DE2112582C3 - Heat-absorbing, colored, Fe2 O3, CoO and Se containing sodium-calcium-silicate glass and its use - Google Patents

Description

SiO ₂ 60 to 75 percent by weight

B ₂ O ₃ O to 7 percent by weight

AJ ₂ O ₃ O to 5 percent by weight

Na ₂ O 10 to 20 percent by weight

K ₂ OO to 10 percent by weight

(K ₂ O + Na ₂ O between

10 and 20 percent by weight)

CaO 0 to 16 percent by weight

MgO 0 to 10 percent by weight

(with CaO -f- MgO between 6 and 18 percent by weight)

contains the following colorants in the following amounts to achieve a spectral color component below 14%, a total transmission of solar energy of less than 50% and a brightness factor Y between 35 and 55%:

Fe ₂ O ₃
CoO.
Se ....
Cr ₂ O ₃
UO ₂ .

0.2 to 1.5 percent by weight, 0.0010 to 0.0300 percent by weight, 0 to 0.0200 percent by weight 0 to 0.0200 percent by weight 0 to 0.2'0O percent by weight,

where UO ₂ + Cr ₂ O ,. between 0.0010 and 0.2500 percent by weight lie * _

2. Glass according to claim 1, characterized in that the coloring agent amounts for a bronze glass with a brightness factor Y between and 55% and a main wavelength between and 585 nm in the following ranges:

Fe ₂ O ₃ ... 0.2 to 1.5 percent by weight

CoO 0.0010 to 0.0200 percent by weight

Se 0.0015 to 0.0200 weight percent

Cr ₂ O ₃ ... 0 to 0.0100 percent by weight

UO ₂ 0 to 0.1500 percent by weight,

where UO ₂ + Cr ₂ O ₃ between 0.0010 and ^4S

0.1500 percent by weight.

3. Glass according to claim 2, characterized in that for a bronze glass of a strength in the On the order of 6 mm the dye content So is within the following limits:

Fe ₂ O ₃ ... 0.25 to 0.40 percent by weight

CoO 0.0010 to 0.0060 percent by weight

Sc 0.0015 to 0.0060 percent by weight

Cr ₅ O ₃ ... 0 to 0.0100 percent by weight

UO ₂ 0 to 0.1000 percent by weight

where UO ₂ 4- Cr ₂ O _{3 is} between 0.0010 and 0.1000 percent by weight.

4. Glass according to claim 1, characterized in that for a gray-colored glass with a spectrum of less than 7% and a brightness factor Y between 35 and 45%, the colorants are present in the following amounts:

Cr ₂ O ₃ ... 0 to 0.0200 percent by weight

UO ₂ 0 to 0.2500 percent by weight,

where UO ₂ + Cr ₂ O ₃ between 0.0030 and
0.2500 percent by weight.

5. Glass according to claim 4, characterized in that the main wavelength (dominant) between 400 and 490 nm.

6. Glass according to claim 4, characterized in that the main wavelength (dominant) between 565 and 700 nm.

7. Glass according to claim 4, characterized in that the main wavelength in the so-called »PurpuM area lies.

8. Glass according to claim 4, characterized in that for a gray glass of a strength in the In the order of 6 mm, the dye content is within the following limits:

Fe ₂ O ₃
CoO.
Se ....
Cr ₂ O ₃
UO ₂ .

0.25 to 0.40 percent by weight
0.0030 to 0.0100 percent by weight
0 to 0.0030 weight percent
0 to 0.0150 percent by weight
0 to 0.1500 percent by weight,

where UO ₂ + Cr ₂ O ₃ between 0.0050 and
0.1500 percent by weight.

9. Use of the glasses according to one of claims 1 to 8, in particular in the form of Flat glass, for building.

A.
COO
Se ...

0.2 to 1 percent by weight 0.0030 to 0.0300 percent by weight O to 0.0100 percent by weight The invention relates to a heat-absorbing, colored _{sodium-calcium-silicate glass containing Fe 2} O ₃ , CoO and Se, in particular for use as glazing for building purposes.

The color of a body is generally defined by its spectral remission curve. If it is a transparent body, such as B. is building glazing, this curve is replaced by the spectral transmission curve. Since the appearance of a body depends on the conditions under which it is illuminated, it is advisable to use colorimetric terms that take these conditions into account. The calculation norms as defined by the CIE in 1931 will be used, and the light source C will be used as the source of illumination, which occupies a certain place in the color table and represents white.

