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Bioinspired stiff–soft gradient network structure for high-performance impact-resistant elastomers 用于高性能抗冲击弹性体的生物启发式软硬梯度网络结构
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-06 DOI: 10.1016/j.giant.2024.100320
Jin Huang , Hangsheng Zhou , Li Zhang , Hao Zha , Wei Shi , Tianyi Zhao , Mingjie Liu

Traditional impact-resistance materials relying on the combination of supporting materials and energy-dissipation elastomers can effectively reduce shock load, yet the sharp interface between two types of materials causes discontinuous stress transfer and cracking. Here, inspired by the squid beak, we report a type of high impact-resistance gradient elastomers with large-scale modulus gradient with about three orders of magnitude (modulus range of 7 × 103 ∼ 7 × 106 Pa) and high energy dissipation (loss factor > 0.6) over a wide temperature range by diffusively introducing stiff polymers in a highly damping elastomer with controlled mechanical properties. Under the action of an external force, our gradient elastomers exhibit soft-while-stiff attributes, combining cushioning and support. In drop hammer impact tests, our gradient materials can reduce impact strength by 80 %, significantly better than commercial protective gear. It is worth mentioning that the modulus of the bottom layer matches that of the tissues for better protection.

传统的抗冲击材料主要依靠支撑材料和消能弹性体的组合来有效降低冲击载荷,但两类材料之间的尖锐界面会导致不连续的应力传递和开裂。在此,我们受乌贼喙的启发,通过在具有可控机械性能的高阻尼弹性体中扩散引入刚性聚合物,报告了一种在宽温度范围内具有约三个数量级的大规模模量梯度(模量范围为 7 × 103 ∼ 7 × 106 Pa)和高能量耗散(损耗因子为 0.6)的高抗冲击梯度弹性体。在外力作用下,我们的梯度弹性体表现出软中带硬的特性,兼具缓冲和支撑作用。在落锤冲击测试中,我们的梯度材料可降低 80% 的冲击强度,明显优于商用防护装备。值得一提的是,底层的模量与组织的模量相匹配,可提供更好的保护。
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引用次数: 0
Cross-linkable binder for composite silicon-graphite anodes in lithium-ion batteries 用于锂离子电池中硅-石墨复合阳极的可交联粘合剂
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-04 DOI: 10.1016/j.giant.2024.100319
Yi-Tong Zhang , Jin-Xin Xue , Rui Wang , Si-Xin Jia , Jian-Jun Zhou , Lin Li

Silicon (Si) is a promising substitute for graphite anode due to the high theoretical specific capacity (4200 mAh g−1). However, too large volume change exists during the lithiation/delithiation process. Composite anode, prepared by mixing Si with graphite, can realize higher specific capacity than graphite and much better cycle performance than Si anode. However, the capacity decay caused by pulverization of Si particles is still a great challenge. Here, a cross-linkable binder rich in nitrile, carboxyl and hydroxyl groups is designed for composite silicon-graphite (Si-C) anode. The nitrile and hydroxyl groups can be in situ cross-linked in the batteries through Ritter reaction. The cross-linked binder has excellent resilience and good adhesion to the active materials and current collector. The cycle performance of the cell with cross-linked binder is much better than the counterpart. Scanning electron microscopy results of the cycled Si-C anode show that the cross-linked binder can suppress the volume expansion and pulverization. Moreover, the investigation with X-ray photoelectronic spectrum and density function theory calculation demonstrate that the decomposition of ester solvent and LiPF6 on Si anode has been mitigated and more stable SEI film is formed on the Si-C anode. Our strategy of in situ cross-linking binder in the batteries has provided a feasible way for designing the next generation of silicon-based anodes with higher specific capacity and longer cycling life.

