FR2476065A1 - METHOD AND APPARATUS FOR OBTAINING ABRASION RESISTANT GLASS SURFACES AND ARTICLES OBTAINED BY SAID METHOD AND APPARATUS - Google Patents

Abstract

PROCESS AND APPARATUS FOR OBTAINING ABRASION-RESISTANT GLASS SURFACES AND ARTICLES OBTAINED BY THIS PROCESS AND APPARATUS. IN THE PROCESS ACCORDING TO THE PRESENT INVENTION, THE COATING OF SELECTED PARTS OF THE EXTERIOR SURFACE OF THE BODY OF THE CONTAINER IS OBTAINED BY MAKING THE CONTAINERS GO ONE THAN ONE OTHERS IN A GAS CURRENT FORMED BY TWO CONSTITUENTS, ONE OF WHICH IS STRONGLY REACTIVE. TO HUMIDITY AND OF WHICH THE OTHER IS LESS REACTIVE TO HUMIDITY. THE MOST REACTIVE CONSTITUENT IS SURROUNDED BY THE LESS REACTIVE COMPONENT AND EACH OF THESE COMPONENTS CONTAINING A DIFFERENT METAL, SO THAT THE CONTAINER IS OBTAINED A COATING OF COMBINED METAL OXIDE GIVING SCRATCHES OR OTHER SUSCEPTIBLE DEFECTS. MECHANICAL RESISTANCE.

Description

Method and apparatus for obtaining glass surfaces resistant to

  abrasion and articles obtained using these method and apparatus. It is known in a general way that the glass holds

  its considerable mechanical resistance of an initial surface state ,.

  that is to say without defects, and that any scratches or cracks that appear or develop on its surface diminish several times its mechanical strength. Normally, the glass containers have maximum mechanical strength immediately after their formation and this resistance

  mechanics decreases as the containers come

  in contact with each other and with others

  surfaces, for example during their automatic handling.

  It goes without saying that if the outer glass surfaces are coated with a composition having good resistance to dry scratching or in the presence of moisture, as well as

  good resistance to abrasion, which decreases

  the risk of breakage, filling and packaging equipment can handle a larger number of containers during the same period of time thanks to a smaller spacing of the containers and an increase in the speed of the handling conveyors, even that if the glass surfaces are subject to greater contact with similar surfaces and with different surfaces. In addition, because many products, such as soft drinks, are packaged under pressure, it is highly desirable that the outer surfaces of the glass containers have no or at least few scratches to reduce to a minimum

the risk of rupture.

  Various types of single and double surface coating compositions have been used previously to provide good abrasion and scratch resistance as well as smooth nature and durability to withstand operations.

Handling.

  U.S. Patent No. 3,323,889 discloses a method for increasing the scratch resistance of a glass surface by treating it by pyrolysis and then coating it with an olefin polymer. U.S. Patent No. 3,368,915 discloses an abrasion resistant glass article on which a dual protective coating obtained with the above method has been deposited. In addition, US Pat. Nos. 3,403,015, 3,577,257, 3,598,632, 3,645,778,

  2,813,045, 2,881,566, 2,982,672, 3,258,444, 3,407,085, 3,414,429,

  3,418,153, 3,418,154, 3,425,859, 3,432,331, 3,438,801, 3,441,399,

  3,441,432 and 3,445,269 all relate to a process for rendering abrasion-resistant glass surfaces and to glass articles obtained by this method. In none

  processes mentioned above, mention is not made of the application

  simultaneous cation of two metal oxide

  and a stream of dry, very hot air to form a main coating of metal oxides combined on glass surfaces in an economical manner, one of the compounds being highly reactive with respect to atmospheric moisture and the other compound being less reactive and playing a role of

  desiccator to protect the application of the first compound.

  Therefore, an object of the present invention is to obtain on glass surfaces an improved double main coating which is extremely resistant to abrasion and scratches or other similar defects and which is economical to apply, the characteristics resistance

  inherent mechanics of the glass thus being maintained.

