EP1127948A2 - Superalliages monocristallins à base de nickel résistant à la corrosion à haute température - Google Patents

Superalliages monocristallins à base de nickel résistant à la corrosion à haute température Download PDF

Info

Publication number
EP1127948A2
EP1127948A2 EP95116194A EP95116194A EP1127948A2 EP 1127948 A2 EP1127948 A2 EP 1127948A2 EP 95116194 A EP95116194 A EP 95116194A EP 95116194 A EP95116194 A EP 95116194A EP 1127948 A2 EP1127948 A2 EP 1127948A2
Authority
EP
European Patent Office
Prior art keywords
percent
superalloy
single crystal
weight
casting
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
Application number
EP95116194A
Other languages
German (de)
English (en)
Other versions
EP1127948A3 (fr
EP1127948B1 (fr
Inventor
Gary L. Erickson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cannon Muskegon Corp
Original Assignee
Cannon Muskegon Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cannon Muskegon Corp filed Critical Cannon Muskegon Corp
Priority to ES95116194T priority Critical patent/ES2184779T3/es
Priority to DE69527557T priority patent/DE69527557T2/de
Priority to AT95116194T priority patent/ATE221138T1/de
Priority to EP95116194A priority patent/EP1127948B1/fr
Priority to DK95116194T priority patent/DK1127948T3/da
Publication of EP1127948A2 publication Critical patent/EP1127948A2/fr
Publication of EP1127948A3 publication Critical patent/EP1127948A3/fr
Application granted granted Critical
Publication of EP1127948B1 publication Critical patent/EP1127948B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%

