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Wed, 10 Apr 2013 11:16:50 -0700
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Hi Harvey, 
   
I cannot believe this! Below, please find my response: 
   
Dear Gordon, 
   
You are not serious are you? Please check your facts before you make such “bold” statements. 
I say only this much:  
Please review the extensive literature on melting point depression of nanostructured materials. There are literally hundreds of articles out there detailing work by many groups all over the world dating back to the 1970ties (Buffat/Borel)
 and several handbooks. Here are just a few to get you started: 

-         
Nanoparticle Technology Handbook
by 
Masuo Hosokawa, 
Kiyoshi Nogi (Editor), 
Makio Naito (Editor), 
Toyokazu Yokoyama (Editor) 

o  
Pub. Date: November 2007, Publisher: Elsevier Science, Format: Hardcover, 644pp 

o  
ISBN-13: 9780444531223;   ISBN: 044453122X 

-         
CRC Nanomaterials Handbook  -
Yury
 Gogotsi (Editor)
– 2006 

-         
Nanomaterials: An Introduction to Synthesis, Properties and Applications – 2008 Dieter Vollath 

-         
Understanding Nanomaterials – 2011 -
Malkiat S. Johal
(Author) 

-         
Size effect on the melting temperature of gold particles 

o  
Phys. Rev. A 13, 2287–2298 (1976)  
There are a number of nanoAg products commercially available from Virginia Tech and Cookson, the third largest solder manufacturer in the world. They do claim fusion/processing temperatures below 300 C. Just google.
 
   
You caught me on that 9 year gap - cannot hide it anymore. I admit it, I was in Alcatraz -
J. Just google my name. 
   
Hope to see you June 12.    
   
------------------------------- 
   
Thank you, 
  
Alfred 
  
office: 650 354 5185 
mobile: 650 492 0133 

From: harvey [mailto:[log in to unmask]]


Sent: Wednesday, April 10, 2013 9:52 AM

To: Zinn, Alfred A

Cc: Bob Landman

Subject: EXTERNAL: Fw: Re: [TN] copper nanosolder 

   








--- On Wed, 4/10/13, Bob Landman <[log in to unmask]> wrote: 


From: Bob Landman <[log in to unmask]>

Subject: Re: [TN] copper nanosolder

To: [log in to unmask]

Date: Wednesday, April 10, 2013, 9:19 AM 

(posting on behalf of Gordon Davy)



Bob, Denny, or Mike,  since you're subscribed to TechNet, feel free to post this reaction to Zinn's  abstract (and bio). Perhaps if he sees it, he'll be able to respond before his  June 12 presentation.



Gordon Davy

Peoria, AZ



I don't want to deprecate Zinn's work. Learning how to  make copper nanoparticles and keep them from oxidizing or agglomerating is  difficult. But I am concerned with his claim that reducing the copper particle  size reduces the melting temperature to 200°C.
 It is true that surface  atoms are not as tightly bonded to their neighbors as bulk atoms, so reducing  a substance's particle  size, by increasing the surface-to-volume ratio, does reduce the melting  temperature somewhat below the bulk value. That is the
 basis of  sintering, which occurs below the bulk melting temperature. Presumably, if the  particles were small enough, no atom would have the full number of  nearest neighbors – it would be all "surface." But the melting temperature for bulk copper is just 
 short of 1100°C. That's a stretch! 



The particles of  copper in powders sold for sintering are mostly smaller than 44 µm (-325  mesh). The process requires  compacting the powder (plus lubricant) at 4,000 to 8,000 atmospheres pressure,  then and heating at 750-900°C for 5-7 minutes (see  copper-powders.com).



Dr. Zinn's copper is  in the form of "nano-particles,"  so they are presumably smaller than  1 µm. One can  contemplate whether that  roughly 1½ to 2 orders of magnitude size reduction is  sufficient to account for the differences between the above conditions
 necessary  for sintering and for conventional reflow soldering. A differential  thermal analysis curve would support the  claim that, with or without compaction, his nano-copper  "solder" melts at 200°C.




