Patent Application
20150225840
The present invention relates to a cutting tool for chip forming metal machining onto at least part of which a layer is deposited by means of highly ionised physical vapour deposition, preferably cathodic arc evaporation.
The increased productivity in modern chip forming metal machining requires tools with high reliability and excellent wear properties. It has been known since the end of the 1960s that tool life can be significantly improved by applying a suitable coating to the surface of the tool. Chemical vapour deposition (CVD) was the first deposition technique used for cutting tools and this method is still commonly used for deposition of TiN, Ti(C,N), and Al2O3. Physical Vapour Deposition (PVD) was introduced in the 1980s and has since then been developed from deposition of stable metallic compounds like TiN or Ti(C,N) to include deposition of multicomponent, metastable compounds like (Ti,Al)N, (Ti,Si)N, (Al,Cr)N, or (Al,Cr)2O3 by such methods as sputtering or cathodic arc evaporation. As is well known in the art the substrate bias potential is an important process parameter which has to be adapted to the specific coating composition and application. In addition, US2007218242 and EP2298954 describe variations in substrate bias potentials in order to further improve performance. Although the tool performance has been greatly improved by the mentioned findings, the inventors have noticed the need of a means for further improving the wear resistance of the cutting tools.
It is thus an object of the present invention to provide a coated cutting tool giving increased wear resistance.
To our surprise, we have found that the above object is attained by depositing a layer onto a tool body by means of a highly ionised physical vapour deposition technique, preferably cathodic arc evaporation, using a very high (negative) substrate bias potential during at least 5% of the total layer deposition time.
According to a first aspect, the present invention provides a method for depositing a hard and wear resistant coating onto a tool body of a hard alloy of, e.g., cemented carbide, cermet, ceramics, cubic boron nitride based material or high speed steel, wherein said coating comprises a layer, and said method comprises depositing the layer by highly ionised physical vapour deposition using elemental, composite and/or alloyed source material comprising the elements Me, where Me is one or more of Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W, B, Al, and Si, preferably one or more of Ti, V, Cr, Y, Zr, Nb, Al, and Si, most preferably one or more of Ti, Cr, Al, and Si, and in addition the source material may contain traces of impurities, using a process gas comprising one or more of the elements C, N, O, and S, preferably one or more of C, N, and O, most preferably one or more of N2 and O2, and in addition the process gas may contain a noble gas, hydrogen, and traces of impurities, and applying a first substrate bias potential, Ub1, where −900 V<Ub1<−300 V, during at least one fraction, Dhi, i=1, 2, 3, . . . , of the total layer deposition time, Dtot, where Dhi>0.05Dtot, preferably Dhi>0.1Dtot, whereby one first sublayer is formed during the at least one fraction. The method also comprises applying a second substrate bias potential, Ub2, where −150 V<Ub2<0 V, during at least one fraction, Dli, i=1, 2, 3, . . . , of the total deposition time, Dtot, where Dli>0.05Dtot, preferably Dli>0.1Dtot said fractions Dli being located before, after, and/or between fractions Dhi.
Thereby a coated cutting tool having increased wear resistance is achieved. The first substrate bias potential, Ub1, can vary within each fraction Dhi, but is always between −300 and −900 V during each fraction Dhi. The second bias potential, Ub2, can vary within each fraction Dli, but is always between 0 and −150 V during each fraction Dli. The layer thus produced contains at least one first sublayer, each first sublayer being deposited during a fraction Dhi, and at least one second sublayer in addition to the at least one first sublayer, each second sublayer being deposited during a fraction Dli.
According to one embodiment of the invention the substrate bias potential ramping time, between a fraction Dhi and a fraction Dli or between a fraction Dli and a fraction Dhi, is less than 0.02Dtot, preferably less than 0.01Dtot. Such substrate bias potential ramping may take place several times during one layer deposition and according to this embodiment of the invention each ramping time is less than 0.02Dtot. The short ramping time is beneficial under many process conditions in order to avoid excessive residual stress produced by deposition using a substrate bias potential in the intermediate range between −150 and −300 V.
According to one embodiment of the invention the first substrate bias potential, Ub1, is between −300 and −700 V, preferably between −350 and −700 V, most preferably between −350 and −650 V.
