CN111268978A - Carbon fiber doped conductive cement-based material and preparation method and application thereof - Google Patents

Carbon fiber doped conductive cement-based material and preparation method and application thereof Download PDF

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Publication number
CN111268978A
CN111268978A CN202010177877.3A CN202010177877A CN111268978A CN 111268978 A CN111268978 A CN 111268978A CN 202010177877 A CN202010177877 A CN 202010177877A CN 111268978 A CN111268978 A CN 111268978A
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cement
carbon fiber
based material
parts
conductive cement
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金祖权
李树鹏
杜丰音
李师财
蒋继宏
宋华苗
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Qingdao University of Technology
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Qingdao University of Technology
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Priority to CN202010177877.3A priority Critical patent/CN111268978A/en
Publication of CN111268978A publication Critical patent/CN111268978A/en
Priority to PCT/CN2020/102788 priority patent/WO2021017900A1/en
Priority to LU102505A priority patent/LU102505B1/en
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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
    • C04B28/06—Aluminous cements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/52—Producing shaped prefabricated articles from the material specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/08—Producing shaped prefabricated articles from the material by vibrating or jolting
    • B28B1/087—Producing shaped prefabricated articles from the material by vibrating or jolting by means acting on the mould ; Fixation thereof to the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/29—Producing shaped prefabricated articles from the material by profiling or strickling the material in open moulds or on moulding surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B23/00—Arrangements specially adapted for the production of shaped articles with elements wholly or partly embedded in the moulding material; Production of reinforced objects
    • B28B23/0062—Arrangements specially adapted for the production of shaped articles with elements wholly or partly embedded in the moulding material; Production of reinforced objects forcing the elements into the cast material, e.g. hooks into cast concrete
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
    • B28C5/40—Mixing specially adapted for preparing mixtures containing fibres
    • B28C5/402—Methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
    • B28C5/40—Mixing specially adapted for preparing mixtures containing fibres
    • B28C5/404—Pre-treatment of fibres
    • 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
    • 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
    • C04B40/0003—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability making use of electric or wave energy or particle radiation
    • C04B40/0007—Electric, magnetic or electromagnetic fields
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/34—Non-shrinking or non-cracking materials
    • 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
    • C04B2111/90—Electrical properties
    • C04B2111/94—Electrically conducting materials

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Abstract

The invention provides a carbon fiber doped conductive cement-based material which comprises the following components in parts by weight: 85-90 parts of cement, 200 parts of sand 125 and sand, 10-15 parts of mineral powder, 1-3 parts of redispersible latex powder, 40-50 parts of water, 0.5-0.8 part of water reducing agent and 0.03-0.06 part of defoaming agent; and carbon fibers, wherein the volume of the carbon fibers accounts for 0.6-1% of the volume of the mixture. The preparation method of the conductive cement-based material comprises the following steps: s1, preparing a carbon fiber dispersion liquid; s2, preparing cement-based mortar; and S3, forming the conductive cement-based material. The conductive cement-based material has the properties of early strength and quick hardening, and is suitable for repair engineering; the durability and the toughness are higher, the resistivity is lower, and the shrinkage of the cement-based material is effectively reduced; has the functions of repairing and conducting, and has wide development prospect when being applied to the fields of electrochemical dechlorination and the like.

Description

Carbon fiber doped conductive cement-based material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of cement-based composite materials, and particularly relates to a conductive cement-based material and a preparation method and application thereof.
Background
Under the action of external environmental conditions, some buildings are corroded and damaged, so that the service life of the buildings is influenced. The building is generally a reinforced concrete structure, and the structure and the service performance of the reinforced concrete structure are greatly influenced after the reinforced concrete structure is corroded. Impressed current cathodic protection is one of the most effective protective measures for rusted reinforced concrete. The selection of anode materials in a cathodic protection system is the most critical technology, and for a reinforced concrete system polluted by chlorine salt, in order to improve the protection efficiency of a cathode, the anode materials with excellent performance coated on the surface of concrete need to meet the following basic requirements: (1) the electrons are conductive, the resistivity is low, and the required protection current is provided; (2) the electrochemical inertia is provided, so that a longer service life is ensured; (3) has excellent mechanical property, especially higher adhesive strength with base concrete and better toughness.
