U.S. patent application number 10/498111 was filed with the patent office on 2005-02-10 for blue glass composition for making glass panes.
Invention is credited to Jeanvoine, Pierre, Sachot, Dominique, Teyssedre, Laurent.
Application Number | 20050032624 10/498111 |
Document ID | / |
Family ID | 8870685 |
Filed Date | 2005-02-10 |
United States Patent
Application |
20050032624 |
Kind Code |
A1 |
Teyssedre, Laurent ; et
al. |
February 10, 2005 |
Blue glass composition for making glass panes
Abstract
The invention relates to a glass composition of silica-soda-lime
type colored blue which comprises the coloring agents below in a
content varying within the following limits, by weight: 1
Fe.sub.2O.sub.3 (total iron) 0.2 to 0.51% CoO 10 to 50 ppm
Cr.sub.2O.sub.3 10 to 300 ppm CuO 0-400 ppm the glass exhibiting a
redox factor of less than 0.35, a dominant wavelength XD Of between
485 and 489 nm, an excitation purity of less than 13% and a
selectivity at least equal to 1.1 under a thickness of between 3
and 5 mm. It also relates to the glass sheet obtained from the
above-mentioned composition, said sheet being intended in
particular to form an automobile window or for the construction
industry.
Inventors: |
Teyssedre, Laurent; (Paris,
FR) ; Sachot, Dominique; (Ozoire La Ferriere, FR)
; Jeanvoine, Pierre; (Poissy, FR) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
8870685 |
Appl. No.: |
10/498111 |
Filed: |
October 7, 2004 |
PCT Filed: |
December 11, 2002 |
PCT NO: |
PCT/FR02/04282 |
Current U.S.
Class: |
501/71 |
Current CPC
Class: |
C03C 3/087 20130101;
C03C 4/02 20130101; C03C 1/105 20130101; C03C 1/10 20130101 |
Class at
Publication: |
501/071 |
International
Class: |
C03C 003/087 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 19, 2001 |
FR |
01/16455 |
Claims
1. A blue glass composition of silica-soda-lime, comprising: the
coloring agents below in a content varying within the following
limits, by weight:
12 Fe.sub.2O.sub.3 (total iron) 0.2 to 0.51 CoO 10 to 50 ppm
Cr.sub.2O.sub.3 10 to 300 ppm CuO 0 to 400 ppm
wherein the glass comprises a redox factor of less than or equal to
0.35, a dominant wavelength .lambda..sub.D of between 485 and 489
nm, an excitation purity of less than 13% and a selectivity at
least equal to 1.1 under a thickness of between 3 and 5 mm.
2. The glass composition as claimed in claim 1, wherein the iron
content is greater than 0.3%.
3. The glass composition as claimed in claim 1, wherein the CoO
content varies from 15 and 40 ppm.
4. The glass composition as claimed in claim 1, whrein the
Cr.sub.2O.sub.3 content is greater than or equal to 20 ppm.
5. The glass composition as claimed in claim 4, wherein the
Cr.sub.2O.sub.3 content is between 30 and 80 ppm.
6. The glass composition as claimed in claim 1, wherein the CuO
content is less than 250 ppm.
7. The glass composition as claimed in claim 1, wherein the glass
composition comprises a selectivity of at least equal to 1.3.
8. The glass composition as claimed in claim 1, wherein the glass
composition comprises a light transmission LTA at least equal to
60%.
9. The glass composition as claimed in claim 1, wherein the
contents of Cr.sub.2O.sub.3 and of CoO satisfy the relationship:
100.times.Cr.sub.2O.sub.3/(CoO).sup.2>7.
10. The glass composition as claimed in claim 1, wherein the glass
composition comprises a redox of greater than 0.20.
11. The glass composition as claimed in claim 1, wherein the glass
composition comprises an excitation purity of less than 9%.
12. The glass composition as claimed in claim 1, wherein the glass
composition comprises a dominant wavelength at least equal to 487
nm.
13. The glass composition as claimed in claim 1, which further
comprises agents which modify the optical properties in certain
parts of the spectrum, in particular in the ultraviolet region,
such as wherein said agents are selected from the group consisting
of CeO.sub.2, TiO.sub.2, WO.sub.3, La.sub.2O.sub.3, V.sub.2O.sub.5,
and mixtures thereof.
14. The glass composition as claimed in claim 13, wherein the
content of agents does not exceed 2%.
15. The glass composition as claimed in claim 1, wherein the glass
composition comprises:
13 Fe.sub.2O.sub.3 (total iron) >0.45% FeO >0.15% CoO 10 to
50 ppm Cr.sub.2O.sub.3 10 to 300 ppm CuO 0 to 400 ppm
the glass exhibiting a light transmission LTA of greater than 70%
and a selectivity of greater than 1.3 under a thickness of the
order of 3.15 mm.
