Diamonds – the Russian Connection

Diamonds – the Russian Connection

Last week”s column concerned Hedy Lamarr, a glamour queen of

the 1930s and 1940s. Later, another sex symbol, Marilyn

Monroe, sang a song about diamonds being a girl”s best friend.

A few weeks ago I watched a Nova program on Public

Television and sure enough, a film clip of Marilyn”s song was

included. (I just saw the same film clip on “Sunday Morning”.)

You”re right in surmising that the Nova program was about

diamonds. The DeBeers hold on the diamond market has existed

for well over a century. That virtual monopoly is what keeps the

supply and demand for diamonds under control and allows the

gems to maintain their value. In several of his Hott Spott

columns, Brian Trumbore has written in depth about the DeBeers

history and concerns that Russia may jump ship and sell outside

the DeBeers market. Russia could flood the market with

diamonds, undercutting the price and destabilizing the whole

diamond market.

One reason that Russia can threaten the stability of the diamond

market is that Russia has diamond mines of its own, the output of

which Russia has been selling to DeBeers. Along with other

countries doing the same thing, this has allowed DeBeers to dole

out diamonds as the market demands. But there is another

potential problem of concern in Russia. This was the subject of

the Nova program – synthetic diamonds. It”s hard to tell, at least

for me, whether some of the sparkling jewelry adorning women

today contains real diamonds or the fake stuff. A jeweler, of

course, would have no problem distinguishing diamonds from

today”s lookalikes, which are completely different materials.

These lookalikes are typically cubic zirconia or moissanite and

are not synthetic diamonds. They are chemical compounds, not

simply the element carbon. As we”ve discussed on a number of

occasions here, diamond is just plain carbon, the same carbon

that is the graphite in your “lead” pencil. We”ve talked about

graphite having a layered structure with the bonds between the

layers being so weak that the graphite easily slides layer by layer

onto your sheet of paper as you write. In graphite, each carbon is

bonded strongly to three other carbons in the layer.

In diamond the carbon is not layered but each carbon is bonded

to four other carbons in a very stable structure; hence its

hardness. The hardness of diamond makes it extremely valuable

as an abrasive for cutting tools. I used diamond-coated wheels

daily during certain periods of my Bell Labs career to cut glass

or quartz tubing for my experiments. The small diamond chips

are bonded to the wheel, which rotates like a rotary bench saw

used to cut wood.

The Nova program traced the history of synthetic diamond back

to the days of World War II. Industrial diamonds for cutting

tools to fashion such items as airplane parts were critical to the

war effort. Sources in South Africa were deemed unreliable due

to submarine warfare and other aspects of war. Accordingly, an

effort was funded to try to grow synthetic diamond. It was well

known that diamond is the stable form of carbon at very high

pressure. The problem was how to take ordinary graphite and

put it under high pressure and make it convert to diamond. Not

only was high pressure needed, but also a high temperature was

required to loosen the carbon bonds so the carbon atoms could

rearrange themselves into the diamond structure. Two General

Electric scientists, H. Tracy Hall and Herbert Strong, were

assigned to the task and they went to work. They squeezed and

heated the graphite for several years without any success. Those

bonds of the carbons in the layers of graphite just wouldn”t be

broken.

Stymied, they decided that the only way to accomplish the task

was to dissolve the graphite into solution. They hoped that

would break up the graphite structure and the carbon atoms

would be free to move around and then precipitate out of solution

in the diamond form at high pressure. This approach may have

been prompted by the finding of fine diamonds in the awesome

impact crater of that meteorite in Arizona. Those tiny diamonds

were found in connection with a metallic ore. The feeling was

that the metallic ore had melted and dissolved the carbon. Hall

and Strong added some metallic stuff to the graphite in their high

pressure, high temperature machine and, Voila! Tiny crystals of

diamond were formed.

Some years later at Bell Labs, I had two brilliant ideas. One was

to try to make diamond by passing benzene or some other

organic vapors over a diamond seed crystal. The idea was to

trick the carbon atoms into growing on the seed diamond even

though that was not the stable form of carbon at ordinary

pressures. It didn”t work. However, John Angus at Case

Western carried out a similar type experiment but with hydrogen

added. What do you know? Diamonds! So much for my idea.

