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At least 19 records

New insights on carbon black suspension rheology—Anisotropic thixotropy and antithixotropy

We report a detailed experimental study of peculiar thixotropic dynamics of carbon black (CB, Vulcan XC-72) suspensions in mineral oil, specifically the observation of sequential stress increase then decrease at a fixed shear rate in a step-down test. We verify that such dynamics, though peculiar, come from a true material response rather than experimental artifacts. We also reveal how this long-time stress decay is associated with antithixotropic structural change rather than viscoelastic stress relaxation by using orthogonal superposition (OSP) rheometry to probe viscoelastic moduli during the step-down tests. The orthogonal storage and loss moduli are present, showing this two-timescale recovery then decay response, which demonstrates that this response is antithixotropic, and it involves shear-induced structuring. We further show a mechanical anisotropy in the CB suspension under shear using OSP. Based on the rheological results, a microstructural schematic is proposed, considering qualitatively thixotropic structure build-up, antithixotropic densification, and anisotropic structure evolution. Our observation for these CB suspensions is outside the standard paradigm of thixotropic structure-parameter models, and the elastic response provides us with new insight into the transient dynamics of CB suspensions.

Mechanics↗

Rheo-electric measurements of carbon black suspensions containing polyvinylidene difluoride in N -methyl-2-pyrrolidone

Lithium-ion battery cathode slurries have a microstructure that depends sensitively on how they are processed due to carbon black's (CB) evolving structure when subjected coating flows. While polyvinylidene difluoride (PVDF), one of the main components of the cathode slurry, plays an important role in modifying the structure and rheology of CB, a quantitative understanding is lacking. In this work, we explore the role of PVDF in determining the structural evolution of Super C65 CB in N-methyl-2-pyrrolidinone (NMP) with rheo-electric measurements. We find that PVDF enhances the viscosity of NMP resulting in a more extensive structural erosion of CB agglomerates with increasing polymer concentration and molecular weight. We also show that the relative viscosity of all suspensions can be collapsed by the fluid Mason number (Mnf), which compares the hydrodynamic forces imposed by the medium to cohesive forces holding CB agglomerates together. Using simultaneous rheo-electric measurements, we find at high Mnf, the dielectric strength (Δε) scales with Mnf, and the power-law scaling can be quantitatively predicted by considering the self-similar break up of CB agglomerates. The collapse of the relative viscosity and scaling of Δε both suggest that PVDF increases the hydrodynamic force of the suspending medium without directly changing the CB agglomerate structure. These findings are valuable for optimizing the rheology of lithium ion battery cathode slurries. We also anticipate that these findings can be extended to understand the microstructure of similar systems under flow.

Mechanics↗

Evaluation of a catalytically aided thermal regeneration method for quartz filter-based black carbon sensing

Black carbon (BC)–a strong indicator of diesel particulate matter and other sources of incomplete carbonaceous fuel combustion–is an important air pollutant that affects public health, yet low-cost sensors capable of long-term, autonomous BC monitoring remain underdeveloped. We report on the development and evaluation of a novel BC prototype sensor that integrates soot collection on a quartz filter, in-situ optical transmission measurement, and thermal filter regeneration. To enable regeneration at lower temperatures, we evaluated the catalytic effects of various alkali metal salts pre-applied to the filter. Among these, cesium carbonate (Cs 2 CO 3 ) exhibited the strongest catalytic activity, lowering the temperature required for complete BC removal by up to 190 °C and reducing energy consumption by more than 75% compared to that required for untreated filters. The catalytic effect persisted through 10 BC collection–regeneration cycles. These findings demonstrate the potential of catalytically aided thermal regeneration in BC sensors and suggest a pathway toward energy-efficient and reduced maintenance air quality monitoring suitable for distributed BC monitoring networks.

