Thermochimica Acta最新文献

{"title":"Kinetics of thermal decomposition and hydrogen reduction of Cobalt compounds: A review","authors":"Sonja Pöyhtäri ,&nbsp;Eetu-Pekka Heikkinen ,&nbsp;Anne Heikkilä","doi":"10.1016/j.tca.2025.179952","DOIUrl":"10.1016/j.tca.2025.179952","url":null,"abstract":"<div><div>Cobalt is an important transition metal that plays a critical role in the growing battery industry, and in hard metal applications and super alloys. Cobalt powder can be produced via solid-state hydrogen reduction of different cobalt compounds from which cobalt oxides have been widely studied since 1960s. Hydrogen is an efficient and environmentally friendly reductant and its utilization in metal refining is being increasingly studied. This paper presents an overview of important findings regarding hydrogen reduction kinetics of cobalt oxides alongside thermal decomposition kinetics of cobalt carbonates and hydroxides. This will assist researchers in the future to choose and modify hydrogen reduction parameters by identifying the factors affecting the overall reduction reaction of different cobalt compounds and characteristics of derived cobalt products.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"746 ","pages":"Article 179952"},"PeriodicalIF":3.1,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394464","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advanced avrami formula and its application to describing the isothermal crystallisation of polymers","authors":"László Mihály Vas ,&nbsp;Emese Slezák ,&nbsp;Kolos Molnár ,&nbsp;Ferenc Ronkay","doi":"10.1016/j.tca.2025.179950","DOIUrl":"10.1016/j.tca.2025.179950","url":null,"abstract":"<div><div>The classic Avrami formula has widely been used to describe and characterize the crystallisation process of polymers. We showed that the Avrami formula is not correct for the random nucleation. To eliminate this and some problems of fitting the Avrami formula with integer exponent revealed in the literature, we modified the Avrami equation and derived a new extended formula that can describe instantaneous and random (time-dependent) nucleation simultaneously. This formula may give information on the crystalline structure of both types of nuclei; moreover, it makes it possible to determine the crystalline fraction developed from the instantaneous nuclei. The latter enables us to estimate, for example, the effect of nucleating agents numerically on the crystallisation process and the ultimate crystallinity. The applicability of the new formula was validated by performing isothermal crystallisation tests on poly(ethylene-terephthalate) (PET), polypropylene (PP), low- and high-density polyethylene (LDPE and HDPE) samples at various temperatures, which resulted in a better fit characterized by the much smaller relative maximum absolute error (0.4–2.9 %) related to that for the Avrami equation (1.9–15.9 %).</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"746 ","pages":"Article 179950"},"PeriodicalIF":3.1,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lyophilized globular proteins under rapid heating: High thermal stability and properties of the resulting material","authors":"Timur Mukhametzyanov ,&nbsp;Sanjarbek Nazimov ,&nbsp;Christoph Schick","doi":"10.1016/j.tca.2024.179919","DOIUrl":"10.1016/j.tca.2024.179919","url":null,"abstract":"<div><div>A notable feature of globular proteins is their relatively poor thermostability. Water, while being important in maintaining the native protein structure, participates in many thermal degradation processes either directly (hydrolysis, deamidation) or indirectly by enhancing the mobility of protein molecules. It has been long known that reducing hydration enhances the thermal stability of proteins. However, the temperature stability of essentially dry proteins is unexplored because the traditional means of heating cause the charring of proteins. Fast Scanning Calorimetry (FSC) is a technique that allows rapid heating and cooling of micrometer-size samples. It was previously used to determine the melting point of silk fibroin. Here we demonstrate that under rapid heating, the dried powders of globular proteins remain stable up to ca. 200 °C. Further heating produces a glass-like material without charring. The glass transition temperature of the produced material is above 200 °C. The results may be of potential interest for additive manufacturing of biocompatible products.