Getters for glass bulbs (upper row) and getter strip assemblies.
THE USE of getter materials is based on the ability of certain solids to collect free gases by adsorption, absorption or occlusion. This effect is widely utilized in the field of electronics to shorten the exhaust period and to improve and maintain a high vacuum or the purity of an atmosphere of noble gases.
Bulk getters are sheets or wires of gas-absorbing metals, which usually are heated for this purpose by mounting them on hot electrodes of the tube. In some cases the heating is accomplished by a separate heating source.
Coating getters are generally applied to those electrodes of vacuum tubes, which during service are maintained continuously at temperatures between 200 and 1,200 °C. Such getters usually consist of nonvolatile metal powders that are sintered upon the electrode surfaces.
Flash gettering means, chemically active, comparatively volatile metals-mostly metals of the alkaline earth group are evaporated by heating their supports at the conclusion of the pumping process. The metal vapor before and during condensation reacts instantaneously with all other than noble gaseous residues and forms on all cold parts of the tube, particularly on the tube walls, the so-called getter mirror. This surface, because of its large area, is capable of binding chemically or physically gases that are liberated during the life of the tube. With respect to the mechanism of gettering and the action of gases getter materials may be divided into two groups : "corrosion type and "solution type. From this aspect, barium (Ba) is the typical example of chemical corrosion by gases and Zirconium (Zr) an example of solution of gases in a metal. Corrosion takes place if the oxide film is porous and incoherent, thus not preventing further oxidation, which usually happens only if the volume of the oxide is smaller than that of the metal to be oxidized. In this case, the sorption of gas from the surrounding atmosphere can continue uninterruptedly, Oxides of the alkali and alkaline earth metals have less volume than the metal.
From a technical aspect the wide application of earth alkali metals for flashing getters in vacuum tubes is founded upon the fulfillment of the following requirements:
The first requirement is satisfied by all earth alkali metals. As seen from Fig. 1, Mg is near the border line, and cannot be used in tubes with high operating temperature because of the danger of migration of Mg atoms. Requirement 2 is met by all earth alkali metals but not by aluminum. Requirement 3 is met by all earth alkali metals with the exception of Magnesium. The fourth requirement, with emphasis on activity, is met by all earth alkali metals with the exception of Magnesium and aluminum. In a similar manner requirement of an incoherent oxide layer is not met by Magnesium and aluminum. Requirement 5 (stable reactions) is met by all earth alkali metals but only up to a temperature of 200 °C (regarding the oxides created even up to higher temperatures).
The materials Sr, Ba and Ca, are the most suitable for flash getters in high-vacuum electron tubes. Concerning the replacement of absorbed gases by mercury vapor, however, all earth alkali metals fail with the exception of Magnesium, which is the reason that the latter metal is used in mercury tubes.
The practical choice of the proper getter material is a function of factors other than efficiency alone. The broad use of high-efficiency flash getters requires considerations of insulation, inter electrode capacitance, contact potential and secondary emission of vacuum-tube electrodes and insulators, which often suggest their avoidance. On the other hand, Ba flash getters are preferred for oxide-coated cathodes because the Ba does not poison the cathodes and in some cases will improve the BaO cathodes. Judicious use of shields and proper positioning of the flash getters avoids most of their disadvantages.
It has been known for a long time that almost all metals (after thorough degassing) are capable of adsorbing gases on their surfaces.
Certain metals are capable of incorporating gases, even noble gases, by solution in their bulk volume. The classical example is tantalum which, on account of this property, plays a predominant role in the construction of high-power transmitting tubes. After degassing in a high vacuum for several hours at a temperature of 1,600 to 2,000 C, tantalum is capable of absorbing gases in amounts up to several hundred times its own volume. The optimum gettering temperature for tantalum appears to be in the neighborhood of 1,000 °C. At temperatures above 1,500 C, the gettering action is reversed. The maximum getter effect is secured, therefore, by dimensioning tantalum anodes so that during normal service the electrodes operate at red to yellow heat. Generally, the high price of tantalum sheets and wires limits the use of whole tantalum electrodes to particularly valuable tubes and suggests the coating of electrodes with tantalum powder. This is mostly performed by applying very fine tantalum powder on the surface of anode sheets in the finished assemblies. They are sintered together while simultaneously degassing these powders during the pumping operation by means of high-frequency heating or by electron bombardment On account of the high degassing temperature required for tantalum, only molybdenum or tungsten is suitable as a base metal for tantalum powder. Tantalum should never be hydrogen-fired because of embrittlement and consequent destruction by this gas.
