A Study of Vulcanization Accelerators. I. Compounds Which React Analogously to Rubber

1957 ◽  
Vol 30 (3) ◽  
pp. 952-961
Author(s):  
J. Shimozato ◽  
K. Ura
Keyword(s):  
Zinc Oxide ◽  
Zinc Sulfide ◽  
Hydrogen Abstraction ◽  
Reaction System ◽  
Detailed Examination ◽  
The Other ◽  
Chemical Behavior ◽  
Model Compounds ◽  
Rapid Decomposition ◽  
Series Of Experiments

Abstract 1. To elucidate the chemical behavior of rubber toward sulfur, a series of experiments was carried out using model compounds : tetralin, toluene, xylene, aniline, phenol, chlorobenzene, dichlorobenzene and naphthalene. Similar reactivities between rubber and the model compounds were observed. 2. The effects of the accelerators in the reactions of the model compounds with sulfur were different according to whether or not zinc oxide was present in the reaction system. 3. A detailed examination of the quantities of zinc sulfide formed in the reaction of tetralin with sulfur in the presence of zinc oxide showed that several vulcanization accelerators have similar activating effects in rubber vulcanization. 4. With tetralin as reactant, the quantity of zinc sulfide decreased suddenly at the reaction temperature 150° C, which was ascribed to the rapid decomposition of tetralin peroxide at this temperature. 5. The accelerating action of CPB, contrary to that of the other accelerators, was promoted by tetralin peroxide. 6. Tetralin peroxide had only a small inhibiting influence upon reactions with the amine accelerators, which is ascribed to the antioxidative nature of the amine derivatives; the inhibiting influence becomes larger in reactions with thiol derivatives or without any added accelerators. 7. Substituent effect on the hydrogen abstraction of the model compounds was primarily determined by the negativity of the relevant carbon atom. The order of the reactivity was found to be in accord with that toward the general “cationoid reagents”. 8. Analytical methods during and after the reactions were simplified for industry use.

The Chemistry of Vulcanization. VII. Role of Zinc Butyrate in the Reaction of Diphenylmethane, Sulfur and 2-Mercaptobenzothiazole

1960 ◽  
Vol 33 (1) ◽  
pp. 217-228 ◽  
Author(s):  
Jitsuo Tsurugi ◽  
Haruko Fukuda
Keyword(s):  
Zinc Oxide ◽  
Kinetic Study ◽  
Butyric Acid ◽  
Model Compound ◽  
Reaction System ◽  
The Other ◽  
Zinc Salt ◽  
Reaction Products ◽  
Molecular Dispersion

Abstract In previous Parts of this series, the accelerating mechanism of thiazole type accelerators, namely, 2-mercaptobenzothiazole (MBT), 2,2′-benzothiazolyl disulfide (MBTS) and zinc salt of 2-mercaptobenzothiazole (ZMBT) in the absence of zinc oxide or zinc soap, was investigated with diphenylmethane (DPM) as a model compound of rubber hydrocarbon. The significance of DPM as a model was discussed in some of the earlier papers. Parts IV, V and VI of this series indicated that 2-mercaptobenzothiazolyl radical generated from accelerators splits the sulfur ring, and that the processes by which accelerators generate the radical differ with each other according to their types. These results were obtained in the absence of zinc oxide or zinc soap. The present study will report the role of zinc butyrate in the reaction involving DPM, sulfur and MBT. Experience in the industry indicates that zinc oxide (or zinc soap) is indispensable to the thiazole type accelerators and that the efficiency of zinc oxide or soap is more prominent in MBT than in MBTS or ZMBT. The results obtained in the previous papers also suggest that zinc oxide or soap may have an influence on the rate at which the accelerator generates 2-mercaptobenzothiazolyl radical, since it is shown in Parts IV, V and VI that the radical has an accelerating effect. Therefore, it may be considered that zinc oxide or zinc soap activates MBT more effectively than does the other thiazole type accelerators in order to produce this radical. As will be seen later in this study, interaction of MBT with zinc butyrate in the absence of sulfur produces ZMBT and butyric acid. The ZMBT will interact with sulfur and generate the 2-mercaptobenzothiazolyl radical as reported in Part VI. The zinc salt thus formed will be dispersed in a state of molecular dispersion in the reaction system, while the same compound prepared in Part VI was not dissolved in DPM even at the reaction temperatures. In this respect the former is considered more effective than the latter. In order to verify the above assumptions the reaction involving DPM, sulfur and MBT in the presence of zinc butyrate were investigated. The reaction products and mechanism were compared with those in the absence of zinc soap. Since zinc butyrate is soluble in the reaction system at the reaction temperatures, a kinetic study also was carried out and compared with that in the absence of zinc soap.

