2,2′,7,7′-Tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (Spiro-OMeTAD) is widely used as a hole-transporting material in perovskite solar cells (PSCs); however, its intrinsic thermal stability remains insufficiently understood. Here, the thermal stability and high-temperature behaviour of pristine Spiro-OMeTAD films prepared by solution processing and vacuum deposition are systematically investigated using real-time and standard x-ray photoelectron spectroscopy, with annealing temperatures up to 500 °C under ultra-high vacuum. Spiro-OMeTAD films deposited on different substrates exhibit similar chemical environments and photoemission characteristics, demonstrating that the surface chemistry is largely insensitive to deposition method and substrate. Pristine Spiro-OMeTAD remains chemically stable up to 300 °C. Above an onset temperature of approximately 350 °C, partial decomposition of surface molecules occurs, characterised by progressive detachment of the terminating methoxy groups. In contrast, the spirobifluorene and phenylamine backbones retain structural integrity up to 500 °C, without evidence of evaporation or fragmentation, even for vacuum-deposited films. The loss of methoxy groups leads to a modification of the valence band structure, with the valence band maximum shifting towards higher binding energy and the ionisation potential increasing accordingly. These results define intrinsic thermal limits for pristine Spiro-OMeTAD and indicate that, provided other functional layers permit, processing temperatures up to 300 °C may be accessible, whereas exposure above 350 °C is expected to compromise interfacial electronic properties in PSCs.

Operando style, non-contact infrared thermography has been used to study the change in surface metal temperature between the zinc bath compared to just above the gas jet knives at an industrial, continuous galvanising line (CGL). Measuring photons in the wavelength range 7-12 mu m at 30 frames per second (fps), the change in photon count was 4608. Using an emissivity of 0.069, corresponding to zinc, this correlates to a minimum temperature drop of 14 degrees C. Using higher emissivities, linked with oxidized surfaces, suggests an even higher temperature drop (up to 19 degrees C). These data are key in understanding the influence of coating weight processing parameters on continuously galvanised sheet steel with implications for surface finish, microstructural morphology and resultant corrosion resistance of the material. The infrared data is validated using static measurements of molten zinc and zinc dross between 430 degrees C and 470 degrees C in a hot dip galvaniser simulation pot containing 40 kg of molten GI (Zn 0.2 wt. %Al).

A method has been developed to delaminate the organic components (paint, foam) from the steel skins of composite polyisocyanurate (PIR) steel insulation panels at ambient temperature and in 20 min using selected solvents combined with ultrasonication. Using this method, polyisocyanurate foam can be selectively delaminated from polymer-based paint (PVC plastisol) and, in turn, the polymer paint can be selectively delaminated from the galvanised steel. Both the foam and paint are removed as intact layers, leaving the galvanised steel intact for the next steps of recycling, enabling the subsequent individualised recycling of each sub-component or layer. Several solvents have been tested, and the data show that H-bonding solvents (e.g., H2O, alcohols) are less effective at delaminating these polymers. Whilst high polarity, medium H-bonding acetonitrile and DMSO remove PVC paint and some PIR foam, the most effective solvent for both PIR foam and PVC paint removal is medium polarity, medium H-bonding acetone.