硅(Si)具有很高的理论比容量(4200 mAh g-1),因此很有希望成为石墨负极的替代品。然而,在石化/脱硅过程中体积变化太大。通过将硅与石墨混合制备的复合负极可以实现比石墨更高的比容量,循环性能也比硅负极好得多。然而,硅颗粒粉化导致的容量衰减仍然是一个巨大的挑战。在此,我们设计了一种富含腈基、羧基和羟基的可交联粘合剂,用于硅-石墨(Si-C)复合负极。腈基和羟基可通过里特反应在电池中原位交联。交联后的粘合剂具有优异的回弹性,与活性材料和集流器的粘附性良好。交联粘合剂电池的循环性能远远优于同类电池。循环硅-碳阳极的扫描电子显微镜结果表明,交联粘结剂可抑制体积膨胀和粉化。此外,X 射线光电子能谱研究和密度函数理论计算表明,酯溶剂和 LiPF6 在硅阳极上的分解得到了缓解,Si-C 阳极上形成了更稳定的 SEI 膜。我们在电池中原位交联粘合剂的策略为设计比容量更大、循环寿命更长的下一代硅基阳极提供了一种可行的方法。
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引用次数: 0
Updated view of new liquid-matter ferroelectrics with nematic and smectic orders 具有向列和共晶阶的新型液态物质铁电的最新观点
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-04 DOI: 10.1016/j.giant.2024.100318
Yaohao Song , Satoshi Aya , Mingjun Huang

The recent discovery of liquid-matter ferroelectrics not only opens a door to explore novel polar matter states and properties in the term of condensed matter physics but also provides unprecedented opportunities for developing new liquid crystal materials and technologies. The progression from the ferroelectric nematic phase to many other liquid-matter ferroelectrics represents a remarkable journey in emerging polar soft matter. In this perspective, we briefly introduce the latest quick rise and advancements of liquid-matter ferroelectrics that display the nematic and smectic characteristics. We summarize the recently-discovered new polar phases, their new physics, and potential technological innovations, and then give some hints that we consider critical for further exploration. More importantly, we seek to delve into broader discussions on chemical structure design, the underlying physical interactions driving various polar states, and their connections to a range of intriguing phenomena.

最近发现的液态物质铁电不仅为探索凝聚态物理学中的新型极性物质状态和性质打开了一扇大门,而且为开发新型液晶材料和技术提供了前所未有的机遇。从向列铁电相发展到许多其他液态物质铁电相,代表了新兴极性软物质的非凡历程。在这一视角中,我们简要介绍了显示向列和共晶特性的液态物质铁电的最新快速发展和进步。我们总结了最近发现的新极性相、它们的新物理学和潜在的技术创新,然后给出了一些我们认为对进一步探索至关重要的提示。更重要的是,我们试图深入探讨化学结构设计、驱动各种极性态的基本物理相互作用以及它们与一系列有趣现象之间的联系。
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引用次数: 0
Biomineralization strategy: from material manufacturing to biological regulation 生物矿化战略:从材料制造到生物调节
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-03 DOI: 10.1016/j.giant.2024.100317
Kexin Qin , Zitong Zheng , Jie Wang , Haihua Pan , Ruikang Tang

Biomineralization plays an important role in various physiological activities in both nature and living organisms. Organisms regulate the crystal nucleation, crystal phase, and crystal growth kinetics of inorganic phases through organic regulation, forming minerals with multi-level order, thereby playing a role in biological support, protection, and metabolic regulation. Unlike general inorganic minerals, biominerals are subtly regulated by organic organisms (such as small organic molecules, peptides, proteins, nucleic acids) and complex environments, possessing biological characteristics and becoming a part of living organisms. It can be seen that the process of biomineralization is not only the process of manufacturing biomaterials, but also the process of using materials to regulate organisms themselves. The biomimetic strategy based on biomineralization can achieve a huge transformation from the biomimetic preparation of functional materials to the biomimetic composite of organisms and materials. In this review, we briefly introduce biomimetic structures inspired by nature itself, and emphasize the important role of the relationship between organisms and materials in the process of biomineralization. We also briefly explore biominerals and their mechanisms. At the same time, a series of functional materials (such as self-cleaning hydrophobic materials, artificial spider silk fibers, mother of pearl like composite materials, humidity responsive materials, and bioprinting materials) synthesized through biomimetic strategies inspired by biomanufacturing materials were systematically elucidated. And a brief discussion was given on the synthesis of new functional organisms using biomimetic strategies to regulate organisms, such as using functional materials to regulate biomimetic repair of hard tissues, using biomineralization strategies to coat vaccines to improve their thermal stability during transportation and drug delivery efficiency in vivo, and constructing functional biomimetic artificial organelles on demand. Finally, this article summarizes the current opportunities and challenges based on biomineralization, providing further feasible guidance for future material regulation of life.

