Encyclopedia of Liquid Fuels

4519 Pages·2022·38.777 MB·English

by  Eckart W. Schmidt (Editor)

EckartW.Schmidt
EncyclopediaofLiquidFuels
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Eckart W. Schmidt
Encyclopedia
of Liquid Fuels
Volume 1: Alcohols – Amides and Imides
Author
EckartW.Schmidt
BellevueWA98007
USA
ISBN978-3-11-075025-6
e-ISBN(PDF)978-3-11-075028-7
e-ISBN(EPUB)978-3-11-075038-6
LibraryofCongressControlNumber:2022944042
BibliographicinformationpublishedbytheDeutscheNationalbibliothek
TheDeutscheNationalbibliothekliststhispublicationintheDeutscheNationalbibliografie;
detailedbibliographicdataareavailableontheInternetathttp://dnb.dnb.de.
©2023WalterdeGruyterGmbH,Berlin/Boston
Coverimage:AerojetRocketdynedevelopmentrocketengineoperatingonLOX/liquidmethane
underaNASAcontractin2007(PhotocourtesyofAerojetRocketdyne)
Typesetting:le-texpublishingservicesGmbH,Leipzig
Printingandbinding:CPIbooksGmbH,Leck
www.degruyter.com
Foreword
Rocketpropellantsarehugelyimportantmembersofthelargergroupofenergeticma-
terials.Thiscontinuouslydevelopingfieldrequiresknowledgeandunderstandingof
awide-rangeofcompoundsfromthehighlyreactivefluorineandnitrogenoxides,to
organicalkylboranesandalcohols.Forrocketpropulsion,itisessentialthataccurate
informationonthephysicalandchemicalpropertiesofthechemicalsinvolvedhas
beendeterminedpreciselyandcanbereliedupon.Thisisnotonlythecaseforknown
rocketpropellants,butisequallyessentialfordevelopingnew,“greener”(lesstoxic)
propellantsforthefuture.Thedemandsonrocketpropellantsarecontinuouslydevel-
opingandchangingwithtime,asnewneedsandrequirementsforsatellitesandrock-
etsemerge.Therefore,theEncyclopediaofRocketPropellantsisanessentialresource
forunderstandingcurrentandpastrocketpropellants,aswellasfordesigningthose
forthefuture.Acollectionofthevastphysicalandchemicaldataforpast,presentand
modernrocketpropellantsystemshasbeenmissing,anditisessentialthatasource
is available in which all reliable data has been collected together and presented in
aclearandinformativemanner.
Amongstthemanywaystocategorizepropellantsforchemicalrockets,theycan
be separatedinto twogroups,namely, solid propellants or liquid propellants, with
theformerbeingsubdividedintodouble-baseorcompositepropellants.Liquidpro-
pellantscanbesubdividedintomonopropellantsorbipropellants,thelatterofwhich
canbeagainsubdividedintohypergolicornonhypergolic.Therefore,thecomplexity
ofthesesystemsisself-evident.Hydrazineandthemethylatedderivativesmethylhy-
drazine(MMH)andunsymmetricaldimethylhydrazine(UDMH)incombinationwith
nitricacidordinitrogentetroxidearecurrentlythemostwidely-usedhypergolicpro-
pellants, however, hydrazine and its methylated derivatives are not only toxic, but
alsocarcinogenicintestanimals,andthereforeitisofconsiderableimportancetofind
less-toxicandnon-carcinogenicalternativeswhichcanstillformhypergolicmixtures.
Propertiesofmanycandidatesinthiscontextaresummarizedinthisbook.However,
manymorepromisingalternativesneedtobefoundforthefuture.Despitetheharm-
fulpropertiesof“traditional”rocketpropellantssuchasMMHorUDMH,orthehighly
corrosiveWFNAandRFNA,theycontinuetobeused,whilesaferandmoreenergetic
alternativesaresoughtforthefuture.
Searching for new, environmentally friendly and/or increased performance
rocket propellants requires knowledge of a large and diverse number of chemical
compounds, many of which are not easy to handle. Despite this, since the publi-
cation of the book Raketentreibstoffe (Springer) in 1968 by the same author as this
https://doi.org/10.1515/9783110750287-201
VI Foreword
encyclopedia,noothersuchcomprehensiveanddetailedbookhasbeenpublished
onrocketpropellantsmakingtheEncyclopediaofRocketPropellantsaseminalwork
forpast,presentandfuturedevelopmentsinthisarea.
