CN114180878B - Metal organic framework supported rust inhibitor and preparation method and application thereof - Google Patents
Metal organic framework supported rust inhibitor and preparation method and application thereof Download PDFInfo
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- CN114180878B CN114180878B CN202010961407.6A CN202010961407A CN114180878B CN 114180878 B CN114180878 B CN 114180878B CN 202010961407 A CN202010961407 A CN 202010961407A CN 114180878 B CN114180878 B CN 114180878B
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
The invention belongs to the technical field of building functional materials, and particularly relates to a metal organic framework supported rust inhibitor and a preparation method thereof. The metal organic framework loaded rust inhibitor loads high-efficiency rust inhibitor components by constructing a core-shell structure of the reinforcing steel bar rust inhibitor loaded in the metal organic framework and utilizing the porous or adsorption performance of the metal organic framework, so that the loaded rust inhibitor reduces the hydration process of the reinforcing steel bar rust inhibitor and cement in the mixing process of the cementing material, thereby reducing the influence of the reinforcing steel bar rust inhibitor on the hydration process of the cement and further influencing the working and mechanical properties of the hydraulic cementing material; the loaded steel bar rust inhibitor component can be gradually and slowly released through the through holes on the surface of the metal organic frame after the hydraulic material is hardened, so that the long-acting and high-efficiency rust inhibition effect is achieved, and the ion transmission resistance of concrete is improved. The load type rust inhibitor can be applied to concrete in a direct doping mode, and has long-acting and efficient rust inhibiting effect.
Description
Technical Field
The invention belongs to the technical field of building functional materials, and particularly relates to a metal organic framework supported rust inhibitor and a preparation method and application thereof.
Background
The corrosion and damage phenomena of the reinforced concrete are more and more, and serious safety accidents can be caused when the corrosion and damage phenomena are serious. With the rapid development of the economic society and the continuous widening of the engineering application field, the severe corrosion environment will be more and more common, and the technical measures of long-term effectiveness of steel bar rust resistance and concrete corrosion resistance need to be provided urgently.
Generally, a method for controlling corrosion of reinforcing steel bars includes: corrosion-resistant steel bars, cathodic protection, coating (plating) layer steel bars, concrete surface coating, steel bar rust inhibitor and the like, wherein the steel bar rust inhibitor is added into the concrete, has the advantages of obvious effect, simple and convenient construction and economy and effectiveness, and is the most common technical measure for preventing the steel bars from being corroded. In recent years, with the increasing scale of the application of the steel bar rust inhibitor and the gradual manifestation of the application effect, research on the development and application of the steel bar rust inhibitor is more and more extensive.
Japan and the united states are the countries that have first used rebar rust inhibitors. The reinforcing steel bar rust inhibitor comprises an inorganic rust inhibitor and an organic rust inhibitor according to the composition of the substances, and is divided into a migration type rust inhibitor and an doped type rust inhibitor according to the application mode. Early reinforcing steel bar rust inhibitors were mainly doped and mainly included sodium nitrite, sodium benzoate, chromate, and the like. Organic rust inhibitors have been developed since the 80 s of the 20 th century because of environmental concerns with inorganic nitrite rust inhibitors. Meanwhile, the organic rust inhibitor is mostly used as a migration type rust inhibitor for research and application due to strong permeability and adsorption film-forming property. Organic rust inhibitors are generally classified into types of amines, aldehydes, alkynols, organic phosphorus compounds, organic sulfur compounds, carboxylic acids and salts thereof, sulfonic acids and salts thereof, heterocyclic compounds and the like according to substance classification, but since many organic components have an influence on the working and mechanical properties of concrete, the types of practically applicable organic rust inhibitors are few. For example, US 7125441B1 reports a composition for inhibiting corrosion of metal materials in concrete, including gluconate, nitrite and alkanolamine benzoate, because gluconate has a strong retarding effect, inhibits hydration of cement, seriously affects the development of concrete work and mechanical properties, although nitrite can promote cement hydration, the improvement of concrete work and mechanical properties by the combination of the two is still limited, and nitrite itself has carcinogenicity, causes great environmental pollution, and is increasingly limited in application. In addition, in order to develop more environmentally friendly and efficient organic rust inhibitors, alkylol amines and derivatives thereof have been widely studied. For example, mapei and Sika corporation of switzerland (WO 2015/059238A1, US 6149725A3 A1) in italy both report the application of the alkylol amine steel bar rust inhibitor, the molecular structure can be coated on the surface of concrete or doped in the concrete or mortar as a protective or repair layer of a reinforced concrete structure, but the long-term effect of the rust inhibitor is limited due to the high permeability and volatility of the alkylol amine, and most of the alkylol amine can be dissipated and lost in the application, so that the long-term effect of the rust inhibitor is uncertain. In order to reduce the loss of the rust inhibitor, delay the release of molecules of the rust inhibitor and enhance the long-term effect of the rust inhibitor, a load-type reinforcement rust inhibitor is developed; however, at present, the reinforcing steel bar rust inhibitor generally uses hydrotalcite or calcined hydrotalcite as a carrier, the release of the rust inhibitor is difficult to control efficiently and accurately, so that the corrosion resistance of the rust inhibitor is insufficient, the long-term effect is still difficult to guarantee, and meanwhile, the hydrotalcite serving as a load has strong adsorption on an additive, and the working regulation and control difficulty in application is large.
