Specific refractive index increments of segmented polyurethanes

Specific refractive index increments ν of polyester-based segmented polyurethanes in N,N-dimethyl formamide have been determined, and the quotient dν/df_d has been evaluated (where f_d is the weight fraction of hard-segment units). The results are in good agreement with the values calculated from group contributions to the molar refraction, using the Vogel or the Gladstone–Dale equations. The values calculated with the Lorenz–Lorentz equation are too low. A potential explanation of this fact is proposed. The same methods have been applied to reported ν values for polyether-based polyurethanes. An explanation is proposed for differences in dν/df_d for polyester- and polyether-based polyurethanes. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1917–1923, 1998     

Physical properties of fatty acid methyl esters. II. Refractive index and molar refraction

The refractive indices of methyl oleate, linoleate, linolenate, erucate, and the saturated fatty acid methyl esters from acetate to nonadecanoate have been measured at 20C and 40C for the Na_d, H _α , H _β , H _γ lines. The values for the saturated series have been correlated with the Smittenberg relation. Molar refractions have been computed and checked for additivity. The limiting refractive indices obtained from the Smittenberg relation are compared to those obtained from the molar refraction.     

Study of segmented ethylene terephthalate–caprolactone copolymer by differential refractometry and light scattering

A segmented ethylene terephthalate (ET)–caprolactone (CL) copolymer was characterized by light scattering in chloroform tetrahydrofuran and butanone. The flexibility of the copolymer chain is comparable with that of typical flexible chains, such as polystyrene. In the process of applying the Bushuk–Benoit light scattering theory to the segmented PET–PCL copolymer, we encountered not only the problem of finding three solvents with different refractive index but also the problem of determining the specific refractive index increments for the PET and PCL segments in the copolymer, i.e., ν_PET and ν_PCL . In principle, the approximate values of ν_PET and ν_PCL can be obtained from the PET and PCL homopolymers, respectively. In reality, it involves many practical problems, e.g., to find three solvents not only for copolymer but also for the PET and PCL homopolymers. In this study, a different method was used to find both ν_PET and ν_PCL , wherein the ν values of at least two segmented PET–PCL copolymers with different PET compositions were used. With ν_PET , ν_PCL , and ν, we characterized the absolute molecular weight. Further, we show that the composition of an unknown segmented PET–PCL copolymer can be estimated from ν_PET , ν_PCL , and ν. © 1994 John Wiley & Sons, Inc.     

Optical properties,thermal stability,and forming region of high refractive index La2O3–TiO2–Nb2O5 glasses

The high refractive index La₂O₃–TiO₂–Nb₂O₅ glasses were prepared by containerless processing, and the glass‐forming region was determined. The refractive index showed the range from 2.20 to 2.32, and the values were much higher than those of most optical glasses. The completely miscible 30LaO_3/2–(70?x)TiO₂–xNbO_5/2 (0 ≤ x ≤70) system was fabricated to study the compositional dependence of refractive index and optical transmittance. The crucial determinants of the refractive index of oxide glasses, oxygen molar volume, and electronic polarizability of oxygen ions were calculated. The principle of additivity of glass properties was suitable for the calculation of refractive index between glass and compositional oxides. All the glasses were colorless and transparent in the visible to 6.5 μm middle infrared (MIR) region. These results are useful for designing new optical glasses with high refractive index and low wavelength dispersion in wide optical window.     

Medium-range order and physicochemical properties of (100 ? x)(0.5PbO · 0.5P2O5) · xTeO2 glasses in terms of the constant stoichiometry grouping concept

