DE1696067A1 - Phototropic glass - Google Patents

Description

H. SEILER, J. PFENNING _{$ 1} 90067 ti _m »19th Mfc» I968 DIPLOM-ΙΝΘ ENIEURE * _VV ν * "* 'OldenbUr ₀ allee ICT * PATtNTAKWJLTE Telephone: 304 BB Si 1 22 Telecromm-Adreaae: rope defense patent

UBBB Y-OWENShJ ¹ OEI) GIaSS COMPANY, 811 Madison Avenue iDoledo, OMo, T.St.A.

Phototropic glass

Mr this notification will be the priority of the corresponding one Claimed U.S. Application Ser. No. 624,502 filed March 20, 1967.

The invention relates generally to photosensitive glasses and in particular the improvement of the reactions of such borosilicate glasses with metal halide mechanisms be made phototropic by heat treatment, as well Process for making the improved glasses.

Phototropic glasses of this general type are on known to the relevant area »however, the

known »relevant glasses action characteristics an Arjfc and / or a speed on the same unsuitable for many industrial needs, especially in the field of motor vehicles,

An important problem underlying the invention pun is to create a borosilicate glass that a fast and practically real phototropic or solar heating with remarkably fast reversal below the normally occurring conditions combined.

Jüline is another object underlying the invention in creating a glass of this kind, the one relative dense darkening potential and a book formation speed which is hyperbolic.

These and other objects are briefly outlined in accordance with the invention solved in that in an Anaatz potentially phototropic Glases special activators are introduced, which preserve the solarisibility in the, g of the heat treatment increase subjected glass and / or accelerate the reversal of the phototropic effect of the same.

The invention is explained in the following, for example, with reference to the attached sheet of drawings , which shows a graphical representation with curves, the photographic effect and regression of three exemplary glasses being recorded.

According to the invention, an object made of phototropic glass is created, which has a borosilicate glass matrix, a Has metal halide mechanism and an activator and characterized in that the activator is ceria is, and further in that the glass when exposed to Sunlight approximated within the first 60 seconds Reached $ 90 of its darkness.

According to the invention, a method for producing phototropic glass objects is also provided in which an approach including the components for forming a borosilicate matrix and components for forming a metal halide mechanism is compounded, mixed and melted. ** ^π1 * then the seschmolaene & las in

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a predetermined form is transferred, theee Mold or shaped body is then subjected to a heat treatment in order to make it phototropic and is thereby characterized in that an Öerverbindungen the approach as an activator before melting it is added.

As indicated above, the phototropic glasses according to the invention are essentially silicate glasses and consist of a base glass or matrix, which is preferably an alumina-borosilicate glass that is approximately 40 to 60% on a weight basis. SxO ₈ , 4 to 26 $ Al ₈ O ₃ , 4 to 26- / C. B ₃ O ₃ , 0 to 10jt. ZrO ₂ and 8 to 16 $ of at least one alkali metal oxide, consisting of the group Na ₈ O, K ₈ O, Eb ₈ O and Cs ₂ O, and 0 to 1.5 $ F.

To make such a glass phototropic, one finds Silver halide mechanism application and it is a Balance of "solubility" and the network structure required for the phototropic mechanism to work.

This equilibrium appears to result from the boron and the clay in the base glass or matrix, with the boron acting as a universal solvent and plasticizer and clay acting as network formers or modifiers Proportions leads to an ideal fluid for the mechanism, and ela boron oxide to aluminum oxide ratio of about 2 B20 _a to 1 Al ₈ O ₀ gives excellent results.

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In this context, the clay can be completely or partially replaced by other network formers or modifiers, such as zirconium oxide, increased amount of silica or niobium, can be replaced with zirconium oxide borosilicate glasses Practically, they are white as white.

Thus, the mechanism can develop, it is preferred that approximates the following range of silver and halides are present should s
Ag ₈ O 0.05 to 0 _f 3 #

Br ₄ $ 0.1 to $ 0.3

I ₈ 0.05 to 0.7 #

Gl ₄ $ 0.0 to $ 0.5

CuO is also required in the mechanism and should be in an amount of about $ 0.01 to $ 0.10.

