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Materials Science & Engineering A 577 (2013) 197–201
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Materials Science & Engineering A
0921-50http://d
n CorrE-m
T. Bentr1 Te2 Te
journal homepage: www.elsevier.com/locate/msea
The effect of vanadium impurity on Nickel Σ5(012) grain boundary
EL Tayeb Bentria n, Ibn Khaldoun Lefkaier 1, Bachir Bentria 2
Laboratoire de Sciences Fondamentales, Université Amar Telidji de Laghouat, BP 37G, Laghouat 03000, Algeria
a r t i c l e i n f o
Article history:Received 18 February 2013Received in revised form12 April 2013Accepted 13 April 2013Available online 21 April 2013
Keywords:Grain boundaryDFTNickelTensile strengthSegregation energy
93/$ - see front matter & 2013 Elsevier B.V. Ax.doi.org/10.1016/j.msea.2013.04.047
esponding author. Tel.: +213 792 33 68 39; faxail addresses: [email protected], t.bentia)[email protected].(I.K. Lefkaier)bentria_bl./fax: +213 29 92 00 66.l.: +213 553 35 47 05.
a b s t r a c t
We report first-principle density functional theory investigation on the effect of vanadium impurity inthe nickel Σ5(012) symmetrical tilt grain boundary (GB) using Norm-conserving pseudopotentials. Wefirst calculate segregation energies for interstitial and different substitutional sites in order to determinesite preference and the segregation properties of V in the Ni GB. It is found that vanadium atoms prefer tosegregate in the substantial sites of the GB. Furthermore, the calculations of tensile strength for differentV positions in Ni Σ5(012) GB show an enhancement of the maximum tensile strength sMax up to 17%,indicating that vanadium acts as a strengthening element in Ni GB, which is in agreement withexperimental observations.
& 2013 Elsevier B.V. All rights reserved.
1. Introduction
Nickel-Based superalloys are an important class of metallicmaterials, they present exceptional properties of toughness, hightemperature strength and resistance to degradation in corrosive oroxidizing environments. These materials are widely used inpower-generation turbines, aircraft, rocket engines, and otherchallenging environments, including nuclear power and chemicalprocessing plants [1]. In fact, during the past few decades, turbineairfoil temperature capability has increased on average by about4 K/year [2]. Two major factors have made this increase possible:advanced processing techniques which improved alloy cleanlinessand crystallization and superalloys development by strengtheningthrough solid-solution and precipitation. The precipitation-strengthened alloys of our interest are used in applicationsrequiring high-temperature strength, good corrosion and creepresistance. For example, the enhancement of turbine blades andvanes in gas turbines, is made possible through the additions ofrefractory elements. It was found that impurities such as B, S, P, V,Nb added in ppm concentrations can drastically change materialproperties [3,4].
Among refractory elements, vanadium is one of the key alloyingelements contributing to the strengthening of superalloys, espe-cially as precipitation-hardening agent [3–6]. In Ni-based super-alloys, precipitations are formed at the grain boundaries after heat
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: +213 29 93 21 [email protected].([email protected].(B. Bentria)
treatment or an aging process usually as carbide precipitations. Thisprecipitation prevents grain boundary sliding and therefore thecreep rupture life is improved [6–8]. To the best of our knowledgeno quantitative work has been presented so far to determine thestrengthening effect of vanadium precipitations on nickel grainboundaries. Therefore, the study of vanadium segregation and itsenhancing effect on tensile strength in nickel matrix seems to be arequirement in order to further widen basic understanding of thestrengthening mechanisms of nickel based superalloys.
In order to carry out a theoretical investigation on the role ofimpurities in nickel GB, it is first necessary to identify which GBconfigurations are most stable. The coincidence site lattice (CSL)concept can be used to create GB models. Using the CSL method,computer simulated samples can be generated to study GBs at anatomistic level by means of ab initio investigations. These methodsare a promising and cost-effective research strategy widely used inrecent years to study the role of impurities segregated atoms.Among the different possible GB configurations in BCC nickel, theΣ5(012) GB is wildly studied because of its simplicity and stability.Yamaguchi et al. and Kart et al. independently conducted the first-principles density functional theory (DFT) calculations to under-stand why and how Sulfur impurity atoms weaken Ni GB [9,11]and how the increasing concentration of boron impurities in Ni GBleads to its mechanical enhancement [10]. Other works wereconducted in order to study the segregation of niobium in nickelΣ5(012) GB [13] and many sp-impurities from the 3rd, 4th and 5thperiod and the 13–16th groups of the Periodic Table [14].
