WO2016038257A1

WO2016038257A1 - Composite gas conditioning vessel comprising a plurality of superimposed envelopes

Info

Publication number: WO2016038257A1
Application number: PCT/FR2015/052060
Authority: WO
Inventors: Emmanuel Baune; Chiara TARANTELLO
Original assignee: L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority date: 2014-09-09
Filing date: 2015-07-24
Publication date: 2016-03-17
Also published as: FR3025584B1; FR3025584A1

Abstract

The invention relates to a composite gas conditioning vessel comprising a hollow cylindrical body (1) defining an inner space (2) for receiving gas, a filament winding (3) coiled around said cylindrical hollow body (1), and a plurality of envelopes (7, 8) superimposed one over the other. Furthermore, it comprises a first envelope (7) arranged directly around, and in contact with, the filament winding (8), and a second envelope arranged directly around, and in contact with, said first envelope (7). At least one of said envelopes (7, 8) is designed to react by a visual change in the event of a mechanical impact which is potentially critical or damaging in terms of the integrity of the recipient, or in the event of exposure to a flame or to a temperature higher than 70°C for a duration of at least 30 seconds.

Description

Composite gas conditioning container

comprising several overlapping envelopes

The invention relates to a composite gas conditioning container, in particular a medical gas cylinder. Such a bottle is preferably used to condition an oxygen type gas but can also be used in the industrial field, food or otherwise.

Gases and gas mixtures, especially industrial and medical gases, are conventionally packaged in gas containers, such as gas cylinders, under pressure, that is to say at a pressure of up to several hundred absolute bar.

A container of the gas bottle type is typically formed of a hollow cylindrical body closed, at its base, by a bottom and comprising, at the top, an ogive carrying a neck provided with an outlet orifice through which the gas can be introduced or, conversely, extracted from the body of the bottle.

The hollow cylindrical body may be formed entirely of a metallic material, such as steel or an aluminum alloy, or may be composite, that is to say formed of a hollow part forming the cylindrical body, commonly called "liner", which is covered with a coil of filaments fixed by an epoxy resin for example.

Usually, the surface of a composite container is either polished to give it a durable and durable aesthetic appearance, or coated with a paint designed to be aesthetically pleasing and durable.

Sometimes, there is arranged around the body of the container one (or more) overpack intended to remain at least partly on the container during the phases of use of said container by a user and / or during the phases of packaging, transport, storage ... This or these overpacks forming one or more protective layers, may carry various markings.

As such, mention may be made of the documents WO-A-98/16776, WO-A-2012/035289 and CN-U-201651751 describing gas cylinders externally coated with a sleeve (s) or protective layer (s) (s). ), for example a plastic film. In the case of a composite container whose outer surface is simply covered with a polished epoxy resin or coated with a paint, there is the problem of tracing and a visual detection of damage and shocks that can suffer the container, which can affect its mechanical integrity over time.

Indeed, these damages and shocks are not easily detectable, all the less when communication, operational and regulatory constraints must be fulfilled because they can mask any shocks or deteriorations.

Thus, in the case of a container with a gel-coated epoxy finish (gel coat), the tracing or the detection of the damages is based on the resistance of the "gel coat" and on the frosting of the glass fibers underlying the "gel coat". In this case, a very localized low energy shock can strongly lower certain mechanical characteristics of the container without the resin and / or the glass fibers appearing on the surface of the container.

Moreover, in the case of a container with a "gel coat" type of paint, again, under certain conditions of low energy impact and very localized, the paint may be too strong, so do not present peeling and / or impact cracking, while the mechanical characteristics of the container are affected.

Thus, Figures 2 and 3 appended hereto show the damage generated inside a composite container (volume 2 liters) to metal liner subjected to an energy of 170J via an impactor 100 mm in diameter. As can be seen (Fig. 2), the inner wall of the liner is very damaged and deformed following the shock of the impactor, whereas externally (Fig. 3), these deteriorations are not easily detectable because the impact does not occur. is not or only very little visible.

