The invention generally relates to the field of heat protection glazings. More particularly, the invention relates to heat protection glazings that are provided with infrared-reflective coatings. Heat protection glazings are used, for example, as oven windows and as glass in wood-burning stoves. To reflect infrared radiation back into the hot space of such a unit, it has been known to use transparent, electrically conductive coatings. Suitable, for example, are indium tin oxide and fluorine-doped tin oxide. However, long-term stability of such layers is insufficient, since, generally, due to the exposure to high temperatures the plasma edge of these layers shifts such that reflection efficiency decreases significantly. Moreover, the particularly effective indium tin oxide layers are comparatively expensive to manufacture. Furthermore, the transparency of the layers may change.
EP 1 518 838 B1 discloses an observation window having a multilayer coating for high-temperature applications, such as for glass melting furnaces and incinerators. Indium tin oxide is used as one of the layers as an alternative to metallic titanium. At the same time the coating is intended to have a light-shielding effect, so that a high degree of transparency is not desired here. The transmittance in the visible spectral range is intended to be not more than 10%. Another problem with the durability of coatings arises is the substrate has a small coefficient of thermal expansion. However, it's just a small thermal expansion coefficient that is favorable for temperature-resistant glasses and glass ceramics. With a small coefficient of thermal expansion, the coating may tear or even flake off when the heat protection glazing is heated strongly, due to the differences in the thermal expansion coefficients of the coating and the substrate and the mechanical stresses associated therewith.
Accordingly, there is a need to provide a low cost infrared-reflective coating on temperature resistant transparent substrates, which is stable and effective even under very long lasting thermal loads, but which is transparent in the visible spectral range. This object of the invention is achieved by the subject matter of the independent claims. Advantageous embodiments and modifications of the invention are set forth in the respective dependent claims.
Accordingly, the invention provides a heat protection glazing with a high-temperature infrared reflecting filter coating, wherein the heat protection glazing comprises a glass or glass-ceramic sheet having a linear coefficient of thermal expansion α of less than 4.2*10−6/K, preferably even less than 3.5*10−6/K, wherein at least one surface of the glass or glass-ceramic sheet is coated with a titanium dioxide layer which is doped with at least one transition metal compound, preferably a transition metal oxide, so that the titanium dioxide layer has a sheet resistance of not more than 2MΩ, and wherein the titanium dioxide layer has a layer thickness of an optical thickness corresponding to one quarter of the wavelength of the maximum of a black body radiator at a temperature between 400° C. and 3000° C. Surprisingly, it has been found that the titanium dioxide layers doped according to the invention remain free of haze, even in long-term operation under high temperature loads.
The invention further relates to a thermal process unit with a hot space and a window closing the hot space, which comprises a heat protection glazing with a high-temperature infrared reflecting filter coating according to the invention.
The method for producing such a heat protection glazing with a high-temperature infrared reflecting filter coating, accordingly, is based on depositing a titanium dioxide layer doped with a transition metal or a compound of a transition metal on a glass or glass-ceramic sheet, wherein the layer is doped such that it has a sheet resistance of not more than 2MΩ, and with an optical thickness corresponding to one quarter of the wavelength of the maximum of a black body radiator at a temperature between 400° C. and 3000° C. According to a first embodiment of the invention, the coating is deposited on a glass or glass-ceramic substrate having a low linear coefficient of thermal expansion α of less than 4.2*10−6/K.
According to another embodiment, the low thermal expansion may be obtained by a further process step following the deposition. In particular, ceramization is considered in his case. Accordingly, the titanium dioxide layer is deposited on a glass sheet, and the coated glass sheet is subsequently ceramized, so that a glass-ceramic sheet coated with the doped titanium dioxide layer is obtained that has a linear coefficient of thermal expansion α of less than 4.2*10−6/K.
Very surprisingly here, the coating according to the invention remains free of haze following ceramization. In accordance with yet another embodiment of the invention it is even possible, to deform the glass or glass-ceramic sheet in a hot-forming step after the high-temperature infrared reflecting filter coating has been deposited. According to a variation of this embodiment of the invention, the doped titanium dioxide layer is deposited on a sheet of ceramizable glass. Such glass sheets of ceramizable glass are also known as green glass sheets. According to this embodiment, hot-forming is accomplished while the sheet softens during ceramization.
Titanium dioxide is a compound semiconductor, and by adding the transition metals, preferably in form of oxides, it is stimulated to provide free carriers. As a result thereof, a conductive coating can be obtained from purely dielectric titanium oxide.
