CN106587758A - Emulsion modification based graphene-cement based composite material and preparation and application thereof - Google Patents
Emulsion modification based graphene-cement based composite material and preparation and application thereof Download PDFInfo
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- CN106587758A CN106587758A CN201611004915.5A CN201611004915A CN106587758A CN 106587758 A CN106587758 A CN 106587758A CN 201611004915 A CN201611004915 A CN 201611004915A CN 106587758 A CN106587758 A CN 106587758A
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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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Abstract
The invention relates to an emulsion modification based graphene-cement based composite material and preparation and application thereof. The composite material contains water, cement, graphene and an emulsion which are mixed uniformly according to the mass ratio of (3.5 to 4.5): 10: (0 to 1): (0 to 2), wherein both the mass of the graphene and the mass of the emulsion are not 0. The preparation of the composite material comprises the steps: firstly, adding the graphene into the water, and carrying out stirring for a period of time while adding the emulsion into the water until uniform stirring is achieved, so as to obtain a mixed solution; and adding the cement into the mixed solution, and carrying out staged uniform stirring, thereby obtaining the composite material. The composite material is used for carrying out health monitoring on buildings as a strain transducer. Compared with the prior art, the composite material has the advantages of excellent electrical conductivity, mechanical properties and pressure-sensitive coefficient, thereby being very suitable for carrying out health monitoring on the buildings as the strain transducer.
Description
Technical field
The present invention relates to build health monitoring field, and in particular to a kind of multiple based on emulsion modified Graphene-cement based
Condensation material and its preparation and application.
Background technology
Used as the pillar material that urban modernization is built, cement has extremely wide application in the world.With
The demand that people grow with each passing day to structure of intelligence, traditional cement material is also faced with series of challenges.In recent years, building
Health detection and monitoring itself are realized, a major trend of construction industry development instantly is had become, this is because many heavy
The mortality destruction that part occurs during use is wanted to often lead to huge loss.The primary hand of health monitoring is realized traditionally
Section is by voltage sensitive sensor is embedded in cement material.The strain conversion that cement material can be damaged and be produced by this method
Into the signal of telecommunication, so as to realize the monitoring to building health status, the risk during use is effectively reduced.But this method
Defect it is also obvious that embedded due to voltage sensitive sensor so that the durability and mechanical strength of cement material is all subject to necessarily
The reduction of degree.
The proposition of alert and resourceful cement, to realize that the health monitoring of building itself provides a more feasible and practical way
Footpath.What the preparation of alertness cement at present was realized mainly by carbon nanomaterial is added in cement matrix.Carbon nanomaterial
It is scattered in concrete base material, while strengthening phase and function phase as structure, forms a kind of cement-base composite material.It is sharp at present
The alert and resourceful cement characteristics prepared with carbon fiber and CNT have been widely studied.But defect is it is also obvious that essentially consist in
Performance inconsistency caused by its of a relatively high price, poor dispersibility and institute.
The content of the invention
The purpose of the present invention is exactly to provide a kind of electric conductivity and power to overcome the defect of above-mentioned prior art presence
Learn that performance is good, good dispersion, pressure-sensitive coefficient are high based on emulsion modified Graphene-cement-base composite material and its prepare with should
With.
The purpose of the present invention can be achieved through the following technical solutions：It is a kind of based on emulsion modified Graphene-cement
Based composites, including the water of mix homogeneously, cement, Graphene and emulsion, the quality of the water, cement, Graphene and emulsion
Than for (3.5～4.5)：10：(0～1)：(0～2), wherein, the quality of Graphene and emulsion 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 properties, bigger serface etc..After compound with cement-based material, Graphene can be filled 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, improve cement based composite wood
The toughness of material and cracking resistance seam ability, while also conductive network can be internally formed at which, improve conductive capability.The incorporation of Graphene,
The electric conductivity and pressure-sensitive of material, but excessive incorporation can be improved obviously for its performance can also produce impact, therefore adopted
The ratio of the present invention, it is ensured that composite has good electric conductivity and pressure-sensitive.
