DE2652445C2 - Brown colored glass based on SiO 2 -Al 2 O 3 - Na? 2? O- (K? 2? O) - CaO-MgO-Fe? 2? O? 3? -Se (CoO) - (NiO) - (Cr? 2? O? 3?) - Google Patents

Description

50

The invention relates to a brown-colored glass which, when using the illumination source C and with a thickness of 6 mm, has a brightness factor (Y) of 45 to 60%, a dominant wavelength (A ₀ ) of 578 to nm and a total energy transmission factor (FET) of 35 to 55% and 68 to 72% by weight SiO ₂ , 0 to 4% by weight AlOO3, 11 to 15% by weight Na ₂ O, 0 to 3% by weight K ₂ O, 7 to 12% by weight. -% CaO, 1 to 5% by weight MgO and, as a colorant, oxides of iron and selenium and optionally oxides of cobalt, nickel and chromium.

Such a glass is known from DR-PS 20 82 459. A similar glass is also from FR-PS 20 74 983 known.

The known glasses, however, are not real brown-colored glasses, but practically only neutral gray Glasses and only have a very vaguely defined dominant wavelength. They also only assign one very low spectral color content. They also have a strong transmission in the UV range.

The object of the invention is to create a brown-colored glass, the entirety of which is colorimetric Features an improved compromise for the viewer between protection against the Eye fatigue, comfort and quality of rendering of colors in objects corresponds if it passes directly through the pane or if it is filtered through the panes Daylight can be viewed.

According to the invention, this object is achieved in that the glass contains 0.2 to 0.8% by weight Fe ₂ O ₃ , 0.002 to 0.01% by weight selenium, less than 0.001% by weight CoO, less than 0, Contains 01% by weight Cr ₇ O ₃ and less than 0.02% by weight NiO, the amounts of the coloring agents being matched to one another in such a way that a transmission coefficient is obtained that is between 400 and 470 nm up to approximately ± 10% is constant and the mean value corresponds to 35 to 60% of the mean value of this coefficient between 600 and 700 nm

Further developments of this glass are described in claims 2 to 6.

The glasses according to the invention have considerably improved inactinic properties.

The colorimetric properties of the invention Glasses were determined using procedures described in the publication “Recommandations officielles de la Commission Internationale de l'Eclairage ", publication ClE No. 15 (E-13.1.) 1971 are described (in accordance with DIN 5033), based on a specified transmission spectrum for vertical Incidence with the aid of a CARY 14 spectrophotometer at radiation in the range between 320 nm and 2200 nm. Furthermore, the standard light source used for the calculations was the Light source recognized by the International Commission C.

In the following, exemplary embodiments of the glasses according to the invention are to be explained in more detail. to For this purpose, glass compositions should be specified which are therefore particularly advantageous, because their basic components are in the usual proportions of common industrial silicate-soda-lime glasses are included. Thus, taking certain special precautions resulting from the use of the Coloring agents result, the glass compositions using the techniques customary in the glass industry Manufactured for the same reasons, the glass compositions are well suited for mass production, such as for the production of flat glass or float glass.

In addition, changes in coloration can occur without major difficulties in this production process the oven journey can be made by other colored glasses due to the fact that the possibility there is a choice between different solutions, which will be explained in more detail below target.

Suitable compositions of silicate-soda-lime glasses for the production of glasses according to the invention consist, for example, essentially of 68 to 72% by weight SiO ₂ , 0 to 4% by weight Al ₂ O ₃ , 11 to 15% by weight Na ₂ O , 0 to 3 wt .-% K ₂ O, 7 to 12 wt .-% CaO and 1 to 5 wt .-% MgO and also contain to achieve the desired colorimetric properties

shanks for glass panes of 6 mm thickness 0.2 to 0.8 wt .-% Fe ₂ O ₃ , 0.002 to 0.01 wt.% selenium, 0 to 0.001 wt .-% CoO, 0 to 0.001 wt. -% Cr ₂ O ₃ and 0 to 0.02% by weight NiO.

It should be noted that the extreme values for the proportions of the main components are generally not are critical, but represent limits that are customary in practice, essentially the price of the Starting materials, the manufacturing costs and the stresses related to physical and chemical properties are taken into account, which are usually required of industrial glasses.

Within the large range resulting from the limits given above for the proportions of The applicant has indicated preferred sub-ranges from which a choice has been made can be, with the composition including the available starting materials of the cullets, their prices, their dependence on the manufacturing conditions and their possibly additional desired properties for the glasses must be taken into account.

Because of this, there are three main preferred areas indicated, which relate to the elements of the main coloring agents; the first area refers to iron oxide and selenium, the second refers refers to the same two elements with the addition of chromium oxide and the third area refers to the two identical elements with the addition of nickel oxide, with cobalt oxide as a trace element in all cases may be present.

These three areas are summarized in Table I.

Table I.

