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Formation of LiF-rich cathode-electrolyte interphase is highly desirable for wide-temperature battery, but its application is hindered by the unwanted side reactions associated with conventional method of introducing fluorinated additives. Here, we developed an additive-free strategy to produce LiF-rich cathode electrolyte interphase (CEI) by low-temperature formation cycling. Using LiNi0.33Mn0.33Co0.33O2 as a model cathode, the atomic ratio of LiF in the CEI formed at -5 °C is about 17.7%, enhanced by ~550% compared to CEI formed at 25 °C (2.7%). The underlying mechanism is uncovered by both experiments and theoretic simulation, indicating that the decomposition of LiPF6 to LiF is transformed into spontaneous and exothermic on positively charged cathode surface and lowering the temperature shift chemical equilibrium towards the formation of LiF-rich CEI. Superior to conventional fluorinated additives, this approach is free from unwanted side reactions, imparting batteries with both high-temperature (60 oC) cyclability and low-temperature rate performance (capacity enhanced by 100% at 3 C at -20 oC). This low-temperature formation cycling to construct LiF-rich CEI is extended to various cathode systems, such as LiNi0.8Mn0.1Co0.1O2, LiCoO2, LiMn2O4, demonstrating the versatility and potential impact of our strategy in advancing the performance and stability of wide-temperature batteries and beyond.
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Elevated temperature landfills (ETLFs) are municipal solid waste (MSW) landfills that have been impacted by subsurface exothermic reactions (SERs) and display unusual gas and leachate composition. Leachate quantity and quality data were analyzed to identify indicators of a SER at an ETLF in Ohio, USA. ETLF leachate generation increased from 2.04 to 14.4 m3/hectare-day (218 to 1,539 gallons/acre-day), peaking 16 months after the reaction was first noticed. The leachate generation rate for this ETLF remains about two times greater than the average Ohio MSW landfill. Several general parameters such as pH, electrical conductivity (EC), and total dissolved solids (TDS) remain impacted 5 years later. Similarly, metals such as arsenic, iron, calcium, potassium, and magnesium have increased in concentration. Volatile organic compounds (VOCs) behavior was less consistent as a group of chemicals. Increases of VOCs such as acetone, benzene, and methyl ethyl ketone (MEK) also increased. Importantly, in one year, benzene exceeded its toxicity characteristic threshold meaning the leachate was a hazardous waste, substantially increasing treatment and disposal costs. It is not clear if the VOCs are produced directly by the SER or if they are an indicator that microbial processes -which would otherwise consume them- have been disrupted. ETLFs likely do not all undergo the same exothermic reaction(s) and, unlike the analysis of landfill gas composition, temporal changes in leachate constituents' concentrations may be more important than comparing to absolute values.
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Pultrusion is a high-volume manufacturing process for Fibre-Reinforced Polymer (FRP) composites. It requires careful tuning and optimisation of process parameters to obtain the maximum production rate. The present work focuses on the correlation between the set die temperatures of 80 °C, 100 °C, 120 °C, and 140 °C and the resin cure state at constant pull speeds. Lab-scale oven trials were conducted to understand the thermal behaviour of the resin system and to provide a temperature range for the pultrusion trials. Dielectric Analysis (DEA) was used during pultrusion trials to monitor the effect of die temperature on the cure progression. The DEA results showed that, by increasing die temperature, the exothermic peak shifts closer towards the die entry. Moreover, the degree of cure for samples processed at 140 °C was 97.7%, in comparison to 86.2% for those cured at 100 °C. The rate of conversion and the degree of cure correspond directly to the set die temperatures of the pultrusion trials, contributing to understanding the effect of die temperature on cure progression. Mechanical and thermal material properties were measured. Samples cured at 120 °C showed the highest mechanical performance, exceeding those cured at 140 °C, linked to the generation of higher internal stress due to the higher rate of conversion. This work can be used as a guide for pultruded composite sections, to understand the cure behaviour of resin systems under various applied temperatures and the impact of the die temperature conditions on thermal and mechanical properties.
