Coffee Ring Research Articles

Designing of a functional paper-tip substrate for sensitive surface-enhanced Raman spectroscopy (SERS) detection

A simple and flexible fabrication method of paper SERS substrate was developed by nanoparticles (NPs) droplet self-assembly at the paper tip with a temperature gradient (PTTG). We turned the drawback of the coffee ring effect into an effective way of preparing paper SERS substrate. When the NPs droplets were continuously dripped onto the PTTG, NPs were densely and uniformly distributed at the paper-tip front based on the combination of gravity and the coffee ring effect, which could achieve 91.2-fold improvement of SERS performance compared to a flat filter paper. Meanwhile, the analytes could also be enriched at the paper-tip front, which could achieve 9.3-fold signal enhancement compared to the paper-tip tail. Thus, the PTTG realized an excellent signal amplification for SERS detection. The paper-tip SERS substrate combined with a portable Raman spectrometer yielded an excellent analytical enhancement factor of 1.15 × 105 with the detection limit of 10 nM Rhodamine 6G (R6G). The whole fabrication procedure was completed within 2 h, and the paper-tip substrate showed a satisfactory substrate-to-substrate reproducibility with a relative standard deviation (RSD) of 5.13% (n = 10). It was successfully applied for quantitatively detecting real samples of oxytetracycline and malachite green with recoveries of 83.84–105.25% (n = 3). Meanwhile, we further evaluated the SERS performance of the PTTG using a laboratory-based Raman spectrometer, and it could realize the detection as low as 10 pM R6G. The proposed paper-tip substrate would offer a promising potential application for the on-site SERS analysis of food safety and environmental health.

Direct printing of graphene terahertz closed-ring resonator array from periodic single droplets via enhanced coffee-ring effect

Graphene terahertz (THz) devices have emerged as a pivotal player in the THz area, and drop-on-demand (DOD) printing technology enables cost-effective patterning of THz microstructures. However, fast printing of THz microstructures and devices suffers from low efficiency owing to the drop-by-drop overlapping process. Here, we have developed a facile direct printing method to fabricate graphene THz closed-ring resonator (CRR) arrays from periodic single droplets ascribing to the enhanced coffee-ring effect. The construction of a complete graphene micro-ring was achieved using small reduced graphene oxide sheets, enabling the strategy of a graphene CRR from one single droplet. We attributed the mechanism of strengthened coffee-ring effect to the swift pinning, gapless between the contact line and the solute line, and close packing. Finally, we prepared a graphene THz CRR array featuring fine rings with widths of ∼12.3 μm, a high THz extinction ratio of 66.9%, and the highest measurement λ (relative THz response) of 9.8 documented so far for graphene-based THz microstructures and devices. Such an array from the expeditious DOD printing process exhibits a pronounced THz response and possible fast switching speed, which suggests new possibilities in building graphene THz microstructures, benefiting the future development of graphene THz devices.

Ink droplet drying analysis for understanding the ink-catalyst layer transition in proton exchange membrane fuel cells

There is still limited understanding of ink structure and the transition process from ink to the catalyst layer (CL) in proton exchange membrane fuel cells despite recent interest in the field. This study proposes a methodology for analyzing the CLs formed after drying single- and multi-ink droplets produced using an ultrasonic spray. Two model inks, Pt/Vulcan Carbon and Pt/Ketjen Black, are prepared using these catalysts, and their characteristics are analyzed through sedimentation behavior, ionomer adsorption quantification, and rheology. The structural properties of the spray-dried CLs are examined using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and scanning electron microscopy-Auger electron spectroscopy. These analyses reveal distinct differences in the CLs' structures, influenced by physical phenomena such as coffee ring formation and droplet coalescence, which are dependent on the ink properties. Furthermore, the structural characteristics of the CLs produced by the two model inks affect the electrochemical behavior of the 25 cm2 fuel cell. This study establishes a correlation between the ink structure, CL structure, and fuel cell performance, emphasizing the usefulness of the ultrasonic spray coating method in advancing such investigations.

