Short Induction Period Research Articles

Isothermal thermo-analytical study and decomposition kinetics of non-activated and mechanically activated indium tin oxide (ITO) scrap powders treated by alkaline solution

Isothermal decomposition process of chemically transforming indium tin oxide (ITO) powders into indium (III) hydroxide powders was investigated. Two types of powders were analyzed, i.e., non-activated and mechanically activated. It has been found that in the case of activated sample, shorter induction periods appear, which permits growth of smaller crystals, while in the case of non-activated sample, long induction periods appear, characterized by the growth of larger crystals. DAEM approach has shown that decomposition processes of non-activated and mechanically activated samples can be described by contracting volume model with a linear combination of two different density distribution functions of apparent activation energies (Ea), and with first-order model, with a single symmetrical density distribution function of Ea, respectively. It was established that specific characteristics of particles not only affect the mechanism of decomposition processes, but also have the significant impact on thermodynamic properties.

Preparation of super-microporous WO3–SiO2 olefin metathesis catalysts by the aerosol-assisted sol–gel process

Highly effective tungsten oxide-based catalysts are prepared by a one-pot aerosol-assisted sol–gel method. Their catalytic performances are evaluated in the cross-metathesis of ethene and trans-2-butene for the production of propene. The catalysts are comprehensively characterized by N2-physisorption, ICP-OES, SEM, TEM, XRD, UV–Vis spectroscopy, NH3-TPD, NH3-chemisorption, XPS, and TPR. Benefiting from the advantage of the aerosol process, the new WO3–SiO2 catalysts display outstanding textural properties, with a high specific surface area (500–600 m2 g−1) solely generated by calibrated super-micropores of about 2 nm. The catalyst particles are perfectly spherical in shape and feature high W dispersion and appropriate reducibility and surface acidity. As compared to reference catalysts prepared by traditional impregnation on a commercial silica support, the aerosol catalysts exhibit higher metathesis activity and shorter induction period. Conversion and selectivity are shown to increase with WO3 loading (up to 15 wt.%). Calcination temperature (450–850 °C) is identified as an essential parameter impacting significantly the texture, the surface acidity, and therefore also the catalytic activity.

Achievement of favorable uniform crystal size distribution of alpha-lactose monohydrate (α-LM) through swift cooling process

The impact of initial concentration on size, morphology and nucleation kinetics of alpha-lactose monohydrate (α-LM) was investigated by adopting novel swift cooling crystallization process. The supersaturation dependent induction period estimated from the experiment were used to derive the nucleation kinetics based on the classical nucleation theory. Size and morphology of the nucleated crystals were analyzed with different initial concentrations. The lower concentration (S=4.51–6.99) yields individual crystals with needle and pyramidal morphologies and the higher concentration (S=6.99–8.14) yields aggregated crystals with fan-like morphology. The nucleation kinetics study reveals that, the transition in interfacial energy leads to the nucleation of aggregated crystals and the rate of aggregation increases with increase in concentration. Characterization analysis of the individual and aggregated crystals infers their crystalline phase purity and the form of crystallization. This method enables to produce α-LM crystals with a shorter induction period and the interfacial energy play an important role in producing good quality crystals suitable for dairy and dry powder inhaler applications at lower concentration levels (i.e., S=4.51–6.99).

Viral capsids: kinetics of assembly under transient conditions and kinetics of disassembly.

The available kinetic models of assembly of viral protein capsids are focused primarily on the situations in vitro where the amount of protein is fixed. In vivo, however, the viral protein synthesis and capsid assembly occur under transient conditions in parallel with viral genome replication. Herein, a kinetic model describing the latter case of capsid assembly is proposed with emphasis on the period corresponding to the initial stage of viral genome replication. The analysis is aimed at small icosahedral capsids. With biologically reasonable values of model parameters, the model predicts rapid exponential growth of the populations of monomers and fully assembled capsids during the transient period of genome replication. Under the subsequent steady-state conditions with respect to replication, the monomer population is predicted to be nearly constant while the number of fully assembled capsids increases linearly. The kinetics of capsid disassembly, described briefly as well under conditions of negligible monomer concentration, exhibit a short induction period when the number of proteins in a capsid is only slightly smaller than in the beginning, followed by more rapid protein detachment. According to calculations, the latter kinetics may strongly depend on protein degradation.

