GB2222792A - Continuous casting of a hollow metallic ingot - Google Patents

Continuous casting of a hollow metallic ingot Download PDF

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Publication number
GB2222792A
GB2222792A GB8821553A GB8821553A GB2222792A GB 2222792 A GB2222792 A GB 2222792A GB 8821553 A GB8821553 A GB 8821553A GB 8821553 A GB8821553 A GB 8821553A GB 2222792 A GB2222792 A GB 2222792A
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United Kingdom
Prior art keywords
core
molten metal
peripheral surface
refractory heat
continuous casting
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GB8821553A
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GB2222792B (en
GB8821553D0 (en
Inventor
Shigeru Yanagimoto
Kazuyuki Hamachi
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Resonac Holdings Corp
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Showa Denko KK
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Priority to AU22208/88A priority Critical patent/AU619759B2/en
Priority to GB8821553A priority patent/GB2222792B/en
Priority to CA000578061A priority patent/CA1324478C/en
Priority to DE3832306A priority patent/DE3832306C2/en
Publication of GB8821553D0 publication Critical patent/GB8821553D0/en
Publication of GB2222792A publication Critical patent/GB2222792A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/006Continuous casting of metals, i.e. casting in indefinite lengths of tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/07Lubricating the moulds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/08Accessories for starting the casting procedure

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)

Description

METHOD FOR CONTINUOUS CASTING A HOLLOW METALLIC INGOT AND APPARATUS
THEREFOR 22227192
BACKGROUND OF INVENTION
1. Field of Invention
The present invention relates to a method for continuous casting a hollow metallic ingot and an apparatus therefor. More particularly, the present invention relates to a method and apparatus for continuous casting a hollow ingot having a smooth cast skin on the inner peripheral surface and a small inverse segregation- layer.
The present invention also relates to a casting-start method in the continuous casting of a hollow ingot, in which are prevented such troubles at the beginning of casting of a hollow ingot that: the core is encased in the cast metal solidified thereon; and, the molten metal flows out through an inner peripheral part of hollow ingot.
2. Description of Related Arts
A metallic tube and a long hollow material are used as the final products in their forms. Besides, a metallic tube and long hollow material are indispensable as blank materials of various annular or tubular members, such as wheel rims of like. This blan vehicles, cylinders of compressors and the k material is produced by a die-extrusion method of a columnar metallic ingot, a continous casting method, or a centrifugal casting method. The continous castirg method provides, at a low cost, a hollow ingot, having homogeneous and fine casting structure free of a texture generating a directional property. The continous casting method is therefore appropriate for producing the blank material which is subjected to plastic working, such as the ring-rolling and forging.
The continuous casting of a hollow ingot is generally carried out as follows. Namely, a core or a mandrel (hereinafter collectively referred to as the core) is concentrically held within a forcedly cooled, tubular mold to form an annular clearance between the mold and core, an'd the molten metal is continuously poured into the annular clearance. A solidified shell is formed around the hollow metallic mold in the mold. The solidification then proceeds until the interior of ingot, -v and is -directly. aprayed by the 11 while it issues outside the mold. cooling water. The thus formed hollow ingot is withdrawn outside the mold at a controlled casting speed. The above described continuous casting method is generally embodied as: the so-called float casting method, in which a refractory floating member is disposed on the level of molten metal in a tubular mold so as to control the pouring quantity of molten metal; and, the so-called hot-top method, in which a relatively deep, refractory reservoir of molten metal is l6cated integrally on the top of a forcedly cooled mold, and the level of molten metal in the reservoir is adjusted to the same level as that in the trough for feeding molten metal to the reservoir. In a casting method not with the aid of a mold, the molten metal is held in the columnar form by means of magnetic force and the columnar body is directly subjected to the water cooling to solidify the same. This method is implemented in a limited field of continuous casting. No matter which casting method is carried out, a multi-strand casting is commercially carried out while arranging a number of molds and the like in parallel.
The above described continuous casting methods for a hollow ingot can be distinguished from one another from the view point of the following kinds of core: (A) refractory, non-cooled core; (B) forcedly cooled core; and (C) a core, in force is applied for shaping. Methods are the following (1) and (2). In the of plaster is preliminarily shaped in an elongated form, molten metal is poured between the core and mold to form a hollow metal and to bond the metal with the core, and a solidified, long ingot is withdrawn outside the mold together with the bonded core, and body and core are disassembled from one which an electromagnetic belonging to (A), above, floating method (1), a gas-permeable core made subsequently the hollow another (c.f. Japanese Examined Patent Publication No.
35-1106). In the float-casting method (2), a refractory core is made of material which is difficult to be wetted with molten metal and is maintained within a mold at a predermined level (c.f. Japanese Examined Patent Publication No. 55-42655).
Methods belonging to (B), above, are the following (3), (4) and (5). In the method (3) disclosed in Japanese Unexamined Patent Publication No. 57-127584, vibration is imparted to a core by means of an electromagnetic vibrator and the like during casting. In the method (4) disclosed in Japanese Unexamined Patent Publication No. 56-141944, a rotary core is used and is provided on the outer peripheral surface with a longitudinal slit for feeding lubricating oil on this surface. In the method (4) disclosed in Japanese Unexamined Patent Publication No. 57-181759, a refractory core used is provided with cooling conduits embedded therein. Methods belonging to the (C), above, are the following (6) disclosed in USP No. 4126175, in which an inductor disposed in a water-cooled mold generates electromagnetic force for forming the inner peripheral surface of molten metal and the ingot is brought into contact with neither the mold nor core but is directly water- cooled.
The qualities required for a hollow ingot, particularly the one subjected to plastic working, such as forging, ring rolling, swaging and the like, are smooth cast skin of the inner peripheral surface and fine and homogeneous structure with few inverse segregations. The additional qualities required for a hollow billet are roundness of the hollow part and uniformity in thickness of round wall part of billet. When these qualities are not fulfilled, a hollow billet needs to be subjected to machining for removing the inner peripheral surface layer, in a large quantity. This necessitates in the casting to increase the thickness of hollow ingot or the like by an amount corresponding to the destined machining depth. The machining cost is additionally required. A great amount of machined chips are lost during remelting thereof. Consequently, the cost increase incurred due to the above machining is serious. Furthermore, when the hollow part of a long ingot having small-diameter is machined, the operation is so difficult that the productivity is reduced.
The above described, conventional methods for continuously casting a hollow ingot have merits and demerits. It is difficult by means of these methods to industrially stably 3. produce hollow ingots throughly fulfilling the above described properties. In the methods (1) and (2), homogeneous structure is not obtained.
In addition, since the core of method-(1) i& consumable, the cost is disadvantageously increased. Since it is difficult to prevent the leakage of molten metal through the solidified shell besides core, a stable operation is difficult in the method (1). Method (3) is effective for reducing the engulfment of superficial oxide film. Leakage of molten metal through thin solidified sh'ell is- however likely to occur and, therefore, formation of smooth cast skin is difficult. In method (4), stable rotation of a core is difficult, since molten metal shrinks on the water-cooled core and exerts fastening force impeding the rotation of core during solidification thereof. The rotary movement and lubrication are therefore not effective for forming smooth cast skin on the inner peripheral surface. In method (5), cooling conduits, through which the air and the like is blown, are embedded in a core to control the temperature of core. This method involves, as in methods (1) and (2), the drawbacks of leakage of molten metal at a core. The method (6) is effective for lessening the surface defects and inverse segregation of a hollow ingot but necessitates expensive installation expenditure for generating the electromagnetic field. In this method, the distance between multi-strand molds are limited and the roundness of an ingot is impaired. Furthermore, since an inductor is assembled in the core, the space required therefor makes it difficult to reduce the size of a core. This method is therefore not applied for the production of ingots having a small-diameter hollow part.
When the continuous casting operation is to be started, a tubular watercooled mold is closed at its withdrawal end by a movable bottom block which is capable of displacing in the casting direction. Molten metal is then continuously poured into the mold cavity formed between the tubular mold and core. The poured molten metal succesively solidifies in the mQld cavity and then forms a bonding part with the movable bottom block which has been placed at the beginning to close the withdrawal end of mold cavity. Upon arrival at this condition, the movable bottom block is caused to displace so as to withdraw a hollow ingot. During withdrawal, the cooling water is injected onto the inner and outer peripheral surfaces of a hollow ingot to cool it. The spontaneous cooling of a hollow ingot without injection of cooling water may be occasionally carried out. Upon initiation of the above outlined start of casting, the tapping temperature of molten metal, cooling water-flow rate in mold and the like are monitored to estimate the solidification timing of molten metal on movable bottom block. During the displacement of movable bottom block, its speed is controlled in a delicate manner. For performing the sequence of start operations under the present circumstances, the skill of operator is indispensable. Although the casting 0 start is carried out based on experience, such casting parameters as tapping temperature may vary beyond the criterion range. In this case, the molten metal solidifies due to drastic cooling by core and rigidly encases the core. Alternatively, when the cooling by core is weak, the solidified shell is too thin to hold the molten metal therein. In this case, the molten metal may flow out the solidified shell besides the core. The continuation of casting operation becomes difficult due to such trouble.
