CN107021691A - A kind of marine environment corrosion resistant composite toughening concrete and preparation method thereof - Google Patents
A kind of marine environment corrosion resistant composite toughening concrete and preparation method thereof Download PDFInfo
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- CN107021691A CN107021691A CN201710400689.0A CN201710400689A CN107021691A CN 107021691 A CN107021691 A CN 107021691A CN 201710400689 A CN201710400689 A CN 201710400689A CN 107021691 A CN107021691 A CN 107021691A
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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
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
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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
- C04B28/02—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 containing hydraulic cements other than calcium sulfates
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/24—Sea water resistance
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Abstract
The present invention provides a kind of marine environment corrosion resistant composite toughening concrete and preparation method thereof, and the primary raw material of concrete includes by weight：200 300 parts of cement, 46 parts of water reducer, 100 120 parts of water, 20 30 parts of composite toughening material, 10 15 parts of dispersant, 100 200 parts of filler, fine aggregate 400 500,200 300 parts of coarse aggregate, 300 500 parts of sea sand, 10 20 parts of polyacrylate.Concrete corrosion resistant performance can improve 50 80%, and durability can improve more than 60%.
Description
Technical field
The invention belongs to building material technical field, and in particular to a kind of marine environment corrosion resistant composite toughening concrete and its
Preparation method.
Background technology
With the large-scale economic society construction of China, especially sea island ecosystem job facilities construction increases increasingly, existing rank
Section, the facility of common water-proof concrete material processing can not resist the long-time immersion of seawater, corrode, and reduce making for facility
With life-span and using effect.For marine ecology engineering, existing marine ecology engineering concrete facility is due to by sea
Water erosion, is highly vulnerable to breakage, the effect that influence marine ecology engineering ecology is built.In order to improve marine ecology engineering concrete facility
Service life, effectively resistant to sea water can corrode, it is necessary to which a kind of feedstock capture is easy to process, adhesive force strong, the high-strength height of anti-seawater
Toughness concrete.
The composite of the concrete activeness and quietness of the present invention, by the halloysite nanotubes and first of activeness and quietness excellent performance
Base cellulose is combined, by multi-step surface covalent reaction, forms a kind of unique compound system, the composite wood prepared
Material can be fully dispersed in concrete, effectively plays the effect of material coordination plasticizing, concrete is integrally had well tough
Property, fatigue resistance and isotropism, be a kind of high performance concrete activeness and quietness composite, assign concrete good tough
Property, isotropism, fatigue resistance, the marine environment corrosion resistant composite toughening concrete of preparation has good strength and toughness, has
There is good durability, meet ocean engineering and use.
The content of the invention
It is an object of the invention to provide a kind of marine environment corrosion resistant composite toughening concrete and preparation method thereof, the present invention
Using a kind of composite available for concrete activeness and quietness, it is the basis of the activated processing of original halloysite nanotubes
On, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into after acid chloride functional groups, organised with difunctional
Compound reacts, then is reacted with Cyanuric Chloride, obtains the halloysite nanotubes that surface has active chloride triazine ring, finally and methyl
Cellulose is prepared by nucleophilic substitution.In the composite, the quality of halloysite nanotubes and methylcellulose
Content ratio about 1:0.1-0.5, can make gained concrete have good toughness, fatigue resistance, isotropism, shock resistance, resist
Shake and cracking resistance.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of marine environment corrosion resistant high tenacity concrete its raw materials used include by weight：
200-300 parts of cement, 4-6 parts of water reducer, 100-120 parts of water, 20-30 parts of composite toughening material, 10-15 parts of dispersant,
100-200 parts of filler, fine aggregate 400-500,200-300 parts of coarse aggregate, 300-500 parts of sea sand, 10-20 parts of polyacrylate.
The water reducer is commercially available naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 18-24%.
The dispersant is methylcellulose.
The preparation method of composite toughening material, it comprises the following steps：
（1）By the halloysite nanotubes and thionyl chloride of activated processing in organic solvent P, 6-15 is stirred at 40-55 DEG C
After 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 centrifuges 30-40 min, after separating solid and being cleaned through organic solvent Q, then is dried in vacuo 30-50 at 25-35 DEG C
h；
（2）By above-mentioned steps（1）Halloysite nanotubes, difunctional organic compound and the triethylamine of processing are 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）By above-mentioned steps（2）The halloysite nanotubes and Cyanuric Chloride of processing are mixed in tetrahydrofuran, are 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）By above-mentioned steps（3）After the halloysite nanotubes of processing 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, then in 40 kHz, 300 KW
Supersonic wave cleaning machine in ultrasound 1-5 h at 10-20 DEG C, 40-60 DEG C of isothermal reaction 36-56 h is warming up under nitrogen protection
Afterwards, then 80-95 DEG C of isothermal reaction 24-48h is warming up to, removes solvent under reduced pressure, after being eluted with water, 24- is dried in vacuo at 40 DEG C
Composite toughening material product is obtained after 48 h.
