SET OF COLORED TABLEWARE WITHOUT ADDED CHROME AND NICKEL AND TABLEWARE ITEMS

Abstract

[COMPOSITION OF COLORED TABLEWARE WITHOUT ADDED CHROME AND NICKEL AND TABLEWARE ITEM Composition of colored tableware, without intentional addition of Ni and Cr, comprising by mass SiO2 + Al2O3 more than 70.0%, SiO2 from 60.0 to 75.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 12.0%, Al2O3 from 0.5 to 9.0%, MgO less than 6.0%, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO at most 5.0%, F2 less than 9.0%, SO3 less than 0.25%, total Fe2O3 1200 to 3000 ppm, Se 5 to 100 ppm and exhibiting a redox expressed as a FeO / Fe2O3 total ratio between 0.08 and 0.2.]

Description

Title of the invention: Composition of coloured tableware without the addition of chrome and nickel, and tableware item

[0001] The present invention relates to the field of colored glass or vitroceramic tableware.

[0002] In glassmaking, there are glasses with specific compositions that meet particular specifications. Some pharmaceutical glasses must resist specific chemical agents. Optical glasses have selected wavelengths of visible or non-visible light transmission. Industrial glasses meet a variety of requirements. For example, vehicle windshield glass requires high IR and UV absorption while allowing for flat production. Glazing glass in the building sector, or architectural glass, aims to reduce heat transmission and is produced in specific flat-film glass production furnaces.

[0003] In the field of colored glass or glass-ceramic tableware, production takes place by pressing, centrifugation, or blow molding. The glass may be soda-lime. The glass-ceramic may be borophosphate or fluorosilicate. Such a glass-ceramic is obtained from a bath of molten glass by controlled cooling. Partial crystallization, through liquid-liquid separation, occurs during the flow between the furnace outlet and a forming machine. The glass-ceramic at room temperature comprises at least one crystalline phase and one glassy phase. Heat treatment of the glass-ceramic at a temperature below the glass transition temperature is possible to relieve internal stresses in the material.

[0004] On the contrary, conventional glass-ceramics, in particular LAS, especially for cooktops, are obtained by a ceramicizing treatment at a temperature higher than the glass transition temperature after the forming of the article.

[0005] Glass or vitroceramic tableware can be transparent or opaque, i.e., reflective. Glass or vitroceramic tableware can be colorless or colored. Coloring is obtained by adding coloring raw materials, generally in quantities less than 1% by mass.

[0006] Conventionally, brown and gray tints are obtained by adding nickel oxide and chromium oxide. However, nickel oxide is classified as CMR (Carcinogenic, Mutagenic, Reprotoxic). Chromium oxide should also be avoided, the The CrVI form is toxic. Therefore, extraction and filtration equipment is used during manufacturing. Furthermore, new shades have been researched.

[0007] The Applicant sought to improve the situation.

[0008] The Applicant has conducted research aimed at providing a high-quality colored tableware item suitable for production in an industrial glass furnace under normal operating conditions, exhibiting color stability while reducing the risk of operator exposure to toxic substances. The risk to users, through migration and release, is so low that it falls below the detection threshold. Nevertheless, some markets demand glassware free of such chemical species.

[0009] The composition of colored, soda-lime, borophosphate, or fluorosilicate tableware, without the intentional addition of Ni and Cr, comprises by mass SiO2 + Al2O3 more than 70.0%, SiO2 from 60.0 to 75.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 12.0%, Al2O3 from 0.5 to 9.0%, MgO less than 6.0%, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO at most 5.0%, F2 less than 9.0%, SO3 less than 0.25%, total Fe2O3 1200 to 3000 ppm, Se 5 to 100 ppm, and has a redox potential expressed as a FeO / total Fe2O3 ratio between 0.08 and 0.2. A grey or brown colour is obtained without the addition of nickel, which was generally previously used for brown, and grey is obtained without the addition of chromium, which was previously used for grey.

[0010] In one embodiment, the composition has a brown color without intentional addition of CoO.

[0011] In one embodiment, the composition has a grey colour and comprises by mass 25 to 70 ppm CoO, preferably 25 to 55 ppm.

