CN114538840A - Preparation method of high-strength anti-freezing foam concrete with in-situ generated whiskers - Google Patents

Preparation method of high-strength anti-freezing foam concrete with in-situ generated whiskers Download PDF

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CN114538840A
CN114538840A CN202210273511.5A CN202210273511A CN114538840A CN 114538840 A CN114538840 A CN 114538840A CN 202210273511 A CN202210273511 A CN 202210273511A CN 114538840 A CN114538840 A CN 114538840A
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stirring
curing
temperature
foaming
solution
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董莉
张立萍
吕灵灵
管洪乐
李大鹏
王沿森
张贝贝
孔慧
赵洁
张新功
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Qingdao Hui Cheng Environmental Technology Co ltd
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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
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/18—Waste materials; Refuse organic
    • C04B18/24—Vegetable refuse, e.g. rice husks, maize-ear refuse; Cellulosic materials, e.g. paper, cork
    • 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
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • 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
    • C04B2111/76—Use at unusual temperatures, e.g. sub-zero
    • 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
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)

Abstract

The invention discloses a technological process of preparing high-strength anti-freezing foam concrete by using gasification furnace slag, which can enable a product to obtain higher strength, enhance the anti-freezing property of the product, and has simple flow and easy operation.

Description

Preparation method of high-strength anti-freezing foam concrete with in-situ generated whiskers
Technical Field
The invention aims to directly generate and modify the whiskers in the process of preparing the high-strength anti-freezing foam concrete with in-situ generated whiskers, provides a preparation method of the high-performance and high-strength foam concrete, and simultaneously realizes the comprehensive utilization of coal gasification furnace slag.
Background
In recent years, the application of calcium sulfate whiskers to the preparation of concrete is very mature, and the Wang Xiaoqing and the like in 'development test research on mechanical properties of calcium sulfate whisker concrete' show that the basic mechanical properties of the concrete are obviously improved by the doping of the calcium sulfate whiskers, and the compressive strength of the concrete under the optimal doping amount of the whiskers is improved by 30 percent compared with that of the common concrete. The research on the influence of calcium sulfate whiskers on the durability of recycled concrete in Zhang Dongmei, Gunn Europe and the like shows that the durability of concrete can be greatly improved by the incorporation of the calcium sulfate whiskers. Liuming brightness and the like in the research on calcium sulfate whisker concrete carbonization under the action of bending load show that the whiskers and cement paste form a stable space structure, partial stress is transferred to the whiskers under the action of load, the development of cracks is hindered, CO2 is further hindered from entering the interior of concrete, and the carbonization rate of the concrete is reduced.
In the preparation of concrete, there are many related patents related to the application of whiskers, for example, chinese patents CN201811388859.9, CN202110937283.2, CN202111010662.3 and CN202110044072.6 all incorporate a small amount of whiskers in the preparation process of concrete, and because the dispersibility of whiskers is not good, in the use process of whiskers, a dispersant needs to be added or whiskers and a cementing agent are first prepared into a thickening solution so that whiskers are dispersed in a cementing system of concrete; on the other hand, the concrete has certain requirements on the length-diameter ratio of the whiskers, generally within the range of 10-500, and the diameter of the whiskers is 1-10 um, so that the performance of the concrete is prevented from being deteriorated due to poor proportion of coarse and fine aggregates of the concrete caused by too short or too long whisker fibers. Finally, because the calcium sulfate hemihydrate crystal whisker is easy to hydrate, the fiber of the crystal whisker after hydration is shortened, and the strength of concrete is reduced, the crystal whisker needs to be modified to stabilize the crystal form. The Chinese patent CN202110939033.2 adopts calcium sulfate whiskers to prepare the antifreezing agent, directly adopts finished whiskers to prepare the antifreezing agent, and then is applied to concrete, so that the process is complicated and the cost is high. The invention provides CN202111270008.6 an in-situ whisker reinforced autoclaved aerated concrete prepared by using gasified slag and a preparation method thereof, and the concrete is prepared by adopting a method for generating whiskers in situ from the gasified slag, but the method for treating carbon residue in the gasified slag is to float and capture carbon to the surface of the concrete by chloride and a surfactant, the utilization of the waste after cutting is still difficult to solve, and the whisker is hydro-thermally synthesized at 170-190 ℃, so the shape of the whisker is hammer-shaped, the combination with tobermorite is not as close as that of a needle-shaped whisker, and the whisker can absorb moisture in air to be hydrated due to the fact that the whisker is not modified in the preparation process, so that the durability of the concrete is poor.
