Fluorine: A Paradoxical Element: Volume 5 (Progress in Fluorine Science)

264 Pages·2018·20.759 MB·English

by  Alain Tressaud

Genuinenewdirectionsinresearchareunanticipated.Itistheunanticipatedevent
whichissoimportantandhastobefollowedup;anewviewpointthendevelops.
NeilBartlett,
“TheOxidationofOxygenandRelatedChemistry”,WorldScientificEd.,2001
Fluorine
Progress in Fluorine Science Series
Volume 1– Photonic and Electronic Properties of Fluoride Materials
A. Tressaud, K.Poeppelmeir, Eds.
Volume2–NewFluorinatedCarbons:FundamentalsandApplications
O. Boltalina, T. Nakajima,Eds.
Volume 3– ModernSynthesis Processes and Reactivity ofFluorinated Compounds
H. Groult, F. Leroux,A. Tressaud, Eds.
Volume 4 – Fluorine in Life Sciences: Pharmaceuticals, Medicinal Diagnostics,
and Agrochemicals
G. Haufe, F. Leroux, Eds., ISBN: 9780128127339.
Progress in Fluorine Science Series - Volume 5
Fluorine
A Paradoxical Element
Alain Tressaud
ICMCB-CNRS, University Bordeaux,
Pessac, France
Elsevier
Radarweg29,POBox211,1000AEAmsterdam,Netherlands
TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom
50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates
©2019ElsevierInc.Allrightsreserved.
Coverimagecredit:FromF.J.Zu´n˜iga,A.Tressaud,J.Darriet,Thelow-temperatureformof
Rb KCrF andRbKGaF:thefirstexampleofanelpasolite-typestructurewithpentagonalbipyramid
2 6 2 6
intheB-sublattice,176,3607–3614,JournalofSolidStateChemistry,CopyrightElsevier(2006).
Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans,electronic
ormechanical,includingphotocopying,recording,oranyinformationstorageandretrievalsystem,
withoutpermissioninwritingfromthepublisher.Detailsonhowtoseekpermission,further
informationaboutthePublisher’spermissionspoliciesandourarrangementswithorganizations
suchastheCopyrightClearanceCenterandtheCopyrightLicensingAgency,canbefoundatour
website:www.elsevier.com/permissions.
Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythe
Publisher(otherthanasmaybenotedherein).
Notices
Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperience
broadenourunderstanding,changesinresearchmethods,professionalpractices,ormedicaltreatment
maybecomenecessary.
Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluating
andusinganyinformation,methods,compounds,orexperimentsdescribedherein.Inusingsuch
informationormethodstheyshouldbemindfuloftheirownsafetyandthesafetyofothers,including
partiesforwhomtheyhaveaprofessionalresponsibility.
Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assume
anyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproductsliability,
negligenceorotherwise,orfromanyuseoroperationofanymethods,products,instructions,orideas
containedinthematerialherein.
LibraryofCongressCataloging-in-PublicationData
AcatalogrecordforthisbookisavailablefromtheLibraryofCongress
BritishLibraryCataloguing-in-PublicationData
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
ISBN:978-0-12-812990-6
ForinformationonallElsevierpublicationsvisit
ourwebsiteathttps://www.elsevier.com/books-and-journals
Publisher:CandiceJanco
AcquisitionEditor:EmilyMcCloskey
EditorialProjectManager:KaterinaZaliva
ProductionProjectManager:OmerMukthar
CoverDesigner:KaterinaZaliva
TypesetbySPiGlobal,India
Foreword
ThehistoryoffluorinebecomeslivelywhenAlainTressaudreportsontheSection1
ofthebookwiththetitle, “Fluorine: AParadoxicalElement.”Indeedfluorinehas a
Janusheadwithtwofaces,andtheauthorelegantlyshowsitsprosandcons.Thisisa
realmasterpieceofabook.Sections2and3areentitled,“Fluorine:AKeyElementof
the 21st Century,” and “Fluorinated Compounds in Our Environment.” On the one
hand, both chapters demonstrate how important fluorine compounds contribute to
thetechnicaldevelopment ofourdailylife.Ontheotherhand,wefacetheproblem
ofcontaminationfromfluorine-containingcompounds.Inprinciple,thishasalready
been known since the Swiss medical doctor Paracelsus (1493–1541) wrote, “All
thingsarepoisonandnothingexistswithoutpoison,alonetheamountisresponsible
for being a poison.” Presently, everyone faces daily contamination of the air with
increasingamountsofexhaustgasesfromburningcoalandgasoline, orlearnsfrom
the newspaper about the contamination of water with nitrates and large amounts of
plasticintheoceans.Hugeconsumerdemandforproductscreatesanenormousprob-
lemtodayandforthefuture.AlainTressaudshowsthisconvincinglyinhisdiscussion
of the development of fluorine-containing products. Therefore, this book is a very
valuableandkeycontributionandaneye-openerfortheresearcher,producer,andcon-
sumer interested in sustainable development. I hope that this book will not only be
read by fluorine experts but also distributed to others who are involved in research
and environmental issues.
