable plastic products are composed of Polyethylene terephthalate (PET). In 2016, researchers discovered PETase, an enzyme from the bacteria Ideonella sakaiensis which breaks down PET and nonbiodegradable plastic. However, PETase has low efficiency at high temperatures. In this project, we optimized the rate of PET degradation by PETase by designing new mutant enzymes which could break down PET much faster than PETase, which is currently the gold standard. We used machine learning (ML) guided directed evolution to modify the PETase enzyme to have a higher optimal temperature (Topt), which would allow the enzyme to degrade PET more efficiently. First, we trained three machine learning models to predict Topt with high performance, including Logistic Regression, Linear Regression and Random Forest. We then used Random Forest to perform ML-guided directed evolution. Our algorithm generated hundreds of mutants of PETase and screened them using Random Forest to select mutants with the highest Topt, and then used the top mutants as the enzyme being mutated. After 1000 iterations, we produced a new mutant of PETase with Topt of 71.38℃. We also produced a new mutant enzyme after 29 iterations with Topt of 61.3℃. To ensure these mutant enzymes would remain stable, we predicted their melting temperatures using an external predictor and found the 29-iteration mutant had improved thermostability over PETase. Our research is significant because using our approach and algorithm, scientists can optimize additional enzymes for improved efficiency.

Sequence Effect on the Activity of DNAzyme with Covalently Attached Hemin and Their Potential Bioanalytical Application

In this work we investigated the effect of a DNA oligonucleotide sequence on the activity of a DNAzyme with covalently attached hemin. For this purpose, we synthesized seven DNA-hemin conjugates. All DNA-hemin conjugates as well as DNA/hemin complexes were characterized using circular dichroism, determination of melting temperatures and pKa of hemin. We observed that hemin conjugation in most cases led to the formation of parallel G-quadruplexes in the presence of potassium and increased thermal stability of all studied systems. Although the activity of DNA-hemin conjugates depended on the sequence used, the highest activity was observed for the DNA-hemin conjugate based on a human telomeric sequence. We used this DNAzyme for development of “sandwich” assay for detection of DNA sequence. For this assay, we used electric chip which could conduct electricity after silver deposition catalyzed by DNAzyme. This method was proved to be selective towards DNA oligonucleotides with mismatches and could be used for the detection of the target. To prove the versatility of our DNAzyme probe we also performed experiments with streptavidin-coated microplates. Our research proved that DNAzyme with covalently attached hemin can be used successfully in the development of heterogeneous assays.

A Promising Thermodynamic Study of Hole Transport Materials to Develop Solar Cells: 1,3-Bis(N-carbazolyl)benzene and 1,4-Bis(diphenylamino)benzene

The thermochemical study of the 1,3-bis(N-carbazolyl)benzene (NCB) and 1,4-bis(diphenylamino)benzene (DAB) involved the combination of combustion calorimetric (CC) and thermogravimetric techniques. The molar heat capacities over the temperature range of (274.15 to 332.15) K, as well as the melting temperatures and enthalpies of fusion were measured for both compounds by differential scanning calorimetry (DSC). The standard molar enthalpies of formation in the crystalline phase were calculated from the values of combustion energy, which in turn were measured using a semi-micro combustion calorimeter. From the thermogravimetric analysis (TGA), the rate of mass loss as a function of the temperature was measured, which was then correlated with Langmuir’s equation to derive the vaporization enthalpies for both compounds. From the combination of experimental thermodynamic parameters, it was possible to derive the enthalpy of formation in the gaseous state of each of the title compounds. This parameter was also estimated from computational studies using the G3MP2B3 composite method. To prove the identity of the compounds, the 1H and 13C spectra were determined by nuclear magnetic resonance (NMR), and the Raman spectra of the study compounds of this work were obtained.

