CN109734384A - A kind of modified carbon nano-tube enhancing cement base composite mortar and preparation method thereof - Google Patents
A kind of modified carbon nano-tube enhancing cement base composite mortar and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of modified carbon nano-tube enhancing cement base composite mortar and preparation method thereof, according to parts by weight, composite mortar includes following components: 0.5~3.5 part of modified carbon nano-tube, 0.5~2 part of water-reducing agent, 1~5 part of dispersing agent, 100~300 parts of water, 0.5~3 part of defoaming agent, 300~800 parts of cement.The preparation method of modified carbon nano-tube provided by the invention enhancing cement base composite mortar include: be first multi-walled carbon nanotube is carried out it is loaded modified；Then dispersing agent, water-reducing agent are added in tap water, after dissolution, obtain surfactant solution；Modified carbon nanotube is added in configured solution again, mechanical stirring and ultrasonic disperse processing；It is subsequently added into defoaming agent, obtains modified carbon nano-tube solution；Finally, modified carbon nano-tube solution and cement mixing are obtained cement base composite mortar.Cement base composite mortar obtained in the present invention has high-intensitive, high volume stability and impermeability.
Description
Technical field
The invention belongs to cement material technical fields, and in particular to a kind of modified carbon nano-tube enhancing cement base composite mortar
And preparation method thereof.
Background technique
Cement is as building trade common used material, and because of material abundance, moderate cost is widely used.Conventional cement concrete
Material, intensity is high, and brittleness is big, and crackle and fracture are also easy to produce under external impacts, and novel high-performance cement material overcomes tradition
The shortcomings that cement, is subject to reformed AHP on the basis of conventional cement performance, is widely used on the market now.Novel high property
Can cement-based material, because its excellent resistance to compression, bending resistance draw, it is high it is resistance to wait so long performance due to be applied in each engineering construction now, come
It solves the problems, such as to face in current construction industry all kinds of.
However high-performance cement also has some drawbacks in performance, high performance cement-based material is promoting a certain performance
In the case of, the corresponding decline of other performances can be accompanied by.Existing research shows that mixing nanometer titanium dioxide in cement-based material
Silicon, obtained composite mortar intensity are obviously improved than cement material mechanical property itself, but bending resistance draw performance do not have it is aobvious
Writing improves.
Carbon nano-tube material is mixed in cement-based material can be obviously improved the flexural strength of cement-based material, crack resistance
Energy and volume stability reduce volume contraction, but limited to the promotion effect of compression strength.In the prior art not yet
The intensity of cement-based material and the preparation process of toughness can be promoted simultaneously.
Accordingly, it is desirable to provide a kind of be directed to the insufficient improved technology scheme of the above-mentioned prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of modified carbon nano-tube enhancing cement base composite mortars and preparation method thereof, change
Property after carbon nanotube be added in cement material, the cement base composite mortar of preparation is provided simultaneously with high-intensitive and high tenacity, greatly
The mechanical property of cement-based material is improved greatly.
To achieve the goals above, the invention provides the following technical scheme:
A kind of modified carbon nano-tube enhancing cement base composite mortar, according to parts by weight, the composite mortar includes following
Component:
0.5~3.5 part of modified carbon nano-tube, 0.5~2 part of water-reducing agent, 1~5 part of dispersing agent, 100~300 parts of water, defoaming
0.5~3 part of agent, 300~800 parts of cement.
Enhance cement base composite mortar in modified carbon nano-tube as described above, it is preferable that the modified carbon nano-tube is more
Wall carbon nano tube, the multi-wall carbon nano-tube pipe diameter are 10~100nm, and length is 1~100 μm.
Preferably, the multi-wall carbon nano-tube pipe diameter is 10~40nm, and length is 5~30 μm.
Enhance cement base composite mortar in modified carbon nano-tube as described above, it is preferable that the modified carbon nano tube pipe surface
Load has silica, and the silica is the silica of undefined structure；
Preferably, the silicon dioxide layer thickness of the modified carbon nano-tube area load is 5~100nm.
