Note: Descriptions are shown in the official language in which they were submitted.
3 3 7
The present invention relates to compositions
of binders. Most advantageously the invention can be
used for manufacturing concrete and reinforced concrete
products.
It is well known that the properties and para-
meters of a binder determine the physical and chemical
properties of concrete as well as the cost thereof.
Therefore many attempts have been made to improve binder
compositions.
Known in the art are binders comprising
granulated slag and compounds of alkali metals.
For manufacturing said binders, use is made of
granulated blast furnace slags and electrothermophosphoric
slags having a specific surface of not more than 300 m2Jkg.
Used as compounds of alkaline metals are carbonates,
fluorides, hydroxides and, most widelyj sodium silicates
and potassium silicates which are soluble glasses.
Such binders are very active, and concrete
stone based thereon possesses high corrosion resistance,
cold resistance, water impermeability, heat resistance,
air resistance, water resistance, adhesion to fillers,
reinforcement, etc. They solidify in the air and in
water and possess high hydraulic properties (V.D.
Gluhovsky et al-Shchelochnyie i shelochno-zemelnyie
gidravlicheskie viazhushchie i betony, Kiev, Vyshcha
shkola Publishers, pp. 103-104).
However, because of considerable variations
of chemical, mineralogical and phase composition of
slags the prior art binders gain strength slowly.
Therefore said binders are not used as quick-hardening
binders.
In addition, cement stone based on such
binders in some cases possesses increased shrinking
deformation and increased time of damping thereof as
compared to portland cement stone.
~ ~ 6~37
-- 2 --
There is also kn~wn in the art a binder dis-
closed in USSR Inventor s Certificate No. ~08,928 and
comprising in % by weight:
- granulated blast furnace slag... 55~5 to 61~0
- soluble glass..... ~..... ~... ~... 29.0 to 33.0
- portland cement... ......... ~... 10.0 to 11.0
To obtain the above binder, the granulated
blast furnace slag is preliminarily ground until the
s~ecific surface of the slag is 2,800 to 3,000 cm2/g
and then mixed with the portland cement. Thereafter
the obtained mixture is sealed by an alkali component.
The alkali component is a solution of sodium (or
potassium) glass having a modulus of 1.8 to 2.3 and a
density of 1.3 to 1.35 g/cm3 in an amount of 40 to 43%
of the weight of dry components.
The tests of the prior art binder have shown
that the activity thereof both at early stages of
solidification and later is low. In addition, the
prior art binder gains strength slowlyO Thus, the
compressive strength of the prior art binder in one
day is 10.6 MPa, and in 28 days, 32.6 MPa.
This is due to the fact that the binder com-
prises portland cement which contains gypsum intensify-
ing the solidification process. The gypsum reacts with
the alkali component and neutralizes it, which results
in the formation of salts. This reduces the content of
the alkali component in the binder, which brings about
a decrease in the activity and atmospheric durability
thereof.
An object of the invention is to provide a
binder possessing high operation properties due to an
increase in the rate of strengthening and activity
thereof.
The object set forth is attained by that
there is provided a binder comprising a granulated
1 ~ 65337
-- 3 --
blast furnace slag, a compound of an alkali metal and
an additive, wherein, according to the invention, the
additive is a portland cement clinker, or sodium
sulphate, or potassium sulphate, the components being
taken in the following ratio~ % by weight:
- granulated blast furnace slag.... 79 to 98.5
- compound of an alkali metal....... 1 to 12
- portland cement clinker, or sodium
sulphate, or potassium sulphate
as the additive.................. 0.5 to 9
The invention makes it possible to improve
the operation properties of the binder due to both an
increase in the rate of strengthening and activity
thereof.
The above effect is attained due to the
optimum ratio between gel and crystals of low-basic
compounds in the gel-and-crystalline structure being
formed.
It is recommended that the binder comprise
granulated blast furnace slag, carbonates or silicates,
or hydroxides, or fluorides of sodium or potassium, and
a portland cement clinker as an additive in the follow-
ing ratio, % by weight:
- granulated blast furnace slag.... 79 to 96
- carbonates or silicates, or
hydroxides, or fluorides of
sodium or potassium..... ~... O.. ~........... 3 to 12
- portland cement clinker.O....-..-- 1 to 9
This modification of the binder provides for a
high and stable strength during the whole period of
solidification of the binder, durability and weather-
proofness thereof, and in addition allows the utiliza-
tion of granulated slags of various basicity for
producing a binder possessing said properties.
