DE1771358C - Luminescent glass and process for its manufacture - Google Patents

Description

The lirlind refers to iumineszicrendc Glasses, in particular on fluorescent glasses for fluorescent lamps or lampshades. With radiation Such luminescent glasses with short-wave radiation emit fluorescent light in such glasses different areas of the visible spectrum, which are used for lighting purposes, for example can be.

A whole series of different luminescent crystalline substances are known, which are known as phosphors for fluorescent lamps. Oscillographic screens and TV channels can be used. In fluorescent lamps, calcium tungstate and zinc beryllium silicate phosphors have primarily been used as crystalline phosphors to achieve different color tones. More recently, the crystalline halophosphates have become more prevalent. In addition to the advantageous lighting properties, these phosphors are also characterized by good stability against electrical discharge in the fluorescent tubes . In addition, doubly activated crystalline calcium silicate is also widely used. Crystalline, ultraviolet light-emitting phosphors are also used to a lesser extent, e.g. B. Lenard's CaSAgK phosphor. The number of crystal phosphors that have recently been used for fluorescent screens is particularly diverse. Cathode ray tubes and oscilloscope screens are mainly made to luminesce by a mixture of three kinds of sulfide phosphors, the mixture causing certain spectral intensity distributions of the luminescent light. More recently, crystalline calcium halophosphors have also been used here with success.

In addition to such doubly activated phosphors,

those that have long been known for both fluorescent screens and fluorescent lamps (fluorescent tubes) Zinc sulfide based crystal phosphors, cadmium sulfide based or similar phosphors are used. Also luminescent glasses with fluorescent color ben, some of which are visible over the whole Spectrum ranging from dark blue-violet to the reddish spectral range have been around for a long time long time in trade. An addition of uranium. Rare earths and other suitable substances allowed to make clear, translucent glasses with fluorescent properties.

The known methods such as silk printing, vapor deposition or sedimentation have almost all major drawbacks. Except for the fact thing that those applied by normal methods Phosphorus layers are relatively expensive in the process, the phosphors are additionally inclined to agglomeration and in this way create uneven layers. Because of that this is did not emit luminescent light throughout

Area of the emitting surface of the same intensity. The loose packing of the phosphors has at the same time

also interference phenomena in the wake. Also on the loose packing apparent refractive index differences are due. These disadvantages are avoided in the normal production of luminescent layers on a substrate by the additional use of a binder with which the phosphors are cemented to the substrate. However, these binders do not have great chemical stability. It is also disadvantageous that the mechanical resistance of such screens with cemented-on phosphors is very low. Post-processing is therefore also relatively expensive. Apart from that is

fio the manufacture of crystalline Phosphormatcrialicn also technologically not simple and expensive.

Recently there is another type of luminescent vitreous material became known. These are not real glasses.

ds but materials that are in the manner of a glass ceramic Although they have been manufactured as glass, by means of suitable temperature control conditions based on a keratinization process but at least in certain

Layers have completely crystallized. It is in accordance with the USA patent application 486 197 (French patent specification 1 498 645) to glasses with zinc contents over 25%, on the other hand, according to US patent application 504 068 (French patent specification 1 499 538) for calcium borate glasses, which are endowed with rare earths. Both ceramized types have crystallized Form luminescent properties after suitable temperature treatment. Only the crystalline ones Precipitations are the carriers of luminescence and have the same function as those above mentioned normal crystal phosphors.

Furthermore, according to US Pat. No. 2,219,895, a technique is known in which a zinc silicate phosphorus in crystalline form in a glass material is precipitated to a transparent, luminescent glass to create. In this US Pat. No. 2,219,895 it is proposed to use a glass from the Glaskomponeni.cn and the components of a luminescent material to melt and then subsequently to deform. This deformed glass becomes another Subjected to temperature treatment after cooling it to room temperature, with devitrification leads to precipitation of crystalline phosphors within the glass at suitable temperatures.

The production of fluorescent lamps and fluorescent screens that is customary today is based in principle on the fact that on a carrier material, which mostly consists of normal glass, crystalline phosphors in some form Way to be applied. This side of the glass, on which the crystalline phosphors are applied, is in Use turned towards the excitation light source. The fluorescent light of the phosphors penetrates from this Layer through the carrier glass to the outside. Often the carrier glass also has the function of stimulating radiation (usually it is a matter of excitation by mercury lines in the UV range) only to allow it to penetrate into the phosphor layer and to shield it from the outside space.

