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Search Results (19,294)

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18 pages, 1890 KiB  
Systematic Review
Diagnostic Performance and Interobserver Agreement of the Vesical Imaging–Reporting and Data System (VI-RADS) in Bladder Cancer Staging: A Systematic Review
by Alexandru Nesiu, Dorin Novacescu, Silviu Latcu, Razvan Bardan, Alin Cumpanas, Flavia Zara, Victor Buciu, Radu Caprariu, Talida Georgiana Cut and Ademir Horia Stana
Medicina 2025, 61(3), 469; https://doi.org/10.3390/medicina61030469 - 7 Mar 2025
Abstract
Background and Objectives: The Vesical Imaging–Reporting and Data System (VI-RADS) represents a standardized approach for interpreting multiparametric magnetic resonance imaging (mp-MRI) in bladder cancer (BC) evaluation. This systematic review aimed to assess the VI-RADS’ diagnostic performance and interobserver agreement in distinguishing muscle-invasive [...] Read more.
Background and Objectives: The Vesical Imaging–Reporting and Data System (VI-RADS) represents a standardized approach for interpreting multiparametric magnetic resonance imaging (mp-MRI) in bladder cancer (BC) evaluation. This systematic review aimed to assess the VI-RADS’ diagnostic performance and interobserver agreement in distinguishing muscle-invasive from non-muscle-invasive BC, a crucial differentiation for treatment planning. Materials and Methods: A systematic literature search was conducted through PubMed, Google Scholar, and Web of Science, over an initial five-year time span, from VI-RADS’ inception (May 2018) to November 2023. Studies reporting VI-RADS’ diagnostic performance with histopathological confirmation and interobserver agreement data were included. The diagnostic accuracy was assessed using sensitivity and specificity, while interobserver agreement was evaluated using Cohen’s κ coefficient. Results: Nine studies comprising 1249 participants met the inclusion criteria. Using a VI-RADS score cutoff of ≥3, the pooled sensitivity and specificity for detecting muscle invasion were 88.2% and 80.6%, respectively. Interobserver agreement showed excellent consistency with a mean κ value of 0.82. Individual study sensitivities ranged from 74.1% to 94.6%, while specificities varied from 43.9% to 96.5%. Conclusions: VI-RADS demonstrates high diagnostic accuracy and excellent interobserver agreement in BC staging, supporting its role as a reliable non-invasive diagnostic tool. However, it should be used as a complementary tool to, not a replacement for, histopathological confirmation. Moreover, the variability in specificity suggests the need for standardized training and interpretation protocols. Clinical correlation and adequate reader experience are essential for optimal implementation. Future integration with pathological data may further enhance its predictive value. Full article
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<p>Flow diagram of search algorithm.</p>
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<p>Multiparametric magnetic resonance imaging of the pelvis, at initial presentation of a bladder tumor case, scored as VI-RADS 4, on a 1.5-Tesla machine: (<b>A</b>) post-contrast fat-saturated axial T1-weighted sequence; (<b>B</b>) axial T2-weighted sequence; (<b>C</b>) diffusion-weighted imaging (DWI), axial sequence; (<b>D</b>) apparent diffusion coefficient (ADC) axial map. The mean ADC value for this tumor was 0.85 × 10<sup>−3</sup> mm<sup>2</sup>/s.</p>
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<p>Multiparametric magnetic resonance imaging of the pelvis, at initial presentation of a bladder tumor case, with an indwelling Foley catheter, scored as VI-RADS 5, on a 1.5-Tesla machine: (<b>A</b>) axial T2-weighted sequence; (<b>B</b>) sagittal T2-weighted sequence; (<b>C</b>) diffusion-weighted imaging (DWI), axial sequence; (<b>D</b>) apparent diffusion coefficient (ADC) axial map. The mean ADC value for this tumor was 0.82 × 10<sup>−3</sup> mm<sup>2</sup>/s.</p>
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15 pages, 2959 KiB  
Article
Machine Learning-Assisted Design of Doping Strategies for High-Voltage LiCoO2: A Data-Driven Approach
by Man Fang, Yutong Yao, Chao Pang, Xiehang Chen, Yutao Wei, Fan Zhou, Xiaokun Zhang and Yong Xiang
Batteries 2025, 11(3), 100; https://doi.org/10.3390/batteries11030100 - 7 Mar 2025
Abstract
Doping lithium cobalt oxide (LiCoO2) cathode materials is an effective strategy for mitigating the detrimental phase transitions that occur at high voltages. A deep understanding of the relationships between cycle capacity and the design elements of doped LiCoO2 is critical [...] Read more.
Doping lithium cobalt oxide (LiCoO2) cathode materials is an effective strategy for mitigating the detrimental phase transitions that occur at high voltages. A deep understanding of the relationships between cycle capacity and the design elements of doped LiCoO2 is critical for overcoming the existing research limitations. The key lies in constructing a robust and interpretable mapping model between data and performance. In this study, we analyze the correlations between the features and cycle capacity of 158 different element-doped LiCoO2 systems by using five advanced machine learning algorithms. First, we conducted a feature election to reduce model overfitting through a combined approach of mechanistic analysis and Pearson correlation analysis. Second, the experimental results revealed that RF and XGBoost are the two best-performing models for data fitting. Specifically, the RF and XGBoost models have the highest fitting performance for IC and EC prediction, with R2 values of 0.8882 and 0.8318, respectively. Experiments focusing on ion electronegativity design verified the effectiveness of the optimal combined model. We demonstrate the benefits of machine learning models in uncovering the core elements of complex doped LiCoO2 formulation design. Furthermore, these combined models can be employed to search for materials with superior electrochemical performance and processing conditions. In the future, we aim to develop more accurate and efficient machine learning algorithms to explore the microscopic mechanisms affecting doped layered oxide cathode material design, thereby establishing new paradigms for the research of high-performance cathode materials for lithium batteries. Full article
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<p>The flow chart of this research.</p>
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<p>Results histogram of Pearson coefficient correlations for every pair of variables in the data set.</p>
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<p>The feature importance plots of the selected nine features of the doped elements. We used the best-performing RF model for 1DC (<b>a</b>) and the best-performing XGBoost model for 25DC (<b>b</b>) predictions on the test set. The order of the <span class="html-italic">y</span>-axis labels indicates the importance of varied features. The <span class="html-italic">x</span>-axis shows the SHAP values, reflecting their contributions to the prediction model.</p>
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<p>(<b>a</b>–<b>c</b>) SEM images of (<b>a</b>) PLCO, (<b>b</b>) La–LCO, and (<b>c</b>) Bi–LCO. Insets in (<b>b</b>,<b>c</b>) are the EDS mappings of cross-section fabricated by FIB. (<b>d</b>) XRD patterns of PLCO, La–LCO, and Bi–LCO. (<b>e</b>) Enlarged view of (003) peaks derived from PLCO, La–LCO, and Bi–LCO. (<b>f</b>) Enlarged view of (104) peaks in the XRD patterns of cycled PLCO, La–LCO, and Bi–LCO.</p>
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<p>(<b>a</b>) XPS spectra of PLCO, Bi–LCO, and La–LCO before cycling. (<b>b</b>) XPS spectra of PLCO, Bi–LCO, and La–LCO after cycling. (<b>c</b>) The morphologies of the cycled 0.1% Bi–LCO. (<b>d</b>) The morphologies of the cycled 0.1% La–LCO.</p>
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<p>(<b>a</b>) Cycling performance of PLCO, 0.1%La–LCO, and 0.1%Bi–LCO. (<b>b</b>) Rate performance of PLCO, 0.1%La–LCO, and 0.1%Bi–LCO. (<b>c</b>) The dQ–dV curves of PLCO, 0.1%La–LCO, and 0.1%Bi–LCO at the first cycle. (<b>d</b>) Nyquist plots of the electrochemical impedance spectra measured at room temperature, and the equivalent circuit applied for data fit. (<b>e</b>) <span class="html-italic">Z</span>′ plotted against <span class="html-italic">w</span><sup>−1/2</sup> at the low-frequency region.</p>
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16 pages, 249 KiB  
Article
Evaluation of the Microbiological Performance and Potential Clinical Impact of New Rapid Molecular Assays for the Diagnosis of Bloodstream Infections
by Mateo Tićac, Tanja Grubić Kezele, Maja Abram and Marina Bubonja-Šonje
Microorganisms 2025, 13(3), 616; https://doi.org/10.3390/microorganisms13030616 - 7 Mar 2025
Viewed by 36
Abstract
Bloodstream infection (BSI) is a critical medical emergency associated with a high mortality rate. Rapid and accurate identification of the causative pathogen and the results of antimicrobial susceptibility testing are crucial for initiating appropriate antimicrobial therapy. The aim of this study was to [...] Read more.
