The present invention relates to a channel structure which is configured for connection to and/or for integration into a bioreactor, a biochemical reactor, a chemical reactor and/or a reformer of an electrochemical cell (in particular of a fuel cell, of an accumulator or of a battery). The invention furthermore relates to corresponding bioreactors, biochemical reactors, chemical reactors and/or reformers having a connected and/or integrated channel structure. The invention finally relates to uses of such channel structures for supplying and removing liquids and/or gases or for mixing liquids and/or gases.
Various processes are known for producing channel structures, e.g. in the form of mixed structures: Thus, for example, stamping processes, laser ablation processes, punching processes or micro-milling processes.
However, to produce more complex channel structures formed from individual channel structures (e.g. mixed structures or evaporator structures or also defined reaction spaces), a combination of a plurality of the aforesaid processes is necessary. However, this requires a considerable effort of labor and time. In addition, there are in part problems in the individual aforesaid processes with respect to the handling capability, with respect to the manufacturability of larger aspect ratios between the channel depth and the substrate thickness, with respect to the unwanted deformation of smaller channels by mechanical effects and/or, in dependence on the materials used, with respect to unwanted vitrification or outbreaks.
Starting from the prior art, it is therefore the object of the invention to provide channel structures which can be manufactured simply, fast, flexibly, without defects and inexpensively and which can serve the supply and the mixing of media of all kinds (e.g. of reactants) in reactors or in reformers of electrochemical cells. It is furthermore an object to provide correspondingly constructed bioreactors, biochemical reactors, chemical reactors and/or reformers of electrochemical cells.
This object is achieved by a channel structure in accordance with claim 1 and by a reactor or reformer in accordance with claim 22. Uses in accordance with the invention result from claim 24. Advantageous embodiments can in each case be seen from the dependent claims.
The present invention will first be described generally in the following and then with reference to individual embodiments. The individual features of the present invention realized in combination with one another in the embodiments can in this respect also be realized in different combinations with one another within the framework given by the claims, i.e. they do not have to correspond to the example configurations shown. Individual ones of the features shown in the embodiments can also be omitted or can be combined in a different manner with further of these or other features.
The underlying idea of the present invention is to provide a plurality of individual layers which are stacked on one another and which then form the channel structure. For this purpose, the individual layers have openings (hole structures) which completely pass through the corresponding layer and which are arranged at least sectionally in the individual layers in the form of regular patterns. The layer sections of adjacent individual layers of the channel structures provided with corresponding patterns are then stacked on one another or are arranged adjacent to one another such that layer sections of directly adjacent (viewed in the layer surfaces of the individual layers) individual layers provided with such a pattern of openings overlap at least partly, wherein the openings of the overlapping layer sections are rotated and/or offset relative to one another in the respective overlap region.
A stamping process can, for example, be used to produce openings in the individual layers. The individual layers are produced so that the openings formed in them overlap only partly at least layer-section-wise, that is, are rotated and/or offset relative to one another. A variable three-dimensional channel structure which can then, for example, be configured as a mixed structure, is made possible by this partial overlapping by stacking a plurality of such individual layers on one another with openings arranged offset and/or rotated with respect to one another. Any desired shape and/or size variations of the channel structure (for example: a mixed structure) are possible by a suitable choice of the shape of the openings (for example by stamping out the openings, for example, by stamping tools with round, square or rectangular geometries), of the stringing together of individual manufacturing steps for the openings (e.g. stamping steps) and the stacking of a plurality of individual layers (in the following also: sheets) with openings. It is, however, common to respective adjacent sheets that together they have a three-dimensional guidance of channels through a partial overlap of openings (that is a rotation and/or offsetting of individual openings in the adjacent sheets relative to one another) of the different sheets.
Ceramics, in particular low-temperature cofired ceramics (so-called LTCC ceramics) or high-temperature cofired ceramics (so-called HTCC ceramics) can in particular be considered as the basis substrate for the individual layers. The individual layers can, however, also be manufactured from plastics or from mats which are suitable for stamping processes.
What is decisive for the material selection for the individual layers in this respect is that the selected material is temperature-stable, that is stable at the reaction temperatures to be selected in the reactor or in the reformer, and chemically stable, that is stable with respect to the individual reactants in the reactor or reformer.
