EP0421039B1 - Lost foam pressure casting process for metal pieces - Google Patents

Lost foam pressure casting process for metal pieces Download PDF

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Publication number
EP0421039B1
EP0421039B1 EP89420446A EP89420446A EP0421039B1 EP 0421039 B1 EP0421039 B1 EP 0421039B1 EP 89420446 A EP89420446 A EP 89420446A EP 89420446 A EP89420446 A EP 89420446A EP 0421039 B1 EP0421039 B1 EP 0421039B1
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Prior art keywords
metal
mpa
pressure
mould
value
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German (de)
French (fr)
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EP0421039A1 (en
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Michel Garat
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Rio Tinto France SAS
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Aluminium Pechiney SA
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D18/00Pressure casting; Vacuum casting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C9/00Moulds or cores; Moulding processes
    • B22C9/02Sand moulds or like moulds for shaped castings
    • B22C9/04Use of lost patterns
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/09Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting by using pressure
    • B22D27/13Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting by using pressure making use of gas pressure

Definitions

  • the present invention relates to a lost foam and pressure molding process for aluminum and aluminum alloy parts according to the preamble of claim 1.
  • This request teaches that after filling the mold with the molten metal, that is to say when the model has been completely destroyed by the metal, that the vapors emitted by the foam have been evacuated, and preferably before as the solidification of the metal does not begin, an isostatic gas pressure is exerted on the whole of the mold and of the metal. This pressure is applied according to increasing values over time in order to avoid the phenomenon of watering and so that the maximum value is reached in less than 15 seconds.
  • the molded parts obtained have an increased compactness which results in an improvement in the mechanical characteristics, in particular in terms of resistance.
  • the document FR-A-2254387 describes a process for molding metals in which pressures between 2 and 25 MPa are applied, but this process applies to metals having a melting temperature above 1000 ° C. and n is not part of the lost foam molding.
  • the present invention which consists of a lost foam and pressure molding process for aluminum parts and its alloys, in which an organic foam model of the part to be molded is immersed in a mold whose walls are delimited. by a dry sand bath containing no bonding agent, the mold is filled with the metal in the liquid state which replaces the foam and gradually solidifies and an increasing isostatic gas pressure is applied simultaneously to the mold and the metal at the earliest at the end of filling, characterized in that, in order to increase the fatigue life of said parts, the pressure exerted rises to a value between 1.5 and 10 MPa, a value which is reached before the amount of solidified metal exceeds 90% by weight.
  • the invention consists in using pressures between 1.5 and 10 MPa and preferably between 5 and 10 MPa.
  • the pressurization can be carried out using a sealed box in which the mold is placed, said box being equipped with one or more pipes distributed suitably on its wall and connected to a source of pressurized gas.
  • the pressure is mainly used to accelerate the flow of liquid metal between the dendrites of the metal being solidified and the effect stops when the solid network has reached a certain development .
  • these low pressures allow the counterweight to act effectively to avoid the phenomenon of shrinkage due to the contraction of the metal during solidification.
  • Figure 1 attached is a micrograph of an alloy A-S7G03 molded according to the invention under a pressure of 7 MPa, then heat treated. This micrograph reveals the plastic deformation imposed on the dendritic network and which has the effect of filling the porosities, and illustrates well the forging effect to which the metal is subjected in this process.
  • This new pressure range is preferably applied before the quantity of solidified metal reaches 40% by weight so as to be able to act on the liquid flow.
  • the application of the pressure be made by progressive increase in particular at the start of solidification in order to avoid watering ", phenomenon which results from a transient imbalance between pressure exerted directly on the metal and the pressure exerted on the metal by means of the sand bath.
  • the bath causes a relatively large pressure drop in the transmission of pressure and this results, at the level of the metal in contact with the sand, a tendency of this pressure to drive the metal through the grains of sand and to cause a deformation of the molded part.
  • the invention can be illustrated using the following example of application: Cylindrical bodies with an outside diameter of 45mm, a wall thickness of 4mm, having adjacent ribs and bosses of 20x20x80mm were molded according to the prior process and that of the invention, that is to say applied inside the enclosure containing the mold and just before solidification begins, an isostatic gas pressure corresponding respectively to atmospheric pressure, 1 MPa, 5 MPa and 10 MPa.
  • the fatigue life F in MPA was measured from tests in rotary bending on a test piece machined at 107 cycles according to the staircase method. F is valid for both thick and thin areas, since it does not depend on the speed of solidification but on the porosity and therefore on the pressure applied.

