J. Am. Ceram. Soc.

, 88 [4] 1057–1059 (2005)

DOI: 10.1111/j.1551-2916.2005.00208.x

Journal
Hydration of Aluminum Powder in Magnesia-Containing Water
Shaowei Zhang,w Shinobu Hashimoto*, and William Edward Lee
*Department of Engineering Materials, The University of Sheffield, Sheffield S1 3JD, U.K.
Q1 Department of Materials Science and Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan

Small amounts (e.g. 0.25 wt%) of MgO in water greatly accel- of High Purity Chemicals, Japan) and Aldrich MgO powder
erate the hydration of Al powder, attributable to increased ba- (catalogue no. 30774-2) were used as the main raw materials.
sicity of the solution. This leads to dissolution of the native Al powder (B2 g), along with different amounts of MgO (0–4
Al2O3 film and early hydration products, decreasing the thick- wt% of Al amount), was immersed in B100 mL distilled water
ness of these protective layers and/or exposing new Al surface. preheated to 401C (in a glass beaker). Solution temperatures
The effect of this is exacerbated by additional heat released by were controlled to within 711C on a standard stirrer hotplate.
the accelerated hydration of Al and MgO. The significance of After hydration for 6 h, the hydrated powders were separated
this on the use of Al powder in refractories castable matrices is from the water by centrifuge and oven-dried 2 h at 801C.
discussed. The phases present on the Al powders before and after hy-
dration tests were examined by powder X-ray diffraction (XRD)
analysis. The spectra were recorded at 30 mA and 50 kV, using
I. Introduction Ni-filtered CuKa radiation. JCPDS cards used for identification
were Al (4-787), boehmite (21-1307), and bayerite Al(OH)3 (20-
A LUMINUM (Al) metal powder is used extensively as an ad-
ditive to both monolithic and shaped refractories, perform-
ing different functions in oxide- and carbon-based systems. In
11). The Al powders were also carbon coated and examined by
backscattered electron imaging (BEI) and secondary electron
oxide-based castables, it is used to improve spalling resistance imaging (SEI) modes in a Camscan Series 2A SEM (Obducat
because Al hydration leads to release of hydrogen, which in- CamScan, Waterbeach, U.K.) or in some cases in a JEOL 6400 Q2
(Tokyo, Japan) using its windowless energy-dispersive spectros- Q3
creases permeability,1 according to2
copy (EDS) detector (Oxford Instruments, Abingdon, U.K.). Q4
EDS analysis was performed in the SEM using a LINK detector Q5
2Al þ 6H2 O ¼ 2AlðOHÞ3 þ 3H2 (1)
(Oxford Instruments) and AN10000 package. To attempt to
quantify the extent of hydration, hydrated Al powders were also
2Al þ 4H2 O ¼ 2AlOOH þ 3H2 (2) mounted in cold setting resin, cross-sectioned, and polished. Af-
ter carbon coating, the Al/hydration product interface was ex-
2Al þ 3H2 O ¼ Al2 O3 ðgelÞ þ 3H2 (3) amined using SEM and EDS.

In carbon-containing refractories systems, however, Al powder

is used as an antioxidant to protect carbon from oxidation.3 In III. Results
this application, Al hydration is undesirable because it causes Al (1) Unhydrated Microstructure
to lose its effectiveness as an antioxidant. In both applications,
As-received Al metal powder (not shown) consists of both lath-
Al hydration warrants detailed investigation.
shaped and rounded particles up to 20 mm diameter, but with
Compared with extensive researches on the hydration be-
many o5mm diameter.
havior of Al foil or plate in pure water4,5 only a few studies have
investigated the hydration behavior of Al powder, of the kind
used for refractories castable systems.6–9 Nevertheless, they have (2) Hydrated Microstructure
highlighted several factors that could affect the hydration of Al XRD from Al powders after 6 h hydration at 401C in water
powder. As well as hydration temperature and time, the pres- containing 0–4 wt% MgO (Fig. 1) reveals no other crystal phas-
ence of other phases in the water, such as calcium aluminate es, except for bayerite Al(OH)3, although a small broad peak
cement (CAC), used extensively in castable systems as a binder between B101 and B171 was found. This small broad peak is
significantly accelerated Al hydration.8,9 likely because of formation of a small amount of amorphous
Besides CAC, other phases located in the pore water of casta- phases such as boehmite and Al2O3 gel, as indicated by reactions
ble systems could similarly affect Al hydration. It is thus the (2) and (3). Because the main objective of this paper is to com-
purpose of this paper to address the effect of magnesia (MgO), pare the relative hydration rate of Al in pure water and water
used extensively in both oxide- and carbon-based castables as containing different contents of MgO, rather than detailed anal-
grain phase or matrix fines.3,10 ysis of the hydration mechanism, no further characterization
of this amorphous phase was carried out. In the absence of
MgO, only small peaks of Al(OH)3 appeared (Fig. 1(a)). How-
II. Experimental Procedure ever, when 0.25 wt% MgO was present, Al(OH)3 peak heights
increased dramatically with a decrease in Al peak heights
Al powder (average particle size B10 mm, B99.9 wt% A1,
(Fig. 1(b)). On further increasing MgO content from 0.25 to
0.001% Cu, 0.08% Fe, and 0.06% Si, supplied by the Institute
4 wt%, Al(OH)3 peak heights increased gradually with a con-
comitant decrease in Al peak heights (Figs. 1(b)–(e)).
D. W. Johnson, Jr.—contributing editor Figure 2 reveals the morphology of some hydrated Al pow-
ders whose XRD are shown in Fig. 1. In the absence of MgO,
slightly roughened particle surfaces because of fine hydrate
Manuscript No. 10999. Received July 26, 2004; approved October 4, 2004. phases were observed (Fig. 2(a)). When MgO was present, for-
w
Author to whom correspondence should be addressed. e-mail: s.zhang@sheffield.ac.uk mation of hydration product phases became much more evident.
1057
1058 Communications of the American Ceramic Society Vol. 88, No. 4