Glasses in the (100 − x)(0.5PbO · 0.5P₂O₅) · xTeO₂ section of the PbO-P₂O₅-TeO₂ system have been synthesized over the entire composition range for the first time and their properties (Raman spectra, refractive index n, density d, glass transition temperature T _g , and light scattering losses) have been investigated. It has been demonstrated that the Raman spectra can be represented as a superposition of constant spectral forms corresponding to constant stoichiometry groupings PbO · P₂O₅, TeO₂ · 2PbO · 2P₂O₅, TeO₂ · PbO · P₂O₅, 2TeO₂ · PbO · P₂O₅, and TeO₂. The existence of crystals of the corresponding stoichiometry has been predicted using the constant stoichiometry grouping concept. The diagram of the constant stoichiometry grouping contents (determined from the Raman spectra) in glasses of the system under investigation has made it possible to determine the partial properties of constant stoichiometry groupings, to calculate the dependences of the refractive index and density on the composition, and to refine the values of n and d for vitreous tellurium dioxide and lead metaphosphate. The practical importance of glasses in the system under consideration for the use in photonic devices has been discussed.     

VARIATIONS OF REFRACTIVE INDEX OF GLASS WITH TIME AND TEMPERATURE IN ANNEALING REGION*

The refractive index of a rapidly cooled fiber of borosilicate glass was found to increase according to the equation, 1/(N₆–N) – 1/(N₆–N₀) =At, where t is time, N₆ is equilibrium index, and A is a constant at constant temperature. Index data were plotted according to this equation to determine, graphically, values of N₆ and A for several temperatures between 914° and 1060°F. Values of N₆ for temperatures from 1060° to 1180°F. were determined by prolonged heating of the glass at each 20° interval. The change of A with temperature was found to be well represented by the equation, log A=K/T+C, where T is the absolute temperature and K and C are constants.     

Studies on syntheses and properties of episulfide‐type optical resins with high refractive index

A series of novel high refractive index episulfide‐type optical resins were prepared by ring‐opening copolymerization of bis(β‐epithiopropylthioethyl) sulfide (BEPTES) with episulfide derivative of diglydicyl ether of bisphenol A (ESDGEBA) and 2,4‐tolylene diisocyanate (TDI), respectively, in the presence of triethylamine as a curing catalyst. The episulfide monomers, BEPTES and ESDGEBA, were synthesized from their corresponding epoxy compounds, respectively. The cured transparent resins exhibit high refractive index (n_d > 1.63) and relatively low dispersion. The refractive index (n_d) and Abbe's number (ν_d) of the BEPTES/ESDGEBA curing system increased linearly with the weight content of BEPTES monomer in the range from 1.633 and 34.0 for the copolymer with 10 wt % of BEPTES to 1.697 and 38.1 for the homopolymer of pure BEPTES. For the BEPTES/TDI curing system, the refractive index and Abbe's number varied linearly with the molar ratio of BEPTES to TDI from 1.652 and 28.7 to 1.669 and 34.6. High glass‐transition temperatures (T_g > 130°C) of the cured BEPTES/TDI resins were observed, which indicate that the cured BEPTES/TDI resins possess a good heat resistance. The optical, physical, and thermal properties of the episulfide‐type cured optical resins were also discussed in this study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2426–2430, 2003     

Permeability alterations in unilamellar liposomes due to betaine-type zwitterionic and anionic surfactant mixed systems

The alterations caused by betaine-type zwitterionic and anionic surfactant mixed systems in the permeability of unilamellar liposomes have been investigated. The partition coefficient of these systems, at different molar fractions, between the aqueous phase and the lipid bilayer of liposomes has been determined. These surfactant mixed systems were formed byN-dodecyl-N,N-dimethylbetaine (C₁₂-Bet) and sodium dodecyl sulfate (SDS) in the presence of 20 mM PIPES buffer and 110 mM Na₂SO₄, at pH 7.21. Unilamellar liposomes were prepared from egg phosphatidylcholine and phosphatidic acid (9:1 molar ratio). The release of the fluorescent agent 5-(6)-carboxyfluorescein induced by the systems has been studied at sub-solubilizing concentrations. When the molar fraction of C₁₂-Bet/SDS is about 0.4, the critical micelle concentration values of these systems exhibit a minimum, whereas their partition coefficient between the aqueous phase and lipid bilayer of lipid bilayers shows a maximum. There is a consistent correlation between the partition coefficient and the ability of the different systems of surfactants to modify the permeability of liposomes.     