Graphene, in the composite as conducting function phase, is the basic structural unit of three-dimensional conductive network.Without outer
In the case of loading lotus, in matrices of composite material, from larger, resistance is larger for graphene film interlamellar spacing；When being made by plus load
There is strain in used time, composite, in collective, from reduction, conductive phase mutually to overlap graphene film interlamellar spacing occurs, conductive net
In local constantly improve, resistance reduces rapidly, so as to show pressure-sensitive character.And the addition of emulsion so that Graphene cement is multiple
The elastic deformability of condensation material strengthens, and the larger graphene sheet layer of script interlamellar spacing under pressure, can be produced mutually
Overlap joint, so that the voltage-dependent characteristic of composite is improved.Using Graphene-cement-base composite material made by the composition proportion
Original mechanical strength can not only be kept, and preferable pressure-sensitive character can be shown.
In described Graphene, the number ratio of carbon atom and oxygen atom is (4～12)：1.
Described emulsion includes the one kind in styrene-acrylic emulsion, styrene-butadiene emulsion or acrylic acid ester emulsion.
Described styrene-acrylic emulsion is preferably BASF Acronal S400 type styrene-acrylic emulsions, Acronal PS608 type phenylpropyl alcohols
One kind in emulsion, Acronal PA619 types styrene-acrylic emulsions or GB833 type styrene-acrylic emulsions.
A kind of preparation method as mentioned above based on emulsion modified Graphene-cement-base composite material, first by Graphene
Be added to the water, stirring a period of time, and emulsion added in period, until stirring, obtain mixed liquor；Add in mixed liquor
Cement, segmentation stirring, obtains final product the composite.
As dispersibility of the Graphene in water is poor, jitter time is longer, therefore first graphene aqueous solution is stirred
Mix, then add the preferable emulsion of dispersibility.After liquid dispersion fully to be mixed, cement is added, is stirred in blender
Mix.Thus obtained cement-based compound fluidity of slurry preferably, each component also mix homogeneously.
Graphene is carried out in high-speed shearing machine with the stirring of water, and stir speed (S.S.) is 10000～28000r/min, described to stir
The time is mixed for 25～40min.
The mixed liquor is carried out in agitator for cement mortar with the stirring of cement, and the stirring is divided into two sections, respectively slowly
Stirring and fast stirring；
The stir speed (S.S.) of the slow stirring is 55～70r/min, and the time of slow stirring is 100～150s；
The stir speed (S.S.) of the fast stirring is 110～140r/min, and the time of slow stirring is 100～150s.
Slowly stir primarily to prevent the spatter loss of initial agitation phases material, make cement and mixed liquor form slip.
Above-mentioned requirements can be reached under the stir speed (S.S.) and time.And stir soon, it is for the mix homogeneously for further improving slip
Degree, prevents the appearance lumpd, above-mentioned requirements can be reached under the stir speed (S.S.) and time.
A kind of application as mentioned above based on emulsion modified Graphene-cement-base composite material, the composite should
For building, health monitoring is carried out as strain transducer.
In architectural some easy positions for producing stress deformation, using this kind based on emulsion modified Graphene-cement
Based composites are built or are repaired, and connect resistor detecting device, can be realized by the resistance variations for monitoring the position
Health monitoring.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects：
(1) composite of the invention has good electric conductivity and mechanical property, and being highly suitable as alert and resourceful cement is carried 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 preparation process of the invention is simple, and low cost, workability are preferable.
Description of the drawings
Fig. 1 is for detecting the apparatus structure schematic diagram of composite property in embodiment 1；
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 is copper electrode, and 3 is hard plastic sheet, and 4 is circuit tester.
Specific embodiment
Below embodiments of the invention are elaborated, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following enforcements
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.From Graphene C/O (carbon oxygen atom number ratio) be 4.5：1.Graphene is added in deionized water, with height
Fast cutter high-speed stirred 30min, until stirring, pours in agitator for cement mortar.In agitator for cement mortar at the uniform velocity
In the case of stirring, cement is slowly added into, stirs 120s slowly, stir 120s soon.
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) conserve 28 days, obtain composite sample 1.
Composite sample 1 is taken out, pressure-sensitive test is carried out：First will be the polishing of 1 two sides of composite sample smooth, then with leading
Electric glue pastes copper electrode 2 on the two sides of composite sample 1.24h will be dried under sample ventilation condition, obtain test sample.
