US20070068608A1 - Method for the production of drop forge parts containing ti, zr, hf - Google Patents
Method for the production of drop forge parts containing ti, zr, hf Download PDFInfo
- Publication number
- US20070068608A1 US20070068608A1 US10/580,896 US58089604A US2007068608A1 US 20070068608 A1 US20070068608 A1 US 20070068608A1 US 58089604 A US58089604 A US 58089604A US 2007068608 A1 US2007068608 A1 US 2007068608A1
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- United States
- Prior art keywords
- process according
- drop
- titanium
- drop forged
- forged part
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
Definitions
- the invention concerns a process for production of drop forged parts, which are essentially comprised of titanium, zirconium, hafnium or a corresponding alloy. Besides this, the invention concerns drop forged parts of this type.
- Titanium in particular, is an interesting light metal, since it is almost 50% lighter than steel. For this reason Ti, Zr and Hf components are interesting in the manufacture of motor vehicles, particularly if unsprung or rotating, for example, oscillating masses are to be reduced.
- forged parts of bar stock, wires
- forged connecting rods, crankshafts and camshafts or valve parts can be mentioned.
- Titanium however exhibits, in comparison to metallic materials, a comparatively low modulus of elasticity (abbreviated: E-modulus in GPa; Materials Properties Handbook: Titanium Alloys, Editors: Boyer, Welsch, Collings, ASM International, Materials Park, OH 44073-002).
- E-modulus of titanium alloy is approximately 90 GPa, that of steel is approximately 210 GPa, that of Al-alloys is approximately 70 GPa and that of Mg-alloys is approximately 30-40 GPa.
- Drop forged moving titanium parts of motors such as, for example, connecting rods, crankshafts, camshafts and/or valve parts, can as a result tolerate only low loads.
- the task is solved by a process, in which materials containing 80 wt. % or more Ti and/or Zr and/or Hf, or alloys thereof, during deformation, are heated 5-15K above the ⁇ / ⁇ phase boundary (transition temperature) and subsequently are cooled. Preferably, the heating takes place over a period of approximately 20-60 minutes. Thereby it is achieved, that the E-modulus and rigidity of the employed Ti, Zr, Hf materials is increased in and during the manufacture of drop forge parts.
- the oscillating mass in a motor in particular connecting rods, crankshafts and camshafts and/or valves, can be reduced up to 35% or more, in comparison with steel components. Advantages are achieved with respect to improved motor dynamics, lower noise emissions, dispensing of the Lancester counter-weight as well as savings in fuel.
- FIG. 1 is a diagrammatic representation of FIG. 1 :
- FIG. 2
- FIG. 3 is a diagrammatic representation of FIG. 3 :
- ⁇ / ⁇ web arrangement (microstructure) of a Ti connecting rod of Ti Al 6 Fe2 Si deformed at 975° C. and then relaxation treated at 650° C. (white ⁇ - and grey ⁇ -lamella).
- Ti, Zr, Hf materials suited for purposes of the invention are titanium as such, zirconium as such, hafnium as such; preferred however are alloys containing up to 80 wt. % or more Ti and/or Zr and/or Hf, preferably 90 wt. %. Particularly preferred are however titanium alloys with 80 wt. % titanium, preferably 90 wt. % titanium. Zr and Hf can be contained as minor components in the range of 1-20 wt. %, preferably 5-15 wt. %. Likewise, incidental amounts of conventional metals can be contained, such as Al, Si, Mg, Se, Ni, Co, Mo, V or other light and heavy metals. Further preferred alloys for employment in motor vehicle construction include Ti Al 6 V 4 or Ti Al 6 Fe2 Si.
- ⁇ / ⁇ -Ti-alloys or, as the case may be, ⁇ / ⁇ -Ti containing materials are employed which have both a high strength, cubic space-centered ⁇ -phase as well as hexagonal ⁇ -phase with high E-modulus.
- high temperature deformation more ⁇ -phases are produced and in the low temperature deformation, more ⁇ -phases are produced.
- deformation occurs in the ⁇ / ⁇ zone, and namely, with heating 5-15° C., preferably 8-10-12° C. above the ⁇ / ⁇ phase boundary (transition temperature).