Disclosure of Invention
In order to solve the problems of difficult guarantee of long-term effect and difficult practical application of the existing load-type rust inhibitor in the prior art, the inventor of the invention actively researches and innovates on the basis of long-term research and provides a brand-new load-type rust inhibitor which takes a metal organic framework as a carrier and can effectively solve the problems of excessive consumption of the rust inhibitor in the early stage, excessive corrosion resistance in the early stage and insufficient corrosion resistance in the later stage.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a metal organic framework supported rust inhibitor comprises a metal organic framework with a hollow structure and a reinforcing steel bar rust inhibitor filled in the metal organic framework; the metal organic framework is doped with nano materials, and the surface of the metal organic framework is provided with through holes for the steel bar rust inhibitor to escape.
Further, the reinforcing steel bar rust inhibitor is selected from any one of monofluorophosphate, nitrite, organic alcohol amine and imidazoline.
Further, the nano material is selected from at least one of nano silicon, nano aluminum, nano CaO and graphene.
Further, the frame material of the metal-organic frame is a metal-organic chelate; wherein, the organic group in the metal-organic chelate is derived from any one of dicarboxylic acid, tricarboxylic acid, diamine compound, polyethylene polyamine, disulfonic acid and trisulfonic acid which have O-containing heteroatom group and/or N-containing heteroatom group and/or S-containing heteroatom group, and the metal ion in the metal-organic chelate is at least one of Be, mg, ca, sr, ba, al, cu, co, ni and Zn.
The metal organic framework loaded rust inhibitor takes a metal organic chelate formed by polycarboxylic acid or amine or polysulfonic acid chelated with metal ions and provided with O, N and S heteroatom groups as a framework structure, presents a shell with a hollow structure, and on one hand, the framework structure can be loaded with a steel bar rust inhibitor inside, and on the other hand, the framework structure can also ensure that the steel bar rust inhibitor inside is slowly released in the using process through a through hole penetrating through the wall of the framework structure; in addition, the nano material uniformly dispersed on the metal organic framework can improve the overall stability and compactness of the metal organic framework, and also ensures that the load type rust inhibitor can improve the ion permeability resistance of concrete when being applied to the concrete.
The invention also aims to provide a preparation method of the metal organic framework supported rust inhibitor, which comprises the following steps:
s1, dispersing a metal ion source, an organic compound, a dispersing agent and a nano material in an organic solvent, and carrying out solvothermal reaction for at least 5 hours at 80-300 ℃ and 1-30 atmospheric pressures to obtain a metal organic framework; wherein the organic compound is an organic substance capable of undergoing a chelation reaction with the metal ions in the metal ion source;
s2, mixing the metal organic framework and the steel bar rust inhibitor and stirring for at least 2h to obtain the metal organic framework supported rust inhibitor.
The chelation reaction between the metal ion source and the organic compound is an important process for forming the metal organic framework, so that the organic solvent is selected from a solvent with strong solubility so as to ensure the sufficient dissolution of the metal ion source and the organic compound and be beneficial to the formation of the metal organic framework; meanwhile, in the process of forming the metal-organic framework, besides the chelation reaction between the metal ion source and the organic compound, the method also comprises the uniform distribution process of the nano material, namely, the nano material is ensured to be uniformly doped in the formed metal-organic framework, so that the dispersing agent is adopted to ensure the uniform distribution of the nano material in the reaction system, and the doping effect of the nano material in the metal-organic framework is improved through the efficient dispersion effect.
