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Acla metal/. Vol. 34, No. 9, pp.

1847-1851, 1986 Printed in Great Britain

oooi-6160/86 $3.00 + 0.00 Pergamon Journals Ltd


Physics Department, Faculty of Education, Faculty of Science,

and S. A. KHAIRY
Physics Department,

Ain Shams University, Cairo and Cairo University. Cairo, Egypt 12 Mu! 1985)


Abstract-Thermoelectric power (TEP) measurements for Al4 wt% Cu alloy samples in the form of wires 0.5 mm diameter quenched then deformed torsionally to different degrees were carried out after isothermal annealing in the temperature range 383423 K. Precipitation of excess solute Cu atoms, as traced through TEP measurements was enhanced by predeformation and attained different stable sizes depending on the annealing temperatures as revealed by the observed final stable TEP values. The energy activating precipitation process (Q) was found to be deformation dependent. The time exponent 1.06 as calculated from the volume fraction of Cu atoms precipitated at a certain time t to form Guinier-Preston (GP) zones was found to be independent on predeformation over all the investigated temperature range and consisted with Hams theory for precipitation on dislocations. The results were interpreted on the basis of the dominating and predeformation and the different contributions of the solute atoms when dispersed in the matrix or included in the formed GP zones to the measured TEP. Rbum&Nous avons effectut des mesures du pouvoir thermo-klectrique (PTE) sur des &chantillons dun alliage Al_4%Cu (en poids) en forme de fils de 0,5 mm de diamttre trem@s puis d&form&s en torsion B diffirents degrks, apres un recuit isotherme entre 383 et 423 K. La prkcipitation datomes de cuivre en excts, suivie par des mesures de PTE, &tait favorisCe par la prCdCformation et atteignait diffirentes tailles stables selon les tempkratures de recuit, comme lont montre les valeurs finalis stables. Nous avons trouvC que ltnergie dactivation (Q) du phtnomtne de prCcipitation dCpendait de la diformation. Nous avons trouvt. que Iexposant du temps I,06 calcult g partir de la fraction volumique datomes de cuivre prtcipitks $ un temps t pour former des zones de Guinier et Preston (GP) &tait indtpendant de la pr&dtformation pour tout le domaine de tempkratures ttudik et quil Ctait compatible avec la thkorie de Hams de la prkcipitation sur les dislocations. Nous avons interpr&C ces rtsultats B partir des micanismes de diflusion dominants, du rBle des difauts rtticulaires induits par tempe et predeformation et des diff&rentes contributions des atomes de sol& au PTE measurk, quand ces atomes sont dispersCs dans la matrice ou contenus dans les zones GP. Zusammenfassung-An 0,5 mm Diinnen Drlhten der Legierung AI-4 Gew.-% Cu, die abgeschreckt und danach unterschiedlich stark in Torsion verformt worden waren, wurde die thermoelektrische Kraft nach isothermem Ausheilen im temperaturbereich zwischen 383 und 423 K gemessen. Die Ausscheidung der iiberschiissigen Cu-Atome, ermittelt mit der thermoelektrischen Messung, Wurde durch die Vorverformung verstlrkt; je nach Auscheiltemperature ergaben sich unterschiedlicht stabile GrGBen der Ausscheidungen, wie die beobachteten Endwerte der thermoelektrischen Kraft anzeigen. Die Aktivierungsenergie des Ausscheidungprozesses hing von der Verformung ab. Der Zeitexponent 1,06, berechnet aus dem Volumanteil der bei einer gewissen Zeit t in Guinier-Preston-Zonen ausgeschiedenen Cu-Atome, war im gesamten untersuchten Temperaturbereich unabhingig von der Vorverformung und entsprach der Theorie von ham Fiir die Ausscheidung an Versetzungen. Die Ergebnisse werden auf der Grundlage der dominierenden Streuprozesse, der Rolle der durch die Abschreckung und die Vorverformung eingefiihrten Defekte und der unterschiedlichen Beitrige der Fremdatome, ob verteilt in der Matrix oder enthalten in den Guinier-Preston-Zonen, gedeutet.


When a metal is isothermal at temperature T, electron collisions with phonons or with static defects in the lattice such as impurities or physical imperfections such as dislocations will tend to restore the electrons to overall thermodynamic equilibrium. But when a temperature gradient is present electron diffusion and phonon-drag effect take place. It was indicated [l] that, thermoelectric power (TEP) measurements were consistent with a phonon-drag component which is appreciable at room temperature and persists up to 700 K. Although the diffusion S, and

phonon-drag S, components of TEP were supposed to be linearly [2] dependent on temperature, yet it was found [3] that, the diffusion component of the TEP of Al cannot be represented completely by a term linear in temperature. Nielsen and Tylor [4] derived an expression for the diffusion TEP of dilute alloy which predicts effects that in the past have been ascribed solely to phonon-drag. Possibly the Nielsen-Taylor effect and phonon-drag are complementary in many alloys [5]. It was concluded [6] that, TEP is potentially a useful probe for the study of precipitation phenom-




THERMOPOWER OF AlCu temperatures. Also, it is aimed at studying the effect of predeformation on the aging process of this alloy.

