The present invention relates generally to the structuring of glasses, and more particularly, to a laser-based process for structuring glass, and also the glass elements which can be produced thereby.
The precise structuring of transparent, opaque and nontransparent glasses is of great interest in many fields of application. Here, precisions in the region of a few microns are required. The structuring relates to holes (round and angular), cavities, channels or any free shapes. In order to be used in a wide range of applications, the working should leave behind no damage, residues or stresses in the outer region or volume of the substrate. Furthermore, the process should allow a very efficient manufacturing process. Various methods can be employed for producing holes. Apart from sandblasting through appropriate masks, ultrasonic vibratory lapping is an established process. However, both methods are, due to their scale, restricted to small structures which are typically at about 400 μm in the case of ultrasonic vibratory lapping and at a minimum of 100 μm in the case of sandblasting. Owing to the mechanical removal of material, stresses in the glass, associated with flaking at the peripheral region of the hole, are produced in the case of sandblasting. Both processes are fundamentally unsuitable for the structuring of thin glasses.
In recent times, many laser sources have been used for the structuring of various materials. Here, virtually all known laser sources, e.g. CO2 or CO lasers, diode-pumped ns, ps, and fs solid-state lasers having an infrared (e.g. 1064 nm), green (532 nm) and UV (365 nm) wavelength, have been used. Excimer lasers, which work at extremely short wavelengths (e.g. 193 nm, 248 nm), are also used for processing. The working of glasses is particularly demanding since they generally have a low thermal conductivity and a high susceptibility to fracture. All laser ablation processes therefore lead to more or less strong thermal stressing or heat input, which does decrease at shorter wavelengths and shorter pulse lengths but sometimes still leads to critical stresses through to microcracks and deformations in the peripheral region of the holes. At the same time, clearly measurable roughnesses are still produced on the hole walls when this process is used since all laser processes ablate in a cluster-like manner, i.e. the respective cluster size determines the residual roughness of the walls.
To produce very small structures in the surfaces, the laser ablation process is used. A disadvantage here is that deep structures can be achieved only with multiple passes over the work piece to be processed. The processing time is correspondingly slow. The process is therefore of only limited suitability for use in industrial manufacture. This applies particularly when through-openings or structures in general which extend from one side face to the opposite side face are to be introduced in glasses. The walls of such structures, e.g. of furrows, also have an inclination, i.e. are not perpendicular.
A further problem is, especially in the structuring of glasses as brittle-hard materials, that the structures introduced can significantly decrease the strength under flexural stresses. This applies particularly when the structures produced form part of an edge or an opening going through the glass.
What is needed in the art is a glass element having fine structures which extend between the side faces of the glass element but reduce the strength very little or even increase the strength.
The invention accordingly provides a plate-like or tabular glass element having two opposite side faces, generally running parallel to one another, and a channel which has been introduced into the glass of the glass element and joins the two side faces and opens into the side faces and has a rounded wall and a transverse dimension of less than 100 μm, for example less than 70 μm. The longitudinal direction of the channel runs transverse to the side faces. Here, the wall of the channel has a plurality of rounded, substantially hemispherical depressions. The longitudinal direction of the channel particularly may run perpendicular to the side faces, or accordingly parallel to the normal to the side faces. The channel opens into the side faces.
Such a glass element is produced by a laser-based process. The process of the invention for producing the plate-like glass element is based on:
The pulse energy of the individual pulse is selected so that it is below the ablation threshold of the glass, so that the laser light can penetrate into the glass and the laser energy is not consumed at the surface by the ablation process.
The particular structuring of the lateral surface of the channels with substantially hemispherical depressions results in a number of advantages. Firstly, the rounded structures may represent a particularly advantageous shape in order to dissipate tensile stresses occurring on the surface down to the lowest point of the surface, namely the lowest points of the substantially hemispherical depressions. This effectively suppresses crack growth at possible defects in the surface.
In particular, parts of the glass element 1 can also be separated off by introduction of the channels when these are produced next to one another and edges, in particular also internal edges of openings, can thus be produced. Such openings may have a transverse dimension of at least 200 μm, for example at least 300 μm.