The strengthening service life of the titanium-based anode electrode of the existing anode material is long, but the cost is too high; the anode of the conductive coating can be damaged in the process of alternation of dry and wet, cold and hot circulation, ultraviolet exposure, serious chlorine salt corrosion or overlarge current density; the conductive cement-based material can repair a damaged structure and simultaneously utilize the conductive performance of the conductive cement-based material to monitor and evaluate the structure, and has excellent use performance. However, the conductive fillers such as graphite, carbon black, carbon fiber and the like added into the conductive cement-based material are not easy to disperse in the cement-based material, and the service performance of the conductive cement-based material is affected. For buildings needing to repair the concrete surface damage, the anode material is required to have early strength and early hardness, and Portland cement used in common cement base is not easy to construct and long in setting time during repair, is not beneficial to repair and limits the application.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a carbon fiber doped conductive cement-based material, and a preparation method and application thereof, which are used for solving the problems of difficult dispersion of fillers, low mechanical property and deficient repair function of the traditional conductive cement-based material and providing the conductive cement-based material with excellent conductivity, mechanical property and durability.
In order to achieve the above purpose, the invention provides the following technical scheme:
the carbon fiber doped conductive cement-based material comprises the following components in parts by weight:
85-90 parts of cement, 200 parts of sand 125 and sand, 10-15 parts of mineral powder, 1-3 parts of redispersible latex powder, 40-50 parts of water, 0.5-0.8 part of water reducing agent and 0.03-0.06 part of defoaming agent;
and carbon fibers, wherein the volume of the carbon fibers accounts for 0.6-1% of the volume of the mixture.
In the carbon fiber-doped conductive cement-based material as described above, preferably, the length of the carbon fiber is 6 to 9 mm.
In the carbon fiber-doped conductive cement-based material as described above, preferably, the cement is a sulphoaluminate cement.
The carbon fiber doped conductive cement-based material preferably further comprises a dispersant, wherein the doping mass of the dispersant is 0.4-0.6% of the mass of a cementing material, and the mass of the cementing material is the sum of the mass of the cement and the mass of the mineral powder;
preferably, the dispersant is methylcellulose.
In the carbon fiber doped conductive cement-based material, preferably, the redispersible latex powder is an ethylene/vinyl acetate copolymer;
preferably, the water reducing agent is a polycarboxylic acid type water reducing agent.
A preparation method of a carbon fiber doped conductive cement-based material comprises the following steps:
s1 preparation of carbon fiber dispersion liquid
Dissolving the weighed carbon fibers in water, and uniformly dispersing to obtain a pre-dispersed carbon fiber liquid; adding a dispersing agent and a defoaming agent into the pre-dispersed carbon fiber liquid, and stirring and ultrasonically dispersing to obtain a carbon fiber dispersion liquid;
s2 preparation of cement-based mortar
Adding cement, mineral powder, redispersible latex powder, water and a water reducing agent into a stirrer and uniformly stirring; then adding the carbon fiber dispersion liquid obtained in the step S1 into a stirrer to be continuously stirred uniformly; adding the sand into a stirrer, and uniformly stirring to obtain a cement-based mortar mixture;
s3 forming of conductive cement-based material
Filling the cement-based mortar obtained in the step S2 into a mould, compacting and leveling, and inserting an electrode material; and (5) standing for 4-24h, demoulding and curing to obtain the conductive cement-based material.
In the preparation method of the carbon fiber-doped conductive cement-based material, preferably, the specific preparation process of the pre-dispersed carbon fiber liquid in the step S1 is as follows: dissolving carbon fibers in water, heating the water to 65-75 ℃, and performing ultrasonic dispersion for 5-15min to obtain the pre-dispersed carbon fiber liquid.
In the preparation method of the carbon fiber-doped conductive cement-based material, preferably, in step S1, the dispersant is added into the pre-dispersed carbon fiber liquid, and the mixture is stirred and ultrasonically dispersed for 5-15 min;
preferably, the water for dissolving the carbon fibers in the step S1 accounts for 1/3-2/3 of the water amount in the mixture.
In the above method for preparing a carbon fiber-doped conductive cement-based material, preferably, in step S3, the curing conditions are as follows: curing in a curing chamber with the temperature of 15-25 ℃ and the relative humidity of more than or equal to 90 percent.
The application of the conductive cement-based material prepared by the preparation method of the carbon fiber doped conductive cement-based material is preferably to apply the conductive cement-based material to electrochemical dechlorination.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the preparation method of the carbon fiber doped conductive cement-based material has the following excellent effects:
1. the sulphoaluminate cement is used as the cement in the conductive cement-based material, compared with the traditional Portland cement, the sulphoaluminate cement is more environment-friendly and has more excellent performance, so that the conductive cement-based material has the performance of early strength and rapid hardening, and is more suitable for repair engineering.
