CN115340350B - Cement composite undisturbed titanium gypsum-based foam concrete and preparation method thereof - Google Patents
Cement composite undisturbed titanium gypsum-based foam concrete and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses cement composite undisturbed titanium gypsum-based foam concrete and a preparation method thereof, belonging to the technical field of building materials, wherein the foam concrete comprises the following components in parts by weight: 15-40 parts of titanium gypsum, 20-40 parts of P.O42.5-grade cement, 5-10 parts of mineral powder, 3-8 parts of glass beads, 1-4 parts of quick lime, 15-25 parts of metal ionic solution, 3-5 parts of active admixture, 0.1-0.5 part of carboxymethyl starch ether, 0.1-0.5 part of early strength polycarboxylic acid water reducing agent, 0.5-1.2 parts of AOS foaming agent and 3-10 parts of water. The invention optimizes the formula of the concrete, only needs mixing during preparation, does not need steam pressurization or high-temperature drying, can directly utilize the original state byproduct titanium gypsum, and can improve various performance indexes such as the compressive strength, the softening coefficient and the like of the titanium gypsum foamed concrete.
Description
Technical Field
The invention relates to the field of foam concrete, in particular to cement composite undisturbed titanium gypsum-based foam concrete and a preparation method thereof.
Background
Titanium gypsum is a chemical byproduct waste residue generated in the production of titanium dioxide by an industrial sulfuric acid method, 5-6t of gypsum residue is generated when 1t of titanium dioxide is produced, and about 1000 ten thousand of titanium white gypsum is generated in China every year. Titanium gypsum is the industrial byproduct gypsum with the lowest utilization rate, only a small part of the gypsum is applied to the fields of cement, roadbed backfill, building materials and the like, most of the existing titanium gypsum disposal is accumulated, the accumulated disposal can affect the surrounding environment, pollute the water body and damage the ecology, and meanwhile, enterprises are also under great environmental protection pressure, so that huge economic burden is caused to titanium dioxide enterprises.
At present, the country attaches more and more importance to land resources and environmental protection, and pushes forward the development and research of novel energy-saving, environment-friendly and multifunctional green materials, and among numerous materials, foam concrete becomes the material with the highest cost performance. The foaming gypsum material is a novel green wall material prepared by a foaming process by taking industrial byproduct gypsum or building gypsum as a raw material; however, domestic industrial gypsum must be modified, calcined, dehydrated, ground and the like to produce semi-hydrated gypsum powder, and then the semi-hydrated gypsum powder is used as a raw material to produce a gypsum building material product, certain energy is consumed for calcination or drying, the utilization cost is high and even exceeds that of natural gypsum, and in addition, the foamed gypsum block produced by the conventional process is light and porous, has low strength and poor water resistance, and hinders large-scale popularization and application of the foamed gypsum block. For example, chinese patent application No. CN202011064969.7 discloses a method for preparing a foamed concrete product by using titanium gypsum, which is described in the following, placing the demolded product in a closed kettle, introducing steam into the kettle, converting the product for 7 to 8 hours under the pressure of 1.15 to 1.20MPa, and finally drying the product to constant weight under natural conditions, wherein the process is complex, and the energy consumption and the work efficiency are low;
chinese patent application No. CN202010820808.X discloses gypsum-based foam concrete with high content of phosphogypsum and a preparation method thereof, wherein the phosphogypsum is recorded to be dried in a drying oven at a constant temperature of 130 ℃ for 60min, and the gypsum-based foam concrete is energy-consuming and complex in process.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides cement composite undisturbed titanium gypsum based foam concrete which is easy to prepare and a preparation method of the cement composite undisturbed titanium gypsum based foam concrete.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
15-40 parts of titanium gypsum, 20-40 parts of P.O42.5-grade cement, 5-10 parts of mineral powder, 3-8 parts of glass beads, 1-4 parts of quicklime, 15-25 parts of metal ionic solution, 3-5 parts of active admixture, 0.1-0.5 part of carboxymethyl starch ether, 0.1-0.5 part of early strength type polycarboxylic acid water reducing agent, 0.5-1.2 parts of AOS foaming agent and 3-10 parts of water.
Preferably, 15-20 parts of titanium gypsum, 20-40 parts of P.O42.5-grade cement, 5-10 parts of mineral powder, 3-8 parts of glass beads, 1-4 parts of quicklime, 15-25 parts of metal ion type solution, 3-5 parts of active admixture, 0.1-0.5 part of carboxymethyl starch ether, 0.1-0.5 part of early strength type polycarboxylic acid water reducing agent, 0.5-1.2 parts of AOS foaming agent and 3-10 parts of water.
