Surface Free Energy Research Articles

Fully Biodegradable Elastomer-Based Device for Oral Macromolecule Delivery.

Oral devices, such as foil-type devices, show great potential for the delivery of poorly permeable macromolecules by enabling unidirectional release of the loaded pharmaceutical composition in close proximity to the epithelium in the small intestine or colon. However, one of the primary concerns associated with the use of foil-type devices so far has been the utilization of nonbiodegradable elastomers in the fabrication of the devices. Therefore, research into biodegradable substitute materials with similar characteristics enables drug delivery in a sustainable and environmentally friendly manner. In this study, a biodegradable elastomer, polyoctanediol citrate (POC), was synthesized via a one-pot reaction, with subsequent purification and microscale pattern replication via casting. The microstructure geometry was designed to enable fabrication of foil-type devices with the selected elastomer, which has a high intrinsic surface free energy. The final elastomer was demonstrated to have an elastic modulus ranging up to 2.2 ± 0.1 MPa, with strain at failure up to 110.1 ± 1.5%. Devices were loaded with acetaminophen and enterically coated, demonstrating 100% release at 2.5 h, following dissolution for 1 h in 0.1 M hydrochloric acid and 1.5 h in pH 6.8 phosphate-buffered saline. The elastomer demonstrated promising properties based on mechanical testing, surface free energy evaluation, and degradation studies.

Phosphate Esters: New Coating Materials for a Sustainable Release Paper.

AbstractPaper manufacturers have long used silicone as the coating agent for release liners. However, silicone‐based release paper is very difficult to recycle due to covalent bonds between silicone and fibers. The most suitable solution to overcome this problem is to use alternative coating materials with adequate release properties, provided that they can be easily repulped in typical paper recycling facilities. We proposed a coating agent composed of phosphate esters and dimethylacetamide in order to manufacture a recyclable and efficient release paper. Analyses carried out on coated sheets showed that phosphate esters allowed the formation of a surface with adequate release properties (low peeling force and surface free energy). In addition, the residual adhesion values obtained with phosphate esters confirmed that they are well anchored on the backing paper surface, thus limiting the mass transfer to the adhesive tape.

Quantitative Prediction of Dissociation Rates of PYK2 Ligands Using Umbrella Sampling and Milestoning.

We used umbrella sampling and the milestoning simulation method to study the dissociation of multiple ligands from protein kinase PYK2. The activation barriers obtained from the potential of mean force of the umbrella sampling simulations correlated well with the experimental dissociation rates. Using the zero-temperature string method, we obtained optimized paths along the free-energy surfaces for milestoning simulations of three ligands with a similar structure. The milestoning simulations gave an absolute dissociation rate within 2 orders of magnitude of the experimental value for two ligands but at least 3 orders of magnitude too high for the third. Despite the similarity in their structures, the ligands took different pathways to exit from the binding site of PYK2, making contact with different sets of residues. In addition, the protein experienced different conformational changes for dissociation of the three ligands.

Effect of Electrolytic Plasma Polishing on Surface Properties of Titanium Alloy

Effect of Electrolytic Plasma Polishing on Surface Properties of Titanium Alloy

Dispersive surface free energy of adsorbents modified by supramolecular structures of heterocyclic compounds

Dispersive surface free energy of adsorbents modified by supramolecular structures of heterocyclic compounds

Nanoconfinement of Carbon Dioxide within Interfacial Aqueous/Ionic Liquid Systems.

Nanoporous, gas-selective membranes have shown encouraging results for the removal of CO2 from flue gas, yet the optimal design for such membranes is often unknown. Therefore, we used molecular dynamics simulations to elucidate the behavior of CO2 within aqueous and ionic liquid (IL) systems ([EMIM][TFSI] and [OMIM][TFSI]), both confined individually and as an interfacial aqueous/IL system. We found that within aqueous systems the mobility of CO2 is reduced due to interactions between the CO2 oxygens and hydroxyl groups on the pore surface. Within the IL systems, we found that confinement has a greater effect on the [EMIM][TFSI] system as opposed to the [OMIM][TFSI] system. Paradoxically, the larger and more asymmetrical [OMIM]+ molecule undergoes less efficient packing, resulting in fewer confinement effects. Free energy surfaces of the nanoconfined aqueous/IL interface demonstrate that CO2 will transfer spontaneously from the aqueous to the IL phase.

