CN114477809B - Inorganic cementing material with strength and volume stability coordinately developed and application thereof - Google Patents

Inorganic cementing material with strength and volume stability coordinately developed and application thereof Download PDF

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CN114477809B
CN114477809B CN202210161991.6A CN202210161991A CN114477809B CN 114477809 B CN114477809 B CN 114477809B CN 202210161991 A CN202210161991 A CN 202210161991A CN 114477809 B CN114477809 B CN 114477809B
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cementing material
inorganic
inorganic cementing
mass
strength
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CN114477809A (en
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崔素萍
郑焱
毛倩瑾
王剑锋
王亚丽
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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
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • C04B7/326—Calcium aluminohalide cements, e.g. based on 11CaO.7Al2O3.CaX2, where X is Cl or F
    • 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
    • C04B7/02—Portland cement
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/10—Coherent pavings made in situ made of road-metal and binders of road-metal and cement or like binders
    • E01C7/14—Concrete paving
    • E01C7/142—Mixtures or their components, e.g. aggregate
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01D—CONSTRUCTION OF BRIDGES, ELEVATED ROADWAYS OR VIADUCTS; ASSEMBLY OF BRIDGES
    • E01D1/00—Bridges in general
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01D—CONSTRUCTION OF BRIDGES, ELEVATED ROADWAYS OR VIADUCTS; ASSEMBLY OF BRIDGES
    • E01D2101/00—Material constitution of bridges
    • E01D2101/20—Concrete, stone or stone-like material
    • E01D2101/24—Concrete

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

Abstract

The invention relates to the technical field of cement-based materials, in particular to an inorganic cementing material with strength and volume stability coordinately developed and application thereof. The invention provides an inorganic cementing material, the mineral composition comprises C 3 S、C 2 S、C 3 A、C 4 AF、
Figure DDA0003515190120000013
And
Figure DDA0003515190120000012
wherein C is 3 S and C 2 The sum of the mass of S is less than 68 percent of the total mass of the inorganic cementing material; c 3 A and
Figure DDA0003515190120000014
the mass sum of (a) and (b) accounts for 16-18% of the total mass of the inorganic cementing material. The inorganic cementing material has higher strength and better volume stability, and the blending mode is more time-saving and labor-saving, thereby having more guiding significance for practical application; in addition, the inorganic cementing material has higher strength and volume stability, and can obviously improve the durability of a concrete structure when being applied to concrete.

