WO2014014428A1 - Building material based on calcium silicate comprising boron oxide compounds - Google Patents

Building material based on calcium silicate comprising boron oxide compounds Download PDF

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Publication number
WO2014014428A1
WO2014014428A1 PCT/TR2013/000223 TR2013000223W WO2014014428A1 WO 2014014428 A1 WO2014014428 A1 WO 2014014428A1 TR 2013000223 W TR2013000223 W TR 2013000223W WO 2014014428 A1 WO2014014428 A1 WO 2014014428A1
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WIPO (PCT)
Prior art keywords
cement
building material
boron oxide
material according
boron
Prior art date
Application number
PCT/TR2013/000223
Other languages
French (fr)
Inventor
Taner KAVAS
Abdullah Dogan SOYAL
Melike DEMIRAY
Abdullah TAN
Original Assignee
Akg Gazbeton Isletmeleri San. Tic. A.S.
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Application filed by Akg Gazbeton Isletmeleri San. Tic. A.S. filed Critical Akg Gazbeton Isletmeleri San. Tic. A.S.
Priority to EP13777172.1A priority Critical patent/EP2874972A1/en
Priority to EA201500016A priority patent/EA029640B1/en
Publication of WO2014014428A1 publication Critical patent/WO2014014428A1/en
Priority to TNP2015000016A priority patent/TN2015000016A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/18Compositions 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 mixtures of the silica-lime type
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/30Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention is related to an inorganic building material comprising boron oxide compounds which are different to conventional raw material mixtures.
  • the mixture having a gel consistency formed following the mixture of raw materials with different characteristics, chemical content, and organic and metallic foaming agents with water is then sized by being foamed after dragged in air as a function of time, following this it is cured under high pressure and is given mechanical resistance, low density and nonflammability characteristics.
  • the alkali silicate mixtures that are turned into solution by adding water are dissolved in aqueous medium under service and usage conditions and they will lose all of their volumetric stability. Thus the mechanical characteristics expected from these materials are not formed under different usage conditions.
  • binders such as cement and inorganic light materials within the field of artificial rocks such as concrete, are quite resistant against water and aqueous medium, and their mechanical resistances increase continuously in time.
  • light concrete are formed with an addition of a binder such as cement into natural light aggregates such as pearlite, diatomite and vermiculate however these materials cannot reach the desired pore, density and thermal insulation despite all efforts and high mechanical resistances.
  • the phases contained within the structure of these materials form hydrate crystals together with water and these instae products are decomposed around 400°C and their micro structural characteristics are changed which makes them suddenly lose their mechanical resistances.
  • wastes with boron content were added into the cement suspension.
  • clay waste comprising concentrated boron oxide were added into Portland cement together with coal bottom ash and fly ash, and the effects on the hidration process of cement was monitored and at the end of the process the initial en eventual setting and mechanical characteristics were examined.
  • NPQ Normal Portland Cement
  • the increase in mechanical characteristics were obtained through using the clay comprising boron oxide compounds together with coal bottom ash and fly ash.
  • waste with only boron oxide content did not provide the desired technical characteristics (Targan 2003).
  • the effects of mixing waste with boron oxide content whose particle size was smaller than 25mm, and slurry dried with hot air flow taken from the concentration process from the related facility with Portland and Trass Cement, on setting and mechanical characteristics were investigated.
  • waste with boron oxide content up to 5% by weight could be used as cement admixture (Erdogan, 1998).
  • boron ores are used in the production of many boron compounds.
  • One of these products is boric acid.
  • Boric acid waste is another boron waste obtained from sulphuric acid reaction and concentrated boron oxide compounds.
  • the usage of these wastes to produce cement has been examined by differen tinvestigators.
  • these wastes, different to boron waste have been tried as delaying agents to delay the setting in Portland cement.
  • cement with boron gypsum admicture have been produced and examined.
  • Raw materials comprising boron oxide used in literature are completely waste materials. For this reason they contain clay and quartz minerals at a content higher then boron oxide compositions which are contaminating and during usage dependant on the usage conditions these contaminants can play a more active role than said boron minerals. Whereas the raw material used in the present invention, has been granulated until having a certain particle size and its chemical content is a commercial product comprising high amounts of boron oxide compositions (Table 1).
  • the low percentage amounts of B 2 0 3 within the boron ores with different types and nature, a high porous and resilient product obtained with the usage of any of the commercial products supplied to the market, is produced by converting concentrated ulexite, concentrated tincal, calcinated tincal, acqueous disodium tetraborate dehydrated disodium tetraborate or refined boron oxide, refined boric acid, refined borax pentahydrate and refined borax decahydrate and similar boron products and concentrated colemanite obtained with the increase in the percentage amount of B 2 0 3 following the preparation processes of ores such as crushing, granulating, sieving using heating, and chemical dissolving methods or methods similar to these.
  • the process of decreasing the particle size of the ore comprising low B 2 0 3 percentage is established by bringing together clay, quartz, dolomite, colemanite and other different minerals) and obtaining a high B 2 0 3 content product following the separation procedures carried out by separating the product from unwanted minerals (except minerals with boron content) by using a physical, chemical or another method is called enrichment of said product and the product obtained as a result of all these procedures is called a concentrated product.
  • the building material subject to the imvention can be prepared with boron oxide compounds mentioned above.
  • Colemanite which is a concentrated boron oxide compound is used in the application of the present invention in the below mentioned samples.
  • the samples in which colemanite is used below should not be perceived as being limiting to the building material applications subject to the invention.