Incidentally, it is important for stablizing the casting start and for providing smooth cast skin to provide the core with such a draft that diameter is great at the top part (inlet of metal flow) and is small at the bottom part. When metal solidifies and shrinks during the continuous withdrawal of an ingot, the friction resistance is caused between the outer peripheral surface of a core and the solidified shell or molten metal's surface destined to form the hollow surface. Since the solidification and shrinkage are intensified in the casting direction, the friction resistance is increased at a lower part of core. The draft of core can mitigate the friction resistance. With increase in draft, its effect becomes great but particular casting defects, i.e., lapping pattern or dropping pattern of unsolidified molten metal, become liable to form on the inner peripheral surface of a hollow ingot. When the draft is too small, the friction resistance is increased to a level where cracks are formed on the inner peripheral surface of a hollow ingot. Molten metal may leak through the cracks. The core may then be rigidly encased by the leaked molten metal, which makes the casting operation impossible. The draft of a core is therefore determined, depending upon the - 6 respective kinds of alloy and-dimension of hollow in-gots within an optimum range for attaining criterion qualities of cast skin.
The trouble of rigid core-encasement is most likely to occur in the case of using a forcedly cooled core, because the solidified shell rapidly grows on the forcedly cooled core during the initiation period of casting. Thickness and height approximately 8 forcedly cooled heat-insulative of solidified shell varies locally on the movable bottom block, because cooling intensity of molten metal varies depending upon the position in the mold cavity, such as inflow position and its opposite position. The casting parameters, such as the descending timing of a movable bottom block and the like, are therefore set within narrow ranges. It is very difficult to start the casting of a hollow ingot with thin wall ranging from to 50 mm by means of a mold equipped with a core. Meanwhile, heat conductivity of the core is dependent upon material and dimension of the particular core used. In the case of graphite core, which is generally known as the heat insulative core, the heat conductivity is high as compared with the refractory and heat-insulative core. When the graphite core is used at normal temperature, similar troubles as encountered in forcedly cooled core, are liable to occur. The graphite core is therefore occasionally preheated before using. This preheating is not only very complicated in the mass production of hollow ingots but is extremely difficult to attain always constant range of temperature of cores at the casting start.
SUMMARY OF INVENTION
The present invention is made under the circumstances of casting hollow ingot as described above.
It is an object of the present invention to provide a continuous casting method which enables a stable and efficient production a hollow ingot of particularly light metals, such as aluminum and magnesium, which has a smooth cast skin particularly on the inner peripheral surface, a homogeneous and fine structure with a small layer of inverse segregation, a high roundness, and a uniform thickness of wall.
It is another object of the present invention to provide an apparatus for implementing the method as described above.
It is a further object of the present invention to provide a method for eliminating the drawbacks encountered incasting start of a hollow ingot, thereby providing a hollow ingot which is free of cast defects on the inner peripheral surface thereof and which has improved qualities.
The present inventors variously investigated methods for solving the problems involved in the continuous casting of a hollow ingot and discovered a method which can be applied to any one of the float method, hot-top method tapping method with the aid of a spout.
The first invention of present application resides in a continuous casting method of a hollow ingot, comprising the steps of closing, at the casting start, an end of an annular space formed between a forcedly cooled tubular mold.and a forcedly cooled core by a movable bottom block, continuously pouring molten metal into the annular space, holding the molten metal in the annular space, cooling and solidifying the molten metal by the tubular mold or the tubular mold and core, thereby forming a hollow ingot, and continuously lowering the movable bottom block, thereby withdrawing the hollow ingot from the tubular mold, characterized by introducing gas around an outer peripheral surface of the core, forming, by said introduced gas, an annular gap surrounding an inner peripheral surface of a hollow molten metal held in the annular space, and applying gas pressure of the annular gap onto the inner peripheral surface of the hollow molten metal.
The second invention is an apparatus appropriate for carrying out the first in casting apparatus of a hollow ingot comprising a forcedly cooled tubular mold and a core which is held inside the tubular mold, characterized by further comprising: an overhang which is formed on an outer peripheral surface of the core in contact with molten metal during casting and which uniformly and horizontally protrudes outwards of the core; and apertures which end on the outer peripheral surface of the core beneath the overhang and which are communicated with a gas source. The core used in the present invention may or may not be forcedly cooled. The hollow ingot, to which the present application is applied, is mainly. cylindrical hollow ingot, i.e., a hollow or a direct billet, whidh is blank material of various annular or tubular products. The present invention may also be applied to a hollow ingot having square columnar form.
The gap, which is formed as a result of the pressure application, is positioned such that direct contact of molten metal with the core is impeded. The direct contact mentioned above is displaced downwards due to the formation of gap. The means for forming the annular gap in the case of a forcedly cooled core is an overhang which is formed on an outer peripheral surface of the core in contact with molten metal during casting and which uniformly and horizontally protrudes outwards of the core; and introduction of pressured gas toward beneath the overhang. The means for forming the annular gap in the case of a non-forcedly cooled core is an overhang of the core which is formed directly above an outer peripheral position of a core where the solidified shell starts to f orm the overhang s may be introduced through any passage provided that directed beneath the overhang. The apertures pertures rein and introduction of pressured gas toward beneath The ga gas is fo the r introducing gas are minute clearances or a designed that molten metal does not invade the The apertures may be embodied in various structures. For example, in the hot-top casting method, a refractory and heatinsulative reservoir in the columnar or tubular form is located continuously on the top of a cooling core, and the lower peripheral surface of overhang protrudes beyond the higher peripheral surface of core to form an overhang. The slits for introducing gas are formed at the continuous parts and are gas in the communicated with passages of 30 According to another example, which are so cooling core. the apertures for introducing gas may be embodied as gaspermeable refractory material which constitutes the outer peripheral part of a core beneath the overhang and which is communicated with the introducing passages of gas in the core. The refractory and heatinsulative reservoir mentioned above is preferably made of material which is difficult to be wetted with molten metal, such as the materials known under trade names of LUMIBOARD L100 (NICHIAS CO., LTD.), INSURAL (FOSECO Ltd.), and FIBERFLUX (TOSHIBA CERAMICS Co., Ltd.). The gas-permeable refractory material mentioned above is preferably the one which has a high heat conductivity, and is difficult to be wetted with molten metal. Preferably, the pores of such material is such that molten metal is difficult to enter. Porous graphite, ceramics, e.g., silicon carbide bonded with porous silicon nitride, and refractory sinterd metals are appropriate as the gas-permeable refractory material.
Gas introduced as described above is stored beneath the overhang of top part of cooling core and forms beneath the overhang an annular gap around the outer peripheral surface of core. The gap is therefore formed between the outer peripheral surface of core and the inner peripheral surface of molten metal. If the overhang is not provided, the gas introduced floats through the molten metal without stagnation and bubbles on the top level of molten metal. The annular gap is therfore not formed.
Dimension of an overhang, i.e., the external protrusion of outer peripheral surface of a forcedly cooled core, is preliminarily determined by experiments and is dependent upon the kinds of metals and alloys, shape and dimension of an ingot, casting speed, height of molten metal and mold, and the like. For example, in the case of the aluminum or magnesium based alloys and a hollow ingot having inner diameter of form 20 to 100 mm, the protrusion is 1.5 mm or more, preferably 3.0 mm or more. Less than this value, it is difficult to stably maintain the annular gap for gas application. The upper limit of protrusion is not specifically limited but the protrusion exceeding 15 mm is insignificant.
Pressure to be applied in the annular gap is in the vicinity of hydrostatic pressure of molten metal at a level of the annular gap, which is formed beneath the overhang. The pressure to be applied should be: below such a value that the gas overflows above the overhang and then floats to bubble on the level of molten metal; and, above such a value that contact area of molten metal with the outer peripheral surface of a core is essentially reduced by the annular gap.
The annular gap formed as a result of gas introduction is not gas tight. Excessive part of gas, which is greater than the one for forming annular gap having a pressure nearly in - 10 commensurdte with the hydrostatic pressure mentioned-above, flows downwards through minute clearances between the outer peripheral surface of a cooling core and thin solidified shell around the metal body. During flowing the gas forms a curtain. It is presumed based on the experiments by the inventors that: the clearances mentioned above pulsate and their positions vary in the circumferential direction around metal body; and, shrinkage of molten metal due to cooling causes expansion of annular gap and expansion of molten metal due to hydrostatic pressure causes diminishing of annular gaps; the annular gaps move along the ccre surface; and, every gaps pulsate. Accordingly, when certain casting parameters are given, virtually constant flow rate of gas needs to be kept so as to maintain the gap, where deter-mined gas pressure is applied.
Gases, which can be used for aluminum-base alloys, are argon, nitrogen, helium and the other inert gases. According to experiments by the present inventors, air, nitrogen, thermal decomposition gas of lubricating oil and alcohol, and steam unexpectedly bring about good results for a number of the above mentioned base alloys. These gases and vapor containing oxygen at a concentration of 80 % by volume or less were discovered to be appropriate for light metals and their alloys. When the volume of oxygen exceeds 80 %, qombustion reaction of lubricating oil with oxygen takes place to impair the lubricating effect of the oil. In the case of continuous casting of aluminum-lithium alloys, the volume of oxygen should be 15 % or less, since these alloys have high viscosity. Appropriate gases magnesium base alloys are argon, dioxide and the other inert gases used for continuous casting nitrogen, helium carbon 30 and of sulfur hexafluoride, alone or in combination.
