The Vulcanization of Elastomers. VII. The Vulcanization of Natural Rubber with Thiuram Disulfides. Part IV

1957 ◽  
Vol 30 (1) ◽  
pp. 69-76 ◽  
Author(s):  
Walter Scheele ◽  
Peter Stange
Keyword(s):  
Zinc Oxide ◽  
Natural Rubber ◽  
Constant Temperature ◽  
Rate Constants ◽  
Experimental Error ◽  
Oxide Content ◽  
Oxide Crystals ◽  
Kinetics Of ◽  
Limiting Value

Abstract The present paper deals with the kinetics of the thiuram vulcanization at varying thiuram disulfide concentrations as well as with the influence of the zinc oxide content upon vulcanization at constant temperature (120° C). It was found : 1. The limiting value of dithiocarbamate formation of 66 mole per cent relative to the amount of thiuram disulfide used is—within wide limits—independent of the initial thiuram disulfide concentration. 2. At constant thiuram disulfide concentration the limiting value of dithiocarbamate formation is unchanged when the zinc oxide content is successively increased. 3. Changing the zinc oxide content while the thiuram disulfide concentration is kept constant exerts an influence on the kinetics of the decrease of thiuram as well as on the increase of dithiocarbamate. The rate constants of both reactions increase. 4. It is concluded from these results that in all probability vulcanization is initiated on the surface of the zinc oxide crystals. 5. Even in stocks containing as much as 40 g. zinc oxide per hundred g. of compounds, the limiting value of dithiocarbamate formation remains unchanged. This was verified by the analysis of vulcanizates after extremely long cure times. The average limiting value of two experiments after 24 hours of cure was 65 mole per cent which corresponds to a two-thirds reaction within the experimental error.

Vulcanization of Elastomers. 18. Vulcanization of Natural Rubber with Sulfur in the Presence of Mercaptobenzothiazole. III

1958 ◽  
Vol 31 (3) ◽  
pp. 548-558 ◽  
Author(s):  
Otto Lorenz ◽  
Elisabeth Echte
Keyword(s):  
Zinc Oxide ◽  
Natural Rubber ◽  
Zinc Stearate ◽  
Oxide Content ◽  
Square Root ◽  
Initial Concentration ◽  
Velocity Constant ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Limiting Value

Abstract The present work is concerned with the influence of the concentration of sulfur and the zinc oxide content on the kinetics of the vulcanization of natural rubber with sulfur in the presence of mercaptobenzothiazole, zinc stearate and zinc oxide. The following results were obtained. 1. The velocity constant of the sulfur decrease, kSI, is inversely proportional to the initial concentration of sulfur. 2. The velocity constant of the change with time of the reciprocal equilibrium swelling, kQI, is inversely proportional to the square root of the initial concentration of sulfur. 3. The limiting value of the reciprocal equilibrium swelling, 1/Q∞ (degree of crosslinking), at constant stearate content, is proportional to the square root of the initial concentration of sulfur. 4. The amount of accelerator consumed during vulcanization increases with increase in the initial amount of sulfur. The decrease in the accelerator is a first order reaction having approximately the same rate as the decrease of sulfur. 5. The velocity constants of the sulfur decrease and the change with time of the reciprocal equilibrium swelling are practically independent of the amount of zinc oxide. Other situations exist, of course, for compounds without zinc oxide. 6. Empirical equations were derived to express the dependence of the constants kSI, kQI and 1/Q∞ on the composition of the mixture.

Kinetics of Crosslinking and Network Changes in Natural Rubber Vulcanizates with a Dithiodimorpholine Based Accelerator System

1980 ◽  
Vol 53 (5) ◽  
pp. 1015-1022 ◽  
Author(s):  
A. K. Bhowmick ◽  
S. K. De
Keyword(s):  
Natural Rubber ◽  
Rate Constants ◽  
Crosslink Density ◽  
Curing Temperature ◽  
Side Reactions ◽  
Filler Surface ◽  
Natural Rubber Vulcanizates ◽  
Kinetics Of ◽  
Accelerator System

Abstract Kinetics of crosslinking and network changes in unfilled and filled natural rubber vulcanizates with a dithiodimorpholine based accelerator system have been studied at 150° and 180°C. Results show that addition of HAF black enhances the polysulfidic crosslinks as well as the total crosslinks. This has been explained with the help of Coran's model wherein HAK black increases the rate constants. It is likely that the filler surface prevents desulfuration and undesirable side reactions involving the crosslink precursors. Increase of curing temperature by 30°C lowers the total crosslink density and increases the sulfur inefficiency.