Insulating rigid plastic sheet 3 on test sample upper and lower surface pad, it is ensured that big deformation will not be produced in pressure process, with wire by copper
The tip of electrode 2 is connected with the electrode of circuit tester 4, after connection diagram is as shown in figure 1, wait resistance stabilization, uses pressure testing machine
Apply pressure F on 3 surface of hard plastic sheet, start applied voltage test, loading speed is 0.5mm/min, pressure dwell record strain
With corresponding resistance.
The data that test is obtained are processed, and obtain the resistance change rate-strain curve shown in Fig. 2.Curve shows, with
The increase (strain increases therewith) of load, the resistance change rate of sample also increases therewith, and changes more substantially, 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, with 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.From Graphene C/O (carbon oxygen atom number ratio) be 8.7：1.Graphene is added in deionized water, is used
High-speed shearing machine high-speed stirred 30min, until stirring, pours in agitator for cement mortar.It is even in agitator for cement mortar
In the case of speed stirring, cement is slowly added into, 120s is stirred slowly, 120s is stirred soon.
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) conserve 28 days.
Sample is taken out, pressure-sensitive test is carried out.First will be the polishing of sample two sides smooth, then with conducting resinl the two of circular specimen
Paste copper sheet in face.24h will be dried 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 produced in pressure process.Electrode with wire by the tip of copper sheet with circuit tester connects
Connect, after waiting resistance stabilization, start applied voltage test, loading speed is 0.5mm/min, the strain of pressure dwell record and corresponding resistance.
The data that test is obtained are processed, and obtain the resistance change rate-strain curve shown in Fig. 3.Curve shows, with
The increase (strain therewith increase) of load, the resistance change rate of sample also increases therewith, and more substantially, and with compared with
Good linear relationship, this shows that the sample shows good pressure sensitive quality.By calculate, obtain the emulsion modified Graphene-
The pressure-sensitive coefficient GF of cement composite material is 3.845, with 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.From Graphene C/O (carbon oxygen atom number ratio) be 12：1.Graphene is added in deionized water, is used
High-speed shearing machine high-speed stirred 30min, until stirring, pours in agitator for cement mortar.It is even in agitator for cement mortar
In the case of speed stirring, cement is slowly added into, 120s is stirred slowly, 120s is stirred soon.
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) conserve 28 days.
Sample is taken out, pressure-sensitive test is carried out.First will be the polishing of sample two sides smooth, then with conducting resinl the two of circular specimen
Paste copper sheet in face.24h will be dried 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 produced in pressure process.Electrode with wire by the tip of copper sheet with circuit tester connects
Connect, after waiting resistance stabilization, start applied voltage test, loading speed is 0.5mm/min, the strain of pressure dwell record and corresponding resistance.
The data that test is obtained are processed, and obtain the resistance change rate-strain curve shown in Fig. 4.Curve shows, with
The increase (strain increases therewith) of load, the resistance change rate of sample also increases therewith, and changes clearly, and has
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, with 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.From Graphene C/O (carbon oxygen atom number ratio) be 4.5：1.Graphene is added in deionized water, is used
High-speed shearing machine high-speed stirred 30min, until stirring, pours in agitator for cement mortar.It is even in agitator for cement mortar
In the case of speed stirring, cement is slowly added into, 120s is stirred slowly, 120s is stirred soon.
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) conserve 28 days.
Sample is taken out, pressure-sensitive test is carried out.First will be the polishing of sample two sides smooth, then with conducting resinl the two of circular specimen
Paste copper sheet in face.24h will be dried 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 produced in pressure process.Electrode with wire by the tip of copper sheet with circuit tester connects
Connect, after waiting resistance stabilization, start applied voltage test, loading speed is 0.5mm/min, the strain of pressure dwell record and corresponding resistance.
The data that test is obtained are processed, and obtain the resistance change rate-strain curve shown in Fig. 5.Curve shows, with
The increase (strain increases therewith) of load, the resistance change rate of sample also increases therewith, and has preferable linear relationship,
This shows that the sample shows pressure sensitive quality.By calculating, the pressure-sensitive coefficient GF for obtaining the Graphene-cement composite material is
0.495。
Knowable to comparative example and embodiment 1～3 compare, after adding styrene-acrylic emulsion in the composite, can greatly improve
The pressure-sensitive coefficient of composite.