Evaporation of alcohol droplets on surfaces in moist air

Droplets of alcohol-based formulations are common in applications from sanitizing sprays to printing inks. However, our understanding of the drying dynamics of these droplets on surfaces and the influence of ambient humidity is still very limited. Here, we report the drying dynamics of picoliter droplets of isopropyl alcohol deposited on a surface under controlled humidity. Condensation of water vapor in the ambient environment onto alcohol droplets leads to unexpectedly complex drying behavior. As relative humidity (RH) increases, we observed a variety of phenomena including enhanced spreading, nonmonotonic changes in the drying time, the formation of pancake-like shapes that suppress the coffee-ring effect, and the formation of water-rich films around an alcohol-rich drop. We developed a lubrication model that accounts for the coupling between the flow field within the drop, the shape of the drop, and the vapor concentration field. The model reproduces many of the experimentally observed morphological and dynamic features, revealing the presence of unusually large spatial compositional gradients within the evaporating droplet and surface-tension-gradient-driven flows arising from water condensation/evaporation at the surface of the droplet. One unexpected feature from the simulation is that water can evaporate and condense concurrently in different parts of the drop, providing fundamental insights that simpler models based on average fluxes lack. We further observed rim instabilities at higher RH that are well-described by a model based on the Rayleigh-Plateau instability. Our findings have implications for the testing and use of alcohol-based disinfectant sprays and printing inks.

Development of a Low-Cost Paper-Based Platform for Coffee Ring-Assisted SERS.

The need for highly sensitive, low-cost, and timely diagnostic technologies at the point of care is increasing. Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopic technique that is an advantageous technique to address this need, as it can rapidly detect analytes in small or dilute samples with improved sensitivity compared to conventional Raman spectroscopy. Despite the many advantages of SERS, one drawback of the technique is poor reproducibility due to variable interactions between nanoparticles and target analytes. To overcome this limitation, coupling SERS with the coffee ring effect has been implemented to concentrate and localize analyte-nanoparticle conjugates for improved signal reproducibility. However, current coffee ring platforms require laborious fabrication steps. Herein, we present a low-cost, two-step fabrication process for coffee ring-assisted SERS, utilizing wax-printed nitrocellulose paper. The platform was designed to produce a highly hydrophobic paper substrate that supports the coffee ring effect and tested using gold nanoparticles for SERS sensing. The nanoparticle concentration and solvent were varied to determine the effect of solution composition on ring formation and center clearance. The SERS signal was validated using 4-mercaptobenzoic acid (MBA) and tested with Moraxella catarrhalis bacteria to ensure functionality for chemical and biological applications. The limit of detection using MBA is 41.56 nM, and the biochemical components of the bacterial cell wall were enhanced with low spectral variability. The developed platform is advantageous due to ease of fabrication and use, representing the next step toward implementing low-cost coffee ring-assisted SERS for point-of-care sensing.

Coupling effects of human serum albumin and sodium chloride on biological desiccation patterns

Desiccation patterns of plasma sessile drops have attracted increasing attention, not only because of the fantastic underlying physics, but also due to their potential of being health diagnostic tools. However, plasma is a multicomponent system, which contains macromolecular proteins and inorganic salts; these components have complicated interactions to define pattern morphologies. Unfortunately, mechanisms of coupling effects of main components on pattern morphologies are still not clear, thus limiting their diagnostic applications. Here we show the coupling effects of human serum albumin (HSA) and sodium chloride (NaCl) on plasma desiccation patterns. Our experiments indicate that NaCl enhances the “coffee ring” effect of HSA to promote its aggregation at the peripheral region and narrows down its aggregation area; this would influence the distribution of internal stresses, resulting in a larger number of radial cracks, with a larger width but a shorter length, than cracks in pure HSA. In the meantime, HSA experiences the gelation process that propagates from the peripheral region to central region and causes the spatiotemporal deviation in the degree of solidification, which induces a higher concentration of NaCl in the central region, thus leading to the formation of crystal patterns. Our further experiments demonstrate that these characteristic patterns are correlated to the variation in the concentration of NaCl, which can be caused by hyponatremia and hypernatremia in real biofluids. Our findings not only provide a new mechanistic insight into biological desiccation patterns, but also bridge the gap between the understanding and diagnostic applications of these desiccation patterns.

