A kind of preparation method of early strong concrete additive
Technical field:
The present invention relates to a kind of early strong concrete additive, and in particular to aquation silicon prepared by a kind of utilization interfacial reaction
The hollow nanoparticle concrete early strength agent of sour calcium, belongs to technical field of concrete additives.
Background technology:
Early strength agent is a kind of acceleration cement early hydration, improves early age strength of concrete to meet construction with structural requirement
Additive.Current global economy development is slowed down, and environmental problem becomes increasingly conspicuous, and accelerates the early hydration of concrete, improves its early stage
Intensity is to increase economic efficiency, accelerating construction progress, reduce CO2 discharge be particularly important.Meanwhile, with concrete technology
Development, application of the trade waste as basic raw material in mixed soil be more and more extensive, in the production of Large Precast Members
In in order to reduce early hydration heat, improve concrete durability, the mineral admixture such as substantial amounts of use breeze, flyash, therefore,
The early strength development of concrete is more slow, affects the technique progress such as mould turnover and prestressing force loading.
Nano level hydrated calcium silicate is a kind of common early strength agent, and which has phase with hydrolysis product of cement C-S-H gels
Near chemical constitution, can grow crystal seed as hydrated product, accelerate the early hydration reaction of cement, potent with significant morning
Really.
At present, calcium nitrate and the aqueous solution direct reaction of sodium silicate is generally selected to generate hydrated calcium silicate, afterwards will precipitation
Hydrated calcium silicate powder is made after product filtering drying.But during practical application, this powder is difficult dispersed in concrete
Open, have impact on its early strong effect;There are some document announcements in the presence of dispersant, from calcium nitrate and the water of sodium silicate
Solution direct reaction generates hydrated calcium silicate colloidal sol, and this colloidal sol stable storing may be directly applied to concrete field.
It is early strong as cement-based material that such as Chinese patent CN201410593398 discloses a kind of hydrated calcium silicate colloidal sol
The preparation method of agent, its in the presence of dispersant naphthalenesulfonate formaldehyde condensation compound, directly by the water-soluble of calcium nitrate and sodium silicate
Liquid hybrid reaction obtains hydrated calcium silicate sol dispersion, and the dispersion liquid is stable liquid, cement paste is had certain
Early strong effect.
Chinese patent CN201410591887 is then announced and is directly obtained the aqueous solution reaction of calcium nitrate and sodium silicate
Hydrated calcium silicate colloidal sol, is scatter with naphthalenesulfonate formaldehyde condensation compound after this colloidal sol is filtered again, is similarly obtained aquation silicic acid
Calcium sol dispersion liquid.
Hydrated calcium silicate colloidal sol essence prepared by said method is the induction nucleation that make use of sol particles surface, its
Play inducing action is only the part hydrated calcium silicate on surface, and internal big quantity of material does not have early strength function, causes volume
It is higher, the wasting of resources.
The content of the invention:
Or being difficult to effectively dispersion, or the too high shortcoming of volume, the present invention for existing hydrated calcium silicate class early strength agent
Early strength agent that a kind of early strong effect is projected, consumption is less and preparation method thereof is provided.
The applicant it has been investigated that, hydrated calcium silicate is prepared into into hollow nanoparticle, on the one hand its induction crystallization
The effect of nucleation is retained, with obvious early strong effect;On the other hand, as with hollow structure, use can be greatly reduced
Amount.
That is, early strong concrete additive of the present invention, its composition is comprising a kind of hollow nanoparticle of hydrated calcium silicate.
The preparation method of early strong concrete additive of the present invention, i.e., the hollow nanoparticle of described hydrated calcium silicate
Preparation method, by being water-soluble Ca salt in water phase in dispersion phase, and in continuous phase be non-polar solven in positive silicic acid
Tetra-ethyl ester, in the presence of catalyst ammonia water, is prepared from by interfacial reaction.
The water-soluble Ca salt is calcium nitrate, calcium nitrite.
The non-polar solven refers to hexamethylene, white oil, toluene.
