From: chuck@coplex.com (Chuck Sites)
Subject: Postmortem analysis of Tom's cells
Organization: Copper Electronics, Inc.
Date: Sat, 19 Dec 1992 06:06:29 GMT
Summary: A brief on postmortem analysis of Tom Droege's CF cathodes.
Keywords: electron-microscopy, Cold Fusion, Tom Droege

Hi folks,

    As Tom has noted in the past, I have been doing a postmortem of some of
his cathodes with an SEM looking for anything interesting that might appear.
So far I've looked at two cells and one unused control cell.  This SEM is
outfitted with and EDAX X-ray backscatter system for element analysis, which 
we were using to look for any measurable transmutaions of Pd from cold
fusion.  We were hoping to find a smoking gun to the age old question of
"where is the ash."  We didn't find any smoking gun, but there is enough
good material in the form of surface effects, complex chemistry, and Pd
crystal formations that I think everyone in this group would say it's worth
while.  Over the next weeks, I will be posting some uuencoded GIFs of what
was seen. From the point of view of a electronmicroscopist, a picture is
worth a million words (and getting better). 

   The question about fusion ash in Pd, can take two tracts.  One is the
direct measurements of neutrons, charge particles, x-rays, etc.  The other
is to look postmortem at the casing in which fusion took place.  This is
based on the simple assumption that: 

Transmutations/gm*Pd = Fusions/gm*Pd/s * Cross_section_Pd * s  

   While this would seem simple to calculate, the reality it is far more
complicated.  For example simple geometries present a problem (for localized
fusion like 'fracto-fusion').  Also It ignores the fact that there are several
isotopes of Pd and with each the cross section and reaction products change.
Additionally since the final number of transmuations are dependent on upon the
previous isotope volumes, which in turn was dependent upon the earlier
transmuations, and the fusion rates of the time, it's difficult even to 
estimate.  This is an interesting problem that could be solved with a computer
program if the cross section data and reaction products is available. I haven't
persuaded this mainly because of the lack of cross section information and
reaction product tables.  If someone has such a table, please let me know
because such estimates could be important to this method of CF analysis.     

    Of the transmuations from a DD fusion in Pd, the only obvious one that
I know of is d(d,t)p -> Pd(p, gamma)Ag.  So it is that interaction I was
looking for first.  With all expectations of finding a distinct signature
of silver in the Pd, the whole idea of finding trace amounts of silver in
Pd by  backscatter X-ray was nearly shot down when we found that Pd and
Ag are so close in the main peaks, that the Pd peak easily overwhelms any
Ag peak that could be used to indicate postmortem fusion ash. These spectral
lines are so close in the X-ray K-bands and L-bands, trace amounts of one or
the other can not be distiguised.  Except one spectral peak.  This is known
as the escape peak.  In Tom's first cell (what I called "fractured
electrode"), I did see a very-very small peak at this location that did
not appear in the control.  But because this is easily a localized
contamination or perhaps fracto-fusion (in this case I was looking at
the fracture edge of one of Tom's electrodes), the parts per million
range seems very probable, all I can ask is are we looking at a Jones level,
slightly above, or background?  Honestly folks, I just can't say either way
with quantitative certainty. What I can say is we did observe a blip where
the Ag escape should be in the cell I labeled "Fractured electrode".

COMING CLEAN: 

    Tom's was asked whether there are micro-fractures in his cells.
I did not see any except in his first cell where there are several
nodual like fractal separations from the main alpha-beta phase induced
split. Let me change that.  In all of the active cathodes we looked
at, all showed some fracturing around the connection lead wire and
cathode. The first cell is so profoundly fractured, (it was split
open like a burst hot dog) that fracto-fusion residual was my first
thought and was one of the reasons I asked Tom to look at his cells.
The other was that he offered the net access to his cells for further
analysis.  It sounded interesting so in May, we did our first runs.
Anyway back to the question of micro-fractures.  There are several
scratches left over from grinding, but I was surprised to find that
there is very-very little residual material left over from this process.
We didn't see anything significant.