Tang, Xiaochen [Lawrence Berkeley National Laborat↗

A review of black carbon in snow and ice and its impact on the cryosphere

Black carbon (BC) has emerged as an important short-lived climate forcer. Due to its light absorption properties, BC can darken the snow/ice surface, affect the energy balance, and further lead to acceleration of the cryospheric melting. By reviewing the recent published literatures, we present an overview of the historical changes, spatial distribution of BC in snow/ice, and how these changes are related to the melting of the cryosphere (e.g., glaciers, snow cover, and sea ice). Ice core records show an abrupt increase of BC concentrations that began in the 1850s and continued throughout the 20th century, which is consistent with an increase in BC emissions owing to industrialization. A decrease in the amount of BC since 1970s in Arctic and European ice cores has been partially attributed to the Clean Air Act. However, in the Himalayas, BC records show a continuous increase during this period. BC concentrations in snow and ice in the mid-latitude regions are one to two orders of magnitude higher than those in the polar regions. In particular, BC concentrations in aged snow and granular ice in ablation areas of mountain glaciers are one to three orders of magnitude higher than those in fresh snow or snowpits in the glacier accumulation areas due to BC accumulation during melting season. BC in the surface snow/ice is responsible for about 20% of the albedo reduction in the Tibetan Plateau during glacier melt season. Globally, observations and modeling results indicate that radiative forcing (RF) induced by BC in snow and ice is highest in the mid-latitudes, ranging from several W m–2 in fresh snow to hundreds of W m–2 in aged snow and granular ice in glacier ablation areas. The large BC-in-snow RF and associated snow albedo feedback lead to an acceleration in the total glacier melt (approximately 20%) and/or a reduction in the duration of the snow cover by several days, resulting in an increase of glacier discharge. Given our limited understanding of the role of BC in cryospheric melting, it is important to synthesize the existing research on the multi-scale processes related to BC in snow and ice to identify the gaps in our understanding of these processes and to propose a path forward to improve the quality of our observations of the aforementioned phenomena to fill these gaps.

Kang, Shichang↗

Black Carbon Deposited in Hariqin Glacier of the Central Tibetan Plateau Record Changes in the Emission from Eurasia

Black carbon (BC), by the combustion of fossil fuels and biomass, has profound effects on climate change and glacier retreat in industrial eras. In the present study, we report refractory BC (rBC) in an ice core spanning 1850–2014, retrieved from the Hariqin Glacier of the Tanggula Mountains in the central Tibetan Plateau, measured using a single particle soot photometer (SP2). The rBC concentration shows a three-fold increase since the 1950s. The mean rBC concentration was 0.71±0.52 ng mL-1 during 1850s–1940s and 2.11±1.60 ng mL-1 during 1950s–2010s. The substantial increase in rBC since the 1950s is consistent with rBC ice core records from the Tibetan Plateau and Eastern Europe. According to the predominant atmospheric circulation patterns over the glacier and timing of changes in regional emissions, the post-1950 amplification of rBC concentration in the central Tibetan Plateau most likely reflects increases in emissions in Eastern Europe, former USSR, the Middle East, and South Asia. Despite the low-level background rBC concentrations in the ice cores from the Tibetan Plateau, the present study highlights a remarkable increase in anthropogenic BC emissions in recent decades and the consequent influence on glaciers in the Tibetan Plateau.

Black carbon, Ice core, Tibetan Plateau, Industria↗

Simulated aging processes of black carbon and its impact during a severe winter haze event in the Beijing-Tianjin- Hebei region

