Polymer Relaxation Research Articles

Dynamics of HPAM flow and injectivity in sandstone porous media

Polymer flooding is a prominent chemical enhanced oil recovery (CEOR) method that involves the injection of polymer solution into the oil reservoirs to improve the sweep efficiency and maximize the ultimate oil recovery. Selecting an appropriate polymer type, molecular weight, and concentration is crucial for success of any polymer flooding project. This paper studies the flow behavior of HPAM-based EOR polymers with different molecular weights through porous media. Dynamic adsorption and injectivity tests were performed through 5 Darcies sandpacks using polymer solutions prepared with low (LM; 8–10 MDa) and high (HM; 20–25 MDa) molecular weight polymers. Polymer solutions with different target viscosity values of 7, 15 and 30 cP were flooded through sandpacks at the reservoir temperature of 80 ºC and pore pressure of 1000 psi. The results showed that HM solutions with different target viscosity have higher polymer retention through sandpacks compared to LM solutions. Furthermore, results of residual resistance factor (RRF) measurements were in line with dynamic adsorption tests results. That is, permeability reduction due to irreversible polymer retention was higher when HM polymer solutions were injected. Furthermore, the results showed that although the resistance factor (RF) and in-situ viscosity of HM and LM polymers are in the same range, however, shear thickening regime becomes pronounced in the case of HM polymer with higher target viscosity. Polymer relaxation time measurements, and consequently, Deborah number calculations were performed to describe the shear thickening behavior by polymers viscoelastic characteristics. Results demonstrate that occurrence of shear thickening regime is controlled by Deborah number which is a function of polymer molecular weight, polymer concentration and injection rate. These results shed light on the importance of the selection of optimal polymer molecular weight and concentration during the design of polymer flooding projects.

Insight into the “synergistic-relaxation effects” in amorphous polymer: Thermodynamic modeling, multiphysics simulation and application in 4D printing

Structure and stress relaxation in shape memory polymers (SMPs), which show the time-dependent response to temperature and mechanical loading, respectively, are usually thought to be the primary mechanisms of shape memory effects (SMEs). However, the synergistic effect of structure and stress relaxation has not been well investigated. What's more, convenient and economic manufacturing and structural customization of SMPs can be easily achieved by four-dimensional (4D) printing technology. Thus, in this paper, we comprehensively analyze the working mechanisms of synergistic-relaxation effects in both traditional and 4D-printed SMPs using theoretical calculations and experimental confirmation. Specifically, the calculations are based on the thermo-mechanical and electro-thermo-mechanical models, and multiple sets of experimental data are used to verify the model results. The model results agree well with the experimental data and demonstrate that synergistic-relaxation mechanisms play an important role in thermo-mechanical behaviors.

In vitro skin permeation of flavonoid esters enzymatically derived from natural oils: release mechanism from gel emulsion, stability, and dermatological compatibility

Due to their broad spectrum of biological activities and attractive pharmacological properties, flavonoids are very promising molecules for application in skin care products. In this study, phloridzin and naringin medium- and long-chain fatty acid esters were enzymatically synthesized in reaction with natural oils (coconut and linseed oil) and in vitro transdermal delivery of synthesized esters through artificial Strat-M® membrane was investigated. Experimental results were succesfully fitted using Peppas and Sahlin model which includes the lag phase. Release kinetics of all examined flavonoid esters from gel emulsions through the membrane depended on both diffusion and polymer relaxation effect (0.5<n < 1). The estimated effective diffusion coefficients ranged from 0.168·10-8 to 6.149·10-8 cm2 s-1 for phloridzin esters and from 0.116·10-8 to 4.210·10-8 cm2 s-1 for naringin esters. The effective diffusion coefficients decreased with the increase in ester molecular weight indicating the size-dependent diffusion. All formulation showed good stability, excellent hydration effect, and excellent dermatological compatibility without irritating effect. It can be concluded that gel emulsions with a mixture of flavonoid esters enzymatically synthesized in reaction with vegetable oils can be effectively topically applied as a skin care products.