Above-mentioned steps（1）In activated processing halloysite nanotubes be 6-30 kg, thionyl chloride be 10-60 kg；Have
Machine solvent P is 50-230 L.
Above-mentioned steps（1）In organic solvent P be toluene, 1-METHYLPYRROLIDONE or N, in N '-dimethyl acetamide
It is one or more of.
Above-mentioned steps（1）In organic solvent Q be one kind in anhydrous propanone or carbon tetrachloride.
Above-mentioned steps（2）In halloysite nanotubes be 5-30 kg；Difunctional organic compound is 1-8 kg；Three second
Amine is 1-6 L；Organic solvent P is 50-220 L.
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（2）In mixed solvent R be made up of ethanol, acetone and water, the wherein volume ratio of ethanol, acetone and water
For 2:2:6.
Above-mentioned steps（3）In halloysite nanotubes be 5-20 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 60-
230 L。
Above-mentioned steps（4）In halloysite nanotubes be 5-20 kg；Dissolve the N of halloysite nanotubes, N '-dimethyl first
Acid amides is 50-200 L；Methylcellulose is 1-5 kg；The N of methylcellulose is dissolved, N '-dimethyl formamide is 10-50 L.
Above-mentioned steps（4）In methylcellulose viscosity average molecular weigh be 3000-20000, substitution value is 0.5-2.0.
In above-mentioned steps（1）Described in the activation process of halloysite nanotubes of activated processing comprise the following steps：
1）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding through step 1）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；
3）Take step 2）It is the water-soluble of the polysorbas20 that 8, concentration is 15 wt% that the halloysite nanotubes after handling that are chopped, which are added to pH,
Ultrasonic 24 h in liquid, filtering after being eluted with water, is received in being dried in vacuo galapectite that activation process is obtained after 30 h at 68-70 DEG C
Mitron.
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.
Compared with the prior art, technical scheme has the advantages that：
Composite environment provided by the present invention available for concrete activeness and quietness is friendly, has in conventional organic solvent
Good dissolubility, has good dispersiveness in water.The preparation condition of the composite is readily satisfied, and raw material sources are rich
Richness, cost is relatively low.
The composite of the concrete activeness and quietness of the present invention, by the halloysite nanotubes and first of activeness and quietness excellent performance
Base cellulose is combined, by multi-step surface covalent reaction, forms a kind of unique compound system, can be in concrete
It is fully dispersed, effectively play the effect of material coordination plasticizing, make concrete integrally have good toughness, fatigue resistance and it is each to
The same sex, is a kind of high performance concrete activeness and quietness composite.
The preparation method of sea sand described in B comprises the following steps：
（1）Sea sand pre-sifted：Sea sand is sieved, the sea sand that particle diameter is 5-10mm is obtained；
（2）Sea sand purged with fresh water：By step（1）Sea sand and desalinize seawater by quality and volume ratio 3g：7ml ratio mixing,
Appropriate diatomite and magnetic particle valency hole carbon are added, 2-3h is handled in stirring at normal temperature；
（3）Separation：By step（2）Sea sand after purified treatment is drained；
（4）Heat treatment：By step（3）The sea sand that drains adds that mixer is dry to be stirred 2-3 minute, drying box is inserted after taking-up, heating
Heated 20-30 minutes to 50-60 DEG C, then proceed to 80-100 DEG C of heating and continue to heat 30 minutes, be then further continued for being heated to
190-210 DEG C, continue to heat 25 minutes, be then quickly cooled to take out after 25-30 DEG C, 15 minutes, sieve, remove again
Desalted sea sand finished product is obtained after diatomite and magnetic particle valency hole carbon.
