CN116023061A - Concrete polyaniline-basic copper carbonate compound additive, preparation method and application - Google Patents
Concrete polyaniline-basic copper carbonate compound additive, preparation method and application Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 63
- 230000000996 additive effect Effects 0.000 title claims abstract description 57
- 229940116318 copper carbonate Drugs 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 copper carbonate compound Chemical class 0.000 title abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 37
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 229920000767 polyaniline Polymers 0.000 claims abstract description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
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- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
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- 238000003756 stirring Methods 0.000 claims description 18
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a concrete polyaniline-basic copper carbonate compound additive, a preparation method and application thereof, and the preparation process comprises the following steps: respectively preparing aniline hydrochloride solution and copper sulfate solution, mixing, adding ethylene carbonate to obtain a mixed solution, adding ammonium sulfate solution to the mixed solution to obtain suspension, adding saturated solution of sodium bicarbonate to the suspension until the pH value of the suspension is greater than 8, forming basic copper carbonate precipitate on the surface of polyaniline, standing for aging, centrifuging or suction filtering to obtain polyaniline-basic copper carbonate composite powder in a wet state, and repeatedly leaching to remove soluble impurities to obtain the polyaniline-basic copper carbonate composite product. The additive disclosed by the invention is kept in a composite suspension state with good dispersibility when being mixed into concrete, and the two components used have obvious repellent effect on organisms, have the characteristics of uniform dispersion and slow release and long-acting, play a role in protecting, can not pollute the marine environment, and have a wide application prospect in protecting concrete members in the marine environment.
Description
Technical Field
The invention belongs to the technical field of concrete additives, and particularly relates to a concrete polyaniline-basic copper carbonate compound additive, a preparation method and application thereof.
Background
The concrete has wide application prospect in the field of ocean engineering. However, in marine environments, concrete needs to be protected to ensure application safety. On one hand, the marine environment is rich in chloride ions, magnesium salts and sulfates, and corrosion, leaching and crystallization of the chemical components often lead to corrosion of reinforcing steel bars in the concrete and destruction of the concrete structure, and seriously affect the long-term service and durability of the concrete structure; on the other hand, over 2000 kinds of attached organisms (i.e., fouling organisms) in the ocean have been recorded in coastal areas of China, and they are attached to a concrete matrix through secreted mucus, and in metabolic activities, they generate various chemical substances, wherein the generated acid substances have great corrosiveness to concrete, biological metabolizing acids act on the concrete body to generate ettringite, which causes swelling, cracking and flaking of the concrete body, and in addition, some secretions can infiltrate into gaps on the concrete surface to form strong adsorption force, thereby causing damage. Meanwhile, the mass adhesion of benthos and drilling organisms in the ocean can obviously increase the weight of the concrete member, so that the recycling is difficult and the like. In summary, the combination of biofouling and corrosion poses a serious threat to the durability of large ocean engineering concrete structures, limiting the development of the ocean industry.
At present, a surface coating method is mainly used for concrete protection, but the method can only prevent external harmful ions from continuously penetrating into reinforced concrete, but can not inhibit the continuous damage of the existing harmful ions to the reinforced concrete, and has limited effect especially for the concrete using sea sand; in the case of reinforced concrete coated with a coating, localized corrosion still occurs due to the damage of transportation and construction to the fragile thin coating, and the coating is destroyed by the stretching of the hard and sharp calcareous floor around in the growth process of the marine organisms, in particular barnacles, oysters and the like, so that the concrete cannot be effectively protected once the coating is peeled off successively. In order to achieve the protection effect, most of concrete additives are solid powder, and when the concrete additives are mixed in the process of mixing concrete, the concrete additives are often not uniformly adhered to the mixture, so that the dispersibility of the additives in the concrete is difficult to ensure; meanwhile, the concrete protection in the marine environment is not excessively considered from the viewpoint of seawater corrosion prevention, and has a certain defect in the anti-biological performance.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a concrete polyaniline-basic copper carbonate compound additive, a preparation method and application thereof.
The invention adopts the additive with antibiotic-antiseptic efficacy, keeps the composite suspension state with good dispersibility when being mixed into concrete, the two components used have obvious repellent effect on organisms, and the surfactant is adopted when the additive is prepared, so that the additive has the characteristics of uniform dispersion and slow release long-acting, has the protection effect, does not pollute the marine environment, and has wide application prospect in protecting concrete members under the marine environment.
