CN108706908A - A kind of antirust for reinforced concrete and its preparation and application - Google Patents
A kind of antirust for reinforced concrete and its preparation and application Download PDFInfo
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- CN108706908A CN108706908A CN201810585325.9A CN201810585325A CN108706908A CN 108706908 A CN108706908 A CN 108706908A CN 201810585325 A CN201810585325 A CN 201810585325A CN 108706908 A CN108706908 A CN 108706908A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention proposes a kind of antirust for reinforced concrete and its preparation method and application, is prepared by the raw material of following parts by weight：50-60 parts of schiff bases -30-50 parts of aluminium chelate compound, 20-40 parts of antioxidant, 20-40 parts of compound amino acid, 10-20 parts of surfactant and water.The antirust for reinforced concrete of the preparation can release Al under seawater alkaline condition3+, reinforcing bar can be effectively protected not by seawater corrosion under the synergistic effect of compound amino acid, antioxidant and surfactant in one layer of fine and close oxide layer of Surface Creation of Fe.
Description
Technical field
The present invention relates to corrosion inhibitor fields, and in particular to a kind of antirust for reinforced concrete.
Background technology
Since the twenties in 19th century, Portland cement came out, concrete material has more than 100 years usage history, due to
It is big with the rigidity of structure, is easy to construction, many advantages, such as low engineering cost, later period maintenance expense are lacked, and has become building work
Preferred material in journey structure design, 2015, which are only Chinese cement yield, just reaches 2,300,000,000 tons.In fact, being applied to from concrete
Between civil engineering so far more than 100 years, a large amount of reinforced concrete structure premature failure due to various, up to not
To scheduled Years Of Service.Caused by having plenty of the drag deficiency due to structure design among these, some is then due to the use of lotus
The undesirable change of load and caused by, but be more due to the durability of structure is insufficient and caused by caused by failure.Especially
Coastal and offshore area concrete structure, due to a large amount of Cl contained in marine environment-, concrete is caused to corrode, is caused
Steel bar corrosion and make structure that earlier period damage occur, lose the endurance quality of structure, what this had become in Practical Project important asks
Topic.The method for slowing down or preventing steel bar corrosion has very much, including：Rebar surface coating, cathodic protection, electrochemical dechlorination and make
With corrosion inhibitor etc..Wherein, reinforcing steel bar corrosion inhibitor is a kind of easy for construction and economical and effective resistance rust method.Corrosion inhibitor is to reinforcing bar
Suction-operated has physical absorption (Van der Waals force, electrostatic interaction) and chemisorption (not key absorption, supplied for electronic, for proton), passes through
It improves corrosion reaction activation energy and corrosive medium is isolated with metal, to prevent the progress of corrosion.
Schiff bases is a kind of very important containing n-donor ligand, typically refers to primary amine and active carbonyls condensation reaction institute
What is formed contains azomethine base (R2R1C=NR3, R1, R2, R3 are respectively H, alkyl, cyclohexyl, aromatic radical or heterocycle) one kindization
Close object.This kind of compound is gained the name due to H.Schi livers find for 1864 for the first time.Its main feature is that synthesis is relatively easy, can neatly select
Select various carbonyls and different amines reacted, change the substituent group of connection, change donor atomic nature and its
Position can open many from chain to cyclization, and from monodentate to multiple tooth, performance is totally different, the changeable schiff base ligand of structure, it
Can form the complex that stability differs with most of metal ion in periodic table.One of Schiff bases compound is most heavy
The characteristics of wanting is exactly to be easily opened coordinate bond in the environment of acid or alkali, release metal ion, because of this characteristic so that
Schiff bases becomes a kind of good corrosion inhibitor ingredient.
Invention content
In order to solve the above technical problems, the present invention provides a kind of antirust for reinforced concrete and preparation method thereof and answers
With it is intended that a kind of antirust for reinforced concrete is provided, by adding schiff bases-aluminium chelate compound, compound amino acid, resisting
Oxygen agent and surfactant, aluminium ion can be released under seawater alkaline condition by obtaining one kind, and densification is formed on the surfaces Fe
Oxidation film is not corroded in the seawater so as to effective protection armored concrete.