Chitosan xerogel embedded with green synthesized cerium oxide nanoparticle: An effective controlled release fertilizer for improved cabbage growth

With the growing awareness on the adverse effects of conventional fertilizers; the use of sustainable and controlled release fertilizers has garnered much significance. In the present study, we report the synthesis of chitosan-benzaldehyde Schiff base xerogel incorporated with green synthesized cerium oxide nanoparticle using Psidium guajava leaves extract as a sustainable fertilizer. Spherical CeO2 NPs having an average particle size of 15.3 nm and zeta potential of – 39.9 mV was obtained. The urea-loaded nanocomposite xerogel (CsB@U/CeO2) was examined for cabbage growth. The water retention capacity extended for >2 weeks. A controlled release profile for urea was accomplished from CsB@U/CeO2 for a period extending for 30 days. The kinetics assay suggested that presence of CeO2 NPs asserted a greater role in urea-controlled release from the CsB@U/CeO2 nanocomposite hydrogel owing to polymer relaxation. The growth parameters of cabbages such as head height, diameter, fresh head weight, head circumference was enhanced in plants fertilized by CsB@U/CeO2 as compared to urea. Furthermore, the phenolic content, free radical scavenging activity, protein content, sugar and flavonoid content were also found higher in CsB@U/CeO2 fertilized plants. This study puts forth CsB@U/CeO2 xerogel can be potentially harnessed as an alternative to urea in sustainable agriculture.

Interrelation of macroscopic mechanical properties and molecular scale thermal relaxation of biodegradable and non-biodegradable polymers

Comparative analysis of macroscopic mechanical properties of a biodegradable polymer polypropylene carbonate (PPC) is carried out concerning two most commonly used, non-biodegradable synthetic polymers-high-density polyethylene (HDPE) and linear-low density polyethylene (LLDPE). Responses of the films of these polymers when subjected to mechanical and thermal stresses are analyzed. Response to tensile stress reveals the highest elongation at break (EB) in PPC films (396 ± 104 mm), compared to HDPE (26 ± 0.5 mm) and LLDPE (301 ± 143 mm), although the elastic modulus (YM) of PPC is around 50 ± 6 MPa, 3-fold lesser than LLDPE (YM = 153 ± 7 MPa) and 6-fold lesser than HDPE (YM = 305 ± 32 MPa). The plastic deformation response of PPC is intermediate to that of HDPE and LLDPE; initial strain softening is followed by strain hardening in LLDPE, a plateau region in PPC, and prolonged strain softening in HDPE. Crystalline domains in HDPE produce restriction on molecular motion. Crystallinity abruptly decreases by 70% in HDPE following a thermal quench, showing the possibility of free chain molecular mobility during plastic deformation. High correlation among Raman modes for all polymers reveals cooperative relaxation processes after thermal quench; C-C stretching modes and C-H bending, CH2wagging modes have Pearson's correlation coefficient 0.9. The integrated peak intensity and width of the C-C stretching Raman mode is 3-fold higher in PPC than HDPE after a thermal quench, showing enhanced molecular mobility and contributing modes in PPC. The peak width of this mode shows a strong negative correlation of -0.7 with the YM and a strong positive correlation of 0.6 with EB, showing that higher amorphicity leads to enhanced molecular mobility and EB at the cost of YM. This study reveals importance of molecular-scale response in governing the macroscopic properties of polymers.

Molecular Structures of Poly(methyl methacrylate) at Different Buried Interfaces Revealed by Sum Frequency Generation Vibrational Spectroscopy.

Silica or calcium fluoride (CaF2) substrate-supported poly(methyl methacrylate) (PMMA) thin films as insulating layers are commonly used in photoelectric/photovoltaic devices to improve the efficiency or stability of these devices. However, a comparative investigation of molecular structures at buried PMMA/silica and PMMA/CaF2 interfaces under thermal stimuli remains unexplored. In this study, we qualitatively and quantitatively revealed different molecular orderings and orientations of PMMA at two interfaces before and after annealing using sum frequency generation (SFG) vibrational spectroscopy. SFG vibrations were carefully assigned by using various deuterated PMMAs. SFG results indicated that, at the buried PMMA/silica interface, the side OCH3 groups were prone to lie down before annealing and tended to stand up after annealing. In contrast, the case was the opposite at the buried PMMA/CaF2 interface. The relative hydrophobicity/hydrophilicity of the two substrates and the developed hydrogen bonds upon annealing at the buried PMMA/silica interface, which is absent at the CaF2 surface, are believed to be the driving forces for different interfacial molecular structures. This study benefits the molecular-level understanding of the interfacial local structural relaxation of polymers at buried interfaces and the rational design of photoelectric/photovoltaic devices from the molecular level.

