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Journal of Advanced Ceramics  2015, Vol. 4 Issue (2): 142-151    doi: 10.1007/s40145-015-0147-z
Research Article     
The effect of milling additives on powder properties and sintered body microstructure of NiO
aDepartment of Chemistry, New York City College of Technology, City University of New York,300 Jay St., Brooklyn, NY 11201, USA
bThe Air Force Research Labs, Wright-Patterson Air Force Base, OH 45433, USA
cDepartment 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.

Key wordsnickel oxide      impact milling      sintering      densification      grain growth     
Received: 15 December 2014      Published: 15 April 2015
Corresponding Authors: L. Jay DEINER   
Cite this article:

L. Jay DEINER,Michael A. ROTTMAYER,Bryan C. EIGENBRODT. The effect of milling additives on powder properties and sintered body microstructure of NiO. Journal of Advanced Ceramics, 2015, 4(2): 142-151.

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NiO/C (1.5%)Printex L amorphous carbon, 1.5 wt%
NiO/methanolMethanol (Sigma Aldrich, Anhydrous, 99.8%)
NiO/VertrelVertrel XF (1,1,1,2,2,3,4,5,5,5-decafluoropentane, DuPont)
Table 1 Summary of the samples and milling conditions employed for grinding NiO
SampleMilling time (min)BET surface area (m2/g)BET average particle size (nm)
NiO/C (1.5%)48016.854
Table 2 BET surface areas and estimated particle sizes of NiO powders before and after 480 min of milling
Fig. 1 SEM images of NiO powders after: (a) no milling; (b) 480 min of milling with no additive; (c) 480 min of milling with 1.5% Printex L carbon; (d) 480 min of milling with Vertrel XF; and (e) 480 min of milling with methanol.
Fig. 2 X-ray diffraction data for: (a) unmilled NiO; (b) NiO slurry milled in methanol; (c) NiO slurry milled in Vertrel; (d) dry milled NiO; and (e) NiO dry milled with carbon.
Fig. 3 X-ray photoelectron spectroscopy data for the (a) Ni 2p3/2 region and (b) O 1s region of: (i) unmilled NiO; (ii) NiO milled for 480 min with no additive; (iii) NiO milled for 480 min with carbon Printex L; (iv) NiO milled for 480 min with Vertrel XF; and (v) NiO milled for 480 min with methanol.
Unmilled NiONiO milled with no additiveNiO milled with Printex carbonNiO milled with VertrelNiO milled with methanol
Binding energy (eV)529.4529.5529.5529.4529.4
AssignmentLattice oxygenLattice oxygenLattice oxygenLattice oxygenLattice oxygen
Binding energy (eV)531.0531.2531.1530.7531.2
AssignmentDefect oxygenDefect oxygenDefect oxygenDefect oxygenDefect oxygen, alkoxy, OH
Binding energy (eV)528.5528.5
FWHM (eV)1.92.2
AssignmentNon-equilibrium oxygenNon-equilibrium oxygen
Binding energy (eV)533.5
FWHM (eV)1.6
Table 3 Peak fits for the O 1s region of X-ray photoelectron spectroscopy data for NiO before and after undergoing high energy milling treatments
Fig. 4 SEM images of NiO powders sintered in N2 to (a) 1100 ℃ and (b) 1500 ℃. Powders are: (i) NiO unmilled; (ii) NiO milled for 480 min with carbon; (iii) NiO milled for 480 min with methanol; and (iv) NiO milled for 480 min with Vertrel XF.
Fig. 5 (a) Thermogravimetric analysis and (b) differential scanning calorimetry for unmilled NiO (black line), NiO milled with carbon (black line + triangle symbols), NiO milled with methanol (black line + circle symbols), and NiO milled with Vertrel XF (black line + square symbols). In the differential scanning calorimetry traces, exothermic events produce an upward peak.
Fig. 6 Temperature derivative of the weight corrected heat flow from differential scanning calorimetry measurements of unmilled NiO (black line), NiO milled with carbon (black line + triangle symbols), NiO milled with methanol (black line + circle symbols), and NiO milled with Vertrel XF (black line + square symbols) for the temperature ranges of (a) 100–900 ℃ and (b) 1200–1500 ℃. Inset in (b): derivative of the weight corrected heat flow for NiO/C and NiO/methanol (as labeled) in both the forward and reverse scans. The NiO/methanol trace has been multiplied by four in order to be visible on the same scan as the NiO/C trace.
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