Making glass-to-metal seals for home­made vacuum tubes

Kovar[1] was typically used in commercial applications where tubes were constructed from hard (borosilicate) glass. In fact, there were special formulations of borosilicate, such as Corning 7052, and later 7073, which were designed to match with Kovar. So both the metal and the glass were designed to work together. This involves engineering the metal and glass such that they shrink at about the same rate from the glass's setting point (temperature where the glass's internal stresses start to align, but before the glass solidifies) down to room temperature.

An aside on how Kovar works, because it's neat: Kovar is ferromagnetic, and the mixture of metals changes the Curie Point - the temperature above which which a ferromagnetic material stops being magnetic due to the atoms being too energetic. The Curie Point isn't a single point, it's a region. Ferromagnetic materials' lattices actually expand as they become more magnetic - this is the Magnetovolume Effect. So by adjusting the ratios of materials, Westinghouse was able to balance the Magnetovolume Effect (materials wants to expand as it cools and regains its magnetism) with the natural lattice shrinking due to cooling, and create a region where the metal matches the shrink rate of glass.

Conversely, consumer-grade vacuum tubes, such as the ones in radios, guitar amplifiers, incandescent bulbs, and televisions, typically use cheaper soda-lime or lead-alkalai silicate glass[2]. This glass had completely different thermal expansion characteristics, so different materials for leads were required. For thin leads, what they typically[3] did is use a Dumet (42/58 Nickel/Iron) wire clad in a copper sheath and coated with borax. The bonded dumet-copper (about 80/20 by weight) expands at a compromise between the two, so it can be matched to the thermal expansion of glass. The borax aided in oxide control and bonding to the glass (this is copper's "red oxide" as mentioned in the article). But this format only works for thin wires, because as we accumulate surface area we start to have to worry about axial stress from the wire expanding along its axis. So for larger leads, a (more expensive, less conductive) one-piece alloy of 52/48 Nickel/Iron had to be used instead[4].

The anodes of CRTs used yet another alloy, designed for higher expansion volume, known as "Glass-Sealing 42-6", and standardized as ASTM F31. These are 42/6/52 Ni/Cr/Fe alloys.

Lastly, to bring it all back home, the glass matters as much as the metal, and the author of this article is using an exceptionally poor glass for vacuum tube work. It seems like they are using regular Pyrex, which has a much lower expansion coefficient than most vacuum tube glass, and in fact, most metals.

[1] - The generic term for Kovar is Fernico (from Iron-Nickel-Cobalt, Fe-Ni-Co). It was invented by Westinghouse in the 1930s. Other names for Kovar are: ASTM F-15, NILO K, Pernifer 2918, Rodar, and Dilvar P1.

[2] - An exception is tubes that experienced high temperatures that might melt normal glass - such as Xenon flash tubes. Another exception is metal vacuum tubes which had small glass borosilicate beads around each lead wire, bonded to both the wire and the surrounding metal. These were common in 1940s radios.

[3] - US Patent 4824459 - Marker Pin for a Universal Stem Mold - https://image-ppubs.uspto.gov/dirsearch-public/print/downloa...

[4] - Interesting footnote: Platinum also works great as a soft-glass seal wire, if you have the $$$$. Dumet was originally marketed as "platinite" - a platinum substitute.

If vacuum tubes had pins of copper, the glass-metal joining would have cracked very soon during normal usage cycles, and there would have been no vacuum left in the tube.

Real vacuum tubes and gas tubes had pins made of kovar, which is a Fe-Ni-Co alloy with a TCE matched to a certain composition of borosilicate glass.

The kovar pins were normally plated with nickel on their external parts, to enable soldering, because molten solder does not wet kovar.

If I may offer an anecdote, the output stage in my guitar amplifier is powered by a GEC tube that is now 55 years old. It sounds great. When I found the tube, it had been rolling around for a couple of decades at the bottom of a wooden box.

This could simply be survivorship bias, but it does appear that back in the day, they knew how to build these things to last.