In U.S. Patent 3,300,670 it is stated that continuously crystallized glasses, which are made in the manner of Glass ceramics lead to luminescent properties, have the disadvantage that they crystallize out Particles the excitation radiation from the side exposed to the excitation radiation seen, do not let it go far into the glass, but let the crystals, which are evenly distributed in the glass, the Do not let luminescent radiation through to the other side of the glass. This is the effect of luminescence on the back of the glass, which is supposed to emit the luminescence radiation, can only be seen faintly. The aforementioned U.S. Patent 3,300,670 and U.S. Application 486 197 (French patent specification 1 498 645) therefore suggest that crystals should only be deposited on the surface of the glass. Here is that In the interior of the glass there is only one substrate on which the layer or layers of the precipitated Crystals rests more or less firmly.

The aim of this invention is homogeneous, translucent Glasses which, when excited by suitable short-wave radiation, emit fluorescence in the visible Part of the spectrum / own. These glasses should be translucent, not transparent and only a relatively low permeability for the excitation shaft length own. It is another object of the invention. homogeneous, translucent glasses with the above-mentioned fluorine, tcnzcienschaftcn im To create visible, which under technologically known, simple conditions in the form of Tubes and flat glass can be drawn continuously. This results in an essential »Eration in the production of z. B. fluorescent tubes or fluorescent screens compared to the one described above, up to now common manufacturing method. The phosphors that emit the fluorescent light must can no longer be applied to the glass afterwards, but are already in the process of shaping of the glasses contained in the glass.

The object of the invention is a method for the production of glasses, which in addition to the above Properties have a high degree of diffuse light transmission.

Another object of the invention is a method of manufacturing an umbrella or tube with luminescent phosphors, which has improved properties.

Another object of the present invention is to manufacture glass articles or articles with luminescent properties, which including particularly improved physical properties higher mechanical strength and scratch resistance as well as better thermal resistance compared to have the well-known luminescent screens. Another object of the invention is manufacture a glass body which, when illuminated with suitable electromagnetic radiation, emits other electromagnetic radiation with a longer wavelength.

Another object of the present invention is the production of a glass screen or tube, which shows luminescence when exposed to stimulating radiation. Also one Another object of the invention is to produce a glass and a glass screen with cathode luminescence, the when he is on at least one surface with a stimulating bundled radiation is illuminated, a clearly visible luminescence image on the opposite, non-illuminated side this excitation radiation shows.

Another object of the invention is to produce a luminescent glass which thereby is characterized in that segregation areas exist in it within a basic glass matrix which, in terms of composition approximately correspond to the composition of known crystalline phosphors, these X-ray amorphous segregation areas Possess luminescent properties.

Another object of the invention is a material with improved luminescent properties.

Another object of the invention is to produce an improved luminescent material, which contains luminescent, X-ray amorphous segregation areas in a glass matrix, which in situ can be generated within the glass.

Another object of the present invention is to produce a new and effective one Phosphorus, which is created by the segregation of a glassy material.

A special characteristic of the glasses according to the invention is that the crystallization of phosphors is consciously avoided. In this way, ad-

H? Sorption phenomena of luminescent light avoided by deposited crystals.

It is another characteristic of the glasses described. that the areas which the luminescence

cause, arise through a segregation process and approximately correspond in composition to known crystalline phosphors. These glassy ones Regions., Embedded as droplet-shaped segregation in a basic glass matrix, show anyway real luminescence.

Another characteristic of the glasses described is that they are more or less translucent, but are not transparent.

Another characteristic of the glasses according to the invention is that they owing to their viscosity properties can be produced in the form of tubular or flat glass without major technological difficulties.

It has been found that the relationships that have recently become known about the tendency to segregate in SiJicat and borosilicate glasses are used can be used to produce fluorescent properties in glasses, such as the silicate and Borosilicate glasses per se have no luminescent properties own.