Poly(acrylic acid)-Sodium Alginate Superabsorbent Hydrogels Synthesized by Electron-Beam Irradiation-Part II: Swelling Kinetics and Absorption Behavior in Various Swelling Media.

Hybrid hydrogels with superabsorbent properties based on acrylic acid (20%), sodium alginate (0.5%) and poly(ethylene oxide) (0.1%) were obtained by electron-beam irradiation between 5 and 20 kGy, and are characterized by different physical and chemical methods; the first results reported showed gel fractions over 87%, cross-link densities under 9.9 × 103 mol/cm3 and swelling degrees of 400 g/g. Two types of hydrogels (without and with 0.1% initiator potassium persulfate) have been subjected to swelling and deswelling experiments in different swelling media with different pHs, chosen in accordance with the purpose for which these superabsorbent materials were obtained, i.e., water and nutrients carriers for agricultural purposes: 6.05 (distilled water), 7.66 (tap water), 5.40 (synthetic nutrient solution) and 7.45 (organic nutrient solution). Swelling kinetics and swelling dynamics have been also studied in order to investigate the influence of swelling media type and pH on the absorption phenomenon. The swelling and deswelling behaviors were influenced by the hydrogel characteristics and pH of the swelling media. Both the polymeric chain relaxation (non-Fickian diffusion) and macromolecular relaxation (super case II) phenomenon were highlighted as a function of swelling media type.

In vitro assessment of skin permeation properties of enzymatically derived oil-based fatty acid esters of vitamin C.

Current topical formulations containing vitamin C face limitations in therapeutic effectiveness due to the skin's selective properties that impede drug deposition. Consequently, the widespread use of toxic and irritating chemical permeation enhancers is common. Hereby, we investigated enzymatically derived fatty acid ascorbyl esters (FAAEs) obtained using natural oils for their skin permeation properties using the Strat-M® skin model in a Franz cell diffusion study. By evaluating various cosmetic formulations without added enhancers, we found that emulgel is most suitable for enhancing the cutaneous and transdermal delivery of FAAEs. Furthermore, medium-chain coconut oil-derived FAAEs exhibited faster diffusion rates compared to sunflower oil-based FAAEs with long-side acyl residues, including the commonly applied ascorbyl palmitate. Experimental data were successfully fitted using the Peppas and Sahlin model, which accounted for a lag phase and the combined effect of Fickian diffusion and polymer relaxation. In the case of long-chain esters, the lag phase was prolonged, and the calculated effective diffusion coefficients (Deff) were lower compared to medium-chain FAAEs. Accordingly, the highest Deff value was observed for ascorbyl caprylate, being even 60 times higher than for ascorbyl palmitate. These results suggest the emerging potential of emulgel with incorporated coconut oil-derived FAAEs for efficiently delivering vitamin C into the skin.

Effects of Dye Addition on the Rheological Properties of Aqueous Polymer Solutions.