Similarly, a plastic deformation of the liner may occur, permanent or not, according to the cycles of re-pressurization / emptying of the container, thus lowering certain mechanical characteristics of the container, and may jeopardize its safety over time.

In fact, these deformations or liner detachments are visible externally to the container only by the use of non-destructive control techniques, often expensive and slow, so impossible to implement industrially according to the current state of these techniques.

In one case as in the other, it follows that an effective detection of the shock is not possible by the operator and therefore it is not easy to distinguish such a container of deteriorated mechanical characteristics of the same healthy container, that is to say having not suffered shock or the like.

It may also be mentioned EP-A-300931 which describes a reservoir comprising an inner casing intended to ensure internal sealing and an outer casing serving as mechanical protection. These envelopes are not removable but constitute the body of the tank since they also maintain cups forming the bottom and bottom ends of the tank.

Furthermore, the document EP-A-1489350 teaches a gas cylinder whose body comprises an external marking covered with a transparent protective coating against abrasion, for example polyurethane. This coating is intended to protect the marking from premature wear.

In addition, the document WO-A-98/16776 proposes a gas cylinder whose body is covered with one or more sleeves serving to protect markings affixed to the body of the bottle, such as sticky labels. These sleeves may be formed of a sheet, a woven or a fabric. They are transparent or colorized.

However, none of the documents provides a solution for distinguishing a container affected by shock, severe deterioration or the like of a healthy container.

The problem is therefore to be able to distinguish a container affected by shock, deterioration or the like of a healthy container so as to overcome the aforementioned drawbacks and problems.

The solution of the invention is a composite gas conditioning container, in particular a pressurized gas cylinder, comprising:

a cylindrical hollow body, also called a "liner", defining an internal volume for receiving gas,

a filament winding wound around said cylindrical hollow body, and

- several envelopes superimposed on each other,

characterized in that it comprises:

a first envelope arranged directly around and in contact with the filament winding, and a second envelope arranged directly around and in contact with said first envelope, and

at least one of said envelopes is designed to react by a visual change during a mechanical impact potentially critical or damaging to the integrity of the container, or exposure to a flame or at a temperature greater than 70 ° C for a period of at least 30 seconds. As the case may be, the composite container according to the invention may comprise one or more of the following technical characteristics:

the cylindrical hollow body is made of polymeric or metallic material, for example steel or aluminum alloy.

the cylindrical hollow body is a cylinder 5 to 100 cm in external diameter, preferably 8 to 50 cm.

- The cylindrical hollow body is a cylinder having a wall thickness of between 0.1 mm and 20 mm, preferably 0.4 to 10 mm.

the filament winding comprises carbon, glass, Kevlar or aramid fibers, or combinations thereof.

the filament winding comprises fibers impregnated with resin.

at least the second envelope is removable.

the first envelope and the second envelope are removable.

the total thickness of the superposed envelopes is between 0.05 and 5 mm, preferably less than 3 mm, more preferably less than 2 mm.

- the second envelope is transparent.

- The second envelope is thicker than the first, giving it a better wear resistance, preferably without the possibility of tearing or breaking into several easy pieces, while allowing tracing to mechanical impacts or stresses at the relevant temperature and recognizable.

a third envelope is arranged around said second envelope.

- The envelopes are formed of a polymer material selected from polyester (PET), polyolefin (PAO), polyurethane (PUR), and polyvinyl chloride (PVC).

- The envelopes are made of PVC; PVC being preferred.

the thickness E1 of the first envelope is smaller than the thickness E2 of the second envelope, that is to say E1 <E2.

the thickness E1 of the first envelope is less than 500 μιη, in general less than 300 μιη, typically less than 200 μιη, for example of the order of 50 to 175 μιη.

the thickness E2 of the second envelope is less than 5 mm, preferably between 0.5 mm and 4.5 mm.