To explain the segregation and the tendency to segregate in glasses, refer to the theory the phase separation in the glass will be discussed in more detail in this context. The segregation of Melting into liquid phases can often be observed, and glass melts also often show this tendency. In terms of melting technology, the temperature at which a complete miscibility occurs, at which the miscibility gap closes, usually easy to achieve. However, a tendency to segregate in the melt can also be determined above the critical segregation temperature. This tendency to segregate manifests itself in an aggregation of the particles, through which the onset at lower temperatures Segregation is indicated. In this temperature range are the fluctuations of the chemical Composition larger than it corresponds to the statistical fluctuations. One can in this Stage in no case can we speak of crystallization. This tendency to segregate mentioned here and the aggregation of particles caused thereby is used in the present invention. at As the temperature increases, the fluctuations become smaller and smaller. As long as there are no special interactions exist between the various components, one can speak of a latent tendency to separate.

Another phenomenon observed is that a melt is above the melting temperature is homogeneous. but segregated on further cooling without crystallization occurring beforehand. Remains in certain cases the crystallization from. So there can be a tendency to segregate or in some In cases, even segregation has a particularly clear effect as droplet-like phase separations and to make noticable. Because of the high toughness of all Processes during the cooling of glasses, a crystallization process is suppressed. I show in heat then a complete glass cooled down to room temperature Phase separation (for example, mixing in two phases).

Numerous investigations dealt with the real homogeneity of cooled glasses. On Silicon and borosilicate glasses are different by electron microscopy Investigations into the homogeneity of the glass and the degree of segregation or phase separation have been carried out. at The solution to the problem underlying this invention has been found that it can be achieved by suitable Glass compositions is possible with the help of phase separation translucent glasses that are not are more transparent to sound, with the substances that have the luminescent properties of the glass effect, are concentrated in the segregation areas. The tendency to segregate causes a Phase separation, whereby the substances that make up the

ίο cause luminescence, enrich in one phase and after the cooling process of the glass in the partly droplet-shaped precipitations of the second Phase are localized. This second phase is X-ray amorphous. Let with the electron microscope within this second phase, some of the glasses described become cubic in a few places Generate electron diffraction images, but their contribution is insignificant within this phase. Two glasses the same composition and the same degree of segregation, one of which is completely free was of those areas in the separation phase which still allow electron diffraction images others containing some such areas showed no difference in fluorescence behavior. These mentioned Areas from which diffraction images can still be obtained therefore have no particular influence on the fluorescence behavior.

It has also been found that the particularly cheap crystalline ones that have recently become known Calcium halophosphate phosphors in the above-mentioned silicate and borosilicate base glasses as Let the segregation phase separate or at least enrich it particularly strongly in a segregation phase leave, where they are present in the radiographic sense in non-crystalline form.

With suitable additions of CaCO ₃ , P ₂ O ₅ , CaF ₂ , MnO ₂ and sufficient amounts of chlorine in the form of NaCl, and doping with manganese, antimony and cerium to silicate or borosilicate base glasses, luminescent, translucent glasses with luminescent colors of Create light blue through white, pink, yellow, orange to reddish, depending on the relative concentration of halogens, sensitizers and activators in the Gtos.

It has also been found that the addition of calcium halophosphate promotes the translucent character of the glasses. The result is milky-white, well-opacified glasses with the most varied of phase separation capacities and degrees of opacity. It has been found that the ratio of the concentration of CaO to P ₂ O _{5 has} a particular influence on the degree of opacity of these glasses and that they are well luminescent. translucent glasses create translucent

sen when the ratio ρ η " ^m range of 0.8

up to 4.9.

Table I gives an overview of various Examples of melting.

( _{) 0} The examples listed in Table I relate to various silicate and borosilicate glasses of various basic types: composition. which contain CaC). P ₂ O ₅ and possibly sensitizers such as MnO ,. Sb ₂ O, as well as in two

(, _S cases cerium oxide is also common. All these GÜiscr Table 1 give a snan- after a normal Schmclzprozeß. A normal deformation and a subsequent cooling in order to achieve

Normally frcien glass more or less strongly opacified glasses, which all show phase separation. Electron microscopic examinations show drop-shaped or spherical segregation areas, which are particularly enriched _{with calcium oxide and P 2} O _5. The segregation areas of this phase are all X-ray amorphous and only rarely show crystalline cubic diffraction patterns under the electron microscope; the segregation has no adverse effect on the deformation process. The sensitizers manganese oxide, antimony oxide and cerium oxide and, to a certain extent, the halogens are also enriched in this mixing phase.

