ISSN 10876596, Glass Physics and Chemistry, 2010, Vol. 36, No. 1, pp. 110115. Pleiades Publishing, Ltd.

., 2010.

A Study on Waterglass Aging by Determination of Oligomers

using Feasible TrimethylsilylGasChromatography Method1
Pan MingChua, Deng WenJingb, Yang YuXianga, b, *, and Chen YaRub
a
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035 P.R. China
*email: yuxyang@online.sh.cn
bDepartment of Chemistry, East China University of Science and Technology, Shanghai, 200237 P.R. China

Received October 25, 2007

AbstractIn this paper, the trimethyisilyl method was used to study the aging process of waterglass, in which
HCl was successfully used as acidic catalystes and a strong polar acetone was used as organic solvent. The
results show, all the oligomeric silicate species can be completely converted into trimethylsilyl (TMS) deriv
atives, when waterglass was stored, the content of monosilicate gradually increases, and the content of sili
cate oligomers decreases, but total amount of high polysilicates increases instead, leading to the phenomenon
of bipolar differentiation occurring. However when waterglass is modified, content of oligomeric silicate
species increases, but content of polymeric silicate species decreases, and when waterglass is refluxcon
densed, the composition tends to return back to its original orientation.

Key words: silylation process, strong polar solvent, waterglass, aging

DOI: 10.1134/S1087659610010189

1
INTRODUCTION
Waterglass (Na2O nSiO2) is also called sodium sil
icate, often used as adhesive, inorganic binder, clean
ers and detergents, waterproof coating, fireproof coat
ing, zincrich anticorrosion coating, concrete gelati
nizer, quicklimes retarder and so on [1]. However,
waterglass composition is very complicate, there are
various types of species: monomeric species Si O 4 ,
4 Silylation and chromatography (TMSGC) have
6
linear dimeric species Si2 O 7 , linear trimeric species
8 4
Si3 O 10 and linear tetrameric species Si4O8 ( OH ) 4 ,
which can be identified by converting them to the cor
responding organosilyl derivatives and determining
them using gas chromatography [2]. By reason of very
easy polymerization of silicic acid during storage, the
structure and composition of the waterglass will
change with time, leading to waterglass aging, this
decreases the performance of waterglass and bring
about lots of difficulties in practice work.
According to Lentz [2], the oligomeric silicate spe
cies can be readily converted into trimethylsilyl (TMS)
derivatives by silylation reaction in the presence of iso
propyl alcohol.
H4SiO4 + 4TMSCl (TMS)4SiO4,
where TMS represents the trimethylsilyl group
(CH3)3Si. It is a reaction of the silicic acid with sily
lating reagents that blocks the reactiveacid groups
and yields the stable TMS derivatives [2]. The follow
1 The article is published in the original.
ing figure shows the structure of trimethylsilyl deriva
tives of the oligomeric silicate species (Fig. 1).
The derivatives are chemically inert substances sol
uble in organic solvents, low melting, and thermally
stable. Most important, derivatives with a limited
number of silicate units are volatile and amenable to
analysis by gas chromatograph and mass spectrometry.
been used successfully to determine the anionic con
stitution of silicate minerals [2], but TMSGC has not
been used in the determination of silicate species in
waterglass solution, owing to the persistent problem in
silylation of silicate species with large amount of water.
Free silicic acids participate in rapid and reversible
hydrationdehydration equilibria, and other silicic
acids may form in the presence of water before they
can be stabilized as TMS derivatives.
It is noted that sylylation can be viewed as occur
ring in two steps [2, 3]. The first is the exchange of
sodium ions in the waterglass for the hydrogen ions to
give the corresponding silicic acid. The second is a
reaction of the silicic acid with silylating reagents to
block the reactiveacid groups and to yield the stable
TMS derivatives. Thus the acid such as 2 : 1 (V/V) HCl
is necessary to the sylylation process, it can offer the
hydrogen ions for the waterglass, and catalyze change
of waterglass into the corresponding silicic acid. This
can overcome the difficulties in preparation of TMS
derivatives. In this paper, the proportions of 2 : 1 (V/V)
HCl to 0.85 mol/l waterglass solutions were screened
out as 9 : 10 (V/V).