The substantially hemispherical depressions form, in particular, when a slow etching process is carried out. The abovementioned low etching rate of less than 15 μm per hour is therefore provided. Furthermore, the substantially hemispherical depressions are presumably brought about by structures which occur on introduction of the filament-shaped flaws. The burst mode with the inward radiation of a pulse packet can be used to achieve elongated, uniform flaws.
As etching medium, particular preference is given to an etching solution. In this embodiment, etching is thus carried out wet-chemically. This may be advantageous in order to remove glass constituents from the surface during etching. As etching solution, it is possible to use both acidic and alkaline solutions. As acidic etching media, HF, HCl, H2SO4, ammonium bifluoride, HNO3 solutions or mixtures of these acids are particularly suitable. For basic etching media, KOH or NaOH solutions may be used. Greater rates of removal of material can typically be achieved using acidic etching solutions. However, basic solutions can be used, especially since only a slow removal of material is sought in any case.
Furthermore, etching can be carried out in a temperature range from 40° C. to 150° C., for example from 50° to 120°, for example up to 100° C.
In general, siliceous glasses having a low alkali metal content are particularly suitable for the structuring according to the invention. Excessively high alkali metal contents make etching more difficult. One embodiment of the invention therefore provides for the glass of the glass element to be a silicate glass having a content of alkali metal oxides of less than 17 percent by weight.
In the burst operating mode provided for the invention, the laser energy is not supplied as a single pulse but as a sequence of pulses which follow one another at short intervals and together form a pulse packet, known as a burst. Such a pulse packet typically has somewhat more energy than a single pulse in the conventional single-shot mode of operation. However, the pulses of a burst themselves contain significantly less energy than a single pulse. With regard to pulses within a burst, the pulse energies can be set flexibly, in particular so that the pulse energies either remain essentially constant or so that the pulse energies increase or so that the pulse energies decrease. In any case, the surface structure according to the invention with a channel having the concave, rounded pits or the substantially hemispherical depressions is obtained particularly when the filament-shaped flaws are introduced by laser pulses in the burst mode.
One suitable laser source according to the present invention is a neodymium-doped yttrium-aluminum garnet laser having a wavelength of 1064 nanometers.
The laser source produces, for example, an initial beam having a (1/e2) diameter of 12 mm; a biconvex lens having a focal length of 16 mm can be used as optics. To produce the initial beam, it is optionally possible to use suitable beam-forming optics, for example a Galileo telescope.
The laser source operates, with a repetition rate in the range from 1 kHz to 1000 kHz, for example from 2 kHz to 100 kHz, for example from 3 kHz to 200 kHz.
The repetition rate and/or the scanning rate can be selected so that the desired distance between neighboring filament-shaped flaws is achieved.
A suitable pulse duration of a laser pulse can be in the range of less than 100 picoseconds, for example than 20 picoseconds.
The typical power of the laser source can be in the range from 20 to 300 watt. In order to achieve the filament-shaped flaws, a pulse energy in the burst of more than 400 microjoule is used in an embodiment of the invention; a total burst energy of more than 500 microjoule may be more advantageous.
When the ultrashort pulse laser is operated in the burst mode, the repetition rate is the rate of repetition of the release of bursts. The pulse duration depends mainly on whether a laser is operated in single-pulse operation or in the burst mode. The pulses within a burst typically have a similar pulse length as a pulse in single-pulse operation. The burst frequency can be in the range from 15 MHz to 90 MHz, for example in the range from 20 MHz to 85 MHz, and is for example 50 MHz and the number of pulses in the burst can be in the range from 1 to 10 pulses, e.g. 6 pulses.
In order to achieve opening of the channels into both side faces, the filament-shaped flaw can go essentially completely across the glass element, but it is not necessary for a flaw going all the way through to be observed. The filament-shaped flaw can, for instance, also be a sequence of local defects arranged in succession. In order to produce a channel running through the glass element 2, however, relatively thin glass elements are generally suitable in any case. The thickness range for the glass elements may be from 30 microns to 3 millimeters.