    Tom runs his cells with very clean pure Pd cathodes from what we see.
While the scratches might lead to some minor localized effects, their depth
is is minor compared to the bulk, and the frequency is small compared to
surface area. In the last cell we looked at, the surface was so smooth, the
only micro fracturing we saw, was around the connection between cathode
lead and the cathode.  Again, this looks like stress induced fracturing
due to a difference in expansion rates.  On this cell there is a visible
dark spot near the center of a flat sheet Pd cathode. (This was Tom's
Takahashi style experiment).  The dark spot looks like heat stress, and
we did observe some small faceted crystals of what looks like electrolyte
material in the area.  The hot spot occurs where the end of the cathode
lead wire (I assume this was Pt) ends in the cell.  The gap between these
two metals may be a collecting point for D gas, and a potential hot spot
for cold fusion, so the next time I get beam time, I'll look at this area 
closer.  It's on my list of places to look. 

SURFACE FUN:

   The active cathodes I've looked at have some wild chemistry going on. 
In the first cell, Tom was using D2SO4 for an electrolyte, and as 
one would expect, sulfur was a predominate peak in our analysis. 
I think John Logajan's comments about D2O2 formation as a source of
heat when using sulfur based electrolytes is probably correct. If
cathode surface chemistry is the key, then there should be by-products.
D2O2 or even H2O2 would be tricky to observe except by fine changes
in pH, and anomalies in the recombination of escaping gases.  In our
postmortums we did find several metals on the surface apparently
transported by the electrolytes that include Pt, Cu, Zn, S.  These
were not minor concentrations, and the source of Cu, Zn was from a
brass connector  that made contact with the electrolyte. In the other
active cathode (Takahashi style) we saw Pt, Cu, Fe, Zn.  This cell had
an inactive stainless steel part submerged in the solution. To me, it
is some what amazing that stainless steel which is pretty inert and
fairly resistive to chemical attacks, becomes apparent in our analysis
even though its not suppose to be an active electrolysis participant.
It was only in contact with the electrolyte, and yet we see deposits Fe
on the Pd cathode. Tom mentioned to me that stainless should have Ni in it. 
It I recall it could also have Vanadium too.  If it does, these weren't
apparent in our analysis. It may be that that the electrolytic etching of
the electrodes is somewhat selective, since neither of these metals migrated
to the Pd. Obviously metal transport in an electrolyte is not new, (can you say
electroplating?) but to find something as inert as a Pt anode and metals
from an inactive stainless steel component this active in the electrolyte 
deposits, was a surprise to me. Regardless, it suggest that all thermocouples
that are used in these types of experiments should be protected by some type
of sheath. I think glass would be good. Ahh, but what about Si?.  We did see
this too, but only when glass was in direct contact with the Pd.  Si does
not appear to migrate naturally under electrolysis from what we see.    

EQUIPMENT:

   We used an ISI600 SEM (scanning electron microscope) outfitted with
an EDAX backscatter X-ray spectrometer for materials analysis. The EDAX
uses x-rays created by the SEM's electron beam on the surface area being
examined to determine the areas composition.  Its detection capabilities
are in the parts per million but it is limited. It cannot detect elements
below boron, and due to the potential of damaging the SiLi detector from
D and Li residual in the cathode cells, we ran the system with the light
element window closed. This limited us to elements above Oxygen.  Also the
system cannot resolve isotopes of a specific elements so we cannot say there
is or isn't isotope shifts indicating a nuclear ash. This leaves us with
only the ability to observe direct transmutation (like Pd->Ag if fusion of
rates occurs) and surface composition indicating the cell's chemistry for
heavier elements.

