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    • 专利摘要:
    CALCIUM FERROALUMINUM COMPOUND, CEMENT MIXTURE AND SUS MANUFACTURING METHODS, AND CEMENT COMPOSITION. It is the aim of the invention to provide a mixture of cement and a cement composition that can provide sufficiently good resistance to rust to reinforcing rods in hardened cement concrete, and can present resistance to the penetration of chloride ions that enter from the outside, prevent that hardened cement concrete becomes porous by reducing Ca ion leaching, and have a self-healing capacity. The invention provides a cement mixture characterized by the fact that it contains a calcium ferroaluminum compound comprising a CAO-AL2O3-Fe2O3 system, and having a Fe2O3 content of 0.5 to 15% in passes and a structure of CAO.2AL2O3 with a CAO/AL2O3 molar ratio ranging from 0.15 to 0.7. It is preferable that the fineness is from 2000 to 7000 CM2/g represents in terms of the specific surface area value of blaine; a potentially hydraulic substance and/or pozzolan substance (pozzolan substance or the like) is also used; the substance of pozzolan or the like contains one or two or more two or more of the group consisting of slag from (...).
    公开号:BR112012022020B1
    申请号:R112012022020-9
    申请日:2010-11-25
    公开日:2021-04-20
    发明作者:Mori Taiichiro；Taiichiro Mori；Kazuto Tabara；Kenji Yamamoto；Minoru Morioka；Takayuki Higuchi
    申请人:Denki Kagaku Kogyo Kabushiki Kaisha；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
    The present invention primarily relates to a cement mixture and a cement composition used in the fields of civil engineering and construction. DESCRIPTION OF TECHNICAL STATUS
    Calcium aluminoferrite is a well-known CaO-Al2O3-Fe2O3-based compound used for cement mixtures. The calcium aluminoferrite known to date in the art includes 4CaO. A12O3. Fe2O3 (C4AF), 6CaO.2Al2O3 (CgA2F) and 6CaO. A12O3.2F2O3 (C6AF2) .
    These calcium aluminoferrites have a crystal structure of 2CaO.Fe2O3 (C2F) which is a kind of calcium ferrite. In summary, they maintain a crystal structure of C2F, although a large amount of Al2O3 is solubilized as a solid in C2F, and has a variety of Al2O3/Fe2O3 molar ratios in terms of composition. The crystal structure of C2F is an orthorhombic system where a = 5.32 , b - 14.48 and c = 5.51 with a unit lattice volume of 424.95 2.
    On the other hand, CaO.2Al2O3 (CA2) is known as a 25 species of calcium aluminate. The crystal structure of CA2 is a monoclinic system where a = 12.89 , b = 8.88 and c = 5.45 Â with a unit lattice volume of 596.41 Â2.
    Thus, C2F and CA2 have very different crystal structures, and until now no compound has been known with a Fe2O3 component solubilized in solid in CA2.
    By the way, there has recently been a growing demand for improvements in the durability of concrete structures in the fields of civil engineering and construction.
    A factor of degradation of concrete structures is the damage caused by salt, whereby reinforcing rods are visibly corroded in the presence of chloride ions, and to reduce this damage there is a method to provide resistance to chlorine penetration in concrete structures.
    In order to prevent chloride ions from penetrating the concrete structure, thereby giving the concrete structure resistance to this penetration, there is a known method in the technique of reducing water/cement ratios (see Non-Patent Publication 1). However, the method of reducing water/cement ratios is not only detrimental to workability, it may not be a drastic measure either.
    There is also a method of using a cement mixture composed mainly of CaO.2Al2O3 and gypsum and additionally containing an inorganic chloride for the purpose of imparting early strength to the concrete and to prevent corrosion of the rebar (see Patent Publication 1).
    In addition, there is a method of using a cementitious mixture containing calcium aluminate having a molar ratio of CaO/Al2O3 of 0.3 to 0.7 and a Blaine specific surface area of 2000 to 6000 cm2/g, thus , ensuring good resistance to penetration of chloride ions and preventing temperature cracking of the concrete mass (see Patent Publication 2). A problem with this cement mix, however, is that a fast hardening characteristic appears in high temperature environments with detriment to the workability of cement concrete mixed with it. For example, the fast hardening characteristic appears not only in regions where high temperature prevails and chloride attack and acid degradation are accelerated such as in Okinawa and Singapore, however it emerged from numerous studies by the inventors that resistance penetration of chloride ions is not completely achieved. Thus, there is still an expectation of developing a corrosion proof technology that works more effectively where the diffusion speed of corrosive components is high and corrosion reactions are accelerated.
    On the other hand, cement compositions mixed with finely pulverized, quenched, granulated blast furnace slag, and pozzolan substances are known to increase the resistance to penetration of chloride ions. The fact that they inhibit the penetration of chloride ions is that the Al component in the finely pulverized, quenched, granulated blast furnace slag contributes to the chemical fixation, or electrical absorption, of the chloride ions. Referring here to the reduction of calcium hydroxide in hardened cement, pozzolan substances appear to reduce the voids from a few tens to a few hundred micrometres that are formed in the case where the calcium hydroxide is leached to seawater. However, the reactions of finely pulverized, quenched, granulated blast furnace slag and pozzolan substances tend to occur over an extended period of time, preventing the development of initial strength, and causing a problem as they are immersed in water. from the sea at an early stage in age, the resistance to penetration of chloride ions is reduced, resulting in the degradation of the concrete. In order to increase durability, that is, resistance to sea water, it is thus required to accelerate the reactions in the hardened cement, thus reducing the penetration of chloride ions under the action of sea water at an early stage of material age.
