Granulated blast furnace slag powder-based binder, dry and wet formulations made therefrom and method of making same
阅读说明：本技术 基于粒化的高炉矿渣粉的黏结剂，由其制得的干式制剂和湿式制剂及其制备方法 (Granulated blast furnace slag powder-based binder, dry and wet formulations made therefrom and method of making same ) 是由 劳伦特·弗鲁安 莫亨德·沙乌什 阿图尔·基阿什科 尼古拉斯·米西卡斯 于 2018-11-16 设计创作，主要内容包括：本发明涉及基于矿渣的黏结剂或包含所述基于矿渣的黏结剂的砂浆或混凝土组合物。本发明的目的是提出一种黏结剂,其是基于OPC的组合物的有吸引力的替代品,其环保、便宜且有竞争力,在卫生和安全问题上比基于OPC的组合物更令人满意,它产生具有适当流变性质的湿式制剂,即在所述湿式制剂的使用者通常所需的凝固时间(例如一小时至数小时-3小时)内具有稳定的流变性质,而不会增加由该湿式制剂获得的硬化材料的W/B比,也不会损害其机械性能。为了实现该目的,本发明是基于矿渣的黏结剂,其包含：A.至少一种矿渣；A’,任选地,至少一种含CO<Sub>3</Sub>的矿物粉末；B.任选地,至少一种不同于黏结剂A并且不同于CO<Sub>3</Sub>粉末A’的共黏结剂；C’.任选地,至少一种不同于C的共激活剂C’；C.至少一种水/炉渣反应的激活剂；D.至少一种螯合剂和/或至少一种螯合剂源,所述螯合剂优选为阻垢剂；E.以及至少一种不同于螯合剂D的高效减水剂。本发明还涉及用于制造黏结剂的套装、包含黏结剂和骨料的干式混凝土或砂浆、用于制备湿式制剂(黏结剂/水或水泥砂浆/水)的方法以及由湿式制剂制造建筑物或土木工程或其要素、涂料、填料、整平板、瓷砖胶黏剂和/或内部或外部保温系统的方法。(The present invention relates to a slag-based binder or a mortar or concrete composition comprising the same. The object of the present invention is to propose a binder which is an attractive alternative to OPC-based compositions, which is environmentally friendly, inexpensive and competitive, and which is more satisfactory than OPC-based compositions with respect to hygiene and safety issues, which results in a wet formulation with appropriate rheological properties, i.e. a setting time (e.g. one to several hours-3 hours) which is usually required by the user of said wet formulationTime) without increasing the W/B ratio of the hardened material obtained from the wet formulation and without impairing its mechanical properties. To achieve this object, the present invention is a slag-based binder comprising: A. at least one slag; a', optionally, at least one CO-containing 3 The mineral powder of (1); B. optionally, at least one is different from binder A and different from CO 3 Co-binder of powder a'; optionally, at least one co-activator C' different from C; C. at least one activator of the water/slag reaction; D. at least one chelating agent, preferably a scale inhibitor, and/or at least one source of chelating agent; E. and at least one high-efficiency water reducing agent different from the chelating agent D. The invention also relates to a kit for manufacturing a binder, a dry concrete or mortar comprising a binder and an aggregate, a method for preparing a wet formulation (binder/water or cement mortar/water) and a method for manufacturing a building or civil engineering or elements thereof, coatings, fillers, screeds, tile adhesives and/or internal or external insulation systems from a wet formulation.)
1. A slag-based binder comprising:
A. at least one slag;
optionally, at least one CO-containing3The mineral powder of (1);
B. optionally, at least one is different from binder A and different from CO3Co-binder of powder a';
C. at least one activator of the water/slag reaction;
optionally, at least one co-activator C' different from C;
D. at least one chelating agent, preferably a scale inhibitor, and/or at least one source of chelating agent;
E. And optionally at least one high range water reducer different from chelant D.
2. The binder of claim 1 or 2, wherein slag a is a powder, preferably selected from the following particle size grades:
a1) d50 is ]7.0 to 20.0 μm ], ]7.0 to 60 μm ] or ]7.0 to 100.0 μm ];
a2) d50 is 3.0 to 7.0 μm ];
a3) d50 is 0.5 to 3.0. mu.m ], preferably [1.0 to 2.0. mu.m ];
a4) and mixtures thereof.
3. The binder of at least one of the preceding claims, wherein the binder comprises CO3The mineral A' is selected from the group consisting of limestone, dolomite, precipitated CaCO3Chalk, marble, aragonite, crystalline travertine, travertine and mixtures thereof.
4. The binder of at least one of the preceding claims, wherein the binder comprises CO3The mineral a' of (a) is a powder or slurry selected from the following particle size grades:
a'1) D50 is ]250 to 40 μm ];
a'2) D50 is ]16.0 to 250.0 μm ];
a'3) D50 is ]6.0 to 16.0 μm;
a'4) D50 is ]3.0 to 6.0 μm;
a'5) D50 is 0.9 to 3.0 μm, preferably [1.0 to 2.0 μm ];
a'6) D50 is 0.02 to 0.9 μm ];
a'7) and mixtures thereof.
5. The binder of at least one of the preceding claims, wherein at least one co-binder B different from slag a is present, said co-binder B preferably comprising at least one compound selected from the group consisting of slaked/quick lime, slaked lime, sulfate-rich cement, calcium aluminate cement, calcium sulfoaluminate cement, portland ground clinker, (class F and/or class C) fly ash, pozzolanic binders, (class F and/or class C) natural and synthetic pozzolans, silica fume, rice hull ash, paper sludge ash, bottom ash, incineration bottom ash, recycled glass, steel slag, phosphorous slag, ladle slag, red mud, cement kiln dust, biomass ash and mixtures thereof.
6. The binder of at least one of the preceding claims 1 to 4, wherein at least one co-binder B different from slag A is present, said co-binder B comprising at least one Layered Double Hydroxide (LDH) and/or at least one precursor for in situ LDH formation.
7. The binder of claim 6, wherein the LDH is characterized by the general formula (I):
[Mp z+M'q y+(OH)2]a+(Xa-)a/n·bH2O
wherein M isp z+M'q y+Is a metal cation or a mixture of metal cations; z is 1 or 2; y is 3 or 4; p + q ═ 1; b is 0 to 10; xa-Is an anion and is 1 to 5, and a is defined by p, q, y and z, such that a ═ zp + yq-2;
m is preferably selected from the group comprising-desirably of the composition-Mn, Li, Mg, Zn, Fe, Ni, Co, Cu, Ca or mixtures of two or more thereof;
y is preferably 3 and M' is preferably selected from the group comprising-ideally the composition-Cr, Mn, Co, V, Sc, Al, Ga, Fe or mixtures thereof; preferably selected from the subgroups comprising-ideally consisting of-Al, Ga, Fe or mixtures thereof; al is the most preferred element M';
in a very preferred embodiment, M/M' is selected from Zn/Al, Ni/Al, Mg/Al and/or Ca/Al.