Micro(nano)plastics (MNPs) are plastic particles ranging in size from < 1 & micro;m to 5 mm, posing immense challenges owing to their ubiquitous and polydisperse nature, ecological and human health risks, and environmental remediation challenges. Biochar is a promising tool to remove legacy and emerging environmental pollutants, including MNPs, from aquatic and terrestrial matrices. This review systematically collates studies on pristine and modified biochar in terms of their potential to remove MNPs from laboratory and environmental samples (freshwater, seawater, wastewater, and soil), factors affecting MNP-biochar interactions, adsorption mechanisms, biochar regeneration methods, and research gaps. Our data analyses showed that the modified biochar (8.25-897.7 m(2)/g, p = 0.035) exhibited significantly higher surface area than that of pristine biochar (1.30-540.36 m(2)/g). Similarly, the adsorption capacity of modified biochar (10.92-1723 mg/g, p = 0.030) was significantly higher than that of the pristine biochar (0.56-80.3 mg/g). Pearson correlation analysis showed a significantly positive correlation between surface area and pyrolysis temperature for pristine biochar (r = 0.81, p < 0.05); and adsorption capacity showed a significantly positive correlation with the size of MNPs (r = 0.78, p < 0.05) for modified biochar. Further, properties of MNPs, biochar, and environmental conditions were the major factors affecting the MNP-biochar interface, plastic removal, and biochar regeneration. Removal mechanisms mainly involved pore filling, physical trapping, electrostatic interaction, hydrophobic interaction, hydrogen bonding, and pi-pi interactions. Depending on the type of MNPs and biochar, either single or multiple removal mechanisms can be involved in the adsorption of MNPs on biochar. Pyrolysis, ultrasonication, chemical methods, and hydrothermal degradation were mainly used individually or in combination to regenerate biochar with high reuse efficiencies. Lack of field studies; polymer mixture and environmental MNP removal; aging of biochar and MNPs; optimization and sustainable modification and regeneration of biochar; MNP-biochar-specific interaction mechanisms; scale-up applications; and fate of spent MNP-biochar complexes are the major research gaps and future research perspectives.

The steel industry is responsible for between 7

A comprehensive study was conducted to simultaneously simulate thermodynamic behavior and predict catalyst performance for CH4 production via CO and CO2 methanation, using blast furnace gas (BFG) and basic oxygen furnace gas (BOFG) as feedstocks. Thermodynamic equilibrium simulations based on Gibbs free energy minimization identified optimal reaction conditions at moderate temperatures (150-250 degrees C) and elevated pressures, achieving over 98 % CO2 conversion with less than 1 wt% carbon formation. In parallel, machine learning models were developed using an augmented dataset of 2777 experimental observations. Atomic-level structural and electronic descriptors were incorporated into the dataset, including unit cell density and formation energy for active metals, promoters, and supports. Feature selection through Pearson correlation and RFECV identified active phase weight, support density, and reduction conditions as the most influential variables. Among all tested algorithms, XGBoost and CatBoost demonstrated the highest accuracy, with R2 values exceeding 0.93 for predicting CH4 yield, selectivity, and CO2 conversion. SHAP and partial dependence analyses showed that catalyst stability and textural properties govern overall performance. This integrated thermodynamic and machine learning approach defines the operating limits for high-efficiency methanation and provides a data-driven framework for catalyst optimization in industrial applications.

Microplastics and metals are increasingly recognised as major water contaminants with profound environmental and health consequences. The environmental co-occurrence of microplastics and metals are well documented in waterways, including urban runoff, highway balancing ponds, industrial wastewater, and mine-impacted waters, posing a multifaceted environmental threat. Urgent remedial action is required to remove co-occurring microplastics and metals from water, giving consideration to how their co-occurrence can affect remediative efforts. However, information on the sorption of microplastics and Pb and Zn simultaneously by biochar is lacking. In this current study, changes in the quantity of metal adsorbed by pristine larch biochar and magnetised larch biochar due to the presence of microplastics was assessed using spectroscopic techniques. This study demonstrated that magnetised larch biochar and pristine larch biochar both remove co-occurring microplastics, Pb, and Zn from solution. Neither magnetised larch biochar nor pristine larch biochar show any statistical difference in the sorption of Pb with the inclusion of microplastics into the aqueous matrix. However, the inclusion of microplastics result in the reduced sorption of Zn by 43% for magnetised larch biochar (p < 0.01) and 69% for pristine larch biochar (p < 0.01). Magnetised larch biochar also demonstrated greater sorption than pristine larch biochar for microplastics (p < 0.05), Zn co-occurring with microplastics (p < 0.05), and Zn with no microplastics present (p < 0.01). Despite the effects of competitive sorption between Zn and microplastics, the removal of Pb, Zn, and microplastic from a multi-contaminant system indicate that magnetic larch biochar is a viable option to remove multiple contaminants from aqueous environs where metals and microplastics are seen to co-occur.

