CN114213095A - Alkali-activated phosphogypsum self-leveling mortar - Google Patents
Alkali-activated phosphogypsum self-leveling mortar Download PDFInfo
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- CN114213095A CN114213095A CN202111674569.2A CN202111674569A CN114213095A CN 114213095 A CN114213095 A CN 114213095A CN 202111674569 A CN202111674569 A CN 202111674569A CN 114213095 A CN114213095 A CN 114213095A
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- phosphogypsum
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- leveling mortar
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
- C04B2103/465—Water-sorbing agents, hygroscopic or hydrophilic 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
- C04B2111/60—Flooring materials
- C04B2111/62—Self-levelling compositions
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to alkali-activated phosphogypsum self-leveling mortar, which comprises 55-70 parts of phosphogypsum, 10-20 parts of slag, 1-3 parts of alkali activator, 30-50 parts of fine aggregate, 0.02-0.1 part of retarder, 0.05-0.12 part of defoaming agent, 0.02-0.06 part of water-retaining agent and 0.1-0.3 part of water-reducing agent. The invention uses the industrial waste phosphogypsum and mineral powder as main raw materials, changes waste into valuable, has low cost and high economic benefit, has more market competitiveness compared with similar products, reduces environmental pollution, and is beneficial to the phosphogypsumA new way is opened up; calcium hydroxide is used as an alkali activator, can be used for jointly activating the alkali-activated cementing material in the phosphogypsum self-leveling mortar with sulfate in the phosphogypsum, regulating and controlling the fluidity and the setting time of the prepared phosphogypsum self-leveling mortar, solving the problem of poor mechanical property and water resistance of the phosphogypsum self-leveling mortar, and in addition, the calcium hydroxide can preferentially adsorb an inert salt Ca generated by precipitation of eutectic phosphorus in the phosphogypsum3(PO4)2And the adverse effect of the self-leveling mortar on the phosphogypsum is avoided.
Description
Technical Field
The invention relates to the technical field of inorganic building materials, in particular to alkali-activated phosphogypsum self-leveling mortar.
Background
The self-leveling mortar is a novel ground leveling material, can automatically level with the help of the characteristics of fluid flow, is quickly dried, greatly saves materials and labor compared with a manual ground leveling process, and shortens the construction period. In the era of increasing manpower cost, the self-leveling mortar is more competitive in terms of economy. The cement-based self-leveling mortar is applied to a large number of construction projects at present, but the later-stage cracking of the cement-based self-leveling mortar is serious, and then the problems of hollowing, cracking and the like are caused. Compared with cement-based self-leveling mortar, the gypsum-based self-leveling mortar has the great advantages of early strength, quick hardening, light weight, high strength, simplicity and high efficiency in construction, no need of watering maintenance, accurate leveling, stable volume, difficulty in cracking and hollowing, unlimited construction thickness, good ground impression and the like. In addition to this, cement is an energy source and CO2The main source of emission is that the gypsum building material has obvious environmental protection advantage compared with cement, and becomes a green environmental protection building material which is recognized in the world and widely used in developed countries. However, natural gypsum mineral product is a non-renewable resource, and is consumed in large quantities with the development of large-scale industrialization, and chemical gypsum is gradually replacing natural gypsum and is widely applied to gypsum building materials. However, in recent years, the maturity of the application technology and the expansion of the application field of the desulfurized gypsum have caused the resource shortage thereof.
Phosphogypsum is the most abundant industrial by-product gypsum in the world at present, and a phosphoric acid plant discharges about 5 tons of phosphogypsum per 1 ton of phosphoric acid produced. It is estimated that the current annual emission of phosphogypsum is about 1.5 million tons and may exceed 2 million tons in the coming years. But the comprehensive utilization rate of the phosphogypsum is still lower, and most national regions still adopt stockpiling treatment. The method not only wastes land resources, but also causes air pollution and seriously damages ecological environment because the soluble phosphorus and fluorine in the phosphogypsum flow into underground water along with rainwater and acidic substances and dust volatilized by the accumulated phosphogypsum also cause air pollution. However, the impurities in the phosphogypsum can obviously prolong the setting time of the gypsum, reduce the mechanical strength of the gypsum, seriously restrict the recycling of the phosphogypsum and generally need to be pretreated. The phosphogypsum pretreatment method can be divided into a chemical treatment method, a physical treatment method and a heat treatment method, but the chemical treatment method and the physical treatment method cannot remove eutectic phosphorus in the phosphogypsum, and the energy consumption and the cost of the heat treatment are high, so that the cost of the phosphogypsum as a building material is increased undoubtedly.
