Self-compacting concrete and preparation method thereof
Technical Field
The invention belongs to the technical field of building materials. And more particularly, to a self-compacting concrete and a method for preparing the same.
Background
Self-Compacting Concrete (Self Compacting Concrete or Self-Compacting Concrete SCC) is a Concrete which can flow and compact under the action of Self gravity, can completely fill a formwork even if compact steel bars exist, and simultaneously obtains good homogeneity without additional vibration.
The red mud is industrial solid waste discharged after alumina is extracted from bauxite, and can be divided into sintering process red mud and Bayer process red mud according to different production modesThe red mud produced by the otic method and the red mud produced by the combined method (namely the sintering method and the Bayer method are combined). Because the red mud of the sintering process has higher pozzolanic activity than the red mud of the Bayer process, the red mud of the sintering process is generally used in the concrete at present. However, the bayer process red mud has a good internal curing effect on concrete, and the inventor of the chinese patent application CN105198324A uses the bayer process red mud as a self-compacting concrete admixture, so that the strength of the self-compacting concrete material is improved, and the shrinkage of the self-compacting concrete is reduced. However, if the Bayer process red mud is required to play an internal curing role, the addition amount is very large, the mass ratio of cement to red mud in the concrete reaches 2: 1-1: 1, and the Bayer process red mud contains high proportion of Na2O, the existence of a large amount of red mud can cause serious efflorescence and alkali aggregate reaction of the cement-based material. If a small amount of Bayer process red mud is added, the curing effect can be exerted, and the pozzolanic activity of the Bayer process red mud needs to be improved. Research reports that the activity of Bayer process red mud can be improved by calcining Bayer process red mud and oil shale at the temperature of 600-700 DEG C[1]However, the authors do not continue to study the application performance of activated red mud in concrete; meanwhile, Chinese patent CN10451881A discloses a self-compacting cement concrete doped with Bayer process red mud, which adopts porcelain stone tailings to replace oil shale, and after calcining at 600-700 ℃, a calcined product with higher activity is prepared by cooling in a fast-heating and slow-cooling mode, and the strength and the shrinkage performance of the concrete can be obviously improved after the calcined product is added into the concrete, but the final setting time of the concrete is also prolonged. Therefore, the difficulties to be overcome by the application of the bayer process red mud at present are as follows: the activity of the volcanic ash is improved, and the volcanic ash can play a role of internal curing by being added into self-compacting concrete in a small amount; secondly, the defect of overlong final setting time of concrete caused by Bayer process red mud activated by a calcination mode is eliminated.
The coal gangue is a black grey rock with lower carbon content and harder than coal, which is associated with the coal bed in the process of coal formation. Spontaneous combustion gangue due to the presence of amorphous SiO2And Al2O3And thus has a certain pozzolanic activity, is usually added to concreteThe coarse aggregate (CN101439952A, CN105000832A) was used. The strength and water absorption of concrete can be obviously improved by adding the calcined and activated coal gangue, and the cost of concrete engineering is reduced, but generally, in order to achieve the particle size, the coal gangue needs to be crushed for multiple times, a large amount of fine aggregates with smaller particle size are generated in the crushing process, and the fine aggregates are not reasonably utilized at present, so that the pollution to the environment and the waste of resources are caused. At present, no literature reports that coal gangue with smaller grain size is used as an active admixture of self-compacting concrete.
Meanwhile, unburnt waste rocks are actually abundantly existed and cannot be fully utilized at present, and X-ray diffraction structural analysis shows that active SiO is hardly found in the waste rocks2And Al2O3. If unburnt gangue is used, the problem of activity is solved firstly. At present, the patent reports that the red mud is used for activating the red mud (CN103420406B), but the red mud used in the method is preferably sintering red mud, and the activating effect of the Bayer red mud is not ideal. Meanwhile, according to chemical components, the coal gangue can be divided into claystone gangue, sandstone gangue, aluminum gangue and calcareous gangue, the composition difference of each type of gangue is large (each type of main mineral forms the following table 1), and sandstone unburnt gangue is more commonly used for preparing aggregate, but the patent does not mention which type of gangue is activated by red mud, and the influence of the coal gangue on the activity of the red mud in the activation process cannot be known.
TABLE 1 composition of different types of gangue minerals
Reference [1 ]: saussurea involucrate, Fengpeng, sun-shaped tiger, snow white, Bayer red mud heat alteration activity optimization research.
Disclosure of Invention
The invention aims to solve the technical problems of large admixture of Bayer process red mud and easy overlong final setting time of concrete in the existing self-compacting concrete, and provides the self-compacting concrete with good mechanical property and small shrinkage.