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  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Powder Metallurgy (AREA)
  • Forging (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Measuring Fluid Pressure (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Mold Materials And Core Materials (AREA)
  • Continuous Casting (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to a lost foam pressure casting process for metal pieces. This process consists, after having filled the mould with metal in the liquid state and before the solidified fraction of metal exceeds 40% by weight, in applying an isostatic gaseous pressure over the entire mould/metal, of which the value is between 1.5 and 10 mPa. The invention applies to the production of pieces, particularly made from aluminium alloys, having improved mechanical characteristics and, in particular, better resistance to fatigue. <IMAGE>

Description

La présente invention est relative à un procédé de moulage à mousse perdue et sous pression de pièces en aluminium et en ses alliages suivant le préambule de la revendication 1.The present invention relates to a lost foam and pressure molding process for aluminum and aluminum alloy parts according to the preamble of claim 1.

Il est connu de l'homme de l'art, principalement par l'enseignement de l'USP n° 3157924, d'utiliser pour le moulage des modèles en mousse de polystyrène plongés dans un moule constitué par du sable sec ne contenant aucun agent de liaison. Dans un tel procédé, le métal à mouler, qui a été préalablement fondu, est amené par l'intermédiaire de canaux traversant le sable au contact du modèle et se substitue progressivement à ce dernier en le brûlant et en le transformant en vapeurs qui s'échappent entre les grains de sable.It is known to those skilled in the art, mainly from the teaching of USP No. 3157924, to use for molding models of polystyrene foam immersed in a mold consisting of dry sand containing no agent link. In such a process, the metal to be molded, which has been previously melted, is brought through channels passing through the sand in contact with the model and gradually replaces the latter by burning it and transforming it into vapors which escape between the grains of sand.

Cette technique s'est avérée séduisante à l'échelle industrielle, parce qu'elle évite la fabrication préalable, par compactage et agglomération de matériaux réfractaires pulvérulents, de moules rigides associés de façon plus ou moins compliquée à des noyaux par l'intermédiaire de canaux, et qu'elle permet une récupération facile des pièces moulées ainsi qu'un recyclage aisé des matériaux de moulage.
Cependant, cette technique est handicapée par deux facteurs :

  • la relative lenteur de la solidification qui favorise la formation de piqûres de gazage
  • la relative faiblesse des gradients thermiques qui peut causer une microretassure si le tracé de la pièce en rend le masselottage difficile.
This technique has proven to be attractive on an industrial scale, because it avoids the prior manufacture, by compacting and agglomeration of powdery refractory materials, of rigid molds associated in a more or less complicated way with cores via channels. , and that it allows easy recovery of the molded parts as well as easy recycling of the molding materials.
However, this technique is handicapped by two factors:
  • the relative slowness of solidification which promotes the formation of gassing pits
  • the relative weakness of the thermal gradients which can cause micro-back-up if the layout of the part makes its weighting difficult.

C'est dans le but d'éviter de tels inconvénients que la demanderesse avait mis au point un procédé de moulage à mousse perdue décrit dans le document EP-A-0274964, sur lequel le préambule de la revendication 1 est basé.It is with the aim of avoiding such drawbacks that the Applicant had developed a lost foam molding process described in document EP-A-0274964, on which the preamble of claim 1 is based.

Cette demande enseigne qu'après avoir rempli le moule avec le métal fondu, c'est-à-dire quand le modèle a été détruit complètement par le métal, que les vapeurs émises par la mousse ont été évacuées, et de préférence avant que la solidification du métal ne s'amorce, on exerce sur l'ensemble du moule et du métal une pression gazeuse isostatique. Cette pression est appliquée suivant des valeurs croissantes dans le temps afin d'éviter le phénomène d'abreuvage et de manière que la valeur maximum soit atteinte en moins de 15 secondes.This request teaches that after filling the mold with the molten metal, that is to say when the model has been completely destroyed by the metal, that the vapors emitted by the foam have been evacuated, and preferably before as the solidification of the metal does not begin, an isostatic gas pressure is exerted on the whole of the mold and of the metal. This pressure is applied according to increasing values over time in order to avoid the phenomenon of watering and so that the maximum value is reached in less than 15 seconds.