Definitions

  • U.K. Patent Application Publication No. 2153848A discloses nickel-base alloys having a composition within the range of 13-15.6% chromium, 5-15% cobalt, 2.5-5% molybdenum, 3-6% tungsten, 4-6% titanium, 2-4% aluminum, and the balance essentially nickel without intentional additions of carbon, boron or zirconium, which are fabricated into single crystals.
  • the alloys taught by this reference claim an improvement in hot corrosion resistance accompanied by an increase in creep rupture properties, the need remains in the art for single crystal superalloys for industrial gas turbine applications having a superior combination of increased hot corrosion resistance, oxidation resistance, mechanical strength, large component castability and adequate heat treatment response.
  • Single crystal articles are generally produced having the low-modulus (001) crystallographic orientation parallel to the component dendritic growth pattern or blade stacking axis.
  • Face-centered cubic (FOC) superalloy single crystals grown in the (001) direction provide extremely good thermal fatigue resistance relative to conventionally cast polycrystalline articles. Since these single crystal articles have no grain boundaries, alloy design without grain boundary strengtheners, such as carbon, boron and zirconium, is possible. As these elements are alloy melting point depressants, their essential elimination from the alloy design provides a greater potential for high temperature mechanical strength achievement since more complete gamma prime solution and microstructural homogenization can be achieved relative to directionally solidified (DS) columnar grain and conventionally cast materials, made possible by a higher incipient melting temperature.
  • DS directionally solidified
  • alloys must be designed to avoid tendency for casting defect formation such as freckles, slivers, spurious grains and recrystallization, particularly when utilized for large cast components. Additionally, the alloys must provide an adequate heat treatment "window" (numeric difference between an alloy's gamma prime solvus and incipient melting point) to allow for nearly complete gamma prime solutioning. At the same time, the alloy compositional balance should be designed to provide an adequate blend of engineering properties necessary for operation in gas turbine engines. Selected properties generally considered important by gas turbine engine designers include: elevated temperature creep-rupture strength, thermo-mechanical fatigue resistance, impact resistanoe, hot corrosion and oxidation resistance, plus coating performance. In particular, industrial turbine designers require unique blends of hot corrosion and oxidation resistance, plus good long-term mechanical properties.
  • An alloy designer can attempt to improve one or two of these design properties by adjusting the compositional balance of known superalloys.
  • the unique superalloy of the present invention provides an excellent blend of the properties necessary for use in producing single crystal articles for operation in industrial and marine gas turbine engine hot sections.
  • This invention relates to a hot corrosion resistant nickel-based superalloy comprising the following elements in percent by weight: from about 14.2 to about 15.5 percent chromium, from about 2.0 to about 4.0 percent cobalt, from about 0.30 to about 0.45 percent molybdenum, from about 4.0 to about 5.0 percent tungsten, from about 4.5 to about 5.8 percent tantalum, from about 0.05 to about 0.25 percent columbium, from about 3.2 to about 3.6 percent aluminum, from about 4.0 to about 4.4 percent titanium, from about 0.01 to about 0.06 percent hafnium, and the balance nickel plus incidental impurities, the superalloy having a phasial stability number N V3B less than about 2.45.
  • the sum of aluminum plus titanium in this superalloy composition is from 7.2 to 8.0 percent by weight. Also, it is advantageous to have a Ti:Al ratio greater than 1 and a Ta:W ratio greater than 1 in the composition of the present invention.
  • the superalloy can also be comprised of from about 0 to about 0.05 percent carbon, from about 0 to about 0.03 percent boron, from about 0 to about 0.03 percent zinconium, from about 0 to about 0.25 percent rhenium, from about 0 to about 0.10 percent silicon, and from about 0 to about 0.10 percent manganese.
  • the base element is nickel. This invention provides a single crystal superalloy having an increased resistance to hot corrosion, an increased resistance to oxidation, and increased creep-rupture strength.
  • the article can be a component for a gas turbine engine and, more particularly, the component can be a gas turbine blade or gas turbine vane.
  • the superalloy compositions of this invention have a critically balanced alloy chemistry which results in a unique blend of desirable properties, including an increased resistance to hot corrosion, which are particularly suitable for industrial and marine gas turbine applications. These properties include: excellent bare hot corrosion resistance and creep-rupture strength; good bare oxidation resistance; good single crystal component castability, particularly for large blade and vane components; good solution heat treatment response; adequate resistance to cast component recrystallization; adequate component coatability and microstructural stability, such as long-term resistance to the formation of undesirable, brittle phases called topologically close-packed (TCP) phases.
  • TCP topologically close-packed
  • FIG. 1 is a chart of hot corrosion test results performed at three exposure temperatures on one embodiment of this invention and on four other alloys.
  • FIG. 2 is a graphical comparison of hot corrosion data from tests performed at 732°C (1350°F) on one embodiment of this invention and on two other alloys.
  • FIG. 3 is a graphical comparison of hot corrosion data from tests performed at 899°C (1650°F) on one embodiment of this invention and on two other alloys.
  • FIG. 4 is a graphical comparison of alloy strength and hot corrosion data from tests performed on one embodiment of this invention and on six other alloys.
