CN114933322A - Calcium-aluminum type hydrotalcite of intercalation rust inhibitor and preparation method and application thereof - Google Patents
Calcium-aluminum type hydrotalcite of intercalation rust inhibitor and preparation method and application thereof Download PDFInfo
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000003112 inhibitor Substances 0.000 title claims abstract description 117
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 79
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 79
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 79
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000009830 intercalation Methods 0.000 title abstract description 25
- 230000002687 intercalation Effects 0.000 title abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 84
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 67
- 230000032683 aging Effects 0.000 claims abstract description 44
- 238000000975 co-precipitation Methods 0.000 claims abstract description 39
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011150 reinforced concrete Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 150000001450 anions Chemical class 0.000 claims abstract description 21
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims abstract description 20
- 230000005595 deprotonation Effects 0.000 claims abstract description 14
- 238000010537 deprotonation reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002585 base Substances 0.000 claims abstract description 8
- 238000005349 anion exchange Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000005260 corrosion Methods 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910001424 calcium ion Inorganic materials 0.000 claims description 15
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- -1 aluminum ions Chemical class 0.000 claims description 11
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 5
- 230000002265 prevention Effects 0.000 claims description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000005536 corrosion prevention Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 42
- 238000012360 testing method Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 24
- 235000010344 sodium nitrate Nutrition 0.000 description 21
- 239000004317 sodium nitrate Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 239000012265 solid product Substances 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 238000007873 sieving Methods 0.000 description 13
- 239000004568 cement Substances 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 238000001453 impedance spectrum Methods 0.000 description 9
- 229910000975 Carbon steel Inorganic materials 0.000 description 8
- 239000010962 carbon steel Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011083 cement mortar Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 230000002431 foraging effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOYKKWXSDFNANU-UHFFFAOYSA-M (3-cyano-2-hydroxypropyl)-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)CC#N ZOYKKWXSDFNANU-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention belongs to the technical field of building material corrosion prevention, and particularly relates to calcium-aluminum type hydrotalcite of an intercalation rust inhibitor, and a preparation method and application thereof. The method comprises the steps of dropwise adding a mixed aqueous solution of calcium nitrate and aluminum nitrate into an aqueous solution of alkali metal nitrate, and carrying out coprecipitation reaction under an alkaline condition to obtain a coprecipitation reaction solution; sequentially carrying out low-temperature aging treatment and high-temperature aging treatment on the coprecipitation reaction solution to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite; mixing an organic rust inhibitor and an inorganic strong base solution for deprotonation treatment to obtain an organic rust inhibitor anion solution; mixing the nitrate radical intercalated calcium-aluminum type hydrotalcite and the organic rust inhibitor anion solution, and carrying out anion exchange to obtain the calcium-aluminum type hydrotalcite intercalated with the rust inhibitor. The calcium-aluminum hydrotalcite intercalated with the rust inhibitor prepared by the invention has high loading capacity of the rust inhibitor, and has excellent rust-preventing effect when being applied to a reinforced concrete structure.
Description
Technical Field
The invention belongs to the technical field of building material corrosion prevention, and particularly relates to calcium-aluminum type hydrotalcite of an intercalation rust inhibitor, and a preparation method and application thereof.
Background
China has abundant ocean resources, and is a marine big country since ancient times. However, in the process of ocean construction, it is important to solve the problem of corrosion of reinforced concrete in the ocean, such as bridges, ships, ocean resource development platforms and the like. The chloride ions in free state (accounting for 88% of the total amount of corrosive anions in seawater) cause the corrosion of the reinforced concrete, and the corrosion of the reinforced concrete caused by the permeation and diffusion of the chloride ions is a symptom cause of the degradation of structural materials and structural performance of the concrete engineering. The steel bar rust inhibitor has the outstanding advantages of simplicity, economy and high efficiency, and has become a hotspot for research and application. However, the traditional rust inhibitor has the problems of single function, environmental pollution, insufficient stability and adaptability and the like, and cannot meet the increasingly complex service environment and high durability requirements of major infrastructure.
The hydrotalcite material is also called Layered Double Hydroxides (LDHs), has strong ion exchange performance, and is widely applied to the field of reinforced concrete corrosion prevention. The LDHs can improve the compactness and the mechanical property of the mixed soil and simultaneously improve the chloride ion corrosion resistance of the concrete by combining the physical and chemical actions and the ion exchange performance. Compared with the method of directly adding the rust inhibitor, the hydrotalcite of the intercalated rust inhibitor can release the rust inhibitor as required and simultaneously cure chloride ions, and becomes a leading-edge hotspot for improving the durability of reinforced concrete.
However, the low loading capacity (the loading capacity is less than or equal to 25%) of the rust inhibitor in the LDHs of the intercalation rust inhibitor at present becomes a bottleneck for limiting the further development and the large-scale application of the LDHs/rust inhibitor slow release technology.