The color of the observed body is determined in the CIE system by the trichromatic coordinates, ie the so-called color value components χ and y and the brightness factor Y. The trichromatic coordinates χ and ν can be expressed in the form of an excitation purity or a spectral excitation color element P _e in connection with a main wavelength Xd .

In the drawing, the part of the color chart is plotted with X plotted against y, which is located in the vicinity of the C light source. The locations of this color table, which are arranged in a radiating shape around point C, each correspond to a main waveform (dominant), the value of which is given in nanometers, nm (see FIG. 1).

On the other hand, the closed curves surrounding the point C steep the same spectral curves

3 4

The point C is not to be made to appear unnatural by a colored glazing. These

proportion of 0 and any main wavelength character- rendering the green color is obtained by adding

terized. The order of the curve closest to point Cam in the transmission curve of the glazing

the same proportion of color corresponds to a proportion of color from a more or less pronounced secondary

2%, the second curve represents a color component of 4% 5 maximums, which lies between 555 and 565 nm. It is

etc. with increasing distance from point C. Namely, it is known that yellow-green at 555 nm and mid-

If the spectral transmission curve of a more transparent green is around 520 nm and that on the other hand

parent substance in the entire visible range the sensitivity of the eye at 0.710 to 520 nm,

has a horizontal course, it will be 0.954 to 540 nm and 0.995 to 560 nm. One sees

Substance called "neutral gray". In the CI Ε-System io from this the whole meaning of these secondary maxima in

it has no main wavelength. Your spectral rendering of green colors.

Color component is zero, and their coordinates x, y fall It should be noted that this color rendering

with those of point C (reference white) together. can be partially modified by clicking on the

In a figurative sense, a body is also acted as a dye introduced into the glass, without being viewed as "gray", but whose spectral curve in the visible 15 - the trichromatic coordinates of the conserving range - is relatively flat. To change the occurring ten glasses. This result does not allow weak absorption bands to be contradicting the fact that one acquires the color of this body a special main wave - present that this coordination is obtained, length and for this main wave length one determined - by taking a series of sumrr ions from transtes , of 0 different spectral color components! to make niission curves and to give them as a result, which is still very small in the order of magnitude of one and n percent of which the same value of the coordinates is obtained. One can, for example, referring to two transmission curves as "gray", the bodies of which are more spectral, which are quite far from being superimposed color component, independent of the main wavelength. The transmission curves of the invention (dominant) does not exceed 7%. The pixels of the 35 glasses according to the invention are determined by the resulting AbColour of such a body are inside the sorption, which goes back to the totality of the area delimited by curve A (more spectral dyes. Depending on the nature and color proportion 7%) of the diagram in FIG 1. Outside the relative concentration of these different colors on this surface, the spectral color component is sufficient; one obtains an indistinguishable one in the visible range, depending on the dominant, so that these bodies are not moderately flat transmission curve, which is more than "gray", but rather to be regarded as colored. or the secondary maxima that are determined by the aesthetic

For building purposes it is necessary to see the spectral viewpoint, especially for the

Color of a colored protective glazing is not required to reproduce the green colors. Man

is high, around the ambient lighting that is let through is then given a "gray" glass, regardless of the

to let through relatively neutrally. In general 35 main wavelength Xd, if the spectral color component

one would mean the spectral color component which is below 7%, and a colored glass, for example

Building purposes specific glazing, except when wise a bronze glass, if the spectral fiber portion

special applications, to 14% (curve B of the slide is between 7 and 14%, at one main wavelength

gramms) i.e. limits. On the other hand it is necessary in between 575 and 585 nm.

the glazing for building purposes a large proportion 40 so far it was for the manufacture to eliminate the sun's energy to hen living such colored absorbent glasses used to improve comfort, especially in the countries dyeing mainly around the oxides of iron, with strong sunlight. So that a glass as cobalt and nickel, to which metalloid selenium is added "Heat-absorbing" can be considered, it was allowed to be. Nickel oxide has the following disadvantages: according to American standards oei a thickness of 45 regardless of certain difficulties 6.2 mm only less than 50% of the solar energy through procurement, the main part is in the act, thing that there is an uncontrollable pollution

