Composite storage tank for gaseous hydrogen

Abstract

A composite storage tank comprises a composite wall enclosing a gas storage volume and defining a cylindrical portion of the tank. The composite wall incorporates first and second sets of metallic fibres each of which is susceptible to embrittiement by hydrogen and has ends extending through the exterior surface of the composite wall. By measuring the electrical resistances of the metallic fibres, a measure of the amount of hydrogen that has leaked through the composite wall over a period of time, and the present physical condition of the tank, may be determined. The approximate axial and azimuthal coordinates of a particular leakage point may also be determined.

Claims

1. A composite storage tank for gaseous hydrogen, the tank comprising a composite wall enclosing a gas storage volume and a metallic fibre which is susceptible to embrittlement by hydrogen incorporated within the composite wall, wherein ends of the metallic fibre extend through the exterior surface of the composite wall.

2. A composite storage tank according to claim 1, wherein the composite wall defines a cylindrical portion of the tank and the metallic fibre extends substantially parallel to the central longitudinal axis of the cylindrical portion of the tank.

3. A composite storage tank according to claim 2, wherein the composite wall includes a plurality of metallic fibres each of which is susceptible to embrittlement by hydrogen and which extends substantially parallel to the central longitudinal axis of the cylindrical portion of the tank, the ends of each metallic fibre extending through the exterior surface of the composite wall, and wherein each metallic fibre is located at a respective azimuthal position with respect to the central longitudinal axis of the cylindrical portion of the tank.

4. A composite storage tank according to claim 1, wherein the composite wall defines a cylindrical portion of the tank, the metallic fibre extends azimuthally at a single axial position with respect to the central longitudinal axis of the cylindrical portion of the tank and the ends of the metallic fibre extend through the exterior surface of the composite wall.

5. A composite storage tank according to claim 4, wherein the composite wall includes a plurality of metallic fibres each of which is susceptible to embrittlement by hydrogen and which extends azimuthally at a respective axial position with respect to the central longitudinal axis of the cylindrical portion of the tank, and wherein the ends of each metallic fibre extend through the exterior surface of the composite wall.

6. A composite storage tank according to claim 1, wherein the composite wall defines a cylindrical portion of the tank and includes first and second sets of metallic fibres each metallic fibre being susceptible to embrittlement by hydrogen, metallic fibres of the first set each extending substantially parallel to the central longitudinal axis of the cylindrical portion of the tank at a respective azimuthal position and metallic fibres of the second set each extending azimuthally at a respective axial position with respect to the central longitudinal axis of the cylindrical portion of the tank, and wherein the ends of each metallic fibre extend through the exterior surface of the composite wall.

7. A composite storage tank according to claim 1, wherein the composite wall comprises an organic matrix composite.

8. A composite storage tank according to claim 1, wherein the tank comprises a polymer liner in contact with the interior surface of the composite wall.

9. A composite storage tank according to claim 1, wherein at least one metallic fibre incorporated within the composite wall is pre-stressed.

10. A composite storage tank system comprising a composite storage tank according to claim 1 and means for measuring the electrical resistance of the or each metallic fibre.

11. An aircraft comprising a composite storage tank system according to claim 10, and at least one of a polymer electrolyte membrane (PEM) fuel cell and a hydrogen-burning gas turbine engine, the PEM fuel cell and/or the gas turbine engine being arranged to receive gaseous hydrogen from the composite storage tank of the composite storage tank system.

Description

DESCRIPTION OF THE DRAWINGS

(1) Embodiments of the invention are described below by way of example only and with reference to the accompanying drawings in which:

(2) FIG. 1A illustrates a first stage in the process of embrittlement of metal in the presence of gaseous hydrogen;

(3) FIG. 1B illustrates a second stage in the process of embrittlement of metal in the presence of gaseous hydrogen;

(4) FIG. 1C illustrates a third stage in the process of embrittlement of metal in the presence of gaseous hydrogen;

(5) FIG. 2 shows a longitudinal section of a first example composite storage tank of the invention;

(6) FIG. 3 shows a transverse section through the tank of FIG. 2;

(7) FIG. 4 illustrates variation in resistance of a metallic fibre comprised in the FIG. 2 tank;

(8) FIG. 5 shows a longitudinal section though a second composite storage tank of the invention;

(9) FIG. 6 shows a longitudinal section though a third composite storage tank of the invention respectively; and

(10) FIG. 7 shows a longitudinal section of a fourth composite storage tank of the invention.