Dans ces conditions, les pièces moulées obtenues présentent une compacité accrue qui se traduit par une amélioration des caractéristiques mécaniques notamment au niveau de la résistance.Under these conditions, the molded parts obtained have an increased compactness which results in an improvement in the mechanical characteristics, in particular in terms of resistance.

Toutefois, la demanderesse a estimé dans cette demande, qu'il était préférable d'utiliser une pression maximum comprise entre 0,5 et 1,5 MPa et qu'il était superflu d'aller au-delà de cette dernière limite.However, the Applicant considered in this request that it was preferable to use a maximum pressure of between 0.5 and 1.5 MPa and that it was superfluous to go beyond this latter limit.

En fait, elle s'est aperçue après des recherches plus poussées que si on augmentait davantage la pression, on améliorait non seulement les caractéristiques mécaniques telles que la résistance à la rupture Rm, la limite élastique LE et l'allongement A, mais également la tenue à la fatigue F.In fact, it became apparent after further research that if the pressure were increased further, not only would the mechanical characteristics such as the tensile strength Rm, the elastic limit LE and the elongation A be improved, but also the fatigue resistance F.

Certes, le document FR-A-2254387 décrit un procédé pour mouler des métaux dans lequel on applique des pressions comprises entre 2 et 25 MPa mais, ce procédé s'applique à des métaux ayant une température de fusion supérieure à 1000°C et n'entre pas dans le cadre du moulage à mousse perdue.Certainly, the document FR-A-2254387 describes a process for molding metals in which pressures between 2 and 25 MPa are applied, but this process applies to metals having a melting temperature above 1000 ° C. and n is not part of the lost foam molding.

D'où la présente invention qui consiste en un procédé de moulage à mousse perdue et sous pression de pièces en aluminium et en ses alliages, dans lequel on plonge un modèle en mousse organique de la pièce à mouler dans un moule dont les parois sont délimitées par un bain de sable sec ne contenant aucun agent de liaison, on remplit le moule avec le métal à l'état liquide qui se substitue à la mousse et se solidifie progressivement et on applique une pression gazeuse isostatique croissante simultanément sur le moule et le métal au plus tôt à la fin du remplissage caractérisé en ce que, dans le but d'augmenter la tenue à la fatigue desdites pièces, la pression exercée s'élève jusqu'à une valeur comprise entre 1,5 et 10 MPa, valeur qui est atteinte avant que la quantité de métal solidifié dépasse 90% en poids.Hence the present invention which consists of a lost foam and pressure molding process for aluminum parts and its alloys, in which an organic foam model of the part to be molded is immersed in a mold whose walls are delimited. by a dry sand bath containing no bonding agent, the mold is filled with the metal in the liquid state which replaces the foam and gradually solidifies and an increasing isostatic gas pressure is applied simultaneously to the mold and the metal at the earliest at the end of filling, characterized in that, in order to increase the fatigue life of said parts, the pressure exerted rises to a value between 1.5 and 10 MPa, a value which is reached before the amount of solidified metal exceeds 90% by weight.

Ainsi, l'invention consiste à mettre en oeuvre des pressions comprises entre 1,5 et 10 MPa et de préférence entre 5 et 10 MPa.Thus, the invention consists in using pressures between 1.5 and 10 MPa and preferably between 5 and 10 MPa.

Comme dans le document EP-A-0274964, la mise sous pression peut être réalisée à l'aide d'un caisson étanche dans lequel on place le moule, ledit caisson étant équipé d'une ou de plusieurs tubulures réparties convenablement sur sa paroi et reliées à une source de gaz sous pression.As in document EP-A-0274964, the pressurization can be carried out using a sealed box in which the mold is placed, said box being equipped with one or more pipes distributed suitably on its wall and connected to a source of pressurized gas.