110
 A STUDY ON WATERGLASS AGING BY DETERMINATION OF OLIGOMERS 111

T T T T T T
O O O O O O
TO Si OT TO Si O Si OT TO Si O Si O Si OT
O O O O O O
T T T T T T
QM4 : Monomer Q2M6 : Dimer Q3M8 : Linear Trimer

T T
O O
T Si O Si O
T T T T T
O O O O
O O O O
Si O Si O
TO Si O Si OT TO Si O Si OT
O Si O Si
T T O
O O O O OO
T T
O Si O O Si O Si OT O Si O Si T
O O O O O
T T T T T
Q3M6 : Cyclictrimer Q4M8 : Cyclictetramer Q8M8 : Cyclicoctamer

CH3
Fig. 1. Schematic structure of trimethylsilyl derivatives of silicate anions, T CH3 Si .
CH3

The water is more soluble in strong polarizable ace
tone, while silylation reagent hexamethyl disiloxane is
also soluble in polar solvent acetone, this can induce
rapid silylation reaction of a waterglass solution with
silylation reagent. For this reason, the polar acetone
solvent was used in silylation process. The content of
oligomeric silicate species was determined by TMSGC
method, and the changes of oligomeric silicate species
after storage were also studied. To prevent the water
glass from aging, the modification of waterglass was
also performed by adding antiaging agent polyacryla
mide or by refluxcondensing, the antiaging mecha
nism of polyacrylamide and refluxcondensing was
further discussed.
EXPERIMENTAL
Reagent
Amberlyst15 cation exchange resin, olivine
((Mg, Fe)2SiO4, the content is 88.0%), (all above is
produced in America); acetone (AR), tetradecane
(GR), NaOH (AR), polyacrylamide (CP); hexame
thyl disiloxane (99%) (abbreviated as HMDS)
(Bengbu chemical industry research institute in
Anhui, China); Silica gel (AR).
Apparatus
Ultrasonic cleaner, gaschromatography (analysis
instrument factory in Beijing).
Experiment Methods and Procedures
In this paper, the tetradecane (abbreviated as
n C *14 ) is chosen as internal standard to quantitatively
calculate the content of each oligomeric silicate spe
cies. So 5 g tetradecane was first dissolved in 100 ml
HMDS to prepare solution of internal standard.
The three kinds of waterglass selected in studies
have a SiO2 content of 25% by weight and a
SiO2/Na2O molar ratio () of (1.8, 2.4, or 3.6) : 1. In
the experiments, the waterglass samples were stored
respectively for two months and four months. Then
the samples had to be diluted to certain concentration
that favors silylation process, the optimum concentra
tion of waterglass samples was 0.85 mol/l by repeated
screening.
Next, the diluted waterglass samples were silanized
immediately, the silylation method can be seen in the
following.
9 ml 2 : 1 (V/V) HCl, 9 ml HMDS and 1 ml of
internal standard solution were added into 15 ml ace
tone with strong magnetic stirring for 30 min, then
10 ml diluted waterglass samples were added into the
mixture solution to hold the total amount of various
silicate species at 8.5 mmol. All of these mixtures were
kept stirring for 90 min. After that, the reacted solution
was separated by tundish, and the organic solution was
washed with water for three times.
Finally, Amberlyst15 cation exchange resin was
added into the organic solution, ultrasonic treatment
for 1 h, then filtrated and the leaching liquid as silyla
tion derivation was analyzed by gaschromatograph,

