CN117303775A - Fibrous inorganic toughening composite material and preparation method thereof - Google Patents
Fibrous inorganic toughening composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000000378 calcium silicate Substances 0.000 claims abstract description 41
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 41
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 30
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000292 calcium oxide Substances 0.000 claims abstract description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 47
- 238000001354 calcination Methods 0.000 claims description 33
- 229920006395 saturated elastomer Polymers 0.000 claims description 23
- 239000005543 nano-size silicon particle Substances 0.000 claims description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 53
- 230000036571 hydration Effects 0.000 abstract description 13
- 238000006703 hydration reaction Methods 0.000 abstract description 13
- 230000002411 adverse Effects 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 35
- 239000000243 solution Substances 0.000 description 33
- 239000004567 concrete Substances 0.000 description 23
- 238000001816 cooling Methods 0.000 description 19
- 239000002086 nanomaterial Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 239000011083 cement mortar Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of building material additives, and particularly discloses a fibrous inorganic toughening composite material for reinforcing toughness of cement-based materials and a preparation method thereof. The fibrous inorganic toughening composite material provided by the invention is a polycrystalline material composed of calcium silicate fibers, calcium oxide, silicon dioxide and metal oxide attached to the surfaces of the calcium silicate fibers. The fibrous inorganic toughening composite material has the main component of calcium silicate substances, not only shows an inner toughening mechanism through chemical component induced hydration products, but also shows an outer toughening mechanism through the fibrous appearance of the fibrous inorganic toughening composite material in the form of rivets in the cement hydration products, and realizes crack resistance of cement-based materials. The fibrous inorganic toughening composite material has good compatibility with the similar components in the cement-based material; and the cement is inorganic, does not contain organic matters, and can not adversely affect the hydration of the cement in application.
Description
Technical Field
The invention belongs to the technical field of building material additives, and particularly relates to a fibrous inorganic toughening composite material for reinforcing toughness of cement-based materials and a preparation method thereof.
Background
The brittleness and the poor toughness are one of the most obvious mechanical characteristics of the concrete material. Because of the extremely low ultimate tensile rate of concrete, the tensile stress born by the steel bar when the concrete cracks is less than 50MPa, the tensile strength of the steel bar is lower than that of the high-strength steel bar by an order of magnitude, the performance of the steel bar is far from that of the steel bar, and the steel bar cannot be matched with the high-speed development of steel bars in China. In addition, the important engineering of China is traversing things, going through north and south, and most of the points are exposed to more severe environments such as high salt, high humidity, high ultraviolet exposure and the like. Once the concrete structure is cracked, the durability is obviously reduced, the maintenance cost is increased, and a heavy burden is brought to national economy. Therefore, there is a higher demand for toughness of the concrete material itself, both from the viewpoint of the structure and from the viewpoint of durability.
Aiming at the defects of poor toughness and large brittleness of concrete, scholars at home and abroad develop researches on fiber toughening, organic matter modification, nano material regulation and control and the like. The brittleness of the concrete can be effectively improved by incorporating a certain amount of fibers. In recent years, scholars at home and abroad develop a great deal of research on the development of the toughness of concrete around the aspects of fiber types, thickness, doping amount, section shape, length-diameter ratio, distribution, surface modification and the like. The current application is more widely steel fibers, polypropylene fibers, and polyvinyl alcohol fibers. Fiber toughening acts on the concrete before and after cracking. Before cracking, the fibers can transfer stress in a concrete matrix, so that the strength and toughness of the fiber concrete are improved; after cracking, the fiber absorbs a large amount of energy for crack propagation through the binding force with a concrete matrix, the friction force generated by relative displacement and the deformation of the fiber, so that the fracture energy of the fiber concrete is improved, the crack development is restrained, and the cracking resistance and toughness are improved. Compared with common concrete, the high-toughness cement-based material designed based on micromechanics and fracture mechanics has the advantages that the tensile strength can be improved by 9% -50% (depending on fiber types, doping amount and the like), the flexural strength is improved by 196%, the brittle fracture property is reduced, and the ductility and toughness in the fracture process are enhanced.
Polymers are used to improve the brittleness of concrete materials due to their excellent toughness. Common polymers include ethylene-vinyl acetate copolymer emulsions, styrene-butadiene copolymer emulsions, water-soluble methylcellulose, polyvinyl alcohol, polyacrylamide, epoxy resins, unsaturated polyester resin-based polymers, and the like. However, the polymer toughening material has the defects of higher price, large doping amount, poor weather resistance, easy decomposition at high temperature and the like, thereby limiting the application of the polymer toughening material.