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Negative electrode materials with high thermal stability are a key strategy for improving the safety of lithium-ion batteries for electric vehicles without requiring built-in safety devices. To search for crucial clues into increasing the thermal stability of these materials, we performed differential scanning calorimetry (DSC) and in situ high-temperature (HT)-X-ray diffraction (XRD)/X-ray absorption (XAS) up to 450 °C with respect to a solid-solution compound of Li4/3-2x/3ZnxTi5/3-x/3O4 with 0 ≤ x ≤ 0.5. The DSC profile of fully discharged x = 0.5 (Li2ZnTi3O8) with a LiPF6-based electrolyte could be divided into three temperature (T) regions: (i) T ≤ 250 °C for ΔHaccumi, (ii) 250 °C < T ≤ 350 °C for ΔHaccumii, and (iii) T > 350 °C for ΔHaccumiii, where ΔHaccumn is the accumulated change in enthalpy in region n. The HT-XRD/XAS analyses clarified that ΔHaccumi and ΔHaccumii originated from the decomposition of solid electrolyte interphase (SEI) films and the formation of a LiF phase, respectively. Comparison of the DSC profiles with x = 0 (Li[Li1/3Ti5/3]O4) and graphite revealed the operating voltage, i.e., amount of SEI films, and stability of the crystal lattice play significant roles in the thermal stability of negative electrode materials. Indeed, the highest thermal stability was attained at x = 0.25 using this approach.
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This paper presents the implementation of the first stage of a study on the synthesis of the intermetallic compound in the Ni-Al system under shock-wave extrusion (SWE). A method was developed and experiments involving SWE of the reactive Ni-Al powder mixture were carried out. As a result, it was possible to obtain up to 56 vol.% of the final product and achieve 100% synthesis of NiAl. The results of metallographic analysis indicate that the process of high-velocity collapse of the tube created conditions for the formation of a cumulative flow, which directly affects the phase formation in NiAl. It was shown that the presence of the central hole in the powder sample reduced the effect of the Mach stem on the homogeneity of the NiAl structure. It was also determined that with a central hole with a 5 mm diameter, the effect of the Mach stem could not be observed at all. The goals of further studies are achieving 90-100 vol.% of the final product and reducing the porosity in the final product. Preliminary experimental studies have shown great potential for SWE to produce composite metal-intermetallic materials.
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The interaction of curcumin (Cur) with human angiogenin (hAng), a potent blood vessel inducer responsible for angiogenesis is found to change following encapsulation within the ß-cyclodextrin (ßCD) cavity. The enhanced bioavailability and increase in the binding stoichiometry of hAng:Cur-ßCD (1:2) leads to increased affinity, hence an increase in the association constant. The altered mode of hAng inhibition of Cur from a non-competitive (KI = 23.7 ± 2.2 µM) to a mixed type (KI = 19.8 ± 1.4 µM), after encapsulation provides an insight into interaction patterns. Isothermal titration calorimetry (ITC) experiments indicate the formation of multiple favorable non-covalent interactions (also confirmed by docking studies), which implies negative enthalpy changes (-ΔHo) and restriction in the dynamic mobility of the free protein molecule resulting in a very less positive entropy change (TΔSo). This leads to a medium magnitude for the spontaneous free energy change associated with the interaction/binding process. The spontaneity of binding indicates a more favorable value for the Cur-ßCD (ΔGo = -7.75 kcal/mol) compared to Cur (ΔGo = -7.49 kcal/mol). In vivo studies also demonstrate the anti-angiogenic effect of Cur/Cur-ßCD confirmed by the significant decrease in blood vessel density and branching index.
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Curcumina , beta-Ciclodextrinas , Calorimetría/métodos , Curcumina/química , Curcumina/farmacología , Humanos , Ribonucleasa Pancreática , Termodinámica , beta-Ciclodextrinas/química , beta-Ciclodextrinas/farmacologíaRESUMEN
Locust powder was converted into water-soluble fluorescent nitrogen-doped carbon dots (N-CDs) with gram-scale yield through a self-exothermic reaction between nitric acid and diethylenetriamine (DETA) within 10 min. The morphology, elemental information, and optical properties of the N-CDs were characterized using high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared, ultraviolet-visible and fluorescence spectroscopy. Spectroscopic investigation indicated that the fluorescence emission behaviour of N-CDs is excitation wavelength dependent, with the strongest emission peak at 470 nm using a 390 nm excitation wavelength. The strong absorption peak of sunset yellow (SY) at 482 nm overlaps substantially with the blue emission peak (470 nm) of N-CDs. This enables the fluorescence emission of N-CDs to be obviously quenched by SY through the inner filter effect. There was a good linear relationship between the fluorescence quenching degree and the concentrations of SY within the range 0.5-40 µM. The detection limit of developed fluorescence assay for SY is 28 nM, and the relative standard deviation is 2.3% (c = 10 µM). The N-CDs derived from locusts by the self-exothermic reaction are highly selective and sensitive fluorescent probes for SY, which were applied to the fluorescence sensing of SY in different food samples with satisfactory results.
