NZ717480B2 - Air entraining agent for mineral binder compositions - Google Patents
Air entraining agent for mineral binder compositions Download PDFInfo
- Publication number
- NZ717480B2 NZ717480B2 NZ717480A NZ71748014A NZ717480B2 NZ 717480 B2 NZ717480 B2 NZ 717480B2 NZ 717480 A NZ717480 A NZ 717480A NZ 71748014 A NZ71748014 A NZ 71748014A NZ 717480 B2 NZ717480 B2 NZ 717480B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- reducing agent
- mineral binder
- composition
- binder composition
- binder
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 239000011230 binding agent Substances 0.000 title claims abstract description 112
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 63
- 239000011707 mineral Substances 0.000 title claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 10
- 239000003638 reducing agent Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004567 concrete Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229960003563 Calcium Carbonate Drugs 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 description 51
- 150000003839 salts Chemical class 0.000 description 22
- 239000011780 sodium chloride Substances 0.000 description 22
- 239000011148 porous material Substances 0.000 description 15
- 239000004568 cement Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 239000008032 concrete plasticizer Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 241001243925 Sia Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 230000001419 dependent Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 125000001145 hydrido group Chemical group *[H] 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- -1 thiolufates Chemical class 0.000 description 2
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- 229960005069 Calcium Drugs 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000282619 Hylobates lar Species 0.000 description 1
- 241000229754 Iva xanthiifolia Species 0.000 description 1
- 229920000126 Latex Polymers 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 241001438449 Silo Species 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000000240 adjuvant Effects 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000004572 hydraulic lime Substances 0.000 description 1
- 230000002706 hydrostatic Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229910052904 quartz Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/26—Carbonates
- C04B14/28—Carbonates of calcium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0076—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials characterised by the grain distribution
- C04B20/0088—Fillers with mono- or narrow grain size distribution
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/42—Pore formers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/02—Elements
- C04B22/04—Metals, e.g. aluminium used as blowing agent
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/10—Acids or salts thereof containing carbon in the anion
- C04B22/106—Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
Abstract
The invention relates to a method for producing a mineral binder composition, in particular a concrete or mortar composition. At least one mineral binder is prepared using water, and an air entraining agent is added prior to and/or during the preparation of the mineral binder composition. The air entraining agent comprises a particulate reducing agent with an average particle size of at least 25 µm. training agent comprises a particulate reducing agent with an average particle size of at least 25 µm.
Description
AIR ENTRAINING AGENT FOR L BINDER COMPOSITIONS
Technical field
The invention relates to a method for producing a mineral binder composition,
5 more particularly a concrete or mortar composition, in which at least one mineral
binder is mixed with water and in which before and/or during the mixing of
the mineral binder composition an air ner is added. The invention further
pertains to the use of the air entrainers for introducing air pores and/or improving
the freeze/de-icing salt resistance in mineral binders. rer aspects of
10 the invention relate to a ition comprising an air entrainer and also to a
minerally binder composition.
Prior art
Mineral binder compositions such as concrete and mortar in particular must be
aerated in order, for example, to improve workability or in order to achieve suf-
15 ficient freeze/de-icing salt resistance.
One of the properties of water is to expand on freezing. In binder compositions,
therefore, on cooling below 0°C, liquid water is displaced by freezing water,
and a hydrostatic pressure is generated. If the tensile strength of the binder
ition is exceeded, the uences are instances of flaking or even
20 the destruction of the system.
If an air entrainer is added to the binder composition during mixing, stable air
pores can be produced, which are present in the binder composition even after
.
The prior art has disclosed various air entrainers, examples being various cati-
25 onic, anionic and nonionic surfactants or else tall oil (see WO 95/26936, CH
689619 and DE 195 28 912, for example).
2
Also in use in practice are solid air entrainers such as the product Sika® Aer
Solid (Sika Schweiz AG), for example, which consist of polymer-clad hollow air
beads.
The known air entrainers, however, have various disadvantages. A particular
5 problem is the customarily vely high metering sensitivity of the air entrainers.
Thus the required amount of air entrainers is customarily heavily dependent
on the mixing ion, on the binder used, on the aggregates, on the
quality of the mixing water, on the transport time, or on the viscosity during
processing of the binder composition.