Measurements on Al alloy systems [3] emphasized that the TEP is extremely sensitive to the presence of constituent elements in solid solution and the annealed state is considerably different from that in the cold-worked condition. On the basis of the simple model of dilute alloy TEP proposed by Gold et al. [7] which assumes different independent scattering mechanisms, the TEP is given by

s =1


C Pt

where S, and pi are the TEP and the resistivity of the ith scattering mechanism. The dependence of TEP on structural variations is therefore valid through the structure dependence of electrical resistivity. For Al4 wt% Cu alloy the change of electrical resistivity during isothermal aging may has the form [8] AP =P -((PT+~,&) (2)

where pT is the contribution from lattice vibrations, pi is the residual resistivity and m, is the alloy composition. The present work is an attempt to throw lights on the structural variations through the time dependence of the TEP for AlA wt% Cu alloy aged at different

The investigated Al4 wt% Cu alloy in the form of wires 0.5 mm diameter is composed from high purity (99.999) Al and Cu. The TEP was determined by the measurements of the temperature dependence of the Seebeck potential from a thermocouple composed from the alloy and Pt as a suitable reference element in the presence of temperature gradient. Measurements of temperature were carried out with Pt and Pt-10% Rh thermocouples. The emfs from all thermocouples were determined with a precision of 0.1 PV using a direct current PYE precision decade potentiometer. The samples were solution heat treated at 813 K for 1 h then quenched in water at room temperature. Immediately after quenched the specimens were torsionally deformed to different degrees determined by the dimensionless quantity ND/L with N the number of turns twist, D and L the diameter and length of the sample respectively. The deformed samples were aged at different temperatures and the TEP values corresponding to different annealing times were obtained.



.u . $

16.4 17.2F


q 423

Fig. 1. Time dependence of the TEP of Al4 wt% Cu alloy samples deformed to different ND/L values then aged at the indicated temperatures.




Fig. 2. TEP dependence of predeformed Al-4 wt% Cu alloy samples.


_.--- ND/L= E=0.35 0.0 ev

RESULTS Figure 1 shows the time dependence of the TEP S for Al4 wt% Cu alloy samples predeformed to different degrees after quenching then isothermally annealed in the temperature range 383-423 K. In general, TEP increased and reached stable values depending on both the annealing temperature and the degree of predeformation. The irregular contribution of predeformation to the TEP of quenched samples before aging is shown in Fig. 2. The predeformation dependence of the final TEP stable values is given in Fig. 3. Figure 4 shows the equivalent times and temperatures required to reach a certain value of the undeformed samples as deduced from Fig. 1, from which the activation energy was obtained, In a similar manner, the activation energies for the predeformed states were determined. Predeformation dependence of the energy activating the isothermal annealing process is shown in Fig. 5. The kinetics of the annealing process was analysed using the equation [9] 1 --w =exp(-pt)K (3)



Fig. 4. Equivalent times and temperatures for undeformed samples.

with siopes equal to the time exponent K. Figure 6(a) gives K values of samples deformed with different degrees then annealed at 383 K. Calculations showed that K values do not deviate significantly from their mean. For the other temperatures, curves like that of 383 K were found to have the same features of Fig. 6(a). For each degree of predeformation, the mean values of K for all temperatures are given in Fig. 6(b). It is clear that the mean values of K are independent on the degree of predeformation and amounted to the value 1.06.

where w is the fraction of the solute precipitated at time t, K is the time exponent constant and p is constant. Equation (3) when rearranged gives log In [l/( 1 - o)] = K log t + K log /I. (4)
0.1 I 0 I 0.06 I 012 ND/i I 0.16 I 0.24

Using Fig. 1 and plotting the relation between log ln[I/( 1 - u)] vs log t, straight lines were obtained

Fig. 5. Predcfo~ation

dependence of the activation energy


K 423 413 403 393 383

17 0

I 0.06

I 0.12 AWL

I 0.18

I 0.24

Fig. 3. Final stable values of TEP dependence of the degree of predeformation for Al-4 wt% Cu alloy samples aged at the indicated temperatures.

Fig. 6. (a) Time exponent K for alloy samples predeformed to different degrees then annealed at 110C. (b) Time exponent mean values K for samples aged at different ^ .^ oegrees 01 preoetormatton.