Above-mentioned steps（2）In magnetic particle valency hole carbon preparation method comprise the following steps:
1）By SBA-15, sucrose, the concentrated sulfuric acid, water in mass ratio 1:1.5:0.16:7 well mixed prepare turn into solution, at 60 DEG C
Lower heating 1-2 hours, is then warming up to 100-120 DEG C and dries 1.5 hours, continues to be heated to 180 DEG C, carries out pre- carbonization 3 hours
It is stand-by；
2）By step 1）The material of preparation, sucrose, the concentrated sulfuric acid, iron chloride, water in mass ratio 2:10:1:10:65 mixing, it is quick to add
Heat continues to be carbonized 1 hour, then proceedes to be warming up to 185 DEG C, be carbonized 30 min again, be then cooled fast to often to 160 DEG C
Temperature, adds commercially available ammoniacal liquor, removes SBA-15 templates, that is, obtains magnetic particle valency hole carbon.
Intermediary hole carbon of the present invention has big specific surface area and pore volume, compensate for the deficiency of activated carbon.
The preparation method of filler described in C comprises the following steps：
（1）Coral is crushed, sieved, particle size range 1-3mm coral fragment is chosen, is rinsed with water, dry standby；
（2）Modifying agent is configured, SBS and organobentonite are well mixed, loads high
In fast mixer, disperse under 350-400r/min rotating speeds after 1-2 h, be warming up to 50-80 DEG C, add solubilizer, in 500-
Disperse under 600 r/min rotating speeds after 10-20 min, be put into cold mixing pot and cool down, adjust pH value to 7-8 with sodium hydroxide, changed
Property agent；
（3）Coral fragment is put into step（2）Modifying agent in modification, under 350-400r/min rotating speeds disperse 30-
After 50min, 100-110 DEG C is warming up to, normal temperature is then cooled fast to, infiltrated 2-3 hours in stirring at normal temperature, mended in impregnation process
It is hydrogenated with sodium oxide molybdena maintenance system pH value 7-8；
（4）Coral sand after modification is drained at normal temperatures, the filler needed.
Hole in coral sand includes intergranular outer hole and the inner pore of particle in itself, porosity 50%.Relatively
It is coral sand light weight, porous for other materials, gathered materials on the spot on island, coral is modified and prepares filler, for sea
The purification of island engineering water, good purification, filtrate cost is low, can realize that seawater is a certain degree of using natural coral sand
Purification, but because coral sand porosity is high and aperture is larger, the function that impurity is stored after adsorbing contaminant is weak, in filter process
Impurity is easily again introduced into seawater, influences clean-up effect, method of modifying of the invention solves this problem well, by its property
More than 100% can be improved.
D is by cement, water reducer, composite toughening material, dispersant, filler, fine aggregate, coarse aggregate, sea sand, polyacrylic acid
Ester is mixed in proportion, is stirred 10-15 minutes, is then proportionally added into water, is stirred 30 minutes, obtains the compound increasing of marine environment corrosion resistant
Tough concrete, concrete corrosion resistant performance can improve 50-80%, and durability can improve more than 60%.
Specific embodiment：
Illustrate technical scheme with specific embodiment below, but the present invention includes scope not limited to this：
Embodiment 1：
It is as follows using matching：250 parts of cement, 5 parts of water reducer, 100 parts of water, 25 parts of composite toughening material, 15 parts of dispersant, are filled out
150 parts of material, 400 parts of fine aggregate, 300 parts of coarse aggregate, 300 parts of sea sand, 15 parts of polyacrylate.
The water reducer is commercially available naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 18-24%.
The dispersant is methylcellulose.
The preparation method of composite toughening material, comprises the following steps：
（1）By the halloysite nanotubes and thionyl chloride of activated processing in organic solvent P, stirred at 50 DEG C after 10 h,
In ultrasonic 13 h at 75 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then 35 are centrifuged with 4500 rpm rotating speed
Min, after separating solid and being cleaned through organic solvent Q, then at 30 DEG C is dried in vacuo 40h；
（2）By above-mentioned steps（1）Halloysite nanotubes, difunctional organic compound and the triethylamine of processing are in organic solvent P
Middle mixing, at 55 DEG C stir 10h after, under nitrogen protection, in 20 kHz, 150 KW supersonic wave cleaning machine in 80 DEG C
After lower ultrasonic reaction 8h, triethylamine and organic solvent P are removed under reduced pressure, then after blended solvent R is cleaned, be dried in vacuo at 15 DEG C
36h；
（3）By above-mentioned steps（2）The halloysite nanotubes and Cyanuric Chloride of processing are mixed in tetrahydrofuran, are stirred at 5 DEG C
18h, in after ultrasonic 5 h at 5 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then reacts after 48 h at 5 DEG C, through four
Hydrogen furans is cleaned, and 40 h are dried in vacuo at 12 DEG C；
（4）By above-mentioned steps（3）After the halloysite nanotubes of processing dissolve in N, N '-dimethyl formamide, dissolving is added to
Have in the N of methylcellulose, N '-dimethyl formamide solution, 8 h are stirred at 15 DEG C, then in 40 kHz, 300 KW ultrasound
In ultrasound 3h at 15 DEG C in ripple cleaning machine, it is warming up under nitrogen protection after 50 DEG C of h of isothermal reaction 46, then be warming up to 90 DEG C of perseverances
Temperature reaction 36h, removes solvent under reduced pressure, after being eluted with water, is dried in vacuo at 40 DEG C after 36 h and obtains composite toughening material product.
