Szpak,S.,etal.SPAWARSystemsCenter-PacificPd:DCo-DepositionResearch:OverviewofRefereedLENR PublicationsinICCF-14InternationalConferenceonCondensedMatterNuclearScience.2008.Washington,DC. SPAWAR Systems Center-Pacific Pd:D Co-Deposition Research: Overview of Refereed LENR Publications S.Szpak1,P. A.Mosier-Boss 1,F.Gordon1,J.Dea1,J.Khim2,L. Forsley2 1 SPAWARSystems Center-Pacific,SanDiego,CA92152 2 J WK International,Annandale,VA. Abstract Scientists at theUS NavySPAWARSystems Center-Pacific(SSC-Pacific), and its predecessors, havehadextraordinarysuccess inpublishingLENR papers in peer-reviewedjournals. This success hasn’t come easilyandis duetoseveral factors. Onekeyreason forthis success was the courageoftheSSC-Pacificupper management inallowing scientists toconduct researchandpublish results ina controversial field. Thefewjournal editors,whohadthefortitudetoconsiderour work,also contributedto this success.This contrasts withthemajorityoftheir peers who,takingthepathofleast resistance,ignoredourworkout ofhand and returned manuscripts with, ‘the subject matter is not in the purview of the journal’. Thereviewers also playedaroleinthesuccessful publicationof LENR-related papers. Amultitudeofreviewers, manyoutsidethe LENR field,hadtoput aside theirbiases andlookobjectivelyat ourdata. Inturn,thereviewers’relentless concerns forcedus totenaciouslyaddress theirissues. Ultimately,theSSC-Pacific team published21refereedpapers insevenjournals andabookchapter,spanning 19 years beginningin1989.This paperis abriefsynopsis ofthosepublications. 1.S.Szpak,P.A.Mosier-Boss,andJ.J.Smith,“OntheBehaviorofPdDepositedinthePresence ofEvolvingDeuterium,” J.Electroanal.Chem.,302 (1991)255-260 This was apreliminarynoteintroducingthePd/D co-depositionprotocol as analternative experimental approach toinitiate LENR.Temperaturemeasurements usingthermocouples placedinthecathodeand solutionshowthat thecathodewas hotterthanthe solution.This indicates that theobservedheat is not duetoJouleheating. Atenfoldincreaseintritium content inthesolutionwas observed.Experiments were conducted withphotographicfilm inclose proximityofthecathode. Afterdevelopment,thefilm showedagridpattern dueto theNi screen cathodeand was attributabletotheemissionofsoft X-rays. 2.S.Szpak,C.J.Gabriel,andR.J.Nowak,“Electrochemical ChargingofPdRods,”J. Electroanal.Chem.,309(1991)273-292 Amodel was developedtodescribethe electrochemical chargingofpalladium rods. This model coupledtheinterfacial processes withthetransport ofinterstitials intheelectrodeinterior. It was shownthat boundaryconditions arisefrom thesolutionofequations governingtheelementary adsorption-desorption andadsorption-absorptionsteps as well as thesymmetryoftheelectrode. 1 3. S.Szpak,P.A.Mosier-Boss,S.R.Scharber,andJ.J.Smith,“ChargingofthePd/nHSystem: Roleofthe Interphase,” J.Electroanal.Chem.,337 (1992)147-163. Slowscancyclicvoltammetricstudies ofAu/Pd/nHwereconducted toexaminethedynamics of transport ofelectrochemicallydeuterium/hydrogenacross theelectrode/electrolyteinterphase. It was foundthat a coupled,two-layermodel oftheinterphasedescribes theobservedbehavioras a functionofscan rate and electrolytecomposition.Theeffect of chemisorbingspecies, thiourea, andpHonthetransport across theinterphasewas also investigated. 