8. The binder of claim 6 or 7 wherein the LDH precursors are selected from the group consisting of-ideally composition-
i. Ordinary Portland Cement (OPC) finely ground clinker minerals;
ii.OPC；
iii, D50 is 1.0 to 5.0 μm slag powder;
an alumina source;
v. a source of iron;
a source of magnesium;
a calcium source;
a lithium source;
ix, a zinc source;
x. a manganese source;
a copper source;
a mineral belonging to the hydrotalcite super group;
xiii.
9. The binder according to at least one of claims 6 to 8, wherein the concentration of co-binder B-in% by dry weight relative to A, relative to A and A ', relative to A and B or relative to A and A' and B-is in the following range with increasing priority: [0 to 50 ]; [0 to 20 ]; [0 to 15 ]; [0.1 to 7 ].
10. Binder according to at least one of the preceding claims, wherein chelating agent D is a limescale growth inhibitor, preferably a precipitated calcium-containing phase, more preferably a compound selected from the group consisting of:
phosphonic acids, preferably monophosphonic acids and/or diphosphonic acids;
phosphoric acids, preferably triphosphates and/or hexametaphosphoric acids;
carboxylic acids, preferably polyacrylic acids, citric acids, tartaric acids and/or gluconic acids;
amines;
derivatives thereof, salts thereof;
and mixtures thereof;
even more preferably a compound selected from: PBTC (phosphonobutane-1, 2, 4-tricarboxylic acid), ATMP (amino-trimethylene phosphonic acid), HEDP (1-hydroxyethylene-1, 1-diphosphonic acid), DTPA (diethylenetriaminopentaacetic acid), DCTA (diaminocyclohexane tetraacetic acid), PAA (polyacrylic acid), PPCA (phosphino polyacrylate), PMA (polymaleic acid), MAT (maleic acid terpolymer), SPOCA (sulfonated phosphonocarboxylic acid), PPCA (polyphosphonocarboxylic acid), EDTMP (ethylenediamine-tris [ methylenephosphonic acid ]) and DTPMP (diethylenetriamine-penta [ methylenephosphonic acid ]), derivatives thereof, salts thereof, and mixtures of these compounds.
11. The binder of at least one of the preceding claims comprising at least one high range water reducer E, wherein the high range water reducer E is a compound selected from the group consisting of: NBSP (naphthalene based superplasticizers), PNS (polynaphthalenesulfonates), MBSP (melamine based superplasticizers), PMS (polymelamine sulfonates), HCA (hydroxycarboxylic acids), (P) AA [ (poly) acrylic acids ], LS (lignosulfonates) in particular ammonium, calcium or sodium lignosulfonates, PCE (polycarboxylic ether), PCA (polycarboxylic acids), phosphonates, salts and/or derivatives of these compounds and mixtures of these compounds.
12. Kit comprising at least a part of the binder according to at least one of the preceding claims and instructions for preparing a wet formulation comprising the binder, at least one aggregate and water in such an amount that the water/binder ratio is within the following ranges of increasing priority:
0.1≤W/B≤1；0.2≤W/B≤0.55；0.2≤W/B≤0.5。
13. a dry composition comprising a binder according to at least one of claims 1 to 12 and at least one aggregate.
14. A wet formulation comprising the binder according to at least one of claims 1 to 12, at least one aggregate and water in such an amount that the water/binder ratio is within the following ranges of increasing priority:
0.15≤W/B≤0.5；0.2≤W/B≤0.55；0.2≤W/B≤0.5。
15. A method for preparing the wet formulation of claim 18, comprising mixing binder, aggregate and water in an amount such that the water/binder ratio is within the following ranges of increasing priority:
0.15≤W/B≤0.5；0.2≤W/B≤0.55；0.2≤W/B≤0.5；
preferably, a portion of the binder and at least a portion of the water are mixed together prior to mixing with the aggregate.
16. A method for manufacturing buildings or civil engineering works or elements thereof, coatings, fillers, screeds, tile adhesives and/or internal or external insulation systems from a wet formulation according to claim 18, which hardens when exposed to air.
Technical Field
The technical field of the present invention relates to a hydraulic mineral binder comprising at least one slag, such as granulated blast furnace slag powder (GGBS or slag), for use in settable and hardenable compositions such as mortar or concrete compositions.
More particularly, the invention relates to binders for the construction industry and to settable and hardenable compositions comprising at least one slag as hydraulic binder and at least one functional additive.
The invention also relates to a method for preparing these slag-based binders, these dry or wet settable and hardenable compositions.
The use of the set and hardened products obtained from these compositions in construction is also within the field of the present invention.
Background
The production of portland cement has a large negative impact on the environment due to the emission of large amounts of carbon dioxide. During calcination of raw materials at high temperature (1450 ℃) in cement production processes, CO is inherently produced in the furnace by limestone decarburization2(formula (1)):
CaCO3(s)→CaO(s)+CO2(g) (1)
in addition, fossil fuels required for the furnace are burned to release carbon dioxide. By increasing the grinding additional emissions are generated, nearly one ton of CO per ton of Portland cement2. Overall, the carbon dioxide emissions from the cement industry account for 7% to 9% of the world.
This adverse effect is exacerbated by the large demand for water from complete hydration of portland cement.
Furthermore, the handling of portland cement may cause health problems (e.g. allergy), especially due to the high alkalinity of portland cement (pH higher than 13). In addition, harmful elements such as hexavalent chromium (cr (vi)) may be released during kneading, which is also toxic to workers. Although cr (vi) reducing agents (e.g., ferrous sulfate) are typically included in cement powders, their efficacy is limited by time. It is expected that construction workers, particularly third world construction workers, will not frequently check the expiration dates associated with such treatments.
Most current research on new binders aims at replacing cement in various applications with binders that have less impact on the environment. One approach is to use resources that are not expensively processed, such as by-products from other industries (waste for one industry, but primary resources for other industries). This is the case with blast furnace slag, which is a by-product of the steel industry. By grinding this product to a fine powder (GGBS), a cementitious material is obtained which can partially replace cement or can be used alone by adding some chemical activator (e.g. alkali or sulphate).
It is important to note that the use of GGBS is not only environmentally friendly, but also has a variety of enhanced properties, such as high resistance to sulfate attack, low permeability, good resistance in chemically aggressive environments, low hydration heat (required for large structures), overall excellent durability, the possibility to immobilize heavy metals or radionuclides, and the like.
Another benefit of GGBS-based products is that they require low amounts of water to achieve the proper rheological properties. This is also important from an environmental and social point of view. In fact, not only in arid regions, water resources are drastically reduced worldwide, which leads in particular to geopolitically stressful situations and wars. In this respect, the benefit of reducing the amount of kneading water in the cement is not incidental, considering the large quantities of cement consumed worldwide.