The organic solvent P is 1-METHYLPYRROLIDONE；The organic solvent Q is carbon tetrachloride；The difunctional has
Machine compound ethylenediamine；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。
Step（1）In activated processing halloysite nanotubes be 20kg, thionyl chloride be 40 kg；Organic solvent P is
150 L。
Step（2）In halloysite nanotubes be 15 kg；Difunctional organic compound is 5 kg；Triethylamine is 4 L；
Organic solvent P is 170 L.
Step（3）In halloysite nanotubes be 10 kg；Cyanuric Chloride is 2 kg；Tetrahydrofuran is 150L.
Step（4）In halloysite nanotubes be 10 kg；The N of halloysite nanotubes is dissolved, N '-dimethyl formamide is
100 L；Methylcellulose is 3 kg；The N of methylcellulose is dissolved, N '-dimethyl formamide is 30 L.
Step（4）In methylcellulose viscosity average molecular weigh be 10000, substitution value is 1.0.
Step（1）Described in the activation process of halloysite nanotubes of activated processing comprise the following steps：
1）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
2）Respectively load 60 a diameter of 5 mm stainless steel ball and 50 a diameter of 10 mm in two L nylon tanks of identical 15
Stainless steel ball, be then respectively adding through step 1）The kg of halloysite nanotubes 6 after processing, then that 600 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are 350 rpm and every in rotating speed
Under conditions of 30 minutes automatic conversion direction of rotation after the h of ball milling 50, the chopped galapectite nanometer that average length is 220 nm is obtained
Pipe；
3）Take step 2）It is the water-soluble of the polysorbas20 that 8, concentration is 15 wt% that the halloysite nanotubes after handling that are chopped, which are added to pH,
Ultrasonic 24 h in liquid, filtering, after being eluted with water, in be dried in vacuo at 69 DEG C activation process is obtained after 30 h galapectite nanometer
Pipe.
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 method of sea sand described in B comprises the following steps：
（1）Sea sand pre-sifted：Sea sand is sieved, the sea sand that particle diameter is 5-10mm is obtained；
（2）Sea sand purged with fresh water：By step（1）Sea sand and desalinize seawater by quality and volume ratio 3g：7ml ratio mixing,
Appropriate diatomite and magnetic particle valency hole carbon are added, 2h is handled in stirring at normal temperature；
（3）Separation：By step（2）Sea sand after purified treatment is drained；
（4）Heat treatment：By step（3）The sea sand that drains adds that mixer is dry to be stirred 2 minutes, and drying box is inserted after taking-up, is warming up to
55 DEG C are heated 25 minutes, are then proceeded to 90 DEG C of heating and are continued to heat 30 minutes, be then further continued for being heated to 200 DEG C, continue to heat
Processing 25 minutes, is then quickly cooled to take out after 25 DEG C, 15 minutes, sieves again, remove diatomite and magnetic particle valency hole
Desalted sea sand finished product is obtained after carbon.
Above-mentioned steps（2）In magnetic particle valency hole carbon preparation method comprise the following steps:
1）By SBA-15, sucrose, the concentrated sulfuric acid, water in mass ratio 1:1.5:0.16:7 well mixed prepare turn into solution, at 60 DEG C
Lower heating 1 hour, is then warming up to 110 DEG C and dries 1.5 hours, continue to be heated to 180 DEG C, carries out pre- carbonization 3 hours stand-by；
2）By step 1）The material of preparation, sucrose, the concentrated sulfuric acid, iron chloride, water in mass ratio 2:10:1:10:65 mixing, quickly
160 DEG C are heated to, continues to be carbonized 1 hour, then proceedes to be warming up to 185 DEG C, be carbonized 30 min again, be then cooled fast to often
Temperature, adds commercially available ammoniacal liquor, removes SBA-15 templates, that is, obtains magnetic particle valency hole carbon.
