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USOO5356671A

Unlted States Patent [19] [11] Patent Number: 5,356,671

Drs [45] Date of Patent: Oct. 18, 1994

[54] CONCRETE SPRAYING PROCESS 2629196 1/1978 Fed. Rep. Of Germany .

_ _ , 3246604 6/1984 Fed. Rep. of Germany.
[75] Inventor: Josef F. Drs, Vlenna, Austria 3740783 V1939 Fed_ Rep of Germany _
- _ - 3838029 5/1989 Fed. Rep. of Germany .
[73] Assignee. Sandoz Ltd., Basle, Sw1tzerland 2643629 2/1990 France _
[21] Appl. No.: 32,215 60-151266 8/1985 Japan .
, 154801 9/ 1986 Norway .
[22] F1led= Mar-17, 1993 655296 11/1983 Switzerland.
2131409 6/1984 United Kingdom .............. .. 106/737
Related US, Application Data W087/02978 5/1987 World Int. Prop. 0. .
[63] Continuation of Ser. No, 929,650, Aug. 12, 1992, aban- OTHER PUBLICATIONS
Ygif‘aifagdgj’fggfmm" °f Se‘ N°' 662’873’ Chemical Abstract No. 102:66471k (1984).
_ _ _ _ _ Chemical Abstract No. 110:198226j (1989).
[30] Forelgn Apphcatwn Prwnty Data “Betonwerk & Fertigteil-Technik,” Issue 11 (1989) pp.
Mar. 1, 1990 [DE] Fed. Rep. of Germany ..... .. 4006725 6251751 and 88-90. 1989 7
“ ,” November , p. 52.‘
[52] us.
Int. (11.5
01. ..................................
.............................................
.. 427/427; .. 106/724; “T‘‘6 fb a“ _BG ’ 99 De c 6 mb er p‘ ‘
“Zement-Kalp-Gips,” Nr. 6, 1968, pp. 263-266.
106/727; 106/729; 106/737; 106/802; 106/805; “Concrete,” March 1986, vol. 110, pp. 19-21 (UK).
106/ 808; 427/215; 427/220; 427/221; 427/384; “Concrete,” October 1985, vol. 104, pp. 20-23 (UK).
427/385.5 “Betonwerk & Fertigteil-Technik,” Issue 8 (1989), pp.
[58] Field of Search ............. .. 106/737, 724, 802, 808, 571-580.
106/727, 729, 805; 427/427, 397.7, 215, 220, “Portland Cement-Composition, Production and
221, 384, 385.5; 428/403, 404, 688, 703 Properties,” G. C. Bye (1983), Pergman Press, pp. 4-5.
[56] References Cited “Cement and Mortar Additives,” A. .1. Franklin (1976),
U.S. PATENT DOCUMENTS Noyes Data Corporation, pp. 169-170.
3,503,771 3/1970 Kroyer .............................. .. 106/712
Primary Examiner-Anthony Green
4,292,351 9/1981 Ito et a1. .... .. 427/403 Attorney, Agent, or Firm-Robert S. Honor; Richard E.
4,345,037 8/ 1982 Fyles et a1. ........ .. 106/711 Vila; Carol A. Loeschorn
4,363,666 12/1982 Johnson et a1. 106/711
4,373,957 2/ 1983 Pedersen ........... .. 106/711
[57] ABSTRACT
4,377,415 3/1983 Johnson et a1. . 106/711 A process for improving the rebound properties of
4,384,896 5/1983 Aitcin et a1. 106/288 sprayed concrete comprises the inclusion therein of
4,654,165 3/ 1987 Eisenberg 252/4081 micro-silica which has been pretreated with from 2 to
4,656,049 4/ 1987 Noto . . ... ... .... . . . . .. 427/10
25% by weight thereof of a liquid selected from water,
4,673,659 6/1987 Wood et al. 106/737
4,707,453 11/1987 Wagner et al. 436/501 an alkanolamine, a polyol and an aqueous solution of at
4,804,563 2/ 1989 Hillemeier et a1. ............... .. 427/397 least one concrete additive, an alkanolamine, a polyol
and a water-soluble cellulosic compound. The process
FOREIGN PATENT DOCUMENTS is especially effective when used in conjunction with
0263606 9/1987 European Pat. Off. . the dry spraying process.
0289720 2/ 1988 European Pat. Off. .
