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Research Article | Open Access

The effect of milling additives on powder properties and sintered body microstructure of NiO

Department of Chemistry, New York City College of Technology, City University of New York,300 Jay St., Brooklyn, NY 11201, USA
The Air Force Research Labs, Wright-Patterson Air Force Base, OH 45433, USA
Department of Chemistry, Villanova University, 800 E. Lancaster Ave., Villanova, PA 19085, USA
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The evolution of powder particle size, crystal structure, and surface chemistry was evaluated for micron scale NiO powders subjected to impact milling with commonly employed milling additives: methanol, Vertrel XF, and amorphous carbon. The effect of the different comminution protocols on sintered body microstructure was evaluated for high temperature sintering in inert atmosphere (N2). X-ray photoelectron spectroscopy showed that NiO powder surface chemistry is surprisingly sensitive to milling additive choice. In particular, the proportion of powder surface defect sites varied with additive, and methanol left an alcohol or alkoxy residue even after drying. Upon sintering to intermediate temperatures (1100 ℃), scanning electron microscopy (SEM) showed that slurry milled NiO powders exhibit hindered sintering behaviors. This effect was amplified for NiO milled with methanol, in which sub-500 nm grain sizes dominated even after sintering to 1100 ℃. Upon heating to high temperatures (1500 ℃), simultaneous differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) showed that the powders containing carbon residues undergo carbothermal reduction, resulting in a melting transition between 1425 and 1454 ℃. Taken together, the results demonstrated that when processing metal oxide powders for advanced ceramics, the choice of milling additive is crucial as it exerts significant control over sintered body microstructure.


