CN110128077A - Low viscous easily pumping ultra-high performance concrete of one kind and preparation method thereof - Google Patents
Low viscous easily pumping ultra-high performance concrete of one kind and preparation method thereof Download PDFInfo
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- CN110128077A CN110128077A CN201910490204.0A CN201910490204A CN110128077A CN 110128077 A CN110128077 A CN 110128077A CN 201910490204 A CN201910490204 A CN 201910490204A CN 110128077 A CN110128077 A CN 110128077A
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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
- 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
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
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Abstract
The invention discloses a kind of low viscous easily pumping ultra-high performance concretes and preparation method thereof.Each composition of concrete of the present invention is calculated in parts by mass: 300 ~ 500 parts of cement, 100 ~ 200 parts of silicon ash, 300 ~ 600 parts of admixture, 400 ~ 800 parts of sand, 300 ~ -700 parts of rubble, 80 ~ 240 parts of fiber, 5 ~ 30 parts of thixotroping reinforcing agent, 15 ~ 30 parts of water-reducing agent, 0.1 ~ 0.3 part of defoaming agent, 140 ~ 180 parts of water.Low viscous easily pumping ultra-high performance concrete mobility with higher and lower viscosity, pumping resistance of the present invention are only 0.015 ~ 0.025MPa/m, and compression strength reaches 180MPa or more after standard curing 28d.Furthermore low viscous easily pumping ultra-high performance concrete of the present invention has the characteristics that typical low cement, not only significantly reduces the contraction of ultra-high performance concrete, and significantly reduce cement consumption, reduces environmental pollution.
Description
Technical field
The invention belongs to building material technical fields, are related to a kind of ultra-high performance concrete, and in particular to a kind of low viscous easy
Pump ultra-high performance concrete and preparation method thereof.
Background technique
Ultra-high performance concrete (Ultra-high performance concrete, UHPC) have superelevation strong, high-ductility,
The excellent properties such as high-impermeable, highly corrosion resistant and high antiknock, be well positioned to meet civil engineering structure lightweight, high stratification, greatly across
Change the requirement durable with height, it is great or special engineered in Large Span Bridges, thin-wall construction, defence engineering and deep water ocean platform etc.
Have important strategic importance and broad application prospect.With Reactive Powder Concrete (Reactive Powder
Concrete writes a Chinese character in simplified form RPC) be main representative ultra-high performance concrete, mainly by large dosage superfine powder and extremely low
Water consumption improves density, realizes the very-high performance of concrete.However, this to also result in ultra-high performance concrete viscosity larger,
Cause a series of construction problems such as concrete stirring, transport, pumping, largely limits pushing away for ultra-high performance concrete
Extensively with application.Ultra-high performance concrete is mainly used for prefabricated components at present, and the application example of large scale structure engineering does not have also substantially
Have, let alone pumping construction.With ultra-high performance concrete large-scale promotion application, it is mixed to develop low viscous easily pumping very-high performance
Solidifying soil becomes inexorable trend.
Patent CN201510987930 discloses a kind of with the super high strength concrete of super high pump-conveying property and its preparation side
Method, using cement, sand, stone, mountain flour, water, flyash, zeolite powder, miberal powder, water-reducing agent, silicon powder and air entraining agent as primary raw material.
The patented technology mainly on the basis of high-strength concrete, is changed by short-side chain polycarboxylate high performance water-reducing agent and air entraining agent
Kind concrete viscosity and pump-conveying property, and concrete strength is being improved by reducing water-cement ratio and improving the accumulation of particle, but
Concrete strength is only 120MPa or so, and without fiber, not ultra-high performance concrete.2014108531899 disclosure of patent CN
A kind of lower shrinkage low viscosity super high strength concrete improves the viscosity of concrete by double-doped large dosage microballon and super finely ground slag,
But concrete strength is only 120MPa or so, and without fiber.Patent CN2017102107384 discloses a kind of dress for being easy to pump
Decorations ultra-high performance concrete, using white cement, silicon ash and metakaolin, quartz sand, color, water-reducing agent, aluminium-magnesium silicate, fibre
It ties up plain ether and fiber etc. and prepares ultra-high performance concrete.The patented technology increases the viscosity of concrete by higher territory, and
Improve the thixotropy of ultra-high performance concrete using aluminium-magnesium silicate, and then improves the pump-conveying property of ultra-high performance concrete.However
Ultra-high performance concrete is free of coarse aggregate (rubble) in patented technology, and does not consider to pour since concrete viscosity is caused greatly
Difficult problem.
Summary of the invention
It is big for current conventional ultra-high performance concrete viscosity, pump-conveying property is poor, it is difficult to scale is constructed this problem, this
Invention provides low viscous easily pumping ultra-high performance concrete of one kind and preparation method thereof.The ultra-high performance concrete viscosity is low, flowing
Degree is big, and shear shinning characteristic is presented in pumping procedure, and pumping resistance is greatly lowered；And there is apparent thixotropic behavior, it mixes
Wrapped higher when solidifying soil static condition, fiber and aggregate can be uniformly distributed, and reduce stifled pump risk, while ensuring very-high performance
Homogeneity with higher in concreting process.In addition to this, water is substituted using the mineral-filled material of large dosage in the present invention
Mud has the characteristics that typical low cement, not only significantly reduces the contraction of ultra-high performance concrete, and significantly reduces cement
Dosage reduces environmental pollution.
