Coffee Ring Structure Research Articles

Space-Confined Synthesis of Thinner Ether-Functionalized Nanofiltration Membranes with Coffee Ring Structure for Li+/Mg2+ Separation.

Positively charged nanofiltration membranes have attracted much attention in the field of lithium extraction from salt lakes due to their excellent ability to separate mono- and multi-valent cations. However, the thicker selective layer and the lower affinity for Li+ result in lower separation efficiency of the membranes. Here, PEI-P membranes with highly efficient Li+/Mg2+ separation performance are prepared by introducing highly lithophilic 4,7,10-Trioxygen-1,13-tridecanediamine (DCA) on the surface of PEI-TMC membranes using a post-modification method. Characterization and experimental results show that the utilization of the DCA-TMC crosslinked structure as a space-confined layer to inhibit the diffusion of the monomer not only increases the positive charge density of the membrane but also reduces its thickness by ≈35% and presents a unique coffee-ring structure, which ensures excellent water permeability and rejection of Mg2+. The ion-dipole interaction of the ether chains with Li+ facilitates Li+ transport and improves the Li+/Mg2+ selectivity (SLi,Mg=23.3). In a three-stage nanofiltration process for treating simulated salt lake water, the PEI-P membrane can reduce the Mg2+/Li+ ratio of the salt lake by 400-fold and produce Li2CO3 with a purity of more than 99.5%, demonstrating its potential application in lithium extraction from salt lakes.

Deposition patterns formed by the evaporation of linear diblock copolymer solution nanodroplets on solid surfaces.

The evaporation-induced deposition pattern of the linear diblock copolymer solution has attracted attention in recent years. Given its critical applications, we study deposition patterns of the linear diblock copolymer solution nanodroplet on a solid surface (the wall) by molecular dynamics simulations. This study focuses on the influence of the nonbonded interaction strength, including the interaction between the wall and polymer blocks (ɛAW and ɛBW), the interaction between the solvent and the wall (ɛSW), and the interaction between polymer blocks (ɛAB). Conditions leading to diverse deposition patterns are explored, including the coffee-ring and the volcano-like structures. The formation of the coffee-ring structure is attributed to receding interfaces, the heterogeneity inside the droplet, and the self-assembly of polymer chains. This study contributes to the establishment of guidelines for designing deposition patterns of the linear diblock copolymer solution nanodroplet, which facilitates practical applications such as inkjet printing.

Rapid and ultra-sensitive trace metals detection of water by partial Leidenfrost superhydrophobic array surface enhanced laser-induced breakdown spectroscopy

The rapid and ultra-sensitive detection of trace elements in liquid is a primary concern for researchers. In this study, a partial Leidenfrost effect superhydrophobic (PLSHB) array surface was used for rapid in situ evaporation enrichment of sample droplets. Within 4 min, a 50 μL droplet sample was completely evaporated, resulting in all solutes in it being concentrated within a circular range measuring approximately 350 μm in diameter, without the formation of a coffee ring structure. The limits of detection for six metals (Pb, Ba, Be, Mn, Cr, Cu) in water were determined to be as follows: 0.82 μgL−1, 0.27 μgL−1, 0.033 μgL−1, 0.136 μgL−1, 0.241 μgL−1, and 0.083 μgL−1. Furthermore, laser-induced breakdown spectroscopy (LIBS) was employed to detect the enriched solutes from ten liquid samples with identical concentrations on the PLSHB array surface; these measurements exhibited a relative standard deviation (RSD) of only 3.7%. Spike experiments involving the addition of the aforementioned six metals into drinking water demonstrated recovery rates ranging from 85.7% to 117.7%. Therefore, the application potential of PLSHB array surface enhanced LIBS for rapid, stable, and ultra-sensitive detection and analysis of trace metal elements across various fields such as industry, environmental science, and biomedicine might be highly promising.

Light-Scattering Analysis of Drying Behavior in Suspension Droplets with Silica and Polystyrene Particles and a Hydrosoluble Polymer.