Colorant elements (in percent by weight based on the glass)

material

Area I.

II

III

Fe ₂ O ₃ 0.3 Examples -0.6 Se 0.003 -0.006 CoO 0 - 0.001 Cr ₂ O ₃ 0 - 0.001 NOK 0 - 0.0005

The compositions given below as _exemplary embodiments illustrate different possibilities of glasses, glasses 1, 2 and 3 referring in particular to area 1, glasses 4, 5, 6 and 9 to area II and glasses 7 and 8 refer to area III. The glass 10 is a commercially available bronze glass not belonging to the invention, which is used for comparison purposes in order to make the advantages of the invention clear.

The corresponding glasses are produced with the help of the usual glass starting materials, namely both in terms of their type and in terms of their form of use, d. H. for example in terms of Grit. The preparation of the vitrifiable batches and the manufacture of the glasses are carried out with the usual processes that enable the production of homogeneous glasses, which are important meaningful Measurements and experiments are suitable. Table II gives the proportions of the vitrifiable

Table II

Proportions of the coloring agents in percent by weight

0.3-0.6
0.004-0.01
0 - 0.001
0.002-0.01
0-0.0005

0.2-0.6
0.003-0.005
0 - 0.001

0 - 0.001

0.0005 - 0.002

Batch imported coloring agents, while in Table III the proportions of the corresponding Elements are given which were determined during the analysis of the glasses produced; in Table IV different properties of the glasses are put together.

In Table II the totality of the constituents of the vitrifiable batch is not given because the proportions of the main components are practically the same for all glasses. These The proportions of the main components, based on approximately 100 kg of glass to be produced, have the following values:

Nepheline syenite 1.41 kg dolomite 21.62 kg limestone 3.61 kg sand 70.97 kg Sodium sulfate 0.53 kg Sodium nitrate 0.40 kg sodium 23.12 kg

No. of glasses 1 2

Iron red

(Potee de fer)

Potassium dichromate

Cobalt oxide

Nickel oxide

0.3708 0.4535 0.5362 0.3708 0.3708 0.3708 0.3708 0.3708 0.3708

0.0467 0.0333 0.0333 0.0467 0.0467 0.0533 0.0333 0.0300 0.0500

0.00973 0.00585 0.00973 0.00973

0.00055 0.00055 0.00055

0.0100 0.0070 0.0004

Table III also shows the results of the chemical analysis with regard to the proportions, specifically only with regard to those elements which play a role in the transmission of the glasses, ie: the total iron proportion, expressed in proportions calculated as Fe ₂ O ₃ ; Selenium (Se), cobalt oxide (CoO), chromium oxide (Cr ₂ O ₃ ) and nickel oxide (NiO). The other elements are present in essentially equal proportions in all of these glasses, on the order of:

SiO ₂

AI ₂ O ₃

CaO

MgO

Na ₂ O

K ₂ O

SO ₃

71.6% by weight
0.4 wt%
9.4 wt%
4.0% by weight

14.0% by weight
0.1 wt%
0.3 wt%.

In Table III, the proportion of reducing elements is also given, expressed in the form of FeO.

Table III

Analysis of the coloring constituents in% by weight.

No. of glasses
1 2

10

Fe ₂ O ₃ total

0.37
0.0048

0.48
0.0038

0.55 0.0034

0.40 0.0056

0.40 0.0047

0.0050 0.0020 0.40
0.0078
0.0005
0.0050

0.37
0.0050

0.39

0.0034

0.0004

0.010 0.007

0.38 0.39

0.0065 0.0019

0.0004 0.0040

0.0050 0.0005

0.0004 0.0006

0.055 0.074 0.090 0.055 0.056 0.052 0.053 0.060 0.052 0.062

In practice, in order to carry out comparative tests between the various compositions, the melt and the production of the glasses were carried out according to an identical program. A port furnace heated with propane was used, namely a laboratory model, with which two crucibles with a capacity of 3 kg of glass could be treated at the same time. The combustion control contained approximately 5% excess air. The vitrifiable batch was prepared by making a first mix with only the colorants and dolomite, while adding the remainder of the ingredients to that first mix and remixing. The insertion of the batch was carried out in two stages, the operation of the actual melting was carried out at 1450 ° C for about one hour, while the purification was performed within two and a half hours at 1460 ⁰ C and the protrusion of one and a half to two hours at 1330 ⁰ C. The plates were poured onto a hot table and then slowly cooled. The transmission curve was recorded with the aid of a CARY 14 spectrophotometer, the measurement being carried out at normal incidence without bringing the samples to a previously defined thickness. Appropriate correction was therefore made to relate all colorimetric properties to the same thickness of 6 mm.