Depending on the concentration of the sensitizers, the fluorescent color ranges from light blue to white, pink, orange and reddish.

Table 1

SiO ₂ ...
B ₂ O ₃ ...
Al ₂ O ₃ ..
PbO ...
CaF ₂ ...
CaO ...
MgF ₂ ...
MgO ...
BaO ....
SrO ....
ZnO ...
Na ₂ O ..
NaCl ...
Na ₂ SiF ₆
Κ, Ο ...
KCl ....
KHF ₂ ..
Li ₂ O ...
LiF ....
P ₂ O ₅ ...
MnO ... Sb, O ₃ ..
Ce " ₂ O ₃ ..
ZrO ₂ ...

Ill

68.84
13.03
1.00
2.00
0.80
1.50

0.50

7.82
3.01

1.50

75.70

13.63

1.51

1.31
0.51

0.51

4.14
0.51

0.30

1.41
0.30
0.10
0.08

77.60

10.35

2.69

2.07

0.52 2.69

2.07 0.10

1.24 0.05 0.62

IV

65.61 4.94

5.93

2.96

11.86 2.96 3.56

1.98 0.10

0.10 Composition No.

v I vi I VIi

in percent by weight

68.72
0.49 -

VIII

IX

XI

57.35 44.38 46.63 62.68 67.11 50.68 - 19.72 16.87 - 12.39 - - 2.96 6.85 - 2.07 8.77 1.85 4.93 7.94 5.21 4.13 6.82 - 0.99 - 8.33 1.03 3.90 1.85 2.76 3.08 2.92 - 2.44 0.93 0.99 - - - - 1.11 - - - 0.93 - -. - 1.49 - - 2.92 - - 1.49 - - 1.46 15.73 7.89 - - - - - - - 7.29 - 7.80 3.70 - 4.96 5.21 - 3.41 2.96 - 1.98 3.12 - 1.95 9.25 3.94 1.98 - 7.23 4.87 - 1.97 - - 2.68 - - 2.96 - - 1.24 1.46 - - 1.56 - 1.46 1.85 - 0.62 - - 1.11 1.58 1.98 2.60 0.83 1.95 0.14 - 0.40 0.21 0.15 - 0.23 - 0.40 0.26 0.21 - 0.09 - - - - 0.10 1.85 4.93 3.97 - - ——

Table 1 also contains some glass compositions containing zinc oxide. Zinc oxide is also known as a phosphor in combination with sulfur. In the glass compositions of Table 1, which contain zinc oxide, however, the zinc oxide does not appear to have any primary influence on the fluorescence behavior. It will assumed that the zinc oxide behaves as a neutral glass former in the base glass. How far that Zinc oxide also acts as an additional sensitizer, cannot be clarified properly. In the segregation phase there was no excessive proportion of Zinc oxide can be detected in comparison to the general composition of the glass.

The glasses described do not require a ceramization process as is used in glass ceramics. They are fluorescent without ceramization. It has been found that in suitably composed silicate and borosilicate glasses, phase separations based on the contents of CaO and P ₂ O ₅ can be enforced, whereby by doping the glass with halogens and sensitizers, such as

For example, manganese, antimony and cerium, in the droplet-shaped precipitates in the glass compositions can be forced that the known crystalline phosphors correspond to:

Ca ₃ (PO ₄ J ₂ CaF ₂ (Mn, Sb) Ca ₃ (PQO ₂ CaF ₂ CaCl ₂ (Mn, Sb) Ca ₃ (PO ₄ J ₂ (Mn, Ce)

In contrast to these crystalline phosphors, which are known per se, however, the areas of segregation in the glass show in a radiographic sense never crystalline character. The fluorescent colors of the glass correspond approximately to the emission colors of the crystalline phosphors, depending on the relative concentration of the halogens and sensitizers.