  • FIG. 5 is a graphical comparison of oxidation data from tests performed at 1000°C (1832°F) on one embodiment of this invention and on two other alloys.
  • FIG. 6 is a graphical comparison of oxidation data from tests performed at 1010°C (1850°F) on one embodiment of the present invention and on two other alloys.
  • FIG. 7 is a graphical comparison of alloy strength and oxidation data from tests performed on one embodiment of this invention and on six other alloys.
  • the hot corrosion resistant nickel-based superalloy of the present invention comprises the following elements in percent by weight: Chromium about 14.2-15.5 Cobalt about 2.0-4.0 Molybdenum about 0.30-0.45 Tungsten about 4.0-5.0 Tantalum about 4.5-5.8 Columbium about 0.05-0.25 Aluminum about 3.2-3.6 Titanium about 4.0-4.4 Hafnium about 0.01-0.06 Nickel + Incidental impurities balance
  • This superalloy composition also has a phasial stability number N V38 less than about 2.45. Further, this invention has a critically balanced alloy chemistry which results in a unique blend of desirable properties useful for industrial and marine gas turbine engine applications.
  • These properties include a superior blend of bare hot corrosion resistance and creep-rupture strength relative to prior art single crystal superalloys for industrial and marine gas turbine applications, bare oxidation resistance, single crystal component castability, and microstructural stability, including resistance to TCP phase formation under high stress, high temperature conditions.
  • Superalloy chromium content is a primary contributor toward attaining superalloy hot corrosion resistance.
  • the superalloys of the present invention have a relatively high chromium content since alloy hot corrosion resistance was one of the primary design criteria in the development of these alloys.
  • the chromium is about 14.2-15.5% by weight.
  • the chromium content is from 14.3% to 15.0% by weight.
  • chromium provides hot corrosion resistance, it may also assist with the alloys' oxidation capability. Additionally, this superalloys' tantalum and titanium contents, as well as its Ti:Al ratio being greater than 1, are beneficial for hot corrosion resistance attainment.
  • chromium contributes to the formation of Cr and W-rich TCP phase and must be balanced accordingly in these compositions.
  • the cobalt content is about 2.0-4.0% by weight. In another embodiment of the present invention, the cobalt content is from 2.5% to 3.5% by weight.
  • the chromium and cobalt levels in these superalloys assist in making the superalloy solution heat treatable, since both elements tend to decrease an alloy's gamma prime solvus.
  • Proper balancing of these elements in the present invention in tandem with those which tend to increase the alloy's incipient melting temperature, such as tungsten and tantalum result in superalloxy compositions which have desirable solution heat treatment windows (numerical difference between an alloy's incipient melting point and its gamma prime solvus), thereby facilitating full gamma prime solutioning.
  • the cobalt content is also beneficial to the superalloy's solid solubility.
  • the tungsten content is about 4.0-5.0% by weight and, advantageously, the amount of tungsten is from 4.2% to 4.8% by weight.
  • Tungsten is added in these compositions since it is an effective solid solution strengthener and it can contribute to strengthening the gamma prime. Additionally, tungsten is effective in raising the alloy's incipient melting temperature.
  • the molybdenum content is about 0.30-0.45% by weight.
  • molybdemm is present in an amount of from 0.35% to 0.43% by weight.
  • Molybdenum is a good solid solution strengthener, but it is not as effective as tungsten and tantalum, and it tends to be a negative factor toward hot corrosion capability.
  • the addition of molybdenum is a means of assisting control of the overall alloy density in the compositions of this invention. It is believed that the relatively low molybdenum content is unique in this class of bare hot corrosion resistant nickel-based single crystal superalloys.
  • the aluminum content is about 3.2-3.6% by weight. Furthermore, the amount of aluminum present in these compositions is advantageously from 3.3% to 3.5% by weight.
  • Aluminum and titanium are the primary elements comprising the gamma prime phase, and the sum of aluminum plus titanium in the present invention is from 7.2 to 8.0 percent by weight. These elements are added in these compositions in a proportion and ratio consistent with achieving adequate alloy castability, solution heat treatability, phasial stability and the desired blend of high mechanical strength and hot corrosion resistance. Aluminum is also added to these alloys in proportions sufficient to provide oxidation resistance.
  • the titanium content is about 4.0-4.4% by weight.
  • titanium is present in this composition in an amount from 4.1% to 4.3% by weight.
  • These alloys' titanium content is relatively high and, therefore, is beneficial to the alloys' hot corrosion resistance. However, it can also have a negative effect on oxidation resistance, alloy castability and alloy response to solution heat treatment. Accordingly, it is critical that the titanium content is maintained within the stated range of this composition and the proper balancing of the aforementioned elemental constituents is maintained. Furthermore, maintaining the alloys' Ti:Al ratio greater than 1 is critical in achieving the desired bare hot corrosion resistance in these compositions.
  • the columbium content is about 0.05%-0.25% by weight and, advantageously, the columbium content is from 0.05% to 0.12% by weight.
  • Columbium is a gamma prime forming element and it is an effective strengthener in the nickel-based superalloys of this invention. Generally, however, columbium is a detriment to alloy oxidation and hot corrosion properties, so its addition to the compositions of this invention is minimized. Moreover, Columbium is added to this invention's compositions for the purpose of gettering carbon, which can be chemi-sorbed into component surfaces during non-optimized vacuum solution heat treatment procedures.