Furthermore, the presence of slag in the cementitious binder is known to reduce the release of toxic cr (vi).
Solving these environmental and toxicological problems should not compromise neither the proper rheology nor the properties of the final hardened product, i.e. mechanical strength and durability, which are directly related to the final porosity of the hardened product.
Another parameter to be controlled is the water/binder ratio (W/B), which should be less than or equal to 1.0, preferably 0.7, more preferably 0.4 or 0.35.
Alkali activated slag cement (AAS) may replace Ordinary Portland Cement (OPC).
WO2015087255a1 discloses a base-activated slag composition comprising:
-a source of slag: blast Furnace Slag (BFS);
on metal oxide equivalent (i.e. for Na)2CO3Is Na2O), a source of alkali metal carbonate (activator) comprising 0.5 to 6.0% by weight of the slag source: sodium carbonate, potassium carbonate and lithium carbonate;
-an amorphous polymorphic source of silica comprising from 0.5 to 10.0% by weight of the slag source: silica fume;
-an alkali metal hydroxide source comprising 0.5 to 10.0 wt.% of the slag source: slaked lime;
-a non-aqueous plasticizer source in the form of sodium lignosulfonate;
possibly some aggregates, such as stones or sand.
Such alkali-activated slag compositions can be improved by providing an optimized concrete/mortar wet formulation obtained by mixing the composition with aggregate and water.
The optimized concrete/mortar wet formulation may have a low water/binder (W/B) ratio, e.g., less than or equal to 1.0, preferably 0.7, more preferably 0.4 or 0.35, while having good workability, e.g., as defined by ACI standard 116R-90(ACI 1990B), which is defined as "this property of fresh concrete/mortar determines its ease and homogeneity with which it can be mixed, placed, set and plastered". ASTM defines this as "this property determines the amount of work required to treat the amount of fresh concrete/mortar with minimal loss of homogeneity". A reference test for workability of wet concrete/mortar formulations is the "slump test".
In other words, this means a stable rheology over a period of several hours of open time, for example 1 to 3 hours.
These suitable application properties should be obtained without increasing the W/B ratio. Excess water does maintain rheological properties for the desired setting time, making it suitable for good workability, but this seriously jeopardizes the mechanical properties of the hardened concrete/mortar.
Furthermore, it is also preferred to limit the concentration and retarder in the concrete/mortar composition, as long as the retarder is preferably used carefully to control cost and avoid excessive retardation, rapid slump loss, and excessive plastic shrinkage (change in volume of fresh concrete/mortar as surface water evaporates).
Object of the Invention
In this case, the present invention aims to solve at least one of the above problems and/or needs by achieving at least one of the following objects:
o1-providing a slag-based binder or mortar or concrete composition comprising the slag-based binder, which is an attractive alternative to OPC-based compositions.
O2-providing a slag-based binder or a mortar or concrete composition comprising the slag-based binder, which is environmentally friendly.
O3-providing a slag-based binder or a mortar or concrete composition comprising the slag-based binder, which is cheap and competitive.
O4-providing a slag-based binder or a mortar or concrete composition comprising the slag-based binder, which is more satisfactory than the OPC-based composition in terms of hygiene and safety issues.
O5-providing a slag-based binder or mortar or concrete composition comprising the slag-based binder, which results in a dry or semi-dry precast concrete formulation with suitable capacity made by a vibrocompaction process.
O6-provides a slag-based binder or mortar or concrete composition comprising said slag-based binder, which produces a wet formulation with appropriate rheological properties, i.e. stable rheological properties (good workability), within the usual setting times (e.g. minutes to hours) required by the user of the wet formulation, without increasing the W/B ratio and without impairing the mechanical properties of the hardened material obtained from the wet formulation.
O7-providing a slag-based binder or a mortar or concrete composition comprising said slag-based binder, which results in a hardened material having the required mechanical properties, in particular an acceptable early strength (e.g. 24 hours).
O8-providing a slag-based binder or a mortar or concrete composition comprising said slag-based binder, thereby producing a hardened material having a desired durability.
O9-providing a slag-based binder or mortar or concrete composition comprising the GGBS-based binder, which produces a hardened material with a generally desired setting time (e.g., several minutes to several hours).
O10-providing a slag-based binder or a mortar or concrete composition comprising said GGBS-based binder, which results in a hardened product with an acceptable W/B ratio, for example less than or equal to 1.0, preferably 0.7, more preferably 0.4 or 0.35 or 0.30.
O11-provides a simple and inexpensive method of preparing a slag-based binder or a mortar or concrete composition comprising the slag-based binder that meets at least one of the purposes-O1-to-O10-.
O12-provides a simple and inexpensive method of preparing a wet slag-based binder or a mortar or concrete composition comprising the slag-based binder.
O13-hardened products for the construction industry are provided, comprising slag as at least part of the binder.
Disclosure of Invention
Accordingly, the present invention relates to a slag-based binder comprising:
A. at least one slag;
optionally, at least one CO-containing3The mineral powder of (1);
B. optionally, at least one is different from binder A and different from CO3Co-binder of powder a', if present;
C. at least one activator of the water/slag reaction;
optionally, at least one co-activator C' different from C;
D. At least one chelating agent, preferably a scale inhibitor, and/or at least one source of chelating agent;
E. and at least one high-efficiency water reducing agent different from the chelating agent D.
With regard to the objectives-O1-to-O12-, in particular with regard to workability, with regard to a reduction in the initial water demand and with regard to an increase in the final strength of the hardened concrete/mortar, the inventors have worked to find the benefits of component D in combination with the other components A and C and optionally A 'and/or B and/or C' and/or E. In addition, the new composition counteracts the reduction in initial strength of hardening at ambient temperatures associated with neutral and acidic slag cements.
Such slag-based binders can control the properties of the final hardened material, including mechanical strength and durability. In particular, the hardened material has no or little shrinkage and exhibits good freeze-thaw properties and good chemical resistance. This slag-based binder also has a limited environmental impact, which is very important.
In another aspect, the invention relates to a kit comprising at least a portion of the binder component according to the invention and instructions for preparing a wet formulation comprising the binder, at least one aggregate and water in an amount such that the water/binder ratio is in the following range of increasing priority:
0.1≤W/B≤1；0.2≤W/B≤0.5；0.25≤W/B≤0.4。
In another aspect, the invention relates to a dry composition, such as concrete or mortar, comprising a binder according to the invention and at least one aggregate.
According to a variant of the invention, the slag-based binder composition and/or the dry composition [ slag-based binder/aggregate ] may also incorporate at least one ingredient, preferably at least one functional additive.
