CN110642550B - Composite microsphere for improving early performance of cement-based material - Google Patents
Composite microsphere for improving early performance of cement-based material Download PDFInfo
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- CN110642550B CN110642550B CN201910956252.4A CN201910956252A CN110642550B CN 110642550 B CN110642550 B CN 110642550B CN 201910956252 A CN201910956252 A CN 201910956252A CN 110642550 B CN110642550 B CN 110642550B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention relates to a composite microsphere for improving early performance of cement-based materials, which is a powder material composed of submicron spherical cores with diameters of 100-500 nm and nanoparticles with diameters of 1-30 nm, wherein the surfaces of the spherical cores are provided with hydrophilic chain segments, the nanoparticles have the effect of promoting cement hydration, and the spherical cores and the nanoparticles are combined in such a way that the surface parts of the spherical cores are adhered by the nanoparticles in a dispersing way, so that a strawberry-shaped composite microsphere structure is formed. The microspheres have uniform size, are capable of forming a dispersion in water, and have the property of promoting the hydration process of cement.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a composite microsphere for improving early performance of cement-based materials.
Background
Cement-based materials are widely used in various civil engineering as the most da Zong amount of artificial materials in the world at present. In recent years, the demand for cement-based materials has gradually progressed from the single strength demand to the comprehensive properties of higher strength, higher durability, better workability, etc. Among them, the early strength of cement-based materials is becoming more of a concern due to factors such as the rapid construction period and the reduction of construction cost. At present, for cast-in-place concrete and concrete prefabricated parts with early strength requirements, people often need to add early strength agents such as nitrate or triethanolamine, but the early strength agents still need to be improved in the aspects of hardening body shrinkage rate, durability and the like. Therefore, people are also constantly developing novel early strength agents to meet the early strength requirements under different construction conditions. Because a large amount of C-S-H gel can be generated in the cement hardening process, part of the nano particles can change the generation rate of the C-S-H gel in the system and participate in hydration reaction to a certain extent. Therefore, a method of improving early strength and the like of cement-based materials using nanoparticles has attracted attention.
To the nanometer SiO which is most widely applied in cement systems 2 For example, the cement-based material can fill gaps among C-S-H gels, and improve the interface microstructure of cement stones and aggregates, so that the mechanical property, the impermeability and the durability of the cement-based material are obviously improved. Furthermore, nano SiO 2 Can also be combined with cement hydration product Ca (OH) 2 More C-S-H gel is generated by reaction, so that Ca (OH) enriched in early interface is generated 2 The absorption forms secondary hydrate, and obviously reduces Ca (OH) 2 Degree of orientation of crystals, ca (OH) 2 The size of the crystal grain is reduced, and the boundary is effectively improvedIn the surface condition, the void ratio in the cement stone is reduced, so that the void of the cement stone is reduced, the microstructure is more compact, and the mechanical property is improved.
However, due to, for example, nano SiO 2 The nano powder with hydration activity has large specific surface area and high surface atomic ratio, so that agglomeration is easy to occur among particles, the secondary particle size of the nano powder reaches the micron level, and the sufficient reinforcing effect is difficult to be exerted. It is difficult to uniformly disperse the nano powder particles if they are directly blended during the preparation of cement-based slurry. Even if the nano powder particles are made into suspension by ultrasonic dispersion or ball milling, a certain degree of agglomeration still exists among the nano powder particles. The agglomeration phenomenon can lead the nano powder particles to weaken the hydration promotion effect of the nano powder particles on cement.
Disclosure of Invention
In order to solve the problems, the invention provides a composite microsphere for improving early performance of cement-based materials. The composite microsphere can realize good dispersion in water, can participate in cement hydration reaction, and promotes the hydration process of cement.
The invention provides a composite microsphere for improving early performance of cement-based materials, which is a powder material composed of submicron spherical cores with diameters of 100-500 nm and nanoparticles with diameters of 1-30 nm, wherein the surfaces of the spherical cores are provided with hydrophilic chain segments, the nanoparticles have the effect of promoting cement hydration, and the spherical cores and the nanoparticles are combined in such a way that the surface parts of the spherical cores are adhered by the nanoparticles in a dispersing way, so that a strawberry-shaped composite microsphere structure is formed.
The spherical core is a copolymer of one or more of acrylic ester monomers, styrene monomers, butadiene monomers and acrylamide monomers, or is composed of one or more of modified silica fume, fly ash, carbon particles and ceramics.