The invention achieves the purpose of simultaneously activating the claystone gangue and the Bayer process red mud by calcining the claystone gangue and the Bayer process red mud at a certain temperature, and the mutual activation mechanism is as follows: at 400-650 ℃, the kaolinite contained in the claystone gangue undergoes dehydration reaction and is converted into metakaolinite, and at 600-700 ℃, the metakaolin is decomposed into gamma-Al2O3And amorphous SiO2The activated claystone gangue is added into the self-compacting concrete to improve the frost resistance of the self-compacting concrete; h generated by dehydration reaction of kaolinite2O belongs to a strong polar substance and can generate a strong alteration effect on the surface of the Bayer process red mud, so that the lattice distortion degree of the material surface is increased, the volcanic ash activity of the Bayer process red mud is improved, and finally, the effect of simultaneously activating claystone gangue and the Bayer process red mud is realized.
In order to achieve the purpose, the invention adopts the following technical scheme: the self-compacting concrete comprises the following raw materials in parts by weight: 200-325 parts of Portland cement, 100-135 parts of active admixture, 1350-1600 parts of aggregate, 8-15 parts of naphthalene-based high-efficiency water reducing agent and 150-190 parts of water; the active admixture is an activated product obtained by calcining Bayer process red mud and coal gangue at 600-700 ℃ for 1-2 hours.
Further, the grain size of the coal gangue is less than 0.1 mm. The gangue residual material with the grain diameter less than 0.125mm is preferably adopted, the residual material generated by the gangue in multiple crushing is utilized, on one hand, the environmental pollution and the resource waste are avoided, on the other hand, the rheological property of the concrete can be improved by blending the admixture with small grain diameter into the self-compacting concrete
Further, the coal gangue is claystone gangue and/or calcareous rock gangue. Of the four types of coal gangue, the claystone gangue is the only gangue containing Al at the same time2O3And SiO2Of (SiO)2:40~70%,Al2O3: 15-30%) and gangue Al2O3And SiO2Of (1) containsAmount, especially active Al2O3And SiO2The content is the main factor for determining the activity of the coal gangue. However, if only one type of coal gangue is added, claystone gangue needs to be calcined at 850 ℃ to activate the activity, and the calcined product is used as an admixture of concrete, and the problem of long final setting time is also existed. And if claystone gangue and calcareous rock gangue are added simultaneously, the test result proves that the obtained effect is surprising: the existence of the calcareous rock gangue improves the reaction capability of the claystone gangue, the activity of the claystone gangue can be excited by calcining at 650 ℃, and more active Al is generated2O3And SiO2The frost resistance of the concrete is better; meanwhile, the obtained activated product is added into concrete, so that the final setting time is obviously shortened. Further investigating the above mechanism, the inventors thought that: the calcareous rock gangue contains a large amount of calcium oxide (more than 30 percent), the calcium oxide plays a role in promoting the active reaction of the claystone gangue, but the reason for shortening the final setting time needs to be further researched.
Further, the weight ratio of the Bayer process red mud to the claystone waste rock to the calcareous rock waste rock is 5: 1-3: 0.5-1.5. Furthermore, the weight ratio of the Bayer process red mud, the claystone gangue and the calcareous rock gangue is 5:2: 1. It is considered that the weight ratio of the bayer process red mud to the coal gangue is important in the co-activation process, and tests show that when the weight ratio of the bayer process red mud to the coal gangue is 5:3, the formed activated product is added into concrete, and the influence on the strength and the shrinkage performance of the concrete is the largest.
Further, the preparation method of the active admixture comprises the following steps:
mixing Bayer process red mud, claystone waste rock and calcareous rock waste rock according to the weight ratio of 5: 1-3: 0.5-1.5, slowly heating to 600-700 ℃, calcining for 1-2 hours, naturally cooling a calcined product at room temperature, and dry-grinding by using a ball mill to obtain an activated product. Further, the temperature was slowly raised to 650 ℃.
Further, the aggregate is composed of fine aggregate and coarse aggregate according to the weight ratio of 1: 0.5-1. The self-compacting concrete needs larger mortar amount, medium sand or coarse medium sand can be selected, and the fineness modulus of the sand is 2.5-3.0.
Furthermore, various types of coarse aggregates can be used as the coarse aggregates, and limestone mechanically crushed stones with the particle size of 5-20 mm are preferably used, so that the strength of concrete is improved.
Another object of the present invention is to provide a method for preparing the self-compacting concrete, comprising the following steps: uniformly mixing the portland cement and the active admixture, adding the aggregate, uniformly stirring and mixing to obtain a mixture, adding the naphthalene-based superplasticizer into water, uniformly mixing, adding the mixture into the mixture, and uniformly stirring to obtain the self-compacting concrete.
