EP2483020A1 - Method of production of nano-structural titanium semis for implants - Google Patents
Method of production of nano-structural titanium semis for implantsInfo
- Publication number
- EP2483020A1 EP2483020A1 EP10755078A EP10755078A EP2483020A1 EP 2483020 A1 EP2483020 A1 EP 2483020A1 EP 10755078 A EP10755078 A EP 10755078A EP 10755078 A EP10755078 A EP 10755078A EP 2483020 A1 EP2483020 A1 EP 2483020A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium
- nano
- powder
- casing
- production
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
- B22F3/204—Continuous compaction with axial pressure and without reduction of section
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
- B22F2003/208—Warm or hot extruding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/04—Nanocrystalline
Definitions
- the invention relates to the field of metal forming and metallurgy, for which it resolves the method of production of nano-structural titanium semis suitable for use for implants, particularly for dental applications.
- the dental implants based on titanium are produced either from titanium alloys or from castings made by melting of commercially pure coarsegrained titanium. Materials for the manufacture of implants must meet high requirements concerning their strength, chemical purity, bio-compatibility, conditions for osteo-integration, wetting, adherence of tissue cells, etc.
- Titanium alloys have high strength, but their disadvantage is the presence of impurities, which act in human body as allergens.
- a super-plastic duplex alloy of a and ⁇ titanium Ti-6AL-4V is known, which was previously considered as suitable for implants. Later on it was, however, established that vanadium in these alloys is toxic, and also aluminium is also considered as potentially toxic element.
- Other known titanium alloys also contain elements that are toxic for human organism.
- the alloys used in dental applications Ti-20Cr0.2Si, Ti-20Pd-5cr, Ti-13Cu-4.5Ni contain elements that are classified as allergens.
- CZ U 17408 describes the problems arising from the use of titanium alloys for the implants caused by the fact that due to allergies it is recommended to perform a specific surface treatment on the implant, which creates a modified surface layer with qualitatively more satisfactory mechanical properties, and removes part of undesirable ingredients.
- the cited source for example recommends application of surface treatment by effects of an aqueous solution of hydrofluoric acid, or with addition of nitric acid.
- ECAP Equal Channel Angular Pressing
- a matrix in a form of a casing containing a cavity is used, in which the cavity form a through channel of circular cross-section, into which a wire is inserted wire and here a pressure from two sides is applied to it by mechanical devices called extruders. Pressure from two sides is achieved by the fact that the channel is bent at an angle and/or it is tapered, and the extruder is pushed in direction of the channel taper.
- Arrangement of matrices is described for example in CZ U 18713. Disadvantage of that solution, in comparison with dental metals in the form of alloys, consists in low values of strength properties, normally around 650 MPa. It is therefore desirable, in order to maintain low modulus of elasticity, to increase the strength of the final product without the use elements that may be only potentially toxic or allergenic.
- the CEC method of cyclic extrusion is generally known.
- This method of forming also uses a matrix with a through channel, through which the repeated extrusion of material is conducted by an extruder, while this material is usually based on metal casting.
- Preparation of nano-materials from any types of metals or metal alloys is not yet sufficiently known. Successful implementation depends on choosing the appropriate method and specific equipment, on the structure, chemical composition, purity and size of material and on many other circumstances. Possible success or failure depends on the findings and compliance with specific conditions for each material, which is still under investigation.
- New method of production of titanium semis for implants has been resolved, which involves first production of titanium powder of at least technical purity by powder metallurgy, which is, however, not melt but compressed, the titanium powder in the compressed is sintered, and afterwards the sintered material is processed by repeated extrusion by the CEC technology to a compact poly-crystalline nano-titanium, from which the implant is shaped by commonly used methods.
- Titanium powder without toxic ingredients is advantageously used, with the grain size up to 100 nm and titanium content of 98 weight %, is placed into the casing closed from one side, the casing with the powder is placed into the forming matrix and the powder in the casing is pressed using push of extruder on the powder in the casing to a density of at least 4050 kgm 3 , which corresponds approximately to 90% of theoretical density of compact titanium.
- Titanium powder is advantageously placed into the channel of circular cross-section situated in a metallic casing, where this channel has advantageously a height to diameter ratio of 2.5 : 1 and it is closed at one end by a bottom. Compression of titanium powder is made by pushing of the extruder through the channel open end inside on the contained powder in direction against the bottom of the channel. At the same time casing with the powder may be extruded through the matrix.
- the titanium powder When the titanium powder is compressed to a specified density, it is appropriate to remove the excess part of the casing with free space above the compressed powder. The open end of the casing is then hermetically closed and the compressed powder is sintered.
