Scripta

METALLURGICA

V o l . 14, pp. 4 3 1 - 4 3 5 , 1980 Printed in the U.S.A.

Pergamon Press Ltd. All rights reserved.

D I S L O C A T I O N R E S I S T I V I T Y IN IN SITU FORMED C u - N b M U L T I F I L A M E N T A R Y C O M P O S I T E S

K e i t h R. K a r a s e k and J. Bevk D i v i s i o n of A p p l i e d S c i e n c e s Harvard University, Cambridge, M A 02138

(Received February

14,

1980)

Introduction D i s l o c a t i o n r e s i s t i v i t y in fcc metals, p a r t i c u l a r l y copper, has b e e n studied in c o n s i d e r a b l e detail. The e x p e r i m e n t a l e v i d e n c e (I) suggests that e l e c t r o n s c a t t e r i n g from d i s l o c a t i o n s in copper is isotropic or n e a r l y isotropic and r a t h e r localized. Consequently, d i s l o c a t i o n scattering p o w e r at a g i v e n t e m p e r a t u r e can be c o n s i d e r e d a c o n s t a n t i n d e p e n d a n t of d i s l o c a t i o n d e n s i t y and, hence, the d i s l o c a t i o n contribution, PD, to the total r e s i s t i v i t y should be d i r e c t l y p r o p o r tional to the d i s l o c a t i o n density. The r e l a t i v e m a g n i t u d e of this c o n t r i b u t i o n at room t e m p e r a ture is not more than 2-3% even in h e a v i l y c o l d - w o r k e d copper, but can be d o m i n a n t at low temperatures in very pure metals. E l e c t r o n s c a t t e r i n g from d i s l o c a t i o n s should be of p a r t i c u l a r interest in C u - b a s e d c o m p o s i t e with in situ formed u l t r a f i n e filaments. D i s l o c a t i o n d e n s i t y in these m a t e r i a l s has been estim a t e d from t r a n s m i s s i o n e l e c t r o n m i c r o s c o p y to be one to two orders of m a g n i t u d e h i g h e r than in s i n g l e - p h a s e m a t e r i a l s r e d u c e d to the same size (2,3). M e a s u r e m e n t s of e l e c t r i c a l r e s i s t i v i t y in A g - C u in situ c o m p o s i t e s (4) indeed showed a p r o n o u n c e d increase with d e c r e a s i n g f i l a m e n t spacing but the r e l a t i v e c o n t r i b u t i o n to the total r e s i s t i v i t y from interface and d i s l o c a t i o n s c a t t e r i n g could not be determined. In this note we report on m e a s u r e m e n t s of e l e c t r i c a l r e s i s t i v i t y in Cu-Nb in situ c o m p o s i t e s as a f u n c t i o n of f i l a m e n t volume f r a c t i o n and c o m p o s i t e diameter. The C u - N b system is p a r t i c u l a r ly suitable for this i n v e s t i g a t i o n b e c a u s e of its e x c e l l e n t h i g h t e m p e r a t u r e stability; d i s l o c a tion c o n t r i b u t i o n to the total r e s i s t i v i t y can be t h e r e f o r e d e t e r m i n e d d i r e c t l y by m e a s u r i n g res i s t i v i t y of the a s - d r a w n and a n n e a l e d composites. We show that in C u - N b c o m p o s i t e s w i t h s u f f i c i e n t l y small and c l o s e l y spaced filaments the m a g n i t u d e of QD can be as high as that of the p h o n o n c o n t r i b u t i o n even at r o o m t e m p e r a t u r e and, furthermore, that values of PD can be t a k e n in the first a p p r o x i m a t i o n as a direct m e a s u r e of d i s l o c a t i o n density. The o b s e r v e d I/D d e p e n d e n c e of QD, where D is the c o m p o s i t e diameter, is shown to be c o n s i s t e n t with the s t r e n g t h e n i n g m o d e l w h i c h takes into account m a t r i x w o r k - h a r d e n ing c o n t r i b u t i o n (5). Experimental A n rf t e c h n i q u e i n v o l v i n g l e v i t a t i o n m e l t i n g (2) was e m p l o y e d to p r o d u c e Cu-Nb t w o - p h a s e alloys with n i o b i u m volume fractions of .075, .i0, and .15. The copper and n i o b i u m rods used for s t a r t i n g m a t e r i a l s had a p u r i t y of 99.98% or better. The surface layers of the a s - c a s t samples w e r e m a c h i n e d off so that the d i a m e t e r of each was about 7.6 n~n. The ingots w e r e swaged down to 2.08 m m in d i a m e t e r and then c o l d - d r a w n w i t h o u t any i n t e r m e d i a t e a n n e a l i n g up to 99.999% reduction in the cross s e c t i o n a l area. B e g i n n i n g at 0.51 mm, parts of the w i r e were cut off at interm e d i a t e r e d u c t i o n s for testing. A p a r a l l e l set of samples was also p r e p a r e d from 1.6 m m d i a m e t e r

