EP0612276A1 - Heat treatment of metal castings and in-furnace sand reclamation - Google Patents
Heat treatment of metal castings and in-furnace sand reclamationInfo
- Publication number
- EP0612276A1 EP0612276A1 EP93904665A EP93904665A EP0612276A1 EP 0612276 A1 EP0612276 A1 EP 0612276A1 EP 93904665 A EP93904665 A EP 93904665A EP 93904665 A EP93904665 A EP 93904665A EP 0612276 A1 EP0612276 A1 EP 0612276A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sand
- furnace
- fluidizer
- hopper
- casting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004576 sand Substances 0.000 title claims abstract description 207
- 238000010438 heat treatment Methods 0.000 title claims abstract description 14
- 238000005058 metal casting Methods 0.000 title description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 52
- 238000005266 casting Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000002485 combustion reaction Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 14
- 230000001706 oxygenating effect Effects 0.000 abstract description 2
- 238000005243 fluidization Methods 0.000 description 35
- 238000005299 abrasion Methods 0.000 description 29
- 230000000153 supplemental effect Effects 0.000 description 16
- 239000011162 core material Substances 0.000 description 15
- 239000000523 sample Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- 238000004891 communication Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000746 Structural steel Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C5/00—Machines or devices specially designed for dressing or handling the mould material so far as specially adapted for that purpose
- B22C5/08—Machines or devices specially designed for dressing or handling the mould material so far as specially adapted for that purpose by sprinkling, cooling, or drying
- B22C5/085—Cooling or drying the sand together with the castings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
- B22D29/001—Removing cores
- B22D29/003—Removing cores using heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D31/00—Cutting-off surplus material, e.g. gates; Cleaning and working on castings
- B22D31/002—Cleaning, working on castings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/08—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of toothed articles, e.g. gear wheels; of cam discs
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
- C21D1/53—Heating in fluidised beds
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/06—Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
- B22F3/164—Partial deformation or calibration
- B22F2003/166—Surface calibration, blasting, burnishing, sizing, coining
Definitions
- the present invention relates generally to the field of heat treating metal castings and the field of reclaiming sand from sand cores and sand molds used to make metal castings.
- prior art methods and apparatus require that two or three distinctly separate steps be taken in order to heat treat a metal casting formed by a permanent mold or sand mold with a sand core, and reclaim sufficiently pure sand from the sand mold or sand core.
- the present invention allows for heat treating and reclamation of sufficiently pure sand in a single step.
- Molds and cores are used to displace molten material so that when the molten material is solidified, a casting is formed that reflects the features of the mold and core. Molds have the exterior features of the casting formed on the interior walls of the mold and cores have the interior features of the casting formed on the exterior surface of the core.
- the cores are typically made from sand whereas the molds are sometimes made from sand.
- Sand molds and cores are typically pre-molded from a mixture of sand and a combustible binder. For simplicity, sand molds and sand cores are referred to hereafter as simply sand cores.
- the first step separates portions of sand core from the casting.
- the sand core is typically separated from the casting by one or a combination of means. For example, sand may be chiseled away from the casting or the casting may be physically shaken to break-up the sand core and remove the sand.
- the second and third steps are carried out. In this typical, three-step prior art, the order in which the second and third steps are taken is not important, since the sand has already been separated from the casting.
- the second step consists of heat treating the casting.
- the casting is typically heat treated if it is desirable to strengthen or harden the casting.
- the third step consists of purifying the sand that was separated from the casting.
- the purification processes is typically carried out by one or a combination of means. These may include burning the binder that coats the sand, abrading the sand, and passing portions of the sand through screens. It is important that the reclaimed sand be sufficiently pure in order for it to be properly reused in the construction of new sand cores. It is also helpful if the reclaimed sand is rounded, at least to some degree, so as to assist in the casting of smooth surfaces and to assist in good bonding of the sand grains which causes strong cores. Therefore, portions of sand may be re-subjected to reclaiming processes until sufficiently pure sand is reclaimed.
- the purity of the reclaimed sand can be measured in terms of the quantity of unburned binder. The less unburned binder, the more pure the sand. While seeking increased purity, some sand is reduced to "fines". Fines is the term used for sand particles smaller than a specified size. Fines are so small that they require excessive amounts of binder.
- 07/705,626 ejects sand from the furnace in a sufficiently pure state for some applications; but, that system is not capable of combusting a sufficient amount of binder (or otherwise processing the sand core) so as to render sand that is sufficiently pure for certain other applications. Also, that system does not make provisions for varying the characteristics of the reclaimed sand; no selective control over sand roundness, amount of fines, or amount of unburned binder in the reclaimed sand is possible. Therefore, the sand reclaimed using the method and apparatus disclosed in application Serial No. 07/705,626 may require further processing in order to obtain sand that is sufficiently pure for certain applications or sand that has certain characteristics.
- previous sand reclaiming systems are inherently inefficient in that they require at least a two step process, carried out in two separate venues by separate, specialized equipment, in order to heat treat a metal casting formed by a sand core and reclaim sufficiently pure sand from the sand core.
- the present invention provides an improved method and apparatus for heat treating metal castings that are manufactured using sand cores and for reclaiming sand from the sand cores. More specifically, the present invention provides an improved method and apparatus for collecting sand within a heat treating furnace, purifying the sand, and ejecting the sand from the furnace. The present invention can reclaim sand that is more pure than that typically extracted from heat treating furnaces. The method and apparatus of the present invention also allows for selective control over the amount of binder and fines in the sand ejected from the furnace.