[0012] In one embodiment, the composition is composed without the intentional addition of TiO2, MnO2, and Pr2O5. Since manganese oxide can react depending on the redox potential and other dyes, it is advantageous to work without adding manganese. Pr2O5 has weak coloring power even at high concentrations.

[0013] In one embodiment, the composition comprises by mass 70.0 to 75.0% SiO2, at least 9.0% CaO + MgO, 10.0 to 15.0% Na2O, 8.0 to 12.0% CaO, less than 2.0% Al2O3, less than 5.0% MgO, less than 2.0% K2O, less than 2.0% BaO, less than 2.0% SrO, less than 1.50% F2, less than 1.0% Fe2O3 total 1500 to 3000 ppm and Se 10 to 80 ppm. A gray or brown soda-lime glass is obtained.

[0014] In one embodiment, the composition comprises by mass SiO2 of 72.0 to 74.0%, CaO + MgO of at least 11.0%, Na2O of 12.0 to 14.0%, CaO of 10.0 to 12.0%, Al2O3 of 1.0 to 1.8%, MgO less than 2.0%, K2O less than 1.0%, BaO less than 1.0%, SrO less than 1.0%, F2 less than 0.5%, total Fe2O3 2000 to 3000 ppm, Se 10 to 60 ppm, preferably 10 to 40 ppm.

[0015] In one embodiment, the composition comprises by mass 70.0 to 75.0% SiO2, less than 5.0% CaO + MgO, 10.0 to 14.0% Na2O, less than 4.0% CaO, 1.0 to 6.0% CaO + ZnO, 4.0 to 9.0% Al2O3, less than 2.0% MgO, 1.0 to 3.0% BaO, less than 2.0% SrO, 1.0 to 8.0% F2, 1200 to 3000 ppm total Fe2O3, and 7 to 80 ppm Se. A gray or brown fluorosilicate glass is obtained.

[0016] In one embodiment, the composition comprises by mass: SiO2 from 71.0 to 73.0%, CaO + MgO less than 3.0%, Na2O from 11.0 to 13.0%, CaO less than 3.0%, Al2O3 from 7.0 to 8.50%, MgO less than 1.0%, K2O from 1.0 to 2.0%, BaO from 1.5 to 2.5%, SrO less than 1.0%, F2 from 3.0 to 6.0%, Fe2O3 total 1200 to 3000 ppm, preferably 1300 to 3000 ppm in grey colour and 1200 to 2500 ppm in brown colour, Se 7 to 60 ppm, preferably 8 to 40 ppm.

[0017] In one embodiment, the composition comprises less than 4000 ppm of CeO2 by mass, preferably 1000 to 2000 ppm. Cerium is used to adjust the redox potential of the composition.

[0018] In one embodiment, the composition comprises by mass CaO from 0.20 to 8.0%, MgO less than 2.0%, preferably less than 1.0%, Al₂O₃ 2.0 to 9.0%, F₂ less than 1.0%, ZnO at most 1.0%, B₂O₃ from 4.0 to 15.0%, P₂O₅ from 1.0 to 8.0%, and B₂O₃ + P₂O₅ from 5.0 to 20.0%. A grey or brown borophosphate glass is obtained.

[0019] In one embodiment, the composition comprises SiO2 from 62.0 to 68.0%, preferably from 64.0 to 65.0%, CaO + MgO less than 4.0%, Na2O from 6.0 to 13.0%, K2O from 1.0 to 3.0%, preferably from 1.50 to 2.30%, CaO from 0.20 to 3.0%, preferably from 1.0 to 2.50%, B2O3 from 4.0 to 12.0%, preferably from 5.0 to 7.0%, P2O5 from 1.0 to 6.0%, preferably from 5.0 to 6.0%, B2O3 + P2O5 from 10.0 to 16.0%, preferably from 10.0 to 12.0%, Al2O3 of 4.0 to 8.0%, MgO without voluntary contribution, BaO from 1.0 to 4.0%, SrO less than 1.0%, without voluntary contribution of F2, total Fe2O3 1200 to 2500 ppm and Se 10 to 80 ppm.

[0020] In one embodiment, a piece of tableware has a composition as above. The glass or vitroceramic item is particularly economical to manufacture.

[0021] The glass or ceramic glass item is dishwasher safe.