0056-9748/80/040431-055O2.00/0
Copyright (c) 1980 P e r g a m o n P r e s s Ltd.

431

432

DISLOCATION

RESISTIVITY

Vol.

14,

No.

7.5

4
V v

wires which had been previously annealed at 973 K for 168 hours. The experimental apparatus for the hightemperature testing consisted of a pair of four-point probes mounted on a Gorning Macor machinable glass-ceramic base, used for its excellent outgassing properties at high temperature. The whole assembly fitted inside a 25 mm diameter quartz tube with vacuum and electrical connections. During the experiment, high purity argon gas was allowed to slowly flow through the airtight system in order to reduce oxidation. Thermocouples mounted near the voltage contacts indicated that the temperature variation across the samples was typically less than 2 K during temperature increase and 5 K during the down swings. A standard 4probe DC technique was employed. Thermal emfs were significant, but these could be eliminated by averaging the voltages for reversed current directions.

6.C
~F

(D

&
345
v

t'

v
v

v v

~0

Figure 1 shows a plot of the resistivity versus temperature for one of the smallest wires. The general shape of the graph is rather 300 typical, although specimens with larger diameT(K) ters have lower overall resistivities and smaller separation between the top and bottom curves. The upper curve was obtained for the FIG. i. Typical resistivity versus temperature initial temperature increase from the as-drawn plot for Cu-Nb in situ composites state. Clearly, substantial recovery takes place at elevated temperatures, leading to the transition to the lower part of the graph. The exact point at which this occurred varied for different samples, although the initial part of the curve was always linear below 523 K. Data taken during additional cycles fell reproducibly on the bottom curve. Separate least-squares fits were made for the two parts of the graph, providing 273 K intercepts and slopes for the asdrawn and annealed wires. Only data for temperatures below 523 K and 698 K for the upper and lower curves, respectively, were used in order to avoid nonlinear effects.
i

460 ~o

060 7~o 8~o

The main source of error in the measurements is due to the uncertainty in the cross-sectional area of the wires. The diameter of the largest wires was measured with a micrometer. When the diameter was smaller than 61 ~m, however, the area was determined by comparing the wire to a 96+/-1 pm glass callibration sphere,using a scanning electron microscope. This contribution to the overall uncertainty is, thus, held to less than 3%. Considering other possible sources, the total error was about 3.5% or better. Results and Discussion Microstructure As-cast ingots consist of a uniform distribution of 1 to i0 pm niobiu/n precipitates in a copper matrix (2). The niobium filaments which develop in situ resemble curled or folded ribbons. This morphology is due to the <ii0> texture developed in mechanically reduced bcc crystals(6). The final microstructure can be characterized by an extremely dense dispersion of very fine filaments. In the smallest wires, typical filament thickness and spacing can be much less than i00 am, while the width is about an order of magnitude greater. These small dimensions, the large interfacial area, and the twisted nature of niobium ribbons lead to the imposition of an extremely fine cellular structure upon the copper matrix. During the annealing and high-temperature tests, the samples were exposed to temperatures above half the melting point of the copper matrix. Hence, a question arises as to the microstructural stability. Metallographic investigation of the 1.6 nun diameter wires annealed for 168 hours

Vol.

14,

No.

