CN112979238A - Low-shrinkage high-performance concrete - Google Patents
Low-shrinkage high-performance concrete Download PDFInfo
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- CN112979238A CN112979238A CN202110170706.2A CN202110170706A CN112979238A CN 112979238 A CN112979238 A CN 112979238A CN 202110170706 A CN202110170706 A CN 202110170706A CN 112979238 A CN112979238 A CN 112979238A
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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
- C04B28/04—Portland 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/34—Non-shrinking or non-cracking materials
- C04B2111/343—Crack resistant materials
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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
Abstract
The invention discloses low-shrinkage high-performance concrete, which consists of the following materials: 500 parts of P.O 52.5 ordinary portland cement 400-containing material, 30-50 parts of biomass incineration ash, 25-50 parts of viscosity modified mineral admixture, 650 parts of continuous graded river sand with fineness modulus of 2.8 and 1-5 mm, 60-150 parts of ceramic sand, 1000 parts of continuous graded broken stone with 5-20 mm, 3.0-6.5 parts of super-dispersion high-adaptability water reducing agent, 1.0-2.5 parts of super slump retaining and viscosity reducing slump retaining agent, 0.5-1.0 part of stabilizing pumping agent and 170 parts of water 145-containing material. According to the invention, the viscosity modification effect of the mineral admixture is utilized, and the ultra-dispersion high-adaptability and ultra-slump-retaining viscosity-reducing characteristics of the chemical admixture are combined, so that the working performance of high-performance concrete is improved, and stable pumping is realized; the synergistic internal curing effect of the biomass incineration ash and the ceramic sand is utilized to regulate and control the internal relative humidity of the high-performance concrete, reduce early self-shrinkage, inhibit the cracking of cast-in-place beams and other bridges, reduce self weight, improve mechanical properties and have important application value.
Description
Technical Field
The invention belongs to the field of building materials, relates to a silicate material, and particularly relates to low-shrinkage high-performance concrete.
Background
With the development of the national traffic industry, the proportion of bridges in traffic engineering is gradually increased. The cast-in-place beam structure is widely applied to bridge structures due to the clear stress, simple design, easy construction and short construction period. In order to realize the high bearing capacity of the bridge, strict requirements are put on the strength and the durability of concrete. The high-performance concrete has the characteristics of good workability, high early strength, high toughness, high volume stability and high durability, and has wide application prospect in cast-in-place beams.
However, the following problems still exist in the prior high-performance concrete: the high-performance concrete has the problems of large viscosity, large loss of fluidity over time and inconvenience for pumping due to low water consumption, poor adaptability of additives and materials and the like in the preparation process; the high-performance concrete cementing material has large consumption, so that the early hydration speed is high, the self-drying degree is high, the self-shrinkage is large, and the cast-in-place beam is easy to crack. Due to the characteristics of low water-gel ratio and compact structure of high-performance concrete, the traditional curing method cannot meet the requirements at all, and because external moisture is difficult to enter the interior of the concrete, the effect of inhibiting shrinkage cracking is low. The problem of early cracking of the high-performance concrete can be greatly reduced by adopting an internal curing method. The super-absorbent resin is adopted for internal curing, so that the self-shrinkage of concrete can be obviously reduced, but the density of the super-absorbent resin is low, the super-absorbent resin is easy to agglomerate in the stirring process, the uniform distribution and the curing effect of the super-absorbent resin in a cement-based material are influenced, pumping is not facilitated, holes can be formed in the concrete after water release, and the strength is reduced. These disadvantages all limit the widespread use of high-performance concrete in civil engineering. In view of the problems of the high-performance concrete, it is urgently needed to provide a low-shrinkage high-performance concrete, so that the concrete has good working performance, stable pumping performance and long-term mechanical performance, and meanwhile, the self-shrinkage can be reduced, and the early cracking of a cast-in-place beam can be inhibited.
Disclosure of Invention
The invention aims to provide low-shrinkage high-performance concrete aiming at the defects of the prior art, wherein the high-performance concrete has good working performance, stable pumping performance and long-term mechanical property, and simultaneously reduces self-shrinkage and inhibits early cracking of cast-in-place beams and other bridges.
In order to achieve the purpose, the invention adopts the following technical scheme:
the low-shrinkage high-performance concrete comprises the following components in percentage by weight: 500 parts of P.O 52.5 ordinary portland cement 400-containing material, 30-50 parts of biomass incineration ash, 25-50 parts of viscosity modified mineral admixture, 650 parts of continuous graded river sand with fineness modulus of 2.8 and 1-5 mm, 60-150 parts of ceramic sand, 1000 parts of continuous graded broken stone with 5-20 mm, 3.0-6.5 parts of super-dispersion high-adaptability water reducing agent, 1.0-2.5 parts of super slump retaining and viscosity reducing slump retaining agent, 0.5-1.0 part of stabilizing pumping agent and 170 parts of water 145-containing material.
Further, the biomass incineration ash SiO2The content is more than or equal to 80 percent, the water absorption is more than or equal to 10 percent, and the specific surface area is more than or equal to 40000m2/kg。
Further, the biomass incineration ash is composed of any one or more of rice hull ash, bamboo leaf ash, corncob ash, straw ash and elephant grass ash.
Further, the viscosity modified mineral admixture is composed of fly ash micro-beads and slag micro-powder.
Furthermore, the water demand ratio of the fly ash micro-beads is less than or equal to 95 percent, and the strength activity index in 28 days is more than or equal to 80 percent.
Furthermore, the moisture content of the slag micro-powder is less than or equal to 0.08 percent, and the 28d strength activity index is more than or equal to 100 percent.
Furthermore, the granularity range of the ceramic sand is 1mm-5mm, the cylinder pressure strength is more than or equal to 8MPa, and the saturated surface dry water absorption is more than or equal to 9%.