By adopting the process, the columnar calcium sulfate hemihydrate crystal whisker with better shape is directly generated in the process of preparing the high-strength anti-freezing foam concrete, and the crystal whisker is modified in the brick making process, so that the crystal whisker has stable property, and the prepared concrete has better freezing resistance and durability; meanwhile, the gasification slag is used as a raw material, the method is economical and environment-friendly, and the prepared foam concrete has excellent compressive strength and frost resistance. Provides a new method for preparing high-strength frost-resistant foam concrete for the public.
Disclosure of Invention
Aiming at the defects of the existing problems, the invention aims to provide a preparation method of high-strength anti-freezing foam concrete capable of generating whiskers in situ, wherein the whiskers are directly generated and modified in the preparation process of the high-strength anti-freezing foam concrete, the dispersion problem of calcium sulfate whiskers is not worried about, the whiskers are modified in one step, the property of the whiskers is stable, the whole preparation process of the concrete is simple, gasified slag is used as a raw material, the method is economical and environment-friendly, and the prepared foam concrete has excellent compressive strength and anti-freezing performance.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of high-strength anti-freezing foam concrete with in-situ generated whiskers comprises the following steps:
1) raw material treatment: calcining the gasification furnace slag, and performing ball milling and sieving to obtain the granularity of more than 150 meshes;
2) preparing a modifier carrier: soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0-2.2%, stirring for 30-35 min, and drying at the temperature of 100-110 ℃ for 1h to obtain the modifier carrier.
3) Preparing a foaming solution: mixing and stirring a foaming agent, a foam stabilizer and 25-30% of the total amount of water for 10-15 min at a rotating speed of 300-350 r/min to obtain a foaming solution;
4) preparing a whisker stock solution: stirring sodium sulfate, sodium alginate, a crystal transformation agent and water accounting for 10 percent of the total amount of the water, adjusting the pH of the solution to 8-10 by using a calcium hydroxide solution, continuously stirring for 30min, and reacting at the temperature of 30-40 ℃ to obtain a whisker stock solution.
5) Preparing a gelling stock solution: and mixing and stirring all the rest of the cementing materials, the water reducing agent, the modifier carrier and the rest of the water for 5-10 min at the rotating speed of 130-150 r/min to obtain the cementing slurry.
6) And (3) foaming process: stirring the whisker stock solution obtained in the step 4) and the gelling slurry obtained in the step 5) for 5-10 min, uniformly mixing, adding a foaming solution, continuously stirring for about 1-2 min, uniformly stirring, immediately pouring the mixed slurry into a prepared mould, covering the surface with a preservative film, and standing and foaming for 30 min.
7) Steam pressure curing: putting the product obtained in the step 6) into an autoclave for autoclave curing, curing at a low temperature of 120-140 ℃ for 1-3 h, and then heating to 165-185 ℃.
As a preferable scheme of the application, in the step 1), the gasification furnace slag is firstly burned until the ignition loss is less than 5%, so as to stabilize the ash property, reduce the water demand of concrete, enhance the strength of a product and reduce the shrinkage of the product; then ball-milling and screening the slag until the grain diameter is less than 150 meshes, increasing the surface active points, increasing and accelerating the active SiO2The dissolution and hydration speed of the slag are reduced, and the average grain size of the slag is reduced, so that the system has better filling property.
As a preferable scheme of the application, in the step 2), the straw fiber is soaked in a silane coupling agent with the mass concentration of 2.0-2.2%, stirred for 30-35 min, and then dried for 1h at the temperature of 100-110 ℃ to obtain the modifier carrier. The modified straw fibers are fixed in a plurality of capillary fiber pores of the concrete due to the good permeation effect of the silane coupling agent on the straw fibers, the silane coupling agent is filled in the capillary pores of the whole concrete in the steam-pressing process, and the silane coupling agent is attached to an internal material after a product is taken out of a kettle and dried, so that the generated calcium sulfate hemihydrate whiskers cannot be rehydrated into calcium sulfate dihydrate, the property of the calcium sulfate hemihydrate whiskers is stabilized, the toughness of the concrete is increased, and the freeze-thaw crack resistance of the freeze-thaw resistant concrete is improved. Meanwhile, the straw fiber can also fill and compact the pore structure of the concrete, so that the structural strength of the concrete is improved.