Black carbon (BC) can mitigate or worsen air pollution through perturbing meteorological conditions. BC aging processes are important for the evolution of particle size, concentration, and optical properties of BC that determines its influence on the meteorology. Here we use the online coupled Weather Research and Forecasting-Chemistry (WRF-Chem) model to quantify the role of BC aging processes, including physical processes (PP) and absorption enhancements (AE), in exerting BC-induced meteorological changes and the associated feedback to PM2.5 (particulate matter less than 2.5 µm in diameter) and O3 concentrations during a severe haze event in Beijing-Tianjin-Hebei (BTH) region during 21-27 February 2014. Our results show that, compared to the simulation without the PP treatment, the simulated near-surface BC concentration and BC mass loading in BTH region is lowered by 6.6 % and 12.1 %, respectively, during the haze event with the PP included. PP increases the proportion of large-size BC (particle diameter greater than 0.312 µm) from 28 %-33 % to 59 %-64 % below 1000 m in BTH region. Both PP and AE enhance the “dome effect” of BC. With both PP and AE considered, a reduction in PBL height due to BC-PBL interaction is 116.3 m (20.7 %), compared to 75.7 m (13.5 %) without AE and 66.6 m (11.9 %) without both PP and AE. However, during this haze event, anomalous northeasterly winds are produced by the direct radiative effect of BC, which further affects the mixing and transport of aerosols. When PBL height is decreased (from 10:00 to 21:00), combining all the impacts on multiple meteorological factors, BC effect without PP and AE, without AE, and with PP and AE, respectively, increases surface concentrations of PM2.5 by 8.3 µg m-3 (6.1 % relative to the mean value), 6.1 µg m-3 (4.5 %) and 9.6 µg m-3 (7.0 %) but decreases surface O3 concentrations by 2.8 ppbv (7.4 %), 4.0 ppbv (9.0 %) and 5.0 ppbv (10.8 %) in BTH region averaged over 21-27 February 2014. Our results highlight the importance of the aging processes and absorption enhancements of BC in simulating weather and air quality.

Chen, Donglin↗

Evaluating the Rheo-electric Performance of Aqueous Suspensions of Oxidized Carbon Black

Here, the macroscopic properties of carbon black suspensions are primarily determined by the agglomerate microstructure built of primary aggregates. Conferring colloidal stability in aqueous carbon black suspensions should thus have a drastic impact on their viscosity and conductivity. Carbon black was treated with strong acids following a wet oxidation procedure. An analysis of the resulting particle surface chemistry and electrophoretic mobility was performed in evaluating colloidal stability. Changes in suspension microstructure due to oxidation were observed using small-angle X-ray scattering. Utilizing rheo-electric measurements, the evolution of the viscosity and conductivity of the carbon black suspensions as a function of shear rate and carbon content was thoroughly studied. The carboxyl groups installed on the carbon black surface through oxidation increased the surface charge density and enhanced repulsive interactions. Electrostatic stability inhibited the formation of the large-scale agglomerates in favor of the stable primary aggregates in suspension. While shear thinning, suspension conductivities were found to be weakly dependent on the shear intensity regardless of the carbon content. Most importantly, aqueous carbon black suspensions formulated from electrostatically repulsive primary aggregates displayed a smaller rise in conductivity with carbon content compared to those formulated from attractive agglomerates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rheological and microstructural characterization of aqueous suspensions of carbon black and reduced graphene oxide

Carbon black is often used as a conductivity enhancer in battery electrodes. Reduced graphene oxide is another conducting material, with a high aspect ratio sheet-like morphology, and offers the possibility of generating a conducting network at loadings that are small compared to carbon black. Suspensions of conducting carbon, active materials and binders are typically coated on current collectors during the formation of electrodes. The rheology of these suspensions is an important indicator of the connectivity of particles in the suspension and impacts the electrical conductivity as well as the thickness of the coated layer. In this work, the rheology and microstructures of aqueous suspensions of para-aminobenzoic acid terminated carbon black (CB) with and without reduced graphene oxide (RGO) were investigated. The CB loading varied between 0.05 wt.% -10 wt.%, while the samples containing RGO had an RGO loading of 0.05 wt.%. The pH of the suspension was varied from 7.5 to 3. The carboxyl groups on the CB surface are deprotonated at pH 7.5, making the particles hydrophilic. Protonation of the carboxylate groups at pH 3 makes the particles partially hydrophobic. Suspensions of CB showed Newtonian behavior at all loadings for pH 7.5, and at loadings below 1.5 wt.% for pH 3. They are shear thinning at loadings between 1.5–10 wt.%. Interestingly, the low shear viscosity is non-monotonic with CB loading, rising up to a CB loading of 7.5 wt.%, and then dropping at 10 wt.%. Cryogenic scanning electron microscopy (SEM) showed CB particles forming aggregates at pH 3 for CB loadings greater than 1.5 wt.%. At pH 3, addition of 0.05 wt.% RGO resulted in a viscosity increase for suspensions containing 0.5 wt.% CB, as the RGO formed connections with CB particles that enhanced network formation. Adding RGO had little effect on suspensions that had 1.5 wt.% CB. The combination of SEM imaging and suspension rheology provides insight into the particle connectivity for the carbon-based materials studied here. These insights will be useful in determining coating conditions for slurries used in rechargeable battery electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Black carbon emissions and reduction potential in China: 2015–2050