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Saltamontes , Puntos Cuánticos , Animales , Compuestos Azo , Carbono , Colorantes Fluorescentes , Nitrógeno , Espectrometría de FluorescenciaRESUMEN
For the integration of a reactive multilayer system (iRMS) with a high exothermic reaction enthalpy as a heat source on silicon wafers for low-temperature bonding in the 3D integration and packaging of microsystems, two main conflicting issues should be overcome: heat accumulation arising from the layer interface pre-intermixing, which causes spontaneous self-ignition during the deposition of the system layers, and conductive heat loss through the substrate, which leads to reaction propagation quenching. In this work, using electron beam evaporation, we investigated the growth of a high exothermic metallic Pd/Al reactive multilayer system (RMS) on different Si-wafer substrates with different thermal conduction, specifically a bare Si-wafer, a RuOx or PdOx layer buffering Si-wafer, and a SiO2-coated Si-wafer. With the exception of the bare silicon wafer, the RMS grown on all other coated wafers underwent systematic spontaneous self-ignition surging during the deposition process once it reached a thickness of around 1 µm. This issue was surmounted by investigating a solution based on tuning the output energy by stacking alternating sections of metallic reactive multilayer Pd/Al and Ni/Al systems that have a high and medium enthalpy of exothermic reactions, respectively. This heterostructure with a bilayer thickness of 100 nm was successfully grown on a SiO2-coated Si-wafer to a total thickness of 3 µm without any spontaneous upsurge of self-ignition; it could be electrically ignited at room temperature, enabling a self-sustained propagating exothermic reaction along the reactive patterned track without undergoing quenching. The results of this study will promote the growth of reactive multilayer systems by electron beam evaporation processing and their potential integration as local heat sources on Si-wafer substrates for bonding applications in microelectronics and microsystems technology.
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It was known for long that Ni-Al composite powders can be used to deposit self-bonding coating as a bond coat for common ceramic coatings due to the exothermic reaction between Ni and Al. However, it was found that with commercial Ni-Al composite powders with a large particle size, it is difficult to ignite the self-propagating reaction between Ni and Al to form Ni-Al intermetallics by plasma spraying. In this study, Ni-Al composite powder particles of different sizes were used to prepare Ni-Al intermetallics-based coatings by plasma spraying. The dependencies of the exothermic reaction between Ni and Al and the coating microstructure on powder particle size and spray parameters were investigated. The phase composition, microstructure, porosity and oxide content of the coatings were characterized by x-ray diffraction, scanning electron microscope and image analyzing. The results show that particle size of Ni-Al composite powders is the dominant factor controlling the exothermic reaction for the formation of Ni-Al intermetallics during plasma spraying. When the powders larger than about 50 µm are used, the reaction forming aluminide cannot complete even by heating of plasma flame generated at high plasma arc power. However, when smaller powders less than 50 µm are used, the exothermic reaction can completely occur rapidly in plasma spraying, contributing to heating of Ni-Al droplets to the highest temperature for development of the self-bonding effect. The positive relationship between molten droplet temperature and tensile adhesive strength of the resultant coatings is recognized to confirm the contribution of high droplet temperature to the adhesive or cohesive strength.