- Sintering creates is from the powder a compact material. If the casing according to the invention is used a titanium body of cylindrical shape is formed form the powder. Before repeated extrusion, between individual extrusions or after extrusion of the sintered material through the matrix by the CEC method it is appropriate to remove the casing from the sintered material.
- Sintering of the compressed titanium powder is advantageously carried out at the temperature from 1250 to 1450°C, which corresponds to approximately 0.8 of the melting temperature of pure titanium, for a period of 1.5 to 2.5 hours
- the sintered material is then repeatedly extruded through the matrix by the CEC method of cyclic compression, advantageously at the temperature from 220 to 250°C, which corresponds to a homologous temperature of approximately 0.25 to 0.27.
- homologous temperature we understand the ratio of the forming temperature to the melting temperature.
- the sintered material according to the invention is extruded repeatedly through the matrix by the CEC method of cyclic compression until it achieves the specified average grain size of at least 100 nm.
- Refinement of the structure is satisfactory if extrusion of the sintered titanium material through the matrix by the CEC method of cyclic compression is performed under the conditions according to this invention at least five times, advantageously at least ten times.
- nano-titanium body is made of nano-titanium with grains of satisfactory structure, advantageously with an average size of 100 to 150 nm, thus produced nano-titanium body is further processed by drawing through a die, advantageously at the temperature from 160 to 200 ° C, which corresponds approximately to homologous temperature of 0.22 to 0.25.
- the invention is usable in the field of human and veterinary medicine. It makes it possible to produce material, which is a semis suitable for implants, especially for dental implants.
- material which is a semis suitable for implants, especially for dental implants.
- a compact, polycrystalline, semis is obtained, from which it possible to produce with use of common machining technologies for example dental implants, which in comparison to classical coarse-grained titanium are characterised by high strength Rm 1070 to 1200 MPa and high yield strength, an optimal elongation of approximately 12%, better bio-compatibility in comparison with titanium alloys, and in comparison with other implants, such as dental metallic implants, it has low value of modulus of elasticity in tension E, 100 GPa or less.
- Strength of nano- titanium produced according to the invention is approximately three times higher than strength of normal coarse-grained titanium, which will allow use of implants of a smaller diameter with preservation of comparable load capacity as that of standard implant of larger diameter, made of coarse-grained titanium.
- Material produced by the method according to the invention is usable in particular for dental technology.
- the implant thus prepared can be used for example as a pillar in the area of insufficient alveolar thickness.
- Nano-structural titanium retains all the important properties from the viewpoint of medicine, thanks to which pure titanium became the preferred material also for dental implants. At the same time nano- titanium outperforms other materials used in this application by its specific mechanical properties that are important for maintaining long-term safety function of the implant.
- nTiGr4 has 2.25 times higher ultimate tensile strength than the coarse-grained titanium cpTiGr4, 1.35 times higher breaking strength than the implants made of alloy Ti-6 AI-4V, which contains potentially toxic elements, 1.37 times and 1.44 times higher breaking strength than the alloy Ti-6AI-7Nb and Ti-15Mo-SZr.
- FIG. 1 shows a casing with titanium powder closed from one side
- Figure 2 shows process of compression of the titanium powder in the casing situated in the matrix by action of extruder
- Figure 3 shows the casing with the compressed powder and free space above the powder after compression
- Figure 4 shows the compressed powder in the rest of the casing after cutting of the open part of the casing along the line AA shown in the previous figure
- Figure 5 shows the process of refining the material structure by illustration of three stages A, B and C of the condition of the casing with the sintered material during extrusion through a matrix by the CEC method
- A, B shows a compact body of nano-titanium, where A shows the casing with nano-titanium, and B shows the same after removal of the casing, Figure 7 shows processing of nano-titanium by its drawing through the die to a wire, and Figure 8 shows the final product in the form of wire made of nano-titanium.
- An illustrative example of carrying out the invention is the following procedure for the production of nano-structural titanium semis for implants, the individual production stages of which are shown progressively, as they should follow each other, in the Figures 1 to 8
- Production of nano-structural titanium semis for implants starts by manufacture of titanium powder of at least technical purity by using known methods of powder.
- a powder with grain size up to 100 nanometers, nm and the following composition was used: element weight % in titanium powder
- Titanium powder was poured from one side of the closed casing 1, as it is shown in Figure 1.
- the casing 1 made of stainless steel, contains for this purpose the channel 2 of circular cross-section.