Dans la gamme de pression choisie, la demanderesse a constaté que les phénomènes qui se produisaient au cours de la mise sous pression étaient tout à fait différents de ceux de l'art antérieur.In the pressure range chosen, the Applicant has found that the phenomena which occurred during the pressurization were quite different from those of the prior art.

En effet, entre 0,5 et 1,5 MPa, la pression sert principalement à accélérer l'écoulement du métal liquide entre les dendrites du métal en cours de solidification et l'effet s'arrête quand le réseau solide a atteint un certain développement. C'est ainsi en particulier que ces basses pressions permettent à la masselotte d'agir avec efficacité pour éviter le phénomène de retassure dû à la contraction du métal en cours de solidification.Indeed, between 0.5 and 1.5 MPa, the pressure is mainly used to accelerate the flow of liquid metal between the dendrites of the metal being solidified and the effect stops when the solid network has reached a certain development . Thus, in particular, these low pressures allow the counterweight to act effectively to avoid the phenomenon of shrinkage due to the contraction of the metal during solidification.

Par contre, sous des pressions supérieures à 1,5 MPa et notamment au-delà de 5 MPa, à l'effet d'écoulement du métal liquide, qui demeure prépondérant en début de solidification, se substitue progressivement un effet de déformation à chaud du réseau de métal déjà solidifié, phénomène qui devient dominant puis exclusif lorsque le taux de solidification atteint des valeurs voisines de 50 à 70% suivant le type d'alliage coulé. L'emploi de pressions élevées réalise ainsi une sorte de forgeage isostatique s'appliquant à la totalité de la surface de la pièce moulée.On the other hand, under pressures greater than 1.5 MPa and in particular above 5 MPa, the flow effect of the liquid metal, which remains predominant at the start of solidification, gradually replaces a hot deformation effect of the already solidified metal network, a phenomenon which becomes dominant and then exclusive when the solidification rate reaches values close to 50 to 70% depending on the type of cast alloy. The use of high pressures thus achieves a kind of isostatic forging applying to the entire surface of the molded part.

De plus, on cherche à ce que la pression maximum appliquée soit atteinte avant que la quantité de métal solidifié ne dépasse 90% afin de pouvoir bénéficier à plein de l'effet de déformation.In addition, it is sought that the maximum pressure applied is reached before the quantity of solidified metal does not exceed 90% in order to be able to fully benefit from the deformation effect.

La figure 1 ci-jointe est une micrographie d'un alliage A-S7G03 moulé suivant l'invention sous une pression de 7 MPa, puis traité thermiquement. Cette micrographie révèle la déformation plastique imposée au réseau dendritique et qui a pour effet de combler les porosités, et illustre bien l'effet de forgeage auquel est soumis le métal dans ce procédé.Figure 1 attached is a micrograph of an alloy A-S7G03 molded according to the invention under a pressure of 7 MPa, then heat treated. This micrograph reveals the plastic deformation imposed on the dendritic network and which has the effect of filling the porosities, and illustrates well the forging effect to which the metal is subjected in this process.

Dans ces conditions on constate que les caractéristiques mécaniques des pièces sont notablement améliorées et en particulier la tenue à la fatigue. Des pressions supérieures à 10 MPa n'apportent que des améliorations très peu sensibles.Under these conditions, it can be seen that the mechanical characteristics of the parts are significantly improved, and in particular the resistance to fatigue. Pressures above 10 MPa bring only very insignificant improvements.

Cette nouvelle gamme de pression est appliquée de préférence avant que la quantité de métal solidifié n'atteigne 40% en poids de manière à pouvoir agir sur l'écoulement liquide.This new pressure range is preferably applied before the quantity of solidified metal reaches 40% by weight so as to be able to act on the liquid flow.

