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17 pages, 1527 KiB  
Review
Mechanisms Behind the Soil Organic Carbon Response to Temperature Elevations
by Yonglin Wu, Haitao Li, Xinran Liang, Ming Jiang, Siteng He and Yongmei He
Agriculture 2025, 15(11), 1118; https://doi.org/10.3390/agriculture15111118 - 22 May 2025
Viewed by 704
Abstract
Soil organic carbon (SOC) represents the most dynamic component of the soil carbon pool and is pivotal in the global carbon cycle. Global temperature rise and increasing drought severity are now indisputable realities, making soil organic carbon cycling under climate warming a critical [...] Read more.
Soil organic carbon (SOC) represents the most dynamic component of the soil carbon pool and is pivotal in the global carbon cycle. Global temperature rise and increasing drought severity are now indisputable realities, making soil organic carbon cycling under climate warming a critical research priority. This review elucidates the mechanism of the SOC response to temperature increase in terms of both extrinsic and intrinsic factors. The extrinsic factors are temperature elevation methods, rainfall, and land use. Different methods of temperature increase have their own unique advantages and disadvantages. Indoor warming methods exclude other factors, making temperature the only variable, but tend to ignore carbon inputs. In situ field warming and soil displacement methods help researchers explore the response of the complete ecosystem carbon cycle to temperature increase but cannot exclude the interference of factors such as rainfall. Elevated rainfall mitigates the adverse effects of elevated temperatures on organic carbon sequestration. In addition, the response of SOC to temperature elevations vary among different land use types. The temperature sensitivity of SOC is higher in peatland (high organic matter) alpine meadows (colder regions). The intrinsic factors that affect the response of SOC to elevated temperatures are SOC components, microorganisms, SOC temperature sensitivity, and SOC stability. The SOC decomposition rate is influenced by variations in the ratios of decomposable (easily oxidizable organic carbon (EOC), dissolved organic carbon (DOC), and microbial biomass carbon (MBC)) and stabilizing (inert organic carbon (IOC), alkyl carbon, and aromatic carbon) SOC to total organic carbon (TOC). Furthermore, temperature elevations also affect the soil microenvironment, resulting in microbial community reorganization such as changes in bacterial and fungal ratios and abundance. At the same time, soil aggregates, clay minerals, and iron and aluminum oxides protect the SOC, making it difficult to be utilized by microbial decomposition. The systematic clarification of the mechanism behind the SOC response to higher temperatures is crucial for accurately predicting and modeling global carbon cycles and effectively responding to the loss of SOC pools due to global temperature elevations. Full article
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22 pages, 6072 KiB  
Article
Understanding the Effect of IM-5 Zeolite Treated with Hexafluorosilicic Acid for the Methanol Alkylation of Pseudocumene
by Shumin Hao, Yongrui Wang, Enhui Xing and Xuhong Mu
Materials 2025, 18(10), 2252; https://doi.org/10.3390/ma18102252 - 13 May 2025
Cited by 1 | Viewed by 459
Abstract
A study systematically investigating the structural modifications and catalytic performance of IM-5 zeolite treated with hexafluorosilicic acid in pseudocumene alkylation with methanol was carried out. Characterization techniques revealed significant alterations in crystal structure, morphology, textural properties, coordination environment, and acidity induced by the [...] Read more.