As a preferred technical scheme of the application, in the step 4), the mass ratio is 3.3: 5: stirring 10 percent of the total amount of sodium sulfate, sodium alginate, magnesium sulfate and water, wherein the sodium sulfate can quickly react with Ca (OH)2 to generate calcium sulfate, adjusting the pH of the solution to be 8-10, stirring for 30min, and reacting at the temperature of 30-40 ℃ to preliminarily generate a calcium sulfate dihydrate crystal nucleus with a columnar shape; sodium alginate contains a large amount of-COO-, can show polyanion behavior in aqueous solution, hydrophilic group is combined with water, forms a network structure by virtue of hydrogen bond and Van der Waals force and is adsorbed on the surface of a calcium sulfate crystal nucleus, because of the existence of Ca2+, Na + on a sodium alginate G unit and Ca2+ generate ion exchange reaction, and the G unit is stacked to form a cross-linked network structure; finally, the magnesium sulfate is attached to the cross-linked network structure, and then the calcium sulfate dihydrate plays an inducing role in crystal transformation, so that conditions are provided for subsequent crystal phase transformation of the calcium sulfate whisker.
As a preferred technical scheme of the application, in the step 6), the foaming solution and the gelling slurry are stirred for 10min and uniformly mixed, the whisker stock solution is added, the stirring is continued for 2min and uniformly stirred, and a calcium sulfate crystal nucleus system in the whisker stock solution is dispersed in the foam slurry to provide a growth space for the subsequent growth of the calcium sulfate hemihydrate whiskers.
As a preferred technical scheme of the application, in the step 7), the product is placed into an autoclave together with a mold for autoclave curing, the product is cured at 130 ℃ for 1 hour, after the temperature reaches 130 ℃, the viscosity of calcium alginate is reduced, the intermolecular activation performance is enhanced, under the action of a crystal transformation agent, calcium sulfate dihydrate is gradually converted into calcium sulfate hemihydrate whiskers, the whiskers grow and act on concrete to play roles in reinforcing, toughening and filling to be dense, and the later-stage compressive strength of the concrete is improved. The calcium sulfate whiskers are intertwined with each other and filled in the concrete, when the concrete is frozen and cracks are formed, the phenomenon that the concrete cracks are broken due to continuous expansion of the cracks in a freezing and thawing environment is prevented through stress of the calcium sulfate whiskers, and meanwhile, the silane coupling agent attached to the straw fibers has the same modification effect on the generated calcium sulfate hemihydrate whiskers, so that the calcium sulfate whiskers are inhibited from being hydrated and reduced into calcium sulfate dihydrate whiskers. And then heating to 180 ℃, maintaining for more than 4h, further converting the hydrated calcium silicate component in the cementing material to tobermorite phase, and improving the compression resistance of the concrete again.
Advantageous effects
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the process of the invention directly generates and modifies the crystal whisker in the concrete steaming and pressing process, so that the aperture of the high-strength anti-freezing foam concrete is reduced, the distribution uniformity of air holes is improved, the dispersion problem of calcium sulfate crystal whisker is solved, the property of the crystal whisker is stable, and the whole concrete preparation process is simple.
2. As sodium alginate is added in the preparation process, on one hand, the invention can provide environment for the growth of calcium sulfate whiskers; on the other hand, the micro-morphology of the light foam concrete can be changed, the pore wall structure is more compact, and the compressive strength of the high-strength anti-freezing foam concrete is obviously improved.
3. Because the modified straw fiber is added in the preparation process, on one hand, the pore structure of the concrete can be filled and compacted, so that the structural strength of the concrete is improved; on the other hand, the modified calcium sulfate hemihydrate can be used as a carrier of a silane coupling agent and is uniformly contacted with the calcium sulfate whisker, so that the silane coupling agent is uniformly dispersed on the calcium sulfate whisker in the high-temperature steam pressing process, and the calcium sulfate hemihydrate is directly modified, thereby improving the stability of the whisker.
4. The preparation method has the advantages of environmental protection, high price, simple preparation method and the like, and the prepared foam concrete has high compressive strength and excellent frost resistance, and is worthy of large-scale preparation of high-strength frost-resistant foam concrete.
