RES EARCH

NANOMATERIALS g-Al2O3 (21, 22). Nonequilibrium processes in-

volved in breaking and making chemical bonds
High-surface-area corundum by mechanochemically by mechanical energy input enable this phase
transformation to take place at room temper-
induced phase transformation of boehmite ature. However, g-Al2O3 undergoes continuous
agglomeration until it fully transforms to
Amol P. Amrute1*, Zbigniew Łodziana2, Hannah Schreyer1, Claudia Weidenthaler1, Ferdi Schüth1* a-Al2O3, which severely reduces the specific
surface area (by a factor of >2.2) (21).
In its nanoparticulate form, corundum (a-Al2O3) could lead to several applications. However, its The observed effect might be related to the
production into nanoparticles (NPs) is greatly hampered by the high activation energy barrier for its so-called “milling equilibrium” between cold
formation from cubic close-packed oxides and the sporadic nature of its nucleation. We report a simple welding, leading to the formation of larger
synthesis of nanometer-sized a-Al2O3 (particle diameter ~13 nm, surface areas ~140 m2 g−1) by the agglomerates, and fragmentation, producing
mechanochemical dehydration of boehmite (g-AlOOH) at room temperature. This transformation is smaller particles (23). The dominance of one
accompanied by severe microstructural rearrangements and might involve the formation of rare process over the other determines the even-
mineral phases, diaspore and tohdite, as intermediates. Thermodynamic calculations indicate that this tual size of the produced particles. As g-Al2O3
transformation is driven by the shift in stability from boehmite to a-Al2O3 caused by milling impacts on the is softer (bulk modulus, BVR = 196.9 GPa, and
surface energy. Structural water in boehmite plays a crucial role in generating and stabilizing a-Al2O3 NPs. shear modulus, GVR = 97.45 GPa; see table S1),
it could undergo excessive cold welding, which
would cease with the formation of harder a-Al2O3

C
orundum (a-Al2O3) in high-surface-area a loss in surface area, generally to values well (BVR = 239.6 GPa and G VR = 138.6 GPa), as

