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Impact of slurry preparation method on the rheological behaviour of dense anode slurries for lithium-ion batteries 浆料制备方法对锂离子电池致密正极浆料流变特性的影响
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-03-19 DOI: 10.1007/s00397-024-01440-4
Soichiro Makino, Yusuke Akimoto, Masahiko Ishii, Hiroshi Nakamura

Understanding and controlling the rheology of electrode slurries for lithium-ion batteries is critical both for improving their manufacturing efficiency and for achieving desirable battery performance. Here, we show drastic “slurry-preparation-dependent” rheology in an anode slurry for lithium-ion batteries, focusing on the behaviour of carboxymethyl cellulose (CMC), which is the most popular dispersant for graphite particles in anode slurries. Slurry preparation with dry-state mixing, where water is added to a dry mixture of graphite and CMC powder, results in much higher viscosity, yield stress, and elastic modulus than those achieved with conventional wet-state mixing, where graphite is added to a CMC solution. Cryogenic scanning electron microscopy reveals strange CMC “clumps” formed among the graphite particles in the slurry prepared with dry-state mixing. We attribute the increases in viscosity, yield stress, and elastic modulus for the slurries prepared with dry-state mixing to these clumps of CMC, which can enhance the adhesion between graphite particles and thereby constrain their motion. We also show that pre-shearing irreversibly decreases viscosity, yield stress, and elastic modulus, suggesting that the clumps of CMC are irreparably broken down by applied shear. The influence of the slurry preparation method on the rheological properties of anode slurries has not received attention in previous studies. Hence, we believe that our results might provide new strategies for controlling the rheology of the anode slurry in the manufacturing process for lithium-ion batteries.

了解和控制锂离子电池电极浆料的流变性对于提高其生产效率和实现理想的电池性能至关重要。在这里,我们展示了锂离子电池负极浆料中剧烈的 "浆料制备依赖性 "流变,重点是羧甲基纤维素(CMC)的行为,CMC 是负极浆料中石墨颗粒最常用的分散剂。采用干态混合法制备浆料,即在石墨和 CMC 粉末的干混合物中加水,其粘度、屈服应力和弹性模量远高于传统湿态混合法(即在 CMC 溶液中加入石墨)所获得的粘度、屈服应力和弹性模量。低温扫描电子显微镜显示,在干态混合制备的浆料中,石墨颗粒之间形成了奇怪的 CMC "团块"。我们将干态混合制备的浆料粘度、屈服应力和弹性模量的增加归因于这些 CMC 团块,它们可以增强石墨颗粒之间的粘附力,从而限制石墨颗粒的运动。我们还发现,预剪切会不可逆地降低粘度、屈服应力和弹性模量,这表明在施加剪切力时,CMC团块会被不可修复地分解。在以往的研究中,浆料制备方法对阳极浆料流变特性的影响尚未引起重视。因此,我们相信我们的研究结果可能会为锂离子电池制造过程中负极浆料流变性的控制提供新的策略。
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引用次数: 0
Controlling the rheo-electric properties of graphite/carbon black suspensions by ‘flow switching’ 通过 "流动切换 "控制石墨/炭黑悬浮液的流变电特性
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-03-13 DOI: 10.1007/s00397-024-01439-x
Thomas Larsen, John R. Royer, Fraser H. J. Laidlaw, Wilson C. K. Poon, Tom Larsen, Søren J. Andreasen, Jesper de C. Christiansen

The ability to manipulate rheological and electrical properties of colloidal carbon black gels makes them attractive in composites for energy applications such as batteries and fuel cells, where they conduct electricity and prevent sedimentation of ‘granular’ active components. While it is commonly assumed that granular fillers have a simple additive effect on the composite properties, new phenomena can emerge unexpectedly, with some composites exhibiting a unique rheological bi-stability between high-yield-stress and low-yield-stress states. Here we report such bi-stability in suspensions of non-Brownian graphite and colloidal carbon black in oil, a model system to mimic composite suspensions for energy applications. Steady shear below a critical stress elicits a transition to a persistent mechanically weak and poorly conducting state, which must be ‘rejuvenated’ using high-stress shear to recover a stronger, high-conductivity state. Our findings highlight the highly tunable nature of binary granular/gel composite suspensions and present new possibilities for optimising mixing and processing conditions for Li-ion battery slurries.

