Pergamon

NanoStruchued Matiab, Vol. 6. pp. 533-538.1995 Cqyight Q 1995 Elsevia Science Ltd F rinted in the USA. All ri@ts -ed 0965-9773195 $9.50 + .OO

09659773(95)ooll4-x

ELECTRODElQSlTED NANOCRYSTALS: SYNTRESIS, PROPERTIES AND INDUSIIUAL APPLICATIONS

U. Erb

Dept.

of Materials and Metallurgical Eng., Queen University, s

Kingston, Ontario, Canada. K7L 3N6

Abshct -- Electrodeposition of nanocrystalsis a technologically and economically viable pr&ction route to metals,alloys and metal matrix compositesboth in bulk form and as coatings. Certain properties of nanostructuredelectrodepositssuch as hardness,wear resistanceand electrical resitivity are strongly affected by grain size. On the other hand;properties such as thermal expansion, Young modulusand saturation magnetization s show little grain size dependence. Potential applicationsof nanostructured electrodeposits range jrom corrosion and wear resistant coatings to sop magnetic materials for magnetic recording.

INTRODUCTION
The processingof nanostructured materialscan be considereda distinct form of grain boundary engineeringwhich involves the increaseof the overall volume fraction of grain boundariesand triple junctions in a material. Nanocrystallinematerialswere first describedby G leiter (1) and, as a result of their attractive properties(2), numeroussynthesistechniquesfor the production of thesematerials in large quantitiesare presentlybeing explored. Theseinclude gas-condensation, ball-milling, sol-gel techniques,spark erosion,etc.. Our researchefforts over the past 10 years have been concernedwith electrochemicalproduction methods. The techniques applied in our laboratory to synthesize nanocrystalline structures include conventional DC electroplating,pulsed-currentdeposition,auto-catalytic plating as well as codeposition processes to produce nano-compositematerials. Electrodeposition has many advantages over other nano-processing techniquesincluding 1) the potentially very large number of pure metals, alloys and compositematerials which can be electrodeposited with grain sizes less than 100 run, 2) few shape and size limitations, 3) high production rates, 4) low initial capital investmentrequirementsand 5) easy technologytransfer from the researchlaboratory to existing infrastructure in electroplating and electroforming industries. In addition, electrodeposition can yield porosity-free finished products which do not require further consolidation processing.

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SYNTHESIS OF ELECTRODEPOSITED NANOCRYSTALS

Although there had beennumerousreports in the literature on electrodeposits with ultrafme grain structures (eg.3), no systematicstudieson the synthesisof equiaxednanocrystallinematerialsby electrodepositionmethodsto optimize certain propertiesby deliberatelyintroducing large volume fractions of grain boundariesand triple junctions into the material were published prior to 1989 (4,s). Over the past few years, we have identified the electrochemicalprocessingwindows for a number of pure metals, binary and ternary alloys as well as nano-structuredmetal matrix composites (see Table I). These materials can be depositedas thin fdms (1 to 100 p) or in bulk form (several m m thick). Fundamentally, electrodepositionyields grain sizes in the nanocrystalline range when the electrodeposition variables (eg. bath composition, pH, temperature,current density, etc.) are chosen such that nucleation of new grains is favoured rather than the growth of existing grains. In practice, this can be achieved by using high deposition rates, formation of appropriatecomplexes in the bath, addition of suitable surface active elementsto reduce surface diffusion of ad-atoms,etc.. TABLE I Examples of materials produced by electrodepositionand potential industrial applications. Materials Ni, NJ-P, Ni-Mo, Ni-Zn, Ni-Fe, Ni-Fe-Cr Ni-A&O,, Ni-SiC co, co-w, CO-P Pd, Pd-Ni Applications Corrosion protection, stress corrosion cracking resistance,soft magnets,catalysts Corrosion protection, wear resistance Magnetic materials, hard coatings Hydrogen storage and purification, electrodes for hydrogen evolution reaction and fuel cells

PROPERTIES OF NANOCRYSTALLINE

ELECTRODEPOSITS

From the property measurementsperformed on materials produced in our laboratory, the following picture is emerging: certain properties are strongly dependenton grain size while others vary little with grain size. Table II summarizesthe grain size dependentproperties for nanocrystallineNi. Two examples,the variation of hardness(16) and electrical resistivity (17) of nickel with grain sizes ranging from 100 p to 6 mn are shown in Figures 1 and 2 The hardnessof Ni (Figure 1) initially increaseswith decreasinggrain size following regular HallPetch behaviour. However, at grain sizes below 30 nm, considerabledeviation from the HallPetch behaviour is observed leading to softening at the smallest grain size. This behaviour which has also been observed on other electrodeposited nanocrystals(4,22) is consistent with recent observations on materials produced by other techniques(23,24). Although the exact reasons for this change in hardness with grain size are presently unknown, a number of contributing factors have been discussed,including texture changes,diffusional creep, triple junctions, dislocation network formation and pile-up, etc. (eg.25).

