CN107140887A - A kind of marine environment corrosion resistant high tenacity concrete and preparation method thereof - Google Patents
A kind of marine environment corrosion resistant high tenacity concrete and preparation method thereof Download PDFInfo
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- CN107140887A CN107140887A CN201710401004.4A CN201710401004A CN107140887A CN 107140887 A CN107140887 A CN 107140887A CN 201710401004 A CN201710401004 A CN 201710401004A CN 107140887 A CN107140887 A CN 107140887A
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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
- 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
- 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
- C04B20/04—Heat 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
- 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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- 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 present invention provides a kind of marine environment corrosion resistant high tenacity concrete and preparation method thereof, and the primary raw material of the concrete includes by weight：200 300 parts of cement, 46 parts of water reducer, 100 120 parts of water, 20 30 parts of 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.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 high tenacity concrete and its system
Preparation Method.
Background technology
With the large-scale economic society construction of China, especially sea island ecosystem job facilities construction increases increasingly, existing
Stage, the facility of common water-proof concrete material processing can not resist the long-time immersion of seawater, corrode, and reduce facility
Service life and using effect.For marine ecology engineering, existing marine ecology engineering concrete facility due to
By sea water intrusion, it is highly vulnerable to breakage, the effect that influence marine ecology engineering ecology is built.In order to improve marine ecology engineering coagulation
The service life of native facility, effectively resistant to sea water can corrode, it is necessary to which a kind of feedstock capture is easy to process, adhesive force strong, anti-seawater
High-strength and high-ductility concrete.
The concrete toughness reinforcing of the present invention is fine using the excellent modification galapectite of toughness reinforcing efficiency and ethoxy with modified galapectite
Dimension element, by multi-step surface modification reaction, two kinds of toughening materials is effectively combined, so as to form a kind of unique composite toughening
System.The modification galapectite prepared can be fully dispersed in concrete, effectively plays the effect of material coordination plasticizing, assigns mixed
The good toughness of solidifying soil, isotropism, fatigue resistance, are a kind of high performance concrete toughening materials.The concrete of the present invention increases
It is tough to be easily well mixed with modified galapectite with other concrete components, then can obtain toughness reinforcing coagulation after marking and supporting
Native product, the marine environment corrosion resistant high tenacity concrete of preparation has good strength and toughness, with good durability, full
Sufficient ocean engineering is used.
The content of the invention
It is an object of the invention to provide a kind of marine environment corrosion resistant high tenacity concrete its preparation method, the present invention is used
A kind of modification galapectite available for concrete toughness reinforcing, it is anti-with thionyl chloride first using the galapectite of activated processing
Should, then with difunctional organic compound reaction, make galapectite area load labile functional groups, then reacted with Cyanuric Chloride,
The galapectite that surface has active chloride triazine ring is obtained, is finally prepared into hydroxyethyl cellulose by nucleophilic substitution
Arrive.In the modification galapectite, the mass content ratio of hydroxyethyl cellulose and galapectite is about 0.1-0.3:1.
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 toughening material, 10-15 parts of dispersant, filler
100-200 parts, 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.
Toughening material described in A is modified galapectite, and its preparation method comprises the following steps：
（1）By the galapectite and thionyl chloride of activated processing in organic solvent J, stirred at 30-50 DEG C after 5-12 h,
In ultrasound 8-12 h at 60-80 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then with 3500-5000 rpm turn
Speed centrifugation 20-30 min, after separating solid and being cleaned through organic solvent K, then the vacuum drying 24-48 h at 30-40 DEG C；
（2）By above-mentioned steps（1）Galapectite, difunctional organic compound and the 3- picolines of processing are in organic solvent J
Mixing, is stirred after 3-12 h at 40-50 DEG C, under nitrogen protection, in 20 kHz, 100 KW supersonic wave cleaning machine in
At 80-90 DEG C after ultrasonic reaction 5-8 h, 3- picolines and organic solvent J are evaporated off, then after blended solvent L is cleaned, in 10-
24-36 h are dried in vacuo at 20 DEG C；
（3）By above-mentioned steps（2）The galapectite and Cyanuric Chloride of processing are mixed in tetrahydrofuran, and 12- is stirred at 0-10 DEG C
24 h, in after ultrasound 2-6 h at 0-10 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then react at 0-10 DEG C
After 30-72 h, cleaned through tetrahydrofuran, 24-48 h are dried in vacuo at 10-15 DEG C；
（4）By above-mentioned steps（3）After the galapectite of processing dissolves in 1-METHYLPYRROLIDONE, it is added to and is dissolved with ethoxy fibre
In the pyridine solution for tieing up element, 3-10 h are stirred at 10-20 DEG C, in 10-20 in 40 kHz, 200 KW supersonic wave cleaning machine
Ultrasound 1-3 h at DEG C, are warming up to after 40-60 DEG C of isothermal reaction 24-48 h, then be warming up to 83-95 DEG C of constant temperature under nitrogen protection
24-48 h are reacted, solvent is evaporated off, after being eluted with water, obtain being modified galapectite product after being dried in vacuo 24-48 h at 50 DEG C.