[0022] Other features and advantages of the invention will become apparent from an examination of the detailed description below, and the accompanying drawings, in which:

[0023] [Fig.1] is a colorimetric diagram of a soda-lime glass according to one aspect of the invention.

[0024] [Fig.2] is a colorimetric diagram of a fluorosilicate glass according to one aspect of the invention.

[0025] The attached drawings may not only serve to complete the invention, but also contribute to its definition, if necessary.

[0026] During its research, the Applicant observed that a brown color can be obtained for glass or glass-ceramics using an iron-selenium coloring system. This color is due to a charge transfer phenomenon between ferrous iron (FeO or Fe2+) and selenium, which forms an Fe-Se complex. Thus, the brown color develops when some of the iron is in a reduced form. The Applicant succeeded in stabilizing the Fe-Se complex within an oxidized glass, specifically with a redox potential expressed as a total FeO / Fe2O3 ratio between 0.08 and 0.2.

[0027] However, adding iron in its reduced form FeO risks disrupting the redox equilibrium of the vitrifiable mixture and degrading the quality of the glass, inducing gaseous defects. Therefore, the feasibility of such a coloring process is challenging. A study is being conducted on the chemistry of the coloring elements and on redox adjustment.

[0028] Industrial trials lasting at least 24 hours were conducted on lines equipped to produce blown, pressed, and centrifuged articles, respectively. The objective was to stabilize the color, understand the coloring mechanisms involved, and obtain good glass quality.

[0029] In gray tint, the tests were carried out with a soda-lime glass without intentional addition of Ni and Cr, comprising by mass SiO2 + Al2O3 more than 70.0%, SiO2 from 60.0 to 75.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 12.0%, Al2O3 from 0.5 to 9.0%, MgO less than 6.0%, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO at most 5.0%, F2 less than 9.0%, SO3 less than 0.25%, total Fe2O3 1200 to 3000 ppm, Se 10 to 100 ppm and having a redox potential expressed as a FeO / total Fe2O3 ratio between 0.08 and 0.2. The FeO content can be between 150 and 600 ppm.

[0030] More specifically, the soda-lime glass comprises, by mass, 20 to 70 ppm of CoO, preferably 25 to 55 ppm. More specifically, the soda-lime glass is free from the intentional addition of TiO2, MnO2, and Pr2O5. More specifically, the soda-lime glass comprises, by mass, 70.0 to 75.0% of SiO2, at least 9.0% of CaO + MgO, 10.0 to 15.0% of Na2O, 8.0 to 12.0% of CaO, less than 2.0% of Al2O3, less than 5.0% of MgO, less than 2.0% of K2O, less than 2.0% of BaO, less than 2.0% of SrO, less than 1.50% of F2, less than 1.0% of Fe2O3, 1500 to 3000 ppm of total Fe2O3, and 10 to 80 ppm of Se. The FeO content can be between 200 and 500 ppm.

[0031] More specifically, soda-lime glass comprises by mass SiO2 from 72.0 to 74.0%, CaO + MgO at least 11.0%, Na2O from 12.0 to 14.0%, CaO from 10.0 to 12.0%, Al2O3 from 1.0 to 1.8%, MgO less than 2.0%, K2O less than 1.0%, BaO less than 1.0%, SrO less than 1.0%, F2 less than 0.5%, total Fe2O3 2000 to 3000 ppm, Se 10 to 60 ppm, Preferably from 10 to 40 ppm. The FeO content can be between 200 and 400 ppm.

[0032] In the CIELab color space, chromatic characteristics are defined by colorimetric or chromacity coordinates corresponding to lightness (L*), red / green color component (a*), and yellow / blue color component (b*). In other words, the CIELab color space is based on a sequential or continuous Cartesian representation on three orthogonal axes L*, a*, and b*. The coordinate L* denotes lightness (L* = 0 black and L* = 100 colorless), a* denotes the red / green color component (a* > 0 red, a* < 0 green), and b* denotes the yellow / blue color component (b* > 0 yellow, b* < 0 blue). The resulting grey soda-lime glass exhibits a color with L between 60 and 85 and is limited within a coordinate system b* = f(a*) in a quadrilateral defined by the four points with coordinates (-2, -4), (-2, 1), (8, 5), and (8, 0). a* is between -1 and 7.5. b* is between -3 and 4.5. The results of the tests are shown below:

