Tungsten Carbides: Structure, Properties and Application in Hardmetals

253 Pages·2013·7.574 MB·English

by  Alexey S. Kurlov, Aleksandr I. Gusev (auth.)

Springer Series in Materials Science 184
Alexey S. Kurlov
Aleksandr I. Gusev
Tungsten Carbides
Structure, Properties and Application
in Hardmetals
Springer Series in Materials Science
Volume 184
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Alexey S. Kurlov Aleksandr I. Gusev
•
Tungsten Carbides
Structure, Properties and Application
in Hardmetals
123
Alexey S.Kurlov
AleksandrI.Gusev
Instituteof SolidStateChemistry
UralDivision of theRussianAcademy ofSciences
Ekaterinburg
Russia
ISSN 0933-033X ISSN 2196-2812 (electronic)
ISBN 978-3-319-00523-2 ISBN 978-3-319-00524-9 (eBook)
DOI 10.1007/978-3-319-00524-9
SpringerChamHeidelbergNewYorkDordrechtLondon
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Foreword
Thismonographisentirelydevotedonlytotungstencarbides.Atthesametimeit
provides not only a deep theoretical insight into tungsten carbides and considers
the physical essence of phenomena taking place in them, but also covers very
important issues of tungsten carbide application for producing hardmetals.
The interest in this book is due in the first place to systematic description and
critical analysis of the results of experimental and theoretical studies performed
over the last 10–20 years reflecting the relationship between the structure, phase
equilibria, and physicochemical properties of tungsten carbides.
Most of the original results for tungsten carbide described in the monograph
were obtained after 1992 in the Laboratory of Refractory Compounds at the
Institute of Solid State Chemistry of the Ural Division of the RAS (ISSC UD
RAS), which in 2008 was renamed to the Laboratory of Nonstoichiometric
Compounds. This is how the investigations into tungsten carbide began.
In1993, theauthorofthis foreword took partinthe 13th International Plansee
Seminar for the first time. Plansee Seminars deal with refractory compounds and
theirapplicationindifferentindustries.Theyaretraditionallyheldeachfouryearsin
asmallAustriantownReutte.Austriaistheseminarsitesinceitisinthiscountrythat
thescienceofcarbidesandotherrefractorycompoundsemergedandfirmedup.
In 1970–1980s, the research team of the Laboratory of Refractory Compounds
at the ISSC UD was concerned with tungsten-free hardmetals based on titanium
carbonitride.Theiraveragegrainsizewasseveralmicrometers.Mycoauthorsand
I proposed nonstoichiometric carbides as an alternative to these and other tradi-
tional hardmetals. My report [1] at the Seminar on behalf of a group of scientists
from Russia and Germany became later the basis of a large international project
[2]resultinginapatent[3]forproducingnonstoichiometriccarbideswithdesired
composition.
Among hundreds of reports presented at the Seminar, attention was drawn to
the works of B. H. Kear, L. E. McCandlish, and etc. considering the methods for
producing nanocrystalline powder compositions of tungsten carbide and cobalt,
whichareintendedforthemanufactureofnanostructuredhardmetals.Theseworks
gave impetus to the beginning of examination of atomic defects in tungsten car-
bide [4] and to the production, by different methods, of nanocrystalline tungsten
carbide powders and nanostructured hardmetals [5–8]. Earlier, these objects have
not been studied at the Institute of Solid State Chemistry UD RAS.
v
vi Foreword
In the present book, the authors involved in these studies have classified and
generalizedfromaunifiedpositiontheavailableexperimentalandtheoreticaldata
on the structure,physicaland chemical properties oftungsten carbides,aswell as
on the application of nanocrystalline tungsten carbide for producing nanostruc-
tured hardmetals. Each chapter is concluded with a large list of references.
The book is meant first of all for researchers dealing with materials science,
although for specialists in solid state physics, on the one hand, and for engineers
engaged in the production of hardmetals, on the other hand, it will be of consid-
erable interest. The book can be used as a teaching guide for students in higher
training and for post-graduates specialized in chemistry, physics, and materials
science.