Finally, and this is very important, according to the invention, the incorporation of special activators into these glasses is considered, which can be solarizing agents as well as accelerators Increase photosensitivity, pre-eminently with zinc to speed up the reversal. J2p titanium can also be used to increase the speed of tanning. According to the invention, a 0er compound is added to the glass batch in an amount of 0. QDl to 1.0 wt. ^ B, expressed as C er oxide based on the total batch. Where arsenic is used * should dae same as an arsenic compound in an amount of 0.01 to 1.0 wt. ^ Expressed are added as As ₈ O _8. In similar

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Zinc, in so far as it is used, should be considered a zinc compound in an amount of 0.001 to 1.0 wt. # in terms of ZnO, can be added ο

In the molten form, the invention Glasses are poured, rolled or drawn into slices or hollow rings of the desired thickness and the obtained Disks or blanks are made phototropic by exposing them to relatively high temperatures for extended periods of time be subjected, and "was either with or without preliminary" annealing and this in accordance with those customary in the field of phototropic glasses Working methods

example 1

According to a preferred embodiment according to the invention will. Green blanks with remarkable phototrophic properties are made by an approach of the following Composition is mixed. s

Sand :

Boric acid

Aluminum trioxide

Sodium nitrate
Sodium fluoride

forming a matrix with;

Sodium chloride
Silver bromide
Sodium bromide
Sodium iodide
Copper oafid

228.0 parts 142.2 44.0 110.0 4.0

2.964 parts 1.570 1.404 1.890 0.056

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to form the metal halide meohaniamus, and:

Zinc oxide 0.020 parts

Areen Oxide 0.400

Peroxide 0.20

Ferric oxide 0.24

as a solarizing agent and accelerator.

Generally speaking, the iron content of these glasses can be set in a range from 0 to Q 5 $ to ground so to improve the color, or the achievement of the color.

After 2 hours of melting in a vessel in an oven at 14? 0 ° 0, the molten glass is poured into a thick raw body with a thickness of approximately 6.35 mm, which by means of cooling from 625 ⁰ C to normal temperature at one speed annealed can of approximately 3 to 4 ⁰ O per minute and then ground and polished "ground.

The polished A latte is then subjected by means of insertion into a muffle furnace and 25 minlltiges holding in the furnace at a temperature of about 735 ⁰ C the heat treatment. The oven temperature door is then increased to about 760 ⁰ G in 5 minutes and after 5 mintlgen Keep bie di "he temperature, the plate is then removed and allowed to have the same cool to 625 ⁰ C, and then, in turn, as described above, to about 625 ⁰ C tempered down to normal temperature.

The glass and this plate have essentially the following calculated composition;

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SiO ₂ 56.99b

B ₈ O ₈ 20.0

Al ₈ O ₈ 11.0

Na ₈ O 11.0 P ₈ 0.45

Cl ₈ 0.30

Ag ₈ O 0.11

Br ₈ 0.29

I ₈ '0.10

CuO 0.014

ZnO 0.005

As ₈ O ₆ 0.12

CeO ₈ 0.05

Pe ₈ O ₈ 0.06

O ₈ equivalents of the halides 0.29

and showing pieces cut from the plate, calling them exposed to mimicked sunlight and then putting them in the dark, phototropic effect and regression, as shown by the curves A in the pig. I reproduced, on.

Example 2

Bs is made by making an approach from another glass the following ingredients are mixed in the specified proportions:

Sand 228.0!

Boric acid 142.2

Aluminum trioxide 44.0

sodium nitrate 110.0 K'.trium fluoride 4.0

forming a matrix with:

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- 8 sodium chloride 2.96 parts

SiIb er oxi el 0.995

Sodium bromide '2.12

Sodium iodide 1.60

Copper oxide * 0.064

forming a metal halide mechanism, and:

Zinc oxide 0.02 part

Arsenic Oxide 0.48

Oeroxide * 0.16

as a solarizing agent and accelerator.

After 2 continuous smelting in a vessel in an oven at 143o ⁰ G, the molten glass is introduced into a blank having a thickness of 9.5 mm gegoeeen, the veroittels cooling from 595 ⁰ C to normal temperature door with a rate of about 2,5 - 3 ° / min. annealed and then ground and polished to a thickness of 6.35 mm.

The ground and polished plate is then introduced into a muffle furnace and held for 5 minutes in the oven at a temperature of approximately 735 ⁰ G, then removed and allowed to color change - to cool (315430 ⁰ G) and then in turn, as further described above, ^{annealed from 595 0} C up to normal temperature.