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nanoparticle (NP) form (1, 2) would enable
a number of applications. For example,
in auto-exhaust catalysis, gamma alumina
(g-Al2O3) is used in wash-coat formu-
lations, but a-Al2O3 has higher mechanical
stability and could be used directly as support
without wash coating if available as NPs (3, 4).
It could also provide improved hydrothermal
stability when water is present in the exhaust
gas. For ammonia synthesis, the presence of
a-Al2O3 in the catalyst formulation was shown
to increase catalyst activity by threefold (5).
Corundum is widely used in ceramic applica-
tions, including dental implants, prostheses, and
high-speed cutting tools, where high fracture
strength and toughness is desired (6, 7). The
use of nanoparticulate, fine-grained corundum
precursors would allow the manufacture of
ceramics with improved fracture toughness
and high density at reduced sintering temper-
atures, enabling energy savings (6, 7).
A number of studies—mostly theoretical
(1, 8–10) but a few experimental (1, 2)—have
addressed the thermodynamics and synthesis
of corundum NPs. However, none of the ef-
forts made has thus far resulted in a method
for the fabrication of high-purity corundum
with surface areas reaching or even exceeding
100 m2 g−1 (1, 2, 11). One reason for this lack of
success may be the high activation energy
barrier (485 kJ mol−1), requiring temperatures
above 1473 K, to facilitate a rearrangement of
oxide ions from the cubic close-packed struc-
ture found in transition aluminas to the hex-
agonally close-packed form in corundum
(Fig. 1, middle) (9, 12). This transition typical-
ly leads to substantial mass transfer during
the transformation that is associated with
1
Department of Heterogeneous Catalysis, Max-Planck-Institut
für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim
an der Ruhr, Germany. 2INP, Polish Academy of Sciences, ul.
Radzikowskiego 152, PL- 31-342 Kraków, Poland.
*Corresponding author. Email: amrute@kofo.mpg.de (A.P.A.);
schueth@kofo.mpg.de (F.S.)
below 10 m2 g−1.
Thermodynamic calculations coupled to ad-
sorption microcalorimetry and thermogravi-
metric analyses by Navrotsky et al. suggest that
at room temperature, g-Al2O3 could actually
be the thermodynamically most stable phase
for NPs, corresponding to surface areas of 100
to 200 m2 g−1 (1, 13). At 800 K, g-Al2O3 might
become stable even at lower surface areas.
Thus, a high-temperature process, which tends
to lead to the formation of the most stable
phase, should never lead to high-surface-area
a-Al2O3. However, density functional theory
simulations by Nørskov et al. showed that
the surface energy, and thus the stability, of an
alumina polymorph depends strongly on the
size of the crystallite and degree of hydrox-
ylation (9).
Accordingly, some hydroxylated surfaces of
alumina polymorphs, especially q-Al2O3, but
also a-Al2O3, should have negative surface
energies, and the nanocrystalline form of alu-
mina should become thermodynamically most
stable. In fact, a later study by Navrotsky et al.
also showed lower surface energy for the hy-
droxylated form of a-Al2O3 than for a similarly
hydroxylated g-Al2O3 irrespective of the surface
area (13). Hence, a-Al2O3 with a high surface
area >100 m2 g−1 could be accessible and syn-
thesizable, but numerous studies to date have
proven unsuccessful at producing it through
the thermal route at 1500 K.
The topotactic transformation of diaspore
(a-AlOOH) to a-Al2O3 produces corundum at
moderate temperatures of 800 to 873 K (Fig. 1,
top) (1, 14), but the synthesis of stable diaspore
requires very harsh conditions (723 K, 1200 bar,
35 days) (15, 16). Mechanochemical reactions
such as that induced by ball milling, which
finds increasing attention as a simple, eco-
nomical, and scalable method for the prep-
aration of nanomaterials and for carrying
out chemical reactions (17–20), have also been
reported as a method to obtain a-Al2O3 from
harder materials are difficult to cold weld and
also difficult to further fragmentize without
external aids.
We first approached this problem by perform-
ing ball milling of g-Al2O3 in the presence of
process control agents (PCAs), which are known
to limit cold welding and enhance fragmen-
tation (23). Stearic acid, alcohols, and heavier
alkanes are commonly used as PCAs (23). How-
ever, we opted for water as an environmentally
benign and cost-effective PCA. The ball-milling
experiments were performed in a vibration mill.
Typically, 1 g of precursor powder is charged
in the tungsten carbide (WC) vessel with three
WC balls (see section S2 of the supplementary
materials for more details). The effect of abra-
sion of milling balls, the vessel, or both caused
contamination of the samples with WC after
milling. WC was selectively removed by an
oxidative leaching step for all the samples ob-
tained using the WC milling jar and media
(supplementary text and fig. S1). Ball milling of
g-Al2O3 (denoted as g-Al2O3-1, SBET = 109 m2 g−1;
see fig. S2A for morphology) in the presence
of 1 to 5 weight % (wt %) H2O for 120 min
fully transformed the material into a-Al2O3,
but the surface area dropped to 70 m2 g−1 (fig.
S2B). This decrease in surface area is simi-
lar to its ball milling without water (fig. S2C).
A further increase in H2O to 15 wt % resulted
in no phase transformation of g-Al2O3, sug-
gesting that an excess amount of water in
the system is detrimental because it might
reduce the energy transfer during the mill-
ing impact.
These results suggest that high-surface-area
g-Al2O3 is a suitable precursor for the produc-
tion of a-Al2O3 with moderately high surface
area, but that alternative precursors might be
better. Ball milling was also reported to convert
boehmite to a-Al2O3 (24), but there is no in-
formation on the surface area, intermediates,
or agglomeration phenomena, and thus it re-
mains unclear whether boehmite could lead to

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RES EARCH | R E P O R T

Fig. 1. Methods for the synthesis of a-Al2O3.

