EP1543170A1 - Procede de refroidissement rapide de pieces par transfert convectif et radiatif - Google Patents
Procede de refroidissement rapide de pieces par transfert convectif et radiatifInfo
- Publication number
- EP1543170A1 EP1543170A1 EP03712227A EP03712227A EP1543170A1 EP 1543170 A1 EP1543170 A1 EP 1543170A1 EP 03712227 A EP03712227 A EP 03712227A EP 03712227 A EP03712227 A EP 03712227A EP 1543170 A1 EP1543170 A1 EP 1543170A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cooling
- gas
- cooling gas
- cooling method
- gases
- 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
- 238000001816 cooling Methods 0.000 title claims abstract description 40
- 238000012546 transfer Methods 0.000 title claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 80
- 239000000203 mixture Substances 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000112 cooling gas Substances 0.000 claims abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 238000009434 installation Methods 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052734 helium Inorganic materials 0.000 claims abstract description 16
- 239000001307 helium Substances 0.000 claims abstract description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000005855 radiation Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000000470 constituent Substances 0.000 claims description 9
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 34
- 238000010791 quenching Methods 0.000 description 24
- 230000000171 quenching effect Effects 0.000 description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- 239000001569 carbon dioxide Substances 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005256 carbonitriding Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- 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
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
- C21D1/613—Gases; Liquefied or solidified normally gaseous material
-
- 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
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/767—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material with forced gas circulation; Reheating thereof
-
- 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
- C21D2241/00—Treatments in a special environment
- C21D2241/01—Treatments in a special environment under pressure
Definitions
- the present invention relates generally to the heat treatment of metals and more particularly to the gaseous quenching operation of steel parts which have previously undergone a heat treatment (such as heating before quenching, annealing, tempering) or thermochemical (such as carburizing, carbonitriding) .
- a heat treatment such as heating before quenching, annealing, tempering
- thermochemical such as carburizing, carbonitriding
- gas quenching is generally carried out by circulating a pressurized gas in a closed circuit between a load and a cooling circuit.
- gas quenching systems generally operate at pressures between four and twenty times atmospheric pressure (4 to 20 bars or 4,000 to 20,000 hectopascals). To designate the pressure, the bar will be used in this description as a unit, it being understood that a bar is equal to 1000 hPa.
- FIG. 1 very schematically shows an example of a gas quenching installation.
- This installation 1 contains a charge 2 to be cooled arranged in a sealed enclosure 3.
- the charge is typically surrounded by deflection plates 4 to guide the circulation of gas.
- a gas inlet 5 makes it possible to introduce a desired gas mixture under pressure, it being understood that the cooling gases can for example be introduced in the form of a pre-formed mixture or that several separate gas inlets can be provided to introduce various cooling gases separately.
- a turbine 6 actuated by a motor 7 makes it possible to ensure the circulation of the gases, for example by passing from a cooling circuit 9 towards the load to be cooled 2.
- the cooling circuit 9 commonly consists of pipes in which a fluid circulates cooling.
- FIG. 1 The installation of FIG. 1 has only been shown as an example of one of many possible and existing structures for ensuring the circulation of a gas of cooling in an enclosure.
- the pressure is of the order of 4 to 20 bars during the cooling phase.
- Many variations are possible, as to the arrangement of the load, the direction of circulation of the gases and the mode of circulation of these gases.
- the most commonly used gas for cooling is nitrogen since it is an inert and inexpensive gas.
- its density is well suited to simple blower or turbine installations and its heat transfer coefficient is sufficiently satisfactory.
- the temperature drop must be as rapid as possible so that the transformation of the steel takes place satisfactorily from the austenitic phase to the martensitic phase without going through pearlitic and / or bainitic phases.
- one of the objects of the present invention is to provide a quenching installation using a thermally more efficient cooling gas than nitrogen but which is inexpensive and simple to use, making it possible to cool the most expensive materials. demanding.
- Another object of the present invention is to provide a cooling process using a gas compatible with existing installations currently operating with nitrogen (and therefore requiring no significant modification of installation).
- the present invention provides, in a process for rapidly cooling metal parts using a cooling gas under pressure, the use of a cooling gas which comprises one or more gases absorbing the radiation. infrared, chosen so as to improve the heat transfer to the part by combining the phenomena of radiative and convective transfers, and so as to improve the convective transfer coefficient compared to traditional nitrogen cooling conditions.
- the cooling gas also comprises an additive gas chosen from helium, hydrogen or their mixtures.
- the cooling gas also comprises an additional gas.
- the composition of the cooling gas is also adjusted so as to obtain an average density of the cooling gas thus formed which is of the same order of magnitude as that of nitrogen.
- the composition of the cooling gas is also adjusted so as to optimize the convective transfer coefficient with respect to the convective transfer coefficients of each of the constituents of the cooling gas taken individually.