The preparation method of filler described in C comprises the following steps：
（1）Coral is crushed, sieved, particle size range 1-3mm coral fragment is chosen, is rinsed with water, dry standby；
（2）Modifying agent is configured, SBS and organobentonite are well mixed, loads high
In fast mixer, disperse under 350r/min rotating speeds after 1h, be warming up to 70 DEG C, add solubilizer, under 600 r/min rotating speeds
After scattered 15 min, it is put into cold mixing pot and cools down, adjusts pH value to 7 with sodium hydroxide, obtain modifying agent；
（3）Coral fragment is put into step（2）Modifying agent in modification, under 350r/min rotating speeds disperse 40min after, rise
Then temperature is cooled fast to normal temperature to 100 DEG C, is infiltrated 2 hours in stirring at normal temperature, and sodium hydroxide is added in impregnation process and maintains body
It is pH value 7；
（4）Coral sand after modification is drained at normal temperatures, the filler needed.
D is by cement, water reducer, composite toughening material, dispersant, filler, fine aggregate, coarse aggregate, sea sand, polyacrylic acid
Ester is mixed in proportion, is stirred 12 minutes, is then proportionally added into water, is stirred 30 minutes, is obtained marine environment corrosion resistant composite toughening
Concrete, compression strength is 42Mpa, and concrete corrosion resistant performance can improve 60%, and durability can improve 62%.
Embodiment 2：
It is as follows using matching：300 parts of cement, 4 parts of water reducer, 100 parts of water, 30 parts of composite toughening material, 10 parts of dispersant, are filled out
150 parts of material, 450 parts of fine aggregate, 300 parts of coarse aggregate, 300 parts of sea sand, 15 parts of polyacrylate.
The water reducer is commercially available naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 18-24%.
The dispersant is methylcellulose.
The preparation method of composite toughening material, comprises the following steps：
（1）By the halloysite nanotubes and thionyl chloride of activated processing in organic solvent P, stirred at 55 DEG C after 15 h,
In ultrasonic 16 h at 80 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then 40 are centrifuged with 5000 rpm rotating speed
Min, after separating solid and being cleaned through organic solvent Q, then is dried in vacuo at 35 DEG C 50 h；
（2）By above-mentioned steps（1）Halloysite nanotubes, difunctional organic compound and the triethylamine of processing are in organic solvent P
Middle mixing, is stirred at 60 DEG C after 15 h, under nitrogen protection, in 20 kHz, 150 KW supersonic wave cleaning machine in 85
At DEG C after the h of ultrasonic reaction 10, triethylamine and organic solvent P are removed under reduced pressure, then after blended solvent R is cleaned, the vacuum at 20 DEG C
Dry 48 h；
（3）By above-mentioned steps（2）The halloysite nanotubes and Cyanuric Chloride of processing are mixed in tetrahydrofuran, are stirred at 10 DEG C
24 h, in after ultrasonic 8 h at 10 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then react after 72 h at 10 DEG C,
Cleaned through tetrahydrofuran, 56 h are dried in vacuo at 15 DEG C；
（4）By above-mentioned steps（3）After the halloysite nanotubes of processing dissolve in N, N '-dimethyl formamide, dissolving is added to
Have in the N of methylcellulose, N '-dimethyl formamide solution, stir 10 h at 20 DEG C, then 40 kHz, 300 KW it is super
In ultrasonic 5 h at 20 DEG C in sound wave cleaning machine, it is warming up under nitrogen protection after 60 DEG C of h of isothermal reaction 56, then be warming up to 95 DEG C
Isothermal reaction 48h, removes solvent under reduced pressure, after being eluted with water, and is dried in vacuo at 40 DEG C after 48 h and obtains the production of composite toughening material
Product.
The organic solvent P is N, N '-dimethyl acetamide；The organic solvent Q is carbon tetrachloride；The difunctional
Organic compound is l, 6- hexamethylene diamines；The mixed solvent R is made up of ethanol, acetone and water, wherein the body of ethanol, acetone and water
Product is than being 2:2:6.
Step（1）In activated processing halloysite nanotubes be 30 kg, thionyl chloride be 60 kg；Organic solvent P is
230 L。
Step（2）In halloysite nanotubes be 30 kg；Difunctional organic compound is 8 kg；Triethylamine is 6 L；
Organic solvent P is 220 L.
Step（3）In halloysite nanotubes be 20 kg；Cyanuric Chloride is 5 kg；Tetrahydrofuran is 230 L.
Step（4）In halloysite nanotubes be 20 kg；The N of halloysite nanotubes is dissolved, N '-dimethyl formamide is
200 L；Methylcellulose is 5 kg；The N of methylcellulose is dissolved, N '-dimethyl formamide is 50 L.
Step（4）In methylcellulose viscosity average molecular weigh be 20000, substitution value is 2.0.
