CN109553319B - High alkalinity high strength sulphoaluminate cement - Google Patents
High alkalinity high strength sulphoaluminate cement Download PDFInfo
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- CN109553319B CN109553319B CN201811475545.2A CN201811475545A CN109553319B CN 109553319 B CN109553319 B CN 109553319B CN 201811475545 A CN201811475545 A CN 201811475545A CN 109553319 B CN109553319 B CN 109553319B
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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
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
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- 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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Abstract
The invention provides high-alkalinity high-strength sulphoaluminate cement. The cement comprises 30-90% of sulphoaluminate clinker by mass percentage; 0.1 to 5 percent of potassium hydroxide; 4.9-55% of component A; 5% -30% of gypsum; the component A is a silicon-aluminum material and/or a silicon material; the sulphoaluminate clinker comprises C in percentage by mass2S, 30% -60% (alpha' type C)2S, 30% -60%; beta form C2S，40％‑70％)；C4AF，5％‑30％；2C2S·CaSO41% -5%; 28% -64% of component B; the component B is CaSO4And
Description
Technical Field
The invention relates to the field of marine building materials, in particular to high-alkalinity high-strength sulphoaluminate cement, which is particularly suitable for marine engineering.
Background
The sulphoaluminate cement is a cementing material with the characteristics of quick strength exertion and small-scale service excellent performance, is often used for quick construction of ocean engineering, and has wide application in China in the future in view of increasing importance of ocean strategies.
Although sulphoaluminate cement has the advantages, it has certain disadvantages, wherein the following two disadvantages prevent the application of the sulphoaluminate cement in ocean engineering to a certain extent:
1. if the sulphoaluminate cement is used for reinforced concrete, the main source of the increase of the pH value of a hydration system after hydration by adding water is C in the cement2Hydration of S and hydration of anhydrous calcium sulphoaluminate. As is well known, C2S has a low hydration speed and is difficult to provide more hydroxide radicals for the system in early service, which causes the problems of low alkalinity, insufficient protection capability on reinforcing steel bars and easy occurrence of reinforcing steel bar corrosion of a sulphoaluminate cement reinforced concrete system.
2. The sulphoaluminate cement has good small-grade early strength, the development of the monthly-grade later strength is slow, the later strength is not satisfactory, and the marine building engineering is expected to have good later strength due to the continuous seawater corrosion and scouring action so as to prolong the service life of the marine building engineering.
In order to widely popularize and apply the sulphoaluminate cement as a cementing material in ocean engineering, the two technical problems need to be overcome.
Disclosure of Invention
The invention mainly aims to provide high-alkalinity high-strength sulphoaluminate cement, which is used for construction of ocean engineering, can provide high alkalinity to prevent corrosion of reinforcing steel bars in the early construction period, can provide high strength to prolong the service life in the later construction period, has good comprehensive performance and is more practical.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The sulphoaluminate cement provided by the invention comprises the following components in percentage by mass:
the component A is a silicon-aluminum material and/or a silicon material.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the sulfoaluminate cement comprises, by mass percent, the sulfoaluminate clinker:
the component B is CaSO4And
a mixture of (a).
Preferably, the above-mentioned sulfoaluminate cement, wherein said C2S comprises the following components in percentage by mass: alpha' type C2S, 30% -60%; beta form C2S，40％-70％。
Preferably, the sulfoaluminate cement comprises, by mass percent, the sulfoaluminate clinker:
preferably, the sulphoaluminate cement comprises the following components in percentage by mass:
preferably, the sulphoaluminate cement is a mixture of a alumino-silicate material and a siliceous material.
Preferably, the sulphoaluminate cement is prepared from alumino-silicate materials such as slag, phosphorous slag and/or fly ash.
Preferably, the alumino-silicate cement is one in which the alumino-silicate material is slag powder, phosphorous slag powder and/or ultrafine fly ash powder.
Preferably, the sulphoaluminate cement is prepared from the siliceous material of wollastonite powder, nano-silica and/or siliceous aerogel.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The application of the sulphoaluminate cement in ocean engineering is provided according to the invention.