A channel structure in accordance with the invention thus has a plurality of individual layers which are stacked on one another, wherein the individual layers each have a plurality of openings (e.g. stamped cuttings or incised holes) completely passing through the respective individual layer and wherein directly adjacent individual layers are each arranged adjacent to one another and/or are connected to one another. At least two directly adjacent individual layers each have at least one layer section whose openings are arranged in the form of a pattern respectively regular in two dimensions viewed in the respective layer surface of the respective individual layer. At least two of the layer sections of directly adjacent individual layers provided with such a pattern in this manner then overlap partially (viewed in the respective layer surfaces of these individual layers). In this respect, the openings of the two at least partly overlapping layer sections are rotated and/or offset relative to one another in the overlap region (again viewed in the respective layer surfaces of these individual layers); these openings thus only overlap in part.
Openings of directly adjacent individual layers are connected to one another by this partial overlap (that is, they form a common throughflow section for liquids and/or gases) such that channels are formed in the individual layers over a plurality of adjacent individual layers. These channels can then be connected to one another by suitable formation and arrangement of a plurality of openings in a plurality of individual layers such that a complex channel structure arises, for example in the form of a mixed structure.
A chemical reactor is understood within the framework of the present invention as a structure in which chemical processes take place and/or in which chemical conversions are carried out (this can take place, for example, at increased temperature and/or at increased pressure). A bioreactor is accordingly understood as a structure in which biological processes can be carried out. A biochemical reactor is accordingly a structure for biochemical procedures and/or for biochemical conversion. Such structures can in particular also be structures of orders of magnitude in the millimeter or micrometer ranges; the corresponding individual layers and openings of the present invention can thus have thicknesses or heights, widths and/or lengths which are formed in the range of 10 μm to 10 cm, in particular in the range from 100 μm to 1 cm.
When it is stated that a channel structure in accordance with the invention is made for integration into a reactor and/or reformer, this also includes the case that the corresponding reactor or reformer only comprises the channel structure.
In this respect, the individual layers can be formed in the manner of curved surfaces (e.g. convex or concave surfaces); as a rule, the individual layers are, however, made as planar, two-dimensional or areal layers so that as a rule the corresponding layer plane is meant when a corresponding layer surface is spoken of in the following.
A layer section is then accordingly understood as a rule as a real partial region of the corresponding layer in the layer surface (that is e.g. in the layer plane); such a layer section does not only have to comprise a part of the layer surface, but can rather also correspond to the total layer surface.
An opening is understood as a structure formed in any desired manner in the layer surface which completely passes through the corresponding individual layer in the corresponding form (that is, the material of the individual layer is removed at the location of the opening in the corresponding form). As a rule, such an opening is a hole in the individual layer having a simple structure or shape, in particular e.g. an elongate rectangular, oval or elliptical hole.
An arrangement of such openings (in the layer surface of an individual layer) in the form of a respective regular pattern in two dimensions is understood in the following as a layer section in which a plurality of openings (preferably of the same shape and of the same size) are arranged such that the openings repeat at regular intervals in two spatial directions which have an angle to one another unequal to 0° and unequal to 180°. These two spatial directions, which are preferably arranged at an angle of 90° with respect to one another, that is, stand perpendicular on one another, are also called the two dimensions of the regular pattern of openings of a layer section formed in this manner in the following.
The spacing of two directly adjacent openings in one of these two directions or dimensions is understood, provided nothing else is stated in the following, as the minimal spacing of two edge points of these openings in the corresponding direction or dimension (in the following also: edge-to-edge spacing). The spacing of the centers of mass of two openings is understood as the spacing of the geometrical centers of mass of the two openings.
When it is stated in the following that two layer sections (which are provided with a pattern of openings) of two directly adjacent individual layers overlap at least in part, this means that the two layer sections are arranged lying at least partly over one another viewed perpendicular to the layer surfaces or layer planes of these individual layers (so that the two patterns of the adjacent individual layers cover one another at least in part). The same applies accordingly to the overlap of openings: When it is stated that two openings of directly adjacent individual layers (or of the layers sections of these individual layers provided with opening patterns) overlap or cover one another in part, this means that the two openings admittedly are not arranged superimposed (in the direction perpendicular to the layer surface or layer plane) over one another, but rather have a common section or opening section viewed in the layer surface or in the layer plane so that a common aperture section or throughflow section passing through the two adjacent individual layers is formed.