DETAILED DESCRIPTION

(11) Many metals embrittle on contact with hydrogen. Referring to FIG. 1A, at room temperature, hydrogen atoms 10 can be absorbed by carbon steel alloys & other metals. Hydrogen which is absorbed may be present in either atomic or molecular form. Given enough time, the hydrogen diffuses to metal grain boundaries 12 and forms bubbles 14 at these metal grain boundaries as shown in FIG. 1B. These bubbles coalesce (FIG. 1C) to form larger bubbles 16 which exert pressure on the corresponding metal grains. The pressure can increase to levels where the metal has reduced ductility and strength.

(12) Hydrogen can enter and diffuse through steel even at room temperature. This can occur during various manufacturing and assembly operations or operational use—anywhere that metal comes into contact with atomic or molecular hydrogen. In common metal processing operations, there is a possibility of absorption of hydrogen during acid pickling and electroplating operations where hydrogen is evolved in chemical reactions. Hydrogen absorption can also occur when a component is in service if steel is exposed to acids or if corrosion of the steel occurs.

(13) As a result of hydrogen adsorption, hydrogen embrittlement occurs when a metal becomes brittle as a result of the introduction and diffusion of hydrogen into the metal. The degree of embrittlement is influenced both by the amount of hydrogen absorbed and the microstructure of the metal. Microstructures which bestow high strength, often monitored by hardness level, or having specific distributions of grain boundary particles or inclusions, can result in increased susceptibility to embrittlement. This phenomenon usually becomes significant when it leads to cracking. This happens when sufficient stress is applied to a hydrogen-embrittled object. Such stress states can be caused both by the presence of residual stresses, associated fabrication operations such as forming and welding, and applied service stresses. The severity of hydrogen embrittlement is a function of temperature: most metals are relatively immune to hydrogen embrittlement, above approximately 150° C.

(14) lntergranular cracking occurs when cracks form and grow along weakened grain boundaries in a metal. In the case of hydrogen embrittlement, the hydrogen bubbles at the grain boundaries of the alloy weaken the metal. There are three key requirements for failure due to hydrogen embrittlement: (i) a susceptible material; (ii) exposure to an environment that contains hydrogen; and (iii) the presence of tensile stress on the component.

(15) High-strength steels with tensile strength greater than about 145 ksi (1000 MPa) are the alloys most vulnerable to hydrogen embrittlement. Normally these are used as ‘design rules’ to avoid hydrogen embrittlement failures, however this invention uses the hydrogen embrittlement effect as the sensing element in a hydrogen tank.

(16) Referring to FIGS. 2 and 3, a first example organic composite storage tank 100 of the invention comprises an organic matrix composite wall 102 defining a storage volume 116 for storing gaseous hydrogen. The tank 100 comprises a polymer liner 118 (e.g. polypropylene or polyethylene) in contact with the internal surface of the composite wall 102, i.e. the tank 100 is a so-called “Type IV” tank. The tank 100 comprises a cylindrical central section 106 formed integrally with domed or hemispherical end sections 108A, 108B and has a central longitudinal axis 101. A metallic coupling element 110 passes through the composite wall 102 and the polymer liner 118 at the end section 108B and allows for filling and emptying of the tank 100. A metallic fibre 112, which is selected specifically for its susceptibility to embrittlement in the presence of hydrogen, is incorporated into the lay up of the tank 100 and has a lead-out region 113 extending beyond the tank 100 to an electrical interrogation unit 114. The metallic fibre 112 is located within the composite wall 102 at a radial position r greater than that of the polymer liner and extends longitudinally and substantially parallel to the central longitudinal axis 101 of the tank 100. The azimuthal position of the metallic fibre 112 over the cylindrical central section 106 is indicated by ϕ in FIG. 3.

