Rheo-kinetics of bovine serum albumin in catanionic surfactant systems

The effects of catanionic surfactant systems consisting of mixtures of cationic cetyltrimethylamonium bromide (CTAB) and anionic sodium dodecyl sulfate (SDS) on the rheological properties and kinetics of bovine serum albumin (BSA) were investigated. The ionic strength of the solution was varied by using different mixing ratio of SDS and CTAB. Gelation curves observed in dynamic viscoelastic measurements were fitted with gelation kinetics models to describe the gelation under isothermal and non-isothermal conditions. Overall, the gelation of BSA in cationic-rich solutions was found to be more energetically favorable when compared with BSA solvated in anionic-rich solutions. Consequently, highest gel temperature (T_gel) and time (t_gel) were observed for anionic-rich solutions with SDS/CTAB molar ratio of 4.0 (i.e., SDS/CTAB=4.0), while lowest gel temperature and time were found for cationic-rich solutions with SDS/CTAB molar ratio of 0.25 (SDS/CTAB=0.25). BSA in equal molar ratio of the mixed surfactants (SDS/CTAB=1.0) showed a gel temperature and time in the halfway between the anionic and cationic-rich regions. Interestingly, under isothermal and non-isothermal conditions, BSA in equimolarly mixed and anionic-rich solutions showed a heat-dependent protective effect against thermal denaturation and gelation. The protective effect on BSA gelation in equimolar and anionic-rich solutions was diminished by increasing the catanionic concentration under non-isothermal conditions, while under isothermal conditions, protective effect on BSA gelation increased with catanionic concentration. On the other hand, cationic-rich solutions did not protect BSA from thermal denaturation and gelation, and therefore the gelation rate increased with catanionic concentration in all heating conditions examined.     

Reversible gelation of acrylonitrile–vinyl acetate copolymer solutions. II. Mechanical properties

Concentrated solutions of acrylonitrile polymers exhibit reversible gelation. The rate of gelation at 25°C. was determined for various solutions of an acrylonitrile copolymer containing 7.7% vinyl acetate in mixtures of dimethylacetamide (solvent) and water (nonsolvent) by measuring the shear modulus of the forming gel as a function of time. The mechanical properties were also measured on a series of gels formed by cooling solutions to ?78°C. It was found that both the rate of gelation at 25°C. and the modulus of gels formed at ?78°C. increase very rapidly as either the solids level of the solution of the water content of the solvent is increased. The gelation rate data wree correlated with the gel melting points of the gels. The results are discussed and compared with the analogous but limited data available for other systems.     

Convective and radiant (IR) curing of bulk and waterborne epoxy coatings as thin layers. Part II: Infrared curing

In the first part of this paper, a method for studying the curing of 100-μm-thick epoxy-based layers on steel substrates was described. In this second part, we extend our study to radiative (infrared) heating conditions. A simple waterborne epoxy reactive system based on a diglycidylether of bisphenol-A prepolymer and a polyether triamine was used. The chemical kinetics during infrared heating were studied with the reaction kinetics recorded during convective heating. A second order autocatalytic model described the data. The curing mode had no significant influence on the heating kinetics but the heating rate had a significant influence on the curing kinetics. Higher heating rates can be achieved by infrared heating conditions compared with convective heating. The gelation phenomenon was changed for infrared conditions. Microdielectrometry can be used to record in situ the extent of reaction of the epoxy reactive system for thin layers during radiant heating.     

Effect of ionizing irradiation and blending of natural rubber latex on polyvinylalcohol gelation by using chemical and freezing–thawing processes for use in the field of construction engineering

The aim of this work is to study the gelation behavior of polyvinylalcohol (PVA) and natural rubber latex (NRL) using two methods: The first was chemical gelation by adding sodium borate as a crosslinking to obtain a modeling clay gel able to draw easily under tension (using drum mill) or by using hand pressing. Irradiation was then applied at 2.5 Mrad to possess more crosslinking effect, where stable and rubbery‐gel shape in the dimension was obtained. The second method, where samples of liquid PVA were frozen and thawed for three consecutive cycles. The obtained gel was quite rubbery but completely soluble in hot water at 70°C. Irradiation was performed at 2.5 Mrad to produce a highly rubbery gel and resistant to boiled water. Also, blending of NRL with PVA induced a significant increase in gel‐elasticity and resistivity to boiled water. Factors affecting the properties of the prepared gel such as gel draw ability and gel strength were studied. The study was supported with thermal and scanning electron microscopy (SEM) to investigate the modification of PVA‐gel behavior through irradiation and blending with NRL processes. The results indicated that the PVA‐gel obtained by chemical method or blended with NRL through freezing–thawing gelation gave a superior ability for cement loading. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Solvent‐solubility‐parameter‐dependent homogeneity and sol–gel transitions of concentrated polyacrylonitrile solutions

