CN106587758B - Based on emulsion modified graphene-cement-base composite material and its preparation and application - Google Patents
Based on emulsion modified graphene-cement-base composite material and its preparation and application Download PDFInfo
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- CN106587758B CN106587758B CN201611004915.5A CN201611004915A CN106587758B CN 106587758 B CN106587758 B CN 106587758B CN 201611004915 A CN201611004915 A CN 201611004915A CN 106587758 B CN106587758 B CN 106587758B
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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
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- 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
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
- B28B11/245—Curing concrete articles
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/18—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a kind of based on emulsion modified graphene-cement-base composite material and its preparation and application, the composite material includes with mass ratio (3.5~4.5): 10:(0~1): the quality of (0~2) uniformly mixed water, cement, graphene and lotion, graphene and lotion is not 0；Graphene is first added to the water by the preparation of the composite material, stirring a period of time, and lotion is added in period, until stirring evenly, obtains mixed liquor；Cement is added in mixed liquor, segmentation can be obtained after mixing evenly, which is used for the health monitoring built as strain transducer.Compared with prior art, the present invention has excellent electric conductivity, mechanical property and pressure-sensitive coefficient, is highly suitable as the health monitoring that strain transducer is built.
Description
Technical field
The present invention relates to building health monitoring fields, and in particular to a kind of multiple based on emulsion modified graphene-cement base
Condensation material and its preparation and application.
Background technique
As the pillar material of urban modernization construction, cement has extremely wide application in the world.With
People's demand growing day by day to intelligence structure, traditional cement material be also faced with series of challenges.In recent years, building
Itself realizes health detection and monitoring, has become a main trend of construction industry development instantly, this is because many heavy
The mortality destruction for wanting component to occur during use often leads to huge loss.Traditionally realize the primary hand of health monitoring
Section is by being embedded in voltage sensitive sensor in cement material.The strain that cement material can be damaged and be generated by this method is converted
At electric signal, to realize the monitoring to building health status, the risk in use process is effectively reduced.But this method
Defect it is also obvious that due to voltage sensitive sensor insertion so that the durability and mechanical strength of cement material are all by certain
The reduction of degree.
The it is proposed of alert and resourceful cement, to realize that the health monitoring of building itself provides a more feasible and practical way
Diameter.The preparation of alertness cement is mainly realized by the way that carbon nanomaterial is added in cement matrix at present.Carbon nanomaterial
It is scattered in concrete base material, while as structure reinforced phase and function phase, forming a kind of cement-base composite material.Benefit at present
It has been widely studied with alert and resourceful cement characteristics prepared by carbon fiber and carbon nanotube.But defect is it is also obvious that essentially consist in
Its relatively high price, poor dispersibility and caused performance inconsistency.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of electric conductivity and power
Learn that performance is good, good dispersion, pressure-sensitive coefficient are high based on emulsion modified graphene-cement-base composite material and its preparation and answers
With.
The purpose of the present invention can be achieved through the following technical solutions: a kind of based on emulsion modified graphene-cement
Based composites, including uniformly mixed water, cement, graphene and lotion, the quality of the water, cement, graphene and lotion
Than for (3.5~4.5): 10:(0~1): (0~2), wherein the quality of graphene and lotion is not 0.
A kind of two-dimensional layer nano material of the graphene as unique texture possesses many excellent performances, including high electricity
Conductance, high mechanical strength, bigger serface etc..With cement-based material it is compound after, graphene can fill in cement hydration process
Work as template action, control the structure and pattern of hydrolysis product of cement, improve the intensity of petrifying water mudstone, improves cement base composite wood
The toughness and cracking resistance of material stitch ability, while can also be formed in the interior thereof conductive network, improve conductive capability.The incorporation of graphene,
The electric conductivity and pressure-sensitive of material can be improved, but excessive incorporation obviously can also have an impact its performance, therefore uses
Ratio of the invention, it is ensured that composite material has good electric conductivity and pressure-sensitive.
