Method of strengthening by coating bodies made of vitreous or partly vitreous material

METHOD OF STRENGTHENING BY COATING

BODIES MADE OF VITREOUS OR PARTLY

VITREOUS MATERIAL

This Invention relates to a method of strengthening bodies made of vitreous of partly vitreous material,

e.g., vitro-ceramic material, and to bodies strengthened by such method.

The mechanical strength of bodies made of normally annealed glass or a material comprising a certain proportion of a vitreous phase or phases, such as vitroceramic or vitrocrystalline material is adversely affected by the presence of microscopic surface cracks or scratches.

Such flaws act as stress-raisers when the defective surface is subjected to tensile stress. The microcracks may even propagate spontaneously. This explains why the tensile strength of a sheet of ordinary glass is twenty times lower than its compressive strength.

It is well known that the tensile strength of glass can be improved by thermally tempering it. The temperature conditions involved in such treatment are liable to deform certain articles and thermal tempering is not therefore always a satisfactory solution to the problem.

Special glasses which have appreciable hardness and resistance to scratching and/or which can be thermally devitrified to increase their surface hardness, are also known. The compositions of such glasses makes them expensive.

According to the present invention, a body made of vitreous or partly vitreous material, e.g,, vitro-cerajnic, is strengthened by forming on at least a part of the body a vitreous, crystalline or vitro-crystalline coating which 30 adheres to said body and which differs in chemical composition from said, body and. is composed, so that a solidsolid phase transformation which leaves or makes the coating at least as hard as said body, occurs or can be brought about in the coating.and then allowing or bringing about the occuriSK© of such phase transformation.

It has been found that if a piece of glass having surface scratches is provided by this method with a surface coating (which can be quite thin) which covers the scratched surface or surfaces, the coated glass can withstand appreciably higher tensile stresses than the uncoated glass. By virtue of the phase transformation in situ, the coating acts in some way to prevent propagation of the cracks but the reason for this phenomenon is not really understood.

The invention is particularly, although not exclusively intended for use in strengthening glass bodies, e.g., flat or curved glass sheets or continuous glass ribbons ( including drawn sheet glass and plate glass) and flasks, bottles, insulators, ampules and other manufactured glass articles. The strengthening of a sheet or ribbon of glass 20 will usually involve coating at least one or each major surface of the sheet or ribbon, if not the edges of the sheet or ribbon also. However, depending on the nature of the coating composition, advantages can sometimes be gained by coating only the edges or only the edges and the adjacent margins of the major surfaces of the sheet or ribbon. The application of the coating composition to the edges of a glass sheet and the subsequent treatment of the coating in accordance with the invention is particularly beneficial.

The invention can be applied with particular

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advantage for strengthening bodies made of glasses of ordinary composition, i.e., glasses formed frpm_; easily available inexpensive constituents,, e.g,, silica, soda,, lime and feldspar, since such glasses have remarkably: good optical, acoustic and thermal properties and for many purposes require improvement only in regard to their. mechanical'properties. Embodiments of the invention which are/of'special importance are processes in which a body of such an inexpensive glass :.is coated with a more easily crystallisable glass arid crystallisation,or recrystallisation is brought about in situ in the coating.

If the coating applied to the body is amorphous, this has certain advantages in that such an amorphous coating can be easily applied as a film with an even surface and: uniform thickness.

According to certain embodiments of the fvention, the coating composition is selected and applied to form a vitreous film in which solid phase transformation, e.g,, separation of vitreous and crysialline phases, can be '

20. brought about by thermaltreatment. Vitreous films adhere particularly wellto vitreous and partly vitreous surfaces. Compact vitreous films can moreover have a considerable thickness, say of thefot 1 mm.

As will hereafter be exemplified, it is possible . to coat a body with a vitreous film in which at least one crystalline phase can then easily be caused to separate by appropriate thermal treatment. Such a crystalline phase׳ or phases may form a fairly fine network on the. surface of , the coated vitreous or vitro-crystallirie material and.

3.0 ensure that if this material is broken it shatters into

-:.4 ־ very small fragments which do not cut. However certain vitreous films when subjected to appropriate thermal treatment exhibit phase separation in the sense that one or more new vitreous phases appear. A coating exhibiting different vitreous phases and which has undergone phase transformation in situ in that way can also prevent fracture of glass into cutting pieces or fragments. It has been found that various glass compositions which have not hitherto been thought to fall into the category of . demixing glasses, are in fact susceptible to the inducement of phase separation by suitable thermal treatment. Examples of such glasses will be given hereafter.