0307066 3/1989 European Pat. Off. . 15 Claims, No Drawings
 5,356,671
1 2
known method in the spray nozzle and is sprayed. In
CONCRETE SPRAYING PROCESS this dry spraying process, a reduction in rebound is
attained, which is at least as good as that obtained when
This is a continuation of application Ser. No. using an aqueous suspension of micro-silica, but there is
07/929,650, ?led Aug. 12, 1992, now abandoned, which no increased dust formation. In addition, the micro
in turn is a continuation of application Ser. No. silica which is pretreated in the manner hereinabove
07/662,873, filed Mar. 1, 1991, now abandoned. described is a pourable powder which is easy to handle
The invention relates to a concrete spraying process, and simple to measure out. If an aqueous solution of
and in particular to the use of micro-silica in dry spray additives (for example, hardening accelerators) is used
ing processes. 10 for pretreatment, there is produced a micro-silica pow
In a dry concrete spraying process, all of the compo der which can be added to the dry mix as a combination
nents of a concrete mixture, apart from water and op of active materials, and this permits the exact and eco
tional additives which are dissolved in water, are mixed nomical dispensing of these active materials.
whilst dry and introduced pneumatically into a spray Micro-silica (silica fume), as it is used in the above
nozzle, where the dry mix is mixed with water and described process, is an extremely fmely-divided amor
subsequently sprayed on to a substrate. phous powder, comprising at least 90 percent by weight
One of the disadvantages of this dry spraying process of silicon dioxide. The particles are globular and have a
is the unacceptable degree of loss by rebound of the diameter of from 0.1 to 0.2 pm and a speci?c surface of
concrete mixture from the substrate, and it has been from 15 to 30 m2/g. This micro-silica is a by-product in
proposed to reduce this rebound loss by adding micro the production of silicon or ferro-silicon.
silica (also known as silica fume) to the dry mix. If this As an alternative, pure silicon dioxide can also be
material is added as a powder, the reduction in rebound used, and this is produced synthetically (precipitation of
is less than that obtainable when an aqueous suspension silicic acid). This enables a considerably higher degree
of micro-silica is used. However, use of the powder in of ?neness (up to 200 mZ/g) to be achieved.
this manner brings the disadvantages of increased dust 25 Other ?nely-divided pozzolanic materials can be
formation and the handling difficulties encountered mixed with the micro-silica powder of this invention.
with finely-dispersed powders. Examples of such materials include ?y ash, shell ash,
If, on the other hand, micro-silica is used in the form ground blast-furnace slag, etc. Such a mixture should
of an aqueous suspension, it cannot be admixed with the contain at least 50% micro-silica in order to attain the
dry mix, but must be added to the mixing water or desired reduction in rebound. It is preferred that pure
introduced to the nozzle through its own pipe. Surpris micro-silica be used alone.
ingly however, the dust formation in such a process is For pretreatment, micro-silica is mixed with 2 to 25
not reduced. There therefore remains a need for a prod percent by weight of a liquid selected from the group
uct which permits the reduction of rebound losses, yet hereinabove described. The reference to “liquid” en
which avoids the disadvantages hereinabove described. compasses not only individual liquids but also blends of
It has now been found that a micro-silica powder any two or more of these liquids. In the case of those
which is pretreated with certain liquids ful?ls these liquids which are aqueous solutions of materials, any
requirements, and that a micro-silica powder which has two or more of the specified materials may be dissolved
been pretreated with an aqueous solution of hardening therein. Pretreatment is carried out preferably by spray
accelerators or other additives has further advantages. 40 ing, and the sprayed powder is then stirred in a mixer
There is therefore provided, according to the present until a uniformly moistened powder is obtained. The
invention, a process for improving the rebound proper preferred liquids are water and aqueous solutions of
ties of sprayed concrete, comprising the inclusion concrete additives. Other substances which have been
therein of micro-silica powder which has been pre found to be especially useful are glycerol and aqueous
treated with from 2 to 25% by weight thereof of a liquid 45 solutions of glycerol, polyethylene glycols, triethanol
selected from water, an alkanolamine, a polyol and an amine, methyl cellulose and hydroxyethyl cellulose.
