CN107188464A - A kind of regenerated aggregate concrete and preparation method thereof - Google Patents
A kind of regenerated aggregate concrete and preparation method thereof Download PDFInfo
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- CN107188464A CN107188464A CN201710398517.4A CN201710398517A CN107188464A CN 107188464 A CN107188464 A CN 107188464A CN 201710398517 A CN201710398517 A CN 201710398517A CN 107188464 A CN107188464 A CN 107188464A
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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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- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/10—Clay
- C04B14/104—Bentonite, e.g. montmorillonite
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1048—Polysaccharides, e.g. cellulose, or derivatives thereof
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/10—Mortars, concrete or artificial stone characterised by specific physical values for the viscosity
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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Abstract
The invention discloses a kind of regenerated aggregate concrete and preparation method thereof, its raw material composition percentage is：Cement 15 20%, water 5 15%, natural coarse aggregate 0.5 40%, waste and old concrete regenerated coarse aggregate 30 70%, methacrylic acid 0.03 0.05%, neopentyl glycol 0.02 0.08%, composite toughening material 0.5 1%, flyash 5 10%, polyacrylate 0.5 1%, early strength agent 0.01 0.03% and water reducer 0.01 0.03%.Concrete produced by the present invention integrally has good toughness, fatigue resistance and isotropism, effectively plays the effect of material coordination plasticizing, and intensity can reach 60 80Mpa, it is adaptable to the preparation of load-carrying members, can make up the domestic deficiency studied in this respect at present.
Description
Technical field
The invention belongs to the preparation field of concrete, and in particular to a kind of regenerated aggregate concrete and preparation method thereof.
Background technology
Both at home and abroad to regeneration concrete quality and Original concrete and mortar performance, Original concrete deterioration extent, broken
Relation between method and new compound composition is studied, it is believed that the original concrete cement bonded sand sticked on regeneration aggregate
Content of mortar is to determining regeneration concrete performance lifting in the quality and original concrete of slurry cementitious matter, mortar and interface area
Influence.Recycled concrete strength characteristic is mixed by the ratio of coarse-fine aggregate, matrix in such as Matrix-concrete strength, original concrete
The abrasion loss and water imbibition of maximum aggregate size with the when regeneration aggregate of Aggregate of recycled concrete maximum particle diameter etc. in solidifying soil
The influence of some key factors.In addition, the ratio of mud, maximum aggregate size and dry mixing time also have to recycled concrete strength characteristic
Certain influence.
In actual applications, domestic situation also has a certain distance with external.Due to domestic shortage original concrete
Data, this makes the control of regeneration concrete quality have certain difficulty, thus when in use, it is necessary to regeneration aggregate and regeneration
The performance of concrete is tested.Result of study shows simultaneously, and regenerated aggregate concrete uses mechanical property in load-carrying members
It is restricted, because the performance of regenerated aggregate concrete is more relatively poor than the aggregate effect of normal concrete, moreover, strong concrete
Degree is higher, and fragility is bigger, therefore the regenerated aggregate concrete that obtain in load-carrying members has technical bottleneck, needs pair for this
Regenerated aggregate concrete carries out toughness reinforcing.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of regenerated aggregate concrete and its preparation side
Method.Gained regenerated aggregate concrete has good shock resistance, antidetonation and cracking resistance, it is adaptable to the preparation of load-carrying members, can
Make up the domestic deficiency studied in this respect at present.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of regenerated aggregate concrete, its raw material constitutes percentage and is：Cement 15-20%, water 5-15%, natural thick bone
Expect 0.5-40%, waste and old concrete regenerated coarse aggregate 30-70%, methacrylic acid 0.03-0.05%, neopentyl glycol 0.02-0.08%,
Composite toughening material 0.5-1%, flyash 5-10%, polyacrylate 0.5-1%, early strength agent 0.01-0.03% and water reducer 0.01-
0.03%, the percetage by weight sum of above-mentioned each raw material is 100%；Wherein natural coarse aggregate and waste and old concrete regenerated coarse aggregate
Content sum is 50%-70.5%.
Described water reducer is naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 18-24%.
The early strength agent is one kind in villaumite, sulfate, nitrate, nitrite, triethanolamine, acetic acid, acetate
Or it is a variety of.