   The ISI600 is not a High-res SEM, but it is mature. The same is true of
the EDAX system.  If I had to fault EDAX's maturity it would be that their
auto peak analysis has a tendency to pick K lines over other M lines for
identification of elements.  This lead to a problem where we thought we
found a strong Yttrium K-alpha line, which was actually a strong Pt-M
line.  Because Y is pretty rare, this sent several of us scrambling thinking
we had the smoking gun. Pd and other transition metals can be fissioned
into various light elements, and Y is one candidate from Pd+d.  Alas, it
wasn't true. It was a software design presumption that the K lines would
be stronger than the L and M's. This happened again where the in the
Takahashi style experiment, Tm was chosen over Si. As Tom has said, we
all learn from mistakes and those of others. This was mine. 

PRELIMINARY DATA:

   Here is the data. The first column is unprocessed data.  The ZAFS
is a correction to the spectrum based on the atomic weight and atomic
number (Z & A) of the elements and is the better value.  CPS is the
Counts per Second for the channel numbers expected for that peak.
The %Wt is the percent weight for the sample under beam.  

LIVE TIME: 159.842 sec
11-JUN-92 21:21:37                11-JUN-92 21:21:50       
Sample: Fractured Electrode	  Sample: Fractured Electrode
Inside Edge. Photo 47.       	  Inside Edge. Photo 47.  (After ZAFS)  
Element    CPS      %Wt		  Element    CPS      %Wt  
-------- ------- --------	  -------- ------- --------
Pt M      19.156    5.808	  Pt M      19.1564   7.67 
S  K      18.280    1.616	  S  K      18.2604   3.33 
Pd L      77.155   16.974	  Pd L      77.1553  24.79 
Ag L       5.362    1.332	  Ag L       5.3615   1.63 
Cu K     271.561   62.857	  Cu K     271.5612  53.40 
Zn K      12.938    3.474	  Zn K      12.9377   2.94 
Pt L       8.077    5.939	  Pt L       8.0767   6.24 

Note: This samples was done at an area where the metal edge of
      the fracture was peeking through electrolyte build up. 
      The surface was extremely etched, looking like a sponge.
      The Ag could be an artifact of Pd L.  

LIVE TIME: 176.573 sec.
11-JUN-92 20:11:02                11-JUN-92 20:11:50       
Sample: Fractured Electrode	  Sample: Fractured Electrode
Cleaned area. Photo 32.       	  Cleaned area. Photo 32.  (After ZAFS)  
Element    CPS      %Wt		  Element    CPS      %Wt  
-------- ------- --------	  -------- ------- --------
Pd L     224.491   97.740	  Pd L     224.4907  97.64 
Pt L       1.303    1.696	  Pt M       1.3026   1.83 
Y  K       0.176    0.564  *      Y  K       0.1756   0.53  *

* We used this one to prove to ourselves that Y peak we had 
  found in an earlier runs was probably an artifact of the 
  Pt M spectra. The values suggest what to expect from the 
  possibility of Pd-L to Ag-K spectral artifact. The area
  was cleaned by scraping a deep gouge out of the surface
  with a razor.    

LIVE TIME: 178.728 sec.
11-JUN-92 20:39:03                11-JUN-92 20:39:15       
Sample: Fractured Electrode    	  Sample: Fractured Electrode          
Surface (Cross) Photo 33.    	  Surface (Cross) Photo 33. (After ZAFS)
Element    CPS      %Wt		  Element    CPS      %Wt  
-------- ------- --------	  -------- ------- --------
Pt M       8.079    4.996	  Pt M       8.0793   4.83 
S  K       4.792    0.864	  S  K       4.7920   1.27 
Pd L     172.222   86.375	  Pd L     172.2224  86.61 
Cu K       7.242    3.419	  Cu K       7.2424   3.07 
Pt L       2.898    4.346	  Pt L       2.8983   4.23 

Note: This was a spectular Pd crystal formation we found on the
      surface. We speculate it formed during electrolysis due to
      it's relative purity and lack of electrolyte deposits.  