16. The glass composition as claimed in claim 15, wherein the glass
composition comprises an excitation purity of less than 9%.
17. The glass composition as claimed in claim 1, wherein the glass
composition comprises:
14 Fe.sub.2O.sub.3 (total iron) >0.4%, FeO >0.12%, CoO <35
ppm Cr.sub.2O.sub.3 10 to 300 ppm CuO 0 to 400 ppm
the glass exhibiting a light transmission LTA of greater than 60%
and a selectivity of greater than 1.3 under a thickness of the
order of 3.85 mm.
18. The glass composition as claimed in claim 17, wherein the glass
composition comprises a light transmission of greater than 70% and
a selectivity of greater than 1.4.
19. The glass composition as claimed in claim 1, wherein the glass
composition comprises:
15 Fe.sub.2O.sub.3 (total iron) >0.3%, FeO >0.1%, CoO <25
ppm Cr.sub.2O.sub.3 10 to 300 ppm CuO 0 to 400 ppm
the glass exhibiting a light transmission LTA of greater than 60%
and a selectivity of greater than 1.3, under a thickness of the
order of 4.85 mm.
20. The glass composition as claimed in claim 19, wherein the glass
composition comprises a dominant wavelength at least equal to 487
nm.
21. A glass sheet formed by floating on a bath of molten metal,
with a chemical composition as defined by claim 1.
22. A window, in particular an automobile window, characterized in
that it comprises at least one glass sheet as claimed in claim 21.
Description
[0001] The invention relates to a glass composition of
silica-soda-lime type colored blue. More particularly, the
invention relates to a blue glass composition for the preparation
of flat glasses by floating on a bath of molten metal, such as tin
(float process), these flat glasses being intended in particular,
but not exclusively, to form windshields and side windows situated
at the front of a vehicle.
[0002] Automobile windows are subject to very strict requirements.
As regards optical properties, these requirements are governed by
regulations, for example with regard to the light transmission of a
windshield or else with regard to the comfort of the user, in
particular as concerns the energy transmission.
[0003] In addition to the constraints related to the light
transmission and to the energy transmission, the windows situated
at the front of vehicles also have to meet the wishes of automobile
manufacturers as regards the color, in particular relating to the
dominant wavelength and to the purity.
[0004] Iron is a coloring agent which fully satisfies these
requirements. The presence of iron in the form of ferrous ions
Fe.sup.2+, distinct from ferric ions Fe.sup.3+, makes it possible
to reduce the transmission of infrared radiation through the glass
and therefore to lower the energy transmission. In addition, iron
introduces a green coloring which matches well the color of the
majority of automobiles.
[0005] Nevertheless, the combination of a bluish body and of a
green window proves in many cases to be rather unsatisfactory from
an esthetic viewpoint. This is why automobile manufacturers wish to
have available glasses exhibiting a relatively neutral blue color,
that is to say exhibiting a wavelength which is not too low and a
purity which is not too high, for a significant level of light
transmission and also a moderate energy transmission.
[0006] A blue coloring can be obtained simply by adding cobalt
oxide to the glass composition. The major disadvantage of this
oxide is that it leads to a reduction in the light transmission of
the glass, the transmission of infrared radiation through the glass
for its part being only very slightly affected.
[0007] Another way of coloring the glass blue consists in using
iron as sole coloring agent, provided, however, that the redox
factor (content of ferrous ions FeO/total content of ferrous ions
and of ferric ions Fe.sub.2O.sub.3) is maintained at a relatively
high value, of the order of 50%. Such a high redox factor presents
problems with regard to the implementation of the process as the
melting of the glass is rendered more difficult, which increases in
proportion the risk of seeing the appearance in the glass of
inclusions of incompletely melted material, such as silica. In
addition, under such reducing conditions, the iron is liable to
react with the sulfate used for the refining of the glass in the
bath to form iron sulfide, which gives the glass a yellow to brown
coloring.
[0008] Blue-colored glasses can also be obtained by combining
several coloring agents.
[0009] In EP-A-0 820 964, a mixture combining iron (0.4 to 1.1%)
and cobalt oxide (10 to 75 ppm) is used to form a blue glass having
a dominant wavelength varying from 480 to 490 nm and an excitation
purity of at least 6%. The proportion of iron in the ferrous state
is between 20 and 40%. The coloring effect, related essentially to
the presence of cobalt oxide in the glass, is reflected by a very
strong blue color.
[0010] In EP-A-0 814 064, provision is made to combine iron (0.53
to 1.1%), cobalt oxide (5 to 40 ppm) and optionally chromium oxide
(up to 100 ppm) to form blue glasses exhibiting a dominant
wavelength varying from 485 to 491 nm and a purity varying from 3
to 18%. The redox is between 0.25 and 0.35.
