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GB2061320A - Production of ferrosilicoaluminozirconium and zirconium corundum - Google Patents

Production of ferrosilicoaluminozirconium and zirconium corundum Download PDF

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GB2061320A
GB2061320A GB7936970A GB7936970A GB2061320A GB 2061320 A GB2061320 A GB 2061320A GB 7936970 A GB7936970 A GB 7936970A GB 7936970 A GB7936970 A GB 7936970A GB 2061320 A GB2061320 A GB 2061320A
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zirconium
iron
weight
silicon
aluminium
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TSNII CHER METAL IM I P BARDIN
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Priority to FR7927830A priority patent/FR2469463A1/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653Processes involving a melting step
    • C04B35/657Processes involving a melting step for manufacturing refractories
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C35/00Master alloys for iron or steel
    • C22C35/005Master alloys for iron or steel based on iron, e.g. ferro-alloys

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

An alloy containing zirconium, iron, silicon and aluminium, and zirconium corundum, are produced by melting together a zirconium concentrate, an iron ore and aluminium in a weight ratio of 51-69 : 9.9-16.5 : 19.8-34.8 respectively, at 1,950 to 2,000 DEG C and separate casting of the resulting alloys, the zirconium corundum being cast first. Before the remaining alloy is cast, there are added thereto fluxes in an amount of 5 to 35% by weight of the zirconium concentrate and charge materials, such as ferrosilicon, in an amount of 3 to 102% by weight of silicon of the total weight of the zirconium concentrate and ferrosilicon, ferromanganese or metallic manganese in an amount of 3 to 26% by weight of manganese of the total weight of the zirconium concentrate, the fluxes and charge materials then being melted at 1,950 to 2,000 DEG C. Ferrosilicotitanium, ferrotitanium or metallic titanium may be added to the metallic alloy in an amount of 4 to 41% based on the weight of titanium relative to the weight of the zirconium concentrate.

