Journal of Crystal Growth 87 (1988) 287—294 287

North-Holland, Amsterdam

CRYSTALLIZATION OF SODIUM OXALATE ON METAL SURFACES

N. BROWN
Leichtmetall-Forschungsinstitut der Vereinige Aluminium- Werke AG, Georg-von-Boeselager-Slrasse 25, D-5300 Bonn 1,
Fed. Rep. of Germany

Received 29 September 1987

Crystallization of sodium oxalate in caustic aluminate solutions can occur on metal surfaces provided the supersaturation with
respect to sodium oxalate is high enough. Heterogeneous nucleation occurs most readily on polycrystalline surfaces which also
provide for strong adherability of the crystalline oxalate. The nature of the sodium oxalate that crystallizes is strongly dependent on
the presence in solution of high molecular weight humic-type organics. Not only are the acicular sodium-oxalate “needles” reduced in
size, they intergrow and form ball-like structures directly on the metal surface.

1. Infroduction sodium oxalate in a side-stream operation by

Sodium oxalate forms in the caustic aluminate
solution of the Bayer process (for the production
of alumina from bauxite) from the degradation of
high molecular weight humic type organic carbon
substances which enter the process with the start-
ing bauxite [1].
Sodium oxalate presents a special problem in
that it is the only one of the many degradation
products formed which accumulates to a con-
centration exceeding its solubility in solution,
Caustic aluminate solutions are thus su-
persaturated with respect to sodium oxalate and
are, to some extent, stabilized in this condition by
the other organic carbon compounds in solution
[2].
Difficulties arise when the dissolved sodium
oxalate crystallizes at the temperatures and caustic
concentrations employed in the main crystalliza-
tion step of the Bayer process, i.e. the seeded
crystallization of aluminium trihydroxide [2]. Con-
sequently, a number of sodium-oxalate removal
systems have been developed aimed at controlling
sodium oxalate concentrations at levels below the
critical concentration at which nucleation takes
place [3]. One such control method separates
0022-0248/88/$03.50 © Elsevier Science Publishers B.V.
(North-Holland Physics Publishing Division)
crystallizing on metal surfaces confined within a
tubular reactor [3,4].
Little is known, however, about the crystalliza-
tion of sodium oxalate on metal surfaces and the
role played by humic type organic carbon corn-
pounds normally present in caustic aluminate
solution. In the work described in this paper, the
crystallization of sodium oxalate on metal surfaces
has been examined using scanning electron mi-
croscopy and associated EDAX X-ray analysis
technique.
2. Experimental
2.1. Caustic aluminate solution
Caustic aluminate solutions of industrial com-
position were used to examine the crystallization
of sodium oxalate on metal surfaces in the pres-
ence of the major organic impurities. Synthetic
solutions, prepared to a similar caustic concentra-
tion, essentially free of organic carbon compounds
were used to examine the effect of selective ad-
ditions (0.2 g/l organic carbon equivalent) of a
 5’. Born ii ( rvvtall,:aiirn, ~l srnliuni HO//Ole oil 1001(1/ /111/ Uii’

hurnic extract from Australian (Weipa) bauxite. 2.3. Metal .cw’/ace~

The hurnic extract was prepared from a 2000 g/l
char°e of Weipa bauxite (0.20~oroanic carbon
Metal surfaces used in the industrial process
content) held with aGitation under nitrogen atmo—
are oener~illsbased on iron and stainless steel. In
sphere for 30 mm at 70°C in 4N NaOH. Hurnic - .
the cr~stallizationexperiments ol the present work.
matter is known to contain carhoxyl. phenolic and
two t~pesol metal surface were used:
hvdroxvl groups and behaves in solution as an .- - ,
(a) polyelectrolyte
anionic [5]. n,~\ -coated
had been surfaceiron (ca. 4 iii m diameter>,
“roughened” which
by exposure to