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TABLE II Properties of electrodepositedNi nanocrystalswhich are strongly affected by grain size.

II

pv-9

ObS@lWBtiOll

I I

Ref. 45

11Solid solubility 11Hydrogen solubility

1 greatly enhanced [ greatly enhanced 1 nearly eliminated I shifted to more noble potential higher defect density greatly reduced greatly enhanced

7-6

II Localized corrosion
II Corrosion potential Defect structure in passive layer Thermal stability Hydrogen diftusivity I[ Coercivity Coefficient of friction Wear resistance Strength Ductility Hardness Electrical resistivity

~ TV-73 ~ I 778
9 10,ll
6,12

I single domain effects

reducedby a factor of 2 enhancedby 170 times increasedby a factor of 3 to 10 greatly reduced increasedby a factor of 5 increasedbv a factor of 3

13 14 14 15 15 16 17

50

100

150

200

250

300

350

Temperature

(K)

Figure 1 Hall-Petch plot for bulk nickel electrodeposits(16).

Figure 2 Resistivities of nanocrystalline Ni compared with normal crystalline Ni (17).

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Table III Properties of electrodeposited nanocrvstalswhich are little affected bv nrain size. Ni
PVJ-tY Observation Ref.

Bulk density Thermal expansion Young modulus s Adhesion to substrate(for coatings) Thickness of passive layer 11Saturation magnetization

reducedby < 1% unchanged unchanged unchanged same as for polycrystalline (1.3 nm) I I reducedby m 5%

18 19 20 21 9 21 II

11Resistanceto salt spray environment [ unchanged

I 13 II

The electrical resistivity of nickel as a function of temperatureis shown in Figure 2 for various grain sizes. At room temperature, the resistivity of materialwith 10 nm grain size is enhanced by a factor of 3 over the resistivity value observedfor conventionalpolyc~ystallinematerial. The excess resistivity (ie. total rcsistivity of nanocrystalline Ni m inus the rcsistivity of the conventional polycrystalline Ni) was found to increaselinearly with the total intercrystalline volume fraction (17). Therefore, the increasein resistivity with decreasinggrain size can be attributed to electron scattering events on intercrystalline defects. In contrast to these structure-dependent properties,other properties such as shown in Table III were found to be little affected by grain size. For example, the saturation magnetization of nanocrystalline Ni (10 mu grain size) was only reducedby 5% of the value measuredfor

6oo r-----l
500 F M ---&
. . Present Gong Study et al. 1991

200

10

LO2 Grain Size

lo3 (nm)

lo4

Figure 3 Saturation magnetization of pure bulk Ni electrodeposits as a function of grain size (13).

Figure 4 Salt spray corrosion resistancefor m icrocrystalline and nanocrystalline nickel on steel substrates(21).

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conventional polycrystalline Ni of 100 p grain size (see Figure 3) (13). This observation is consistent with recent calculationswhich showedthat the averagemagnetic moment of Ni atoms in structurally different grain boundariesis not reducedby a large amount (26). Therefore, even at grain sizes as small as 10 mn, the overall contribution of the grain boundary volume fraction to the saturation magnetization is rather small. Another example of properties which are little affected by grain size is the corrosion resistanceof Ni electrodeposited onto mild steel substrates in a salt spray environment (ASTM B-117). As shown in Figure 4, the developmentof red rust on the Ni coating is essentially the same for nanocrystalline and polycrystalline material indicating that the corrosion resistanceis not affected by nano-processing(21). It is interesting to note that some of the properties listed in Table III which are essentially independentof grain size for electrodepositedmaterials were previously found to be strongly affected by grain size in materials produced by other synthesis techniques. For example, considerable increaseswere found for the thermal expansion of gas-condensed nanocrystalline materials, whereas significant reductions in the Young modulus and the saturation s magnetization were reported for nanocrystals producedby same technique (2). This discrepancy indicates that some properties of nanocrystalline materials are strongly dependent on the method of synthesis and therefore are not necessarily the result of the nanocrystalline structure per se. Clearly, future work on nano-structuredmaterials must address the complete range of microstructural parameters (eg. grain boundary and triple junction character distribution, porosity, residual stress, impurity content, crystallographic texture, etc.) before a full understandingof the intrinsic properties of the nano-structureis reached.