In contrast to the harsh conditions needed in
conventional routes (top and middle), ball milling
(bottom) enables us to synthesize a-Al2O3 in
the nanoparticulate form at room temperature from
easily accessible boehmite precursors. Bottom
insets show the crystal structures (two-unit cells)
of boehmite [crystal system: orthorhombic; space
group: Cmcm (27)], diaspore [crystal system:
orthorhombic; space group: Pbnm (28)], tohdite
[crystal system: hexagonal; space group:
P63mc (10)], and a-Al2O3 [crystal system:
hexagonal-trigonal; space group: R3c no. 167 (29)]
along the c-axis. In boehmite, aluminum and oxygen
atoms form double layers of octahedra that
sandwich hydrogen atoms in a zigzag manner. The
diaspore structure consists of the “double rutile
strings” formed by the aluminum-centered oxygen
octahedra and involves hexagonal close packing
of the oxygen ions (AB-AB…). The tohdite structure

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is composed of oxygen planes stacked in the
sequence of A-B-A-C-A… and a unit cell contains
10 Al atoms, eight of which occupy octahedral and
two tetrahedral sites. In the a-Al2O3 structure,
each Al3+ center is octahedrally coordinated and
the oxygen ions form a hexagonal close-packed
structure with the aluminum ions filling two-thirds
of the octahedral interstices. Atom colors are as
follows: Al, blue; O, pink; and H, black.

Fig. 2. Evolution of the a-Al2O3 phase and changes in the surface area
upon ball milling of boehmite. (A) Diffractograms of g-AlOOH-1 before and
after ball milling at room temperature in the vibration mill. Milling conditions: WC
jar (25 cm3), 3 × 12 mm WC balls, 1 g of powder charge, fMill = 25 Hz, t = 10 to
720 min. Identified crystalline phases: }, g-AlOOH; , a-Al2O3; and 4, a-AlOOH.
(B) Surface area and hydrodynamic diameter of particles versus milling time for
g-AlOOH (circles) and g-Al2O3 (triangles) precursors. (C and D) TEM images of
60-min ball-milled g-AlOOH-1 (C) and 180-min ball-milled g-AlOOH-1 (D). The ball
milling of boehmite leads to the formation of a-Al2O3 with diaspore and/or
tohdite (fig. S4A) intermediates. The formation of the latter relies on the milling
conditions. The phase transformation to a-Al2O3 proceeds through severe
microstructural rearrangements.

high-surface-area corundum. Boehmite attracted
our interest also because it formally has one
water molecule in its structure per alumina
(i.e., 15 wt % water with respect to alumina)
and can be economically produced, for ex-
ample, by a modified Bayer process of bauxite
refining (25). With this material, an effective
milling impact can still be achieved, and the
structural water of boehmite, which will be
released upon its dehydration to alumina,
could act as a PCA to limit cold welding or to
facilitate the fragmentation of agglomerates.
On the basis of these considerations, we ball
milled a boehmite sample (denoted as g-AlOOH-1;
SBET = 89 m2 g−1; see fig. S3 for morphology)
for different times using a WC jar and media
(Fig. 2A). The boehmite phase remained mostly
unaltered upon ball milling for up to 30 min,

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RES EARCH | R E P O R T

Fig. 3. Free energy of g-Al2O3 and g-AlOOH

with respect to a-Al2O3 as a function
of surface area at standard state
(T = 298.15 K and P = 1 bar). Data in
(A) correspond to the conditions discussed
in (1), where at high surface area, g-Al2O3 is
thermodynamically more stable than a-Al2O3.
(B) Modification of boehmite surface in the
milling process effectively increases the surface
energy of this compound (above 4 J m−2; fig. S7),
which drives the conversion to a-Al2O3 above
108 m2 g−1. (C) Alumina surface hydroxylation
changes the mutual stability of the phases, where
a-Al2O3 becomes the most stable phase above
52 m2 g−1. For the corresponding data for
diaspore and tohdite, see figs. S8 and S9.

Table 1. Surface area, phase composition, and domain size of boehmite before and after ball milling using a WC jar and media in the vibration mill

Downloaded from http://science.sciencemag.org/ on October 24, 2019

and after calcination of the ball-milled sample.