Electron Irradiation Effects in Polyoxymethylene Crystals Grown Inside Trioxane Crystals

1971 ◽  
Vol 29 ◽  
pp. 78-79
Author(s):  
J. P. Colson ◽  
D. H. Reneker
Keyword(s):  
Cross Section ◽  
Cross Sections ◽  
Detailed Examination ◽  
The Other ◽  
Electron Micrograph ◽  
Irradiation Effects ◽  
Threefold Axis ◽  
Typical Sample ◽  
Polymer Crystals ◽  
Chain Axis

Polyoxymethylene (POM) crystals grow inside trioxane crystals which have been irradiated and heated to a temperature slightly below their melting point. Figure 1 shows a low magnification electron micrograph of a group of such POM crystals. Detailed examination at higher magnification showed that three distinct types of POM crystals grew in a typical sample. The three types of POM crystals were distinguished by the direction that the polymer chain axis in each crystal made with respect to the threefold axis of the trioxane crystal. These polyoxymethylene crystals were described previously.At low magnifications the three types of polymer crystals appeared as slender rods. One type had a hexagonal cross section and the other two types had rectangular cross sections, that is, they were ribbonlike.

Low-Temperature Thermal Expansion of Zinc Oxide. Vibrations in Zinc Oxide and Sphalerite Zinc Sulfide

1971 ◽  
Vol 4 (4) ◽  
pp. 1314-1323 ◽  
Author(s):  
B. Yates ◽  
R. F. Cooper ◽  
M. M. Kreitman
Keyword(s):  
Zinc Oxide ◽  
Thermal Expansion ◽  
Low Temperature ◽  
Zinc Sulfide

Methylene. III. Gas phase reactions with 1-chloropropane

1969 ◽  
Vol 312 (1509) ◽  
pp. 141-161 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
The Other ◽  
Gas Phase Reactions ◽  
Other Hand ◽  
Chlorine Substituent ◽  
High Degree ◽  
Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon mon­oxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

scholarly journals VIII. On the descending degenerations which follow lesions of the gyrus marginalis and gyrus fornicatus in monkeys

1889 ◽  
Vol 180 ◽  
pp. 331-354
Keyword(s):  
The Other ◽  
Post Mortem ◽  
Cerebral Lesions ◽  
Series Of Experiments ◽  
The Government ◽  
Government Grant

The following paper contains the record of an investigation into the degenerations which follow lesions of the gyrus marginalis and gyrus fornicatus in Monkeys. The work has been carried on under my direction by Mr. France, with the aid of a grant from the Government Grant Fund, and represents part of a long investigation into the degenerations which follow artificially produced cerebral lesions, the material for which has been furnished by cases operated upon in conjunction respectively with Professor V. Horsley and Dr. Sanger Brown. These cases and the physiological results of the operations have already been published in the ‘Philosophical Transactions.’ The experiments here dealt with, twelve in number, comprise only the lesions of the gyrus marginalis and gyrus fornicatus, and, with one exception (case 12), are taken from the series of experiments performed in conjunction with Mr. Horsley. Of the twelve cases, six were of removal, or attempted removal, of the gyrus marginalis, and six of removal, or attempted removal, of the gyrus fornicatus. But in only one or two instances was the lesion, as determined by post-mortem examination, exactly limited to the convolution which it was attempted to remove, for in most cases the adjacent gyrus was to a certain extent involved in the injury. This was especially the case when removal of the gyrus fornicatus had been attempted, on account of its deep situation, and the difficulty of getting at it without some manipulation of the superjacent gyrus. Nevertheless, the removal of one or the other gyrus was sufficiently complete in all the cases here selected to produce characteristic symptoms and characteristic descending degenerations.

scholarly journals XXI. On the construction of a new calorimeter for determining the radiating powers of surfaces in air; and its application to the surfaces of various mineral substances

1860 ◽  
Vol 150 ◽  
pp. 379-408
Keyword(s):  
Surrounding Medium ◽  
The Other ◽  
Absolute Amount ◽  
Present Communication ◽  
Atmospheric Air ◽  
Glass Bulb ◽  
Heated Body ◽  
Series Of Experiments ◽  
Quantity Of Heat ◽  
Limited Induction