Embodiment 4
A kind of preparation based on emulsion modified Graphene-cement-base composite material, comprises the following steps：Weigh mass ratio
For 4.5：10：1：Graphene is first added to the water, is carried out in high-speed shearing machine by 2 water, cement, Graphene and styrene-butadiene emulsion
Stirring, stir speed (S.S.) is 28000r/min, and mixing time is 25min, and interior addition styrene-butadiene emulsion during this period, is mixed
Liquid；Cement is added in mixed liquor, segmentation stirring is carried out in agitator for cement mortar, the stirring is divided into two sections, respectively slowly
Stirring and fast stirring；Wherein, the stir speed (S.S.) of slow stirring is 70r/min, and the time of slow stirring is 100s；The stirring speed of fast stirring
Rate is 140r/min, and the time of slow stirring is 100s, obtains final product the composite.
In the present embodiment, in Graphene used, the number ratio of carbon atom and oxygen atom is 12：1.
Composite obtained above is carried out into performance test according to embodiment methods described, the Graphene-cement is obtained
The pressure-sensitive coefficient GF of composite is 6.578.
Embodiment 5
A kind of preparation based on emulsion modified Graphene-cement-base composite material, comprises the following steps：Weigh mass ratio
For 3.5：10：0.1：Graphene is first added to the water by 0.067 water, cement, Graphene and acrylic acid ester emulsion, is being cut in high speed
It is stirred in cutting machine, stir speed (S.S.) is 10000r/min, and mixing time is 40min, and interior addition acrylate during this period
Emulsion, obtains mixed liquor；Cement is added in mixed liquor, segmentation stirring is carried out in agitator for cement mortar, the stirring is divided into
Two sections, respectively slow stirring is stirred with fast；Wherein, the stir speed (S.S.) of slow stirring is 55r/min, and the time of slow stirring is 150s；
The stir speed (S.S.) of fast stirring is 110r/min, and the time of slow stirring is 150s, obtains final product the composite.
In the present embodiment, in Graphene used, the number ratio of carbon atom and oxygen atom is 4：1.
Composite obtained above is carried out into performance test according to embodiment methods described, the Graphene-cement is obtained
The pressure-sensitive coefficient GF of composite is 3.012.
Claims (7)
1. it is a kind of based on emulsion modified Graphene-cement-base composite material, it is characterised in that the composite includes that mixing is equal
Even water, cement, Graphene and emulsion, the mass ratio of the water, cement, Graphene and emulsion is (3.5～4.5)：10：(0～
1)：(0～2), wherein, the quality of Graphene and emulsion is not 0.
2. according to claim 1 a kind of based on emulsion modified Graphene-cement-base composite material, it is characterised in that
In described Graphene, the number ratio of carbon atom and oxygen atom is (4～12)：1.
3. according to claim 1 a kind of based on emulsion modified Graphene-cement-base composite material, it is characterised in that
Described emulsion includes the one kind in styrene-acrylic emulsion, styrene-butadiene emulsion or acrylic acid ester emulsion.
4. a kind of preparation side as described in claims 1 to 3 is arbitrary based on emulsion modified Graphene-cement-base composite material
Method, it is characterised in that first Graphene is added to the water, stirring a period of time, and emulsion is added in period, until stir,
Obtain mixed liquor；In mixed liquor, add cement, segmentation stirring to obtain final product the composite.
5. a kind of preparation method based on emulsion modified Graphene-cement-base composite material according to claim 4, its
It is characterised by, Graphene is carried out in high-speed shearing machine with the stirring of water, stir speed (S.S.) is 10000～28000r/min, described
Mixing time is 25～40min.
6. a kind of preparation method based on emulsion modified Graphene-cement-base composite material according to claim 4, its
It is characterised by, the mixed liquor is carried out in agitator for cement mortar with the stirring of cement, and the stirring is divided into two sections, respectively slowly
Stirring and fast stirring；
The stir speed (S.S.) of the slow stirring is 55～70r/min, and the time of slow stirring is 100～150s；
The stir speed (S.S.) of the fast stirring is 110～140r/min, and the time of slow stirring is 100～150s.
7. a kind of application as described in claims 1 to 3 is arbitrary based on emulsion modified Graphene-cement-base composite material, its
It is characterised by, the composite is applied to building, carries out health monitoring as strain transducer.
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| CN114507045A (en) * | 2022-02-22 | 2022-05-17 | 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 |
| 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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