PROCESS FOR DEGASSING ALUMINUM MELTS, AND GAS FOR USE THEREIN

Abstract: Aluminum and aluminum alloy melts are purified by removing entrained gaseous impurities and solid particulate impurities, primarily aluminum oxides, by bubbling a non-corrosive intimate mixture of sulfur hexafluoride in an inert gas. Magnesium levels, if present, are not significantly reduced. The process is reliable and the gas mixture safe for aluminum purifying operations and procedures.

Description: PROCESS FOR DEGASSING ALUMINUM MELTS, AND GAS FOR USE THEREIN 1. Field of the Invention The present invention relates to the refining of aluminum and, more specifically, to a system for degassing molten aluminum without significantly reducing magnesium levels, if present. 2. Background art Molten aluminum typically is contaminated with hydro¬ gen and unwanted elements such as sodium, calcium, and lithium. If magnesium is present in the melt to an excess¬ ive extent, the excessive magnesium likewise can be re¬ garded as a contaminant; however, in working with many aluminum melts, the level of magnesium that is present is not excessive, and it is desirable to effect removal of hydrogen and other unwanted elements without significantly altering the level of magnesium that is present in the melt. A problem with prior processes for removing hydrogen and the other contaminants mentioned above is that the magnesium content of the melt often is altered undesirably as the processes are performed. Prior proposals to remove the aforementioned contami¬ nants have included the use of gases bubbled up through the melt to chemically react with the impurities or to physi¬ cally remove the impurities. Suitable gases include inert gases, such as argon and nitrogen, reactive gases such as chlorine (from chlorine-containing salts, chlorine gas generating tablets, typically hexachloroethane, chlorine gas and halocarbon gases), and fluorine, as well as mix¬ tures of inert gases (nitrogen and argon) or mixtures of reactive gases (chlorine and fluorine) . The patent literature contains proposals for removing specific contaminants. Small quantities of alkali metal and alkaline earth metal impurities are removed from an alumi¬ num melt by introducing a source of sulfur, such as ele- mental sulfur, according to a process that is described in U.S. Patent No. 4,354,869. An impurity-containing slag is formed and is removed from the melt. Lithium is removed from molten aluminum alloys by introducing sulfur hexa¬ fluoride as a gas or with a carrier gas such as nitrogen or argon according to Austrian Patent No. 354,114. The fluor¬ ine in the SF,, reacts with the lithium to form a LiF pre- 6 cipitate, while the sulfur reacts with the lithium to form Li^S. The lithium content of the alloy is reduced to the parts per million level. Gaseous and solid impurities such as occluded hydrogen and metal oxides are removed from molten aluminum using a fully fluorinated or chlorinated lower hydrocarbon mixed with a relatively inactive or inert gas, as is described in U.S. Patent No. 3,854,934. A liqui¬ fied salt cover, lower in density than the molten aluminum, floats on the metal surface to inhibit discharge of poten¬ tially harmful gases. Three physical mechanisms are active in the removal of these elements. When a gas of the type described is intro¬ duced into the melt, hydrogen that is present in the melt diffuses into the rising gas bubbles, and slag particles adhere to the surface of the gas bubbles - which causes the slag particles to be flushed up to the surface of the bath. In addition, the elements to be removed may react with one or more of the reactive components of the gas introduced into the melt. Hydrogen is removed from the melt by diffusion into the rising gas bubbles. This occurs as a result of the difference in partial pressure between the melt and the gas, the rate of diffusion* is determined by the partial pressure difference between the gas and the melt, as well as by the surface area of contact between the gas and the melt. The contact time between the gas and the melt is also an important consideration. A gas which bubbles through a melt must have as low a hydrogen or moisture content as possible. If the partial pressure of the hydrogen in the gas is assumed to be about zero, the difference in hydrogen partial pressure will be substantial at the beginning of the flushing. The large difference in pressure forces hydrogen from the melt into the gas bubble. This means that hydrogen easily diffuses into the gas bubbles and that large quantities of hydrogen are removed. The partial pressure of hydrogen in the melt decreases with increased flushing time, and as the difference in partial pressure decreases, the removal of the hydrogen diminishes. This means the flow of the gas used for degas¬ sing should be increased at the end of the process to faci¬ litate the removal of the final amounts of hydrogen. Thus while the hydrogen content in a melt containing a large amount of hydrogen can be quickly decreased, further reduc¬ tion of the hydrogen content will require a