In other embodiments of the invention, the coating composition is selected and applied to form a crystalline coating in which solid phase transformation can be brought about by thermal treatment. As will be later exemplified, coatings containing one or more crystalline phases can be formed in which one or more new crystalline phases can be induced to form by thermal treatment. The phase transformation may involve the interdiffusion of interpenetration of different crystalline phases, which promotes the homegeneity of the coating. It has been found that in such crystalline coatings, mineral compounds with advantageous mechanical or optical or chemical properties, e.g־, spinels, can be easily and quickly formed. Vitreous phases can also be induced to appear in certain crystalline coating films. In general, thermal treatments for effecting this type of phase transformation comprise heating the coating to the melting temperature and then cooling it fairly rapidly. This procedure is of course only applicable if the phase transformation occurs at a temperature lower than the deformation point of the coated vitreous or partly vitreous material־

For achieving special optical effects, e.g., increased light-reflection, it is of advantage to provide a coating which in its final, transformed, state comprises vitreous phases with a high refractive index, e.g־, phases comprising inter alia, an oxide of lead, bismuth or' titanium.

The method according to the invention has the additional advantage that the final material may have higher . surface hardness as well as improved tensile strength. It will be apparent that this feature is of importance in enabling a material with a high degree of surface hardness to be fabricated using a substrate of glass without special constituents, e.g., a simple glass with a Mohs surface hardness of 7 or less. The coating conferring the requisite surface hardness may comprise hard constituents which have a melting temperature too high for them to be used in the manufacture of glass for drawing or otherwise forming into shaped bodies but which can be applied to form a thin film by one or other of the techniques hereinafter described. In order to achieve a high degree of surface hardness it ׳. is useful to form a coating comprising at least one crystalline phase formed by quartz (S10₂), zircon (ZrSiO^), . beryl (AlgBe^SigO.^), topaz (Al₂SiO^)(F־OH)₂, ZrB₂, TIN, TaC, ZrC, corundum (Al₂0^), B₂C, TiC, SiC or A1B, A body of glass having such a crystalline coating is not expensive and can have a surface hardness which is greater 30 than that of the mineral crystal. For instance, the Mohs hardness of topaz is 8, whereas a film formed of wide topaz crystals on glass having a Mohs hardness of 65־ was found to have a Mohs hardness of 85־«

Improved, surface hardness can be confered not only by coatings which are entirely crystalline but also by coatings which in their final state comprise both a crystalline phase or phases and a vitreous phase or phases. The vitreous phase may be integral with the׳vitreous material of the substrate. For example if one or more crystalline powders, such as quartz or corundum are sprinkled on. a substrate of glass heated to softening temperature, the crystalline phase is mechanically integrated in the surface layer of the glass and diffusion often occurs between the lattices of the crystals and the vitreous phase.

It is to be understood that the coating in which phase transformation occurs need not be absolutely continuous. Thus, small portions of a vitreous coated surface may be exposed. Moreover the phase transformation 20 can extend a little into the substrate surface and the adherence of the coating is thereby improved.

The coating can of course contain hard crystals formed in the phase transformation either from another crystalline phase or phases or by devitrification of a vitreous phase or phases. The latter procedure is favourable to the formation of a hard thin film of uniform thickness.

A body coated by a method according to the invention can be subjected to a tempering or toughening treatment,

e.g,, in a manner analogous to the thermal tempering of glass, if the body is able to withstand this treatment without deformation־ Alternatively compressive surface stresses can be produced or increased by the diffusion of ions into the coating from a contacting medium as in the known processes for chemically tempering glass־

The solid-solid phase transformation in the coating can in most case be brought about or initiated by thermal treatment. The expression solid-solid phase transformation is. not intended to exclude transformations 10 in which the constituents undergoing transformation pass through an Intermediate molten or flowable state. In fact a suitable thermal treatment may in some cases involve heating of the initially formed coating to bring it to an at least partially molten condition followed by cooling to a temperature zone favourable to the appearance of a solid phase or phases different in physical structure and/or composition from any phase present in the initial vitreous, crystalline or vitro-crystalline coating. In all cases however there is a solid-solid phase trans20 formation in that a material forming or forming part of a solid coating on the substrate is transformed after effluxion of time so that it forms a phase or phases of different structure and/or composition from that which it previously formed in the solid coating.