According to one embodiment of the invention the method comprises
According to one embodiment of the invention the method comprises
According to one embodiment of the invention the layer deposition includes at least two fractions Dhi.
According to one embodiment of the invention Dhi>0.3Dtot.
According to one embodiment 0.05Dtot<Dh1<0.9Dtot, preferably 0.05Dtot<Dh1<0.8Dtot, most preferably 0.05Dtot<Dh1<0.5Dtot.
According to one embodiment of the invention the layer deposition consists of at least one sequence Dli+Dhi, i=1, 2, 3, . . . , each fraction Dhi being located at the end of each sequence Dli+Dhi. Thereby a layered structure of alternating second and first sublayers is achieved.
According to one embodiment of the invention the layer deposition comprises a single fraction Dh1, and a single fraction Dl1, said fraction Dh1 being located at the end of the layer deposition time.
According to one embodiment 0.05Dtot<Dh1<0.6Dtot, preferably 0.05Dtot<Dh1<0.3Dtot, when the layer deposition comprises a single fraction Dh1, and a single fraction Dli, said fraction Dh1 being located at the end of the layer deposition time.
According to one embodiment of the invention the method comprises using a source material having a composition according to the chemical formula Ti1-X1-Y1AlX1MeY1, where 0.2<X1<0.7, preferably 0.4<X1<0.7, 0≦Y1<0.3, preferably 0≦Y1<0.15, most preferably Y1=0, and a process gas containing one or more of the elements N, C, and O, preferably said process gas is N2.
According to one embodiment of the invention the method comprises using a source material having a composition according to the chemical formula Ti1-X1-Y1AlX1MeY1, where 0.2<X1<0.7, preferably 0.4<X1<0.7, 0≦Y1<0.3, preferably 0≦Y1<0.15, most preferably Y1=0, using a process gas containing one or more of the elements N, C, and O, preferably said process gas is N2, and the layer deposition contains only one fraction, Dh1, said fraction Dh1 being located at the end of the layer deposition time.
According to one embodiment of the invention the method comprises using a source material having a composition according to the chemical formula Ti1-X2-Y2SiX2MeY2 where 0.02<X2<0.30, 0≦Y2<0.3, preferably 0≦Y2<0.15, most preferably Y2=0, and a process gas containing one or more of the elements N, C, and O, preferably said process gas is N2.
According to one embodiment of the invention the method comprises using a source material having a composition according to the chemical formula Cr1-X3-Y3AlX3MeY3, where 0≦X3<0.75, preferably 0.3<X3<0.75, 0≦Y3<0.3, preferably 0≦Y3<0.15, most preferably Y3=0, and a process gas containing one or more of the elements N, C, and O, preferably said process gas is O2.
According to one embodiment of the invention the method comprises using a source material having a composition according to the chemical formula Cr1-X3-Y3AlX3MeY3, where 0.3<X3<0.75, 0≦Y3<0.3, preferably 0≦Y3<0.15, most preferably Y3=0, and a process gas consisting of N2.
According to one embodiment of the invention, the method comprises using a source material consisting of Ti and a process gas containing one or more of the elements N, C, and O, preferably said process gas is N2.
According to one embodiment of the invention, the method comprises using at least two different, simultaneously active, source materials having different chemical compositions.
According to one embodiment of the invention, the method comprises using two different, simultaneously active, source materials having compositions according to the chemical formulas Ti1-X1-Y1AlX1MeY1, where 0.2<X1<0.7, preferably 0.4<X1<0.7, 0≦Y1<0.3, preferably 0≦Y1<0.15, most preferably Y1=0, and Ti1-X2-Y2SiX2MeY2 where 0.02<X2<0.30, 0≦Y2<0.3, preferably 0≦Y2<0.15, most preferably Y2=0, and using a process gas containing one or more of the elements N, C, and O, preferably said process gas is N2.
According to a second aspect of the present invention, a cutting tool for metal machining by chip removal is provided, wherein said tool comprises a tool body of a hard alloy of, for example, cemented carbide, cermet, ceramics, cubic boron nitride based material or high speed steel, onto at least part of which a hard and wear resistant coating is deposited, said coating comprising at least one layer deposited according to any of the above described embodiments of the inventive method. According to one embodiment said layer has a thickness of between 0.5 and 10 μm, preferably between 0.5 and 7 μm, most preferably between 1 and 5 μm, as measured in a region S of a cross section C, where
According to one embodiment of the invention, the coating comprises inner, outer, and/or intermediate deposits. Thereby a multilayer structure is formed. By deposit is herein meant a part of the coating structure which is not a layer or sublayer as defined in the present description.