Disclosure of Invention
The invention aims to provide calcium-aluminum type hydrotalcite of an intercalation rust inhibitor and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of calcium-aluminum type hydrotalcite of an intercalation rust inhibitor, which comprises the following steps:
dropwise adding a mixed aqueous solution of calcium nitrate and aluminum nitrate into an aqueous solution of alkali metal nitrate, and carrying out coprecipitation reaction under an alkaline condition to obtain a coprecipitation reaction solution;
sequentially carrying out low-temperature aging treatment and high-temperature aging treatment on the coprecipitation reaction liquid to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite;
mixing an organic rust inhibitor and an inorganic strong base solution to carry out deprotonation treatment on the organic rust inhibitor to obtain an organic rust inhibitor anion solution;
mixing the nitrate radical intercalated calcium-aluminum type hydrotalcite and the organic rust inhibitor anion solution, and carrying out anion exchange to obtain the calcium-aluminum type hydrotalcite intercalated with the rust inhibitor.
Preferably, the organic rust inhibitor comprises 2-methoxy-4- (2-propenyl) phenol and/or 3-cyano-2-hydroxy-N, N, N-trimethyl-1-propanaminium chloride.
Preferably, in the mixed aqueous solution of calcium nitrate and aluminum nitrate, the molar concentration of calcium ions is 0.66-0.71 mol/L; the molar ratio of the calcium ions to the aluminum ions is (2-2.5): 1.
Preferably, in the alkali metal nitrate aqueous solution, the molar concentration of nitrate ions is 2.28-2.33 mol/L; the volume ratio of the mixed aqueous solution of the calcium nitrate and the aluminum nitrate to the aqueous solution of the alkali metal nitrate is 1 (2-2.5).
Preferably, the pH value of the coprecipitation reaction is 9.5-12.5.
Preferably, the temperature of the low-temperature aging treatment is 50-70 ℃, and the heat preservation time of the low-temperature aging is 22-26 h; the temperature of the high-temperature ageing is 100-115 ℃, and the heat preservation time of the high-temperature ageing is 46-50 h.
Preferably, the coprecipitation reaction further comprises: and continuously introducing protective gas into the aqueous solution of the alkali metal nitrate, wherein the protective gas is nitrogen.
Preferably, the mass ratio of the organic rust inhibitor to the nitrate radical intercalated calcium-aluminum type hydrotalcite is (3.5-5.5): (1-2).
The invention provides the calcium-aluminum hydrotalcite of the intercalation rust inhibitor prepared by the preparation method in the technical scheme, wherein in the calcium-aluminum hydrotalcite of the intercalation rust inhibitor, the mass of anions of the rust inhibitor accounts for 70-80 wt% of the mass of the calcium-aluminum hydrotalcite.
The invention provides an application of calcium-aluminum type hydrotalcite of the intercalation rust inhibitor in rust prevention of a reinforced concrete structure.
The invention provides a preparation method of calcium-aluminum type hydrotalcite of an intercalation rust inhibitor, which comprises the following steps: dropwise adding a mixed aqueous solution of calcium nitrate and aluminum nitrate into an aqueous solution of alkali metal nitrate, and carrying out coprecipitation reaction under an alkaline condition to obtain a coprecipitation reaction solution; sequentially carrying out low-temperature aging treatment and high-temperature aging treatment on the coprecipitation reaction liquid to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite; mixing an organic rust inhibitor and an inorganic strong base solution to carry out deprotonation treatment on the organic rust inhibitor to obtain an organic rust inhibitor anion solution; mixing the nitrate radical intercalated calcium-aluminum type hydrotalcite and the organic rust inhibitor anion solution, and carrying out anion exchange to obtain the calcium-aluminum type hydrotalcite intercalated with the rust inhibitor. The preparation method provided by the invention combines a coprecipitation method and an ion exchange method, the coprecipitation method is adopted to prepare the nitrate radical intercalated calcium-aluminum type hydrotalcite with a high-quality and complete structure through dropwise adding and low-temperature and high-temperature aging treatment in sequence, then the organic rust inhibitor is deprotonated and then is subjected to anion exchange with the nitrate radical intercalated calcium-aluminum type hydrotalcite, and the prepared intercalated rust inhibitor calcium-aluminum type hydrotalcite has high loading capacity of the rust inhibitor, and has excellent rust-proof effect when being applied to a reinforced concrete structure. Meanwhile, the preparation method provided by the invention adopts the calcium-aluminum type hydrotalcite load corrosion inhibitor, so that the adverse effect that the Mg-Al hydrotalcite system may bring unstable volume structure to the cement-based material is effectively solved, and the compressive strength performance of the cement can be improved.
Drawings
FIG. 1 is an impedance spectrum of a reinforced concrete test block prepared from a blank control group;
FIG. 2 is an impedance spectrum of a reinforced concrete test block prepared by adding the product of comparative example 1;
FIG. 3 is an impedance spectrum of a reinforced concrete test block prepared by adding the product of example 1;
FIG. 4 is an impedance spectrum of a reinforced concrete test block prepared by adding the product of example 2;
FIG. 5 is an impedance spectrum of a reinforced concrete test block prepared by adding the product of example 3;
FIG. 6 is a graph showing UV spectroscopic absorbances of reinforced concrete test pieces prepared by adding the products of examples 2 and 4.
