|1.||The process of preparing a length of carrier foil carrying a pyrophoric coating, which process is characterized by using plain carbon steel foil not over 50 microns thick as the carrier foil, and sintering to the foil powdered Raney precursor metals in stages that do not embrittle the foil so much that it will not wrap at least 20 degrees around a mandrel 3 centimeters in diameter.|
|2.||A pyrophoric article in the form of a disc about 100 to about 500 microns thick of sintered and pyrophorically activated metal aluminide powder, the disc including a layer of inactive metal having a thickness about 1/10 the disc thickness.|
|3.||The combination of claim 2 in which the inactive layer is not at a surface of the disc.|
|4.||In the discharging of pyrophoric material into the air to generate heat and thus decoy a heatseeking missile, the improvement according to which the material is a mass that holds itself together so that the hot cloud produced is not over about 10 meters wide.|
|5.||The combination of claim 4 in which the pyrophoric material is in the form of one or more coils.|
|6.||The combination of claim 5 in which one or more coils is partially slit.|
|7.||In the process of preparing pyrophoric aluminide by preparing precursor aluminide particles on a supporting web, and before leaching those particles, compacting them on the web at a temperature above about 400°C to essentially fill all voids.|
|8.||The process for preparing pyrophoric iron, characterized by the provision of unmelted Raney type ironaluminum alloy, and then leaching the alloy to dissolve ■ out most of the aluminum to thus leave an activated iron.|
|9.||The process of claim 8 in which the unmelted alloy is in the form of particles not over about 100 microns in size.|
|10.||The process of claim 9 in which the unmelted alloy is provided by the low temperature diffusion aluminizing of iron particles.|
|11.||The process of claim 10 in which the leaching is effected with aqueous caustic containing dissolved tin.|
|12.||A mass of pyrophoric particles produced by the process of claim 11.|
|13.||In the process of discharging a mass of activated iron particles as a countermeasure against a heatseeking missile, the improvement according to which the mass is a dry mass according to claim 12. SUBSTITUTESHEET.|
The present invention relates to the surface treatment of metals to activate them or prepare them for receiving coatings.
Among the objects of the present invention is the provision of novel methods for effecting activation and preparation.
Additional objects of the present invention include the provision of novel forms of activated metal.
The foregoing as well as further objects of the present invention will be more fully understood from the following ' description of several of its exemplifications, reference being made to the accompanying drawing in which:
Fig. 1 is a somewhat diagrammatic illustration of an activating treatment according to the present invention. The activating treatment is described in detail in U.S. Patent 4,895,609 issued 1/23/90.
By way of additional illustration, a readily ignited metal such as titanium or magnesium in foil or wire form can be given a nickel coating, as by rolling, and the nickel coating then activated to render it pyrophoric. To ignite the ignitable metal the coating should be at least about 0.4 mil thick.
Activated powders containing boron, or even free of boron, are stored out of contact with air or oxygen to preserve their pyrophoricity. Water is not a suitable preserving liquid for the activated boron-containing powders. Acetone preserves them for at least three weeks, as does an azeotropic mixture of trifluoro-trichloro ethane with methylene chloride, described in U.S. Patent 2,999,817. Ordinary fluoro-chloro ethanes and methanes that are nor¬ mally used as refrigerants or propellants are also suitable and they can be used by themselves or mixed with each other or with acetone. Mixtures of the activated powders with preserving liquids that, are also propellants, are particularly desirable in that they can be packed in an aerosol-type container from which they are readily discharged to provide a cloud of pyrophorically oxidizing particles.
Titanium can also be aluminized and/or boronized by modified treatment, to make it more resistant to corrosive attack. For this purpose, the aluminum is not- leached out as it is when activating. It is also very desirable to diffusion coat titanium in the absence of hydrogen and in the complete or substantially complete absence of conventional halide activators like A1C1, and NH.C1. Thus engine compressor blades made of Ti6A14V can be embedded in a pack of 20% Al-Si alloy powder containing 12% silicon, and 80% aluminum, completely free of energizer, and at 1300°F for 14 hours under argon, acquires a protective aluminide case 0.5 to 1 mil thick. Using pure aluminum instead of the Al-Si alloy reduces the case thickness by about half.
Adding 1/4% A1C1., or NH.C1 energizer to the pack causes the titanium substrate to be significantly embr.ittled. However, the aluminizing can be speeded by using a pack that had been pre-fired with such a halide energizer for a time long enough to drive out essentially all the energizer at least one to two hours at 700°F or higher. It appears that some energizer remains or some change is caused, to make the pre-fired pack much more effective in aluminizing the titanium. In any event the resulting aluminizing produces thicker cases, and can be readily effected at temperatures as low as 1000°F or in times as short as 5 hours.
The addition to the pack of about 1/10% of a titanium halide such as TiCl-, preferably sealed in a polyethylene tube so as to be protected against exposure to the atmosphere, is also helpful to speed up the diffusion coating. The polyethylene tube melts before the pack reaches diffusion temperature, releasing its contents.
The aluminized titanium compressor blades can then be boronized instead of or before applying a top coating as described in connection with Canadian patent 779,173. A suitable boronizing pack for this purpose is a diluent-containing pack using ammonium fluoborate as the energizer and with added titanium powder in an amount about half the amount of boron powder, by weight. A 0.3 mil boronized case is thus formed at 1075°F for 14 hours in argon. The titanium powder helps keep the titanium
substrate from being attacked by the halide in the pack, and can also be added to the pack used for aluminizing titanium. It can also be omitted, particularly when only a thin diffusion coating is desired. When the powdered titanium is used, it can range from about 1/5 the boron content to about equal the boron content by weight. Boron being a very high melting material, it can be used with little or no refractory diluent, particularly at diffusion temperatures low enough to keep the workpiece surfaces from reaching a sintering condition. On the other hand, the boron content of a boronizing pack can be as low as 2%, although at least 4% is preferred. To be sure that no sintering takes place, an inert refractory diluent like Al-O.-,, kaolin or MgO can be present in the pack in a concentration of at least 30%.
The re-use of packs containing sodium fluoborate energizer can be complicated by the gradual build-up of sodium fluoride with each use. This problem does not appear to arise when ammonium fluoborate is the energizer.
Masking can also be used to localize the top coating of metals like titanium that, are to be protected as by aluminizing, boronizing, nitriding or the like. Thus pack formulations can be applied to those localized areas to prevent coating. For this purpose, the titanium content in the pack should be at least about 35% to assure the desired masking effect, and the thickness of the masking layer at least about 3 millimeters. For best results the masking formulation should contain about 43% titanium diluted with an inert powder such as alumina . or kaolin or magnesia. Inasmuch as such high titanium concentrations can cause alloying ingredients in the workpiece to diffuse out from the workpiece to the mask, and to inhibit such loss, the mask preferably contains such alloying ingredients in addition to the titanium. The most preferred masking formulations thus contain about 43% by weight titanium powder plus an aluminum metal content equal to the aluminum content in the pre-alloyed workpiece, and in addition a content of other metals equal to about one-fifth their content in the pre-alloyed workpiece.
By way of example, for localized masking against the boronizing or aluminizing of Ti-6A1-4V, a very effective formulation is:
43% titanium 6% aluminum 0.8% vanadium balance alumina For similarly masking Ti-3Al-llCr-13V, the preferred formulation is:
43% titanium 3% aluminum 2.2% chromium 2.6% vanadium balance alumina These highly effective formulations -. can have their ingredient percentages varied plus or minus about 10% without significantly detracting from their effectiveness. The formulations should also be broken in by a pre-heat to between about 750 to about 1000°C for about 4 to about 15 hours with about 1/2 to about 1% activator added. Suitable activators are NH 4 C1 and HN.Br. A 980°C pre-heat for 10 hours is preferred. The masking compositions can be applied to the workpieces as a slurry in a vaporizable liquid like water or methylchloroform, and the coated workpiece then packed in place in the pack of a coating retort before the coating dries and loosens. Alternatively a little binder such as Poly(ethylmethacrylate) resin can be added to the masking composition as a 1 to 3% solution in methylchloroform, for example, to hold the masking coat in place during the coating heat. Where the . heat is hot enough to drive off such resin binder and loosen the mask, non-fugitive binders such as bentonite can be used.
For some purposes it is helpful to have pyro¬ phoric decoy pieces that when discharged into the air from a rapidly moving aircraft, do not immediately slow down and stop their discharge movement. To this end the pieces can be contained in a wire netting that permits them to spread out to only about 10 meters when dis¬ charged. Alternatively or additionally, the decoy pieces can be made so that their air resistance is small and inertia high. Thus the carrier web can be tantalum, silver or lead foil as much as 3/4 mil thick, and only about 1 square centimeter discs. Silver webs also contribute very good electrical conductivity that provides the pieces with an electrical dipole that helps decoy against radar signals. Copper has a similar dipole effect.
