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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.
1
INTRODUCTION ing figure shows the structure of trimethylsilyl deriva
Waterglass (Na2O nSiO2) is also called sodium sil tives of the oligomeric silicate species (Fig. 1).
icate, often used as adhesive, inorganic binder, clean The derivatives are chemically inert substances sol
ers and detergents, waterproof coating, fireproof coat uble in organic solvents, low melting, and thermally
ing, zincrich anticorrosion coating, concrete gelati stable. Most important, derivatives with a limited
nizer, quicklimes retarder and so on [1]. However, number of silicate units are volatile and amenable to
waterglass composition is very complicate, there are analysis by gas chromatograph and mass spectrometry.
various types of species: monomeric species Si O 4 ,
4 Silylation and chromatography (TMSGC) have
been used successfully to determine the anionic con
6
linear dimeric species Si2 O 7 , linear trimeric species stitution of silicate minerals [2], but TMSGC has not
8 4 been used in the determination of silicate species in
Si3 O 10 and linear tetrameric species Si4O8 ( OH ) 4 , waterglass solution, owing to the persistent problem in
which can be identified by converting them to the cor silylation of silicate species with large amount of water.
responding organosilyl derivatives and determining Free silicic acids participate in rapid and reversible
them using gas chromatography [2]. By reason of very hydrationdehydration equilibria, and other silicic
easy polymerization of silicic acid during storage, the acids may form in the presence of water before they
structure and composition of the waterglass will can be stabilized as TMS derivatives.
change with time, leading to waterglass aging, this It is noted that sylylation can be viewed as occur
decreases the performance of waterglass and bring ring in two steps [2, 3]. The first is the exchange of
about lots of difficulties in practice work. sodium ions in the waterglass for the hydrogen ions to
According to Lentz [2], the oligomeric silicate spe give the corresponding silicic acid. The second is a
cies can be readily converted into trimethylsilyl (TMS) reaction of the silicic acid with silylating reagents to
derivatives by silylation reaction in the presence of iso block the reactiveacid groups and to yield the stable
propyl alcohol. TMS derivatives. Thus the acid such as 2 : 1 (V/V) HCl
H4SiO4 + 4TMSCl (TMS)4SiO4, is necessary to the sylylation process, it can offer the
where TMS represents the trimethylsilyl group hydrogen ions for the waterglass, and catalyze change
(CH3)3Si. It is a reaction of the silicic acid with sily of waterglass into the corresponding silicic acid. This
lating reagents that blocks the reactiveacid groups can overcome the difficulties in preparation of TMS
and yields the stable TMS derivatives [2]. The follow derivatives. In this paper, the proportions of 2 : 1 (V/V)
HCl to 0.85 mol/l waterglass solutions were screened
1 The article is published in the original.
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 Experiment Methods and Procedures
tone, while silylation reagent hexamethyl disiloxane is In this paper, the tetradecane (abbreviated as
also soluble in polar solvent acetone, this can induce n C *14 ) is chosen as internal standard to quantitatively
rapid silylation reaction of a waterglass solution with calculate the content of each oligomeric silicate spe
silylation reagent. For this reason, the polar acetone cies. So 5 g tetradecane was first dissolved in 100 ml
solvent was used in silylation process. The content of HMDS to prepare solution of internal standard.
oligomeric silicate species was determined by TMSGC The three kinds of waterglass selected in studies
method, and the changes of oligomeric silicate species have a SiO2 content of 25% by weight and a
after storage were also studied. To prevent the water SiO2/Na2O molar ratio () of (1.8, 2.4, or 3.6) : 1. In
glass from aging, the modification of waterglass was the experiments, the waterglass samples were stored
also performed by adding antiaging agent polyacryla respectively for two months and four months. Then
mide or by refluxcondensing, the antiaging mecha the samples had to be diluted to certain concentration
nism of polyacrylamide and refluxcondensing was that favors silylation process, the optimum concentra
further discussed. tion of waterglass samples was 0.85 mol/l by repeated
screening.
