Patent Application
20200140324
The invention concerns a method for increasing the strength and durability of glass containers, particularly their ability to withstand internal pressure and the processes associated with treatment of such containers for re-use. The invention also concerns glass containers produced by said method.
In a number of applications, glass containers are required to hold pressurised contents. For example, glass bottles are a favoured storage and transit container for beer or carbonated drinks, and must be able to withstand significantly higher pressures on the interior surfaces than on the outside. The bottle's ability to withstand this higher internal pressure is referred to as its ‘burst strength’.
On the other hand, glass is a fairly heavy material which makes it more expensive and inconvenient to handle and transport. Since the burst strength of a glass container increases with its thickness, any attempt to reduce its weight by reducing its thickness will result in a reduced burst strength. Any attempt to improve the burst strength by increasing the thickness will result in an increased weight.
Thus, any means of increasing the burst strength of a glass container of a given thickness, without increasing that thickness would be particularly beneficial.
U.S. Pat. No. 4,961,796A describes a method of improving the strength of a glass container by applying a coating material which cures when subjected to radiation of suitable energy.
U.S. Pat. No. 7,029,768 B1 describes a food container on which surface titanium oxide particles are fixed by bonding, using a sintering aid or both. Where the container is formed of glass, an increased mechanical strength is observed.
US 2012217181 A1 describes a glass container having a hybrid sol-gel coating across at least a portion of its exterior.
U.S. Pat. No. 9,090,503 B2 discloses Methods of manufacturing and coating a glass container by applying an aminofunctional silane coating composition to an exterior surface of the glass container, and then curing the silane coating composition to form a crosslinked siloxane coating on the exterior surface of the glass container.
U.S. Pat. No. 8,940,396 B1 discloses a glass container and a process for forming a graphene-containing coating on an exterior surface of the glass container to increase the strength of the glass container.
The manufacture of glass bottles or jars by modern methods is well known (see for example “Glass Making Today”; edited by P. J. Doyle; Portcullis Press, ISBN 0 86108 047 5). Typically, a blank shape is first formed by blowing or pressing a slug or ‘Gob’ of molten glass against the walls of a blank mould. The ‘blank’ so formed is transferred to a ‘blow’ mould where the final shape of the article is imparted by blowing against the interior of the latter. Variations on this process may occur but modern production methods typically give rise to a shaped glass container emerging from a mould, the container still bearing significant residual heat from the shaping process.
The deposition of tin (IV) oxide on glass bottles during production, by chemical vapour deposition (CVD) techniques, is also known. Monobutyl tintrichloride is a preferred precursor which is directed to the surface of hot bottles, where it decomposes and the desired coating is formed. The tin (IV) oxide coating offers a number of benefits including improved adherence of a subsequent protective polymer layer.
According to the invention, a method of increasing the resistance of a glass container to internal pressure comprises the steps set out in claim 1 attached hereto.
In a preferred embodiment, the container is provided with a temperature of between 450° C. and 650° C. This temperature is conveniently provided by residual heat from casting of the glass container when the method is incorporated in a continuous manufacturing process for glass containers.
Preferably, the method is incorporated in a continuous manufacturing process for glass containers, and wherein the temperature of between 450° C. and 650° C. is provided by residual heat from casting of the glass container.
Preferably, the titanium dioxide is deposited to a total thickness of between 5 and 66 coating thickness units (CTU).
More preferably, the method includes the steps of:
arranging a tunnel on a conveyor belt such that the conveyor belt transports the glass container from an upstream end, at which articles enter the tunnel, to a downstream end, at which articles exit the tunnel,
the tunnel having
Preferably, the precursor of titanium dioxide comprises titanium tetraisopropoxide (TTIP).
Preferably the titanium tetraisopropoxide is introduced to the evaporator at a rate of between 10 and 30 cc/minute, more preferably between 20 and 28 cc/min.
Preferably, the carrier gas is directed through the evaporator at a rate of 20-30 slm, more preferably between 23 and 27 slm.
Preferably, the evaporator is heated to a temperature of between 170° C. and 210° C., more preferably between 190° C. and 205° C.
Preferably, the diluent gas is added at a rate of between 65 and 85 slm, more preferably between 70 and 80 slm
Preferably, an extraction pressure of between 80 and 120 Pa, more preferably between 90 and 110 Pa is applied to the at least one exhaust apertures.
Preferably, one or both of the carrier gas and the diluent gas comprises nitrogen.
Preferably, the method is used to produce a glass container having a titania coating having a thickness in the range 9 to 15 nm having a thickness variation of less than 5 nm.
