Article comprising a protective top layer based on mixed oxide of zirconium and aluminum

Abstract

An article includes a substrate that is transparent, the substrate being covered on at least one of its faces, totally or partly, with a protective layer based on zirconium and aluminum mixed oxide.

Claims

1. An article comprising a substrate that is transparent, said substrate being covered on at least one of its faces, totally or partly, with a protective layer based on zirconium and aluminum mixed oxide, wherein the Al/Zr atomic ratio in the zirconium and aluminum mixed oxide is between 0.05 and 0.5, wherein a thickness of the protective layer is between 1 and 50 nm.

2. The article as claimed in claim 1, wherein the protective layer based on zirconium and aluminum mixed oxide is the layer that is the most remote from the substrate.

3. The article as claimed in claim 1, wherein the Al/Zr atomic ratio in the zirconium and aluminum mixed oxide is between 0.05 and 0.4.

4. The article as claimed in claim 3, wherein the Al/Zr atomic ratio in the zirconium and aluminum mixed oxide is between 0.1 and 0.4.

5. The article as claimed in claim 4, wherein the Al/Zr atomic ratio in the zirconium and aluminum mixed oxide is between 0.2 and 0.3.

6. The article as claimed in claim 1, wherein the atomic proportions of aluminum and zirconium in the protective layer relative to the proportions of all the elements other than oxygen and nitrogen are greater than 50%.

7. The article as claimed in claim 1, wherein the mass proportions of aluminum in the protective layer relative to the mass proportions of all the elements other than oxygen and nitrogen present in the protective layer are greater than 10% and less than 60%.

8. The article as claimed in claim 1, wherein the mass proportions of zirconium in the protective layer relative to the mass proportions of all the elements other than oxygen and nitrogen present in the protective layer are greater than 40% and less than 90%.

9. The article as claimed in claim 1, wherein a thickness of the protective layer is between 5 and 35 nm.

10. The article as claimed in claim 1, further comprising a coating located between said protective layer and said substrate.

11. The article as claimed in claim 1, wherein the substrate is coated with a stack of thin layers comprising at least one functional layer and said at least one protective layer based on zirconium and aluminum mixed oxide.

12. The article as claimed in claim 11, wherein the protective layer based on zirconium and aluminum mixed oxide is located over the functional layer.

13. The article as claimed in claim 11, wherein the stack of thin layers comprises at least one silver-based functional metal layer, at least two coatings based on dielectric materials, each coating comprising at least one dielectric layer, such that each functional metal layer is arranged between two coatings based on dielectric materials.

14. The article as claimed in claim 11, wherein the at least one functional layer is metallic.

15. The article as claimed in claim 1, such that the transparent substrate is: made of glass, or made of polymer.

16. The article as claimed in claim 15, wherein the glass is silico-sodic-calcium glass, and wherein the polymer is polycarbonate, polymethyl methacrylate, polyethylene, polyethylene terephthalate or polyethylene naphthalate.

17. The article as claimed in claim 1, wherein the article is heat treated.

18. The article as claimed in claim 17, wherein the article is heat treated by annealing, toughening and/or bending.

19. A glazing for a vehicle or glazing for a building, or glazing included in the composition of a table, a counter, a cooking hob, a shower wall, a partition or a radiator, comprising an article as claimed in claim 1.

20. A process for manufacturing an article that includes a substrate that is transparent, said substrate being covered on at least one of its faces, totally or partly, with a protective layer based on zirconium and aluminum mixed oxide, wherein the Al/Zr atomic ratio in the zirconium and aluminum mixed oxide is between 0.05 and 0.5, wherein a thickness of the protective layer is between 1 and 50 nm, the method comprising depositing said protective layer based on zirconium and aluminum mixed oxide: (i) by magnetron cathode sputtering, or (ii) by chemical vapor deposition using a suitable precursor based on zirconium and aluminum, or (iii) by gas-phase pyrolysis under ambient pressure.

21. The process as claimed in claim 20, wherein said protective layer is deposited by co-sputtering of zirconium oxide and aluminum oxide or by reactive sputtering using a target of zirconium and aluminum in the presence of O.sub.2, or a mixed target of zirconium and aluminum oxide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a view in cross section of one embodiment of an article coated according to the invention;

(2) FIG. 2 is a view in cross section of another embodiment of an article coated according to the invention;

(3) FIG. 3 represents the coefficient of friction as a function of the number of wear cycles;

(4) FIG. 4 represents the coefficient of friction for a protective layer of ZrOx:CuO of Comparative Examples 4a to 12a deposited onto glass sheets;

(5) FIG. 5 represents the coefficient of friction for a protective layer of ZrOx :CuO of Comparative Examples 4b to 12b deposited onto glass sheets;

(6) FIG. 6 represents the coefficient of friction for a protective layer of ZrOx :AlOx of Examples 13 a to 21a according to the invention deposited onto glass sheets, and

(7) FIG. 7 represents the coefficient of friction for a protective layer of ZrOx :AlOx of Examples 13b to 21b according to the invention deposited onto glass sheets.