  Another object of the present invention is to obtain a substantially uniform thin coating on glass surfaces, which coating is transparent and extremely resistant to scratching and abrasive action to prevent weakening of said glass surfaces. This uniform coating can be obtained during the passage of the glass articles through a treatment chamber in front of fixed inlet ports for the process gas and without rotating the

glass items.

  Another object of the present invention is to provide a method for coating glass surfaces, for example selected outer surfaces of glass containers, to impart scratch or scratch resistant properties to them so that they can Significant decrease in mechanical strength, normal handling, filling, processing and shipping operations during which glass surfaces

  rub against similar surfaces and different surfaces.

  and come into repeated contact with these surfaces.

  In order to achieve the objectives of the present invention, a main feature of this lies, firstly, in the treatment of the glass surfaces simultaneously with at least two metal-containing constituents and which can be decomposed by pyrolysis, that is to say -describe materials that chemically decompose under the action of heat to form metal oxides on glass surfaces at a temperature above the temperature

  pyrolysis of the constituents and, on the other hand, in the cooling

  This is followed by the double metal oxide treated surfaces, for example in a annealing furnace, so as to obtain reinforced glass articles 5. The treatment operation is carried out by protecting the most moisture-responsive constituent with a less moisture-responsive constituent during application.

  combined these constituents to the glass surfaces.

  Another feature of the present invention resides, on the one hand, in the treatment of glass surfaces with a compound containing tin and a titanium-containing compound, both compounds being susceptible to pyrolysis, that is, chemically decomposable by the action of heat to form double oxides on the glass surfaces while these surfaces are at a temperature above

  pyrolysis of said compounds and, on the other hand, in the cooling

  Consecutively the glass articles thus treated, for example in a annealing furnace. The treatment with metal oxides can then be followed by the application of a

  underlying organic coating of very different types.

  The present invention will now be described with reference to the accompanying drawings, in which: FIG. 1 is a diagram showing the flow of gases in the coating apparatus in question and where the bottles transported and the conveyor belt are shown; carrier; Fig. 2 is a schematic plan view of the coating apparatus of Fig. 1, this figure showing gas flow, bottles and conveyor;

  Figure 3 is a partial side elevational view;

  3 -3 in FIG. 2, this view showing the tubular discharge device for the first gaseous component and the various conduits of the coating apparatus; FIG. 4 is an enlarged partial perspective view

  showing the tubular discharge device for discharging

  handle the first gaseous component on the bottle; and Fig. 5 is a block diagram showing the flow

  gases to the coating apparatus.

  In the practice of the present invention, the glass articles are processed immediately after leaving the glass forming machine and during their transportation by a continuous conveyor to the annealing furnace. This treatment takes place immediately after forming while they still have a considerable amount of heat from the molten state in which they are during the forming operation. Two distinct solutions of pyrolysis-susceptible compounds are sprayed onto the selected outer surfaces of the glass articles in a form.

  vaporized and in a prescribed configuration at a temperature

  higher than the pyrolysis temperature of the two compounds

  individual. Pyrolysis temperatures for many -

  Typical types of tin compounds and titanium compounds that can be used in the present invention are from about 371 ° C to 704 ° C, with the most preferred temperatures being from 4820C to 6490C for

  halide compounds of these metals.

  As can be seen in FIG. 1, the conveyor is used to transfer the newly formed glass bottles 11 from a forming machine to an annealing annealing furnace and being evenly spaced from each other. The bottles are transported in a vertical position on the upper arm of the conveyor surface through a treatment apparatus or enclosure 12. The bottles are not rotated during

  this transport is generally horizontal and we obtain a

  surface effect quite adequate and uniform without rotation. The treatment chamber 12 is constituted by two lateral ducts 13 and 14 each of which has inlet or inlet orifices 15 and 16 at one of their ends and exhaust or outlet orifices 17 and 18 at their other ends. Inlets and ports

  of the enclosure 12 are placed in a trans-

  on both sides of the carrier in a

diametrically opposite.