The method is realized by the following technical scheme:
the preparation method of the concrete polyaniline-basic copper carbonate composite additive comprises the following steps:
1) Dissolving aniline hydrochloride in distilled water to obtain aniline hydrochloride solution;
2) Dissolving copper sulfate in distilled water to obtain a copper sulfate solution;
3) Mixing the aniline hydrochloride solution prepared in the step 1) and the copper sulfate solution prepared in the step 2) according to the volume ratio of 1:5 to prepare a mixed solution, adding ethylene carbonate into the mixed solution, and stirring to completely dissolve the ethylene carbonate; obtaining a mixed solution;
4) Dissolving ammonium persulfate in distilled water to obtain ammonium persulfate solution, dropwise adding the ammonium persulfate solution into the mixed solution prepared in the step 3) under the stirring state, and continuously stirring by using an electromagnetic stirrer after the dropwise adding is finished to obtain dark green suspension;
5) While monitoring the pH value, dropwise adding a saturated solution of sodium bicarbonate into the dark green suspension prepared in the step 4) while stirring until the pH value of the suspension is greater than 8, continuously stirring for 30min, and again confirming that the pH value of the suspension is greater than 8, otherwise, continuously supplementing and dropwise adding the sodium bicarbonate solution to enable the polyaniline surface to form basic copper carbonate sediment, wherein the color is dark blue;
6) And standing and aging polyaniline for 6 hours, centrifuging or suction filtering to obtain polyaniline-basic copper carbonate composite powder in a wet state, and repeatedly leaching to remove soluble impurities to finally obtain the polyaniline-basic copper carbonate composite product.
Further, the addition amount of the ethylene carbonate in the step 3) accounts for 1% of the total weight of the mixed solution.
Further, the volume ratio of the ammonium persulfate solution to the aniline hydrochloride solution in the step 4) is 1:1, the dropping speed is 3s to 5s, and the continuous stirring time of the electromagnetic stirrer is 2 hours.
Further, the dark green suspension prepared in step 4) is kept at a temperature of less than 5 ℃ in an ice bath all the time.
Further, if the surfactant used in the process of preparing the compound is replaced by cetyl trimethyl ammonium chloride, sodium cetyl sulfonate, etc., or other schemes formed by changing the feeding ratio and the formation sequence of polyaniline and basic copper carbonate are within the scope of the invention.
The polyaniline-basic copper carbonate composite additive for concrete prepared by the method for preparing a polyaniline-basic copper carbonate composite additive for concrete according to any one of claims 1 to 5.
The application of the concrete polyaniline-basic copper carbonate compound additive in protecting concrete members in marine environment.
Further, the method comprises the following specific steps: the polyaniline-basic copper carbonate composite additive of the concrete is mixed with water to form a uniformly dispersed suspension system under the state of maintaining the wet powder, and is added into the concrete in the form of composite suspension in the concrete mixing process.
Further, the additive amount of the concrete polyaniline-basic copper carbonate composite additive is as follows: the dry weight of the concrete composite additive accounts for 0.05 to 0.15 percent of the mass of the concrete.
Compared with the prior known concrete protection means, the polyaniline-basic copper carbonate compound is adopted as an antibiotic-antiseptic additive of concrete, and has the following advantages and effects:
1) Sustained release long-acting: in the prior art, concrete is protected by adopting an external coating mode in the concrete member anti-biological/anti-corrosion technology research, but the invention adopts an additive mode, can be directly added while preparing the concrete member, and omits the step of coating the concrete member, thereby simplifying the flow of the concrete protection technology. Meanwhile, the compound is added into the concrete as an additive, so that the protection effect on the concrete can be better achieved, the effective protection time of the concrete can be prolonged, and the situation that the concrete cannot be continuously protected due to spalling of the coating can be avoided;
2) And (5) in-situ compounding. The polyaniline-basic copper carbonate compound prepared by the invention has the characteristic of in-situ compounding, can combine two chemical substances together, and simultaneously plays the roles of the two chemical substances;
3) And uniformly dispersing. The compound additive prepared by the invention can better ensure the dispersibility, and as the surfactant is used in preparation, the corresponding hydrophilic group of the surfactant is adsorbed on the surface layer of the surfactant after the surfactant acts with ions in the solution, and a certain ordered arrangement is realized, so that free ions in the solution are greatly reduced, and the hydrolysis speed is effectively promoted. Under the adsorption action of the surfactant, the surface tension of the solid and the liquid is reduced, so that ions are gradually diffused from a liquid phase to the surface of a solid phase, uniform dispersion is realized, and the ions are added in the form of a compound suspension in the concrete forming stage, so that the ions are more easily uniformly dispersed in the concrete, and the effect is stably exerted;
4) Has evasiveness to living things. The composite additive can effectively prevent organisms in the ocean from adhering, and can slow down the corrosion of reinforced concrete from the perspective of organism avoidance, thereby playing a role in protecting the concrete.