According to one embodiment of the invention, the thickness of one layer is more than half of the total coating thickness, both thicknesses being evaluated as the maximum thickness of the layer and the coating, respectively, in region S.
According to one embodiment of the invention, each first sublayer has a thickness, tsi, greater than 0.05 μm, preferably greater than 0.1 μm, as evaluated in region S.
According to one embodiment of the invention, each first sublayer has a thickness distribution such that tei/tsi<1.5, preferably tei/tsi<1.2, as evaluated on the cross section C through the main cutting edge, where
In one embodiment of the invention the layer has a composition according to (Me,Q), where Me is one or more of Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W, B, Al, and Si, preferably one or more of Ti, V, Cr, Y, Zr, Nb, Al, and Si, and where Q is one or more of B, C, N, O, and S, preferably one or more of C, N, and O.
The above definitions of Me and Q also apply for the other embodiments of the invention being concerned with the composition of the layer and described herein.
In one embodiment of the invention the average grain width, w, within a first sublayer is 2 nm<w<200 nm, preferably 2 nm<w<100 nm, more preferably 2 nm<w<75 nm as measured by scanning or transmission electron microscopy analysis in region S and averaged over at least 20 representative grains in the middle part of the first sublayer, i.e. within 20% to 80% of the first sublayer thickness.
In one embodiment of the invention the layer has a composition according to the chemical formula Me1-xQx, where 0.3<x<0.7, preferably 0.45<x<0.7, as evaluated by, for example, energy or wavelength dispersive x-ray spectroscopy in region S.
In one embodiment of the invention the layer has a composition according to the chemical formula Me1-xQx, where Me is at least two elements, Me1 and Me2, Me1≠Me2, and the chemical composition within a first sublayer varies such that ΔCMe1>2 atomic percent, preferably ΔCMe1>5 atomic percent, where ΔCMe1=CMe1,si−CMe1,ei, CMe1,si is the maximum value of CMe1=AMe1/(AMe1+AMe2) in region S of said first sublayer, CMe1,ei is the minimum value of CMe1 in region E of said first sublayer, AMeX, X=1 or 2, is the average atomic content of MeX as measured by cross sectional analysis in the corresponding E or S regions by, e.g., energy or wavelength dispersive x-ray spectroscopy of a representative area in the middle part of the first sublayer, i.e. within 20% to 80% of the first sublayer thickness, and Me1 and Me2 are selected from the elements present in the first sublayer in order to give the highest possible value ΔCMe1.
In one embodiment of the invention the layer contains mainly NaCl phase, preferably a single NaCl phase as identified by, e.g., x-ray or electron diffraction in the middle of the tool face where region S is located.
In one embodiment of the invention the layer contains mainly corundum structured crystalline grains as identified by, e.g., x-ray or electron diffraction in the middle of the tool face where region S is located.
In one embodiment of the invention all first and second sublayers have compositions, as evaluated by, e.g., energy or wavelength dispersive x-ray spectroscopy in region S, according to the chemical formula (Ti1-x1-y1Alx1Mey1)(N1-a1Qa1)z1, where 0.1<x1<0.7, preferably 0.3<x1<0.7, 0≦y1<0.3, preferably 0≦y1<0.15, most preferably y1=0, 0.8<z1<1.2, preferably 0.9<z1<1.1, 0≦a1<0.5, preferably 0≦a1<0.3, most preferably a1=0.
In one embodiment of the invention all first and second sublayers have compositions, as evaluated by, e.g., energy or wavelength dispersive x-ray spectroscopy in region S, according to the chemical formula (Ti1-x2-y2Six2Mey2)(N1-a2Qa2)z2, where 0.01<x2<0.25, 0≦y2<0.3, preferably 0≦y2<0.15, most preferably y2=0, 0.8<z2<1.2, preferably 0.9<z2<1.1, 0≦a2<0.5, preferably 0≦a2<0.3, most preferably a2=0.