Comme dans le document EP-A-0274964, il est préférable que l'application de la pression se fasse par accroissement progressif notamment au début de la solidification afin d'éviter l'abreuvage", phénomène qui résulte d'un déséquilibre transitoire entre la pression exercée directement sur le métal et la pression exercée sur le métal par l'intermédiaire du bain de sable. En effet, le bain provoque une perte de charge relativement importante dans la transmission de la pression et il en résulte, au niveau du métal en contact avec le sable, une tendance de cette pression à chasser le métal à travers les grains de sable et à provoquer une déformation de la pièce moulée.As in document EP-A-0274964, it is preferable that the application of the pressure be made by progressive increase in particular at the start of solidification in order to avoid watering ", phenomenon which results from a transient imbalance between pressure exerted directly on the metal and the pressure exerted on the metal by means of the sand bath. In fact, the bath causes a relatively large pressure drop in the transmission of pressure and this results, at the level of the metal in contact with the sand, a tendency of this pressure to drive the metal through the grains of sand and to cause a deformation of the molded part.

L'invention peut être illustrée à l'aide de l'exemple d'application suivant :
Des corps cylindriques de diamètre extérieur 45mm, d'épaisseur de paroi 4mm, comportant des nervures adjacentes et des bossages de 20x20x80 mm ont été moulés suivant le procédé antérieur et celui de l'invention, c'est-à-dire qu'on a appliqué à l'intérieur de l'enceinte contenant le moule et juste avant que la solidification s'amorce, une pression de gaz isostatique correspondant respectivement à la pression atmosphérique, à 1 MPa, à 5 MPa et à 10 MPa.
The invention can be illustrated using the following example of application:
Cylindrical bodies with an outside diameter of 45mm, a wall thickness of 4mm, having adjacent ribs and bosses of 20x20x80mm were molded according to the prior process and that of the invention, that is to say applied inside the enclosure containing the mold and just before solidification begins, an isostatic gas pressure corresponding respectively to atmospheric pressure, 1 MPa, 5 MPa and 10 MPa.

Ces corps ont été réalisés à partir de deux types d'alliages à hautes caractéristiques mécaniques :

  • l'A-S7G03 de composition en poids %: Fe 0,20; Si 6,5-7,5; Cu 0,10; Zn 0,10; Mg 0,25-0,40; Mn 0,10; Ni 0,05; Pb 0,05; Sn 0,05; Ti 0,05-0,20; solde Al;
  • l'A-U5GT de composition : Fe 0,35; Si 0,20; Cu 4,20-5 00; Zn 0,10; Mg 0,15-0,35; Mn 0,10; Ni 0,05; Pb 0,05; Sn 0,05; Ti 0,05-0,30; solde Al.
These bodies were made from two types of alloys with high mechanical characteristics:
  • A-S7G03 of composition by weight%: Fe 0.20; If 6.5-7.5; Cu 0.10; Zn 0.10; 0.25-0.40 Mg; Mn 0.10; Ni 0.05; Pb 0.05; Sn 0.05; Ti 0.05-0.20; balance Al;
  • A-U5GT of composition: Fe 0.35; If 0.20; Cu 4.20-5 00; Zn 0.10; Mg 0.15-0.35; Mn 0.10; Ni 0.05; Pb 0.05; Sn 0.05; Ti 0.05-0.30; balance Al.

Les essais mécaniques effectués sur lesdits corps après des traitements thermiques normalisés Y23 pour l'A-S7G03 et Y24 pour l'A-U5GT ont permis de mesurer les caractéristiques suivantes en fonction des pressions appliquées.

  • Dans l'A-S7G03, l'indice de qualité Q en MPa qui correspond à la formule Q = R + 150 log A où R est la résistance en MPa et A l'allongement en % et ce à la fois sur les zones épaisses et minces des pièces.
  • dans l'A-U5GT, les limites élastiques LE en MPa, la résistance R en MPa et l'allongement A en % et ce également à la fois sur les zones épaisses et minces.
Mechanical tests carried out on said bodies after standardized heat treatments Y23 for the A-S7G03 and Y24 for the A-U5GT made it possible to measure the following characteristics as a function of the pressures applied.
  • In A-S7G03, the quality index Q in MPa which corresponds to the formula Q = R + 150 log A where R is the resistance in MPa and A the elongation in% and this both on thick areas and thin parts.
  • in the A-U5GT, the elastic limits LE in MPa, the resistance R in MPa and the elongation A in%, also on both thick and thin areas.