The present invention provides a kind of low viscous easily pumping ultra-high performance concretes, are made of following each component by mass parts:
The cement is the portland cement or ordinary portland cement of 42.5 or more strength grade, average grain diameter 10
~20 μm；
SiO in the silicon ash2Content 90wt% or more, the average grain diameter of silicon ash are 0.2 μm~1 μm；
The admixture is the composition of SILICA FUME, microballon and filler；Wherein the average grain diameter of the SILICA FUME be 1~
5μm；The average grain diameter of the microballon is 2~10 μm；The filler is flyash, ground blast furnace slag, any one in silica flour
Or the mixing of more than one arbitrary proportions, the average grain diameter of the filler are 10~100 μm；
The sand is 0.075~4.75mm of partial size continuous grading sand；
The rubble is limestone, granite, diabase, any one in basalt, grain diameter is 4.75~
19mm continuous grading；
The fiber is metallic fiber, 3~25mm of length, 0.1~0.3mm of diameter；
The thixotroping reinforcing agent is selected from one or both of inorganic thixotroping reinforcing agent, organic thixotroping reinforcing agent arbitrary proportion
Mixing；
The water-reducing agent is viscosity reduction type high-performance water reducing agent；
The defoaming agent is Polyether Modified Polysiloxanes Defoaming Agent or polyether antifoam agent any one or two kinds of arbitrary proportions
Mixing；
The inorganic thixotroping reinforcing agent is modified Nano clay, and preparation method is made of following step:
1. nano clay is poured into beaker, it is 5 that mass concentration, which is added, by mass ratio 1:3~1:20 of nano clay and acid
~30% acid keeps 5~20min of constant temperature and is stirred continuously, filters, put after standing cooling 2~4h after being heated to 40~60 DEG C
Permanent quality is dried in 105 DEG C to drying box；
Wherein any one or two kind arbitrary proportions mixing of the acid in hydrochloric acid, sulfuric acid and phosphoric acid；
2. the nano clay obtained after taking step 1. to dry is mixed with water according to 1:3~1:10 mass ratio, using ultrasound
L~2h is shaken, nano clay slurries are obtained；
3. the nano clay slurries for taking step 2. to obtain are mixed with silane coupling agent with 100:1~200:1 mass ratio, and
It uses high-speed mixer to stir 10~20min with the revolving speed of 2000~10000rpm, uses 0.5~1h of ultrasonic vibration later；
4. the slurry for taking step 3. to obtain is mixed with anionic surfactant with the mass ratio of 5:1~20:1, in 40
1~2h is stirred in~80 DEG C of waters bath with thermostatic control, is used 0.5~1h of ultrasonic vibration later, is obtained the modified Nano clay；
Step 4. described in anionic surfactant be selected from odium stearate, neopelex, polyacrylic acid, poly-
Acrylamide, alkyl phosphorus carboxylate, any one or more than one arbitrary proportion mixing in alkyl alcohol ether carboxylate；
Organic thixotroping reinforcing agent is complexing type polyurethane water-soluble polymer, guar gum, xanthan gum, alginic acid the third two
Alcohol ester, polyacrylamide, starch ether, any one or two kinds in polyvinyl alcohol are mixed with arbitrary proportion；
The viscosity reduction type high-performance water reducing agent is the polymer with following general formula (1):
Wherein z is indicated and functional group R0The connection quantity of the repetitive structure X of connection, value range are the integer of 1-4；R0
Indicate H or straight chain or the hydrogen functional group of saturated carbon containing branch containing 1-12 carbon atom, R0When for H, z must be 1；X is to meet
Any one in functional group shown in following general formula (2):
Wherein, X1、X1'、X1" separately indicate carbonyl or-CH2Or-CH2CH2-；X2It indicates in following functional group
Any one: (1) saturated alkyl or-(CH containing 1-12 carbon atom2CH2O)mCH2CH2, wherein it is single to indicate that ethyoxyl repeats by m
First number, value range are the integer of 1-11, and (2)-CH (NH2)-, C are L chiral；R2、R2'、R2" separately indicate H or
Person CH3；R4' expression-CH2CH2-、 -CH2CH2SCH2CH2-、-CH2CH2SCH2CH2OCH2CH2-、-CO-CH2CH2SCH2CH2-、 -
CO-CH2CH2CH2CH2OCH2CH2In any one；R5Indicate H or the saturated alkyl containing 1-12 carbon atom；M2 +Indicate H+, alkali metal ion or ammonium ion；R9Indicate the saturated alkyl containing 1-12 carbon atom；
General formula (2) is not limited through-X1" connection side-chain structure in ethyoxyl and isopropoxy chain link connection it is suitable
Sequence, ethyoxyl and isopropoxy chain link can be block distributed, can also be random distribution.Similarly, general formula (2) does not also limit
Determine the order of connection for the ethoxy unit that main polymer chain respectively replaces, these ethoxy units replaced can be block distributed
, it is also possible to random distribution.C, d respectively indicates the molar average addition of ethyoxyl and isopropoxy chain link in polymer
Number, and meet 11≤(c+d)≤114, d/c < 1/2；
x1、x2The molar average adduct number of each chain link in polymer superplasticizer is respectively represented with y, and meets following relationship:
(1)(x1+x2+ y) it with the value range of the product of z is 8-150；(2)y/(x1+x2+ y) value range be 0.15-0.5；(3)
(x1+x2)/(x1+x2+ y) value range be 0.5-0.85；(4)x2/x1Value range be 0-0.5；
The viscosity reduction type high-performance water reducing agent molecular weight distributing index PDI is not more than 1.4, and weight average molecular weight range is
5000-100000。
Preferably, the low viscous easily pumping ultra-high performance concrete of one kind of the present invention presses mass parts group by following each component
At:
The viscosity reduction type high-performance water reducing agent can be prepared by following steps:
(1) deoxygenation is removed water in the reactor, and monomer a passes through bulk polymerization or polymerisation in solution under the conditions of highly basic initiator
And anionic ring-opening polymerization preparation intermediate polymer is carried out, main chain is polyglycol chain, is grafted with a large amount of double bonds thereon；
(2) in the presence of a catalyst, by the Michael addition reaction of sulfydryl and double bond connect adsorption functional group and
It is viscosity reduction type high-performance water reducing agent that the polymer, which is made, in long polyether lateral chain with steric hindrance effect；Wherein adsorb function
Group comes from function small molecule monomer b, and long polyether lateral chain is from the polymeric monomer E simultaneously with sulfydryl and polyethers chain structure；
Monomer a described in step (1) is the monomer containing double bond and epoxy-functional simultaneously, meets following general formula (3) institute
Show any one in structure:
Wherein R2Indicate H or CH3, Y expression carbonyl ,-CH2Or-CH2CH2-；
Highly basic initiator described in step (1) is sodium alkoxide or potassium alcoholate, and " alcohol " refers to " by the straight chain containing 1-12 carbon atom
Or the Organic Alcohol of the composition of the hydrogen functional group of saturated carbon containing branch and 1-4 terminal hydroxy group "；
Step (1) is according to polymerisation in solution, then the solvent in solution is tetrahydrofuran, dioxane, dimethyl sulfoxide, N, N-
Dimethyl acetamide, N-methylmorpholine, N-ethylmorpholine, any one in N-Methyl pyrrolidone；The quality of the solvent
It is equivalent to the 0-300% of monomer a mass, includes 0% and 300%.
