CN112851254B - Preparation method of cement-based modified porous material - Google Patents
Preparation method of cement-based modified porous material Download PDFInfo
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- CN112851254B CN112851254B CN202110164073.4A CN202110164073A CN112851254B CN 112851254 B CN112851254 B CN 112851254B CN 202110164073 A CN202110164073 A CN 202110164073A CN 112851254 B CN112851254 B CN 112851254B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
- C04B38/106—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam by adding preformed foams
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/40—Porous or lightweight materials
-
- 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
-
- 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
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention provides a preparation method of a cement-based modified porous material, which mainly comprises the following steps: weighing raw materials, preparing cement-based slurry, preparing enhanced foam, and preparing the cement-based modified porous material. The method has simple process and lower cost, and the prepared cement-based modified porous material has good strength, toughness and heat conductivity, can be used as a phase-change material adsorption carrier, remarkably improves the heat storage performance of the composite phase-change material, and can meet the requirements of different projects.
Description
Technical Field
The invention relates to the technical field of energy-saving and energy-storing materials, in particular to a preparation method of a cement-based modified porous material.
Background
Under the current shortage of global energy, the research and development of the phase change energy storage technology solve the problem of supply and demand mismatching caused by the instantaneity and instability of renewable energy. The composite phase-change material is used as an important branch of a phase-change energy storage technology, can effectively inhibit the leakage problem of the liquid phase-change material, and has become a research hotspot in the field of novel phase-change heat storage materials. The composite phase-change material can be prepared by a porous adsorption method, namely, a porous material with a rich pore structure is used as a carrier to adsorb the liquid phase-change material under the action of negative pressure. Therefore, the selection of the porous carrier determines to some extent the properties of the composite phase change material.
The porous carriers used in the present research mainly include porous carbons, inorganic porous lightweight aggregates, recycled aggregates, and the like. Porous carbons generally include expanded graphite, activated carbon, graphene, and the like. In patent document CN106701033A, "a method and an apparatus for preparing a porous medium composite phase-change material", activated carbon, expanded graphite, carbon aerogel, carbon fiber, carbon nanotube, graphene or ceramic are used as a porous support material for the phase-change material. The inorganic porous light aggregate generally comprises ceramsite, expanded perlite, high titanium slag, bentonite, sepiolite and the like. In patent document CN105621918A, "a building phase-change heat storage composite material capable of being used as lightweight aggregate", one or more of sepiolite, bentonite, zeolite, expanded perlite, vitrified micro bubbles, waste EPS, etc. are used as phase-change adsorption materials. The recycled aggregate generally comprises waste concrete crushed particles, waste autoclaved aerated concrete crushed particles and the like. In patent document CN104987000A, "ecological recycled fine aggregate phase change temperature adjustment mortar and preparation method thereof", the recycled fine aggregate obtained by crushing and screening waste concrete is used as an adsorption carrier of phase change material. In patent document CN104944819A "a phase change energy storage aggregate and a preparation method thereof", the phase change energy storage aggregate is prepared by using waste building autoclaved aerated concrete.
However, the porous carriers of the prior art all have the following problems: firstly, the porosity of the material is small and unstable, the adsorption rate of the phase-change material is directly influenced, and the energy storage effect of the composite phase-change material is restricted; secondly, the inorganic lightweight aggregate and the recycled aggregate porous carrier have poor heat conductivity and small heat storage capacity per unit volume; in addition, porous carbon, especially graphene, carbon nanotubes and the like, are poor in economy when used as porous carriers, and limit the popularization and application of the composite phase change material.
Therefore, the porous material with high porosity, stable performance, good heat conductivity and excellent economy is invented to be used as the adsorption carrier of the phase-change material, and has important significance for the development and application of the high-performance composite phase-change material.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a cement-based modified porous material with controllable porosity, good heat conductivity and excellent economy, which specifically comprises the following steps:
1) weighing the following raw materials in parts by weight: 150-280 parts of cement, 0-120 parts of mineral admixture, 0.1-0.3 part of early strength agent, 0.2-0.5 part of water reducing agent, 0.2-1 part of glass fiber, 0.8-1.5 parts of heat conducting carbon fiber, 40-100 parts of water, 25-45 parts of enhanced foam and 0.2-0.8 part of modifier;
2) preparing cement-based slurry: mixing and stirring cement, mineral admixture, early strength agent, glass fiber and heat-conducting carbon fiber according to a proportion uniformly, then adding water and water reducing agent, mixing and stirring uniformly to prepare cement-based slurry;
3) preparing an enhanced foam: firstly diluting the foaming agent by 35-40 times, then uniformly mixing the foaming agent with the foam reinforcing agent and the foam stabilizing agent, and preparing the enhanced foam by adopting a mechanical foaming mode;
4) preparing a cement-based modified porous material: and mixing the enhanced foam and the cement-based slurry in proportion, adding a modifier, mechanically stirring to uniformly disperse the enhanced foam, pouring and filling a mold quickly after the modifier fully acts, and performing steam curing to obtain the finished cement-based modified porous material.