The coffee-ring structure, which is the final drying pattern of a sessile suspension droplet, is a key factor in controlling the uniformity of the particulate deposits in various coatings. Two light-scattering methods, diffusing wave spectroscopy (DWS) and multispeckle DWS (MSDWS), were used to quantitatively distinguish temporal changes in particle mobility in evaporating suspension droplets containing micrometer-sized silica and polystyrene (PS) particles. The characteristic particle mobility was measured in terms of the mean square displacement in the early stage of drying, and the local particle dynamics around the edge and center regimes of the droplets during drying were analyzed using MSDWS. Hydroxyethyl cellulose (HEC), a hydrosoluble polymer, was added to the silica and PS suspensions to further investigate its role in suppressing or enhancing coffee-ring patterns based on particle-polymer interactions. Consequently, dried microstructures can be directly correlated with real-time drying dynamics, as well as the interactions between solutes by comprehensive light-scattering methods.

Dynamic Observations on Formation of Coffee-Ring Structures from the Degradation of Cesium Lead Halide Perovskite Nanocrystals.

Nanomaterials of halide perovskites have attracted increasing attention for their remarkable potential in optoelectronic devices, but their instability to environmental factors is the core issue impeding their applications. In this context, the microscopic understanding of their structural degradation mechanisms upon external stimuli remains incomplete. Herein, we took an emerging member of this material family, Cs4PbBr6 nanocrystals (NCs), as an example and investigated the degradation pathways as well as underlying mechanisms under an electron beam by using in situ transmission electron microscopy. Our atomic-scale study identified the distinct degradation stages for the NCs toward interesting coffee-ring PbBr2 structures, which are caused by the organic surface capping agents as well as surface energy of NCs. Our findings present a fundamental insight for the degradation of halide perovskite NCs and may provide indispensable guidance for their structural design and stability improvement.

Printable Epsilon‐Type Structure Transistor Arrays with Highly Reliable Physical Unclonable Functions (Adv. Mater. 16/2023)

Physical Unclonable Functions In article number 2210621, Bowen Zhu, Hong Wang, and co-workers use printed epsilon-type-structure transistor arrays with a modified indium tin oxide coffee-ring structure to construct physical unclonable functions (PUFs) that demonstrate near-ideal uniformity, uniqueness, randomness, reliability, and low power consumption. Additionally, the PUFs are secure against attack by a powerful machine-learning model without post-processing. The epsilon-type structure provides a printable, simple strategy for high-quality and large-scale hardware secure primitives.

Printable Epsilon-Type Structure Transistor Arrays with Highly Reliable Physical Unclonable Functions.

Printed electronics promises to drive the future data-intensive technologies, with its potential to fabricate novel devices over a large area with low cost on nontraditional substrates. In these emerging technologies, there exists a large digital information flow, which requires secure communication and authentication. Physical unclonable functions (PUFs) offer a promising built-in hardware-security system comparable to biometrical data, which can be constructed by device-specific intrinsic variations in the additive manufacturing process of active devices. However, printed PUFs typically exploit the inherent variation in layer thickness and roughness of active devices. The current in devices with enough significant changes to increase the robustness to external environment noise is still a challenge. Here, printable epsilon-type-structure indium tin oxide transistor arrays are demonstrated to construct high-reliability PUFs by modifying the coffee-ring structure. The epsilon-type structure improves the printing scalability, film quality, and device reliability. Furthermore, the print-induced uncertainty along the channel thickness and length can lead to changes in the carrier concentration. Notably, the randomly distributed printing droplets in a small area significantly increase this uncertainty. As a result, the PUFs exhibit near-ideal uniformity, uniqueness, randomness, and reliability. Additionally, the PUFs are resilient against machine-learning-based attacks with a prediction accuracy of only 55% without postprocessing.

