Radical copolymerization between methyl methacrylate and N‐cyclohexylmaleimide with thiol as an inifer

N‐dodecanethiol (RSH) was found efficient to initiate the radical copolymerization of methyl methacrylate (MMA) with N‐cyclohexylmaleimide (NCMI) at 40–60°C. The initial copolymerization rate, R_p, increases respectively with increasing [RSH] and the mol fraction of NCMI in the comonomer feed, f_NCMI. The molecular weight of the copolymer decreases with increasing [RSH]. The initiator transfer constant of RSH was determined to be C_I = 0.21. The apparent activation energy of the overall copolymerization was measured to be 46.9 kJ/mol. The monomer reactivity ratios were determined to be r_NCMI = 0.32 and r_MMA = 1.35. The glass transition temperature of the copolymer increases obviously with increasing f_NCMI, which indicates that adding NCMI may improve the heat resistance of plexiglass. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1417–1423, 1999     

Evaluation of radial voidage profiles in packed beds of low‐aspect ratios

The relationship between the radial voidage profile, ?(r), and the radial distribution of centres of mono‐sized spherical particles, f(r), is revised. A close expression is given for the section S(r₁, r_c), the area of the segment of a cylindrical surface of radius r intersected by a particle centred at r_C. From this expression, ?(r) can be evaluated straightforwardly from the knowledge of f(r). The range 1≥ a ≥ 2 of aspect ratios (a = d_T/d_p is then analysed specifically. For this range, the distribution of spherical particles has been characterized theoretically (Govindarao et al., 1992) and a simple expression allows the evaluation of ?(r). The use of this expression for actual catalyst particles, imperfect spheres showing a distribution of sizes, in finally analyzed.     

Effect of Glass Addition on the Microwave Dielectric Properties of CaMgSi2O6 Ceramics

CaMgSi₂O₆ (CMS) ceramics prepared by the solid-state ceramic route have a sintering temperature of 1300°C/2 h. The sintering temperature of CMS was reduced below the melting point of Ag using low-melting LBS and LMZBS glasses. In the case of CMS+15 wt% LMZBS sintered at 900°C/2 h, the dielectric properties obtained were ɛ_r=8.2, Q_u×f=32,000 GHz (10.15 GHz), and τ_f=–48 ppm/°C. The CMS+15 wt% LBS composite, sintered at 925°C/2 h, showed ɛ_r=8, Q_u×f=15,000 GHz (10.17 GHz), and τ_f=–49 ppm/°C. The chemical compatibility of Ag with the ceramic–glass composites was also investigated for low-temperature co-fired ceramic applications.     

Investigation of phase composition and microwave dielectric properties of MgO‐Ta2O5 ceramics with ultrahigh Qf value

Four MgO‐Ta₂O₅ ceramics with the MgO/Ta₂O₅ mole ratio x = 1, 2, 3, and 4 were prepared by traditional solid‐state reaction method, and the influence of x on the phase composition, microstructure, and dielectric properties (the dielectric constant ε_r, the temperature coefficient of resonant frequency τ_f and the quality factor Qf) of the materials was investigated using XRD, SEM, etc. The results indicated that the ceramics were composed of two crystalline phases MgTa₂O₆ and Mg₄Ta₂O₉ in the composition range studied, and that the dielectric properties ln ε, 1/Qf, and τ_f changed proportionally to the fraction of main crystal phases, which meet perfectly with the mixing model proposed in this study. It is obvious that the proportion of the two crystal phases could be precisely controlled by x, and thereby, the dielectric properties can be conveniently and precisely tailored. Our research provided a new microwave dielectric ceramic with the composition of 2MgO‐Ta₂O₅, which has an ultrahigh Qf value (211 000 GHz), low dielectric constant ε_r (19.9), and near zero temperature coefficient of resonant frequency τ_f (8 ppm/°C).     

Mathematical modeling and simulation studies of scale-down fermentation systems

In this study, a scale-down approach has been used for the simulation of the imperfect mixing on the growth processes by considering several configurations of continuous stirred tank reactor (CSTR, aerated) and plug flow tubular reactor (PFTR, not aerated). The steady-state concentrations of biomass and enzyme in a continuous culture were calculated as a function of dilution rate using modified Monod growth kinetics. A mathematical model for each combination of two bioreactors was developed to account for growth, substrate utilization (oxygen and glucose) and enzyme synthesis and decay. The model was then used to investigate biomass production and enzyme expression in relation to the volumetric fraction U_f = V_PFTR /(V_CSTR + V_PFTR ) and the recirculation ratio R = f_r/(f + f_r) of the fermentation system. These two mixing parameters were found to be significant factors in the biomass and enzyme production from the fermentation system. This model was also compared with some of the existing models.     