Enhance cement base composite mortar in modified carbon nano-tube as described above, it is preferable that the water-reducing agent subtracts for polycarboxylic acids
Aqua.
Enhance cement base composite mortar in modified carbon nano-tube as described above, it is preferable that the dispersing agent is polyethylene pyrrole
Pyrrolidone or cetyl trimethylammonium bromide.
Enhance cement base composite mortar in modified carbon nano-tube as described above, it is preferable that the defoaming agent is tricresyl phosphate fourth
Ester；Preferably, the cement is P.C composite Portland cement.
A kind of preparation method of modified carbon nano-tube enhancing cement base composite mortar, the preparation method includes following step
It is rapid:
(1) the modified carbon nano-tube preparation of nonloaded silica
Multi-walled carbon nanotube is mixed with ethyl orthosilicate, obtains the modified carbon nano tube of nonloaded silica after treatment
Pipe；
(2) preparation of surfactant solution
It is put into water in a reservoir, then adds a dispersant in water, the container for filling dispersant solution is heated to 50
~60 DEG C, and mechanical stirring, to being completely dissolved, standing after dissolution is cooled to room temperature dispersant solution；Take water-reducing agent that dispersion is added
In agent solution, surfactant solution is obtained after mechanical stirring；
(3) prepared by modified carbon nano-tube solution
The load prepared in step (1) is taken to have the modified carbon nano-tube of silica to be added to the table prepared in step (2)
In the activator solution of face, mechanical stirring dissolves modified carbon nano-tube sufficiently, obtains mixed liquor；Then mixed liquor is subjected to ultrasound
Disperse, defoaming agent is added after ultrasonic disperse, obtains modified carbon nano-tube solution；
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution and cement mixing that will be prepared in step (3), and mechanical stirring is carried out, obtain cement base
Composite mortar.
In the preparation method of modified carbon nano-tube as described above enhancing cement base composite mortar, it is preferable that in parts by weight
It counts, the mass ratio of multi-walled carbon nanotube and ethyl orthosilicate is 1:(5~10 in the step (1))；
Preferably, the mass ratio of multi-walled carbon nanotube and ethyl orthosilicate is 1:(5~7).
In the preparation method of modified carbon nano-tube as described above enhancing cement base composite mortar, it is preferable that the step (3)
In to mixed liquor carry out ultrasonic disperse time be 1~1.5h.
In the preparation method of modified carbon nano-tube as described above enhancing cement base composite mortar, it is preferable that the step (2)
It is 1500~3000r/min with the churned mechanically revolving speed in step (3).
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect:
Multi-walled carbon nanotube used in the present invention (MCNTs) has big L/D ratio, has significant one-dimensional material characteristic, energy
Performance is drawn in the bending resistance for enough dramatically increasing cement concrete material, is added in cement-based material and is played the work of fiber reinforcement technology
With.Meanwhile the nanoscale of multi-walled carbon nanotube, there is nano-filled effect, keep cement-based material finer and close, it is high-intensitive,
High permeability resistant.
The multi-wall carbon nano-tube pipe surface SiO of nanoscale2It is loaded modified, SiO2Using the method for chemical precipitation, carbon nanotube
The SiO of upper cladding2There are stronger binding force, SiO between multi-walled carbon nanotube2It can be carried out with the hydrated product of cement minerals secondary
Reaction, the gap of further filling concrete slurry, reaction form even closer chemical bonding, cement base obtained in the present invention
Composite mortar has high-intensitive, high volume stability and impermeability.
Using nonionic surface active agent as dispersing agent in preparation process of the invention, obtained by Ultrasound Instrument dispersion method
The preferable modified carbon nano-tube of dispersion effect disperses solution, and the modified carbon nano-tube solution adduction cement with good dispersion is mixed
The mechanical property of cement base composite mortar is also further enhanced with after.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.Wherein:
Fig. 1 is the SEM figure for the modified carbon nano-tube being added in the embodiment of the present invention 1.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention be can be combined with each other.