It is expedient that the binder comprise the
~ i~ 1 65337
granulated blast furnace slag, sodium silicate, and
sodium sulphate or potassium sulphate as the additive
in the following ratio of the components, % by weight:
- granulated blast furnace slag..... 80 to 98.5
- sodium silicate ................. ~.O 1 to 10
- sodium sulphate or potassium
sulphate ~............... ~............ ~. 0.5 to 1.0
Said modification of the binder allows for
acceleration of tha hydration process, which provides
for a higher strength of the binder at early time of
-solidification.
Now the invention will be described by
specific Examples thereof.
Example 1
The binder of the present invention comprises,
% by weight:
- granulated blast furnace slag................ 79
- compound of an alkali metalO............... ~ 12
- additive ..................................... 9
The granulated blast furnace slag of the
following ccmposition was used, % by weight: SiO2, 33.6;
A12O3, 15-85, Fe2~3, 2-45, CaO, 35.67, MgO, 8.90,
SO3, 1.34, MnO, 1.40.
9~/O Na2CO3 and l~/o NaOH were used as the com-
pound of an alkali metal, and portland cement clinker as
the additiveO
To produce the binder, the granulated blast
furnace slag and portland cement clinker were ground in
a ball mill till the specific surface thereof was
3,160 cm ~g. Then to the obtained mixture a solution
;~ containing 9~/O Na2CO3 and l~/O NaOH was added.
~; ~ The produced binder was tested to determine the
bending strength and the compressive strength thereof in
1, 3, 7 and 28 days, the bending strength and the compress-
ive strength thereof after steaming~ and shrinkage deforma-
1 ~B~337
-- 5 ~
tion thereof in 28 and 100 da~s.
The testing procedures are given below. Theresults of the tests are given in Table 1. For com-
parison purposes the Table represents the results of
testing the binder disclosed in USSR Inventor s
Certificate ~o. 408,~28.
To determine the consistency of the cement
solution (binder solution), sand taken in an amount of
1,500 g and having a size of 0.5 to 0.85 mm and a
powder taken in an amount of 500 g and consisting of
the granulated slag and the additive are mixed toget-
her. The blast furnace granula~ed slag and the
additive are preliminarily dried until the residual
moisture content thereof is 1% by mass and ground to
a specific surface thereof of 3,000 to 3,400 cm2/g.
The mixture is poured into a spherical cup preliminarily
wiped with a moist cloth and stirred therein for 1 min.
In the centre of the mixture there is prepared
a hollow for a solution of an alkali component to be
poured therein at a temperature o~ 20 + 2C and in an
amount of 150 g, the ratio between the quantity of the
solution of the alkali component and the quantity of
the cement (binder) being 0.3. Further hereinbelow
this ratio will be represented as S/C=0-3- The obtained
sand-and-cement mixture is held for 0.5 min. and stirred
~or 1 min., whereupon it is poured into a cup of a
stirrer and stirred therein for 2.5 min.
A conical mould having the dimensions of
D = 100 mm, d = 70 mm and h = 60 mm is placed in the
centre of a 300 mm in dia. disk of a vibrating platform.
Prior to the testing procedure the inner surface of the
cone and the disc of the platform are wiped with a humid
cloth.
After the stirring has been finished, the
conical mould is filled with the mixture to a half height
, ' '' ' .
.
~ ~ ~533~
thereof, wherein the mixture is compacted by driving
thereinto a rod of d = 20 mm and 1 = 150 to 180 mm
15 times~ Then the cone is filled to an excess with the
mixture which is compacted by driving thereinto a rod
10 times. Following the compaction the excess of the
mixture is cut off with a knife level with the edge of
the cone, whereupon the mould is taken off in a vertical
direction.
