CN105060790B - Electrostatic self-assembly carbon nano tube/nano-carbon black composite mortar as well as preparation method and application thereof - Google Patents
Electrostatic self-assembly carbon nano tube/nano-carbon black composite mortar as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses electrostatic self-assembly carbon nano tube/nano-carbon black composite mortar. Raw materials of the mortar comprise cement, silica fume, electrostatic self-assembly carbon nano tubes/nano-carbon black, a water reducing agent, sand and water. The minimum static resistivity of the mortar reaches 0.45 omega*m, the range of an absolute value of the resistivity change rate is 3.3%-22.1%, the change range of stress sensitivity is 0.40%-2.69%/MPa, and the change range of the strain sensitivity is 105-704. Compared with the prior art, the electrostatic self-assembly carbon nano tube/nano-carbon black composite mortar and the preparation method thereof solve the problem about dispersion of nanofiller in the mortar very well, and the carbon nano tubes and the nano-carbon black have the collaborative conductive effect, so that the mortar can acquire very low static resistivity and has excellent pressure-sensitivity by the aid of a small mixing amount of electrostatic self-assembly carbon nano tubes/nano-carbon black.
Description
Technical field
The present invention relates to building material technical field, and in particular to cement mortar composite, more particularly to electrostatic are from group
Dress carbon nanotube/nano carbon black composite mortar and preparation method thereof.
Background technology
Cement-based material is the construction material being most widely used, large-scale with cement-based material as structural material in recent years
Building is being on the increase.However, cement-based material has the defect that pull resistance is poor, toughness is low, to the application of cement-based material
Bring very big potential safety hazard.The destruction of the building that cement-based material failure is caused not only results in huge economic loss,
And great casualties may be caused.Nano-carbon material, with good corrosion resistance, mechanical property and electrical property
Energy.Wherein, CNT not only can to a certain extent improve the mechanical property of cement-based material, and can assign cement
The preferable electric conductivity of sill and pressure-sensitive.However, the CNT of small volume can not be effectively reduced the electricity of cement-based material
Resistance rate and its good pressure-sensitive of imparting, and the CNT of high additive is difficult to disperse in cement-based material.And carbon is received
The price of mitron is high, which has limited the application of CNT cement-based material.The conventional nanometer carbon filler of another kind is Nano carbon
It is black.Nano carbon black cement-based material reaches percolation threshold and the volume of the nano carbon black needed for possessing good pressure-sensitive is very high,
And the nano carbon black of high additive can be greatly reduced the mechanical property and durability of nano carbon black cement-based material.
The content of the invention
Dispersion, large dosage nano-sized carbon are difficult in cement mortar present invention aim to address CNT and nanometer carbon black
The black problem for reducing material property, there is provided it is a kind of be easily dispersed, volume is low, electric conductivity and the good electrostatic self-assembled carbon of pressure-sensitive
Nanotube/nano carbon black composite mortar.Technical scheme is as follows：
Electrostatic self-assembled carbon nanotube/nano carbon black composite mortar, the raw material of the mortar include cement, silicon ash, quiet
Electric self assembly carbon nanotube/nano carbon black, water reducer, Sha Heshui.
As preferred technical scheme, raw material include following weight than：Cement 80-90 parts；Silicon ash 10-20 parts；It is quiet
1-10 parts of electric self assembly carbon nanotube/nano carbon black；Water reducer 0.1-3 parts；Sand 100-200 parts；Water 40-80 parts.
Water reducer of the present invention is preferably polycarboxylate water-reducer.
Cement of the present invention is preferably Portland cement.
Sand of the present invention is river sand or normal sand (versatile material of cement field).
Used as preferred technical scheme, the static resistance rate minimum of the mortar is followed up to 0.45 Ω m in elastic range
Under ring compression/effects of strain, the excursion of maximum resistivity rate of change absolute value is 3.3%-22.1%, stress sensitivity
Excursion for 0.40-2.69%/MPa, strain sensitivity excursion be 105-704.
