CN114620987B - Marine concrete with microbial corrosion effect - Google Patents
Marine concrete with microbial corrosion effect Download PDFInfo
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- CN114620987B CN114620987B CN202210458369.1A CN202210458369A CN114620987B CN 114620987 B CN114620987 B CN 114620987B CN 202210458369 A CN202210458369 A CN 202210458369A CN 114620987 B CN114620987 B CN 114620987B
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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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/04—Portland 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
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses marine concrete with a microbial corrosion effect, which is prepared from the following raw materials in parts by weight: 1800-2000 parts of aggregate, 220-240 parts of cement, 150-180 parts of water, 20-40 parts of fly ash, 2-6 parts of zinc oxide and 2-6 parts of calcium tungstate. The concrete provided by the invention takes zinc oxide and calcium tungstate as additives, and the zinc oxide inhibits the growth of bacteria and even causes bacterial death due to the damage of cell membranes and egg self-bodies caused by the reactions of isomerism, polycondensation and the like, so that the formation of biological sulfuric acid or biological sulfate radical is reduced, and the microbial corrosion damage of the concrete is reduced. The calcium tungstate powder can also improve the early strength of a cement matrix, improve the compactness of concrete, have obvious effects on improving the workability, the setting time, the mechanical property and the durability of the concrete, and can also effectively relieve the decrease of the PH value of the concrete.
Description
Technical Field
The invention relates to the technical field of ocean constructional engineering, in particular to ocean concrete with a microbial corrosion effect.
Background
The marine concrete is applied to ocean engineering, and besides the strength and the workability of the mixture, the concrete must have the required properties of impermeability, freezing resistance, corrosion resistance, steel bar corrosion resistance and slush impact resistance. As the application of marine concrete becomes wider, research on corrosion resistance of marine concrete becomes more important. Studies have shown that the failure of concrete is related to the metabolism of microorganisms, namely biological sulfuric acid generated by the metabolism of bacteria such as sulfate reducing bacteria, sulfur oxidizing bacteria and the like is a main cause of corrosion of concrete.
The action mechanism of the concrete microorganism corrosion: the initial pH value of the concrete surface is as high as 11-13, and the concrete surface is not suitable for the growth of bacteria and needs H 2 S and CO 2 The pH value of the surface of the concrete is reduced firstly, mesophilic bacteria can grow in an environment with a higher pH value (about 9), the pH value of the surface of the concrete is reduced to 4-5, environmental conditions and nutrients are provided for mass propagation of acidophilic bacteria, and the pH value of the surface of the concrete is further reduced to 1-2 under the acid production action of acidophilic bacteria metabolism, so that the concrete is severely corroded. The existing microbial corrosion mechanism proves that before the biological sulfuric acid is formed, the microorganisms are firstly adhered to the surface of the concrete to form a biological film, and then the biological film can corrode the concrete.
At present, the research on the microbial corrosion of concrete is mainly focused on the corrosion of the land sewage disposal pipe in the sewage environment, and the corrosion of the concrete in the marine environment is focused on the chloride ion corrosion of reinforced concrete, but the microbial corrosion does not pay attention to and pay attention to people. If a method for killing or inhibiting the growth and reproduction of microorganisms in contact with concrete or reducing the activity of microorganisms in a marine environment can be found, the generation of biological sulfuric acid or biological sulfate radical can be reduced, and the microbial corrosion damage of the concrete can be further reduced.
Trace amounts of metal ions (e.g. Zn 2+ ) Is balanced and fineThe survival of the bacteria is crucial, not only to participate in the metabolism of a large number of enzymes but also to balance and stabilize a variety of protein structures. However, znO dissolved in water continuously releases Zn 2+ A large amount of Zn 2+ Not only does not regulate balance, but also damages the structure of the machine body. Due to Zn 2+ The particle size is small enough to penetrate the cell wall and the cell membrane of bacteria and enter the inside of the bacteria, and the bacteria are divided into two parts to act on bacterial bodies, and one part of Zn 2+ Changes phospholipid arrangement mechanism by reacting with transport functional protein while passing through cell wall and cell membrane, influences cell membrane permeability, and damages relatively stable internal environment required for cell life activity, and another part of Zn 2+ The cell membrane enters the bacteria to react with the groups with transfer and transport functions on the cell membrane, and simultaneously the electron transfer system is destroyed to inhibit the release of internal energy, so that the internal activity of the bacteria is destroyed to achieve the aim of sterilization. Accordingly, the present invention provides a marine concrete incorporating zinc oxide.
The foregoing background is only for the purpose of providing an understanding of the inventive concepts and technical aspects of the present invention and is not necessarily prior art to the present application and is not intended to be used to evaluate the novelty and creativity of the present application in the event that no clear evidence indicates that such is already disclosed at the filing date of the present application.