The present invention provides a kind of antirust for reinforced concrete, is prepared by the raw material of following parts by weight：Schiff bases-aluminium chela
Close 50-60 parts of 30-50 parts of object, 20-40 parts of antioxidant, 20-40 parts of compound amino acid, 10-20 parts of surfactant and water.
As further improvement of the invention, it is prepared by the raw material of following parts by weight：Schiff bases-aluminium chelate compound 40
Part, 30 parts of antioxidant, 30 parts of compound amino acid, 15 parts of surfactant and 55 parts of water.
As further improvement of the invention, antioxidant is selected from three monooctyl esters, three last of the ten Heavenly stems esters, three (Lauryl Alcohol) esters and three (ten
Six carbon alcohol) ester, 2,6- three-level butyl -4- methylphenols, bis- (3,5- three-level butyl -4- hydroxy phenyls) thioethers, four (β-(3,5-
Three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol ester and double Lauryl Alcohol esters, bi-myristoleyl and double octadecanol esters,
The compounds such as diphenylamines, p-phenylenediamine and dihydroquinoline and its one or more of derivative or polymer.
As further improvement of the invention, compound amino acid is selected from methionine, lysine, glycine, threonine, smart ammonia
At least two in acid, Diglycocol, triglycine, phenylalanine, tyrosine.
As further improvement of the invention, surfactant is quaternary cationics, is selected from halogenated hydrocarbons
Class quaternary cationics, dialkyl sulfates quaternary cationics, alkylene oxides quaternary ammonium salt
Cationic surfactant, one or more of sulfonic acid esters quaternary cationics.
The present invention further protects a kind of preparation method according to above-mentioned antirust for reinforced concrete, according to the following steps into
Row：
S1. the synthesis of schiff base ligand：Adjacent diamine compounds and sodium hydroxide are dissolved in organic solvent, substitution is added
Salicylide, heating reflux reaction 5-7h generate white solid, continue back flow reaction 1h postcoolings to room temperature, filtering, ethyl alcohol is repeatedly
Solid is washed, obtains schiff base ligand, structural formula is：
S2. the synthesis of schiff bases-aluminium chelate compound：Schiff base ligand is dissolved in ethanol solution, AlCl is added3, 50-70 DEG C
12-24h, cold filtration are reacted, ethyl alcohol washs solid, obtains schiff bases-aluminium chelate compound repeatedly, and structural formula is：
Wherein R1、R2、R3=hydrogen, halogen, C1-C20Linear or branched alkyl group, C2-C20Linear chain or branched chain alkenyl, C2-C20Directly
Chain or branch alkynyl, C1-C20Linear chain or branched chain miscellaneous alkyl, C2-C20Linear chain or branched chain miscellaneous thiazolinyl, C2-C20The miscellaneous alkynes of linear chain or branched chain
Base, C3-C20Linear chain or branched chain naphthenic base, C2-C20Heterocyclylalkyl, C2-C20Linear or branched alkyl group carboxyl, C2-C20 straight chains or branch
Alkyl group formamido, C2-C20Linear or branched alkyl group imino group, C1-C20Linear or branched alkyl group sulfonic group, C1-C20Straight chain
Or branched alkyl itrile group；
S3. schiff bases-aluminium chelate compound, antioxidant, compound amino acid, surfactant and water are mixed in proportion and are mixed well,
40-50 DEG C stirring 2-5h to get.
As further improvement of the invention, organic solvent is selected from alkane, alkene, alcohol, aldehyde, amine, ester, ether, ketone, fragrance
One or more of hydrocarbon, hydrogenate hydrocarbon, terpene hydrocarbon, halogenated hydrocarbons, heterocycle compound, nitrogenous compound and sulfur-containing compound solvent.
As further improvement of the invention, the ratio between amount of substance of adjacent diamine compounds and substituted salicylic aldehydes is 1：
(1.8-2.2)。
The present invention further protects a kind of above-mentioned antirust for reinforced concrete to concrete mild steel material and its reinforcing bar
Product carries out the application in corrosion protection, reparation.