(8) FIG. 1 is a view in cross section of one embodiment of an article coated according to the invention. In FIG. 1, the substrate 1 is optionally surmounted with a coating 2 constituted successively, starting from said substrate 1, of a layer 4 that acts as a barrier to the diffusion of oxygen and ions, among which Na+, of a wetting layer 5 and then of a low-emissivity stack (6) and/or of a solar-control stack (7), surmounted with a protective layer 3 based on zirconium and aluminum mixed oxide.

(9) FIG. 2 is a view in cross section of another embodiment of an article coated according to the invention. In FIG. 2, the substrate 1 is surmounted with a stack constituted successively, in the following order, (i) of a layer 4 that acts as a barrier to the diffusion of oxygen and Na+ ions, inter alia, (ii) of a wetting layer 5, (iii) of a functional layer 8 made of silver, (iv) of a blocking layer 9 also known as the “sacrificial” layer and then finally, again, (v) of a layer based on dielectric material 10, (vi) of an oxygen-barrier layer 11, (vii) surmounted with a protective layer 3 based on zirconium and aluminum mixed oxide.

(10) These FIGS. 1 and 2 are very schematic and, for greater clarity, do not adhere to the proportions as regards the thicknesses of the various materials represented.

(11) A protective layer 3 whose purpose is to protect the substrate 1 against scratches is deposited on said substrate, in direct contact therewith or otherwise. Specifically, a coating 2 may optionally be arranged on said substrate 1 so as to be between said substrate 1 and said protective layer 3. In this case, said protective layer 3 is the outermost layer of the stack arranged on said substrate, i.e. the layer that is the most remote from said substrate 1.

(12) The article according to the invention thus comprises at least one transparent substrate 1, especially made of glass, at least one protective layer 3 and optionally a coating 2.

(13) According to FIG. 1, this coating 2 comprises, starting from the substrate 1:

(14) (i) at least one intermediate barrier layer 4,

(15) (ii) at least one wetting layer 5 and

(16) (iii) at least one stack of low-emissivity layers 6 and/or a stack of solar-control layers 7.

(17) According to FIG. 2, the coating 2 comprises in greater detail, starting from the substrate 1, besides at least one intermediate barrier layer 4 and at least one wetting layer 5:

(18) (i) at least one functional layer 8, in particular a metal layer with infrared properties, which is preferably silver-based,

(19) (ii) optionally at least one blocking layer 9 also known as the “sacrificial layer”, placed immediately over and in contact with said functional layer 8 with infrared properties,

(20) (iii) at least one layer 10 of dielectric material that is not susceptible to substantial structural modification, especially of crystallographic order, at high temperature, and

(21) (iv) at least one barrier layer 11 based on dielectric material, preferably based on a compound comprising silicon such as silicon nitride and aluminum nitride.

(22) By way of illustration, stacks of layers in accordance with the invention may thus be of the type:

(23) Glass//Si3N4 or AlN//ZnO/Ag/Nb//Si3N4//AlZrO or

(24) Glass//Si3N4//ZnO/Ag/Nb//ZnO//Si3N4//AlZrO or

(25) Glass//SiO2 or SiOxCy//ZnO/Ag/Nb//ZnO//Si3N4 or AlN//AlZrO or

(26) Glass//SnO2//ZnO/Ag/Nb//Si3N4//AlZrO.

(27) The invention thus allows the production of highly transparent, low-emissivity, toughenable and/or bendable, scratch-resistant articles. These properties, and especially the scratch resistance, are maintained virtually intact whether or not the substrates bearing said stacks are subjected, after deposition, to heat treatments such as bending, annealing or toughening. Very few colorimetric modifications are also observed, especially in terms of reflection.

(28) A whole series of advantages follows therefrom: a single configuration of scratch-resistant stack of layers for each type of toughenable glazing, i.e. both toughened and non-toughened glazing.

(29) It is also possible to assemble without preference, for example on a building facade, toughened and non-toughened glazings: the eye will not be able to detect differences in the overall optical appearance of the facade. It also becomes possible to sell non-toughened coated glazings, the act of toughening or not toughening them being left to the buyer's discretion, while at the same time being able to ensure said buyer of the consistency not only of their optical and thermal properties, but above all of their scratch resistance.

