WO2021235922A1 - Mélange de construction à base de ciment avec additif à base de scories de fabrication d'acier - Google Patents

Mélange de construction à base de ciment avec additif à base de scories de fabrication d'acier Download PDF

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Publication number
WO2021235922A1
WO2021235922A1 PCT/KZ2020/000012 KZ2020000012W WO2021235922A1 WO 2021235922 A1 WO2021235922 A1 WO 2021235922A1 KZ 2020000012 W KZ2020000012 W KZ 2020000012W WO 2021235922 A1 WO2021235922 A1 WO 2021235922A1
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WO
WIPO (PCT)
Prior art keywords
cement
slag
steelmaking slag
steelmaking
portland cement
Prior art date
Application number
PCT/KZ2020/000012
Other languages
English (en)
Russian (ru)
Inventor
Асель Ермековна ДЖЕКСЕМБАЕВА
Original Assignee
Асель Ермековна ДЖЕКСЕМБАЕВА
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Асель Ермековна ДЖЕКСЕМБАЕВА filed Critical Асель Ермековна ДЖЕКСЕМБАЕВА
Priority to PCT/KZ2020/000012 priority Critical patent/WO2021235922A1/fr
Publication of WO2021235922A1 publication Critical patent/WO2021235922A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/08—Slag cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to the field of building materials, in particular to compositions based on cement containing ferritic waste from steel production for the construction and repair of industrial, engineering and social infrastructure facilities.
  • a known method of producing steel and hydraulically active binders from slags including the reduction treatment in a vessel of a slag melt containing more than 5% iron oxide, to a clinker phase, followed by its separation from the metal melt, release and cooling, refining the metal melt, while as a melt Of metal, blast furnace iron is used, which is refined with a slag containing iron oxides, which is reduced during the refining process to a clinker phase, while steelmaking slags, or Si-converter slags after reaction with a lead bath, or oxidized slags from waste incinerators are used as the slag.
  • the ratio of the components is as follows, wt%: cement - 13-17, quartz sand - 4-7, spent pickling solution - 4-8, the specified slag fraction 0-3 mm - 18-24, filler - 24-48, hardener - 8 -12, water - 5-8.
  • the disadvantages of the known building mixture are the long setting period, which makes it impossible to use it in urgent emergency work, and the mixture is also characterized by low binder strength (RU2647010C1, 03/13/2018).
  • the problem to be solved by this invention is the development of new compositions of cement mixtures with the content of steelmaking slag (SSS) as an additive.
  • SSS steelmaking slag
  • steelmaking slag (SSSh) is used in an amount of 1-15% by weight, and Portland cement (SPC) is 85-99% by weight.
  • Steelmaking slag is a waste of metallurgical production obtained by melting cast iron with lime or dolomite flux in a gaseous oxygen atmosphere. Impurities in cast iron are carbon, phosphorus, silicon and manganese,
  • Carbon dioxide is volatilized, while other oxides (eg iron, silicon, manganese) combine with lime or dolomite in the slag, which can have a positive effect on the cement mix.
  • oxides eg iron, silicon, manganese
  • the chemical composition of the steelmaking slag should include (wt.% Not less) CaO-45, SiO-10, AIO-I and ⁇ Play ⁇ -4 present in the role of hydraulic binders that affect the strength cement stone.
  • these compounds as a result of the hydration of the cement slurry with steel-making slag, form hexagonal crystals of portlandite Ca (OH) 2 , calcium hydrosilicates CS-H, which determines the most important properties of the cement stone: strength, volume stability, permeability, shrinkage, creep.
  • Table 1 Chemical composition of oxides (wt.%) In ordinary Portland cement and steelmaking slag;
  • Table 3 The ratio of the mass of Portland cement with the amount of additives% SPSH;
  • Figure 1 Particle size distribution of steelmaking slag and Portland cement
  • Figure 10 Curves of porosity of samples of conventional Portland cement and cement mixture with 5% SPSH content.