The present invention has the advantages that：
1, an important active constituent is exactly to chelate Al in corrosion inhibitor of the present invention3+Schiff bases, it is in seawater alkalinity item
Under part, coordinate bond is opened, Al is released3+, Al3+It is adsorbed on the surface of reinforcing bar, is reacted with oxygen and generates one layer of fine and close oxidation film
Al2O3, reinforcing bar is protected to be no longer influenced by Cl-Erosion, to play the role of resistance rust；
2, compound amino acid can form complex with Fe, eliminate the local corrosion phenomena caused by passivation layer gage distortion,
With chelating Al3+Schiff bases play synergistic effect, improve resistance rust effect；
3, the addition of antioxidant can make Fe be not easy to O2Reaction avoids generating Fe2O3Accelerate the rustization of Fe in reinforcing bar anti-
It answers；
4, surfactant is reunited near Fe, and hydrophobic branch chain is distributed in outer, reduces being in direct contact for water and Fe..
Description of the drawings
The preparation technology figure for the antirust for reinforced concrete that Fig. 1 is.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete description,
Obviously, the embodiment described is the embodiment of the part of representative of the present invention, rather than whole embodiments, this field are general
Other all embodiments that logical technical staff is obtained without making creative work belong to the protection of the present invention
Range.
The preparation of 1 antirust for reinforced concrete of embodiment
Raw material forms：30 parts of schiff bases-aluminium chelate compound, four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) seasons penta
Four alcohol esters and double 20 parts of Lauryl Alcohol esters, compound amino acid (lysine and glycine, mass ratio 2：1) 20 parts, sulfuric acid dioxane
50 parts of 10 parts of base ester class quaternary cationics and water；
Preparation method：
S1. the synthesis of schiff base ligand：1mol neighbour's diamine compounds and 0.1mol sodium hydroxides are dissolved in acetonitrile, are added
Enter 1.8mol substituted salicylic aldehydes, heating reflux reaction 5h generates white solid, continues back flow reaction 1h postcoolings to room temperature, mistake
Filter, ethyl alcohol wash solid, obtain schiff base ligand repeatedly, and structural formula is：
S2. the synthesis of schiff bases-aluminium chelate compound：Schiff base ligand is dissolved in ethanol solution, AlCl is added3, 50 DEG C anti-
It answers 12h, cold filtration, ethyl alcohol to wash solid repeatedly, obtains schiff bases-aluminium chelate compound, structural formula is：
Wherein R1、R2、R3=hydrogen, halogen, C1-C20Linear or branched alkyl group, C2-C20Linear chain or branched chain alkenyl, C2-C20Directly
Chain or branch alkynyl, C1-C20Linear chain or branched chain miscellaneous alkyl, C2-C20Linear chain or branched chain miscellaneous thiazolinyl, C2-C20The miscellaneous alkynes of linear chain or branched chain
Base, C3-C20Linear chain or branched chain naphthenic base, C2-C20Heterocyclylalkyl, C2-C20Linear or branched alkyl group carboxyl, C2-C20 straight chains or branch
Alkyl group formamido, C2-C20Linear or branched alkyl group imino group, C1-C20Linear or branched alkyl group sulfonic group, C1-C20Straight chain
Or branched alkyl itrile group；
S3. by schiff bases-aluminium chelate compound, four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters and
Double Lauryl Alcohol esters, compound amino acid, dialkyl sulfates quaternary cationics and water mix tune in proportion
Even, 40 DEG C of stirring 2h are to get total yield 72%.