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In this study, the exothermic temperature performance of various Al/Ni multilayer powders with particle sizes ranging from under 75 to over 850 µm, which generate enormous heat during self-propagating exothermic reactions, was determined using a high-speed sampling pyrometer. The Al/Ni multilayer powders were prepared by a cold-rolling and pulverizing method. The multilayer constitution of the Al/Ni multilayer powders was examined by observing the cross-section of the powders using scanning electron microscopy; the results indicate that the powders had similar lamellar structures regardless of the particle size. Exothermic reactions were carried out to measure the temperature changes during the experiment using a pyrometer. We found that the maximum temperature and the duration of the exothermic reaction increased with an increase in the particle size caused by the heat dissipation of the surface area of the Al/Ni multilayer powder. This indicates that the thermal characteristics of the exothermic reaction of the Al/Ni multilayer powder can be controlled by adjusting the particle size of the Al/Ni multilayer powder. Finally, we concluded that this controllability of the exothermic phenomenon can be applied as a local heating source in a wide range of fields.
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Frost tolerance is an important factor influencing plant growth, plant species distribution and competitive balance among plant species in the face of climate change. Traditional methods for estimating frost tolerance are often time consuming and require a large sample size, limiting the temporal and spatial resolutions. Differential thermal analysis (DTA) can be advantageous compared to other methods used to determine frost tolerance, most importantly by (1) increasing the number of tested species, tissue types and sampling dates, (2) allowing to test frost tolerance in situ, and (3) more realistically testing the influence of freezing rate and duration. Here, we discuss a typical procedure for DTA, compare its use to other frost tolerance methods and point out its limitations.
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Adaptación Biológica , Análisis Diferencial Térmico , Congelación , Fenómenos Fisiológicos de las Plantas , Estaciones del Año , Análisis Diferencial Térmico/métodos , Especificidad de Órganos , FenotipoRESUMEN
Metal matrix composites (MMCs) are promising alternatives to metallic alloys. Their high strength-to-weight ratios; high temperature stabilities; and unique thermal, electrical, and chemical properties make them suitable for automotive, aerospace, defense, electrical, electronic, energy, biomedical, and other applications. The wide range of potential combinations of materials allows the properties of MMCs to be tailored by manipulating the morphology, size, orientation, and fraction of reinforcement, offering further opportunities for a variety of applications in daily life. This Special Issue, "Metal Matrix Composites", addresses advances in the material science, processing, material modeling and characterization, performance, and testing of metal matrix composites.
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Cyanoacrylate is an acrylic resin that is used as an adhesive in acrylic nail glues and various other strong, rapidly acting adhesives, such as "Dermabond" and "Super Glue." This adhesive is very effective in a variety of settings; however, when cyanoacrylate comes into contact with cotton fibers, an exothermic reaction occurs that is severe enough to cause a full-thickness burn to the underlying skin. Full-thickness burns requiring excision and skin grafting can be psychologically devastating for patients, especially the pediatric population and their parents, who may believe they are to blame for their child's burn. We present the case of a 2-year-old boy who developed a full-thickness burn after spilling acrylic nail glue onto his cotton shirt. Fortunately, his burn was small enough that excision with primary closure was able to be performed. However, he unfortunately developed hypertrophic scarring postoperatively. Owing to the widespread use of cyanoacrylate adhesives in the general population, it is important to spread awareness of the potential dangers associated with these adhesives to prevent potential physical and psychological injuries related to improper use of these adhesives.
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Soil contamination with polycyclic aromatic hydrocarbons (PAHs) is a serious problem in Northeast China, especially in the steel industrial area. The objective of this study was to evaluate the feasibility of using basic oxygen furnace (BOF) slag to activate the Fenton-like remediation of PAH-contaminated soil to achieve the objectives of "waste control by waste" and "resource recycling" in Chinese steel industry. The effects of BOF slag dosages, H2O2 concentrations, and exothermicity-driven evaporation were evaluated with respect to the removal efficiencies of phenanthrene (Phe) and pyrene (Pyr). Results indicated that PAH oxidation was proportional to the BOF slag dosages and was increased exponentially with H2O2 concentrations. Evaporation due to increasing temperature caused by exothermic reaction played an important role in total soil PAH losses. The sequential Fenton-like oxidation with a 3-times application of 15% H2O2 and the same BOF slag repeatedly used were able to remove 65.87% of Phe and 58.33% of Pyr, respectively. Soluble iron oxides containing in BOF slag were reduced, while amorphous iron oxide concentration remained stable during the repeated Fenton-like process. Column study mimics real field applications showing high removal efficiencies of Phe (36.05-83.20%) and Pyr (21.79-68.06%) in 30-cm depth of soil profile. The tests on soluble heavy metal concentrations after the reactions with high slag dosage or high H2O2 concentration confirmed that BOF slag would not cause heavy metal contamination. Consequently, BOF slag may provide an efficient way for enhancing the Fenton-like based remediation of heavily PAH-polluted soil with little risk on collateral heavy metal contamination. However, an external gas collection and purification equipment would be essential to eliminate the evaporated PAHs.