Composite Materials Based on Waste Chicken Feather Fibers for Oil-Spill Management

ABSTRACT Oil spills remain one of the greatest man-made ecological threats, despite numerous advanced cleanup approaches. They still pose a major challenge in the search for materials and technologies that work as efficiently and sustainably as possible. Promising natural materials include poultry feathers, which are produced in large quantities every day as a byproduct of the meat industry. In this study, the influence of different forms of absorbents (loose feathers, pillows, and sheets) based on chicken feathers and the addition of an inorganic absorbent, sepiolite, on their absorption capacity was investigated. The chemical and physical surface properties, like morphology, chemical composition, zeta potential, surface free energies and oil absorption capacities were analyzed. The Gibbs free energy of immersion wetting with oil and the work of adhesion of the adsorbents, calculated based on contact angle measurements, were confirmed by the tests of adsorption capacities according to the ASTM 726–12 standard. The results showed that pure loose feathers have the highest oil adsorption capacity, while feather pillows have only half, and composite sheets have only a quarter of this capacity. The addition of inorganic adsorbent sepiolite did not increase the absorption capacity of the composites.

Towards the icephobicity evolution of metallic surfaces affected by transitional wettability

In light of the escalating demands for ice protection related applications in diverse fields, including wind energy, power lines and aerospace, there is a notable surge in interest and attention toward the icephobic materials. The increased focus reflects a growing recognition of the crucial role of materials that demonstrate superior resistance to icing phenomenon. However, the intricate correlation between material wettability and icephobicity remains inadequately elucidated. This study aimed to investigate the factors that influence the relationship between icephobicity and different wetting states. The impact of varying surface topographies was examined within the scope of this investigation. A comprehensive analysis was conducted to evaluate the anti-icing and de-icing performances of the surfaces, encompassing anti-frost, ice shear adhesion strength and electro-thermal heating de-icing aspects. Furthermore, the static and dynamic wettability, along with surface free energy measurements, were also performed to enhance the comprehension of icephobicity variation. The detailed water condensation on various surfaces was meticulously observed using environmental scanning electron microscopy (ESEM). The findings elucidated a strong correlation between the icing behaviour and surface topography. It was observed that the surface topography acted as an amplifier, intensifying the deteriorating effect in icephobicity: the formed glaze per unit area exhibited a significant increase with rough asperities; the ice adhesion strength suffered an obvious increase with rough surface and lower hydrophobicity as well as the prolonged ice detachment and overall energy consumption. Therefore, careful consideration should be devoted to the tailoring of surface morphology and wettability when designing and fabricating icephobic surfaces.

A facile strategy for the preparation of monatomic silver

The surface free energy of metal increases with the decrease of the metal particle sizes, which contributes to the aggregation of isolated single atoms into nanoparticles during synthesis and reaction processes. The common disadvantages of traditional methods for preparing monatomic catalysts are low loading capacity, easy aggregation of atoms and complex preparation methods. These disadvantages limit the application of monatomic catalysts. In this paper, a simple, stable and repeatable method for preparing monatomic silver catalyst without high temperature is explored. Preyssler-type polyoxometalate is a metal oxide with a cavity disk structure, and Na+ in the cavity structure can be replaced by Ag+ by hydrothermal method. Under the action of reducing agent, Ag+-containing polyoxometalate can be converted into monatomic silver, and under the protection of surfactant, monatomic silver can be stably maintained for one month.

Rate theory of gas-liquid nucleation: Quest for the elusive quantitative accuracy.

The task of a first principles theoretical calculation of the rate of gas-liquid nucleation has remained largely incomplete despite the existence of reliable results from unbiased simulation studies at large supersaturation. Although the classical nucleation theory formulated by Becker-Doring-Zeldovich about a century ago provides an elegant, widely used picture of nucleation in a first-order phase transition, the theory finds difficulties in predicting the rate accurately, especially in the case of gas-to-liquid nucleation. Here, we use a multiple-order parameter description to construct the nucleation free energy surface needed to calculate the nucleation rate. A multidimensional non-Markovian (MDNM) rate theory formulation that generalizes Langer's well-known nucleation theory by using the Grote-Hynes MDNM treatment is used to obtain the rate of barrier crossing. We find good agreement of the theory with the rate obtained by direct unbiased molecular dynamics simulations-the latter is feasible at large supersaturation, S. The theory gives an experimentally strong dependence of the rate of nucleation on supersaturation, S. Interestingly, we find a strong influence of the frequency-dependent friction coefficient at the barrier top. This arises from multiple recrossings of the barrier surface. We find that a Markovian theory, such as Langer's formulation, fails to capture the rate quantitatively. In addition, the multidimensional transition state theory expression performs poorly, revealing the underlying role of the friction coefficient.