Herbert W. Roesky
G€ottingen,Germany
Introduction
Lastfewdecades,fluorineandfluorinatedproductshaveattractedsignificantattention,
becausetheyaregreatlyinvolvedinourdailylifeandenvironment.Althoughmanyben-
eficial breakthroughs have been brought to us thanks to fluorine and fluoride com-
pounds, they are decried today because of some environmental drawbacks. The goal
ofthisbookistoprovideabetterunderstandingofthemanyadvantages,butalsosome
disadvantages,oftheseproducts,focusingontherealplaceandimportanceoffluorine
andfluorinatedproductsinourcurrentenvironmentandeverydaylife.Ofcourse,every-
oneknowsthatthiselementispresentintoothpastesweuseregularly,butwhoisreally
awarethatitsurroundsusinmostinstancesofourlife?Fluorineisnotarareelement.In
fact,itisthe13thmostabundantelementconstitutingtheEarth’scrust,whereitispre-
sentatabout0.06%toadepthof16km.Itisthesecondanionafteroxygen.Itismost
foundinmineralssuchasfluorite,apatite,topaz,andtourmalines,butalsointheoceans,
groundwater,lakes,andrivers.Muchclosertous,itisalsoanessentialconstituentofour
teethandourskeleton,aswellasthoseofallmammals.Finally,fluorinatedmolecules
alsoexistinseveralplants.Unlikeoxygen(O ),whichistheessentialconstituentofour
2
atmosphere,fluorinegas(F )couldnotbefoundinnatureuntilveryrecently,duetoits
2
highchemicalreactivity.Indeed,duetoitselectronicstructure(1s22s22p5),oneelectron
is missing in the 2p electronic layer to complete the valence shell to eight electrons
(2s2,2p6),whichcorrespondstotheelectronconfigurationofthenearestnoblegas,neon
(octetrule).Thus,becauseofthereaction½F +e(cid:1)!F(cid:1),theelementoxidizesalmost
2
all other elements, leading to generally very stable compounds in which it is present
(cid:1)
undertheformofafluorideion,F .However,forsimplicity,thewordfluorineisoften
usedtoidentifythespeciespresentinaproduct,whateverthecharge.
Physicalchemicalproperties offluorinewill illustrate how it iscertainly themost
paradoxicaloftheelements,becausethemajorityofitspropertiesderivefromaduality:
soreactiveononehandthatitcouldnotbeisolatedforcenturies,andontheotherhand,
givingmoststablebondswithalmostallotherelements(particularlywithcarbon),so
stablethat theformedproductsoften stayunmodifiedinthestratosphere.Obviously,
wewilldiscussthecontributionoftherefrigerantgasescontainingfluorine,CFCand
HCFC, to the depletion of the ozone layer, and perfluorocarbons and other per-
fluorinated molecules’ contributionto thegreenhouse effect.