Step (1) polymerization temperature is 50-150 DEG C, and reaction time 2-24h, related fields professional can be according to anti-
Rate is answered to adjust reaction temperature and reaction time in range；
The molar ratio of highly basic initiator described in step (1) and monomer a are 1:8-150.
Step (2) described catalyst is similarly catalyst known to related fields professional technician, specifically refers to
Document Chem.Mater.2014,26,724-744.The catalyst is preferably sodium hydroxide or potassium hydroxide or contains 1-12
The corresponding sodium alkoxide of the Organic Alcohol of the saturated alkyl of carbon atom or potassium alcoholate meet (4-1) shown in general formula, in general formula (4-2) structure
Any one:
In general formula (4-1), R10、R11、R12Separately represent H or the saturated alkyl containing 1-6 carbon atom, general formula
In (4-2), R13、R14、R15Separately represent H or saturated alkyl or phenyl or cyclohexyl or ring containing 1-6 carbon atom
The cyclohexyl or 1-3 carbon that the phenyl or 1-3 carbon atom saturated alkyl that amyl or 1-3 carbon atom saturated alkyl replace replace
The cyclopenta that atom saturated alkyl replaces.
Functionality small molecule monomer b described in step (2) is while having sulfydryl and carboxyl or sulfonic monomer, described
Monomer b is a kind of composition, and the composition is the mixing of component A and B component, and B component mole accounts for A and B component is always rubbed
The 0-50% of your amount；
Wherein component A is (a) or one or both of (b): (a) being met any in structure shown in following general formula (5)
A kind of or more than one any combination:
R8Indicate saturated alkyl or-(CH containing 1-12 carbon atom2CH2O)mCH2CH2, wherein m indicates that ethyoxyl repeats
Unit number, value range are the integer of 1-11.
Or (b) hydrochloride or sulfate of cysteine；
B component is any one or the more than one any combination met in structure shown in following general formula (6):
Wherein M2 +Indicate H+, alkali metal ion or ammonium ion, R9Indicate the saturated alkyl containing 1-12 carbon atom.
Polymeric monomer E described in step (2) is one of structure shown in following general formula (7) or more than one any mixes
It closes:
R5Indicate H or the saturated alkyl containing 1-12 carbon atom, R4Indicate the organic functional that a sulfydryl is contained in end
Group is following functional group-CH2CH2SH、-CH2CH2SCH2CH2SH、 -CH2CH2SCH2CH2OCH2CH2SH、-CO-
CH2CH2SCH2CH2SH or-CO-CH2CH2CH2CH2OCH2CH2Any one in SH, c, d respectively indicate second in polyethers H structure
The molar average adduct number of oxygroup and isopropoxy chain link, and meet 11≤(c+d)≤114, d/c < 1/2.General formula (5) is not
The order of connection of ethyoxyl and isopropoxy chain link is limited, ethyoxyl and isopropoxy chain link can be block distributed, can also be
Random distribution.Polymeric monomer is commercially available business product or can simply be prepared by document with industrial method, related manufacturing processes
Referring to embodiment part.Meanwhile the molecular weight distributing index PDI for needing to control polymeric monomer is not higher than 1.3, if the molecular weight of the two
Wider distribution, although as a result will lead to can equally prepare super plasticizer sample, the molecular weight distribution of sample may be wider.
Step (2) addition reaction temperature is 0-100 DEG C, reaction time 3-24h.
The mole of polymeric monomer E accounts for the 15-50% of monomer a mole in step (2)；The mole of catalyst accounts for monomer a
The 0.2-5% of mole；The mole of functional small molecule monomer b is calculated respectively with the mole of sulfydryl contained therein, total
Mole accounts for the 50-85% of monomer a mole, and the integral molar quantity of polymeric monomer E and functional small molecule monomer b are not less than monomer
The mole of a.
Preferably, admixture component of the present invention and each component mass ratio are SILICA FUME: microballon: filler=80:70:
300；The filler component and each component mass ratio are flyash: ground slag: silica flour=80:120:100.
Preferably, fiber of the present invention is length 13mm, the straight fine high-strength steel fibre of diameter 0.2mm and length
25mm, diameter 0.25mm the high-strength steel fibre of end hook type example 2:1 in mass ratio mix.
The preparation method of low viscous easily pumping ultra-high performance concrete of the present invention includes the following steps: water first
Mud, silicon ash, admixture, sand and rubble mix 0.5~2min, add the water mixed in advance, defoaming agent, thixotroping reinforcing agent
And water-reducing agent stirs 2~4min, and fiber is added later and stirs 2~4min, and the low viscous easily pumping very-high performance coagulation is made
Soil.
It is of the present invention to have the beneficial effect that
(1) it is improved using the mineral-filled material substitution cement of large dosage by the optimum organization of different-grain diameter powder granule
Gelling material particles gradation improves packing density, improves the compactness of concrete, and then realizes that concrete strength is promoted；This
Outside, have the characteristics that typical low cement, significantly reduce cement consumption, reduce environmental pollution.