aqueous solution of at least one material selected from a The concrete additives which are used in the above
concrete additive, an alkanolamine, a polyol and a mentioned aqueous solutions are those which are usu
water-soluble cellulosic compound. ally used in concrete mixtures which are applied by
Although this invention may be used with a wet 50 spraying, for example, air entraining agents, stabilizers,
spraying process, use with a dry spraying process gives water reducing agents and in particular hardening ac
especially good results. The invention therefore also celerators. One preferred additive is a mixture of so
provides a dry spraying process for applying concrete dium or potassium aluminate and potash (potassium
to a substrate by the steps of mixing dry components of carbonate), which is known as a hardening accelerator
a concrete, introducing the mixture thus formed to a 55 for spraying concrete mixtures and which can also be
nozzle wherein it is mixed with water and spraying it used as in the form of an aqueous solution. In a pre
from the nozzle on to a substrate, the concrete compris ferred composition, an admixture comprises from 50 to
ing dry micro-silica powder which has been pretreated 70 parts of micro-silica, from 8-12 parts of potash and
with from 2 to 25 percent by weight thereof of a liquid from 22-38 parts of sodium or potassium aluminate per
as hereinabove described. 100 parts admixture solids.
The invention additionally provides a powdery ad The use of an aqueous solution of such an accelerator
mixture for use in concrete mixtures which are to be in the process of the present invention results in consid~
applied by spraying, particularly by dry spraying, com~ erable practical advantages when a dry spraying pro
prising micro-silica which has been treated with a liquid cess is used. In this case, the previous practice has been
as hereinabove described. 65 to introduce a solution of accelerators into the spray
The micro-silica is preferably incorporated into a dry nozzle, there to be combined with the dry mix, by
mix comprising cement, aggregate and other admixed means of a separate hose line. Optimum dosing is diffi
materials, and this mixture is admixed with water by any cult in this case and over-dosing can lead to inferior
 5,356,671
3 4
?nal strength of the sprayed concrete. However, if this
EXAMPLE 6
aqueous solution is used according to the invention to
pretreat the micro-silica, the appropriate quantity of Example 4 is repeated with the 8 parts of water being
hardening accelerator may be incorporated into the dry replaced by 8 parts of a solution of 0.5 parts of hydroxy
mix and the abovementioned disadvantages may be ethyl cellulose in 99.5 parts of water.
avoided. EXAMPLE 7
Micro-silica and the solution of hardening accelera
tors can be mixed in any quantities, so long as the water 50 parts of micro,silica is mixed with 25 parts soda, 5
content of the micro-silica thus treated is no more than parts of potassium hydroxide and 20 parts of sodium
25 percent by weight. If larger quantities of water are aluminate. This mixture is granulated with 8 parts of
employed, an aqueous suspension of micro-silica is pro water as described in Example 3.
duced, and this no longer confers the advantages of this EXAMPLE 8
invention. Thus, it is advantageous to mix together
those quantities of micro-silica and aqueous solution 15 50 parts of micro-silica is mixed with 8 parts of water
which are normally used together in the concrete mix as described in Example 3. The resulting granular solid
ture. The bene?cial effects of the invention are achieved is then mixed with 25 parts of soda, 5 parts of calcium
by the use of from 3 to 20%, preferably 5-15% by hydroxide and 20 parts of sodium aluminate.
weight of cement of micro-silica and 3 to 8%, prefera EXAMPLE 9
bly 4-6% by weight of cement of hardening accelera 20
tor.
Example 8 is repeated, with the substitution of the
When mixing micro-silica with an aqueous solution of following quantities for those of that example:
hardening accelerators, it is preferable ?rst to mix mi
cro-silica with potash, and then coat this mixture with micro-silica 50
an aqueous solution of sodium or potassium aluminate. 25 water 6.5
However, micro-silica or precipitated silicic acid or soda 12.5
calcium hydroxide 2.5
mixtures thereof with ?y ash and similar materials can sodium aluminate l0
also be pre-mixed with a dry mixture of accelerating
substances (soda, potash and/or other alkali hydroxides,
calcium hydroxide and sodium aluminate), and this 30 EXAMPLE 10
powdery mixture can be treated with liquid.