10 When using liquid air entrainers, specifically, it is necessary to adjust the metering
separately for each application, and comprehensive quality control must
be performed. This gives rise to considerable effort and to corresponding costs.
More recent products such as Sika® Aer Solid have the advantage over the
liquid air entrainers that the air pores are added already in prefabricated form
15 and therefore that the sensitivity in relation to binder, for example, is lower. A
disadvantage, however, is that some of the solid air pores are destroyed during
the mixing ion. This on varies ing to mixer type, mixing time,
mixture viscosity, and the form of the ates.
Achieving adequate freeze/de-icing salt resistance in mineral binders is there-
20 fore relatively costly and inconvenient with the measures known to date. As a
result, there continues to be a need for new ons for improving the
freeze/de-icing salt resistance of mineral binder compositions, such solutions
having the entioned disadvantages to as small an extent as possible or
not at all.
25 Outline of the invention
It is an object of the present invention, therefore, to overcome the disadvantages
described above. The aim therewith is to provide new solutions for
improving the freeze/de-icing salt resistance of mineral binder compositions.
The solutions in particular are to operate as far as possible independently of
3
the particular processing method or of the specific binder composition, and are
to allow the production of mineral binder compositions having a very high
/de-icing salt resistance.
Surprisingly it has been found that this can be achieved by the method for pro-
5 ducing a l binder composition as claimed in claim 1.
The core of the present invention, accordingly, is the use of a reducing agent in
particle form as air entrainer, the average particle size of the reducing agent
being less than 25 µm. The air entrainer is added beforehand and/or during
mixing to at least one component of the mineral binder composition.
10 singly it has emerged that as a result it is possible to achieve excellent
freeze/de-icing salt resistances in various mineral binder compositions. This
may be attributable to an extremely mly distribution of the air pores with a
defined size in the range of 20 – 300 µm (diameter). The air entrainers here
function essentially ndently of the respective binder composition and of
15 the specific mixing technique. The metering sensitivity is therefore correspondingly
low, producing reliable control over the freeze/de-icing salt resistance.
Further aspects of the invention are t matter of further independent
claims. Particularly preferred embodiments of the invention are subject matter
of the dependent claims.
20 Ways of performing the invention
In a first aspect, the present ion comprises a method for producing a
mineral binder composition, more particularly a concrete or mortar composition,
preferably having a density of ≥ 1.0 kg/dm3, in which at least one mineral binder
is mixed with water and in which before and/or during the mixing of the mineral
25 binder ition an air entrainer is added, the air entrainer sing a reducing
agent in particle form having an average particle size of less than 25
µm.
The term "air entrainers" in this context stands in particular for a substance
which when t or added during the production of a mineral binder compo-
4
sition, generates air pores in the mineral binder composition. The air pores are,
in particular, substantially stable during the mixing operation and the processing
of the mineral binder composition. The term "air" should be interpreted
y in the present context, encompassing all substances which are gase-
5 ous under standard conditions.
A "reducing agent" refers presently in particular to material capable of reducing
water. The reducing agent advantageously possesses a standard potential or
reduction potential of less than -0.7 V, more particularly less than -0.9 V, preferably
less than -1.5 V, ally in the range from -0.9 to -2.5 V, relative to
10 the standard hydrogen ode under standard conditions (T = 298.15 K; p =
1 atm; ionic activity = 1).
The reducing agent is used in particle form. This means that the reducing
agent comprises a multiplicity of individual les. This reducing agent may
be present as or used in the form of a solid, such as a powder, a liquid, for ex-
15 ample in the form of a suspension or slurry, or in the form of a paste or a suspension
with high solids content. A suspension, a , or a paste may comprise
, for example, water and/or one or more c solvents, such as one or
more glycols, for example.
The particle size, its distribution, or the average particle size of the reducing
20 agent are ined in particular by means of laser diffraction, preferably in
accordance with standard ISO 13320:2009. Use is made more particularly of a
Mastersizer 2000 ment with a Hydro 2000G dispersing unit and the Mas-
tersizer 2000 re, from Malvern Instruments GmbH (Germany). An example
of a suitable measuring medium is isopropanol. The average particle
25 size corresponds presently in particular to the D50 (50% of the particles are
r than the stated value, 50% accordingly, larger).