An investigation of methods to enhance adhesion of conductive layer and dielectric substrate for additive manufacturing of electronics

Additive manufacturing of conductive layers on a dielectric substrate has garnered significant interest due to its promise to produce printed electronics efficiently and its capability to print on curved substrates. A considerable challenge encountered is the conductive layer’s potential peeling due to inadequate adhesion with the dielectric substrate, which compromises the durability and functionality of the electronics. This study strives to facilitate the binding force through dielectric substrate surface modification using concentrated sulfuric acid and ultraviolet (UV) laser treatment. First, polyetheretherketone (PEEK) and nanoparticle silver ink were employed as the studied material. Second, the surface treatment of PEEK substrates was conducted across six levels of sulfuric acid exposure time and eight levels of UV laser scanning velocity. Then, responses such as surface morphology, roughness, elemental composition, chemical bonding characteristics, water contact angle, and surface free energy (SFE) were assessed to understand the effects of these treatments. Finally, the nanoparticle silver ink layer was deposited on the PEEK surface, and the adhesion force measured using a pull-off adhesion tester. Results unveiled a binding force of 0.37 MPa on unmodified surface, which escalated to 1.99 MPa with sulfuric acid treatment and 2.21 MPa with UV laser treatment. Additionally, cross-approach treatment investigations revealed that application sequence significantly impacts results, increasing binding force to 2.77 MPa. The analysis further delves into the influence mechanism of the surface modification on the binding force, elucidating that UV laser and sulfuric acid surface treatment methods hold substantial promise for enhancing the binding force between heterogeneous materials in the additive manufacturing of electronics.

Magnetic field assisted centrifugal acceleration thin-layer chromatography: An approach to investigate the magnetic field effects on separation parameters including retention factor difference, selectivity factor, and resolution

The effect of internal and external magnetic fields on the separation of antifungal drugs by centrifugal acceleration thin-layer chromatography was reported for the first time. External and internal magnetic fields were applied using neodymium magnets and CoFe2O4@SiO2 ferromagnetic nanoparticles. Separation of ketoconazole and clotrimazole was performed using a mobile phase consisting of n-hexane, ethyl acetate, ethanol, and ammonia (2.0:2.0:0.5:0.2, v/v). The influence of the magnetic field on the entire chromatographic system led to changes in the properties of the stationary and mobile phases and the analytes affecting the retention factor, shape, and width of the separated rings. The extent of this impact depended on the structure of the analyte and the type and intensity of the magnetic field. In the presence of the external magnetic field, there were more significant changes in the chromatographic parameters of the drugs, especially the width of the separated rings, and ketoconazole was more affected than clotrimazole. The changes are conceivably due to the effect of the magnetic field on the analyte distribution between the stationary and mobile phases, which is also caused by the possibility of the magnetic field affecting the viscosity, surface tension, and surface free energy between the stationary and mobile phases.

Predict the surface free energy of Ti/Zr/V chemical conversion coating on nickel by machine learning approach: Trees vs. neurons

The surface properties of chemical conversion treated materials have received increasing attention and surface free energy (SFE) is an important indicator of it. In this study, an environment-friendly Ti/Zr/V chemical conversion coating was deposited on the nickel and Artificial Neural Network (ANN), Random Forest (RF), and Extra Trees (ET) models were applied to further investigate the relationship between the SFE and the compositions of the conversion bath. The accuracy of SFE prediction of three machine learning models was quantified, and the obtained results reveal that the correlation coefficients for the ANN, RF, and ET models are 0.958, 0.979, and 0.963 for the prediction of dispersion components and 0.964, 0.942 and 0.921 for the prediction of polar components, respectively, and the ANN model shows more outstanding performance in general. The errors in the prediction of the ANN model for the polar and dispersion components of SFE are 0.336 and 0.421, respectively, which are smaller than the extended uncertainties obtained from conventional experimental methods. The obtained machine learning models can accurately predict the variations of SFE for modest changes in the conversion bath components, thus linking the formation mechanism of coating with the variations of SFE.