Detailed Description
The invention provides a preparation method of calcium-aluminum type hydrotalcite of an intercalation rust inhibitor, which comprises the following steps:
dropwise adding a mixed aqueous solution of calcium nitrate and aluminum nitrate into an aqueous solution of alkali metal nitrate, and carrying out coprecipitation reaction under an alkaline condition to obtain a coprecipitation reaction solution;
sequentially carrying out low-temperature aging treatment and high-temperature aging treatment on the coprecipitation reaction solution to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite;
mixing an organic rust inhibitor and an inorganic strong base solution to carry out deprotonation treatment on the organic rust inhibitor to obtain an organic rust inhibitor anion solution;
mixing the nitrate radical intercalated calcium-aluminum type hydrotalcite and the organic rust inhibitor anion solution, and carrying out anion exchange to obtain the calcium-aluminum type hydrotalcite intercalated with the rust inhibitor.
In the present invention, all the preparation starting materials/components are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of dropwise adding a mixed aqueous solution of calcium nitrate and aluminum nitrate into an aqueous solution of alkali metal nitrate, and carrying out coprecipitation reaction under an alkaline condition to obtain a coprecipitation reaction solution.
In the present invention, the molar ratio of calcium ions to aluminum ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is preferably (2 to 2.5):1, and more preferably (2.1 to 2.4): 1.
In the invention, the molar concentration of calcium ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is preferably 0.66-0.71 mol/L, and more preferably 0.68-0.7 mol/L.
In the present invention, the water in the mixed aqueous solution of calcium nitrate and aluminum nitrate is preferably boiled water.
In the present invention, the raw material of calcium nitrate in the mixed aqueous solution of calcium nitrate and aluminum nitrate is preferably Ca (NO) 3 ) 2 ·4H 2 O。
In the present invention, the raw material of aluminum nitrate in the mixed aqueous solution of calcium nitrate and aluminum nitrate is preferably Al (NO) 3 ) 3 ·9H 2 O。
In the present invention, the water in the aqueous solution of an alkali metal nitrate is preferably boiled water.
In the present invention, the alkali metal nitrate in the aqueous alkali metal nitrate solution is specifically preferably sodium nitrate.
In the invention, the molar concentration of nitrate ions in the alkali metal nitrate aqueous solution is preferably 2.28-2.33 mol/L, and more preferably 2.3-2.32 mol/L.
In the present invention, the volume ratio of the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of alkali metal nitrate is preferably 1 (2 to 2.5), more preferably 1 (2.1 to 2.3).
In the present invention, the dropping speed is preferably 0.3 to 0.5mL/s, and preferably 0.4 to 0.5 mL/s.
In the present invention, the dropping of the aqueous solution of an alkali metal nitrate is preferably performed under stirring, and in the present invention, the rotation speed of the stirring is preferably 200 to 300 rpm.
In the invention, the temperature of the coprecipitation reaction is preferably 60-70 ℃, and more preferably 65 ℃.
In the invention, the pH value of the coprecipitation reaction is preferably 9.5-12.5, and more preferably 10-12.
In the present invention, the pH of the coprecipitation reaction is preferably obtained by dropping a strong alkali solution simultaneously with dropping the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of alkali metal nitrate. In the present invention, the strongly alkaline solution is preferably a boiled aqueous sodium hydroxide solution, and in the present invention, the molar concentration of the boiled aqueous sodium hydroxide solution is preferably 2 mol/L.
In the present invention, during the coprecipitation reaction, the present invention preferably further comprises continuously feeding a protective gas, preferably nitrogen, into the aqueous alkali metal nitrate solution. The present invention has no particular requirement on the flow rate of the shielding gas.
After the coprecipitation reaction liquid is obtained, the coprecipitation reaction liquid is subjected to low-temperature aging treatment and high-temperature aging treatment in sequence to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite.
In the invention, the temperature of the low-temperature aging treatment is preferably 50-70 ℃, and more preferably 55-65 ℃.
In the invention, the low-temperature aging heat preservation time is preferably 22-26 h, and more preferably 24 h.
In the invention, the high-temperature aging temperature is preferably 100-115 ℃, and more preferably 110 ℃.
In the invention, the heat preservation time of the high-temperature aging is preferably 46-50 h, and more preferably 48 h.
In the invention, the high-temperature aging treatment is carried out to obtain an aging treatment liquid, and the aging treatment liquid is preferably subjected to post-treatment to obtain the nitrate radical intercalated calcium-aluminum type hydrotalcite. In the present invention, the post-treatment preferably comprises: and sequentially carrying out solid-liquid separation, water washing, drying, grinding and screening. In the present invention, the solid-liquid separation is preferably centrifugal separation, and in the present invention, the solid product of the solid-liquid separation is preferably washed with water, and in the present invention, the washing with water is particularly preferably washing with distilled water, and in the present invention, the number of times of washing with water is preferably 4 to 5. In the present invention, the washed solid product is preferably dried, in the present invention, the drying temperature is preferably 105 ℃, and in the present invention, the drying is particularly preferably drying. The invention is not particularly limited to the specific embodiment of the grinding, and in the invention, the sieving is preferably 200 mesh sieving.
In the present invention, the nitrate radical intercalated calcium aluminum type hydrotalcite has preferably particle size of < 74 μm.
The invention mixes the organic rust inhibitor and the inorganic strong base solution to carry out deprotonation treatment on the organic rust inhibitor, thus obtaining the anion solution of the organic rust inhibitor.
