[0001] The present invention relates to a process for treating filled containers closed
with metal closures to prevent rust formation, i.e. oxidative attack on iron.
[0002] During filling, closing and storing all kinds of beverages and foodstuffs in jars,
ceramic or metal containers, such as tins, bottles and pots, the foodstuff and beverage
industry frequently has to cope with the problem that certain iron parts of the closed
containers or the closures tend to corrode or rust. Particularly when the containers
are filled with acid-reacting products, which will often be the case from a viewpoint
of preservation, the presence of slight amounts of the product near or under the edge
of the closure can give rise to rust formation, as will be explained below.
[0003] For instance, when glass bottles filled with beer are closed with a crown cork, the
situation occurs that after filling rests of beer are present on the top and on the
exterior of the bottle at the moment of closing the bottle with the crown cork. Since
during manufacture the bottles have been treated with metal oxides which may also
be present on the top of the bottle near the crown cork, both metal oxides, rests
of beer and free metal, more particularly iron surface, are found near the crown cork.
On the one hand, this free metal surface originates from the cutting edge of the crown
cork, and, on the other hand, damage caused to the interior and the exterior of the
crown cork during closing leads to removal of a part of the protective layer on the
crown cork. Since the rests of beer consist of water having dissolved therein, among
other things, electrolytes with a pH in the acid range, there is a risk of corrosion
owing to electrolytic interaction of the various substances present near the crown
cork. This may manifest itself in a more or less perceptible rust formation on the
bottle next to the crown cork or on the crown cork.
[0004] The same problem occurs with other containers closed with metal closures, such as
jam jars with screw caps, mustard jars, but also with beer tins and vegetable tins.
[0005] To prevent rust formation, a great many researches were conducted in the past, which
researchers were mainly concentrated on improving the coating of the crown cork, cap,
etc., minimizing the amount of metal oxide on the bottle surface near the crown cork,
and, after the container has been closed, removing moisture as much as possible near
the closure. This moisture may be removed, e.g., by blow drying the container near
the closure.
[0006] For certain products the practice obtains of providing the container-with-closure
with a foil e.g., an aluminum foil which leads to a situation that moisture, if any,
can evaporate less easily, so that in this situation rust formation can occur sooner
and more easily. This is particularly the case in combination with containers, e.g.,
of ceramic material, which more readily give rise to corrosion of the iron in the
closure.
[0007] Accordingly, there is a marked need for a good economical method of preventing rust
formation on metal parts of containers closed with metal closure.
[0008] To that end, the invention is characterized by treating the assembly of closure and
container in closed condition with a diluted aqueous alkali metal silicate solution.
[0009] According to a preferred embodiment of the invention this assembly is treated with
sodium silicate, the silicate content in the alkali metal silicate solution preferably
ranging from 0.1 to 5 wt.%, more specifically from 0.2 to 1.0 wt.%. It is particularly
advantageous in the treatment of the closed containers to start from a diluted water
glass solution, which solution can be obtained by diluting commercially available
water glass with normal water.
[0010] At alkali metal silicate concentrations lower than 0.01% the activity is too poor,
while at concentrations above the upper limit there is a risk of discoloration of
the metal.
[0011] Surprisingly, it has been found that when the containers-with-closures are treated
near the metal closure with such a solution, rust formation does not occur at all,
even not when the treated containers are provided in wet condition with an aluminum
foil. An additional advantage is that the substances used, water and alkali metal
silicate are hardly objectionable from a viewpoint of security, health and appearance
of the treated containers.
[0012] In this connection it is observed that it is known per se indeed to use sodium silicate
for preventing corrosion of, e.g., central heating systems, but this is a situation
which is absolutely incomparable to the treatment of crown corks or comparable closures.
[0013] Furthermore, U.S. patent 4,351,883 discloses a process for treating aluminum surfaces
against the formation of tarnish and corrosion. In this process the aluminum surface
is provided with a solution containing an alkali metal silicate in combination with
certain film-forming organic polymers, which is followed by a heat treatment. The
prevention of rust formation is not involved here.
[0014] The treatment preferably takes place by spraying the diluted solution to the boundary
face of the closure and the container.
[0015] As containers, there may be used all the containers known for storing beverages and
foodstuffs, such as glass bottles, ceramic bottles, glass jars, but also deep-drawn
metal tins for carbonated beverages, and so-called "open tops", i.e. three-piece metal
tins capable of being closed on the top, such as vegetable tins, etc. The containers
may therefore be made of both glass, ceramic materials and metals. In the last case,
special mention may be made of tinplate which is often used for tins for carbonated
beverages.
[0016] According to the invention the above-mentioned containers are to be closed with metal
closures, in which connection it is of course material that the invention is effective
only if either the container or the closure is at least partly made on the basis of
iron. Suitable closures are in this connection crown corks which are to comprise not
only the conventional crown corks for beer or milk bottles, but also "twist crowns",
screw caps, flip tops, etc. The term metal closures, however, also comprises metal
screw caps, as used for jam jars, or mayonnaise, picalilli, gherkin and mustard jars.