(2) by 1~5 μm of SILICA FUME and 2~10 μm of microballon, pattern effect and surface charge based on powder granule
Effect reduces particles' interaction power, increases the water film thickness of particle surface, and improve the adsorption efficiency of additive,
Ultra-high performance concrete viscosity is effectively reduced, and then reduces pumping resistance.
(3) hydrophilic, narrow molecular weight distribution the viscosity reduction type high-performance water reducing agent using main chain, realizes the superelevation of extremely low water-cement ratio
The uniform rapid dispersion of large dosage superfine powder in performance concrete reduces in slurry superfine powder due between superpower particle
Agglomeration traits caused by active force increase the wet packing density of particle in slurry, release more Free waters, Jin Erti
The high fluidity of ultra-high performance concrete, reduces viscosity, and then reduce pumping resistance.
(4) pass through modified Nano clay or complexing type polyurethane water-soluble polymer, guar gum, xanthan gum, alginic acid third
Diol ester, polyacrylamide, starch ether, organic thixotroping reinforcing agent such as polyvinyl alcohol realize that lower present of concrete shearing effect is cut
The dilute characteristic of shear, viscosity are substantially reduced, and fluidity significantly improves, and frictional resistance substantially reduces in lubricant layer in pumping procedure,
I.e. pumping resistance significantly reduces；And after shear removal, concrete viscosity restore, concrete workability is preferable, avoid due to
Aggregate caused by fluidity is excessive and fiber settlement issues are not only reduced since aggregate and fiber are unevenly distributed caused stifled pump
Risk, and the homogeneity of hardening UHPC is improved, and then improve ultra-high performance concrete intensity.
(5) the increase problem of the air content due to caused by large dosage fiber, water-reducing agent is eliminated by introducing defoaming agent, simultaneously
It also avoids ultra-high performance concrete air content caused by gas introducing in pumping procedure to increase considerably, and then ensures coagulation
The superelevation density of soil, to realize the very-high performance of concrete.
By abovementioned technology, the pumping resistance of the low viscous easily pumping ultra-high performance concrete of preparation is 0.015~
Compression strength reaches 180MPa or more after 0.025MPa/m, standard curing 28d.
Specific embodiment
In order to more fully explain implementation of the invention, following low viscous easily pumping ultra-high performance concrete preparations are provided and are implemented
Example.These embodiments are only to explain, are not intended to limit the scope of the invention.
Unit used below is mass parts, and all compound used therefors are business product, or according to synthesis reported in the literature
Product；
The all cities in source of highly basic initiator, monomer a, solvent, catalyst, polyether macromonomer, function monomer b (removing b3)
Sell (lark prestige reagent, TCI reagent, Sigma-Aldrich and Huntsman)；
B3 is according to composite reported in the literature (J.Phys.Chem.C 2009,113,12950-12953).
1 embodiment compound used therefor title of table
The part of compounds structure that table 1 is enumerated is shown below:
" cement " in embodiment is II 52.5 portland cement of P；
" silicon ash " in embodiment is angstrom willing 95 grades of silicon ashes, SiO2Content 95%, 0.2 μm of average grain diameter；
1.8 microns of " SILICA FUME " average grain diameter in " admixture " in embodiment, 6 μm of " microballon " average grain diameter " are filled out
50 μm of average grain diameter of material "；
" sand " in embodiment is the continuous grade river sand of 0.075~4.75mm of partial size；
" rubble " is the basaltic broken stone of 4.75~19mm of partial size continuous grading in embodiment；
In embodiment " fiber " be fiber be length 13mm, the straight steel fibre and length 25mm, diameter of diameter 0.2mm
The end hook fiber type of 0.25mm mixes by a certain percentage；
" inorganic thixotroping reinforcing agent " in embodiment is modified Nano clay, the preparation method is as follows:
(1) nano clay is poured into beaker, by solid-to-liquid ratio 1:10,8% hydrochloric acid of concentration, constant temperature after being heated to 60 DEG C is added
10min is simultaneously stirred continuously, and is filtered after standing cooling 2h；It is put into drying box and is dried to permanent quality in 105 DEG C；(2) step (1) is taken to obtain
The nano clay and water obtained is mixed according to 1:5 ratio, using ultrasonic vibration lh；(3) slurry and silane for taking step (2) to obtain are even
Join agent with the mixing of 100:1 ratio, and high-speed mixer is used to stir 10min with the revolving speed of 8000rpm；Ultrasonic vibration is used later
1h；(4) slurry and neopelex for taking step (3) to obtain are mixed with the ratio of 8:1, in 60 DEG C of waters bath with thermostatic control
2h is stirred, uses ultrasonic vibration 0.5h later；
" viscosity reduction type high-performance water reducing agent " in embodiment is PCE1, PCE2, PCE3, PCE4；
The molecular weight distributing index 1.38 of PCE1, weight average molecular weight 31.1kDa, preparation process are as follows:
(1) reactor is removed water into deoxygenation, 142.15 parts of solvents 1 is added into reactor under inertia (nitrogen) atmosphere protection,
1.922 parts of highly basic initiators 1 are added thereto again, reactor is adjusted to 100 DEG C, is gradually equably added thereto in 8h
Enter 142.15 parts of monomer a1, obtains midbody polymer after being stirred to react 12h；
(2) 500 parts of polyether macromonomers 1 are added into another reactor, reactor is adjusted to 50 DEG C, is added thereto
The intermediate polymerization that 0.27 part of catalyst, 1,57.37 part of function monomer b1,11.72 parts of function monomer b2 and step (1) obtain
Object is stirred to react the volatilizable small molecule of vacuum removal after 6h, reactor is restored atmospheric pressure at room, obtains viscosity reduction type high-performance diminishing
Agent sample P CE1；
The molecular weight distributing index 1.26 of PCE2, weight average molecular weight 6.4kDa, preparation process are as follows:
(1) reactor is removed water into deoxygenation, 128.13 parts of solvents 2 is added into reactor under inertia (nitrogen) atmosphere protection,