摘要胶体炭黑凝胶具有流变和电学特性,因此在电池和燃料电池等能源应用领域的复合材料中很有吸引力,因为它们能导电并防止 "颗粒状 "活性成分沉积。虽然人们通常认为颗粒填料对复合材料的性能具有简单的叠加效应,但新现象可能会出乎意料地出现,一些复合材料在高屈服应力和低屈服应力状态之间表现出独特的流变双稳态性。在这里,我们报告了油中非布朗石墨和胶体炭黑悬浮液的这种双稳态性,这是一种模拟能源应用中复合悬浮液的模型系统。低于临界应力的稳定剪切会导致向持续的机械弱导电状态过渡,这种状态必须通过高应力剪切才能 "恢复活力",从而恢复到较强的高导电状态。我们的研究结果突显了二元颗粒/凝胶复合悬浮液的高度可调性,为优化锂离子电池浆料的混合和加工条件提供了新的可能性。 图文摘要
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引用次数: 0
Correction to: A metamodel for confined yield stress flows and parameters’ estimation 更正:约束屈服应力流元模型及参数估计
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-03-06 DOI: 10.1007/s00397-024-01441-3
Clément Berger, David Coulette, Paul Vigneaux
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引用次数: 0
Generalized second-grade fluid flow over a tilted plate with bump topography 带有凹凸地形的倾斜板上的广义二级流体流动
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-03-02 DOI: 10.1007/s00397-024-01438-y
Mahesh T, Satyananda Panda

The long-wave theory is used to model the thin film flow of a generalized second-grade fluid (GSGF) down a tilted plate with a bump topography. The derived single non-linear partial differential equation for the film thickness describes the surface wave generated by the bump, which disturbs the uniform flow. The model involves the non-Newtonian and geometrical parameters that investigate the wave’s shape and amplitude. The model equation is strongly non-linear due to the GSGF’s constitutive equations, and it is solved numerically using the finite volume method, where the flux function is approximated implicitly using the upwind scheme. The simulation reveals that the bump creates the surface wave, it splits and propagates, and its shape and size are influenced by the bump’s height and the non-Newtonian fluid properties.

长波理论用于模拟广义第二级流体(GSGF)在具有凹凸地形的倾斜板上的薄膜流动。推导出的薄膜厚度单非线性偏微分方程描述了凹凸产生的表面波,它扰乱了均匀流动。该模型涉及研究波形和振幅的非牛顿参数和几何参数。由于 GSGF 的构成方程,该模型方程具有很强的非线性,采用有限体积法对其进行数值求解,其中通量函数采用上风方案隐式近似。模拟结果表明,凹凸产生表面波,表面波分裂并传播,其形状和大小受凹凸高度和非牛顿流体特性的影响。
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引用次数: 0
A metamodel for confined yield stress flows and parameters’ estimation 约束屈服应力流和参数估计的元模型
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-02-27 DOI: 10.1007/s00397-024-01436-0
Clément Berger, David Coulette, Paul Vigneaux

With the growing demand of mineral consumption, the management of the mining waste is crucial. Cemented paste backfill (CPB) is one of the techniques developed by the mining industry to fill the voids generated by the excavation of underground spaces. The CPB process is the subject of various studies aimed at optimizing its implementation in the field. In this article, we focus on the modelling of the backfill phase where it has been shown in Vigneaux et al. (Cem. Concr. Res. 164:107038, 2023) that a viscoplastic lubrication model can be used to describe CPB experiments. The aim here is to propose an accelerated method for performing the parameters’ estimation of the properties of the paste (typically its rheological properties), with an inverse problem procedure based on observed height profiles of the paste. The inversion procedure is based on a metamodel built from an initial partial differential equation model, thanks to a polynomial chaos expansion coupled with a principal component analysis.