A. A. Rempel
Corresponding Member of the RAS
References
1. Rempel AA, Gusev AI, Berger L-M. Nonstoichiometric transition metal carbides as
alternative hard materials. In: Bildstein H, Eck R, editors. Proceedings of the 13th
InternationalPlanseeSeminar.Reutte:MetallwerkPlansee;1993.V.2,p.671–684.
2. Berger L-M, Gusev AI, Rempel AA. Die Anwendung nichtstöchiometrischer Karbide des
Titans, Niobiums und Tantals für die Herstellung von Hartmetallen mit verbesserten
Eigenschaften.Projekt-Nr:03M2103(ProgrammMaterialforschungdesBundesministeriums
fürForschungundTechnologie,Deutschland);1993–1994.
3. Berger L-M, Hermann M, Gusev AI, Rempel AA. Verfahren zur Herstellung nichtstöchio-
metrischerCarbidedefinierterZusammensetzung.OffenlegungsshriftDE19807589A1.Int.
Cl.6: C 01 B 31/30 (C 04 B 35/36). Bundesrepublik Deutschland: Deutsches Patentamt:
Anmeldetag23.02.1998,Offenlegungstag10.09.1998;p.1–3.
4. Rempel AA, Würschum R, Schaefer H-E. Atomic defects in hexagonal tungsten carbide
studiedbypositronannihilation.PhysRevB.2000;961:5945–5948.
5. Kurlov AS, Borisenko NI, Moldaver VA, Valeeva AA, Rempel AA. Certification of hard
alloys produced from nanocrystalline tungsten carbide powder. Proceedings of the XVII
mendeleev congress on general and applied chemistry (September 21–26, 2003, Kazan).
Kazan:RussianAcademyofSciences;2003.V.3,p.358.
6. Kurlov AS, Leenaers A, Van den Berghe S, Van Houdt L, Scibetta M, Schröttner H, et al.
MicrostructureandstrengthoftungstencarbideWC-Cohardalloyssinteredfromnanopow-
ders. Proceedings of the international conference on dislocation structure and mechanical
propertiesofmetalsandalloys(April10–14,2008,Ekaterinburg).Ekaterinburg:UralDivision
oftheRAS;2008.p.137–138.
7. KurlovAS,RempelAA.EffectofWCnanoparticlesizeonthesinteringtemperature,density,
andmicrohardnessofWC-8wt.%Coalloys.InorgMater.2009;445:380–385.
8. Kurlov AS, Leenaers A, van den Berghe S, Scibetta M, Schröttner H, Rempel AA.
MicrostructureofnanocrystallineWCpowdersandWC-Cohardalloys.RevAdvMaterSci.
2011;227:165–172.
Preface
Since the discovery of tungsten carbide in 1893 by Henri Moissan and the first
usingofWCforindustrialproductionofhardmetalsatthebeginningoftwentieth
century, basic research on the chemistry and physics of high-melting tungsten
carbides and wear-resistant hardmetals has been carried out for three decades
mainly in Austria, Germany, USA and USSR. In the 1950s, 1960s the interest in
research of WC-based hardmetals, however, relaxed somewhat. Scientific and
technological results offirst stage of research and production of tungsten carbide
and WC-based hardmetals were generalized in two monographs: Kieffer and
Benesovsky [1] and Samsonov et al. [2]. Also, the structure and properties of
tungsten carbides were partially and very small discussed in the following books
on transition metal carbides: Goldschmidt [3]; Storms [4]; Toth [5]; Upadhyaya
[6]. Noted that these books contain the limited data on tungsten carbides, and the
part of these data is specified repeatedly.
Butthissituationabruptlychangedatthebeginningofthe1980swhenthefirst
indication for possible creation of fine-grained and nanocrystalline hardmetals
have appeared. This aspect immensely stimulated research of phase equilibria in
the ‘‘tungsten-carbon’’ system and of new methods for producing fine tungsten
carbide powders and fine-grained hardmetals. Thousands original studies and
articlesappearedintheliteraturedealingwithphaseequilibriaandphasediagrams
of the tungsten-carbide system, with the crystal and electronic structure and
propertiesoftungstencarbidesindifferentstructuralstates.Inthelast30years,the
most active efforts were made in synthesis and application of the nanocrystalline
WC powders for the production of nanostructured hardmetals.