Description

Inorganic cementing material with strength and volume stability coordinately developed and application thereof
Technical Field
The invention relates to the technical field of cement-based materials, in particular to an inorganic cementing material with strength and volume stability coordinately developed and application thereof.
Background
At present, the emission of carbon dioxide generated directly and indirectly in the cement production process is high, so that the research and development of high-performance inorganic cementing materials and the reduction of the consumption of traditional cement clinker are one of the important ways for realizing energy conservation, emission reduction and sustainable development in the current cement industry.
The results of the prior research show that the method is introduced into the traditional portland cement ore phase systemOther mineral constituents (such as anhydrous calcium sulphoaluminate,
Figure BDA0003515190100000011
) Or compound cement (such as silicate-sulphoaluminate cement system) is prepared, and the characteristics of improving the early strength of the cement, improving the volume stability of the cement-based material and the like are proved.
The existing blending modes of the composite cement are divided into two types: one is to mix the raw materials from the front end, and calcine the raw materials according to the designed raw material proportion to obtain the single-system cement clinker containing minerals contained in the silicate-sulphoaluminate cement system; the other is to mix from the end product, and directly compound the cement clinkers of two different systems of silicate and sulphoaluminate according to the designed proportion.
However, the existing compound cement blending method has the following problems:
(1) For the first front-end raw material blending method, an uncontrollable byproduct is often generated in the calcining process, the temperature difference between the calcining temperature of the effective mineral (such as anhydrous calcium sulfoaluminate) and the calcining temperature of other minerals is large, secondary calcining is often needed, the calcining process is complex, the stability of the mineral composition is poor, and the energy consumption in the calcining process is high.
(2) For the second latter-stage product blending mode, although the problem of high calcining energy consumption is avoided, the silicates and sulphoaluminates of different types and grades have deviation in mineral composition and content, so that the optimal ratio needs to be verified by multiple tests, and the blending is long in time consumption and complicated to operate; according to experience, the volume stability is improved, and simultaneously, the compression strength/breaking strength of the cement-based material is reduced, and particularly, the problems of insufficient strength development, reduced durability and the like can occur at the later stage of hydration.
Disclosure of Invention
In a first aspect, the present invention provides a novel inorganic cementitious material that combines high strength with volume stability.
The mineral composition of the inorganic cementing material comprises C 3 S、C 2 S、C 3 A、C 4 AF、
Figure BDA0003515190100000021
And
Figure BDA0003515190100000022
wherein: c 3 S and C 2 The sum of the S mass is less than 68 percent of the total mass of the inorganic cementing material; c 3 A and
Figure BDA0003515190100000023
the mass sum of (a) and (b) accounts for 16-18% of the total mass of the inorganic cementing material.
Six minerals are screened from the existing common mineral components to serve as compound components, and C is further controlled on the basis 3 S and C 2 Mass sum of S and C 3 A and
Figure BDA0003515190100000024
the mass sum of the inorganic cementing material is proportional, and the obtained inorganic cementing material has higher strength and volume stability by controlling the proportional relation of the two groups, so that the durability of concrete can be effectively improved.
According to the invention, by reasonably designing the mineral composition, the compounding efficiency of the composite cement in practical application is obviously improved by using a simpler composite cement composition design, the development and the volume stability of the early, middle and later strength of hydration are considered, and the problems of high energy consumption, complex calcination process, poor mineral stability and the like in a raw material blending mode and the problems of insufficient later strength development, reverse shrinkage and the like in a later-stage product blending mode are solved.
The durability of the inorganic cementing material provided by the invention is improved, so that the long-term demand of the cement-based material can be effectively reduced, and further, the carbon emission reduction of the whole process from a production source to application is realized.
Further, the invention further improves the strength and the volume stability of the obtained inorganic cementing material by optimizing the content of each mineral component. The method specifically comprises the following steps:
control of said C 3 S is contained in the inorganic cementing material by mass percent20～25％。
Control of said C 2 The mass percentage of S in the inorganic cementing material is 42-48%.
Control of said C 3 The mass percentage of A relative to the inorganic cementing material is 10-12%.
Control of said C 4 The mass percentage of AF in the inorganic cementing material is 7-10%.
Control the
Figure BDA0003515190100000027
The mass percentage of the inorganic gelled material is 5-8%.
Control the
Figure BDA0003515190100000026
The mass percentage of the inorganic gelled material is 6-10%.
By controlling the content range and the proportional relation of the components in the system, the mineral components play a synergistic effect, can meet the stable increase of early and later strength, effectively relieves the phenomenon of retraction commonly existing in the existing inorganic cementing material, and has better volume stability.
As one embodiment of the invention, the inorganic cementing material comprises the following components in parts by weight: c 3 S (20-25) parts, C 2 S (42-48) and C 3 A (10-12) parts, C 4 7 to 10 portions of AF,
Figure BDA0003515190100000031
(5-8) parts of,
Figure BDA0003515190100000032
(6-10).
Preferably, the inorganic cementing material comprises the following components in parts by weight: c 3 S (22-24) and C 2 S (43-45) and C 3 A (11-12) parts, C 4 8 to 9 portions of AF,
Figure BDA0003515190100000033
(5-7) parts of,
Figure BDA0003515190100000034
(7～9)。
In the inorganic cementing material, the chemical component is CaO-Al 2 O 3 -SiO 2 -Fe 2 O 3 -SO 3 A quinary system, wherein CaO (55-65)%, siO 2 (19～21)％、Al 2 O 3 (5～8)％、Fe 2 O 3 (3～5)％、SO 3 (2-8)%, and other components (MgO, na) 2 O、TiO 2 f-CaO, etc.) is less than 5%.
In the inorganic cementitious material of the present invention, the component C 3 S、C 2 S、C 3 A、C 4 AF、