  • any carbon pick-up will tend to form columbium carbide instead of titanium or tantalum carbide, thereby preserving the greatest proportion of titanium and/or tantalum for gamma prime and/or solid solution strengthening in these alloys. Furthermore, it is critical that the sum of columbium plus hafnium is from 0.06 to 0.31 percent by weight in these compositions in order to enhance the strength of these superalloys.
  • the balance of this invention's superalloy compositions is comprised of nickel and small amounts of incidental impurities.
  • incidental impurities are entrained from the industrial process of production, and they should be kept to the least amount possible in the composition so that they do not affect the advantageous aspects of the superalloy.
  • these incidental impurities may include up to about 0.05 percent carbon, up to about 0.03 percent boron, up to about 0.03 percent zirconium, up to about 0.25 percent rhenium, up to about 0.10 percent silicon, and up to about 0.10 percent manganese. Amounts of these impurities which exceed the stated amounts could have an adverse effect upon the resulting alloy's properties.
  • the superalloys of this invention can be used to suitably make single crystal articles, such as components for industrial and marine gas turbine engines.
  • these superalloys are utilized to make a single crystal casting to be used under high stress, high temperature conditions characterized by an increased resistance to hot corrosion (sulfidation) under such conditions, particularly high temperature conditions involving corrosive atmospheres containing sulfur, sodium and vanadium contaminants, up to about 1922°F (1050°C). While these superalloys can be used for any purpose requiring high strength castings produced as a single crystal, their particular use is in the casting of single crystal blades and vanes for industrial and marine gas turbine engines.
  • the single crystal components made from this invention's compositions can be produced by any of the single crystal casting techniques known in the art.
  • single crystal directional solidification processes can be utilized, such as the seed crystal process and the choke process.
  • the single crystal castings made from the superalloys of the present invention can be aged at a temperature of from about 1800°F (982°C) to about 2125°F (1163°C) for about 1 to about 50 hours.
  • a temperature of from about 1800°F (982°C) to about 2125°F (1163°C) for about 1 to about 50 hours.
  • the optimum aging temperature and time for aging depends on the precise composition of the superalloy.
  • This invention provides superalloy compositions having a unique blend of desirable properties. These properties include: excellent bare hot corrosion resistance and creep-rupture strength; good oxidation resistance; good single crystal component castability, particularly for large blade and vane components; good solution heat treatment response; adequate resistance to cast component recrystallization; adequate component coatability and microstructural stability, such as long-term resistance to the formation of undesirable, brittle phases called topologically close-packed (TCP) phases.
  • TCP topologically close-packed
  • Test materials were prepared to investigate the compositional variations and ranges for the superalloys of the present invention.
  • One of the alloy compositions tested and reported below falls outside the claimed scope of the present invention, but is included for comparative purposes to assist in the understanding of the invention.
  • Representative alloy aim chemistries of materials tested are reported in Table 1 below.
  • AIM CHEMISTRIES ELEMENT CMSX-11C CMSX-11C' CMSX-11C" CMSX-11B C Lap Lap Lap Lap Cr 14.5 14.5 14.4 12.5 Co 3.0 2.5 2.9 6.0 Mo .40 .35 .40 0.55 W 4.4 4.6 4.5 5.0 Ta 4.95 5.1 5.1 5.15 Cb .10 .08 .10 0.20 Al 3.40 3.40 3.4 3.60 Ti 4.20 4.15 4.2 4.20 Hf .04 .03 .04 0.040 Ni BAL BAL BAL BAL N v3B 2.41 2.40 2.42 2.42 NOTE: Chemistries are in wt. %.
  • test specimens were further heat treated by aging initially at 2050°F (1121°C) to encourage a desirable ⁇ ' morphology and distribution, followed by secondary ages at 1600°F (871°C) and 1400°F (760°C), respectively (see Table 3 below).
  • HEAT TREATMENT ALLOY PEAK SOLUTION TEMP All test specimens were further heat treated by aging initially at 2050°F (1121°C) to encourage a desirable ⁇ ' morphology and distribution, followed by secondary ages at 1600°F (871°C) and 1400°F (760°C), respectively (see Table 3 below).
  • test bars were machined and low-stress ground to ASIM standard proportional specimen dimension for subsequent stress - and creep-rupture testing at various conditions of temperature and stress, according to standard ASTM procedure. Specimens removed from solid turbine blades were prepared similarly.
  • Table 5 shows the results of stress - and creep-rupture tests undertaken with the CMSX-11C alloy specimens. The tests were performed at conditions ranging 1400-1900°F (760-1038°C).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Powder Metallurgy (AREA)
EP95116194A 1995-10-13 1995-10-13 Superalliages monocristallins à base de nickel résistant à la corrosion à haute température Expired - Lifetime EP1127948B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES95116194T ES2184779T3 (es) 1995-10-13 1995-10-13 Superaleaciones monocristalinas a base de niquel resistente a la corroosion a temperatura elevada.
DE69527557T DE69527557T2 (de) 1995-10-13 1995-10-13 Einkristalline Superlegierungen mit guter Korrosionsbeständigkeit bei hohen Temperaturen
AT95116194T ATE221138T1 (de) 1995-10-13 1995-10-13 Einkristalline superlegierungen mit guter korrosionsbeständigkeit bei hohen temperaturen
EP95116194A EP1127948B1 (fr) 1995-10-13 1995-10-13 Superalliages monocristallins à base de nickel résistant à la corrosion à haute température
DK95116194T DK1127948T3 (da) 1995-10-13 1995-10-13 Højtemperaturkorrosionsresistente monokrystallinske nikkelbaserede superlegeringer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP95116194A EP1127948B1 (fr) 1995-10-13 1995-10-13 Superalliages monocristallins à base de nickel résistant à la corrosion à haute température