In this study, we systematically explored the dependence of the homogeneity and sol–gel transition temperatures of various polyacrylonitrile (PAN) solutions on the solvent solubility parameters. The Cole–Cole slope was used to characterize the solution homogeneity, and we found that the PAN/dimethyl sulfoxide (DMSO) solution, which had a smaller Hansen solubility parameter distance between the solvent and PAN, showed better solution homogeneity than the PAN/dimethylformamide and PAN/dimethylacetamide solutions. Additionally, we found that both heating and cooling were able to cause the gelation of the PAN solution, although their mechanisms were totally different. The gelation caused by heating was ascribed to the nitrile–nitrile coupling of PAN chains, whereas the gelation caused by cooling was due to the solvent bridge effect. In this case, DMSO, which had the highest polarity and the strongest interactions with nitrile groups, caused the highest gelation temperature of the PAN solution during cooling. The gelation temperature of the PAN solution exhibits dependence on its solvent polarity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45405.     

Hot embossing in microfabrication. Part I: Experimental

The relationship among processing conditions, material properties, and part quality in hot embossing was investigated for three optical polymers: polycarbonate (PC), polymethyl methacrylate (PMMA), and polyvinyl butyral (PVB). A series of systematic embossing experiments was conducted using mold inserts having either single or multiple feature depths. The feature dimensions varied from 90 to 3000 μm. The processing conditions studied include embossing pressure, thermal cycles, and heating methods. The displacement profile, replication accuracy and molded‐in stresses were measured experimentally. It was found that for isothermal embossing, both replication accuracy and birefringence pattern depend strongly on the processing conditions. For non‐isothermal embossing, the molded parts showed excellent replication as long as the feature transfer was completed. The flow pattern under isothermal embossing resembles a biaxial extensional flow. Under non‐isothermal embossing, the polymer deformation involves an upward flow along the wall of mold features, followed by downward compression and outward squeezing. Rheological characterization and hot embossing analysis are presented in Part II.     

Thermoreversible and salt-sensitive turbidity of methylcellulose in aqueous solution

The turbidity of methylcellulose (MC) aqueous solutions without or with salt was investigated by optical transmittance. The optical transmittance was found to decrease with heating, while it recovered upon cooling. This phenomenon reflected the micro-phase transition from an unassociated state to a hydrophobically associated state in the solution when the system underwent the sol-gel transition. The derivative of absorbance (dA/dT) was used to determine the clouding point during gelation and the melting point during degelation. A salt-out salt (NaCl), a salt-in salt (NaI) and a salt mixture (NaCl+NaI) were, respectively, added into a MC solution to further investigate effects of salts on the gelation behavior. The critical transition temperatures obtained from rheological and micro thermal measurements were found to be consistent with the clouding points obtained by turbidity measurements. In the MC solutions with the salt mixtures, the critical temperatures followed a linear rule of mixing, indicating that the effects of salts on the sol-gel transition of MC are completely independent.     

A polyacrylamide hydrogel for application at high temperature and salinity tolerance in temporary well plugging

In addition to conventional approach to ensure the successful application of polymer hydrogels in maintaining temporary well plugging, exact analysis of gel formation and gel strength properties in wellbore are necessary. In this work, bottles and rheology tests are used to investigate the polymer hydrogel gelation time and cross-linking kinetics of sol–gel systems which consist of polyacrylamide and chromium acetate hydroxide as a cross-linker. The effects of temperature of 90 °C and pressure of 3000 psi (typical Iranian oil well condition) were studied in relation to gelation time, strength and the mechanical properties of the hydrogel. The average molecular weight of the polymer chains between cross-link ties was evaluated using an oil-well laboratory system and compressive strength test. Differential scanning calorimeter (DSC) analysis of dried gel and the effect of temperature on the kinetics of the gel swelling in different solutions such as distilled water, tap water, formation water and oil were studied. The results showed that the number of tie points between each entanglement has not much reduced under pressure. Therefore, the prepared hydrogel can maintain its chemical structure under the Iranian oil well pressure and can be proposed to field studies. The degree of sol–gel reaction of prepared hydrogel and the activation energy based on the Arrhenius equation were calculated to be 1.5 and 274 kJ/mol, respectively.     