When my paper on the Conductivity of various Substances was presented to the Society, it was intimated to me on the part of the Council of the Society, that it might be advisable to determine absolute instead of relative conductivities, the latter being alone attempted in my previous experiments. It has been partly in consequence of this intimation, as well as from the desire to make my investigations the more complete, that I have given my attention to the construction of a calorimeter which might serve for this purpose. The present communication contains a description of this instrument, with the results which it has enabled me to obtain respecting the absolute quantities of heat which emanate from the surfaces of certain substances under given conditions. 1. When a body is placed in atmospheric air (or any gas), the quantity of heat which is lost from its surface in a given time, when its temperature is higher than that of the surrounding medium, will be greater than if it were placed in a vacuum, other conditions remaining unaltered. In the latter case the heat escapes by simple radiation; in the other case a portion of the heat also escapes in consequence of the contact of the air with the surface of the heated body. Dulong and Petit ascertained by a careful series of experiments, the laws according to which the mercury contained in the bulb of a thermometer cools, or those which govern the quantity of heat which escapes from the surface of the containing bulb, when placed in a vacuum, in air, or in several kinds of gases. These experiments were made with the glass bulb naked, and also when it was silvered, so that the laws of radiation which they established were strictly in reference only to surfaces of glass and those of silver. Certain laws were identical in both these cases, and hence it was concluded, though by a limited induction, that the same laws were applicable to all other surfaces. They did not, however, give the absolute quantity of heat which, under given circumstances, and in a given time, emanates from the surfaces of the glass or silver with which they experimented. The instrument which I have constructed gives very easily this absolute amount of heat, as I believe, with very approximate accuracy.

Resolving the Lourinia armata (Claus, 1866) complex with remarks on the monophyletic status of Louriniidae, Monard 1927 (Copepoda: Harpacticoida)

Zootaxa ◽  
2021 ◽  
Vol 5051 (1) ◽  
pp. 346-386
Author(s):  
SÜPHAN KARAYTUĞ ◽  
SERDAR SAK ◽  
ALP ALPER ◽  
SERDAR SÖNMEZ
Keyword(s):  
Comparative Evaluation ◽  
Species Complex ◽  
Detailed Examination ◽  
The Other ◽  
Phylogenetic Position ◽  
Nicobar Island ◽  
Other Hand ◽  
The Family ◽  
Close Relationship ◽  
Almost All

An attempt was made to test if Lourinia armata (Claus, 1866)—as it is currently diagnosed—represents a species complex. Detailed examination and comparisons of several specimens collected from different localities suggest that L. armata indeed represents a complex of four closely related morphospecies that can be differentiated from one another by only detailed observations. One of the four species is identified as Lourinia aff. armata and the other three species are described as new to science and named as Lourinia wellsi sp. nov., L. gocmeni sp. nov., and L. aldabraensis sp. nov. Detailed review of previous species records indicates that the genus Lourinia Wilson, 1924 is distributed worldwide. Ceyloniella nicobarica Sewell, 1940, originally described from Nicobar Island and previously considered a junior subjective synonym of L. armata is reinstated as Lourinia nicobarica (Sewell, 1940) comb. nov. on the basis of the unique paddle-shaped caudal ramus seta V. It is postulated that almost all of these records are unreliable in terms of representing true Lourinia aff. armata described herein. On the other hand, the comparative evaluation of the illustrations and descriptions in the published literature indicates the presence of several new species waiting to be discovered in the genus Lourinia.                 It has been determined that, according to updated modern keys, the recent inclusion of the monotypic genus Archeolourinia Corgosinho & Schizas, 2013 in the Louriniidae is not justified since Archeolourinia shermani Corgosinho & Schizas, 2013 does not belong to this family but should be assigned to the Canthocamptidae. On the other hand, it has been argued that the exact phylogenetic position of the Louriniidae still remains problematic since none of the diagnostic characters supports the monophyly of the family within the Oligoarthra. It has also been argued that the close relationship between Louriniidae and Canthocamptidae is supported since both families share the homologous sexual dimorphism (apophysis) on P3 endopod. The most important characteristic that can possibly be used to define Louriniidae is the reduction of maxilliped.  