DISLOCATION

RESISTIVITY

433

o 7.5/
x I0% , A 15%

TABLE I Numerical values of coefficients Q1 and P2 for experimental data plotted in Figure 2. Ap = Pl + P2/D vol.% Nb pl(H~-cm) p 2 ( ~ - c m 2)

m IO%ANNEALED
AT .I 6 C M

I.~-

oi (Z~l. Q.. <l

7.5 i0 15

.21 .20 .14 - .03

.0023 .0026 .0043 .0024

0.5

I0 (annealed at 1.6 mm)

,~0

D-~(CM-~)

~o

450 at 973 K indicated no noticable changes. This is expected since the filament spacing and thickness were still quite large at this wire diameter. The same can not be said for the finest wires which were held at temperatures

FIG. 2.

of the order of 700 K to 825 K for as long as two hours during the course of the resistivity measurement. In fact, examination of the niobium filaments in a scanning electron microscope showed that after the test the ribbons were still intact, but they had a fuzzy appearance rather than the smooth texture exhibited in the as-drawn wires. This is probably due to precipitation of niobium dissolved in the copper matrix. Alternatively, the initial stages of filament coarsening may have begun. Nevertheless, a ribbon-like filamentary structure was maintained throughout the test. Dislocation Resistivity The slopes of the top and bottom curves shown in Figure 1 are virtually the same, and this is true for all wires tested. Hence, the effect of cold work on resistivity can be considered to be constant over the temperature range from 273 K to ~ 550 K. Figure 2 shows the difference of the 273 K intercepts plotted as a function of the inverse wire diameter. Since the conductivity of niobium is much lower than that of copper, it acts like an insulator for the purpose of the following analysis. Hence, the values shown in Figure 2 are the original numbers multiplied by the volume fraction of copper. Table I lists the numerical values of intercepts (Pl) and slopes (p2) for the data plotted in Figure 2, assuming a linear dependence of ~p on I/D. The main contribution to the experimental values of ~p is the resistive scattering by the dislocations which were annealed out during the high temperature test. Values as high as 1.6 ~ - c m can be attributed to this effect in the finest wires. This is about 30-40 times higher than what is normally seen in heavily cold-worked single-phase copper, but so is the dislocation density in the as-drawn Cu-Nb wires. It is, therefore, interesting to compare these results with previous experiments which, of necessity, involved samples with lower dislocation densities (less than i0 II cm/cm 3 versus up to 1013 cm/cm 3 for the in situ composites). Although early work was hampered by the indirect methods used to determine dislocation density, some of the more recent studies appear tQ be reliable. Basinski and Saimoto (i) obtained a resistivity per unit dislocation of 1.0"i0 -I~ ~ - c m 3, while Rider and Foxon (7) found a similar value of (1.3+/-.1)'10 -19 ~ - c m 3. A theoretical calculation by Brown (8) yielded the same result

273 K resistivity change plotted as a function of inverse wire diameter.

434

DISLOCATION

RESISTIVITY

Vol.

14,

No.