The term "density" refers presently in particular to the specific gravity. The
density or specific gravity is ined in particular in accordance with standard
EN 1015-6.
5
The sion "mineral binder ition" refers present in particular to a
composition comprising at least one mineral binder and also, optionally aggregates
, adjuvants, admixtures and/or water. In principle, moreover, there may
also be further components t in the mineral binder composition, an ex-
5 ample being reinforcing fibers. The mineral binder composition can be mixed
by addition of water and mixing to form a curable mineral binder composition.
In principle the mineral binder composition may be liquid, pasty, or in solid
state.
The mineral binder composition is more particularly a cementitious binder
10 composition. A "cementitious binder" or a titious binder composition"
refers presently in particular to a binder or a binder composition having a cement
fraction of at least 5 wt%, more ularly at least 20 wt%, preferably at
least 50 wt%, especially at least 75 wt%.
A mineral binder is a binder which in the presence of water reacts in a hydra-
15 tion reaction to form solid hydrates or hydrate phases. It may be, for example,
a hydraulic binder (e.g. cement or hydraulic lime), a latent hydraulic binder (e.g.
slag), a pozzolanic binder (e.g. fly ash), or a non-hydraulic binder (e.g. gypsum
or white lime).
The mineral binder or the binder composition in particular ses a hydrau-
20 lic binder, preferably cement. Particularly preferred is cement of type CEM I, II,
III or IV (as per standard EN 197-1). A fraction of the hydraulic binder as a tion
of the overall mineral binder is advantageously at least 5 wt%, more
particularly at least 20 wt%, preferably at least 50 wt%, especially at least
75 wt%. According to another ageous embodiment, the mineral binder
25 comprises at least 95 wt% of hydraulic , more particularly cement.
It may, however, also be advantageous for the binder composition to comprise
other s as well as or instead of a hydraulic . Such binders are, in
particular, latent hydraulic binders and/or pozzolanic binders. Suitable latent
hydraulic and/or pozzolanic binders are, for example, slag, fly ash and/or silica
30 dust. The binder composition may also comprise inert materials such as finely
ground limestone, finely ground quartz and/or pigments, for example. In one
6
advantageous embodiment, the mineral binder comprises 5 – 95 wt%, more
ularly 20 – 50 wt%, of latent hydraulic and/or pozzolanic binders.
t being tied to the theory, it is assumed that the reducing agent reacts
with the mixing water in redox reactions during the mixing of the mineral binder
5 composition. One of the products of such reactions is hydrogen which provides
in turn for the formation of pores in the mineral binder composition.
It was found here that in order to achieve good freeze/de-icing salt resistance it
is critical for the average particle size of the reducing agent to e
< 25 µm, more particularly < 20 µm. If an average le size of 25 µm is ex-
10 ceeded, there is a significant drop in particular in the freeze/de-icing salt ance.
This may be utable to inadequate distribution of the pores in the
binder matrix and to a pore size distribution that is not suitable for the
achievement of freeze/de-icing salt resistance.
According to a further-preferred embodiment, an average particle size of the
15 reducing agent is 0.1 – 20 µm, more particularly 0.2 – 18 µm, preferably 0.5 –
15 µm, in particular 1 - 10 µm. With very particular ence the average
le size is 2 – 8 µm.
In particular the D90 of the particle size of the reducing agent is 25 µm, more
particularly 20 µm, especially 15 µm, especially preferably 10 µm or 8 µm. In
20 other words, 90% of the particles of the reducing agent in particular are smaller
than 25 µm, more particularly smaller than 20 µm, especially smaller than
15 µm, especially preferably smaller than 10 µm or smaller than 8 µm.
The D10 of the particle size of the reducing agent is preferably 0.1 µm, more
particularly 0.5 µm, especially 1 µm or 3 µm. In other words, 10% of the parti-
25 cles of the reducing agent are in particular less than 0.1 µm, more particularly
less than 0.5 µm, especially less than 1 µm or less than 2 µm.
