Patent Application
20160214892
The present invention relates to binders comprising calcium sulfoaluminate based cement/clinker types and supplementary cementitious materials, a method of manufacturing composite binders and to their use for making hydraulically setting building materials or special construction chemical compositions.
Calcium sulfoaluminate (CSA) cements are made from clinkers that include ye'elimite (Ca4(AlO2)6SO4 or C4A3$ in cement chemist's notation) as a major phase. These binders are used as constituents in expansive cements, in ultra-high early strength cements and in “low-energy” cements. Hydration of CSA cements leads to the formation of mainly ettringite and/or monophases as e.g. monosulfate. Aluminium hydroxide may probably be another hydration product of this binder. The amount and kinetics of formation strongly depend on the cement composition as e.g. the amount and type of sulfate bearing phases being present. Special physical properties (such as intentional expansive behaviour or rapid reaction) are obtained by the adjustment of the availability of calcium and sulfate ions. The use of CSA cement as a low-energy alternative to Portland cement has been pioneered in China, where several million tons per year are produced. The energy demand for production is lower because of the decreased kiln temperatures required for reactions, the better grindability and the lower amount of limestone in the raw mix, which needs to be endothermically decarbonated. In addition, the lower limestone content and lower fuel consumption leads to a CO2 emission around half of that of Portland cement clinker.
Within the context of the present invention, clinker shall mean a sinter product which is obtained by burning a raw material mixture at an elevated temperature and which contains at least one hydraulically reactive phase. Cement denotes a clinker that is ground with or without adding further components. Binder or binder mixture denotes a mixture hardening hydraulically and comprising cement and typically, but not necessarily, additional finely ground components, and which is used after adding water, optionally admixtures and/or additives and aggregate. A clinker may already contain all the necessary or desired phases and be used directly as a binder after being ground to cement.
Another approach to save energy and valuable raw materials is the application of secondary raw materials or industrial by-products as raw meal components to replace primary mineral based raw materials during clinker production.
In a further approach supplementary cementitious materials, which are often industrial by-products or wastes, are used to replace parts of the clinker during cement production and therefore save energy and primary raw material sources. These materials most often possess a pozzolanic or latent hydraulic reactivity and contribute to the mechanical performance of these composite binders.
Constituents that are permitted in Portland-composite cements are artificial pozzolans (like e.g. blastfurnace slag, silica fume, synthetic glasses and fly ashes) or natural pozzolans (like e.g. siliceous or siliceous aluminous materials such as volcanic ash glasses, calcined clays and shale). Portland blastfurnace cement contains up to 70% ground granulated blast furnace slag, the rest being Portland clinker and a little sulfate as e.g. gypsum. These composite cements typically produce high ultimate strength, but as slag content is increased, early strength is reduced, while potentially sulfate resistance increases and heat evolution diminishes. Portland fly ash cement contains up to 35% fly ash. The fly ash possesses a pozzolanic behaviour, so that ultimate strength is maintained or even increased. Because fly ash addition allows a lower water to binder ratio and as a result thereof a lower total water content, early strength can also be maintained.
Supplementary cementitious materials can be divided into latent hydraulic materials and pozzolans. Latent hydraulic materials are not hydraulic on their own or react only very slowly. They need an activation to undergo hydraulic reaction within useful time periods. Activation is typically achieved by (addition of) earth alkali metal or alkali metal compounds (e.g. Ca(OH)2, NaOH, KOH, etc.) or sulfate providing materials (CaSO4, Na2SO4, K2SO4, etc.), which are able to support the formation of calcium (aluminium) silicate hydrates and/or ettringite and/or others like e.g. AFm-phases (strätlingite, monosulfate, monocarbonate hemicarbonate etc.) or zeolite-like mineral. Pozzolans are siliceous or alumino-siliceous materials that react with calcium hydroxide from other components of a binder to form calcium silicate hydrates. The foregoing distinction is not always applied strictly, i.e. many fly ashes contain considerable amounts of calcium and are latent hydraulic materials, therefore, but usually they are designated pozzolans, nonetheless. For the present invention the distinction is not important and both are summarized as supplementary cementitious materials, partly abbreviated SCM herein.
Typical supplementary cementitious materials are natural or artificial pozzolans and latent hydraulic materials, e.g. but not exclusively ground granulated blast furnace slag, and natural or artificial pozzolans, e.g. but not exclusively type-C and/or type-F fly ashes, calcined clays or shales, trass, brick-dust, artificial glasses, silica fume, and burned organic matter residues rich in silica such as rice husk ash or mixtures thereof.