Further, the super-dispersion high-adaptability water reducing agent is prepared from a water reducing agent J1 and a water reducing agent J2 according to the proportion of 1:1-1: 5.
The water reducing agent J1 is prepared by the following steps:
(1): adding 16.80 parts of phenolic alcohol head and 0.8 part of boron trifluoride and lithium aluminum hydride with the mass ratio of 0.8: 2.3 into a 5L high-pressure reaction kettle provided with a stirrer and a temperature control device, performing nitrogen replacement for 3 times, then starting vacuumizing to gauge pressure of-0.09 MPa, then heating to 125 ℃, starting vacuum dehydration for 1h, continuing introducing nitrogen for replacement, measuring the oxygen content, stopping introducing nitrogen after the oxygen content is qualified, cooling to 115 ℃, starting to continuously introduce 61.0 parts of ethylene oxide and 242.1 parts of propylene oxide, controlling the pressure to be less than 0.4MPa, keeping the temperature at 120 ℃ after the introduction is finished, aging to negative pressure, cooling and discharging to obtain crude polyether;
(2): adding the prepared finished polyether into a reaction kettle, heating to 45 ℃ by adopting water bath, and then preserving heat for 0.5 hour; preparing 6.7 parts by mass of ammonium persulfate and azodiisobutyronitrile in a ratio of 2:1, 3.2 parts by mass of thioglycolic acid, mercaptoethanol and water in a ratio of 2:1.3 into solution A; preparing 5.6 parts by mass of ascorbic acid and sodium formaldehyde sulfoxylate in a ratio of 1:1.2, 33.0 parts by mass of acrylic acid and 0.7 part by mass of phenol alcohol head into solution B; dripping A, B into the reaction kettle by using a dripping pump, wherein the dripping of A is carried out for 2 hours, and the dripping of B is carried out for 1.5 hours, thus obtaining the polyether dispersant; adding 7.3 parts by mass of sodium bicarbonate and triisopropanolamine into the prepared water reducer according to the mass ratio of 1.3:1, and supplementing water until the total mass is 1000 to obtain a required polyether water reducer solution, namely the water reducer J1;
the water reducing agent J2 is prepared by the following steps:
(1): 99.22 parts of 2-methoxy-6-allylphenol and 1.2 parts of sodium hydroxide are added into a high-pressure reaction kettle provided with a stirrer and a temperature control device, after 3 times of nitrogen replacement, vacuumizing is started to gauge pressure of-0.098 MPa, then the temperature is increased to 120 ℃, vacuum dehydration is started for 1.5h, then nitrogen gas replacement is continuously introduced, the oxygen content is measured, after the oxygen content is qualified, the introduction of nitrogen gas is stopped, and the temperature is reduced to 115 ℃; introducing a cyclic monomer into the reaction kettle, introducing 83.91 parts of ethylene oxide and 55.42 parts of propylene oxide into the reaction kettle, controlling the pressure to be less than 0.4MPa, carrying out heat preservation and aging at the temperature of 125-140 ℃ to negative pressure after the introduction is finished, cooling and discharging to obtain crude polyether;
(2): placing the crude polyether in a reaction kettle, performing nitrogen negative pressure displacement for 3 times, heating to 125 ℃, stirring for 1.7h, cooling to 90 ℃, adding distilled water, stirring for 1h, heating to 120 ℃ while vacuumizing, cooling, and discharging to obtain a finished polyether product;
(3): adding the prepared finished product polyether into a reaction kettle, and heating to 45 ℃ by adopting water bath; preparing solution A from 5.9 parts of a composition of sodium hydrosulfite and sodium metabisulfite in a mass ratio of 1:1, 9.2 parts of a composition of ammonium persulfate and benzoyl peroxide in a mass ratio of 2:3, 4.3 parts of a composition of thioglycolic acid and mercaptoethanol in a mass ratio of 1:3 and water; 158.37 parts of vinyl sulfonic acid, 1.0 part of 2-methoxy-6-allyl phenol and water are prepared into solution B; respectively dripping the solution A and the solution B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is 1.1 hours, and the dripping of the solution B is 1.7 hours; after the A, B liquid is dripped, preserving heat for 1 hour to prepare the polyether water reducer;
(4): and adding 7.8 parts of potassium hydroxide into the prepared polyether water reducer, and supplementing water until the total mass is 1000 to obtain a required polyether water reducer solution, namely the water reducer J2.
Further, the super slump-retaining and viscosity-reducing slump retaining agent is prepared by the following steps:
(1): adding 18 parts of 2-ethoxy-3-butene-1-ol and 0.8 part of lithium aluminum hydride into a high-pressure reaction kettle provided with a stirrer and a temperature control device, performing nitrogen displacement for 3 times, vacuumizing to gauge pressure of-0.15 MPa, heating to 130 ℃, performing vacuum dehydration for 1h, introducing 305 parts of propylene oxide into the reaction kettle, controlling the pressure to be less than 0.5MPa, performing heat preservation and aging at 140 ℃ to negative pressure after introducing, cooling, and discharging to obtain the polyether monomer with the molecular weight of about 2000.
(2): adding the prepared finished product polyether into a reaction kettle, and heating to 55 ℃ by adopting water bath; preparing 3.4 parts of ammonium persulfate and water into solution A; preparing solution B from 46.0 parts of diethyl acrylate, 2 parts of 2-ethoxy-3-butene-1-ol, 4.6 parts of sodium bisulfite, 1.2 parts of mercaptopropionic acid, thioglycolic acid and water in a mass ratio of 1: 4.2; respectively dripping the solution A and the solution B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is carried out for 3 hours, and the dripping of the solution B is carried out for 2.5 hours; and (3) after the A, B liquid is dripped, preserving heat for 1 hour to obtain a polyether slump retaining agent, adding 12.4 parts of sodium hydroxide into the prepared polyether slump retaining agent, and supplementing water until the total mass is 1000 to obtain the super slump retaining and viscosity reducing slump retaining agent.