- the cooling operation is carried out within an enclosure where the parts to be treated are arranged, provided with a gas stirring system, and the composition of the cooling gas is also adjusted so as to obtain an average density cooling gas thus formed which is adapted to said agitation system of the enclosure, without it being necessary to make significant modifications to it.
- the composition of the cooling gas is also adjusted so that, during the cooling phase of the parts, endothermic chemical reactions between one or more of the absorbent gases and another of the constituents of the cooling gas.
- said gas absorbing infrared radiation is C0 2 .
- Said gas absorbing infrared radiation is chosen from the group formed by saturated or unsaturated hydrocarbons, CO, H 2 0, NH 3 , NO, N 2 0, N0 and their mixtures.
- the content of absorbing gas in the cooling gas is between 5 and 100%, preferably between 20 and 80%.
- the cooling gas is a binary mixture C0 2 - He, whose C0 2 content is between 30 and 80%.
- the cooling gas is a binary mixture C0 2 - H 2 , whose C0 content is between 30 and 60%.
- a cooling gas recycling operation is carried out after use, capable of re-compressing the gas before subsequent use, and if necessary also separating and / or purifying so as to recover all or part of the constituents of the cooling gas.
- the invention also relates to the use in a rapid cooling installation of metal parts using a pressurized cooling gas, installation optimized for operation under nitrogen, of a cooling gas comprising from 20 to 80% of a gas absorbing infrared radiation and 80 to 20% of hydrogen or helium or their mixtures, the composition of the cooling gas being adjusted so that it is not necessary to make significant modifications at installation.
- a cooling gas comprising from 20 to 80% of a gas absorbing infrared radiation and 80 to 20% of hydrogen or helium or their mixtures, the composition of the cooling gas being adjusted so that it is not necessary to make significant modifications at installation.
- FIGS. 2A and 2B show the convective heat transfer coefficient of different mixtures of gases at various pressures, in the case of a fluid flowing parallel between cylinders;
- quenching gas a gas absorbing infrared radiation or a mixture based on such gases absorbing infrared radiation (hereinafter referred to as absorbing gas), such as carbon dioxide. (CO2) and added, if necessary, one or more gases having a good ability to transfer convective heat (hereinafter referred to as additive gas), such as helium or hydrogen.
- absorbing gas such as carbon dioxide. (CO2)
- additive gas one or more gases having a good ability to transfer convective heat
- Such a mixture has the advantage, compared with traditional quenching gases or mixtures of gases using transparent gases with infrared radiation, such as nitrogen, hydrogen, and helium, of absorbing heat at both by convective and radiative phenomena, thereby increasing the overall heat flow extracted from a charge to be cooled.
- complementary gas such as nitrogen
- nitrogen envisaged both as a simple carrier gas and in a more active role allowing, as will be seen below, to optimize the properties of the gas mixture such as density, thermal conductivity, viscosity, etc.
- Optimization should therefore be understood here to mean being at the maximum of the curve considered, or much lower (for example for economic reasons) but in any event so as to have a convective transfer coefficient which is better than each of the convective transfer coefficients of each of the constituents of the cooling gas taken individually.
- a mixture of absorbent gas (and if necessary additive gas), possibly with the addition of complementary gases, under optimized density conditions such as 1 can be carried out in quenching facilities usually provided and optimized to operate in the presence of nitrogen.
- nitrogen for example, carbon dioxide is mixed with helium, taken as an additive gas, so as to combine an optimization of the coefficient of heat transfer by convection and an average density of the mixture which is of the same order of magnitude as that of nitrogen.
- Existing installations can then be used with comparable ventilation speeds and powers, and existing ventilation and gas deflection structures, without having to make significant modifications to the installation.
- FIG. 2A represents, for pressures of 5, 10 and 20 bars, the convective heat transfer coefficient jj of a mixture of ⁇ 2 and helium, for various proportions of ⁇ 2 in the mixture.
- the abscissa gives the relationship between the concentration of CO2, c (C02), and the total concentration of CO2 and He, c (C02 + He).
- the convective heat transfer coefficient has a maximum for CO2 concentration values of between approximately 40 and 70%, in this case approximately 650 W / m ⁇ / K at 20 bars for a concentration of around 60%.
- the mixture not only has the advantage of having a density close to that of nitrogen but in addition of having a higher convective heat transfer coefficient than that of pure CO2.
- Figure 2B shows similar curves for mixtures of carbon dioxide (CO2) and hydrogen (H2).
- CO2 carbon dioxide
- H2 hydrogen
- the convective heat transfer coefficient k jj is better for a mixture of carbon dioxide and hydrogen than for a mixture of C0 2 and helium.