The sand-and-cement mixture having a shape of
a cone is shaken on the platform 30 times in 30 - s~
whereupon the lowest diameter of the cone is measured
in two mutually perpendicular directions so as to
determine the average value thereof. With S/C = 0.3 the
,spread of the cone should be within the range of 106 to
115 mm. If the spread of the cone is less than 106 mrn,
the amount of the solution of the alkali component is
increased to obtain the spread of the cone within the
range of 106 to 108 mm. If the spread of the cone is
more than 115 mm, the amount of the solution of the
alkali component is decreased to obtain the spread of
the cone within the range of 113 to 115 mm.
The ratio between the amount of the alkali
component and the amount of the cement ~binder),
obtained after the cone has spread to 106 to 115 mm,
is accepted for further tests.
To determine the strength characteristics of
the cements (binder), there are produced specimens
having a size of 40x40xlO0 mm and made from the cement
solution prepared as described above and having a
consistency characterized by the spread of the cone
within the range of 106 to 115 ~n~
Prior to making the specimens, the inner
surface of the moulds is slightly lubricated with
machine oil. At least 3 specimens are made for each
test.
~r
3 3 7
The moulds for making specimens are rigidly
secured onto the vibrating platform. The mould is
filled with the solution approximately to 1 cm of its
height, whereupon the mould ~ shaken. During the
first two minutes the mould is gradually filled with
small portions of the solution. After three minutes
the shaking is completed. The mould is taken off from
the vibrating platform, the excess of the solution is
cut off with a knife moistened with water, and the
surface is levelled off.
Having thus been made~ the specimens con-
tained in the moulds are held in a bath with a seal
water for 24 + 2 hours. Thereafter the specimens are
carefully removed from the moulds and placed horizontally
into baths with water so that they do not contact one
another~ The water should cover the specimens by not
less than 2 cm. The temperature of the water should be
20 + 2C. Then the specimens are taken out of the water,
and not later than in one hour are tested to determine
the bending strength and the compressive strength
thereof.
The bending strength is determined by applying
a bending load until a specimen is broken. The halves
of the specimens obtained after bending strength testing
are placed between two plates, the area of each plate
being 25 cm2, and the compressive strength is determined.
To determine the strength after steaming, there
are again made specimens as described above. Then closed
m ~ ds containing specimens are placed into a steaming
chamber and held therein for 120 + 10 min. at a tempera-
ture of 20 + 3C, the heater being disconnected. The
steaming process is carried out in accordance with the
following conditions: gradual raising of temperature up
to 85 + 50C for 180 - 10 min.~ holding the specimens at
this temperature for 360 + 10 min., cooling the specimens
1,~
~ 1 ~5337
-- 8 -
for 120 + 10 min. with the heater being disconnected.
In 24 + 2 hours from the moment of production the
specimens are removed from the mouldsl and the bending
strength and the compressive strength thereof are
determined.
To determine the shrinkage deformation, again
specimens are prepared. In the centre of the butt-end
walls of the mould there are made sockets to be filled up
with plasticine. 5 to 6 in dia. balls are impressed
thereinto. Further on, the production of the specimens
proceeds similarly to that described above. In 48 + 2
hours, counting from the moment of production, the
specimens are removed from the moulds and immediately
immersed into water having a temperature of 20 + 2C
for 5 days. Thereafter the specimens are placed into
an exicator containing 200 g of dry K2CO3 and 150 ml of
the supersaturated solution thereof. The specimens are
held under the solution at the temperature of the air
in the room being 20 + 2C. Then the lengths of the
specimens are measured by any conventional method to
an accurac~ of 0.01 mm and its variation is calculated
relative to the length of the specimen of the age of
8 days-
Example 2
The binder of the present invention comprises,
% by weight:
- granulated blast furnace slag ............ 96
- ccmpound of an alkali metal .............. 3
- additive
The granulated blast furnace slag of the follow-
ing composition was used, % by weight: SiO2, 4~.21;
A12O3~ 5038; Fe203, 0.~7; CaO, 46.3; MgO, 4.50; SO3, 0.56;
MnO, 2.200
Sodium metasilicate was used as the compound of
an alkali metal, and portland cement clinker as the
~,, .
3 3 7
additive.
To produce the binder, the granulated blast
furnace slag and portland cement clinker were ground
in a ball mill till the specific surface thereof was
3,000 cm2/g. Then the obtained mixture was sealed by
a solution of sodium metasilicate.
