Quantifying Chemical Reactions and Interfacial Properties at Buried Polymer/Polymer Interfaces.

Maleic anhydride (MAH)-modified polymers are used as tie layers for binding dissimilar polymers in multilayer polymer films. The MAH chemistry which promotes adhesion is well characterized in the bulk; however, only recently has the interfacial chemistry been studied. Sum frequency generation vibrational spectroscopy (SFG) is an interfacial spectroscopy technique which provides detailed information on interfacial chemical reactions, species, and molecular orientations and has been essential for characterizing the MAH chemistry in both nylon and ethyl vinyl alcohol copolymer (EVOH) model systems and coextruded multilayer films. Here, we further characterize the interfacial chemistry between MAH-modified polyethylene tie layers and both EVOH and nylon by investigating the model systems over a range of MAH concentrations. We can detect the interfacial chemical reaction products between MAH and the barrier layer at MAH concentrations of ≥0.022 wt % for nylon and ≥0.077 wt % for EVOH. Additionally, from the concentration-dependent reaction reactant/product SFG peak positions and the product imide or ester/acid C═O group tilt angles extracted from the polarization-dependent SFG spectra, we quantitatively observe concentration-dependent changes to both the interfacial chemistry and interfacial structure. The interfacial chemistry and molecular orientation as a function of MAH concentration are well correlated with the adhesion strength, providing important quantitative information for the future design of MAH-modified tie layers for a variety of important applications.

Molecular behavior of silicone adhesive at buried polymer interface studied by molecular dynamics simulation and sum frequency generation vibrational spectroscopy.

Silicones have excellent material properties and are used extensively in many applications, ranging from adhesives and lubricants to electrical insulation. To ensure strong adhesion of silicone adhesives to a wide variety of substrates, silane-based adhesion promotors are typically blended into the silicone adhesive formulation. However, little is known at the molecular level about the true silane adhesion promotion mechanism, which limits the ability to develop even more effective adhesion promoters. To understand the adhesion promotion mechanism of silane molecules at the molecular level, this study has used sum frequency generation vibrational spectroscopy (SFG) to determine the behavior of (3-glycidoxypropyl)trimethoxy silane (γ-GPS) at the buried interface between poly(ethylene terephthalate) (PET) and a bulk silicone adhesive. To complement and extend the SFG results, atomistic molecular dynamics (MD) simulations were applied to investigate molecular behavior and interfacial interaction of γ-GPS at the silicone/PET interface. Free energy computations were used to study the γ-GPS interaction in the sample system and determine the γ-GPS interfacial segregation mechanism. Both experiments and simulations consistently show that γ-GPS molecules prefer to segregate at the interface between PET and PDMS. The methoxy groups on γ-GPS molecules orient toward the PDMS polymer phase. The consistent picture of interfacial structure emerging from both simulation and experiment provides enhanced insight on how γ-GPS behaves in the silicone - PET system and illustrates why γ-GPS could improve the adhesion of silicone adhesive, leading to further understanding of silicone adhesion mechanisms useful in the design of silicone adhesives with improved performance.

Elucidating the Changes in Molecular Structure at the Buried Interface of RTV Silicone Elastomers during Curing.

Silicone elastomers are widely used in many industrial applications, including coatings, adhesives, and sealants. Room-temperature vulcanized (RTV) silicone, a major subcategory of silicone elastomers, undergoes molecular structural transformations during condensation curing, which affect their mechanical, thermal, and chemical properties. The role of reactive hydroxyl (-OH) groups in the curing reaction of RTV silicone is crucial but not well understood, particularly when multiple sources of hydroxyl groups are present in a formulated product. This work aims to elucidate the interfacial molecular structural changes and origins of interfacial reactive hydroxyl groups in RTV silicone during curing, focusing on the methoxy groups at interfaces and their relationship to adhesion. Sum frequency generation (SFG) vibrational spectroscopy is an in situ nondestructive technique used in this study to investigate the interfacial molecular structure of select RTV formulations at the buried interface at different levels of cure. The primary sources of hydroxyl groups required for interfacial reactions in the initial curing stage are found to be those on the substrate surface rather than those from the ingress of ambient moisture. The silylation treatment of silica substrates eliminates interfacial hydroxyl groups, which greatly impact the silicone interfacial behavior and properties (e.g., adhesion). This study establishes the correlation between interfacial molecular structural changes in RTV silicones and their effect on adhesion strength. It also highlights the power of SFG spectroscopy as a unique tool for studying chemical and structural changes at RTV silicone/substrate interface in situ and in real time during curing. This work provides valuable insights into the interfacial chemistry of RTV silicone and its implications for material performance and application development, aiding in the development of improved silicone adhesives.

Effects of an integrated childbirth education program to reduce fear of childbirth, anxiety, and depression, and improve dispositional mindfulness: A single-blind randomised controlled trial.

