CN109336502A - A kind of self film anti-corrosion marine structure concrete material and preparation method thereof - Google Patents
A kind of self film anti-corrosion marine structure concrete material and preparation method thereof Download PDFInfo
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- CN109336502A CN109336502A CN201811267849.XA CN201811267849A CN109336502A CN 109336502 A CN109336502 A CN 109336502A CN 201811267849 A CN201811267849 A CN 201811267849A CN 109336502 A CN109336502 A CN 109336502A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- 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
- C04B40/0042—Powdery mixtures
-
- 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
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/24—Sea water resistance
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/26—Corrosion of reinforcement resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
Abstract
The invention discloses a kind of self film anti-corrosion marine structure concrete materials and preparation method thereof, by the way that aluminium is connect with graphene, using graphene two-dimensional structure grinding when aluminium with piece shape two-dimensional structure dispersion, when for concrete, the compound aluminium powder of nanometer sheet shape is with high salt by seawater in concrete, soda acid etch aoxidizes, self film is aoxidized into fine and close protective layer, which can close the deep action of rust of chloride ion, slow down steel bar corrosion in maritime concrete.To reach maritime concrete to high-intensitive, high-durability and highly corrosion resistant requirement, and then improve the service life of maritime concrete.
Description
Technical field
The present invention relates to maritime concrete technical fields, and in particular to a kind of self film anti-corrosion marine structure concrete material
Material and preparation method.
Background technique
With the development of ocean engineering, concrete is required higher and higher.Traditional portland cement concrete material exists
It is played an important role in national economy, and portland cement concrete material is difficult to keep out the erosion of seawater.Main development at present
The maritime concrete built with Yu Haiyang.Under marine environment, the destructive factor of building structure mainly has: steel bar corrosion effect,
Carbonization, corrosion, salt corrosion effect, Frozen-thawed cycled effect, alkali, soda acid corrosion function, impact wear
With mechanical damage effect etc..Wherein, most important Slope protection is steel bar corrosion effect and salt corrosion effect.In seawater and sea
For the concrete works on bank due to being corroded for a long time by Cl-, the phenomenon that Rust of Rebar in Concrete, is very universal, built harbour code
The requirement of projected life is not achieved in first-class engineering majority.
The preparation measure of maritime concrete mainly on the basis of normal concrete, add high-quality active mineral mixture and
The comprehensive technical measures such as high-performance water reducing agent are started with, its corrosion-resistant property is improved.There is no fundamentally solve portland cement
The defect of concrete erosion resisting difference.It is high to the performance requirement of concrete material under the harsh environment of ocean including high-intensitive, high resistance to
Long property and high volume stability, however traditional concrete technology can not adapt to the requirement of modern marine engineering, compel to be essential
The superior in durability for wanting research and development new, high-performance marine engineering construction new material that environment is good.
Application No. is a kind of corrosion proof high performance marine concrete and its manufacturer are proposed in CN200510025690.7
Method, the disclosure of the invention a kind of maritime concrete being formulated by cement admixture and water, the cement admixture include water
Mud, admixture, aggregate and water-reducing agent, wherein admixture and cement weight ratio are the volume of admixture with cement and admixture
Total weight is 65 ~ 70%, and cement is 30 ~ 35%；The weight ratio of water-reducing agent volume and cement and admixture be admixture with
The total weight of cement and admixture is 1.0 ~ 1.4%, the volume of aggregate with the total weight of cement and admixture be 70 ~
76%.Although the program effectively reduces concrete voids rate, guarantee maritime concrete under the preferred water-cement ratio of effective solution
Endurance issues under strength conditions, but limited sky can only be reduced only according to the admixtures such as grading of aggregates and miberal powder, flyash
Gap rate.And usually reducing water-cement ratio and concrete early stage anticracking needs to add and subtract aqua, the program, which passes through, adds water-reducing agent,
Water-cement ratio is effectively reduced, but program water-reducing agent additional amount is larger, excessive water-reducing agent is added and is bound to cost to be increased.
Application No. is CN200810146926 to propose the maritime concrete cement of a kind corrosion resistance of chloride ion, the marine worker
The percentage of the material prescription of concrete cement by weight is as follows: clinker 30-35%；Ground slag powder 40-45%；Powder
Coal ash 20-25%；Gypsum 5-8%.Such concrete improves the resistance to corrosion of concrete to a certain extent, still, makes
It uses gypsum (calcium sulfate) as raw material, on the one hand improves the material cost of concrete, on the other hand, when concrete cement is in water
When lower work, gypsum component slightly soluble in the seawater, is that concrete structure is destroyed.
