EP1844169B1 - Gasabschreckkammer für stahlgusswerke - Google Patents

Gasabschreckkammer für stahlgusswerke Download PDF

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Publication number
EP1844169B1
EP1844169B1 EP06709405.2A EP06709405A EP1844169B1 EP 1844169 B1 EP1844169 B1 EP 1844169B1 EP 06709405 A EP06709405 A EP 06709405A EP 1844169 B1 EP1844169 B1 EP 1844169B1
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EP
European Patent Office
Prior art keywords
speed
quenching
plateau
gas
load
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Application number
EP06709405.2A
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English (en)
French (fr)
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EP1844169A1 (de
Inventor
Aymeric Goldsteinas
Jean Berlier
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Etudes et Constructions Mecaniques SA
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Etudes et Constructions Mecaniques SA
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62Quenching devices
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/613Gases; Liquefied or solidified normally gaseous material
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/767Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material with forced gas circulation; Reheating thereof
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2241/00Treatments in a special environment
    • C21D2241/01Treatments in a special environment under pressure
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/32Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for gear wheels, worm wheels, or the like

Definitions

  • the present invention relates to a gas quenching cell for steel parts and more particularly to a method of gas quenching of steel parts used in such a quenching cell.
  • Methods of gas quenching of steel parts have many advantages over liquid quenching processes, including the fact that treated parts come out dry and clean.
  • Gaseous quenching of steel parts which have previously undergone a heat treatment (heating before quenching, annealing, tempering, etc.) or thermochemical treatment (carburizing, carbonitriding, etc.) is generally carried out with a pressurized gas, generally between 4 and 20 bars.
  • the quenching gas is, for example, nitrogen, argon, helium, carbon dioxide or a mixture of these gases.
  • a quenching operation involves rapidly cooling steel parts which are generally at temperatures between 750 ° C and 1000 ° C. At such temperatures, the steel is essentially in the form of austenite which is stable only at elevated temperatures.
  • An operation of quenching allows by rapid cooling to obtain a transformation from austenite to martensite which has high hardness properties.
  • the quenching operation must be relatively fast so that all the austenite is transformed into martensite without formation of other phases of pearlite or bainite type steel which have properties of hardness lower than martensite.
  • a quenching cell generally comprises at least one motor, generally of the electric type, rotating a stirring element, for example a helix, adapted to circulate the quenching gas in the quenching cell.
  • the quenching gas is usually circulated at the level of the pieces to be cooled at the highest possible rate during the entire quenching operation.
  • the present invention aims to obtain a quenching process of steel parts and a quenching cell for the implementation of such a method for obtaining quenched parts with improved fatigue strength and / or reduced deformations.
  • Another object of the present invention is to obtain a quenching cell for carrying out the quenching process according to the invention and whose structure is little modified compared to a conventional quenching cell.
  • the present invention provides a method of quenching a steel charge by flowing a gas at the charge through a gas drive means, the gas, after being discharged at the charge, being cooled by an exchanger in which circulates a cooling fluid.
  • the drive means is controlled to flow the gas at the load at a speed which varies according to a velocity profile of which at least a portion comprises, successively, a first bearing a first speed, a second bearing a second speed lower than the first speed and a third bearing at the first speed, the transition between the first bearing at the first speed and the second bearing at the second speed being carried out during a rising phase of the fluid temperature. cooling.
  • the static pressure of the gas at the load is decreased during the second bearing at the second speed with respect to the first bearing at the first speed.
  • the drive means is controlled to flow the gas at the first bearing load at the first speed at the second bearing at the second speed when the coolant temperature exceeds a given threshold temperature.
  • the drive means is controlled to flow the gas at the second bearing load at the second speed at the third bearing at the first speed when the coolant temperature decreases below a given additional threshold temperature.
  • the drive means is controlled to flow the gas at the first bearing load at the first speed at the second bearing at the second speed after a specified time.
  • the driving means is controlled to flow the gas at the level of the charge of the fourth bearing at the third speed at the first step at the first speed after a determined duration.
  • the Figures 1A and 1B schematically represent a side sectional view and a front sectional view of a gas quenching cell that can be used according to the invention.
  • the cell comprises an enclosure 10 of generally cylindrical or parallelepipedal shape with a horizontal axis.
  • the cell is closed at one end while the other end comprises a guillotine door system 12 giving access to the cell to introduce or extract a load to be treated 14.
  • the door 12 can close the quenching cell tightly.
  • the load 14 is maintained substantially in the center of the cell on a plate 16.