  • the purpose of the research work was to determine the optimal dosage for replacing part of the cement with ferritic waste of steelmaking slag, which directly contributes to an increase in cement activity and an improvement in physical and mechanical properties.
  • the following materials were used for laboratory tests:
  • Table 1 Chemical composition of oxides (wt.,.%) Of ordinary Portland cement and steel-making slag Chemical composition shows that the steel slag has a CaO of calcium oxide as the predominant compound in an amount of 46.17%, and other compounds like Si0 2 (12.03%) A1 2 0 3 (1.53%), MgO (4.53%) present as a hydraulic binders that affect the strength of the cement stone.
  • these compounds as a result of the hydration of the cement slurry with steel-making slag, form hexagonal crystals of portlandite Ca (OH) 2 , calcium hydrosilicates of the CSH plate, which determines the most important properties of the cement stone: strength, volume stability, permeability, shrinkage compensation and creep.
  • the mineralogy of the considered mixed cements was assessed using the X-ray diffraction (XRD) method.
  • XRD X-ray diffraction
  • a Bruker D8 X-ray diffractometer equipped with Cu-X-rays was used to perform X-ray tests at a speed of 2 ° / min, covering a 2Q angle range of 5-60 °
  • microstructural characteristics of mixed cement pastes with 1%, 3%, 5%, 10%, 15% SS dosage were assessed by X-ray diffraction analysis (XRD), scanning electron microscope (SEM), and semi-adiabatic calorimetry.
  • Figure 5 shows the results of heat release and heat release rate of cement pastes based on standard Portland cement and with the addition of 1%, 3%, 5%,
  • FIG. 5 (b) indicates a decrease in the heat release rate for samples with 10% and 15% SN, which can be considered as an indicator of the retardation of the process of hydration of the cement composition and leads to a decrease in the compressive and flexural strength in these samples of cement pastes (see table 4).
  • This conclusion can also be explained by the setting time presented in Table 2.
  • An increase in the dosage of SPSH increases the initial and final setting time, which is associated with a slowdown in the hardening process caused by a lack of cement and a low rate of hydration of additives. In the case of 1% SS, the initial and final setting times are observed to be almost the same.
  • the hydration process is accelerated, which can also be associated with the fineness of grinding.
  • Test methods for determining the normal consistency, start and end times of hydraulic cement paste were carried out according to ASTM C187 and ASTM C191. It should be noted that the correct proportion of water to cement is necessary to achieve proper strength when using cement in the structure. Thus, this method is intended to determine the amount of water (in% of the mass of dry cement) required for the preparation of cement and mixed pastes for further testing.
  • the normal consistency and setting time of cement pastes of standard Portland cement SPTs and mixed pastes PC-SPSh1, PC-SPShZ, PC-SPSh5, PC-SPShYu and PC-SPSh15 were measured on a Vika device.
  • the amount of water required for a standard consistency of cementitious pastes was determined by penetrating a standard pestle "Vika" (10 mm in diameter) into a ring filled with paste. The initial and final setting times of the samples were determined using Vika needles. The air temperature was maintained at 24 ° C, the humidity in the mixing room was 54%.
  • test methods provide the ability to determine the flexural and compressive strength of standard Portland cement and mixed slurries containing steelmaking slag in percentages of 1%, 3%, 5%, 10% and 15% by weight of dry cement, the results of which are used to determine compliance technical requirements.
  • the compressive strength of 50 mm slag slag cubes was measured after 3, 7 and 28 days of curing.
  • the procedure for preparing the cement composition was carried out according to ASTM C10 9.
  • the proportions of materials for the standard slurry ranged from one part of cement to 2.75 parts of sorted standard sand by weight.
  • the number of materials mixed at one time in a batch of solution for nine tests are presented in table 3.