- the duration of heating in the indicated temperature range is at least to twenty minutes to forty-five minutes or longer, preferably however not longer than one hour.
- FIG. 1 An ⁇ / ⁇ microstructure, or as the case may be, an inventive composite, is produced ( FIG. 1 ), which combines the high strength characteristics of the ⁇ phase with the higher E-modulus of the ⁇ phase.
- This temperature-dependent deformation range is to be selected very narrowly, or as the case may be, heating or deformation temperatures are to be adjusted to ⁇ 15 K, preferably ⁇ 5 K, from the optimal deformation temperature of 10 K above the ⁇ / ⁇ phase limit. Departing from this range, then either isolated ⁇ or ⁇ phases exists in a ⁇ or, as the case may be, ⁇ base matrix ( FIG.
- the desired ⁇ / ⁇ microstructure or grain structure can be improved inventively with respect to a stronger interlacing of the ⁇ and ⁇ phases, in that after the deformation, it is slowly cooled in air or, as the case may be, in a gas atmosphere. Thereby the ⁇ / ⁇ microstructure is further interfused by the ⁇ -phase. As a result, an alternating of the arrangement of the ⁇ phase and the ⁇ phase in the material is achieved. Basically, a mixed phase in an ⁇ / ⁇ web structure is obtained.
- a relaxation treatment can follow at 650 ⁇ 50° C.
- the break elongation achieved by the inventive process lies, in the case of alloys, (for example, Ti Al 6 V 4 Ti Al 6 Fe2 Si) at above 1,100 MPa or, as the case may be, the technical elastic limit lies above 1,000 MPa.
- alloys for example, Ti Al 6 V 4 Ti Al 6 Fe2 Si
- the technical elastic limit lies above 1,000 MPa.
- the oscillating mass can be reduced by up to 35%-45% in the case of Ti Al 6 Fe2 Si connecting rods in comparison to high stiffness steel connecting rods.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Forging (AREA)
- Shafts, Cranks, Connecting Bars, And Related Bearings (AREA)
- Heat Treatment Of Articles (AREA)
Abstract
The invention relates to a method for the production of drop forge parts essentially comprising titanium, zirconium, hafnium or a corresponding alloy, enabling rigidity thereof to be increased.
Description
- This application is a national stage of PCT/EP2004/012952 filed Nov. 16, 2004 and based upon DE 103 55 892.6 filed on Nov. 29, 2003 under the International Convention.
- 1. Field of the Invention
- The invention concerns a process for production of drop forged parts, which are essentially comprised of titanium, zirconium, hafnium or a corresponding alloy. Besides this, the invention concerns drop forged parts of this type.
- Titanium, in particular, is an interesting light metal, since it is almost 50% lighter than steel. For this reason Ti, Zr and Hf components are interesting in the manufacture of motor vehicles, particularly if unsprung or rotating, for example, oscillating masses are to be reduced. In this connection drop forged parts (of bar stock, wires), in particular forged connecting rods, crankshafts and camshafts or valve parts can be mentioned. Titanium however exhibits, in comparison to metallic materials, a comparatively low modulus of elasticity (abbreviated: E-modulus in GPa; Materials Properties Handbook: Titanium Alloys, Editors: Boyer, Welsch, Collings, ASM International, Materials Park, OH 44073-002). Thus, the E-modulus of titanium alloy is approximately 90 GPa, that of steel is approximately 210 GPa, that of Al-alloys is approximately 70 GPa and that of Mg-alloys is approximately 30-40 GPa.
- Drop forged moving titanium parts of motors, such as, for example, connecting rods, crankshafts, camshafts and/or valve parts, can as a result tolerate only low loads.
- 2. Description of Related Art
- In the state of the art, coating processes for components are described, which lead to a hardening of the titanium alloy. DE 36 15 425 concerns a time and labor intensive plasma coating process for improving abrasion resistance of surface layers of titanium alloy machine components.
- It is the task of the present invention to provide a process for production of drop forge parts, which are comprised essentially of Ti, Zr, Hf or a corresponding alloy, in which a higher E-modulus of the drop forge parts is achieved.