The aim of this paper is to study the segregation effects ofvanadium on nickel Σ5(012) GB by means of DFT by calculating thetensile strength and segregation energies. Different segregationpreferential sites and cut planes will be considered. This paper is
a=<110>b=<121>c=<012>
c
a
b
E.T. Bentria et al. / Materials Science & Engineering A 577 (2013) 197–201198
organized as follow. After this introduction, Section 2 brieflydescribes the structural models as well as method and parametersused in our theoretical calculations. Section 3 presents the resultsof our calculations and a thorough discussions on V segregationand tensile strength. Conclusions are drawn in Section 4.
Vacuum GB Bulk FS
Fig. 1. Unit cell model of Ni Σ5(012) ⟨001⟩ symmetrical tilt grain boundary, modelused in segregation study. Unit cell shapes are shown by solid lines. Axes directionsand orientations are also presented. Atomic sites used in segregation are indicatedby numbers (0–11).
2. Model and computational details
2.1. Electronic structure calculation
Total energy calculations and geometry optimizations have beencarried out using DFT pseudopotential plane wave method asimplemented in Cambridge serial total energy package (CASTEP)[15]. Local density approximation LDA CA-PZ is used for theexchange-correlation potentials (CA-PZ: Ceperley–Alder [16], dataas parameterized by Pedrew–Zunger [17]). Norm-conserving pseu-dopotentials (NCP) [18] with the following valence electronicconfigurations Ni:3d84S2 and V:3d34S2 were used with a planewave cutoff energy of 720 eV. The k points sampling of Ni unit cellwas carried out using 8�8�8 Monkhorst Pack mesh grid whichcorresponds to 3�5�1 k-points sampling of our grain boundarymodel. Based on conclusions of Tian et al., the spin effect is takeninto consideration in all our calculations due to its effect in reducingthe GB cohesive energy which has important influence on tensilestrength [19]. The calculations assure a high level convergence ofthe total-energy difference with respect to the number of atomswithin 10−6 eV and maximum Hellmann–Feynman force within0.1 meV/Å for pure Ni Σ5(012) GB and energy difference of2.10−5 eV for segregation and tensile test calculations. For reason-able and fast convergence of the total energy, electronic occupan-cies were determined according to the Gaussian scheme [20] withan energy smearing of 0.2 eV. The Pulay scheme of density mixingwas used for self-consistent field (SCF) calculations [21].
2.2. Grain boundary modeling
The FCC Σ5(012) ⟨001⟩ symmetrical tilt boundary is formed byrotating one grain 53.11 with respect to the other about a common⟨001⟩ tilt axis with the boundary plane parallel to (012) [12]. Thisprocedure produces an ideal structure. Since we study the effect ofonly one atom of vanadium and its concentration in GB is out ofour scoop, 44-atoms supercell is used as a model of the GB,distributed on 11 layers. The influence of the surface on our GBmodel is expected to be sufficiently reduced so as to be negligiblebecause it is well known that the disordering of atomic positionsat the GB almost disappears over 2 or 3 atomic layers. For thisreason, the unit cell used in tensile strength calculations hassufficient length (2.5 nm) in the c-axis direction with a grain sizeof 0.55 nm. Due to the symmetry of the grain boundary sites [12],the study of segregation effects in one grain is sufficient, so weprefer to build one side of GB with more layers than the other inorder to investigate a large number of segregation possibilities.Fig. 1 shows our GB model used to study the segregation processwhere the atomic sites are labeled by numbers. Site 0 indicatesgrain boundary vacancy site used for V insertion while the other Nisites (1–11) are impurity substitution sites.
