DE102013104212A1 - Bird protection glass used for exterior glazing, has bird-resistant coating comprising nitride(s) of titanium, zinc, tin, strontium-titanium, tungsten-bismuth, iron, silver, iron-silver, niobium, zirconium, tantalum or their alloy - Google Patents

Abstract

A bird protection glass (1) consists of a transparent, preferably silicate, substrate (2) coated with a bird-resistant coating comprising layer(s) (3) of nitride(s) of titanium, zinc, tin, strontium-titanium, tungsten-bismuth, iron, silver, iron-silver, niobium, zirconium, tantalum, and/or their alloys. An independent claim is included for manufacture of bird protection glass.

Description

The invention relates to a bird protection glass and a method for producing a bird protection glass.

A bird protection glass is for example from the DE 103 22 500 A1 known. In the known Vogelschutzglas is produced by laser processing on a glass or a transparent plastic disc or in a vapor-deposited on the UV-absorbing or reflective metal oxide layer, a fine structure, which is indeed recognizable for certain species of birds, but not for humans. The UV-visibility of some bird species is exploited. The structures produced by laser processing produce absorptions or reflections in the UV range, ie in the ultraviolet spectral range, and are thus visible to the UV-visible bird species, but not to humans. Due to the structures made visible for the various bird species, the glass panes for the birds become recognizable, so that the bird strike on glass panes, in particular on large glass panes, can be reduced. The metal oxide of the metal oxide layer is not specified. A laser processing requires a corresponding laser system, which is associated with additional effort.

The US 2009/0047487 A1 also discloses a bird protection glass patterned into patterns of UV-reflective and UV-absorbing regions, particularly in permanent or non-permanent coatings on a transparent glass or polymeric disk.

The US 5,480,722 A discloses UV-absorbing coatings of glass for UV protection in motor vehicles, but not a bird protection glass. As materials for the layer system, there are disclosed zinc oxide, titanium oxide and cerium oxide for the UV absorbing layer and a metal oxide intermediate layer of at least two components which may be selected from zinc oxide, silica, alumina, germania, zirconia, titania and ceria. A liquid solution is applied and then baked at 200 ° C for the intermediate layer and then another solution applied by spin coating and baked at 600 ° C to obtain the UV absorbing film. In addition to such wet coatings also transfer printing or flexographic printing is specified.

The US Pat. No. 6,420,032 B1 also discloses a coating system for UV protection in motor vehicles, but not a bird protection glass. On a transparent polymer substrate, a transparent intermediate metal layer and thereon a transparent UV-absorbing metal oxide layer are arranged. The metal layer comprises aluminum or silver, but nickel, iron, copper, tin or gold may also be used, and the metal oxide layer comprises zinc oxide, titanium oxide, cerium oxide, indium-doped zinc oxide or aluminum-doped zinc oxide. In addition, zinc sulfide or titanium oxide, tantalum oxide, niobium oxide, cerium oxide, indium oxide, indium tin oxide or zinc oxide doped with fluorine, boron, aluminum, gallium, thallium, copper or iron can also be used for the UV-absorbing layer. The metal interlayer is deposited by sputtering, organometallic CVD, arc plasma deposition, evaporation or electron beam evaporation. The UV-absorbing metal oxide layer is deposited by CVD, reactive evaporation, sputtering, plasma deposition or reactive sputtering.

Based on this, an object of the invention is to provide a new bird protection glass and a corresponding manufacturing method.

This object is achieved with respect to the bird protection glass by the features of, at least optional, independent claims 1, 3 and 5 and with respect to the manufacturing process solved by the features of claims 8 and 9. Embodiments and variants will become apparent from the further features of the respective dependent claims.

According to the invention, a bird protection glass is provided, which comprises a transparent substrate, in particular a transparent substrate on a silicate basis such as a (silicate) glass, with a bird protection coating. For the term bird protection "glass" the transparent (in the visible for human optical spectrum between about 400 and 800 nm) transparent property of the substrate is sufficient. A glass in the narrower inorganic chemical sense does not have to exist. It may also be an organic or polymer-based transparent substrate. The substrate is preferably a, in particular flat, disc. Thus, for example, a conventional glass pane, preferably flat glass, but also a transparent polymer pane can be used as a glass substitute as the substrate.