In the present invention on the carbon nanotubes by coated with silica, the modified carbon nano-tube obtained overcomes single dioxy
The defects of cement-based material is added in SiClx, although can promote cement-based material in single nano silica incorporation cement
Performances such as resistance to compression, impervious, but nano silica is also easy to produce reunion, dispersing non-uniform nano material, to will affect cement base compound
The overall performance of size performance；Load has the modified carbon nano-tube of silica to be also equipped with the big L/D ratio of carbon nanotube, plays
Fiber reinforced effect and nano-filled effect, the two combine so that Microstructure of Cement-based Material is fine and close, uniformly, intensity height,
Impermeability is strong.
The preparation method of modified carbon nano-tube enhancing cement base composite mortar provided by the invention, main includes three big steps
It is rapid: firstly, be to multi-walled carbon nanotube carry out it is loaded modified, make SiO2It loads to form clad structure in carbon nano tube surface, obtain
To area load SiO2Modified multiwalled carbon nanotube material；Then, dispersing agent is added in tap water, is stirred evenly, then
Water-reducing agent is added, stirring obtains surfactant solution to dissolving completely；Modified carbon nanotube is added again configured molten
In liquid, mechanical stirring and ultrasonic disperse processing；Then defoaming agent is added, is stirred evenly, modified carbon nano-tube solution is obtained；Most
Afterwards, it by modified carbon nano-tube solution and cement mixing, is sufficiently stirred using blender, obtains cement base composite mortar.
A kind of modified carbon nano-tube provided by the invention enhances cement base composite mortar, according to parts by weight, the composite pulp
Material includes following components:
0.5~3.5 part of modified carbon nano-tube (such as 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 parts, 1.1 parts, 1.2 parts,
1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5
Part, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts, 3.0 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts), 0.5~2 part of water-reducing agent (such as
0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8
Part, 1.9 parts, 2.0 parts), 1~5 part of dispersing agent (such as 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts,
5.0 parts), 100~300 parts of water (such as 120 parts, 140 parts, 160 parts, 180 parts, 200 parts, 220 parts, 240 parts, 260 parts, 280
Part, 300 parts), 0.5~3 part of defoaming agent (such as 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts,
1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6
Part, 2.7 parts, 2.8 parts, 2.9 parts, 3.0 parts), 300~800 parts of cement (such as 320 parts, 360 parts, 400 parts, 450 parts, 500 parts,
550 parts, 600 parts, 650 parts, 700 parts, 750 parts, 800 parts).
In a specific embodiment of the present invention, modified carbon nano-tube is multi-walled carbon nanotube, and multi-wall carbon nano-tube pipe diameter is
10~100nm (such as 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm,
75nm, 80nm, 85nm, 90nm, 95nm), length is 1~100 μm of (such as 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μ
m、35μm、40μm、45μm、50μm、55μm、60μm、65μm、70μm、75μm、80μm、85μm、90μm、95μm、100μm)。
Preferably, multi-wall carbon nano-tube pipe diameter is 10~40nm (such as 15nm, 20nm, 25nm, 30nm, 35nm, 40nm),
Length is 5~30 μm (such as 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm).
In a specific embodiment of the present invention, modified carbon nano-tube area load has silica, and silica is without fixed
The silica of type structure；Preferably, the silicon dioxide layer thickness of modified carbon nano-tube area load be 5~100nm (such as
6nm、8nm、10nm、15nm、20nm、25nm、30nm、35nm、40nm、45nm、50nm、55nm、60nm、65nm、70nm、
75nm、80nm、85nm、90nm、95nm)。
In a specific embodiment of the present invention, water-reducing agent is polycarboxylate water-reducer；Dispersing agent is polyvinylpyrrolidone
(PVP) or cetyl trimethylammonium bromide (CTAB)；Defoaming agent is tributyl phosphate；Cement is P.C composite Portland cement；
Mixing water is tap water or the water for meeting cement concrete water standard.