In many commercial applications, polymer-dye interactions are frequently encountered from food to wastewater treatment, and while shear rheology has been well characterized, the extensional properties are not well known. The extensional viscosity ηE and relaxation time λE are the extensional rheological parameters that provide valuable insights into how aqueous polymers respond during deformation, and this study investigated the effect of dyes on the extensional rheology of three different aqueous polymer solutions (e.g., anionic, cationic, and neutral) paired with two different dye salts (e.g., anionic and cationic) using drop pinch-off experiments. We have found that the influence of dyes on the pinch-off dynamics is complex but generally leads to a decrease in, for example, the apparent extensional relaxation time. We have utilized the dripping-onto-substrate method to probe the uniaxial deformation of widely used polymers such as xanthan gum (XG), poly(diallyldimethylammonium chloride) (PDADMAC), and poly(ethylene oxide) (PEO) as the anionic, cationic, and neutral polymers, respectively, paired with either fluorescein (Fl) or methylene blue (MB) as the anionic and cationic dyes, respectively. Polymer-dye pairs with opposite charges (e.g., XG-MB and PDADMAC-Fl) displayed a pronounced decrease in pinch-off times, but even PEO, which is a neutral polymer, resulted in decreased pinch-off times, which was restored by the addition of NaCl. The pinch-off times for the Boger fluid (mixture of poly(ethylene glycol) and PEO), however, were surprisingly uninfluenced by dyes. These results showed that not only did the small addition of dyes strongly decrease the polymer relaxation times, but the relative importance of the dye salts on the polymer pinch-off dynamics was also different from that of pure salts such as NaCl.

Robust Recovery of Optimally Smoothed Polymer Relaxation Spectrum from Stress Relaxation Test Measurements.

The relaxation spectrum is a fundamental viscoelastic characteristic from which other material functions used to describe the rheological properties of polymers can be determined. The spectrum is recovered from relaxation stress or oscillatory shear data. Since the problem of the relaxation spectrum identification is ill-posed, in the known methods, different mechanisms are built-in to obtain a smooth enough and noise-robust relaxation spectrum model. The regularization of the original problem and/or limit of the set of admissible solutions are the most commonly used remedies. Here, the problem of determining an optimally smoothed continuous relaxation time spectrum is directly stated and solved for the first time, assuming that discrete-time noise-corrupted measurements of a relaxation modulus obtained in the stress relaxation experiment are available for identification. The relaxation time spectrum model that reproduces the relaxation modulus measurements and is the best smoothed in the class of continuous square-integrable functions is sought. Based on the Hilbert projection theorem, the best-smoothed relaxation spectrum model is found to be described by a finite sum of specific exponential-hyperbolic basis functions. For noise-corrupted measurements, a quadratic with respect to the Lagrange multipliers term is introduced into the Lagrangian functional of the model's best smoothing problem. As a result, a small model error of the relaxation modulus model is obtained, which increases the model's robustness. The necessary and sufficient optimality conditions are derived whose unique solution yields a direct analytical formula of the best-smoothed relaxation spectrum model. The related model of the relaxation modulus is given. A computational identification algorithm using the singular value decomposition is presented, which can be easily implemented in any computing environment. The approximation error, model smoothness, noise robustness, and identifiability of the polymer real spectrum are studied analytically. It is demonstrated by numerical studies that the algorithm proposed can be successfully applied for the identification of one- and two-mode Gaussian-like relaxation spectra. The applicability of this approach to determining the Baumgaertel, Schausberger, and Winter spectrum is also examined, and it is shown that it is well approximated for higher frequencies and, in particular, in the neighborhood of the local maximum. However, the comparison of the asymptotic properties of the best-smoothed spectrum model and the BSW model a priori excludes a good approximation of the spectrum in the close neighborhood of zero-relaxation time.

Full-scale polymer relaxation induced by single-chain confinement enhances mechanical stability of nanocomposites

Polymer nanocomposites with tuning functions are exciting candidates for various applications, and most current research has focused on static mechanical reinforcement. Actually, under service conditions of complex dynamic interference, stable dynamic mechanical properties with high energy dissipation become more critical. However, nanocomposites often exhibit a trade-off between static and dynamic mechanics, because of their contradictory underlying physics between chain crosslinking and chain relaxation. Here, we report a general strategy for constructing ultra-stable dynamic mechanical complex fluid nanocomposites with high energy dissipation by infusing complex fluids into the nanoconfined space. The key is to tailor full-scale polymer dynamics across an exceptionally broad timescale by single-chain confinement. These materials exhibit stable storage modulus (100 ~ 102 MPa) with high energy dissipation (loss factor > 0.4) over a broad frequency range (10−1 ~ 107 Hz)/temperature range (−35 ~ 85°C). In the loss factor > 0.4 region, their dynamic mechanical stability (rate of modulus change versus temperature (k)) is 10 times higher than that of conventional polymer nanocomposites.