Then 9.415 parts of highly basic initiators 2 are added thereto, reactor are adjusted to 120 DEG C, in 1h thereto gradually equably
128.13 parts of monomer a2 are added, obtain midbody polymer after being stirred to react 2h；
(2) add 583.6 parts of polyether macromonomers 2 into another reactor, reactor is adjusted to 20 DEG C, is added thereto
The midbody polymer that 2.623 parts of catalyst, 2,161 parts of function monomer b3,26.73 parts of function monomer b4 and step (1) obtain,
It is stirred to react the volatilizable small molecule of vacuum removal after 6h, reactor is restored into atmospheric pressure at room, obtains viscosity reduction type high-performance water reducing agent
Sample P CE2；
The molecular weight distributing index 1.29 of PCE3, weight average molecular weight 21.0kDa, preparation process are as follows:
(1) reactor is removed water into deoxygenation, 426.45 parts of solvents 3 is added into reactor under inertia (nitrogen) atmosphere protection,
4.991 parts of highly basic initiators 3 are added thereto again, reactor is adjusted to 150 DEG C, is gradually equably added thereto in 3h
Enter 142.15 parts of monomer a1, obtains midbody polymer after being stirred to react 8h；
(2) into another reactor be added 284.6 parts of polyether macromonomers 3, by reactor adjust to 0 DEG C, thereto plus
Enter the intermediate polymerization that 0.32 part of catalyst, 3,21.33 parts of function monomer b2,131.02 parts of function monomer b5 and step (1) obtain
Object is stirred to react the volatilizable small molecule of vacuum removal after 12h, reactor is restored atmospheric pressure at room, obtains viscosity reduction type high-performance and subtracts
Water sample PCE3；
The molecular weight distributing index 1.21 of PCE4, weight average molecular weight 59.0kDa, preparation process are as follows:
(1) reactor is removed water into deoxygenation, 1.348 parts of highly basic is added into reactor under inertia (nitrogen) atmosphere protection and draw
Agent 3 is sent out, reactor is adjusted to 125 DEG C, 128.13 parts of monomer a2 is gradually homogeneously added into thereto in 3h, is stirred to react
Midbody polymer is obtained after 4h；
(2) into another reactor be added 772.2 parts of polyether macromonomers 4, by reactor adjust to 50 DEG C, thereto plus
Enter the intermediate polymerization that 2.002 parts of catalyst 4,7.11 function monomer b2,214.66 parts of function monomer b3 and step (1) obtain
Object is stirred to react the volatilizable small molecule of vacuum removal after 4h, reactor is restored atmospheric pressure at room, obtains viscosity reduction type high-performance diminishing
Agent sample P CE4；
" defoaming agent " is Polyether Modified Polysiloxanes Defoaming Agent in embodiment.
Low viscous easily pumping ultra-high performance concrete each component content in each embodiment of table 1
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 80:70:300 ratio in embodiment 1；Filler group
Divide and each component mass ratio is flyash: ground blast furnace slag: silica flour=80:120:100；Thixotroping reinforcing agent is inorganic thixotroping enhancing
Agent, organic thixotroping reinforcing agent are mixed in the ratio of quality 10:5, and organic thixotroping reinforcing agent is propylene glycol alginate；Water-reducing agent is
PCE1；Fiber is that straight steel fibre and end hook fiber type are mixed in quality 2:1 ratio.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 80:70:300 ratio in embodiment 2；Filler group
Divide and each component mass ratio is flyash: ground blast furnace slag: silica flour=80:120:100；Thixotroping reinforcing agent is inorganic thixotroping enhancing
Agent, organic thixotroping reinforcing agent are mixed in the ratio of quality 10:5, and organic thixotroping reinforcing agent is starch ether；Water-reducing agent is PCE2；It is fine
Dimension is that straight steel fibre and end hook fiber type are mixed in quality 2:1 ratio.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 100:100:250 ratio in embodiment 3；Filler
Component and each component mass ratio are flyash: ground blast furnace slag: silica flour=70:80:100；Thixotroping reinforcing agent is inorganic thixotroping increasing
Strong agent；Water-reducing agent is PCE3；Fiber is end hook type steel fibers.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 120:80:250 ratio in embodiment 4；Filler group
Divide and each component mass ratio is flyash: ground blast furnace slag: silica flour=100:80:70；Thixotroping reinforcing agent is inorganic thixotroping enhancing
Agent, organic thixotroping reinforcing agent are mixed in the ratio of quality 10:5, and organic thixotroping reinforcing agent is polyvinyl alcohol；Water-reducing agent is PCE4；
Fiber is that straight steel fibre and end hook fiber type are mixed in quality 1:1 ratio.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 120:80:200 ratio in embodiment 5；Filler group
Divide and each component mass ratio is flyash: ground blast furnace slag: silica flour=80:70:50；Thixotroping reinforcing agent is inorganic thixotroping enhancing
Agent；Water-reducing agent is PCE1；Fiber is that straight steel fibre and end hook type steel fibers are mixed in quality 3:1 ratio.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 40:60:200 ratio in embodiment 6；Filler group
Divide and each component mass ratio is flyash: ground blast furnace slag: silica flour=50:50:100；Thixotroping reinforcing agent is inorganic thixotroping enhancing
Agent, organic thixotroping reinforcing agent are mixed in the ratio of quality 5:10, and organic thixotroping reinforcing agent is guar gum；Water-reducing agent is PCE4；It is fine
Dimension is that straight steel fibre and end hook type steel fibers are mixed in quality 1:1 ratio.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 50:100:200 ratio in embodiment 7；Filler group
Divide and each component mass ratio is flyash: ground blast furnace slag: silica flour=80:70:50；Thixotroping reinforcing agent is complexing type polyurethane water
Soluble polymer；Water-reducing agent is PCE2；Fiber is end hook type steel fibers.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 70:80:350 ratio in embodiment 8；Filler group
Divide and each component mass ratio is flyash: ground blast furnace slag: silica flour=100:150:100；Thixotroping reinforcing agent is inorganic thixotroping increasing
Strong agent；Water-reducing agent is PCE3；Fiber is that straight steel fibre and end hook type steel fibers are mixed in quality 1:2 ratio.
