Micro-architectured structures, or “microstructures,” including microlattices and microsandwiches, have recently emerged as promising structural and functional frameworks for small-scale multi-functional devices. The open architecture of such structures not only leads to low areal density and high damage tolerance, but also provides channels for heat and fluid flow, which are critical to multi-functional devices, such as high capacity batteries, insect-like robots, and micro-air vehicles.
Sandwich structures, which comprise a core that extends between opposed end plates, exhibit higher bending rigidity than lattices by effectively redistributing the mass to the outer surfaces (instead of the core), similar to natural cellular materials found in insects and plants. Such superior properties have led to extensive studies on the structural performance of sandwich structures, mostly with physical dimensions above tens of centimeters. The damage tolerance of sandwich structures is highly dependent on the density, strength, and geometry of the core. It was found that a periodic sandwich core can be optimized to sustain loads at much lower relative densities than stochastic foams. Further improvement of mechanical properties may also be achieved by hybridizing the core material.
Existing fabrication procedures for large-scale sandwich structures typically involve welding or adhesive bonding of the face sheets and the core. These techniques become challenging as the size of the sandwich's core decreases to the nano- or micro-scale. Recently there have been several successful attempts to create microlattice and microsandwich structures from polymers, ceramics, and metals. Unfortunately, the fabrication processes used to construct these microstructures are complicated or limited to specific materials. It can therefore be appreciated that it would be desirable to have a more simple fabrication technique for such microstructures.
The present disclosure may be better understood with reference to the following figures. Matching reference numerals designate corresponding parts throughout the figures, which are not necessarily drawn to scale.
As described above, it would be desirable to have a simple fabrication technique for microstructures. Disclosed herein are example methods for fabricating microstructures, such as microsandwich structures. In some embodiments, a non-conductive polymer membrane comprising a plurality of elongated pores formed therein is coated with a conductive material, such as a metal, and a metal alloy, such as an aluminum (Al) alloy, is electrodeposited on the conductive material at room temperature in an ionic liquid electrolyte under galvanostatic control. In some embodiments, the composition (i.e., microstructure) of the alloy can be altered by changing the concentration of the alloyed metal present within the electrolyte.
In the following disclosure, various specific embodiments are described. It is to be understood that those embodiments are example implementations of the disclosed inventions and that alternative embodiments are possible. All such embodiments are intended to fall within the scope of this disclosure.
Disclosed in the following disclosure are methods for fabricating crystalline and amorphous alloy microstructures, such as microtube and microsandwich structures, using template electrodeposition. In some embodiments, the alloy comprises an alloy of Al and a transition metal that increases the strength of the metal. By way of example, the alloy can comprise an Al-manganese (Mn) alloy. The microstructures can be fabricated using a one-step electrodeposition process using a room temperature ionic liquid. The disclosed methods offer an opportunity to create Al alloy microstructures with low density, open architecture, and high specific strength and damage tolerance. Such microstructures can, for example, be used in applications as plasmonic pixels in color displays, anodes for lithium (Li) ion batteries, energy adsorbers, and the like.
Beginning with
With reference to
Next, the Al alloy can be electrodeposited on the conductive material. In some embodiments, the Al alloy is deposited using a one-step, three-electrode galvanostatic electrodeposition process in which the coated membrane 10 acts as the cathode or working electrode in the process. The coated membrane 10 can be placed in a room temperature ionic liquid electrolyte that contains Al and the other metal to be deposited on the copper coating through electrodeposition. In some embodiments, the electrolyte comprises a solution of AlCl3, 1-ethyl-3-methyl-imidazolium chloride (EMIC), and MnCl2. As described below, the microstructure of the Al alloy to be formed can depend upon the concentration of the alloyed metal (e.g., Mn) within the electrolyte. In some embodiments, the Al alloy can have a crystalline microstructure. In other embodiments, the Al alloy can have an amorphous microstructure.
