CN112830757A - Modified sodium silicate quick-setting material and preparation method thereof - Google Patents

Abstract

The invention provides a modified sodium silicate quick-setting material and a preparation method thereof. The modified sodium silicate quick-setting material comprises a component A and a component B; the component A comprises ordinary portland cement and fly ash, and the component B comprises ethylene glycol, adipic acid and water glass. The preparation method of the modified sodium silicate quick-setting material comprises the steps of adding water to the component A and the component B respectively, and preparing according to the process steps. The modified sodium silicate quick-setting material has the advantages of low cost, convenient construction, excellent performance and comprehensive functions, and grouting slurry can be quickly cured and cemented in a channel containing dynamic (static) water, so that the flow resistance of the leakage-stopping slurry is improved, and the slurry leakage is reduced.

Description

Modified sodium silicate quick-setting material and preparation method thereof

Technical Field

The invention relates to a quick-setting material and a preparation method thereof, in particular to a modified sodium silicate quick-setting material and a preparation method thereof, belonging to the technical field of building materials and mining materials.

Background

With the progress of grouting theory and the accumulation of engineering practice, the application range and scale of grouting are gradually enlarged, and grouting materials and construction technology are greatly developed. The development of grouting materials has been over 200 years since the record, and the grouting materials are developed from the original clay and lime, cement, to cement-water glass slurry, chemical slurry and the like. Underground works surrounding rocks are complicated and changeable, different geological conditions have different requirements on the types and the performance of grouting materials, and proper grouting materials are selected, so that the construction safety can be realized while the grouting quality is ensured, and the method has important significance in researching the grouting materials. Although the types of the existing grouting materials are more, the reinforcing effects of different grouting materials are different, and the difference of geological conditions is large, so that the grouting performance of the selected grouting material is often difficult to meet the engineering requirements; on the other hand, chemical or polymer materials generally have the advantages of short gel time, good cementing property and the like, but have high manufacturing cost, high requirements on construction technology and difficult realization of long-term calculus effect, and cannot ensure long-term reinforcement safety of underground engineering.

In the grouting reinforcement engineering with moving and static water, for example, in some coal mine goafs and the like, the novel rapid-hardening grouting plugging material is a reinforcing mode with strong pertinence, economy and effectiveness. The quick-setting material is formed by mixing cement fly ash and modified water glass, integrates the advantages of high strength of common cement slurry and high setting speed of water glass slurry, can form a stone body with short setting time and high early strength in water, is convenient to construct, has excellent performance, low price, environmental protection and no pollution, and can be widely welcomed in water-rich soft rock stratums needing water stopping and reinforcement.

At present, scholars at home and abroad develop a series of quick-setting grouting materials, promote the development of the grouting materials to a certain extent and provide guidance for engineering practice.

(1) Chinese patent CN 111777389A introduces a quick-setting adjustable cement-based underwater anti-dispersion ultrafast hard grouting material, a preparation method and application thereof, wherein the material comprises a component A and a component B; the component A comprises: 80-90% of a cementing material, 3-10% of an active admixture, 3-7% of an expanding agent, 2-3% of a high-performance underwater anti-dispersant and 0.1-0.3% of a polycarboxylic acid high-performance water reducing agent; the component B comprises: 80-90% of a quick-hardening cementing material, 4-10% of an active admixture, 3-7% of an expanding agent, 2-3% of a high-performance underwater anti-dispersing agent, 0.1-0.3% of a polycarboxylic acid high-performance water reducing agent, 0.1-0.2% of a retarder, 0.1-0.2% of an early strength agent, 0.1-0.15% of a thixotropic agent and 0.05-0.1% of an interface wetting agent. The grouting material has good underwater anti-dispersion capability, can be cured and cemented quickly, improves the flow resistance of the leaking stoppage slurry, and reduces slurry loss.

(2) Chinese patent CN 103626454A introduces a method for preparing a quick-setting early-strength double-fluid grouting material, which is prepared by mixing a component A and a component B, wherein the component A comprises sulphoaluminate cement, a water reducing agent, an early strength agent, a retarder and a suspending agent, and the component B comprises gypsum, lime, a water reducing agent, an accelerator, a suspending agent and a retarder. The invention has simple processing technology, adjustable coagulation time, high early strength, long single-liquid storage time, rapid coagulation after mixing of two liquids, no drying shrinkage deformation due to micro-expansion of the calculus body and good stability.

(3) Chinese patent CN 110002815A introduces a quick-setting water-dispersion-resistant cement-based grouting material and a preparation method thereof, wherein the quick-setting water-dispersion-resistant cement-based grouting material is prepared from dry powder and water according to the weight ratio of 1: (0.36-0.40), wherein the dry powder comprises the following raw materials in percentage by weight: 91-94% of cement, 6-8% of an accelerator, 0.03-0.05% of a retarder, 0.1-0.2% of an excitant, 0.2-0.3% of a water reducer, 0.1-0.15% of a thickener, 0.1-0.2% of an early strength agent and 0.05-0.1% of a surfactant; the material has short setting time, initial setting time of not more than 5min, good water dispersibility resistance, no dispersion under water, high stone strength, 1-day compressive strength of not less than 5MPa and 3-day compressive strength of not less than 20MPa, and can be well applied to the treatment of tunnel water inrush disasters.