In using the expression thermal treatment we do not only include treatments in which an increase in the temperature of the coating occurs to bring about the phase-transformation־ For example constituents for forming an initial coating may be applied in molten condition and JO if the constituents are suitably chosen the only thermal treatment subsequently necessary is control of cooling so that the coating passes through a cooling schedule appropriate for ensuring that after or during solidification of the coating a solid phase transformation will occur within the coating, this transformation becoming apparent either during the cooling, or subsequently, after a time interval which may be short or long. Depending on the oomposition of the coating, phase transformation may take several seconds to several days.

There are important advantages in applying the coating composition to a vitreous or partly vitreous body while it is at an elevated temperature during a forming process, e.g., a drawing process in the case of sheet glass. In particular there is a considerable economy in heat consumption as compared with processes in which the body is allowed to cool and is then heated again preparatory to application of a coating. The coating of glass in the course of drawing it into sheets is one important field of use of the Invention. In such drawing processes the continously drawn ribbon of glass is cut up into sheets as it leaves the drawing machine. The coating composition can be applied in the drawing chamber of the drawing machine, e.g., a little above the glass meniscus. The coating ingredients may, e.g־, be salts, applied in atomised or vapourised form, or high melting powders, applied by sprinkling, and may form on one or each surface of theglass a film which is firmly held by or integrated with the glass. If the phase transformation which occurs in the coating or coatings gives the coating or coatings a hardness which makes cutting difficult, this is not necessarily a disadvantage since in some cases the phase transformation will not normally occur or be complete until after the time when cutting takes place in sheet glass manufacture« In cases in which the phase transformation normally occurs more quickly, it can be delayed«

The application, of a coating composition to the vitreous or partly vitreous substrate while this is at a temperature above its softening point ensures that the coating is well bonded to the substrate. In some cases there will be a release of volatile materials such as HgO, Hg, in the form of microscopic bubbles which also signifies a phase transformation. Such bubbles may form active centres promoting solid phase transformation״

If a coating composition is applied in molten condition to a cooled glass surface, the applied composition tends to improve such surface by a kind of polishing action, so that this procedure also has its advantage.

A variety of coating techniques can be used for applying a coating composition in carrying out the invention« The choice of technique will of course have to take account of the nature of the composition ingredients in any given case״ By way of example, the coating substances may be ¹'sputtered¹' or brought in the vapour state into contact with the substrate, e.g,, by evaporation of coating substances in vacuo. By these methode, thick or very thin amorphous layers of uniform thickness can be formed. Different constituents can be sputtered simultaneously or successively at rates which may be /2.

controlled during deposition. Alternatively coating.may take,place by immersion of the vitreous or partly vitreous body. This method enables fairly thick coatings to i>e formed of a glass which has a lower melting temperature than the material of the substrate. By way of example the substrate or a surface thereof to be coated can be immersed in molten salts to form a crystalline coating or a coating of relatively soft glass.

Different coating methods may be used for applying different constituents of a given coating, either simultaneously or successively,: Thus, for example, one constituent can be applied by evaporation in vacuo, and another constituent can be applied by immersion or sputtering. In actual tests, coatings were formed on ordinary glass by sputtering SiO and CaSiO followed by immersion in a suspension of AgCl + NaOH and then by a thermal treatment to induce a phase separation. It was found that when a thermal treatment was performed at low temperature the final coating possessed photographic properties. The phase transformation consisted mainly of the appearance of a new-crystalline, phase. When the thermal treatment was performed at a higher temperature the final coating possessed phototropic properties, i.e., it became reversibly less transparent to light when exposed to light of increasing intensity, the original transparency being recovered automatically with decrease in the intensity of the irradiating light. The phase transformation occurring as a result of the thermal treatment at the highter temperature resulted mainly in the appearance of a new vitreous phase.