OBJECTIVE: To evaluate the effects of an integrated childbirth education intervention on reducing childbirth fear, anxiety, and depression, and improving dispositional mindfulness. DESIGN: A two-arm parallel, single-blind randomised controlled trial. SETTING: A teaching hospital in Northern Taiwan. PARTICIPANTS: Pregnant women ≥ 20 years of age with a singleton pregnancy (12-24 weeks gestation) and their support partners were recruited. All women included in the study had a score of ≥ 7 points on a fear of childbirth visual analogue scale. INTERVENTIONS: The intervention group (n = 53) received an 8-week course in a childbirth education programme, which included (1) childbirth education using simulation-based learning that highlighted coping with labour pain and (2) instruction in mindfulness breathing, body scans, stretching, sitting meditation, and mindfulness walking. Support partners were invited to participate. The control group (n = 53) received the usual standard prenatal care. MEASUREMENTS: The primary outcome of fear of childbirth was assessed using the Wijma Delivery Expectancy/Experience Questionnaire. The secondary outcomes of anxiety, depression, and dispositional mindfulness were assessed with the Edinburgh Postpartum Depression Scale, State-Trait Anxiety Inventory Scale, and the Mindful Attention Awareness Scale, respectively. Repeated data were collected at baseline, 36 weeks gestation, and 1 week postpartum. FINDINGS: Ninety-one mothers completed the study, with a mean age of 33.9 years (SD = 4.4), and most were primipara (n = 83). The baseline measurements did not differ between the groups. Compared with the control group, there were significant differences in all measures from baseline for the intervention group: the scores were significantly lower for fear of childbirth (mean difference (MD) =-14.8 ∼ -23.7, p < .01), symptoms of anxiety (MD =-7.4 ∼ -6.4, p < .01), and depression (MD =-3.7 ∼ -3.5, p < .01); the levels of dispositional mindfulness were significantly higher (MD =4.9 ∼ 5.7, p < .01) at 36 weeks gestation, and 1 week postpartum. CONCLUSION AND IMPLICATIONS FOR PRACTICE: The 8-week integrated childbirth education intervention was effective in reducing the fear of childbirth in pregnant women. The mindfulness techniques were easily learnt and applied by the participants. Using these techniques during pregnancy and labour enhanced participants' mental health and coping. The integrated childbirth education which includes pregnant women and their support partners could be easily taught by midwives in other contexts.

Effect of Ethylcellulose on the Rheology and Mechanical Heterogeneity of Asphaltene Films at the Oil-Water Interface.

Asphaltenes are surface-active molecules that exist naturally in crude oil. They adsorb at the water-oil interface and form viscoelastic interfacial films that stabilize emulsion droplets, making water-oil separation extremely challenging. There is, thus, a need for chemical demulsifiers to disrupt the interfacial asphaltene films, and, thereby, facilitate water-oil separation. Here, we examine ethylcellulose (EC) as a model demulsifier and measure its impact on the interfacial properties of asphaltene films using interfacial shear microrheology. When EC is mixed with an oil and asphaltene solution, it retards the interfacial stiffening that occurs between the oil phase in contact with a water phase. Moreover, EC introduces relatively weak regions within the film. When EC is introduced to a pre-existing asphaltene film, the stiffness of the films decreases abruptly and significantly. Direct visualization of interfacial dynamics further reveals that EC acts inhomogeneously, and that relatively soft regions in the initial film are seen to expand. This mechanism likely impacts emulsion destabilization and provides new insight to the process of demulsification.

Interfacial Rheology and Heterogeneity of Aging Asphaltene Layers at the Water-Oil Interface.

Surface-active asphaltene molecules are naturally found in crude oil, causing serious problems in the petroleum industry by stabilizing emulsion drops, thus hindering the separation of water and oil. Asphaltenes can adsorb at water-oil interfaces to form viscoelastic interfacial films that retard or prevent coalescence. Here, we measure the evolving interfacial shear rheology of water-oil interfaces as asphaltenes adsorb. Generally, interfaces stiffen with time, and the response crosses over from viscous-dominated to elastic-dominated. However, significant variations in the stiffness evolution are observed in putatively identical experiments. Direct visualization of the interfacial strain field reveals significant heterogeneities within each evolving film, which appear to be an inherent feature of the asphaltene interfaces. Our results reveal the adsorption process and aged interfacial structure to be more complex than that previously described. The complexities likely impact the coalescence of asphaltene-stabilized droplets, and suggest new challenges in destabilizing crude oil emulsions.

High-Throughput Industrial Coatings Research at The Dow Chemical Company.

At The Dow Chemical Company, high-throughput research is an active area for developing new industrial coatings products. Using the principles of automation (i.e., using robotic instruments), parallel processing (i.e., prepare, process, and evaluate samples in parallel), and miniaturization (i.e., reduce sample size), high-throughput tools for synthesizing, formulating, and applying coating compositions have been developed at Dow. In addition, high-throughput workflows for measuring various coating properties, such as cure speed, hardness development, scratch resistance, impact toughness, resin compatibility, pot-life, surface defects, among others have also been developed in-house. These workflows correlate well with the traditional coatings tests, but they do not necessarily mimic those tests. The use of such high-throughput workflows in combination with smart experimental designs allows accelerated discovery and commercialization.