As in the conventional continuous casting, lubricating interface is formed on the outer peripheral surface of a cooling core so as to prevent sticking of molten metal on such surface. The lubricating interface is formed by well known methods, such as a method for continuously or semi-continuously feeding liquid lubricating oil onto such surface to wet it, and a method for forming a core by material having heat resistance and self-lubricating effect, such as the graphite and boron nitride have.
In -the present first and second inventions, the heat flow rate from the inner surface of molten metal held in a hollow columnar form to the cooling core is decreased, and the friction between core and semisolidified or solidified ingot is decreased. As a result, the cast skin of a hollow ingot is smooth at the inner peripheral surface, the inverse segregation layer is small in the metal structure at a directly beneath region of the cast skin, and the structure is uniform throughout the inner and outer peripheral layers of a hollow ingot.
In a non-forcedly cooled core, predominant cooling factors that advance the solidification of molten metal held in a columnar form are the cooling by a forcedly cooled mold and the direct cooling (chilling) by cooling water injected onto theouter peripheral surface of a solidified ingot beneath the mold. The solidification interface of molten metal has therefore a configuration like a slope which descends from the outer peripheral surface of molten metal toward the core. Increase in viscosity of molten metal occurs in the molten metal besides the core, because the proportion of solid phase to liquid phase increases in the outer peripheral surface of molten metal until solidification is completed. This in turn causes increase in the friction between the molten metal and outer peripheral surface of a core, thereby frequently generating various casting defects, such as cracks and streaks, and casting troubles, e.g., break out.
When the first and second inventions are applied for the non-forcedly cooled core, an annular gap is formed around the outer peripheral surface of core and decreases the contact area between the outer peripheral surface of core and molten metal, particularly molten metal in the vicinity of solid-liquid interface. The friction is also decreased by curtain of gas which flows down along the boundary between the solid ingot and core. The present invention is therefore advantageous for the continuous casting with the aid of a non-forcedly cooled core and allows to stably produce, without casting troubles, e.g., break out, hollow ingots having smooth cast skin around the inner peripheral surface.
In accordance with an object of the -present invention, there is provided a continuous casting method:of a hollow ingot according to the first invention further comprising, when starting casting, the steps of: covering, before pouring the molten metal into the annular space, the inner peripheral surface of the cover with a refractory heat-insulative material, bringing the refractory heat-insulative material into contact with the molten metal; poured into the annular space at the casting start; encasing the refractory heat-insulative material with cast metal being solidified on said refractoy heat-insulative material; and, withdrawing, together with the refractory heat-insulative material, the hollow ingot. This method is referred to as the third invention. The third invention can be embodied as: the first embodiment, in which only the outer peripheral surface of a core is covered with a refractory heat-insulative ring; the second embodiment, in which the outer peripheral surface of a core and the forcedly cooled mold are covered with a refractory heat-insulative ring; and, the third embodiment, in which the outer peripheral of a core, the forcedly cooled mold, and the top of a movable bottom block are covered with refractory heat-insulative material. In the first embodiment, the outer peripheral surface of a core is covered with refractory heat-insulative ring, so as to improve the thermal influence of contact part of the core with molten metal and to retard growth of solidified shell on the outer peripheral surface of a core. In the second embodiment, not only the thermal influence of core but also the thermal influence of a contact part of mold with molten metal are improved. Namely, the inner surface of a forcedly cooled mold is covered with material which is refractory and heat-insulative. As a result,an oriented solidification is realized so that the solidification advances predominantly by cooling by a movable bottom block. In this embodiment, solidification of molten metal is retarded in the casting passage formed by the core, mold and bottom block. In the third embodiment, the thermal influence of movable bottom block is also improved so as to realize heat-insulation state in the casting passage and hence to attain stable casting-start of a hollow ingot with a thin wall.
surface 20 surface The third invention can be embodied as the fourth embodiment. Namely, lugs made of material resistant against erosion by the molten metal are rigidly provided on the movable bottom block, in carrying out the first, second and third embodiments. Since the lugs are encased in cast metal being solidified thereon, and the movable bottom block is subsequently withdrawn, this embodiment furthermore stablizes casting start.
The refractory heat-insulative material used in the above embodiments of third invention is selected among various materials having refractory and heat-insulative properties at a temperature of molten metal. For example, for molten metal of aluminum and its alloys, are used sheets made of various ceramic fiber or sheets which are formed by slip casting ceramics into a form of ring. Alumina fiber, silica fiber, glass fiber, carbon fiber, preformed LUMIBOARD (trade name of NICHIAS CO., LTD.), and the like are preferred as the ceramic fiber. As commercial products, Ceramics Paper (trade name of Toshiba Monoflux Co., Ltd.) and Ibiwool paper (trade name of Ibiden Co., Ltd.) are representative ceramic wools. These materials have a low heat conductivity, for example, 0.11 0.08 Kcal/mhC at 700 -600'C for Ibiwool paper (1 mm thick). Materials and their thickness are selected considering the kind of molten metal, temperature, heat capacity of a mold block as a whole, cooling condition, and the like. Thickness of refractory heat-insulative material is usually in the range of from 0.5 to 3 mm.
The refractory heat-insulative ring is preferably embodied as follows. That is, the ring is provided, on the surface brought into contact with molten metal, with lugs made of material which is resistant against erosion by molten metal. The ring is provided, on an intermeiate or top part, with holes which reach the core and/or mold. The ring is provided, on an intermediate part, with holes reaching the top surface of movable bottom block. The lugs and holes mentioned above may be provided in combination. In these embodiments, the lugs and holes are rigidly engaged with the soli'dified metal at casting start, thereby allowing stable separation of refractory heat-insulative material from the outer peripheral surface of a core or the inner peripheral surface of a mold.
The lug(s) on a movable bottom block, which are---app.ropriate in the fourth embodiment may be a single or plurality of nails or rods. Two or six nails or rods spaced at equal distance apart are usually satisfactory.
BRIEF DESCRIPTIONS OF DRAWINGS
Fig. 1 and Figs. 2(A) and (B) show an apparatus of Example 1, in which the first invention is applied for the hot-top casting. Fig. 1 is an overall view. Fig. 2(A) is a cross sectional view of the essential parts of a core. Fig. 2(B) is a plan view of the core.
Fig. 3 shows an apparatus of Example 2, in which the first invention is applied to the float casting method.
Figs. 4 and 5 show the apparatuses of Examples 3 and 4, respectively. in which a gas-permeable refractory ring is is fitted around the outer peripheral surface of a cooling core.
Fig. 6(A) is a vertical cross sectional view of the core used in Example 5.
Fig. 6(B) is an elevational view of the cross section of a core of Fig. 6(A).
Fig. 7 illsutrates an application of the present invention to the hot-top casting method and shows a vertical cross sectional view of a nonforcedly cooled core.
Fig. 8 is a microstructure photograph of the inner peripheral surface layer of a hollow ingot of aluminum alloy (AA 5052) produced by the inventive Example 1.
Fig. 9 is a microstructure photograph of the inner peripheral surface layer of a hollow ingot of aluminum alloy (AA 5052) produced by the comparative Example Fig. 10 is a macrostructure photograph of peripheral surface layer of a hollow ingot of (AA 5052) produced by the inventive Example 1.
Fig. 11 is a macrostructure photograph of the inner peripheral surface layer of a hollow ingot of aluminum alloy (AA 5052) produced by Comparative Example 1.
Fig. 12 is a partial cross sectional view of a vertical continuous casting apparatus, in which a core is covered with a refractory heat- insulative ring.
Fig. 13 is a partial enlarged view of Fig. 12.
Fig. 14 illustrates that solidification is advanced as 1. the inner aluminum alloy - 15 compared with the state shown in Fig. 12 to enable withdrawal of a movable bottom block.
Figs. 15 and 16 illustrate the casting start with the aid of a refractory heat-insulative ring provided with the lugs shown in Fig. 17.
Fig. 17(A) illustrates an example of lugs provided on the refractory heatinsulative ring.
Fig. 17(B) is a cross sectional view along the line A - A' of Fig. 17(A).
Fig. 18 illustrates an example of cooling holes of a ref- ractory heat-insulative ring.
Fig. 19 is a drawing similar to Fig. 12 and illustrates an embodiment, in which both core and mold are covered with a refractory heat-insulative ring.
Figs. 20 and 21 embodiment, in with the aid of refractory heat-insulative Fig. 22 is a drawing similar to Fig. in which all of the core, a embodiment, 20 block are covered with Fig. 23 are cross sectional views illustrating the which withdrawal of a hollow ingot is started ring with lugs.
12 11 mold and movable bottom refractory heat-insulative ring.
illustrates an example, in which the refractory shown in Fig. 22 is integrally formed.
illustrate modification of the embodiments and i ustrates an heat-insulative cover Figs. 24 and 25 shown in Fig. 21.
Fig. 26 illustrates an embodiment, in which the third in vention is applied to the horizontal continuous casting method.
Fig. 27 illustrates casting-start according to the conventional method.
Fig. 28 is a partial cross sectional view of continuous casting apparatus according to an example of the present invention, illustrating a nail rigidly secured on a movable bottom block.
Fig. 29 is casting apparatus according to an invention, illustrating a partial cross sectional view of continuous example of the present a lug made of an inverse L shaped rigidly located on the movable bottom block.
Fig. 30 is a partial cross sectional view of continuous casting apparatus shown in Fig. 25 and having a steel nail rigidly located on the movable bottom block.