(4) Chinese patent CN 109608143A introduces a quick-setting early strength cement-water glass double-liquid grouting material and a use method thereof, the grouting material is prepared by a matrix component and an external doping component, the matrix component comprises a cementing material and water, and the external doping component comprises an accelerator and a water reducing agent; the cement water-cement ratio is 3: and 5, the volume ratio of the accelerator to the prepared cementing material slurry is 1: 1, the adding amount of the water reducing agent is 1.0-3.0% of the cementing material. The grouting material has the characteristics of short setting time, high early strength, high calculus rate, good pumpability and good stability, can be applied to the advanced grouting reinforcement of the broken roof surrounding rock to prevent roof collapse during roadway excavation, and can improve the roadway excavation efficiency.

(5) Chinese patent CN 103265260A introduces a high-strength quick-setting double-fluid grouting material and a use method thereof, the grouting material consists of a component A and a component B, and the percentage content of each component in the total mass is as follows: the component A comprises: 40-45% of sulphoaluminate cement and 5-10% of gypsum; and B component: 40-45% of Portland cement and 5-10% of gypsum. When in use: a, B components are respectively added with water to prepare slurry with a water-cement ratio of 0.5: 1-0.7: 1, then the slurry of the component A and the slurry of the component B are fully mixed at a filling position through a slurry mixer of a double-liquid grouting pump, the mixed slurry is in a fluid state and self-levels and is dense, initial setting can be completed within 2-3 minutes, final setting can be completed within 5-10 minutes, and the purpose of quick setting and high-strength grouting is achieved. The high-strength rapid-setting double-fluid grouting material has the characteristics of high setting speed and high initial strength, and is low in price, non-toxic, non-flammable and free of potential safety hazard.

The comprehensive analysis of the existing patent results has the following defects:

1. various additives such as an accelerating agent, a water reducing agent, a retarder, a thickener and the like are needed, the raw materials are complex, and the needed cost is high;

2. the addition of some additives is less, the required process precision is high, and the construction operation is more complex;

3. after various materials are mixed, pollution is easy to generate, and potential safety hazards are caused;

4. the problems of poor structural stability and poor underground water erosion resistance of the solidified double-liquid grouting material due to the self structure of the water glass are still not solved;

5. is not suitable for projects containing dynamic and static water conditions such as coal mine goafs and the like, and has limited construction conditions.

Disclosure of Invention

In order to overcome the defects of the existing grouting material, the invention provides a modified sodium silicate quick-setting material and a preparation method thereof.

In order to achieve the purpose, the invention is realized by the following technical scheme:

the modified sodium silicate quick-setting material is characterized in that: comprises a component A and a component B;

the component A comprises ordinary portland cement and fly ash, and the component B comprises ethylene glycol, adipic acid and water glass;

the component A comprises the following components: 40-70 parts of ordinary portland cement, 30-60 parts of fly ash and inevitable impurities.

The component B comprises the following components: 0.6-1 part of ethylene glycol, 1-1.4 parts of adipic acid, 97.6-98.4 parts of water glass and inevitable impurities.

A preparation method of a modified sodium silicate quick-setting material comprises the following steps:

(1) and (3) putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring while mixing according to the mass ratio of water to solid of 1: 1, adding water, and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: the mass ratio of the component B is 1: 2, heating water to 60-70 ℃, sequentially adding the ethylene glycol material and the adipic acid material in the component B, stirring by using a glass rod until the adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) mixing the mixture I and the mixture III according to a volume ratio of 1: putting the mixture into a high-stirring cup together in a ratio of 0.4-0.6, performing high stirring for 5-10 s at a stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.

The invention has the advantages that:

the modified water glass material is prepared by adjusting the proportion of the water glass material and various reagents, and then the cement fly ash with different proportions is matched to prepare a new cement fly ash-modified water glass material under the synergistic action of all the components, so that the cost is low, the construction is convenient, the performance is excellent, the functions are comprehensive, and meanwhile, the grouting slurry can be rapidly solidified and cemented in a channel containing dynamic (static) water, the flow resistance of the plugging slurry is improved, and the slurry leakage is reduced.

Detailed Description

The following detailed description is to be taken in conjunction with the specific embodiments, but the specific embodiments below should not be construed as limiting the invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention.

Example 1

The invention provides a modified sodium silicate quick-setting material, which comprises a component A and a component B; the component A comprises ordinary portland cement and fly ash, and the component B comprises Ethylene Glycol (EG), Adipic Acid (AA) and water glass;

the component A comprises: 70% of ordinary portland cement, 30% of fly ash and inevitable impurities;

and B component: EG: AA: water glass = 0.7%: 1%: 98.3%, and inevitable impurities.

The cement in the component A is a powdery hydraulic cementing material, and not only has higher strength after hardening, but also can resist the erosion of fresh water or salt-containing water; the fly ash can save cement consumption, reduce water consumption, improve the workability of concrete mixture, enhance the pumpability of concrete, reduce creep of concrete, reduce hydration heat and thermal expansion and improve the impermeability of concrete.

The water glass in the component B is a solid sodium silicate aqueous solution with the characteristics of strong cohesive force, high acid corrosion resistance, good heat resistance and the like, plays a role of a catalyst in the activity effect of the fly ash, and has the effect of an accelerator; EG is the simplest diol and can be used as a solvent; AA is an important organic diacid, can be condensed with dihydric alcohol to form a high molecular polymer and plays a role of a catalyst.