4.S.Szpak,P.A.Mosier-Boss,C.J.Gabriel,andJ.J.Smith,“AbsorptionofDeuterium in Palladium Rods: Modelvs. Experiment,”J.Electroanal.Chem.,365(1992)275-286. Amodel that incorporates variables such as electrochemical rateconstants, bulkdiffusion coefficient,andchargingcurrent has beendeveloped.Suchamodel canbe usedtopredict the overpotential,surface coverage, andbulkloadingoftheelectrodeduringcharging. The computedtimedependenceofthebulkloadinghas beencomparedwithpublishedexperimental chargingcurves. MicroscopicexaminationofachargingPd cathodeusingNomarski optics has shownthat,evenwithinasingle grain,therearepreferredsites of absorption. In-situ XRD measurements ofthechargingPdcathodeshows that deuterium preferentiallyenters thePd latticethroughthe111sites. With additional charging,abroadeningand ashift tolower2 angles was observedwhichsuggestedthepresenceofasuperchargedlayer. 5.S.Szpak,P.A.Mosier-Boss,R.D.Boss,andJ.J.Smith,“Comments ontheAnalysis ofTritium Content inElectrochemical Cells,”J.Electroanal. Chem.,373(1994)1-9. Thetimedependenceoftritium content ofanopen cell operatinggalvanostaticallywith intermittent samplinghas beenderivedandis givenbythefollowingexpression: S1  S1 m(0)r(i)t q  m(0)r(i)t  f(t)  f(0)      1     m(0)  (S 1)r(i)   m(0)     where f is thetritium massfraction,m is themass oftheelectrolytephase, r(i)denotedtherate ofchange associated withthecell current,qis the rateat whichtritium is added/removed,ands is theisotopicseparation factor. It was concludedthat acompletemass balancebetweenthe liquidandgas phases was necessaryinordertodeterminethat tritium was producedinthePd/D system. 6.S.Szpak,P.A.Mosier-Boss,andJ.J.Smith,“Deuterium UptakeDuringPd-DCodeposition,” J.Electroanal.Chem.,379 (1994)121-127. Deuterium uptakeduringPd-Dco-depositionwas examinedusinggalvanostaticperturbation techniques. Theresultant potential relaxationcurves exhibit fourdistinct potential-timeintervals wherethe relaxationprocess is controlledbytheinteractionbetweenthetransport ofdeuterium from insidethelatticeto thesurfacetoform adsorbeddeuterium andthe reductionofpalladium from solution. 7.S.Szpak,P.A.Mosier-Boss,S.R.Scharber, and J.J.Smith,“CyclicVoltammetryofPd+ D Codeposition,”J.Electroanal.Chem.,380(1995) 1-6. Processes associatedwiththePd+Dalloycodepositionwereexaminedbycyclicvoltammetry. Thedynamics oftheinterphaseregionarediscussed. 2 8.S.Szpak,P.A.Mosier-Boss,andJ.J.Smith,“OntheBehavioroftheCathodicallyPolarized Pd/DSystem: Searchfor EmanatingRadiation,”Phys. Lett.A.210(1996)382-390. Pd/Dco-depositionexperiments wereconductedinsideleadcaves whilemeasuringgamma and X-rays, as afunctionoftime,usinga HPGedetectorwithanAl windowanda Si(Li)detector withaBe window.ThecathodicallypolarizedPd/Dsystem was observedtoemit X-rays witha broadenergydistributionandwithanoccasional emergenceofrecognizablepeaks attributableto thePdK andPt Llines. TheemissionofX-rays is sporadicandoflimited duration. α 9.S.SzpakandP.A.Mosier-Boss, “Onthe BehavioroftheCathodicallyPolarizedPd/DSystem: AResponsetoVigier’s Comments,”Phys. Lett.A.221(1996)141-143. Preliminaryresults ofthermal imagingofthePd/Dcathodepreparedusingtheco-deposition techniquearepresented. Hot spots areobservedthat appear/disappearchaotically.Withtime thesehot spots mergeintolargerislands that exhibit oscillatorybehavior. SEM images of aPd/D cathodethat hadmeltedduringelectrolysis areshown. 10.S.Szpak,P.A.Mosier-Boss,R.D. Boss,andJ.J.Smith,“OntheBehaviorofthePd/D System: Evidence forTritium Production,”Fus. Technol.,33(1998)38-51. Intheseexperiments, the D andO gases were recombinedinaseparate chamber.Thetritium 2 2 content intheliquidandgas phases weremeasureddailyusingaliquidscintillation.The measureddatawereanalyzedusingthemass balanceexpressionthat was derivedearlier. It was observedthat tritium productionoccurredinbursts andsporadically.Duringaburst,therateof tritium productionwas estimatedtobe103 to104 atoms s-1.Tritium producedduringprolonged electrolysis was transportedout oftheelectrodeinteriorbytwodistinct paths. Onepathresults in enrichment oftritium inboththeelectrolyteand gas phases. Thesecondresults inenhancement onlyinthe gas phase. 11.S.SzpakandP.A.Mosier-Boss, “OntheReleaseof from cathodicallypolarized Palladium Electrodes,”Fus. Technol.34(1998)273-278. nH 1 Thereleasepaths fortritium producedduringelectrochemical compression ofdeuterium inaPd latticewereexamined.Theresults indicatethat tritium productionrequires highD/Pdatomic ratios. This requirement is met iftherearenochannels reachingthecontact surface.The electrogeneratedtritium is distributedamongthevoids andbulkmaterial.Gas evolution promotes acontinuous exchangebetweenthenH atoms residinginthesubsurfacelayerand 1 withthoseintheadsorbedstate. Atoms intheadsorbedstateexchangewiththemolecules ofthe contactingelectrolytephaseor gaseous phase,leadingtotwodistinct transferpaths. 12.P.A.Mosier-Boss andS.Szpak,“ThePd/nHSystem: Transport Processes and Development ofThermal Instabilities,” NuovoCimentoSoc.Ital.Fis. A,112(1999)577-587. Thesurfacetemperature distributionofthecathodepreparedbyPd/Dco-depositiononaNi screen was measuredusinganinfraredcamera. It was observedthat,unlikejouleheating, excess enthalpygenerationoccurs intheform oflocalizedevents incloseproximitytothecontact surface. It was also observedthat,thehigherthe electrolytetemperature,themorefrequent the events. Inthelimit,theseevents overlap toproduceoscillatingislands. 13.S.Szpak,P.A.Mosier-Boss, andM. H.Miles, “CalorimetryofthePd+ DCodeposition,” Fus. Technol.,36(1999) 234-241. 3 Calorimetricmeasurements indicatethat theexcess enthalpygeneratedin cells using cathodes preparedbytheco-depositionprocess is, onaverage,higherthanthat producedincells using solidPdrods. Infraredimagingofthe cathodes preparedbyPd/Dco-depositionshows that the heat sources arehighlylocalized.Thesteepness of thetemperature gradients indicatethat the heat sources arelocatedincloseproximitytotheelectrode-solutioncontact surface. 14.S.Szpak,P.A.Mosier-Boss,M. H.Miles, and M. Fleischmann,“Thermal Behaviorof PolarizedPd/DElectrodes PreparedbyCo-deposition,”ThermochimicaActa,410(2004)101- 107. Thethermal behaviorof Pd/Delectrodes, preparedbythe co-depositiontechnique,was examinedusingaDewar-type electrochemical cell calorimeter.Results indicatedthat excess enthalpyis generatedduringand afterthecompletionoftheco-deposition process.The rates of excess enthalpygeneratedusingtheco-depositiontechniquewerehigherthanthoseobtained usingPdwires orotherforms ofPdelectrodes. Positivefeedbackandheat-after-deatheffects wereobserved.Therates ofexcess power generationwere foundtoincreasewithanincreasein bothcell current andcell temperature. 15.S.Szpak,P.A.Mosier-Boss,C.Young,andF.E.Gordon,“TheEffect ofanExternal Electric FieldonSurfaceMorphologyofCo-depositedPd/DFilms,”J.Electroanal.Chem.,580(2005) 284-290. Afterplatingout thePdonaAufoil,thecell current was increasedand anexternal electricfield was appliedacross thecell.Theexperiment was terminatedafter48h.The cell was disassembledandthecathodewas subjectedtoanalysis usinganSEM. Intheabsenceof an external electric field,the Pddeposit exhibits acauliflowerstructure. After exposuretoan external electric field,significant changes inthemorphologyofthePd/Ddeposit wereobserved. Fractal features wereobservedas well as dendriticgrowths, rods, wires, andcraters. Considerableworkis neededtoaccount forthevarietyofshapes. Theprocess ofshape changeis drivenbyenergytransferredfrom the electrostatic fieldanddirectedbythe field. 16.S.Szpak,P.A.Mosier-Boss,C.Young,andF.E.Gordon,“Evidenceof NuclearReactions in thePd Lattice,”Naturwissenschaften,92(2005)394-397. Whenacathodeprepared byPd/Dco-depositionis subjectedtoanexternal electrostaticfield, SEM analysis ofthedeposit shows discretesites exhibitingmolten-likefeatures. Suchfeatures requiresubstantial energyexpenditureinorderto form. EDXanalysis ofthesefeatures shows thepresenceofnewelements (Al,Mg,Ca,Si, Zn,…)that couldnot beextractedfrom cell components. 17.S.Szpak,P.A.Mosier-Boss, andF.E.Gordon, “FurtherEvidenceofNuclearReactions inthe Pd/D Lattice: EmissionofChargedParticles,”Naturwissenschaften,94(2007)511-514. CR-39is asolidstatenucleartrackdetectorthat is usedtodetect energetic particles suchas alphas, protons, tritons, andhelium-3.Pd/Dco-depositionwas done,inthepresenceofan external electricormagneticfield,withthecathodeindirect contact witha CR-39detector. Tracks ontheCR-39detectorwereobservedwherethecathodewas in contact withtheplastic indicatingthat thesource ofthetracks is the cathode.Thefeatures ofthese tracks (optical contrast,shape, andbright spot inthecenterofthepit)are consistent withthoseobservedforpits inCR-39that areofanuclearorigin.Theemissionoftheenergeticparticles is sporadicand occurs inbursts. 4 18.P.A.Mosier-Boss,S. Szpak,F.E.Gordon,and L.P.G. Forsley,“Useof CR-39inPd/DCo- depositionExperiments,”Eur. Phys. J.Appl.Phys., 40(2007)293-303. Aseries of control experiments were conducted. It was shownthat thetracks observedinCR-39 detectors subjectedtoPd/Dco-depositionwerenot duetoradioactive contaminationofthecell components. Notracks wereobservedwhenCuwas electrochemicallyplatedonthesurfaceof theCR-39detectors. This indicates that thepits cannot beattributedtochemical attackofthe surfaceoftheCR-39byeitherD ,O ,orCl present intheelectrolyte.Norcanthepits be 2 2 2 attributedtothemetal dendrites piercingintothesurfaceofthedetectors. Additional experiments showedthat LiCl is not essential fortheproductionofpits andthat thedensityofpits significantlydecreases whenlight wateris substitutedforD O.Quantitativeanalysis usingan 2 automatedscannershows that therearethreepopulations oftracks (0.1-0.5 μm,0.9-4.0μm,and 4.1-12μm)andthat thepits canbeeitherperfectlycircularorelliptical inshape. 19.P.A.Mosier-Boss,S. Szpak,F.E.Gordon,and L.P.G. Forsley, “DetectionofEnergetic Particles andNeutrons EmittedduringPd:DCo-deposition,”Low EnergyNuclear Reactions SourceBook,American Chemical Society,Chapter14,pp311-334.(2008). Co-depositionprocedures andcontrol experiments specificallyidentifiedtheconditions under whichnuclearparticles wereobserved, andruled out chemical means of mimickingnuclear tracks. The nuclear tracks are quantitatively examined and are consistent with neutron knock-ons. Tripletracks arepresentedas evidenceof12C(n,n´)3αindicativeof DTfusion. 20.P.A.Mosier-Boss,S. Szpak,F.E.Gordon,and L.P.G. Forsley, “TripleTracks inCR-39as theResult ofPd/DCo-deposition: EvidenceofEnergeticNeutrons,”Naturwissenschaften,in press.(2008). Tripletracks havebeenobservedinCR-39detectors usedinPd/Dco-depositionexperiments. Microscopicexaminationofthebottom ofthetripletrackpit shows that the threelobes ofthe trackaresplittingapart from acenterpoint.Thepresenceofthreeα-particle tracks outgoing from asinglepoint is diagnosticofthe12C(n,n´)3αcarbonbreakupreactionand is easily differentiatedfrom other neutroninteractions occurringwithintheCR-39detector.Thepresence oftripletracks suggests that DTreactions that produce≥9.6MeVneutrons areoccurringinside thePdlattice. 21.P.A.Mosier-Boss,S. Szpak,F.E.Gordon,and L.P.G. Forsley, ““Useof CR-39inPd/DCo- depositionExperiments:AResponsetoKowalski,”Eur. Phys. J.Appl.Phys., 41(2008)inpress. Earlierwereportedthat thepits generatedinCR-39detectors duringPd/Dco-deposition experiments areconsistent withthoseobservedforpits that areof anuclear origin.Recently,that interpretationhas beenchallenged. Inthis communication,additional experimental dataand furtheranalysis ofourearlierresults areprovided that support ouroriginal conclusions. 5