  • the free lime rate in cement mixtures need to be quite low (such as 1-2%). Otherwise with the volumetric expansion of the produced cement, the end product may become a non standard product (max. ⁇ 10mm).
  • the high CaO content within Farin which is added into the system is sintered in a rotating oven at approximately 1450°C, and the silicates, ferrites, and aluminates at this point come together and turn into C 3 S, C 2 S, C 3 A and C4AF stabile phases. Moreover each of these phases have a specific hydration periods and behaviours. Whereas in the raw material mixtures into which concentrated boron oxide compounds are added and prepared within the scope of this invention, as opposed to the cement phases, stabile phases are not present.
  • boron oxide compounds are divided into different chemical compounds such as ulexite and tincalconite and into raw materials comprising different boron and contaminants in different crystal forms. It is known as a scientific fact in literature that even if one of the characteristics change such as the crystal structure or the chemical content changes, the entrance of this mineral into a structure shall cause different mineralogical, chemical, physical and rheological changes in said structure.
  • the raw material mixtures comprising boron oxide compositions prepared within the scope of the invention are crystallized under high pressure.
  • the amounts of boron oxide content is at very low percentages. In studies carried out according to the invention, however have been included into the prescription in high percentages (such as 10%) and concentrated products with high boron oxide content have been used. This situation forms a significant difference in terms of the behaviour in a structure into which the boron oxide content has entered into.
  • the boron oxide compounds obtained according to this invention it has been determined from many studies that the extrinsic porous insulation plates have gained neuron retention characteristics, and due to this characteristic, they can be used at a more comprehensice field.
  • the boron element has two stabile isotopes namely B 10 and B 11 in nature.
  • Isotope B 10 has a very high thermal neutron capturing characteristics thus it can be used in nuclear materials, and nuclear energy plants.
  • boron compounds can absorb neutrons, they have been evaluated as cement and concrete admixture materials by many scientists.
  • Zeybek et al. have used the concentrated waste of concentrated boron oxide compounds as an admicture material and have investigated the neutron capturing capacities of cement mixtures that have been obtained. They have deduced that the concrete blocks produced with said cement can be used in neutron armouring (Zeybek 2000).
  • Raw material mixture numbered 1 to 8 boron oxide compounds numbered 9 is added and a calcium silicate based porous building material is produced with a higher mechanical strength and lower density.
  • Figure 1 is the Scanning Electron Microscope (SEM) view of the sample of example 1, which does not contain colemanite.
  • Figure 2. s the Scanning Electron Microscope (SEM) view of the sample of example 1, which contains colemanite.
  • the mixture which is obtained after the wet gasconcrete is acqueously granulated which has returned from the cutting procedure within the production process is known as waste slurry.
  • Quartzite (comprises reoxide Si02compounds) 25 - 45
  • Aluminium paste (thin type) 0,3 - 0,8
  • a hydrophobic material is used, for example as mentioned in EP 0 997 469 A2 (example 2), and after the curing of the building material that has been produced is completed the increase in hydrophobic quality is obtained.
  • the building material subject to the invention can be used as a supporting material and infilled wall building material, floor covering filler, facade panel, reinforced precast building material, heat insulation blocks and plates and building block and plates preventing radioactivity.
  • Kavas T. (Proje Yi broadlytiiciisii), Olgun A., Ersoy B., Karasu B., Arioz O., Kavas F. M., Tiirk A., igduygu M. G., "Bor igerikli Atiklann Cementnun Hidratasyonuna Etkisi ve Cementda Kullanilabilirligi", 107M087, TUBITAK, Kasim 2009, Ankara

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The present invention is related to an inorganic building material comprising boron oxide compounds which are different to conventional raw material mixtures. The mixture having a gel consistency formed following the mixture of raw materials with different characteristics, chemical content, and organic and metallic foaming agents with water is then sized by being foamed after dragged in air as a function of time, following this it is cured under high pressure and is given mechanical resistance, low density and nonflammability characteristics.

Description

DESCRIPTION
BUILDING MATERIAL BASED ON CALCIUM SILICATE COMPRISING BORON OXIDE
COMPOUNDS
Technical Field
The present invention is related to an inorganic building material comprising boron oxide compounds which are different to conventional raw material mixtures.
The mixture having a gel consistency formed following the mixture of raw materials with different characteristics, chemical content, and organic and metallic foaming agents with water is then sized by being foamed after dragged in air as a function of time, following this it is cured under high pressure and is given mechanical resistance, low density and nonflammability characteristics.
Prior Art
There are several known methods in literature to produce inorganic foam material from aqueous solutions which are alkali silicate suspensions. A general example to these methods, is to mix the suspension homogenously following an addition of foaming agent, and crystallizing the structure parallel to the realization of gas output from the structure during heat treatment thus giving the material strength. In these kind of production processes, in order to obtain a porous structure, an approximate temperature between 195- 900 °C is needed. Alkali silicates and foaming agents, are not reactive in temperatures and pressures below notmal conditions (even though they do react the targeted micro-structure cannot be obtained) thus in such a structure the desired pore size and number cannot be achieved. Moreover under these conditions, the alkali silicate mixtures that are turned into solution by adding water, are dissolved in aqueous medium under service and usage conditions and they will lose all of their volumetric stability. Thus the mechanical characteristics expected from these materials are not formed under different usage conditions.
As it is known in literature, binders such as cement and inorganic light materials within the field of artificial rocks such as concrete, are quite resistant against water and aqueous medium, and their mechanical resistances increase continuously in time. For example light concrete are formed with an addition of a binder such as cement into natural light aggregates such as pearlite, diatomite and vermiculate however these materials cannot reach the desired pore, density and thermal insulation despite all efforts and high mechanical resistances. On the other hand, the phases contained within the structure of these materials form hydrate crystals together with water and these hidrate products are decomposed around 400°C and their micro structural characteristics are changed which makes them suddenly lose their mechanical resistances.
