Dear Awane,

Excellent initiative by your team. At present I do not have any such information. I will update you as soon as possible.

Dear Dr. Omkar Singh Kushwaha,

Thank you for your interest in my work. I look forward to hearing of your information.

As of January in 2015, I have achieved the following research results.

[Methodology]

I developed a new method that consists of a reduction method (silicon sputtering method) and an estimation method (before-and-after hydrogen background estimation method) for the background-originated hydrogen (HBG) to estimate net hydrogen (HN) in metallic materials using SIMS and demonstrated its effectivity [1]. 

[Accuracy assessment]

I have investigated time variation of hydrogen in austenitic stainless steel using the developed method. I have predicted time variation of hydrogen distribution in austenitic stainless steel by a physicochemical calculation, and compared predicted values with measured values by SIMS.[2]

[Detection limit]

Hydrogen of 0.12 wt. ppm charged into a ferritic steel sample is the minimum hydrogen content detected by the developed method.[3]

 [Reference]

[1] "Highly Sensitive Detection of Net Hydrogen Charged into Austenitic Stainless Steel with Secondary Ion Mass Spectrometry”

Tohru Awane, Yoshihiro Fukushima, Takashi Matsuo, Saburo Matsuoka, Yukitaka Murakami, and Shiro Miwa

Analytical Chemistry, Vol.83 (2011), 2667-2676.

[2] "Highly Sensitive Secondary Ion Mass Spectrometric Analysis of Time Variation of Hydrogen Spatial Distribution in Austenitic Stainless Steel at Room Temperature in Vacuum"

Tohru Awane, Yoshihiro Fukushima, Takashi Matsuo, Yukitaka Murakami, and Shiro Miwa

International Journal of Hydrogen Energy, Vol.39 (2014), 1164-1172.

[3] "Detection of Charged Hydrogen in Ferritic Steel through Cryogenic Secondary Ion Mass Spectrometry"

Atsushi Nishimoto, Motomichi Koyama, Shigeru Yamato, Yasuji Oda, Tohru Awane and Hiroshi Noguchi

ISIJ International, Vol. 55 (2015), No. 1, pp. 335–337.

Dear Doctor Tohru Awane,

I represent a group of organizations (Manufacturer of equipment, research institute, university).

We develop and produce specialized equipment for measuring the concentration of hydrogen in various media (metals, polymers, crystalline materials, glass, ceramics, liquid). [1]

We are also making all kinds of research and development associated with the influence and the accumulation of hydrogen. For example: timing critical accumulation of hydrogen, strength calculation of structures operating in hydrogen medium, and so on. [2,3,4,5,6]

For your purposes, I can recommend industrial hydrogen analyzer AV-1. It allows you to measure the microscopic flow of hydrogen. (The minimum weight of the measured sample is 3 micrograms).

This equipment is ready to use. We can collaborate with you in any form. For example, we can prepare and make the measurement in our laboratory.

With Best Regards,

Dr., prof. Vladimir Polyanskiy

mob.+7(921)7480637

Director of the SEC IPM RAS in

St.-Petersburg State Polytechnical University

Director of the Engineering Center at the Institute for Problems in

Mechanical Engineering of the Russian Academy of Sciences,

V.O., Bolshoj pr., 61

St. Petersburg, 199178

Russia

A profile of H in the surface (few micrometer) of metals might be analysed with NRA (resonant nuclear reaction analysis) with nitrogen-15 with a depth resolution of about 100nm. The lateral resolution depnds on the beam size.

Dear Professor Vladimir Polyanskiy,

Thank you for your giving interesting information and precious references about the hydrogen analyzer AV-1. Now I am reading the first reference.  

Dear Dr. E. Strub,

Thank for your helpful information about the NRA. I will check it.

The analytical target is hydrogen of several ppm or less distributed in surface region of a cross-section sample cut out from a metallic pipe or tank used for fuel cell system. Since hydrogen diffuses over a range of several millimeters in the metallic materials at the condition of hydrogen gas of fuel cell system (tempereture or pressure), it is necessary to prepare a cross-section sample. In this case, it is difficult to analyze hydrogen with "surface analysis" method such as static SIMS because hydrogen escapes from the surface region (approximately 10 um deep in case of austenitic stainless steel) due to frictional heat when cutting or polishing. I will investigate whether the NRA is effective or not to analyze hydrogen in such a cross-section sample.

Thank you again.

Dear Doctor Tohru Awane,

Thank you for your interest.

In any case, these is my profile in google scholar ( https://scholar.google.ru/citations?hl=en&user=ThzU7vcAAAAJ&view_op=list_works&sortby=pubdate&cstart=0&pagesize=20)

Unfortunately, our results about the investigation of the hydrogen distribution by the  depth  in metals are in Russian.

But we have experience in determination of the hydrogen content in zinc layer on steels, in nano Pt layers on silicon, determination the hydrogen absorbed on the surface  and so on.  The main our advantage are the high sensitivity and the industrial method of the calibration. For example, we can measure the 0.01 ppm in aluminum alloy with separation the hydrogen on the surface and dissolved.    

With Best Regards,

Dr., prof. Vladimir Polyanskiy

mob.+7(921)7480637

Director of the SEC IPM RAS in

St.-Petersburg State Polytechnical University

Director of the Engineering Center at the Institute for Problems in

Mechanical Engineering of the Russian Academy of Sciences,

V.O., Bolshoj pr., 61

St. Petersburg, 199178

Russia

Dear Thoru, the real advantage of NRA would be in situ measurements without the need of cross sections (any cutting might influence the H concentration). Of course, it's only surface (few micrometer ) but you get the chance to look at an undisturbed sample. If you take data in listmode, you can correct for dynamic effects like effusion or diffusion.