Graphene is used as conducting function phase in the composite, is the basic structural unit of three-dimensional conductive network.Without outer
In the case where loading lotus, for graphene film interlamellar spacing from larger, resistance is larger in matrices of composite material；When the work by plus load
Used time, composite material strain, and from reduction, mutually overlap joint, conductive net occur graphene film interlamellar spacing for conductive phase in collective
It is constantly improve locally, resistance is reduced rapidly, to show pressure-sensitive character.And the addition of lotion, so that graphene cement is multiple
The elastic deformability of condensation material enhances, and the biggish graphene sheet layer of script interlamellar spacing under pressure, can produce mutually
Overlap joint, so that the voltage-dependent characteristic of composite material be made to improve.Using graphene-cement-base composite material made of the composition proportion
It is not only able to maintain original mechanical strength, and preferable pressure-sensitive character can be shown.
The number of carbon atom and oxygen atom ratio is (4~12) in the graphene: 1.
The lotion includes one of styrene-acrylic emulsion, styrene-butadiene emulsion or acrylic acid ester emulsion.
The styrene-acrylic emulsion is preferably BASF Acronal S400 type styrene-acrylic emulsion, Acronal PS608 type phenylpropyl alcohol
One of lotion, Acronal PA619 type styrene-acrylic emulsion or GB833 type styrene-acrylic emulsion.
It is a kind of as described above based on emulsion modified graphene-cement-base composite material preparation method, first by graphene
It is added to the water, stirring a period of time, and lotion is added in period, until stirring evenly, obtains mixed liquor；It is added in mixed liquor
Cement, segmentation stirring is to get the composite material.
Since the dispersibility of graphene in water is poor, jitter time is longer, therefore first stirs graphene aqueous solution
It mixes, then adds the preferable lotion of dispersibility.After liquid dispersion sufficiently to be mixed, cement is added, is stirred in blender
It mixes.Thus obtained cement-based compound fluidity of slurry is preferable, and each component is also uniformly mixed.
The stirring of graphene and water carries out in high-speed shearing machine, and stirring rate is 10000~28000r/min, described to stir
Mixing the time is 25~40min.
The stirring of the mixed liquor and cement carries out in agitator for cement mortar, which is divided into two sections, respectively slowly
Stirring and fast stirring；
Slowly the stirring rate stirred is 55~70r/min, and the time stirred slowly is 100~150s；
The stirring rate stirred fastly is 110~140r/min, and the time stirred slowly is 100~150s.
Slowly it stirs primarily to prevent the spatter loss of starting agitation phases material, cement and mixed liquor is made to form slurry.
Above-mentioned requirements can be reached under the stirring rate and time.And stir fastly, it is to further increase being uniformly mixed for slurry
Degree prevents the appearance of agglomeration, above-mentioned requirements can be reached under the stirring rate and time.
It is a kind of as described above based on emulsion modified graphene-cement-base composite material application, the composite material is answered
For building, health monitoring is carried out as strain transducer.
Upper certain positions for being easy to produce stress deformation are being built, using this kind based on emulsion modified graphene-cement
Based composites are built or are repaired, and connect resistor detecting device, and the resistance variations by monitoring the position are able to achieve
Health monitoring.
Compared with prior art, the beneficial effects of the present invention are embodied in following several respects:
(1) composite material of the invention has good electric conductivity and mechanical property, is highly suitable as alert and resourceful cement and carries out
The health monitoring of building itself；
(2) pressure-sensitive coefficient of the invention is high, so that the data of health monitoring are accurate.
(3) composite material preparation process of the invention is simple, and at low cost, workability is preferable.
Detailed description of the invention
Fig. 1 is in embodiment 1 for detecting the apparatus structure schematic diagram of composite property；
Fig. 2 is resistance change rate-strain curve in embodiment 1；
Fig. 3 is resistance change rate-strain curve in embodiment 2；
Fig. 4 is resistance change rate-strain curve in embodiment 3；
Fig. 5 is resistance change rate-strain curve in comparative example；
Wherein, 1 is composite sample, and 2 be copper electrode, and 3 be hard plastic sheet, and 4 be multimeter.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
Weigh a certain amount of cement, deionized water, styrene-acrylic emulsion (in terms of solid content) and graphene.Its mass ratio is
10:4:1:0.2.The graphene C/O (carbon oxygen atom number ratio) of selection is 4.5:1.Graphene is add to deionized water, with height
Fast cutter high-speed stirred 30min is poured into agitator for cement mortar until stirring evenly.Agitator for cement mortar at the uniform velocity
In the case where stirring, it is slowly added into cement, 120s is stirred slowly, stirs 120s fastly.