Compared with desulfurized gypsum, the phosphogypsum has complex components and unstable performance, and the gypsum prepared by taking the phosphogypsum as a cementing material has low self-leveling strength and poor water resistance, thereby limiting the great application of the phosphogypsum in the field.
The alkali-activated cementing material, also called alkali-activated cement, is prepared by using industrial waste residue which is activated by an alkali activator and has potential activity, the energy consumption for preparing the alkali-activated cementing material is low, a large amount of industrial waste residue can be consumed, the research and the application of the alkali-activated cementing material are developed rapidly, and the hydration product of the alkali-activated cementing material is [ AlO ]4]5-And [ SiO ]4]4-The three-dimensional network type product formed by polymerizing the tetrahedral structural unit has the advantages of compact structure, high strength, good durability and the like. Part of alkali-activated cementing materials are doped into the phosphogypsum self-leveling mortar, the alkali-activated cementing materials generate hydration products with higher strength and better water resistance under the combined action of sulfate in the phosphogypsum and an alkali activator, the problems of low strength and poor water resistance of the phosphogypsum self-leveling mortar are solved, besides, the resource recycling of solid waste slag is realized, the production cost of the gypsum self-leveling mortar is reduced, and the market competitiveness is further improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the defects in the prior art, the alkali-activated phosphogypsum self-leveling mortar is provided.
The technical scheme adopted by the invention is as follows: the alkali-activated phosphogypsum self-leveling mortar comprises the following raw materials in parts by weight:
furthermore, the slag adopts S95-grade slag, granulated blast furnace slag powder, the alkalinity coefficient is more than 1, and the mass coefficient is more than 1.2. The slag with high alkalinity coefficient and high quality coefficient is selected, so that the structure of the sample is more compact, and the compressive strength of the sample is higher.
Further, the alkali activator adopts calcium hydroxide. Calcium hydroxide as an alkaline activator can excite the activity of slag powder to generate hydrated calcium silicate, ettringite and other hydrated products which are insoluble in water and have higher strength, and the hydrated products grow among calcium sulfate dihydrate crystals of phosphogypsum hydrated products in a staggered manner, so that the self-leveling microstructure of gypsum is improved, the microstructure is more compact, and the water resistance and the mechanical property of the phosphogypsum self-leveling mortar are improved; when the phosphogypsum is hydrated, eutectic phosphorus is separated out, and Ca is generated in an alkaline environment3(PO4)2Precipitation, deposition on the surface of phosphogypsum particles and dihydrate gypsum crystals, hindering hemihydrate dissolution and dihydrate gypsum nucleation and growth, but calcium hydroxide due to the presence of large amounts of Ca all around2+Will preferentially adsorb Ca3(PO4)2Thereby reducing Ca3(PO4)2The influence on the crystal face of the dihydrate gypsum improves the microstructure and the strength.
Furthermore, the retarder is protein retarder, the protein retarder is easy to regulate and control the setting time of the gypsum self-leveling mortar, and compared with organic acid retarder and inorganic salt retarder, the protein retarder has less strength loss on the alkali-activated phosphogypsum self-leveling mortar.
Furthermore, the protein gypsum retarder is formed by polymerizing one or more of modified amino acid, modified polypeptide, natural protein hydrolysate and the like.
Further, the defoaming agent is one or more of a polyether defoaming agent, a modified polyether defoaming agent, an organic silicon defoaming agent and a polyether modified polysiloxane defoaming agent.
Further, the water-retaining agent adopts cellulose ether with the viscosity of less than 1000 mPa.s.
Further, the water reducing agent is a polycarboxylic acid water reducing agent. By using the polycarboxylic acid water reducing agent with proper mixing amount, the phosphogypsum self-leveling mortar can achieve good dispersion effect, has good fluidity and can reduce the fluidity loss of the phosphogypsum self-leveling mortar.