The preparation method of the modified sodium silicate quick-setting material comprises the following steps:

(1) firstly, putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring at the water-solid ratio of 1: adding water in an amount of 1 (mass ratio), and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: component B = 1: 2 (mass ratio), heating water to 60-70 ℃, sequentially adding the EG material and the AA material in the component B, stirring by using a glass rod until adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) the mixture I and the mixture III obtained in the first step were mixed in a ratio of 1: and (3) putting the mixture into a high-stirring cup together according to the volume ratio of 0.6, performing high stirring for 5-10 s at the stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.

Laboratory tests were carried out under the following experimental conditions: the environmental temperature is (20 +/-2) DEG C, and the relative humidity is 60% -80%; the water temperature of the curing pool is (20 +/-1) DEG C; the temperature of a curing box or a fog chamber for curing the test piece with the mold is kept at (20 +/-1) DEG C, and the relative humidity is not lower than 90 percent.

a) Initial setting time measurement: quickly taking 200mL of prepared IV serous fluid in the cup A, taking an empty cup B, and beginning to time; the mixture was poured out by hand at A, B for two cups, and the gel time (initial setting time) was the time elapsed until the slurry no longer flowed.

b) Final setting time determination: quickly taking 200mL of prepared IV slurry, pouring the prepared IV slurry into a circular mold, immediately taking the test mold together with the slurry from a glass plate by a translation method after the initial setting time is reached, turning the test mold and the slurry for 180 degrees, placing the test mold and the slurry on the glass plate with the large end of the diameter upward and the small end downward, placing the test mold and the slurry into a standard curing box for continuous curing, measuring the time close to the final setting time every 10s, and when a test needle is sunk into a test body for 0.5mm, namely the annular accessory cannot leave marks on the test body, determining that the cement reaches the final setting state.

c) And (3) fluidity measurement: placing paper boards with concentric circles and with the same radius increase in the same amount on a horizontal position, placing a glass plate above the paper boards, placing a clean slurry fluidity test mold in the center of the glass plate, quickly injecting mixed IV slurry into the clean slurry fluidity test mold, leveling the mixed IV slurry by using a scraper, lifting the clean slurry fluidity test mold in the vertical direction, starting a stopwatch to time at the same time, allowing the cement clean slurry to flow on the glass plate for 30s, taking the maximum diameter of the flowing part in two mutually perpendicular directions by using a ruler, and taking the average value as the cement clean slurry fluidity.

d) And (3) measuring the calculus rate: putting the IV slurry into a measuring cylinder, and sealing the measuring cylinder; the reading was observed every 2min until the slurry stabilized. Water extraction = volume of clear water extracted (ml)/volume of slurry (ml), expressed as a percentage, calculus rate = 1-water extraction rate.

e) Quickly filling the prepared IV serous fluid into a test mold (a cylinder with the thickness of 50mm multiplied by 100 mm), uniformly vibrating from outside to inside by using a vibrating rod according to a spiral direction if necessary, inserting and tamping for a plurality of times along the mold wall by using a scraper to prevent air holes from possibly being left after the low-consistency serous fluid is inserted and tamped, wherein the serous fluid is 6 mm-8 mm higher than the top surface of the test mold, and scraping by using a scraper; forming 2 groups of test pieces for each sample; curing (24 +/-2) hours under standard test conditions after molding, and then demolding; and then continuously maintaining the test piece in water at the temperature of (20 +/-1) DEG for 7 days, taking out the test piece, absorbing free water visible on the surface by using soft cloth, and measuring the compressive strength by using a pavement material strength tester.

The test results are given in the following table:

test of	Initial setting time/min	Final setting time/min	Fluidity/mm	Calculus rate/%	7d compressive strength/MPa
						Results	0.583	4.333	390	100	8.362

Example 2:

the invention provides a modified sodium silicate quick-setting material, which comprises a component A and a component B; the component A comprises ordinary portland cement and fly ash, and the component B comprises Ethylene Glycol (EG), Adipic Acid (AA) and water glass;

the component A comprises: 60% of ordinary portland cement, 40% of fly ash and inevitable impurities;

and B component: EG: AA: water glass = 0.7%: 1%: 98.3%, and inevitable impurities.

The cement in the component A is a powdery hydraulic cementing material, and not only has higher strength after hardening, but also can resist the erosion of fresh water or salt-containing water; the fly ash can save cement consumption, reduce water consumption, improve the workability of concrete mixture, enhance the pumpability of concrete, reduce creep of concrete, reduce hydration heat and thermal expansion and improve the impermeability of concrete.

The water glass in the component B is a solid sodium silicate aqueous solution with the characteristics of strong cohesive force, high acid corrosion resistance, good heat resistance and the like, plays a role of a catalyst in the activity effect of the fly ash, and has the effect of an accelerator; EG is the simplest diol and can be used as a solvent; AA is an important organic diacid, can be condensed with dihydric alcohol to form a high molecular polymer and plays a role of a catalyst.