Bloodstream infection (BSI) is a critical medical emergency associated with a high mortality rate. Rapid and accurate identification of the causative pathogen and the results of antimicrobial susceptibility testing are crucial for initiating appropriate antimicrobial therapy. The aim of this study was to evaluate the performance of a new rapid PCR Molecular Mouse System (MMS) for the identification of Gram-negative bacteria (GNB) and GNB resistance genes directly from a positive blood culture (BC). The validation of these rapid multiplex assays was carried out in a real hospital setting. A total of 80 BSI episodes were included in our study and the results were compared with culture-based methods. BC samples in which GNB had previously been detected microscopically and which originated from different hospital wards were analysed. The MMS GNB identification assay achieved a sensitivity of 98.7% and a specificity of 100% for the covered pathogens. In one BC sample, Klebsiella aerogenes was identified at the family level (Enterobacteriaceae) with MMS. However, in three polymicrobial samples, MMS identified bacteria that were not detected by culture-based methods (Klebsiella pneumoniae, K. aerogenes and Stenotrophomonas maltophilia). MMS also showed excellent overall performance in the detection of GNB resistance markers (100% sensitivity and 100% specificity). The type of extended-spectrum beta-lactamase (ESBL) resistance gene identified correctly with MMS was CTX-M-1/9 (n = 17/20), alone or in combination with SHV-type β-lactamase or with the different types of carbapenemase genes. MMS detected one carbapenemase gene of each type (KPC, NDM and OXA-23) and six OXA-48 genes. In addition, the colistin resistance gene mcr-1 was detected in one positive BC with Escherichia coli (E. coli). The time to result was significantly shorter for MMS than for routine culture methods. A retrospective analysis of the patients’ medical records revealed that a change in empirical antimicrobial therapy would have been made in around half of the patients following the MMS results. These results support the use of MMS as a valuable complement to conventional culture methods for more rapid BSI diagnosis and adjustment of empirical therapy. Full article
(This article belongs to the Special Issue Novel Approaches in the Diagnosis and Control of Emerging Pathogens)
20 pages, 2200 KiB  
Article
Quality of Single-Cone Obturation Using Different Sizes of Matching Gutta-Percha Points of Two Reciprocating Single-File Systems in Curved and Straight Root Canals
by Shakiba Arvaneh, René Schwesig, Shahpar Haghighat and Christian Ralf Gernhardt
Medicina 2025, 61(3), 465; https://doi.org/10.3390/medicina61030465 - 7 Mar 2025
Viewed by 56
Abstract
Background and Objectives: Endodontic success depends on eliminating infection and creating a durable seal to prevent recontamination. The goal of this study was to assess the impact of different ISO sizes on the obturation quality using two reciprocating single-file systems, WaveOne® Gold [...] Read more.
Background and Objectives: Endodontic success depends on eliminating infection and creating a durable seal to prevent recontamination. The goal of this study was to assess the impact of different ISO sizes on the obturation quality using two reciprocating single-file systems, WaveOne® Gold and Procodile®, in two different canal morphologies. Material and Methods: Overall, 140 root canals from human permanent teeth were randomly assigned to 14 groups based on selected ISO sizes and straight and curved canal curvatures, and the two file systems, WaveOne® Gold files in ISO sizes 20, 25, and 45, and Procodile® files in ISO sizes 20, 25, 40, and 45, were employed for canal preparation. These 140 canals were obturated using corresponding gutta-percha points and AH-Plus sealer and the quality of the obturation was assessed after sectioning the roots (apical, middle, coronal third) by evaluating the resulting 420 sections under a digital fluorescence microscope with regard to the proportion of gutta-percha, sealer, and unfilled areas. The results were analyzed using nonparametric tests. Results: For both systems, there was a significant difference in the percentage of gutta-percha-filled areas (PGFA, p < 0.001) and sealer-filled areas (PSFA, p < 0.001 among the different ISO sizes). However, no significant difference was observed in the percentage of unfilled areas (PUA, p = 0.354). ISO 40 demonstrated the best results, with the highest percentage of gutta-percha-filled areas (87%) and the lowest percentages of sealer-filled areas (13%) and voids (0.5%). In contrast, the lowest percentages of gutta-percha filled areas were observed in root canal fillings with ISO 20 (81%) and ISO 25 (81%). Regarding both reciprocating file system sizes, ISO 45 in WaveOne® Gold and ISO 40 in Procodile® demonstrated significantly improved (p < 0.05) filling quality, with PGFA of 85% and 87%, respectively. The differences between both systems were not significant. Conclusions: The results presented suggest that larger sizes provide better filling results, especially in the apical region. These results underline the importance of selecting appropriate preparation sizes adjusted to the initial anatomical specifications to optimize root canal obturation and ensure a high quality and durable seal. Full article
(This article belongs to the Section Dentistry and Oral Health)
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<p>Sample selection and distribution within the different experimental groups.</p>
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<p>Steps in root canal treatment: 1. trepanation; 2. shaping and cleaning; 3. obturation using a single cone Gutta-percha and sealer.</p>
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<p>(<b>a</b>) The root-filled tooth was sectioned at three levels (apical, middle, and coronal). (<b>b</b>) A schematic representation of sections under a microscope (magnification 6×): red—gutta-percha; yellow—sealer; black—voids.</p>
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<p>Percentage of gutta-percha, sealer, and unfilled areas regarding different ISO sizes.</p>
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<p>Percentage of gutta-percha, sealer, and unfilled area per ISO size depending on two systems.</p>
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<p>Percentage of areas filled with gutta-percha, sealer, and unfilled area for ISO size depending on curved and straight canals.</p>
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20 pages, 3687 KiB  
Article
Towards a Comprehensive Framework for Made-to-Measure Alginate Scaffolds for Tissue Engineering Using Numerical Simulation
by Alexander Bäumchen, Johnn Majd Balsters, Beate-Sophie Nenninger, Stefan Diebels, Heiko Zimmermann, Michael Roland and Michael M. Gepp
Gels 2025, 11(3), 185; https://doi.org/10.3390/gels11030185 - 7 Mar 2025
Viewed by 141
Abstract
Alginate hydrogels are integral to many cell-based models in tissue engineering and regenerative medicine. As a natural biomaterial, the properties of alginates can vary and be widely adjusted through the gelation process, making them versatile additives or bulk materials for scaffolds, microcarriers or [...] Read more.
Alginate hydrogels are integral to many cell-based models in tissue engineering and regenerative medicine. As a natural biomaterial, the properties of alginates can vary and be widely adjusted through the gelation process, making them versatile additives or bulk materials for scaffolds, microcarriers or encapsulation matrices in tissue engineering and regenerative medicine. The requirements for alginates used in biomedical applications differ significantly from those for technical applications. Particularly, the generation of novel niches for stem cells requires reliable and predictable properties of the resulting hydrogel. Ultra-high viscosity (UHV) alginates possess alginates with special physicochemical properties, and thus far, numerical simulations for the gelation process are currently lacking but highly relevant for future designs of stem cell niches and cell-based models. In this article, the gelation of UHV alginates is studied using a microscopic approach for disc- and sphere-shaped hydrogels. Based on the collected data, a multiphase continuum model was implemented to describe the cross-linking process of UHV alginate polysaccharides. The model utilizes four coupled kinetic equations based on mixture theory, which are solved using finite element software. A good agreement between simulation results and experimental data was found, establishing a foundation for future refinements in the development of an interactive tool for cell biologists and material scientists. Full article
(This article belongs to the Special Issue Recent Research on Alginate Hydrogels in Bioengineering Applications)
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Graphical abstract

Graphical abstract
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<p>Time-lapse sequence of alginate gelation with different concentrations of cross-linking agents. (<b>a</b>) 10 mM BaCl<sub>2</sub> solution, (<b>b</b>) 20 mM BaCl<sub>2</sub> solution and (<b>c</b>) 40 mM BaCl<sub>2</sub> solution. The gelation kinetics of the alginate are derived from the course of the traveling gelled/liquid interface. Due to low contrast, dashed white lines are used to indicate segments of the gelled/liquid interface. Scale bar indicates 1000 μm. Images are enhanced using a bandpass filter in ImageJ.</p>
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<p>Analysis of the gelation process of alginate discs. (<b>a</b>) Gelation kinetics analyzed by the decreasing diameter of the gelation front. The kinetics of gelation depend strongly on the applied cross-linker concentration: the higher the BaCl<sub>2</sub> concentration, the faster the overall gelation of the alginate droplet. (<b>b</b>) Velocity of the gelation front of alginates. Doubling the cross-linker concentration leads to a linear increase in gelation velocity. The velocity of gelation in this work is defined as the reduction of the ungelled core and is negative. Data are expressed as mean value ± standard deviation (n = 5 gelation experiments). Standard deviation in (<b>a</b>) is shown as a ribbon for visualization purposes.</p>
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<p>Analysis of the alginate gelation process of alginate spheres (beads, microcarriers). Gelation kinetics were analyzed by the decreasing diameter of the gelation front. The kinetics of gelation depend strongly on the applied cross-linker concentration: the higher the BaCl<sub>2</sub> concentration, the faster the overall gelation of the alginate droplet. (<b>a</b>) Single gelation experiments using 10 mM BaCl<sub>2</sub> solution; (<b>b</b>) single gelation experiments using 20 mM BaCl<sub>2</sub> solution; (<b>c</b>) single gelation experiments using 40 mM BaCl<sub>2</sub> solution; (<b>d</b>) the velocity of gelation front of alginates from (<b>a</b>) to (<b>c</b>) extracted by linear curve fitting. The velocity of gelation in this work is defined as the reduction of the ungelled core and is negative. Doubling the cross-linker concentration leads to a linear increase in gelation velocity. Data colors in (<b>a</b>–<b>c</b>) refer to different gelation experiments. Data in (<b>d</b>) are expressed as mean values ± standard deviation (n = 5 gelation experiments).</p>
