Barrier layers comprising ni and ti, coated articles including barrier layers, and methods of making the same

Barrier Layers Comprising Ni and/or Ti Coated Articles Including Barrier Layers, and Methods of Making the Same

Full description

Background of the invention

Examples of certain embodiments of this application relate to a coated article comprising at least one infrared (IR) reflecting layer composed of a material such as silver or the like and a low-E coating. In other embodiments, at least one layer of the coating is or comprises nickel and/or titanium [e.g., (NixTiy, NixTiyOz), etc.]. In examples of certain embodiments, providing a coating on nickel titanium and/or its oxide thereof allows a layer that has good adhesion to the infrared (IR) reflecting layer to be used, achieving reduced absorption of visible light. (Which leads to a coated material with higher visible transmission). When a layer containing nickel titanium oxide is provided directly over and/or under an infrared (IR) reflecting layer (e.g., barrier layer), mechanical and chemical durability may be achieved. Durability in examples of specific models. Therefore, in certain embodiment examples, permeability and transmission may be improved if desired, although with a reduced effect on bearing strength. Coated materials may be used here in the field of insulating glass (IG) window units, or in the field of vehicle windows, or in the field of other suitable applications and uses such as applications or uses of monolithic windows, and/or multi-layered windows, And/or similar.

General description of the invention

Packaging materials in such an area of the art have been known for use in window applications such as insulating glass (IG) window units, vehicle windows, monolithic windows, and/or the like. In specific instances, often, coating material designers strive to achieve a combination of higher visible transmission, low-emissivity, and/or low sheet resistance. The high visible transmittance of coated materials may allow them to be used in applications where such special properties are required and desired such as architectural applications or vehicle window applications and uses, while the low emissivity and thin film resistance properties of such coated materials allow them to retard large amounts of value. Considering it as significant amounts of IR radiation in order to, for example, reduce the hottest temperature of unwanted vehicles or reduce the hottest temperature of parts. Interior of buildings. Therefore, typically, it is often required and desirable for coatings used on architectural glass, in order to block significant amounts of infrared radiation, to have a higher visible transmission. visible spectrum visible spectrum.

The infrared (IR) reflective layer found in low-E coatings affects the entire coating, and in some cases the IR reflective layer is the most sensitive layer in the pile or The stack. Inadequately, IR reflective coatings may sometimes be damaged by deposition, subsequent weathering, and/or heat treatment.

In certain cases, the silver layer in low-E coatings may need to be protected from oxygen while other layers are deposited on top of the silver layer. If the infrared (IR) reflective coatings are not adequately protected, the durability, visible transmission, and/or other optical characteristics of the coated material may suffer or suffer a lot of damage.

Accordingly, it is recognized by those skilled and experienced in the art that there is an urgent need for low-E coatings with improved durability and improved optical properties or essentially or largely unchanged optical properties. .

Examples of certain embodiments of this invention relate to an improved barrier layer material used in connection with infrared (IR) reflective layers comprising silver. In certain examples or situations, infrared (IR) reflective coatings may allow the durability of the coated material to be improved.

Examples of particular embodiments relate to a method for making or manufacturing a coated article. The first dielectric layer is placed or deposited on top of the glass substrate. A bottom contact layer is placed or deposited over the first dielectric layer. An infrared (IR) reflective layer is then placed or deposited over and in contact with the first contact layer. Next, a top contact layer consisting of oxide nickel and oxide titanium is placed over and in contact with the infrared (IR) reflecting layer. A layer containing oxide and/or silicon nitride is then deposited over the upper contact layer as the outermost layer of the encapsulation.

Examples of specific embodiments relate to making or manufacturing coated material. The first dielectric layer is placed or deposited on top of the glass substrate. A bottom contact layer is placed or deposited over the first dielectric layer. An infrared (IR) reflective layer is then placed or deposited over and in contact with the first contact layer. An upper contact layer is formed over and in contact with the infrared (IR) reflective layer by performing a cathodic sputtering coating of nickel and titanium from a target containing from (1%) by weight to (50%) by weight nickel, and ranging from ( 50% by weight to 99% by weight titanium in the packaging or manufacturing process.

Examples of specific embodiments also relate to laminated materials and/or insulating glass (IG) window units manufactured by using one of the methods described above and/or by using other methods.

Brief explanation of the drawings

Figure No. (1): A cross-sectional view of a coated article according to an example of an embodiment of this invention.

Figure No. (2): A cross-sectional view of a coated material according to another example of an embodiment of this invention.

Figure No. (3): A cross-sectional view of a coated material according to an additional example of an embodiment of this invention.

Figure No. (4): A cross-sectional view of a coated material according to another additional example of an embodiment of this invention.

Figure No. (5): A cross-sectional view of a coated material according to another additional example of an embodiment of this invention.

Detailed description

Referring now to the figures and illustrations and using them, in which the reference numbers show parts similar to those that are present in the many different scenes. Laminated materials may be used in applications and uses of laminated materials such as monolithic windows, insulating glass (IG) window units, vehicle windows, and/or any other suitable application or use including A single substrate or multiple substrates such as glass substrates. As explained above, in certain cases, a silver-based layer in low-E coatings may need to be protected during successive operations. For example, the oxygen in the plasma is used to deposit successive layers that may be highly ionized, and the layer consisting mainly of silver may need to be protected. Also, in deposition processes following “atmospheric processes,” the silver-based layer may be susceptible to attack by oxygen, moisture, acids, bases, and/or the like. And he talked to her about undressing. This is particularly realistic and true if the layer between the silver layer and the air has any defects or damage, such that the silver layer is not completely covered (for example, scratches, pin holes, etc).

Furthermore, problems may arise during the heat treatment procedure in some examples of certain models. In such cases, oxygen may diffuse into low-E coatings. In examples of certain embodiments, oxygen reaching low-E coatings may affect its properties, for example by reducing the sheet resistance, affecting the emissivity, and/or affecting the Producing haze, etc., may result in reduced layer stack performance.

In examples of certain embodiments, insulating layers with primarily silver layers (and/or other infrared (IR) reflecting layers) may thus be used in low-E encapsulations in order to reduce the occurrence of some or all of the foregoing Other undesirable consequences are prescribed and/or reduced.