The invention will now be described by non-limiting example, with reference to the appended figures in which:
and
The inventors have shown that inclusion of a titania layer on the container surface significantly improves the bursts strength of the container relative to an uncoated to container or a container coated with tin (IV) oxide coating only. Durability of the coating is also improved and the susceptibility of the SnO2 coating to ‘blow out’—where small areas of the coating become detached from the substrate—is reduced.
Following initial experimental data, which suggested these benefits of a titania layer, a series of work was performed to develop a method for depositing such coatings on glass bottles by CVD, during a continuous process for manufacturing glass bottles, and evaluating bottles so produced.
The titania coatings were deposited directly on the glass bottles at the ‘hot end’ of the continuous production cycle, that is at a point in the cycle soon after the bottles emerge from the blank and while they still bear residual heat from the casting step.
Referring to
At least one pair of linear arrays of inlet nozzles 15 is provided, one array 15 from the pair being located on each sidewall 13. Preferably each of the pair are located at substantially the same distance along the path of the articles (i.e. they are located substantially opposite each other). (N.B. while a pair of nozzle arrays is illustrated in this embodiment, a single array is adequate for some chemistries).
Further along the path of the articles, at least one pair of exhaust apertures 16 is provided, again one from the pair on each sidewall 13 and preferably substantially opposite each other.
During operation, chemical precursors of the coating to be deposited are directed to the interior of the tunnel via inlet nozzles 15 and travel along the tunnel in substantially the same direction (23 of
The effective length of exhaust apertures 16 may be varied by adjusting the height of damper 19. Damper 19 comprises a plate arranged to block a part of the slot forming the exhaust apertures
CVD reactants may be delivered to the nozzles 15 via heated delivery lines (not shown) in order to prevent condensation of vapour before it enters the hood. In some circumstances, formation of liquid can occur at the nozzles and the hood described here includes reflective plates 20, arranged to direct thermal radiation from the articles on to the nozzles in order to provide heating thereof.
Referring to
The inventors have found this arrangement especially effective in drawing exhaust gases from the hood. This arrangement not only draws exhaust gases and any excess reactant but ambient air is also drawn from the exit of the tunnel as illustrated by arrows 24. This air, entering the tunnel in the direction of arrows 24 provides a barrier to exhaust gases or excess reactants that might otherwise leak from the apparatus to the surroundings.
The total area of the slot 16 should be small, compared with the cross-sectional area of the conduit defined by walls 21a-21d and 22 to ensure uniform flow. However the smaller the area, the greater the suction that must be applied to the conduit for effective extraction and the final design choice represents a compromise between these two conflicting factors. A tunnel cross-sectional area to slot area ratio of between 1.5 and 2.5 is found to serve well (an area ratio of 1.6 represents about 10% variation in flow velocity when comparing the flow velocity at the top of the slot and the bottom).
The linear velocity of the CVD reactants exiting the nozzles 15 is an important factor in the achievement of effective coatings.
The articles enter the coating hood with a known velocity (typically 0.3 m/s to 1.5 m/s, or ˜90 to 700 articles per minute). The motion of the articles drag a flow of gas through the coater in a fashion similar to the action of a train moving through a tunnel. This gas flow is also driven by suction from the two exhaust apertures 16. To gain a uniform coating on the articles, a jet of coating precursor is preferably blown into the flow path, in one embodiment, perpendicular to the direction of the articles 23 during transit through the hood. The jet must have sufficient momentum so that a concentrated plume of coating gases is directed onto the centre line of the articles' motion. The process becomes inefficient if the highly concentrated plume of coating gases is instead directed to either wall 13 of the coating hood 11.
The choice of jet velocity is optimally identified by fluid flow modelling, but an approximate measure can be found by considering a fluid “kinetic energy ratio”. The flow of gases moving along the coating hood has a kinetic energy density given by approximately Kair=density-of-air×width-of-coater×bottle-velocity2 [units J/m2]. The injected jets of coating precursor have a kinetic energy of approximately Kjet=density-of-coating-precursor×width-of-nozzle×jet-velocity2 [unit J/m2].
A kinetic energy density ratio R=Kair/Kjet with R=0.5 is preferred, but good coatings have been seen for 0.1<R<3. If the inlet jet is faster than given by this ratio, i.e. the ratio R is too small, then the jet tends to pass through the path of the containers and is wasted on the opposing coating hood walls. If the inlet jet is slower than given by this ratio, the jet is not thrown far enough and the precursor is wasted on the wall adjoining the inlet nozzle. Similarly, if the coater hood must be made wider, then the jet velocity must increase to throw the jet far enough and so the jet velocity would be increased to maintain the target kinetic-energy ratio.