  • the upper part of the cell is provided with two external motors vertical axis 18, arranged next to each other in the longitudinal direction of the cell. These motors drive respective brewing elements within the cell.
  • the motors 18 are electric motors.
  • the cell is provided with an exchanger 22 disposed on either side of the load 14 in a horizontal plane.
  • the exchanger 22 comprises a circulation duct for a cooling fluid and is adapted to cool the quenching gas passing therethrough.
  • guide plates 24 which join the stirring devices 20 so as to direct the flow of gas produced by the latter between the load 14 and the exchanger 22.
  • the quenching gas s flows, for example down through the charge 14 and up through the exchanger 22.
  • the stirring elements 20 are turbines or fans.
  • the quenching gas is, for example, nitrogen or a mixture of carbon dioxide and helium.
  • the present invention consists in modifying in a controlled manner the flow rate of the quenching gas at the level of the charge 14 during a quenching operation.
  • the quenching cell 18 is equipped with a speed variation system.
  • the speed variation can be obtained via a frequency converter for electric motors.
  • the motors 18 are hydraulic motors, it is possible to provide a system for varying the flow rate of the oil supplying the engines 18.
  • the figure 2 illustrates the principle underlying the choice of the temperature of the cooling fluid at the outlet of the exchanger 22 as a characteristic parameter for varying the flow rate of the quenching gas.
  • the figure 2 represents a classic example of curve 26 of evolution of the the quenching gas velocity at the level of the charge 14, in which the flow rate of the quenching gas is constant and corresponds to the maximum of the capacities of the engines 18.
  • figure 2 also represents a curve 30 of evolution of the temperature of the cooling fluid at the outlet of the exchanger 22 obtained for such a velocity profile.
  • Curve 30 comprises an ascending portion 32 that bends at a peak 34 and is followed by a downward portion 36.
  • the Applicant has demonstrated that the austenite-martensite transformation of the steel constituting the load 14 occurs substantially at the level of the crown 34 of the curve 30.
  • the Applicant has shown that an improvement in the fatigue strength can be obtained by limiting the temperature variations of the charge 14 during the austenite-martensite transformation so as to allow the austenite-martensite transition to take place at relatively homogeneous charging temperatures.
  • the transition from the first maximum speed stage 42 to the intermediate speed stage 44 is carried out when the temperature of the cooling fluid reaches a first given threshold temperature, which corresponds to a temperature slightly lower than the temperature at the summit 34 of the curve 30. It is therefore substantially the temperature of the cooling fluid for which the austenite-martensite transformation of the load 14 begins.
  • the transition from the intermediate speed bearing 44 to the second maximum speed stage 46 is effected when the temperature of the coolant towards the end of the low variation portion 50 decreases below a given second threshold temperature, for example equal to the first given threshold temperature, and which is representative of the fact that the austenite-martensite transformation of the charge 14 is complete.
  • the austenite-martensite transformation of the charge 14 is then performed in its entirety for a flow rate of the quenching gas that is lower than the maximum speed.
  • the intermediate speed is adjusted to a value such that the thermal power recovered by the exchanger 22 corresponds to the thermal power released by the load 14 during the austenite-martensite conversion which is an exothermic reaction.
  • the temperature of the filler 14 is then maintained at a substantially constant and homogeneous temperature during the entire austenite-martensite transformation. 14.
  • the intermediate speed is adapted to obtain the temperature of the coolant as constant as possible during the portion 50.
  • the static pressure of the quenching gas can be maintained at a constant value throughout the quenching operation between 4 and 20 bar.
  • the static pressure of the quenching gas in the quenching cell is reduced during the application of the intermediate speed bearing in a range from 30% to 80% of the static pressure of the quench gas. quenching during the first and second maximum speed stages. This makes it possible to control, in combination with the intermediate speed of the quenching gas, the thermal power taken from the charge 14 during the austenite-martensite transformation.
  • the figure 4 represents two curves 54, 56 of temperature evolution measured at the level of the load 14 during a quenching operation of the load 14 respectively for a conventional quenching process during which the flow rate of the quenching gas remains constant and maximum and the first example of quenching process according to the invention. More precisely, the curve 56 has been obtained in the case where the duration T1 of application of the first maximum speed stage 42 is 50 seconds and the duration T2 of the intermediate speed stage 44 is 310 seconds. The intermediate speed corresponds in this example to 30% of the maximum speed.
  • the static pressure of the quenching gas which in this example is nitrogen, is 16 bar during the first and second maximum speed stages 42, 46 and 2 bar during the intermediate speed bearing 44. note that after 50 seconds, the curve 56 decreases significantly less than the curve 54.
  • the variation in the temperature of the load 14 is limited during the austenite-martensite transformation.
  • the Applicant has demonstrated an improvement in the fatigue strength of the parts constituting the quenched load 14 according to the first example of quenching process of the invention.