CE2908聚酯粉末涂料固化反应特性

用示差扫描量热法(DSC)在动态条件下对CE2908聚酯/异氰尿酸三缩水甘油酯(TGIC)体系的固化反应动力学进行了研究。运用温度-升温速率图外推法确定了该体系的特征参数∶凝胶温度(T0)、固化温度(Tp)和后固化温度(Tf)分别为113℃、146℃和195℃。采用Kissinger方程和Crane方程计算CE2908聚酯/TGIC酯体系的动力学参数,平均表观活化能Ea为62.32 kJ/mol、频率因子A为8.50×106min-1、反应级数n为0.95。建立了该树脂体系的固化动力学模型。利用所建立的固化动力学方程分别讨论了等温和动态条件下CE2908聚酯/TGIC的固化反应特性,为优化聚酯/TGIC体系粉末涂料固化工艺提供了理论依据,并在生产工艺中验证了其正确性。     

Plugging behavior of gellan in porous saline media

In this article, the hydrodynamic behavior of dilute aqueous solutions of a natural polysaccharide—gellan in the porous media under the modeled oilfield conditions is described. The hydrodynamic properties of gellan and poly(acrylamide) solutions in saline porous media are compared. The influence of inorganic salts NaCl, KCl, CaCl₂, MgCl₂, and BaСl₂ on sol–gel and gel–sol transitions of dilute gellan solutions was evaluated. The mechanism of sol–gel transition in the presence of individual alkaline and alkaline‐earth metal salts is described on the basis of literature data. The viscometric measurements revealed that the effectiveness of salts to enhance gelation of gellan changes in the following order: BaСl₂ > CaCl₂ ≈ MgCl₂ > KCl > NaCl. The sol–gel and gel–sol phase transitions of gellan solution were also observed upon addition of oil field water containing 73 g L^?1 of alkaline and alkaline earth metal ions. During the injection of gellan solutions into the porous media saturated by saline water an oscillation of the injection pressure was observed. Such behavior of gellan is explained by either the sol‐to‐gel and the gel‐to‐sol transitions of the polymer taking place in saline water or the step‐by‐step plugging of high permeable channels until all high permeable channels of sand packs are plugged due to gellan invasion. The application of brine‐initiated gelation of gellan for water shutoff operations (WSO) in field conditions was demonstrated. Higher technological effectiveness of gellan injection in comparison with existing gelation systems was shown. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41256.     

Percolation of glassy regions during photopolymerization of epoxy acrylate in DMF

The gelation of epoxy acrylate (EA) 80% and tripropyleneglycol diacrylate (TPGDA) 20% was studied through the use of photo-differential scanning calorimetric (photo-DSC) technique in the presence of a thioxanthone based initiator. Photo-induced polymerization reactions were performed under identical conditions of temperature, initiator concentration and UV light intensity in various N,N-dimethylformamide (DMF) contents. Photo-DSC technique allowed us to monitor the gelation without disturbing the system mechanically, and to test the universality of the gelation as a function of DMF content. During gelation, it was observed that all conversion curves presented useful sigmoidal behavior which was predicted by employing a percolation model. Observations around the glass transition point, t_g, revealed that gel fraction exponent β obeyed the percolation picture. A significant solvent effect on the photopolymerization kinetics of EA/TPGDA was observed with changes in DMF content. DMF is used as solvent, which acts as a diluent and proton donor during photogelation.     