A study systematically investigating the structural modifications and catalytic performance of IM-5 zeolite treated with hexafluorosilicic acid in pseudocumene alkylation with methanol was carried out. Characterization techniques revealed significant alterations in crystal structure, morphology, textural properties, coordination environment, and acidity induced by the modifications. Catalytic evaluations demonstrated altered pseudocumene conversion, durene selectivity, and products distribution for optimized samples, with IM-5-0.01 (treated with 0.01 M modifier) showing superior activity stability. The improved performance was attributed to two key factors: a stable framework with high-density medium-strength Brønsted acid sites facilitating complete alkylation and expanded mesoporous volume promoting efficient product diffusion to mitigate deactivation. Conversely, reduced durene selectivity in modified samples stem from intensified isomerization reactions driven by increased external surface area, resulting in higher C9 product fractions. In contrast, the parent IM-5 zeolite exhibited rapid deactivation, with durene selectivity peaking at 40 h before declining. Mechanistic insights revealed dynamic processes including dealumination, defect formation, silicon repair, and aluminum redistribution during treatment, providing a theoretical foundation for rational catalyst design in alkylation reactions. Full article
(This article belongs to the Section Catalytic Materials)
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12 pages, 2948 KiB  
Article
Green Synthesis and Particle Size Control of High-Purity Alumina Based on Hydrolysis of Alkyl Aluminum
by Shuang Zheng, Yao Lu and Huanyu Zhao
Materials 2025, 18(9), 2100; https://doi.org/10.3390/ma18092100 - 3 May 2025
Viewed by 561
Abstract
This study introduces a green synthesis strategy for producing high-purity alumina (≥99.99%) through the controlled hydrolysis of aluminum isopropoxide, coupled with a novel impurity removal protocol to address persistent challenges in conventional methods, such as residual silicon/iron impurities and particle agglomeration. The experimental [...] Read more.
This study introduces a green synthesis strategy for producing high-purity alumina (≥99.99%) through the controlled hydrolysis of aluminum isopropoxide, coupled with a novel impurity removal protocol to address persistent challenges in conventional methods, such as residual silicon/iron impurities and particle agglomeration. The experimental results indicate that La2O3, 1-(2-pyridylazo)-2-naphthol (PAN), and phenolphthalein exhibit effective removal capabilities for silicon/iron impurities. The addition of 1 wt% La2O3 reduces silicon content from 99.7 ppm to 16.4 ppm, whereas 0.6 wt% PAN and 0.2 wt% phenolphthalein, employed as iron-binding agents, lower iron content from 66.4 ppm to 20.7 ppm and 9.7 ppm, respectively. Through optimized dropwise hydrolysis and subsequent calcination at 1200 °C for 4 h, nanosized alumina powders with uniform morphology and controlled particle sizes (274–832 nm) were successfully synthesized. The proposed method offers a scalable and efficient pathway for synthesizing high-purity alumina with tailored particle characteristics. Full article
(This article belongs to the Section Green Materials)
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25 pages, 18900 KiB  
Article
Fabrication of Papillary Composite Microstructured Aluminum Surfaces by Laser Shock Imprinting and Ablation
by Zongbao Shen, Qizhi Xu, Yansong Yu, Dong Liu and Jie Ji
Metals 2024, 14(12), 1346; https://doi.org/10.3390/met14121346 - 26 Nov 2024
Viewed by 820
Abstract
Laser shock ablation is incorporated into laser shock imprinting for the fabrication of papillary composite microstructures on aluminum surfaces. The primary papillary structures are fabricated using laser shock imprinting. Subsequently, secondary structures were fabricated on the surface of these primary structures using laser [...] Read more.
Laser shock ablation is incorporated into laser shock imprinting for the fabrication of papillary composite microstructures on aluminum surfaces. The primary papillary structures are fabricated using laser shock imprinting. Subsequently, secondary structures were fabricated on the surface of these primary structures using laser shock ablation, forming composite papillary microstructures. The influence of various laser shock ablation process parameters on the formation effect of these papillary composite microstructure surfaces was investigated. The results indicate that both laser shock energy and shock frequency affect the integrity of the secondary microstructure coverage on the material surface, the height of the composite microstructure, and the surface morphology. Through comparative optimization, the optimal process parameters were determined to be 675 mJ of energy and one shock ablation. Additionally, the differences in the flow behavior of metallic materials between the center and the periphery of the beam spot, caused by the shock wave, were analyzed. The wettability of the composite microstructure aluminum surface was also explored. The variation mechanism of wettability was explained by detecting changes in the contact angle on the aluminum surface at different time intervals and analyzing changes in surface chemical composition before and after aging. Specifically, after laser shock ablation, the aluminum surface contains a large number of polar groups, making it hydrophilic. During aging treatment, these polar groups continuously adsorb non-polar alkyl organic compounds, eventually leading to hydrophobicity, with a stabilized average surface contact angle of 143°. Fluorination treatment can further achieve superhydrophobicity, with a contact angle of 151° achieved shortly after processing the composite microstructure aluminum surface. Full article
(This article belongs to the Special Issue Advanced Digital Design and Laser Manufacturing in Metallic Materials)
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14 pages, 3441 KiB  
Article
Metal-Exchanged Phosphomolybdic Acid Salts-Catalyzed Esterification of Levulinic Acid
by Márcio José da Silva, Alana Alves Rodrigues and Wilton Keisuke Taba
Processes 2024, 12(11), 2574; https://doi.org/10.3390/pr12112574 - 17 Nov 2024
Cited by 1 | Viewed by 934
Abstract
We examined the effectiveness of metal-exchanged phosphomolybdic acid salts in converting levulinic acid, derived from biomass, into valuable products (alkyl levulinate). We prepared salts of phosphomolybdic acid using different metals (Fe3+, Al3+, Zn2+, Cu2+, Mn [...] Read more.