In the present invention, the organic rust inhibitor comprises 2-methoxy-4- (2-propenyl) phenol and/or 3-cyano-2-hydroxy-N, N, N-trimethyl-1-propanammonium chloride, more preferably 2-methoxy-4- (2-propenyl) phenol or 3-cyano-2-hydroxy-N, N, N-trimethyl-1-propanammonium chloride, and further preferably 2-methoxy-4- (2-propenyl) phenol.
In the invention, the mass ratio of the organic rust inhibitor to the nitrate radical intercalated calcium-aluminum type hydrotalcite is preferably (3.5-5.5): 1-2, and more preferably (4-5): 1-2.
In the present invention, the strong inorganic alkaline solution is preferably a sodium hydroxide solution.
In the invention, the molar concentration of the inorganic strong alkali solution is preferably 0.1-0.2 mol/L.
In the present invention, the organic rust inhibitor is preferably used in the form of an aqueous organic rust inhibitor solution, and in the present invention, when the organic rust inhibitor is preferably used in the form of an aqueous organic rust inhibitor solution, the molar concentration of the aqueous organic rust inhibitor solution is preferably 0.1 mol/L.
In the invention, when the organic rust inhibitor is preferably used in the form of an organic rust inhibitor aqueous solution, the volume ratio of the organic rust inhibitor aqueous solution to the inorganic strong base solution is preferably (1-2): 1.
In the invention, the deprotonation treatment of the organic rust inhibitor is preferably carried out by carrying out neutralization reaction on the organic rust inhibitor and inorganic strong base to obtain the metal salt of the organic rust inhibitor.
In the present invention, the organic rust inhibitor is deprotonated to a pH of preferably 10.
In the present invention, the temperature of the deprotonation treatment of the organic rust inhibitor is preferably room temperature.
In the invention, the time of deprotonation treatment of the organic rust inhibitor is preferably 30-40 min.
In the present invention, the deprotonation treatment of the organic rust inhibitor is preferably carried out under stirring, and the present invention has no particular requirement for the specific implementation of the stirring.
After the nitrate radical intercalated calcium-aluminum type hydrotalcite and the organic rust inhibitor anion solution are obtained, the nitrate radical intercalated calcium-aluminum type hydrotalcite and the organic rust inhibitor anion solution are mixed for anion exchange, and the calcium-aluminum type hydrotalcite intercalated with the rust inhibitor is obtained.
In the invention, the ion exchange is preferably carried out under the heating condition of a water bath, and the temperature of the water bath heating is preferably 70-80 ℃.
In the present invention, the incubation time for the ion exchange is preferably 48 hours.
In the present invention, the ion exchange is preferably carried out under stirring conditions, and the present invention has no particular requirement on the rotation speed of the stirring.
In the present invention, the pH of the ion exchange is preferably 10.
In the invention, ion exchange reaction liquid is obtained after the ion exchange, and the invention preferably carries out post-treatment on the ion exchange reaction liquid to obtain the calcium-aluminum type hydrotalcite of the intercalation rust inhibitor. In the present invention, the post-treatment preferably comprises: and sequentially carrying out solid-liquid separation, drying, grinding and screening. In the present invention, the solid-liquid separation is preferably centrifugal separation, and in the present invention, the solid product of the solid-liquid separation is preferably dried, in the present invention, the temperature of the drying is preferably 105 ℃, and in the present invention, the drying is particularly preferably oven drying. The invention is not particularly limited to the specific embodiment of the grinding, and in the invention, the sieving is preferably 200 mesh sieving.
In the invention, the particle size of the calcium-aluminum type hydrotalcite of the intercalation rust inhibitor is preferably less than 74 μm.
The invention provides the calcium-aluminum hydrotalcite of the intercalation rust inhibitor prepared by the preparation method in the technical scheme, wherein in the calcium-aluminum hydrotalcite of the intercalation rust inhibitor, the mass of anions of the rust inhibitor accounts for 70-80 wt% of the mass of the calcium-aluminum hydrotalcite.
The invention provides an application of calcium-aluminum type hydrotalcite of the intercalation rust inhibitor in rust prevention of a reinforced concrete structure.
In the invention, when the intercalated rust inhibitor is applied, the calcium-aluminum hydrotalcite of the intercalated rust inhibitor in the technical scheme is preferably added into cement mortar, stirred uniformly and poured into a mold with carbon steel in the middle for hardening, so that a reinforced concrete structure is obtained.
In the present invention, the cement mortar includes cement, sand and water.
In the present invention, the mass ratio of the cement, the sand and the water is preferably 450:1350: 225.
In the present invention, the cement mortar preferably has a water cement ratio of 0.5: 1.
In the invention, the mass ratio of the calcium-aluminum type hydrotalcite of the intercalation rust inhibitor to the cement in the cement mortar is preferably 0.1: 1.
The invention starts from the nucleation growth of LDHs and the intercalation exchange mechanism of interlayer objects, and realizes the controllable synthesis of the intercalated LDHs with high quality and high load organic rust inhibitor by detecting the influence rule of the synthesis conditions and step parameters on the structure, size, composition and load capacity of the LDHs; on the basis, a continuous flow synthesis process of the LDHs/organic rust inhibitor is constructed, so that batch production of the LDHs is finally realized, and important reference is provided for further development and application of the LDHs in the field of concrete durability.