Reaction equation is as follows：
The preparation of 2 antirust for reinforced concrete of embodiment
Raw material forms：50 parts of schiff bases-aluminium chelate compound, 20 parts of three monooctyl ester, 20 parts of three last of the ten Heavenly stems ester, compound amino acid (methionine
And glycine, mass ratio 1:1) 60 parts of 40 parts, 20 parts of halogenated hydrocarbon quaternary cationics and water；
Preparation method：
S1. the synthesis of schiff base ligand：1mol neighbour's diamine compounds and 0.1 sodium hydroxide are dissolved in dichloromethane,
2mol substituted salicylic aldehydes are added, heating reflux reaction 7h generates white solid, continues back flow reaction 1h postcoolings to room temperature, mistake
Filter, ethyl alcohol wash solid, obtain schiff base ligand repeatedly；
S2. the synthesis of schiff bases-aluminium chelate compound：Schiff base ligand is dissolved in ethanol solution, AlCl is added3, 70 DEG C anti-
Should for 24 hours, cold filtration, ethyl alcohol washs solid repeatedly, obtains schiff bases-aluminium chelate compound；
S3. by schiff bases-aluminium chelate compound, three monooctyl esters, three last of the ten Heavenly stems esters, compound amino acid, halogenated hydrocarbon quaternary ammonium salt cationic table
Face activating agent and water mix in proportion to be mixed well, and 50 DEG C of stirring 2-5h are to get total yield 84%.
The preparation of 3 antirust for reinforced concrete of embodiment
Raw material forms：40 parts of schiff bases-aluminium chelate compound, 30 parts of 2,6- three-level butyl -4- methylphenols, compound amino acid
(Diglycocol, triglycine and tyrosine, mass ratio 1:1:1) 30 parts, alkylene oxides quaternary cationics
15 parts and 55 parts of water；
Preparation method：
S1. the synthesis of schiff base ligand：1mol neighbour's diamine compounds and 0.1 sodium hydroxide are dissolved in methanol, are added
2.2mol substituted salicylic aldehydes, heating reflux reaction 6h generate white solid, continue back flow reaction 1h postcoolings to room temperature, filter,
Ethyl alcohol washs solid repeatedly, obtains schiff base ligand；
S2. the synthesis of schiff bases-aluminium chelate compound：Schiff base ligand is dissolved in ethanol solution, AlCl is added3, 60 DEG C anti-
It answers 18h, cold filtration, ethyl alcohol to wash solid repeatedly, obtains schiff bases-aluminium chelate compound；
S3. by schiff bases-aluminium chelate compound, 2,6- three-level butyl -4- methylphenols, compound amino acid, alkylene oxides quaternary ammonium
Cationic surfactants and water mix in proportion to be mixed well, and 45 DEG C of stirring 4h are to get total yield 91%.
Reference examples 1 are prepared according to a kind of patent ZL 201610123473.X " preparation method of concrete corrosion resistant agent " method
Concrete corrosion resistant agent
By 10mol ethylenediamines and 20mol glucolactones (DGAL), 0.3mol N, N- diformazan basic rings are added at 50 DEG C
Required concrete corrosion resistant agent is obtained after hexylamine reaction 4h.
Reference examples 2 are prepared according to patent ZL 201511017229.7 " glucosides ketone reinforcing steel bar corrosion inhibitor and preparation method thereof "
Glucosides ketone reinforcing steel bar corrosion inhibitor
(1) 36g (0.2mol) glucose is added in round-bottomed flask, then sequentially adds 100mL water, 25g
(0.3mol) sodium bicarbonate, 23mL (0.22mol) acetylacetone,2,4-pentanedione react 15 hours under the conditions of magnetic agitation at 85 DEG C, are cooled to room
Temperature, rotary evaporation remove solvent, are re-dissolved in ethyl alcohol, are filtered to remove the inorganic salts insoluble in ethyl alcohol, remove after ethyl alcohol to get sugar
Glycosides ketone.
(2) glucosides ketone made from 15g is dissolved in 70g tap water, be added 15g ethanol amines, stirring to be completely dissolved to get
Glucosides ketone reinforcing steel bar corrosion inhibitor.
Influence of the test case 1 to concrete performance
With reference to GB/T8076-2008《Concrete admixture》Middle regulation prepares concrete, for testing corrosion inhibitor to coagulation
The influence of soil nature energy.Wherein, reference cement dosage 330kg/m3, water-cement ratio 0.55, corrosion inhibitor volume is 2kg/m3, sand, stone and
Sand coarse aggregate ratio is satisfied by standard requirement.Test incorporation Examples 1 to 3 and 1~2 corrosion inhibitor of reference examples are to concrete coagulating time and intensity
Influence, be shown in Table 1.