long flushing time and relatively large quantities of gas. The surface area of the gas bubbles into which the hydrogen diffuses determines the area of contact surface between the melt and the inert gas; thus a larger contact surface area will have a positive influence on the removal of the hydrogen. A larger contact surface area is obtained by increasing the amount of gas, or by decreasing the size of the bubbles. The amount of gas supplied to the melt may be increased by utilizing a longer flushing time, or by utilizing a greater volume of gas per time unit. A disad¬ vantage of utilizing an increased flow of gas is that the gas flow through the melt causes a temperature drop, and the temperature drop that results with an increased flow likely will be greater than desired. Further, the increased flow of gas likely will create such violent movement in the bath that particles from the surface of the bath may be pulled down into the melt. For reasons of economy, it is desirable to use as little gas as possible. Thus, it is preferable to reduce the size of the bubbles so that the surface area to volume relationship is improved. Apart from the difference in the hydrogen partial pressure and the size of the bubbles, the diffusion of hydrogen into the gas bubble is also time dependent. This means that decreasing bubble size serves a double function. In ad¬ dition to improving the surface area to volume relation¬ ship, smaller bubbles tend to rise more slowly in the melt, thus providing a longer contact time with the melt. The average contact time that bubbles spend moving through a melt is also dependent on the geometry of the furnace. With a given melt volume, increased bath depth will have a positive influence on the flushing effect since the gas bubbles will then be in contact with the melt for a longer period of time. The direction in which bubbles are injected into a melt also will have a marginal effect on contact time. If gas is injected in a downward direction, the bubbles will be forced down into the melt before they begin to rise to the surface, whereby contact time will be increased. Oxides and nonmetallic inclusions adhere to the bubble surface and are flushed out of the melt via flotation. Particles in the size range of 1 micrometer to 1 millimeter that are suspended in the melt readily attach themselves to the surfaces .of the upward rising bubbles and are given sufficient upward movement to be flushed to the surface of the bath. Flushing is influenced by the size of the bub¬ bles, the route the bubbles take, and the surface tension of the bubble. The degassing agent used can cause a wetting effect on the bubble surface which will increase the ability of the gas to remove oxides and particles. Bubble size and path are an expression of the likelihood that a particle will be encountered by a bubble; surface tension determines to what extent a particle will adhere to the bubble which it en¬ counters. The unwanted elements in aluminum melts normally con¬ cerned are sodium, calcium and lithium. Another element that is present in aluminum melts, but which often is de- sirably left in the melt, is magnesium. While the removal of these elements has been widely discussed, the mechanisms of their removal are not fully understood. There are three basic methods in commercial use for removing impurities from aluminum melts. One method uses argon. A second uses nitrogen. A third uses chlorine. Using the inert gases argon and nitrogen is effective to remove hydrogen, at least to a certain level, but is relatively ineffective in removing active species im¬ purities such as sodium, calcium, lithium and excessive magnesium. A more detailed discussion of the relative ad¬ vantages and disadvantages of the use of the inert gases, argon and nitrogen, and the reactive gas, chlorine, will conclude this discussion of the practices of the prior art. y Argon and nitrogen work fairly well for degassing, but they can only remove up to a certain absolute level of remaining hydrogen. A further problem with industrial grades of argon or nitrogen is that these gases can contain moisture and oxygen which can form hydrogen and aluminum oxides; an ultra high purity gas avoids this problem. Neither nitrogen or argon have much of an effect on oxides ■ or particles present in the melt. Argon is an inert gas, i.e., it does not react with the melt, thus hydrogen is removed by diffusion into the argon bubbles. Particles are removed by the purging mechan¬ ism. Argon has no effect on the elements apart from a poss¬ ible mechanical agitation effect. In principle, nitrogen acts in the same way as argon. It is, however, generally accepted that, under similar circumstances, the removal of hydrogen takes place somewhat quicker when using argon than nitrogen. Also, the absolute value of the hydrogen remaining in the melt will be slight¬ ly lower when using argon than when using nitrogen. Nitrogen gives a wetter slag than argon and can be a problem in alloys containing more than 1% magnesium. This is because nitrogen is not completely inert, but reacts