In one embodiment of the invention all first and second sublayers have compositions, as evaluated by, e.g., energy or wavelength dispersive x-ray spectroscopy in region S, according to the chemical formula (Cr1-x4-y4Alx4Mey4)(O1-a4Qa4)z4, where 0≦x4<0.75, preferably 0.3<x4<0.75, 0≦y4<0.3, preferably 0≦y4<0.15, most preferably y4=0, 0.8<z4<1.7, preferably 0.9<z4<1.7, most preferably 1.3<z4<1.7, 0≦a4<0.5, preferably 0≦a4<0.3, most preferably a4=0.
In one embodiment of the invention all first and second sublayers have compositions, as evaluated by, e.g., energy or wavelength dispersive x-ray spectroscopy in region S, according to the chemical formula (Cr1-x3-y3Alx3Mey3)(N1-a3Qa3)z3, where 0.3<x3<0.75, 0≦y3<0.3, preferably 0≦y3<0.15, most preferably y3=0, 0.8<z3<1.2, preferably 0.9<z3<1.1, 0≦a3<0.5, preferably 0≦a3<0.3, most preferably a3=0.
In one embodiment of the invention all first and second sublayers have compositions, as evaluated by, e.g., energy or wavelength dispersive x-ray spectroscopy in region S, according to the chemical formula Ti(N1-a3Qa3)z3, where, 0.8<z3<1.2, preferably 0.9<z3<1.1, 0≦a3<0.5, preferably 0≦a3<0.3, most preferably a3=0.
In one embodiment of the invention, all first and second sublayers are nanolaminates consisting of alternating nanolayers of different chemical composition, where the average thicknesses of said nanolayers are between 1 and 100 nm, preferably between 1 and 50 nm, most preferably between 1 and 30 nm, as evaluated in region S over at least 10 adjacent nanolayers in the middle part of the first or second sublayer, i.e. within 20% to 80% of the sublayer thickness.
In one embodiment of the invention, all first and second sublayers are nanolaminates consisting of alternating nanolayers having nominal compositions according to the chemical formulas (Ti1-x1-y1Alx1Mey1)(N1-a1Qa1)z1, where 0.2<x1<0.7, 0≦y1<0.3, preferably 0≦y1<0.15, most preferably y1=0, 0.8<z1<1.2, preferably 0.9<z1<1.1, 0≦a1<0.5, preferably 0≦a1<0.3, most preferably a1=0, and (Ti1-x2-y2Six2Mey2)(N1-a2Qa2)z2, where 0.02<x2<0.25, 0≦y2<0.3, preferably 0≦y2<0.15, most preferably y2=0, 0.8<z2<1.2, preferably 0.9<z2<1.1, 0≦a2<0.5, preferably 0≦a2<0.3, most preferably a2=0, and where the average thicknesses of said nanolayers are between 1 and 100 nm, preferably between 1 and 50 nm, most preferably between 1 and 30 nm, as evaluated in region S over at least 10 adjacent nanolayers in the middle part of the first or second sublayer, i.e. within 20% to 80% of the sublayer thickness. By nominal compositions is meant that the compositions are evaluated, by, e.g., energy or wavelength dispersive x-ray spectroscopy in region S, on corresponding thick deposits produced with the same process parameters.
By applying the above described embodiments of the invention a cutting tool with increased wear resistance is achieved. The increased performance is related to the use of the first substrate bias potential during a significant fraction of the layer deposition time.
Among the observed effects on coating properties gained by the invention the following are possible reasons for the increased performance:
a-e are schematic graphs showing the substrate bias potential, Ub, as a function of normalised deposition time according to embodiments of the invention.
a-e are schematic drawings of example coatings deposited according to embodiments of the invention.
a-h are schematic drawings showing examples of the position of a cross section C (dashed line) for some insert types.
