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Katsushi Fukuda (Komatsu, Japan) tells us of the attached 1905 Japanese patent on thermoelectric applications of Zinc-Antimony-Bismuth.

The patent is in Japanese, naturally, but the figures alone are worth a look even if you can't read Japanese. Fortunately Fukuda-san's has provided some generous comments in English. His edited comments follow.

Dear Dr.Vining

I am katsushi Fukuda. I have met you at Komatsu Electronics about ten years ago. Mr. Uemura sent me your e-mail. About old patent, I found it 2 years ago.

And recently, I read it again to write a text for a seminer which is memorial
seminar for foundation of the Thermolelctrics Society of Japan. It is held 9th Dec 2004. I did not read it enough at first time, but I read again I was very interested in it.

In the patent, P-type material is made of the mixture of Bi:Sb:Zn=12.0:48.0:36.8.

I think this ratio is weight ratio, so transrate to chemical ratio is Zn3Sb4Bi0.4!! It is very close to Zn3Sb4. Maybe this mixture is not single phase, but segregated material.

The date of the application was 23th April 1905, pateted in 20th of Nov. 1905. "Partisan's Pan" ["Partisan's Kit"] were used [in the Soviet Union] in 1940's. It used ZnSb. Before Ioffe era, such mixture was considered in Japan, which surprised me.

I will send you this patent PDF file. If it could be send. [attached below]

Unfortunately, In Japanese old application format had only Inventor's name, and Original patent had gone out by Tokyo Earthquake of 1923. So we can know only Inventor is Kinzo Yamamoto.

In the figure, D is P-type "Bullet" and E is rag of Nickel. F is the pin to
collect heat flow from the flame.
A is electrical and thermal metal conection. B is fin.

In the patent, this generator would be low product cost compared with another Themolectric generator!!
I am not sure that thermoelectric genarators were popular at the time.
But at the time, radio transmission was used for military and batteries became popular.

I will report it in the seminar and ask participants to give me information
about Mr.Yamamoto.

Next year is the 100 years anniversary of this patent. I would like to this fact will be opened to the world from Thermolelctrics Society of Japan.
So please keep it in your bosom until it will opened.

I think, in the history of Thermoelectric, most of the fact of the period of
between Seebeck/Peltier and Ioffe was gone out. Perhaps there are some important invents and works.

If you have a interest, please check US patent office web.
There is a Altenkirch Patent (USP 1120781) 1914. He is a famous thermoelectian before Ioffe.
This patent is intered too.

Sincerely

Katsushi Fukuda
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Komatsu Electrinics Inc.
Katsushi Fukuda

TEL 0463-23-8219
FAX0463-22-3692
E-mail:katsushi_fukuda at kelktech.komatsu.co.jp
http://www.komatsu-electronics.co.jp
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(See attached file )