By "bird protection" and a "bird protection coating" is to be understood that, in comparison to conventional transparent panes (or in general: substrates), in particular glass panes, without bird protection measures, by the coating protection for birds from bird strike, especially bird death, to the Slices can be achieved. The bird protection coating thus serves to reduce bird strike on corresponding transparent panes. Preference is given to a visible and / or dissuasive structuring for birds, for example with fine lines or Stripes, or design, for example in the form of birds of prey or the like, the bird protection coating provided.

According to a first embodiment of the invention, the bird protection coating comprises at least one layer comprising at least one nitride of at least one of titanium (Ti), zinc (Zn), tin (Sn), strontium titanate (SrTi), tungsten bismuthate (WBi), iron (Fe ) Comprises silver (Ag), FeAg, niobium (Nb), zirconium (Zr), tantalum (Ta) and alloys thereof of the broad group of metallic materials of selected base material, in particular nitrides of at least two of the base materials.

• – Abscheiden zumindest einer metallischen Schicht aus zumindest einem aus der Ti, Zn, Sn, SrTi, WBi, Fe, Ag, FeAg, Nb, Zr, Ta und Legierungen derselben umfassenden Gruppe von metallischen Materialien ausgewählten Basismaterial und
• – reaktiv thermisches Behandeln der metallischen Schicht in einer Stickstoff-Atmosphäre, wodurch oder wobei das oder die Metall(e) oder Basismaterial(ien) nitriert wird bzw. werden bzw. Metallnitrid(e) entsteht bzw. entstehen.

According to a preferred method for producing such a bird protection glass, a transparent, preferably silicate, substrate is coated with the following steps:

• Depositing at least one metallic layer of at least one base material selected from the group of metallic materials comprising Ti, Zn, Sn, SrTi, WBi, Fe, Ag, FeAg, Nb, Zr, Ta and alloys thereof
• Reactive thermal treatment of the metallic layer in a nitrogen atmosphere, whereby or wherein the metal (s) or base material (s) is / are nitrated or metal nitride (s) is formed or formed.

According to a second embodiment of the invention which can also be combined with the first embodiment, the bird protection coating has at least one layer comprising at least one oxide of at least one of titanium (Ti), zinc (Zn), tin (Sn), strontium titanate (SrTi), tungsten bismuthate (WBi), iron (Fe), silver (Ag), FeAg, niobium (Nb), zirconium (Zr), tantalum (Ta) and alloys of the same group of metallic materials selected base material, preferably at least one of the SrTi, WBi , FeAg and alloys of the same comprehensive group of materials selected base material, preferably oxides of at least two of said base materials.

• – Abscheiden zumindest einer metallischen Schicht aus zumindest einem aus der Ti, Zn, Sn, SrTi, WBi, FeAg, Fe, Ag, Nb, Zr, Ta und Legierungen derselben umfassenden Gruppe von metallischen Materialien ausgewählten Basismaterial und
• – reaktiv thermisches Behandeln der metallischen Schicht (3) in einer Sauerstoff-Atmosphäre, wodurch oder wobei das oder die Metall(e) oder Basismaterial(ien) oxidiert wird bzw. werden bzw. Metalloxid(e) entsteht bzw. entstehen.

According to a preferred method for producing such a bird protection glass, a transparent, preferably silicate, substrate is coated with the following steps:

• Depositing at least one metallic layer of at least one base material selected from the group of metallic materials comprising Ti, Zn, Sn, SrTi, WBi, FeAg, Fe, Ag, Nb, Zr, Ta and alloys thereof
• Reactive thermal treatment of the metallic layer ( 3 ) in an oxygen atmosphere, whereby or the metal (s) or base material (s) is / are oxidized or metal oxide (s) arises or arise.

As far as metal oxide layers are concerned, it may be advantageous in terms of the desired reflection properties to form substoichiometric oxides, in particular mixed oxides.

