This invention relates to the monitoring of the condition of subsea metal parts such as cable connectors and in particular to providing a warning of the incidence of de-lamination of polymeric sheaths for such parts.
In seawater metal corrosion occurs because of the generation of a corrosion cell. Steel and many other metals are not electrochemically stable in seawater and hence would corrode without preventative measures. Therefore, most metals used in seawater are coupled to a sacrificial anode. Galvanic corrosion will cause the more active metal (the sacrificial anode) to dissolve. In a corrosion cell the cathode does not dissolve, thereby protecting the metal of importance. However, protecting subsea infrastructure in this way can cause cathodic delamination of subsea cables, and it is recognised as the major cause of subsea cable failure.
The invention recognises the possibility of monitoring a subsea part by means of monitoring the local pH at an interface between a metal part, such as the metal shell of a connector, and its protective polymeric sheath. In its preferred form the invention provides a device which can provide such monitoring for very long periods of time.
In one form the invention provides a subsea device comprising a metal part disposed in a polymeric sheath, and including means for providing a sensible indication of pH at an interface between the part and the sheath.
The part may be the metal shell of a connector. The term ‘connector’ is intended to mean any form of connector for a cable to a subsea housing or other structure, whether releasable or non-releasable, whether making external connection or internal connection (as in the example of a ‘penetrator’). When a cable extends from the connector, the cable adjacent the connector would be covered by the polymeric sheath. The said means may comprise a chemical indicator and the sheath is preferably sufficiently translucent to allow visual observation of the indicator. The chemical indicator may comprise phenolphthalein.
The invention also provides a method of making a pH indicator for a subsea connector which has a metal shell, comprising:
The method preferably further comprises moulding a translucent polymeric sheath over the sleeve and the cable adjacent the connector.
As previously mentioned, in seawater metal corrosion occurs because of the generation of a corrosion cell.
At the interface between the anode 4 and seawater 2 the metal (zinc) ionises:
Zn→Zn+++2e−
At an interface 5 between the metal 8 of the connector and the moulding 6, as the polymer moulding 6 becomes saturated with seawater and dissolved oxygen, there occurs the formation of hydroxide ions by virtue of the reaction:
2H2O+O2+4e−→4OH−
The reaction produces a very high pH (alkaline) at a region 7 of the interface between the cathodically polarised surface and the material directly connected to it, as shown in
As a pH change at the interface between the polymer and the metal part is a precursor of the blistering, a pH indicator at the metal polymer interface should give an early indication of cable delamination before any delamination occurs. Importantly, the pH change is significant (highly alkaline) and it is therefore feasible to detect the change by means of a chemical indicator.
One example is shown in
A pH indicator used as described needs to be stable for a long time, typically at least several years. Phenolphthalein is a standard solution used for pH indication. It remains clear at pH levels from pH 1 (highly acidic) to (approximately) pH 9 (alkaline), where it turns red or pink to pH 14 (highly alkaline). The powdered form of phenolphthalein is highly stable and has no specified shelf life. For use as a pH indicator phenolphthalein may be mixed with ethanol. The stability of this indicator solution is dependent on the concentration of the solution which changes over time due to evaporation or other loss of the alcohol. In this subsea context, a phenolphthalein solution may be contained in an air-tight and water-tight moulding inhibiting the loss of alcohol and therefore preserving the stability of the indicator solution.
The invention is not confined to the use of phenolphthalein. Other possible chemical indicators include thymol blue, congo red, methyl red , methyl orange, azolitmin, phenol red and so on.
The chemical pH sensor described will change colour to red or pink to warn of a pending cathodic delamination failure. Therefore, the connector with the embedded indicator must be visually observed at regular intervals. This observation can be included in a routine survey of subsea structures by a ROV (or by a diver in shallow water). Alternatively it may be observed by a camera or CCTV.
Other chemical indicators might be used instead of the phenolphthalein-based indicator described above, provided that they are sufficiently stable for the long periods of use that may be required.
Furthermore it is feasible to employ an electronic pH sensor to provide an electrically sensible indication of pH at the metal-sheath interface instead of a visually sensible indication required for a chemical indicator. Power and communication for this electronic sensor could be provided via spare pins on the connector. Such a sensor would not require visual monitoring. However, en electronic sensor is not at present preferred because commercial available electronic sensors are not proven to have the ability to remain stable for a long time (at least several years).
Number | Date | Country | Kind |
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1208986.8 | May 2012 | GB | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/GB2013/000215 | 5/14/2013 | WO | 00 | 2/6/2014 |