Preparation method of the present invention is:
First by water-soluble Ca salt and catalyst ammonia water and water wiring solution-forming, then by the aqueous solution with contain emulsifying agent
And the non-polar solven of co-stabilizer is in 20~40 DEG C of water-bath, under high-speed stirred, mix pre-emulsification, then by ultrasonic emulsification,
Make anti-phase miniemulsion;
Afterwards tetraethyl orthosilicate (TEOS) is slowly dropped in the emulsion, time for adding is 5-10 hours, and TEOS is dissolved in
In continuous phase, when TEOS is diffused into continuous phase and dispersed phase interface, due to there is catalyst ammonia water in dispersion phase, TEOS will be
Interface generates hydrated calcium silicate shell with calcium salt reaction;
Ultimately form the hollow nanoparticle of hydrated calcium silicate.
Emulsifying agent adopts lipophile nonionic surfactant, and HLB is 3~8.The consumption of emulsifying agent accounts for the 3 of whole system
~5% (emulsifying agent/(continuous phase+dispersion phase (not including inorganic salt))), emulsifying dosage is difficult to obtain the breast of expected particle diameter very little
Liquid, stability are also short of.
The emulsifying agent is Span40, Span60, Span80 and their two or more mixed in any proportion
Compound.
Co-stabilizer adopts polyvinyl pyrrolidone (PVP), hexadecyltrimethylammonium chloride (CTAC), cetyl
Trimethylammonium bromide (CTAB).
The consumption of co-stabilizer account for whole system 0.5~1% (co-stabilizer/(continuous phase+dispersion phase is (not comprising inorganic
Salt))).
Co-stabilizer can further improve stability of emulsion with emulsifying agent synergism.In obtaining after the completion of synthesis
Empty particle is dispersed in water, and may also function as Stabilization, improves storage stability and ease of use.
Preparation method of the present invention is broadly divided into three below step:
(1) the anti-phase miniemulsion containing calcium salt and catalyst is prepared first, by the water-soluble of water-soluble Ca salt and catalyst ammonia water
Liquid is mixed under high-speed stirred and ultrasonic emulsification with the non-polar solven containing emulsifying agent and co-stabilizer.
Dispersion phase is the aqueous solution of calcium salt and ammonia.Ammonia is the important catalyst that TEOS is reacted with calcium salt, its use
Measure 1~2% for TEOS mass.Water-soluble Ca salt includes the nothing that calcium nitrate, calcium nitrite, calcium acetate etc. can be dissolved in water
Machine calcium salt, its mass concentration are 10~20%.
The concentration for increasing water-soluble Ca salt can alleviate laplace pressure, make stability of emulsion obtain a certain degree of carrying
Height, but after the mass concentration of water-soluble Ca salt is more than 20%, there is detrimental effect to emulsion intercalation method.
Continuous phase accounts for whole system using hexamethylene, toluene, white oil etc. and the immiscible non-polar solven of water, continuous phase
Mass ratio (continuous phase/(continuous phase+dispersion phase (including inorganic salt))) is 50~70%.
After mixing above-mentioned dispersion phase and continuously, it is placed in 20~40 DEG C of water-bath, 15 points of pre-emulsification under high-speed stirred
Clock, then by ultrasonic emulsification 15 minutes, in 50~200nm, particle was too little in above-mentioned bar for the particle diameter of the reversed-phase emulsion for finally giving
It is difficult under part, and emulsion intercalation method is also bad, the hollow-particle specific surface area for finally giving greatly very much is little, under same quality
Early epistasis necessarily can be reduced, and have impact on the application performance of final product.
(2) keeping temperature is 20~40 DEG C, under stirring condition in 5~10h Deca TEOS, the follow-up continuation of insurance temperature of completion of dropwise addition
Reaction 24h.The consumption of TEOS is determined by the consumption of calcium salt, it is necessary to meet Ca/Si mol ratios 2:1~1:1.
(3) 80 DEG C of breakdowns of emulsion are increased the temperature to, water is collected and is mutually obtained the prepared hollow nanoparticle of hydrated calcium silicate
Dispersion liquid.
The early-strength dose of nanoscale calcium silicates nucleus provided needed for cement early hydration crystal growth, shortens
The time that the ionic liquid phase supersaturation of aquation initial stage, nucleus are formed, so as to significantly accelerating cement early hydration.Meanwhile, this
Bright early strength agent is hollow nanoparticle, compared with conventional hydrated calcium silicate colloidal sol, eliminates inside and does not play crystallization nucleation work
Part calcium silicates, therefore volume is greatly lowered, effect is more preferable.
