Creative Chemistry - Part 16
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Part 16

We have to carry on this eternal conflict against rust because oxygen is the most ubiquitous of the elements and iron can only escape its ardent embraces by hiding away in the center of the earth. The united elements, known to the chemist as iron oxide and to the outside world as rust, are among the commonest of compounds and their colors, yellow and red like the Spanish flag, are displayed on every mountainside. From the time of Tubal Cain man has ceaselessly labored to divorce these elements and, having once separated them, to keep them apart so that the iron may be retained in his service. But here, as usual, man is fighting against nature and his gains, as always, are only temporary. Sooner or later his vigilance is circ.u.mvented and the metal that he has extricated by the fiery furnace returns to its natural affinity. The flint arrowheads, the bronze spearpoints, the gold ornaments, the wooden idols of prehistoric man are still to be seen in our museums, but his earliest steel swords have long since crumbled into dust.

Every year the blast furnaces of the world release 72,000,000 tons of iron from its oxides and every year a large part, said to be a quarter of that amount, reverts to its primeval forms. If so, then man after five thousand years of metallurgical industry has barely got three years ahead of nature, and should he cease his efforts for a generation there would be little left to show that man had ever learned to extract iron from its ores. The old question, "What becomes of all the pins?" may be as well asked of rails, pipes and threshing machines. The end of all iron is the same. However many may be its metamorphoses while in the service of man it relapses at last into its original state of oxidation.

To save a pound of iron from corrosion is then as much a benefit to the world as to produce another pound from the ore. In fact it is of much greater benefit, for it takes four pounds of coal to produce one pound of steel, so whenever a piece of iron is allowed to oxidize it means that four times as much coal must be oxidized in order to replace it.

And the beds of coal will be exhausted before the beds of iron ore.

If we are ever to get ahead, if we are to gain any respite from this enormous waste of labor and natural resources, we must find ways of preventing the iron which we have obtained and fashioned into useful tools from being lost through oxidation. Now there is only one way of keeping iron and oxygen from uniting and that is to keep them apart. A very thin dividing wall will serve for the purpose, for instance, a film of oil. But ordinary oil will rub off, so it is better to cover the surface with an oil-like linseed which oxidizes to a hard elastic and adhesive coating. If with linseed oil we mix iron oxide or some other pigment we have a paint that will protect iron perfectly so long as it is unbroken. But let the paint wear off or crack so that air can get at the iron, then rust will form and spread underneath the paint on all sides. The same is true of the porcelain-like enamel with which our kitchen iron ware is nowadays coated. So long as the enamel holds it is all right but once it is broken through at any point it begins to scale off and gets into our food.

Obviously it would be better for some purposes if we could coat our iron with another and less easily oxidized metal than with such dissimilar substances as paint or porcelain. Now the nearest relative to iron is nickel, and a layer of this of any desired thickness may be easily deposited by electricity upon any surface however irregular.

Nickel takes a bright polish and keeps it well, so nickel plating has become the favorite method of protection for small objects where the expense is not prohibitive. Copper plating is used for fine wires. A sheet of iron dipped in melted tin comes out coated with a thin adhesive layer of the latter metal. Such tinned plate commonly known as "tin" has become the favorite material for pans and cans. But if the tin is scratched the iron beneath rusts more rapidly than if the tin were not there, for an electrolytic action is set up and the iron, being the negative element of the couple, suffers at the expense of the tin.

