Method to make Yttrium-barium-copper oxide superconductor(YBCO)

There are a number of methods of producing ceramic superconductors like this, but the simplest is the
so-called “shake and bake” method, which involves a four step process:
1.Mixing the chemicals; 2. Calcination(the initial firing); 3. The intermediate firing(s) (oxygen
annealings); 4. The final oxygen annealing.

The number of intermediate firings and the length of the firings are largely up to the user. In general, the
more intermediate firings, and the longer the duration of the firings under oxygen flow, the better the
superconductor. But definite signs of superconductivity can usually be obtained without any
intermediate firing at all. In fact, if the initial mixing of the chemicals is sufficiently thorough, the
intermediate firing is not necessary at all.
Mixing the chemicals
The starting mix is a grey powder made by thoroughly mixing yttrium oxide, barium carbonate and
cuprix oxide in the ratios 1:2:3 (This superconductor is often referred to as “1-2-3” as a result) –
* Yttrium Oxide, Y2O3 – 11.29 grams
* Barium Carbonate, BaCO3 – 39.47 grams
* Cupric Oxide, CuO – 23.86 gram
2. Calcination
For the initial heat treatment, called calcination, the mix is heated at 925-950 degrees Celsius for about
18-24 hours. This first treatment may be done in a crucible or evaporating dish made of alumina or of a
good grade of laboratory porcelain. This forms the basic crystal structure of YBa2Cu3O6.5, and gets rid of
the carbon dioxide from the barium carbonate. (Barium carbonate is used instead of barium oxide
because barium oxide of any reasonable purity is difficult to obtain. Also, exposing barium oxide to air
tends to quickly convert much of it to barium carbonate and barium hydroxide.) The result of this first
firing is a porous black or very dark gray clump. The coloration should be fairly even.
An uneven green coloration is an indication that the powders are not as thoroughly mixed as they should
have been, and that extra time and care should be taken to insure thorough grinding and mixing on
subsequent steps. The material will seem to shrink rather dramatically during the initial firing as it loses
its carbon dioxide and becomes much denser than the original powder mix.
3. Intermediate firing(s)
The porous black clump is ground into a fine powder and placed in the furnace in an alumina dish. After
the furnace temperature reaches about 500 degrees Celsius, begin a slow flow of oxygen into the furnace.
This heat treatment under oxygen flow is called oxygen annealing. A final furnace temperature of 925 to
975 degrees Celsius is recommended for the intermediate firings. A temperature much higher than this
will result in a material that is much harder to re-grind. Temperatures above 1030 degrees Celsius may
destroy the crystal structure.After the mix has heated in the furnace for at least 18 hours at 925-975
degrees Celsius, reduce the temperature slowly. If you plan to test the sample for superconductivity after
this firing, the cooling rate must be no more than 100 degrees per hour until 400 degrees Celsius is
reached. The rate of cooling from 400 degrees down to room temperature can be increased to about 200
degrees per hour. If you do not plan to test for superconductivity after this firing, a cooling rate in excess
of 100 degrees per hour may be used; however a cooling rate in excess of 250 degrees per hour is not
recommended. Do not remove the oxygen flow until the indicated furnace temperature has fallen below
400 degrees Celsius.
The material should be thoroughly re-ground in a mortar and pestle (or similar device) between each
firing. (If, after an intermediate firing, there is some green coloration in the resultant disk, it is important
to take extra time and care in re-grinding and mixing the material before the next firing.) Problems that
occur in the mixing and grinding process in any of these steps are often due to hard, coarse particles
being mixed in with the finely powder material. An ordinary kitchen tea strainer can come in handy at
this point to separate the coarser particles or lumps so they may be ground separately. IMPORTANT: If
you an ordinary tea strainer, make sure it is made of a non-magnetic material, or make sure you are
satisfied that none of the material in the sifter or strainer will contaminate the chemicals.
Even very small quantities of magnetic materials in the chemical mix can diminish or destroy the
potential superconductivity. (It is also for this reason that “ceramic grade” chemicals, which tend to have
iron impurities, are not often usable for making superconductors.) Shortcuts in grinding the materials,
such as using an electric coffee grinder, often contaminate the compound with elements that destroy the
superconducting properties. Some contaminates will destroy superconductivity in very tiny amounts. To
keep your chances of success high, grinding with a good-quality mortar and pestle is the best method.
This manual grinding can be an arduous process, but the results are worth the trouble.
4. The final oxygen annealing
The sample should be thoroughly reground, and the resultant black powder placed back in the alumina
dish. The thickness of the layer of loose powder in the dish should match the desired thickness of the final
superconducting disk. For this final firing, the powder should be as finely-ground and as densely-packed
as possible. Do NOT pack the powder into the dish by pressing on it from the top (as this can makes the
superconductor tend to stick to the alumina dish). Better results can usually be obtained by tapping the
alumina dish with a pestle or a similar object so that the particles of the mix settle together in an evenly
packed disk.
For this final heat treatment, heat the sample to between 950 degrees and 1000 degrees Celsius for about
18 hours. The higher temperature is better, but be sure of the accuracy of your temperature indicator
before getting too close to 1000 degrees. Temperatures above 1020 degrees risk decomposition of the
crystal structure and the possiblity of the material sticking to the alumina dish. On the other hand, a final
oxygen annealing at only 950 degrees Celsius will yield a superconductor that will crack easily, but will
otherwise be satisfactory.
It is absolutely necessary that the cool-down take place very slowly and under adequate oxygen flow. The
rate of cooling must be no more than 100 degrees Celsius per hour, especially during the critical
temperature region between 750 and 400 degrees Celsius. Take special care to insure that the sample has
access to plenty of oxygen, especially in during the cool-down from 900 to 300 degrees. Brief
interruptions in oxygen flow when the material is above 900 are unimportant, but continuous flow must
be maintained during cool-down. If the atmosphere in the furnace is not oxygen-rich while the sample is
still above about 400 degrees, the material can lose vital oxygen from its crystal structure. After the
furnace temperature reaches about 500 degrees, the rate of cooling can be increased.
During this final heat treatment, a superconductor that is more resistant to cracking during thermal
stress can be produced by subjecting the sample to high-temperature thermal cycling. To do this, vary the
temperature between 750 and 1000 degrees at rates of change of about 200 per hour. Then raise the
temperature to about 1000 degrees for an hour or more before beginning the final slow cool-down. This
thermal cycling is not a necessity at all, but it will add significantly to the mechanical strength of the
sample.