Lattice structure and microwave dielectric properties of La[Al1−x(Mg0.5Ti0.5)x]O3 (x = 0-0.2)-based ceramics

La[Al_1−x(Mg_0.5Ti_0.5)_x]O₃ (LAMT, x = 0-0.2) ceramics were synthesized by the conventional solid-state reaction method and formed a solid solution. The pure solid solutions were recorded by X-ray diffraction (XRD) in every range. Relative permittivity (ε_r) and structural stability were greatly affected because the Al³⁺ site was replaced by [Mg_0.5Ti_0.5]³⁺. The total ionic polarizability gradually increased with x, and ε_r gradually increased. The trend of τ_f is due to the change in structural stability. The variation in Q × f value increased firstly and then decreased due to the change in the symmetric stretching mode of Al/MgTi–O. The optimum microwave dielectric properties of LAMT were obtained at x of 0.1 after sintering at 1650°C for 5 hours, and ε_r = 24.9, Q × f = 79 956 GHz, and τ_f = −33 ppm/°C. The CaTiO₃ have a large positive τ_f (+800 ppm/°C), thus, the τ_f achieved near zero when CaTiO₃ and LAMT (x = 0.1) ceramics were mixed with a certain molar mass, and the optimum microwave dielectric properties of 0.65CaTiO₃–0.35LaAl_0.9(Mg_0.5Ti_0.5)_0.1O₃ were as follows: ε_r = 44.6, Q × f = 32 057 GHz, and τ_f = +2 ppm/°C.     

Computer calculation of heat capacity of natural gases over a wide range of pressure and temperature

This paper presents a method whereby specific heats or heat capacities of natural gases, both sweet and sour, at elevated pressures and temperatures may be made suitable to modern day machine calculation. The method involves developing (1) a correlation for ideal isobaric heat capacity as a function of gas gravity and pseudo reduced temperature over the temperature range of 300 to 1500 K and (2) a mathematical equation for the isobaric heat capacity departure based on accepted thermodynamic principles applied to an equation of state that adequately describes the behavior of gases to which the Standing and Katz Z factor correlation applies. The heat capacity departure equation is applicable over the range of 0.2 ≤ P_r ≤ 15 and 1.05 ≤ T_r ≤ 3. The significance of the method presented here lies in its utility and adaptability to computer applications.     

Update for combustion properties of wood components

The combustion properties of various biomass and wood materials from various references and from our laboratory were reanalysed. The net heat of combustion for cellulosic materials was found to be 13.23 kJ/g times the ratio of stoichiometric oxygen mass to fuel mass, r_o, regardless of the material composition. Bomb calorimeter data for original, charred and volatilized material components provide gross heating values, while elemental analysis of the materials for carbon, hydrogen, oxygen and ash provide direct evaluation for r_o. We corrected these data as provided in various references by converting gross heating values to lower heating values and converting elemental compositions, char fractions and r_o to a moisture‐free and ash‐free basis. Some existing formulae were found to disagree with data from vegetation, charred wood with high ash content, and with volatiles from cellulose treated with the fire retardant NaOH. We also established various functional correlations of r_o with elemental compositions, or volatization fractions of untreated and treated materials, or material fractions for cellulose, lignin and extractives, or volatile fractions for tar, combustible gases and inert gases in pure nitrogen carrier gas. An interesting predictive result provides nearly constant heat of combustion while the volatile tar fraction is decreasing and combustible and inert gas fractions are increasing with time during the charring of Douglas‐fir wood. Published in 2002 John Wiley & Sons, Ltd.     

