Glass-to-metal seals are a very important element of the construction of vacuum tubes, electric discharge tubes, incandescent light bulbs, glass encapsulated semiconductor diodes, reed switches, pressure tight glass windows in metal cases, and metal or ceramic packages of electronic components.
The first technological use of a glass-to-metal seal was the encapsulation of the vacuum in the barometer by Torricelli. The liquid mercury wets the glass and thus provides for a vacuum tight seal. Liquid mercury was also used to seal the metal leads of early mercury arc lamps into the fused silica bulbs.
The next step was to use thin platinum wire. Platinum is easily wetted by glass and has a similar coefficient of thermal expansion as typical soda-lime and lead glass. It is also easy to work with because of its non-oxidibility and high melting point. This type of seal was used in scientific equipment throughout the 19th century and also in the early incandescent lamps and radio tubes.
In 1911 the Dumet-wire seal was invented which is still the common practice to seal copper leads through soda-lime or lead glass. If copper is properly oxidised before it is wetted by molten glass a vacuum tight seal of good mechanical strength can be obtained. Simple copper wire is not usable because its coefficient of thermal expansion is much higher than that of the glass. Thus, on cooling a strong tensile force acts on the glass-to-metal interface and it breaks. Glass and glass-to-metal interfaces are especially sensitive to tensile stress. The Dumet-wire is a copper wire with a core of an iron-nickel alloy with a low coefficient of thermal expansion. This way it is possible to make a wire with a coefficient of radial thermal expansion which is slightly lower than the linear coefficient of thermal expansion of the glass, so that the glass-to-metal interface is under a low compression stress. About 27% of the volume of the wire is copper. It is not possible to adjust the axial thermal expansion of the wire as well. Because of the much higher mechanical strength of the iron/nickel-core compared to the copper, the axial thermal expansion of the Dumet-wire is about the same as of the core. Thus, a sheer stress builds up which is limited to a safe value by the low tensile strength of the copper. This is also the reason why Dumet is only useful for wire diameters lower than about 0.5 mm. In a typical Dumet seal through the base of a vacuum tube a short piece of Dumet-wire is butt welded to a nickel wire at one end and a copper wire at the other end. When the base is pressed of lead glass the Dumet-wire and a short part of the nickel and the copper wire are enclosed in the glass. Then the nickel wire and the glass around the Dumet-wire are heated by a gas flame and the glass seals to the Dumet-wire. The nickel and copper do not seal vacuum tight to the glass but are mechanically supported. The butt welding also avoids problems with gas-leakages at the interface between the core wire and the copper.
Another possibility to avoid a strong tensile stress when sealing copper through glass is the use of a thin walled copper tube instead of a solid wire. Here a sheer stress builds up in the glass-to-metal interface which is limited by the low tensile strength of the copper combined with a low tensile stress. The copper tube is insensitive to high electrical current compared to a Dumet-seal because on heating the tensile stress converts into a compression stress which is again limited by the tensile strength of the copper. Also, it is possible to lead an additional solid copper wire through the copper tube.
If large parts of copper are to be fitted to glass like the water cooled copper anode of a high power radio transmitter tube or an x-ray tube historically the Houskeeper (not Housekeeper!) knife edge seal is used. Here the end of a copper tube is machined to a sharp knife edge. In the original method described by Houskeeper the outside or the inside of the copper tube right to the knife edge is wetted with glass and connected to the glass tube. In later descriptions the knife edge is just wetted several milimeters deep with glass and then connected to the glass tube. This is much easier, of course.
If copper is sealed to glass, it is an advantage to get a very thin bright red Cu2O layer between copper and glass. This is done by borating. After W.J. Scott a copper plated tungsten wire is immersed for about 30 s in chromic acid and then washed thoroughly in running tap water. Then it is dipped into a saturated solution of borax and heated to bright red heat in the oxidizing part of a gas flame. Possibly followed by quenching in water and drying.
It is also possible to make a bright seal between copper and glass where it is possible to see the blank copper surface through the glass, but this gives less adherence than the seal with the red Cu2O layer. If glass is melted on copper in a reducing hydrogen atmosphere the seal is extremely weak.
Copper-plated tungsten wire can be used to seal through borosilicate glass with a low coefficient of thermal expansion which is matched by tungsten. The tungsten is electrolytically copper plated and heated in hydrogen atmosphere to fill cracks in the tungsten and to get a proper surface to easily seal to glass. There are also combinations of glass and iron-nickel-cobalt alloys (Kovar) where even the non-linearity of the thermal expansion is matched.
Another widely used method to seal through glass with low coefficient of thermal expansion is the use of stripes of thin molybdenum foil. This can be done with matched coefficients of thermal expansion or unmatched after Houskeeper. Then the edges of the strip also have to be knife sharp. The disadvantage here is that the tip of the edge which is a local point of high tensile stress reaches through the wall of the glass container. This can lead to low gas leakages. In the tube to tube knife edge seal the edge is either outside, inside, or buried into the glass wall.
Another possibility of seal construction is the compression seal. This type of glass-to-metal seal can be used to feed through the wall of a metal container. Here the wire is usually matched to the glass which is inside of the bore of a strong metal part with higher coefficient of thermal expansion.
Also the mechanical design of a glass-to-metal seal has an important influence on the reliability of the seal. In practical glass-to-metal seals cracks usually start at the edge of the interface between glass and metal either inside or outside the glass container. If the metal and the surrounding glass are symmetric the crack propagates in an angle away from the axis. So, if the glass envelope of the metal wire extends far enough from the wall of the container the crack will not go through the wall of the container but it will reach the surface on the same side where it started and the seal will not leak despite of the crack.
Another important aspect is the wetting of the metal by the glass. If the thermal expansion of the metal is higher than the thermal expansion of the glass like with the Houskeeper seal, a high contact angle (bad wetting) means that there is a high tensile stress in the surface of the glass near the metal. Such seals usually break inside the glass and leave a thin cover of glass on the metal. If the contact angle is low (good wetting) the surface of the glass is everywhere under compression stress like an enamel coating. Ordinary soda-lime glass does not flow on copper at temperatures below the melting point of the copper and, thus, does not give a low contact angle. The solution is to cover the copper with a solder glass which has a low melting point and does flow on copper and then to press the soft soda-lime glass onto the copper. The solder glass must have a coefficient of thermal expansion which is equal or a little lower than that of the soda-lime glass. Classically high lead containing glasses are used, but it is also possible to substitue these by multi-component glasses e.g. based on the system Li2O-Na2O-K2O-CaO-SiO2-B2O3-ZnO-TiO2-BaO-Al2O3.