(17) The metallic fibre 112 may be formed from any one of a range of metallic alloys which are susceptible to hydrogen embrittlement, for example high strength steel (typically greater than 32 Rockwell C hardness/UTS >1000 MPa), stainless steel, titanium alloy (e.g. Ti 6-4), vanadium, vanadium alloys and nickel alloys. Preferably the metallic fibre 112 is thin (less than 100 μm in diameter) and laid into the composite wall 102 with a pre-stress applied to it in order to increase its stress sensitivity and its propensity to break during hydrogen embrittlement. During fabrication of the tank 100, the metallic fibre 112 is co-wound or laid-up into the structure of the tank 100 with a tensile pre-stress applied to it during lay-up and cure.

(18) FIG. 4 shows the variation in resistance of the metallic fibre 112 as a function of time. During normal operation of the tank 100, the metallic fibre 112 exhibits no change in electrical resistance as measured by the interrogator 114. This corresponds to portion 1 of the graph shown in FIG. 4. If the polymer liner 118 is defective, hydrogen will diffuse through the composite wall 102 and interact with the metallic fibre 112, embrittling it. The rate at which hydrogen diffuses through the composite wall 102 depends on the extent of any cracking or delamination in the composite wall 102. This diffusion results in an increase in electrical resistance of the metallic fibre 112, as indicated by portion 2 of the graph of FIG. 4. Strain cycles on the tank 100 resulting from repeated charging/discharging cycles, combined with pre-stress in the metallic fibre 112, will eventually cause the metallic fibre 112 to undergo brittle failure, indicated by portion 3 of the graph in FIG. 4. The electrical interrogator 114 will detect this as an open circuit (infinite) resistance. The resistance of the metallic fibre 112 therefore represents an integrated history of leakage through the polymer liner 118 and the composite wall 102.

(19) FIG. 5 shows a longitudinal section though a second example organic composite storage tank 200 of the invention. Parts of the tank 200 which correspond to parts of the tank 100 of FIGS. 2 and 3 are labelled with reference signs differing by 100 from those labelling the corresponding parts in FIGS. 2 and 3. The tank 200 has multiple metallic fibres such as 212A, 212B, 212C at different azimuthal positions within the composite wall 202 of the tank 200. Electrical interrogators such as 214A, 214B, 214C therefore provide information on leaks over a range of azimuthal positions within the composite wall 202. The azimuthal position of a particular leakage point may be determined.

(20) FIG. 6 shows a longitudinal section through a third example organic composite storage tank 300 of the invention. Parts of the tank 300 which correspond to parts of the tank 100 of FIGS. 2 and 3 are labelled with reference signs differing by 200 from those labelling the corresponding parts in FIGS. 2 and 3. The tank 300 has multiple metallic fibres such as 312A, 312B, 312C at different axial positions within the composite wall 202 of the tank 200. Electrical interrogators such as 314A, 314B, 314C therefore provide information on leaks over a range of axial positions within the composite wall 202. The axial position of a particular leakage point may be determined.

(21) FIG. 7 shows a longitudinal section through a fourth example organic composite storage tank 400 of the invention. Parts of the tank 400 which correspond to parts of the tank 100 of FIGS. 2 and 3 are labelled with reference signs differing by 300 from those labelling the corresponding parts in FIGS. 2 and 3. The tank 400 has multiple metallic fibres such as 412A, 412B, 412C at different azimuthal positions within composite wall 402. Multiple metallic fibres such as 412D, 412E, 412F are provided at different axial positions. Electrical interrogators such as 414A-F therefore provide information on leaks over a range of azimuthal and axial positions. The azimuthal and axial positions of a particular leakage point such as 499 may be determined in the case of the tank 400; for example a leakage point 499 will give rise to increases in the electrical resistance of the metallic fibres 412A and 412F but will not affect the electrical resistances of the other metallic fibres 412B-E.

(22) The composite storage tanks 100, 200, 300, 400 provide for leakage to be detected within the composite walls of the tanks and also leakage resulting from defects in the polymer liners of the tanks 100, 200, 300, 400. Early warning of tank failure as a result of leakage is therefore provided for. The metallic fibres used provide a simple, robust and cheap mechanism for detecting leakage of hydrogen.

(23) Although metallic fibres in tanks 100, 200, 300, 400 extend either longitudinally or azimuthally, other embodiments may have off-axis metallic fibres.

(24) The metallic fibres comprised in a tank of the invention may be co-wound with a carbon-fibre tow during manufacture of the tank.