[0011] In EP-A-1 023 245, use is made, as above, of iron (0.4 to
1.0%), cobalt oxide (4 to 40 ppm) and optionally chromium oxide (up
to 100 ppm) to form a glass exhibiting a dominant wavelength
varying from 485 to 489 nm and an excitation purity ranging from 3
to 18%. This glass is prepared at a redox of between 0.35 and 0.6,
which is not a usual redox value for the float process. It is
therefore necessary in this case to use specific heating means to
melt the composition, as already specified above. This is
consequently reflected by an increase in the cost of the glass
produced.
[0012] To rapidly respond to market demand is a constant concern of
manufacturers of glass in general and more particularly of colored
glasses for the automobile industry, where the color range is
relatively broad. The processes for producing the blue glasses
mentioned above are carried out with a total iron content at least
equal to 0.4% and/or under relatively high redox conditions. They
generally operate with a given glass composition and it is not
recommended to adjust the nature or the content of the components
participating in the composition of the vitrifiable mixture. This
is because any change in the composition of the glass in the
furnace requires a transition time during which the glass produced
does not have the expected optical properties and the expected
coloring. This transition time increases in proportion as the
content of coloring agents increases. Furthermore, limiting the
content of iron, in particular of ferrous iron, introduces an
additional advantage as the energy requirement for melting the
glass composition is less, which contributes to reducing the cost
of the glass.
[0013] The present invention intends to provide a glass composition
of silica-soda-lime type which makes it possible to form a
blue-colored glass which overcomes the abovementioned
disadvantages. More specifically, an aim of the present invention
is to provide a composition capable of being employed under the
conditions of the float process to form a glass exhibiting a blue
coloring and having spectral properties compatible with use as
automobile window or in the construction industry, said composition
comprising a reduced content of coloring agents, in particular of
iron. The low content of iron in the composition according to the
invention makes it possible to be able to prepare the glass in a
float plant suited to the production of "clear" glass, in which the
content of iron generally does not exceed 0.6%. This type of plant
proves to be particularly advantageous economically for the reasons
explained above.
[0014] Better still, the invention makes it possible to provide a
blue glass suitable for forming an automobile window which, for a
thickness varying from 3 to 5 mm, exhibits a light transmission
LT.sub.A at least equal to 60% and a selectivity at least equal to
1.1.
[0015] These aims are achieved according to the present invention
by the blue glass composition of silica-soda-lime type which
comprises the coloring agents below in a content varying within the
following limits, by weight:
2 Fe.sub.2O.sub.3 (total iron) 0.2 to 0.51% CoO 10 to 50 ppm
Cr.sub.2O.sub.3 10 to 300 ppm CuO 0 to 400 ppm
[0016] the glass exhibiting a redox factor of less than or equal to
0.35, a dominant wavelength .lambda..sub.D of between 485 and 489
nm, an excitation purity of less than 13% and a selectivity at
least equal to 1.1 under a thickness varying between 3 and 5
mm.
[0017] The expression "silica-soda-lime" is used here in the broad
sense and relates to any glass composition which comprises the
following constituents (as % by weight):
3 SiO.sub.2 64-75% Al.sub.2O.sub.3 0-5% B.sub.2O.sub.3 0-5% CaO
5-15% MgO 0-5% Na.sub.2O 10-18% K.sub.2O 0-5% BaO 0-5%
[0018] It is admitted here that the silica-soda-lime glass
composition can comprise, in addition to inevitable impurities, a
small proportion (up to 1%) of other constituents, for example
agents which help in the melting or in the refining of the glass
(SO.sub.3, Cl, Sb.sub.2O.sub.3, As.sub.2O.sub.3) or which originate
from a possible addition of recycled cullet to the vitrifiable
mixture.
[0019] In the context of the invention, the term "redox" is
understood to mean the ratio of the content by weight of the
ferrous oxide, expressed in the form of FeO, to the content by
weight of total iron, expressed in the form of oxide
Fe.sub.2O.sub.3. Still in this same context, the "selectivity" is
defined as being the ratio of the light transmission under
illuminant A (LT.sub.A) to the total energy transmission (T.sub.E)
for a given thickness.
[0020] The composition according to the invention makes it possible
to obtain a blue-colored glass of high purity even for a
significant level of light transmission. In addition, the glass
formed from the composition according to the invention exhibits a
high selectivity, which is particularly advantageous when the
latter is intended to form windows for the construction industry or
the automobile industry. This is because, with such a glass,
heating related to solar radiation is limited and, for this reason,
the comfort with regard to the temperature of the occupants of the
building or automobile is increased. Preferably, the selectivity of
the glass is equal to or greater than 1.3 and even better still is
greater than or equal to 1.4.