We examined the effectiveness of metal-exchanged phosphomolybdic acid salts in converting levulinic acid, derived from biomass, into valuable products (alkyl levulinate). We prepared salts of phosphomolybdic acid using different metals (Fe3+, Al3+, Zn2+, Cu2+, Mn2+, Ni2+, and Co2+). The influence of metal cations on the conversion and selectivity of the reactions was assessed. We found that the salts prepared with iron and aluminum phosphomolybdate were the most effective catalysts for the esterification of levulinic acid with methanol, with the conversion and selectivity tending towards 100% after 6 h of reaction at a temperature of 323 K. The effect of catalyst loading and its recovery and reuse was evaluated; the results from the reaction using aluminum phosphomolybdate remained similar for four cycles of use. The influence of temperature on conversion and selectivity was investigated between 298 and 353 K. The reactivity of different alcohols with a carbon chain size of C1-C4 was assessed and conversions above 65% were obtained for all alcohols tested under the conditions evaluated, except for tert-butyl alcohol. These catalysts are a promising alternative to the traditional soluble and corrosive Brønsted acid catalysts. The superior performance of these catalysts was ascribed to the higher pH decline triggered by the hydrolysis of these metal cations. Full article
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16 pages, 3885 KiB  
Article
Hydrogen Bond Donors in the Catalytic Pocket: The Case of the Ring-Opening Polymerization of Cyclic Esters Catalyzed by an Amino-Propoxide Aluminum Complex
by Salvatore Impemba, Antonella Viceconte, Irene Tozio, Shoaib Anwar, Gabriele Manca and Stefano Milione
Polymers 2024, 16(21), 3047; https://doi.org/10.3390/polym16213047 - 30 Oct 2024
Viewed by 1003
Abstract
A new aluminum complex (NSO)AlMe2 featuring a hydrogen bond donor on the ligand backbone has been synthesized via the reaction of AlMe3 with 1-((2-(isopropylamino)phenyl)thio)propan-2-ol (NSO-H) and spectroscopically characterized. In the complex, the aluminum atom is in a distorted tetrahedral coordination sphere [...] Read more.