From this starting point, the velocity of the inlet jet is tuned during coating trials to give the thickest and most evenly distributed coating possible for the given chemistry and bottle velocity. For one particular coater dimensions and bottle velocity, an inlet jet of 8 m/s was found to be adequate with 0.5 m/s conveyor speed.
In the application used to generate the data below, the coating chamber was 165 mm wide, 285 mm tall and 1000 mm long. The coating chamber dimensions are chosen to give just enough room for the glass article to move through without causing crashes at the entrance. If the chamber is too small, then misalignment of glass containers on the conveyor can cause them to collide with the entrance to the coating hood.
A mask (not shown) is fitted to the entrance to the coating hood of approximately the same shape as the outline of the glass articles. This mask restricts the air drawn into the coating hood by the bottles and so gives a higher concentration of coating precursor inside the reaction chamber. The mask is designed to block as much air entering the start of the hood as possible without causing crashes of the glass containers on the conveyor.
The inlet nozzles are positioned at least 100 mm downstream of the entrance and preferably 300 mm. If the nozzles are close to the entrance, then coating gases escape from the entrance to the hood due to occasional backward travelling eddies in the coating plume. The length of the coating hood is chosen so that the chemical reaction has had sufficient time and distance to complete.
A pair of opposing vertical inlet nozzles are used in one embodiment as this helps to position the coating plume at the centre line of the coating hood. Using a nozzle on only one side of the hood may give a good enough coating uniformity for some applications.
The two exhaust ports at the end of the coating hood are specified to just prevent leakage from the end of the coater. The negative pressure on the exhaust slots is determined by fluid simulations. In the present case, the exhaust port has a 12 mm wide flow restriction which runs the full height of the exhaust port (285 mm). At least 100 Pa of suction behind the 12 mm flow restriction was found necessary to prevent gas leakage from the ends of the hood.
Care must be taken to ensure air cannot be drawn into the coating hood from underneath the conveyor belt. An adequate seal needs to be made between the edges of the conveyor belt and the coating hood.
Titanium tetraisopropoxide (TTIP) served as the precursor for titania coatings. This was delivered to the coating hood via an evaporator of the type known in the art. Essentially this comprises a heated metal tube within which the reactant is dropped into a stream of carrier gas.
The overall reaction for the deposition of titania may be represented as:
Ti(OC3H7)4+O2=>TiO2+4C3H6+2H2O
The inventors have found that titania coatings were conveniently deposited using the following parameter ranges:
TTIP delivery rate: 10-30 cc/min
Evaporator temperature: 170° C.-210° C.
Evaporator carrier gas: nitrogen, 20-30 slm
Diluent gas (added to carrier gas stream): nitrogen, 65-85 slm.
Extraction pressure (applied to exhaust apertures 16) 80-120 Pa
(slm=standard litre per minute, a unite well known in the art which refers to volumetric gas flow corrected for standardized conditions of temperature and pressure).
For comparative purposes, a series of bottles coated with SnO2, as is common in the industry, using the chemistry below, were also produced.
The tin oxide was also deposited by CVD during continuous bottle manufacture. This was done by a method that is well known in the art, using monobutyltin trichloride (MBTC) as the precursor. MBTC readily decomposes in the vicinity of the hot glass surface to provide tin (IV) oxide. Again, residual heat from the bottle casting step facilitates the deposition reaction:
C4H9SnCl3+H2O+6O2−>SnO2+2H2O+4CO2+3HCL
The tin oxide was deposited using a coating apparatus that was similar to that described in EP0519597B1 but purging of the ‘finish’ as referred to therein was achieved by a horizontal protective stream in an arrangement similar to
Referring to
Coating thicknesses are shown in Coating Thickness Units (CTU). This is an optical thickness unit that is well known in the glass industry. For oxide coatings as described herein, 1 coating thickness unit may be estimated to correspond with about 3 Angstrom.
The coated bottles were then tested for internal pressure resistance using a Ramp Pressure Tester 2 (RPT2), provided by AGR International Inc., 615 Whitestown Road, Butler, Pa. 16001, USA. Failure pressure after 1, 5, 10 and 20 line cycle similations was measured.
A line cycle represents is the repeated cycle of filling, emptying, washing (including caustic wash) that each bottle is subject to during its lifetime. These were simulated using a Line Simulator, which provides an accelerated and reproducible abuse treatment for evaluation of container designs in the laboratory environment. The Line Simulator is also provided by AGR International Inc.
The results of these measurements are shown in table 2, with pressures shown in psi.