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<p>Alginate micro-layer formation during gelation. (<b>a</b>) <b>Top</b>: Microscopic image of the formed layer at the outer border of the alginate disc; scale bar: 200 µm. Inset: Lower magnification of the area indicated by the black dashed line. Black arrow: Line scan of intensity in the graph. <b>Bottom</b>: The graph illustrates the data from the line scan of intensity. (<b>b</b>) Schematic illustration of layer formation in alginate disc-like hydrogels (adapted from [<a href="#B52-gels-11-00185" class="html-bibr">52</a>]; created with BioRender.com).</p>
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<p>Time-lapse of alginate gelation simulation with different concentration boundary conditions of the cross-linking agent. The left half of each time point shows the visualization of the numerical model, while the right half shows the microscopic image of one experimental replicate. (<b>a</b>) 10 mM BaCl<sub>2</sub> solution, (<b>b</b>) 20 mM BaCl<sub>2</sub> solution and (<b>c</b>) 40 mM BaCl<sub>2</sub> solution. Brighter areas indicate a higher amount of the ongoing gelling reaction. Scale bar indicates 1000 µm.</p>
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<p>Comparison of experimental data (solid line) and numerical modeling (dotted lines).</p>
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<p>Setup and principle of observing the gelation process. (<b>a</b>) A thin disc-like volume of alginate is poured into a dish and covered by a thin silicone spacer for gelation with different BaCl<sub>2</sub> solutions. This process can be observed using phase contrast microscopy, and a concentric decrease in the traveling liquid/gelled interface can be tracked and used for the quantification of the gelation process. (<b>b</b>) Schematic drawing at two different time points of alginate gelation. The disc-like volume of alginate is surrounded by the BaCl<sub>2</sub> cross-linker solutions and, consequently, barium (and chloride) ions diffuse into the alginate sol, triggering the gelation that can be tracked by the traveling liquid/gelled interface over time. The diameters of the circular interfaces decrease over time and disappear after the complete gelation of the alginate discs. (<b>b</b>) generated with BioRender.com.</p>
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<p>(<b>a</b>) Representative volume filled with the free polymer, barium ions and cross-linked polymer (and water). (<b>b</b>) Macroscopic domain and RVE as a magnification of a spatial point. The mass of constituent φ<sup>α</sup> inside the RVE changes due to the flux over the boundary and the mass exchange. Created with BioRender.com.</p>
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12 pages, 7645 KiB  
Article
Dynamic Mechanical and Failure Properties of Grouted Fractured Rock Based on Nano-Grouting Material
by Yuhao Jin, Shuo Yang, Hui Guo, Lijun Han, Pengcheng Huang, Miao Chen, Hao Shan, Lanying Huang, Shanjie Su, Shengcheng Wang, Peitao Qiu, Xiaoxi Bi and Zu-an Liu
Processes 2025, 13(3), 765; https://doi.org/10.3390/pr13030765 - 6 Mar 2025
Viewed by 169
Abstract
Fractured rock masses are extremely common in geological engineering. In order to improve the stability of surrounding rock under dynamic conditions, new grouting materials and their reinforcement characteristics were studied. In this paper, split Hopkinson pressure bar (SHPB) tests were employed to analyze [...] Read more.
Fractured rock masses are extremely common in geological engineering. In order to improve the stability of surrounding rock under dynamic conditions, new grouting materials and their reinforcement characteristics were studied. In this paper, split Hopkinson pressure bar (SHPB) tests were employed to analyze the dynamic mechanical and failure characteristics of grouted fractured rock with nano-grouting material (nano-grouted fractured rock). Simultaneously, high-speed camera tests were utilized to examine the macroscopic dynamic deformation and failure processes. The following was found: (1) Under a relatively low impact air pressure of 0.1 MPa, the mechanical properties of nano-grouted fractured rock are considerably better than those of traditional cement-based grouted rock. However, when the impact air pressure is increased to 0.3 MPa, the superiority of nano-grouting material diminishes, the possible cause of which is explained from the microscopic point of view. This means the nano-grouting material is more suitable for low-engineering-disturbance conditions (e.g., shield construction). (2) Both for the nano- and superfine cement grouting material, the impact fractures initially emerge at the two ends of the original grouted fracture and form a pair of parallel lines. (3) In comparison with 0.1 MPa, the impact pressure of 0.3 MPa leads to more severe damage to the rock specimen. These findings contribute to a deeper understanding of the behavior of nano-grouted fractured rock under dynamic loading and provide valuable insights for relevant engineering applications in the field of rock mechanics and grouting technology. Full article
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<p>Fractured rock masses.</p>
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<p>Preparation of nano-grouting material.</p>
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<p>Fractured rock specimen and sealing treatment.</p>
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<p>Production of grouted fractured specimens.</p>
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<p>Hopkinson experimental system with high-speed camera.</p>
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<p>Dynamic stress–strain curves of grouted fractured rock specimens with impact air pressure of (<b>a</b>) 0.1 and (<b>b</b>) 0.3 MPa.</p>
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<p>Dynamic peak strength of grouted fractured rock specimens.</p>
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<p>SEM pictures of 0.3 MPa nano-grouting material in the fracture (<b>a</b>,<b>b</b>).</p>
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<p>Dynamic deformation and failure processes of grouted fractured rock under impact air pressure of 0.1 MPa.</p>
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<p>Dynamic deformation and failure processes of grouted fractured rock under impact air pressure of 0.1 MPa.</p>
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<p>Dynamic deformation and failure processes of grouted fractured rock under impact air pressure of 0.3 MPa.</p>
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16 pages, 14943 KiB  
Article
Immunohistochemical Evaluation of the Tumor Immune Microenvironment in Pancreatic Ductal Adenocarcinoma
by Gelu Mihai Breaza, Raluca Maria Closca, Alexandru Cristian Cindrea, Florin Emil Hut, Octavian Cretu, Laurentiu Vasile Sima, Marina Rakitovan and Flavia Zara
Diagnostics 2025, 15(5), 646; https://doi.org/10.3390/diagnostics15050646 - 6 Mar 2025
Viewed by 107
Abstract
Background: Pancreatic ductal adenocarcinoma is an aggressive neoplasm with a complex carcinogenesis process that must be understood through the interactions between tumor cells and tumor microenvironment cells. Methods: This study was retrospective with a chronological extension period of 16 years and [...] Read more.
Background: Pancreatic ductal adenocarcinoma is an aggressive neoplasm with a complex carcinogenesis process that must be understood through the interactions between tumor cells and tumor microenvironment cells. Methods: This study was retrospective with a chronological extension period of 16 years and included 56 cases of pancreatic ductal adenocarcinoma. This study identified, quantified, and correlated the cells of the tumor immune microenvironment in pancreatic ductal adenocarcinoma with major prognostic factors as well as overall survival, using an extensive panel of immunohistochemical markers. Results: Three tumor immunotypes were identified: subtype A (hot immunotype), subtype B (intermediate immunotype), and subtype C (cold immunotype). Patients with immunotype C exhibit considerably higher rates of both pancreatic fistulas and acute pancreatitis. Immunotypes B and C significantly increased the risk of this complication by factors of 3.68 (p = 0.002) and 3.94 (p = 0.001), respectively. The estimated probabilities of fistula formation for each immunotype are as follows: 2.5% for immunotype A, 25% for immunotype B, and 28% for immunotype C. There was a statistically significant difference in median survival times according to tumor immunotype (p < 0.001). Specifically, patients with immunotype C tumors had a median survival time of only 120.5 days, compared to 553.5 days for those with immunotype A and 331.5 for immunotype B tumors. Conclusions: The identification of the immunotype of pancreatic ductal adenocarcinoma can be a predictive factor for the occurrence of complications such as pancreatic fistula as well as for overall survival. Full article
(This article belongs to the Special Issue Diagnosis of Pancreatic Diseases)
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<p>Flowchart of the case selection.</p>
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<p>Morphological aspect and immunohistochemical profile of the pancreatic ductal adenocarcinoma immunotype A, ob.10× (ob.40× in the corner): (<b>a</b>) hematoxylin-eosin staining; (<b>b</b>) LCA; (<b>c</b>) CD20; (<b>d</b>) CD3; (<b>e</b>) CD4; (<b>f</b>) CD8; (<b>g</b>) CD5; (<b>h</b>) CD117; (<b>i</b>) CD68; (<b>j</b>) CD1a; FI: front of invasion.</p>
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<p>Morphological aspect and immunohistochemical profile of the pancreatic ductal adenocarcinoma immunotype B, ob.10× (ob.40× in the corner): (<b>a</b>) hematoxylin-eosin staining; (<b>b</b>) LCA; (<b>c</b>) CD20; (<b>d</b>) CD3; (<b>e</b>) CD4; (<b>f</b>) CD8; (<b>g</b>) CD5; (<b>h</b>) CD117.</p>
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<p>Morphological aspect and immunohistochemical profile of the pancreatic ductal adenocarcinoma immunotype C, ob.10× (ob.40× in the corner): (<b>a</b>) hematoxylin-eosin staining; (<b>b</b>) LCA; (<b>c</b>) CD20; (<b>d</b>) CD3; (<b>e</b>) CD4; (<b>f</b>) CD8; (<b>g</b>) CD5; (<b>h</b>) CD117.</p>
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<p>Histochemical aspects of tumor immunotypes in Masson’s trichrome staining, ob.5×: (<b>a</b>) immunotype A; (<b>b</b>) immunotype B; (<b>c</b>) immunotype C.</p>
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<p>Box plots for survival time by cancer subtype.</p>
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<p>Survival curves by cancer subtype.</p>
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24 pages, 18833 KiB  
Article
Impact of Microstructure on the In Situ Formation of LDH Coatings on AZ91 Magnesium Alloy
by Nan Wang, Yulai Song, Anda Yu, Yong Tian and Hao Chen
Materials 2025, 18(5), 1178; https://doi.org/10.3390/ma18051178 - 6 Mar 2025
Viewed by 147
Abstract
Layered Double Hydroxide (LDH) coatings were synthesized on as-cast, T4 (solution treatment), and T6 (aging treatment) AZ91 magnesium alloys using a hydrothermal method. XRD (X-Ray Diffraction) and SEM (Scanning Electron Microscope) analyses showed that the large β-phases in as-cast AZ91 initially promoted LDH [...] Read more.