A sieve residue of the particles of the ng agent ≥ 45 µm is preferably less
than 1 wt%, more preferably less than 0.5 wt%, more preferably still less than
0.2 wt% or less than 0.1 wt%.
7
Such particle sizes are particularly advantageous in relation to the freeze/deicing
salt resistance. It has emerged, moreover, that in these cases the distribution
of pore sizes is extremely homogeneous.
The reducing agent preferably comprises a metal, more particularly a non-
5 noble metal. The metal is preferably selected from the group consisting of aluminum
, magnesium, manganese, zinc and/or vanadium. Also le here in
particular are ations of a plurality of different metals. Metals presently
are in particular in the 0 (zero) oxidation state. Salts or metal oxides, accordingly
, are not included under the term "metals".
10 In particular the reducing agent comprises aluminum or consists of it. This aluminum
is, more particularly, metallic aluminum and not an aluminum salt. Aluminum
as reducing agent has emerged as being particularly ous since it is
particularly advantageous in relation to the freeze/de-icing salt problem, is simple
to handle, and can be incorporated well into mineral binder compositions by
15 mixing.
ing on requirements, however, other metals as well, or other nonmetallic
reducing , may be suitable.
With advantage, the reducing agent is added with a fraction of 0.0005 –
0.1 wt%, preferably 0.001 – 0.05 wt%, more ularly 0.002 – 0.03 wt%,
20 especially 0.002 – 0.02 wt% or 0.0025 – 0.01 wt%, based on the binder content
of the binder composition. This produces an optimum pore distribution and further
improves the freeze/de-icing resistance.
In praxis it has d that a reducing agent sing or consisting of pulverulent
aluminum having an average particle size of 0.1 – 20 µm, in particular
25 0.1 – 18 µm, more particularly 0.1 – 15 µm, preferably 1 – 10 µm or 2 – 8 µm,
is very ageous for many applications.
The reducing agent y consists of or comprises pulverulent aluminum having
an average particle size of 2 – 8 µm, which is added more particularly with
8
a fraction of 0.002 – 0.01 wt%, based on the binder content of the mineral
binder composition.
According to another preferred embodiment, the reducing agent is added as
part of a mixture with at least one filling material.
5 Filling material suitably includes, for example, chalks, fly ashes, silica fume,
slag, slag sands, gypsum, calcium carbonate, burnt lime, hydraulic powder,
e.g. cement, a latent hydraulic power, pozzolans, inert powders or mixtures
thereof. An especially preferred filling material is calcium carbonate.
Ideally the mixture contains 0.1 – 10 wt%, more particularly 0.5 – 5 wt%, of the
10 reducing agent and 90 – 99.9 wt%, more particularly 95 – 99.5 wt%, of the at
least one filling material.
Given that even small amounts of reducing agent are sufficient for effective
pore formation, the reducing agent can be provided in a form with better handling
qualities for practice h being mixed with a filling material. As a re-
15 sult, in particular, the metering of the reducing agent is simplified.
The ng agent and/or a mixture comprising the reducing agent may be
added to the l binder composition, for example, before, during and/or
after the addition of the mixing water. The mineral binder composition in this
case may for example already be in dry or wet ed form.
20 An alternative iliity is to premix the reducing agent and/or a mixture
sing the reducing agent with one or more ents of the mineral
binder composition, the binder, for example, and then to mix up the mineral
binder composition in a conventional way.
In the solid aggregate state, the reducing agent and/or a mixture sing
25 the reducing agent may also, for example, be part of what is called a dry mix,
which can be stored for a very long time and which is typically packaged in
sacks or stored in silos prior to use.
9
The reducing agent and/or a mixture comprising the reducing agent may also
be mixed beforehand with a further admixture, such as a cizer, for example
, in the form of a suspension, a slurry, or a solids mixture. That mixture can
then be added, again conventionally, during the mixing of the mineral binder
5 composition.
As further admixtures it is possible to use plasticizers, such as, for example,
ulfonates, ated naphthalene-formaldehyde condensates, sulfonated
melamine-formaldehyde condensates and/or polycarboxylate ethers (PCE).
Polycarboxylate ether-based plasticizers (PCE) are ularly preferred here.
