Library

feed icon rss

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
  • 1
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Chaos 9 (1999), S. 315-322 
    ISSN: 1089-7682
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Front dynamics in the frontal polymerization of two multifunctional acrylate monomers, 1,6-hexanediol diacrylate (HDDA) and trimethylolpropane ethoxylate triacrylate (TMPTA), with Lupersol 231 [1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane] as the initiator, are studied. In most frontal polymerization systems, the dynamics are associated with a planar front propagating through the sample. However, in some cases, front behavior can be altered: the front becomes nonplanar characterized by complex patterns like spin modes and pulsations. To determine how these periodic and aperiodic modes arise, reactant solutions consisting of HDDA diluted with diethyl phthalate (DEP) and TMPTA diluted with dimethyl sulfoxide (DMSO) were used in the study. In the study we reveal frontal behavior characteristic of period-doubling behavior, a doubling of spin heads that degenerate into an apparently chaotic mode. Also, a pulsating symmetric mode has been observed. These observations have a striking similarity to observations made in studies of self-propagating high-temperature synthesis (SHS) in which the addition of an inert diluent afforded a rich variety of dynamical behavior. The degree of cross-linking has also been found to be a bifurcation parameter. The energy of activation of multifunctional acrylate polymerization is a strong function of the degree of polymerization. By adding a monoacrylate (benzyl acrylate: BzAc), such that the front temperature was invariant, we observed a period-doubling bifurcation sequence through changes in the energy of activation, which has not been previously reported. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 2
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Chaos 7 (1997), S. 331-340 
    ISSN: 1089-7682
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Frontal propagation of a highly exothermic polymerization reaction in a liquid is studied with the goal of developing a mathematical model of the process. As a model case we consider monomers such as methacrylic acid and n-butyl acrylate with peroxide initiators, although the model is not limited to these reactants and can be applied to any system with the similar basic polymerization mechanism. A three-step reaction mechanism, including initiation, propagation and termination steps, as well as a more simple one-step mechanism, were considered. For the one-step mechanism the loss of stability of propagating front was observed as a sequence of period doubling bifurcations of the front velocity. It was shown that the one-step model cannot account for less than 100% conversion and product inhomogeneities as a result of front instability, therefore the three-step mechanism was exploited. The phenomenon of superadiabatic combustion temperature was observed beyond the Hopf bifurcation point for both kinetic schemes and supported by the experimental measurements. One- and two-dimensional numerical simulations were performed to observe various planar and nonplanar periodic modes, and the results for different kinetic schemes were compared. It was found that stability of the frontal mode for a one-step reaction mechanism does not differ for 1-D and 2-D cases. For the three-step reaction mechanism 2-D solutions turned out to be more stable with respect to the appearance of nonplanar periodic modes than corresponding 1-D solutions. Higher Zeldovich numbers (i.e., higher effective activation energies or lower initial temperatures) are necessary for the existence of planar and nonplanar periodic modes in the 2-D reactor with walls than in the 1-D case. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 3
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Chaos 6 (1996), S. 461-465 
    ISSN: 1089-7682
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Dynamic behavior of the pH-regulated oscillations has been studied for the hydrogen peroxide oxidation of thiosulfate ions in the presence of trace amounts of copper(II) ions in a semibatch reactor. A solution of 0.08 M Na2S2O3 and 0.112 M NaOH was flowed at 0.160 mL/min into 300 mL of solution containing the H2O2 and Cu2+ in a vessel. There exists a critical value of the H2O2 or Cu2+ concentrations below which the system does not oscillate. The oscillations appear due to an infinite period bifurcation at low initial concentrations of the H2O2. The initial concentration of Cu2+ may be considered as a bifurcation parameter in this case. Increase of the initial hydrogen peroxide concentration causes the pH-regulated oscillations through a nondegenerate supercritical Hopf bifurcation. The classification of bifurcations is based on the analysis of the behavior of oscillation amplitude and period at different initial concentrations of the H2O2 and Cu2+. Our results show a possibility to distinguish different scenarios for the appearance of transient oscillations in semibatch experiments. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 5385-5388 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 5