In many cases phase transformation can be promoted by incorporating a doping agent in the coating composition. The effect of such agents can be to reduce the time required for phase transformation to occur or to induce phase transformation in glasses which would normally, on theoretical grounds, be considered incapable of demixing. As doping agents, particular reference is made to oxides of the following elements: Ti, Mn, Ou, Co, Cd, Ni, Al, Zr, Rb, Fe, Mg, Be, V, rare earths and precious metals, the selection in a given case being such that the valency of the cation of the doping agent is different from that of the cations of the new phases the formation of which i is to be encouraged. The doping agents referred to can become associated with other compounds in complex phases of the coating film, or they can form a,distinct phase.

For instance, a film formed from S10_n, Al0״, and Na_n0, in 2 ά כ ά which phase separations as a rule occur after 10 hours at 800°C, can be separated into the same phases after 1 hour at 700°C, if 2% by weight of TiO£ is incorporated, but the 20 final film then includes a phase composed almost exclusively of Ti02 in the form of rutilium.

Phase transformation in a coating can also be promoted by exposing the coating film to sound waves or ultrasonic waves of a frequency higher than 10,000 cycles/sec, and even exceeding 10 million cycles/sec. This treatment can be combined with some other treatment, for instance a thermal treatment. It has been found that in this way the incipient separation of phases, either vitreous or crystalline, can be hastened to a considerable 30 extent. Moreover, by this process unusual crystallographic phases are sometimes obtained, as is the case with zinc, cadmium and their oxides. Preferably, the waves are produced by electrostriction or piezoelectric processes, or by means of barium titanate generators, but more particularly at excessively high frequencies by magnetostriction, by superimposing a continuous magnetic field and a high frequency magnetic field vibrating at the specific frequency, e.g., of a sheet of steel disposed parallel with the surface of the sheet of glass or other 10 substrate bearing the coating film, or even vibrating at , the specific frequency of the film itself. More particularly, p electrical power varying from 50-3,000 watts/m has been used. The phase separation speeds are multiplied by 10... 1,000, depending on the power utilised,

The coating film formed in accordance with the invention can have, whether as a result of the thermal treatment or otherwise, a coefficient of expansion different from that of the vitreous or partly vitreous substrate. If the coating has a coefficient of expansion 20 higher than that of the substrate then the performance of the invention can exert the further beneficial effect of producing or increasing compressive stresses in the coated substrate surface. However it is permissible for the coating to have a lower coefficient of thermal expansion than the substrate because the effect of the coating in preventing or reducing the risks of propagation of surface cracks in the substrate can predominate over the reduction of compressive stresses in the substrate surface or the production of tensile stresses therein, so that the 30 tensile strength of the substrate is still improved.

Various specific embodiments of the invention will now be described and reference will be made to the accompanying drawings in which:

Fig. 1 is a vertical sectional elevation of part of a machine for drawing glass by the Pittsburg process;

Fig2 ־ is a section on line II-II in Fig. 1; and

Fig. 3 is a phase separation graph. Example I

Figs. 1 and 2 show a glass drawing kiln 1 comprising a bottom 2, a side wall 3 and a crown having a front element 4 and a central element 5־ The surface level of the glass is indicated by reference 6. A ribbon of glass 6 is drawn from the molten mass, in drawing chamber 14. The meniscus 7 of the drawn glass ribbon 8 is stabilised by a drawbar 9 disposed centrally with respect to two L-blocks 10. Inclined walls 11 connect the top end of the blocks 10 to a tower section 12 housing pairs of drawing rollers, only one 13 of which is shown. The drawing rollers draw the ribbon 8 upwardly through the tower section. The cooled glass leaves the tower section at its top and is cut into sheets.

Two main coolers 15 are disposed abreast of the glass ribbon 8 in the drawing chamber, close to the meniscus. Gas burner tubes 16 with gas discharge orifices 17 are disposed along the inner faces of the coolers 15 and provide series of flames 18, Higher in the drawing chamber 14 there are two auxiliary coolers 19 supported at one end by conduits 20 for supplying cooling fluid. The auxiliary coolers 19 are also fitted with a gas supply /2 conduit 21 formed with apertures 22 to provide flames 22'.

A hopper JO can be fed with one or more impalcable powders from distributors (not shown)« This hopper is formed by an inclined wall JI touching a rotary distributing cyclinder J2, the surface 3J of which is sanded, . and by an inclined wall 34 of adjustable height the bottom end 35 of which is a little distance away from the surface of the cylinder 32. The bottom end of the hopper JO communicates with an inclined chute 36, which extends through the wall 11, 10 the bottom end 37 of this chute being near the glass ribbon 8.

