Proceedings: Symposium on
Evolution of
‘Abandoned Mine Land Technologies
Riverton, Wyoming
dune 14 16, 1989,
Sodium Silicate Grouts:
The Solution to Difficult Subsidence Problems
Richard H. Reifsnyder-
John F. Peters
Introduction
In 1982, the PQ Corporation was: approached: by
the Office’ of Surface Mining, Reclamation ‘and
Enforcement and asked to develop a grouting
technique that would enhance the placement of
cement mixes under water. The standard technique
being used in. remedial » actions : to prevent
subsidence was to inject a fly ash/cement grout
into the void to form high strength columns that
would provide support to the collapsing
‘overburden. Once the overburden was stabiized,
the void is then filed using a backfill or low
strength grout. This technique worked well in dry
mines but has not proven effective when water was,
Present within the mine void."
To form high angle of repose support columns
using a fly ash/cement grout, the self-supp
properties of the mix is controlled by adjusting the
‘solids content of the grout. The higher the solids
of the grout, the lower the slump value and the
faster the grout would build a column. The problem
encountered in flooded mines was that once the
grout was injected into the void the surrounding
water would penetrate into the mix diluting the
grout and reducing its self-supporting properties.”
This dilution caused the grout to level out forming
a low angle of repose mass on the void floor. To
achieve roof contact and adequate support, large
Volumes of grout would have: to::be injected
thereby raising the total.cost of the raw: materials,
needed to complete a job.”
Other problems were encountered when grouting
flooded mines. Typical mixes were designed to
reduce costs by increasing the ratio of fy ash to.
cement used. Mixes based on 6 to 1 fly ash to
cement by volume are commonly used to control
‘costs.’ When high compressive strength grouts
(@,000 to 5,000 psi) are required, a sand aggregate
also included in the mix. These grouts are
effective:in dry environments but when injected
into water, the fly ash and cement components
were found to separate due to their differences in
density. This results in a large mass of grout
‘composed mainly of fy ash that does not set up
and has no load bearing, capacity to provide
support to the overburden.’ Also, in many cases
the water in the mine would be flowing, which
tended to displace the grout away from the
placement site. Moving water can also erode
structures builtin the void before the grout can set.
‘These were the major problems the OSMR&E
asked PQ to solve. To accomplish this, a
laboratory study was conducted to evaluate the
behavior of fly ash cement grouts in water on a
{Senior Technical Service Reprosantative, PQ Corporation,
“*Markot Development Project Managar, PQ CorporationSodium Silicate Grouts:
‘small scale. Different grout mixes were injected
into water and then observed for rate of height
development and durabiity of the final structure.
Compressive strength was also measured for
samples which had set in water. This study
revealed that silicate can significantly improve the
performance of grouts placed in water.” When
‘mixed into the grout prior to injection, the silicate
improved the final strength of the grout and had a
positive effect on column formation. It was also
found that if silicate was injected into the water
prior to or during grout placement there was a
significant improvement in column angle of repose
and the final structure had improved physical
properties. Based on these results, a pilot scale
mine simuiation was conducted to evaluate these
effects under conditions found in actual mines. The
results ofthis study have been published under the
title "Sodium Silicate Grout Technology for
Effective Stabilization of Abandoned Flooded
Mines" and U.S. patent 4,804,297.
Chemistry
The chemistry that allows this process to work is.
based on the reactivity of soluble silicon dioxi
with muttivalent cationic metals such as calcium.
Historically, soluble silicates have been used as
‘cement modifies to yield mixtures with accelerated
set times; increased compressive strengths and
improved acid resistance.’ Established end uses
where the improved properties imparted by
silicates are made use of include water resistant
grouting, oil field cementing, hazardous waste
solidification and acid resistant cements. In these
applications, the silicon dioxide component of the
soluble’ silicate reacts with sources of calcium
present in the cement (soluble calcium, calcium
‘oxide and calcium hydroxide) to form various
calcium silicate compounds that hydrate with water
and increase the rate and number of bond sites
formed between aggregates.’ When added to a
cement sluny, the silicate quickly reacts to
produce these bonds and accelerates the setting
of the mix.