According to a third embodiment of the invention, which can also be combined with the first and / or second embodiment, the bird protection coating has at least one binary metallic layer, which consists of the titanium (Ti), zinc (Zn), tin (Sn), strontium titanate (SrTi). , Tungsten bismuthate (WBi), iron (Fe), silver (Ag), FeAg, niobium (Nb), zirconium (Zr), tantalum (Ta) and alloys of the same broad group of metallic materials selected base materials. Corresponding binary metallic layers, d. H. based on two of the base materials produced metallic layers can be produced in a particularly simple manner. In particular, a binary metallic layer with the base materials Zn and Ti or Zn and Nb has proved to be suitable, with Zn showing more absorption properties and Ti and Nb showing more reflection properties.

The term "metallic" may in the following refer to metals in elemental form, also to metal compositions and mixtures as well as alloys as well as to metal compounds such as metal oxides and metal nitrides, if no further specification is specified in the individual case.

By "oxygen atmosphere" or "nitrogen atmosphere" is meant an atmosphere having a sufficient (or sufficient) partial pressure of the oxygen or nitrogen for the chemical reaction (oxidation or nitration, respectively).

Surprisingly, it has been found that the degree of reflection and / or the degree of absorption of the proposed bird protection coating in the perceptible for various types of birds ultraviolet (UV) spectral range, in particular in the range of about 315 nm to 380 nm, compared to an uncoated substrate and / or with respect to the human perceivable spectral range is increased between about 400 nm and 800 nm. As a result, the bird protection glass can be seen for various bird species with UV visibility in the range of 315 nm to 380 nm, so that these bird species can escape corresponding glass panes. Bird strike and bird death on the glass panes can thus be reduced.

According to a further embodiment, it is provided that the at least one layer is covered by an oxide layer, in particular a silicon dioxide layer. Preferably, the oxide layer has a thickness of about 1 nm to 3 nm. In particular, a silicon dioxide layer is substantially transparent to UV radiation in the relevant spectral range, so that the advantageous properties of the metallic layer are substantially not impaired, but a kind of protective layer for the underlying metallic layer can be achieved. According to a further embodiment of the production method, it is provided that the silicon dioxide layer is applied in a sputtering process. This results in process engineering advantages, especially if already the metallic layer is applied by sputtering. In particular, in this case, the silicon dioxide layer may be deposited prior to the step of thermal treatment, after depositing the metallic layer in vacuum sequence. Advantageously, a massive silicon planar or tube target is used to deposit the silicon oxide layer.

Overall, it has also been shown that with the combination of the metallic layer, in particular in the variants metal oxide and / or metal nitride, with the oxide layer, in particular silicon oxide layer, a particularly advantageous weather resistance can be achieved.

According to one embodiment, it is provided that the metallic layer has a thickness of at least 25 nm, preferably up to 50 nm, or is generated accordingly. Layer thicknesses in this range have proven to be effective and at the same time sufficient to obtain the desired increase in reflection, in particular in the ultraviolet perception range of about 315 nm to 380 nm.

With the proposed manufacturing method, a bird protection coating, in particular according to the embodiments and variants described above, can be realized on glass panes in a particularly simple manner, and in particular with existing coating systems for glass panes. Elaborate additional installations, such as required according to the prior art laser systems can be avoided.

According to one embodiment of the production method, the thermal treatment takes place at a temperature of more than 600 degrees Celsius (° C), preferably up to 760 degrees Celsius. In particular, advantageous degrees of oxidation and / or degrees of nitration can be achieved at layer-side temperatures in the range between in the range of 685-705 ° C. On the layer side, this should concern the side of the bird protection glass on or on which the metallic layer is applied. Temperatures in the abovementioned ranges have proved to be particularly advantageous for the formation of corresponding metal oxides or metal nitrides, in particular substoichiometric metal oxides or metal nitrides. Substoichiometric metal oxides or metal nitrides are of importance insofar as they have advantageous properties with regard to weather resistance and the like in addition to the intended effect of increasing the reflection in the ultraviolet spectral range.