A new aluminum complex (NSO)AlMe2 featuring a hydrogen bond donor on the ligand backbone has been synthesized via the reaction of AlMe3 with 1-((2-(isopropylamino)phenyl)thio)propan-2-ol (NSO-H) and spectroscopically characterized. In the complex, the aluminum atom is in a distorted tetrahedral coordination sphere determined by the anionic oxygen and neutral nitrogen atoms of the ligand and by the two carbon atoms of the alkyl groups. After proper activation, the complex (NSO)AlMe2 was able to promote the ring-opening polymerization of L-, rac-lactide, ε-caprolactone and rac-β-butyrolactone. The polymerization of rac-lactide was faster than that of L-lactide: in a toluene solution at 80 °C, the high monomer conversion of 100 equivalents was achieved in 1.5 h, reaching a turnover frequency of 63 molLA·molAl–1·h–1. The experimental molecular weights of the obtained polymers were close to those calculated, assuming the growth of one polymer chain for one added alcohol equivalent and the polydispersity indexes were monomodal and narrow. The kinetic investigation of the polymerization led to the determination of the apparent propagation constants and the Gibbs free energies of activation for the reaction; the terminal groups of the polymers were also identified. The complex (NSO)AlMe2 was active in harsh conditions such as at a very low concentration or in the melt using technical-grade rac-lactide. A relatively high level of activity was observed in the ring-opening polymerization of ε-caprolactone and rac-β-butyrolactone. DFT calculations were performed and revealed the central role of the NH function of the coordinated ligand. Acting as a hydrogen bond donor, it docks the monomer in the proximity of the metal center and activates it toward the nucleophilic attack of the growing polymer chain. Full article
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14 pages, 6570 KiB  
Article
Dewaterability Enhancement of Anaerobic Sludge Using Polymeric Aluminum Chloride and Polyoxyethylene Alkyl Ether Surfactants
by Eunhye Song, Eunju Kim, Gyeong Woo Kim, Cheol Jin Jeong, Wonbae Lee and Seong Kuk Han
Water 2024, 16(16), 2303; https://doi.org/10.3390/w16162303 - 15 Aug 2024
Viewed by 1469
Abstract
The use of coagulants, such as ferric chloride hexahydrate, in wastewater treatment processes is known to induce pipe corrosion and to contribute to the discoloration of treated water. This study explores alternative approaches to sludge dewatering by evaluating the effectiveness of polymeric aluminum [...] Read more.
The use of coagulants, such as ferric chloride hexahydrate, in wastewater treatment processes is known to induce pipe corrosion and to contribute to the discoloration of treated water. This study explores alternative approaches to sludge dewatering by evaluating the effectiveness of polymeric aluminum chloride (PAC) as a coagulant and polyoxyethylene alkyl ether (POAE) as a surfactant. The impacts of coagulation/flocculation were assessed using time to filtration (TTF) and a pressure filter press. The effects of certain coagulant and surfactant dosages were studied. The inputs were in the range of 105–1750 mg/L for PAC and 28–152 mg/L for POAE, which were determined based on zeta potential (ZP) measurements. The optimal concentrations were 876 mg/L for PAC and 114 mg/L for POAE, resulting in a TTF of less than 1 min. Moreover, the effect of pH on anaerobic sludge dewaterability was investigated. At a low pH below 8, the ZP reached the maximum value, and a higher pH resulted in a reduction in ZP. Under low-pH adjustments, it was observed that the dewatering performance of the POAE surfactant improved more significantly than that of the PAC coagulant. In addition, the effect of pressure was analyzed using a pressure filter under conditions favoring POAE, with relatively lower dosages and greater cost-effectiveness. In order to evaluate the solubility of organic matter under pressurized conditions, the filtrate’s removal efficiency, chemical oxygen demand (COD), and total phosphorus (TP) were investigated. Solubilization did not occur at an increased pressure of around 10 bars. The findings presented in this study provide technical assistance for sludge treatment. Full article
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16 pages, 5516 KiB  
Article
Polyethylene Film Surface Modification via Benzoic Acid Grafting
by Ana Luisa Grafia and Silvia Elena Barbosa
Polymers 2024, 16(9), 1291; https://doi.org/10.3390/polym16091291 - 5 May 2024
Cited by 2 | Viewed by 1959
Abstract
A polyethylene (PE) film surface modification method is proposed via benzoic acid (BA) alkylation grafting to improve the surface affinity to polar substances. The procedure involves sequentially spraying AlCl3 and BA onto the heat-softened PE surface. The occurrence of the alkylation reaction [...] Read more.