with the melt to form nitrides, particularly Mg 3 N_. Chlorine added to the melt quickly reacts to A1C1_ which is gaseous at temperatures above about 190 C (374 F) , so that, in reality, the melt is flushed by upward rising AlCl- bubbles. Chlorine is extremely effective for removing hydrogen, which is removed by diffusion, because the hydro¬ gen partial pressure in A1C1_ is virtually zero. However, chlorine gas is used in a stoichiometric excess and exits the melt as pure chlorine which presents safety and en¬ vironmental concerns. In addition, chlorine reacts rather slowly with aluminum as compared with other metals. AlCl gas bubbling through the melt is reactive and continues to react with the melt. Salt particles formed collect like slag on the surface of the melt, but some remain suspended in the melt. It has been shown that these particles can be the cause of the creation of agglomerates (an aluminum droplet encrusted with a salt film to which small particles of magnesium oxide and aluminum nitride are adhered) with diameters of about 20 to 200 micrometers. Chlorine reacts with the elements sodium, calcium, magnesium, lithium, etc. , and with aluminum; but where mag¬ nesium removal is not desired, this presents a problem. Chlorine removes substantial quantities of magnesium and in consequence, the magnesium must often be replaced. Fluorine acts in a manner similar to chlorine. Chlorine and fluorine are available in several forms, the most common of which are chlorine gas, salts, and halocarbons. Dry chlorine gas gives the same effects as described for chlorine. Hexachloroethane salt produces the same reaction as described for chlorine and/or fluorine, but the salt is very often hygroscopic. This means that salt can introduce moisture into the melt depending on how the salt has been stored, the relative humidity at the time of storage and/or use, and the type of salt. The effect of a halogen releasing salt on the hydrogen content of the melt depends upon the reactions which create gas.bubbles. The creation of bubbles is uncontrolled after the addition of the salt - bubbling begins violently and then tapers off as the salt is consumed, which is inconsis¬ tent with the need for greater -quantities of gas at the end of the degassing process in order to remove the last ppm of hydrogen. Halocarbons are normally introduced into the melt in the form of a gas which also have the same reactions as described above for chlorine and fluorine. In addition to the usual reactions as with chlorine and fluorine, reac¬ tions with the carbon component of the halocarbon gas also take place. Sulfur hexafluoride (SF β ) can also be added as a gas to the melt. As with chlorine and fluorine, sulfur hexa¬ fluoride can successfully cope with diffusion and flushing; however, reaction is minimal. Sulfur hexafluoride uses the flushing action more efficiently to rival the quality ob¬ tained by the reaction of chlorine and fluorine. Safety of these gas.es and gas-producing materials is a concern. Although nitrogen and argon are nontoxic, chlor¬ ine (and fluorine) gas is corrosive and poisonous and strict limits are placed on worker exposure to chlorine as well as transport and storage of the gas. Halocarbon gases are virtually nontoxic and noncorrosive; however, many can replace oxygen in the air presenting a suffocation poten¬ tial for those near the gas. Certain halocarbons decompose at degassing temperatures. Sulfur hexafluoride is similar to halocarbon 12 (di- fluorodichloromethane) in that it is a nontoxic, noncor¬ rosive gas. The time threshold limit value-TWA ("TWA" stands for "time weighted average") for sulfur hexafluoride is 1000 ppm. As with halocarbon 12, it can replace the oxygen in the air so there is a danger of suffocation. Sulfur hexafluoride does not decompose as does halocarbon 12; it is more stable at high temperatures and is often used to blanket high temperature operations. Any breakdown into sulfur and fluorine is immediately consumed by alumi¬ num and is flushed to the surface. Description of the Preferred Embodiment We have discovered and hereby disclose a process for degassing aluminum melts an purifying aluminum melts by removing aluminum oxides ' , particulates and gaseous impuri¬ ties in a safe, reliable manner without environmental ex¬ posure to hazardous, reactive gases such as chlorine. A significant and unexpected feature of the process is that degassing and purification are carried out without substan¬ tially altering the magnesium concentration of the melt. In accordance with the practice of the present inven¬ tion, an aluminum melt is contacted with an intimate mix¬ ture of an inert gas and helogenated sulfur compound in gaseous form, preferably by bubbling the gas mixture through the melt using a lance or other conventional inlet device. Solid particles of debris entrained in the melt are brought to the surface, hydrogen is removed, and the melt effectively degassed in this manner. The preferred halogenated sulfur compound that is used is fluorinated, preferably sulfur hexafluoride (see The Merck