Step（1）Described in the activation process of halloysite nanotubes of activated processing comprise the following steps：
1）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
2）Respectively load 60 a diameter of 5 mm stainless steel ball and 50 a diameter of 10 mm in two L nylon tanks of identical 15
Stainless steel ball, be then respectively adding through step 1）The kg of halloysite nanotubes 6 after processing, then that 600 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are 350 rpm and every in rotating speed
Under conditions of 30 minutes automatic conversion direction of rotation after the h of ball milling 56, the chopped galapectite nanometer that average length is 230 nm is obtained
Pipe；
3）Take step 2）It is the water-soluble of the polysorbas20 that 8, concentration is 15 wt% that the halloysite nanotubes after handling that are chopped, which are added to pH,
Ultrasonic 24 h in liquid, filtering, after being eluted with water, in be dried in vacuo at 70 DEG C activation process is obtained after 30 h galapectite nanometer
Pipe.
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 method of sea sand described in B comprises the following steps：
（1）Sea sand pre-sifted：Sea sand is sieved, the sea sand that particle diameter is 5-10mm is obtained；
（2）Sea sand purged with fresh water：By step（1）Sea sand and desalinize seawater by quality and volume ratio 3g：7ml ratio mixing,
Appropriate diatomite and magnetic particle valency hole carbon are added, 3h is handled in stirring at normal temperature；
（3）Separation：By step（2）Sea sand after purified treatment is drained；
（4）Heat treatment：By step（3）The sea sand that drains adds that mixer is dry to be stirred 3 minutes, and drying box is inserted after taking-up, is warming up to
60 DEG C are heated 30 minutes, are then proceeded to 100 DEG C of heating and are continued to heat 30 minutes, be then further continued for being heated to 210 DEG C, continue to heat
Processing 25 minutes, is then quickly cooled to take out after 30 DEG C, 15 minutes, sieves again, remove diatomite and magnetic particle valency hole
Desalted sea sand finished product is obtained after carbon.
Above-mentioned steps（2）In magnetic particle valency hole carbon preparation method comprise the following steps:
1）By SBA-15, sucrose, the concentrated sulfuric acid, water in mass ratio 1:1.5:0.16:7 well mixed prepare turn into solution, at 60 DEG C
Lower heating 2 hours, is then warming up to 120 DEG C and dries 1.5 hours, continue to be heated to 180 DEG C, carries out pre- carbonization 3 hours stand-by；
2）By step 1）The material of preparation, sucrose, the concentrated sulfuric acid, iron chloride, water in mass ratio 2:10:1:10:65 mixing, quickly
160 DEG C are heated to, continues to be carbonized 1 hour, then proceedes to be warming up to 185 DEG C, be carbonized 30 min again, be then cooled fast to often
Temperature, adds commercially available ammoniacal liquor, removes SBA-15 templates, that is, obtains magnetic particle valency hole carbon.
The preparation method of filler described in C comprises the following steps：
（1）Coral is crushed, sieved, particle size range 1-3mm coral fragment is chosen, is rinsed with water, dry standby；
（2）Modifying agent is configured, SBS and organobentonite are well mixed, loads high
In fast mixer, disperse under 400r/min rotating speeds after 2 h, be warming up to 80 DEG C, add solubilizer, in 600 r/min rotating speeds
Disperse after 20 min down, be put into cold mixing pot and cool down, adjust pH value to 8 with sodium hydroxide, obtain modifying agent；
（3）Coral fragment is put into step（2）Modifying agent in modification, under 400r/min rotating speeds disperse 50min after, rise
Then temperature is cooled fast to normal temperature to 110 DEG C, is infiltrated 3 hours in stirring at normal temperature, and sodium hydroxide is added in impregnation process and maintains body
It is pH value 8；
（4）Coral sand after modification is drained at normal temperatures, the filler needed.
D is by cement, water reducer, composite toughening material, dispersant, filler, fine aggregate, coarse aggregate, sea sand, polyacrylic acid
Ester is mixed in proportion, is stirred 15 minutes, is then proportionally added into water, is stirred 30 minutes, is obtained marine environment corrosion resistant composite toughening
Concrete, compression strength is 48Mpa, and concrete corrosion resistant performance can improve 65%, and durability can improve 68%.