Detailed Description
Example 1:
1) firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelling slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mould, covering the surface with a preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 2:
the difference from example 1 is that the ratio of the crystal transformation solution is different.
1) Firing the gasification furnace slag, and carrying out ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) 1.8 in mass ratio: 0.3: 2.5 stirring the sodium sulfate, the sodium alginate, the magnesium sulfate and 10 percent of the total amount of water, adjusting the pH of the solution to 9 by using lime, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2 hours, then heating to 165-185 ℃ for curing for 5 hours, and taking the product out of the autoclave to obtain a finished product.
Example 3:
the difference from example 1 is that the ratio of the crystal transformation solution is different.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 3: 1.5: and 4, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 4:
the difference from example 1 is that potassium sulfate is used as the crystal modifier.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the potassium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 5:
the difference from example 1 is that magnesium chloride is used as the crystal modifier.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium chloride and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 6:
the difference from example 1 was that the pH of the crystallization stock solution was adjusted to 8.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 8 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 7:
the difference from example 1 was that the pH of the crystallization stock solution was adjusted to 10.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 10 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 8:
the difference from example 1 is that the reaction temperature of the crystallization stock solution was 20 ℃.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 20 ℃ to obtain a whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 9:
the difference from example 1 is that the reaction temperature of the crystallization stock solution was 60 ℃.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 60 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Example 10:
the difference from example 1 is that the first stage autoclaving temperature is 80 ℃.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃ to obtain a whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 100 ℃ for 2 hours, then heating to 165-185 ℃ for curing for 5 hours, and taking out of the autoclave to obtain a finished product.
Example 11:
the difference from example 1 is that the first stage autoclaving temperature is 150 ℃.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃ to obtain a whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 1:
different from the example 1, 10% of the total amount of sodium alginate and magnesium sulfate and water are added and stirred when preparing the whisker stock solution in the step 4), and sodium sulfate is not added.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 0.6: and 3, stirring 10 percent of the total amount of the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃ to obtain a whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 2:
different from the example 1, the preparation method comprises the steps of 4) stirring 10% of the total amount of the sodium sulfate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using saturated lime water, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution. Sodium alginate was not added.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: and 3, stirring 10 percent of the total amount of the sodium sulfate, the magnesium sulfate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃ to obtain a whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 3:
different from the example 1, the preparation method comprises the steps of 4) stirring 10% of the total amount of the sodium sulfate, the sodium alginate and the water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution. Magnesium sulfate was not added.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6 stirring 10% of the total amount of sodium sulfate, sodium alginate and water, adjusting the pH of the solution to 9 with calcium hydroxide solution, reacting for 30min at 40 deg.C to obtain whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 4:
the difference from the example 1 is that the straw fiber in the step 2) is not modified, and the straw fiber is directly added after being stirred with other cementing materials in the step 5).
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
3) stirring 10% of the total amount of sodium sulfate, sodium alginate, magnesium sulfate and water according to the mass ratio, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃, and preparing the whisker stock solution.
4) And pouring all the rest cementing materials, straw fibers and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, uniformly mixing the materials with the rest water, and stirring for 10min to obtain the cementing slurry.
5) Then stirring the foaming solution and the gelling slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mould, covering the surface with a preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 5:
the difference from the embodiment 1 is that the product is put into an autoclave for autoclave curing in the step 7) together with the mold, the product is not required to be cured for 1 hour at 130 ℃, the temperature is directly increased to 180 ℃ instead, the curing time is 5 hours, and the cured billet is taken out to obtain the finished product.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) stirring 20% of the total amount of sodium sulfate, sodium alginate, magnesium sulfate and water according to the mass ratio, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃, and preparing the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 6:
the difference from the embodiment 1 is that the product is put into an autoclave for autoclave curing in the step 7) together with the mold, the product is firstly cured at 90 ℃ for 1 hour, the temperature is increased to 180 ℃ for 5 hours, and the cured compact is taken out, thus obtaining the finished product.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) stirring 10% of the total amount of sodium sulfate, sodium alginate, magnesium sulfate and water according to the mass ratio, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, reacting for 30min at the reaction temperature of 40 ℃, and preparing the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 7:
the difference from example 1 was that the pH of the crystallization stock solution was adjusted to 7.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 7 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 8:
the difference from example 1 was that the pH of the crystallization stock solution was adjusted to 11.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 11 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 9:
the difference from example 1 is that the foaming manner is chemical foaming. And 3) adding a foam stabilizer into aluminum powder with weight being one thousandth of that of the dry material, adding 25 percent of the total weight of water, mixing and stirring for 30 seconds to obtain a foaming solution.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain a modifier carrier.