1 Fig. 31 shows a continuous casting apparatus according to an embodiment of the present invention, in which a movable bottom block including two slopes therein, which slopes having arris lines. Fig. 31(A) is a vertical cross sectional drawing of general view of the apparatus. Fig. 31 (B) is a side view of the bottom block and a cross sectional view along line A A'. Fig. 31 (C) is a cross sectional view of bottom block along the line B - B'.
Fig. 32 shows a continuous casting apparatus according to an embodiment of the present invention, in which a movable bottom block including one slope having arris line. Fig. is a vertical cross sectional drawing of apparatus. Fig. 32 (B) 32(A) general view of the is a side view of the bottom block and a cross sectional view along line A - A'. Fig. 32 (C) a cross sectional view of bottom block along the line B - B'.
is The The rence to the non-limitative embodiments.
Fig. first invention which is applied to the hot top illutrated apparatus can be summarized as follows. A hot-top continuous casting apparatus with the pressure application disclosed in USP No. 4157728 (West Germany Patent No. 2734388) is additionally provided with a core so as to carry out the first invention and to form smooth cast skin on both the inner and outer peripheral surfac-es of a hollow ingot. A tubular mold 1 is made of material which is highly heat-conductive and heat-resistant, such as metal and graphite. The tubular mold 1 has an appropriate shape defining the outer peripheral surface of a hollow ingot 15 and surrounds the space where a hollow ingot 15 is formed. The tubular mold 1 has a traversally circular shape, when, for example, a cylindrical ingot is cast. The mold 1 has a cavity, into which the forcedly cooling media, such as water 4, flows through the water-feeding conduit 3. On the top surface of tubular mold 1, a molten metal reservoir 2 made of refractory heat-insulative material (for example, trade name "LUMIBOARD") is rigidly connected. The molten metal reservoir 2 is located concentrically with respect to the tubular mold 1.
present invention is hereinafter described with refe- 1 is a drawing which illustrates an example of the castina method.
- 17 The peripheral-surface of lower end of molten metal reservoir 2 uniformly protrudes_beyond the inner surface of tubular mold 1 and hence forms an overhang 5. Minute slits 6 are formed at a contact area of the top surface of tubular mold 1 and bottom end surface of molten metal reservoir 2. The slits 6 are directed to the inside of mold. Pressured gas is fed to the slits 6 from introduction port 7 and is then introduced beneath the overhang 5. Lubricating oil in liquid form is pressured and fed through an introduction port 8. Minute slits 8a for feeding the lubricating oil are formed in the tubular mold 1 and oriented toward the inner peripheral surface near the top end of mold. The lubricating oil is therefore fed through the minute slits 8a and consequently flows over the inner peripheral surface of tubular mold 1.
Molten metal 9 is poured through the feeding port 10 into the molten metal reservoir 2, until molten metal reaches the level 11. The molten metal 9 is brought into contact with and cooled by the peripheral surface of mold 1 which is cooled by water 4. The solidification of molten metal 9 thus starts. The gas introduced as described above flows in beneath the overhang 5 and forms there an annular gap, where gas pressure is applied. The starting point of solidification is forced to displace downwards due to the annular gap. The annular gap extends along the inner peripheral surface of tubular mold 1, and the top and bottom ends of annular gap are located directly beneath the overhang 5 and a somewhat distant part from the overhang. The contact of molten metal with inner peripheral surface of mold is impeded by the annular gap.
A movable bottom block 13 is placed on the table 12 which is supported by a hydaulitic mechanism in a liftable manner.
The solidified ingot 15 is lowered by means of hydraulic mechanism and is subjected, during the lowering movement, to the direct action of secondary cooling water 14, 22 which is injected through the slits elongated through lower end of mold and core and oriented downwards. When certain length of an ingot issues, pouring of molten metal into the molten metal reservoir 2 and lowering movement of table 12 are stopped, the tubular mold 1 is displaced away, and the table 12 is elevated to carry the ingot 15.
A core 1-6, which is forcedly cooled, is held inside concentrically or coaxially with respect to the tubular mold 1 which is forcedly cooled. The core 16 is made of material which is the same as or similar to that of tubular mold 1. The core 16 has an appropriate shape for defining the inner peripheral configuration of a hollow ingot 15. The shape of core 16 is cylindrical, when, for example a round tubular ingot is to be cast. The core 16 occupies the space where the hollow part 19 of an ingot 15 is formed. The outer peripheral surface 16a of core is tapered, as shown in the drawing, toward inside, commensurate with the solidification shrinkage of molten metal. The core 16 is supported by a pipe 17 which is integrally attached to the axial center of core 16 and which extends vertically upwards. The pipe 17 is operably connected with supporting mechanism (not shown). This mechanism supports the core 16 at a fixed position or supports the core 16 verically movably. This mechanism controls the horizontal and vertical positions of a core 16. In the embodiment illustrated in Fig. 1, the top level of a core 16 is flush with the top level of the tubular mold 1. The top level of a core 16 can, however, optionally selected higher or lower than the top level of tubular mold 1, depending upon the kind of cast metals, dimension of a hollow ingot, thermal equilibrium conditions of continuous casting apparatus and the like.
Pipe 17 opens at its lower end to the cavity 21 of core 16. Cooling water is fed from the upper end 20 of pipe 17- and then cools the core 16. The cooling water is then injected through the slits or holes having small diameter which are formed in the lower peripheral end of core 16 and directed downwards. The thus injected water constitutes the secondary cooling water 22.
Header 18, which is made of cylindrical refractory heat-insulative material (trade name "LUMIBOARD"), is fixed on the top surface of core 16 at a concentrical position of the core 16. The pipe 17 vertically protrudes the header 18. In the present embodiment, the material of header is the same as that of molten metal reservoir 2. Their materials may however be different from one another. The outer peripheral lower surface of a header 18 uniformly protrudes beyond the outer peripheral b e - 19 upper surface of core 16 and thus forms an overhang 23. Minute slits 24 are formed at a contact part of top end of core 16 and bottom end of header 18 and are directed outwards. The minute slits 24 have uniform dimension around the contact part.
Pressured gas is fed to the slits 24 through the introduction conduit 25 which protrudes through the header 18. Gas pressure is therefore applied toward the inner peripheral surface of molten metal beneath the overhang 23. An introduction pipe is 26 also provided for feeding the lubricating oil therethrough.
Minute apertures 26a (Fig. 2) are radially formed around the wall part of a core 16, and are directed to the outer peripheral surface of a core 16. The lubricating oil therefore exudes at the outer peripheral surface of a core 16 and consequently uniformly wets such surface.
Referring to Fig. 2, the essential part of the core shown in Fig. 1 is illustrated in an enlarged view. Fig. 2(A) is a vertical cross sectional view of the core. Fig. 2(B) is a cross sectional view along the line A A' of Fig. 2(A). At a contact part of the lower surface of header 18 and the top surface of core 16, 0 rings 28 and 29 are inserted. The 0 rings 28 and 29 are disposed at positions surrounding the gas-introduction pipe 25 and the lubricating oil-introduction pipe 26. 0 ring 30 is also inserted at the contact part inside the grooves for distributing gas around the core. Accordingly, the 0 rings 28,
29 and 30 prevent at the c-ontact part the leakage of the gas and lubricating oil. The groove 31 ior distributing gas around core has an annular configuration and is formed on the top surface of a core 16 and near the outer peripheral surface of core 16. The gas is introduced from the gas-introduction groove 31 via the slits 24 to beneath the overhang 23, where the gas forms the annular gap 23a and applies the pressure to the inner peripheral surface of molten metal 10. Minute clearances are formed between the thin, deformable solidified shell of molten metal having not yet rigidity and the inner peripheral sur- face of a core 16. Excessive gas flows downwards out of the annular gap 23a through the minute clerances.
Annular groove 26b is formed in the outer peripheral part of core 16, so as to distribute the lubricating oil around the core 16. The lubricating oil is fed through the introduction - 20 conduit 26, then fills the annular gr-aorve 26b, and exudes to' the outer peripheral surface of core 16 to wet such s'urface. Natural vegetable oil, such as castor oil, peanut oil, and rapeseed oil, or synthetized lubricating oil can be used alone or in combination as the lubricating oil. The lubricating oil used is however not limited to these oils.
Referring to the apparatus shown in Fig. 3, an application of the first invention to the float casting method is illustrated. The tubular mold 1 is forcedly cooled by the cooling water which flows in through the introduction conduit 3.
A cylindrical core 16 is held concentrically inside the tubular mold 1. 'The core 16 is forcedly cooled by the cooling water which flows in through the introduction conduit of 17 into the core 16. The top surface of tubular mold 1 is flush with that of core 16. Metallic molten metal 10 is stored in a tundish 27 and is then poured into an annular clearance between the tubular mold 1 and core 16 via the bottom end of a tapping plug 10a, spout 28 and then the float 29. The float 29 controls the level of molten metal surface 11 within mold. An overhang 23 is formed in the proximity of and above the level, where the solidification starts, for mitigating the cooling of molten metal by the core 16. Refractory heat-insulative felt 2a surrounds the outer peripheral surface of a core 16, and the overhang 23 is defined by the lower end of the felt 2a. The outer peripheral surface of a core 16 is provided with an inversely conical shape which is in commensurate with progress of shrinkage of an ingot in the axial direction during pressured gas protrudes through the core 16 from its top side to interior. A conduit 26 is provided for introducing the liquid lubricating agent. These conduits 25 and 26 are communicated with the distributing grooves having the same structure as in Example 1. From these slits via the respective slits, the pressured gas and lubricating agent flow off. As a result, the pressured gas is fed directly beneath (23a) the overhang and the lubricating to the outer peripheral surface of a core. The and lubricating agent are fed, as in Example 1, via mechanisms for controlling the pressure and flow rate of fluids (not-shown).
solidification. A conduit 25 for introducing agent is fed pressured gas a pipe The apparatus shown in Fig. 4 is used as a core in the hot-top method described in Example 1. The core 16 is forcedly cooled. A header 18 which is made of refractory heat-insulative material is rigidly connected to the top surface of a core 16. The header 18 protrudes, at its bottom end, uniformly outwards beyond the outer peripheral surface of a core 16. The overhang 23 is therefore formed around the outer peripheral surface of a core 16. A heat conduc tive and gas-permeable ring 32 is inserted around the outer peripheral surface of a core 16.