Reaction kinetics of dolomite and portlandite

The reactions of dolomite with portlandite have been studied at well-spaced temperatures between 20°C and 85°C using XRD Rietveld, TG and SEM methods. The results show quantitatively the faster rates of reaction at higher temperature. Isothermal reaction has, at most, a short induction period after which the degree of reaction is linear with time. An exponential equation is presented to predict the initial rate of reaction as a function of temperature. The microstructure shows that large equant calcite crystals, up to 30μm, develop on the rhomboid cleavage surfaces of dolomite. Pressed pellets of dolomite develop calcite at both exterior surfaces and in the interior, where calcite develops as a secondary phase but is not morphologically well-formed crystals. Pellets remain coherent in the course of reaction. The porous pellets have much unfilled space inside and often exhibit portlandite agglomerates with development of Hadley grain structures at the sites of former dolomite crystals, especially when reacted at lower temperatures. The reaction is not topotactic but requires dissolution, transport, nucleation and growth. Transport occurs often over considerable distance relative to the sizes of crystals.

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

Iron-mediated AGET ATRP of styrene and methyl methacrylate using ascorbic acid sodium salt as reducing agent

Atom transfer radical polymerization of styrene (St) and methyl methacrylate (MMA) in bulk and in different solvents using activators generated by electron transfer (AGET ATRP) were investigated in the presence of a limited amount of air using FeCl3·6H2O as the catalyst, ascorbic acid sodium salt (AsAc-Na) as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide (TBABr) as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET ATRP of St, while referring to AGET ATRP of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene: 1) shortening the induction period, 2) enhancing the polymerization rate and 3) having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.

Comparative Analysis of the Influence of Sodium and Potassium Silicate Solutions on the Kinetics and Products of Slag Activation

Abstract This paper primarily explores the influence of the alkali cation (Na or K) on the reaction kinetics, product formation, gel structure, and mechanical properties of alkali activated slag systems. For the same activator Ms, i.e., molar SiO2–M2O ratio (M = Na or K), a shorter induction period, a larger acceleration peak, and consequently, a higher amount of total heat release under isothermal conditions is observed for the K-silicate activated slag pastes. The early-age compressive strengths in these systems roughly relate to the heat release response. The later-age (7 days and beyond) compressive strengths are observed to be higher for the Na-silicate activated systems, which is corroborated by: (1) higher amounts of C–(A)–S–H gel in this system indicated by a thermal analysis-based approximate quantification method, and (2) higher combined intensities of Q1 and Q2 structures that point to increased degrees of reaction, and lower amounts of unreacted slag obtained from 29Si magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The NMR spectra also show evidences of Al-substituted C–S–H gel, with a higher amount of substitution when Na-silicates are used.

Effects of ultrasonic radiation on induction period and nucleation kinetics of sodium sulfate

The effects of ultrasound on crystal nucleation and particle size distribution of sodium sulfate were investigated via determining the induction period and particle size. Crystal nucleation parameters and equations for primary nucleation were calculated. The experimental results show that the induction time decreases under the ultrasound irradiation, therefore, we can get a shorter induction period at a higher supersaturation level. Based on these observations, the growth mechanism of sodium sulfate is continuous growth because the value of the surface entropy factor f is smaller than 3. The induction period was observed shorter and particle size was smaller when the ultrasonic radiation time increased. Crystal growth improved with the longer crystallization time.

Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation of N-Acetyl Homocysteine Thiolactone by Acidified Bromate and Aqueous Bromine