The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate embodiments of the invention and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
The focusing optics 23 then focus the laser beam 27 to form a focus which is elongated in the direction of the beam, i.e. accordingly transverse, in particular perpendicular, to the irradiated side face 2. Such a focus can, for example, be produced by way of a conical lens (known as an axikon) or a lens having great spherical aberration. The control of the positioning device 17 and of the ultrashort pulse laser 30 may be effected by way of a programmed computer 15. In this way, predetermined patterns of filament-shaped flaws 32 distributed laterally along the side face 2 can be produced, in particular by input of positional data, for example from a file or via a network.
According to one embodiment, the following parameters can be used for the laser beam:
The wavelength of the laser beam is 1064 nm, typical for a YAG laser. A laser beam having an initial beam diameter of 12 mm is produced, and this is then focused by way of optics in the form of a biconvex lens having a focal length of 16 mm. The pulse duration of the ultrashort pulse laser is less than 20 ps, for example about 10 ps. The pulses are emitted in bursts of 2 or more, for example 4 or more pulses. The burst frequency is 12-48 ns, e.g. about 20 ns, the pulse energy is at least 200 microjoule and the burst energy is accordingly at least 400 microjoule.
Subsequently, after introduction of one or in particular more than one filament-shaped flaw(s) 32, the glass element 1 is taken out and placed in an etching bath where, in a slow etching process, glass is removed along the filament-shaped flaws 32 so that a channel is introduced into the glass element 1 at the position of such a flaw 32.
A basic etching bath may have a pH of >12, for example a KOH solution having a concentration of >4 mol/l, for example >5 mol/l, for example >6 mol/l, but <30 mol/l. Etching is, in one embodiment of the invention, carried out at a temperature of the etching bath of >70° C., for example >80° C., or >90° C., irrespective of the etching medium used.
The channels 5 which have been introduced and are arranged next to one another to form a row along the path over which the laser travels can now serve as predetermined fracture positions in order to separate off part of the glass element 1, or the glass element 1, along this path.
Quite generally, without being restricted to the specific working example, a plate-like glass element 1 having a channel 5 which is open at the side and forms part of an edge 10 of the glass element 1 is formed by parting along a line running through one or more channels 5.
Furthermore, as shown in
In order to detach an inner part and/or produce an opening 13 in a glass element 1, a variant of the above-described method can be suitable. This embodiment of the invention is based on the diameter of the channels 5 being increased by etching to such an extent that the glass between the channels 5 is removed and the channels 5 join.
A glass element 1 in which the channels 5 have joined at the sides as a result of etching is shown in
Furthermore, all these examples are based on an embodiment of the process of the invention in which
The channels 5 generally have a tubular cylindrical basic shape, or are tubular with a cylindrical wall. Here, a slight taper from the opening at the side face to the middle of the glass element 1 can be present. When the generally cylindrical channels 5 are joined in the course of widening during the etching operation, ridges are formed at the abutting positions. In general, without being restricted to the example of
These ridges or ribs accordingly run parallel to the longitudinal direction of the channels and can therefore be seen only as serrations or tooth-like elements at the position of the transition region between neighbouring channels 5 in the depiction of
The spacing of the channels 5 is relatively large at about 50 μm in this example. The spacing can also be made smaller, especially in the case where the channels 5 go directly into one another without flat edge sections 11. In general, the spacing of the channels (also referred to as “pitch”) may be in the range from 3 to 70 microns. This spacing is measured from the middle to the middle of the channels. The transverse dimension, or the diameter of the channels 5, is, as indicated above, less than 100 microns. The diameter may be in a similar region to the spacing of the channels 5. Without being restricted to the examples described here, the diameter may be in the range from 3 microns to 50 microns. In the example of
The depth of the substantially hemispherical depressions 7 is typically less than 5 μm, at transverse dimensions of typically 5-20 μm.