Photo-crosslinked chitosan-gelatin xerogel-like coating onto “cold” plasma functionalized poly(lactic acid) film as cell culture support

This paper reports on biofunctionalisation of a poly(lactic acid) (PLA) film by surface activation through cold plasma treatment followed by coating with a chitosan-gelatin xerogel. The UV cross-linking of the xerogel precursor was simultaneously performed with the fixation onto the PLA support. This has a strong effect on surface properties, in terms of wettability, surface free energy, morphology and micromechanical features. The hydrophilic – hydrophobic character of the surface, determined by contact angle measurements, was tuned along the process, passing from moderate hydrophobic PLA to enhanced hydrophilic plasma activated surface that favors coating adhesion then to moderate hydrophobic chitosan-gelatin coating. The coating has a Lewis amphoteric surface with a porous xerogel-like morphology as revealed by scanning electron microscopy images. By riboflavin mediated UV cross-linking the chitosan-gelatin coating becomes high adhesive and with a more pronounced plasticity, as shown by AFM force-distance spectroscopy. Thus prepared surface coated PLA supports were successfully tested for growth of dermal fibroblasts, which are known for their induction potential of chondrogenic cells, which is very important in cartilage tissue engineering.

High-performance lithium metal anode enhanced by multifunctional film of PAN@AgNWs with antimicrobial activity

Lithium metal is expected to be the perfect anode material for the next generation of rechargeable batteries owing to its ultra-high theoretical specific capacity, low density and the lowest redox potential. However, the practical application of lithium metal batteries faces serious challenges, including uneven lithium deposition, negative electrode volume expansion, and short circuits brought by dendritic protrusions. Although the 3D structure of silver nanowires is effective in inhibiting lithium dendrite growth and lithium metal volume expansion, it still suffers from lithium inhomogeneity caused by uneven distribution of silver nanowires and complicated preparation. Therefore, PAN@AgNWs collector was prepared by a simple suction filtration method, and uniform dispersion of silver nanowires and uniform deposition of lithium were achieved. Lithium nucleation overpotential and lithium dendrite formation can be effectively reduced by PAN@AgNWs hosts due to the reduction of local current density by 3D collectors and the improved lithiophilicity of silver nanowires. With low voltage hysteresis, the symmetric battery constructed with its composite anode may cycle steadily for 4500 hours at 1 mA cm−2 and 1 mAh cm−2. At the same time, the Li-PAN@AgNWs||LFP full cell still possesses a reversible of 144.18 mAh g−1 after 500 cycles at 1C. Moreover, due to large specific surface area and high surface energy of 3D silver nanowires, it exhibits excellent antimicrobial properties, with an inactivation efficiency of 96.3% after contacting with E. coli for 2.5 h. This work shows the possibility of using PAN@AgNWs in a large scale for LMBs, and paves the way for development of high-performance antimicrobial materials.

The driving force of water absorption in cementitious materials: An analysis of surface-free energies and pore structure

The driving force of water absorption in cementitious materials: An analysis of surface-free energies and pore structure

UV-mediated photochemical synthesis and investigation of the antiviral properties of Silver nanoparticle-polyvinyl butyral nanocomposite coatings as a novel antiviral material with high stability and activity