Preferably, the composition comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylic acid water reducing agent, 1 part of AOS foaming agent and 9.5 parts of water.
Preferably, the metal ionic solution contains Fe 3+ 、Al 3+ 、Mn 2+ 、Ca 2+ And Mg 2+ Of any one or more of (a) or (b).
Preferably, the metal ion type solution consists of 500g of silica sol, 15-30ml of calcium chloride aqueous solution and analytically pure anhydrous FeCl 3 40-50 g; the particle size of the silica sol is 9-11nm, and the concentration of the calcium chloride aqueous solution is 1-3g/ml.
Preferably, the active blending agent is formed by mixing an active siliceous material, an active aluminum material and a non-reactive siliceous material.
Preferably, the active siliceous material is any one of rice hull ash or silica ash, the active aluminous material is any one of aluminosilicate cement and sulphoaluminate cement, the non-reactive siliceous material is diatomite, and the weight ratio of the active siliceous material to the active aluminous material to the diatomite is 3-6:1:1.
preferably, the active admixture is prepared by the following method:
b1: preparing 4 parts by mass of silica fume or fully combusted rice hull ash;
b2: 1 part by mass of active aluminum material is processed into the fineness of more than 6000 meshes;
b3: putting 1 part by mass of dried diatomite into the diatomite to perform ultra-pure and ultra-fine processing so that the fineness of the diatomite reaches more than 6000 meshes;
b4: the active siliceous material, the active aluminous material and the diatomite are put into and mixed at one time.
Preferably, the preparation method of the early strength type polycarboxylate water reducer comprises the following steps:
c1, mixing 500g of solution of 10-30 mass percent of isobutylene alcohol polyoxyethylene ether macromonomer and 500g of deionized water, and heating to 60-70 ℃;
c2, adding the components in a mass ratio of 1:1:1, 200g of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and deionized water;
and C3, adding aqueous solution of thioglycolic acid and 15g of composite initiator with the concentration of 0.01-0.02mol/L, wherein the composite initiator is formed by compounding ammonium persulfate and diethanolamine, and the mass ratio of the thioglycolic acid to the ammonium persulfate to the diethanolamine is 1-5:1-5:1, stirring and keeping the temperature at 60-70 ℃, and reacting to graft a monomer with an early strength function on a isobutylene alcohol polyoxyethylene ether copolymer molecular chain;
and C4, neutralizing by using a sodium hydroxide solution until the pH value is neutral to obtain the early-strength polycarboxylate superplasticizer, wherein the concentration, namely the solid content, of the water reducer solution is controlled to be 30-45%.
The preparation method of the cement composite undisturbed titanium gypsum-based foam concrete comprises the following steps:
s1: mixing and dissolving the metal ion type solution, the early strength type polycarboxylate superplasticizer and water, and stirring for 1-5min at normal temperature to obtain a mixed solution;
s2: adding undisturbed titanium gypsum into the slurry through a conveyer belt by adopting a powerful vibration stirrer, strongly stirring and vibrating for 5-10min, and then adding a stirring solution to obtain titanium gypsum slurry;
s3: accurately metering cement, mineral powder, glass beads, quicklime, an active admixture and carboxymethyl starch ether, then dry-mixing for 1-5min, then putting into the titanium gypsum slurry, and continuously stirring for 3-5min to obtain cement composite titanium gypsum slurry;
s4: preparing an AOS foaming agent into physical foam;
s5: and respectively pumping the physical foam and the cement composite titanium gypsum slurry, and uniformly passing through a stirrer to obtain the cement composite undisturbed titanium gypsum based foam concrete which is uniformly mixed.