By the technical scheme, the high-alkalinity high-strength sulphoaluminate cement provided by the invention at least has the following advantages:
1. the high-alkalinity high-strength sulphoaluminate cement is prepared by introducing a certain amount of alpha' type C with high hydration speed into a cement system2S, the cement system can generate a large amount of hydrogen containing hydroxyl at the early stage of constructionCalcium oxide, thereby improving the alkalinity of the early hydration system of the cement and protecting the reinforcing steel bars in the concrete from being corroded;
2. the high-alkalinity high-strength sulphoaluminate cement has the advantages that 0.1-5% of potassium hydroxide is added into a cement system, so that the cement system contains a large amount of hydroxide radicals in the early hydration stage, the alkalinity of the early hydration system of the cement is improved, and reinforcing steel bars in concrete are protected from being rusted;
3. the high-alkalinity high-strength sulphoaluminate cement keeps higher content of C in a cement system4AF, so that the cement system contains more hydroxide radicals in the hydration process, thereby improving the alkalinity of the early hydration system of the cement and protecting reinforcing steel bars in concrete from corrosion;
4. the high-alkalinity high-strength sulphoaluminate cement is prepared by introducing a certain amount of 2C into a cement system2S·CaSO4A certain amount of alpha' type C with higher hydration speed2S and higher C content4AF enables a cement system to generate more active gelled substances during hydration, and the later strength of the cement is improved, so that the service life of the cement is prolonged;
5. the high-alkalinity high-strength sulphoaluminate cement enables a cement system to generate a large amount of active gelled substances in the later hydration stage by introducing the alumino-silicate material and/or the siliceous material and 0.1-5% of potassium hydroxide into the cement system, so that the later strength of the cement is improved, and the service life of the cement is prolonged.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following embodiments are combined with the preferred embodiments to describe the specific implementation, structure, characteristics and effects of the high-alkalinity high-strength sulphoaluminate cement according to the present invention in detail.
The invention provides sulphoaluminate cement, which comprises the following components in percentage by mass:
the component A is a silicon-aluminum material and/or a silicon material.
The sulphoaluminate cement system also comprises gypsum besides the sulphoaluminate clinker, the alumino-silicate material and/or siliceous material and the potassium hydroxide, and the content range of the gypsum is not critical to the invention, but is also an important component of the sulphoaluminate cement.
The gypsum can be anhydrite.
Preferably, the sulfoaluminate cement comprises, by mass percent, the sulfoaluminate clinker:
the component B is CaSO4And
a mixture of (a).
Said C2S is dicalcium silicate; said C4AF is tetracalcium aluminoferrite; said 2C2S·CaSO4Calcium sulfosilicate; said
Is anhydrous calcium sulphoaluminate.
In the sulfoaluminate clinker system, except the C2S、C4AF. And 2C2S·CaSO4Besides, component B is also included, the content range of the component B is not critical to the invention, but is also an important component in the sulphoaluminate clinker.
Preferably, beforeThe sulphoaluminate cement, wherein C2S comprises the following components in percentage by mass: alpha' type C2S, 30% -60%; beta form C2S，40％-70％。
Preferably, the sulfoaluminate cement comprises, by mass percent, the sulfoaluminate clinker:
preferably, the sulphoaluminate cement comprises the following components in percentage by mass:
preferably, the sulphoaluminate cement is a mixture of a alumino-silicate material and a siliceous material.
According to the construction requirements of marine environment, if the post strength is mainly improved, the high-alkalinity high-strength sulphoaluminate cement is a mixture of a silicon-aluminum material and a silicon material in a cement system, rather than the silicon-aluminum material or the silicon material. The mixing ratio of the silicon-aluminum material and the silicon material in the component A can be adjusted according to performance requirements.
Preferably, the sulphoaluminate cement is prepared from alumino-silicate materials such as slag, phosphorous slag and/or fly ash.
Preferably, the alumino-silicate cement is one in which the alumino-silicate material is slag powder, phosphorous slag powder and/or ultrafine fly ash powder.
Preferably, the sulphoaluminate cement is prepared from the siliceous material of wollastonite powder, nano-silica and/or siliceous aerogel.
The silicon-aluminum material can be selected from the following materials, but is not limited to the following materials: slag, slag powder, fly ash ultrafine powder, phosphorus slag and phosphorus slag powder.
The siliceous material can be selected from, but is not limited to, the following materials: silica fume powder, nano silicon dioxide and silica aerogel.
The invention also provides application of the sulphoaluminate cement in ocean engineering.
The high-alkalinity high-strength sulphoaluminate cement meets the construction requirements of marine environment, if the early alkalinity is mainly improved, the alpha' type C in the clinker system composition2The S content should be as high as possible.