LIVE TIME: 174.524 sec.
25-OCT-92 13:36:59                25-OCT-92 13:37:43       
Sample: Pd Takahashi Style        Sample: Pd Takahashi Style          
Blackened Surface (No Photo)  	  Blackened Surface        (After ZAFS)  
Element    CPS      %Wt		  Element    CPS      %Wt  
-------- ------- --------	  -------- ------- --------
Na K       1.954    0.587         Na K       1.9539   1.73
Pd L     130.280   45.258         Pd L     130.2798  48.76
Ag L       3.586    1.259         Ag L       3.5857   1.32
Fe K      17.350    6.340         Fe K      17.3500   5.03
Cu K       6.716    4.924         Cu K       6.7154   3.77
Zn K       8.423    8.109         Zn K       8.4228   6.19
Pt L       7.766   33.489         Pt L       7.7665  33.58

Note:  This was from the blacked surface of Tom's Takahashi style
       experiment.  The electrolyte was LiDO and thus we can't 
       resolve the true surface chemistry.  Na K may be an artifact. 

LIVE TIME: 177.078 sec.
25-OCT-92 13:55:48                25-OCT-92 13:56:35       
Sample: Pd Takahashi Style        Sample: Pd Takahashi Style          
Clean edges      (No Photo)  	  Clean Edges             (After ZAFS)  
Element    CPS      %Wt		  Element    CPS      %Wt  
-------- ------- --------	  -------- ------- --------
Tm M      31.268    5.703  *(1)   Tm M      31.2687   8.91   *(1)
Pd L     204.870   75.258         Pd L     204.8701  78.68
Fe K       0.988    0.413         Fe K       0.9883   0.34
Cu K       3.089    2.589         Cu K       3.0890   2.05
Zn K       1.502    1.635         Zn K       1.5002   1.29
Pt L       0.384    1.892         Pt L       0.3838   1.94
Pb L       0.361    6.398         Pb L       0.3614   6.79

* Tm M is misidentified.  It should be Si K.  The %Wt is thus wrong.
Note:  This was where a glass holder pinched onto the surface.  This 
       left a clean edge about 2 mm on two sides.  The Pb was
       probably from the glass.

CONCLUSIONS:

   When we first started this work, it was done to briefly get a 
run down of the constituents of the surface specifically looking
for transmutation without regard to quantitative analysis.  This 
hap-hazard approach was good in that it allowed us to get a handle
on what to expect, but it also caused some problems for us when we
did comparative analysis and couldn't use our initial quantitative
work.  We plan to do one more run where all three samples will be
looked at simulataniously and a good comparative analysis can be 
made and allow us to verify Ag contents.

   Still, in all of our analysis we did find significant surface
deposits of Pt, up to 33% in one case, and this leads me to wonder if
these deposits are catalyizing the recombination of H + OH -> H2O. In a
closed cell, this would be of no consequence, but in an open cell where
recombination is considered 0, this could give the appearance of excess
heat. The heat of a cell is given as P = V I = [(V - k*1.48)*I] + k[1.48*I]
where k represents the recombination factor (from 0 to 1).  If in-solution
remcombination is taking place at the cathode, this should create a
solution higher in hydrogen, which might be seen as a change in pH to
acid or neutral in the case of alkali solution.  This pH change may even
be seen in closed cells, as un-recombined oxygen fills the head space of
the recombiner leaving a higher hydrogen concentration in the electrolyte.
This may be something to look for.

   Finally, while our analysis could not prove the presents of Ag as
a fusion by-product, and metal transport problems may religate further 
analysis moot if the anode is Ag bearing (at least for surface analysis).
Still this method does suggest a new method for CF exploration. If an alloy
can be made that indicates the distinct effects of irradiation by a distinct
low energy induced transmutation, this type of postmortem analysis could be
a valuable tool.       
 
Happy Holidays,
Chuck Sites
chuck@coplex.com