Coatings for glass

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:` 13271~ . ~ ',.:''', ~' COATINGS FOR GLASS The inventlon relates co coatings, and in particular to ~he productlon of underlayers useful ln ehe suppression of iridescence and in che procectlon of overlying layers sensitive to alkali metal ions from migraeion of such lons from an underlying glass surface.

G.B. paten~ 2 031 756B is concerned with thin transparene infra-red reflecting semiconductor coacings ~hlch are useful in i; improving the insulation proper~ies of wlndows and which, being -` eleccrically conduccive, can serve as reslscance heacers, for example to remove ice or condensation from windows.

According to ` GB 2 031 756B, the use of such coatings has been limited by che ;

fact ehae ehey exhibit iridescence colours, especially ln reflected `;~ light; these iridescence e~fects are widely regarted as aesthetically unsatisfaceory, and the problem is made worse by the ` variaeion in irldescence colour which occurs ~ich small varia~ions in coating thickness. GB 2 031 756B proposes to overco~e the problem of iridescence by depositing an appropriate iridescence reducing underlayer under the semiconductor coating and reco~mends, ~ ~ as a preferred form of underlayer, a layer having a refractive ;

index`in the range from 1.7 to 1.8 and a thickness in the range 64nm and to 80nm.

According to GB 2 031 756B, the underlayers may be produced by co-deposlting a mixture of components calcula~ed co provide che required refractive lndex, for example a mixture of 84+3~ slllcon nltride and che balance sllica, referred co as slllcon oxyn~cride. -~ : ~ .` ,, ~ ,' 1327143 - 2 Such sllicon oxynierlde fllms may be formed by chemical va~our teposltlon from a source of sillcon (e.g.

SiH4,(CH~)~ SiH2, (C2HS) SiH2, (CH~)4Si, SiC~ , SiBr~, a source of oxygen (e.g. 2~ H~0, N20) and a source of nierogen (e.gs N~H4, NH3, HN3, CH3NHNH2, (CH3) UNH~) or a source of both oxygen and nitrogen (N0, NH20H, N2H4 H20) on hot glass at a temperature of 500C to 600C.

However, although there ls a requirement for a sultable lridescence reducing underlayer, the underlayers proposed in GB patent 2 031 756B have noe been used commercially to any signlflcant extent. This may be because of difficuleies, ln parelcular ehe long deposition time required, in producing ;

underlayers of sufficient quality and thlckness by the known methods.

GB patent specification 2 163 146A is concerned with the production of barrier coatings on a glass surface to prevent migratlon of alkali metal ions from the glass inCo an overlying layer sensitive eo alkali metal ions, for example lntium tin oxide.

It describes ehe producelon of transparent barrler coatings~ having good lighe eransmlssion and excellent barrier propereles by pyrolysis of silane on a hot glass surface above 600C in the presence of a gaseous electron donatlng compound; the presence of the eleceron donatlng compound is found to result in incorporation of oxygen from glass into the coating so formlng a eransparene barrier coating up to 50nm thick on ehe glass surface.

The electron donating compounds which may be used in the process of G8 pacent speclfication 2 163 146A are compounds which ~ ~ 3 ~ 13271~3 contaln, eleher ln bonds or as lone palr electrons, electrons whlch can be donated inco ehe electronlc structure of suitable acceptor molecules. The use of the electron donatlng compound ls found to result in the incorporatlon of oxygen from the glass wlth silicon from the silane eo form ehe eransparent barrier coatlng on ehe glass. Although the mechanism ls noe u~derstood, it ls believed to involve adsorption of the electron donating compound on tbe glass ~ surface.

Ie ls preferred to use an electron donaelng compound ;

; whlch is oxygen free, for example ethylene, or which, although it concains some oxygen, ls generally regarded as reducing, for example carbon monoxide and alcohols.

Bécause ~he transparent barrier coatings may be prepared in the absence of free oxygen and compounds generally regarded as oxidising agents, ehe barrier coaeing may be applied to a ribbon of float glass as ie ls advanced over the molten metal bath on which ie is formed without undue risk of oxidising the molten meeal.