The preparation method of the modified sodium silicate quick-setting material comprises the following steps:

(1) firstly, putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring at the water-solid ratio of 1: adding water in an amount of 1 (mass ratio), and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: component B = 1: 2 (mass ratio), heating water to 60-70 ℃, sequentially adding the EG material and the AA material in the component B, stirring by using a glass rod until adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) the mixture I and the mixture III obtained in the first step were mixed in a ratio of 1: and (3) putting the mixture into a high-stirring cup together according to the volume ratio of 0.6, performing high stirring for 5-10 s at the stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.

Laboratory tests were carried out under the following experimental conditions: the environmental temperature is (20 +/-2) DEG C, and the relative humidity is 60% -80%; the water temperature of the curing pool is (20 +/-1) DEG C; the temperature of a curing box or a fog chamber for curing the test piece with the mold is kept at (20 +/-1) DEG C, and the relative humidity is not lower than 90 percent.

a) Initial setting time measurement: quickly taking 200mL of prepared IV serous fluid in the cup A, taking an empty cup B, and beginning to time; the mixture was poured out by hand at A, B for two cups, and the gel time (initial setting time) was the time elapsed until the slurry no longer flowed.

b) Final setting time determination: quickly taking 200mL of prepared IV slurry, pouring the prepared IV slurry into a circular mold, immediately taking the test mold together with the slurry from a glass plate by a translation method after the initial setting time is reached, turning the test mold and the slurry for 180 degrees, placing the test mold and the slurry on the glass plate with the large end of the diameter upward and the small end downward, placing the test mold and the slurry into a standard curing box for continuous curing, measuring the time close to the final setting time every 10s, and when a test needle is sunk into a test body for 0.5mm, namely the annular accessory cannot leave marks on the test body, determining that the cement reaches the final setting state.

c) And (3) fluidity measurement: placing paper boards with concentric circles and with the same radius increase in the same amount on a horizontal position, placing a glass plate above the paper boards, placing a clean slurry fluidity test mold in the center of the glass plate, quickly injecting mixed IV slurry into the clean slurry fluidity test mold, leveling the mixed IV slurry by using a scraper, lifting the clean slurry fluidity test mold in the vertical direction, starting a stopwatch to time at the same time, allowing the cement clean slurry to flow on the glass plate for 30s, taking the maximum diameter of the flowing part in two mutually perpendicular directions by using a ruler, and taking the average value as the cement clean slurry fluidity.

d) And (3) measuring the calculus rate: putting the IV slurry into a measuring cylinder, and sealing the measuring cylinder; the reading was observed every 2min until the slurry stabilized. Water extraction = volume of clear water extracted (ml)/volume of slurry (ml), expressed as a percentage, calculus rate = 1-water extraction rate.

e) Quickly filling the prepared IV serous fluid into a test mold (a cylinder with the thickness of 50mm multiplied by 100 mm), uniformly vibrating from outside to inside by using a vibrating rod according to a spiral direction if necessary, inserting and tamping for a plurality of times along the mold wall by using a scraper to prevent air holes from possibly being left after the low-consistency serous fluid is inserted and tamped, wherein the serous fluid is 6 mm-8 mm higher than the top surface of the test mold, and scraping by using a scraper; forming 2 groups of test pieces for each sample; curing (24 +/-2) hours under standard test conditions after molding, and then demolding; and then continuously maintaining the test piece in water at the temperature of (20 +/-1) DEG for 7 days, taking out the test piece, absorbing free water visible on the surface by using soft cloth, and measuring the compressive strength by using a pavement material strength tester.

The test results are given in the following table:

test of	Initial setting time/min	Final setting time/min	Fluidity/mm	Calculus rate/%	7d compressive strength/MPa
						Results	0.633	4.5	405	100	7.073

Example 3:

the invention provides a modified sodium silicate quick-setting material, which comprises a component A and a component B; the component A comprises ordinary portland cement and fly ash, and the component B comprises Ethylene Glycol (EG), Adipic Acid (AA) and water glass;

the component A comprises: 40% of ordinary portland cement, 60% of fly ash and inevitable impurities;

and B component: EG: AA: water glass = 0.7%: 1%: 98.3%, and inevitable impurities.

The cement in the component A is a powdery hydraulic cementing material, and not only has higher strength after hardening, but also can resist the erosion of fresh water or salt-containing water; the fly ash can save cement consumption, reduce water consumption, improve the workability of concrete mixture, enhance the pumpability of concrete, reduce creep of concrete, reduce hydration heat and thermal expansion and improve the impermeability of concrete.

The water glass in the component B is a solid sodium silicate aqueous solution with the characteristics of strong cohesive force, high acid corrosion resistance, good heat resistance and the like, plays a role of a catalyst in the activity effect of the fly ash, and has the effect of an accelerator; EG is the simplest diol and can be used as a solvent; AA is an important organic diacid, can be condensed with dihydric alcohol to form a high molecular polymer and plays a role of a catalyst.

The preparation method of the modified sodium silicate quick-setting material comprises the following steps:

(1) firstly, putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring at the water-solid ratio of 1: adding water in an amount of 1 (mass ratio), and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: component B = 1: 2 (mass ratio), heating water to 60-70 ℃, sequentially adding the EG material and the AA material in the component B, stirring by using a glass rod until adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) the mixture I and the mixture III obtained in the first step were mixed in a ratio of 1: and (3) putting the mixture into a high-stirring cup together according to the volume ratio of 0.6, performing high stirring for 5-10 s at the stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.