The hydrated calcium silicate compounds
produced from this reaction improve the final
physical properties of the cement mixture by
increasing the number of bonds formed between
the cement and aggregate particles.” Calcium
silicate is the active component of all Portiand
Cement systems and is responsible for the setting
‘and solidfication reactions when water is added.
By adding a soluble silicate to the mix and
introducing a source of reactive silicon dioxide, a
reactive form of Portland cement in situ ‘is
produced." Since the silicon dioxide is already in
a soluble form, the resultant calcium silicate
produced is hydrated more quickly than the
anhydrous. calcium slicate contained in the
cement." This is why controling the additon level
of silicates in modified cement systems allows
significant changes in the rate of set.
While the addition of sicate into a cement grout
does improve its behavior when placed under
water, it does not completely eliminate all the
problems that prevent effective stabilization of
flooded mines. The increased number of bonds
between the grout particles does help reduce the
separation of fy ash and cement when the grout
is injected in water, and the controlled set of the
grout helps to eliminate erosion of grout columns.
by moving water, but there can be limitations to
this approach. The most important of these is the
speed of the reaction when cement and silicate are
combined before placement. When mixed, the
calcium silicate formed immediately stats to bond
aggregate particles together."” The initial bonds
formed are sensitive to shear and when the
‘modified mix is pumped through the grout lines,
the bonds are easily disrupted or broken. Once
broken, these bonds are not readliy reformed, 30
there is a reduction in the benefits associated with
the addition of siicate.* Laboratory data indicates
that the breaking of the initial bonds formed can
reduce the final compressive strength of a siicate
modified cement by as much as 23%."*
‘An even greater limitation associated with mixing
silicate directly into a cement grout is the negative
effect. has on the handling and pumping
characteristics of the mix. To successfully place
the grout into a mine void, the mix must be
transferred through lines or hoses trom the mixer
to the. void. The lengths of these lines and the
distances the grout must travel are large and in
some cases can exceed 700 feet." The effect
silicate has on grout set times can-cause the mix
tolincrease in viscosity rapidly, which increases the
resistance the grout has to moving and the
pumping pressures required. In many cases, the
grout will have the tendency to set up too quickly
Which resutts in plugging of the grout lines and
causing considerable down time and increased
labor to clear the lines.
Through extensive testing, it has been
demonstrated that_ the self-supporting
characteristics of the silicate modified grout and
the final angle of repose of the formed columns
can be effected by penetration of the surrounding
water into the grout matrix after placement. When
intially injected into water, a silicate modified grout
will form a high angle of repose structure (35° or
greater) but with time, water is forced into the
grout due to osmotic pressure, which causes the
grout mass to swell and disrupts many of the
calcium silicate bonds that have been formed."
This results in a slumping of the grout and aSodium Silicate Grouts:
-
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outer Pipe = 2002080 #42
sosulus = oroaost £22
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NOT TO SCALE
eiicate
atx out
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reduction of the column height and angle of
repose. Grout structures formed underwater
havebeen found to deteriorate rapidly and lose
height and subsequent roof contact in as litle as,
fifteen minutes."”
To eliminate these problems associated with
silicate modified grouts, a grouting technique was
developed that would allow for effective placement
of these mixes. This technique relies on the use of
an annulus nozzle (figure 1) which combines
silicate and cement grout at the point of placement
instead of in the grout mixer. As the grout stream
‘enters the water at the line exit point, a stream of
liquid si rout by the
nozzle. This forms a curtain of silicate around the
grout which reacts with the grout stream surface
before the grout come into contact with the water.
This surface reaction promotes the formation of a
calcium silicate gel layer that prevents water from
Penetrating the mix and reducing its self
‘Supporting properties."” As a result, the grout can
form high angle of repose columns which will not
degrade over time.
Laboratory and field data have demonstrated that
this technique is superior to the process of mixing
the silicate into the grout mix prior to injection.
Data on compressive strength of grouts set this
way underwater shows that the silicate enhances
the ultimate strength of the set grout while
providing the other benefits that contribute to good