(30) The articles according to the invention are able to be heat-treated, in particular by annealing, toughening and/or bending. However, whether or not they are bent, annealed or toughened, they have, by virtue of the invention, improved and consistent surface hardness relative to the prior art.

(31) The article may be in the form of monolithic glazing, laminated glazing or multiple glazing, especially double glazing or triple glazing.

(32) The protective layer based on zirconium and aluminum mixed oxide may be on faces 1, 2, 3 and/or 4 for laminated glazings comprising an intermediate PVB layer, located between face 2 and 3 of said glazing or on faces 1, 2, 3 and/or 4 of a multiple glazing, for example a double glazing comprising an air or gas space between face 2 and 3 of said glazing.

(33) The article according to the invention finds particularly advantageous applications in the manufacture

(34) (i) of glazings, especially of windshields in the motor vehicle sector or of windows in the building sector, of mirrors,

(35) (ii) of interior furnishing items, such as tables, counters, cooking hobs, shower walls, partitions, radiators, and wall coverings, such as facade coverings, inter alia.

(36) The details and advantageous characteristics of the invention will now emerge from the following nonlimiting examples. Throughout the examples, the successive depositions of thin layers are performed via a magnetic-field-assisted cathode sputtering technique, but may also be performed via any other technique that allows good control of the layer thicknesses obtained.

(37) The substrates onto which the stacks of thin layers are deposited are clear silico-sodic-calcium glass substrates of the Planilux® type, sold by SAINT-GOBAIN VITRAGE.

(38) 1. Measurement of the Coefficient of Friction

(39) In the Examples and Comparative Examples that follow, the coefficient of friction was measured in the following manner:

(40) A steel bead 10 mm in diameter is rubbed on glass (Comparative Example 1) or on a protective layer sputtered beforehand onto glass, in the other cases, with a constant load of 0.5N over a distance of 10 mm, the aim being to rub the surface of the glass or of the layer without degrading it. The test consists in performing a certain number of wear cycles (1 cycle=1 to-and-fro motion) defined below, at the same place and recording at each passage said coefficient and then calculating its mean value. After each test, the bead is turned in its bead holder so as to use a new surface in contact with the layer when the sample to be tested is changed.

COMPARATIVE EXAMPLE 1

(41) A silico-sodic-calcium glass plate 2.1 mm thick is subjected to one or more wear cycles ranging from 2 to 10 cycles allowing the scratch resistance of the glass to be shown.

COMPARATIVE EXAMPLE 2

(42) A protective layer of TiOx 20 nm thick is deposited by magnetron cathode sputtering onto a glass plate identical to that of Comparative Example 1. As previously, Comparative Example 2 is subjected to one or more wear cycles ranging from 2 to 10 cycles allowing the scratch resistance of the glass to be shown.

COMPARATIVE EXAMPLE 3

(43) A protective layer of TiOx 20 nm thick is deposited by magnetron cathode sputtering onto a glass plate identical to that of Comparative Example 1. The glass plate thus coated is then subjected to a heat treatment at 640° C. for 10 minutes. As previously, Comparative Example 3 is subjected to one or more wear cycles ranging from 2 to 10 cycles allowing the scratch resistance of the glass to be shown.

(44) The coefficient of friction measured is reported for each case in FIG. 3. FIG. 3 represents the coefficient of friction as a function of the number of wear cycles:

(45) (i) for the naked glass (see the “glass1” points on the graph),

(46) (ii) for a protective layer of 20 nm of TiOx deposited on a sheet of glass (see the “TiOx” points on the graph) and

(47) (iii) for a protective layer of 20 nm of TiOx deposited on a sheet of glass, after heat treatment (see the “TiOx T” points on the graph).

(48) The coefficient of friction measured for the naked glass is 0.7, whereas it is about 0.4 for the Comparative Examples with a titanium oxide protective layer, before or after toughening.

COMPARATIVE EXAMPLES 4a to 12a

(49) A protective layer 20 nm thick of ZrOx:CuO, the Cu and Zr content of which is given for each Comparative Example 4a to 12a in table 1 below, is deposited by magnetron cathode sputtering, in particular by co-sputtering of zirconium oxide and copper oxide onto a glass plate identical to that of Comparative Example 1.

COMPARATIVE EXAMPLES 4b to 12b

(50) As for the Comparative Examples 4a to 12a, a protective layer 20 nm thick of ZrOx:CuO, the Cu and Zr content of which is given for each Comparative Example 4b to 12b in table 1 below, is deposited by magnetron cathode sputtering, in particular by co-sputtering of zirconium oxide and copper oxide onto a glass plate identical to that of Comparative Example 1. The plates thus coated are then subjected to a heat treatment at 640° C. for 10 minutes.