Disclosure of Invention
In order to solve the problems, the invention provides marine concrete with a microbial corrosion effect. The concrete provided by the invention takes zinc oxide and calcium tungstate as additives, and the zinc oxide inhibits the growth of bacteria and even causes bacterial death due to the damage of cell membranes and egg self-bodies caused by the reactions of isomerism, polycondensation and the like, so that the formation of biological sulfuric acid or biological sulfate radical is reduced, and the microbial corrosion damage of the concrete is reduced. The calcium tungstate powder can also improve the early strength of a cement matrix, improve the compactness of concrete, have obvious effects on improving the workability, the setting time, the mechanical property and the durability of the concrete, and can also effectively relieve the decrease of the PH value of the concrete.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the marine concrete with the microbial corrosion effect is prepared from the following raw materials in parts by weight: 1800-2000 parts of aggregate, 220-240 parts of cement, 150-180 parts of water, 20-40 parts of fly ash, 2-6 parts of zinc oxide and 2-6 parts of calcium tungstate.
The invention adopts the following preferred technical scheme: the aggregate consists of natural broken stone and river sand.
The weight portions of the natural crushed stone and the river sand are respectively 800-850 portions and 1100-1200 portions.
The invention adopts the following preferred technical scheme: the natural crushed stone is 20-40 mm natural limestone crushed stone, the water absorption rate is 0.59%, and the compact stacking density is 1570kg.m -3 Apparent density of 2690kg.m -3 Close-packed porosity of 42%
The invention adopts the following preferred technical scheme: the aggregate is further subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate.
The invention adopts the following preferred technical scheme: the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducer to the lignosulfonate is 7:15:22, and the dosage is 0.5-1% of the weight of the aggregate.
The invention adopts the following preferred technical scheme: the modification treatment method of the aggregate comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
The invention also provides a preparation method of the marine concrete, which comprises the following steps: weighing the raw materials according to the proportion, sequentially adding aggregate, cement and fly ash into a stirrer, dry-mixing for 10-30s, adding zinc oxide and calcium tungstate after uniform mixing, adding water, continuously stirring for 2-3min, and turning and uniformly stirring after discharging to obtain the marine concrete.
Compared with the prior art, the invention has the advantages that:
the zinc oxide added by the invention has stronger photocatalysis effect, and generates holes (h+) with oxidability under the irradiation of sunlightHas reducing electrons (e-). At the same time as H 2 O contacts and oxidizes it to a strong oxidant, hydroxyl radical (0H), which can oxidize bacteria, viruses and various organics to C0 2 And H 2 0, etc. And water and O 2 H is generated on the surface of nano zinc oxide through multi-step reaction under the condition of existence simultaneously 2 02 and the like, and the bacterial growth is inhibited by the injury of cell membranes and egg self-bodies caused by isomerism, polycondensation and the like, and even bacterial death is caused, so as to reduce the formation of biological sulfuric acid or biological sulfate radical, thereby reducing the microbial corrosion damage of concrete. The calcium tungstate powder can also improve the early strength of the cement matrix, and can accelerate the early strength of tricalcium silicate (C) 3 S) prevents ettringite (AFt) from converting to mono-sulfur hydrated calcium sulfoaluminate (AFm). In addition, the calcium tungstate can improve the grain composition of the cementing material, has good filling effect, replaces free water, further improves the compactness of concrete, has obvious and beneficial effects on the workability, the setting time, the mechanical property and the durability of the concrete, and can effectively relieve the decrease of the PH value of the concrete.
1. According to the invention, sodium nitrite, the polycarboxylic acid high-efficiency water reducer and the lignosulfonate modified aggregate are used, and the dispersion performance of the polycarboxylic acid water reducer can be improved and the compactness of concrete can be improved when the lignosulfonate is compounded with the polycarboxylic acid water reducer; sodium nitrite early strength agent promotes C 3 Ato AFt, C 3 S and C 2 S-direction Ca (OH) 2 Thereby promoting an increase in the strength of the concrete.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The cement used in the following examples was PO42.5 Portland cement. The crushed stone is natural limestone crushed stone with the grain diameter of 20-40 mm, the water absorption rate is 0.59 percent, and the compact stacking density is 1570kg.m -3 Apparent density of 2690kg.m -3 The close-packed porosity was 42%.
Example 1
The marine concrete with the microbial corrosion effect is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water, 27kg of fly ash, 2.7kg of zinc oxide and 2.7kg of calcium tungstate.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.7% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Example 2
The marine concrete with the microbial corrosion effect is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water, 27kg of fly ash, 5.4kg of zinc oxide and 2.7kg of calcium tungstate.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.7% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Example 3
The marine concrete with the microbial corrosion effect is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water, 27kg of fly ash, 2.7kg of zinc oxide and 5.4kg of calcium tungstate.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.7% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Example 4
The marine concrete with the microbial corrosion effect is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water, 27kg of fly ash, 5.4kg of zinc oxide and 5.4kg of calcium tungstate.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.7% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Example 5
The marine concrete with the microbial corrosion effect is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 937kg of river sand, 223kg of cement, 153kg of water, 32kg of fly ash, 3.6kg of zinc oxide and 2.7kg of calcium tungstate.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.6% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Example 6
The marine concrete with the microbial corrosion effect is prepared from the following raw materials in parts by weight: 1152kg of natural limestone macadam, 845kg of river sand, 233kg of cement, 162kg of water, 30kg of fly ash, 3.6kg of zinc oxide and 4.5kg of calcium tungstate.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.8% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Comparative example 1
The marine concrete is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water, 27kg of fly ash and 2.7kg of zinc oxide.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.7% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Comparative example 2
The marine concrete is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water, 27kg of fly ash and 2.7kg of calcium tungstate.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.7% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Comparative example 3
The marine concrete is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water and 27kg of fly ash.