This is a very active field at high energy x-ray Synchrotron sources due to the ability for performing real time in-situ structural studies during hydrogen loading and unloading. Here are some links that may be a bit out of date since I have not been involved with this for a while. I'm sure there is a lot more out there. The number of groups around the world doing these measurements using Synchrotron facilities is extremely large, and it is a prime focus for many Synchrotron beamlines:

http://www.hydrogen.energy.gov/pdfs/review05/stp_22_clemens.pdf

http://ftp.esrf.eu/pub/UserReports/36812_C.pdf

http://www.esrf.eu/news/general-old/general-2007/hydrogen/hydrogen/

http://www.aps.anl.gov/Science/Highlights/Content/APS_SCIENCE_20100323.php

Dear Prof. Vladimir Polyanskiy, Dr. E. Strub, and Dr. Lawrence Margulies,

   I greatly appreciate you giving me the helpful informations about hydrogen analysis. I will scrutinize the informations and discuss the right way of hydrogen analysis of the future in my institute or scientific conferences targeted for hydrogen analysis based on them.

   In the near future, millions of metallic samples exposed to hydrogen gas in hydrogen facilities will be analyzed for durability improvement against hydrogen embrittlement, residual life prediction, or fracture accident investigation. We must find analytical methods that meet the following conditions (1) ~ (6) prior to the complete arrival of the hydrogen energy society.

(1) Sensitivity (for several mass ppm or less because such trace amount of hydrogen causes hydrogen embrittlement)

(2) Accuracy and quantitative capability

(3) Capability for local area analysis (less than several micrometers in diameter) over the range of a several millimeters (It is good to imagine that we analyze elements such as P or S in steel, which cause embrittlement of the steel, with SEM-EDX or EPMA.)

(4) Capability for standardization of analytical methodology

(5) Cost

(6) Readiness for emergent analysis request (e.g., for fracture accident investigation)

I could show that my method using the D-SIMS meets the conditions from (1) to (4). However, it doesn’t satisfy (5) and (6) because the D-SIMS is a rare and extremely expensive analytical instrument (for example, a D-SIMS ” IMS-7f ” made by Cameca, France is 1.8 million Euros).

   Your informations are very helpful to find the better way. I will greatly appreciate your further information or advice.

Thank you again,

Tohru Awane,

Fukuoka, Japan

Dear Doctor Tohru Awane,

I would like to o respond you in accordance with paragraphs

1. Sensitivity

It is a main parameter, because 0,02 ppm H it is a normal in modern industrial aluminum alloys. And we can measure such concentrations.

2. Accuracy and quantitative capability

The accuracy of our equipment is about  1-8%. But calibration sample has accuracy minimum 10% . So, the absolute measurements we can do  with errors that limited by the state etalons.

3. Capability for local area analysis (less than several micrometers in diameter)

You are going to solve at least two problems simultaneously: high sensitivity and high resolution of three-dimensional. I think that it is hardly possible. 

High-resolution methods do not provide the sensitivity even  10 ppm They have a small depth of detection of hydrogen.  Surface-adsorbed hydrogen will distort the picture of the distribution.

For research purposes may be used various approaches, such as the gradual removal of the layers  by 1-10 micrometers thickness or making a cross-sectional. For Millions of samples necessary to develop a reliable method of monitoring. This is possible on the basis of our equipment.

4. Capability for standardization of analytical methodology

– not problem

5. Cost

We have a competitive market price for our equipment.  It is about 120 000 euro.

6. Readiness for emergent analysis request (e.g., for fracture accident investigation)

In our laboratory, we usually deal with such cases. Furthermore we solve the technological problems associated with the hydrogen, such as: cracking during rolling and welding, degassing techniques, elucidation of the causes of the fracture.  

With Best Regards,

Dr., prof. Vladimir Polyanskiy

Dear Dr Tohru

Are you gonna to produce hydrogen from the metals and alloys? In fact, hydrogen  

embrittlement is an old problem for the metallic materials, especially, it is formed during cleaning and pickling processes. Blisters of hydrogen are formed as an electrochemical reaction. Therefore, controlling the embrittlement problem should be done during making of the metals and alloys. It could be a source for hydrogen production. Also, If you would like to cooperate in the filed of hydrogen productions from metals and alloys, I am willing to cooperate. See my publications in the Inter. J. of Hydrogen Energy about hydrogen production form steel and aluminium alloys.

Best regards

Prof. A A El-Meligi

Dear Prof. Vladimir Polyanskiy,

Thank you very much for your minute and valuable infromation about the hydrogen analyzer AV-1. Your answers are very helpful.

Dear Prof. Amin El-Meligi,

Thank you for your answering. My purpose is not hydrogen production but local area analysis of hydrogen to investigate the health of metallic materials exposed to hydrogen gas in hydrogen facilities such as fuel cell systems or hydrogen stations. Though the purpose is different, I will read your publication in the Inter. J. of Hydrogen Energy.

Dear Dr Tohru

Thanks a lot for your kind reply, hydrogen is an important candidate for research, still  we can benefit from the presence of hydrogen in the metallic materials, if you are interested send me an e-mail.

Dear Dr Tohru,

Thank you for your kind attention.

I would like to add that we have 20 years of experience in measuring the concentration of hydrogen in metals and we can develop specialized devices for this purpose. AV-1 is designed, tested and produced commercially, so we may to write articles about it.

With Best Regards,

Dr., prof. Vladimir Polyanskiy