A problem of portland cement and portland-composite cements is the increasing demand of high early strength. Time granted for construction is continuously decreasing. In the manufacturing of building elements a fast form removal is desired to optimize investment return. Therefore, binders providing high early strength are required, of course without decreasing ultimate strength, durability or workability. There further remains the object to provide cements that have a minimal environmental impact with regard to energy and natural raw materials.
There have been some proposals to add SCM to calcium sulfoaluminate cements.
According to GB 2490010 describes cementitious compositions containing (a) 60-94% of at least one pozzolanic material; (b) at least 0.5% calcium sulfoaluminate; (c) 1.2-11%, expressed as SO3, of at least one inorganic sulfate; and (d) a total sulfate content, expressed as SO3, of at least 3%, wherein the cementitious composition includes, at most 3% natural lime, and at most 10% alumina cement. Strength development of this system is mainly based on ettringite, it is a so called super sulfated system with a ratio of calcium sulfate to ye'elimite+aluminates+ferrites of more than 1, the CSA and at least one source of CaO/Ca(OH)2, originating from the addition of e.g. CaO or OPC, is used as activator for early strength.
In Zivica V., “Possibility of the modification of the properties of sulfoaluminate belite cement by its blending”, Ceramics—Silikaty 45 (1), 24-30, (2001) the addition of 5%, 15% and 30% SCM to a CSA cement containing about 53% C2S, 34% C4A3$, 8% C4AF and 5% C$ is studied. From the explanations it is apparent that overburned or “dead burned” anhydrite is part of the clinker and that the SCMs are mostly performing as inactive fillers. Consequently, the article suggests that SCM contents below 15% are optimal. A significant energy saving seems not possible therewith.
In Quillin K., BRE “Low-CO2 Cements based on Calcium Sulfoaluminate” (http://www.soci.org/News/˜/media/Files/Conference%20Downloads/Low%20Carbon%20Cements%20Nov%2010/Sulphoaluminate_Cements_Keith_Quillin_R.ashx, status June 2013), the impact of adding 30 or 50% ground granulated blast furnace slag or 30% fly ash as well as the impact of sulfate content to a CSA cement containing about 22% C2S, 60% C4A3$, 7% C4AF, 8% C3S and 5% C3A is studied. The ratio of calcium sulfate to the sum of C4A3$, aluminates and ferrites is adjusted to 0, 0.35, 0.93 or above 1.
Surprisingly it was now found that composite binders comprising calcium sulfoaluminate cement and supplementary cementitious materials with a weight ratio R$/(Y+A+F) of calcium sulfate to the sum of ye'elimite, aluminates and ferrites in the range from 0.5 to 0.85 provide good early and ultimate strength, while further diminishing the environmental impact compared to binders based on calcium sulfoaluminate cements without addition of SCMs. R$/(Y+A+F) especially stands for CaSO4/(Σye'elimite+Σaluminates+Σferrites), wherein
Calcium sulfate can also be present within the supplementary cementitious materials or in the CSA clinker. This calcium sulfate also has to be taken into account for the calculation of R$/(Y+A+F). Amorphous aluminate or ferritic phases are special forms of e.g., but not exclusively, C12A7, CA, C4AF, CF. Aluminates and/or ferrites introduced by the addition of further components like calcium aluminate or Portland cements to the binder have to be considered as well for the calculation of R$/(Y+A+F).
The present invention solves the above mentioned problems with a composite binder comprising calcium sulfoaluminate cement and supplementary cementitious materials with a weight ratio of sulfate to the sum of ye'elimite, aluminates and ferrites in the range from 0.5 to 0.85, wherein preferably
To simplify the description, the following abbreviations, which are common in the cement industry, are used: H—H2O, C—CaO, A—Al2O3, F—Fe2O3, M—MgO, S—SiO2 and $—SO3. Additionally, compounds are generally indicated in the pure forms thereof, without explicitly stating series of solid solutions/substitution by foreign ions and the like, as are customary in technical and industrial materials. As any person skilled in the art will understand, the composition of the phases mentioned by name in the present invention may vary, depending on the chemism of the raw meal and the type of production, due to the substitution with various foreign ions, such compounds likewise being covered by the scope of the present invention.