Entry Sample Before milling After 180 min of milling* After calcination of the milled sample at 823 K
−1 −1
2
SBET (m g ) Phase† Domain size (nm)‡ SBET (m g ) 2
Phase SBET (m2 g−1) Phase Domain size (nm)
g-AlOOH-1
1............................................................................................................................................................................................................................................................................................................................................
89 b 17 125 c+d 120 c 18
g-AlOOH-2
2............................................................................................................................................................................................................................................................................................................................................
64 b 20 115 c+d 136 c 18
3 g-AlOOH-3 10 b 52 103 c+d 130 c 19
............................................................................................................................................................................................................................................................................................................................................
4 g-AlOOH-4, dried 366 b 4 132 c + d 140 c 18
............................................................................................................................................................................................................................................................................................................................................

*Other ball-milling conditions can be found in the legend to Fig. 2A. †Identified crystalline phases: b, boehmite; d, diaspore; and c, corundum. ‡Domain size determined by the
application of the Scherrer equation to the corresponding XRD pattern (see section S3 in the supplementary materials for more details).

but x-ray diffraction (XRD) reflections corre- after 180 min of milling can be topotactically order g-AlOOH > a-Al2O3 > g-Al2O3 and above
sponding to a-Al2O3 and a-AlOOH appeared converted to a-Al2O3 by a mild calcination at a surface area of 190 m2 g−1, g-Al2O3 becomes
after 60 min of milling. Further continuation 823 K; Fig. 2A, green diffractogram). This re- more stable than corundum. This trend agrees
of milling for 180 min fully converted boehmite sult indicates that the conversion of these phases with those reported for these alumina poly-
to a mixture of corundum (major, ~70 to 80%) is slower compared with that of boehmite, morphs (13). Assuming that water vacancies
and diaspore (minor, ~20 to 30%). Similar re- likely because they are mechanically harder are the primary defects among others (see sec-
sults were obtained upon ball milling of boehmite (table S1). Increased milling frequency (30 Hz) tion S4 in the supplementary materials), the
with a steel milling jar and media (fig. S4A), ex- led to a faster transformation of boehmite and modification of g-AlOOH by ball milling effect-
cept instead of diaspore, another mineral phase, intermediates to a-Al2O3 (fig. S4B and table S2). ively increases its surface energy and reverses
tohdite (5Al2O3·H2O, which is structurally sim- These results show that the formation of the mutual stability orders as follows: a-Al2O3 >
ilar to a-Al2O3, see Fig. 1, bottom insets, and intermediates depends on the milling condi- g-AlOOH > g-Al2O3 (Fig. 3, B and C, and fig. S7).
rearranges to the latter upon dehydration), tions and that high impact energy favors the At a surface area >108 m2 g−1 for the anhydrous
was detected. nucleation of the a-Al2O3 phase. This finding state and 52 m2 g−1 for the hydroxylated state,
The observation of these rare phases by ball was substantiated by ball milling of boehmite a-Al2O3 becomes the thermodynamically most
milling of boehmite was surprising because their in the planetary mill using steel, sintered corun- stable phase, which provides the driving force
formation normally requires extremely harsh dum, or zirconia milling jars and media. The for the boehmite-to-corundum transformation.
conditions (16, 26). However, in view of the higher impact and friction forces involved in Mechanochemical conversion is a nonequi-
thermodynamic analysis (see below), the for- planetary milling led to the direct formation of librium process in which intermediates can be
mation of such phases is possible for the high- a-Al2O3 (see fig. S6). Notably, milling equip- observed. Comparison of the surface energies
surface-area systems, which was confirmed by ment made of corundum can also be used to of diaspore and tohdite with boehmite and
performing experiments under variable condi- exclude the presence of any foreign material corundum suggests that boehmite has the
tions (fig. S5). In the ball milling of g-Al2O3, no by abrasion. largest thermodynamic driving force for its
intermediate phase was observed (21, 22), which We obtained deeper insight into the phase conversion under our milling conditions (figs.
we confirmed by milling g-Al2O3-1 for different transformation discussed above from the thermo- S8C and S9). Thus, intermediate phases such
times (fig. S2C). dynamic analysis of the involved phases (see as diaspore or tohdite could also form, to-
Ball milling of boehmite for 720 min led to section S4 of the supplementary materials). gether with the most stable a-Al2O3. Diaspore
the formation of pure a-Al2O3 (Fig. 2A and At standard state, g-AlOOH should be the most or tohdite would also ultimately convert to
fig. S4A), showing that these intermediates can stable phase irrespective of the surface area a-Al2O3, but the driving force for their con-
also be transformed to the desired corundum (Fig. 3A and table S3). For the dense bulk phases, version is lower and requires longer times or
phase (alternatively, the remaining diaspore the thermodynamic stability decreases in the higher milling intensity.

