WO2002072901A1 - Micro-alloyed oxygen-free copper alloy and its use - Google Patents
Micro-alloyed oxygen-free copper alloy and its use Download PDFInfo
- Publication number
- WO2002072901A1 WO2002072901A1 PCT/FI2002/000184 FI0200184W WO02072901A1 WO 2002072901 A1 WO2002072901 A1 WO 2002072901A1 FI 0200184 W FI0200184 W FI 0200184W WO 02072901 A1 WO02072901 A1 WO 02072901A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper alloy
- oxygen
- free copper
- ppm
- alloyed
- Prior art date
Links
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 7
- 238000003466 welding Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012925 reference material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
Definitions
- the present invention relates to a copper alloy according to the preamble of claim 1.
- the invention also relates to the use of said copper alloy, particularly in weldable applications.
- Good weldability is an important property in copper, particularly in connection with the manufacturing of tubes and conducting wires for tubular cables.
- the material often used in the conducting wires of tubes and tubular cables, such as coaxial cables and the like, is thin copper strip, which in the manufacturing process is bent to be tubular, and the free edges of the strip are typically welded together.
- the obtained tube is further processed by drawing or by corrugating after welding.
- Said cables are used for instance in connection with cables designed for various telecommunication purposes or for example in underwater cables.
- oxygen-free copper for instance Cu-OF/ Cu-OFE.
- the need has arisen to further develop the good welding and working qualities of oxygen-free copper.
- the object of the present invention is to realize a copper alloy with an excellent electroconductivity and with an excellent weldability and post-welding workability.
- the alloy according to the invention has several remarkable advantages.
- When adding small amounts of alloy agents, particularly tin and/or manganese, into the oxygen-free copper extremely good results have been achieved as regards weldability and workability.
- By micro-alloying small amounts of tin and/or manganese into oxygen-free copper the properties of the molten material melted in connection with the joining process have been improved, particularly as regards viscosity and surface tension. Both of said properties have a significant effect in the weldability of the copper alloy.
- the alloy according to the invention there is achieved both a welding process that is easier to control, and a joint that is mechanically stronger.
- the achieved alloy is very well suited to be used in connection with products - for example tubes, profile tubes, corrugated tubes and tubular cable wires - that are manufactured of copper strips by welding, and in connection with the working of said products, for example drawing, bending, corrugating, profiling etc.
- the employed materials were oxygen-free copper micro-alloyed with tin (Cu- OF+Sn) and oxygen-free copper micro-alloyed with manganese (Cu-OF+Mn), and the employed reference materials were oxygen-free copper (Cu-OF, applicant's quality type OF-OK).
- the micro-alloyed samples were the following: Cu-OF+Sn alloying: 25 ppm Sn Cu-OF+Mn alloying: 8-9 ppm Mn
- the references used in the experiments were oxygen-free copper (Cu-OF).
- the thickness of the strip to be welded was 0.26 mm.
- the welding experiments were performed by bending the material strip into tubular form and by welding the strip edges together with TIG welding.
- the employed equipment was a typical equipment used for welding tubes, where the material strip is first conducted, via bending rollers, into a welding position, where the opposite edges of the strip that is bent into tubular form are welded together. After the welding step, the welded tube is wound or conducted to a coil.
- the employed welding method was TIG welding, which is typically used In the welding of copper tubes.
- the employed protective gas was Argon.
- the welding rate was 20 m/min.
- the welding current fluctuated within the range of 100 - 250 A, and the welding voltage was roughly 9 - 12 V.
- the welded tubes were subjected to an eddy current control.
- the evaluation was carried out by observing the results given by an eddy current meter.
- the evaluations are collected in table 2 and in figure 1.
- Part of the welded tubes were subjected to eddy current measurements.
- the evaluation was carried out by observing the results given by the eddy current meter.
- the obtained grade was affected by the height of the background noise caused by the weld, and possible peaks in the signal reduced the grade.
- a measurement carried out throughout a stretch of 30 m was applied.