In another aspect, the invention relates to a wet formulation comprising a binder according to the invention, at least one aggregate and water in such an amount that the water/binder ratio is in the following ranges with increasing priority:
0.1≤W/B≤1；0.2≤W/B≤0.5；0.25≤W/B≤0.4。
in another aspect, the invention relates to a method for preparing a wet formulation according to the invention, the method comprising mixing binder, aggregate and water in an amount such that the water/binder ratio is in the following range of increasing priority:
0.1≤W/B≤0.5；0.2≤W/B≤0.5；0.25≤W/B≤0.4；
preferably, a portion of the binder and at least a portion of the water are mixed together prior to mixing with the aggregate.
In a further aspect, the invention relates to a method for producing buildings or civil engineering works or elements thereof, coatings, fillers, screeds, tile adhesives and/or internal or external insulation systems from a wet formulation according to the invention which hardens when exposed to air or water.
Definition of
According to the terminology herein, the following non-limiting definitions must be considered:
-not using a quantitative term to denote a plurality,
"slag" means a stone waste separated from the metal during smelting or refining of the ore.
- "GGBS" or "GGBFS": granulated blast furnace slag powder is equivalent to blast furnace slag, blast furnace slag (GBFS), blast furnace granulated slag powder and blast furnace slag fine aggregate.
"cement" is understood to mean a pulverulent substance used for the manufacture of mortars or concretes. It is a mineral binder and may not contain any organic compounds. It includes slag portland blended cement and geopolymer-based cement.
"adhesive" means any material or substance that holds or pulls together other materials, either mechanically, chemically or as a binder, to form a cohesive whole.
"mortar" means a material consisting of a binder and aggregates, such as sandy soil.
"concrete" means a material consisting of a binder and aggregates such as sand and (fine) gravel.
The term "non-aqueous" is understood to mean a substance in solid form which is insoluble or non-dispersible in aqueous solutions. The solid form may comprise constituent water molecules contained in a crystalline network. Solid forms may also include powders, flakes, granules, and the like.
"mixing" is to be understood as any form of mixing and may include grinding or milling of the substance in solid form.
"D50" gives the median size of the particle size distribution of the material particles (typically microns for gel materials). This means that 50% of the particles are smaller than the specified number, or that 50% of the particles are larger than the specified number. The measurement of D50 was carried out in a wet process by means of a laser diffraction analyzer, also known as laser diffraction spectroscopy, by means of a laser diffraction analyzer known as "Mastersizer 3000" and commercialized by MALVERN corporation.
"dry weight" -the weight of the material in its natural state (without addition of water or other external solution).
"in situ LDH formation" refers to the preparation of LDH after mixing the binder with water, e.g. by precipitation.
The expression "different" in "B different from a" or "C different from C'" especially means at least one chemical and/or at least one physical difference.
Detailed Description
Adhesive agent
A.Slag of mine
Slag a is preferably GGBS.
GGBS is a glassy particulate material obtained by quenching molten slag in a blast furnace in water and then finely grinding the quenched product to improve GGBS reactivity. GGBS is an amorphous aluminosilicate glass mainly composed of SiO 2CaO, MgO and Al2O3And (4) forming. There are many glass network cationic modifiers: ca. Na, Mn, etc.
GGBS is preferably manufactured according to European Standard [ NF EN 15167-1 ].
According to a noteworthy feature of the invention, slag a is a powder or a slurry, preferably obtained as a by-product from different industries, either in its natural state or synthetically obtained. The chemical composition is as follows:
the numbers in the table are relative to the dry weight% of a.
In a preferred embodiment of the invention, slag a is a powder, preferably selected from the following particle size grades:
a1) d50 is ]7.0 to 20.0 μm ], ]7.0 to 60 μm ] or ]7.0 to 100.0 μm ]; [ e.g., standard GGBS ];
a2) d50 is 3.0 to 7.0 μm ]; [ e.g., fine GGBS ];
a3) d50 is 0.5 to 3.0 μm, preferably [1.0 to 2.0 μm ] or [0.5 to 2.0 μm ]; [ e.g., ultrafine GGBS ];
a4) and mixtures thereof.
In another embodiment, the slag a powder comprises (relative to a):
α 1.100% by dry weight of a1) grade A powder, or
α 2.99 to 50% dry weight, preferably 99 to 60% dry weight, of a1) grade a powder, and 1 to 50% dry weight, preferably 1 to 40% dry weight, of a2) grade a powder, or
α 3.1 to 40% by dry weight, preferably 1 to 30% by dry weight, of a3) grade a powder.
Slag a may also be defined by its boehmeria fineness. Given below in cm2The Brinell fineness (Bf) (ASTM C204 Brinell fineness) of the slag A in terms of/g and arranged in order of increasing priority is:
·500≤Bf≤20000；
·1000≤Bf≤10000；
·2000≤Bf≤8000；
·3000≤Bf≤7000；
·3500≤Bf≤6000；
according to one particular variant of the invention, slag a comprises from 70% to 99.1% by weight, preferably from 80% to 99.1% by weight, of particles whose Bf is: bf is more than or equal to 2500 and less than or equal to 8000; preferably 3500. ltoreq. Bf. ltoreq.7000; from 30 to 0.1% by weight, preferably from 20 to 0.1% by weight, of particles whose Bf is: bf is more than or equal to 8000 and less than or equal to 16000; preferably 10000 ≦ Bf ≦ 14000.
It should be emphasized that slag, such as GGBS, is a hydraulic binder (as opposed to fly ash or silica fume, for example). This means that the slag reacts only with water.
A′. 3Mineral A 'containing CO'
Containing CO3The mineral A' of (A) is preferably selected from the group comprising-ideally consisting of-limestone, dolomite, precipitated CaCO3Chalk, marble, aragonite, crystalline travertine, travertine and mixtures thereof.
In an advantageous embodiment, the CO is contained3The mineral a' of (a) is a powder or slurry preferably obtained as a by-product from different industries, or obtained in its natural state, or obtained by synthesis, selected from the following particle size grades:
a'1) D50 is ]250 to 40 μm ];
a'2) D50 is ]16.0 to 250.0 μm ];
a'3) D50 is ]6.0 to 16.0 μm;
a'4) D50 is ]3.0 to 6.0 μm;
a'5) D50 is 0.9 to 3.0 μm, preferably [1.0 to 2.0 μm ];
a'6) D50 is 0.02 to 0.9 μm ];
a'7) and mixtures thereof.
For example, containing CO3The mineral a' of (a) is a crystalline solid or an ionic solid.