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"744 ","pages":"Article 179919"},"PeriodicalIF":3.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143165562","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Facile preparation of functional decorated of phase change materials composites based on paraffin @ sodium alginate","authors":"Xiangyun Kong ,&nbsp;Jinge Lu ,&nbsp;Mengkun Xu,&nbsp;Mengyuan Song,&nbsp;Keqing Li,&nbsp;Wenshuai Qiu,&nbsp;Jiali Zhang,&nbsp;Xi Chen,&nbsp;Yongxin Liu","doi":"10.1016/j.tca.2024.179922","DOIUrl":"10.1016/j.tca.2024.179922","url":null,"abstract":"<div><div>A novel and simple one-step method was proposed for the preparation of multifunctional microencapsulated phase change materials to satisfy the requirements of different application scenarios. Here, with the help of the super reaction ability and coordination effect of metal ions Zn²⁺, the paraffin (PCM) was well encapsulated by the sodium alginate (SA) shell by the cross-linking between SA and Zn²⁺. At the same time, Na₂S·9H₂O and 2-MeIM were selected to realize the loading of ZnS quantum dots and ZiF-8 in the materials by their coordination with excess Zn²⁺ in the system. The results of differential scanning calorimeter (DSC), Ultraviolet-visible-near-infrared (UV–vis-NIR), Photoluminescence and Brunauer–Emmett–Teller (BET) indicated that the obtained PCM@SA/ZnS and PCM@SA/ZiF-8 not only retained good heat resistance and heat storage properties, but also had new functions such as fluorescence and adsorption. This work would provide a new idea for the development of multi-functional composite materials.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"744 ","pages":"Article 179922"},"PeriodicalIF":3.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143165561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Determination of polymorphic forms of hydroxy-2-naphthoic acid and the corresponding solubility in twelve mono-solvents","authors":"Huanxin Li ,&nbsp;Xin Ding ,&nbsp;Bingling Yu ,&nbsp;Feilong Sun ,&nbsp;Bo Zhu ,&nbsp;Kenan Sun","doi":"10.1016/j.tca.2024.179921","DOIUrl":"10.1016/j.tca.2024.179921","url":null,"abstract":"<div><div>The polymorphs of 1‑hydroxy-2-naphthoic acid (HNA) were screened in twelve organic solvents. Five aprotic solvents – acetone, acetonitrile, methyl acetate, ethyl acetate, and n-propyl acetate – along with n-butanol crystalized HNA in Form II. Meanwhile, HNA in Form I was obtained from methanol, ethanol, n-propanol, isopropanol, 2-butanol, and isobutanol. Solubility data of the two polymorphs was determined with static method, and fitted with λh equation, van't Hoff equation, Apelblat model, NRTL, and Wilson model, with Apelblat the most accurate based on ARD and RMSD. The dissolving process was affected significantly by hydrogen bond propensity and cohesive energy density. Moreover, Hansen solubility parameters analyses indicate that the smaller <span><math><mrow><mstyle><mi>Δ</mi></mstyle><mover><mrow><msub><mi>δ</mi><mi>t</mi></msub></mrow><mo>‾</mo></mover></mrow></math></span>, the better solubility of HNA. Additionally, the intermolecular interactions imply that both the van der Waals interaction and hydrogen bonding interaction take the leading role in affecting the solubility. The thermodynamic parameters suggest that the dissolving process is spontaneous and entropy increasing.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"744 ","pages":"Article 179921"},"PeriodicalIF":3.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143165564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New insights on thermal energy storage using nanoparticle enhanced tin","authors":"Tagore M ,&nbsp;Suganthi K S ,&nbsp;Haariz J A ,&nbsp;Rajan K S","doi":"10.1016/j.tca.2024.179918","DOIUrl":"10.1016/j.tca.2024.179918","url":null,"abstract":"<div><div>This work investigates the influence of different nanoparticles on the reduction of the supercooling degree of tin (phase change material) and the quantity of latent heat recovered during the early stages of freezing in nanoparticle-enhanced phase change materials (NePCM). Different nanoparticles (Cu, CuO, MgO, SiO_x, TiO₂, ZnO) at various concentrations (0.125 wt. %, 0.25 wt. %, 0.5 wt. %, 1 wt. %, 2 wt. %) were used to prepare NePCM using planetary ball milling. The supercooling degree of tin (43.9 K) was found to be suppressed to 22 K in NePCM. The NePCM containing 0.25 wt. % of Cu and the one containing 0.5 wt. % of MgO allowed extraction of 64.2 % and 54.8 % of thermal energy stored, respectively, at temperatures greater than the onset temperature of freezing of pure tin. Thus, our study has uniquely demonstrated the impact of chosen nanomaterials in improving the freezing characteristics of tin.