10 The further admixtures may also comprise, for example, accelerators, corrosion
tors, pigments, retardants, shrinkage reducers, defoamers and/or
foam formers.
Specific substances which may be used as further admixtures are, for example
, thiocyanates, thiolufates, sulfates, nitrates, nitrites, ides, acetates,
15 formates, chlorides, glycerol, amino alcohols, organic acids, inorganic acids
and/or latex.
One possible achievement of combination with a further admixture is the acquisition
of multi-functional admixtures.
A further aspect of the present invention relates to the use of a reducing agent
20 in particle form, more particularly a reducing agent as tly described, for
the introduction of air pores into a l binder ition, more particularly
a te or mortar composition, and/or for improving the freeze/de-icing salt
resistance of the mineral binder composition.
The improvement in the freeze/de-icing salt resistance is determined in particu-
25 lar in accordance with standard SIA 262-1 Annex C and in relation to a correspondingly
reference sample without air entrainer.
The invention further relates to a composition comprising a reducing agent in
le form having an average particle size of less than 25 µm, and also at
10
least one further component selected from a g material, aggregates, a mineral
binder and/or a concrete admixture.
The reducing agent here is defined in particular as described above.
Accordingly, in the composition, the reducing agent advantageously comprises
5 pulverulent aluminum having a particle size of 0.1 – 20 µm, more particularly
0.1 – 15 µm, preferably 1 – 10 µm or 2 – 8 µm. Very preferably the reducing
agent consists of or comprises pulverulent aluminum having an average particle
size of 2 – 8 µm.
The at least one further component in the composition is more particularly a
10 g material, preferably calcium carbonate.
y the composition contains 0.1 – 10 wt%, more particularly 0.5 – 5 wt%, of
the reducing agent and 90 – 99.9 wt%, more particularly 95 – 99.5 wt%, of the
at least one filling material.
A further aspect of the present invention pertains to a mineral binder composi-
15 tion. The mineral binder composition may be present, for example, in liquid,
paste-like or solid state.
The mineral binder composition comprises at least one l binder and also
a composition as described above that ses a reducing agent in particle
form having an e particle size of less than 25 µm and also at least one
20 further ent selected from a filling material, aggregates, a binder and/or
a concrete admixture.
The mineral binder composition may also be obtained by a method as described
above for producing a l binder composition.
A weight ratio of water to binder ("w/c") during mixing of the mineral binder
25 composition is advantageously 0.2 – 0.8, more particularly 0.3 – 0.6, more ularly
0.35 – 0.55.
The pH during the production of the mineral binder composition is in the basic
range, preferably in the range ≥ 8, more preferably in the range ≥ 10 or ≥ 12.
11
The mineral binder composition 6 minutes after mixing preferably has an air
t of at least 4%, preferably at least 4.5%, especially ably 4% -
10%. The air content here is determined preferably in accordance with standard
EN 1015-7.
5 A density of the mineral binder composition, more particularly in the cured
state, is more particularly ≥ 1.0 kg/dm3, preferably ≥ 1.5 kg/dm3, especially ≥
2.0 kg/dm3, more ably 2.1 – 2.6 kg/dm3.
In particular the mineral binder composition is not a eight concrete composition
or a mineral binder composition with a density < 1.5 kg/dm3 or < 1.0
10 kg/dm3.
The l binder composition advantageously meets exposure class XF1,
preferably XF2, more particularly XF3, very preferably XF4 as relevant for the
freeze/de-icing salt resistance in accordance with standard EN 206-1.
A further aspect of the invention relates to a cured shaped body, more particu-
15 larly an edifice or part of an edifice, comprising a water-cured mineral binder
composition as described above.
Further advantageous embodiments of the invention are apparent from the
working examples below.
Working examples
20 Provision of an air pore-forming composition
In order to e an air pore-forming composition, 1 wt% of aluminum powder
(reducing agent) having an average particle size (D50) of 5 µm and a sieve
e at 45 µm of < 0.1 wt% (available from Benda-Lutz, Austria) was mixed
with 99 wt% of ulent calcium ate (product "Neckafill", available
25 from Kalkfabrik Netstal, Switzerland). The pulverulent mixture is referred to below
as air entrainer LP-1.
