Studies Directed to the Development of Long Lived Palladium Membranes for Hydrogen Purification

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University of Montana
ScholarWorks at University of Montana
Graduate Student Theses, Dissertations, &
Graduate School
Professional Papers
2012
Studies Directed to the Development of Long Lived Palladium
Membranes for Hydrogen Purifcation
William Glenn Pinson
The University of Montana
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Hydrogen Purifcation" (2012). Graduate Student Theses, Dissertations, & Professional Papers. 924.
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STUDIES DIRECTED TO THE DEVELOPMENT OF LONG LIVED PALLADIUM MEMBRANES FOR
HYDROGEN PURIFICATION
By
William Glenn Pinson
B.Sc. Chemistry, University of Montana

Dissertation
Presented in partial fulfillment of the requirements
for the degree of

Doctor of Philosophy in Chemistry, Applied Inorganic Chemistry

The University of Montana
Missoula, MT

Summer 2012
Approved by:

Dr. Sandy Ross, Associate Dean
Graduate School

Dr. Edward Rosenberg, Co-Chair
Department of Chemistry

Dr. Garon Smith, Co-Chair
Department of Chemistry

Dr. Sandy Ross
Department of Chemistry

Dr. Valeriy Smirnov
Department of Chemistry

Dr. Tony Ward
The Center for Environmental Health services

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Pinson, William G. Ph.D., Summer 2012 Chemistry

Studies Directed to the Development of Long Lived Palladium Membranes
for Hydrogen Purification

Dr. Edward Rosenberg, Co-Chair, Department of Chemistry

Dr. Garon Smith, Co-Chair, Department of Chemistry

The focus of this study was to systematically investigate the variables involved in
electroless deposition of palladium and palladium alloy membranes on a known porous stainless
steel substrate, and apply the results to a new and novel porous stainless steel substrate.
Different oxide pore and surface treatments were studied. The effect of silica as a diffusion
barrier, surface pore modifier, and palladium nucleation site was examined. Silica sol-gel coating
treated stainless steel substrates were explored. Several different formulas of sol-gel coatings
and their impact on palladium and palladium copper deposition were researched. The roles of
sintering and annealing and their effect on the metal membrane deposition and metal flow
were inspected.
It was observed that varying the plating conditions can alter the morphology of the
deposited Pd and Pd/Cu alloy membrane. New silica sintering techniques were developed, and
implemented. It was observed that the use of silica sol-gel treated , and sintered silica particles
allowed Pd and Pd/Cu alloy deposition of a new and novel micro fabricated porous stainless
steel support matrix. Sol-gel coating the stainless steel substrates allowed the application of a
membrane that significantly decreased the migration of iron and chromium into the membrane,
0
and in some cases totally stopping it, even after annealing at 1000 C.