The invention has the beneficial effects that:
the invention relates to a cement composite undisturbed titanium gypsum based foam concrete, which is based on the principle that the hydration process of a cement system is the dissolving-crystallizing-precipitating process of various minerals, namely, the concentration of various ions in an aqueous solution is continuously accumulated along with the dissolution of various mineral phases. When the ion concentration in the liquid phase exceeds the solubility of the hydration product and reaches a certain supersaturation degree, the hydration product begins to precipitate. The dynamic process of dissolution-crystallization-precipitation affects the concentration of various ions in the fluid phase of the cement slurry. Based on the principle, the metal ion type solution in the components is used as an ion catalyst, an activation stabilizer and silica gel loaded ferric trichloride (FeCl) 3 /SiO 2 ) The catalyst is an important iron catalyst and is also a heterogeneous catalytic system, and the catalyst often has the advantages of high reaction speed, good selectivity, simple post-treatment, no need of solvent for reaction and the like. Therefore, the method has unique advantages in multi-molecule tandem reaction. In addition, silica gel-loaded calcium chloride (CaCl) in metal ion type solution 2 /SiO 2 ) Has the functions of early strengthening agent and provides more calcium ions. The diatomite in the active admixture also plays a role of crystal nucleus as a non-reactive siliceous material at normal temperature, can quickly adjust the coagulation rate of the foam concrete, has good coagulation acceleration effect on cement, can also make the performance of the concrete greatly leap, and enhances the strength of the foam concrete. Active admixture with active matter grain size in 0.22-0.26 nm to raise the specific surface greatly and to exceed 85000m 2 The activity of the concrete is greatly improved, so that the performance of the foam concrete is greatly improved, such as impermeability and softening coefficient; the fly ash belongs to light aggregate, plays an excellent ball effect in the mixing process, enables bubbles to become 'balls' of slurry freely and uniformly under the condition of difficult unreal extinction, effectively improves the fluidity of the fresh slurry, and increases fly ash glass beadsBesides the fluidity of the gypsum slurry, the titanium gypsum-based foam concrete can also participate in hydration reaction to form silicate crystals so as to enhance the strength of the titanium gypsum-based foam concrete matrix; the carboxymethyl starch ether molecules are in a net structure, so that the viscosity of foam liquid-phase foam walls can be improved, the toughness of the foam walls is improved, the generation of air bubble exhaust and liquid discharge is prevented, and meanwhile, a high-strength interfacial film is formed, so that the stability of foam is improved; the early-strength polycarboxylate superplasticizer can obviously accelerate mineral hydration of cement clinker, has obvious promotion effects on shortening the setting time and improving the early strength, and long side chains in the molecular structure of the early-strength polycarboxylate superplasticizer are easier to play a steric hindrance role in cement slurry, so that the early-strength polycarboxylate superplasticizer is beneficial to enhancing the dispersion effect of the early-strength polycarboxylate superplasticizer, promoting the hydration of cement and improving the mechanical strength; meanwhile, the polymerization reaction is accelerated by heating on the basis of adding a reducing agent, namely mercaptoacetic acid. After being mixed and foamed, the AOS foaming liquid is relatively stable in titanium gypsum slurry, is not easy to break foam, and can greatly reduce the volume weight of concrete, thereby producing light concrete.
The invention optimizes the formula of the concrete, only needs mixing during preparation, does not need steam pressurization or high-temperature drying, can directly utilize the original state byproduct titanium gypsum, and can improve various performance indexes such as the compressive strength, the softening coefficient and the like of the titanium gypsum foamed concrete.
Detailed Description
The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
1. The preparation process of the cement composite undisturbed titanium gypsum-based foam concrete comprises the following steps:
s1: mixing and dissolving the metal ion type solution, the early strength type polycarboxylate superplasticizer and water, and stirring for 1-5min at normal temperature to obtain a mixed solution;
s2: adding undisturbed titanium gypsum into the slurry through a conveyer belt by adopting a powerful vibration stirrer, strongly stirring and vibrating for 5-10min, and then adding a stirring solution to obtain titanium gypsum slurry;
s3: accurately metering cement, mineral powder, glass microspheres, quicklime, an active admixture and carboxymethyl starch ether, then dry-mixing for 1-5min, then adding into the titanium gypsum slurry, and continuously stirring for 3-5min to obtain cement composite titanium gypsum slurry; the glass microspheres are 3M hollow glass microspheres with the particle size range of 15-120um.
S4: foaming the blended AOS foaming liquid by a foaming machine to obtain physical foam;
s5: and respectively pumping the physical foam and the cement composite titanium gypsum slurry, and uniformly passing through a stirrer to obtain the cement composite undisturbed titanium gypsum based foam concrete which is uniformly mixed.
S6: and (3) directly pouring the cement composite titanium gypsum foam concrete into a mould or a template, spraying water, covering and curing for at least 7d to obtain the titanium gypsum foam concrete product.