Surface deposition characteristics of water-based SiO2 nanofluids on coal

Water-based SiO2 nanofluids, a type of wetting agent for water injection of coal seams, have been well recognized by many scholars due to being environment-friendly and having a stable modification effect. The key of the modification effect of water-based SiO2 nanofluids on coal seam is the deposition behavior of nanofluids on coal surface. Based on this issue, this research conducted real-time monitoring of the morphological evolution characteristics and deposition images of water-based SiO2 nanofluid droplets with different concentrations on coal surface. Moreover, the deposition behavior of water-based SiO2 nanofluids on coal surface was microscopically expounded. The results indicate that the initial contact angle between the nanofluid droplets and coal surface is small, and the spreading degree of water-based SiO2 nanofluids is better than that of deionized water. With the increase of time, the contact angles between water-based SiO2 nanofluid droplets and coal surface tend to linearly decrease. However, the relative length of contact line features flattening at first and then a sharp decline. As the nanoparticles are completely precipitated, water-based SiO2 nanofluid droplets form a deposition pattern with a coffee ring structure on coal surface. In addition, as the particle concentration increases, the relative width of the coffee ring increases stepwise. The particle aggregate on the middle of the deposition pattern gradually connects to coalesce and forms a relatively uniform and flat deposition layer. Based on the research results aforementioned, this research divided the deposition behavior of the water-based SiO2 nanofluid droplets on coal surface into initial stage, the contact angle dominance change, the contact angle and line co-dominance change and complete deposition. Among which, the duration of the angle dominance change stage is longest. With the increase of the particle concentration, the proportion of the angle dominance change stage increases. The research can fill the gap of the research on the deposition behavior of nanofluids on coal surface, which lays a foundation for further research of coal seam water injection using nanofluids.

Laser Induced Coffee-Ring Structure through Solid-Liquid Transition for Color Printing.

Metallic micro/nano structures with special physicochemical properties have undergone rapid development owing to their broad applications in micromachines and microdevices. Ultrafast laser processing is generally accepted as an effective technology for functional structures manufacture, however, the controllable fabrication of specific metallic micro/nano structures remains a challenge. Here, this work proposes a novel strategy of laser induced transient solid-liquid transition to fabricate unique structures. Through modulating the transient state of metal from solid to liquid phase using the initial pulse excitation, the subsequent ultrafast pulse-induced recoil pressure can suppress the plasma emission and removal of liquid phase metals, resulting in the controllable fabrication of coffee-ring structures. The solid-liquid transition dynamics, which related with the transient reflectivity and plasma intensity, are revealed by established two temperature model coupled with molecular dynamics model. The coffee-ring structure exhibits tunable structure color owing to various optical response, which can be used for color printing with large scale and high resolution. This work provides a promising strategy for fabricating functional micro/nano structures, which can greatly broaden the potential applications.

An Experimental Investigation of Evaporation of Ethanol-Water Droplets Laden with Alumina Nanoparticles on a Critically Inclined Heated Substrate.

We experimentally investigate the evaporation of water-ethanol binary sessile droplets loaded with alumina nanoparticles on a critically inclined heated surface and compare it to the no-loading condition. In contrast to a droplet of pure fluids, several distinct and interesting phenomena observed in a binary-nanofluid droplet on a critically inclined substrate are reported for the first time. The critical angle at which a droplet begins to slide increases for ethanol-rich binary droplets up to 0.6 wt % nanoparticle loading. The critical angle for binary droplets also increases as the substrate temperature increases and as the ethanol concentration decreases for modest loading conditions. It is observed that the advancing side of a binary droplet is pinned in both the loading and no-loading scenarios, whereas the receding side is pinned in the loading case but shrinks continuously in the no-loading case. The pinning effect caused by nanoparticles results in a larger perimeter and surface area for the nanoparticle-laden droplets, enhancing the evaporation rates and significantly decreasing the lifetime of the nanoparticle-containing droplets compared to the no-loading case. Increasing the ethanol percentage in the binary droplet placed on an inclined substrate produces complex thermosolutal Marangoni convection, which becomes more affluent in the case of nanoparticles loading than the no-loading condition. The radial symmetry of the circular coffee ring structure observed on a horizontal surface is shattered in the inclined case because the droplet elongates and preferentially deposits toward the advancing side of the triple line due to the action of the body force. Despite its fundamental nature, the present study can contribute to understanding many practical applications.