When it is stated in the following that the openings of a layer section (or of a pattern) have a preferred direction, this means that they have a different extent in one direction, viewed in the layer surface, than in (at least) one other direction. In this respect, that direction is defined as the preferred direction, if nothing else is stated, in which the openings have the greatest extent (the preferred direction is then the longitudinal direction of the openings). As a rule, this preferred direction will also coincide with one of the two dimensions of the regular pattern of the openings, but this does not have to be the case. The openings can thus be arranged in a two-row and column matrix (with the two dimensions of the pattern then standing perpendicular to one another), the openings can be formed in the manner of elongate holes and the longitudinal direction of the holes can be aligned either in the column direction or in the row direction (this is then preferred direction). Alternatively to this, however, it is also possible to form the longitudinal direction of the openings in such an array pattern not along the direction of the rows or columns, but rather e.g. along a diagonal or at any desired angle (e.g. of 30°) to the direction of the columns or rows.
When it is thus stated in the following that two openings of two layer sections of directly adjacent individual layers are rotated relative to one another, this as a rule means that the preferred directions of these openings of the two patterns have an angle relative to one another of >0° and <180°. If two openings of two such patterns are offset relative to one another, this as a rule means that the preferred directions are admittedly arranged parallel to one another (and frequently also that the openings of the two patterns are arranged at the same level viewed in the layer surface and perpendicular to the preferred direction), but the two openings do not lie completely over one another in a superimposed manner, but rather only have, viewed in the partition surface between the two directly adjacent individual layers, a common part section in accordance with a real part of the total opening surface and/or of both opening surfaces of the two openings.
If the center of mass spacing of two directly adjacent openings of one and the same pattern or layer section of one and the same individual layer is defined in the direction of one of the two dimensions in which the pattern is made as regular as the pattern period of the corresponding pattern in this dimension, an arrangement of the openings of the patterns of two directly adjacent individual layers offset by half a period (in this dimension) means an initially identical placing over one another of the two patterns and then subsequently a displacement of one of the two patterns in the corresponding dimension direction by half this center of mass spacing.
The opening patterns of adjacent overlapping layer sections are advantageously made identical apart from a rotation and/or offset relative to one another. The openings of the individual patterns in this respect advantageously have, as described above, a preferred direction, that is, they have a larger or smaller extent in a first direction of the layer surface than in a second direction (not equal to the first direction) in the layer surface. The first direction is preferably one of the two dimensions in which the corresponding pattern is made as regular.
In a further advantageous variant, at least one of the individual layers has a plurality of layer sections with regular patterns so that the regular patterns of different layer sections do not coincide and/or have different preferred directions in at least one of the two regular pattern dimension directions.
Pairwise overlapping layer sections thus preferably result between directly adjacent individual layers, wherein the openings of the one layer section of an overlapping pair are rotated and/or offset to the openings of the other layer section of the pair.
In this respect, the openings of the two adjacent individual layers are preferably made, despite the previously described offsets and/or rotations, so that a respective opening of the one individual layer and an opening of the other individual layer form a clear connection, that is, a throughflow possibility from one opening into the other opening.
The openings of overlapping layer sections of different individual layers can be arranged rotated (with the angle of rotation preferably amounting to 90°, measured e.g. with respect to a preferred direction such as the longitudinal axial direction of the openings of one of the layer sections) and not offset relative to one another. Equally, however, it is possible to arrange the openings of overlapping layer sections of adjacent individual layers offset relative to one another and not rotated relative to one another. The offset can in this respect in particular take place by half a pattern period of one of the two dimensions of the opening pattern in one of the individual layers (or in both individual layers).
The regular pattern can in particular be made in the form of a two-dimensional matrix with rows and columns of openings (with the row direction then being perpendicular to the column direction).