- The task is solved by a process, in which materials containing 80 wt. % or more Ti and/or Zr and/or Hf, or alloys thereof, during deformation, are heated 5-15K above the α/β phase boundary (transition temperature) and subsequently are cooled. Preferably, the heating takes place over a period of approximately 20-60 minutes. Thereby it is achieved, that the E-modulus and rigidity of the employed Ti, Zr, Hf materials is increased in and during the manufacture of drop forge parts.
- With the aid of the inventive process the oscillating mass in a motor, in particular connecting rods, crankshafts and camshafts and/or valves, can be reduced up to 35% or more, in comparison with steel components. Advantages are achieved with respect to improved motor dynamics, lower noise emissions, dispensing of the Lancester counter-weight as well as savings in fuel.
- Description of the figures:
-
FIG. 1 : - α/β web arrangement (microstructure) of a Ti connecting rod of Ti Al 6 Fe2 Si forged at 975° C. (white α- and grey β-lamella).
-
FIG. 2 : - α/β web arrangement (microstructure) of a Ti connecting rod forged at 990° C. of Ti Al 6 Fe2 Si with isolated white α islands.
-
FIG. 3 : - α/β web arrangement (microstructure) of a Ti connecting rod of Ti Al 6 Fe2 Si deformed at 975° C. and then relaxation treated at 650° C. (white α- and grey β-lamella).
- As the Ti, Zr, Hf materials, suited for purposes of the invention are titanium as such, zirconium as such, hafnium as such; preferred however are alloys containing up to 80 wt. % or more Ti and/or Zr and/or Hf, preferably 90 wt. %. Particularly preferred are however titanium alloys with 80 wt. % titanium, preferably 90 wt. % titanium. Zr and Hf can be contained as minor components in the range of 1-20 wt. %, preferably 5-15 wt. %. Likewise, incidental amounts of conventional metals can be contained, such as Al, Si, Mg, Se, Ni, Co, Mo, V or other light and heavy metals. Further preferred alloys for employment in motor vehicle construction include Ti Al 6 V 4 or Ti Al 6 Fe2 Si.
- In accordance with the invention, α/β-Ti-alloys or, as the case may be, α/β-Ti containing materials are employed which have both a high strength, cubic space-centered β-phase as well as hexagonal α-phase with high E-modulus. In the so-called high temperature deformation, more β-phases are produced and in the low temperature deformation, more α-phases are produced. In accordance with the invention, deformation occurs in the α/β zone, and namely, with heating 5-15° C., preferably 8-10-12° C. above the α/β phase boundary (transition temperature). With pure titanium, for example at 882.5° C., α-Ti transitions into β-Ti (so-called α/β phase boundary limit), that is, the heating should inventively occur at 887-897° C. For Ti Al 6 V 4 or Ti Al 6 Fe2 Si, the corresponding preferred heating value is 975° C.±15° C.
- The duration of heating in the indicated temperature range is at least to twenty minutes to forty-five minutes or longer, preferably however not longer than one hour.
- Thereby, during heating, the α-low temperature phase is replaced by the β-high temperature phase in such a manner, that an α/β microstructure, or as the case may be, an inventive composite, is produced (
FIG. 1 ), which combines the high strength characteristics of the β phase with the higher E-modulus of the α phase. This temperature-dependent deformation range is to be selected very narrowly, or as the case may be, heating or deformation temperatures are to be adjusted to ±15 K, preferably ±5 K, from the optimal deformation temperature of 10 K above the α/β phase limit. Departing from this range, then either isolated α or β phases exists in a β or, as the case may be, α base matrix (FIG. 2 ), so that disadvantageously the low E-modulus of the β phase results. The desired α/β microstructure or grain structure can be improved inventively with respect to a stronger interlacing of the α and β phases, in that after the deformation, it is slowly cooled in air or, as the case may be, in a gas atmosphere. Thereby the α/β microstructure is further interfused by the α-phase. As a result, an alternating of the arrangement of the α phase and the β phase in the material is achieved. Basically, a mixed phase in an α/β web structure is obtained. Inventively, after the deformation, a relaxation treatment can follow at 650±50° C. in order to achieve, besides the reduction of undesired deformation tensions, a stronger intermixing of the α/β microstructure with the α-phase with high E-modulus (FIG. 3 ). Thereby, the heating or glowing time is to be limited in such a manner that the α/β microstructure is not destroyed. With these Ti connecting rods drop forged at 975° C.±5° C., which after the deformation are slowly cooled in air, there can be achieved in an α/β alloy Ti Al 6 V with an E-modulus of 130 GPa or, as the case may be, a Ti Al 6 Fe2 Si an E-modulus of 140 GPa be realized. A subsequent relaxation heating at 650° C. brings about an additional E-modulus increase of at least 5 GPa. The break elongation achieved by the inventive process lies, in the case of alloys, (for example, Ti Al 6 V 4 Ti Al 6 Fe2 Si) at above 1,100 MPa or, as the case may be, the technical elastic limit lies above 1,000 MPa. This corresponds to the rigidity values of high stiffness β-Ti alloys, which lie above that of steel. Thus, advantageously the oscillating mass can be reduced by up to 35%-45% in the case of Ti Al 6 Fe2 Si connecting rods in comparison to high stiffness steel connecting rods.