Described composite toughening material is a kind of composite available for concrete activeness and quietness, and its preparation method is：
After the activated processing of halloysite nanotubes, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into acyl chlorides
After functional group, and difunctional organic compound reaction, then reacted with Cyanuric Chloride, obtain surface and there is active chloride triazine ring
Halloysite nanotubes, finally prepared with methylcellulose by nucleophilic substitution；In the composite toughening material, angstrom
The mass content ratio about 1 of Lip river stone nanotube and methylcellulose:0.1-0.5, preparation method specifically includes following steps：
（1）By the halloysite nanotubes of activated processing（6-30 kg）And thionyl chloride（10-60 kg）In organic solvent P（50-
230 L）Middle mixing, is stirred after 6-15 h at 40-55 DEG C, in 70-80 in 40 kHz, 200 KW supersonic wave cleaning machine
Ultrasound 10-16 h at DEG C, then centrifuge 30-40 min with 4000-5000 rpm rotating speed, separate solid and through organic solvent Q
After cleaning, then the vacuum drying 30-50 h at 25-35 DEG C；
（2）Take step（1）Handle obtained halloysite nanotubes（5-30 kg）, difunctional organic compound（1-8 kg）With
Triethylamine（1-6 L）In organic solvent P（50-220 L）Middle mixing, is stirred after 5-15 h at 50-60 DEG C, in nitrogen protection
Under, in 20 kHz, 150 KW supersonic wave cleaning machine in after ultrasonic reaction 6-10 h at 70-85 DEG C, remove triethylamine under reduced pressure
With organic solvent P, then after blended solvent R is cleaned, 24-48 h are dried in vacuo at 10-20 DEG C；
（3）Take step（2）Handle obtained halloysite nanotubes（5-20 kg）And Cyanuric Chloride（0.5-5 kg）In tetrahydrofuran
（60-230 L）Middle mixing, stirs 12-24 h, in 0-10 in 40 kHz, 200 KW supersonic wave cleaning machine at 0-10 DEG C
It is clean through tetrahydrofuran at DEG C after ultrasound 3-8 h, then at 0-10 DEG C after reaction 24-72 h, it is dried in vacuo at 10-15 DEG C
24-56 h；
（4）Take step（3）Handle obtained halloysite nanotubes（5-20 kg）In N, N '-dimethyl formamide（50-200 L）
After middle dissolving, it is added to and is dissolved with methylcellulose（1-5 kg）N, N '-dimethyl formamide solution（10-50 L ）In,
5-10 h are stirred at 10-20 DEG C, in ultrasound 1-5 h at 10-20 DEG C in 40 kHz, 300 KW supersonic wave cleaning machine, in nitrogen
It is warming up under gas shielded after 40-60 DEG C, isothermal reaction 36-56 h, then is warming up to 80-95 DEG C, isothermal reaction 24-48h, decompression steaming
Except solvent, after being eluted with water, it is dried in vacuo at 40 DEG C after 24-48 h, obtains the composite toughening material.
Organic solvent P in above-mentioned steps is one kind in toluene, 1-METHYLPYRROLIDONE and N, N '-dimethyl acetamide
Or it is several；Organic solvent Q is anhydrous propanone or carbon tetrachloride；The mixed solvent R is made up of ethanol, acetone and water, wherein second
The volume ratio of alcohol, acetone and water is 2:2:6.
Above-mentioned steps（2）In difunctional organic compound be 1,3- propane diamine, ethylenediamine and l, 6- hexamethylene diamine in
It is a kind of.
Above-mentioned steps（4）In methylcellulose viscosity average molecular weigh be 3000-20000, substitution value is 0.5-2.0.
Above-mentioned steps（1）Described in halloysite nanotubes activation process step：
（A）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（B）In two L ball grinders of identical 15（Nylon tank）In each stainless steel ball for loading 60 a diameter of 5 mm and 50
A diameter of 10 mm stainless steel ball, is then respectively adding through step（A）The kg of halloysite nanotubes 6 after processing, then drip respectively
Plus 600 ml absolute ethyl alcohols, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are in rotating speed
Under conditions of 350 rpm and every 30 minutes automatic conversion direction of rotation after ball milling 40-56 h, average length is obtained for 200-230
Nm chopped halloysite nanotubes；
（C）Take step（B）The halloysite nanotubes after handling that are chopped are added to the water that pH is the polysorbas20 that 8, concentration is 15 wt%
Ultrasonic 24 h in solution, filtering is stand-by after 30 h in being dried in vacuo at 68-70 DEG C after being eluted with water.
