Mesoscale and Microscale Manufacturing Processes: Challenges for Materials, Fabrication and Metrology. T. A. Dow and R. O. Scattergood Precision Engineering Center North Carolina State University, Raleigh, NC 27695-7918 Introduction Length scales for processes and materials are generally classified as nanoscale (< 100 nm), microscale (100 nm to 100 µm) and mesoscale (> 100 µm). The length can be an external dimension of a component, or the internal dimension of a material such as the crystalline grain size. A comprehensive summary of the recent state-of-the art for Micro Meso Mechanical Manufacturing (M4) is given in the NSF workshop report [1]. Material properties play an important role for all of the manufacturing processes. The M4 report concludes that "understanding mechanics and physics of materials at the microscale is essential", and that "material can no longer be considered homogeneous when the process size dimensions approach the material grain size". The overview presented in this paper will focus on material properties, and in particular the structural properties of metals that will be used for the production of miniaturized mechanical components and assemblies. Many of the other papers in this conference will address the specific fabrication processes or metrology methods for manufacturing down to the microscale or nanoscale. Mechanical Micromachining and Materials Milling, drilling, turning or grinding are basic mechanical manufacturing processes used for the production of complex 3D components. Metallic materials used are steels and nonferrous alloys of aluminum, copper, titanium and other metals. These engineering materials provide the range of mechanical properties required for fabrication and end use. Manufacturing at the microscale using mechanical processes, ie., mechanical micromachining, requires suitable adaptation of the conventional processes. Fig. 1a shows an example of miniaturized tooling used to turn the demonstration microgrooves in 6061 aluminum shown in Fig. 1b [2]. Fig. 2 shows commercially micromachined components with overall dimensions on the order of 1-2 mm [3]. The need for further miniaturization of components will require that internal features on assembled components of this size, or smaller, be the order of 20 µm or less, similar to the features shown in Fig. 1. What kind of engineering materials will be best suited for these applications ? A general engineering guideline for materials selection is that the grain size be at least two orders of magnitude smaller than the section or feature size for the component of interest. Otherwise, the material response will not be uniform or predictable. Uniformity of material response in this context means 2003 Winter Topical Meeting - Volume 28

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(b) Figure 1. a) Miniature cutting tool. b) Grooves cut with the tool.

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that directional-dependent (anisotropic) material properties must be averaged over a sufficiently large number grains so that fluctuations over the length scale of interest are negligible. Both the elastic and plastic properties of crystalline materials are anisotropic with very few exceptions. Fig. 3 shows an example of grooves produced in a very large grain-size, high-purity tin lap plate by diamond turning [4]. The tin is soft and very ductile which leads to extensive burr formation on the groove overlaps. The burr formation is produced by dislocationcontrolled plastic deformation (slip) and this is strongly dependent on the local crystal orientation. Nonuniform material response is manifest as dramatic changes in the extent of burr formation when a grain boundary is crossed in Fig. 3. If the tin Figure 2. Micromachined parts. Note grain size were reduced below 1 µm, burr formation viewed at the scale with respect to the fingers the same magnification would appear quite uniform. on the hand. Furthermore, burr size could be substantially reduced because fine-grained tin is harder and less ductile. Currently, one of the most hotly pursed research areas in materials science is the synthesis of nanocrystalline (nc) materials with grain sizes in the nanoscale size range. If mechanical micromachining techniques are developed which push section sizes down to 10 µm or less, the guidelines discussed above for uniformity and predictability of properties points to the need for nc metals and alloys, ie., grain sizes < 100 nm. Furthermore, optimal process development will require interdisciplinary research efforts between precision engineers and material scientists. This has not yet been undertaken in a concerted fashion. In the following sections, a brief overview of the synthesis and properties of nc metals and alloys will be given with the aim of introducing the precision engineering community to this novel class of materials and hopefully encouraging more interdisciplinary research for mesoscale and microscale manufacturing processes. Synthesis of Nanocrystalline Metals and Alloys Research on nc materials includes the synthesis of particles, thin or thick films and bulk material along with the characterization of their properties. The state of the art is described in recent reviews [5]. Materials can be metals, ceramics or polymers. Since mechanical micromachining is a bulk fabrication process for metallic materials, only bulk synthesis techniques for metals are relevant. There are two type of processing methods in widespread use. They are classified as two-step or one-step synthesis Figure 3. Burrs formed along grooves cut in a tin techniques. Two-step techniques involve the plate. A grain boundary lies along the dashed line. production of a powder, which must then be compacted. Powder production has been done using condensation of a gas to form nanoscale particles or high-energy ball milling to produce powders from the starting materials. In the case of milling, the final powder size can be large, on American Society for Precision Engineering

