Injection of sodium silicate solutions into

rock salt long-term behaviour

H.-J. Engelhardt & L.E. von Borstel
DBE Technology GmbH, Peine, Germany
K. Mengel & Th. Schirmer
Technical University of Clausthal, Clausthal-Zellerfeld, Germany
Sodium silicate solutions have been used for decades as a grout to
seal flowpaths of water or brines in underground structures.
Subsequent to a pregrouting with suspensions, it is possible to reduce
the permeability of the rock significantly, as the penetrating capability
of particles into very small fissures is limited. Silicate solutions react
with soluble salts as well as with brines. For the grouting of rock salts,
investigations were carried out to determine the reaction processes
and to identify the products. The results correspond to the findings of
other investigations described in literature. In MgCl2-dominated
brines, present in marine salt formations, silicate phases, magnesium
oxichlorides (phase 3), and halite are the major reaction products. As
the silicates and oxichlorides are characterized by an extremely low
solubility and halite is insoluble in the brines, this study documents the
capability of sodium silicate solutions to seal rock salts permanently.
The investigations refer to the grouting of rock salt with halite as the
main component. In accordance with the chemical and mineralogical
composition of marine evaporites, halite saturated brines belonging to
the Quinary System with the dissolved salts NaCl, KCl, MgCl2, and
MgSO4 were used. Anhydrite and the corresponding CaSO4 content
were neglected. In order to evaluate the long-term behaviour of the
grouts, knowledge about the mineralogical products of the reactions
with halite and brines as well as about their solubility is of utmost
importance. The work included a summary of the actual scientific
knowledge, laboratory investigations, geochemical modelings, as
well as an evaluation of natural analogues.

SEM image of a salt-sodium silicatemixture injected with concentrated

MgCl2-solution. The different levels of
gray are layers dominated by Mgsilicates and magnesium oxichlorides.
The small fissures arose during the
preparation of the sample.

XRD-analysis from solids during the experiment

h: halite, a: maybe cristobalite; sy: sylvite; Am1, AM2: amorphous areas
MOC-318: 3 Mg(OH)2 MgCl2 8 H2O ; MOC-518: 5 Mg(OH)2 MgCl2 8 H2O

Backscattered electron image of

silicate and halite in NaCl-solution
after 1, 40 and 360 days of contact.
halite-n means secondary halite

xx: main phase; x: ancillary phase; o: present (o): assumed; -: inexistend

experiment/day

10

40

90

360

h (31.722 2Q
)

xx

xx

xx

xx

xx

Am1 (50-53 2Q
)

a (28.559 2Q
)

h (31.722 2Q
)

xx

xx

xx

xx

xx

Am1 (50-53 2Q
)

Am2 ( 20 - 25 2Q
)

MOC-518 (11.86 2Q
)

MOC-318 (10.86 2Q
)

a (28.559 2Q
)

xx

xx

NaCl-solution

NaCl-MgCl 2-solution

Experiments show the behavior of a solid mixture of halite and sodium

water-glas in contact with saturated salt solutions.
Halite before and after the contact with sodium water-glass 37/40.
There is a rapid reaction of the water-glass and the salt.

NaCl-KCl-MgCl 2MgSO 4-solution

h (31.722 2Q
)

xx

no specimen taken

Am1 (50-53 2Q
)

Am2 ( 20 - 25 2Q
)

MOC-518 (11.86 2Q
)

(o)

MOC-318 (10.86 2Q
)

Sylvin (28.346 2Q
)

Backscattered electron image of

silicate and halite in NaCl-MgCl2
solution after 1, 40 and 360 days of
contact.
halite-n means secondary halite
MOC-Magnesium-Oxi-Chlorides

Halite dry

Halite directly after contact with water-glas

After 14 days, dentrital growth of

halite crystals in the silicate
layers

Backscattered electron image of silicate,

halite and MOC-phases in NaCl-KClMgCl2-MgSO4-solution solution after 1,
40 and 360 days of contact.
SiO2 solubility of the solids within the experimental solutions, compared to solubilities in
differend concentrated single salt solutions at 25 C (data from Marshall & Warakomski,
1980), amorphous SiO2 at different pH and age as well as quartz.

A simplified reaction between halite and sodium water-glass

assuming a SiO2/Na2O mol ratio of 3.5 are shown in equation 1.

EDX analyses of single silicagrains from raw material compared with

material in contact with solution (mass. %)
Raw material

NaCl-solution
(90 days)

element

Na2O3,5SiO2 + NaCl + n H2O

NaOH + 3,5 SiO2 + 2 NaCl + n1 H2O (1)

NaOH will be fixed within the silicate. In contact with saturated MgCl2solutions brucite and MOC-phases can be observed. The present of
MgSO4 will lead to MOS-phases.

NaCl-MgCl2-solution
(90 days)
(Mg-Si-phases)

(Si-phases)

47.0

51.0

42.4

52.0

Na

15.0

3.9

0.6

0.6

Mg

16.4

0.9

Si

36.4

43.4

31.3

44.3

Cl

0.8

1.1

2.7

0.8

Sum.

99,2

99.5

98.4

98.6

Backscattered electron images

of silicate and halite after the
preparation of the dried raw
material
Optical photomicrograph illustrating the reaction of a silicate-halite-mixture with concentrated
MgCl2-solution. Dentritical halite and needles of magnesium oxichlorides (MOC) are seen.

Expert Knowledge and

Comprehensive Know-how

halite-n means secondary halite

MOC-Magnesium-Oxi-Chlorides

Chemical and mineralogical investigations document that the most

important reaction products of sodium silicate grouts are halite,
magnesium oxichlorides, and amorphous silicates in the brines which
must be expected under the realistic conditions in a salt mine.
Concerning the long-term sealing of fissures in rock salt, it is
necessary to investigate their thermodynamic stability and solubility in
the brines. The thermodynamic stability is important, because phase
reactions may form new minerals with a deviating solubility.
Despite the fact that the structures of the amorphous silicates are
difficult to determine, the analysis results show that the high salt
contents of the brines limit their solubility to an extremely low level.
Magnesium oxichlorides impede an increase of the pH milieu (cf.
Bodine 1976) which may cause an increase of SiO2 solubility. The
detected contents of SiO2 dissolved in the Mg-containing brines,
documents a lower solubility than quartz in water.
Sodium silicates are used to accelerate the hydration of cement- and
magnesia-based systems. Furthermore, experience proves that
sodium silicates can be combined with these building materials
without any restrictions. Thus, there is no objection to the use of
sodium silicate solutions as a grout in rock salt, even if the rock was
pregrouted with a cement or magnesia slurry.