[0033] [Tables 1] gopOsd; gÿësipizez 2 11 / il / / / ÊSëPijàlz U 075 / 7175 / / 175 / / 7115 / 71B| / 171 / / / KS A12O3 EÈ 1 / 5 / / LS / Z 11 / 1 / 1 / 11 / 705 / 13.35 13.35 105 / 13.35 13.35 13.35 BO / / .cs Os / / / O / / 11 / 1 / 11 B / 1 / 1 / 0 / M / / Oi P2OS 1.4 1 / 4 / / 11 / 14 / / li / / zli / 19 11 / ii / 21 UZ / / 1 / / 9 25 2250 Ois 111 / 2660 Ol / 2629 OB / / ChoQ (ppm) 39 / 27 / 27 / B / 21 B O / z 01 / 365 IO / / 233 Ol / z 585 o / / / / / ii 031 / 011 / 011 / 53.46 7111 / iii / / 7411 / AO / / 3.83 4.23 3 / 9Z9: / 117 / 13 / 1 / B / 1 / os / 1 / 1 / o ® / ili / z 1 / 1.26 / 10 / / 1 / 1 / / / Hl / Z color iB / / ü / z 01 / Os go / s O / / gO / /

[0034] In brown tint, the tests were carried out with a soda-lime glass without intentional addition of Ni and Cr, comprising by mass SiO2 + Al2O3 more than 70.0%, SiO2 from 60.0 to 75.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 12.0%, Al2O3 from 0.5 to 9.0%, MgO less than 6.0%, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO at most 5.0%, F2 less than 9.0%, SO3 less than 0.25%, total Fe2O3 1200 to 3000 ppm, Se 10 to 100 ppm and having a redox expressed as a FeO / total Fe2O3 ratio between 0.08 and 0.2. The FeO content can be between 150 and 600 ppm.

[0035] More specifically, the soda-lime glass is free from the intentional addition of CoO. More specifically, the soda-lime glass is free from the intentional addition of TiO2, MnO2, and Pr2O5. More specifically, the soda-lime glass comprises by mass 70.0 to 75.0% SiO2, at least 9.0% CaO + MgO, 10.0 to 15.0% Na2O, 8.0 to 12.0% CaO, less than 2.0% Al2O3, less than 5.0% MgO, less than 2.0% K2O, less than 2.0% BaO, less than 1.50% SrO, less than 1.0% F2, total Fe2O3 1500 to 3000 ppm, and Se 10 to 80 ppm. The FeO content may be between 150 and 500 ppm.

[0036] More specifically, the soda-lime glass comprises by mass 72.0 to 74.0% SiO2, at least 11.0% CaO + MgO, 12.0 to 14.0% Na2O, 10.0 to 12.0% CaO, 1.0 to 1.8% Al2O3, less than 2.0% MgO, less than 1.0% K2O, less than 1.0% BaO, less than 1.0% SrO, less than 1.0% F2, less than 0.5%, total Fe2O3 1950 to 3000 ppm, and Se 10 to 60 ppm, preferably 10 to 40 ppm. The FeO content may be between 180 and 400 ppm.

[0037] The resulting brown soda-lime glass exhibits a color with L between 75 and 85 and is limited in a coordinate system b* = f(a*) within a quadrilateral defined by the four points with coordinates (2; 5), (2; 11), (13; 17), and (13; 23). a* is between 2.5 and 12.5. b* is between 9 and 21. The tests are reported below:

[0038] [Tables2] Exempt Exempt 3 Example 4 Exempt 5 Example 6 Example 10 Example 1 1 Ois liiii 72,75 7P 7^ 72,75 77 7^. 72.75 72 JS mis 1.5 ili Lll ill iis üli 13.35 13.35 13.?ï 19.35 15.35 13.35 Mi 10.8 19.8 1C.8 10.8 10.8 19.8 10.8 ÜII ioi B2O3 P2O5 1.4 lis 1.1 1 4 Lli 1 1 iOi 18 21 25 16 lis 27 27 Fe20.3 ieiihüWss 2661 27 68 2955 2486 2973 2510 1987 FeO ( 396 382 345 334 377 290 fil 79.07 77.61 76 39.6 80.45 75.36 80.91 6.14 9 6G 10.33 lül 6.55 Élis ils 12.29 15.08 18.24 q 23 13.87 20.02 13.83 cost may ron riarron marrc-n brown laugh brown

[0039] The colorimetric data were measured by a Perkim Elmer UV / Vis spectrophotometer in transmission measurement on a one-centimeter double-sided polished glass, illuminating D65 at a 10° angle. The chemical data were measured by X-ray fluorescence. The FeO content was determined by spectral measurement.