Furthermore, the acid-ether ratio of the polycarboxylate superplasticizer is not less than 4, and the water reducer with a proper acid-ether ratio is selected, so that the fluidity of the alkali-activated phosphogypsum self-leveling mortar can be improved, the setting time can be prolonged, and the polycarboxylate superplasticizer can be used together with a retarder to regulate and control the setting time of the alkali-activated phosphogypsum self-leveling mortar.
Compared with the phosphogypsum self-leveling mortar, the alkali-activated phosphogypsum self-leveling mortar has the advantages that the setting time is reduced to some extent compared with the phosphogypsum self-leveling mortar, the initial setting time is about 2 hours, and the final setting time is about 2.5 hours. The ardealite self-leveling mortar has poor strength and water resistance and is difficult to meet the standard requirements, but the alkali-activated ardealite self-leveling mortar has high strength and can meet the standard of gypsum self-leveling mortar. The alkali-activated phosphogypsum self-leveling mortar has better water resistance and higher softening coefficient than the phosphogypsum self-leveling mortar.
Compared with the prior art, the invention has the following advantages:
1. the invention uses the phosphogypsum and the slag powder of industrial wastes as main raw materials, changes waste into valuable, has low cost and high economic benefit, has more market competitiveness compared with similar products, reduces environmental pollution and opens up a new way for the utilization of the phosphogypsum;
2. under the action of sulfate in phosphogypsum and a calcium hydroxide alkali activator, an alkali-activated cementing material generates hydrated products such as calcium silicate hydrate and ettringite which are difficult to dissolve in water and have higher strength, the hydrated products grow among calcium sulfate dihydrate crystals of the phosphogypsum hydrated product in a staggered manner, the microstructure of gypsum self-leveling is improved, the fluidity and the setting time of the prepared phosphogypsum self-leveling mortar can be regulated and controlled by adding the alkali-activated cementing material into the phosphogypsum, and the problem of poor mechanical property and water resistance of the phosphogypsum self-leveling mortar can be solved;
3. the calcium hydroxide used as the alkaline activator can not only excite the activity of slag powder, but also can precipitate eutectic phosphorus in the phosphorus building gypsum to form Ca3(PO4)2During precipitation, Ca is preferentially adsorbed3(PO4)2Precipitate and reduce Ca3(PO4)2The influence on the crystal face of the dihydrate gypsum improves the microstructure and the strength.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the embodiments of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Uniformly mixing 55 parts by weight of phosphogypsum, 10 parts by weight of slag, 1.4 parts by weight of calcium hydroxide, 30 parts by weight of fine aggregate, 0.02 part by weight of protein retarder, 0.05 part by weight of organic silicon defoamer, 0.02 part by weight of cellulose ether and 0.1 part by weight of polycarboxylic acid water reducer to prepare the alkali-activated phosphogypsum self-leveling mortar.
Example 2
Uniformly mixing 60 parts by weight of phosphogypsum, 20 parts by weight of slag, 1.4 parts by weight of calcium hydroxide, 30 parts by weight of fine aggregate, 0.02 part by weight of protein retarder, 0.05 part by weight of organic silicon defoamer, 0.02 part by weight of cellulose ether and 0.1 part by weight of polycarboxylic acid water reducer to prepare the alkali-activated phosphogypsum self-leveling mortar.
Example 3
Uniformly mixing 60 parts by weight of phosphogypsum, 10 parts by weight of slag, 1.6 parts by weight of calcium hydroxide, 40 parts by weight of fine aggregate, 0.05 part by weight of protein retarder, 0.12 part by weight of organic silicon defoamer, 0.06 part by weight of cellulose ether and 0.2 part by weight of polycarboxylic acid water reducer to prepare the alkali-activated phosphogypsum self-leveling mortar.
Example 4
Uniformly mixing 60 parts by weight of phosphogypsum, 15 parts by weight of slag, 1.6 parts by weight of calcium hydroxide, 50 parts by weight of fine aggregate, 0.02 part by weight of protein retarder, 0.05 part by weight of organic silicon defoamer, 0.02 part by weight of cellulose ether and 0.1 part by weight of polycarboxylic acid water reducer to prepare the alkali-activated phosphogypsum self-leveling mortar.
