The Pd-H system : basic knowledge

This page (under construction) is dedicated to the Pd-H system.

Thomas Graham (1805-1869)

One of the pioneers of the "H in M" field (among the 1st "Hydriders" let says)
who contributed to the discovery of H absorption in Metals.
Specific post(s) will be made later about him and his work on H-in-M.
The objective of this page (in the long term) is to :
gather some key scientific knowledge about the Pd-H system,
for the benefit of researchers, engineers, students, etc ...
with the simple goal of saving time for the beginner.

The typical content of this page will include : short, medium and long reviews, books chapters, Students' Thesis, etc ... etc ... etc ...
Such a goal will obviously take a huuuuuuge time before to be achieved, so that this page will likely be "under construction" for a pretty long endless period.

First, we will give the various unavoidable general materials (from book to small review paper) which present a general overview of the acquired knowledge on this system, at given periods. Then, we will try to gather key materials (from big to small) on selected subjects, again for this specific M-H system, namely Pd-H,D,T. There are many properties to be addressed (mechanical, transport, thermodynamical, kinetics, etc ...). Amongst this ocean of properties, the SAV question (Super Abundant Vacancies) will be addressed, as we are particularily interested (for years) in this controversial question.

At the moment, this page is "managed" by Nicolas ARMANET, the i2-HMR's member whose work is exclusively focused on the Pd-H(D) system.
What you see below is the very beginning of this page.

Table of Content

To find a given item :
just use CTRL + F on your keyboard

0) Thomas Graham

 0.a) ...   

 0.x) His pioneer investigations on PdHx


1) General Material

 1.a) F.A. Lewis' two famous books

    1.a.1) Lewis historical book (1967)

    1.a.2) Update of Lewis' historical book (2000)

 1.b) Three inevitable and good reviews

    1.b.1) Hydrogen in Palladium and Palladium alloys (Wicke et al., 1978)

   1.b.2) The Palladium-Hydrogen system (Flanagan et al., 1991)

    1.b.3) The H-Pd (Hydrogen-Palladium) system (Manchester et al., 1994)


2) Theses

 2.a) On Pd-H(D) only

    2.a.1) in English

    2.a.2) in ...

    2.a.3) in ...

 2.b) On Pd-H(D) alloys

    2.b.1) in English

   2.b.2) in ...

    2.b.3) in ...





.) ...

 ..a) ...

    ..a.1) Thermal properties for Pd Hydride and Deuteride (from 9 K to 270 K)





X) Special Collection
 X.1) Thomas Graham commemorative issue (1866 - 1966)
 X.2) Papers difficult to find (i.e. without DOI number)
   X.2.a) References cited in "High pressure synthesis and thermodynamic stability of PdH(1+/-epsilon) up to 8 GPa"
   X.2.b) References cited in "First-principles study of the atomic volume of Hydrogen in Palladium"
Y) Acknowledgements
 Y.1) to The IChF-PAN's Biblioteka (Poland)
 Y.2) linked to the paper : "High pressure synthesis and thermodynamic stability of PdH(1+/-epsilon) up to 8 GPa"
 Y.3) linked to the paper : "First-principles study of the atomic volume of Hydrogen in Palladium"

N.B. : all papers / chapters / books mentioned in this page can be downloaded via LibGen or Sci Hub
(except : those directly downloadable thanks to the blue/black boxes, or a few exceptions).
Via Sci-Hub : just enter the DOI number, bingo !
Via Libgen : just enter the keys words, bingo !

0) Thomas Graham

0.a) ...

...

...

0.x) His pioneer investigations on Pd-H

Graham's first paper on the Pd-H system was published in 1866 (see below).
In the literature (at least up to 2019), when referring to the discovery of Pd-H, an overwhelming amount of authors do only cite his first paper, yet Graham's work on this system was pursued after 1866 :

His 1st paper (1866) : https://doi.org/10.1098/rstl.1866.0018 see page 426.
His 2nd paper (1868) : https://doi.org/10.1098/rspl.1867.0090
His 3rd paper (1869) : https://doi.org/10.1098/rspl.1868.0030
His 4th paper (1869) : https://doi.org/10.1098/rspl.1868.0103

One can remark that this work was done at the end of Grahams's career (he passed away in 1869).