Above-mentioned steps（1）In activated processing galapectite be 1-20 kg, thionyl chloride be 5-50 kg；Organic solvent J
For 30-200 L.
Above-mentioned steps（1）In organic solvent J be dimethylbenzene, 1-METHYLPYRROLIDONE or N, in N '-dimethyl formamide
One kind.
Above-mentioned steps（1）In organic solvent K be one kind in tetrahydrofuran or acetone.
Above-mentioned steps（2）In galapectite be 3-20 kg；Difunctional organic compound is 1-5 kg；3- picolines
For 1-5 L；Organic solvent J is 50-200 L.
Above-mentioned steps（2）In difunctional organic compound be ethylene glycol and 1,3- propane diols in one kind.
Above-mentioned steps（2）In mixed solvent L be made up of ethanol, acetone and water, the wherein volume ratio of ethanol, acetone and water
For 3:1:6.
Above-mentioned steps（3）In galapectite be 2-18 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 50-200 L.
Above-mentioned steps（4）In galapectite be 2-15 kg；1-METHYLPYRROLIDONE is 50-260 L；Hydroxyethyl cellulose
For 1-5 kg；Pyridine is 20-80 L.
Above-mentioned steps（4）In hydroxyethyl cellulose viscosity average molecular weigh be 5000-30000, substitution value is 0.5-2.5.
In above-mentioned steps（1）Described in the activation process of galapectite of activated processing comprise the following steps：
1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
2）Respectively load 55 a diameter of 5 mm stainless steel ball and 50 a diameter of 10 mm in two L nylon tanks of identical 12
Stainless steel ball, be then respectively adding through step 1）The kg of galapectite 5 after processing, then 500 ml absolute ethyl alcohols are added dropwise respectively, and
Sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every 60 minutes in rotating speed
Under conditions of automatic conversion direction of rotation after ball milling 45-50 h, the chopped galapectite that average length is 180-200 nm is obtained；
3）Take step 2）The galapectite after handling that is chopped is added in the aqueous solution that pH is the Tween 40 that 8, concentration is 12 wt%
20 h of ultrasound, filtering, after being eluted with water, in being dried in vacuo galapectite that activation process is obtained after 24 h at 65-67 DEG C.
Described galapectite is commercially available, its main specifications：Character：White powder；Density：2.4-2.5g/cm3；Constitute into
Point：SiO2：58.23、Al2O3：40.96、Fe2O3：0.34、TiO2：0.15、P2O5：0.14；Pipe external diameter：40-60 nm；Bore：
15-20 nm；Length：<1.1 μm；Specific surface area：52.6 m2/g。
Described Tween 40 (CAS No. 9005-66-7) is commercially available, its main specifications：Character：Amber oily liquid
Body；Acid number (KOHmg/g)：≤2.0；Hydroxyl value (KOHmg/g)：85-100；HLB value：15.5；Saponification number (KOHmg/g)：40-55；
Moisture content (%)：≤2.5.
Compared with the prior art, technical scheme has the advantages that：
Concrete toughness reinforcing provided by the present invention is environment-friendly with modified galapectite, has good dispersiveness in water.This changes
Property galapectite preparation condition readily satisfy, and raw material sources are abundant, and cost is relatively low.
