Journal of Crystal Growth 41(1977) 228234

North-Holland Publishing Company

EFFECT OF pH ON THE GROWTH OF Mg(OH)2 CRYSTALS IN AN AQUEOUS ENVIRONMENT AT 60C

V.A. PHILLIPS, J.L. KOLBE and H. OPPERHAUSER

Martin Marietta Laboratories, Baltimore, Maryland 21227, USA

Received 13 January 1977; manuscript received in final form 15 May 1977

Magnesium hydroxide was precipitated at 60Cat various constant pH levels in the range 8.7 to 12.5 from magnesium chloride
and ammonium (or sodium) hydroxide. The particles of 0.050.30 pm diameter were characterized by transmission electron
microscopy, electron diffraction, and surface area measurements. Increase in pH in the range 9.0 to 11.0 favored edgewise growth
of the platelets. Decrease in pH tended to decrease the diameter to thickness ratio and surface area of the platelets, culminating in
a change in shape to dense equiaxed particles with a stacked-plate morphology at pH 8.75, where excess magnesium chloride
was present, and the growth rates in the c- and a-directions were nearly equal. At pH 10.0, nearly circular plates with indented
outline were observed, whereas,
2~ions at somewhat
affected the growthhigher
rate inor lower pH, direction
a particular the plates were hexagonal
differently, causinginchanges
shape. The results
in shape, indicated
and that
diameter to
excess 0Hratio.
thickness or Nucleation
Mg appeared easier at higher pH.

1. Introduction ditions of sparing solubility, as encountered in com-

A preliminary account of this work has been given
by the authors [I]. The precipitation of magnesium
hydroxide is of great interest in connection with the
manufacture of magnesium oxide from magnesium
chloride contained in seawater [2,3] or natural brines
[3}. Lime slaked to calcium hydroxide is employed as
the precipitating agent, however, in practice it is
advantageous to employ dolime (CaO MgO), which
provides an additional source of magnesium, the mag-
nesium oxide being slaked to hydroxide. Since a
variety of shapes of magnesium hydroxide particles
occur in practice, there is a need to understand the
factors affecting cyrstal growth. The present experi-
ments were carried out using a simple model system,
in order to provide a basis for experiments of
increasing complexity approaching conditions
encountered in practice.
It is well known [47] that crystal shape can be
modified by changing crystallization conditions, such
as the solvent used, supersaturation, temperature, pH,
specific impurity levels, degree of stirring, and by the
mercial magnesium hydroxide production.
There appears to have been no work on the
morphology of magnesium hydroxide precipitated at
elevated temperatures. Murotani and Shirasaki [8]
precipitated Mg(OH)
2 by adding ammonia to a mixed
solution of MgC12 and NH4C1 at 10Cand obtained
widely different sizes of platelets depending on
reagent proportions and concentrations. The sizes ob-
tamed ranged from colloidal dimensions to about 0.5
pm. Large particles were obtained by adding ammo-
nia to magnesium chloride solution containing a little
citric acid. Hexagonal shaped crystals were (excep-
tionally) obtained by adding NaOH to a mixture of
MgC12, NH4OH, and NH4C1 and aging for one week.
Using electron microscopy, Shirasaki [9] claimed
that at low temperature, four sorts of cotton-type
precipitates having blossom-petal patterns could be
obtained using MgSO4 and NH4OH. These gradually
redissolved and were replaced by plate-like crystals on
standing for several days or weeks. He also obtained
evidence [10] of the existence of hydrated magne-
sium hydroxide of composition Mg(OH)2 m(H20) .

addition of surfactants. Much less is known about fac- where 1 <m <2, which was stable for several
tors controlling the morphology of precipitates pro- months in dry form at room temperature. This hy.
duced by a continuous chemical reaction under con- drated form apparently consisted of random single