With zinc it is quite the opposite. Zinc is negative toward iron, so when the two are in contact and exposed to the weather the zinc is oxidized first. A zinc plating affords the protection of a Swiss Guard, it holds out as long as possible and when broken it perishes to the last atom before it lets the oxygen get at the iron. The zinc may be applied in four different ways. (1) It may be deposited by electrolysis as in nickel plating, but the zinc coating is more apt to be porous. (2) The sheets or articles may be dipped in a bath of melted zinc. This gives us the familiar "galvanized iron," the most useful and when well done the most effective of rust preventives. Besides these older methods of applying zinc there are now two new ones. (3) One is the Schoop process by which a wire of zinc or other metal is fed into an oxy-hydrogen air blast of such heat and power that it is projected as a spray of minute drops with the speed of bullets and any object subjected to the bombardment of this metallic mist receives a coating as thick as desired. The zinc spray is so fine and cool that it may be received on cloth, lace, or the bare hand. The Schoop metallizing process has recently been improved by the use of the electric current instead of the blowpipe for melting the metal. Two zinc wires connected with any electric system, preferably the direct, are fed into the "pistol." Where the wires meet an electric arc is set up and the melted zinc is sprayed out by a jet of compressed air. (4) In the Sherardizing process the articles are put into a tight drum with zinc dust and heated to 800 F.

The zinc at this temperature attacks the iron and forms a series of alloys ranging from pure zinc on the top to pure iron at the bottom of the coating. Even if this cracks in part the iron is more or less protected from corrosion so long as any zinc remains. Aluminum is used similarly in the calorizing process for coating iron, copper or bra.s.s.

First a surface alloy is formed by heating the metal with aluminum powder. Then the temperature is raised to a high degree so as to cause the aluminum on the surface to diffuse into the metal and afterwards it is again baked in contact with aluminum dust which puts upon it a protective plating of the pure aluminum which does not oxidize.

[Ill.u.s.tration: PHOTOMICROGRAPHS SHOWING THE STRUCTURE OF STEEL MADE BY PROFESSOR E.G. MARTIN OF PURDUE UNIVERSITY

1. Cold-worked steel showing ferrite and sorbite (enlarged 500 times)

2. Steel showing pearlite crystals (enlarged 500 times)

3. Structure characteristic of air-cooled steel (enlarged 50 times)

4. The triangular structure characteristic of cast steel showing ferrite and pearlite (enlarged 50 times)]

[Ill.u.s.tration: Courtesy of E.G. Mahin

THE MICROSCOPIC STRUCTURE OF METALS

1. Malleabilized casting; temper carbon in ferrite (enlarged 50 times)

2. Type metal; lead-antimony alloy in matrix of lead (enlarged 100 times)

3. Gray cast iron; carbon as graphite (enlarged 500 times)

4. Steel composed of cement.i.te (white) and pearlite (black) (enlarged 50 times)]

Another way of protecting iron ware from rusting is to rust it. This is a sort of prophylactic method like that adopted by modern medicine where inoculation with a mild culture prevents a serious attack of the disease. The action of air and water on iron forms a series of compounds and mixtures of them. Those that contain least oxygen are hard, black and magnetic like iron itself. Those that have most oxygen are red and yellow powders. By putting on a tight coating of the black oxide we can prevent or hinder the oxidation from going on into the pulverulent stage. This is done in several ways. In the Bower-Barff process the articles to be treated are put into a closed retort and a current of superheated steam pa.s.sed through for twenty minutes followed by a current of producer gas (carbon monoxide), to reduce any higher oxides that may have been formed. In the Gesner process a current of gasoline vapor is used as the reducing agent. The blueing of watch hands, buckles and the like may be done by dipping them into an oxidizing bath such as melted saltpeter. But in order to afford complete protection the layer of black oxide must be thickened by repeating the process which adds to the time and expense. This causes a slight enlargement and the high temperature often warps the ware so it is not suitable for nicely adjusted parts of machinery and of course tools would lose their temper by the heat.