My second brilliant idea was to take a diamond seed crystal (it

only cost about twenty bucks), seal it in a quartz tube with some

graphite and some tin. I then put the tube in a furnace positioned

so the top of the tube was hot and the bottom at a lower

temperature. The idea was that the tin would melt, the graphite,

which floats in tin, would dissolve and travel down to the cooler

seed at the bottom of the tube. Because the graphite is less

soluble at the lower temperature, the carbon would precipitate

out of the solution and would be tricked into growing on the seed

as diamond. It turned out my diamond seed dissolved! Another

brilliant idea down the drain.

So, what did I see on the Nova program? Would you believe that

this Russian, Boris Feigelson, and his colleagues are putting

graphite in a vessel with some kind of molten metal and they

have a diamond seed at the bottom. The only thing different

from the experiment of yours truly is that they have this vessel in

a pressure chamber. And what happens? They grow gem

quality diamonds of a carat or more! Look out DeBeers! When I

saw this on Nova, I must admit to uttering a “Damn!” However,

I consoled myself with the fact I didn”t have a high-pressure

system to perform such an experiment.

The only problem with their first diamonds – they were yellow!

Obviously, DeBeers breathed a sigh of relief. It would be easy to

tell diamonds mined from nature from these synthetic diamonds

just by looking at them. But then the reason for the yellow color

was determined to be something quite simple – nitrogen in the

diamond. In the light emitting diode business at Bell Labs, we

used nitrogen in gallium phosphide to give us green light, a good

thing. It turns out that in nature, over a period of millions or

billions of years, the nitrogen atoms gradually move around in

the diamond and clump together. When the nitrogen atoms

clump together they no longer give a yellow color. At GE they

showed that the synthetic yellow diamonds could be made less

yellow by heating for prolonged periods. However, the time

required to get colorless diamonds would be prohibitively long

and the process would be too expensive. DeBeers is happy!

Obviously, the way to get rid of the yellow color is to get rid of

the nitrogen. In the semiconductor game we often worked with a

principle known as “gettering” to get rid of an unwanted

impurity. This would typically involve using a metal, usually a

liquid metal, that would getter, or gobble up the offending

element, often copper in the early days. Wouldn”t you know, the

Nova program says the Russians have added aluminum to their

secret solvent and the aluminum acts as a getter by reacting with

nitrogen. Result – colorless diamonds! Now DeBeers is really

sweating!

In the program, the background music at this point was Henry

Mancini”s theme from “The Pink Panther”, appropriate for the cat

and mouse game going on between DeBeers and the Russians.

With colorless synthetic diamonds, the question is how to tell

them from the natural ones. The DeBeers counter sleuths have

indeed come up with a method using ultraviolet light of a certain

frequency and intensity. The synthetic diamonds glow under this

wavelength light while the natural diamonds stay dark. When

the UV light is turned off, the synthetic diamonds phosphoresce.

That is, they continue to glow for a several seconds. Advantage

DeBeers.

Why do the synthetic diamonds phosphoresce? Without going

into detail, it”s related to how the crystals of diamond grow.

This growth property differs in nature from the property found in

the synthetic diamonds. Naturally, the Russians are working on

this problem. Another complication for DeBeers – an American,

retired general Carter Clarke, heads a company that has invested

in the Russian technology. He was interviewed on the Nova

program and posed a very appropriate question. If a woman has

a choice between two pieces of diamond jewelry, one containing

very expensive natural diamond and another, identical but much

cheaper piece containing synthetic diamond, which will she

choose? Remember that the only difference will be that the

synthetic piece will phosphoresce under UV light. General

Clarke is betting that the choice will most often be the synthetic

choice.

The above example is obviously a sexist one. Males must also

buy a fair amount of jewelry, mostly for the ladies I would

presume. Would a male be intimidated by the possibility the

recipient of his gift might have a UV light source handy? What

would your choice be? The fate of the world diamond market

and the value of all your precious jewelry could depend upon it!

Allen F. Bortrum