Multiple effects of operating variables on heat transfer in three-phase slurry bubble columns

Characteristics of heat transfer were investigated in pressurized slurry bubble column reactors whose diameter was either 0.051, 0.076, 0.102 or 0.152 m (ID) and 1.5 m in height, respectively. Effects of gas velocity (U _G ), solid contents (S _C ), pressure (P), liquid viscosity (μ _L ) and column diameter (D) on the heat transfer coefficient (h) between the immersed vertical heater and the column were determined. Multiple effects such as UG and D, P and D, μ _L and D, and S _C and D on the value of heat transfer coefficient were discussed. Temperature fluctuations were also measured and analyzed by adapting chaos theory, which was used to explain the effects of operating variables on the heat transfer in the column. The heat transfer coefficient increased with increasing gas velocity, pressure or solid content in the slurry phase, but decreased with increasing liquid viscosity or column diameter. The decrease trend of h with increasing column diameter was somewhat sensitive when the gas velocity was relatively high (U _G ⩾12 cm/s). The effects of column diameter on the h value became almost linear when the operating pressure (P=4−10 kg _f /cm²), liquid viscosity (μ _L =20−38 mPa·s) or solid content in the slurry phase (S _C =10−20 wt%) was relatively high and gas velocity was relatively low, within these experimental conditions. The heat transfer coefficient was well correlated in terms of dimensionless groups as well as operating variables.     

Castor oil and PEG‐based shape memory polyurethane films for biomedical applications

A series of polyurethane film were prepared from poly(ethylene glycol) with different molecular weight (PEG 1500, 3000, and 8000) and castor oil by one‐shot bulk polymerization method. Hexamethylene diisocyanate and 1,4‐buthane diol were used as diisocyanate and chain extender, respectively. In order to characterize the samples, their density, swelling ratio, water contact angle, surface free energy, gel content, thermal, and viscoelastic properties were determined. The effect of the soft segment length (SSL) and hard segment content (HSC) of all polyurethane films on their shape memory behavior such as shape fixity (R_f) and shape recovery (R_r) rates were investigated by bending test. Direct contact and MTT tests were used for assessment of cell adhesion and proliferation. The relatively high R_f and R_r values were obtained for the samples programmed at high temperature difference. R_f increased with decreasing HSC. On the other hand, R_r tended to decrease with increasing SSL. After evaluating experimental data by a nonlinear equation, it was found that HSC is more effective parameter on shape memory property than SSL. The gel content, swelling ratio, and water contact angle of the samples were dependent on both SSL and HSC in their structures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40590.     

Microstructural and Microwave Dielectric Properties of Bi12GeO20 and Bi2O3‐Deficient Bi12GeO20 Ceramics

Bi₁₂GeO₂₀ ceramics sintered at 800°C had dense microstructures, with an average grain size of 1.5 μm, a relative permittivity (ε_r) of 36.97, temperature coefficient of resonance frequency (τ_f) of ?32.803 ppm/°C, and quality factor (Q × f) of 3137 GHz. The Bi_12‐xGeO_20‐1.5x ceramics were well sintered at both 800°C and 825°C, with average grain sizes exceeding 100 μm for x ≤ 1.0. However, the grain size decreased for x > 1.0 because of the Bi₄Ge₃O₁₂ secondary phase that formed at the grain boundaries. Bi_12‐xGeO_20‐1.5x (x ≤ 1.0) ceramics showed increased Q × f values of >10 000 GHz, although the ε_r and τ_f values were similar to those of Bi₁₂GeO₂₀ ceramics. The increased Q × f value resulted from the increased grain size. In particular, the Bi_11.6GeO_19.4 ceramic sintered at 825°C for 3 h showed good microwave dielectric properties of ε_r = 37.81, τ_f = ?33.839 ppm/°C, and Q × f = 14 455 GHz.     

Investigations on the Droplet Entrainment in a Forced Circulation Flash Evaporator

This contribution presents results from entrainment measurements in a forced circulation flash evaporator which was designed to systematically investigate the droplet entrainment under real evaporating conditions. Operating pressures in a range of 100 to 800 mbar(a) and temperature differences between 5 and 55 K were conducted. Gas load factors up to f_G = 4.0 Pa^0.5 were achieved with glycerol-water and water as evaporating liquids. A conductivity measurement was used to determine the absolute entrained liquid and entrainment ratios. The results show an exponential behavior between entrainment, gas load factor, and heat flux due to superimposing effects. Investigation on the pressure drop across the orifice plate showed no influence for operation at gas load factors of f_G < 2.5 Pa^0.5.     