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Fig. 4. Properties of nanoparticulate a-Al2O3 derived by ball milling of boehmite. (A) TEM and (B and C) high-resolution TEM of nanoparticulate a-Al2O3
obtained by 180-min ball milling of g-AlOOH-1, followed by calcination at 823 K. (D) Particle size (dParticle) distribution from TEM images of nanoparticulate a-Al2O3.
(E) Pore size distribution determined by the application of density functional theory model to the N2 isotherm. Inset in (E) shows N2 adsorption-desorption isotherms.
Ball-milling–derived a-Al2O3 from boehmite is composed of rounded NPs (dParticle = 13 nm) with surface roughness and defects and pores in the range of 3 to 10 nm.

To determine whether these phase changes
involve agglomeration, fragmentation, or both
phenomena, we further characterized the ball-
milled boehmite and g-Al2O3 samples. The sur-
face area gradually decreased with milling time
for g-Al2O3 and reached a plateau after 120 min
(full conversion to a-Al2O3; Fig. 2B). This result
is in agreement with previous work (21). Like-
wise, boehmite also displayed a loss in surface
area during the first 60 min of milling, which
suggests that agglomeration was also promi-
nent for boehmite in the initial phase of milling.
A faster decrease in surface area for boehmite
compared with g-Al2O3 likely reflects their dif-
ferent mechanical properties (table S1); boeh-
mite is softer and prone to cold weld faster
than g-Al2O3.
However, in contrast to g-Al2O3, the surface
area was recovered after 60 min for the boeh-
mite precursor (Fig. 2B; see table S2 for steel
milling jar and media). To understand this
difference, the samples were characterized by
dynamic light scattering (Fig. 2B). An increase
in the hydrodynamic diameter during the first
hour of milling and a subsequent decrease upon
further milling indicated that the sample was
agglomerated during the first hour of milling,
and then these agglomerates were fragmented
into smaller NPs. This process was visualized
by transmission electron microscopy (TEM)
analysis (Fig. 2, C and D). Agglomeration of
the sample milled for 60 min was seen, and
finely rounded NPs were detected after 180 min
of milling. Thus, the structural water in boeh-
mite seems to play a crucial role in generating
and stabilizing the corundum NPs. Water re-
leased during the dehydration of boehmite to
a-Al2O3 could create fissures in the agglomer-
ates that facilitate their disintegration during
milling, and the formed NPs of a-Al2O3 would
be stabilized through hydroxylation of the sur-
face by the released water. Hydroxylation has
been demonstrated to lower the surface energy
of a-Al2O3 (13). Further evidence highlighting
the effect of structural water was derived by
ball milling of boehmite at elevated temper-
atures (373 to 473 K) (fig. S10).
The a-Al2O3 NPs derived by ball milling using
WC jar and balls, followed by mild calcination,
were further characterized in depth (Fig. 4).
TEM images showed that the NPs ranged in
size from 4 to 32 nm, with an arithmetic aver-
age particle size (dParticle) of 13 nm (standard
deviation = 6 nm) (Fig. 4, A and D). The domain
size determined by the application of the
Scherrer equation to the corresponding XRD
pattern was 18 nm (Table 1). High-resolution
TEM showed that the NPs display a crystalline
rather than an amorphous surface (Fig. 4B).
Determination of the d spacing at different
spots provided an average value of 2.079 Å,
which agrees well with the 2.085 Å d spacing
for the (113) plane of a-Al2O3.
The TEM images also showed some irregu-
larity, surface roughness, or defects as well as
some pores on the NPs (Fig. 4C). Pore size deter-
mined from N2 sorption analysis using the den-
sity functional theory model indicated that pores
in the size range from 3 to 10 nm were present
(Fig. 4E), which might include a contribution
from interparticle pores. The surfaces were also
highly dehydrated (fig. S11). Thus, the observed
surface area can be attributed to nanometer-
sized particles and a combination of surface
roughness, defects, and pores. Similar results
were obtained for other boehmite precursors
of a different nature (i.e., different particle size,
surface area, and water contents; see Table 1,
figs. S12 to S14, and corresponding captions). In
all cases, full boehmite conversion was achieved
after 180 min of milling, with surface areas for
a-Al2O3 exceeding 130 m2 g−1.
Boehmite and related compounds were found
to be highly effective and economically accessible

