阅读说明：本技术 全废弃物制备的地聚合物基人工备防石及其制备方法 (Geopolymer-based artificial prepared stone prepared from full wastes and preparation method thereof ) 是由 李克亮 杜晓蒙 陈爱玖 卢鹏 汪志昊 廖亦聪 付海强 谢晓洁 位文哲 王聪豪 于 2019-09-29 设计创作，主要内容包括：本发明公开了一种全废弃物制备的地聚合物基人工备防石及其制备方法,包括以下重量份数的原材料：废硅铝质材料288～412份；含碱废弃物85～150份；废硫酸盐矿物29～75份；再生骨料1501～1860份；中水216～241份；废旧纤维0～2份；农作物废弃物0～5份。该发明工艺简单,制备得到的人工备防石无外观缺陷,具有体积密度大,强度高(34MPa以上),抗风化、抗冻和抗冲磨性能好等优点,且在使用过程中,抛投方便,整体性好,稳定性强,抗冻融,耐风化,耐高速含砂水流冲磨,在高速水流下不易走失,是天然石材备防石的理想替代产品。(The invention discloses a geopolymer-based artificial prepared stone prepared from full wastes and a preparation method thereof, wherein the stone comprises the following raw materials in parts by weight: 288-412 parts of waste silicon aluminum material; 85-150 parts of alkali-containing waste; 29-75 parts of waste sulfate minerals; 1501-1860 parts of recycled aggregate; 216-241 parts of reclaimed water; 0-2 parts of waste fibers; 0-5 parts of crop wastes. The artificial backup stone has the advantages of being large in volume density, high in strength (more than 34 MPa), good in weather resistance, frost resistance and abrasion resistance and the like, convenient to throw, good in integrity, strong in stability, resistant to freezing and thawing, weather resistance and high-speed sand-containing water flow abrasion resistance in the using process, not prone to loss under high-speed water flow, and is an ideal substitute product for natural stone backup stones.)

1. The geopolymer-based artificial stone-proof material prepared from full wastes is characterized by comprising the following raw materials in parts by weight: 288-412 parts of waste silicon aluminum material; 85-150 parts of alkali-containing waste; 29-75 parts of waste sulfate minerals; 1501-1860 parts of recycled aggregate; 216-241 parts of reclaimed water; 0-2 parts of waste fibers; 0-5 parts of crop wastes.

2. The all-waste-prepared geopolymer-based artificial stone of claim 1, wherein the waste alumino-silica material is composed of the following raw materials in percentage by weight: 20-90% of granulated blast furnace slag powder, 0-40% of fly ash, 0-50% of waste concrete powder, 0-50% of waste red brick powder, 0-10% of silica fume, 0-10% of calcined gangue powder, 0-20% of tailing powder and 0-10% of crop waste ash.

3. The all-waste-prepared geopolymer-based artificial stone-proof device as claimed in claim 1, wherein the alkali-containing waste is composed of the following raw materials in percentage by weight: 50-100% of steel slag powder, 0-20% of red mud, 0-15% of alkaline residue and 0-15% of carbide slag.

4. The all-waste-prepared geopolymer-based artificial stone according to claim 1, wherein the waste sulfate mineral is composed of the following raw materials in percentage by weight: 20-100% of desulfurized gypsum, 0-50% of phosphogypsum and 0-30% of fluorgypsum.

5. The all-waste-prepared geopolymer-based artificial stone of claim 1, wherein the recycled aggregate is composed of the following raw materials in percentage by weight: 30-45% of regenerated fine aggregate and 70-55% of regenerated coarse aggregate.

6. The all-waste-prepared geopolymer-based artificial stone according to claim 1, wherein the waste fibers are waste spun yarns or/and woven fabrics.

7. The total waste produced geopolymer-based artificial stone-proofing system according to claim 1, wherein the crop waste is at least one of corn, sorghum, wheat, rice, and cotton stalks.

8. The method for preparing geopolymer-based artificial stone-proof according to claim 1, characterized by comprising the following steps:

(1) weighing the raw materials according to the parts by weight of claim 1, and uniformly mixing the recycled coarse aggregate and the raw materials except the reclaimed water;

(2) adding reclaimed water into the mixture obtained in the step (1) and uniformly mixing;

(3) adding the recycled coarse aggregate into the mixture obtained in the step (2) and uniformly mixing;

(4) preparing artificial prepared waterproof stones from the mixture obtained in the step (3) according to a concrete layered charging layered vibration forming method and the required size;

(5) and (4) coating a plastic film on the surface of the artificial stone-proof prepared in the step (4), and maintaining after removing the mold.