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Restauración y Remediación Ambiental/métodos , Peróxido de Hidrógeno/química , Fenantrenos/análisis , Pirenos/análisis , Contaminantes del Suelo/análisis , Catálisis , China , Residuos Industriales , Oxidación-Reducción , Oxígeno , Hidrocarburos Policíclicos Aromáticos , Suelo , AceroRESUMEN
We present the mixing and merging of two reactive droplets on top of an open surface. A mobile droplet (1.0 M HCl solution + iron oxide particles) is magnetically-actuated to merge with a sessile droplet (1.0 M NaOH + phenolphthalein). The heat from the exothermic reaction is detected by a thermocouple. We vary the droplet volume (1, 5 and 10 µL), the magnet speed (1.86, 2.79, 3.72 and 4.65 mm/s) and the iron oxide concentration (0.010, 0.020 and 0.040 g/mL) to study their influences on the mixing time, peak temperature and cooling time. The sampled recording of these processes are provided as supplementary files. We observe the following trends. First, the lower volume of droplet and higher speed of magnet lead to shorter mixing time. Second, the peak temperature increases and cooling time decreases at the increasing speed of magnet. Third, the peak temperature is similar for bigger droplets, and they take longer to cool down. Finally, we also discuss the limitations of this preliminary study and propose improvements. These observations could be used to improve the sensitivity of the open chamber system in measuring the exothermic reaction of biological samples.
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INTRODUCTION: Due to thermal hazard during composite restorations, this study was designed to scan the pulp temperature by thermocouple and infrared camera during photo polymerizing different composites. METHODS AND MATERIALS: A mesio-occlso-distal (MOD) cavity was prepared in an extracted tooth and the K-type thermocouple was fixed in its pulp chamber. Subsequently, 1 mm increment of each composites were inserted (four composite types were incorporated) and photo polymerized employing either LED or QTH systems for 60 sec while the temperature was recorded with 10 sec intervals. Ultimately, the same tooth was hemisected bucco-lingually and the amalgam was removed. The same composite curing procedure was repeated while the thermogram was recorded using an infrared camera. Thereafter, the data was analyzed by repeated measured ANOVA followed by Tukey's HSD Post Hoc test for multiple comparisons (α=0.05). RESULTS: The pulp temperature was significantly increased (repeated measures) during photo polymerization (P=0.000) while there was no significant difference among the results recorded by thermocouple comparing to infrared camera (P>0.05). Moreover, different composite materials and LCUs lead to similar outcomes (P>0.05). CONCLUSION: Although various composites have significant different chemical compositions, they lead to similar pulp thermal changes. Moreover, both the infrared camera and the thermocouple would record parallel results of dental pulp temperature.
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This paper is devoted to the modeling of the pyrolysis process in order to predict mass and heat loss profiles of a used tire sample and ultimately prevent eventual difficulties in pyrolysis reactors. Once assumptions are made, the thermal balances and kinetics of each reaction were written. The resolution of the differential equations allowed us to present the profile of heat variation within the sample as a function of temperature in a fixed bed reactor. The modeling is based on the energy behavior of each reaction, the rate conversion of which was also modeled and compared with that obtained experimentally. There is a satisfactory agreement between the theoretical and the experimental results in one hand and a good fit with experimental and regression results of other researchers in another hand. It was shown in particular, that some exothermic reactions intervene during the pyrolysis of the used tires. Indeed, the exothermic heat at the center of 2â¯cm particle exceeds 1500â¯kJ/kg which presents an economic and energetic payoff for the plant. It has also been noted that the small particle size can result in faster heat transfer and shorten the process completion time. At the same time, rapid heat transfer can trigger more endothermic reactions, increasing thus the overall energy consumption of the process.
