:uropaisches Patentamt 0 1 08 1 07 $ QJll Europeaniuropean Patent Office ® Publication number: B 1 Office)ffice europeen des brevets
g) EUROPEAN PATENT SPECIFICATION
§) Date of publication of patent specification: 13.01.88 (g) int. CI.4: C 22 C 33/08
|j) Application number: 83901516.1
Date of filing: 28.03.83 ® International application number: PCT/US83/00428
@ International publication number: WO 83/03848 10.11.83 Gazette 83/26
g) MAGNESIUM FERROSILICON ALLOY AND USE THEREOF IN MANUFACTURE OF NODULAR CAST IRON.
(§) Priority: 21.04.82 US 370185 (73) Proprietor: SKW ALLOYS INC. 3801 Highland Avenue Niagara Falls New York 14305 (US) (§) Date of publication of application: 16.05.84 Bulletin 84/20 ® Inventor: DREMANN, Charles Earl Buckwalter Road (§) Publication of the grant of the patent: Phoenixville, PA 19460 (US) 13.01.88 Bulletin 88/02 @ Representative: Hale, Stephen Geoffrey et al ® Designated Contracting States: J.Y. & G.W. Johnson Furnival House 14/18 High DE FR GB Holborn London WC1V 6DE (GB)
(58) References cited: FR-A-2443 510 GB-A-746406 GB-A- 885 896 GB-A-1 273 319 CD US-A-2 762 705 US-A-2873188 US-A-3 537 842 O US-A-3 703 922 US-A-4004 630 US-A-4224 069 00
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall CL be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been LU paid. (Art. 99(1 ) European patent convention). Courier Press, Leamington Spa, England. 0 108 107
Description
This invention relates to a novel magnesium ferrosilicon alloy, and to an improved process for the production of nodular or spheroidal graphite iron castings using a magnesium ferrosilicon alloy. 5 The carbon present in molten iron is normally in so-called flake form, and, if the metal solidifies with the carbon in such form, the cast metal has low elongation and low tensile strength, making it unsuitable for certain uses. For a number of years it has been known that flake graphite can be converted to nodular form by the use of so-called nodulizing agents, which initially were used to treat gray iron as it flowed from the melting furnace or when it was received in the ladle from which castings were poured. w More recently, the so-called in-mold process for producing nodular cast iron was developed. In this process, the mold is provided with a separate reaction chamber which contains a nodulizing agent. Molten metal to be cast comes into contact with the nodulizing agent before it enters the mold cavity. The nodulizing agent is taken up into the molten metal at a relatively uniform rate whereby the metal is uniformly treated leading to uniformity of properties throughout the cast metal. 75 In the in-mold process for producing nodular iron, the nodulizing agent used commercially to the substantial exclusion of all others is a magnesium ferrosilicon alloy containing on the order of 5 to 7 percent, by weight, of magnesium, about 43 to 48 percent silicon and balance iron. In certain alloys of this type, a small amount of rare earth metal, such as cerium, has been added to neutralize the effects of so-called tramp elements, and small amounts of calcium and aluminum have been included to provide 20 graphite nucleation resulting in high nodule counts in the cast metal. There has also been offered for sale a nodulizing agent comprising a. mechanical mixture of granular magnesium and granular ferrosilicon alloy (50% Si), in the weight ratio of about one part of the former to about 15 parts of the latter, but the portion of the market represented by this product is substantially negligible. Both the above-described commercial products have undesirable characteristics. Magnesium 25 ferrosilicon (43 — 48% Si) alloy dissolves in the molten iron at a relatively slow rate. Since casting parameters, such as casting time, temperature of metal being cast, etc. vary widely from foundry to foundry, the obtaining of inconsistent results has been a problem. Also, with such a relatively slow dissolving nodulizer, the configuration of the reaction chamber must be such as to expose to the molten metal being cast the largest possible surface area. With such an arrangement, the nodulizer, which 30 generally is used in particulated form, may be carried as such into the casting causing undesirable defects and a less uniform casting. Further, by reason of the relatively slow rate of dissolution of the magnesium ferrosilicon (43 — 48% Si), there are limitations on pour time and minimum temperature of metal being poured. The mechanical mixture of magnesium and ferrosilicon (50% Si), in addition to suffering from the 35 same deficiencies of the magnesium ferrosilicon alloy discussed above, can undergo particle segregation in manufacture and shipment by reason of the substantial disparity between the density of magnesium (1.7 g/cc) and 