The brightness factor Y must not be too strong in order to avoid the ovens and, as a result, the glare produced in these ovens and also cause the desired glasses. The nickel oxide can provide protection, but it must not be too weak, given the physico-chemical properties, in order to ensure a pleasant appearance and the conditions that prevail in the ovens, the formation of sufficient brightness at times of shade guaranteed to cause NicMsulfidkugelchen, which cause the chipping, seeing of the glass and, above all, its mechanical

One chooses the brightness factor in general impair the durability, whereby in the case of a previous

between 35 and 45% in the case of gray glasses 55 tension of the glass after a certain time

(spectral color content below 7%) and such a break can go.

between 40 and 55% for colored glasses with a The present invention enables these post-spectral Color content between 7 and 14%, such as B. Avoid parts.! By supplying protective glasses that with bronze glass. as a coloring agent iron oxide, cobalt oxide and

The glasses according to the invention have a row 60 if they contain metallic selenium, but in which the

of spectral _{transmission properties (} together, nickel oxide by chromium oxide and / or uranium oxide

which on the one hand supersedes the conditions set out above; draws such a glass according to the invention

fills and, on the other hand, the achievement of a sufficient one from the fact that it is at a strength of 2 to

Color rendering enabled. The concept of coloring 12 mm and the following basic composition:

rendering is not yet fully standardized, it is O5

but it is easy to understand that from the aesthetic SiO ₂ 60 to 75 wt .-%

From a standpoint, it is particularly important to use B ₂ O _{3 from} 0 to 7% by weight

the appearance of a green landscape through a mixture of Al ₂ O ₃ , 0 to 5% by weight

Na ₂ O 10 to 20% by weight

KjO,.,, 0 to 10% by weight

between 10 and
20wt. *% J

CaO <...... 0 to 16 wt>%

MgO, ,,. Ö to 1Ö% by weight

(with CaO + MgO
between 6 and
18% by weight)

contains the following colorants in the following amounts to achieve a spectral color component below 14%, a total transmission of solar energy of less than 50% and a brightness factor Y between 35 and 55%:

Fe ₂ O ₃ 0.2 to 1.5% by weight

Se O

Cr ₂ O ₃ 0

UO ₂ 0

where UO ₂ + Cr ₂ O ₃
0.2500% by weight.

up to 0.0200% by weight

up to 0.0200% by weight

up to 0.2500% by weight,

between 0.0010 and

The exact percentages of the colorants introduced are matched to the thickness of the glass to be produced so that it has the desired overall transmission properties. When adjusting to the relative percentages of the various dyes, the desired transmission curve and in particular the main wavelength (dominant) and the desired spectral color component for this wavelength are obtained in the visible spectrum. It is generally known that the iron in the glasses is present in two ion forms in equilibrium of Fe ¹¹ and Fe ¹¹¹ , the proportion of which is determined by the matrix of the base glass and by the working conditions (oxidizing-reducing atmosphere and temperature). Each of the two forms of iron has its own characteristics:

Bas Fei ¹ absorbs in the infrared range, a certain amount is required if the glass is to absorb the heat and comply with building standards. It is assumed that the FeO content of a 6 mm thick glass must be above 0.06% in order to meet the usual conditions.

The Fe ⁱⁿ absorbs in the ultraviolet range and plays a negligible role in coloring.

The cobalt oxide has a main wavelength in the Blue-violet (blue-violet dominant) and strong absorption in the visible range. That Selenium forms a chromophore with iron oxide, which is a main wavelength in orange (orange dominant) and provides strong absorption in the visible range. The chromium oxide gives a main wavelength in the green and a medium absorption in the visible range. The uranium oxide gives a main wavelength in the green-yellow and weak absorption in the visible range.

The use according to the invention of chromium and / or uranium oxides as a substitute for nickel oxide in the furnaces offers in this way a great deal of adaptability for producing the desired color. Among the wide range of glasses that can be produced by varying the proportions of the various coloring agents within the limits given above, reference should be made to several areas of optical properties that provide glasses whose coloring is particularly pleasant to the eye and the required comfort ( Comfort) when used in the construction sector »
S On the color table according to Fig; 1 before they are ^j ferred ranges mh 1, II, III and IV numbered.