Possibly containing CO3The mineral a' powder of (a) comprises (relative to a):
α α 1.100 dry weight% of a '1) grade a' powder;
or
α α 2.100 dry weight% of a '3) grade a' powder;
or
α α 3.90 to 10% dry weight, preferably 80 to 30% dry weight, of a '1) grade a' powder, and 10 to 90% dry weight, preferably 20 to 70% dry weight, of a '2) grade a' powder;
or
α α 4.1 to 40% by dry weight, preferably 10 to 30% by dry weight, of a '3) grade a' powder;
or
α α 5.1 to 20, preferably 5 to 15 dry weight% of a '3) grade a' powder and 99 to 80, preferably 95 to 85 dry weight% of a '5) grade a' powder.
Examples of a '1) to a'6) D50 are as follows: 10mm +/-5; 100+/-10 μm; 10+/-1 μm; 4.5+/-1 μm; 1.5+/-0.1 μm; 0.5+/-0.01 μm.
With respect to the particle size grade a '6) of the A ' powder, precipitated calcium carbonate (called PCC) is a CO-containing product belonging to a '6)3Examples of the purpose of the mineral. PCC is a precipitated powder of very pure calcium carbonate limestone (99.0 +/-1%). The PCC particles are nano-sized. Examples of PCC D50 are as follows: 0.05+/-0.01 μm; 0.08+/-0.01 μm.
The specific surface is another one which can promote the CO-containing reaction according to the invention3Selected parameters of the mineral a' powder of (a).
Advantageously, containing CO3The BET of the mineral A' of (a) may be 1m2G to 60m2G, e.g. equal to 25+/-5m2/g and/or equal to 8+/-5m2/g。
B.Co-binder
Slag a is preferably used with a co-binder B.
Thus, according to the invention, the binder comprises at least one binder different from slag A and possibly different from the CO-containing binder when A' is present3The hydraulic co-binder of mineral a' of (a).
According to one embodiment Eb1Preferably, the co-binder B comprises at least one compound selected from the group consisting of hydrated lime/quicklime, slaked lime, sulfate-rich cement, calcium aluminate cement, calcium sulfoaluminate cement, Portland fine ground clinker, (class F and/or class C) fly ash, pozzolanic binders, (class F and/or class C) natural and synthetic pozzolans, silica fume, rice hull ash, paper sludge ash, bottom ash, incinerated bottom ash, recycled glass, steel slag, stainless steel slag, phosphorous slag, copper slag, ladle slag, red mud, cement kiln dust, biomass ash, and mixtures thereof 。
Co-binders such as OPC binders (OPC: ordinary portland cement, in particular CEM I, II, III, IV and V), for example CEM I.
According to one embodiment Eb2There is at least one co-binder B different from slag a, the co-binder B comprising at least one Layered Double Hydroxide (LDH) and/or at least one precursor for in situ LDH formation.
LDHs are ionic solid materials whose layered structure comprises [ hydroxide layer/metal cation layer/hydroxide layer/anion-neutral molecular layer/hydroxide layer/metal cation layer/hydroxide layer ].
Metal cations, e.g. trivalent cations, e.g. Al3+、Fe3+Etc. and divalent cations, e.g. Ca2+、Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+Or Zn2+And the like.
The co-binder LDH may be a single LDH or a mixture of different LDHs. According to another upcoming feature of the invention, the LDH is characterized by the general formula (I):
[Mp z+M'q y+(OH)2]a+(Xa-)a/n·bH2O
wherein M isp z+M'q y+Is a metal cation or a mixture of metal cations; z is 1 or 2; y is 3 or 4; p + q ═ 1; b is 0 to 10; a. thea-Is an anion and is 1 to 5, and a is defined by p, q, y and z, such that a ═ zp + yq-2;
m is preferably selected from the group comprising-desirably of the composition-Mn, Li, Mg, Zn, Fe, Ni, Co, Cu, Ca or mixtures of two or more thereof.
y is preferably 3 and M' is preferably selected from the group comprising-ideally the composition-Cr, Mn, Co, V, Sc, Al, Ga, Fe or mixtures thereof; preferably, selected from the subgroup comprising-ideally the composition-Al, Ga, Fe or mixtures thereof; al is the most preferred element M'; in a very preferred embodiment, M/M' is selected from Zn/Al, Ni/Al, Mg/Al and/or Ca/Al.
Advantageously, the anion a is selected from halides, inorganic oxyanions, anionic surfactants, anionic chromophores and/or anionic UV absorbers.
In particular, the inorganic oxyanion may be carbonate, bicarbonate, hydrogenphosphate, dihydrogenphosphate, nitrite, borate, nitrate, sulfate, sulfite, or phosphate, or a mixture of two or more thereof.
For example, the inorganic oxyanion is preferably nitrate, carbonate, chloride and/or sulfate.
According to a remarkable feature of the invention, the LDH is in the form of particles, and the particles have a size of not more than 10000nm, preferably not more than 2000nm, more preferably not more than 300nm, even more preferably not more than 100 nm.
The particle size of the LDH may be from 50nm to 350nm in diameter, for example from 200nm to 300nm (measured using transmission electron microscopy). For example, LDH is [ Ca ] 2Al(OH)6](NO3)·bH2O or [ Ca ]2Al(OH)6](SO4)0.5·bH2O。
Under appropriate conditions, for example at a pH of greater than or equal to 10, for example in the
According to a particular feature of the invention, wherein the LDH precursor is selected from the group comprising-ideally consisting of
i. Ordinary Portland Cement (OPC) finely ground clinker minerals;
ii.OPC；
iii, D50 is 1.0 to 5.0 μm slag powder;
an alumina source;
v. a source of iron;
a source of magnesium;
a calcium source;
a lithium source;
ix, a zinc source;
x. a manganese source;
a copper source;
a mineral belonging to the hydrotalcite super group;
xiii.
(i) OPC finely ground clinker is made by heating a homogeneous mixture of raw materials in a rotary kiln at high temperature. The products of the chemical reaction are agglomerated together at a sintering temperature of about 1300 ℃ to 1450 ℃. The main raw materials for clinker production are typically limestone and another material containing clay as a source of aluminosilicate. Some of the second starting materials used were: clay, shale, sandy soil, iron ore, bauxite, fly ash and slag.
In one notable feature of the invention, the OPC finely ground clinker portland cement (i) may be as follows:
the advantageous feature of the OPC finely ground clinker Portland cement (i) is that it is given below in cm2The Brinell fineness (ASTM C204 Brinell fineness) (Bf) in terms of/g and arranged in ascending order of priority is:
·500≤Bf≤10000；
·1000≤Bf≤9000；
·2000≤Bf≤8000。
one particular variant according to the invention, given below in cm2The (Bf) of the OPC finely ground clinker Portland cement (i) in terms of/g is: bf is more than or equal to 2000 and less than or equal to 3000;
one particular variant according to the invention, given below in cm2The (Bf) of the OPC finely ground clinker Portland cement (i) in terms of/g is: bf is more than or equal to 3000 and less than or equal to 4500;
one particular variant according to the invention, given below in cm2The (Bf) of the OPC finely ground clinker Portland cement (i) in terms of/g is: 5500-Bf-6500.