  • samples PC-SPSh5 have the highest average compressive strength: 3 days-36. 4 MPa, 7 days - 38.3 MPa, 28 days - 42.2 MPa, as can be seen from the dynamics of increasing strength in figure 8.
  • This increase in strength can be explained by the improvement in the reactivity of the slag during the hydration period, which may be due to the fineness of the grinding, the reaction in an alkaline medium associated with the mineralogical content of the slag, and also to the fact that the appropriate content of the used slag led to the formation of a large amount of CSH gel and ettringite during hydration and a small amount of C 3 A phase during early hydration. Microparticles of crushed slag form unsaturated compounds that are unstable and tend to react faster, i. E. they become very active.
  • the fineness of the slag particles in size can increase the early and late compressive strength of the cement slurry, and improve the microstructure of the cement stone.
  • the flexural strength of the samples of the cement-slag mortar was measured after 3, 7 and 28 days of hardening.
  • the samples were cast into prismatic molds of 40x40x160 mm in accordance with ASTM C348. Dosing, consistency, and mixing of the standard solution and the slag-added solution were carried out in accordance with the procedure section of the ASTM test method C109 / C109M.
  • the test solution used consisted of 1 part cement and 2.75 parts sand in a ratio by weight.
  • Test prisms were formed by ramming in two layers. The prisms were solidified in a humid room at 98% humidity for one day in the molds and released immediately before testing with a center point load (Figure 7 (b)). For each specified test period (3, 7, 28 days), three samples were made to obtain the average bending strength for each hardening period.
  • the axial load method was used.
  • a device for testing samples of building mortars for bending was installed with taking into account the following principles: the distance between the supports and the points of application of the load must remain constant; the load shall be applied normally to the loaded surface of the specimen and in such a way as to avoid any eccentricity of the load; the direction of the reactions should always be parallel to the direction of the applied load during the test; the load must be applied at a uniform rate and in such a way as to avoid electric shock.
  • the Forney testing machine on which the compression and flexural tests were carried out (Figure 7) met the requirements of ASTM C109 / C109M. Test conditions corresponded to the requirements of ASTM ⁇ 109 / ⁇ 109 ⁇ , ASTM ⁇ 511. Raw materials at room temperature.
  • FIG. 10 shows the curves of the porosity of Portland cement and 5% cement-slag composition, where it is seen that the pores decrease with age. If on the 3rd day the pores of the PC were 22.5%, on the 28th day the pores decreased to 17.5%, the curve represents the dynamics of a slow decrease in the number of pores. In comparison with the curve of 5% cement-slag composition, the dynamics of a decrease in porosity was also observed, but the number of pores decreased more intensively in comparison with the SPC sample. At 28 days of age, with a dosage of 5% SPH in the cement slurry, the number of pores was 16.9%. Thus, the porosity of the cement mortar PC-SPSh5 significantly decreased with the age of hardening, which means that the cement stone with a dosage of 5% steelmaking slag at 28 days of age acquires a denser structure and increases the strength indicators.
  • Figure 9 shows the results of hydration of samples at the age of 3 days of hardening.
  • the main The compounds found on X-ray diffraction patterns are calcium silicate hydrate (CS-H), calcium hydroxide (CH), tricalcium silicate (C 3 S), dicalcium silicate (C 2 S), and calcium sulfoaluminate / Ettringite (E).
  • Calcium hydroxide, known as portlandite (CH) is formed in significant quantities at an early age as a result of the hydration of calcium silicates.
  • a slag-containing cement composite was fabricated and cast into cubic and beam molds for compression and three-point bending tests, and the compressive and flexural strengths were experimentally established.
  • X-ray studies were carried out, tests for porosity using the method of vacuum water absorption, semi-adiabatic calorimetry, and the results showed that with the addition of 5% SSS to the cement mixture is the optimal ratio to accelerate the hydration process and increase the amount of hydration products, especially in early 3 -x day-old hardening age. Scanning electron microscope (SEM) images were obtained, indicating that SSS can be used to prevent the development of microcracks while softening their propagation in the cement slurry.