随着矿产消费需求的不断增长,采矿废料的管理至关重要。水泥浆回填(CPB)是采矿业开发的技术之一,用于填补挖掘地下空间时产生的空隙。CPB 工艺是各种研究的主题,旨在优化其现场实施。在本文中,我们将重点关注回填阶段的建模,Vigneaux 等人(Cem. Concr. Res. 164:107038, 2023)的研究表明,粘弹性润滑模型可用于描述 CPB 实验。本文的目的是提出一种加速方法,根据观察到的浆料高度剖面,利用反问题程序对浆料特性(通常是流变特性)进行参数估计。由于多项式混沌扩展与主成分分析相结合,反演程序基于从初始偏微分方程模型建立的元模型。
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引用次数: 0
Influence of various pretreatments on molecular and rheological properties of a linear and a long-chain branched polypropylene 各种预处理对线性和长链支化聚丙烯分子和流变特性的影响
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-02-26 DOI: 10.1007/s00397-024-01437-z
Helmut Münstedt, Joachim Kaschta

The influence of a mechanical or a thermal pretreatment of a linear (L-PP) and a long-chain branched polypropylene (LCB-PP) in the molten state was studied. The molar mass distributions and the branching structure were determined by high-temperature gel permeation chromatography HT-GPC coupled with laser-light scattering. The samples were extruded through long or short capillaries of various geometries corresponding to a predominant shear or elongational deformation. As a rheological probe, the extrudate swell at low stresses was measured for the differently pretreated samples. For the L-PP, neither molecular nor rheological changes were observed. However, the extrudate swell of the LCB-PP was found to decrease with increasing volume throughput. It was more strongly affected by shear in the capillary than by molecule stretching in the entry region. The smaller extrudate swell was accompanied by a decrease of the high molar mass tail of the LCB-PP, which could be the reason for the decay of swell, in principle. However, a comparable degradation of the high molar mass tail was obtained by a pure thermal treatment that was shown to leave the extrudate swell unchanged. This result and the unaffected branching structures found by high-temperature gel permeation chromatography (HT-GPC) support the hypothesis of a change of the branching topography by the mechanical pretreatment.

研究了线性聚丙烯(L-PP)和长链支化聚丙烯(LCB-PP)在熔融状态下机械预处理或热预处理的影响。采用高温凝胶渗透色谱法 HT-GPC 和激光光散射法测定了摩尔质量分布和支化结构。样品通过不同几何形状的长毛细管或短毛细管挤出,这些毛细管的几何形状与主要的剪切变形或拉伸变形相对应。作为流变学探针,测量了不同预处理样品在低应力下的挤出膨胀率。对于 L-PP 样品,既没有观察到分子变化,也没有观察到流变变化。不过,随着体积产量的增加,LCB-PP 的挤出物膨胀率会降低。毛细管中的剪切力比入口区域的分子拉伸对其影响更大。在挤出物膨胀变小的同时,LCB-PP 的高摩尔质量尾部也随之减小,这在原则上可能是膨胀变小的原因。然而,通过纯热处理,高摩尔质量尾部的降解程度相当,这表明挤出物的膨胀率保持不变。这一结果以及高温凝胶渗透色谱法(HT-GPC)发现的未受影响的支化结构支持了机械预处理改变支化拓扑结构的假设。
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引用次数: 0
Frequency response analysis of the Bautista-Manero-Puig model with normal stress: analytical and numerical solution for large amplitudes 具有法向应力的 Bautista-Manero-Puig 模型的频率响应分析:大振幅的分析和数值解法
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-02-16 DOI: 10.1007/s00397-024-01434-2
E. Hernandez, F. Bautista, J. P. García-Sandoval, O. Manero

We derive explicit analytical expressions for the recurrence relations using the analytical matrix method for frequency response and the Bautista-Manero-Puig model for complex fluids. The BMP model is derived from the Extended Irreversible Thermodynamics formalism and has been shown to be useful in predicting the complex rheological behavior of self-associative systems. All harmonics of the alternating normal and shear stresses in oscillatory shear with various amplitude oscillatory regimes (AOS) can be calculated analytically, i.e., small amplitude oscillatory shear (SAOS), medium amplitude oscillatory shear (MAOS), and large amplitude oscillatory shear (LAOS). We show that incorporating the effects of the first and second normal stress differences for all AOS regimes leads to the emergence of higher harmonics. We establish the limits between the different AOS regimes based on criteria suggested by the analytical method. For some typical systems, such as CTAB-NaSal, we found a satisfactory quantitative agreement with the measured behavior of AOS.