228
 V.A. Phillips eta!. I Effect of pHon growth of Mg(OH)2 crystals 229

layers of brucite-type lattice with water layers sand-
wiched between. Added ions, such as citrate, tended
to stabilize the hydrated form [11]. The same ions
tended to stabilize basic MgSO4 hydrate formed by
reacting MgSO4 with ammonia in aqueous solution,
and were thought to be chemically bonded [11].
Liu and Nancollas [12] studied the kinetics of
Mg(OH)2 crystal growth from a seeded supersaturated
mixture of MgCl2 and NaOH, but did not make
morphological
2~ions,observations. Mixtures
or stoichiometric containing
mixtures, showed
excess Mg
a smaller cyrstallization rate constant than those with
excess OH ions. The crystallization rate constant
was reduced by various phosphonate additives,
Copperthwaite and Brett [13] added varying amounts
of KOH solution to stirred MgC1
2 solution, moni-
toring the final pH. Average plate diameter, deter-
mined by X-ray analysis, increased from about 135
to 155 A with increase in (final) pH from 9.65 to
10.2, then levelled off up to pH 12.15.
2. Experimental procedure
The Analar purity reagents, namely 0.75 M magne-
slum chloride and either 1.50 M ammonium hydrox-
ide or 1.50 M sodium hydroxide, at ambient tempera-
ture, were separately added from burettes, at about
1.5 ml/min into 800 ml of distilled water at 60Cin a
reaction vessel. The latter consisted of a 3-necked
flask fitted with pH electrodes connected to a pH
meter and recorder. The meter was provided with
manual control for bath temperature compensation.
The reactor was immersed in a water bath giving 1C
temperature control, and stirred fairly vigorously to
keep the precipitated solids in suspension. Two
metering pumps (Milton Roy Company) were used to
control the reagent addition rates, the amounts added
being read off from the burettes.
The run times were about one hour. Although
equal reagent addition rates gave the correct stoichio-
metric ratio to form Mg(OH)2, initially it was neces-
sary
order totoadd excess
set the pH of
at aone or the
desired other
value reagent
between in
8.60
and 12.5, which was then held constant during the
run, adjusting the addition slightly from time to time
as needed. At pH ~ 8.75, excess magnesium chloride
was needed. At pH ~ 9.0, excess ammonia was
needed. In order to attain the 12.5 pH level, caustic
soda was substituted for ammonia.
A note was made on the pH record chart of the
time at which turbidity appeared, indicating the start
of precipitation. From then on, the crystals were
growing in a seeded environment under very low
effective supersaturation. Values
2~and of 0H ion concen-
MgOH~ion concen-
tration, and
trations, computed
versus pH areMg shown in table 1. In some
cases, crystals were aged for one hour at 60Cin the
bath liquor after completion of a run. The crystals
were filtered, washed repeatedly with hot (60C)
distilled water, and redispersed in water.
Reaction in dilute solution combined with rapid
stirring, under standardized reactor conditions, per-
mitted good reproduceability of both size and shape
of the particles. Many of the runs were repeated two
or three times to prepare material for other experi-

Table 1

Estimated molar equilibrium concentrations in solutions of Mg2+ ions at various pH a

pH [0H) [Mg21] [MgOH~] [Mg2+]/[MgOH~]

8 106 12 4.2 X i0~ 2.9 x ~

9 i0~ 0.12 4.2 x 10~ 2.9 x 102
10 i0~ 1.2 x i~~ 4.2 x 10~ 2.9 x iO
11 io~ 1.2 X 10~ 4.2 X 106 2.9 x 100
12 102 1.2 x l0~ 4.2 x io~ 2.9 X 101
13 101 1.2 x 10~ 4.2 x l0_8 2.9 X 102

a Values of constants used: Ref.