Enhance cement base composite mortar for a further understanding of modified carbon nano-tube of the invention, the present invention also provides one
The preparation method of kind of modified carbon nano-tube enhancing cement base composite mortar, preparation method specifically includes the following steps:
(1) the modified carbon nano-tube preparation of nonloaded silica
Multi-walled carbon nanotube is mixed with ethyl orthosilicate, is received by the carbon modified that chemical precipitation method obtains nonloaded silica
Mitron；
(2) preparation of surfactant solution
It is put into water in a reservoir, then adds a dispersant in water, the container for filling dispersant solution is heated to 50
~60 DEG C (such as 52 DEG C, 53 DEG C, 54 DEG C, 55 DEG C, 56 DEG C, 57 DEG C, 58 DEG C, 59 DEG C), and mechanical stirring is dissolved to being completely dissolved
Standing afterwards is cooled to room temperature dispersant solution；It takes water-reducing agent to be added in dispersant solution, surface-active is obtained after mechanical stirring
Agent solution；
(3) prepared by modified carbon nano-tube solution
The load prepared in step (1) is taken to have the modified carbon nano-tube of silica to be added to the table prepared in step (2)
In the activator solution of face, mechanical stirring dissolves modified carbon nano-tube sufficiently, obtains mixed liquor, and mixed liquor is then carried out ultrasound
Disperse, defoaming agent is added after ultrasonic disperse, obtains modified carbon nano-tube solution；
In a specific embodiment of the present invention, the mass ratio of multi-walled carbon nanotube and ethyl orthosilicate is 1 in step (1):
(5~10) (such as 1:6,1:7,1:8,1:9,1:10)；Preferably, the mass ratio of multi-walled carbon nanotube and ethyl orthosilicate is 1:
(5~7) (such as 1:5,1:6,1:7).
It in a specific embodiment of the present invention, is 1~1.5h to the time of mixed liquor progress ultrasonic disperse in step (3)
(such as 1.1h, 1.2h, 1.3h, 1.4h, 1.5h).
In a specific embodiment of the present invention, the churned mechanically revolving speed in step (2) and step (3) be 1500~
3000r/min (such as 1600r/min, 1800r/min, 2000r/min, 2200r/min, 2500r/min, 2600r/min,
2800r/min、3000r/min)。
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution and cement mixing that will be prepared in step (3), and mechanical stirring is carried out, obtain cement base
Composite mortar.
Embodiment 1
The preparation method of modified carbon nano-tube enhancing cement base composite mortar provided in an embodiment of the present invention, including following step
It is rapid:
(1) the modified carbon nano-tube preparation of nonloaded silica
The ethyl orthosilicate of the multi-walled carbon nanotube of 1g and 5ml is handled into obtain nonloaded silica according to chemical precipitation method
Modified carbon nano-tube, wherein the load thickness mean value of the silica of modified carbon nano-tube is 30nm.
(2) preparation of surfactant solution
It takes the polyvinylpyrrolidone dispersing agent of 1.4g that the tap water of 168g is added, is heated in thermostat water bath,
Temperature is set as 60 DEG C, and carries out mechanical stirring 15min to being completely dissolved, and the speed of agitator of blender is 2000r/min, is obtained
Dispersant solution；Dispersant solution is cooled to room temperature after dissolution sufficiently, then takes the polycarboxylate water-reducer of 0.6g that dispersion is added
In agent solution, mechanical stirring 2000r/min obtains surfactant solution to being completely dissolved.
(3) prepared by modified carbon nano-tube solution
It takes 0.8g to be added in surfactant solution modified carbon nano-tube obtained during (1), continues mechanical stirring
7min makes to be sufficiently mixed, and revolving speed 2000r/min is then placed into Ultrasound Instrument and carries out dispersion 1.5h, stands 2min, instills
The tributyl phosphate of 1ml eliminates mixed solution blibbing, obtains modified carbon nano-tube solution.