- the preferred embodiment of the present invention includes, associated with a furnace, apparatus or agitating sand which has been collected within Lue furnace.
- this agitation apparatus utilizes pressurized air to accomplish the agitating function through a process of "fluidization", and shall be referred to herein as a fluidizer.
- This fluidization process passes air, from a pressurized source, through sand collected in the furnace causing portions of the sand to be suspended and act like a turbulent fluid.
- the fluidizer in conjunction with other components in the furnace, causes the binder portion of sand cores to sufficiently combust within the furnace so that sufficiently pure sand is reclaimed.
- the sand cores, from which binder is combusted are attached to the castings that are transported into the furnace.
- a preferred furnace embodiment, and some of the elements within the furnace are disclosed in application Serial No.
- the fluidizer of the preferred embodiment of the present invention causes the fluidization of sand that has collected within the furnace hopper.
- the fluidizing causes portions of sand to abrade against one another, and in at least one embodiment, to also abrade against a metal target, in a manner that exposes the binder.
- the exposed binder then combusts. The process is repeated until a sufficient amount of binder has been combusted to satisfy the user as to the purity of the sand.
- the fluidizer adds oxygen to the furnace hopper so as to promote binder combustion.
- the fluidizer is supplied with preheated air from a secondary heat source so as to further promote binder combustion.
- the air of the fluidizer is not pre-heated.
- multiple fluidizers are employed, and, in such embodiment, appropriate fluidizer embodiments are chosen and selectively placed along a multiple zoned furnace.
- the present invention further includes methods and apparatus for discharging reclaimed sand from the furnace.
- this discharging is controlled so as to control the volume of sand contained in the furnace.
- An alternate embodiment of the present invention includes a supplemental sand reclamation unit (the
- the supplemental sand reclamation unit which functions in conjunction with the furnace heat source and in conjunction with the fluidizer and other components in the furnace, provides supplemental reclamation of sand previously reclaimed from casting cores. For example, sand collected from prior art shakers and sand discharged from the troughs of the furnace of serial number 07/705,626 is reprocessed by the supplemental sand reclamation unit.
- the supplemental sand reclamation unit includes a bin that is outside of the furnace. A tube is connected to a bin outlet and passes into the furnace. The tube passes, within the furnace, in close proximity to furnace heaters and terminates toward the furnace hopper.
- an object of the present invention to provide an improved method and apparatus for heat treating castings, with sand core material attached thereto, and reclaiming sand from the sand core material.
- Another object of the present invention is to provide an improved method and apparatus for removing sand core material from a casting and reclaiming sand from the sand core material.
- Another object of the present invention is to provide a method and apparatus for reclaiming, within a furnace, sand from portions of sand core that are separated from castings within the furnace.
- Yet another object of the present invention is to provide a method and apparatus for controlling the amount of time that sand core material is exposed to sand reclamation processing within a furnace so that the characteristics of the reclaimed sand can be controlled.
- Fig. 1 is a cut-away view of a combination heat treating furnace and in-furnace sand reclamation unit, in accordance with the preferred embodiment of the present invention.
- Fig. 2 is a cut-away view of selected elements of the sand reclamation unit of Fig. 1.
- Fig. 3 is a cut-away top view of selected elements of the sand reclamation unit of Fig. 1, showing some of the elements that are cut-away in Fig. 1.
- Fig. 4 is a cut-away top view of selected elements of the sand reclamation unit of Fig. 1, showing some of the elements that are cut-away in Fig. 1.
- Fig. 5 is a cut-away side view of the discharge valve assembly of Fig. 1.
- Fig. 6 is a cut-away top view of a portion of an in-furnace sand reclamation unit, in accordance with an alternate, preferred embodiment of the present invention.
- Fig. 7 is a cut-away side view of a portion of the apparatus of Fig. 6.
- Fig. 8 is a cross-sectional view of the fluidizer conduit of Fig. 6, taken along line 8-8 of Fig. 7.
- Fig. 9 is a side view of an in-furnace sand reclamation unit, in accordance with an alternate, preferred embodiment of the present invention.
- Fig. 10 is a detailed perspective view of the fluidizing ring of Fig. 9.
- Fig. 11 is a cross-sectional view of the fluidizing ring of Fig 9, taken along line 11-11 of Fig. 10.
- Fig. 12 is a cross-sectional view of the fluidizing ring of Fig 9, taken along line 12-12 of Fig. 11.
- Fig. 13 is a cut-away view of a portion of an in- furnace sand reclamation unit, in accordance with an alternate embodiment of the present invention.
- Fig. 14 is a cut-away view of a multi-zone embodiment of the heat treating furnace and in-furnace sand reclamation system, in accordance with the present invention.
- Fig. 15 is an isolated side view of a supplemental sand reclamation unit which is part of an alternate embodiment of the present invention.
- Fig. 16 is a cut-away, side view of the supplemental sand reclamation unit of Fig. 15 mounted on top of the combination heat treating furnace and in- furnace sand reclamation unit.
- Fig. 17 is a cut-away view of the reclaimer hopper of Fig. 15.
- the first part introduces components and describes their orientation and interconnections.
- the second part describes the operation of the components and provides some examples of acceptable components.