3) Taking aluminum powder with one thousandth of dry material weight, adding a foam stabilizer, adding 25% of the total amount of water, mixing and stirring for 30S to obtain a foaming solution;
4) according to the mass ratio of 2: 0.6: and 3, stirring 10 percent of the total amount of the sodium sulfate, the sodium alginate, the magnesium sulfate and the water, adjusting the pH of the solution to 7 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelling slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mould, covering the surface with a preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 10:
the difference from the embodiment 1 lies in that 2.5 parts of calcium sulfate whiskers modified by the silane coupling agent directly in the step 4) are added.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain a modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) adding 2.5 parts of silane coupling agent modified calcium sulfate whisker and other cementing materials, and uniformly mixing.
5) And pouring all the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, uniformly mixing the cementing materials and the water reducing agent with the rest water, and stirring for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
Comparative example 11:
the difference from example 1 is that the ratio of the crystal transformation solution is different.
1) Firing the gasification furnace slag, and performing ball milling and screening to obtain the gasification furnace slag with the loss on ignition less than 8% and the fineness less than 150 meshes;
2) soaking the straw fibers in a silane coupling agent with the mass concentration of 2.0%, stirring for 30min, and then drying for 1h at the temperature of 105 ℃ to obtain the modifier carrier.
3) Mixing and stirring a foaming agent, a foam stabilizer and 25% of the total amount of water for 10min according to the mass ratio at the rotating speed of 330r/min to obtain a foaming solution;
4) according to the mass ratio of 4: 0.7: 5.5 stirring the sodium sulfate, the sodium alginate, the magnesium sulfate and 10 percent of the total amount of water, adjusting the pH of the solution to 9 by using a calcium hydroxide solution, and reacting for 30min at the reaction temperature of 40 ℃ to obtain the whisker stock solution.
5) And pouring all the rest of the cementing materials and the water reducing agent into a stirrer according to the mass ratio at the rotating speed of 140r/min, and uniformly mixing the cementing materials and the water reducing agent with the rest of the water for 10min to obtain the cementing slurry.
6) Then stirring the foaming solution and the gelled slurry for 10min, uniformly mixing, adding the whisker stock solution, continuously stirring for about 2min, uniformly stirring, immediately pouring the mixed slurry into a prepared 100mm by 100mm mold, covering the surface with a layer of preservative film, and standing for foaming for 30 min;
7) and putting the product and the die into an autoclave for autoclave curing, curing at the low temperature of 120-140 ℃ for 2h, then heating to 165-185 ℃ for curing for 5h, and taking the product out of the autoclave to obtain a finished product.
According to JC/T266-:
TABLE 1 compression Strength and Dry Density of examples 1 to 11, comparative examples 1 to 1128 d
Figure BDA0003554884750000151
Figure BDA0003554884750000161
Table 2 Freeze-thawing 50-time performance tests of examples 1 and 6-11 and comparative examples 1-11
Figure BDA0003554884750000162
As can be seen from tables 1 and 2, the concrete prepared in examples 1 to 11 has higher compressive strength, and examples 1 and 6 to 11 have less strength loss and higher splitting tensile strength after freeze-thaw testing. The calcium sulfate whiskers generated in one step can be tangled and filled in concrete, and in the process that the concrete is frozen and cracks are formed, the phenomenon that the concrete cracks are expanded continuously under a freeze-thaw environment to cause the concrete to crack is prevented through stress of the tangled fibers, so that the freeze-thaw resistance of the freeze-thaw resistant concrete can be improved. Examples 1-3 and comparative example 11 show that when the addition amount of the whisker stock solution is gradually increased, the strength of the concrete is increased and then decreased, because when too many calcium sulfate whiskers are generated, the volume expansion and surface cracking are generated in the interior of the concrete, and the strength of the concrete is reduced, so that the compressive strength of the concrete can be improved by adding the whisker stock solution with a proper proportion, and examples 1, 4 and 5 prove that the same effect can be achieved by adding different crystal transformation agents; examples 1, 6 and 7 and comparative examples 7 and 8 show that the use effect of the crystal transition stock solution is best when the pH value is 8-10; examples 1, 8 and 9 show that the preparation temperature of the stock solution for crystal transformation is better than 20 ℃ at 40 ℃, but the effect is not much different from 40 ℃ when the temperature reaches 60 ℃, and 40 ℃ is preferred for saving energy consumption. Examples 10 and 11 and comparative examples 5 and 6 prove that the optimum temperature for generating the whiskers is 115-150 ℃, the whisker conversion rate is low below the temperature, the growth of the whiskers is influenced by generating part of tobermorite above the temperature, and the growth of the whiskers is influenced by over-high or over-low temperature, so that the compression resistance and the frost resistance of the concrete are low.