The individual openings can be made in the form of elongate apertures, wherein the longitudinal axis of these elongate apertures can be aligned in the direction of one of the two aforesaid dimensions of the pattern. In this case, the longitudinal axis of these apertures stands perpendicular to the direction of the other dimension of the pattern. Viewed in the direction of the longitudinal axis, directly adjacent elongate apertures can then have an edge-to-edge distance which is smaller than the extent of such an elongate aperture in the direction of its longitudinal axis. The edge-to-edge spacing is in this respect the minimal spacing of two edge points of such elongate apertures in the direction of the longitudinal axis of the apertures (or in the direction of that dimension of the pattern in which this longitudinal axis is aligned). The edge-to-edge spacing of two directly adjacent elongate apertures in the direction of the longitudinal axis defined in this manner and the extent of an aperture in the direction of this longitudinal axis thus form the pattern period in the direction of the said dimension or in the direction of the aligned longitudinal axes. In this respect, the said edge-to-edge spacing in the longitudinal direction is preferably smaller than or equal to half, particularly preferably equal to a third of the extent of the elongate apertures in the direction of the longitudinal axis. The edge-to-edge spacing perpendicular to the direction of the above-described dimension (that is, the transverse spacing in the direction of the other of the two dimensions of the pattern)of elongate apertures arranged directly adjacent to one another can also be equal to the above-described edge-to-edge spacing in the direction of the longitudinal axis. The transverse spacing is then the minimal spacing of two edge points of adjacent apertures in the direction perpendicular to the direction of the longitudinal axis of the openings.
In a further advantageous variant, layers sections of two directly adjacent individual layers overlap so that their elongate apertures not only have the same shape and size, but are also aligned parallel to one another (that is, all face in the same direction with respect to their longitudinal axes), with an offset of the elongate apertures being realized in the direction of the longitudinal axis. The offset in this respect preferably amounts to half a pattern period in the direction of the dimension of the direction of the longitudinal axis of the pattern.
It is equally possible that two overlapping layer sections of two directly adjacent individual layers (whose elongate apertures have the same shape and size) are made with respect to their apertures that the apertures of the layer section of the one individual layer are arranged rotated relative to the apertures of the layer section of the other individual layer. The angle of rotation here preferably amounts to 90°.
A plurality of individual layers is advantageously made completely identical with respect to their layer sections, their patterns and the openings of the patterns. The individual layers made identical in this manner can then be rotated and/or offset relative to one another.
In all the variants described above, the openings of respective directly adjacent individual layers and/or layer sections are preferably made at least in part so that they overlap pairwise in real part sections. This means that two such overlapping openings of adjacent individual layers have a common intersection viewed in the layer surface or layer plane, that therefore the two openings together form a suitable passage (for the conducting of a liquid and/or of a gas, optionally also of a powder such as with a catalyst in the fixed bed or with metal hydrides as a hydrogen tank) between the two individual layers; however, without the two openings being arranged in an identical position lying over one another (the surface of the passage in the layer plane is thus smaller than the base surface of the openings in this plane).
The individual layers are preferably made in planar form and are stacked over one another in the form of a layer stack. The openings can, for example, be realized in the form of stamped cuttings or cut-outs (e.g. with the help of lasers) of part sections from the individual layers.
As will be described in more detail in the following, it is in particular possible to form a bioreactor, a biochemical reactor, a chemical reactor and/or a reformer in accordance with the invention of an electrochemical cell by stacking a plurality of individual layers in which then layer sections having regular patterns of openings are then formed in each case in a suitable manner and by suitable offset and/or rotation of the layer sections of adjacent individual layers relative to one another such that the total reactor and/or reformer comprises only these structured individual layers. (As a rule, it is still necessary for this purpose to arrange individual top or bottom layers above the topmost individual layer and below the bottommost individual layer, with as a rule either no openings or only individual openings being structured in said individual top or bottom layers, with said individual openings then serving as supply or removal channels.
The walls of the openings, that is, the inner walls of the channels of the channel structure in accordance with the invention, can in this respect be coated with a suitable catalyst which serves as a catalyst for a reaction to be carried out in the reactor.
The channel structure can furthermore also be formed for the transport of material and/or heat (e.g. as a heat exchanger).