  • One explanation would be that since the austenite-martensite transformation is carried out at temperatures whose variations are limited, fewer internal mechanical stresses appear in the load 14, which results in an improvement in the fatigue strength.
  • the first and second threshold temperatures depend on many parameters, including the type of steel constituting the charge 14 and the area of the exchange surface between the charge 14 and the quenching gas.
  • the determination of the first and second threshold temperatures can be performed by quenching the charge 14 with a maximum gas flow rate so as to determine the curve shown in FIG. figure 2 14.
  • the first and second threshold temperatures then correspond to a given percentage of the maximum temperature of the curve 30. It is then possible for the same type of charge to implement the first example of the process of the present invention.
  • the passages of the first maximum speed bearing 42 to the intermediate speed bearing 44 and the intermediate speed bearing 44 to the second maximum speed stage 46 are respectively performed when the temperature of the coolant exceeds the first threshold temperature and decreases below the second threshold temperature.
  • the time T1 necessary for the temperature of the coolant to reach the first threshold temperature can be determined. It is not then necessary, in normal operation, to provide a temperature sensor at the exchanger 22, the passage of the first maximum speed bearing 42 to the intermediate speed bearing 44 being automatically achieved at the end of the period T1 .
  • the transition from the intermediate speed bearing 44 to the second maximum speed stage 46 can then be automatically performed after the duration T2, determined, for example, empirically.
  • the intermediate speed bearing 44 is maintained even after the temperature of the cooling fluid decreases below the second given threshold temperature, as defined above, towards the end of the weak portion. Variations 50.
  • the passage of the intermediate speed bearing 44 to the second level of maximum speed 46 is then performed only after the lapse of a duration greater than the duration T 2 as defined above.
  • the curve 42 comprises, after the portion of small variations 50, a downward portion whose slope is, in absolute value, lower than the slope of the downward portion 52 represented in FIG. figure 3 and which is prolonged by an additional portion of small variations.
  • the second embodiment of the quenching process of the invention consists in controlling the motors 18 so that the flow rate of the quenching gas at the level of the charge 14 corresponds successively to a first intermediate speed stage 62 for a period of time. T1 'and at a maximum speed level 64 until the end of the quenching operation.
  • the motors 18 are controlled so that the flow rate of the quenching gas varies between 0% and 70% of the maximum speed.
  • the curve 60 of evolution of the temperature of the cooling fluid comprises an upward portion 66 less marked than the upward portion 32 of the curve 30. The temperature of the cooling fluid therefore increases less rapidly than in the case where the quenching speed is maximum.
  • the ascending portion 66 continues to a vertex 68 and is extended by a downward portion 70.
  • the duration T1 'can extend from 5 to 30 seconds depending on the total duration of the operation quenching. In addition, the duration T1 'can be determined empirically.
  • the cooling rate of the charge 14 is lower than that which would result from a maximum flow rate of the quenching gas. Cooling being slower, the deformations of the load 14 are less important.
  • the mechanical inertia of the load 14 has increased. Such an increase in the mechanical inertia limits the subsequent deformations of the load 14 when the flow rate of the quenching gas is subsequently increased.
  • the local deformations of the charge 14, during the quenching operation are thus reduced overall since the cooling of the charge 14 with the flow rate of the maximum quenching gas is performed when the charge has already acquired a mechanical inertia. sufficient and therefore opposes a higher resistance to deformations.
  • the figure 6 represents a curve 72 representative of the evolution of the flow rate of the quenching gas at the level of the charge 14 for the third example of quenching process according to the invention and a curve 74 representative of the evolution of the temperature of the quenching gas.
  • exchanger cooling fluid 22 obtained with such a quenching gas velocity profile.
  • the curve 30 of evolution of the temperature of the cooling fluid for a quench gas circulating at maximum speed during the entire quenching operation has been reproduced in dotted lines.
  • the third embodiment of the quenching process of the invention consists in controlling the motors 18 so that the flow rate of the quenching gas at the level of the charge 14 successively corresponds to an intermediate speed bearing 76 during a period T1 ", a maximum speed bearing 78 for a duration T2", an intermediate speed bearing 80 for a duration T3 "and a maximum speed bearing 82 until the end of the quenching operation.
  • the motors 18 are controlled so that the flow velocity quenching gas varies between 0% and 70% of the maximum speed and during the intermediate speed stage 80, the flow rate of the quenching gas varies between 40% and 70% of the maximum speed.
  • the curve 74 for changing the temperature of the cooling fluid comprises an upward portion 84 less marked than the upward portion 32 of the curve 30.
  • the curve 74 comprises an ascending portion 86 at the intermediate speed bearing 80, the curve 74 comprises a bearing 88 of small variations and at the maximum speed bearing 82, the curve 74 comprises a downward portion 90.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Control Of Heat Treatment Processes (AREA)
  • Furnace Details (AREA)