It can be seen that the area of the edge 10 is greater than the area of a flat edge as a result of channels 5 having an approximately semicircular cross section through the lateral opening. If the channels 5 were to adjoin one another directly and have a precisely semicircular cross section, the length of the edge line parallel to the side faces 2, 3 would be greater by a factor of π/2 than the edge line of a smooth edge. The increases in the area which can be achieved by the process of the invention are somewhat smaller and are generally in the region of from 10 to 40 percent. According to one aspect of the invention, a plate-like glass element 1 having two opposite side faces 2, 3 and an edge 10, where the edge has a plurality of channels 5 which run parallel to one another and are open at the side and have a rounded wall 54 and a transverse dimension of less than 200 μm and whose longitudinal direction 51 runs transverse, e.g. perpendicular, to the side faces 2, 3 and which also end at the side faces 2, 3, or open into these, with the surface area of the edge 10 being increased by a factor of from 1.1 to 1.4 by the channels 5 compared to a smooth edge face without channels 5, is therefore provided. The edge 10 can be an outer edge or else, as in the examples of
This increase in the surface area gives a comparatively fracture-stable edge under flexural stresses, which is surprising in so far as the fracture probability normally correlates with the surface area. The structures projecting beyond the rounded channel probably lead to defects on these projected structures (ridges or flat edge sections) not being able to propagate far. Crack propagation is thus suppressed by the structuring of the edge 11.
This effect is reinforced further by the inventive fine structure of the channels 5 which is explained in more detail below. In
Furthermore, it can be seen that the ridges 70 form polygonal delimiting lines 71 of the depressions 7 when looked at in plan view onto the depressions 7. Here, the average number of the corners 72 of the delimiting lines 71 of the depressions 7 may also be less than eight, for example less than seven. The latter feature is obtained when the regions included by most of the substantially hemispherical depressions are convex in the mathematical sense.
The ridges 70 of the channel 5 shown in
The glass element 1 of the example shown in
A further glass from the class of low-alkali siliceous glasses which is well suited to the process of the invention is an alkali metal-free aluminasilicate glass. A glass may have the following composition:
Without being restricted to the abovementioned compositions, the glasses may have basicities in the range from 0.45 to 0.55, for example in the range from 0.48 to 0.54. This makes the glasses suitable for slow, controlled etching using basic etching media, but etching using acidic etching media also remains possible.
The embodiments described hitherto can have the disadvantage that not only the filament-shaped flaw but also both side faces 2, 3 of the glass element 1 are etched. Although the etching rate here is lower than within the channels 5, the decrease in thickness can nevertheless be undesirable. It may also be desirable not to alter the surface of the glass by way of the etching process. To avoid these disadvantages, a further embodiment of the invention provides for the surface of the glass element 1 to be covered in a first step by a polymer coating (for example a film or a surface coating) which is removed locally on introduction of the laser light. Thus, the polymer coating remains in the regions which surround the point of impingement of the laser and thus also the filament-shaped flaw and thus protects these regions of the side faces during subsequent etching.
The process and the glass element obtained are depicted in
This embodiment of the invention is thus based on at least one side face 2, 3, for example both side faces 2, 3 as shown in
A glass element 1 as is shown schematically in
It can be seen even from
A very circular cross section superimposed by small deviations from the circular shape as a result of the substantially hemispherical depressions 7 can also be achieved by way of the process of the invention.
The invention is suitable, inter alia, for producing interposers for electronic or microfluidic applications. For electronic applications, the channels 5 or openings having inner edges according to the invention can be filled with a conductive material in order to produce electric contacts from one side face to the other side face. Likewise, the channels 5 or larger openings produced by the channels 5 can serve for the conduction of fluids. If material is introduced into the channels 5, for instance to produce electric conduits through the glass element, the substantially hemispherical depressions 7 offer the advantage that this material can anchor readily in the channels 7. In the conduction of fluids, the depressions 7 can, on the other hand, reduce the flow resistance. Suitable applications are MEMS components. Here, particular mention may be made of a pressure sensor in which the glass element is fastened to a cap which deforms under the action of pressure. Here, openings for leading electric contacts to the cap and, particularly for a differential or relative pressure measurement, to allow pressure equilibration to the gas volume enclosed in the cap can be provided. Such a pressure sensor can measure capacitively, piezoresistively or resistively. In a resistive measurement, electric resistance layers which are connected to form a Wheatstone bridge can be provided in the cap. The voltage measured at the bridge is then proportional to the pressure-related deformation of the membrane.
A pressure sensor comprising a glass element according to the invention can, inter alia, be used in the following applications: a fuel pressure sensor in injection systems, an oil pressure sensor in gearboxes, a sensor in an airbag or for air pressure, e.g. for altitude measurements, a tyre pressure sensor.
