CA1291849C

CA1291849C - Process of dyeing concrete

Info

Publication number: CA1291849C
Application number: CA000539217A
Authority: CA
Inventors: Axel Ekkehard Jungk
Original assignee: Chemische Werke Brockhues AG
Current assignee: Chemische Werke Brockhues AG
Priority date: 1986-06-09
Filing date: 1987-06-09
Publication date: 1991-11-12
Anticipated expiration: 2008-11-12
Also published as: NO177530C; DK172089B1; DK62188A; AU7483087A; ATE66909T1; IE60037B1; EP0268645A1; IE871521L; ATE68451T1; ZA873918B; JPH0662324B2; EP0365046B1; AU592202B2; ATE58116T1; EP0361543B1; NO880175L; EP0365046A1; EP0268645B1; NO880175D0; NZ220446A

Abstract

ABSTRACT

Process of Dyeing Concrete Coloring materials used in a process of dyeing concrete consist of pigment granules other than compacted or bri-quetted granules. The granules consist of one or more pig-ments, one or more binders for promoting the dispersing of the pigments in the concrete, and optional other additi-ves. Such pigment granules, particularly bead granules, will easily dissolve in the concrete mixer and will be homogeneously dispersed in the concrete.

Description

~91~845~

PROCESS OF DYEING CONCRETE

This invention relates to a process of dyeing concrete.

For the purposes of the invention, concrete is a cement--containing material for making concrete blocks and con-crete slabs, concrete roofing tiles, composite blocks, as well as fibrated cement mortar and/or cement mortar.

Concrete is a proven material of construction and as ex-posed concrete serves also for aesthetic purposes. Exposed concrete made from a dyed concrete mix will have a color for many years without a need for maintenance.

On the other hand, concrete surfaces which have been de-corated by means of paints must be renewed after short in-tervals of time. Dyed concrete is used, e.g., in façades, slabs, pavement blocks, roofing tiles, nose barrier walls, bank-stabilizing structures, bridges and similar struc-tures and, for instance, also in the form of dyed mortar for fasade decoration.

Concrete is dyed with inorganic pigments and more recently also with organic pigments.

Pigments which are suitable for concrete and have proved satisfactory for a prolonged time are, e.g., manganese oxide, iron oxides and carbon. Particularly pigments based on carbon or iron oxide have proved highly satisfactory in practice.

But problems arise in the production of dyed concrete.
Dust is raised from the pigment powder and its use results in a soiling of human beings, machines and premises.

12'~849 Pigments have also the disadvantage that owing to their small particle size they tend to form bridges in storage, particularly in the presence of some moisture.

For this reason pigment powders are no longer freely flow-able after a silo storage for a short time.

As a result, their removal from a silo is difficult and involves a human effort and a high expenditure in equip-ment.

For this reason it is also rather difficult to meter them by means of screw conveyors or vibrating trough conveyors.

It has been endeavored in the prior art to solve the pro-blems arising with pigment powders owing to the raising of dust and in silo storage and in automatic metering and for that purpose the pigments in the form of aqueous plgment pastes were used in concrete.

Most of such pastes contain about 70 to 30 % water as a vehicle as well as surface-active substances.

Whereas such aqueous pigment pastes have advantages over dry pigment powders, considerable disadvantages are in-volved in the use of such pastes.

In practice it is not possible to store the pastes in silos or other high-capacity containers for a prolonged time because the pastes would segregate by settling and would form solid deposits in part.

Owing to the high water content, the costs of packaging and transporting the aqueous pigment pastes are doubled.
Another important disadvantage resides in that such pastes cannot be used at all if the initial moisture content of sand and coarse aggregate used in making concrete is so high that an addition of water even in the form of aqueous 1~9~849 concrete pastes will intolerably reduce the conslstency of the concrete.

When paints and plastlcs are to be dyed, the last-mention-ed disadvantages can be avoided on principle if the pig-ment is used in the form of granules rather than pastes or powders.

Particularly pigments which are deleterious to health have been used in the form of granules in the plastic industry for many years.