Nanomaterials regulate the toughness of cement-based materials are a recent research focus. The nanometer materials with the most remarkable toughness improvement of the cement-based materials comprise nanometer silicon dioxide, graphene oxide, carbon nanotubes and the like. Researches show that the nano material can improve the interface transition area and the bonding force between the aggregate and the cement mortar matrix. The nanoparticles hinder the propagation of microcracks, forming a spatial interlocking effect between slip planes, thereby improving the toughness of the cement-based material. However, nanoparticles are extremely easy to agglomerate when being directly applied to cement-based materials due to extremely high specific surface area and surface energy, so that the functions of the nano materials are greatly limited, and meanwhile, the high economic cost also hinders a large amount of engineering application of the nano materials.
In conclusion, the fiber, polymer, nano material and other regulating methods can improve the toughness of the cement concrete to a certain extent, but the methods still belong to external toughening methods, the disordered distribution state of hydration products of the cement-based materials is not changed essentially, and the limitation of the modification methods on the improvement of the toughness of the cement concrete is basically determined.
Although there are related studies on improvements in the toughening mechanism, it is required to rely on high molecular polymer dispersants for preparation, which leads to problems in which these organic solvents adversely affect the hydration of cement-based materials upon application.
Therefore, there is a need to develop a toughening material which is excellent in toughening effect and does not adversely affect hydration of cement-based materials when applied.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides an inorganic composite material for enhancing the toughness of a cement-based material, which not only endows the cement-based material with better toughness, durability and mechanical properties after being applied to the cement-based material, but also does not have adverse effects on the hydration of the cement-based material due to the components.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a fibrous inorganic toughening composite material is a polycrystalline material composed of calcium silicate fibers, and calcium oxide, silicon dioxide and metal oxide attached to the surfaces of the calcium silicate fibers; wherein the content of the calcium silicate fiber is 35 to 55 weight percent, the content of the calcium oxide is 15 to 22 weight percent, the content of the silicon dioxide is 23 to 45 weight percent, and the content of the metal oxide is below 5 weight percent.
The inorganic toughened composite material is fibrous in shape, and has a length of 5-10 μm and a diameter of 300-600 nm.
The invention also aims to provide a preparation method of the fibrous inorganic toughening composite material, which comprises the following steps:
s1, calcining a mixture formed by mixing calcium silicate, nano silicon dioxide and metal oxide at 1200-1400 ℃ to obtain a calcined substance;
s2, mixing the calcined product with silicon dioxide and alkali liquor, and introducing acid gas into the mixture to saturate the mixture to obtain a saturated gas solution;
s3, carrying out hydrothermal reaction on the saturated gas solution at 120-180 ℃ to obtain the fibrous inorganic toughening composite material.
The metal oxide in step S1 may be at least one selected from the group consisting of calcium oxide, aluminum oxide, and iron oxide, and is added in an amount of not more than 5% by mass of the total mass of the mixture. The metal oxides are used as raw materials, can play a role in defining the morphology, and can be adsorbed on the surface of calcium silicate in the reaction process, so that the morphology of the calcium silicate is influenced in the nucleation process, and fibrous morphology is promoted to be generated; these metal oxides also give the product a polycrystalline structure. And the existence of the metal oxides also ensures that the fibrous inorganic toughening composite material with the metal oxides can improve the surface roughness of cement when being applied to cement-based materials.
The high temperature calcination operation in step S1 can allow the elements to achieve solid phase migration between the metal oxide and other inorganic components.
The particle size of the calcium silicate in the mixture is 50 nm-10 mu m, and the particle size of the nano silicon dioxide is 20 nm-100 nm; in the metal oxide, the particle size of the calcium oxide is 5-50 μm, and the particle sizes of the aluminum oxide and the iron oxide are 10-50 μm.
The calcium silicate can be commercial calcium silicate powder or nano calcium silicate prepared by reacting calcium chloride with sodium silicate.
The high-temperature calcination in the step S1 can be realized by adopting a muffle furnace and a temperature control program, namely, gradient temperature rise from normal temperature. The step heating process can have 2-3 steps, and the total time is 5-8 h. The final reaction temperature is controlled between 1200 ℃ and 1400 ℃, and calcination treatment is preferably carried out at the final reaction temperature for 1h to 3h. And (5) naturally cooling after calcining to obtain a calcined product.