    On the other hand, there is also a method for adding nitrides or the like proposed for the purpose of preventing the formation of rust in rebars (see Patent Publications 3 and 4). However, nitrides were found to have no effect on acid resistance.
    Prior Art Listing Patent Publications Patent Publication 1: JP(A) 47-035020 Patent Publication 2: JP(A) 2005-104828 Patent Publication 3: JP(A) 53-003423 Patent Publication 4: JP (A) 01-103970 Non-Patent Publication 1: "Durability Series for Concrete Structures, Chloride Attack (I)" edited by K. Kishitani, N. Nishizawa, etc., Gihodobook, pg. 34-37, May 1986 SUMMARY OF THE INVENTION
    By providing a solution to the problems described above, the present invention has the purpose of providing a cement mixture that can provide good resistance to rust to rebars in hardened cement concrete, even in high temperature environments, presenting resistance to penetration of chloride ions from the outside in the hardened cement concrete, prevent the hardened cement concrete from becoming porous because of less leaching of Ca ions from the hardened cement concrete, and present a self-healing capability enabling cracks to be healed, its method of manufacture, and a cement composition containing the cement mixture.
    In order to achieve the above-mentioned objective, the present invention is carried out as follows: (1) A calcium ferroaluminate compound, comprising a CaO-Al2O3-Fe2O3 system, and having a Fe2O3 content of 0.5 to 15% in mass and a CaO.2Al2O3 structure. (2) A cement mixture characterized by containing a calcium ferroaluminate as stated in (1), where the molar ratio of CaO/Al2C>3 varies from 0.15 to 0.7. (3) A cement mixture as referred to in (2) which exhibits a fineness of 2000 to 7000 cm2/g as represented in terms of Blaine's specific surface area value. (4) A cement mixture as referred to in (3) or (3) which additionally contains a potentially hydraulic substance and/or a pozzolan substance. (5) A cement mixture as referred to in (4), wherein said potentially hydraulic substance and/or a pozzolan substance is one or more of the group consisting of finely pulverized, quenched, granulated blast furnace slag, fly ash, silica active, metakaolinite, incinerated cellulose sludge ash, incinerated sewage sludge ash, and tailings glass dust. (6) A cement mixture as referred to in (4) or (5), wherein said calcium ferroaluminate and said potentially hydraulic substance and/or said pozzolan substance are mixed in a ratio of 10/1 to 110 in mass. (7) A method for manufacturing a cement mixture characterized in that a raw material containing CaO, a raw material containing Al2O3 and an raw material containing iron are mixed in such a way that the molar ratio of CaO/AlaCh varies from 0.15 to 0.7 and the Fe2Os content varies from 0.5% to 15% by mass, and by heat treatment at 1400°C to 1600°C a clinker is obtained, said clinker is sprayed to a value of Blaine's specific surface area from 2000 to 7000 cm2/g. (8) A cement composition containing cement and a cement mixture as indicated in any one of (1) to (6). ADVANTAGES OF THE INVENTION
    The cement mixture of the invention has some considerable advantages: it ensures longer working time even in high temperature environments, ensures a good rust resistance characteristic combined with resistance to penetration of chloride ions from the outside, and prevents the concrete from hardened cement becomes porous due to less leaching of Ca ions. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an XRD diagram for calcium ferrite and calcium aluminoferrite. Fig. 2 is an XRD diagram for ferroaluminate and calcium aluminate. BEST MODE FOR CARRYING OUT THE INVENTION
    The present invention will now be explained in more detail. Note that unless otherwise specified, "part(s)" and "%" are given on a mass basis. It should also be noted that "cement concrete" referred to here is a generic term for cement pastes, cement mortars and concretes.
    Through several experiments, the inventors found that the Fe2C>3 component can be solubilized in solid in CA2, and revealed that this solid solution still maintains the CA2 structure intact, providing a different compound from calcium aluminoferrites such as C4AF, C6A2F , and C6AF2 in terms of composition and crystal structure. The compound containing Fe2O3 solubilized in solid in CA2 while keeping the crystalline structure of CA2 intact is called calcium ferroaluminate.
    Calcium ferroaluminate compound (hereinafter referred to as CFA compound) used herein is a generic term for containing compounds consisting primarily of CaO, AI2O3 and Fe2O3 and obtained by mixing raw materials containing calcium, alumina, ferrite, etc., and burning the resulting mixture in an oven, melting in an electric oven, or some other form of heat treatment.
    Referring now to the composition of the CFA compound, it has a CaO/AlaCb molar ratio of 0.15 to 0.7 and a Fe2O3 content of 0.5 to 15%. More preferably, the molar ratio of CaO/A^Cb is from 0.4 to 0.6. Below 0.15, there is often not sufficient resistance to penetration of chloride ions, and above 0.7, on the contrary, the fast hardening characteristic can often appear, failing to obtain pot life. The Fe 2 O 3 content of the CFA compound should preferably be from 0.5 to 15%, more preferably from 1 to 12%, most preferred being from 3 to 10%. At less than 0.5%m there can often be a large amount of unreacted aluminum oxide remaining in the heat treatment, which not only makes the calcium ferroaluminate formation reaction unlikely to continue, but also causes rapid hardening characteristics in the environments at high temperature, resulting in a reduction in workability and a reduction in resistance to penetration of chloride ions. Above 15%, on the contrary, the effect on maintaining the continuity of the efficient reaction drops, and the resistance to chloride ion penetration tends to worsen as well.
    The fineness of the CFA compound should preferably be from 2000 to 7000 cm2/g, more preferably from 3000 to 6000 cm2/g, most preferred being from 4000 to 5000 cm2/g, as represented in terms of the specific surface area value of Blaine (hereafter called Blaine's value). If the CFA compound is in a coarser particulate form, there is often not sufficient resistance to penetration of chloride ions, and if the CFA compound is in a powder form finer than 7000 cm2/g, the hardening characteristic can often occur. fast, resulting in failure to ensure pot life.
    The raw materials used to prepare the CFA compound will now be explained. As an example, but not a limitation, raw material containing CaO includes quicklime (CaO), hydrated lime (Ca(OH)2) and limestone (CaCOβ), all materials commercially available as industrial materials. As an example, but not a limitation, raw material containing AI2O3 includes AI2O3, aluminum hydroxide and bauxite, all materials commercially available as industrial materials, among which bauxite is the most suitable because it contains both AI2O3 and Fe2O3. As an example, but not a limitation, iron-containing raw material includes Fe2C>3 obtained from pulverizing, processing and refining iron ore, and Fe2O3 obtained from recovering and refining hydrochloric acid from steel treatment, all commercially available materials as industrial materials, FeO, Fβ3θ4, and even pure iron can also be used, if heat-treated in an oxidizing atmosphere.
    These iron-containing raw materials can also be used in combination with, for example, SiO2 and R2O (R being an alkali metal) without prejudice to the scope of the invention.
    The CFA compound can be obtained by mixing raw material containing CaO, raw material containing Al2O3, raw material containing iron, etc., and burning the resulting mixture in an oven, melting in an electric furnace, or any other heat treatment. Although depending on the mixture of raw materials, the heat treatment temperature should preferably be from 1400 to 1600°C inclusive, and more preferably from 1450 to 1550°C inclusive. Below 1400°C, the reaction involved is less likely to continue efficiently, leaving some AI2O3 unreacted and making calcium ferroaluminate impossible to obtain. Above 1600°C, in contrast, raw materials are likely to harden, making operation difficult and leading to a reduction in energy consumption efficiency.
    In the present invention, the CFA compound having a molar ratio of CaO/Al2O3 of 0.15 to 0.7 and a Fe2O3 content of 0.5 to 15%, can be used in combination with the potentially hydraulic substance and/or substance of pozzolan for the purpose of maintaining sufficient strength and the effect of preventing the leaching of Ca ions, increasing initial strength and improving self-recovery ability.
    Specifically, but not exclusively, the potentially hydraulic substance and/or pozzolan substance used herein include finely pulverized, quenched, granulated, blast furnace slag, fly ash, silica fume, metakaolinite, incinerated cellulose sludge ash, sludge ash. incinerated sewage, and tailings glass dust. In order to obtain further enhancements of the effects mentioned above, finely pulverized, quenched, granulated blast furnace slag, fly ash, silica fume, metakaolinite, are preferred.
    Specifically, but not exclusively, the proportion of CFA compound mixed with the potentially hydraulic substance and/or pozzolan substance should preferably be from 10/1 to 1/10 by mass, and more preferably from 5/1 to 1/5 by mass .
    If the mixture ratio of the CFA compound to the pozzolan substance (potentially hydraulic substance) is adjusted in the range mentioned above, the resistance to rust is sufficient, the resistance to penetration of chloride ions, the inhibition effect of the leaching of Ca ions, and the self-healing capabilities are much higher than that of the CFA compound when used alone.
    The cement used here includes a variety of Portland cements, such as normal Portland cement, high initial strength Portland cement, super early strength Portland cement, low heat hydration Portland cement, and moderate heat hydration Portland cement; a variety of mixed cements of these Portland cements with blast furnace slag, fly ash or silica; mixed filler cements with limestone powders, cooled finely pulverized blast furnace slag; and Portland cements such as environmental cements (eco-cements) produced using incinerated municipal waste ash, and incinerated sewage sludge ash, as raw materials, which can be used separately or in two or more.
    Specifically, but not exclusively, when only the calcium ferroaluminate compound is used as the cement mix, the amount of the cement mix is preferably from 1 to 15 parts, and more preferably from 2 to 12 parts per 100 parts of the cement composition. containing cement and the cement mixture. As the amount of cement mixture used is smaller, it often may not provide sufficient resistance to rust, resistance to penetration of chloride ions and the effect on the prevention of leaching of Ca ions, and excessive use can often cause the appearance of the characteristic of fast hardening, failing to ensure sufficient pot life. When the calcium ferroaluminate compound and the potentially hydraulic substance and/or pozzolan substance are used as the cement mixture, the cement mixture is used in an amount preferably from 1 to 50 parts, and more preferably from 5 to 30 parts per 100 parts of cement composition obtained from cement and cement mixture. As the amount of cement mixture is smaller. It often may not provide sufficient rust resistance, resistance to penetration of chloride ions and the leaching-preventing effect of Ca ions, and excessive use can often cause the rapid hardening characteristic to appear, failing to ensure a sufficient pot life .
    In the present invention, cement is mixed with the cement mixture or the CFA compound in a cement composition.
    In the cement composition of the invention, the water/binder ratio should preferably be from 25 to 70%, and more preferably from 30 to 65%. A smaller amount of water can often cause reduced pumping or workability, shrinkage and the like, and too much water can often cause the ability to develop lower strength. The "binder" here refers to the cement and CFA compound combined.
    In the cement mix or cement composition of the invention, the respective materials can be mixed in place or can be partly or fully mixed.
    In the present invention, cement and cement mix as well as fine aggregates such as sand and coarse aggregates such as gravel can be used with one or two or more in the group consisting of expanding materials, fast hardening mortar accelerators, reducing agents AE water reducing agents, high performance water reducing agents, high performance AE water reducing agents, defoamers, thickeners, conventional anti-corrosion agents, antifreeze, shrinkage reducing agents, hardening modifiers , clay minerals such as bentonite, ion exchangers such as hydrocalcite, finely pulverized, quenched, granulated, and finely pulverized, cooled blast furnace slag and mixing materials such as finely pulverized limestone without substantial damage to the object of the invention.
    The mixing apparatus used can be any of the existing mixers, such as tumble mixers, omini mixers, Henschel mixers, type V mixers, and Nauta mixers.
    More specifically, but not exclusively, the present invention will now be explained with reference to the examples of the invention and comparatives. EXAMPLES
    Identification of the crystal structure of the compound Calcium ferrite (C2F), calcium aluminoferrites (C4AF, C6A2F, CgAF2), calcium ferroaluminate and calcium aluminate (CA2) were synthesized.
    Shown in Fig. 1 are XRD diagrams for calcium ferrite (C2F) and calcium aluminoferrites (C4AF, C6A2F, C6AF2), from which it is found that these compounds have the same crystal structure. On the other hand, XRD diagrams for calcium ferroaluminate and calcium aluminate (CA2) are shown in Fig. 2, from which it can be observed that in calcium ferroaluminate, Fe2O3 is solubilized in solid while maintaining the structure CA2 intact. It can also be observed that the Fe2O3 exceeds 15%, there is no solubilization in solid occurring, resulting in the precipitation of magnetite. It has been shown that calcium ferroaluminate is a different compound from calcium ferroaluminate which is a CaO-Al2O3-Fe2O3 system known in the art. Experimental Example 1
    The calcium carbonate primary reagent and aluminum oxide primary reagent were mixed in molar proportions as defined in Table 1 based on the oxide, and the iron oxide primary reagent was added to the mixture with Fe2O contents as shown in Table 1 for burning the resulting mixture in an electric oven. A mixture containing a CaO/Al2C>3 molar ratio of 0.7, a mixture containing a CaO/Al2O3 molar ratio of 0.6, a mixture containing a CaO/Al2C>3 molar ratio of 0.4, a mixture containing a CaO/Al2C>3 molar ratio of 0.15, were fired at 1400°C, 1450°C, 1500°C, and 1550°C, respectively, for 3 hours, and then cooled for synthesis. The samples were all adjusted to a Blaine value of 4000 cm2/g. For the purpose of comparison, a sample that was free of iron oxide, a sample containing SiO2, and a sample containing R2O were also synthesized. It was estimated by means of x-ray diffraction whether or not there was unreacted matter. The results are shown in Table 1.
    X-ray diffraction estimate The X cross indicates that the diffraction peak for unreacted matter (aluminum oxide) has been clearly identified; the triangle Δ indicates that there is a small peak identified; and circle O indicates that no peaks were identified. Table 1

    *: Silicon oxide was added instead of iron oxide **: Instead of iron oxide, sodium carbonate was added in an amount of 3% calculated on the basis of Na2O From Table 1, it is found that the incorporation of iron enables the CFA compound to be synthesized without leaving any unreacted alumina yet with high energy efficiency.
    With reference to the iron-free samples, the diffraction peak for unreacted aluminum oxide disappeared with the burning of the sample showing a Caθ/A12θ3 molar ratio of 0.7 to 1500°C or above, of the sample showing a CaO/Al2O3 molar ratio from 0.6 to 1550°C or above, the sample having a CaO/Al2O3 molar ratio of 0.4 to 1600°C or above, and the sample having a Caθ/A12θ3 molar ratio of 0.15 1650°C or above . Experimental Example 2 The CFA compounds shown in Table 2 were each mixed with cement in an amount of 7 parts per 100 parts of cement and the CFA compound in order to prepare a cement composition, and a mortar sample having a water/ ratio. 0.5 binder was prepared in accordance with JIS R 5201. This mortar sample was measured in terms of setting time, rust resistance, compressive strength, chloride penetration depth, Ca ion leaching and resistance to attack by sulfate. The results are shown in Table 2. Note that the tests were conducted in an environment at 30°C. Compounds CFA Compound CFA A The calcium carbonate primer and aluminum oxide primer were mixed in a given ratio, and the iron oxide primer reagent was further mixed with the mixture so as to provide a Fe2O3 content of 3%. As in Experimental Example 1, the mixture was fired at 1550°C in an electric oven and cooled for synthesis. The CaO/Al2O3 molar ratio was 0.1, and the Blaine value was 4000 cm2/g. Compound CFA B In Experiment 1-3, the CaO/Al2O3 molar ratio was 0.15, the Fe2O3 content was 3%, and the Blaine value was 4000 cm2/g. Compound CFA C In Experiment 1-9, the CaO/Al2O3 molar ratio was 0.4, the Fe2O3 content was 3%, and the Blaine value was 4000 cm2/g. Compound CFA D In Experiment 1-15, the CaO/Al2O3 molar ratio was 0.6, the Fe2O3 content was 3%, and the Blaine value was 4000 cm2/g. Compound CFA E In Experiment 1-21, the CaO/Al2O3 molar ratio was 0.7, the Fe2O3 content was 3%, and the Blaine value was 4000 cm2/g. Compound CFA F This compound was synthesized by burning at 1400°C in an electric furnace, and cooling; the CaO/Al2O3 molar ratio was 0.9, the Fe2O3 content was 3%, and the Blaine value was 4000 cm2/g. Compound CFA G In Experiment 1-26, the molar ratio CaO/Al2C>3 was 0.4, and the Blaine value was 4000 cm2/g. Compound CFA H In Experiment 1-29, the CaO/Al2O3 molar ratio was 0.4, the SiO2 content was 3%, and the Blaine value was 4000 cm2/g. Compound CFA I In Experiment 1-30, the CaO/Al2O3 molar ratio was 0.4, the Na2O content was 3%, and the Blaine value was 4000 cm2/g. Cement Commercially available normal Portland cement. Fine Aggregate Standard sand used in accordance with JIS R 5201. Water Tap water. Estimates
    For the hardening time, when hardening ended and was measured according to JIS R 5201. For the effect of resistance to rust, the accelerated test was performed in which chloride ions were incorporated as intrinsic chloride ions in a mortar sample at a concentration of 10 kg/m3 and a round steel rebar was placed in the mortar for aging by heating at 50°C. The rust on none of the rebars was considered good; rebar rust in an area of 1/10 was acceptable; and rebar rust beyond the 1/10 area was unacceptable. For the compressive strength, this was measured after a time interval of one day and 28 days according to JIS R 5201. For the depth of penetration of chlorides, the resistance to penetration of chloride ions was estimated. More specifically, a 10 cm x 20 cm column mortar sample was aged in water at 30°C until the material reached an age of 28 days. After the sample was immersed in synthetic seawater that was brine at 30°C having a salt concentration of 3.5% for 12 weeks, the depth of penetration of chloride ions was measured. A portion of the mortar sample section that did not turn brown in the fluorescein-silver nitrate method was taken as the chloride penetration depth, and 8 measurements were taken per caliper were used for the average. For Ca ion leaching, a 4 x 4 x 16 cm mortar sample was immersed in 16 liters of pure water for 28 days to measure the concentration of Ca ions dissolved in a liquid phase. For resistance to sulfate attack, a 4 x 4 x 16 cm mortar sample was immersed in a 10% NasSCh solution for 25 weeks to measure the expansion coefficient. Table 2
    No cement was used in Experiment No. 2-1 *: No samples could be prepared in view of fast hardening. **: The sample was adjusted in 4 minutes, considering its fluidity reduction. For the rust resistance, no rust on the rebar was considered to be good; rebar rust in an area of 1/10 was acceptable; and rebar rust beyond an area of 1/10 was unacceptable.
    As can be seen from Table 2, if the compounds CFA B, C, D and E with a molar ratio CaO/A12C>3 of 0.15 to 0.7 and containing iron (Fe2O3) are used as a cement mixture (Experiments in 2-3 to 2-6), sufficient working time can be ensured in high temperature environments in particular, and the effect of rust resistance and resistance to penetration of chloride ions can be maintained much longer, not only with prevention of a reduction in the initial resistance, but also with increases in the Ca ion leaching inhibiting effect and the resistance to sulfate attack, in strong contrast to Experiment 2-1, where no CFA cçç was used. In particular, CFA compounds C and D having a CaO/Al2O3 molar ratio of 0.4 to 0.6 are preferred. The use of compound CFA A containing iron, but having a CaO/Al2C>3 molar ratio of 0.1 (Experiment No. 2-2, and compound G having a CaO/Al2O3 molar ratio of 0.4, but not containing iron (compound G is conveniently classified as compound CFA in Table 2, although it belongs to compound CA) (Experiment No. 2-8), resulted in a reduction in the resistance to penetration of chloride ions, in view of an insufficient effect on the inhibition of Ca ion leaching. The use of the CFA F compound having a CaO/Al2C>3 molar ratio of 0.9 (Experiment No. 2-7) made it impossible to ensure pot life due to rapid hardening.
    The use of compound H containing SiO2 instead of Fe2C>3 (compound H is conveniently classified as compound CFA in Table 2, although it does not belong to compound CFA) (Experiment No. 2-9), made the effect of rust resistance low, caused a reduction in the initial resistance, and failed to obtain sufficient resistance to chloride ion penetration, sufficient effects on the inhibition of Ca ion leaching with a reduction in resistance to sulfate attack.
    The use of compound I containing Na2O instead of Fe2C>3 (compound I is conveniently classified as compound CFA in Table 2, although it does not belong to compound CFA) (Experiment 2-9) resulted in a reduction in flowability within a short time. period of time, leading to an early sedimentation of the cement composition. Experimental Example 3
    Experimental Example 2 was repeated with the exception of the combined use of the CFA compound which was synthesized by mixing the primary reagent calcium carbonate and the primary reagent aluminum oxide in a CaO/Al2O3 molar ratio of 0.4, with mixing of the primary reagent. iron oxide in order to provide the Fe2C>3 contents shown in Table 3, and burning the mixture in an electric furnace as in Example 1, followed by cooling. The results are shown in Table 3. Table 3
    As can be seen from Table 3, if CFA compounds containing iron in an amount of 0.5 to 15% by mass are used as a cement mixture (Experiments 3-1 to 3-6, sufficient working times can be ensured even in high temperature environments in particular, and the effect of rust resistance and resistance to penetration of chloride ions can be maintained much longer, not only preventing a reduction in the initial resistance, but also increasing the inhibition effect of the 5 Ca ion leaching and resistance to sulfate attack, in strong contrast to Experiment No. 2-8 where the iron-free CA compound was used. The use of the CFA compound containing iron in an amount of 20% by mass ( Experiment No. 3-7) failed to obtain sufficient resistance to chloride ion penetration and sufficient effect on the inhibition of Ca ion leaching. Experimental Example 4
    Experimental Example 2 was repeated with the exception of using the compound CFA D whose fineness is shown in Table 15 4. The results are also shown in Table 4. Table 4


    For rust resistance, no rebar rust was considered good; rebar rust in an area of 1/10 was acceptable; rebar rust beyond an area of 1/10 was unacceptable.
    As can be seen from Table 4, if the fineness of the CFA compound is adjusted to the cement mix, the effect of rust resistance and the resistance to penetration of chloride ions can then be maintained much more, not just by preventing the reduction of the resistance, but also with an increase in the effect of inhibition of Ca ion leaching and resistance to sulfate attack. The fineness of the CFA compound should preferably be from 2000 to 7000 cm2/g, more preferably from 3000 to 6000 cm2/g, and most preferred being from 4000 to 5000 cm2/g. Experimental Example 5
    Experimental Example 2 was repeated with the exception that the CFA D compound was used in the amounts shown in Table 5. For the purpose of comparison, a similar experiment was conducted using conventional rust proof materials. The results are also shown in Table 5. Conventional Rust Proof Materials I: Commercially available lithium nitride II: Commercially available nitride type hydrokalumite Table 5
    The amount of CFA compound is given in parts per 100 parts of the cement composition consisting of cement and CFA compound. In Experiment n° 2-1, no cement mixture was used *: Conventional rust proof material is used.
    For rust resistance, no rebar rust was considered good; rebar rust in an area of 1/10 was acceptable; rebar rust beyond an area of 1/10 was unacceptable.
    As can be seen from Table 5, if an amount of the CFA compound used is adjusted to the cement mix, the effect of rust resistance and resistance to chloride ion penetration can then be maintained much more, not just with prevention of a resistance reduction, but also with increased effect on the inhibition of Ca ion leaching and resistance to sulfate attack.
    From Table 5, it is found that when only the calcium ferroaluminate compound is used as the cement mixture, it should be used in an amount preferably from 1 to 15 parts, and more preferably from 2 to 12 parts per 100 parts of the composition of cement consisting of cement and cement mixture. Experimental Example 6
    The CFA compounds having a variable CaO/Al2O3 molar ratio as shown in Table 6 were mixtures with the potentially hydraulic substance and/or pozzolan substance I at a weight ratio del/2 in the 30 cement mixtures. This cement mixture was used with cement to prepare a cement composition containing 21 parts of the cement mixture per 100 parts of the cement composition, and a mortar sample having a water/binder ratio of 0.5 was prepared in accordance with JIS R 5201. This mortar sample was measured in terms of rust resistance, compressive strength, chloride ion penetration depth, Ca ion leaching and self-healing capacity. The results are shown in Table 6. Potentially Hydraulic Substance and/or Pozzolan I Substance
    Finely pulverized, quenched, granulated blast furnace slag commercially available in the art and having a Blaine value of 4000 cm2/g. Estimation of Self-Recovery Ability A 10 x 10 x 40 mortar sample was prepared with which 6 mm nylon fibers were mixed in an amount of 0.15% by mass, and a 0.3 mm crack of width was introduced by bending effort. After the sample had been immersed in synthetic seawater for 180 days, the crack width was measured. The double circle with dot © indicates that the crack has been fully closed; circle O indicates the crack width has decreased to 0.1 mm or less; the triangle Δ indicates that the crack width has reduced to about 0.2 mm, and the cross X indicates that the crack width has not reduced, but rather increased. Table 6
    In Experiment No. 2-1, no cement mixture was used *: No sample could be prepared due to rapid hardening As can be seen from Table 6, if the CFA compounds B, C, D and E of the invention show a molar ratio CaO/Al2C>3 from 0.15 to 0.7 are used in combination with the potentially hydraulic substance and/or substance 10 of pozzolan (Experiments nos. 6-2 to 6-5), the effect of rust resistance and strength chloride ion penetration can then be increased not only with an increase in the initial strength, but also with an increase in the Ca ion leaching inhibiting effect as well as the self-healing capacity, in sharp contrast to the comparative example where the compounds are not used (Experiment No. 2-1). CFA compounds C and D having a Caθ/A12θ3 molar ratio of 0.4 to 0.6 are particularly preferred. With the CFA A compound having a CaO/Al2O3 molar ratio of 0.1 (Experiment No. 6-1), both the resistance to penetration of chloride ions and the effect on the inhibition of the leaching of Ca ions remained insufficient with the reduction in capacity. of self-healing, and with the CFA F compound having a CaO/Al2O3 molar ratio of 0.9 (Experiment No. 6-6), pot time cannot be assured due to rapid hardening. Experimental Example 7 Experimental Example 6 was repeated with the exception of using the CFA compounds shown in Table 7 with varying Fe2Ü3 contents in combination with the potentially hydraulic substance and/or pozzolan substance I. The results are also shown in Table 7. Compounds CFA Compound CFA JO calcium carbonate primary reagent and aluminum oxide primary reagent were mixed in a given proportion with addition of iron oxide primary reagent at a Fe2C>3 content of 0.5%. Then, the mixture was fired at 1450°C in an electric oven, and finally cooled for synthesis. The molar ratio CaO/Al2C>3 was 0.6, and the Blaine value was 4000 cm2/g. Compound CFA KO calcium carbonate primer reagent and aluminum oxide primer reagent were mixed in a given proportion with addition of iron oxide primer reagent at a Fe2O3 content of 1%. Then, the mixture was fired at 1450°C in an electric oven, and finally cooled for synthesis. The CaO/AlaCb molar ratio was 0.6, and the Blaine value was 4000 cm2/g. Compound CFA LO Calcium carbonate primer reagent and aluminum oxide primer reagent were mixed in a given proportion with addition of iron oxide primer reagent at a Fe2O3 content of 7%. Then, the mixture was fired at 1450°C in an electric oven, and finally cooled for synthesis. The CaO/A12O3 molar ratio was 0.6, and the Blaine value was 4000 cm2/g. Compound CFA MO calcium carbonate primer reagent and aluminum oxide primer reagent were mixed in a given proportion with addition of iron oxide primer reagent at a Fe2O3 content of 10%. Then, the mixture was fired at 1450°C in an electric oven, and finally cooled for synthesis. The CaO/Al2O3 molar ratio was 0.6, and the Blaine value was 4000 cm2/g. Compound CFA NO calcium carbonate primer reagent and aluminum oxide primer reagent were mixed in a given proportion with addition of iron oxide primer reagent at a Fe2O3 content of 20%. Then, the mixture was fired at 1450°C in an electric oven, and finally cooled for synthesis. The CaO/Al2O3 molar ratio was 0.6, and the Blaine value was 4000 cm2/g. Compound CFA O The primary reagent calcium carbonate and primary reagent 5 aluminum oxide were mixed in a given ratio. Then, the mixture was fired at 1450°C in an electric furnace in the absence of Fe2O3, and finally cooled for synthesis. The CaO/Al2O3 molar ratio was 0.6, and the Blaine value was 4000 cm2/g. Table 7

    In Experiment No. 2-1, no cement mixture was used.
    As can be seen from Table 7, if the CFA compounds D, J, K, L, M, N and O having a CaO/Al2O3 molar ratio of 0.5 to 20% are used in combination with the potentially hydraulic substance and/ or pozzolan substance (Experiment nos. 6-4 and 7-1 to 7-5), the effect of rust resistance and resistance to penetration of chloride ions can then be increased not only with an increase in the initial strength, but also with increase in the inhibition effect of Ca ions leaching, as well as in the self-recovery capacity. When the CFA O compound having a Fe2O2 content of 0 (this compound is conveniently classified as CFA compound in Table 7, although it belongs to the CA compound) it was used in combination with the potentially hydraulic substance and/or pozzolan substance (Experiment no. 7-6), the initial resistance has been reduced. Experimental Example 8 Experimental Example 6 was repeated with the exception of using the compound CFA D whose fineness is shown in Table 8 in combination with the potentially hydraulic substance and/or pozzolan substance I. The results are also shown in Table 8. Table 8

    As can be seen from Table 8, if the fineness of the CFA compound is adjusted, then the effect of rust resistance and resistance to penetration of chloride ions can then be maintained not only with preventing a reduction in strength, but also with increase in the inhibition effect of Ca ions leaching, as well as in the self-recovery capacity. The fineness of the CFA compound should preferably be from 2000 to 7000 cm2/g, more preferably from 3000 to 6000 cm2/g, and most preferred being from 4000 to 5000 cm2/g.
    Experimental Example 6 was repeated with the exception of using the compound CFA D in combination with potentially hydraulic substances and/or pozzolan substances (hereinafter referred to briefly as pozzolan substances). Pozzolan Substances Pozzolan Substance II: Commercially available active silica having a BET surface area of 20 m2/g. Pozzolan III Substance: Commercially available fly ash having a Blaine value of 4000 cm2/g. Pozzolan IV Substance: Commercially available metakaolinite having a BET surface area of 10 m2/g. Pozzolan V Substance: Commercially available incinerated cellulose sludge ash having a Blaine value of 4000 cm2/g. Pozzolan substance VI: Commercially available incinerated sewage sludge ash having a Blaine value of 9000 cm2/g. Pozzolan Substance VII: Commercially available tailing glass powders having a Blaine value of 4000 cm2/g. Pozzolan Substance VIII: Mixture of 50 parts of Pozzolan Substance I and Pozzolan Substance II having a Blaine value of 10000 cm2 /g. Table 9

    As can be seen from Table 9, even with any of the pozzolan substances, the effect of resistance to rust and resistance to penetration of chloride ions could be maintained not only with prevention of resistance reduction, but also with increased effect on the inhibition of Ca ion leaching, as well as the self-recovery capacity. In particular, finely pulverized, quenched, granulated blast furnace slag (pozzolan substance I), silica fume (pozzolan substance II), fly ash (pozzolan substance III), and metakaolinite (pozzolan substance IV) are preferred. Experimental Example 10
    The Experimental Example was repeated with the exception that the compound CFA D and the pozzolan substance I were mixed in the proportions shown in Table 10 in the cement mixtures. Table 10

    In Experiment No. 2-1, no cement mixture was used. As can be seen from Table 10, if the mixture ratio of CFA compound to pozzolan substance is adjusted to from 1/20 to 20/1 by mass, so the effect of resistance to rust and resistance to penetration of chloride ions can be maintained not only with prevention of a reduction in the resistance, but also with an increase in the effect on the inhibition of Ca ion leaching as well as the self-healing capacity. . The mixing ratio mentioned above preferably is from 1/10 to 10/1 by mass, most preferred being from 1/5 to 5/1 by mass. Experimental Example 11
    Experimental Example 6 was repeated with the exception that the compound CFA D was used to prepare the cement mixtures (compound CFA D plus pozzolan substance I) in the amounts shown in Table 11. For the purpose of comparison, similar experiments were conducted using conventional rust proof materials. The results are also shown in Table 11. Table 11

    The cement mix was used in an amount (part) per 100 parts of the cement composition made of cement plus the cement mix. **: Conventional rust proof materials were used. No rust on the rebar was considered good; rust in an area of 1/10 was acceptable; and rebar rust beyond an area of 1/10 was unacceptable.
    As can be seen from Table 11, if the amount of cement mixture used is adjusted, then the effect of resistance to rust and resistance to penetration of chloride ions can be maintained not only with prevention of a reduction in strength, but also with increase in the effect on the inhibition of Ca ions leaching, as well as in the self-recovery capacity. From Table 11, it can be found that when CFA compound and pozzolan substance are used as cement mixture, the amount of cement mixture used preferably ranges from 1 to 50 parts, and more preferably from 5 to 30 parts per 100 parts of cement composition made of cement and cement mixture. INDUSTRIAL APPLICABILITY
    The use of the cement mixture of the invention can ensure sufficient working time even in high temperature environments, and ensure good resistance to rust and resistance to penetration of chloride ions combined with the inhibition effect of Ca ion leaching and resistance to the attack of sulfate; in this way, it can be well compatible with a wide range of applications, including mainly in structures used in water, water tanks, concrete slabs, etc., in seawater and rivers in the fields of civil engineering and construction.
    权利要求:
    Claims (8)
    [0001]
    1. Calcium ferroaluminate compound characterized by the fact that it comprises a CãoCaO-Al2O3-Fe2O3 system, and has a Fe2O3 content of 0.5 to 15% by mass and a CaO.2Al2O3 structure.
    [0002]
    2. Cement mix characterized by the fact that it contains a calcium ferroaluminate as defined in claim 1, where a CaO/Al2O3 ratio ranges from 0.15 to 0.7.
    [0003]
    3. Cement mix according to claim 2, characterized in that it has a fineness of 2000 to 7000 cm2/g as represented in terms of a Blaine specific surface area value.
    [0004]
    4. Cement mixture according to claim 2, characterized in that it additionally contains a potentially hydraulic substance and/or a pozzolan substance.
    [0005]
    5. Cement mixture according to claim 4, characterized in that said potentially hydraulic substance and/or said pozzolan substance contain one or more of the elements selected from the group consisting of granulated, quenched, finely powdered blast furnace slag, fly ash, silica fume, metakaolinite, incinerated cellulose sludge ash, sewage sludge ash, and tailings glass dust.
    [0006]
    6. Cement mix according to claim 4, characterized in that said ferroaluminate and said potentially hydraulic substance and/or said pozzolan substance are mixed in a mixing ratio of 10/1 to 1/10 by mass.
    [0007]
    7. Method for manufacturing a cement mixture characterized in that a raw material containing CaO, a raw material containing Al2O3 and a raw material containing iron are mixed in such a way that a molar ratio of CaO/Al2O3 varies from 0.15 at 0.7 and an iron content ranging from 0.5% to 15% by mass, and is heat treated at from 1400°C to 1600°C inclusive to obtain a clinker, and said clinker is pulverized to a Blaine's specific surface area value ranging from 2000 to 7000 cm2/g.
    [0008]
    8. Cement composition characterized in that it contains cement and a cement mixture as defined in any one of claims ^—2 to 6.
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    同族专利:
    公开号 | 公开日
    EP2543648A4|2016-06-08|
    KR101799611B1|2017-11-20|
    NO2543648T3|2018-07-07|
    EP2543648B1|2018-02-07|
    WO2011108159A1|2011-09-09|
    SG183833A1|2012-10-30|
    CN102869633A|2013-01-09|
    CN102869633B|2014-04-02|
    JPWO2011108159A1|2013-06-20|
    HRP20180634T1|2018-06-01|
    EP2543648A1|2013-01-09|
    US20120318172A1|2012-12-20|
    JP5688073B2|2015-03-25|
    ES2666344T3|2018-05-04|
    WO2011108065A1|2011-09-09|
    US8425679B2|2013-04-23|
    PL2543648T3|2018-08-31|
    KR20130049177A|2013-05-13|
    BR112012022020A2|2020-09-01|
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    法律状态:
    2020-09-15| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-09-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 20/04/2021, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP2010/053270|2010-03-01|
    PCT/JP2010/053270|WO2011108065A1|2010-03-01|2010-03-01|Cement admixture and cement composition|
    JPPCT/JP2010/053270|2010-03-01|
    PCT/JP2010/070972|WO2011108159A1|2010-03-01|2010-11-25|Calcium ferroaluminate compound, cement admixture and process for producing same, and cement composition|
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