0.y) Thomas Graham commemorative issue (1866-1966)

See below the section X.1).

1) General Material

1.a) F.A. Lewis' two famous books :


 

1.a.1) Lewis' historical book
The Palladium Hydrogen system
Frederick Alastair Lewis
1967
178 pages

How to download this book :
- go to the LibGen website,
- and enter "palladium hydrogen lewis",
- bingo !
The version available in the LibGen website was scanned by The i2-HMR.
N.B. : at the time of the scan, this book was not available from Publishers (and is maybe still not), explaining why we shared it in LibGen. We're sorry for the low quality of the scan.

Photo by N. Armanet

The paper under the 1967 red book is an appreciation made by Ted B. Flanagan in 2008 about F.A. Lewis (deceased in 2007). This appreciation can be found here. This paper is interesting for various reasons, including : Ted reviewed the major Lewis' contributions on Pd-H and its alloys.
F.A. Lewis made a gigantic amount of contributions on the Pd-H(D) system and its alloys. Specific post(s) will be made later for that.


1.a.2) Update of Lewis' historical book
Palladium Hydrogen system
F.A. Lewis, K. Kandasamy, and X.Q. Tong
2000
234 pages

 

1.b) Three inevitable and good reviews

 

1.b.1) Hydrogen in Palladium and Palladium alloys

E. Wicke, H. Brodowsky, H. Züchner
Page : 73 - 155 (82 pages)
1978
Chapter 3 in : "Hydrogen in Metals II, application-oriented properties", Ed. G. Alefeld and J. Völkl, Springer-Verlag, 1978.

How to download this review :
DOI : 10.1007/3-540-08883-0_19


1.b.2) The Palladium-Hydrogen system
T.B. Flanagan and W.A. Oates
1991
36 pages

How to download this review :
DOI : 10.1146/annurev.ms.21.080191.001413

An almost identical material was presented by T.B. Flanagan in 1989 at the EPRI-NSF Workshop on anomalous effects in Deuterided metals, Wasington D.C., USA, published in the proceedings* and can be found here below in the black box. This version is worth exploring for various reasons, notably it includes an interesting dialogue between Flanagan and some attendees such as R.A. Oriani, J.O'M. Bockris, ...

Besides, it is a great pity that dialogues between the speaker and attendees (during questions session) do not appear in the proceedings anymore (as it was apparently the case in the past).

* : The book of proceedings can be found in the ResearchGate profile of T.B. Flanagan : here.


1.b.3) The H-Pd (Hydrogen-Palladium) system
F.D. Manchester, A. San-Martin, and J.M. Pitre
1994
22 pages

How to download this review :
DOI : 10.1007/BF02667685

2) Theses

The objective of this section (Theses dealing with the Pd-H(D) system and its alloys) is the following one :


gathering as much Theses* as possible (in any languages) :

- exclusively focused on it (i.e. on the Pd-H(D) system and its alloys),

- or where this system occupies an important role (in the Thesis document), or where it is addressed in a section long enough to motivate people consulting it.

We think that these Theses could be interesting for people who start working on this M-H system. 

* most of them are Ph.D. Theses ; the others are Bachelor or Master Theses (in this case, we will specify it).

Theses are sorted by alphabetical order of the authors.

If your Thesis is not listed, please feel free to inform us (by email) : contact@i2-hmr.com . 

Note that we consider the following principle :

if your Thesis is available on-line (somewhere in the web), it means that it's public in the sense that anyone can consult it ; we thus feel that it's OK for us to gather it on our website. We have the same reasoning for Theses which are available for consultation directly at University libraries.

If, for any reason, you don't want to see your Thesis here, please feel free to inform us (we will delete it).


Theses can be downloaded :

- either by clicking on the Thesis title (through the University website) (in this case, the Thesis is available on-line),

- or by clicking on the related box (in this case, the Thesis is not available on-line, but is available for consultation directly at the University's library).


This section is under construction ...

We've just started ...