[0040] Proportions are given as mass percentages unless otherwise specified, such as ppm for minor species. K₂O, BaO, F₂, B₂O₃, and P₂O₅ are not intentionally added. They may be present if recycled glass containing them is used. CoO is not intentionally added for the brown tint. CoO may be present if recycled glass containing it is used. Total iron is expressed as Fe₂O₃. Examples with Se content below 20 ppm show a light brown tint. The higher the Se content, the more intense the tint. The resulting quality is satisfactory.

[0041] The above tests were duplicated and then adapted to fluorosilicate glass to obtain a high-quality product. Fluorosilicate glass-ceramics consist of crystalline phases dispersed in a glassy matrix. During manufacturing, depending on the cooling rate, the products can have a different thermal history, which influences the colorimetric data. Thus, two sets of colorimetric data can be obtained for the same product, designated panel A and panel B.

[0042] In grey tint, the tests were carried out with a fluorosilicate glass without voluntary addition of Ni and Cr. Fluorosilicate glass comprises by mass SiO2 + A12O3 more than 70.0%, SiO2 from 60.0 to 75.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 12.0%, A12O3 from 0.5 to 9.0%, MgO less than 6.0%, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO at most 5.0%, F2 less than 9.0%, SO3 less than 0.25%, total Fe2O3 1200 to 3000 ppm, Se 5 to 100 ppm and having a redox expressed as a ratio of FeO / total Fe2O3 between 0.08 and 0.2.

[0043] More specifically, the fluorosilicate glass comprises 25 to 70 ppm CoO by mass, preferably 30 to 50 ppm. More specifically, the fluorosilicate glass is free from the intentional addition of TiO2, MnO2, and Pr2O5. More specifically, fluorosilicate glass comprises by mass SiO2 70.0 to 75.0%, CaO + MgO less than 5.0%, Na2O 10.0 to 14.0%, CaO less than 4.0%, CaO+ZnO 1.0 to 6.0%, Al2O3 4.0 to 9.0%, MgO less than 2.0%, BaO 1.0 to 3.0%, SrO less than 2.0%, F2 1.0 to 8.0%, total Fe2O3 1200 to 3000 ppm and Se 7 to 80 ppm.

[0044] More specifically, the fluorosilicate glass comprises by mass SiO2 of 70.0 to 74.0%, CaO + MgO less than 3.0%, Na2O of 11.0 to 13.0%, CaO less than 3.0%, Al2O3 of 7.0 to 8.50%, MgO less than 1.0%, K2O of 1.0 to 2.0%, BaO of 1.5 to 2.5%, SrO less than 1.0%, F2 of 3.0 to 6.0%, total Fe2O3 1300 to 3000 ppm, Se 7 to 60 ppm, preferably 8 to 50 ppm.

[0045] The resulting grey fluorosilicate glass exhibits a colour with L between 60 and 85 and is limited in a coordinate system b* = f(a*) within a quadrilateral defined by the four points with coordinates (-2; -6), (-2; 1), (2; 1) and (2; -6). a* is between -1 and 1.5. b* is between -5.5 and 1.

[0046] The FeO content is estimated from the quantities introduced and the color in the range of 150 to 450 ppm.