  The inlet or inlet ports and the juxtaposed exhaust or outlet ports, with their parallel side ducts, can thus form a process gas recycle loop for the selected gases used to process the containers. The relative locations of the admissions or entrances, the exhausts or outlets and the lateral ducts connecting them are shown in FIGS. 1 and 2 above a portion of the horizontal strand of the conveyor, the enclosure enclosing the receptacles for a brief period of time.

  during their horizontal transport.

  A first gas is introduced into one of the lateral ducts, namely the duct 13, at a point preferably situated at the inlet orifice 20. This gas serves to fill substantially the lateral duct 13 and surrounds a second gas introduced at

  center of the gas stream at the inlet port 15 of the conveyor.

  The first gas has a desiccation function vis-à-vis the second gas that is introduced into the gas stream at a point

  immediately adjacent to the transported container 11.

  Another duct 21 is mounted above the duct

  lateral 13 for delivering pure auxiliary air trans-

  to the conveyor at a location adjacent thereto and between the upper region of the inlet port 15 and the

  upper region of the outlet orifice 18. A conduit for

  separate main exhaust 22 for clean air is disposed to the right of the conduit 21 for the evacuation of air and gases

  exceeding after their transverse scanning of the conveyor.

  The clean air sweeps around the upper or lower ends of the containers 11 to prevent the deposition of metal oxide there. A separate loop or secondary exhaust duct 23 extends from a central region of the enclosure parallel to the conveyor 10 and up to

  main exhaust pipe 22 so that the process gases

  excessively, and clean air, are for sure

  picked and directed into the main exhaust pipe 22.

  Similarly, another auxiliary fresh air duct 24 is mounted adjacent the inlet and outlet ports 16 and 19, respectively, to discharge clean air over the neck portions of the containers 11. to a main exhaust or outlet port 25. Another exhaust or secondary outlet conduit 26 extends from a region adjacent to the inlet and outlet ports 16 and 19 above the downstream central side of the carrier to collect the process gases and clean air by exceeding and discharging them into

  the main exhaust pipe 25.

  Figure 2 shows, schematically, the inlet and outlet ports juxtaposed at each of two adjacent coating locations along the conveyor, the respective orifices being in a diametral arrangement in an almost closed loop. Figure 3 shows one of the inlet ports, namely the orifice 15, with the first gas discharged from its inlet port 20 and then through the lateral conduit 13 to the inlet port. The clean air is directed on the neck and the neck of the containers from the upper conduit 21. A second gas is introduced in the center of this stream, by a perforated tube 30 having a series of openings 30adans

  the entrance zone below the fresh air duct 21

  iary. The openings are directed towards the containers

  in order to direct the second gas towards the center of the con-

  flow representation to the container 11 immediately adjacent. As mentioned, two distinct solutions of hydrolytic compounds are discharged onto the

  body parts of glass containers. The vaping solutions

  are fed to the containers according to the configuration

  prescribed flow so as to fall on said containers

  at a temperature above the pyrolysis temperatures of the two individual coating compounds,

  preferably containing tin and titanium.

  FIG. 5 shows in a block diagram how the tin-containing compound, preferably tin chloride, is vaporized with the air at point A before being discharged into the lateral duct 20 and then into the two lateral ducts 13 and 14 for delivery to the inlet ports 15 and 16.

  second compound containing titanium, preferably tetra-

  titanium chloride, is discharged at point B where it is introduced into a mixing tee where it is mixed with dry and very hot compressed air from points C and D. The titanium compound vaporized with air is then discharged into the two tubes 30 each having a network

Linear OpenEr30a.

  The two gases are preferably mixed in a volume ratio between the first component and the second component in the range of about 2: 1 to 8: 1 when the two vapor constituents are generated at the same pressure and temperature. the

same temperature.