Conditions of enhanced evaporation for nanofluids droplet and inhibition of coffee-ring effect under buoyancy and Marangoni convection

Evaporation of nanofluid droplets whose size is larger than capillary length is common in industrial processes, but there is currently a lack of research on the evaporation kinetics and more complex deposition patterns under the combined effects of buoyancy and Marangoni convection of large evaporating droplet. Experimental investigations on evaporation of Al2O3H2O nanofluid sessile droplet with initial contact line diameter of 4 mm on heating PTFE coating substrate are reported. The variation in contact angle, contact radius, and droplet volume over time under different conditions were obtained through experiments. The average evaporation rate is calculated. Internal flow characteristics are inferred through the surface temperature distribution detected by the top view infrared camera. The constant contact radius mode takes place at the beginning of evaporation. Then mixed evaporation mode and stick slip mode may occur for different substrate temperature, nanoparticle mass concentration and nanoparticle size. Increasing nanoparticle size causes a decrease in average evaporation rate. Whether the use of nanofluids can improve evaporation rate and heat transfer or not depends on multiple factors. Convection cells exist, and three kinds of deposition patterns are formed due to the underlying coupled transport phenomena. Under the combined effect of buoyancy and Marangoni convection in this article, the most common coffee-ring pattern does not appear. The deposition patterns are directly affected by the pinning stability, which decrease at higher temperature.

Moisture control enables high-performance sprayed perovskite solar cells under ambient conditions

Morphology and crystallization control are critical for metal halide perovskite films in enabling high-performance photovoltaic devices. However, they remain particularly challenging for sprayed devices due to the inherent flaw of the spraying technology—the “coffee-ring” effect (CRE). Herein, we report a moisture-assisted strategy that effectively eliminates CRE and enhances film crystallization through the combined utilization of humidity control and water additives. This approach leads to the formation of Cs0.19FA0.81PbI2.5Br0.5 perovskite films with homogeneous morphology and excellent crystallization, and the power conversion efficiency (PCE) of the champion perovskite solar cells increases from 18.25% to 19.74%. Moreover, unencapsulated devices exhibit excellent stability, with 80% of their initial efficiency retained after operating at 50 °C for over 800 h. Furthermore, the large-area perovskite film (10 × 10 cm2) exhibits significant uniformity throughout the entire film, and the corresponding devices exhibit high consistency and reproducibility. The small-area devices utilizing the same large-area perovskite film show an average PCE of 19.53 ± 0.25%, while mini-modules with an active area of 64.8 cm2 yield an optimal PCE of 16.75%, with an average PCE of 16.08 ± 0.32%.

Evaporation-induced hydrodynamics control plasmid transfer during surface-associated microbial growth

Droplet evaporation is a general process in unsaturated environments that results in micro-scale hydrodynamic flows which in turn determine the spatial distributions of microbial cells across surfaces. These spatial distributions can have significant effects on the development and functioning of surface-associated microbial communities, with consequences for important processes such as the spread of plasmids. Here, we experimentally quantified how evaporation-induced hydrodynamic processes modulate the initial deposition patterns of microbial cells (via the coffee ring effect and Marangoni convection) and how these patterns control the spread of an antibiotic resistance-encoding plasmid during surface-associated growth. We found that plasmid spread is a function of the initial density of cells deposited along the droplet periphery, which is a manifestation of the coffee ring effect. Using an individual-based model, we systematically linked how the different initial cell deposition patterns caused by the relative strengths of the coffee ring effect and Marangoni convection determine the extent of plasmid transfer during surface-associated growth. Our study demonstrates that evaporation-induced hydrodynamic processes that are common in nature can alter crucial ecological properties of surface-associated microbial communities and control the proliferation of plasmids, with consequences on the spread of antibiotic resistance and other plasmid-encoded traits.