In order to obtain the equilibrium lattice parameters of pureferromagnetic nickel, we performed a volume relaxation. Thelattice constant is found to be equal to 3.506 Å (the experimentalvalue is 3.524 Å). The dimensions of the unit cell of GB model arethen 3.5�4.3�24.5 Å3. To avoid the effect of V–V interaction dueto lattice periodicity, we double the lowest model parameter(Fig. 1), so we get a 7.0�4.3�24.5 Å3 cell. This unit cell has avacuum region. In order to guarantee negligible interactionbetween the two surfaces that sandwich the vacuum region, the
width of this region was set to 1 nm for segregation calculationsand 1.5 nm for tensile strength calculations. This vacuum region isintroduced also to allow GB sliding (Fig. 1). Furthermore and orderto get relevant and comparable total energies, all calculations werecarried out with P1 symmetry by forcing symmetry breaking.
We introduce the GB energy (γGB) and free surface (FS) energy(γFS) to characterize GB cohesive properties which are defined asthe energies needed to create a GB and FS in the bulk. They aregiven by the following relations:
γGB ¼ EGBtot−EBulktot
2SGBand γFS ¼ EFStot−E
Bulktot
2SFSð1Þ
where EGBtot, EFStot and EBulktot are total energies of the GB, FS and bulk
system respectively, and SGB and SFS refer to GB and FS areas in theGB model. In order to obtain all energies on equal footing and tomake suitable comparisons, the calculation of EBulktot and EFStot for theunperturbed FCC ferromagnetic nickel is carried out using a modelwith the same number of atoms and also with the same orienta-tion of our GB model.
2.3. Segregation energy and tensile test calculations
The segregation energy is defined as the difference between thetotal energy of a systemwith the impurity in the surface layer (or GB)and the energy with the impurity is in the bulk: (Eseg¼EFS/GB−EBulk).Hence, our sign convention is that the negative segregation energycorresponds to impurities that want to segregate [22].
Here, we recall how to calculate the cohesive energy 2γ and thetensile strength sMax (maximum tensile stress), as presented in[12,23]. We set a fracture plane that gives the minimum cohesiveenergy (Fig. 2), then the upper and lower half crystal blocks arerigidly separated by five equal increments (from 0 nm to 0.5 nm).It should be noted that the use of larger number of incrementsgave always identical results. Each time in the separation process,we perform structure relaxation of the GB region, while fixingatomic layers close to the free surface in order to mimic the bulkstructure. Then the cohesive energy (2γ) of the GB is the differencebetween the two total energies; one is the energy of the GBwithout separation (point 0), and the other is the total energy forwhich the separating distance is so large that it does not changeany more, typically after 0.5 nm separation.
The maximum tensile stress is calculated as follow. A simplefunction f ðxÞ is fitted to the calculated total energy versus separa-tion distance x.
f ðxÞ ¼ 2γ−2γ 1þ xλ
� �exp −
xλ
� �ð2Þ
here 2γ and λ are fitting parameters where λ is the Thomas–Fermiscreening length. This function is known as the universal bindingcurve proposed by Rose et al. [24]. It describes well the bondingnature between atoms and constitutes the best fit to metallicbinding energies versus atomic distances. The tensile stress is the
Fig. 2. Atomic configurations surrounding the fracture plane after structural relaxation. (a) For clean Ni Σ5(012) GB; (b) S1 case; (c) S2 case and (d) S3 case. The originalenvironment positions corresponding these sites are presented in Fig. 1. The atomic distances are in Å.
Table 1Calculated grain boundary (GB) energy and free surface (FS) energy of Ni Σ5(210)GB in J m−2.
J m−2 Our NCP PP-PAW US-GGA Exp. (POLYCRYST)
GB energy 1.23 1.23a, 1.43b, 1.33c 1.41e 0.93d, 1.24f
FS energy 2.53 2.34a, 2.65b, 2.29c 2.40e 2.59d, 2.02f
a Data taken from Ref. [14].b Data taken from Ref. [27].c Data taken from Ref. [12].d Data taken from Ref. [25].e Data taken from Ref. [28].f Data taken from Ref. [26].
Table 2Formation energies Ef and segregation energies Eseg for different V site occupanciesin Ni Σ5(2 1 0) GB in eV.