Development and Characterisation of deep Eutectic Mixture of the Atorvastatin Calcium for Oral Drug Delivery

The poor aqueous solubility and low oral bioavailability of atorvastatin calcium pose significant challenges in optimising its therapeutic efficacy. This study explores the formulation of deep eutectic solvents (DES) to enhance the solubility and bioavailability of atorvastatin calcium for oral delivery. Various DES formulations were prepared using choline chloride, choline bitartrate, and selected carboxylic acids. The formulations were characterised through physicochemical analysis, including pH, drug content, particle size, zeta potential, and Fourier-transform infrared spectroscopy. The most promising formulation, F12, exhibited a yellowish transparent appearance, a mean particle size of 74.21 nm, and a zeta potential of -22.3 mV, indicating good colloidal stability. In vitro drug release studies revealed a delayed release profile for F12 compared to the pure drug, potentially offering advantages in prolonged therapeutic effect and reduced dosing frequency. Kinetic modelling analysis suggested a diffusion-controlled release mechanism influenced by drug diffusion and polymer relaxation. Overall, this study demonstrates the potential of DES formulations in enhancing the solubility and bioavailability of atorvastatin calcium, paving the way for improved therapeutic outcomes and patient compliance.

Numerical investigation on the enhanced heat transfer characteristics of non-Newtonian viscoelastic fluids in microchannel with chip arrays

Elastic turbulence is an efficient heat transfer method at microscale. In this work, we conduct a systematic investigation on the flow and heat transfer performances of viscoelastic polymer solutions in microchannels with chip arrays by means of high-fidelity numerical simulations. Focusing on the effects of fluid elasticity [i.e. polymer relaxation time (λ)] and flow Reynolds number (Re), we find that the synergistic interplay between inertial and elastic forces is strategically exploited to amplify convection, thereby facilitating an enhanced heat transfer performance. For highly elastic fluid, the Nusselt number (Nu) can be improved by 76.13 % compared to that of less elastic fluid, while the pressure drop is reduced appropriately. In addition, as the fluid elasticity increases, the pressure drop decreases and eventually converges to a constant. In the zone of elastic turbulence, the fluid reinforces the convective heat transfer, which can be ascribe to the deformation of long-chain polymer molecules. Particularly, we consider the effect of temperature-dependent λ on the heat transfer performance. Our results demonstrate that the increased temperature-dependent λ decreases the value of Nu, and the variation between values of variable and constant λ is reduced with increasing Re or λ. Hence, in some cases of large fluid elasticity or high Re, it is possible to safely ignore the impact of temperature-dependent λ with an acceptable accuracy. The present work provides important insights into the enhanced heat transfer via elastic turbulence, which could guide the applications in the field of chip cooling.

Kinetic study of in vitro release of curcumin from chitosan biopolymer and the evaluation of biological efficacy

Sustained release of curcumin from the polymeric carrier system chitosan, a natural biopolymer material derived from chitin originated from natural shrimp shell waste, was studied. Six kinetic models, zero order, first order, Korsmeyer–Peppas (KP), Peppas – Sahlin (PS), Higuchi, and Hixson–Crowell, were applied to study the drug release kinetics. The release mechanism of the drug from the curcumin-chitosan composite was evaluated by changing the pH, ionic strength of the release media, and drug concentration. KP and PS models were selected among the studied models to investigate the drug release mechanism from the chitosan biopolymer based on the R2 values (R2 > 0.99). The model constants m in the PS model and n in the KP model stand for the case II relaxation and Fickian diffusion contribution, respectively. The n being < 0.43 in the KP model suggests that the Fickian diffusion governs the drug release. Furthermore, there is a noticeable difference between the values obtained for model parameters m and n in the PS and KP models, indicating that Case II relaxation and Fickian diffusion play crucial roles in the curcumin release mechanism from chitosan. Polymer relaxation has been proven to play a predominant role in releasing curcumin from the composite at lower ionic strengths and higher pH values. Anti-inflammatory activity was tested using the egg-albumin denaturation assay, and the diphenyl-2-picrylhydrazyl assay was carried out to determine the antioxidant activity of the composite. The composite material showed IC50 values of 0.29 mg/ mL and 1.08 mg/ mL for anti-inflammatory and anti-oxidant activities, respectively. The drug composite has shown antibacterial activity against Pseudomonas aeruginosa, Klebsiella pneumoniae, and Staphylococcus aureus, which are highly effective against S.aureus. The resulting inhibition zones for S.aureus were 13.34 ± 0.34 mm, 16.34 ± 0.60 mm, and 13.34 ± 0.73 mm for 5, 10, and 20 mg/ml concentrations, respectively. The drug composite’s minimum inhibitory concentration/ minimum bactericidal concentration ratio for S.aureus, K. pneumoniae, and P.aeruginosa was greater than 4, suggesting that they cause bacteriostatic effects.