The supplementary cementitious materials can be chosen from all available materials showing latent hydraulic and/or pozzolanic properties. Preferred are ground granulated blast furnace slag, fly ashes type C and F and natural pozzolans, calcined clays or shales, trass, artificial glasses, other slags than ground granulated blast furnace slag, brick-dust and burned organic matter residues rich in silica such as rice husk ash. Especially preferred are calcium-rich artificial glasses, type C fly ashes and ground granulated blast furnace slags.
Calcium sulfoaluminate clinkers contain mainly polymorphs of ye'elimite. Depending on the raw materials used and the burning temperature they typically also contain belite, ferrites and/or aluminates, anhydrite and may further contain ternesite, see e.g. WO 2013/023728 A2. Calcium sulfoaluminate cements are obtained from CSA clinkers by grinding, usually calcium sulfate is added. Manufacturing of the calcium sulfoaluminate cements takes place in a manner known per se. Typically raw materials are mixed in appropriate amounts, ground and burnt in a kiln to give a clinker. Usually, the clinker is then ground together with calcium sulfate and optionally some or all of the other components to give the cement. A separate grinding is also possible and may be advantageous when the grindability of the components is largely different. The calcium sulfate can be gypsum, bassanite, anhydrite or mixtures thereof. Anhydrite is preferably used.
A calcium sulfoaluminate cement can be obtained by grinding a CSA clinker when that already contains the desired amount of calcium sulfate. Typically, it is obtained by combining CSA clinker with adequate amounts of calcium sulfate. This means that as defined for the present invention the component CSA cement provides ye'elimite and sulfate, as well as optionally aluminates, ferrites, belite and other components, regardless of whether they originate from the CSA clinker or from a mixing of CSA clinker with them, either before, during or after grinding of the CSA clinker. Of course, sulfate, ye'elimite, aluminates, and ferrites can also originate from the SCM component or the optional additional components of the composite binder, so that less is desired in the CSA cement. This means that for manufacturing the binder the sulfate (and also any other phase) can originate from the CSA clinker, the CSA cement, the SCM and even from additional components. With respect to the the sulfate it does not matter whether it is added to the CSA clinker before mixing with the SCM or during mixing, i.e. the CSA cement can be added as one component or as two components, namely ground CSA clinker and ground sulfate.
Calcium sulfoaluminate clinkers and cements containing C4A3$ as a main phase are known and available in different qualitites/compositions. For the present invention all are suitable. For example, the following CSA cements are (commercially) available/known:
Belite (α; +/−β) C2S 40-75%; Ye'elimite C4A3$ 15-35%;
Ferrite C2(A,F) 5-25%; Minor phases 0.1-10%
Belite (α; +/−β) C2S 0-10%; Ye'elimite C4A3$ 50-65%
Ferrite C2(A,F) 0-10%; Minor phases 0-10%
Belite (α; +/−β) C2S 10-25%; Ye'elimite C4A3$ 50-65%;
Anhydrite C$ 0-25%; Minor phases 1-20%
Belite (α; +/−β) C2S 10-30%; Ye'elimite C4A3$ 20-40%
Free lime CaO <0.5-6%; Portlandite Ca(OH)2 0-7%;
Minor phases 0-10%
Belite (α; +/−β) C2S 0-10%; Ye'elimite C4A3$ 15-25%;
Anhydrite C2(A,F) 30-40%; Portlandite Ca(OH)2 20-35%;
Free lime CaO 1-10%; Minor phases 0-10%
Belite (α; +/−β) C2S 10-25%; Ye'elimite C4A3$ 60-70%;
Ferrite C2(A,F) 1-15%; Minor phases 1-15%
Belite (α; +/−β) C2S 22%; Ye'elimite C4A3$ 60%;
Aluminate C12A7 5%; Alite C3S 8%;
Ferrite C2(A,F) 4%; Minor phases 1%
Belite (α; +/−β) C2S 1-80%; Ye'elimite ΣC4A3$ 5-70%;
Ternesite C5S2$ 5-75%; Minor phases 0-30%;
The calcium sulfoaluminate clinker or cement usually comprises 10-100% by weight, preferably 20-80% by weight and most preferred 25 to 50% by weight C4A3-xFx$, with x ranging from 0 to 2, preferably from 0.05 to 1 and most preferably from 0.1 to 0.6. It typically further comprises 0-70% by weight, preferably 10 to 60% by weight and most preferred 20 to 50% by weight C2S, 0-30% by weight, preferably 1 to 15% by weight and most preferred 3 to 10% by weight aluminates, 0-30% by weight, preferably 3 to 25% by weight and most preferred 5 to 15% by weight ferrites, 0-30% by weight preferably 3 to 25% by weight and most preferred 5 to 15% by weight ternesite, 0-30% by weight, preferably 5 to 25% by weight and most preferred 8 to 20% by weight calcium sulfate and up to 20% minor phases. As indicated, phases can be present in the CSA clinker or added for obtaining the CSA cement.