Influence of the table 1 to concrete performance
2 corrosion-prevention rust-resistance performance test of test case
Saturated calcium hydroxide solution is prepared, 0.3mol/LNaCl solution as a comparison is added thereto.It is molten to comparing respectively
The solution system that the embodiment that mass fraction is 1% is tested as reinforcing bar corrosion resistance is added in liquid.Using three-electrode system
It is tested.Cylindric Q235 reinforcing bars are selected, around with epoxy resin enclosed, stay 1cm2Work area, with 600#, 1000#,
2000# sand paper is polished and is polished, and steeps the ultrasound 15min in acetone later, and working electrode is used as after drying, and platinum electrode is opposed electricity
Pole, saturated calomel electrode make reference electrode.Work in 1~2 corrosion inhibitor solution of test comparison solution and Examples 1 to 3 and reference examples
The linear polarization resistance for making electrode changes over time, and is denoted as R respectivelyp、R’p, according to η=R 'p-RP/R’pIt calculates and is hindered after impregnating 7 days
The inhibition efficiency of rust agent, test result are shown in Table 2.
The resistance rust effect of table 2
As can be seen from the test results, 1-3 of the embodiment of the present invention shows significantly to hinder under high villaumite concentration levels
Rust effect, hence it is evident that be better than reference examples 1-2.After impregnating 7 days, resistance rust efficiency partly reaches 98.9% all 98% or more.Prove this
The antirust for reinforced concrete of invention can be well protected reinforcing bar in bar in chlorine salt solution, greatly slow down the hair of steel bar corrosion
It is raw, while a large amount of hydroxyl is conducive to dispersion performance of the corrosion inhibitor in concrete, reduces corrosion inhibitor to concrete mixing performance
Influence.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention of claims determination, also
Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by
The range of claims determines.
Claims (9)
1. a kind of antirust for reinforced concrete, which is characterized in that be prepared by the raw material of following parts by weight：Schiff bases-aluminium chela
Close 50-60 parts of 30-50 parts of object, 20-40 parts of antioxidant, 20-40 parts of compound amino acid, 10-20 parts of surfactant and water.
2. a kind of antirust for reinforced concrete according to claim 1, which is characterized in that prepared by the raw material of following parts by weight
It forms：55 parts of 40 parts of schiff bases-aluminium chelate compound, 30 parts of antioxidant, 30 parts of compound amino acid, 15 parts of surfactant and water.
3. a kind of antirust for reinforced concrete according to claim 1, which is characterized in that the antioxidant be selected from three monooctyl esters,
Three last of the ten Heavenly stems esters, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters, 2,6- three-level butyl -4- methylphenols, bis- (3,5- three-level fourths
Base -4- hydroxy phenyls) thioether, four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters and double Lauryl Alcohols
Compounds and its derivative such as ester, bi-myristoleyl and double octadecanol esters, diphenylamines, p-phenylenediamine and dihydroquinoline are poly-
Close one or more of object.
4. a kind of antirust for reinforced concrete according to claim 1, which is characterized in that the compound amino acid is selected from egg ammonia
At least two in acid, lysine, glycine, threonine, arginine, Diglycocol, triglycine, phenylalanine, tyrosine.
5. a kind of antirust for reinforced concrete according to claim 1, which is characterized in that the surfactant is quaternary ammonium salt
Cationic surfactant, selected from halogenated hydrocarbon quaternary cationics, dialkyl sulfates quaternary ammonium salt sun from
Sub- surfactant, alkylene oxides quaternary cationics, in sulfonic acid esters quaternary cationics
One or more.