Further, the concrete stabilizing pumping agent is prepared from a pumping agent W1 and a pumping agent W2 according to the proportion of 1:1-3: 1.
The pumping agent W1 is prepared by the following steps:
(1): adding 25 parts of cyclohexyl-1, 4-dimethanol monovinyl ether into a high-pressure reaction kettle, adding 0.10 part of lithium aluminum hydride, then under the stirring, nitrogen is replaced for 4 times, heating is started, the temperature is raised to about 110 ℃, then 80 parts of ethylene oxide is slowly introduced into the reactor for induction reaction, the temperature is gradually raised to about 100-115 ℃ in the induction process, maintaining the constant temperature at 120 deg.C, maintaining the pressure at 0.25MPa, and maintaining the temperature for about 2 hr, when the pressure of the reactor is not reduced any more, adding 0.12 part of potassium hydroxide again, slowly introducing 240 parts of ethylene oxide and 13 parts of difluoromethanesulfonic acid into the container for induction reaction, maintaining the temperature at 125 ℃, when the pressure in the reactor is not reduced any more, reducing the temperature to 80 ℃, vacuumizing and degassing, and discharging to obtain an unsaturated intermediate with the molecular weight of about 400-;
(2): adding the unsaturated intermediate prepared in the step (1) and 350 parts of deionized water into a four-neck flask to serve as a bottom material, adding 120 parts of deionized water into 30 parts of acrylic acid to serve as a material A, preparing 1.2 parts of mercaptopropionic acid and thioglycollic acid in a mass ratio of 1:2, 4.5 parts of sodium hypophosphite and 50 parts of deionized water into a material B, and adding 60 parts of deionized water into 1.2 parts of ammonium persulfate to prepare a material C; heating a water bath to 35 ℃, placing a four-neck flask filled with basic materials into the water bath, adding 1/3C materials into the four-neck flask at one time, dropwise adding A materials and B materials at a constant speed, dropwise adding the A materials for 3 hours, dropwise adding the B materials for 3 hours and 10 minutes, adjusting the pH value in the reaction kettle to be 5 by using dilute sulfuric acid after 1.2 hours of reaction, then adding the rest C materials at one time, adding alkali for neutralization after the A materials and the B materials are dropwise added, adding water to the total mass of 1000 parts, curing for 1 hour, naturally cooling to room temperature, and synthesizing a dispersant solution with the mass fraction of about 40%, namely pumping aid W1.
The pumping agent W2 is prepared from the following materials:
(1): adding 25 parts of poly (1, 2-propylene glycol) into a high-pressure reaction kettle, adding 0.10 part of lithium aluminum hydride, performing nitrogen replacement for 4 times under stirring, starting heating, raising the temperature to about 120 ℃, then slowly introducing 80 parts of propylene oxide into the reactor to perform induction reaction, gradually raising the temperature to about 110-plus-150 ℃ in the induction process, maintaining the constant temperature at 130 ℃, maintaining the pressure at 0.25MPa relatively constant, and keeping the temperature for about 2 hours, when the pressure of the reactor does not decrease any more, adding 0.12 part of potassium hydroxide again, slowly introducing 240 parts of propylene oxide into the container to perform induction reaction with 15 parts of 2-propane sodium sulfonate, maintaining the temperature at 135 ℃, when the pressure in the reaction container does not decrease any more, reducing the temperature to 110 ℃, vacuumizing and degassing, and discharging to obtain an unsaturated intermediate with the molecular weight of about 400-plus-600;
(2): adding the unsaturated intermediate prepared in the step (1) and 220 parts of deionized water into a four-neck flask to serve as a bottom material, adding 120 parts of deionized water into 50 parts of acrylic acid to serve as a material A, preparing 1.2 parts of mercaptopropionic acid and thioglycollic acid in a mass ratio of 1:2, 4.5 parts of sodium hypophosphite and 50 parts of deionized water into a material B, and adding 60 parts of deionized water into 1.2 parts of ammonium persulfate to prepare a material C; heating a water bath to 35 ℃, placing a four-neck flask filled with basic materials into the water bath, adding 1/3C materials into the four-neck flask at one time, dropwise adding A materials and B materials at a constant speed, dropwise adding the A materials for 3 hours, dropwise adding the B materials for 3 hours and 10 minutes, adjusting the pH value in the reaction kettle to 5 by using dilute sulfuric acid after 1.2 hours of reaction, then adding the rest C materials at one time, adding alkali for neutralization after the A materials and the B materials are dropwise added, adding water to the total mass of 1000 parts, then curing for 1 hour, naturally cooling to room temperature, and synthesizing a polymer solution with the mass fraction of about 40%, namely pumping aid W2.
The invention also provides a preparation method of the low-shrinkage high-performance concrete, which comprises the following steps:
step 1, uniformly mixing 500 parts of cement 400-containing material, 30-50 parts of biomass incineration ash, 25-50 parts of viscosity modified mineral admixture, 650 parts of river sand 500-containing material, 60-150 parts of ceramic sand, 1000 parts of crushed stone 1150-containing material, 3.0-6.5 parts of super-dispersion high-adaptability water reducing agent, 1.0-2.5 parts of super slump loss preventing and reducing slump retaining agent, 0.5-1.0 part of stable pumping agent and 170 parts of water 145-containing material to prepare a concrete mixture;
step 2, pouring the concrete mixture prepared in the step 1 into a mold for molding;
and 3, curing the concrete to a certain age to obtain the low-shrinkage high-performance concrete.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, by utilizing the viscosity modification effect of the modified mineral admixture and combining the properties of ultra-dispersion, high adaptability and ultra-slump retaining and viscosity reduction of the chemical admixture, the working performance of the high-performance concrete is improved, the loss of fluidity over time is reduced, the adaptability and the pumping performance are improved, the construction difficulty is reduced, and the mechanical property and the volume stability of the high-performance concrete are improved.