2. The preparation method of the metal ion type solution comprises the following steps:
a1: selecting commercially available high-quality silica sol (manufactured by Zhejiang Deliver micro-nano technology Limited company, type: sodium type, specification: JN 10-30/1) with particle size range of 9-11nm and solid content of 30 +/-1%, and weighing 500g; the silica sol has higher specific surface area and can be used for catalyst manufacture and catalyst carriers;
a2: pouring the mixture into a 1000ml flask, and heating the mixture in a constant temperature furnace at constant temperature of 100 +/-10 ℃;
a3: adding a calcium chloride solution with the concentration of 3g/ml into the solution obtained in the step A1, wherein the total mass of calcium chloride is 30g, heating to 100-120 ℃, uniformly stirring by using a glass rod for at least 60 times/min, and stirring until the liquid is homogeneous and has no precipitate;
a4: after the constant temperature is kept for 5min, 40g to 50g of analytically pure anhydrous FeCl powder is accurately weighed 3 Pouring into a flask, and uniformly stirring with a glass rod for at least 60 times/min until the upper part and the lower part become light yellow homogeneous sol; except that pure anhydrous FeCl was analyzed in example 13 3 The dosage is 50g, and other metals are adoptedExamples of Ionic solutions pure anhydrous FeCl was analyzed 3 The dosage is 40g;
a5: cooling to room temperature.
3. Preparation of active admixtures
The active admixture is formed by mixing an active siliceous material, an active aluminum material and a non-reactive siliceous material. The active siliceous material is any one of rice hull ash or silica ash, the active aluminous material is any one of aluminosilicate cement and sulphoaluminate cement, the non-reactive siliceous material is diatomite, and the weight ratio of the active siliceous material to the active aluminous material to the diatomite is (3-6): 1:1.
the preparation method comprises the following steps:
b1: preparing silica fume or rice hull ash after sufficient combustion, siO 2 The content of the active additive accounts for about 90 percent of the total amount of the smoke dust, the granularity is very small, the average granularity is nearly nano-grade, and the active additive is used as an efficient active admixture for standby. In all the examples using the active admixture, silica fume was used in an amount of 4 parts by mass, except that silica fume was used in an amount of 6 parts by mass in example 14.
B2: performing ultra-pure ultra-fine processing on 1 part by mass of active aluminum material by using a jet mill to ensure that the fineness of the active aluminum material reaches more than 6000 meshes;
b3: putting 1 part by mass of dried diatomite into the diatomite to perform ultra-pure and ultra-fine processing so that the fineness of the diatomite reaches more than 6000 meshes;
b4: and (3) adding the active siliceous material, the active alumina material and the diatomite at one time by adopting an air flow mixer, and mixing for 5-10min to obtain the nano-grade active admixture.
4. The preparation method of the early strength type polycarboxylate superplasticizer comprises the following steps:
c1, adding 500g of solution of 20 mass percent of isobutylene polyoxyethylene ether macromonomer and 500g of deionized water into a four-neck flask with a thermometer and a peristaltic pump; stirring and heating, and heating to 60-70 deg.C; the isobutylene alcohol polyoxyethylene ether macromonomer is isobutylene alcohol polyoxyethylene ether with the molecular weight of 2400.
C2, after the temperature is stable, adding a mixed solution of 200g of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and deionized water by using a pipette, wherein the mass ratio of the acrylic acid to the 2-acrylamide-2-methylpropanesulfonic acid to the deionized water is 1;
c3, adding aqueous solution of mercaptoacetic acid and 15g of composite initiator with the concentration of 0.01-0.02mol/L, wherein the composite initiator is formed by compounding ammonium persulfate and diethanol amine, the mass ratio of the mercaptoacetic acid to the ammonium persulfate to the diethanol amine is 2;
and C4, cooling the solution to room temperature after the reaction is finished, and neutralizing the solution by using a sodium hydroxide solution with a certain concentration until the pH value is neutral to obtain the early strength type polycarboxylate superplasticizer with the total solution amount of 1620ml, 20g of the aqueous solution of thioglycolic acid and the composite initiator and the sodium hydroxide solution, wherein the concentration of the water reducer solution, namely the solid content, is controlled to be about 30.9%.
The concentration of the water reducing agent solution, namely the solid content, is the ratio of the total amount of the isobutylene alcohol polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-methylpropanesulfonic acid to the total water reducing agent amount, wherein the influence of the thioglycolic acid, the composite initiator and the sodium hydroxide on the solid content is neglected.
The concentration of the isobutylene alcohol polyoxyethylene ether in example 15 was 8%, and the other steps were the same as those of the above-mentioned preparation method of the early strength type polycarboxylic acid water reducing agent.
The following examples are prepared by the above preparation process, and the water-cement ratio is controlled to be 0.5-0.6.
Example 1:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.5 parts of water.