生物矿化在自然界和生物体的各种生理活动中发挥着重要作用。生物通过有机调控无机相的晶体成核、晶相和晶体生长动力学,形成具有多级有序的矿物,从而在生物支持、保护和代谢调节中发挥作用。与一般无机矿物不同,生物矿物受有机物(如有机小分子、肽、蛋白质、核酸等)和复杂环境的微妙调控,具有生物特性,成为生物体的一部分。可见,生物矿化过程不仅是制造生物材料的过程,也是利用材料调节生物体本身的过程。基于生物矿化的生物仿生策略可以实现从功能材料的生物仿生制备到生物与材料的生物仿生复合的巨大转变。在这篇综述中,我们简要介绍了受自然本身启发的生物仿生结构,并强调了生物与材料之间的关系在生物矿化过程中的重要作用。我们还简要探讨了生物矿物及其机理。同时,系统阐述了在生物制造材料的启发下,通过生物仿生策略合成的一系列功能材料(如自洁疏水材料、人造蜘蛛丝纤维、类珍珠母复合材料、湿度响应材料、生物打印材料等)。并简要论述了利用生物仿生策略调控生物体合成新的功能生物体,如利用功能材料调控硬组织的生物仿生修复、利用生物矿化策略包覆疫苗以提高疫苗在运输过程中的热稳定性和体内给药效率、按需构建功能性生物仿生人工细胞器等。最后,本文总结了当前基于生物矿化的机遇与挑战,为未来的生命材料调控提供了进一步的可行性指导。
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引用次数: 0
Nonlinear optical director reorientation in heliconical cholesteric liquid crystals: a brief review 螺旋胆甾型液晶中的非线性光学导向重新定向:简要回顾
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-28 DOI: 10.1016/j.giant.2024.100311
Liana Lucchetti , Giovanni Nava

Cholesteric liquid crystals, also known as chiral nematics, possess a right-angle helicoidal structure with pitch in the submicrometer and micrometer range. Although the possibility of getting optical reorientation in this kind of materials has been considered since the discovery of giant optical nonlinearity in nematic liquid crystals, a significant light-induced modulation of the helical structure has shown to be a challenging task. The recent experimental realization of a chiral phase with an oblique helicoidal structure, identified as the heliconical phase predicted by Meyer and DeGennes in 1968, offers the opportunity to observe such an optical reorientation of the optic axis. This paper is a brief review of the nonlinear optical properties of these unconventional chiral nematic liquid crystals and is aimed at showing that the world of liquid crystalline phases can still amaze with new material properties and new physics.

胆甾型液晶又称手性向列液晶,具有直角螺旋结构,间距在亚微米和微米范围内。虽然自从发现向列液晶的巨大光学非线性以来,人们就一直在考虑在这类材料中实现光学重新定向的可能性,但要在光的诱导下对螺旋结构进行明显的调制,已被证明是一项具有挑战性的任务。最近通过实验发现了一种具有斜螺旋结构的手性相,即 Meyer 和 DeGennes 于 1968 年预测的螺旋相,这为观察这种光轴的光学重新定向提供了机会。本文简要回顾了这些非常规手性向列液晶的非线性光学特性,旨在说明液晶相的世界仍然可以通过新的材料特性和新的物理学而令人惊叹。
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引用次数: 0
Chiral ferroelectric nematic liquid crystals as materials for versatile laser devices 作为多功能激光设备材料的手性铁电向列液晶
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1016/j.giant.2024.100316
César L. Folcia , Josu Ortega , Teresa Sierra , Alejandro Martínez-Bueno , Jesús Etxebarria