In addition, the adoption of the solvothermal reaction conditions of high temperature and high pressure can promote the chemical reaction between the metal ion source and the organic compound, promote the formation of covalent bonds in the chelate system and improve the structural stability of the formed metal organic framework; meanwhile, the structure and the number of the formed metal organic frames can be regulated and controlled by controlling different temperatures and pressures, so that the steel bar rust inhibitor can be conveniently applied and loaded with various steel bar rust inhibitors of different types and different molecular sizes.
Further, in the step S2, the reinforcing steel bar rust inhibitor is selected from any one of monofluorophosphate, nitrite, organic alcohol amine and imidazoline.
Preferably, in the step S2, the reinforcing steel bar rust inhibitor is firstly dissolved in water or a dissolving solvent, and then is slowly added into the metal organic framework in a dropwise manner, so as to further ensure uniform mixing of the reinforcing steel bar rust inhibitor and the metal organic framework. Wherein, the dissolving solvent is preferably at least one organic solvent capable of dissolving and diluting the steel bar rust inhibitor, such as methanol, ethanol, DMF, DMSO, etc.
Further, in the step S1, the metal ion source is acetate, oxalate, carbonate, basic carbonate or hydroxide of at least one metal ion of Be, mg, ca, sr, ba, al, cu, co, ni, zn; the organic compound is any one of dicarboxylic acid, tricarboxylic acid, diamine compound, polyethylene polyamine, disulfonic acid and trisulfonic acid which have O-containing heteroatom group and/or N-containing heteroatom group and/or S-containing heteroatom group; the nano material is selected from at least one of nano silicon, nano aluminum, nano CaO and graphene.
Further, in the step S1, the dispersant is at least one of polycarboxylic acid, polyphosphoric acid, polyvinylpyrrolidone, and a span or tween type surfactant; the organic solvent is at least one of methanol, ethanol and DMF.
Further, in step S2, the metal organic framework supported rust inhibitor is dispersed in water or an organic dispersion liquid, or dried into powder by a spray drying method.
The invention also aims to provide application of the metal organic framework supported rust inhibitor, namely, the metal organic framework supported rust inhibitor is blended in a concrete mixing process.
According to the metal organic framework loaded rust inhibitor provided by the invention, a core-shell structure of a reinforcing steel bar rust inhibitor loaded in a metal organic framework is constructed, and a high-efficiency rust inhibitor component is loaded by utilizing the porous or adsorption property of the metal organic framework, so that the loading type rust inhibitor reduces the hydration process of the reinforcing steel bar rust inhibitor and cement in the process of mixing a cementing material used in concrete, thereby reducing the influence of the high-efficiency reinforcing steel bar rust inhibitor on the hydration process of the cement and further influencing the working and mechanical properties of a hydraulic cementing material; the loaded high-efficiency reinforcing steel bar rust inhibitor component can be gradually and slowly released through the through holes on the surface of the metal organic framework after a hydraulic material is hardened, so that the long-acting and high-efficiency rust inhibition effect is achieved, and the ion transmission resistance of concrete is improved.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic structural view of a metal organic framework supported rust inhibitor according to the present invention;
FIG. 2 is a graph comparing the long term rust resistance of the metal organic framework supported rust inhibitor with the unsupported oleic amine rust inhibitor of example 6 according to the present invention;
FIG. 3 is a graph comparing the effect of metal organic framework supported corrosion inhibitors according to examples 1-6 of the present invention and a control sample without the incorporation of corrosion inhibitor on chloride penetration depth.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
Based on the technical problems that the long-term effect of the load-type rust inhibitor in the prior art is difficult to guarantee and practical application is difficult, the inventor of the invention actively makes research and innovation on the basis of long-term research, and provides a brand-new load-type rust inhibitor which takes a metal organic framework as a carrier and can effectively solve the problems that the corrosion resistance in the early stage is excessive due to excessive consumption of the rust inhibitor and the corrosion resistance in the later stage is insufficient.
Specifically, the metal organic framework supported rust inhibitor provided by the invention comprises a metal organic framework with a hollow structure and a steel bar rust inhibitor filled in the metal organic framework; the metal organic framework is doped with nano materials, and the surface of the metal organic framework is provided with through holes for the steel bar rust inhibitor to escape.