Moreover expanded clay aggregates can be used besides natural aggregates during the production of building materials with light concrete. But the clay that is used as raw materials when producing said aggregates are actually fertile soil obtained from agricultural areas. Besides this disadvantage, these clay materials can only expand between temperatures of 800-1200°C. This situation leads to high energy consumption thus preventing the widespread usage of said clay materials. In the recent years, when producing these kind of artificial aggregates, in order to provide thermal energy efficiency and decrease firing temperatures; studies that utilize clay waste with high boron content has been observed (Kavas, 2011). However a high amount of cement is used as a binder in such concrete produced with said artificial aggregates, thus the structure loses its insulation characteristics and becomes dense.
Due to their insufficient characteristics such as density, lightness, thermal degradation resistence and thermal insulation, an alternative raw material, method and product is being sought. As a result of said searches, hydrogen gas discharge is established with the addition of aluminium metal dust into alkali silicates and dragging air into the structure form. Thus in order for the expanded cake to obtain mechanical resistance vapor curing is carried out at a temperature between 190-225°C and pressure between 10-12 atm. Following the curing process, the mineral phase transformation is realized, and a tobermorite phase is formed within the structure which can correspond to the desired characteristics rather than phases which have low thermal degradation resistances and mechanical characteristics such as portlandite and larnite. By this means, insulating materials which have sufficient mechanical resistance together with low thermal conductivity and high porous amounts with low density have been produced. Moreover organic wastes together with minerals and conventional raw materials used during the production process of said material studies directed to increase mechanical resistance, and decrease density and thermal conductivity are carried out.
In some studies wastes with boron content were added into the cement suspension. For example, clay waste comprising concentrated boron oxide were added into Portland cement together with coal bottom ash and fly ash, and the effects on the hidration process of cement was monitored and at the end of the process the initial en eventual setting and mechanical characteristics were examined. As a result, a significant level of increase was observed in resistance, with the addition of clay wastes having concentrated boron oxide compounds as 3% in mass, to Normal Portland Cement (NPQ. However the increase in mechanical characteristics, were obtained through using the clay comprising boron oxide compounds together with coal bottom ash and fly ash. It has been noted that using the clay waste containing only boron oxide compounds delayed the initial and eventual setting of cement and deterioriated its early mechanical characteristics (Kula, 2001). In another study, the effects of natural Pozzuolana, waste containing boron oxide, bottom and fly ash on Normal Portland Cement has been studied, and parameters such as compressive strength, bending strength, volumetric expansion and setting times have been examined. The results have show that, the eventual setting time of the cement cake was shortened when cement was exchanged with natural Pozzuolana admixture. However, the usage of natural Pozzuolana admixture together with the waste comprising boron oxide significantly delayed he setting time. Again in this study it has been noted that an increase in the bending strength was achieved in comparison to the control sample following the 60 day curing period of samples after Portland cement in the presence of waste comprising boron oxide was exchanged with natural Pozzuolana. In addition it has been perceived that setting time was significantly delayed when mixtures comprising natural Pozzuolana was used together with waste with 4% boron oxide content. Together with this, it has been determined that the strength of concrete could be increased when the wast with boron oxide content was brought together with Pozzuolana as admixture.
Despite this, it has also been determined that waste with only boron oxide content did not provide the desired technical characteristics (Targan 2003). In another study, the effects of mixing waste with boron oxide content whose particle size was smaller than 25mm, and slurry dried with hot air flow taken from the concentration process from the related facility with Portland and Trass Cement, on setting and mechanical characteristics were investigated. As a result of this study, it has been determined that waste with boron oxide content up to 5% by weight could be used as cement admixture (Erdogan, 1998). In a different study, the effects of bentonite, waste with boron oxide content, fly ash and bottom ash on cement and concrete was researched into by applying a group of tests, and following said tests parameters such as setting time, bending strength, volumetrice expansion, compressive strength and the water requirement of the soil mixture was examined. In conclusion, following the exchange of cement with bentonite, it has been noted that the setting time shortened, and setting time was significantly delayed when Portland cement was again exchanged in small amounts, and when used in high amounts that it had the effect of accelerating the setting time, and despite this it has been noted that compressive strength in samples containing 5-10% bentonite was increased and when a mixture which was brought together by mixing other admixtures was used, it has been noted that the compressive strength levels decreased (Targan, 2002).
During the examination of the physical-chemical characteristics of cement comprising chemically activated boron the long term resistance of waste concrete containing boron oxide, have been developed; and besides this advantage it has been determined that the low early resistance of concrete was limited due to waste usage in such systems; thus the empricial studies have been divded into two groups; waste comprising boron oxide instead of natural limestone was used in the first group; and chemicals such as sulphonate melamine, formaldehyde, sulphonate naphthaline formaldehyde, sodium sulphates and calcium chloride was used and the changes in characteristics have been observed. As a result it has been determined that the exchanging of waste comprising boron oxide with natural limestone did not significantly change the initial and eventual setting values of cement, that the soil mixtures in the long term were more resistant, that generally the addition of the chemicals into the system moved the Pozzuolanaic reaction to an earlier time and established betterment in the early resilience of the soil mixture, and that the addition of the chemical activator not only changed the cement hydration but also changed the micro structure of the solidified soil mixture (Olgun 2007).