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 (7)
1. a kind of marine environment corrosion resistant composite toughening concrete, it is characterised in that the concrete primary raw material is by weight
Including：200-300 parts of cement, 4-6 parts of water reducer, 100-120 parts of water, 20-30 parts of composite toughening material, 10-15 parts of dispersant,
100-200 parts of filler, fine aggregate 400-500,200-300 parts of coarse aggregate, 300-500 parts of sea sand, 10-20 parts of polyacrylate；
The water reducer is commercially available naphthalene series high-efficiency water-reducing agent, and its water-reducing rate is 18-24%；
The dispersant is methylcellulose.
2. marine environment corrosion resistant composite toughening concrete according to claim 1, it is characterised in that the composite toughening material
The preparation method of material, comprises the following steps：
（1）By the halloysite nanotubes and thionyl chloride of activated processing in organic solvent P, 6-15 is stirred at 40-55 DEG C
After 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 centrifuges 30-40 min, after separating solid and being cleaned through organic solvent Q, then is dried in vacuo 30-50 at 25-35 DEG C
h；
（2）By above-mentioned steps（1）Halloysite nanotubes, difunctional organic compound and the triethylamine of processing are 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）By above-mentioned steps（2）The halloysite nanotubes and Cyanuric Chloride of processing are mixed in tetrahydrofuran, are 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）By above-mentioned steps（3）After the halloysite nanotubes of processing 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, then in 40 kHz, 300 KW
Supersonic wave cleaning machine in ultrasound 1-5 h at 10-20 DEG C, 40-60 DEG C of isothermal reaction 36-56 h is warming up under nitrogen protection
Afterwards, then 80-95 DEG C of isothermal reaction 24-48h is warming up to, removes solvent under reduced pressure, after being eluted with water, 24- is dried in vacuo at 40 DEG C
Composite toughening material product is obtained after 48 h；
The organic solvent P is the one or more in toluene, 1-METHYLPYRROLIDONE or N, N '-dimethyl acetamide；It is described
Organic solvent Q is one kind in anhydrous propanone or carbon tetrachloride；The difunctional organic compound is 1,3- propane diamine, second two
One kind in amine and l, 6- hexamethylene diamine；The mixed solvent R is made up of ethanol, acetone and water, wherein the body of ethanol, acetone and water
Product is than being 2:2:6；
Above-mentioned steps（1）In activated processing halloysite nanotubes be 6-30 kg, thionyl chloride be 10-60 kg；It is organic molten
Agent P is 50-230 L；
Above-mentioned steps（2）In halloysite nanotubes be 5-30 kg；Difunctional organic compound is 1-8 kg；Triethylamine is
1-6 L；Organic solvent P is 50-220 L；
Above-mentioned steps（3）In halloysite nanotubes be 5-20 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 60-230
L；
Above-mentioned steps（4）In halloysite nanotubes be 5-20 kg；Dissolve the N of halloysite nanotubes, N '-dimethyl formamide
For 50-200 L；Methylcellulose is 1-5 kg；The N of methylcellulose is dissolved, N '-dimethyl formamide is 10-50 L；
Above-mentioned steps（4）In methylcellulose viscosity average molecular weigh be 3000-20000, substitution value is 0.5-2.0.
3. marine environment corrosion resistant composite toughening concrete according to claim 2, it is characterised in that step（1）Described in
The activation process of the halloysite nanotubes of activated processing comprises the following steps：
1）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding through step 1）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；
3）Take step 2）It is the water-soluble of the polysorbas20 that 8, concentration is 15 wt% that the halloysite nanotubes after handling that are chopped, which are added to pH,
Ultrasonic 24 h in liquid, filtering after being eluted with water, is received in being dried in vacuo galapectite that activation process is obtained after 30 h at 68-70 DEG C
Mitron.
4. marine environment corrosion resistant composite toughening concrete according to claim 1, it is characterised in that the preparation of the sea sand
Method comprises the following steps：
（1）Sea sand pre-sifted：Sea sand is sieved, the sea sand that particle diameter is 5-10mm is obtained；
（2）Sea sand purged with fresh water：By step（1）Sea sand and desalinize seawater by quality and volume ratio 3g：7ml ratio mixing,
Appropriate diatomite and magnetic particle valency hole carbon are added, 2-3h is handled in stirring at normal temperature；
（3）Separation：By step（2）Sea sand after purified treatment is drained；
（4）Heat treatment：By step（3）The sea sand that drains adds that mixer is dry to be stirred 2-3 minute, drying box is inserted after taking-up, heating
Heated 20-30 minutes to 50-60 DEG C, then proceed to 80-100 DEG C of heating and continue to heat 30 minutes, be then further continued for being heated to
190-210 DEG C, continue to heat 25 minutes, be then quickly cooled to take out after 25-30 DEG C, 15 minutes, sieve, remove again
Desalted sea sand finished product is obtained after diatomite and magnetic particle valency hole carbon.
