Solder - Glass Solder

Glass Solder

Glass solders are used to join glasses to other glasses, ceramics, metals, semiconductors, mica, and other materials, in a process called glass frit bonding. The glass solder has to flow and wet the soldered surfaces well below the temperature where deformation or degradation of either of the joined materials or nearby structures (e.g., metallization layers on chips or ceramic substrates) occurs. The usual temperature of achieving flowing and wetting is between 450 and 550 °C.

Two types of glass solders are used: vitreous, and devitrifying. Vitreous solders retain their amorphous structure during remelting, can be reworked repeatedly, and are relatively transparent. Devitrifying solders undergo partial crystallization during solidifying, forming a glass-ceramic, a composite of glassy and crystalline phases. Devitrifying solders usually create a stronger mechanical bond, but are more temperature-sensitive and the seal is more likely to be leaky; due to their polycrystalline structure they tend to be translucent or opaque. Devitrifying solders are frequently "thermosetting", as their melting temperature after recrystallization becomes significantly higher; this allows soldering the parts together at lower temperature than the subsequent bake-out without remelting the joint afterwards. Devitrifying solders frequently contain up to 25% zinc oxide. In production of cathode ray tubes, devitrifying solders based on PbO-B₂O₃-ZnO are used.

Very low temperature melting glasses, fluid at 200–400 °C, were developed for sealing applications for electronics. They can consist of binary or ternary mixtures of thallium, arsenic and sulfur. They are used for sealing of electronic components. Zinc-silicoborate glasses can also be used for passivation of electronics; their coefficient of thermal expansion must match silicon (or the other semiconductors used) and they must not contain alkaline metals as those would migrate to the semiconductor and cause failures.

The bonding between the glass or ceramics and the glass solder can be either covalent, or, more often, van der Waals. The seal can be leak-tight; glass soldering is frequently used in vacuum technology. Glass solders can be also used as sealants; a vitreous enamel coating on iron lowered its permeability to hydrogen 10 times. Glass solders are frequently used for glass-to-metal seals and glass-ceramic-to-metal seals.

Glass solders are available as frit powder with grain size below 60 micrometers. They can be mixed with water or alcohol to form a paste for easy application, or with dissolved nitrocellulose or other suitable binder for adhering to the surfaces until being melted. The eventual binder has to be burned off before melting proceeds, requiring careful firing regime. The solder glass can be also applied from molten state to the area of the future joint during manufacture of the part. Due to their low viscosity in molten state, lead glasses with high PbO content (often 70–85%) are frequently used. The most common compositions are based on lead borates (leaded borate glass or borosilicate glass). Smaller amount of zinc oxide or aluminium oxide can be added for increasing chemical stability. Phosphate glasses can be also employed. Zinc oxide, bismuth trioxide, and copper(II) oxide can be added for influencing the thermal expansion; unlike the alkali oxides, these lower the softening point without increasing of thermal expansion.

Glass solders are frequently used in electronic packaging. CERDIP packagings are an example. Outgassing of water from the glass solder during encapsulation was a cause of high failure rates of early CERDIP integrated circuits. Removal of glass-soldered ceramic covers, e.g., for gaining access to the chip for failure analysis or reverse engineering, is best done by shearing; if this is too risky, the cover is polished away instead.

As the seals can be performed at much lower temperature than with direct joining of glass parts and without use of flame (using a temperature-controlled kiln or oven), glass solders are useful in applications like subminiature vacuum tubes or for joining mica windows to vacuum tubes and instruments (e.g., Geiger tube). Thermal expansion coefficient has to be matched to the materials being joined and often is chosen in between the coefficients of expansion of the materials. In case of having to compromise, subjecting the joint to compression stresses is more desirable than to tensile stresses. The expansion matching is not critical in applications where thin layers are used on small areas, e.g., fireable inks, or where the joint will be subjected to a permanent compression (e.g., by an external steel shell) offsetting the thermally introduced tensile stresses.

Glass solder can be used as an intermediate layer when joining materials (glasses, ceramics) with significantly different coefficient of thermal expansion; such materials cannot be directly joined by diffusion welding. Evacuated glazing windows are made of glass panels soldered together.

A glass solder is used, e.g., for joining together parts of cathode ray tubes and plasma display panels. Newer compositions lowered the usage temperature from 450 to 390 °C by reducing the lead(II) oxide content down from 70%, increasing the zinc oxide content, adding titanium dioxide and bismuth(III) oxide and some other components. The high thermal expansion of such glass can be reduced by a suitable ceramic filler. Lead-free solder glasses with soldering temperature of 450 °C were also developed.

Phosphate glasses with low melting temperature were developed. One of such compositions is phosphorus pentoxide, lead(II) oxide, and zinc oxide, with addition of lithium and some other oxides.

Conductive glass solders can be also prepared.