The hydrophilic chain segment on the surface of the spherical core contains one or more of hydroxyl, carboxyl, amino, sulfonic acid group or phosphoric acid group.
The content of the hydrophilic chain segments on the surface of the spherical core is between 0.05mmol/g and 0.5mmol/g, wherein mmol/g represents the mole number of the hydrophilic chain segments on the surface of the spherical core per unit mass.
The nano particles on the surface of the spherical core are formed by hydrated calcium silicate gel and SiO 2 、Al 2 O 3 、CeO 2 、TiO 2 One or more of the components.
The coverage area of the nanoparticle on the spherical core accounts for 20% -70% of the total surface area of the spherical core.
The composite microsphere powder has good dispersibility in water, and can form aqueous dispersion liquid with PDI index smaller than 0.3 and Z average diameter smaller than 1 μm.
When the dosage of the composite microsphere is 4% -10% of the mass of the cementing material, the early strength of the cement-based material can be improved by more than 10%.
The application of the composite microsphere for improving the early performance of the cement-based material in the preparation of the cement-based material.
Compared with the prior art, the invention has the following advantages: the nano powder particles with hydration activity are easy to agglomerate, and are difficult to realize good dispersion in cement paste, so that the early strength effect of the nano powder when the nano powder is applied to cement-based materials is reduced. The invention combines the nano powder particles with the spherical core with the hydrophilic chain segment on the surface to prepare the strawberry-shaped composite microsphere. The composite microsphere sacrifices part of the activity of nano powder in a surface fixing mode, but the aggregation of the powder is avoided to a great extent, so that the composite microsphere still has more obvious improvement effect on the early strength performance of cement-based materials on the whole.
Detailed Description
In order to describe the features and effects of the present invention in detail, the following examples and comparative examples are described in detail
Example 1
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.2 mmol/g, and the size of the microspheres is 350 nm. Micro-scaleThe surface of the ball is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Example 2
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.2 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano C-S-H gel, and the size is 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Example 3
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.2 mmol/g, and the size of the microspheres is 450 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Example 4
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.4 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Example 5
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.2 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 8 percent of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compression resistance of the cement powder in different timeFolding strength.
Example 6
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are sulfonic acid groups, the content is 0.2 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Comparative example 1
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.7 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Comparative example 2
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.2 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano C-S-H gel, and the size is 80 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Comparative example 3
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.2 mmol/g, and the size of the microspheres is 150nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Comparative example 4
Dissolving a certain amount of composite microsphere in water, stirring uniformly, wherein the exposed hydrophilic group on the surface of the composite microsphere is carboxylThe content is 0.01 mmol/g, and the microsphere size is 350 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Comparative example 5
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed hydrophilic groups on the surfaces of the composite microspheres are carboxyl groups, the content of the hydrophilic groups is 0.2 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 15% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
Comparative example 6
And dissolving a certain amount of composite microspheres in water, and uniformly stirring, wherein the exposed groups on the surfaces of the composite microspheres are ethyl groups, the content is 0.2 mmol/g, and the size of the microspheres is 350 nm. The microsphere surface is nano SiO 2 Particles having a size of 10 nm. The dosage is 5% of the mass of the colloid material. Mixing a certain amount of cement powder with microsphere dispersion liquid, uniformly stirring, and measuring the compressive and flexural strength of the cement powder at different times.
The cement paste was prepared by the methods of examples 1 to 6 and comparative examples 1 to 6, respectively, while the paste was prepared as a control group by the existing cement paste preparation method. Comparing the cement products obtained by each group, and measuring the flexural strength and the compressive strength of the cement test block at 3d, 7d and 28d by adopting a DKZ-5000 electric flexural testing machine and a WE-600B universal testing machine according to GB/T17671-1999 cement mortar strength test method (ISO).
Example 1 has improved flexural strength and compressive strength as compared to the control and comparative example 1. The main reason that the early strength of the cement is not obviously improved in the comparative example 1 is that the microsphere in the comparative example 1 has too high content of hydrophilic groups, and the groups are agglomerated and cannot have a dispersing effect.
Example 2 improved early strength properties of cement-based materials compared to control, example 1 and comparative example 2 to a greater extent than example 1, mainly because nano C-S-H gels promote cement hydration to a greater extent than nano SiO 2 The effect is good. The nano C-S-H gel is directly used as crystal nucleus in cement system to participate in cement hydration process. The effect of improving the early strength performance of the cement-based material of comparative example 2 is not obvious, mainly because the size of the nanoparticle in comparative example 2 is 80 nm, the size of the nanoparticle is too large, and fewer sites capable of promoting cement hydration are provided in the microsphere of the same mass.