5) Is environment-friendly. Because of the water-insoluble nature of basic copper carbonate, when used as an anti-corrosion additive for concrete, such chemicals are not soluble in the marine environment and can remain in the concrete for environmental protection. Polyaniline has excellent environmental stability, and has extremely poor solubility, and can not influence and damage the environment.
6) The cost is low. The preparation of polyaniline-basic copper carbonate complex as an antibiotic-preservative is an economical means, which has a certain advantage in terms of cost, since most of the chemicals used for preparing the polyaniline-basic copper carbonate complex are inexpensive and easily available chemicals and do not involve expensive chemicals. The cost of polyaniline itself is very low, but the method of preparing polyaniline in the laboratory is selected in consideration of the dispersibility of the additive in concrete, but this can also be explained sideways, and the advantage of polyaniline in terms of preparation cost.
Detailed Description
The invention is further described below in connection with specific examples to provide a better understanding of the present technical solution.
The invention provides a preparation method of a concrete composite additive, which comprises the following steps:
1) Dissolving 0.2mol (25.918 g) of aniline hydrochloride in distilled water, and fixing the volume to 100mL to obtain 2mol/L aniline hydrochloride solution;
2) Dissolving 0.2mol (31.920 g) of copper sulfate in distilled water, and fixing the volume to 500mL to obtain a copper sulfate solution with the concentration of 0.4 mol/L;
3) Mixing the two solutions uniformly, adding 6g (1% of the total weight of the solution) of ethylene carbonate into the mixed solution, and stirring to completely dissolve the ethylene carbonate;
4) Dissolving 0.2mol (45.6402 g) of ammonium persulfate in distilled water, fixing the volume to 100mL to obtain a 2mol/L ammonium persulfate solution, dropwise adding all the ammonium persulfate solution into the mixed solution while stirring (the dropwise adding speed is 3s to 5s, and the dropwise adding is completed for about 90 min), and continuously stirring for 2h by using an electromagnetic stirrer after the dropwise adding is completed to obtain a dark green suspension (the temperature is always kept below 5 ℃ in an ice bath);
5) While monitoring the pH value, dropwise adding a saturated solution of sodium bicarbonate into the dark green suspension while stirring until the pH value of the suspension is greater than 8, continuously stirring for 30min, and again confirming that the pH value of the suspension is greater than 8, otherwise, continuously adding dropwise a sodium bicarbonate solution (about 33.604g of sodium bicarbonate is needed) to ensure that basic copper carbonate precipitate is formed on the surface of polyaniline, wherein the color is dark blue;
6) Standing and aging for 6 hours, centrifuging or suction filtering to obtain polyaniline-basic copper carbonate composite powder (in a wet state), and repeatedly leaching to remove soluble impurities to finally obtain a product polyaniline-basic copper carbonate composite.
The invention also provides a concrete composite additive prepared by the preparation method, which is mixed with water to form a uniformly dispersed suspension system under the state of the wet powder, and finally the additive is added into concrete in the form of composite suspension in the mixing process of the concrete, wherein the addition accounts for 0.05-0.15% of the mass of the concrete by dry weight.