Therefore, the invention has the following beneficial effects:
1) according to the invention, claystone gangue, calcareous rock gangue and Bayer process red mud are calcined at a certain temperature, so that the purposes of simultaneously activating the claystone gangue and the Bayer process red mud are realized, the strength and the frost resistance of the self-compacting concrete are improved by adding the activated product, the shrinkage performance of the self-compacting concrete is improved, the possibility of cracking of the concrete is reduced, and better frost resistance and shrinkage performance can be obtained without adding an air entraining agent and an expanding agent.
(2) The invention utilizes the leftover materials generated in the coal gangue crushing process and the industrial solid wastes discharged after refining the alumina as the admixture of the self-compacting concrete, and solves the problems of environmental pollution and resource waste caused by the leftover materials and the industrial solid wastes.
Detailed Description
The invention is further illustrated by the following description and specific examples, which are not intended to limit the invention in any way. The reagents, methods and apparatus employed in the present invention are conventional in the art, unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
EXAMPLE one preparation of an active admixture
Mixing Bayer process red mud, claystone waste rock and calcareous rock waste rock according to the weight ratio of 5:2:1, slowly heating to 650 ℃, calcining for 2 hours, naturally cooling the calcined product at room temperature, and dry-grinding by using a ball mill to obtain an activated product.
EXAMPLE two preparation of active admixtures
Mixing Bayer process red mud, claystone waste rock and calcareous rock waste rock according to the weight ratio of 5:3:1.5, slowly heating to 650 ℃, calcining for 2 hours, naturally cooling the calcined product at room temperature, and dry-grinding by using a ball mill to obtain an activated product.
EXAMPLE III preparation of active admixtures
Mixing Bayer process red mud, claystone waste rock and calcareous rock waste rock according to the weight ratio of 5:1:0.5, slowly heating to 650 ℃, calcining for 2 hours, naturally cooling the calcined product at room temperature, and dry-grinding by using a ball mill to obtain an activated product.
EXAMPLE four self-compacting concrete (parts by weight)
Raw materials
|
Example four
|
EXAMPLE five
|
EXAMPLE six
|
Portland cement
|
202
|
225
|
324
|
Active admixture
|
127
|
125
|
130
|
River sand
|
1033
|
1000
|
1000
|
Limestone machine crushed stone
|
520
|
600
|
500
|
Naphthalene series high efficiency water reducing agent
|
10
|
12
|
15
|
Water (W)
|
175
|
168
|
180 |
Note: examples four to six active admixtures correspond to the active admixtures prepared in examples one to three, respectively.
The preparation method comprises the following steps:
uniformly mixing the silicate cement and the active admixture, adding the river sand and the limestone machine crushed stone, uniformly stirring and mixing to obtain a mixture, adding the naphthalene-based superplasticizer into water, uniformly mixing, adding the mixture into the mixture, and uniformly stirring to obtain the self-compacting concrete.
According to the calcination parameters in the following table 1, the # 1-5 active admixture is prepared according to the method in the example one, and the self-compacting concrete in the comparative examples one-five is respectively prepared by adopting the active admixture instead of the active admixture in the example one.
TABLE 1 calcination parameters
Note: the remaining parameters, such as calcination temperature and calcination time, were as in example one.
Test example I, Performance evaluation
1.1 working Properties of self-compacting concrete
The working performance of the self-compacting concrete of the four to six examples was tested according to the working performance test standards and methods of the self-compacting concrete of table 2 below, and the test results are shown in table 3 below.
TABLE 2 working Performance test standards and methods for self-compacting concrete
Test items
|
Method of producing a composite material
|
Unit of
|
Typical range of measured values
|
①
|
Slump constant
|
mm
|
240~270
|
②
|
Degree of expansion
|
mm
|
650±50
|
③
|
T50cmSlump flow
|
Second of
|
5~15
|
④
|
Flow time of V-shaped funnel
|
Second of
|
9~20
|
⑤
|
L-shaped box
|
(h2/h1)
|
0.8~1.0
|
⑥
|
Test filling height of U-shaped box
|
(h2-h1)mm
|
>320
|
⑦
|
Filling box
|
%
|
>80 |
TABLE 3 self-compacting concrete workability test results
Note: the items (c) to (c) correspond to the test items and test methods shown in the table of table 2.
As can be seen from Table 3, the self-compacting concretes prepared in the fourth to sixth examples have good fluidity and filling property, strong gap passing property and excellent working performance.
1.2 mechanical Properties and shrinkage Properties of self-compacting concrete
Testing the mechanical properties of concrete samples of the fourth to sixth examples and the first to fifth comparative examples according to the general concrete mechanical property test method (GB/T50081-2002), and curing the formed samples in a standard curing chamber; the concrete test pieces of the four to six molded examples and the first to five molded comparative examples are subjected to standard curing for 28d, and then are moved into a shrinkage chamber for testing, and the measurement results of the mechanical properties and the shrinkage properties are shown in the following tables 4 to 5.