  Titanium compounds are much more moisture reactive than tin compounds and, therefore, have a great tendency to react with this moisture by hydrolysis reactions before striking the glass surfaces. Titanium compounds that reacted with available moisture

  are no longer able to form metal oxide

  liquefied or durable on glass surfaces. This is often the case when titanium tetrachloride alone is sprayed on very hot glass surfaces as the first coating. The titanium compounds, in their reaction with water and water vapor, tend to clog the spray nozzles with hydration products, thus disturbing the spray patterns and providing irregular results. According to the present invention, it is preferable to use a prescribed spray configuration in which the titanium compound centered in the stream is surrounded by the tin compound to obtain a uniform deposit of the two metal oxides on the glass surface under the shape of a very adherent combined coating and

very uniform.

  The titanium compound used in the present invention is a compound which, when in contact with the surface

  heated, reacts to form titanium oxide.

  Suitable titanium-containing compounds include titanium tetrahalides and especially titanium tetrachloride. The ammonium salts of titanium lactate are also suitable. In addition, volatile organometallic compounds such as alkyl titanates, preferably where the alkyl group contains from 1 to 8 carbon atoms, are also suitable. Among the alkyl titanates that can be used are tetrabutyltitanate, tetraisopropyltitanate,

  tetramethyltitanate, tetraethyltitanate, tetranonyl-

  titanate and other similar products.

  The tin compounds that can be used for the purpose of the present invention include both the compounds

  stannous and stannic compounds. Among the standard compounds

  suitable for this purpose are stannic halides and alkyl stannic carboxylates. Examples of stannic halide are stannic chloride, stannic bromide and stannic iodide. The alkyl stannic carboxylates have the general formula (R1) xSn (OOCR2) wherein R1 and R2 are alkyl groups and x and y are integers ranging from 1 to 3 and the sum of which is equal to four. The alkyl groups may be a straight or branched chain. The alkyl group R 2 preferably contains from 1 to 18 carbon atoms, such as, for example, stearate, paimitate, laurate and the like. The alkyl group R 1 preferably contains 1 to 8 carbon atoms such as, for example, methyl, propyl, butyl, isopropyl, isobutyl, hexyl, octyl and the like. Among the compounds falling within the scope of the above enumeration, there is the dichloride

  dibutyltin, butyltin acetate, dipropyl diacetate

  tin, diacetatooctyltin, distearoylibutyltin, dipalmitatedibutyltin, dilauratedibutyltin,

  maleatebutyltin, and other like bodies.

  Among the stannous tin compounds suitable for the purposes of the present invention are stannous dihalides, such as stannous chloride, stannous bromide, iodide

  stannous and stannous tin salts of the carboxylic acid.

  The latter comprises compounds having the formula Sn (OOCR) 2 o R is an aliphatic or aromatic group. Among the aliphatic groups, there are alkyl, both substituted

  unsubstituted with up to 18 carbon atoms.

  Aromatic groups include cyclic carboxylic acids wherein the aryl radical is benzyl, phenyl, naphthyl, or the like. Suitable carboxylic acid salts for the purposes of the present invention include stannous oleate, stannous palmitate, stannous stearate, stannous caproate, stannous laurate, stannous maphenate, stannous tartrate, stannous gluconate, acetate stannous and other similar body. It will be understood that any titanium or tin compound can be used, provided that this compound can form an oxide on the glass surface at the indicated reaction temperatures. The titanium and tin compounds which are preferably used in the present invention are those which, when they come into contact with the heated surface of the glass, react to form a substantially color and transparent layer or coating of metal oxides and coals. both TiO2 and SnO2, on the surfaces of the glass. The combined oxide coating adheres firmly to the glass surface and has a thickness of the order of a few microns. This double coating serves as the main coating for a second or underlying coating, preferably organic material,

  applied at a lower temperature.