weathering conditions. Although there were a

2.2. Analytical
Metal surfaces and sodium—oxalate—coated
surfaces were examined by combined SEMi
EDAX X-ray analysis technique. The SEM micro-
graphs were obtained using a JEOL-840 scanning
electron microscope, operating at an accelerating
voltage of 20 --25 kV. The topochernical analyses
of metal surfaces were carried out Lising the at—
tached EDAX analyser, an energy-dispersive X-ra\
analysis Links System Model 860 with Si( Li) de-
tector. A channel width of 10 eV was used.
All solutions were analysed for sodium oxalatc
by ion chromatography using a Dionex 2000i SF
system.
number of isolated, relatively smooth areas, most
of the surface consisted of a polycrystalline as—
semblage of individual particles of oxidii~d iron
(see fig. hi). The EDAX anal\sis confirmed that
the Zn/V coating was complcte1~disrupted where
the underlying iron had emerged (fig. I b>.
(h) (‘u-coated iron (ca. 2 mm diameter) which had
not been exposed to weathering conditions and
thus retained a relatively smooth surface (fig. 2a.
FDAX analysis confirmed that the observed cracks
in the copper—coating exposed the underl~ingiron
(figs. 2h and 2c>.
Thus, the two t~pcsof metal surface used in thc
present work provided both physical and chemical
differences.

II~IFe RI Pb

Fig. 1. (a) Surf:ice of Zn/V—coated iron: marker rcpre~ents 1(5) y. (hi Fl)AX ,iiialvsis. /n V—coated
V

eV
roil.
Zn
 1v. Brown / Crvstalli:aonn of os/turn usa/ate on metal surfaces 289

— b

~i Cu

Ii
Fe ft

— Cu r: b Cu
m-m~rti~rrrrn-rrryt4 ii r~ 4 ii~

2.4. Crystallization

The crystallization experiments on metal c

surfaces were carried out under stagnant condi-
tions in a cylindrical glass vessel of 1 litre volume.
To begin an experiment, 500 ml of sodium-
oxalate-containing solution was brought to a tem-
perature of 600 C and the appropriate metal posi-
tioned within the solution. Although each piece of
metal was ca. 15 cm in overall length, the metal
was bent into a form that could sit upright in the F
solution with most of the metal off the bottom of e
the vessel and in more or less horizontal position.
The system was then cooled to room temperature
over an 8 h period to induce sodium oxalate L
crystallization on the metal surface Ii
Prelinunary tests were earned out to establish Ca
the experimental conditions necessary to provide RI ~‘l F~
optimum results m e conditions under which a
sodium oxalate would crystallize on the metal iii if ifrr1uTrrj”r~t1’rr’]tflt74~t ill),’,

surfaces as opposed to the walls of the glass vessel 0 - ~ 10. 1

or within the body of the solution. Fig. 2. (a) Surface of copper-coated iron; marker represents
At the end of each crystallization expenment, .
100 jam. (b) EDAX analysis, copper-coated iron — smooth
the sodium-oxalate-coated metal was removed, surface. (c) EDAX analysis, copper-coated iron — surface
washed with cold (ca. 40 C) 4N NaOH followed within a crack.
290 A’. Broiin / C’rrstalli:anon oJ coclium nra/ate au metal sal/ni ~

by methanol and then dried in air at room temper-

ature.

3. Crystallization in caustic aluminate solution of

industrial composition

The starting solution composition was as fol-

lows:

caustic concentration 105 g/l(as Na~O).

carbonate concentration 20 g/l(as Na
20).
alumina concentration 60 g/l.
organic carbon 14 g/l.
sodium oxalatc 5.5 g/l.

The equilibrium solubility of sodium oxalate as

a function of caustic concentration, temperature Fig. ~. Hetereogeneous nucleation and err stal griasth at sodium
and the major solution impurities is known [2,61. oralate nit 7.n/V-coated surface. Marker represents 10 jim.
Thus, at the starting temperature of 60°C. the
solution was stable although approximately 100% ture surface shown in fig. 4 indicates that the
supersaturated with respect to dissolved sodium . .

oxalate deposited is built up from acicular sodiuni

oxa ate. oxalate crystals intergrowing in a highly branched
The system was then cooled to room tempera- .