When the existing sulphoaluminate cement is used for preparing reinforced concrete for ocean engineering, the basicity of a sulphoaluminate cement system is low because hydroxide radicals generated when the sulphoaluminate cement system is hydrated are less, and the corrosion of seawater to the steel bars in the concrete can not be effectively prevented in the early service period. The invention designs the composition of a novel sulphoaluminate cement system, and simultaneously introduces a plurality of materials which can generate hydroxide radicals during hydration, such as a certain content of alpha' type C2S, 0.1-5% of potassium hydroxide and 5-30% of C4AF, so that the alkalinity of the sulphoaluminate cement system in the early stage of cement hydration is improved, and the effect of well protecting the reinforcing steel bars is achieved.
When the existing sulphoaluminate cement is used for preparing reinforced concrete for ocean engineering, the long-age month-level later strength of the sulphoaluminate cement develops slowly, and the ocean engineering is expected to have good later strength due to continuous seawater corrosion and scouring. The invention designs the composition of a novel sulphoaluminate cement system, and simultaneously introduces a plurality of materials which can generate high-activity gelled substances during a long-term hydration period, such as a certain amount of 2C2S·CaSO4Silicon-aluminum material and/or silicon material, 0.1-5% of potassium hydroxide and a certain amount of alpha' type C with higher hydration speed2S, when the materials exist simultaneously, the materials can react with each other, so that a cement system generates a large amount of active gelled substances through calcium-silicon reaction and calcium-sulfur-aluminum reaction at the later stage of hydration, the synergistic effect of the materials is better than that of the materials existing independently, the strength of the sulphoaluminate cement system in the long-term hydration period is improved, and the materials can be well used in the oceanAnd (4) the function of the environment.
This is further illustrated by the following specific examples.
Examples 1-3 and comparative examples 1-3:
a sample of the sulphoaluminate clinker is prepared according to the formula listed in the following table 1, the alkalinity of the sulphoaluminate clinker hydration system is measured according to GB20472-2006, and the detection result is shown in the following table 1, wherein the proportion in the table is weight percent.
TABLE 1 formulation and Properties of sulphoaluminate Clinker
As can be seen from the data presented in Table 1 above, when C is the sulfoaluminate clinker2S comprises 30% of alpha' type C2And when S is higher, the alkalinity of the hydration system of the sulphoaluminate clinker is increased, and the PH value is increased by 0.7, which is shown in the data of example 1 and comparative example 1.
As can be seen from the data presented in Table 1 above, when C is the sulfoaluminate clinker2S comprises 53.3% of alpha' type C2And when S is higher, the alkalinity of the hydration system of the sulphoaluminate clinker is increased, and the PH value is increased by 1.1, which is shown in the data of example 2 and comparative example 2.
As can be seen from the data presented in Table 1 above, when C is the sulfoaluminate clinker2S comprises 60% of alpha' type C2S, the alkalinity of the sulphoaluminate clinker hydration system is increased, and the PH value is increased by 0.8, which is shown in the data of example 3 and comparative example 3.
As can be seen from the data of examples 1-3 and comparative examples 1-3, a certain amount of alpha' form C is introduced into the system composition of the sulfoaluminate clinker2S, the alkalinity of the cement hydration system is favorably improved; furthermore, with the introduction of alpha' form C2The content of S is increased because the mixture ratio of other components in the clinker is also increasedAnd the change shows the law that the influence on the alkalinity of a hydration system is increased and then decreased. Based on the above experimental data, it can be seen that C is used in the sulfoaluminate clinker in order for the cement to exhibit early high alkalinity2S starting material, in which the alpha' form C2The content of S is greater than or equal to 30% and less than or equal to 60%; beta form C2The content of S is greater than or equal to 40% and less than or equal to 70%.
Example 4-example 7 and comparative example 4-comparative example 7:
the formula of the sulphoaluminate clinker with the highest early alkalinity, namely the sulphoaluminate cement of the example 2, is selected, samples of the sulphoaluminate cement are prepared according to the formula listed in the following table 2, the alkalinity of a hydration system of the sulphoaluminate cement is measured according to the standard GB20472-2006, the compressive strength of the sulphoaluminate cement is measured according to the standard GB/T17671-1999, and the detection result is shown in the table 2, wherein the proportion is weight percent.