Claims (7)

  1. Verfahren zum Abschrecken einer Stahlcharge (14) durch Leiten eines Gases auf einem Niveau der Charge mittels Gasleitungsmitteln (18, 20), wobei das Gas, nachdem es auf dem Niveau der Charge (14) geflossen ist, durch einen Tauscher (22) gekühlt wird, in welchem ein Kühlströmungsmittel fließt, dadurch gekennzeichnet, dass, die Leitungsmittel so gesteuert werden, dass sie das Gas auf dem Niveau der Charge mit einer Geschwindigkeit fließen lassen, welche gemäß einem Geschwindigkeitsprofil variiert, wobei zumindest ein Teil davon in aufeinander folgenden Weise ein erstes Plateau mit einer ersten Geschwindigkeit (42), ein zweites Plateau mit einer zweiten Geschwindigkeit (44), die niedriger ist als die erste Geschwindigkeit, und ein drittes Plateau mit der ersten Geschwindigkeit (46) aufweist, wobei der Übergang zwischen dem ersten Plateau mit der ersten Geschwindigkeit und dem zweiten Plateau mit der zweiten Geschwindigkeit während einer Phase des Zunehmens der Temperatur des Kühlströmungsmittels ausgeführt wird.
  2. Verfahren nach Anspruch 1, wobei der statische Druck des Gases auf dem Niveau der Charge (14) während des zweiten Plateaus mit der zweiten Geschwindigkeit (44; 80) bezüglich des dritten Plateaus mit der ersten Geschwindigkeit (46; 82) verringert wird.
  3. Verfahren nach Anspruch 1, wobei die Leitungsmittel so gesteuert werden, dass sie das Gas auf dem Niveau der Charge (14) vom ersten Plateau mit der ersten Geschwindigkeit (42) zum zweiten Plateau mit der zweiten Geschwindigkeit (44) fließen lassen, wenn die Temperatur des Kühlströmungsmittels eine gegebene Temperaturschwelle erreicht.
  4. Verfahren nach Anspruch 1, wobei die Leitungsmittel so gesteuert werden, dass sie das Gas auf dem Niveau der Charge (14) vom zweiten Plateau mit der zweiten Geschwindigkeit (44) zum dritten Plateau mit der ersten Geschwindigkeit (46) fließen lassen, wenn die Temperatur des Kühlströmungsmittels unter eine gegebene zusätzliche Temperaturschwelle absinkt.
  5. Verfahren nach Anspruch 1, wobei die Leitungsmittel so gesteuert werden, dass sie das Gas auf dem Niveau der Charge (14) vom ersten Plateau mit der ersten Geschwindigkeit (42) zum zweiten Plateau mit der zweiten Geschwindigkeit (44) nach einer vorbestimmten Zeit fließen lassen.
  6. Verfahren nach Anspruch 1, wobei die Bewegungsmittel (18, 20) so gesteuert werden, dass sie das Gas auf dem Niveau der Charge gemäß einem Geschwindigkeitsprofil fließen lassen, welches vom Beginn eines Abschreckvorgangs in aufeinander folgender Weise ein viertes Plateau mit einer dritten Geschwindigkeit (62), die niedriger ist als die erste Geschwindigkeit, und das erste Plateau mit der ersten Geschwindigkeit (64) aufweist, wobei der Übergang zwischen dem vierten Plateau mit der dritten Geschwindigkeit und dem ersten Plateau mit der ersten Geschwindigkeit während einer Phase der Zunahme der Temperatur des Kühlströmungsmittels ausgeführt wird.
  7. Verfahren nach Anspruch 6, wobei die Leitungsmittel so gesteuert werden, dass sie das Gas auf dem Niveau der Charge (14) vom vierten Plateau mit der dritten Geschwindigkeit (62) zum ersten Plateau mit der ersten Geschwindigkeit (64) nach einer vorbestimmten Zeit fließen lassen.
EP06709405.2A 2005-01-17 2006-01-16 Gasabschreckkammer für stahlgusswerke Active EP1844169B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0550134A FR2880898B1 (fr) 2005-01-17 2005-01-17 Cellule de trempe au gaz pour pieces en acier
PCT/FR2006/050017 WO2006075120A1 (fr) 2005-01-17 2006-01-16 Cellule de trempe au gaz pour pieces en acier