Performance of fly ash based polymer gels for water reduction in enhanced oil recovery: Gelation kinetics and dynamic rheological studies

The complexity of well and reservoir conditions demands frequent redesigning of water plugging polymer gels during enhanced oil recovery (EOR). In the present study, we developed coal fly ash (CFA) based gels from polyacrylamide (PAM) polymer and polyethyleneimine (PEI) crosslinker for water control in mature oil fields. The CFA acts as an inorganic additive to fine-tune gelation performance and rheological properties of PAM/PEI gel system. Hence, effects of various CFA (0.5 to 2 wt%), PAM (2 to 8.47 wt%) and PEI (0.3 to 1.04 wt%) concentrations on gelation kinetics and dynamic rheology of pure PAM/PEI gel and PAM/PEI-CFA composite gels were studied at a representative reservoir temperature of 90 oC. Experimental results reveal that gelation time of pure PAM/PEI gel increases with increasing CFA addition. Further observation demonstrates that increasing PAM and PEI concentrations decreases the gelation times of PAM/PEI-CFA composite gels. Gelation time was found to be within 3-120 hours. Understanding the property of reaction order enables better prediction of gelation time. Dynamic rheological data show that viscoelastic moduli (G′ and G″) of various PAM/PEI-CFA composite gels improved better as compared to the pure PAM/PEI gel across the strain-sweep and frequency-sweep tests. SEM analysis of selected samples at 72 hours and 720 hours of gelation activity consolidated gelation kinetics and dynamic rheological results. These polymer gels are excellent candidates for sealing water thief zones in oil and gas reservoirs.     

不同增压方式对空气源吸收式热泵性能影响的模拟分析

我国建筑采暖和生活热水能耗较大,基于空气源吸收式热泵的供热系统是北方寒冷地区具有较大节能潜力的解决方案。由于单效空气源吸收式热泵无法运行在气温较低的环境下,提出采用增压循环来提高空气源吸收式热泵的低温性能,并根据增压方式的不同分为低压增压和高压增压两种形式。以NH₃-LiNO₃作为工质对,对不同形式空气源吸收式热泵进行了对比分析。结果表明:两种增压方式均能有效提高吸收式热泵的低温性能,在不同的室外气温、热源温度和热水温度下,能够实现20%~45%的节能率;此外,低压增压的一次能源效率比高压增压更高。综合节能性和实现难易程度,低压增压是提高空气源吸收式热泵低温性能的较好手段。     

Mechanism of solvent entrapment within the network scaffolding in organogels: thermodynamic and kinetic investigations

A detailed investigation on the thermodynamic behaviour of the physical and chemical organogels, using differential scanning calorimetry (DSC) and modulated thermogravimetric analysis (MTGA), is presented. Aluminium soap of fatty acid was used as the physical gelator and in situ crosslinking of siloxane copolymer was used for chemical gelation. The effects of the type and concentration of the gelators and the corresponding mesh‐size distribution of the gel network scaffolding on the trapped‐solvent crystallization, melting and evaporation mechanism, and kinetics are examined. It appears that the kinetics of crystallization of the trapped‐solvent are significantly affected by the quality of the gel network scaffolding and can be treated successfully by the Avrami equation of crystallization. From the melting behaviour of the entrapped‐solvent crystallites, quantitative information about the number of solvent molecules bound per molecule of the gelator has been extracted. The effect of gelation network structure on the kinetics of evaporation of the solvent from the gel network scaffolding has been evaluated. DSC appears to be the reliable technique to evaluate the population distribution of solvent molecules trapped in the gel network scaffolding. Copyright © 2003 Society of Chemical Industry     

A microwave-based method for the synthesis of carbon xerogel spheres

Carbon xerogel spheres with millimeter-scale diameters were synthesized by a simple process using microwave radiation as the heating source. Using this type of heating it is possible to establish the gelation point of different resorcinol–formaldehyde solutions and stop the gelation step of the material at the exact time of gelation. Organic gel spheres can then be directly obtained by stirring in a silicone bath at 80 °C. Finally, carbonization is performed to obtain carbon xerogels with a spherical shape. The size and porous texture of the spheres can be controlled by adjusting the synthesis conditions.     