In order to further illustrate the present invention, the following detailed description of the technical solutions provided by the present invention is made with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing Ca (NO) 3 ) 2 ·4H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in boiled water to obtain a mixed aqueous solution of calcium nitrate and aluminum nitrate, wherein the molar ratio of calcium ions to aluminum ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is 2:1, and the molar concentration of the calcium ions is 0.66 mol/L; the mixed water solution of calcium nitrate and aluminum nitrate is controlled by a peristaltic pump to be dripped into NaNO at the dripping speed of 0.3mL/s 3 And boiled water, wherein the molar concentration of nitrate radicals in the sodium nitrate aqueous solution is 2.33 mol/L; the volume ratio of the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of sodium nitrate is 1:2, an electric stirrer is adopted to stir the aqueous solution of sodium nitrate during the dripping, the stirring speed is 200rpm, and simultaneously 2mol/L NaOH and boiled water are dripped to form an aqueous solution of NaOH so as to regulate the pH value of the coprecipitation reaction to be 10; meanwhile, when the coprecipitation reaction is carried out by dropwise adding, nitrogen is continuously introduced into the sodium nitrate aqueous solution to be used as protective gas;
after the dropwise addition is finished, aging the mixed suspension for 22h at the temperature of 65 ℃, then heating to 110 ℃ for aging for 46h, and meanwhile, continuously introducing nitrogen into the mixed suspension as protective gas in the aging process; after centrifugally separating the aging reaction liquid, cleaning the solid product with distilled water for 4 times, drying and grinding the solid product into powder, and sieving the powder with a 200-mesh sieve to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite;
selecting 2-methoxy-4- (2-propenyl) phenol (EG) as a rust inhibitor, and carrying out deprotonation treatment on the rust inhibitor: mixing 0.1mol/L EG aqueous solution and 0.1mol/L NaOH solution, wherein the volume ratio of the EG aqueous solution to the NaOH solution is 2:1, the volume of the mixed solution is 500mL, the pH value of the solution is 10, and carrying out neutralization reaction for 30min under the stirring condition to obtain the NaEG solution;
adding 2g of nitrate radical intercalated calcium-aluminum type hydrotalcite into a NaEG solution, continuously stirring the mixed solution for reaction for 48 hours in a water bath at 70-80 ℃, simultaneously controlling the pH value of the solution to be 10, recovering a solid product through centrifugation, drying, grinding into powder, and sieving with a 200-mesh sieve to obtain a calcium-aluminum type hydrotalcite product of the intercalated rust inhibitor. Recorded as LDH-EG.
In the calcium-aluminum type hydrotalcite with the intercalation rust inhibitor prepared in this example, the mass of the anions of the rust inhibitor accounts for 73% of the mass of the calcium-aluminum type hydrotalcite.
Example 2
Mixing Ca (NO) 3 ) 2 ·4H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in boiled water to obtain a mixed aqueous solution of calcium nitrate and aluminum nitrate, wherein the molar ratio of calcium ions to aluminum ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is 2:1, and the molar concentration of the calcium ions is 0.66 mol/L; the mixed water solution of calcium nitrate and aluminum nitrate is dripped into NaNO at the dripping speed of 0.4mL/s by using a peristaltic pump 3 And boiled water, wherein the molar concentration of nitrate radicals in the sodium nitrate aqueous solution is 2.33 mol/L; the volume ratio of the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of sodium nitrate is 1:2, an electric stirrer is adopted to stir the aqueous solution of sodium nitrate during the dropwise adding, the stirring speed is 250rpm, and simultaneously 2mol/L NaOH and boiled water are dropwise added to form an aqueous solution of NaOH so as to regulate the pH value of the coprecipitation reaction to be 11; meanwhile, when the coprecipitation reaction is carried out by dropwise adding, nitrogen is continuously introduced into the sodium nitrate aqueous solution to be used as protective gas;
after the dropwise addition is finished, aging the mixed suspension for 24 hours at the temperature of 65 ℃, then heating to 110 ℃ for aging for 48 hours, and meanwhile, continuously introducing nitrogen into the mixed suspension as protective gas in the aging process; after centrifugally separating the aging reaction liquid, cleaning the solid product with distilled water for 4 times, drying and grinding the solid product into powder, and sieving the powder with a 200-mesh sieve to obtain nitrate radical intercalated calcium aluminum type hydrotalcite;
selecting 2-methoxy-4- (2-propenyl) phenol (EG) as a rust inhibitor, and carrying out deprotonation treatment on the rust inhibitor: mixing 0.1mol/L EG aqueous solution and 0.15mol/L NaOH solution, wherein the volume ratio of the EG aqueous solution to the NaOH solution is 1.5:1, the volume of the mixed solution obtained after mixing is 500mL, the pH value of the solution is 10, and carrying out neutralization reaction for 30min under the stirring condition to obtain a NaEG solution;
adding 1.5g of nitrate radical intercalated calcium-aluminum type hydrotalcite into a NaEG solution, continuously stirring the mixed solution for reaction for 48 hours in a water bath at 70-80 ℃, simultaneously controlling the pH value of the solution to be 10, recovering a solid product through centrifugation, drying, grinding into powder, and sieving with a 200-mesh sieve to obtain a calcium-aluminum type hydrotalcite product of the intercalated rust inhibitor. As LDH-EG.