2. The redispersible latex powder is added into the conductive cement base, so that the bonding force between the conductive cement base and the reinforced concrete is improved, the durability and the toughness of the cement-based material are improved, and the conductive cement base is used for a longer time in a harsh environment.
3. The conductive filler used by the conductive cement base is carbon fiber with proper length, the dispersibility is good, the carbon fiber is distributed in the cement base material to form a coherent conductive network, compared with conductive materials such as graphite, carbon nano tubes and the like, the consumption of the carbon fiber is less, the conductive network is easier to form, and the resistivity of the cement base material is lower; and the addition of the carbon fiber can improve the toughness of the material and effectively reduce the shrinkage of the cement-based material.
4. The conductive cement-based material prepared by combining the modified sulphoaluminate cement and the carbon fiber has the functions of repairing and conducting, not only has excellent mechanical property and durability, but also has lower resistivity, and has wide development prospect when being applied to the fields of electrochemical dechlorination and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a schematic diagram of the four-electrode method for measuring resistivity of a conductive cement-based material according to example 1 of the present invention;
FIG. 2 is a graph of resistivity of conductive cement-based materials obtained with different amounts of carbon fibers in test example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The carbon fiber doped conductive cement-based material is applied to electrochemical dechlorination of rusted reinforced concrete, and the filler carbon fiber is added into the conductive cement-based material, so that the carbon fiber has high strength, corrosion resistance and excellent conductivity, and can improve the mechanical property of the cement-based material, improve the toughness and reduce the dry shrinkage after being added into cement; in the invention, proper carbon fiber size and a dispersing agent are selected, and a reasonable dispersing process is added, so that the carbon fibers can form a conductive network in a cement base more easily. The cement adopted in the invention is sulphoaluminate cement, and the sulphoaluminate cement has the advantages of short setting time, high early strength and the like compared with common silicate cement, and is more suitable for being used as a repairing material of some projects.
The modified sulphoaluminate cement-based material is combined with the well-dispersed carbon fibers to prepare a novel conductive cement-based material, the defects that the traditional conductive filler is high in mixing amount in the cement-based material and is not easy to disperse are overcome, and the novel conductive cement-based material has excellent conductive performance by adding a small amount of the well-dispersed carbon fibers; meanwhile, the conductive cement-based material uses the sulphoaluminate cement, so that the conductive cement-based material is easier to construct, has high early strength, short setting time and good cohesiveness with a concrete matrix and is beneficial to rush repair compared with common portland cement. The conductive cement-based material prepared by the invention has good conductive effect, excellent mechanical property and durability, long service life and wide development and application prospect in the fields of electrochemical desalting, steel bar corrosion monitoring and the like.
The invention provides a carbon fiber doped conductive cement-based material which comprises the following components in parts by weight:
85-90 parts (such as 86 parts, 87 parts, 88 parts, 89 parts and 89.5 parts) of cement, 125-200 parts (such as 130 parts, 135 parts, 140 parts, 145 parts, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, 180 parts, 185 parts, 190 parts and 195 parts) of sand, 10-15 parts (such as 10.5 parts, 11 parts, 12 parts, 13 parts, 14 parts and 15 parts) of mineral powder, 1-3 parts (such as 1.5 parts, 2 parts, 2.5 parts and 3 parts) of redispersible latex powder, 40-50 parts (such as 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts and 49 parts) of water reducer, 0.5-0.8 part (such as 0.6 part, 0.7 part and 0.8 part) of defoaming agent, 0.03-0.06 part (such as 0.04 part, 0.05 part and 0.06 part);
and carbon fibers, the volume of the carbon fibers accounts for 0.6-1% (such as 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%) of the volume of the mixture.
Preferably, the conductive cement-based material further comprises a dispersant, wherein the dispersant is mixed in 0.4-0.6% (such as 0.45%, 0.5%, 0.55%, 0.6%) of the mass of the cementing material; the mass of the cementing material is the sum of the mass of cement and mineral powder.