  Glass articles, when coated by the

  thin double oxide main coating, are then

  in an annealing furnace where they are gradually cooled and subjected to annealing under stress for a certain period of time. When they have been cooled to a temperature of about 20 ° C. and lower, during a final phase of the annealing cycle, they are normally covered with a second coating of a polyethylene emulsion, for example, to provide them with a coating. protective lubricant. This second coating or layer can vary widely depending on the end use requirements and is not part of the

  present invention. Such a second coating or layer

  A polyethylene emulsion form a typical final coating, for example the polyethylene emulsion sold by Owens-Illinois, Inc., Toledo, Ohio, under the trademark "Duracote". U.S. Patent No. 2,995,533 discloses the preparation and use of a polyethylene emulsion as a lubricant coating for glass containers, which patent belongs to the Applicant. The organic coating composition can be applied using any suitable device, such as

  for example a spray nozzle with a movement of-and-

  comes, spraying a uniform amount of coating material

  per unit area of the oven belt. The amount is often set at a value between 0.030 liter and 0.070 liters per square meter of oven belt. It is preferable that the final organic coating is applied

  by spraying near the cold end of the oven,

  that is to say, when the glass articles are at a temperature

  ure between about 380C and ú040C.

  With regard to the first main coating to which the present invention is mainly related, the second

  component of gaseous treatment is normally an extreme gas

  moisture-reactive, such as tetrachloro-

  It can not normally be satisfactorily applied alone to the surface of the glass. At the very least, this vaporized reactive component often raises sealing problems when used alone for coating glass articles during a period of time. long-term campaign. According to the present invention, this gaseous compound is contained in a controlled amount with a dry, heated stream of compressed air for delivery to a central region.

  at the inlet port of the treatment chamber.

  The ratio of the process gas to the very hot dry air is carefully controlled, the air usually being

  exceeding to avoid hydrolysis of the process gas.

  The second gas is preferably titanium tetrachloride, because its price is economical and it is easily available. It is combined with dry air heated in a mixing tee immediately before use. The hot dry air is heated to about 1490C and has a dew point below -60C. The very hot dry air and mixed TiCl4 are decanted together in a perforated tube

  which is mounted vertically in the center of the inlet.

  Two of these inlet ports are used in the processing chamber on the diametrically opposite sides of the container conveyor belt; Each perforated tube has a series of openings directed towards the transported containers and in the immediate vicinity of the latter, the openings preferably having a diameter of approximately 1.6 mm. Each tube is placed in the center of the inlet duct which conveys the second less reactive gas to moisture> coam for example stannic chloride, to the region of the inlet orifice. SnCl4 is normally transported by dry compressed air into the inlet conduit and serves to surround the second, more moisture-reactive gas such as TiCl4. TiCl is thus protected from reaction with atmospheric moisture before being discharged onto the very hot adjacent surfaces of the glass. The two metal-containing gases are directed to the very hot glass surface of the container and are deposited therein as a metal oxide. The body portion of the container normally comprises the surface areas selected for this coating, the portion formed by the neck of the container being protected by the dry and very hot auxiliary air discharge preventing

  deposit of metal oxide on this part.

  The first and second gaseous constituents that flow under pressure within the treatment chamber and

  transversely to the carrier, surround and clothe

  formally the outer surfaces of the body portion of the container. The excess process gas is transported through the exhaust port transversely from the inlet port and through the extending side duct.

  parallel to the conveyor to the second inlet port.

  The secondary perforated tube is aligned vertically with

  the second input port oriented transversely to the trans-

  carrier. An amount of second treatment gas, i.e. TiCl4, equivalent to that introduced into the inlet port

  initial, is then introduced into the secondary inlet

  dary. The two metal-containing gases, i.e. TiCl4 and SnCl4, are then forced directly transverse to the conveyor belt from the opposite direction so as to strike the other side of the body surfaces.

  containers. At the two inlet ports of the processing chamber

  the second gas, i.e. TiCl4, is surrounded by the first gas, i.e. SnCl4, so that no visible reaction of the second gas sensitive to moisture or steam water, can not occur. The outer surfaces of

  containers are then coated in essentially uni-

  form on their circumference from the top to the bottom of their

  part of the body, the part formed by the neck or

  end of the container not being coated. The outer surfaces, from the sides facing the inlet to the sides oriented in the axis of the conveyor, of the container which has not rotated have a certain variation in thickness in

  the desired range of uniformity for improved durability.