- the channel 2 has a height to diameter ratio of 2.5:1 and it is closed at the lower end by the bottom 3. Compression of the powder is shown in Fig.2. It was carried with use of methods of forming, namely by extrusion through the matrix 4, by pushing the forming extruder 5 against the bottom 3 of the channel 2, as indicated by an arrow in Figure 2.
- the extrusion represents such a pressure, that the casing 1 deforms under it adequately to the space in the matrix 4.
- the powder has been compressed after one extrusion to a specified density of 4050 kgm "3 .
- the casing1 containing the sintered titanium material was removed from the furnace and inserted into the thermostat, where it was cooled down to 250°C.
- the casing 1 containing the sintered material was then repeatedly extruded through the matrix 4 by the extruder 5 by the CEC method of cyclic compression at temperatures ranging from 220 to 250°C, as shown in Fig.5.
- the images marked as A, B, C illustrate various positions of extruded material and method of material compression in the casing 1 during the extrusion process, with the arrows indicating the direction of pressure forces F1 and F2 on exerted on the extruders 5 in the matrix 4.
- the extrusion was carried out repeatedly through the tapered part of the matrix 4 by alternation of the dominance of the force exerted on the upper or lower extruder 5, until the limit of the specified average grain size of 100 nm was reached.
- repeated extrusion by the CEC method under the conditions according to the invention resulted in changes of the structure of the processed material to nano-titanium. At this temperature and with observation of the optimal conditions according to the invention this happens after approximately ten extruions. In this particular case, the extrusion was performed twelve times, by which an average grain size from 100 to 150 nm was achieved.
- Fig. 6 illustrates at the position A the encapsulated body made of nano- titanium material, and at the position B the same body after removal of the original elements and elements added later of the casing 1. This concerned specifically removal of the original part of the casing 1 with the bottom 3, and cutting-off of the lid 6.
- the body thus obtained had a shape of a cylinder.
- the nano-titanium body thus produced after removal of the casing was processed by drawing through the die 7 at the temperature of approx. 180°C to a wire with diameter of 6 mm, as shown in Figure 7 and 8.
- Figure 7 shows drawing through the die 7, i.e. the next step at processing of nano-titanium realised by method of unidirectional drawing through the die 7 with use of the force F, where the arrow shows the direction of drawing of the nano-titanium wire in the die 7, and Figure 8 illustrates schematically the produced semis.
- the above procedure according to the invention produced material with the following mechanical properties. Strength Rm was 1070 MPa, modulus of elasticity in tension E was 100 GPa, elongation A was 2%, limit size of contained grain d z was 100 to 150 nm.
- This material could already be processed by common methods of shaping, e.g. by machining, to produce an implant.
- procedure according to the invention produced from titanium powder poured into the channel 2 with diameter of 26 mm in the casing 3 a nano-titanium wire with diameter of 6 mm, suitable for the manufacture of dental mini implants.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CZ20090640A CZ302421B6 (en) | 2009-10-01 | 2009-10-01 | Process for producing nanostructural titanium half-finished product for implants |
PCT/CZ2010/000071 WO2011038702A1 (en) | 2009-10-01 | 2010-06-15 | Method of production of nano-structural titanium semis for implants |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2483020A1 true EP2483020A1 (en) | 2012-08-08 |
EP2483020B1 EP2483020B1 (en) | 2013-12-04 |
Family
ID=43528341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10755078.2A Not-in-force EP2483020B1 (en) | 2009-10-01 | 2010-06-15 | Method of production of nano-structural titanium semis for implants |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2483020B1 (en) |
CZ (1) | CZ302421B6 (en) |
WO (1) | WO2011038702A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140271336A1 (en) | 2013-03-15 | 2014-09-18 | Crs Holdings Inc. | Nanostructured Titanium Alloy And Method For Thermomechanically Processing The Same |
CN110508635B (en) * | 2019-08-27 | 2021-07-30 | 太原理工大学 | Asymmetric reciprocating extrusion device with separated male die and machining method |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5573401A (en) * | 1989-12-21 | 1996-11-12 | Smith & Nephew Richards, Inc. | Biocompatible, low modulus dental devices |
US5494541A (en) * | 1993-01-21 | 1996-02-27 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Production of aluminum alloy |
US6399215B1 (en) * | 2000-03-28 | 2002-06-04 | The Regents Of The University Of California | Ultrafine-grained titanium for medical implants |
US8043404B2 (en) * | 2005-02-22 | 2011-10-25 | Dynamet Technology, Inc. | High extrusion ratio titanium metal matrix composites |
WO2007035805A2 (en) * | 2005-09-20 | 2007-03-29 | Purdue Research Foundation | Biocompatable nanophase materials |
CZ17408U1 (en) | 2006-12-01 | 2007-03-26 | Dluhos@Ludek | Metallic implant |
US20090088845A1 (en) * | 2007-09-24 | 2009-04-02 | Stanley Abkowitz | Titanium tantalum oxygen alloys for implantable medical devices |