The concrete toughness reinforcing of the present invention is fine using the excellent modification galapectite of toughness reinforcing efficiency and ethoxy with modified galapectite
Dimension element, by multi-step surface modification reaction, two kinds of toughening materials is effectively combined, so as to form a kind of unique composite toughening
System.The modification galapectite prepared can be fully dispersed in concrete, effectively plays the effect of material coordination plasticizing, assigns
Concrete integrally has good toughness, isotropism, fatigue resistance, is a kind of high performance concrete toughening material, the present invention
The modified galapectite of concrete toughness reinforcing can easily mix and be uniformly dispersed with other concrete components.
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 3:10:1:10:65 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.
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 etc. is mixed in proportion, is stirred 10-15 minutes, is then proportionally added into water, is stirred 30 minutes, you can obtain marine environment corrosion resistant
High tenacity 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 toughening material, 15 parts of dispersant, filler 150
Part, 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.
Toughening material described in A is modified galapectite, and its preparation method comprises the following steps：
（1）By the galapectite and thionyl chloride of activated processing in organic solvent J, stirred at 40 DEG C after 8 h, 20
In ultrasonic 10 h at 70 DEG C in kHz, 100 KW supersonic wave cleaning machine, 25 min are then centrifuged with 4000 rpm rotating speed, point
After being cleaned from solid and through organic solvent K, then it is dried in vacuo at 35 DEG C 36 h；
（2）By above-mentioned steps（1）Galapectite, difunctional organic compound and the 3- picolines of processing are in organic solvent J
Mixing, stirred at 45 DEG C after 8 h, under nitrogen protection, in 20 kHz, 100 KW supersonic wave cleaning machine at 85 DEG C
After the h of ultrasonic reaction 6,3- picolines and organic solvent J are evaporated off, then after blended solvent L is cleaned, be dried in vacuo at 15 DEG C
30 h；
（3）By above-mentioned steps（2）The galapectite and Cyanuric Chloride of processing are mixed in tetrahydrofuran, and 18 h are stirred at 5 DEG C,
In after ultrasonic 4 h at 5 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then react after 51h at 5 DEG C, through tetrahydrofuran
Clean, 36 h are dried in vacuo at 12 DEG C；
（4）By above-mentioned steps（3）After the galapectite of processing dissolves in 1-METHYLPYRROLIDONE, it is added to and is dissolved with ethoxy fibre
In the pyridine solution for tieing up element, 7 h are stirred at 15 DEG C, in ultrasonic at 15 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine
2h, is warming up to after 50 DEG C of h of isothermal reaction 36 under nitrogen protection, then is warming up to 90 DEG C of h of isothermal reaction 36, and solvent is evaporated off, and uses
After water is cleaned, it is dried in vacuo at 50 DEG C after 36 h and obtains being modified galapectite product.
The organic solvent J is 1-METHYLPYRROLIDONE；The organic solvent K is acetone；The difunctional organises
Compound is 1,3- propane diols；The mixed solvent L is made up of ethanol, acetone and water, and the volume ratio of wherein ethanol, acetone and water is
3:1:6。
Step（1）In activated processing galapectite be 10 kg, thionyl chloride be 20 kg；Organic solvent J is 100 L.
Step（2）In galapectite be 10kg；Difunctional organic compound is 3 kg；3- picolines are 3 L；It is organic
Solvent J is 150 L.
Step（3）In galapectite be 10 kg；Cyanuric Chloride is 2 kg；Tetrahydrofuran is 100L.
Step（4）In galapectite be 10 kg；1-METHYLPYRROLIDONE is 150 L；Hydroxyethyl cellulose is 3 kg；Pyrrole
Pyridine is 50L.
Step（4）In hydroxyethyl cellulose viscosity average molecular weigh be 10000, substitution value is 1.0.
Step（1）Described in the activation process of galapectite of activated processing comprise the following steps：
1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
2）Respectively load 55 a diameter of 5 mm stainless steel ball and 50 a diameter of 10 mm in two L nylon tanks of identical 12
Stainless steel ball, be then respectively adding through step 1）The kg of galapectite 5 after processing, then 500 ml absolute ethyl alcohols are added dropwise respectively, and
Sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every 60 minutes in rotating speed
Under conditions of automatic conversion direction of rotation after the h of ball milling 48, the chopped galapectite that average length is 190 nm is obtained；
3）Take step 2）The galapectite after handling that is chopped is added in the aqueous solution that pH is the Tween 40 that 8, concentration is 12 wt%
20 h of ultrasound, filtering, after being eluted with water, in being dried in vacuo galapectite that activation process is obtained after 24 h at 66 DEG C.