Publications (2)

Publication Number Publication Date
EP1844169A1 EP1844169A1 (de) 2007-10-17
EP1844169B1 true EP1844169B1 (de) 2019-04-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP06709405.2A Active EP1844169B1 (de) 2005-01-17 2006-01-16 Gasabschreckkammer für stahlgusswerke

Country Status (10)

Country Link
US (1) US20060157169A1 (de)
EP (1) EP1844169B1 (de)
JP (1) JP5638737B2 (de)
KR (1) KR20070099648A (de)
CN (1) CN101107368A (de)
BR (1) BRPI0606652B1 (de)
CA (1) CA2595020A1 (de)
FR (1) FR2880898B1 (de)
MX (1) MX2007008652A (de)
WO (1) WO2006075120A1 (de)

Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
SE0801263L (sv) * 2007-05-29 2008-11-30 Indexator Ab Metod & arbetsstycke
JP4916545B2 (ja) * 2009-12-21 2012-04-11 エジソンハード株式会社 熱処理装置
JP6288413B2 (ja) * 2013-10-11 2018-03-07 三菱重工業株式会社 ステンレス部材の熱処理方法、及びステンレス鍛造品の製造方法。
CN111575460B (zh) * 2020-07-02 2022-07-26 武汉轻工大学 一种热处理冷却装置
CN112556426B (zh) * 2020-12-15 2022-08-23 江西科技学院 一种具有气相淬火功能的烧结炉及其淬火工艺

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US3224910A (en) * 1963-02-18 1965-12-21 Monsanto Co Quenching process
DE3346884A1 (de) * 1983-12-23 1985-07-11 Ipsen Industries International Gmbh, 4190 Kleve Industrieofen zur waermebehandlung metallischer werkstuecke
JPS63149313A (ja) * 1986-12-12 1988-06-22 Daido Steel Co Ltd ガス焼入炉
DE4004295A1 (de) * 1990-02-13 1991-08-14 Karl Heess Gmbh & Co Verfahren und vorrichtung zum haerten von werkstuecken mittels presswerkzeugen
DE4135313A1 (de) * 1991-10-25 1993-04-29 Ipsen Ind Int Gmbh Verfahren zum abkuehlen einer werkstueckcharge innerhalb eines waermebehandlungsprozesses
JP3289949B2 (ja) * 1992-04-27 2002-06-10 パーカー熱処理工業株式会社 密閉循環式ガス焼入装置及びガス焼入方法
US5478985A (en) * 1993-09-20 1995-12-26 Surface Combustion, Inc. Heat treat furnace with multi-bar high convective gas quench
JPH1081913A (ja) * 1996-09-06 1998-03-31 Ishikawajima Harima Heavy Ind Co Ltd ガス冷却による等温焼き入れ装置
FR2779218B1 (fr) * 1998-05-29 2000-08-11 Etudes Const Mecaniques Cellule de trempe sous gaz
JP2000129341A (ja) * 1998-10-20 2000-05-09 Toyota Motor Corp 低歪み焼入れ方法
GB9929956D0 (en) * 1999-12-17 2000-02-09 Boc Group Plc Qenching heated metallic objects
DE10030046C1 (de) * 2000-06-19 2001-09-13 Ald Vacuum Techn Ag Verfahren und Vorrichtung zum Bestimmen der Abkühlwirkung einer strömenden Gasatmosphäre auf Werkstücke
JP2002249819A (ja) * 2001-02-22 2002-09-06 Chugai Ro Co Ltd 金属材料のガス冷却方法

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Also Published As

Publication number Publication date
JP2008527176A (ja) 2008-07-24
EP1844169A1 (de) 2007-10-17
WO2006075120A1 (fr) 2006-07-20
MX2007008652A (es) 2007-10-18
JP5638737B2 (ja) 2014-12-10
CA2595020A1 (en) 2006-07-20
CN101107368A (zh) 2008-01-16
FR2880898B1 (fr) 2007-05-11
KR20070099648A (ko) 2007-10-09
US20060157169A1 (en) 2006-07-20
BRPI0606652A2 (pt) 2009-07-07
FR2880898A1 (fr) 2006-07-21
BRPI0606652B1 (pt) 2015-06-02

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