50% ferrosilicon (4.5 g/cc), resulting in erratic casting results. In GB — A — 885896 there is disclosed an inoculant for addition to molten iron before casting in order to increase the tendency of the iron to cast gray rather than white and to cause the graphite in the solidified 40 iron to be in a desirable form, the inoculant being an alloy containing from 0.1 to 60% in all of nickel or iron or both (preferably from 10 to 25%), from 0.1 to 5% magnesium (preferably from 1 to 4%), from 0.1 to 10% aluminum (preferably from 1 to 4%), from 0.1 to 10% calcium (preferably from 1 to 4%), and the balance apart from incidental impurities silicon. An object of this invention is to provide an improved alloy for use in the manufacture of nodular iron, 45 which alloy is relatively fast dissolving making possible decreased pouring times even with vertically parted (Disamatic) molds. Another object of this invention is the provision of improved inoculation for production of ductile iron having a higher nodular count and a higher ferrite content. Still another object of the invention is to provide an improved in-mold process for the manufacture of so nodular iron employing a novel nodulizing agent whereby cleaner castings are obtained at lower casting temperatures using reaction chambers of improved geometry. In accordance with this invention there is provided a novel magnesium ferrosilicon alloy particularly suitable for the in-mould nodulization of ductile iron, comprising 5.9 to 15 percent magnesium, 60 to 80 percent silicon, 0.1 to 1.5 percent calcium, 0.1 to 3.0 percent aluminum, optionally up to 2.5 percent rare 55 earth, and balance apart from incidental impurities iron. Preferably such alloy contains 7.5 to 9.5 percent magnesium, 65 to 70 percent silicon, 0.3 to 0.5 percent calcium, 0.8 to 1.3 percent aluminum, 0.2 to 0.5 percent rare earth, especially cerium, and balance apart from incidental impurities iron. All composition percentages quoted herein are by weight based on the total weight of the alloy. According to the process of this invention, nodular graphite iron castings are obtained by introducing so molten carbon-containing iron to a mold by way of a mold inlet so that it travels to a mold cavity by way of a gating system which includes at least one intermediate reaction chamber containing as nodulizing agent a magnesium ferrosilicon alloy according to this invention. The nodulizing agent is in particulate form and dissolves rapidly in the molten iron as the iron passes through the intermediate reaction chamber. It is present in an amount to convert the carbon to nodular graphite. 65 It has been discovered that the magnesium ferrosilicon alloys specified herein provide a number of
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distinct advantages over alloys heretofore used to produce nodular graphite iron castings. More particularly, the alloys are faster dissolving and thus are able to respond to faster pouring times. This is the case even when the alloys are used in vertically parted (Disamatic) molds. As noted previously, prior known alloys for producing nodular iron dissolve in molten metal relatively 5 slowly. For this reason, in-mold casting of iron, wide, relatively shallow reaction chambers have been used. Unfortunately, it is difficult to place alloy granules uniformly in such a reaction chamber, resulting in uneven treatment of the molten metal and, in some cases, alloy granules have been swept into the casting resulting in defects. Advantageously, by reason of the fast dissolving characteristics of the alloys specified herein, reaction chambers of improved geometry, e.g. deeper and of narrower cross section, can be used 10 whereby the chance of alloy drag over into the casting is greatly reduced. Being faster dissolving the alloys specified herein provide desired results with molten iron at lower temperatures, and lend themselves better to pouring delays. Also, the resulting castings are cleaner for the alloys rapidly dissolve in and react with the molten metal before the metal reaches the mold cavity. Alloy which is still reacting as it enters the mold cavity will produce undesirable reaction products such as is magnesium oxide, magnesium sulfide and magnesium silicate, which cause unwanted inclusions and surface defects in the casting. For alloys, such as those specified herein, which completely dissolve in the chamber, any reaction products formed have time to float out of the molten metal and be trapped on the way to the casting cavity and, thus do not form undesirable inclusions in the cast metal. In addition, the alloys specified herein provide ductile iron having a higher nodule count and a higher ferrite count. 20 The alloys used in the process of this invention have the composition as set forth in Table I, below: TABLE I