[0021] The composition according to the invention proves to be
advantageous in forming glasses which, for a thickness varying from
3 to 5 mm, have a light transmission LT.sub.A at least equal to
60%, preferably 70%, and are thus suitable for forming front side
windows and windshields of automobiles.
[0022] Preferably again, the glass in accordance with the invention
has an excitation purity of less than 9% and advantageously of
greater than 4%.
[0023] Advantageously, the dominant wavelength of the glass
obtained by virtue of the composition according to the invention is
at least equal to 487 nm.
[0024] Preferably again, the glass composition in accordance with
the invention comprises contents of chromium oxide and of cobalt
oxide which satisfy the relationship:
100.times.Cr.sub.2O.sub.3/(CoO).sup.2>7.
[0025] The use of the coloring agents within the limits of the
invention makes it possible to achieve the best adjustment of the
optical properties of the glass and to confer the desired blue
coloring.
[0026] As already stated above, the addition of cobalt oxide to a
composition comprising iron gives the glass a blue coloring but
also results in a decrease in the light transmission. It is
therefore essential to control the content of cobalt oxide in order
for the light transmission of the glass to remain compatible with
the use for which it is intended. In the majority of cases, the
content of cobalt oxide varies from 15 to 40 ppm, preferably from
20 to 35 ppm.
[0027] The presence of iron in the glass composition can result
from the starting materials, as impurities, or from a deliberate
addition. It is known that, if the iron content is increased, the
glass takes on a green color and its light transmission is reduced.
Conversely, on reducing the proportion of iron, in particular in
the form of ferrous ions, the performance in terms of energy
transmission deteriorates without affecting the light transmission.
Preferably, the total iron content in the composition is greater
than 0.30%, better still greater than 0.40% and advantageously
greater than 0.45%.
[0028] The chromium oxide confers a green/yellow coloring on the
glass and also reduces its light transmission. The addition of
chromium to a composition comprising cobalt softens the vivid blue
coloring and thus moderates the intensity of the coloring, which
makes it possible to retain a dominant wavelength which is not very
high while having a lower purity than with cobalt alone. In the
present invention, the content of chromium oxide is preferably
greater than or equal to 20 ppm, better still less than or equal to
250 ppm. In a particularly advantageous way, the content of
chromium oxide is between 30 to 80 ppm.
[0029] The copper oxide gives a turquoise blue coloring to the
glass. It absorbs infrared radiation and, for this reason,
contributes to reducing the overall energy transmission T.sub.E
without significantly modifying the light transmission, which makes
it possible to increase the selectivity of the glass. The
introduction of copper oxide under the conditions of the float
process nevertheless remains difficult as the copper has a tendency
to migrate to the surface of the glass where, by reduction, it
takes on a brown coloring. In order to avoid the appearance of
reduced copper in the form of brown streaks in the glass ribbon,
the content of copper is limited to less than 400 ppm, preferably
250 ppm. Generally, it is not necessary to add copper.
[0030] As a general rule, the optical and energy properties of a
glass comprising several coloring agents are difficult to predict.
They result from a complex interaction between the various coloring
agents, the behavior of which is directly related to their
oxidation/reduction state occasioned by the other elements present
in the composition.
[0031] In the present invention, the choice of the coloring agents
and of their content in the composition is the determining factor
in producing the blue glass having the desired optical and energy
properties.
[0032] The composition according to the invention can additionally
comprise additives, for example agents which modify the optical
properties in certain parts of the spectrum, in particular in the
ultraviolet region, such as CeO.sub.2, TiO.sub.2, WO.sub.3,
La.sub.2O.sub.3 and V.sub.2O.sub.5, the total content of these
additives not exceeding 2%, preferably 1%.
[0033] According to the invention, the redox of the glass is
maintained at a value of less than or equal to 0.35, preferably of
greater than 0.20 and even better still of less than 0.30, for
reasons related essentially to the melting and to the refining of
the glass. The redox is generally controlled using oxidizing
agents, such as sodium sulfate, and reducing agents, such as coke,
the relative contents of which are correctly adjusted to produce
the desired redox.
[0034] According to a particularly advantageous embodiment of the
invention, and in particular for applications of automobile
windshield and side windows type, the overall light transmission
under illuminant A (LT.sub.A) is greater than or equal to 70% and
the energy transmitted is less than 50%, preferably less than 48%,
for a thickness of 3.85 mm.