Adams TA, Nease J, Tucker D, et al. Energy conversion with solid oxide fuel cell systems: A review of concepts and outlooks for the short- and long-term. Ind Eng Chem Res 2013, 52:3089-3111.
Cowin PI, Petit CTG, Lan R, et al. Recent progress in the development of anode materials for solid oxide fuel cells. Adv Energ Mater 2011, 1:314-332.
Clemmer RMC, Corbin SF. The influence of pore and Ni morphology on the electrical conductivity of porous Ni/YSZ composite anodes for use in solid oxide fuel cell applications. Solid State Ionics 2009, 180:721-730.
Guo W, Liu J. The effect of nickel oxide microstructure on the performance of Ni–YSZ anode-supported SOFCs. Solid State Ionics 2008, 179:1516-1520.
Itoh H, Yamamoto T, Mori M, et al. Configurational and electrical behavior of Ni–YSZ cermet with novel microstructure for solid oxide fuel cell anodes. J Electrochem Soc 1997, 144:641-646.
Wang Y, Walter ME, Sabolsky K, et al. Effects of powder sizes and reduction parameters on the strength of Ni–YSZ anodes. Solid State Ionics 2006, 177:1517-1527.
Jiang SP. Sintering behavior of Ni/Y2O3–ZrO2 cermet electrodes of solid oxide fuel cells. J Mater Sci 2003, 38:3775-3782.
Wilson JR, Barnett SA. Solid oxide fuel cell Ni–YSZ anodes: Effect of composition on microstructure and performance. Electrochem Solid-State Lett 2008, 11:B181-B185.
Cho HJ, Choi GM. Effect of milling methods on performance of Ni–Y2O3-stabilized ZrO2 anode for solid oxide fuel cell. J Power Sources 2008, 176:96-101.
Hong HS, Chae U-S, Choo S-T. The effect of ball milling parameters and Ni concentration on a YSZ-coated Ni composite for a high temperature electrolysis cathode. J Alloys Compd 2008, 449:331-334.
Restivo TAG, de Mello-Castanho SRH. Nickel–zirconia cermet processing by mechanical alloying for solid oxide fuel cell anodes. J Power Sources 2008, 185:1262-1266.
Tietz F, Dias FJ, Simwonis D, et al. Evaluation of commercial nickel oxide powders for components in solid oxide fuel cells. J Eur Ceram Soc 2000, 20:1023-1034.
Bowen P, Carry C. From powders to sintered pieces: Forming, transformations and sintering of nanostructured ceramic oxides. Powder Technol 2002, 128:248-255.
Chaim R, Levin M, Shlayer A, et al. Sintering and densification of nanocrystalline ceramic oxide powders: A review. Adv Appl Ceram 2008, 107:159-169.
Koch CC. The synthesis and structure of nanocrystalline materials produced by mechanical attrition: A review. Nanostruct Mater 1993, 2:109-129.
Jung S-H, Oh H-C, Kim J-H, et al. Pretreatment of zirconium diboride powder to improve densification. J Alloys Compd 2013, 548:173-179.
Castro RHR, Pereira GJ, Gouvêa D. Surface modification of SnO2 nanoparticles containing Mg or Fe: Effects on sintering. Appl Surf Sci 2007, 253:4581-4585.
Phung X, Groza J, Stach EA, et al. Surface characterization of metal nanoparticles. Mat Sci Eng A 2003, 359:261-268.
Burda C, Chen X, Narayanan R, et al. Chemistry and properties of nanocrystals of different shapes. Chem Rev 2005, 105:1025-1102.
Eser O, Kurama S. The effect of the wet-milling process on sintering temperature and the amount of additive of SiAlON ceramics. Ceram Int 2010, 36:1283-1288.
Ivanov E, Suryanarayana C. Materials and process design through mechanochemical routes. J Mater Synth Proces 2000, 8:235-244.
Koch CC, Cho YS. Nanocrystals by high energy ball milling. Nanostruct Mater 1992, 1:207-212.
Zhang DL. Processing of advanced materials using high-energy mechanical milling. Prog Mater Sci 2004, 49:537-560.
Lu K, Liang Y, Li W. Hindered sintering behaviors of titania nanoparticle-based materials. Mater Lett 2012, 89:77-80.
Faudot F, Gaffet E, Harmelin M. Identification by DSC and DTA of the oxygen and carbon contamination due to the use of ethanol during mechanical alloying of Cu–Fe powders. J Mater Sci 1993, 28:2669-2676.
Peck MA, Langell MA. Comparison of nanoscaled and bulk NiO structural and environmental characteristics by XRD, XAFS, and XPS. Chem Mater 2012, 24:4483-4490.
Biesinger MC, Payne BP, Lau LWM, et al. X-ray photoelectron spectroscopic chemical state quantification of mixed nickel metal, oxide and hydroxide systems. Surf Interface Anal 2009, 41:324-332.
Barr TL, Seal S. Nature of the use of adventitious carbon as a binding energy standard. J Vac Sci Technol A 1995, 13:1239-1246.
Jang HD, Kim S-K, Kim S-J. Effect of particle size and phase composition of titanium dioxide nanoparticles on the photocatalytic properties. J Nanopart Res 2001, 3:141-147.
Sánchez LC, Arboleda JD, Saragovi C, et al. Magnetic and structural properties of pure hematite submitted to mechanical milling in air and ethanol. Physica B 2007, 389:145-149.
Spearing DR, Huang JY. Zircon synthesis via sintering of milled SiO2 and ZrO2. J Am Ceram Soc 1998, 81:1964-1966.
Zhou S, Chen H, Ding C, et al. Effectiveness of crystallitic carbon from coal as milling aid and for hydrogen storage during milling with magnesium. Fuel 2013, 109:68-75.
Huang ZG, Guo ZP, Calka A, et al. Effects of carbon black, graphite and carbon nanotube additives on hydrogen storage properties of magnesium. J Alloys Compd 2007, 427:94-100.
Richardson JT, Yiagas DI, Turk B, et al. Origin of superparamagnetism in nickel oxide. J Appl Phys 1991, 70:6977.
Gonçalves NS, Carvalho JA, Lima ZM, et al. Size–strain study of NiO nanoparticles by X-ray powder diffraction line broadening. Mater Lett 2012, 72:36-38.
Biesinger MC, Payne BP, Grosvenor AP, et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl Surf Sci 2011, 257:2717-2730.
Payne BP, Grosvenor AP, Biesinger MC, et al. Structure and growth of oxides on polycrystalline nickel surfaces. Surf Interface Anal 2007, 39:582-592.
McIntyre NS, Cook MG. X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper. Anal Chem 1975, 47:2208-2213.
Uhlenbrock S, Scharfschwerdt C, Neumann M, et al. The influence of defects on the Ni 2p and O 1s XPS of NiO. J Phys: Condens Matter 1992, 4:7973.
Payne BP, Biesinger MC, McIntyre NS. Use of oxygen/nickel ratios in the XPS characterisation of oxide phases on nickel metal and nickel alloy surfaces. J Electron Spectrosc Relat Phenom 2012, 185:159-166.
Jung J, Kim DL, Oh SH, et al. Stability enhancement of organic solar cells with solution-processed nickel oxide thin films as hole transport layers. Sol Energy Mater Sol Cells 2012, 102:103-108.
Rocha TCR, Oestereich A, Demidov DV, et al. The silver–oxygen system in catalysis: New insights by near ambient pressure X-ray photoelectron spectroscopy. Phys Chem Chem Phys 2012, 14:4554-4564.
Au CT, Hirsch W, Hirschwald W. Adsorption and interaction of methanol with zinc oxide: Single crystal faces and zinc oxide–copper catalyst surfaces studied by photoelectron spectroscopy (XPS and UPS). Surf Sci 1989, 221:113-130.
Deiner LJ, Serafin JG, Friend CM, et al. Insight into the partial oxidation of propene: The reactions of 2-propen-1-ol on clean and O-covered Mo(110). J Am Chem Soc 2003, 125:13252-13257.
Iida Y. Sintering of high-purity nickel oxide. J Am Ceram Soc 1958, 41:397-406.
Arico E, Tabuti F, Fonseca FC, et al. Carbothermal reduction of the YSZ–NiO solid oxide fuel cell anode precursor by carbon-based materials. J Therm Anal Calorim 2009, 97:157-161.
Haynes WN. CRC Handbook of Chemistry and Physics. Boca Raton, FL:CRC Press/Taylor and Francis, 2014.
Natile MM, Glisenti A. Surface reactivity of NiO: Interaction with methanol. Chem Mater 2002, 14:4895-4903.
Shiau F-S, Fang T-T, Leu T-H. Effects of milling and particle size distribution on the sintering behavior and the evolution of the microstructure in sintering powder compacts. Mater Chem Phys 1998, 57:33-40.
Journal of Advanced Ceramics
Pages 142-151
Cite this article:
DEINER LJ, ROTTMAYER MA, EIGENBRODT BC. The effect of milling additives on powder properties and sintered body microstructure of NiO. Journal of Advanced Ceramics, 2015, 4(2): 142-151.








Web of Science






Received: 15 December 2014
Revised: 26 February 2015
Accepted: 27 February 2015
Published: 30 May 2015
© The author(s) 2015

Open Access: This article is distributed under the terms of the Creative Commons Attribution License which permits any use, distribution, and reproduction in any medium, provided the original author(s) and the source are credited.