By fresh cement paste be molded over cake pattern tool in, be put into standard cement fog room (20 ± 1 DEG C, relative humidity
About 90% or so) maintenance 28 days, obtain composite sample 1.
Composite sample 1 is taken out, pressure-sensitive test is carried out: first 1 two sides of composite sample being polished smooth, then with leading
Electric glue pastes copper electrode 2 on the two sides of composite sample 1.Drying under sample ventilation condition for 24 hours, is obtained into test sample.?
Insulating rigid plastic sheet 3 on test sample upper and lower surface pad, it is ensured that big deformation will not be generated in pressure process, with conducting wire by copper
The tip of electrode 2 is connect with the electrode of multimeter 4, after connection schematic diagram is as shown in Figure 1, wait resistance stabilizations, uses pressure testing machine
Apply pressure F on 3 surface of hard plastic sheet, starts applied voltage test, loading speed 0.5mm/min, pressure dwell record strain
With corresponding resistance.
It tests obtained data to be handled, obtains resistance change rate-strain curve shown in Fig. 2.Curve show with
The increase of load (strain therewith increase), the resistance change rate of sample also increases with it, and changes more obvious, and has
There is preferable linear relationship, this shows that the sample shows preferable pressure sensitive quality.By calculating, the emulsion modified graphite is obtained
The pressure-sensitive coefficient GF of alkene-cement composite material is 3.407, has good pressure sensitivity.
Embodiment 2
Weigh a certain amount of cement, deionized water, styrene-acrylic emulsion (in terms of solid content) and graphene.Its mass ratio is
10:4:1:0.133.The graphene C/O (carbon oxygen atom number ratio) of selection is 8.7:1.Graphene is add to deionized water, is used
High-speed shearing machine high-speed stirred 30min is poured into agitator for cement mortar until stirring evenly.It is even in agitator for cement mortar
In the case where speed stirring, it is slowly added into cement, 120s is stirred slowly, stirs 120s fastly.
By fresh cement paste be molded over cake pattern tool in, be put into standard cement fog room (20 ± 1 DEG C, relative humidity
About 90% or so) maintenance 28 days.
Sample is taken out, pressure-sensitive test is carried out.First sample two sides is polished smooth, then with conducting resinl the two of circular specimen
Paste copper sheet in face.For 24 hours by drying under sample ventilation condition.When being pressurizeed with pressure testing machine, insulate on sample upper and lower surface pad
Hard plastic sheet, it is ensured that big deformation will not be generated in pressure process.The electrode of the tip of copper sheet and multimeter is connected with conducting wire
It connects, starts applied voltage test, loading speed 0.5mm/min, the strain of pressure dwell record and corresponding resistance after waiting resistance stabilizations.
It tests obtained data to be handled, obtains resistance change rate-strain curve shown in Fig. 3.Curve show with
The increase of load (strain therewith increase), the resistance change rate of sample also increases with it, and more obvious, and have compared with
Good linear relationship, this shows that the sample shows good pressure sensitive quality.By calculating, the emulsion modified graphene-is obtained
The pressure-sensitive coefficient GF of cement composite material is 3.845, has preferable pressure sensitivity.
Embodiment 3
Weigh a certain amount of cement, deionized water, styrene-acrylic emulsion (in terms of solid content) and graphene.Its mass ratio is
10:4:1:0.067.The graphene C/O (carbon oxygen atom number ratio) of selection is 12:1.Graphene is add to deionized water, is used
High-speed shearing machine high-speed stirred 30min is poured into agitator for cement mortar until stirring evenly.It is even in agitator for cement mortar
In the case where speed stirring, it is slowly added into cement, 120s is stirred slowly, stirs 120s fastly.
By fresh cement paste be molded over cake pattern tool in, be put into standard cement fog room (20 ± 1 DEG C, relative humidity
About 90% or so) maintenance 28 days.
