Role of Carbon in Oxidation of GR-S Vulcanizates

1947 ◽  
Vol 20 (2) ◽  
pp. 469-478 ◽  
Author(s):  
Hugh Winn ◽  
J. Reid Shelton ◽  
David Turnbull

Abstract 1. Carbon black is a catalyst for the oxidation of GR-S vulcanizates. The increased rate of oxygen absorption with increased loading is, however, a function of surface area rather than weight. Different types of carbons show different degrees of activity for a given surface area; the furnace carbons studied were, for example, only 55 per cent as active as channel black in promoting oxidation. 2. The rate constant for the initial rapid absorption of oxygen by GR-S tread stocks is independent of carbon loading. The presence of carbon is, however, essential to activate the centers involved in this initial stage, and the number of activated centers increases with carbon loadings, so that the amount of oxygen absorbed in a given time is also increased. 3. The second or linear stage of oxygen absorption involves two types of reaction with the remaining oxidizable centers in the polymer: a reaction with centers not under the catalytic influence of the carbon black, and a reaction catalyzed by carbon. 4. A theoretical equation was presented which permits the calculation of oxygen absorption by stocks containing either furnace- or channel-type carbons with various surface areas and loadings. The validity of the theory on which the derivation was based is supported by the quantitative correlation of calculated and observed rates of oxygen absorption for stocks containing carbons of both types, with surface areas ranging from 3.7 to 15.7 acres per pound and with loadings of 0 to 75 parts per 100 parts of GR-S. 5. The additional oxygen absorbed at higher loadings of carbon was shown to produce a correspondingly greater deterioration of physical properties.

2008 ◽  
Vol 100 (4) ◽  
pp. 2048-2061 ◽  
Author(s):  
En Hong ◽  
Fatma Gurel Kazanci ◽  
Astrid A. Prinz

Neuronal activity arises from the interplay of membrane and synaptic currents. Although many channel proteins conducting these currents are phylogenetically conserved, channels of the same type in different animals can have different voltage dependencies and dynamics. What does this mean for our ability to derive rules about the role of different types of ion channels in neuronal activity? Can results about the role of a particular channel type in a particular type of neuron be generalized to other neuron types? We compare spiking model neurons in two databases constructed by exploring the maximal conductance spaces of two models. The first is a model of crustacean stomatogastric neurons, and the second is a model of rodent thalamocortical neurons, but both models contain similar types of membrane currents. Spiking neurons in both databases show distinct fast and slow subpopulations, but our analysis reveals that related currents play different roles in fast and slow spiking in the stomatogastric versus thalamocortical neurons. This analysis involved conductance-space visualization and comparison of voltage traces, current traces, and frequency-current relationships from all spiker subpopulations. Our results are consistent with previous work indicating that the role a membrane current plays in shaping a neuron's behavior depends on the voltage dependence and dynamics of that current and may be different in different neuron types depending on the properties of other currents it is interacting with. Conclusions about the function of a type of membrane current based on experiments or simulations in one type of neuron may therefore not generalize to other neuron types.


1965 ◽  
Vol 38 (3) ◽  
pp. 636-646
Author(s):  
J. T. Gruver ◽  
K. W. Rollmann

Abstract The thermal antioxidant behavior of carbon black was studied in vulcanized cis-polybutadiene and related to the surface chemistry of the black. Continuous and intermittent stress relaxation and oxygen absorption measurements were employed to determine the antioxidant ability of the carbon blacks. The blacks were characterized by the surface concentrations of oxygen-containing functional groups, using methods described in the literature. Antioxidant activity was found to be highest in carbons containing relatively large amounts of bound oxygen. These carbons are also acidic and decompose peroxides by the ionic mechanism. This was demonstrated with cumyl peroxide. However, even though the acidity and ability to decompose cumyl peroxide to phenol and acetone could be destroyed by methylation, this treatment did not seriously impair the antioxidant activity, so that the role of acidic groups appears to be minor. Evidence is presented which suggests strongly that the antioxidant behavior of carbon blacks is due to surface quinones, possibly hydrogen-bonded with adjacent hydroxyl groups. Measurements made on samples vulcanized in peroxide and sulfur curing systems indicate that the antioxidant behavior of carbon black is independent of the method of vulcanization in the absence of other antioxidants. A characteristic feature of the antioxidant action of carbon blacks is their tendency to repress the oxidative crosslinking reactions, the relative amount of compensation of chain scission by crosslinking being smaller than in gum vulcanizates.


2017 ◽  
Vol 114 (7) ◽  
pp. E1046-E1053 ◽  
Author(s):  
Nancy Birkner ◽  
Alexandra Navrotsky

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides.