GLASS PHYSICS AND CHEMISTRY Vol. 36 No. 1 2010

112 PAN MINGCHU et al.
N14
QM4 2 then programmed at 8C/min from an initial temper
1 Q2M6
3 Q4M8 Q M
3 8
4 Q8M8 Q4M10
5
6 7
Q16M16 Q5M12
8 9
Fig. 2. Chromatogram of various silicate oligomer deriva
tives in waterglass ( = 1.8) that had been just made up
(SiO2 concentration 25%): QM4 mono; Q2M6 linear
di; Q4M8 cyclic tetra; Q3M8 linear tri; Q8M8
cyclic octa; Q4M10 linear tetra; Q16M16 cyclic hexa
decane; Q5M12 chain penta.
the results were treated by DPchromatograph data
integration instrument.
Silylation of Olivine standard sample: 2.2544 g
of grinded olivine (containing Si 8.41 mmol) was
silanized by the above silylation method. But it took
45 h to dissolve grinded olivine completely.
In order to prevent waterglass from aging, poly
acrylamide as modifier reagent was added into water
glass solution ( = 2.44) with 47.4% concentration, in
which polyacrylamide content was kept at 0.3%. This
waterglass is called modified waterglass.
The modified waterglass and the unmodified
waterglass were stored for two months. After that, each
of them was respectively diluted to the concentration
0.85 mol/l, then the diluted samples comprising
8.5 mmol of total silicate species were silanized imme
diately by the above mentioned silylation method.
After storage for two months, the modified
waterglass and the unmodified waterglass were respec
tively heated and refluxed for 4 h, then each of them
was respectively diluted to the concentration
0.85 mol/l. Next, the diluted samples comprising
8.5 mmol of total silicate species were silanized imme
diately by the above mentioned silylation method.
RESULTS AND DISCUSSION
Selection of the Chromato Operation Parameter
A quantitative Gas chromatography determination
of the silylation derivatives using tetradecane as inter
nal standard was performed on a stainless steel column
(3 m 3 mm) packed with 3% SE30 stationary phase
coated Chromosorb GAW (DMCS, 80100 mesh)
and detected by FID with N2 carrier gas flow rate of
38 ml/min. The best resolution and peak shape was
GLASS PHYSICS AND CHEMISTRY
obtained with the temperature of (FID) up to 250C,
the air flow rate at 70 ml/min, and the hydrogen flow
rate at 40 ml/min. The GC column temperature was
ature of 90C to a final temperature of 270C, the gas
ification room was held at 250C to keep the silylation
derivatives entering FID in the state of gas. The opti
mum injection amount was 4 l in order to get the best
peak shape and column separation efficiency on
organic silicon derivatives.
Determination of Various Oligomeric Silicate
Species Content in Waterglass
Figure 2 is the chromatogram of various silicate oli
gomer derivatives in waterglass ( = 1.8) that had been
just made, the derivative chromatograms of the water
glasses ( = 1.8, 2.4, and 3.6) stored for two or four
months are similar to those in Fig. 2, only the peaks
area shows different in various chromatogram.
According to qualitative identification of hyphen
ated technology of GCMS (gas chromatographmass
spectrometer) [3], each chromatogram peak in Fig. 2
is corresponding to the monosilicic acid and various
oligomer species respectively, among which peak 2 is
assigned to standard sample of tetradecane.
Because column separation of high molecular
weight oligomers must be performed at higher temper
ature than the temperature of gasification room [4], so
the amount of high molecular weight polysilicates can
only be estimated by the difference between the total
amount of various silicate species and amount of vari
ous oligomer species.
Each monosilicic acid and oligomer species con
tent in waterglass with different molar ratio is listed in
Table 1.
Quantitative Calculation
of Oligomeric Silicate Species
The internal standard method of tetradecane was
used in determination of each monosilicic acid and
oligomer content in waterglass, in which peaks area is
proportional to the content of component i.
Cs = fs As
(1)
Ci = fi Ai .
In Eq. (1), Cs is mol concentration of interior stan
dard sample, Ci is mol concentration of the tested
composition, As and Ai are the peak area of interior
standard sample and the tested composition respec
tively. When fs = 1, the relative mol correction factor
fi = Ci As/Cs Ai, the relative mol corresponding factor
Fi = 1/fi, whose value can be obtained from the chro
matogram of the standard sample (Olivine).
Since the ratio (Fi/aM) of mol correction factor (Fi)
to the number (aM) of trimethylsilyl is a constant value
[5], the correction factor of the other silanization
Vol. 36 No. 1 2010
 A STUDY ON WATERGLASS AGING BY DETERMINATION OF OLIGOMERS 113

Table 1. Polysilicate content in waterglass with different molar ratio and its variations with time
Molar Total amount Total
ratio Time, of monosi amount
QM4 n C14 Q2M6 Q4M8 Q3M8 Q8M8 Q4M10
( = months licic acid and of highpoly
SiO2/Na2O) oligomers silicates

A s*
= 1.8 0 155.9 100.0 51.8 13.6 132.7 25.4 97.4
mmol 3.25 0.72 0.14 1.38 0.25 0.81 6.56 1.94
2 As 175.0 100.0 40.5 5.3 92.9 11.1 73.3
mmol 3.65 0.56 0.06 0.97 0.12 0.61 5.97 2.53
4 As 191 100.0 24.8 6.1 24.5 19.5 16.1
mmol 3.98 0.34 0.06 0.26 0.20 0.13 4.97 3.53
= 2.4 0 As 137.2 100.0 29.0 12.0 72.4 37.0 63.6
mmol 2.86 0.40 0.13 0.75 0.39 0.53 5.06 3.44
2 As 191.0 100.0 25.8 4.5 20.6 4.2 3.0
mmol 3.98 0.36 0.05 0.21 0.04 0.03 4.67 3.83
4 As 200.0 100.0 13.4 1.9 13.2 5.9 9.5
mmol 4.17 0.19 0.02 0.14 0.06 0.08 4.63 3.84
= 3.6 0 As 122.6 100.0 20.0 1.9 38.1 5.8 40.0
mmol 2.55 0.28 0.02 0.40 0.06 0.33 3.64 4.86
2 As 151.2 100.0 13.3 0.3 14.7 1.3 6.8
mmol 3.15 0.18 0.00 0.25 0.01 0.08 3.65 4.85
4 As 160.7 100.0 9.0 2.3 7.8 2.6 4.3
mmol 3.35 0.13 0.02 0.08 0.03 0.04 3.65 4.85
Olivine 403.7
Mol correction factor of F1 12 18 24 24 24 30
Note: A *
s peak area.