= [H~] [0H] = i0~ (~=40C) [14]
= [Mg21] [0H]2 = 1.2 X 10h1 (18C) [15]
K
1 [MgOH~]/[Mg2f] [0H] = 350 (25C) [12]
230 V.A. Phillips eta!. / Effect of pH on growth of Mg(OH)
2 crystals

ments. Our experience indicates that washed

Mg(OH)2 crystals can be stored wet in a filled flask or
tube from which air is excluded for substantial
periods of time without appreciable change in mor-
phology or size. Once they are allowed to dry out,
the particles tend to stick together, and there is no
satisfactory way of redispersing for electron micro-
scopic examination. The solubility of magnesium hy-
droxide in water is very low and our experience indi-
cates that the very brief process of washing in hot
(60C)distilled water, caused no significant change in
particle size or shape.
A microdrop of the Mg(OH)2 aqueous suspension
was transferred onto a carbon film substrate on an
electron microscope grid and allowed to dry. This
procedure was found to give the most satisfactory
results of a number tried, and appears to give good
sampling of the sizes present and reasonable freedom
from agglomeration. Reproduceabiity was good.
Transmission electron microscope examination was
then carried out at 100 kV and 25,000X magnifica- i ~-i
tion. Average particle diamters were measured on 50
lig. 1. Magnesium hydroxide crystals precipitated with
particles in a given area of an enlarged print. It was NaOH at pH 12.5. Unaged.
possible to obtain diameter/thickness ratios in many
samples on a few (4 to 10) platelets which happened
to lay parallel to the electron beam. Surface area mea-
surements were made in a Quantachrome Monosorb
adsorption equipment on 0.20.5 g samples, which
had been oven dried overnight at 120C.

3. Results

Substantial changes in the size, shape, and perfec-

tion of the precipitated Mg(OH)2 particles were ob-
served as a function of pH (figs. 17, and table 2). At
pH 12.5 (fig. 1), pH 11, and pH 10.5 (fig. 2), very
thin plates were obtained with moderately well devel-
oped hexagonal shape. Most of the plates lay flat on
the substrate so that the electron beam was parallel to
the c-axis of the hexagonal structure, as confirmed by
selected-area electron diffraction. Approximate diam-
eter to thickness ratios were measured on those
which lay edge-on (table 2). At pH 12.5, the particles 02
were so thin that useful thickness measurements
could not be made. The ratio tended to increase with I I
pH, indicating that edge growth was favored over Fig. 2. Magnesium hydroxide crystals precipitated with
growth parallel to the c-axis. These average ratios NH4OH at pH 10.5. Unaged.
 V.A. Phillips eta!. / Effect ofpH on growth of Mg(OH)2 crystals 231

Effe:tof pH on morphology, perfection and size of Mg(OH)2

particles formed from MgCI2/NH4OH during 1 h run at 60C
P
Run details Average particle Ratio ______________________________

pH a diameter (pm) diameter/thickness

Unaged Aged Range Average ___________________________________

at 60C

12.45
10.90
xsNaOH
xsNH4OH
0.047

0.090

814

10.9
__________ -

10.45 xsNH4OH 0.050 510 7.3

9.95 xsNH4OH 0.183 0.256 26 4.3
9.50 xs NH4OH 0.147 0.164 46 5.1
9.00 xsNH4OH 0.112 0.112 26 4.5
8.75 xsMgCl2 0.303 13 2.3

a~005

divided by the average particle diameters indicated

that the average plate thicknesses were only 7090 A 0.2/i.
in this 10.5 to 10.9 pH range, compare with 200500 ______

A in the 9 to 10 pH range.
At pH 10.0, the crystals tended to be imperfect Fig. 4. Magnesium hydroxide crystals precipitated with
with indented outlines both before aging (fig. 3), and NH4OH at pH 9.5. Unaged.