Kinetics of hydrolyses of o-methylbenzylideneaniline and o-hydroxybenzylideneaniline

1968 ◽  
Vol 46 (9) ◽  
pp. 1589-1592 ◽  
Author(s):  
Alfred V. Willi ◽  
José F. Siman
Keyword(s):  
Hydrogen Bond ◽  
Schiff Base ◽  
Rate Constants ◽  
Experimental Error ◽  
Steric Effect ◽  
Hydrolysis Rate ◽  
Aqueous Methanol ◽  
Buffer Solutions ◽  
Acid Catalyzed ◽  
Kinetics Of

Rates of hydrolysis have been measured for o-methylbenzylideneaniline, o-hydroxybenzylideneaniline, and benzylideneaniline in various buffer solutions in 20% (by volume) aqueous methanol at 29.9 °C. Rate constants for the o-CH3 compound and the unsubstituted Schiff base agree within experimental error which indicates that there is no appreciable rate retarding steric effect. The o-OH group decreases the hydrolysis rate at pH = 5.6 – 6.6 by approximately one power of ten. This effect is caused by the hydrogen bond between the OH group and the azomethine N, which renders the Schiff base less accessible to acid-catalyzed hydrolysis.

Vulcanization of Elastomers. 40. Vulcanization of Natural Rubber and Synthetic Rubber with Sulfur in Presence of Sulfenamides. III

1965 ◽  
Vol 38 (1) ◽  
pp. 189-203 ◽  
Author(s):  
W. Scheele ◽  
J. Helberg
Keyword(s):  
Activation Energy ◽  
Reaction Mechanism ◽  
Natural Rubber ◽  
Rate Constants ◽  
Sulfur Concentration ◽  
Kcal Mole ◽  
Synthetic Rubber ◽  
Chemical Constitution ◽  
Induction Times ◽  
Kinetics Of

Abstract Vulcanization of natural rubber with sulfur was studied in presence of six sulfenamides, to determine the effect of the chemical constitution of the sulfenamide on sulfur decrease and on crosslinking. The results can be condensed as follows: (1) The kinetics of sulfur disappearance is in every respect qualitatively independent of the chemical constitution of the sulfenamide. (2) For the sulfenamides investigated, the smallest and largest rate constants for sulfur decrease differed only by a factor of two. (3) Greater differences are encountered in the induction times for sulfur decrease and for crosslinking. The latter are notably longer than those for sulfur disappearance. (4) The same activation energy, 23 kcal/mole, is derived from the temperature dependence of the induction times for all the sulfenamides. (5) The dissociation of sulfenamides in solution and their reaction with mercaptobenzothiazole were investigated further. The results provide the basis for a proposed reaction mechanism, which is presented in detail and can account for a number of the features typical of sulfenamide-accelerated vulcanization. (6) The drop in sulfur concentration goes at practically the same rate, if one introduces, instead of N, N-dicyclohexyl-2-benzothiazolesulfenamide, the corresponding ammonium mercaptide in equimolar concentration.

The Vulcanization of Elastomers. XI. The Vulcanization of Natural Rubber with Sulfur in the Presence of Mercaptobenzothiazole. I

1957 ◽  
Vol 30 (3) ◽  
pp. 911-927 ◽  
Author(s):  
Otto Lorenz ◽  
Elisabeth Echte
Keyword(s):  
Activation Energy ◽  
Zinc Oxide ◽  
Natural Rubber ◽  
Kinetic Analysis ◽  
Rate Constants ◽  
Network Formation ◽  
Zinc Salt ◽  
Kcal Mole ◽  
Minimum Quantity ◽  
First Order

Abstract 1. The decrease of free sulfur occurs according to the first order law during the vulcanization of natural rubber accelerated by mercaptobenzothiazole in the presence of zinc oxide. The activating energy for this reaction amounts to 30.5 kcal./mole. 2. If zinc benzothiazolylmercaptide is used as an accelerator, one obtains the same rate constants for the sulfur decrease as in the presence of mercaptobenzothiazole. These seem to be equivalent as regards their effectiveness of acceleration. 3. A kinetic analysis of the reciprocal swelling, which represents a measure of network formation, indicates that the reaction is first order. Sulfur decrease and reciprocal swelling prove to be equal processes as regards rate. This is true where vulcanization is accelerated with mercaptobenzothiazole or with the zinc salt. 4. During vulcanization there occurs a decrease of accelerator concentration. This is dependent upon the temperature and is tied in with the combination sulfur with rubber. 5. If the quantity of the accelerator added is changed, the rate constants for sulfur decrease and for reciprocal swelling do not change, provided that a minimum quantity of accelerator is present. 6. In vulcanization accelerated with zinc benzothiazolylmercaptide, zinc oxide being absent, sulfur decrease again occurs according to the first order law but considerably faster, without thereby changing the activation energy. These investigations are being continued and the results will be discussed in detail in relation to other published contributions in this field.