Described halloysite nanotubes are commercially available prod, its main specifications：Character：White powder；Composition：SiO2：58.1、
Al2O3：41.02、TiO2：0.17、Fe2O3：0.38、P2O5：0.16；Bore：15-22 nm；Pipe external diameter：40-70 nm；It is long
Degree：<1.5 μm；Specific surface area：53.4 m2/g；Density：2.5-2.6g/cm3。
Described polysorbas20 is commercially available, its main specifications：Character：Pale yellow viscous liquid；Active matter：98-99%；Acid number
(KOHmg/g)：≤1.0；Hydroxyl value (KOHmg/g)：80-108；HLB value：16.7；Saponification number (KOHmg/g)：40-50；Moisture content
(%)：≤1.0.
The preparation process of regenerated aggregate concrete as described above is as follows：
1）Cement, natural coarse aggregate, waste and old concrete regenerated coarse aggregate and flyash are added into mixer, it is dry to stir 2-3 minutes；
2）Then sequentially add methacrylic acid, neopentyl glycol, composite toughening material, polyacrylate, early strength agent, water reducer and
Water continues to stir 5-10 minutes；
3）By concreting, mark is supported and obtains within 28 days regenerated aggregate concrete, and the intensity of concrete can reach 60-80Mpa.
The beneficial effects of the present invention are：
（1）Composite environment provided by the present invention available for concrete activeness and quietness is friendly, in conventional organic solvent
With good dissolubility, there is good dispersiveness in water, the preparation condition of the composite is readily satisfied, and raw material comes
Source is enriched, and cost is relatively low,；
（2）The composite for the concrete activeness and quietness that the present invention is added, by the galapectite nanometer of activeness and quietness excellent performance
Pipe and methylcellulose are combined, and by multi-step surface covalent reaction, form a kind of unique compound system, can be mixed
It is fully dispersed in solidifying soil, the effect of material coordination plasticizing is effectively played, makes concrete that integrally there is good toughness, fatigue resistance
And isotropism, it is a kind of high performance concrete activeness and quietness composite；
（3）Concrete produced by the present invention integrally has good toughness, fatigue resistance and isotropism, effectively plays material association
With the effect of toughness reinforcing, intensity can reach 60-80Mpa.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of regenerated aggregate concrete, its raw material constitutes percentage and is：Cement 18%, water 12%, natural coarse aggregate
20%th, waste and old concrete regenerated coarse aggregate 40%, methacrylic acid 0.05%, neopentyl glycol 0.05%, composite toughening material 0.66%,
Flyash 8.2%, polyacrylate 1%, early strength agent 0.02% and water reducer 0.02%.
Described water reducer is naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 20%.
The early strength agent is that villaumite, sulfate and nitrate are 1 in mass ratio:1:1 mixing.
Described composite toughening material is a kind of composite available for concrete activeness and quietness, and its preparation method is：
After the activated processing of halloysite nanotubes, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into acyl chlorides
After functional group, and difunctional organic compound reaction, then reacted with Cyanuric Chloride, obtain surface and there is active chloride triazine ring
Halloysite nanotubes, finally prepared with methylcellulose by nucleophilic substitution, specifically include following steps：
（1）By the halloysite nanotubes of activated processing（18 kg）And thionyl chloride（35 kg）In N, N '-dimethyl acetamide
（140 L）Middle mixing, is stirred at 50 DEG C after 10 h, in super at 75 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine
The h of sound 13, then centrifuges 35 min with 4500 rpm rotating speed, after separating solid and being cleaned through anhydrous propanone, then at 30 DEG C very
Sky dries 40 h；
（2）Take step（1）Handle obtained halloysite nanotubes（20 kg）, l, 6- hexamethylene diamines（5 kg）And triethylamine（4 L）
N, N '-dimethyl acetamide（150 L）Middle mixing, is stirred at 55 DEG C after 10 h, under nitrogen protection, in 20 kHz, 150
In after the h of ultrasonic reaction 8 at 78 DEG C, removing triethylamine and N under reduced pressure in KW supersonic wave cleaning machine, N '-dimethyl acetamide, then
Blended solvent R（It is made up of ethanol, acetone and water, wherein the volume ratio of ethanol, acetone and water is 2:2:6）After cleaning, 15
35 h are dried in vacuo at DEG C；
（3）Take step（2）Handle obtained halloysite nanotubes（12 kg）And Cyanuric Chloride（3 kg）In tetrahydrofuran（150
L）Middle mixing, stirs 18 h at 5 DEG C, in after ultrasonic 6 h at 5 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then
Reacted at 5 DEG C after 36 h, cleaned through tetrahydrofuran, 38 h are dried in vacuo at 12 DEG C；
（4）Take step（3）Handle obtained halloysite nanotubes（12 kg）In N, N '-dimethyl formamide（150L）Middle dissolving
Afterwards, it is added to and is dissolved with methylcellulose（3 kg, viscosity average molecular weigh is 12000, and substitution value is 1.0）N, N '-dimethyl first
Amide solution（30 L ）In, 8 h are stirred at 15 DEG C, in ultrasonic at 15 DEG C in 40 kHz, 300 KW supersonic wave cleaning machine
3 h, are warming up to after 50 DEG C, the h of isothermal reaction 46 under nitrogen protection, then are warming up to 90 DEG C, and isothermal reaction 36h is removed under reduced pressure molten
Agent, after being eluted with water, is dried in vacuo after 36 h at 40 DEG C, obtains the composite toughening material.