2) According to the invention, the biomass incineration ash is used for replacing silica fume, and the ceramic sand is used for replacing part of river sand to prepare the high-performance concrete, so that on one hand, the self weight and the cost of the concrete can be reduced, and on the other hand, the internal relative humidity of the high-performance concrete is regulated and controlled by utilizing the water release mechanism of the two internal curing materials in different humidity environments, the self-shrinkage is reduced, and the interface cracks are reduced. Meanwhile, the synergistic effect of the two internal curing materials enables the surrounding slurry to be hydrated more fully, the strength of the interface transition area is increased, and the mechanical property of the concrete is improved.
3) The fluidity of the high-performance concrete prepared by the invention can reach more than 550mm, the compressive strength grade can reach more than C55, the internal relative humidity of 7d is improved by 10%, the self-shrinkage is reduced by more than 70%, and the high-performance concrete has good working performance and mechanical property, can inhibit shrinkage cracking, simultaneously reduces the cost and provides the construction efficiency.
Drawings
FIG. 1 SEM image of concrete sample of comparative example 1.
FIG. 2 SEM image of concrete sample of comparative example 2.
FIG. 3 SEM image of concrete sample of example 1.
Detailed Description
The applicant will make further detailed descriptions of technical solutions and advantages of the present invention with reference to specific examples, but it should be understood that the following examples should not be construed as limiting the scope of the claims of the present application in any way.
In the following examples, the cement is Huaxin P.O 52.5 ordinary portland cement; biomassIncineration ash prepared by laboratory, SiO285% of the total amount, 12% of water absorption, an average particle diameter of 8 μm, and a specific surface area of 48000m2Per kg; the fly ash microbeads are provided by a power plant in the solar logical in Hubei province, the water demand ratio is 88 percent, and the 28-day activity index is 85 percent; the slag micro powder is provided by Wuhanhua Shenzhi Zhi Tech Co Ltd, the water content is 0.06%, and the activity index in 28 days is 108%; the fineness modulus is 2.8, and the fineness modulus is 1mm-5 mm; the pottery sand is provided by Yichang Baozhu haydite development limited company, the barrel pressure strength is 9MPa, and the saturated surface dry water absorption is 10 percent; 5mm-20mm continuous graded crushed stone; the super-dispersion high-adaptability water reducing agent is prepared from a water reducing agent J1 and a water reducing agent J2 according to the proportion of 1:1-1: 5; super slump-retaining and viscosity-reducing slump retaining agent; the stable pumping agent is prepared from pumping agent W1 and pumping agent W2 according to the proportion of 1:1-3: 1.
The water reducing agent J1 is prepared by the following steps:
(1): adding 16.80 parts of phenolic alcohol head and 0.8 part of boron trifluoride and lithium aluminum hydride with the mass ratio of 0.8: 2.3 into a 5L high-pressure reaction kettle provided with a stirrer and a temperature control device, performing nitrogen replacement for 3 times, then starting vacuumizing to gauge pressure of-0.09 MPa, then heating to 125 ℃, starting vacuum dehydration for 1h, continuing introducing nitrogen for replacement, measuring the oxygen content, stopping introducing nitrogen after the oxygen content is qualified, cooling to 115 ℃, starting to continuously introduce 61.0 parts of ethylene oxide and 242.1 parts of propylene oxide, controlling the pressure to be less than 0.4MPa, keeping the temperature at 120 ℃ after the introduction is finished, aging to negative pressure, cooling and discharging to obtain crude polyether;
(2): adding the prepared finished polyether into a reaction kettle, heating to 45 ℃ by adopting water bath, and then preserving heat for 0.5 hour; preparing 6.7 parts by mass of ammonium persulfate and azodiisobutyronitrile in a ratio of 2:1, 3.2 parts by mass of thioglycolic acid, mercaptoethanol and water in a ratio of 2:1.3 into solution A; preparing 5.6 parts by mass of ascorbic acid and sodium formaldehyde sulfoxylate in a ratio of 1:1.2, 33.0 parts by mass of acrylic acid and 0.7 part by mass of phenol alcohol head into solution B; dripping A, B into the reaction kettle by using a dripping pump, wherein the dripping of A is carried out for 2 hours, and the dripping of B is carried out for 1.5 hours, thus obtaining the polyether dispersant; adding 7.3 parts by mass of sodium bicarbonate and triisopropanolamine into the prepared water reducer according to the mass ratio of 1.3:1, and supplementing water until the total mass is 1000 to obtain a required polyether water reducer solution, namely the water reducer J1;
the water reducing agent J2 is prepared by the following steps:
(1): 99.22 parts of 2-methoxy-6-allylphenol and 1.2 parts of sodium hydroxide are added into a high-pressure reaction kettle provided with a stirrer and a temperature control device, after 3 times of nitrogen replacement, vacuumizing is started to gauge pressure of-0.098 MPa, then the temperature is increased to 120 ℃, vacuum dehydration is started for 1.5h, then nitrogen gas replacement is continuously introduced, the oxygen content is measured, after the oxygen content is qualified, the introduction of nitrogen gas is stopped, and the temperature is reduced to 115 ℃; introducing a cyclic monomer into the reaction kettle, introducing 83.91 parts of ethylene oxide and 55.42 parts of propylene oxide into the reaction kettle, controlling the pressure to be less than 0.4MPa, carrying out heat preservation and aging at the temperature of 125-140 ℃ to negative pressure after the introduction is finished, cooling and discharging to obtain crude polyether;
(2): placing the crude polyether in a reaction kettle, performing nitrogen negative pressure displacement for 3 times, heating to 125 ℃, stirring for 1.7h, cooling to 90 ℃, adding distilled water, stirring for 1h, heating to 120 ℃ while vacuumizing, cooling, and discharging to obtain a finished polyether product;
(3): adding the prepared finished product polyether into a reaction kettle, and heating to 45 ℃ by adopting water bath; preparing solution A from 5.9 parts of a composition of sodium hydrosulfite and sodium metabisulfite in a mass ratio of 1:1, 9.2 parts of a composition of ammonium persulfate and benzoyl peroxide in a mass ratio of 2:3, 4.3 parts of a composition of thioglycolic acid and mercaptoethanol in a mass ratio of 1:3 and water; 158.37 parts of vinyl sulfonic acid, 1.0 part of 2-methoxy-6-allyl phenol and water are prepared into solution B; respectively dripping the solution A and the solution B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is 1.1 hours, and the dripping of the solution B is 1.7 hours; after the A, B liquid is dripped, preserving heat for 1 hour to prepare the polyether water reducer;
(4): and adding 7.8 parts of potassium hydroxide into the prepared polyether water reducer, and supplementing water until the total mass is 1000 to obtain a required polyether water reducer solution, namely the water reducer J2.