The produced binder was tested to determine
the bending strength and the compressive strength
thereof in 1, 3, 7 and 28 days, the bending strength
and the compressive strength thereof after steaming,
and the shrinkage deformation thereof in 28 and 100
days.
The tests were carried out in a manner similar
to that described in Example 1. The results of the
tests are given in Table 1.
Example 3
The binder of the present invention comprises,
% by weight:
- granulated blast furnace slag .......... ~ 87
- compound of an alkali metal ............... 8
- additive .................................. 5
The granulated blast furnace slag of the
following composition was used, % by weight: SiO2, 37.52;
A12O3, 9.50; Fe203. 2.2; CaO, 34.9, MgO, 11.25; SO3, 0.66,
25 MnO, 0.36.
9~/O Na2CO3+1C/O ~aOH was used as the compound of
an alkali metal, and portland cement clinker as the
additive.
To produce the binder, the granulated blast
~urnace slag and portland cement clinker were ground in
a ball mill till the specific surface thereof was 3,120
cm2/gA Then the obtained mixture was sealed by the
mixture comprising 90/O Na2CO3 + l~/o NaOH.
The produced binder was tested to determine the
bending strength and the compressive strength thereof in
~` I
i,, .
~ ~ 6533~
- 10 -
1, 3, 7 and 28 days, the bending strength and the com-
pressive strength thereof after steaming, and the
shrinkage deformation thereof in 28 and 100 days.
: The tests were carried out in a manner
similar to that described in Example 1. The results
of the tests are given in Table 1.
Table 1
The binder of the clos d in USSR
Example Example Example Certificate No.
Indices 1 2 3 408,928
. . . ~
1 2 3 4 5
Compressive strength, MPa:
in 1 day 15.2 46.8 31.4 13.6
in 3 days 26.4 64.1 51.5 19.5
in 7 days 49.4 73.0 56.6 21.8
in 28 days 89.6 102.4 81~2 30.1
Compressive strength after
steaming, MPa 91.2 106.5 88.7 31.4
Bending st~ength,
MPa:
in 1 day 2.2 602 4.9 1.4
in 3 days . 2.3 6.3 6.2 2.0
in 7 days 3.9 6.8 7.8 2.3
in 28 days 8.4 9.8 8.9 3.7
:~ Bending strength
after steaming
: MPa: 9.1 9.3 8.9 3~8
30 Shrinkage deforma-
tion, mm~m:
in 28 days 0.5 0061 0.81 1.2
in 100 days 1.38 1.41 1.5 2.45
:
.
3 3 7
Example 4
The binder of the present invention comprises,
% by weight:
- granulated blast Eurnace slag ....... 89
- 5 - compound of an alkali metal ......... 10
- additive ~
The granulated blast furnace slag was of the
following composition, % by weight: SiO2, 35.71;
A12O3, 11.0, Fe2O3~ 2.8, CaO, 43.35; MgO, 5.25;
10 SO3, 1.23; MnO, 0.49.
Sodium metasilicate was used as the compound
of an alkali metal, and portland cement clinker as the
additive.
To produce the binder, the granulated blast
furnace slag and portland cement clinker were ground
in a ball mill till the specific surface thereof was
3,190 cm /g. Then to the obtained mixture a solution
of sodium metasilicate was added.
The produced binder was treated to determine
the bending strength and the compressive strength
thereof in 1, 3, 7 and 28 days, the bending strength
and the compressive strength thereof after steaming,
: and the shrinkage deformation thereof in 28 and 100
days.
The tests were carried out in a manner
~ similar to that described in Example 1. The results of
: the tests are given in Table 2.
Example 5
: The binder of the present invention comprises,
30 % by weight:
- granulated blast furnace slag ............. 98.5
- compound of an alkali metal ~ 1.0
_ .
- additive .................................. 0.5
: The granulated blast furnace slag was of the
35 following composition, % by weight: ~iO2, 35.71,
-~ J 8~337
- 12 -
A12O3, 11.00 Fe2O3, 2.8 CaO, 43~35, MgO, 5.28,
SO3~ 1.23 MnO~ 0.49.
Sodium metasilicate was used as the compound
of an alkali metal, and portland cement clinker as the
: 5 additive.
To produce the binder, the granulated blast
furnace slag and sodium sulphate were ground in a ball
mil.l till the specific surface thereof was 3,270 cm2/g.