Index, 10th edition, monograph 8853) . The halogenated sulfur compound is present in the inert gas in an amount of from about 2% to about 20% of the gas mixture and prefer¬ ably is used in an amount of about 5% when mixed with ni¬ trogen. Inert gases to be used include argon, helium and, preferably, nitrogen; mixtures of two * or more of-these inert gases may be used. A previously prepared homogeneous mixture of the halogenated sulfur compound and inert gas, called a "premix", is preferred for reasons explained below. " In this specification the term "aluminum melt" is used to designate molten aluminum (i.e., a melt of relatively pure aluminum) or alloys of aluminum in their molten con¬ dition. Parts per million and percentages are expressed on a volume/volume basis unless indicated otherwise. The aluminum-containing melt to be purified is custom¬ arily maintained at usual degassing temperatures of from about 650°C (1200 °F) to about 840°C (1550°F). Bubbling a gas through the melt inherently removes heat energy from the melt, thus a temperature decrease of up to 56 C (100°F), but preferably less than 28°C (50°F), is well tolerated under usual processing conditions. Aluminum and aluminum alloyus are purified and unwanted impurities, particulates and metal oxides arc removed together with entrained hydrogen when the SF fi /inert gas mixture is sup¬ plied to the melt at an effective rate and for an appropri¬ ate time until the impurity level is reduced to a preselec¬ ted level. The resultant dross which contains these im¬ purities on the surface of the aluminum is a dry, powdery material which enhances effective removal when skimmed from the surface, reducing dross impurities in the finished casting and minimizing waste of primary aluminum. Exact operational parameters of the process will be quickly de¬ termined by empirical means by an experienced operator following the teachings presented herein. An important feature resides in the fact that the magnesium content of the melt is not substantially reduced by the process of this invention. Included in this invention is a composition adapted for purifying aluminum and alloys of aluminum consisting essentially of an intimate mixture of up to 10% gaseous sulfur hexafluoride balance substantially an inert or non- reactive gas or gases * selected from nitrogen, argon, helium or mixtures thereof. Sulfur hexafluoride does not represent any known en¬ vironmental problem and is not corrosive. A mixture of 3-10% of sulfur hexafluoride in nitrogen or argon may be packaged in a standard industrial steel cylinder. An advan¬ tage of sulfur hexafluoride over the halocarbons, notably R-12, is that a 5% SF-/nitrogen mixture contains nearly twice as much gas as a 5% R-12/nitrogen mixture. This vol¬ ume difference increases to four times at a 10% concentra¬ tion. The removal of hydrogen from the aluminum melt using an SF β /nitrogen mixture is completely mechanical. An S F ^ /nitrogen mixture is faster than an R-12/nitrogen mix- 6 ture and it is assumed that the change in surface tension and speed limiting effect are even greater with SF g than R-12. The smaller bubbles that are formed will also rise at at a slower rate to the surface allowing for more contact time between the melt and the degassing agent. Oxide removal using an SF g /nitrogen mixture is almost totally mechanical since these mixtures have a high moist¬ ening effect on the surface providing better adhesion of oxides and particles. This combined with the smaller bub¬ bles which expose more gas to the melt, allows SF fi to be an excellent medium for removing particles and oxides. Sulfur hexafluoride is generally non-reactive with contaminating elements in the melt; these are removed by the flushing action of the gas as it bubbles upwardly through the melt. This can be a benefit if the removal of elements such as magnesium and sodium is undesirable. Refining using only inert gas is simple in practice. The gas is taken from cylinder bundles or from a tank where it is stored in a liquid state, and is vaporized before it enters the pipe supply system. The inert gas passes through a pressure regulator and a dosing unit. In refining, the gas is introduced into the melt through porous plugs, lances, or by rotating equipment or similar devices, depen¬ ding on the choice of equipment. The amount of gas is about 3 1 m (35 cubic feet) per ton (2000 lbs) of aluminum at a pressure of about 2-3 bars (30-45 psig), and the flushing time is about 10-15 minutes. This reduces the melt tem¬ perature about 2U-40°C (36-72°F). Pure inert gases such as nitrogen and argon are only able to achieve a certain absolute level of hydrogen gas removal. To go lower than this predetermined value, another gas must be mixed with nitrogen or argon. Also, pure inert gases do not perform well in removing particles, oxides, and elements, thus it is necessary to mix the inert gas with a reactive gas. When mixing inert gas with SF fi , it is important that the gases are properly mixed; if SF_ enters the melt in the form of unmixed, concentrated volumes of the