Comparison of viscoelastic flows in two- and three-dimensional serpentine channels.

Polymer solutions in the dilute regime play a significant role in industrial applications. Due to the intricate rheological properties of these highly viscoelastic fluids, especially in complex flow geometries, a thorough numerical analysis of their flow dynamics is imperative. In this research, we present a numerical investigation of purely elastic instability occurring in two- and three-dimensional serpentine channels under conditions where fluid inertia is negligible and across a broad spectrum of polymer relaxation times. Our findings reveal a strong qualitative agreement between the existing experimental results obtained from dilute solutions of flexible polymers in microfluidic devices and the numerical simulations conducted in two and three dimensions using the Oldroyd-B model. Spatial flow observations and statistical analysis of temporal flow features indicate that this purely elastic turbulent flow exhibits nonhomogeneous, non-Gaussian, and anisotropic characteristics across all scales. Additionally, our comparison of two- and three-dimensional simulations demonstrates that the elastic instability is primarily driven by the curvature of the streamlines induced by the flow geometry, rather than the weak secondary flow in the azimuthal direction. Therefore, our two-dimensional numerical simulations successfully replicate, at least qualitatively, the features observed in three-dimensional experiments. Furthermore, spectral analysis suggests that, in comparison to elastic turbulence in the dilute regime, the range of scales for the excited fluctuations is narrower.

Interfacial molecular structure and orientation evolution of the polystyrene under confinement during annealing revealed by sum frequency generation vibrational spectroscopy

The geometrical confinement directly affects many crucial properties of polymer thin films by interfacial interactions. A key to understanding the role of these interfacial interactions is to specifically probe the confined interface at the molecular level and in situ. However, the direct and nondestructive detection of interfacial polymer structures under confinement is very difficult. In this study, specific interface-sensitive sum frequency generation (SFG) spectroscopy was applied to study the deuterated PS (d8-PS) film confined between hydrogenated poly (methyl methacrylate) (PMMA) films at the molecular level and in situ. The results showed that the ordering/orientation of the PS chain (backbone and phenyl group) evolved at the buried d8-PS/PMMA interface during annealing. The tilt angle of the PS phenyl group increased while the twist angle decreased with elevated annealing temperature. Both overall SFG ssp and ppp intensities decreased after annealing at 433 K for 24 h, indicating that PS chains entangled with or penetrated the PMMA chains at the confined interface. This study qualitatively and quantitatively revealed the interfacial structure and structural evolution of the PS chain confined between PMMA films in situ during annealing, which is beneficial to the molecular-level understanding of the interfacial chain conformational relaxation of polymers under confinement.

A Novel Intrauterine Device for the Spatio-Temporal Release of Norethindrone Acetate as a Counter-Estrogenic Intervention in the Genitourinary Syndrome of Menopause.