Interpreting the optical properties of oxide glasses with machine learning and Shapely additive explanations

Due to their excellent optical properties, glasses are used for various applications ranging from smartphone screens to telescopes. Developing compositions with tailored Abbe number (V_d) and refractive index at 587.6 nm (n_d), two crucial optical properties, is a major challenge. To this extent, machine learning (ML) approaches have been successfully used to develop composition–property models. However, these models are essentially black boxes in nature and suffer from the lack of interpretability. In this paper, we demonstrate the use of ML models to predict the composition-dependent variations of V_d and n_d. Further, using Shapely additive explanations (SHAP), we interpret the ML models to identify the contribution of each of the input components toward target prediction. We observe that glass formers such as SiO₂, B₂O₃, and P₂O₅ and intermediates such as TiO₂, PbO, and Bi₂O₃ play a significant role in controlling the optical properties. Interestingly, components contributing toward increasing the n_d are found to decrease the V_d and vice versa. Finally, we develop the Abbe diagram, using the ML models, allowing accelerated discovery of new glasses for optical properties beyond the experimental pareto front. Overall, employing explainable ML, we predict and interpret the compositional control on the optical properties of oxide glasses.     

Spontaneous Vesicle Formation in Mixtures of Quaternary Ammonium Compounds with Carbamate and Sodium Dodecylbenzene Sulfonate

Spontaneous vesicles formation in the aqueous mixtures of 2,3‐bis (dodecylcarbamoyloxy)‐N, N‐dimethyl‐N‐(2‐hydroxyalkyl) propyl ammonium chloride (C₁₂PAC) and sodium dodecylbenzene sulfonate at different mixing molar ratios have been investigated. The characterizations are demonstrated by electrical conductivity measurements, dynamic light scattering and zeta (ζ) potential measurements. The ζ‐potential results indicate the C₁₂PAC/SDBS systems are stable. The shapes of the catanionic vesicles are observed by negative‐staining transmission electronic microscopy. Meanwhile, from the viewpoint of molecular geometry structure, the electrostatic interaction between anionic and cationic molecules is regarded as the main driving force for spontaneous formation of vesicles.     

Swelling kinetics of poly(acrylamide)/poly(mono-n-alkyl itaconates) hydrogels

Hydrogels of mono-n-alkyl itaconate/N-acrylamide have been synthesised. The swelling process at three different pH values (acid, neutral and basic) has been studied. The experimental data indicate that our hydrogels follow second-order swelling kinetics. According to this, the kinetic constant, K_∞, and the swelling capacity at equilibrium, W_∞, have been calculated. The influence of the solvent pH and the molar mass of the mono-n-alkyl itaconate monomeric unit has been analysed. It seems that the general balance between the hydrogen bonding and the hydrophobic interactions regulates the swelling process of these hydrogels.     

The effect of geometrical parameters on the flow field of an opposed jet rim mix head: Equal flow and matched fluids

The effect of geometrical parameters on the flow field present in the mix head used in reaction injection molding (RIM) are presented for Re_d (Re_d = 4Q/πdv, nozzle diameter d, fluid kinematic viscosity v and the volumetric flow rate Q through the nozzle) representative of commercial practice. Quantitative velocity measurements of the flow field in a mix head have not been reported in the literature despite the extensive use of the mix head for reaction injection molding. Flow visualization and velocity measurements using a laser Doppler anemometer have been obtained for different values of geometrical parameters such as mix chamber diameter (D), distance from the nozzle inlet to the closed end of the chamber (H), and nozzle needle position (N). The ratio of the mix chamber to nozzle diameter (d) (D* = D/d) was a significant parameter affecting the flow field. The distance from the impingement point to the closed end of the chamber was found to have little effect on the observed flow field beyond the impingement area. A nozzle needle position that partially constricted the nozzle opening was found to decrease the axial distance to unidirectional flow within the mix chamber.     