Description

SPECIFICATION Production of ferrosilicoaluminozirconium and zirconium corundum The present invention relates to ferrous metallurgy and more particularly to the production of metal alloys, containing zirconium, iron, silicon and aluminium, and of a zirconium corundum.
Ferrosilicoaluminozirconium alloys are used for deoxidizing and alloying steel, iron and various alloys, while zirconium corundum is employed in the manufacture of abrasive tools for grinding steel ingots and billets prior to rolling.
According to the present invention, there is provided a method for the production of zirconium corundum and ferrosilicoaluminozirconium, which comprises melting together a zirconium concentrate, and iron ore and aluminium, in a weight ratio of 51-69:9.9-16.5:1 :19.834.8 respectively, at a temperature of 1,950 to 2,0000 C, casting the resulting zirconium corundum phase, adding to the remaining phase, at a temperature of 1,950 to 2,0000C, 5 to 35% based on the weight of the concentrate of at least one flux, 3 to 120% of ferrosilicon, the percentage of the latter being expressed as silicon based on the weight of the concentrate, and 3 to 26% of -silicomanganese, ferromanganese or metallic manganese, the percentage of the latter being expressed as the weight of manganese based on the weight of the concentrate, and casting the resulting ferrosilicoaluminozirconium phase. The resulting ferrosilicoaluminozirconium (which also contains manganese) is suitable for alloying cast iron without chilling thereof during casting of thinwalled parts.
In order to further prevent the chilling of cast iron during casting and to improve the mechanical strength of the iron castings, it is preferable to add ferrosilicotitanium, ferrotitanium or metallic titanium in an amount of 4 to 41% based on the weight of titanium relative to the weight of the zirconium concentrate to the ferrosilicoaluminozirconium phase along with the fluxes and other additives prior to the melting thereof, such that the resulting alloy also contains titanium along with zirconium, iron, silicon and aluminium. The presence of titanium in the alloy enhances mechanical strength of iron castings.
For example, a mould of iron alloyed with the metal alloy of the above composition has a service life of up to 1 15 days, no cracks or cavities being observed in the mould during this period, while a mould of iron not containing the alloy has a service life under the same conditions less by a factor of 2 to 4 than the mould frorn the alloyed cast iron, the plain cast iron mould failing because of the formation therein of cracks and cavities.
In the method according to the invention, the zirconium used is all converted to a useful product (the production of zirconium-containing slags is avoided). The joint production of ferrosilicoaluminozirconium and zirconium corundum enables the production costs to be substantially lower than when they are produced separately, and the product quality is similar to that when they are produced separately. For example, the resultant ferrosilicoaluminozirconium melts in the range of from 1,230 to 1,3800C, has good solubility in steels, cast irons and other alloys and can be readily crushed to particles ofthe required size. The zirconium corundum obtained by the method according to the invention has good abrasive properties.
The zirconium concentrate, iron ore and aluminium and other starting materials used in the method according to the invention are preferably charged to the melting apparatus, such as an electric arc furnace, in powdered form.
When the above materials are melted together at 1,950 to 2,0000C a ferrosilicoaluminozirconium phase and a zirconium corundum phase are formed, the former being denser and therefore below the zirconium corundum phase.
The zirconium The zirconium corundum phase is therefore cast (before the ferrosilicoaluminozirconium phase in the method according to the invention), for example, into heavy metallic moulds with air or liquid cooling, and then the flux (such as calcium oxide, magnesium oxide, calcium fluoride), the ferrosilicon, and the ferrosilicomanganese, ferromanganese or metallic manganese are added to the remaining alloy and melted at a temperature within the range of 1,950 and 2,0000 C. As a result, there is obtained a metal alloy consisting of zirconium, iron, silicon, aluminium and manganese and a waste slag free from zirconium, the alloy and the waste slag being cast separately from the arc furnace into metallic moulds and cooled.
In order that the present invention may be more fully understood, the following Examples are given by way of illustration only. Unless indicated to the contrary, all percentages are by weight.
EXAMPLE 1 An arc furnace was charged with 2400 kg of zirconium concentrate containing 65% zirconium dioxide and 32% of silicon dioxide,480 kg of iron ore containing 96% iron oxide and 840 kg of aluminium powder of 90% purity. The proportions by weight of these starting materials were 64.5:12.9:22.6, respectively.
The charged materials were melted at 2,0000C for 3.5 hours, whereby there were obtained 1100 kg of ferrosilicoaluminozirconium consisting of 40.7% of zirconium,27% of iron, 29.4% silicon, 1.1% aluminium and 1.8% of incidental impurities (such as copper and carbon), and 2400 kg of a zirconium corundum consisting of 39.3% zirconium dioxide, 54.3% aluminium oxide, 2.0% silicon dioxide, 0.8% calcium oxide, 2.1% manganese oxide and 1.5% iron (i.e., metallic iron and iron oxide).