It has been found that the titanium dioxide layers doped with the transition metal or a transition metal compound are very temperature-stable and at the same time do not degrade substantially by a shift of the plasma edge under the operation-related temperature influence in the thermal process unit. Additionally, according to the invention, optical interference of the titanium dioxide layer is exploited, as the layer acts as a λ/4 layer for the infrared radiation incident thereon. Thus, the high-temperature infrared reflecting filter coating according to the invention acts as both as a transparent conductive oxide and as an optical interference reflective layer.
The above-mentioned property of a λ/4 layer for thermal radiation at temperatures between 400° C. and 3000° C. may typically be achieved with a layer thickness ranging from 80 to 750 nanometers, preferably from 80 to 250, more preferably from 100 to 150 nanometers. A layer thickness of 750 nanometers, with typical indices of refraction of the doped layer, corresponds to an optical thickness of λ/4 adapted to a maximum of a spectral intensity distribution of a temperature radiator with a temperature of 400° C. However, layers adapted for higher temperatures, i.e. thinner layers, are preferred. This is partly because the energy content increases as the wavelength decreases, so that an adaptation to smaller wavelengths than that of the maximum of the spectral intensity distribution may be useful.
Good conductivity of the coating may in particular be achieved by replacing cations in the lattice by higher-valence ions, so that electrons are emitted into the conduction band and thus produce conductivity.
Dopants which do not differ too significantly from titanium in shape and size have proven particularly suitable for achieving a high doping efficiency, i.e. a large number of emitted electrons per impurity atom. These conditions are in particular met by compounds of at least one of transition metals Nb, Ta, Mo, V. Among the above mentioned transition metals, niobium and tantalum are especially suitable as a dopant to achieve a low sheet resistance or a high conductivity. When doping with these metals or compounds thereof, electrical resistivities of less than 2*10−3 Ω·cm may be achieved, in particular around 1*10−3 Ω·cm. The sheet resistance of layers according to the invention may thus be less than 1 kΩ. Such low sheet resistances may possibly also be achieved when using other transition metals or compounds thereof as a dopant.
For depositing the titanium dioxide layer, a sputter process is particularly suitable. The sputter process may comprise reactive sputtering using a metallic target. According to another embodiment a ceramic target is used. The simplest way to incorporate the dopant is to use a target doped with the transition metal. In case of oxidized ceramic targets, this additionally provides for a sufficient conductivity of the target in correspondence with the deposited layer. However, co-deposition from two targets is likewise possible.
A sheet resistance of the titanium dioxide layer of not more than 2 MΩ may typically be obtained by doping with a transition metal compound in an amount from 1 to 10 percent by weight, preferably from 3 to 6 percent by weight. Moreover, with such doping ranges good transparency of the layer is achieved. Higher amounts of doping result in increased occupancy of the interstitial sites and hence in reduction of transparency. For example, a titanium oxide target doped with 1 to 10 percent by weight of niobium oxide may be used for this purpose. Alternatively, the doped titanium dioxide layer may be formed by reactive sputtering in an oxygen containing atmosphere.
Furthermore, it has been found to be particularly advantageous if the titanium dioxide layer contains a crystalline phase. An anatase crystalline phase exhibits particularly favorable properties. This is surprising in that at high temperatures anatase transforms to rutile. As such, one would expect that the anatase-containing layer is less temperature-stable, whereas the deposited layers exhibit a high long-term stability without significant changes in film morphology.
Moreover, anatase-containing layers have proved to be advantageous for their good conductivity that is achievable. It has been found that for the same doping the sheet resistance of an anatase-containing layer is lower than that of for example a rutile-containing layer.
Preferably, however, the titanium dioxide layer is not purely crystalline. Rather, best results in terms of temperature stability and conductivity were obtained when the titanium dioxide layer also included an X-ray amorphous phase. This, again, is surprising, since one could assume that the equilibrium between the phases might change due to the influence of temperature. So, according to a particularly advantageous embodiment of the invention, the titanium dioxide layer contains a crystalline phase and an X-ray amorphous phase, to achieve high conductivity and high temperature stability.
Furthermore, it is advantageous if the anatase crystalline phase at least predominates other crystalline phases, and preferably, if the anatase crystalline phase is the only existing crystalline phase of the titanium dioxide layer.
The term “X-ray amorphous” in the present context means that this phase does not exhibit any sharp X-ray diffraction maxima in an X-ray diffraction measurement.
Also, based on X-ray diffraction spectra, thoroughly investigated layers in particular exhibit the property that the substance amount fraction of the X-ray amorphous phase is greater than the substance amount fraction of the anatase crystalline phase. Other crystalline phases are preferably not present, as mentioned above, or are present in a smaller fraction as compared to the anatase phase. In other words, these layers are partially amorphous, with a minor proportion of an anatase phase. Also surprising herein is the good electrical conductivity of such layers, although amorphous materials typically exhibit a comparatively low conductivity.