EXPERIMENTAL Next, the diluted waterglass samples were silanized
immediately, the silylation method can be seen in the
Reagent following.
9 ml 2 : 1 (V/V) HCl, 9 ml HMDS and 1 ml of
Amberlyst15 cation exchange resin, olivine internal standard solution were added into 15 ml ace
((Mg, Fe)2SiO4, the content is 88.0%), (all above is tone with strong magnetic stirring for 30 min, then
produced in America); acetone (AR), tetradecane 10 ml diluted waterglass samples were added into the
(GR), NaOH (AR), polyacrylamide (CP); hexame mixture solution to hold the total amount of various
thyl disiloxane (99%) (abbreviated as HMDS) silicate species at 8.5 mmol. All of these mixtures were
(Bengbu chemical industry research institute in kept stirring for 90 min. After that, the reacted solution
Anhui, China); Silica gel (AR). was separated by tundish, and the organic solution was
washed with water for three times.
Apparatus Finally, Amberlyst15 cation exchange resin was
added into the organic solution, ultrasonic treatment
Ultrasonic cleaner, gaschromatography (analysis for 1 h, then filtrated and the leaching liquid as silyla
instrument factory in Beijing). tion derivation was analyzed by gaschromatograph,
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.
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.
After the modified waterglass solution was heated Project Program of State Key Laboratory of Inorganic
and refluxed, the content of monosilicate, cyclictet Synthesis and Preparative Chemistry, Jilin University
rameric silicate and cyclicoctameric silicate was very much for financial support.
almost kept unchanged, but the content of dimeric sil
icate, lineartrimeric silicate and lineartetrameric sil
icate increased obviously, leading to an increase of the REFERENCES
content of low and middlemolecularweight silicate 1. Chinese Ceramic Society, Thesaurus of Silicates,
oligomers, and a corresponding decrease of the total Beijing: China Construction Industry Press, 1984.
amount of high polysilicates. It demonstrates that the 2. Lentz, C.W., Silicate Minerals as Sources of Trimethyl
composition of the modified waterglass tends to return silyl Silicates and Silicate Structure Analysis of Sodium
back to its original orientation after being heated and Silicate Solutions, Inorg. Chem., 1964, vol. 3, no. 4,
refluxed. The results also show the modifier agent pp. 574579.
polyacrylamide can exert protective effect on the 3. Chen, R., Yang, Y., Guo, L., Wang, Z., Liu, H., and
dimeric silicate, lineartrimeric silicate and lineartet Dai, A., Studies on Silicic Acid and Its Salts: XXI.
rameric silicate, and thus decrease the polymerization Determination of Dissociation Constant of Monosi
rate of silicates, then stop them from polymerizing licic Acid through TrimethylsilyationGas Chromatogra
phy, Chin. J. Inorg. Chem., 1991, vol. 7, no. 1, pp. 9397.
into high polysilicates.
4. Calhoun, H.P. and Masson, C.R., Trimethylsilyl
Finally the conclusion can be obtained that the Derivatives for the Study of Silicate Structures: Part 7.
content of monosilicate and various silicate oligo Calcium Silicate Structures, J. Chem. Soc., Dalton
mers can be determined through the study on water Trans., 1980, no. 8, pp. 12821291.
glass aging by using TMSGC, and so leading to find 5. Garz, G., Hoebbel, D., Ecsery, Z.J., and Ujszszi, K.,
ing the aging mechanisms and antiaging methods Gas Chromatography of Trimethylsilylated Silicate
concerning waterglass by modification, heating and Anions: Separation with Glass Capillary Columns and
reflux. New Aspects in Derivatization, J. Chromatogr., 1978,
vol. 167, issue C, no. 21, pp. 321336.
We thank the National Natural Science Founda 6. Iler, R.K., The Chemistry of Silica, New York: John
tion of China (no. 20577010) as well as the Open Wiley and Sons, 1979.