The production and use of granules in general have a long-standing tradition in many fields (see H. Rumpf in "Che-mie-Ing.-Technik, 30, 1958, No. 3, No. 4, No. 5", W.C.
Peck in "Chemistry and Industry, issue of December 12, 1958, pages 1674 FF"; and for making granules from molten material see U.A.W. Boretzky in "Fette-, Seifen-, An-strichmittel, No. 4, 1967").

For instance, the use of briquettes is common in the coal and ore fields; microcapsules are used in copying paper;
animal feed consisting of compact granules is found in silos in agriculture; nitrocellulose pigment concentrates are satisfactorily dissolved in solvents in the production of paints; carbon black pellets are used in the production of rubber; and PVC is used in the form of bead granules made by spraying.

On the other hand, it is not known in the art to dye con-crete with pigment granules because the pigment granules known in the art exhibited disadvantages when used in the dyeing process.

During the mixing cycle the shear forces exerted in the concrete on the granules are not sufficient for a disper-sion of the pigment. As a result:

129~849 1. In the concrete, the pigment granules form spots and color nests mar the surface of the concrete.

2. Because the pigments are much less effectively dis-persed than pigment powders in the concrete mixer during the mixing cycle, the coloring power of the granules is inadequately utilized so that the pigment granules must be used in a larger quantity than pig-ment powders in order to impart a given hue to the concrete mix.

3. With the binder-containing pigment granules, foreign matter is introduced into the concrete whereas the undesired dispersing properties are not improved.

4. The moisture content of the concrete and the time available are not sufficient for a dissolving of bin-der-containing granules.

Owing to these disadvantages it is currently usual to grind even spray-dried pigments so as to transform them to a powder before they are used to dye concrete.

For this reason it is an object of the invention to pro-vide for the dyeing of concrete a process in which the disadvantages involved in the use of dye powders, of aqueous pigment pastes, or of pigment granules known in the art are avoided.

In accordance with the invention that object is accom-plished in that the coloring material used to dye concrete consists of granules which essentially consist of pigment and one or more binders for promoting the dispersing of the pigment in the concrete. Whereas suitable pigment gra-nules can be made by any of numerous methods known in the art, granules made by briquetting and compacting processes cannot be used in the process in accordance with the in-vention because they can be dispersed only with difficul-ty.

Pellets may be used.

It is also possible to use particulate granules which are made by a drying of mixtures consisting of pigments, bin-ders, liquid, preferably water, and optional other sub-stances.

Bead granules are particularly suitable.

It has surprisingly been found that the granules mentioned above are effectively dissolved in the concrete ~ixer.

For this reason they can well be used in practice.

They will become homogeneously distributed in the concrete so that exposed concrete will be dyed satisfactorily with-out a formation of spots and color nests.

Their use is economical because a dyeing to a given color saturation can be effected with pigment in granules in the same quantity as with the pigment in powder form.

The granules used in accordance with the invention flow freely from a silo and can be pneumatically conveyed.

Virtually no dust will be raised as the granules are hand-led. In that respect the bead granules are superior in handling properties to granules of other forms.

For this reason the process in accordance with the inven-tion is particularly suitable for a clean automatic dyeing of concrete.

Suitable pigments are, e.g., manganese oxide, iron oxides, organic pigments and/or carbon.

A preferred pigment is the carbon pigment.

Finely ground coal is less preferred because it has only a low coloring power.

Mixtures of the several pigments are also used.

In the granules used in accordance with the invention and consisting preferably of bead granules the pigment is mix-ed with a binder which promotes the dispersing of the pig-ment in the concrete.

Other binders which will not be disturbing in the concrete may be used in addition, if desired.

The following commercially available binders, which will promote the dispersing of the pigments in concrete, may be incorporated in the granules used for dyeing:

Alkylphenol, such as Igepal CR;
a protein-fatty acid condensation product, such as Lam-peonR;
Alkylbenzene sulfonate, also in the form of its salt, such as MarlonR;
Alkylnaphthalene sulfonate, such as Necal BXRR;
Lignin sulonate, such as spent sulfite liquor, e.g., WaldhoflaugeR;
Sulfated polyglycol ether, e.g., of fatty alcohols or alkyl phenols, or its salt;
a melanine-formaldehyde condensate, a naphthalene-formal-dehyde condensate; gluconic acid, other polyhydroxy com-pounds which are innocuous to the concrete, salts of low-molecular-weight partial esters of styrene-maleic anhy-dride copolymers and of copolymers of vinyl acetate and crotonic acid.

lX':~849 A particularly preferred binder is lignin sulfonate, such as ammonium lignin sulfonate.