In the past, insulating layer materials consisted of thin metal layers, such as aluminum (Al), that were oxidized during the following anodization process in specific cases. In other cases, coatings consisting mainly of indium tin oxide (ITO) were also used. However, these materials may completely compromise the optical properties and/or durability of the layer stack in certain such cases.

Materials such as chromium may be used in insulating layers in certain cases, specifically in low-E laminated materials used in the architectural market. However, chromium may absorb significant amounts of visible light in examples of certain embodiments. The absorption of chromium oxide at a wavelength of 550 nm is equal to 0.033942. Accordingly, the transmittance or visible transmission of the coated material may be reduced if the chromium-containing layer is too thick and/or if the coated material is not sufficiently oxidized.

However, the silver layer is not completely protected if the barrier thickness is not sufficient.

Another insulating layer material that may be used is titanium [for example, titanium oxides].

However, titanium's adhesion to infrared (IR) reflecting layers, specifically those containing silver, is lacking or incomplete.

Therefore, when the material consists of or includes primarily titanium and/or titanium oxides, it is used as an insulating layer to protect the silver layer and the durability of the coated material may be compromised and/or reduced.

From the point of view of all of the above, it would be beneficial to provide an insulating layer that includes a material(s) that has sufficient and good adhesion at the interface between the silver (and/or infrared (IR) reflecting layers). layer) and the insulating material, where oxide barrier materials have low absorption within the visible spectral range.

Certain embodiments of this invention relate to a coated article comprising at least one glass substrate that supports and reinforces the packaging. Typically, the packaging has at least one layer that reflects infrared (IR) radiation and/or blocks at least some significant amounts of IR radiation. The infrared (IR) reflective layers may be composed of or include a material such as silver, gold, nickel chromium or the like in various embodiments of this invention. Often, the infrared (IR) reflective layers are sandwiched between a first contact layer and at least a second contact layer of the packaging.

In examples of certain embodiments of this invention, it is found that providing a layer consisting primarily of, or comprising primarily oxide nickel and/or oxide titanium [e.g. (NixTiy), (NixTiyOz), etc.] in the form of a layer Contact layer (for example, contact with infrared (IR) reflecting layer) has led such packaging to unexpectedly significantly improve the mechanical and chemical durability of the packaging. In such a way that other optical properties of the coated material such as visible transmittance and/or color are not significantly degraded or degraded. One or more such overall layers of nickel and/or titanium (which are oxidized in examples of certain embodiments) may be provided and supplied in a particular packaging in several different embodiments of this invention. Furthermore, such comprehensive nickel and/or titanium coatings may be provided in any type of witness level coating or low-E coatings (low-emissivity, low-emittance). ) in embodiments of this invention (e.g., in the form of a contact layer), the specific low-E coatings described herein are for illustrative purposes only unless otherwise noted in appended claims. When a layer containing nickel titanium oxide is provided as the upper contact layer of the coated material (for example, over infrared (IR) reflective layers), this improves the mechanical durability and chemical durability in examples of specific models. Surprisingly, the use of a layer of nickel titanium oxide here (for example, as a contact layer) has been found to improve the chemical and mechanical durability of the coated material, and it has also been found to improve (or at least not The permeability or visible transport of the encapsulated material has been substantially or significantly reduced or degraded. In examples of certain embodiments, an insulating layer may be provided comprising nickel titanium, and/or their oxide thereof. This combination of nickel and titanium may provide good adhesion with low absorption, both of which are desirable qualities for low-E coatings in certain embodiment examples. Advantageously, the provision of an insulating layer containing nickel titanium or its oxide thereof [eg NixTiy, NixTiyOz, etc.] may allow a single-layer coated material with strong chemical and mechanical durability to be used with a single single layer An infrared (IR) reflecting layer (for example, composed primarily of silver) without causing reverberation or degradation of the coating properties due to insufficient protection of the primarily silver layer.

Figure No. (1) is a cross-section view of a coated article according to an example of an embodiment of this invention. In examples of certain embodiments, the coated material shown in Figure 1 may be used as a single-layer window with low-E coatings on surface 1 and/or surface 2, wherein Low-E packaging on only one single infrared (IR) reflective layer. However, in another example of certain other embodiments, the coated material shown in Figure 1 may include additional layers. Furthermore, a coated article made in accordance with one example of certain embodiments described herein may be used in insulated glass unit (IGU) units, with encapsulation or surface coatings No. (1), and/or No. (2), and/or No. (3), and/or No. (4); In the form of laminated single layers (stacked in thin layers one layer on top of the other) with the packaging embedded against the inner layer on surfaces No. (2), No. (3), or exposed above surface No. (4), in the form of insulating glass materials insulated glass unit (IGU) laminated (thin layers pressed on top of each other) far outward with the packing embedded against the inner layer on surfaces No. 2, No. 3, or exposed above surface No. 4, in the form of insulated glass materials. glass unit (IGU) laminated (thin layers pressed on top of each other) far inwards with the cladding exposed over surface 3 and/or surface 6, or embedded in surface 4 and/or surface (5), according to other examples of various other models and many other applications. In other words, this packaging may be used in a single layer form, or in the form of insulating glass (IG) window units that include two or more bottom layers, or more than one in an insulated glass unit ( IGU), and may be supplied to any surface of the unit in various examples of various other embodiments.

The coating material includes a glass substrate (1) [for example, a glass substrate that is clear, green, green, bronze, or "blue-green", and has a thickness of From (1.0) mm to (10.0) mm, or more, preferably, with a thickness ranging from (1.0) mm to (6.0) mm], and packaging in multiple layers (35) (or a multi-layer system) is provided above Glass substrate (1), whether directly or indirectly.

As shown in Figure (1), the packaging (35) includes optional dielectric layers (3) and/or (5), and a bottom contact layer (7), which may be or include nickel and/or titanium, and/or their oxides thereof [e.g. (NixTiy), (NixTiyOz), etc.], or which may be the material for another suitable contact layer such as oxides and/or nitrides of Zinc, nickel Chromium and/or combinations thereof, and/or the like, and the infrared (IR) reflecting layer, including one or more layers consisting primarily of silver, gold, or the like, and a layer upper contacts (11) being or comprising nickel and/or titanium, and their oxide thereof [e.g. (NixTiy), (NixTiyOz), etc.] or other suitable contact layer material, or optionally electrically insulating layers (13) , and/or (15), and an electrically insulating layer (16) which is or includes a material Such as silicon oxide, silicon nitride, silicon oxynitride, zirconium oxide, zirconium oxynitride, or zirconium silicon oxynitride which in certain cases may be an overly protective coating. Other layers and/or other materials may also be provided in examples of certain embodiments of this invention, and it is also possible that certain layers may be removed or separated in cases of certain examples. Layer (16) may or may not be provided according to different examples of various other embodiments.