- The thickness E3 of the third envelope is less than the thickness E2 of the second envelope, that is to say E3 <E2. the thickness E3 of the third envelope is less than 500 μιη, in general less than 300 μιη, typically less than 200 μιη, for example of the order of 50 to 175 μιη.

the first envelope and / or the second envelope form sleeves covering more than 60% of the outer surface of the cylindrical hollow body covered with the filament winding, preferably from 80% to 100% of said outer surface and advantageously the whole of the cylindrical hollow body.

the envelopes are sheets (i.e. films), preferably rectangular or square, or cylindrical sleeve (i.e.) sheath.

- He understands :

. a first envelope bearing one or more markings,

. a second transparent envelope, designed to react by a visual change during a mechanical impact or exposure to a flame or temperature exceeding 70 ° C, and

a third transparent envelope, the second envelope being arranged between the first envelope and the third envelope.

- the first envelope, the second envelope and the third envelope are in

PVC.

- he is a bottle of gas.

- It comprises the body of the container comprises, at one end, a bottom and at the other end, a neck provided with an orifice communicating with the internal volume of the container.

- It includes a valve block or integrated pressure regulator valve attached to the neck.

According to a preferred embodiment, the composite container of the invention, as described above, comprises:

a cylindrical hollow body defining an internal volume for receiving gas,

a filament winding wound around said cylindrical hollow body, and

several envelopes superimposed on each other, comprising a first envelope arranged directly around and in contact with the filament winding, and a second envelope arranged directly around and in contact with said first envelope, and is such that:

the thickness E 1 of the first envelope is smaller than the thickness E 2 of the second envelope, a third envelope is arranged around said second envelope, said envelopes being formed of a polymer material chosen from polyester (PET), polyolefin (PAO), and polyvinyl chloride (PVC),

- the first envelope bearing one or more markings,

the second envelope is transparent, and

- the third envelope is transparent.

Preferably, according to this preferred embodiment, the thickness E1 of the first envelope is smaller than the thickness E2 of the second envelope, and the thickness E3 of the third envelope is smaller than the thickness E2 of the second envelope. . Advantageously, the thickness E2 of the second envelope is less than 500 μιη.

Advantageously, the thicknesses E1, E3 of the first and third envelopes, respectively, are less than 500 μιη, typically less than 300 μιη, preferably less than 200 μιη, advantageously of the order of 50 to 175 μιη.

Furthermore, the thickness E2 of the second envelope is advantageously less than 5 mm, preferably between 0.5 mm and 4.5 mm.

In all cases, it is ensured that the total thickness of the superposed envelopes is between 0.05 and 5 mm, preferably less than 4 mm, more preferably less than 3 mm, and even less than 2 mm.

Advantageously, the first, second and third envelopes are all formed of PVC.

Such a superposition of envelopes having the thicknesses E1, E2 and E3 mentioned above, preferably made of PVC, makes it possible to distinguish visually and simply a container which has been affected by a shock or the like of a healthy container, ie having not undergone mechanical shock, which makes it possible to solve the disadvantages and problems existing in the prior art.

The invention further relates to a use of a container according to the invention, in particular a gas cylinder, for storing a gas or gas mixture at a pressure up to 700 bar abs, generally less than 500 bar, typically between 150 and 320 bar abs.

Typically, the gas or gas mixture stored in the container comprises one or more gaseous compounds chosen from air, oxygen, nitrogen, hydrogen, argon or mixtures thereof, helium , xenon, krypton, NO, N ₂ 0, CO, C0 ₂ , breathable mixtures, such as those used for underwater diving (Heliox, Nitrox ...) and mixtures thereof. The invention will now be better understood thanks to the following detailed description, given by way of illustration but without limitation, with reference to the appended figures among which:

FIG. 1 schematizes a view in longitudinal section of an embodiment of a gas container according to the invention,

FIG. 2 illustrates a deterioration of the internal liner of a conventional gas cylinder according to the prior art, following a violent impact on its outer peripheral wall,

- Figure 3 shows the impact not visible on the body of the bottle of Figure 2, and

- Figures 4 and 5 show the result of the same impact on a non-coated container according to the prior art and a coated container according to the invention, respectively.