A new method of rust proofing which is free from these disadvantages is the phosphate process invented by Thomas Watts Coslett, an English chemist, in 1907, and developed in America by the Parker Company of Detroit. This consists simply in dipping the sheet iron or articles into a tank filled with a dilute solution of iron phosphate heated nearly to the boiling point by steam pipes. Bubbles of hydrogen stream off rapidly at first, then slower, and at the end of half an hour or longer the action ceases, and the process is complete. What has happened is that the iron has been converted into a basic iron phosphate to a depth depending upon the density of articles processed. Any one who has studied elementary qualitative a.n.a.lysis will remember that when he added ammonia to his "unknown" solution, iron and phosphoric acid, if present, were precipitated together, or in other words, iron phosphate is insoluble except in acids. Therefore a superficial film of such phosphate will protect the iron underneath except from acids. This film is not a coating added on the outside like paint and enamel or tin and nickel plate. It is therefore not apt to scale off and it does not increase the size of the article. No high heat is required as in the Sherardizing and Bower-Barff processes, so steel tools can be treated without losing their temper or edge.

The deposit consisting of ferrous and ferric phosphates mixed with black iron oxide may be varied in composition, texture and color. It is ordinarily a dull gray and oiling gives a soft mat black more in accordance with modern taste than the shiny nickel plating that delighted our fathers. Even the military nowadays show more quiet taste than formerly and have abandoned their glittering accoutrements.

The phosphate bath is not expensive and can be used continuously for months by adding more of the concentrated solution to keep up the strength and removing the sludge that is precipitated. Besides the iron the solution contains the phosphates of other metals such as calcium or strontium, manganese, molybdenum, or tungsten, according to the particular purpose. Since the phosphating solution does not act on nickel it may be used on articles that have been partly nickel-plated so there may be produced, for instance, a bright raised design against a dull black background. Then, too, the surface left by the Parker process is finely etched so it affords a good attachment for paint or enamel if further protection is needed. Even if the enamel does crack, the iron beneath is not so apt to rust and scale off the coating.

These, then, are some of the methods which are now being used to combat our eternal enemy, the rust that doth corrupt. All of them are useful in their several ways. No one of them is best for all purposes. The claim of "rust-proof" is no more to be taken seriously than "fire-proof." We should rather, if we were finical, have to speak of "rust-resisting"

coatings as we do of "slow-burning" buildings. Nature is insidious and unceasing in her efforts to bring to ruin the achievements of mankind and we need all the weapons we can find to frustrate her destructive determination.

But it is not enough for us to make iron superficially resistant to rust from the atmosphere. We should like also to make it so that it would withstand corrosion by acids, then it could be used in place of the large and expensive platinum or porcelain evaporating pans and similar utensils employed in chemical works. This requirement also has been met in the non-corrosive forms of iron, which have come into use within the last five years. One of these, "tantiron," invented by a British metallurgist, Robert N. Lennox, in 1912, contains 15 per cent. of silicon. Similar products are known as "duriron" and "Buflokast" in America, "metilure" in France, "ileanite" in Italy and "neutraleisen" in Germany. It is a silvery-white close-grained iron, very hard and rather brittle, somewhat like cast iron but with silicon as the main additional ingredient in place of carbon. It is difficult to cut or drill but may be ground into shape by the new abrasives. It is rustproof and is not attacked by sulfuric, nitric or acetic acid, hot or cold, diluted or concentrated. It does not resist so well hydrochloric acid or sulfur dioxide or alkalies.

The value of iron lies in its versatility. It is a dozen metals in one.

It can be made hard or soft, brittle or malleable, tough or weak, resistant or flexible, elastic or pliant, magnetic or non-magnetic, more or less conductive to electricity, by slight changes of composition or mere differences of treatment. No wonder that the medieval mind ascribed these mysterious transformations to witchcraft. But the modern micrometallurgist, by etching the surface of steel and photographing it, shows it up as composite as a block of granite. He is then able to pick out its component minerals, ferrite, austenite, martensite, pearlite, graphite, cement.i.te, and to show how their abundance, shape and arrangement contribute to the strength or weakness of the specimen. The last of these const.i.tuents, cement.i.te, is a definite chemical compound, an iron carbide, Fe_{3}C, containing 6.6 per cent. of carbon, so hard as to scratch gla.s.s, very brittle, and imparting these properties to hardened steel and cast iron.