The electrically insulating layers may optionally include (3) and/or (5) silicon nitride, titanium oxide, tin oxide, silicon oxide, silicon oxynitride, and/or electrically insulating materials. Others according to different examples of different other models.

Preferably, the infrared (IR) reflective layer (9) is largely metallic or entirely metallic and/or conductive, and may include or consist primarily of silver, gold, Or any suitable infrared (IR) reflective material. The infrared (IR) reflecting layer (9) helps allow the packaging to be low-E coatings and/or have good solar control and control properties, such as low-emittance. , low thin film resistance, and so on. However, the infrared (IR) reflective layer (9) may be slightly oxidized in examples of certain embodiments of this invention.

The infrared (IR) reflecting layer shown in Figure 1 and described herein may include or consist primarily of silver in many different examples of various other embodiments. Therefore, it should be recognized that examples of certain embodiments may include silver alloys. In such cases, silver alloys may be formed with an appropriate amount of zirconium, titanium, nickel, chromium, and/or palladium (Pd), and/or combinations thereof. In examples of certain embodiments, silver (Ag) may be alloyed with both Palladium (Pd) and Copper (Cu), in proportions ranging from (0.5%) to (2%) (by weight or atomic percent) for each Of Palladium (Pd) and Copper (Cu). Other potential or possible alloys include silver (Ag) and one or more of the following elements or compounds Co, C, Mg, Ta, W, NiMg, and/or PdGa , and/or CoW, and/or Si, and/or Ge, and/or Au, and/or Pt, and/or Ru, and/or Sn, and/or Al, and/or Mn, and/or V , and/or In, and/or Zn, and/or Ir, and/or Rh, and/or Mo. In general, dopant concentrations may range from (0.2%) to (5%) (by weight or atomic %), and, more preferably, from (0.2%) to (2.5%) (by weight or atomic %). . Within such limits, this may help the silver maintain the required and desired optical characteristics of the silver layer that might otherwise be lost by the action or effect of the alloying process, thus Helping to maintain the overall optical properties of the stack while also enhancing chemical and/or corrosion durability, And/or mechanical. Material representative of the silver bullion target, for example, identified and identified herein, may be sputtered using a single target, deposited by combined sputter depositing, using two or more targets, etc. In addition to providing improved corrosion resistance, the use of silver (Ag) alloys may in certain cases help reduce the diffusivity of silver at high temperatures, although it may also help reduce or inhibit significant amounts of oxygen movement in the layer stacks. This may also lead to enhanced diffusivity of the silver and may alter the silver's growth and structural properties which may potentially or potentially lead to poor durability.

The upper and lower contact layers (7), (11) may be or include nickel and/or titanium, their oxides thereof, and/or their nitrides thereof. In examples of certain embodiments, the upper and lower contact layers (7), (11) may be or comprise nickel, titanium, chromium, and/or a nickel alloy such as nickel titanium (NiTi ), and/or nickel Chromium [e.g. (NiCr)], Haynes alloy, zinc, and oxide, nitride, or oxynitride of any of these elements [e.g. (NixTiyOz)], or other suitable material(s). For example, one of these layers may be or include oxide zinc instead of NiTi (and/or oxide thereof).

The use of (NiTi) and/or (NixTiyOz), for example, in these layers allows the durability and/or permeability or visual transmission of the coated material to be improved in specific cases. In examples of certain embodiments, if there is a fully oxidized layer of NiCrOx, it will have a high residual absorption due to the absorption of chromium oxides, where Potassium (550 nm) = (0.033942). However, it has been usefully found that because titanium oxides (TiOx) have a much lower absorption value and significance than chromium oxides (CrOx), so in certain embodiments, inclusion of titanium oxides (TiOx) in an insulating layer may barrier layer to achieve higher visible transmission of visible light for the coated material. For example, the absorption of titanium oxide (TiOx) (550 nm) = (0.004806) which is approximately equal to (1/10) the absorption of chromium oxides (CrOx). Therefore, when a metal or metal oxide with a lower absorption than Chromium oxides (CrOx) is used in an insulating layer, the visual transmittance of the coated material may be improved.

However, in certain embodiments, an insulating layer comprising titanium oxides may not adhere adequately to an infrared (IR) reflecting layer. Therefore, if the insulating layer being used consists of or contains only titanium oxides, the durability of the coating material may suffer and suffer a lot of damage. However, it has been found usefully that, by using an alloy containing the material that adheres well to infrared (IR) reflective coatings, and by using titanium and/or titanium oxide, the durability of the coated material will not be compromised by substitution of titanium oxide and/or titanium oxide (TiOx) (or other material with relatively low absorption) relative to Chromium and/or chromium oxide (CrOx). Helpfully, nickel is thought to adhere well to infrared (IR) reflective coatings. Therefore, the use of an insulating layer that includes nickel and titanium, as well as their oxides thereof and/or nitrates, can advantageously result in a coated material with improved visible transmittance and adequate durability.

The contact layers (7), (11) [e.g., being or comprising nickel and/or titanium] may be continuous, discontinuous, or discontinuous in many different embodiments of this invention via the infrared reflective layer (IR) reflecting the whole layer completely. In examples of certain embodiments, one or both of the NiTi layers No. (7) or No. (11) comprise from (1%) to (50%) nickel, and from (50%) to (99%) titanium. For example, it contains (80%) titanium and (20%) nickel. In examples of certain embodiments, the layer comprising NixTiy is fully oxidized and/or partially oxidized. Oxidation may occur in the form of layer deposition, and this may be due to processes that occur after deposition of the contact layer, for example, from the deposition of successive layers in the presence of oxygen, from heat treatment, etc.