If the spacing of the filament-shaped flaws is small, the channels 5 can quickly go over into one another during etching. The longer the etching process continues, the more do the structures produced by the channels 5 flatten. In contrast, the structure of the adjoining substantially hemispherical depressions 7 is retained. A further embodiment of the invention accordingly provides a plate-like glass element 1 having two opposite side faces 2, 3 and an edge 10 joining the two side faces 2, 3, with the edge 10 having a plurality of adjoining, rounded, substantially hemispherical depressions 7. Regardless of whether channels 5 can additionally be discerned, the lateral dimension or average transverse dimension of the depressions 7 is typically on average less than the depth thereof. The depressions 7 thus represents flat pans.
In order to obtain an essentially flat edge 10 without visible channels 5 running next to one another, a spacing of the filament-shaped flaws of less than 6 μm, e.g. less than 5 μm, can be used. An embodiment of the invention accordingly provides a process for producing a plate-like glass element 1 having a structured edge 10, wherein
A particular aspect of the invention when the process is used for separating off parts, in particular detaching inner parts and thus producing openings 13, is that very thin webs are produced as glass structures by two edges which run close to one another and have the inventive structure being introduced.
An embodiment of the invention therefore provides a plate-like glass element 1 which has a thickness in the range from 30 microns to 3 millimetres and has two opposite side faces 2, 3, wherein the contour of the glass element 1 comprises an elongated web 40 whose length 41 is at least five times, for example at least ten times, greater than its width, with length and width in each case being measured in a direction along a side face, and the edges 10 of the web 40 running next to one another each having a plurality of adjoining, rounded, substantially hemispherical depressions 7. The web 40 may be produced by separating off parts at the edges 40, using the above-described process in which the channels 5 are widened until they go over into one another and then flattened further as a result of etching, so that these may no longer be discernible as parallel structures perpendicular to the longitudinal direction of the edge 10. However, it is also possible to produce webs 40 having edges 10 as are shown in
The abovementioned aspect ratio of web length to web width reflects the fact that the webs 40 are elements having a highly filigree structure. As an alternative or in addition, the web width 42 of such a web 40 can be not more than four times the thickness of the glass element 1, for example not more than twice the thickness of the glass element 1. In one embodiment of the invention, the web width can even be smaller than the thickness of the glass element 1.
Regardless of the ratio of the width to the glass thickness of the aspect ratio, webs having a width of 400 μm or less, for example not more than 200 μm, or even 100 μm or less, can also be produced according to the invention.
The example shown in
As can also be seen in the example of
The edges 10 produced according to the invention are generally characterized, due to the substantially hemispherical depressions 7, by high strength and favourable statistical parameters, especially a high Weibull modulus. This can be advantageous in the case of fragile elements having edges such as the webs 40 shown in
Due to high stability and strength of the edges produced according to the invention, the invention is suitable for complex and fragile structures which are not producible by using other processes. Thereto belong also non-symmetrical structures with thin and/or long webs. However, at the same time, it was also ascertained that the stability of the products considerably depends on the geometry. In more detail, it was ascertained that it is more favourable to comply with a certain geometric specification, in case of a structure which is held in openings in the glass element, by one or more webs. A sufficient stability and manageability is ensured by this specification. Particularly, a glass element is provided for that purpose which has at least two openings 13 such that a structure having at least one web 40 is formed between the openings 13. In doing so, a parameter G may be assigned to the structure that is given by the relation
In doing so, glass elements according to the invention may still be realized with well mechanic stability, if the parameter G is at least 10 mm−1/3, for example at least 50 mm−1/3, for example 100 mm−1/3. Vice versa, it is sufficient, if the parameter is at most 400 mm−1/3, for example at most 300 mm−1/3, for example at most 200 mm−1/3.
The variable h in the above relation denotes the thickness of the glass element 1.
For clarifying the parameters of the relation,
In the above relation, l1 denotes the longest edge length between two adjacent contact points or contact regions 45 positioned along the edge of the structure, of one or two different webs 40 with the glass element 1. Therefore, this quantity denotes the arc length of the longest edge between two adjacent contact regions 45. The edges 46, 47 of the web 40 may, as also shown by the example of
The length l2 denotes the shortest straight-line distance of two contact regions 45 at the ends of the web 40. The edge-to-edge distance of the circular contact region 45 is significant for both lengths l1 and l2. In case of more than two contact regions 45, the paths of the lengths l1 and l2 do not necessarily continue between the same contact regions 45. The double arrow delineated in
The parameter b finally denotes the smallest distance of the openings 13 from each other, along the web 40, or, with other words, the minimal web width.