Moreover in another study carried out, the effects of the addition of pectin admixture in changing ratios by percentage weight between 0,1 and 1, to the technical characteristics of both normal Portland cement and cement comprising boron oxide waste have been examined. As a result of the investigation it has been confirmed that the addition of pectin admixture shortened the setting time of Portland cement and delayed the setting when used up to the rate of 0,1 for Portland cement comprising waste with boron oxide, and accelerated the setting time when used higher than 1% (or exactly 1%). Moreover it has been determined that, in test samples activated with pectin, the early compressive strengths were lower in comparison to control samples, that the lowest early compressive value was reached mostly in test samples which contained pectin, however that the compressive strengths of test samples comprising pectin at the percentage of 0,1-05% in the following curing periods (28 days) were higher in durability when compared with the compressive strengths of the control samples, that the presence of pectin in cements with boron oxide admixture had an positive effect on both the early and the late resiliences of soil mixtures, that the hydration products shaped with cement cakes comprising boron oxide were differen to cements activated with pectin and that when the pectin content increased in a 2 days curing period the calcium hydrate amount partially decreased and that the preence of pectin within the mixture led to two new phases to be shaped one of which is calcium boron hydrate and the other allophone (Kavas, 2007).
In a study, that aims to use clay waste comprising boron obtained from concentrator borax (CWl) and borax pentahydrate (CW2) units as cement admixture, the effects of such waste on the mechanical and chemical characteristics of cements prepared with clay waste containing clinker and limestone have been examined. The results obtained have initially been compared with Portland cement characteristics and the Turkish Standards (TS) values. The main conclusions obtained from this study can be listed as follows: it has been determined that the mixture with an admixture of clay waste containing 1% boron oxide, had a higher compressive strength than Portland cement and under other conditions the cement mixture showed the best result, moreover it has been determined that the soil mixture comprising up to 5% CWl and 10% CW2 showed comparable results comparable to TS values and also that when the B203 rate in CW except 1% CWl, increased and CW rate increased, the mechanical strength of the soil mixture decreased. In addition as a result of this study it has been proposed that CWl and CW2 could be used as cement admixtures up to 5% and 10% respectively (Ozdemir, 2003).
In a similar study, the effects on the mechanical characteristics of Portland cement obtained with the addition of the rotary screen waste arising during the production of borax from tincal, into the clinker was examined. It has been determined following the study that the mechanical resistances of the cement produced with rotary screen wastes comprising boron oxide was higher than conventional cement, that the unit weight and setting time of the concrete produced from said cement was decreased, that the resistance of the concrete also decreased dependant on the increased amount of waste, that the cement and concrete produced with waste admixtures were resistant against bacteria formation and that the radioactive conductance was also decreased (Boncukoglu, 2002a). Moreover parallel to this study, the mechanical and radioactive conductances of Portland cement modified with rotary screen waste comprising boron oxide and Normal Portland cement have been compared. It has been found out, similarly to the previous study, following the comparison that; the rotary screen waste comprising boron oxide improved the mechanical characteristics of cement, that the mechanical characteristics of the concrete decreased parallel to the increased waste admixtures, that said cements and concretes produced were resistant against bacterial formation as the boron compounds have anticeptic qualities, that said cement and concrete produced with waste, were lower in radioactive conductivity when compared with normal cement and concrete samples, that waste could be added into the cement up to 25%, that the theoretical mass attenuation coefficient values of wastes, were lower than cement values when compared in experimental studies and that this situation was based on different cement phases whose formula is not exactly known and in addition to all this that the difference between the experimental and theoretical values could be dependent on the effects of the chemical environment (Boncukoglu, 2005).
On the other hand boron ores are used in the production of many boron compounds. One of these products is boric acid. Boric acid waste, is another boron waste obtained from sulphuric acid reaction and concentrated boron oxide compounds. The usage of these wastes to produce cement has been examined by differen tinvestigators. However these wastes, different to boron waste, have been tried as delaying agents to delay the setting in Portland cement. With this aim, instead of natural plaster stone, cement with boron gypsum admicture have been produced and examined. As a result it has been noted that, the mechanical strengths of cement samples increased, the strength of the concrete decreased parallel to the increase in the usage amount of natural plaster stone and boron gypsum, that the natural gypsum admixture negatively effected the cement quality produced as a dehydrate during granulation, that during the usage of boron gypsum, a lower granulation energy was required because of its structure and that the during granulation the crystals dsd not lose their water, and dependent on this, the cement quality was not negatively effected, that the boron gypsum additive could be used as a setting delaying agent up to 10% by weight, and again that the cement and concrete produced by this means prevented bacteria formation and showed decreased radioactive conductivity (Boncukoglu, 2002b). In similar studies, the therman analysis of boron gysum was carried out and its effects on the physical characteristics of Portland cement was examined (Elbeyli, 2003) and besides the setting and solidifying of Portland cement with boron gypsum with an admixture of fly ash, the effects on the soil micture comprising molasses of boron gypsum were examined (Kavas 2005).
In both studies, similarly, boron gypsum and hemihydrate boron gyspsum were found to increase/delay the setting time of cement. Moreover, it has been determined that hemihydrate boron gypsum admixture gave better mechanical characteristic results in comparison to cements prepared with natural gysum and that it increased the mechanical characteristics of cement and said admixture decreased the mass expansion values, and that the increase in the amount of B203 extended the setting time and led to the loss of mechanical characteristics. It has been reported that the addition at the rate of 0,1% molass admixture into the cement comprising boron, delayed the initial and eventual setting time of the cement, however following the 7 day curing period, it has been reported that this admixture slowly developed mechanical characteristics.