Above-mentioned steps（1）Described in halloysite nanotubes activation process step：
（A）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（B）In two L ball grinders of identical 15（Nylon tank）In each stainless steel ball for loading 60 a diameter of 5 mm and 50
A diameter of 10 mm stainless steel ball, is then respectively adding through step（A）The kg of halloysite nanotubes 6 after processing, then drip respectively
Plus 600 ml absolute ethyl alcohols, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are in rotating speed
Under conditions of 350 rpm and every 30 minutes automatic conversion direction of rotation after ball milling 50h, it is the short of 220 nm to obtain average length
Cut halloysite nanotubes；
（C）Take step（B）The halloysite nanotubes after handling that are chopped are added to the water that pH is the polysorbas20 that 8, concentration is 15 wt%
Ultrasonic 24 h in solution, filtering is stand-by after 30 h in being dried in vacuo at 70 DEG C after being eluted with water.
Described halloysite nanotubes are commercially available prod, its main specifications：Character：White powder；Composition：SiO2：58.1、
Al2O3：41.02、TiO2：0.17、Fe2O3：0.38、P2O5：0.16；Bore：15-22 nm；Pipe external diameter：40-70 nm；It is long
Degree：<1.5 μm；Specific surface area：53.4 m2/g；Density：2.5-2.6g/cm3。
Described polysorbas20 is commercially available, its main specifications：Character：Pale yellow viscous liquid；Active matter：98-99%；Acid number
(KOHmg/g)：≤1.0；Hydroxyl value (KOHmg/g)：80-108；HLB value：16.7；Saponification number (KOHmg/g)：40-50；Moisture content
(%)：≤1.0.
The preparation process of regenerated aggregate concrete as described above is as follows：
1）Cement, natural coarse aggregate, waste and old concrete regenerated coarse aggregate and flyash are added into mixer, it is dry to stir 2 minutes；
2）Then sequentially add methacrylic acid, neopentyl glycol, composite toughening material, polyacrylate, early strength agent, water reducer and
Water continues to stir 8 minutes；
3）By concreting, mark is supported and obtains regenerated aggregate concrete in 28 days.
The present embodiment measure 28 days regenerated aggregate concretes compression strength, rupture strength, adhesion strength and water absorption rate and
Shrinkage factor is 79.15MPa, 35.8MPa, 5.7MPa, 0.25% and 0.28% respectively.
Embodiment 2
A kind of regenerated aggregate concrete, its raw material constitutes percentage and is：Cement 15%, water 9%, natural coarse aggregate 40%,
Waste and old concrete regenerated coarse aggregate 30%, methacrylic acid 0.03%, neopentyl glycol 0.02%, composite toughening material 0.41%, fine coal
Ash 5%, polyacrylate 0.5%, early strength agent 0.01% and water reducer 0.03%.
Described water reducer is naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 24%.
The early strength agent is that nitrite and acetate are 1 in mass ratio:1 mixing.