The results in table 2 indicate that the titania coated bottles were consistently resistant to higher internal pressure than bottles having only the standard SnO2 coating.
The glass thickness of the bottles was also determined and these measurements are summarised in table 3 (thicknesses are quoted in inches).
Tensile breaking strength of the coated bottles was determined from an analysis of the internal pressure resistance data, wall thickness data and fracture analyses. This service is provided by AGR International Inc. The results of this determination are summarised in table 4 (units are PSI).
The tensile strength measurements summarised in table 4 suggest a significant improvement in the titania coated bottles over those coated with SnO2.
A further set of bottle samples were prepared having the following coatings:
1. SnO2 (industry standard)
2. TiO2/SnO2
SnO2 was deposited using reaction conditions previously described. TiO2 was deposited using the following conditions:
TTIP delivery rate: 25 cc/min
Evaporator temperature: 200° C.
Evaporator carrier gas: nitrogen, 25 slm
Diluent gas (added to carrier gas stream): nitrogen, 75 slm.
Extraction pressure (applied to exhaust apertures 16)—100 Pa
Only the lowest three nozzles (item 15 in
In order to determine the thickness and uniformity of titania coatings obtained, Time Of Flight Secondary Ion Mass Spectroscopy (TOF-SIMS) analysis was performed on the bottles having the TiO2/SnO2 and TiO2 coatings.
The results of these analyses are shown in tables 5 and 6 where “shoulder 2”, “shoulder 4”, “shoulder 6” and “shoulder 8” refer to four approximately equally spaced points around the circumference of the bottle at the shoulder with similar naming applied to points around the body and heel of the bottle.
Tables 5 and 6 indicate good, continuous (unbroken) coatings of typically about 10 nm for each of TiO2 and SnO2 on the dual coated bottles and 10 nm for the TiO2 only coated bottle.
The coating uniformity for SnO2 (reference), TiO2 and TiO2/SnO2 is also illustrated in
Uniformity of coatings is an important feature because if the coating thickness varies too much, this can give rise to optical effects which are undesirable in the finished product. The coated bottles on which tables 5 and 6, and
The data represented in table 6 has a mean of 11.7+/−3.7 nm [1 standard deviation]. Hence the data represents a coating that is in the approximate range 9 to 15 nm having a thickness variation of approximately 5 nm.
In order to establish whether the various coating combinations provided bottles with a higher tensile strength than the standard industry SnO2 coating, the coated bottles were tested for caustic wash resistance and bottle strength at a predetermined number of filling cycles using the methods previously described herein.
12 samples each of SnO2 (ref), TiO2/SnO2 and TiO2 were subjected to 2% NaOH at 80° C. for between 5 and 180 minutes. Scanning Electron Microscopy (SEM) imaging indicated that, while all coatings were still good after 30 minutes, the ref (SnO2) coating and the SiO2/SnO2 started to show degradation after 90 minutes. By 120 minutes the coating was completely gone.
The TiO2 coating was still present after 180 minutes.
42 samples were selected at a set of intervals of 1, 5, 10 and 20 line cycle simulations as previously described. Each simulated cycle consisted of 13.5 minutes of caustic exposure and a 30 minute pasteurisation step (filled and maintained at 65° C. for 30 Minutes).
Table 7 shows how the average tensile strength of the bottles varied with number of simulated cycles for the various coatings.
Table 7 shows that the tensile strength of bottles having a TiO2 coating is less affected by the repeated line cycles. In particular, they have a 30% greater average tensile strength, after 20 simulated filling line cycles, than the standard SnO2 coated bottle.
Moreover, visual inspection of the of the various bottles after 20 simulated line cycles showed a very high degree of ‘scuffing’ on the SnO2 coated bottles and very little on the TiO2 coated bottles. The former were unsuitable for further service whereas the latter were suitable.
Thus the results of the caustic wash resistance testing and tensile strength measurements indicate that the TiO2 coated bottles, according to the invention, provide a vessel having improved tensile strength that is durable under the cleaning and refilling cycles used in industry and thereby is suitable for re-use.
Thus the inventors have provided a method with reaction conditions, for coating glass containers to provide improved tensile strength (hence improved resistance to internal pressure). The coatings so produced are durable and, in particular, resistant to the treatment steps associated with recycling of bottles. The method lends itself in particular to implementation as part of a continuous production process by utilising residual heat from the bottle casting step.
The ability to recycle and the use of residual heat from an existing process offer considerable environmental benefits.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1523160.8 | Dec 2015 | GB | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/GB2016/054086 | 12/29/2016 | WO | 00 |