According to a particularly advantageous embodiment of the manufacturing method is provided that the metallic layer is applied in a sputtering process. Sputtering processes are already known for applying various other layers or layer systems in the case of glass panes, so that the proposed bird protection pane can be produced comparatively inexpensively and simply.

In the sputtering method, a mosaic target comprising the base materials to be deposited is preferably used. Mosaic targets as such are also known by the term segment target. Mosaic targets comprise or contain the base materials to be deposited in separate, mosaic-like individual targets. The use of mosaic or segment targets has proved to be particularly advantageous in order to achieve the desired increase in the reflectance of the disc in the ultraviolet spectral region of interest. The targets preferably have dimensions of up to 15 cm in at least one dimension.

Particularly advantageous bird protection coatings can be achieved if, according to a further embodiment of the invention, respective targets of the base materials provided for the sputtering process are arranged alternately in the sputtering process. In particular, it is advantageous if the targets are arranged alternately in strips next to each other. The strip-shaped targets may, for example, and preferably have a width of about 7 cm transverse to the longitudinal direction. In the longitudinal direction, the strip-shaped targets can correspond to the dimensions of the respective pane, in particular glass pane.

The bird's eye shield produced according to the proposed production method has, in analogy to the above-described bird's eye shield in the ultraviolet spectral range around 315 nm to 380 nm, a 400 nm to 800 nm compared to the uncoated substrate and / or the human visible spectral range increased reflectance. The increased reflectance in the ultraviolet spectral range means that birds with UV visibility in this area can better recognize and identify glass panes and glass surfaces. Consequently, the bird strike and bird death can be reduced to glass panes and corresponding glass surfaces.

Embodiments of the invention are described below, in particular in connection with the accompanying figures. Show it:

1 a perspective, partially broken view of a bird protection glass; and

2 a diagram of the reflectance of bird protection glasses according to the invention.

1 shows a perspective, partially broken view of a bird protection glass 1 , The bird protection glass comprises a transparent silicate substrate, more precisely a glass pane 2 , On the glass 2 is a metallic layer 3 deposited. The metallic layer 3 is with a silicon dioxide layer deposited thereon 4 covered in the 1 is shown broken.

The bird protection glass 1 , especially those on the glass 2 applied bird protection coating, was prepared as follows.

The coating of the glass pane 2 took place in a sputtering plant, in particular a magnetron plant, in which also large-sized slices with dimensions of up to 6 m × 3.20 m can be made. Glass panes with the proposed bird protection coating can be produced essentially in all pane formats, in particular up to the aforementioned dimension.

In the sputtering plant was the glass 2 successively sputtered in vacuum sequence by means of a planar mosaic target and a massive planar Si target O ₂ -reactive.

The mosaic target comprised 7 cm wide tiles that were alternately arranged over the entire target width. The individual tiles comprised two base materials of the Ti, Zn, Sn, SrTi, WBi, Fe, Ag, FeAg, Nb, Zr and Ta group of metallic base materials, so that, for example, for the base materials Ti and Zn for the mosaic target Tile sequence Zn / Ti / Zn etc. resulted.

After the deposition of the metallic layer 3 and the silicon dioxide layer 4 ie SiO ₂ layer 4 , an annealing process, also known as distortion, was carried out in oxygen atmosphere. This was the glass 2 and in particular the metallic layer 3 heated.

For 6 mm thick glass panes 2 the heating time was about 400 to 420 seconds. During the heating process, the glass was 2 on the coating side to about 685 ° C to 705 ° C, and the coating is heated to about 720 ° C-750 ° C warmed.

In particular, the deposited metal layers, for example Zn and Ti layers, were oxidized by this heating process, and a binary substoichiometric mixed oxide formed on the glass pane 2 out. Overall, revealed on the surface of the glass 2 a sequence of metallic sublayers, for example ZnO _x / TiO _x / ZnO _x / etc. The individual sublayers are 1 indicated by dashed lines, wherein the layers with a metal oxide, for. ZnO _x layers, with A and the layers with another metal oxide, for. B. TiO _x layers are denoted by B.