In some studies however, the mechanical and physical characteristics of cement and concrete with the usage of boron waste together with other waste have been examined and reported. As an example, the setting behaviours, compressive strengths, volumetric expansion values, the water need of the soil mixture and the micro structure analysis of the samples prepared with the adition of tincal ore waste, fly ash and bottom ash into the cement in varying amounts have been carried out. Following the study, it has been determined that following the substitution of Portland cement with the tincal waste which is higher that 5% respectively caused significant losses in the compressive strength values, that following the addition of tincal waste up to 1% value, together with bottom ash into the system and following a 28 day curing period that the mechanical strength increased considerably, that in curing periods which are 2 days, lower mechanical strength values were reached for all samples, that depending on the curing time and admixture rates, improvement in mechanical characteristics were seen, and as a result it has been expressed that tincal waste, fly ash and bottom ash could be used together within the cement industry (Kula, 2002).
In the project supported by TUBITAK titled, "The effect of waste containing Boron on the hydration of cement and the usability of said waste in cement" which is a considerably detailed study, Alite (C3S), Belite (C2S), Scheelite (C3A) and Ferrite (C4AF) which are pure clinker phases have been produced and by adding Kirka tincal waste in changing rates for each phase respectively, hydrating temperature designation with micro calorimeter, mineral phase developments with XRD, concentration of ions passing into the water from the suspension with ICP dependent on time, assigning of initial and eventual setting time with vicat, expansion with Le Chatelier, density, specific surface area and mechanical strength analysis have been carried out.
Following this comprehensive study, it has been determined that the material known as boron waste, included fine particle sized clay together with boron waste inside it, and that said clay could play a more dominant role in the hydration process of cement, that Borax minerals evolved into tincal alconite mineral following an average of 60°C temperature when drying of said waste, that this situation in return could lead to different mechanisms in the hydration of cement clinker phases as a result of the crystal structure changes, that in order to be able to obtain healthy data, it could be more convenient to dry the waste in room temperatures, that this played a limited and negative role in the micro calorimeter data dependant on the increased amount of waste, that an increase in the Ca+2 ion concentration is observed in connection with the increase in the amount of the admixture containing boron waste in studies carried out in all of the pure clinker phases according to the ICP analysis data, that this situation dearly showed that the waste admixture increased the ion solubility, and that it interrupted the cyrstalization formation of calcium hydrate (CH) and it initially extended the crystallization period for this phase and later the crystallization period for the phase of tobermorite (CSH), that not only did it play a significant role on the boron ions received from the waste within the hydration kinetics of the pure cement phase but also on the cations received from clay, that the waste admixture did not effect the volumetric stability of the cement cake, that following the entrance of the boron ions into the system after the initial stage of the hydration of C3A and dAF phases, it did not play an efficient role in the hydration kinetics of said phases, that on the contrary to the known literature that the C4AF phase was hydrated first rather than the C3A phase and during the initial solidification process that it could play a more efficient role, and that the phases C3S and C2S together showed different surface characteristics, and that the C3S phase showed positive Zeta potential (ZP) values within all measured time ranges whereas the C2S phase initially showed negative within the first 15-120 minutes time range and then later showed positive values, that either Portland cement or the clinker phases on their own established more Ca+2 ion concentrations than the PH value of the medium of the factor playing a determining role in the ZP values, and that the stability and instability arising between the Ca+2 ion amount that passes from being in the solid phase in a unit time to being a solution and then from being a solution to being a solid enabled the formation of said surface loads, and that among all phases and the usage of Portland cement, the phase that supplied the highest amount of Ca+2 ion into the system was C3S (Kavas, 2009). Data which are similar to the general data given above, have also been emphasized in another study mentioned below. It has been determined in said study that salts comprising boron that are dissolvable, changed the hydration mechanics of Portland cement and delayed solidification and setting time. Moreover as a result, it has been emphasized that boron negatively effected the hydration of Portland cement however the addition of lime, improved the hydration speed of normal Portland Cement within the presence of boron (Palomo, 2003).
Besides the usages mentioned above, there are also studies present in literature wherein the waste comprising boron, is added to the prescription in order to provide admixture for the sintering of ceramic structures (Kurama, 2006; Abah, 2007; Kavas 2006). It has been reported as a common feature in said studies that boron, alkali and soil alkali oxides together contained in the waste, play a dissolving agent role and thus lead to much lower mineral phase development in structures that they enter into.
The differences in the studies carried out and given within the scope of the literature with this invention, have been specified below in detail and the differences from said invention have been emphasized in terms of method, product characteristic, place and conditions of usage.
Raw materials comprising boron oxide used in literature are completely waste materials. For this reason they contain clay and quartz minerals at a content higher then boron oxide compositions which are contaminating and during usage dependant on the usage conditions these contaminants can play a more active role than said boron minerals. Whereas the raw material used in the present invention, has been granulated until having a certain particle size and its chemical content is a commercial product comprising high amounts of boron oxide compositions (Table 1).
The low percentage amounts of B203 within the boron ores with different types and nature, a high porous and resilient product obtained with the usage of any of the commercial products supplied to the market, is produced by converting concentrated ulexite, concentrated tincal, calcinated tincal, acqueous disodium tetraborate dehydrated disodium tetraborate or refined boron oxide, refined boric acid, refined borax pentahydrate and refined borax decahydrate and similar boron products and concentrated colemanite obtained with the increase in the percentage amount of B203 following the preparation processes of ores such as crushing, granulating, sieving using heating, and chemical dissolving methods or methods similar to these. The process of decreasing the particle size of the ore comprising low B203 percentage (is established by bringing together clay, quartz, dolomite, colemanite and other different minerals) and obtaining a high B203 content product following the separation procedures carried out by separating the product from unwanted minerals (except minerals with boron content) by using a physical, chemical or another method is called enrichment of said product and the product obtained as a result of all these procedures is called a concentrated product.