- the alloy symbol SN means oxygen-free copper alloyed with tin (Cu-OF+Sn)
- the alloy symbol MN means oxygen-free copper alloyed with manganese (Cu-OF+Mn)
- OF means ordinary oxygen-free copper (Cu-OF).
- the oxygen-free copper alloyed with tin (Cu-OF+Sn) is marked with a square.
- the oxygen-free copper alloyed with manganese (Cu-OF+Mn) is marked with a circle.
- the oxygen-free copper (Cu-OF) used as reference material is marked with a triangle.
- the copper alloy according to the invention comprises oxygen-free copper (for example Cu-OF/ Cu-OFE) and, micro-alloyed therein, about 1 - 250 ppm, typically 1 - 120 ppm, preferably 10 - 30 ppm, tin (Sn) and/or about 1 - 150 ppm, typically 1 - 70 ppm, preferably 5 - 20 ppm, manganese (Mn).
- oxygen-free copper for example Cu-OF/ Cu-OFE
- Mn manganese
- the electroconductivity of the copper alloy is over 100% IACS, typically over 101% IACS, preferably over 101.5% IACS.
- the invention also relates to the use of copper alloy:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Arc Welding In General (AREA)
- Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
An oxygen-free copper alloy comprising oxygen-free copper and, micro-alloyed therein, about 1 250 ppm tin (Sn) and/or about 1 150 ppm manganese (Mn). The invention also relates to the use of said copper alloy.
Description
Micro-alloyed oxygen-free copper alloy and its use
The present invention relates to a copper alloy according to the preamble of claim 1. The invention also relates to the use of said copper alloy, particularly in weldable applications.
Good weldability is an important property in copper, particularly in connection with the manufacturing of tubes and conducting wires for tubular cables. The material often used in the conducting wires of tubes and tubular cables, such as coaxial cables and the like, is thin copper strip, which in the manufacturing process is bent to be tubular, and the free edges of the strip are typically welded together. In many cases the obtained tube is further processed by drawing or by corrugating after welding. Said cables are used for instance in connection with cables designed for various telecommunication purposes or for example in underwater cables. In known arrangements where an excellent electroconductivity is needed, there is typically used so-called oxygen-free copper (for instance Cu-OF/ Cu-OFE). However, the need has arisen to further develop the good welding and working qualities of oxygen-free copper.
The object of the present invention is to realize a copper alloy with an excellent electroconductivity and with an excellent weldability and post-welding workability.
The invention is characterized by what is specified in the claims.
The alloy according to the invention has several remarkable advantages. When adding small amounts of alloy agents, particularly tin and/or manganese, into the oxygen-free copper, extremely good results have been achieved as regards weldability and workability. By micro-alloying small amounts of tin and/or manganese into oxygen-free copper, the properties of the molten material melted in connection with the joining process have been improved, particularly as regards viscosity and surface tension. Both of said properties have a
significant effect in the weldability of the copper alloy. By means of the alloy according to the invention, there is achieved both a welding process that is easier to control, and a joint that is mechanically stronger. The achieved alloy is very well suited to be used in connection with products - for example tubes, profile tubes, corrugated tubes and tubular cable wires - that are manufactured of copper strips by welding, and in connection with the working of said products, for example drawing, bending, corrugating, profiling etc.
The invention is described in more detail below with reference the appended drawing, where the results of an example illustrating the invention are represented in graphical form.
Example 1
Table 1. Copper alloys, their electroconductivity, weldability and post-welding workability.
Material samples, bent into tubular form and illustrated in table 1 , were welded. The employed materials were oxygen-free copper micro-alloyed with tin (Cu- OF+Sn) and oxygen-free copper micro-alloyed with manganese (Cu-OF+Mn), and the employed reference materials were oxygen-free copper (Cu-OF, applicant's quality type OF-OK). The micro-alloyed samples were the following: Cu-OF+Sn alloying: 25 ppm Sn Cu-OF+Mn alloying: 8-9 ppm Mn
The references used in the experiments were oxygen-free copper (Cu-OF). The thickness of the strip to be welded was 0.26 mm.