Described composite toughening material is a kind of composite available for concrete activeness and quietness, and its preparation method is：
After the activated processing of halloysite nanotubes, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into acyl chlorides
After functional group, and difunctional organic compound reaction, then reacted with Cyanuric Chloride, obtain surface and there is active chloride triazine ring
Halloysite nanotubes, finally prepared with methylcellulose by nucleophilic substitution；Specifically include following steps：
（1）By the halloysite nanotubes of activated processing（6 kg）And thionyl chloride（10 kg）In toluene（50 L）Middle mixing,
Stirred at 40 DEG C after 15 h, in ultrasonic 16 h at 70 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then with 4000
Rpm rotating speed centrifuges 40 min, after separating solid and being cleaned through anhydrous propanone, then is dried in vacuo at 25 DEG C 50 h；
（2）Take step（1）Handle obtained halloysite nanotubes（5 kg）, 1,3- propane diamine（1 kg）And triethylamine（1 L）
Toluene（50 L）Middle mixing, is stirred at 50 DEG C after 15 h, under nitrogen protection, in 20 kHz, 150 KW ultrasonic wave cleaning
In after the h of ultrasonic reaction 10 at 70 DEG C, removing triethylamine and toluene, then blended solvent R under reduced pressure in machine（By ethanol, acetone and
Water is constituted, and wherein the volume ratio of ethanol, acetone and water is 2:2:6）After cleaning, 48 h are dried in vacuo at 10 DEG C；
（3）Take step（2）Handle obtained halloysite nanotubes（5 kg）And Cyanuric Chloride（0.5 kg）In tetrahydrofuran（60
L）Middle mixing, stirs 24 h at 0 DEG C, in after ultrasonic 8 h at 0 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then
Reacted at 0 DEG C after 72 h, cleaned through tetrahydrofuran, 56 h are dried in vacuo at 10 DEG C；
（4）Take step（3）Handle obtained halloysite nanotubes（5 kg）In N, N '-dimethyl formamide（50 L）Middle dissolving
Afterwards, it is added to and is dissolved with methylcellulose（1 kg, viscosity average molecular weigh is 3000, and substitution value is 0.5）N, N '-dimethyl formyl
Amine aqueous solution（10 L ）In, 10 h are stirred at 10 DEG C, in ultrasound 5 at 10 DEG C in 40 kHz, 300 KW supersonic wave cleaning machine
H, is warming up to after 40 DEG C, the h of isothermal reaction 56 under nitrogen protection, then is warming up to 80 DEG C, and isothermal reaction 48h is removed under reduced pressure molten
Agent, after being eluted with water, is dried in vacuo after 24 h at 40 DEG C, obtains the composite toughening material.
Above-mentioned steps（1）Described in halloysite nanotubes activation process step：
（A）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（B）In two L ball grinders of identical 15（Nylon tank）In each stainless steel ball for loading 60 a diameter of 5 mm and 50
A diameter of 10 mm stainless steel ball, is then respectively adding through step（A）The kg of halloysite nanotubes 6 after processing, then drip respectively
Plus 600 ml absolute ethyl alcohols, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are in rotating speed
Under conditions of 350 rpm and every 30 minutes automatic conversion direction of rotation after the h of ball milling 40, it is the short of 200 nm to obtain average length
Cut halloysite nanotubes；
（C）Take step（B）The halloysite nanotubes after handling that are chopped are added to the water that pH is the polysorbas20 that 8, concentration is 15 wt%
Ultrasonic 24 h in solution, filtering is stand-by after 30 h in being dried in vacuo at 68 DEG C after being eluted with water.
Described halloysite nanotubes are commercially available prod, its main specifications：Character：White powder；Composition：SiO2：58.1、
Al2O3：41.02、TiO2：0.17、Fe2O3：0.38、P2O5：0.16；Bore：15-22 nm；Pipe external diameter：40-70 nm；It is long
Degree：<1.5 μm；Specific surface area：53.4 m2/g；Density：2.5-2.6g/cm3。
Described polysorbas20 is commercially available, its main specifications：Character：Pale yellow viscous liquid；Active matter：98-99%；Acid number
(KOHmg/g)：≤1.0；Hydroxyl value (KOHmg/g)：80-108；HLB value：16.7；Saponification number (KOHmg/g)：40-50；Moisture content
(%)：≤1.0.
The preparation process of regenerated aggregate concrete as described above is as follows：
1）Cement, natural coarse aggregate, waste and old concrete regenerated coarse aggregate and flyash are added into mixer, it is dry to stir 2 minutes；
2）Then sequentially add methacrylic acid, neopentyl glycol, composite toughening material, polyacrylate, early strength agent, water reducer and
Water continues to stir 5 minutes；
3）By concreting, mark is supported and obtains regenerated aggregate concrete in 28 days.