Weight percent based on total weight of alloy Constituent Essential Preferred
Magnesium 5.9 — 15 7.5—9.5
Silicon 60—80 65—70
Calcium 0.1—1.5 0.3—0.5
Aluminum 0.1 — 3.0 0.8 — 1.3
Rare earth 0.0 — 2.5 0.2—0.5
Iron Balance apart from Balance apart from incidental impurities incidental impurities
In the novel alloys of the present invention the rare earth, concentration is preferably at least 0.1 percent. Preferably the rare earth is predominately cerium and/or lanthanum. 45 The alloys may be prepared by plunging magnesium into nominal 75% ferrosilicon alloy. The alloys are relatively easy to manufacture using such procedure since the higher silicon content of the ferrosilicon alloy reduces the violence of the reaction, smoke and flare being markedly reduced. The 75% ferrosilicon alloy in which the magnesium metal is plunged can be prepared by standard smelting techniques well known in the metallurgical art and need no description here. In the alloy the so calcium and aluminum are usually present as impurities. However, the calcium and aluminum serve a useful function in that they prevent or lessen the formation of hard iron carbides in those areas, e.g. thin sections, of a casting which cool first. The presence of hard iron carbides interferes with the machinability of the casting. Rare earths give protection against deleterious impurities occasionally found in cast iron. The fact that the alloys specified herein dissolve faster than similar alloys containing on the order of 55 45 — 50% silicon is believed to be due to three important factors, namely, the melting point of the alloys, the exothermic influence of silicon on the iron, and the magnesium content. As the silicon content is increased above 60% the melting point of the alloy increases. At the same time, the heat of solution increased markedly. For a given magnesium content in the alloy, the combination of these two opposing influences — melting point and the exothermic nature of silicon in iron — produces a maximum overall so dissolution rate of about 65 — 75% silicon. As the magnesium content of the alloy is increased, dissolution rate of the alloy also increases. However, a practical limit of magnesium contents is reached beyond which actual recovery of magnesium in the cast iron begins to markedly decrease. This is due to the fact that, since casting temperatures are above the boiling point of magnesium (1090°C, 1994°F.), magnesium enters the molten iron as a gas which must be metered carefully to the iron to avoid poor recovery in the iron and 55 build up of back pressure which inhibits metal flow into the casting chamber. Thus, the preferred range of
3 0 108 107 magnesium in the alloy is about 7.5 to 9.5% in order to provide rapid dissolution without appreciably decreasing the flow of metal into the mold or recovery of magnesium in the cast iron. The following examples serve to further illustrate this invention:
5 Examples 1 to 6 A number of separate magnesium ferrosilicon alloys were prepared by plunging solid magnesium into nominal 75% ferrosilicon in an amount such that the alloys had the composition set forth in Table II below. In casting the iron, the apparatus comprised a mold having a gating system which included an intermediate reaction chamber provided with a fused silica window. The molten iron at 2550°F (1400°C) w introduced to the gating system was permitted to exit the mold and samples were caught in separate molds, and the cast metal was studied to determine its degree of nodularity. 110 cc portions of various alloys of this invention having the respective compositions given in Table II, and having a particle size such that all particles passed through a 5 mesh screen but were retained on an 18 mesh screen, were placed in the intermediate reaction zone. Moving pictures were taken of the fused silica window on the side of the 15 reaction chamber employing a camera fitted with an 8:1 telephoto lens. Wide angle motion pictures were also taken of the overall apparatus, which included the mold, pouring ladle, molten metal collector and a clock. The pictures enabled determination of the total pouring time and dissolution time. Nodularity was determined by studies of the microstructure of the cast samples. The results of the several tests are given in Table II. 20 The tests were repeated employing two different alloys of the type heretofore used commercially, which alloys contain on the order of about 46 percent silicon. These tests are identified in Table II as Examples 7 and 8, and it can be seen that the dissolution times for the prior known alloys is generally about 50 to 100 percent longer than for alloys of the present invention (See Examples 1 to 6).