For depositing the doped titanium dioxide layer as an anatase-containing layer of high temperature resistance, it has proved to be favorable to preheat the glass or glass-ceramic sheet to at least 250° C. during the deposition of the layer.
The invention will now be described by way of exemplary embodiments and with reference to the attached figures, wherein:
The thickness of the titanium dioxide layer 5 is chosen such that in addition to the reflectance due to the free charge carriers there is an optical interference reflection effect. To this end, the thickness of the titanium dioxide layer is adapted to the spectrum of the incident infrared radiation. In particular, appropriately, the optical thickness is selected such that the wavelength of the maximum or center of gravity of the radiation spectrum is about to or equal to four times the layer thickness, so that the layer has a reflective optical interference effect on the highest-energy portion of the radiation spectrum. Preferably, for optical interference reflection of thermal radiation, the layer thickness is selected in a range from 80 to 250 nanometers, more preferably from 100 to 150 nanometers.
In the simple example shown in
Other than in the example shown in
According to one embodiment of the invention, niobium is used as a transition metal, and the niobium is incorporated into the titanium dioxide layer in form of niobium oxide.
It could be demonstrated that the total reflection of heat radiation by a heat protection glazing according to the invention that includes a niobium-doped titanium dioxide layer can be enhanced by a factor of two as compared to a non-doped TiO2 layer.
In a practical test, experiments with niobium-doped TiO2 have shown that the reflection of heat radiation can be increased by a factor of 2 as compared to pure TiO2. This can be explained on the basis of the reflectance spectra of
Moreover, when deposited on a heated substrate the layers exhibit an anatase crystalline structure and thus, in principle, offer the possibility to produce layer systems that are deformable during ceramization.
In this context,
The anatase diffraction peak, on the other hand, virtually does not exhibit any change in intensity across the entire temperature range in which the anatase phase occurs. This shows, first, that the X-ray amorphous phase predominates in the range up to about 900° C., and on the other hand that it is specifically the layer composition of an X-ray amorphous phase with a smaller fraction of the anatase phase which is very temperature stable up to temperatures of 900° C.
Two exemplary embodiments for producing a heat protection glazing according to the invention will now be explained below:
On a green state transparent glass ceramic, niobium-doped TiO2 layers are sputter-deposited from a ceramic Nb2O5:TiO2 target having a niobium doping of 4 percent by weight using a pulsed or non-pulsed magnetron sputter technique. For this purpose, the vitreous substrate placed on a carrier is first preheated to temperatures in a range from 250° C. to 400° C. to start the sputter process in a hot state.
In the subsequent sputter process, the layers are either produced in a pure DC mode (i.e. using direct current) or in a pulsed mode at frequencies from 5 to 20 kHz, so obtaining resistivities of about 10−3 Ωcm. This is accompanied by a formation of a plasma edge and thus an increase of reflectivity in the infrared.
Following subsequent cooling and processing such as cutting and edge grinding, the sheet is transformed, in a ceramizing process, into a HQMK (high quartz mixed crystals) and/or KMK (keatite mixed crystals) phase.
An optional deformation of the sheet is also accomplished during ceramizing. The Nb:TiO2 coating may be provided on the surface facing the mold, or on the surface of the sheet facing away from the mold, or on both sides thereof.
In a second embodiment, niobium-doped TiO2 is sputtered from a metallic Nb:Ti target having a doping of 6 percent by weight. In this case, the substrate is not additionally heated but is coated in a “cold state”. The coating process is carried out at medium frequencies in a range from 5 to 20 kHz with reactive gas control using plasma emission monitoring. The conductivity of the layers is obtained in a subsequent annealing process at about 400° C. By this process, likewise, resistivities in a range around 10−3 Ωcm may be achieved.
Generally, without being limited to the above exemplary embodiments, there are thus two preferred variations of producing the heat protection glazing: According to a first variation, the layer is deposited onto a heated glass or glass-ceramic sheet, preferably heated to at least 250° C. According to another variation, an amorphous layer is deposited, which is subsequently subjected to a tempering process so that an anatase phase is formed in the doped layer.
The good long-term stability of the infrared reflection properties of heat protection glazings according to the invention will now be explained with reference to
The substrates used for the measurement results shown in
The other curves represent measurements on layers with a sheet resistance of 61 kΩ and 28 kΩ, respectively. Compared to the layer having a sheet resistance of 1.6 MΩ, there is another significant reduction in transmission resulting, which is due to the larger contribution of the reflection at the free charge carriers and thus to the doping.
However, the reflection properties of the layers are very similar, the layer with a sheet resistance of 28 kΩ exhibits a reduction of 38% in infrared transmission, which is only one percent better than that of the layer having a sheet resistance of 61 kΩ. Since at very low sheet resistances the transparency also decreases, it is advantageous for many applications to use coatings which have a sheet resistance of not less than 20 kΩ.