The glass and the plate essentially have the following calculated composition:

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SiO ₈ 56.9 # B ₈ O ₉ 20.0 Al ₈ O _a 11.0 Na ₈ O 11.0 * a 0.45 Cl ₈ 0.30 Ag ₈ O 0.12 Br ₈ 0.27 Yes 0.08 CuO 0.016 ZnO 0.005 As ₈ O ₈ 0.14 OeO ₈ 0.04 O ₈ ^ equivalent of the halide 0.29

and show pieces cut from this plate if they
exposed to simulated sunlight and then brought into the dark, phototropic effect and regression, as shown by curve B in the accompanying drawing.

Example 3 2 Mixing an An 0 parts He becomes another Glass mediate 1 the specified 2 theorem of the following Components in 1 0 parts manufactured: 1 228 0 sand 0 142, 0 Boric acid 44, Aluminum trioxide 110, share Sodium nitrate 4, Sodium fluoride forming one Matrix with .964 Well tri umchlurid , 570 Silver bromide , 404 Sodium bromide , 890 Sodium iodide , 064 Copper oxide

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forming a metal halide mechanism, and;

Zinc oxide 0.02 part

Arsenic oxide 0.40

Geroxide 0.40

as a solarization device and accelerator.

After 1.25 Btündigem melting in a Pxatintiegel in an electric furnace at 1430 ⁰ C, the molten glass is approximated into a blank having a thickness of 6.35 mm molded by means of cooling from 570 ⁰ G to normal temperature at a rate of about 3.5 ° C / min. annealed and then sanded and polished.

The tempered and polished blank is then introduced into an electric muffle furnace and kept in the same at a temperature of about 705 ° C. for 30 minutes. It is then removed from the oven and ^{quenched to complete the color change (315-430 0} G). Then, in turn, as described above, annealed of 570 ⁰ C down to Bäumtemperatur.

The glass of this blank or plate has essentially the following calculated composition:

SiO ₈ 56.95 »

B ₃ O ₃ 20.0

Al ₈ O, 11.0

Na ₈ O 11.0 P ₈ 0.45.

Eq ₄ 0.30

Ag _a 0-0.113

Be ₈ 0.29

I _a 0.10

CuO 0.016

^Zn0 10984 7/036 6 ^0> °° ⁵ BAD ORIGINAL

As ₈ O ₅ 0.12

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OeO ₈ 0.10

0 _a equivalent dee halide 0.29

and show pieces cut from this plate if they exposed to simulated sunlight and then transferred into the dark, phototropic effect and regression, as represented by curve Gin of the drawing.

The transmittance values according to curves A, B and 0 in the drawing are obtained by means of 51 x 51 x 6.35 mm pieces of the glasses of Examples 1, 2 and 3 under simulated sunlight conditions by illuminating the plates with a UV lamp and at the same time the transmittance is measured using Illuminant 0 as a light source with activation of a selenium photocell which is arranged behind the plates and is connected to a galvanometer.

The percent transmittance is read on the galvanometer at 5, 10 and 30 second intervals so as to to obtain the values plotted in the curves.

The drawing shows that the curves of the glasses in all three examples follow a similar pattern. That Darkness is most intense and fastest within the first 60 seconds after exposure and the fading is fastest during the first 60 seconds after performing the treatment. 90> or more of the total ">" occurs in the first 60 seconds, and in the first 60 seconds of fading the glasses form approximately $> of the entire loss of permeability back again.

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On the basis of the calculated analytical values, it can be seen in particular that the glass according to Example 2 contains the smallest amount of oil, that the glass according to Example 1 contains slightly more and the glass according to Example 3 contains the greatest amount. Taking this fact into account, it follows that on the basis of the transmittance values, the complete phototropic effect of these glasses depending on the exact proportions and combinations of all the factors present, it can be said that under this condition (1), with heights of the Cerraenge the same extent the glass becomes dark, is reduced (due to the change in the proportions of cerium compared to other activators) and (2) when increasing the amount of cerium, both the speed of darkening and the speed of regression are increased.