However, both nickel and titanium may still be present in the same ratio as described above, regardless of the presence of oxygen. For example, even in the case of a layer containing nickel titanium oxide, the ratio of nickel to titanium may still range from (1:99) to (50:50) [these percentages are given by weight].

As already mentioned above, layers (NixTiy), (NixTiyOz) No. (7) and/or No. (11) may be fully oxidized in certain embodiments of this invention (e.g., fully oxidized in elemental union ratios ), or alternatively, they may be partially oxidized (e.g. in elemental ratios) [before and/or after heat treatment optional]. In other cases, layers (7) and/or (11) may be deposited as mineral layers, which may be completely or partially oxidized during subsequent deposition processes, such as successive layer deposition in the presence of oxygen, heat treatment, and the like. that. In certain cases, layers (NixTiy) and/or (NixTiyOz) No. (7) and/or No. (11) may be oxidized by at least 50%.

The contact layer or layers (7) and/or (11) may be [e.g., are or comprise oxide nickel and/or oxide titanium] and may not have stepwise oxidation in embodiments of this invention. As is known in such a field of the art, oxidation gradation involves changing the degree of oxidation in the layer through the thickness of the layer, so the contact layer may, for example, be oxidized to be less oxidized than the contact interface with the adjacency immediately adjacent to the layer. (9) The infrared (IR) reflecting layer from any part of the contact layer that is one or more/most distant from the infrared (IR) reflecting layer immediately. Descriptions or specifications of several different types of oxidation graded contact layers are given in US Patent No. 6,576,349, which are hereby incorporated in their entirety by reference. The contact layer(s) (7), (11) [e.g., being or comprising nickel and/or titanium] may be continuous, discontinuous, or discontinuous in many different embodiments of this invention via the ray-reflecting layer Infrared (IR) all fully (9).

In examples of certain embodiments, the contact layer below the infrared (IR) reflecting layer [e.g., lower contact layer (7)] may be or comprise zinc and/or oxide zinc. The optionally electrically insulating layers (13) and/or (15) may be or comprise silicon nitride [eg (SixNy)], or any other suitable material in examples of certain embodiments of this invention such as titanium oxide, and/ or tin oxide, and/or silicon oxynitride, and/or silicon oxide. These layers may assist with durability results, and/or may also protect the underlying substrates and, in some cases, for optional anti-reflective purposes.

An optional over-coated layer may also be included (16) including for example zirconium oxide. U.S. Patent Application Series 12/213,879, the entire contents of which are incorporated herein by reference, explains and illustrates the advantages and disadvantages associated with the use of zirconium oxide as an over-the-counter encapsulation. In examples of certain other embodiments, the optional coating may be excessively (16) or include silicon nitride, and/or silicon oxynitride. The optional packaging may also excessively include (16) other zirconium-containing compounds in examples of certain other embodiments in addition to the foregoing.

In examples of certain embodiments, the coated material shown in Figure 1 may be used as a monolithic window with low-E coatings with a single infrared (IR) reflective layer. However, in examples of certain other embodiments, a coated article as described herein may be used in combination with any number of other underlying glass layers to create or constitute a laminated glass unit and/or an insulated glass unit. Encapsulations can also be used for self-propelled insulated glass units (IGU), VIG, and other applications according to other examples of different embodiments.

Figure (2) is another example of a model with low-E coatings (35ﹶ) equipped with a single infrared (IR) reflecting layer. In the model shown in Figure (2), the layer consisting mainly of (NixTiyOz) is used as the lower and upper contact layers. Moreover, in Figure (2), a layer consisting mainly of silicon nitride is used in the form of an electrically insulating layer (3), while the electrically insulating layer (5) is cancelled. The electrically insulating layer (13) includes silicon nitride; The over-coated layer (16) is eliminated, since the electrically insulating layer (13) may assist in maintaining the purposes of the over-coated layer (for example, by providing protection or protection to the underlying substrates) described in the model. Shown in Figure No. (2). In examples of certain embodiments, the coating material of Figure 2 may have improved visual permeability, and may also have improved mechanical and chemical durability and/or be essentially or largely unaffected and unchanged.

Table No. (1): Examples of materials/thicknesses; For the model shown in Figure No. (2)

Class

preferredrange()

Most preferred range()

Example ()

Glass [thickness (1-10) mm]

Silicon nitride (SixNy) (Layer 3)

70-1200

250-400

382

(NixTiyOz) (Tier 7)

5-200

10-50

15

Silver (Ag) (Class 9)

20-700

30-300

120

(NixTiyOz) (Tier 11)

5-200

10-45

15

Silicon nitride (SixNy) (Layer 14)

40-1200

250-400

330

Table No. (2): Examples of distinctive properties; For the model shown in Figure No. (2)

the description

Y

L*

a*

b*

As packaged (permeable)

66.16

85.08

-1.59

-3.44

As packaged (glass side)

6.79

31.32

3.53

6.71

As packaged (thin film side)

5.62

28.43

3.73

-7.18

After heat treatment (permeability)

69.18

86.59

-2.6

-3.89

After heat treatment (glass side)

6.44

30.5

7.25

8.14

After heat treatment (thin layer side)

5.74

28.74

5.92

-4.9

The example model shown in Figure (2) may have a thin layer resistance of (11.15) ohms/square in implementations or realizations of specific examples.

However, as is well known to those skilled and experienced in such an art, the resistance and/or emissivity of the "specific" thin layer may be controlled, inter alia, by adjusting the thickness of the layer consisting mainly of silver (Ag). ).

In other words, in examples of certain embodiments, the monolayer coated material may have a single infrared (IR) reflecting layer with a visible transmittance of at least 55%, preferably at least 60%, and Most preferably, at least 65%, and sometimes, at least 67%, as placed and deposited.

After heat treatment (HT), the single-layer coated material may have a higher visible transmittance, such as at least 60% and, preferably, at least 65%. Subtracted permeability to at least (70%).

As packaged, the material may have a glass aspect (a*) with a value ranging from (0) to (5), and more preferably, from (1) to (4), with the example given having a value of (3.5) in examples of certain embodiments. As packaged, the material may have a glass side (b*) with a value ranging from 0 to 10, and more preferably, from 1 to 7, with the example given having a value of 6.7 in examples of certain embodiments. In some cases, the material may have a thin-layer aspect (a*) value ranging from (0) to (5), and more preferably, from (1) to (4), and in the example given value (3.7) as it is coated. In examples of other certain embodiments, the material may have a thin-layer aspect (b*) of (-10) to (1), and more preferably, (-8) to (-2), and in the given example it has a value of (-7.18).