derivatives can be obtained, the results can be seen in So the total amount of high polysilicates is esti
Table 1. mated by the difference between the total amount of
From Fi = 1/fi, Cs = W n C14 / M n C14 and Ci = various polysilicates and amount of low molecular
weight silicate oligomers, i.e.,
Wi/Mi, the equation was acquired:
Wi
W A 1 Wn C
i = i  14 .
A s F i M n C
(2)
8.5 
i
M
 ( mmol ) .
i
Ms 14

In the equation, Wi and Mi represent the mass and And thus the content of differentlength oligomers
relative mol mass of the tested composition respec in waterglass is obtained by considering experimental
value of Ai and Fi in Eq. (3).
tively, W n C14 and M n C14 represent interior standard
mass and relative mol mass.
In this paper: CALCULATED RESULTS
5  1 = 50 mg, M
W n C14 =  The composition of waterglass is very complicate, it
n C 14 = 198.4. Sup
100 contains not only monosilicate, but also silicate oli
posed As = 100%, then gomers, such as dimeric silicate, cyclictetrameric,
lineartrimeric, cyclicoctameric, lineartetrameric,
Wi Ai 1 50 A
   = i 0.25,
 =  (3) cyclichexadecanemeric and linearpentameric. The
Mi 100% f i 198.4 Fi content of monosilicate and these silicate oligomers
W can be seen in Table 1. The results demonstrate that
where, i is the molar amount of the component i. the content of monosilicate and these silicate oligo
Mi mers varies with molar ratio of waterglass.

GLASS PHYSICS AND CHEMISTRY Vol. 36 No. 1 2010

114 PAN MINGCHU et al.

Table 2. Polysilicate content in modified or unmodified waterglass and its variations with reflux
Derivatives of oligomers Total Total
amount amount
Manipulation methods Sam oligomeric of high
QM4 ple Q2M8 Q4M8 Q3M8 Q8M8 Q4M10 Q16M16 Q5M12 silicate spe polysili
n C14 cies cates
Un Unmodified A* 256.2 100.0 59.2 0.2 81.0 6.4 11.8 6.7 1.7
s
reflux
mmol 5.34 0.82 0.00 0.84 0.07 0.10 0.03 0.01 7.21 1.29
Modified As 255.2 100.0 57.1 0.1 108.8 9.2 71.8
mmol 5.32 0.79 0.00 1.13 0.10 0.60 7.94 0.56
Re Unmodified As 247.0 100.0 51.7 0.36 96.0 5.5 109.3
flux
mmol 5.15 0.72 0.00 1.00 0.06 0.91 7.84 0.66
Modified As 256.6 100.0 88.1 0.37 174.7 8.9 143.0 3.2
mmol 5.35 1.22 0.00 1.82 0.09 1.19 0.02 9.69 0
Correction factor of mol F1 12 18 24 24 24 30 48 36
Note: A s* peak area.