Namely, the metal frame loaded rust inhibitor provided by the invention has a core-shell structure, wherein the metal organic frame doped with the nano material is a shell, and the reinforcing steel bar rust inhibitor loaded in the metal organic frame is an inner core; and the 'shell' is provided with a plurality of through holes, and the 'inner core' objects escape to the outside through the through holes to play a role of rust resistance.
It is worth to be noted that, the reinforcing steel bar rust inhibitors positioned in the metal organic framework are all substances at a molecular level, so the size of the through hole does not need to be specially limited; generally speaking, as long as a plurality of through holes exist, the steel bar rust inhibitor can be enabled to escape.
Specifically, the reinforcing steel bar rust inhibitor as the 'inner core' material can be selected from one of monofluorophosphate, nitrite, organic alcohol amine and imidazoline. The nano material doped in the metal organic framework as the shell is selected from at least one of nano silicon, nano aluminum, nano CaO and graphene; the frame material is a metal organic chelate, wherein the organic group is derived from any one of dicarboxylic acid, tricarboxylic acid, diamine compound, polyethylene polyamine (a specific amine substance, CAS number: 68131-73-7), disulfonic acid and trisulfonic acid which have O-containing heteroatom group and/or N-containing heteroatom group and/or S-containing heteroatom group, and the metal ion is at least one of Be, mg, ca, sr, ba, al, cu, co, ni and Zn.
It should be noted that, especially for nitrite, which is a steel bar corrosion inhibitor, if it is applied to concrete by other methods such as direct incorporation in the prior art, the nitrite will flow out of the concrete block in a short time due to its fast release property (i.e. the action time is far earlier than the time when the concrete is attacked by corrosive ions in the environment), thereby causing environmental pollution due to its toxicity. However, in the load type rust inhibitor provided by the invention, the metal organic frame is loaded inside, so that the speed of releasing the metal organic frame into concrete is greatly limited, the problem of environmental pollution caused by nitrite serving as a steel bar rust inhibitor is avoided, and the dosage is reduced due to controllable release of the nitrite. According to the load-type rust inhibitor with the structure part, the novel rust inhibitor with the core-shell structure is constructed, so that an effective rust inhibitor with serious application defects in the prior art can be reused, a brand new application method of the existing mature rust inhibitor is provided, and the application cost is greatly reduced.
The preparation method of the metal organic framework supported rust inhibitor provided by the invention comprises the following steps:
in step S1, a metal ion source, an organic compound, a dispersant and a nano material are dispersed in an organic solvent, and a solvothermal reaction is carried out for at least 5 hours at 80-300 ℃ and 1-30 atmospheric pressures to obtain a metal organic framework.
Specifically, the organic compound is an organic substance capable of undergoing a chelating reaction with the metal ion in the metal ion source; preferably any one of dicarboxylic acids, tricarboxylic acids, diamine compounds, polyethylenepolyamines, disulfonic acids, and trisulfonic acids having an O-containing heteroatom group and/or an N-containing heteroatom group and/or an S-containing heteroatom group. That is, the basic structure of these organic compounds is any one of dicarboxylic acid, tricarboxylic acid, diamine compound, polyethylene polyamine, disulfonic acid, and trisulfonic acid, and the molecule of the basic structure further has at least one of hetero atom groups such as O-containing hetero atom group, N-containing hetero atom group, and S-containing hetero atom group.
Wherein the metal ion source is acetate, oxalate, carbonate, basic carbonate or hydroxide of at least one metal ion of Be, mg, ca, sr, ba, al, cu, co, ni and Zn; the nano material is selected from at least one of nano silicon, nano aluminum, nano CaO and graphene; the dispersant is at least one of polycarboxylic acid, polyphosphoric acid, polyvinylpyrrolidone and span or tween type surfactant; the organic solvent is at least one of methanol, ethanol and DMF.
In the step S2, the metal organic framework and the steel bar rust inhibitor are mixed and stirred for at least 2 hours to obtain the metal organic framework supported rust inhibitor.
Specifically, the reinforcing steel bar rust inhibitor is selected from one of monofluorophosphate, nitrite, organic alcohol amine and imidazoline.
Preferably, the reinforcing steel bar rust inhibitor is firstly dissolved in water or a dissolving solvent and then is added into the prepared metal organic framework in a slow dropwise manner, so as to further ensure the uniform mixing of the reinforcing steel bar rust inhibitor and the metal organic framework. Wherein, the dissolving solvent is preferably at least one organic solvent capable of dissolving and diluting the steel bar rust inhibitor, such as methanol, ethanol, DMF, DMSO, etc.