Claims (16)
1-10. (canceled)
11. A process for production of a drop forged part made of a metal alloy containing 80 wt. % or more Ti and/or Zr and/or Hf, wherein the drop forged part during deforming is heated 5-15 K above the α/β phase boundary to form β phases and is subsequently cooled.
12. A process according to claim 11 , wherein said drop forged part is a moving part of a motor.
13. A process according to claim 11 , wherein said drop forged part is a connecting rod, crankshaft, camshaft or a valve.
14. A process according to claim 11 , wherein the material is heated for 20-60 minutes.
15. A process according to claim 11 , wherein the relaxation thermal treatment occurs at 600-700° C. after cooling.
16. A process according to claim 11 , wherein the E-modulus and the rigidity of the Ti and/or Zr and/or Hf containing materials, or alloys thereof, are increased.
17. A process according to claim 11 , wherein the alloy is a titanium alloy containing 1-20 wt. % Zr and/or Hf and optionally incidental amounts of other light or heavy metals.
18. A process according to claim 11 , wherein the alloy is a titanium alloy containing 5-15 wt. % Zr and/or Hf and optionally incidental amounts of other light or heavy metals.
19. A process according to claim 11 , wherein the alloy is a titanium alloy containing 90 wt. % titanium.
20. A process according to claim 11 , wherein the alloy is a titanium alloy selected from Ti Al 6 V 4 and Ti Al 6 Fe2 Si.
21. A process according to claim 11 , wherein an α/β micro structure or composite material is formed.
22. A process according to claim 11 , wherein the drop forge part after forging is slowly cooled in air.
23. A drop forged part made of a metal alloy containing 80 wt. % or more Ti and/or Zr and/or Hf, made by a process comprising:
heating, during deforming, 5-15 K above the α/β phase boundary to form β phases; and
subsequently cooling.
24. A drop forged part as in claim 23 , wherein said part is a connecting rod, a crankshaft, a camshaft or a valve part.
25. A drop forged part made of a metal alloy containing 80 wt. % or more Ti and/or Zr and/or Hf, made by a process comprising:
heating, during deforming, 5-15 K above the α/β phase boundary to form β phases; and
subsequently cooling in such a manner that the E-modulus is increased.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10355892A DE10355892B4 (en) | 2003-11-29 | 2003-11-29 | Process for producing Ti, Zr, Hf-containing drop forgings |
| DE10355892.6 | 2003-11-29 | ||
| PCT/EP2004/012952 WO2005052201A2 (en) | 2003-11-29 | 2004-11-16 | METHOD FOR THE PRODUCTION OF DROP FORGE PARTS CONTAINING Ti, Zr, Hf |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20070068608A1 true US20070068608A1 (en) | 2007-03-29 |
Family
ID=34625400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/580,896 Abandoned US20070068608A1 (en) | 2003-11-29 | 2004-11-16 | Method for the production of drop forge parts containing ti, zr, hf |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20070068608A1 (en) |
| JP (1) | JP2007512433A (en) |
| DE (1) | DE10355892B4 (en) |
| WO (1) | WO2005052201A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104019184A (en) * | 2013-03-01 | 2014-09-03 | 福特环球技术公司 | Internal combustion engine with compensation weight arranged on crankshaft and serving as imbalance |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104439981B (en) * | 2014-12-11 | 2017-05-10 | 西部钛业有限责任公司 | Manufacturing method of TA6 titanium alloy large-width thin plate |