The lower end portion of the chute which is exposed to the high temperatures is surrounded by a sleeve J8 through which water is circulated via apertures 54 and 4θ» Electric vibrating elements 41 are attached to the bottom of the chute J6.

Powder feed equipment identical with that having references JO-41 is installed symmetrically at the other side of the drawing chamber for feeding powder to the other side of the glass ribbon but this further equipment has been 20 omitted from the drawing»

Powdered material is supplied in strictly metered amounts into the hopper JO so as to keep this filled to a .level slightly higher than that of the bottom end of the inclined wall 34־ The cylinder J2 rotates clockwise as shown by the arrow and feeds the powder into the chute J6. The powder is delivered in a fine shower onto the surface of the glass ribbon 8 above the meniscus 7־

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<td colspan="3"> Glass made from a batch of the following coposition</td>

<td></td><td> by weight!</td><td></td>

<td></td><td> Si°₂</td><td> ! 70%</td>

<td></td><td> Na₂0</td><td> 1 12%</td>

<td></td><td> CaO</td><td> 1 10%</td>

<td></td><td> MgO</td><td> 8 3%</td>

<td></td><td> Fe₂°3</td><td> ! traces</td>

<td></td><td>^A12°3</td><td> « 5%</td>

<td></td><td colspan="2"> was drawn in apparatus according to Figs. 1 and 2. The</td>

<td> 10</td><td> temperature of the glass at the</td><td> meniscus 7 was 920 C. A</td>

ribbon drawn from such a glass, has, in ths ooolsd stats, a surface hardness of about 6.6 in the Mohs soale.

The|ppper 30 (and the other hopper which is not shown) were fed with a powdered special glass (dimensions between 10 and 50 microns), obtained by melting a batch of the following od|osition at 1000 0, following by refining, sudden cooling and.crushing!

ZnO . ! 60% ³2°3

SiO_{2 ;}!10%

*־ .¥5

Λ1.0,I 2¢

צ 2

Na₂0 1 2%

The powder leaving the chute 36 and, the chute on the other side of the drawing ohamber, formed adherent coatings such as 42 on the glass ribbon 8, the glass at the contact zone being still soft, The applied powder became formed into vitreous coating films in the tower section, the temperature 0 at the upper end of whioh was 60 C. The coated glass could 30 be readily out even after storage for one hour at ambiant temperature. However a solid phase transformation

245/2 had already commenced in the coatings by that time and due to that fact the glass was found to divide strictly along the cutting line«

The phase transformation continued during storage and after 100 hours at ambifint temperature the coatings comprised a vitreous phase of zinc borate and another vitreous phase of aluminium phosphosilicate. The coating film 42 on each side of the drawn glass had a uniform thickness of some fractions of a millimeter.

The bending strength of the glass was increased tenfold by the coatings.

A.process was performed identical to that just described except that 1$ by weight of industrial Ti0₂(grain size 20 microns) was added to the above powdered glass in the hoppers.

The coating films were given the same thermal treat» « ment, i.e., cooling from 920 C to Θ0 C in the tower section

12. The cooled coated glass could still be easily cut, but phase transformation in the coatings was completed in ten hours» This acceleration is possibly to be attributed to the titanium cations having a valency of 4 which differs from that of the aluminium catipns (+ 5) and the zinc cations (+ 2). Moreover, in addition to the vitreous phases which farmed in the coatings in the comparative process, the coatings included a practically pure crystalline phase of Ti0₂. When the coated glass was bent to breaking point following the completion of the phase transformation, it shattered into very small non-cutting pieces.

A further process was then performed identical with that just described save in that 5% by weight of alumina

- IT 245/2 (grain size^L ?0 microns) was added to the powdered glass in the hopper JO, in addition to the 1/ by weight of titanium dioxide. The resulting coated glass had similar properties to that obtained by the previous process but the surface hardness was greater. The Mchs hardness reached a value of Θ.5 in ten hours. This is attributable to the appearance of a crystalline phase rich in corundum, in the coating layers. After the treatment it was found to be very difficult to score or scratch the coatings. 10 Example II

Vitroceramic sheets were produced from a batch having the following composition by weight« s!0₂ «50/־

A1₂0j «25/

Li₂0 . «8/

Ti0₂ «4/

CaO «7/

P₂°₅ «6/ by melting, refining, moulding and thermal treatment for 0 80 hours at 700 C. The vitroosramio material was crystalline 20 in the body of the sheets and opaque, but contained at least in the surface regions of the sheets, about 25/ vitreous phase.