Laboratory tests were carried out under the following experimental conditions: the environmental temperature is (20 +/-2) DEG C, and the relative humidity is 60% -80%; the water temperature of the curing pool is (20 +/-1) DEG C; the temperature of a curing box or a fog chamber for curing the test piece with the mold is kept at (20 +/-1) DEG C, and the relative humidity is not lower than 90 percent.

a) Initial setting time measurement: quickly taking 200mL of prepared IV serous fluid in the cup A, taking an empty cup B, and beginning to time; the mixture was poured out by hand at A, B for two cups, and the gel time (initial setting time) was the time elapsed until the slurry no longer flowed.

b) Final setting time determination: quickly taking 200mL of prepared IV slurry, pouring the prepared IV slurry into a circular mold, immediately taking the test mold together with the slurry from a glass plate by a translation method after the initial setting time is reached, turning the test mold and the slurry for 180 degrees, placing the test mold and the slurry on the glass plate with the large end of the diameter upward and the small end downward, placing the test mold and the slurry into a standard curing box for continuous curing, measuring the time close to the final setting time every 10s, and when a test needle is sunk into a test body for 0.5mm, namely the annular accessory cannot leave marks on the test body, determining that the cement reaches the final setting state.

c) And (3) fluidity measurement: placing paper boards with concentric circles and with the same radius increase in the same amount on a horizontal position, placing a glass plate above the paper boards, placing a clean slurry fluidity test mold in the center of the glass plate, quickly injecting mixed IV slurry into the clean slurry fluidity test mold, leveling the mixed IV slurry by using a scraper, lifting the clean slurry fluidity test mold in the vertical direction, starting a stopwatch to time at the same time, allowing the cement clean slurry to flow on the glass plate for 30s, taking the maximum diameter of the flowing part in two mutually perpendicular directions by using a ruler, and taking the average value as the cement clean slurry fluidity.

d) And (3) measuring the calculus rate: putting the IV slurry into a measuring cylinder, and sealing the measuring cylinder; the reading was observed every 2min until the slurry stabilized. Water extraction = volume of clear water extracted (ml)/volume of slurry (ml), expressed as a percentage, calculus rate = 1-water extraction rate.

e) Quickly filling the prepared IV serous fluid into a test mold (a cylinder with the thickness of 50mm multiplied by 100 mm), uniformly vibrating from outside to inside by using a vibrating rod according to a spiral direction if necessary, inserting and tamping for a plurality of times along the mold wall by using a scraper to prevent air holes from possibly being left after the low-consistency serous fluid is inserted and tamped, wherein the serous fluid is 6 mm-8 mm higher than the top surface of the test mold, and scraping by using a scraper; forming 2 groups of test pieces for each sample; curing (24 +/-2) hours under standard test conditions after molding, and then demolding; and then continuously maintaining the test piece in water at the temperature of (20 +/-1) DEG for 7 days, taking out the test piece, absorbing free water visible on the surface by using soft cloth, and measuring the compressive strength by using a pavement material strength tester.

The test results are given in the following table:

test of	Initial setting time/min	Final setting time/min	Fluidity/mm	Calculus rate/%	7d compressive strength/MPa
						Results	1.117	5.833	410	100	1.292

Example 4:

the invention provides a modified sodium silicate quick-setting material, which comprises a component A and a component B; the component A comprises ordinary portland cement and fly ash, and the component B comprises Ethylene Glycol (EG), Adipic Acid (AA) and water glass;

the component A comprises: 60% of ordinary portland cement, 40% of fly ash and inevitable impurities;

and B component: EG: AA: water glass = 0.7%: 1%: 98.3%, and inevitable impurities.

The cement in the component A is a powdery hydraulic cementing material, and not only has higher strength after hardening, but also can resist the erosion of fresh water or salt-containing water; the fly ash can save cement consumption, reduce water consumption, improve the workability of concrete mixture, enhance the pumpability of concrete, reduce creep of concrete, reduce hydration heat and thermal expansion and improve the impermeability of concrete.

The water glass in the component B is a solid sodium silicate aqueous solution with the characteristics of strong cohesive force, high acid corrosion resistance, good heat resistance and the like, plays a role of a catalyst in the activity effect of the fly ash, and has the effect of an accelerator; EG is the simplest diol and can be used as a solvent; AA is an important organic diacid, can be condensed with dihydric alcohol to form a high molecular polymer and plays a role of a catalyst.

The preparation method of the modified sodium silicate quick-setting material comprises the following steps:

(1) firstly, putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring at the water-solid ratio of 1: adding water in an amount of 1 (mass ratio), and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: component B = 1: 2 (mass ratio), heating water to 60-70 ℃, sequentially adding the EG material and the AA material in the component B, stirring by using a glass rod until adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) the mixture I and the mixture III obtained in the first step were mixed in a ratio of 1: and (3) putting the mixture into a high-stirring cup together according to the volume ratio of 0.6, performing high stirring for 5-10 s at the stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.