The present invention will be described in the following with reference to a plurality of embodiments. There are shown
a to 1e a first embodiment in the form of two identically structured individual layers (that is identical patterns at individual layers having openings) in the form of plastic foils which are laminated onto one another in offset form (
a to 2e a mixer structure which is formed by the introduction of an individual layer rotated by 90° between two identical and uniformly aligned individual layers (wherein then all three individual layers have one and the same pattern of openings);
a to 3f mutually concentrically nested helical structures manufactured by stacking a plurality of individual layers;
a shows a single individual layer 1A usable for a channel structure in accordance with the invention or for stacking on one another in the form of a foil from which a plurality of openings 3 are stamped out in the form of elongate apertures. The openings 3 are arranged in the foil, which is planar here, in the form of a two-dimensional matrix, that is, in the direction of columns and rows (with the direction of the columns being perpendicular to the direction of the rows). The individual openings 3 thus form a two-dimensional perforated grid, wherein a plurality of individual holes is arranged at regular, sequential intervals in the row direction (or in the direction of a first dimension D1 of the opening pattern 4) in every row. The direction of the longitudinal axis or the longitudinal direction of the openings 3 is identical to the dimension D1 here. Equally, a plurality of openings is arranged at regular intervals behind one another in the column direction (or in the direction of the second dimension D2 of the opening pattern standing perpendicular on the first dimension D1) in every column.
Viewed in the direction of the first dimension D1 (longitudinal direction), two directly adjacent openings or elongate apertures 3 have the edge-to-edge spacing A (cf.
a thus shows an individual layer 1A having precisely one layer section 2A1 in the form of a pattern 4 of elongate apertures 3 respectively regularly formed in the direction of the two dimensions D1, D2.
b now shows the already described individual layer 1A and a further, identically formed second individual layer 1B lying thereunder (only one individual layer section 2B1 is thus also realized in the second individual layer 1B having a plurality of openings 3 which are in turn formed in the layer plane of the individual layer 1B in the form of a pattern 4 respectively regular in two dimensions; these two dimensions of the second individual layer 1B coincide here with the two corresponding dimensions of the first individual layer 1A due to the arrangement over one another described below in more detail of the two individual layers 1A, 1B).
The two identically formed individual layers or foils 1A, 1B are now arranged directly adjacent to one another with their layer planes parallel to one another, that is, stacked over one another in the direction perpendicular to the layer plane. This stacking is realized by an offset in the direction of the first dimension D1 (that is in the direction of the longitudinal axis of the individual openings). The two pattern matrices 4 of the upper layer 1A and of the lower layer 1B were in this respect offset by half a period P1 in the direction D1 relative to one another. No offset is realized in the direction perpendicular thereto (direction D2). Due to this one-dimensional offset of the two individual layers only in the direction of the dimension D1, a meander-like extent (viewed perpendicular to the layer plane, cf.
If now the upper plate 1A or its openings 3 are now covered by a closed individual layer 6a and if a plurality of such three-layered structures 6a, 1A, 1B are stacked over one another in the direction perpendicular to the layer plane, the construction shown in
e shows a sectional representation (the section is, just as in
a to 2e show a further embodiment in which the individual layers are generally formed in the same manner as is described with respect to
In the case shown in
An intermediate layer 1B, which likewise has only one layer section 2B1 extended over the total layer plane is introduced in the manner of a sandwich between these two layers 1A and 10 and directly adjacent to these two layers. The overlap region of the three layer sections 2A1, 2B1, 2C1, as the region 5 thus corresponds to the respective total layer plane.
In contrast to the two layers 1A, 10, however, the direction of the longitudinal axis of the openings 3 of the individual layer 1B is not aligned in the direction of the first dimension D1, but rather perpendicular thereto, that is, in the direction of the second dimension D2 (in other words, the middle individual layer 1B represents an individual layer rotated by 90° in the layer plane). The first plane 1A is thus (viewed with respect to the first dimension D1) directed lengthways, the second plane is laminated on transversely to the first plane and the third plane is in turn directed or laminated on lengthways and is offset, viewed with respect to the first plane 1A and the dimension D1, by half a pattern period.
A mixer structure thus arises by introduction of a plane 1B rotated about 90° between two planes 1A, 1C made lengthwise (with respect to their channels or openings 3).
Complex mixer structures can thus be constructed on a very small construction space in a simple manner with the help of the above-described individual layers and the structured formations 3, 4 of the same. In this respect, only stamping procedures are required per layer (subsequently a lamination of the individual layers must still take place) so that a fast and inexpensive structuring variant results for channel structures.
a shows a first individual layer 1A in the form of an LTCC ceramic. The first individual layer 1A here includes a total of four individual layer sections 2A1, 2A2, 2A3 and 2A4. The four layer sections are realized in that the first individual layer 1A, square here, is divided by its two diagonals d1, d2 into four isosceles, right-angled triangles which are identical with respect to their shapes, with one of the layer sections 2A1 to 2A4 corresponding to each of these triangles.