我们利用频率响应的解析矩阵法和复杂流体的 Bautista-Manero-Puig 模型推导出了递推关系的明确解析表达式。BMP 模型源于扩展不可逆热力学形式主义,已被证明可用于预测自耦合系统的复杂流变行为。振荡剪切中交变法向应力和剪切应力的所有谐波以及各种振幅振荡区(AOS)都可以通过分析计算出来,即小振幅振荡剪切(SAOS)、中振幅振荡剪切(MAOS)和大振幅振荡剪切(LAOS)。我们的研究表明,将第一和第二法向应力差的影响纳入所有 AOS 体系会导致高次谐波的出现。我们根据分析方法提出的标准,确定了不同 AOS 状态之间的界限。对于一些典型的系统,如 CTAB-NaSal,我们发现其与 AOS 的测量行为在定量方面达到了令人满意的一致。
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引用次数: 0
Theoretical study on Poiseuille flow of thixotropic yield stress fluids: an exact solution 触变屈服应力流体的 Poiseuille 流动理论研究:精确解法
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-02-08 DOI: 10.1007/s00397-024-01431-5
Ren Jiangtao, Yin Deshun, Zhao Bin, Ma Liangzhu

The steady pipe flow of thixotropic yield stress fluids has been investigated theoretically based on a modified isotropic kinematic hardening (mIKH) model. Analytical solution is derived for a specific case (m = n = 1) and a general semi-analytical solution is put forward as well. The effect of thixotropic yield stress on shear rate and velocity profiles is illustrated by comparing to other well-known solutions. Moreover, the influences of model parameters are examined. It is worth noting that shear banding may occur at the yielded surface in case of a sufficiently large Bingham number, thixotropic number, and flow index, but a sufficient small value of structure-related exponent.

基于修正的各向同性运动硬化(mIKH)模型,对触变屈服应力流体的稳定管道流动进行了理论研究。针对特定情况(m = n = 1)得出了分析解,并提出了一般的半分析解。通过与其他著名解法的比较,说明了触变屈服应力对剪切速率和速度曲线的影响。此外,还考察了模型参数的影响。值得注意的是,在宾汉数、触变数和流动指数足够大,但结构相关指数足够小的情况下,屈服表面可能会出现剪切带。
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引用次数: 0
Fully angularly resolved 3D microrheology with optical tweezers 利用光学镊子实现完全角度分辨的三维微流变学
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-02-08 DOI: 10.1007/s00397-024-01435-1
Andrew B. Matheson, Tania Mendonca, Matthew G. Smith, Ben Sutcliffe, Andrea Jannina Fernandez, Lynn Paterson, Paul A. Dalgarno, Amanda J. Wright, Manlio Tassieri

Microrheology with optical tweezers (MOT) is an all-optical technique that allows the user to investigate a materials’ viscoelastic properties at microscopic scales, and is particularly useful for those materials that feature complex microstructures, such as biological samples. MOT is increasingly being employed alongside 3D imaging systems and particle tracking methods to generate maps showing not only how properties may vary between different points in a sample but also how at a single point the viscoelastic properties may vary with direction. However, due to the diffraction limited shape of focussed beams, optical traps are inherently anisotropic in 3D. This can result in a significant overestimation of the fluids’ viscosity in certain directions. As such, the rheological properties can only be accurately probed along directions parallel or perpendicular to the axis of trap beam propagation. In this work, a new analytical method is demonstrated to overcome this potential artefact. This is achieved by performing principal component analysis on 3D MOT data to characterise the trap, and then identify the frequency range over which trap anisotropy influences the data. This approach is initially applied to simulated data for a Newtonian fluid where the trap anisotropy induced maximum error in viscosity is reduced from ~ 150% to less than 6%. The effectiveness of the method is corroborated by experimental MOT measurements performed with water and gelatine solutions, thus confirming that the microrheology of a fluid can be extracted reliably across a wide frequency range and in any arbitrary direction. This work opens the door to fully spatially and angularly resolved 3D mapping of the rheological properties of soft materials over a broad frequency range.