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution finally prepared in (3) is mixed with the P.C composite Portland cement of 450g, uses water
Cement paste blender is stirred, and obtains cement base composite mortar.
The cement base composite mortar prepared in the present embodiment is subjected to blanks and moulding and conserving, prepares cement according to national current standard
Glue sand sample, standard chamber were conserved to test age, then took out resistance to compression, the flexural strength of 3d, 7d, 28d of sample testing, data
It see the table below 1.
Fig. 1 is the SEM picture of the modified carbon nano-tube used in the present embodiment.
Embodiment 2
A kind of preparation method of modified carbon nano-tube enhancing cement base composite mortar provided in an embodiment of the present invention, including with
Lower step:
(1) the modified carbon nano-tube preparation of nonloaded silica
The ethyl orthosilicate of the multi-walled carbon nanotube of 1.5g and 9ml are handled into obtain nonloaded silica according to chemical precipitation method
Modified carbon nano-tube, wherein the load thickness mean value of the silica of modified carbon nano-tube be 45nm.
(2) preparation of surfactant solution
It takes the polyvinylpyrrolidone dispersing agent of 1.6g that the tap water of 175g is added, is heated in thermostat water bath,
Temperature is set as 60 DEG C, and carries out mechanical stirring 15min to being completely dissolved, and the speed of agitator of blender is 2500r/min, is obtained
Dispersant solution；Dispersant solution is cooled to room temperature after dissolution sufficiently, then takes the polycarboxylate water-reducer of 0.7g that dispersion is added
In agent solution, mechanical stirring 2500r/min obtains surfactant solution to being completely dissolved.
(3) prepared by modified carbon nano-tube solution
It takes 0.95g to be added in surfactant solution modified carbon nano-tube obtained during (1), continues mechanical stirring
8min makes to be sufficiently mixed, and revolving speed 2500r/min is then placed into Ultrasound Instrument and carries out dispersion 1.5h, stands 2min, instills
The tributyl phosphate of 1ml eliminates mixed solution blibbing, obtains modified carbon nano-tube solution.
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution finally prepared in (3) is mixed with the P.C composite Portland cement of 470g, uses water
Cement paste blender is stirred, and obtains cement base composite mortar.
The cement base composite mortar prepared in the present embodiment is subjected to blanks and moulding and conserving, prepares cement according to national current standard
Glue sand sample, standard chamber were conserved to test age, then took out resistance to compression, the flexural strength of 3d, 7d, 28d of sample testing, data
It see the table below 1.
Embodiment 3
A kind of preparation method of modified carbon nano-tube enhancing cement base composite mortar provided in an embodiment of the present invention, including with
Lower step:
(1) the modified carbon nano-tube preparation of nonloaded silica
The ethyl orthosilicate of the multi-walled carbon nanotube of 1.5g and 11ml are handled into obtain load titanium dioxide according to chemical precipitation method
The modified carbon nano-tube of silicon, wherein the load thickness mean value of the silica of modified carbon nano-tube is 65nm.
(2) preparation of surfactant solution
It takes the cetyl trimethylammonium bromide dispersing agent of 1.8g that the tap water of 180g is added, is carried out in thermostat water bath
Heating, temperature are set as 55 DEG C, and carry out mechanical stirring 20min to being completely dissolved, and the speed of agitator of blender is 2500r/
Min obtains dispersant solution；Dispersant solution is cooled to room temperature after dissolution sufficiently, then takes the polycarboxylate water-reducer of 0.8g
It is added in dispersant solution, mechanical stirring 2500r/min obtains surfactant solution to being completely dissolved.
(3) prepared by modified carbon nano-tube solution
It takes 1.28g to be added in surfactant solution modified carbon nano-tube obtained during (1), continues mechanical stirring
10min makes to be sufficiently mixed, and revolving speed 2500r/min is then placed into Ultrasound Instrument and carries out dispersion 2h, stands 2min, instills 1ml
Tributyl phosphate eliminate mixed solution blibbing, obtain modified carbon nano-tube solution.