The super slump-retaining viscosity-reducing slump-retaining agent is prepared by the following steps:
(1): adding 18 parts of 2-ethoxy-3-butene-1-ol and 0.8 part of lithium aluminum hydride into a high-pressure reaction kettle provided with a stirrer and a temperature control device, performing nitrogen displacement for 3 times, vacuumizing to gauge pressure of-0.15 MPa, heating to 130 ℃, performing vacuum dehydration for 1h, introducing 305 parts of propylene oxide into the reaction kettle, controlling the pressure to be less than 0.5MPa, performing heat preservation and aging at 140 ℃ to negative pressure after introducing, cooling, and discharging to obtain the polyether monomer with the molecular weight of about 2000.
(2): adding the prepared finished product polyether into a reaction kettle, and heating to 55 ℃ by adopting water bath; preparing 3.4 parts of ammonium persulfate and water into solution A; preparing solution B from 46.0 parts of diethyl acrylate, 2 parts of 2-ethoxy-3-butene-1-ol, 4.6 parts of sodium bisulfite, 1.2 parts of mercaptopropionic acid, thioglycolic acid and water in a mass ratio of 1: 4.2; respectively dripping the solution A and the solution B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is carried out for 3 hours, and the dripping of the solution B is carried out for 2.5 hours; and (3) after the A, B liquid is dripped, preserving heat for 1 hour to obtain a polyether slump retaining agent, adding 12.4 parts of sodium hydroxide into the prepared polyether slump retaining agent, and supplementing water until the total mass is 1000 to obtain the super slump retaining and viscosity reducing slump retaining agent.
The pumping agent W1 is prepared by the following steps:
(1): adding 25 parts of cyclohexyl-1, 4-dimethanol monovinyl ether into a high-pressure reaction kettle, adding 0.10 part of lithium aluminum hydride, then under the stirring, nitrogen is replaced for 4 times, heating is started, the temperature is raised to about 110 ℃, then 80 parts of ethylene oxide is slowly introduced into the reactor for induction reaction, the temperature is gradually raised to about 100-115 ℃ in the induction process, maintaining the constant temperature at 120 deg.C, maintaining the pressure at 0.25MPa, and maintaining the temperature for about 2 hr, when the pressure of the reactor is not reduced any more, adding 0.12 part of potassium hydroxide again, slowly introducing 240 parts of ethylene oxide and 13 parts of difluoromethanesulfonic acid into the container for induction reaction, maintaining the temperature at 125 ℃, when the pressure in the reactor is not reduced any more, reducing the temperature to 80 ℃, vacuumizing and degassing, and discharging to obtain an unsaturated intermediate with the molecular weight of about 400-;
(2): adding the unsaturated intermediate prepared in the step (1) and 350 parts of deionized water into a four-neck flask to serve as a bottom material, adding 120 parts of deionized water into 30 parts of acrylic acid to serve as a material A, preparing 1.2 parts of mercaptopropionic acid and thioglycollic acid in a mass ratio of 1:2, 4.5 parts of sodium hypophosphite and 50 parts of deionized water into a material B, and adding 60 parts of deionized water into 1.2 parts of ammonium persulfate to prepare a material C; heating a water bath to 35 ℃, placing a four-neck flask filled with basic materials into the water bath, adding 1/3C materials into the four-neck flask at one time, dropwise adding A materials and B materials at a constant speed, dropwise adding the A materials for 3 hours, dropwise adding the B materials for 3 hours and 10 minutes, adjusting the pH value in the reaction kettle to be 5 by using dilute sulfuric acid after 1.2 hours of reaction, then adding the rest C materials at one time, adding alkali for neutralization after the A materials and the B materials are dropwise added, adding water to the total mass of 1000 parts, curing for 1 hour, naturally cooling to room temperature, and synthesizing a dispersant solution with the mass fraction of about 40%, namely pumping aid W1.