With this knowledge at his disposal the iron-maker can work with his eyes open and so regulate his melt as to cause these various const.i.tuents to crystallize out as he wants them to. Besides, he is no longer confined to the alloys of iron and carbon. He has ransacked the chemical dictionary to find new elements to add to his alloys, and some of these rarities have proved to possess great practical value.

Vanadium, for instance, used to be put into a fine print paragraph in the back of the chemistry book, where the cla.s.s did not get to it until the term closed. Yet if it had not been for vanadium steel we should have no Ford cars. Tungsten, too, was relegated to the rear, and if the student remembered it at all it was because it bothered him to understand why its symbol should be W instead of T. But the student of today studies his lesson in the light of a tungsten wire and relieves his mind by listening to a phonograph record played with a "tungs-tone"

stylus. When I was a.s.sistant in chemistry an "a.n.a.lysis" of steel consisted merely in the determination of its percentage of carbon, and I used to take Sat.u.r.day for it so I could have time enough to complete the combustion. Now the chemists of a steel works' laboratory may have to determine also the tungsten, chromium, vanadium, t.i.tanium, nickel, cobalt, phosphorus, molybdenum, manganese, silicon and sulfur, any or all of them, and be spry about it, because if they do not get the report out within fifteen minutes while the steel is melting in the electrical furnace the whole batch of 75 tons may go wrong. I'm glad I quit the laboratory before they got to speeding up chemists so.

The quality of the steel depends upon the presence and the relative proportions of these ingredients, and a variation of a tenth of 1 per cent. in certain of them will make a different metal out of it. For instance, the steel becomes stronger and tougher as the proportion of nicked is increased up to about 15 per cent. Raising the percentage to 25 we get an alloy that does not rust or corrode and is non-magnetic, although both its component metals, iron and nickel, are by themselves attracted by the magnet. With 36 per cent. nickel and 5 per cent.

manganese we get the alloy known as "invar," because it expands and contracts very little with changes of temperature. A bar of the best form of invar will expand less than one-millionth part of its length for a rise of one degree Centigrade at ordinary atmospheric temperature. For this reason it is used in watches and measuring instruments. The alloy of iron with 46 per cent. nickel is called "platinite" because its rate of expansion and contraction is the same as platinum and gla.s.s, and so it can be used to replace the platinum wire pa.s.sing through the gla.s.s of an electric light bulb.

A manganese steel of 11 to 14 per cent. is too hard to be machined. It has to be cast or ground into shape and is used for burglar-proof safes and armor plate. Chrome steel is also hard and tough and finds use in files, ball bearings and projectiles. t.i.tanium, which the iron-maker used to regard as his implacable enemy, has been drafted into service as a deoxidizer, increasing the strength and elasticity of the steel. It is reported from France that the addition of three-tenths of 1 per cent. of zirconium to nickel steel has made it more resistant to the German perforating bullets than any steel hitherto known. The new "stainless"

cutlery contains 12 to 14 per cent. of chromium.

With the introduction of harder steels came the need of tougher tools to work them. Now the virtue of a good tool steel is the same as of a good man. It must be able to get hot without losing its temper. Steel of the old-fashioned sort, as everybody knows, gets its temper by being heated to redness and suddenly cooled by quenching or plunging it into water or oil. But when the point gets heated up again, as it does by friction in a lathe, it softens and loses its cutting edge. So the necessity of keeping the tool cool limited the speed of the machine.

But about 1868 a Sheffield metallurgist, Robert F. Mushet, found that a piece of steel he was working with did not require quenching to harden it. He had it a.n.a.lyzed to discover the meaning of this peculiarity and learned that it contained tungsten, a rare metal unrecognized in the metallurgy of that day. Further investigation showed that steel to which tungsten and manganese or chromium had been added was tougher and retained its temper at high temperature better than ordinary carbon steel. Tools made from it could be worked up to a white heat without losing their cutting power. The new tools of this type invented by "Efficiency" Taylor at the Bethlehem Steel Works in the nineties have revolutionized shop practice the world over. A tool of the old sort could not cut at a rate faster than thirty feet a minute without overheating, but the new tungsten tools will plow through steel ten times as fast and can cut away a ton of the material in an hour. By means of these high-speed tools the United States was able to turn out five times the munitions that it could otherwise have done in the same time. On the other hand, if Germany alone had possessed the secret of the modern steels no power could have withstood her. A slight superiority in metallurgy has been the deciding factor in many a battle.