A kind of maritime concrete is proposed application No. is 201410131941.9, and primary raw material includes cementitious material, thin
Gather materials, coarse aggregate, water and additive, cementitious material include cement, miberal powder, flyash, it is characterized in that, primary raw material quality
Proportion are as follows: 380-500 parts of cementitious material, in which: 175-225 parts of cement, 135-163.8 parts of miberal powder, flyash 79-100
Part, 730-773 parts of fine aggregate, 1050-1112 parts of coarse aggregate, 150 parts of water, 14.22-19.5 parts of additive.Such coagulation
The self-compaction degree of soil is not high, and the chloride ion in seawater is easy through concrete pore corrosion reinforcing bar, but also containing a large amount of
Calcium hydroxide ingredient, when working under water, the substances such as easy sulfate with seawater react, and concrete structure is by broken
It is bad.
Currently, have using organosilicon intrusion type Concrete Protective Agent the application in concrete in marine environment engineering,
Graphene has been used for anti-corrosion concrete etc..
Summary of the invention
The purpose of the present invention is to provide a kind of self film anti-corrosion marine structure concrete material and preparation method, preparation
Self film anti-corrosion marine structure concrete material improves the comprehensive performance of maritime concrete, has good property.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention provides a kind of preparation method of self film anti-corrosion marine structure concrete material, it is characterised in that specific system
Preparation Method is as follows:
Aluminium is melted under nitrogen protection, and uniform with graphene dispersion, spraying liquid nitrogen chilling, aluminium chilling at graphene interface,
Then it grinds under nitrogen protection, obtains the nano combined aluminium powder that aluminium is connect with graphene interface;By nano combined aluminium powder, mineral
Admixture, clinker, aggregate and additive, are stirred, and obtain self film anti-corrosion marine structure concrete material.
Preferably, the mass ratio of aluminium and graphene is 5:1, and ball mill, mill machine or airslide disintegrating mill are selected in the grinding
It is ground；It is preferred that ball mill is preferably come aluminium with piece shape grinding distribution by the impact of ball mill.
Since maritime concrete is often with high salt by seawater, soda acid etch, maritime concrete is proposed higher
It is required that nano combined aluminium powder is added in the present invention in the preparation process of maritime concrete, to improve the corrosion-resistant of maritime concrete
Property.After first aluminum substrate is melted, realize the fusing of aluminum substrate, by after melting aluminum substrate and graphene mix dispersion,
The evenly dispersed purpose effectively both realized, then by the method for liquid nitrogen rapid cooling by aluminium rapid cooling in graphene
Surface, the combination at the interface both realized.By the way that aluminum substrate to be connect with graphene, the two-dimensional structure using graphene is being ground
Aluminium is when mill with the dispersion of piece shape two-dimensional structure, and when being used for concrete, the compound aluminium powder of nanometer sheet shape is with high salt by seawater, sour in concrete
Alkali etch oxidation, oxidation self film is at fine and close protective layer, while graphene can also form erosion resistant coating, which can close Cl- depth
The action of rust entered slows down steel bar corrosion in maritime concrete, to reach maritime concrete to high-intensitive, high-durability and height
The requirement of corrosion resistance.
The mineral admixture is one or more of slag, steel slag, flyash, red mud.
The clinker is portland cement or sulphoaluminate cement clinker.
The aggregate that selects is one or more of river sand, sea sand, machine-made sand, tailing sand.
The additive is one or more of water-reducing agent, early strength agent, antifreezing agent.
It is further preferred that the weight ratio of nano combined aluminium powder and mineral admixture, clinker, aggregate, additive is
10-15:55-100:45-85:45-80:5-10。
The water-reducing agent is to have one of lignosulfonates, naphthalene sulphonate formaldehyde polymer, polycarboxylate water-reducer.
The early strength agent is calcium chloride.
The antifreezing agent is ethylene glycol or triethanolamine.
Nano combined aluminium powder can significantly improve the mechanical properties such as tensile strength and the yield strength of aluminum substrate, also show
Good plasticity and processing performance, hence it is evident that improve the corrosion resistance of marine structure；Mineral admixture can reduce hydration heat of concrete,
Improve concrete workability, reduce isolation and bleeding, reduce temperature difference of mass concrete variation and internal stress, inhibit the temperature difference and
The crack of generation improves the pore structure in concrete, so that aperture is fined and is homogenized, improve the impervious, freeze proof of concrete
Melting property and durability；Aggregate all has significance to flexural strength, the durability of concrete；Additive can be according to concrete
It is required that addition, in order to improve the additive, including various water-reducing agents, antifreezing agent, early strength agent etc. of concrete mix workability energy.