This prompted to publish a volume devoted to tungsten carbides in the series
‘‘MaterialsScience’’.Accordingtothepurposeofthisseries,thisvolumemustfill
the gap between the scarce information about tungsten carbides in physicochem-
ical textbooks and in monographs devoted to transition metal carbides and
numerous review and original articles written for specialists. This monograph is
the first work generalizing all up-to-date information about tungsten carbides.
Themainsubjectofthemonographiscomprehensive analysisofstructureand
properties ofall stoichiometric andnonstoichiometrictungsten carbidesincluding
disordered and ordered phases. With this in mind, in Chap. 2 we considered in
detail the phase equilibria and crystal structure of phases of the binary W–C and
ternary W–Co–C systems, as well as the electronic structure of these phases.
vii
viii Preface
Chapter 3 is devoted to discussing the phenomenon of ordering of tungsten
carbides. Until now the literature data on the crystal structure of disordered and
differentorderedphasesofW C carbidearelimitedandcontradictory.InChap. 3
2 y
the symmetry analysis of all possible superstructures of lower tungsten carbide
W C isperformedandthephysicallypossiblesequenceofphasetransformations
2 y
in this carbide is established. The obtained theoretical results are compared with
the experimental data on the crystal structure and temperature-concentration
regionsofexistenceoforderedanddisorderedphasesoftungstencarbides.Onthe
basis of this comparison, the phase boundaries are determined and phase diagram
of the W-C system is refined.
According to the modern concepts, tungsten carbides in the nanocrystalline
state,i.e.carbides,whosegrainsorparticlesarelessthan80or100 nm,showthe
most promise. Therefore in Chap. 4 we described in detail the plasma-chemical
and high-energy ball-milling methods for production of nanocrystalline tungsten
carbideandconsidertheX-rayandelectronmicroscopicmethodsforestimationof
theaverageparticle(grain)size.Themodelofmechanicalgrinding,whichallows
theoretical estimation of the ball-milling parameters necessary for production of
powderswithpre-assignedaverageparticlesize,isdescribedforthefirsttime.The
application of this model is illustrated by the example of grinding of coarse-
grained tungsten carbide powders.
Production offine-grained WC–Co hardmetals has been examined repeatedly,
but for a long time there were no available experimental data in the literature on
theeffectofparticlesizeoftungstencarbidepowdersonthephasetransformations
taking place in hardmetals from the WC–Co system at different sintering tem-
perature, on the peculiarities of interaction of nanocrystalline WC powders with
cobalt, on thermal stability of phase and chemical composition, as well as on the
particlesizeofnanocrystallineWCpowdersduringtheir heatingto1400–1600 K
in vacuum or in air. These problems as well as the peculiarities of sintering of
WC–Co hardmetals with different cobalt content from nanocrystalline powders
WC having different particle sizes, microstructure and mechanical properties of
the sintered hardmetals are discussed in Chap. 5.
Wehopethatthismonographwillbeusefultospecialistsinsolidstatephysics,
to materials science engineers, as well as to students of physical, chemical and
materials science faculties.
We wish to thank our nearest colleague Prof. A. A. Rempel for useful dis-
cussions, and the Executive Physics Editor of the publisher, Dr. Claus E. Asch-
eron, for an effective collaboration during the preparation of this monograph.
Ekaterinburg Alexey S. Kurlov
Aleksandr I. Gusev
Preface ix
References
1. KiefferR,BenesovskyFH.NewYork:Springer;1965.
2. Samsonov GV, Vitryanuk VK, Chaplygin FI. Tungsten carbides. Kiev: Naukova Dumka;
1974.
3. GoldschmidtHJ.Interstitialalloys.NewYork:PlenumPress;1967.
4. StormsEK.Therefractorycarbides.London:AcademicPress;1967.
5. TothLE.Transitionmetalcarbidesandnitrides.London:AcademicPress;1971.
6. Upadhyaya GS. Nature and properties of refractory carbides. New York: Nova Science
Publishers;1996.