The thickness of the SiO ₂ layer 4 was in the range between 2 nm and 3 nm. The thickness of the entire bird protection coating was about 30 nm. However, other thicknesses and thickness ratios come into question.

In the method described above, the annealing was carried out in an oxygen atmosphere, whereby the metallic layers, in particular Zn and Ti layers or Sn, SrTi, WBi, Fe Ag, FeAg, Nb, Zr and / or Ta layers that have been oxidized. This oxygen variant or O variant is almost neutral in color.

Also, the oxides of SrTi, WBi and / or Fe or Ag or FeAg show good bird protection properties, in particular depending on the alloying proportions.

In addition to the mentioned variant, it is also possible in another variant according to the invention to carry out the annealing in a nitrogen atmosphere, ie N ₂ atmosphere, whereby metal nitrides are formed instead of the metal oxides. In contrast to the oxygen variant, the nitrogen variant is not neutral in color, but is colored, in particular yellowish to yellow, and bluish depending on the layer structure.

Both variants, d. H. the nitrogen variant and the oxygen variant, and also mixtures thereof, are effective to reduce bird strike on window panes or glass surfaces, which will be discussed in more detail below.

Typical partial pressures of O ₂ and N ₂ are in the range of 0.002 to 0.005 Torr.

2 shows diagrams of the reflectance of the above-mentioned variants of Vogelschutzgläser, ie the oxygen variant and the nitrogen variant, which are referred to below with O variant and N variant.

Exactly is in 2 the reflectance versus wavelength is plotted. On the ordinate the reflection is plotted in% and on the abscissa the wavelength in nm.

A first reflection curve R1 shows, depending on the wavelength, a typical reflectance of the underlying glass pane 2 without coating. A second reflection curve R2 shows, depending on the wavelength, a typical degree of reflection of the O variant of the bird protection glass 1 , A third reflection curve shows, depending on the wavelength, a typical reflectance of the N variant of the bird protection glass 1 ,

Out 2 It can be seen that the reflectance of the O variant and the N variant in the ultraviolet range, in particular in the, in 2 represented by hatching, range of 315 nm to 380 nm is significantly increased. The bird protection glasses in O variant and N variant show a centroid wavelength of about 364 nm.

The reflectance is increased in the range of the centroid wavelength 364 nm in the O variant and N variant in about 3-fold to 4-fold.

Against the background that many species of birds, especially songbirds, are UV-aware, d. H. UV receptors with sensitivities in the UV range of 315 nm to 380 nm, it is clear that the bird protection glass can be better recognized by the increased in just this UV range reflectance of UV-sensitive bird species. Overall, the bird strike and bird death can be reduced to window panes.

In a field trial, a conventional glass panes without Vogelschutzmaßnahme with the bird protection glass proposed here 1 compared to the absolute number of bird strikes. The size of the glazed area was 15 m ^{2 in} each case, with the glazed areas being tested at the same location, ie successively for at least one year. In the conventional glass pane, 6 to 8 bird strikes were registered annually. When bird protection glass 1 No bird strike was recorded during the year. This proves the effectiveness of the bird protection coating proposed here.

It should also be noted that the reflectance in the spectral range of 400 nm and 800 nm perceptible by humans is indeed increased. However, the reflectance decreases toward longer wavelengths and is only moderately elevated over the uncoated glass so that the effects on the human perceivable spectral range are quite acceptable.

As a further advantage of the proposed coating was also found that in addition to the increased reflectance in the UV range, an advantageous weather resistance can be achieved. Both advantages make the proposed as proposed glass sheet particularly suitable for exterior glazing, such as buildings, facades, noise barriers, etc.

Overall, it is clear that with the proposed coating bird strike can be reduced to windowpanes. The coating is thus particularly well, d. H. can be preferably used as bird protection coating.