Publications (3)

Publication Number Publication Date
EP1127948A2 true EP1127948A2 (fr) 2001-08-29
EP1127948A3 EP1127948A3 (fr) 2001-09-05
EP1127948B1 EP1127948B1 (fr) 2002-07-24

Family

ID=8219715

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95116194A Expired - Lifetime EP1127948B1 (fr) 1995-10-13 1995-10-13 Superalliages monocristallins à base de nickel résistant à la corrosion à haute température

Country Status (5)

Country Link
EP (1) EP1127948B1 (fr)
AT (1) ATE221138T1 (fr)
DE (1) DE69527557T2 (fr)
DK (1) DK1127948T3 (fr)
ES (1) ES2184779T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115044805A (zh) * 2022-05-30 2022-09-13 北京科技大学 一种多性能平衡的镍基单晶高温合金及制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2153848A (en) * 1984-02-10 1985-08-29 United Technologies Corp High strength hot corrosion resistant single crystals
EP0207874A2 (fr) * 1985-05-09 1987-01-07 United Technologies Corporation Revêtements protecteurs pour superalliages, bien adaptés aux substrats
US4677035A (en) * 1984-12-06 1987-06-30 Avco Corp. High strength nickel base single crystal alloys
EP0240451A2 (fr) * 1986-04-03 1987-10-07 United Technologies Corporation Articles monocristallins à anisotropie réduite
EP0577316A2 (fr) * 1992-06-29 1994-01-05 Cannon-Muskegon Corporation Superalliage monocristallin à base de nickel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2153848A (en) * 1984-02-10 1985-08-29 United Technologies Corp High strength hot corrosion resistant single crystals
US4677035A (en) * 1984-12-06 1987-06-30 Avco Corp. High strength nickel base single crystal alloys
EP0207874A2 (fr) * 1985-05-09 1987-01-07 United Technologies Corporation Revêtements protecteurs pour superalliages, bien adaptés aux substrats
EP0240451A2 (fr) * 1986-04-03 1987-10-07 United Technologies Corporation Articles monocristallins à anisotropie réduite
EP0577316A2 (fr) * 1992-06-29 1994-01-05 Cannon-Muskegon Corporation Superalliage monocristallin à base de nickel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115044805A (zh) * 2022-05-30 2022-09-13 北京科技大学 一种多性能平衡的镍基单晶高温合金及制备方法