CZ18713U1 (en) | 2008-06-13 | 2008-06-30 | Vysoká škola bánská - Technická univerzita Ostrava | Die for producing nanomaterials using extreme plastic deformation |
-
2009
- 2009-10-01 CZ CZ20090640A patent/CZ302421B6/en not_active IP Right Cessation
-
2010
- 2010-06-15 EP EP10755078.2A patent/EP2483020B1/en not_active Not-in-force
- 2010-06-15 WO PCT/CZ2010/000071 patent/WO2011038702A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2011038702A1 * |
Also Published As
Publication number | Publication date |
---|---|
CZ2009640A3 (en) | 2011-05-11 |
EP2483020B1 (en) | 2013-12-04 |
WO2011038702A1 (en) | 2011-04-07 |
CZ302421B6 (en) | 2011-05-11 |
WO2011038702A8 (en) | 2011-07-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6622761B2 (en) | Thermomechanical treatment of nickel-titanium alloys | |
KR101237122B1 (en) | Titanium alloy microstructural refinement method and high temperature-high strain superplastic forming of titanium alloys | |
CN105143483B (en) | Magnesium alloy with adjustable degradation rate | |
CA2741524C (en) | Nanostructured commercially pure titanium for biomedicine and a method for producing a rod therefrom | |
US5580516A (en) | Powders and products of tantalum, niobium and their alloys | |
RU2572928C2 (en) | Powder mix for production of titanium alloy, titanium alloy made thereof and methods of their fabrication | |
Luo et al. | High oxygen-content titanium and titanium alloys made from powder | |
JP2016512287A5 (en) | ||
CN107406911B (en) | Method for producing titanium and titanium alloy products | |
EP2483020B1 (en) | Method of production of nano-structural titanium semis for implants | |
EP3445281A1 (en) | Nickel-titanium- yttrium alloys with reduced oxide inclusions | |
JP5772731B2 (en) | Aluminum alloy powder forming method and aluminum alloy member | |
Butler et al. | Production of nitinol wire from elemental nickel and titanium powders through spark plasma sintering and extrusion | |
JP5915910B2 (en) | COMPOSITE MATERIAL FOR MEDICAL EQUIPMENT AND METHOD FOR PRODUCING THE SAME | |
CN108165811A (en) | A kind of preparation method of high-strength degradable nanometer medical porous titanium magnesium base composite material | |
RU2492256C9 (en) | Pure titanium-based nanostructured composite and method of its production | |
EP4022104A1 (en) | Magnesium alloy based objects and methods of making and use thereof | |
ZA200405764B (en) | Stabilized grain size refractory metal power metallurgy mill products. | |
RU2594548C1 (en) | Method of thermal hydrogen processing of semi-fabricated products from porous material based on titanium and its alloys | |
CZ2014929A3 (en) | Titanium-based alloy and heat and mechanical treatment process thereof | |
Watazu et al. | Commercial purity titanium processed by rotary-die equal channel angular pressing method | |
Popa et al. | Researches on the influence of thermal treatment on the mechanical properties of titanium dental prostheses | |
CN116334445A (en) | Rare earth doped Ti-Nb-Dy alloy and preparation and processing methods thereof | |
KR20070021115A (en) | Titanium alloy microstructural refinement method and high temperature-high strain superplastic forming of titanium alloys | |
CN117900482A (en) | Preparation method of high-purity magnesium rod for preparing degradable medical anchor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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 |
|
17P | Request for examination filed |
Effective date: 20120308 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20130711 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
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: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Ref country code: AT Ref legal event code: REF Ref document number: 643309 Country of ref document: AT Kind code of ref document: T Effective date: 20140115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602010012220 Country of ref document: DE Effective date: 20140206 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20131204 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 643309 Country of ref document: AT Kind code of ref document: T Effective date: 20131204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140304 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140404 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602010012220 Country of ref document: DE |
|
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 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
26N | No opposition filed |
Effective date: 20140905 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602010012220 Country of ref document: DE Effective date: 20140905 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140615 |
|
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: 20140615 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150227 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140615 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140615 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140630 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20150626 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140305 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20100615 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602010012220 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131204 |