INDUSTRIAL APPLICATIONS
As a result of the unique properties observed on electrodepositednanocrystals, a number of industrial applications are emerging, some of which are indicated in Table I. For example, the combination of increasedhardness/ wear resistanceand reducedlocalized corrosion results in improved protective coating performance. The material could be used as hardfacing on softer, less wear resistant substrates. For electroformed products such as printing mandrels and CD stampers, longer run life is expected. The magnetic and electrical properties make them attractive as soft magnetsfor high efficiency transformer, power supply and motor applications. The next generationof recording head materials could also benefit from the excellent magnetic, electrical and wear properties. The exceptionalcatalytic propertiesmake them strong contenders for applications such as electrodes for hydrogen evolution reaction and fuel cells. Some nanocrystalline alloys exhibit very large solubility for hydrogen,making them suitable candidates for hydrogen storagematerials. As a result of the enhanced solubility, a wide range of new alloy systems can be synthesized which are not available in conventional form. Commercialization efforts in a number of these and other areas are presently in progress using electrodeposited nanocrystals both as coatings and in bulk form (27).

ACKNOWLEDGEMENT
Financial support by NanometalsCorporation, the Natural Sciences and Engineering Research Council of Canada,and the Ontario Centre for Materials Researchis gratefully acknowledged.

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REFERENCES
1. H. Gleiter, 2nd Ris+ Int. Symp. Metall. and Mat. Sci., eds. N. Hansen,A. Horsewell and H. Lilholt ( Ris4 National Laboratory, Demnark), 15 (1981). 2. H. Gleiter, Progr. Mat. Sci., 33, 224 (1989). 3. A. Brenner, Electr&position of Alloys - Principles and Practice, Academic Press (1963). 4. G. McMabon and U. Erb, M icro&. Sci., g 447 (1989). 5. G. McMahon and U. Erb, J. Mat. Sci. Lett., 3 865 (1989). 6. D.M. Doyle, G. Palumbo, K.T. Aust, A.M. El-Sherik and U. Erb, Acta Metall. et Mater., submitted (1994). 7. R Rofagha, R I-anger, A.M. El-She& U. Erb, G. Palumboand KT. Aust, Scripta Metall. et Mater., 25, 2867 (1991). 8. R. Rofagha, R. Langer, A.M. El-Sherik, U. Erb, G. Palumboand K.T. Aust, Mat. Rcs. Sot. Symp. Proc., 238, 751 (1992). 9. R Rofagha, S.J. Splinter, U. Erb and N.S. McIntyre, Nanostr. Mat., 5 1 (1994). 10. K. Boylan, D. Ostrander,U. Erb, G. Palumboand KT. Aust, Scripta Metall. et Mater., 25. 2711 (1991). A.M. El-Sherik, K Boylan, U. Erb, G. Palumbo and KT. Aust, Mat. Res. Sot. Symp. 11. Proc., 238. 727 (1992). 12 G. Palumbo,D.M. Doyle, A.M. El-Sherik, U. Erb and KT. Aust, Scripta Metall. et Mater., 25. 679 (1991). 13. M .J. Aus, B. Szpunar,A.M. El-She& U. Erb, G. Palumboand KT. Aust, Scripta Metall. et Mater., 27, 1639 (1992). 14. A.T. Alpas, University of Windsor, Windsor, Ontario, private communication(1994). 15. N. Wang et al., to be published. 16. A.M. El-Sherik, U. Erb, G. Palumbo and KT. Aust, Scripta Metall. et Mater., 27, 1185 (1992). 17. M .J. Aus, B. Szpunar,U. Erb, A.M. El-Sherik, G. Palumboand KT. Aust, J. Appl. Phys., 75. 3632 (1994). 18. T.R Haasz, KT. Aust, G. Palumbo,A.M. El-Sherik and U. Erb, Scripta Metall. et Mater., accepted(1994). 19. T. Turi et al., to be published. 20. L. Wong, D. Ostrander, U. Erb, G. Palumbo and KT. Aust, in Nanophuses and Nanocrystalline Structures, cds. RD. Shull and J.M. Sanchez,TMS, 85 (1994). 21. AM. El-Sherik and U. Erb, Plat. and Surf. Fin., submitted (1994). 22. C. Cheung, G. Palumbo and U. Erb, Scripta Metall. et Mater., 31. 735 (1994). 23. A.H. Chokshi, A. Rosen,J. Karch and H. Gleiter, Scripta Metall., 23. 1679 (1989). 24. H. Chang, H.J. Hofler, C.J. Altstetter and RS. Averback, Scripta Metall. et Mater., 25, 1161 (1991). 25. C. Cheung, F. Djuanda, U. Erb and G. Palumbo,Acta Metall. et Mater., submitted (1994). 26. B. Szpunar,U. Erb, K-T. Aust and G. Palumboand L.J. Lewis, Mat. Res. Sot. Symp., 318. 527 (1994). 27. D. Wood, NanometalsCorporation,London, Ontario, private communication(1994).