In the specific embodiment of the invention, the glue-sand ratio is 1 (1.25-2) such as (1:1.3, 1:1.35, 1:1.4, 1:1.45, 1:1.5, 1:1.55, 1:1.6, 1:1.65, 1:1.7, 1:1.75, 1:1.8, 1:1.85, 1:1.9 and 1:1.95), wherein the glue-sand ratio is the mass ratio of the total amount of cement and mineral powder to sand; the mixture of cement and mineral powder is also called as gel material; a water-to-gel ratio of 0.4 to 0.5, i.e., a ratio of water to cementitious material of 0.4 to 0.5 (e.g., 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49); the mass of the redispersible latex powder is 1-3 percent of that of the gel material, the mass of the water reducing agent is 0.5-0.8 percent of that of the gel material, and the mass of the defoaming agent is 0.03-0.06 percent of that of the gel material.
Different water-cement ratios and water reducing agent mixing amounts in the conductive cement-based material can influence the fluidity of the conductive cement-based material, so that the dispersion of carbon fibers in the cement-based material is influenced, the formation of a conductive network of the conductive cement-based material is finally influenced, and the reasonable dispersing agent mixing amount is more favorable for the dispersion of the carbon fibers in the cement-based material.
In a specific embodiment of the present invention, the carbon fibers have a length of 6 to 9mm (e.g., 6.5mm, 7mm, 7.5mm, 8mm, 8.5 mm). Because the carbon fibers are too short and are not easy to overlap to form a conductive network, and the carbon fibers are too long, the carbon fibers are not beneficial to the dispersion of the carbon fibers in the cement base, the carbon fibers with the length of 6-9mm can be selected to be mutually overlapped to form a better conductive network, and can be well dispersed in the cement base, so that the stability of the conductive cement base material is improved, and the resistivity is reduced.
In a specific embodiment of the invention, the cement is a sulphoaluminate cement.
In the specific embodiment of the invention, the redispersible latex powder is an ethylene/vinyl acetate copolymer; preferably, the dispersant is methylcellulose; still more preferably, the water reducing agent is a polycarboxylic acid type water reducing agent.
In order to further understand the conductive cement-based material, the invention also provides a preparation method of the carbon fiber doped conductive cement-based material, which comprises the following steps:
s1 preparation of carbon fiber dispersion liquid
Dissolving the weighed carbon fibers in water, and uniformly dispersing to obtain a pre-dispersed carbon fiber liquid; adding a dispersing agent and a defoaming agent into the pre-dispersed carbon fiber liquid, and stirring and ultrasonically dispersing to obtain a carbon fiber dispersion liquid;
in the specific embodiment of the invention, in step S1, the dispersing agent is added to the pre-dispersed carbon fiber liquid, and the mixture is stirred and ultrasonically dispersed for 5-15min (for example, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14 min).
Preferably, the water for dissolving the carbon fibers in the step S1 accounts for 1/3-2/3 of the water content in the mixed material, and more preferably, the water for dissolving the carbon fibers accounts for 1/3 of the water content in the mixed material.
Preferably, the specific preparation process of the pre-dispersed carbon fiber liquid in the step S1 is as follows: dissolving carbon fiber in water, heating water to 65-75 deg.C (such as 66 deg.C, 67 deg.C, 68 deg.C, 69 deg.C, 70 deg.C, 71 deg.C, 72 deg.C, 73 deg.C, and 74 deg.C), and ultrasonically dispersing for 5-15min (such as 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, and 14min) to obtain pre-dispersed carbon fiber solution.
S2 preparation of cement-based mortar
Adding cement, mineral powder, redispersible latex powder, water and a water reducing agent into a stirrer and uniformly stirring; then adding the carbon fiber dispersion liquid obtained in the step S1 into a stirrer and continuously stirring uniformly; adding the sand into a stirrer, and uniformly stirring to obtain a cement-based mortar mixture;
s3 forming of conductive cement-based material
Filling the cement-based mortar obtained in the step S2 into a mould, compacting and leveling, and inserting an electrode material; standing for 4-24h (such as 5h, 10h, 15h, 17h, 20h, 21h, 22h, 23h and 24h), demolding, and curing to obtain the conductive cement-based material. Preferably, the electrodes are copper sheet electrodes.
In the embodiment of the present invention, in step S3, the curing is performed under the specific conditions that the curing is performed in a curing chamber having a temperature of 15 to 25 ℃ (e.g., 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃) and a relative humidity of not less than 90%.
The conductive cement-based material prepared by the preparation method of the carbon fiber doped conductive cement-based material is applied to electrochemical dechlorination of rusted reinforced concrete.