Laboratory tests were carried out under the following experimental conditions: the environmental temperature is (20 +/-2) DEG C, and the relative humidity is 60% -80%; the water temperature of the curing pool is (20 +/-1) DEG C; the temperature of a curing box or a fog chamber for curing the test piece with the mold is kept at (20 +/-1) DEG C, and the relative humidity is not lower than 90 percent.

a) Initial setting time measurement: quickly taking 200mL of prepared IV serous fluid in the cup A, taking an empty cup B, and beginning to time; the mixture was poured out by hand at A, B for two cups, and the gel time (initial setting time) was the time elapsed until the slurry no longer flowed.

b) Final setting time determination: quickly taking 200mL of prepared IV slurry, pouring the prepared IV slurry into a circular mold, immediately taking the test mold together with the slurry from a glass plate by a translation method after the initial setting time is reached, turning the test mold and the slurry for 180 degrees, placing the test mold and the slurry on the glass plate with the large end of the diameter upward and the small end downward, placing the test mold and the slurry into a standard curing box for continuous curing, measuring the time close to the final setting time every 10s, and when a test needle is sunk into a test body for 0.5mm, namely the annular accessory cannot leave marks on the test body, determining that the cement reaches the final setting state.

c) And (3) fluidity measurement: placing paper boards with concentric circles and with the same radius increase in the same amount on a horizontal position, placing a glass plate above the paper boards, placing a clean slurry fluidity test mold in the center of the glass plate, quickly injecting mixed IV slurry into the clean slurry fluidity test mold, leveling the mixed IV slurry by using a scraper, lifting the clean slurry fluidity test mold in the vertical direction, starting a stopwatch to time at the same time, allowing the cement clean slurry to flow on the glass plate for 30s, taking the maximum diameter of the flowing part in two mutually perpendicular directions by using a ruler, and taking the average value as the cement clean slurry fluidity.

d) And (3) measuring the calculus rate: putting the IV slurry into a measuring cylinder, and sealing the measuring cylinder; the reading was observed every 2min until the slurry stabilized. Water extraction = volume of clear water extracted (ml)/volume of slurry (ml), expressed as a percentage, calculus rate = 1-water extraction rate.

e) Quickly filling the prepared IV serous fluid into a test mold (a cylinder with the thickness of 50mm multiplied by 100 mm), uniformly vibrating from outside to inside by using a vibrating rod according to a spiral direction if necessary, inserting and tamping for a plurality of times along the mold wall by using a scraper to prevent air holes from possibly being left after the low-consistency serous fluid is inserted and tamped, wherein the serous fluid is 6 mm-8 mm higher than the top surface of the test mold, and scraping by using a scraper; forming 2 groups of test pieces for each sample; curing (24 +/-2) hours under standard test conditions after molding, and then demolding; and then continuously maintaining the test piece in water at the temperature of (20 +/-1) DEG for 7 days, taking out the test piece, absorbing free water visible on the surface by using soft cloth, and measuring the compressive strength by using a pavement material strength tester.

The test results are given in the following table:

test of	Initial setting time/min	Final setting time/min	Fluidity/mm	Calculus rate/%	7d compressive strength/MPa
						Results	0.433	9	358	100	6.230

Example 5:

the invention provides a modified sodium silicate quick-setting material, which comprises a component A and a component B; the component A comprises ordinary portland cement and fly ash, and the component B comprises Ethylene Glycol (EG), Adipic Acid (AA) and water glass;

the component A comprises: 30% of ordinary portland cement, 70% of fly ash and inevitable impurities;

and B component: EG: AA: water glass = 0.7%: 1%: 98.3%, and inevitable impurities.

The cement in the component A is a powdery hydraulic cementing material, and not only has higher strength after hardening, but also can resist the erosion of fresh water or salt-containing water; the fly ash can save cement consumption, reduce water consumption, improve the workability of concrete mixture, enhance the pumpability of concrete, reduce creep of concrete, reduce hydration heat and thermal expansion and improve the impermeability of concrete.

The water glass in the component B is a solid sodium silicate aqueous solution with the characteristics of strong cohesive force, high acid corrosion resistance, good heat resistance and the like, plays a role of a catalyst in the activity effect of the fly ash, and has the effect of an accelerator; EG is the simplest diol and can be used as a solvent; AA is an important organic diacid, can be condensed with dihydric alcohol to form a high molecular polymer and plays a role of a catalyst.

The preparation method of the modified sodium silicate quick-setting material comprises the following steps:

(1) firstly, putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring at the water-solid ratio of 1: adding water in an amount of 1 (mass ratio), and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: component B = 1: 2 (mass ratio), heating water to 60-70 ℃, sequentially adding the EG material and the AA material in the component B, stirring by using a glass rod until adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) the mixture I and the mixture III obtained in the first step were mixed in a ratio of 1: and (3) putting the mixture into a high-stirring cup together according to the volume ratio of 0.6, performing high stirring for 5-10 s at the stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.