TABLE 2 formulation and Properties of sulphoaluminate cements
As can be seen from the data presented in table 2 above, in comparative examples 4 to 7, potassium hydroxide was not added, but only anhydrite, alumino-silica materials (such as slag powder and/or phosphorous slag powder) and/or siliceous materials (such as silica fume powder and/or nano-silica) were introduced, which somewhat reduced the basicity of the sulphoaluminate cement; moreover, the higher the proportion of the above-mentioned raw material introduced, the more its basicity is decreased, for example, in comparative example 4, 65% of the above-mentioned material is introduced, its basicity is decreased by 1.6; in comparative example 7, 55% of the above material was introduced, and its basicity was reduced by 2.2; in comparative example 6, 30% of the above material was introduced, and its basicity was reduced by 0.8; in comparative example 5, 10% of the above material was introduced, and its basicity was reduced by 0.6; further, the degree of influence varies slightly depending on the kind of the silica-alumina material and the silica material. However, in practice, the abovementioned substances anhydrite, alumino-silica and/or siliceous material, such as wollastonite, must be introduced in order to ensure good long-term strength of the system.
The introduction of potassium hydroxide into the cement system has great influence on the hydration alkalinity and the long-term compressive strength of the cement system.
In examples 4 to 7, the sulphoaluminate cement system has high alkalinity by introducing 0.1 to 5 percent of potassium hydroxide, and as can be seen from example 5 and comparative example 5, the alkalinity is increased by 0.5 by introducing 0.1 percent of potassium hydroxide; as can be seen from example 6 and comparative example 6, the basicity of potassium hydroxide is increased by 0.8 by introducing 1%; as can be seen from example 7 and comparative example 7, the basicity of potassium hydroxide is increased by 1.5 by introducing 1% potassium hydroxide; as can be seen from example 4 and comparative example 4, the basicity was increased by 1.0 by the introduction of 5% potassium hydroxide.
The introduction of potassium hydroxide not only affects the alkalinity of the cement system, but also has a great influence on the improvement of the long-term strength of the cement. In comparative examples 4 to 7, the increase in the 180-day compressive strength relative to the 90-day compressive strength was less than or equal to 3MPa, with little change. In examples 4-7, the compressive strength of the cement is improved very significantly by introducing 0.1% -5% of potassium hydroxide, for example: by introducing 0.1 percent of potassium hydroxide into the mixture in the example 5, compared with the comparative example 5, the compressive strength of the mixture is improved by 8MPa in 90 days and 18MPa in 180 days; compared with the comparative example 6, the compressive strength of the steel plate is improved by 15MPa in 90 days and 23MPa in 180 days by introducing 1% of potassium hydroxide into the steel plate in the example 6; compared with the comparative example 7, the compressive strength of the steel plate is improved by 6MPa in 90 days and 12MPa in 180 days by introducing 1% of potassium hydroxide into the steel plate in the example 7; in example 4, 5% of potassium hydroxide was introduced, and the 90-day compressive strength was increased by 11MPa and the 180-day compressive strength was increased by 18MPa, as compared with comparative example 4. As can be seen from the data in Table 2, as the content of potassium hydroxide is changed in the cement system, the influence of the potassium hydroxide on the long-term strength of the cement is increased rapidly first and then gradually decreased, and the efficiency of increasing the pH value shows a rule of increasing first and then decreasing.
The results of the above-mentioned specific examples 1 to 7 show that it has high early alkalinity and high long-age compressive strength as compared with the samples of comparative examples 1 to 7, and can be suitably used for construction applications in marine engineering.
The recitation of numerical ranges herein includes all numbers subsumed within that range and includes any two numbers subsumed within that range.
The features of the invention claimed and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to the scope of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (8)
1. The sulphoaluminate cement is characterized by comprising the following components in percentage by mass:
the component A is a silicon-aluminum material and/or a silicon material;
the sulphoaluminate clinker comprises the following components in percentage by mass:
the component B is CaSO4And
a mixture of (a);
said C2S comprises the following components in percentage by mass:
alpha' type C2S，30％-60％；
Beta form C2S，40％-70％。
2. The sulphoaluminate cement of claim 1, wherein the sulphoaluminate clinker comprises, in mass percent:
3. the sulphoaluminate cement of claim 1, comprising, in mass percent:
4. sulphoaluminate cement according to claim 3,
the component A is a mixture of a silicon-aluminum material and a silicon material.
5. The sulfoaluminate cement of claim 1,
the silicon-aluminum material is slag, phosphorous slag and/or fly ash.
6. The sulfoaluminate cement of claim 1,
the silicon-aluminum material is slag powder, phosphorus slag powder and/or ultrafine coal ash powder.
7. The sulfoaluminate cement of claim 1,
the siliceous material is silica fume, nano silicon dioxide and/or siliceous aerogel.
8. Use of the sulphoaluminate cement according to any of claims 1 to 7 in marine engineering.
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