0 rings 32a and 32b are disposed at the contact part of this ring 32 and core 16 so as to make this contact part gas tight. An annular groove 33 is formed at the contact part of the heat conductive and gas- permeable ring 32 and is communicated with an introduction conduit 26 of lubricating agent which pro- trudes through the header 18. Lubricating agent is fed to the annular groove 33 and then exudes on the outer peripheral surface of the ring 32. Porous graphite (for example, commercially available under the trade name of ATJ produced by the Union Carbide Corporation) or sintered powder metal can be used as the heat conductive and gas-permeable material. Size of the pores of this material is so fine that the molten metal does not infiltrate therein.
A spacer 34 made of metal is inserted in the lower end of the header 18 so as to enhance gas tightness. A conduit 25 for introducing the pressured gas protrudes through the header 18 and the spacer 34 and is connected with a part of an annular groove 35 which is formed on the lower end of spacer. Slits 24 radially extend from the annular groove 35 toward the overhang 23. Gas therefore passes through the slits 24. An 0 ring 29 prevents the leakage of introduced gas.
The groove 33 in the refractory and gas-permeable ring 32 is preferably positioned as close as possible to the overhang 23 and in such a vertical position that: molten metal contacts with a part of this ring 32 which is approximately flush with the level of the groove 33. The groove is preferably in the form of a strip around the core body.
Desirably, the outer peripheral surface of refractory and gas-permeable ring 32 is provided with a taper in the - 22 casting. direction. A pipe 36 is positioned inside the pipe 17 for introducing cooling water, protrudes through the core 16 and is positioned concentrically with this pipe 17. The pipe 36 is opened to ambient air at the top end (not shown) thereof and is opened to the inner space 37 of a hollow ingot 15. The pressure of inner space 37 of a hollow ingot can therefore be maintained atmospheric pressure due to the pipe 36. This pipe 36, which has the function of pressure maintainance mentioned above, is however not essential.
The apparatus shown in Fig. 5 is another embodiment shown in Fig. 4 and is appropriate for a core used.in the hot-top casting method.
A heat conductive and gas permeable ring 32 made of ref ractory material is inserted around the outer peripheral sur face of a core 16, as in Fig. 4. This ring 32 includes an upper part which is in the form of a flange uniformly protruding outwardly and thus forms an overhang 23. A refractory heat-insulative header 18 is rigidly provided on the core 16 and the flange. 0 rings 38a and 38b are inserted at a contact part between the header 18, the flange and the core 16 so as to prevent leakage of gas and lubricating oil from the contact parts. Lubricating oil is passed through the header 18 and is then introduced into the core body with the aid of a conduit 26. The lubricating oil is then distributed around the annular groove 39 which groove is formed in the core inside the gas permeable ring 32. Vertical position of annular groove 39 is above the contact position of molten metal with an outer peripheral surface of the gas permeable ring 32 and is beneath the overhang 23. The top part of an annular groo-ve 39 extends upwards thereby directing lubricating oil directly beneath the overhang 23. Lubricating oil fills the annular groove 39, then permeates through the gas-permeable ring 32, and wets its outer peripheral surface.
Meanwhile, the gas is introduced through the header 18 and then the core body with the aid of a conduit 25. This conduit is connected with one part of a horizontal annular groove 40, which is provided inside the flange of gas permeable ring 38 near the overhang 23. The gas is therefore distributed around the horizontal annular groove 40 and is then fed directly beneath the overhang 23. The gap 23a, where gas pressure is applied, is therefore formed.
The apparatus shown in vertical cross sectional view of Fig. 6A is an example of core used in the hot-top method shown in Fig.l. A header 18 is provided with a recess on the bottom end 41. The core 16, which is forcedly cooled, is inserted, at its top end, in the recess 41. The header 18 includes, in its lower periphery, a downward part 42 which covers the upper outer peripheral surface of a core 16. This downward part 42 protrudes uniformly outward beyond the outer peripheral surface of a core 16.
The conduit 26 for feeding lubricating oil protrudes downwards through the header 18 and is connected, at its lower end, with one part of annular groove 26b in the core 16.
is Capillaries 26a branch off from the annular groove 18 and end on the outer peripheral surface of a core 16. The lubricating oil passes through the capillaries 26a and wet the outer peri pheral surface of a core 16. The conduit 25 for introducing pressured gas protrudes downwards through the header 18 and is connected, at its lower end, with a part of annular groove 31.
A minute slit 24 is connected with the annular groove 31.
Minute slits 24a are formed between the outer peripheral surface of a core 16 and the downward part 42 of a header 18 and are connected in turn with the minute slit 24. The minute slits 24a are opened directly beneath the overhang 23.
Pressured gas is therefore fed through 25, 31, 24 and 24a and forms an annular gap 23a, where the gas pressure is applied, so as to decrease contact area of molten metal with the core surface, which is forcedly cooled.
Referring to Fig. 6B, a partial cross sectional and eleva tional view of Fig. 6A is shown. Minute slits 24a are formed by knurling tool in the form of vertical minute grooves. These minute slits 24a are preferred for the passage of gas, since the minute slits 24 do not clog.
Referring to Fig. 7, a modification of the hot top cast ing method illsutrated in Fig. 1 is illustrated. In this embodiment the present invention is applied to a non-force dly cooled core. A core 16 made of refractory heat-insulative material (trade name, LUMIBOARD) is integrally bonded by means - 24 of a bolt 36a with a header 18 which is made af the identical refractory heat-insulative material. The lower end of header 18 protrudes externally beyond the outer peripheral surface of core at its upper end and hence forms an overhang 23---Pressured gas and lubricating oil are fed through the conduits 25 and 26, respectively, which protrude through the header 18. Pressured gas, for example sir, is fed toward 23a, directly beneath the overhang, and, lubricating oil is fed toward the outer peripheral surface of core, as in the embodiment illustrated in Fig. 1. The overhang is positioned in molten metal and directly above the solid-liquid interface 15a, such that distance between the level of overhang 23 and the solid-liquid interface 15a is preferably 30 mm or less, more preferably 10 mm or less.
In Figs. 12 through 30, except for Fig. 27, the embodiments of the third invention are illustrated. The same is parts of a continuous casting apparatus shown in Figs. 12 through 30 as in Figs. 1 through 7 are denoted by the same reference numerals. These parts are not described with reference to Figs. 12 through 30 for the sake of brevity.
In Figs. 12 and 13, the reference numeral 51 denotes a conduit for feeding gas. The fed gas is then introduced to the annular groove 51a which is formed on the top surface of tubular mold 1 and circumferentially around the conduit 7. The core 16 is suspended in the cavity of tubular mold 1 by a suspension mechanism (not shown). The secondary cooling water 22, which flows out from the core 16, cools the movable bottom block 13 during an initial casting period and then cools, after the initiation of casting withdrawal, the inner surface of a hollow ingot. Due to this cooling function,.--he solidification interface is maintained at an appropriate position as seen in the casting direction during the continuous casting of a hollow ingot.
Annular gas-passage 54 is formed between the header 18 and the conduits 26 for feeding lubricating oil. Before casting, a refractory heat- insulative ring 59 is fitted around the outer peripheral surface of a core 16. When molten metal is poured into a continuous casting apparatus, it is subjected to the primary cooling action by means of the movable bottom block 13 and tubular mold 1. The solidified shell 58 is consequently is formed. Since the refractory heat-insulative ring 59 is present besides the core 16, the solidified shell 58 grows relatively slowly on this ring 59 as compared with the growth on the movable bottom block 13 and the tubular mold 1. Referring to Fig. 27, the growth of solidified shell in the case of absence of refractory heat-insulative ring 59 is illustrated. The solidified shell 58 on the outer peripheral surface of a core 16 and the other surfaces grows in a uniform thickness. In accordance with solidification-shrinkage of solidified shell 58, the core 16 is encased by the cast metal solidified thereon. Although the draft 16a is formed on the outer peripheral surface of a core 16, the draft 16a does not function to realize smooth withdrawal of an ingot in cases where the encasement force of cast metal is high.