  The excess process gas from the second inlet port is returned through the side conduit parallel to the conveyor axis to the initial inlet port where the gas treatment loop is completed. Except for openings for the passage of receptacles

  existing at the opposite ends of the processing

  and through which the conveyor belt passes

  on which the glass receptacles are moved, the enclosure is completely closed for maximum

of the treatment of the containers.

  The titanium tetrachloride compound is a much less expensive component than the stannic chloride compound, which allows a more economical coating of the glass articles. The quantity ratio between the second component and the first component can be varied within wide limits so that very large quantities of the cheapest component can be used, thereby significantly reducing the cost of the coating. The volume ratio between the second component and the first component may conveniently be between 2: 1 and 8: 1 when both components are generated at the same pressure and temperature. Thus, substantially more TiCl 4 can be combined with SnCl 4 for their co-deposits on a single-layered coating on the glass surfaces. Since the two metals are of the same periodic group, they can be homogenized as a thin coating with physical and chemical properties somewhat similar to those of the individual oxides when they are deposited alone in the form of thin dandruff. The results of the treatment using mixtures of tin oxide and titanium in combination are very similar to the results obtained with tin oxide alone. We can

  significantly reduce the expenditure on the subject in use.

  reading mixtures of tin compound and titanium instead

of a tin compound alone.

  The dimensions of the apertures of the perforated tubes for discharging the TiCl4 into the gas stream are not critical, but it is important that this component be combined with the very hot and extremely dry air and that it be introduced in the center of this stream. combination in one point immediately

  adjacent to the point of deposit. The amount of dry air is important

  A typical 1,440 m3 to 2,800 m 3 / hour of extremely dry heated propellant is used to transport CiCl 4 to the discharge tubes. Total flow rates of 0.840 m 3 to 2800 m 3 / hour of the mixed working vapor containing TiCl 4 is discharged into the gas stream to coat the containers. Maintaining the metal oxide coating outside the container neck area substantially prevents or reduces the corrosion of the steel capsules when the

  containers are filled and closed with such capsules.

  The double coating of tin oxide and titanium oxide makes it possible to obtain a coating of metal oxides, uniformly distributed and chemically reactive on the glass containers before they are annealed, this coating being combined with

  organic surfactants applied at a lower temperature than

  better to obtain a smooth, solid and scratch-resistant outer coating. The double coating of tin and titanium uses the best characteristics of both materials, ie the uniformity of the application of SnCl4

  and the low price of TiCl4 to ensure an acceptable distribution

  coating tablecomparable to that obtained with tin materials used alone but with a considerably lower cost for each container. The present method can be used with many existing types of chambers or treatment chambers designed for treatment with SnCl4 alone. Only perforated tubes and equipment for mixing hot air for transporting TiCl should be used for the second gas. The two materials can therefore be applied in the same apparatus and, if desired, only with a slight

  modification of ordinary types of speakers or rooms.

  The recirculating SnCl4 vapors tend to protect the TiCl4 vapors whereby the resulting coating is

  very uniform and is considerably cheaper.

  Stannic chloride (SnCl4) is usually generated at a given temperature (normally at room temperature) by bubbling dry air (dew point at -400C or below), or dry nitrogen, or by passing through this dry air on the matter

  liquid to form a vapor. Tetra steam

  Titanium chloride (TiCl4) is generated in the same way by using very hot dry air (dew point at -510C or below), or dry nitrogen on liquid TiCO4 so as to form a vapor. The two vapors are introduced into the treatment chamber, the tin vapor being introduced from a single source into a recirculating vapor / air stream. The titanium vapor is mixed with the dry air (as mentioned) heated preferably above about 150 ° C and introduced into the two-point treatment chamber in the immediate vicinity of the current glass articles.

treatment.

  In general, when 0.840 m / hr of sparging gas is required to obtain tin oxide coatings on glass vessel surfaces, it is possible, between the minimum necessary to obtain good protection against scratches (when an overlying coating of a suitable organic lubricant is present) and an upper limit defined by the visibility limit of the coating, to obtain a double tin / titanium coating with 2,240 m3 / I hour of dry air having is bubbled through the TiC14, only 0.280 to 0.420m3 / hour of SnCl4 gas being required. At any given ambient temperature, flow ratios of 1: 6 to 1: 8 between tin and titanium

  give the desired combined coating on the glass surfaces.