In the calcium-aluminum hydrotalcite of the intercalation rust inhibitor prepared in this example, the mass percentage of the anions of the rust inhibitor in the calcium-aluminum hydrotalcite is 76%.
Example 3
Mixing Ca (NO) 3 ) 2 ·4H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in boiled water to obtain a mixed aqueous solution of calcium nitrate and aluminum nitrate, wherein the molar ratio of calcium ions to aluminum ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is 2.5:1, and the molar concentration of the calcium ions is 0.71 mol/L; the mixed water solution of calcium nitrate and aluminum nitrate is controlled by a peristaltic pump to be dripped into NaNO at the dripping speed of 0.3mL/s 3 And boiled water, wherein the molar concentration of nitrate radicals in the sodium nitrate aqueous solution is 2.28 mol/L; the volume ratio of the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of sodium nitrate is 1:2.5, an electric stirrer is adopted to stir the aqueous solution of sodium nitrate during the dropwise adding, the stirring speed is 200rpm, and simultaneously 2mol/L of NaOH and boiled water are dropwise added to form an aqueous solution of NaOH so as to regulate the pH value of the coprecipitation reaction to be 12; meanwhile, when the coprecipitation reaction is carried out by dropwise adding, nitrogen is continuously introduced into the sodium nitrate aqueous solution to be used as protective gas;
after the dropwise addition is finished, aging the mixed suspension at the temperature of 65 ℃ for 26h, heating to 110 ℃ and aging for 50h, and meanwhile, continuously introducing nitrogen into the mixed suspension as protective gas in the aging process; after centrifugally separating the aging reaction liquid, cleaning the solid product for 5 times by using distilled water, drying and grinding the solid product into powder, and sieving the powder by using a 200-mesh sieve to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite;
selecting 2-methoxy-4- (2-propenyl) phenol (EG) as a rust inhibitor, and carrying out deprotonation treatment on the rust inhibitor: mixing 0.1mol/L EG aqueous solution and 0.2mol/L NaOH solution, wherein the volume ratio of the EG aqueous solution to the NaOH solution is 1:1, the volume of the mixed solution is 500mL, the pH value of the solution is 10, and carrying out neutralization reaction for 40min under the stirring condition to obtain the NaEG solution;
adding 1g of nitrate radical intercalated calcium-aluminum type hydrotalcite into a NaEG solution, continuously stirring the mixed solution for reaction for 48 hours in a water bath at 70-80 ℃, simultaneously controlling the pH value of the solution to be 10, recovering a solid product through centrifugation, drying, grinding into powder, and sieving with a 200-mesh sieve to obtain a calcium-aluminum type hydrotalcite product of the intercalated rust inhibitor. As LDH-EG.
In the calcium-aluminum hydrotalcite of the intercalation rust inhibitor prepared in this example, the mass of the corrosion inhibitor anion accounts for 78% of the mass of the calcium-aluminum hydrotalcite.
Example 4
Mixing Ca (NO) 3 ) 2 ·4H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in boiled water to obtain a mixed aqueous solution of calcium nitrate and aluminum nitrate, wherein the molar ratio of calcium ions to aluminum ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is 2:1, and the molar concentration of the calcium ions is 0.66 mol/L; the mixed water solution of calcium nitrate and aluminum nitrate is dripped into NaNO at the dripping speed of 0.4mL/s by using a peristaltic pump 3 And boiled water, wherein the molar concentration of nitrate radicals in the sodium nitrate aqueous solution is 2.33 mol/L; the volume ratio of the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of sodium nitrate is 1:2, an electric stirrer is adopted to stir the aqueous solution of sodium nitrate during the dropwise adding, the stirring speed is 250rpm, and simultaneously 2mol/L NaOH and boiled water are dropwise added to form an aqueous solution of NaOH so as to regulate the pH value of the coprecipitation reaction to be 11; meanwhile, when the coprecipitation reaction is carried out by dropwise adding, nitrogen is continuously introduced into the sodium nitrate aqueous solution to be used as protective gas;
after the dropwise addition is finished, aging the mixed suspension for 24 hours at the temperature of 65 ℃, then heating to 110 ℃ for aging for 48 hours, and meanwhile, continuously introducing nitrogen into the mixed suspension as protective gas in the aging process; after centrifugally separating the aging reaction liquid, cleaning the solid product with distilled water for 4 times, drying and grinding the solid product into powder, and sieving the powder with a 200-mesh sieve to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite;
3-cyano-2-hydroxy-N, N, N-trimethyl-1-propanammonium Chloride (CHT) is used as a rust inhibitor, and deprotonation treatment is carried out on the rust inhibitor: mixing 0.1mol/L CHT aqueous solution and 0.15mol/L NaOH, wherein the volume ratio of the CHT aqueous solution to the NaOH solution is 1.5:1, the volume of the mixed solution obtained after mixing is 500mL, the pH value of the solution is 10, and carrying out neutralization reaction for 30min under the stirring condition to obtain a NaCHT solution;
adding 1.5g of nitrate radical intercalated calcium-aluminum type hydrotalcite into a NaCHT solution, continuously stirring the mixed solution at 70-80 ℃ in a water bath for reaction for 48 hours, simultaneously controlling the pH value of the solution to be 10, recovering a solid product through centrifugation, drying, grinding into powder, and sieving with a 200-mesh sieve to obtain a calcium-aluminum type hydrotalcite product of the intercalated rust inhibitor. As LDH-CHT.