Effectively developing new antimicrobial surfaces for viral diseases requires considerable research, money, and time. Moreover, new species of microorganisms and pathogens are constantly appearing or entering from other regions, which can cause epidemics or pandemics. The ongoing presence of SARS-CoV-2 underscores the need to develop new antimicrobial materials. In this context, a novel UV-irradiated photochemical in-situ synthesis method is introduced for producing durable, long-lasting antiviral silver-polymer (AgNP-PVB) nanocomposite coatings. These coatings are intended to mitigate infectious disease transmission across various frequently touched surfaces, such as door handles, keypads, bank encoders, telephone locks, lift buttons, etc. Additionally, the significance of the size and concentration of AgNP in influencing the physical and antiviral properties of these nanocomposite coatings is illustrated. Detailed studies of AgNP-PVB coatings were conducted using X-ray diffraction, Raman spectroscopy, atomic force microscopy (AFM), and ultraviolet-visible-near-infrared spectroscopy, and contact angle measurements. The antiviral properties of the coatings were evaluated by a one-step reverse transcription real-time polymerase chain reaction (one-step qRT‒PCR) using synthetic SARS-CoV-2 RNA. Raman spectra signatures confirm AgNPs in the PVB matrix by matching identified peaks in X-ray diffractograms. AFM analysis revealed a reduction in AgNP size in the nanocomposite with an increase in the irradiation duration from 5 to 30 min. Spectroscopic results corresponding to AFM measurements highlighted specific wavelengths related to different AgNP size ranges. Contact angle measurements suggest that antiviral activity can be predicted by calculating the surface free energy (SFE) of the sample. As the SFE value increases, antiviral activity decreases. Nanocomposite coatings (with concentrations of 150, 200, 500, and 1000 ppm AgNP) are effective in reducing the activity of SARS-CoV-2, indicating their potential as long-acting preventive agents against viral infections. A methodology incorporating a specialized algorithm was devised for the application of the investigated coatings, which also integrates 3D scanning and printing techniques for fabricating complex geometry flexible protective cover. Subsequently, this coating was applied to produce a protective cover for the widely utilized public object, the door handle, employing 3D printing technology. As a result of the work, a long-term, durable antiviral AgNP-PVB nanocomposite coating with varying AgNP sizes (ranging from 15 to 118 nm) and concentrations (150, 200, 500, and 1000 ppm) was successfully developed.

DNA recovery and substrate considerations; more than a superficial relationship

ABSTRACT A comprehensive investigation into the substrate and deposit characteristics was conducted to address key physicochemical parameters that influence the substrate deposit interactions for the deposition, adhesion, transfer, recovery, and persistence of DNA containing biological materials. It was established that small changes in surface roughness and physicochemical interactions, including hydrophobicity, surface free energy (SFE), and protein adsorption, resulted in observable impacts on the spread and adhesion of touch, saliva, semen, and blood deposits. This finding may have consequences for the transfer, persistence and recovery of DNA deposits.

Influence of air DBD plasma treatment on the shear and flexural strength of adhesively bonded glass fiber reinforced epoxy composite joints

In this study, air dielectric barrier discharge (DBD) plasma treatment was applied at various voltages and treatment durations to improve the bonding strength of glass fiber reinforced epoxy composites (GF/EP). In addition, single lap shear and three-point bending strengths of adhesively bonded joints were compared between untreated and surface-treated (sanding, peel ply, and plasma) samples. Surface properties of GF/EP composites were examined using contact angle, surface free energy, X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), and Atomic Force Microscopy (AFM). Then, mechanical tests (single lap shear and three point bending) were performed and the damage modes were determined. Surface analyses revealed that wettability and polar functional groups increased on the GF/EP surface after plasma treatment. From the mechanical test results, it was observed that the plasma treatment applied to GF/EP composites increased both single lap shear and flexural strength compared to untreated, sanding and peel ply surface treatments. After both single lap shear and 3-point bending tests, adhesive, and light fiber tear failure modes were observed.

Optimization and Mechanism Study of Bonding Properties of CFRP/Al7075 Single-Lap Joints by Low-Temperature Plasma Surface Treatment

This paper studied favorable low-temperature plasma (LTP) surface treatment modes for Carbon Fiber Reinforced Polymer (CFRP)/Al7075 single-lap joints using complex experimental methods and analyzed the failure modes of the joints. The surface physicochemical properties of CFRP after LTP surface treatment were characterized using scanning electron microscopy (SEM), contact angle tests, and X-ray photoelectron spectroscopy (XPS). The influence mechanism of LTP surface treatment on the bonding properties of CFRP/Al7075 single-lap Joint was studied. The results of the complex experiment and range analysis showed that the favorable LTP surface treatment parameters were a speed of 10 mm/s, a distance of 10 mm, and three repeat scans. At these parameters, the shear strength of the joints reached 30.76 MPa, a 102.8% improvement compared to the untreated group. The failure mode of the joints shifted from interface failure to substrate failure. After low-temperature plasma surface treatment with favorable parameters, the CFRP surface exhibited gully like textures, which enhanced the mechanical interlocking between the CFRP surface and the adhesive. Additionally, the surface free energy of CFRP significantly increased, reaching a maximum of 78.77 mJ/m2. XPS results demonstrated that the low-temperature plasma surface treatment led to a significant increase in the content of oxygen-containing functional groups, such as C-O, C=O, and O-C=O, on the CFRP surface.