Nanoengineered Reactive Materials and Their Combustion and Synthesis Revised
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Transcript of Nanoengineered Reactive Materials and Their Combustion and Synthesis Revised
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Nanoengineered ReactiveMaterialsd th i C b ti d S th iandtheirCombustionandSynthesis
Richard A YetterRichardA.YetterPennStateUniversity
2012PrincetonCEFRCSummerSchoolOnCombustionC L th 3 hCourseLength:3hrsJune25 29,2012
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AbstractIn the nanotechnology community, there has been
tremendous progress in the molecular sciences toward thetotal command of chemistry at all length scales. This progressy g p ghas been inspired by advances in the structural determinationof biological systems. Similar advancements in assembly ofmolecular and nanoscale elements have been made in thepharmaceutical and microelectronics fields as well. Thesedevelopments make it clear that in the foreseeable future itwill be possible to synthesize any desired macroscopict t ith i l ti f t Thistructure with precise location of every atom. This courseexamines how nanotechnology methodologies are currentlybeing applied to develop multifunctional smart reactivematerials for combustion applications and the combustionmaterials for combustion applications and the combustionmethods for materials synthesis.
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Outline
IntroductionIntroduction BasicsS h i d bl SynthesisandAssembly
Combustion Applications
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Howsmallissmall?
Micrometerandnanometer Bothareinvisiblysmall
Micrometer Sizeofredbloodcell
NanometerNanometer SizeofsmallmoleculeFive times the size of the hydrogen atom Fivetimesthesizeofthehydrogenatom
S.F.SonandR.A.Yetter,Nanoenergetics,2012
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ReasonsforNanotechnologyNoSmallMatter,byFrankelandWhitesides
InformationTechnology Smallestpartsoftransistorsarenanoscale Connecting wires are < 40 nm (less than 100 gold atoms laid end to end!)Connectingwiresare
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ReasonsforNanotechnology continued Materials
Nanoscale phenomenacontrolgrainboundaries,behaviorofcracktips,voids,andotherinterfaces
Wecanalsomakenewmaterialswithnewproperties Selfassembledmonolayers,rodsorothershapes,tubes,etc. THISISBECOMINGMOREIMPORTANTINNANOENERGETICSANDNANOREACTIVEMATERIALS
Q t Ph QuantumPhenomena Nano isatthescalewherequantumeffectsbegintoemerge
Medicine Nanostructuresandnanoscience shouldbeusefulinselectingspecific
cellstodestroyorprotect,inprecisedeliveryofdrugstotissues,etc. EnergyandtheEnvironment
Nanoscale catalystsareusedtoconvertcrudeoiltousablefuels Nanoscale particlesnaturallyformedareimportantincloudformation NANOENERGETICSCANAPPLYTOENERGYAPPLICATIONS
e.g.,ultrahighsurfaceareametalfoamsmadeviacombustionsynthesisforcatalystsorhydrogenstorage
Risks?Certainly.Safetyisacurrentareaofresearch.FrankelandWhitesides,NoSmallMatter,Belknap/Harvard,2009 S.F.SonandR.A.Yetter,Nanoenergetics,2012
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WhatNanotechnologyIsNOT Itisnotapanacea
ItdoesNOTsolveallmaterialsproblemsF ti d ti t i l it t ti ll b Forenergeticandreactivematerials,itcanpotentiallybeagamechangerwithrespecttokinetics(ignitionandreactiontimes)
It ll ill t h th t t b t ld ll Itgenerallywillnotchangetheenergycontent,butcouldallowsomereactives thatcouldnotbeconsideredotherwise(nSi isanexample)
Nano is sexy but micro still pays many of the bills Nano issexy,butmicrostillpaysmanyofthebills. FrankelandWhitesides
Nanotechnologyisnew,right? Romancup,Mayanpaint,cartires,stoplights,etc.,alluse(d)nanomaterials
SEMs, TEMs, AFM, etc. make difference today! WeveSEMs,TEMs,AFM,etc.makedifferencetoday!We veonlybeenabletoimagenanomaterials forafewdecades
S.F.SonandR.A.Yetter,Nanoenergetics,2012
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TheLycurgusCup ARomanNanotechnology
Whenilluminatedfromoutside,itappearsgreen
However,whenilluminatedfromwithinthecup,itglowsred
Colloidsofgoldandsilveralloyg ynanoparticles (~50100nm)withaAg/Auratioof7:3scatter/absorb lightyieldingthedichroic effects.
Thetransmittedredcolorisduetotinygoldparticlesembeddedintheglass,whichhaveanabsorptionpeakataround520nm.Thereflectedgreenishcolorresultsfromthesilverparticles.
TEMofsilvergoldalloyparticle within glass
TEMofsodiumchlorideparticles within glass
Freestone,I.,Meeks,N.,Sax,M.,Higgitt,C.,GoldBulletin,40,4,270,2007
particlewithinglass particleswithinglass
S.F.SonandR.A.Yetter,Nanoenergetics,2012
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Why Combustion andWhyCombustionandNanotechnology?
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CombustionandNanotechnology
140 160
Wherearetheybeingstudied?Numberofpublicationsdevotedtofuelsandenergeticmaterials
100
120
140
120
140
160
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80
100
60
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100
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40
0
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40
01995 2000 2005 2010
Year
0
Country
Numberofpublicationsbyyearandcountryforthesearchtermsnano AND(fuelORpropellant ORenergeticmaterial ORexplosive)from19962010.
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SurfacetoBulkAtomRatioforSphericalIronCrystalsCrystals
100
60
80 bulk atoms
40
60
0
20 surface atoms
00 5 10 15 20 25 30
particle size (nm)
K.J.Klabunde,J.Stark,O.Koper,C.Mohs,D.G.Park,S.Decker,Y.Jiang,I.LagadicandD.J.Zhang,J.Phys.Chem.100,(1996)1214212153.
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MeltingPointandNormalizedHeatofFusion for Tin NanoparticlesFusionforTinNanoparticles
480
500
4050
60
440
460
2030
40
4200 20 40 60 80 100
particle diameter (nm)
100 20 40 60 80 100
particle diameter (nm)
S.L.Lai,J.Y.Guo,V.Petrova,G.Ramanath,andL.H.Allen,Phys.Rev.Lett.77(1996)99102.
Foraluminumparticles:Al i S d Th D L JPC A 110 1518 2006Alavi,S.andThompson,D.L.,JPCA 110,1518,2006.Puri,P.andYang,V.,JPCC110,11776,2007.AlsoAIAA2008938andAIAA20071429.
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OtherFeaturesofNanoparticles
Increased specific surface area Increasedspecificsurfacearea Increasedreactivity Increased catalytic activity Increasedcatalyticactivity Lowermeltingtemperatures Lower sintering temperatures Lowersinteringtemperatures Superparamagneticbehavior Superplasticity Superplasticity
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StructureoftheAbaloneShell
Structureofthenacre:95 wt.% inorganic material95wt.%inorganicmaterial5wt.%organicmaterial
inorganiclayers:CaCO3 aragonite
organiclayers:
A.LinandA.Meyers,Mat.Sci.Eng.A390,2741,2005.
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Nanoparticle SelfAssembly
Sanders,J.V.,Murray,M.J.,Naturev275,1978.
Shevchenko,E.V.,Talapin,D.V.,Kotov,N.A.,OBrien,S.,Murray,C.B.,Naturev439,2006
Kalsin,A.M.,Fialkowski,M.,Paszewski,M.,Smoukov,S.K.,Bishop,K.J.,Grzybowski,B.A.,Science v312,2006
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Multiscale StructuresGeckofoothairmicro/nanostructures Climbrapidlyupsmoothverticalsurfaces Footstickingandreleasingmechanismcritical Compliantmicro andnanoscale highaspectratiobetakeratinstructuresattheirfeettoadheretoanysurfacewithapressurecontrolledcontactarea
Adhesionisduemainlytomolecularforces(vander Waalsforces)
Setae
Rowsofsetaefromatoe
Geckofoot Singleseta Finestterminalbranchofsetacalledspatulae Foothairsstartfromthemicrometerscale(stalksorseta)andgodownto100200nmdiameter
Autumn,K.,etal.,Nature,405,681684,2000
( ) g(spatular stalks)bybranching.
Eachfoothas~500ksetae,each30130mlongwith100sofspatular stalks. Attheendsofthespatular stalksareorientedcaps(spatulae)withdiametersof300500nm.
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OrganizationandAssemblyattheNanoscale:Example of an Energetic MaterialExampleofanEnergeticMaterial
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ProbingQuestions
Limited fundamental understanding of which type ofsupramolecular structures provide desirable performance incombustion mechanical and hazard characteristicscombustion, mechanical, and hazard characteristics.
How do we systematically prepare fuel nanostructures withcontrolled shapes and sizes?
What are the desirable shapes and sizes of thesenanostructures?
What kind of synthetic passivation layers are needed toWhat kind of synthetic passivation layers are needed toproduce rugged systems resisting oxidation during storage,while decreasing sensitivity?
What sorts of oxidizer nanostructures can be synthesized? What sorts of oxidizer nanostructures can be synthesized? Given fuel nanostructure, what are the best forms for theoxidizer: fuel coatings, oxidizer nanostructures, or polymermatrix oxidizer?
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ProbingQuestions contd At what length scales do chemical reaction dynamics becomesignificant/dominant?
What structures allow us to control the rate of energy releaseWhat structures allow us to control the rate of energy releaseover a wide range of conditions: passivation layers, 3Darchitectures, or concentration gradients?
What structures lead to focused or directional energy release? What structures lead to focused or directional energy release? What structures lead to reduced sensitivity? What are the fundamental mechanisms of initiation? How dothermal and shock initiation differ?
What structures lead to detonation? Can the structures be made smart? Can the structures be made smart? How best to couple the output of nanoenergetics to usablefunctions (e.g., power, mechanical force, desired chemicals)
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EnergyContentasaFunctionofParticleDiameterDiameter
1
0.8
0.6 2 nm
3
0 2
0.4 3 nm
0
0.2
9 8 7 610-9 10-8 10-7 10-6
particle diameter (m)
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SomeBasics
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HeatsofOxidationofSeveralMaterials
120
140Gravimetric (kJ/gm
fuel)
80
100
120 fuelVolumetric (kJ/cm3
fuel)
i
d
a
t
i
o
n
40
60
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0
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C
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i
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(
Z
A
B
M
a
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T
Z
i
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ThermodynamicConsiderations
Foroxygencontainingenvironments,earlystudies (Glassman Von Grosse and Conway)studies(Glassman,VonGrosseandConway)recognized
The importance of the volatility of the metal vs Theimportanceofthevolatilityofthemetalvsthemetaloxide
The relationship between the energy required to Therelationshipbetweentheenergyrequiredtogasifythemetalormetaloxideandtheoverallenergyavailablefromtheoxidationreaction agylimitingflametemperature
H > Q (Ho Ho ) HHvapdissoc >QR (HoT,vol Ho298)=HavailGlassman,Combustion,AcademicPress,3rd Edition,1996
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ThermodynamicConsiderations Contd
Metal Tbp(K)
Oxide Tvol(K)
Hf,298(kJ/mol)
Hvol(kJ/mol)
HTvol-H298 + Hvol(kJ/mol)(kJ/mol)
Al 2791 Al2O3 4000 -1676 1860 2550B 4139 B2O3 2340 -1272 360 640Be 2741 BeO 4200 -608 740 1060Cr 2952 Cr2O3 3280 -1135 1160 1700Fe 3133 FeO 3400 -272 610 830Hf 4876 HfO2 5050 -1088 1014 1420Li 1620 Li2O 2710 -599 400 680
Mg 1366 MgO 3430 -601 670 920Si 3173 SiO2 2860 -904 606 838Ti 3631 Ti3O5 4000 -2459 1890 2970Zr 4703 ZrO2 4280 -1097 920 1320
Glassman,Combustion,AcademicPress,3rd Edition,1996
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ClassificationofMetalCombustion
I VolatileProduct NonvolatileproductII Volatile metal Nonvolatile metal Volatile Metal Nonvolatile MetalII Volatilemetal
Gasphasecombustion
NonvolatilemetalSurfacecombustion
VolatileMetalGasphasecombustion
NonvolatileMetalSurfaceorcondensedphasecombustion
III Soluble Nonsoluble Soluble Nonsoluble Soluble Nonsoluble Soluble Nonsoluble
Productmaydilutemetalduring
Nofluxofproducttometal
Productmaybuildupinmetalduring
Noproductpenetrationintometal
Ifproductreturnstometalitmay
Disruptionstronglyfavoredifproduct
Metalmaydiffusethrough
Productcoatingmakesignitiondifficult
burningandcausedisruptionifitsboilingpoint
d th t
burning diluteitandcausedisruption
returnstometal growingproductlayer,purelycondensedphase
b tiexceedsthatofmetal
combustionpossible
F.A.Williams,"SomeAspectsofMetalParticleCombustion,"PhysicalandChemicalAspectsofCombustion:ATributetoIrvGlassman,F.L.DryerandR.F.Sawyer,eds.,GordonandBreach,TheNetherlands,1997,pp.267289.
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ThermodynamicConsiderations EffectofPressure and OxidizerPressureandOxidizer
6000
2Al+1.5O2
(
K
)
5000
2Al 1.5O2
2Al+1.5(O2+3.76N2)
p
e
r
a
t
u
r
e
4000
2Al+3CO2,Reactants at 298K
T
e
m
p
30002Al+3H2O(g),
0 1 1 10 1002000
Al vaporization2Al+3H2O(l),Reactants at 298K
2 (g),Reactants at 398K
Pressure (atm)0.1 1 10 100
GlassmanandYetter,Combustion,AcademicPress,4th Edition,2008
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MicronAluminumParticleCombustionOxidizerEffects PressureEffects
Air
60 t2 t 60 atm2 atm1 atm
R.A.YetterandF.L.Dryer,inFireinFreeFall:MicrogravityCombustion,H.Ross,Ed.,AcademicPress,Chapter6,2001.
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EquilibriumProductCompositionandTemperature vs Input EnthalpyTemperaturevs.InputEnthalpy
1 4500
Stoichiometric MixtureofAlandO2 at298Kand1atm
0.8
1
4000
4500
T
TAl2O
3(l)
0.63500
4000
F
r
a
c
t
i
o
n
Tempera
O
0 2
0.4
3000
M
o
l
e
F
ture (K)
Al
AlO
O
0
0.2
2500-15 -10 -5 0 5 10 15
O2
Al2O
-15 -10 -5 0 5 10 15
Assigned Enthalpy (kJ/g)Glassman,Combustion,AcademicPress,3rd Edition,1996
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FlameStructureofMicronAluminumParticle Burning in AirParticleBurninginAir
c
t
i
o
n
s
1 0 ]
NaturalLuminosity
M
o
l
e
F
r
a
c
0.60.81.0
e
r
a
t
u
r
e
[
K
]
3500
4000
T AlO
Simulated
AlO PLIF
Al2O3 EPMA
r
m
a
l
i
z
e
d
M
0 00.20.4
T
e
m
p
e
2000
2500
3000
Al2O3
T PLIF
AlO PLIF
r / rp
1 2 3 4 5 6 7 8 9 10No
r 0.0 2000AlOPLIF
Burninterruptedparticleon silicon waferr / rp onsiliconwafer
Bucher,P.,etal.Proc.Combust.Inst.,27,2421,1998.
EPMA
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ThermodynamicsofCombustionSynthesisHeatsofFormationofChlorides
Chloride Hfo,298K(kJ/mol)
PerClatom
HeatsofFormationofNitrides
Nitride Hfo,298K(kJ/mol)
PerNatom
CsCl 443 443
KCl 437 437
BaCl2 859 430
HfN 369 369
ZrN 365 365
TiN 338 3382RbCl 430 430
SrCl2 829 415
NaCl 411 411
AlN 318 318
BN 251 251
Mg3N2 461 231
LiCl 408 408
CaCl2 796 398
CeCl3 1088 362
g3 2Si3N4 745 186
Li3N 165 165
N2 0 0CeCl3 1088 362
AlCl3 706 235
TiCl4 815 204
SiCl4 663 166
N2 0 0
NaN3 22 7
MClx +xNa +(y/2)N2 xNaCl +MNySiCl4 663 166 MClx +nMCly +(x+ny)Na
(x+ny)NaCl +MMnMClx +xNaxNaCl +M
Glassman,Combustion,AcademicPress,3rd Edition,1996
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ExamplesofEnergyContentofThermite andIntermetallic ReactionsIntermetallic Reactions
Reactants HeatofReaction Reactants HeatofReaction
cal/g cal/cm3 cal/g cal/cm3
TNT 649 1073 TNT 649 1073
l l2Al+3CuO 974 4976 Al+Ni 330 1706
2Al+MoO3 1124 4279 Al+Pd 327 2890
2Al + 3NiO 822 4288 2B + Hf 401 33032Al+3NiO 822 4288 2B+Hf 401 3303
Si+2CuO 762 4354 B+Ti 670 2558
3Si +2MoO3 720 3000 3Si+5Ti 428 1590
Si+2NiO 569 3420 C+Ti 736 2760
C +2CuO 11 66 C+Zr 455 2400
Fischer,S.H.andGrubelich,M.C.,32nd AIAA/ASME/SAE/ASEEJointPropulsionConference,LakeBuenaVista,Fl,July13,1996.
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ModesofParticleCombustion
11
DiffusionControlledwithEnvelopeFlame
DiffusionControlledwithoutEnvelopeFlame
KineticallyControlled
T/T
T/T
fuel
1T/T
fuel
products
1 T/T1
oxidizerproducts
s0oxidizer
products
s0oxidizer
fuelproducts
s0ss
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Diffusionvs KineticControl
B)1(D8d
t20p
b,diff = l )iY1(D8d
t20p
b,diff = l
Diffusioncontrolledcombustionwithvaporizationorsurfacereaction
B)1(D8b,diff +ln )iY1(D8 O,b,diff +ln
dKineticcontrolledsurfacereaction
=
O,p
0pb,kin kPXMW2
dt
As particle size is decreased two conditions defined by Da =1 and Kn =1 arise
XkPdMWtDa O,0pb,diff ==
Asparticlesizeisdecreased,twoconditionsdefinedbyDa=1andKn=1arise
)iY1(D4tDa
O,b,kin +ln
d2Kn = 1 2= 21
2 /
=pd N2
2 21
RTMW8P
/
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ShrinkingCoreModelforSphericalParticlesofUnchanging Size
Product Unreactedcore
Low HighUnreacted
core
UnchangingSizeDiffusionthroughProductLayerControls
t
i
o
n
o
f
r
e
a
c
t
a
n
t Typicalpositionindiffusionregion
Lowconversion conversion
Time Time
Product
Reactionzone
R Rrc rc0
C
o
n
c
e
n
t
r
a
t
g
a
s
p
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a
s
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r
CAg
CA
0 r
region
n
t
r
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r
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a
c
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a
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Product Unreactedcore
Radialposition
R R R R R R00 0
C
o
n
c
e
n
s
o
l
i
d
ChemicalReactionControls
e
n
t
r
a
t
i
o
n
o
f
a
s
e
r
e
a
c
t
a
n
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CAg
Radialposition
R R R R R R00 0
RadialpositionR Rrc rc0
C
o
n
c
e
g
a
s
p
h
a
Seeforexample,Levenspiel,O.,ChemicalReactionEngineering,ThirdEdition,J.WileyandSons,1999
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ShrinkingCoreModelforSphericalParticlesofUnchanging Size
2pR = pR =
DiffusionthroughProductLayerControls ChemicalReactionControls
UnchangingSize
Ag2 3
2 / 3
6bDCt r r1 3 2
R Rt
= +
Ag
1/ 3
bkCt r1
Rt 1 (1 X)
= =
1 1 0
2 / 3t 1 3(1 X) 2(1 X)= + 1 (1 X)=
Radiusvs.Time Conversionvs.TimeRateofChangeof
Conversionvs.Conversion
0.6
0.8
R
0.6
0.8
X
-0.4
-0.2
/
d
(
t
/
)
Diff i
Diffusioncontrolled
Kineticcontrolled
Kineticcontrolled
0.2
0.4
r
/
R
0.2
0.4
1
-
X
-0.8
-0.6
d
(
1
-
X
)
/Diffusioncontrolled
Diffusioncontrolled
Kineticcontrolled
00 0.2 0.4 0.6 0.8 1
t/0
0 0.2 0.4 0.6 0.8 1t/
-10 0.2 0.4 0.6 0.8 1
X
Seeforexample,Levenspiel,O.,Chemical ReactionEngineering,ThirdEdition,J.WileyandSons,1999
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EffectofParticleDiameteronAlBurningTimeTime
100000Wilson and Williams [7]Wong and Turns [2]P ti [4]
Davis [8]Parr et al. [9] (T=1500 K)P t l [9] (T 2000 K)
1000
10000Prentice [4]Olsen and Beckstead [1]Hartman [3]Friedman and Macek [5,6]
Parr et al. [9] (T=2000 K)Park et al. [10] (T=1173 K)Eisenreich et al. [11] (T=900 K)
e
[
m
s
]
100
1000
r
n
i
n
g
T
i
m
e
1
10
B
u d1.8T=1500K
0.10.01 0.1 1 10 100 1000
Diameter [m]
T=2000K
[ ]T.Bazyn,H.Krier,andN.Glumac,ProcCombust.Inst.31(2007)2021&Combust.Flame 145(2006)703.Y.L.Shoshin andE.L.Dreizin,Combust.Flame145(2006)714.
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EffectofParticleDiameteronAlIgnitionTemperatureTemperature
3500Parr et al. [20]
3500Derevyaga et al. [34]
e
,
K
3000
[ ]Bulian et al. [38]Assovskiy et al. [40]Yusasa e tal. [37,39]Brossard et al. [36]Ermakove tal. [35]
e
,
K
3000
y g [ ]Merzhanov et al. [33]Friedman et al. [31,32]Trunov et al. [26]CurveFit
T
e
m
p
e
r
a
t
u
r
e
2000
2500
T
e
m
p
e
r
a
t
u
r
e
2000
2500
I
g
n
i
t
i
o
n
T
1000
1500
I
g
n
i
t
i
o
n
T
1000
1500
i l i10-2 10-1 100 101 102 103 104
500
1000
i l i10-2 10-1 100 101 102 103 104
500
1000
Particle Diameter, mParticle Diameter, m
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ThermalGravimetricAnalysisofNanoaluminum with CONanoaluminum withCO2
1 6
1.8 7
38nm
1.2
1.4
1.6
5
6
M
a
s
s
(
T
G
)
10m3m
108nm
45nm(2.5nm)45nm(3.6nm)
1.0
3
4
45nm(2.5nmoxide)38nm
10m
1
2
n
e
r
g
y
(
D
S
C
)
3m108nm
45nm(3.6nmoxide)
( )
250 450 650 850 1050 12500
1
E
n10m
Temperature(oC)
K.Brandstadt,D.L.Frost,andJ.A.Kozinski,inAdvancementsinEnergeticMaterialsandChemicalPropulsion,ed.K.K.KuoandJ.deDiosRivera,BegallHouse,2007.IlinAP,GromovAA,andYablunovskiiGV(2001)Combustion,explosion,andshockwaves,37n.4:418422.
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PolymorphicPhaseTransformationsinAl2O3 LayerAl2O3 Layer
M.A.Trunov,M.SchoenitzandE.L.Dreizin,CombustionTheoryandModelling,10,2006,603623
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AluminumNanoparticle OxidationwithSingleParticle Mass Spectrometry
2
ParticleMassSpectrometryIncreasedrateconstantwith
decreasingparticlesize Shrinkingcoremodel
0.5
0.6
0.7
r
s
i
o
n
,
s
T = 700oC0
2
s
e
c
)
< 50 nmE ~ 32kJ/ l
0 2
0.3
0.4
f
o
r
h
a
l
f
c
o
n
v
e
r
t ~ r1.58-4
-2
(
K
c
o
n
v
)
,
L
n
(
1
/
s
50 - 100 nm
Ea~32kJ/mol
0
0.1
0.2
0 5 10 15 20 25 30 35
T
i
m
e
f
time(s) = 0.0025r(nm)1.582
-8
-6
L
n
(
Ln(Kconv
) = 17.8 - 21000(1/T)
Ln(Kconv
) = 5.2 - 6847(1/T)
Ln(Kconv
) = 3.2 - 3824(1/T)100 -150 nm
Ea~95kJ/mol
radius, nm-80.0008 0.0009 0.001 0.0011 0.0012
1/T (1/K)
Effectivediffusioncoefficient(De)ofoxygeninashlayer=109 ~108 cm2/sfor
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OxidationofanAlNanoparticle byMultimillion Atom MD SimulationsMultimillionAtomMDSimulations
35
(
)
15
25T
h
i
c
k
n
e
s
s
95
105
115
Inner Radius
s
(
)
5
15
0 100 200
O
x
i
d
e
T
75
85
95 Outer Radius
R
a
d
i
u
s
1-1 0Pressure (GPa)
0 100 200Time (ps)
P.Vashishta,R.K.Kalia,andA.Nakano,J.Phys.Chem.B2006,110,37273733
-
S h i d A bl ?SynthesisandAssembly?
-
HowareNanoenergetics Made? Thecreationofnanoenergeticsisstilla
Nitrated Carbon
currentresearcharea Manyapproachestaken
l l d
100 nm
Nano-CrystallineExplosives Nitrated Carbon
Tube Structures Forexample,NanoAlmadevia:
exploding wires
Explosives Encapsulated
explodingwires condensationtechnique plasmamethods wetchemistryapproaches
S.F.SonandR.A.Yetter,Nanoenergetics,2012
-
SynthesisMethodsS h i G I G h d i b d h i f d i SynthesisGroupI:Gasphasecondensationbasedtechniquesforproductionofnanosized metalparticles,e.g.,wireexplosion,PVD(PhysicalVaporDeposition;e.g.,usingvacuum),CVC(ChemicalVaporDeposition),supercriticalprocessingp p g
SunX.K,Xu J.,.ChenW.D,WeiW.D.,Nanostruct.material ,4,337(1994) Tohno S.,Itoh M.,andTakanoH.,J.AerosolSci.25,839(1994) MagnussonM.H.,Deppert K.,Malm J.O.,Svensson S.,SamuelsonL.,JAerosolSci 28(Suppl1),S471,(1997) MurataT.,Itatani K.,HowellFS,Kishioka A.,andKinosita M.,JAmCeramSoc 76,2909(1993) Danen,W.C.,Martin,J.A.,USPatent5266132(1993);USPatent5606146(1997) B.H.Kear andG.Skandan,Nanostruct.Mater.8,765(1997) HahnH.,Nanostruct.Mater.9,3(1997). Ivanov G.V.,andTepper,F.,.InKuo,K.K.,etal.,Eds.,ChallengesinPropellantsandCombustion100YearsafterAfter Nobel,
Begell House,NewYork,(1997),p.636. Jiang,W.,Yatsui,K.,IEEETransactionsonPlasmaScience,26(5):14981501(1998)
SynthesisGroupII:Plasma,arc,andflamesynthesis FineParticles:synthesis,characterization,andmechanismofgrowth,SugimotoT.,Ed.NewYork,MarcelDekker,Inc.,pp.114,
404(2000) Tomita,S.,Hikita,M.,Fujii,M.,Hayashi,S.,andYamamoto,K., ChemicalPhysicsLetters316:361364(2000) ChopraN.G.,Luicken R.J.,Cherrey K.,Crespi V.H.,CohenM.L.,LouieS.G.,andZettl A.,Science 266,966(1995) Loiseau A.,Willaime F.,Demoncy N.,Hug,G.,andPascard H.,Phys.Rev.Lett.76,4737(1996) Ruoff R.S.,Lorents D.S.,ChanB.,Malhotra R.,andSubramoney S.,Science 259,346(1993) Hwang,J.H.,Dravid,V.P.,Teng,M.H.,Host,J.J.,Elliott,B.R.,Johnson,andD.L.,MasonT.O.,J.Mater.Res.12,1076(1997). SunX.,GutierrezA.,Yacaman M.J.,DongX.,andJinS.,MaterialsScienceandEngineering A286,157(2000). Pratsinis S E Progress in Energy and Combustion Science 24 197 (1998) Pratsinis S.E.ProgressinEnergyandCombustionScience,24,197(1998) Balabanova E.,Vacuum 69,207212(2002) Keil,D.G.,Calcote,H.F.andGill,R.J.,MaterialsResearchSocietySymposiumProceedings 410,167(1996). Axelbaum R.L.,Lottes C.R.,Huertas J.I.,andRosenL.J.,TwentySixthSymposium(International)onCombustion,TheCombustion
Institute,Pittsburgh,(1996),p.1891.S.F.SonandR.A.Yetter,Nanoenergetics,2012
-
SynthesisMethodscontinued SynthesisGroupIII:Wetchemistry,SolGel,etc.
HyeonLee,J.,Beaucage,G.,Pratsinis,S.E.,ChemMatter,9:24002403(1997) Tillotson,T.M.,Hrubesh,L.W.,Simpson,R.L.,Lee,R.S.,Swansiger,R.W.,Simpson,L.R.,JournalofNon
CrystallineSolids 225:358363(1998)Till t TM G h A E Si R L H b h LW S t h J H J P J F J l f N C t lli Tillotson,T.M.,Gash,A.E.,Simpson,R.L.,Hrubesh,L.W.,Satcher,J.H.,Jr.,Poco,J.F.,JournalofNonCrystallineSolids 285:338345(2001)
SynthesisGroupIV:Mechanicalalloying/activation Suryanarayana C Progress in Materials Science 46 (1 2): 1 184 (2001) Suryanarayana C.,ProgressinMaterialsScience,46(12):1184(2001) Wen,C.E.,Kobayashi,K.,Sugiyama,A.,Nishio,T.,andMatsumoto,A.,JournalofMaterialsScience 35:2099
2105(2000)
Shoshin,Y.L.,Mudryy,R.,S.,andDreizin,E.L.,CombustionandFlame 128:259269(2002) Lu,L.,Lai,M.O.,MechanicalAlloying.Kluwer AcademicPubl.,Boston,1998 ElEskandarany,M.S.,MechanicalAlloying.NoyesPublications.,Norwich,NY,2001
SynthesisGroupV: SoftLithographicPatterning,DecalTransferLithography, PhotolithographyLithography,Photolithography
S.F.SonandR.A.Yetter,Nanoenergetics,2012
-
Nanosized ReactiveMaterials Nanoscale powders
Availableinlargequantitiesnow Potentialingredientinpropellants,pyrotechnics,and
explosives
Smallersizemeanslargersurfacearea Greaterreactivity Fasterburning
Good for combustion efficiency
ThecolorofAlisstronglyrelatedtoparticlesize.Typically200nmpowderisgray(left)and40nmpowderisblack(right),fromPesiri etal.,JournalofPyrotechnics,19,192004 Goodforcombustionefficiency
OriginalnAl wasALEX(EXploded ALuminum) Explodingwires Still sold good value
50 nm; 44 m2/g
Stillsold,goodvalue Consistencynotgoodandsizedistributionbroadandincludes
largeparticles(extremelysphericalparticles,sizerangesfrom50to250nm,oxidelayerthickness~3.1nm)
However some original claims of excess surface energy
40nm
However,someoriginalclaimsofexcesssurfaceenergy Itistruethatatverysmalldiametersthereisasurfaceenergy Notsignificantinparticles>10nm KuoandothersshowedtherewasnoexcessenergyinALEX
aluminumusingcalorimetry
10 m, 0.22 m2/g
10m
S.F.SonandR.A.Yetter,Nanoenergetics,2012
-
AgeingandCoatingofParticles
Ageing test with Alex (air saturated 60 C)
AcceleratedAgeing,RoomTemperature,SaturatedHumidity AgeingtestwithAlex (air,saturated,60 C)y
1
1.2H-15 (Al, 38m)
0.6
0.8
t=0hr t=5hrs t=24hrs0.2
0.4
ALEX (nAl)0
0 5 10 15 20 25Time (days)
C.Dubois,P.G.Lafleur,C.Roy,P.BrousseauandR.A.Stowe,JPPVol.23,No.4,JulyAugust2007
-
SurfacePassivation ofBareAlNanoparticles UsingPerfluoroalkyl CarboxylicAcids(C13F27COOH)y y ( 13 27 )
FTIRSpectrum
C=O
OH
100nmSEM(225000magnification)ofAlC13F27COOH
R.J.Jouet,A.D.Warren,D.M.Rosenberg,V.J.Bellitto,K.Park,andM.R.Zachariah,Chem.Mater.17(2005)29872996.R.J.Jouet,J.R.Carney,R.H.Granholm,Sandusky,H.W.andA.D.Warren,Mater.Sci.Technol.22(2006)422429.
-
LowTemperatureStabilityandHighTemperatureReactivityofIronBasedCoreShellNanoparticlesy p
Ironnanoparticles madefromsonochemical methodSelfassembledmonolayerofdioctyl sulfosuccinate sodiumsalt(AOT)oroleicacidHexanesolutionofnanoparticles (withandwithoutSAM),airsaturated,andwithpyrene
Fluorescene lifetimeofpyrene usedasanindicationofpresenceofoxygen~450 ns => no oxygen450ns=>nooxygen~20ns=>oxygen(bimolecularquenchingreaction)
TEMofFe0AOT
C.E.BunkerandJ.J.Karnes,JACS126,10852,2004
-
SelfAssembledNanoscale Thermite Microspheres
60nm 100nm
nAl(38nm) nCuO(33nm)Kalsinetal.,Science, v312,2006
CreateSelfAssembledMonolayer(SAM)onsurfaceofindividualparticles
Monolayers contain a functionalized group atMonolayerscontainafunctionalizedgroupattailend(either+or charged)
Whenmixedinadilutedandslightlyelevatedtemperaturetheyformmacroscalestructureswithnanoscaleconstituents
~4mnAlTMA(trimethyl(11mercaptoundecyl)
nCuOMUA(11 t d i id )(trimethyl(11 mercaptoundecyl)
ammoniumchloride(11mercaptoundecanoicacid)
Malchi,J.,Foley,T.,Yetter,R.A.,ACSAPPLIEDMATERIALS&INTERFACES,1,11,2420,2009
-
Nanoenergetic CompositesofCuO Nanorods,Nanowires,andAlNanoparticlesp
R.Shendeetal.,Propellants,Explosives,Pyrotechnics33,No.2(2008)
-
FabricationofReactiveMultilayerFoils Ni/Al,Monel/Al,andNb/Si MagnetronSputterDeposited FreestandingFoils(10150mThick)
&
Stepper
Motor
Bilayer Thicknesses 25to600nm DepositionTemperature~75C
18"SubstrateCarousel
Water&Power
Ni/Al Foil as depositedSputterGuns
34"(5"x12")
Ni/AlFoilasdeposited
Ni/AlRapidReacted
AsDepositedCuOx/AlMultilayerFoilElementalDistributions
FromTimWeihs,TheJohnsHopkinsUniversityCu Al O Cu+O
-
NanoPatterning ofNanosized Thermites onaChip
PVDbasedprocesstogrownanoscale thermites (Al/CuO andAl/NiO)onaSi/glasschip
EvaporatedCu
C O/Al450C,5hair
Zhang,Rossietal,Applied Physics Letters,2007,2008Petrantoni etal.,J.Phys Chem.OfSolids,2010
Diam.:40 80nm Al/CuO ~150250nm
Al/CuO onsetT=500oCH 2 9 kJ/ 693 l/
CuO/Al
H=2.9kJ/g=693cal/g
Evaporated
xsec tiltedview
h i l l d h
Al/NiO onsetT=400oCH=2.2kJ/g=526cal/g
450C,2h, underaN2/O2 gasflow
NiO/AlNi
30oC,5x106 mbar
Zhang,Rossietal,Applied Physics A94,2009/g /g
Benefits:(1)Enhancedinterfacialcontactandreactivity,(2)impuritiesandAloxidationduringfabricationsmall,(3)sincedimensionsofCuO nanowires canbetailored,theoxidizerfueldimensionscanbecontrolledatthenanoscale,(4)processusesstandardmicrofabrication techniquesformassproductionandintegrationintofunctionaldevices.
-
TheSolgelMethodology
Condense Super-criticalextraction
Non-supercriticalextraction of
Sola colloid
Gela 3D structure
AerogelLow density / high porosity
extraction ofliquid phase
Inexpensive homogeneity on nanoscale type and amount of
Xerogel
type and amount of components easily varied
Cast complex shapes Low temp. processing g
Low porosity / high densityLow temp. processing
FromGash,LLNLS.F.SonandR.A.Yetter,Nanoenergetics,2012
-
LLNLDevelopedFourClassesofMaterialsandProcesses
Crystallites grownin pores may beenergetic
Solid skeleton may be energetic
Energetic powdersare added by a gelmending method
1. Solution crystallization 3. Skeletal Synthesis2. Powder addition
This may be a fuel or oxidizer
This may containan oxidizer or fuel
Can be straight-forward to dope with materials
4. Nano-compositesFromGash,LLNL
S.F.SonandR.A.Yetter,Nanoenergetics,2012
-
ArrestedReactiveMillingNanocomposites Top down approach to composite designStarting Materials Topdown approachtocompositedesign
vs.bottomupapproachofsolgelmethodsoruseofnanoparticles
Micronsized,nanocompositepowdersprepared
Starting Materials
byArrestedReactiveMilling:ahighenergyballmillingprocess
Eachindividualparticle is subjected to pressures as high as 5 GPaARM issubjectedtopressuresashighas5GPa
duringcollisions hasthesamecompositionasbulk hasneartheoreticalmaximumdensity
Milling is arrested before the self-Milling is arrested before the selfsustaining reaction is triggered Cross-sectioned starting
mixture: 2Al + MoO3 ARM nanocomposite
Nanocomposite A range of highly reactive materials produced; B/Ti, B/Mg, B/Zr,
Al/Fe2O3, Al/MoO3, Al/CuO, Al/Bi2O3, MgH2/CuO, Al/SrO2, Al/NaNO3, Mg/MoO3, Si/CuO, Zr/Bi2O3, MgH2/MoO3, Mg/CuO
Backscattered electron SEM ImagesFalse color maps: Al: green; MoO3: red
FromDreizen,NJIT
Liquid surfactant (hexane, kerosene) and type of grinding media are selected to adjust the powder size and the degree of refinement at which the reaction is triggered
Batch sizes: 2 g 400 g; batch synthesis time: 20 200 min
-
HighVelocityParticleConsolidation(Cold Spray)(ColdSpray)
Particlesareinjectedintoaninertgasstream(N2 orHe),thenacceleratedthroughadeLavalnozzletohighspeed.
Void
Particlesimpactsubstrateorpreviouslydepositedmaterialandmechanicallybondwithit.
Nearfullydense(
-
SiliconReactives CanAlsoBeUsedWh ili f l ?Whysiliconfuels? Theoxidelayerisonly12nmnaturally Aging(oxidation)likelybetterthanAl Generally less sensitive than Al GenerallylesssensitivethanAl Reactives couldbeintimatelyincorporatedinsiliconbasedmicroscale devices
Tuning and switching possibilities (doping/eTuningandswitchingpossibilities(doping/efield/electrowetting)
Somesystemsproducehighertemperatures Nanoporous Si(PSi)vs.NanoSiliconpowder(nSi)p ( ) p ( ) Surfacepropertiescanbemanipulated
Selfassembledmonolayers areappliedtothesurfaceofsilicon,oneithernanoporous substratesorsilicon
i lExamplesofsurfacesproducedth h hit li ht t dparticles
OxidelayerisstrippedoffwithHFleavingahydrogenterminatedsurface.
Fluorocarbonligands arethenattachedtothesurfaceby
throughwhitelightpromotedhydrosilylation reaction.M.StewartandJ.Buriak (2001).
g yThermallyInducedHydrosilylation producingareactivecompositedevoidofunreactive oxide.
-
Nanoporous SiliconFabrication
ElectrochemicalEtching Typicaletchdepthsof100200mwithreporteddepthsofover500m(thicknessofwafer)
Dopant TypeandConcentration
PoreMorphology(CrossSection)
PlanView TypicalPoreDimensions
nSi 101000nm
wafer). Porediametersand%porositycanverydramaticallydependingontheHFconcentrationandcurrent.
p,p+,n+ Si 101000nm
310nmp Si
HF BathOxidizerLoadingTechniques
Schematicdiagramillustratingthecharacteristicporemorphologiesandtypicaldimensionsasafunctionofdopant typeandconcentration.Searson andMacaulay(1992)
g q Dropcastmethod fillPSi byplacingthePSi inanoxidizersolventsolutionandallowthesolventtoevaporate(canbedoneunderlowpressuretominimize voids and with surfactant additives)
Cross-section SEM image of PSi etched 60mA/cm2 at x35k magnification.
minimizevoidsandwithsurfactantadditives) Meltcasting(e.g.,sulfur) Supercriticalfluidfilling
-
FunctionalizedGraphene SheetsasCatalystsSupports
SA~850m2/gbyBET&>1800m2/gbymethylene blueadsorptioninsolventsp
TheC/Oratioisadjustablefrom2to500,i.e.,FGS2 toFGS500. GObyStaudenmaier Method(1898) 4foldvolumeexpansion
H.C.Schniepp,etal.,J.Phys.Chem.B (2006)
Theedgescanbecarboxylated.
Additionalfunctionalgroups can be attached
Withfunctionalgroups,thicknessofgraphene sheet~0.78nm
pThermalexpansion(>500fold)at1050C Bhm(1962)
groupscanbeattached.Latticedefectscanfunctionasradicalsites.
FGSisanideal2Dmacromolecularcarrierfornanoparticles.
Exothermicsurfacereactions
a: epoxide ongraphene,b: hydroxideongraphenec,d: inplaneandoverheadviewofaFGS
reactionsTheparticlesizeisbelow1m.
Aksay, I., Princeton 2010.
-
MetalDecoratedGraphene Sheets
Graphene asatemplatefornanoparticlel i
DFTcalculationsshowthestabilizationofPtnanoparticles attheITOgraphene junctions.
nucleation.
Indiumtinoxide (ITO)nanoparticles arestabilizedonFGSatlatticedefectsites.
Pt ti l t bili d t th ITO Ptnanoparticles arestabilizedattheITOgraphene junctions.
Coarsening/sinteringofPtnanoparticlesis arrested due to their pinning at the ITOisarrestedduetotheirpinningattheITOgraphene junctions.
Theapproachissuitableforotheroxide/metaljunctionsongraphene/ j g ptemplates.
Aksay, I., Princeton and PNNL 2010.
-
PolymericNitrogenChainsinaGraphene MatrixandConfinedinsideaCarbonNanotube
LargeenergydifferencebetweensingleNNordoubleN=NandtripleNNbonds.Nitrogenbondenthalpies
NN 159kJ/molN=N 419kJ/molNN 946kJ/mol
(N=N)i159+419
|NN|946
368
ab initioelectronicstructureandmoleculardynamicscalculationsdemonstratestabilityofthei h bi d h i l d i l ilnitrogenphaseatambienttemperatureandpressurewhenintercalatedinamultilayer
graphene matrixorusingcarbonnanotube confinement. Thechargetransferfromthegraphene matrixtothenitrogenchainstabilizestheentirethree
dimensionalstructure.The hybridizationbetweenthenanotube andtheNchainconductionybandsleadstothestabilityofthepolymericnitrogen.
Timoshevskii et al., Phys Review B 80, 115409, 2009; Abou-Rachid, H., et al., Phys. Review Letters, 100, 196401, 2008. Christe, K.O., PEP 32, 3, 2007, 194.
-
UltraHighPressureSupercriticalFluidProcessing of Reactive MaterialsProcessingofReactiveMaterials
RapidExpansionofaSupercriticalSolution(RESS) RapidExpansionofaSupercriticalSolutionintoanAqueousSolution(RESSAS)
S t ti V l Expansion Nozzle C ll ti S tSupercriticalSolution
Controlledat
RapidExpansionforParticleFormationbyHomogeneous
NanosizedParticleRecovery
SaturationVessel ExpansionNozzle CollectionSystem
SelectedTandPHomogeneousNucleation
Recovery
SCF Solute
FESEMimagesof(a)RESSproducedRDXparticlesand(b)militarygradeRDX
ParticleDistributionofRESSRDXParticles FESEMimagesofRDX
coatedALEXnAl particlesfromtheRESSNprocess
Essel,J.,andKuo,K.,PennState,2012
-
Aluminum clusters have been studied and consist of metallic Al cores surrounded by a monolayer of a
ClusterAssembledReactiveMaterials
AlI + LiN(SiMe ) Al [N(SiMe ) ] 2-
AluminumclustershavebeenstudiedandconsistofmetallicAlcoressurroundedbyamonolayerofaprotectiveshell.
Particles/clustershavebetween10and100aluminumatomsanddiametersbetween0.5and1.3nm.
AlI + LiN(SiMe3)2 Al77[N(SiMe3)2]202
ThreedimensionalperiodicTableofcluster elements. Castleman, A. W., Jr.;
Al cluster (far right) consists of nested shells containing (from left
clusterelements.Castleman,A.W.,Jr.;Khanna,S.N.J.Phys.Chem.C2009,113,26642675.
Alcluster(farright)consistsofnestedshellscontaining(fromlefttoright)13,44,and20Alatoms,A. Ecker,E. Weckert,and H. Schnckel Nature 1997,387,379.
Metalhalidecocondensationreactor(MHCR)andmetalhalidechemistryenablescreationofotherlowvalent metalclusters(e.g.i f Si) ( i hh i i f l d 20 )Ti,Hf,Si) (B.Eichhorn,UniversityofMaryland,2011).
Reactionsofmetalclusterswithsmallmoleculesoftendependonclustersize andvarydiscontinuously withthenumberofatomsandcomposition,ratherthanscalelinearlywithsize,i.e.,oneatommakesadifference.
Clusterscanactasbuildingblocksfornewmaterials.Selfassembledmonolayers (SAMs)forclusterpassivation andsizecontrol.Liganddirectedassociationforaggregateformation.
-
Some Examples of NanoenergeticsSomeExamplesofNanoenergeticsCombustion
-
Nanoscale Thermite Combustion
Nanoscale thermites arepreparedviasonication inasolvent(hexanes)( )
Combustionpropagationtestedininstrumentedburntube
AlCuO
S.F.SonandR.A.Yetter,Nanoenergetics,2012
-
Nanothermite CombustionEff t f E i l R ti Eff t f Ch l Si
1000
104
FuelRichPropagationLimit600
700
nAl/nMoO3
EffectofEquivalenceRatio EffectofChannelSize
10
100
000
e
r
a
t
i
n
g
F
r
o
n
t
300
400
500
nAl/nMoO3
0.1
1
FuelLeanPropagationLimit
A
c
c
e
l
e
100
200
300/ 3
0.010 20 40 60 80 100
Mass Weight Percent nAl
p g
00 100 200 300 400 500 600 700 800
Channel Hydraulic Diameter ( m)
Dutro,G.M.,Son,S.F.,Risha,G.,R.A.Yetter,ProceedingsoftheCombustionSymposium,2009
-
Nanothermites
42 5
3Al/M O
EffectofPackingDensity EffectofParticleDiameteronIgnitionDelay
2 5
3
3.5
11.5
22.5 nanoAl/MoO3
micronAl/MoO3Al/MoO3
1 5
2
2.5
0 50
0.51
1
1.5
1 1.5 2 2.5 3 3.5 4 4.5log (d) [nm]
-1-0.5
0 0.5 1 1.5 2 2.5 3density [g/cm3] g ( ) [ ]y [g ]
J.J.GranierandM.L.Pantoya,Combust.Flame138(2004)373383.M.L.PantoyaandJ.J.Granier,PropellantsExplosivesPyrotechnics30(2005)5362.V.E.Sanders,B.W.Asay,T.J.Foley,B.C.Tappan,A.N.Pacheco,andS.F.Son,J.Propul.Power23(2007)707714.
-
PropagationMechanismsofNanothermite Reactions
P Pressure Gradient drives gases forwardP Pressure Gradient drives gases forwardConvectionwave
Whenignitedinaburntube,fastnanothermites( l/ l/ l/ )
Pressuregradientdrivesreactionforward
(Al/CuO,Al/MoO3,Al/Bi2O3)reactthroughaconvectivemechanism
Convective burning is driven
Heat Conduction
Convectiveburningisdrivenbythecreationofalargepressuregradientintheporousmixture,andnotbya temperature gradient
Hot gases penetrate the granular mixtureFlame Zone
Temp= Tf
Porous Reactants
atemperaturegradient
PressureTransducers
FiberOpticCables
Conduction waveTemperature gradient drives reaction forward
ConductionwaveTemperaturegradientdrivesreactionforward
ThT0
PowderFilledTube
-
EffectofPressureonthePropagationRateinaAl/CuONanothermite
/
s
)
V
e
l
o
c
i
t
y
t
i
n
g
i
n
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V
e
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c
i
t
y
m
/
s
/
s
/
s
NanoaluminumfromNovacentrix (avg.dp=38nm) Nano CuO fromSigmaAldrich(avg.dp=33nm) Studiesconductedinanopticalstrandburner(V=23liters)
V
f
(
m
/
Aspressureisincreased,severaldifferentmodesofpropagationareobservedP t hi h ti d h d d
F
a
s
t
C
o
n
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t
a
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t
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s
m
~
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k
m
~
1
m
/ Pressurizedwith3differentgases(Ar,He,orN2)
Pressure(MPa)
Pressureatwhichpropagationmodechangesdependsonpressurizinggas;Hehasahighthermalconductivity
1000 10002 32 3 3+ +Al CuO Al O Cu
100
1000
]
100
1000
]
Ar He
10
100
o
o
t
[
M
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a
]
10
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m
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]
a
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10 5 10 15
Pa[MPa]
O
s
c
i
l
0.10 5 10 15P
r
e
s
Pa[MPa]
O
s
-
TemperatureMeasurementsSuggestthattheFinalProductsarenotGasified
2500
3000
3500
[
K
]
e
r
a
t
u
r
e
r
e t
o
i
n
t
t
2 32 3 3+ +Al CuO Al O CuBurnTubePropagationRate~1km/s
u
m
P
r
e
(
K
)
Al/CuO
0
500
1000
1500
2000
Al/CuO
T
e
m
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A
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p
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p g /CombustionTemperature~2350150K
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3500
4000
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t
n
t
3 2 32 + +Al MoO Al O MoAl/CuO
BurnTubePropagationRate~1km/sCombustionTemperature~2150150K
u
m
B
P
P
r
a
t
u
r
e
(
K
)
Al/MoO3
0
500
1000
1500
2000
Al/MoO3
T
e
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35002 3 2 32 2+ +Al Fe O Al O Fe
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e
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Al/F O
1500
2000
2500
3000
3500
p
e
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[
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]
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2 3 2 32 2+ +Al Fe O Al O FeBurnTubePropagationRate~0.1m/sCombustionTemperature~1700150K
u
m
B
P
O
3
B
P
B
P
e
r
a
t
u
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e
(
K
)
Al/Fe2O3
0
500
1000
1500
Al/Fe2O3
T
e
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p
E
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e
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-
MetalOxidesVaporizeorDecomposeatLowTemperatures
2 212 +CuO Cu O O
Compound Tmp(K)
Tbp(K)
Tvol(K)
Al 1687 3013 n/a 2 22 2 +CuO Cu O O
2 3 3 4 213 22
+Fe O Fe O O
Al 1687 3013 n/a
Al2O3 2345 3253 n/a
CuO 1500 decomposes 1400
14 8000 14 1 104
2Fe2O3 1855 decomposes 1750
MoO3 1075 1428 n/a
8
10
12
5000
6000
7000
n
[
m
o
l
/
k
g
]
V
Volume
Cu
O
Cu2O (l)
8
10
12
6000
8000
n
[
m
o
l
/
k
g
]
V [Fe2O
3 (s)
FeO (l)
4
6
8
2000
3000
4000
C
o
n
c
e
n
t
r
a
t
i
o
n
[cm3/g]
OCu2O (s)
O2 4
6
8
2000
4000
C
o
n
c
e
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t
r
a
t
i
o
n
[cm3/g]
2 3
O
Fe3O
4 (s) O
2
Volume
0
2
0
1000
0 1000 2000 3000 4000 5000
C
Temperature [K]
Cu2 CuO
0
2
00 1000 2000 3000
C
Temperature [K]
O2
-
EffectsofOxidizervs FuelParticleSizeAl min m nanoparticles (38nm) from Technanog micron particles (2 m) from Valimet
Linear Burning Mass Burning Energetic Mass Burning Rate Avg. mass per
Aluminum:nanoparticles (38nm)fromTechnanogy,micronparticles(2m)fromValimetCopperOxide:nanoparticles (33nm)andmicronparticles(3m)fromSigmaAldrich
Rate [m/s] Rate [kg/s] [kg/s] run [g] % mass Al2O3Nano Al/ Nano CuO 977 3.79 3.14 0.31 17.1Micron Al/Nano CuO 658 4.77 4.72 0.58 1.0Nano Al/Micron CuO 197 1.31 1.08 0.53 17.1
Micron Al/Micron CuO 182 2.02 2.00 0.89 1.0
Linear propagation micron Al - micron CuO20
30
e
[
M
P
a
]
1 82 [MPa/s]
microAl/nanoCuO
Linearpropagationratewasmore
dependantontheCuO particlessize
micron Al micron CuO
nm Al - micron CuO
micron Al - nm CuO
nm Al nm CuO
micronAl/micronCuO
nmAl/micronCuO
micron Al / nm CuO
0
10
0 0.0005 0.001
P
r
e
s
s
u
r
e
Time [s]
1.82[MPa/s]
nm Al-nm CuOmicronAl/nmCuO
nmAl/nmCuO20
30
u
r
e
[
M
P
a
]
Time [s]
0.50[MPa/s]
nanoAl/microCuO
22 212 OOCuCuO +
0 200 400 600 800 1000Linear Burn Rate [m/s]LinearBurningrate[m/s]
0
10
0 0.0005 0.001
P
r
e
s
s
u
Time [s]
Evidencethattheoxidedecompositiondrivesconvectiveburning
-
SiliconReactives Backgroundk Previouswork:
Siliconpowdershavebeenusedinpyrotechnicformulationssincethe19thcentury,howeveritscombustionhasbeenrelatively unstudiedrelativelyunstudied
Thefastreactionofnanoporous siliconfirstreportedin1992byMcCordetal
In 2002 Mikulec et al reported the first solidstate explosive In2002Mikulec etalreportedthefirstsolidstateexplosiveusingporoussiliconandaGd(NO3)3x6H2O
Clment andcoworkersdevelopedanairbagigniterusingoxidizerfillednanoporous siliconwafersp
Examplesofporefillers:NaClO4 x1H2O,Ca(ClO4)2 x4H2O,MagnesiumPerchlorate,Sulfur,PFPE
Thecombustionofsiliconbasedcompositeshasnotbeenpadequatelystudied
PrototypeofPorousSibasedAirbagyp gIgniter(Clment etal.,2007)
S.F.SonandR.A.Yetter,Nanoenergetics,2012
-
PsiNaClO4 BurningRates>3000m/s Poroussiliconfilms6590mthickwerefabricatedusinggalvanicetchingapproachthatdoesnotrequireanexternalpowersupplyaswell as electrochemical etch
PsiNaClO4 reactionusedtodriveflyerplate:
Plateforce~67mN,wellaselectrochemicaletch. 3.2MsolutionofNaClO4inmethanoldropcastonthechip
HR =9.9kJ/ginN2 and27.3kJ/gO2.
,Equivalentpressureonplatearea~3.4kPa
BeckerC.R.,Apperson,S.,Morris,C.J.,Gangopadhyay,S.,Currano,L.J.,Churaman,W.A.,andStoldt,C.R.,NanoLetters,2011
EnergyoutputandinitiationaredependentonthehydrogenterminationofthePsi.
Currano andChuraman,J.MEMs,18,2009.
Propertiesandflamepropagationvelocities
Electrolyte Thickness Poresize Porosity Surface Velocity Velocityy(HF;EtOH) (m) (nm)
y(%) area
(m2/g)
yfromvideo
(m/s)
yfromwires
(m/s)
20:1 6595 2 42 5 6567 830850 3050 310020:1 6595 2.42.5 6567 830850 3050 3100
3:1 6595 2.82.9 7983 890910 2170 2150
-
ReactionTuningusingOrderedMultiscaleStructureswithnPS:TheReferenceCase
Degeneratelydoped(1 5mcm)substrateswereusedforreferenceSi Substrateswithlowerdopant concentrationsyieldfragileporouslayers Equivalenceratioofthecompositecannotbeaccuratelydetermined
Experimentalprocedure:p p Porouslayerswereetchedon4wafersusingelectrochemicalprocess Theprocesswastunedtoyieldmechanicallystablethickporouslayerswhosesurfacescanbecleanedevenafterimpregnationwiththeoxidizer
Porosity determined gravimetrically by dissolving porous layers in aqueous NaOHPorositydeterminedgravimetricallybydissolvingporouslayersinaqueousNaOH 5mmwidesampleswerescribedsoakedinMg(ClO4)2 methanolsolutions Variedcompositionswerepreparedusingsolutionsofdifferentconcentrations. Equivalenceratiowasdeterminedgravimetricallyaftercleaningthesurfaces
TopviewSideview
5020nm
FESEMimagesofporouslayersetchedondegeneratelydopedsubstrates.BETmeasurementsindicateasurfacearea~350m2/g
50m 300nm
V.K.Parimi,S.A.Tadigadapa,andR.A.Yetter
-
PropagationRatesandTemperaturesforDegeneratelyDopedSubstrates
Samplesignitedwith10mspulsefrom200WCO2 laser. Propagationrateobtainedfromxtplotsusinghighspeedvideo Reactiontemperatureestimatedusingmultiwavelengthpyrometry witha
t t d l th b t 475 615
No. th measured Speed (m/s)
Temperature (K) = const ~ 1/ ~ 1/2
spectrometerandwavelengthsbetween475615nm.
1 3.8* 1.2-1.24 5-7.7 2044 1897 17692 4.6* 1.2-3.8 2.6-7.7 1869-2184 1747-2018 1639-18763 5 6 3 3-4 6 4 1-4 53 5.6 3.3 4.6 4.1 4.54 6.7 2.4-3.4 2.5-3.3 1844-1930 1723-1798 1617-16835 8.3 4.7-5.1 3.9-4.9 1706-2043 1824-1897 1647-17716 13.5 3.9-5.2 2.4-2.8 1792-1870 1677-1746 1577-16377 16.5 10.3-19.5 3.2-4 2002 1862 17408 33.1 20.4-20.8 2.6 -3 1886-1993 1760-1853 1650-1732
Fuelrichflameextinctionlimit: Samples soaked in 0 1 M solution ( = 80) did not ignite Samplessoakedin0.1Msolution(th =80)didnotignite Samplessoakedin0.15Msolution(th =56,measured =39)ignitedbutdidnotpropagate
V.K.Parimi,S.A.Tadigadapa,andR.A.Yetter
-
ElectrochemicalEtchofSiliconWaferswithDifferentDopingProducesDifferentStructures
Higherspeedsreportedwithmoderatelydopedptypesubstrates(1 20cm) Moderately doped (25 cm boron) substrates were tested to verify higher ratesModeratelydoped(2 5 cmboron)substratesweretestedtoverifyhigherrates Reactionfrontpropagationsbetween3001,000m/swereobservedforthesesubstrates Micrometerscalecrackswereobservedintheporouslayer Porosityandequivalenceratioestimatesarebelievedtobeincorrect(P0.54,th 9.6)
b d d ll d h h h Porositycannotbedeterminedgravimetricallyduetothehighsensitivity
25cmnPS (topview) 120cmnPS25cmnPS (sideview)
(fromPhysicalOpticsCorporation)V.K.Parimi,S.A.Tadigadapa,andR.A.Yetter
-
OrderedStructuresFabricatedonDegeneratelyDopedSubstrates
Siwafers(highlydoped0.0010.005cm)werephotolithographically patternedusingthicklayersofphotoresist(KMPRorSPR2207)
AnRFRIEprocesswasusedtoetchpillaredstructuresH i h f h i li i d 35 b id ll fil d h i i Heightofthestructuresislimitedto~35mbysidewallprofileandphotoresistproperties
Usingthickerphotoresistlayersaffectsfeaturesizes Thephotoresistwasstrippedandnanopores wereetchedusingtheelectrochemicalprocess
Topview Sideview SurfaceofPillars
p Thickporouslayersareetchedbelowthesurfaces
Thepillarsare~35mtallandhave8msquarebasesseparatedby~8m.Theporediametersonthepillarsandthesubstrateare~20nm.
V.K.Parimi,S.A.Tadigadapa,andR.A.Yetter
-
ReactionPropagationthroughPatternednPS/Mg(ClO4)2 Composite
PatternednPS
r
o
p
a
g
a
t
i
o
n
.................................................................................................................................................................................................................................................................................................................................................................................................................................................................................
D
i
r
e
c
t
i
o
n
o
f
P
r
4
0
m
m
........................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................
D
=
4
1
8
5
sTopView SideView
=
8
9
2
4
s
=
5
9
0
0
s
=
9
8
6
9
s
=
9
8
8
2
s
=
9
8
9
6
s
Thepillarsare~35mtallandhave8msquarebasesseparatedby~8m.Theporediametersonthepillarsandthesubstrateare~20nm.
V.K.Parimi,S.A.Tadigadapa,andR.A.Yetter
-
EffectofDopingSiliconReactives? Why could doping make a difference? Whycoulddopingmakeadifference?
Oxidation-reduction reaction needs the transfer of electrons,likenp semiconductor
Reducing agent is the electron donor oxidizer is the electron acceptorReducingagentistheelectrondonor,oxidizeristheelectronacceptor Therefore,ann-type reducing agent andp-type oxidizer shouldbe
morereactive(McClain(1982)) Schwab & Gerlach (1967) demonstrated this with the thermiteSchwab&Gerlach (1967)demonstrated this with the thermite
reaction,
3 2 22 2Ge MoO GeO MoO+ + ntypeGe acceleratedreaction,ptypeGe slowedreaction EffectonoxidizerdopingalsoshownbyMcClain&Schwabtoimprove
oxidizerreactivity
ExtraElectron
G.M.Schwab,J.Gerlach.TheReactionofGermaniumwithMolybdenum(VI)OxideintheSolidState,Z.PhysikChem.,56:121,1967.
Phos.