Comparative example 1
Uniformly mixing 60 parts by weight of phosphogypsum, 40 parts by weight of fine aggregate, 1 part by weight of calcium hydroxide, 0.02 part by weight of protein retarder, 0.05 part by weight of organic silicon defoamer, 0.02 part by weight of water-retaining agent and 0.1 part by weight of water-reducing agent to prepare the phosphogypsum self-leveling mortar.
Table 1 table of performance parameters of alkali activated phosphogypsum self-levelling mortars prepared in examples 1 to 4 and unmodified phosphogypsum self-levelling mortar of comparative example 1
Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
Initial setting time/min | 135 | 127 | 106 | 113 | 180 |
Final setting time/min | 178 | 181 | 158 | 159 | 215 |
24h flexural strength/Mpa | 5.8 | 5.3 | 4.9 | 5.6 | 1.1 |
Compressive strength/Mpa for 24h | 14.1 | 15.2 | 12.8 | 14.9 | 4.4 |
Absolute dry rupture strength/Mpa | 6.3 | 7.1 | 6.5 | 7.0 | 4.8 |
Absolute dry compressive strength/Mpa | 25.3 | 30.5 | 27.3 | 29.8 | 11.8 |
Coefficient of softening | 0.71 | 0.79 | 0.69 | 0.74 | 0.45 |
As can be seen from table 1, the alkali-activated phosphogypsum self-leveling mortar prepared in examples 1 to 4 modified by the alkali activator has a reduced initial setting time and final setting time compared with those of comparative example 1 without the alkali-activated binding material, and has improved strength and softening coefficient compared with those of the unmodified phosphogypsum self-leveling mortar.
Claims (8)
2. the alkali-activated phosphogypsum self-leveling mortar according to claim 1, is characterized in that: the slag is granulated blast furnace slag powder, the alkalinity coefficient is more than 1, and the mass coefficient is more than 1.2.
3. The alkali-activated phosphogypsum self-leveling mortar according to claim 1, is characterized in that: the alkali activator adopts calcium hydroxide.
4. The alkali-activated phosphogypsum self-leveling mortar according to claim 1, is characterized in that: the retarder adopts protein retarder.
5. The alkali-activated phosphogypsum self-leveling mortar according to claim 4, which is characterized in that: the protein gypsum retarder is formed by polymerizing one or more of modified amino acid, modified polypeptide and natural protein hydrolysate.
6. The alkali-activated phosphogypsum self-leveling mortar according to claim 1, is characterized in that: the defoaming agent is one or more of a polyether defoaming agent, a modified polyether defoaming agent, an organic silicon defoaming agent and a polyether modified polysiloxane defoaming agent, the water-retaining agent is cellulose ether, and the water-reducing agent is a polycarboxylic acid water-reducing agent.
7. The alkali-activated phosphogypsum self-leveling mortar according to claim 6, which is characterized in that: the viscosity of the cellulose ether is lower than 1000 mPa.s.
8. The alkali-activated phosphogypsum self-leveling mortar according to claim 7, is characterized in that: the acid-ether ratio of the polycarboxylic acid water reducing agent is not less than 4.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114735998A (en) * | 2022-05-18 | 2022-07-12 | 湖北工业大学 | High-performance phosphogypsum composite cementing material based on hydration synergistic effect |
CN115321930A (en) * | 2022-07-26 | 2022-11-11 | 武汉理工大学 | Modified beta phosphogypsum-based waste concrete reclaimed sand self-leveling mortar and preparation method thereof |
CN116023108A (en) * | 2022-12-26 | 2023-04-28 | 北京东方建宇混凝土科学技术研究院有限公司 | High-water-resistance gypsum product and preparation method thereof |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114735998A (en) * | 2022-05-18 | 2022-07-12 | 湖北工业大学 | High-performance phosphogypsum composite cementing material based on hydration synergistic effect |
CN114735998B (en) * | 2022-05-18 | 2023-06-02 | 湖北工业大学 | High-performance phosphogypsum composite cementing material based on hydration synergistic effect |
CN115321930A (en) * | 2022-07-26 | 2022-11-11 | 武汉理工大学 | Modified beta phosphogypsum-based waste concrete reclaimed sand self-leveling mortar and preparation method thereof |
CN116023108A (en) * | 2022-12-26 | 2023-04-28 | 北京东方建宇混凝土科学技术研究院有限公司 | High-water-resistance gypsum product and preparation method thereof |
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