(ii) The OPC used as a precursor to the LDH may be CEM I, II, III, IV and V, for example CEM I.
Of OPC (ii)An advantageous feature is that in cm is given below2The Brinell fineness (ASTM C204 Brinell fineness) (Bf) in terms of/g and arranged in ascending order of priority is:
·500≤Bf≤10000；
·1000≤Bf≤9000；
·2000≤Bf≤8000。
according to a particular variant of the invention, given below in cm2(Bf) of OPC (ii) in terms of/g is: bf is more than or equal to 2000 and less than or equal to 3000;
according to a particular variant of the invention, given below in cm 2The (Bf) of the OPC finely ground clinker Portland cement (i) in terms of/g is: bf is more than or equal to 3000 and less than or equal to 4500;
according to a particular variant of the invention, given below in cm2The (Bf) of the OPC finely ground clinker Portland cement (i) in terms of/g is: 5500-Bf-6500.
(iii) Slag powders whose D50 is 1.0 to 5.0 μm may be those defined above.
(iv) The alumina source may be:
-aluminates, in particular sulphates, chlorides, nitrates; alum;
alumina, aluminium hydroxide, sodium aluminate, potassium aluminate
-calcium aluminate cement; calcium sulfoaluminate cement, tricalcium aluminate, tricalcium aluminoferrite;
-aluminosilicate clay minerals, in particular kaolinite group minerals;
alumina-containing minerals, such as bauxite;
all forms thereof, in particular forms with different amounts of water, calcined forms, non-calcined forms, dried forms, slurry forms and mixtures thereof;
-mixtures thereof.
As an example of sodium aluminate, NaAlO can be cited2、NaAl(OH)4、Na2O·Al2O3、Na2Al2O4、Na5AlO4、Na17Al5O16、Na7Al3O8、NaAl11O17An inorganic salt; mixed sodium hydroxide (NaOH) and alumina (Al)2O3) Sources and mixtures thereof.
(vi) The following are examples of Mg sources: magnesium acetate, magnesium bromate, magnesium bromide, magnesium chlorate, magnesium chlorite, magnesium chromate, magnesium fluosilicate, magnesium formate, magnesium iodide, magnesium iodate, magnesium molybdate, magnesium nitrate, magnesium perchlorate, magnesium sulfate and magnesium thiosulfate;
(vii) The following are examples of calcium sources: calcium aluminate cement, calcium sulfoaluminate cement, calcium carbonate, calcium sulfate, calcium chloride, calcium bromide, calcium fluoride, calcium oxide, calcium hydroxide, calcium hydride, calcium iodide, calcium oxalate, calcium nitrate, calcium nitrite, calcium perchlorate, calcium phosphate, calcium pyrophosphate, calcium thiocyanate, calcium formate, calcium hydroxyapatite, calcium permanganate, calcium acetate, calcium azide, calcium bicarbonate, calcium chlorate and the like.
(viii) The following are examples of lithium sources: lithium hydroxide, lithium carbonate, lithium nitrite, lithium nitrate, lithium perchlorate, lithium permanganate, lithium selenide, lithium selenite, lithium sulfate, lithium (III) sulfate, lithium tartrate, lithium thiocyanate, lithium formate, lithium fluorosilicate, lithium acetate, lithium azide, lithium benzoate, lithium bromate, lithium bromide, lithium chlorate, lithium chromate, lithium dichromate, lithium dihydrogen phosphate, lithium iodide, lithium molybdate;
(xii) Belongs to minerals of hydrotalcite supergroup.
Hydrotalcite supergroups (also known as Mg-Al carbonate hydrotalcite groups) are the best known examples of natural LDH phases. It comprises
The hydrotalcite group(s) is (are),
the quintinite group, in the form of a single crystal,
the natural "green rust" phase of patina (fougerite),
copper aluminum alum hydrate group,
the antimony-aluminum-copper ore group,
A zinc-copper-aluminum-vanadium group,
a cluster of aluminum-calcium-magnesium hydroxide stones, and
hydrocalumite group.
According to the possibility of the invention, these minerals (v) belonging to the hydrotalcite supergroup are calcined. For example, the hydrotalcite is heated during the heat treatment to a temperature of, for example, about 500 ℃.
The incorporation of LDH into the slag binder composition according to the invention can be carried out either in dry (powder) or in wet (solution, slurry).
Whatever the form of the precursor to be incorporated in the slag binder composition according to the invention (dry or wet), the aim is to comply with the following quantitative conditions:
the concentration of co-binder B-in dry weight% relative to a, relative to a and a ', relative to a and B, or relative to a and a' and B-is in the following ranges with increasing priority: [0 to 50 ]; [0 to 20 ]; [0 to 15 ]; [0.1 to 7 ].
For precursors (i) [ Ordinary Portland Cement (OPC) finely ground clinker minerals ] and (ii) [ OPC ], preferred concentration ranges are-in relation to a, in relation to a and a ', in relation to a and B or in relation to the dry weight% of a and a' and B-: [0 to 30 ]; [0 to 15 ]; [0.1 to 10 ].
Due to this advantageous embodiment Eb2The slag binder according to the invention makes it possible to obtain early strengths (at least 0.5Mpa) of 1 to 3 days and setting times of 5 minutes to 12 hours (rheology compatible with correct workability) under different curing conditions. Needless to say, these are favorable results.
C.Activating agent
It should be emphasized that slag a is a hydraulic binder (as opposed to, for example, fly ash or silica fume). This means that the slag reacts only with water. The addition of a chemical activator (or heat) is beneficial to accelerate the reaction. The action of activator C is generally to increase the pH to a suitable level to enhance the nucleophilic attack of hydroxide ions on the glass network.
The activator promotes the setting and/or curing and/or hardening of the binder, mortar/concrete composition.
The activator may be in hydrated or anhydrous solid form, for example in powder form or in solid form, for example as a solution or suspension.
All or a portion of the activator can be incorporated into the water for mixing with the composition comprising the binder.
The activator is preferably incorporated in the dry composition in powder form prior to mixing with water, thereby producing a so-called ready-mixed mortar/concrete composition.
The dry activator may be mixed with a binder and/or aggregate/filler.
Alternatively, an aqueous, preferably alkali-activated solution may be added to the other powdered components. In this case, the term two-component binder is used.
