Vulcanization. Part V. The Formation of Crosslinks in the System: Natural Rubber-Sulfur-MBT-Zinc Ion

1964 ◽  
Vol 37 (3) ◽  
pp. 679-688 ◽  
Author(s):  
A. Y. Coran
Keyword(s):  
Natural Rubber ◽  
Delay Time ◽  
Zinc Ion ◽  
Reaction Scheme ◽  
Specific Rate ◽  
First Order ◽  
Zn Chelates

Abstract The response of the delay time and specific rate of vulcanization (treated as first order) to changes in starting concentrations of accelerator, sulfur and activator in the system: natural rubber-sulfur-MBT-Zn++ was defined by empirically derived relationships. The effects of compounding variables on the number and types of crosslinks formed in the vulcanizate were also studied. A reaction scheme was proposed to explain the role of soluble Zn++. The scheme is consistent with the fact that increases in the concentration of soluble Zn++ give slower specific rates of crosslink formation but more crosslinks. In the scheme, it was proposed that Zn++ chelates certain crosslink presursors.

The Role of Starting Potential in the Kinetics of Chemical Reactions under Electrodeless Discharge

1970 ◽  
Vol 25 (11) ◽  
pp. 1772
Author(s):  
T.S.R Ao ◽  
A. Patil
Keyword(s):  
Gas Phase ◽  
Chemical Reactions ◽  
Electric Discharge ◽  
Specific Rate ◽  
Gas Phase Reactions ◽  
Electrodeless Discharge ◽  
First Order ◽  
Kinetics Of

Abstract It has been shown that in kinetically first order gas phase reactions occuring under electric discharge, such as the decomposition of N2O, the application, at various initial pressures, of the same multiple of the respective starting potential ensures that the reaction occurs at the same specific rate.

Kinetics of zinc ion incorporation in base into a centrally aprotic beta-octabrominated cationic water-soluble porphyrin and its monolithium complex

2001 ◽  
Vol 05 (12) ◽  
pp. 829-834 ◽  
Author(s):  
SABRINA L. BAILEY ◽  
P. HAMBRIGHT
Keyword(s):  
Formation Constant ◽  
Zinc Ion ◽  
Water Soluble ◽  
Specific Rate ◽  
First Order ◽  
Specific Rate Constant ◽  
Zinc Concentrations ◽  
Water Soluble Porphyrin ◽  
Ion Incorporation ◽  
Kinetics Of

The kinetics of zinc incorporation from pH 12 to 13 into the centrally aprotic BrP (4)2+ form of beta-octabromo-meso-tetrakis(N-methyl-4-pyridyl)porphyrin and its monolithium complex were studied at 25.0 °C, ionic strength (I) = 0.10. The reactions were first order in porphyrin and total zinc concentrations. For BrP (4)2+, the specific rate constant was 5.1 × 105 M -1 s -1 for Zn ( OH )2 aq , 9.9 × 104 M -1 s -1 for [Formula: see text] and [Formula: see text] was unreactive. The Li - BrP (4)3+ complex had a formation constant with BrP (4)2+ of 1.1 × 103 M -1 from both kinetic and equilibrium measurements. In solutions containing both BrP (4)2+ and Li - BrP (4)3+, zinc incorporation proceeded only through BrP (4)2+.

Exploring Baryon Rich Matter with Heavy-Ion Collisions

2019 ◽  
Vol 64 (7) ◽  
pp. 583 ◽  
Author(s):  
S. Harabasz
Keyword(s):  
Center Of Mass ◽  
Heavy Ion ◽  
State Density ◽  
Heavy Nuclei ◽  
First Order ◽  
Center Of Mass Energy ◽  
Ion Collisions ◽  
Deconfinement Phase Transition ◽  
Ground State Density

Collisions of heavy nuclei at (ultra-)relativistic energies provide a fascinating opportunity to re-create various forms of matter in the laboratory. For a short extent of time (10-22 s), matter under extreme conditions of temperature and density can exist. In dedicated experiments, one explores the microscopic structure of strongly interacting matter and its phase diagram. In heavy-ion reactions at SIS18 collision energies, matter is substantially compressed (2–3 times ground-state density), while moderate temperatures are reached (T < 70 MeV). The conditions closely resemble those that prevail, e.g., in neutron star mergers. Matter under such conditions is currently being studied at the High Acceptance DiElecton Spectrometer (HADES). Important topics of the research program are the mechanisms of strangeness production, the emissivity of matter, and the role of baryonic resonances herein. In this contribution, we will focus on the important experimental results obtained by HADES in Au+Au collisions at 2.4 GeV center-of-mass energy. We will also present perspectives for future experiments with HADES and CBM at SIS100, where higher beam energies and intensities will allow for the studies of the first-order deconfinement phase transition and its critical endpoint.