[0035] A composition particularly suited to the production of
relatively thin glass, with a thickness of the order of 3.15 mm,
comprises the coloring agents below within the following limits, by
weight:
4 Fe.sub.2O.sub.3 (total iron) >0.45% FeO >0.15% CoO 10 to 50
ppm Cr.sub.2O.sub.3 10 to 300 ppm CuO 0 to 400 ppm
[0036] This thin glass can be paired with another clear glass and
the combination can subsequently be rolled to form a laminated
glass exhibiting a light transmission LT.sub.A of greater than 70%
and a selectivity of greater than 1.3 which can be used as a
windshield. Preferably, such a glass exhibits an excitation purity
of less than 9%.
[0037] Another composition particularly suited to the production of
glasses with a thickness of the order of 3.85 mm, of use in forming
automobile windows, comprises the coloring agents below within the
following limits, by weight:
5 Fe.sub.2O.sub.3 (total iron) >0.4%, preferably >0.45% FeO
>0.12%, preferably >0.15% CoO <35 ppm Cr.sub.2O.sub.3 10
to 300 ppm CuO 0 to 400 ppm
[0038] Such a composition makes it possible to obtain a glass
exhibiting a light transmission LT.sub.A of greater than 60% and a
selectivity of greater than 1.3, preferably a light transmission of
greater than 70% and a selectivity of greater than 1.4.
[0039] Another composition particularly suited to the production of
glasses with a thickness of the order of 4.85 mm, of use in forming
windows for trucks or buses, comprises the coloring agents below
within the following limits, by weight:
6 Fe.sub.2O.sub.3 (total iron) >0.3%, preferably >0.4% FeO
>0.1%, preferably >0.13% CoO <25 ppm Cr.sub.2O.sub.3 10 to
300 ppm CuO 0 to 400 ppm
[0040] Such a composition makes it possible to obtain a glass
exhibiting a light transmission LT.sub.A of greater than 60% and a
selectivity of greater than 1.3, preferably of greater than 1.4.
Advantageously, the glasses exhibit a dominant wavelength at least
equal to 487 nm.
[0041] In the glasses according to the invention, the silica is
generally maintained within very narrow limits for the following
reasons: above approximately 75%, the viscosity of the glass and
its ability to devitrify greatly increase, which makes it more
difficult to melt it and to cast it on a bath of molten tin, and,
below 64%, the hydrolytic resistance of the glass rapidly decreases
and the transmission in the visible region also decreases.
[0042] The alkali metal oxides Na.sub.2O and K.sub.2O make it
easier for the glass to melt and make it possible to adjust its
viscosity at high temperatures in order to keep it close to that of
a standard glass. K.sub.2O can be used up to approximately 5% as,
beyond this level, the problem arises of the high cost of the
composition. Furthermore, the increase in the percentage of
K.sub.2O can essentially only be carried out at the expense of
Na.sub.2O, which contributes to increasing the viscosity. The sum
of the contents of Na.sub.2O and K.sub.2O, expressed as percentages
by weight, is preferably equal to or greater than 10% and
advantageously less than 20%.
[0043] The alkaline earth metal oxides make it possible to adjust
the viscosity of the glass to the conditions for the preparation of
the glass.
[0044] MgO plays an important role with regard to the viscosity and
it can be used up to approximately 5%. The complete elimination of
MgO, which plays an important role with regard to the viscosity,
can be compensated for, at least in part, by an increase in the
content of Na.sub.2O and/or SiO.sub.2. Advantageously, the content
of MgO is less than 2%, which has the effect of increasing the
absorption capability in the infrared region without harming the
transmission in the visible region.
[0045] BaO makes it possible to increase the light transmission and
it can be added to the composition according to the invention in a
content of less than 5%. BaO has a much weaker influence than MgO
and CaO on the viscosity of the glass and the increase in its
content takes place essentially at the expense of the alkali metal
oxides, of MgO and in particular of CaO. Any significant increase
in BaO thus contributes to increasing the viscosity of the glass,
in particular at low temperatures. Preferably, the glasses
according to the invention are devoid of BaO.
[0046] In addition to observing the limits defined above for the
variation in the content of each alkaline earth metal oxide, it is
preferable, in order to obtain the desired transmission properties,
to limit the sum of the percentages by weight of MgO, CaO and BaO
to a value equal to or less than 15%.
[0047] The glass composition in accordance with the invention is
capable of being melted under the conditions for the production of
float glass. Melting generally takes place in fired furnaces,
optionally provided with electrodes, which provide for the heating
of the glass in the body of the material by passing an electric
current between the two electrodes. To facilitate the melting, and
in particular to render the latter mechanically advantageous, the
glass composition advantageously exhibits a temperature
corresponding to a viscosity .eta. such that log.eta.=2 which is
less than 1500.degree. C., preferably a temperature corresponding
to the viscosity .eta., expressed in poises, such that log.eta.=3.5
(recorded as T(log.eta.=3.5)) and a temperature at the liquidus
(recorded as T.sub.liq) which satisfy the relationship:
T(log.eta.=3.5)-T.sub.liq>20.degree. C.,
[0048] and preferably the relationship:
T(log.eta.=3.5)-T.sub.liq>50.degree. C.