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution finally prepared in (3) is mixed with the P.C composite Portland cement of 490g, uses water
Cement paste blender is stirred, and obtains cement base composite mortar.
The cement base composite mortar prepared in the present embodiment is subjected to blanks and moulding and conserving, prepares cement according to national current standard
Glue sand sample, standard chamber were conserved to test age, then took out resistance to compression, the flexural strength of 3d, 7d, 28d of sample testing, data
It see the table below 1.
Embodiment 4
A kind of preparation method of modified carbon nano-tube enhancing cement base composite mortar provided in an embodiment of the present invention, including with
Lower step:
(1) the modified carbon nano-tube preparation of nonloaded silica
The ethyl orthosilicate of the multi-walled carbon nanotube of 2g and 14ml are handled into obtain nonloaded silica according to chemical precipitation method
Modified carbon nano-tube, wherein the load thickness mean value of the silica of modified carbon nano-tube be 70nm.
(2) preparation of surfactant solution
It takes the polyvinylpyrrolidone dispersing agent of 3g that the tap water of 240g is added, is heated in thermostat water bath, temperature
Degree is set as 50 DEG C, and carries out mechanical stirring 20min to being completely dissolved, and the speed of agitator of blender is 2500r/min, is divided
Dispersant solution；Dispersant solution is cooled to room temperature after dissolution sufficiently, then takes the polycarboxylate water-reducer of 1g that dispersing agent is added molten
In liquid, mechanical stirring 2500r/min obtains surfactant solution to being completely dissolved.
(3) prepared by modified carbon nano-tube solution
It takes 2g to be added in surfactant solution modified carbon nano-tube obtained during (1), continues mechanical stirring
10min makes to be sufficiently mixed, and revolving speed 2500r/min is then placed into Ultrasound Instrument and carries out dispersion 2h, stands 2min, instills
The tributyl phosphate of 1.5ml eliminates mixed solution blibbing, obtains modified carbon nano-tube solution.
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution finally prepared in (3) is mixed with the P.C composite Portland cement of 650g, uses water
Cement paste blender is stirred, and obtains cement base composite mortar.
The cement base composite mortar prepared in the present embodiment is subjected to blanks and moulding and conserving, prepares cement according to national current standard
Glue sand sample, standard chamber were conserved to test age, then took out resistance to compression, the flexural strength of 3d, 7d, 28d of sample testing, data
It see the table below 1.
Embodiment 5
A kind of preparation method of modified carbon nano-tube enhancing cement base composite mortar provided in an embodiment of the present invention, including with
Lower step:
(1) the modified carbon nano-tube preparation of nonloaded silica
The ethyl orthosilicate of the multi-walled carbon nanotube of 2g and 13ml are handled into obtain nonloaded silica according to chemical precipitation method
Modified carbon nano-tube, wherein the load thickness mean value of the silica of modified carbon nano-tube be 60nm.
(2) preparation of surfactant solution
It takes the polyvinylpyrrolidone dispersing agent of 4g that the tap water of 280g is added, is heated in thermostat water bath, temperature
Degree is set as 60 DEG C, and carries out mechanical stirring 20min to being completely dissolved, and the speed of agitator of blender is 2000r/min, is divided
Dispersant solution；Dispersant solution is cooled to room temperature after dissolution sufficiently, then takes the polycarboxylate water-reducer of 2g that dispersing agent is added molten
In liquid, mechanical stirring 2000r/min obtains surfactant solution to being completely dissolved.
(3) prepared by modified carbon nano-tube solution
It takes 2.3g to be added in surfactant solution modified carbon nano-tube obtained during (1), continues mechanical stirring
10min makes to be sufficiently mixed, and revolving speed 2500r/min is then placed into Ultrasound Instrument and carries out dispersion 2h, stands 2min, instills 3ml
Tributyl phosphate eliminate mixed solution blibbing, obtain modified carbon nano-tube solution.