Microwave dielectric properties of SnO‐SnF2‐P2O5 glass and its composite with alumina for ULTCC applications

Ultralow‐temperature sinterable alumina‐45SnF₂:25SnO:30P₂O₅ glass (Al₂O₃‐SSP glass) composite has been developed for microelectronic applications. The 45SnF₂:25SnO:30P₂O₅ glass prepared by melt quenching from 450°C has a low T_g of about 93°C. The SSP glass has ε_r and tanδ of 20 and 0.007, respectively, at 1 MHz. In the microwave frequency range, it has ε_r=16 and Q_u × f=990 GHz with τ_f=?290 ppm/°C at 6.2 GHz with coefficient of thermal expansion (CTE) value of 17.8 ppm/°C. A 30 wt.% Al₂O₃ ‐ 70 wt.% SSP composite was prepared by sintering at different temperatures from 150°C to 400°C. The crystalline phases and dielectric properties vary with sintering temperature. The alumina‐SSP composite sintered at 200°C has ε_r=5.41 with a tanδ of 0.01 (1 MHz) and at microwave frequencies it has ε_r=5.20 at 11 GHz with Q_u × f=5500 GHz with temperature coefficient of resonant frequency (τ_f)=?18 ppm/°C. The CTE and room‐temperature thermal conductivity of the composite sintered at 200°C are 8.7 ppm/°C and 0.47 W/m/K, respectively. The new composite has a low sintering temperature and is a possible candidate for ultralow‐temperature cofired ceramics applications.     

Fixed bed catalytic reactor modelling—the radial heat transfer problem

An interpretation of the state‐of‐the‐art in modelling radial heat transfer in fixed bed catalytic reactors is presented. The persistence of the classical k_r–h_w model is discussed, problems with typical approaches to obtaining and analysing experimental heat transfer data to get k_r and h_w are explained, current correlations for k_r are evaluated and the contentious history of h_w is elaborated. A brief discussion of alternatives to the k_r–h_w approach and their pros and cons is attempted, and the review is concluded by a look at computational fluid dynamics (CFD) in fixed bed radial heat transfer modelling. © 2011 Canadian Society for Chemical Engineering     

Polymerization of acrylic bone cement investigated by differential scanning calorimetry: Effects of heating rate and TCP content

The polymerization reaction of a bone cement (standard Surgical Simplex-P Radiopaque) upon heating has been investigated by differential scanning calorimetry (DSC). The effects of the addition of tricalcium phosphate (TCP) on the rate and the heat of polymerization during DSC heating were evaluated. The rate and polymerization heat (ΔH) were characterized by the initial curing temperature (T_i), peak temperature (T_p), completing curing temperature (T_f), the curing range (ΔT = T_f ? T_i) and the area of the DSC exotherm. It was found that T_i, T_p, T_f, ΔT, and ΔH all increase with increasing heating rate. Increasing TCP content also induced increases in T_i, T_p, T_f, ΔT, and ΔH. From the kinetic analysis, the polymerization of acrylic bone cement was found to be a first order reaction. The effects of heating rate and TCP contents on the rate and the heat of polymerization could be explained based on the frequency factor and the activation energy extracted from the kinetic analysis. Increases in both heating rate and TCP content depressed the frequency factor and the activation energy.     

Principal element design of garnets to access structure stability and excellent microwave dielectric properties

Guided by the tolerance factor and average electronegativity difference, two stable garnets with compositions Ca₃BTiGe₃O₁₂ (B = Mg, Zn) were designed, synthesized followed by structural, and dielectric characterization. The phase purity and structural characteristics were analyzed using X-ray, Rietveld refinement, and microstructural analysis through scanning electron microscopy. A cubic structure with an Ia-3d space group was confirmed for synthesized compositions. A combination of microwave dielectric properties for both garnets suggested that Ca₃MgTiGe₃O₁₂ ceramic possessed a much higher quality factor (Q × f) ∼ 84 000 ± 3000 GHz coupled by a higher dielectric constant (ε_r) ∼ 12.97 ± 0.03, and a smaller temperature coefficient of resonance frequency (τ_f) ∼ −29.4 ± 1.5 ppm/°C compared to its Zn counterpart (Q × f ∼ 45 000 ± 2000 GHz, ε_r ∼ 12.84 ± 0.03, and τ_f ∼ −33.19 ± 1.6 ppm/°C). Such differences in dielectric performances were further explored utilizing packing fraction, ion polarizability, bond valence, Raman, and infrared spectrum to understand structure–property relationship.     