Admixture group is divided into SILICA FUME, microballon and filler and mixes in quality 120:130:350 ratio in embodiment 9；Filler
Component and each component mass ratio are flyash: ground blast furnace slag: silica flour=100:100:150；Thixotroping reinforcing agent is inorganic thixotroping
Reinforcing agent, organic thixotroping reinforcing agent are mixed in the ratio of quality 10:5, and organic thixotroping reinforcing agent is xanthan gum；Water-reducing agent is
PCE1；Fiber is that straight steel fibre and end hook type steel fibers are mixed in quality 2:1 ratio.
Comparative example
Low viscous easily pumping ultra-high performance concrete each component content in each comparative example of table 2
Comparative example 1: water-reducing agent is common high-performance water reducing agent, and other components are same as Example 1.
Comparative example 2: lacking micro- silicon ash, microballon in admixture, other components are same as Example 1.
Comparative example 3: lacking thixotroping reinforcing agent, and other components are same as Example 1.
Comparative example 4: conventional ultra-high performance concrete match ratio, admixture are levigate silica flour, and water-reducing agent is common high property
Energy water-reducing agent, other components material is the same as embodiment 1.
The very-high performance coagulation in low viscous easily pumping ultra-high performance concrete and comparative example 1-4 in above-described embodiment 1-9
Soil is added and is mixed in advance in the preparation first by cement, silicon ash, admixture, silica flour, river sand and rubble mixing 1min
Water, defoaming agent, thixotroping reinforcing agent and water-reducing agent stir 3min, fiber is added later and stirs 3min, it is mixed that very-high performance is made
Solidifying soil.
Application Example
Slump flow test, viscosity, pumping resistance are carried out with the ultra-high performance concrete in embodiment 1-9 and comparative example 1-4
And compression strength comparative test.
Ultra-high performance concrete divergence is according to GB50080-2016 " Standard for test methods of properties of ordinary concrete mixture mark
It is quasi- " in prescriptive procedure test；Viscosity passes through T50Time reflects, according to CECS203-2006 " self-compacting concrete application technology
Regulation " in prescriptive procedure tested, the time is longer to illustrate that concrete viscosity is bigger；Pumping resistance passes through friction gauge test result
It obtains, is lost and characterized with unit distance pumping pressure；Compression strength according to GBT 31387-2015 " Reactive Powder Concrete " into
Row test.
Test result is as follows:
Low viscous easily pumping ultra-high performance concrete performance in 3 embodiment of table
Ultra-high performance concrete performance in 4 comparative example of table
As can be seen from the test results, using admixture of the invention, thixotroping reinforcing agent, viscosity reduction type high-performance diminishing and lead to
Cross adjustment fiber consumption, sand, stone, water consumption and the ultra-high performance concrete not only flowing with higher of defoaming agent preparation
Property, lower viscosity and lower pumping resistance, also there is advantages of higher compressive strength, after standard curing 28d, agent on crack resistance of concrete pressure
It spends up to 180MPa or more.In addition to this, cement is substituted using the mineral-filled material of large dosage in the present invention, there is typical low water
Cement content feature, significantly reduces cement consumption, reduces environmental pollution.
Common high-performance water reducing agent is used in comparative example 1, other components are same as Example 1, and performance data is shown: using
Common high-performance water reducing agent, concrete fluidity, viscosity, pumping resistance and compression strength are significantly worse than embodiment 1.Main chain
Hydrophilic, narrow molecular weight distribution viscosity reduction type high-performance water reducing agent realizes the uniform rapid dispersion of superfine powder, therefore improves super
High performance concrete mobility reduces viscosity, reduces pumping resistance.
Lack micro- silicon ash, microballon in comparative example 2, other components are same as Example 1, and performance data is shown: micro- silicon ash and
After microballon, concrete viscosity, pumping resistance are significantly worse than embodiment 1.Made by the pattern of SILICA FUME and microballon powder granule
Particles' interaction power is reduced with surface charge effect, increases the water film thickness of particle surface, and improve additional
The adsorption efficiency of agent effectively reduces ultra-high performance concrete viscosity, and then reduces pumping resistance.
Lack thixotroping reinforcing agent in comparative example 3, other components are same as Example 1, and performance data is shown: lacking thixotroping increasing
After strong agent, concrete viscosity, pumping resistance are significantly higher than embodiment 1.Incorporation thixotroping reinforcing agent can realize that concrete shearing acts on
Lower presentation shear shinning characteristic, viscosity are substantially reduced, and frictional resistance substantially reduces in lubricant layer in pumping procedure, i.e. pumping resistance
Power significantly reduces.
Comparative example 4 is conventional ultra-high performance concrete match ratio, and admixture is levigate silica flour, and water-reducing agent is common high property
Energy water-reducing agent, with embodiment 1, performance data is shown other components material: low viscous easily pumping ultra-high performance concrete of the invention
Not only mobility is significantly better than common very-high performance, but also viscosity and pumping resistance are greatly lowered.In addition, of the invention is low
The compression strength of easy pump concrete is glued also superior to conventional ultra-high performance concrete.