Full and In Situ Printing of Nanogenerators that Are Based on an Inherently Viscous Piezoelectric Polymer: An Effort to Minimize “Coffee Ring Effect” and Nonprinting Operations

Full and In Situ Printing of Nanogenerators that Are Based on an Inherently Viscous Piezoelectric Polymer: An Effort to Minimize “Coffee Ring Effect” and Nonprinting Operations

Gravitational effects on coffee-ring formation during the evaporation of sessile droplets

We consider the role of gravity in solute transport when a thin droplet evaporates. Under the physically relevant assumptions that the contact line is pinned and the solutal Péclet number, ${Pe}$ , is large, we identify two asymptotic regimes that depend on the size of the Bond number, ${Bo}$ . When ${Bo} = O(1)$ as ${Pe}\rightarrow \infty$ , the asymptotic structure of solute transport follows directly from the surface-tension-dominated regime, whereby advection drives solute towards the contact line, only to be countered by local diffusive effects, leading to the formation of the famous ‘coffee ring.’ In the distinguished limit in which ${Bo} = O({Pe}^{4/3})$ as ${Pe}\rightarrow \infty$ , this interplay between advection and diffusion takes place alongside that between surface tension and gravity. In each regime, we perform a systematic asymptotic analysis of the solute transport and compare our predictions to numerical simulations. We identify the effect of gravity on the nascent coffee ring, providing quantitative predictions of the size, location and shape of the solute mass profile. In particular, for a fixed Péclet number, as the effect of gravity increases, the coffee ring is diminished in height and situated further from the contact line. Furthermore, for certain values of ${Bo}$ , ${Pe}$ and the evaporation time, a secondary peak may exist inside the classical coffee ring. The onset of this secondary peak is linked to the change in type of the critical point in the solute mass profile at the droplet centre. Both the onset and the peak characteristics are shown to be independent of ${Pe}$ .

Biomimetic Ag/ZnO@PDMS Hybrid Nanorod Array-Mediated Photo-induced Enhanced Raman Spectroscopy Sensor for Quantitative and Visualized Analysis of Microplastics.

Microplastics are persistent pollutants that accumulate in the environment and can cause serious toxicity to mammals. At present, few technologies are able to quantitatively detect chemicals and provide morphological information simultaneously. Herein, we developed a dragonfly-wing-mimicking ZnO nanorod array decorated with AgNPs on polydimethylsiloxane (PDMS) as a surface-enhanced Raman spectroscopy (SERS) and photo-induced enhanced Raman spectroscopy (PIERS) substrate for trace analysis of microplastics. The Ag/ZnO@PDMS hybrid nanorod array endows the sensor with high sensitivity and signal repeatability (RSD ∼ 5.89%), ensuring the reliable quantitative analysis of microplastics. Importantly, when the noble metal-semiconductor substrate was pre-radiated with ultraviolet light, a surprising PIERS was attained, achieving an additional enhancement of 11.3-fold higher than the normal SERS signal. By combining the PIERS technology with the "coffee ring effect", the sensor successfully discerned microplastics of polyethylene (PE) and polystyrene (PS) at a trace level of 25 μg/mL even with a portable Raman device. It was capable of identifying PS microspheres in contaminated tap water, lake water, river water, and seawater with detection limits of 25, 28, 35, and 60 μg/mL, respectively. The recovery rates of PS microspheres in four water environments ranged from 94.8 to 102.4%, with the RSD ranging from 2.40 to 6.81%. Moreover, quantitative and visualized detection of microplastics was readily realized by our sensor. This portable PIERS sensor represents a significant step toward the generalizability and practicality of quantitative and visual sensing technology.

Single versus Double Coffee-Ring Effect Patterns in Thin-Layer Chromatography Coupled with Surface-Enhanced Raman Spectroscopic Analysis of Anti-Diabetic Drugs Adulterated in Herbal Products.