In step S2, the alkali solution may ensure a more adequate deposition of calcium silicate. The alkali solution is not particularly limited, and may be, for example, a sodium hydroxide solution, or a calcium hydroxide solution, or a mixed solution of both, wherein the concentration of the sodium hydroxide solution may be 0.1mol/L to 0.5mol/L, and the calcium hydroxide solution may be a saturated calcium hydroxide solution.
While introducing acid gas to saturated state for bufferingSlowly dissolve the material in the solid phase. The acid gas may be CO 2 The aeration time is generally controlled to be about 5 min-10 min, so that saturation can be achieved.
Preferably, in step S2, the calcine is milled to a particle size of 1 μm to 50 μm before mixing it with the silica and the lye. Smaller calcine particle size may allow for more complete subsequent reactions.
Generally, in step S3, the hydrothermal reaction product may be washed, dried, and ground to obtain the fibrous inorganic toughening composite material described above.
Compared with the prior art, the invention has the following beneficial effects:
1) The main component of the fibrous inorganic toughening composite material provided by the invention is calcium silicate substances, when the fibrous inorganic toughening composite material is applied to cement-based materials, on one hand, the existence of elements such as silicon, calcium and the like can induce the formation of cement hydration products, and the fibrous inorganic toughening composite material can be used as nucleation sites to dissolve out the obtained Ca in cement 2+ 、SiO 4 2- The fibrous morphology is further grown due to the higher tendency to deposit on the surface of the cement-based material, so that the hydration path of the cement-based material is changed, the overall internal structure of the cement-based material is changed (the morphology of cement hydration products is changed), and an internal toughening mechanism is shown; on the other hand, the fibrous morphology of the composite material can exist in a cement hydration product in a rivet form, and the composite material can effectively prevent cracks in a matrix from generating by combining the high-strength characteristic of the composite material, and when the cracks generate and develop to the position, the stress can be effectively released, so that the extension of the cracks is slowed down, the effect of slowing down the extension and growth of the cracks is achieved, and an external toughening mechanism is shown.
2) The fibrous inorganic toughening composite material provided by the invention has good compatibility with cement-based materials when being applied to the cement-based materials based on components similar to the components in the cement-based materials; and the cement is inorganic, does not contain organic matters, and can not adversely affect the hydration of the cement in application.
3) In the preparation process of the fibrous inorganic toughening composite material provided by the invention, nano silicon dioxide is added into the system in a calcined form and is used as a nucleation site for the growth of fibrous products, so that the advantage that nano particles can enhance the mechanical properties of cement-based materials is utilized, and the problem of agglomeration caused by direct addition and application in the cement-based materials in the prior art is solved.
4) The preparation method of the fibrous inorganic toughening composite material provided by the invention has the advantages that the sources of raw materials are wide, the raw materials are inorganic components, the preparation method is safe and environment-friendly, and the preparation process is simple and easy to control.
Drawings
FIG. 1 is a microscopic topography of a fibrous inorganic toughening composite material according to example 8 of the present invention;
FIGS. 2 and 3 are nanostructure diagrams of fibrous components in a fibrous inorganic toughening composite material according to example 8 of the present invention at different multiples after electron beam irradiation;
FIG. 4 is an SEM image of the surface of a cement coupon obtained by application of the fibrous inorganic toughening composite material of example 8 according to the present invention;
fig. 5 is an SEM image of the surface of a reference cement block.
Detailed Description
The present invention will be further described in detail with reference to examples, which are, however, only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The fibrous inorganic toughening composite material provided by the embodiment is prepared by the following method:
(1) The premixed mixture A (55 wt% of calcium silicate, 15wt% of calcium oxide, 25wt% of nano silicon dioxide and 5wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 min-60 min-1300 ℃. Calcining for 1h at 1300 ℃, and naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.1mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening composite material S01.
Example 2
(1) The premixed mixture A (50 wt% of calcium silicate, 22wt% of calcium oxide, 24wt% of nano silicon dioxide, 2wt% of aluminum oxide and 2wt% of ferric oxide) is put into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, and the temperature is 50-30 min-100-90 min-700-110-1200-30 min-1200-60-1300 ℃. Calcining for 2 hours after reaching 1300 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle sizes of the aluminum oxide and the ferric oxide are 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.3mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S02.