The present invention also provides a kind of self film anti-corrosion marine structure concrete materials prepared by the preparation method.
The beneficial effects of the present invention are:
By the way that aluminium to be connect with graphene, using the two-dimensional structure of graphene, in grinding, aluminium is used with the dispersion of piece shape two-dimensional structure
When concrete, the compound aluminium powder of nanometer sheet shape is with high salt by seawater in concrete, soda acid etch aoxidizes, and aoxidizes self film into densification
Protective layer, which can close the deep action of rust of chloride ion, slow down steel bar corrosion in maritime concrete.To reach marine worker
Concrete improves the service life of maritime concrete to high-intensitive, high-durability and highly corrosion resistant requirement.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.
Embodiment 1
700 DEG C aluminium is melted, and be dispersed with stirring uniformly with graphene with mass ratio 5:1 under nitrogen protection, then utilizes 1MPa
Pressure high-pressure fog and ball mill is then added under nitrogen protection by aluminium chilling at graphene interface in liquid nitrogen chilling,
Obtain the nano combined aluminium powder that aluminium is connect with graphene interface, by nano combined aluminium powder, slag, portland cement, river sand and
Additive is stirred with weight ratio 10:55:45:45:5, obtains self film anti-corrosion marine structure concrete material.It is wherein additional
Agent is lignosulfonates, calcium chloride, ethylene glycol are cooperated with mass ratio 1:1:1.
Embodiment 2
700 DEG C aluminium is melted, and be dispersed with stirring uniformly with graphene with mass ratio 5:1 under nitrogen protection, then utilizes 2MPa
Pressure high-pressure fog and in liquid nitrogen chilling, by aluminium chilling at graphene interface, then under nitrogen protection be added mill machine
Grinding, obtains the nano combined aluminium powder that aluminium is connect with graphene interface, and nano combined aluminium powder, steel slag, sulphate aluminium cement is ripe
Material, river sand, additive are stirred with weight ratio 15:6060:45:5, obtain self film anti-corrosion marine structure concrete material.
Wherein additive is naphthalene sulphonate formaldehyde polymer, calcium chloride, ethylene glycol are cooperated with mass ratio 1:1:1.
Embodiment 3
700 DEG C aluminium is melted, and be dispersed with stirring uniformly with graphene with mass ratio 5:1 under nitrogen protection, then utilizes 1MPa
Pressure high-pressure fog and in liquid nitrogen chilling, by aluminium chilling at graphene interface, then under nitrogen protection be added air-flow powder
Broken machine grinding, obtains the nano combined aluminium powder that aluminium is connect with graphene interface, by nano combined aluminium powder, flyash, aluminium sulfate
Clinker, machine-made sand, additive are stirred with weight ratio 15:80:85:45:10, and it is mixed to obtain self film anti-corrosion marine structure
Solidifying soil material.Wherein additive is polycarboxylate water-reducer, calcium chloride, ethylene glycol are cooperated with mass ratio 1:1:1.
Embodiment 4
700 DEG C aluminium is melted, and be dispersed with stirring uniformly with graphene with mass ratio 5:1 under nitrogen protection, then utilizes 1MPa
Pressure high-pressure fog and ball mill is then added under nitrogen protection by aluminium chilling at graphene interface in liquid nitrogen chilling
Grinding, obtains the nano combined aluminium powder that aluminium is connect with graphene interface, by nano combined aluminium powder, red mud, portland cement, river
Husky, additive is stirred with weight ratio 15:55:85:80:10, obtains self film anti-corrosion marine structure concrete material.Wherein
Additive is lignosulfonates, calcium chloride, ethylene glycol are cooperated with mass ratio 1:1:1.
Comparative example 1
Aluminium powder, red mud, portland cement, river sand, additive are stirred with weight ratio 15:55:85:80:10, obtain anti-corrosion
Marine structure concrete material.Wherein additive be lignosulfonates, calcium chloride, ethylene glycol with mass ratio 1:1:1 cooperation and
At.
Comparative example 1 is compound with graphene melting to use, and aluminium is used for concrete rather than microplate shape in granular form.Influence oxygen
Change the anti-corrosive properties of self film.