[0047] The tests are reported below:

[0048] [Tables3] Exemple 10 Exemple 17 Exemple 18 Exemple 19 Exemple 20 Exemple 23 Exemple 2.-4 SiG2 Bi 72 72 72 72 72 72 8 8 8 8 8 8 8 Na2O 12 12 12 12 12 12 12 K 20 1.5 IA 15 1.5 1.5 lil iii Cap. MgO 2 2 2 2 iLL ■T:<: 2 BaO 2 2 2 2 2 2 2 B 203 il 5 c O ; 5 5 c .J ■■■ / 13 23 30 31 17 48 Fe2O? 1540 1860 3000 2430 1480 2100 2203 CoO (ppm) 32 4SI Bi ||| 39 68 Ül 31.6 / 8 46 72.52 73.86 81.05 77.2 79.2 -0.53 û.27 -0.5 -0.21 0.34 -0.7 -0.5:1 -1.58 0.C2 -1.29 -0.06 Ôpi t.*(Panel B) 73.35 67.73 61.11 61.55 72.71 67 0.31 1.17 0.71 0.87 1.09 :Oll lüll -5.43 -2.67 -3.4 -1.36 -3.49 -2.2 iiiiB couleur gris gris gris gris gns gris BU

[0049] In brown tint, the tests were carried out with a fluorosilicate glass without voluntary addition of Ni and Cr. Fluorosilicate glass comprises by mass SiO2 + A12O3 more than 70.0%, SiO2 from 60.0 to 75.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 12.0%, A12O3 from 0.5 to 9.0%, MgO less than 6.0%, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO at most 5.0%, F2 less than 9.0%, SO3 less than 0.25%, total Fe2O3 1200 to 3000 ppm, Se 5 to 100 ppm and having a redox expressed as a ratio of FeO / total Fe2O3 between 0.08 and 0.2.

[0050] More specifically, the fluorosilicate glass is free from the intentional addition of CoO. More specifically, the fluorosilicate glass is free from the intentional addition of TiO2, MnO2 and Pr2O5. More specifically, the fluorosilicate glass comprises by mass SiO2 from 70.0 to 75.0%, CaO + MgO less than 5.0%, Na2O from 10.0 to 14.0%, CaO less than 4.0%, CaO + ZnO 1.0 to 6.0%, Al2O3 from 4.0 to 9.0%, MgO less than 2.0%, BaO from 1.0 to 3.0%, SrO less than 2.0%, F2 from 1.0 to 8.0%, total Fe2O3 1200 to 3000 ppm and Se 7 to 80 ppm.

[0051] More specifically, the fluorosilicate glass comprises by mass 70.0 to 74.0% SiO2, less than 3.0% CaO + MgO, 11.0 to 13.0% Na2O, less than 3.0% CaO, 7.0% Al2O3 at 8.50%, MgO less than 1.0%, K2O from 1.0 to 2.0%, BaO from 1.5 to 2.5%, SrO less than 1.0%, F2 from 3.0 to 6.0%, total Fe2O3 1200 to 2500 ppm, Se 7 to 60 ppm, preferably from 8 to 50 ppm.

[0052] The brown fluorosilicate glass obtained has a color with L between 70 and 90 and is limited in a coordinate system b* = f(a*) in a quadrilateral defined by the four points with coordinates (1; 4), (5; 13), (8; 13) and (4; 4). a* is between 1.5 and 6.5. b* is between 4.5 and 12.

[0053] The FeO content is estimated from the quantities introduced and the color within the range of 150 to 450 ppm. The tests are reported below:

[0054] [Tables4] loO!ësll Example 22 Example 25 Example 26 ixïOOâi SÎO2 72 72 72 72 ■ AL? 03 b 8 8 8 il Na2G 12 12 12 12 111 k?O 1.5 1.5 1SI Üi CaO 2 ? 2 11 il BaO 11 2 2 2i i 11; B2O3 P2O5 51 51 51 5 if Se {pptn) Fe2O3 36 711 28 45 il CoO {ppm) 21 7o 2073 Bill 1285 1151s 80. i 86,a Bll 80 üiai A) iBi 3.17 5111 lÜs 7171 S <65 8.19 8.8 / 0.8 78.3 70.06 72.43 iili a'JPanel B) 6.07 5.53 6.98 111 bx{P^nel B) 5147 4151 10.81 10.83 lli coeisjur brown brown thief brown

[0055] The colorimetric data were measured by a Perkim Elmer UV / Vis spectrophotometer by reflection measurement on a glass product, illuminating D65 at an angle of 10°. The chemical data were measured by X-ray fluorescence.