The building material subject to the imvention can be prepared with boron oxide compounds mentioned above. Colemanite which is a concentrated boron oxide compound is used in the application of the present invention in the below mentioned samples. The samples in which colemanite is used below should not be perceived as being limiting to the building material applications subject to the invention.
Table 1. The Chemical Compound of granulated Colemanite and its particle size dispersion
(The values of Colemanite which has been granulated as a commercial product have been obtained from the internet site of Eti Maden)
Figure imgf000011_0001
The free lime rate in cement mixtures need to be quite low (such as 1-2%). Otherwise with the volumetric expansion of the produced cement, the end product may become a non standard product (max. < 10mm). In short, the high CaO content within Farin which is added into the system, is sintered in a rotating oven at approximately 1450°C, and the silicates, ferrites, and aluminates at this point come together and turn into C3S, C2S, C3A and C4AF stabile phases. Moreover each of these phases have a specific hydration periods and behaviours. Whereas in the raw material mixtures into which concentrated boron oxide compounds are added and prepared within the scope of this invention, as opposed to the cement phases, stabile phases are not present. All of the system is formed of active oxides which are nearly completely granulated and are easily dissolved in water (CaO, Si02, S gibi). Moreover boron mineral is a salt and it dissolves in low temperatures and changes the structure of the crystal. For this reason it is not possible scientifically for the concentrated boron oxide mineral admixtures, to show the same characteristics in both systems whose productions are completely different to each other such as cement and gasconcrete.
Even though in some studies waste containing boron are grouped under the same name, in different studies they are used in reference with quite different minerals. Whereas boron oxide compounds, are divided into different chemical compounds such as ulexite and tincalconite and into raw materials comprising different boron and contaminants in different crystal forms. It is known as a scientific fact in literature that even if one of the characteristics change such as the crystal structure or the chemical content changes, the entrance of this mineral into a structure shall cause different mineralogical, chemical, physical and rheological changes in said structure. The raw material mixtures comprising boron oxide compositions prepared within the scope of the invention are crystallized under high pressure. Whereas prescriptions used for the production of cement added into the structure of Farin and Clinker are mixed with water in room temperatures and under pressure thus obtaining hydrate compounds. Accordingly different pressure and conditions are valid in related methods. In addition, all of the studies given above, separate the two usage methods from each other where in the product is a produce of only laboratory wide empirical studies however wherein only the industrial production conditions within the scope of the invention is valid.
Moreover in the boron waste studies presented within the scope of the literature, the amounts of boron oxide content is at very low percentages. In studies carried out according to the invention, however have been included into the prescription in high percentages (such as 10%) and concentrated products with high boron oxide content have been used. This situation forms a significant difference in terms of the behaviour in a structure into which the boron oxide content has entered into. On the other hand, the boron oxide compounds obtained according to this invention it has been determined from many studies that the extrinsic porous insulation plates have gained neuron retention characteristics, and due to this characteristic, they can be used at a more comprehensice field. The boron element has two stabile isotopes namely B10 and B11 in nature. The availability rates of said isotopes in nature are respectively %19,l-20,3 and %79,7-80,9. Isotope B10 has a very high thermal neutron capturing characteristics thus it can be used in nuclear materials, and nuclear energy plants. As boron compounds can absorb neutrons, they have been evaluated as cement and concrete admixture materials by many scientists. Zeybek et al., have used the concentrated waste of concentrated boron oxide compounds as an admicture material and have investigated the neutron capturing capacities of cement mixtures that have been obtained. They have deduced that the concrete blocks produced with said cement can be used in neutron armouring (Zeybek 2000). In another study that was carried out, concentrated boron oxide compounds have been mixed with barite and a boron frit has been prepared and have been added to the concrete aggregates with a thin polymer layer thus it has been determined that here the absorbance of neutrons have increased by fourfold in comparison to standard mixtures (Gundijz 1982). It has been reported that the B10 isotope captured the neutrons in the control systems of atom reactors, in cooling pools, and when the reactor is closed with an alarm and that said isotope produces a Li and alpha particle (Kula 2000).
Brief Description of the Invention
During the production of the building material which is an aim of the present invention the following have been used inside the gel phase prepared with water: 1) Qaurtzite 2) Limestone 3) Water 4) Lime 5) Waste slurry 6) Cement 7) Material providing hydrophobicity 8) Air dragging metal agent and 9) Boron oxide compounds.
The most significant characteristic of this study is that in addition to the conventional
Raw material mixture numbered 1 to 8, boron oxide compounds numbered 9 is added and a calcium silicate based porous building material is produced with a higher mechanical strength and lower density.
Brief Descriptions of the Drawings
Figure 1. is the Scanning Electron Microscope (SEM) view of the sample of example 1, which does not contain colemanite. Figure 2. s the Scanning Electron Microscope (SEM) view of the sample of example 1, which contains colemanite.