[0049] The examples of glass compositions given below make possible
a better appreciation of the advantages of the present
invention.
[0050] In these examples, the values of the following properties,
measured under a given thickness, are shown:
[0051] the factor for overall light transmission under illuminant A
(LT.sub.A) between 380 and 780 nm
[0052] the factor for overall energy transmission (T.sub.E)
integrated between 295 and 2 500 nm according to the ISO 9050
standard (Parry Moon Mass of air 2)
[0053] the selectivity (SE), measured by the ratio of the total
light transmission for the illuminant A (LT.sub.A) to the total
energy transmission (T.sub.E)
[0054] the dominant wavelength (.lambda..sub.D) under illuminant
D65
[0055] the excitation purity (PD65) under illuminant D65
[0056] the redox.
[0057] The calculations of the light transmission (LT.sub.A), of
the dominant wavelength (.lambda..sub.D) and of the purity (P) are
carried out by taking the CIE 1931 (Commission Internationale de
l'Eclairage de 1931 [International Commission on Illumination of
1931]) colorimetric reference observer. For the determination of
the redox, the total iron (Fe.sub.2O.sub.3) content is measured by
X-ray fluorescence and the ferrous iron (FeO) content is measured
chemically using the wet route. In the examples where the
composition is theoretical, the redox is determined using an
optical simulation program.
[0058] Each of the compositions which appears in table 1 was
prepared from the following glass matrix, the contents of which are
expressed as percentages by weight, this matrix being corrected
with regard to the silica in order to fit the total content of
coloring agents which are added:
7 SiO.sub.2 71.00% Al.sub.2O.sub.3 0.70% CaO 8.90% MgO 3.80%
Na.sub.2O 14.10% K.sub.2O 0.10%
[0059] The glasses of examples 1, 11, 18 and 30 are examples
prepared according to the invention, the compositions of which were
measured, whereas the glasses of the other examples are given with
their theoretical compositions.
[0060] These various examples show that, within a broad range of
coloring agents, the compositions according to the invention make
it possible to obtain blue glasses which satisfy the constraints of
overall light transmission (LT.sub.A>60%) and which, in
addition, exhibit a selectivity at least equal to 1.1 (tables 2 to
4).
[0061] Examples 1 to 42, prepared according to the invention, show
that it is possible to obtain glasses exhibiting the desired blue
coloring, that is to say a wavelength of between 485 and 490 nm,
and a purity of less than or equal to 13% while offering a high
light transmission (greater than 60%) and a selectivity at least
equal to 1.1. These good properties of the glasses result from the
combination of the coloring agents in the form of iron, cobalt,
nickel and, if appropriate, copper oxides. The examples also show
that the targeted optical properties can be achieved with a
relatively low iron content (less than or equal to 0.51%), which is
particularly advantageous when it is a matter of employing the
composition in plants for the production of "clear" glass operating
according to the float process.
[0062] The glasses obtained from the compositions according to the
invention are compatible with the usual techniques for the
manufacture of flat glass. The thickness of the glass ribbon
obtained by coating the molten glass on a tin bath can vary between
0.8 and 10 mm, preferably between 3 and 5 mm, for automobile
windows and between 5 and 10 mm for windows intended for the
construction industry.
[0063] The window obtained by cutting from the glass ribbon can
subsequently be subjected to a bending operation, in particular
when it is an automobile window. It can also be subjected to other
subsequent treatment operations, for example targeted at coating it
with one or more layers of metal oxides for the purpose of reducing
the heating thereof by solar radiation and, consequently, of
reducing the heating of the passenger compartment of a vehicle
fitted with it.