Example 3
(1) The premixed mixture A (50 wt% of calcium silicate, 24wt% of calcium oxide, 24wt% of nano silicon dioxide and 2wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 ℃. Calcining for 3 hours after reaching 1200 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.5mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S03.
Example 4
(1) The premixed mixture A (50 wt% of calcium silicate, 24wt% of calcium oxide, 24wt% of nano silicon dioxide and 2wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 min-60 min-1400 ℃. Calcining for 2 hours at 1400 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.1mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S04.
Example 5
(1) The premixed mixture A (50 wt% of calcium silicate, 24wt% of calcium oxide, 24wt% of nano silicon dioxide and 2wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 min-60 min-1300 ℃. Calcining for 2 hours after reaching 1300 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.3mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S05.
Example 6
(1) The premixed mixture A (50 wt% of calcium silicate, 24wt% of calcium oxide, 24wt% of nano silicon dioxide and 2wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 min-60 min-1300 ℃. Calcining for 2 hours after reaching 1300 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.5mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S06.
Example 7
(1) The premixed mixture A (35 wt% of calcium silicate, 24wt% of calcium oxide, 24wt% of nano silicon dioxide and 2wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 min-60 min-1300 ℃. Calcining for 2 hours after reaching 1300 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.1mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, performing hydrothermal reaction at 180 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S07.
Example 8
(1) The premixed mixture A (50 wt% of calcium silicate, 24wt% of calcium oxide, 24wt% of nano silicon dioxide and 2wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 min-60 min-1300 ℃. Calcining for 2 hours after reaching 1300 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.3mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, performing hydrothermal reaction at 180 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S08.
Example 9
(1) The premixed mixture A (35 wt% of calcium silicate, 19wt% of calcium oxide, 45wt% of nano silicon dioxide and 1wt% of aluminum oxide) is filled into a crucible, and is put into a muffle furnace for calcination, and the temperature is raised and the calcination adopts a program temperature control mode, wherein the temperature is 50-30 min-100 min-90 min-700 min-110 min-1200-30 min-1200 min-60 min-1300 ℃. Calcining for 2 hours after reaching 1300 ℃, and then naturally cooling to obtain a calcined product.
The particle sizes of the components in the mixture A are respectively as follows: the particle size of the calcium silicate is 50 nm-10 mu m, the particle size of the nano silicon dioxide is 20 nm-100 nm, the particle size of the calcium oxide is 5 mu m-50 mu m, and the particle size of the aluminum oxide is 10 mu m-50 mu m.
(2) The calcined product was ball-milled for 1 hour, and the obtained powder was further hand-milled using an agate mortar for 0.5 hour, and sieved through a 400-mesh sieve to obtain a small-particle-size mixture B (particle size: 1 μm to 50 μm).
(3) The refined mixture B (3.6 parts) was blended with silica (1 part) and 100 parts of 0.5mol/L sodium hydroxide while CO was introduced into the solution 2 And (5) carrying out gas for 10min to obtain saturated gas solution C.
(4) And (3) placing the saturated gas solution C into a hydrothermal reaction kettle, performing hydrothermal reaction at 180 ℃ for 12 hours, and cooling to obtain a product D.
(5) And (3) cleaning, drying and grinding the product D to obtain the fibrous inorganic toughening nano material S09.
The material obtained in the above example 8 was subjected to electron microscopy characterization, and the microscopic morphology chart is shown in fig. 1. As can be seen from FIG. 1, the product is fibrous in its entire microstructure, and has a length of about 5 μm to 10 μm and a diameter of about 300nm to 600nm.
The fibrous components in the material were simultaneously subjected to electron beam irradiation, after which the nanostructures at different multiples are shown in fig. 2 and 3. It can be seen that this is shown in figure 2. The electron beam breaks down the fiber and a number of small particles are visible, each of which is polycrystalline, indicating that the material is in a distinct polycrystalline morphology.
In order to more intuitively observe the influence of the fibrous inorganic toughening composite material provided by the invention on hydration of cement-based materials, the following test was performed.
The fibrous inorganic toughening composite material in the above example 8 was added to cement, and the surface of a cement block obtained by hydrating 28d thereof was subjected to a scanning electron microscope test, and the SEM image thereof was shown in fig. 4.
Meanwhile, a standard cement test block under the same condition is prepared, namely, the cement test block obtained without adding the fibrous inorganic toughening composite material. The SEM image is shown in fig. 5.