using a model based on the assumption that dislocation scattering is dominated by the effects of the dislocation core, rather than the long-range elastic strain field. Such a model might be particularly applicable to the materials discussed here since dislocations are so crowded together that the effective range of strain fields is very limited. All of the above values apply at 4.2 K; further experimental work (9,10) indicates that the resistivity due to dislocations in copper typically rises to somewhat less than twice the value at 4.2 K over a very narrow temperature range below i00 K. It then remains fairly constant up to at least room temperature. Assuming a room-temperature value of PD of 2.0.10 -19 ~ - c m 3 and using experimental data of ~p from Figure 2, dislocation densities in the range from 1012 - 1013 cm/cm 3 are obtained. This agrees with the order-of-magnitude estimate from transmission electron microscopy (2). Thus, although the accuracy is somewhat limited, the results of this work are consistent with the earlier experimental studies involving lower dislocation densities and with recent theoretical calculations. It should be noted here, that electron scattering from dislocations and other possible mechanisms, particularly phonon scattering, are not completely independent; it is beyond the scope of this paper, however, to discuss this in more detail. Likewise, the correction term, stemming from the intersection of dislocation lines, is ignored in the present analysis. The slopes (p2) of the curves corresponding to the composites which had not been annealed during the drawing process (Table I) increase with niobium volume fraction. Such behavior is consistent with the general dependence of resistivity upon filament spacing. For a given diameter, the spacing decreases with increasing volume fraction of niobium. A smaller spacing in turn reduces the slip contribution from each dislocation. Thus, to accommodate a given strain (or diameter), the number of dislocations generated during mechanical reduction will be greater in composites with higher niobium content. The upper three curves in Figure 2 intersect the left hand axis at about .20 ~ ~ c m . In contrast, the values of AQ, measured in previously annealed samples containing i0 vol.% Nb, fall on the line which is parallel to that from the as-drawn samples, but has almost zero intercept. This difference arises, no doubt, because of the presence of relatively high levels of niobium retained in the matrix after the final casting of the ingot in a water-cooled copper boat. Niobium then precipitates out of solution during the high temperature resistivity test. Since such an effect can be expected to be independent of wire diameter, the change in impurity scattering will show up as a constant offset in Figure 2. The wires that were annealed while at 1.6 mm diameter will not exhibit such behavior because the niobium would already have precipitated out during the long anneal. Finally, the observed I/D dependence of Ap should be considered. A simple dislocation model (5), based on the assumption that the presence of filaments (i.e. interfaces) effectively inhibits dynamic recovery in the matrix, yields a prediction that during composite reduction dislocation density, Ndisl., increases with l/d, where d is the average interfilament spacing. Moreover, an analysis of the resistivity component due to electron scattering from the filaments indicates that d scales in direct proportion with composite diameter D (5). Hence, Ndisl" and should depend linearly on l/D, in agreement with experimental results presented in this paper. The validity of this model is further supported by the mechanical measurements on the in situ formed Cu-Nb composites (2,11). The ultimate tensile strength of the highly reduced composites was found to approach the estimated theoretical strength of the material and equal the strength of the best copper whiskers. This remarkable behavior can be again linked to the presence of a large number of]dislocationsand the resulting work hardening. Since the flow stress in work-hardened materials scales with N ~ 2. , it is clear that increasing Ndisl by a factor u~s of 30-40 over the values attainable in a slngle-phase material should result in a dramatic increase in strength. The estimated contribution from the matrix work hardening is indeed in good agreement with the predictions based on dislocation densities determined from electrical resistivity measurements.

Vol.

14,

No.

DISLOCATION

RESISTIVITY

4S5

Summary Cu-Nb filamentary composites containing 7.5, i0, and 15 volume percent niobium were produced in situ and their resistivity measured as a function of temperature (300 - 823 K) and composite diameter. The contribution to electron scattering from dislocations was determined by comparing the results for the as-drawn wires with the corresponding data after annealing and recovery. In composites with sufficiently small (i0 - 50 nm) and closely spaced filaments, extremely high density of dislocations (up to 1013 cm/cm 3) leads to correspondingly high value of dislocation resistivity. The present results are in agreement with experimental findings for copper containing much lower dislocation densities and with theoretical calculations. The linear dependence of the dislocation resistivity upon inverse wire diameter is consistent with the strengthening model which takes into account matrix work-hardening contribution. Acknowledgment This work has been supported by the National Science Foundation, References i. 2. 3. 4. 5. 6. 7. 8. 9. i0. ii. Z.S. Basinski and S. Saimoto, Canad. J. Phys. 4~5, 1161 (1967). J. Bevk, J.P. Harbison, and J.L. Bell, J. Appl. Phys. 49, 6031 (1979). G. Frommeyer and G. Wassermann, Acta Met. 23, 1353 (1975). G. Frommeyer and G. Wassermann, Phys. Stat. Sol. (a) 27, 99 (1975). K.R. Karasek and J. Bevk, to be published. W.F. Hosford, Jr., Trans. AIME 230, 12 (1964). J.G. Rider and C.T.B. Foxon, Phil. Mag. 16, 1133 (1967). R.A. Brown, J. Phys. F: Metal Phys. 7, 1283 (1977). Z.S. Basinski, J.S. Dugdale and A. Howie, Phil. Mag. 8, 1989 (1963). V.F. Gantmakher and G.I. Kulesko, Soy. Phys.-JETP 40, 1158 (1975). K.R. Karasek and J. Bevk, Scripta Met. 13, 259 (1979). grant number DMR76-01111.