Those of my readers who have had the advantages of Sunday school training will recall the case described in I Samuel 13:19-22.

By means of these new metals armor plate has been made invulnerable--except to projectiles pointed with similar material.

Flying has been made possible through engines weighing no more than two pounds per horse power. The cylinders of combustion engines and the casing of cannon have been made to withstand the unprecedented pressure and corrosive action of the fiery gases evolved within. Castings are made so hard that they cannot be cut--save with tools of the same sort.

In the high-speed tools now used 20 or 30 per cent, of the iron is displaced by other ingredients; for example, tungsten from 14 to 25 per cent., chromium from 2 to 7 per cent., vanadium from 1/2 to 1-1/2 per cent., carbon from 6 to 8 per cent., with perhaps cobalt up to 4 per cent. Molybdenum or uranium may replace part of the tungsten.

Some of the newer alloys for high-speed tools contain no iron at all.

That which bears the poetic name of star-stone, stellite, is composed of chromium, cobalt and tungsten in varying proportions. Stellite keeps a hard cutting edge and gets tougher as it gets hotter. It is very hard and as good for jewelry as platinum except that it is not so expensive.

Cooperite, its rival, is an alloy of nickel and zirconium, stronger, lighter and cheaper than stellite.

Before the war nearly half of the world's supply of tungsten ore (wolframite) came from Burma. But although Burma had belonged to the British for a hundred years they had not developed its mineral resources and the tungsten trade was monopolized by the Germans. All the ore was shipped to Germany and the British Admiralty was content to buy from the Germans what tungsten was needed for armor plate and heavy guns. When the war broke out the British had the ore supply, but were unable at first to work it because they were not familiar with the processes.

Germany, being short of tungsten, had to sneak over a little from Baltimore in the submarine _Deutschland_. In the United States before the war tungsten ore was selling at $6.50 a unit, but by the beginning of 1916 it had jumped to $85 a unit. A unit is 1 per cent. of tungsten trioxide to the ton, that is, twenty pounds. Boulder County, Colorado, and San Bernardino, California, then had mining booms, reminding one of older times. Between May and December, 1918, there was manufactured in the United States more than 45,500,000 pounds of tungsten steel containing some 8,000,000 pounds of tungsten.

If tungsten ores were more abundant and the metal more easily manipulated, it would displace steel for many purposes. It is harder than steel or even quartz. It never rusts and is insoluble in acids. Its expansion by heat is one-third that of iron. It is more than twice as heavy as iron and its melting point is twice as high. Its electrical resistance is half that of iron and its tensile strength is a third greater than the strongest steel. It can be worked into wire .0002 of an inch in diameter, almost too thin to be seen, but as strong as copper wire ten times the size.

The tungsten wires in the electric lamps are about .03 of an inch in diameter, and they give three times the light for the same consumption of electricity as the old carbon filament. The American manufacturers of the tungsten bulb have very appropriately named their lamp "Mazda" after the light G.o.d of the Zoroastrians. To get the tungsten into wire form was a problem that long baffled the inventors of the world, for it was too refractory to be melted in ma.s.s and too brittle to be drawn. Dr.

W.D. Coolidge succeeded in accomplishing the feat in 1912 by reducing the tungstic acid by hydrogen and molding the metallic powder into a bar by pressure. This is raised to a white heat in the electric furnace, taken out and rolled down, and the process repeated some fifty times, until the wire is small enough so it can be drawn at a red heat through diamond dies of successively smaller apertures.