Unfortunately, while the use of oxygen free electron donating compound alleviaees ehe risk of ehe silane being oxidised before it reaches the glass surface and of ehe reactane gas oxidising a moleen meeal bath on which ehe glass ribbon is supported, there is insufficient oxygen availability from the glass for the formation of the thicker irldescence reducing underlayers recommended in GB patent 2 031 756B. While thicker layers may be produced by using oxygen-containing electron donating compounds, for example carbon ;

dioxide, it is found that the use of a combination of silane and carbon dioxide results in elther thin coatings of poor durability _ 4 _ 1 3 2 7 1 4 3 or, when aetempts are made to thicken ehe coatlngs, a whlte hazy deposle.

Moreover, when attempts are made to produce barrler coatings of very hlgh transparency (e.g. a light transmlsslQn not less than 2Z below thae of the base glass) uslng a comblnatlon of sllane and ethylene in accordance wlth GB 2 163 146A, the barrier properties of the coatings were found to be lnsufficiently conslstent for some applicatlons.

There is a need for a process, sultable for commercial operatlon on a floae glass producelon llne, for produclng an lridescence reduclng underlayer as recommended ln GB patent 2 031 756B.

There ls also a need for a process, suleable for :

commerclal operaelon on a float glass produceion line, for producing coaeings whlch are effectlve as barrlers to che mlgraclon of alkall metal ions from the glass and have a very high degree of ~transparency.

It has now been found that these needs can be met by a process in whlch a gaseous mixture of a silane, an ethylenlcally unsaturated hydrocarbon and carbon dloxlde is direceed on to a hot glass surface to deposlt a coatlng containing silicon and oxygen on the glass surface.

Accordlng to the present invention there is provided a process for forming a useful underlayer on a glass surface comprising directing on to che hoc glass surfac~ at a cemperacure of 600C to 750C a gaseous mixture of a sllane, an unsaturated ` - 5 - 1 327~4~ hydrocarbon compaund and carbon dloxide thereby deposlting a tran~parent layer containlng slllcon and oxygen on the glass surface.

Underlayers produced by the process of the lnvenelon act as barrlers to the mlgratlon of alkall metal ions from the glass and are useful when an overlylng layer, sensltive to the migration of alkali metal lons from the glass, ls applied dlrectly or indirectly over the underlayer. Accordlng to a further aspect of the invenelon, the process addieionally comprlses the seep of applylng a layer, sensitive to the mlgratlon of alkali metal ions from the glass, over the underlayer.

To produce an infra red reflecting and/or electrically conduceing coating of reduced iridescence~ an infra-red reflecting and/or elecerically conductlng layer is deposited over the -~ lS underlayer.

Thus, according eo a still further aspect of the invention, ehe process additionally comprises the step of deposlting an infra red reflecting and/or electrlcally conductlng layer over the underlayer.

This overlayer may be of a semicontuctor metal oxlde, for example tln doped lndlum oxlde or doped ein oxlde, especially fluorine dopet tin oxlde. ;~ Both the underlayer ant ehe overlayer may be appliet to float glass on the protuction line on which it is mate.

In this case the overlayer may be a fluorlne dopet ein oxide layer deposieed by pyrolylic decomposition from a solid (as described, for example, in G8 paeene specificaeion 2 lS6 386B), liquid (as described, for example~ in GB patent specificaeion l 523 991) or vapour sourc~ - 6 - 1 327~ ~ (for example, gaseous stannlc chlorlde in ehe presence of water vapour and hydrogen fluorlde).

The decomposltlon ~ay be carrled oue ln the entrance co the lehr.

When the coatlng is to be used as an lnfra red reflecting coatlng, the lnfrared reflectlng layer will usually have a thlckness in the range 200nm to 500nm.

Thicker layers, for example up to lOOOnm, may be used ~f desired but are generally unnecessary ln view of the iridescence reducing properties of the underlayer.