A polyethylene (PE) film surface modification method is proposed via benzoic acid (BA) alkylation grafting to improve the surface affinity to polar substances. The procedure involves sequentially spraying AlCl3 and BA onto the heat-softened PE surface. The occurrence of the alkylation reaction was evaluated through comparative chemical, morphological, and thermal analyses. It was demonstrated that the grafting reaction of BA onto the PE film surface took place, limited to the surface layer, while preserving the bulk properties of PE. The reaction resulted in the formation of aluminum benzoate complexes, which improved the surface affinity to polar compounds. The impact of grafting on the surface properties of PE was further assessed by comparing the behavior of PE films treated with BA and untreated PE films when painted with watercolors. The PE film grafted with BA exhibited increased affinity towards watercolors, providing strong evidence of a change in surface polarity from hydrophobic to hydrophilic. These findings indicate that the proposed methodology effectively renders the PE surface paintable, even with non-toxic water-based inks, making it suitable for applications such as packaging. Full article
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17 pages, 5822 KiB  
Article
Selective Alkylation of Benzene with Methanol to Toluene and Xylene over H-ZSM-5 Zeolites: Impact of Framework Al Spatial Distribution
by Shu Ren, Fan Yang, Chao Tian, Yinghong Yue, Wei Zou, Weiming Hua and Zi Gao
Catalysts 2023, 13(9), 1295; https://doi.org/10.3390/catal13091295 - 14 Sep 2023
Cited by 9 | Viewed by 4116
Abstract
The alkylation of benzene with methanol can effectively generate high-value-added toluene and xylene out of surplus benzene, which is now achieved primarily using solid acids like H-ZSM-5 zeolites as catalysts. In this work, two H-ZSM-5 samples with distinct framework aluminum (AlF) [...] Read more.
The alkylation of benzene with methanol can effectively generate high-value-added toluene and xylene out of surplus benzene, which is now achieved primarily using solid acids like H-ZSM-5 zeolites as catalysts. In this work, two H-ZSM-5 samples with distinct framework aluminum (AlF) distributions, but otherwise quite similar textural and acidic properties, have been prepared by employing tetrapropylammonium hydroxide (TPAOH) and n-butylamine (NBA) as organic structure-directing agents (OSDAs). Systematical investigations demonstrate that AlF is preferentially located at the intersections in MFI topology when TPAOH is adopted. In contrast, less AlF is positioned therein as NBA is utilized. Density functional theory (DFT) calculations reveal that the transition-state complexes cannot be formed in the straight and sinusoidal channels due to their much smaller sizes than the dynamic diameters of transition states, whereas there are adequate spaces for the formation of transition states at the intersections. Benefitting from abundant AlF at the intersections, which provides more acid sites therein, H-ZSM-5 synthesized from TPAOH is more active relative to the counterpart obtained from NBA. At a WHSV of 4 h−1 and 400 °C, the former catalyst gives a 52.8% conversion, while the latter one affords a 45.9% conversion. Both catalysts display close total selectivity towards toluene and xylene (ca. 84%). This study provides an efficient way to regulate the distribution of acid sites, thereby enhancing the catalytic performance of H-ZSM-5 zeolite in the titled reaction. Full article
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13 pages, 6553 KiB  
Article
Lubricating Ability of Protic Ionic Liquids as Additives to a Biodegradable Oil for Aluminum-Steel Contact: Effect of Alkyl Chain Length and Propensity to Hydrogen Bonding
by Hong Guo, Brandon Stoyanovich, Junru Pang and Patricia Iglesias
Lubricants 2023, 11(8), 329; https://doi.org/10.3390/lubricants11080329 - 3 Aug 2023
Cited by 5 | Viewed by 3040
Abstract
Although aluminum alloys are widely used in the automotive and aerospace industries due to their excellent strength-to-weight ratio and good corrosion resistance, the poor tribological performance and low compatibility of these materials with lubricant anti-wear and anti-friction additives in conventional mineral oils are [...] Read more.