In the calcium-aluminum hydrotalcite of the intercalation rust inhibitor prepared in this example, the mass percentage of the anions of the rust inhibitor in the calcium-aluminum hydrotalcite is 58%.
Comparative example 1
Mixing Mg (NO) 3 ) 2 ·4H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in boiled water to obtain a mixed aqueous solution of magnesium nitrate and aluminum nitrate, wherein the molar ratio of calcium ions to aluminum ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is 2:1, and the molar concentration of magnesium ions is 0.66 mol/L; the mixed water solution of calcium nitrate and aluminum nitrate is controlled by a peristaltic pump to be dripped into NaNO at the dripping speed of 0.3mL/s 3 And boiled water, wherein the molar concentration of nitrate radicals in the sodium nitrate aqueous solution is 2.33 mol/L; the volume ratio of the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of sodium nitrate is 1:2, an electric stirrer is adopted to stir the aqueous solution of sodium nitrate during the dripping, the stirring speed is 200rpm, and simultaneously 2mol/L NaOH and boiled water are dripped to form an aqueous solution of NaOH so as to regulate the pH value of the coprecipitation reaction to be 10; meanwhile, when the coprecipitation reaction is carried out by dropwise adding, nitrogen is continuously introduced into the sodium nitrate aqueous solution to be used as protective gas;
after the dropwise addition is finished, aging the mixed suspension for 24 hours at the temperature of 65 ℃, then heating to 110 ℃ for aging for 48 hours, and meanwhile, continuously introducing nitrogen into the mixed suspension as protective gas in the aging process; and (3) after centrifugally separating the aging reaction liquid, cleaning the solid product with distilled water for 4 times, drying and grinding the solid product into powder, and sieving the powder with a 200-mesh sieve to obtain nitrate radical intercalated magnesium-aluminum type hydrotalcite.
Application example 1
LDH-EG prepared in examples 1-3 and magnesium aluminum hydrotalcite intercalated by nitrate radical prepared in comparative example 1 are added into cement mortar according to the proportion of 10 wt% of the cement (the products in examples 1-3 and comparative example 1 are not added as blank control group), and after being uniformly stirred, the cement mortar is respectively poured into a mould filled with carbon steel and a mould without carbon steel, wherein the specification of the carbon steel is as follows: the length is 200mm, and the length is 200mm,
the wire was wrapped 30mm from the ends of the carbon steel and sealed with epoxy. After hardening, mortar test pieces (40mm multiplied by 160mm) and pure mortar test pieces (40mm multiplied by 160mm) wrapped with carbon steel are obtained. Carrying out subsequent electrochemical tests on the mortar test block wrapped with the carbon steel; and carrying out subsequent compressive strength tests on the pure mortar test blocks, wherein the compressive strength values of the mortar in each group are maintained in a standard way for 3d and 28 d. Table 1 shows the components of the mortar raw material used in the present application example, and table 2 shows the mixing ratio of the mortar raw material used in the present application example.
Table 1 application example 1 mortar raw material composition
TABLE 2 mortar for application example 1 raw material composition mixing ratio (kg/m) 3 )
The electrochemical impedance of the mortar test block coated with the carbon steel is obtained after hardening, the result is shown in figures 1-5, and figure 1 is an impedance spectrogram of a reinforced concrete test block prepared by a blank control group; FIG. 2 is an impedance spectrum of a reinforced concrete test block prepared by adding the product of comparative example 1; FIG. 3 is an impedance spectrum of a reinforced concrete block prepared by adding the product of example 1; FIG. 4 is an impedance spectrum of a reinforced concrete test block prepared by adding the product of example 2;
FIG. 5 is an impedance spectrum of a reinforced concrete block prepared by adding the product of example 3. In fig. 1, in the initial period of the test, because the steel bar is not corroded, the blank test block is in the passivation period, the passive film impedance and capacitance of the steel bar are maximum values, and the capacitive arc shows a raised straight line. With the continuous extension of the corrosion time, the steel bar enters the corrosion development period, the capacitive reactance arc is gradually changed from a raised straight line into an arc with gradually reduced radius, which shows that the impedance and capacitance of the passivation film on the surface of the steel bar are gradually reduced, the passivation film of the steel bar falls off, and the steel bar begins to be corroded at the moment. When the corrosion time is prolonged to 21h, the capacitive arc radius reaches the minimum value state, which indicates that the passive film on the surface of the steel bar is basically and completely damaged, the volume of rusty matters generated by the corrosion of the steel bar is increased, and expansion pressure is generated on concrete, so that obvious cracks appear on the surface of a test block, and a large amount of rust is discharged. As can be found in FIGS. 3-5, after LDH-EG prepared by the method is doped in a test block, the topological structure of an alternating current impedance spectrogram of the test block is kept stable all the time in a stage of electric acceleration of 0-30 h, no qualitative change occurs, and no obvious change occurs in capacitive reactance arc, which indicates that the addition of LDH-EG can prevent Cl - The corrosion of the steel bar is inhibited. And after 48 hours, the topological structure of the low-frequency part is gradually changed into a flattened capacitive reactance arc from a raised straight line, the radius of the capacitive reactance arc is obviously reduced, the impedance and the capacitance of the passivation film on the surface of the steel bar are reduced, the passivation film on the surface of the steel bar is damaged, and the steel bar enters the corrosion development period. When the electrically accelerated corrosion time reaches 72h, the capacitive arc radius tends to be in a minimum state, and obvious rust cracking occurs on the surface of the test block finally due to the action of the expansion pressure of the steel bar rusty substance. Compared with a blank test block, the corrosion time of the steel bar TCI is prolonged by more than 2 times. It is shown that the addition of LDH-EG has a positive effect on the prevention of reinforcing steel bar corrosion of the cement-based material, and the performance and the state of the reinforced concrete sample obtained by using the product prepared in example 2 as an antirust agent are the most stable.