The genitourinary syndrome of menopause (GSM) is a widely occurring condition affecting millions of women worldwide. The current treatment of GSM involves the use of orally or vaginally administered estrogens, often with the risk of endometrial hyperplasia. The utilization of progestogens offers a means to counteract the effects of estrogen on the endometrial tissue, decreasing unwanted side effects and improving therapeutic outcomes. In this study, a norethindrone acetate (NETA)-loaded, hollow, cylindrical, and sustained release platform has been designed, fabricated, and optimized for implantation in the uterine cavity as a counter-estrogenic intervention in the treatment of GSM. The developed system, which comprises ethyl cellulose (EC) and polycaprolactone (PCL), has been statistically optimized using a two-factor, two-level factorial design, with the mechanical properties, degradation, swelling, and in vitro drug release of NETA from the device evaluated. The morphological characteristics of the platform were further investigated through scanning electron microscopy in addition to cytocompatibility studies using NIH/3T3 cells. Results from the statistical design highlighted the platform with the highest NETA load and the EC-to-PCL ratio that exhibited favorable release and weight loss profiles. The drug release data for the optimal formulation were best fitted with the Peppas-Sahlin model, implicating both diffusion and polymer relaxation in the release mechanism, with cell viability results noting that the prepared platform demonstrated favorable cytocompatibility. The significant findings of this study firmly establish the developed platform as a promising candidate for the sustained release of NETA within the uterine cavity. This functionality serves as a counter-estrogenic intervention in the treatment of GSM, with the platform holding potential for further advanced biomedical applications.

Fast Processing Affects the Relaxation of Polymers: The Slow Arrhenius Process Can Probe Stress at the Molecular Level.

Polymer materials are commonly processed at rates higher than those at which their molecules spontaneously reach equilibrium conditions. The resulting nonequilibrium conformations might significantly affect the mechanical behavior and the shelf time of the final products. To understand how processing-properties relations work, we investigated the impact of spin coating, an archetypical method to fabricate thin polymer layers. By using a geometry in which nonequilibrium conformations are frozen over sufficiently long experimental times, we could identify how molecular relaxation is affected by fast preparation methods. We find that while the (α-)segmental relaxation is not affected by the rate at which films are processed, the intensity of the slow Arrhenius process (SAP), a relaxation mechanism active both above and below the glass transition, can be used as a probe of the degree of mechanical stress experienced by the material.

Multiplex vortex instability in the flow of non-Newtonian fluids through microcavity arrays

Complex fluids always possess obvious non-Newtonian properties that facilitate the occurrence and development of vortex instability in porous media, which is of critical significance in many natural and industrial processes. It is widely known that this flow instability is regulated by both fluid flow and solid structure. However, the quantitative understanding of how structural characteristics of porous space affect the evolution of vortex instability is still nascent, especially in the case of fluids with varying rheological properties. Herein, the flow of polymer solutions with distinct non-Newtonian properties through microcavity arrays is experimentally studied, by which we systematically explore the effect of structural parameters of the cavity array on vortex instability. We find that, for both Newtonian and shear-thinning fluids with negligible elasticity, the vortex evolution behavior in each cavity of the cavity array is identical to those in an isolated cavity. In contrast, for viscoelastic fluids, the vortex instability is visibly affected by cavity number and cavity–cavity interval, and this effect exhibits different forms when the fluid shear-thinning participates or not. Multiplex vortex instabilities are observed under these tested conditions. By multiplex, we mean the vortex formation dynamics and evolution patterns are diversified. These unusual evolution phenomena are then interpreted in terms of the interplay between the elongation and relaxation of polymers as they navigate among neighboring cavities. These results can help us to further understand the flow instability of complex fluids in porous media and evoke new strategies for microfluidic applications of efficient mixing.

From ionic clusters dynamics to network constraints in ionic polymer solutions.

Physical networks formed by ionizable polymers with ionic clusters as crosslinks are controlled by coupled dynamics that transcend from ionic clusters through chain motion to macroscopic response. Here, the coupled dynamics, across length scales, from the ionic clusters to the networks in toluene swollen polystyrene sulfonate networks, were directly correlated, as the electrostatic environment of the physical crosslinks was altered. The multiscale insight is attained by coupling neutron spin echo measurements with molecular dynamics simulations, carried out to times typical of relaxation of polymers in solutions. The experimental dynamic structure factor is in outstanding agreement with the one calculated from computer simulations, as the networks are perturbed by elevating the temperature and changing the electrostatic environment. In toluene, the long-lived clusters remain stable over hundreds of ns across a broad temperature range, while the polymer network remains dynamic. Though the size of the clusters changes as the dielectric constant of the solvent is modified through the addition of ethanol, they remain stable but morph, enhancing the polymer chain dynamics.