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the order of 1-100 µm, but the crystalline grain size within each powder particle is nanoscale. Milling is quite versatile since any composition can be made, and the alloys produced can be a non-equilibrium mixture of normally insoluble constituents. The second part of the two-step technique is compaction of the powder into a fully dense solid. Compaction requires application of pressure for densification combined with elevated temperature to promote plastic deformation and diffusion processes that lead to interparticle bonding and removal of porosity. The primary difficulty for nc materials is that temperatures must be kept low to avoid extensive grain growth during compaction. Since a large fraction of the atoms in nc materials are in high-energy grain boundaries, there is a large driving force for grain growth. For example, at a grain size of 5 nm, about 50 % of the atoms are grain boundaries. Much of the early work on nc metals produced by two-step methods was inconclusive due to processing defects introduced by poor compaction. One-step synthesis techniques avoid the compaction step. The most widely used one-step techniques are electrodeposition of thick films which can be stripped from substrates, large-strain plastic deformation, and crystallization of metallic glasses. Each of these has limitations. Varying composition is difficult with electrodeposition. Large plastic strain techniques based on rolling or extrusion can be used with ductile starting materials, but it is usually difficult to get the grain size below 100 nm. Certain zirconium-based, aluminum-based or iron-based alloys can be cast in bulk form as fully amorphous metallic glasses. These can then be crystallized to form nc alloys. Mechanical Properties of Nanocrystalline Metals and Alloys The mechanical properties of nc metals and alloys will be a key factor in determining their success as optimum materials for manufacturing. For machining, properties such as strength, ductility and work-hardening capacity determine tool forces, surface finish and features such as shear localization or burr formation. For end use of a component or an assembly, performance can be limited by properties such as fatigue life, wear resistance and fracture toughness. Although a large number of studies have been done on the mechanical properties of nc materials, a fundamental understanding of the deformation mechanisms and a reliable database of the engineering properties is just beginning to emerge [6,7]. As already noted, many of the earlier results are inconclusive due to processing defects introduced during synthesis. In addition, there is the fact that laboratory-scale synthesis methods generally produce small quantities of nc material, insufficient to make standard-size specimens for mechanical testing. However, the state of the art is improving because better synthesis techniques and small-scale mechanical testing techniques are being developed. A very large increase in yield strength and hardness due to a reduction in grain size is the most striking and best understood effect for nc metals. For example the yield strength of 20 µm grain size, high purity annealed copper is about 50 MPa and the strength approaches 1 GPa when the grain size is reduced to 16 nm. This is a result of a grain-size strengthening mechanism that inhibits the motion of dislocations on slip planes. The increase in yield strength σy, or the hardness H ≈ 3 σy, as a function of grain size is given by the Hall-Petch relation [8], σy = σo +

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k d

(1)

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where d is the grain size and σo and k are material constants which depend on the temperature and strain rate. Extrapolating the Hall-Petch relation for conventional grain size materials (d ≈ 5 50 µm) to the nanoscale size range predicts large increases in the strength. Large increases are observed for nc metals. Moreover, as shown by the Hall-Petch plot in Fig. 4, when the grain size decreases, the strength passes through a maximum at a critical value of the grain size and then decreases. Considerable controversy has surrounded this inverse Hall-Petch effect since processing defects might also cause the strength reduction. However, there are now reliable measurements, like those shown in Fig. 4, which confirm the inverse effect and imply that a new plastic deformation mechanism becomes operative at very small grain sizes A number of different mechanisms have been proposed [6]. It appears Figure 4. Hall-Petch plot of hardness vs. that dislocations no longer control plastic 1/√d for electrodeposited nc nickel. The deformation in nc metals with grain sizes less than straight line represents eq. (1) for large about 10-20 nm. Alternate mechanisms depend on grain-size nickel [6]. plastic deformation controlled by grain-boundary diffusion processes that do not involve dislocation motion. The simplest picture for a mechanism transition follows from the well-known equation for plastic deformation due to grain-boundary controlled diffusion creep [8], Q

dε Aσ − RTb = 3 e dt d

(2)

where dε/dt is the strain rate, σ is the applied stress, Qb is the activation energy for grainboundary diffusion, R is the gas constant and A is a material constant. The yield strength of a material is always measured at a specified temperature and strain rate. Assuming that plastic deformation is controlled by the diffusion creep mechanism, σ = σy in equation (2) and thus σy is proportional to d3 at a fixed temperature and strain rate. In contrast, equation (1) shows that σ y is inversely proportional to √d for the dislocationcontrolled plastic deformation mechanism. Consequently, as grain size decreases the yield strengths for the two mechanisms must cross over such that the diffusion mechanism would be favored below a critical grain size. The effects of grain size on mechanical properties other than yield strength or hardness remain uncertain at this time. The data in Fig. 5 indicate that the ductility in tension for nc metals Figure 5. Plot of ductility in tension vs. grain decreases as the grain size decreases. This loss in size for the nc metals indicated [9]. ductility is not desirable, but there is encouraging evidence that ductility can be improved at the American Society for Precision Engineering