The zirconium corundum layer was then cast from the arc furnace into heavy metal moulds and cooled in the air. The arc furnace containing ferrosilicozirconium was then charged with 120 kg of lime (flux) containing 96% calcium oxide, 1600 kg of ferrosilicon containing 75% silicon and 24% iron, and 332 kg metallic manganese of 94% purity, followed by melting at 2,0000C for 2 hours to yield 2990 kg of a metallic alloy consisting of 14.9% zirconium, 22.7% iron, 50.8% silicon, 0.4% aluminium, 10.4% manganese and 0.8% of incidental impurities (such as copper and carbon) and 110 kg of a waste slag free from zirconium. The metallic alloy and the waste slag-were cast separately.
The resultant alloy of the above composition was alloyed with gray iron and cast to form thinwalled parts without chilling.
The resultant zirconium corundum was employed to manufacture abrasive tools for grinding steel ingots and billets prior to rolling.
EXAMPLE 2 An arc furnace was charged with 2400 kg of zirconium concentrate, 635 kg of iron ore and 1620 kg of aluminium powder, the proportions by weight being 51.6:13.6:34.8, respectively. The charge was melted at 1 ,9600C for 3.6 hours to yield 1 680 kg of an alloy consisting of 48% zirconium, 22.1% iron, 19.2% silicon, 9.5% aluminium and 1.2% incidental impurities (such as copper and carbon) and 2600 kg cf zirconium corundum consisting of 17.5% zirconium dioxide, 76.9% aluminium oxide, 1.1% silicon dioxide, 1% calcium oxide, 2.7% magnesium oxide and 0.8% iron.
The zirconium corundum layer was then cast into heavy metallic moulds and cooled. The arc furnace containing the remaining metal alloy was charged with 160 kg of fluxes (80 kg of calcium oxide and 80 kg of magnesium oxide), 1900 kg of ferrosilicon containing 75% silicon and 24% iron and 380 kg of ferrosilicomanganese containing 68.5% manganese, 28.5% silicon and 1.4% iron, followed by melting at 1 ,9500C for 2.6 hours to obtain 3920 kg of a metal alloy consisting of 20.6% zirconium, 21% iron, 47.3% silicon, 4% aluminium, 6.6% manganese and 0.5% of incidental impurities and 1 50 kg of a waste slag free from zirconium. The alloy and the waste slag were cast separately.
EXAMPLE 3 An arc furnace was charged with 2000 kg of zirconium concentrate, 400 kg of iron ore and 1000 kg of an aluminium powder, the proportions by weight being 58.8:11.8:29.4, respectively.
The charge was melted at 1 ,9800C for 2.6 hours to yield 1160 kg of an alloy consisting of 43.2% zirconium,20.9% iron, 27.3% silicon, 6.2% aluminium and 2.4% incidental impurities and 2240 kg of zirconium corundum composed of 27.3% zircbnium dioxide, 68.5% aluminium oxide, 1.4% silicon dioxide, 0.7% calcium oxide, 0.9% magnesium oxide and 1.2% iron.
The zirconium corundum layer was cast into heavy metal moulds and cooled in the air. The arc furnace containing the remaining metal alloy was then charged with 700 kg of calcium fluoride, 2210 kg of ferrosilicon containing 75% silicon and 24% iron and 213 kg of ferromanganese containing 87% manganese, 2% silicon and 10% iron, followed by melting at 2,0000C for 2.5 hours, to obtain 3364 kg of a metallic alloy consisting of 14.9% zirconium, 26.4% iron, 50.5% silicon, 2.1% aluminium, 5% manganese, 1.1% associated impurities, and 620 kg of a waste slag free from zirconium. The alloy and the waste slag were cast separately.
EXAMPLE 4 An arc furnace was charged with 1 600 kg of zirconium concentrate,252.8 kg of iron ore and 539.2 k.g of-aluminium- powder, the proportions by weight being 66.9:10.6:22.5, respectively. The charge was melted at 2,0000C for 2.1 hours to produce 600 kg of an alloy consisting of 35.9% zirconium,-25.4% iron, 35.3% silicon, 0.8% aluminium and 2.6% incidental impurities and 1790keg of or a zirconium corundum consisting of 43.5% zirconium dioxide, 51.5% aluminium oxide, 2.2% silicon dioxide, 1.2% calcium oxide, 0.6% magnesium oxide and 1% iron.
The zirconium corundum layer was cast into heavy metallic moulds and cooled in the air. The metallic alloy remaining in the arc furnace was then melted at 2,0000C for 2.2 hours with the addition of 320 kg of lime containing 96% calcium oxide, 1 768 kg of ferrosilicon containing 75% silicon and 24% iron and 568 kg of ferrosilicomanganese containing 68.5% manganese, 28.5% silicon and 1.4% iron. This resulted in 2726 kg of an alloy consisting of 7.9% zirconium, 22.2% iron, 55.7% silicon,0.3% aluminium, 12.9% manganese and 1% incidental impurities, and 302 kg of a waste slag free from zirconium. The alloy and the waste slag were cast separately.
EXAMPLE 5 An arc furnace was charged with 2400 kg of a zirconium concentrate containing 65% zirconium dioxide and 32% silicon dioxide, 571 kg of iron ore, containing 96% iron oxide and 1464 kg of aluminium powder of 90% purity, the ratio by weight of the charge materials being 54.1:12.9:33, respectively. The charge was melted at 1 ,9600C for 3.4 hours to yield 1760 kg ' of an alloy consisting of 45.8% zirconium, 19.5% iron, 23.4% silicon, 9% aluminium and 2.3% incidental impurities and 2670 kg of zirconium corundum consisting of 16.9% zirconium dioxide, 78.9% aluminium oxide, 1.1% silicon dioxide, 0.7% calcium oxide, 1% magnesium oxide and 1.4% iron.
The zirconium corundum layer was cast into heavy metal moulds and cooled in the air. The remaining metal alloy was then melted in the arc furnace together with 360 kg of caicium oxide, 778 kg of ferrosilicon containing 75% silicon and 24% iron and 254 kg of manganese of 94% purity for 1.1 hours at 2,000 C, whereby 2652 kg of an alloy consisting of 30.5% zirconium, 24% iron, 30.8% silicon, 5.3% aluminium, 8.1% manganese and 1.3% incidental impurities, and 312 kg of a waste slag free from zirconium were produced.
The alloy and the waste slag were cast separately.
EXAMPLE 6 An arc furnace was charged with 2400 kg of zirconium concentrate, 343.2 kg of iron ore and 732 kg of aluminium powder, the ratio by weight of the charge materials being 69:9.9:21.1, respectively. The charge was melted at 2,0000C for 3.3 hours to produce 820 kg of an alloy consisting of 34.9% zirconium, 25.1% iron, 36.8% silicon, 0.7% aluminium and 2.5% incidental impurities and 2650 kg of a zirconium corundum consisting of 46.2% zirconium dioxide, 48.8% aluminium oxide, 2.3% silicon dioxide, 1.1% calcium oxide, 0.7% magnesium oxide and 0.9% iron.