  • SEM scanning electron microscope

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention se rapporte au domaine des matériaux de construction, et concerne notamment des compositions à base de ciment ayant un contenu en déchets issus de la fabrication de l'acier afin d'édifier et de réparer des bâtiments d'infrastructures industrielles, d'ingénierie et sociales. Le but de la présente invention est d'élaborer de nouvelles compositions de mélanges de ciment ayant un contenu en scories de fabrication d'acier (SFA) en qualité d'additif. Ainsi, le résultat technique de l'utilisation de ce mélange de construction et de réparation de divers bâtiments, y compris des ouvrages techniques hydrauliques et souterrains, consiste en une amélioration des indices de leur imperméabilité, de la résistance aux fissurations, de solidité, et de compensation de retrait. Le résultat économique résulte du fait que l'ajout de déchets de scories de la production d'acier permet de réduire les dépenses sur les ressources en matières premières afin de produire un ciment de Portland, et permet de résoudre les questions économiques sur l'achat de ciment de Portland onéreux. Afin de produire ce mélange, on utilise des scories de production d'acier (SPA) dans une quantité de 1-15% en poids et du ciment de Portland (SP) dans une quantité de 85-90% en poids, et les scories de production d'acier comprennent (en % en poids au moins) СаО-45, SiO2-10, Аl2OЗ-1 et МgО-4.
PCT/KZ2020/000012 2020-05-19 2020-05-19 Mélange de construction à base de ciment avec additif à base de scories de fabrication d'acier WO2021235922A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000044320A (ja) * 1998-07-27 2000-02-15 Matsushita Electric Works Ltd 無機硬化体とその製造方法
RU2317271C1 (ru) * 2006-06-06 2008-02-20 Белгородский государственный технологический университет им. В.Г. Шухова (БГТУ им. В.Г. Шухова) Способ получения цементного клинкера и добавка в сырьевую смесь для получения цементного клинкера
RU2340577C2 (ru) * 2006-07-07 2008-12-10 ИНОСТРАННОЕ ДОЧЕРНЕЕ ОБЩЕСТВО С ОГРАНИЧЕННОЙ ОТВЕТСТВЕННОСТЬЮ "Транс Ворлд Технолоджи" Сульфатно-шлаковое вяжущее
RU2547866C2 (ru) * 2009-08-17 2015-04-10 Лафарж Добавка для гидравлического вяжущего материала на основе клинкера из белита и сульфоалюмината-феррита кальция
RU2647010C1 (ru) * 2017-02-27 2018-03-13 Алсу Рамилевна Хаматова Быстротвердеющая строительная смесь на основе сталеплавильного шлака

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000044320A (ja) * 1998-07-27 2000-02-15 Matsushita Electric Works Ltd 無機硬化体とその製造方法
RU2317271C1 (ru) * 2006-06-06 2008-02-20 Белгородский государственный технологический университет им. В.Г. Шухова (БГТУ им. В.Г. Шухова) Способ получения цементного клинкера и добавка в сырьевую смесь для получения цементного клинкера
RU2340577C2 (ru) * 2006-07-07 2008-12-10 ИНОСТРАННОЕ ДОЧЕРНЕЕ ОБЩЕСТВО С ОГРАНИЧЕННОЙ ОТВЕТСТВЕННОСТЬЮ "Транс Ворлд Технолоджи" Сульфатно-шлаковое вяжущее
RU2547866C2 (ru) * 2009-08-17 2015-04-10 Лафарж Добавка для гидравлического вяжущего материала на основе клинкера из белита и сульфоалюмината-феррита кальция
RU2647010C1 (ru) * 2017-02-27 2018-03-13 Алсу Рамилевна Хаматова Быстротвердеющая строительная смесь на основе сталеплавильного шлака

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