The material was fragile and had a tensile strength of 11 kg/mm .

First 10/ by weight AgCl, and then simultaneously 20/ Si50/ CaSiO20/ AlgO^ by weight were deposited on the sheets by evaporation in vacuo and in darkness . 0 The sheets were then heated at 600 C in darkness for 20 hours. Phase transformation took place in the deposited coating films with the result that the coatings comprised

245/2 three phases« aluminium silicate, calcium aluminate and silver chloride. The sheets had photographic properties.

Their tensile strength was 100 kg/mm .

Example III

Bottles and electrio insulators of borosilicate glass formed from a batch having the following composition by weight*

Si0₂ 60% ן

Na^O 8 12%

CaO 8 10%

MgO 8 6%

B₂O₅ 8 6% p₂0₅ 8 1% ^a12°5 8 5% were coated by evaporation in vacuo with a deposit of 60% SiO , 10% Al Q_, 10% CaO, 5% MgO, 5% Ti010% ,״ Na0״ d d ע d d (percentage by weight), the coatings having a thickness of 0.1 mioron. ¹

The bottles were then irradiated with X-rays to initiate nucleation therein and subsequently heated for one hour at 500 C during which time the bottles were intermittently subjected for periods of 5 seconds at intervals of JO seconds to ultrasonic pulsations with a frequency of 50000־ cycles per second. Vitreous crystalline^appeared in the coatings, inter alia rutiltum, sphene, wollastonite, diopside, enstatite albite, in a vitreous phase. The impact and vibrational strength of the bottles was doubled by the process, and on breakage, the articles shattered into small substantially non-cutting fragments.

Example IV « »»n uriraffe!..*»-. .ד.»: t-J t

Fig« 3 is a graph of a phase separation glass formed from 5% PgO^ and 95% of a mixture of SiO₂ and MeO, Me being a cation, such as barium. The relative proportions of SiOg and MeO are plotted on the abscissa, and the temperature on the ordinate. The liguidus curve 51 is also shown and a horizontal line 52 indicating the end of the liguidus and the start of the solid. In the liguidus curve there is a depression 53 believed to be attributable to a demixing zone 54. A glass was formed having a composition of which the representative ordinate intersects the depression 53־ On cooling the glass it was found that in fact a demixing or phase separation zone 54 existed below and above the horizontal line 52. A glass of the same composition was used to form a film on a glass substrate and then cooled so that phase separation occurred. In the result the substrate was strengthened and could withstand tensile loads which would otherwise have caused surface cracks in the substrate to be propagated.

The diagram serves to indicate the manner in which other glass batches of which the demixing properties has not hitherto been recognised can be investigated. Example V

A glass of ordinary composition in the form of a sheet 1 m x 1 m x 0.003 m in size with a ?lohs surface hardness of 6.2 was coated at 80°C by deposition of the following oxides by simultaneous vaporisation in vacuo., in the molar proportions indicated:

<td></td><td> F 0 2^U3 0.5 MgO 1 Mn0₂ 1 Ti0₂ 5 a1₂0₃ 5 CaO 3</td>

The thickness of the coating was about 0.02 micron. The coating was exposed to radiant heat to increase its temperature progressively up to 1000°C while the sheet was 10 disposed on a flat surface. After cooling, an abundant crystallisation became manifest, the crystalline phases comprising ilmenite and anatase, which were present in an amorphous phase of calcium aluminate. The coated glass now having a Mohs, surface, hardness of .6,5 could be readily cut. The coated surface was then irradiated with X-rays for 24 hours at 800°C. On cooling of the glass it was found that the phases previously formed had been transformed, with the appearance of rutilium, corundum, pyrolusite, calcium aluminate, hematite and a little 20 ilmenite, which were finely dispersed and overlapped one another. The surface hardness was then 8.2 on the Mohs scale.