12
As a reference, a 1 wt% aluminum powder having an average particle size of
40 µm und 99 wt% calcium carbonate air entrainer was prepared. This pulverulent
mixture is referred to below as air ner LP-R.
The average particle size (D50) was determined in accordance with standard
5 ISO 13320:2009 using a Mastersizer 2000 ment, a Hydro 2000G dispers-
ing unit, and the Mastersizer 2000 re from Malvern Instruments GmbH
(Germany) with isopropanol as measuring medium.
Mortar tests
The activity of the air entrainers LP and LP-R was tested in various mortar mix-
10 tures. Table 1 lists the general dry composition of the mortar mixture used.
Table 1: Dry composition of the mortar mixture
Mortar mixture composition
ty in g
(maximum grain size 8mm)
Cement (for type see below) 750
Limestone filler 141
Sand 0-1 mm 738
Sand 1-4 mm 1107
Sand 4-8 mm 1154
In a first mortar mixture MM1, a CEM I 42.5 N Portland cement (1:1:1 mixture
of Swiss cement grades Holcim, Vigier, Jura cement) having a Blaine fineness
15 of about 3'400 cm2/g was used.
A second mortar mixture MM2, a CEM III A 32.5 N blast furnace cement
m, Modero 3A) was used.
For the mixing of mortar compositions, the sands, the limestone filler, and the
respective cement of the mortar mixture were mixed dry in a Hobart mixer for 1
20 minute. Over the course of 10 seconds, the mixing water, in which additionally
a concrete plasticizer had been ved or dispersed, and also the air entrainer
LP-1 or LP-R, respectively, were added and mixing was carried out for
13
a further 170 s. The total wet mixing time was 3 minutes. The water
/cement index (w/c) was 0.43 for MM1 and 0.39 for MM2.
Added to all of the mortar compositions, additionally, was a concrete plasticizer
(Sika® Viscocrete® 3010-S; available from Sika z AG) in order to im-
5 prove the workability of the mortar compositions. For MM1 0.8 wt% and for
MM2 0.7 wt% of the concrete plasticizer was used, based in each case on the
cement weight.
One minute after the mixing of the mortar compositions, the respective slump
flow (SF) was determined in accordance with standard EN 1015-3.
10 The testing for determining the freeze/de-icing salt resistance (FDR) took place
on cubes (15 x 15 x 15 cm at 20°C) in accordance with standard SIA 262-1
Annex C.
The specific gravity and the air content were determined 6 minutes after mixing
in ance with standards EN 1015-6 (specific gravity) and EN 1015-7 (air
15 content).
The results of the mortar tests are summarized in tables 2 (for mortar mixture
MM1) and 3 (for mortar mixture MM2). R1 is a reference sample, ed
rly to the other mortar mixtures on the basis of MM1 but without addition
of an air entrainer. R3 is a corresponding reference sample based on MM2.
20
14
Table 2: Results of mortar tests with mortar mixture MM1
Sample Air entrainer/ SF Specific gravity Air content FDR*
level of addition [mm] [g/dm3] [%] [gm2]
[wt%]
R1 - 185 2370 3.1 1300
R2 LP-R / 0.75 196 2327 5.0 1100
A LP-1 / 0.25 197 2321 5.2 300
B LP-1 / 0.50 198 2310 5.9 100
C LP-1 / 0.75 196 2320 5.8 20
D LP-1 / 1.00 195 2293 7.1 80
Table 3: Results of mortar tests with mortar mixture MM2
Sample Air entrainer/ SF Specific gravi- Air content FDR*
level of on [mm] ty [%] [gm2]
[wt%] [g/dm3]
R3 - 191 2352 3.3 1540
R4 LP-R / 0.75 192 2320 4.5 1250
E LP-1 / 0.25 188 2335 4.8 410
F LP-1 / 0.50 195 2310 5.4 130
G LP-1 / 0.75 195 2319 5.6 40
H LP-1 / 1.00 193 2297 6.8 60
* The smaller the measured value, the better the freeze/de-icing salt resistance.