The zirconium corundum layer was cast into heavy metal moulds and cooled in the air. The metal alloy remaining in the arc furnace was melted together with 240 kg of fluxes (120 kg of calcium oxide and 120 kg of magnesium oxide), 100 kg of ferrosilicon containing 75% silicon and 24% iron, 90 kg of manganese of 89% purity and 624 kg of ferrosilicotitanium containing 30% titanium, 20% silicon, 35% iron and 10% aluminium, at 2,0000C for 0.9 hour, whereby 1 623 kg of an alloy consisting of 17.7% zirconium, 32.8% iron, 29.9% silicon 4.2% aluminium, 4.4% manganese,9.7% titanium and 1.3% incidental impurities and 202 kg of waste slag free from zirconium were produced.The alloy and the waste slag were cast separately.
The resulting alloy was used to alloy gray iron of the following percentage composition: carbon, 3.65; silicon, 2.4; manganese, 1.1; sulphur, 0.12; iron, the balance. The metal alloy was added in an amount of 0.8% based on the molten iron, and the alloying resulted in a cast iron of the following percentage composition: carbon, 3.62; silicon, 2.62; manganese, 1.13; sulphur, 0.08; titanium, 0.08; zirconium, 0.12 and iron, the balance.
The alloyed iron was employed to cast an iron mould which cpntained no chilled iron. The mould from the alloyed cast iron had a service life of 91 days, neither cracks nor cavities were observed in the mould during this period. A mould from plain iron had a service life under the same conditions of 27 days, cracks and cavities having occurred.
EXAMPLE 7 An arc furnace was charged with 2400 kg of zirconium concentrate, 517.2 kg of iron ore and 732 kg of aluminium powder, the ratio by weight of the charge materials being 64.8:1 5.4:1 9.8, respectively. The charge was melted at 2,0000C for 3.3 hours to yield 868 kg of an alloy consisting of 23.9% zirconium, 39.7% iron, 33.4% silicon, 0.6% aluminium and 2.4% incidental impurities, and 2892 kg of zirconium corundum consisting of 48.1% zirconium dioxide, 46.2% aluminium oxide, 2.4% silicon dioxide, 0.9% calcium oxide, 1% magnesium oxide and 1.4% iron.
The zirconium corundum layer was cast into heavy metal moulds and cooled in the air, while the alloy remaining in the arc furnace was melted together with 240 kg of calcium oxide, 510 kg of ferrosilicon containing 75% silicon and 24% iron, 248 kg of ferrqmanganese containing 87% manganese, 2.5% silicon and 10% iron and 334 kg of ferrosilicotitanium, containing 32% titanium, 10% silicon, 46% iron and 10% aluminium, at 2,0000C for 1.1 hours, to produce 1939 kg of an alloy consisting of 10.8% zirconium, 35.3% iron, 36% silicon, 2% aluminium,10.1 manganese, 4.7% titanium and 1.1% incidental impurities, and 205 kg of a waste slag free from zirconium. The alloy and the waste slag were cast separately.
The resultant alloy was used in an amount of 1% to alloy a gray iron of composition as given in the Example 6, yielding a cast iron of the following percentage composition: carbon, 3.61; silicon, 2.73; manganese, 0.19; sulphur, 0.08; titanium, 0.05; zirconium, 0.09 and iron, the balance.
A metal mould was cast from the alloyed iron, and no chilling occurred. The metal mould from the alloyed iron had a service life of 11 5 days, and no cracks or cavities were observed in the metal mould. A mould of non-alloyed iron had a service life under the same conditions of 27 days and failed through formation of cracks and cavities.
EXAMPLE 8 An arc furnace was charged with 1 600 kg of zirconium concentrate, 420.8 kg of iron ore and 539.2 kg of aluminium powder, the ratio by weight of the charge materials being 62.5 :16.4:21.1, respectively. The charge was melted at 2,0000C for 2.1 hours, to yield 650 kg of an alloy consisting of 28% zirconium, 39% iron, 30.3% silicon, 0.6% aluminium and 2.10/0 incidental impurities, and 1 900 kg of a zirconium corundum consisting of 44.5% zirconium dioxide, 50.3% aluminium oxide, 2.2% silicon-dioxide, 0.8% calcium oxide, 1.2% magnesium oxide and 1% iron.
The zirconium corundum layer was cast into heavy metallic moulds and cooled in the air, while the alloy remaining in the arc furnace was melted together with 560 kg of calcium fluoride, 2165 kg of ferrosilicon containing 75% silicon and 24% iron, 550 kg of ferrosilicomanganese containing 73.8% manganese, 18.6% silicon and 5.3% iron and 704 kg of metallic titanium of 92% purity, at 2,0000C for 3.5 hours. There were produced 3888 kg of an alloy consisting of 4.9% zirconium, 24.1% iron, 47% silicon, 0.1% aluminium, 9.4% manganese,14.1 titanium, 0.4% associated impurities, and 490 kg of a waste slag free from zirconium. The alloy and the waste slag were cast separately.
EXAMPLE 9 A zirconium concentrate, an iron ore and an aluminium powder were melted in an arc furnace under the same conditions and in the same ratio as in Example 7. The resulting zirconium corundum layer was cast into heavy metal moulds and cooled. The arc furnace containing the remaining metal alloy was charged with 120 kg of lime containing 96% calcium oxide, 500 kg of ferrosilicon containing 75% silicon and 24% iron, 650 kg of ferrosilicomanganese containing 73.8% manganese, 18.6% silicon and 5.3% iron and 520 kg of titanium of 92% purity, followed by melting at 2,000 C for 1.8 hours. This resulted in 2400 kg of a metal alloy consisting of 8.6% zirconium, 19.6% iron, 32.7% silicon, 0.2% aluminium, 19.9% manganese,18.1 titanium and 0.9% incidental impurities, and 110 kg of a waste slag free from zirconium. The alloy and the waste slag were cast separately.