As mentioned above, the invention in particular also relates to heat protection glazing exhibiting high transparency in the visible spectral range. Therefore, the doped titanium dioxide layers according to the invention preferably exhibit a mean transmittance of at least 60%, preferably at least 70%, in the visible spectral range. In order to further improve the transparency in the visible spectral range, according to one embodiment of the invention the titanium dioxide coating doped according to the invention may now be combined with an anti-reflective coating effective in the visible spectral range. Moreover, this is favorable because titanium dioxide has a very high refractive index, which results in strong and possibly disturbing reflections.
Particularly suitable is a low refractive index layer, preferably an SiO2 layer with an optical thickness of λ/4 for a wavelength of the visible spectral range. For example, the layer may be designed as a λ/4 layer for green light, i.e. a wavelength of about 550 nanometers. In this case, for a λ/4 layer that is effective at a wavelength of 550 nanometers, a layer thickness of 550/(4*n) nanometers results, wherein n denotes the refractive index of the layer.
Such an anti-reflective coating may in particular be formed as a single layer. The thickness of such an anti-reflective single layer of SiO2 which is deposited on the doped titanium dioxide layer according to the invention preferably ranges from 30 nanometers to 90 nanometers. In the example shown in
According to one embodiment of the invention, the doped titanium dioxide layer is deposited by medium-frequency sputtering. For this purpose, the sheet is thermally pretreated in a pretreatment step, preferably at a temperature from 250° C. to 450° C. for a period of at least 3 minutes, preferably for 10 minutes, or is continuously heated during the sputtering process to the temperatures indicated.
The temperature treatment is preferably performed under vacuum and results in evaporation of excess water from the substrate surface.
Subsequently, the sheet is transferred into vacuum chamber 20, and the titanium oxide layer is reactively deposited in a single or multiple pass along the sputter device. A pulse frequency may be set to between 5 and 10 kHz, and a high sputtering power of 15 W/cm2 may be selected.
Due to the high particle flux achieved thereby, and under a low process pressure of about 10−3 mbar, dense titanium oxide layers with the above-mentioned properties can be produced.
The sputter process may be performed reactively from a metallic titanium target. A control scheme will be advantageous to stabilize the process.
Alternatively, sputtering may be performed using a ceramic TiO2 target. In this case, complex controlling of the plasma intensity may then optionally be omitted.
When the green glass sheet has been coated, it is placed onto a carrier 27 in a ceramizing oven 25, as shown in
Green glass sheet 30 is then heated in ceramizing oven 25 to the temperature required for ceramization, so that ceramization occurs in the green glass. As shown in
As a result, a non-planar glass ceramic sheet 3 is obtained provided with an infrared-reflective titanium dioxide coating 5 and an anti-reflection layer 6 effective in the visible spectral range. In similar manner the method is also suitable for producing heat protection glazings using glass sheets. In this case, the glass sheet with the deposited coating is heated and deformed without leading to ceramization.
In the embodiments of heat protection glazing described above, the titanium dioxide coating 5 doped with at least one transition metal compound was deposited directly on the surface of a glass or glass-ceramic substrate. According to yet another embodiment of the invention, an intermediate layer may be provided. In particular, in a modification of the invention, a preferably pure titanium dioxide coating which is not doped with a transition metal is used as the intermediate layer.
The intermediate layer may in particular be produced using a deposition method as described in German Patent Application No. 10 2009 017 547. The disclosure of this application with respect to the deposition method for producing a titanium dioxide intermediate layer is fully incorporated in the present application by reference. Accordingly, the glass or glass-ceramic sheet is preferably heated prior to applying the intermediate layer, in particular to between 200° C. and 400° C., in order to improve the adhesive strength of the intermediate layer. The intermediate layer is preferably produced by magnetron sputtering, reactive sputtering using a metallic titanium target being particularly suitable. For depositing, a pulse frequency of the electromagnetic field may be selected in a range from 5 to 10 kHz, and a high sputtering power of 10 W/cm2 or more may be selected.
1 Heat protection glazing
3 Glass or glass-ceramic sheet
4 Intermediate layer
5 Titanium dioxide coating
10 Thermal process unit
11 Wall of 12
12 Hot space
13 Window
15 Infrared radiation source
17 Surface thermocouple
19 Measuring device
20 Vacuum chamber
21 Magnetron sputter device
22 Nb:Ti target
23 Si target
25 Ceramizing oven
27 Support for 30
30 Green glass sheet
Number | Date | Country | Kind |
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10 2010 046 991.2 | Sep 2010 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2011/004864 | 9/29/2011 | WO | 00 | 9/3/2013 |