_____ 0. 2p.
Fig. 3. Magnesium hydroxide crystals precipitated with Fig. 5. Magnesium hydroxide crystals precipitated with
NH4OH at pH 10.D. Unaged. NH4OH at pH 9.0. Unaged.
 232 V.A. Phillips et al. / Effect of pH on growth of Mg(OH)2 crystals

after aging for one hour on the liquor at 60C.At perfection were too small to be apparent and even the
pH 9.5, relatively perfect crystals of well defined ragged crystal outline obtained at pH 10.0 (fig. 3) was
hexagonal shape were obtained. At pH 9.0, the crys- preserved.
tals appeared to be of poorer quality, with less well Surface areas were measured on unaged material
developed hexagonal shape than at pH 9.5, and some made in further 4 h runs at similar constant pH levels.
tendency to layering, i.e. plates were present showing The surface 2/g,
areaincreased
in the lowest pHabruptly
rather runs at 8.78.9
at pH 9.0was
to
twoAordramatic
more distinct
changelayers.
in morphology occurred when 10 m2/g,
26 to 12 mand stayed in the range 25 to 36 m2/g up to
precipitation was carried out at pH 8.75 [1]. This pH 11.0 (fig. 8). At pH 11.5 to 12.1, a big increase
yielded almost equiaxed particles which showed a occurred to 6368 m2/g, presumably corresponding
stacked-plate morphology (figs. 6, 7). The average to an increase in diameter/thickness ratio and
diameter was 0.3 pm (table 2). Selected-area electron increased peripheral area of the smaller particles (fig.
diffraction on an individual particle (fig. 7) showed it 8).
to be a single crystal with the c-axis normal to the
apparent layers. The term stacked plate morphol-
ogy is intended to be descriptive, rather than imply-
ing a particular mechanism of formation.
Aging for one hour in the liquor, maintained at the I 1
precipitation temperature of 60C,tended to result in
modest selective growth of the particles at pH 9.5 and
10.0 which eliminated the smallest particles and
increased the average size (table 2). At pH 9.0, aging
had no apparent effect (table 2)~changes if any, in

~ LJ~

:ri
___ 0.2p
I I
Fig. 6. Magnesium hydroxide crystals precipitated with Fig. 7. Single particle precipitated at pH 8.75 with electron
NH
4OH at pH 8.75. Aged 1 h at 60C. diffraction pattern.

.
 V.A. Phillips eta!.
70 I tion it becomes energetically favorable to grow a
/ fresh layer rather than to continue growing existing
60
50 - /
/ Shirasaki [10] for the existence of a metastable hy-
~ 40 - /
/ single layers of brucite type lattice with water layers
~ 30
20
10 - served in the electron microscope, it was difficult to
9 i~ ii
pH
Fig. 8. Variation of BET surface area of magnesium hydrox-
ide crystals with pH during precipitation,
4. Discussion
These experiments in which magnesium hydroxide
was precipitated by reacting magnesium chloride solu-
tion with ammonium (or sodium) hydroxide at 60C
at pH levels of 12.5 to 8.75 showed that the particle
morphology, average diameter, diameter to thickness
ratio and surface area varied with pH. At high pH
levels (10.5 to 12.5) the precipitates were plates
which tended to be small and very thin, and had rela-
tively high diameter to thickness ratio and surface
area. Thus, high pH favored edgewise growth of plates
in directions lying in the basal crystallographic plane
rather than growth along the c-axis. Conversely, at low
pH near 8.75, growth along the c-axis was about as
great as growth in the basal plane and roughly
equiaxed particles tended to be formed. The rela-
tively small variation in surface area over the pH
range from 9.0 to 11.0, with a somewhat higher value
at pH 10.0 where rather imperfect particles with
indented outline (fig. 3) were observed, suggests that
particle imperfection had a significant effect on sur-
face area. This would require higher resolution elec-
tron microscopy for evaluation,
Although the stacked-plate morphology ob-
served at pH 8.75 suggested that separate plates might
have
to formedthis
envisage andmechanism
become agglomerated,
giving rise to ait single
is difficult
crys-
tal, as observed by electron diffraction. It seems more
likely that with decrease in hydroxyl ion concentra-
/ Effect of pH on growth of Mg(OH,)2 crystals 233
- layers in the a-direction, thus minimizing the surface
area of the particle. The evidence obtained by
- drated form of magnesium hydroxide, consisting of
sandwiched between, suggests that chemisorbed water
may play a role in assisting growth in the c-direction.
Although clumps of particles were commonly ob-
I decide whether these were present in the liquid or
12 formed during drying out on the carbon substrate.
Precipitated magnesium hydroxide particles should
carry a charge below and above the isoelectric point
which occurs at about pH 12 [16]. Experiments were
made in an electrophoretic Zeta Meter equipment
[17], using distilled water electrolyte adjusted with
ammonia, a molybdenum cathode and platinum
anode. These showed that the charge was positive
below the isoelectric point, indicating that magne-
sium ions are more strongly adsorbed than hydroxyl
ions on the basal crystal surface. Since the charge will
increase the further the solution pH is moved away
from the isoelectric value, any tendency to clumping
should decrease. This is compatible with the micro-
graphic evidence.
The hexagonal plate morphology shown most
clearly at pH 9.5, results from the fact that crystals of
hexagonal structure have anisotropic growth rates.
The slow rate perpendicular to the close-packed basal
planes results in a plate form with the c-axis perpen-
dicular to the plate. The hexagonal outline results
from the formation of prism faces perpendicular to
the close-packed, slow growth, directions in the basal
plane. It was at first thought that the occurrence of
plates with indented outline at pH 10.0 might corre-
spond to a changeover point from the growth of first
order prism faces to second order as a function of pH.
Selected area electron diffraction on hexagonal plates
grown at pH levels above and below pH 10.0 dis-
proved this and indicated that both had the same
faces developed. It appears that at pH 10.0, which is
about that there
2+ ions, for equimolar concentrations
was a retardation of OH and
of development of
Mg
the usual prism faces. The reason for this is not clear.
The results indicate that excess OH anions or
Mg2~cations affect the growth rate in a particular
234 V.A. Phillips et al. / Effect of pH on growth of Mg(OH)2 crystals