The principle of using polyaniline-basic copper carbonate compound as concrete antibiotic-antiseptic additive in the invention is as follows:
the two components for compounding are polyaniline and basic copper carbonate, wherein the polyaniline has certain antibacterial and antifouling functions, and is a well-selected concrete coating material as a corrosion protective agent through extensive research. And polyaniline can be prepared by various technologies, has high availability and good environmental stability, and has extremely poor solubility due to the strong interaction between the chain rigidity and the chains. Even aqueous dispersion systems with antibiotic-antiseptic function can be synthesized under the action of auxiliary agents such as surfactants, but polyaniline is generally used as a coating to coat concrete, and few studies have been made on the use of polyaniline as an additive. In addition, some inorganic compounds of copper elements, such as Ag, cu, bi, sb, sn, have good anti-corrosion properties, and although the insoluble salts are insoluble in water, the trace cations emitted by the insoluble salts can kill bacteria and algae microorganisms, thereby achieving good biological repellency. The copper ions have strong biotoxicity and have obvious effect in sterilization. Among them, basic copper carbonate has a very wide range of applications in production activities, and is also used in a large amount as one of the components of agricultural bactericides. Polyaniline and basic copper carbonate have antibiotic-antiseptic effect, and the polyaniline-basic copper carbonate compound is added into concrete as an additive, so that the problem that the concrete cannot be continuously protected after the coating is peeled off in the marine environment can be solved, and meanwhile, the compound is insoluble in water and cannot pollute the marine environment.
After the polyaniline-basic copper carbonate compound is prepared, a complete technical method for corrosion prevention/antibiosis of concrete in marine environment can be obtained by combining the preparation process of the concrete member.
Taking the standard of C25 common concrete as an example, concrete test pieces (divided into test blocks and test plates) are prepared. The density of the concrete test piece is 2356kg/m 3 The mixing ratio is water: and (3) cement: desalting sand: machine-made sand: lithotripsy (Φ5-15): coal ash: mineral powder: high-efficiency water reducer: synergist = 167:208:297:445:1085:61:70:6.77:2.71, slump of 60.+ -.20 mm. The test block size was 100 mm. Times.100 mm,2.356 kg/block. The test board has the specification of 200mm multiplied by 100mm multiplied by 20mm, and 0.9424 kg/test board is internally provided with an iron wire mesh sheet so as to achieve the purposes of reinforcing the test board and ensuring that the test board is not easy to break.
The test piece preparation process is as follows:
(1) And (3) washing the stirrer, pre-mixing a small amount of the same concrete, wetting the inner wall of the stirring tester and the ground iron plate with cement mortar, and discharging the pre-mixed concrete.
(2) Weighing according to the calculated result of the concrete mixing ratio, and carrying out secondary re-weighing, wherein the weighing precision is as follows: cement and water of + -0.5% and aggregate of + -1%. The materials except the water and the additive are sequentially poured into a stirrer to be stirred for 10 seconds. The non-dehydrated composite additive is added with water and stirred to obtain a composite suspension, and other additives are preferably added into a stirrer together with the stirring water. The concrete mixture is stirred for more than 120 seconds until the mixture is uniformly stirred, and then the mixture is manually turned over and stirred on the ground iron plate for two times after the mixture is poured out.
(3) Cleaning the test mould, and coating a layer of mineral oil on the inner wall of the test mould to ensure that the oil layer on the inner wall of the test mould is uniformly distributed and no obvious deposition exists.
(4) The mixture is added into the test mould at one time, and a spatula is used for tamping along the inner wall of the mould during charging, so that the mixture is higher than the mould.
(5) The test mould is fixed on the vibrating table to prevent the test mould from jumping on the vibrating table, and the test mould vibrates until the surface is pulped and no big bubbles overflow.
(6) Demoulding is carried out after solidification in the mould for one day, and the concrete solidification time has smaller floating according to the different use amount of the additive.
(7) And (3) placing the test piece in a standard curing room for curing for 28 days to obtain the concrete test piece containing the novel additive.
Example 1: the addition amount of the compound is 0.05% of the total weight of the concrete, and each 25L of concrete contains 29.45g of polyaniline-basic copper carbonate compound.
Example 2: the addition amount of the compound is 0.10 percent of the total weight of the concrete, and each 25L of the concrete contains 58.90g of polyaniline-basic copper carbonate compound.