The present embodiment measure 28 days regenerated aggregate concretes compression strength, rupture strength, adhesion strength and water absorption rate and
Shrinkage factor is 72.15MPa, 32.8MPa, 4.6MPa, 0.26% and 0.30% respectively.
Embodiment 3
A kind of regenerated aggregate concrete, its raw material constitutes percentage and is：Cement 19%, water 8%, natural coarse aggregate
0.5%th, waste and old concrete regenerated coarse aggregate 65%, methacrylic acid 0.05%, neopentyl glycol 0.08%, composite toughening material 0.63%,
Flyash 6%, polyacrylate 0.7%, early strength agent 0.03% and water reducer 0.01%.
Described water reducer is naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 18%.
The early strength agent is that nitrite, triethanolamine and acetic acid are 1 in mass ratio:1:1 mixing.
Described composite toughening material is a kind of composite available for concrete activeness and quietness, and its preparation method is：
After the activated processing of halloysite nanotubes, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into acyl chlorides
After functional group, and difunctional organic compound reaction, then reacted with Cyanuric Chloride, obtain surface and there is active chloride triazine ring
Halloysite nanotubes, finally prepared with methylcellulose by nucleophilic substitution, specifically include following steps：
（1）By the halloysite nanotubes of activated processing（30 kg）And thionyl chloride（60 kg）In 1-METHYLPYRROLIDONE（230
L）Middle mixing, is stirred at 55 DEG C after 6 h, in ultrasound 10h at 80 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine,
Then 30 min are centrifuged with 5000 rpm rotating speed, after separating solid and being cleaned through carbon tetrachloride, then the vacuum drying at 35 DEG C
30 h；
（2）Take step（1）Handle obtained halloysite nanotubes（30 kg）, ethylenediamine（8 kg）And triethylamine（6 L）In N- first
Base pyrrolidones（220 L）Middle mixing, is stirred at 60 DEG C after 5 h, under nitrogen protection, in 20 kHz, 150 KW ultrasound
In after the h of ultrasonic reaction 6 at 85 DEG C, removing triethylamine and 1-METHYLPYRROLIDONE, then blended solvent R under reduced pressure in ripple cleaning machine
（It is made up of ethanol, acetone and water, wherein the volume ratio of ethanol, acetone and water is 2:2:6）After cleaning, it is dried in vacuo at 20 DEG C
24 h；
（3）Take step（2）Handle obtained halloysite nanotubes（20 kg）And Cyanuric Chloride（5 kg）In tetrahydrofuran（230
L）Middle mixing, stirs 12 h at 10 DEG C, in after ultrasound 3h at 10 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then
Reacted at 10 DEG C after 24 h, cleaned through tetrahydrofuran, 24 h are dried in vacuo at 15 DEG C；
（4）Take step（3）Handle obtained halloysite nanotubes（20 kg）In N, N '-dimethyl formamide（200 L）Middle dissolving
Afterwards, it is added to and is dissolved with methylcellulose（5 kg, viscosity average molecular weigh is 20000, and substitution value is 2.0）N, N '-dimethyl first
Amide solution（50 L ）In, 5 h are stirred at 20 DEG C, in ultrasonic at 20 DEG C in 40 kHz, 300 KW supersonic wave cleaning machine
1 h, is warming up to after 60 DEG C, the h of isothermal reaction 36 under nitrogen protection, then is warming up to 95 DEG C, and isothermal reaction 24h is removed under reduced pressure molten
Agent, after being eluted with water, is dried in vacuo after 48 h at 40 DEG C, obtains the composite toughening material.
Above-mentioned steps（1）Described in halloysite nanotubes activation process step：
（A）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（B）In two L ball grinders of identical 15（Nylon tank）In each stainless steel ball for loading 60 a diameter of 5 mm and 50
A diameter of 10 mm stainless steel ball, is then respectively adding through step（A）The kg of halloysite nanotubes 6 after processing, then drip respectively
Plus 600 ml absolute ethyl alcohols, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are in rotating speed
Under conditions of 350 rpm and every 30 minutes automatic conversion direction of rotation after the h of ball milling 56, it is the short of 200 nm to obtain average length
Cut halloysite nanotubes；
（C）Take step（B）The halloysite nanotubes after handling that are chopped are added to the water that pH is the polysorbas20 that 8, concentration is 15 wt%
Ultrasonic 24 h in solution, filtering is stand-by after 30 h in being dried in vacuo at 68-70 DEG C after being eluted with water.