Referring to Fig. 14, the solidification is more advanced than that shown in Fig. 12. The solidified shell 58 grows further and finally grows on the refractory heat-insulative ring 59. The refractory heat-insulative ring 59 is therefore encased by the cast metal of solidified shell 58 as shown in Fig. 14. This ring 59 is so detachably fitted around the core 16 that the ring 59 is withdrawn at casting start. If the refractory heat- insultaive ring 59 is rigidly secured with the core 16, and, when the movable bottom block 15 and hence the ring 59, which is encased in the cast metal of solidified shell 59, are withdrawn at casting start, then the ring 59 is partly broken and its fragments are engulfed in the solidified shell 58 to form cast defects. In this case, an object of the third invention is not attained. The refractory heat-insulative ring 59 may be loosely fitted around the coTe 16, be roughened on the surface thereof, or be made integrally in the'form of a net, so as to firmly bond solidified shell 58 with the ring 59.
Referring to Figs. 15 through 18, preferred embodiments for ensuring withdrawal of a refractory heat-insulative ring 59 together with a movable bottom block 13 and for ensuring bond-ing between the solidified shell 58 and the.ring 59 is illustrated.
In Fig. 15, the details of tubular mold 1 and core 16 omitted. Reference numeral 60 denotes lugs made of material difficult to erode with molten metal 9 (for example, in the are merelv reinforceE - 26 case of aluminum molten metal, steel). The lugs 60 protrude through the refractory heat-insulative ring 59 and.extend intothe mold cavity. The lugs 60 are therefore encased-by-the cast metal which solidifies on them. The lugs 60shown in Fig. 15 is in the form of " = " having a part facing the core 16 and reinforcing the protrusions. This part is not essential, since it the protrusions. The solidified shell 58 grows as shown in Fig. 15, and solidifies on and encases the lugs 60. The solidified shell 58 and refractory heat-insulative ring 59 are therefore bonded with each other securely. When a hollow ingot, in which the bonding mentioned above has been attained, is withdrawn, the entity (58, 59 and 60) lowers while growth of the solidified shell 58 is promoted further as shown in Fig. 16.
Referring to Figs. 17(A) and (B), a partial magnified view of refractory heat-insulative ring 59 is shown. The lugs 60 are made of staples. Reference numeral 61 denotes cooling grooves 0 in U or V shape, formed by notching the upper edge of a refractory heat- insulative ring 59. Molten metal enters the grooves 61 and solidification starts there. The grooves 61 therefore behave as the solidification starting points in the molten mftal 7. The encasement is therefore improved by both grooves 61 and lugs 60, thereby completely encasing the refractory heat-insulative ring 59 with the metal solidified on it 59 and hence ensuring the withdrawal of ring 59 together with a movable bottom block.
Referring to Fig. 18, cooling holes 62 having the same function as the cooling grooves are illustrated. When molten metal enters the cooling holes 62 during the initial casting period, the solidification occurs earlier in the cooling holes 62 than on the major surfaces of a refractory heat-insulative ring 59. The cooling holes 62 therefore behave as the solidification starting ponts in the molten metal 7. Preferred diameter of the cooling holes 62 is in the range of from 1.5 to 15 mm. Below this range, the effects of cooling holes are poor.
Above this range, it is difficult to mitigate, by the major surface of a refractory heat-insulative ring 59, chilling action of the core. The shapes of cooling holes are not limited to round ones. They may be rectangular, triangle, polygonal or slot.
Referring to Figs. 19, 20, and 21, are illustrated several embodiments, in which refractory heat-insulative rings are located in the positions different from that shown in Fig. 12. In Fig. 19 the casting period is the same as in Fig. 12. In Fig. 19, the refractory heat-insulative rings 59 and 70 are located facing the outer peripheral surface of a core 16, and the inner peripheral surface of a tubular mold 1, respectively. The solidification on the peripheral surfaces of mold 1 and core 16 is therefore suppressed, while the solidification on the movable bottom block 13 is promoted due to heat withdrawal through this plate 13. Oriented solidification is consequently realized, so that the growth interface of solidified layer 58 becomes flat. This in turn leads to a considerable delay in the solidification in the hollow casting passage surrounded by the core 16, mold 1 and movable bottom block 13. In this case, withdrawal timing of a hollow ingot, which is determined by the instance of appropriate growth of solidified shell, allows a large deviation from a criterion timing, because solidified shell grows slowly. The refractory heat-insulative ring 70 besides the tubular mold 1 must be withdrawn together with a hollow ingot as is described with reference to Fig. 12. Figs. 20 and 21 correspond to Figs. 15 and 16, respectively. In these drawings, the solidified shell 58 is rigidly bonded with the refractory heat-insulative rings 59 and 60 at both mold- and core-sides with the aid of the lugs 60 and 60'.
Referring to Fig. 22, another embodiment is illustrated. In Fig. 22, the refractory heat-insulative rings 59 and 70 are located facing the outer peripheral surface of a core 16, and the inner peripheral surface of a tubular mold 1, respectively.
A refractory heat-insulative sheet 71 is placed on the movable bottom block 13. As a result, solidification in the hollow casting passage surrounded by the core 16, mold 1 and movable bottom block 13 is considerably delayed. In this case, withdrawal timing of a hollow ingot allows a larger deviation from a criterion value than in the case of Fig. 19. The refractory heat- insulative rings 59, 70, and the refractory heat-insulative sheet 71 must be withdrawn together with a hollow ingot as is described with reference to Fig. 14.
is Referring to Fig. 23, tefractory heat-insulative rings 59, and sheet 71 are integrally formed in the form of "Lj". A number of cooling holes 62 and 63 for providing the solidi fication initiation points are formed on the wall of refractory heat-insulative material 59, 70 and 71. Number and area of the cooling holes 62 and 63 are determined such that the retarda tion effect by the above material be maintained active.
Referring to Figs. 24 and 25, other embodiments are illu strated. In Figs. 24 and 25, only a part of the top surface of a movable bottom block is covered with the refractory heat- - -insulative material. In the case of Fig. 25, the solidified shell begins to grow on the uncovered surface of movable bottom block and then grows vertically and horizontally. The solidi f4ed shell then reaches a peripheral end of the refractory heat-insulative ring 71. During subsequent period of solidified shell, it grows as if it creeps on the refractory heat-insulative ring 71. In a somewhat later period, a thin solidified shell is formed even on the refractory heat-insulative ring 59 which covers the core 16 and tubular mold 1. Upon attaining such state of solidification, the solidified shell is rigidly bonded with the movable bottom block 13 and refractory heat-insulative ring 59. The solidified shell and the ring 59 can therefore be withdrawn together when the movable bottom block 13 is withdrawn. 25 Referring to Figs. 28, 29 and 30, other embodiments are illustrated. In Fig. 28, the same casting period as in Fig. 15 and essential parts of a continuous casting apparatus are shown. A hole 81 is formed on the movable bottom block 13. A nail 82 made of copper is driven in the movable bottom block 13. In Fig. 29, the same casting period as in Fig. 20 and essential parts of a continuous casting apparatus are shown. A steel rod 93, the top of which is bent in an inverse L shape, is driven into a hole 81. In the cases Figs. 28 and 29, the nail 92 and steel rod 93 are encased with the solidified shell 58 growing on them 92 and 93. The solidified shell 58 is therefore furthermore rigidly bonded with the movable bottom block 13. As a result, the casting start is extremely stabilized.
29 - In Fig. 30, the same casting period as in Fig. 25 and essential parts of a continuous casting apparatus are shown.
A refractory heat-insulative ring 71 covers the mold and core as well as a part of the movable bottom block 13. A hole 91 is formed on the non-covered part of the movable bottom block 13.
A steel nail 92 is forced into the hole 91. The solidified shell starts to grow on the non-covered surface of a movable bottom block. The solidification then occurs along the steel nail 92, and, a thin solidified layer is formed on the refractory heat-insulative ring 71. After the lapse of time, the steel nail 92 is encased with solidified layer formed thereon, and this solidified layer is connected with a solidified layer which has grown on the uncovered part mentioned above. The steel nail 92 therefore contributes to rigid bonding between the solidified layer 58 and refractory heat-insulative rings 59 and 71. They (92, 58 and 59) are withdrawn alltogether at withdrawal of an ingot. The casting start is very stable in the present embodiment.
Although the embodiments of present third invention are described hereinabove with reference to vertical continuous casting apparatuses, the present third invention is equally applied to a horizontal continuous casting apparatus such as illustrated in Fig. 26. In Fig. 26, the parts of a continuous casting appratus denoted by the same reference numerals as in Fig. 12 denote the same parts. A core 16 is made of non-cooled graphite. Reference numeral 100 denotes a molten metal reservoir. Reference numeral 101 denotes an intermediate orifice plate which is located between the molten metal ieservoir 100 and tubular mold 1 and secure them 100 and 1.
Reference numeral 102 denotes a conduit for pouring molten metal. Reference numeral 103 denotes a movable bottom block.
Reference numeral 104 denotes a withdrawing rod of the movable bottom block 103. Temperature of molten metal is high in the tubular mold cavity at an inflow part through the conduit 102 for pouring molten metal, and is low at a side opposite to the inflow part. Temperature drop is for example by 20 'C for the case of aluminum alloy. The solidification becomes unbalanced due to such temperature drop, particularly in the case of casting a hollow ingot having a thin wall. It becomes - 30 consequently very difficult to set withdrawal timing of the movable bottom block 103. It is very advantageous for overcoming this difficulty to dispose refractory heat-insulative material 59 on the outer peripheral surface of a core 16 and on the movable bottom block 103, where solidification is drastic.