- Fig. 1 shows a partially cut-away view of a combination heat treating furnace 19 and in-furnace sand reclamation unit 20, in accordance with the preferred embodiment of the present invention.
- the in-furnace sand reclamation unit 20 includes a hopper 30 which has a hopper wall 31 and defines a hopper inlet 33 and a hopper outlet 35. A portion of the hopper wall 31 and other elements are cut-away in Fig. 1 so that elements shown can be clearly seen.
- the in-furnace sand reclamation unit 20 further includes a fluidizer 40, guidance tube 80, abrasion disk 90 and a discharge valve assembly 100.
- the fluidizer 40 is shown passing through the hopper wall 31.
- the guidance tube 80 is shown oriented above the fluidizer within the hopper 30.
- the abrasion disk 90 is shown oriented above the guidance tube 80 within the hopper 30.
- the discharge valve assembly 100 is shown connected to the hopper outlet 35.
- the hopper 30 of the in-furnace sand reclamation unit 20 doubles as the hopper 30 of the heat treating furnace 19.
- An appropriate heat treating furnace 19 is disclosed in application Serial No. 07/705,626.
- the specification of U.S. patent application Serial No. 07/705,626 is hereby incorporated herein by reference.
- the discharge valve assembly 100 provides a path to the outside of the furnace.
- Fig. 2 which is a cut-away side view of selected elements of Fig. 1, shows the fluidizer 40 of the preferred embodiment of the present invention, in greater detail.
- Sand 25 is also shown, in representative form, collected at the hopper outlet 35.
- the fluidizer 40 is seen as including a fluidizer conduit 41; the fluidizer conduit 41 has a fluidizing end 42 that is within the hopper 30 and a source end 43 that is outside of the hopper 30. A portion of the fluidizer conduit 41 has been cut-away to expose a conduit interior 44 which is defined by the fluidizing conduit 41.
- the source end 43 of the fluidizer conduit 41 is sealed by an end plate 47.
- the end plate 47 is attached to the source end 43 in a manner that would be understood by those reasonably skilled in the industry; for example, by welding.
- a portion of the end plate 47 is cut away in Fig. 2, to fully expose a heater 60.
- the heater 60 is secured through the end plate 47 in a manner that facilitates removal for repair or replacement with a different type of heater.
- the heater 60 has an exhaust end 61 located within the conduit interior 44 and an intake end 62 outside of the fluidizer conduit 41. Pressurized air is supplied into the intake end 62 of the heater 60 through an air intake 65.
- the heater 60 is a high pressure gas burner.
- the heater 60 consists of an electric heating element. Other heater types are acceptable.
- a signal generating pressure gauge 70 is connected to the fluidizer conduit 41 by a gauge conduit 71.
- the signal generating pressure gauge 70 is in communication with the conduit interior 44 and can sense the pressure within the fluidizer conduit 41.
- a signal adjuster 74 is associated with the signal generating pressure gauge 70.
- the signal generating pressure gauge 70 is connected to an electric power supply by a gauge power cable 72.
- the signal generating pressure gauge 70 is connected by a signal cable 73 to the discharge valve assembly 100, which is not shown in Fig. 2.
- the fluidizer end 42 of the fluidizer conduit 41 is turned upward in Fig. 2 toward a the guidance tube 80 and the abrasion disk 90.
- the guidance tube 80 part of which is cut away in Fig. 2, has a tube wall 81 and defines a tube passage 82.
- the abrasion disk 90 part of which is cut away in Fig. 2, has disk back 92 and a concave disk face 91.
- Fig. 3 is a top view of the apparatus of Fig. 2 in greater detail and with the abrasion disk 90 removed.
- the guidance tube 80 is connected to tube support rods 85a,b which are connected to the hopper wall 31. These connections are made in a manner as would be understood by those reasonably skilled in the industry; for example, by welding or bolting.
- the guidance tube 80 is positioned such that the guidance tube 80 is oriented above the fluidizer end 42 of the fluidizer conduit 41 and the tube passage 82 is in-line with the conduit interior 44 at the fluidizer end 42.
- Fig. 4 is a top view of the apparatus of Fig. 2 in greater detail. In Fig.
- the disk face 91 of the abrasion disk 90 is oriented toward the fluidizer end 42 and is therefore not seen.
- the abrasion disk 90 is connected to disk support cables 95 which are attached to the hopper wall 31.
- the cables 95 have a disk end 96, a hook end 97, and a turnbuckle 98 disposed between the disk end 96 and the hook end 97.
- the disk ends 96 of the cables 95 are attached to the abrasion disk 90 in a manner that would be understood by those reasonably skilled in the industry; for example, by welding or bolting.
- the hook end 97 of each cable 95 is attached to the inner hopper wall 31 by an eyehook 99; the hook ends 97 are hooked to eyehooks 99.
- the eyehooks 99 are connected to the hopper wall 31 in a manner that would be understood by those reasonably skilled in the industry; for example, by welding or bolting. There are a plurality of eyehooks 99, each of which is oriented so that the height of the abrasion disk 90 above the fluidizer end 42 is capable of being adjusted, as will be explained below.
- the fluidizer end 42, conduit interior 44, and guidance tube 80 are not seen in Fig. 4 because they are concealed by the abrasion disk 90.
- Fig. 5 is a cut-away side view of the discharge valve assembly shown in Fig. 1.
- the discharge valve assembly 100 includes a double dump valve 110 and a pneumatic valve operator 130.