Figure 3. are representative XRD peaks of example 1
Figure 4. Is the SEM view of the representative sample belonging to example 2 which does not contain colemanite
Figure 5. Is the SEM view of the representative sample belonging to example 2 which contains colemanite
Figure 6. are the representative XRD peaks of example 2
Figure 7. Is the SEM view of the representative sample of Example 3 that does not contain Colemanite compounds
Figure 8. Is the SEM view of the representative sample belonging to example 3 which contains colemanite
Figure 9. are the representative XRD peaks of example 3
Figure 10. is the XRD report of the representative sample of example 3
Detailed Description of the Invention
The mixture which comprises quartzite, limestone and water, is granulated in a watermill and is pressed into tanks and this watery mixture is named as soil mud. The mixture which is obtained after the wet gasconcrete is acqueously granulated which has returned from the cutting procedure within the production process is known as waste slurry.
Mixture water, soil mud (quartzite, limestone and water), boron oxide, hydrophobic material, waste slurry, lime and cement is respectively poured into the main mixer and following this finally aluminium is added and said raw materials have been mixed and the mixture is poured into moulds.
The prescription samples which have differen product ranges prepared within the scope of the invention studies, and the product characterization results have been given below.
Example 1:
Table 2. Formula of Example 1 Denisty: 115-200 kg/m3
% by
Raw material
weight
Quartzite (comprises reaktive Si02compounds) 25 - 45
Limestone 3 - 8
Waste Slurry 10 - 30
Lime (Comprises reactive CaO compound) 3 - 12
Portland Cement 20 - 50
Aluminium paste (thin type) 0,3 - 0,8
Hidrophobic product 0,1 - 0,5
Colemanite 0,2 - 4,0
Water /Solid Rate 0,7- 1,20
The characteristics table of the mechanical and thermal conductivity values belonging to the product that has been produced according to Example 1 have been given below.
Table 3. The mechanical and thermal conductivity values of example 1
Figure imgf000015_0001
Example 2:
Table 4. Formula of example 2
Figure imgf000015_0002
The characteristics table of the mechanical and thermal conductivity values belonging to the product that has been produced according to EExample 2 have been given below.
Table 5. The mechanical and thermal conductivity values of example 2
Figure imgf000016_0001
Example 3:
Table 6. Formula of Example 3
Figure imgf000016_0002
The characteristics table of the mechanical and thermal conductivity values belonging to the product that has been produced according to Example 3 have been given below.
Table 7. The mechanical and thermal conductivity values of exam
Figure imgf000016_0003
Colemanite that is ever increasingly added to the prescriptions (Table 1,3, and 5) increased the consumption amount of the Quartz (Q) in the structure and provides admixture to the formation of Tobermorite (T) and Calcium Silicate Hydrate (CSH). Such that in Figure 3,6,9 the quartz peak intensities have decreased and the Tobermorite and Calcium Silicate Hydrate peak intensities have increased.
Without the colemanite added to the prescriptions, instead of the shapeless pores formed within a standard (not containing colemanite) structure (Figure 1, 4 and 7), a pore formation which has equal dimensions, which are more spherical, which are more homogenous and have sharper edges can be obtained (Figure 2, 5 and 8).
It is observed that the colemanite admixture added into the prescriptions, absorbed the gas emanating during the H gas discharge which is caused by the foaming agent added to the Raw Material mixture and that it caused the formation of crystal NaBH4 with the effect of heat and pressure within the medium (Figure 3, 6, 9 ve 10).
The production of materials whose neutron capturing characteristics have been improved with the heat insulation plates produced with the colemanite admixture added to the prescriptions and their usage during the application stages of the high intensity products is very important for such products to be able to be used in a wider field.
During the production of the calcium silicate based material which contains boron oxide compounds according to the invention, a hydrophobic material is used, for example as mentioned in EP 0 997 469 A2 (example 2), and after the curing of the building material that has been produced is completed the increase in hydrophobic quality is obtained.
Thus the mechanical characteristics of the building material's and the heat insulation plates which have varying intensities produced by means of the characteristics obtained via the boron oxide compound admixtures which have been mentioned above according to the invention increases, and the A factor values increase, the neutron capturing abilities improve and at the same time the elastic module value which is an indication of rigidity also improves.
The building material subject to the invention can be used as a supporting material and infilled wall building material, floor covering filler, facade panel, reinforced precast building material, heat insulation blocks and plates and building block and plates preventing radioactivity. REFERENCES
Abah Y.I, Yurdusev M.A., Zeybek M.S., Kumanlioglu A. A. "Using phosphoavpsume and boron concentrator wastes in light brick production" Original Research Article Construction and Building Materials, Volume 21, Issue 1, January 2007, Pages 52-56
Boncukcuoglu3 R., Kocakerim M.M., Tosunoglu V., Yilmaz M.T. "Utilization of trommel sieve waste as an additive in Portland cement production" Cement and Concrete Research, Volume 32, Issue 1, January 2002, Pages 35-39
Boncukcuoglu R., igelli 0., Erzeneoglu S., Kocakerim M. M. "Comparison of radioactive transmission and mechanical properties of Portland cement and a modified cement with trommel sieve waste" Cement and Concrete Research, Volume 35, Issue 6, June 2005, Pages 1082-1087