Formation, preservation and extinction of high-pressure minerals in meteorites: temperature effects in shock metamorphism and shock classification

The goal of classifying shock metamorphic features in meteorites is to estimate the corresponding shock pressure conditions. However, the temperature variability of shock metamorphism is equally important and can result in a diverse and heterogeneous set of shock features in samples with a common overall shock pressure. In particular, high-pressure (HP) minerals, which were previously used as a solid indicator of high shock pressure in meteorites, require complex pressure–temperature–time (P–T–t) histories to form and survive. First, parts of the sample must be heated to melting temperatures, at high pressure, to enable rapid formation of HP minerals before pressure release. Second, the HP minerals must be rapidly cooled to below a critical temperature, before the pressure returns to ambient conditions, to avoid retrograde transformation to their low-pressure polymorphs. These two constraints require the sample to contain large temperature heterogeneities, e.g. melt veins in a cooler groundmass, during shock. In this study, we calculated shock temperatures and possible P–T paths of chondritic and differentiated mafic–ultramafic rocks for various shock pressures. These P–T conditions and paths, combined with observations from shocked meteorites, are used to constrain shock conditions and P–T–t histories of HP-mineral bearing samples. The need for rapid thermal quench of HP phases requires a relatively low bulk-shock temperature and therefore moderate shock pressures below ~ 30 GPa, which matches the stabilities of these HP minerals. The low-temperature moderate-pressure host rock generally shows moderate shock-deformation features consistent with S4 and, less commonly, S5 shock stages. Shock pressures in excess of 50 GPa in meteorites result in melt breccias with high overall post-shock temperatures that anneal out HP-mineral signatures. The presence of ringwoodite, which is commonly considered an indicator of the S6 shock stage, is inconsistent with pressures in excess of 30 GPa and does not represent shock conditions different from S4 shock conditions. Indeed, ringwoodite and coexisting HP minerals should be considered as robust evidence for moderate shock pressures (S4) rather than extreme shock (S6) near whole-rock melting.

Investigation of the chemical ordering and thermal properties of the Rh–Ag–Au nanoalloys

In this paper, the melting behaviors of Rh–Ag–Au nanoalloys are investigated with MD simulation. For Rh–Ag–Au nanoalloys, icosahedron structure was considered. The local optimizations of Rh–Ag–Au nanoalloys were carried out with the BH algorithm. The interatomic interactions were modeled with the Gupta potential. The local optimization results of Rh–Ag–Au nanoalloys show that Au and Ag atoms prefer to locate on the surface, and Rh atoms prefer to locate in the inner shells. The bond order parameter result is compatible with the excess energy analysis. It is noted that structures with more Ag–Au bonds are more energetically stable. Caloric curve, heat capacity, Lindemann index, and RMSD methods were used for estimating the melting temperatures of Rh–Ag–Au nanoalloys. According to the simulation results, melting temperatures depend on the composition. Also, it is discovered that nanoalloys are generally melting in two stages. Surface melting of the third shell is occupied by Ag and Au atoms, and then homogeneous melting of the inner shells is occupied by Rh atoms. It is found that the difference between surface melting temperatures and homogeneous melting temperatures in Ag-poor compositions is more significant than that of Ag-rich nanoalloys. In addition, the melting temperatures of the nanoalloys are found to be increased as the size of nanoalloys increases.

The melting properties of D-α-glucose, D-β-fructose, D-sucrose, D-α-galactose, and D-α-xylose and their solubility in water: A revision

Saccharides are still commonly isolated from biological feedstock by crystallization from aqueous solutions. Precise thermodynamic data on solubility are essential to optimize the downstream crystallization process. Solubility modeling, in turn, requires knowledge of melting properties. In the first part of this work, following our previous work on amino acids and peptides, D-α-glucose, D-β-fructose, D-sucrose, D-α-galactose, and D-α-xylose were investigated with Fast Scanning Calorimetry (FSC) in a wide scanning rate range (2000 K·s−1 to 10000 K·s−1). Using the experimental melting properties of saccharides from FSC allowed successfully modeling aqueous solubility for D-sucrose and D-α-galactose with the equation of state PC-SAFT. This provides cross-validation of the measurement methods to determine accurate experimental melting properties with FSC. Unexpectedly, the experimental FSC melting temperatures, extrapolated to zero scanning rates for thermal lag correction, were higher than results determined with DSC and available literature data. To clarify this inconsistency, FSC measurements towards low scanning rates from 10000 K·s−1 to 1 K·s−1 (D-α-glucose, D-β-fructose, D-sucrose) overlapping with the scanning rates of DSC and literature data were combined. At scanning rates below 1000 K·s−1, the melting properties followed a consistent non-linear trend, observed in both the FSC and the literature data. In order to understand the non-linear decrease of apparent melting temperatures with decreasing heating rate, the endothermic peaks were investigated in terms of isoconversional kinetics. The activation energies in the non-linear dependency region are in the range of $$300<{E}_{A}< 600 {\text{kJ}}\bullet {\text{mo}}{\text{l}}^{-1}$$ 300 < E A < 600 kJ ∙ mol - 1 . These values are higher than the enthalpy of sublimation for D-α-glucose, indicating that the non-linear behavior does not have a physical nature but attributes to chemical processes corresponding to the decomposition of molecular compounds within the crystal lattice before melting. The melting properties reported in the literature, commonly determined with conventional methods such as DSC, lead to inaccurate results due to the decomposition of these biomolecules at low heating rates. In addition, the FSC results at lower scanning rates coincide with results from DSC and literature in the overlapping scanning rate range, further validating the accuracy of FSC measurements to determine reliable melting properties of thermally labile biomolecules. The experimental FSC melting properties determined at higher scanning rates are considered as the correct equilibrium melting properties, which are not influenced by any chemical processes. The combination of FSC and PC-SAFT opens the door to model solubility of solid compounds that commonly decompose before melting.