- the double dump valve 110 has a valve inlet 111 and a valve outlet 112.
- the valve inlet 111 is connected to the hopper outlet 35 (see Fig. 1) in a manner that would be understood by those reasonably skilled in the industry; for example, by welding or bolting.
- the valve outlet 112 is located outside of the heat treating furnace 19 such that the double dump valve 110 provides a path from within the hopper 30 to the outside of the furnace 19.
- a portion of the double dump valve 110 is cut away in Fig. 5 to expose a first disk 116, a second disk 117, a first seat 118, and a second seat 119.
- the pneumatic valve operator 130 is connected to the double dump valve 110, in a manner that is understood by those reasonably skilled in the art, such that the pneumatic valve operator 130 controls the operation of the double dump valve 110.
- the pneumatic valve operator 130 is connected to a pneumatic supply line 131 and the signal cable 73.
- the pneumatic valve operator 130 is replaced with an electric, motorized valve operator; hydraulic valve operator; or some other type of valve operator.
- Fig. 6 and Fig. 7 show an alternate, preferred embodiment of the present invention.
- Fig. 6 is a cut ⁇ away top view of portions of the present invention in accordance with the alternate embodiment.
- This alternate embodiment does not include the guidance tube 80 or abrasion disk 90.
- This alternate embodiment does include a fluidizer 40' which is somewhat similar to the fluidizer 40 of the preferred embodiment.
- the fluidizer 40* has a fluidizer conduit 41' that splits into three fluidizer conduits 41'a,b,c, each of which pass through the hopper wall 31.
- the fluidizer conduits 41'a,b,c originate from a conduit header 55.
- the conduit header 55 originates from the source end 43 of the fluidizer conduit 41' .
- the fluidizer ends 43'a,b,c are sealed in a manner that would be understood by those reasonably skilled in the industry; for example, with a plug 50.
- Fig. 7 which is a side view of the fluidizer 40' showing a portion of the hopper 30, each fluidizer conduit 41'a,b,c defines a plurality of fluidizing holes 51 that are oriented toward the hopper outlet 35.
- FIG. 8 is a cross-sectional view taken along line 8 - 8 in Fig. 7; only one fluidizer conduit 41'a is shown for simplicity; the other conduits 41'b,c being similarly constructed.
- the fluidizing holes are in communication with the conduit interior 44'.
- the fluidizing holes 51 are spaced linearly and radially along the portion of the fluidizer conduit 41'a that faces the hopper outlet 35.
- the angle between the center-lines 52 defined by two fluidizing holes 51 that are radially positioned with respect to one another is ninety degrees.
- the fluidizing holes 51 are spaced in a different manner.
- FIG. 6-8 Another alternate embodiment of the present invention, which is not shown, is similar to the previously disclosed alternate embodiment of Figs. 6-8, except that the fluidizer conduit 40 splits into six fluidizer conduits. Three of the six fluidizer conduits penetrate one furnace hopper 30 and the other three of the six fluidizer conduits penetrate a different furnace hopper 30. Actually, there are a variety of alternate embodiments of the present invention that are variations upon those just disclosed. Although not shown in Figs. 6 and 7, the signal generating pressure gauge 70, with all of its associated elements, is included in these alternate embodiments of the present invention.
- Fig. 9 shows an alternate, preferred embodiment of the present invention which does not include the guidance tube 80 or the abrasion disk 90.
- a fluidizing ring 140 is disposed between the hopper outlet 35 and the valve inlet 111.
- the fluidizing ring 140 is connected to the hopper outlet 35 and the valve inlet 111 in a manner that would be understood by those reasonably skilled in the industry; for example, by welding or bolting.
- a fluidizer conduit 41' ' is also shown in Fig. 9 .
- the fluidizer conduit 41' ' defines a conduit interior 44 ' ' (not shown) .
- the fluidizer conduit 41' ' has a fluidizing end 42" ', which is connected to the fluidizing ring 140, and a source end 43' ', into which pressurized air is supplied.
- Fig. 10 is a detailed perspective view of the fluidizing ring 140 of Fig 9.
- the fluidizing ring 140 includes a hollow ring frame 141 which defines a ring interior 142 (see Fig. 11).
- the fluidizing ring 140 bounds an open area 145 that is in communication with the ring interior 142 by way of a plurality of fluidizing holes 146 that are defined by the ring frame
- the ring frame 141 further defines a conduit connection hole 147.
- the ring frame 141 is connected at the conduit connector hole 147 to the fluidizing end 42' ' of the fluidizer conduit 41' ' such that the conduit interior 44' ' is in communication with the ring interior 142. This connection is made in a manner that would be understood by those reasonably skilled in the industry; for example, by welding.
- Fig. 11 is a cross-sectional view taken along line 11 - 11 in Fig. 10.
- Fig. 11 shows the ring interior
- Fig. 12 is a cross sectional view taken along line 12 - 12 in Fig. 11.
- Fig 12 shows one of the plurality of fluidizing holes 146 defined by the ring frame 141.
- the fluidizing holes 146 are angled steeply enough so that portions of sand core which pass through the open area 145 defined by the ring frame 141 cannot easily migrate up, through the fluidizing holes 146, into the ring interior 142.
- no signal generating pressure gauge 70 is included.
- this alternate embodiment of the present invention includes signal generating sensors 170a,b,c that are mounted within the hopper 30, to the hopper wall 31.