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution finally prepared in (3) is mixed with the P.C composite Portland cement of 750g, uses water
Cement paste blender is stirred, and obtains cement base composite mortar.
The cement base composite mortar prepared in the present embodiment is subjected to blanks and moulding and conserving, prepares cement according to national current standard
Glue sand sample, standard chamber were conserved to test age, then took out resistance to compression, the flexural strength of 3d, 7d, 28d of sample testing, data
It see the table below 1.
Reference examples 1
Reference examples 1 the difference from embodiment 1 is that, the multi-walled carbon nanotube not Jing Guo modification is mixed in reference examples 1,
The quality for the multi-walled carbon nanotube being added in step (3) is 0.8g, other steps are same as Example 1, and details are not described herein.
The cement base composite mortar prepared in this reference examples is subjected to blanks and moulding and conserving, prepares cement according to national current standard
Glue sand sample, standard chamber were conserved to test age, then took out resistance to compression, the flexural strength of 3d, 7d, 28d of sample testing, data
It see the table below 1.
Reference examples 2
Reference examples 2 the difference from embodiment 1 is that, be not incorporated into modified carbon nano-tube in reference examples 2, other steps and reality
Apply that example 1 is identical, and details are not described herein.
The cement base composite mortar prepared in this reference examples is subjected to blanks and moulding and conserving, prepares cement according to national current standard
Glue sand sample, standard chamber were conserved to test age, then took out resistance to compression, the flexural strength of 3d, 7d, 28d of sample testing, data
It see the table below 1.
The flexural strength and compression strength of 1 embodiment of table and reference examples
From table 1 it follows that embodiment 1-5 is the cement based sizing test block of incorporating modified carbon nanotube compared to control
The test block of carbon nanotube is not added for example 2, and 3d, 7d and 28d compression strength of embodiment 1-5 is obviously higher than reference examples 2；Embodiment
3d, 7d and 28d flexural strength of 1-5 is equally also obviously higher than reference examples 2；The wherein embodiment 4 of incorporating modified carbon nanotube
The test block 28d compression strength of middle preparation improves 34.7%, and flexural strength improves 52.6%；The compression strength of 3d improves
39.8%, flexural strength improves 61.8%；The compression strength of 7d improves 36.4%, and flexural strength improves 56.2%.
What reference examples 1 mixed is the multi-walled carbon nanotube without modification, compared to pair that carbon nanotube is not added
As usual 2, it is added strong without the compression strength and anti-folding that can also improve cement base test block after the multi-walled carbon nanotube of modification
Degree, but compression strength and increasing for flexural strength will be lower than the carbon nanotubes being added Jing Guo modification.
In summary: modified multiwalled carbon nanotube used in the present invention is coated with silicon oxide on the carbon nanotubes, and
The silica bond strength of load is high, is added into the activeness and quietness effect for having carbon nanotube in cement base composite mortar,
But also with the filling densification effects of silica, while also overcoming easy to reunite after single silica is added, dispersion unevenness
The even overall performance performance for influencing cement based sizing.
The multi-walled carbon nanotube of the cement based sizing prepared in the present invention, incorporation has nano-filled effect and fiber reinforcement
The effect of toughening keeps cement-based material finer and close, high-intensitive, and high permeability resistant can dramatically increase cement concrete material
Performance is drawn in bending resistance；The multi-wall carbon nano-tube pipe surface SiO of nanoscale simultaneously2It is loaded modified, SiO2Using the method for chemical precipitation,
SiO2There are stronger binding force, SiO between multi-walled carbon nanotube2Secondary response can be carried out with the hydrated product of cement minerals, into one
The gap of filling concrete slurry is walked, reaction forms even closer chemical bonding, so that cement base obtained in the present invention is compound
Slurry has high-intensitive, high volume stability and impermeability.