Laboratory tests were carried out under the following experimental conditions: the environmental temperature is (20 +/-2) DEG C, and the relative humidity is 60% -80%; the water temperature of the curing pool is (20 +/-1) DEG C; the temperature of a curing box or a fog chamber for curing the test piece with the mold is kept at (20 +/-1) DEG C, and the relative humidity is not lower than 90 percent.

a) Initial setting time measurement: quickly taking 200mL of prepared IV serous fluid in the cup A, taking an empty cup B, and beginning to time; the mixture was poured out by hand at A, B for two cups, and the gel time (initial setting time) was the time elapsed until the slurry no longer flowed.

b) Final setting time determination: quickly taking 200mL of prepared IV slurry, pouring the prepared IV slurry into a circular mold, immediately taking the test mold together with the slurry from a glass plate by a translation method after the initial setting time is reached, turning the test mold and the slurry for 180 degrees, placing the test mold and the slurry on the glass plate with the large end of the diameter upward and the small end downward, placing the test mold and the slurry into a standard curing box for continuous curing, measuring the time close to the final setting time every 10s, and when a test needle is sunk into a test body for 0.5mm, namely the annular accessory cannot leave marks on the test body, determining that the cement reaches the final setting state.

c) And (3) fluidity measurement: placing paper boards with concentric circles and with the same radius increase in the same amount on a horizontal position, placing a glass plate above the paper boards, placing a clean slurry fluidity test mold in the center of the glass plate, quickly injecting mixed IV slurry into the clean slurry fluidity test mold, leveling the mixed IV slurry by using a scraper, lifting the clean slurry fluidity test mold in the vertical direction, starting a stopwatch to time at the same time, allowing the cement clean slurry to flow on the glass plate for 30s, taking the maximum diameter of the flowing part in two mutually perpendicular directions by using a ruler, and taking the average value as the cement clean slurry fluidity.

d) And (3) measuring the calculus rate: putting the IV slurry into a measuring cylinder, and sealing the measuring cylinder; the reading was observed every 2min until the slurry stabilized. Water extraction = volume of clear water extracted (ml)/volume of slurry (ml), expressed as a percentage, calculus rate = 1-water extraction rate.

e) Quickly filling the prepared IV serous fluid into a test mold (a cylinder with the thickness of 50mm multiplied by 100 mm), uniformly vibrating from outside to inside by using a vibrating rod according to a spiral direction if necessary, inserting and tamping for a plurality of times along the mold wall by using a scraper to prevent air holes from possibly being left after the low-consistency serous fluid is inserted and tamped, wherein the serous fluid is 6 mm-8 mm higher than the top surface of the test mold, and scraping by using a scraper; forming 2 groups of test pieces for each sample; curing (24 +/-2) hours under standard test conditions after molding, and then demolding; and then continuously maintaining the test piece in water at the temperature of (20 +/-1) DEG for 7 days, taking out the test piece, absorbing free water visible on the surface by using soft cloth, and measuring the compressive strength by using a pavement material strength tester.

The test results are given in the following table:

test of	Initial setting time/min	Final setting time/min	Fluidity/mm	Calculus rate/%	7d compressive strength/MPa
						Results	1.5	7.167	420	100	0.084

Example 6:

the invention provides a modified sodium silicate quick-setting material, which comprises a component A and a component B; the component A comprises ordinary portland cement and fly ash, and the component B comprises Ethylene Glycol (EG), Adipic Acid (AA) and water glass;

the component A comprises: 60% of ordinary portland cement, 40% of fly ash and inevitable impurities;

and B component: EG: AA: water glass = 0.7%: 1%: 98.3%, and inevitable impurities.

The cement in the component A is a powdery hydraulic cementing material, and not only has higher strength after hardening, but also can resist the erosion of fresh water or salt-containing water; the fly ash can save cement consumption, reduce water consumption, improve the workability of concrete mixture, enhance the pumpability of concrete, reduce creep of concrete, reduce hydration heat and thermal expansion and improve the impermeability of concrete.

The water glass in the component B is a solid sodium silicate aqueous solution with the characteristics of strong cohesive force, high acid corrosion resistance, good heat resistance and the like, plays a role of a catalyst in the activity effect of the fly ash, and has the effect of an accelerator; EG is the simplest diol and can be used as a solvent; AA is an important organic diacid, can be condensed with dihydric alcohol to form a high molecular polymer and plays a role of a catalyst.

The preparation method of the modified sodium silicate quick-setting material comprises the following steps:

(1) firstly, putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring at the water-solid ratio of 1: adding water in an amount of 1 (mass ratio), and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: component B = 1: 2 (mass ratio), heating water to 60-70 ℃, sequentially adding the EG material and the AA material in the component B, stirring by using a glass rod until adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) the mixture I and the mixture III obtained in the first step were mixed in a ratio of 1: and (3) putting the mixture into a high-stirring cup together according to the volume ratio of 0.6, performing high stirring for 5-10 s at the stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.

Laboratory tests were carried out under the following experimental conditions: the environmental temperature is (20 +/-2) DEG C, and the relative humidity is 60% -80%; the water temperature of the curing pool is (20 +/-1) DEG C; the temperature of a curing box or a fog chamber for curing the test piece with the mold is kept at (20 +/-1) DEG C, and the relative humidity is not lower than 90 percent.

a) Initial setting time measurement: quickly taking 200mL of prepared IV serous fluid in the cup A, taking an empty cup B, and beginning to time; the mixture was poured out by hand at A, B for two cups, and the gel time (initial setting time) was the time elapsed until the slurry no longer flowed.