- the sensors 170a,b,c are mounted such that they detect a predetermined level of sand core in the hopper 30.
- Each signal generating sensor 170a, ,c is connected by signal cable 73' to the discharge valve assembly 100 (not shown in Fig. 13).
- a selector 171 is associated with the signal generating sensors 170a,b,c.
- the signal generating sensors 170a,b,c are electric probes.
- Fig. 14 shows a multi-zone embodiment of the present invention, which includes a multi-sone furnace 211 employing several embodiments of the in-furnace sand reclamation unit 20.
- An example of furnace 211 is disclosed in application Serial No. 07/705,626. As disclosed, in Fig.
- the furnace 211 includes: a work chamber 215; zones 216A-H; furnace heaters 218; a pre-heat chamber 224; a furnace input door 225; a furnace upper end 226; a furnace discharge door 227; a furnace lower end 228; a roller hearth 234; rollers 236; baskets 240, for transporting castings; axial fans 244; a furnace top 245; screens 252; baffles 253; a sand conveyor 259; and a central collection bin 260.
- the furnace 211 further includes hoppers 30 and discharge valve assemblies 100.
- Zones 216A,B are equipped with the fluidizer 40 (see Figs. 1, 2, 3, and 4) guidance tube 80, and abrasion disk 60.
- the pre-heat chamber and Zone 216E are equipped with the fluidizer 40' (see Figs. 6, 7, and 8), and Zones 216F,G,H are equipped with the fluidizer 40' ' (see Figs. 9, 10, 11, and 12).
- Sand 25 is shown, in representative form, collected at the hopper outlet 35.
- Fig. 15 shows a supplemental sand reclamation unit 180 which is part of an alternate embodiment of the present invention.
- the supplemental sand reclaiming unit 180 includes a reclaimer hopper 181 which has a reclaimer inlet 182, a reclaimer outlet 183, and a reclaimer wall 184.
- the supplemental sand reclamation unit 180 further includes a discharger 190 that has a discharger inlet 191 and a discharger outlet 192.
- the discharger 190 is a screw auger.
- the discharger inlet 191 is connected to the hopper outlet 183 in a manner that would be understood by those reasonably skilled in the industry; for example, by welding or bolting.
- the supplemental sand reclamation unit 180 further includes a delivery tube 195 that defines a tube interior 199.
- the delivery tube 195 also has a tube inlet 196, a tube outlet 197, and an oxygen supply line 198 that is in communication with the tube interior 199.
- the tube inlet 196 is connected to the discharger outlet 192 in a manner that would be understood by those reasonably skilled in the industry; for example, by welding or bolting.
- Fig. 16 is a cut-away view of the supplemental sand reclamation unit 180 of Fig. 15 mounted on top of the combination heat treating furnace 19 and in-furnace sand reclamation unit 20 in accordance with an alternate embodiment of the present invention.
- the reclaimer hopper 181 and discharger 190 are located outside of the heat treating furnace 19.
- Fig. 17 is a cut-away view of the reclaimer hopper 181 of Fig. 15. A portion of the reclaimer wall 184 is cut-away to show a reclaimer interior 185 that is defined by the reclaimer wall 184. Included within the reclaimer interior 185 are heaters 186, oxygen suppliers 187 and a level indicator 188.
- the reclaimer hopper 181 also includes a recycle exhaust duct 189 that exhausts into the heat treating furnace 19 and a baghouse exhaust duct 198.
- Figs. 1, 2, 3, and 4 disclose the first, preferred embodiment of the present invention.
- the equipment and process that are at the heart of the first, preferred embodiment are referred to as "high temperature fluidization with a target".
- pressurized air is supplied through the air intake 65.
- Oxygenated and heated exhaust from the heater 60 discharges from the fluidizer end 42 of the fluidizer conduit 41.
- the oxygenated and heated exhaust fluidizes portions of sand core that are above the fluidizer end 42. That is, the exhaust passes up through the sand, causing the sand to be suspended and act like a turbulent fluid.
- the fluidization further propels portions of sand through the guidance tube passage 82 where the trajectory of the entrained portions of sand is oriented toward the disk face 91 of the abrasion disk
- the fluidizer 40 promotes combustion by providing a hot and oxygenated environment.
- the exposed binder combusts to promote purification of the sand reclaimed from the sand core. Since the "high temperature fluidization with a target" incorporates a variety of techniques to reclaim sand (which include, at least, fluidization, fluidization in combination with an abrasion disk, heating to promote combustion, and oxygenating to promote combustion) it has a relatively high capacity as compared the processes referred to below.
- Hot fluidization does not propel portions of sand core toward a target. However, “hot fluidization” is otherwise similar to “hot fluidization with a target”. Pressurized air is supplied through the air intake 65. Oxygenated and heated exhaust from the heater 60 discharges from the fluidizer holes 51. As the level of sand approaches the level of the fluidizing holes
- fluidization begins. Fluidization is promoted and enhanced by the placement and orientation of the fluidizing holes 51.
- the portions of sand that are fluidized abrade against each other. The abrasion caused by this process knocks away ash that is adhered to the sand. This exposes unburned binder and thus promotes binder combustion.
- the fluidizer 40' promotes combustion by providing a hot and oxygenated environment. Thus, the exposed binder combusts to promote purification of the sand reclaimed from the sand core. Since "hot fluidization" does not utilize a target, it does not typically cause as much abrasion as "hot fluidization with a target”.
