DE1696110B1 - PROCESS FOR THE PRODUCTION OF GLASSY COATINGS ON SUBSTATE MATERIALS BY VACUUM EVAPORATION USING ELECTRON BEAMS - Google Patents

Description

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The invention relates to a method of manufacturing glass in several layers one on top of the other from glassy layers to any steam.

Substrate materials by means of electron beam furnace in By the method according to the invention

High vacuum. a multitude of new areas of application

Several methods are known to produce glassy 5 sen.

Layers by vapor deposition on substrates. Care must be taken that the water content is through

place. Inserting dry raw materials kept as low as possible

One is based on the fact that it is easily oxidizable. Furthermore, glass compositions are few

Metals or metal alloys, such as. B. lead - SiIi- suitable for the delivery of larger amounts of acid

zium, lead — tellurium, aluminum — silicon, in an io substance tend to be.

Oxygen-argon atmosphere under a total during the melting process are suitable as a protective gas

pressure of about 2.5 · 10 ~ ² Torr in the form of an electrolyte - for example, dried air, nitrogen or noble

Trode is sprayed and gasses down as an oxide on the substrate.

be beaten. This method is used on metals as furthermore, it has been found to be unfavorable to use glasses

Starting material and also to use the solid-15 large contents of components, their

limited to atomization than vapor deposition. You vapor pressure is much greater than the pressure in the recipient

also requires a relatively high level of oxygen when it is treated in a vacuum. Therefore, invent

partial pressure of about 1.2 x 10 ^-2 Torr, which is why they dung according to the multicomponent glasses Although alkali

for evaporation by means of electron beams that contain, but not more than 10 percent by weight, alkali

run at pressures less than 10 ~ ⁴ Torr, not suitable 20 oxide.

is. The quality of the vapor-deposited films has proven to be particularly advantageous.

nothing said. The method has been proven on the manufacturable glass, whose boric acid content is no more than

Alloys restricted, it therefore does not allow, is 25 percent by weight.

the network converters, such as lithium, sodium, potassium Also, according to the invention, some crystalline

etc., to be introduced into the glass layer produced. 25 mixed or segregated multi-component glasses

Another method involves multiple metal vapors and deposition. Through this

oxides, which are heated separately in the boat and we succeed in making glasses usable for the process,

10 ~ ⁵ torr can be evaporated. The disadvantage of heat treatment is the same for other cases

The method is that disadvantageous crystallization or separation occurs from separately evaporated.

Oxides very difficult to obtain homogeneous glasses 30 It has been found that to use the

permit. Method according to the invention multi-component

It has also become known that glassy, single-composite glasses are particularly suitable, the following components

nent layers by means of electron beam furnace in single or mixed contain: oxides of L, IL,

Evaporate high vacuum. These are made of quartz III., IV. And V main group as well as oxides of the L, IL,

standing layers turned out to be composed of many 35 HL, IV., V., VL, VII. and VIII

Individual particles consisting and therefore not dense Periodic Table of the Elements, in particular

and cracked, so that their possible uses are those of lithium, sodium, potassium, barium,

were limited. Titanium, vanadium, niobium, tantalum, boron, aluminum,

It has also come to be known as vaporizable gallium, silicon, germanium and phosphorus.

The method according to the invention can also be used in FIG

turn around. These glasses usually contain zinc- the way that a hard one can be done

Lead borates with amounts of 50 to 80 ° / ₀ PbO. Alkali fusible, but easily vaporizable alkali borosilicate

is not contained in these glasses, so that difficult katglas in an easily meltable, but very difficult

volatile oxides are not evaporated. vaporizable glass dissolved or intimately with this

The object of the invention is a method for mixing and this solution or mixture is used as a position of vitreous layers on any substrate to be evaporated multi-component glass. Here materials by means of an electron beam furnace in the high through the number of possible vacuums in which layers are obtained, the multi-component glasses with their special inherent homogeneity, do not form cracks and the other shafts are increased considerably.
The known methods do not have the disadvantages of the known methods, expediently, the oxides used according to the invention also enable the evaporation of difficult multicomponent glasses. Based on:

According to the invention, this object is achieved by

that an alkali-containing, at most 10 percent by weight SiO ₂ 35 to 85 percent by weight