Discoveriesandanecdotesabouttherealhistoryoffluorinatedmaterialsthroughout
centuries will be illustrated using some major examples in the first section. We will
present some decisive discoveries and stages of development in fluorinated products
that took place during the 20th century following the isolation of fluorine by
H.Moissanin1886,withparticularemphasisonthetechnologicaladvancesthathave
followed.Thecontributionsoffluorinatedproductstheselast50yearswillbedescribed
xii Introduction
in the second section. Issues relative to these products are of primary concern for
humansinimportantareassuchasmoderntechnology,medicine,pharmacy,andbio-
technology. Examples will be given in various fields: photonics, energy production,
newdrugs,surfactants,fireemulsions,TVcomponents,fluorinatedpolymers,alterna-
tive materials in cardiovascular surgery, anti-decay products, and medical imaging
applications. A third section will deal with the presence of fluorine and fluorinated
productsaroundusandtheireffectonourenvironment(atmosphere,lithosphere,water,
gaseous emissions), focusing on efforts to limit harmful consequences. We will con-
clude this section on fluorine’simpact on man by giving examples of different types
of fluoride contaminations (water, food, industrial environmental), together with the
physiological effects of fluorides on living organisms; the solutions that have been
proposed tosolve these problems will bealso considered.
Because of the importance of this element, international meetings are regularly
devotedtoallfieldsinvolvingFluorine.ThelastInternationalSymposiumonFluorine
ChemistrywasheldinOxford,UKonJuly2018andthenextEuropeanonewilltake
place in Warsaw on August 2019. It can be added that several “Fluorine Networks”
havebeencreatedinvariouscountries,includingFrance,USA,UK,Germany,Russia
andJapan,topromoteactivitiesrelatedtofluorineinvarioussectorsofchemistry,new
technologies, life sciences, medicine and the environment. It should be noted that
several specialized books have appeared in recent years dealing with many fields of
fluorine chemistry and fluorinated materials: organic and inorganic compounds,
fluoropolymers, pharmaceutical molecules, industrial and biomedical applications,
etc. These volumes, which propose highly specialized information, are collected in
a table at the end of this book. But so far, no attempt had been made to produce an
English-language work with a comprehensive and global approach to this element’s
impact on humanity, that is, advanced technologies we use every day, the air we
breathe,thewaterwedrink,thelandweliveon,etc.Ratherthanlistingtediousdoc-
umentsonthevariousclassesoffluorinatedproducts(thefeaturesandapplicationsof
whichcanbebetterfoundinmorespecializedbooks),itwasdecidedthatthefollowing
pagesshouldproposeanoriginalglobalapproachtothetopic,illustrating(Ihope)the
importance of this element on our environment and life. The varied fields involving
fluorine, such as history, cosmochemistry, global warming, radiative forcing, natural
and anthropogenic emissions, the water cycle, etc., will be thus evoked, but without
ignoringsomenegativeaspectsoftheseproducts.Theplaceoffluorineandfluorinated
productsinkeyareasforourfuturewillbealsoevoked,dealingwithwastereduction,
global warming,energyindependence, microelectronics, nanotechnologies, etc.
Inthisbook,theauthorwantedtoshowapersonalversionoftheimageoffluorine
andfluorinatedproducts,oftheirimportanceinourdailylives,aswellasalltheprom-
isingcontributionsinmanyfieldsofscienceandtechnology.However,thedisadvan-
tagescausedtoourhealthandenvironmentbysomeoftheseproductshavenotbeen
underestimated.Unfortunately,theauthorcouldnotconsiderallpropertiesandappli-
cations of these materials, and begs concerned colleagues to excuse him in case of
important omissions.
Note:Inthisbook,theword“fluorine”maybetakeneitherfortheelementorforthe
F gas (difluorine); on the other hand, the word “fluoride” may be taken either for a
2
(cid:1)
compound/material orthe anion F .