Figure BDA0003515190100000035
And
Figure BDA0003515190100000036
can be obtained by commercially purchasing or calcining portland cement clinker.
Wherein
Figure BDA0003515190100000037
It can also be obtained by the following calcination method: mixing calcium carbonate, aluminum oxide and CaSO 4 ·2H 2 The mass fraction of O is respectively according to (1.5-2): (1.5-2): 1, mixing and grinding into raw materials; mixing the raw materials with water, press molding, oven drying, and firing at 1300-1400 deg.C.
In a second aspect, the invention provides the application of the inorganic cementing material in road and bridge construction, ocean engineering and rush-repair engineering.
In a third aspect, the present invention provides a concrete structure, which employs the above inorganic cementitious material.
The beneficial effects obtained by the invention are as follows:
according to the invention, through screening specific six mineral components and optimizing the proportioning relation, the inorganic cementing material has higher strength and better volume stability, and breakthrough progress is achieved. Although the prior art also discloses a material consisting of six minerals, the relationship between the proportional relationship among the minerals and the overall application performance of the material has not been clearly studied, and therefore, the proportioning relationship proposed by the invention for ensuring the synergistic development of both the strength and the volume stability is not obvious.
Meanwhile, the invention adopts a mineral component allocation mode, so that the time and the labor are saved, the calcining energy consumption is reduced, the carbon emission reduction of the whole process from the preparation from a production source to the application is realized, and the method has more guiding significance to the practical application; and has certain reference value for the design of the composite cement containing similar mineral components which also needs to take the strength and the volume stability into consideration.
In addition, the inorganic cementing material has higher strength and volume stability, and can obviously improve the durability of a concrete structure when being applied to concrete.
Drawings
FIG. 1 shows the results of a concrete limited expansion test.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Each of the components in the following examples can be obtained by commercially purchasing or calcining portland cement clinker.
Wherein
Figure BDA0003515190100000044
It can also be obtained by the following calcination method:
mixing calcium carbonate, aluminum oxide and CaSO 4 ·2H 2 The mass fraction of O is respectively according to (1.5-2): (1.5-2): 1, mixing and grinding into raw materials; mixing the raw materials with water, press molding, oven drying, and firing at 1300-1400 deg.C.
Examples 1 to 3
This example provides 3 groups of inorganic gelled materials with strength and volume stability developed in harmony, and the specific mineral composition is as follows:
table 1 examples mineral composition of inorganic cementitious material
Figure BDA0003515190100000041
Wherein, C of examples 1 to 3 3 S and C 2 The sum of the mass of S accounts for 66.2%, 66.7% and 65.7% of the total mass of the inorganic cementing material respectively; c 3 A and
Figure BDA0003515190100000042
the mass sum of (a) and (b) accounts for 17.2%, 16.9% and 17.5% of the total mass of the inorganic cementing material.
Comparative example 1
This comparative example provides an inorganic cementitious material having a mineral composition as shown in table 2 for comparative example 1. Wherein, C 3 S and C 2 The mass sum of the S accounts for 71 percent of the total mass of the inorganic cementing material; c 3 A and
Figure BDA0003515190100000043
the sum of the mass of (a) and (b) accounts for 14.4% of the total mass of the inorganic cementitious material.
Comparative example 2
This comparative example provides a portland cement having a mineral composition as shown in comparative example 2 of table 2. Wherein, C 3 S and C 2 The mass sum of S accounts for 78% of the total mass of the inorganic cementing material; c 3 The mass of A accounts for 7% of the total mass of the inorganic cementing material.
Table 2 comparative examples 1-2 mineral compositions of inorganic cementitious materials
Figure BDA0003515190100000051
Comparative test of effects
1. Compressive strength and volume stability
The inorganic cement materials obtained in examples 1 to 3 and comparative examples 1 and 2 were tested, and the results of strength and volume stability were as follows:
in the test, the compressive strength of the cement mortar sample is measured by using national standard GB/T17671-1999 method for testing the strength of cement mortar (ISO method).
And meanwhile, the expansion rate limit test is adopted to verify the concrete compensation shrinkage performance of different inorganic cementing materials. And when the sample is hydrated for 14 days, the sample curing condition is changed from standard curing to constant-temperature and constant-humidity curing with the temperature of 20 +/-2 ℃ and the relative humidity of 60 +/-2%.
The test adopts the national standard GB/T50082-2009 test method standard for testing the long-term performance and the durability of the common concrete to measure the frost resistance, the carbonization resistance and the penetration resistance of the test sample.
The test results are shown in the following table and fig. 1.
TABLE 3 compressive Strength
Figure BDA0003515190100000052
The results show that the inorganic cement materials obtained in examples 1 to 3 have both high compressive strength and high volume stability, and particularly show high early strength. In contrast, comparative example 1, which is not well matched, has difficulty in obtaining high compressive strength and volume stability.
Comparative example 2 is a mineral composition of a conventional portland cement clinker which has inferior compressive strength and volume stability to those of comparative example 1 and examples 1-3.
2. Durability
The inorganic cementing materials obtained in example 1, comparative example 1 and comparative example 2 are applied to concrete respectively, and the durability of the obtained concrete test block is tested, and the test results are as follows:
TABLE 4 durability test
Figure BDA0003515190100000061
The results show that, compared with the durability test results of comparative example 1, the change of the anti-carbonization performance of example 1 is not obvious, and the anti-freezing performance and the anti-permeability performance are much higher than the indexes of comparative example 1. Compared with common portland cement (comparative example 2), the impermeability and the freeze-thaw resistance of example 1 are both improved by more than 45%, and the carbonization resistance is not obviously different.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.