In thin-layer chromatography coupled with surface-enhanced Raman spectroscopy (TLC-SERS), the coffee ring effect (CRE) describes the formation of a ring-shape spot (blank in the middle and darker on the edge) caused by the aggregation of silver nanoparticles (Ag NPs), alone (single CRE) or with the analytes (double CRE). In this work, the SCRE and DCRE were investigated in two anti-diabetic drugs, hydrophobic glibenclamide (GLB) and more hydrophilic metformin (MET). The SCRE occurred in GLB analysis, as opposed to the DCRE that occurred in MET. It was proven that for optimization of the TLC-SERS analytical procedure, it is necessary to distinguish the CRE patterns of analytes. Additionally, MET and GLB were analyzed with the developed TLC-SERS method and confirmed by another validated method using high-performance liquid chromatography. Four herbal products collected on the market were found to be adulterated with GLB or/and MET; among those, one product was adulterated with both MET and GLB, and two products were adulterated with GLB at a higher concentration than the usual GLB prescription dose. The TLC-SERS method provided a useful tool for the simultaneous detection of adulterated anti-diabetic herbal products, and the comparison of the SCRE and DCRE provided more evidence to predict CRE patterns in TLC-SERS.

Quasi-phase extraction-based surface plasmon resonance imaging method for coffee ring effect monitoring and biosensing.

Wavelength interrogation surface plasmon resonance imaging (WSPRi) sensing has unique advantages in high-throughput imaging detection. The refractive index resolution (RIR) of WSPRi is limited to the order of 10-6 RIU. This paper demonstrates a novel WSPRi sensing system with a wavelength scanning device of an acousto-optic tunable filter (AOTF) and a low-cost speckle-free SPR excitation source of a halogen lamp. We developed a sensitive quasi-phase extraction method for data processing. The new technique achieved an RIR of 8.84×10-7 RIU, which is the first WSPRi system that has an RIR in the order of 10-7 RIU. Moreover, we performed a real-time recording of the formation of the coffee ring effect during brine evaporation and enhanced the biosensor performance of SPR for the first time. We believe the higher RIR and accuracy of the system will benefit more potential applications toward exploring the biomolecules' behaviors in biological and biochemistry studies.

Triple-enhanced Raman scattering sensors from flexible MXene/Au nanocubes platform via attenuating the coffee ring effect

Developing substrates that combine sensitivity and signal stability is a major challenge in surface enhanced Raman scattering (SERS) research. Herein, we present a flexible triple-enhanced Raman Scattering MXene/Au nanocubes (AuNCs) sensor fabricated by selective filtration of Ti3C2Tx MXene/AuNCs hybrid on the Ti3C2Tx MXene membrane and subsequent treatment with 1H,1H,2H,2H-perfluoro-octyltriethoxysilane (FOTS). The resultant superhydrophobic MXene/AuNCs-FOTS membrane not only provides the SERS substrate with environmental stability, but also imparts analyte enrichment to enhance the sensitivity (LOD = 1 × 10−14 M) and reliability (RSD = 6.41%) for Rhodamine 6G (R6G) molecules owing to the attenuation of the coffee ring effect. Moreover, the triple enhancement mechanism of combining plasmonic coupling enhancement from plasmonic coupling (EM) of nearby AuNCs at lateral and longitudinal direction of MXene/AuNCs-FOTS membrane, charge transfer (CT) from Ti3C2Tx MXene and target molecules and analyte enrichment function provides the substrate with excellent SERS performance (EF = 3.19 × 109), and allows efficient quantification of biomarkers in urine. This work could provide new insights into MXenes as building blocks for high-performance substrates and fill existing gaps in SERS techniques.

Drying Acoustically Levitated Droplets as Signal-Amplifying Platforms for Ultrasensitive and Multimode Laser Sensing.

Ultrasensitive sensing to trace atomic and molecular analytes has gained interest for its intimate relation to industrial sectors and human lives. One of the keys to ultrasensitive sensing for many analytical techniques lies in enriching trace analytes onto well-designed substrates. However, the coffee ring effect, nonuniform distribution of analytes onto substrates, in the droplet drying process hinders the ultrasensitive and stable sensing onto the substrates. Here, we propose a substrate-free strategy to suppress the coffee ring effect, enrich analytes, and self-assemble a signal-amplifying (SA) platform for multimode laser sensing. The strategy involves acoustically levitating and drying a droplet, mixed with analytes and core-shell Au@SiO2 nanoparticles, to self-assemble an SA platform. The SA platform with a plasmonic nanostructure can dramatically enrich analytes, enabling enormous spectroscopic signal amplification. Specifically, the SA platform can promote atomic detection (cadmium and chromium) to the 10-3 mg/L level by nanoparticle-enhanced laser-induced breakdown spectroscopy and can promote molecule detection (rhodamine 6G) to the 10-11 mol/L level by surface-enhanced Raman scattering. All in all, the SA platform, self-assembled by acoustic levitation, can intrinsically suppress the coffee ring effect and enrich trace analytes, enabling ultrasensitive multimode laser sensing.