The range I lies between the Aß values from 400 to 490 nm,
the area II lies between the Aβ values between

ίο 565 and 700 nm,

area III corresponds to the purple area,
the range IV lies between the Aβ values of 575 and 585 nm.
The first three areas correspond to gray glasses (spectral color content less than 7%). Area IV corresponds to bronze glasses (spectral color content between 7 and 14%). For the production of gray

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If the factor Y is between 35 and 45% and a specific color content below 7%, amounts of colorants are used within the following limits:

Fe ₂ O ₃ 0.2 to 1%

CoO 0.0030 to 0.0300%

Se 0 to 0.0100%

^a5 Cr ₂ O ₃ 0 to 0.0200%

UO ₂ 0 to 0.2500%,

where UO ₂ + Cr ₂ O ₃ between 0.0030 and
0.2500%.

For the production of bronze glasses of area IV with a brightness factor Y between 40 and 55% and a spectral color component between 7 and 14%, the same coloring agents are used in amounts within the following limits:

Fe ₂ O ₃ 0.2 to 1.5%

CoO 0.0010 to 0.0200%

Se 0.0015 to 0.0200%

Cr ₂ O ₃ 0 to 0.0100%

UO ₂ 0 to 0.1500%,

⁺⁰ where UO ₂ + Cr ₂ O ₃ between 0.0010 and

For the production of these glasses you can use the basic glasses that are usually used in the Manufacture of flat or hollow glasses can be used, the added colorants being reasonable be dimensioned in such a way that the intended thickness of the glass plate is taken into account, so that the desired optical properties are obtained. One can assume that that for given optical properties the thickness of the Product multiplied by the concentration for each dye within the for the thickness and concentration permissible limits is practically constant.

It is known that the vitrifiable mixtures according to the invention, if they contain selenium, must be free of Be carbon, and they can expediently contain oxidizing agents at a lower temperature, for example sodium nitrate, its effect on the

So selenium in the finished glass is cheap is. The vitrifiable mixtures can also contain a certain amount of suitable melting or fluxing agents (Substances containing fluorine or boron, etc.) to increase the yield of selenium. The colorants used in very small amounts are expediently beforehand with a certain amount of one of the vitrifiable main primary materials mixed. You can

can also be introduced in the sintered state or in the molten glass state. Your encore can at at any point in the furnace compatible with the homogenization of the finished glass.

Below are a number of examples of gray and bronze glasses that are according to the invention were manufactured. The permeability curves accompanying each example were calculated using the Beckmann DK 2A Spcktrophotometer determined. They lead to the colorimetric properties of glasses.

Examples

In the table are the chemical and colorimetric properties of glasses according to the invention summarized representing exemplary embodiments of the invention. For each of them are in the table below shows the theoretical analyzes, the corresponding vitrifiable mixtures and the colorimetric properties indicated obtained from those obtained with a Beckmann spectrophotometer type DK 2A recorded transmission curves were determined. The F i g. 1 shows the location of each lens the color chart. The F i g. 2 through 5 contain two curves, one of which is a gray glass and the other corresponds to a bronze glass.

example 1

The glass in this example is a bronze glass which contains Fe ₂ O ₃ , CoO, Se and UO ₂ as colorants; due to its optical properties, it is in the middle of the desired range despite its low selenium content (cf. the transmission curve in FIG. 2).

Example 2

The glass in this example is very similar to the previous one, seen from both the chemical and the optical point of view (see the TransmissionskuiVe the F i g. 3).

Example 3

The glass in this example is a bronze glass that contains Fe ₂ O ₃ , CoO, Se and Cr ₂ O ₃ as colorants. Due to its optical properties, it is close to the edge of the desired area (cf. the transmission curve in FIG. 4).

Example 4

The glass in this example is a bronze glass that contains Fe ₂ O ₃ , CoO, Se and Cr ₂ O ₃ as colorants. Its optical properties show that a high chromium content only seems to favor the reduction in luminance (brightness) (cf. the transmission curve in FIG. 5).

Example

The glass of this example is a gray glass that contains Fe ₂ O ₃ , CoO, Se and Cr ₂ O ₃ as colorants. Its optical properties show that this is a glass that can be regarded as neutral from the colorimetric point of view (cf. the transmission curve in FIG. 5).

3 £ i ε ⁿ ! S! 6th

The glass of this example is a gray glass that contains Fe ₄ O ₃ , CoO, Se and Cr ₂ O ₃ as coloring agents. It is in the middle range of gray tones with a warm dominant.