-
DopedSiPowders ProductionandCharacterizationD d d d d b illi ili
D d Si W f D d Si P d
Dopedpowderswereproducedbymillingsiliconwafersinaplanetaryballmillfor3hours
PowderDesignation
Dopant SSA(m2/g)
www.retsch.com
DopedSiWafer DopedSiPowder intrinsic N/A 10.1
lowpdoped boron 10.6
ndoped arsenic 8.9
highpdoped boron 10.2
Powder Type Dopant Resistivity (-cm)
Conductivity (S/m)
wt% dopant
intrinsic N/A 80 1.25 N/Alow p-doped boron 0.015 6.67103 7.910-5 2.1310-4
BETanalysisshowsSSAshouldnotaffectburningrates
SEM images show that all
ParticlesizingcarriedoutbylaserdiffractionuniformparticlesizesweremeasuredbyMalvern
o p doped bo o 0 0 5 6 6 0 9 0 3 0n-doped arsenic 510-3 2.0104 6.5410-2high p-doped boron 3.510-3 2.86104 1.5510-2 4.3510-2
SEMimagesshowthatallpowdershavesimilarmorphologies
Agreewellwithparticlesizinglmastersizer 2000
XRDanalysisperformedwithBruker D8xraydiffractometer Nocrystallineimpuritiesdetected
results Fracturesurfacesonallparticles
S.F.Son,Purdue,2011
-
DopedPowders ReactionCharacterization BurningratesofpressedpelletsofdopedSi/PTFEat200psiwereanalyzed DopinghasalargeapparenteffectThe effect contradicts the theory Theeffectcontradictsthetheory
Differentialthermalanalysissupportsburningratedata Apparentactivationenergymeasuredbythe dopedSi/PTFEburningratespp gy yKissingermethod
Higherburningratesamplescorrelatewithloweractivationenergysamples
The effect may be kinetic but not according toTheeffectmaybekinetic,butnotaccordingtotheoriginalhypothesis!
ThermalpropertiesverifiedbyTPSmethodtobenearlyidentical
C ld th ll t f d t h
dopedSi/PTFEapparentactivationenergies
Couldtheverysmallamountofdopant havethesameeffectasdopingoftheSicrystals? Thermodynamicallytheamountofdopant hasanegligibleeffectonenergyortemperature
Couldtherebeacatalyticeffect?
S.F.Son,Purdue,2011
-
DopedPowders Summary
S ll t f b d dd d t SmallamountofboronpowderaddedtointrinsicSi/PTFEduringprocessing
Nanoborondidnotaffectburningrates Howcanobservedresultsbeexplained?Newhypotheses latticedefectsorelectronmobilityaffectskinetics:
Si/PTFE/Bburningrates
Electronmobility Proportionaltodopantconcentration Substitutional impurity
h l [ ] Latticedefectandstrainenergyduetosubstitutionalimpurities
Proportionaltodopant
enthalpy[20]
concentration
GedopedSineededtoeliminateoneoftheabove
20T.Yoshikawa,K.Morita,S.Kawanishi,andT.Tanaka,ThermodynamicsofImpurityElementsinSolidSilicon,JournalofAlloysandCompounds,Vol.490,2010,pp.3141.S.F.Son,Purdue,2011
-
LikeCarbonNanotubes andNanothermites,Nanosilicon canbeLightActivatedforIgnitiong g
N.Wang,*B.D.Yao,Y.F.Chan,andX.Y.Zhang,NanoLetters,2003,3,475n
-
CoalDirectChemicalLoopingProcess:ReactionMechanismsofSolidFuelswithMetalOxides
ReductionIndirectreductionwithaidofgaseousintermediates
CO+MO CO2 +MCO2 +C 2CO
Withcoal,volatilesmayinitiatethereactionC l l l til (CO H t ) CO H O
SpentAirforPower GenerationCoal coalvolatiles(CO,H2,etc)
ChemicalloopingoxygenuncouplingprocessMO M+O2C + O CO Reducer/Fuel Oxidizer/
MOCO2,H2O
Coal
PowerGeneration
C+O2 CO2Directsolidsolidreactions
C+2MO CO2 +2MFuel
ReactorAirReactor
M
Ai
OxidationHeterogeneousversusvaporphasecombustion
M + O2 MO
EnhancerGas Air
M O2 MOM+H2O MO+H2
-
IgnitionandFlamePropagationofCarbonCopperOxideMixtures
8
FingeringRegime
ContinuousRegimeTemperatureControlled
TubeFurnace0.8cmIDquartztube Embeddedfine
5
6
7 nCuOCuO
e
e
d
[
m
m
/
s
]
DirectSolid
~
5
4
0
o
C
CWCO2 Laser(10.6m)70W
for 0.5 s
wireTC
PC/DAQ
2
3
4
p
a
g
a
t
i
o
n
S
p
e
SolidReactionUncoupledReaction
A
u
t
o
i
g
n
i
t
i
o
n
~
for0.5s
C/CuOpowder
Quartzwool(usedforfilling)
HighSpeed
0
1
0 100 200 300 400 500 600
P
r
o
Preheat Temperature [oC]
CuO mixturedidnotselfpropagateat400oC
Camera
800
900
C
)
ContinuousRegime700
800
C
)
FingeringRegime p [ ]
400
500
600
700
e
m
p
e
r
a
t
u
r
e
(
o
C
150C,video1/10th speed 300C,video1/10th speed
300400500600
e
m
p
e
r
a
t
u
r
e
(
o
C
u = 2 0 mm/s
300
400
0 1 2 3 4 5 6
T
e
Time (s)
u = 5.9 mm/s
WeismillerandYetter,PSU
100200
0 1 2 3 4 5 6
T
e
Time (s)
u100
= 2.0 mm/s
u150
= 2.3 mm/s
-
How are nano reactive systems beingHowarenano reactivesystemsbeingapplied?
-
SomeExamplesofNanoenergeticsApplicationsApplications
Ingredientsinpropellantsandexplosives Insitu soldering and weldingIn situsolderingandwelding Gunprimers,detonators,electricmatches Airbags MicroactuatorsMicro actuators Micropumps Microthrusters Micro switches Microswitches Microvalves Dispersedcatalysts Drug injection Druginjection Visiblelightemission Activedenial Chemical looping particles Chemicalloopingparticles and,manyothers
-
N Al i ( Al) h b
ApplicationsofNano Aluminum(nAl)
2
Nano Aluminum(nAl)hasbeenusedinpropellants,explosives,andpyrotechnics
Propellants
1
1.5 rb = 2.538P0.618
Propellants Alcouldignitenear/onthesurface Wouldimproveheatfeedback
fasterburningE l i
0.5
1
0 390
Explosives Reactinthereactionzoneand
affectdetonation Mixedresults
00 0.5 1 1.5 2
log (P) [MPa]
rb = 2.092P0.390
PropellantInitialtemperature=25oC Pyrotechnics
Canpossiblyextendapplicationsofcomposites,suchasthermites(metal/metaloxidereaction,redoxlog (P) [MPa]
Compositepropellantwith18%Al Compositepropellantwith9%nAl (ALEX)/9%Al
( / ,reactions)orintermetalic (suchasAl+NiAlNi)
Reactivestructures
Mench,M.M.,Yeh,C.L.,andKuo,K.K.,PropellantBurningRateEnhancementandThermalBehaviorofUltrafineAluminumPowders(ALEX),inProc.ofthe29thAnnualConferenceofICT,1998,pp.301 3015.G.V.Ivanov,andF.Tepper,ChallengesinPropellantsandCombustion100YearsafterNobel,pp.636645,(Ed.K.K.Kuoetal.,Begell House,1997).
-
NanoAluminum/IcePropellantsforReplacementofCryogenicHydrogen
Motivation Cyro-propellant performance without cryo shortcomings Nanotechnology for designing and assembling future propellants Multi-functionality for both propulsion and power applications
y g y g1.5dia.x1.5longcenterperforated80nAlicegrain
2Al+3H2OAl2O3 +3H2
Research nAlH2OcompositesarestudiedasameanstogeneratehydrogenathightemperaturesandatfastratesC it h hi h d it d l iti it Compositeshavehighenergydensityandlowsensitivity
Combustionoccurswithoutheatreleasinggasphasereactions&thusmanyflamespreadingandinstabilityproblemsofconventionalpropellantsareeliminated.
10 rb [cm/s] = 4.5*(P[MPa])0.47
Burningratesof38nAl&liq.H2O
nAlicegraininphenolic tube
80
100
EfficiencyofH2production
1
n
i
n
g
R
a
t
e
[
c
m
/
s
]
ADN* CL-20*
HNF*
20
40
60
80
Dp = 38 nm
0.1
0.1 1 10
B
u
r
n
Pressure [MPa]
JA2# HMX* * Altwood, 1999# Kopicz, 1997
0
20
0 20 40 60 80 100 120 140Pressure [atm]
p
= 1.0Risha,G.A.,Son,S.F.,Yang,V.,&Yetter,R.A.,2008
-
FGSColloidsforEnhancedCombustionLiquid Strand Burner: NM gas-phase chemistry well understood; liquid-phase chemistry not important at low pressures
ab-initio molecular dynamics simulations show that only vacancies functionalized with groups, such as hydroxyls, ethers, and carbonyls greatly accelerate thermal greatly accelerate thermal decomposition of nitromethanethrough reaction pathways in which protons or oxygens are exchanged between the functional groups and nitromethane or its products
CatalysisatVacancies
DecreasingOcontent
Solids loading ~ 0.05 wt% More reduced FGS is a better accelerant than carbon black or FGS of low C/O (mol/mol). Lower deflagration pressure-limit with carbon additives. Reduced performance of carbon black and FGS19 at ~0.2wt% may be due to particle aggregation at liquid/vapor interface, preventing passage of particles into vapor phase. p p p At low FGS concentrations, the loss of surface defects/surface area lowers the burning rate.
(a)and(b)initialconfiguration;(c)and(d)after10 ps;(e)and(f)finalconfiguration
LM.Liu,R.Car,A.Selloni,D.M.Dabbs,I.A.Aksay,andR.A.Yetter,2012.
J.Sabourin,R.A.Yetter,D.M.Dabbs,I.A.Aksay,andF.L.Dryer,2010.
-
FGSColloidsforEnhancedFuelDecompositionLiquid Sub/Supercritical Reactor
R t T t 820 K (T 1 4)
Liquid Fuel/Particles Mixtures: 0.005wt% FGS in methylcyclohexane (MCH)
Reactor Temperature 820 K (Tr = 1.4)
Reactor Pressure 4.7 Mpa (Pr = 1.3)
Reactor Coil Length 6.4 m
Pump flow rate 0.5 mL/min
Reynolds Number 844
Residence time 14.9 sec
MCH was ~20 % more decomposed with 0.005wt% FGS than without FGS at above conditions. Gaseous products increased by ~ 20%.