Described galapectite is commercially available, its main specifications：Character：White powder；Density：2.4-2.5g/cm3；Constitute into
Point：SiO2：58.23、Al2O3：40.96、Fe2O3：0.34、TiO2：0.15、P2O5：0.14；Pipe external diameter：40-60 nm；Bore：
15-20 nm；Length：<1.1 μm；Specific surface area：52.6 m2/g。
Described Tween 40 (CAS No. 9005-66-7) is commercially available, its main specifications：Character：Amber oily liquid
Body；Acid number (KOHmg/g)：≤2.0；Hydroxyl value (KOHmg/g)：85-100；HLB value：15.5；Saponification number (KOHmg/g)：40-55；
Moisture content (%)：≤2.5.
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 3:10:1:10:65 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 1 h, be warming up to 70 DEG C, add solubilizer, in 600 r/min rotating speeds
Disperse after 15 min down, be put into cold mixing pot and cool down, adjust 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 etc. is mixed in proportion, is stirred 10 minutes, is then proportionally added into water, is stirred 30 minutes, you can obtain marine environment corrosion resistant high
Toughness concrete, compression strength is 42Mpa, and concrete corrosion resistant performance can improve 63%, and durability can improve 65%.
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.
Toughening material described in A is modified galapectite, and its preparation method comprises the following steps：
（1）By the galapectite and thionyl chloride of activated processing in organic solvent J, stirred at 50 DEG C after 12 h, 20
In ultrasonic 12 h at 80 DEG C in kHz, 100 KW supersonic wave cleaning machine, 30 min are then centrifuged with 5000 rpm rotating speed, point
After being cleaned from solid and through organic solvent K, then it is dried in vacuo at 40 DEG C 48 h；
（2）By above-mentioned steps（1）Galapectite, difunctional organic compound and the 3- picolines of processing are in organic solvent J
Mixing, stirred at 50 DEG C after 12 h, under nitrogen protection, in 20 kHz, 100 KW supersonic wave cleaning machine in 90 DEG C
After the lower h of ultrasonic reaction 8,3- picolines and organic solvent J are evaporated off, then after blended solvent L is cleaned, vacuum is done at 20 DEG C
Dry 36 h；
（3）By above-mentioned steps（2）The galapectite and Cyanuric Chloride of processing are mixed in tetrahydrofuran, and 24 h are stirred at 10 DEG C,
In after ultrasonic 6 h at 10 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then react after 72 h at 10 DEG C, through four
Hydrogen furans is cleaned, and 48 h are dried in vacuo at 15 DEG C；
（4）By above-mentioned steps（3）After the galapectite of processing dissolves in 1-METHYLPYRROLIDONE, it is added to and is dissolved with ethoxy fibre
In the pyridine solution for tieing up element, 10 h are stirred at 20 DEG C, in ultrasonic at 20 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine
3 h, are warming up to after 60 DEG C of h of isothermal reaction 48 under nitrogen protection, then are warming up to 95 DEG C of h of isothermal reaction 48, and solvent is evaporated off, and use
After water is cleaned, it is dried in vacuo at 50 DEG C after 48 h and obtains being modified galapectite product.
The organic solvent J is N, N '-dimethyl formamide；The organic solvent K is tetrahydrofuran；The difunctional
Organic compound is ethylene glycol；The mixed solvent L is made up of ethanol, acetone and water, wherein the volume ratio of ethanol, acetone and water
For 3:1:6.
Step（1）In activated processing galapectite be 20 kg, thionyl chloride be 50 kg；Organic solvent J is 200 L.
Step（2）In galapectite be 20 kg；Difunctional organic compound is 5 kg；3- picolines are 5 L；Have
Machine solvent J is 200 L.
Step（3）In galapectite be 18 kg；Cyanuric Chloride is 5 kg；Tetrahydrofuran is 200 L.
Step（4）In galapectite be 15 kg；1-METHYLPYRROLIDONE is 260 L；Hydroxyethyl cellulose is 5 kg；Pyrrole
Pyridine is 80 L.
Step（4）In hydroxyethyl cellulose viscosity average molecular weigh be 30000, substitution value is 2.5.