Nanoparticle deposition pattern during colloidal droplet evaporation as in-situ investigated by Low-Field NMR: The critical role of bound water

The evaporation of a colloidal droplet on a solid surface produces a ring-like structure at the pinned contact line due to induced capillary flow, also known as the coffee-ring effect (CRE). However, the addition of certain additives can significantly reduce CRE, whose physical origin remains in debate. In this study, the time-resolved low field (LF)-NMR technique highlights the effect of different water fractions in colloidal droplets on the ultimate distribution of silica nanoparticles during evaporation. With the assistance of 1H T2 relaxometry, the impact of decreasing evaporation rate (J) and additives on the fractions of bound, trapped, and free water can be obtained. Utilizing the T2 Carr-Purcell-Meiboom-Gill (CPMG) sequence approach, in-situ tracking during droplets evaporation, with varying J, was obtained to conclude the minimum existence time of bound water required during evaporation for CRE suppression. As the droplet J decreases, the competition between the time scale of totally droplet evaporation tF and the time spent of bound water during evaporation tB may influence the ring formation. Experimentally a shorter duration of tB/tF ≤ 0.5 is required for formating the coffee ring structure and successfully suppressed when its existence time surpasses a particular threshold ≥ 0.5.

Rapid enrichment detection of patulin and alternariol in apple using surface enhanced Raman spectroscopy with coffee-ring effect

Patulin (PAT) and alternariol (AOH) are the main mycotoxin contaminants in fruits and their products, which have great toxic effects on human body due to their teratogenicity and carcinogenicity. This study proposed a surface enhanced Raman spectroscopy (SERS) technology combining chemometrics and coffee-ring effect to build high-throughput label-free detection models for PAT and AOH. A stable coffee ring structure was built by optimizing the drying temperature and droplet volume. Comparing the partial least squares (PLS) models grounded on variables selection method, the best performance was obtained by using synergy interval (Si) and genetic algorithm (GA) for PAT (Rc = 0.9905, Rp = 0.9759) and AOH (Rc = 0.9829, Rp = 0.9808), respectively. The limits of detection (LOD) for PAT and AOH were as low as 1 μg L−1, and the recovery rates were 92.80%–114.83% with relative standard deviation (RSD) ≤ 4.86 for PAT and 82.06%–108.13% with RSD ≤2.28% for AOH. The SERS technology combined with chemometrics and coffee-ring effect holds promise for high-throughput label-free detection of PAT and AOH in fruits and their products.

The nascent coffee ring: how solute diffusion counters advection

We study the initial evolution of the coffee ring that is formed by the evaporation of a thin, axisymmetric, surface-tension-dominated droplet containing a dilute solute. When the solutal Péclet number is large, we show that diffusion close to the droplet contact line controls the coffee-ring structure in the initial stages of evaporation. We perform a systematic matched asymptotic analysis for two evaporation models – a simple, non-equilibrium, one-sided model (in which the evaporative flux is taken to be constant across the droplet surface) and a vapour-diffusion limited model (in which the evaporative flux is singular at the contact line) – valid during the early stages in which the solute remains dilute. We call this the ‘nascent coffee ring’ and describe the evolution of its features, including the size and location of the peak concentration and a measure of the width of the ring. Moreover, we use the asymptotic results to investigate when the assumption of a dilute solute breaks down and the effects of finite particle size and jamming are expected to become important. In particular, we illustrate the limited validity of this model in the diffusive evaporative flux regime.

Enhanced Water Permeability and Antifouling Property of Coffee-Ring-Textured Polyamide Membranes by In Situ Incorporation of a Zwitterionic Metal-Organic Framework.