In the following examples, all references to parts are Example 9 is repeated, with 0.5 parts of glycerol
understood to be parts by weight, and temperatures are being added to the water prior to granulation.
expressed in degrees celsius. EXAMPLE ll
35
EXAMPLE 1 50 parts of micro-silica is granulated with 8 parts of a
57 parts of micro-silica are pre-mixed in a powder 45% by weight aqueous solution of sodium aluminate,
according to the method of Example 3.
mixer with 11.9 parts of soda, 9.9 parts of sodium alumi
nate and 2.6 parts of calcium hydroxide, and coated EXAMPLE 12
with 18.6 parts of an aqueous solution of 0.5 parts of 40 Example 11 is repeated with the substitution of 8
hydroxy ethyl cellulose in 99.5 parts of water. parts of a 45% aqueous solution of potassium aluminate
EXAMPLE 2 for the sodium aluminate solution of Example 11.
55 parts of micro-silica are pre-mixed in a powder EXAMPLE 13
mixer with 11.4 parts of soda, 9.5 parts of sodium alumi Example 11 is repeated with the substitution for the
nate and 2.5 parts of calcium hydroxide, and coated sodium aluminate solution of that example of 15 parts of
with 21.6 parts of glycerol. an aqueous solution having the overall composition 45
EXAMPLE 3 parts potassium aluminate, 15 parts potassium carbonate
and 40 parts water.
8.33 parts of water are added to 50 parts of micro
silica (bulk density 0.25 kg/dm3) in a ?uidising mixer EXAMPLE 14
equipped with ?ne spraying nozzles. The resulting Preparation of a dry mix concrete according to the
product is a granular solid of bulk density 0.56 kg/dm3. invention and comparison with a conventional dry mix
EXAMPLE 4 55 concrete.
Two dry spraying mixtures were prepared by con
Example 3 is repeated with 50 parts of micro-silica ventional mixing of ingredients and applied by spraying
(bulk density 0.307 kg/dm3) and 8 parts of water. The to a substrate. The ingredients and their quantities were
resulting granular solid has a bulk density of 0.553 as follows:
kg/dm3.
EXAMPLE 5 Invention Comparison
Example 4 is repeated three times, with 0.5 parts of (8) EM;
one of the following substances being added each time cement 400 400
micro-silica 20 —
to the water: 65
(from Example 4)
(a) hexylene glycol aggregate 1740 1740
(b) diethylene glycol (b) Mixing at nozzle:
(0) glycerol water 200 200
 5,356,671
6
-continued cally to a spraying nozzle where they are blended with
a further component (water in the case of the invention
Invention Comparison
composition, water and micro-silica aqueous slurry in
micro-silica slurry1 -— 40
accelerator2 24 24
the case of the comparison composition) and sprayed on
5 to a substrate.
IA micro-silica aqueous slurry prepared by the dispersion of 50 parts of micro-silica
in 50 parts of water. The two sprayed concretes display similar properties,
2The material used is MEYCO "Gunit" F 100 but the composition according to the invention gives
several significant practical advantages. Firstly, there is
It can be seen from the quantities table above that the the greatly decreased dust production of the composi
composition according to the invention has the pre tions according to the invention. Secondly, there is the
treated micro-silica powder in the dry mix, whereas in simpler equipment previously referred to in Example
the conventional mix, the micro-silica is incorporated as 14. Thirdly, there is the simpli?ed procedure brought
a slurry at the nozzle. This latter necessitates the extra about as a result of the incorporation of the accelerator
complexity of a separate line to the nozzle to convey the into the micro-silica (one less component to add).
slurry. 15 Fourthly, there is the fact that there is no danger with
The hardening and rebound properties of the two the present invention of overdosing the composition
compositions are similar. However, the compositions with accelerator as there is with the conventional accel
according to the invention generate considerably less erator.
dust, which makes the working environment much What is claimed is:
more pleasant and less hazardous. Moreover, as previ 1. A process for improving the rebound properties of
ously mentioned, the equipment needed to apply the sprayed concrete, which comprises adding to a dry
composition according to the invention is less complex, concrete mix, prior to spraying, a micro-silica powder
leading to greater reliability and ef?ciency. which has been pretreated by spraying said powder
EXAMPLE 15 with from 2 to 25% by weight thereof of at least one
25
An example of the use of the invention in a wet spray liquid chosen from water, an alkanolamine, a polyol, or
an aqueous solution of at least one material chosen from
ing process, with a comparative example.