Step（1）Described in the activation process of galapectite of activated processing comprise the following steps：
1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
2）Respectively load 55 a diameter of 5 mm stainless steel ball and 50 a diameter of 10 mm in two L nylon tanks of identical 12
Stainless steel ball, be then respectively adding through step 1）The kg of galapectite 5 after processing, then 500 ml absolute ethyl alcohols are added dropwise respectively, and
Sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every 60 minutes in rotating speed
Under conditions of automatic conversion direction of rotation after the h of ball milling 50, the chopped galapectite that average length is 200 nm is obtained；
3）Take step 2）The galapectite after handling that is chopped is added in the aqueous solution that pH is the Tween 40 that 8, concentration is 12 wt%
20 h of ultrasound, filtering, after being eluted with water, in being dried in vacuo galapectite that activation process is obtained after 24 h at 67 DEG C.
Described galapectite is commercially available, its main specifications：Character：White powder；Density：2.4-2.5g/cm3；Constitute into
Point：SiO2：58.23、Al2O3：40.96、Fe2O3：0.34、TiO2：0.15、P2O5：0.14；Pipe external diameter：40-60 nm；Bore：
15-20 nm；Length：<1.1 μm；Specific surface area：52.6 m2/g。
Described Tween 40 (CAS No. 9005-66-7) is commercially available, its main specifications：Character：Amber oily liquid
Body；Acid number (KOHmg/g)：≤2.0；Hydroxyl value (KOHmg/g)：85-100；HLB value：15.5；Saponification number (KOHmg/g)：40-55；
Moisture content (%)：≤2.5.
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 3: 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 etc. is mixed in proportion, is stirred 15 minutes, is then proportionally added into water, is stirred 30 minutes, you can obtain marine environment corrosion resistant high
Toughness concrete, compression strength is 48Mpa, and concrete corrosion resistant performance can improve 68%, and durability can improve 71%.
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 high tenacity concrete, it is characterised in that the concrete primary raw material is wrapped by weight
Include：200-300 parts of cement, 4-6 parts of water reducer, 100-120 parts of water, 20-30 parts of toughening material, 10-15 parts of dispersant, filler
100-200 parts, 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 high tenacity concrete according to claim 1, it is characterised in that the toughening material is to change
Property galapectite, its preparation method comprises the following steps：
（1）By the galapectite and thionyl chloride of activated processing in organic solvent J, stirred at 30-50 DEG C after 5-12 h,
In ultrasound 8-12 h at 60-80 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then with 3500-5000 rpm turn
Speed centrifugation 20-30 min, after separating solid and being cleaned through organic solvent K, then the vacuum drying 24-48 h at 30-40 DEG C；
（2）By above-mentioned steps（1）Galapectite, difunctional organic compound and the 3- picolines of processing are in organic solvent J
Mixing, is stirred after 3-12 h at 40-50 DEG C, under nitrogen protection, in 20 kHz, 100 KW supersonic wave cleaning machine in
At 80-90 DEG C after ultrasonic reaction 5-8 h, 3- picolines and organic solvent J are evaporated off, then after blended solvent L is cleaned, in 10-
24-36 h are dried in vacuo at 20 DEG C；
（3）By above-mentioned steps（2）The galapectite and Cyanuric Chloride of processing are mixed in tetrahydrofuran, and 12- is stirred at 0-10 DEG C
24 h, in after ultrasound 2-6 h at 0-10 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then react at 0-10 DEG C
After 30-72 h, cleaned through tetrahydrofuran, 24-48 h are dried in vacuo at 10-15 DEG C；
（4）By above-mentioned steps（3）After the galapectite of processing dissolves in 1-METHYLPYRROLIDONE, it is added to and is dissolved with ethoxy fibre
In the pyridine solution for tieing up element, 3-10 h are stirred at 10-20 DEG C, in 10-20 in 40 kHz, 200 KW supersonic wave cleaning machine
Ultrasound 1-3 h at DEG C, are warming up to after 40-60 DEG C of isothermal reaction 24-48 h, then be warming up to 83-95 DEG C of constant temperature under nitrogen protection
24-48 h are reacted, solvent is evaporated off, after being eluted with water, obtain being modified galapectite product after being dried in vacuo 24-48 h at 50 DEG C；
The organic solvent J is one kind in dimethylbenzene, 1-METHYLPYRROLIDONE or N, N '-dimethyl formamide；It is described organic
Solvent K is one kind in tetrahydrofuran or acetone；The difunctional organic compound is in ethylene glycol and 1,3- propane diols
It is a kind of；The mixed solvent L is made up of ethanol, acetone and water, and wherein the volume ratio of ethanol, acetone and water is 3:1:6；
Above-mentioned steps（1）In activated processing galapectite be 1-20 kg, thionyl chloride be 5-50 kg；Organic solvent J is 30-
200 L；
Above-mentioned steps（2）In galapectite be 3-20 kg；Difunctional organic compound is 1-5 kg；3- picolines are 1-5
L；Organic solvent J is 50-200 L；
Above-mentioned steps（3）In galapectite be 2-18 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 50-200 L；
Above-mentioned steps（4）In galapectite be 2-15 kg；1-METHYLPYRROLIDONE is 50-260 L；Hydroxyethyl cellulose is 1-5
kg；Pyridine is 20-80 L；
Above-mentioned steps（4）In hydroxyethyl cellulose viscosity average molecular weigh be 5000-30000, substitution value is 0.5-2.5.