Black carbon is a product of the incomplete combustion of carbonaceous fuels and has significant adverse effects on climate change, air quality, and human health. China has been a major contributor to global anthropogenic black carbon emissions. This study develops a black carbon inventory in China, using 2015 as the base year, and projects annual black carbon emissions in China for the period 2016–2050, under two scenarios: a Reference scenario and an Accelerated Reduction scenario. The study estimates that the total black carbon emissions in China in 2015 were 1100 thousand tons (kt), with residential use being the biggest contributor, accounting for more than half of the total black carbon emissions, followed by coke production, industry, agricultural waste burning, and transportation. This study then projects the total black carbon emissions in China in 2050 to be 278 kt in the Reference scenario and 86 kt in the Accelerated Reduction Scenario. Compared to the Reference scenario, the Accelerated Reduction scenario will achieve much faster and deeper black carbon reductions in all the sectors. The dramatic reductions can be attributed to the fuel switching in the residential sector, faster implementation of high-efficiency emission control measures in the industry, transportation, and coke production sectors, and faster phase-out of agricultural waste open burning. This analysis reveals the high potential of black carbon emission reductions across multiple sectors in China through the next thirty years.

54 ENVIRONMENTAL SCIENCES↗

Improved representation of black carbon mixing structures suggests stronger direct radiative heating

Black carbon significantly influences the Earth system because of its strong solar radiation absorption. However, its direct radiative effect remains poorly understood in current climate models, partly because current climate models oversimplify the diverse structures formed when black carbon mixes with other atmospheric components. Here we show that incorporating more realistic, multi-mixing-structure representations of black carbon increases the direct radiative effect. We find that aged black carbon particles, with thicker coatings and higher embedded fractions, enhance the direct radiative effect more efficiently. Using machine learning alongside the Community Earth System Model, we show that the direct radiative effect at the top of the atmosphere in regions with heavy black carbon pollution is 31.6% greater when multi-mixing structures are considered. These findings highlight the importance of modeling complex mixing structures of particle-resolved black carbon to accurately capture their warming impacts on global atmosphere, particularly in highly polluted regions.

54 ENVIRONMENTAL SCIENCES↗

Wildfire Smoke Demonstrates Significant and Predictable Black Carbon Light Absorption Enhancements

Abstract Black carbon (BC) is estimated to have the second largest anthropogenic radiative forcing in earth‐systems models (ESMs), but there is significant uncertainty in its impact due to complex mixing with organics. Laboratory‐generated particles show that co‐mixed non‐absorbing material enhances absorption by BC by a factor of 2–3.5 as predicted by optical models. However, weak or no enhancements are often reported for field studies. The cause of lower‐than‐expected absorption is not well understood and implies a lower radiative impact of BC compared to how many ESMs currently treat aerosols. By analyzing BC aerosol particle‐by‐particle we reconcile observed and expected absorption for ambient smoke plumes varying in geographic origin, fuel types, burn conditions, atmospheric age and transport. Although particle‐by‐particle tracking is computationally prohibitive for sophisticated ESMs we show that realistic BC absorption is reliably estimated by bulk properties of the plume providing a suitable parameterization to constrain black carbon radiative forcing.