The concrete that embodiment 1-4, comparative example 1 are obtained under equal conditions hydrous water mix, is made with mobility
After the concrete mix of energy, 25 days, 50 days are voluntarily hardened after molding, test the intensity and corrosion resistance of concrete.Test knot
Fruit such as table 1:
For 4d compression strength 46.6MPa or more, 28d compression strength in 58.2MPa or more, it is strong that early anti pressured intension has reached design
The 80% of degree, can satisfy the requirement of prestressed stretch-draw；56d chloride diffusion coefficient test result is 2.0 × 10-12m2/s
Below
1 test result of table
By above-mentioned table 1 it can be seen that from stability, 25d chloride diffusion coefficient, coefficient against corrosion, intensity and flexural strength totally 5
A aspect is tested, and test result shows: the stability in 1-4 of the embodiment of the present invention is qualification, and comparative example 1 is unqualified,
And the permeance property of the resisting chloride ion penetration in 1-4 of the embodiment of the present invention is relatively high, and coefficient against corrosion is high.Determine the expansion of 25d chloride ion
Dissipate the compression strength and flexural strength of system, coefficient against corrosion and 25d and 50d, the embodiment of the present invention it can be seen from measurement result
The permeance property of the maritime concrete chloride ion of middle preparation is relatively high, and coefficient against corrosion is high, and flexural strength and flexural strength are obviously high
In the corresponding numerical value of current conventional maritime concrete.
Claims (9)
1. a kind of preparation method of self film anti-corrosion marine structure concrete material, it is characterised in that it is specific the preparation method is as follows:
Aluminium is melted under nitrogen protection, and uniform with graphene dispersion, spraying liquid nitrogen chilling, aluminium chilling at graphene interface,
Then it grinds under nitrogen protection, obtains the nano combined aluminium powder that aluminium is connect with graphene interface;By nano combined aluminium powder, mineral
Admixture, clinker, aggregate and additive, are stirred, and obtain self film anti-corrosion marine structure concrete material.
2. a kind of preparation method of self film anti-corrosion marine structure concrete material according to claim 1, it is characterised in that:
The mass ratio of aluminium and graphene is 5:1, and the grinding selects ball mill, mill machine or airslide disintegrating mill to be ground.
3. a kind of preparation method of self film anti-corrosion marine structure concrete material according to claim 1, it is characterised in that:
The mineral admixture is one or more of slag, steel slag, flyash, red mud.
4. a kind of preparation method of self film anti-corrosion marine structure concrete material according to claim 1, it is characterised in that:
The clinker is portland cement or sulphoaluminate cement clinker.
5. a kind of preparation method of self film anti-corrosion marine structure concrete material according to claim 1, it is characterised in that:
The aggregate that selects is one or more of river sand, sea sand, machine-made sand, tailing sand.
6. a kind of preparation method of self film anti-corrosion marine structure concrete material according to claim 1, it is characterised in that:
The additive is one or more of water-reducing agent, early strength agent, antifreezing agent.
7. a kind of preparation method of self film anti-corrosion marine structure concrete material according to claim 1, it is characterised in that:
The weight ratio of nano combined aluminium powder and mineral admixture, clinker, aggregate, additive is 10-15:55-100:45-85:45-
80:5-10。
8. a kind of preparation method of self film anti-corrosion marine structure concrete material according to claim 6, it is characterised in that:
The water-reducing agent is one of lignosulfonates, naphthalene sulphonate formaldehyde polymer, polycarboxylate water-reducer；The early strength agent is
Calcium chloride；The antifreezing agent is ethylene glycol or triethanolamine.
9. a kind of self film anti-corrosion marine structure concrete material, which is characterized in that the self film anti-corrosion marine structure coagulation
Soil material is prepared using preparation method of any of claims 1-8.
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| CN201811267849.XA CN109336502A (en) | 2018-10-29 | 2018-10-29 | A kind of self film anti-corrosion marine structure concrete material and preparation method thereof |
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| CN201811267849.XA CN109336502A (en) | 2018-10-29 | 2018-10-29 | A kind of self film anti-corrosion marine structure concrete material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563351A (en) * | 2019-10-16 | 2019-12-13 | 河海大学 | Cement-based material for improving chloride ion binding rate and preparation method thereof |
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2018
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563351A (en) * | 2019-10-16 | 2019-12-13 | 河海大学 | Cement-based material for improving chloride ion binding rate and preparation method thereof |
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Application publication date: 20190215 |