It was also found that a silica! - or

Borosilicate base glass, in which a phase separation was _{forced by the contents of calcium oxide and P 2} O ₅ , in the same way as the crystalline phosphors based on calcium halophosphate by adding

209637/303

but certain metals act as sensitizers in their immission color can be varied. In Table 2, a silicate and a borosilicate glass are shown with otherwise : constant composition with the sensitizers lead, tellurium, cerium, thorium, tin and woolen been endowed. There were different colors of the fluorescent light, all in the area between 520 and 630 mn.

Table 2

SiO ₂ ..
B ₂ O ₃ .
Al ₂ O ₃
CaF ₂ .
CaO.
MgO.
K ₂ O.
KCl ..
KHF ₂
Na ₂ O
Li ₂ O.
P ₂ O ₅ -
PbO .
TeO ₂ .
Ce ₂ O ₃
ThO ₂ .
SnO ₂ .
WHERE ₃ .
MnO ₂
Sb ₂ O ₃

Xl!

XIII

XIV

68.41
12.95
1.00
0.80
1.49
0.50
7.77
2.99
0.80
1.00

1.49
0.30
0.10
0.02

0.20
0.20

68.87 68.51 13.03 12.96 1.00 1.00 0.80 0.80 1.50 1.50 0.50 0.50 7.82 7.78 3.01 2.99 0.80 0.80 1.00 1.00 1.50 1.50 0.10 - 0.05 0.07 - 0.20 0.20 0.20

Ziisiiinnicnsci / iing No.

XV I XVI

in percent by weight

68.09
12.88

0.99

0.79

1.49

0.50

7.73

2.97

0.79

0.99

1.49

0.50

0.40
0.20
0.20

65.76

0.51 8.09 2.02

7.08 4.05 7.69 1.01 3.64

0.10

0.05

XVlI

65.10

0.50 8.01 2.00

7.01 4.01 7.61 1.00 3.61 0.50 0.20 0.04

0.20 0.20

XVlIl

65.39

0.50 8.05 2.01

7.04 4.02 7.65 1.01 3.62

0.30

0.40

XlX

65.76

0.51 8.09 2.02

7.08 4.05 7.69 1.01 3.64 0.10

0.05

The content of various halogens in the glass composition also has a considerable influence on the color of the fluorescent light. Except the compositions given in Tables 1 and 2, in which only chlorine and fluorine have been used, glasses were also melted according to the invention, as well as chlorine and fluorine Contained bromine and iodine.

Table 3

SiO ₂

B ₂ O ₃

Al ₂ O ₃

CaO

MgO

K ₂ O

Na ₂ O

Li, O

P ₂ O ₅

PbO

Mn ₂ O ₃

Sb ₂ O ₃

KHF ₂

KCl

KBr

KJ

XX

69.11 13.08 1.01 2.01 0.50 7.85 1.01

1.61 0.40 0.20 0.20 3.02

XXl

69.46 13.14 1.01 2.02 0.51 6.89 1.01

1.62 0.40 0.20 0.20 1.00 2.53

XXII XXIIl XXIV

68.43 12.95 1.00 1.99 0.50 6.77 1.00

1.59 0.40 ■ 0.20 0.20 1.00

3.98

68.43 12.95 1.00 1.99 0.50 6.77 1.00

1.59 0.40 0.20 0.20 1.00

3.98 Composition No.

XXV I xxvi I xxvii | xxvm | xxix | xxx | χχχι in percent by weight

67.42 12.76 0.98 1.96 0.49 7.65 0.98

1.57 0.39 0.20 0.20 2.94 67.75 12.82 0.99 1.97 0.49 7.19 0.99

1.58 0.39 0.20 0.20 0.50 2.47 2.47 2.45 -

69.68 13.18 1.01 2.03 0.51 7.91 1.01

1.62 0.41 0.20 0.20 1.01 1.01

0.20

68.15 12.90 0.99 1.98 0.50 7.74 0.99

1.59 0.40 0.20 0.20 1.98 1.98

0.40

65.30 12.36 0.95 1.90 0.48 7.41 0.95

1.52 038 0.19 0.19 3.80 3.80

0.76

67.25

0.52 8.02

6.54 7.86 1.03

3.72

0.19 0.23 0.50

4.14

66.22

0.51 7.90

6.93 7.74 1.02 3.67

.0.18 0.22 3.06

2.55

66.56

0.18 0.23 1.00 2.56 2.56

The compositions of two selected SiIicat and borate glasses in Table 3 show that one Change of the fluorescent light by adding different halogens to glasses with segregation areas, whose overall composition approximates a calcium phosphate composition resembles, is possible. The addition of bromine and iodine in particular causes favorable fluorescence properties.