scholarly journals Enhancing methane production from the invasive macroalga Rugulopteryx okamurae through anaerobic co-digestion with olive mill solid waste: process performance and kinetic analysis

2021 ◽  
Author(s):  
D. de la Lama-Calvente ◽  
M. J. Fernández-Rodríguez ◽  
J. Llanos ◽  
J. M. Mancilla-Leytón ◽  
R. Borja
Keyword(s):  
Anaerobic Digestion ◽  
Solid Waste ◽  
Methane Production ◽  
Methane Yield ◽  
Specific Rate ◽  
Order Kinetic ◽  
Two Phase ◽  
First Order ◽  
Olive Mill Solid Waste ◽  
Olive Mill

AbstractThe biomass valorisation of the invasive brown alga Rugulopteryx okamurae (Dictyotales, Phaeophyceae) is key to curbing the expansion of this invasive macroalga which is generating tonnes of biomass on southern Spain beaches. As a feasible alternative for the biomass management, anaerobic co-digestion is proposed in this study. Although the anaerobic digestion of macroalgae barely produced 177 mL of CH4 g−1 VS, the co-digestion with a C-rich substrate, such as the olive mill solid waste (OMSW, the main waste derived from the two-phase olive oil manufacturing process), improved the anaerobic digestion process. The mixture improved not only the methane yield, but also its biodegradability. The highest biodegradability was found in the mixture 1 R. okamurae—1 OMSW, which improved the biodegradability of the macroalgae by 12.9% and 38.1% for the OMSW. The highest methane yield was observed for the mixture 1 R. okamurae—3 OMSW, improving the methane production of macroalgae alone by 157% and the OMSW methane production by 8.6%. Two mathematical models were used to fit the experimental data of methane production time with the aim of assessing the processes and obtaining the kinetic constants of the anaerobic co-digestion of different combination of R. okamurae and OMSW and both substrates independently. First-order kinetic and the transference function models allowed for appropriately fitting the experimental results of methane production with digestion time. The specific rate constant, k (first-order model) for the mixture 1 R. okamurae- 1.5 OMSW, was 5.1 and 1.3 times higher than that obtained for the mono-digestion of single OMSW and the macroalga, respectively. In the same way, the transference function model revealed that the maximum methane production rate (Rmax) was also found for the mixture 1 R. okamurae—1.5 OMSW (30.4 mL CH4 g−1 VS day−1), which was 1.6 and 2.2 times higher than the corresponding to the mono-digestions of the single OMSW and sole R. okamurae (18.9 and 13.6 mL CH4 g−1 VS day−1), respectively.

scholarly journals Biocomposites of Epoxidized Natural Rubber/Poly(lactic acid) Modified with Natural Fillers (Part I)

2021 ◽  
Vol 22 (6) ◽  
pp. 3150
Author(s):  
Anna Masek ◽  
Stefan Cichosz ◽  
Małgorzata Piotrowska
Keyword(s):  
Tensile Strength ◽  
Lactic Acid ◽  
Natural Rubber ◽  
Epoxidized Natural Rubber ◽  
Poly Lactic Acid ◽  
Uv Aging ◽  
High Elasticity ◽  
Natural Fillers ◽  
Natural Additives

The study aimed to prepare sustainable and degradable elastic blends of epoxidized natural rubber (ENR) with poly(lactic acid) (PLA) that were reinforced with flax fiber (FF) and montmorillonite (MMT), simultaneously filling the gap in the literature regarding the PLA-containing polymer blends filled with natural additives. The performed study reveals that FF incorporation into ENR/PLA blend may cause a significant improvement in tensile strength from (10 ± 1) MPa for the reference material to (19 ± 2) MPa for the fibers-filled blend. Additionally, it was found that MMT employment in the role of the filler might contribute to ENR/PLA plasticization and considerably promote the blend elongation up to 600%. This proves the successful creation of the unique and eco-friendly PLA-containing polymer blend exhibiting high elasticity. Moreover, thanks to the performed accelerated thermo-oxidative and ultraviolet (UV) aging, it was established that MMT incorporation may delay the degradation of ENR/PLA blends under the abovementioned conditions. Additionally, mold tests revealed that plant-derived fiber addition might highly enhance the ENR/PLA blend’s biodeterioration potential enabling faster and more efficient growth of microorganisms. Therefore, materials presented in this research may become competitive and eco-friendly alternatives to commonly utilized petro-based polymeric products.