Claims (6)

1. An inorganic cementitious material characterised in that the mineral composition comprises C 3 S、C 2 S、C 3 A、C 4 AF、
Figure FDA0003879320970000011
And
Figure FDA0003879320970000012
wherein:
C 3 s and C 2 The sum of the mass of S is less than 68 percent of the total mass of the inorganic cementing material;
C 3 a and
Figure FDA0003879320970000013
the mass sum of the components accounts for 16 to 18 percent of the total mass of the inorganic cementing material;
control of said C 3 The mass percentage of S in the inorganic cementing material is 20-25%;
control of said C 2 The mass percentage of S in the inorganic cementing material is 42-48%;
control of said C 3 The mass percentage of A relative to the inorganic cementing material is 10-12%;
control of said C 4 The mass percentage of AF in the inorganic cementing material is 7-10%;
control the
Figure FDA0003879320970000014
The mass percentage of the inorganic cementing material is 5-8%;
control the
Figure FDA0003879320970000015
The mass percentage of the inorganic cementing material is 6-10%.
2. The inorganic cementitious material according to claim 1, characterised in that it comprises the following components in parts by weight: c 3 S (20-25) parts, C 2 S (42-48) parts, C 3 A (10-12) parts, C 4 7 to 10 portions of AF,
Figure FDA0003879320970000016
Portions are,
Figure FDA0003879320970000017
And (4) portions are obtained.
3. The inorganic cementitious material according to claim 2, characterised by comprising the following components in parts by weight: c 3 S (22-24) and C 2 S (43-45) and C 3 A (11-12) parts, C 4 AF (8-9) portions,
Figure FDA0003879320970000018
Portions are,
Figure FDA0003879320970000019
And (4) portions are obtained.
4. The inorganic cementitious material according to claim 2, characterised in that its chemical composition is CaO-SiO 2 -Al 2 O 3 -Fe 2 O 3 -SO 3 A quinary system, wherein CaO (55-65)%, siO 2 (19～21)％、Al 2 O 3 (5～8)％、Fe 2 O 3 (3～5)％、SO 3 (2-8)%, and the sum of other components is less than 5%;
other components include MgO and Na 2 O、TiO 2 、f-CaO。
5. The use of the inorganic cementitious material according to any one of claims 1 to 4 in the construction of roads and bridges, marine engineering, and emergency repair works.
6. A concrete structure characterized in that the inorganic cementitious material according to any one of claims 1 to 4 is used.
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DE4204227C1 (en) * 1992-02-13 1993-02-11 Ivan Prof. Dr. 3380 Goslar De Odler Portland cement clinker prepn. - by firing mixt. of calcium oxide, silica, aluminium@ and ferric oxide in presence of additive contg. sulphate and fluorine ions
CN101041560A (en) * 2003-09-17 2007-09-26 中国建筑材料科学研究院 High-magnesium low-heat portland cement clinker aggregate and preparation method thereof
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CN107935423B (en) * 2017-11-22 2020-12-08 唐山北极熊建材有限公司 Corrosion-resistant high belite sulphoaluminate cement clinker, preparation method thereof, corrosion-resistant high belite sulphoaluminate cement and preparation method thereof
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