1967 ◽  
Vol 40 (5) ◽  
pp. 1305-1310 ◽  
Author(s):  
G. Kraus ◽  
K. W. Rollmann

Abstract The Harkins and Jura (HJ) absolute method of surface area determination (Harkins and Jura, J. Am. Chem. Soc. 66, 919, 1944) has been applied to a large number of carbon blacks. Surface area is calculated from the heat of immersion of the solid powder covered by a preadsorbed multilayer of the immersion liquid. For non-porous carbon blacks good agreement with nitrogen adsorption surface areas is obtained, but with porous blacks the HJ method gives smaller values since micropores are filled and bridged over by the pre-adsorbed film. Thus the HJ areas are more nearly representative of particle size and may be used to calibrate indirect methods of particle size determination. An example of this is shown using light reflectance values on dry carbon black and possible complications due to particle size distribution in the use of the reflectance test are discussed.


1973 ◽  
Vol 46 (1) ◽  
pp. 192-203 ◽  
Author(s):  
R. A. Klyne ◽  
B. D. Simpson ◽  
M. L. Studebaker

Abstract 1. The various tint tests correlate with each other—it does not make much difference which of the three procedures is used. The discrimination between similar blacks is comparable. Specific surface areas obtained by the three methods are comparable and differences appear to be due to experimental errors. (Compare Figures 5–7). 2. Surface areas larger than some 90 to 100 m2/g cannot be reliably determined from tint strength measurements alone. 3. Structure exerts a pronounced effect on tint strength of furnace blacks, especially above 90 to 100 m2/g. Porosity and/or composition are apparently also variables which affect tinting strength. 4. Densichron reflectance on the dry carbon black can be used to estimate specific surface areas up to about 140 m2/g; but, since theabsoluteerrorincreases as the specific surface area increases, this method loses some of its reliability at values above about 110 m2/g. The relative error in reflectance determinations does not vary greatly over the furnace-black range. Densichron reflectance is influenced by composition, evidently due to composition-related differences in optical properties of the carbons. 5. In CTAB adsorption measurements, titration errors and handling errors tend to be rather constant for blacks of different surface area. Hence, CTAB permits better discrimination among blacks of small particle size. 6. The errors in Densichron reflectance surface area increase with specific surface area. Hence, the deviations between CTAB and reflectance surface area which are due to experimental error increase with the surface area of the sample.


Molecules ◽  
2020 ◽  
Vol 25 (19) ◽  
pp. 4445 ◽  
Author(s):  
Zuzana Jankovská ◽  
Marek Večeř ◽  
Ivan Koutník ◽  
Lenka Matějová

Waste scrap tyres were thermally decomposed at the temperature of 600 °C and heating rate of 10 °C·min−1. Decomposition was followed by the TG analysis. The resulting pyrolytic carbon black was chemically activated by a KOH solution at 800 °C. Activated and non-activated carbon black were investigated using high pressure thermogravimetry, where adsorption isotherms of N2, CO2, and cyclohexane were determined. Isotherms were determined over a wide range of pressure, 0.03–4.5 MPa for N2 and 0.03–2 MPa for CO2. In non-activated carbon black, for the same pressure and temperature, a five times greater gas uptake of CO2 than N2 was determined. Contrary to non-activated carbon black, activated carbon black showed improved textural properties with a well-developed irregular mesoporous-macroporous structure with a significant amount of micropores. The sorption capacity of pyrolytic carbon black was also increased by activation. The uptake of CO2 was three times and for cyclohexane ten times higher in activated carbon black than in the non-activated one. Specific surface areas evaluated from linearized forms of Langmuir isotherm and the BET isotherm revealed that for both methods, the values are comparable for non-activated carbon black measured by CO2 and for activated carbon black measured by cyclohexane. It was found out that the N2 sorption capacity of carbon black depends only on its specific surface area size, contrary to CO2 sorption capacity, which is affected by both the size of specific surface area and the nature of carbon black.


1983 ◽  
Vol 56 (2) ◽  
pp. 440-449 ◽  
Author(s):  
Jerry B. Pausch ◽  
Caroline A. McKalen

Abstract For practical use of this method as a quality control procedure for carbon black, a combination of 4 mm3 and 6 mm octane doses appears to be the best compromise for a sample size of 0.1 g. These conditions cover well, a surface area range of 10–140 m2/g and surface areas up to 180 m2/g can be estimated. Larger doses of octane will extend the linear range on the high side, but the slope of the calibration curve is reduced significantly. A smaller slope yields lower precision. The regular testing of standards appears necessary to achieve optimum accuracy of surface area. At the present time, the method is calibrated against nitrogen surface area data, so the advantage of octane more closely simulating the rubber molecule is lost. We need to obtain adsorption isotherms that are better defined throughout the linear adsorption coefficient range for a number of carbon blacks, and thus become self-calibrated against octane. A more versatile dosing technique is preferred to enable these experiments to be run. An alternate approach is to correlate the headspace results with data obtained by other techniques such as CTAB. The advantages of automated headspace gas chromatography for measuring surface area have been outlined before . It is a rapid and simple method, which also exhibits relatively low labor involvement. The number of samples capable of being analyzed per day is significantly higher than by any other technique.