Melting at Mg/Al interface in Mg-Al-Mg nanolayer by molecular dynamics simulations

The melting at the magnesium/aluminum (Mg/Al) interface is an essential step during the fabrications of Mg-Al structural materials and biomaterials. We carried out molecular dynamics simulations on the melting at the Mg/Al interface in a Mg-Al-Mg nanolayer via analyzing the changes of average atomic potential energy, Lindemann index, heat capacity, atomic density distribution and radial distribution function with temperature. The melting temperatures (T m) of the nanolayer and the slabs near the interface are significantly sensitive to the heating rate (v h) over the range of v h≤4.0 K/ps. The distance (d) range in which the interface affects the melting of the slabs is predicted to be (-98.2, 89.9) Å at v h→0, if the interface is put at d=0 and Mg (Al) is located at the left (right) side of the interface. The (T m) of the Mg (Al) slab just near the interface (e.g., d=4.0 Å) is predicted to be 926.8 K (926.6 K) at v h→0, with 36.9 K (37.1 K) below 963.7 K for the nanolayer. These results highlight the importance of regional research on the melting at an interface in the nanolayers consisting of two different metals.

Ionic Liquid-Based Gels for Applications in Electrochemical Energy Storage and Conversion Devices: A Review of Recent Progress and Future Prospects

Ionic liquids (ILs) are molten salts that are entirely composed of ions and have melting temperatures below 100 °C. When immobilized in polymeric matrices by sol–gel or chemical polymerization, they generate gels known as ion gels, ionogels, ionic gels, and so on, which may be used for a variety of electrochemical applications. One of the most significant research domains for IL-based gels is the energy industry, notably for energy storage and conversion devices, due to rising demand for clean, sustainable, and greener energy. Due to characteristics such as nonvolatility, high thermal stability, and strong ionic conductivity, IL-based gels appear to meet the stringent demands/criteria of these diverse application domains. This article focuses on the synthesis pathways of IL-based gel polymer electrolytes/organic gel electrolytes and their applications in batteries (Li-ion and beyond), fuel cells, and supercapacitors. Furthermore, the limitations and future possibilities of IL-based gels in the aforementioned application domains are discussed to support the speedy evolution of these materials in the appropriate applicable sectors.

Ash Melting Behavior of Rice Straw and Calcium Additives

Rice straw is potentially an appropriate feedstock material for biofuel production, since a huge amount of this postharvest residue is generated every year. The transformation of such agricultural biomass into densified products with a higher energy value and their subsequent combustion is associated with several questions. One of them is that rice straw exhibits a large formation of ash during combustion; thus, it is essential to know the nature of its ash melting behavior. Generally, during the combustion of straw biomass, ash sintering occurs in relatively low temperatures, resulting in the damaging of heating equipment. This negative aspect can be overcome by the addition of calcium-based additives. This paper aimed to study the ash melting behavior at a laboratory scale and to determine the ash melting points of rice straw mixed with calcium carbonate (CaCO3) and calcium hydroxide (Ca(OH)2) in different proportional ratios. The standardly produced ash samples from the rice straw obtained from Cambodia were constantly heated up in a muffle furnace, and characteristic temperatures of ash melting, i.e., shrinkage, deformation, hemisphere, and flow temperature, were recorded. The results showed that increasing the additive ratio did not bring linear growth of the melting temperatures. The addition of 1% CaCO3 showed an optimal positive impact of higher ash melting temperatures, and thus a better ability to abate the sintering of the rice straw ash.