The German method of making the lamp filaments is to squirt a mixture of tungsten powder and thorium oxide through a perforated diamond of the desired diameter. The filament so produced is drawn through a chamber heated to 2500 C. at a velocity of eight feet an hour, which crystallizes the tungsten into a continuous thread.

The first metallic filament used in the electric light on a commercial scale was made of tantalum, the metal of Tantalus. In the period 1905-1911 over 100,000,000 tantalus lamps were sold, but tungsten displaced them as soon as that metal could be drawn into wire.

A recent rival of tungsten both as a filament for lamps and hardener for steel is molybdenum. One pound of this metal will impart more resiliency to steel than three or four pounds of tungsten. The molybdenum steel, because it does not easily crack, is said to be serviceable for armor-piercing sh.e.l.ls, gun linings, air-plane struts, automobile axles and propeller shafts. In combination with its rival as a tungsten-molybdenum alloy it is capable of taking the place of the intolerably expensive platinum, for it resists corrosion when used for spark plugs and tooth plugs. European steel men have taken to molybdenum more than Americans. The salts of this metal can be used in dyeing and photography.

Calcium, magnesium and aluminum, common enough in their compounds, have only come into use as metals since the invention of the electric furnace. Now the photographer uses magnesium powder for his flashlight when he wants to take a picture of his friends inside the house, and the aviator uses it when he wants to take a picture of his enemies on the open field. The flares prepared by our Government for the war consist of a sheet iron cylinder, four feet long and six inches thick, containing a stick of magnesium attached to a tightly rolled silk parachute twenty feet in diameter when expanded. The whole weighed 32 pounds. On being dropped from the plane by pressing a b.u.t.ton, the rush of air set spinning a pinwheel at the bottom which ignited the magnesium stick and detonated a charge of black powder sufficient to throw off the case and release the parachute. The burning flare gave off a light of 320,000 candle power lasting for ten minutes as the parachute slowly descended.

This illuminated the ground on the darkest night sufficiently for the airman to aim his bombs or to take photographs.

The addition of 5 or 10 per cent. of magnesium to aluminum gives an alloy (magnalium) that is almost as light as aluminum and almost as strong as steel. An alloy of 90 per cent. aluminum and 10 per cent.

calcium is lighter and harder than aluminum and more resistant to corrosion. The latest German airplane, the "Junker," was made entirely of duralumin. Even the wings were formed of corrugated sheets of this alloy instead of the usual doped cotton-cloth. Duralumin is composed of about 85 per cent. of aluminum, 5 per cent. of copper, 5 per cent. of zinc and 2 per cent. of tin.

When platinum was first discovered it was so cheap that ingots of it were gilded and sold as gold bricks to unwary purchasers. The Russian Government used it as we use nickel, for making small coins. But this is an exception to the rule that the demand creates the supply. Platinum is really a "rare metal," not merely an unfamiliar one. Nowhere except in the Urals is it found in quant.i.ty, and since it seems indispensable in chemical and electrical appliances, the price has continually gone up.

Russia collapsed into chaos just when the war work made the heaviest demand for platinum, so the governments had to put a stop to its use for jewelry and photography. The "gold brick" scheme would now have to be reversed, for gold is used as a cheaper metal to "adulterate" platinum.

All the members of the platinum family, formerly ignored, were pressed into service, palladium, rhodium, osmium, iridium, and these, alloyed with gold or silver, were employed more or less satisfactorily by the dentist, chemist and electrician as subst.i.tutes for the platinum of which they had been deprived. One of these alloys, composed of 20 per cent. palladium and 80 per cent. gold, and bearing the telescoped name of "palau" (palladium au-rum) makes very acceptable crucibles for the laboratory and only costs half as much as platinum. "Rhotanium" is a similar alloy recently introduced. The points of our gold pens are tipped with an osmium-iridium alloy. It is a pity that this family of n.o.ble metals is so restricted, for they are unsurpa.s.sed in tenacity and incorruptibility. They could be of great service to the world in war and peace. As the "Bad Child" says in his "Book of Beasts":