The cement adopted in the following embodiment of the invention is high belite sulphoaluminate cement produced by Hebei Tangshan polar bear building materials GmbH; the carbon fiber is prepared by chopping Nippon adhesive-free and pulp-free carbon fiber filaments, and has specification of 6-9mm, strength of 4900Mpa, modulus of 240Gpa, and resistivity of 1.5 x 10-3Omega, cm, monofilament diameter 7 μm; the sand is river sand with fineness modulus of 2.7; the water reducing agent is a polycarboxylic acid type high-efficiency water reducing agent produced by Jiangsu Borter new material company Limited.
Example 1
The preparation method of the carbon fiber doped conductive cement-based material provided by the embodiment comprises the following steps:
step S1, putting 10.8g of carbon fibers (the doping amount of the carbon fibers is 0.6 percent of the volume of the mixture) into a 500ml beaker, adding 134g of water heated to 70 ℃ into the beaker, uniformly stirring the mixture by using a glass rod, putting the mixture into an ultrasonic cleaning instrument, and ultrasonically dispersing the mixture for 10min to obtain pre-dispersed carbon fiber liquid; weighing 3.2g of methyl cellulose, putting the methyl cellulose into the pre-dispersed carbon fiber liquid, uniformly stirring the mixture by using a glass rod, adding 0.24g of defoaming agent by using a rubber head dropper, and continuing to carry out ultrasonic dispersion for 10min to obtain the dispersed carbon fiber dispersion liquid for later use.
Step S2, weighing 720g of sulphoaluminate cement, 80g of mineral powder and 266g of water, wherein the water consumption is 2/3 of the total water consumption, 1/3 g of redispersible latex powder and 4g of water reducing agent which use the total water consumption for dissolving and dispersing carbon fibers are added into a mortar stirring pot, stirring is carried out at a low speed for 30S at a stirring speed of 140 +/-5 r/min, the stirring is stopped, the dispersed carbon fiber dispersion liquid is added, stirring is carried out at a low speed for 30S at a stirring speed of 140 +/-5 r/min, 1200g of sand is added, and stirring is carried out at a low speed for 180S at a stirring speed of 140 +/-5 r/min.
And step S3, pouring the mixture into a cement mortar triple die, putting the cement mortar triple die into a vibrating table, compacting and grinding the cement mortar triple die to be flat, inserting a copper sheet electrode, removing the die after 12 hours, and moving the copper sheet electrode into a standard curing room with the temperature of 20 ℃ and the relative humidity of 95% for curing.
Performance testing
Resistivity tests generally have three test modes, multimeter,And testing by a two-electrode method and a four-electrode method. When a multimeter is used for measuring the resistivity of the cement-based material, if the result of direct measurement by the multimeter usually has larger deviation, because the contact between the copper sheet and the test block can generate contact resistance, the measured resistance value is the sum of the contact resistance and the sample resistance, and great error is caused. The two-electrode method is usually used when the target resistance value is small because the resistance of the connecting wire is added to the measured resistance value during measurement. The problem in the test can be effectively avoided by adopting a four-electrode method, and the influence of circuit impedance on the resistance value of a measured target can be greatly reduced by adopting an independent current source and an inductive voltage circuit in the four-electrode method. Therefore, the resistivity test method adopts a four-electrode method, a schematic diagram is shown in figure 1, and the connection of a lead, a power supply, a voltmeter and an ammeter is carried out according to the schematic diagram. The resistivity calculation is based on the formula R ═ U/I, ρ ═ RS/L, where S — the cross-sectional area of the test piece (mm)2) L-distance between two electrodes in the middle.
The electrically conductive cement-based material prepared in this example had a resistivity value of 121.65 Ω · cm, as measured by the four-electrode method.
Example 2
In this embodiment, the mass of the carbon fiber in step S1 is changed to 14.4g (the amount of the carbon fiber is 0.8% of the volume of the mixture), and the other method steps are the same as those in embodiment 1 and are not repeated herein.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 69.16. omega. cm.
Example 3
In this embodiment, the mass of the carbon fiber in step S1 is changed to 18g (the carbon fiber content is 1% of the volume of the mixture), and the other method steps are the same as those in embodiment 1, and are not repeated herein.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 49.02 Ω · cm.
Example 4
In this embodiment, the mass of the redispersible latex powder in step S2 is replaced by 24g, and the other method steps are the same as those in embodiment 2, and are not repeated herein.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 61.27 Ω · cm.
Example 5
In this embodiment, the mass of the redispersible latex powder in step S2 is replaced by 8g, and the other steps of the method are the same as those in embodiment 2, and are not repeated herein.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 75.87 Ω · cm.