The electrostatic self-assembled carbon nanotube/nano carbon black that the present invention is used, with good electric conductivity and stability, its shape
Looks be grape string structure, wherein CNT be " stalk ", nano carbon black be " grape berry ", specifically use document 1 (Lu Hao, Dong Li,
Xu Lei, waits electrostatic assemblies method to prepare CB/CNTs conducing composite material [J] scientific and technical innovation Leaders .2014 (11):74-76.) institute
State method preparation.This " grape cluster " structure (such as Fig. 1) is still can see in mortar, this explanation is preparing mortar specimen mistake
Stirred in journey, vibrate " grape cluster " structure that will not destroy raw material electrostatic self-assembled carbon nanotube/nano carbon black.This " Portugal
Grape string " structure is conducive to electrostatic self-assembled carbon nanotube/nano carbon black to be disperseed in mortar (such as Fig. 2).Work as composite mortar
During in no-load state, by field emission effect and tunnel-effect between electrostatic self-assembled carbon nanotube/nano carbon black
The collaboration electric action of conduction, its good dispersiveness and electric conductivity and CNT and nano carbon black so that small volume
The static resistance rate of electrostatic self-assembled carbon nanotube/nano carbon black composite mortar is with regard to very little.When composite mortar is in pressured state
When, the average distance between CNT and CNT, the average distance between nano carbon black and nano carbon black, CNT
Average distance between nano carbon black can all reduce, and this can make tunnel-effect odds become big.Macro manifestations are compound
The specific insulation of mortar diminishes.When unloaded, then conversely, the specific insulation of composite mortar becomes big.Due to there is multiple not
Change with the distance between conductive material, the change in resistance rate of composite mortar becomes apparent from, and sensitivity is higher.
The present invention also provides the preparation method of the electrostatic self-assembled carbon nanotube/nano carbon black composite mortar, pressure-sensitive
Stable, reproducible, sensitivity is high, and preparation process is simple, energy consumption are small, and technical scheme is comprised the following steps：
(1) take the weight than raw material；
(2) the carbon nanotube/nano carbon black of electrostatic self-assembled, silicon ash are sequentially added in cement mortar mixer, water, is subtracted
Aqua, cement and sand, stir, and obtain mixture；
(3) described mixture is poured into mould, then mould is placed on shake table, be vibrated to the mix in mould
The surface grout of thing；
(4) according to the size of mixture in mould, insert for connecting the electrode of external circuit, then somewhat vibrate, it is ensured that
Electrode and mixture contact are good；
(5) mould is put into glue sand curing box, in 20 ± 1 DEG C of temperature, humidity>Under conditions of 95%, conserve 24 hours
The demoulding afterwards, obtains mortar specimen.
Electrode of the present invention is conductive mesh electrode, preferably stainless steel cloth.
The present invention also provides the electrostatic self-assembled carbon nanotube/nano carbon black composite mortar in exothermic material, electromagnetism material
Applied in material or concrete structure health monitoring material.
Compared with prior art, the present invention is provided electrostatic self-assembled carbon nanotube/nano carbon black composite mortar and its system
Preparation Method, preferably solves scattering problem of the nano-sized filler in mortar, and exist between CNT and nano carbon black
Collaboration conductive effect, this causes that the electrostatic self-assembled carbon nanotube/nano carbon black of small volume can just make mortar acquisition smaller quiet
State resistivity and good pressure-sensitive, specifically include following beneficial effect：
1st, using the electrostatic self-assembled carbon nanotube/nano carbon black of smaller volume, the static resistance rate of mortar is significantly
Reduce；
2nd, using the electrostatic self-assembled carbon nanotube/nano carbon black of small volume, the mortar with superior pressure-sensitive is obtained,
The sensitivity of this mortar is high, the repeatability and good stability of pressure-sensitive；
3rd, with single carbon-doped nanometer tube or compared with singly mixing nano carbon black, electrostatic self-assembled carbon nanotube/nano carbon black can be very
Good disperses in mortar matrix, and scattering problem of the nano material in mortar is solved to a certain extent；
4th, compared with nano carbon black, the volume of electrostatic self-assembled carbon nanotube/nano carbon black is small, in the bar of the identical ratio of mud
Do not have infringement, or even the rupture strength that composite mortar can be improved under part to mechanical property；
5th, the price of electrostatic self-assembled carbon nanotube/nano carbon black is the half of CNT, with good economy；
6th, preparation method is simple, it is not necessary to ultrasound, energy saving.
From performance, electrostatic self-assembled carbon nanotube/nano carbon black composite mortar static resistance rate is low, pressure-sensitive stabilization
And sensitivity is high, good mechanical performance.Economically see, the cost of composite mortar greatly reduces, widened it and applied model
Enclose.
Brief description of the drawings
The width of accompanying drawing of the present invention 8,
Existence of Fig. 1 electrostatic self-assembled carbon nanotube/nano carbon blacks in mortar；
Deployment conditions of Fig. 2 electrostatic self-assembled carbon nanotube/nano carbon blacks in mortar；
The relation of the compression of Fig. 3 test specimens 1 and resistance change rate；
The compressive strain of Fig. 4 test specimens 1 and the relation of resistance change rate；
The relation of the compression of Fig. 5 test specimens 2 and resistance change rate；
The compressive strain of Fig. 6 test specimens 2 and the relation of resistance change rate；
The relation of the compression of Fig. 7 test specimens 3 and resistance change rate；
The compressive strain of Fig. 8 test specimens 3 and the relation of resistance change rate.
Specific embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Maintenance process：Obtained body test specimen is put into 20 ± 1 DEG C of water and is conserved.During test, the handle from curing pool
Test specimen is taken out, and dries the water of surface of test piece, and dries in the air naturally indoors 3 hours.