9. The method for preparing the geopolymer-based artificial stone matrix according to claim 8, wherein in the step (5), the condition which is met when the template is removed is that when the ambient temperature is more than or equal to 5 ℃, the compressive strength of the prepared artificial stone matrix reaches at least 3MPa, and the template is removed; when the environmental temperature is lower than 5 ℃, the compression strength of the prepared artificial prepared waterproof stone is at least 5MPa, and the template is removed.

10. The method for preparing geopolymer-based artificial stone-proofing agent according to claim 8, wherein in the step (5), the curing time is at least 28 days when the ambient temperature is more than or equal to 20 ℃, at least 42 days when the ambient temperature is more than or equal to 5 ℃ and less than 20 ℃, and at least 56 days when the ambient temperature is less than 5 ℃.

Technical Field

The invention belongs to the field of hydraulic materials, and particularly relates to a geopolymer-based artificial prepared stone prepared from full wastes and a preparation method thereof.

Background

A certain amount of reserve stones are often required to be reserved at a river dike engineering rescue workshop section, a control and guidance engineering position and nearby areas so as to meet emergency needs of flood prevention and emergency rescue. The traditional backup stone is obtained by exploiting natural stone, and the source causes permanent damage to the natural mountain, worsens the natural environment and is not sustainable. The demand of flood-prevention stones is high, the stones are non-renewable resources, the policies of mountain sealing and forest cultivation are adopted in various places, and the price of the transported oil rises, so that the price of the stones has a continuous rising trend in recent years, and the shortage of natural stones becomes an important problem to be solved urgently in the river flood-prevention emergency work.

The existing stone-proof technology prepared by people still has some defects, such as: the alkali excitation technology has the problems of low compressive strength of the prepared waterproof stone, serious saltpetering and the like; the high-temperature sintering method has the problems of high sintering temperature, high energy consumption, complex process and the like; the concrete core-wrapping technology has complex preparation process, and needs to use materials with higher cost, such as steel bars, steel wire meshes or plastic steel geogrids, and the like, and the steel slag aggregate has stability problem, and the used cement has poor environmental compatibility.

Therefore, the geopolymer-based artificial stone-proof material prepared by the full wastes has high strength, strong frost inhibition capability, large volume density, strong frost resistance, abrasion resistance and weather resistance, low manufacturing energy consumption, simple and convenient process, low cost and good environmental harmony, and is necessary for preparing the stone-proof material.

Disclosure of Invention

The invention provides a geopolymer-based artificial prepared stone prepared from full wastes, which aims to solve the problems of replacement of natural stone prepared stone and the problems of low strength, serious saltpetering, small bulk density, freezing resistance, impact and weathering resistances, high energy consumption during manufacturing, complex process, high cost and the like in the prior art.

In order to solve the technical problems, the invention adopts the following technical scheme:

designing a geopolymer-based artificial preparation stone prepared from full wastes, which comprises the following raw materials in parts by weight:

288-412 parts of waste silicon aluminum material; 85-150 parts of alkali-containing waste; 29-75 parts of waste sulfate minerals; 1501-1860 parts of recycled aggregate; 216-241 parts of reclaimed water; 0-2 parts of waste fibers; 0-5 parts of crop wastes.

Preferably, the waste silicon-aluminum material is composed of the following raw materials in percentage by weight: 20-90% of granulated blast furnace slag powder, 0-40% of fly ash, 0-50% of waste concrete powder, 0-50% of waste red brick powder, 0-10% of silica fume, 0-10% of calcined gangue powder, 0-20% of tailing powder and 0-10% of crop waste ash.

Preferably, the alkali-containing waste consists of the following raw materials in percentage by weight: 50-100% of steel slag powder, 0-20% of red mud, 0-15% of alkaline residue and 0-15% of carbide slag.

Preferably, the waste sulfate mineral is composed of the following raw materials in percentage by weight: 20-100% of desulfurized gypsum, 0-50% of phosphogypsum and 0-30% of fluorgypsum.

Preferably, the recycled aggregate is prepared from the following raw materials in percentage by weight: 30-45% of regenerated fine aggregate and 70-55% of regenerated coarse aggregate.

Preferably, the waste fibers are waste spun yarns or/and woven fabrics.

Preferably, the crop waste is at least one of corn, sorghum, wheat, rice and cotton straws.