6. it is a kind of according to a kind of preparation method of antirust for reinforced concrete described in claim 1-5 any claims, it is special
Sign is, follows the steps below：
S1. the synthesis of schiff base ligand：Adjacent diamine compounds and sodium hydroxide are dissolved in organic solvent, substitution bigcatkin willow is added
Aldehyde, heating reflux reaction 5-7h generate white solid, continue back flow reaction 1h postcoolings to room temperature, filter, ethyl alcohol washs repeatedly
Solid, obtains schiff base ligand, and structural formula is：
S2. the synthesis of schiff bases-aluminium chelate compound：Schiff base ligand is dissolved in ethanol solution, AlCl is added3, 50-70 DEG C of reaction
12-24h, cold filtration, ethyl alcohol wash solid repeatedly, obtain schiff bases-aluminium chelate compound, and structural formula is：
Wherein R1、R2、R3=hydrogen, halogen, C1-C20Linear or branched alkyl group, C2-C20Linear chain or branched chain alkenyl, C2-C20Straight chain or
Branch alkynyl, C1-C20Linear chain or branched chain miscellaneous alkyl, C2-C20Linear chain or branched chain miscellaneous thiazolinyl, C2-C20The miscellaneous alkynyl of linear chain or branched chain,
C3-C20Linear chain or branched chain naphthenic base, C2-C20Heterocyclylalkyl, C2-C20Linear or branched alkyl group carboxyl, C2-C20 linear chain or branched chains
Alkyl amido, C2-C20Linear or branched alkyl group imino group, C1-C20Linear or branched alkyl group sulfonic group, C1-C20Straight chain or
Branched alkyl itrile group；
S3. schiff bases-aluminium chelate compound, antioxidant, compound amino acid, surfactant and water are mixed in proportion and is mixed well, 40-50
DEG C stirring 2-5h to get.
7. a kind of preparation method of antirust for reinforced concrete according to claim 6, which is characterized in that the organic solvent
Selected from alkane, alkene, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenate hydrocarbon, terpene hydrocarbon, halogenated hydrocarbons, heterocycle compound, nitrogen
Close one or more of object and sulfur-containing compound solvent.
8. a kind of preparation method of antirust for reinforced concrete according to claim 6, which is characterized in that neighbour's Diamines
The ratio between compound and the amount of substance of substituted salicylic aldehydes are 1：(1.8-2.2).
9. it is a kind of according to a kind of antirust for reinforced concrete described in claim 1-5 any claims to concrete medium carbon steel
Material and its reinforcing bar product carry out the application in corrosion protection, reparation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109811346A (en) * | 2019-01-11 | 2019-05-28 | 东南大学 | A kind of gas phase corrosion inhibitor and preparation method thereof and the application in terms of building iron corrosion protection |
| CN111587056A (en) * | 2020-05-14 | 2020-08-25 | 湖南省国银新材料有限公司 | Electromagnetic shielding silver paste for communication equipment and preparation method thereof |
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| CN105366978A (en) * | 2015-11-18 | 2016-03-02 | 刘志勇 | Permeable steel bar corrosion inhibitor for durability repair of concrete structure and preparation method thereof |
| CN106278061A (en) * | 2016-09-10 | 2017-01-04 | 江苏省建筑工程集团丰达混凝土有限公司 | A kind of weight concrete |
| CN106543977A (en) * | 2016-10-28 | 2017-03-29 | 江苏省特种设备安全监督检验研究院 | A kind of Graphene heat conduction oil additive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102432220A (en) * | 2011-09-09 | 2012-05-02 | 中交武汉港湾工程设计研究院有限公司 | Organic composite reinforced concrete rust inhibitor and preparation method thereof |
| CN102757197A (en) * | 2012-06-26 | 2012-10-31 | 江苏博特新材料有限公司 | Surface coating type reinforced concrete corrosion inhibitor and preparation method thereof |
| CN105366978A (en) * | 2015-11-18 | 2016-03-02 | 刘志勇 | Permeable steel bar corrosion inhibitor for durability repair of concrete structure and preparation method thereof |
| CN106278061A (en) * | 2016-09-10 | 2017-01-04 | 江苏省建筑工程集团丰达混凝土有限公司 | A kind of weight concrete |
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| CN109811346A (en) * | 2019-01-11 | 2019-05-28 | 东南大学 | A kind of gas phase corrosion inhibitor and preparation method thereof and the application in terms of building iron corrosion protection |
| CN111587056A (en) * | 2020-05-14 | 2020-08-25 | 湖南省国银新材料有限公司 | Electromagnetic shielding silver paste for communication equipment and preparation method thereof |
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