Layered Double Hydroxide (LDH) coatings were synthesized on as-cast, T4 (solution treatment), and T6 (aging treatment) AZ91 magnesium alloys using a hydrothermal method. XRD (X-Ray Diffraction) and SEM (Scanning Electron Microscope) analyses showed that the large β-phases in as-cast AZ91 initially promoted LDH growth via galvanic corrosion, but later compromised coating integrity. In contrast, T6 and T4 alloys, with refined microstructures, formed uniform and compact LDH coatings. Corrosion resistance was enhanced in T6 and T4 alloys, as evidenced by higher impedance from EIS (Electrochemical Impedance Spectroscopy), and HER (Hydrogen Evolution Reaction) tests, due to the formation of dense LDH layers. Full article
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<p>Preparation process of LDHs coating on the surface of AZ91 magnesium alloy.</p>
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<p>Optical microscopy of (<b>a</b>) cast-AZ91, (<b>b</b>) T4-AZ91, (<b>c</b>) T6-AZ91.</p>
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<p>XRD patterns on (003) and (006) peaks: (<b>a</b>) cast-a-5min, T4-a-5min, T6-a-5min; (<b>b</b>) cast-a-20min, T4-a-20min, T6-a-20min; (<b>c</b>) cast-b-5min, T4-b-5min, T6-b-5min; (<b>d</b>) cast-b-20min, T4-b-20min, T6-b-20min; (<b>a1</b>–<b>d1</b>) is magnified view of (<b>a</b>–<b>d</b>) at 5–30°.</p>
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<p>The morphology of coatings formed on magnesium (<b>a1</b>–<b>a4</b>) Cast-AZ91 samples: (<b>a1</b>) Cast-a-5 min, (<b>a2</b>) Cast-a-20 min, (<b>a3</b>) Cast-b-5 min, (<b>a4</b>) Cast-b-20 min; (<b>b1</b>–<b>b4</b>) T4-AZ91 samples: (<b>b1</b>) T4-a-5 min, (<b>b2</b>) T4-a-20 min, (<b>b3</b>) T4-b-5 min, (<b>b4</b>) T4-b-20 min; (<b>c1</b>–<b>c4</b>) T6-AZ91 samples: (<b>c1</b>) T6-a-5 min, (<b>c2</b>) T6-a-20 min, (<b>c3</b>) T6-b-5 min, (<b>c4</b>) T6-b-20 min.</p>
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<p>The morphology of LDH coatings formed on the magnesium: (<b>a</b>–<b>c</b>) Cast-a-12h, T4-a-12h, T6-a-12h; (<b>d</b>–<b>f</b>) Cast-b-12h, T4-b-12h, T6-b-12h. The arrows in (<b>a</b>,<b>d</b>) point to the β-phase depression areas of the coating, and the square area in (<b>c</b>) is the magnified region of the arrowed parts.</p>
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<p>Cross-sectional morphologies (<b>a</b>–<b>c</b>) and EDS mapping results of oxygen element (<b>a1</b>–<b>c1</b>) and line scanning images (<b>a2</b>–<b>c2</b>). (<b>a</b>,<b>a1</b>,<b>a2</b>) Cast-a-12h, (<b>b</b>,<b>b1</b>,<b>b2</b>) T4-a-12h, (<b>c</b>,<b>c1</b>,<b>c2</b>) T6-a-12h.</p>
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<p>Cross-sectional morphologies (<b>a</b>–<b>d</b>) and EDS mapping results of oxygen element (<b>a1</b>–<b>d1</b>) and line scanning images (<b>a2</b>,<b>a3</b>,<b>b2</b>,<b>c2</b>,<b>d2</b>). (<b>a</b>,<b>a1</b>,<b>a2</b>,<b>a3</b>) Cast-b-12h, the marker ① represents the LDH coatings on the α-Mg matrix, while the marker ② represents the LDH coatings on the β phase. (<b>b</b>,<b>b1</b>,<b>b2</b>) T4-b-12h, (<b>c</b>,<b>c1</b>,<b>c2</b>) T6-b-12h coating grown at the grain boundary of T6-AZ91, (<b>d</b>,<b>d1</b>,<b>d2</b>) T6-b-12h coating grown at intracrystalline of T6-AZ91.</p>
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<p>Potentiodynamic polarization curves of substrate and Mg-Al LDHs coatings: (<b>a</b>) substrate, (<b>b</b>) Cast-a-20min, T4-a-20min, T6-a-20min, (<b>c</b>) Cast-a-12h, T4-a-12h, T6-a-12h.</p>
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<p>EIS results: (<b>a</b>–<b>c</b>) Cast-AZ91, T4-AZ91, T6-AZ91; (<b>d</b>–<b>f</b>) Cast-a-20min, T4-a-20min, T6-a-20min; (<b>g</b>–<b>i</b>) Cast-a-12h, T4-a-12h, T6-a-12h.</p>
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<p>Equivalent circuits used to fit the EIS data of (<b>a</b>) Cast-AZ91, T4-AZ91, T6-AZ91 and Cast-a-20min, T4-a-20min, T6-a-20min; (<b>b</b>) Cast-a-12h, T4-a-12h, T6-a-12h.</p>
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<p>Hydrogen evolution volume of 12h in-situ LDH on magnesium.</p>
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<p>Domain diagram of Al(OH)<sub>3</sub>, Mg(OH)<sub>2</sub>, and Mg/Al-NO<sub>3</sub>-LDH (The yellow area represents Al(OH)<sub>3</sub>, while the purple area represents Mg(OH)<sub>2</sub>. Line a represents the LDH solubility line for x = 0.33, while Line b represents the LDH solubility line for x = 0.2; Region ① represents the reaction area of Al(OH)<sub>3</sub> with Mg<sup>2+</sup>, Region ② represents the reaction area of Al(OH)<sub>3</sub> with Mg(OH)<sub>2</sub>, Region ③ represents the reaction area of Mg(OH)<sub>2</sub> with Al(OH)<sub>4</sub><sup>−</sup>, and Region ④ represents the reaction area of Mg<sup>2+</sup> with Al(OH)<sub>4</sub><sup>−</sup>).</p>
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<p>Mechanism of LDH layer formation on AZ91 matrix: (<b>a</b>) Cast-a-20min, (<b>b</b>) Cast-a-12h, (<b>c</b>) T4-a-20min, (<b>d</b>) T4-a-12h, (<b>e</b>) T6-a-20min, (<b>f</b>) T6-a-12h.</p>
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<p>Corrosion mechanism (<b>a</b>) cast-a-12h (<b>b</b>) T4-a-12h, (<b>c</b>) T6-a-12h.</p>
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22 pages, 11838 KiB  
Article
Catalytic Performance of Iron-Based Oxygen Carriers Mixed with Converter Steel Slags for Hydrogen Production in Chemical Looping Gasification of Brewers’ Spent Grains
by Miao Yuan, Huawei Jiang, Xiangli Zuo, Cuiping Wang, Yanhui Li and Hairui Yang
Energies 2025, 18(5), 1298; https://doi.org/10.3390/en18051298 - 6 Mar 2025
Viewed by 124
Abstract
Iron-based oxygen carriers (OCs) have received much attention due to their low costs, high mechanical strengths and high-temperature stabilities in the chemical looping gasification (CLG) of biomass, but their chemical reactivity is very ordinary. Converter steel slags (CSSs) are steelmaking wastes and rich [...] Read more.