TABLE 4 measurement results of mechanical properties (compressive strength in MPa, modulus of elasticity in GPa)
Test piece
|
3 day compressive strength
|
Compressive strength of 7 days
|
28 day compressive strength
|
Modulus of elasticity for 28 days
|
Example four
|
52.6
|
63.1
|
89.5
|
35.6
|
EXAMPLE five
|
48.4
|
61.5
|
88.2
|
34.2
|
EXAMPLE six
|
48.5
|
59.2
|
85.3
|
31.9
|
Comparative example 1
|
38.2
|
51.0
|
64.9
|
29.6
|
Comparative example No. two
|
30.5
|
41.6
|
58.3
|
24.7
|
Comparative example No. three
|
43.2
|
56.4
|
75.4
|
31.8
|
Comparative example No. four
|
28.9
|
36.4
|
54.5
|
28.2
|
Comparative example five
|
34.4
|
44.5
|
61.8
|
26.6 |
As can be seen from Table 4, the self-compacting concrete samples of the four to six examples have excellent mechanical properties, which are superior to those of the other groups; in other comparative examples, the third comparative example and the first comparative example also contain Bayer process red mud and claystone gangue and have mutual activation, so that the compressive strength and the elastic modulus of the self-compacting concrete test piece are slightly reduced compared with those of the fourth example, but no obvious difference exists; in other comparative examples, no mutual activation between the Bayer process red mud and the claystone gangue occurs, so that no obvious effect on improving the mechanical property of the test piece is achieved.
TABLE 5 measurement results of shrinkage creep property of self-compacting concrete
Test piece
|
Creep load shrinkage value of 90d (× 10)-6)
|
Example four
|
135
|
EXAMPLE five
|
140
|
EXAMPLE six
|
142
|
Comparative example 1
|
184
|
Comparative example No. two
|
261
|
Comparative example No. three
|
176
|
Comparative example No. four
|
243
|
Comparative example five
|
285 |
As can be seen from table 5 above, the test pieces of comparative examples two, four and five showed larger shrinkage than those of examples four to five, wherein comparative example five did not contain bayer process red mud and showed the largest dry shrinkage; in comparative examples II and IV, the main components of the calcareous rock gangue are calcite, dolomite, iron dolomite, phosphosiderite, pyrite, organic sulfur and the like; the main components of the aluminum gangue are gibbsite, hydraulic aluminum ore, quartz, limonite, muscovite, calcite and the like, and the two contain a small amount of kaolinite, so that the aluminum gangue cannot fully activate the Bayer process red mud, and has no obvious effect on the shrinkage of the self-compacting concrete.
1.3 setting time of self-compacting concrete
TABLE 6 test results of setting time of self-compacting concrete
Test piece
|
Initial setting time/min
|
Final setting time/min
|
Example four
|
182
|
258
|
EXAMPLE five
|
175
|
260
|
EXAMPLE six
|
177
|
253
|
Comparative example 1
|
162
|
374
|
Comparative example No. two
|
146
|
227
|
Comparative example No. three
|
159
|
351
|
Comparative example No. four
|
153
|
246
|
Comparative example five
|
138
|
218 |
As can be seen from table 6 above, the activated bayer process red mud is the main cause of the overlong final setting time of the self-compacting concrete, and the bayer process red mud is activated by clay-type gangue in the first and third comparative examples, so the final setting time of the test piece is longer; comparative examples two, four and five, however, did not have the above-described mutual activation, so you did not show too long final set times. The result shows that on the basis of the claystone gangue, if the calcareous rock gangue is added in the calcination, the problem of prolonging the final setting time of the self-compacting concrete caused by activating the red mud in the Bayer process is favorably inhibited.
1.4 Freeze resistance
The test pieces were subjected to freeze-thaw cycle test by the rapid freezing method according to the method in "SL 352-.
TABLE 7 test results of anti-freeze Properties
Note: compared with the fourth embodiment, claystone gangue and calcareous gangue are not added in the calcination process.
As can be seen from Table 7, the self-compacting concretes of the four to six examples of the invention have excellent frost resistance, and the mass loss rate is not more than 3% after 200 times of freeze-thaw cycles. From the results of the first to fifth comparative examples, it can be seen that the addition of claystone gangue activated by red mud has a better effect of improving the frost resistance of the self-compacting concrete than other types of gangue. Of these, comparative example four was the worst in terms of freeze resistance, probably because comparative example four contained no clay-rock ore and no significant activation of bayer process red mud was observed with alumino-rock ore and calcareous ore.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, and simplifications are intended to be included in the scope of the present invention.