The following components are used: an air entraining agent, a stabilizer, a water reducing
agent, a hardening accelerator, an alkanolamine, a
30 polyol or a water-soluble cellulosic compound, to form
Invention Comparison a micro-silica containing dry concrete mix, combining
cement 400 400 said micro-silica containing dry concrete mix with
pretreated micro-silica 2O — water to form an aqueous concrete mixture and spray
(from Example 4) ing said aqueous mixture onto a substrate, wherein said
untreated micro-silica — 2O
aggregate 1740 1740 35 dry concrete mix comprises cement and aggregate.
water 220 240 2. A dry spraying process for applying concrete to a
superplasticiser1 4 4 substrate comprising the steps of mixing cement and
hkheobuild" 1000 is used. aggregate to form a dry concrete mixture, introducing
said dry concrete mixture to a nozzle wherein the dry
The properties of the sprayed concrete are similar, concrete mixture is mixed with water to form a liquid
but here again the comparison composition suffers from mixture and spraying said liquid mixture onto a sub
the dust problem. Moreover, the untreated micro-silica strate, the dry concrete mixture additionally including a
of the comparison composition must be added by hand, dry micro-silica powder which has been pretreated by
whereas the pretreated micro-silica is added mechani spraying said powder with from 2 to 25% by weight
cally. 45 thereof of at least one liquid chosen from water, an
alkanolamine, a polyol, or an aqueous solution of at least
EXAMPLE 16
one material chosen from an air entraining agent, a
Example of a dry mix which comprises an accelera stabilizer, a water reducing agent, a hardening accelera
tor. tor, an alkanolamine, a polyol or a water-soluble cellu
Two dry spraying compositions, one according to the 50 losic compound.
invention and the other a comparative example based 3. A process according to claim 1, wherein the liquid
on the known art, comprise the following materials: is chosen from water or an aqueous solution of at least
one material chosen from an air entraining agent, a
Invention Comparison stabilizer, a water reducing agent, or a hardening accel
55 erator.
(a) BIL-112:; 4. A process according to claim 1, wherein the liquid
cement 400 400
aggregate 1740 1740
is chosen from glycerol or aqueous solutions of glyc
pretreated micro-silica 40 — erol, triethanolamine, methyl cellulose, or hydroxy
(from Example 8) ethyl cellulose.
commercially- — 24 5. A process according to claim 1, wherein the liquid
available acceleratorl
(b) Mixing at nozzle: is an aqueous solution of at least one material chosen
water 200 200 from an air entraining agent, a stabilizer, a water reduc
micro-silica slurry — 40 ing agent, or a hardening accelerator.
(as used in Example 14) 6. A process according to claim 5, wherein said liquid
‘BARRA "Gunit” LL is used. 65 is an aqueous solution of a hardening accelerator.
7. A process according to claim 6, wherein the micro
The dry components are blended by means of a con silica is present in an amount of 3 to 20% by weight
veyor belt dosing apparatus and conveyed pneumati based on the weight of cement and said hardening ac
 5,356,671
7 8
celerator is present in an amount of 3 to 8% by weight material chosen from a hardening accelerator, an alka
based on the weight of cement. nolamine, a polyol or a water-soluble cellulosic com
8. The process according to claim 7, wherein the pound.
micro-silica is present in an amount of 5—15% by weight 12. A shotcrete admixture according to claim 11,
based onthe weight of the cement and the hardening wherein the liquid is a aqueous solution of a hardening
accelerator is present in an amount of 4 to 6% by weight accelerator.
based on the weight of cement. 13. A shotcrete admixture according to claim 12,
9. A process according to claim 7, wherein the micro wherein said micro-silica is premixed with a potash in
silica is premixed with a potash in dry form prior to dry form.
being pretreated with said aqueous solution of a harden 14. A shotcrete admixture according to claim 13,
ing accelerator. wherein the hardening accelerator is sodium or potas
10. A process according to claim 9, wherein said sium aluminate.
hardening accelerator is sodium or potassium aluminate. 15. A shotcrete admixture according to claim 14,
11. A powdery shotcrete admixture comprising mi wherein the admixture comprises from 50 to 70 pans of
cro-silica powder which has been pretreated by spray 15 micro-silica, from 8-12 parts of potash and from 22-38
ing said powder with from 2 to 25% by weight thereof parts of sodium or potassium aluminate per 100 parts
of at least one liquid chosen from water, an alkanola admixture solids, all parts being by weight.
it * * * *
mine, a polyol, or an aqueous solution of at least one

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