2.a) On Pd-H(D) only

In this section, we are dealing with Theses addressing the Pd-H(D) system only, in the sense : not its alloys.


2.a.1) in English

Narrowed list (Theses sorted alphabetically) : 


Bönisch -- On the influence of Hydrogen on the stability of lattice defects in metals, 2011,

Castano Giraldo -- Evidence of superconductivity in the magnetic properties of specially prepared Palladium Hydride and Deuteride samples (Pd/PdO:Hx and Pd/PdO:Dx), 2002,

Delmelle -- Effect of internal stress and microstructure on the hydriding of Pd thin films, 2012,

McLennan -- Structural studies of the Palladium-Hydrogen system, 2005,

Moorthy -- Theoretical and experimental study of pressure hysteresis in the Palladium Hydride phase transition, 2018,

Orondo -- A theoretical analysis of interstitial Hydrogen : Pressure-Composition-Temperature, Chemical Potential, Enthalpy and Entropy, 2012,

Pitt -- In-situ powder diffraction studies of Metal-Hydrogen microstructures, 2003,

Robinson -- Computational studies of Hydrogen in Palladium, 2015,

Shtaya-Suleiman  -- Size-selective synthesis of nanometer-sized Palladium clusters and their Hydrogen solvation behaviour, 2003,

Steel -- Study of the properties of Hydrogen and Deuterium in Beta phase Palladium Hydride and Deuteride, 2018,

Syed -- Transient high-temperature Superconductivity in Palladium Hydride, 2016,

Webb -- Structure-function relationships in Metal Hydrides : origin of the pressure hysteresis, 2017,

Wheeler -- Nanoindentation under dynamic conditions, 2009,

M. Bönisch,

On the influence of Hydrogen on the stability of lattice defects in metals,

Master Thesis,

University of Vienna, Vienna, Austria, 2011,
and it is [X75] in our own classification.


C.H. Castano Giraldo,

Evidence of superconductivity in the magnetic properties of specially prepared Palladium Hydride and Deuteride samples (Pd/PdO:Hx and Pd/PdO:Dx),

Master Thesis,

University of Illinois at Urbana-Champaign, USA, 2002,

and it is [X1440] in our own classification.


R. Delmelle,

Effect of internal stress and microstructure on the hydriding of Pd thin films,

Université Catholique de Louvain, Louvain-la-Neuve, Belgique, 2012,

and it is [X100] in our own classification.


K.G. McLennan,

Structural studies of the Palladium-Hydrogen system,

Griffith University, Griffith, Australia, 2005,

and it is [X770] in our own classification.


A. Moorthy,

Theoretical and experimental study of pressure hysteresis in the Palladium Hydride phase transition,

Bachelor Thesis,

California Institute of Technology, California, USA, 2018,

and it is [X1444] in our own classification.


P.O. Orondo,

A theoretical analysis of interstitial Hydrogen : Pressure-Composition-Temperature, Chemical Potential, Enthalpy and Entropy,

MIT, Cambridge, USA, 2012,

and it is [X1715] in our own classification.


M.P. Pitt,

In-situ powder diffraction studies of Metal-Hydrogen microstructures,

Griffith University, Griffith, Australia, 2003,

and it is [X834] in our own classification.

Abstract :
it is not possible to extract it because the document is protected by a password. To find the Abstract : use the link on the left, download the PDF, and go to page III (or page PDF 4).

Table of Content (TOC) :
it is not possible to extract it because the document is protected by a password. To find the TOC : use the link on the left, download the PDF, and go to page IV (or page PDF 5).


I.K. Robinson,

Computational studies of Hydrogen in Palladium,

University of Salford, Manchester, UK, 2015,

and it is [X713] in our own classification.


M.A.M. Shtaya-Suleiman,
Size-selective synthesis of nanometer-sized Palladium clusters and their Hydrogen solvation behaviour,
University of Georg August, Göttingen, Germany, 2003,
and it is [X79] in our own classification.

Abstract :
It can be read on the University page (click on the left link). No Abstract is present in the Thesis.


S.S. Steel,

Study of the properties of Hydrogen and Deuterium in Beta phase Palladium Hydride and Deuteride,

University of Salford, Manchester, UK, 2018,

and it is [X1428] in our own classification.