After the metal organic framework load type rust inhibitor is prepared through the two steps, the metal organic framework load type rust inhibitor can be stored by dispersing the metal organic framework load type rust inhibitor in water or organic dispersion liquid or drying the metal organic framework load type rust inhibitor into powder by adopting a spray drying method.
The application method of the metal organic framework supported rust inhibitor is simple, and the metal organic framework supported rust inhibitor can be directly blended in the mixing process of concrete. The load type rust inhibitor can obviously reduce the influence on the performance of concrete, and can release the reinforcing steel bar rust inhibitor loaded in the concrete according to the change of ion concentration in the surrounding environment in the concrete pore liquid, thereby realizing the long-acting and high-efficiency rust inhibition of reinforcing steel bars. In addition, the nano material doped in the metal organic framework can improve the compactness of concrete, thereby achieving the effect of resisting corrosive ion transmission.
The above-mentioned supported rust inhibitor and the preparation method thereof of the present invention will be embodied by specific examples below, but it will be understood by those skilled in the art that the following examples are only specific examples of the above-mentioned products and the preparation method thereof, and are not intended to limit the entirety thereof.
Example 1
Firstly, calcium oxalate, succinic acid, polycarboxylic acid dispersant (molecular weight 20000) and nano-silicon with the particle size of 10nm are added into dimethyl acetamide, and the solvation reaction is carried out for 10h under the conditions of 3MPa and 140 ℃ of pressure and temperature, so as to obtain the metal organic framework.
And then adding sodium monofluorophosphate into the obtained metal organic framework, continuously stirring for 3 hours, and extracting the solvent under vacuum negative pressure to prepare the nano-scale metal organic framework supported rust inhibitor.
That is to say, the metal organic frame supported rust inhibitor provided by this embodiment includes a metal organic frame doped with nano-silicon and calcium succinate chelate as a frame material, and sodium monofluorophosphate filled in the metal organic frame.
Example 2
Firstly, aluminum carbonate, sunflower diamine, polyphosphoric acid dispersant (molecular weight 40000) and nano Al with the particle size of 50nm are mixed 2 O 3 And adding the mixture into ethanol, and performing solvation reaction for 6 hours under the conditions of pressure and temperature of 10MPa and 100 ℃ to obtain the metal organic framework.
And then adding calcium nitrite into the obtained metal organic framework, continuously stirring for 2 hours, and extracting the solvent under vacuum negative pressure to prepare the nano-scale metal organic framework supported rust inhibitor.
That is, the metal-organic framework supported rust inhibitor provided by this embodiment includes a sunflower diamine aluminum chelate complex as a framework material and doped with nano Al 2 O 3 And calcium nitrite filled inside the metal organic framework.
Example 3
Firstly, adding basic copper carbonate, citric acid, polyvinylpyrrolidone (molecular weight 10000) and nano CaO with the particle size of 100nm into a mixed solvent of methanol and DMF, and carrying out a solvation reaction for 7 hours under the conditions of pressure and temperature of 30MPa and 80 ℃ to obtain a metal organic framework.
And then adding dimethylethanolamine into the obtained metal organic framework, continuously stirring for 4 hours, and extracting the solvent to prepare the nano metal organic framework supported rust inhibitor.
That is to say, the metal-organic framework supported rust inhibitor provided by this embodiment includes a metal-organic framework with copper citrate chelate as a framework material and doped with nano-CaO, and dimethylethanolamine filled inside the metal-organic framework.
Example 4
Firstly, adding magnesium hydroxide, cobalt acetate, polyethylene polyamine, span 85 and nano silicon with the particle size of 30nm into a mixed solvent of ethanol and DMF, and carrying out a solvation reaction for 3h under the conditions of pressure and temperature of 20MPa and 200 ℃ to obtain a metal organic framework.
And then, adding oleic acid imidazoline into the obtained metal organic framework, continuously stirring for 5 hours, and extracting the solvent to prepare the nano-scale metal organic framework loaded type rust inhibitor.
That is to say, the metal organic framework supported rust inhibitor provided by this embodiment includes a metal organic framework doped with nano silicon and oleic acid imidazoline filled in the metal organic framework, with polyethylene polyamine magnesium chelate and polyethylene polyamine cobalt chelate as framework materials.