Multi-component glass containing alkali oxide to 55 ^B iA 5 to 25 percent by weight

is vaporized, which previously largely under vacuum Li ₂ O 0 to 5 percent by weight

degassed or under a protective gas atmosphere, Na ₂ O 0.5 to 10 percent by weight

has been melted. K ₂ O 0.5 to 10 percent by weight

Depending on the manufacturing conditions and use, Al ₂ O ₃ 3 to 40 percent by weight

appropriately, these layers can contain one or more of the 60 CaO 0 to 25 percent by weight

Have the following properties: They can be dense, BaO 0 to 25 percent by weight

hard, flexible, either electrically non-conductive or TiO ₂ 0 to 20 percent by weight

semiconducting, antistatic, hydrolytically good resistance, ^ O ₅ ° to 50 percent by weight

transparent, of high or low refractive index

be, they can be both colorless and colored, 65 To obtain thick layers or layer packages, In accordance with the invention, one or more multiple impact strengths can be thermally insulating and of great electrical penetration. For special purposes, they can be opened, component glasses simultaneously or alternately be vaporized by different multi-component.

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Because when using an electron beam furnace this is melted down in portions. The platinum crucible is brought to a high temperature very quickly and is placed in an evacuable and inductive heating system and suffers a thermal shock. The melted glass is heated up to 1620 ° C to ring the thermal expansion coefficient preference. Now, carefully, <40 · 10 ~ ⁷ / ° C will be in the range of 20 to 300 ° C. 5 evacuated until a pressure of less than 10 torr is reached

To other multi-component glasses for that is. This is accomplished in around 12 hours. Thereafter To make the process usable, the multi-component is poured and cooled in the usual way, nentenglas expediently before the start of evaporation. The evacuation time is expedient by stirring Shortened to one temperature by a heating device. The glass made in this way has heated above the lower cooling temperature. io the following composition:

While the previously known vapor-deposited _{siQ g2 3} percent by weight

Layers, in particular those with a crystalline structure- g q -q γ percent by weight

for mostly more or less strong tensile stresses ^ ['[]]] [] [[[]] ₂ ', 9 percent by weight

have, which sometimes even with thicknesses above _{NQ 2n weight percent}

0.1 μΐη to cracking or peeling from the under- 15 _{K o 0 4} percent by weight

situation are those according to the described

Process made vitreous layers largely It has the following properties:

free of tensile stress and because of its excellent _α _ 29 0-10 ~ ⁷ l / ° C

Adhesion to the common substrate material j _ ^ O q

alien still stable even with relatively large thicknesses. 20 VA = 1412 ^° C

Due to these properties, it is also density = 2 20 a / cm ³

possible to give the layers a strength-increasing jj, ^ ₆ J ^ qq __ 254 ° q

To give effect by using a suitable substance - hydrolytic class 1

selected the condensation of the evaporated glass as η = 1 4679

carries out that permanent compressive stresses 25 _ 55'41

form in the layer. This works best on ^D '

Documents with good adhesion, such as B. Glass A pane of this glass is inserted into an elec-

surfaces, if a multi-component glass, the electron beam furnace of the usual design is used in such a way that thermal expansion coefficient before and / or it can be rotated during steaming, after evaporation and condensation on the 30 The electron beam is deflected by 180 ° C, see above Substrate is lower than that of the substrate material so that the glass can evaporate freely onto the substrate evaporated and deposited on the substrate. Before the electron beam is switched on, is, while this is on a opposite of the sample is diminished. With this glass he can normal use temperature increased temperature electron beam are immediately fully switched on, is located. After cooling to normal temperature without the thermal stresses occurring in the glass then according to a known principle in the disturb. It can be used on any substrate material condensed layer tangential compressive stresses, any shape can be evaporated. Body with which need to increase the mechanical strength of three-dimensional expansion in two planes and surface hardness of the base. That are rotated.

For this purpose, the layer thickness is expediently at least 40. The vapor-deposited layer has the following properties. For what has not yet been solved, it is: dense, transparent, bendable in a tight radius, problem, effective surface hardening of antistatic, scratch-resistant, electrically insulating, thermal glasses or ceramic materials through vapor-deposited insulating, very good hydrolytic resistance.
Coatings without the use of diffusion processes

are thus achieved by the new method 45 Example2

Opportunities for simple technical implementation opened up. A glass with the following composition

The compact structure obtained _{according to the invention siQ g0 90} percent by weight

ten layers, which have a volume factor very much according to jq -j2 8 percent by weight

1, gives them a high £ 50 '.'. '.'. '.'. '.'. '.'. '.'. '.'. '. 2 ^ 2 percent by weight

Degree of protective effect against atmospheric and _{N Q} 5 percent by weight

chemical influences, which are usually already at low _{KQ 0 6} percent by weight