The preparation method of the geopolymer-based artificial stone-proof material comprises the following steps:

(1) weighing the raw materials in parts by weight, and uniformly mixing the recycled coarse aggregate and the raw materials except the reclaimed water;

(2) adding reclaimed water into the mixture obtained in the step (1) and uniformly mixing;

(3) adding the recycled coarse aggregate into the mixture obtained in the step (2) and uniformly mixing;

(4) preparing artificial prepared waterproof stones from the mixture obtained in the step (3) according to a concrete layered charging layered vibration forming method and the required size;

(5) and (4) coating a plastic film on the surface of the artificial stone-proof prepared in the step (4), and maintaining after removing the mold.

Preferably, the conditions met during the form removal in the step (5) are that when the ambient temperature is more than or equal to 5 ℃, the compression strength of the prepared artificial prepared waterproof stone reaches at least 3MPa, and the template is removed; when the environmental temperature is lower than 5 ℃, the compression strength of the prepared artificial prepared waterproof stone is at least 5MPa, and the template is removed.

Preferably, the curing time in the step (5) is at least 28 days when the ambient temperature is more than or equal to 20 ℃, at least 42 days when the ambient temperature is more than or equal to 5 ℃ and less than 20 ℃, and at least 56 days when the ambient temperature is less than 5 ℃.

Compared with the prior art, the invention has the main beneficial technical effects that:

1. the raw material components of the invention act synergistically, the prepared artificial preparation has high stone-proof volume density, high strength, impact resistance, abrasion resistance, frost resistance and weather resistance, and can inhibit the phenomenon of blooming, and the main cooperation mechanism among the raw materials is as follows:

the mechanism of the activity excitation composite additive effect is as follows: (1) the alkali-containing waste has high pH value and can provide a high alkali environment, and OH-can break Si-O bonds and Al-O bonds of vitreous bodies in the superfine powder under the high alkali environment, so that the vitreous body structure is depolymerized and further condensed into low alkali metal aluminosilicate gel and C-S-H gel with C/S ratio, and the C-S-H gel is accompanied by C₄AH₁₃CrystalWaiting for the generation of hydration products; (2) under the action of OH < - >, the reaction grade number of the waste silicon-aluminum material is lower, the reaction degree is lower, and the process is slower; the waste sulfate mineral contains sulfate, and the excitation of the sulfate and OH-is mutually promoted in the presence of the sulfate and OH-, so that a composite superposition effect is generated, the reaction number is greatly increased and is 2-5 times of that of the sulfate or OH-under the condition of independent excitation, the reaction process is accelerated, and the waste silicon-aluminum material is better excited; (3) more hydration products are obtained, a plurality of hydration products of colloid and crystal are mutually overlapped, the crystals are mutually overlapped, the colloid fills gaps among the crystals, and the hydration products fill most of the gaps, so that the microstructure is more compact, and higher strength, frost resistance, impact resistance and weather resistance are obtained.

The waste silicon aluminum material has the following composition enhancement principle: the main active ingredient in the waste silicon aluminum material is vitreous body, and the main factors influencing the activity of the vitreous body are two: one of them is a vitreous body structure, the more Si content of the network former, the lower the amount of oligo [ SiO ]₄]^4-The less anions, the less vitreous active; in addition, the more the content of ionic bonds (related to the content of K, Na, Ca, Mg) in the glass, the higher the activity of the glass. The invention adopts the compounding of various wastes such as high-granulation blast furnace slag powder, fly ash, waste concrete powder, waste red brick powder, silica fume, calcined coal gangue powder, tailing powder, crop waste ash and the like, and optimizes the content of network formers and the content of ionic bonds in the system, thereby improving the reaction degree of waste silica-alumina materials under the action of activators such as alkali-containing wastes and waste sulfate minerals and the like, and obtaining better performance.

The mechanism of bloom inhibition is: alkali-activated cementitious materials use a large amount of alkali and salt as the activator, and if measures are not taken to fully react and inhibit the alkali and salt, part of the alkali and salt easily migrates to the surface, crystallizes on the surface, and the blooming phenomenon occurs. In the invention, the blooming is well inhibited due to the following action mechanism: (1) when the artificial stone-proof board is prepared, the artificial stone-proof board is wrapped by the plastic film, so that the humidity gradient inside and on the surface is reduced,the evaporation of water is avoided, so that the migration of the alkali and salt inside along with water to the surface is avoided, and the plastic film wrapping and maintaining period is prolonged to 28 days to ensure that more alkali and salt participate in chemical reaction; (2) in the invention, the activity-excited composite superposition effect and the composite enhancement effect of each component of the waste silicon-aluminum material are fully exerted, and particularly, the silica fume, the calcined coal gangue powder and the waste ash of crops with extremely high reaction activity are introduced, so that the reaction of alkali, salt and the waste silicon-aluminum material is fully carried out, the early reaction degree and the final reaction degree are improved, and Na is enabled to be obtained⁺、K⁺、Ca²⁺The isocations are more fixed into the alkali metal aluminosilicate colloid and the C-S-H gel in an ionic bond form, so that the excessive alkali and salt in the system are reduced; (3) the activity-excited composite superposition effect and the composite enhancement effect of each component of the waste silicon-aluminum material can generate more hydration products such as colloid, crystal and the like, and the hydration products are filled in the pores, so that the porosity is greatly reduced, the structure is more compact, the channel for alkali and salt to migrate from the inside to the surface is blocked, the migration becomes extremely difficult, and the migration amount is less; (4) the hydration product of the geopolymer contains C-S-H gel with low C/S ratio and alkali metal aluminosilicate gel, and the gels have stronger adsorption capacity, can solidify a large amount of alkali and reduce the precipitation of the alkali.