Example 3: the addition amount of the compound is 0.15 percent of the total weight of the concrete, and each 25L of the concrete contains 88.35g of polyaniline-basic copper carbonate compound.
Comparative example 1: the addition amount of the compound is 0.20 percent of the total weight of the concrete, and each 25L of the concrete contains 117.80g of polyaniline-basic copper carbonate compound.
Comparative example 2: no polyaniline-basic copper carbonate complex additive was added.
Comparative example 3: and when the early-stage test piece is prepared, a polyaniline-basic copper carbonate compound additive is not added, after the test piece is cured, the test piece is taken, the polyaniline-basic copper carbonate compound coating is used for coating the concrete test piece, and a protective film is formed on the surface of the test piece to serve as a coating control group.
The specific method comprises the following steps: adding components such as a surfactant (propylene carbonate 5 g), a wetting dispersant, a thickener and the like into polyaniline-basic copper carbonate compound suspension (58.90 g,500 mL), preparing a coating, coating the surface of a concrete test piece, and drying the surface to obtain the coating.
Test example 1
The concrete test pieces of the different compound use modes and use amount groups in examples 1 to 3 and comparative examples 1 to 3 were hung to the offshore area intertidal zone, and the mechanical properties (including the compressive strength test and the split tensile strength test) before and after hanging were tested to obtain the following results (tables 1 and 2).
TABLE 1 results of concrete test block compressive strength test before and after sea test
Table 2 results of concrete coupon split tensile strength test before and after sea test
The mechanical property test of the concrete test blocks before and after the sea test suspension is carried out, so that the following steps are found: excessive polyaniline-basic copper carbonate compound can influence the strength of concrete, when the compound is used as an additive for concrete protection, if the addition amount exceeds 0.15%, the strength of the concrete can be negatively influenced to different degrees, but when the addition amount is within 0.05-0.15%, the strength of the concrete is not reduced; after the concrete test block without the compound additive is hung in the sea, the mechanical property of the concrete test block is obviously reduced along with the increase of hanging time due to the corrosion damage of the marine environment, the mechanical property of the concrete test block added with the compound additive is not obviously reduced after being hung, and the compressive strength loss rate and the splitting tensile strength loss rate of the concrete test block are smaller than those of the concrete test block without the compound additive under the same condition; the concrete application effect of the polyaniline-basic copper carbonate compound in concrete is tested, and the polyaniline-basic copper carbonate compound can play a role in protecting the concrete no matter being used as a concrete coating or an additive, but can play a larger role when being used as the additive in the concrete from the aspect of slow release and long acting.
Test example 2
The concrete test pieces of the different compound use modes and use amount groups in examples 1-3 and comparative examples 1-3 were hung to the offshore area intertidal zone, the biological attachment condition of the concrete test pieces was observed after salvaging, and the biological attachment amount of each group of test pieces was counted to obtain Table 3.
TABLE 3 biological adhesion count of sea test concrete test blocks
As can be seen from Table 3, the number of bioadhesions of the concrete block of comparative example 2 is significantly higher than that of the other experimental groups, and the number of bioadhesions increases with the increase of the suspension time; when the content of the compound additive was 0.05% (example 1), a small amount of organisms was attached, and after 30 days of hanging, the amount of attachment of the barnacles was 20.0% of the amount of addition of group 0 (comparative example 2), no sea anemone was attached, and after 90 days of hanging, the amount of attachment of the barnacles was only 7.0% of the amount of addition of group 0 (comparative example 2), and the amount of attachment of sea anemone was 11.1% of the amount of addition of group 0 (comparative example 2); when the content of the composite additive is not less than 0.10%, the concrete test block has no biological adhesion; the coating group (comparative example 3) had no organism attached after hanging for 30 days, but had a small amount of organism attached after 90 days, the amount of adhesion of the barnacle was 9.3% of that of the 0 group (comparative example 2), and the amount of adhesion of the sea anemone was 22.2% of that of the 0 group (comparative example 2). Therefore, the polyaniline-basic copper carbonate compound has good biological adhesion preventing capability when in sea test hanging, can obviously reduce the biological adhesion amount of concrete and reduce the adhesion of marine organisms, and has better effect than the effect of being directly added into a coating when the compound is used as a concrete additive.