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A magnesium ferrosilicon alloy particularly suitable for the in-mold nodulization of ductile iron, comprising magnesium, iron, from 60 to 80 percent silicon, from 0.1 to 1.5 percent calcium and from 0.1 to 5 3.0 per cent aluminum, characterised in that the alloy contains from 5.9 to 15 per cent magnesium and optionally up to 2.5 per cent rare earth, and the balance apart from the specified ingredients and incidental impurities is iron, all said percentages being by weight based on the total weight of said alloy. 2. An alloy according to claim 1, characterised in that it contains from 7.5 to 9.5 per cent magnesium. 3. An alloy according to claim 1, characterised in that it contains at least 0.1 per cent rare earth. w 4. An alloy according to claim 3, characterised in that it contains cerium as rare earth. 5. An alloy according to claim 3 or 4 comprising iron from 65 to 70 per cent silicon, from 0.3 to 0.5 per cent calcium and from 0.8 to 1 .3 per cent aluminum, characterised in that it contains from 7.5 to 9.5 per cent magnesium and from 0.2 to 0.5 per cent rare earth and the balance apart from the specified ingredients and incidental impurities is iron. 15 6. A process for the production of nodular graphite iron castings in which molten carbon-containing iron is introduced to a mold by way of a mold inlet and travels to a mold cavity by way of a gating system which includes at least one intermediate chamber containing a nodulizing agent comprising a magnesium ferrosilicon alloy containing calcium, aluminum and optionally rare earth in an amount to convert the carbon to nodular graphite, characterised in that the magnesium ferrosilicon alloy employed as nodulizing 20 agent comprises from 5.9 to 15 per cent magnesium, from 60 to 80 per cent silicon, from 0.1 to 1.5 per cent calcium, from 0.1 to 3.0 per cent aluminum, optionally up to 2.5 per cent rare earth, and balance apart from incidental impurities iron, said percentages being by weight based on the total weight of said alloy. 7. A process according to claim 6 characterised in that a magnesium ferrosilicon alloy according to any of claims 2 to 5 is employed as the nodulizing agent. 25 Patentanspriiche 1. Magnesium-Ferrosilicium-Legierung insbesondere zur Herstellung von GuBeisen mit Kugelgraphit nach dem Inmold-Verfahren bestehend aus Magnesium, Eisen, 60 bis 80% Silicium, 0,1 bis 1,5% Calcium 30 und 0,1 bis 3,0% Aluminium, dadurch gekennzeichnet, daB die Legierung 5,9 bis 15% Magnesium und gegebenenfalls bis zu 2,5% Seltenerdmetalle und als Rest, neben den angegebenen Bestandteilen und eventuellen Verunreinigungen, Eisen enthalt, wobei alle Prozentangaben Gewichtsprozent, berechnet auf das Gesamtgewicht der Legierung, sind. 2. Legierung nach Anspruch 1, gekennzeichnet durch einen Gehalt von 7,5 bis 9,5% Magnesium. 35 3. Legierung nach Anspruch 1, gekennzeichnet durch einen Gehalt von mindestens 0,1% Seltenerd- metallen. 4. Legierung nach Anspruch 3, dadurch gekennzeichnet, daB sie Cer als Seltenerdmetall enthalt. 5. Legierung nach den Anspruchen 3 oder 4 mit einem Gehalt an Eisen, 65 bis 70% Silicium, 0,3 bis 0,5% Calcium und 0,8 bis 1,3% Aluminium, dadurch gekennzeichnet, daB sie 7,5 bis 9,5% Magnesium und 40 0,2 bis 0,5% Seltenerdmetalle und als Rest, neben den angegebenen Bestandteilen und eventuellen Verunreinigungen, Eisen enthalt. 