The decoying action can be modified by arranging for a succession of decoy charges to be expelled by a moving aircraft in 20 to 30 second intervals, for example. This appears to a heat-seeking missile as a series of hot clouds that move with the aircraft, and thus becomes a more attractive decoy target.
The pyrophoric behavior of activated iron particles is different when they are prepared in different.
ways. The most vigorous behavior is obtained when the particles and the precursor aluminides from which they are made, are kept from melting during the preparation. The following is an example:
40 grams minus 325 mesh iron powder are mixed with 60 grams similarly sized aluminum powder and 1 gram anhydrous aluminum chloride powder, and the mixture placed in a steel retort, the retort loosely covered and placed in a larger retort through which a stream of argon flushes. The retort assembly is then inserted in a furnace, heated to 1200°F and kept there for 1 1/2 hours. During the initial heat-up, a stream of hydrogen is substituted for the stream of argon. After cooldown, the powder particles have sintered together to a large degree, and the resulting masses are ground, as with a chopper blade such as used in a micro-mill type grinder, to very fine particle size, for example 325 mesh. These particles can be screened out, if desired and constitute particles that can be somewhat larger in size than the original particles. These aluminized particles can now be subjected to a caustic leach treatment to produce highly pyrophoric iron powder, the particles of which are about, the same overall size as the aluminized particles. The grinding can be controlled to provide activated particles of larger or smaller size.
To reduce the tendency for the particles to sinter together during the diffusion coating, the diffusion temperature and/or time can be lowered to as low as about 800°F to 900°F and/or inert refractory particles such as alumina powder can be mixed with the iron and aluminum powders. After such a mixture has completed its diffusion coating treatment or the leaching treatment, the inert alumina can be separated out magnetically. The leached iron particles are magnetic,whereas the alumina particles are nonmagnetic, so that pouring a stream of the mixtures through a magnetic field causes the iron particles to be deflected away from the alumina particles. There may be some tendency for the fine alumina or other refractory
particles to physically adhere to the diffusion-coated iron particles, in which event the diffusion-coated mixture can be forcefully agitated in water preferably containing a little surface active agent to wash the fine alumina or the like off the heavier iron particles and permit those heavier particles to settle out.
Powdered pyrophoric metal or powdered precursor alloys can also be separated from inert diluents or other ingredients in diffusion coating packs by having different sizes for the particles to be separated and sieving the mixture to effect the separation. Thus cobalt or iron balls at least about 20 mils in diameter can be diffusion coated in a pack whose particles are all smaller than 2 mils thick.
The pyrophoric particles can be used to generate a hot cloud, as for example to decoy heat-seeking missiles. Thus the pyrophoric particles produced according to Example 1 can be rinsed with water then with acetone and packed under argon in a simple container or in a spray can, and about 100 grams of such powder projected into the air. These particles promptly heat up and oxidize. The resulting cloud of particles rises as a result of the heating. It is only after several minutes that the oxidized particles settle down to the ground.
The pyrophoric particles are conveniently discharged to form the desired cloud, by loading them into a shotgun shell in place of the shot and the shot-dispersing gunpowder. A relatively short 12-gauge paper shell can thus be packed with about 50 grams of the powder sealed airtight in a plastic enclosure around which the shell is crimped. The usual primer charge will be enough, when detonated, to expel the powder and create the desired cloud.
Larger quantities, up to a pound or more, can be poured into a valved pressure-resistant container which is then pressurized to about 200 to 600 pounds per square inch gauge with argon. Upon opening the valve, the powder contents are propelled out with the arqon.
Modifying Example 1 by using particle size of about 30 to 100 microns for the iron powder and for the aluminum powder and reducing the diffusion time to one hour after it reaches 900°F, yields iron-aluminum alloy particles
not heavily sintered together; a light crushing in a mortar and pestle yields a powder that can be somewhat coarser. A one-hour leaching of that powder in 17% aqueous NaOH by weight while keeping the leaching temperature no higher than 100°F leaves a pyrophoric powder that when discharged produces a hot cloud that does not rise much before eventually settling out.
An alloy in which before leaching the aluminum content is at least about 40% by weight should be used to make the desired cloud, but an aluminum content of at least about 50% by weight is preferred. Cooling of the leaching reaction may be required, depending on the quantity of reactants and the volume of the leach solution. Because of the fineness of the particles, the entire leaching step takes about one hour or less; shorter leaching times (e.g., 30 minutes) give the best results. Caustic potash can be used in place of caustic soda under the same con¬ ditions. The addition to the caustic of. stannite or εtannate to the leaching caustic, as described in U.S. Patent 4,435,481, is desirable.
The foregoing leaching leaves the leached particles with only a small aluminum content and highly pyrophoric. More vigorous leaching leaves a smaller aluminum content in the leached particles, but appears to attach the active iron sites and also leaves them somewhat less pyrophoric and less effective.
Pyrophoricity is readily measured by exposing a 25 to 35 milligram sample of the activated powder to air and using a two-mil platinum-platinum/rhodium wire thermocouple to measure the temperature rise during the exposure. A temperature of 600°F should be reached, but preferred temperatures are as high as 1100°F or higher.
Substituting nickel for the iron in the diffusion coated particles, or using commercial Raney nickel powder, gives somewhat better results in producing a rising cloud of pyrophorically heated particles. Thus, nickel-aluminum alloys containing as little as about 35% aluminum before leaching can be very effectively used.
Where, before leaching, the pyrophoric particles are made by diffusing aluminum into iron or nickel, it is
important to conduct the diffusing operation at relatively low temperatures, such as below 1200°F and preferably below 1000°F. Even at temperatures as low as 850°F the time at temperature can be as short as about 45 minutes when a diffusion activator such as AlCl, is used.
The alloy particles can also contain other ingredients such as boron, titanium, carbon, zirconium and magnesium that help generate heat. Excluding the aluminum, the content of pyrophoric metal in the leached alloy should be at least about half by weight in order to have enough pyrophoricity to cause the remaining ingredients to react and generate their reaction heat.
The pyrophoric particles used to make the hot cloud can be mixed with other materials that increase or decrease the heat generation and/or vertical cloud movement.
Thus the activity of the pyrophoric particles can be reduced as by too vigorous leaching or by particularly light leaching, and the sizes of the pyrophoric particles can be increased to 100 or more microns to keep them from rising much in the hot cloud. Alloying the particles with other ingredients such as silicon or chromium that are not rendered pyrophoric, also reduces the upward movement of the cloud they generate after activation.
Alternatively, the pyrophoric particles can be mixed with non-pyrophoric particles such as unactivate iron powder or carbon powder which act as diluents and also burn.
Another example is
PACK COMPOSITION 210g minus 325 Al powder 210g minus 325 Fe powder
4g A1C1 3
The above is mixed and placed in a plain steel retort fitted with an internal thermocouple. The retort so loaded is placed in a furnace and fired at 1000°F under Hydrogen. When the internal temperature reached about 400°F, an exothermic reaction occured as revealed by an
instantaneous surge of the internal temperature to 1735°F. The retort was maintained in the 1000°F furnace for two hours. It was then cooled under Hydrogen and purged with Argon after reaching room temperature.
The pack in the retort was hard but it could be unloaded and ground with mortar and pestle to pass through a minus 100 mesh sieve. The yield was 96%. 200g of the sieved FeAl_ product was gradually added to a solution of 267g NaOH + 7g SnCl 2 2H 2 C1 in 2 liters of water at 140-160°F. The resulting leaching was carried out. under an argon atmosphere to insure no oxidation of the activated iron particles. The activated iron now contains less than about 2% Al, and it was rinsed in water to pH 8, then rinsed in acetone to remove the water, and dried in argon.
The dried activated iron was very pyrophoric. Similarly activated iron particles prepared by leaching an alloy having the same proportion but supplied as a solidified melt from commercial sources, was far less pyrophoric. Dispersing of the powders by throwing out into the air 50 grams of the respective activated products resulted in immediate incandescence of essentially all unmelted particles, but only delayed or no incandescence from the particles that had a history of melting. It was also noted that the latter particles tended to become passivated and generated less total heat. Subjecting the respective particles to the mild acid after-treatment of U.S. Patent 4,927,798 further increases their heat generation and reduces their response time.