The early strength agent is acted on without villaumite, to the reinforcing bar non-corroding in concrete, does not affect the durability of concrete.The morning
Strong agent is extremely stable suspension system, is easy to addition, it is easy to dispersed in concrete preparation process.Additionally, the morning
Strong agent promotes cement just to produce substantial amounts of calcium hydroxide in age earlier, is advantageous to the activity excitation of mineral admixture,
It is particularly evident for the concrete early strong effect using high content mineral admixtures, it is particularly well-suited to the life of concrete prefabricated element
Produce, can effectively reduce or even remove steam curing process from.
Description of the drawings
Fig. 1:Synthetic example 1, embodiment 2, the TEM photos of 3 gained sample of embodiment.
Specific embodiment:
Following examples are described in further detail the process that the method according to the invention prepares polymerizate, and these realities
Apply example to be given by way of illustration, its object is to allow person skilled in the art to will appreciate that present disclosure according to this
Implement, but these embodiments are in no way intended to limit the scope of the present invention.All equivalence changes made according to spirit of the invention are repaiied
Decorations, should all be included within the scope of the present invention.
Synthetic example 1
50 grams of calcium nitrate tetrahydrates and 0.55 gram of ammonia are dissolved in 227.78 grams of water, then by this solution be added to dissolved with
In 648.15 grams of hexamethylene of 43.80 grams of Span80 and 7.88 gram of PVP, in 25 DEG C of high-speed stirred pre-emulsifications 15 minutes, Ran Houzai
Ultrasonic emulsification 15 minutes, obtains emulsion;At 25 DEG C and under stirring, 36.75 grams of TEOS are slowly dropped to into emulsifying in 7 hours
In liquid, after completion of dropwise addition continues reaction 24h, 80 DEG C of breakdowns of emulsion are increased the temperature to, collect water and mutually obtain prepared aquation silicic acid
The dispersion liquid of the hollow nanoparticle of calcium.
Synthetic example 2
50 grams of calcium nitrate tetrahydrates and 0.59 gram of ammonia are dissolved in 283.33 grams of water, then by this solution be added to dissolved with
In 676.77 grams of hexamethylene of 43.20 grams of Span80 and 7.68 gram of CTAB, in 30 DEG C of high-speed stirred pre-emulsifications 15 minutes, Ran Houzai
Ultrasonic emulsification 15 minutes, obtains emulsion;At 30 DEG C and under stirring, 29.40 grams of TEOS are slowly dropped to into emulsifying in 6 hours
In liquid, after completion of dropwise addition continues reaction 24h, 80 DEG C of breakdowns of emulsion are increased the temperature to, collect water and mutually obtain prepared aquation silicic acid
The dispersion liquid of the hollow nanoparticle of calcium.
Synthetic example 3
50 grams of calcium nitrate tetrahydrates and 0.27 gram of ammonia are dissolved in 366.67 grams of water, then by this solution be added to dissolved with
In 575.4 grams of hexamethylene of 35.80 grams of Span60 and 7.54 gram of CTAC, in 35 DEG C of high-speed stirred pre-emulsifications 15 minutes, Ran Houzai
Ultrasonic emulsification 15 minutes, obtains emulsion;At 35 DEG C and under stirring, 24.50 grams of TEOS are slowly dropped to into emulsifying in 5 hours
In liquid, after completion of dropwise addition continues reaction 24h, 80 DEG C of breakdowns of emulsion are increased the temperature to, collect water and mutually obtain prepared aquation silicic acid
The dispersion liquid of the hollow nanoparticle of calcium.
Synthetic example 4
50 grams of calcium nitrate tetrahydrates and 0.44 gram of ammonia are dissolved in 283.33 grams of water, then by this solution be added to dissolved with
In 407.41 grams of hexamethylene of 22.10 grams of Span40 and 3.45 gram of PVP, in 25 DEG C of high-speed stirred pre-emulsifications 15 minutes, Ran Houzai
Ultrasonic emulsification 15 minutes, obtains emulsion;At 25 DEG C and under stirring, 36.75 grams of TEOS are slowly dropped to into emulsifying in 7 hours
In liquid, after completion of dropwise addition continues reaction 24h, 80 DEG C of breakdowns of emulsion are increased the temperature to, collect water and mutually obtain prepared aquation silicic acid
The dispersion liquid of the hollow nanoparticle of calcium.