According to one object embodiment of the invention, the activator C is selected from:
Alkali metal carbonates, alkali metal silicates, alkali metal hydroxides, alkali metal sulfates and mixtures thereof; the alkali metal is preferably Li, Na, K;
mineral waste comprising at least one alkali metal carbonate and/or soda and/or potassium salt, and/or alkali metal silicate and/or alkali metal sulfate and/or lime;
the mineral waste is preferably selected from mineral wastes comprising-ideally consisting of: coal gangue tailings, iron ore mine tailings, copper mine tailings, tungsten mine tailings, chromite tailings, vanadium mine tailings, red mud, incinerator bottom ash, coffee waste, incinerator products of waste paper sludge, incinerator products of sludge produced by water treatment, rock mineral wool, glass mineral wool, fluid catalytic cracking oil residue, rice hull bark ash, palm oil fuel ash silicon manganese ore residue, ceramic red clay bricks, ceramic stoneware and mixtures thereof;
phosphoric acid;
and mixtures thereof;
preferably alkali metal carbonates, especially Na2CO3Or K2CO3。
According to one noteworthy characteristic of the invention, the concentration of activator C-in% by dry weight relative to a, relative to a and a ', relative to a and B or relative to a and a' and B-is in the following range with increasing priority: [0.1 to 30.0 ]; [1.0 to 16.0 ]; [4.0 to 12.0 ].
According to one example, the GGBS-based binder composition may include as component B: fly ash 55 wt% or B: 30 wt% fly ash, 20 wt% OPC and 5 wt% LDH precursors (Al source and Mg source), the remainder being a: GGBS and C.
Co-activator
In a particular embodiment, the activator C is combined with at least one co-activator C' different from C, selected from soluble salts of chlorides and/or fluorides and/or sulfates, hydrates thereof, anhydrous forms thereof and mixtures thereof-preferably with the composition-NaCl, CaCl2、NaF、Na2SiF6、KCl、Na2SO4、K2SO4、CaSO4Hydrates thereof, anhydrous forms thereof, and mixtures thereof.
These preferred activators and co-activators C and C ' can accelerate or slow down the reaction of the systems AA ', AB or AA ' B and alter the properties of the systems AA ', AB or AA ' B.
Advantageously, the concentration of co-activator C ', in dry weight% relative to a, relative to a and a ', relative to a and B, or relative to a and a ' and B, is in the following range of priority delivery: [0.001 to 30.0 ]; [0.01 to 16.0 ]; [0.05 to 10 ].
D.Chelating agents
In a preferred embodiment, the chelating agent D is a scale inhibitor,
preferred are precipitated calcium scale growth inhibitors containing calcium or aluminium phases (e.g. calcium carbonate, monocalcite, C-S-H °, C-a-S-H), more preferred are compounds selected from:
Phosphonic acids, preferably monophosphonic acids and/or diphosphonic acids;
phosphoric acids, preferably triphosphates and/or hexametaphosphoric acids;
carboxylic acids, preferably polyacrylic acids, citric acids, tartaric acids and/or gluconic acids;
amines;
derivatives thereof, salts thereof;
and mixtures thereof;
even more preferably a compound selected from: PBTC (phosphonobutane-1, 2, 4-tricarboxylic acid), ATMP (amino-trimethylene phosphonic acid), HEDP (1-hydroxyethylene-1, 1-diphosphonic acid), DTPA (diethylenetriaminopentaacetic acid), DCTA (diaminocyclohexane tetraacetic acid), PAA (polyacrylic acid), PPCA (phosphino polyacrylate), PMA (polymaleic acid), MAT (maleic acid terpolymer), SPOCA (sulfonated phosphonocarboxylic acid), PPCA (polyphosphonocarboxylic acid), EDTMP (ethylenediamine-tris [ methylenephosphonic acid ]) and DTPMP (diethylenetriamine-penta [ methylenephosphonic acid ]), derivatives thereof, salts thereof, and mixtures of these compounds.
The chelating agent D may be selected from compounds comprising-preferably consisting of the formula:
salts or acid forms thereof and mixtures thereof; (D.5) is particularly preferred.
According to the invention, D is advantageously a Ca and/or Al chelating agent.
It is also preferred that the stability constants of Ca + + of the chelating agent D are, in the preferred increasing order, less than or equal to 10, 5, 0 and ideally from-10 to-1.
According to another outstanding feature of the invention, the chelating agent D is capable of adsorbing itself to the reactive solid portion of the binder during the mixing process that takes place during the curing process. Preferably adsorption by electrostatic attraction, e.g. the solid part is negatively charged (oxide) and the chelating agent D is neutral and/or positively charged.
The concentration of chelating agent D-in dry weight% relative to slag a-is advantageously selected in the following ranges with increasing priority:
[0.001 to 2.0 ]; [0.01 to 0.1 ]; [0.01 to 0.5 ].
E.High-efficiency water reducing agent
When the binder according to the invention comprises at least one superplasticizer E, the latter is preferably a compound chosen from the following compounds: NBSP (naphthalene based superplasticizers), PNS (polynaphthalenesulfonates), MBSP (melamine based superplasticizers), PMS (polymelamine sulfonates), HCA (hydroxycarboxylic acids), (P) AA [ (poly) acrylic acids ], LS (lignosulfonates) in particular ammonium, calcium or sodium lignosulfonates, PCE (polycarboxylic ethers), phosphonates, salts and/or derivatives of these compounds and mixtures of these compounds; MSSP, PMS, NBSP, PNS and PCE are particularly preferred.
Preferential concentration of superplasticizer E-relative to slag in dry weight%, within the following ranges of increasing priority:
[0.01 to 10.0 ]; [0.05 to 5.0 ]; [0.05 to 2.0 ].
F.Other ingredients
The binder is advantageously enriched with one or more other components, which are particularly preferred components of the functional additives selected from the following list:
F.1. an activator other than C and C',
F.2. a water-retaining agent.
The water retention agent has the property of retaining mixed water prior to setting. The water is so trapped in the wet formulation paste that its cohesiveness is improved. To some extent, water is rarely absorbed by the carrier. Salt precipitation on the surface is limited and evaporation is reduced.
The water retaining agent is preferably selected from: modified cellulose, modified guar, modified cellulose ether and/or guar ether and mixtures thereof, more preferably consisting of: methylcellulose, methylhydroxypropylcellulose, methylhydroxyethylcellulose and mixtures thereof.
F.3. Rheological agent other than F.2
Possible rheological agents (also called "thickeners") are preferably selected from the group comprising, more preferably consisting of: clays, starch ethers, cellulose ethers and/or gums (e.g. vinylon guar xanthan, succinoglycan), modified polysaccharides of which modified starch ethers, polyvinyl alcohol, polyacrylamide, clays, sepiolite, bentonite and mixtures thereof are preferred, more preferably selected from clays, bentonite, montmorillonite.
F.4. Defoaming/antifoaming agent
Possible anti-foaming agents are preferably selected from the group comprising, more preferably consisting of: polyether polyols and mixtures thereof.
F.5. Biocide agent
Possible biocides are preferably selected from the group comprising, more preferably consisting of: mineral oxides such as zinc oxide and mixtures thereof.