Vulcanization of Elastomers. 36. Vulcanization of Natural Rubber and Synthetic Rubbers with Sulfur in Absence of Accelerators. II

1964 ◽  
Vol 37 (4) ◽  
pp. 910-926 ◽  
Author(s):  
W. Scheele ◽  
H. Müller ◽  
W. Schulze
Keyword(s):  
Natural Rubber ◽  
Concentration Dependence ◽  
Good Description ◽  
Kcal Mole ◽  
First Order ◽  
Different Temperatures ◽  
In Cis ◽  
Kinetics Of ◽  
Limiting Value ◽  
Homolytic Dissociation

Abstract In continuation of earlier work with natural rubber, the kinetics of sulfur decrease were studied in certain synthetic rubbers for different temperatures and sulfur concentrations. At the same time the formation of polysulfide bound sulfur was studied, using as example the reaction of sulfur with natural rubber and synthetic rubbers. It was found that: 1) When the decrease in sulfur concentration is portrayed by curves which are convex to the time axis (Perbunan), the 0.6th order time-law is fulfilled, (as in the case of natural rubber independent of temperature and concentration. 2) In contrast, the concentration dependence of the rate at which sulfur decreases, both in Perbunan and cis 1,4-polybutadiene, denotes a first-order reaction in agreement with experience with natural rubber. 3) The activation energy of sulfur decrease has the same magnitude for all the elastomers investigated (34 to 36 kcal/mole). 4) The disagreement between the time law and the concentration dependence of the rate of sulfur disappearance encountered in all the experiments with 1,5-polyenes, is interpreted as indicating autocatalysis, which likewise explains the shape of the curves for sulfur disappearance. 5) Sulfur reacts considerably faster in natural rubber and Perbunan than in cis 1,4-polybutadiene; consequently a homolytic dissociation of the S8-ring cannot be rate-determining. 6) Polysulfide sulfur shows, in each case, a maximum with reaction time, and in completely reacted vulcanizates it tends toward a limiting value. An equation was found, which provides a good description of change with time of polysulfide concentration (natural rubber and cis 1,4-polybutadiene). 7) An explanation is given for the appearance of the polysulfide maximum; and how the reaction of sulfur with 1,5-polyenes can be represented, making use of all available results, is discussed.

The diffusion of aluminium and gallium in zinc oxide

1969 ◽  
Vol 22 (2) ◽  
pp. 325 ◽  
Author(s):  
VJ Norman
Keyword(s):  
Zinc Oxide ◽  
Diffusion Coefficient ◽  
Chemical Method ◽  
Surface Concentration ◽  
Activation Energies ◽  
Temperature Range ◽  
Polycrystalline Zinc ◽  
Substitutional Diffusion ◽  
Oxide Crystals ◽  
Limiting Value

Solubilities and rates of substitutional diffusion of aluminium and gallium in polycrystalline zinc oxide have been determined in the temperature range 750-1000� by a chemical method previously described. The solubility of aluminium in zinc oxide, expressed in ions cm-3, is given by the expression n = 1.0 x 1023exp(-1.08k-1T-1), and the solubility of gallium by n = 2.7 x 1021exp(-0.59k-1T-1), where the activation energies are expressed in eV. The rates of diffusion of both aluminium and gallium were found to be dependent on surface concentration up to a limiting value, at which the diffusion coefficient of aluminium is D = 5.3 x 10-2 exp(-2.74k-1T-1) cm2 sec-1, and that of gallium is D = 3.6 x 104 exp(-3.75k-1T-1) cm2 sac-1. ��� It is shown that supersaturation of both aluminium and gallium in the zinc oxide crystals occurs above 800�.

Effect of CMCS on Vulcanization Kinetics of Natural Rubber

2012 ◽  
Vol 535-537 ◽  
pp. 1214-1217
Author(s):  
Yong Zhou Wang ◽  
Hong Xing Gui ◽  
Tao Chen ◽  
Hong Hai Huang ◽  
Fu Quan Zhang ◽  
...  
Keyword(s):  
Activation Energy ◽  
Natural Rubber ◽  
Induction Period ◽  
Rate Constants ◽  
Carboxymethyl Chitosan ◽  
Curing Period ◽  
Vulcanization Kinetics ◽  
Kinetics Of ◽  
Work Effect

In this work, effect of carboxymethyl chitosan (CMCS) on vulcanization kinetics of natural rubber was studied using the Rheometer MDR2000.The results showed that both the rate constants of induction period and curing period of natural rubber (K-N) was greater than that of natural rubber added CMCS and the dosage is 0.05% of fresh latex (CMCS-1), but less than that of natural rubber added CMCS and the dosage is 0.1% of fresh latex (CMCS-2), and the activation energy 100.8kJ/mol of induction period of K-N is greater than the activation energy 96.7kJ/mol, 93.7kJ/mol of induction period of CMCS-1, CMCS-2, respectively and that the activation energy 104.4 kJ/mol of curing period of K-N is less than the activation energy111.9kJ/mol of curing period of CMCS-1, and bigger than the activation energy 103.4 of CMCS-2 at the same temperature.

Sign in / Sign up

Export Citation Format

Share Document