- hot fluidization typically exposes less binder than and therefore causes less combustion than "hot fluidization with a target”. Therefore, “hot fluidization” typically has less capacity than "hot fluidization with a target”.
- hot fluidization with a target is used where relatively large portions of sand and sand core fall through the hopper inlet 33 and "hot fluidization” is used where relatively moderate portions of sand and sand core fall through the hopper inlet 33.
- Other alternate embodiments of the present invention one of which is shown in Figs. 9, 10, 11, and 12, are referred to as “cool fluidization”.
- Cool fluidization is somewhat similar to "hot fluidization” except that it does not incorporate heating.
- Pressurized air is supplied to the source end 43' ' of the fluidizer conduit 41' ' .
- the pressurized air passes into the ring interior 142 by way of the fluidizer end 42' ' of the fluidizer conduit 41' ' and the conduit connection hole 147.
- the pressurized air then escapes from the fluidizing ring 140 through the fluidizing holes 146.
- the portions of sand that are fluidized abrade against each other.
- the abrasion caused by this process knocks away ash that is adhered to the sand. This exposes unburned binder and thus promotes binder combustion.
- the fluidizer 40' ' promotes combustion by providing added oxygen to the environment (the heat necessary for combustion is provided by the heat treating furnace 19).
- the exposed binder combusts to promote purification of the sand reclaimed from the sand core. Since "cool fluidization” does not add heat to promote combustion, it does not typically cause as much combustion as "hot fluidization”.
- Cool fluidization typically has less capacity than “hot fluidization”.
- cool fluidization is used where relatively small portions of relatively clean sand fall through the hopper inlet 33.
- Cool fluidization in addition to reclaiming sand, cools portions of sand before they pass through the double dump valve 110. This protects the double dump valve 110 from heat related stress and strain and allows for the use of a less expensive double dump valve 110.
- the different embodiments of the present invention have different capacities. As specified in application Serial No. 07/705,626, different zones 216 (see Fig. 14) within a continuous- process furnace 211 have different capacities for loosening sand core from castings. Therefore, it is necessary to reclaim more sand in some zones 216 and less from others.
- higher capacity embodiments of the in-furnace sand reclamation unit 20 (for example Figs. 1 - 4) are employed in high capacity zones 216A,B; moderate capacity embodiments of the in-furnace sand reclamation unit 20 (for example Figs.
- the signal generating pressure gauge 70 and the equipment associated with it serves to provide positive control over the level, and therefore the volume, of sand that accumulates within the hopper 30 (refer to Figs. 2 and 9). As portions of sand continue to fall through the hopper inlet 33, the level of sand within the hopper 30 increases. As the level increases there is more resistance to the flow of air from the fluidizer end of the conduit 42 and the back-pressure in the fluidizer conduit 41 increases.
- the signal adjuster 74 associated with the signal generating pressure gauge 70 is set such that when a certain back ⁇ pressure is detected within the conduit interior 44 by the signal generating pressure gauge 70, a "high level" signal is generated.
- the pneumatic valve operator 140 receives the "high level" signal by way of the signal cable 73. While the pneumatic valve operator 140 receives the signal it operates the double dump valve 120.
- the double dump valve 120 is operated such that the first disk 126 and second disk 127 alternately move away from and then return to the first seat 118 and second seat 119, respectively. This operation is such that while the first disk 116 is not in contact with the first seat 118, the second disk 117 is in contact with the second seat 119, and visa-versa.
- back-pressure is maintained at the hopper outlet 35 such that fluidization is not disrupted.
- the double dump valve 110 is replaced with a star valve or screw auger, or another type of device that performs a discharging and a sealing function.
- signal generating sensors 170 mounted to the hopper wall 31 (see Fig. 13), serve to provide positive control over the level, and therefore the volume, of sand that accumulates within the hopper 30.
- the signal generating sensors 170 consist of electric capacitance probes.
- An electric capacitance probe is mounted to the hopper wall at each position that corresponds to a level at which it is desired to operate the double dump valve 110.
- the particular level at which the double dump valve will operate is established by operating the selector 171 which establishes which electric probe is controlling. As the level of sand increases and comes into contact with the controlling electric probe, a "high level" signal is generated.
- the pneumatic valve operator 140 receives the "high level" signal by way of the signal cable 73' .
- the pneumatic valve operator 140 receives the s_ 1 it operates the double dump valve 110 as is disclosed above.
- the characteristics of reclaimed sand are controlled by controlling the dwell time of portions of sand within the hopper 30. The longer the dwell time, the longer the amount of time that the portions of sand are fluidized. When portions of binder coated sand are fluidized for a relatively longer period of time, less binder is contained in the reclaimed sand but more fines are contained in the reclaimed sand.
- the dwell time is controlled by controlling the volume of sand that is allowed to accumulate in the hopper 30.
- the volume of sand that is allowed to accumulate in the hopper 30 is selected by adjusting the signal adjuster 74 in the one disclosed preferred embodiment of the present invention or by adjusting the selector 171 in the second disclosed embodiment of the present invention.
- a larger volume of sand accumulates in the hopper 30 when the signal adjuster 74 is adjusted so that the signal generating pressure gauge 70 emits a "high level” signal at a higher pressure.