Culinary fluid mechanics and other currents in food science

This review describes recent scientific advances in the context of the culinary arts. It is written as a menu, starting with the physics of drinks, followed by the main course, and ending with complex desserts. Recent discoveries are reviewed, particularly in fluid mechanics and soft matter physics, and their relevance to food science is highlighted. Many phenomena like the Cheerios effect, coffee-ring effect, Brazil nut effect, Leidenfrost effect, and Marangoni effect are described and illustrated by epicurean examples.

Monte Carlo simulation of the coffee-ring effect on porous papers

Monte Carlo simulation of the coffee-ring effect on porous papers

Networks of Conjugated Polymer-Wrapped Single-Walled Carbon Nanotubes through Controlled Drop-Dispensing for Thin-Film Transistors

Despite the simplicity of the drop-casting method to deposit films of single-walled carbon nanotubes (SWNTs) for applications such as printed electronics, this technique presents many challenges and uncertainties that are yet to be addressed. The coffee-ring effect is a known example, which results in an accumulation of solids around the edge of the drop. This can be mitigated by increasing the temperature of the substrate to induce Marangoni flows, but it is unknown what the repercussions of this change would be on dispersions of conjugated polymer-wrapped SWNTs and resulting thin-film transistor devices. In this study, we demonstrate that the drop-casting method benefits greatly from the use of an automated drop-dispenser coupled with a desktop robot, leading to more consistent and improved charge-carrier mobilities (μ) and threshold voltages. We then present the effect of drop size and substrate temperature on the surface coverage, linear density, and appearance of the resulting SWNT networks. A reduction in surface coverage and linear density was noted with increasing temperature above 50 °C, in addition to increased bundling of the SWNTs, as observed in atomic force microscopy images. Raman spectroscopy demonstrated that drops cast at higher temperatures allow for a more even distribution of the SWNTs throughout the drop due to the formation of deposits during transitions between constant contact radius and constant contact angle modes. The devices resulting from drop-casting at higher temperatures also exhibit decreased mobilities (μ) at smaller drop volumes.

Assessment of coffee-ring effect on wool and cotton fabrics inkjet printed with herbal inks

In this study, the ecologically pre-treated wool and cotton fabrics were digitally printed with eco-friendly plant-based inks of blue, red, yellow, and black colours obtained from the plant extracts of bio indigo leaves, quebracho red bark and the flame of the forest flowers and evaluated for coffee-ring effect. The plant-based inks constituted from the Quebracho red bark and the flame of the forest flowers extract both demonstrated reduced dispersion diameter (i.e. diffused) for the Plasma Surface Treated (PST) wool and cotton fabric than the untreated. These findings could be applied for digital printing on photonics to combat the Coffee-ring effect. The possible explanation for the reduced coffee ring effect is the phenomenon known as Marangoni flow. The predominant phytochemicals functioning as chromophores namely indigotin, tannin and butein enclosed in inks constituted from the plant extracts of bio indigo leaves, quebracho red bark and the flame of the forest flowers respectively are highlighted. Additionally, the synthesis of plant-based ink, the colour scheme adapted for determining the inks colours, and the technique of print process as implemented in the study are explained. Likewise, the Colour patch, Percentage (%) Reflectance, and, Colour difference graphs as acquired from Datacolor tools are demonstrated. To end, the wash fastness, rub fastness, and light fastness test results obtained on wool and cotton fabrics digitally printed with innovative plant-based inks are detailed. The Life Cycle Analysis and assessment of functional phytochemicals on the resultant printed fabrics are suggested for future work.