After heat treatment has been performed [expressed in Table 2 by the abbreviation (HT)], the material may have a glass aspect (a*) with a value ranging from (0) to (10), and more preferably, from (1). To (8), and with the example presented, the value of (7.25) in examples of specific models. As packaged, the material may have a glass side (b*) with a value ranging from (0) to (10), and more preferably, from (1) to (9), with the given example having a value of (8.14) in examples of certain embodiments. In some cases, the material may have a thin-layer aspect (a*) with a value ranging from (0) to (8), and more preferably, from (1) to (6), with the example given having a value of (5.92). In examples of certain embodiments, the material may have a thin layer aspect (b*) of (-8) to (1), and more preferably, (-6) to (-2), with the example given having a value of (-4.9). ).

Figure (3) is an example of another model with low-E coatings (35ﹶﹶ) equipped with a single infrared (IR) reflecting layer. The model shown in Figure No. (3) is similar to the two models shown in both Figure No. (1) and Figure No. (2), but in the model shown in Figure No. (3), the layer consisting mainly of (NixTiyOz) is used in the form of The upper contact layer (11), while a layer consisting mainly of zinc is used. In the form of the lower contact layer (7).

Moreover, in Figure (3) the layer consisting mainly of silicon nitride is used in the form of a dielectric layer (3), while the electrically insulating layer (5) is then cancelled. In examples of certain embodiments, the coated material shown in Figure 3 may have improved and/or unaffected chemical and mechanical durability, and may also be permeable. Have increased visible transmission.

Figure No. (4) is a cross-sectional view of a coated article according to an example of an embodiment of the present invention. In examples of certain embodiments, the coating material shown in Figure 4 may be used as a single-layer window with low-E coatings with dual infrared (IR) reflecting layers. The coated article includes a glass substrate (1) [which, for example, is a clear, green, green, bronze, or 'blue-green' glass substrate, with a thickness of 1 (mm to 10 mm, and more preferably, with a thickness ranging from (1.0) mm to (6.0) mm], and in a multi-layer packaging (or layer system) provided over a glass substrate (1), whether directly Or indirectly.

Similar to Figure (1), the coating (45) of Figure (4) includes optional dielectric layers (3) and/or (5), and the first lower contact layer (7) The first IR reflecting layer (9) is or includes silver, gold, or the like, and the upper contact layer (11) is or includes oxide of nickel. titanium [eg, (NixTiyOz)], and layer layers Optional dielectric layers (13) and/or (15) [e.g., which is or includes silicon nitride (SixNy)], a second lower contact layer (17), and a second infrared reflective layer second IR reflecting layer (19), second upper contact layer (21), optional dielectric layers (23) and/or (25), and optional dielectric layer (16) which is or Contains a material such as silicon nitride, or... silicon oxynitride, zirconium oxide, zirconium oxynitride, or zirconium silicon oxynitride which in certain cases may all be overly protective coatings. Other layers and/or other materials may also be provided in examples of particular embodiments of this invention, and certain layers may also be removed or separated in instances of particular examples.

In examples of certain embodiments, one of the contact layers (7), (11), (17), (21) may comprise nickel titanium and/or nickel titanium nitride. In examples of certain additional embodiments, the upper contact layers may be or comprise NixTiy and/or NixTiyOz, while the lower contact layers may be or comprise zinc oxides and/or nitrides , nickel, chromium, titanium, and/or combinations of such materials.

However, in examples of certain additional embodiments as well, more than one or even all of the contact layers may be or comprise nickel titanium and/or its oxides and/or nitrides thereof.

Figure No. (5) is a cross-sectional view of a coated article according to another additional example of an embodiment of the present invention.

In examples of certain embodiments, the encapsulated material shown in Figure 5 may comprise three infrared (IR) reflecting layers [e.g., a three-layer pile or pile of waste]. The coated article comprises a glass substrate (1) [which is, for example, a clear, green, green, bronze, or 'blue-green' glass substrate, with a thickness of ( 1) mm to 10 mm, and more preferably, with a thickness ranging from (1.0) mm to (6.0) mm], and in a multi-layer packaging (or layer system) provided over a glass substrate (1), whether This is done directly or indirectly.

In examples of certain embodiments, the packaging (55) shown in Figure (5) may include an optional dielectric layer (3) that is or includes silicon nitride, an optional dielectric layer (5) that is or includes On oxide titanium, a lower contact layer (7) which is or comprises zinc oxide, an infrared (IR) reflective layer (9) which is or comprises silver, an upper contact layer (11) which is or comprises Nickel and/or chromium, or their oxide thereof, is an optional layer optional dielectric layer (12) being or comprising titanium oxide, optional dielectric layer (13) being or comprising tin oxide, optional dielectric layer (14) being or comprising silicon nitride (or Incorporating some other silicon or other material), an optional electrically insulating layer (015) which is or comprises tin oxide, a second lower contact layer (17) which is or comprises zinc oxide, an infrared reflective layer. (IR) reflecting second layer (19) which is or comprises silver, a second upper contact layer (21) which is or comprises nickel and/or titanium or their oxides, an electrically insulating layer (23) which is or comprising tin oxide, an electrically insulating layer (24) being or comprising silicon nitride (or including some other silicon or other material), an electrically insulating layer (24) being or comprising tin oxide, a third bottom contact layer (27) It is or includes zinc oxide, a reflective layer For infrared (IR) reflecting a third layer (29) which is or includes silver, a third upper contact layer (31) which is or includes nickel and/or titanium or their oxide thereof, an electrically insulating layer (32) It is or comprises tin oxide, an electrically insulating layer (16) which is or comprises silicon nitride, which in certain cases may be an overly protective coating.

Other layers and/or materials may also be provided in examples of certain embodiments of the present invention, and it is also possible that certain layers in examples of certain embodiments may be removed or separated. Furthermore, in examples of certain other embodiments, one or more upper contact layers (11), (21), (31) may comprise nickel chromium and/or their oxide thereof, as well as oxide nickel titanium.