The pumping agent W2 is prepared from the following materials:
(1): adding 25 parts of poly (1, 2-propylene glycol) into a high-pressure reaction kettle, adding 0.10 part of lithium aluminum hydride, performing nitrogen replacement for 4 times under stirring, starting heating, raising the temperature to about 120 ℃, then slowly introducing 80 parts of propylene oxide into the reactor to perform induction reaction, gradually raising the temperature to about 110-plus-150 ℃ in the induction process, maintaining the constant temperature at 130 ℃, maintaining the pressure at 0.25MPa relatively constant, and keeping the temperature for about 2 hours, when the pressure of the reactor does not decrease any more, adding 0.12 part of potassium hydroxide again, slowly introducing 240 parts of propylene oxide into the container to perform induction reaction with 15 parts of 2-propane sodium sulfonate, maintaining the temperature at 135 ℃, when the pressure in the reaction container does not decrease any more, reducing the temperature to 110 ℃, vacuumizing and degassing, and discharging to obtain an unsaturated intermediate with the molecular weight of about 400-plus-600;
(2): adding the unsaturated intermediate prepared in the step (1) and 220 parts of deionized water into a four-neck flask to serve as a bottom material, adding 120 parts of deionized water into 50 parts of acrylic acid to serve as a material A, preparing 1.2 parts of mercaptopropionic acid and thioglycollic acid in a mass ratio of 1:2, 4.5 parts of sodium hypophosphite and 50 parts of deionized water into a material B, and adding 60 parts of deionized water into 1.2 parts of ammonium persulfate to prepare a material C; heating a water bath to 35 ℃, placing a four-neck flask filled with basic materials into the water bath, adding 1/3C materials into the four-neck flask at one time, dropwise adding A materials and B materials at a constant speed, dropwise adding the A materials for 3 hours, dropwise adding the B materials for 3 hours and 10 minutes, adjusting the pH value in the reaction kettle to 5 by using dilute sulfuric acid after 1.2 hours of reaction, then adding the rest C materials at one time, adding alkali for neutralization after the A materials and the B materials are dropwise added, adding water to the total mass of 1000 parts, then curing for 1 hour, naturally cooling to room temperature, and synthesizing a polymer solution with the mass fraction of about 40%, namely pumping aid W2.
Examples 1 to 6
The mixing proportion of the low-shrinkage high-performance concrete is shown in a table 1. Wherein, the biomass incineration ash in the example 1 is prepared by mixing rice husk ash and bamboo leaf ash according to the ratio of 1: 1; in example 2, the biomass incineration ash was prepared by mixing rice hull ash and corncob ash at a ratio of 2: 1; in example 3, the biomass incineration ash was prepared by mixing rice hull ash and straw ash at a ratio of 3: 1; in example 4, the biomass incineration ash was prepared by mixing rice hull ash and elephant grass ash in a ratio of 1: 1; in example 5, the biomass incineration ash was prepared by mixing bamboo leaf ash and elephant grass ash at a ratio of 2: 1; in example 6, the biomass incineration ash was prepared by mixing rice hull ash, straw ash and elephant grass ash in a ratio of 2:1: 1. The cement is P.O 52.5 ordinary portland cement.
TABLE 1 Low shrinkage high Performance concrete mix proportions (parts) as described in examples 1-6
Comparative example 1, the water reducing agent used was basf 415, the slump retaining agent used was basf 416, and the other materials were the same as in example 1.
Comparative example 2, biomass incineration ash was replaced with silica fume, and the other materials were the same as in example 1.
The working properties, mechanical properties, self-shrinkage and crack resistance of examples 1-6 were compared with those of comparative examples 1-2, and the results are shown in Table 2.
TABLE 2 results of performance test of high-performance concrete obtained in examples 1 to 6 and comparative examples 1 to 2
As can be seen from Table 2, the low-shrinkage high-performance concrete prepared by the invention has good working performance (slump/expansion), good slump retaining performance (the loss of fluidity is small in 1 hour with time), the compressive strength grade reaches above C55, the early self-shrinkage is reduced by more than 60%, and the concrete has good crack resistance (crack resistance grade).
The concrete samples of comparative examples 1 and 2, which were hydrated for 28d, and the sample of example 1 were subjected to SEM examination, and the apparent morphology thereof was observed, and the results are shown in fig. 1 to 3. Obviously, the hydrated product in the embodiment 1 has a relatively compact structure and no cracks, because the chemical admixture has the characteristics of high ultra-dispersion adaptability and ultra-slump retaining and viscosity reducing performance, the working performance of the high-performance concrete can be improved, the internal structure is tightly stacked, and meanwhile, the internal relative humidity of the high-performance concrete is regulated and controlled by the synergistic internal curing effect of the biomass incineration ash and the ceramic sand, so that the early self-shrinkage is reduced, and the surface cracks of the concrete are reduced. Therefore, the low-shrinkage high-performance concrete prepared by the invention can be applied to civil engineering such as cast-in-place beams and the like, can improve the construction efficiency, effectively reduce the risk of shrinkage cracking, reduce the cost and has important economic and environmental benefits.
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (10)
1. The low-shrinkage high-performance concrete is characterized by comprising the following raw materials in parts by weight:
400 portions of cement;
30-50 parts of biomass incineration ash;
25-50 parts of viscosity modified mineral admixture;
500-650 parts of continuous graded river sand with fineness modulus of 2.8 and 1-5 mm;
60-150 parts of pottery sand;
1000-1150 parts of 5mm-20mm continuous graded broken stone;
3.0-6.5 parts of a super-dispersed high-adaptability water reducing agent;
1.0-2.5 parts of super slump loss and viscosity reduction type slump retaining agent;
0.5-1.0 part of stable pumping aid;
145 portions of water and 170 portions of water.
2. A low shrinkage, high performance concrete according to claim 1, wherein: SiO of the biomass incineration ash2The content is more than or equal to 80 percent, the water absorption is more than or equal to 10 percent, and the specific surface area is more than or equal to 40000m2/kg。
3. A low shrinkage, high performance concrete according to claim 2, wherein: the biomass incineration ash is composed of any one or more of rice hull ash, bamboo leaf ash, corncob ash, straw ash and elephant grass ash.
4. A low shrinkage, high performance concrete according to claim 1, wherein: the viscosity modified mineral admixture consists of fly ash micro-beads and slag micro-powder.