Iron-based oxygen carriers (OCs) have received much attention due to their low costs, high mechanical strengths and high-temperature stabilities in the chemical looping gasification (CLG) of biomass, but their chemical reactivity is very ordinary. Converter steel slags (CSSs) are steelmaking wastes and rich in Fe2O3, CaO and MgO, which have good oxidative ability and good stability as well as catalytic effects on biomass gasification. Therefore, the composite OCs prepared by mechanically mixing CSSs with iron-based OCs are expected to be used to increase the hydrogen production in the CLG of biomass. In this study, the catalytic performance of CSS/Fe2O3 composite OCs prepared by mechanically mixing CSSs with iron-based OCs on the gasification of brewers’ spent grains (BSGs) were investigated in a tubular furnace experimental apparatus. The results showed that when the weight ratio of the CSSs in composite OCs was 0.5, the relative volume fraction of hydrogen reached the maximum value of 49.1%, the product gas yield was 0.85 Nm3/kg and the gasification efficiency was 64.05%. It could be found by X-ray diffraction patterns and scanning electron microscope characterizations that the addition of CSSs helped to form MgFe2O4, which are efficient catalysts for H2 production. Owing to the large and widely distributed surface pores of CSSs, mixing them with iron-based OCs was beneficial for catalytic steam reforming to produce hydrogen. Full article
(This article belongs to the Section A5: Hydrogen Energy)
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<p>Preparation procedure of iron-based oxygen carriers.</p>
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<p>Schematic illustration of experimental apparatus for gasification of BSGs.</p>
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<p>Effects of gasifier temperature on relative volume fractions of gas components.</p>
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<p>Effects of temperature on gas yield and gasification efficiency.</p>
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<p>Effects of OC/SG ratio on relative volume fractions of gas components.</p>
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<p>Effects of OC/SG ratio on gas yield and gasification efficiency.</p>
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<p>Effects of steam flow rate on relative volume fractions of gas components.</p>
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<p>Effects of steam flow rate on product gas yield and gasification efficiency.</p>
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<p>Effects of weight ratio of CSSs on relative volume fractions of gas components.</p>
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<p>Effects of weight ratio of CSSs on gas yield and gasification efficiency.</p>
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<p>The XRD patterns of fresh iron-based oxygen carriers (a), calcined CSSs (b), fresh CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (c) and used CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (d).</p>
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<p>The reference XRD patterns of Fe<sub>2</sub>O<sub>3</sub>, Fe<sub>3</sub>O<sub>4</sub>, Al<sub>2</sub>O<sub>3</sub>, CaO, MgO, MgFe<sub>2</sub>O<sub>4</sub> and SiO<sub>2</sub>.</p>
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<p>The SEM images of different OCs. (<b>a</b>) Fresh iron-based OCs (5000×), (<b>b</b>) fresh iron-based OCs (10,000×), (<b>c</b>) calcined CSSs (5000×), (<b>d</b>) calcined CSSs (10,000×), (<b>e</b>) fresh CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (5000×), (<b>f</b>) fresh CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (10,000×), (<b>g</b>) used CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (5000×) and (<b>h</b>) used CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (10,000×).</p>
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<p>The SEM images of different OCs. (<b>a</b>) Fresh iron-based OCs (5000×), (<b>b</b>) fresh iron-based OCs (10,000×), (<b>c</b>) calcined CSSs (5000×), (<b>d</b>) calcined CSSs (10,000×), (<b>e</b>) fresh CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (5000×), (<b>f</b>) fresh CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (10,000×), (<b>g</b>) used CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (5000×) and (<b>h</b>) used CSS/Fe<sub>2</sub>O<sub>3</sub> oxygen carriers (10,000×).</p>
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<p>The H<sub>2</sub>-TPR patterns of different oxygen carriers. (<b>a</b>) Fresh iron-based OCs, (<b>b</b>) fresh CSS/Fe<sub>2</sub>O<sub>3</sub> composite oxygen carriers.</p>
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<p>Relative volume fractions of gas components at different cycle numbers.</p>
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25 pages, 10440 KiB  
Article
Analysis of Three-Dimensional Micro-Contact Morphology of Contact Groups Based on Superpixel AMR Morphological Features and Fractal Theory
by Jiahang Shen, Defeng Cui, Wenhua Li, Peidong Zhao, Xianchun Meng, Jiyuan Cai, Zheng Han and Haitao Wang
Appl. Sci. 2025, 15(5), 2842; https://doi.org/10.3390/app15052842 - 6 Mar 2025
Viewed by 121
Abstract
At the microscale, the three-dimensional morphological features of contact surfaces have a significant impact on the performance of electrical contacts. This paper aims to reconstruct the microscopic contact state of contact groups and to deeply study the effect of contact morphological features on [...] Read more.
At the microscale, the three-dimensional morphological features of contact surfaces have a significant impact on the performance of electrical contacts. This paper aims to reconstruct the microscopic contact state of contact groups and to deeply study the effect of contact morphological features on electrical contact performance. To fully obtain multimodal data such as the three-dimensional micro-morphological features and chemical composition distribution of contact surfaces, this paper proposes a contact surface feature-matching method based on entropy rate superpixel seed point adaptive morphological reconstruction. This method can adaptively retain meaningful seed points while filtering out invalid seed points, effectively solving the problem of over-segmentation in traditional superpixel segmentation method. Experimental results show that the proposed method achieves a segmentation accuracy of 92% and reduces over-segmentation by 30% compared to traditional methods. Subsequently, on the basis of the moving and static contact group difference plane model and the W-M model, this paper constructs a three-dimensional surface fractal contact model with an irregular base. This model has the ability to layer simulate multi-parameter elastic and plastic and to extract fractal parameter point cloud height, which can more accurately reflect the actual contact state of the contact group. The model demonstrates a 15% improvement in contact area prediction accuracy and a 20% reduction in contact resistance estimation error compared to existing models. Finally, this paper compares and verifies the theoretical feasibility of the model, providing a new theoretical contact model for the study of the impact of three-dimensional micro-morphology on the electrical contact reliability. Full article
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<p>Contact group image: (<b>a</b>) visual image; (<b>b</b>) three-dimensional reconstruction image (the color range from blue to red in this image indicates a change in surface height from low to high).</p>
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<p>Normalized intensity contact group morphology mirror image: (<b>a</b>) moving contact; (<b>b</b>) static contact.</p>
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<p>Contact group gradient direction degree image: (<b>a</b>) moving contact; (<b>b</b>) static contact.</p>
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<p>Segmentation of contact group morphological images using superpixel entropy rate with different clustering numbers: (<b>a</b>) clustering number is 500; (<b>b</b>) pseudo color effect, where clustering number is 500; (<b>c</b>) clustering number is 100; (<b>d</b>) pseudo color effect, where clustering number is 100.</p>
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<p>The result of AMR: (<b>a</b>) AMR segmentation, where <span class="html-italic">n</span> = 3; (<b>b</b>) AMR segmentation, where <span class="html-italic">n</span> = 4.</p>
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<p>ARM feature recognition flowchart based on LOG features.</p>
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<p>Contact group feature-matching diagrams: (<b>a</b>) static contact image; (<b>b</b>) moving contact image; (<b>c</b>) mixed image.</p>
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<p>Differential plane diagram (the color range from blue to red in this image indicates a change in surface height from low to high).</p>
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<p>3D fractal contact model diagram (blue represents moving contact points, while white represents stationary contact points).</p>
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<p>Base curved surface 3D model diagram (the color range from blue to yellow in this image indicates a change in surface height from low to high).</p>
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<p>Schematic diagram of multi-frequency micro−asperities synthesis: (<b>a</b>) <span class="html-italic">f</span> = 1; (<b>b</b>) <span class="html-italic">f</span> = 2; (<b>c</b>) <span class="html-italic">f</span> = 3; (<b>d</b>) <span class="html-italic">f</span> = 28.</p>
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<p>Schematic diagram of multi-frequency micro−asperities synthesis: (<b>a</b>) <span class="html-italic">f</span> = 1; (<b>b</b>) <span class="html-italic">f</span> = 2; (<b>c</b>) <span class="html-italic">f</span> = 3; (<b>d</b>) <span class="html-italic">f</span> = 28.</p>
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<p>Schematic diagram of the fractal model base.</p>
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<p>Schematic diagram of the micro-asperity deformation process.</p>
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<p>Normal total stiffness and normal load (this figure cited references [<a href="#B16-applsci-15-02842" class="html-bibr">16</a>,<a href="#B17-applsci-15-02842" class="html-bibr">17</a>]).</p>
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<p>Contact area and normal load.</p>
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<p>The ratio of normal load to total normal stiffness.</p>
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<p>Micro-asperity distribution map (the color range from blue to yellow in this image indicates a change in surface height from low to high).</p>
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<p>Relay design module schematic diagram.</p>
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<p>Relay electromagnetic module structure diagram.</p>
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<p>Environmental test box.</p>
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<p>The 3D non-contact analysis system.</p>
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20 pages, 10269 KiB  
Article
Viscoelasticity of PPA/SBS/SBR Composite Modified Asphalt and Asphalt Mixtures Under Pressure Aging Conditions
by Zongjie Yu, Xinpeng Ling, Ze Fan, Yueming Zhou and Zhu Ma
Polymers 2025, 17(5), 698; https://doi.org/10.3390/polym17050698 - 6 Mar 2025
Viewed by 81
Abstract
The viscoelastic behavior of asphalt mixtures is a crucial consideration in the analysis of pavement mechanical responses and structural design. This study aims to elucidate the molecular structure and component evolution trends of polyphosphoric acid (PPA)/styrene butadiene styrene block copolymer (SBS)/styrene butadiene rubber [...] Read more.