Sample is taken out, pressure-sensitive test is carried out.First sample two sides is polished smooth, then with conducting resinl the two of circular specimen
Paste copper sheet in face.For 24 hours by drying under sample ventilation condition.When being pressurizeed with pressure testing machine, insulate on sample upper and lower surface pad
Hard plastic sheet, it is ensured that big deformation will not be generated in pressure process.The electrode of the tip of copper sheet and multimeter is connected with conducting wire
It connects, starts applied voltage test, loading speed 0.5mm/min, the strain of pressure dwell record and corresponding resistance after waiting resistance stabilizations.
It tests obtained data to be handled, obtains resistance change rate-strain curve shown in Fig. 4.Curve show with
The increase of load (strain therewith increase), the resistance change rate of sample also increases with it, and changes clearly, and have
There is preferable linear relationship, this shows that the sample shows good pressure sensitive quality.By calculating, the emulsion modified graphite is obtained
The pressure-sensitive coefficient GF of alkene-cement composite material is 7.783, has good pressure sensitivity.
Comparative example
Weigh a certain amount of cement, deionized water, styrene-acrylic emulsion (in terms of solid content) and graphene.Its mass ratio is
10:4:0:0.067.The graphene C/O (carbon oxygen atom number ratio) of selection is 4.5:1.Graphene is add to deionized water, is used
High-speed shearing machine high-speed stirred 30min is poured into agitator for cement mortar until stirring evenly.It is even in agitator for cement mortar
In the case where speed stirring, it is slowly added into cement, 120s is stirred slowly, stirs 120s fastly.
By fresh cement paste be molded over cake pattern tool in, be put into standard cement fog room (20 ± 1 DEG C, relative humidity
About 90% or so) maintenance 28 days.
Sample is taken out, pressure-sensitive test is carried out.First sample two sides is polished smooth, then with conducting resinl the two of circular specimen
Paste copper sheet in face.For 24 hours by drying under sample ventilation condition.When being pressurizeed with pressure testing machine, insulate on sample upper and lower surface pad
Hard plastic sheet, it is ensured that big deformation will not be generated in pressure process.The electrode of the tip of copper sheet and multimeter is connected with conducting wire
It connects, starts applied voltage test, loading speed 0.5mm/min, the strain of pressure dwell record and corresponding resistance after waiting resistance stabilizations.
It tests obtained data to be handled, obtains resistance change rate-strain curve shown in fig. 5.Curve show with
The increase of load (strain therewith increase), the resistance change rate of sample also increases with it, and has preferable linear relationship,
This shows that the sample shows pressure sensitive quality.By calculating, obtaining the pressure-sensitive coefficient GF of the graphene-cement composite material is
0.495。
After comparing from comparative example and Examples 1 to 3 it is found that adding styrene-acrylic emulsion in the composite, it can greatly improve
The pressure-sensitive coefficient of composite material.
Embodiment 4
It is a kind of based on emulsion modified graphene-cement-base composite material preparation, comprising the following steps: weigh mass ratio
For the water of 4.5:10:1:2, cement, graphene and styrene-butadiene emulsion, first graphene is added to the water, is carried out in high-speed shearing machine
Stirring, stirring rate 28000r/min, mixing time 25min, and interior addition styrene-butadiene emulsion during this period, are mixed
Liquid；Cement is added in mixed liquor, segmentation stirring is carried out in agitator for cement mortar, which is divided into two sections, respectively slowly
Stirring and fast stirring；Wherein, the stirring rate stirred slowly is 70r/min, and the time stirred slowly is 100s；The stirring speed stirred fastly
Rate is 140r/min, and the time stirred slowly is 100s to get the composite material.
The number of carbon atom and oxygen atom ratio is 12:1 in graphene used in the present embodiment.
Composite material obtained above is tested for the property according to embodiment the method, obtains the graphene-cement
The pressure-sensitive coefficient GF of composite material is 6.578.
Embodiment 5
It is a kind of based on emulsion modified graphene-cement-base composite material preparation, comprising the following steps: weigh mass ratio
For the water of 3.5:10:0.1:0.067, cement, graphene and acrylic acid ester emulsion, first graphene is added to the water, is being cut at a high speed
It cuts in machine and is stirred, stirring rate 10000r/min, mixing time 40min, and interior addition acrylate during this period
Lotion obtains mixed liquor；Cement is added in mixed liquor, segmentation stirring is carried out in agitator for cement mortar, which is divided into
Two sections, respectively slow stirring is stirred with fast；Wherein, the stirring rate stirred slowly is 55r/min, and the time stirred slowly is 150s；
The stirring rate stirred fastly is 110r/min, and the time stirred slowly is 150s to get the composite material.