Refractive index and compressibility of the KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glass at pressures up to 6.0 GPa

The refractive index of potassium aluminosilicate glass of the KAlSi₃O₈ composition in the pressure range up to 6.0 GPa has been measured using a polarizing interference microscope and an apparatus with diamond anvils. The changes in the relative density, which characterize the compressibility of the K₂O · Al₂O₃ · 6SiO₂ glass, have been estimated in the pressure range under investigation from the measured refractive indices within the framework of the theory of photoelasticity. The results have been compared with the data previously obtained for the Na₂O · Al₂O₃ · 6SiO₂ glass. Although the molar contents of Al₂O₃ and M ₂O (where M = K or Na) are identical in these glasses, the KAlSi₃O₈ glass exhibits a higher compressibility, which agrees with the lower degree of depolymerization of this glass as compared to that observed in the NaAlSi₃O₈ glass. The pressure derivative of the bulk modulus K′ _t , which is calculated from the Birch-Murnaghan equation for the KAlSi₃O₈ glass (K′ _t = 7–9), is higher than that for the NaAlSi₃O₈ glass (K′ _t = 5.5–6.0). An increase in the pressure derivative of the bulk modulus K′ _t upon replacement of the Na⁺ cations by the K⁺ cations is explained by the inhibition of compression of the large K⁺ cations, which are located in cavities and have a considerably larger orbital radius than the Na+ cations. This manifests itself in the fact that the curves describing the dependences of the change in the relative density (d − d0)/d (compressibility) on the pressure P for the KAlSi₃O₈ and NaAlSi₃O₈ glasses converge at pressures above 4.0 GPa.     

Optical and colorimetric studies of thorium nitrate‐doped poly(vinyl alcohol) films

In this study, poly(vinyl alcohol) (PVA) films doped with thorium nitrate hydrate [Th(NO₃)₄] have been prepared using casting technique. The optical absorption spectra were recorded at room temperature in the wavelength range 200–800 nm. From the absorption edge studies, the values of the Urbach energy (E_u) have been evaluated. These energy values vary slightly with composition, indicating that the model based on electronic transitions between localized states is not preferable. Optical parameters such as refractive index and complex dielectric constant have been determined. The dispersion of the refractive index is discussed in terms of the single‐oscillator Wemple‐DiDomenico model. Color properties of the prepared samples were discussed in the framework of CIE L*u*v* color space. POLYM. COMPOS., 35:1786–1791, 2014. © 2013 Society of Plastics Engineers     

Thermodynamic properties of 1‐ETHYL‐3‐methylimidazolium methanesulphonate with aromatic sulphur,nitrogen compounds at T = 298.15–323.15 K and P = 1 bar

This work investigates the ability of 1‐ethyl‐3‐methylimidazolium methanesulphate ([EMIM][MeSO₃]) as a green and tuneable solvent for denitrification and desulphurisation studies. Experimental density, surface tension and refractive index data have been measured for the following systems: [EMIM][MeSO₃] (1) + pyridine (2), [EMIM][MeSO₃] (1) + pyrrole (2), [EMIM][MeSO₃] (1) + quinoline (2), [EMIM][MeSO₃] (1) + indoline (2), [EMIM][MeSO₃] (1) + thiophene (2) and [EMIM][MeSO₃] (1) + water (2) over the entire mole fraction of [EMIM][MeSO₃] at T = 298.15–323.15 K and P = 1 bar. Further from experimental density, surface tension and refractive index, coefficient of thermal expansivity, excess molar volume, deviation of surface tension and refractive index deviation were also calculated. It was found that the heteroaromatic nitrogen/sulphur compounds are completely miscible in [EMIM][MeSO₃]. The surface tension values were found to increase while the refractive index decreases with increasing mole fraction of [EMIM][MeSO₃]. The experimental values for surface tension increased in the order: pyridine > thiophene > pyrrole > indoline > quinoline > water and for refractive index: pyridine > pyrrole > indoline > quinoline > thiophene > water. It was found that the composition of [EMIM][MeSO₃] has a greater influence than temperature in deciding the surface, optical and thermodynamic properties for similar molecular interaction such as IL–thiophene and IL–pyrrole than dissimilar molecules such as IL–water. Further quantum chemical‐based COSMO‐RS tool was used to estimate the activity coefficient at different composition. © 2012 Canadian Society for Chemical Engineering     