Then the obtained mixture was sealed by a solution of
10 sodium metasilicate.
The produced binder was tested to determine
the bending strength and the compressive strength there-
~ of in 1, 3, 7 and 28 days, the bending strength and the
; compressive strength thereof after steaming, and the
; 15 shrinkage deformation thereof in 28 and 100 days.
The tests were carried out in a manner
similar to that described in Example 1. The results
- of the tests are given in Table 2.
Example 6
The binder of the invention comprises, % by
weight:
- granulated blast furnace slag ............ 93.25
- compound of an alkali metal ............... 6.0
- additive .~ 0.75
: 25 m e granulated blast furnace slag was of the
following composition, % by weight: SiO2, 36.39,
A12O3, 6.75; Fe2O3~ 2.6; CaO, 45.85, MgO, 2.94; SO3,
2.61; MnO, 1.63.
Sodium metasilicate was used as the compound
of an alkali metal, and sodium sulphate as the additive.
To produce the binder, the granulated blast
~ furnace slag and sodium sulphate were ground in a ball
:~:: mill till the specific surface thereof was 3,310 cm2/g.
-
Then the obtained mixture was sealed by a solution of
; 35 sodium metasilicate.
I 1 65~37
- 13 -
The produced binder was tested to determine
the bending strength and the compressive strength
thereof in 1~ 3, 7 and 28 days, the bending strength
and the compressive strength thereof after steaming,
and the shrinkage deformation thereof in 28 and 100
days.
The tests were carried out in a manner
similar to that described in Example 1. The results of
the tests are given in Table 2.
Table 2
Indices Example 4 Example 5 Exarnple 6
.
Compressive strength,
MPa:
in 1 day 33.5 32.1 30.2
in 3 days 69.0 60.5 58.7
in 7 days 83.4 69.0 68.1
in 28 days 115.0 104.0 90.7
Compressive strength
after steaming, MPa: 111.3 106.2 91.4
: 20 Bending strength, MPa:
in 1 day 5 5 4O9 4 0
in 3 days 5.8 5.2 4.8
in 7 days 6.1 6~3 6.2
in 28 dayq 11.4 11.2 7.4
25 Bending strength after
steaming, MPa: 11.5 11.6 8.2
Shrinkage deformation,
,
ml~ m: ~
in 28 ~ays 0.71 0.80 0.76
in 100 days 1.40 1.49 1.42
~,
1 6~33~
- 14 -
; Example 7 (negative)
A hinder comprises, % by weight:
- granulated hlast furnace slag ... ~........ 80
- compound of an alkali metal ........ .. ~ . 10
- additive .~......................... ...... 10
The granulated blast furnace slag was of the
following composition, % by weight: SiO2, 33.6, A1203,
15.85; Fe203, 2.45, Cao9 35.67, MgO, 8.90, S03, 1.34,
MnO, 1.40.
The compound of an alkali metal was sodium
metasilicate, and the additive was portland cement
clinker.
To produce the binder, the granulated blast
furnace slag and the portland cement clinker were ground
in a ball mill till the specific surface thereof was
3S400 cm2/g. Then to the obtained mixture a solution
of sodium metasilicate was added.
Thus produced binder was tested to determine
the bending strength and the compressive strength
thereof in 1, 3, 7 and 28 days, the bending strength and
the compressive strength thereof after steaming, and the
shrinkage deformation thereof in 28 and 100 days.
The binder was tested in accordance with the
testing procedures described in Example 1. The obtained
results were as follows:
- Compressive strength~ M2a:
in 1 day .... ~........................... 0. 15.0
in 3 days ... 0........................... ...24.0
in 7 day~ ... ~........................... ..45.0
in 28 day~ .. ~........................... ..60.7
~ ~ - Compressive strength after steaming, MPaO62.0
; ~ Bending strength, MPa:
in 1 day ................................ .0 1.8
in 3 days ... ~.u.. `......... O.. O......... ....2.0
in 7 days ... `........................... ....2.8
in 28 days .. ~.... ~...................... ....4.2
- Bending strength after steaming, MPa: 4.2
3 3 7
- Shrinkage deformation, mm/m:
in 28 days ~ 0.9
in 100 days ~.......................... 1.3
Thus, if the amount of the additive contained in
the binder is greater than that indicated in the
claims, both the bending strength and the compressive
strength of the binder are reduced.