  The following table compares the results obtained in the case of a coating with tin alone, a coating with titanium alone, and a double coating using both metals. This table shows material consumption, coating thickness and flow rates.

Spraying.

Material Flow Rate

  Portionization 1. SnC14 alone 0.640 m3 / h Thickness ratio Weight Weight max / min. average of titanium tin coating coated conscotm consanmé 2.8: 1 33.5 CTU 0.560g / h 2. TiCl4 alone 3. Double

coating

  SnCl4 TiCl4 2.040 m3 / h 0.280 m3 / h 2.040 m3 / h 72: 1 4.8: 1

22.0 CTU

  - O, 19Cn3 / h 41.2 CTU 0.19om3 / h 0.190m3 / h 4. Double

coating

  SnCl4 TiC14 0.420 m3 / h 2.040 m3 / h 41.0 CTU 0.275m3 / h 0.19m3 / hr

3.05: 1

Claims (20)

  A process for forming a protective coating for selected portions of the outer surface of a glass vessel, characterized in that it comprises: forming an atmosphere of a pyrolytically decomposable process gas and containing at least two components; introducing the process gas into a process chamber through inlet ports and discharging the process gas from said process chamber through exit means so as to thereby create a positive flow configuration from the inlet ports to the outlet means, said flow pattern being substantially limited to the selected outer surface portions of the glass vessel, a first moisture-responsive first component being confined to the center of said flow configuration; flow and a second component less responsive to moisture surrounding said first component of said flow pattern; passing a glass container at a temperature above the decomposition point temperature of the gaseous process components through the process chamber, the neck portion of said glass container extending out of the gaseous chamber; treatment; forming a substantially uniform coating of the two constituents on the outer surface portions   chosen from said container inside the processing chamber.   from the decomposition products of the gaseous process components; and evacuating said container from the process chamber, the neck portion of the container not being coated and the outer surface portions   selected from the container being coated in a protective manner.   2. Process according to claim 1, characterized by   the fact that it consists, moreover, in forming the first   the process gas is highly moisture reactive with titanium tetrachloride and the second component of the process gas is less reactive with respect to   moisture with stannic chloride.   3. A method according to claim 2, characterized in that it further comprises mixing said treatment gas with dry air which has a dew point temperature of less than about -620C and which has been heated up to at least about 1490C.   4. Process according to claim 2, characterized by the fact that it consists, in addition, of injecting the first very reactive component with respect to moisture and formed by titanium tetrachloride in the center of the flow configuration. of said process gas at said inlet ports, and injecting the second less moisture reactive constituent formed by stannic chloride around the center of the flow configuration of said flow gas at said inlet ports.   The process of claim 2 further comprising injecting the process gas having a volume ratio between the first component and the second component of from about 2: 1 to 8: 1 when both components in vapor form are generated at the same   pressure and at the same temperature.   6. A method according to claim 1, characterized in that said glass container is kept aligned, in a vertical position and without being rotated, between said inlet ports and said outlet means during its passage through said treatment chamber. 7. A method according to claim 1, characterized in that it consists, in addition, to create a recirculation stream of said treatment gas to constitute a configuration of flow ventilationudit treatment gas between the inlet ports and the means from and out   said output means to said inlet ports.   8. A method according to claim 3, characterized in that it consists, in addition, to form at least two treatment zones inside said treatment chamber, the two aforementioned treatment zones being adjacent and their orifices d inlet and their output means being arranged diametrically opposite transversely to the path of said container and being mutually connected to each other.   to form a process gas recycle loop.   9. A method for applying an abrasion-resistant coating to glass articles, characterized in that it comprises: transporting the glass articles onto the surface of a conveyor; applying a vapor containing a decomposable titanium compound surrounded by a vapor containing a decomposable tin compound to selected exterior surfaces of said glass articles while maintaining said selected exterior surfaces in contact with said vapors at a temperature above the temperatures; decomposition point of the decomposable compounds, whereby a combined tin and titanium coating is formed on said outer surfaces of the glass articles thereby forming a substantially uniform scratch-resistant protective coating and formed by tin oxides and of titanium. 