reactive gases or plugs, it will result in very poor utilization of the gas and increased operating expense. Homogeneous mixing is necessary because of the large differences in viscosity and density between gas, yet achieving a homogeneous mix is extremely difficult with SF fi , Merely running two pipes together through a flowmeter will not accomplish proper mixing. A mixing chamber or heating is required; this is then followed by analyzing the gas. Premixed cylinders filled with the appropriate SF g inert gas mixture are well suited to the process and are con¬ venient to use. Commercially available in-situ gas blenders can also be utilized when bulk quantities of gases are required due to large quantities of aluminum or aluminum alloys to be purified. Premixed cylinders can be prepared at a central supply point using sophisticated equipment to assure that the gas mixing process has been carried out in a manner that provides an intimate mixture of proper per¬ centages of constituents. The preferred method of introducing SF fi / to a melt is similar to that of a pure gas. A gas supply cylinder is connected to a regulator and the gas flows through a tube into a lance of graphite, graphite coated or enamel coated steel into the aluminum melt. A Comparative Exemple In this example, not according to the present inven¬ tion, a comparative experiment in accordance with prior procedures was performed in a gas-fired 600 pound furnace of 355 alloy. Chlorine at a 20% level mixed with nitrogen was bubbled through the metal through a single 0.5 inch I.D. graphite tube at a rate of 20 scfh for 20 minutes. The 20% chlorine/nitrogen mixture yielded a density of 2.67 cc per gram as measured by a Stahl vacuum tester. The spectro- graphiσ quantometer indicated a drop in the magnesium con- tent from 0.54 to 0.38%. This correlated to normal operat¬ ing procedures and required a further modification in the form of a magnesium addition to a level of 0.68 or 0.70 in order to meet specification after degassing. Additional Example No. 1 A second 600 pound 355 alloy was melted and degassed using the same described procedure described in the com¬ parative Example, except that the 20% chlorine/nitrogen gas was replaced with 5% sulfur hexafluoride in nitrogen sup¬ plied in a premixed cylinder. The data obtained are summar¬ ized in the following: Quantometer Lab Report: Averages 4.87 0.19 1.27 0.005 0.52 0.13 0.12 0.020 Thus, similar aluminum specific gravities were reached in the same time period without any associated loss of alloy components, notably magnesium content. No further modifi¬ cation was necessary. Additional Example No. 2 Two 300 pound gas fired furnaces containing 356 alloy aluminum were held at a temperature of 805 C (1480 F) . Ultra high purity nitrogen from a cryogenic source was bubbled through a 12.7 mm (-) ") I.D. graphite fluxing tube in one furnace and a mixture of 5% sulfur hexafluoride in nitrogen was bubbled through an identical graphite fluxing tube in the second furnace. The nitrogen was bubbled through the 356 alloy at 25 scfh and the 5% sulfur hexa¬ fluoride in nitrogen mixture was bubbled at 15 scfh. Bub¬ bling took place for 20 minutes and samples were taken at 5 minute intervals. Samples were solidified in a Stahl vacuum tester. Hydrogen levels in both furnaces were elevated to the same level. Specific gravity increased as an' indirect measure of dissolved gas level. The initial specific grav¬ ity was 2.46 for both furnaces. A specific gravity of 2.65 was desired. This level was obtained under the above men¬ tioned conditions in 10 minutes with the 5% sulfur hexa¬ fluoride in nitrogen mixture and in 15 minutes for the ultra high purity nitrogen. Degassing continued for the full 20 minutes in each crucible to monitor any possible changes in alloy composition. A sample was taken from each furnace at time zero and after 20 minutes of bubbling. These were analyzed with a Jarrel Ash Spectrograph. Results are as follows: A 600 pound gas fired furnace was used containing aluminum alloy 535. The mixture of 5% sulfur hexafluoride in nitrogen was bubbled through a 6.4 mm (1/4") I.D. gra¬ phite lance at 20 scfh for 20 minutes to obtain the desired level of hydrogen entrainment. The desired level of hydro¬ gen was measured at a specific gravity of 2.60. A sample ' was taken at time zero and later after 20 minutes of bub¬ bling to monitor the change in composition of the alloy. Of particular concern were the magnesium concentrations which were successfully maintained within acceptable limits. Results are as follows: Time Alloy Mg Fe Cu Mn Si ^ _i 0 535 7.39 0.10 0.015 0.15 0.23 0.15 20 535 7.36 0.10 0.012 0.14 0.076 0.10 As can be seen, once the desired hydrogen levels have been obtained, the alloy composition of the aluminum remains intact. Although features of the present invention have been described with a certain degree of particularity, it will be understood that the patent shall cover, by suitable expression in the appended claims, whatever features of patentable novelty that exist in the invention disclosed.