The main disadvantages of tantalum are the high material and the high temperature range required for proper degassing and subsequent gettering operation.
During recent years columbium getter pellets have been introduced to the vacuum technique. These pellets are approximately three to five millimeters in diameter and one to three millimeters high, and consist of oxide-free columbium metal.
The getter pellets must occupy a position in the tube where they can be heated to a high temperature during exhaust by either high-frequency induction or electron bombardment. The position of the pellet must be such that the temperature is maintained by either radiation or electron bombardment at approximately 500 °C. This temperature is not critical but must be above 400 and less than 900 °C. A temperature of 1,650 °C is needed to outage columbium pellets because at this temperature occluded and absorbed gases are expelled and columbium oxide is volatilized. A temperature lower than 1,650 °C will not accomplish this expulsion of columbium oxide. The out gassing time may vary from a period of five minutes to a somewhat longer time. The preferred manner for supporting the columbium getter pellet is to weld a molybdenum wire to it. The temperature of out-
Zirconium has valuable gettering characteristics and has come into wide use during the past decade. It forms very stable solid solutions (or compounds) with such gases as O, N, CO and CO2. Zirconium metal is cheaper than Tantalum and requires somewhat lower operating temperatures. Zirconium is available either in solid metal form (sheets or wires) or it may be applied in the form of a powder to base metals (Molybdenum) as described above. The proper out gassing temperature for Zirconium lies between 1,000 and 1,700 C, which is attained by either direct or indirect heating of the Zirconium metal or of the base metal to which Zirconium metal or Zirconium powder has been applied. Wherever it is deemed inadvisable to heat the getter material to this temperature range, an out gassing temperature of 700 °C must be considered minimum for activating the surface of the Zirconium getter. While Zirconium is effective as a getter from about 400 °C on, it is most active at temperatures up to 1,600 °C if used, for example, on molybdenum and carbon anodes.The solubility of H2 in Zr at room temperature equals 1,500 times its own volume at 1 atmosphere. Sorption begins at 300 to 400 °C and is completed at 500 °C. As the temperature is increased, the metal frees H2, but at 850 °C the H2 is again taken up during transition from alpha to beta Zr. Above 850 C, H2 is evolved. Sorption and desorption are reversible with decrease in temperature. Preliminary heating to a high temperature is a necessary condition for the sorption of H2 at lower temperatures. During a rapid passage from a high temperature (above 1,200 °C) to room temperature, a large amount of H2 is quickly taken up. Oxygen as well as N, dissolve homogeneously in Zr. When a Zr rod covered with a thick white oxide layer is heated in vacuum, the metallic luster reappears. Water vapor is cleaned up between 200 to 250 °C. Care must be taken that a part of the Zr getter remains at a low temperature (approximately 400 °C) during operation in order to bind the H2, while another part must assume much higher temperatures (approximately 800 °C) in order to absorb 02, N2 and other gases.Zirconium metal in sheet form 0.002 to 0.005 inch thick is used on locations that can be properly out gassed and which operate in the temperature range indicated above. Very often Zirconium sheets are mounted to grid shields, cathode supports, and other structures, which during operation attain a temperature of 600 to 800 °C. In small tubes Zirconium sheets, cylinders, or ribbons are used for cathode supports, grid supports and radiation shields. Zirconium wire of 0.005 to 0.020-inch diameter can be mounted for direct heating, being heated whenever absorption of gas is required, or it may be mounted for the same purpose by winding Zirconium wire around Molybdene rods or other suitable structures. Continuous gas absorbers such as that shown in Fig. 2 provide a support for the Zr wire and are operated from 350 to 1,700 C, for example, in x-ray tubes in series or in parallel with the filament (the temperature being adjusted by proper length of the wire). They have also been used for shortening the degassing time of electrode systems during pumping.
Using a Zr wire spiral of fifteen turns on a 0.040 inch Mo mandrel, treated and out gassed for one hour at 1,700 C, a pressure of 5 x 10-4 mm Hg was reached in ten minutes instead of thirty minutes with the high vacuum pump alone. This auxiliary pumping getter can be used repeatedly even though exposed to atmospheric pressure between pumping cycles, no additional out gassing between cycles being required. In every case the Zr absorber maintained a higher vacuum at a considerably higher effective pumping speed than the 20-liter-per-second high-vacuum pump.
A convenient way of using Zirconium is to spray the tube parts with fine Zirconium powder. Such powders, of particle size between 1 and 8 microns, may be suspended in a temporary binder such as nitrocellulose dissolved in amyl acetate. For high voltage tubes a permanent binder such as colloidal silica acid has been used with success. Such a binder has the further advantage of not giving off gaseous products during out gassing and operation. The amount of binder is usually two to five percent.