10. A method according to claim 9, characterized in that it consists in injecting a first component extremely reactive vis-à-vis the moisture and formed by   titanium tetrachloride at the center of the sample configuration.   treatment vapors and injecting a second less moisture-reactive component formed by stannic chloride around the center of the   flow of the process gas vapors.   11. A method according to claim 9, characterized by the fact that it consists in transporting a glass container with its neck portion protruding beyond the treatment gas vapors so as to protect said portion forming a neck against these vapors.   12. Glass container with a protective coating   on selected parts of its external surfaces,   characterized in that said coating is formed by subjecting the newly formed container still having a substantial portion of its forming heat to an atmosphere of a pyrolytically decomposable process gas, said gas containing   minus two constituents and being managed according to a   positive flow ration from the inlet ports to outlet means, the first of these highly moisture-responsive constituents being confined to the   center of said flow configuration and the second   less responsive to moisture surrounding said first component in said flow configuration, said container passing through the flow configuration of the   process gas at a temperature above the temperature   decomposition point structure of the gaseous process components, the neck portion of said vessel extending beyond the flow configuration of the process gas, said neck portion and extending outwardly; being not coated and the selected portions of the outer surface of said coated container protective.   13. Glass container according to claim 12, characterized in that it comprises a thin uniform coating of tin and titanium oxides combined on its parts selected outer surface.   Glass container according to claim 12, characterized in that said treatment gas flow configuration contains dry air having a dew point less than about -620 ° C and which is   heated to at least about 1490C.   15. Glass container according to claim 12, characterized in that said treatment gas has, between the first component and the second component, a volume ratio of the order of about 2: 1 to 8: 1 when the two components in the form of steam are generated at the   same pressure and at the same temperature.   16. Apparatus for steam treatment for coating selected portions of the outer surface of a glass container, wherein the containers are moved in a vertical position, one after the other and at a distance from each other through an enclosure closed treatment that   has openings at its juxtaposed ends,   characterized in that said enclosure comprises a pair of vertical walls spaced apart from each other and extending along both sides of the line of movement of said glass containers and forming side ducts, a pair of orifices inlet and exhaust means for gaseous treatment vapor mounted transversely to the line of displacement of said containers at the ends of said lateral ducts, the inlet orifices and the aforesaid output means being arranged diametrically so as to form a loop of treatment gas closed through said lateral ducts; means for introducing a first highly moisture reactive gaseous component at the center of the flow pattern to said inlet ports; means for combining the dry heated air with said first gaseous component before it is delivered to the center of said inlet ports;   means for introducing, at said inlet ports, -   a less moisture responsive constituent around said first centrally disposed gaseous component; and means for introducing additional air at an upper region of said inlet ports facing said exhaust means to protect the neck top portion of said containers against said first and second coating gaseous components that the selected areas of the outer surface of the body parts of said   containers are uniformly coated.   17. Treatment apparatus according to claim 16, characterized in that said means for introducing the first component very reactive vis-à-vis moisture   comprises a perforated tube arranged vertically and mounted sensitively   in the center of each of said inlet ports.   18. Processing apparatus according to claim 17, characterized in that said first highly moisture reactive component comprises titanium tetrachloride. 19. Treatment apparatus according to claim 17, characterized in that said second constituent less   Moisture-sensitive reagent includes stannic chloride.   20. Treatment apparatus according to claim 17, characterized in that it comprises a pair of lateral ducts extending parallel to the direction of movement of said containers through said enclosure, two inlet ports located on diametrically opposite sides. of said enclosure, two outlet ports each facing one of said inlet ports, said side ducts, inlet ports and outlet ports forming a closed process gas recycle loop for the first and second gaseous components combined for transport in the form of a continuous stream of gas that strikes the transported containers twice on opposite sides.