FIG. 1 schematizes an embodiment of a container according to the invention, namely a composite type gas bottle which comprises a cylindrical hollow body 1 with a bottom 6 at its base, and an ogival-shaped upper part. 4 having a neck provided with an orifice 5 communicating with the inner volume 2 of the container where the gas is stored.

Bottles with a flat bottom are called type 2, while those with a convex bottom, as in Figure 1, are called type 3 or 4.

The cylindrical hollow body 1 is in fact formed of a cylinder or liner of polymeric or metallic material (steel, aluminum alloy, etc.) around which is wound a filament winding 3 of carbon, glass or Kevlar fibers. aramid, or combinations thereof. The fibers are impregnated with resin, preferably epoxy resin. This filament winding 3 forms a layer formed of fiber and resin on the surface of the liner 1.

In other words, the container is of composite construction with metal liner or polymer, and finished in the form of a layer of epoxy resin and fibers, for example glass fibers, visible underlying, without finishing paint on the part of the container, that is to say its cylindrical part 1.

On the other hand, a coating of paint or the like may be affixed to the ogival-shaped upper part 4 of the container.

Several removable envelopes 7, 8 are arranged directly around the cylindrical body while being superimposed on each other. More specifically, a first envelope 7 is arranged around and in contact with the filament winding 3 wound around the liner 1, and a second envelope 8 is arranged directly around and in contact with said first envelope 7. One (or more) additional envelope 9 superimposed on the second envelope 8 can be provided. These envelopes 7, 8, 9 form overpacks of the gas container, which provide functions of protection against dirt and abrasions and other mechanical stresses, various communication and / or commercial and / or regulatory coloring, or texturing, tracing external aggression (shocks ...), assistance with laying / removal.

More specifically, according to the invention, in order to distinguish a container

"Affected" by a shock, deterioration or the like, of a "sound" container, at least one of said envelopes 7, 8 is designed to react by a visual change during a mechanical impact, that is to say -or shock, or exposure to a flame or temperature greater than 70 ° C for a period of at least 30 seconds. On the contrary, as already explained above and visible in Figures 2 and 3, a significant deterioration of the inner liner (Figure 2) of a conventional bottle shocked on the outer wall of its barrel (Figure 3). is not easily detectable, especially when the barrel of the bottle is covered with surface paint.

The envelopes of a container according to the invention are designed and dimensioned to cover at least the cylindrical barrel portion 1 of the container. Optionally, other parts, for example the ogive 4 or the bottom 6, may also be equipped with one (or more) overpack according to the invention.

In all cases, at least two superimposed removable envelopes 7, 8 are provided constituting cylindrical sleeves or rectangular-shaped films wound around the cylindrical body 1 of the gas container.

The first casing 7 is thus put in place directly in contact with the layer formed by the winding of fibers and epoxy resin, while the second casing 8 is arranged on the first casing 7. If a third casing 9 is used, it is superimposed on the second envelope 8.

The first casing 7 preferably has a thickness E1 between 50 and 200 μιη, whereas the second casing 8 preferably has a thickness E2, such that E2> E1, for example E2 is between 0.4 and 1.3 mm. . The third envelope 9 which is optional, preferably has a thickness E3 less than or equal to 300 μιη, typically between 50 and 200 μιη.

In all cases, the total thickness (E1 + E2 + E3) of all the envelopes 7, 8, 9 superimposed is between 0.05 and 5 mm, preferably less than 3 mm, more preferably between 0.05 and 1.5 mm about.