When the coating is to carry an electrical current, for example in a resistance heacer or a liquld cryscal dlsplay, the thlckness of Che coacing will depend on the electrlcal conductlvity requlred but will typically be in the range lOOnm to lOOOnm.

The sllane is preferab~y monosilane (SiH4), alehough ocher substituced or unsubsCituCed silanes in gaseous form e.g.

dimechylsilane (CH3)2SiHland disilane Si2H~, may be used if desired. The unsaturated hydrocarbon may be an ethylenically unsaturaced hydrocarbon compound, an acetylenically unsaturated compound (for example acetylene) or an aromatic compound (for example toluene), although it is generally most convenient to use an unsaturated hydrocarbon which ls gaseous under ambient condltions.

The unsacuraced hydrocarbon is preferably an olefin, conveniently an olefin concaining 2 co 4 carbon atoms.

Ethylene is especially preferred.

The proportlons of che componenc gases present in the gaseous mlxcure and che flow race of che gaseous ~ixcure over che glass may ~ ~ 7 ~ 1327143 be regulated to provide an underlayer of a deslred thlckness ant refractlve lndex.

The carbon dloxlde aces as a source of oxygen so ehae, although there is only limited availability of oxygen from th~ glass surface, eransparene layers havlng a ehickness up to 80nm as taught by GB paeent 2 031 756B can readily be achleved.

Moreover, by approprlate regulaelon of ehe relative proporeions of the component gases present, an underlayer havlng a refractlve index ln the range 1.7 eo 1.8 taught by GB patene 2 031 756B can be achleved. In a preferred aspect of the inveneion, ehe proportions of ehe component gases present in the gaseous mlxeure used to deposit ehe underlayer and the flow raee of ehe gaseous mixeure over the hot glass are regulated to deposit an underlayer having a ehickness in ehe range 60 nm to 80 nm and a refractive index in the range 1.6 to 1.8.

In another embodiment of the lnveneion, ehe proportions of the component gases present in the gaseous mixeure used to deposlt the underlayer and the flow raCe of the gaseous mixture over the hot glass are regulated to deposlt an underlayer whlch has a thickness and refractive index such that the glass coated with the underlayer has a llght transmlsslon wlthln 2% of the llght transmlsslon of ehe uncoaeed glass and ~hlch provides an effectlve barrier to migraeion of alkali metal ions from the glass. The llght eransmisslon of the coated glass is preferably within lZ of the light transmission of the base glass. By the expression "effective barrier it is meant that, on testlng by the meehod described herein, the underlayer - 8 - 132714~ ~ ~ : .

allows the passage oÇ not more thsn 100 (and preferably noc more than 60) mlcrograms of sodium expressed as Na~0 per square teclmetre of glass.

In genersl, the hlgher the raelo of unsaturaced hydracarbon to sllane, the thlnner the coatlngs and the lower the refractlve Index of ehe coating. It is generally preferred to operate at a ratlo of unsaeurated hydrocarbon: silane in the range 2:1 to 5:1 by volume, although ratios outslde this range, for example, 1:1 to 8:1 (or :even higher) ~ay be used.

The unsaturated hydrocarbon is believed 10 to act by being adsorbed on the glass surface so that, ln general, the more strongly the unsaturated hydrocarbon is adsorbed on the glass, the lower the proportlon of unsaeurated hydrocarbon to ~ ;

silane is required for a given affect.

The ratio of carbon dioxide eo silane is preferably in the range 2:1 to 8:1 by volume, although ratios outside this range, for example 1:1 to 20:1 (or even hlgher~ may be used.

The higher ratios will generally only be used when operating at very low silane concentrations.

The gaseous mixture used will generally contain an inert carrier gas, for example nitrogen, in an amount of, for example, 10% to 90X by volume of the ga~eous mixture.

Increasing the total flow rate of a gaseous mixture of given composition results, as might be expected, in an underlayer of increased chickness.

