Saipta Metalhrgica et Materialia, Vol. 32, No. 3, pp. 423-426,1995 Copyright(B1994 Elsevier Science Ltd printed io the USA.

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INTERCRYSTALLINE

DENSITY OF NANOCRYSTALLINE

NICKEL

T.R. Haasz, K.T.Aust, G. Palumbo, A.M. El-Sherik3 and U. Erb3 Department of Metallurgy and Materials Science University of Toronto, Toronto, Canada, M5S lA4 Ontario Hydro Research Division, 800 Kipling Ave., Toronto, Canada, MSZ 5S4 3Department of Materials & Metallurgical Engineering, Queens University, Kingston, Canada, K7L 3N6 (Received August l&1994) (Revised September 9,1994) Introduction Most methods currently available for the synthesis of nanostructured materials result in considerable residual porosity. Studies concerned with the novel structures and properties of these materials (1, 2) are thus compromised by the intrinsically high levels of porosity. As recently shown by Kristic et al. (3) porosity can have a significant effect on fundamental materials properties such as Youngs modulus. One of the most promising techniques for the production of fully dense nanocrystalline materials is electrodeposition. In the present work, the residual porosity and density of nanostructured nickel produced by the electrodeposition method is assessed and discussed in light of the intrinsic intercrystalline density of nickel Experimental Density measurements and calculations presented in this work are based upon Archimedes Principle. The nanocrystalline nickel studied in this investigation was produced by electrodeposition with a purity of 99.9 wt.% (4). The average grain sizes of the electrodeposited material used were 1 l+l nm and 18s nm. The nanocrystalline materials were in the form of 10 mmx 10 mmx0.3 mm sheets. In order to calculate intercrystalline density, 99.999 wt.%f pure single-crystalline nickel was also used. The single-crystalline nickel was in the form of a 1.5 mm thick, 10 mm in diameter disk. The experimental technique used to measure sample weights was developed with the goal of ensuring precision and accuracy. The technique addressed minimizing: (i) reference medium evaporation, (ii) gas absorption by the reference medium, (iii) gas adsorption by materials immersed into the reference medium and (iv) surface contamination. All samples studied in this investigation were lightly polished with 240 grit Sic paper and cleaned in ultrasonic baths of trichloroethane, methanol and distilled water, respectively. By means of a Mettler AB163 analytical balance, five atmospheric weight measurements were taken of each sample to establish the weight of each sample in air (w& To accommodate buoyant weight measurement, the AB163 balance was fitted with an arch attached to the weighing pan of the balance and a beaker filled with Edwards 704 Silicone fluid was placed on an elevated stand below the arch. Utilizing this configuration, sample buoyant weights were determined by measuring: (i) the combined buoyant weight of each sample and a clasping device (wcn+& and (ii) the buoyant weight of the clasping device (w,& itself, Values for both weight configurations were established by performing five weight measurements of each weight configuration. To minimize absorbed gas content in the reference medium and adsorbed gas content on all immersed materials, all buoyant weight measurements were preceded by a vacuum residency period. In order to facilitate this operation, the clasping device and/or sample was hooked upon a rest arm attached to the beaker and the complete unit was placed in a 10. Pa vacuum chamber until the majority of these gases were removed.

?Purity levels are based upon metallic and non-metallic

contributions

423

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DENSITY OF Ni

Vol. 32, No. 3

Following adjustment of all raw weight data to account for effects due to evaporation, impurities and oxide films, specific density (sp) was calculated according to Archimedes Principle. Also, the error associated with each specific density calculation (asp), based upon a theory proposed by Doebelin (5) was determined to be,

where each term preceded by a A corresponds to the + error associated with the subscript quantity, To avoid sources of error associated with the chosen reference medium, all material densities were left as specific densities. Results and Discussion Table 1 shows the effect of grain structure and porosity on specific density. Decreases in specific density associated with decreases in grain size are representative of the larger intercrystalline component found in nanostructured materials (6) and any possible residual porosity. The apparent increase in specific density with decreasing nanocrystalline grain sizes (i.e. 18tinm to 1l+lnm) may be due to porosity. The amount of porosity can be approximated by using two sources of reference: (i) the density difference between the single-crystalline structure and the nanocrystalline structures and (ii) the density difference between the two nanocrystalline structures, The former establishes an ultimate nanocrystalline porosity content of approximately 0.6 % and the latter establishes a minimum nanocrystalline porosity content of approximately 0.3 % with respect to volume. However realistically, porosity contents are expected to be less than the ultimate porosity predicted because of the finite excess volume associated with the intercrystalline regions in the nanocrystalline samples. TABLE I. Specific density results with respect to Edwards 704 Silicone fluid for different Ni grain structures.

II

Grain Structure

Specific Density

I [Dimensionless] 1 8.387M.002
8.345~0.02 8.32kO.02

II

II Single crvstal 11&l nm 18s nm

II

Porosity content calculations can be further refined by comparing the magnitude of each specific density difference with the corresponding structural difference. The resulting outcome suggests that the magnitude of the transition from the 1151 nm grained material to the 1852 nm grained material is half as profound as the transition from the single crystalline material to the nanocrystalline materials (i.e. the 1If1 nm and the 18+2 nm grained materials). Also, the decrease in grain size from 18152 nm to 1 If1 nm produces a decrease in free volume. Conceptually, this is difficult to accept. A more reasonable explanation assumes that the 18ti nm grained material is virtually free of porosity and the 1 l+l nm grained material contains 0.3M.l % porosity. Intercrvstalline Density

Intercrystalline density (p,J can be viewed as crystalline density (pcRYs.) less the mass density equivalent of intercrystalline free volume density (pIc voL,MASS ) This is mathematically expressed as, EQv,
PIG = kRYs.-Pn: Pm
eqv

VOL MASS

(2)
This quantity

However in order to evaluate equation (2), an expression for pFREE MASS must be introduced. voL. rev, can be described by the ratio below.