Specification of retinotectal connexions during development of the toad Xenopus laevis

Development ◽  
1980 ◽  
Vol 55 (1) ◽  
pp. 77-92
Author(s):  
S. C. Sharma ◽  
J. G. Hollyfield
Keyword(s):  
Xenopus Laevis ◽  
Ganglion Cell ◽  
Retinal Ganglion Cells ◽  
Optic Tectum ◽  
Ganglion Cells ◽  
The Other ◽  
Retinal Ganglion ◽  
Visual Projection ◽  
Series Of Experiments ◽  
The Right

The specification of central connexions of retinal ganglion cells was studied in Xenopus laevis. In one series of experiments, the right eye primordium was rotated 180° at embryonic stages 24–32. In the other series, the left eye was transplanted into the right orbit, and vice versa, with either 0° or 180° rotation. After metamorphosis the visual projections from the operated eye to the contralateral optic tectum were mapped electrophysiologically and compared with the normal retinotectal map. In all cases the visual projection map was rotated through the same angle as was indicated by the position of the choroidal fissure. The left eye exchanged into the right orbit retained its original axes and projected to the contralateral tectum. These results suggest that retinal ganglion cell connexions are specified before stage 24.

I. On the volumetric relations of ozone and the action of the electrical discharge on oxygen and other gases

1860 ◽  
Vol 10 ◽  
pp. 427-428 ◽  
Keyword(s):  
Electrical Discharge ◽  
The Other ◽  
Pure Oxygen ◽  
Silent Discharge ◽  
Gaseous Substance ◽  
Series Of Experiments ◽  
The One

This paper contains the full details of the authors’ experiments on the volumetric changes which occur in the formation of ozone. From three distinct series of experiments, performed by different methods, they show that when ozone is formed from pure oxygen by the action of the electrical discharge, a condensation takes place, as had already been announced in a former Note published in the 'Proceedings.’ But the condensation is much greater than the earlier experiments of the authors on the expansion by heat of electrolytic ozone had indicated. It is, in fact, so great, that if the allotropic view of the constitution of ozone be correct, the density of that body, as compared with oxygen, would be represented by a number corresponding to the density of a solid or liquid rather than that of a gaseous substance. This conclusion follows necessarily from the authors’ experiments, unless it be assumed that when ozone comes into contact with such substances as iodine, or a solution of iodide of potassium, one portion of it is changed back into common oxygen, while the remainder enters into combination, and that these portions are so related to one another, that the expansion due to the one is exactly equal to the contraction arising from the other. For the details of the experiments and of the methods of investigation employed, reference must be made to the original paper. The second part of the communication is devoted to the action of the silent discharge and of the electrical spark on other gases. Hydrogen and nitrogen undergo no change of volume when exposed to the action of either form of discharge. Cyanogen is readily decomposed by the spark, but presents so great a resistance to the passage of electricity, that the action of the silent discharge can scarcely be observed. Protoxide of nitrogen is readily attacked by both forms of discharge, with increase of volume and formation of nitrogen and hyponitric acid. Deutoxide of nitrogen exhibits the remarkable example of a gas which, under the action either of the silent discharge or of the spark, undergoes, like oxygen, a diminution of volume. It also is resolved into nitrogen and hyponitric acid. Carbonic oxide has given results of great interest; but the nature of the reaction has been only partially investigated. The silent discharge decomposes this gas with production of a substance of a bronze colour on the positive wire. The spark acts differently, destroying, as in the case of oxygen, the greater part of the contraction produced by the silent discharge. The authors are engaged in the further prosecution of this inquiry.

The Effect of Sand/Cement Ratio and Cement Grade on the Compressive Strength of Foam Concrete

2013 ◽  
Vol 405-408 ◽  
pp. 2933-2937
Author(s):  
Ji Chuan Geng ◽  
Kun Ni ◽  
Shan Qi Fang ◽  
Yun Xing Shi ◽  
Yi Ning Ding ◽  
...  
Keyword(s):  
Compressive Strength ◽  
The Other ◽  
Foam Concrete ◽  
Cement Ratio ◽  
Series Of Experiments

A series of experiments have been undertaken to investigate the effects, on compressive strength, of variable sand/cement ratios and cement grade. Ten mixtures of different s/c ratios used two kinds of cement were cast and the compressive strength at different curing ages was tested. The results indicate that the compressive strength gets lower as the s/c ratio increases for both 42.5R and 32.5R cement. For the mixtures used 32.5R cement, the 28-day compressive strength is pretty low for the s/c ratios of 1.5 and 2. The specimens used 42.5R cement have higher compressive strength than those with 32.5R cement. The compressive strength decreases from 42.5R to 32.5R cement are significantly smaller for the s/c ratios of 0.5 and 1 than the other three s/c ratios.

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