Synthetic example 5
50 gram of two hydration calcium nitrite and 0.74 gram of ammonia are dissolved in 283.33 grams of water, then this solution are added to molten
In having 500.00 grams of toluene of 27.42 grams of Span60 and 5.48 gram of PVP, in 25 DEG C of high-speed stirred pre-emulsifications 15 minutes, Ran Houzai
Ultrasonic emulsification 15 minutes, obtains emulsion;At 25 DEG C and under stirring, 41.34 grams of TEOS are slowly dropped to into emulsifying in 8 hours
In liquid, after completion of dropwise addition continues reaction 24h, 80 DEG C of breakdowns of emulsion are increased the temperature to, collect water and mutually obtain prepared aquation silicic acid
The dispersion liquid of the hollow nanoparticle of calcium.
Synthetic example 6
50 gram of two hydration calcium nitrite and 0.65 gram of ammonia are dissolved in 283.33 grams of water, then this solution are added to molten
In having 500.00 grams of hexamethylene of 31.33 grams of Span60 and 6.27 gram of PVP, in 25 DEG C of high-speed stirred pre-emulsifications 15 minutes, then
Ultrasonic emulsification 15 minutes, obtain emulsion again;At 25 DEG C and under stirring, 34.45 grams of TEOS are slowly dropped to into breast in 7 hours
Change in liquid, after completion of dropwise addition continues reaction 24h, increase the temperature to 80 DEG C of breakdowns of emulsion, collect water and mutually obtain prepared aquation silicon
The dispersion liquid of the hollow nanoparticle of sour calcium.
Synthetic example 7
50 grams of calcium acetates and 0.57 gram of ammonia are dissolved in 283.33 grams of water, then this solution is added to dissolved with 28.98
In 500.00 grams of white oils of gram Span60 and 4.70 gram of PVP, in 25 DEG C of high-speed stirred pre-emulsifications 15 minutes, then ultrasonic emulsification again
15 minutes, obtain emulsion;At 25 DEG C and under stirring, 43.90 grams of TEOS are slowly dropped in emulsion in 9 hours, are dripped
Plus after terminating to continue reaction 24h, increase the temperature to 80 DEG C of breakdowns of emulsion, collect water and mutually obtain that prepared hydrated calcium silicate is hollow to be received
The dispersion liquid of rice corpuscles.
Synthetic example 8
50 grams of calcium acetates and 0.66 gram of ammonia are dissolved in 283.33 grams of water, then this solution is added to dissolved with 27.42
In 500.00 grams of hexamethylene of gram Span60 and 3.92 gram of PVP, in 25 DEG C of high-speed stirred pre-emulsifications 15 minutes, then ultrasound breast again
Change 15 minutes, obtain emulsion;At 25 DEG C and under stirring, 43.90 grams of TEOS are slowly dropped in emulsion in 9 hours,
After completion of dropwise addition continues reaction 24h, 80 DEG C of breakdowns of emulsion are increased the temperature to, it is hollow that collection water mutually obtains prepared hydrated calcium silicate
The dispersion liquid of nanoparticle.
Contrast synthesis example
Contrast synthesis example is according to Chinese patent CN201410593398 embodiments two, the solid hydrated calcium silicate of synthesis
Early strength agent, it is specific as follows:Weigh 236 grams of calcium nitrate tetrahydrates and be dissolved in 1300 grams of water, stirring added naphthalene sulfonate after 20 seconds
3.07 grams of formaldehyde condensation products (commercially available standard type high efficiency water reducing agent) continue stirring 30 seconds;Weigh 284 grams of sodium silicate nanahydrates molten
In 1300 grams of water, stirring adds 3.07 grams of continuation of naphthalenesulfonate formaldehyde condensation compound (commercially available standard type high efficiency water reducing agent) after 20 seconds
Stirring 30 seconds;Above-mentioned two solution stirring is mixed 360 seconds, milky gel state liquid, as solid hydrated calcium silicate is obtained
Early strength agent
Application Example
Application Example 1
Using transmission electron microscope (TEM:JEM-200CX;Japanese JEOL companies) the hollow grain of observation gained calcium silicate hydrate nano
The pattern of son, the TEM photos of the sample of embodiment 1 are shown in Fig. 1, from electromicroscopic photograph it can be seen that hydrated calcium silicate receive define it is hollow
Spheroidal particle.