Furthermore, any of the layers (7), (11), (17), (21), (27), and/or (31) may be Or it includes nickel, titanium, chromium, zinc, and combinations/alloys thereof, and may also include oxygen and/or nitrogen.

Therefore, any or all of the upper contact layers (11), (21), (31) may be layers that include nickel and/or titanium [e.g., layers containing (NiTiOx)] in many Examples of this invention.

Layers containing NiTiOx may help provide high-performance coatings, since nickel titanium helps reduce overall emissivity while maintaining good silver quality.

Moreover, as already mentioned above, the presence of nickel in such layers may help to obtain good durability results, while the presence of titanium in such layers may help to obtain good permeability.

It should be noted that in examples of certain embodiments, the nickel titanium oxides may be replaced with titanium metal or titanium oxide. In examples of certain embodiments, layers containing titanium oxide may be slightly oxidized, slowly deposited, and then eventually become essentially or substantially completely oxidized by successive treatment in succession (e.g., during a spraying procedure for deposited layers).

NiTiOx may also be graded or graded in specific embodiment examples as deposited.

Examples of thicknesses

Table No. (3): Examples of materials/thicknesses; Sample Figure No. (5) (annealed)

Class

preferredrange()

Most preferred range()

Example ()

Glass [thickness (1-10) mm]

SixNy(Layer 3)

70-1200

200-350

294

TiOx (Layer 5)

10-300

100-140

116

ZnOx (layer 7)

10-110

40-80

60

Ag (layer 9)

10-200

100-160

120

NixTiyOz (Layer 11)

10-100

15-40

25

TiOx (layer 12)

10-150

40-60

50

SnOx (Layer 13)

70-1200

200-700

270

SixNy (layer 14)

10-300

100-140

110

SnOx (Layer 15)

70 - 1200

100-200

163

ZnOx (Layer 17)

15-115

50-150

130

Ag(Layer 19)

10-300

100-145

130

NiTiOx (Layer 21)

10-150

20-50

25

SnOx (Layer 23)

70-1200

300-700

501

SixNy (layer 24)

10-300

60-140

100

SnOx (Layer 25)

10-300

100-200

150

ZnOx (Layer 27)

10-110

40-80

60

Ag(Layer 29)

10-300

120-180

161

NiTiOx (Layer 31)

10-150

15-50

25

SnOx (Layer 32)

10-300

100-210

155

SixNy (layer 16)

70-1200

200-300

256

In examples of certain embodiments, the top layer consisting primarily of silver is the thicker layer. It has been found that this arrangement helps improve the emissivity of the packing. Also, in certain embodiment examples, the primarily silver middle layer is thinner than the primarily silver top layer, which has been found to help achieve improved emissivity, although it itself also improves off-axis color stability and helps In that higher visible transmission is provided.

It is surprising and unexpected that introducing a second layer containing titanium oxide (12) into the lower middle dielectric layer stack was found to improve the quality of a glass substrate composed mainly of silver (9). This is believed to be a result of the lack or lack of tin oxide from layer (13), and the introduction or intercalation with the first underlying contact layer (11) directly and adjacent or very close to the first layer, which is mainly composed of silver (9).

Furthermore, in examples of certain laminated embodiments of this invention, the laminated material has optionally been heat treated to a sufficient extent of heat strengthening or intensity, and this is then combined or coupled with another glass substrate to form a glass window unit. Insulating glass (IG) window units, and may have the following IG unit/solar characteristics.

In the field of IG units, the use of nickel titanium oxides advantageously allows obtaining high LSG values. For example, in example cases, an LSG value of (2.15) or higher is possible, while an LSG value of (2.1) or less is possible or likely if primarily composed layers are used Of (NiCr) only without including (NiTiOx) layers. As will be recognized by those skilled and experienced in such an art, a high LSG value is useful because it is indicative of a high visible transmission value combined with or combined with a low SHGC, thus maintaining heat to the outside. keeping heat out and letting light in.

The example model shown in Figure 5 is particularly well suited for use in a plasticized product. Modifications may or may not be made to heat treatable embodiments.

For example, in examples of heat treatable embodiments one or both of layers (5) and/or (12) containing or including TiOx may be removed or eliminated. As another example, in a heat-treatable coating, some or all of the layers (14), (24), (16) containing SiN may be made more metallic than in the complementary annealed view. Also, in addition to the above, some or all of the layers containing (NiTiOx) may be replaced or replaced by layers containing (NiCr) or its oxide.

The following table shows an example of materials and thicknesses of a coated material that is heat treatable and similar to that shown in Figure (5), but modified in the previous view.

Table No. (4): Example of materials/thicknesses; For the model shown in Figure No. (5) modified (heat treatable)

Class

Preferred range (nm)

Most preferred range (nm)

Example (nm)

glass

silicon nitride(SiN)

25.9-38.9

29.2-35.6

32.4

zinc oxide (ZnO)

5.6-8.4

6.3-7.7

7

silver

10.2-15.2

11.4-14

12.7

nickel chromium oxide (NiCrOx)

2.4-3.6

2.7-3.3

3

tin oxide (SnO)

35.9-53.9

40.4-49.4

44.9

silicon nitride(SiN)

8-12

9-11

10

tin oxide (SnO)

12.2-18.2

13.7-16.7

15.2

zinc oxide (ZnO)

5.2-7.8

5.9-7.2

6.5

Silver (Ag)

11.2-16.8

12.6-15.4

14

nickel chromium oxide (NiCrOx)

2.4-3.6

2.7-3.3

3

tin oxide (SnO)

36.6-55

41.2-50.4

45.8

silicon nitride(SiN)

8-12

9-11

10

tin oxide (SnO)

12-18

13.5-16.5

15

zinc oxide (ZnO)

5.2-7.8

5.9-7.2

6.5

Silver (Ag)

15.1-22.7

17-20.8

18.9

nickel chromium oxide (NiCrOx)

2.4-3.6

2.7-3.3

3

tin oxide (SnO)

11.2-16.8

12.6-15.4

14

silicon nitride(SiN)

23.4-35.2

26.4-32.2

29.3

Furthermore, in examples of heat-treated embodiments, the thickness of the “gummy” layers containing tin oxide may be reduced and/or removed completely. In such cases, it may be desirable to increase the thickness of the underlying substrates containing tin oxide. For example, layer (15) and/or layer (25) may have a reduced thickness [e.g., from (15) nm to (10) nm] and/or may be completely removed. Similarly, layers (13) and/or (23) may be of increasing thickness.