scholarly journals Ganglioside incorporation and release by the isolated perfused rat liver

1991 ◽  
Vol 274 (2) ◽  
pp. 581-585 ◽  
Author(s):  
S C Kivatinitz ◽  
A Miglio ◽  
R Ghidoni
Keyword(s):  
Rat Liver ◽  
The Other ◽  
Regulatory Role ◽  
Isolated Perfused Rat Liver ◽  
Order Kinetic ◽  
Perfused Rat Liver ◽  
Ganglioside Gm1 ◽  
First Order ◽  
Pseudo First Order

The fate of exogenous ganglioside GM1 labelled in the sphingosine moiety, [Sph-3H]GM1, administered as a pulse, in the isolated perfused rat liver was investigated. When a non-recirculating protocol was employed, the amount of radioactivity in the liver and perfusates was found to be dependent on the presence of BSA in the perfusion liquid and on the time elapsed after the administration of the ganglioside. When BSA was added to the perfusion liquid, less radioactivity was found in the liver and more in the perfusate at each time tested, for up to 1 h. The recovery of radioactivity in the perfusates followed a complex course which can be described by three pseudo-first-order kinetic constants. The constants, in order of decreasing velocity, are interpreted as: (a) the dilution of the labelled GM1 by the constant influx of perfusion liquid; (b) the washing off of GM1 loosely bound to the surface of liver cells; (c) the release of gangliosides from the liver. Process (b) was found to be faster in the presence of BSA, probably owing to the ability of BSA to bind gangliosides. The [Sph-3H]GM1 in the liver underwent metabolism, leading to the appearance of products of anabolic (GD1a, GD1b) and catabolic (GM2, GM3) origin; GD1a appeared before GM2 and GM3 but, at times longer than 10 min, GM2 and GM3 showed more radioactivity than GD1a. At a given time the distribution of the radioactivity in the perfusates was quite different from that of the liver. In fact, after 60 min GD1a was the only metabolite present in any amount, the other being GM3, the quantity of which was small. This indicates that the liver is able to release newly synthesized gangliosides quite specifically. When a recirculating protocol was used, there were more catabolites and less GD1a than with the non-recirculating protocol. A possible regulatory role of ganglioside re-internalization on their own metabolism in the liver is postulated.

Radical Mechanisms in Saturated and Olefinic Systems. II. Disubstitutive Carbon-Carbon Cross-Linking by Tertiary Alkoxy Radicals in Isoprenic Olefins and Rubber

1951 ◽  
Vol 24 (4) ◽  
pp. 777-786
Author(s):  
E. H. Farmer ◽  
C. G. Moore
Keyword(s):  
Natural Rubber ◽  
Cross Linking ◽  
Chain Molecules ◽  
Alkoxy Radicals ◽  
Full Extent ◽  
Carbon Chains ◽  
Butyl Peroxide ◽  
High Degree ◽  
Vulcanization Process

Abstract The high degree of dehydrogenation effected by tert.-butoxy radicals at the α-methylenic groups of olefins enables these radicals to be used for the carbon-to-carbon cross-linking of unsaturated carbon chains, and especially of the polyisoprenic chains of natural rubber. Such cross-linking amounts to a vulcanization process in which the connecting links between chain molecules are just C—C bonds, which may be expected to have appropriate attributes. An examination has first been made of the cross-linking produced by tert.- butoxy radicals (from di-tert.-butyl peroxide) at 140° between the short iso-prenic chains in 1-methylcyclohexene, 4-methylhept-3-ene, 2,6-dimethylocta-2, 6-diene, and digeranyl. Cross-linking proceeds efficiently in each case, and the points of union in these isoprene units which become directly joined are not confined to original α-methylenic carbon atoms. Where the reagent radicals are in considerable deficit, e.g., one per two or three of the isoprene units present, those olefin molecules which are attacked become linked together mostly by single unions to form aggregates containing two, three or four molecules; but in the tetraisoprenic olefins the extent to which more than one union is formed between some of the directly linked molecules becomes appreciable. In natural rubber, cross-linking occurs smoothly and to nearly the full extent corresponding to the (in practice restricted) proportion of peroxidic reagent employed. Good vulcanizates can be so obtained in which the tensile stength is found to increase towards a maximum and then to decline rapidly as the degree of cross-linking steadily increases. Thus to obtain vulcanizates of the optimum physical characteristics, the degree of cross-linking must be suitably chosen. The role of the peroxidic reagent is almost entirely non-additive and non-degradative.