The welding experiments were performed by bending the material strip into tubular form and by welding the strip edges together with TIG welding. The employed equipment was a typical equipment used for welding tubes, where the material strip is first conducted, via bending rollers, into a welding position, where the opposite edges of the strip that is bent into tubular form are welded together. After the welding step, the welded tube is wound or conducted to a coil. The employed welding method was TIG welding, which is typically used In the welding of copper tubes. The employed protective gas was Argon. The welding rate was 20 m/min. The welding current fluctuated within the range of 100 - 250 A, and the welding voltage was roughly 9 - 12 V.
The welding experiments were successful. As regards the setting of welding values, with a quality that was micro-alloyed with tin it was easier to reach the correct setting values both for the shaping roller arrangement that bends the material strip to be welded, and for the welding values. The behavior of the melt of the Sn alloy could be controlled extremely well throughout a wide range of parameters. Also the Mn-alloyed material had better weldability than normal oxygen-free copper.
In the experiments that were carried out, it was found out that the weldability of oxygen-free copper micro-alloyed with tin (tin 25 ppm) was remarkably improved and was found excellent. Weldability was also improved by micro- alloying oxygen-free copper with small amounts of manganese (manganese 8 - 9 ppm). In the experiments, the weldability of oxygen-free copper micro-alloyed with manganese was estimated to be weaker than the weldability of oxygen- free copper micro-alloyed with tin. For a man skilled in the art, it is obvious that also other oxygen-free copper qualities (for instance Cu-OFE, Cu-OFXLP and C10910 (CDA code)) can be micro-alloyed in a similar way.
The welded tubes were subjected to an eddy current control. The evaluation was carried out by observing the results given by an eddy current meter. The evaluations are collected in table 2 and in figure 1. Part of the welded tubes
were subjected to eddy current measurements. The evaluation was carried out by observing the results given by the eddy current meter. The obtained grade was affected by the height of the background noise caused by the weld, and possible peaks in the signal reduced the grade. In the eddy current analysis, a measurement carried out throughout a stretch of 30 m was applied.
Table 2. Welding parameters and evaluation of the welds
In the table, the alloy symbol SN means oxygen-free copper alloyed with tin (Cu-OF+Sn), the alloy symbol MN means oxygen-free copper alloyed with manganese (Cu-OF+Mn) and OF means ordinary oxygen-free copper (Cu-OF).
In figure 1 , the oxygen-free copper alloyed with tin (Cu-OF+Sn) is marked with a square. The oxygen-free copper alloyed with manganese (Cu-OF+Mn) is marked with a circle. The oxygen-free copper (Cu-OF) used as reference material is marked with a triangle.
On the basis of figure 1 and table 2, it is found out that oxygen-free copper alloyed with tin (Cu-OF+Sn) was absolutely best in quality and made it possible to use the widest range of welding current. The welds obtained good grades throughout a wide range of current, i.e. 105 - 190 A. Likewise, oxygen-free copper alloyed with manganese (Cu-OF+Mn) also resulted in better-quality welds within a wider welding current range than ordinary oxygen-free copper (Cu-OF) used as reference material. On the basis of the deviation of results and the current range (current window) of the different materials, it can be maintained that the weldability of oxygen-free copper micro-alloyed with tin and/or manganese is clearly better. In particular, it was found out that among the tested materials, oxygen-free copper micro-alloyed with tin was best in terms of weldability.
The copper alloy according to the invention comprises oxygen-free copper (for example Cu-OF/ Cu-OFE) and, micro-alloyed therein, about 1 - 250 ppm, typically 1 - 120 ppm, preferably 10 - 30 ppm, tin (Sn) and/or about 1 - 150 ppm, typically 1 - 70 ppm, preferably 5 - 20 ppm, manganese (Mn). The electroconductivity of the copper alloy is over 100% IACS, typically over 101% IACS, preferably over 101.5% IACS.