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"744 ","pages":"Article 179918"},"PeriodicalIF":3.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143165563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polymorphism and thermal stability of nesquehonite (MgCO3·3H2O) regulated by magnesium L-aspartate: For CO2 mineral sequestration","authors":"Mengxu Xu ,&nbsp;Shushuang Yao ,&nbsp;Yujuan Gao ,&nbsp;Yang Bai ,&nbsp;Jiayong Teng ,&nbsp;Weiyao Liu ,&nbsp;Wanshun Cui ,&nbsp;Zilin Meng ,&nbsp;Pingke Yan","doi":"10.1016/j.tca.2024.179920","DOIUrl":"10.1016/j.tca.2024.179920","url":null,"abstract":"<div><div>Prepared by hydrothermal method, the nesquehonite (MgCO₃·3H₂O) was characterized through different testing and analysis techniques. The study investigated the influence of <span>l</span>-aspartic acid regulation on the morphology, structure, and thermal stability of the nesquehonite. SEM and DSC results indicated that the sample had larger size and higher thermal stability. Building on it, the reaction mechanism using magnesium <span>l</span>-aspartate as a reactant was further explored, confirming that the formation of O-Mg coordination bonds induced nucleation self-assembly of crystals, effectively enhancing thermal stability. Compared to conventional methods, the initial decomposition temperature of the crystals prepared in this study increased by 42.5 %. This study provides a theoretical basis for the indirect mineralization of CO₂ to produce magnesium carbonates. Furthermore, the direct incorporation of biomolecular polymeric salts offers a novel perspective for understanding the role of organic additives in the process of crystals mineralization.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"744 ","pages":"Article 179920"},"PeriodicalIF":3.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigating secondary crystallisation of polyamide-12 using fast scanning calorimetry","authors":"Benjamin Sanders ,&nbsp;Matthew North ,&nbsp;Edward Cant ,&nbsp;Michael Jenkins","doi":"10.1016/j.tca.2025.179948","DOIUrl":"10.1016/j.tca.2025.179948","url":null,"abstract":"<div><div>Polyamide 12 (PA-12) is a strong and durable thermoplastic commonly used within advanced polymer processing techniques, such as powder bed fusion (PBF). The use of PA-12 for the fabrication of functional, end-use components is highly dependent on the morphology, size, shape, and stability of the crystalline phase. Secondary crystallisation, an aging process rarely studied in previous PA-12 Lature, can cause further developments in crystallinity that also alter the property profile of the material during PBF. To the best of the authors knowledge, this is the first in-depth investigation into the secondary crystallisation behaviour of PA-12 using fast scanning calorimetry (FSC). Results indicated that, across a wide isothermal crystallisation temperature (T_c) range, the crystalline structure, rate of secondary crystallisation, and the mechanism of lamellar thickening, are all closely correlated to crystallisation time (t_c) and temperature (T_c). At crystallisation temperatures between 100 °C and 130 °C, PA-12 crystallises into the hexagonal gamma (γ) phase, whilst T_c ≥ 140 °C, larger and more thermodynamically stable alpha-prime (α’) crystals are able to grow. Independent of crystal polymorph, there is significant evidence of secondary crystallisation. For extended t_c, the melting endotherm progressively shifts to higher temperatures, indicative of a slow, yet continuous lamellar thickening process. In γ crystals, the melting enthalpy and melting temperature increase linearly as a function of the logarithm of t_c (R² &gt; 0.96), suggesting that solid-state diffusion processes such as chain-sliding and chain refolding are the dominant cause of lamellar thickening. However, within the α’ phase, hydrogen bonding can be more easily attained, resulting in a more rigid crystal structure that reduces chain mobility and prevents lamellar thickening via chain sliding or refolding. Thickening instead occurs through the incorporation of inter-lamellae amorphous chains, across the