Example 5
Firstly, adding calcium oxalate, zinc carbonate, nonylphenyl disulfonic acid, span 60, tween 20 and graphene with the particle size of 50nm into a mixed solvent of ethanol and DMF, and carrying out a solvation reaction for 5 hours under the conditions of pressure and temperature of 15MPa and 300 ℃ to obtain a metal organic framework.
And adding ammonium laurate into the obtained metal organic framework, continuously stirring for 3 hours, and extracting the solvent to prepare the nano-scale metal organic framework supported rust inhibitor.
That is to say, the metal organic framework supported rust inhibitor provided by this embodiment includes a metal organic framework doped with graphene and having calcium nonylphenyl disulfonate chelate and zinc nonylphenyl disulfonate chelate as framework materials, and laurylamine filled inside the metal organic framework.
Example 6
Firstly, barium hydroxide, nickel hydroxide and phenylTrisulfonic acid, span 20, tween 60 and nano Al with particle size of 40nm 2 O 3 Nano SiO with particle size of 30nm 2 And adding the mixture into a methanol solvent, and carrying out solvation reaction for 10 hours under the conditions of pressure and temperature of 8MPa and 300 ℃ to obtain the metal organic framework.
And then adding oleylamine into the obtained metal organic framework, continuously stirring for 2 hours, and extracting the solvent to prepare the nano-scale metal organic framework supported rust inhibitor.
That is to say, the metal-organic framework supported rust inhibitor provided by this embodiment includes a barium phenyl trisulfonate chelate and a nickel phenyl trisulfonate chelate as framework materials, and is doped with nano Al 2 O 3 And nano SiO 2 And the oleic acid amine is filled in the metal organic framework.
The metal organic framework supported rust inhibitor can be applied to concrete in a direct doping mode.
The performance of each of the supported rust inhibitors provided in examples 1 to 6 above will be tested and compared.
Testing one: and (5) testing the rust resistance.
Preparing saturated calcium hydroxide solution, adding 3.5% NaCl as comparison solution, and recording as 0 # 。
Respectively to 0 # The load type rust inhibitor provided in the above examples 1 to 6 is added to the comparative solution in a mass fraction of 2%, and the solution system is respectively marked as 1 as a solution system for testing the corrosion resistance of the steel bar # 、2 # 、3 # 、4 # 、 5 # 、6 # 。
The comparative sample is selected from the samples of the alcohol amine organic migration type rust inhibitor commonly used in the market and is recorded as Ref.1.
The test was performed using a three-electrode system. Selecting cylindrical Q235 steel bar, encapsulating with epoxy resin, and keeping 1cm 2 Working area, in turn 600 # 、1000 # 、2000 # Sanding and polishing with sand paper, soaking in acetone for 15min, drying, using as working electrode, platinum electrode as counter electrode,saturated calomel electrode as reference electrode. The linear polarization resistance of the working electrode in the test contrast solution and the solution containing different load type rust inhibitor changes along with time and is respectively marked as R p 、R p ', calculating the corrosion current density of the steel bar according to Stern-Geary equation shown in formula 1:
i corr ＝B/R p formula 1
Wherein R is p Is the polarization resistance, and B is the anode and cathode Tafel slope related constant, here taken collectively at 26mV.
And calculating the corrosion inhibition efficiency of the rust inhibitor after being soaked for 14 days according to the formula 2. The test results are shown in table 1.
At the same time, the same test was carried out using as a comparison a mature, commonly available commercial rust inhibitor product, organic rust inhibitor aminoalcohol (noted ref. 1), the test results of which are also given in table 1.
Table 1 corrosion inhibiting effect of the supported rust inhibitor and the commercially available rust inhibitor on reinforcing steel bars in examples 1 to 6
As can be seen from table 1, the supported rust inhibitors provided in examples 1 to 6 all show very good rust inhibition effect in a high-concentration chloride environment, and the rust inhibition efficiency after 14 days is over 95%, and is significantly higher than that of ref.1, thus showing very excellent rust inhibition performance.
And (2) testing: and (3) testing the influence of the loading effect on the long-term rust resistance.
The supported rust inhibitor provided in example 6 above was used as the test object, while the oleic amine rust inhibitor without being supported was used as the comparative example. The long-term rust resistance of both is shown in FIG. 2.