A Novel High-Throughput Viscometer.

A novel, rapid, parallel, and high-throughput system for measuring viscosity of materials under different conditions of shear rate, temperature, time, etc., has been developed. This unique system utilizes the transient flow of a complex fluid through pipettes. This approach offers significant practical advantages over microfluidic-based devices for viscosity screening: no cleanup is required, the method is high throughput (<1 h for 100 samples), and only small sample volumes (<1 mL) are used. This paper details for the first time the experimental and modeling efforts to implement this mass- and pressure-based viscosity measurement concept as a robust viscosity estimation tool. This approach is very well-suited for viscosity measurements in high-throughput formulation workflows, as it is rapid and parallel and operates directly on samples in various microtiter plate formats. We present systematic experimental observations together with numerical and analytical modeling approaches to characterize instrument capabilities and limitations. The complex transient flow of fluids through these pipettes leads to data-rich pressure profiles. Numerical and analytical modeling is then used to extract viscosity and other rheological parameters from these pressure profiles. We have successfully utilized this viscosity screening tool for a multitude of complex fluids including oils, paints, solvents, and detergents.

High-Throughput Raman Spectroscopy Screening of Excipients for the Stabilization of Amorphous Drugs.

Low aqueous solubility of active pharmaceutical ingredients (APIs) is an enduring problem in pharmaceutical development, and it is becoming increasingly prevalent among new drug candidates. It is estimated that about 40% of drugs in the development pipeline and approximately 60% of the drugs coming directly from discovery suffer from poor aqueous solubility and slow dissolution, thereby reducing their bioavailability and efficacy and thus preventing their commercialization. It is well known that utilizing the amorphous form of a drug can be a useful approach to improve the dissolution rate and solubility of poorly water-soluble APIs. Amorphous compounds are thermodynamically unstable, but they can be stabilized by combining them with a carrier polymer (excipient) to form a solid dispersion. High-throughput Raman spectroscopy was used in this study to identify excipients that promote formation and stabilization of the amorphous drug form in solid dispersions. Four model APIs were used as poorly soluble drug candidates: ketoprofen, danazol, griseofulvin, and probucol. The Raman signals of excipients were generally negligible, and therefore Raman bands from the drugs were used with minimal spectral pre-processing. By comparing Raman spectra collected from the APIs in the crystalline and molten state, appropriate spectral features and regions were identified for the development of semi-quantitative methods to determine the amorphous content for each API. It is demonstrated that methods based on peak intensity ratio, peak width, peak distance, and classical least squares can all be effective methods for the screening of excipients. Interesting excipient-dependent phase transformation behavior was also observed for probucol.

Nanocapillary array interconnects for gated analyte injections and electrophoretic separations in multilayer microfluidic architectures.

An electrokinetic injection technique is described which uses a nuclear track-etched nanocapillary array to inject sample plugs from one layer of a microfluidic device into another vertically separated layer for electrophoretic separations. Gated injection protocols for analyte separations, reported here, establish nanocapillary array interconnects as a route to multilevel microfluidic analytical designs. The hybrid nanofluidic/microfluidic gated injection protocol allows sample preparation and separation to be implemented in separate horizontal planes, thereby achieving multilayer integration. Repeated injections and separations of FITC-labeled arginine and tryptophan, using 200-nm pore-diameter capillary array injectors in place of traditional cross injectors are used to demonstrate gated injection with a bias configuration that uses relay switching of a single high-voltage source. Injection times as rapid as 0.3 s along with separation reproducibilities as low as 1% for FITC-labeled arginine exemplify the capability for fast, serial separations and analyses. Impedance analysis of the micro-/nanofluidic network is used to gain further insight into the mechanism by which this actively controlled nanofluidic-interconnect injection method works. Gated sample introduction via a nanocapillary array interconnect allows the injection and separation protocols to be optimized independently, thus realizing the versatility needed for real-world implementation of rapid, serial microchip analyses.

Gateable nanofluidic interconnects for multilayered microfluidic separation systems.

The extension of microfluidic devices to include three-dimensional fluidic networks allows complex fluidic and chemical manipulations but requires innovative methods to interface fluidic layers. Externally controllable interconnects, employing nuclear track-etched polycarbonate membranes containing nanometer-diameter capillaries, are described that produce hybrid three-dimensional fluidic architectures. Controllable nanofluidic transfer is achieved by controlling applied bias, polarity, and density of the immobile nanopore surface charge and the impedance of the nanocapillary array relative to the microfluidic channels. Analyte transport between vertically separated microchannels has three stable transfer levels, corresponding to zero, reverse, and forward bias. The transfer can even depend on the properties of the analyte being transferred such as the molecular size, illustrating the flexible character of the analyte transfer. In a specific analysis implementation, nanochannel array gating is applied to capillary electrophoresis separations, allowing selected separated components to be isolated for further manipulation, thereby opening the way for preparative separations at attomole analyte mass levels.