The viscoelastic behavior of asphalt mixtures is a crucial consideration in the analysis of pavement mechanical responses and structural design. This study aims to elucidate the molecular structure and component evolution trends of polyphosphoric acid (PPA)/styrene butadiene styrene block copolymer (SBS)/styrene butadiene rubber copolymer (SBR) composite modified asphalt (CMA) under rolling thin film oven test (RTFOT) and pressure aging (PAV) conditions, as well as to analyze the viscoelastic evolution of CMA mixtures. First, accelerated aging was conducted in the laboratory through RTFOT, along with PAV tests for 20 h and 40 h. Next, the microscopic characteristics of the binder at different aging stages were explored using Fourier-transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) tests. Additionally, fundamental rheological properties and temperature sweep tests were performed to reveal the viscoelastic evolution characteristics of CMA. Ultimately, the viscoelastic properties of CMA mixtures under dynamic loading at different aging stages were clarified. The results indicate that the incorporation of SBS and SBR increased the levels of carbonyl and sulfoxide factors while decreasing the level of long-chain factors, which slowed down the rate of change of large molecule content and reduced the rate of change of LMS by more than 6%, with the rate of change of overall molecular weight distribution narrowing to below 50%. The simultaneous incorporation of SBS and SBR into CMA mixtures enhanced the dynamic modulus in the 25 Hz and −10 °C range by 24.3% (AC-13), 15.4% (AC-16), and reduced the φ by 55.8% (AC-13), 40% (AC-16). This research provides a reference for the application of CMA mixtures in the repair of pavement pothole damage. Full article
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<p>Main performance indexes of BA and CMA before and after RTFOT.</p>
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<p>The designed gradation curves: (<b>a</b>) AC-13; (<b>b</b>) AC-16.</p>
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<p>Dynamic modulus test.</p>
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<p>Rheological properties before and after RTFOT aging of BA and CMA. (<b>a</b>) <math display="inline"><semantics> <mrow> <mi mathvariant="sans-serif">δ</mi> </mrow> </semantics></math>; (<b>b</b>) <math display="inline"><semantics> <mrow> <msup> <mrow> <mi mathvariant="normal">G</mi> </mrow> <mrow> <mo>∗</mo> </mrow> </msup> </mrow> </semantics></math>; (<b>c</b>) <math display="inline"><semantics> <mrow> <msup> <mrow> <mi mathvariant="normal">G</mi> </mrow> <mrow> <mo>∗</mo> </mrow> </msup> <mo>/</mo> <mi mathvariant="normal">s</mi> <mi mathvariant="normal">i</mi> <mi mathvariant="normal">n</mi> <mi mathvariant="sans-serif">δ</mi> </mrow> </semantics></math>; (<b>d</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> </mrow> <mrow> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">I</mi> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">P</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">I</mi> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>FTIR spectra of BA and CMA with different aging conditions. (<b>a</b>) FTIR spectra of BA and CMA with different aging conditions; (<b>b</b>) BA and CMA; (<b>c</b>) RTFOT; (<b>d</b>) PAV20; (<b>e</b>) PAV40.</p>
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<p>Changes in functional group indicators: (<b>a</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>I</mi> </mrow> <mrow> <mi>c</mi> <mo>=</mo> <mi>o</mi> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>I</mi> </mrow> <mrow> <mi>s</mi> <mo>=</mo> <mi>o</mi> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>Changes in functional group indicators: (<b>a</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>I</mi> </mrow> <mrow> <mi>L</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>I</mi> </mrow> <mrow> <mi>B</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>Changes in functional group indicators: (<b>a</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>I</mi> </mrow> <mrow> <mi>L</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>I</mi> </mrow> <mrow> <mi>B</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>Changes in functional group indicators: (<b>a</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">I</mi> </mrow> <mrow> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">r</mi> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) variation of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">I</mi> </mrow> <mrow> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">l</mi> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>Changes in functional group indicators at different aging stages.</p>
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<p>GPC results of BA and CMA: (<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>M</mi> </mrow> <mrow> <mi>w</mi> </mrow> </msub> </mrow> </semantics></math> distribution of BA; (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>M</mi> </mrow> <mrow> <mi>w</mi> </mrow> </msub> </mrow> </semantics></math> of BA of different aging conditions; (<b>c</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>M</mi> </mrow> <mrow> <mi>w</mi> </mrow> </msub> </mrow> </semantics></math> distribution of CMA; (<b>d</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>M</mi> </mrow> <mrow> <mi>w</mi> </mrow> </msub> </mrow> </semantics></math> of CMA of different aging conditions.</p>
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<p>Changes in molecular weight of BA and CMA before and after aging: (<b>a</b>) division of LMS, MMS, and SMS; (<b>b</b>) molecular weight distribution results.</p>
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<p>Marshall test results.</p>
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<p>Results of the analysis of road performance indicators.</p>
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<p><math display="inline"><semantics> <mrow> <msup> <mrow> <mi mathvariant="normal">E</mi> </mrow> <mrow> <mo>∗</mo> </mrow> </msup> </mrow> </semantics></math>: (<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>13</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>16</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>c</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>13</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>d</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>16</mn> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p><math display="inline"><semantics> <mrow> <mi>φ</mi> </mrow> </semantics></math>: (<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>13</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>16</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>c</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>13</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>d</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>16</mn> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>Master curve of <math display="inline"><semantics> <mrow> <msup> <mrow> <mi mathvariant="normal">E</mi> </mrow> <mrow> <mo>∗</mo> </mrow> </msup> </mrow> </semantics></math>: (<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>13</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>16</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>c</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>13</mn> </mrow> </msub> </mrow> </semantics></math>; (<b>d</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">M</mi> <mi mathvariant="normal">A</mi> </mrow> <mrow> <mi mathvariant="normal">A</mi> <mi mathvariant="normal">C</mi> <mo>−</mo> <mn>16</mn> </mrow> </msub> </mrow> </semantics></math>.</p>
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12 pages, 5153 KiB  
Article
Preparation of CL-20 with Controllable Particle Size Using Microfluidic Technology
by Zihao Zhang, Jin Yu, Yujia Wen, Hanyu Jiang, Siyu Xu, Yubao Shao, Ergang Yao, Heng Li and Fengqi Zhao
Molecules 2025, 30(5), 1176; https://doi.org/10.3390/molecules30051176 - 6 Mar 2025
Viewed by 183
Abstract
As a typical high-energy-density material, the sensitivity of CL-20 severely limits its application in explosives and propellants. Adjusting its structure at the microscopic level can effectively solve such problems. In this study, a microfluidic recrystallization technique was used to prepare ε-CL-20 with three [...] Read more.
As a typical high-energy-density material, the sensitivity of CL-20 severely limits its application in explosives and propellants. Adjusting its structure at the microscopic level can effectively solve such problems. In this study, a microfluidic recrystallization technique was used to prepare ε-CL-20 with three different particle sizes, with narrow particle size distributions (D50 = 2.77 μm, 17.22 μm and 50.35 μm). The prepared samples had fewer surface defects compared to the raw material. As the particle size decreased, the density of CL-20 increased and its impact sensitivity was significantly reduced. The activation energy of the CL-20 prepared using microfluidic technology increased with increases in particle size. Laser ignition experiments revealed that smaller CL-20 particles had the highest energy release efficiency, while larger particles exhibited a higher energy density and more stable energy release. The combustion performance and safety of CL-20 can be effectively improved by improving the crystal size distribution and surface morphology. Controllable preparation of multiple particle sizes of CL-20 was achieved using microfluidic recrystallization technology, which provides a reference for the preparation of multiple particle sizes of other energetic materials. Full article
(This article belongs to the Section Materials Chemistry)
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<p>SEM and statistical plots of particle size. (<b>a</b>) Raw CL-20, (<b>b</b>) S1, (<b>c</b>) S2, (<b>d</b>) S3. (<b>a1</b>,<b>a2</b>) SEM and particle size distribution of Raw CL-20; (<b>b1</b>,<b>b2</b>) SEM and particle size distribution of S1; (<b>c1</b>,<b>c2</b>) SEM and particle size distribution of S2; (<b>d1</b>,<b>d2</b>) SEM and particle size distribution of S3.</p>
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<p>Axial concentration distribution of solute on the (0 0 1) crystal face (<b>a</b>) before adsorption; (<b>b</b>) after adsorption [<a href="#B21-molecules-30-01176" class="html-bibr">21</a>]. (The black dashed box indicates that the axial concentration distribution curve of the ε-CL-20 molecule intersects the concentration curve of the crystal surface, indicating that some solutes have entered the groove area of the crystal face).</p>
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<p>XRD of raw CL-20, S1, S2, and S3.</p>
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<p>The angle of repose and density of raw CL-20, S1, S2 and S3.</p>
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<p>DSC curves of raw CL-20, S1, S2, and S3. (<b>a</b>) Raw CL-20, (<b>b</b>) S1, (<b>c</b>) S2, (<b>d</b>) S3.</p>
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<p>Images of flame propagation at 192 W/cm<sup>2</sup> for (<b>a</b>) raw CL-20, (<b>b</b>) S1, (<b>c</b>) S2, (<b>d</b>) S3.</p>
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<p>Ignition delay time of raw CL-20, S1, S2, and S3.</p>
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<p>Impact sensitivity and electrostatic spark sensitivity of raw CL-20, S1, S2, and S3.</p>
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<p>The microfluidic system.</p>
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25 pages, 14389 KiB  
Article
Investigating Traffic Characteristics at Freeway Merging Areas in Heterogeneous Mixed-Flow Environments
by Shubo Wu, Yajie Zou, Danyang Liu, Xinqiang Chen, Yinsong Wang and Amin Moeinaddini
Sustainability 2025, 17(5), 2282; https://doi.org/10.3390/su17052282 - 5 Mar 2025
Viewed by 234
Abstract
The rapid development of Connected and Autonomous Vehicles (CAVs) presents challenges in managing mixed traffic flows. Previous studies have primarily focused on mixed traffic flow involving CAVs and Human-Driven Vehicles (HDVs), or on the combination of trucks and cars. However, these studies have [...] Read more.