Although aluminum alloys are widely used in the automotive and aerospace industries due to their excellent strength-to-weight ratio and good corrosion resistance, the poor tribological performance and low compatibility of these materials with lubricant anti-wear and anti-friction additives in conventional mineral oils are major limitations. In addition, environmental awareness has increased the need for more environmentally friendly lubricants. Ionic Liquids (ILs) have exhibited significant potential as lubricants and lubricant additives. One of the more interesting properties of ILs is that they can form physically-adsorbed or chemically-reacted layers that reduce friction and wear of the surfaces in contact. Among ILs, Protic Ionic Liquids (PILs) have received more attention recently because of their simple and economic synthesis route. Furthermore, the anions and cations of PILs can be selected to be considered environmentally benign. In this article, the tribological behavior of a family of six PILs are studied as additives to a biodegradable oil (BO), under aluminum-steel contact. Al2024 disks slid against AISI52100 steel balls under a normal load of 3 N and a frequency of 5 Hz at room temperature and using a ball-on-flat reciprocating tribometer. PILs used in this study, were synthesized using two strong acids, with short and long hydrocarbon chains, and three weak bases with different propensities to hydrogen bonds. Results show that, although adding just 1 wt.% of any PIL to BO reduced friction and wear, the alkyl chain length influenced the lubricating ability of these ordered fluids. Wear mechanisms and surface interaction are discussed on the basis of 3D profilometry, SEM-EDX and RAMAN spectroscopy. Full article
(This article belongs to the Special Issue Green Tribology: New Insights toward a Sustainable World 2023)
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16 pages, 7889 KiB  
Article
Interaction of Aluminum and Platinum Surfaces with the Ionic Liquids 1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
by Fabien Krebs, Oliver Höfft and Frank Endres
Coatings 2023, 13(7), 1182; https://doi.org/10.3390/coatings13071182 - 30 Jun 2023
Cited by 5 | Viewed by 2081
Abstract
The processes at the interface between ionic liquids (ILs) and metals are a key factor for understanding especially in electrochemical deposition, nanoscale tribology applications and batteries. In the present work, the interfaces of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py1,4]TFSI) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]TFSI) and [...] Read more.
The processes at the interface between ionic liquids (ILs) and metals are a key factor for understanding especially in electrochemical deposition, nanoscale tribology applications and batteries. In the present work, the interfaces of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py1,4]TFSI) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]TFSI) and platinum and aluminum were investigated by depositing thin IL films and studying them with X-ray photoelectron spectroscopy (XPS) in ultrahigh vacuum. It is found that there is no evidence of a decomposition reaction of either IL on platinum; however, the imidazolium cation of [EMIm]TFSI shows a strong interaction with the surface in the monolayer regime. In contrast, [Py1,4]TFSI and [EMIm]TFSI show massive decomposition on the aluminum surface without applying any electrochemical potential. The spectra for the [TFSI] anion components show cleavage of C-F or N-S bonds in both cases. Both cleavage of a single fluorine atom and complete cleavage were observed, leading to further decomposition reactions of the anion. Consequently, new components such as AlOOH, Al(OH)3, Al2S3, Al2(SO4)3 and AlF3 appear at the interface. In addition, there is also evidence of decomposition of the cation by the splitting off hydrogen atoms or parts of the alkyl chain in both ILs. Full article
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18 pages, 12943 KiB  
Article
Effect of Cutting Fluid on Milled Surface Quality and Tool Life of Aluminum Alloy
by Shuoshuo Pang, Wenxiang Zhao, Tianyang Qiu, Weiliang Liu, Pei Yan, Li Jiao and Xibin Wang
Materials 2023, 16(6), 2198; https://doi.org/10.3390/ma16062198 - 9 Mar 2023
Cited by 6 | Viewed by 3062
Abstract
The machining process of aluminum alloy usually produces built-up edge and tool sticking problems due to their low hardness and large plastic deformation, which may further affect the machined surface quality and tool life. This paper aims to investigate the influence of different [...] Read more.