Detection shows that the test block is formed well, has a good and uniform pore structure, has the 28d compressive strength of 6.25MPa, and has the dry density of 706kg/m for high speed and soft speedThe chemical coefficient is 0.86, the fluidity is 200mm, the compressive strength and the dry density reach the compressive strength of more than 5.3MPa specified by qualified BO 7-grade air-entrapping block products in GB/T11968-2006 autoclaved aerated concrete Block, and the dry density is less than 730kg/m 3 The requirements of (2).
Example 2:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of cement foaming reinforcing agent (gallery general chemical Co., ltd.), 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylic acid water reducing agent, 1 part of AOS foaming agent and 9.5 parts of water.
In comparison with example 1, example 2 does not add a metal ionic solution, but replaces it with 20 parts of a cement foaming enhancer. Through detection, the test block is better in forming, has a good and uniform pore structure except for individual large bubbles, but has lower 28d compressive strength which is 1.73MPa, has dry density of 767kg/m for plantation, and has both compressive strength and dry density exceeding the requirements of qualified BO 7-grade aerated block products in GB/T11968-2006 autoclaved aerated concrete Block.
It can be seen that the commercial cement foaming enhancer is less effective than the self-developed metal ion solution at the same dosage.
Example 3:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 15 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylate superplasticizer, 1 part of AOS foaming agent and 14.5 parts of water.
Through detection, the test block is good in forming and has a good and uniform hole structure, the 28d compressive strength is 5.63MPa, the dry density is 717kg/m, the softening coefficient is 0.81, and both the compressive strength and the dry density meet the requirements of qualified BO 7-grade aerated block products in GB/T11968-2006 autoclaved aerated concrete Block, but the strength is reduced to a certain extent.
It can be seen that the amount of the metal ion type solution is important for strength, and the water-proof effect is also not small.
Example 4:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
22 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early-strength polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.5 parts of water.
Compared with the embodiment 1, the embodiment 4 does not add the quicklime and improves the mixing amount of the titanium gypsum. Through detection, the 28d compressive strength is 4.35MPa, the dry density is 725kg/m, and the 28d compressive strength is lower than the requirement of qualified BO 7-grade aerated block products in GB/T11968-2006 autoclaved aerated concrete Block.
Therefore, because the activity ratio of the mineral powder is lower, a certain alkaline activator needs to be added to provide the activity of fully exciting the mineral powder in an alkaline environment, and when the content of the quicklime is 1% -4%, the activity of the mineral powder can be effectively excited.
Example 5:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 34 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ionic solution, 0.2 part of carboxymethyl starch ether, 0.3 part of early-strength polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.5 parts of water.
Compared with the embodiment 1, the embodiment 5 does not add the active admixture and improves the mixing amount of the P.O42.5 grade cement. Through test detection, the test block is good in forming and has a good and uniform pore structure, the 28d compressive strength is 4.72MPa, the dry density is 719kg/m and the softening coefficient is 0.82, wherein the 28d compressive strength is lower than the requirement of qualified BO 7-grade aerated block products in GB/T11968-2006 autoclaved aerated concrete Block, and the softening coefficient is also reduced.
Therefore, under the condition of the same quality of the active admixture and the cement, the active admixture has extremely high activity, and can greatly improve the strength of the foam concrete, so that the performance of the foam concrete is greatly improved, such as compressive strength, softening coefficient and the like.
Example 6:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 31 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 3 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylic acid water reducing agent, 1 part of AOS foaming agent and 9.5 parts of water.
Example 6 decreased the amount of the active admixture and increased the amount of the p.o42.5 grade cement compared to example 1. Through test detection, the test block is better in forming and has a good and uniform pore structure, the 28d compressive strength is 5.65MPa, the dry density is 715kg/m, and the softening coefficient is 0.85, wherein the 28d compressive strength and the dry density meet the requirements of qualified products of BO 7-grade aerated blocks in GB/T11968-2006 autoclaved aerated concrete block, but the strength is reduced compared with that of example 1.
Therefore, the active admixture has extremely high activity, can greatly improve the strength of the foam concrete, and can meet the requirements of the current standard within a proper mixing amount range.
Example 7:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 29 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 5 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylic acid water reducing agent, 1 part of AOS foaming agent and 9.5 parts of water.
Example 7 increased the amount of active admixture and decreased the amount of p.o42.5 grade cement compared to example 1. Through test detection, the test block is good in forming and has a good and uniform pore structure, the 28d compressive strength is 5.91MPa, the dry density is 692kg/m, and the softening coefficient is 0.89, wherein the 28d compressive strength and the dry density meet the requirements of qualified BO 7-grade aerated block products in GB/T11968-2006 autoclaved aerated concrete Block, and the compressive strength and the softening coefficient are both improved compared with those of the test block in example 1.