The amount of increased thickness may range from (8) nanometers to (12) nanometers. Therefore, in examples of certain embodiments, layer 15 may have a reduced thickness of 8-12 nm, more preferably 9-11 nm, and sometimes 10 nm, while the layer (13) It has an increasing thickness ranging from (40.9) nm to (61.3) nm, and more preferably, from (46) nm to (56.2) nm, and sometimes, it reaches (51.1) nm. Similarly, layer (25) may have a reduced thickness of (8-12) nm, and more preferably, by (9-11) nm, and sometimes by (10) nm, while layer (23) has a thickness Increasingly, it ranges from (40.6) nm to (61) nm, and more preferably, from (45.7) nm to (55.9) nm, and sometimes, it reaches (50.8) nm. Additionally, or alternatively, one or more stacks of dielectric middle layers may include a layer comprising ZnSnO. This layer may be formed, for example, by a co-splash or splash [for example from zinc or zinc oxide targets and from tin or tin oxide].

Layers may be provided that include tin oxide zinc instead of or in addition to layers that include tin oxide on one or both sides.

The following table includes performance data for the example model shown in Figure No. (5) in the case that it is plasticized, as well as the modifications that were made in Figure No. (5) shown for this example model, in which the two layers (5) and (12) containing the titanium oxide, where the coated material is heat treated, for example when it is placed and deposited on a clear float glass with a thickness of (6.0) mm, for example according to the table previously described above. Of course, underlayments of different thicknesses and/or underlayments with different compositions may be used in many different models.

It will be recognized that the preferred range may be the same or similar to that of annealed or heat-treated models.

It will also be realized that the performance will be almost comparable for the annealed and heat-treated models, but this will be with models treated outside the scope of the performance of the annealed models, in the form of permeability or expressed in the form of permeability.

Table No. (5): An example of the performance of the distinctive properties of single-layer laminated materials

Parameter

the favorite

Most preferred

Example

Plasticized sample

Heat treated (HT) sample

Permeability Y(%)

>=55

>=65

68.9

67.7

68.7

T a*

-7.0--3.1

-6--4.1

-5.1

-6.1

-5.6

Tb*

-1.3-2.7

-0.3-1.7

0.7

4.5

6.0

TL*

84.9-88.0

85.7-87.3

86.5

85.9

86.4

Reflectivity of thin film side Y(%)

1.6-8.6

3.3-6.9

4.9

8.5

7.1

Rf a*

-2.0-6.0

-0.08-3.9

1.9

-6.0

-1.0

Rf b*

-16.0--8.1

-14.0--10.1

-12.1

-2.9

-5.1

Rf L*

16.4-36.4

21.4-31.5

26.4

35.1

32.0

Reflectivity of glass side Y(%)

4.3-10.7

5.9-9.2

7.4

5.5

4.5

Rg a*

-5.1-0.9

-3.6--0.7

-2.1

-3.6

-1.0

Rg b*

-11.3--3.4

-9.3--5.4

-7.3

-1.4

-4.5

Rg L*

25.7-39.7

29.2-36.2

32.7

28.0

25.2

Reflectivity of a glass side at an angle of (45) Y(%)

5.4-12.8

7.3-11.0

9.0

Rg a*

-3.8-2.1

-2.3-0.7

-0.9

Rg b*

-4.1-3.8

-2.1-1.9

-0.1

Rg L*

28.9-43.0

32.4-39.5

36.0

Thin film resistance (ohms/square)

1.1-1.9

1.3-1.7

1.5

1.2

1.0

Normal emissivity(%)

1-4

1-3

2.00

The following table includes data for the performance of insulating glass (IG) window units that include a coated article as shown in the example model shown in Figure No. (5) in the annealed state, as well as in the case of modification to the example model shown. In Figure No. (5), in which the two layers (5) and (12) containing titanium oxide have been eliminated, as the coated material is heat treated, for example, when it is placed and deposited on surface No. (2) of the unit (IG).

Examples shown in the following table include a first and second basic sublayer of 6.0 mm thickness separated from each other by a 12 mm gap filled with air.

Of course, substrates of different thicknesses, substrates with different compositions, different gap sizes, different gases, etc. may be used in different embodiments.

It will be recognized that the preferred range may be the same or similar to that of annealed or heat-treated models. It will also be realized that the performance will be almost comparable for the annealed and heat-treated models, but this will be with models treated outside the scope of the performance of the annealed models, in the form of permeability or expressed in the form of permeability.

Table No. (6): An example of the performance of the distinctive properties of insulating glass (IG) window units

Parameter

the favorite

Most preferred

Example

Plasticized sample

Heat treated (HT) sample

TVIS(orTY) (%)

>=55

>=60

61.6

60.7

61.6

THV(%)

<= 10

<= 4

4.7

4.6

6

Tsol (%)

<=30

<= 23

23.6

23.2

22.9

Rsol(%)

<=50

<= 40

38.6

38.6

39.4

SHGC

<=30

<== 27

27.4

27.1

26.8

U-Value

<=1.8

<= 1.63

0.29

0.286

0.285

LSG

>=2.10

>= 2.20 (eg 2.26, 2.33, etc.)

2.25

2.24

2.3

In the previous two tables (4) and (5), visual data were collected using the “C” III (2°) observer. Thermal performance was compiled according to NFRC (2001) specifications.

In examples of certain embodiments, the layer consisting primarily of nickel titanium may be deposited by sputter depositing from a source to a metallic target. In some cases, the target source may include (20%) by weight nickel, (80%) by weight titanium. In examples of other certain embodiments, the target source may comprise (50%) by weight nickel, (50%) by weight titanium. The source of the metallic sputter depositing target may be or contain from 1% by weight to 50% by weight nickel (including any sub-range in between these ranges), and, more preferably, a range of (2%) by weight to (50%) by weight nickel (including any subrange in between) and, more preferably, from (5%) by weight to (20%) by weight nickel (including any subrange in between These two ranges), in examples of specific models. The source of the metallic sputter depositing target may also be or contain between 50% by weight and 99% by weight titanium (including any sub-range in between), and, more preferably, between From (50%) by weight to (98%) by weight titanium (including any sub-range in between) and, more preferably, from (80%) by weight to (95%) by weight titanium (including any sub-range falls between these two ranges) in examples of certain models.