N-acetyl homocysteine thiolactone (NAHT), medically known as citiolone, can be used as a mucolytic agent and for the treatment of certain hepatic disorders. We have studied the kinetics and mechanisms of its oxidation by acidic bromate and aqueous bromine. In acidic bromate conditions the reaction is characterized by a very short induction period followed by a sudden and rapid formation of bromine and N-acetyl homocysteine sulfonic acid. The stoichiometry of the bromate-NAHT reaction was deduced to be: BrO3(-) + H2O + CH3CONHCHCH2CH2SCO → CH3CONHCHCH2CH2(SO3H)COOH + Br(-) (S1) while in excess bromate it was deduced to be: 6BrO3(-) + 5CH3CONHCHCH2CH2SCO + 6H(+) → 3Br2 + 5CH3CONHCHCH2CH2(SO3H)COOH + 2H2O (S2). For the reaction of NAHT with bromine, a 3:1 stoichiometric ratio of bromine to NAHT was obtained: 3Br2 + CH3CONHCHCH2CH2SCO + 4H2O → 6Br(-) + CH3CONHCHCH2CH2(SO3H)COOH + 6H(+) (S3). Oxidation occurred only on the sulfur center where it was oxidized to the sulfonic acid. No sulfate formation was observed. The mechanism involved an initial oxidation to a relatively stable sulfoxide without ring-opening. Further oxidation of the sulfoxide involved two pathways: one which involved intermediate formation of an unstable sulfone and the other involves ring-opening coupled with oxidation through to the sulfonic acid. There was oligooscillatory production of aqueous bromine. Bromide produced in S1 reacts with excess bromate to produce aqueous bromine. The special stability associated with the sulfoxide allowed it to coexist with aqueous bromine since its further oxidation to the sulfone was not as facile. The direct reaction of aqueous bromine with NAHT was fast with an estimated lower limit bimolecular rate constant of 2.94 ± 0.03 × 10(2) M(-1) s(-1).

Influence of Injected Projectiles on the Induction Period of Crystallization Fouling

Projectiles of various shapes and hardness are increasingly used in process industries to mitigate fouling in tubular heat exchangers. It is a common practice to inject the projectiles at the early stage of fouling, though laboratory results are quite scarce in the open literature to assess whether this is an appropriate operating procedure. The present work aims at investigating the influence of injected projectiles on the induction period of CaSO4 crystallization fouling. Fouling experiments have been performed in a plain heated tube. The projectiles were of spherical shape with diameter of 20.2 mm, that is, 1% bigger than the inner diameter of the heated tube, and were injected at various intervals. It has been observed that overall the attempted projectile reduced the induction period and thus expedited the fouling process. The asymptotic behavior of crystallization fouling is also approached more quickly but much less so than that of no injection. The induction period increased linearly with the flow velocity in case of no injection, while it was independent of the flow velocity when the projectile was injected as long as the injection rate was kept constant. Increasing the injection rate decreased the induction period and started the fouling process earlier. This is because the propulsion of projectiles induces air bubbles into the heat exchanger tube, which would in turn promote fouling to occur more quickly, and thus shorter induction periods are expected. Therefore, it is highly recommended to inject projectiles only after the induction period, to make use of the fouling-free operation during the induction period.

Crystallization kinetics of Sn-MFI molecular sieve formation by dry gel conversion method

The conversion of amorphous stannosilicate dry gel into crystalline molecular sieve with MFI structure (Sn-MFI) was achieved by dry gel conversion (DGC) method at 413, 443 and 473K. For comparison purpose, Sn-MFI molecular sieve with similar SiO2/SnO2 mole ratio was also obtained by hydrothermal crystallization route. Crystallization curves were established by conducting time dependant studies on progressive crystallization processes for both the systems. The values of activation energy of nucleation (En), activation energy of crystallization (Ec), and their pre-exponential factors (lnAn, lnAc respectively) were calculated from Arrhenius plots. Compared to the hydrothermal method, shorter induction period was observed when DGC method was employed. Both the En (49.70kJ/mol) and Ec (52.82kJ/mol) for DGC method were found to be lower than that of the En (55.70kJ/mol) and Ec (60.23kJ/mol) for hydrothermal method. The kinetics parameters viz. K and q were derived from kinetic expressions and DGC method showed higher value of K and lower value of q compared to hydrothermal crystallization method at identical temperature. Various DGC method parameters such as water content at the bottom of autoclave and SiO2/SnO2 mole ratio have shown the influence on the kinetics of crystallization of Sn-MFI.