2008 ◽  
Vol 23 (2) ◽  
pp. 579-587 ◽  
Author(s):  
Chien-Cheng Li ◽  
Jow-Lay Huang ◽  
Ran-Jin Lin ◽  
Hong-Ping Lin ◽  
Ding-Fwu Lii ◽  
...  

Highly porous Ti and TiZrV getter film coatings have been successfully grown on (100) silicon substrates using the glancing-angle direct-current magnetron sputtering method. The evolution of the microstructures of the Ti and the TiZrV films strongly depends on the sputtering flux rate, surface diffusion rate, nucleation rate, compositions, and self-shadowing geometry of the nuclei on the sputtering flux. The larger the glancing angle, the higher the porosity and specific surface area of the Ti and TiZrV films. The weight-gain results strongly depend on several factors, such as specific surface area, the surface structure of the getter film, the diffusion rate of O in the getter film, the reactivity of Ti, Zr, and V on O, and the order of the stabilities of Ti, Zr, and V oxides on the film’s surface. Porous Ti film absorbs oxygen better than porous TiZrV film does due to its higher surface area and the high diffusion rate of O in Ti films.


2014 ◽  
Vol 14 (6) ◽  
pp. 7859-7887 ◽  
Author(s):  
W. Nie ◽  
A. J. Ding ◽  
Y. N. Xie ◽  
Z. Xu ◽  
H. Mao ◽  
...  

Abstract. Nitrous acid (HONO) plays a key role in atmospheric chemistry via influencing the budget of hydroxyl radical (OH). In this study, a two-month measurement period of HONO and related quantities were analyzed during a biomass burning season in 2012 at a suburban site in the western Yangtze River delta, eastern China. An overall high HONO concentration with the mean value of 1.1 ppbv was observed. During biomass burning (BB) periods, both HONO concentration and HONO / NO2 ratio were enhanced significantly compared with non-biomass burning periods. A correlation analysis showed that the HONO concentration was not associated potassium (a tracer of BB) in BB plumes, but showed a high correlation with the NO2 concentration, suggesting a principle role of secondary production rather than direct emissions in elevated HONO concentrations. A further analysis based on comparing the surface area at similar PM levels and HONO / NO2 ratios at similar surface area levels suggested larger specific surface areas and higher NO2 conversion efficiencies of BB aerosols. A mixed plume of BB and anthropogenic fossil fuel (FF) emissions was observed on 10 June with even higher HONO concentrations and HONO / NO2 ratios. The strong HONO production potential (high HONO / NO2 to PM2.5 ratio) was accompanied with a high sulfate concentration in this plume, suggesting a promotion of mixed aerosols to HONO formation. In summary, our study suggests an important role of BB in atmospheric oxidation capacity by affecting the HONO budget. This can be especially important in eastern China, where agricultural burning plumes are inevitably mixed with urban pollutions.


2020 ◽  
Vol 93 (1) ◽  
pp. 172-182 ◽  
Author(s):  
Vineet Kumar ◽  
Najib Alam ◽  
Dong-Joo Lee ◽  
Ulrich Giese

ABSTRACT Nanofillers of type few layer graphene (FLG) characterized with “low” surface area (<40 m2/g) were studied as reinforcing agents in poly (1,4-cis-isoprene) (IR matrix), and their roles in enhancing mechanical properties of rubber nanocomposites were demonstrated. The adsorption isotherms show that FLG surface areas were 13.8 m2/g for SFG6, 23.8 m2/g for KS4, and 39.5 m2/g for EXG 9840. All FLG had remarkable in-plane crystallinity and were characterized by a lower number of layers stacked (45–48) in the crystalline domain. Rheometric curves were studied to estimate the scorch time (t′05) and curing time (t′90). Tensile and dynamic–mechanical analyses show that FLG forms filler networks at low filler content. Tensile properties show that EXG 9840/IR has a lower reinforcing factor and elongation at break than KS4 FLG nanofiller. A series of experiments shows the dependency surface area of FLG in enhancing mechanical properties of nanocomposites. The work suggests that lower surface area should be selected in order to have lower dissipation of energy and efficient filler networking.


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