Claims (8)
1. a kind of low viscous easily pumping ultra-high performance concrete, which is characterized in that be made of following each component by mass parts:
The cement is the portland cement or ordinary portland cement of 42.5 or more strength grade, and average grain diameter is 10~20
μm；
SiO in the silicon ash2Content 90wt% or more, the average grain diameter of silicon ash are 0.2 μm~1 μm；
The admixture is the composition of SILICA FUME, microballon and filler；Wherein the average grain diameter of the SILICA FUME is 1~5 μm；
The average grain diameter of the microballon is 2~10 μm；The filler be flyash, ground blast furnace slag, in silica flour any one or one
Kind any of the above ratio mixing, the average grain diameter of the filler are 10~100 μm；
The sand is 0.075~4.75mm of partial size continuous grading sand；
The rubble is limestone, granite, diabase, any one in basalt, and grain diameter is that 4.75~19mm connects
Continuous gradation；
The fiber is metallic fiber, 3~25mm of length, 0.1~0.3mm of diameter；
The thixotroping reinforcing agent is mixed selected from one or both of inorganic thixotroping reinforcing agent, organic thixotroping reinforcing agent arbitrary proportion
It closes；
The water-reducing agent is viscosity reduction type high-performance water reducing agent；
The defoaming agent is any one or two kinds of arbitrary proportions mixing of Polyether Modified Polysiloxanes Defoaming Agent or polyether antifoam agent；
The inorganic thixotroping reinforcing agent is modified Nano clay, and preparation method is as follows:
1. nano clay is poured into beaker, it is 5~30% that mass concentration, which is added, by mass ratio 1:3~1:20 of nano clay and acid
Acid, keep 5~20min of constant temperature and being stirred continuously after being heated to 40~60 DEG C, filtered after standing cooling 2~4h, be put into drying
Case is dried to permanent quality in 105 DEG C；
Wherein any one or two kind arbitrary proportions mixing of the acid in hydrochloric acid, sulfuric acid and phosphoric acid；
2. the nano clay obtained after taking step 1. to dry is mixed with water according to 1:3~1:10 mass ratio, using ultrasonic vibration l
~2h obtains nano clay slurries；
3. the nano clay slurries for taking step 2. to obtain are mixed with silane coupling agent with 100:1~200:1 mass ratio, and are used
High-speed mixer stirs 10~20min with the revolving speed of 2000~10000rpm, uses 0.5~1h of ultrasonic vibration later；
4. the slurry for taking step 3. to obtain is mixed with anionic surfactant with the mass ratio of 5:1~20:1, in 40~80
1~2h is stirred in DEG C water bath with thermostatic control, is used 0.5~1h of ultrasonic vibration later, is obtained the modified Nano clay；The wherein yin
Ionic surface active agent be selected from odium stearate, neopelex, polyacrylic acid, polyacrylamide, alkyl phosphorus carboxylate,
Any one or more than one arbitrary proportion mixing in alkyl alcohol ether carboxylate；
Organic thixotroping reinforcing agent is complexing type polyurethane water-soluble polymer, guar gum, xanthan gum, propylene glycol alginate
Ester, polyacrylamide, starch ether, any one or two kinds in polyvinyl alcohol are mixed with arbitrary proportion；
The viscosity reduction type high-performance water reducing agent is the polymer with following general formula (1):
Wherein z is indicated and functional group R0The connection quantity of the repetitive structure X of connection, value range are the integer of 1-4；R0Indicate H
Or straight chain or the hydrogen functional group of saturated carbon containing branch containing 1-12 carbon atom, R0When for H, z must be 1；X is to meet following lead to
Any one in functional group shown in formula (2):
Wherein, X1、X1'、X1" separately indicate carbonyl or-CH2Or-CH2CH2-；X2Indicate any in following functional group
It is a kind of: (1) saturated alkyl or-(CH containing 1-12 carbon atom2CH2O)mCH2CH2, wherein m indicates ethoxy repeating units number,
Its value range is the integer of 1-11, and (2)-CH (NH2)-, C are L chiral；R2、R2'、R2" separately indicate H or CH3；
R4' expression-CH2CH2-、-CH2CH2SCH2CH2-、-CH2CH2SCH2CH2OCH2CH2-、-CO-CH2CH2SCH2CH2-、-CO-
CH2CH2CH2CH2OCH2CH2In any one；R5Indicate H or the saturated alkyl containing 1-12 carbon atom；M2 +Indicate H+、
Alkali metal ion or ammonium ion；R9Indicate the saturated alkyl containing 1-12 carbon atom；C, d respectively indicate in polymer ethyoxyl and
The molar average adduct number of isopropoxy chain link, and meet 11≤(c+d)≤114, d/c < 1/2；x1、x2Polymerization is respectively represented with y
The molar average adduct number of each chain link in object super plasticizer, and meet following relationship: (1) (x1+x2+ y) value with the product of z
Range is 8-150；(2)y/(x1+x2+ y) value range be 0.15-0.5；(3)(x1+x2)/(x1+x2+ y) value range be
0.5-0.85；(4)x2/x1Value range be 0-0.5；
The viscosity reduction type high-performance water reducing agent molecular weight distributing index PDI is not more than 1.4, weight average molecular weight range 5000-
100000。
2. the low viscous easily pumping ultra-high performance concrete of one kind according to claim 1, which is characterized in that the low viscous easily pump
Ultra-high performance concrete is sent to be made of following each component by mass parts:
3. the low viscous easily pumping ultra-high performance concrete of one kind according to claim 1 or 2, which is characterized in that the viscosity reduction
Type high-performance water reducing agent can be prepared by following steps:
(1) deoxygenation is removed water in the reactor, and monomer a is gone forward side by side under the conditions of highly basic initiator by bulk polymerization or polymerisation in solution
Row anionic ring-opening polymerization prepares intermediate polymer, and main chain is polyglycol chain, is grafted with a large amount of double bonds thereon；
The molar ratio of the highly basic initiator and monomer a are 1:8-150；
The monomer a is the monomer containing double bond and epoxy-functional simultaneously, is met any in structure shown in following general formula (3)
It is a kind of:
Wherein R2Indicate H or CH3, Y expression carbonyl ,-CH2Or-CH2CH2-；
The highly basic initiator is sodium alkoxide or potassium alcoholate, and " alcohol " refers to " by the straight chain containing 1-12 carbon atom or containing branch saturation