Site number Ef Eseg Site number Ef Eseg
0 −3.85 −0.02 6 −3.90 −0.051 −4.44 −0.60 7 −3.84 0.002 −3.96 −0.11 8 −4.01 −0.163 −4.18 −0.34 9 −3.96 −0.124 −3.88 −0.04 10 −4.72 −0.885 −3.90 −0.05 11 −5.20 −1.35
E.T. Bentria et al. / Materials Science & Engineering A 577 (2013) 197–201 199
derivative of f(x):
f ′ðxÞ ¼ 2γxλ2
e−x=λ ð3Þ
The maximum of f ′ðxÞ is at x¼λ and corresponds to the maximumtheoretical tensile stress or tensile strength sMax, therefore
sMax ¼ f ′ðλÞ ¼ e−12γλ
ð4Þ
3. Results and discussion
3.1. Grain boundary, free surface and segregation energies
To verify whether the present GGA norm-conserving Pseudo-potentials (NCP) basis sets are suitable to our Ni GB model, wecalculated surface and grain boundary energies of nickel GB andcompared them with known results of previous experimental andtheoretical works, Table 1. Indeed, our results agree well with bothexperimental results [25,26] and previous theoretical calculations[14,12,27,28]. Thus we have a strong confidence in the constructedGB configuration of this paper.
The segregation energy of vanadium impurities on the Ni Σ5(012)symmetrical tilt grain boundary is calculated for 12 different impur-ity positions in order to study the segregation processes (Fig. 1). S0 isthe GB vacancy insertion site and S1–S11 are substitution sites. In thisrespect, we get 4 impurity positions in the grain boundary region (S0,S1, S2 and S3), four in the bulk (S4–S8) and three sites in the surfaceregion (S9, S10 and S11). For each configuration we performstructural relaxations of V atom and 4–5 close neighboring Ni atomswhile fixing all other atoms. Table 2 shows the calculated segregationenergies of V at the 12 various sites. The surface segregation energy isnegative and at least lower by 0.76 eV/atom than any GB segregationenergies. This value is known as embrittling potency energy in theRice–Wang model [29]. Our calculated embrittling potency of V in NiΣ5(012) is smaller than that of sulfur in Ni Σ5(012) which is about
1.5 eV [12]. The negative values of S1, S2 and S3 V segregationenergies show that vanadium has a potential to segregate to Ni GBand confirms experimental observations [8]. Furthermore, V atomprefers substitutional sites rather than possible interstitial one (S0)which presents near zero segregation energy E¼−0.02 eV. This valueindicates a very low probability of occupation of S0 site by the Vatom according to McLean's curve [30]. With −0.60 eV, S1 is the mostfavorable site for V atom to segregate. This situation can be deducedalso from the formation energies, since the difference between theformation energy and the segregation energy is always constant andequal to −3.8 eV in our case. The later energy is the differencebetween bulk energies of Ni and V in the solid solution and in theirenergies in pure states. The values of the formation energies in thesites near the GB or the surface are affected by the displacement ofatomic positions in these regions due to relaxation. sites 6 and 7 canbe considered as the safe bulk sites (Fig. 1) since their formationenergies are equal to −3.8 eV which is the same as the formationenergy of V atom in pure bulk Ni.
3.2. Tensile strength
In order to fully investigate the effect of vanadium impuritysegregation on tensile strength, three typical V-segregated casesnamely S1, S2 and S3 as depicted in Fig. 1, were thoroughly studiedin this work. Furthermore, and for comparison purposes, thetensile strength of clean Ni GB and pure Ni single crystal werealso calculated. As a result, Fig. 2(a) shows pure grain boundaryregion with small change in the GB tilt angle by 21 induced bystructure relaxation. On the other hand, Fig. 2(b), (c) and (d) showsthe optimized atomic configuration surrounding the V atom in S1,S2 and S3 sites respectively. In all Five cases, (012) is the fractureplane used in tensile strength calculations. The interlayer separa-tion distance is parallel to the z direction of the GB model.
Fig. 3(a) shows the calculated results of the evolution of thecohesive energies as a function of the separation distance betweenthe two grains in the tensile process fitted to the Rose universalbinding curve. In accordance with the finding of Yamaguchi [12]for Ni Σ5(012) GB, we found that total energies and forces do not
0.0 0.1 0.2 0.3 0.4 0.5
0
1
2
3
4
5
6
Coh
esiv
e en
ergy
γ /J
m-2
Separation distance in nm
Single crystalClean GBS1S2S3
0.0 0.1 0.2 0.3 0.4 0.5
0
10
20
30
40
Theo
retic
al te
nsile
str
engt
h in
GPa
Separation distance in nm
Single crystalClean GBS1S2S3
Fig. 3. (a) Cohesive energy in J m−2 and (b) tensile stress in GPa of the Ni Σ5(012) ⟨001⟩ GB as a function of the separation distance. The interlayer distances of a perfect bulkin the ⟨c⟩ direction is taken as a reference for separations in all configurations.