Prof.Dr.ThomasM.Klapötke
DepartmentofChemistry
Ludwig-MaximiliansUniversity
Munich,Germany
Preface
EncyclopediaofLiquidFuels
ThisisthesecondsetofaseriesofsetsintheEncyclopediaofRocketPropellantssum-
marizing the existing literature on rocket propellants, both liquid and solid rocket
propellants.Thefirstset,EncyclopediaofOxidizers,publishedafewmonthsago,con-
tainsinformationonbothliquidandsolidoxidizers.Thissecondset,Encyclopediaof
LiquidFuels,isasummaryofliteratureonliquidfuels.Thedifferentiationbetween
liquidfuelsandsolidfuelswasnecessarybecausesolidfuelsusuallyarethebinders
forsolidpropellants,atopicreservedforafuture,plannedsetinthisseries.Thethird
set,EncyclopediaofMonopropellants,plannedtobepublishednextyear,willbeavery
comprehensivesummaryofthechemistryofmonopropellants.Thefourthandfifth
sets,plannedforthecomingyears,willdescribetheperformanceofhypergolicand
nonhypergolicbipropellantcombinations,usuallycombinationsofoxidizersandfu-
els.Iftimepermits,futuresetswilleventuallydealwithvariousaspectsofsolidpro-
pellants,suchas“CompositeSolidPropellants”and“Double-BaseSolidPropellants”,
and they would also include gas generants which have found numerous industrial
applicationssuchasinairbaginflatorsinautomobilepassengerpassiverestraintsys-
tems.“HybridPropellants”mayfindahomeinafuturesetinthedistantfuture.
InspiteoftheincreasedcapabilitiesofonlinesearchengineslikeGoogleScholar,
thecurrentsetsofbookswillbeanindispensabletoolforscientistsandengineersin
therocketpropulsionindustryandresearchorganizations.Thehazardsofworking
withrocketpropellantsneedtobewellunderstood.
Our Encyclopedia of Rocket Propellants book series will be the preferred refer-
encesourceforfuturegenerationsofrocketpropellantchemists.Whenreferringto
theprofessionofrocketpropellantchemists,thisshouldnotbedonewithoutquot-
ing,tongue-in-cheek,theprefacewrittenbyI.AsimovforJ.D.Clark’slandmarkbook
Ignition!:
“Nowitisclearthatanyoneworkingwithrocketfuelsisoutstandinglymad.Idon’t
meangarden-varietycrazyoramerelyravinglunatic.Imeanarecord-shatteringex-
ponentoffar-outinsanity.”
The reader will notice, though, that the correct terminology should have been
“rocketpropellants”andnotjust“rocketfuels”.Theauthorofthecurrentbookfeels
thatthisquotefromtheliteratureadequatelydescribestherisksinvolvedforchemists
involvedwithdevelopingmoreenergeticrocketpropellantsandexplosives.Thedivid-
inglinebetweenpowerfulrocketpropellantsandpotentialexplosivesisverynarrow
androcketpropellantchemistsareoftentreadingonanarrowpath.Nevertheless,or
justbecauseoftheinherentrisk,thisisoneofthemostexcitingbranchesofchem-
https://doi.org/10.1515/9783110750287-202
VIII Preface
istrytobeinvolvedwith.Itisthechemistryofrocketpropellantsthathasenabledthe
dramaticadvancesinspacetechnology,withmanybenefitstothecommonconsumer.
Reviewingtherecentliteratureonrocketpropellantsandotherenergeticmateri-
als,onewillnoticethattheincreasedcapabilitiesofmoderncomputershaveenabled
chemiststopredicttheperformanceofnewmoleculesevenbeforethesecompounds
were ever made and tested in the laboratory. Numerous publications referenced in
ourbooksdealjustwiththeoreticalexplorationsofthistype,andthatisadifference
topreviousbookpublicationsonthissubject.
Rocketpropellantsgenerallyconsistofoxidizersandfuels.Theterm“rocketfu-
els”isoftenmisusedtodescriberocketpropellantsingeneral.Correctuseoftheterm
“rocketfuel”wouldonlyapplytothecombustible,fuel-richpartofapropellantcom-
bination.Oxidizersarenotrocketfuels.Oxidizersforliquidrocketpropellantsaregen-
erallysubdividedbyphysicalpropertiesand/orbyreactivity.Sowedifferentiatebe-
tweenstorableandnon-storable(cryogenic)oxidizers.Whenlookingatthereactivity
ofhypergoliccombinations,itismoreoftentheoxidizerandnotthefuelthatdeter-
minesiftheresultingcombinationisself-ignitingoncontactornot.Hypergolicoxidiz-
erslikefluorineorchlorinetrifluoridewillbehypergolicwithmost,butnotallfuels.