The envelopes 7, 8, 9 are fixed either by stretching them mechanically, by gluing, by thermal shrinkage, or by welding. Some envelopes can combine several effects for their placement around the barrel, for example a stretching effect and a thermal shrinkage effect, or a mechanical effect with a gluing action

The constituent material (s) of the various envelopes 7, 8, 9 can be chosen from polyester (PET), polyolefin (PAO), polyurethane (PUR) and polyvinyl chloride (PVC), preferably the envelopes are all PVC .

Preferably, the second envelope 8 is transparent, preferably the outermost envelope to the container barrel, and advantageously completely covers the outer surface of the barrel of the container.

Moreover, at least one of the envelopes 7, 8, 9 is printed by an inkjet, laser or other technique, preferably the first envelope 7.

For example, at least one envelope is predominantly white or light in color, preferably the first envelope 7, over at least 60% of its surface. This envelope can also be printed to communicate information of commercial order (name of mark, logo ...) or regulation (instructions of use ...).

Preferably, the transparent outer shell 8 is replaced before each filling of the container with gas.

The installation and removal of the envelopes 7, 8, 9 on the container can be operated manually and / or with (semi-) automatic equipment.

In addition, stickers, such as adhesive films of reduced size (<5% of the developed outer surface of the drum) can be affixed between two envelopes, in particular for regulatory or commercial reasons.

Optionally, one or more accessories, such as a foot fitted or glued bottle, and / or a skirt arranged on the ogive 4, may also be installed on the container.

Example of realization

A composite gas bottle according to the invention for containing medical grade oxygen has been made in the following manner.

It is fixed on a liner 1 or cylindrical hollow tube, metal or polymer, wound of a filament winding consisting of glass fibers, aramid, Kevlar and / or carbon embedded in an epoxy resin, 10 cm in outer diameter, several envelopes 7, 8, 9, namely here three successive envelopes superimposed on each other.

These include from the surface of the shaft to the outside:

a first casing 7 or thin sheath forming a cylindrical sleeve made of PVC having a first thickness El of the order of 100 μιη, the surface of which is white in color and is printed with various markings, such as brand name, logo, registration This first casing 7 is put in place by stretching or by heat-shrinking around the filament winding 3 (ie glass fibers and epoxy resin) wound around the liner 1.

a second envelope 8 or transparent thick sheath also forming a cylindrical sleeve made of PVC, having a second thickness E2 of the order of 1 mm. This second envelope 8 is put in place by heat shrink. It can detect severe impacts or shocks affecting the body of the container since they leave a trace or residual mark immediately detectable visually and irreversibly naturally.

- A label (optional), transparent or not, and adhesive of size of about 2 cm x 5 cm is placed manually on second envelope 8.

a third shell 9 or thin sheath of cylindrical shape and formed of PVC of the order of 100 μιη of thickness E3, also transparent, which can be removed before each filling of the container with gas. It is put in place by stretching or heat shrinking.

In order to test such a bottle when it is subjected to an impact, comparative tests were carried out between a gas cylinder according to the invention and a conventional gas cylinder.

In both cases, a 50J impact energy impactor with a diameter of 13 mm was applied to the body or to the bottles. The resulting damage is shown in Figures 4 and 5.

As can be seen, the impact that has taken place is not easily detectable on the body of the bottle of the prior art (FIG. 4), whereas it is clearly visible on that of the bottle according to the invention ( Figure 5) due to the damage of the combination of envelopes 7, 8, 9 covering the fut of the bottle according to the invention, in particular the three successive envelopes of PVC and thicknesses E1, E2 and E3 mentioned above.

However, such a shock has resulted in a lowering of the cycling performance of the two bottles by approximately 70% attributable to an internal detachment (depression of about 2.7 mm) of the underlying metal liner (same phenomenon as in FIG. ), which is virtually undetectable on the uncoated container (Fig. 4) according to the prior art, but easily identifiable by the circular mark left (diameter about 6 mm) on the coated container according to the invention (Fig. 5).