Further, the weight part of the glass fiber in the step 1) is 0.5 part.
Further, the cement in the step 1) is ordinary portland cement, the early strength agent is calcium stearate, and the water reducing agent is a polycarboxylic acid water reducing agent.
Further, the mineral admixture in the step 1) is one or more of fly ash, slag powder and silica fume.
Further, the heat conductive carbon fiber is vapor grown carbon fiber.
Further, the water-cement ratio in the step 2) is 0.2-0.35, and the volume ratio of the enhanced foam to the cement-based slurry is 3-7: 1.
The cement variety is selected according to the dry apparent density of the cement-based modified porous material, and the dry apparent density of the cement-based modified porous material is not less than 400kg/m3In this case, P.O 42.5 cement is preferable; the dry apparent density of the cement-based modified porous material is less than 400kg/m3In this case, P.O 52.5 cement is preferred.
Further, the weight ratio of the foaming agent to the foam reinforcing agent to the foam stabilizing agent in the step 3) is 25.0:2.0: 1.8.
Further, the foam reinforcing agent is polyvinyl alcohol.
Further, the foam stabilizer is one or more of triethanolamine, polyethylene glycol, dodecanol and hexadecanol.
Further, the modifier is one or two of sodium carbonate and sodium bicarbonate, and the adding amount of the modifier accounts for 0.4% of the mass of the cement-based slurry.
The dry apparent density of the finished cement-based modified porous material prepared by the method is 200-600kg/m3The porosity is 70-90%, the interconnected porosity is 50-84%, the thermal conductivity is 0.15-0.38W/(m.K),the compressive strength is 1.0-4.5 MPa.
The invention also provides application of the cement-based modified porous material as a phase change material adsorption carrier. The material can be used as an adsorption carrier of a phase-change material and used for preparing a novel efficient composite phase-change material.
The invention changes the foam hole type through the action of the modifier, changes the closed hole into a communicating hole, and simultaneously achieves the effect of improving the hole type through controlling the water-gel ratio and the mixing amount of the enhanced foam; in addition, the technical scheme of the invention can adjust the apparent density of the material, control the porosity and the pore characteristics of the material, and improve the strength, the toughness and the heat-conducting property of the cement-based modified porous material through the coupling treatment of the glass fiber; the enhanced foam prepared by the invention has uniform foam holes and good foam wall toughness by regulating and controlling the raw material ratio of the foaming agent, the foam reinforcing agent and the foam stabilizer and combining a mechanical foaming method.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) according to the invention, by controlling the water-gel ratio and the doping amount of the enhanced foam, especially under the condition of adding the modifier, the proportion of open pores and communicated pores can be improved, so that the adsorption efficiency of the phase-change material is improved, the effects of adjustable porosity and controllable pore type are realized, and the adsorption performance of the phase-change material is improved;
(2) according to the invention, the problem of poor heat conductivity of the inorganic material is solved by adding the heat-conducting carbon fibers, so that the finished cement-based modified porous material has good heat conductivity, and therefore, the heat storage performance of the composite phase-change material can be obviously improved when the modified porous material is used as a phase-change material adsorption carrier;
(3) the size and the shape of the cement-based modified porous material provided by the invention can be prefabricated according to requirements, and the cement-based modified porous material can also be crushed into small particles to be used as a carrier of a phase change material, so that the shape and the size are more flexible, and the requirements of different projects can be met;
(4) the cement-based modified porous material provided by the invention is simple in preparation process, low in cost, capable of accurately controlling the porosity and the pore characteristics, and suitable for large-scale production of composite phase-change materials.
Detailed Description
The invention provides 1 a preparation method of a cement-based modified porous material, which is characterized by comprising the following steps:
1) weighing the following raw materials in parts by weight: 150-280 parts of cement, 0-120 parts of mineral admixture, 0.1-0.3 part of early strength agent, 0.2-0.5 part of water reducing agent, 0.2-1 part of glass fiber, 0.8-1.5 parts of heat conducting carbon fiber, 40-100 parts of water, 25-45 parts of enhanced foam and 0.2-0.8 part of modifier;
2) preparing cement-based slurry: mixing and stirring cement, mineral admixture, early strength agent, glass fiber and heat-conducting carbon fiber uniformly according to a proportion, then adding water and water reducing agent, mixing and stirring uniformly to prepare cement-based slurry;
3) preparing an enhanced foam: firstly diluting the foaming agent by 35-40 times, then uniformly mixing the foaming agent with the foam reinforcing agent and the foam stabilizing agent, and preparing the enhanced foam by adopting a mechanical foaming mode;
4) preparing a cement-based modified porous material: and mixing the enhanced foam and the cement-based slurry in proportion, adding a modifier, mechanically stirring to uniformly disperse the enhanced foam, pouring and filling a mold quickly after the modifier fully acts, and performing steam curing to obtain the finished cement-based modified porous material.