It was also found that borosilicate glasses with relatively low silica contents and even silica-free glasses, as shown in Table 4 in the form of a few, not restricting the invention Selected examples are summarized, can be created in transparent form and are good Possess luminescent properties.

Table 4

Composition No.

XXXlI I XXXIII I XXXIV
in percent by weight

39.04 0.85 - 29.03 46.98 48.41 4.01 17.69 21.92 3.00 ■ 5.04 6.80 3.00 0.98 5.11 5.01 0.20 1.00 4.61 2.15 - 6.01 4.39 4.11 3.00 3.42 2.74 1.00 0.98 0.64 0.80 0.98 1.74 1.00 8.07 - - 1.71 - 0.50 6.55 7.31 - 0.05 0.09 0.14

Al ₂ O ₃

MgO

CaO

PbO

ZrO ₂

NaCl

KBr

KJ

P ₂ O ₅

AlF ₃

BaO

NaF

MnO ₂

SB ₂ O ₃

However, these glasses do not have such a favorable viscosity behavior as the examples listed in Tables 1 to 3. They are therefore not equally suitable for continuous drawing of tube and flat glass. In principle, however, they have the same structure as the luminescent, translucent borosilicate or silicate glasses of the examples in Tables 1 to 3. Thereafter, a luminescent, translucent glass, which does not contain any crystalline phosphors in the radiographic sense, be composed of a base glass with a greater or lesser tendency to separate, containing a separation phase which is more or less identical to the phosphorus composition containing the basic building material of phosphorus, e.g. B. calcium halophosphate and the like, which in the radiographic sense is in non-crystalline form in the demixing phase after glass production, activators of the type Sb ₂ O ₃ , MnO ₂ , PbO etc. and if necessary also from sensitizers of the tellurium, cerium oxide, thorium, tin type , Tungsten, etc.

Making such luminescent, translucent Glasses can be made as follows: (Some of the items listed in Tables 1 to 4 mentioned composition examples selected with respect to their production as possible show great differences. However, these examples are not intended to limit the invention).

example 1

The following are mixed into a mixture in parts by weight:

260.47 g iron-free sand,

3.01 g alumina hydrate,

55.70 g calcium carbonate,

4.00 g calcium fluoride,

40.00 g potash,

16.00 g potassium bromide,

52.23 g soda,

9.90 g lithium carbonate,

14.40 g phosphorus penoxide,

0.78 g manganese oxide,

0.88 g of antimony oxide.

After mixing this mixture is placed at 1480 ° C in a platinum crucible, melted, refined hour at 1495 ° C, cooled to 138O ° C, then stirred for 15 minutes at 1380-1430 ⁰ C, poured into a metal mold in an electric furnace hours annealed at 695 ° C and then at a cooling rate of 40 ° C / hour. cooled from 695 ° C to room temperature. The translucent glass shows luminescence when excited with a mercury spectral lamp.

Example 2 example /.

A mixture is weighed from the following components:

weighed in

275.29 g iron-free sand,
92.11 g H ₃ BO,

6.02 g alumina hydrate,
14.38 g calcium carbonate,

4.72 g magnesium carbonate, 45.88 g potash,
12.35 g potassium bifluoride,

6.87 g soda,

6.4 g phosphorus pentoxide,

1.64 g lead oxide.

0.87 g manganese oxide,

0.80 g of antimony oxide.

After thorough mixing, the mixture is BE 1470 ⁰ C in a platinum crucible inserted, melted at gleichei temperature and purified V2 hour at 1500 ° C, cooled to 1450 ⁰ C, then poured cooled voi at 1400 ° C in 15 minutes under stirring into a metal mold and cooled to room temperature after the GuI at a cooling rate of 50 ° C./hour. The well-clouded, translucent glass shows luminescence when excited with a mercury spectral lamp.