- FIG. 3 illustrates the result of calculations simulating the cooling by convective transfer of a steel cylinder with various cooling gases in the case of the flow of the mixture parallel to the length of the cylinders (cylinders simulating the case of elongated parts).
- Curves have been shown for pure nitrogen (N2) / for a mixture with 60% of CO2 and 40% of helium, for pure hydrogen, and for a mixture with 40% of CO2 and 60% of hydrogen. It is found that it is this latter mixture which gives the best results, that is to say the greatest cooling rate between 850 and 500 ° C.
- the improvement in the quenching rate is of the order of 20% relative to hydrogen alone and of the order of 100% relative to nitrogen alone.
- the present invention is susceptible of various variants and modifications which will appear to those skilled in the art, in particular as regards the choice of gases, the optimization of the proportions of each gas, it being understood that the 'we can if desired use ternary mixtures such C ⁇ 2-H e -U2 and that we can possibly add other gases, called above complementary gases.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Gas Separation By Absorption (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
- Radiation Pyrometers (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Furnace Details (AREA)
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0211680 | 2002-09-20 | ||
| FR0211680A FR2844809B1 (fr) | 2002-09-20 | 2002-09-20 | Procede de refroidissement rapide de pieces par transfert convectif et radiatif |
| PCT/FR2003/000053 WO2004027098A1 (fr) | 2002-09-20 | 2003-01-09 | Procede de refroidissement rapide de pieces par transfert convectif et radiatif |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1543170A1 true EP1543170A1 (fr) | 2005-06-22 |
| EP1543170B1 EP1543170B1 (fr) | 2007-12-05 |
| EP1543170B8 EP1543170B8 (fr) | 2008-04-23 |
Family
ID=31970862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03712227A Expired - Lifetime EP1543170B8 (fr) | 2002-09-20 | 2003-01-09 | Procede de refroidissement rapide de pieces par transfert convectif et radiatif |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US20060048868A1 (fr) |
| EP (1) | EP1543170B8 (fr) |
| JP (1) | JP4490270B2 (fr) |
| KR (1) | KR100953818B1 (fr) |
| CN (1) | CN100567516C (fr) |
| AT (1) | ATE380256T1 (fr) |
| AU (1) | AU2003216799A1 (fr) |
| BR (1) | BRPI0314597B1 (fr) |
| CA (1) | CA2498929C (fr) |
| DE (1) | DE60317912T2 (fr) |
| ES (1) | ES2297138T3 (fr) |
| FR (1) | FR2844809B1 (fr) |
| MX (1) | MXPA05002716A (fr) |
| WO (1) | WO2004027098A1 (fr) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004054627A1 (de) * | 2004-11-11 | 2006-05-18 | Linde Ag | Vorrichtung zum Kühlen von langen Gegenständen |
| FR2890979B1 (fr) * | 2005-09-16 | 2007-11-02 | Air Liquide | Methode pour se premunir de la formation de monoxyde de carbone lors d'une operation de trempe gazeuse |
| DE102006012985A1 (de) * | 2006-03-21 | 2007-10-11 | Linde Ag | Verfahren und Vorrichtung zum schnellen Abkühlen von Werkstücken |
| CN107275251B (zh) * | 2016-04-08 | 2020-10-16 | 上海新昇半导体科技有限公司 | 降低预抽腔体中芯片温度的方法及芯片降温装置 |
| CH713765A1 (de) | 2017-05-10 | 2018-11-15 | Synhelion Sa C/O Avv Luca Tenchio | Verfahren zum Betrieb eines Receivers und Receiver zur Ausführung des Verfahrens. |
| CN120521442A (zh) | 2017-07-07 | 2025-08-22 | 信赫利恩有限公司 | 用于传递气体中所含热量的方法以及用于该目的热交换器 |
| KR102080934B1 (ko) | 2018-04-18 | 2020-02-24 | (주)알룩스메뉴펙처링 | 알루미늄 합금 실린더블록 및 실린더헤드의 급속 에어냉각장치 |
| CH715527A2 (de) * | 2018-11-08 | 2020-05-15 | Eni Spa | Verfahren zum Betrieb eines Receivers und Receiver zur Ausführung des Verfahrens. |
| CH716993A2 (de) * | 2019-12-26 | 2021-06-30 | Synhelion Sa | Receiver. |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3736501C1 (de) * | 1987-10-28 | 1988-06-09 | Degussa | Verfahren zur Waermebehandlung metallischer Werkstuecke |