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ACKNOWLEDGEMENTS
I would like to thank Dr. Smith for his kindness to me when I needed it the most. Thank
you for your offer, so soon after my return from combat. Thank you for opening a space in your
lab for me. Your kindness and support ultimately led to this dissertation.
I would also like to thank Dr. Rosenberg for his patience, friendship, and guidance.
Thanks for answers to all of those questions I ask all of the time. I also want to thank you for
your kick in the butt when I needed it. Thank you for showing me how to find the answers.
Thank you for showing me how to become a true scientist.
I would like to personally thank Dr. Bill Gleason for his friendship and support. Thank
you for giving me the opportunity to work on a project that was suited to my skills. Thanks for
working all of those months without pay, so I could feed my family. Words are truly inadequate
to convey my gratitude.
I would like to thank my loving friend, wife, and soul mate Rozzy. I thank you for your
gentle loving heart and loving push when I needed it. Thank you for your words of belief and
encouragement when I was down or in doubt. Thank you for the support and understanding
during all of those late nights and weekends I had to work. Thank you for making my life so
wonderful and loving.
I want to acknowledge Ayesha Sharmin and Mainul Hossain for all of the help,
friendship, and smiles. I want to thank Rakesh Kumar for the laughs and support during the long
days, go team go. Thanks Mom and Dad for your belief in me and that can do attitude that made
this possible. Thank you to Gay Allison and Rhonda Stoddard for your hugs and help. I would like
to thank Lindsay Mackensie for her invaluable assistance on the XRD. Thanks to Danette Rule
for the assistance on all those admin details that no one thanks you for. I would like to thank
Matt Berlin for his work and assistance on this project. I want to also acknowledge the USMC for
the attitude adjustment and teaching me how not to ever give up or quit.
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Abstract iv
Acknowledgements v
Table of contents vi
List of Figures ix
List of Tables xi
Table of Contents
Chapter 1 Introduction .................................................................................................................... 1
1.1 Statement of the problem ..................................................................................................... 1
1.2 Project history ........................................................................................................................ 3
1.3 Background ............................................................................................................................ 6
Chapter 2 project Goals ................................................................................................................. 15
2.1. The project initial goal ........................................................................................................ 15
2.2 Project secondary goal. ........................................................................................................ 16
Chapter 3: EXPERIMENTAL............................................................................................................. 17
3.1 Materials and methods ........................................................................................................ 17
3.2 Instrumentation ................................................................................................................... 18
3.3 Spectroscopic characterization ............................................................................................ 18
3.4 Experiment 1 ........................................................................................................................ 19
3.5 Experiment 2 ........................................................................................................................ 23
3.6 Experiment series 3 .............................................................................................................. 27
3.6.1 Experiment 3-1 .................................................................................................................. 27
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3.6.2 Experiment 3-2 .................................................................................................................. 28
3.6.3.1 Experiment 3-3-1 ........................................................................................................... 28
3.6.3.2 Experiment 3-3-2 ........................................................................................................... 28
3.7 Experiment series 4 .............................................................................................................. 31
3.7.1 Experiment 4-1 .................................................................................................................. 31
3.7.2 Experiment 4-2 .................................................................................................................. 31
3.8 Experiment series 5 .............................................................................................................. 33
3.8.1 Experiment 5-1 .................................................................................................................. 33
3.8.2 Experiment 5-2 .................................................................................................................. 36
3.8.3 Experiment 5-3 .................................................................................................................. 37
3.8.4 Experiment 5-4 .................................................................................................................. 37
3.8.5 Experiment 5-5 .................................................................................................................. 38
3.8.6 Experiment 5-6 .................................................................................................................. 40
Chapter 4 Results and discussion ................................................................................................... 43
4.1. Project initial goals .............................................................................................................. 43
4.1.1 Experiment series 1. .......................................................................................................... 44
4.1.1.1 Experiment 1-01 ............................................................................................................. 46
4.1.1.1.1 Summary of experimental results in experiment 1 .................................................... 52
4.1.2 Experiment series 2 ........................................................................................................... 53
4.1.2.2 Summary of results in experiment 2 .............................................................................. 63
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4.1.3 Experiment series 3 ........................................................................................................... 63
4.1.3.1 Experiment 3-1 ............................................................................................................... 64
4.1.3.3 Experiment 3-3 ............................................................................................................... 69
4.1.3.3.1 Summary of results experiment 3............................................................................... 77
4.1.4 Summary of initial goal experiments ................................................................................ 78