We present a liquid-crystal laser device based on the chiral ferroelectric nematic phase (NF*). The laser medium is obtained by mixing a ferroelectric nematic material with a chiral agent and a small proportion of a fluorescent dye. Notably, in the NF* phase very low electric fields perpendicular to the helical axis are able to reorient the molecules, giving rise to a periodic structure whose director profile is not single harmonic but contains the contribution of various Fourier components. This feature induces the appearance of several photonic bandgaps whose spectral ranges depend on the field, which can be exploited to build tunable laser devices. Here we report the characterization of home-made NF* lasers that can be tunable under low electric fields and present laser action in two of the photonic bands of the material. The obtained results open a promising route for the design of new and more versatile liquid-crystal based lasers.

我们介绍了一种基于手性铁电向列相 (NF*) 的液晶激光设备。这种激光介质是通过将铁电向列材料与手性剂和少量荧光染料混合而获得的。值得注意的是,在 NF* 相中,垂直于螺旋轴的极低电场能够使分子重新定向,从而产生一种周期性结构,这种结构的方向轮廓不是单次谐波,而是包含各种傅立叶分量。这一特征导致出现了多个光子带隙,其光谱范围取决于场,可用于制造可调谐激光设备。在此,我们报告了自制 NF* 激光器的特性,这种激光器可在低电场下进行调谐,并在材料的两个光子带中产生激光作用。所获得的结果为设计基于液晶的新型多功能激光器开辟了一条前景广阔的道路。
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引用次数: 0
Biodegradable polymer casting films for drug delivery and cell culture 用于给药和细胞培养的生物降解聚合物浇铸膜
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1016/j.giant.2024.100314
Anastasiya V. Murueva , Alexey E. Dudaev , Ekaterina I. Shishatskaya , Fares D.E. Ghorabe , Ivan V. Nemtsev , Anna V. Lukyanenko , Tatiana G. Volova

In this work, for the first time, films were obtained based on biodegradable polyhydroxyalkanoates (PHAs) - a copolymer of 3-hydroxybutyrate-co-3-hydroxyvalerate P(3HB-co-3HV) and a copolymer of 3-hydroxybutyrate-co-4-hydroxybutyrate P(3HB-co-4HB), containing drugs of different chemical structure and action - antibiotics (ceftazidime, doripenem), antiseptic (chlorhexidine) and tissue regeneration stimulator (Actovegin) for drug delivery and cell culture. Using SEM, AFM and measuring the contact angles of water wetting, it is shown how PHAs composition and loading of films of P(3HB-co-3HV) and P(3HB-co-4HB) with drugs affect the porosity, roughness indicators and adhesive properties of the surface. The constructed films are a depot form of drug, the release of which in vitro is realized for a long time, without burst releases, corresponds to Korsmeyer-Peppas and Higuchi models with diffusion character. Films loaded with antibiotics have pronounced antibacterial activity and suppress the development of pathogens S. aureus and E. coli, without a pronounced negative effect on the adhesion and proliferation of epidermal cells. In the cultures of human keratinocytes HaCaT it was shown that the presence of actovegin, as well as ceftazidime in the films, exhibits a stimulating effect, increasing their number. The results demonstrate the suitability of the depot-films for cellular technologies and are promising for the reconstruction of tissues complicated by infection.