Example 6
In this embodiment, the carbon fiber with a diameter of 6mm in step S1 is replaced with the carbon fiber with a diameter of 9mm, and the other steps of the method are the same as those in embodiment 1, and are not repeated herein.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 183.24 Ω · cm.
Example 7
In this embodiment, the carbon fiber with a diameter of 6mm in step S1 is replaced with a carbon fiber with a diameter of 9mm, the mass of the carbon fiber is 14.4g, and the other steps of the method are the same as those of embodiment 2, and are not repeated herein.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 89.1 Ω · cm.
Example 8
The preparation method of the carbon fiber doped conductive cement-based material provided by the embodiment comprises the following steps:
step S1, putting 14.4g of carbon fibers (the carbon fiber content accounts for 0.8% of the volume of the mixture) into a 500ml beaker, adding 266g of water heated to 65 ℃, uniformly stirring by using a glass rod, putting into an ultrasonic cleaning instrument, and ultrasonically dispersing for 15min to obtain pre-dispersed carbon fiber liquid; weighing 3.2g of methyl cellulose, putting the methyl cellulose into the pre-dispersed carbon fiber liquid, uniformly stirring the mixture by using a glass rod, adding 0.48g of defoaming agent by using a rubber head dropper, and continuing to carry out ultrasonic dispersion for 5min to obtain the dispersed carbon fiber dispersion liquid for later use.
Step S2, 680g of sulphoaluminate cement, 120g of mineral powder and 134g of water are weighed, wherein the water consumption is 1/3 of the total water consumption, 2/3 g of redispersible latex powder and 6.4g of water reducing agent which are used for dissolving and dispersing carbon fibers are added into a mortar stirring pot, low-speed stirring is carried out for 30S at the stirring speed of 140 +/-5 r/min, stirring is stopped, the dispersed carbon fiber dispersion liquid is added, stirring is carried out for 30S at the stirring speed of 140 +/-5 r/min, 1600g of sand is added, and stirring is carried out for 180S at the stirring speed of 140 +/-5 r/min.
And step S3, pouring the mixture into a cement mortar triple die, putting the cement mortar triple die into a vibrating table, compacting and grinding the cement mortar triple die to be flat, inserting a copper sheet electrode, removing the die after 24 hours, and moving the copper sheet electrode into a standard curing room with the temperature of 25 ℃ and the relative humidity of 95% for curing.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 71.23 Ω · cm.
Example 9
The preparation method of the carbon fiber doped conductive cement-based material provided by the embodiment comprises the following steps:
step S1, putting 18g of carbon fibers (the carbon fiber doping amount accounts for 1% of the volume of the mixture) into a 500ml beaker, adding 266g of water heated to 75 ℃, uniformly stirring by using a glass rod, putting into an ultrasonic cleaning instrument, and ultrasonically dispersing for 15min to obtain a pre-dispersed carbon fiber liquid; weighing 4.8g of methyl cellulose, putting the methyl cellulose into the pre-dispersed carbon fiber liquid, uniformly stirring the mixture by using a glass rod, adding 0.48g of defoaming agent by using a rubber head dropper, and continuing to perform ultrasonic dispersion for 15min to obtain the dispersed carbon fiber dispersion liquid for later use.
Step S2, weighing 690g of sulphoaluminate cement, 110g of mineral powder and 134g of water, wherein the water consumption is 1/3 of the total water consumption, 2/3 g of redispersible latex powder and 6.4g of water reducing agent which are used for dissolving and dispersing carbon fibers are added into a mortar stirring pot, stirring is carried out at a low speed for 30S at a stirring speed of 140 +/-5 r/min, the stirring is stopped, the dispersed carbon fiber dispersion liquid is added, stirring is carried out at a low speed for 30S at a stirring speed of 140 +/-5 r/min, 1600g of sand is added, and stirring is carried out at a low speed for 180S at a stirring speed of 140 +/-5 r/min.
And step S3, pouring the mixture into a cement mortar triple die, putting the cement mortar triple die into a vibrating table, compacting and grinding the cement mortar triple die to be flat, inserting a copper sheet electrode, removing the die after 20 hours, and moving the copper sheet electrode into a standard curing room with the temperature of 20 ℃ and the relative humidity of 95% for curing.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 51.62 Ω · cm.
Test example 1
The test example is a test for changing the influence of the carbon fiber content on the resistivity of the prepared conductive cement-based material, and comprises the combination of examples 1-3 and other examples, and the steps and the method of the conductive cement-based material prepared in the test example are the same as those of example 1, except that the carbon fiber content is different.