| CN105478521B (en) * | 2016-01-21 | 2017-11-21 | 南京佑天金属科技有限公司 | The process that hafnium filament is drawn |
| CN110076533B (en) * | 2019-05-24 | 2021-11-02 | 宝鸡拓普达钛业有限公司 | Preparation method of TC4 step shaft applied to petroleum lubricator |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474631A (en) * | 1946-06-27 | 1949-06-28 | Cleveland H Jelley | Internal-combustion engine |
| US4055975A (en) * | 1977-04-01 | 1977-11-01 | Lockheed Aircraft Corporation | Precision forging of titanium |
| US6077369A (en) * | 1994-09-20 | 2000-06-20 | Nippon Steel Corporation | Method of straightening wire rods of titanium and titanium alloy |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62170464A (en) * | 1986-01-22 | 1987-07-27 | Hitachi Ltd | Manufacture of moving vane for turbine |
| DE3615425A1 (en) * | 1986-05-07 | 1987-11-12 | Thyssen Edelstahlwerke Ag | PERFORMANCE OF MACHINE ELEMENTS FROM TECHNICAL TITANIUM ALLOYS THROUGH SURFACE COATING IN THE PLASMA OF GLIMMENT CHARGES |
| DE3622433A1 (en) * | 1986-07-03 | 1988-01-21 | Deutsche Forsch Luft Raumfahrt | METHOD FOR IMPROVING THE STATIC AND DYNAMIC MECHANICAL PROPERTIES OF ((ALPHA) + SS) TIT ALLOYS |
| JPS6468454A (en) * | 1987-09-08 | 1989-03-14 | Honda Motor Co Ltd | Method for removing strain of titanium or titanium alloy at the time of forging |
| DE4318424C2 (en) * | 1993-06-03 | 1997-04-24 | Max Planck Inst Eisenforschung | Process for the production of moldings from alloys based on titanium-aluminum |
| DE10150674B4 (en) * | 2000-12-15 | 2008-02-07 | Leistritz Ag | Process for the production of heavy-duty components made of TiAl alloys |
-
2003
- 2003-11-29 DE DE10355892A patent/DE10355892B4/en not_active Expired - Fee Related
-
2004
- 2004-11-16 WO PCT/EP2004/012952 patent/WO2005052201A2/en active Application Filing
- 2004-11-16 JP JP2006540282A patent/JP2007512433A/en not_active Abandoned
- 2004-11-16 US US10/580,896 patent/US20070068608A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474631A (en) * | 1946-06-27 | 1949-06-28 | Cleveland H Jelley | Internal-combustion engine |
| US4055975A (en) * | 1977-04-01 | 1977-11-01 | Lockheed Aircraft Corporation | Precision forging of titanium |
| US6077369A (en) * | 1994-09-20 | 2000-06-20 | Nippon Steel Corporation | Method of straightening wire rods of titanium and titanium alloy |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104019184A (en) * | 2013-03-01 | 2014-09-03 | 福特环球技术公司 | Internal combustion engine with compensation weight arranged on crankshaft and serving as imbalance |
| US20140245985A1 (en) * | 2013-03-01 | 2014-09-04 | Ford Global Technologies, Llc | Internal combustion engine with compensation weight arranged on the crankshaft and serving as an imbalance, and method for production of the crankshaft |
| US9121472B2 (en) * | 2013-03-01 | 2015-09-01 | Ford Global Technologies, Llc | Internal combustion engine with compensation weight arranged on the crankshaft and serving as an imbalance, and method for production of the crankshaft |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10355892B4 (en) | 2007-01-04 |
| JP2007512433A (en) | 2007-05-17 |
| WO2005052201A3 (en) | 2006-02-09 |
| DE10355892A1 (en) | 2005-06-30 |
| WO2005052201A2 (en) | 2005-06-09 |
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Owner name: DAIMLERCHRYSLER AG, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BARTH, ANDREAS;REEL/FRAME:018182/0069 Effective date: 20060424 |
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