Use by or against fast-moving aircraft can be greatly assisted by the immediate incandescence. However, it is sometimes desirable to have immediate heat-up of the particles, but with the heat-up temperature sufficiently low that no incandescence is visible. To this end, the particles are diluted with inactive powder or provided with inactive coatings that delay but do not completely block access to oxygen. Thus the addition to the very reactive particles of about 10 to 28% of minus 325 mesh sharply sharply reduces the incandescence of the mixture. Other inert oxides such as MgO, TiO_ and Zr0 2 have a similar effect. White additives are preferred because they also
lighten up the dark-colored smoke that is produced by the pyrophoric reaction.
Alternatively the iron being activated can be alloyed with non-pyrophoric metal such as chromium or silicon, and only about 5 to 20% of such alloying can completely prevent incandescence.
Incandescence-inhibiting coatings can be of any type including water-soluble and water-diεperible silicates and boro-εilicates. By way of example 10 grams of the highly active iron particles can be stirred into 100 cc of a 10% aqueous solution of a soluble borosilicate containing
65% B 2 ° 3 and 65% s ~° 2 r and fi ltered °ff after 30 minutes • standing, to show essentially no incandescence after drying.
The pyrophoric product is also a very effective catalyst for different kinds of chemical and electrochemical reaction, such as electrolysis of water with very low over-voltages, ammonia oxidation, CO oxidation. and NOX removal. This catalytic quality remains essentially unaffected after the pyrophoric product, is permitted to undergo its pyrophoric reaction with air. The pyrophoric product can also be stabilized by exposure to small concentrations of air under conditions that keep it from getting warm enough to rapidly react, as described in U.S. Patent 4,820,362.
The pyrophoric action of pyrophoric members can be increased by placing in intimate contact, with the member, 'a solid or liquid that undergoes an exothermic reaction when heated. Metals like magnesium and titanium, and even boron can thus be adhered to a pyrophoric foil as by placing a magnesium ribbon over an activated foil and passing the assembly between a pair of pressure rollers. Powdered materials such as magnesium, titanium, manganese, zirconium, carbon, aluminum or boron can be dispersed in a volatile liquid and the dispersion applied to an activated member and dried. Commercially available boron powder is very effective when dispersed in an alcohol such as ethanol.
Such pyrophoric combinations need not be in the form of very thin coated foils, and can take other forms. Thus a 5-mil thick felt of boron or carbon fibers or ordinary paper or cotton cloth can be coated on one or both sides with a paste of pyrophorically activated iron or
if desired a sintering treatment to form a self-supporting sheet in which the pyrophoric particles are embedded in the inter-fiber spaces. A boron felt weighing about. 0.1 gram per square centimeter of gross surface (as measured with a ruler), carrying 0.2 gram pyrophoric iron powder per square centimeter of gross surface, generates a very large amount of heat when exposed to the atmosphere. Ordinary steel wool also makes a very effective porous substrate for impreg¬ nation.
As noted, the pyrophoric material can be prepared as a coating on a thin carrier web. Fig. 1 illustrates an improved modification of this technique.
In Fig. 1, a carrier foil 10 of stainless steel or 1010 steel about 1/40 to about 1/20 millimeter thick is spray coated on both its faces from spray nozzles 12,12 with a binder-containing mixture of iron powder and aluminum powder in a proportion that makes a Raney type allo . The binder is a resin, preferably an acrylate, dissolved in a solvent like methyl chloroform. The powder particles are preferably no larger than about 5 to 20 microns.
The thus coated web 14 is led through an externally fired tube 16 of a tube furnace where it is rapidly heated to over 500°C. By that time the coating layers have been dried, the resin binder volatilized off, and the metal powders have interreacted to form the Raney alloy, FeAl., for example. After leaving the tube furnace but before the coatings have cooled excessively, the coated web 14 is passed between reduction rolls 18,18 where the hot Rayney alloy is compacted to essentially eliminate voids.
A protective gas such as argon is preferably introduced, as at 20, into the furnace tube 16. Some of that gas will rise in tube 16 and thus protect the coated web from the oxidizing action of the ambient air as it heats up. Portions of the gas will also flow down from the exit end of tube 16 and similarly protect the hot emerging web. A cylindrical shell 21 may be positioned about the emerging web to help confine the downwardly-flowing protective gases aginεt the hot web.
The reduction rolls 18,18 should be sufficiently massive so that they are not excessively heated by the hot
web. If desired, the rolls can be liquid cooled to help hold down their surface temperature.
The compacted web is then led through a tank 22 containing aqueous caustic soda which disεolveε much of the aluminum from the Raney particles on the web. The trip through the caustic soda is preferably arranged to take two to 10 minutes, as by adjusting the temperature and concentration of the caustic. The web entering the caustic can be as hot as 600°C and the action of the caustic generates heat, so it is simpler to keep the caustic solution hot, at least about 80°C.
The caustic generates large quantities of hydrogen as it acts on the web, so that a hood 24 can be placed over tank 22, with a suction connection 26 to an aspirator that aspirates off the evolved hydrogen. The web emerging from tank 22 is web with the caustic, and that caustic should be replaced.
The proportions of iron powder to aluminum powde can be varied, nickel powder can be sustituted for εome or all of the iron powder, and iron or nickel aluminides mixed with the incoming powders. The aluminide formation can als be effected in stageε. The presence of a little copper in the sprayed-on coating mixture helps the aluminide coating adhere to a εtainleεε steel web core. Instead of spraying the coating on the web, the web can be dipped in a coating bath, or applied by any other technique. The amount of coating should be such as to leave a compacted web not over about 1/5 millimeter thick.
The following sintering example is preferred: A mixture of the following powders 6 parts by weight aluminum 4 parts by weight iron 1 part by weight copper, and 1 part by weight tin is pressed in a 1 1/4 inch diameter mold with a plunger powered at 30 tons to make a disc about 15 to 20 mils thick. The disc is then removed from the mold and subjected to εintering at 1500°F to provoke the reaction between the aluminum and the other metalε. After subsequent cooling, the sintered disc is leached with
10% aqueous NaOH at 160°F for 20 minutes, then rinsed and dried in argon. Blowing air 6 feet per minute at the dried disc causes pyrophoric reaction that carries the disc to 820°C in less than one second and holds it above 750°C for twelve secondε. Thiε iε a very εtrong responεe believed to be due to the manner in which the activated product iε produced. A similar improvement in catalytic response iε alεo noted.
The presence of the tin in the original powder mixture makes it unnecessary to have diεsolved tin in the leach solution to improve the leaching action. About 5 to about 15 weight % tin content in the powders iε preferred.
Nickel powder can be substituted for the iron powder in the compacts, but iε preferably mixed with 1 1/2 times its weight of aluminum powder. A 50-mil thick disc press-sintered from such a mixture and then leached 14 hours with hot 20% aqueous NaOH is more pyrophoric than the leached iron-aluminum disc of Example , but itε pyrophoricity doeε not laεt aε long. Such a leached nickel-aluminum diεc can have its pores impregnated with inert particles such as the alumina and silica mentioned supra, to stretch out itε pyrophoric heat ourput. It will for example ignite micron-sized boron particles without the need for the lowignition-temperature zirconium.
The press-sintered masεeε can be ' made thicker or thinner than 50 mils. Making them 10 mils thick for
example, makes them sufficiently light in weight so that they will fall through the air relatively slowly, particularly if the discs are 1 1/2 inches or more in diameter. A group of such discs can then be discharged in the air to act as an effective decoy for heat-seeking misεileε. Their effectiveness as a radar decoy iε improved if the discs are given a plating of copper or silver on one or both faces. Not more than about 0.1 mil of such plating is needed. Electroplating is preferred over electroless plating.
The foregoing discε are somewhat friable, particularly when only about 20 mils thick or less. To provide a useful degree of ruggednesε, εuch thin discε can have one face of unactivated metal that when sintered more securely holds the activated particles together. That face need only have a depth about 1/10 the total disc thickness. The following, iε an illustration:
In a square mold having a 1/2 inch by 1/2 inch cross section, there is firεt εpread an 0.8 mil thick layer of minuε 325 meεh iron powder. This is tamped down and then over it is poured a layer about 7.5 mils thick of a uniform mixture of the same size iron powder with an equal weight, of minus 325 mesh aluminum powder. The combination is now subjected to pressing at 5 tons per square inch to form a coherent disc about 8 mils thick and 1/2 inch by 1/2 inch in outline. It has a face about 1/10 of its thickness, of only iron particles. That disc is easily pushed out of the mold without being damaged..
The disc is now placed on a ceramic plate and so held is passed through a tube furnace heated to about 600°C. After a few seconds the disc becomes heated red hot by the inter-reaction of the aluminum and the iron in its top layer. A protective stream of nitrogen or argon can be passed through the furnace tube to keep the disc from oxidizing. The diεc iε then pushed out of the heated part of the furnace and permitted to cool for a few more seconds.