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smallest grain sizes in multi-phase alloys [9]. The effect of grain size on properties such as work hardening capacity, fatigue life and fracture toughness have not yet been established. There is conflicting evidence for the presence or lack of work hardening capacity in pure nc metals. Iron shows very low work hardening over a wide range of nanoscale grain sizes whereas nc copper and zinc generally do work harden. Improved fatigue life has been reported for some nc metals. Establishing the effects of grain size is complicated by the fact that the synthesis techniques for nc metals often produce a rather wide distribution of grains sizes. It has been suggested that this results in a superposition type response wherein the larger grains will deform by dislocation mechanisms and the small grains deform by diffusion mechanisms. The effects of alloying been studied for various nc metals [10]. As in the case of larger grain-size materials, multi-phase microstructures can produce beneficial changes in the mechanical properties. For example, two-phase nc alloys produced by partial crystallization of metallic glasses or by mechanical milling can exhibit high strength along with good ductility at very small grain sizes. The metallic glasses are rather unique in that the fully amorphous glass has no work hardening-capacity. Such glasses fail catastrophically with zero ductility in a tensile test because of shear localization. When fully crystallized to form an nc alloy, the glasses are usually very brittle and will fracture. Intermediate structures formed by partial crystallization consist of nc grains in an amorphous glass matrix. These alloys have shown excellent combinations of strength, ductility, toughness and resistance to shear localization. Furthermore, they are fully dense with no processing defects. More research is needed to explore the benefits of multi-phase microstructures in nc alloys. Modeling Because of the nanoscale grain size, nc materials are suited to molecular dynamics modeling. A large number of very small nano-grains can be incorporated into the computational cell. The structure of the grain boundaries has been studied extensively using modeling and Figure 6. Simulation of the deformation of nc copper (5.2 nm grain size). a) high-resolution electron initial configuration. b) after 3% strain [7]. microscopy [11]. The nature of the boundaries depends in part on the synthesis technique and subsequent thermal treatments. The boundaries can be sharp with a well defined structure and relatively stable, or they can be more diffuse, analogous to a thin amorphous layer surround the grains, and less stable. It is thought that the latter type of boundaries are present in materials with very small nano-grains and that these boundaries promote the diffusion-based plastic deformation mechanisms discussed earlier [6]. Simulations of the dynamic stress-strain response are also being done to provide insight into the 2003 Winter Topical Meeting - Volume 28

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deformation mechanism. The results must be carefully interpreted since molecular dynamics simulations correspond to very high strain rates. Changes in the grain structure and the plasticity mechanisms can be observed in these simulations. Fig. 6 shows typical results for a simulation of the deformation in pure copper [7]. Summary The development of new nc metals and alloys is actively being pursed by materials scientists. One can anticipate that a reliable database of their properties will emerge from this work. Because of the very fine grain size, this class of materials should be well suited to the needs of mesoscale and microscale manufacturing and in particular to mechanical micromachining of very small section sizes and features. Coatings produced by electroplating, for example, copper and electroless nickel, have had wide application for diamond turning. The nanoscale grain size of such coatings produces high hardness, good uniformity of properties at small size scales and excellent surface finish. Encouraged by this, precision engineers and materials scientists can look forward to a wider range of new nc metals and alloys that will enhance the development of mesoscale and microscale manufacturing.

References 1 . K. F. Ehmann, R. E. deVor, S. G. Kapoor and J. Ni., Micro/Meso-Mechanical Manufacturing M4, NSF Workshop, May 16-17 (2000). 2. D. P. Adams, M. J. Vasile and A. S. M. Krishnan, Precision Engineering, 24 [4], 347 (2000). 3. Remelle Engineering, Inc., New Brighton, MN, 55112. 4. D. A. Kametz, PhD thesis, NC State University (2001). 5 . C. C. Koch, ed., Nanostructured Materials: Processing, Properties and Potential Applications, Noyes Publications (2002). 6. J. R. Weertman, in ref. 4, 397 (2002). 7. J. R. Weertman, D. Farkas, K. Hemker, H. Kung, M. Mayo and H. Van Swygenhoven, MRS Bulletin, 24, 44 (1999). 8. T. H. Courtney, Mechanical Behavior of Materials, McGraw Hill (2000). 9. C. C. Koch, D. G. Morris, K. Lu and A. Inoue, MRS Bulletin, 24, 54 (1999). 10. J. Eckert, in ref 4, 423 (2002). 11. V. Vitek, Stability of Materials - NATO Advanced Science Institute, A. Gonis et al, eds., Plenum Press, 53 (1996).

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