In one embodiment, the cement in step 1) is ordinary portland cement, the early strength agent is calcium stearate, and the water reducing agent is a polycarboxylic acid water reducing agent.
In one embodiment, the mineral admixture in step 1) is one or more of fly ash, slag powder and silica fume.
In one embodiment, the thermally conductive carbon fibers are vapor grown carbon fibers.
In one embodiment, the cement-based slurry in step 2) has a water-to-cement ratio of 0.2 to 0.35 and a volume ratio of enhanced foam to cement-based slurry of 3 to 7: 1.
In one embodiment, the weight ratio of the foaming agent to the foam reinforcing agent to the foam stabilizer in the step 3) is 25.0:2.0: 1.8.
In one embodiment, the foam enhancer is polyvinyl alcohol.
In one embodiment, the foam stabilizer is one or more of triethanolamine, polyethylene glycol, dodecanol and hexadecanol.
In one embodiment, the modifier is one or two of sodium carbonate and sodium bicarbonate, and the addition amount of the modifier accounts for 0.4% of the mass of the cement-based slurry.
The invention also provides application of the cement-based modified porous material in serving as a phase change material adsorption carrier. The material can be used as an adsorption carrier of a phase-change material and used for preparing a novel efficient composite phase-change material.
The dry apparent density of the finished cement-based modified porous material prepared by the method is 200-600kg/m3The porosity is 70-90%, the interconnected porosity is 50-84%, the thermal conductivity is 0.15-0.38W/(m.K), and the compressive strength is 1.0-4.5 MPa.
The technical solution provided by the present invention is further illustrated below with reference to examples.
Example 1
A preparation method of a cement-based modified porous material comprises the following steps:
1) 280kg of P & O42.5 cement, 100kg of fly ash, 0.15kg of calcium stearate, 0.6kg of glass fiber and 1.4kg of heat-conducting carbon fiber are stirred and premixed to uniformly disperse the glass fiber and the heat-conducting carbon fiber, 95kg of water and 0.45kg of water reducing agent are added while stirring, and the mixture is stirred into uniform cement-based slurry;
2) weighing 250g of foaming agent, adding 10kg of water for dilution, then adding 20g of foam reinforcing agent and 18g of foam stabilizing agent, uniformly mixing, simultaneously pumping the foaming agent and air into a foaming machine under the action of a vacuum pump, and preparing enhanced foam by a mechanical foaming method;
3) adding 25kg of enhanced foam and 0.8kg of modifier into the cement-based slurry prepared in the step 1), adjusting the speed of a stirrer to 25r/min, stirring for 50s to uniformly disperse the enhanced foam, standing for 60s, after the modifier fully acts, quickly pouring and filling a mold, transferring to a steam curing chamber for curing, removing the mold after 24 hours, transferring to a standard condition curing chamber for continuously curing for 28 days, and obtaining the cement-based modified porous material.
The finished cement-based modified porous material prepared by the embodiment has the total porosity of 75%, the interconnected porosity of 60% and the dry apparent density of 500kg/m3The 28-day compressive strength is 3.8MPa, and the thermal conductivity is 0.35W/(mK).
The adsorption rate of the cement-based modified porous material serving as the carrier for adsorbing the phase-change material can reach 65%, and the surface packaging treatment is performed after the phase-change material is adsorbed, so that the heat storage and heat release efficiency of the obtained composite phase-change material is improved by 20% compared with the heat storage and heat release efficiency of a natural porous stone serving as the carrier.
Example 2
The difference from the example 1 is that the raw materials in the step 1) are as follows:
230 parts of P & O42.5 cement, 80 parts of fly ash, 0.15 part of calcium stearate, 0.5 part of glass fiber, 1.3 parts of heat-conducting carbon fiber, 0.4 part of water reducing agent, 78 parts of water, 30 parts of enhanced foam and 0.7 part of modifier.
The finished cement-based modified porous material prepared by the embodiment has the total porosity of 80%, the interconnected porosity of 68% and the dry apparent density of 400kg/m3The 28-day compressive strength is 3.0MPa, and the thermal conductivity is 0.30W/(mK).
The adsorption rate of the cement-based modified porous material serving as a carrier for adsorbing the phase-change material can reach 75%, and the surface packaging treatment is performed after the phase-change material is adsorbed, so that the heat storage and heat release efficiency of the obtained composite phase-change material is improved by 26% compared with the heat storage and heat release efficiency of a natural porous stone serving as a carrier.