Example 7

The glass of this example is a gray glass that contains Fe ₂ O ₃ , CoO, Se and Cr ₂ O ₃ as coloring agents. It lies in the middle range of the gray tones with a cold dominant (cf. the transmission curve in FIG. 4).

Example 8

The glass of this example is a gray glass that contains Fe ₂ O ₃ , CoO, Se and UO ₂ as colorants. It has a dominant which is quite far removed from that of the classic gray tones (cf. the transmission curve in FIG. 3).

Example 9

The glass of this example is a gray glass that is called

Contains colorant Fe ₂ O ₃ , CoU, Se and UO ₂ . It lies in the middle range of gray tones with cold domi-

UtC Λ. LtllMÖMI Example 10

The glass of this example is a gray glass that contains Fe ₂ O ₃ , CoO, Se and UO ₂ as colorants. It lies in the gray area with a warm dominant at a point almost symmetrical to that of glass No. 7 in relation to point C.

example 2 3 4th 5 6th 7th 8th 9 10 1 bronze bronze bronze Gray Gray Gray Gray Gray Gray bronze composition in% by weight 71.53 71.53 71.53 71.53 71.53 71.53 71.53 71.53 71.53 SiO ₂ 71.53 13.57 13.57 13.57 13.57 13.57 13.57 13.57 13.57 13.57 Na ₂ O 13.57 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 3.10 MgO 3.10 11.60 11.60 11.60 11.60 11.60 11.60 11.60 11.60 11.60 CaO 11.60 0.3500 0.3500 0.3500 0.2950 0.2950 0.2950 0.3500 0.2950 0.2950 Fe ₂ O ₃ 0.3500 0.0056 0.0043 0.0057 0.0082 0.0072 0.0082 0.0056 0.0082 0.0082 CoO 0.0056 - 0.0040 0.0085 0.0075 0.0075 0.0055 - - - Cr ₂ O ₃ - 0.1020 - - - - - 0.1020 0.1120 0.1120 UO ₂ 0.1020 0.0015 0.0021 0.0032 0.0030 0.0025 0.0021 0.0004 0.0022 Se 0.0010

ίο

continuation example 2 3 4th 5 6th 7th 8th 9 10 1 bronze bronze bronze Gray Gray Gray Gray Gray Gray bronze Vitrifiable mixture 718.2 718.2 718.2 718.2 718.2 718.2 718.2 718.2 718.2 for 1000 kg glass 718.2 219 219 219 219 219 219 219 219 219 sand 219 175 175 175 175 175 175 175 175 175 sodium 175 99 99 99 99 99 99 99 99 99 dolomite 99 5 5 5 5 5 5 5 5 5 Limestone 5 15th 15th 15th 15th 15th 15th 15th 15th 15th Sodium sulfate 15th 3,250 3,250 3,250 2,700 2,700 2,700 3,250 2,700 2,700 Sodium nitrate 3,250 0.056 0.043 0.057 0.082 0.072 0.082 0.056 0.082 0.082 Fe ₂ O ₃ 0.056 - 0.040 0.085 0.075 0.075 0.055 - - - CoO - 1.156 : - - - - 1.156 1.269 1.269 Cr ₂ O ₃ 1.156 0.1000 0.1400 0.2140 0.2000 0.1670 0.1400 0.0267 - 0.1470 UOj 0.0667 Se (metallic) 580 579 580 587 577 480 570 484 580 Main wavelength 579 10 13th 12.2 1.5 3.2 4.75 4.2 3.1 5.0 Xd in nm (dominant) 10 Spectral color component 0.3295 0.3360 0.3347 0.3127 0.3160 0.2998 0.3158 0.3025 0.3206 Pe in% 0.3300 0.3328 0.3391 0.3372 0.3176 0.3227 0.3076 0.3260 0.3122 0.3245 X 0.3343 41.78 44.57 40.13 40.95 43.26 44.04 40.99 42.63 38.76 y 41.58 y ™ %

For this purpose 3 sheets of drawings

Claims (1)

Patent claims: 1, _{Heat-absorbing, colored sodium-calcium-silicate glass containing Fe 2} O ₃ , CoO and Se, characterized in that it has a thickness of 2 to 12 mm and the following basic composition: