CN115448681A - Iron aluminate cement for repairing and preparation method thereof - Google Patents

Iron aluminate cement for repairing and preparation method thereof Download PDF

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Publication number
CN115448681A
CN115448681A CN202211271420.4A CN202211271420A CN115448681A CN 115448681 A CN115448681 A CN 115448681A CN 202211271420 A CN202211271420 A CN 202211271420A CN 115448681 A CN115448681 A CN 115448681A
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aluminate cement
gypsum
cement
remedial
calcium oxide
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CN115448681B (en
Inventor
裴天蕊
齐冬有
邹德麟
王剑锋
汪智勇
郝禄禄
王亚丽
张钰
刘洪印
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Beijing University of Technology
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Beijing University of Technology
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    • 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
    • C04B28/14—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 calcium sulfate 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
    • C04B7/32—Aluminous 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/24—Sea water resistance
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72—Repairing or restoring existing buildings or building materials
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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

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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)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to a ferrous aluminate cement with high ultra-early strength and excellent seawater erosion resistance, which quickly generates Al (Fe) ettringite, iron glue, aluminum glue and C-S-H gel in proper proportion by the cooperation of raw materials of ferrous aluminate cement clinker, silica fume, gypsum, a water reducing agent, nitrite, a reinforcing agent and calcium oxide and the synergistic hydration and regulation functions, coordinates the internal stress among hydration products and optimizes the microstructure of the hydration products, thereby promoting the ultra-early strength development of the ferrous aluminate cement and obtaining higher strength in a seawater erosion environment.

Description

Iron aluminate cement for repairing and preparation method thereof
Technical Field
The invention relates to the field of building materials, in particular to a ferric aluminate cement for repairing and a preparation method thereof.
Background
Along with the development of marine resources, more and more concrete is in service in the marine environment, and along with the increase of service time, the damaged part of concrete is repaired in time, so that the service life of the marine engineering concrete is prolonged. The cement is an indispensable composition of concrete, and the quality of the performance of the cement plays a decisive role in the service life and the maintenance cost of the ocean engineering concrete.
The hydration product of the portland cement is easy to be eroded by chloride, sulfate and magnesium salt in sea water, cl-SO 4 2- 、Mg 2+ And the cation exchange reaction is carried out between the modified cement paste and the concrete, so that reinforcing steel bars in the concrete are rusted, the liquid-phase acid-base balance is broken, a dilatancy product is generated, a C-S-H structure is weakened, the concrete is cracked and peeled off, the strength and rigidity are lost, and the service of the concrete is seriously influenced.
The ferrous aluminate cement has excellent seawater corrosion resistance, high early strength and limited ultra-early strength, and the repair progress can be accelerated by improving the ultra-early strength of the ferrous aluminate cement, so that the concrete can be quickly used again. Therefore, the development of the ferrous aluminate cement with high ultra-early strength and excellent seawater corrosion resistance is urgently needed, the repair cement with excellent quality is provided for the market, and the requirement of ocean engineering repair is met.
Disclosure of Invention
The invention aims to provide the iron aluminate cement for repairing and the preparation method thereof, which can effectively improve the ultra-early strength of the iron aluminate cement, keep higher strength increase in later seawater corrosion environment and meet the requirement of ocean engineering repairing.
Specifically, the iron aluminate cement for repairing comprises the following raw materials in percentage by mass: 85-90% of ferrous aluminate cement clinker, 1-7% of silica fume, 4-8% of gypsum, 0.08-0.2% of water reducing agent, 0.1-0.5% of nitrite, 0.03-0.05% of reinforcing agent and 2-3% of calcium oxide.
Preferably, the iron phase content of the iron aluminate cement clinker is more than 20%, and the anhydrous calcium sulphoaluminate content is more than 45%.
Preferably, the gypsum is at least one of natural gypsum and industrial by-product gypsum.
More preferably, the natural gypsum is at least one of anhydrite, hemihydrate gypsum and dihydrate gypsum.
More preferably, the industrial by-product gypsum is at least one of desulfurized gypsum and phosphogypsum.
Preferably, the water reducing agent is a polyphosphoric acid water reducing agent. The iron aluminate cement clinker contains a large amount of iron phase, and the experimental process finds that the naphthalene water reducer and the polycarboxylic acid water reducer have a certain dispersing effect on the iron aluminate cement, but the early strength effect is not obvious, and the polyphosphoric acid water reducer and the iron aluminate cement clinker have better early strength effect and adaptability.
More preferably, the polyphosphoric acid water reducing agent is an early-strength polyphosphoric acid water reducing agent, the average weight-average molecular weight is 35000-45000, and the acid-ether ratio is 4.
Preferably, the nitrite is at least one of sodium nitrite and potassium nitrite.
Preferably, the enhancer is ethylene diamine tetraacetic acid monomethyl ester.
Preferably, the calcium oxide is high-activity calcium oxide obtained by calcining calcium carbonate at 900 ℃.
The invention also relates to a preparation method of the iron aluminate cement for repairing, which comprises the following steps:
1) Grinding the cement clinker of the iron aluminate to 400-500m 2 Grinding gypsum into powder of 450-600m 2 After/kg, uniformly mixing the mixture with silica fume according to a preset proportion by 1 to obtain a mixture 1;
2) Calcining calcium carbonate in a muffle furnace to prepare high-activity calcium oxide;
3) And (3) respectively adding the water reducing agent, the nitrite, the reinforcing agent and the calcium oxide into the mixture 1 according to the dosage and fully grinding.
Preferably, the calcination temperature in step 2) is 30-60min, more preferably 40min.
The invention has the following technical advantages:
1. the invention adopts the iron aluminate cement clinker as the main raw material of the repair cement, the main hydration products of the hydration products are Al, (Fe) ettringite, iron glue, aluminum glue and the like, the test result shows that the crystal strength of the Fe-ettringite is higher than that of the Al-ettringite, the iron glue has better stability in seawater than the aluminum glue, and a large amount of C-S-H gel can be generated by adding the silica fume.
2. The hydration of the cement clinker of the iron aluminate cement is rapid, a large number of interwoven micropores exist in early hydration products, and experimental research shows that the mixed material of the fly ash and the mineral powder can not meet the strength requirement of the super early strength iron aluminate cement, and the hydration process of the fly ash and the mineral powder absorbs more SO in gypsum 4 2- Influences the thickness appearance of the hydration product of the cement clinker of the iron aluminate, reduces the mechanical property of the cement, has larger specific surface area of the silica fume, can play the role of micro-aggregate to be filled in the pores of the hydration product of the cement clinker of the iron aluminate, increases the compactness of slurry, and improves the Ca in the ultra-early stage by quickly dissolving the calcium oxide 2+ The concentration promotes the formation of ettringite, and the alkaline environment provided by the ettringite promotes the active SiO in the silica fume 2 Hydrating to generate C-S-H gel to fill the AFt framework, and further improving the strength of the slurry; the siliceous dust, the gypsum, the calcium oxide and the iron aluminate cement clinker are hydrated cooperatively, the hydration into an alkaline compact environment greatly increases the seawater erosion resistance of the material, and other materials can not achieve the effect.
3. The invention adopts the polyphosphoric acid water reducing agent as the high-performance water reducing agent to disperse cement clinker particles, is not easy to lose efficacy in a strong alkaline environment formed by calcium oxide, has better compatibility and dispersibility with the iron aluminate cement clinker than the traditional naphthalene water reducing agent and polycarboxylic acid water reducing agent, has the early strength function of nitrite, promotes the hydration of the iron aluminate cement clinker and siliceous dust,the adaptability of the ethylene diamine tetraacetic acid monomethyl ester and the cement clinker of the ferroaluminate cement is stronger, the solubilization effect is exerted on the surface of the clinker, the tight wrapping of hydration products on the surface of the clinker is broken, the continuous exposure of hydration active sites is promoted, the dissolution of the clinker in the ferroaluminate cement can be effectively promoted, and the C is remarkably improved 2 The dissolution effect of iron phases such as F, etc., so that more Fe is available in a short period 3+ Participates in hydration, and can chelate with metal ions in seawater when the iron aluminate cement is eroded by seawater, so as to change Ca (OH) in hydration products 2 The shape of the gel ensures the strength increase in the later-stage corrosion environment and improves the seawater corrosion resistance of the ferro-aluminate cement; the water reducing agent, the nitrite, the ethylene diamine tetraacetic acid monomethyl ester and the iron aluminate cement are mutually coordinated, so that the iron aluminate cement slurry has high super-early strength, wherein the optimized early-strength polyphosphoric acid water reducing agent has the best synergistic effect with the iron aluminate cement when the molecular weight is 35000-45000, the super-early strength of the iron aluminate cement is improved while the water is efficiently reduced, and the stable increase of the later strength is ensured.
4. The invention adopts silica fume, gypsum, calcium oxide and iron aluminate cement clinker for hydration coordination, and utilizes polyphosphoric acid water reducing agent, nitrite and ethylene diamine tetraacetic acid monomethyl ester for modification and reinforcement, the generated Al, (Fe) ettringite crystal becomes coarse, the crystal structure is reinforced, the stability of ettringite skeleton in slurry is increased, meanwhile, iron glue and aluminum glue can be refined, and the slurry strength and seawater erosion resistance are improved.
5. The iron aluminate cement for repairing developed by the components has the advantages of simple ingredients and low cost, can be hydrated to realize strength increase when being maintained in a seawater environment, can improve the ultra-early strength of the iron aluminate cement and increase the seawater corrosion resistance of the iron aluminate cement, and meets the repairing requirement of ocean engineering.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
In the experimental process, firstly, preparing cement according to a mass ratio, weighing the cement and standard sand according to a mass ratio of 1. Wherein the mechanical testing is carried out according to the testing method specified in GB/T17671-1999 Cement mortar Strength test method (ISO) method.
The test method of the seawater erosion resistance test is as follows: the proportioning, stirring, molding and moisture curing of the mortar sample meet GB/T17671-1999. And after demoulding, maintaining the sample in artificial seawater for 28 days, taking out the sample, maintaining the control group in clear water, soaking the experimental group in an artificial seawater solution (the preparation method is referred to as ASTM D1141-98), placing the plastic container in which the sample is soaked in the artificial seawater solution at the temperature of 20 +/-1 ℃, and sealing the plastic container by adding a cover to prevent water from evaporating to influence the concentration of the artificial seawater. The compressive strength of the artificial seawater sample and the clean water sample is tested, and the seawater erosion resistance coefficient is calculated according to the formula 1:
K＝R liquid for treating urinary tract infection /R Water (W)
In the formula, R Liquid for treating urinary tract infection And R Water (I) The compressive strength of the mortar samples immersed in the artificial seawater solution and water, respectively, is expressed in MPa.
Example 1
The iron aluminate cement for repairing comprises the following raw materials in parts by mass: 87% of iron aluminate cement clinker, 5% of silica fume, 5% of anhydrite, 0.17% of polyphosphoric acid water reducing agent, 0.2% of sodium nitrite, 0.03% of ethylene diamine tetraacetic acid monomethyl ester and 2.6% of calcium oxide. The detection shows that the 2h clear water curing strength of the cement mortar is 27.7MPa, the 4h clear water curing strength is 35.6MPa, the 1d clear water curing strength is 53.2MPa, the 28d clear water curing strength is 62.3MPa, and the seawater erosion resistance coefficient is 1.28.
Example 2
The iron aluminate cement for repairing comprises the following raw materials in parts by mass: 90% of ferrous aluminate cement clinker, 2% of silica fume, 6% of anhydrite, 0.16% of polyphosphoric acid water reducing agent, 0.3% of sodium nitrite, 0.04% of ethylene diamine tetraacetic acid monomethyl ester and 1.5% of calcium oxide. The detection shows that the 2h clear water curing strength of the cement mortar is 31.3MPa, the 4h clear water curing strength is 39.7MPa, the 1d clear water curing strength is 57.6MPa, the 28d clear water curing strength is 67.4MPa, and the seawater erosion resistance coefficient is 1.32.
Comparative example 1
The ferro-aluminate cement comprises the following raw materials in percentage by mass: 90% of ferrous aluminate cement clinker, 2% of fly ash, 6% of anhydrite, 0.16% of polyphosphoric acid water reducing agent, 0.3% of sodium nitrite, 0.04% of ethylene diamine tetraacetic acid monomethyl ester and 1.5% of calcium oxide. Through detection, the 2h clear water curing strength of the cement mortar is 17.2MPa, the 4h clear water curing strength is 26.3MPa, the 1d clear water curing strength is 45.5MPa, the 28d clear water curing strength is 50.2MPa, and the seawater erosion resistance coefficient is 1.17.
Comparative example 2
The ferro-aluminate cement comprises the following raw materials in percentage by mass: 90% of ferrous aluminate cement clinker, 2% of silica fume, 6% of anhydrite, 0.16% of polycarboxylic acid water reducing agent, 0.3% of sodium nitrite, 0.04% of ethylene diamine tetraacetic acid monomethyl ester and 1.5% of calcium oxide. The detection shows that the cement mortar is subjected to slurry bleeding, the 1d clear water curing strength is 49.1MPa, the 28d clear water curing strength is 53.5MPa, and the seawater erosion resistance coefficient is 1.14.
Comparative example 3
The ferro-aluminate cement comprises the following raw materials in percentage by mass: 90% of iron aluminate cement clinker, 2% of silica fume, 6% of anhydrite, 0.16% of polyphosphoric acid water reducing agent, 0.3% of sodium nitrite, 0.04% of triethanolamine and 1.5% of calcium oxide. Through detection, the 2h clear water curing strength of the cement mortar is 19.1MPa, the 4h clear water curing strength is 25.6MPa, the 1d clear water curing strength is 39.8MPa, the 28d clear water curing strength is 50.7MPa, and the seawater erosion resistance coefficient is 1.08.
Comparative example 4
The ferro-aluminate cement comprises the following raw materials in percentage by mass: 90% of iron aluminate cement clinker, 2% of mineral powder, 6% of anhydrite, 0.2% of polycarboxylic acid water reducing agent, 0.3% of sodium nitrite and 1.5% of calcium oxide. Through detection, the cement mortar is subjected to slurry bleeding, the 1d clear water curing strength is 36.9MPa, the 28d clear water curing strength is 46.3MPa, and the seawater erosion resistance coefficient is 1.03.
Therefore, the iron aluminate cement prepared by the proportion of the invention can still be hydrated in the seawater environment to realize the increase of the strength, and the intensity of the iron aluminate cement for repairing is not reduced after seawater erosion by optimizing the proportion, but because the iron aluminate cement for repairing is not reduced because of seawater erosionSupplement of sulfate ions in seawater to make hydration product Ca (OH) 2 Reacts with aluminum glue and iron glue to generate gypsum and ettringite, and the strength is improved to a certain degree.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The iron aluminate cement for repairing is characterized by comprising the following raw materials in parts by mass: 85-90% of ferrous aluminate cement clinker, 1-7% of silica fume, 4-8% of gypsum, 0.08-0.2% of water reducing agent, 0.1-0.5% of nitrite, 0.03-0.05% of reinforcing agent and 2-3% of calcium oxide.
2. The remedial ferroaluminate cement of claim 1, wherein the gypsum is at least one of natural gypsum and industrial by-product gypsum.
3. The remedial ferroaluminate cement of claim 2, wherein the natural gypsum is at least one of anhydrite, hemihydrate gypsum, and dihydrate gypsum.
4. The remedial iron aluminate cement according to claim 2, wherein the industrial by-product gypsum is at least one of desulfurized gypsum and phosphogypsum.
5. The remedial iron aluminate cement of claim 1, wherein the water reducer is a polyphosphoric acid water reducer.
6. The iron aluminate cement for repairing according to claim 5, wherein the polyphosphoric acid water reducer is an early strength type polyphosphoric acid water reducer, the average weight average molecular weight is 35000-45000, and the acid-ether ratio is 4.
7. The remedial ferroaluminate cement of claim 1, wherein the nitrite is at least one of sodium nitrite and potassium nitrite.
8. The remedial ferroaluminate cement of claim 1, wherein the reinforcing agent is ethylene diamine tetraacetic acid monomethyl ester.
9. The remedial iron aluminate cement according to claim 1, wherein the calcium oxide is a highly active calcium oxide obtained by calcining calcium carbonate at 900 ℃.
10. A method for preparing a ferroaluminate cement for repair as set forth in any one of claims 1 to 9, comprising the steps of:
1) Grinding the iron aluminate cement clinker to 400-500m 2 Grinding gypsum into powder of 450-600m 2 After the pressure is/kg, uniformly mixing the pressure-sensitive adhesive with silica fume according to a preset proportion by 1 to obtain a mixture 1;
2) Calcining calcium carbonate in a muffle furnace to prepare high-activity calcium oxide;
3) And respectively adding the water reducing agent, the nitrite, the reinforcing agent and the calcium oxide into the mixture 1 according to the dosage and fully grinding.
CN202211271420.4A 2022-10-17 2022-10-17 Iron aluminate cement for repairing and preparation method thereof Active CN115448681B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446048A (en) * 2014-12-01 2015-03-25 中国建筑材料科学研究总院 High-calcium sulfoaluminate series cement
CN107935422A (en) * 2017-12-27 2018-04-20 成都锦汇科技有限公司 A kind of ferrous aluminate cement
CN108545972A (en) * 2018-07-18 2018-09-18 扬州大学 A kind of high-strength sulphate aluminium cement and preparation method thereof
CN109650828A (en) * 2019-01-01 2019-04-19 中国人民解放军63653部队 A kind of high temperature resistant low yield gas concrete
CN110790526A (en) * 2019-11-18 2020-02-14 广西云燕特种水泥建材有限公司 Marine engineering cement and production method thereof
AU2020104285A4 (en) * 2020-12-23 2021-03-11 Guilin University Of Technology Marine cement and preparation method and application thereof
CN113698117A (en) * 2021-09-17 2021-11-26 山东大学 Solid waste based high-iron sulphoaluminate marine gelled material and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446048A (en) * 2014-12-01 2015-03-25 中国建筑材料科学研究总院 High-calcium sulfoaluminate series cement
CN107935422A (en) * 2017-12-27 2018-04-20 成都锦汇科技有限公司 A kind of ferrous aluminate cement
CN108545972A (en) * 2018-07-18 2018-09-18 扬州大学 A kind of high-strength sulphate aluminium cement and preparation method thereof
CN109650828A (en) * 2019-01-01 2019-04-19 中国人民解放军63653部队 A kind of high temperature resistant low yield gas concrete
CN110790526A (en) * 2019-11-18 2020-02-14 广西云燕特种水泥建材有限公司 Marine engineering cement and production method thereof
AU2020104285A4 (en) * 2020-12-23 2021-03-11 Guilin University Of Technology Marine cement and preparation method and application thereof
CN113698117A (en) * 2021-09-17 2021-11-26 山东大学 Solid waste based high-iron sulphoaluminate marine gelled material and preparation method and application thereof

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