Example 3

The following components are weighed into a batch:

180.32 g iron-free sand,
141.71 g H ₃ BO ₃ ,
18.05 g of alumina hydrate

4.16 g calcium fluoride,
20.13 g of calcium carbonate
23.53 g potash,

13 ° 14

8.00 g KCl, the mixture is at 1430 "C in a Sillimanit-

12.35 g potassium bifluoride, crucible melted down. Ran for 2 hours at 1470 C

6.40 g phosphorus antoxide, tcrt. left to stand at 1280 C, then into a

20.47 grams of lead oxide. Mctallform cast and with a cooling speed

32.10 g zinc oxide. 5 speed of 70 C / h. cooled to room temperature.

20.04 g zirconium oxide, the milky white glass shows when excited with a

4.38 g of magncsium fluoride. Mercury spectral lamp luminescence.

Example 4

The following components are cooled to one. The slightly cloudy glass is in one

amount weighed: electric furnace ^{heated again to 560 0} C, at this

", U a _a4 μ, _Rn temperature annealed for 6 hours and then

inn οι ⁸ τ Λ h Λ t ^{with a} cooling speed of 7 ° C / hour. on

1S g MTgntium carbonate, ■ * cooled to room temperature. The now heavily clouded

10.06 i calcium carbonate, Jlas shows be, excitation m, t e.ner Quecks.lber-

113 Bl i id spectral lamp good luminescence.

/ cn "i <- I ₁ !] * Depending on the content of the base gas for segregation

inn ο v ^ inmSnmiH inclining "hare occurs a different degree of

λ-m ν ^mmDr ° ^mm '20 Turbidity in the glass after completion. Through

0.70 g potassium iodide,. ^& _ _r ., . ° _ ·,,, ·. ·

1.90 l phosphorus pentoxide, suitable temperature control in the range of the

" _M μ. · Fi α can be seen the demixing temperature, the turbidity

η if ⁸ ' ^Nainumnu ° ^na ''one and the same glass composition but in

ns V ¹ ^ ^nganox ! ^ limits vary. With this variation of the

u, ο g Aniinonoxia. ^ _{bung properties change s} , _{ch also the} Lumines-

This mixture becomes zenze property of the glass after thorough mixing, since with different

at 1430 ^c C placed in a platinum crucible, melted-in degree of opacity, i.e. different particle-

Zen. purged for 1 hour at 1450 ⁰ C to 138O ° C driving rain number and particle size of the Entmischungsbereiche,

let in, ^{stirred at 138O 0} C for 15 minutes, on the concentration of the luminescent phosphor

126O ⁰ C cooled, at 1260 ⁰ C in a metal form 30 phors is changed as long as the carrier of the fluorescence

poured and then more or less coincident with a cooling speed and demixing phase.

speed of 70 ° C / hour from 515 ° C to room temperature.

2549

Claims (9)

Patent claims: 1. Luminescent glass, which when excited shows fluorescence in the visible part of the spectrum with suitable short-wave radiation, thereby characterized in that it contains luminescence-causing components enriched in a separation phase (without crystallization). 2. Luminescent glass according to claim 1, characterized in that it is added as a result of components that promote segregation is not transparent, but translucent. 3. Luminescent glass according to claim 1 or 2, characterized in that it contains predominantly calcium halophosphates enriched with or without activators in a segregation phase. 4. Luminescent glass according to claim 1, 2 or 3, characterized in that it consists of one the base glass tends to separate, to which calcium oxide, phosphoric acid and halogens are added as carriers of the luminescence, which in the separation phase form a glass which has a similar composition such as the crystalline calcium halophosphate phosphors known per se. 5. Luminescent glass according to claims 1 to 4, characterized in that there are activators and sensitizers in the luminescence-causing vitreous separation phase contains, which are known per se from crystalline calcium halophosphate phosphors. 6. Luminescent glass according to claim 4, characterized in that it is fluorine as halogen and / or contains chlorine and / or bromine and / or iodine. 7. Luminescent glass according to claim 4, CiiO characterized in that the ratio -g ^ p ranges from 0.8 to 4.9. 8. A process for the production of luminescent glass, characterized in that a glass composition according to Claims 1 to 6 is segregated in the range of the critical segregation temperature during the melting process and / or the subsequent cooling. 9. The method according to claim 8, characterized in that the segregation using an additional temperature treatment is carried out.