The number of carbon atom and oxygen atom ratio is 4:1 in graphene used in the present embodiment.
Composite material obtained above is tested for the property according to embodiment the method, obtains the graphene-cement
The pressure-sensitive coefficient GF of composite material is 3.012.
Claims (7)
1. a kind of based on emulsion modified graphene-cement-base composite material, which is characterized in that the composite material includes that mixing is equal
Even water, cement, graphene and lotion, the water, cement, graphene and lotion mass ratio be (3.5~4.5): 10:(0~
1): (0~2), wherein the quality of graphene and lotion is not 0；The composite material is prepared by following steps:
First graphene is added to the water, stirring a period of time, and lotion is added in period, until stirring evenly, obtains mixed liquor；
Cement is added in mixed liquor, segmentation stirring is to get the composite material.
2. according to claim 1 a kind of based on emulsion modified graphene-cement-base composite material, which is characterized in that
The number of carbon atom and oxygen atom ratio is (4~12) in the graphene: 1.
3. according to claim 1 a kind of based on emulsion modified graphene-cement-base composite material, which is characterized in that
The lotion includes one of styrene-acrylic emulsion, styrene-butadiene emulsion or acrylic acid ester emulsion.
4. it is a kind of as described in claims 1 to 3 is any based on emulsion modified graphene-cement-base composite material preparation side
Method, which is characterized in that first graphene is added to the water, stirring a period of time, and lotion is added in period, until stir evenly,
Obtain mixed liquor；Cement is added in mixed liquor, segmentation stirring is to get the composite material.
5. it is according to claim 4 a kind of based on emulsion modified graphene-cement-base composite material preparation method,
It is characterized in that, the stirring of graphene and water carries out in high-speed shearing machine, and stirring rate is 10000~28000r/min, described
Mixing time is 25~40min.
6. it is according to claim 4 a kind of based on emulsion modified graphene-cement-base composite material preparation method,
It is characterized in that, the stirring of the mixed liquor and cement carries out in agitator for cement mortar, which is divided into two sections, respectively slowly
Stirring and fast stirring；
Slowly the stirring rate stirred is 55~70r/min, and the time stirred slowly is 100~150s；
The stirring rate stirred fastly is 110~140r/min, and the time stirred slowly is 100~150s.
7. it is a kind of as described in claims 1 to 3 is any based on emulsion modified graphene-cement-base composite material application,
It is characterized in that, the composite material is applied to building, carries out health monitoring as strain transducer.
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| CN107324682A (en) * | 2017-06-13 | 2017-11-07 | 安徽智联管理咨询有限公司 | Crack resistence concrete additive and preparation method thereof |
| CN107814525A (en) * | 2017-11-27 | 2018-03-20 | 广西福美新材料有限公司 | A kind of antistatic flexible floor and preparation method thereof |
| CN108358541B (en) * | 2018-01-31 | 2020-07-31 | 广州大学 | Polypyrrole-coated graphene oxide cement-based composite material and preparation method thereof |
| CN114316645B (en) * | 2021-12-07 | 2022-12-27 | 青岛理工大学 | Cement-based conductive material for monitoring existing building strain and cement-based sensor |
| CN114350188B (en) * | 2021-12-14 | 2023-01-03 | 青岛理工大学 | Energy storage protection type cement-based micro-variation monitoring coating for existing building strain monitoring and cement-based sensor |
| CN114507045B (en) * | 2022-02-22 | 2022-09-27 | 深圳市深建混凝土有限公司 | High-strength, high-toughness, high-impact-resistance and high-wear-resistance cement-based composite material |
| CN117401944A (en) * | 2023-11-06 | 2024-01-16 | 广州航海学院 | Cement-based intelligent material and preparation method thereof |
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| CN103193426A (en) * | 2013-04-10 | 2013-07-10 | 陕西科技大学 | Preparation method of graphene oxide modified polymer cement waterproof coating |
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| CN102515659A (en) * | 2011-11-29 | 2012-06-27 | 南京工业大学 | Photocatalytic cement-based decorative composite material and preparation method thereof |
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