The principle of improving the weathering resistance is as follows: the artificial prepared stone is influenced by the superposition of various adverse effects of wind and rain, temperature change, dry-wet cycle, freeze-thaw cycle and the like in the nature during the storage or use process of the river bank, and must have excellent weather resistance. According to the invention, the weathering resistance of the prepared artificial stone is greatly improved due to the following action mechanism: (1) the activity excitation composite superposition effect and the composite enhancement effect of each component of the waste silicon-aluminum material generate more hydration products such as colloid, crystal and the like, and the hydration products are filled in the pores, so that the porosity, particularly the open porosity, is low, the water permeation channel is reduced, and the damage caused by weathering is reduced; (2) the active excitation composite superposition effect and the composite enhancement effect of each component of the waste silicon-aluminum material ensure that the artificial stone resistance is strongThe degree is high, and the weathering resistance is improved; (3) in the present invention, the hydration product is not easily soluble in water, and the solubility of the C-S-H gel with low C/S ratio is 6.8X 10^-5mol/L, ettringite solubility of 3.3X 10^-6mol/L, alkali metal aluminosilicate gel 3.1X 10^-5The hydration product with low solubility has good erosion resistance; (4) the waste fibers and the straw fibers are used as reinforcing materials, the fibers are distributed in a random direction in the artificial stone-proof matrix, when the matrix is subjected to compression or tensile damage, firstly, the tensile deformation and the stress of the fibers are absorbed, and the matrix begins to be damaged after the fibers are broken, so that the crack resistance of the artificial stone-proof matrix can be improved, the toughness is improved, and the physical damage to the matrix caused by temperature change, dry-wet cycle and freeze-thaw cycle is greatly reduced.

The mechanism for improving the abrasion resistance is as follows: the sand content in the river water of the yellow river is high, the damage of the high-speed sand-containing water flow to the stone preparation prevention is the effects of impact, friction and cutting, and the anti-abrasion performance of the stone preparation prevention is greatly improved by the following mechanism: (1) the waste fibers and the straw fibers improve the brittleness of the stone-proof matrix, the impact resistance and the high-speed sand inclusion water flow impact resistance are obviously improved, and the fibers and cement can bear the impact grinding load together, so that the damage process of the matrix can be delayed; the fibers enable the interior of the matrix to be mutually overlapped, drawn and integrated, so that the development of cracks caused by impact or abrasion is hindered, the fibers also prevent the matrix from being stripped from the fibers, and the fibers are stripped from the matrix and consume energy, so that the abrasion resistance of concrete is improved; (2) the waste fibers and the straw fibers can effectively prevent the generation of micro cracks in the structure, relieve the stress concentration degree of the tips of the cracks, reduce the scale of the micro cracks, enhance the continuity in the material, reduce the local stress concentration degree caused by the blocking of shock waves and obviously improve the shock resistance of the stone; (3) the composite additive effect of the activity excitation and the composite reinforcing effect of each component of the waste silicon-aluminum material (especially the silicon ash with higher activity, the calcined gangue powder and the waste ash of crops) enable the matrix to have high strength, large hardness and improved elastic modulus, and then the composite effect of the matrix and the waste fibers and the straw fibers greatly improves the resistance to impact and abrasion.

2. The geopolymer-based artificial prepared waterproof stone is prepared by adopting full wastes, the utilization rate of the wastes can reach 100 percent, the concepts of circular economy and environmental protection are realized, the environmental harmony is good, the raw materials are easy to obtain, and the energy is saved and the environment is protected; the invention has simple preparation process and excellent product performance, and is an ideal substitute product for preparing natural stone for preventing stone.

Detailed Description

The invention is further illustrated below with reference to specific examples.