The disc is at this point extremely rugged.
It is now dropped into a 20% NaOH solution in water heated to about 80°C, to leach out much of the aluminum that has reacted with the iron. After about 30 minutes to several hours the leached disc is strongly pyrophoric, and can be removed under argon, washed and dried. It is still somewhat, rugged and will easily withstand the handling needed to fully load a decoy shell with a quantity of the discs.
Instead of being square in outline, the discs can be rectangular .or circular or have any other shape that permits them to be loaded with a minimum of unused space.
The final disc thickness can be increased to about 12 mils, the aluminum to iron proportion is changed to 2.1, and the layer of inactive powder i placed in the center of the disc and is increased to aobut 1 1/4 mils. The final product, haε a layer of unreacted metal on both faces of which are sintered pyrophoric layers each a little less than 6 mils thick.
A 1 mil thick iron foil can be subεtituted for the inactive layer, the aluminum to iron ratio iε 2.5, and the pyrophoric layerε are each about 5 milε thick.
The iron foil can be replaced by a 60 by 60 iron wire screen woven from 2 1/2 mil thick wire, the aluminum to iron atom ratio is changed to 1.9 and the overall disc is made 7 mils thick.
Perforated metal having other forms can be used in place of the wire gauze, and powdered nickel can be substituted for some or all of the powdered iron. The inert metal need not be identical to the powdered metal that is mixed with the aluminum. Copper-plated iron or nickel more effectively sinters to the active particles and can be effectively used.
The foregoing discs are very good catalystε and can be used in the catalytic proceεε metioned hereinabove. For catalytic use it is generally safer to first eliminate the pyrophoricity, as by treatment with H 2 0_ and water as described in parent Patent 4,443,557. An active platinum disc made by the press-sintering
technique is also a very good catalyst after leaching, but eliminating its pyrophoricity is best effected by contacting it with dilute hydrochloric acid or other mineral acid. Catalytic platinum prepared this way has the added advantage that itε content of contaminants ■ εuch aε carbon or iron can be kept extremely low. When preparing εuch catalytic platinum with an aluminu -dif- fuεion εtep, the diffuεion retort uεed to contain the diffuεion materialε tends to diffuse some of its constituents into the platinum. Carbon is thus frequently found in platinum that havs been given a diffusion treatment in a εteel retort. The uεe of a diffusion-coating retort made of nickel containing less than 0.9% carbon, does prevent εuch carbon contamination.
However, the diεcε are particularly useful aε decoy material for heat-seeking missileε. Their pyrophoric character and their compactness permit loading of the discε in a discharge shell for example, with very little waεte space and somewhat greater pyrophoric material than the prior art pyrophoric foils.
Other metals, even copper, brass and bronze, can be activated by the press-εintering technique. Not all εuch activated metalε are pyrophoric, but they are all good catalysts. The thus-activated copperε, brasses and bronzes are quite effective in the alcohol synthesis of Fig. 1 for example. The chromium, molybdenum, manganese, vanadium, titanium, tungsten and tin alloy catalysts described above for denitration, are also effectively prepared by the press-sintering technique. Expensive alloys can be replaced by sintered alloys of their constituent metals or only of their essential constituent metals.
For some purposes it is desirable that the activated material be carried by wires. Thus a 3-mil thick nickel wire can be coated to a thickness of 10 mils with a suitable mixture of iron and aluminum powders held in place with a resin binder, and the coated wire then passed through a furnace to drive off the binder and cause the iron and aluminum powders to
while the web is hot, at leaεt 500°C is more effective than on a colder web, and only requires a compacting force of about 30 kilograms per centimeter width of the web. Compacting can also be effected on the leached web, that is the web leaving the caustic solution, but is not as effective. The aluminide particles on the leached web are softer than those on the unleached web when the webs are at room temperature, but heating a pyrophoric leached web in an attempt to soften the leached particles, adversely affects their pyrophoricity. The greater the compaction, the more pyrophoric strips can be packed into a decoy shell used against heat-seeking missiles.
By way of example, a one-meter-long induction coil furnace can be provided for coated foil to move through at the rate of two meters per hour, followed by a five-centimeter gap through which the foil cools by radiating its heat to the surroundings, and then a a ' ten-centimeter travel through a leaching bath held at 190°F. Following that bath the foil moves through a falling stream of rinse water that terminates the leaching, rinεeε off the leachant, and cools the foil to about room temperature. The water-web foil can then be dried under argon and spooled.
There is generally no need to use a diffusion coating energizer εuch as ammonium chloride in the atmosphere adjacent the surface being diffusion coated by the foregoing technique, but it can be used and will then help if the incoming coil has not been completely cleaned. Blasting with a stream of blasting grit generally does an adequate cleaning. With or without an energizer in an inert or reducing diffusion atmosphere, a continuous spray of aluminum on a continuously fed foil, or a continuouε paεεage of such a foil through or on a body of molten aluminum, does not leave the objectionable roughnesε described above for the dipping of individual workpieceε in molten aluminum.
However, the smoothness of the sprayed-on aluminum layer does not assure suitable diffusion aluminizing when the diffusion step is conducted at elevated temperatures, i.e., about 1300°F. Thus a two-mil thick 1010 type steel when εprayed with molten aluminum and rapidly heated to 1450°F where it iε kept for 30 minuteε and then %
cooled, becomes wrinkled and distorted. A similar distortion problem is experienced by a 10-minute diffusion heat at 1600°F. Such wrinkling and/or distortion makes it awkward to manipulate the foils, but essentially entirely disappears during the leaching, and so does not significantly prevent the tight packing of such activated foils in containers for use aε thermal decoyε as described, for example, in Serial No. 281,405. Sprayed-on aluminum coatings weighing from about 5 to about 30 milligrams per square centimeter, whether sprayed on as molten aluminum or aε a εlurry of aluminum particles, lead to the wrinkling and distortion.
For activating only one face of the foil, the other face can be protected or masked against diffusion, or the aluminum spray coating can be confined to the one face to be diffusion coated. This also ledε to distortion and wrinkling.
Pre-alloying the aluminum with 5% ot 15% silicon by weight reduces the wrinkling and distortion, but. does not eliminate them completely. However, the diffusing in of a pre-coated foil yields after leaching an activated product having a thermal output when exposed to air, somewhat less than that of foils pepared by pack diffusion. Alloying with other materials such as zinc, calcium, germanium, magnesium, nickel and boron, also reduces the wrinkling and distortion but has less of an adverse effect on the thermal output . Conducting the leaching at elevated temperatures such as over 220°F, and particularly with aqueous solutions of at leaεt 20% caustic soda or potash by weight also helps.
Wrinkling and distortion can also be reduced by conducting the diffusion at lower temperatures. Below about 1000°F, the wrinkling and distortion is completely prevented, but the diffusion time is increased to as much as four hours or more. Also at these low temperatures ammonium chloride is not a preferred energizer and pack diffusion iε simpler to conduct. Such low-temperature pack diffusion iε best conducted with extra precautionε to avoid εide reactions such as etching, that are caused by the presence of moisture. Thus anhydrous water- insoluble CrCl, can be used as the energizer or the diffusion-coating pack can have
interact. The resulting aluminide-coated wire is then passed through a leach bath to dissulve out much of the aluminum.
The final wire with itε activated coating can then be coiled up or wound on a form for catalytic uεe. For decoying heat-seeking misεiles, the wire can be wound up into a tight coil and loaded into a discharge shell. Upon discharging the shell, the pyrophoric wire uncoils and pyrophorically reacts with the air to provide a decoy heat generator that does not scatter much.
Before loading, the wire can be pasεed between compacting rollers that give the coating a recatangular cross-section to thus make the coiling more compact.
Similar resultε are obtained when the wire carrier iε replaced by a εtrip of 1 mil thick foil about one to two millimeterε wide. In both caεeε the hot cloud developed by the decoys are only about 2 meters wide or less, and more effective in their decoy action. Cutting one radial slit from the coil center to its edge does not increase the cloud εize εignificantly inaεmuch aε the cut lengthε tend to entangle with each other as they unpeel. However the cutting eases the unpeeling.
When the coating layers contain iron aluminide, the caustic solution preferably contains a little dissolved tin, as described in the prior art. Also as described in the prior art, a little hydrogen peroxide can also be added to the caustic solution. Potassium hydroxide can be substituted for all or part of the sodium hydroxide.
The aluminide-forming reaction in tube 16 iε generally completed in a matter of seconds, so that the web can be pasεed through the furnace at a rate of about 3 meters per minute, and the furnace tube need be no longer than about 30 or 40 centimeters.