H.M. Syed,
Transient high-temperature Superconductivity in Palladium Hydride,
Griffith University, Griffith, Australia, 2016,
and it is [X1274] in our own classification.

Abstract :
it is not possible to extract it because the document is protected by a password. A shorter Abstract is however available on the University page (click on the left link).
Table of Content (TOC) :
it is not possible to extract it because the document is protected by a password. To find the TOC : use the link on the left, download the PDF, and go to page VII (or page PDF 9).

T.A. Webb,

Structure-function relationships in Metal Hydrides : origin of the pressure hysteresis,

Griffith University, Griffith, Australia, 2017,

and it is [X1275] in our own classification.

Abstract :
it is not possible to extract it because the document is protected by a password. A shorter Abstract is however available on the University page (click on the left link).

Table of Content (TOC) :
it is not possible to extract it because the document is protected by a password. To find the TOC : use the link on the left, download the PDF, and go to page VII (or page PDF 8).

J.M. Wheeler,

Nanoindentation under dynamic conditions,

University of Cambridge, Cambridge, UK, 2009,

and it is [X57] in our own classification.


2.a.2) in ...

...

2.b) On Pd-H(D) alloys

2.b.1) in English

...

2.b.2) in ...

...

.) ...

..a) ...

..a.1) Thermal properties for Pd Hydride and Deuteride (from 9 K to 270 K)


i) Thermal expansion and lattice anharmonicity of Pd-H and Pd-D alloys
R. Abbenseth and H. Wipf
J. Phys. F : Metal. Phys., 10 (1980) 353 - 366
DOI : 10.1088/0305-4608/10/3/006


ii) Contribution of optical phonons to the thermal expansion of Alpha'-PdHx and Alpha'-PdDx
H. Hemmes, B.M. Geerken and R. Griessen
J. Phys. F : Metal. Phys., 14 (1984) 2923 - 2933

DOI : 10.1088/0305-4608/14/12/014


--> if you think further references should be added, please keep us informed. Thanks !



X) Special Collection 

X.1) Thomas Graham commemorative issue :
1866 --> 1966
Guest Editor : T.B. Flanagan
1966
62 pages


This is a special issue marking the centennial of the discovery by Thomas Graham of the phenomenon of the absorption of Hydrogen by Palladium.
This dedicated booklet is focused on the Pd-H(D) system (and some of its alloys). The i2-HMR is much grateful to Ted B. Flanagan for having sent us a hard copy of this issue, which we naturally scanned and made available in Lib Gen. Maybe the next commemoration will be in : 2066 ?! Who knows ...

How to download this book :
- go to the LibGen website,
- and enter "engelhard industries",
- bingo !


X.2) Papers difficult to find (i.e. without DOI number)


This section deals with specific references (having no DOI number) which are cited in our current or forthcoming papers on Pd-H(D) and its alloys.

The goal here is to prevent colleagues wasting time and money searching for them everywhere (University Library, Journal, directly to the author if still alive, etc ...).

 

X.2.a) References cited in "High pressure synthesis and thermodynamic stability of PdH(1+/-epsilon) up to 8 GPa"

The 9 references below (X.2.a.1 - X.2.a.3 + X.2.a.5 - X.2.a.10), difficult to find, are cited in our paper : 
Title : "High pressure synthesis and thermodynamic stability of PdH(1+/-epsilon) up to 8 GPa".
Authors : Z.M. Geballe, M. Somayazulu, N. Armanet, A.K. Mishra, M. Ahart, R.J. Hemley.
Just accepted in PRB on January 6th, 2021.
Full text : see Publications.
N.B. : note that Ref [59] (referred as "unpublished") is in fact in preparation.

X.2.a.1) Ref [38] is :
S.A. Semiletov, Yu. P. Khodyrev, R.V. Baranova, and R.M. Imamov,
A new palladium hydride,
Soviet Technical Physics Letters, 5 (1979) 191-192,
and is [X314] in our own classification and can be downloaded in the blue box below.
Russian version : unfortunately, we don't have it. If you happen to have it, we're interested !

