Glass-to-metal seals are a type of mechanical seal which joins glass and metal surfaces. They are very important elements in the construction of vacuum tubes, electric discharge tubes, incandescent light bulbs, glass-encapsulated semiconductor diodes, reed switches, glass windows in metal cases, and metal or ceramic packages of electronic components. Properly done, such a seal is hermetic (capable of supporting a vacuum, good electrical insulation, special optical properties e.g. UV lamps). To achieve such a seal, two properties must hold:
The molten glass must be capable of wetting the metal, in order to form a tight bond, and The thermal expansion of the glass and metal must be closely matched so that the seal remains solid as the assembly cools. Thinking for example about a metal wire in a glass bulb sealing, the metal glass contact can break if the coefficients of thermal expansion (CTE) are not well aligned. For the case that the CTE of the metal is larger than the CTE of the glass, the sealing shows a high probability to break upon cooling. By lowering the temperature, the metal wire shrinks more than the glass does, leading to a strong tensile force on the glass, which finally leads to breakage. On the other hand, if the CTE of the glass is larger than the CTE of the metal wire, the seal will tighten upon cooling since compression force is applied on the glass.
According to all requirements that need to be fulfilled and the strong necessity to align the CTE of both materials, there are only a few companies offering specialty glass for glass-metal sealing, such as Schott AG and Morgan Advanced Materials.
Glass-to-metal bonds Glass and metal can bond together by purely mechanical means, which usually gives weaker joints, or by chemical interaction, where the oxide layer on the metal surface forms a strong bond with the glass (the glass itself is about 73% composed of a silicon dioxide (SiO2)) . The acid-base reactions are main causes of interaction between glass-metal in the presence of metal oxides on the surface of metal. After complete dissolution of the surface oxides into the glass, further progress of interaction depends on the oxygen activity at the interface. The oxygen activity can be increased by diffusion of molecular oxygen through some defects like cracks. Also, reduction of the thermodynamically less stable components in the glass (and releasing the oxygen ions) can increase the oxygen activity at the interface. In other words, the redox reactions are main causes of interaction between glass-metal in the absence of metal oxides on the surface of metal. For achieving a vacuum-tight seal, the seal must not contain bubbles. The bubbles are most commonly created by gases escaping the metal at high temperature; degassing the metal before its sealing is therefore important, especially for nickel and iron and their alloys. This is achieved by heating the metal in vacuum or sometimes in hydrogen atmosphere or in some cases even in air at temperatures above those used during the sealing process. Oxidizing of the metal surface also reduces gas evolution. Most of the evolved gas is produced due to the presence of carbon impurities in the metals; these can be removed by heating in hydrogen. The glass-oxide bond is stronger than glass-metal. The oxide forms a layer on the metal surface, with the proportion of oxygen changing from zero in the metal to the stoichiometry of the oxide and the glass itself. A too-thick oxide layer tends to be porous on the surface and mechanically weak, flaking, compromising the bond strength and creating possible leakage paths along the metal-oxide interface. Proper thickness of the oxide layer is therefore critical.
Copper Metallic copper does not bond well to glass. Copper(I) oxide, however, is wetted by molten glass and partially dissolves in it, forming a strong bond. The oxide also bonds well to the underlying metal. But copper(II) oxide causes weak joints that may leak and its formation must be prevented. For bonding copper to glass, the surface needs to be properly oxidized. The oxide layer is to have the right thickness; too little oxide would not provide enough material for the glass to anchor to, too much oxide would cause the oxide layer to fail, and in both cases the joint would be weak and possibly non-hermetic. To improve the bonding to glass, the oxide layer should be borated; this is achieved by e.g. dipping the hot part into a concentrated solution of borax and then heating it again for certain time. This treatment stabilizes the oxide layer by forming a thin protective layer of sodium borate on its surface, so the oxide does not grow too thick during subsequent handling and joining. The layer should have uniform deep red to purple sheen. The boron oxide from the borated layer diffuses into glass and lowers its melting point. The oxidation occurs by oxygen diffusing through the molten borate layer and forming copper(I) oxide, while formation of copper(II) oxide is inhibited. The copper-to-glass seal should look brilliant red, almost scarlet; pink, sherry and honey colors are also acceptable. Too thin an oxide layer appears light, up to the color of metallic copper, while too thick oxide looks too dark. Oxygen-free copper has to be used if the metal comes in contact with hydrogen (e.g. in a hydrogen-filled tube or during handling in the flame). Normally, copper contains small inclusions of copper(I) oxide. Hydrogen diffuses through the metal and reacts with the oxide, reducing it to copper and yielding water. The water molecules however can not diffuse through the metal, are trapped in the location of the inclusion, and cause embrittlement. As copper(I) oxide bonds well to the glass, it is often used for combined glass-metal devices. The ductility of copper can be used for compensation of the thermal expansion mismatch in e.g. the knife-edge seals. For wire feed throughs, dumet wire – nickel-iron alloy plated with copper – is frequently used. Its maximum diameter is however limited to about 0.5 mm due to its thermal expansion. Copper can be sealed to glass without the oxide layer, but the resulting joint is less strong.
Platinum Platinum has similar thermal expansion as glass and is well-wetted with molten glass. It however does not form oxides, so its bond strength is lower. The seal has metallic color and limited strength.
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