Anesthetic regimen for cardiac function evaluation by echocardiography in mice: comparison between ketamine, etomidate and isoflurane versus conscious state

Mice with genetic alterations are used in heart research for the extrapolation of human diseases. Echocardiography is an essential tool for evaluating cardiac and hemodynamic functions in small animals. The purpose of this study was to compare the effect of different anesthetic regimens and the conscious state on the evaluation of cardiac function by echocardiography. Mice were examined in the conscious state after three days of training, and then for a 7 min period after a single intraperitoneal injection of ketamine at 100 mg/kg, etomidate at 10, 20 or 30 mg/kg, or after inhalation of isoflurane at 1.5% with or without a short period of induction with isoflurane 3%. Intra- and inter-observer variabilities were assessed. The operator's comfort was also assessed. Heart rate, left ventricular end diastolic diameter, fraction shortening and cardiac output were measured using echocardiography. Ketamine at 5 and 7 min after induction and isoflurane at 3, 5 and 7 min after induction provided good anesthetic conditions and a quick awakening time, and did not influence cardiac performance, whereas the conscious state was associated with a non-physiological sympathetic activation and other anesthetic drugs induced a significant decrease in heart rate. Etomidate 10 mg/kg and 20 mg/kg were not enough to provide adequate anesthesia. Etomidate 30 mg/kg induced a good anesthetic condition but influenced cardiac performance and had a long awakening time. Our results indicate that ketamine and isoflurane with a short induction period are better anesthetic drugs than isoflurane without induction or etomidate for evaluating cardiac function in healthy mice.

Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives

The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022–0.088mmol/g). HAp (2–8wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding.

RAFT‐mediated emulsion polymerization of styrene using brush copolymer as surfactant macro‐RAFT agent: Effect of the brush copolymer sequence and chemical composition

AbstractThe nonionic amphiphilic brush polymers such as poly[poly(ethylene oxide) methyl ether vinylphenyl‐co‐styrene] trithiocarbonate [P(mPEGV‐co‐St)‐TTC] and poly[poly(ethylene oxide) methyl ether vinylphenyl‐b‐styrene‐b‐poly(ethylene oxide) methyl ether vinylphenyl] trithiocarbonate [P(mPEGV‐b‐St‐b‐mPEGV)‐TTC] with different monomer sequence and chemical composition are synthesized and their application as macro‐RAFT agent in the emulsion RAFT polymerization of styrene is explored. It is found that the monomer sequence in the brush polymers exerts great influence on the emulsion RAFT polymerization kinetics, and the fast polymerization with short induction period in the presence of P(mPEGV‐co‐St)‐TTC is demonstrated. Besides, the chemical composition in the brush polymer macro‐RAFT agent effect on the emulsion RAFT polymerization is investigated, and the macro‐RAFT agent with high percent of the hydrophobic PS segment leads to fast and well controlled polymerization. The growth of triblock copolymer colloids in the emulsion polymerization is checked, and it reveals that the colloidal morphology is ascribed to the hydrophobic PS block extension, and the P(mPEGV‐co‐St) block almost have no influence just on the size of the colloids. This may be the first example to study the monomer sequence and the chemical composition in the macro‐RAFT agent on emulsion RAFT polymerization, and will be useful to reveal the block copolymer particle growth. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Thermal oxidation kinetics of additive free polyamide 6-6

Thermal aging of an additive free PA 6-6 has been elucidated at 90, 100, 120, 140, 150 and 160 °C in air-ventiled ovens by Fourier transform infrared spectrophotometry, viscosimetry in molten state and uniaxial tensile testing. Oxidation of methylene groups starts after a considerably shorter induction period but reaches a lower maximal rate than in additive free PE. Cleavage of C–N bonds constitutes the main source of chain scissions. It leads to the formation of aldehyde chain-ends and a catastrophic decrease in molar mass. Embrittlement occurs at a very low conversion ratio of the oxidation process, in particular when the concentration of aldehyde chain-ends reaches a critical value of [PH=O]F ≈ 5.6 10−3 mol l−1, corresponding to a critical value of the number average molar mass of MnF ≈ 17 kg mol−1. At this stage, the entanglement network in the amorphous phase is deeply damaged.A non-empirical kinetic model has been derived from the oxidation mechanistic scheme previously established for PE, but improved by adding elementary reactions specific to polyamides such as the rapid decomposition of unstable hydroxylated amide groups. This model describes satisfyingly the main features of the thermal oxidation kinetics of PA 6-6, but also of other types of aliphatic polyamides studied previously in the literature such as: PA 6, PA 12 and PA 4-6, as long as it is not controlled by oxygen diffusion. At the same time, it confirms the existence of an universal character for the thermal oxidation kinetics of aliphatic polyamides whatever their origin, i.e. their initial molar mass, crystallinity ratio, concentration of impurities, structural irregularities, etc.