The invention is beneficial to all kinds of calcium sulfoaluminate cements both belite rich and poor ones as well as with differing amounts of aluminates and ferrites as long as the weight ratio R$/(Y+A+F) in the composite binder is maintained in the range from 0.5 to 0.85. With a ratio below 0.5 only minor or even no contribution of the cementitious material is observed as regards strength development. With a ratio above 0.9 an expansion accompanied by the formation of fine to even large cracks has been observed already after 24 hours of hydration of mortar prisms made with the composite cements. Higher levels of sulfate addition lead to even more pronounced expansion and cracking. Preferably, the weight ratio according to the invention is set from 0.55 to 0.85, especially preferred from 0.6 to 0.85. Within the ranges a higher ratio leads to a higher increase of strength within shorter times, i.e. a higher ratio accelerates the strength development. Any sulfate, aluminate, ferrite or ye'elimite from the supplementary cementitious materials and other components is taken into account when calculating the ratio.
The supplementary cementitious materials can be added according to the invention in amounts of at least 10% and up to 90% by weight, preferably 20 to 80% by weight are added. The quantity of latent hydraulic materials in the SCM usually ranges from 0 to 100% by weight, preferably from 20 to 80% by weight and most preferably from 30 to 70% by weight of the of the total amount of SCM. The content of pozzolanic materials ranges from 0 to 40% by weight, preferably from 5 to 35% by weight and most preferably from 10 to 30% by weight of the total amount of supplementary cementitious materials.
The preferred amount of SCM in the binder depends on the reactivity of the SCM. If the SCM is only or mainly latent hydraulic materials the preferred amount of addition ranges from 10 to 90% by weight, most preferred 30 to 60% by weight. When only or mainly pozzolanic materials are used, the SCM is preferably added in an amount of 10 to 40% by weight, most preferred 20 to 30% by weight. The preferred amounts of SCMs that are mixtures of latent hydraulic and pozzolanic materials depends on the reactivity of the SCM mixture used. Namely, more reactive SCM mixtures are preferably used in higher amounts than those with a low, mainly pozzolanic reactivity.
In a further embodiment of the invention the calcium sulfoaluminate cement or binder therefrom has a fineness, according to the particle size distribution determined by laser granulometry, with a d90≦90 μm, preferably a d90≦60 μm and most preferred a d90≦40 μm, whereby the Rosin Rammler Parameter (slope) n can vary from 0.7 to 1.5, preferably from 0.8 to 1.3 and most preferably from 0.9 to 1.15.
The cement according to the invention is obtained by grinding the clinker, with or without addition of further substances. Usually, calcium sulfate is added before or during grinding when its content in the clinker is not as desired. It can also be added after grinding.
Further components chosen from e.g. but not exclusively calcium aluminate cements, portland cement or portland cement clinker, lime stone, dolomite, ternesite, alkali and/or earth alkali salts can be added in amounts of 0.01 to 20% by weight, preferably in amounts ranging from 0.5 to 15% by weight. It is especially preferred when a content of portland cement clinker, limestone, ternesite and/or dolomite ranges from 0.01 to 20% by weight, preferably from 3 to 20% by weight and most preferred from 5 to 15% by weight and a content of alkali salts and earth alkali salts ranges from 0% to 5% by weight, preferable from 0.1 to 3% by weight and most preferred from 0.5 to 2% by weight.
Furthermore, common admixtures and/or additives can be present. Admixtures are preferably added in an amount of up to 20% by weight, additives in an amount of up to 3% by weight. Naturally, the amounts of all components of one specific mixture add up to 100%.
Admixtures are usually added to concrete, mortar etc. made of a binder, but can also be added to the binder. Typical admixtures are:
Typical additives are for example but not exclusively fillers, fibres, fabrics/textiles, silica fume and crushed or ground glass. Fillers are e.g. quartz, limestone, dolomite, inert and/or crystalline fly ashes. Fibres are e.g. steel fibres, glass fibres or plastic fibres.