direction differently, causing changes in the crystal
shape,
area. the diameter to
Magnesium thickness ratio,
hydroxide and the
crystals surface
have the
Cd(OH)
2 structure and can be viewed as having a
more or less perfect packing of anions with the
smaller metal cations lying in interstices. The effect
of excess anions or cations on growth is presumably
connected with this detailed structure and the way in
which ions are added on, which involves consider-
ations of bonding and charge. Two anions must be
added for every cation to maintain charge neutrality,
There was no evidence of any specific ion adsorption
effect due to the presence of sodium ions in the
experiment at pH 12.5.
Although no detailed measurements were possible
of nucleation and growth rates, our observations on
the onset of turbidity suggested that nucleation was
relatively easy at high pH, so that large numbers of
small particles were obtained, and relatively difficult
at pH 8.75, resulting in maximum particle diameter at
this pH. Since once begun, precipitation would occur
at roughly constant rate throughout a one-hour run,
low nucleation rate would favor growth on existing
particles. The larger a particle grows, the greater is the
probability that a screw dislocation will arise due to a
growth error. Even a single screw dislocation is suffi-
cient to facilitate growth in the c-direction on the
Frank mechanism [18]. The small crystals obtained
at high pH appeared to be free from dislocations,
although higher resolution studies are desirable to
confirm this.
The formation of a stable precipitate nucleus
involves bringing together a sufficient number of
Mg(OH)2 molecules to form a nucleus of critical size.
Liu and Nancollas [12] obtained electrical conductiv-
ity evidence for the existence of the MgOH~ion pair
in solution. Although the results of Klein et al. [19]
indicate that Mg(OH)2 is the stable nucleus phase, the
presence of MgOH~ion pairs would tend to ease the
diffusion supply problem, facilitating formation of a
critical nucleus. Molar concentrations of MgOH~ions
were estimated as a function of pH from the data of
Liu and Nancollas [12] (table 1). Looking
2~]/[MgOH~], at the con-
it is apparent that
centration ratio [Mg
any effect of MgOH~ions would be negligible at pH
8 or 9, but would become important at pH 11 and
above.
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York,Read,
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