a-b show schematically the measurement positions of ts and te for the same insert type as in
a-b are maps of the Al/(Al+Ti) atomic ratio on the rake (a) and flank (b) faces fitted to energy dispersive x-ray spectroscopy (EDS) measurements on a (Ti,Al)N first sublayer deposited onto negative 12×12×4 mm square insert with 00 rake angle. The variables X, Y, and Z are defined in
a-e show schematic drawings of a substrate bias potential, Ub, as a function of layer deposition time, D, illustrating examples of some embodiments of the invention where a hard and wear resistant coating is deposited onto a tool body of a hard alloy. The coating comprises a layer 2 comprising at least one first sublayer 3 and at least one second sublayer 4. The method comprises depositing the layer by highly ionised physical vapour deposition using elemental, composite and/or alloyed source material comprising the elements Me, where Me is one or more of Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W, B, Al, and Si, using a process gas comprising one or more of the elements C, N, O, and S. The method further comprises applying a first substrate bias potential, Ub1, where −900 V<Ub1<−300 V, during at least one fraction, Dhi, i=1, 2, 3, . . . , of the total layer deposition time, Dtot, where Dhi>0.05Dtot, whereby a first sublayer 3 is formed. The method also comprises applying a second substrate bias potential, Ub2, where −150 V<Ub2<0 V, during at least one fraction, Dli i=1, 2, 3, . . . , of the total deposition time, Dtot, whereby a second sublayer 4 is formed, said fractions Dli being located before, after, and/or between fractions Dhi.
In
a-e show some illustrations of coatings deposited according to embodiments of the invention, where
a-h show schematically the appropriate positions of a cross section C (dashed line) for some insert types. The cross section C is used in some of the embodiments of the invention for measurements of thickness and chemical compositional. According to these embodiments of the invention the cross section (C) is made through, and approximately perpendicular to, the main cutting edge line at a position away from any extreme curvatures of said cutting edge line, such as corners or noses. If possible, depending on the geometry of the tool, said cross section (C) is made at a position located between 2 and 3 mm away from any such extreme curvatures.
For measurements by x-ray diffraction as mentioned in some embodiments of the invention, it is not possible to measure in region S. Instead the measurement is made in the middle of the insert face where region S is located. As an example, for inserts with holes region S is typically located on the flank face of the insert and the x-ray diffractogram is then recorded in the middle of the flank face.
For evaluation of thicknesses and thickness distributions, some embodiments of the invention specify the measurement of the thicknesses te and ts, which are defined as the maximum thickness within the respective region E and S.
Measurements of the chemical composition according to the embodiments of the invention are made in regions E and S. It is evident that the compositional gradient between the E and S regions depends strongly on, for example, the geometry of the tool and the position of the cross section (C) such that, in general, the compositional difference between E and S regions becomes larger for sharper geometries. It is further evident that if the geometry and/or size of the cutting tool prohibit the described composition evaluations, the coating shall be evaluated by closely related evaluations.
A coating containing solely a (Ti,Al)N layer according to was deposited by cathodic arc evaporation onto cemented carbide inserts with chemical composition 94 wt % WC+6 wt % Co. Three insert geometries were used:
In all three cases the edge radius was about 25 μm, the flank faces were facing the sources during deposition, and 3-fold fixture rotation was applied. Before deposition, the inserts were cleaned in ultrasonic baths of an alkali solution and alcohol. The deposition chamber was evacuated to a base pressure of less than 2.0×10−3 Pa, after which the inserts were sputter cleaned with Ar ions. The coating was deposited from 6 TiAl composite cathodes with composition Ti:Al=34:66 in 99.995% pure N2 atmosphere at a pressure of 4 Pa, a temperature of 450° C. and the evaporator current was set to 70 A on each cathode. The substrate bias potential was initially kept at −40 V for 40 minutes resulting in an inner second sublayer, the potential was then ramped to −400 V at a ramping speed of about 100 V/s, and finally the substrate bias potential was kept at −400 V for the remaining 80 minutes of deposition time resulting in an outer first sublayer.
a-b are maps of the Al/(Al+Ti) atomic ratio as evaluated on the rake,
A corresponding thickness measurement was made for insert type II (having a sharper geometry and a relatively high rake angle). The measured thicknesses for the first sublayer and the inner second sublayer, respectively, were then 1.4 μm and 0.7 μm in region S, 1.5 μm and 1.5 μm in region E, and 0.5 μm and 0.6 μm on the rake face 0.5 mm from the edge. For insert type II the ratio te1/ts1 is thus 1.1 for the first sublayer and the corresponding ratio for the inner second sublayer is 2.1. It is clear that the ratio tei/tsi is influenced by tool geometry and it seems that the thickness on the rake face for the first sublayer is more sensitive to tool geometry than the corresponding thickness for the inner second sublayer.