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The self-propagating exothermic chemical reaction with transient thermovoltage, known as the thermopower wave, has received considerable attention recently. A greater peak voltage and specific power are still demanded, and materials with greater Seebeck coefficients have been previously investigated. However, this study employs an alternative mechanism of transient chemical potential gradient providing an unprecedentedly high peak voltage (maximum: 8 V; average: 2.3 V) and volume-specific power (maximum: 0.11 W mm-3 ; average: 0.04 W mm-3 ) using n-type single-crystalline Bi2 Te3 substrates. A mixture of nitrocellulose and sodium azide is used as a fuel, and ultraviolet photoelectron spectroscopy reveals a significant downshift in Fermi energy (≈5.09 eV) of the substrate by p-doping of the fuel. The induced electrical potential by thermopower waves has two distinct sources: the Seebeck effect and the transient chemical potential gradient. Surprisingly, the Seebeck effect contribution is less than 2.5% (≈201 mV) of the maximum peak voltage. The right combination of substrate, fuel doping, and anisotropic substrate geometry results in an order of magnitude greater transient chemical potential gradient (≈5.09 eV) upon rapid removal of fuel by exothermic chemical reaction propagation. The role of fuel doping and chemical potential gradient can be viewed as a key mechanism for enhanced heat to electric conversion performance.
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AIM: To evaluate ex vivo the effect of several simulated pulpal blood flow rates on the change in pulp chamber temperature during direct fabrication of a provisional restoration using a polymethylmethacrylate (PMMA) resin. METHODOLOGY: Fifteen noncarious human premolars were prepared for complete coverage restorations. A curved needle connected to a peristaltic pump simulated the pulp blood flow. Two K-type thermocouples connected to a digital thermometer were placed in the pulp chamber, and the assembly was placed in an incubator at 37 °C. Three provisional crowns were made for each specimen using no water flow (group 1), a 1-mL min-1 flow rate (group 2) and a 0.5-mL/min-1 flow rate (group 3). The pulp chamber temperature was recorded continuously during polymerization until the temperature increase peaked and started to decrease and reached the baseline temperature (37 °C). The temperature increase was measured for the three water flow conditions. Data were analysed statistically using descriptive statistics, repeated measures one-way analysis of variance (anova) with Greenhouse-Geisser correction and Bonferroni tests. The level of significance was set at P < 0.05. RESULTS: All of the groups were associated with an increased pulp chamber temperature. Groups with flow rates at 1 and 0.5 mL min-1 had a significantly lower temperature rise when compared to the group without water flow (P < 0.001). CONCLUSIONS: Direct fabrication of provisional restorations can cause a critical increase in pulp chamber temperature. However, in the presence of simulated pulpal blood flow rates of 1 or 0.5 mL min-1 , the increase in pulp chamber temperature did not exceed the critical threshold (5.6 °C).
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Velocidad del Flujo Sanguíneo/fisiología , Cavidad Pulpar/irrigación sanguínea , Pulpa Dental/fisiología , Pulpa Dental/irrigación sanguínea , HumanosRESUMEN
Although all-solid-state lithium-ion batteries (ALIBs) have been believed as the ultimate safe battery, their true character has been an enigma so far. In this paper, we developed an all-inclusive-microcell (AIM) for differential scanning calorimetry (DSC) analysis to clarify the degree of safety (DOS) of ALIBs. Here AIM possesses all the battery components to work as a battery by itself, and DOS is determined by the total heat generation ratio (ΔH) of ALIB compared with the conventional LIB. When DOS = 100%, the safety of ALIB is exactly the same as that of LIB; when DOS = 0%, ALIB reaches the ultimate safety. We investigated two types of LIB-AIM and three types of ALIB-AIM. Surprisingly, all the ALIBs exhibit one or two exothermic peaks above 250 °C with 20-30% of DOS. The exothermic peak is attributed to the reaction between the released oxygen from the positive electrode and the Li metal in the negative electrode. Hence, ALIBs are found to be flammable as in the case of LIBs. We also attempted to improve the safety of ALIBs and succeeded in decreasing the DOS down to â¼16% by incorporating Ketjenblack into the positive electrode as an oxygen scavenger. Based on ΔH as a function of voltage window, a safety map for LIBs and ALIBs is proposed.