The fact of being able to detect such internal degradation of the liner via a simple visual inspection of the body of the bottle allows the same to be discarded and to increase the safety for the user. In general, in the context of the invention, we consider that an impact trace, circular or longitudinal, of size (ie diameter or width) at least equal to 4 mm is a reason for isolation of the container , followed by its removal or at least a thorough internal examination after disassembly of the faucet fitted to this container and / or external by appropriate non-destructive testing.

Similarly, a gas cylinder according to the invention, subjected to excessive heat exposure (fire, contact with a flame or the like), will present an outer envelope with brownish traces of discoloration, local, and / or melted and / or deformed areas, even burns. This will also isolate the container. Such detection is not possible or easy with conventional bottles.

In general, a container according to the invention, such as a gas bottle, can be advantageously used to store any type of gas or gas mixture at a pressure up to 700 bar and is therefore usable not only in the medical and health field, for example to condition an oxygen type gas, but also in the industrial field, the food field or any other field.

Claims

claims

A composite gas conditioning container comprising:

a cylindrical hollow body (1) defining an internal volume (2) for receiving gas,

a filament winding (3) wound around said cylindrical hollow body (1), and

- several envelopes (7, 8) superimposed on each other, comprising a first casing (7) arranged directly around and in contact with the filament winding (3), and a second casing (8) arranged directly around and in contact with said first envelope (7),

characterized in that it comprises:

at least one of said envelopes is designed to react by a visual change during a mechanical impact potentially critical or damaging to the integrity of the container, or exposure to a flame or at a temperature greater than 70 ° C for a period of at least 30 seconds.

2. Container according to the preceding claim, characterized in that the cylindrical hollow body (1) is of polymeric material or metal.

Container according to one of the preceding claims, characterized in that the filament winding (3) comprises carbon, glass, Kevlar or aramid fibers, or combinations thereof, preferably the fibers are impregnated with resin. .

4. Container according to one of the preceding claims, characterized in that at least the second casing (8) is removable, preferably the first casing (7) and the second casing (8) are removable.

5. Container according to one of the preceding claims, characterized in that the total thickness of the envelopes (7, 8) superimposed is between 0.05 and 5 mm.

6. Container according to one of the preceding claims, characterized in that the thickness (El) of the first casing (7) is less than 0.5 mm.

Container according to one of the preceding claims, characterized in that the first casing (7) and / or the second casing (8) form sleeves covering more than 60% of the outer surface of the cylindrical hollow body (1) covered. filament winding (3), preferably from 80% to 100% of said outer surface.

8. Container according to one of the preceding claims, characterized in that the thickness (El) of the first casing (7) is less than the thickness (E2) of the second casing (8).

9. Container according to one of the preceding claims, characterized in that a third envelope (9) is arranged around said second envelope (8), preferably the thickness (E3) of the third envelope (9) is lower to the thickness (E2) of the second envelope (8).

10. Container according to one of the preceding claims, characterized in that the second envelope (8) is transparent and / or the third envelope (9) is transparent.

Container according to one of the preceding claims, characterized in that: the thickness (El) of the first envelope (7) is smaller than the thickness (E2) of the second envelope (8),

a third envelope (9) is arranged around said second envelope (8), said envelopes (7, 8, 9) being formed of a polymer material selected from polyester (PET), polyolefin (PAO), and polyvinyl chloride (PVC),

the first envelope (7) bearing one or more markings,

the second envelope (8) is transparent, and

the third envelope (9) is transparent.

Container according to one of the preceding claims, characterized in that the thickness (El) of the first envelope (7) and / or the thickness (E3) of the third envelope (9) are less than 500 μιη, typically less than 300 μιη.

13. Container according to one of the preceding claims, characterized in that the first casing (7), the second casing (8) and the third casing (9) are PVC.

14. Container according to one of the preceding claims, characterized in that it is a gas cylinder.

15. Use of a container according to one of the preceding claims for storing a gas or gas mixture at a pressure up to 700 bar.