Such a geometry, as afore-said described, is, with respect to strength and manageability especially advantageous in connection with the forming of the edge, according to the invention, therefore with hemispherical deepenings. Such a geometry may nevertheless be used with differently formed edges.
In case of the shown example, only one single web 40 is present. But also a plurality of structures is possible which may be carried by more than one web. In that context, it is important that, in that case, the paths l1 and l2 may continue between different contact regions 45. For evaluating the stability of a design, G therefore relates the longest possible distance between two contact regions l1 to the shortest possible connection l2 of two contact points. N≥2 principally applies for the number N of contact regions.
For the sake of further illustration,
By way of the two upper structures 39, it may be seen that the distance l2 and the arc length l1 between the contact regions 45 may be calculated at different webs. The longest edge length l1 between two adjacent contact points positioned along the edge of the structure is relevant for the parameter G. This is each delineated for both structures 39. In case of the example of the upper-most, circular structure 39, in particular a shortest distance l2 between two contact regions 45 and a longest edge length between two other, adjacent contact regions 45.
In one embodiment of the invention, not depending on the morphology of the edges. a plate-like glass element having a thickness in the range from 30 micrometres to 3 millimetres and two side faces 2, 3 facing each other is accordingly provided, wherein at least two openings 13 are inserted in the glass element 1 such that the region of the glass element 1 between the openings forms a structure 39 with at least one web 40 whose minimal width is less than 1 mm, wherein a parameter G is defined for the structure, G given by the above-mentioned relation, wherein the parameter G has a value of at least 10 mm−1/3 and of at most 400 mm−1/3, wherein l1 is the longest edge length between two contact regions 45 being adjacent along the edge of one of the openings 13, and l2 is the length of the shortest possible straight-line connection between two contact regions 45, and wherein a contact region 45 of a web 40 is each defined as a circular region of the glass element 1, having a diameter of 1 mm, the circular region arranged at the web 40 such that its border each touches the borders of both openings 13 at at least one point, the intermediate range of the openings forming the web 40, and wherein b denotes the minimal web width, h the thickness of the glass element 1 and N the number of the contact regions 45. Webs having a minimal width of not less than 300 μm can be used, for this embodiment.
Also in case of the above-described geometry of a glass element with one or more webs, fractures at the web may easily occur during production.
It was furthermore ascertained that, when producing such products, rejects due to web fracture occur, to an increased degree. This risk particularly exists with glass element whose openings are clearly larger than the remaining webs.
When detaching the inner parts, the webs may twist in the glass element and take damage, in doing so. This may be avoided by generally, additionally to the closed separation line, inserting auxiliary intersections, or auxiliary lines, respectively, made of adjacent, filament-shaped damages which divide an inner part limited by the closed separation line into smaller segments. In doing so, it was ascertained that can be advantageous, if an inner part is at least bisected, e.g. quartered, by way of an auxiliary intersection.
In a refinement, the auxiliary lines are selected with regard to course and number such that the inner part 9 is divided into segments of the maximally 20-fold size, for example the maximally 10-fold size, for example the maximally two-fold size of a web between two inner parts 9. In doing so, the size ratio is determined by the ratio of minimal web width to maximal diagonal of a segment. Accordingly, the maximally long diagonal of a segment is therefore 20-times, for example 10-times, for example two-times longer than the minimal web width.
While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
Number | Date | Country | Kind |
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10 2017 101 673.2 | Jan 2017 | DE | national |
10 2018 100 299.8 | Jan 2018 | DE | national |
This is a non-provisional application based upon U.S. provisional patent application Ser. No. 62/451,117, entitled “STRUCTURED PLATE-LIKE GLASS ELEMENT AND PROCESS FOR THE PRODUCTION THEREOF”, filed Jan. 27, 2017, which is incorporated herein by reference.
Number | Date | Country | |
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62451117 | Jan 2017 | US |