This paper reports studies on the thermal chemistry of the flash pyrolysis (heating rate of 20,000 °C/s up to 800 °C) of non-fossil fuel carbon (NFF-C) waste (or refuse-derived fuel, RDF) in the context of using this as an alternative reductant for blast furnace ironmaking. Gas chromatography–mass spectrometry (GCMS) analysis linked to the pyrolyser was used to simulate the thermal processes that take place during injection in the blast furnace raceway, where material experiences extreme temperature (ca. 1000 °C) over very short residence times (<300 ms). Species identification and qualitative analysis of evolved species generated are reported. Whilst the pyrolyser uses flash heating of a static sample, a drop tube furnace was also employed to study a sample moving rapidly through a pre-heated furnace held at 1000 °C to enable reductant burnout rates to be measured. The overarching aim of this piece of work is to study the suitability of replacing fossil fuel with non-recyclable plastic and paper as blast furnace reductants.

Industrial decarbonization requires scalable pathways to recycle carbon-rich waste and produce low-emission fuels. Steelmaking emits substantial CO and CO2 via off-gases, while plastic waste particularly polypropylene (PP) offers a hydrogen-rich feedstock. This work presents a thermodynamic simulation that employs Gibbs free energy minimization to optimize methane synthesis from steelmaking off-gases (CO and CO2). The process is driven by hydrogen produced through polypropylene ((-C3H6-)n, PP) pyrolysis, enabling the conversion of two industrial waste streams into synthetic methane (CH4). Energy and exergy efficiencies were evaluated to assess the viability and performance of this integrated approach. PP pyrolysis at 650 degrees C and 1 bar was found to yield 7 mol h-1 of H2, achieving energy and exergy efficiencies of 65 % and 35 %, respectively. This H2was directly coupled to methanation of CO and CO2 at 250 degrees C and 10 atm, yielding CH4 with an 82 % selectivity and complete (100 %) conversion of both carbon sources. The methanation step displayed peak energy and exergy efficiencies near 78 %, while coke formation remained suppressed due to effective carbon reconversion at <= 300 degrees C. The synergy process enables enhanced thermodynamic performance and system integration, transforming waste plastics and metallurgical off-gases into clean, usable fuels. The combined pathway offers a circular, low-carbon solution for hydrogen and methane synthesis using industrial residues, supporting both energy transition goals and waste management.

The knowledge around the effect of bioenergy on the thermal properties of iron ore sinter is not widely understood. Therefore, the effects of a 30 % biomass hybrid was investigated. Experiments placed samples in thermal environments encapsulating radiant, convective and conductive heating at increasing thermal gradients. Temperature data was collected using a longwave IR thermal camera, prompting a gap in literature knowledge - "Does emissivity vary as sinter undergoes thermal change?" to be studied. Furnace data in the range of 200(degrees) C-600(degrees) C showed an increasing trend in emissivity from 0.82 to 0.93 with a deviation of < 2 % between 0 and 100 % hybrid samples. The results of the subsequent thermal tests indicated an initial barrier to energy absorption caused by the morphology of the sinter that decreased with the thermal gradient. Statistical analysis concluded that the 75 % blend, absorbed energy at a consistently high rate in all the heating environments. Linear regression analysis with x-ray fluorescence and diffraction data showed that the quantity of FeO, prismatic SFCA and platy SFCA had a measurable effect on the heating rate at 400 C-degrees. However, as temperatures increased to 600(degrees)C Fe2O3 had more effect than FeO, with the SFCA phases maintaining their impact on heating rate.

This study investigated a novel method of recovering energy from iron ore sinter using solid iron oxide heat transfer materials. Traditionally, air is passed through the sinter either in an open conveyor or a sealed vessel to recover energy. The bed materials used were a magnetite concentrate, hematite ore, goethite–hematite ore and sinter fines. A shortwave thermal camera and quartz reactor were used measure infrared radiation from the process. The thermal imaging was combined with image analysis techniques to visualise the transfer of thermal energy through the system. The results showed that energy moved rapidly through the system with peak heating rates of 18 °C/min at a lump sinter temperature of 600 °C. The ratio of heating rate to cooling rate was as high as 8.6:1.0, indicating efficient retention of energy by the bed materials. The bed composition, determined by X-ray fluorescence and X-ray diffraction was used to calculate the heat capacity based on pure material properties. The resultant energy balance determined thermal efficiency to be between 32 and 46% for the sinter fines and hematite–goethite ore, resulting in predicted fuel savings of up to 9.4kg/tonne with similar heat utilisations to the air recovery process. Thermal imaging combined with Brunauer–Emmett–Teller surface area measurements and scanning electron microscopy analysis experimentally replicated mathematical heat transfer model predictions that a smaller total pore volume resulted in less thermally resistive bed. Image analysis illustrated the breaking of the heat front between the less resistive solid and more resistive air in porous beds versus even conduction of heat through a dense bed. The oxide distribution in the bed materials impacted heat transfer, as at a lump temperature of 500 °C was controlled by hydrated oxide content whereas at 600 °C Fe2O3 was the more dominant driver.