5. A low shrinkage, high performance concrete according to claim 4, wherein: the water demand ratio of the fly ash micro-beads is less than or equal to 95 percent, and the strength activity index in 28 days is more than or equal to 80 percent.
6. A low shrinkage, high performance concrete according to claim 4, wherein: the water content of the slag micro powder is less than or equal to 0.08 percent, and the strength activity index in 28 days is more than or equal to 100 percent.
7. A low shrinkage, high performance concrete according to claim 1, wherein: the granularity range of the ceramic sand is 1mm-5mm, the cylinder pressure strength is more than or equal to 8MPa, and the saturated surface dry water absorption is more than or equal to 9%.
8. A low shrinkage, high performance concrete according to claim 1, wherein: the ultra-dispersion high-adaptability water reducing agent is prepared from a water reducing agent J1 and a water reducing agent J2 according to the proportion of 1:1-1: 5;
the water reducing agent J1 is prepared by the following steps:
(1): adding 16.80 parts of phenolic alcohol head and 0.8 part of boron trifluoride and lithium aluminum hydride with the mass ratio of 0.8: 2.3 into a 5L high-pressure reaction kettle provided with a stirrer and a temperature control device, performing nitrogen replacement for 3 times, then starting vacuumizing to gauge pressure of-0.09 MPa, then heating to 125 ℃, starting vacuum dehydration for 1h, continuing introducing nitrogen for replacement, measuring the oxygen content, stopping introducing nitrogen after the oxygen content is qualified, cooling to 115 ℃, starting to continuously introduce 61.0 parts of ethylene oxide and 242.1 parts of propylene oxide, controlling the pressure to be less than 0.4MPa, keeping the temperature at 120 ℃ after the introduction is finished, aging to negative pressure, cooling and discharging to obtain crude polyether;
(2): adding the prepared finished polyether into a reaction kettle, heating to 45 ℃ by adopting water bath, and then preserving heat for 0.5 hour; preparing 6.7 parts by mass of ammonium persulfate and azodiisobutyronitrile in a ratio of 2:1, 3.2 parts by mass of thioglycolic acid, mercaptoethanol and water in a ratio of 2:1.3 into solution A; preparing 5.6 parts by mass of ascorbic acid and sodium formaldehyde sulfoxylate in a ratio of 1:1.2, 33.0 parts by mass of acrylic acid and 0.7 part by mass of phenol alcohol head into solution B; dripping A, B into the reaction kettle by using a dripping pump, wherein the dripping of A is carried out for 2 hours, and the dripping of B is carried out for 1.5 hours, thus obtaining the polyether dispersant; adding 7.3 parts by mass of sodium bicarbonate and triisopropanolamine into the prepared water reducer according to the mass ratio of 1.3:1, and supplementing water until the total mass is 1000 to obtain a required polyether water reducer solution, namely the water reducer J1;
the water reducing agent J2 is prepared by the following steps:
(1): 99.22 parts of 2-methoxy-6-allylphenol and 1.2 parts of sodium hydroxide are added into a high-pressure reaction kettle provided with a stirrer and a temperature control device, after 3 times of nitrogen replacement, vacuumizing is started to gauge pressure of-0.098 MPa, then the temperature is increased to 120 ℃, vacuum dehydration is started for 1.5h, then nitrogen gas replacement is continuously introduced, the oxygen content is measured, after the oxygen content is qualified, the introduction of nitrogen gas is stopped, and the temperature is reduced to 115 ℃; introducing a cyclic monomer into the reaction kettle, introducing 83.91 parts of ethylene oxide and 55.42 parts of propylene oxide into the reaction kettle, controlling the pressure to be less than 0.4MPa, carrying out heat preservation and aging at the temperature of 125-140 ℃ to negative pressure after the introduction is finished, cooling and discharging to obtain crude polyether;
(2): placing the crude polyether in a reaction kettle, performing nitrogen negative pressure displacement for 3 times, heating to 125 ℃, stirring for 1.7h, cooling to 90 ℃, adding distilled water, stirring for 1h, heating to 120 ℃ while vacuumizing, cooling, and discharging to obtain a finished polyether product;
(3): adding the prepared finished product polyether into a reaction kettle, and heating to 45 ℃ by adopting water bath; preparing solution A from 5.9 parts of a composition of sodium hydrosulfite and sodium metabisulfite in a mass ratio of 1:1, 9.2 parts of a composition of ammonium persulfate and benzoyl peroxide in a mass ratio of 2:3, 4.3 parts of a composition of thioglycolic acid and mercaptoethanol in a mass ratio of 1:3 and water; 158.37 parts of vinyl sulfonic acid, 1.0 part of 2-methoxy-6-allyl phenol and water are prepared into solution B; respectively dripping the solution A and the solution B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is 1.1 hours, and the dripping of the solution B is 1.7 hours; after the A, B liquid is dripped, preserving heat for 1 hour to prepare the polyether water reducer;
(4): and adding 7.8 parts of potassium hydroxide into the prepared polyether water reducer, and supplementing water until the total mass is 1000 to obtain a required polyether water reducer solution, namely the water reducer J2.