The invention also relates to the use of copper alloy:
As a conductor strip;
To the use of copper alloy as tubular wires in wire cables, such as a coaxial cables;
To the use of copper alloy in weldable conductor arrangements;
To the use of copper alloy in weldable and workable conductor arrangements;
To the use of copper alloy as tubular wire in underwater cables; and
To the use of copper alloy as corrugated tubes.
Claims
1. An oxygen-free copper alloy, characterized in that said alloy comprises oxygen-free copper and, micro-alloyed therein, about 1 - 250 ppm tin (Sn) and/or about 1 - 150 ppm manganese (Mn).
2. A copper alloy according to claim 1 , characterized in that said copper alloy comprises tin (Sn) 1 - 120 ppm, preferably 10 - 30 ppm.
3. A copper alloy according to claim 1 or 2, characterized in that said copper alloy comprises manganese (Mn) 1 - 70 ppm, preferably 5 - 20 ppm.
4. A copper alloy according to any of the claims 1 - 3, characterized in that the electroconductivity of said alloy is over 100% IACS.
5. A copper alloy according to any of the claims 1 - 4, characterized in that the electroconductivity of said alloy is over 101% IACS.
6. The use of a copper alloy according to any of the claims 1 - 6 as conductor strip.
7. The use of a copper alloy according to any of the claims 1 - 6 as tubular wire in conductor cables, such as coaxial cables.
8. The use of a copper alloy according to any of the claims 1 - 6 in weldable conductor arrangements.
9. The use of a copper alloy according to any of the claims 1 - 6 in weldable and workable conductor arrangements.
10. The use of a copper alloy according to any of the claims 1 - 6 as tubular wire in underwater cables.
11. The use of a copper alloy according to any of the claims 1 - 6 in corrugated tubes.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR0207879-1A BR0207879A (en) | 2001-03-09 | 2002-03-08 | Oxygen-free, micro-alloyed copper alloy and its use |
| SK1151-2003A SK11512003A3 (en) | 2001-03-09 | 2002-03-08 | Micro-alloyed oxygen-free copper alloy and its use |
| JP2002571950A JP2004538362A (en) | 2001-03-09 | 2002-03-08 | Microalloyed oxygen-free copper alloy and its use |
| HU0303470A HUP0303470A3 (en) | 2001-03-09 | 2002-03-08 | Oxygen-free copper alloy and its use |
| EP02703649A EP1373588A1 (en) | 2001-03-09 | 2002-03-08 | Micro-alloyed oxygen-free copper alloy and its use |
| US10/471,191 US20040096353A1 (en) | 2001-03-09 | 2002-03-08 | Micro-alloyed oxygen-free copper alloy and its use |
| PL02363969A PL363969A1 (en) | 2001-03-09 | 2002-03-08 | Micro-alloyed oxygen-free copper alloy and its use |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20010473A FI113061B (en) | 2001-03-09 | 2001-03-09 | copper alloy |
| FI20010473 | 2001-03-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002072901A1 true WO2002072901A1 (en) | 2002-09-19 |
Family
ID=8560689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FI2002/000184 WO2002072901A1 (en) | 2001-03-09 | 2002-03-08 | Micro-alloyed oxygen-free copper alloy and its use |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20040096353A1 (en) |
| EP (1) | EP1373588A1 (en) |
| JP (1) | JP2004538362A (en) |
| CN (1) | CN1496416A (en) |
| BR (1) | BR0207879A (en) |
| CZ (1) | CZ20032372A3 (en) |
| FI (1) | FI113061B (en) |
| HU (1) | HUP0303470A3 (en) |
| PL (1) | PL363969A1 (en) |
| SK (1) | SK11512003A3 (en) |