8TABLE 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Fe.sub.2O.sub.3 (%)
0.51 0.51 0.51 0.51 0.50 0.40 0.50 0.50 0.50 0.50 0.40 0.40 0.40
0.40 0.40 FeO (%) 0.175 0.175 0.175 0.175 0.13 0.13 0.13 0.12 0.15
0.16 0.12 0.12 0.13 0.13 0.10 Redox 0.34 0.34 0.34 0.34 0.26 0.33
0.26 0.24 0.30 0.32 0.30 0.30 0.33 0.33 0.25 CoO (ppm) 23 35 38 31
31 15 43 50 25 13 38 43 24 28 20 Cr.sub.2O.sub.3 (ppm) 40 80 40 130
50 70 100 40 70 20 200 120 140 70 80 CuO (ppm) 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Fe.sub.2O.sub.3 (%) 0.45 0.45 0.45 0.41 0.41 0.41 0.41 0.41 0.36
0.35 0.35 0.31 0.31 0.31 0.24 FeO (%) 0.10 0.15 0.14 0.12 0.10 0.10
0.14 0.12 0.12 0.10 0.11 0.09 0.09 0.105 0.08 Redox 0.22 0.33 0.31
0.29 0.24 0.24 0.34 0.29 0.33 0.29 0.31 0.29 0.29 0.34 0.33 CoO
(ppm) 21 36 22 28 22 41 38 38 26 22 39 32 24 40 24 Cr.sub.2O.sub.3
(ppm) 50 120 120 105 40 140 140 175 150 60 210 160 73 225 115 CuO
(ppm) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 31 32 33 34 35 36 37 38 39 40
41 42 Fe.sub.2O.sub.3 (%) 0.24 0.24 0.51 0.50 0.45 0.41 0.41 0.41
0.36 0.38 0.35 0.26 FeO (%) 0.082 0.081 0.175 0.13 0.10 0.12 0.14
0.115 0.123 0.13 0.11 0.08 Redox 0.34 0.34 0.34 0.26 0.22 0.29 0.34
0.28 0.34 0.34 0.31 0.31 CoO (ppm) 38 45 18 37 15 26 32 15 21 38 32
30 Cr.sub.2O.sub.3 (ppm) 125 145 40 95 50 105 140 60 130 80 190 130
CuO (ppm) 0 0 170 240 230 80 225 120 215 245 350 280
[0064]
9TABLE 2 1 2 3 4 5 6 7 8 3.85 mm LT.sub.A (%) 70.8 67.2 67.2 67.2
71.0 74.7 67.1 67.1 T.sub.E (%) 49.4 47.8 48.1 47.5 54.4 56.1 52.7
54.5 SE 1.43 1.41 1.40 1.41 1.31 1.33 1.27 1.23 .lambda..sub.d (nm)
488 487 486 489 489 488 488 486 P.sub.D65 (%) 7.3 8.5 9.3 7.8 6.0
5.5 7.3 8.1 3.15 mm LT.sub.A (%) 74.2 71.0 71.0 71.1 74.4 77.5 71.0
71.0 T.sub.E (%) 54.4 53.1 53.4 52.8 59.4 60.8 57.9 59.5 SE 1.36
1.34 1.33 1.35 1.25 1.27 1.23 1.19 .lambda..sub.d (nm) 488 487 486
489 489 488 488 486 P.sub.D65 (%) 6.0 7.1 7.7 6.4 5.0 4.6 6.1 6.7
4.85 mm LT.sub.A (%) 66.3 62.0 62.0 62.1 66.5 70.8 62.0 61.9
T.sub.E (%) 43.3 41.6 41.9 41.2 48.3 50.2 46.4 48.2 SE 1.53 1.49
1.48 1.51 1.38 1.41 1.34 1.28 .lambda..sub.d (nm) 487 487 485 489
488 488 488 485 P.sub.D65 (%) 9.0 10.6 11.5 9.5 7.5 7.0 9.0 10.1 9
10 11 12 13 14 15 3.85 mm LT.sub.A (%) 71.1 74.6 66.9 67.2 71.0
71.3 74.7 T.sub.E (%) 51.9 52.4 53.7 54.4 54.3 54.9 60.3 SE 1.37
1.42 1.25 1.24 1.31 1.30 1.24 .lambda..sub.d (nm) 489 489 489 486
489 486 489 P.sub.D65 (%) 6.1 5.4 7.1 8.4 6.2 7.3 4.7 3.15 mm
LT.sub.A (%) 74.4 77.5 70.9 71.1 74.3 74.6 77.6 T.sub.E (%) 57.0
57.3 58.9 59.5 59.2 59.8 64.8 SE 1.31 1.35 1.20 1.19 1.26 1.25 1.20
.lambda..sub.d (nm) 489 489 489 486 489 486 489 P.sub.D65 (%) 5.1
4.5 5.9 6.9 5.1 6.1 3.8 4.85 mm LT.sub.A (%) 66.6 70.8 61.8 62.0
66.5 66.8 70.9 T.sub.E (%) 45.8 46.5 47.3 48.1 48.1 48.9 54.6 SE