Therefore, the active admixture has extremely high activity, can greatly improve the strength of the foam concrete, and can meet the requirements of the current standard within a proper mixing amount range.
Example 8:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of commercially available polycarboxylic acid water reducing agent, 1 part of AOS foaming agent and 9.5 parts of water.
In example 8, 0.3 part of a commercially available polycarboxylic acid water reducing agent was used as compared with example 1, and the comparison was made under the same conditions. Tests show that the fluidity of the foam concrete is only 180mm, which is 40mm lower than that of the foam concrete in example 1; the test block is good in forming and has a good and uniform hole structure, the 28d compressive strength is 5.51MPa, the dry density is 748kg/m, and the softening coefficient is 0.84, wherein the dry density does not meet the requirements of qualified BO 7-grade aerated block products in GB/T11968-2006 autoclaved aerated concrete Block, and the compressive strength and the softening coefficient are both reduced compared with those of the embodiment 1.
Therefore, compared with the commercial polycarboxylic acid water reducing agent, the early-strength polycarboxylic acid water reducing agent has obvious dispersion effect, increases the fluidity of foam concrete, accelerates the mineral hydration of cement clinker and improves the mechanical strength.
Example 9:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.4 part of early strength type polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.4 parts of water.
In example 9, 0.4 part of an early strength polycarboxylate water reducing agent was used as compared with example 1. Through test detection, the fluidity of the foam concrete reaches 230mm, which is 10mm higher than that of the foam concrete in example 1; the test block is good in forming and has a good and uniform pore structure, the 28d compressive strength is 6.35MPa, the dry density is 705kg/m for carrying out heavy planting, and the softening coefficient is 0.85, wherein both the compressive strength and the dry density meet the requirements of qualified BO 7-grade aerated blocks in GB/T11968-2006 autoclaved aerated concrete Block, and the compressive strength is improved in comparison with that of example 1.
Therefore, the early-strength polycarboxylate superplasticizer not only has obvious dispersion effect, increases the fluidity of foam concrete, has the effect of reducing water, but also can accelerate the hydration of cement clinker minerals and improve the mechanical strength, and can meet the requirements of the current standard within a proper mixing amount range.
Example 10:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylic acid water reducing agent, 1.2 parts of AOS foaming agent and 9.3 parts of water.
Example 10 the AOS blowing agent loading was increased by 0.2 parts while reducing the water loading compared to example 1. Through test detection, the fluidity of the foam concrete meets the requirement; the test block is good in forming and has a good and uniform pore structure, the 28d compressive strength is 5.12MPa, the dry density is 675kg/m for carrying out heavy planting, and the softening coefficient is 0.75, wherein the compressive strength does not meet the requirement of qualified BO 7-grade aerated blocks in GB/T11968-2006 autoclaved aerated concrete block, and the softening coefficient is greatly reduced compared with that of example 1.
Therefore, when the mixing amount of the foaming agent is increased, the number of air holes formed in the foaming gypsum material is large, and although a large number of air holes are formed in the material, part of hole walls are damaged, so that the phenomenon of hole crossing or hole collapsing is caused; when the mixing amount of the foaming agent is 1 part, the quantity and the size of air holes in the material are suitable and are uniformly distributed in an internal structure, and the phenomenon that the air holes are damaged does not occur. Therefore, the foaming gypsum material with better pore structure can be obtained by adding a proper amount of foaming agent.
Example 11:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
15 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 13 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylic acid water reducing agent, 1 part of AOS foaming agent and 9.5 parts of water.
Compared with the embodiment 1, the titanium gypsum content of the embodiment 11 is reduced by 5 parts, and the mineral powder content is increased. Through test detection, the fluidity of the foam concrete meets the requirement; the test block is good in forming and has a good and uniform hole structure, the 28d compressive strength is 6.31MPa, the dry density is 631kg/m for high speed cultivation, the softening coefficient is 0.89, the compressive strength, the dry density and the like are superior to the requirements of qualified BO 7-grade aerated blocks in GB/T11968-2006 autoclaved aerated concrete block, and the softening coefficient is improved to a certain extent compared with that of example 1.
Therefore, as the original-state titanium gypsum has no activity and needs to be excited by other active ingredients, when the mixing amount of the original-state titanium gypsum is reduced and the mixing amount of the mineral powder is increased, the active ingredients in the foamed gypsum material are more, the pores in the material can be better stabilized, the quantity and the size are more suitable, and the pores are uniformly distributed in the internal structure, so that various indexes are improved. Therefore, if a foam concrete with better performance is desired, the mixing ratio of the raw titanium gypsum can be properly reduced.