6. Verfahren zur Herstellung von GuBeisenstticken mit Kugelgraphit, wobei Kohlenstoff enthaltendes geschmolzenes Eisen uber einen EinguBtrichter in eine Form eingegossen wird und (iber das EinguB- system, das mindestens eine Zwischenkammer zur Aufnahme des Kugelgraphitbildners enthalt, der aus 45 einer Magnesium-Ferrosilicium-Legierung besteht und die Calcium, Aluminium und gegebenenfalls Seltenerdmetalle in einer Menge enthalt, um den Kohlenstoff in Kugelgraphit zu uberfiihren, in den Hohlraum der Form lauft, dadurch gekennzeichnet, daB die als Kugelgraphitbildner verwendete Magnesium-Ferrosilicium-Legierung 5,9 bis 15% Magnesium, 60 — 80% Silicium, 0,1 bis 1,5% Calcium, 0,1 bis 3,0% Aluminium, gegebenenfalls bis zu 2,5% Seltenerdmetalle und als Rest Eisen enthalt, wobei alle so Prozentangaben Gewichtsprozent, berechnet auf das Gesamtgewicht der Legierung, sind. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daB eine Magnesium-Ferrosilicium-Legierung nach den Anspruchen 2 bis 5 als Kugelgraphitbildner verwendet wird. Revendications 55 1. Alliage de magnesium-ferrosilicium particulierement approprie pour la nodularisation en moule de fonte ductile, contenant du magnesium, du fer, de 60 a 80 pour-cent de silicium, de 0,1 a 1,5 pour-cent de calcium et de 0,1 a 3,0 pour-cent d'aluminium, caracterise en ce que I'alliage contient de 5,9 a 15 pour-cent de magnesium et eventuellement jusqu'a 2,5 pour-cent de terres rares, et le solde, mis a part les eo constituants specifies et les impuretes accidentelles, est du fer, tous les pourcentages indiques etant exprimes en poids par rapport au poids total dudit alliage. 2. Alliage suivant la revendication 1, caracterise en ce qu'il contient de 7,5 a 9,5 pour-cent de magnesium. 3. Alliage suivant la revendication. 1, caracterise en ce qu'il contient au moins 0,1 pour-cent de terres 65 rareS- 6 0 108 107 4. Alliage suivant la revendication 3, caracterise en ce qu'il contient du cerium en qualite de terre rare. 5. Alliage suivant la revendication 3 ou 4, contenant du fer, de 65 a 70 pour-cent de silicium, de 0,3 a 0,5 pour-cent de calcium et de 0,8 a 1,3 pour-cent d'aluminium, caracterise en ce qu'il contient de 7,5 a 9,5 pour-cent de magnesium et de 0,2 a 0,5 pour-cent de terres rares, le solde mis a part les constituants 5 specifies et les impuretes accidentelles, etant du fer. 6. Procede de production de piece coulees en fonte a graphite nodulaire, dans lequel la fonte carburee en fusion est introduite dans un moule par I'intermediaire d'un orifice d'entree et s'ecoule dans la cavite du moule par un reseau de canaux qui comprend au moins une chambre intermediate contenant un agent nodulisant comprenant un alliage de magnesium-ferrosilicium qui contient du calcium, de I'aluminium et 10 eventuellement des terres rares en une quantite appropriee pour convertir le carbone en graphite nodulaire, caracterise en ce que I'alliage de magnesium-ferrosilicium employe comme agent nodulisant contient de 5,9 a 15 pour-cent de magnesium, de 60 a 80 pour-cent de silicium, de 0,1 a 1,5 pour-cent de calcium, de 0,1 a 3,0 pour-cent d'aluminium, eventuellement jusqu'a 2,5 pour-cent de terres rares et le solde, mises a part les impuretes accidentelles, etant du fer, lesdits pourcentages etant exprimes en poids is par rapport au poids total dudit alliage. 7. Procede suivant la revendication 6, caracterise en ce qu'un alliage de magnesium-ferrosilicium suivant I'une ou I'autre des revendications 2 a 5 est utilise comme agent nodulisant. 20 30 35 40 45 50 55 60 65 7