| US5173124A (en) * | 1990-06-18 | 1992-12-22 | Air Products And Chemicals, Inc. | Rapid gas quenching process |
| CN1022577C (zh) * | 1990-08-31 | 1993-10-27 | 中国科学院山西煤炭化学研究所 | 金属热处理用氮基可控气氛的生产方法 |
| US5259893A (en) * | 1991-07-08 | 1993-11-09 | Air Products And Chemicals, Inc. | In-situ generation of heat treating atmospheres using a mixture of non-cryogenically produced nitrogen and a hydrocarbon gas |
| AU659719B2 (en) * | 1992-03-10 | 1995-05-25 | Boc Group, Inc., The | Method and apparatus for forming a heat treating atmosphere |
| DE4208485C2 (de) * | 1992-03-17 | 1997-09-04 | Wuenning Joachim | Verfahren und Vorrichtung zum Abschrecken metallischer Werkstücke |
| SE504320C2 (sv) * | 1995-06-22 | 1997-01-13 | Aga Ab | Förfarande och anläggning för behandling av komponenter med en gasblandning |
| FR2746112B1 (fr) * | 1996-03-13 | 1998-06-05 | Procede de traitement thermique en continu de bandes metalliques dans des atmospheres de nature differente | |
| DE19709957A1 (de) * | 1997-03-11 | 1998-09-17 | Linde Ag | Verfahren zur Gasabschreckung metallischer Werkstücke nach Wärmebehandlungen |
| DE19920297A1 (de) * | 1999-05-03 | 2000-11-09 | Linde Tech Gase Gmbh | Verfahren zur Wärmebehandlung metallischer Werkstücke |
| DE59903032D1 (de) * | 1999-09-24 | 2002-11-14 | Ipsen Int Gmbh | Verfahren zur Wärmebehandlung metallischer Werkstücke |
| GB0029281D0 (en) * | 2000-11-30 | 2001-01-17 | Boc Group Plc | Quenching Method & Apparatus |
| US20020104589A1 (en) * | 2000-12-04 | 2002-08-08 | Van Den Sype Jaak | Process and apparatus for high pressure gas quenching in an atmospheric furnace |
-
2002
- 2002-09-20 FR FR0211680A patent/FR2844809B1/fr not_active Expired - Lifetime
-
2003
- 2003-01-09 AU AU2003216799A patent/AU2003216799A1/en not_active Abandoned
- 2003-01-09 AT AT03712227T patent/ATE380256T1/de not_active IP Right Cessation
- 2003-01-09 CN CNB038222221A patent/CN100567516C/zh not_active Expired - Lifetime
- 2003-01-09 EP EP03712227A patent/EP1543170B8/fr not_active Expired - Lifetime
- 2003-01-09 MX MXPA05002716A patent/MXPA05002716A/es active IP Right Grant
- 2003-01-09 WO PCT/FR2003/000053 patent/WO2004027098A1/fr not_active Ceased
- 2003-01-09 BR BRPI0314597-2A patent/BRPI0314597B1/pt not_active IP Right Cessation
- 2003-01-09 CA CA2498929A patent/CA2498929C/fr not_active Expired - Lifetime
- 2003-01-09 US US10/511,785 patent/US20060048868A1/en not_active Abandoned
- 2003-01-09 JP JP2004537189A patent/JP4490270B2/ja not_active Expired - Lifetime
- 2003-01-09 KR KR1020057004677A patent/KR100953818B1/ko not_active Expired - Lifetime
- 2003-01-09 ES ES03712227T patent/ES2297138T3/es not_active Expired - Lifetime
- 2003-01-09 DE DE60317912T patent/DE60317912T2/de not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2004027098A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1543170B8 (fr) | 2008-04-23 |
| KR100953818B1 (ko) | 2010-04-21 |
| FR2844809B1 (fr) | 2007-06-29 |
| US20060048868A1 (en) | 2006-03-09 |
| CN100567516C (zh) | 2009-12-09 |
| DE60317912D1 (de) | 2008-01-17 |
| FR2844809A1 (fr) | 2004-03-26 |
| ATE380256T1 (de) | 2007-12-15 |
| CA2498929A1 (fr) | 2004-04-01 |
| WO2004027098A8 (fr) | 2005-09-29 |
| ES2297138T3 (es) | 2008-05-01 |
| KR20050084565A (ko) | 2005-08-26 |
| AU2003216799A1 (en) | 2004-04-08 |
| BRPI0314597B1 (pt) | 2015-06-09 |
| DE60317912T2 (de) | 2008-06-12 |
| WO2004027098A1 (fr) | 2004-04-01 |
| BR0314597A (pt) | 2005-08-09 |
| CA2498929C (fr) | 2011-04-19 |
| JP2005539142A (ja) | 2005-12-22 |
| EP1543170B1 (fr) | 2007-12-05 |
| MXPA05002716A (es) | 2005-11-17 |
| AU2003216799A8 (en) | 2004-04-08 |
| JP4490270B2 (ja) | 2010-06-23 |
| CN1681947A (zh) | 2005-10-12 |
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