Example 12:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
35 parts of titanium gypsum, 20 parts of P.O42.5-grade cement, 5 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylic acid water reducing agent, 1 part of AOS foaming agent and 7.5 parts of water.
Compared with the example 1, the titanium gypsum doping amount of the example 12 is increased by 15 parts, and the doping amounts of cement, mineral powder and water must be reduced simultaneously under the condition that the mass fraction is not changed totally. Through test detection, the fluidity of the foam concrete is only 155mm; the test block is good in forming and has a good and uniform hole structure, the 28d compressive strength is 4.72MPa, the dry density is 775kg/m, the softening coefficient is 0.72, the compressive strength, the dry density and the like are far lower than the requirements of qualified products of BO 7-grade aerated blocks in GB/T11968-2006 autoclaved aerated concrete Block, and the softening coefficient is greatly reduced compared with that of example 1; but still meets the requirements of national standard JG/T266-2011 foam concrete, and can be applied to occasions such as roadbed filling and the like.
Therefore, as the original titanium gypsum has no activity and strong viscosity, when the mixing amount of the original titanium gypsum is increased and the mixing amount of cement, mineral powder and water is reduced, the active ingredients in the foaming gypsum material are less, the foaming performance is poorer, so that a part of pore walls of pores in the material are damaged, the phenomena of lower bubble rate and higher dry density occur, and various indexes are softened. Therefore, if a foam concrete with better performance is desired, the blending ratio of the raw titanium gypsum should be properly adjusted.
Example 13:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.5 parts of water.
Through detection, the test block is better in forming and has a good and uniform pore structure, the 28d compressive strength is 6.51MPa, the dry density is 725kg/m, the softening coefficient is 0.87, the compressive strength and the dry density reach the compressive strength of more than 5.3MPa specified by a qualified BO 7-grade aerated block product in GB/T11968-2006 autoclaved aerated concrete Block, and the dry density is less than 730kg/m 3 The requirements of (1).
Same as in example 1In contrast, the analytically pure ferric chloride weight increased to 50g in the metal ion type solution, in which ferric chloride (FeCl) supported on silica gel was added 3 /SiO 2 ) Is an important iron catalyst and a heterogeneous catalytic system, and has the advantages of high reaction speed and improved strength.
Example 14:
the cement composite undisturbed titanium gypsum-based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.5 parts of water.
Detection shows that the test block is good in forming and has a good and uniform pore structure, the 28d compressive strength is 6.81MPa, the dry density is 690kg/m, the softening coefficient is 0.87, the compressive strength and the dry density reach the compressive strength larger than 5.3MPa specified by BO 7-grade aerated block qualified products in GB/T11968-2006 autoclaved aerated concrete Block, and the dry density is less than 730kg/m 3 The requirements of (1).
Compared with the example 1, the weight of the silica fume in the active admixture is increased to 6 parts, and the excellent activity and the filling effect thereof enable the strength of the foam concrete to be increased to a certain extent and have the characteristic of better water retention.
Example 15:
the cement composite undisturbed titanium gypsum based foam concrete comprises the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.5 parts of water.
Detection shows that the test block is good in forming and has a good and uniform pore structure, the 28d compressive strength is 6.57MPa, the dry density is 740kg/m, the softening coefficient is 0.85, and the fluidity is 155mm. Compared with the example 1, the isobutenol polyoxyethylene in the early-strength polycarboxylate superplasticizerThe concentration of vinyl ether is reduced to 8 percent, the compressive strength is improved to a certain extent, and the dry density is increased because the water reducing effect is poor, the fluidity is small, the foam breaking rate is high, the foam content is reduced, the compressive strength which does not meet the qualification requirement of BO 7-grade air-entraining block in GB/T11968-2006 is more than 5.3MPa, and the dry density is less than 730kg/m 3 The requirements of (1).