| WO (1) | WO2002072901A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009024132A2 (en) * | 2007-08-21 | 2009-02-26 | Prymetall Gmbh & Co. Kg | Cable having a coaxial design for transmitting high-frequency signals and method for producing such a cable |
| ITUA20163211A1 (en) * | 2016-05-06 | 2017-11-06 | De Angeli Prod S R L | ELECTRIC CONDUCTOR FOR ELECTRIC WINDINGS, ESPECIALLY FOR CONTINUOUS TRAVEL CABLE |
| DK3622094T3 (en) | 2017-05-10 | 2021-09-27 | Haldor Topsoe As | Method for reducing the oxygen content of metallic copper |
| CN111549254A (en) * | 2020-04-29 | 2020-08-18 | 铜陵有色金属集团股份有限公司金威铜业分公司 | Oxygen-free copper-based microalloy and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3525605A (en) * | 1966-05-04 | 1970-08-25 | Outokumpu Oy | Method for decreasing the softening temperature and improving the electrical conductivity of high conductivity oxygen-free copper |
| US4059437A (en) * | 1975-07-02 | 1977-11-22 | Phelps Dodge Industries, Inc. | Oxygen-free copper product and process |
| US4233067A (en) * | 1978-01-19 | 1980-11-11 | Sumitomo Electric Industries, Ltd. | Soft copper alloy conductors |
| US4311522A (en) * | 1980-04-09 | 1982-01-19 | Amax Inc. | Copper alloys with small amounts of manganese and selenium |
| US5077005A (en) * | 1989-03-06 | 1991-12-31 | Nippon Mining Co., Ltd. | High-conductivity copper alloys with excellent workability and heat resistance |
-
2001
- 2001-03-09 FI FI20010473A patent/FI113061B/en not_active IP Right Cessation
-
2002
- 2002-03-08 US US10/471,191 patent/US20040096353A1/en not_active Abandoned
- 2002-03-08 WO PCT/FI2002/000184 patent/WO2002072901A1/en not_active Application Discontinuation
- 2002-03-08 SK SK1151-2003A patent/SK11512003A3/en unknown
- 2002-03-08 EP EP02703649A patent/EP1373588A1/en not_active Withdrawn
- 2002-03-08 HU HU0303470A patent/HUP0303470A3/en unknown
- 2002-03-08 PL PL02363969A patent/PL363969A1/en not_active Application Discontinuation
- 2002-03-08 CZ CZ20032372A patent/CZ20032372A3/en unknown
- 2002-03-08 JP JP2002571950A patent/JP2004538362A/en not_active Abandoned
- 2002-03-08 CN CNA028062434A patent/CN1496416A/en active Pending
- 2002-03-08 BR BR0207879-1A patent/BR0207879A/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3525605A (en) * | 1966-05-04 | 1970-08-25 | Outokumpu Oy | Method for decreasing the softening temperature and improving the electrical conductivity of high conductivity oxygen-free copper |
| US4059437A (en) * | 1975-07-02 | 1977-11-22 | Phelps Dodge Industries, Inc. | Oxygen-free copper product and process |
| US4233067A (en) * | 1978-01-19 | 1980-11-11 | Sumitomo Electric Industries, Ltd. | Soft copper alloy conductors |
| US4311522A (en) * | 1980-04-09 | 1982-01-19 | Amax Inc. | Copper alloys with small amounts of manganese and selenium |
| US5077005A (en) * | 1989-03-06 | 1991-12-31 | Nippon Mining Co., Ltd. | High-conductivity copper alloys with excellent workability and heat resistance |
Non-Patent Citations (1)
| Title |
|---|
| AHLSTROEM EWA: "Koppar och kopparlegeringar", SMS HANDBOK 8, no. 3, 2000 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ20032372A3 (en) | 2003-12-17 |
| US20040096353A1 (en) | 2004-05-20 |
| HUP0303470A3 (en) | 2005-10-28 |
| FI20010473L (en) | 2002-09-10 |
| JP2004538362A (en) | 2004-12-24 |
| HUP0303470A2 (en) | 2004-01-28 |
| BR0207879A (en) | 2004-03-02 |
| PL363969A1 (en) | 2004-11-29 |
| CN1496416A (en) | 2004-05-12 |
| FI113061B (en) | 2004-02-27 |
| FI20010473A0 (en) | 2001-03-09 |
| SK11512003A3 (en) | 2004-04-06 |
| EP1373588A1 (en) | 2004-01-02 |
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