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RES EARCH | R E P O R T
precursors to produce phase-pure nanocrys-
talline a-Al2O3 with surface areas exceeding
120 m2 g−1 through mechanochemistry. These
results may have high practical relevance, for
instance, for the optimization of alumina pro-
cessing in ceramics and for the design of stable
industrial catalysts (e.g., as supports for auto-
motive or Fischer–Tropsch synthesis catalysts).
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ACKN OWLED GMEN TS
The electron microscopy department at the Max-Planck-Institut für
Kohlenforschung is gratefully acknowledged for the electron
microscopy and the EDX analyses. We thank G. Prieto for providing
boehmite samples (g-AlOOH-1 and g-AlOOH-4). PL-Grid is
acknowledged for CPU allocation. Funding: Max-Planck-Institut für
Kohlenforschung is acknowledged for financial support. Author
contributions: F.S. conceived the idea of investigating ball milling
to produce high-surface-area a-Al2O3. A.P.A. and F.S. designed a
strategy to study boehmite compounds. A.P.A. synthesized the
starting materials for ball milling, designed and executed ball-
milling experiments, and performed characterizations. Z.Ł.
formulated the thermodynamic model, performed the
calculations of elastic and thermodynamic properties, and
wrote the corresponding part of the text. H.S. first detected
the transformation of g-Al2O3 to a-Al2O3 in experiments
to synthesize supported catalysts in the ball mill and performed
some of the experiments involving ball milling of g-Al2O3.
C.W. assisted in the measurement of selected samples on a
PANalytical X'Pert Pro diffractometer and performed
Rietveld refinement of selected samples. A.P.A. and F.S.
wrote the manuscript. All authors commented on the
manuscript. Competing interests: The authors have filed
a patent application on the synthesis process to obtain
high-surface-area alpha-alumina. Data and materials
availability: All data are available in the main text or
the supplementary materials.
SUPPLEMENTARY MATERIALS
science.sciencemag.org/content/366/6464/485/suppl/DC1
Materials and Methods
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Supplementary Text
Figs. S1 to S14
Tables S1 to S3
References (30–40)
14 March 2019; resubmitted 22 July 2019
Accepted 27 September 2019
10.1126/science.aaw9377
5 of 5
High-surface-area corundum by mechanochemically induced phase transformation of
boehmite
Amol P. Amrute, Zbigniew Lodziana, Hannah Schreyer, Claudia Weidenthaler and Ferdi Schüth

Science 366 (6464), 485-489.

DOI: 10.1126/science.aaw9377

Milling corundum nanoparticles

High-purity corundum (α-Al2O3) nanoparticles could enable applications such as more stable catalyst supports or
precursors for high-strength ceramics. Milling of corundum only produces micrometer-scale particles, and direct
synthesis from other aluminum oxides that would be likely starting materials, such as γ-Al2O3, fails because of the high

Downloaded from http://science.sciencemag.org/ on October 24, 2019

activation barrier for converting the lattice structure of these cubic close-packed oxides. Amrute et al. show that ball
milling of boehmite, γ-AlOOH, created ∼13-nanometer-diameter corundum nanoparticles of high purity through a
mechanically induced dehydration reaction and by the effect of milling impacts on the surface energy of the particles.
Science, this issue p. 485

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REFERENCES This article cites 38 articles, 4 of which you can access for free
http://science.sciencemag.org/content/366/6464/485#BIBL

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