LIST OF REFERENCE NUMBERS

1

Bird protection glass

2

pane

3

metallic layer

4

silicon dioxide

A

first metal oxide

B

second metal oxide

R1

first reflection curve

R2

second reflection curve

R3

third reflection curve

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 10322500 A1 [0002]
• US 2009/0047487 A1 [0003]
• US 5480722A [0004]
• US 6420032 B1 [0005]

Claims (11)

Bird protection glass ( 1 ) comprising a transparent, preferably silicate, substrate ( 2 ) with a bird protection coating, the bird protection coating comprising at least one layer ( 3 comprising at least one nitride of at least one base material selected from the group of metallic materials comprising Ti, Zn, Sn, SrTi, WBi, Fe, Ag, FeAg, Nb, Zr, Ta and alloys thereof. Bird protection glass ( 1 ) according to claim 1, wherein the bird protection coating comprises at least one layer ( 3 ) comprising nitrides of at least two of the base materials. Bird protection glass ( 1 ), in particular according to claim 1 or claim 2, comprising a transparent, preferably silicate, substrate ( 2 ) with a bird protection coating, the bird protection coating comprising at least one layer ( 3 comprising at least one oxide of at least one selected from the group consisting of Ti, Zn, Sn, SrTi, WBi, FeAg, Fe, Ag, Nb, Zr, Ta and alloys thereof, preferably at least one of the SrTi, WBi, FeAg, Fe, Ag and alloys of the same comprehensive group of materials selected base material. Bird protection glass ( 1 ) according to claim 3, wherein the bird protection coating comprises at least one layer ( 3 ) comprising oxides of at least two of the base materials. Bird protection glass ( 1 ), in particular according to one of claims 1 to 4, comprising a transparent, preferably silicate, substrate ( 2 with a bird protection coating, the bird protection coating comprising at least one binary metallic layer ( 3 comprising two base materials selected from the group consisting of Ti, Zn, Sn, SrTi, WBi, Fe, Ag, FeAg, Nb, Zr, Ta and alloys thereof. Bird protection glass ( 1 ) according to one of claims 1 to 5, wherein the at least one layer ( 3 ) has a thickness of at least 25 nm, preferably up to 50 nm. Bird protection glass ( 1 ) according to one of claims 1 to 6, wherein the at least one layer ( 3 ) by a cover layer, in particular an oxide cover layer, preferably a silicon dioxide layer ( 4 ), which preferably has a thickness of about 1 nm to 3 nm. Method for producing a bird protection glass ( 1 ) according to claim 1 or claim 2 or one of the claims dependent on claims 1 and 2, wherein a transparent, preferably silicate, substrate ( 2 ) is coated with the following steps: deposition of at least one metallic layer ( 3 of at least one base material selected from the group of metallic materials comprising Ti, Zn, Sn, SrTi, WBi, Fe, Ag, FeAg, Nb, Zr, Ta and alloys thereof and reactive thermal treatment of the metallic layer (US Pat. 3 ) in a nitrogen atmosphere. Method for producing a bird protection glass ( 1 ) according to claim 1 or claim 2 or one of the claims dependent on claims 1 and 2, wherein a transparent, preferably silicate, substrate ( 2 ) is coated with the following steps: deposition of at least one metallic layer ( 3 of at least one base material selected from the group of metallic materials comprising Ti, Zn, Sn, SrTi, WBi, Fe, Ag, FeAg, Nb, Zr, Ta and alloys thereof and reactive thermal treatment of the metallic layer (US Pat. 3 ) in an oxygen atmosphere. A method according to claim 8 or claim 9, wherein the thermal treatment is carried out at a temperature of at least 600 ° C, preferably up to 760 ° C. Method according to one of claims 8 to 10, wherein the metallic layer ( 3 ) is deposited in a thickness of at least 25 nm, preferably up to 50 nm, and / or wherein the metallic layer ( 3 ) is applied in a sputtering process in which preferably a mosaaiktarget comprising the base materials to be deposited is used, wherein preferably respective targets of the base materials are arranged alternately, in particular strip-like alternating, and / or wherein on the at least one metallic layer a silicon dioxide layer ( 4 ), preferably with a thickness of about 1 to 3 nm, wherein the silicon dioxide layer ( 4 ) preferably after deposition of the metallic layer ( 3 ), in particular in vacuum sequence, is applied in a sputtering process, wherein preferably a solid silicon planar or tubular target is used.

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