The rapid development of Connected and Autonomous Vehicles (CAVs) presents challenges in managing mixed traffic flows. Previous studies have primarily focused on mixed traffic flow involving CAVs and Human-Driven Vehicles (HDVs), or on the combination of trucks and cars. However, these studies have not fully addressed the heterogeneous mixed traffic flow consisting of CAVs and HDVs, including trucks and cars, influenced by varying human driving styles. Therefore, this study investigates the influences of the market penetration rate (MPR) of CAVs, truck proportion, and driving style on operational characteristics in heterogeneous mixed traffic flow. A total of 1105 events were extracted from highD dataset to analyze four car-following types: car-following-car (CC), car-following-truck (CT), truck-following-car (TC), and truck-following-truck (TT). Principal Component Analysis (PCA) and clustering techniques were employed to categorize distinct driving styles, while the Intelligent Driver Model (IDM) was calibrated to represent the various car-following behaviors. Subsequently, microscopic simulations were conducted using the Simulation of Urban Mobility (SUMO) platform to evaluate the impact of CAVs on sustainable traffic operations, including road capacity, stability, safety, traffic oscillations, fuel consumption, and emissions under various traffic conditions. The results demonstrate that CAVs can significantly enhance road capacity, improve emissions, and stabilize traffic flow at high MPRs. For instance, when the MPR increases from 40% to 80%, the road capacity improves by approximately 25%, while stability enhances by approximately 33%. In contrast, higher truck proportions lead to reduced capacity, increased emissions, and decreased traffic flow stability. In addition, an increased proportion of mild drivers reduces capacity, raises emissions per kilometer, and improves stability and safety. However, a high proportion of mild human drivers (e.g., 100% mild drivers) may negatively impact traffic safety when CAVs are present. This study provides valuable insights into evaluating heterogeneous traffic flows and supports the development of future traffic management strategies for more sustainable transportation systems. Full article
(This article belongs to the Section Sustainable Transportation)
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<p>Research framework of this study.</p>
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<p>Trends of evaluation metrics for different clustering methods applied to CC events. (<b>a</b>) silhouette score; (<b>b</b>) DB index.</p>
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<p>Classification diagrams for different car-following types. (<b>a</b>) CC; (<b>b</b>) CT; (<b>d</b>) TC; (<b>d</b>) TT.</p>
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<p>Kernel density estimation distributions for driving behavior parameters. (<b>a</b>) Acceleration; (<b>b</b>) deceleration; (<b>c</b>) THW; (<b>d</b>) CIF. The colors are for visual distinction only.</p>
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<p>Fitting performance for different optimization algorithms.</p>
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<p>Schematic diagram of the simulation road segment.</p>
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<p>Density–flow plots for different traffic conditions.</p>
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<p>Impact of IDM parameters on stability. (<b>a</b>) <span class="html-italic">B</span> = 4.07, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>s</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math> = 3.83, and <span class="html-italic">τ</span> = 1.33; (<b>b</b>) <math display="inline"><semantics> <mrow> <mi>A</mi> </mrow> </semantics></math> = 1.13, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>s</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math> = 3.83, and <math display="inline"><semantics> <mrow> <mi>τ</mi> </mrow> </semantics></math> = 1.33; (<b>c</b>) <math display="inline"><semantics> <mrow> <mi>A</mi> </mrow> </semantics></math> = 1.13, <math display="inline"><semantics> <mrow> <mi>B</mi> </mrow> </semantics></math> = 4.07, and <math display="inline"><semantics> <mrow> <mi>τ</mi> </mrow> </semantics></math> = 1.33; (<b>d</b>) <math display="inline"><semantics> <mrow> <mi>A</mi> </mrow> </semantics></math> = 1.13, <math display="inline"><semantics> <mrow> <mi>B</mi> </mrow> </semantics></math> = 4.07, and <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>s</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math> = 3.83.</p>
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<p>Impact of IDM parameters on stability. (<b>a</b>) <span class="html-italic">B</span> = 4.07, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>s</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math> = 3.83, and <span class="html-italic">τ</span> = 1.33; (<b>b</b>) <math display="inline"><semantics> <mrow> <mi>A</mi> </mrow> </semantics></math> = 1.13, <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>s</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math> = 3.83, and <math display="inline"><semantics> <mrow> <mi>τ</mi> </mrow> </semantics></math> = 1.33; (<b>c</b>) <math display="inline"><semantics> <mrow> <mi>A</mi> </mrow> </semantics></math> = 1.13, <math display="inline"><semantics> <mrow> <mi>B</mi> </mrow> </semantics></math> = 4.07, and <math display="inline"><semantics> <mrow> <mi>τ</mi> </mrow> </semantics></math> = 1.33; (<b>d</b>) <math display="inline"><semantics> <mrow> <mi>A</mi> </mrow> </semantics></math> = 1.13, <math display="inline"><semantics> <mrow> <mi>B</mi> </mrow> </semantics></math> = 4.07, and <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>s</mi> </mrow> <mrow> <mn>0</mn> </mrow> </msub> </mrow> </semantics></math> = 3.83.</p>
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<p>Stability curves of different car-following types.</p>
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<p>Stability analysis of heterogeneous traffic flow. (<b>a</b>) Only normal; (<b>b</b>) realistic proportions; (<b>c</b>) only mild.</p>
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<p>Speeds and accelerations of vehicles under different MPRs of CAV. (<b>a</b>) MPR = 40%; (<b>b</b>) MPR = 60%; (<b>c</b>) MPR = 80%.</p>
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<p>Speeds and accelerations of vehicles under different truck proportions. (<b>a</b>) Truck = 10%; (<b>b</b>) truck = 20%; (<b>c</b>) truck = 30%.</p>
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<p>Speeds and accelerations of vehicles with different compositions of driving styles. (<b>a</b>) Only normal; (<b>b</b>) realistic proportions; (<b>c</b>) only mild.</p>
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<p>Comparison of average CIF values under different scenarios.</p>
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<p>Spatiotemporal diagrams under different scenarios with a truck proportion of 10%. (<b>a</b>) MPR = 40%; (<b>b</b>) MPR = 60%; (<b>c</b>) MPR = 80%.</p>
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<p>Spatiotemporal diagrams under different scenarios with a truck proportion of 20%. (<b>a</b>) MPR = 40%; (<b>b</b>) MPR = 60%; (<b>c</b>) MPR = 80%.</p>
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<p>Spatiotemporal diagrams under different scenarios with a truck proportion of 30%. (<b>a</b>) MPR = 40%; (<b>b</b>) MPR = 60%; (<b>c</b>) MPR = 80%.</p>
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<p>Comparison of fuel consumption and emissions under different scenarios.</p>
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17 pages, 9632 KiB  
Article
Wear and Corrosion Behavior of Diamond-like Carbon Coatings in Artificial Saliva
by Monika Madej, Katarzyna Piotrowska, Martin Vicen and Viera Zatkaliková
Coatings 2025, 15(3), 305; https://doi.org/10.3390/coatings15030305 - 5 Mar 2025
Viewed by 280
Abstract
This study investigates the properties of diamond-like carbon (DLC) coatings deposited onto a Ti6Al4V titanium alloy using plasma-assisted chemical vapor deposition (PACVD). The research encompasses adhesion tests, hardness, surface characterization, as well as corrosion and tribological evaluations. Artificial saliva was employed as both [...] Read more.