Boncukcuo£jlub R., Yilmaz M.T., Kocakerim M.M., Tosunoglu V. "Utilization of borogypsum as set retarder in Portland cement production" Cement and Concrete Research, Volume 32, Issue3, March2002, Pages471 -475
Elbeyli i. Y., Derun E. M., Gulen 1, Pi§kin S. "Thermal analysis of borogypsum and its effects on the physical properties of Portland cement" Cement and Concrete Research, Volume 33, Issue 11, November 2003, Pages 1729-1735 Erdogan Y., Zeybek M.S, Demirbas. A. "Cement Mixes Containing Colemanite from Concentrator Wastes" Cement and Concrete Research, Volume 28, Issue 4, April 1998, Pages 605-609
Gundiiz G., "Nuclear Engineering and Design, Colemanite-baryte frit and polymer impregnated concrete as shielding materials, North Holland Publishing Co., 72, 439-447, 1982"
Kavas T. (Proje Yiiriitiiciisii), Olgun A., Ersoy B., Karasu B., Arioz O., Kavas F. M., Tiirk A., igduygu M. G., "Bor igerikli Atiklann Cementnun Hidratasyonuna Etkisi ve Cementda Kullanilabilirligi", 107M087, TUBITAK, Kasim 2009, Ankara
Kavas T., Christogerou A., Pontikes Y., Angelopoulos G.N. "Valorisation of different types of boron-containing wastes for the production of lightweight aggregates" Journal of Hazardous Materials, Volume 185, Issues 2-3, 30 January 2011, Pages 1381-1389 Kavas T., Olgun A., Erdogan Y., Once G. "The effect of pectin on the physicochemical and mechanical properties of cement containing boron" Building and Environment, Volume 42, Issue 4, April 2007, Pages 1803-1809
Kavas T., Olgun A., Erdogan Y. "Setting and hardening of borogypsum-Portland cement clinker-fly ash blends. Studies on effects of molasses on properties of mortar containing boroQvpsum" Cement and Concrete Research, Volume 35, Issue 4, April 2005, Pages 711- 718
Kavas T. "Use of boron waste as a fluxing aoent in production of red mud brick" Building and Environment, Volume 41, Issue 12, December 2006, Pages 1779-1783
Kula I, "Bor endustri atiklarinin cement iiretiminde admixture maddesi olarak degerlendirilmesi" Sakarya Universitesi, Fen Bilimleri Enstitusii, Doktora Tezi, 2000"
Kula I., Olgun A., Erdogan Y., Sevinc V. "Effects of colemanite waste, cool bottom ash, and fly ash on the properties of cement" Cement and Concrete Research, Volume 31, Issue 3, March 2001, Pages 491-494
Kula I., Olgun A., Sevinc V., Erdogan Y. "An investigation on the use of tincal ore waste, fly ash, and coal bottom ash as Portland cement replacement materials" Cement and Concrete Research, Volume 32, Issue 2, February 2002, Pages 227-232
Kurama S., Kara A., Kurama H. "The effect of boron waste in phase and microstructural development of a terracotta body during firing" Journal of the European Ceramic Society, Volume 26, Issues 4-5, 2006, Pages 755-760
Olgun A., Kavas T., Erdogan Y., Once G. "Physico-chemical characteristics of chemically activated cement containing boron" Building and Environment, Volume 42, Issue 6, June 2007, Pages 2384-2395
Ozdemir M., Oztiirk N. U. "Utilization of clay wastes containing boron as cement additives" Cement and Concrete Research, Volume 33, Issue 10, October 2003, Pages 1659-1661
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Claims

1. A building material characterized in that;
a) it comprises quartz, limestone, water, lime, cement, a metal agent used in dragging air, at least a boron oxide compound and optionally waste slurry, and optionally material that increases hydrophobicity
b) its heat conductivity coefficient is higher than 0,046 W/mK, and
c) its density is between 115 kg/m3 to 415 kg/m3.
2. A building material according to Claim 1, characterized in that the quartz is between 25 to 65% by weight, limestone is 3 to 8% by weight, waste slurry is between 10 to 30% by weight, lime is between 3 to 18% by weight, cement is between 20 to 50% by weight, air dragging metal agent is between 0,1 to 0,8% by weight, hidrophobocity increasing material is between 0,05 to 0,6, bor oksit compound is between 0,2 to 8 % by weight and su/solid rate is between 0,6 to 1,2% by weight.
3. A building material according to Claim 1 characterized in that, at least on boron oxide compound is chosen from the group of concentrated colemanite, concentrated ulexide, concentrated tincal, calcined tincal, acqueous disodium tetraborate, dehydrated disodium tetraborate or refined boron oxide, refined boric acid, refined borax pentahydrate, and refined borax decahydrate.
4. A building material according to Claim 1 characterized in that, said boron oxide compound is colemanite.
5. A building material according to Claim 1 characterized in that said air dragging metal agent is aluminium paste.
6. A building material according to Claim 1 characterized in that, said cement is Portland cement.
7. A building material according to Claim 1 characterized in that, the heat conductivity coefficient is between 0,046 W/mK to 0,12 W/mK.
8. A building material according to Claim 1 characterized in that, the compressive strength is between 0,1 N/mm2 to 4,5 N/mm2 .
9. A building material according to Claim 1 characterized in that, it has a heat conductivity coefficient between 0,046 W/mK to 0,065 W/mK at a density between
115 kg/m3 to 200 kg/m3.
10. A building material according to Claim 1 characterized in that, it has a heat conductivity coefficient of 0,060 W/mK to 0,095 W/mK at a density between 200 kg/m3 to 350 kg/m3.
11. A building material according to Claim 1 characterized in that it has a heat conductivity coefficient between 0,090 W/mK to 0,12 W/mK when at densities between 350 kg/m to 415 kg/m3.
12. A production method of a building material according to Claim 1, characterized in that, water, soil slurry made with quartzite, limestone and water, boron oxide compound, hydrophobicity increasing material, waste slurry, lime and cement mixture is respectively added into the mixer and finally aluminium suspension is added into said mixture to produce said building material.
Figure imgf000021_0001
PCT/TR2013/000223 2012-07-18 2013-07-10 Building material based on calcium silicate comprising boron oxide compounds WO2014014428A1 (en)

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