ture over an 8 h period and then left to crystallize

I he tenacity with which the crystalline oxalate
for a further 16 h on Zn/V-coated iron. During
was held to the underlying surface was such that it
this period, the dissolved sodium oxalate con- .
could he physically removed only with difficulty.
centration decreased to 3.2 g/l, i.e. at the end of
the experiment, the solution was still approxi-
mately 100% supersaturated with respect to dis-
solved sodium oxalate. The first signs of crystalli-
zation activity during the experiment, however.
were observed at a temperature of 30—40 °C, which
meant that the sodium oxalate supersaturation at
the time of nucleation would have been of the
order of 200%. This is in broad agreement with
previously published data for secondary nuclea-
tion * of sodium oxalate in caustic aluminate solu-
tion of industrial composition [2]. That heteroge-
neous nucleation of sodium oxalate takes place on
the Zn/V-coated iron surface can be seen in fig. 3.
The overall impression in these experiments
however is of a mass of crystalline sodium oxalate
advancing on a broad front irrespective of the
nature of the underlying metal surface. The frac-

* Secondary nucleation refers to new crystal formation which Ui . 4. Fracture surfa e of sodium o\alate ro~th on Zn \
occurs in only the presence of sodium oxalate seed crystals. coated iron Marker represents 100 jam
 N. Brown / Crystallization ofsodium oxalate on metal surfaces 291

revealing the under surface of the oxalate in con- At the starting temperature of 600 C, the
tact with the metal. sodium-oxalate-containing synthetic liquor was
brought into contact with Cu-coated iron metal
and cooling of the system commenced. Before the
4. Crystallization in synthetic caustic aiwninate temperature had reached 50°C, i.e. within the
solutions first hour, the crystals of sodium oxalate had
already started to grow on the metal surfaces.
The starting solution composition in these tests After the 8 h period, the sodium-oxalate con-
was as follows: centration had decreased to 1.6 g/l at room tem-
perature.
caustic concentration 100 g/l (as Na
20), . - -
Typical examples of the actcular sodium oxalate
carbonate concentratton 2 g/l (as Na 2°), .
- that crystallized are shown in figs. 5 and 6. Note
alumina concentration 22 g/l.
that the exposed iron appears to offer the lowest
To this stock solution was added the desired energy sites for heterogeneous nucleation of
amounts of sodium oxalate and organic carbon
compounds in the form of humic extract from
Weipa bauxite.

4,1. Crystallization in the absence of non-sodium-

oxalate organics

In the absence of non-sodium-oxalate organics

the caustic aluminate solution was prepared so
that it was only saturated with respect to sodium
oxalate at 600 C. Thus, the sodium-oxalate con-
centration of 3.5 g/l corresponded approximately
to equilibrium solubility.

Fig. 5. Sodium oxalate crystaltized on copper-coated iron — Fig. 6. Sodium oxalate crystaltized on copper-coated iron —
synthetic caustic aluminate solution, Marker represents 100 synthetic caustic aluminate solution. Marker represents 100
pm. pm.
292 \ Bros’, ,t ( fl
II. Fig. 7. Sodium-oxalate crystals showing common growth flaws Markers represents I)) pill.
sodium oxalate crystals which tend to grow prefer-
entially out of the cracks in the copper coating.
The sodium oxalate crystals are relatively large
and well-formed, extending outwards from the
metal surface in long “fingers” reaching into the
supersaturated solution during crystallization.
They also split and branch in order to increase the
surface area exposed to the solution.
Although single crystals of sodium oxalate are
monoclinic, the acicular crystals generally assume
a pseudo-hexagonal form, i.e. they grow with six
sides instead of four, at least during the early
stages of growth. In fig. 6 can be seen sodium-
oxalate crystals which are virtually diamond-
shaped (when viewed from above) as the two extra
sides are eliminated.
The tips of the oxalate crystals, i.e. the (001)
faces, which are the fastest growing, tend to he
defective and exhibit most of the common growth
flaws including holes and voids (fig. 7a). Uneven
(001) crystal surfaces are also observed where
sta//t ,.atton of (odium 05(1/all oil metal (urlal
L1
internal surfaces with a slight degree of mismatch
on either side of the boundary emerge (fig. 7h).
4.2. Crystallization in the presence of added hunt/c
extract
The sodium-oxalate concentration of the syn-
thetic caustic aluminate solution was raised to 5.0
g/l in order to overcome the inherent stability of
the solution in the presence of 0.2 g/I added
humic extract. Crystallization was carried out for
the initial 8 h period with cooling and then con-
tinued for a further 16 h at room temperature. The
sodium-oxalate concentration of the solution at
the end of the 24 h period was 2.8 g/l.
The dramatic effect of the humic organics on
the form and structure of the sodium oxalate that
crystallized on copper-coated iron is shown in fig.
8.
The ball-like structures are composed of a net-
work of “needles” and whiskers of sodiuni oxalate.
 N. Broiin (ri stalljzation of sodium oxalate on metal surfaces 293