With reference next to
Irrespective of whether microtubes or microrods are formed, the non-conductive polymer of the membrane 10 can next be removed, as indicated in
The process used to fabricate a microsandwich structure is similar to the process described above in relation to
With reference to
Next, referring to
The non-conductive polymer of the membrane 10 can next be removed, as indicated in
Structures of the types described above were fabricated using the above-described methods. Track-etched polycarbonate membranes (Cyclopre) having average nominal pore diameters of 5 μm were sputtered (CRC sputter coater, 99.99% argon (Ar), 5 mTorr) with a Cu layer of approximately 250 nm thickness on both sides of the membrane prior to electrodeposition. The electrodeposition was performed at room temperature using a three-electrode setup inside an Ar-filled glovebox (Mbraun Labstar, O2<1 ppm, H2O<1 ppm). Al wire (99.99%, Alfa Aesar) was used as the reference electrode. The Cu-coated polycarbonate membranes (working electrodes) were placed in the middle of two parallel Al anodes (99.99%, Alfa Aesar), enabling Al-Mn to be deposited from both ends of the pores. The ionic liquid electrolyte was made by mixing AlCl3 (anhydrous, 99.999%, Alfa Aesar) and EMIC (>98%, lolitec) in 2:1 molar ratio. As-received EMIC was dried under vacuum at 60° C. for at least 24 hours prior to mixing. The electrolyte was then purified using Al plate under agitation until a vanish yellow color was achieved. MnCl2 (98%, GFS Chemicals) was added to the electrolyte in different molarities and agitated for 24 hours. Galvanostatic electrodeposition was performed using Gamry Reference 600 potentiostat/galvanostat at 10 mA/cm2 for 1 hour. Finally, free-standing microsandwich structures were obtained by dissolving the polycarbonate membrane using dichloromethane.
Cyclic voltammetry experiments were performed on a tungsten wire (˜1 mm diameter) working electrode at a scan rate of 20 mV/s. The deposited structures were characterized using X-ray diffraction (XRD) (PANalytical X'Pert PRO), scanning electron microscopy (SEM) (Hitachi SU-70), and energy-dispersive X-ray spectroscopy (EDS) (EDAX-Phoenix). Cross-sections of the microsandwich structures were obtained by ion milling using focused ion beam microscopy (FIB) (FEI Quanta 200). Special care was taken to minimize gallium (Ga) contamination by using reduced current density during the final milling steps. Nanoindentation of the deposits was performed using a triboindenter (Hysitron, Ti900) with a diamond Berkovich tip (˜125 nm radius) at a 7 mN maximum load, a 1.4 mN/s loading/unloading rate, and a 2 second holding time. Micro-indentation (UMT-2, CETR) tests were performed using an alumina ball (4 mm diameter) tip under a constant normal load (varied from 20 to 25 N).
Mn2++2e−↔Mn, and (1)
4Al2Cl7−+3e−↔Al+7AlCl4− (2)
In the reverse scan, Al-Mn dissolution occurred at potentials higher than approximately 0.3 V versus Al/Al3+. Increasing [Mn2+] in the electrolyte shifted the reduction potential in the anodic direction and the dissolution potential in the cathodic direction. In addition, the current densities decreased by approximately 40% as [Mn2+] increased from 0.05 to 0.25 M. This is similar to that reported by others, who found that the addition of [Mn2+] inhibits the nucleation of Al. EDS (EDAX-Phoenix) analysis showed that increasing [Mn2+] from 0.05 to 0.25 M increased the Mn concentration in the deposits from 9.0±0.3 at. % to 26.2±0.4 at. %. During co-deposition of Al and Mn, the alloy composition is mainly governed by the concentrations of the electroactive species Al2Cl7− and Mn2+. [Al2Cl7−] strongly depends on the acidity of the electrolyte. Under Lewis base conditions (molar fraction of AlCl3<0.5), [Al2Cl7−] is close to zero (<10−7 M). Thus, maintaining a Lewis acid electrolyte is desirable for the deposition of an Al-Mn binary alloy. It should also be noted, however, that this condition is not necessary for Al-Mn deposition in inorganic chloroaluminate electrolyte systems in which the deposition can take place involving the discharge of Al2Cl4− in basic solution.