The Organic Alcohol of the composition of hydrocarbon functional group and 1-4 terminal hydroxy group "；
The polymerization temperature is 50-150 DEG C, reaction time 2-24h；
(2) in the presence of a catalyst, adsorption functional group is connected by the Michael addition reaction of sulfydryl and double bond and had
It is viscosity reduction type high-performance water reducing agent that the polymer, which is made, in the long polyether lateral chain of steric hindrance effect；Wherein adsorption functional group is come
From function small molecule monomer b, and long polyether lateral chain is from the polymeric monomer E simultaneously with sulfydryl and polyethers chain structure；
Functionality small molecule monomer b described in step (2) is while having sulfydryl and carboxyl or sulfonic monomer, the monomer
B is a kind of composition, and the composition is the mixing of component A and B component, and B component mole accounts for A and B component integral molar quantity
0-50%；
Wherein component A is (a) or one or both of (b): (a) meeting any one in structure shown in following general formula (5)
Or more than one any combination:
R8Indicate saturated alkyl or-(CH containing 1-12 carbon atom2CH2O)mCH2CH2, wherein m indicates ethoxy repeating units
Number, value range are the integer of 1-11；
Or (b) hydrochloride or sulfate of cysteine；
B component is any one or the more than one any combination met in structure shown in following general formula (6):
Wherein M2 +Indicate H+, alkali metal ion or ammonium ion, R9Indicate the saturated alkyl containing 1-12 carbon atom；
Polymeric monomer E described in step (2) is one of structure shown in following general formula (7) or more than one any mixing:
R5Indicate H or the saturated alkyl containing 1-12 carbon atom, R4Indicate the organo-functional group that a sulfydryl is contained in end,
For following functional group-CH2CH2SH、-CH2CH2SCH2CH2SH、-CH2CH2SCH2CH2OCH2CH2SH、-CO-CH2CH2SCH2CH2SH
Or-CO-CH2CH2CH2CH2OCH2CH2Any one in SH, c, d respectively indicate ethyoxyl and isopropoxy in polyethers H structure
The molar average adduct number of chain link, and meet 11≤(c+d)≤114, d/c < 1/2；And the molecular weight distributing index of polymeric monomer E
PDI is not higher than 1.3；
Step (2) addition reaction temperature is 0-100 DEG C, reaction time 3-24h；
The mole of polymeric monomer E accounts for the 15-50% of monomer a mole in step (2)；The mole of catalyst accounts for a moles of monomer
The 0.2-5% of amount；The mole of functional small molecule monomer b is calculated respectively with the mole of sulfydryl contained therein, total moles
Amount accounts for the 50-85% of monomer a mole, and the integral molar quantity of polymeric monomer E and functional small molecule monomer b are not less than monomer a's
Mole.
4. the low viscous easily pumping ultra-high performance concrete of one kind according to claim 3, which is characterized in that the viscosity reduction type is high
According to polymerisation in solution in the preparation step (1) of performance water-reducing agent, then the solvent in solution is tetrahydrofuran, dioxane, two
First sulfoxide, DMAC N,N' dimethyl acetamide, N-methylmorpholine, N-ethylmorpholine, any one in N-Methyl pyrrolidone；It is described
The quality of solvent is equivalent to the 0-300% of monomer a mass, includes 0% and 300%.
5. the low viscous easily pumping ultra-high performance concrete of one kind according to claim 3, which is characterized in that the viscosity reduction type is high
Catalyst described in the preparation step (2) of performance water-reducing agent is sodium hydroxide or potassium hydroxide or satisfying containing 1-12 carbon atom
Sodium alkoxide corresponding with the Organic Alcohol of alkyl or potassium alcoholate meet (4-1) shown in general formula, any one in general formula (4-2) structure:
In general formula (4-1), R10、R11、R12Separately represent H or the saturated alkyl containing 1-6 carbon atom, general formula (4-2)
In, R13、R14、R15Separately represent H or saturated alkyl or phenyl or cyclohexyl or cyclopenta containing 1-6 carbon atom
Or 1-3 carbon atom saturated alkyl phenyl replaced or the cyclohexyl or 1-3 carbon atom of the substitution of 1-3 carbon atom saturated alkyl
The cyclopenta that saturated alkyl replaces.
6. the low viscous easily pumping ultra-high performance concrete of one kind according to claim 1 or 2, which is characterized in that the blending
Expect component and each component mass ratio is SILICA FUME: microballon: filler=80:70:300；The filler component and each component mass ratio
For flyash: ground slag: silica flour=80:120:100.
7. the low viscous easily pumping ultra-high performance concrete of one kind according to claim 1 or 2, which is characterized in that the fiber
End hook type high-strength steel for length 13mm, the straight fine high-strength steel fibre of diameter 0.2mm and length 25mm, diameter 0.25mm is fine
Dimension example 2:1 in mass ratio mixes.
8. the preparation method of the low viscous easily pumping ultra-high performance concrete of the described in any item one kind of claim 1 to 7, feature exist
In, include the following steps: first by cement, silicon ash, admixture, sand and rubble mix 0.5~2min, add and mix in advance
Water, defoaming agent, thixotroping reinforcing agent and the water-reducing agent of conjunction stir 2~4min, and fiber is added later and stirs 2~4min, institute is made
State low viscous easily pumping ultra-high performance concrete.
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| CN111517714A (en) * | 2020-04-07 | 2020-08-11 | 中铁大桥科学研究院有限公司 | Easily-pumped coarse aggregate-containing ultra-high performance concrete and preparation method thereof |
| CN111533510A (en) * | 2020-05-08 | 2020-08-14 | 昭通公路局 | Concrete formula |
| CN111995327A (en) * | 2020-09-01 | 2020-11-27 | 中国建材检验认证集团北京天誉有限公司 | Ultrahigh-performance concrete and preparation method thereof |
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| CN113845347A (en) * | 2021-10-28 | 2021-12-28 | 重庆伍圣建材有限公司 | High-strength high-toughness composite compact cementing material |
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| CN115716734B (en) * | 2022-11-22 | 2023-12-26 | 深圳市海维科技研发有限责任公司 | Anti-cracking corrosion-resistant ultra-high-performance concrete with thixotropic property and preparation method thereof |
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