The granules which may be used in the process in accord-ance with the invention can be made by any of numerous processes. In the form of pellets they are preferably made by means of conventional rotating suitable pelletizing plates, such as are available from Eirich, in that the pigment powders are fed via metering screw conveyors and the binders dissolved in water are delivered in drops to the plate, and the pellets having a size of about 1 mm are separated via an overflow and are then dried.

Instead of a pelletizing plate, an inclined rotating pel-letizing drum, such as is available from Dela Granulier-technik, may be used. The pigment particles roll on the pelletizing plate and in the drum and are thus caused to agglomerate and to be consolidated.

In another embodiment, granules for use in the process in accordance ~ith the invention may be obtained by drying a mixture of binder, pigment and liquid, preferably water, and optional other additives.

For instance, such mixtures may be applied as a paste in a thin layer to a roll dryer and may then be dried and re-duced to fine granules.

Such a mixture may alternatively be dried as a thin layer on a belt drier and may be reduced thereon to fine gra-nules.

The granules used in the process in accordance with the invention preferably consist of bead granules.

3ead granules are produces from mixtures of pigment, bin-der and liquid, preferably water, and optional other addi-tives by means of spray driers using nozzles for discharg-~291~349 ing one substance or a plurality of substances or usingatomizing discs in a spray tower.

The bead granules are obtained as microgranules so that 90 % of the pigme~t particles have a slze from 20 to 500 mi-crons, particularly from 50 to 300 microns.

The binder for promoting the dispersing of the pigment in the concrete is used in an amount of 0.1 to 15 % by weight of the granules, preferably 1 to 8 % by weight and parti-cularly 2 to 6 % by weight.

The invention will now be explained more in detail with reference to the Examples.

Exam~le 1 Production of Bead Granules Which Contain 31ac~ Iron Oxide A slurry of 53 !~ by weight black iron oxide and 2.0 % by weight binder (Hansa~m, an ammonium lignin sulfonate powder available from Lignin Chemie Waldhof-Holmen GmbH), balance water, is spray-dried in a countercurrent/cocur-rent operation in a spray-drying plant comprising nozzles for atomizing under pressure.

~he ~tomizing pressure is 13 to 18 bars, the entrance tem perature of the drying air is 280 to 325C, and the ex-haust air temperature 115 to 130C.

The product obtained consists of freely flowable, coarse bead granules, which are f-ee of dust and have a residual moisture content of 0.3 to 1.3 % and an apparen~ density from 810 to 820 g/l.

The bead granules had a mean particle size of 150 ~o 250 ~m and a high mechanic21 s.abili.y.
,,! ; 1 *~rac,e-mar:~

12~ 849 Exam~le 2 Production of Carbon-containinq Bead Granules In the same manner as in Example 1, bead granules were made from an aqueous slurry which contained 33 % by weight carbon pigmen~ and 1.5 % by weight ammonium lignin sulfo-nate as a binder (AM 250 Hansa*available from Lignin-Chemie Waldhof-~olmen GmbH.

But the atomizing noz~les were operated under an atomizing pressure of 10 to 16 bars, the entrance temperature of the drying air amounted to 320 to 400C and the exhaust air temperature amounted to 125 to 150C.

Freely flowable, coarse bead granules were obtained, which has a low dust content and had a residual moisture content from 1.2 to 4.2 % and an apparent density from 370 to 400 g/l.

The bead gxanules had a mean particle size from 150 to 200 ~m and had an even higher stability than the bead granules which had been o~tained in Example 1 and contained iron oxide pigment.

Exam~le 3 PreParation of Bead Granules from a Picment Dispersion Which Contained Iron Oxide and Carbon By the same method as in Example 1, bead granules were made from an aqueous slurry consisting of 1.3 parts ammonium li.qnin sulfonate 4.7 parts carbon pigment 22 parts yellow iron oxide *trade-mark 34~

22 parts red iron oxide and parts water The atomizing pressure amounted to 11 to 16 bars, the en-trance temperature of the drying air was 280 to 300C and the exhaust air temperature 90 to 110C.