Convective and radiant (IR) curing of bulk and waterborne epoxy coatings as thin layers. Part I: Methodology

A method for studying the curing of 100 μm-thick epoxy-based layers coated on steel substrates is described. A simple waterborne epoxy reactive system based on a diglycidylether of bisphenol-A prepolymer and with a polyether triamine was set up by emulsifying the epoxy resin with the use of an ethoxylated-nonylphenol emulsifier. The parliculur phenomena involved during the isothermal curing of such an epoxy emulsion were decomposed by considering the same formulation without water and without water + emulsifier. The chemical kinetics were determined by DSC and by size exclusion chromatography. As previously proposed for numerous epoxy-amine reactive systems, for the three types of coatings, a second-order autocatalytic law was able to interpret the data. The presence of water delays the gelation characterized by rheological measurements. As a consequence, the epoxy conversion at the gel point increases. This phenomenon can be related to the inhomogeneous polymerization process during which the epoxy groups can be trapped into the initial epoxy particles. In addition, the microdielectrometry technique was used to follow the curing degree of the epoxy reactive system of thin layers during the drying and curing processes under radiant heatings such as infrared curing.     

低温下提高CO2空气源热泵进水温度对系统性能的影响

在低温工况下,因跨临界循环CO₂热泵系统气体冷却器的进水温度和CO₂出口温度降低,压缩机吸气压力和温度随之降低。当系统的吸气压力低于压缩机的吸气压力下限时,将导致系统无法稳定运行。为了改变这种现象,采用在气体冷却器冷水入口处混水的方法,将热水箱的热水旁通至气体冷却器冷水入口。采用三通调节阀调节混水比例,适当提高气体冷却器的进水温度,以期实现系统在低温工况下的稳定运行。实验测试结果表明,采用混水方法不仅可保证低温工况下跨临界循环CO₂空气源热泵热水系统的稳定运行,同时可降低结霜频率,延长系统运行时间,但系统的制热量和COP将小幅下降。兼顾系统的热力性能及运行稳定性,当环境温度为-20℃、制热温度为60℃时,较为适宜的混水温度为12~18℃。     

Depletion kinetics of perfluoropolyether films with functional end groups using molecular dynamics simulation

Molecular dynamics simulation coupled with a coarse-grained model is employed to investigate the surface depletion kinetics of functional polyether film under heat treatment. The real-time evolutions of lubricant film desorption and decomposition are examined during rapid heating and isothermal stages. The reaction order of lubricant depletion is evaluated during the rapid heating using a constant heating rate and various coverages. It reveals that a peak in the desorption (decomposition) rate is formed and is independent of the mass (bond) coverage, which gives rise to a first-order, coverage independent depletion kinetics. The rate constants for lubricant desorption and decomposition are thus calculated based on a first-order kinetics-controlled reaction during the isothermal stage. The kinetics of functional lubricant depletion shows that desorption is the main mechanism of lubricant depletion under rapid and isothermal heat treatment and is the major cause of lubricant thermal instability on the surface.     

Air convective drying and curing of polyurethane-based paints on sheet molding compound surfaces

In this study the kinetics and phase changes which occurred during the convective drying of a model car paint based on the polyurethane chemistry is described. The competition between the kinetics of the solvent removal and the phase changes, such as the gelation and/or the vitrification of the polyurethane, needs to be taken into account to avoid the defects in the resulting dried coating. The kinetics of polycondensation of a two-component polyurethane based on polyester triol and triisocyanate in a mixture of various solvents was studied as a 100 μm thick layer on sheet molding compound (SMC) and zinc plated steel plates. Differential scanning calorimetry (DSC) and Fourier-Transform infrared spectrometry (FTIR) and thermogravimetric analysis (TGA) during isothermal curings allowed us to determine the rate constants and the activation energies by using second and third order autocatalytic models. UPRES-A CNRS Q-5007, CPE Lyon, Bat. G308, Campus de la Doua, 69622 Villeurbanne Cedex, France UMR CNRS 5627, Institut National des Sciences Appliquées de Lyon, Bat. 403, 69621 Villeurbanne Cedex, France     

Reversible gelation of acrylonitrile–vinyl acetate copolymer solutions

The reversible gelation of acrylonitrile–vinyl acetate copolymers in concentrated solutions has been studied with the use of various solvents. These concentrated solutions gel or become rigid with time, but they become fluid again when heated above a certain temperature called the gel melting point. A technique involving the use of mercury drops was developed to measure this transition. This temperature was evaluated as a function of solids level, water content in the solvent, and the amount of vinyl acetate in the copolymer, dimethylacetamide being used as the solvent. Four other solvents were used to obtain limited data. Gel melting was studied further by differential thermal analysis and shear modulus measurements. The results are discussed in terms of network formation and solubility. The x-ray diffraction results imply that the tie points of the gel are crystalline.