在这项工作中,首次获得了基于生物可降解聚羟基烷酸酯(PHAs)的薄膜--3-羟基丁酸酯-3-羟基戊酸酯共聚物 P(3HB-co-3HV) 和 3-羟基丁酸酯-4-羟基丁酸酯共聚物 P(3HB-co-4HB)、含有不同化学结构和作用的药物--抗生素(头孢他啶、多立培南)、杀菌剂(洗必泰)和组织再生刺激剂(Actovegin),用于药物输送和细胞培养。通过使用扫描电镜、原子力显微镜和测量水润湿接触角,说明了 PHAs 的组成以及 P(3HB-co-3HV) 和 P(3HB-co-4HB) 薄膜的药物负载如何影响表面的孔隙率、粗糙度指标和粘附性。所构建的薄膜是一种药物储藏形式,其体外释放时间长,无猝发释放,符合具有扩散特性的 Korsmeyer-Peppas 和 Higuchi 模型。含有抗生素的薄膜具有明显的抗菌活性,能抑制金黄色葡萄球菌和大肠杆菌等病原体的生长,但对表皮细胞的粘附和增殖没有明显的负面影响。在人类角质细胞 HaCaT 的培养中显示,薄膜中的 actovegin 和头孢他啶具有刺激作用,能增加角质细胞的数量。这些结果表明,去势薄膜适用于细胞技术,并有望重建受感染的复杂组织。
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引用次数: 0
Patterning of 2D second harmonic generation active arrays in ferroelectric nematic fluids 铁电向列流体中二维二次谐波发生有源阵列的图案化
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-27 DOI: 10.1016/j.giant.2024.100315
M. Lovšin , A. Petelin , B. Berteloot , N. Osterman , S. Aya , M. Huang , I. Drevenšek-Olenik , R.J. Mandle , K. Neyts , A. Mertelj , N. Sebastian

Ferroelectric nematic liquid crystals exhibit unique non-linear optical properties, with the potential to become transformative materials for photonic applications. A promising direction relies on the fabrication of tailored polar orientational patterns via photoalignment, thus shaping the non-linear optical susceptibility through thin slabs of the ferroelectric fluid. Here, we explore the fabrication of 2D periodic SHG active arrays in ferroelectric nematic fluids, for different materials, cell thicknesses and motifs. Based on polarizing optical microscopy observations in combination with optical simulations, second harmonic generation microscopy and interferometry, the 3D structure of the motifs is revealed. Two different 2D periodic patterns are explored, showing that the balance between flexoelectric and electrostatic energy can lead to different domain structures, an effect which is rooted in the difference between the flexoelectric properties of the materials. It is shown that by combining the surface-inscribed alignment with different spontaneous degrees of twist, 2D SHG active arrays can be obtained in the micrometre scale, in which adjacent areas exhibit maximum SHG signals at opposite angles.

铁电向列液晶具有独特的非线性光学特性,有望成为光子应用领域的变革性材料。一个很有前景的方向是通过光配准制造量身定制的极性取向模式,从而通过铁电流体薄板塑造非线性光学电感。在此,我们针对不同的材料、单元厚度和图案,探索了在铁电向列流体中制造二维周期性 SHG 有源阵列的方法。基于偏振光学显微镜观察,结合光学模拟、二次谐波发生显微镜和干涉测量法,我们揭示了图案的三维结构。研究还探讨了两种不同的二维周期图案,表明挠电能和静电能之间的平衡可导致不同的畴结构,这种效应源于材料挠电特性之间的差异。研究表明,通过将表面刻划排列与不同的自发扭曲度相结合,可以获得微米级的二维 SHG 有源阵列,其中相邻区域以相反的角度显示最大 SHG 信号。
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引用次数: 0
The production of soluble regenerated silk fibroin powder with high molecular weight and silk protein-based materials 生产高分子量可溶性再生丝纤维素粉末和丝蛋白基材料
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-26 DOI: 10.1016/j.giant.2024.100313
Kai Gu , Yixuan Tong , Ruixin Mi, Siyan Leng, Hanwen Huang, Jingrong Yao, Xin Chen, Zhengzhong Shao