Comparative example 1, without the addition of sodium sulfate, produced an article with significantly lower strength and less freeze resistance due to the absence of the whisker growth-providing requirements. The comparative example 2 does not add sodium alginate, and the concrete strength is lower, because the sodium alginate and the generated calcium sulfate whisker can form a cross-linked network structure, and the calcium sulfate whisker can grow to provide an environment; on the other hand, the micro appearance of the light foam concrete can be changed, the hole wall structure is more compact, and the compressive strength of the high-strength anti-freezing foam concrete can be improved. Comparative example 3 no crystal transfer agent is added, an interface inducer is lacked when the crystal whisker grows, the length-diameter ratio of the generated crystal whisker is poor, and the function of improving the performance of concrete cannot be achieved; comparative example 4 is prepared without adding a modifier carrier, and the strength of the modified straw fiber is not greatly influenced compared with that of example 1 in 28d, but after 50 times of freeze-thaw cycles, calcium sulfate whiskers generated in concrete are hydrated to become calcium sulfate dihydrate, so that the strength of the concrete is reduced, and the anti-cleavage tensile strength is reduced. Comparative examples 5 and 6 show that the temperature has a large influence on the growth of the whiskers, and the conversion rate of converting calcium sulfate dihydrate into calcium sulfate hemihydrate is high at 100-150 ℃. Comparative example 5 using one-step autoclaving, calcium sulfate whiskers produced were hammer-shaped and less strongly bonded to tobermorite than columnar whiskers. Comparative examples 7 and 8 show that pH has a great influence on the appearance of calcium sulfate dihydrate, and columnar calcium sulfate dihydrate crystal nuclei can be generated only in a specific acid-base environment. Comparative example 9 adopts chemical foaming, the slurry is thick at the initial stage, no growth space is provided for the growth of the whisker, and the growth of the whisker is hindered, so that the performance of the concrete cannot be improved; comparative example 10 incorporates modified calcium sulfate hemihydrate whiskers directly with a slight increase in strength, but the strength is still lower than the examples because whiskers are added directly, which are only physically dispersed in the cementitious system, whereas whiskers are formed directly in the examples, which grow to make them more tightly bound to the cementitious material and can make the foamed concrete structure denser. Comparative example eleven illustrates that there is an optimum value for the amount of whisker stock added, not more and better.
In conclusion, the preparation method of the high-strength anti-freezing foam concrete capable of generating the whiskers in situ provided by the invention has the advantages that the whiskers are directly generated and modified in the preparation process of the high-strength anti-freezing foam concrete, the problem of poor dispersibility of the calcium sulfate whiskers is solved, the whiskers are stable in property and economical, the preparation method is simple, the prepared concrete is high in early strength and high in later compressive strength, and meanwhile, cracking and cracks are not easy to occur, and the prepared concrete has excellent compressive performance and durability. Is worthy of large-scale preparation.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be protected by the following claims.

Claims (7)

1. The preparation method of the high-strength anti-freezing foam concrete with in-situ generated whiskers is characterized by comprising the following raw materials in parts by weight:
220-300 parts of cement, 800-920 parts of gasified slag, 260-354 parts of lime, 435-670 parts of water, 1-3.5 parts of a water reducing agent, 18-22 parts of sodium sulfate, 1.5-3 parts of a crystal modifier, 0.2-0.8 part of a modifier carrier, 0.1-1 part of sodium alginate, 0.4-0.6 part of a foam stabilizer and 3-5 parts of a foaming agent.