使用光学镊子的微观流变学(MOT)是一种全光学技术,可让用户在微观尺度上研究材料的粘弹性能,尤其适用于那些具有复杂微观结构的材料,如生物样品。MOT 越来越多地与三维成像系统和粒子跟踪方法结合使用,不仅能生成显示样品中不同点之间特性变化的地图,还能显示单点粘弹性特性随方向的变化情况。然而,由于聚焦光束的衍射受限,光学陷阱在三维空间中本身就是各向异性的。这会导致在某些方向上高估流体的粘度。因此,只能沿着平行或垂直于陷阱光束传播轴的方向精确探测流变特性。在这项工作中,我们展示了一种新的分析方法来克服这种潜在的误差。具体做法是对三维 MOT 数据进行主成分分析,以确定陷波器的特征,然后确定陷波器各向异性影响数据的频率范围。这种方法最初应用于牛顿流体的模拟数据,在该模拟数据中,陷波器各向异性引起的最大粘度误差从约 150% 降至 6% 以下。对水和明胶溶液进行的 MOT 实验测量证实了该方法的有效性,从而证实流体的微观流变学可以在很宽的频率范围和任意方向上可靠地提取出来。这项工作为在宽频率范围内绘制软材料流变特性的完全空间和角度分辨三维图打开了大门。
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引用次数: 0
From Alveograph test to extensional behavior of wheat flour dough 从阿尔维图测试到小麦粉面团的扩展行为
IF 2.3 3区 工程技术 Q2 MECHANICS Pub Date : 2024-01-23 DOI: 10.1007/s00397-024-01430-6
Maude Dufour, Laurent Chaunier, Florence Hugon, Aurore Dugué, Kamal Kansou, Luc Saulnier, Guy Della Valle

Dough extensional properties obtained from 14 wheat flours hydrated at 50% (/flour weight) were assessed by the empirical test of Alveograph, a bubble inflation test, and by the rheometric test of uniaxial compression in lubricated conditions (LSF) at large deformations. In baking industry, comparison between flours is based on several parameters (n ≥ 5) defined from the alveogram, which is the time variations of pressure inside dough. In this study, the alveogram is converted into a stress-strain curve (σ = f(εb)). Then, from this curve, the extensional behavior coefficient of the flours, assessed by the consistency k0, is fitted between 0 ≤ εb ≤ 1.5, assuming (dot{varepsilon_b}) = 0.25 s−1 (R2 = 0.99 ± 0.01 for 14 flours). The flow index (n = 0.36) and strain hardening index (SHI = 1.73) are kept constant. The model is validated by comparing the stress values calculated from the alveogram to those measured in LSF for wheat flour doughs hydrated at 50% (R2 = 0.91) at εb = 1 and 0.25.10−2 < (dot{varepsilon_b})< 2.5 s−1. Therefore, the Alveograph, which allows classifying flours according to several dough stretching properties, also provides access to the model of dough extensional behavior.

Determining dough extensional properties for alveograph test and validating by comparison with resutls obtained by LSF

摘要 通过气泡膨胀试验(Alveograph)和大变形润滑条件下单轴压缩流变试验(LSF)评估了 14 种小麦面粉水合 50%(/面粉重量)后的面团扩展特性。在烘焙行业中,不同面粉之间的比较是基于气泡图(即面团内部压力的时间变化)中定义的几个参数(n ≥ 5)。在本研究中,凹凸图被转换成应力-应变曲线(σ = f(εb))。假设 (dot{varepsilon_b}) = 0.25 s-1 (14 种面粉的 R2 = 0.99 ± 0.01),然后根据该曲线,在 0 ≤ εb ≤ 1.5 之间拟合出面粉的延伸行为系数,该系数由稠度 k0 评估。流动指数(n = 0.36)和应变硬化指数(SHI = 1.73)保持不变。在 εb = 1 和 0.25.10-2 < (dot{varepsilon_b})< 2.5 s-1 条件下,对水化程度为 50%(R2 = 0.91)的小麦粉面团,通过比较由凹面图计算出的应力值和在 LSF 中测得的应力值,验证了该模型。因此,可以根据几种面团拉伸特性对面粉进行分类的Alveograph也提供了获得面团延伸行为模型的途径。 图解摘要确定Alveograph测试的面团延伸特性,并通过与LSF获得的结果进行比较来验证。
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引用次数: 0
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