Example 3
The difference from the example 1 is that the raw materials in the step 1) are as follows:
170 parts of P & O52.5 cement, 50 parts of fly ash, 0.2 part of calcium stearate, 0.4 part of glass fiber, 1.4 parts of heat-conducting carbon fiber, 0.35 part of water reducing agent, 55 parts of water, 35 parts of enhanced foam and 0.65 part of modifier.
The total porosity of the finished cement-based modified porous material prepared in the example is about 85%, the interconnected porosity is 79%, and the dry apparent porosity isThe density was 300kg/m3The 28-day compressive strength is 1.5MPa, and the thermal conductivity is 0.24W/(mK).
The adsorption rate of the cement-based modified porous material serving as a carrier for adsorbing the phase change material can reach 82%, and the surface packaging treatment is performed after the phase change material is adsorbed, so that the heat storage and heat release efficiency of the obtained composite phase change material is improved by 30% compared with the heat storage and heat release efficiency of a natural porous stone serving as a carrier.
Example 4
The difference from the example 1 is that the raw materials in the step 1) are as follows:
140 parts of P & O52.5 cement, 0.25 part of calcium stearate, 0.4 part of glass fiber, 1.5 parts of heat-conducting carbon fiber, 0.35 part of water reducing agent, 45 parts of water, 40 parts of enhanced foam and 0.6 part of modifier.
The total porosity of the finished cement-based modified porous material prepared in the example is about 85%, the interconnected porosity is 84%, and the dry apparent density is 200kg/m3The 28-day compressive strength is 0.8MPa, and the thermal conductivity is 0.19W/(mK).
The adsorption rate of the cement-based modified porous material serving as a carrier for adsorbing the phase-change material can reach 86%, and the surface packaging treatment is performed after the phase-change material is adsorbed, so that the heat storage and heat release efficiency of the obtained composite phase-change material is improved by 35% compared with the heat storage and heat release efficiency of a natural porous stone serving as a carrier.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (4)
1. The preparation method of the cement-based modified porous material is characterized by comprising the following steps of:
1) weighing the following raw materials in parts by weight: 150-280 parts of cement, 0-120 parts of mineral admixture, 0.1-0.3 part of early strength agent, 0.2-0.5 part of water reducing agent, 0.2-1 part of glass fiber, 0.8-1.5 parts of heat conducting carbon fiber, 40-100 parts of water, 25-45 parts of enhanced foam and 0.2-0.8 part of modifier;
2) preparing cement-based slurry: mixing and stirring cement, mineral admixture, early strength agent, glass fiber and heat-conducting carbon fiber uniformly according to a proportion, then adding water and water reducing agent, mixing and stirring uniformly to prepare cement-based slurry;
3) preparing an enhanced foam: firstly diluting the foaming agent by 35-40 times, then uniformly mixing the foaming agent with the foam reinforcing agent and the foam stabilizing agent, and preparing the enhanced foam by adopting a mechanical foaming mode;
4) preparing a cement-based modified porous material: mixing the enhanced foam and the cement-based slurry in proportion, adding a modifier, mechanically stirring to uniformly disperse the enhanced foam, pouring and filling a mold quickly after the modifier fully acts, and performing steam curing to obtain a finished cement-based modified porous material;
the cement in the step 1) is ordinary portland cement, the early strength agent is calcium stearate, and the water reducing agent is a polycarboxylic acid water reducing agent;
the mineral admixture in the step 1) is one or more of fly ash, slag powder and silica fume;
the heat-conducting carbon fibers are vapor-grown carbon fibers;
the foam reinforcing agent is polyvinyl alcohol;
the modifier is one or two of sodium carbonate and sodium bicarbonate, and the addition amount of the modifier accounts for 0.4 percent of the mass of the cement-based slurry;
the water-gel ratio in the cement-based slurry is 0.2-0.35, and the volume ratio of the enhanced foam to the cement-based slurry is 3-7: 1.
2. The method for preparing the cement-based modified porous material as claimed in claim 1, wherein the weight ratio of the foaming agent to the foam reinforcing agent to the foam stabilizing agent in step 3) is 25.0:2.0: 1.8.
3. The method for preparing the cement-based modified porous material as claimed in claim 1, wherein the foam stabilizer is one or more of triethanolamine, polyethylene glycol, dodecanol and hexadecanol.
4. Use of a cement-based modified porous material prepared according to any one of claims 1 to 3 as an adsorption carrier for phase change materials.
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| JP2002053379A (en) * | 2000-08-03 | 2002-02-19 | Tsunetaka Yokoyama | Method for manufacturing new lightweight cellular concrete article |
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