Example 3 the effect of example 3 on improving early strength of cement is less pronounced than in the control, example 1 and comparative example 3. Mainly, the composite microsphere in example 3 had a size of 450nm, which is larger than that of the composite microsphere used in example 1, and if the composite microsphere had a larger particle size, a part of defects were likely to be formed in cement. The early strength improvement of the cement-based material is not obvious in comparative example 3 compared with the control group, mainly because the composite microsphere is undersized and the dispersion effect of the strawberry-like structure is deteriorated, resulting in difficulty in dispersion of the composite microsphere in water.
Example 4 has a better effect of improving early strength of cement-based materials than the control group, example 1 and comparative example 4, mainly because the composite microspheres used have a high surface hydrophilic group content, which is more advantageous for dispersion of the composite microspheres in water. The early strength improvement of the cement-based material in comparative example 4 is not obvious, and the main reason is that the used composite microsphere has a small content of hydrophilic groups and cannot realize good dispersion in water.
Compared with the control group, the example 1 and the comparative example 5, the early strength performance of the cement-based material is better, and the main reason is that the composite microsphere in the example 5 is more in dosage and more nano particles can participate in the cement hydration process, so the improvement effect is obvious. Although the amount of the composite microspheres in comparative example 5 was large, the improvement effect was not remarkable, and the main reason for this was that the compressive modulus of the spherical cores was significantly lower than that of cement-based materials, and when the amount of the composite microspheres was large, the modulus and strength lowering effect of the spherical cores themselves was greater than that of the composite microspheres to promote cement hydration.
Example 6 has a remarkable effect of improving early strength performance of cement-based materials as compared with the control group, example 1 and comparative example 6, mainly because hydrophilic groups on the surface of the composite microspheres in example 6 are sulfonic acid groups, and the sulfonic acid groups are better hydrophilic than carboxyl groups. The early strength performance of the cement-based material is not obviously improved in comparative example 6, and the main reason is that the surface of the composite microsphere in comparative example 6 is ethyl and is a hydrophobic group, so that the composite microsphere cannot be well dispersed in water.
Claims (5)
1. A composite microsphere for improving early performance of cement-based materials is characterized in that the composite microsphere is a powder material composed of submicron spherical cores with diameters of 100-500 nm and nanoparticles with diameters of 1-30 nm, the spherical core surface is provided with hydrophilic chain segments, the nanoparticles have the effect of promoting cement hydration, the spherical cores and the nanoparticles are combined in such a way that the spherical core surface is partially adhered by the nanoparticles in a dispersing way to form a strawberry-shaped composite microsphere structure, the spherical cores are copolymers of one or more of acrylate monomers, styrene monomers, butadiene monomers and acrylamide monomers, or are composed of one or more of modified silica fume, fly ash monomers, carbon particles and ceramics, the hydrophilic chain segments on the spherical core surface contain one or more of hydroxyl groups, carboxyl groups, amino groups, sulfonic acid groups or phosphoric acid groups, the hydrophilic chain segments on the spherical core surface have the content of 0.05-0.5 mmol/g, wherein mmol/g represents the hydrophilic mole number of spherical core surfaces per unit mass, and the spherical core surfaces are hydrated by the spherical silica gel particles and the SiO chain segments are hydrated by the nanoparticles 2 、Al 2 O 3 、CeO 2 、TiO 2 One or more of the components.
2. The composite microsphere for improving early performance of cement-based materials of claim 1, wherein the nanoparticle coverage area of the spherical core is 20% -70% of the total surface area of the spherical core.
3. The composite microsphere for improving early performance of cement-based materials according to any one of claims 1 to 2, wherein the composite microsphere powder has good dispersibility in water, and can form an aqueous dispersion with a PDI index of less than 0.3 and a z average diameter of less than 1 μm.
4. The composite microsphere for improving early performance of cement-based materials according to any one of claims 1 to 2, wherein the early strength of cement-based materials can be improved by more than 10% when the composite microsphere is used in an amount of 4 to 10% by mass of the cementing material.
5. Use of composite microspheres according to any one of the claims 1-4 for improving early performance of cement-based materials in the preparation of cement-based materials.
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