Described halloysite nanotubes are commercially available prod, its main specifications：Character：White powder；Composition：SiO2：58.1、
Al2O3：41.02、TiO2：0.17、Fe2O3：0.38、P2O5：0.16；Bore：15-22 nm；Pipe external diameter：40-70 nm；It is long
Degree：<1.5 μm；Specific surface area：53.4 m2/g；Density：2.5-2.6g/cm3。
Described polysorbas20 is commercially available, its main specifications：Character：Pale yellow viscous liquid；Active matter：98-99%；Acid number
(KOHmg/g)：≤1.0；Hydroxyl value (KOHmg/g)：80-108；HLB value：16.7；Saponification number (KOHmg/g)：40-50；Moisture content
(%)：≤1.0.
The preparation process of regenerated aggregate concrete as described above is as follows：
1）Cement, natural coarse aggregate, waste and old concrete regenerated coarse aggregate and flyash are added into mixer, it is dry to stir 3 minutes；
2）Then sequentially add methacrylic acid, neopentyl glycol, composite toughening material, polyacrylate, early strength agent, water reducer and
Water continues to stir 10 minutes；
3）By concreting, mark is supported and obtains regenerated aggregate concrete in 28 days.
The present embodiment measure 28 days regenerated aggregate concretes compression strength, rupture strength, adhesion strength and water absorption rate and
Shrinkage factor is 75.65MPa, 33.4MPa, 4.9MPa, 0.25% and 0.29% respectively.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (9)
1. a kind of regenerated aggregate concrete, it is characterised in that：Percentage, the raw material of the concrete, which is constituted, is：Water
Mud 15-20%, water 5-15%, natural coarse aggregate 0.5-40%, waste and old concrete regenerated coarse aggregate 30-70%, methacrylic acid 0.03-
0.05%th, neopentyl glycol 0.02-0.08%, composite toughening material 0.5-1%, flyash 5-10%, polyacrylate 0.5-1%, morning are strong
Agent 0.01-0.03% and water reducer 0.01-0.03%, the percetage by weight sum of above-mentioned each raw material is 100%；Wherein natural thick bone
The content sum of material and waste and old concrete regenerated coarse aggregate is 50%-70.5%；The preparation method of described composite toughening material is：
After halloysite nanotubes activation process, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into acyl chlorides official
Can be after group, and difunctional organic compound reaction, then reacted with Cyanuric Chloride, obtain surface and there is active chloride triazine ring
Halloysite nanotubes, are finally prepared with methylcellulose by nucleophilic substitution；In the composite toughening material, Ai Luo
The mass ratio of stone nanotube and methylcellulose is 1:0.1-0.5.
2. regenerated aggregate concrete according to claim 1, it is characterised in that：Described water reducer is naphthalene series high-efficiency diminishing
Agent, its water-reducing rate is 18-24%；The early strength agent is villaumite, sulfate, nitrate, nitrite, triethanolamine, acetic acid and second
One or more in hydrochlorate.
3. regenerated aggregate concrete according to claim 1, it is characterised in that：The preparation side of described composite toughening material
Method, specifically includes following steps：
（1）The halloysite nanotubes and thionyl chloride of activated processing are mixed in organic solvent P, stirred at 40-55 DEG C
After 6-15 h, in ultrasound 10-16 h at 70-80 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then with 4000-
5000 rpm rotating speed centrifugation 30-40 min, after separating solid and being cleaned through organic solvent Q, then the vacuum drying at 25-35 DEG C
30-50 h；
（2）Take step（1）Obtained halloysite nanotubes are handled with difunctional organic compound and triethylamine in organic solvent P
Middle mixing, is stirred after 5-15 h at 50-60 DEG C, under nitrogen protection, in 20 kHz, 150 KW supersonic wave cleaning machine
In after ultrasonic reaction 6-10 h at 70-85 DEG C, removing triethylamine and organic solvent P under reduced pressure, then after blended solvent R is cleaned,
24-48 h are dried in vacuo at 10-20 DEG C；
（3）Take step（2）Handle obtained halloysite nanotubes and Cyanuric Chloride is mixed in tetrahydrofuran, stirred at 0-10 DEG C
12-24 h are mixed, in after ultrasound 3-8 h at 0-10 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then at 0-10 DEG C
React after 24-72 h, cleaned through tetrahydrofuran, 24-56 h are dried in vacuo at 10-15 DEG C；
（4）Take step（3）After the halloysite nanotubes that processing is obtained dissolve in N, N '-dimethyl formamide, dissolving is added to
Have in the N of methylcellulose, N '-dimethyl formamide solution, 5-10 h are stirred at 10-20 DEG C, in 40 kHz, 300 KW
In ultrasound 1-5 h at 10-20 DEG C in supersonic wave cleaning machine, 40-60 DEG C, isothermal reaction 36-56 h are warming up under nitrogen protection
Afterwards, then it is warming up to 80-95 DEG C, isothermal reaction 24-48h removes solvent under reduced pressure, after being eluted with water, and 24- is dried in vacuo at 40 DEG C
After 48 h, the composite toughening material is obtained.