The above-described roll compacting carried out
embedded in it one or more packets of anhydrous aluminum chloride in which that energizer iε εealed in an envelope made of plaεtic εheeting that meltε and decompoεed at about 300°F to 600°F. Polyehtylene and polyethylene terephthalate plastics are suitable for thiε purpoεe. Aε the packet-containing diffuεion-coating pack iε heated to diffuεion-coating temperature in a loosely covered retort contained in an outer retort whose interior is kept flushed with argon or the like, any moisture in the inner retort is first driven out and flushed away, after which the packet walls melt and decompoεe to liberate the anhydrouε aluminum chloride εo that it can volatilize and effect the neceεsary energizing. It it iε desired to minimize the presence of carbonaceous material such as that reεulting from the aplaεtic melting and decomposition, the packets can be made of aluminum foil folded over and cemented together by means of a very thin plastic coating.
Wrinkled and distorted foils can also be • subjected to a flattening treatment as by rolling between thickness-reducing rollers. The pressure applied by these rollers should only be enough to effect very little or no thickness reduction.
The leaching of aluminum from aluminized cases to provide an activated subεtrate has been described in the art as conducted in various manners. Reference is hereby made to U.S. Patents Noε. 3,637,437 (col. 5), 3,809,658 (cols. 1 and 2), 3,939,097 (cols. 4, 6 and 7), 4,206,081 (col. 2), 3,809,658 (cols. 1 and 2), 4,292,208 (col. 9 and the listed references), 4,179,412 (cols. 3 and 4), and Japanese publiεhed Application No. 55780/1976.
In some caseε, it iε deεirable to conduct the leaching at relatively low temperatures, at 140°F or 160°F, for example. Thus, a cold leaching bath of 10% to 20% by weight NaOH in water with or without a cold water jacket and/or agitation during leaching of aluminized iron foils originally 1 mil thick, can have its temperature rise limited so that it gets no hotter. About 20 to 40 minutes of such low-temperature leaching yields highly pyrophoric iron foils. Even lower leaching temperatures can be used.
For the most vigorous pyrophoricity, an alumi-
nized case depth about 2 mils thick should be provided on an object in which εuch caεe represents about 80% of the total thickness of the aluminized object. The forming of an aluminized case increases the overall thicknesε of the original object by about three-fourthε the caεe depth. For the above-noted thick caεe, leaching with the 50% εolution at boiling for one minute develops a pyrophoricity that cauεeε the substrate to heat up to over 1000°F when it is subsequently dried and exposed to the air. To get hot enough on a stainleεε steel to εcorch paper, it iε preferred to provide a case depth at least one-sixth the total thickness of the body of a stainless steel article, where the activated case is only on one face, or at least one-twelfth that thickness where both faces are activated.
Pyrophoric stainless steel screens and foils can be prepared on a continuous basis, as described -above for the plain steel foils. Such continuous treatment can be used to prepare pyrophoric or non-pyrophoric products depending upon whether the foregoing control limitations are observed. Thus, very high pyrophoricity iε developed with type 430 εtainleεε steel screening woven from 20 mil thick wire aluminized with a 2-mil-thick case having a surface aluminum content of 50 weight percent, leached for only about 1/2 minute with a 50% aqueous solution of NaOH held at about 280°F. Leaching solutions as strong as saturated aqueous caustic can be used at temperatures as high as 300°F, even shorter leach times being then preferred, but 40% NaOH solutions at 160°F are preferably used for aε long aε 30 minutes to develop high pyrophoricity. It iε not helpful to have stannite tin present in leaching solutionε that are used to leach εtainlesε εteels.
Where the leaching solution is stronger than 50%, as for example when using solutions that are saturated with caustic at the leaching temperatures, the leaching times are further shortened by about 1% for every degree Fahrenheit increase in leaching temperature about 290°F. A leaching solution that has been used loses a little of its activity both because some of its caustic iε consumed and because soluble aluminate saltε are formed in it. A leaching bath originally having a 50% cauεtic concentration but uεed to
the point that its caustic concentration has been reduced to 40% by weight, actually has a leaching action more cloεely correεponding to a freεh 35% caustic concentration.
A type 430 stainless steel 50 X 50 wires per inch screen woven from 10 mil thick wires iε aluminized in a simple pack of 20% aluminum powder and 80% powdered alumina, with 0.5 A1C1- added as energizer. A 20-hour hold at 850°F under hydrogen, yields a 2 mil thick case that iε then leached with 30% aqueous NaOH for 2 1/2 hourε at 110°F to give a product that will scorch paper after rinsing, drying and then expoεed to air. After it has completed its pyro¬ phoric reaction with air it makes a very effective catalyst for reducing NOX in internal combustion engine exhausts and coal-burning furnace smokestacks by reaction by reacting with a little H 3 at about 300° to 375°C. It also makes a good catalyst for oxidizing ammonia to nitric oxide, for decomposing ammonia into nitrogen and hydrogen, and for synthesizing ammonia from nitrogen and hydrogen.
A 60 X 60 wires per inch screen of type 304 stainless steel woven from wires 8 mils thick, is aluminized as in Example 3 but with NH.C1 substituted for the AlCl,_ an aluminizing temperature of 1650°F, and the time at that temperature two hourε. After cool-down the εcreen iε removed from the coating pack and dropped into 25% aqueous caustic by weight held at boiling for 30 to 60 εeconds, then immediately rinsed. Upon drying it showε a pyrophoricity even greater then the screens of Example 3.
Using a fine-wire thermocouple, pyrophoric temperature increases to over 900°F have been measured with type 430 stainless steel εcreenε aluminized aε in Example 3 and leached as in Example 4.
The foregoing pyrophoric activity is imparted by the same process to other iron-chromium and iron-chromium- nickel alloys containing over 5% and as much as 30% chromium. The crystallagraphic εtructure of theεe alloys can be of any type, including auεtenitic, martenεitic and ferritic. Specific εtainless steel alloys suitable for such treatment include 25-12 stainless steels, as well aε typeε 316, 321 and 247 and iron containing 12% chromium and the typeε 304 and 430 εtainleεs steel already noted. Although some of these stainless steelε are not true εteelε inaεmuch aε they contain little or no carbon, they all come within the stainless steel category of the present invention.
As pointed out above, the diffusion aluminizing conducted to provide pyrophoric stainless steelε iε very effective when carried out at temperatures of about 800°F to about 1650°F, and is followed by a vigorous leaching with aqueous caustic having at least 25% NaOH by weight. If more than about 15 milligrams of aluminum is leached out per square inch by vigorous leaching with aqueous caustic having at leaεt 45% caustic, the leached case becomes loosened and can then be removed by rubbing, for instance.
The pyrophoric stainless steels are strongly catalytic aε well aε pyrophoric, and remain strongly catalytic when the pyrophoricity is lost as by reacting with air or by dipping in 3 volume % H 2 0~ in water. Thus, the pyrophoric stainless steelε are particularly effective catalyεts for reducing NOX emissions from furnace stackε and the like with the help of NH- or reducing gaεeε, as described in U.S. Patent 4,897,375. For such use, these pyrophoric catalysts can be merely permitted to react with air before, during or after they are installed in the stack. However, they can alternatively have their pyrophoricity eliminated by H 2 0 2 treatment, if desired.
The pyrophoric stainleεε steelε, like non-pyro¬ phoric stainlesε steels, show their maximum catalytic effectivenesε for NOX reduction at temperatures below about 350°C. They are accordingly very desirable for such use.
The pyrophoric stainleεε steel is also very effective for catalyzing the formation of ammonia as well as its decomposition, and the oxidiation of ammonia to nitric
oxide. For such purposes the catalysts are preferably in the form of wire screening as described in U.S. Patent 4,897,325, or in the form of tubing as described in Japanese Patent Application No. 55780/1976, or can be fabricated or even cast in any other deεired εhape.
The maximum temperature attained by a pyrophoric metal foil or screen when it undergoes its pyrophoric action, also depends on the proportion of activated εurface to non-activated core. Inaεmuch aε the catalytic action of the activated εurface iε essentially unaffected by how much unactivated core is under it, an activated catalyεt can have a very thick core and thuε appear not extremely pyrophoric aε indicated by itε temperature riεe upon exposure to air, yet be a highly effective catalyst. However, for catalytic purposes it is preferred, particularly for gaseouε reactionε, to have the catalyεt surface undiluted as much as practical by inactive core. This preference, conεidered with the greater effectiveneεs of the surfaces that have been more intensively pyrophorically activated, accordingly makeε it deεirable to have the pyrophoricity aε vigorouε aε practical, even when the pyrophoricity iε removed by an after treatment after it iε developed and before catalytic operation iε εtarted.