(51) Table 1 below gives not only the weight percentages of Cu and Zr, but also the resulting weight ratio Cu/Zr, of each Comparative Example 4a to 12a which did not undergo heat treatment, and of each Comparative Example 4b to 12b which underwent a heat treatment.

(52) TABLE-US-00001 TABLE 1 Cp. Ex. 4 5 6 7 8 9 10 11 12 a or b a or b a or b a or b a or b a or b a or b a or b a or b % Cu* 3.1 3.8 4.8 5.4 7.3 8.6 11.9 13.8 15.8 % Zr* 96.9 96.2 95.2 94.6 92.7 91.4 88.1 86.2 84.2 Cu/Zr 0.03 0.04 0.05 0.06 0.08 0.09 0.14 0.16 0.19 *weight percentage relative to the total weight of Cu and Zr

(53) Comparative Examples 4a to 12a and 4b to 12b are then subjected to 1, 4 or 15 wear cycles. The results are collated on the graphs of FIGS. 4 (without heat treatment) and 5 (after heat treatment).

(54) FIG. 4 represents the coefficient of friction for a protective layer of ZrOx:CuO of Comparative Examples 4a to 12a deposited onto glass sheets, said glass sheets thus coated having been subjected to 1, 4 or 15 wear cycles. The composition of Comparative Example 4a having the lowest content of Cu and the composition of Comparative Example 12a having the highest content of Cu of Comparative Examples 4a to 12a.

(55) FIG. 5 represents the coefficient of friction for a protective layer of ZrOx:CuO of Comparative Examples 4b to 12b deposited onto glass sheets, said glass sheets thus coated having been subjected to a heat treatment before undergoing 1, 4 or 15 wear cycles. The composition of Comparative Example 4b having the lowest content of Cu and the composition of Comparative Example 12b having the highest content of Cu of Comparative Examples 4b to 12b.

(56) In FIGS. 4 and 5, the arrow going from “−” to “+” indicates that the Cu content, in the protective layer of the comparative examples mentioned, increases in the direction indicated by the arrow.

(57) For FIG. 4: It is seen that the doping with Cu of ZrOx has no influence on the coefficient of friction up to Comparative Example 10a (high doping with Cu). For the Comparative Examples that follow, on the other hand, the doping has a strong influence and the coefficient of friction increases very markedly to exceed 0.7.

(58) For FIG. 5: The coefficients of friction for the layers of toughened ZrOx:Cu are smaller. Up to Comparative Example 8b, doping with copper has no influence on the coefficient of friction: said coefficient is constant at 0.1, even after 15 wear cycles. On the other hand, for the Comparative Examples that follow, doping with copper has an influence on the coefficient of friction values and a uniform increase which reaches 0.35 for Comparative Example 12b (the one which is the most strongly doped) is noted.

EXAMPLES 13a to 21a ACCORDING TO THE INVENTION

(59) A protective layer 20 nm thick of ZrOx:AlOx, the Al and Zr content of which is given for each Example 13a to 21a in table 2 below, is deposited by magnetron cathode sputtering, in particular by co-sputtering of zirconium oxide and aluminum oxide onto a glass plate identical to that of Comparative Example 1.

(60) The protective layer based on zirconium and aluminum mixed oxide does not comprise any elements other than nitrogen and oxygen.

EXAMPLES 13b to 21b ACCORDING TO THE INVENTION

(61) As for Examples 13a to 21a, a protective layer 20 nm thick of ZrOx:AlOx is deposited by magnetron cathode sputtering, in particular by co-sputtering of zirconium oxide and aluminum oxide onto a glass plate identical to that of Comparative Example 1. The plates thus coated are then subjected to a heat treatment at 640° C. for 10 minutes.

(62) Table 2 below gives: the weight percentages of Al and Zr relative to the total weight of Al and of Zr in the Zr and Al mixed oxide, and the resulting Al/Zr weight ratio, for each Example 13a to 21a, which has not undergone a heat treatment, and for each Example 13b to 21b, which has undergone a heat treatment.

(63) The measurements are taken using a scanning electron microscope via the EDX method.

(64) TABLE-US-00002 TABLE 2 Ex. 13 14 15 16 17 18 19 20 21 a or b a or b a or b a or b a or b a or b a or b a or b a or b % Al** 17.2 21.8 32.3 36.3 43.2 43.6 47.2 50 53.4 % Zr** 82.8 78.2 67.7 63.7 56.8 56.4 52.8 50 46.6 Al/Zr 0.21 0.28 0.48 0.57 0.76 0.77 0.89 1 1.15 **weight percentage relative to the total weight of Zr and Al.