This mixture is sprayed on the electrode parts, which in turn are fired in vacuum in order to remove the binder or to convert the binder to a stable compound . Nickel electrodes (pre-heated at 1,000 C, operating at 200 to 500 °C) , molybdenum electrodes (preheated at 1,300 °C in vacuum and operating at 800 °C) and graphite electrodes can be satisfactorily coated with such mixtures. Quantitative data on the sorption of different gases at different temperatures by powdered Zr are shown in Table II. Other methods of applying Zirconium powder to electrodes have been reported, such as a suspension mixture consisting of paraffin, naphthalene, xylene and methanol or deposition of Zirconium powder by cataphoresis.
Zirconium hydride (ZrH4) may also be applied to MO, Ni, Fe or graphite anodes or grids as a paste, by spraying or cataphoretic precipitation, and reduced to pure Zr upon heating. This compound compared with pure Zr powder presents the advantage that at lower temperatures the Zirconium is tied up and protected against oxidation or poisoning during seal-in and exhaust. Then as the temperature is raised, metallic Zirconium is formed, liberating its hydrogen completely in vacuum at about 800 °C. Thus, for coating on carbonized Anodes, which liberate much adsorbed gas during exhaust, Zirconium hydride may be preferable to the pure metal since not only is the combined Zirconium protected from the evolved gases but furthermore the hydrogen that it liberates at higher temperatures apparently reduces the last traces of adsorbed oxygen in the carbon layer.
Zirconium has been used successfully in high-power transmitting tubes, especially tubes having thoriated tungsten filaments, small microwave tubes and gaseous discharge tubes. Zirconium is inert to mercury vapor.
Stable solutions or compounds of Zr are formed with most gases including water vapor, with the exception of hydrogen.
The chief disadvantage of Zirconium as a getter is that the optimum temperature for the sorption of hydrogen is too low for the effective cleanup of oxygen, nitrogen and the oxides of carbon. If, therefore, the Zirconium-coated part is to operate at a temperature much in excess of 300 C, a supplementary lower temperature Zr getter or a getter of the barium or barium-Magnesium type should be added to absorb the hydrogen. Whether this precaution is necessary or not depends upon the tube and the amount of water vapor or pure hydrogen found within it.
ThoriumDuring World War II, Thorium, Thorium alloys and mixtures of these with other getter materials were developed in Germany for use in vacuum tubes. Thorium metal is manufactured by reduction of ThO2 with Ca. Powdered Th is very pyrophoric; it is inflammable by mere friction. Electrode parts were coated with Thorium powder by cataphoresis and heated for two to three hours in a vacuum furnace. For wires the coating was 5 to 10 microns thick and for sheets 1 to 2.5 mg per sq cm. The heating temperature is about 800 to 1,000 °C for nickel and iron and 1,500 to 1,600 °C for graphite electrodes. Considerable gas absorption is reported to occur around 200 °C but especially in the range from 400 to 500 c. This getter is therefore suitable for power tubes and very small tubes with high anode temperatures. If the anode is covered with Thorium powder its surface finish is rough, resulting in increased emission by blackening.
One alloy of Thorium is the getter called Ceto, which comprises a 20-percent mischmetal, (chiefly cerium) and 80 percent Thorium. This powder mixture is sintered at approximately 1,000 C, and the bars are milled to powder again. It is very inflammable. Ceto getter powder is transformed with amyl acetate into a paste that is applied to the tube electrodes in the amount of 15 to 25 mg powder per sq cm and then sintered upon the base metal in a vacuum furnace. The degassing temperature of the Ceto getter is 800 'C and a marked getter action is exhibited from 80 to 130 °C up, with an absorption maximum at 200 to 500 °C.
Ceto getter material has a lower secondary emission than barium. It is used when it is desired to avoid or to reduce secondary emission that might arise from the use of Ba. It cannot be used above 600 °C. Ceto bridges the gap between the low-temperature flashing getter such as Ba and the high-temperature nonvolatile types (Th, Ta and Zr.) Pure Thorium or compounds of Th and Zr are highly pyrophoric.
TitaniumA recent addition to bulk getter materials is Titanium, which can be used either as bulk or as coating getter. It is not pyrophoric and its getter properties are good, besides being easy to form and machine. Blackening of the parts can be obtained by a short heating in air. At present Titanium sheet is more expensive than Zirconium per unit of gas absorbed.