Vol. 32, No. 3

DENSITYOF Ni

425

prc Fme

nn. 8u.w PQ.

Intercr)rstauinr jke
=

v&me maw equivalent (3)

Interc~lline volume = hsvG~cm..P,)

u;J

where, PSINGLE = single crystalline density of a specified chemistry CRYS opoLY= polycrystalline density of identical chemistry f, = intercrystalline volume fraction Equation 3 can be further simplified by utilizing intercrystalline authors describe intercrystalline volume fraction as, theory proposed by Palumbo et al. (6). The

frc = lwhere,

(1

-;i
Ani

(4)

A = grain boundary thickness dAW = average grain size.

Therefore, the intercrystalline

PIG = PsIhw.ecm. -

density of a nanocrystalline

material can be expressed as,

PsLwLe cws. - PNANG.

l- (1 - F
AVG

(5)

Alternatively,

intercrystalline
shLVGLEC,WS.

density can be expressed in terms of a reference medium, i.e.,

-

%2 = sh,MGLECiW -

%VNO.

l- (1 - y-)3
AVG

(6)

where, so, = the specific density of the subscript quantity x with respect to a chosen reference medium However, to effectively distinguish between crystalline and intercrystalline density, intercrystalline has been presented in terms of a percent reduction of crystalline density (IS%), i.e., 6% = SPCRYS. SPIC XlOOk SPCRYS. (7) density (prc)

Errors associated with 6% were formulated by applying Doebelins technique (described earlier in relation to specific density) to expression 7. Following substitution of the specific densities determined in this investigation, intercrystalline densities of the 1 l&l nm and 1W2 nm samples, expressed in terms of crystalline percent reductions, were calculated to be 2.3k1.8 % and 5.1+3.8 %, respectively. All calculations were based upon a grain boundary thickness of lf0.5 nm. The calculated crystalline density reductions (6%) cannot be assumed to be absolute or without limitations. The proposed intercrystalline theory underlying the derivation of intercrystalline density reduction presented in this paper assumes two material characteristics and thereby imposes two limitations: (i) negligible vacancy and lattice dislocation content and (ii) negligible porosity content. Vacancy and lattice dislocation content becomes a concern when it imposes an effect on the free volume of the material as a whole. This factor can be eliminated by examining one nanocrystalline grain within a nanocrystalline structure. Consider a grain in the form of a tetradaidecahedron with a grain size of 10 nm. If we assume that the surfaces of the tetradaidecahedron are comprised of low angle interfaces, each surface can be described as a collection of dislocations (7). Also, due to the limited size of a 1Onm grain, the probability of finding a dislocation within the grain becomes quite low. Hence, when all sides of the tetradaidecahedron are

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DENSITYOF Ni

Vol. 32, No. 3

considered, the contribution of boundaries are considered, the volume associated with larger display minimal intra-granular

intra-granular dislocations becomes minimal. Furthermore, when larger angled intra-dislocation content becomes even less pronounced due to the enhanced free angled boundaries. Therefore, nanocrystalline materials can be considered to dislocation effects.

However because of the suspected porosity contents in the 18+2 nm grained samples (0.3fO.l %), porosity cannot be assumed to be negligible and therefore, the calculated 6% value above tends to be inflated. A more accurate 6% value would be 3.613.6 %. Due to the considerable overlap of both nanocrystalline 6% values, the 1 l+l nm and 18s nm grained materials were chosen to be described by a common 6% value, i.e. 2.3Ifil.S %. Although the error associated with the calculated 6%++value may appear to cloud the result, it in fact describes the nature of the intercrystalline component: an intricate network of interfaces connected via triple lines and quadruple nodes with each single defect possessing its own specific structure. Conclusions With the use of Archimedes Principle, a maximum porosity of 0.3?0.1 % was found in the electrodeposited nanocrystalline nickel studied. Moreover, the intercrystalline density of these materials was calculated to be 2.31tl.8 % less than the density of single crystalline nickel. These calculations are believed to be void of any significant porosity, intra-granular dislocation and impurity effects. Acknowledgments Haasz would like to thank Mr. N. Wang and Dr. A.A. Haasz for useful discussions dealing with structure theory and experimental technique. Special thanks are also extended to the Natural Sciences and Engineering Research Council of Canada for financially supporting this endeavour. References 1. 2. 3. 4. 5. M.J. Aus, B. Szpunar, U. Erb, A.M. El-Sherik, G. Palumbo and K. T. Aust, J. Appl. Phys., 75(7), 3632 (1994). A.M. El-Sherik, U. Erb, G. Palumbo and K.T. Aust, Scripta Metall. Mat., 27, 1185 (1992). V. Kristic, U. Erb and G. Palumbo, Scripta Metall. Mat., 29, 1501 (1993) A.M. El-Sherik and U. Erb, U.S. Patent Pending (1993). Ernest 0. Doebelin, Measurement Systems: Application and Design, p. 59, McGraw-Hill Book Company, New York (1966). 6. G. Palumbo, S.J. Thorpe and K.T. Aust, Scripta Metall. Mat., 24, 1347 (1990). 7. Robert E. Reed-Hill, Physical Metallurgy Principles - 2nd Edition, p. 214, PWS-KENT Publishing Company, Boston (1973).

++A11 errors assigned to variables describing 6% have been chosen to represent a minimum confidence interval of 80%. Therefore, 6% errors also describe the degree of variation of 6%