15
The results of the mortar tests show that the addition of air entrainer based on
aluminum powder with an e particle size < 25 µm produces an ive
and constant air input of more than 4.0% and at the same time achieves excellent
freeze/de-icing salt resistance on the part of the mortar es. This is so
5 irrespective of the type of binder used.
In contrast, when using coarse-grained air entrainers (samples R2 and R4), the
results e, in particular, substantially poorer freeze/de-icing salt resistances.
The working examples above, however, represent only illustrative actualiza-
10 tions of the ion, which may be modified arbitrarily within the invention.
Thus, for example, aluminum powder can be combined in the air entrainer LP-
1 with a different reducing agent, such as with magnesium powder, for example
, or may be replaced entirely by the other reducing agent.
It is also possible, for example, to replace calcium carbonate in the air entrainer
15 LP-1 by a different filling material or to omit the filling material entirely.
Additionally, for example, the aluminum powder or the air entrainer LP-1 can
be premixed with a component of the dry mortar mixture, such as with dry cement
or dry ates, for e.
It is conceivable, furthermore, for the aluminum powder to be suspended in the
20 concrete plasticizer or in another concrete admixture instead of being mixed
with the calcium carbonate. By this means a multifunctional admixture can be
provided.
In conclusion, therefore, it can be stated that an extremely advantageous
method and also ts suitable therefor have been provided for the intro-
25 duction of air pores into mineral binder compositions and for the production of
binder compositions having high freeze/de-icing salt resistance.
Claims (8)
- ≥1.0 kg/dm3, in which at least one mineral binder is mixed with water and 5 in which before and/or during the mixing of the mineral binder composition an air entrainer is added, characterized in that the air entrainer comprises a reducing agent in particle form having an average particle size of less than 25 μm, n the reducing agent is a metal selected from the group consisting of aluminum, magnesium, manganese, zinc, 10 and/or vanadium, wherein the reducing agent is added as part of a mixture with calcium carbonate, and wherein the mixture contains 0.1 – 10 wt% of the reducing agent and 90 – 99.9 wt% of the calcium carbonate, and wherein the reducing agent comprises pulverulent aluminum having an average particle size of 2 – 8 µm which is added with a fraction of 15 0.002 – 0.01 wt%, based on the binder content of the mineral binder composition.
- 2. The method as claimed in claim 1, terized in that an average particle size of the reducing agent is 0.1 – 20 µm, more particularly 0.2 – 18 µm, preferably 0.5 – 15 µm, in particular 1 - 10 µm or 2 – 8 µm. 20
- 3. The method as claimed in at least one of claims 1 - 2, characterized in that the reducing agent consists of aluminum.
- 4. The method as d in at least one of claims 1 - 3, characterized in that the reducing agent is added with a fraction of 0.0005 – 0.1 wt%, ably 0.001 – 0.05 wt%, more particularly 0.002 – 0.03 wt%, especially 25 0.002 – 0.02 wt%, based on the binder content of the binder composition.
- 5. A composition comprising a reducing agent in particle form having an average particle size of less than 25 µm and calcium carbonate, wherein the ng agent is a metal selected from the group consisting of aluminum, magnesium, manganese, zinc, and/or um, and where 0.1 – 10 wt% 30 of the ng agent and 90 – 99.9 wt% of the calcium carbonate are 17 present, wherein the reducing agent comprises pulverulent aluminum having an average particle size of 0.1 - 18 μm.
- 6. A mineral binder composition comprising at least one mineral binder and also a composition as claimed in claim 5. 5
- 7. A l binder composition obtained by a method as claimed in at least one of claims 1 – 4.
- 8. The mineral binder composition as claimed in claim 6 or claim 7, a density of the mineral binder ition being ≥ 1.0 kg/dm3, preferably ≥ 1.5 kg/dm3, especially ≥ 2.0 kg/dm3, more ably 2.1 – 2.6 kg/dm3. 10
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13180573 | 2013-08-15 | ||
EP13180573.1 | 2013-08-15 | ||
PCT/EP2014/065941 WO2015022168A1 (en) | 2013-08-15 | 2014-07-24 | Air entraining agent for mineral binder compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ717480A NZ717480A (en) | 2021-06-25 |
NZ717480B2 true NZ717480B2 (en) | 2021-09-28 |
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