The resulting bead granules are coarse, freely flowable and free of dust.

The residual moisture content is 2 to 2.2 %.

The apparent density is about 600 to 650 g/l.

ExamPle 4 A concrete mixer (type Schlosser) having a cubic capacity of 1 m3 was operated for 15 minutes to mix 1,560 kg sand and, in accordance with the invention, 18 kg black iron oxide in the from of bead granules prepared in Example 1.
440 kg Portland cement were then added and were homoge-nized with the previously obtained mixture for 15 minutes.
The mixer is then emptied and the mix is used to make con-crete roofing tiles.

Control ExamPle 1 The process is the same as in Example 4.

Instead of the bead granules in accordance with the inven-tion, the same quantity (18 kg) of black iron oxide is used in powder form.

The moist concretes and the roofing tiles hardened for 24 hours were compared in color. Significant differences were not observed.

1;~9~849 Example 5 The procedure is the same as in Example 4.

But 7 kg carbon bead granules obtained in Example 2 were used for dyeing.

Control Example 2 The procedure is the same as in Example 5.

7 kg carbon pigment in powder form were used for dyeing.

The moist concrete and the roofing tiles that had been hardened for 24 hours were compared.

Significant differences in aolor were not observed.

ExamPle 6 The procedure is the same as in Example 4.

20 kg of the brown bead granules obtained in Example 3 were used.

Control ExamPle 3 The procedure is the same as in Example 4.

20 kg of mixed powders consisting of the individual compo-nents of the pigments used in Example 3 are now used for dyeing.

Control ExamPle 4 The procedure is the same as in Example 4.

40 kg of the pigment slurry that was spray-granulated in Example 3 were now used for drying. The quantity of water added to the concrete mix was reduced from 100 kg to 80 kg to allow for the water content of the pigment slurry which was added.

Results of Example 6 and of Control Examples 3 and 4:

The moist concretes and the roofing tiles that had been hardened for 24 hours, which had been obtained in Example 6 and in Control Example 3 and 4, were compared in color.

No differences were observed between the concrete that had been dyed in accordance with the invention and the con-crete obtained in Control Example 4.

The concrete obtained in Control Example 3 had been dyed to a distinctly lower homogeneity.

ExamPle 7 A l-m3 concrete mixer (type Drais) was operated for 10 se-conds to mix 975 kg sand, 580 kg gravel and, in accordance with the invention, 10 kg black iron oxide in the form of bead granules obtained in Example 1. 200 kg Portland ce-ment were then added to the mix, which was subsequently homogenized for 15 seconds. ~he concrete mix was used to make a composite concrete pavement.

Control ExamPle S

The procedure is the same as in Example 7.

Instead of the bead granules in accordance with the inven-tion, 10 kg black iron oxide in the form of a powder were added.

Results of Example 7 and of Control ExamPle 5:

The moist concretes and the composite blocks that had been hardened for 28 days were compared in color. The blocks made in accordance with the invention were somewhat darker and more unirormly dyed than blocks dyed with iron oxide powder.

Example 8 The procedure was the same as in Example 7.

3.3 kg of the carbon bead granules obtained in Example 2 were used as a coloring material in accordance with the invention.

Control Example 6 The procedure was the same as in Example 7.

3.3 kg of the carbon pigment powder obtained in Example 2 were used as a coloring material.

Results of Example 8 and Control ExamPle 6:

The moist concretes and the composite blocks which had been made from the concrete and hardened for 28 days were compared.

Differences in color were not observed.

Example 9 The procedure was the same as in Example 7.

In accordance with the invention, 11 kg bead granules ob-tained in Example 3 were used for dyeing.

t849 Control ExamPle 7 The procedure was the same as in Example 7.

In accordance with the prior art, 22 kg of the slurry used in Example 3 to make bead granules were used for dyeing in accordance with the prior art. Water was used in an amount of 89 kg rather than 100 kg to allow for the water content introduced into the concrete by the slurry.

Results of Example 9 and Control Example 7:

A comparison of the two moist concrete mixes and of the blocks that had been hardened for 28 days did not reveal differences in color quality.