The method of testing of static resistance is：Tested with universal meter, method of testing is, direct current, four electrodes.
Static resistance rate, is calculated by formula ρ=RS/1.
The method of testing of pressure-sensitive：The resistance of test specimen is acquired using universal meter connection electrode；Dynamic strain is gathered
Instrument gathers strain information；Universal testing machine is used to be further applied load.
Embodiment 1
Electrostatic self-assembled carbon nanotube/nano carbon black composite mortar is prepared according to the following steps：
(1) 90 parts of raw material cement is taken；10 parts of silicon ash；4 parts of electrostatic self-assembled carbon nanotube/nano carbon black；Water reducer 2.5
Part；150 parts of normal sand；42 parts of water；
(2) the carbon nanotube/nano carbon black of electrostatic self-assembled, silicon ash are sequentially added in cement mortar mixer, water, is subtracted
Aqua, cement and normal sand, stir, and obtain mixture；
(3) mixture for obtaining is poured into mould, then mould is placed on shake table, be vibrated to the mix in mould
The surface grout of thing；
(4) according to the size of mixture in mould, insert for connecting the electrode of external circuit, then somewhat vibrate, it is ensured that
Electrode and mixture contact are good；
(5) mould is put into glue sand curing box, in 20 ± 1 DEG C of temperature, humidity>Under conditions of 95%, conserve 24 hours
The demoulding afterwards, obtains mortar specimen 1 (40mm × 40mm × 80mm).
Obtained mortar specimen is put into 20 ± 1 DEG C of water and is conserved to 1 day, 3 days, 7 days, 14 days, 28 days, 80 day age
Phase, test specimen is taken out from curing pool, dry the water of surface of test piece, and dried in the air naturally indoors 3 hours.
Measure its static resistance rate and be respectively 1.42 Ω .m, 1.60 Ω .m, 1.43 Ω .m, 1.56 Ω .m, 1.62 Ω .m,
1.68Ω.m。
In 80 day age, pressure-sensitive test is carried out to test specimen 1.Experiment loading amplitude used (is the bullet of test specimen for 8MPa
Sexual stage), loading speed is 0.4mm/min, and the periodicity of CYCLIC LOADING is 7.
And change in resistance rate, stress sensitivity and strain sensitivity are calculated according to equation below, result of calculation
As shown in table 1.
Δρmax=100% × (ρmin-ρ0)/ρ0 (1)
Its Δ ρmax：Maximum resistivity rate of change；ρmin：The minimum specific resistance of test specimen during applying compression；ρ0：Test specimen
Static resistance rate.
Wherein, SES：Stress sensitivity；σmax：Maximum crushing stress.
Wherein, SAS：Stress sensitivity；εmax：Maximum compressive strain.
The change in resistance rate of the test specimen 1 of table 1 and sensitivity
From figs. 3 and 4 it can be seen that the pressure-sensitive of test specimen 1 has good stability and repeatability.Can from table 1
Go out the change in resistance rate maximum absolute value of test specimen 1 up to 6.9%, stress and strain sensitivity is respectively 0.84%/MPa,
231。
Embodiment 2
Electrostatic self-assembled carbon nanotube/nano carbon black composite mortar is prepared according to the following steps：
(1) 90 parts of raw material cement is taken；10 parts of silicon ash；7 parts of electrostatic self-assembled carbon nanotube/nano carbon black；Water reducer 2.5
Part；150 parts of normal sand；56 parts of water；
(2) the carbon nanotube/nano carbon black of electrostatic self-assembled, silicon ash are sequentially added in cement mortar mixer, water, is subtracted
Aqua, cement and normal sand, stir, and obtain mixture；
(3) mixture for obtaining is poured into mould, then mould is placed on shake table, be vibrated to the mixture in mould
Surface grout；
(4) according to the size of mixture in mould, insert for connecting the electrode of external circuit, then somewhat vibrate, it is ensured that
Electrode and mixture contact are good；
(5) mould is put into glue sand curing box, in 20 ± 1 DEG C of temperature, humidity>Under conditions of 95%, conserve 24 hours
The demoulding afterwards, obtains mortar specimen 2 (40mm × 40mm × 80mm).
Obtained body test specimen is put into 20 ± 1 DEG C of water and is conserved to 1 day, 3 days, 7 days, 14 days, 28 days, 80 day age
Phase, test specimen is taken out from curing pool, dry the water of surface of test piece, and dried in the air naturally indoors 3 hours.
Measure its static resistance rate and be respectively 0.61 Ω .m, 0.66 Ω .m, 0.69 Ω .m, 0.67 Ω .m, 0.65 Ω .m,
0.68Ω.m。
In 80 day age, pressure-sensitive test is carried out to test specimen 2.Experiment loading amplitude used (is the bullet of test specimen for 8MPa
Sexual stage), loading speed is 0.4mm/min, and the periodicity of CYCLIC LOADING is 7.