The Propagation Mechanism of a Vortex on the β Plane

2007 ◽  
Vol 37 (9) ◽  
pp. 2316-2330 ◽  
Author(s):  
Peter Jan van Leeuwen
Keyword(s):  
Coriolis Force ◽  
Opposite Sign ◽  
Propagation Mechanism ◽  
Reduced Gravity ◽  
Background Current ◽  
Background Flow ◽  
Coriolis Parameter ◽  
First Order ◽  
Flow Changes

Abstract The propagation velocity and propagation mechanism for vortices on a β plane are determined for a reduced-gravity model by integrating the momentum equations over the β plane. Isolated vortices, vortices in a background current, and initial vortex propagation from rest are studied. The propagation mechanism for isolated anticyclones as well as cyclones, which has been lacking up to now, is presented. It is shown that, to first order, the vortex moves to generate a Coriolis force on the mass anomaly of the vortex to compensate for the force on the vortex due to the variation of the Coriolis parameter. Only the mass anomaly of the vortex is of importance, because the Coriolis force due to the motion of the bulk of the layer moving with the vortex is almost fully compensated by the Coriolis force on the motion of the exterior flow. Because the mass anomaly of a cyclone is negative the force and acceleration have opposite sign. The role of dipolar structures in steadily moving vortices is discussed, and it is shown that their overall structure is fixed by the steady westward motion of the mass anomaly. Furthermore, it is shown that reduced-gravity vortices are not advected with a background flow. The reason for this behavior is that the background flow changes the ambient vorticity gradient such that the vortex obtains an extra self-propagation term that exactly cancels the advection by the background flow. Last, it is shown that a vortex initially at rest will accelerate equatorward first, after which a westward motion is generated. This result is independent of the sign of the vortex.

On the role of Ramsey quantifiers in first order arithmetic

1982 ◽  
Vol 47 (2) ◽  
pp. 423-435 ◽  
Author(s):  
James H. Schmerl ◽  
Stephen G. Simpson
Keyword(s):  
Formal System ◽  
Intended Meaning ◽  
Completeness Proof ◽  
First Order ◽  
Uncountable Cardinal ◽  
Consistent Extension ◽  
Witness Set ◽  
Order Arithmetic ◽  
Infinite Set

The purpose of this paper is to study a formal system PA(Q2) of first order Peano arithmetic, PA, augmented by a Ramsey quantifier Q2 which binds two free variables. The intended meaning of Q2xx′φ(x, x′) is that there exists an infinite set X of natural numbers such that φ(a, a′) holds for all a, a′ Є X such that a ≠ a′. Such an X is called a witness set for Q2xx′φ(x, x′). Our results would not be affected by the addition of further Ramsey quantifiers Q3, Q4, …, Here of course the intended meaning of Qkx1 … xkφ(x1,…xk) is that there exists an infinite set X such that φ(a1…, ak) holds for all k-element subsets {a1, … ak} of X.Ramsey quantifiers were first introduced in a general model theoretic setting by Magidor and Malitz [13]. The system PA{Q2), or rather, a system essentially equivalent to it, was first defined and studied by Macintyre [12]. Some of Macintyre's results were obtained independently by Morgenstern [15]. The present paper is essentially self-contained, but all of our results have been directly inspired by those of Macintyre [12].After some preliminaries in §1, we begin in §2 by giving a new completeness proof for PA(Q2). A by-product of our proof is that for every regular uncountable cardinal k, every consistent extension of PA(Q2) has a k-like model in which all classes are definable. (By a class we mean a subset of the universe of the model, every initial segment of which is finite in the sense of the model.)

Role of Single Word Variables in Recall of Statistical Approximations to English

1966 ◽  
Vol 19 (2) ◽  
pp. 627-634 ◽  
Author(s):  
Mari J. K. Brown
Keyword(s):  
Free Recall ◽  
Higher Order ◽  
Order Of Approximation ◽  
Single Word ◽  
First Order ◽  
Original Order ◽  
Sequential Organization ◽  
The Individual

Free recall of lists at different orders of approximation to English was compared to the recall of the same lists when the order of the words had been scrambled to destroy their sequential organization. Recall of the organized lists showed the typical improvement with increasing order of approximation. Recall of the scrambled lists was unrelated to the original order of approximation. The results indicate that increased recall with increasing order of approximation to English is not produced by systematic differences in the characteristics of the individual words comprising the approximations. When recall of the organized lists was scored in terms of the number of longer sequences present in recall, the number of recalled sequences of any given length increased as order of approximation to English increased, with the first order list showing proportionally less organization in recall than the second and higher order lists.

Sign in / Sign up

Export Citation Format

Share Document