F.6. Pigment (I)
Possible pigments are preferably selected from the group comprising, more preferably consisting of:
F.7. Flame retardant
Possible flame retardants (or fire retardants) are preferably selected from the group comprising, more preferably consisting of, the following which make it possible for the composition to increase the fire resistance and/or reduce the propagation speed of the flame:
■ mineral, preferably aluminium hydroxide [ Al (OH) ]3、ATH]Magnesium hydroxide MDH, hydromagnesite, hydrates, red phosphorus and boron compounds, preferably borates,
■ organic halides, preferably organic chlorides, more preferably derivatives such as chlorendic acid and chlorinated paraffins; organic bromides, such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane,
■ preferably brominated polystyrene, Brominated Carbonate Oligomer (BCO), Brominated Epoxy Oligomer (BEO), tetrabromophthalic anhydride, tetrabromobisphenol A (TBBPA), and Hexabromocyclododecane (HBCD).
■ antimony, preferably antimony pentoxide and sodium pyroantimonate
■ organophosphorus compounds, preferably organic phosphates, TPP, RDP, BPADP, tris-o-cresyl phosphate,
■ the phosphonates are preferably DMMP and phosphinates.
■ Chlorophosphoric acid esters, such as TMCP and TDCP.
F.8. Air entraining agent
The air entraining agent (surfactant) is advantageously selected from the group comprising-ideally consisting of natural resins, sulphated or sulphonated compounds, synthetic detergents, organic fatty acids and mixtures thereof, preferably comprising-ideally consisting of lignosulphonates, basic soaps of fatty acids and mixtures thereof, more preferably comprising-ideally consisting of sulphonic olefins, sodium lauryl sulphate and mixtures thereof.
F.9. Retarder
Retarders (tartaric acid and its salts: sodium or potassium salts, citric acid and its salts: sodium salts (trisodium citrate), and mixtures thereof;
F.10. plasticizer
F.11. Fiber
F.12. Dispersing powder
F.13. Wetting agent
F.14. Polymeric resins
F.15. With D and a different complexing agent; and
F.16. an aqueous dispersion.
F.17. A drying shrinkage-reducing agent based on a polyhydric alcohol,
the concentration of the binder in the additive may be from 0.001 wt% to 10 wt% of the total weight of the composition, particularly the binder composition.
***
In a prominent embodiment of the present invention, the base binder composition comprises:
Ggbs (different particle size distribution);
limestone, e.g. containing CO3Mineral powders of (different particle size distribution/reactivity);
opc or clinker or lime thereof, and mixtures thereof;
C. activators such as sodium carbonate (e.g., about 6% to 10% on GGBS);
D. ethylenediamine trimethylene phosphonate (EDTMP) and/or Hydroxyethylenediphosphonate (HEDP) and
E. high efficiency water reducing agent, etc. (less than 1%).
The slag-based binder or the mortar or concrete composition comprising the slag-based binder has the advantages of-O1-to-O10-described above.
With regard to-O5-, the slag-based binder or the mortar or concrete composition comprising the same according to the present invention makes it possible to produce a dry or semi-dry precast concrete formulation with appropriate capacity manufactured by a vibratory compaction method.
The invention therefore also relates to:
a dry or semi-dry precast concrete formulation comprising the slag-based binder according to the invention or a mortar or concrete composition comprising the slag-based binder;
a method for producing said dry or semi-dry precast concrete formulation, in particular by vibrocompaction.
Suit for manufacturing adhesive
This is a conditioning kit comprising all or part of the components of the binder and instructions for preparing a wet formulation comprising the binder according to the invention, at least one aggregate and water in an amount such that the water/binder ratio is within the following ranges of increasing priority:
0.1≤W/B≤1；0.2≤W/B≤0.55；0.2≤W/B≤0.5。
dry composition binder/aggregate
In other words, a dry composition such as concrete or mortar, comprising a binder according to the invention as defined herein and at least one aggregate, in particular: sand and/or gravel and/or packing of different particle size distributions.
Aggregate/filler
Aggregates include a class of particulate materials used in construction, including sand, gravel, crushed stone, slag (non-finely ground), recycled concrete, and geosynthetic aggregates. They serve to reinforce the strength of the overall composite.
The mortar/concrete composition may also include:
fillers such as dry powders, for example fillers based on quartz, limestone, barite or clay and mixtures thereof;
and lightweight fillers such as perlite, diatomaceous earth (diatomaceous earth), expanded mica (vermiculite), and foamed sand and mixtures thereof.
The amount of aggregate/filler in the mortar or concrete composition may suitably be from 0 to 97 wt%, preferably from 20 to 80 wt%, and more preferably from 50 to 70 wt%, based on the total weight of the mortar or concrete and depending on the application.
Advantageously, the dry composition (e.g. concrete or mortar) comprises, in addition to the aggregate, one or more than one ingredient, in particular a functional adjuvant, which may be identical to the additives f.1 to f.17 as defined above in the detailed description of the binder.
The "admixture" concentration in a dry composition such as a concrete/mortar may range from 0.1 to 10 weight percent based on the total weight of the composition, particularly mortar or concrete composition.
Wet formulation binder/aggregate
The invention also relates to a wet formulation comprising a binder of the invention as defined herein, at least one aggregate and water in an amount such that the water/binder ratio is in the following ranges of increasing priority:
0.1≤W/B≤1；0.2≤W/B≤0.55；0.2≤W/B≤0.5。
method of producing a composite material
The invention also includes:
1. a simple and inexpensive method for preparing a wet formulation according to the invention, which comprises mixing binder, aggregate and water in such an amount that the water/binder ratio is in the following ranges of increasing priority:
0.15≤W/B≤0.5；0.2≤W/B≤0.4；0.25≤W/B≤0.35；
preferably, a portion of the binder and at least a portion of the water are mixed together prior to mixing with the aggregate.
2. A simple and inexpensive method of manufacturing buildings or civil engineering works or elements thereof, paints, fillers, screeds, tile adhesives and/or internal or external insulation systems from a wet formulation according to the invention as defined herein, which hardens upon exposure to air.
The manufacturing process is characterized in that the wet formulation according to the invention as defined herein is shaped or applied onto a support and then the curing step is carried out at a temperature of (with increasing priority) -5 ℃ to 95 ℃, 20 ℃ to 65 ℃, 25 ℃ to 50 ℃ for 1 hour to 48 hours, preferably 5 hours to 36 hours.
The curing step may also comprise at a relative humidity greater than or equal to 40%, preferably equal to 80%, and more preferably equal to 100%; cycling of increasing and decreasing temperatures at pressures of 8Atm to 12Atm or 1 Atm.
The elements thus produced are, for example, paving bricks, concrete, mortar.
Examples
The particle size data D10, D50, D90 used in the following examples were determined by a wet method using a laser analyzer from Malvern under the name "MASTERSIZER 3000".
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