The present invention is applied not only for the case of holding a core concentrically with respect to a tubular mold but also for the case of holding a core non-concentricaly with respect to the core. In the latter case, a hollow ingot having an offset axis is obtained. In this case, the embodiment illustrated in Fig. 22 is preferably applied for a narrow annular clearance between the tubular mold and the core, and the embodiment illustrated in Fig. 12 is preferably applied for a wide clearance between the tubular mold and the core.
This combination contributes to elimination of unbalance of coolina and hence to stabilization of a continuous casting.
As described hereinabove, a refractory heat-insulative ring, which covers at least a core prevents the core from encasement by the cast metal and behaves as the bonding part with molten metal during initial solidification period. A refractory heat- insulative ring is withdrawn together with a hollow ingot. The refractory heat-insulative ring fulfills at a high degree the requirements of smoothening a cast skin and formation of rigid bonding for withdrawal. These requirements are incompatible to one another, unless the present invention is used. In the present third invention, a rather great variation in the timing is allowed for starting the withdrawal of a movable bottom block. Surface qualities of a hollow ingot are improved and casting yield is hence enhanced. In addition, productivity is enhanced.
When molten metal leaks through the inner or peripheral surfaces of a hollow ingot by accidents, the molten metal leaked solidifies on the movable bottom block and the like. It is difficult to remove such solidified material from the movable bottom block and the like. Referring to Fig. 31, another embodiment of a vertical continuous casting apparatus according to the present invention is illustrated. When the solidified materials are leaked through the inner and outer peripheral-surfaces of a hollow ingot and solidified on a movable bottom block and the like, these materials can be easily removed. The parts of this apparatus having the same reference numerals as in Fig. 12 are the same parts. Reference numeral 114 denotes a movable annular bottom block which is lifted, at the beginning of casting, upwards and is fitted in the bottom end of annular clearance between the tubular mold 1 and core 16. Reference numeral 112 denotes a table which is connected with a lifting mechanism (not shown) and which supports the movable annular bottom block 114. A carrier 120 is provided for carrying the movable annular bottom block and for facilitating the removal of solidified material. The movable annular bottom block 114 is placed on the legs 125 which are secured on the table 122. Between the legs 125 a block defined by one arris 119 and two slopes 117a and 117b is inserted. The lower ends of movable annular bottom block 114, which are not supported by the legs 125, face the openings above the slopes 117a and 117b.
Referring to Fig. 32, an embodiment of the present invention, which is applied to a float-type continuous cast ing apparatus, is illustrated. Fig. 32 shows the casting start.
The same reference numerals in Fig. 32 as in Fig. 31 denote the same parts of an apparatus as in Fig. 31. In the present embo diment, one slope 117 is formed at a position inside the mova ble annular bottom block 114 and a opening 118 is formed above this slope 117.
The angle of slope is selected so that molten metal, which streams on the slope 117, smoothly slip down on the slope 117 and is withdrawn on the table 122. This angle is adjusted depending upon the kinds of alloys, physical properties of molten metal, and the like. This angle is 30' or more, generally speaking. Elevation of 45' is preferred. The opening 118 is preferably as great as possible, as long as strength of legs 125 is not impaired. When the opening is narrower than the slopes, molten metal and water are disadvantageously liable to stagnate in the opening. The lower endof slopes 117 are preferably smooth, since any unevenness and steps at such connection impedes smooth falling down of solidified materials.
The apparatuses illustrated in Figs. 31 and 32 are appropriate 118a and 118b - 32 not only for casting of a round hollow ingot but a-Is-o-for casting of a hollow ingot having an irregular cross section.
Molten metal leaked along the outer peripheral surface of a core as well as secondary cooling water 22 of a core does not stagnate on the movable bottom block but is readily drained out from the movalbe bottom block onto a table 122. The table 122 becomes therefore wet. But, the explosion due to contact of molten metal with water does not occur on the table 122, since there is no stagnation of water on the table 122. The solidified material fallen on the table 122 is easily peeled from it 122.
The first and second inventions are described by way of examples. Example 1 is The hot-top casting method illustrated in Figs. 1 and 2 was carried out. Example 2 The float-type casting method illustrated in Fig. 3 was carried out.
Example 3
The hot-top casting method illustrated in Fig. 4 was carried out. Example 4 The hot-top casting method illustrated in Fig.5 was carried out.
Example 5 The hot-top casting method illustrated in Fig. 6 was carried out. Example 6 30 The hot-top casting method illustrated in Fig. 7 was carried out (non-forcedly cooled mold). Comparative Example 1 The hot-top type continuous casting apparatus illustrated in Fig. 1 was used. However, introduction of pressured gas via the conduit 25 through the header 18 was stopped. Accordingly, during the continuous casting, the annular gap, where pressure was applied, was not formed directly beneath the overhang 23.
Comparative Example 2 The float type continuous casting apparatus illustrated in Fig. 3 was used. However, The core was a cylindrical shaped body of refractory and heat-insulative material (trade name: LUMIBOARD). The core was therefore not forcedly cooled. Lubricating oil was fed through minute slits which were formed through a top part of, and opened on, the outer peripheral surface of the core.
The results of Examples 1 through 6 and Comparative Examples 1 and 2 are given in Table 1.
The casting speed given in Table 1 is the o. ne judged to be optimum depending upon the kind of alloys, cooling conditions and the like. The casting speed was set to this value. Gas was air, oxygen-rich argon or nitorgen. During the casting start is period of continuous casting, stability was realized in every one of the inventive examples, without incurring any trouble. However, in the comparative example, such troubles occurred during the casting start period, such as break out, non falling of an ingot due to its sticking to the core, and the like. The casting was therefore interrupted. Cast skin of the inner peripheral surface of ingots were very uniform and smooth in the inventive Examples 1 through 5. In the inventive Example 6, slight periodic remelting skin was observed on parts of ingots, but the cast skin was considerably improved over the conventional one. However, in the comparative examples, periodic remelting was observed on the cast skin and sticking skin in the form of longitudinal flaws occurred on the cast skin due to contact with the core. These phenomena occurred clearly in every ingot formed in the comparative examples. In addition, these phenomena were more frequent in Comparative Example 2 than Comparative Example 1. In Comparative Example 2, circumferential tear flaws were formed on cast skin.
Inverse segregation layer directly beneath the cast skin was from 75 to 95 4m thick in the inventive examples but 450 1m and 1500Lm thick in the comparative examples. This difference in thickness of segregation layer is great.
The microstructure of inner peripheral surface of an ingot is shown in Fig. 8 (Example 1) and Fig. 9 (Comparative Example 1).
It is readily apparent from these drawings that thickness of - 33 - 34 inverse segregation layer and structural uniformity of the inventive examples are superior to those of comparative examples.
Roundness of hollow part of ingots and uniformity in thickness of wall part of hollow ingots of the inventive examples are superior to those of the comparative examples.
T a b 1 e 1 Apparatus Kinds of alloys Outer diameter of ingot (mm) Inner diameter of Fig.1 Fig.2 Fig.3 Fig.4 Fig.5 AA 5052 AA 5052 AA 5056 AA 7075 AA5052 Fig. 7 AA 6063 250 158 250 350 250 350 ingot (mm) 118 118 118 95 118 120 Casting speed (mm/min) 120 120 110 110 116 100 Lubricating oil castor oil rape oil peanut oil castor oil peanut oil castdr oll (ml/min) 10 1.0 1.2 1.6 10 5 Core Gas air 0 2- 40%,N 2 air air 0 2- 73%, Ar air (l/min) 0.8 0.7 0.6 1.5 0.9 1.5 gas pres- -sure 1) (mm Aq.) + 6 + 10 + 5 +12 +7 +1.2 Stability of start stable stable stable stable stable stable 1 Cost skin 2) (inner periphery) Superficial Segregation layer (V m) Rotindness of a hollow part _______good good good good good Deviation of Wall thickness good good good good 4 A A A A B B Ingot good good - good 0 Pressure of annular space formed directly beneath the overhang. The pressure i's indicated by rise or fall relative to the hydrostatic pressure of melt directly beneath the overhang ( mm Aq.) Cast skin on an inner peripheral surface of ingots. A: Very smooth and good over the entire periphery. B: Good. Slight, periodically remelted skin. C: Bad. Strong, periodically remelted skin and crude sticking skin(longitunal) 36 T a b, 1 e ' 1 (2) Items Comparative Examples Nos. Apparatus Kinds of alloys Compara- Comparative tive Example 1 Example 2 AA 5052 AA5056 Outer diameter of ingot (mm) 250 250 Inner diameter of ingot (mm) 118 118 Casting speed (mm/min) 120 120 Core Ingot Lubricating oil (cc/min) castor oil castor oil 6 - Gas not not apply apply Gas 1) pressure (mm Aq.) not not _apply apply Stability of start Cast skin 2) (inner periphery) c Superficial Segregation layer ( WM) - Roundndss of a hollow part Deviation of Wall thickness 1 U nstable unstable c 450 1 rather poor rather _ poor 000 poor poor

Claims (1)

  1. - 37 C L A I M S
    1. A method for continuous casting a hollow ingot (15), comprising the steps of closing, at the casting start, a lower end of an annular space formed between a forcedly cooled tubular mold (1) and a core (16) by a movable bottom block (13), continuously pouring molten metal (19) into said annular space, holding the molten metal (9) in said annular space, cooling and solidifying the molten metal (9) by said tubular mold (1) and core (16), thereby forming the hollow ingot (15), and continuously displacing the movable bottom block (13) thereby withdrawing the hollow ingot (15) from the tubular mold (1) 1 characterized by introducing gas around an outer peripheral surface of the core (16), forming by said introduced gas an annular gap surrounding an inner peripheral surface of hollow metalic molten metal (9) held in the annular space, and applying a pressure of said annular gap onto said inner peripheral surface of the hollow molten metal (9). casting according to claim 1, the steps of covering, before pouring the molten metal into the annular space, the inner peripheral surface of the core (16) with refractory heat-insulative material (59) into contact with the molten metal, bringing said refractory heat-insulative material (59) with the molten metal (9) poured into said annular space at the casting start, encasing said refractory heat-insuldtive material (59) with metal solidified thereon, and withdrawing said encased refractory heat- insulative material (59) together with the hollow ingot (15) being withdrawn.