With molar ratio of waterglass becoming larger, the CONCLUSIONS

content of monosilicate gradually becomes lower, the
amount of silicate oligomers also decreases, but total
amount of high polysilicates increases instead. This is
because the larger molar ratio leads to the higher
degree of polymerization [6], and more high polysili
cates in solution.
By comparing the content of monosilicate with
various silicate oligomers in the waterglass solution
(molar ratio = 1.8, 2.4, or 3.6), which have been just
made up, or stored for two months and four months,
the results can be obtained, that with increasing time
in storage, the content of monosilicate and the con
tent of total amount of high polysilicates all increase,
except the content of silicate oligomers decreases,
leading to the phenomenon of bipolar differentia
tion occurring.
The change tendency is different with the molar
ratio of waterglass, when = 1.8, the change tendency
is obvious, when = 2.4, the change tendency is just
obvious after storage for two months, but the change
tendency decreases after storage for four months.
Table 1 also shows that when = 3.6, the amount of
monosilicate and total amount of high polysilicates
change almost little, because the change tendency is
related to the degree of silicate polymerization [6].
The silanization derivatives chromatogram of the
modified or unmodified waterglass and refluxed
waterglass can be seen in Fig. 1, the content of mono
silicate with various silicate oligomers in the waterglass
solution (the modified or unmodified) can be seen in
Table 2.
The comparison of various oligomeric silicate spe
cies content in the waterglass solution (modified or
unmodified) led to the following results.
The content of monosilicate, dimeric silicate,
cyclictetrameric silicate was almost kept unchanged
in the modified or unmodified waterglass solution dur
ing a storage, but the content of lineartrimeric sili
cate, cyclicoctameric silicate and lineartetrameric
silicate all increased obviously. Besides, there still
existed a little cyclichexadecanemeric and linear
pentameric silicates in unmodified waterglass. But
when the waterglass was modified, the content of mid
dle and high molecular weight silicate oligomers all
increased, because the modifier agent polyacrylamide
can protect lineartrimeric silicate, cyclicoctameric
silicate and lineartetrameric silicate from polymeriz
ing into high polysilicates, and thus the content of
middle and high molecular weight silicate oligomers
all increased, resulting in the total amount of high poly
silicates decreasing in the modified waterglass.
After the unmodified waterglass solution was
heated and refluxed, the content of monosilicate and
dimeric silicate decreased little, the content of cyclic
tetrameric silicate and cyclicoctameric silicate were
kept unchanged, but the content of lineartrimeric sil
icate and lineartetrameric silicate increased a lot, this
led to an increase of the amount of the low and mid
dlemolecularweight silicate oligomers, and a corre
sponding decrease of total amount of high polysili
cates, the results were just reversed to those of Table 1.
It demonstrates that the heat and reflux can take the
antiaging action, the composition of waterglass
tends to return back to its original orientation after
being heated and refluxed.

GLASS PHYSICS AND CHEMISTRY Vol. 36 No. 1 2010

 A STUDY ON WATERGLASS AGING BY DETERMINATION OF OLIGOMERS
After the modified waterglass solution was heated
and refluxed, the content of monosilicate, cyclictet
rameric silicate and cyclicoctameric silicate was
almost kept unchanged, but the content of dimeric sil
icate, lineartrimeric silicate and lineartetrameric sil
icate increased obviously, leading to an increase of the
content of low and middlemolecularweight silicate
oligomers, and a corresponding decrease of the total
amount of high polysilicates. It demonstrates that the
composition of the modified waterglass tends to return
back to its original orientation after being heated and
refluxed. The results also show the modifier agent
polyacrylamide can exert protective effect on the
dimeric silicate, lineartrimeric silicate and lineartet
rameric silicate, and thus decrease the polymerization
rate of silicates, then stop them from polymerizing
into high polysilicates.
Finally the conclusion can be obtained that the
content of monosilicate and various silicate oligo
mers can be determined through the study on water
glass aging by using TMSGC, and so leading to find
ing the aging mechanisms and antiaging methods
concerning waterglass by modification, heating and
reflux.
We thank the National Natural Science Founda
tion of China (no. 20577010) as well as the Open
GLASS PHYSICS AND CHEMISTRY Vol. 36 No. 1
115
Project Program of State Key Laboratory of Inorganic
Synthesis and Preparative Chemistry, Jilin University
very much for financial support.
REFERENCES
1. Chinese Ceramic Society, Thesaurus of Silicates,
Beijing: China Construction Industry Press, 1984.
2. Lentz, C.W., Silicate Minerals as Sources of Trimethyl
silyl Silicates and Silicate Structure Analysis of Sodium
Silicate Solutions, Inorg. Chem., 1964, vol. 3, no. 4,
pp. 574579.
3. Chen, R., Yang, Y., Guo, L., Wang, Z., Liu, H., and
Dai, A., Studies on Silicic Acid and Its Salts: XXI.
Determination of Dissociation Constant of Monosi
licic Acid through TrimethylsilyationGas Chromatogra
phy, Chin. J. Inorg. Chem., 1991, vol. 7, no. 1, pp. 9397.
4. Calhoun, H.P. and Masson, C.R., Trimethylsilyl
Derivatives for the Study of Silicate Structures: Part 7.
Calcium Silicate Structures, J. Chem. Soc., Dalton
Trans., 1980, no. 8, pp. 12821291.
5. Garz, G., Hoebbel, D., Ecsery, Z.J., and Ujszszi, K.,
Gas Chromatography of Trimethylsilylated Silicate
Anions: Separation with Glass Capillary Columns and
New Aspects in Derivatization, J. Chromatogr., 1978,
vol. 167, issue C, no. 21, pp. 321336.
6. Iler, R.K., The Chemistry of Silica, New York: John
Wiley and Sons, 1979.
2010