In examples of certain other embodiments, the layer consisting primarily of nickel titanium may be deposited by sputtering from more than one source to a single metal target. In some cases, the target may be a nickel metal target or a titanium target. In certain examples, the layer consisting primarily of silver nickel and/or titanium may be deposited by a splash method in the presence of one or more noble gases and/or reactive gases. In examples of certain embodiments, nickel and titanium may be deposited in the presence of at least argon and oxygen. In examples of certain other embodiments, one or more of the target sources may be a ceramic material. For example, the barrier or insulating layer may be deposited using a source of at least a metal target comprising nickel, a ceramic target comprising titanium oxide, and/or a metal target comprising titanium and a ceramic target comprising nickel oxide.

Furthermore, in examples of certain other embodiments as well, one, two, or more ceramic targets may be used to deposit a layer comprising nickel titanium oxide.

In examples of certain embodiments, some contact layers may comprise only nickel and/or titanium and/or their oxides thereof and nitrides thereof. In examples of certain other embodiments, other contact layers may include nickel and/or chromium, and/or their oxides thereof and nitrides thereof. In examples of certain other embodiments, other contact layers may also include zinc and/or its oxide thereof.

The use of a contact layer composed primarily of nickel titanium and/or its oxide thereof has been found to be useful in improving the mechanical and chemical durability of the coated material, without sacrificing optical properties, such as a stack of silver. A single layer (e.g., low-E coatings containing only one layer of waste) may be used in single-layer examples, over surface 1 and/or surface 2 of the underlying substrate. Glassware (for example, the packaging may be facing in or out). However, this invention is not limited or limited, as low-E coatings comprising an insulating layer of nickel titanium oxide may be used on any surface in any form according to examples. Different for different models.

Although examples of specific embodiments have been described in relation to low-E packaging, inclusions containing nickel and/or titanium may be used for different types of packaging.

The coated material may or may not be heat treated (e.g., intense heating) as described herein [for example, see Figures 1 through 5] for examples of certain embodiments. . The terms “heat treatment” and “heat treatment” as used herein mean heating the material to a temperature sufficient to achieve tempering and/or heat strengthening of a material containing or including glass. This definition includes, for example, heating a coated material in an oven or furnace at a temperature of at least 550°C, and more preferably, at a temperature of at least 580°C, and more preferably, at a temperature of 600°C. ) At least, and more preferably, at a temperature of at least 620°C, and most preferably, at a temperature of at least 650°C and for a period of time sufficient to allow for the achievement of thermal normalization and/or heat strengthening. This may be for a period of at least two minutes, or up to 10 minutes in examples of certain embodiments.

As described above, examples of certain embodiments may include low-E coatings that are supported or reinforced by a lower glass substrate. This coating material may be used as a single layer or as a laminate consisting of several thin layers stacked on top of each other of another glass or other underlying substrate. The sheathing material can also be constructed from an insulated glass (IG) unit. In general, insulating glass (IG) window units include two primary sublayers, a first and a second, that are parallel and spaced apart from each other. A seal is provided around the perimeter of these two basic sublayers, with a gap between them [which may be at least partially filled with an inert gas such as argon, xenon, and/or Krypton, and/or similar] and this gap is maintained between these two underlying substrata.

The laminated materials shown and described herein may be, or similar laminated materials laminated with another thin layer of glass in examples of certain embodiments. An internal or interfacial layer consisting mainly of polymer may be used in certain implementations or completions. Materials such as PVB, EVA, etc. may be used in various other models. In such cases, encapsulation may be provided between the underlying substrates [for example, on Surface No. 2, or on Surface No. 3] of the resulting thin layered laminated material.

Some or all of the layers described here may be deposited by sputter deposition or by using any other suitable technique, for example, CVD, combustion deposition, etc.

Some or all of the layers described here may be deposited by splash deposition, or by using any other suitable technique, for example, CVD, combustion deposition, etc. For example, layers containing nickel and titanium may be deposited by sputter depositing from one or more sputter targets. Sputter depositing targets may include 1% to 50% nickel, 50% to 99% titanium, and, more preferably, 5% to 40%. %) nickel and (60%) to (95%) titanium, and, most preferably, (10%) to (30%) nickel and (70%) to (90%) titanium. In examples of certain embodiments, the ratio of nickel to titanium in the sputter depositing target may be equal to (20:80). It is possible that there are other ratios [nickel: titanium] present in different comprehensive models, for example (95/5); (75/25); (50/50); (25/75); (20/80); (10/90); etc. It is also possible that there may also be a sub-period located between the perpendiculars of these lineages that have been explained here. Furthermore, it will be understood that such percentages/ratios may be applied with respect to the amount of nickel and/or titanium present in such layers, whether such layers are partially oxidized, fully oxidized, or completely non-oxidized (e.g. in metallic form).

Examples of materials disclosed herein may be used in connection with low-E coatings, anti-condensation coatings, and/or other application of other coatings. Examples of low-E coatings, and/or anti-condensation coatings have been described, for example in patent applications bearing serial numbers 12/926,714; 12/923,082; 12/662,894; 12/659,196; 12/385,234; 12/385,802; 12/461,792; 12/591,611; and 12/654,594, all of which are incorporated herein in their entirety by reference and use. Therefore, in examples of certain embodiments, one or more insulating layer materials described herein may be replaced or supplemented by one or more layers comprising nickel and/or chromium in such packaging and/or in other types of such packaging. As used herein, the terms “above,” “supported,” and the like, should not be construed as directly adjacent to each other unless otherwise indicated.

In other words, the first layer may be said to be "above" or "supported by" a second layer, even if there are one or more layers between them.

Although the present invention has been described in terms of what is currently considered to be the most practically applicable and preferred embodiment, it should be understood that the present invention is not limited or limited to the disclosed embodiment, and, to the contrary, it is intended To cover only the numerous amendments to it and equivalent arrangements that are included in the spirit and scope of the appended safeguards.