Conjugate Addition versus Cycloaddition/Condensation of Nitro Compounds in Water: Selectivity, Acid–Base Catalysis, and Induction Period

Nitroacetates and nitroacetamides react in water as in chloroform with electron-deficient dipolarophiles to give condensation or conjugate addition products under base catalysis. In general, high selectivity towards condensation is observed in water, with shorter induction periods than in chloroform. In water, condensations slowly occur even without base; kinetic profiles evidence the catalytic effect of the base, which should be related to the conversion into the tautomer nitronic acid. Condensations in water provide convenient access to isoxazole derivatives bearing various functional groups including ammonium, carboxy, and carboxyamide.

Rheology and Crystallization of Long-Chain Branched Poly(l-lactide)s with Controlled Branch Length

A series of long-chain branched poly(l-lactide)s (LCB-PLAs) with controlled branch length were prepared by a simple and efficient method through a combination of ring-opening polymerization (ROP) of l-lactide and a coupling reaction between the terminal OH groups of the PLA prepolymers and the NCO groups of HDI. The influences of reaction conditions on the synthesis of the LCB-PLAs were investigated, and the structures of the resultant LCB-PLAs were characterized by 1H NMR spectroscopy and SEC-MALLS. By adjusting the degree of polymerization and the composition of the prepolymers, LCB-PLAs with different branch densities and molecular weights between branch points were obtained. The effect of macromolecular chain branching on the rheology and crystallization of PLA was also investigated. The LCB structure contributed to the enhancement of the zero-shear viscosity, complex viscosity, storage modulus, melt strength, and strain hardening under elongational flow. Thermal behavior indicated that the branch structure resulted in a short nucleation induction period and more rapid crystallization, which can be a guarantee of high-strength foams.

Photoinitiated RAFT polymerization of vinyl acetate

AbstractA photoinitiation process was investigated to develop a rapid and well‐controlled RAFT polymerization method applied to vinyl acetate (VAc) using methyl (ethoxycarbonothioyl)sulfanyl acetate (MESA) and bis(2,4,6‐trimethylbenzoyl)phenylphosphine oxide as the RAFT agent and photoinitiator, respectively. MESA was selected as the photochemically inert RAFT agent to minimize photolysis of the thiocarbonylthio groups during polymerization. Poly(vinyl acetate) with a prespecified well‐controlled molecular weight (MW) and a narrow MW distribution was successfully synthesized. The polymerization reaction proceeded as a living polymerization and was remarkably rapid compared with approaches that use thermally initiated processes with a very short induction period. A detailed kinetic study of the mechanism underlying the polymerization reaction, however, revealed that the chain ends containing xanthate moieties were not perfectly stable upon UV‐irradiation, and they generated radicals via homolytic cleavage. This reaction appeared to proceed by a combination of a degenerative transfer RAFT mechanism and a dissociation‐combination mechanism. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Modelling fouling induction periods

A fouling process is often preceded by an induction period in which no significant fouling is observed. In this paper, a simple lumped parameter model based on fractional surface coverage θ has been developed to correlate experimental data in the induction period. The model assumes that active foulant species stick to the surface and gradually cover it, the rate of change of surface coverage d θ/d t being proportional to the fractional free surface (1 − θ). It is further assumed that the foulant already on the surface acts as a seed, attracting more foulant in a micro-growth manner such that the growth rate is first order in θ with a rate constant k 1. Adopting the concept of removal mechanism similar to that used in adsorption science, the removal rate of the coverage is set to be proportional to the coverage with a rate constant of k 2. The three assumptions are combined to obtain the relationship d θ/d t = k 1 θ(1 − θ) − k 2 θ. The fouling layer grows on the covered surface and the fouling rate can be expressed as θR f′ where R f′ can be any established fouling rate expression. Experimental data, including data obtained during induction periods have been successfully correlated for systems including crude oil fouling, water scaling and whey protein fouling. The physical meanings of the model parameters are discussed. The model supports experimental observations in which shorter induction periods are found with higher surface temperatures. The effects of the surface material and the flow velocity are also analysed.