Comparing fig. 4 and 5, it can be seen that when the fibrous inorganic toughening composite material is added, the roughness of the surface of the cement test block is obviously reduced, the surface is smoother, the degree of order is obviously increased, and the toughness and strength of the material can be obviously enhanced by an ordered structure.
The materials obtained in the examples above were tested for properties that were considered in the application by adding them to cement-based materials and determining the relevant properties of the corresponding cement-based materials.
Cement mortar fluidity testing method
The fluidity of the cement mortar is carried out by referring to national standard GB/T8077-2012 "concrete admixture homogeneity test method", naphthalene-based high-efficiency water reducer is adopted, and the comparison result is shown in Table 1.
Table 1 cement mortar fluidity test comparison
As can be seen from the data in table 1, when the fibrous inorganic toughening composite material of the present invention is added, the fluidity of the corresponding cement-based material is not significantly changed, which proves that the inorganic toughening composite material has no influence on the working performance of cement.
Method for testing mechanical properties of concrete
The fibrous inorganic toughening composite materials provided in the above examples were added to prepare concrete with the mixing ratio shown in table 2:
TABLE 2 concrete mix ratio
Note that: the volume weight is 2350kg/m 3 The sand ratio was 42.5% and the water-gel ratio was 0.4.
The compressive and flexural strength was tested according to GB/T50081 Standard for physical mechanical Properties test of concrete and is shown in Table 3.
TABLE 3 mechanical Properties of concrete (mixing amount based on Cement quality)
As can be seen from table 3, by adding the fibrous inorganic toughening composite material provided by the invention, the flexural data of 7d and 28d of the corresponding obtained cement test block are obviously improved, and the compressive strength is not reduced; and the best 28d flexural strength is enhanced by 32%. Meanwhile, the highest flexural strength of the fiber-shaped calcium silicate is improved by 23 percent (12.88 MPa is improved by 15.88 MPa) according to comparison with the traditional fiber-shaped calcium silicate toughening, and the fiber-shaped calcium silicate toughening agent can be improved by 32 percent (4.3 MPa is improved by 5.7 MPa).
From these examples, it can be demonstrated that the fibrous inorganic toughening composite material provided by the invention can be used for preparing high-toughness cement-based materials.
Claims (7)
1. The fibrous inorganic toughening composite material is characterized by being a polycrystalline material composed of calcium silicate fibers, calcium oxide, silicon dioxide and metal oxide attached to the surfaces of the calcium silicate fibers; wherein the content of the calcium silicate fiber is 35-55wt%, the content of the calcium oxide is 15-22wt%, the content of the silicon dioxide is 23-45wt%, and the content of the metal oxide is below 5wt%.
2. The fibrous inorganic toughening composite material according to claim 1, wherein the fibrous inorganic toughening composite material is fibrous and has a length of 5 μm to 10 μm and a diameter of 300nm to 600nm.
3. The method for preparing a fibrous inorganic toughening composite material according to claims 1 to 2, comprising the steps of:
s1, calcining a mixture formed by mixing calcium silicate, nano silicon dioxide and metal oxide at 1200-1400 ℃ to obtain a calcined substance;
s2, mixing the calcined product with silicon dioxide and alkali liquor, and introducing acid gas into the mixture to saturate the mixture to obtain a saturated gas solution;
s3, carrying out hydrothermal reaction on the saturated gas solution at 120-180 ℃ to obtain the fibrous inorganic toughening composite material.
4. A production method according to claim 3, wherein in the step S1, the metal oxide is at least one selected from the group consisting of calcium oxide, aluminum oxide, and iron oxide, and is added in an amount of not more than 5% by mass of the total mass of the mixture.
5. The method according to claim 4, wherein the particle size of calcium silicate in the mixture is 50nm to 10 μm and the particle size of nano silica is 20nm to 100nm; in the metal oxide, the particle size of the calcium oxide is 5-50 μm, and the particle sizes of the aluminum oxide and the iron oxide are 10-50 μm.
6. The method according to any one of claims 3 to 5, wherein in the step S1, a muffle furnace is used for calcining at a controlled temperature in accordance with a program; the temperature rise process of the steps has 2 to 3 steps, the total time is 5 to 8 hours, and the calcination treatment is carried out for 1 to 3 hours at the final reaction temperature of 1200 to 1400 ℃.
7. The process according to claim 3, wherein in step S2, the calcined product is milled to a particle size of 1 μm to 50. Mu.m, before being mixed with silica and alkali solution.
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