Table IV gives the following colorimetric properties, which correspond to a thickness of 6 mm and which were determined with a lighting source C: brightness _{factor Y, dominant wavelength Ad, spectral color component P e} , factor of total energy transmission FET and the factors of energy transmission in the areas of the ultraviolet (UV), visible (VIS) and infrared (IR) light, all values being given in%, with the exception of the dominant wavelengths Ad, which are given in nanometers (nm).

Table IV

Colorimetric properties

No. of Glasses 3 4th 5 6th 7th 8th 9 10 1 2 48.7 52.4 54.1 50.6 48.8 49.9 49.5 50.5 K (%) 54.8 50.2 580 581 580 581 581 581 581 582 X ₀ (nm) 581 581 26.7 27.5 25.5 29.3 31.3 27.3 30.8 8.0 Pr (%) 27.4 26.7 40.1 49.9 50.1 50.9 48.4 47.6 49.0 49.7 FET (%) 51.4 44.2 14.2 14.8 16.4 11.5 14.2 16.3 10.9 23.0 UV (%) 14.8 14.9 46.0 49.9 51.5 48.2 47.2 48.3 47.1 50.7 VIS (%) 52.3 47.8 36.0 5U 50.2 55.1 50.9 48.4 52.2 50.0 IR (%) 52.2 42.3

The curve shown on the drawing gives the energy transmission factor of the glass according to the example 9 as a function of the wavelength plotted on the abscissa.

The extreme values of the transmission of glass no. 9 are between 400 nm and 470 nm inclusive 28.5% and 29.9%, which is a relative fluctuation of ± 2.4% based on its mean value of 29.2% corresponds to, and between 600 nm and 700 nm including at 60.8% and 57.4%, which is a relative This corresponds to a fluctuation of ± 2.8% in relation to its mean value of 59.6%. You can see that the two Mean values have a ratio of around 50% to one another. Furthermore can be at Examination of Table IV found that the same No. 9 glass in the watch raviolet range was particularly one low factor of energy transmission, so that it is of particular importance for shop window glazing

sung, because it allows the change or deterioration of the colors of the glass slowing down objects exposed to light in a very considerable manner. For the same reason it is possible with the glasses according to the invention to reduce eye fatigue. It is remarkable that the glasses on the other hand ensure a sufficiently strong illumination, which both the values of the brightness factor Y of Table IV in the order of 50% and the pleasant and very show the nuanced reproduction of the colors.

In addition, the glasses according to the invention are found because of their warm and pleasant color tone also used in decorations and furnishings, the effects achieved being very different can and in particular depend on the thickness of the glass.

1 sheet of drawings

Claims (6)

Patent claims: 1. Brown-colored glass, which when using the illumination source C and a thickness of 6 mm has a brightness factor (Y) of 45 to 60%, a dominant wavelength (A _D ) of 578 to 583 nm and a total energy transmission factor (FET) of 35 to 55% and 68 to 72% by weight SiO ₂ , 0 to 4% by weight Al ₂ O ₃ , 11 to 15% by weight Na ₂ O, 0 to 3% by weight K ₂ 0.7 to 12% by weight CaO, 1 to 5% by weight MgO and, as a coloring agent, oxides of iron and selenium and optionally oxides of cobalt, nickel and chromium, characterized in that it contains 0.2 to 0.8% by weight of Fe ₂ O ₃ , 0.002 to 0.01% by weight. % Selenium, less than 0.001 wt.% CoO, less than 0.01 wt.% Cr ₂ O ₃ and less than 0.02 wt Transmission coefficient is obtained which is constant between 400 and 470 nm to about ± 10% and whose mean value corresponds to 35 to 60% of the mean value, this coefficient between 600 and 700 nm 2. Brown-colored glass according to claim 1, characterized in that its spectral color component (P _e ) is 20 to 35%, preferably at least 25%. 3. Brown-colored glass according to claim 2, characterized in that its energy transmission factor in the ultraviolet region is less than 1/3 of the same factor in the visible region. 4. Brown-colored glass according to one of the claims 1 to 3, characterized in that it contains 0.3 to 0.6 wt.% Fe ₂ O ₃ , 0.003 to 0.006 wt.% Selenium, 0 to 0.001 wt.% CoO, 0 to 0.001 wt. -% Cr ₂ O ₃ and 0 to 0.0005% by weight NiO. 5. Brown-colored glass according to one of claims 1 to 3, characterized in that it is 0.3 to 0.6 wt .-% Fe ₂ O ₃ , 0.004 to 0.01 wt .-% selenium, 0 to 0.001 wt % CoO, 0.002 to 0.01% by weight Cr ₂ O ₃ and 0 to 0.0005% by weight NiO. 6. Brown-colored glass according to one of claims 1 to 3, characterized in that it is used as a colorant 0.2 to 0.6 wt .-% Fe ₂ O ₃ , 0.003 to 0.005 wt .-% selenium, 0 to 0.001 wt. % CoO, 0 to 0.001% by weight Cr ₂ O ₃ and 0.0005 to 0.02% by weight NiO.