As indicated above, this is important according to the invention Feature on the finding that a remarkable improvement in the responses of the phototropic glasses can thereby be achieved that in the same single or in combination with arsenic and / or zinc as activators is incorporated, with specific references above Examples of execution according to the invention are given and <= r-Däutert are"

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Claims (13)

Claims 1. Object made of phototropic glass, which has a borosilicate glass matrix, a metal halide mechanism and an activator having, characterized in that is
the activator oeroxide / and the glass when exposed to sunlight reach approximately 90 $ of its darkness within the first 60 seconds, 2. Article according to claim 1, characterized in that zinc oxide is also present as an activator and the glass shows a hyperbolic corner formation in the dark, Article according to claim 1, characterized in that the matrix is an alumina-borosilicate glass, the mechanism consists of silver halide and a compound is present which is selected from the group consisting of arsenic oxide, zinc oxide, titanium oxide and iron oxide is present as an activator . \ 4. The object of claim 3 »characterized in that both arsenic oxide and zinc oxide as additional activators are present and the glass when exposed to sunlight is approximately 90 # of its darkening potential within the reached the first 60 seconds and in the dark the corner formation of approximately $ 50 of the total permeability that was lost within the first 60 seconds. 5. Object according to claim 1, characterized in that the matrix is a zirconium oxide borosilicate glass with a water-white appearance « 109847/0366 .. " ¹⁴ ~ 6. Method of making objects from phototropic Glass, in which the approach is components for the formation of a borosilicate glass matrix and components for the formation of a metal halide mechanism » is compounded, mixed and melted, the melted glass is converted into a predetermined 3-shape or shaped body and the metal body is then the "" armor treatment is subjected in order to make it phototropic, characterized in that a tanning compound the approach as an activator for the melting of the same is added. 7. The method according to claim 6, characterized in that the Ber ic an amount of 0.001 to 1.0 wt. $ £ of the batch, expressed as CeO _{8, is} added. 8. The method according to claim 7 »characterized in that an iron compound also in an amount of up to 0.5% by weight, expressed as ferric oxide, as an activator is added to control the color of the glass. 9. The method according to claim 6, characterized in that a zinc compound is also used as an activator in one Amount of 0.001 to 1.0 weight jb, expressed as ZnO, is added. 10. The method according to claim 6, characterized in that an arsenic compound is also added as an activator in an amount of 0.01 to 1.0j &, expressed as Ae _a 0 ₆ , - 15 109847/0366 11. The method according to claim 6, characterized in that arsenic and zinc compounds are also added as activators and the amounts by weight of these activators are approximately 0.001 to 1.0 wt / * of cerium, expressed as GeO _a , 0.01 to 1 ,, ^ arsenic expressed as as ₂ O _5, and 0.001 to 1.0 wt. f> of zinc expressed as ZnO amount 0 wt. 12. The method according to claim 6, characterized in that the approach consists of the following components essentially has the specified proportions: Sand 228.0 parts Boric acid * 142.2 Aluminum trioxide 44tO Sodium nitrate 110.0 Natriam fluoride 4 »0 Sodium chloride, 2.964 Silver bromide l »57O Sodium bromide 1, ', 04 Sodium iodide 1,890 Copper oxide 0.056 Zinc oxide 0.020 Arsenic oxide 0.400 Geroxide 0.20 ill 3 en-1II oxide 0.24. 13. The method «after claim 6, characterized in that the Ana "U3 essentially consists of the following components liffl has specified proportions! Jana -Ά ν: ·. (. xid 109847-0366 226.0 Parts Boric acid * '· "» ■ -: /. · -. U.V., 142.2 Aluminum ~ i I ■ '-' · * ί α 44.0 N π »ii'iurcn 110.0 H ^ i '{rl · ^τ " ^r 4, υ BAD ORlGlNM. Sodium chloride silver oxide sodium bromide Sodium iodide copper oxide zinc oxide Arsenic oxide geroxid 2.96 0.995 2.12 1.60 0.064 0.02 0.48 0.16 14o method according to claim 6, characterized in that the approach essentially contains the following components in the specified proportions: Sand 228.0 parts Boric acid 142.2 Aluminum trioxide 44.0 Sodium nitrate 110.0 Sodium fluoride 4 »0 Sodium chloride 2.964 Silver bromide 1.570 Sodium bromide 1.404 Sodium iodide 1,890 Copper oxide 0.064 Zinc oxide 0.02 Arsenic oxide 0.40 Ceria 0.40 Patent attorneys 109847/036 $ BATH ORIGINAL