X.2.a.2) Ref [40] is :
R.V. Baranova, Yu. P. Khodyrev, R.M. Imamov, and S.A. Semiletov,
Crystal structure of palladium hydride with primitive cubic lattice (a=2.995A),
Soviet Physics - Crystallography, 25 (1980) 736. There's only 1 page,
and is [X312] in our own classification and can be downloaded in the blue box below.
Russian version [X312bis] : in the blue box below.

X.2.a.3) Ref [39] is :
S.A. Semiletov, R.V. Baranova, Yu. P. Khodyrev, and R.M. Imamov,
Electron-diffraction investigation of tetragonal PdH1.33,
Soviet Physics - Crystallography, 25 (1980) 665-669,
and is [X313] in our own classification and can be downloaded in the blue box below.
Russian version [X313bis] : in the blue box below.

X.2.a.4) In addition, here are two further and earlier papers from the same team (but not cited in our paper) :

Yu. P. Khodyrev, R.V. Baranova, R.M. Imamov, and S.A. Semiletov,
Electron-diffraction investigation of Beta-fcc palladium hydride,
Soviet Physics - Crystallography, 23 (1978) 592-594,
and is [X1269] in our own classification and can be downloaded in the blue box below.
Russian version [X1269bis] : in the blue box below.

Yu. P. Khodyrev, R.V. Baranova, and S.A. Semiletov,
Attachment for producing films of hydrides, oxides, and nitrides in the ER-100 electron-diffraction camera,
Soviet Physics - Crystallography, 21 (1976) 723-724,
and is [X1268] in our own classification and can be downloaded in the blue box below.
Russian version : unfortunately, we don't have it. If you happen to have it, we're interested !

X.2.a.5) Ref [57] is :
M. Tkacz and B. Baranowski,
Solubility of hydrogen in palladium hydride at high pressure of gaseous hydrogen,
Roczniki Chemii, Ann. Soc. Chim. Polonorum, 50 (1976) 2159-2166,
and is [X1160] in our own classification and can be downloaded in the blue box below.

X.2.a.6) Ref [58] is :
A.W. Szafranski,
Pressure-composition studies on the palladium-gold-hydrogen system up to 10 kbar at 25°C,
Polish Journal of Chemistry, 55 (1981) 2137-2141,
and is [X826] in our own classification and can be downloaded in the blue box below.

A high resolution scan of [X826]'s Figure page 2138 can be downloaded here :

X.2.a.7) Ref [22] is :

F. Celani, A. Spallone, P. Tripodi, D. di Gioacchino, P. Marini, A. Mancini,

Observations of strong resistivity reduction in a Palladium thin long wire using ultra high frequency pulsed electrolysis at D/Pd > 1,

Proceedings of the 6th International Conference on Cold Fusion (ICCF6), 1996, Vol. 1, pp. 228-233,

and is [Y45] in our own classification and can be downloaded in the blue box below.

X.2.a.8) Ref [12] is :

H.M. Syed,

Transient high-temperature superconductivity in Palladium Hydride,

Ph.D. Thesis, School of Natural Sciences, Griffith University, Australia, 2016,

and is [X1274] in our own classification and can be downloaded HERE.

 

X.2.a.9) Ref [16] is :

C.H. Castano Giraldo,

Evidence of superconductivity in the magnetic properties of specially prepared Palladium Hydride and Deuteride samples (Pd/PdO:Hx and Pd/PdO:Dx).

Master Thesis, University of Illinois at Urbana-Champaign, USA, 2002,

and is [X1440] in our own classification and can be downloaded HERE.

 

X.2.a.10) Ref [26] is :

R. Kirchheim and A. Pundt,

Hydrogen in metals, Chap. 25, pp. 2597-2705,

in Physical Metallurgy, 5th edition, 2014,

and is [X745] in our own classification and can be found HERE.


X.2.b) References cited in "First-principles study of the atomic volume of Hydrogen in Palladium"



The reference below (Ponyatovskii et al.), difficult to find, is cited in our paper :
Title : "First-principles study of the atomic volume of Hydrogen in Palladium".
Authors : S.S. Setayandeh, T. Gould, A. Vaez, K. McLennan, N. Armanet and E. Gray.
Just accepted in JALCOM on January 9th, 2021.
Full text : see Publications.