Layer thicknesses is achieved. In this way, ²

z. B. on optical glasses or crystals optically perfect protective coatings can be achieved in a porcelain mill with porcelain balls. Also ground for a long time, so that 91% <10μ and 46% <5μ metal and plastic surfaces can be after. 1000 g of this powder will be vitrified in a platinum crucible using a new process. Also suitable are filled, which is located in an inductively heated vacuum oven, the layers for protective cover and encapsulation. The glass powder is used to remove the from mechanically sensitive surfaces such. B. surface water ^{heated to 580 0} C and at the same time thin-film circuits or surface mirrors, and 60 the pressure is lowered to 0.1 Torr. The glass is left for 4 hours at this temperature for sealing and isolating inhomogeneous doors. Then surfaces, e.g. B. of fiber optic disks. the temperature increased to 700 to 720 ⁰ C, at the same time

. -I ₁ ^w i ^f d the pressure is reduced to 0.05 torr. This tempe-

Example 1 _{temperature is} held for 20 hours. This escapes

A mixture of 8080 g SiO ₂ , 2240 g boric acid, 65 water bound in the glass. Subsequently, the 232 g of Al ₂ O _3, 628 g of sodium carbonate, 150 g sodium glass is heated in a short time to HOO ⁰ C. This chloride, 91 g of potassium carbonate were kept in a platinum temperature for 2 hours. Now the crucible is heated at temperatures between 1550 and 1600 ⁰ C glass to 1500 ⁰ C and 1 hour at this temperature

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leave temperature. After that, the glass is as usual. The evaporation properties of the glass are poured and chilled. Because of the low content of alkali oxide and the low water composition, the glass melted in this way has the following melting process: salary very good.

SiO ₂ 81.9 weight percent Example 5

B ₂ O ₃ 13.0 weight percent.

Al ₂ O ₃ 5.1 percent by weight ^Em common with the following composition

Na ₂ O 2.0 weight percent SiO ₂ 7330 g

K ₂ O 0.5 percent by weight B ₂ O ₃ (dehydrated) 1810 g

Further properties: Na O * 143 g

a = 29 · 10 ~ ^{7 1/0} C. is in a platinum-iridium crucible in an electric

heated furnace ^{melted at 155O 0} C, while-

The properties of this glass are largely identical to those mentioned under Example 1, when the oven is flushed with sharply dried air. Also will. After melting, the temperature, the composition and the properties are increased ^{to 1700 ° C. in 2 hours.} The layer steamed for refining hardly differs from that when the temperature is left for 8 hours, as mentioned in Example 1. After that the temperature will be below constant

20 Rinsing with dry air reduced to 1600 ° C and that

Example 3 Glass poured as usual and cooled. By a

Tempering at 1200 ⁰ C is the glass in a

A mixture of the composition can be converted into a partially crystalline state. This glass

. shows how during evaporation in an electron beam furnace

^ ¹ λ ² ', .' ^ * nl ^ ^a 5 described under Example 1, excellent property

B ₂ O ₃ (dehydrated) 400g _properties

Al ₂ O ₃ 200 g

Li ₂ CO ₃ 100 g B eis ρ ie 1 6

r? ^a ; v? ³ Z? ^§ A mixture of composition

CaCO ₃ 'Ig or.

BaCO ₃ 181g ³⁰ SiO ₂ 7015g

LiF 70 g B ₂ O ₃ (dehydrated) 1770 g

is placed in a platinum crucible in an electrically heated BaCO 1300 s

Oven at a temperature of 1500 ⁰ C inserted. CaCO ³ 360 ε

After the mixture has melted, the 35 vr ^ Λ ^ n ^

Temperature increased ^{to 1650 °} C. in 2 hours. For the LiF 175 s

The glass is refined at this temperature for 10 hours

leave long. Thereafter, the temperature of 1500 ⁰ C is lowered at 1400 ⁰ C in a platinum crucible in a elekin a ¹ J ₂ hours and melting the glass, as usual, symmetrical heated furnace, during which poured and cooled. During the loading and unloading period, the oven is flushed with sharply dried air. During the melting process, the furnace is dried with sharp. After melting, the glass is rinsed with stirring air. heated to 1600 ⁰ C and for lautering for 3 hours

Leave it at this temperature due to the low levels of alkali oxide. Under continuing The low water rinse obtained by this method with dry air is the glass with stirring content, the glass shows excellent evaporation 45 cooled to 1400 ° C, cast as usual and properties. cools. Because of the segregation that has occurred

this glass is white-opaque. Example 4 The evaporation properties of this glass are

very good.