Test example 3
The concrete panels of examples 1 to 3 and comparative examples 1 to 3 were placed in laboratory artificial enhanced ocean wastewater for 14 days, and after immersing, the concrete panels were taken out, the mass of the attached matter of each panel was measured, and the average value of each group was obtained to obtain table 4.
TABLE 4 mass average of concrete panels of each group
The concrete test panel of comparative example 2 was susceptible to fouling in a laboratory simulated artificial enhanced marine wastewater environment, and had more attachments on the surface. Therefore, a certain protection means is needed to be adopted for protecting the automobile in practical application. The concrete test panel of comparative example 3 shows good antibacterial and antifouling effects in the laboratory accelerated biological repellency test, the composite coating on the surface of the test panel has obvious biological repellency effect, and compared with other test panel groups, the mass of biological attachments on the surface of the concrete test panel of comparative example 3 is the smallest. In the whole, each group of concrete test panels added with the composite additive has good antibacterial and antifouling effects, and the antibacterial and antifouling effects are slightly improved along with the increase of the dosage of the composite additive.
Claims (8)
1. The preparation method of the concrete polyaniline-basic copper carbonate composite additive is characterized by comprising the following steps of:
1) Dissolving aniline hydrochloride in distilled water to obtain aniline hydrochloride solution;
2) Dissolving copper sulfate in distilled water to obtain a copper sulfate solution;
3) Mixing the aniline hydrochloride solution prepared in the step 1) and the copper sulfate solution prepared in the step 2) according to the volume ratio of 1:5 to prepare a mixed solution, adding ethylene carbonate into the mixed solution, and stirring to completely dissolve the ethylene carbonate; obtaining a mixed solution;
4) Dissolving ammonium persulfate in distilled water to obtain ammonium persulfate solution, dropwise adding the ammonium persulfate solution into the mixed solution prepared in the step 3) under the stirring state, and continuously stirring by using an electromagnetic stirrer after the dropwise adding is finished to obtain dark green suspension;
5) While monitoring the pH value, dropwise adding a saturated solution of sodium bicarbonate into the dark green suspension prepared in the step 4) while stirring until the pH value of the suspension is greater than 8, continuously stirring for 30min, and again confirming that the pH value of the suspension is greater than 8, otherwise, continuously supplementing and dropwise adding the sodium bicarbonate solution to enable the polyaniline surface to form basic copper carbonate sediment, wherein the color is dark blue;
6) And standing and aging polyaniline for 6 hours, centrifuging or suction filtering to obtain polyaniline-basic copper carbonate composite powder in a wet state, and repeatedly leaching to remove soluble impurities to finally obtain the polyaniline-basic copper carbonate composite product.
2. The method for preparing the additive of the polyaniline-basic copper carbonate composite for concrete according to claim 1, wherein the addition amount of the ethylene carbonate in the step 3) is 1% of the total weight of the mixed solution.
3. The method for preparing the additive of the polyaniline-basic copper carbonate composite according to claim 1, wherein the volume ratio of the ammonium persulfate solution to the aniline hydrochloride solution in the step 4) is 1:1, the dropping speed is 3s to 5s, and the duration of the electromagnetic stirrer is 2 hours.
4. The method for preparing a polyaniline-basic copper carbonate composite additive according to claim 1, wherein the dark green suspension prepared in step 4) is always maintained at a temperature below 5 ℃ in an ice bath.
5. A polyaniline-basic copper carbonate composite additive for concrete prepared by the method for preparing a polyaniline-basic copper carbonate composite additive for concrete according to any one of claims 1 to 5.
6. The use of the concrete polyaniline-basic copper carbonate composite additive according to claim 5, for protecting concrete components in marine environments.
7. The use according to claim 6, characterized by the specific steps of: the polyaniline-basic copper carbonate composite additive of the concrete is mixed with water to form a uniformly dispersed suspension system under the state of maintaining the wet powder, and is added into the concrete in the form of composite suspension in the concrete mixing process.
8. The use according to claim 7, characterized in that the concrete polyaniline-basic copper carbonate complex additive is added in the following amounts: the dry weight of the concrete composite additive accounts for 0.05 to 0.15 percent of the mass of the concrete.
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