Claims

1. A material used for dyeing of concrete, comprising pigment granules prepared by built-up granulation, by drying of a mixture comprising pigment, binder, and liquid, or by spray-granulation, as colouring material, wherein said pigment granules comprise one or more pigments under the proviso that when the pigment granule comprises one pigment, the pigment is not a carbon pigment, and one or more binder which promotes dispersing of the pigments in the concrete, the amount of binder being 0.1 to 15 % by weight of the granules.

2. A material according to claim 1, wherein the pigments are iron oxides.

3. A material according to claim 1 or 2, wherein the binder that promotes the dispersing of the pigments in the concrete coloring material consists of an alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, a sulfated polyglycol ether, a melamine-formaldehyde condensate, a naphthalene-formaldehyde condensate, gluconic acid, an other polyhydroxy compound which is innoxious to the concrete, a salt of a low-molecular-weight partial ester of a styrene-maleic anhydride copolymer and/or a copolymer of vinyl acetate and crotonic acid.

4. A material according to claim 1 or 2, wherein the binder is a lignin sulfonate.

5. A material according to claim 1 or 2, wherein the granules have been made by pelletizing.

7153/sza

6. A material according to claim 1 or 2, wherein the granules have been made by the drying of a mixture consisting of pigment, binder, and liquid.

7. A material according to claim 1 or 2, wherein the granules have been made by the spray-granulation of a mixture consisting of pigment, binder, and water.

8. A process of dyeing concrete, wherein pigment granules prepared by built-up granulation, by drying of a mixture comprising pigment, binder, and liquid, or by spray-granulation are used as a colouring material, such granules comprise one or more pigments under the proviso that when the pigment granule comprises one pigment, the pigment is not a carbon pigment, and one or more binders for promoting the dispersing of the pigments in the concrete, characterized in that the pigment granules are used with a water content not in excess of 4.2 %, the amount of binder being 0.1 to 15 % by weight of the granules.

9. A process according to claim 8, characterized in that the pigment is iron oxide.

10. A process according to claim 8, characterized in that the binder for promoting the dispersing of the pigments in the concrete coloring material consists of an alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, a sulfated polyglycol ether, a melamine-formaldehyde condensate, a naphthalene-formaldehyde condensate, gluconic acid an other polyhydroxy compound which is innoxious to the concrete, a salt of a low-molecular-weight partial ester of a styrene-maleic anhydride copolymer and/or a copolymer of vinyl acetate and crotonic acid.

11. A process according to claim 9, characterized in that the binder for promoting the dispersing of the 7153/sza pigments in the concrete coloring material consists of an alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, a sulfated polyglycol ether, a melamine-formaldehyde condensate, a naphthalene-formaldehyde condensate, gluconic acid, an other polyhydroxy compound which is innoxious to the concrete; a salt of a low-molecular-weight partial ester of a styrene-maleic anhydride copolymer and/or a copolymer of vinyl acetate and crotonic acid.

12. A process according to any one of claims 8 to 11, characterized in that the binder is a lignin sulfonate.

13. A process according to any one of claims 8 to 11, characterized in that the granules are prepared by built-up granulation.

14. A process according to any one of claims 8 to 11, characterized in that the granules have been made by the drying of a mixture comprising pigment, binder, and liquid.

15. A process according to any one of claims 8 to 11, characterized in that the granules have been made by the drying of a mixture comprising pigment, binder, and water.

16. A process according to any one of claims 8 to 11, characterized in that the granules have been made by the spray-granulation of a mixture comprising pigment, binder, and liquid.

17. A process according to any one of claims 8 to 11, characterized in that the granules have been made by the spray-granulation of a mixture comprising pigment, binder, and water.

7153/sza

18 18. Concrete produced by using the material of claim 1 or 2 for dyeing thereof.

19. Dyed concrete produced by the process of claim 8, 9 or 10.

20. A material according to claim 7 wherein 90 % of the pigment granules have a size from 20 to 500 micrometers.

21. A process according to claim 16, characterized in that the 90 % of the pigment granules have a size from 20 to 500 micrometers.

22. A process according to claim 17, characterized in that the 90 % of the pigment granules have a size from 20 to 500 micrometers.

7153/sza