In order to evaluate the first sublayer crystal structure by x-ray diffraction without interference from the second sublayer a single (Ti,Al)N first sublayer was deposited onto an insert type I using the same cathodes and deposition conditions as for the first sublayer in example I. The thickness was 2 μm as measured in region S, which was located on the flank face of the insert.
Coatings according to several embodiments of the invention as specified in table 1 were deposited onto cemented carbide and cubic boron nitride based bodies by means of cathodic arc evaporation. All coatings consist of one layer consisting of one or two sublayers and no additional deposits were applied. For each coating the sublayer A in table 1 was deposited onto the body (insert) and the sublayer B was deposited onto sublayer A. Depending on the substrate bias potential used during deposition of the sublayers A and B they correspond to first or second sublayers according to the embodiments of the invention as indicated in table 1.
The comparative coatings specified in table 2 were deposited onto cemented carbide and cubic boron nitride based bodies by means of cathodic arc evaporation. Deposition setup, nitrogen pressure, and temperature were the same as in example 1.
The thicknesses specified in tables 1 and 2 were measured in region S located on the flank faces, which were facing the cathodes during deposition. All samples contained mainly NaCl crystal structure as determined from x-ray diffraction measurements in the middle of the flank faces of the inserts (the insert face where region S is located).
A coating was deposited according to an embodiment of the invention onto an insert of type I from example 1. The process conditions were similar as for the coating in example 1 but using stronger magnetic fields at the cathode surface and a significantly higher plasma density at the substrate position. During the deposition of the first layer the higher plasma density caused a 50% increase in substrate bias current. The surface morphology of the resulting coating was compared to the coating from example 1 and to coating C1 from example 3. This comparison showed that the amount and size of the droplets remaining on the coating surfaces were highest for coating C1, lower for the coating from example 1, and lowest for the coating of the present example. It is believed that the smoother surfaces of coatings deposited according to the embodiments of the invention are due to a sputtering effect of the depositing ions and that the smoother surfaces are beneficial in machining applications.
Coatings C1-C3 and I1-I4 from example 3 were tested under the following conditions:
Application: Dry square shoulder milling
Work piece material: AISI 316L
Cutting speed: 180 m/min
Feed: 0.12 mm/tooth
Tool life criteria: Flank wear (vb)>0.2 mm
It is clear that the coatings deposited according to the method of the invention perform significantly better than the comparative coatings.
Coatings C1, I2, and I3 from example 3 were tested under the following conditions:
Work piece material: AISI 316L
Cutting speed: 275 m/min
Feed: 0.15 mm/rev
Tool life criteria: Edge wear
The coatings deposited according to the method of the invention displayed higher edge wear performance compared to the comparative coating. The edge wear was evaluated by visual inspection of the edge line.
Coatings C1, I3, and I4, from example 3, were tested under the following conditions:
Geometry: 10 mm square shoulder end mill
Application: Square shoulder milling
Work piece material: AISI 316L
Cutting speed: 100 m/min
Feed: 0.075 mm/tooth
Tool life criteria: Edge wear
The coatings deposited according to the method of the invention displayed significantly higher edge wear performance compared to the comparative coating. The edge wear was evaluated by visual inspection of the edge line.
Coatings C1, I4, and I7 from example 3, were tested under the following conditions:
Geometry: 10 mm square shoulder end mill
Application: Square shoulder milling
Work piece material: AISI H13
Cutting speed: 210 m/min
Feed: 0.12 mm/tooth
Tool life criteria: Chipping
The coatings deposited according to the method of the invention displayed significantly higher wear performance compared to the comparative coating.
It should be understood that alternative embodiments within the claimed scope of protection as defined in the annexed patent claims will be obvious to a person skilled in the art, and that that such alternative embodiments are to be regarded as within the claimed scope of protection. For example, the claimed method is also applicable to other material systems than the one specified in the above examples. The following are examples of such material systems: Al—Cr—N, Al—Cr—O, Ti—Al—Si—N, and Ti—Al—Cr—N.
| Number | Date | Country | Kind |
|---|---|---|---|
| 12169796.5 | May 2012 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2013/060902 | 5/28/2013 | WO | 00 |