    3. A method for continuous casting according to claim 2, further comprising the steps of covering, before pouring the. molten metal into the annular space, at least either of the inner peripheral surface of the tubular mold (1) or the upper surface of the movable bottom block (13) with refractory heat-insulative material (70, 71), bringing said refractory heat-insulative material (70, 71) intocontact with the molten metal (9) poured into said annular space at the casting start, encasing said refractory heat-insulative material (70, 71) with metal solidified thereon, and withdrawing said encased 2. A method for continuous further comprising - 38 refractory heat-insulative materials (59., 70, 71) together with the hollow ingot (15) being withdrawn.
    4. A method for continuous casting according to claim 2 or 3, wherein said refractory heat-insulative material(s) (59, 70, 71) is provided with lugs (60) which are made of material resistant against erosion by said molten metal (9) and protrude beyond the inner surface of said material(s) (59, 70, 71), and, further said lugs (60) are encased with the metal solidified thereon and are withdrawn together with the hollow ingot (15).
    5. A method for continuous casting according to claim 2 or 3, wherein said refractory heat-insulative material(s) (59, 70, 71) is provided with holes (62, 63) therethrough and, further said holow ingot is withdrawn after solidification of metal in said holes (62, 63).
    6. A method for continuous casting according to claim anyone of claims 2 through 4, wherein said refractory heat-insulative material(s) (59, 70) covering the tubular mold (1) and core (16) is provided with grooves (61) on an upper edge thereof, further said holow ingot is withdrawn after solidification of metal in said grooves (61).
    7. A method for continuous casting according to claim 3, wherein said refractory heat-insulative material (71) covers a part of the upper surface of the movable bottom block (13).
    8. A method for continuous casting according to claim 7, wherein the uncovered, upper surface of the movable bottom block (13) is provided with a projection (82) made of material which is resistant against erosion by the molten metal (9), and, further, said projection (82) is encased with metal solidified thereon and is withdrawn together with the hollow ingot (15).
    9. A method for continuous casting according to any one of claims 1 through 8, wherein said gas pressure is determined in the range of a hydrostatic pressure of molten metal at the level of the position of said annular gap, at the highest, and, at the lowest, a pressure for essentially decreasing a contact area of the molten metal (9) with the inner peripheral surface of the core (16).
    10. A continous casting apparatus of a hollow ingot comprising a forcedly cooled tubular mold (1) and a core (16) which is held inside said tubular mold (1), characterized by further comprising: an overhang (24) which is formed on an outer peripheral surface of the core (16) in contact with molten metal (9) during casting and which uniformly protrudes outwards the core (16); and apertures which end on the outer peripheral surface of core (16) adjacently to the overhang (24) and which are communicated with a gas source.
    11. A continuous casting apparatus according to claim 10, wherein said overhang (24) is formed by a protruding part of the outer peripheral surface of the core (16).
    12. A continous casting apparatus according to claim 11, wherein a refractory heat-insulative body (18) in a columnar or tubular form is located on the core (16), and said overhang (14) is formed by an outer peripheral part of said refractory heat-insulative body (18) which part protrudes outwards beyond the outer peripheral surface of the core (16).
    13. A continuous casting apparatus according to claim 11, wherein said overhang (14) is formed by a protruding part of non-forcedly cooled core (16) and is positioned directly above an outer peripheral position of the core (16) where the solidified shell starts to form.
    14. A continuous casting apparatus according to claim 10, wherein said apertures are slits formed between the upper surface of the core (16) and the lower surface of the refractory heat-insulative body (18).
    15. A continuous casting apparatus according to claim 10, wherein said core (16) comprises, around the outer peripheral surface, a porous refractory material (2a), and further said apertures are pores of said porous refractory material (2a).
    16. A continuous casting apparatus according to anyone of claims 10 through 15, wherein said movable bottom block (114) is connected to a liftable table (122) via a carrier (120) which comprises legs (125) for carrying the movable bottom block (114) and at least one slope means (117, 118) for flowing down therealong a cooling water (21) of the core (16) and molten metal (9) leaked through the inner peripheral surface of the hollow ingot (15), and, fu rther said legs (125) are - 40 connected to a first part of said liftable.table (122) by the ends thereof (125) and carry said movable bottom block at parts of their lower ends, and, said slope means (117) are located on a second part of the liftable table (122) inside the legs (125), thereby directing the slope surface(s) (117a, 117b) toward the bottom of the core (16).
    lower (114) Publahed 1290 atThe PatentOMes. State House. 867 t F4h Holturri.1cadon WC1R 4TP. Further copies maybe obtLmedftlom The Patent OMcs. Sales Branch. St Mary Cray. Orpingwn. K2n,. BEL5, 3RD. Printed by multiplex rAcbmquos ltd. St Mary Cray, Kent. Coix 187
GB8821553A 1988-09-14 1988-09-14 Method for continuous casting a hollow metallic ingot and apparatus therefor Expired - Fee Related GB2222792B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU22208/88A AU619759B2 (en) 1988-09-14 1988-09-14 Method for continuous casting a hollow metallic ingot and apparatus therefor
GB8821553A GB2222792B (en) 1988-09-14 1988-09-14 Method for continuous casting a hollow metallic ingot and apparatus therefor
CA000578061A CA1324478C (en) 1988-09-14 1988-09-21 Method for continuous casting a hollow metallic ingot and apparatus therefor
DE3832306A DE3832306C2 (en) 1988-09-14 1988-09-23 Method and device for continuous casting of hollow metal blocks

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Application Number Priority Date Filing Date Title
GB8821553A GB2222792B (en) 1988-09-14 1988-09-14 Method for continuous casting a hollow metallic ingot and apparatus therefor
CA000578061A CA1324478C (en) 1988-09-14 1988-09-21 Method for continuous casting a hollow metallic ingot and apparatus therefor

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GB8821553D0 GB8821553D0 (en) 1988-10-12
GB2222792A true GB2222792A (en) 1990-03-21
GB2222792B GB2222792B (en) 1993-01-20

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WO2007062476A1 (en) * 2005-11-30 2007-06-07 Cast Centre Pty Ltd A gas and lubricant delivery apparatus
EP2135693A3 (en) * 2008-06-06 2010-05-26 Ambros Schmelzer & Sohn GmbH & Co. KG Filter element and method for manufacturing a filter element

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DE19712326A1 (en) * 1997-03-25 1998-10-01 Hans Schauff Fahrradfabrik Bicycle frame
DE19918229C2 (en) * 1999-04-22 2002-07-18 Daimler Chrysler Ag Method of manufacturing blanks for cylinder liners
DE19918228C2 (en) * 1999-04-22 2002-08-14 Daimler Chrysler Ag Method of manufacturing blanks for cylinder liners
RU2754336C2 (en) * 2019-10-07 2021-09-01 Александр Викторович Михалёв Method for continuous casting of hollow bills and a device for its use

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JPS5310530B1 (en) * 1971-04-09 1978-04-14
DE2321064C3 (en) * 1973-04-26 1978-06-22 Mannesmann Ag, 4000 Duesseldorf Hollow mandrel for the continuous casting of metallic tubes
JPS5315222A (en) * 1976-07-29 1978-02-10 Showa Denko Kk Method and device for semiicontinuously casting metal
CA1082875A (en) * 1976-07-29 1980-08-05 Ryota Mitamura Process and apparatus for direct chill casting of metals
US4126175A (en) * 1977-02-14 1978-11-21 Getselev Zinovy N Electromagnetic mould for the continuous and semicontinuous casting of hollow ingots
JPS61135452A (en) * 1984-12-06 1986-06-23 Nippon Light Metal Co Ltd Continuous casting device of hollow billet
DE3533517A1 (en) * 1985-09-20 1987-04-02 Vaw Ver Aluminium Werke Ag METHOD AND DEVICE FOR CONTINUOUS CASTING
US4693298A (en) * 1986-12-08 1987-09-15 Wagstaff Engineering, Inc. Means and technique for casting metals at a controlled direct cooling rate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007062476A1 (en) * 2005-11-30 2007-06-07 Cast Centre Pty Ltd A gas and lubricant delivery apparatus
EP2135693A3 (en) * 2008-06-06 2010-05-26 Ambros Schmelzer & Sohn GmbH & Co. KG Filter element and method for manufacturing a filter element

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GB2222792B (en) 1993-01-20
AU619759B2 (en) 1992-02-06
DE3832306A1 (en) 1990-03-29
AU2220888A (en) 1990-06-21
GB8821553D0 (en) 1988-10-12
CA1324478C (en) 1993-11-23
DE3832306C2 (en) 2000-04-06

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