The resistivity performance data of the conductive cement-based material prepared in this test example is shown in fig. 2.
Comparative example 1
The difference between this comparative example and example 2 is that the diameter of the carbon fiber in step S1 is changed to 5mm in diameter, and the other steps and methods are the same as those in example 2 and will not be described again.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 106.46 Ω · cm.
Comparative example 2
The difference between this comparative example and example 2 is that the diameter of the carbon fiber in step S1 is changed to 10mm in diameter, and the other steps and methods are the same as those in example 2 and will not be described again.
In this example, the same test method as in example 1 was used to prepare a conductive cement-based material having a resistivity value of 198.21 Ω · cm.
Comparative example 3
The difference between this comparative example and example 2 is that in this comparative example, the redispersible latex powder is not added in step S2, and other steps and methods are the same as those in example 2 and are not repeated herein.
In the embodiment, the same test method as that in embodiment 1 is adopted, and the fluidity of the conductive cement-based mortar without the addition of the redispersible latex powder is reduced, the cohesive force of the mortar is deteriorated, so that the cohesive force between the conductive cement-based material and the reinforced concrete is reduced, and the resistivity is slightly increased. The resistance value of the conductive cement-based material is 87.27 Ω · cm.
Comparative example 4
The difference between this comparative example and example 2 is that the amount of the dispersant methylcellulose added in step S1 in this comparative example accounts for 0.2% of the mass of the cement, and other steps and methods are the same as those in example 2 and are not described again here.
In this example, the same test method as in example 1 was used, and a decrease in the amount of the dispersant added reduced the dispersion of the carbon fibers, resulting in an increase in the resistivity, at which the conductor cement-based material had a resistivity of 87.82 Ω · cm.
Comparative example 5
The difference between this comparative example and example 2 is that the amount of the water reducing agent added in step S2 is 0.3% of the mass of the cementitious material (cement + mineral powder), and other steps and methods are the same as those in example 2 and are not described again here.
In the embodiment, the same test method as that in the embodiment 1 is adopted, and the reduction of the addition amount of the water reducing agent can reduce the fluidity of the mortar and deteriorate the workability of the conductive cement base, so that the carbon fibers are not easy to disperse and agglomerate in the cement base, and the resistivity of the conductive cement-based material is increased, wherein the resistivity of the conductive cement-based material prepared in the comparative example is 217.10 Ω · cm.
Comparative example 6
The difference between this comparative example and example 2 is that the cement used in step S1 is replaced with portland cement in this comparative example, and the other steps and methods are the same as those in example 2 and are not described again here.
In this example, the same test method as in example 1 was used, and when the conventional portland cement was used as the cementitious material, the change in the conductive cement-based material was mainly reflected in: the setting time of the conductive cement base is prolonged, compared with the case that the conductive cement base can be set for 4 hours by adopting the sulphoaluminate cement as the raw material in the embodiment 2, the setting time of the Portland cement adopted in the comparative example needs 24 hours, the early strength is slowly increased, the later strength is stably increased, the conductive cement base is not suitable for the engineering of rapid first-aid repair, and the influence on the resistivity of the conductive cement base is small; the electric resistivity of the conductive cement-based material prepared in this comparative example was 73.60 Ω · cm.
In summary, the following steps: in the embodiment 2, when the carbon fiber doping amount is increased to be 0.8% of the volume ratio of the mixture, the resistivity of the prepared conductive cement-based material can be greatly reduced, and the conductivity is improved, and the carbon fiber doping amount accounting for 0.6% -1% of the volume of the mixture is selected by comprehensively considering the cost and the dechlorination effect. The preparation method of the carbon fiber doped conductive cement-based material adopts reasonable water-to-gel ratio and glue-to-sand ratio, reasonably controls the size and content of the carbon fiber and the using amount of the additive to obtain the cement-based material with excellent conductivity, has excellent mechanical property and durability, can be used for a long time, has wide development and application prospects in the fields of electrochemical desalting, steel bar corrosion monitoring and the like, and has the specific effects of:
1. the sulphoaluminate cement is used as the cement in the conductive cement-based material, compared with the traditional Portland cement, the sulphoaluminate cement is more environment-friendly and has more excellent performance, so that the conductive cement-based material has the performance of early strength and rapid hardening, and is more suitable for repair engineering.