BB hydration products formed and the agglomerates appeared to be

A B A B BA
B
disintegrating.
(e) The effect of MgO on hydration extent of Al can be further
revealed by BEI examination of cross-sections of the Al powders
Relative Intensity

after hydration (Fig. 3). Hydration product (gray contrast

(d) phase) and the remaining unhydrated Al (bright contrast phase)
were seen on all samples. In the absence of MgO, a small
amount of hydration product formed whereas a large amount
(c) of unhydrated Al remained (Fig. 3(a)). However, when 4 wt%
MgO was present, only small amounts of unhydrated Al re-
(b) mained whereas large amounts of lath-shaped or rounded hy-
dration product formed (Fig. 3(b)).
(a)
10 20 30 40 50 60 70 IV. Discussion
2 Theta
(1) Effect of MgO on Al Hydration
Fig. 1. X-ray diffraction of Al powders after 6 h hydration at 401C in
water containing 0–4 wt% MgO. (a) No MgO; (b) 0.25 wt% MgO; (c)
In the absence of MgO, only small Al(OH)3 peaks were found
0.5 wt% MgO; (d) 2 wt% MgO; (e) 4 wt% MgO (A—Al; B—Al(OH)3). by XRD, whereas high Al peaks remained (Fig. 1(a)). However,
when MgO was present, Al(OH)3 peak heights increase and Al
peaks decrease dramatically. Although XRD detected only one
As shown in Figs. 2(b) and (c), with increasing MgO from 0.25 crystal hydration product, Al(OH)3, and the exact chemical
to 4 wt%, more and more rounded or lath-shaped hydration identity of the amorphous hydration products has not been
products formed, randomly distributed to form porous agglom- identified, the fact that Al peaks decreased substantially with
erates. With MgO at 4 wt% (Fig. 2(c)), significant amounts of increasing level of MgO clearly indicates the accelerating effect
of MgO on Al hydration. This conclusion can be further sup-
ported by the hydrated microstructures shown in Figs. 2 and 3.
In the absence of MgO, only small amounts of hydration prod-
uct formed (Figs. 2(a) and 3(a)); however, when a small amount
(0.25 wt%) of MgO was present, more hydration products and
less unreacted Al were observed (Fig. 2(b)), and on increasing
MgO (4 wt%), the extent of hydration product formation was
significant (Figs. 2(c) and 3(b)).
As is well documented,11,12 a native Al2O3 film is always
formed on the surface of as-received Al in air. Because Al2O3
has a low solubility in pure water at near-neutral pH,13 the na-
tive film on the Al surfaces, without MgO in the water, would
act as a barrier between the Al and water, so water has to diffuse
through this film to initiate the hydration. After hydration start-
ed through the diffusion process, the hydration products such as
Al(OH)3 formed on the Al surface would continuously inhibit
the later stages of Al hydration. As a result, Al hydration in the
absence of MgO had been inhibited, resulting in a lower extent
of hydration (Figs. 1(a), 2(a), and 3(a)). On the other hand,
when MgO was present, the pH value of the water is much
higher (10–10.5).14 The increased pH increases the solubility of
Al2O3 or aluminum hydroxides (Al(OH)3 or AlOOH) in water,
according to reactions (4)–(6).15 As a result, the native film on
the as-received Al and the hydration product layer later formed
would be at least partially removed, decreasing the thickness of
the protective layers and/or exposing new surface area, which
would accelerate the Al hydration:

1=2Al2 O3 ðsÞ þ 3=2H2 O þ OH
ðaqÞ ¼ Al½OH

4 ðaqÞ (4)

AlðOHÞ3 ðsÞ þ OH
ðaqÞ ¼ Al½OH

4 ðaqÞ (5)

AlOOHðsÞ þ H2 O þ OH
ðaqÞ ¼ Al½OH

4 ðaqÞ (6)

Because the hydration reactions of Al and MgO are exothermic,

the initial accelerating effect of MgO on the Al hydration be-
cause of the increased pH would lead to release of more heat
than with no MgO present. This heat, along with that released
by hydration of MgO (especially at high levels, 4 wt%), would
increase the local temperature at the Al/water interface, accel-
erating the diffusion rate of water through the remaining pro-
tective layer resulting in more rapid Al hydration. This also
Fig. 2. Secondary electron imaging of Al powders after 6 h hydration at explains why when high levels (4 wt%) of MgO were present, a
401C in water containing 0–4 wt% MgO. (a) No MgO; (b) 0.25 wt% much greater extent of hydration was observed (Figs. 1(e), 2(c),
MgO; (c) 4 wt% MgO. and 3(b)).
April 2005 Communications of the American Ceramic Society 1059

Fig. 3. Backscattered electron imaging of polished surfaces of Al powders after 6 h hydration at 401C. (a) No MgO; (b) 4 wt% MgO.

(2) Significance of Effect of MgO on Al Hydration more difficult to use Al as an antioxidant for MgO–C castables,
In alumina-based castables, MgO is often used as matrix fine to so techniques to improve the hydration resistance of Al should
form in situ spinel.10 As shown in Figs. 1–3, the presence of even be developed. The accelerated hydration of Al will also adverse-
a small amount (0.25 wt%) of MgO could greatly accelerate Al ly affect the hydration of MgO, and thus affect, e.g. the castables
hydration, and the accelerating effect is greater with higher lev- flowing and setting behavior.
els of MgO. Therefore, the optimum amount of Al powder with
appropriate surface reactivity should thus be used in castable
matrices. For example, in castables using higher levels of MgO,
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