Composition-dependent properties of segmented polyurethanes

We studied segmented polyurethanes (SPU) from poly(diethylene glycol adipate) with molar masses M_SFT = 780, 1365, 1780 and 3200 g/mol (soft fragments, SFT), 2,4-toluene diisocyanate and 2,4-toluene diamine (stiff fragments, STF) with essentially monodisperse molar mass distribution of STF. They were characterized by WAXS, SAXS, heat capacity measurements, mainly from 150–450 K, and enthalpies of solution in dimethyl formamide at room temperature, ΔH_sol. The experimental results may be summarized as follows.

• The glass transition temperatures of SFT decrease with an increase of M_SFT, but remain essentially composition-invariant at fixed M_SFT, whatever the STF volume fraction φ.
• The surface-to-volume ratio of STF domains exhibits sudden, jump-like transitions at volume fractions φ* = 0.23 and φ** = 0.40, respectively.
• Exothermic (i.e., negative) values of ΔH_SOl exhibit a jump-like decrease at φ* = 0.23.

It has been shown that the main cause of the latter effect is the transition of SFT from a somewhat extended to an essentially unperturbed conformation.     

Densities,ultrasonic speeds,refractive indices,and COSMO analysis for binary mixtures of dichloromethane with acetone and dimethylsulfoxide at T = (298.15, 303.15, and 308.15) K

Experimental densities (ρ), ultrasonic speeds (u), and refractive indices (n_D) of binary mixtures of dichloromethane (DCM) with acetone (ACT) and dimethylsulfoxide (DMSO) were measured over the whole composition range at T?=?298.15, 303.15, and 308.15?K. From the experimental data, excess molar volume (V^E), deviations in isentropic compressibility (Δk_s), deviations in intermolecular free length (ΔL_f), deviations in refractive index (Δn_D), and deviations in ultrasonic speed (Δu) were calculated. Moreover, the Benson–Kiyohara theory was applied to the binary mixtures to obtain the theoretical Δk_s values. The COSMO calculations depending on density functional theory were utilized to estimate the σ-profiles for the DCM, ACT, and DMSO. The interpreted σ-profile trends were found supportive with the experimental findings. Applicability of different empirical and semi-empirical relations of refractive index data were tested against the measured results, and good agreement has been obtained. The possible results of intermolecular molecular interactions among mixture components were interpreted.     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Axial mixing of liquid in a turbulent-bed contactor

The axial dispersion of liquid in a 12-in. turbulent-bed contactor has been investigated for three packing sizes: ½-in., 1-in. and 1½-in. The gas and liquid flow rates were varied from 500 to 2700 lb./(hr.)(sq. ft.) and from 1500 to 11,000 lb./(hr.)(sq. ft.) respectively. The transient response technique using KCl solution as the tracer was employed for this purpose. The experimentally determined residence-time distribution curves were interpreted by means of a one-dimensional dispersion model. The axial dispersion coefficient, D_L, was found to increase with increasing gas flow rate, liquid flow rate, or packing size. In terms of Peclet number (N_Pe = ū d_p/D_L), the present data showed that N_Pe was dependent on Reynolds number (N, = d_p ū ρ/μ), Gallileo number (N_Ga = d_p³ ρ³ g/μ²), and reduced gas mass velocity (Δ = (G-G_mf)/G_mf), but the ratio of the Peclet number for a turbulent contactor to the Peclet number for a fixed-bed contactor, N_Pe/N_Peo, depended only on Δ, and the diameter ratio d_p/d_t. A correlation of N_Pe/N_Peθo with Δ and d_p/d_t is presented.