Change in resistance rate, stress sensitivity and strain sensitivity are counted according to formula (1), (2) and (3) respectively
Calculate, result of calculation is as shown in table 2.
The change in resistance rate of the test specimen 2 of table 2 and sensitivity
From figs. 5 and 6, it can be seen that the pressure-sensitive of test specimen 2 has good stability and repeatability.Can from table 2
Go out the change in resistance rate maximum absolute value of test specimen 2 up to 22.1%, stress and strain sensitivity is up to 2.69%/MPa respectively
With 704.
Embodiment 3
Electrostatic self-assembled carbon nanotube/nano carbon black composite mortar is prepared according to the following steps：
(1) 90 parts of raw material cement is taken；10 parts of silicon ash；Electrostatic self-assembled carbon nanotube/nano carbon black is multiple 10 parts；Water reducer
2.5 parts；150 parts of normal sand；72 parts of water；
(2) the carbon nanotube/nano carbon black of electrostatic self-assembled, silicon ash are sequentially added in cement mortar mixer, water, is subtracted
Aqua, cement and normal sand, stir, and obtain mixture；
(3) mixture for obtaining is poured into mould, then mould is placed on shake table, be vibrated to the mixture in mould
Surface grout；
(4) according to the size of mixture in mould, insert for connecting the electrode of external circuit, then somewhat vibrate, it is ensured that
Electrode and mixture contact are good；
(5) mould is put into glue sand curing box, in 20 ± 1 DEG C of temperature, humidity>Under conditions of 95%, taken off after maintenance 24h
Mould, obtains mortar specimen 3 (40mm × 40mm × 80mm).
Obtained body test specimen is put into 20 ± 1 DEG C of water and is conserved to 1 day, 3 days, 7 days, 14 days, 28 days, 80 day age
Phase, test specimen is taken out from curing pool, dry the water of surface of test piece, and dry in the air naturally indoors 3 hours.
Measure its static resistance rate and be respectively 0.42 Ω .m, 0.44 Ω .m, 0.42 Ω .m, 0.45 Ω .m, 0.45 Ω .m,
0.45Ω.m。
In 80 day age, pressure-sensitive test is carried out to test specimen 3.Experiment loading amplitude used (is the bullet of test specimen for 8MPa
Sexual stage), loading speed is 0.4mm/min, and the periodicity of CYCLIC LOADING is 7.
Maximum resistivity rate of change, stress sensitivity and strain sensitivity are carried out according to formula (1), (2) and (3) respectively
Calculate, result of calculation is as shown in table 3.
The change in resistance rate of the electrostatic self-assembled carbon nanotube/nano carbon black mortar of table 3 and sensitivity
As can be seen from Figures 7 and 8, the pressure-sensitive of test specimen 3 has good stability and repeatability.Can be tried from table 3
The change in resistance rate maximum absolute value of part 3 up to 19.0%, stress and strain sensitivity be up to respectively 2.31%/MPa and
541。
Claims (3)
1. electrostatic self-assembled carbon nanotube/nano carbon black composite mortar, the raw material of the mortar include cement, silicon ash, electrostatic
Self assembly carbon nanotube/nano carbon black, water reducer, Sha Heshui, raw material include following weight than：90 parts of cement；Silicon ash 10
Part；7 parts of electrostatic self-assembled carbon nanotube/nano carbon black；2.5 parts of water reducer；150 parts of sand；56 parts of water；
The absolute value 22.1% of the maximum resistivity rate of change of the mortar, stress sensitivity 2.69%/MPa, strain sensitivity
704。
2. the preparation method of composite mortar described in claim 1, it is characterised in that comprise the following steps：(1) the weight ratio is taken
Raw material；(2) sequentially added in cement mortar mixer the carbon nanotube/nano carbon black of electrostatic self-assembled, silicon ash, water,
Water reducer, cement and sand, stir, and obtain mixture；(3) described mixture is poured into mould, then mould is put
In the surface grout of the mixture on shake table, being vibrated in mould；(4) according to the size of mixture in mould, inserting is used for
The electrode of external circuit is connected, is vibrated again；(5) mould is put into glue sand curing box, in 20 ± 1 DEG C of temperature, humidity>95%
Under conditions of, the demoulding after conserving 24 hours obtains mortar specimen.
3. electrostatic self-assembled carbon nanotube/nano carbon black composite mortar described in claim 1 is in exothermic material, electromagnetic material or mixed
Applied in Xtah Crude Clay structure health monitoring material.
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| CN109897616B (en) * | 2019-04-25 | 2020-04-14 | 大连理工大学 | Nano composite toughened oil well cement and preparation method and application thereof |
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