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[Kuczkowski, 1988; Morrison and Porter, 1989]. The most used accelerators are sulfenamide derivatives of 2-mercaptobenzothiazole (XVI). Actually, the use of accelerators alone usually gives only small increases in crosslinking ef ciency. Maximum ef ciency is achieved by using accelerators together with a metal oxide and fatty acid. The latter substances are referred to as the activator. Zinc oxide and stearic acid are the most commonly used. The fatty acid solubilizes the zinc oxide by forming the zinc carboxylate salt. Vulcanization is achieved in minutes using the accelerator activator combination compared to hours for sulfur alone. Analysis of the crosslinked product shows a large decrease in the extent of the wastage reactions. The crosslinking ef ciency in some systems is increased to slightly less than two sulfur atoms per crosslink. Most of the crosslinks are monosul de or disul de with very little vicinal or cyclic sul de units. Studies with model alkenes indicate that the action of accelerators is to increase the extent of sulfur substitution (crosslinking) at the allylic positions of the diene polymer [Skinner,

9-19

1972]. The mechanism of vulcanization by XVI involves the initial formation of 2,20 -dithiobisbenzothiazole (XVII) via cleavage of XVI to 2-mercaptobenzothiazole followed by oxidative coupling. 2,20 -Dithiobisbenzothiazole reacts with sulfur to form the accelerator

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The states pledged their credit to finance canal construction and turnpikes; railroad construction began in earnest; and there was speculation in Western lands Commodity prices rose moderately Government funds were transferred to private banks, and state bank notes flooded the country Foreign capital poured in freely The crisis of 1837 was one of the country s four great economic catastrophes Its immediate causes were financial trouble in England, crop failures in 1835 and 1837, and a fall in the price of cotton The government suddenly reversed its land policy and required prompt payment for public lands in hard money instead of state bank notes Security prices declined and banks suspended specie payments Although specie payments were generally resumed in 1839, depression continued for years, banks continued to fail, some states defaulted on their public improvement bonds, and commodity prices fell.

polysul de (XVIII). The accelerator polysul de reacts with the polydiene at an allylic hydrogen in a concerted process to form a rubber polysul de (XIX):

Think similarly as to soldering the switch lugs. Any excess solder will further encroach upon the circuit after it s re-mounted. You ll need to remove the four wires emerging from the circuit s top right the wires that went to the original Play and Record switches. Heat these junctions as you gently pull on the wire. The wires will come off and the junctions will be ready to accept your new wires. Use a short piece of bare wire (such as a small section of a lead clipped from a resistor) for the jumper (see Figure 30-4). Solder one end to one side of its connection. Let it cool and then bend it down against the remaining connection point. Clip it to exact length (no overhang) and quickly solder it to the second point, completing its placement. Note that the wire that connects all the Picture and Pattern switches to each other does not connect to the circuit anywhere, as it would if it were the common wire in the 1 to X bend (see 9). Here, you re connecting switches to each other in many combinations rather than all to a single circuit point as in the 1 to X bend. You might want to study both circuits until you understand how they work. If you already understand the 1 to X bend, think of this bend, accordingly, as the X to X bend. Each of these two bends will be frequent discoveries within bending. See these two circuits side-by-side in Appendix A, along with further explanation. Line-output circuitry is the same in all projects if not otherwise noted. See the line-output scheme in Appendix A and assume that the speaker in the diagram is the speaker in the project.

9-20

It was not until 1845 that a substantial business recovery occurred Prices rose somewhat The Mexican War of 1846 created no serious pressures The European financial disturbances of 1847 1848 led to only a brief setback Following the California gold strike of 1848, there was a period of great prosperity Banking expanded and prices rose There was another and greater land boom and railroad construction became massive (484) A brief panic on the New York Stock Exchange in 1854, accompanied by tight money and failures, did not spread out to depress the general economy The panic of 1857 was in part a reflection of economic disturbances in Europe There was a sharp decline in security prices and fourteen railroads went into bankruptcy Money became very tight and banks again suspended specie payments In 1858 recovery was rapid and the country was prosperous up to the tragic events of 1860 1861.

Crosslinking occurs by the corresponding reaction between XIX and the polydiene:

9-21

The action of zinc in increasing the ef ciency and rate of crosslinking is thought to involve chelation of zinc with the accelerator as well as species XVIII and XIX. Zinc polysul de compounds such as XX are also likely intermediates. Zinc chelated to sulfur or as zinc sul de bonds probably facilitate cleavage of sulfur sulfur bonds in the concerted reactions described by Eqs. 9-20 and 9-21.

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