The natural limestone macadam and the river sand are subjected to modification treatment by sodium nitrite, a polycarboxylic acid high-efficiency water reducing agent and lignosulfonate, wherein the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducing agent to the lignosulfonate is 7:15:22, and the dosage is 0.7% of the weight of the aggregate. The modification treatment method comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain the modified recycled aggregate.
Comparative example 4
The marine concrete is prepared from the following raw materials in parts by weight: 1141kg of natural limestone macadam, 831kg of river sand, 237.6kg of cement, 162kg of water, 27kg of fly ash, 2.7kg of zinc oxide and 2.7kg of calcium tungstate.
Concrete test pieces were prepared according to the formulations of examples 1-6 and comparative examples 1-4 as follows:
(1) And pouring the weighed aggregate, cement and fly ash into a stirrer in sequence, opening the stirrer after adding a cover, dry-stirring for 20s, adding water, and continuing stirring for 3min. Zinc oxide and calcium tungstate are added.
(2) And (5) manually stirring the mixture of the discharging machine for 2-3 times to make the mixture uniform.
(3) The concrete mixture is filled into the human test mould once, and the vibration of the vibrating table is continuously carried out until the concrete surface is pulped and no obvious large bubbles overflow, so that the concrete mixture is stopped immediately and cannot excessively vibrate, and the mixture layering and the air content loss are avoided.
(4) After the test piece is molded, the mold is removed after the mold is placed in a room with the temperature of (20 ℃ C. And 5 ℃ C.) for 24 hours. And (3) immediately placing the test piece into a standard curing room with the temperature of 20 ℃ of 2 ℃ for curing after removing the die, and placing the test piece in an overhead manner with the distance of 10-20 mm.
(5) Curing for 28 days, and measuring the rebound value, the compressive strength and the PH value, and the test results are shown in Table 1.
Table 1: the invention provides a performance test result of marine concrete
| Group of | Compressive Strength/MPa | PH | Rebound value |
| Example 1 | 41.6 | 13.19 | 33.6 |
| Example 2 | 41.7 | 13.04 | 32.8 |
| Example 3 | 42.2 | 12.98 | 32.1 |
| Example 4 | 43.1 | 13.15 | 33.2 |
| Example 5 | 40.5 | 12.82 | 31.9 |
| Example 6 | 41.2 | 12.67 | 32.3 |
| Comparative example 1 | 35.7 | 12.84 | 30.5 |
| Comparative example 2 | 36.3 | 12.99 | 31.6 |
| Comparative example 3 | 32.0 | 12.75 | 28.61 |
| Comparative example 4 | 38.8 | 13.09 | 31.2 |
From the test results, the concrete has the advantages that through the combination of the change of the compressive strength and the change of the rebound value, when the concrete is doped with zinc oxide and calcium tungstate, the propagation of microorganisms on the surface of the concrete is effectively inhibited, the strength and the durability of the concrete are improved, and the reduction of the PH value of a concrete test block can be effectively relieved. After the aggregate is modified by sodium nitrite, the polycarboxylic acid high-efficiency water reducer and lignosulfonate, the compressive strength is also obviously improved.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and is not intended to limit the practice of the invention to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention.
Claims (1)
1. The marine concrete with the microbial corrosion effect is characterized in that: the marine concrete is prepared from the following raw materials in parts by weight: 1800-2000 parts of aggregate, 220-240 parts of cement, 150-180 parts of water, 20-40 parts of fly ash, 2-6 parts of zinc oxide and 2-6 parts of calcium tungstate;
the aggregate consists of natural crushed stone and river sand;
the weight parts of the natural crushed stone and the river sand are respectively 800-850 parts and 1100-1200 parts;
the aggregate is modified by sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate;
the mass ratio of the sodium nitrite to the polycarboxylic acid high-efficiency water reducer to the lignosulfonate is 7:15:22, and the dosage is 0.5-1% of the weight of the aggregate;
the natural crushed stone is 20-40 mm natural limestone crushed stone;
the modification treatment method of the aggregate comprises the following steps: mixing sodium nitrite, a polycarboxylic acid high-efficiency water reducer and lignosulfonate, dissolving in water, spraying on the aggregate, and fully wetting to obtain modified recycled aggregate;
the preparation method of the marine concrete comprises the following steps: weighing the raw materials according to the proportion, sequentially adding aggregate, cement and fly ash into a stirrer, dry-mixing for 10-30s, adding zinc oxide and calcium tungstate after uniform mixing, adding water, continuously stirring for 2-3min, and turning and uniformly stirring after discharging to obtain the marine concrete.
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