Metal closures on the basis of iron preferably consist of "tin" or steel plate provided
with a tin or chromium layer.
[0017] With deep-drawn metal containers made of tinplate aluminum closures are often also
found. In this case of course, the corrosion does not occur at the closure itself
but at the metal container which can be damaged during applying the aluminum closure
or afterwards.
[0018] The above-mentioned closed containers are preferably filled with foodstuffs or beverages
having an acid pH, i.e. a pH less than 6. In case of carbonated beverages, such as
carbonated lemonades, fruit-juices and beer, this is definitely the case, but also
for non-carbonated beverages and for foodstuffs the aim will generally to slightly
acidify the product so as to improve its keeping qualities.
[0019] When many containers are filled, more particularly with carbonated beverages, the
aim is to achieve a slight foaming of the product during filling so that the air is
completely expelled form the space above the liquid, which will improve the keeping
qualities. Owing to this foaming up or over, liquid arrives at the exterior of the
container and contacts the metal closure, which leads to the "galvanic" effect described
above.
[0020] The treatment according to the invention is carried out at the closed container,
the exact moment of which treatment is not very critical. This may take place, e.g.,
immediately after the container has been closed but also at a later stage of the treatment
of the filled containers, e.g., shortly before applying foil, if any, after or preferably
before labelling or shortly before packaging.
[0021] If required, the treated container may be blow-dried, e.g., with compressed air.
This is not necessary, however, since an excellent anti-rust effect is also obtained
without blow-drying.
[0022] As already indicated, the solution with which the containers are treated is a diluted
alkali metal silicate solution obtainable by diluting water glass with water. It is
of course also possible to use alkali metal silicate solutions obtained otherwise.
The solution preferably has an Na₂O/SiO₂ molar ratio in the range of from 1 to 0.1,
a ratio of about 0.5-0.3 being preferred. The pH of such solutions is preferably from
10 to 14.
[0023] The invention will now be illustrated by some examples, which, however, do not mean
a limitation of the invention.
Example I and Comparative Example 1
[0024] A tank of stainless steel, as also used for sterilization or pasteurization tests,
is filled with normal mains water. Bottles previously filled with beer and closed
with a crown cork are immersed in this tank. Already after 1 day of immersion at room
temperature it can be established that incipient rust formation occurs at the unprotected
cutting edge of the crown cork. Also in those places where the lacquer coatings of
the crown cork would be damaged incipient rust formation can be established. In the
same arrangement but using 1% aqueous water glass solution instead of normal water,
rust formation still cannot be established after weeks of immersion.
Example II
[0025] In well-known techniques and plants bottles are filled with beer and closed with
a crown cork. This is performed with fully automatic machines and at velocities of
20,000-40,000 bottles per hour. Optionally, this process is followed by a pasteurization
process. In this example the invention is preferably used after this stage. For the
labelling machine the bottles are arranged in one row.
[0026] Along both sides of the conveyor belt feeding the bottles in one row, spraying nozzles
are placed at crown cork level. The spraying nozzles are so arranged that both the
crown cork but surely also the cutting edged and the bottom side of the crown cork
are sprayed by the liquid jets. The alkali metal silicate solution is prepared previously,
starting from a commercially available water glass solution (Na₂/O/SiO₂ molar ratio:
0.5) at a concentration of 30-35%, and diluting it with water to obtain a dry content
of 1%. This diluted solution is passed to the spraying nozzles from a reservoir via
a pipe and a pump with a slight excess pressure.
[0027] Depending on the machine speed, two to four spraying nozzles are mounted on each
side of the bottle conveyor belt. Rust protection is obtained by spraying, and, in
addition, rests of beer, if any, are removed from the mouth. Although it is sometimes
usual to blow-dry the last rests of moisture under the crown cork this is not necessary
when the invention is used. In practice, it has even been found that rust protection
will subsist, even if these rests of moisture are enclosed by applying an aluminum
foil over the bottle closure.
1. A process for treating filled containers closed with metal closures to prevent
rust formation, characterized by treating the assembly of closure and container in
closed condition with a diluted aqueous alkali metal silicate solution.
2. A process according to claim 1, characterized by using an aqueous sodium silicate
solution.
3. A process according to claim 1 or 2, characterized in that the content of silicate
is 0.01-5 wt.%, calculated as SiO₂ on the total solution.
4. A process according to claim 3, characterized in that the SiO₂ content is 0.2-1.0
wt.%.
5. A process according to claim 1, characterized by treating a glass container provided
with a metal closure on the basis of iron.
6. A process according to claims 1-4, characterized by treating a metal container
on the basis of iron with a metal closure.
7. A process according to claim 6, characterized by treating a metal container with
an aluminum closure.
8. A process according to claim 5, characterized by treating a bottle provided with
a crown cork.
9. A process according to claim 8, characterized in that the bottle contains beer.
10. A process according to claim 8, characterized by covering the crown cork, after
treatment, with a foil, preferably an aluminum foil.