Modulation of the polyamide structure is critically important for the reverse-osmosis performance of thin-film composite (TFC) membranes in the field of water reuse and desalination. Herein, zwitterionic nanoparticles of zeolitic imidazolate framework-8 (PZ@ZIF-8) were fabricated and incorporated into the polyamide active layer through the interfacial polymerization method. A hydrophilic, zwitterionic coffee-ring structure was formed on the surface of polyamide thin-film nanocomposite (TFN) membranes due to the adjusted diffusion rate of m-phenylenediamine (MPD) from the aqueous phase into the organic phase during the interfacial polymerization process. Surface characterization demonstrated that the coffee-ring structure increased the amounts of water transport channels on the membrane surface and the intrinsic pores of PZ@ZIF-8 maintained the salt rejection. Antifouling and bactericidal activities of TFN membranes were enhanced remarkably owing to the bacterial-"defending" and bacterial-"attacking" behaviors of hydrophilic and zwitterionic groups from PZ@ZIF-8 nanoparticles. This work would provide a promising method for the application of MOFs to enhance the bio-/organic-fouling resistance of TFN membranes with high water permeation and salt rejection.

Self-Assembly CNTs@PANi Coffee Rings on Poly(styrene-ethylene-butylene-styrene) Triblock Copolymer for Largely Stretchable Electronics.

In this paper, CNTs@PANi nanocomposites were prepared by in-situ oxidation polymerization of aniline, and their structure, morphology and conductivity were characterized. A mixed solvent of toluene and tetrahydrofuran was used to prepare dispersions of CNTs@PANi and poly(styrene-ethylene-butylene-styrene) (SEBS) triblock copolymer, and bilayer composite film was prepared. According to the solvent phase separation and uneven evaporation flux, CNTs@PANi self-assembled into the interconnected coffee ring structure on the SEBS matrix. The prepared bilayer composite film had excellent stretchability, and the conductivity of the functional layer was close to that of CNTs@PANi, which could light up an LED lamp under 100% strain and restore the topological structure. Electrochemical tests showed that the bilayer film had obvious heterogeneity. The impedance characteristics of the CNTs@PANi functional layer and the SEBS matrix were analyzed, and its heterogeneous corrosion resistance mechanism further discussed.

Preparation and properties of hollow fibre nanofiltration membrane with continuous coffee-ring structure

Polyamide (PA) hollow fibre composite nanofiltration (NF) membranes with a coffee-ring structure and beneficial properties were prepared by adding graphene oxide (GO) into the interfacial polymerization process. The presentation of the coffee-ring structure was attributed to the heterogeneous, finely dispersed multiphase reaction system and the “coffee-stain” effect of the GO solution. When the piperazine concentration was 0.4 wt-%, the trimesoyl chloride concentration was 0.3 wt-%, and the GO concentration was 0.025 wt-%, the prepared NF membranes showed the best separation properties. The permeate flux was 76 L·m−2·h−1, and the rejection rate for MgSO4 was 98.6% at 0.4 MPa. Scanning electron microscopy, atomic force microscopy, and attenuated total reflectance-Fourier transform infrared spectroscopy were used to characterize the chemical structure and morphology of the PA/GO NF membrane. The results showed that GO was successfully entrapped into the PA functional layer. Under neutral operating conditions, the PA/GO membrane showed typical negatively charged NF membrane separation characteristics, and the rejection rate decreased in the order of Na2SO4 > MgSO4 > MgCl2 > NaCl. The PA/GO NF membrane showed better antifouling performance than the PA membrane.

Direct Exposure of Dry Enzymes to Atmospheric Pressure Non-Equilibrium Plasmas: The Case of Tyrosinase.

The direct interaction of atmospheric pressure non-equilibrium plasmas with tyrosinase (Tyr) was investigated under typical conditions used in surface processing. Specifically, Tyr dry deposits were exposed to dielectric barrier discharges (DBDs) fed with helium, helium/oxygen, and helium/ethylene mixtures, and effects on enzyme functionality were evaluated. First of all, results show that DBDs have a measurable impact on Tyr only when experiments were carried out using very low enzyme amounts. An appreciable decrease in Tyr activity was observed upon exposure to oxygen-containing DBD. Nevertheless, the combined use of X-ray photoelectron spectroscopy and white-light vertical scanning interferometry revealed that, in this reactive environment, Tyr deposits displayed remarkable etching resistance, reasonably conferred by plasma-induced changes in their surface chemical composition as well as by their coffee-ring structure. Ethylene-containing DBDs were used to coat tyrosinase with a hydrocarbon polymer film, in order to obtain its immobilization. In particular, it was found that Tyr activity can be fully retained by properly adjusting thin film deposition conditions. All these findings enlighten a high stability of dry enzymes in various plasma environments and open new opportunities for the use of atmospheric pressure non-equilibrium plasmas in enzyme immobilization strategies.