For NOX reduction the εtainleεε εteelε can, before activation, contain helpful alloying metalε εuch aε vanadium, manganese, and other metals referred to in U.S. Patent 4,897,375. Thuε, type 316 containε molybdenum, type 321 containε titanium, and type 347 containε columbium. Theεe alloying metalε can be preεent in the original εtainleεε steel, or they can be placed or diffused into the surface to be activated, or they can be alloyed with the aluminum that is to be diffused in as the first step in the activation. The content of any of these alloying metals is preferably at. least about 5% weight of the activated case.
The presence of about 10% manganese in the surface of those εtainleεε steel catalysts improves their
effectiveneεε, particularly in stack gases containing high surfur dioxide content, but the improvement is gradually lost over a span of about a day or εo. A typical diffuεion coating with manganese is conducted at 1725°F for five hours with a diffusion coating pack of:
53 g. manganese powder
212 g. Al^ 0 ^ P owc -* er 3 g. NH.C1 powder It can also be used to diffuse manganese into nickel as well as nickel alloys other than εtainless steels. On nickel it gives a weight gain of about 21.9 milligrams per square centimeter, and a case depth of about 1.4 mils.
The manganeεe-carrying nickel and other nickel alloyε have improved catalytic action, for example, in the oxidation of formaldehyde to formic acid, aε well as in the methanation of CO. Nickel-cobalt-molybhenum alloyε heretofore used in such methanation oare particulary im¬ proved.
A manganese content over about 20 weight percent in the outer skin of any of the foregoing catalysts does not seem to be worth the trouble.
For NOX reduction of internal combustion engine exhausts, the foregoing catalysts, or any similarly reacting catalyεt is placed in the exhaust line, preferably close to the exhaust ports of each engine cylinder of combustion discharge. Where the exhaust line includes a converter that oxidizes carbonaceous gases, the catalyst can be fitted to the converter outlet.
A small stream of ammonia is introduced into the exhaust so that it can react with the NOX in the exhaust. Where there is an engine-driven pump that injects air into the exhaust, the intake of that pump can be connected to a source of ammonia such as a container of ammonia-evolving material like ammonium carbamate or ammonium carbonate or ammonium bicarbonate. Liquefied ammonia can also be used, but must be kept under high pressure. The container is kept closed when the engine is not. operating, but. when operating its contents deliver a gradual stream of ammonia or ammonia-containing gases which are pumped into the hot
exhaust with or without the air the pump delivers. A pump with an operating speed controlled by the engine εpeed does a very good job of metering the desired ammonia content into the hot exhaust. The metering rate is easily adjusted εo that the exhauεt aε diεcharged into the atmoεphere has no ammonia odor.
With either arrangement, the ammonia-εupplying container iε conveniently vented to a supply of absorbent such as a carbon-filled caniεter which can be the εame or different from the caniεter uεed to abεorb gasoline vapors. The vent can be controlled by a valve which is normally closed but opens to relieve excess presεure aε well as in response to intake suction.
The use of an ammonia feed reduces the need for exhaust gas recirculation, which can then be diminished or entirely eliminated. More power iε then obtainable from the engine.
For ammonia oxidation to nitrogen oxides, the pyrophoric or non-pyrophoric stainless steel screens
activated by aluminizing and leaching can merely be substituted for the platinum screens used in the prior art- reactors with a reduction in operating temperature to 700°C or below. The pyrophorically activated screens are preferred, particularly when their porous catalytic εurface is partially impregnated with potassium salts such aε potassium carbonate or vanadate.
The radar reflectivity associated with pyrophoric foils is also increased by mixing them with εtandard aluminum radar chaff or foilε. Such aluminum chaff or foilε only about 1/2 mil thick or thinner, mixed with two to five timeε aε many pyrophoric. one-inch diεcε of iron foil, make an effective heat and radar decoy when ejected aε a maεε from an exploding cartridge.
Regardleεε of how an activated leached iron or nickel εurface iε obtained, it can be uεed for many catalytic purpoεes including the oxidation of methane, and such use is improved by depositing on the surface a film of platinum or palladium, or a thin layer of fine zirconium oxide powder. Metal films are readily depoεited by
decomposing the chloride or other salt of such metal. Powders can be applied by mixing them with colloidal alumina or silica in suspension in water, then applying the suεpen- εion and finally permitting the water to evaporate. The ZrO~ changeε the wave length of the radiation emitted when the activated surface pyrophorically reacts.
According to another aεpect of the preεent invention, there are provided highly active-heat-generating compoεitions which burn in air when heated, but are esεentially inert at temperatureε below about 50°C to 100°C so they can be conventiently stored for use when deεired.
Aε εhown, pyrophoric materialε pre ' pared by leaching FeAl, or NiAl, for example, can be εtabilized by εubjecting them to a very small quantity of oxygen in a manner that does not permit them to appreciably heat up, the resulting stability tends to break down at about. 50*°C or a little higher.
According to the present invention, there are provided pyrotechnic compositionε wwhich ignite at temperatureε about 100°C, e.g., at. about. 300°C, and have a εubεtantial aluminum content as well as a high thermal output. These compositions are activated aluminides of metals like molybdenum, zirconium and colombium that when not combined with aluminum ignite in air at about 500°C to 700°C or higher at atmospheric pressure. These metals are easily combined with aluminum to form alloyε or aluminides having two or more atoms of aluminum for each atom of ignitible metal, and when so combined generally have ignition temperatures not much different from that of the pure ignitible metal as noted above. Incorporating about. 2% to about 10% boron in such alloy, based on the weight, of the ignitible metal, generally lowers the ignition temperature by about 20°C or somewhat more. However, the ignition temperature of the aluminide with or without the boron, is lowered about 100°C to about 150°C or more by activating the aluminide.
The activation of the present invention involveε the leaching out of some of the aluminum, as with aqueous caustic soda or caustic potash. For this activation, the aluminum alloy preferably has between about 2.5 and 3.5
atoms of aluminum for every atom of alloyed ignitible metal, and the leaching preferably removeε all the aluminum in exceεε of two atoms per atom of ignitible metal. This is illustrated by the following example:
One kilogram of aluminum covered : by a cryolite flux is melted in a εtainleεε steel retort under argon, and there is then stirred into the melt 600 gramε of powdered molybdenum.. The stirring is continued for about 1/2 hour while the contents of the retort are maintained at about 1200°C to about 1400°C to complete the alloying.
The melt iε then permitted to cool and εolidify, after which the metal layer is crushed into small pieces and the pieces ground to a maximum particle size of about 0.3 millimeter. The ground product is now poured into an exceεs of 25% NaOH solution in water. Bubbles are immediately evolved aε the cauεtic attackε the alloy particleε, and the evolution beginε to noticeably εlow down after εeveral hours, reaching a very low level after about six hourε. The cauεtic is then poured off, and the residual particles washed with water and dried.
Thus activated, the particles have a porous surface and are stable in air at temperatureε aε high as 300°C. However, when a mass of the particles is heated in air to above that temperature, the particles ignite and vigorously react with the air. The reaction is an oxidation and is completed on the smaller particles before it iε completed on the larger particleε of the ground mass, so that the pyrotechnic effect is more intenεe for about the firεt minute, and dropε off somewhat for about another minute. On an asbestos pad the oxidizing particles become red hot and gradually crumble to a powder. Such pyro¬ technics generate temperatures well over 1000°C and can accordingly be used to supply heat for other purposes.
Zirconium and columbium behave very similarly when treated as in the foregoing Example. After activation, they ignite at about 350°C in air at atmoεpheric preεεure, and the ignition point of their aluminum alloy before acti¬ vation is about 500°C, being not much different from the
ignition point of the pure metalε.
The activities of the activated alloyε are lower when the leaching iε terminated earlier, and are alεo lower when the alloyε subjected to the activation have a lesε than 3:1 proportion of aluminum atomε to ignitible metal atomε. There are alεo εome reactivity increases when the leaching is made more intense, as by starting with a hot or boiling caustic solution, and by increasing the caustic concen¬ tration to εaturation. However, very good reactivity iε obtained when the leaching iε effected at 20°C, although the leaching iε εlower at that temperature. At boiling temperatureε with saturated caustic, the leaching can be completed in lesε than two minuteε.
It is not essential for the aluminides of the present invention to be prepared by melting. Thus, iron, zirconium, titanium, molybdenum and columbium can be effectively alloyed with aluminum by a thermal diffusion.