- a smaller volume of sand accumulates in the hopper 30 when the signal adjuster 74 is adjusted so that the signal generating pressure gauge 70 emits a "high level” signal at a lower pressure.
- a larger or smaller volume of sand is allowed to accumulate in the hopper 30 by adjusting the selector 171 to select the signal generating sensor 170 that is mounted at the level that corresponds to the desired volume.
- the characteristics of the reclaimed sand are also controlled, in the preferred embodiment of the present invention, by adjusting the height of the abrasion disk 90 above the fluidizer end 42 of the fluidizer conduit 41.
- the height is adjusted by loosening the turnbuckles 98, unhooking the hook ends 97 from the eyehooks 99, hooking the hook ends 97 to the appropriate eyehooks 99, and tightening the turnbuckles 98.
- These components can be accessed by entering the hopper 30 through the furnace 19 or through trap doors in the hopper wall 31.
- the supplemental sand reclamation unit 180 is used, in conjunction with the fluidizer 40 and other components in the heat treating furnace 19, to further purify sand that has already been reclaimed by some other process, and to reclaim sand from portions of sand core initially reclaimed by another process.
- the portions of sand core and coated sand that are introduced into the supplemental sand reclamation unit 180 are not adhered to castings. For example only, if a core was accidently molded into the wrong shape such that it could not be used for casting, it could be crushed and the portions thereof could be introduced into the supplemental sand reclamation unit 180.
- Portions of sand core and coated sand are introduced into the supplemental sand reclamation unit 180 through the reclaimer inlet 182.
- the heaters 186 and oxygen suppliers 187 maintain an atmosphere within the reclaimer interior 185 that causes some of the binder associated with the introduced sand and portions sand core to combust such that sand is reclaimed within the reclaimer hopper 181.
- the reclaimed sand is transferred from the reclaimer hopper 181 to the delivery tube 195 by the discharger 190.
- the sand within the delivery tube 195 is drawn by gravity from the tube inlet 196 toward the tube outlet 197.
- the sand in the delivery tube 195 is heated due to the fact that the delivery tube 195 is in close proximity to u- tube furnace heaters 218' .
- the sand in the delivery tube 195 is also exposed to oxygen that is supplied through the oxygen supply line 198. Therefore, at least some exposed binder that passes through the delivery tube 195 is combusted. As sand passes from the tube outlet 197 it falls into the hopper 30 where it is further purified by fluidization, as is discussed above.
- the embodiments of the present invention can be constructed from a variety of materials and include a variety of components. The following is offered for example only.
- the hopper 30, guidance tube 80, and abrasion disk could be made out of various abrasion resistant alloys. More specifically, the hopper 30 and guidance tube 80 could be made out of 4130, 4140 or
- the 1020 steel, and the abrasion disk 90 could be made out of a cast high manganese alloy.
- the fluidizing ring 140 could be constructed of A36 structural steel square tubing.
- the high pressure burner, which serves as the heater 60 in one embodiment of the present invention, could be an Eclipse brand.
- the signal generating pressure gauge 70 could be a Dwyer brand photoelectric gauge.
- the electric capacitance probes, that serve as the signal generating sensors 170 in one embodiment of the present invention, and the level indicator 188 could be an Endress Hauser brand, LSC 1110 Series capacitance probe. A low voltage is applied to these probes, and when the probe comes into contact with some material (for example sand) current flows into the material and the probe senses the current flow.
- the double dump valve 110 could be a Ni-Hard and nickel chrome alloy high temperature double dump valve made by Plattco Corporation.
- the Fluidizer conduit 41 can be constructed from stainless steel.
- the heater 186 could be a National brand silicon carbide heating element.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Fluidized-Bed Combustion And Resonant Combustion (AREA)
- Crucibles And Fluidized-Bed Furnaces (AREA)
- Processing Of Solid Wastes (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Casting Devices For Molds (AREA)
- Paper (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US93019392A | 1992-08-13 | 1992-08-13 | |
US930193 | 1992-08-13 | ||
PCT/US1993/000722 WO1994004297A1 (en) | 1992-08-13 | 1993-01-27 | Heat treatment of metal castings and in-furnace sand reclamation |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0612276A1 true EP0612276A1 (en) | 1994-08-31 |
EP0612276A4 EP0612276A4 (en) | 1995-08-23 |
EP0612276B1 EP0612276B1 (en) | 1998-04-15 |
EP0612276B2 EP0612276B2 (en) | 2004-11-17 |
Family
ID=25459039