En outre, pour chacun des alliages et chacune des pressions appliquées, on a mesuré la tenue à la fatigue F en MPA à partir d'essais en flexion rotative sur éprouvette usinée à 10⁷ cycles suivant la méthode staircase. F est valable à la fois pour les zones épaisses et minces, car elle ne dépend pas de la vitesse de solidification mais de la porosité et par suite de la pression appliquée.In addition, for each of the alloys and each of the pressures applied, the fatigue life F in MPA was measured from tests in rotary bending on a test piece machined at 10⁷ cycles according to the staircase method. F is valid for both thick and thin areas, since it does not depend on the speed of solidification but on the porosity and therefore on the pressure applied.

Les résultats figurent dans le tableau suivant.

Figure imgb0001
The results are shown in the following table.
Figure imgb0001

Claims (3)

  1. A process for the lost-foam casting, under pressure, of articles of aluminium and its alloys, in which an organic foam pattern of the article to be cast is immersed into a mould of which the walls are defined by a bath of dry sand containing no binder, the mould is filled with the molten metal which replaces the foam and gradually solidifies and an increasing isostatic gas pressure is applied simultaneously to the mould and to the metal at the earliest on completion of filling, characterised in that, to increase the resistance to fatigue of said articles, the pressure exerted rises to a value of between > 1.5 and ≦ 10 MPa, this value being attained before the quantity of solidified metal exceeds 90% by weight.
  2. A process according to claim 1, characterised in that the pressure exerted rises to a value of between 5 and 10 MPa.
  3. A process according to claim 1, characterised in that the pressure is applied at the latest when the quantity of solidified metal reaches 40% by weight.
EP89420446A 1989-09-07 1989-11-16 Lost foam pressure casting process for metal pieces Expired - Lifetime EP0421039B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8911943 1989-09-07
FR8911943A FR2651453B2 (en) 1989-09-07 1989-09-07 IMPROVEMENT IN THE LOST FOAM AND PRESSURE MOLDING PROCESS OF METAL PARTS.

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EP0421039A1 EP0421039A1 (en) 1991-04-10
EP0421039B1 true EP0421039B1 (en) 1993-07-14

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US6283196B1 (en) * 1997-03-18 2001-09-04 Georg Fischer Disa A/S Method, Pressure-supply member and pressure-supply system for active after-feeding of castings
US7025109B1 (en) * 2005-04-06 2006-04-11 Gm Global Technology Operations, Inc. Method and apparatus for controlling dispersion of molten metal in a mold cavity
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CN101733387B (en) * 2010-01-21 2012-11-07 安徽中兴华汉机械有限公司 Low pressure casting method of aluminium alloy lost foam
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MX170097B (en) 1993-08-06
PT92353A (en) 1991-05-22
DE68907601D1 (en) 1993-08-19
FI92162C (en) 1994-10-10
YU47519B (en) 1995-10-03
CN1017784B (en) 1992-08-12
KR930002837B1 (en) 1993-04-10
HU209641B (en) 1994-09-28
DE68907601T2 (en) 1993-11-11
CN1049991A (en) 1991-03-20
BG92798A (en) 1993-12-24
NO895143D0 (en) 1989-12-20
JPH0399769A (en) 1991-04-24
FR2651453A2 (en) 1991-03-08
RU1819185C (en) 1993-05-30
HU905776D0 (en) 1991-03-28
AU4538989A (en) 1991-03-14
YU168890A (en) 1994-06-24
IE893715A1 (en) 1991-03-13
JPH0626749B2 (en) 1994-04-13
FR2651453B2 (en) 1994-03-25
FI895506A0 (en) 1989-11-17
HUT57106A (en) 1991-11-28
KR910005953A (en) 1991-04-27
ATE91444T1 (en) 1993-07-15
CA2001845A1 (en) 1991-03-07
DK581689D0 (en) 1989-11-20
DK581689A (en) 1991-03-08
CS433890A3 (en) 1992-03-18
EP0421039A1 (en) 1991-04-10
AU613541B2 (en) 1991-08-01
ES2042049T3 (en) 1993-12-01
CA2001845C (en) 1994-08-09
BR8906058A (en) 1991-04-02
NO174187C (en) 1994-03-30
PL286789A1 (en) 1992-03-23
FI92162B (en) 1994-06-30
NO895143L (en) 1991-03-08
NO174187B (en) 1993-12-20

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