A Mixture of Composition 50 The method according to the invention is carried out in one

_{glQ o} 4g ^ 0 Embodiment based on the drawing, in wel-

BO ² (drained) ................ 1500g ^{cher a Vorricntun} E to carry out the

A \ Q H60 _{g is} shown schematically and by way of example,

BaCO ............. 1600 g explained in more detail.

CaCO * 3160 ε ⁵⁵ ^ ^u ^ ^ ^er rotatable bracket 1 by the engine 3

Na »CO 516 ε ^u ^ ^er ° ^ ^e shaft 4 is driven, the majority lies

Ljp ³ YJ ^ component glass 2. For heating, the furnace or radiator 6 attached to the lever arm 7 is opened by means of a

is swiveled over the sample in a platinum crucible and in an electrical rotary feedthrough 8. now

heated oven of conventional design at 1450 ⁰ C inserted 60 the multi-component glass to the desired

and melted, during which the furnace is heated to temperature. If this is reached, the

flushed with sharply dried air. Set the temperature by rotating the feedthrough 8 from the oven

is now increased to 1500 ⁰ C and meanwhile swiveled out the steam jet area of the glass and

Melt stirred to accelerate the lautering. locked. The electron gun 5 is now switched on.

The temperature is left for 3 hours at 1500 ⁰ C 65 switches so that the glass evaporates and on the

and the irrigation continued continuously. The substrates 9 to be vapor-deposited are then deposited. That

The temperature is ^{lowered to 1400 °} C. with stirring and the system is removed from the outside atmosphere

poured the glass as usual and chilled. Recipients 10 completed.

Claims (7)

7 8 Claims: SiO2 35 to 85 percent by weight 1. Process for the production of glassy B ₂ O ₃ 5 to 25 percent by weight Layers on any substrate material by Li ₂ OO up to 5 percent by weight Vacuum evaporation using electron beams, Na ₂ O 0.5 to 10 percent by weight characterized in that an alkali 5 K ₂ O 0.5 to 10 percent by weight Li-containing, at most 10 percent by weight alkali Al ₂ O ₃ 3 to 40 percent by weight oxide containing multi-component glass on CaO O up to 25 percent by weight is evaporated, which previously largely BaO O up to 25 percent by weight under vacuum degassed or under a protective gas atmosphere, TiO ₂ O up to 20 percent by weight has been melted. io V ₂ O ₅ O to 50 percent by weight 2. The method according to claim 1, characterized in that the multi-component glass is an alkali 8. The method according to claims 1 to 7, daborosilicate glass is vaporized. characterized in that a difficult to melt, 3. The method according to claim 2, characterized by this but easily vaporisable glass in a light draws that an alkali borosilicate glass vapor-deposited 15 fusible, but difficult to evaporate ble whose boric acid content does not dissolve more than 25 Ge glass or is intimately mixed with it is true percent. and this solution or mixture as an evaporation 4. The method according to claims 1 to 3, da- fendes multi-component glass is used, characterized in that the partially crystallized 9. The method according to claims 6 and 7, da-multicomponent glass is vaporized. 20 characterized in that one or more multiple 5. The method according to claims 1 to 4, da- component glasses simultaneously or alternately to characterized in that segregated multi-component generation of a layer or of layer packages component glass is vapor-deposited. be vaporized. 6. The method according to claims 1 to 5, 10. The method according to claims 1 to 9, characterized characterized in that multi-component 25 characterized in that the multi-component glasses be vaporized, the oxides of the L, IL, glass before the vapor deposition on a Tempe-III., IV. And V main group and oxides of the L, rature heated above the lower cooling temperature IL, ΙΠ., IV., V., VL, VII. And VIII. Subgroup becomes. of the Periodic Table of the Elements, in particular 11. The method according to claims 1 to 10, dadere but the oxides of lithium, sodium, 30 characterized by that a multicomponent potassium, Barium, titanium, vanadium, niobium, tantalum, boron, glass, their thermal expansion coefficient Aluminum, gallium, silicon, germanium and before and / or after vapor deposition on the subphosphorus included individually or mixed. strat is lower than that of the substrate material, on- 7. The method according to claim 6, characterized in that vaporization is carried out while the substrate is characterized in that multi-component glasses follow 35. compared to the normal usage temperature, the composition can be vaporized: the temperature is maintained at an elevated level. 1 sheet of drawings COPY 109 527/297