3. marine environment corrosion resistant high tenacity concrete according to claim 2, it is characterised in that step（1）Described in pass through
The activation process of the galapectite of activation process comprises the following steps：
1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
2）Respectively load 55 a diameter of 5 mm stainless steel ball and 50 a diameter of 10 mm in two L nylon tanks of identical 12
Stainless steel ball, be then respectively adding through step 1）The kg of galapectite 5 after processing, then 500 ml absolute ethyl alcohols are added dropwise respectively, and
Sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every 60 minutes in rotating speed
Under conditions of automatic conversion direction of rotation after ball milling 45-50 h, the chopped galapectite that average length is 180-200 nm is obtained；
3）Take step 2）The galapectite after handling that is chopped is added in the aqueous solution that pH is the Tween 40 that 8, concentration is 12 wt%
20 h of ultrasound, filtering, after being eluted with water, in being dried in vacuo galapectite that activation process is obtained after 24 h at 65-67 DEG C.
4. marine environment corrosion resistant high tenacity concrete according to claim 1, it is characterised in that the preparation side 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 high tenacity concrete according to claim 4, it is characterised in that step（2）In magnetic
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 3：10:1:10:65 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 high tenacity concrete according to claim 1, it is characterised in that the preparation side 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 high tenacity concrete prepared as described in claim 1-6 is any, its feature exists
In by cement, water reducer, composite toughening material, dispersant, filler, fine aggregate, coarse aggregate, sea sand, polyacrylate etc. is pressed
Ratio is mixed, and is stirred 10-15 minutes, is then proportionally added into water, is stirred 30 minutes, you can obtain marine environment corrosion resistant high tenacity
Concrete, concrete corrosion resistant performance can improve 50-80%, and durability can improve more than 60%.
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|---|---|---|---|---|
| CN1472157A (en) * | 2003-06-19 | 2004-02-04 | 同济大学 | High-toughness fibre mixed concrete and preparing method thereof |
| CN104058676A (en) * | 2014-07-15 | 2014-09-24 | 宏峰集团(福建)有限公司 | High-toughness concrete and preparation method thereof |
| CN105541212A (en) * | 2015-12-30 | 2016-05-04 | 福建江夏学院 | Composite material toughened ceramisite concrete and preparation method thereof |
| 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 |
| CN106625998A (en) * | 2017-01-05 | 2017-05-10 | 周文婧 | Corrosion-resistant concrete prefabricated part for marine ecological engineering and preparation method thereof |
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2017
- 2017-05-31 CN CN201710401004.4A patent/CN107140887A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472157A (en) * | 2003-06-19 | 2004-02-04 | 同济大学 | High-toughness fibre mixed concrete and preparing method thereof |
| CN104058676A (en) * | 2014-07-15 | 2014-09-24 | 宏峰集团(福建)有限公司 | High-toughness concrete and preparation method thereof |
| CN105541212A (en) * | 2015-12-30 | 2016-05-04 | 福建江夏学院 | Composite material toughened ceramisite concrete and preparation method thereof |
| 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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Application publication date: 20170908 |