Also Published As

Publication number Publication date
EP1127948A3 (fr) 2001-09-05
ES2184779T3 (es) 2003-04-16
DK1127948T3 (da) 2002-11-11
ATE221138T1 (de) 2002-08-15
EP1127948B1 (fr) 2002-07-24
DE69527557D1 (de) 2002-08-29
DE69527557T2 (de) 2002-11-07

Similar Documents

Publication Publication Date Title
EP0577316B1 (fr) Superalliage monocristallin à base de nickel
JP2753148B2 (ja) ニッケル基単結晶超合金
AU2007345231C1 (en) Nickel-base alloy for gas turbine applications
WO1994000611A9 (fr) Superalliage monocristallin a base de nickel
CA1206398A (fr) Articles en superalliage monocristallin
US20110076181A1 (en) Nickel-Based Superalloys and Articles
EP0684321B1 (fr) Superalliage monocristallin à base de nickel résistant à la corrosion à haute température
EP1394278A1 (fr) Superalliage ayant un taux réduit de tantale et produit fabriqué à partir de cet alliage, et méthode de sélection d'un alliage avec un taux réduit de tantale
AU630623B2 (en) An improved article and alloy therefor
EP1715068B1 (fr) Alliage a base de nickel a haute resistance thermique et constituant de turbine a gaz l'utilisant
JPS6125773B2 (fr)
EP1127948B1 (fr) Superalliages monocristallins à base de nickel résistant à la corrosion à haute température
AU708992B2 (en) Hot corrosion resistant single crystal nickel-based superalloys
KR100224950B1 (ko) 공업용 가스터어빈 고온단부품
JP3209902B2 (ja) 高温腐食抵抗性の単結晶ニッケル系スーパーアロイ
KR100391184B1 (ko) 고온내식성단결정니켈계초내열합금
CZ266995A3 (en) In hot state corrosion resistant monocrystalline nickel-based high alloyed alloys
CA2160965C (fr) Superalliages monocristaux a base de nickel et resistant a la corrosion a chaud

Legal Events

Date Code Title Description
PUAB Information related to the publication of an a document modified or deleted

Free format text: ORIGINAL CODE: 0009199EPPU

PUAF Information related to the publication of a search report (a3 document) modified or deleted

Free format text: ORIGINAL CODE: 0009199SEPU

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

17P Request for examination filed

Effective date: 19960703

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 221138

Country of ref document: AT

Date of ref document: 20020815

Kind code of ref document: T

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG PATENTANWAELTE

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69527557

Country of ref document: DE

Date of ref document: 20020829

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2184779

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20030425

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20100923

Year of fee payment: 16

Ref country code: FR

Payment date: 20101004

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20100923

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20100912

Year of fee payment: 16

Ref country code: DK

Payment date: 20100923

Year of fee payment: 16

Ref country code: AT

Payment date: 20100923

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20101012

Year of fee payment: 16

Ref country code: DE

Payment date: 20101029

Year of fee payment: 16

Ref country code: CH

Payment date: 20101026

Year of fee payment: 16

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: CANNON-MUSKEGON CORPORATION

Free format text: CANNON-MUSKEGON CORPORATION#2875 LINCOLN#MUSKEGON, MICHIGAN 49441 (US) -TRANSFER TO- CANNON-MUSKEGON CORPORATION#2875 LINCOLN#MUSKEGON, MICHIGAN 49441 (US)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20101021

Year of fee payment: 16

Ref country code: BE

Payment date: 20101013

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20101019

Year of fee payment: 16

BERE Be: lapsed

Owner name: *CANNON-MUSKEGON CORP.

Effective date: 20111031

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20120501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20111013

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120501

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120501

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69527557

Country of ref document: DE

Effective date: 20120501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111102

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111013

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111013

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111014

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 221138

Country of ref document: AT

Kind code of ref document: T

Effective date: 20111013

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111013

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111013

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20130605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111014