This study investigates the properties of diamond-like carbon (DLC) coatings deposited onto a Ti6Al4V titanium alloy using plasma-assisted chemical vapor deposition (PACVD). The research encompasses adhesion tests, hardness, surface characterization, as well as corrosion and tribological evaluations. Artificial saliva was employed as both the lubricating and corrosive medium. Microscopic examination revealed a uniform coating with a thickness of about 3.2 µm. Scratch test results indicated that the deposited DLC coating exhibited superior adhesion, lower frictional resistance, and reduced wear compared to the titanium alloy. The coating deposition increased the hardness of the Ti6Al4V alloy by about 75%. Friction coefficients, measured under dry and lubricated conditions, were approximately 80% lower for the DLC-coated samples. Corrosion studies revealed that both the coated and uncoated surfaces demonstrated typical passive behavior and high corrosion resistance in artificial saliva. For DLC coatings, the corrosion current density and the corrosion rate were reduced by 85%. Microscopic observations of wear tracks following tribological and scratch tests confirmed the inferior wear and scratch resistance of the titanium alloy relative to the DLC coating. Under both dry and lubricated conditions (with artificial saliva), the volumetric wear rate of the titanium alloy was over 90% higher than for the DLC coating. Full article
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Graphical abstract

Graphical abstract
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<p>Three-electrode corrosion cell: 1—heating circuit, 2—auxiliary Pt electrode, 3—SCE reference electrode, 4—sample.</p>
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<p>Friction pair: view (<b>a</b>), diagram (<b>b</b>), 1—load, 2—temperature sensor, 3—ball, 4—coating, 5—sample.</p>
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<p>Linear distribution of elements and coating thickness on the cross-section.</p>
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<p>Ti6Al4V axonometric image 3D (<b>a</b>), primary surface profile (<b>b</b>).</p>
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<p>DLC axonometric image 3D (<b>a</b>), primary surface profile (<b>b</b>).</p>
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<p>Scratch test DLC: optical images (<b>a</b>), graph (<b>b</b>).</p>
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<p>Scratch test Ti6Al4V: optical images (<b>a</b>), graph (<b>b</b>).</p>
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<p>Two-dimensional axonometric image of a scratch: Ti6Al4V (<b>a</b>), DLC (<b>b</b>).</p>
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<p>Potentiodynamic polarization curves.</p>
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<p>Details of potentiodynamic polarization curves in linear axes for comparison of the passive current densities in the passivity regions above 0.15 V vs. SCE. Passivity is sustained when the current density remains below a critical threshold of 0.05 mA/cm<sup>2</sup>. Exceeding this threshold can result in the loss of passivity [<a href="#B47-coatings-15-00305" class="html-bibr">47</a>].</p>
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<p>Example waveforms: coefficients of friction (<b>a</b>), linear wear (<b>b</b>).</p>
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<p>Average values: coefficients of friction (<b>a</b>) and linear wear (<b>b</b>).</p>
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<p>Three-dimensional axonometric images, Ti6Al4V: dry friction (<b>a</b>), artificial saliva (<b>b</b>); DLC: dry friction (<b>c</b>), artificial saliva (<b>d</b>).</p>
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22 pages, 12118 KiB  
Article
Modern Comprehensive Metabolomic Profiling of Pollen Using Various Analytical Techniques
by Petra Krejčí, Zbyněk Žingor, Jana Balarynová, Andrea Čevelová, Matěj Tesárek, Petr Smýkal and Petr Bednář
Molecules 2025, 30(5), 1172; https://doi.org/10.3390/molecules30051172 - 5 Mar 2025
Viewed by 151
Abstract
Pollen is a cornerstone of life for plants. Its durability, adaptability, and complex design are the key factors to successful plant reproduction, genetic diversity, and the maintenance of ecosystems. A detailed study of its chemical composition is important to understand the mechanism of [...] Read more.
Pollen is a cornerstone of life for plants. Its durability, adaptability, and complex design are the key factors to successful plant reproduction, genetic diversity, and the maintenance of ecosystems. A detailed study of its chemical composition is important to understand the mechanism of pollen–pollinator interactions, pollination processes, and allergic reactions. In this study, a multimodal approach involving Fourier transform infrared spectrometry (FTIR), direct mass spectrometry with an atmospheric solids analysis probe (ASAP), matrix-assisted laser desorption/ionization (MALDI) and ultra-high-performance liquid chromatography–mass spectrometry (UHPLC-MS) was applied for metabolite profiling. ATR-FTIR provided an initial overview of the present metabolite classes. Phenylpropanoid, lipidic, and carbohydrate structures were revealed. The hydrophobic outer layer of pollen was characterized in detail by ASAP-MS profiling, and esters, phytosterols, and terpenoids were observed. Diacyl- and triacylglycerols and carbohydrate structures were identified in MALDI-MS spectra. The MALDI-MS imaging of lipids proved to be helpful during the microscopic characterization of pollen species in their mixture. Polyphenol profiling and the quantification of important secondary metabolites were performed by UHPLC-MS in context with pollen coloration and their antioxidant and antimicrobial properties. The obtained results revealed significant chemical differences among Magnoliophyta and Pinophyta pollen. Additionally, some variations within Magnoliophyta species were observed. The obtained metabolomics data were utilized for pollen differentiation at the taxonomic scale and provided valuable information in relation to pollen interactions during reproduction and its related applications. Full article
(This article belongs to the Special Issue Applied Analytical Chemistry: Second Edition)
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<p>ATR-FTIR spectra of conifer, monocot, and dicot representatives. (<b>A</b>)—Pine (<span class="html-italic">Pinus nigra</span>). (<b>B</b>)—Spruce (<span class="html-italic">Picea abies</span>). (<b>C</b>)—Tulip (<span class="html-italic">Tulipa x gesneriana</span>). (<b>D</b>)—King cup (<span class="html-italic">Caltha palustrir</span>).</p>
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<p>PCA score plot from ASAP-MS analysis in positive ionization mode of studied pollen species. (<b>A</b>)—All studied species. (<b>B</b>)—Magnoliophyta species.</p>
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<p>ASAP-MS spectra of conifer, monocot, and dicot representatives. (<b>A</b>)—Pine (<span class="html-italic">Pinus nigra</span>). (<b>B</b>)—Spruce (<span class="html-italic">Picea abies</span>). (<b>C</b>)—Tulip (<span class="html-italic">Tulipa x gesneriana</span>). (<b>D</b>)—King cup (<span class="html-italic">Caltha palustrir</span>). The intensity number in each panel is referred to as the most intense peak in the spectrum (100%). Identified signals are given in bold.</p>
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<p>Boxplots of normalized intensities of selected signals in studied pollen species measured by ASAP-MS. (<b>A</b>)—Dehydroabietic acid (<span class="html-italic">m</span>/<span class="html-italic">z</span> 301.2162). (<b>B</b>)—Ester of linolenic acid and methyloxooctadecanoate (<span class="html-italic">m</span>/<span class="html-italic">z</span> 575.5053). (<b>C</b>)—β-sitosterol (<span class="html-italic">m</span>/<span class="html-italic">z</span> 397.3810). (<b>D</b>)—Octadecatetraendiol (<span class="html-italic">m</span>/<span class="html-italic">z</span> 279.2334).</p>
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<p>LDI-MS spectra of conifer, monocot, and dicot representatives. (<b>A</b>)—Pine (<span class="html-italic">Pinus nigra</span>), (<b>B</b>)—Tulip (<span class="html-italic">Tulipa x gesneriana</span>), (<b>C</b>)—King cup (<span class="html-italic">Caltha palustrir</span>). The intensity number in each panel refers to the most intense peak in the spectrum (100%). Identified signals are given in bold.</p>
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<p>MALDI-MS imaging analysis of selected pollens attached to double-sided tape on the MALDI imaging plate. (<b>A</b>)—Photo of the studied pollen mixture. (<b>B</b>)—Dehydroabietol cinnamate (<span class="html-italic">m</span>/<span class="html-italic">z</span> 455.2228). (<b>C</b>)—Linolenoyl–linoleoyl–palmitoyl–glycerol (<span class="html-italic">m</span>/<span class="html-italic">z</span> 891.6803). (<b>D</b>)—Trilinolenoyl–glycerol (<span class="html-italic">m</span>/<span class="html-italic">z</span> 911.6513).</p>
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<p>Quantity of selected phenolic acids (<b>A</b>) and flavonoids (<b>B</b>) in all studied pollen species.</p>
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<p>Quantity of selected anthocyanins in studied pollens.</p>
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<p>UHPLC-MS analysis of pollen extracts. (<b>A</b>)—King cup (<span class="html-italic">Caltha palustrir</span>). (<b>B</b>)—Pine (<span class="html-italic">Pinus nigra</span>). (<b>C</b>)—Tulip (<span class="html-italic">Tulipa x gesneriana</span>). Chromatograms are reconstructed for <span class="html-italic">m</span>/<span class="html-italic">z</span> 301.0357 (which represents parent ion of quercetin or aglycone arising during fragmentation of its glycosylated forms). Retention time of peaks of following identified compounds are denoted in bold: quercetin (<span class="html-italic">m</span>/<span class="html-italic">z</span> 301.0357, Rt 8.10 min), quercetin dihexoside (<span class="html-italic">m</span>/<span class="html-italic">z</span> 625.1423, Rt 6.40 min), quercetin hexoside (<span class="html-italic">m</span>/<span class="html-italic">z</span> 463.0886, Rt 7.12 min), and its modified form (<span class="html-italic">m</span>/<span class="html-italic">z</span> 447.0967, Rt 7.92 min). Intensity is related to most intensive peak in chromatograms (100%). Identified signals are given in bold.</p>
Full article ">Figure 10
<p>Scheme of another collection and pollen isolation process.</p>
Full article ">Figure A1
<p>Scheme of taxonomical classification of studied pollen species. Magnoliophyta are currently divided into Liliopsida (monocots), Magnoliopsida (magnoliids), and Rosopsida (eudicots). The latter two involved former dicots.</p>
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<p>FTIR-ATR spectra of all studied pollen species. (<b>A</b>)—Wavenumbers 4000−2200 cm<sup>−1</sup>. (<b>B</b>)—Wavenumbers 2200–400 cm<sup>−1</sup>. The top green line represents pine pollen, and the bottom green line represents spruce pollen. The top purple line represents rose pollen, and the bottom purple line represents snowflake pollen. The top dark green line represents magnolia pollen, and the bottom dark green line represents beech pollen. The top dark purple line represents geranium pollen, and the bottom dark purple line represents scilla pollen.</p>
Full article ">Figure A3
<p>Peak area of cyanidin, cyanidin hexoside, and cyanidin dihexoside in different coloured tulip pollens.</p>
Full article ">Figure A4
<p>PCA score plot from UHPLC-MS analysis of studied pollen species in negative ionization mode.</p>
Full article ">Figure A5
<p>Application of capillary tube for direct pollen analysis using ASAP-MS technique. Arrow shows capillary modification and pollen insertion.</p>
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