In addition, being dispersed using nonionic surface active agent as dispersing agent by Ultrasound Instrument in preparation process of the invention
Method obtains the preferable modified carbon nano-tube of dispersion effect and disperses solution, and the modified carbon nano-tube solution with good dispersion sums it up
Also the mechanical property of cement base composite mortar is further enhanced after cement blending.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of modified carbon nano-tube enhances cement base composite mortar, which is characterized in that according to parts by weight, the composite mortar
Including following components:
0.5~3.5 part of modified carbon nano-tube, 0.5~2 part of water-reducing agent, 1~5 part of dispersing agent, 100~300 parts of water, defoaming agent 0.5
~3 parts, 300~800 parts of cement.
2. modified carbon nano-tube as described in claim 1 enhances cement base composite mortar, which is characterized in that the carbon modified is received
Mitron is multi-walled carbon nanotube, and the multi-wall carbon nano-tube pipe diameter is 10~100nm, and length is 1~100 μm；
Preferably, the multi-wall carbon nano-tube pipe diameter is 10~40nm, and length is 5~30 μm.
3. modified carbon nano-tube as claimed in claim 2 enhances cement base composite mortar, which is characterized in that the carbon modified is received
Nanotube surface load has silica, and the silica is the silica of undefined structure；
Preferably, the silicon dioxide layer thickness of the modified carbon nano-tube area load is 5~100nm.
4. modified carbon nano-tube as described in claim 1 enhances cement base composite mortar, which is characterized in that the water-reducing agent is
Polycarboxylate water-reducer.
5. modified carbon nano-tube as described in claim 1 enhances cement base composite mortar, which is characterized in that the dispersing agent is
Polyvinylpyrrolidone or cetyl trimethylammonium bromide.
6. modified carbon nano-tube as described in claim 1 enhances cement base composite mortar, which is characterized in that the defoaming agent is
Tributyl phosphate；
Preferably, the cement is P.C composite Portland cement.
7. a kind of preparation method of the enhancing of the modified carbon nano-tube as described in claim 1~6 is any cement base composite mortar, special
Sign is that the preparation method comprises the following steps:
(1) the modified carbon nano-tube preparation of nonloaded silica
Multi-walled carbon nanotube is mixed with ethyl orthosilicate, obtains the modified carbon nano-tube of nonloaded silica after treatment；
(2) preparation of surfactant solution
It is put into water in a reservoir, then adds a dispersant in water, the container for filling dispersant solution is heated to 50~60
DEG C, and mechanical stirring, to being completely dissolved, standing after dissolution is cooled to room temperature dispersant solution；Take water-reducing agent that dispersing agent is added molten
In liquid, surfactant solution is obtained after mechanical stirring；
(3) prepared by modified carbon nano-tube solution
The load prepared in step (1) is taken to have the modified carbon nano-tube of silica to be added to the surface prepared in step (2) living
In property agent solution, mechanical stirring dissolves modified carbon nano-tube sufficiently, obtains mixed liquor；Then mixed liquor is subjected to ultrasound point
It dissipates, defoaming agent is added after ultrasonic disperse, obtains modified carbon nano-tube solution；
(4) preparation of cement base composite mortar
The modified carbon nano-tube solution and cement mixing that will be prepared in step (3), and mechanical stirring is carried out, it is compound to obtain cement base
Slurry.
8. the preparation method of modified carbon nano-tube enhancing cement base composite mortar as claimed in claim 7, which is characterized in that press
Parts by weight meter, the mass ratio of multi-walled carbon nanotube and ethyl orthosilicate is 1:(5~10 in the step (1))；
Preferably, the mass ratio of multi-walled carbon nanotube and ethyl orthosilicate is 1:(5~7).
9. the preparation method of modified carbon nano-tube enhancing cement base composite mortar as claimed in claim 7, which is characterized in that institute
Stating in step (3) is 1~1.5h to the time of mixed liquor progress ultrasonic disperse.
10. the preparation method of modified carbon nano-tube enhancing cement base composite mortar as claimed in claim 7, which is characterized in that
Churned mechanically revolving speed in the step (2) and step (3) is 1500~3000r/min.
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