Claims (3)

1. A method for the production of zirconium corundum and ferrosilicoaluminozirconium, which comprises melting together a zirconium concentrate, an iron ore and aluminium, in a weight ratio of 51-69:9.9-16.5:1 :9.916.5:19.834.8 respectively, at a temperature of 1,950 to 2,0000C, casting the resulting zirconium corundum phase, adding to the remaining phase, at a temperature of 1,950 to 2,0000C, 5 to 35% based on the weight of the concentrate of at least one flux, 3 to 102% of ferrosilicon, the percentage of the latter being expressed as silicon based on the weight of the concentrate, and 3 to 26% of silicomanganese, ferromanganese or metallic manganese, the percentage of the latter being expressed as the weight of manganese based on the weight of the concentrate, and casting the resulting ferrosilicoaluminozirconium phase.
2. A method according to claim 1, in which the remaining phase is additionally melted with ferrosilicotitanium ,ferrotitanium or metallic titanium, in an amount of 4 to 41% based on the weight of titanium relative to the weight of the concentrate.
3. A method for the production of zirconium corundum and ferrosilicoaluminozircoriium, substantially as herein described in any of Examples 1 to 9.
GB7936970A 1979-10-25 1979-10-25 Production of ferrosilicoaluminozirconium and zirconium corundum Expired GB2061320B (en)

Priority Applications (2)

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GB7936970A GB2061320B (en) 1979-10-25 1979-10-25 Production of ferrosilicoaluminozirconium and zirconium corundum
FR7927830A FR2469463A1 (en) 1979-10-25 1979-11-12 PROCESS FOR THE SIMULTANEOUS MANUFACTURE OF ZIRCONIAN ALLOYS AND CORINDON

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GB7936970A GB2061320B (en) 1979-10-25 1979-10-25 Production of ferrosilicoaluminozirconium and zirconium corundum
FR7927830A FR2469463A1 (en) 1979-10-25 1979-11-12 PROCESS FOR THE SIMULTANEOUS MANUFACTURE OF ZIRCONIAN ALLOYS AND CORINDON

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CN110238763B (en) * 2019-07-15 2020-06-09 湖南工业大学 Metal bonding agent, metal bonding agent diamond grinding tool and preparation method thereof

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FR834528A (en) * 1937-07-28 1938-11-23 Electrochimie Soc Manufacturing process of complex silicon alloys
FR50005E (en) * 1938-06-08 1939-11-10 Electrochimie Soc Manufacturing process of complex silicon alloys

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FR2469463B1 (en) 1981-11-27
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