Al-Mn microsandwich structures were successfully electrodeposited from acidic AlCl3-EMIC-MnCl2 electrolyte contains 0.05 M [Mn2+] following the procedures described above in relation to
To evaluate the microsandwich growth kinetics, selected electrodeposition was carried out for 3 and 10 minutes using one Al plate as an anode. The deposited microstructures were free standing microtubes having various wall thicknesses. Typical SEM images of the microtubes are shown in
XRD results of the microtube and microsandwich structures are presented in
The hardness of the crystalline (Al-9 at. % Mn) and amorphous (Al-26 at. % Mn) deposits was 2.59±0.21 GPa and 6.14±0.35 GPa respectively, obtained using Oliver-Pharr method. Given the low density of Al alloys (ρAl-9Mn≈3.12 g/cm3 and ρAl-26Mn≈3.94 g/cm3) and the open architecture, the density of the microsandwich structures is estimated to be approximately 1.50 g/cm3 (relative density ρ=0.48) and 1.89 g/cm3 (relative density ρ=0.48) for the crystalline and amorphous structure respectively. The estimated specific strengths of the microsandwiches were between 277 and 520 kN·m/kg, which is well in excess of most commercial engineering alloys such as steel (130 kN·m/kg) and Ti-6Al-4V (240 kN·m/kg).
A preliminary study was performed to evaluate the impact damage resistance of the microsandwich structures under a 20 to 25 N normal load. It was observed that top plate cracks began to develop in the crystalline microsandwich at loads larger than approximately 22 N. On the other hand, large scale cracks were observed on the top plates of the amorphous microsandwich structures under all investigated loads.
During indentation of a microsandwich structure, the core yield load (P1) can be estimated as
where the core yield strength (σc, listed in Table 1) is calculated from nanoindentation hardness assuming a Tabor factor of three, the plate thickness t is 11 μm, the sample width b is 1 mm, the core thickness c is 27.6 μm, and the core-to-end plate elastic modulus ratio is approximately 1. The load for top plate fracture (P2) and the plastic zone size (2s, as defined in
and
Where
and
The calculated results are listed in Table 1. For the crystalline microsandwich structure, the predicted plate fracture load was 23.4 N, which is close to the crack initiation load measured experimentally (˜22 N). This load was also larger than the core yield load (18.2 N). Thus, extensive core compression occurred prior to plate crack formation. In addition, the predicted plastic zone size (300 μm) agrees well with the experimentally measured fracture size (dashed arc in
To gain a further understanding of the failure mechanism of the microsandwich structures, finite element analysis (FEA) was performed using Ansys Workbench over an area of 70×70 μm2 with pillars separated 10 μm apart. The dimensions of the microsandwich structure were taken from experimental measurements. Both Al-9 at. % Mn and Al-26 at. % Mn were assumed to be elastic-perfectly plastic with material properties listed in Table 1. The microsandwich structures were loaded at 0.81 N and subsequently unloaded to reproduce the experimentally measured displacement. The FEA results are shown in
From the foregoing disclosure, it can be appreciated that the crystallinity of the electrodeposited Al—Mn alloys of a microstructure can be tuned by controlling [Mn2+] in the electrolyte. Microsandwich pillars were found to grow along the radial direction of the template pores with tunable wall thickness by the deposition time. Given the flexibility and scalability of the electrodeposition process, the methods described herein present an interesting future direction for designing ultra-lightweight energy adsorbers with open architecture, high strength, and high damage resistance.
This application is a divisional application of U.S. Non-Provisional Application entitled “Electrodeposition Of Metal Microstructures,” having Ser. No. 14/935,398 and filed Nov. 7, 2015, and claims priority to U.S. Provisional Application Ser. No. 62/076,591, filed Nov. 7, 2014, both of which are hereby incorporated by reference herein in their entireties.
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20140170303 | Rayner | Jun 2014 | A1 |
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Number | Date | Country | |
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62076591 | Nov 2014 | US |
Number | Date | Country | |
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Parent | 14935398 | Nov 2015 | US |
Child | 15990888 | US |