Two respective oppositely disposed layer sections (that is the layer section pair 2A1 and 2A3 as well as accordingly also the layer section pair 2A2 and 2A4) in this respect have an identical pattern of elongate apertures 3, wherein the directions of the longitudinal axis of each aperture 3 of a layer section pair are each aligned parallel to one another. The elongate apertures 3 of the sectional section pair 2A1, 2A3 thus all extend (with their longitudinal axes) in the direction of the first dimension D1 of the four patterns 4 of the layer sections 2A1 to 2A4 and all the elongate apertures of the layer section pair 2A2, 2A4 extend (with respect to the directions of their longitudinal axes) in the direction of the second dimension D2 of the regular patterns 4 of the four layer sections 2A1 to 2A4.
In other words, all four layer sections 2A1 to 2A4 are completely filled with elongate apertures (whose shapes and sizes and whose spacings are here formed as described with respect to
b shows a further individual section 1B which is made identical with respect to its structuring to the individual layer 1A, but which is formed in the plane shown (which corresponds to that of the layer plane) rotated by 90° about the center of mass or the center S of the individual layer 1A. If the two dimensions D1, D2 of the second individual layer 1B are thus defined identically to that of the individual layer 1A, the opening structure of the individual layer 1B is thus rotated by 90° about the center of the individual layer 1A relative to the opening structure of the individual layer 1A.
The apertures 3 of the second individual layer 1B are thus admittedly also aligned (viewed with respect to the direction of the longitudinal axes) in the two oppositely disposed layer sections 2B2 and 2B4 in the direction of the second dimension D2 and the apertures 3 of the two oppositely disposed layer sections 2B1 and 2B3 are aligned in the direction of the first dimension D1. Since, however, the outermost aperture row of the layer sections 2A2 and 2A4 (or of the layer sections 2B1 and 283) facing the triangle basis respectively has one more aperture 3 than the outer aperture rows of the layer sections 2A1 and 2A3 (or 2B2 and 2B4) and since thus the hole structures in the two individual layers 1A, 1B are not mirror symmetrical to the diagonals d1 and d2, a respective offset results between apertures of the two individual layers 1A, 1B lying over one another on a stacking over one another of the two individual layers 1A, 1B: The individual openings of the two layers 1A, 1B thus do not lie identically above one another, but are rather only made partly overlapping so that twelve independent annular channels result in the overlap region 5 (viewed in the layer planes) which extend concentrically into one another and have a meander-like structure viewed in the section perpendicular to the layer planes (cf. in this respect
d now shows three individual layers stacked over one another, wherein the lower individual layer and the middle individual layer are formed in accordance with the individual layer 1A or with the individual layer 1B respectively in the
If the three-layer structure shown in
With such a stacking, a respective suitably formed, almost closed layer having a suitable channel ducting in the region of the structures 7, 8 then lies between two adjacent three-layer systems (cf.
The layers, which are made almost closed, of the total stack comprising a plurality of three-layer systems plus the almost closed layers are designated by 6a, 6b, . . . in
Channels separate from one another having different lengths in the layer plane are thus produced by superimposition of a plurality of identical structures or individual layers laminated in an offset manner (
The above-described channel ducting of the helical structure enables an extremely compact manner of construction with a reaction surface which is simultaneously as large as possible. Each of the twelve channels extending helically is insulated hermetically per se; different reactions are thus possible in a very tight space. It is also possible to form an insulation by vacuum formation in individual channels.
The reformer here comprises, viewed in the layer plane, a plurality of individual blocks which are each connected to one another by channels conducted in two layers in the manner of a meander.
As
It is in this respect in particular advantageous that any desired channel structures can be produced, with the size and shape of the channels being limited only by the stamped tools used. A very compact construction is possible with the individual layer structure shown; for the insulation of individual channels, only an individual layer thickness is necessary (thickness e.g. 200 μm). Reaction surfaces of practically any desired size can be produced for the reforming.
The present invention in particular has the following advantages:
Number | Date | Country | Kind |
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10 2009 038 019.1 | Aug 2009 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP10/04899 | 8/11/2010 | WO | 00 | 4/17/2012 |