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 5379-5384 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 117 (1995), S. 3611-3612 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 7
    ISSN: 0887-624X
    Keywords: propagating polymerization fronts ; frontal polymerization ; traveling waves ; conversion ; adiabatic polymerization ; temperature profiles ; ceiling temperature ; molecular weight distribution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several properties of propagating fronts of addition polymerization were studied. A power function could be fit to the velocity dependence on initiator concentration, but not with the exponents predicted by current models or in agreement with other published work. Bubbles from the volatile by-products of initiator decomposition were found to affect the front velocity and curvature. The front velocity for triethylene glycol dimethacrylate polymerization was found to depend linearly on temperature over a moderate range. The conversion of methacrylic acid in fronts varied greatly with initiator type and concentration. Benzoyl peroxide produced much lower conversion than t-butyl peroxide, but fronts with tBPO propagated slower. A dual initiator system of BPO and tBPO produced rapidly propagating fronts with good conversion but the contribution of each initiator to the velocity was not additive. The possibility of chain branching was considered. The apparent molecular weight distributions were very broad, often trimodal, and found to depend on initiator type and concentration as well as the tube diameter. The temperature profiles were measured and found to be very sharp for BPO and broader for tBPO but both had front temperatures in excess of 200°C, indicating a high ceiling temperature. © 1995 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 991-995 
    ISSN: 0887-624X
    Keywords: propagating polymerization fronts ; frontal polymerization ; traveling waves ; anhydride ; methacrylic acid ; butyl acrylate ; molecular weight distributions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have analyzed fractionated samples of poly(methacrylic acid) produced in a propagating front for the amount of anhydride that formed and determined that a large percentage of acid groups exist as anhydrides (〉20%). By analyzing the samples after cleavage, we found that the molecular weight dropped significantly (from Mn = 1.4 × 105 to Mn = 1.0 × 104). We conclude that the high molecular weights observed previously were the result of intermolecular anhydride formation. Poly(butyl acrylate), which cannot form anhydride bonds, produced in fronts had broad (Mw/Mn = 1.7-2.0) but unimodal molecular weight distributions with Mu 〈 105. The average molecular weight decreased with increasing initiator concentrations. © 1996 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 227-230 
    ISSN: 0887-624X
    Keywords: IPN ; frontal polymerization ; propagating front ; SIN ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report a new method for the preparation of a simultaneous interpenetrating polymer network (SIN) using a thermal propagating front of two independent and noninterfering polymerization mechanisms. The system consists of the free radical crosslinking of triethylene glycol dimethacrylate (TGDMA) and the amine/BCl3 · amine curing of diglycidyl ether of bisphenol A (DGEBA). The front velocity dependence on the percentage of each monomer shows a minimum at 45% TGDMA. Temperature profile measurements indicate that a single reaction front propagates. A colored opaque material is produced, but SEM and TEM analysis were inconclusive whether phase separation occurred. Samples as large as 5 cm in diameter were prepared with this method. We conclude that this method should be especially suited for preparing large samples of IPNs in which significant phase separation occurs. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 2631-2636 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Exothermic chemical reactions are capable otautocatalytic self-propagation in a condensed reactive medium as a thermal wave. These take place in self-propagating high-temperature synthesis, frontal polymerization, curing of epoxy resins, and various solid-phase reaction processes. The lack of accurate analytical solutions for the front velocity and spatial parameter distributions has led to a period of approximate analytical solutions based on the infinitely narrow reaction zone assumption. A more accurate reaction zone approximation is presented that results in new equations for temperature and concentration spatial distributions as well as the wave velocity. Necessaty conditions for nondegeneration of the combustion wave were also obtained.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...