1. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 A New Technology for Hydrogen Safety: Glass Structures as a Storage System Ronald Meyer BAM Federal Institute for Materials Research and Testing Division II.1 “Gases, Gas Plants” 12205 Berlin, Germany C.En Ltd., 3 Sonnhaldenstrasse Postfach CH-8032 Zurich, Switzerland

2. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 2 Contents 1.Idea 2.Safety aspects 3.Storage principles 4.Conclusion/Perspectives

3. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 3 picture of a round capillary array Model of a capillary array, scale 250:1 Idea 1 mm

4. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 4 Density g/cm 3 Tensile Strength MPa Material 2.949Aluminum 4.51900Titanium Alloy 3.9-4.11900Sapphire (Al 2 O 3 ) 7.8310-2482Steel 1.83530 - 4560Carbon fiber 2.484710S-Glass (fiber) 2.26000Quartz (fiber) Why Use Multi-Capillary Arrays?

5. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 5 Multi-Capillary Arrays have a number of outstanding characteristics of outstanding characteristics: ReusableReusable Chemically durableChemically durable Crash safetyCrash safety Mechanically strongMechanically strong Light weightLight weight Environmentally friendlyEnvironmentally friendly Why Use Multi-Capillary Arrays? Low hydrogen diffusionLow hydrogen diffusion

6. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 6 Contents 1.Idea 2.Safety aspects 3.Storage principles 4.Conclusion/Perspectives

7. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 Pressure Tests Capillaries made of different glass materials have been tested Sodium carbonate● Quartz Alumina silicate● Borosilicate Different gases for pressure tests Maximum Burst Pressure: 132.4 MPa / 19203 psi for single capillaries 117.3 Mpa / 17013 psi for arrays 7

8. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 Pressure Tests Parameters varied: Inner diameters from 120 µm up to 3 mm Wall thicknesses from 10 µm up to 290 µm Different lengths from 100 mm up to 300 mm Different diameter-wall thickness-ratios 8

9. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 Diameter-Wall thickness-Ratios 9

10. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 Burst pressure of single capillaries are important basic information Information about the reliability of complex bundled systems Failure probability statistics of capillaries Statistical Evaluation 10

11. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 It is a statistical distribution which is used for determination of durability in quality management Especially used at material fatigue of brittle materials Different number of samples of the same design and construction have to be tested at defined conditions till a collapse eventuates 11 Weibull-Distribution

12. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 12 Quartz Borosilicate Statistical Evaluation

13. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 13 Quartz Borosilicate Statistical Evaluation

14. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 14 Permeation Measuring H 2 - concentration with mass spectroscopy T < 600 °C release of surface absorbed H 2 T > 650°C release of enclosed permeated H 2 out of closed capillary permeation around 10 -14 mol cm -1 s -1 atm -1 at 200°C Released hydrogen during vacuum hot extraction Open capillary Closed capillary

15. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 15 Material stresses in single capillaries and capillary arrays with and without defects at 500 bar internal pressure, calculated with the COMSOL code using the von Mises plastic distortion hypothesis Stress modeling Reference: Marek Gebauer

16. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 16 Contents 1.Idea 2.Safety aspects 3.Storage principles 4.Conclusion/Perspectives

17. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 17 Array filled with alloy, capillaries properly closed Stopper alloy End of capillary array after completed filling and releasing procedure Ø500µm Alloy for closure

18. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 18 Prototype No. 3 Sealing system Connects storage unit to application Heating coil Coil made of insulated electric wire Electric contacts Connects heating coil to external power supply Glass capillary arrays Main storage device PTFE shell Protection against mechanical damage (shown here as transparent) Ø 16 mm 130 mm storage part sampling point pre-volume

19. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 Storage Principles Stopper Alloy Long time storage Low-melting alloy as closing system for every single capillary Cheap solution without high constructional afford Heat energy for closing and for opening Electronic control unit for heating needed Special setup for filling necessary, no in-situ possible 19

20. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 Prototype with micro valve for closure 20

21. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 Storage Principles Valve Short time storage Alterning demand or quick providing Short release-period with different flows and pressure ratios In-situ filling is possible No or low energy-supply necessary 21

22. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 22 Contents 1.Idea 2.Safety aspects 3.Storage principles 4.Conclusion/Perspectives

23. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 23 Conclusions/Perspectives Capillaries are able to withstand high pressures Glass capillaries systems demonstrate the possibility of lightweight storage systems in every shape and volume In tests for single capillary gravimetric capacity of 33 wt% and vol. capacity of 45 g/l Usage over a wide range of applications, up- and down scaling for adaption possible Long time as well as short time storage systems are realizable

24. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 24 Conclusions/Perspectives System is split into several modules, in case of leakage or impact only the damaged module will release the amount of stored hydrogen Possibility of hazardous situations much lower than of a single-tank-solution Safety evaluation only for a complete system possible

25. Thank you very much for your attention. If there are any questions left don`t hesitate to ask me. Ende 25

26. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 26 Backup

27. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 27 Storage Procedure Operating pressure: 150 MPa (21750 psi) Arrays placed in high pressure vessel in vertical position Stopper alloy is positioned on top of arrays After reaching the storage pressure the whole system is heated up The alloy is melting and is pressed in the arrays with a pressure application After cool down and release of pressure the storage procedure is finished High pressure vessel 3 – array prototype Stopper alloy

28. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 28 ~25% gravimetric storage capacity Release procedure in heatable autoclave

29. Ronald Meyer4 th ICHS – International Conference on Hydrogen Safety 20112011-09-14 29 Updated Hydrogen Storage Targets * U.S. Department of Energy- Hydrogen Program, March 2010