For the result obtained in fig. 2, when the reinforced concrete sample obtained from the product prepared in comparative example 1 is 18-30 hours, the capacitive arc radius tends to be the minimum state, and obvious rust cracking appears on the surface of the test block.
The compressive strength results are shown in table 3:
TABLE 3 various groups of test blocks 28d compressive Strength values (MPa)
As shown in Table 3, for the compressive strength values of the test blocks 28d of each group, it can be found that the test blocks 3d and 28d of the test blocks of examples 1 to 3 have the strength obviously provided compared with the blank group added with LDH-EG because the addition of the Ca-Al system is helpful for the cement hydration process, and the addition of LDH-EG is proved to be helpful for improving the mechanical properties of the cement-based material.
Example 2 and example 4 were tested for rust inhibitor intercalation content by uv spectrophotometer as shown in figure 6. The test results showed that example 2, which used 2-methoxy-4- (2-propenyl) phenol (EG) as a rust inhibitor, had a higher absorbance. The higher intercalation content of the rust inhibitor in the group of example 2 is shown, namely the 2-methoxy-4- (2-propenyl) phenol (EG) is used as the rust inhibitor which has better compatibility with the nitrate radical intercalated calcium aluminum type hydrotalcite system designed by the invention.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A preparation method of calcium-aluminum type hydrotalcite with an intercalated rust inhibitor is characterized by comprising the following steps:
dropwise adding a mixed aqueous solution of calcium nitrate and aluminum nitrate into an aqueous solution of alkali metal nitrate, and carrying out coprecipitation reaction under an alkaline condition to obtain a coprecipitation reaction solution;
sequentially carrying out low-temperature aging treatment and high-temperature aging treatment on the coprecipitation reaction liquid to obtain nitrate radical intercalated calcium-aluminum type hydrotalcite;
mixing an organic rust inhibitor and an inorganic strong base solution to carry out deprotonation treatment on the organic rust inhibitor to obtain an organic rust inhibitor anion solution;
mixing the nitrate radical intercalated calcium-aluminum type hydrotalcite and the organic rust inhibitor anion solution, and carrying out anion exchange to obtain the calcium-aluminum type hydrotalcite intercalated with the rust inhibitor.
2. The method of claim 1, wherein the organic rust inhibitor comprises 2-methoxy-4- (2-propenyl) phenol and/or 3-cyano-2-hydroxy-N, N-trimethyl-1-propanaminium chloride.
3. The preparation method according to claim 1, wherein the molar concentration of calcium ions in the mixed aqueous solution of calcium nitrate and aluminum nitrate is 0.66 to 0.71 mol/L; the molar ratio of the calcium ions to the aluminum ions is (2-2.5): 1.
4. The method according to claim 1 or 3, wherein the molar concentration of nitrate ions in the aqueous solution of alkali metal nitrate is 2.28 to 2.33 mol/L; the volume ratio of the mixed aqueous solution of calcium nitrate and aluminum nitrate to the aqueous solution of alkali metal nitrate is 1 (2-2.5).
5. The preparation method according to claim 1, wherein the pH value of the coprecipitation reaction is 9.5 to 12.5.
6. The preparation method according to claim 1, wherein the temperature of the low-temperature aging treatment is 50-70 ℃, and the holding time of the low-temperature aging is 22-26 h; the temperature of the high-temperature ageing is 100-115 ℃, and the heat preservation time of the high-temperature ageing is 46-50 h.
7. The preparation method according to claim 1, wherein the coprecipitation reaction further comprises: and continuously introducing protective gas into the alkali metal nitrate aqueous solution, wherein the protective gas is nitrogen.
8. The preparation method of claim 1 or 2, wherein the mass ratio of the organic rust inhibitor to the nitrate radical intercalated calcium-aluminum type hydrotalcite is (3.5-5.5) to (1-2).
9. The calcium-aluminum hydrotalcite with the intercalated corrosion inhibitor prepared by the preparation method of any one of claims 1 to 8 is characterized in that the weight percentage of the corrosion inhibitor anions in the calcium-aluminum hydrotalcite with the intercalated corrosion inhibitor is 70-80 wt%.
10. The use of the calcium-aluminum type hydrotalcite of the intercalated rust inhibitor of claim 9 for rust prevention in reinforced concrete structures.
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Application publication date: 20220823 |