Fig. 8. Sodium-oxalate crystallization on copper-coated iron surface — synthetic caustic ahuminaie solution + 9.2 g/l humic exiract
Markers represent: t.ij 100 pm; (b)—(d) 10 pm.

The framework of the structures and the main
support comes from thin oxalate needles growing
outwards in a semi-ordered fashion leaving a net-
work of voids between them. Woven around and
connecting up the needles are very fine wisps or
strands of sodium oxalate giving the impression of
hexagonal-shaped voids within the ball-like struc-
tures.
These ball-like structures of sodium oxalate
clearly form in response to the organics con-
tamination of the sodium oxalate crystals which,
in assuming these structures, create the maximum
amount of new surface area to allow further
oxalate crystallization to occur.
The ball-like structures could be readily re-
moved from the copper-coated metal surface re-
vealing a central contact region surrounded by a
network of sodium oxalate crystals growing out-
 (4 \ /i’i,,O 1) ( si~jl/i.,jIm am ‘‘I o limo , Va/alt’ (11? (0(1(1/ I (0/all’S

1:

_____ - ~—-
i;—

•~ Na
I

0 Cu
i~
— 1.5-it —— ~

I I

0.0 10.1

eV

C
Ma

wards parallel to the metal surface but with no

firm bonding to it (fig. 9).

5. Concluding remarks

Given a sufficiently high supersaturation, there - -

~
is little doubt that sodium oxalate in caustic “u~
aluminate solution can crystallize directly on metal .,, ~ ,

surfaces. Polycrystalline surfaces involving oxi- I e.

dized iron offer suitable sites for heterogeneous eV

nucleation of sodium oxalate. The crystalline Fig. 9. (a) tinder-surface of crystalline sodium oxalate removed
oxalate which subsequently forms is also provided from copper-coated iron metal; marker represents 100 pm. (hI
EDAX analysis — central area of under-surface of crystalline
with a firm grip on the underlying surface, an sodium oxalate removed from copper—coated iron metal. (e)
important practical consideration where there is FDAX analysis — perimeter area of under-surface of crystalline
movement of the crystallizing solution relative to a sodium oxalate removed from copper-coated iron metal.
stationary metal surface.
Crystal habit of the acicular sodium-oxalate References
‘~needles”is particularly sensitive to the presence [1] (i Lever. in Light Metals (‘onf Proc.. 1978. pp 71—84.
of humic organics in the caustic aluminate solu- [2] N Brown and T J Cole. in’ l.ight Metals (cml. Proc
tion. The response of the system to the poisoning 198(1, pp. 105—118.
effect of the organics is to reduce the thickness [3] B. Gnyra and (3. Lever, in: Light Metals Conf. Proc.. 1979.
and length of the sodium-oxalate crystals while PP~151—162.
[4] AN. Carruthers,J.F,. Deutschrnan and MCi. Willis, US
creating an elaborate fine structure, which pre- Patent 4.038,039 26 July 1977
sumably is to increase the surface area of the [5] (3. Lever. Travaux du Cornité International poor rhitude
sodium oxalate thereby permitting a rate of crys- des Bauxites. de lAlumine et de l~Aluminium 13 (18)
tallization the supersaturation of the system can )1983 335—344.
support. [6] P.J. The and J.F. Bush. in: Light Metals Cool. Proc.. 1987.
pp. 5—10.