5. marine environment corrosion resistant composite toughening concrete according to claim 4, it is characterised in that step（2）In magnetic
Property particle valency hole carbon preparation method comprises the following steps:
1）By SBA-15, sucrose, the concentrated sulfuric acid, water in mass ratio 1:1.5:0.16:7 well mixed prepare turn into solution, at 60 DEG C
Lower heating 1-2 hours, is then warming up to 100-120 DEG C and dries 1.5 hours, continues to be heated to 180 DEG C, carries out pre- carbonization 3 hours
It is stand-by；
2）By step 1）The material of preparation, sucrose, the concentrated sulfuric acid, iron chloride, water in mass ratio 2:10:1:10:65 mixing, quickly
160 DEG C are heated to, continues to be carbonized 1 hour, then proceedes to be warming up to 185 DEG C, be carbonized 30 min again, be then cooled fast to often
Temperature, adds commercially available ammoniacal liquor, removes SBA-15 templates, that is, obtains magnetic particle valency hole carbon.
6. marine environment corrosion resistant composite toughening concrete according to claim 1, it is characterised in that the preparation of the filler
Method comprises the following steps：
（1）Coral is crushed, sieved, particle size range 1-3mm coral fragment is chosen, is rinsed with water, dry standby；
（2）Modifying agent is configured, SBS and organobentonite are well mixed, loads high
In fast mixer, disperse under 350-400r/min rotating speeds after 1-2 h, be warming up to 50-80 DEG C, add solubilizer, in 500-
Disperse under 600 r/min rotating speeds after 10-20 min, be put into cold mixing pot and cool down, adjust pH value to 7-8 with sodium hydroxide, changed
Property agent；
（3）Coral fragment is put into step（2）Modifying agent in modification, under 350-400r/min rotating speeds disperse 30-
After 50min, 100-110 DEG C is warming up to, normal temperature is then cooled fast to, infiltrated 2-3 hours in stirring at normal temperature, mended in impregnation process
It is hydrogenated with sodium oxide molybdena maintenance system pH value 7-8；
（4）Coral sand after modification is drained at normal temperatures, the filler needed.
7. a kind of method of the marine environment corrosion resistant composite toughening concrete prepared as described in claim 1-6 is any, its feature
It is,
By cement, water reducer, composite toughening material, dispersant, filler, fine aggregate, coarse aggregate, sea sand, polyacrylate press than
Example mixing, is stirred 10-15 minutes, is then proportionally added into water, is stirred 30 minutes, is obtained marine environment corrosion resistant composite toughening coagulation
Soil.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109250963A (en) * | 2018-09-29 | 2019-01-22 | 福建省昊立建设工程有限公司 | A kind of composite toughening concrete and preparation method thereof |
| CN113716921A (en) * | 2021-10-21 | 2021-11-30 | 深圳市港龙混凝土有限公司 | High-strength durable recycled concrete |
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|---|---|---|---|---|
| CN105621966A (en) * | 2014-10-29 | 2016-06-01 | 西安优信机电工程有限公司 | Fiber-reinforced concrete with uniform surface color |
| CN106045423A (en) * | 2016-05-25 | 2016-10-26 | 象州县科学技术局 | Method for producing prefabricated member of concrete ditch by using coal gangue |
| CN106587855A (en) * | 2017-01-05 | 2017-04-26 | 蔡中元 | Anti-microbial and anti-corrosion concrete material for marine ecological engineering and preparation method for concrete material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105621966A (en) * | 2014-10-29 | 2016-06-01 | 西安优信机电工程有限公司 | Fiber-reinforced concrete with uniform surface color |
| CN106045423A (en) * | 2016-05-25 | 2016-10-26 | 象州县科学技术局 | Method for producing prefabricated member of concrete ditch by using coal gangue |
| CN106587855A (en) * | 2017-01-05 | 2017-04-26 | 蔡中元 | Anti-microbial and anti-corrosion concrete material for marine ecological engineering and preparation method for concrete material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109250963A (en) * | 2018-09-29 | 2019-01-22 | 福建省昊立建设工程有限公司 | A kind of composite toughening concrete and preparation method thereof |
| CN113716921A (en) * | 2021-10-21 | 2021-11-30 | 深圳市港龙混凝土有限公司 | High-strength durable recycled concrete |
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