2. The method for preparing high-strength anti-freezing foam concrete with in-situ generated whiskers, according to claim 1, is characterized in that: the preparation method comprises the following steps:
1) raw material treatment: calcining the gasification furnace slag, and performing ball milling and sieving;
2) preparing a modifier carrier: soaking the straw fibers in a silane coupling agent, stirring, and drying at the temperature of 100-150 ℃ for 1-2 h to obtain the modifier carrier.
3) Preparing a foaming solution: mixing and stirring a foaming agent, a foam stabilizer and 25-30% of the total amount of water for 10-15 min at a rotating speed of 300-350 r/min to obtain a foaming solution; the foaming agent adopts sodium dodecyl benzene sulfonate and/or sodium alpha-olefin sulfonate, and the foam stabilizer adopts calcium stearate and/or hydroxypropyl methyl cellulose.
4) Preparing a whisker stock solution: stirring sodium sulfate, sodium alginate, a crystal transformation agent and water accounting for 10 percent of the total amount of the water, adjusting the pH of the solution to 7-11 by using a calcium hydroxide solution, continuously stirring for 30-60 min at the reaction temperature of 20-60 ℃ to prepare a whisker stock solution.
5) Preparing a gelling stock solution: and mixing and stirring all the rest of the cementing materials, the water reducing agent, the modifier carrier and the rest of the water for 5-10 min at the rotating speed of 130-150 r/min to obtain the cementing slurry.
6) And (3) foaming process: stirring the whisker stock solution obtained in the step 4) and the gelling slurry obtained in the step 5) for 5-10 min, uniformly mixing, adding a foaming solution, continuously stirring for about 1-2 min, uniformly stirring, immediately pouring the mixed slurry into a prepared mould, covering the surface with a layer of preservative film, and standing for foaming.
7) Steam pressure curing: and (3) putting the product obtained in the step 6) into an autoclave for autoclave curing, curing at low temperature, then heating for curing, and taking out the cured compact to obtain a finished product.
3. The method for preparing high strength anti-freezing foam concrete with in-situ generated whiskers according to claims 1 and 2, characterized in that: the gasified slag is waste slag generated by a coal gasification process; the gasified slag needs to be calcined at 500-800 ℃ to reduce the ignition loss to below 8%; ball milling and sieving to obtain particle size over 150 mesh.
4. The method for preparing high strength anti-freezing foam concrete with in-situ generated whiskers according to claims 1 and 2, characterized in that: the mass concentration of the silane coupling agent is 1.0-3.0%, and the stirring time is 30-60 min; the drying temperature is 100-150 ℃;
preferably, the mass concentration of the silane coupling agent is 2.0-2.2%
Preferably, the stirring time is 30-35 min;
preferably, the drying temperature is 100-110 ℃.
5. The method for preparing high-strength anti-freezing foam concrete with in-situ generated whiskers, according to claims 1 and 2, is characterized in that the crystal transformation agent is one or a combination of magnesium sulfate, magnesium chloride and potassium sulfate.
6. The method for preparing the high-strength anti-freezing foam concrete with the in-situ generated whiskers, according to claims 1 and 2, is characterized in that a calcium hydroxide solution is used for adjusting the pH value to 7-11 in the preparation process of the whisker stock solution; the reaction temperature is 20-60 ℃;
preferably, the pH is adjusted to 8-10;
preferably, the reaction temperature is 30-40 ℃.
7. The preparation method of the high-strength anti-freezing foam concrete with the in-situ generated whiskers is characterized in that the steam-pressing process is two-stage temperature control, the steam-pressing process comprises low-temperature curing, curing at the curing temperature of 100-150 ℃ for 1-5 h, heating and curing, the temperature is controlled to be 160-200 ℃, and curing time is 4-10 h.
Preferably, the low-temperature curing temperature is 120-140 ℃;
preferably, the low-temperature curing time is 1-3 h;
preferably, the temperature rise and maintenance temperature is 165-185 DEG C
Preferably, the temperature rise curing time is 6-8 h.
CN202210273511.5A 2022-03-19 2022-03-19 Preparation method of high-strength anti-freezing foam concrete with in-situ generated whiskers Pending CN114538840A (en)

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