Plastic is a material that has become ubiquitous since entering the marketplace in the 1930s and 1940s; as a result, the presence of nano and microplastics (NMPs) are pervasive in natural environments affecting air, soil and water ecosystems. These NMPs are varied in size (categorised as either microplastics at 5 mm–1 µm or nanoplastics at < 1 µm), shape and chemical composition. They represent a potential threat to aquatic life and human health through ingestion and inhalation. The toxicity of NMPs is attributed to chemical additives introduced during production and the absorbance of inorganic and organic chemical contaminants in environmental settings. This review is designed to discuss the use of biochar as a natural adsorbent for the remediation of water contaminated with NMPs. Biochar is a sustainable, affordable material which can remediate water and contribute to ecosystem restoration. Whilst it is well established as a material to sorb organic and inorganic contaminants, its use to remove NMPs is in its infancy and as such this review sets out to outline the mechanisms and modifications of biochar to remove NMPs from aqueous environments. Although removal mechanisms in laboratory settings are becoming clearer this review highlights that remediative studies need to be undertaken in conjunction with the systematic investigation of the effect of key environmental parameters on remediation and the use of environmentally aged NMPs. The future direction of this discipline also needs to incorporate field trials alongside laboratory work to develop a stronger understanding of the viability of biochar to remove NMPs from waterways.

Nickel hydroxide has been successfully employed as a precursor to the widely used, inorganic hole transport material (HTM) nickel oxide (NiOx). However, manufacturing NiOx HTM layers from nickel hydroxide is more complicated than those involving organometallic precursors due to its poor solubility/dispersibility. We report here a substantial increase in nickel hydroxide dispersibility in organic solvents by complexing it with monoethanolamine. These improvements have enabled us to develop a simpler method for processing nickel hydroxide that resemble the known sol-gel method. The new metal complex remains dispersed for months and converts to nickel oxide at a temperature similar to that of nickel hydroxide (270-300 degrees C). An extensive characterisation of NiOx films obtained from the deposited precursor has been carried out. Perovskites solar cells have also been built with these films as a proof of concept, showing promising results for the layers sintered at low (270 degrees C) and high (500 degrees C) temperatures. The pixel with highest efficiency for both sintering temperatures were 14.7 % and 16.7 %, respectively, which are close to or surpass the ones of the control samples (15.4 % and 15.7 %, respectively). The applied unpaired t-test statistical method showed that the mean efficiency values for our thick samples prepared at 270 degrees C are not statistically different from those of the control cells. Furthermore, the samples prepared at 500 degrees C presented a significant statistical difference with the control cells, showing higher average efficiencies (12.8 % and 13.3 % versus 11.4 % and 11.7 %, reverse and forward measurements, respectively). The simplicity of the manufacturing method developed, together with the use of non-toxic organic compounds for its preparation and the promising results observed in solar devices, makes it suitable for being upscaled.

In this work we demonstrate a NASICON film sintered in situ onto a fused silica substrate. This production method drastically reduces the manufacturing time by combining the use of a spray-coated sol-gel solution and near-infrared (NIR) ultrafast sintering technology. This is the first demonstration of NIR sintered ceramics at high temperatures (similar to 1000 degrees C).

In this work we demonstrate a NASICON film sintered in situ onto a fused silica substrate. This production method drastically reduces the manufacturing time by combining the use of a spray-coated sol-gel solution and near-infrared (NIR) ultrafast sintering technology. The first demonstration of NIR sintered ceramics at high temperatures ( 1000^∘C).