Ref [32] is :
E.G. Ponyatovskii, V.E. Antonov, and I.T. Belash,
Properties of high pressure phases in metal-hydrogen systems,
Soviet Physics Uspekhi, 25 (1982) 596-619.





 
Y) Acknowledgements
Y.1) to The IChF-PAN's library (Poland)

We would like to express here our most sincere thanks to The IChF-PAN's library (biblioteka in Polish) who kindly supplied us with a large amount of old papers published in The "Polish Journal of Chemistry" and its previous version "Roczniki Chemii", as well as in "Bulletin de l'Académie Polonaise des Sciences, Série des Sciences Chimiques".

IChF-PAN is (in En) : Institute of Physical Chemistry - Polish Academy of Science, in Warsaw, Poland.


From 2014, we have regularly requested (and still do) many papers, overwhelmingly about the Pd-H system and its alloys, and received them with always the same kindness, cordiality and promptitude. For that, we warmly thanks The Biblioteka and thus : Arleta Nierychlewska, Joanna Bielecka-Madry, Jolanta Szymanska, Agnieszka Rybska, Elzbieta Gorniak. Thank you so much !!!!



Y.2) linked to the paper : "High pressure synthesis and thermodynamic stability of PdH(1+/-epsilon) up to 8 GPa"

Title : "High pressure synthesis and thermodynamic stability of PdH(1+/-epsilon) up to 8 GPa".
Authors : Z.M. Geballe, M. Somayazulu, N. Armanet, A.K. Mishra, M. Ahart, R.J. Hemley.
Reference : just accepted in PRB on January 6th, 2021.
Full text : see Publications. 

In addition to the acknowledgements already present in the paper (which are limited by the journal's policies) : 
Nicolas ARMANET also wishes to express his sincere gratitude to :
(i) Daniel FRUCHART, Vladimir E. ANTONOV, Evan MacA. GRAY for an uncountable number of fruitful and enjoyable conversations since 2014,
(ii) Michel BONNARD, Anthony VOGT, François de GUERVILLE, Mathieu VALAT for their supports and continuous encouragements since 2013,
(iii) V.E. ANTONOV and M.A. KUZOVNIKOV for valuable conversations about Brownsberger's paper.
(iv) Jean-Claude FELICES, Mélinda DALLEAU, Sonia KEITA, for their crucial help in 2016/2018, 2016, 2017 respectively,
(v) my former supervisors Jean-Paul BIBERIAN and Paolo TRIPODI, thanks to whom "I took my very first steps" in the M-H field.

Y.3) linked to the paper : "First-principles study of the atomic volume of Hydrogen in Palladium"

Title : "First-principle study of the atomic volume of Hydrogen in Palladium".
Authors : S.S. Setayandeh, T. Gould, A. Vaez, K. McLennan, N. Armanet and E. Gray.
Reference : just accepted in JALCOM on January 9th, 2021.
Full text : see Publications.

In addition to the acknowledgements already present in the paper :
Nicolas ARMANET also wishes to express his sincere gratitude to :
(i) Daniel FRUCHART, Vladimir E. ANTONOV, Evan MacA. GRAY for an uncountable number of fruitful and enjoyable conversations since 2014,
(ii) Michel BONNARD, Anthony VOGT, François de GUERVILLE, Mathieu VALAT for their supports and continuous encouragements since 2013,
(iii) Jean-Claude FELICES, Mélinda DALLEAU, Sonia KEITA, for their crucial help in 2016/2018, 2016, 2017 respectively,
(iv) my former supervisors Jean-Paul BIBERIAN and Paolo TRIPODI, thanks to whom "I took my very first steps" in the M-H field.
N.B. : all papers / chapters / books mentioned in this page can be downloaded via LibGen or Sci Hub
(except : those directly downloadable thanks to the blue/black boxes, or a few exceptions).
Via Sci-Hub : just enter the DOI number, bingo !
Via Libgen : just enter the keys words, bingo !