(65) Examples 13a to 21a and 13b to 21b are then subjected to 1, 4 or 15 wear cycles. The results are collated on the graphs of FIGS. 6 (without heat treatment) and 7 (after heat treatment).

(66) FIG. 6 represents the coefficient of friction for a protective layer of ZrOx:AlOx of Examples 13a to 21a according to the invention deposited onto glass sheets, said glass sheets thus coated having been subjected to 1, 4 or 15 wear cycles. The composition of Example 13a having the lowest content of Al and the composition of Example 21a having the highest content of Al of Examples 13a to 21a.

(67) FIG. 7 represents the coefficient of friction for a protective layer of ZrOx:AlOx of Examples 13b to 21b according to the invention deposited onto glass sheets, said glass sheets thus coated having been subjected to a heat treatment before undergoing 1, 4 or 15 wear cycles. The composition of Example 13b having the lowest content of Al and the composition of Example 21b having the highest content of Al of Examples 13b to 21b.

(68) In FIGS. 6 and 7, respectively, the arrow going from “−” to “+” indicates that the Al content, in the protective layer of the examples mentioned, increases in the direction indicated by the arrow.

(69) For FIG. 6: It is found that doping with Al has no influence on the coefficient of friction, which remains stable and low at 0.15.

(70) For FIG. 7: the coefficient of friction is a little lower still and in the region of 0.1.

(71) In the context of the invention, a low coefficient of friction of the order of 0.1 to 0.15 is observed, which is not influenced by the degree of doping with Al in the Zr and Al mixed oxide, whether or not a heat treatment is applied (see FIGS. 7 and 6), unlike the case of ZrOx:Cu (see FIGS. 4 and 5) and in all cases is much lower than the coefficient of friction measured for the naked glass or for the Comparative Examples with a protective layer of titanium oxide, before or after toughening (see FIG. 3).

(72) 2. Measurement of the Critical Damage Load

(73) In the Examples and Comparative Examples that follow, the critical damage load Lc was measured in the following manner. A steel bead 1 mm in diameter is rubbed on glass (Comparative Example 1) or on a protective layer sputtered beforehand onto glass, in the other cases, with an increasing load of 0.03N and 30N at a loading rate of 15 N/minute over a scratch length of 10 mm, at a rate of movement of 5 mm/minute. Between each scratch, the bead is turned so as to renew the contact zone. Five scratches were performed each time to determine a mean critical load value Lc. The critical load Lc corresponds to the load at which the protective layer gives way.

(74) TABLE-US-00003 Examples Lc (N) Comp. Ex. 1 11.5 Ex. 13a to 21a >30 Ex. 13b to 21b >30 Comp. Ex. 5a 25 Comp. Ex. 11a 6 Comp. Ex. 6b 27 Comp. Ex. 10b 11 Comp. Ex. 2 5 Comp. Ex. 3 9

(75) The critical load Lc is 11.5±3.2N for naked glass (Comparative Example 1).

(76) The critical load Lc is greater than 30N, which is extremely high, for all the examples according to the invention (Examples 13a to 21a and 13b to 21b), irrespective of the content of Al in the Zr and Al mixed oxide, and whether or not they have undergone toughening. In addition, an absence of fissuring is observed for all the tests performed on the samples.

(77) It is higher than the critical load of the Comparative Examples with a layer of ZrOx:Cu which has undergone toughening (Comparative Examples 4b to 12b) or which has not undergone toughening (Comparative Examples 4a to 12a). In general, the Lc lowers when the Cu doping in the ZrOx increases. It thus passes from 25N for Comparative Example 5a to reach 6N for Comparative Example 11a and it passes from 27N for Comparative Example 6b to reach 11N for Comparative Example 10b.

(78) In the case of the Comparative Examples with a layer of TiOx which has not undergone a heat treatment (Comparative Example 2), the critical load Lc observed is only 5N, whereas it is 9N in the case of the Comparative Examples with a layer of TiOx which has undergone a heat treatment (Comparative Example 3). In this case, an effect of increasing the Lc by toughening is observed.

(79) In conclusion, it is observed that the protective layer based on zirconium and aluminum mixed oxide according to the invention is the most efficient. Specifically, a critical damage load Lc of greater than 30N and a low coefficient of friction of 0.15 are obtained for the protective layer which has not undergone toughening and of 0.1 for the protective layer after toughening, irrespective of the aluminum content in the zirconium and aluminum mixed oxide.