TEP as scattering dependent phenomenon could be related proportionally to electrical resistivity p through equation (1). Electrical resistivity is given by summing the values associated with scattering by phonons, single solute atoms and Guinier-Preston (GP) zones as [8]
P =PT+(~ -w)mp:+nG(D) (5) where m is the solute concentration in the matrix, n is the number of zones per unit volume, and G(D) is the contribution to the resistivity from one zone with an average diameter of D. Accordingly, the variations of TEP will behave like those of resistivity as was observed [lo] for lead. In supersaturated solid solution of Al-base alloys [1I] metastable, solute rich GP zones are formed in preference to a stable phase. It was found [S] that, GP zones formed during isothermal aging in Al4 wt% Cu alloy increased the resistivity of the alloy and that the contribution to resistivity from a solute atom in the zone is larger than one in the matrix. Accordingly, the TEP of the aged alloy is expected to be larger than that of the quenched state (solid solution) in which Cu atoms are homogeneously distributed in the matrix. This explains the increase in the measured values of TEP in Fig. 1 by isothermal aging of the quenched samples. According to HEW theory [12], the resistivity measured during GP zones formation is treated as a parallel circuit because the Fermi surface of pure Al and its dilute alloys has been recognized [8] to be an incomplete sphere divided into two parts-with and without Bragg scattering. In terms of conductivity two partial conductivities exist. As precipitation proceeds one partial conductivity increases because of decreasing solute concentration in the matrix. The other conductivity decreases because the Bragg scattering increases as the GP zones grow in size. The synthesis of both conductivities produces a minimum. Accordingly, the resistivity and in turn the TEP show maxima which is clear from the stable values given in Fig. 1, as obtained during the growth of GP zones, with levels described by the time evolution of the entire microstructure at the different investigated temperatures. It was found [13] that, predeformation activated the formation process of zones and precipitates and increased the rate of rise [ 141of resistivity in the early stages of aging and produced a more rapid fall-off. The defects created by predeformation increase the scattering centres leading to the overall observed increase in the TEP of the deformed samples before aging as shown in Fig. 2. The decrease in the number of scattering centres caused by partial annihilation of predeformation induced defects might explain the observed decrease in the TEP corresponding to higher degrees of predeformation as clear in Fig. 2. For longer annealing times corresponding to the maximum number of precipitated solute atoms in the

zones, the values of TEP in Fig. 3 seem to depend mainly on the interaction between the existing defects and solute Cu atoms. In Fig. 3, the expected temperature dependence of TEP took place but predeformation caused irregular behaviour for the final stable values of TEP. Small degrees of predeformation accelerated precipitation and increased the TEP to maximum value. Increasing predeformation probably increased the annihilation of vacancies which reduced the number of solute atoms migrating to the zones and consequently lowered the TEP to the observed minima for all aging temperatures. The anomally observed in Fig. 3 for TEP curve at 403 K might be due to the following. This temperature 403 K was found [15] to be more suitably for the formation of the first kind of GP zones in Al-Cu alloy. Before 403 K more solute Cu atoms exist in the matrix because the number of formed zones is less than that at 403 K. While after this temperature the formation of the second type of GP zones takes place on the expense of the first formed GP zones [16]. The dissolution of the first zones increases the concentration of the solute atoms in the matrix and lowers the corresponding TEP. The activation energies for the annealing process as given in Fig. 4 and its relation to the degree of predeformation in Fig. 5 can be explained as follows. Vacancies retained by quenching might form vacancy-copper pairs which migrate behind dislocations leading to the formation of copper rich zones. This view agrees with the calculated activation energy 0.35 eV for undeformed samples, which is effectively equivalent to the difference between the energy for vacancy migration [17] in Al (0.55 eV) minus the binding energy for a vacancy-copper pair reported [ 161 as 0.2 eV. Increasing predeformation accelerated the whole precipitation process [ 131 and lowered the activation energy to about 0.2 eV. This value suggests an increased probability of divacancy formation [18] by predeformation. The migration of these divacancies with 0.2eV, which is nearly the energy needed for divacancy [19] migration in Al, seems to play essential role in the formation of zones. Further increase in predeformation increased the dislocation density and lowered the density of mobile dislocations. The less mobile intities therefore, needed higher energies (Fig. 5) to complete the annealing process. The mean values of the time exponent given in Fig. 6(A) shows the independence of the annealing mechanism on deformation. The mean value 1.06 for the time exponent given in Fig. 6(B) for all the degrees of predeformation agrees well with the value of unity predicted by Ham [20] for precipitation on long thin cylinders, such as dislocations.

authors are indebted to Professor Dr R. Kamel, Faculty of Science, Cairo University, for his kind help and encouragement during this work.




10. M. Singh



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