It has also been fount to result in an underlayer of hlgher refractive index. The glass is preferably at a temperarure in the range 630C to 720C. - " 1 32 71 ~ 3 The process of the presene invention facil~tates the on-line production of irldescence retucing underlayers and underlayers whlch serve as a barrier to the mlgration of slkall metal lons and have a very hlgh degree of transparency to vlslble llght.

Moreover, as the reactants used are not strongly oxidising the process can be applled to a ribbon of float glass as lt is advanced over the molten mecal bath on whlch it is formed without undue risk of oxidislng che molten mecal.

The invention is illustrated but not llmited by the following Examples. In the Examples, all percencages are by volume unless otherwise indicated, and the gas flow rates are measured at 69 kPa (lO psl) and approximaeely 20C.

The refractive index and thickness values quoted for che underlayer are calculated, applying chin fllm theory, from che wavelengch and magnltude of ma~imum reflection of the underlayer. The light transparency of the coated glass is expressed as dT, which is the difference between the perceneage light transmission of the glass coated with the underLayer and the percentage light transmission of the uncoated glass. The effectiveness of the underlayers as barrier layers to the migration of alkali metal ions was determined by the following procedure. Two samples of the coated glass, each 10 cm square, were cut and clamped together wlth an annular sllicone rubber ring of lnternal diameter 8.5 cm between them to form a cylindrical cell with its walls defined by che coaced surface of the glass and che inner surface of che silicone rubber ring. The cell was filled wich de-ionised vacer through a hole in Che rubber rlng, the hole - ''':'' , '~ :~ :

` ~327~ -- 10 - ~ealed and che sealed cell Lmmersed ln a water bath at 96C for 48 hours. The solution was removed and analysed for sodlum by flame emisslon spectroscopy. The sodlum extract was deeermlnet and expressed as micrograms of NaaO per square declmetre of glass exposed to the water ln the cell. ;~ Example 1 :

A rlbbon of 6 mm float glass advanclng at a lehr speed of 322 metres per hour was coated wlth an underlayer by applylng a gaseous mixture to the upper surface of the glass as lt advanced over the ~- ;

float bath ac a posltlon where the glass temperature was about 645~C.

The gaseous mlxture comprlsed 11% monosllane, 23~ ethylene, 23% carbon dioxide and 44% nitrogen as a carrier gas.

The gaseous mlxture was caused to flow-parallel to the glass surface ln the dlrectlon of movement of the glass under lamlnar flow conditions using an apparatus as described ln G.B. patene speclflcatlon 1 507 966, modlfied to extend the path of travel of ehe gaseous mlxture over the glass surface to approximately 0.2m.

The flow rate of the gaseoug mixture was 22 litres per minute per metre width of glass coated. A clear, substantlally haze free, underlayer was formed on the glass surface with a thickness of 76.1nm and a refractlve lndex of 1.77.

Examples 2 and 3 The procedure of Example 1 was repeated wlth an increased raclo of flow of ethylene and carbon dioxide.

Thls resulted ln a - ' ' ll- 13271~ small reductlon ln boch the thlckness and refractlve lntex of the layer formed. The condltlons used and results obeained are set oue ln Table 1, wlth correspondlng details for Example 1 for comparlson . .

Examples 4 to ô The procedure of Example l was repeated using dlfferent gaseous mlxtures and varylng the proportion of ethylene to carbon - dloxlde ~hile maintalnlng both the proportion of monosilane:ethylene plus carbon dloxide and the total gas flow rate constant. The condltlons used and results obtained are set out ln Table 2.

The use of a hlgh ratlo of eehylene:silane, as ln Examples 4 and 5, resules in a very thin underlayer (less than 55 nm).

Reducing the ratlo of ethylene:sllane and lncreasing the ratio of carbon dioxide:silane initially leads to an increase ln thickness of the underlayer (Examples 6 and 7), but the thickness of the underlayer is reduced ~hen the ratio of carbon dloxide:silane increases to 8:1.