4. regenerated aggregate concrete according to claim 3, it is characterised in that：The organic solvent P is toluene, N- methyl
One or more in pyrrolidones and N, N '-dimethyl acetamide；The organic solvent Q is anhydrous propanone or carbon tetrachloride；
The mixed solvent R is made up of ethanol, acetone and water, and wherein the volume ratio of ethanol, acetone and water is 2:2:6.
5. regenerated aggregate concrete according to claim 3, it is characterised in that：Step（2）Described in difunctional it is organic
Compound is one kind in 1,3- propane diamine, ethylenediamine and l, 6- hexamethylene diamine.
6. regenerated aggregate concrete according to claim 3, it is characterised in that：Step（1）In, the Ai Luo of activated processing
Stone nanotube is 6-30 kg, and thionyl chloride is 10-60 kg；Organic solvent P is 50-230 L；Step（2）In, the galapectite
Nanotube is 5-30 kg, and difunctional organic compound is 1-8 kg, and triethylamine is 1-6 L, and organic solvent P is 50-220 L；
Step（3）In, the halloysite nanotubes are 5-20 kg, and Cyanuric Chloride is 0.5-5 kg, and tetrahydrofuran is 60-230 L；Step
Suddenly（4）In, the halloysite nanotubes are 5-20 kg, dissolve the N of halloysite nanotubes, and N '-dimethyl formamide is 50-200
L, methylcellulose is 1-5 kg, dissolves the N of methylcellulose, and N '-dimethyl formamide is 10-50 L.
7. regenerated aggregate concrete according to claim 3, it is characterised in that：Step（4）Described in methylcellulose
Viscosity average molecular weigh be 3000-20000, substitution value is 0.5-2.0.
8. regenerated aggregate concrete according to claim 3, it is characterised in that：Step（1）Described in galapectite nanometer
The activation process step of pipe is：
（A）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（B）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L ball grinders of identical 15
Mm stainless steel ball, is then respectively adding through step（A）The kg of halloysite nanotubes 6 after processing, then be added dropwise respectively 600 ml without
Water-ethanol, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, rotating speed be 350 rpm and
Under conditions of every 30 minutes automatic conversion direction of rotation after ball milling 40-56 h, average length being chopped for 200-230 nm is obtained
Halloysite nanotubes；
（C）Take step（B）The halloysite nanotubes after handling that are chopped are added to the water that pH is the polysorbas20 that 8, concentration is 15 wt%
Ultrasonic 24 h in solution, filtering is stand-by after 30 h in being dried in vacuo at 68-70 DEG C after being eluted with water.
9. a kind of method for preparing regenerated aggregate concrete as claimed in claim 1, it is characterised in that：Specifically include following step
Suddenly：
1）Cement, natural coarse aggregate, waste and old concrete regenerated coarse aggregate and flyash are added into mixer, it is dry to stir 2-3 minutes；
2）Then sequentially add methacrylic acid, neopentyl glycol, polyacrylate, composite toughening material, early strength agent, water reducer and
Water continues to stir 5-10 minutes；
3）By concreting, mark is supported and obtains within 28 days the high tenacity regenerated aggregate concrete.
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| CN108892438A (en) * | 2018-09-29 | 2018-11-27 | 福建江夏学院 | A kind of high tenacity lightweight concrete and preparation method thereof |
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| CN105622132A (en) * | 2015-12-30 | 2016-06-01 | 中环建筑（福建）有限公司 | Sponge-city environment-friendly recycled-aggregate pervious concrete and preparing method thereof |
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| CN104030596A (en) * | 2014-06-30 | 2014-09-10 | 湖南省建筑工程集团总公司 | Alkaline-free anti-crack concrete shrinkage reducing agent |
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