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. The cement composite undisturbed titanium gypsum-based foam concrete is characterized by comprising the following components in parts by weight:
15-40 parts of titanium gypsum, 20-40 parts of P.O42.5-grade cement, 5-10 parts of mineral powder, 3-8 parts of glass beads, 1-4 parts of quicklime, 15-25 parts of metal ionic solution, 3-5 parts of active admixture, 0.1-0.5 part of carboxymethyl starch ether, 0.1-0.5 part of early strength polycarboxylate superplasticizer, 0.5-1.2 parts of AOS foaming agent and 3-10 parts of water;
the metal ion type solution is prepared from 500g of silica sol, 15-30ml of calcium chloride aqueous solution and analytically pure anhydrous FeCl 3 40-50g of the mixture is prepared; the particle size range of the silica sol is 9-11nm, and the concentration of the calcium chloride aqueous solution is 1-3g/ml; the active blending agent is formed by mixing an active siliceous material, an active aluminum material and a non-reactive siliceous material; the active siliceous material is any one of rice hull ash or silica ash, the active aluminous material is any one of aluminosilicate cement and sulphoaluminate cement, the non-reactive siliceous material is diatomite, and the weight ratio of the active siliceous material to the active aluminous material to the diatomite is (3-6): 1:1.
2. the cement composite undisturbed titanium gypsum-based foam concrete as claimed in claim 1, wherein 15-20 parts of titanium gypsum, 20-40 parts of P.O42.5 grade cement, 5-10 parts of mineral powder, 3-8 parts of glass beads, 1-4 parts of quicklime, 15-25 parts of metal ion type solution, 3-5 parts of active admixture, 0.1-0.5 part of carboxymethyl starch ether, 0.1-0.5 part of early strength type polycarboxylic acid water reducing agent, 0.5-1.2 parts of AOS foaming agent and 3-10 parts of water.
3. The cement composite undisturbed titanium gypsum-based foam concrete of claim 1, characterized by comprising the following components in parts by weight:
20 parts of titanium gypsum, 30 parts of P.O42.5-grade cement, 8 parts of mineral powder, 5 parts of glass beads, 2 parts of quicklime, 20 parts of metal ion type solution, 4 parts of active admixture, 0.2 part of carboxymethyl starch ether, 0.3 part of early strength type polycarboxylate superplasticizer, 1 part of AOS foaming agent and 9.5 parts of water.
4. The cementitious composite undisturbed titanium gypsum-based foamed concrete of claim 1 wherein said active admixture is prepared by the process of:
b1: preparing 4 parts by mass of silica fume or fully combusted rice hull ash;
b2: 1 part by mass of active aluminum material is processed into the fineness of more than 6000 meshes;
b3: putting 1 part by mass of dried diatomite into the diatomite to perform ultra-pure and ultra-fine processing so that the fineness of the diatomite reaches more than 6000 meshes;
b4: the active siliceous material, the active aluminous material and the diatomite are put into and mixed at one time.
5. The cement composite undisturbed titanium gypsum-based foam concrete of claim 1 wherein the preparation method of the early strength polycarboxylate water reducer is as follows:
c1, mixing 500g of solution of 10-30 mass percent of isobutylene alcohol polyoxyethylene ether macromonomer and 500g of deionized water, and heating to 60-70 ℃;
c2, adding the components in a mass ratio of 1:1:1, 200g of acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and deionized water;
and C3, adding aqueous solution of thioglycolic acid and 15g of composite initiator with the concentration of 0.01-0.02mol/L, wherein the composite initiator is formed by compounding ammonium persulfate and diethanolamine, and the mass ratio of the thioglycolic acid to the ammonium persulfate to the diethanolamine is 1-5:1-5:1, stirring and keeping the temperature at 60-70 ℃, and reacting to graft a monomer with an early strength function on a methacrylate-polyoxyethylene ether copolymer molecular chain;
and C4, neutralizing by using a sodium hydroxide solution until the pH value is neutral to obtain the early-strength polycarboxylate superplasticizer, wherein the concentration, namely the solid content, of the water reducer solution is controlled to be 30-45%.
6. The method for producing a cement composite undisturbed titanium gypsum based foamed concrete according to any one of claims 1 to 5, characterized by comprising the steps of:
s1: mixing and dissolving the metal ion type solution, the early strength type polycarboxylate superplasticizer and water, and stirring for 1-5min at normal temperature to obtain a mixed solution;
s2: putting undisturbed titanium gypsum into a strong vibration stirrer through a conveyer belt, strongly stirring and vibrating for 5-10min, and then adding a stirring solution to obtain titanium gypsum slurry;
s3: accurately metering cement, mineral powder, glass microspheres, quicklime, an active admixture and carboxymethyl starch ether, then dry-mixing for 1-5min, then adding into the titanium gypsum slurry, and continuously stirring for 3-5min to obtain cement composite titanium gypsum slurry;
s4: preparing the AOS foaming agent into physical foam;
s5: and respectively pumping the physical foam and the cement composite titanium gypsum slurry, and uniformly passing through a stirrer to obtain the cement composite undisturbed titanium gypsum based foam concrete which is uniformly mixed.
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