Consider this  analysis taken from everyday observation. When snowflakes, which may have  nano-scale features, fall and land, they sometimes sinter, and sometimes (when  temperatures remain below about -15°C) they do not. People refer to that latter  kind,
 once it has landed, as "powder" snow. Similarly, one cannot skate on very  cold ice because the surface lacks the "liquid-like" layer to lubricate the  blade. (Pressure melting is a minor factor.)




So  if dropping the temperature of ice by fifteen degrees below its melting  temperature prevents sintering and skating, is it likely that copper sintering  will occur at a temperature nearly nine hundred degrees below its melting  temperature? As for melting, 
 even if individual particles were to melt at such  a low temperature and join to form a liquid, what would prevent the liquid, now  with dimensions measuring from micrometers to millimeters, from instantly  freezing?



More likely, the copper particles dissolve into the tin or tin-lead plating  on the board lands and component terminations (to form bronze, if the reaction  goes to completion). Even if the nanoparticles are not melting or sintering,  it's a clever idea, but
 we need to know: 

  * How well these bronze connections, presumably far stiffer than those of a    tin-based solder, survive temperature cycling.    * The microstructure, so we can understand the attachment mechanism.   * The width of the process window.    * Whether the adequacy
 of the attachment can be judged by its appearance,    and if so, by what criteria.   * Whether using Zinn's solder at 200°C gives benefits large enough to    warrant replacing Pb-free reflow soldering (peak local temperature up to 260°C    by convection, lower
 by condensation). (For those still using SnPb solder, the    conditions don't seem different enough to warrant consideration.)   * Whether Zinn has tried his "solder"    with non-tin land finishes such as immersion silver, ENIG,    and ENEPIG, and NiPdAu termination
 finish. Since I suspect that the colloidal copper does    not melt    or sinter at 200°C, I suspect that    it is not going to perform with Ag    or Pd nearly as nicely as with near-molten Sn, and its reaction with Ni would    be even worse.


  

    * If it doesn't make reliable bonds with      all the finishes likely to be present on an assembly, then      it is not a "drop-in replacement"      for solder. (Yes, the designer can specify a compatible finish for the lands      of the board he designs,
 but not the termination finish of the      components he chooses. He can specify, say, immersion tin instead of      ENIG, but must accept NiPdAu on some components.)     * Maybe Zinn can add enough nanoparticle Sn      to the formula to provide the necessary
 wetting to Pd without increasing the      reflow temperature and without introducing a risk of whiskers from the      solder itself.     * The risk of short circuits due to whiskers      growing SAC solder appears to be low, from SnPb solder even lower, and
 with      Zinn's solder it may be zero. But regardless of the solder used, the      overall risk for an assembly remains high due to      portions of Pb-free Sn termination finish that don't get      solder-coated.

Here are two other ways of dealing with the risk of tin  whiskers:



  1. Mitigation – speculative For  assemblies for which Pb is permitted, if components with a Pb-free Sn tin finish  were dipped in SnPb solder paste (or perhaps a paste of colloidal Sn and Pb) and  heated (before or during assembly soldering), all of the original
 finish  might be covered with a layer of SnPb, and the assembly would then have a  low risk of short circuits due to tin whiskers. The paste also might  bridge.



  2. Prevention – reduced to practice After  attaching components by conventional SnPb or SAC soldering, a thin  layer of a whisker-impenetrable metal such as nickel can be applied  to the solder and the remaining (uncoated)  Pb-free Sn finish by electroless 
 deposition. The process requires immersing the entire assembly in  the bath for a minute or two. But because  electroless deposition occurs only on conducting surfaces, insulating surfaces  remain uncoated, and the performance of the assembly is unaffected.
 (Full disclosure: Bob, Denny, and I are the named  inventors on a patent application for this process – see
www.ldfcoatings.com.) 



A few additional  observations:

  * Note the irony, given the meaning of Zinn in his    mother tongue, of him developing a    tin-free solder.  * Note the    nine-year gap (between 1995 and 2004) in his bio.    * The claim of "10-15x    electrical and thermal conductivity improvements" is
 irrelevant:    what counts is overall conductance, and the reduction in a connection's    conductance due to use of conventional solder (compared to copper) is    insignificant.  * A substance's melting    temperature is a thermodynamic property. Some might 
   regard the reduction in the melting temperature of colloidal copper as    "significant" or even "dramatic." But it is not "rapid" (a term    that implies a kinetic effect).



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