AluminumAluminum in its pure state is not used as a flash-getter, mainly because its vapor pressure is too low (see Fig. 1). It vaporizes sufficiently only above 1,300 C, which is much too high for the conventional base metals like Ni. On the other hand, aluminum Anoded on Fe to a thickness of about 15 microns shows a considerable coating-getter effect for traces of O2 being bound by the carbon content of Fe electrodes and released only slowly during the life of the tube. After heating at 700 to 800 °C in vacuum, the aluminum forms a black compound with the Fe base (FeAl3 or FeAl5) . This blackening increases the total emission to a level that is equal to or greater than that of carbonized Ni anodes. Such Al-Anoded sheet-iron has been widely used in Europe for anodes in receiving and amplifier tubes with oxide-coated cathodes.
The trade name for sheet iron Anoded with aluminum on both sides is PZ-iron; Anoded with Al on one side and with Ni on the other-PN- iron.
MagnesiumPure Magnesium possesses many desirable properties for a getter material, such as availability in suitable forms, and being comparatively stable and volatile under vacuum at convenient temperatures around 500 °C. Unfortunately, the gettering power of Magnesium is not high because most gases are only physically absorbed.
As a result, Magnesium by itself is not used in high-vacuum tubes. The only evidence of its use is in Hg-vapor-filled rectifiers and in certain types as a grid coating powder to reduce secondary emission.
In order to obtain a material of greater stability and safety in use than pure Magnesium, the so-called Formier getter was developed, It consists of aluminum-Magnesium alloy powder (55 percent Al, 45 percent Mg) which is applied suspended in a nitrocellulose binder and applied to tube parts as a paint. On account of the limited gettering powers of Magnesium, Formier is used only when other types of getters with higher evaporation temperatures must avoided. Magnesium getters are difficult to degas, have little gas absorption up to temperatures of 175 °C and absorb only oxygen. High vapor pressure precludes use in small tubes and at high operating temperatures.
BariumThe active ingredient of most flash getters is. Barium, which is used in combination with aluminum, Magnesium, tantalum, Thorium, strontium or calcium. The getter is attached to the electrodes in the form of a pellet, or more frequently, to a special metallic support within the tube as shown in the top row of the accompanying photograph. It is mounted in such positions as to insure that the vapor stream produced is not splashed against such parts as the stem or the insulated lead-in wires. Shielding screens of metal, mica or ceramic materials are often provided to prevent this. The getter pellet must be attached to parts that during the pumping process may be readily heated to the evaporation temperature of the getter. This heating is performed by electron bombardment or, more frequently, by high-frequency induction from coils arranged outside the tube.
Flash getters of pure barium have the disadvantage that the unprotected barium reacts at room temperature with oxygen or with water vapor, thereby becoming inactive. This condition may be prevented by using: a protective layer or casing, alloys of Ba that are inert at room temperature or by generating the gettering material in the vacuum tube by a chemical reaction between stable Ba compounds and deoxidizing agents to form a reaction-type getter. Alloys of barium with Magnesium and aluminum are relatively stable at room temperature and yield pure barium upon dispersal or flashing of the getter. The percentage of metals in standard alloys for getter tablets are: Ba 25, Mg 55, Al 20; Ba 37, Mg 37, Al 26 ; Ba 43, Mg 20, Al 37 (known by the trade name Kemet) . The tablets are mounted on nickel flags of various shapes.
Barium-Magnesium alloys yield very little Ba metal in the flashing and are, therefore, seldom used in modern high-vacuum tubes. Ba-Al getters provide much larger amounts of Ba metal, which accounts for their wider use. A common disadvantage of both types of alloys is their rapid rate of deterioration upon exposure to air and the necessity of vacuum packing.
Flash getters have the disadvantage that during flashing metallic vapor is produced, which may settle on insulating parts or build up a conducting layer on the glass envelope. Such layers may become charged during operation or represent inter electrode capacitance. Usually flash getters are inadvisable in high voltage tubes or in microwave tubes, the latter type having very close spacing and only short insulating surfaces . It should also be considered that the opaque mirror interferes with the cooling of electrodes by radiation. In high-voltage types like transmitting and x-ray tubes fast stray electrons may hit the mirror and evaporate sufficient getter material to cause a gas discharge followed by a short circuit and destruction of the tube.
PhosphorusPhosphorus has a comparatively high vapor pressure (indicated in Fig. 1) and for this reason it is not used in radio transmitting, x-ray, or other high-vacuum discharge tubes. Inexpensive and simple to handle, it is used for high-vacuum and gas-filled lamps, Especially for types of below 60 watts with voltages of 90 to 250 volts.
The out gassing, flashing and operating temperatures of typical phosphorus getters are given in Table III.
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