The global steel industry uses fossil fuels to produce millions of tonnes of iron ore sinter each year. Sintering is an energy-intensive process that fuses iron ore and flux to produce material that balances a high mechanical strength at a sufficient particle size to ensure a macroporous burden in the blast furnace to enable rapid gas flow. As significant CO2 greenhouse emissions are emitted, the defossilisation of these CO2 emissions is vital to net-zero carbon targets. Two iterations of a new biomass–coal hybrid fuel (ecoke®(A) and ecoke®(B)) were compared with coke breeze and an anthracite coal using oxygen bomb calorimetry, simultaneous thermal analysis (STA) combining thermogravimetry and differential scanning calorimetry, and isoconversional kinetic modelling and pyrolysis–GCMS to study the volatile matter. The calorific values of both ecoke®(A) and (B) were marginally higher than that of the coke breeze: 27.9 MJ/kg and 27.8 MJ/kg, respectively, compared with 26.5 MJ/kg for the coke breeze. A proximate analysis revealed both ecoke® samples to have higher volatile matter contents (ca. 12–13%) than the coke breeze (7.4%), but less than the anthracite coal (ca. 14%). The thermogravimetric analysis of the burnout kinetics of the fuels heated up to 1000 °C, at heating rates from 5 to 25 °C/min, showed that that the coke breeze and anthracite coal had higher ignition and burnout temperatures than the ecoke® samples. Kinetic analysis using the Freidman and Ozawa methods found that the ecoke® samples showed comparable maximum mass loss rates to the coke breeze but lower activation energies. From these results, both ecoke® samples have the potential to replace some of the coke breeze in the sintering process or EAF processes to help achieve net zero by offsetting up to 30% of the CO2 emissions.

Abstract This study describes the utilization of near edge X‐ray absorption fine structure (NEXAFS) to investigate the hole transporting material (HTM) 2,2ʹ,7,7ʹ‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐ 9,9ʹ‐spirobifluorene (Spiro‐OMeTAD) and its most common dopants, lithium bis‐(trifluoromethylsulfonyl) imide (LiTFSI), 4‐tert‐butylpiridine (tBP), and 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4‐TCNQ). By changing the angle of the sample with respect to the beam, the orientation of the molecules on the surface can be observed. The data suggest that it is difficult to determine any orientational preference for Spiro‐OMeTAD deposited on a surface due to the 3D propeller‐like geometry of this molecule. Both doped and undoped samples show thermal stability beyond the glass transition temperature of the molecules. Significant changes to the Spiro‐OMeTAD spectra are observed with the addition of the dopants, in particular the C K‐edge. Differences are also observed in the valence band spectra when dopants are added. It is also demonstrated how the doping combination of LiFTSI with tBP and, F4‐TCNQ act as p‐type dopants by altering the position of the HOMO levels. The F4‐TCNQ induces a larger change in the HOMO levels when compared to the LiTFSI and tBP. These results are important to increase the understanding of Spiro‐OMeTAD and the effect dopants have on this material for next generation solar cells.

Nine halloysite nanotubes (HNTs) have been examined using scanning electron microscopy (SEM), atomic force microscopy (AFM) and (cross-sectional) transmission electron microscopy (TEM) to evaluate details of their external and internal morphologies. The samples span morphologies within the cylindrical to prismatic-polygonal framework proposed by Hillier et al. (2016). The ‘carpet roll’ model assumed in the conceptualization of most technological applications of HNTs is shown to be far too simplistic. Both cylindrical and prismatic forms have abundant edge steps traversing their surfaces that, by analogy with plates of kaolinite, correspond to prism faces. The mean value for the diameter of the central lumen of the tubes is 12 nm. Numerous slit-like nanopores, with diameters up to 18 nm, also occur between packets of layers, particularly in prismatic forms at the junction between a central cylindrical core and outer packets of planar layers. These pores expose aluminol and siloxane surfaces, but unlike the lumen, which is assumed only to expose an aluminol surface, they do not extend along the entire length of the nanotube. Edge steps seen most clearly by AFM correspond in height to the packets of layers seen in TEM. TEM cross-sections suggest that tube growth occurs by accretion of a spiralled thickening wedge of layers evolving from cylindrical to polygonal form and reveal that planar sectors may be joined by either abrupt angular junctions or by short sections of curved layers. A more realistic model of the internal and external morphologies of HNTs is proposed to assist with understanding of the behaviour of HNTs in technological applications.