1.45 1.52 1.31 1.29 1.38 1.37 1.30 .lambda..sub.d (nm) 489 489 489
486 489 486 489 P.sub.D65 (%) 7.6 6.7 8.8 10.5 7.7 9.1 5.8
[0065]
10TABLE 3 16 17 18 19 20 21 22 23 3.85 mm LT.sub.A (%) 74.8 67.2
71.1 71.1 75.0 67.3 67.0 67.3 T.sub.E (%) 60.3 50.5 53.0 55.8 60.6
56.8 51.6 54.0 SE 1.24 1.33 1.34 1.27 1.24 1.18 1.30 1.25
.lambda..sub.d (nm) 488 487 489 488 487 489 487 489 P.sub.D65 (%)
4.7 8.6 6.3 6.4 5.2 6.6 8.5 7.2 3.15 mm LT.sub.A (%) 77.6 71.0 74.4
74.4 77.8 71.2 70.9 71.2 T.sub.E (%) 64.8 55.7 58.0 60.7 65.1 61.7
56.8 59.1 SE 1.20 1.27 1.28 1.23 1.20 1.15 1.25 1.20 .lambda..sub.d
(nm) 488 487 489 488 487 489 487 489 P.sub.D65 (%) 4.7 7.1 5.2 5.3
4.3 5.4 7.0 6.0 4.85 mm LT.sub.A (%) 71.0 62.0 66.6 66.6 71.2 62.2
61.8 62.2 T.sub.E (%) 54.7 44.2 46.9 49.8 55.0 50.5 45.3 47.7 SE
1.30 1.40 1.42 1.34 1.29 1.23 1.36 1.30 .lambda..sub.d (nm) 488 486
489 488 487 489 487 489 P.sub.D65 (%) 5.9 10.9 7.8 8.0 6.5 8.2 10.5
9.0 24 25 26 27 28 29 30 3.85 mm LT.sub.A (%) 71.0 74.9 67.3 71.1
74.9 67.2 74.9 T.sub.E (%) 55.7 60.7 55.4 60.3 62.4 56.1 64.1 SE
1.27 1.23 1.21 1.18 1.20 1.20 1.17 .lambda..sub.d (nm) 489 487 489
489 487 489 488 P.sub.D65 (%) 6.1 5.4 7.0 5.7 5.3 7.0 4.9 3.15 mm
LT.sub.A (%) 74.4 77.7 71.1 74.4 77.7 71.1 77.7 T.sub.E (%) 60.6
65.1 60.4 64.9 66.6 61.1 68.2 SE 1.23 1.19 1.18 1.15 1.17 1.16 1.14
.lambda..sub.d (nm) 489 487 489 489 487 489 488 P.sub.D65 (%) 5.1
4.4 5.8 4.7 4.4 5.8 4.1 4.85 mm LT.sub.A (%) 66.5 71.1 62.1 66.6
71.0 62.0 71.1 T.sub.E (%) 49.6 55.1 49.1 54.5 56.8 49.8 58.7 SE
1.34 1.29 1.26 1.22 1.25 1.24 1.21 .lambda..sub.d (nm) 489 487 489
489 487 489 488 P.sub.D65 (%) 7.6 6.7 8.7 7.1 6.7 8.7 6.2
[0066]
11TABLE 4 31 32 33 34 35 36 37 38 39 40 41 42 3.85 mm LT.sub.A (%)
71.0 67.1 71.0 67.2 74.8 71.1 67.1 74.8 71.1 67.2 67.1 71.1 T.sub.E
(%) 62.2 60.1 48.7 51.5 58.9 55.4 50.5 57.5 54.3 52.2 53.5 60.6 SE
1.14 1.12 1.46 1.30 1.27 1.28 1.33 1.30 1.31 1.29 1.25 1.17
.lambda..sub.d (nm) 486 489 488 489 489 488 487 488 489 485 489 488
P.sub.D65 (%) 6.9 6.8 7.6 7.8 5.3 6.6 8.9 5.5 7.0 10.1 8.2 7.1 3.15
mm LT.sub.A (%) 74.4 71.0 74.3 71.1 77.6 74.4 71.0 77.6 74.4 71.1
71.0 74.4 T.sub.E (%) 66.6 64.8 53.8 56.8 63.5 60.3 55.8 62.1 59.3
57.4 58.7 65.1 SE 1.12 1.10 1.38 1.25 1.22 1.23 1.27 1.25 1.25 1.24
1.21 1.14 .lambda..sub.d (nm) 486 489 488 489 489 488 487 489 489
485 489 488 P.sub.D65 (%) 5.6 5.6 6.3 6.5 4.3 5.5 7.4 4.5 5.8 8.3
6.8 5.9 4.85 mm LT.sub.A (%) 66.5 62.0 66.5 62.1 71.0 66.6 61.9
71.0 66.6 62.1 62.0 66.6 T.sub.E (%) 56.8 54.1 42.7 45.1 53.1 49.3
44.2 51.7 48.2 45.9 47.1 54.7 SE 1.17 1.15 1.56 1.38 1.34 1.35 1.40
1.37 1.38 1.35 1.32 1.22 .lambda..sub.d (nm) 486 489 488 489 489
488 487 488 489 485 489 488 P.sub.D65 (%) 8.6 8.4 9.4 9.7 6.6 8.3
11.1 6.9 8.7 12.6 10.1 8.9
* * * * *