Fine powders of the separate alloy ingredients can be uniformly mixed in a diffusion coating retort and heated to about 600°C in an A1C1 atmosphere for only about six hours to produce uεable alloy when the ignitible metal powder particles are no larger than about 10 microns. Larger particleε take a little longer. Other halide atmoεphereε, such as of anhy J drous CrCl3-,, ei.t.h.er in i.t,s wat.er-εol.u,bl,e or water-inεoluble form, or elemental chlorine, bromine or iodine, can be used in place of the A1C1 aε the diffusion- energizing atmosphere. Only about 1/2% to about 1% of such . energizer is mixed with the powders to be alloyed.
Tri-aluminides of some of the noted metals are also available as articles of commerce.
The leaching of the present invention can alεo be effected with inhibited hydrochloric acid such as that referred to supra, but the resulting activation iε not aε great aε produced by cauεtic leaches.
There can also be included in the foregoing alloyε ingredientε that improve the pyrotechnic behavior.
Thuε, about 2% to 20% of boron of magnesium or iron or mixtures of these, are helpful in this respect, and can be added to a melt or to a diffusion-alloying mixture. Also, these metals can be introduced by diffusion into a
pre-formed aluminide or by diffuεion with the aluminum. For example, 250 gramε of powdered ZrAl. can be mixed with 10 gramε of powdered boron and 5 grams of solium fluoborate, and εubjected to a diffusion heat as described in U.S. Patent No. 3,801,357, but without using inert solid diluent, for three hours at 1800°F in an argon-bathed atmosphere, to diffuse the zirconium and boron into aluminized nickel powder or NiAl, .
About 1% to about 10% of iron can be similarly introduced into the aluminide with or without the boron, to provide activatable alloys that after activation ignite at temperatures of about 300°C or a little lower. Magnesium- aluminum alloys can also be activated by the foregoing tech- niqueε to provide activated material having ignition temperatureε below 300°C. The nagnesium-aluminum alloys preferably have, before activation, at leaεt two atoms of aluminum for every atom of magneεium, but can be activated even when the aluminum-magnesium atom proportion is as low as 1 1/2:1. The aluminum-to-zirconium atom ratio iε preferably at least 4:1 but can be as low as 2:1.
Including 2% to 20% boron in the magnesium- aluminum or zirconium-aluminum alloyε, based on the weight of the magnesium or zirconium, also increases their pyrotechnic output.
The foregoing pyrotechnic improvements are also obtained with alloys in the form of foils and sheets, aε well as powders.
The boron additions of the present invention can alεo be effected by the procedureε deεcribed in U.S. Patent- No. 4,536,215.
The foregoing low-ignition-point activated alloys are readily ignited with an ordinary household match.
A stainless steel workpiece can be provided with a catalytic pyrophoric surface, by first plating the εtain¬ leεε εteel εurface with nickel or iron, then aluminizing the pla . ted εurface, and finally leaching the aluminum out of the plating. Thuε, a one to two mil thick acid nickel electroplate on 304 stainleεε steel can be aluminized at 750° to 800°F for twelve hourε, as in U.S. Patent No. 4,154,705, to provide an aluminum pick-up of 1.9 to 2
milligrams per square centimeter, after with the aluminized surface can be leached in hot 20% aqueous NaOH to reduce the pick-up to about 1.9 to 2 milligrams per square centimeter. This leaves a stainleεε εteel workpiece with a very active εurface highly suited for a water-electrolyzing electrode, anode or cathode, with reduced over-voltage. It iε alεo suitable for use as a fuel cell electrode, both anode and cathode.
The active nickel εurface becomeε warm when first exposed to air, showing that it is pyrophorically reacting with the air. Its best cathodic electrolyzing effects are provided if kept from exposure to air or oxygen. These results are also obtained when the aluminizing is conducted at other temperatures and for other times and with other diffusion-coating- packs. Similarly, the nickel platings can be deposited by ion bombardment, gas plating or other tech¬ niques, and the stainless steel can be of any other type. The stainless steel support need not be more than about 10 mils thick, and can be a foil or screen.
The high diffusion temperatures suggeεted in U.S. Patent No. 4,116,804 are not deεirable for aluminizing a stainless steel supported thin nickel or iron layer, inasmuch as high diffuεion temepratureε tend to cauεe some of the chromium from the stainlesε steel to diffuse into the thin nickel or iron layer and lower its activity for elec¬ trolytic use. It is accordingly desirable to keep the diffusion temperature below 1100°F and to limit the dwell time at diffusion temperature to prevent chromium from reaching the outer surface of the nickel or iron coating.
The nickel or iron top coating can be given a top flash plating of silver or platinum about 0.05 mil to about 0.5 mil thick, before the aluminizing. Such a flash coat of nickel over an iron-plated stainless steel is alεo helpful.
Similar flash coatings can be applied over the activated nickel or iron plated stainless steels after the activation is completed by aluminizing and leaching.
Even without the stainlesε εteel backingε, a self-supporting iron or nickel screen or foil having itε surfaces activated as noted, with or without the flash top coatings, make very good fuel cell electrodes, much like the similar activated metals of British Specification No.
A εtainless εteel backed activated nickel or iron plating alεo makeε a good catalyεt for NOX reduction.
When electrolyzing water in which an alkali like NaOH iε diεsolved to increase its conductivity, a nickel anode previously activated by aluminizing to give a 2-mil thick case followed by a one-hour treatment in boiling 60% or 70% NaOH, provideε a much greater anodic current denεity than a correεponding anode in which the leaching waε only with hot 20% aqueous caustic. Indeed, at low inter-electrode voltages as against an untreated pure nickel cathode, the anodic current density is increased- as much as seven-fold. The foregoing anodeε are preferably dipped into dilute hydrogen peroxide after the leach is completed, with or without an intervening rinse in hot or boiling water.
A somewhat smaller but still spectacular current density increase is obtained from boiling 40% aqueous NaOH leach for one hour.
In general the leaches with 50% or εtronger cauεtic εhould not be extended εo aε to remove much of the aluminum at the interface between the aluminized caεe and the nickel core under it. Too much removal at that location can reduce the adheεion between the core and the leached caεe and cauεe the leached caεe to εpall off. A one-third hour leach at about 200°F iε appropriate for caεeε aε thin aε 0.5 mil, but boiling 70% cauεtic εhould not be uεed for more than about 10 inuteε unless the case is thicker than two mils. Preferred leaching iε with about 30% to about 60% aqueouε NaOH at temperatureε from about 212°F to about 300°F for at leaεt a half-hour, but not long enough to loosen the leached layer.
The foregoing vigorous leachings alεo improve the cathodic current denεity when the leached nickel electrodeε are uεed aε cathodeε, but here the current denεity increaεeε are only effected at inter-electrode potentialε greater than about 1.5 voltε.
A 1.5 to 2 mil aluminized caεe applied on 430 εtainless steel by powder pack diffuεion below 1000°F iε preferably leached for not over about 1-3/4 hourε when • the leaching iε effected at about 150 to about 190°F with 10% to 30% cauεtic. Moεt preferably εuch leaching is for about 1 to about 1 1/2 hours, particularly for use aε an NOX-reducing catalyst, with NH_, in furnace and internal
combustion engine exhausts. Thinner cases should be leached for proportional times. Leaching at lower temperatureε, e.g., at 90°F, can be extended to about 3 hours.
When leached aluminized stainlesε steel screening is uεed for NOX removal, better reεultε are obtained with the greateεt degree of leaching, but. the aluminized caεe εhould not be completely leached through.
As noted above, the leaching of aluminized ferrous metal is greatly benefitted by the presence of disεolved tin in the leaching liquor. Such leaching buildε up a tin-containing εludge that can be treated to recover and re-uεe the tin valueε. To thiε end the εludge can be filtered off or separated by centrifugation, and washed, as in a perforated barrel washer to carry off most of the adhereing cauεtic liquor. ' The waεhed material iε then dipped in aqueouε acid such, aε 1:1 dilution of concentrated HCl with water, to bring it to approximate neutrality or slightly acid. A pH of about 3 to about 9 iε appropriate.
The approximately neutralized material iε then retorted at a temperature of about 275 to about 375°C in a non-oxidizing atmoεphere for about 5 to about 10 hourε. The reεulting material analyzeε to about 70% tin and is completely soluble in strong HCl or other acid. It can be used as a general source of tin, for example by disεolving it in concentrated HCl warmed to about leaεt about 60°C to yield a stannouε chloride solution that can be added to the caustic leach for the leaching of aluminized ferrous metal.
The retorting is the key treatment, inaεmuch aε without the retorting the sludge will not properly disεolve in the εtrong acid. Hydrogen or inert gaε atmoεphereε such as argon can be used in the retorting. A 10-centimeter tall retort works satiεfactorily in that only about 5 retort, hourε iε then needed. Excess retorting does not help or hurt.