4
5
p y Identified components in gaseous products and condensed phase: similar to those without FGS; however, methane (32% increase), ethane (39% increase), ethylene (18% increase), propane (38% 1
2
3
without FGSwith FGS
), y ( ), p p (increase), propylene (25% increase) all increased.
16 8 10 12 14 16
time (s)
-
Disperable NanocatalystsBoehmite Particle Carboxylatoalumane Particle
+ +
y
M1/Al2O3 CatalystM1nanocatalystFlowreactor
5000ppmi t l
100ppm ind d
SurrogateJP5 =35ms
O2=20%inN2Fuel=0.24vol.%
experiments
intoluene 1000ppm inndodecane
ndodecane
[
C
O
2
]
(
%
)
50ppm 5ppm
0 5 ppmMetalexchangereactiontoreplace aluminum cations (in 0.5ppm
NoCatalyst
~300oC
replacealuminumcations (intheboehmite particle)withmetalcations ofacetylacetonates,e.g.,Pd,Pt,lanthanum cerium etc
Wickman, D.T. et al., J. Russ. Laser Res., 27, 6, 2006T(oC)
ylanthanum,cerium,etc.
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ReactiveFoilsforSolderingandBrazingNanoFoil(IndiumCorporation formerlyReactiveNanocomposites)isanewclassofnanoengineeredmaterial.Itisfabricatedbyvapordepositingthousandsofalternatingnanoscale layersofAluminum(Al)andNickel(Ni).Whenactivatedbyasmallpulseoflocalenergyfromelectrical,opticalorthermalsources,thefoilreactstodeliverlocalizedheatuptotemperaturesof1500Cinfractions(thousandths)ofasecond.Today,thislocalized heat is used in many bonding applications ranging from the bonding of sputter targets to backinglocalizedheatisusedinmanybondingapplicationsrangingfromthebondingofsputtertargetstobackingplates,totheattachingofacomponentsuchasanLEDtoacircuitboard.http://www.indium.com/nanofoil/#ixzz1xQC55sjcNanoFoilProperties
Size thickness40150minfreestandingfforms
CompositionBeforeReaction AlternatinglayersofNiandAlCompositionAfterReaction Ni50Al50FoilDensity 5.66.0g/cm3
HeatofReaction 10501250J/gReaction Velocity 6 58 meters/secondReactionVelocity 6.5 8meters/secondMaximumReactionTemperature
13501500C(24602730F)
ThermalConductivity 3550W/mKRoHS Compliant Pbfree
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ThermalBatteries Advantages:Higherheatofreactionthanpyrotechnicheatpellets,Flamefrontvelocityof9m/sisconsiderably
Schematic of NanoFoil heated
fasterthanheatpaper;TheNiAlfoilsareelectricallyconductivebothbeforeandafterinitiation;NanoFoil generatesasignificantlysteepertemperaturerisethanpyrotechnicpellets.
Issues:Uponinitiation,thefoilstendtoflowunderpressure;Appliedloaddropsuponinitiation,whichleadstoanincreaseinthebatteryinternalresistance.
Compression
SchematicofNanoFoilheated2cellthermalbattery
Name Composition
Electrolyte LiBrLiClLiF eutectic(435oC)
Electrolytepellet
MgO/E:47/53
Cathode FeS2Cathode pellet C/Fe/E:78/2/20
C th d
MicrothermHeatpaper
Fusestrip
Cathodepellet C/Fe/E:78/2/20
Anode Li/Al:20/80
Anodepellet A/E:90/10
Heatpaper Zr/BaCrO4fibermix
CathodeElectrodeAnode
NanoFoilBuffer
PhotoofNanoFoilheated2cellthermalbattery
TC
Dischargecablescables
Poret,J.C.,Ding,M.,Krieger,F.,Swank,J.,Chen,G.,McMullan,C.,NANOFOILHEATINGELEMENTSFORTHERMALBATTERIES,ProceedingsoftheArmyScienceConference(26th),Orlando,Floridaon14,December2008
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DigitalMicrothruster
15-Thruster Unit(Flown on Shuttle)
Three-layer sandwich of silicon and glass
1024-Thruster Component(Silicon Array Nozzle)(Silicon Array Nozzle)
Silicon nitride rupture diaphragms
Divergingnozzles Lead Styphnate
C6H3N3O8PbC6H3N3O8Pb
0.1 mNs of impulse bit 5-100 mN of p100W of power thrust
Lewisetal.,SensorsandActuators80,143154,2000
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MEMSbasedPyrotechnicalMicrothrusters
100 addressable microthrusters with 3 main micromachined layers
Combustion chamber 1.5 x 1.5 x 1 mm
3 3 Th t fil ith th t
glycidyle azide polymer (GAP) mixed with AP and Zr particles propellant
zirconium perchlorate potassium primer
3.3
2.8
2.3
Thrustprofilewithathroatdia.of500m
(
m
N
)
1.6
1.3
0.8
T
h
r
u
s
t
(
Polysilicon resistor igniter at nozzle Insulating groves to eliminate cross-talk
M i i i t d d0.3
0.2300 500 700 900
Time (ms) /
Main grain was screen printed under vacuum
100% ignition success with 250 mW Thrusts ~0.3-2.3 mN
Time(ms)ZPPIgniterpeaks Flamepassesthrough
intermediarychamber
GAP/APcombustioninchamber
Rossietal.,SensorsandActuatorsA,121,508514,2005,SensorsandActuatorsA,126,241252,2006.JournalofMEMs,15,6,18051815,2006.
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MEMSDevice Integrating Nanothermite Al/CuO
Microinitiator/Micodetonator CuO/Alnanothermite onigniterchip(1mm)Ignitionofapropellant hasbeendemonstrated
Au/Pt/Crthinfilmheater
PatternedSiO2&Cufilms
CuO nano wiresAl/CuO nEM
Zhang,etal,Nanotechnology 18(2007)Zhang,etal,J.ofMicroElectroMechanical Systems,2008
~1W i iti~1Wignitionpower,0.1msignitiondelay,0.12mJ ignitionenergy60mJ outputenergy
1cm3 MEMSSafe ArmFireMEMSintegratesensors,circuitry,actuator,electricalprotections(pyrotechnicalswitches),highlyenergeticmaterial([Co(NH3)6]2[Mn(NO3)4]3 , Al/CuO nanothermite), moving barrier.([Co(NH3)6]2[Mn(NO3)4]3,Al/CuO nanothermite),movingbarrier.
Pezous etalJ.Phys &Chem.Solids 71,(2010)Pezouset al,Sensors andActuatorsA159 2010
Gas generator EMthin layerChipsize1cm
IntegratedNanothermite
A159,2010
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JumpingSensorbasedonMEMsFabricationandNanonergetic PorousSilicon
Ignitionofnanoporousenergeticsiliconviaspark
nanoporoussiliconenergetic
resistor
siliconchipIntegratednanoenergeticsiliconandMEMssensor
Churamanetal.,J.MEMs,21,1,198,2012.
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CombustionbasedActuatorsA bi i b t it il (AIBN) Azobisiobutyronitrile (AIBN)decompositionasthesolidchemicalpropellant
Successfullypumpeddeionizedwaterthrougha70mmlongchannelwithacrosssectionof100m*50mataflowrateof17ml/minwhileconsumingonly189mJofelectricpowerdecomposed
(Hongetal.,2003)
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DrugInjection
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Microenergetic Valve
AppliedonARIAN5LaunchVehicle. Designedtoisolate,priorto
actuation, the gaseous fluid presentactuation,thegaseousfluidpresentintheupstreamhighpressuretank(400bar)orpassivation ofthedownstream pressure tankdownstreampressuretank.
Reacttime
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What are new directions forWhatarenewdirectionsfornanotechnologyandcombustion?
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d ll d f l d
DirectionsForward Towards atomicallypreciseandfunctionalizednanoenergetic material.
D l t ti t i l t f Developsmartnanoenergetic materialstoperformadesiredfunctioninsteadofsimplyreactinginanuncontrolled fashionuncontrolledfashion. ActivatedbyT,P,thepresenceofaparticularchemicalcompound,orexternalstimuli,suchasanelectricalfieldorlight,e.g.,initiateareactionataparticularT,releaseaparticularcompoundataparticularT,transitionfromadeflagration to a detonation at a particular instant in time,deflagrationtoadetonationataparticularinstantintime,turnonorturnoffareaction,oraccelerateorslowareactionwithtimeorlocation.
Developmultifunctionalnanoenergetic systems.
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Nanoengineered EnergeticMaterials Atthemicroscale:engineerthenanoenergetic directlyona
MEMSchip
Heat (200 3000C) pressure (kPa Gpa) specific gases Heat(200 3000 C),pressure(kPaGpa),specificgases(neutralgas,ionizedgas)ondemand=>propulsion,power,actuation,instrumentcalibration,pumping,switches,initiators
MEMsfabricationmethodology:softlithography,screenandinkjet printing PVD etc 102inkjetprinting,PVD,etc.
Newfuelsandoxidizers:poroussilicon,nanothermites, 100
101
10
s
i
t
y
(
M
J
/
k
g
)
F
u
e
l
C
e
l
l
NanoEnergetics
andintermetallics
Scaleuptothemacroscale3
102
101E
n
e
r
g
y
D
e
n
s
F
Ultracapacitor
Capacitor
103
102 103 104 106 107105PowerDensity (W/kg)
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ChallengesandIssuesf d Scientificoriented
Thermalquenching NewEMformulation Structuralmaterialdevelopment
Engineeringoriented Selection of EM and structural material SelectionofEMandstructuralmaterial Fabricationandintegrationofthedevice IgnitionP l Pressurecontrol
Filling Sealing(Supergluesofar!)
Publicperception,safety,andregulationsaffectthingsalso
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Summary Nanoenergetics havenumerouscharacteristicsthatmakethemattractiveforuseinfuelsandenergeticmaterials.F i iti d b ti ti h t Fromanignitionandcombustionperspective,heterogeneousandcondensedphaseprocessesbecomesignificantlymoreimportant.
Fabricationandassemblyofenergeticcompositematerials(byvarioustechniques,selfassembly,coldspraying,ballmilling,solgel gasphase processes etc) are research directionsgel,gas phaseprocesses,etc)areresearchdirections.
CurrentresearchisemphasizingmanipulationofindividualatomsandmoleculestoproduceorganizedMEMsembedded
ltif ti l ti t i l f ti fmultifunctionalnano energeticmaterialsforgenerationofgaspressure(kPaGpa),heat(200 3000C),andchemicalspecies(Neutralgas,Ionizedgas)withhighlycontrollableperformances(rateofheatrelease,)andproperties(sensitivity,stability).
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Thank youThankyouQuestions?