Application Example 2
Concrete crushing strength test is carried out according to the concrete mix shown in table 1, concrete raw material is respectively
Reference cement (PI 52.5), meets the II levels flyash and S95 ground slag powders of national standard, and modulus of fineness is 2.7 river
Sand, the rubble of 5-25mm continuous gradings.
1 concrete mix (Kg/m of table3)
Cement |
Breeze |
Flyash |
Sand |
Rubble |
Water |
337.5 |
45 |
67.5 |
700 |
1140 |
138 |
It is not of the same age under standard curing (20 DEG C, relative humidity 90%) and 5 DEG C of curing conditions that concrete is tested respectively
The comprcssive strength of phase.By adjusting polycarboxylate water-reducer(commercially available standard type high-performance water reducing agent, its performance indications meet
The technical requirements of GB8076-2008,20% solid content) method of volume ensures that concrete has identical initialization performance.
Comparison study example 1 is the blank sample for being not added with any early strength agent,
Comparison study example 2 is early strength agent powder body anhydrous sodium sulfate (Na commonly used in the trade2SO4),
Comparison study example 3 is molten according to the solid hydrated calcium silicate of the synthesis of Chinese patent CN201410593398 embodiments two
Glue early strength agent.
To mix comprcssive strength of the concrete of the early strength agent of each embodiment and comparative example under the conditions of mark is supported, table 3 is table 2
Mix the comprcssive strength of the concrete under 5 DEG C of curing conditions of the early strength agent of each embodiment and comparative example.(embodiment of the present invention with
And the early strength agent sample in comparative example is solid volume.)
The mark of table 2 supports the comprcssive strength of Under Concrete
Result in table 2 shows, compared with blank sample (Comparison study example 1), the hydrated calcium silicate that the present invention is provided
Hollow nanoparticle can significantly increase comprcssive strength of the concrete in 6h to 1d, and 28d, 90d intensity also improves,
With significant early strong effect.Compared with sodium sulfate (Comparison study example 2) in the case where consumption is greatly reduced, early strong effect is bright
It is aobvious more excellent.Compared with hydrated calcium silicate colloidal sol (Comparison study example 3), similar early strong effect is reached, consumption is only that its half is left
It is right.
Comprcssive strength under 35 DEG C of curing conditions of table
Result in table 3 shows that the hollow nanoparticle early strength agent of hydrated calcium silicate that the present invention is provided is in 5 DEG C of curing conditions
The early age strength of concrete can equally be significantly increased down.Its early strong effect is far superior to sodium sulfate, and consumption compares water
SiClx acid calcium sol is greatly reduced.
Application Example 3
The concrete using high content mineral admixtures is directed to, and agent on crack resistance of concrete has been carried out according to the match ratio shown in table 4
The test of Compressive Strength, wherein mineral admixture consumption reach the 45% of binder total amount.The same application implementation of concrete raw material
Example 1.
4 concrete mix (Kg/m of table3)
Cement |
Breeze |
Flyash |
Sand |
Rubble |
Water |
247.5 |
112.5 |
90 |
700 |
1140 |
135 |
Table 5 is each embodiment of incorporation and the comprcssive strength of the high content mineral admixtures concrete of comparative example early strength agent.It is logical
Cross adjustment polycarboxylate water-reducerThe method of volume ensures that concrete has identical initialization performance.
Comparison study example 1 is the blank sample for being not added with any early strength agent, and Comparison study example 4 is always to be used using Binder Materials
The sodium sulfate of amount 3% and 3% Gypsum Fibrosum, Comparison study example 3 is according to two synthesis of Chinese patent CN201410593398 embodiments
Solid hydrated calcium silicate early strength agent.
The comprcssive strength of high content mineral admixtures concrete under the conditions of the mark of table 5 is foster
Result in table 5 shows that the present invention is sent out for early stage (12h-3d) intensity of high content mineral admixtures concrete
Exhibition has obvious facilitation.(Comparison study example 4) is compared with Gypsum Fibrosum in the case where consumption is greatly reduced, early by force with sodium sulfate
Effect is significantly superior.Compared with hydrated calcium silicate colloidal sol (Comparison study example 3), similar early strong effect is reached, consumption significantly drops
It is low.