The leaching of aluminized iron foils or powder iε improved when conducted with a little hydrogen peroxide in the leaching liquid. Aε little aε 0.1% H 2 0 2 by weight of the leachant iε enough to εhow such resultε, and from about
0.2% to about 0.5% is preferred. Concentrations of 3% or higher tend to darken the work and diminish its pyrophoric activity.
By way of example, to a liter of 10 weight percent solution of NaOH in water there is added 5 gramε of SnCl 2 2H 2 0 and 5 cc of 30% aqueous H 2 0 2 , and the resulting mixture at room temperature is used to leach 2 mil thick iron foil that has been aluminized to a depth of 1/2 mil on both its faces. The leaching generates a very small amount of gas as compared to corresponding leaching without the H 2 0 2 , and is completed in about 30 minutes even if the leach solution warms up to about 50°C during the leaching. Esεentially no sludge precipitates from the leach solition, even though a large quantity of tin-containing sludge precipitates if the H 2 0 2 is omitted.
About the same results are obtained when the leachant is KOH and εtarting leach solution is at any temperature from about zero to about 50°C, although leachant that starts at 50°C can heat up to about 60°C. The foregoing leachings are conducted with about one hundred times as much leach solution aε substrates being leached, by weight. Preferred caustic concentrations are from about 8% to about 20% NaOH of KOH in water, by weight.
Instead of pouring H_0 2 into a leach εolution, peroxideε such as sodium peroxide, potasεium peroxide and calcium peroxide can be added to the leach εolution to form H 2 0 2 in εitu.
The foil activated in accordance with the foregoing example alεo εhows a small gain in pyrophoric heat output aε compared to the correεponding foil activated with¬ out the help of the H 2 0 2 . Iron powderε also give about the same results aε the foils do.
Leaching of aluminized iron, either foil or powder, is best conducted with some tin or stannite ion diεsolved in the leachant, but the concentration of the tin can be reduced to as little as about 1/2 gram disεolved tin per liter of leachant when the H 2 0 2 of the present invention iε present in the leachant. Preferably the dissolved tin
content iε as high as 1 to 3 grams per liter.
Not only is leεs tin needed in the leachant, but the iron activated with the H 2 0 2 in the leachant containε leεε tin than iε contained in iron activated purεuant to the prior art. Such tin is introduced as metal into the pores of the activated iron and even in very small amounts helps preserve the activation.
It is noted that the presence of the H 2 0 2 in the leachant according to the present invention, has an effect oppoεite to that of the H_0 2 when it iε applied to the activated metal after the leaching is completed. Such later application causeε the activated metal to loεe εome or all of its pyrophoricity, and to turn black.
The small increase in heat output cauεed by the preεence of the H 2 0 2 in the leachant, can be heightened by εubεquently subjecting the activated metal to the short treatment with dilute acid, with or without the folding, as described above.
The foregoing leaching, with or without the H 2 0 2 , iε alεo very effective for leaching the rapidly formed sintered aluminum alloyε. Those alloys are of the Raney type formed by placing the alloy precursor metalε on . a carrier and then rapidly heating the combination to a temperature high enough to trigger the inter-reaction of the precursor metals.
A particularly desirable technique uses as a carrier inexpensive steel such as type 1010, in the form of a foil about 25 to 50 microns thick. Such a foil can be seriously embrittled by the inter-reacting metals at the high inter-reaction temperatures generated, and to avoid excessive damage, the precursor metals are applied in at leaεt two stages, with the first stage arranged to generate relatively low inter-reaction temperatures. Thus the atomic proportion of the aluminum to the iron, nickel or cobalt precursors should be no greater than about 2, or the metal alloying with the aluminum should be mostly iron, or the precursors can be diluted with preformed alloy, or com¬ binations of these techniques uεed. One deεirable
arrangement uses as a first stage a mixture of:
50 grams iron powder 68.4 grams aluminum powder 14.8 grams nickel powder This mixture can be poured onto the εteel foil in a layer about 74 microns thick, or suεpended in a binder εolution that iε applied to the foil or into which the foil iε dipped. A typical binder εolution iε a 6% εolution of poly- ethylacrylate in methyl chloroform. The dried combination iε then heated to about 700°C, setting off the reaction between the aluminum and the other metals. After aboutseven seconds the reaction is completed and the alloy particles formed are sintered to each other and to the foil, with the thus-coated foil retaining some of itε malleability. It can for example be bent at leaεt about 20 degrees around a mandrel 3 centimeters in diameter.
Over the reacted coating there iε then applied another precurεor layer, thiε time a mixture of
108.8 gramε aluminum 51.2 grams nickel 40.0 grams preformed NiAl.,
2.0 gramε boron and the leat treatment repeated. The reεulting coated foil can εtill be bent at least about 20 degrees around a mandrel 3 centimeters in diameter.
The final product, where both the precurεor layerε are about equal in thickness, is esεentially a mixture of iron and nickel trialuminideε, with a very smallcontent of boron, sintered to aluminized iron foil. It is noted that when the precursor layers are applied by dipping, the resulting coatings are on both faces of the foil. Either way, the aluminide-coated foil is still εtrong enough to hold itεelf together and hold the aluminide particleε in place. It iε now leached aε for example in 10% aqueouε NaOH at 50 to 65°C for two to thirty minuteε, perferably with tin diεεolved in the leachant.
After rinsing, the leached product can be compacted between compacting rolls, and will then be about
125 to 200 micronε thick. It iε highly pyrophoric and for maximum pyrophoric heat, output, the heat treatmentε are conducted in a protective atmoεphere. Conducting them in air for a total time less than about. 30 seconds does not materially detract from the pyrophoric heat output. It will be noted that the reacted precursor metals as well aε the carrier foil are rendered pyrophoric by the leaching. Also some of the carrier foil will oxidize during the pyrophoric heat generation, even when the foil iε not rendered pyrophoric.
The foil can also be kept from excessive dete¬ rioration during the sintering operation by holding it in contact with a heat absorber that keeps it from getting too hot. Thuε the foil with a coating on only one face can be fed through the sintering step while its other face iε pressed against the rim of a εtainleεε εteel wheel that rotateε to effect the feeding. The rim should be fairly thin to permit adequate sintering.
The use of very thin foils, e.g., less than 25 microns thick, preferably lesε than 15 micronε thick, makeε possible a decoy action with incandescence that startε immediately upon exposure of the activated material to the air. When carrier foils are over about 50 microns thick, the incandescence is delayed a fraction of a second or more, whether the foil has the sintered-on layer on one or both of its surfaces. In any event the sintered-on layers should be at least about 25 microns thick, before or after compacting.
Such thin foils are preferably stainlesε εteelε, type 302 for example, inasmuch as they better resiεt the sintering operation. By way of example
A coating binder iε prepared by diεεolving 10 parts by weight of acrylate resin in 90 parts of acetone. Into 100 gramε of thiε solution is stirred the following powders:
220 gramε Al (1-3 micron particle size) 207 gramε Fe (minuε 325 mesh) 75 grams Cu (minus 325 mesh)
The resulting diεperεion iε applied by dipping onto both faceε of a 302 steel foil about 12.5 microns thick, to build up coatings that, air dry to a thickness of about 5.0 mils (125 microns). The coated foil, before or after drying, is εubjected to the above-described sintering and leaching treatment and is preferably compacted before the leach. Under argon or under water it iε then cut into 2 cm x 2 cm squares that when dry immediately become incandeεcent upon expoεure to air.
The addition of 5 gramε amorphouε boron to the powderε εharply increaεeε the intenεity of the pyrophoric action. On the other hand, the addition of 5 grams A l 2 ° 3 or MgO powder reduces itε intensity and delays its incandenscence onεet. Reducing or eliminating the copper reduceε somewhatthe adhesion of the sprayed-on coatings, and iε undeεirable.
Type 302 εteel iε sufficiently heat-resistant that a 15 micron thick foil can be perforated, for example, with openings 1 millimeter wide spaced 1 millimeter from each other, and εtill provide the foregoing results.
The pyrophoric material should be kept away from oxygen, aε by being thoroughly wet with water or other protective liquid, to preserve it againεt changes. It can be cut to short lengths for loading into a decoy shell used for protecting aircraft againεt heat-seeking missileε. It can also be stabilized, by contacting it with very low concentrations of oxygen, as described in Patent 4,820,362, to render it non-pyrophoric unlesε heated to above 50°C.
Obviouεly, many modificationε and variationε of the preεent invention are poεεible in the light of the above teachings. It iε, therefore, to be understood that within the scope of the appended claims the invention may be practiced otherwise than aε εpecifically described.