Table 3Cohesive energy (in J m−2), tensile strength (GPa) and separation distance (nm) ofNi single crystal, Ni Σ5(210) grain boundary and for V site occupancies insubstitutional sites (S1, S2, S3) in the Ni Σ5 GB.
Single crystal Clean GB S1 S2 S3
Cohesive energy γ Our 5.42 3.65 4.08 3.81 4.36Exp 4.44a
LDA 5.98b
PAW 4.52b
Tensile strength Our 37 Our 27.25 30.25 28.43 31.88Exp 40c LMTO 28.9e
PAW 30c PAW 26d
Separation distance 0.6 0.7 0.6 0.6 0.6
a Data taken from Ref.[31].b Data taken from Ref.[32].c Data taken from Ref. [11].d Data taken from Ref. [12].e Data taken from Ref. [33].
E.T. Bentria et al. / Materials Science & Engineering A 577 (2013) 197–201200
converge to the required criteria for some fracture cases where theseparation distance is small corresponding to 0.1 nm separation inFig. 2. We mention here the same explanation that the total energydepends on the lateral lattice parameters (a, b) due to Poisson'sratio, and on the number of atomic layers being relaxed near thefracture plane. In addition, it is difficult to converge because strainenergy is stored. For these difficulties, we do not use the obtainedenergy value of point 0.1 nm but we take instead the mean valueof the cohesive energies between 0 and 0.2 nm of separation. Forlarge separation region (0.2–0.5 nm), it is considered that Poisson'sratio does not affect significantly lattice parameters.
For the clean GB, the cohesive energy increases rapidly with theincreasing separation distances up to 0.3 nm, and then convergesto 3.65 J m−2, Table 3. As shown in Fig. 3(a) the GB systems withvanadium impurity exhibit similar trends as the clean GB, butthey converge to higher cohesive energies, which are 4.08 J. m−2,3.81 J. m−2, 4.36 J. m−2 for S1, S2 and S3 sites respectively. For Nisingle crystal case, the calculated cohesive energy γ¼5.42 J m−2
agrees well with other experimental and theoretical findings[31,32].
Fig. 3(b) shows the tensile strength as a function of the separationdistance, calculated according to Eqs. (2) and (3). As expected, for allfive systems, the stress increases with increasing separation distanceto reach the maximum tensile stress sMax and then decreases tofinally reaches 0. For the clean GB, the calculated sMax¼27.3 GPa is ingood agreement with previous theoretical calculation [12,33] seeTable 3. Furthermore, the calculated tensile strength of Ni singlecrystal is 40 GPa, which is very close to ideal tensile strength in the⟨100⟩ direction (37 GPa) estimated from experiment data [11] [34]. Inthe GB model with vanadium impurity, we can see from Fig. 3(b) thatvanadium segregation induces an increase of the maximal tensilestress in all three sites and reaches 31.9 GPa as major value for S3case, Table 3. Thus we can say that vanadium act as enhancingimpurity in the Ni Σ5(012) tilt grain boundary.
4. Conclusions
In summary, we have calculated segregation, formation andcohesive energies together with tensile strength of vanadium impur-ity in the nickel Σ5(012) GB system using the Norm-conservingpseudopotentials as implemented in CASTEP code. The results ofour calculations for sMax of pure GBs and single crystal cases are ingood agreement with experimental data and previous theoreticalcalculations. Furthermore, the calculated GB and free surface energiesagree well with experimental observations and other result based onPAW and Ultra-soft pseudopotentials.
We found that vanadium atoms are more likely located nearthe grain boundary in an interstitial sites rather than inner bulk orin GB substantial site which shows a near zero segregation energy.The interstitial segregation energies of vanadium are negative andlarge, which means that segregation to the GB is favorable,confirming the experimental observations. Tensile theoreticalcalculations on different segregation positions show that vana-dium acts as an enhancer to the nickel Σ5(012) GB tensile strengthfrom 4% to 17% with respect to clean GB.
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