9. A low shrinkage, high performance concrete according to claim 1, wherein: the super slump-retaining viscosity-reducing slump-retaining agent is prepared by the following steps:
(1): adding 18 parts of 2-ethoxy-3-butene-1-ol and 0.8 part of lithium aluminum hydride into a high-pressure reaction kettle provided with a stirrer and a temperature control device, performing nitrogen displacement for 3 times, vacuumizing to gauge pressure of-0.15 MPa, heating to 130 ℃, performing vacuum dehydration for 1h, introducing 305 parts of propylene oxide into the reaction kettle, controlling the pressure to be less than 0.5MPa, performing heat preservation and aging at 140 ℃ to negative pressure after introducing, cooling, and discharging to obtain about 2000 molecular weight polyether monomers;
(2): adding the prepared finished product polyether into a reaction kettle, and heating to 55 ℃ by adopting water bath; preparing 3.4 parts of ammonium persulfate and water into solution A; preparing solution B from 46.0 parts of diethyl acrylate, 2 parts of 2-ethoxy-3-butene-1-ol, 4.6 parts of sodium bisulfite, 1.2 parts of mercaptopropionic acid, thioglycolic acid and water in a mass ratio of 1: 4.2; respectively dripping the solution A and the solution B into the reaction kettle by using a dripping pump, wherein the dripping of the solution A is carried out for 3 hours, and the dripping of the solution B is carried out for 2.5 hours; and (3) after the A, B liquid is dripped, preserving heat for 1 hour to obtain a polyether slump retaining agent, adding 12.4 parts of sodium hydroxide into the prepared polyether slump retaining agent, and supplementing water until the total mass is 1000 to obtain the super slump retaining and viscosity reducing slump retaining agent.
10. A low shrinkage, high performance concrete according to claim 1, wherein: the stable pumping agent is prepared from a pumping agent W1 and a pumping agent W2 according to the proportion of 1:1-3: 1;
the pumping agent W1 is prepared by the following steps:
(1): adding 25 parts of cyclohexyl-1, 4-dimethanol monovinyl ether into a high-pressure reaction kettle, adding 0.10 part of lithium aluminum hydride, then under the stirring, nitrogen is replaced for 4 times, heating is started, the temperature is raised to about 110 ℃, then 80 parts of ethylene oxide is slowly introduced into the reactor for induction reaction, the temperature is gradually raised to about 100-115 ℃ in the induction process, maintaining the constant temperature at 120 deg.C, maintaining the pressure at 0.25MPa, and maintaining the temperature for about 2 hr, when the pressure of the reactor is not reduced any more, adding 0.12 part of potassium hydroxide again, slowly introducing 240 parts of ethylene oxide and 13 parts of difluoromethanesulfonic acid into the container for induction reaction, maintaining the temperature at 125 ℃, when the pressure in the reactor is not reduced any more, reducing the temperature to 80 ℃, vacuumizing and degassing, and discharging to obtain an unsaturated intermediate with the molecular weight of about 400-;
(2): adding the unsaturated intermediate prepared in the step (1) and 350 parts of deionized water into a four-neck flask to serve as a bottom material, adding 120 parts of deionized water into 30 parts of acrylic acid to serve as a material A, preparing 1.2 parts of mercaptopropionic acid and thioglycollic acid in a mass ratio of 1:2, 4.5 parts of sodium hypophosphite and 50 parts of deionized water into a material B, and adding 60 parts of deionized water into 1.2 parts of ammonium persulfate to prepare a material C; heating a water bath to 35 ℃, placing a four-neck flask filled with basic materials into the water bath, adding 1/3C materials into the four-neck flask at one time, then dropwise adding the A materials and the B materials at a constant speed for 3 hours, dropwise adding the B materials for 3 hours and 10 minutes, after the reaction is carried out for 1.2 hours, adjusting the pH in the reaction kettle to be 5 by using dilute sulfuric acid, then adding the rest C materials at one time, after the A materials and the B materials are dropwise added, adding alkali for neutralization, adding water to the total mass of 1000 parts, then curing for 1 hour, naturally cooling to room temperature, and synthesizing a dispersant solution with the mass fraction of about 40%, namely pumping agent W1;
the pumping agent W2 is prepared from the following materials:
(1): adding 25 parts of poly (1, 2-propylene glycol) into a high-pressure reaction kettle, adding 0.10 part of lithium aluminum hydride, performing nitrogen replacement for 4 times under stirring, starting heating, raising the temperature to about 120 ℃, then slowly introducing 80 parts of propylene oxide into the reactor to perform induction reaction, gradually raising the temperature to about 110-plus-150 ℃ in the induction process, maintaining the constant temperature at 130 ℃, maintaining the pressure at 0.25MPa relatively constant, and keeping the temperature for about 2 hours, when the pressure of the reactor does not decrease any more, adding 0.12 part of potassium hydroxide again, slowly introducing 240 parts of propylene oxide into the container to perform induction reaction with 15 parts of 2-propane sodium sulfonate, maintaining the temperature at 135 ℃, when the pressure in the reaction container does not decrease any more, reducing the temperature to 110 ℃, vacuumizing and degassing, and discharging to obtain an unsaturated intermediate with the molecular weight of about 400-plus-600;
(2): adding the unsaturated intermediate prepared in the step (1) and 220 parts of deionized water into a four-neck flask to serve as a bottom material, adding 120 parts of deionized water into 50 parts of acrylic acid to serve as a material A, preparing 1.2 parts of mercaptopropionic acid and thioglycollic acid in a mass ratio of 1:2, 4.5 parts of sodium hypophosphite and 50 parts of deionized water into a material B, and adding 60 parts of deionized water into 1.2 parts of ammonium persulfate to prepare a material C; heating a water bath to 35 ℃, placing a four-neck flask filled with basic materials into the water bath, adding 1/3C materials into the four-neck flask at one time, dropwise adding A materials and B materials at a constant speed, dropwise adding the A materials for 3 hours, dropwise adding the B materials for 3 hours and 10 minutes, adjusting the pH value in the reaction kettle to 5 by using dilute sulfuric acid after 1.2 hours of reaction, then adding the rest C materials at one time, adding alkali for neutralization after the A materials and the B materials are dropwise added, adding water to the total mass of 1000 parts, then curing for 1 hour, naturally cooling to room temperature, and synthesizing a polymer solution with the mass fraction of about 40%, namely pumping aid W2.
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