Research Papers

Laser Induced Chemical Deposition of Ferrihydrite Nanotubes: Exploring Growth Rate and Crystal Structure

[+] Author and Article Information
Zhikun Liu

School of Industrial Engineering,
Purdue University,
West Lafayette, IN 47907
e-mail: liu332@purdue.edu

C. Richard Liu

Fellow ASME
School of Industrial Engineering,
Purdue University,
West Lafayette, IN 47907
e-mail: liuch@purdue.edu

Contributed by the Manufacturing Engineering of ASME for publication in the JOURNAL OF MICRO- AND NANO-MANUFACTURING. Manuscript received August 27, 2013; final manuscript received January 17, 2014; published online February 20, 2014. Assoc. Editor: Nicholas Fang.

J. Micro Nano-Manuf 2(1), 011001 (Feb 20, 2014) (6 pages) Paper No: JMNM-13-1066; doi: 10.1115/1.4026546 History: Received August 27, 2013; Revised January 17, 2014

This paper is one of three papers exploring and confirming a novel high rate nanomanufacturing method using laser to induce and accelerate chemical synthesis and deposition of nanotubes. We have shown elsewhere that the growth rate of SnO2 nanotubes by this method is a few orders faster than that by the state of the art electrochemical deposition method, the growth rate of the nanotubes is favorably affected by increasing the laser power under a constant number of scanning passes, and the process can grow nanotubes coalesced from ultrasmall particle size as small as 2 nm (Liu and Liu, 2013, "Laser Induced Chemical Solution Deposition of Nanomaterials: A Novel Process Demonstrated by Manufacturing SnO2 Nanotubes," Manuf. Lett., 1(1), pp. 42–35). In the second paper, we have shown that this novel method is generic, demonstrated by synthesizing various metal oxide and sulfide nanotubes (Liu and Liu, "Laser-Induced Solution Synthesis and Deposition: A Generic Method to Make Metal Chalcogenide Nanotubes at High Rate With High Consistency," J. Nanoeng. Nanosyst. (accepted)). Since the performance and properties of nanomaterials are highly dependent on its structure, we explore here how the basic processing variables affect the growth rate and crystal size. Our initial finding is that (1) the growth rate can be increased by increasing the pH value of the solution, resulting in little change on the crystal size and (2) the crystal size of the manufactured ferrihydrite nanotube arrays can be controlled by changing laser scanning passes. We found the increase of the pH value from 1.33 to 2.16 almost tripled the growth rate of ferrihydrite nanotubes, while the crystal size remained little changed as revealed by the transmission electron microscopy studies. However, increasing the number of laser scanning passes at a given power could coarsen the ferrihydrite nanocrystals. The crystal structure of the nanotubes could be converted to haematite by dry furnace annealing. These initial findings demonstrated the capability and controllability of the novel process.

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Grahic Jump Location
Fig. 2

Growth of ferrihydrite nanotubes by laser induced chemical deposition: (a) CCD camera photo of ferrihydrite line before the template is removed; (b) SEM image on the edge of the nanotube arrays after the removal of template; (c) and (d) SEM images of the ferrihydrite nanotubes taken from the area indicated by the circle in (b)

Grahic Jump Location
Fig. 3

The relationship between the pH value of the iron nitrate solution and the average height of the nanotubes after 11 laser scanning passes

Grahic Jump Location
Fig. 1

Schematic illustration of the laser induced chemical deposition of ferrihydrite nanotubes

Grahic Jump Location
Fig. 4

(a) and (b) TEM images of ferrihydrite nanotube synthesized under pH of 1.75 by 5 scanning passes; (c) SAED of the nanotube in (a); (d) and (e) nanotube synthesized at pH of 2.25 by 5 scanning passes; (f) SAED of the nanotube in (d)

Grahic Jump Location
Fig. 5

TEM images showing variation of ferrihydrite nanotube by prolonged laser scanning and dry furnace annealing: (a) and (b) nanotube synthesized at pH of 2.25 by 11 scanning passes; (c) SAED pattern of the nanotube in (a); (d) and (e) nanotube synthesized at pH of 2.16 by 13 scanning passes after dry annealing at 500 °C for 1 h; (f) SAED pattern of the annealed nanotube, indicating the haematite crystal structure



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