Radial gas mixing characteristics in a downer reactor

In a downer reactor (0.1 m-I.D.x3.5 m-high), the effects of gas velocity (1.6-4.5 m/s), solids circulation rate (0–40kg/m²s) and particle size (84, 164 Μm) on the gas mixing coefficient have been determined. The radial dispersion coefficient(D _r ) decreases and the radial Peclet number (Pe_r) increases as gas velocity increases. At lower gas velocities, D_r in the bed of particles is lower than that of gas flow only, but the reverse trend is observed at higher gas velocities. Gas mixing in the reactor of smaller particle size varies significantly with gas velocity, whereas gas mixing varies smoothly in the reactor of larger particle size. At lower gas velocities, D_r increases with increasing solids circulation rate (G_s), however, D_r decreases with increasing G_s at higher gas velocities. Based on the obtained D_r values, the downer reactor is found to be a good gas-solids contacting reactor having good radial gas mixing.     

Comparative study on foaming process of thermoplastic polyester and polyether polyurethane with supercritical CO2 as foaming agent

ABSTRACT

The aim of this study was the comparison of beads foaming process and synergistic effect of foaming process parameters on melting crystalline characteristics between thermoplastic polyester and polyether polyurethane(TPU) via batch process using supercritical CO₂(scCO₂) as blowing agent. Method was based on the generation of expandable TPU foam beads (ETPU) prepared by self-designed autoclave foaming apparatus. The surface morphology, cell structure, and crystalline melting characteristics of the ETPU depending on the processing parameters, such as saturation pressure (P_f), saturation temperature (T_f), and saturation time (t_f), were investigated. Results demonstrated both ETPU exhibited fine closed cell morphology with polygons structure and would induce the disappearance of multiple endothermic peaks during the foam process. As any of those three process parameters increased, the HS content, high crystalline melting and E_r were improved, while with regard to cell structure, P_f demonstrated the opposite effect compared with T_f and t_f. Comparing with polyether TPU, polyester TPU possess a larger cell density and a clear bimodal cell structure could be found under certain condition, while beads foaming process had a greater impact on polyether TPU, which had a low density and the appropriate t_f is 2h.     

Kinetics for copolymerization of methyl methacrylate with N‐cyclohexylmaleimide

The kinetics for the radical copolymerization of methyl methacrylate (MMA) with N‐cyclohexylmaleimide (NCMI) was investigated. The initial copolymerization rate R_p is proportional to the initiator concentration to the power of 0.54. The apparent activation energy of the overall copolymerization was measured to be 69.0 kJ/mol. The monomer reactivity ratios were determined to be r_NCMI = 0.42 and r_MMA = 1.63. R_p reduces slightly, and the molecular weight of the resultant copolymer decreases with increasing the concentration of the chain transfer agent N‐dodecanethiol (RSH). The more the transfer agent, the narrower the molecular weight distribution of the resulting copolymer. The following chain‐transfer constant of RSH for the copolymerization of MMA with NCMI in benzene at 50°C was obtained: C_s = 0.23. The glass transition temperature (T_g) of the copolymer increases with increasing f_NCMI, which indicates that adding NCMI can improve the heat resistance of Plexiglas. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1293–1297, 1999     

Microwave dielectric properties of (0.75ZnAl2O4–0.25TiO2)–MgTiO3 ceramics prepared using digital light processing technology

ZTM ceramics comprising of 0.75ZnAl₂O₄–0.25TiO₂ and MgTiO₃ at a ratio of 90:10 wt.% are widely used in the field of communication as filters and resonators owing to their excellent microwave dielectric properties. However, the development of such dielectrics with complex structures, as required by microwave devices, is difficult using traditional fabrication methods. In this study, ZTM microwave dielectric ceramics were prepared using the digital light processing (DLP) technology. The influence of the sintering temperature on the phase composition, microstructure, and microwave dielectric properties of ZTM ceramics was investigated. Results showed that with an increase in the sintering temperature, the dielectric constant (ε_r) and quality factor (Q × f) of ZTM ceramics initially increased owing to the increase in the density and diffusion of ions. However, when the sintering temperature was excessively high, the abnormal growth of crystal grains and micropores led to a decrease in ε_r and Q × f. The ZTM ceramics sintered at 1450°C exhibited the optimum microwave dielectric properties (ε_r = 12.99, Q × f = 69 245 GHz, τ_f = −9.50 ppm/°C) owing to the uniform microstructure and a high relative density of 95.02%. These results indicate that DLP is a promising method for preparing high-performance microwave dielectric ceramics with complex structures.