The aqueous solution of regenerated silk fibroin (RSF) is considered as the raw material to produce various silk protein-based materials, including hydrogel, film, rod and fiber, etc. with significant mechanical properties. However, the aqueous solution of RSF is usually unstable within a few days or even hours in terms of its essential properties, because the conformation of the RSF chain would spontaneously transfer from random coil to β-sheet in water. In this work, we developed a way to harvest the RSF powder through an optimized spray drying method via rapid drying at a relatively low temperature. It was demonstrated that no severe degradation and conformational transition of the RSF chain occurred during powder preparation, and the RSF powder exhibited remarkable solubility in water and long stability at room temperature. Importantly, there are no obvious differences in the mechanical properties of the silk protein-based materials made from the aqueous solution from the spray-dried RSF powder (Sp-RSF) and from fresh RSF solution. Indeed, such amorphous Sp-RSF powder, in which the protein chain was dominated by random coil conformation, not only promised as the raw material for large-scale silk protein-based products in various applications but also provided the basis for fabricating bulk silk protein materials via the untraditional processing of silk fibroin, such as molding with the help of heat and moisture.

再生蚕丝纤维素(RSF)水溶液被认为是生产各种蚕丝蛋白基材料(包括水凝胶、薄膜、棒材和纤维等)的原料,具有显著的机械性能。然而,RSF 的水溶液通常在几天甚至几小时内其基本特性就会变得不稳定,因为 RSF 链的构象会在水中自发地从无规线圈转变为 β 片状。在这项工作中,我们开发了一种通过优化的喷雾干燥方法,在相对较低的温度下快速干燥收获 RSF 粉末的方法。结果表明,在粉末制备过程中,RSF 链没有发生严重降解和构象转变,RSF 粉末在水中具有显著的溶解性和室温下的长期稳定性。重要的是,用喷雾干燥 RSF 粉末(Sp-RSF)水溶液和新鲜 RSF 溶液制成的丝蛋白基材料在机械性能上没有明显差异。事实上,这种蛋白质链以无规线圈构象为主的无定形 Sp-RSF 粉末不仅可以作为大规模丝蛋白基产品的原料用于各种应用,而且还为通过非传统的丝纤维素加工方法(如借助热量和湿度成型)制造大块丝蛋白材料奠定了基础。
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引用次数: 0
Active nematic-isotropic interfaces on flat surfaces: Effects of anchoring, ordering field and activity 平面上的活性向列-各向同性界面:锚定、有序场和活性的影响
IF 5.4 1区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-06-22 DOI: 10.1016/j.giant.2024.100309
Rodrigo C.V. Coelho , José A. Moreira , Duarte M.C. Pedro , Margarida M. Telo da Gama

A surface in contact with the isotropic phase of a passive liquid crystal can induce nematic order over distances that range from microscopic to macroscopic when the nematic-isotropic interface undergoes an orientational-wetting transition. If the nematic is active, what happens to the interface? Does it propagate and, if it does, is its structure different from the passive one? In this paper, we address these questions. We investigate how the active nematic-isotropic interface is affected by the anchoring strength of the surface, the bulk ordering field and the activity. We find that while passive interfaces are one-dimensional the active ones exhibit two dynamical regimes: a passive-like regime and a propagating regime where the interfaces propagate until the entire domain is active nematic. Active interfaces break the translational symmetry within the interfacial plane above a threshold activity, where the active nematic fluctuations, which are ultimately responsible for the emergence of an active turbulent nematic phase, drive non-steady dynamical interfacial regimes.

当向列-各向同性界面发生取向-润湿转变时,与被动液晶各向同性相接触的表面可以在从微观到宏观的距离上诱导向列有序。如果向列是活跃的,界面会发生什么变化?它是否会传播,如果传播,其结构是否与被动界面不同?在本文中,我们将探讨这些问题。我们研究了活性向列-各向同性界面如何受到表面锚定强度、体有序场和活性的影响。我们发现,被动界面是一维的,而主动界面则表现出两种动力学状态:一种是类似被动的状态,另一种是界面传播状态,即界面传播直至整个域都是主动向列。活性界面在活性阈值以上打破了界面平面内的平移对称性,活性向列波动最终导致了活性湍流向列相的出现,并推动了非稳定的动态界面机制。
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引用次数: 0
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