1
History and milestones of fluorine
and fluorinated products through
the centuries
Chapter Outline
1 Historyandusesoffluorinatedminerals 2
1.1 Fluoridecrystalsasgemstonessubstitutes 4
1.2 Fluorinatedpowdersas“therapeutics” 6
1.3 Usesoffluorsparmineralsaspigments 6
1.4 Usesoffluorsparasornamentsandindecorationitems 6
1.5 Middleagesforgeries:fossilizedmastodontuskssoldassynthetic“turquoise” 7
2 Fluorinedatinginarcheology 14
2.1 Relativedatingofbonesandskeletalremains 16
2.2 Datingarcheologicallithicartifactsbyfluorinediffusion 24
3 ThetruenatureoftheRomanmurrhinethroughacriticallecture
ofPlinytheElder’s“NaturalisHistoria” 31
4 GeorgiusAgricola,thefatherofmineralogyandcreatoroftheword“fluoride” 36
5 Insearchofthemissinghalogen,fromtheRenaissanceto1886 41
6 TheisolationoffluorineonJune1886byapharmacistandchemist:
HenriMoissan 45
7 Physicalchemicalcharacteristicsoffluorine 49
8 Somebreakthroughsinthedevelopmentoffluorineandfluorinatedproducts
throughoutthe20thcentury 52
8.1 Therapidgrowthofthealuminumindustry 53
8.2 TheriseandfallofCFC 58
8.3 ThestoryofTeflonandfluoropolymers 68
8.4 Fluorine,adecisiveelementinthenuclearcycle 72
Untilthedawnoftechnological(al)chemistry,thevalueofmanymineralswaswidely
recognizedandexploitedwithoutsuspectingthenatureoftheelementattheoriginof
theseproperties,forexample,aluminuminalumandfluorineinfluorite(fluorsparor
fluβspat). It can be noted that the name of these two elements finally resulted from
the properties of these minerals: i.e. the element that flows for F and the metal from
clay for Al. The word fluorine (fluores in Latin) appeared for the first time in 1530
in a book written by G. Agricola, but long before that, the melting properties (or
“flux”) of the fluorinated minerals had been identified, and the beauty and reputed
magical properties of these crystals had fascinated many ancient civilizations. Some
exampleswillhelpustofollowthehistoryoffluorineandfluorinatedmineralsthrough-
outthecenturies:fluoridecrystalsasgemstones,therealhistoryofthemurrhinevasesof
Fluorine.https://doi.org/10.1016/B978-0-12-812990-6.00001-5
©2019ElsevierInc.Allrightsreserved.
2 Fluorine
Imperial Rome, fossil fluorapatites used as synthetic turquoises by the monks of the
MiddleAges,descriptionoftheuseofcryoliteinsmeltingbyG.Agricoladuringthe
Renaissance period. An important place will be devoted to the fierce competition
between the greatest scientists of the 18th and 19th centuries to characterize fluo-
rocompounds and isolate the F element, a competition that allowed exceptional
2
discoveries,culminatingintheisolationoffluorinebyHenriMoissanin1886.
1 History and uses of fluorinated minerals
In very ancient times, beautiful Egyptian ladies were using fluoride crystals as
ornaments,especiallyfluorite.Carved figurines andbeetleshavebeen foundduring
archeologicalexcavations,hundredsoffluoritesealshavebeenfoundinAegeansites
of the Late Bronze Age,1 and a multitude of various objects were made over many
centuries in ancient China. At Moncy-St-Pierre (France), necklaces with fluorite
beadsaccompaniedwealthyMerovingiansintheirlastrestingplaces(6th–7thcentu-
ries). In Amerindian civilizations, fluorite crystals were likely cut for religious
reasons,asevidencedbythefigurineofasittingmandiscoveredintheAngelpitsite
inIndiana(UnitedStates),whichcouldhavebeenanidolforthemaintemple.2The
importanceofmurrhinevasesinImperialRomewillbelatermentioned.Assuch,itis
said that Hadrian would have launched the conquest of northern England mostly to
appropriate deposits of “Blue John” fluorspar (Fig. 1), a banded mineral with
Fig.1 BandedfluoritecrystalfromCastleton,UnitedKingdom.
PhotoMichaelVickers,UsedwithpermissionfromMichaelVickers.
1A.Dickers,Diesp€atmykenischenSiegelausweichemStein.VLMVerlagMarieLeidoerfGmbH,Rahden,
Germany(2001).
2C.R.Stafford,PrehistoricPeopleofIndiana,INARNGIntegratedCulturalResourcesManagementPlan
A187,IndianaStateUniversity(2001).