melt-crystal interface, via Hay's reptation-diffusion mechanism. This is evidenced by the thickening of α’ crystals becoming dependent on the square root of time (R² &gt; 0.96). Such insight into the secondary crystallisation behaviour of PA-12 could be useful within the PBF industry in order to help predict the volume shrinkage effects associated with polymer crystallisation, allowing improvements to the dimensional precision and performance of final components. Similarly, an enriched understanding of the mechanisms and rate of secondary crystallisation could reveal more information about the thermal properties of un-sintered PA-12 powder, and its suitability for re-use in future build cycles.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"745 ","pages":"Article 179948"},"PeriodicalIF":3.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"How to correctly evaluate kinetics based on experimental data of reaction calorimetry","authors":"Arcady Kossoy,&nbsp;Yury Akhmetshin,&nbsp;Elena Koludarova","doi":"10.1016/j.tca.2025.179947","DOIUrl":"10.1016/j.tca.2025.179947","url":null,"abstract":"<div><div>Reaction calorimetry (RC) is a powerful experimental technique with a wide range of applications. A significant advantage of RC is the ability to simultaneously measure the heat generated by the reaction and the current composition of the reacting mixture, which provides more complete information about the reaction and its kinetics. This makes it a useful tool for studying reaction kinetics, although this method is rather complicated and requires a thorough elaboration of the methodology of experimentation and data processing.</div><div>The literature on RC theory is extensive, yet there is a lack of recognition regarding some methodical aspects of utilizing RC data to construct kinetic models. This paper aims to draw attention to these aspects. In particular:</div><div>the need for careful analysis of experimental data is emphasized and demonstrated,</div><div>the importance of applying the concept of key species to obtain unique kinetics is shown, as is the need to consider the effects of feed rate and reactants’ ratios to properly plan kinetic experiments,</div><div>the usefulness of kinetic modeling for better understanding of reaction progress is demonstrated.</div><div>The material is based on the results of a study of the well-known methanol - acetic anhydride esterification reaction taken from the literature.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"745 ","pages":"Article 179947"},"PeriodicalIF":3.1,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Review of supercooling suppression of phase change materials based on nanoparticles","authors":"Yuguo Gao ,&nbsp;Yanan Zhao ,&nbsp;Xinyu Wang ,&nbsp;Mohammaderfan Mohit ,&nbsp;Minghan Xu ,&nbsp;Agus P. Sasmito","doi":"10.1016/j.tca.2025.179936","DOIUrl":"10.1016/j.tca.2025.179936","url":null,"abstract":"<div><div>The phenomenon of supercooling in phase change materials has been a major obstacle to the effective use of these materials in thermal energy storage systems. Numerous studies have shown that nanoparticles display significant advantages over other methods of supercooling inhibition in terms of increased nucleation rate, enhanced thermal conductivity, reduced supercooling, and improved cycling stability. Yet, the mechanism of supercooling inhibition by nanoparticles has not been comprehensively discussed or reviewed in published articles. The objective of this review is to provide a comprehensive analysis of the mechanisms by which nanoparticles promote nucleation and reduce supercooling in phase change materials, as well as to discuss the most influential factors such as the type, concentration, and size of the nanoparticles, as well as ultrasonic and synergistic effects. Additionally, the paper focuses on an overview of recent advances in the application of machine learning to control the supercooling of nanofluid phase change materials. The potential for practical applications of machine learning techniques to enhance the thermophysical properties of phase change materials and suppress phase change material supercooling is one of our major findings.</div></div>","PeriodicalId":23058,"journal":{"name":"Thermochimica Acta","volume":"745 ","pages":"Article 179936"},"PeriodicalIF":3.1,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143170461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}