54 ENVIRONMENTAL SCIENCES↗

A review of the shear rheology of carbon black suspensions

The microstructural link to the rheology of carbon black suspensions has recently become clear as a result of advances in computational and experimental methods. This understanding reveals the important role of the restructuring, build-up, and break-up of carbon black agglomerates in simple shear, rationalized by a dimensionless balance of the hydrodynamic forces acting to break the agglomerates apart against the cohesive forces holding them together (i.e., the Mason number). The Mason number not only can predict the origin of reversible thixotropy seen in carbon black suspensions observed at higher shear intensities, but can also be used to rationalize the evolution of microstructure at lower shear intensities. This review focuses on carbon black suspension behavior, but the insights derived from carbon black suspensions are broadly applicable to a diverse class of soft matter including colloidal gels relevant to a variety of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pyrolytic carbon black composite and method of making the same

A method of recovering carbon black includes the step of providing a carbonaceous source material containing carbon black. The carbonaceous source material is contacted with a sulfonation bath to produce a sulfonated material. The sulfonated material is pyrolyzed to produce a carbon black containing product comprising a glassy carbon matrix phase having carbon black dispersed therein. The pyrolysis can be conducted at a temperature from 1100° C. to 1490° C. A method of making a battery electrode and a lithium ion or sodium ion battery is also disclosed.

Naskar, Amit K.↗

Assessing outdoor air quality and public health impact attributable to residential black carbon emissions in rural China

Black carbon (BC) is a significant component of particulate matter (PM) that relates to air pollution, climate forcing, and further implications for public health. BC is predominantly released from the combustion of solid fuels. Combustion of low-quality fuels in rural China may induce severe respiratory and cardiopulmonary health outcomes for residents, which have however been inadequately assessed. One major reason for the limited understanding is the lack of a high-resolution inventory. An improved method of estimating the BC-associated public health burden is needed. This work quantified premature mortalities due to residential BC emissions in rural China. Domestic BC emissions at 1×1 km resolution were compiled based on previous field investigation, which were further configured for air quality simulation. A chemistry transport model, WRF–CMAQ v5.2, was employed for simulating BC concentrations. The consequent premature mortalities were quantified by a BC-specific concentration-response function (CRF) derived from an epidemiological study. Results show that residential combustion of solid fuel in rural China emitted 648.0 Gg (95%CI: 361.0–965.9) BC in 2014, after dispersion, accounting for 51.8% of annual mean ground-level BC concentration in China. Such impact was most severe in North and Northeast China, and the Sichuan Basin. The further investigation estimated 171,000 (95%CI: 69,000–387,000) premature mortalities that were attributable to exposure to rural residential BC. These findings reveal the major contribution of rural residential BC emissions to air pollution formation and public health impacts. Our findings are anticipated to provide useful information for enacting the next-stage environmental strategy for the residential sector in China.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

An Exploratory Approach Using Regression and Machine Learning in the Analysis of Mass Absorption Cross Section of Black Carbon Aerosols: Model Development and Evaluation

Mass absorption cross-section of black carbon (MAC BC ) describes the absorptive cross-section per unit mass of black carbon, and is, thus, an essential parameter to estimate the radiative forcing of black carbon. Many studies have sought to estimate MAC BC from a theoretical perspective, but these studies require the knowledge of a set of aerosol properties, which are difficult and/or labor-intensive to measure. We therefore investigate the ability of seven data analytical approaches (including different multivariate regressions, support vector machine, and neural networks) in predicting MAC BC for both ambient and biomass burning measurements. Our model utilizes multi-wavelength light absorption and scattering as well as the aerosol size distributions as input variables to predict MAC BC across different wavelengths. We assessed the applicability of the proposed approaches in estimating MAC BC using different statistical metrics (such as coefficient of determination (R 2 ), mean square error (MSE), fractional error, and fractional bias). Overall, the approaches used in this study can estimate MAC BC appropriately, but the prediction performance varies across approaches and atmospheric environments. Based on an uncertainty evaluation of our models and the empirical and theoretical approaches to predict MAC BC , we preliminarily put forth support vector machine (SVM) as a recommended data analytical technique for use. We provide an operational tool built with the approaches presented in this paper to facilitate this procedure for future users.