Examples 9 to 13 The procedure of Example l was repeated using a gaseous i~ mixture containlng 10% monosllane, 25% ethylene, 25% carbon dloxlde and 40~ nitrogen at dlfferenc total flow raees. The results are shown in Table 3 (Examples 9 to ll). It is found that boeh the ehickness and ehe refracelve lndex of ehe underlayer increases ~ieh , - . , .

- , ~ .

1~27143 - 12 increasing ~otal flow rate.

The procedure of Example 9 was repeated uslng ehe same flow rates of sllane, ethylene and carbon dioxide wlth lncreaslng flows of nltrogen. The flow rates used and characterlstics of the underlayers produced are shown ln Table 3- tExamples 9, 12 and 13)- It was found that the thlckness of the underlayer decreased, whlle its refractlve index lncreased, wlth lncreased nltrogen flow.

Examples 14 to 19 In these Examples, carried out in a similar manner eo Example 1, underlayers were produced on 6 mm float glass under condicions se~ out in Table 4, and found to have the refractive indices and -~ ehicknesses shown in that Table. Fluorine doped tln oxlde layers were then deposited on the float glass rlbbon over the underlayer as lt entered the lehr by chemical vapour depositlon from a gaseous mlxture of stannlc chlorlde, water and hydrogen ~luorlde. The thlckness of the tln oxlde layers was measured, and the colour co-ordinates of light (C.I.E.

Illuminant C) reflected from the coated side of the glass were measured and, ln the case of Examples 14 to 17, compared wlth the colour co-ordinates of light reflected from similar fluorine doped tin oxide coatings without the underlayer. (The use of colour co-ordinates to deflne colours is described in 'The Measurement of Appearances- by R. S.

Hunter, published by John Wiley & Sons, 1975). The results obtained are shown Ln Table 5. - ~ ~ -~'':'-'- :

,~ - 13 - 1 32 71 4 3 It will be seen that Che effect of the underlayers ls to suppre~s the reflection colour of the eln oxlde layers.

Examples 20-23 The procedure of Example 1 was repeated uslng a gaseous mlxture contalnlng lOZ sllane, 20~ ethylene, 30Z carbon tioxide and 40Z nitrogen flowlng at a rate of 50 litres per minuee per meere of glass coated over a rlbbon of 2.1 mm glass advancing at a lehr speed of 1130 metres per hour.

The gaseous mixture was passed over che glass at a posltlon where the glass temperature was a~out 645~C. ` The glass was found to be coated with a layer having a high degree of transparency, the coated glass having a light transmlsslon only 1.1X less than that of the uncoated glass. The effectiveness of the layer as a barrier to the migratlon of alkali was measured as 90 mlcrogram of Na~0 per square teclmetre of glass (see above)~ ~ The procedure was repeated uslng dlfferent gas composltions on ~ 6 mm and 4 mm glass. The glass temperature at the coating station, the lehr speed of the ribbon, ehe gas composieion and flow raee used, togeeher wieh ehe properties of the coated product are shown in Table 6. Comparing Examples 21 and 22, it will be seen that the increase in glass eemperaeure and silane conceneration, and the reduction in the raclos of ethylene and carbon dloxlde to silane, more than compensated for the reduction ln gas flow (from 5S to 24 ' ' ' 13271~ ~ . .

. .

lltres/mlnuee/mecre), ~o ehae the coaelng formed ln Example 22 was approximacely ewice as thlck as the coaelng of Example 21. All the Examples showed a good barrler performance, buc che underlayer of Example 22 gave the highese llghe tranamisslon (relatlve to the llghe transmisslon of the uncoatet glass).

Examples 24 to 30 These Examples lllusera~e the use of butene as ehe unsatura~ed hydrocarbon, ~ieh sllane and carbon dloxide, to produce colour suppressing underlayers and barrler layers in accordance wlth the lnventlon.

The Examples were carried oue by the procedure described in Example 1, bue coaeing only a narrow serip of glass at ehe edge of ~he ribbon.

The glass was 6 cm thick, was moving ae a lehr speed of 360 mecres/hour and was coa~ed ae a posi~ion where lS les tempera~ure was 685C.