The method according to the invention can be carried out with devices known per se. The CSA cement can be mixed with SCM and further components, if applicable, directly after production. Alternatively, the components can be stored prior to mixing. The binder can be stored and transported as known, e.g. packaged into a cement silo or into cement bags or delivered as ready mix concrete after adding aggregate, water and any other desired addition, possibly after having been stored for some time.
As mentioned before, the method is described as mixing CSA cement and SCM, which shall include a situation where a ground CSA clinker with little or even no sulfate is used and sulfate is admixed as separate component together with eventual additional components to provide the binder. With other words, CSA cement includes a single component comprising at least ground ye'elimite and sulfate as well as the separate components sulfate and ground CSA clinker with no or too little sulfate.
It would even be possible to mix CSA clinker and unground SCM and perform the grinding on the mixture, but that is not preferred. The grindability usually differs. A separate grinding also provides more flexibility.
The binder according to the invention can be used to make concrete, mortar, plaster and other hydraulically setting building materials. It is also useful for manufacturing special construction chemical compositions like tile adhesives, floor screeds, etc. The use can take place in the same manner as that of known binders or cements. The binder is specifically suitable for applications that benefit from a lowered heat of hydration, i.e. especially for massive structures like dams. It is also very useful for ready mix concrete for all purposes.
The binder according to the invention provides significant further energy saving compared to binders based only on CSA cement. It shows an enhanced strength development compared to the binders comprising CSA and SCM known from the prior art.
The invention will be illustrated further with reference to the examples that follow, without restricting the scope to the specific embodiments described. If not otherwise specified any amount in % or parts is by weight and in the case of doubt referring to the total weight of the composition/mixture concerned.
The invention further includes all combinations of described and especially of preferred features that do not exclude each other. A characterization as “approximately”, “around” and similar expression in relation to a numerical value means that up to 10% higher and lower values are included, preferably up to 5% higher and lower values, and in any case at least up to 1% higher and lower values, the exact value being the most preferred value or limit.
Composite binders according to the invention and for comparison were formed from a clinker comprising around 45 g/100 g of beta-C2S, 35 g/100 g of ΣC4A3-xFx$ and 11 g/100 g aluminate (C3A, CA). The content of ferrites was below 1 g/100 g. Natural anhydrite was used as sulfate source. As supplementary cementitious material either slag or a mixture of slag and limestone was used. To provide comparison mixtures, quartz was used as an inert compoment instead of the SCM. The composite binder mixture, the ratio R$/(Y+A+F) and their strength development is shown in table 1. The strength development was measured as described in EN 196-1 on mortar cubes of 2 cm edge length from a mixture of 2 parts (by weight) cement, 3 parts sand (ISS1, Øsize of 1 mm) and 1 part water. The water/binder ratio was 0.5. The loading velocity was adjusted to 0.4 kN/s.
It can be seen, that at low R$/(Y+A+F) values like e.g. 0.25 or 0.35 no (measureable) contribution of the slag to the strength development was observed during the investigated period of time. For the samples with R$/(Y+A+F) values of 0.55 and 0.74 already after 90 days of hydration an increase of strength of around 7 MPa (0.55) to 12 MPa (0.74) compared to the quartz containing reference was achieved.
Composite binders according to the invention and for comparison were formed from a clinker comprising 60 g/100 g of beta-C2S, 22 g/100 g of ΣC4A3$ and 11 g/100 g ferrites (C4AF and C2F). No calcium aluminate phases was detectable. Natural anhydrite was used as sulfate source. Slag was used as supplementary cementitious material and quartz to provide a comparison. The binder mixtures and the ratio R$/(Y+A+F) are shown in table 2. Strength development was measured as for example 1.
It can be seen that at low R$(Y+A+F) values like e.g. 0.11 no (measureable) contribution of the slag to the strength development was observed during the investigated period of time and the quartz containing reference achieved even a higher final compressive strength. For the samples with R$/(Y+A+F) values of 0.77 and 0.85 already after 7 days of hydration a clear increase of strength of around 2 MPa (0.77) to 6 MPa (0.85) compared to the quartz containing reference was achieved. At 28 days of hydration the increase was around 7 MPa (0.77) to 12 MPa (0.85) and at 90 days 7 MPa (0.77) to 13 MPa (0.85) compared to the quartz containing reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 13004314.4 | Sep 2013 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2014/002368 | 9/2/2014 | WO | 00 |