[0056] Proportions are given as mass percentages unless otherwise specified, such as ppm for minor species. MgO, B2O3, and P2O5 are not intentionally added. They may be present if recycled glass containing them is used. CoO is not intentionally added for the brown tint. CoO may be present if recycled glass containing it is used. Total iron is expressed as Fe2O3.

[0057] The above tests were duplicated and then adapted to borophosphate glass to obtain a high-quality product. The quantities introduced of Se, CoO and Fe2O3 are identical. The concentrations of these elements in the final product were not measured and are estimated to be close to those measured for fluorosilicate glass. The tests were conducted with borophosphate glass without the intentional addition of Ni and Cr. Borophosphate glass comprises by mass SiO2 + A12O3 more than 60.0%, SiO2 from 60.0 to 70.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 8.0%, A12O3 from 2.0 to 9.0%, P2O5 from 1.0 to 8.0%, B2O3 from 4.0 to 15.0%, MgO without voluntary contribution, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO at most 1.0%, F2 without voluntary contribution, SO3 less than 0.25%, total Fe2O3 from 1200 to 3000 ppm, Se from 5 to 100 ppm and having a redox expressed as a ratio of FeO / total Fe2O3 between 0.08 and 0.2.

[0058] In one embodiment, the borophosphate glass comprises by mass B2O3 + P2O5 from 5.0 to 20.0%.

[0059] More specifically, the borophosphate glass is without intentional addition of TiO2, MnO2 and Pr2O5. More specifically, the borophosphate glass comprises by mass SiO2 from 62.0 to 68.0%, Na2O from 6.0 to 13.0%, CaO less than 4.0%, Al2O3 from 4.0 to 8.0%, P2O5 from 1.0 to 6.0%, B2O3 from 4.0 to 12.0%, P2O5 + B2O3 from 10.0 to 16.0%, BaO from 1.0 to 4.0%, SrO less than 1.0%, K2O from 1.0 to 3.0%, total Fe2O3 from 1200 to 2500 ppm and Se from 10 to 80 ppm.

[0060] More specifically, borophosphate glass comprises by mass SiO2 from 63.0 to 67.0%, Na2O from 10.0 to 13.0%, CaO less than 3.0%, Al2O3 from 4.0 to 6.0%, P2O5 from 3.0 to 6.0%, B2O3 from 4.0 to 7.0%, P2O5 + B2O3 from 10.0 to 12.0%, BaO from 2.0 to 4.0%, SrO without voluntary contribution, total Fe2O3 from 1300 to 2500 ppm and Se from 10 to 60 ppm.

[0061] In a grey tint, the borophosphate glass comprises 25 to 70 ppm CoO by mass, preferably 30 to 50 ppm. The resulting grey borophosphate glass has a colour with L between 60 and 90, preferably between 65 and 85. a* is between -1.5 and 0, preferably between -1.5 and -0.5. b* is between -6 and -4, preferably between -6 and -5.

[0062] In brown tint, the borophosphate glass is without intentional addition of CoO. The brown borophosphate glass obtained has a color with L between 60 and 90, preferably between 80 and 90. a* is between 0 and 3, preferably between 0 and 1. b* is between 0 and 4, preferably between 0 and 2.

[0063] The tests are reported below:

[0064] [Tables5] Example 28 Example 11! Example Ül SI02 64.6 64.6 AÎ2O3 rr || i Na20 12 12 il K20 1.9 1.9 ii^ ÇaO 2 2 li MgO BaQ 3 F ■ii F2 B2O3 6 6 Si P2OS 5.5 5.5 lli L* 66.53 80.15 llli a* -0.82 4.26 ii b* -5.23 lllll 0.98 color grey iiii brown

Claims

Demands

1. Composition of colored tableware, soda-lime, borophosphate or fluorosilicate, without intentional addition of Ni and Cr, comprising by mass SiO2 + Al2O3 more than 70.0%, SiO2 from 60.0 to 75.0%, Na2O from 5.0 to 15.0%, CaO from 0.20 to 12.0%, Al2O3 from 0.5 to 9.0%, MgO less than 6.0%, K2O less than 5.0%, BaO less than 5.0%, SrO less than 2.0%, ZnO not exceeding 5.0%, F2 less than 9.0%, SO3 less than 0.25%, total Fe2O3 1200 to 3000 ppm, Se 5 to 100 ppm and having a redox potential expressed as a FeO / total Fe2O3 ratio between 0.08 and 0.