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93904665A Expired - Lifetime EP0612276B2 (en) | 1992-08-13 | 1993-01-27 | Heat treatment of metal castings and in-furnace sand reclamation |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0612276B2 (en) |
JP (2) | JP2849213B2 (en) |
KR (1) | KR100263975B1 (en) |
CN (1) | CN1090066C (en) |
AT (1) | ATE165030T1 (en) |
AU (1) | AU677774B2 (en) |
BR (1) | BR9305607A (en) |
CA (1) | CA2121047C (en) |
DE (1) | DE69318000T3 (en) |
ES (1) | ES2114039T5 (en) |
MX (1) | MX9302659A (en) |
TW (1) | TW213490B (en) |
WO (1) | WO1994004297A1 (en) |
Cited By (1)
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CN113333434A (en) * | 2021-05-13 | 2021-09-03 | 王春红 | Broken gathering machine of production magnetic material sand mould |
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US5439045A (en) * | 1994-01-19 | 1995-08-08 | Consolidated Engineering Company, Inc. | Method of heat treating metal castings, removing cores, and incinerating waste gasses |
DE4427586C1 (en) * | 1994-06-15 | 1995-07-20 | Johann Muehlbauer | Appts. for treating used foundry sand |
DE19530975B4 (en) * | 1995-08-23 | 2004-04-15 | Consolidated Engineering Co. | Furnace for removing molding sand from castings |
US6453982B1 (en) | 1996-12-20 | 2002-09-24 | General Kinematics Corporation | Sand cleaning apparatus |
US5901775A (en) * | 1996-12-20 | 1999-05-11 | General Kinematics Corporation | Two-stage heat treating decoring and sand reclamation system |
US5924473A (en) * | 1996-12-20 | 1999-07-20 | General Kinematics Corporation | Vibratory sand reclamation system |
JP2001287019A (en) * | 2000-03-31 | 2001-10-16 | Asahi Tec Corp | Method for heating cast material with core |
DE10352180B4 (en) * | 2003-11-05 | 2006-03-02 | Dihag Deutsche Giesserei- Und Industrie-Holding Ag | Casting process for the production of a casting |
DE102007008149A1 (en) | 2007-02-19 | 2008-08-21 | Ashland-Südchemie-Kernfest GmbH | Thermal regeneration of foundry sand |
CN102397984A (en) * | 2011-11-28 | 2012-04-04 | 芜湖火龙铸造有限公司 | Automatic feeding forming device |
WO2015032427A1 (en) | 2013-09-04 | 2015-03-12 | Nemak Dillingen Gmbh | Method for removing a cast part cast from a light metal melt from a casting mould |
DE102014110826A1 (en) | 2014-07-30 | 2016-02-04 | Fritz Winter Eisengiesserei Gmbh & Co. Kg | Method for casting castings |
CN105215263B (en) * | 2015-10-10 | 2017-12-19 | 中车长江车辆有限公司 | A kind of heating means and device for roughing sand |
CN106475512B (en) * | 2016-11-30 | 2018-09-18 | 扬州广润机械有限公司 | A kind of casting finished sand sand storage bin Pneumatic block clearing device and its application method |
CN110899159B (en) * | 2019-11-29 | 2021-03-19 | 含山县兴达球墨铸铁厂 | Casting die bottom plate casting gate clearance mechanism |
CN111531122A (en) * | 2020-05-13 | 2020-08-14 | 安徽华颂再生资源回收有限公司 | Powerful rubbing and grinding regenerator for waste molding sand |
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1993
- 1993-01-27 WO PCT/US1993/000722 patent/WO1994004297A1/en active IP Right Grant
- 1993-01-27 ES ES93904665T patent/ES2114039T5/en not_active Expired - Lifetime
- 1993-01-27 JP JP6506220A patent/JP2849213B2/en not_active Expired - Fee Related
- 1993-01-27 BR BR9305607A patent/BR9305607A/en not_active IP Right Cessation
- 1993-01-27 KR KR1019940701185A patent/KR100263975B1/en not_active IP Right Cessation
- 1993-01-27 CA CA002121047A patent/CA2121047C/en not_active Expired - Lifetime
- 1993-01-27 AU AU35946/93A patent/AU677774B2/en not_active Ceased
- 1993-01-27 DE DE69318000T patent/DE69318000T3/en not_active Expired - Lifetime
- 1993-01-27 AT AT93904665T patent/ATE165030T1/en not_active IP Right Cessation
- 1993-01-27 EP EP93904665A patent/EP0612276B2/en not_active Expired - Lifetime
- 1993-02-06 TW TW082100801A patent/TW213490B/en active
- 1993-05-06 MX MX9302659A patent/MX9302659A/en unknown
-
1994
- 1994-01-27 CN CN94102666A patent/CN1090066C/en not_active Expired - Lifetime
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1998
- 1998-09-02 JP JP10248866A patent/JPH11129055A/en active Pending
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Cited By (1)
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CN113333434A (en) * | 2021-05-13 | 2021-09-03 | 王春红 | Broken gathering machine of production magnetic material sand mould |
Also Published As
Publication number | Publication date |
---|---|
ES2114039T3 (en) | 1998-05-16 |
MX9302659A (en) | 1994-02-28 |
DE69318000T3 (en) | 2005-07-21 |
ATE165030T1 (en) | 1998-05-15 |
DE69318000T2 (en) | 1998-12-24 |
CA2121047C (en) | 1998-01-06 |
JP2849213B2 (en) | 1999-01-20 |
ES2114039T5 (en) | 2005-06-01 |
EP0612276A4 (en) | 1995-08-23 |
BR9305607A (en) | 1995-06-13 |
WO1994004297A1 (en) | 1994-03-03 |
EP0612276B1 (en) | 1998-04-15 |
JPH07506299A (en) | 1995-07-13 |
EP0612276B2 (en) | 2004-11-17 |
AU677774B2 (en) | 1997-05-08 |
DE69318000D1 (en) | 1998-05-20 |
KR100263975B1 (en) | 2000-09-01 |
CN1090066C (en) | 2002-09-04 |
TW213490B (en) | 1993-09-21 |
CN1097662A (en) | 1995-01-25 |
AU3594693A (en) | 1994-03-15 |
CA2121047A1 (en) | 1994-03-03 |
JPH11129055A (en) | 1999-05-18 |
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