2. The redispersible latex powder is added into the conductive cement base, so that the bonding force between the conductive cement base and the reinforced concrete is improved, the durability and the toughness of the cement-based material are improved, and the conductive cement base is used for a longer time in a harsh environment.
3. The conductive filler used by the conductive cement base is carbon fiber with proper length, the dispersibility is good, the carbon fiber is distributed in the cement base material to form a coherent conductive network, compared with conductive materials such as graphite, carbon nano tubes and the like, the consumption of the carbon fiber is less, the conductive network is easier to form, and the resistivity of the cement base material is lower; and the addition of the carbon fiber can improve the toughness of the material and effectively reduce the shrinkage of the cement-based material.
4. The conductive cement-based material prepared by combining the modified sulphoaluminate cement and the carbon fiber has the functions of repairing and conducting, not only has excellent mechanical property and durability, but also has lower resistivity, and has wide development prospect when being applied to the fields of electrochemical dechlorination and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The carbon fiber doped conductive cement-based material is characterized by comprising the following components in parts by weight:
85-90 parts of cement, 200 parts of sand 125 and sand, 10-15 parts of mineral powder, 1-3 parts of redispersible latex powder, 40-50 parts of water, 0.5-0.8 part of water reducing agent and 0.03-0.06 part of defoaming agent;
and carbon fibers, wherein the volume of the carbon fibers accounts for 0.6-1% of the volume of the mixture.
2. The carbon fiber-doped electrically conductive cement-based material according to claim 1, wherein the carbon fibers have a length of 6-9 mm.
3. The carbon fiber doped electrically conductive cement-based material according to claim 1, wherein the cement is a sulphoaluminate cement.
4. The carbon fiber-doped conductive cement-based material as claimed in claim 1, wherein the conductive cement-based material further comprises a dispersant, the dispersant is added in an amount of 0.4-0.6% by mass of the cementing material, and the mass of the cementing material is the sum of the mass of the cement and the mass of the mineral powder;
preferably, the dispersant is methylcellulose.
5. The carbon fiber-doped conductive cement-based material of claim 1, wherein the re-dispersible latex powder is an ethylene/vinyl acetate copolymer;
preferably, the water reducing agent is a polycarboxylic acid type water reducing agent.
6. A method for the preparation of a carbon fiber doped electrically conductive cement-based material according to any one of claims 1 to 5, characterized in that it comprises the following steps:
s1 preparation of carbon fiber dispersion liquid
Dissolving the weighed carbon fibers in water, and uniformly dispersing to obtain a pre-dispersed carbon fiber liquid; adding a dispersing agent and a defoaming agent into the pre-dispersed carbon fiber liquid, and stirring and ultrasonically dispersing to obtain a carbon fiber dispersion liquid;
s2 preparation of cement-based mortar
Adding cement, mineral powder, redispersible latex powder, water and a water reducing agent into a stirrer and uniformly stirring; then adding the carbon fiber dispersion liquid obtained in the step S1 into a stirrer to be continuously stirred uniformly; adding the sand into a stirrer, and uniformly stirring to obtain a cement-based mortar mixture;
s3 forming of conductive cement-based material
Filling the cement-based mortar obtained in the step S2 into a mould, compacting and leveling, and inserting an electrode material; and (5) standing for 4-24h, demoulding and curing to obtain the conductive cement-based material.
7. The method for preparing a carbon fiber-doped conductive cement-based material according to claim 6, wherein the specific preparation process of the pre-dispersed carbon fiber liquid in the step S1 is as follows: dissolving carbon fibers in water, heating the water to 65-75 ℃, and performing ultrasonic dispersion for 5-15min to obtain the pre-dispersed carbon fiber liquid.
8. The method for preparing the carbon fiber-doped conductive cement-based material as claimed in claim 6, wherein in step S1, the dispersant is added into the pre-dispersed carbon fiber liquid, and the mixture is stirred and ultrasonically dispersed for 5-15 min;
preferably, the water for dissolving the carbon fibers in the step S1 accounts for 1/3-2/3 of the water amount in the mixture.
9. The method for preparing a carbon fiber-doped conductive cement-based material according to claim 6, wherein in step S3, the curing conditions are as follows: curing in a curing chamber with the temperature of 15-25 ℃ and the relative humidity of more than or equal to 90 percent.
10. Use of a carbon fiber doped electrically conductive cement-based material according to any one of claims 1 to 5 or of an electrically conductive cement-based material prepared by the preparation method according to any one of claims 6 to 9 for electrochemical dechlorination.
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