The machining process of aluminum alloy usually produces built-up edge and tool sticking problems due to their low hardness and large plastic deformation, which may further affect the machined surface quality and tool life. This paper aims to investigate the influence of different cutting fluids on the machined surface quality and tool life during the milling process of 7050 aluminum alloy. A novel cutting fluid (QC-2803) was considered in the study, which is synthesized by addition of alkyl alcohol amide and chlorinated polyolefin, and the traditional cutting fluid (CCF-10) was used as the control group. The physical and chemical properties of two cutting fluids were characterized. The milling process of 7050 aluminum alloy was carried out under two different cutting fluid conditions. The machined surface morphology, cutting force and tool wear morphology were observed during the process. Results show that the surface tension of the novel cutting fluid is significantly lower than that of the traditional cutting fluid, which makes it easier to produce a lubricating film between the aluminum alloy and tool, and further benefits the machined surface quality and tool life. As a result, the surface roughness and cutting force are reduced by ~20.0% and ~42.9%, respectively, and the tool life is increased by 25.6% in the case of the novel cutting fluid (QC-2803). The results in this paper revealed the important laws of cutting fluid with metal surface quality, cutting performance and tool wear, which helps to control the machined surface quality and tool life by the selection of cutting fluid during metal milling. Full article
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18 pages, 12874 KiB  
Article
New Polymer Composites with Aluminum Phosphates as Hybrid Flame Retardants
by Kamil Dziuba, Krystyna Wnuczek, Patryk Wojtachnio, Rodolphe Sonnier and Beata Podkościelna
Materials 2023, 16(1), 426; https://doi.org/10.3390/ma16010426 - 2 Jan 2023
Cited by 8 | Viewed by 2910
Abstract
Polymeric aluminum organophosphates are a class of nanostructured aluminum-based compounds that can be considered organic and inorganic hybrid materials. Aluminum phosphates have attracted considerable interest due to their ability to enhance composite materials’ mechanical characteristics, lightweight, and thermal properties. Extensive studies have shown [...] Read more.
Polymeric aluminum organophosphates are a class of nanostructured aluminum-based compounds that can be considered organic and inorganic hybrid materials. Aluminum phosphates have attracted considerable interest due to their ability to enhance composite materials’ mechanical characteristics, lightweight, and thermal properties. Extensive studies have shown the potential of aluminum organophosphates as a component in the development of fire-retardant materials. Aluminum–organophosphorus hybrid (APH) materials have been prepared by reacting aluminum oxide hydroxide (boehmite) with alkyl and aryl phosphoric acids and used to prepare composites with epoxy resin. Boehmite is an aluminum oxide hydroxide (γ-AlO(OH)) mineral, a component of the aluminum ore bauxite. In this work, the composites based on epoxy resin Epidian 601 and commercial curing agent IDA were obtained. Pure boehmite and APH hybrids were added as flame retardants. FTIR and TGA analysis showed that obtained APH possesses a hybrid structure, high thermostability, and various morphologies. These new APH were incorporated into epoxy resin. The infrared spectroscopy confirmed the structure of hybrids and composites. Pyrolysis combustion flow calorimetry (PCFC) and cone calorimeter analyses were performed to assess the flame retardant properties of the composites. The results showed that the incorporation of 17 wt% APH allows a reduction of heat release rate but to a limited extent in comparison to pure boehmite, which is due to the different decomposition mechanisms of both boehmite and hybrids. The cone calorimetry test showed that residue contents correspond quite well to the mineral fraction from boehmite only. The hybrid APHs appear no more efficient than pure boehmite because the mineral fraction in APH is reduced while phosphate fraction cannot promote significant charring. Full article
(This article belongs to the Special Issue Polymer Biocomposites: From Design to Application)
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12 pages, 2369 KiB  
Article
Forced Gradient Copolymer for Rational Design of Mussel-Inspired Adhesives and Dispersants
by Takehiro Fujita, Masami Shuta, Mika Mano, Shinnosuke Matsumoto, Atsushi Nagasawa, Akihiro Yamada and Masanobu Naito
Materials 2023, 16(1), 266; https://doi.org/10.3390/ma16010266 - 27 Dec 2022
Cited by 2 | Viewed by 3013
Abstract
In recent years, there has been considerable research into functional materials inspired by living things. Much attention has been paid to the development of adhesive materials that mimic the adhesive proteins secreted by a mussel’s foot. These mussel-inspired materials have superior adhesiveness to [...] Read more.