Claims: CLAIMS 1. A process for purifying aluminum and aluminum al¬ loys by removing solid particulate impurities including aluminum oxides and gaseous impurities from an aluminum melt without substantially altering the magnesium concen¬ tration of the molten aluminum, comprising contacting a body of molten aluminum or molten aluminum alloy with a treating gas consisting essentially of an inert gas con¬ taining a gaseous helogenated sulfur compound, said gas containing up to about 50 percent of said halogenated sul¬ fur compound, thereby transferring solid particle im¬ purities, including aluminum oxides, to the surface of the molten aluminum, and removing gaseous impurities, thus leaving the said aluminum or aluminum alloy in a purified condition. 2. The process of Claim 1 wherein the halogenated sulfur compound is completely flourinated. 3. The process of Claim 2 wherein the halogenated sulfur compound is sulfur hexafluoride. 4. The process of Claim 1 wherein the halogenated sulfur compound represents 2 to 10 percent of the treating gas. 5. The process of Claim 1 wherein the inert gas is selected from the group consisting of nitrogen, argon, and helium. 6. The process of Claim 1 wherein the treating gas is nitrogen containing about 5 percent by volume of sulfur hexafluoride. 7. The process of Claim 1 wherein the step of con¬ tacting the molten body with gas includes the step of bubbling the gas through the molten body. 8. A process for purifying aluminum and aluminum base alloys by removing entrained gaseous impurities and solid particulate impurities from an aluminum-containing melt comprising bubbling a treating gas consisting essentially of an intimate mixture of from about 2 to about 20% of sul¬ fur hexafluoride balance nitrogen, argon or both and allow¬ ing the sulfur hexafluoride to act thereby removing en¬ trained gaseous impurities and solid particulate impurities from the melt while the magnesium content of the melt re¬ mains substantially the same. 9. The process of Claim 8 in which the solid im¬ purities are alkali metals, alkaline earth metals or both. 10. The process of Claim 9 in which the solid im¬ purities are compounds of sodium, calcium, magnesium and lithium. 11. The process of Claim 8 in which hydrogen is the gaseous impurity removed. 12. The process of Claim 11 in which substantially all of the hydrogen is removed from the melt. 13. The process of Claim 8 in which the sulfur hexa¬ fluoride is present in the gas in an amount of from 2 to 10%, with the balance being nitrogen, argon or mixtures thereof. 14. As a composition of matter, an intimate gaseous mixture of from 2 to 10 percent by volume sulfur hexa¬ fluoride homogeneously dispersed in at least one inert or non-reactive gas selected from the group consisting of nitrogen, argon and helium, the intimate gaseous mixture being adapted for removing impurities and entrained hydro¬ gen from an aluminum or aluminum alloy melt. 15. The composition of Claim 14 containing from about 2 to about 20% by volume sulfur hexafluoride. 16. The composition of Claim 15 containing from about 3 to about 10% by volume sulfur hexafluoride. 17. A pressurized container filled with the compo¬ sition of Claim 16. 18. The composition of Claim 14 containing about 5% by volume sulfur hexafluoride, with the balance being nitro¬ gen. 19. The composition of Claim 14 in which the inert gas is nitrogen. 20. A pressurized container filled with the composi¬ tion of Claim 14.

Inventors: CORNS RONALD R, MACNEAL JAMES R, RACK TIMOTHY P, CORNS, RONALD, R., MACNEAL, JAMES, R., RACK, TIMOTHY, P.
Applicants: AGA AB, AGA AKTIEBOLAG
Application year: 1987
Main classification: C22B21
IPC codes: C22B21