54 ENVIRONMENTAL SCIENCES↗

Black carbon aerosol number and mass concentration measurements by picosecond short-range elastic backscatter lidar

Abstract Black carbon aerosol emissions are recognized as contributors to global warming and air pollution. There remains, however, a lack of techniques to remotely measure black carbon aerosol particles with high range and time resolution. This article presents a direct and contact-free remote technique to estimate the black carbon aerosol number and mass concentration at a few meters from the emission source. This is done using the Colibri instrument based on a novel technique, referred to here as Picosecond Short-Range Elastic Backscatter Lidar (PSR-EBL). To address the complexity of retrieving lidar products at short measurement ranges, we apply a forward inversion method featuring radiometric lidar calibration. Our method is based on an extension of a well-established light-scattering model, the Rayleigh–Debye–Gans for Fractal-Aggregates (RDG-FA) theory, which computes an analytical expression of lidar parameters. These parameters are the backscattering cross-sections and the lidar ratio for black carbon fractal aggregates. Using a small-scale Jet A-1 kerosene pool fire, we demonstrate the ability of the technique to quantify the aerosol number and mass concentration with centimetre range-resolution and millisecond time-resolution.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

China's Contribution to Arctic Black Carbon Declined From 2009 to 2022

Black carbon (BC) aerosol is an important driver of Arctic warming, and China used to be a major contributor to the Arctic BC burden through long-range atmospheric transport. Here we show that China's contribution declined significantly from 2009 to 2022, primarily due to reductions in domestic BC emissions following the implementation of clean air policies. Global chemistry-transport model simulations indicate a relative decline of ∼3% yr −1 ( p < 0.05) in China's Arctic BC contribution, exceeding the decrease rate in the underlying emission inventory. Sensitivity simulations further suggest that climate change-induced shifts in atmospheric transport may have amplified this decline. Observations of aerosol absorption coefficients (σ ap ) at Arctic background observatories revealed steeper declines in σ ap when modeled China-to-total BC ratios were higher. Moreover, σ ap correlated positively with modeled BC from China, with stronger relationships as the modeled China-to-total BC ratios increased. Together, these results provide robust evidence that China's emission reductions have diminished its role in Arctic BC, contributing an estimated 0.02 W m −2 decrease in the direct radiative effect during the Arctic haze season.

GEOS-chem model↗

Distinct responses of Asian summer monsoon to black carbon aerosols and greenhouse gases

Black carbon (BC) aerosols emitted from natural and anthropogenic sources induce positive radiative forcing and global warming, which in turn significantly affect the Asian summer monsoon (ASM). However, many aspects of the BC effect on the ASM remain elusive and largely inconsistent among previous studies, which is strongly dependent on different low-level thermal feedbacks over the Asian continent and the surrounding ocean. This study examines the response of the ASM to BC forcing in comparison with the effect of doubled greenhouse gases (GHGs) by analyzing the Precipitation Driver Response Model Intercomparison Project (PDRMIP) simulations under an extremely high BC level (10 times modern global BC emissions or concentrations, labeled BC×10) from nine global climate models (GCMs). The results show that although BC and GHGs both enhance the ASM precipitation minus evaporation (P–E; a 13.6 % increase for BC forcing and 12.1 % for GHGs from the nine-model ensemble, respectively), there exists a much larger uncertainty in changes in ASM P–E induced by BC than by GHGs. The summer P–E is increased by 7.7 % to 15.3 % due to these two forcings over three subregions, including East Asian, South Asian and western North Pacific monsoon regions. Further analysis of moisture budget reveals distinct mechanisms controlling the increases in ASM P–E induced by BC and GHGs. The change in ASM P–E by BC is dominated by the dynamic effect due to the enhanced large-scale monsoon circulation, whereas the GHG-induced change is dominated by the thermodynamic effect through increasing atmospheric water vapor. Radiative forcing of BC significantly increases the upper-level atmospheric temperature over the Asian region to enhance the upper-level meridional land–sea thermal gradient (MLOTG), resulting in a northward shift of the upper-level subtropical westerly jet and an enhancement of the low-level monsoon circulation, whereas radiative forcing of GHGs significantly increases the tropical upper-level temperature, which reduces the upper-level MLOTG and suppresses the low-level monsoonal circulation. Hence, our results indicate a different mechanism of BC climate effects under the extremely high BC level: that BC forcing significantly enhances the upper-level atmospheric temperature over the Asian region, determining ASM changes, instead of low-level thermal feedbacks as indicated by previous studies.

54 ENVIRONMENTAL SCIENCES↗