2.

2. Composition according to claim 1, having a brown color without intentional addition of CoO.

3. Composition according to claim 1, having a grey colour and comprising by mass CoO 25 to 70 ppm, preferably 25 to 55 ppm.

4. Composition according to any one of the preceding claims, without voluntary addition of TiO2, MnO2 and Pr2O5.

5. Composition according to any one of the preceding claims, comprising by mass SiO2 from 70.0 to 75.0%, CaO + MgO at least 9.0%, Na2O from 10.0 to 15.0%, CaO from 8.0 to 12.0%, Al2O3 less than 2.0%, MgO less than 5.0%, K2O less than 2.0%, BaO less than 2.0%, SrO less than 1.50%, F2 less than 1.0%, total Fe2O3 1500 to 3000 ppm and Se 10 to 80 ppm.

6. Composition according to claim 5, comprising by mass SiO2 of 72.0 to 74.0%, CaO + MgO of at least 11.0%, Na2O of 12.0 to 14.0%, CaO of 10.0 to 12.0%, Al2O3 of 1.0 to 1.8%, MgO less than 2.0%, K2O less than 1.0%, BaO less than 1.0%, SrO less than 1.0%, F2 less than 0.5%, total Fe2O3 2000 to 3000 ppm, Se 10 to 60 ppm, preferably 10 to 40 ppm.

7. Composition according to any one of claims 1 to 4, comprising by mass SiO2 from 70.0 to 75.0%, CaO + MgO less than 5.0%, Na2O from 10.0 to 14.0%, CaO less than 4.0%, CaO+ZnO 1.0 to 6.0%, Al2O3 from 4.0 to 9.0%, MgO less than 2.0%, BaO from 1.0 to 3.0%, SrO less than 2.0%, F2 from 1.0 to 8.0%, total Fe2O3 1200 to 3000 ppm and Se 7 to 80 ppm.

8. Composition according to claim 7, comprising by mass: SiO2 from 71.0 to 73.0%, CaO + MgO less than 3.0%, Na2O from 11.0 to 13.0%, CaO less than 3.0%, Al2O3 from 7.0 to 8.50%, MgO less than 1.0%, K2O from 1.0 to 2.0%, BaO from 1.5 to 2.5%, SrO less than 1.0%, F2 from 3.0 to 6.0%, Fe2O3 total 1200 to 3000 ppm, preferably 1300 to 3000 ppm in grey colour and 1200 to 2500 ppm in brown colour, Se 7 to 60 ppm, preferably 8 to 40 ppm.

9. Composition according to claim 7 or 8, comprising by mass CeO2 less than 4000 ppm, preferably 1000 to 2000 ppm.

10. Composition according to any one of claims 1 to 4, comprising by mass CaO from 0.20 to 8.0%, MgO less than 2.0%, preferably less than 1.0%, Al2O3 2.0 to 9.0%, F2 less than 1.0%, ZnO at most 1.0%, B2O3 from 4.0 to 15.0%, P2O5 1.0 to 8.0%, and B2O3 + P2O5 from 5.0 to 20.0%.

11. Composition according to claim 10, comprising by mass SiO2 from 62.0 to 68.0%, preferably from 64.0 to 65.0%, CaO + MgO less than 4.0%, Na2O from 6.0 to 13.0%, K2O from 1.0 to 3.0%, preferably from 1.50 to 2.30%, CaO from 0.20 to 3.0%, preferably from 1.0 to 2.50%, B2O3 from 4.0 to 12.0%, preferably from 5.0 to 7.0%, P2O5 from 1.0 to 6.0%, preferably from 5.0 to 6.0%, B2O3 + P2O5 from 10.0 to 16.0%, preferably from 10.0 to 12.0%, Al2O3 from 4.0 to 8.0%, MgO without voluntary contribution, BaO from 1.0 to 4.0%, SrO less than 1.0%, without voluntary contribution of F2, total Fe2O3 1200 to 2500 ppm and Se 10 to 80 ppm.

12. Tableware item of composition according to one of the preceding claims.

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