Whenlistingcombinationsofrocketpropellants,wealwayslisttheoxidizerfirst.This
isbecausethepropertiesandtheactivityoftheoxidizerdeterminethenatureofthe
combinationmoresothanpropertiesofthefuelwould.Therearefeweroxidizersthan
fuelsinourinventory,soitiseasiertoorganizebookchaptersonrocketpropellant
combinationsfirstbyarrangingthembyoxidizersandlaterbyfuels.
Alessfrequentlyusedtermforpropellantispropellent.Whenconductinglitera-
turesearches,itmaybeadvisabletosearchforbothvariationsofthespelling.
AbouttheFormatoftheSeveralSetsintheEncyclopediaofRocketPropellants
ThemanuscriptfortheEncyclopediaofRocketPropellantshasevolvedthroughsev-
eraliterationsandmodifications,andtheterminologyindesignatingsets,volumes,
chapters,andsectionshaschangedduringthisperiod.AtonetimeEncyclopediaof
OxidizerswasreferredtoasVolume1andEncyclopediaofLiquidFuelswasreferredto
asVolume2,andsoon.ThemostrecentterminologyisnowreferringtoEncyclopedia
ofOxidizersasasetoffivevolumesandsimilarlyreferringtoEncyclopediaofLiquid
Fuelsasasetoffivevolumes.Thesequenceofvolumesinasetandthesequenceof
chaptersinavolumeisarrangedinalphabeticalorder,similartoadictionary.
Acriticalreviewermightdescribetheformatofthebooksasnotmuchmorethan
anannotatedbibliography.Theauthorisawareofthefactthatcollectingandrepro-
ducingreferencesfromtheliteratureisnotaverycreativejob(alibrariancoulddoit),
buttoarrangethesethousandsofreferencesinasystematicmannerrequiresagood
understandingofthesubjectmatter.
EncyclopediaofLiquidFuels IX
Fiftyyearsagoitusedtobecommonpracticetociteliteraturereferencesfollowed
bytheirChemicalAbstractcitation.ProvidingtheChemicalAbstractscitationoften
allowedthereadertoreadamoredetailedabstractandtodecideifitisworthwhile
to obtain a complete copy of the original publication. Nowadays that function has
beentakenoverbyDigitalObjectIndentifiers(DOI)intheInternet.Nevertheless,we
havecontinuedtocarryalongafewChemicalAbstractcitationsinadditiontotheDOI.
SomeofthosecitationsareusefulbecausetheydirectuserstotheChemicalAbstracts
RegistryNumberwhichcanthenbeusedforsubsequent,morespecificsearchesin
computerizeddatabases.Someofthebooksonenergeticmaterialsevencontainan
indexofChemicalAbstractRegistryNumbers.Atthebeginningofsomesections,at
theintroductionofanewchemicalname,usuallyseveralalternatenamesarelisted.
Inthoselists,thenamesbracketedbysemicolons;;arethenamesusedbyChemical
Abstracts.ThatinformationisusefulforliteraturesearchesinChemicalAbstracts.
SelectionofLiquidFuels
Whenselectingcombinationsofbipropellants,hypergolicornonhypergolic,itisusu-
allytheoxidizerthatdeterminesthereactivityofthecombinationonceoxidizerand
fuelmeetintherocketenginecombustionchamber.Thechoiceofoxidizershasless
ofanimpactonthespecificimpulsethanthechoiceoffuelswiththeirwidelyvarying
hydrogencontent.Theselectionoffuels,similartothecriteriaforselectionofoxidiz-
ers,isgovernedbyanumberofconsiderations:
– Specificimpulse
– Reactivitywiththeintendedoxidizerpartner(hypergolicornonhypergolic?)
– Boiling point/critical point temperature (storable at room temperature or cryo-
genic?)
– Storagestability
– Density(importantforcompact,pressure-fedsystems)
– Corrosivity(corrosiveoxidizersrequireexoticmetalsfortankageandtubing)
– Toxicity
– Availability
– Cost
UntilthebeginningoftheSpaceAge,ethanol,gasoline,andkerosenehadbeenused
most extensively as rocket fuels, primarily because of low cost, room temperature
storability,andrelativelyeasyhandlingcharacteristics.
Theworldofliquidrocketfuelschangeddramaticallywiththefirstuseofliquid
hydrogen,whichperformance-wiseisthebestandirreplaceablefuel.Liquidhydro-
gen was first used as the fuel in the second stage CENTAUR, but eventually its use
expandedtofirststages(boosters)aswell,suchasENERGIYA,SPACESHUTTLE,H-II,