Micro-coffee-ring-patterned fiber SERS probes and their in situ detection application in complex liquid environments

Coffee-ring structures, which are easy to prepare, have many hotspots for surface-enhanced Raman scattering (SERS). However, the inhomogeneous distribution of hotspots causes very poor SERS detection reproducibility, which strongly restricts their practical applications. In this paper, by combining a coffee-ring structure with the waveguide effect of optical fibers, we propose novel micro-coffee-ring-patterned fiber SERS probes fabricated by a laboratory-developed laser-induced dynamic dip-coating method. The mechanisms of micro-coffee-ring formation on fiber facet are analyzed in detail. With the help of a programmable dip-coater, micro-coffee-ring-patterned fiber SERS probes can be automatically and reproducibly fabricated, and they simultaneously show high sensitivity and good reproducibility in SERS detections. A detection limit lower than 10−8 M in aqueous solvent for thiram and methyl parathion (MP) is achieved, and the relative standard deviation (RSD) of the SERS peaks is less than 6%. In addition, benefiting from numerous hotspots provided by micro-coffee rings, this micro-coffee-ring-patterned fiber SERS probe presents superior performance in in-situ trace detection of target molecules in complex liquid environments. Detection sensitivities of 10−7 M for thiram in lake water and in orange juice and 10−6 M for melamine and tetracycline in liquid milk are achieved.

Microstructural metrology of tobacco mosaic virus nanorods during radial compression and heating.

We determined stress-induced deformations and the thermal stability of nanorod-shaped tobacco mosaic virus (TMV) capsids in coffee-ring structures by X-ray nanodiffraction. The hexagonal capsids lattice transforms under compression in the outer boundary zone of the coffee-ring into a tetragonal lattice. The helical pitch of the nanorods increases by about 2.5% across the outer boundary zone while the lateral distance between nanorods decreases continuously across the whole coffee-ring structure by about 2% due to compressive forces. The diffraction patterns show a mixture of helical scattering and Bragg peaks attributed to a lattice of nanorods interlocked by their helical grooves. Thermo-nanodiffraction reveals water loss up to about 100 °C resulting in a reduction of the helical pitch by about 6% with respect to its maximum value and a reduction of the nanorods separation by about 0.5 nm. Up to about 200 °C the pitch is increasing again by about 2%. Secondary crystallization in the bulk reaches a maximum at 150-160 °C. At higher temperatures the crystallinity is continuously decreasing up to about 220 °C. Above about 200 °C and depending on the heating history, the nanorods start disintegrating into small, randomly oriented aggregates.

Controlling coffee ring structure on hydrophobic polymer surface by manipulating wettability with O2 plasma

A simple and novel method is firstly reported for controlling coffee ring structure on polystyrene (PS) film surface by O2 plasma. O2 plasma treatment leads to the wettability change of PS surface from hydrophobic to hydrophilic. For hydrophilic PS surface the coffee ring structure is avoided relying on the motion of contact line (CL) while SiO2 microspheres are left. The motion of the CL is produced based on the viscosity and Marangoni effect with the addition of polymer additives. For hydrophobic PS surface coffee ring structure still persists even with polymer additives because SiO2 microspheres transfer with the motion of the CL at the beginning of droplet evaporation and accumulate at the droplet edge at late stage with the pinning of the CL. As a result, uniform and macroscale SiO2 microspheres deposition without coffee ring structure and SiO2 microspheres deposition with coffee ring structure are controlled by O2 plasma. This method provides a new way to tune coffee ring structure with smart surface and may be potentially useful for a range of application at material deposition and diagnosing diseases.