Example 8 (negative)
A binder comprises, % by weight:
- granulated blast furnace slag ~ ....... 97.1
- compound of an alkali metal ............ 2
- additive ........ ~..................................... 0.9
The granulated blast furnace slag was of the
following composition, % by weight: SiO2, 33.6
A1203, 15.85 Ee203, 2.45 CaO, 35.67 MgO, 8.90
SO3, 1.34, MnO, 1.40.
The compound of an alkali metal was sodium
metasilicate, and the additive was portland cement
clinker.
To produce the binder, the granulated blast
furnace slag and the portland cement clinker were ground
in a bal mill till the specific surface thereof was
3,390 cm /g. Then the obtained mixture was sealed by
a solution of sodium metasilicate.
: 25 mus produced binder was tested to determine
the bending strength and the compressive strength
thereof in 1, 3, 7 and 28 days, the bending strength
and the compressive strength thereof after steaming,
and the shrinkage deformation thereof in 28 and l00
days.
The binder was tested in accordance with the
testing procedures described in Example 1. The
obtained results were as -follows:
:
: '
3 3 7
- 16 -
- Compressive strength, MPa:
in 1 day ............................................... ~ 9.3
in 3 days .......................................... 7 ~ 19~ 8
in 7 days ...........~................................... 30.0
in 28 days ........................... ................... 63.6
- Compressive stren~th after steaming, MPa: 64.0
- Bending strength, MPa:
in 1 day ............................. .................. u 1.6
in 3 days ............................ .................... 2.0
in 7 days ............................ ................ ~.O 2.3
in 28 days .......... .............. 5.6
- Bending strength after steaming, MPa: 5.7
- Shrinkage deformation, mm~m:
. in 28 days .......... ~................... 0.9
in 100 days ............................. 1.53
Thus the decrease in the content of the
additive in the binder by lower than indicated in the
claims causes a considerable decrease in both the
bending and compressive strength thereof.
Example 9 ~negative)
A binder comprises, % by weight:
- granulated blast furnace slag .. ~.............. 98.7
- compound of an alkali metal .... ~.............. Ø9
- additive ~ 0~4
The granulated blast furnace slag was of the
following composition, % by weight: SiO2, 33.6,
A12O3, 15-85, Fe2O3, 2-45, CaO~ 35.67, MyO, 8.9
;: SO3, 1.34, MnO~ 1.4.
The compound of an alXali metal was sodium
metasilicate, and the additive was potassium sulphate.
To produce the binder, the granulated blast
furnace slag and potassium sulphate were ground in a
ball mill till the specific surface thereof was
3,320 cm2~g. Then the obtained mixture was sealed by
a solution of sodium metasilicate.
5337
- 17 -
Thus produced binder was tested to determine
the bending strength and the compressive strength
thereof in 1, 3, 7 and 28 days 7 the bending strength
and the compressive strength thereof after steaming,
and the shrinkage deformation thereof in 28 and 100
days.
The binder was tested in accordance with the
testing procedures described in Example l. The
obtained results were as follows:
- Compressive stren~th, MPa:
in l day ~ . 8.1
in 3 days ~ 9.4
in 7 days .................~............................... 21.2
in 28 days ................................................ 49.0
- Compressive strength after steaming, MPa: 49.8
- Bending strength, MPa:
in 1 day ................................................... l.0
in 3 days .................................................. 1.7
in 7 days ............................ ..... 2.1
: 20 in 28 days ................................. . 4.9
- Bending strength after steaming, MPa: 5.1
- Shrinkage deformation, mm/m:
in 28 days ................................. . l.l
:~ in lO0 days ................................ . 2.1
The above ratio of the components of the
binder causes a considerable decrease in the bending
strength and the compressive strength of the binder
: and an increase in the shrinkage deformation thereof.
While particular embodiments of the invention
have been shown and described, various modifications
thereof will be apparent to those skilled in the art and
therefore it is not intended that the invention be
limited to the disclosed embodiments and departures
may be made therefrom within the spirit and scope of
the invention as defined in the claims.
, ~ .