In recent years, there has been considerable research into functional materials inspired by living things. Much attention has been paid to the development of adhesive materials that mimic the adhesive proteins secreted by a mussel’s foot. These mussel-inspired materials have superior adhesiveness to various adherents owing to the non-covalent interactions of their polyphenolic moieties, e.g., hydrogen bonding, electrostatic interactions, and even hydrophobic interactions. Various factors significantly affect the adhesiveness of mussel-inspired polymers, such as the molecular weight, cross-linking density, and composition ratio of the components, as well as the chemical structure of the polyphenolic adhesive moieties, such as l-3,4-dihydroxyphenylalanine (l-Dopa). However, the contributions of the position and distribution of the adhesive moiety in mussel-inspired polymers are often underestimated. In the present study, we prepared a series of mussel-inspired alkyl methacrylate copolymers by controlling the position and distribution of the adhesive moiety, which are known as “forced gradient copolymers”. We used a newly designed gallic-acid-bearing methacrylate (GMA) as the polyphenolic adhesive moiety and copolymerized it with 2-ethylhexyl methacrylate (EHMA). The resulting forced gradient adhesive copolymer of GMA and EHMA (poly(GMA-co-EHMA), Poly1) was subjected to adhesion and dispersion tests with an aluminum substrate and a BaTiO3 nanoparticle in organic solvents, respectively. In particular, this study aims to clarify how the monomer position and distribution of the adhesive moiety in the mussel-inspired polymer affect its adhesion and dispersion behavior on a flat metal oxide surface and spherical inorganic oxide surfaces of several tens of nanometers in diameter, respectively. Here, forced gradient copolymer Poly1 consisted of a homopolymer moiety of EHMA (Poly3) and a random copolymer moiety of EHMA and GMA (Poly4). The composition ratio of GMA and the molecular weight were kept constant among the Poly1 series. Simultaneous control of the molecular lengths of Poly3 and Poly4 allowed us to discuss the effects on the distribution of GMA in Poly1. Poly1 exhibited apparent distribution dependency with regard to the adhesiveness and the dispersibility of BaTiO3. Poly1 showed the highest adhesion strength when the composition ratio of GMA was approximately 9 mol% in the portion of the Poly4 segment. In contrast, the block copolymer consisting of the Poly3 segment and Poly4 segment with only adhesive moiety 1 showed the lowest viscosity for dispersion of BaTiO3 nanoparticles. These results indicate that copolymers with mussel-inspired adhesive motifs require the proper design of the monomer position and distribution in Poly1 according to the shape and characteristics of the adherend to maximize their functionality. This research will facilitate the rational design of bio-inspired adhesive materials derived from plants that outperform natural materials, and it will eventually contribute to a sustainable circular economy. Full article
(This article belongs to the Special Issue Advanced Polymeric Materials: Synthesis, Properties, and Applications)
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5 pages, 1335 KiB  
Proceeding Paper
Approach to the Synthesis of Five-Membered Organophosphorus Compounds via Alumoles and Alumolanes
by Alevtina L. Makhamatkhanova, Tatyana V. Tyumkina and Usein M. Dzhemilev
Chem. Proc. 2022, 12(1), 47; https://doi.org/10.3390/ecsoc-26-13637 - 16 Nov 2022
Viewed by 1323
Abstract
This work summarizes the results of a new approach to the synthesis of previously undescribed, hard-to-obtain five-membered cyclic organophosphorus compounds: 3-alkyl(aryl)-substituted phospholanes, α,ω-bisphospholanes, polycyclic phospholanes, 4,5-dialkyl(diaryl)-disubstituted 2,3-dihydrophospholes, as well as their oxides and sulfides. Alumoles and alumolanes synthesized by the reaction of cycloalumination [...] Read more.
This work summarizes the results of a new approach to the synthesis of previously undescribed, hard-to-obtain five-membered cyclic organophosphorus compounds: 3-alkyl(aryl)-substituted phospholanes, α,ω-bisphospholanes, polycyclic phospholanes, 4,5-dialkyl(diaryl)-disubstituted 2,3-dihydrophospholes, as well as their oxides and sulfides. Alumoles and alumolanes synthesized by the reaction of cycloalumination of available unsaturated compounds (terminal alkenes, α,ω-alkadienes, norbornene derivatives, symmetrical internal alkynes) with Et3Al in the presence of a Cp2ZrCl2 catalyst were used as precursors. The substitution of aluminum atoms in cyclic organoaluminum compounds for phosphorus atoms takes place using alkyl(aryl)phosphorus (III) dichlorides. The developed one-pot method gives high yields of products under mild conditions. Full article
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Scheme 1

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