4.2 Project secondary goals ....................................................................................................... 80
4.2.1 Experiment 4-1 and Experiment 4-2 ................................................................................. 80
4.2.2 Experiment 5 ..................................................................................................................... 81
4.2.2.1 Experiment 5-1 ............................................................................................................... 81
4.2.2.2 Experiment 5-2 and 5-3 ................................................................................................. 87
4.2.2.3 Experiment 5-4 ............................................................................................................... 87
4.2.2.4 Experiment 5-5 ............................................................................................................... 90
4.2.2.5 Experiment 5-6 ............................................................................................................... 92
Chapter 5 Conclusions ................................................................................................................... 98
Chapter 6 Future studies ............................................................................................................. 105
Bibliography for palladium membranes ...................................................................................... 107
Quoted references ....................................................................................................................... 126
List of figures
10 0
Figure 1.31 Gas phase palladium 4d and 5s orbitals ................................................................... 6
Figure 1.3.2 H2 disassociation and electron injection into conduction band of Pd. ........................ 7
Figure 1.3.3 Pd crystal lattice type ................................................................................................... 9
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Figure 1.3.4: a side view of silica sol-gel and silica bead treated CAMP disc with a deposited
Pd/Cu membrane ........................................................................................................................... 10
Figure 1.3.5: SEM of Porous stainless steel (PSS) substrates ......................................................... 11
Figure 1.3.6: Pd/Cu treated PSS substrates ................................................................................... 12
Figure 1.3.7. Sem (a) and XRD (b) of annealed palladium copper alloy MOTT disc ...................... 14
Figure 1.3.8: Schematic of permeance testing apparatus ............................................................. 15
Figure 3.4.1: Disc holder during oxide particle application ........................................................... 19
d2+ 0
Formula 1 reduction of P to Pd ................................................................................................. 22
Figure 3.4.2: Disc holder during Pd ................................................................................................ 22
Figure 3.6.3.2: Holding block and manometer leak testing device ............................................... 29
Formula 2: Reduction of Cu2+ to Cu0 using formaldehyde ........................................................... 38
Figure 4.1: SEM and EDX of initial Pd plating attempt on starting material. ................................. 43
Figure 4.1.1.1.2: Experiment 1 different oxide particles and different sized MOTT discs............. 46
Figure 4.1.1.1.2: Experiment 1 multiple coatings of different oxide particles on MOTT discs. ..... 47
Figure 4.1.1.1.3: Experiment 1 different Pd seeding epitaxial formations. ................................... 48
Figure 4.1.1.1.4: Experiment 1 the effect of multiple seeding steps on MOTT discs. ................... 48
Figure 4.1.1.1.5: Close up of experiment 34 showing coral like formations with secondary fill on
select edges.................................................................................................................................... 49
Figure 4.1.1.1.6: Experiment 1 discs 20,37,43 show twice oxide coated, once seeded and once
plated experiments. ....................................................................................................................... 50
Figure 4.1.1.1.7: Experiment 1 discs 27, 33, 39, 45 show once oxide coated, seeded three times
and once plated experiments. ....................................................................................................... 51
Figure 4.1.1.1.8: Experiments 15, 18, 21, 29 show once oxide coated ,not seeded and once
plated. ............................................................................................................................................ 51
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Figure 4.1.1.1.9: Experiment 1 disc 15 larger image...................................................................... 52
Figure 4.1.2.1: Experiment 2 a series of controls for each oxide coating and seeding step ......... 54
Figure 4.1.2.2: Experiment 2 showing silica bead contamination. ................................................ 55
Figure 4.1.2.3: Effects of the different plating solution stir speeds and plating angle. ................. 56
Figure 4.1.2.4: Effects of the different plating solution stir speeds and plating angle. ................. 57
Figure 4.1.2.5: Effects of the different plating solution stir speeds and plating angle. ................. 58
Figure 4.1.2.6: Comparison of the differing oxide treatments, plating angles and stir speeds. ... 60
Figure 4.1.2.7: Alumina particle treated alternative solution plated MOTT discs. ........................ 61
Figure 4.1.2.8: Silica particle treated alternative solution plated MOTT discs. ............................. 62
Figure 4.1.2.9: Zirconia particle treated alternative solution plated MOTT discs. ........................ 62
Figure 4.1.3.1.1 CAMP disc silica application apparatus ............................................................... 66
Figure 4.1.3.1.2: silica particle treated CAMP discs ....................................................................... 66
Figure 4.1.3.2.1: CAMP discs with silica particles treated with various combinations of solvents,
vacuum and hand application. ....................................................................................................... 67
Figure 4.1.3.2.2: Filaments formed from the silica beads during sinter. ....................................... 68
Figure 4.1.3.2.3: Discs that were successfully treated................................................................... 68
Figure 4.1.3.3.1 : Discs (19, 21) that were successfully SnCl2/PdCl2, sensitized and plated using
Pd(NH3)4Cl2/hydrazine. .................................................................................................................. 69
Figure 4.1.3.3.2: Experiment 3-3-2a discs that were Pd/Cu treated ............................................. 70
Figure 4.1.3.3.3: Comparison of original and final plating system ................................................ 71
Figure 4.1.3.3.4: Full view at high magnification showing the nature of the Pd/Cu depositional
layers on the CAMP substrate ....................................................................................................... 72
Figure 4.1.3.3.5 XRD post anneal disks 3-3-8 and 3-3-11 .............................................................. 74
Figure 4.1.3.3.6 XRD, SEM, EDX disc 3-3-10 post anneal ............................................................... 75
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