As can be seen from fig. 2, as the examination period is prolonged, especially from about 24d, the supported corrosion inhibitor exhibits a more stable corrosion current density, i.e. exhibits extremely excellent long-term corrosion resistance, and is more excellent as the time is prolonged, compared with the same reinforcing steel bar corrosion inhibitor which is not supported.
And (3) testing: and testing the transmission performance of the medium.
In order to comparatively analyze the influence of different supported rust inhibitors on the medium transmission resistance of concrete, the medium transmission resistance of the supported rust inhibitors provided in the above examples 1 to 6 was studied in a cement mortar system.
The water-cement ratio W/C of the cement paste is 0.5, the cement is the reference cement, and the water is tap water.
Soaking in 3.5% NaCl aqueous solution, and testing the penetration depth of chloride ions after soaking; wherein, 0 # The concrete test pieces in which no reinforcing steel bar rust inhibitor was incorporated are shown, and the concrete test pieces in which each of the supported rust inhibitors of examples 1 to 6 was incorporated are referred to as 1 # 、2 # 、3 # 、4 # 、5 # 、6 # . The test results are shown in fig. 3.
As can be seen from FIG. 3, the metal organic framework supported rust inhibitor provided by the invention can significantly reduce the permeability of a cement-based material, so that the penetration depth of chloride ions is reduced by more than 40%, namely the metal organic framework supported rust inhibitor provided by the invention plays a role in efficiently inhibiting rust when being applied to concrete.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (8)
1. The metal organic framework supported rust inhibitor is characterized by comprising a metal organic framework with a hollow structure and a steel bar rust inhibitor filled in the metal organic framework; the metal organic framework is doped with nano materials, and the surface of the metal organic framework is provided with a through hole for the steel bar rust inhibitor to escape; the frame material of the metal-organic frame is a metal-organic chelate; the organic group in the metal organic chelate is derived from any one of dicarboxylic acid, tricarboxylic acid, diamine compound, polyethylene polyamine, disulfonic acid and trisulfonic acid which have O-containing heteroatom group and/or N-containing heteroatom group, and the metal ion in the metal organic chelate is at least one of Be, mg, ca, sr, ba, al, cu, co, ni and Zn.
2. The load type rust inhibitor according to claim 1, wherein the reinforcing steel bar rust inhibitor is selected from any one of monofluorophosphate, nitrite, organic alcohol amine and imidazoline.
3. The supported rust inhibitor as claimed in claim 1, wherein the nanomaterial is selected from at least one of nano-silicon, nano-aluminum, nano-CaO and graphene.
4. A preparation method of a metal organic framework supported rust inhibitor is characterized by comprising the following steps:
s1, dispersing a metal ion source, an organic compound, a dispersing agent and a nano material in an organic solvent, and carrying out solvothermal reaction for at least 5 hours at 80-300 ℃ and 1-30 atmospheric pressures to obtain a metal organic framework; wherein the organic compound is an organic substance capable of undergoing a chelation reaction with the metal ions in the metal ion source; the metal ion source is acetate, oxalate, carbonate, basic carbonate or hydroxide of at least one metal ion of Be, mg, ca, sr, ba, al, cu, co, ni and Zn; the organic compound is any one of dicarboxylic acid, tricarboxylic acid, diamine compound, polyethylene polyamine, disulfonic acid and trisulfonic acid which have O-containing heteroatom group and/or N-containing heteroatom group and/or S-containing heteroatom group; the nano material is selected from at least one of nano silicon, nano aluminum, nano CaO and graphene;
s2, mixing the metal organic framework and the steel bar rust inhibitor and stirring for at least 2h to obtain the metal organic framework supported rust inhibitor.
5. The method according to claim 4, wherein in the step S2, the reinforcing bar rust inhibitor is selected from any one of monofluorophosphate, nitrite, organic alcohol amine and imidazoline.
6. The production method according to claim 4, wherein in the step S1, the dispersant is at least one of polycarboxylic acid, polyphosphoric acid, polyvinylpyrrolidone, and a span-or tween-type surfactant; the organic solvent is at least one of methanol, ethanol and DMF.
7. The method according to any one of claims 4 to 6, wherein in step S2, the metal organic framework supported rust inhibitor is dispersed in water or an organic dispersion liquid, or is dried into powder by a spray drying method.
8. Use of a metal organic framework supported rust inhibitor, characterized in that the metal organic framework supported rust inhibitor according to any one of claims 1-3 is blended during concrete blending.
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