The cond$eions, gas composielon and gas Slow rates used, and the propertles of the underlayers produced, ~ ;

are see oue in Table 7.

Saelsfaceory colour suppresslng layers were produced with a thlckness in the range 60 nm to 80 nm and a refractive index in the range 1.6 to 1.8 in Examples 2S to 27 (and marglnally outslde those ranges ln Example 24).

Examples 28 to 30, whlch were carrled out ~ ...

at lower gas flow rates, resulted ln ehlnner coatlngs havlng an excellent barrler performance wlth the coa~et glass havlng a ~ : . ., " light transmisslon close co tha~ of the uncoa~ed glass. Comparing Examples 24 eo 30 wieh the earlier ~xamples, i~ will be na~ed ~ha~ higher overall gas flows were apparently requlred ~o produce ,' - ,:

",' -:

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- 15 - 1 32 71 4 ~ coatings of similar thlckness.

It is believed that this i8 due, at least in part, eo the process of Examples 24 to 30 being carried out on a narrower strlp of glass wlth slgnlflcant escape of gas away from the sldes of the strlp belng coated.

S Examples 31 to 36 ':

Static samples of 3 mm float glass, 10 cm by 10 cm, were coated in the laboratory by heatlng the glass in a silica tube at a -~ temperature of about 650C and passing a coating gas comprislng a mixture of silane, carbon dioxide, an unsaturated hydrocarbon and nitrogen over the hot glass surface.

The gas compositions used and -treatment times are shown in Table 8, together with the results of measurements on the llght transmlssion and barrier properties of the coated products.

With each of the unsaturated hydrocarbon gases used, a good barrier performance was achieved with a hlgh degree of transparency (within 1% of the transparency of the uncoated glass). `' ' Examples 37 to 40 The procedures of Example 1 was repeated using a gaseous mixture of silane, ethylene and carbon dioxide in nitrogen to coat 2 mm float glass advancing at a lehr speed of 1100 metres/hour.

The light transmission of the glass was measured and compared with the light transmission of the uncoated glass to give the - 16 1~271 ~3 dlfierence dT, and ehe barrier performance of ehe glass was measured as described above.

The thickness of the coatlngs was too small for measurement by the optlcal method descrlbed above, and was measured by an argon lon etchlng eechnlque.

The coating condltlons and resulès obtained are shown in Table 9.

Examples 37 to 40 all illustrate the productlon of barrler layers, such that the coated glass has a llght eransmisslon wlthin l.S% of ehe lighe transmission of ehe uncoated glass (dT).

The ;~ final comparaeive Example shows that, in ehe absence of carbon dloxlde, ehe light transmission is slgniflcantly lower (dT = 2.3%), although the underlayer is ln fact thicker than the underlayers produced in Examples 38 and 40 A comparison of Examples 37 and 38 indicates that increasing the ratio of dopants (ethylene and carbon dioxite) to silane has reduced the underlayer thickness, with a ;;

consequent improvement in lighe eransmission but a reduction ln barrier performance. A small reductlon ln the ratio of dopants to silane (compare Examples 37 and 39) has reduced the light -~ transmission, while leaving the thickness and barrier performance unchanged.

Reducing the ethylene and increasing the carbon dioxide substantially (Example 40), reduces the thickness and increases the lighe transmission but leads to a substantial reductlon in barrier performance.

The foregolng Examples show that, by regulating the proportlons of the component gases present ln the gaseous ~lxture .. ''!,.. .

used in the process of the lnven~ion and the flow rate of the A ~ ~ ~ - .

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- 17 - 1 3 2 71 4~ .

gaseous mixeure over the hot glass surface, underlayers of a desired thickness and refractlve lndex may be produced.

Thus the process of the inventlon ls useful not only for produclng colour suppresslng underlayers of the klnd described ln GB patent 2,031,756B, but also for produclng other colour suppressing underlayers known in the art, as well as underlayers with a high degree of transparency useful for their barrier propertles.

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