b) Final setting time determination: quickly taking 200mL of prepared IV slurry, pouring the prepared IV slurry into a circular mold, immediately taking the test mold together with the slurry from a glass plate by a translation method after the initial setting time is reached, turning the test mold and the slurry for 180 degrees, placing the test mold and the slurry on the glass plate with the large end of the diameter upward and the small end downward, placing the test mold and the slurry into a standard curing box for continuous curing, measuring the time close to the final setting time every 10s, and when a test needle is sunk into a test body for 0.5mm, namely the annular accessory cannot leave marks on the test body, determining that the cement reaches the final setting state.

c) And (3) fluidity measurement: placing paper boards with concentric circles and with the same radius increase in the same amount on a horizontal position, placing a glass plate above the paper boards, placing a clean slurry fluidity test mold in the center of the glass plate, quickly injecting mixed IV slurry into the clean slurry fluidity test mold, leveling the mixed IV slurry by using a scraper, lifting the clean slurry fluidity test mold in the vertical direction, starting a stopwatch to time at the same time, allowing the cement clean slurry to flow on the glass plate for 30s, taking the maximum diameter of the flowing part in two mutually perpendicular directions by using a ruler, and taking the average value as the cement clean slurry fluidity.

d) And (3) measuring the calculus rate: putting the IV slurry into a measuring cylinder, and sealing the measuring cylinder; the reading was observed every 2min until the slurry stabilized. Water extraction = volume of clear water extracted (ml)/volume of slurry (ml), expressed as a percentage, calculus rate = 1-water extraction rate.

e) Quickly filling the prepared IV serous fluid into a test mold (a cylinder with the thickness of 50mm multiplied by 100 mm), uniformly vibrating from outside to inside by using a vibrating rod according to a spiral direction if necessary, inserting and tamping for a plurality of times along the mold wall by using a scraper to prevent air holes from possibly being left after the low-consistency serous fluid is inserted and tamped, wherein the serous fluid is 6 mm-8 mm higher than the top surface of the test mold, and scraping by using a scraper; forming 2 groups of test pieces for each sample; curing (24 +/-2) hours under standard test conditions after molding, and then demolding; and then continuously maintaining the test piece in water at the temperature of (20 +/-1) DEG for 7 days, taking out the test piece, absorbing free water visible on the surface by using soft cloth, and measuring the compressive strength by using a pavement material strength tester.

The test results are given in the following table:

test of	Initial setting time/min	Final setting time/min	Fluidity/mm	Calculus rate/%	7d compressive strength/MPa
						Results	0.333	56	290	100	4.329

Example 7:

the invention provides a cement water glass quick-setting material, which comprises a component A and a component B; the component A comprises ordinary portland cement, and the component B comprises water glass;

the component A comprises: ordinary portland cement, and inevitable impurities;

and B component: water glass, and inevitable impurities.

The cement in the component A is a powdery hydraulic cementing material, and not only has higher strength after hardening, but also can resist the erosion of fresh water or salt-containing water;

the water glass in the component B is a solid sodium silicate aqueous solution with the characteristics of strong cohesive force, high acid corrosion resistance, good heat resistance and the like, and has the effect of an accelerator.

The preparation method of the cement water glass quick-setting material comprises the following steps:

(1) firstly, putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring at the water-solid ratio of 1: adding water in an amount of 1 (mass ratio), and stirring and mixing uniformly to obtain a mixture I;

(2) the mixture I obtained in the first step and the component B are mixed according to a ratio of 1: and (3) putting the mixture into a high-stirring cup together according to the proportion of 0.6 (volume ratio), performing high stirring for 5-10 s at the stirring speed of 100r/min, uniformly mixing to obtain a finished product II, and immediately performing indoor test or field grouting.

Laboratory tests were carried out under the following experimental conditions: the environmental temperature is (20 +/-2) DEG C, and the relative humidity is 60% -80%; the water temperature of the curing pool is (20 +/-1) DEG C; the temperature of a curing box or a fog chamber for curing the test piece with the mold is kept at (20 +/-1) DEG C, and the relative humidity is not lower than 90 percent.

a) Initial setting time measurement: quickly taking 200mL of prepared slurry II in a cup A, taking an empty cup B, and beginning timing; the mixture was poured out by hand at A, B for two cups, and the gel time (initial setting time) was the time elapsed until the slurry no longer flowed.

b) Final setting time determination: quickly taking 200mL of prepared II slurry, pouring the II slurry into a circular mold, immediately taking the test mold together with the slurry from a glass plate by a translation method after the initial setting time is reached, turning the test mold and the slurry for 180 degrees, placing the test mold and the slurry on the glass plate with the large end of the diameter upward and the small end downward, placing the test mold and the slurry into a standard curing box for continuous curing, measuring the time of the test needle close to the final setting time every 10s, and when the test needle is sunk into a test body for 0.5mm, namely the annular accessory cannot leave marks on the test body, obtaining the final setting state for the cement.

c) And (3) fluidity measurement: placing the paperboards with the same increased radius and drawn with concentric circles at the horizontal position, placing the glass plate above the paperboards, placing the clean slurry fluidity test mold at the center of the glass plate, quickly injecting the mixed II slurry into the clean slurry fluidity test mold, leveling the slurry by using a scraper, lifting the clean slurry fluidity test mold in the vertical direction, starting a stopwatch to time at the same time, allowing the cement clean slurry to flow on the glass plate for 30s, taking the maximum diameter of the flowing part in two mutually perpendicular directions by using a ruler, and taking the average value as the cement clean slurry fluidity.

d) And (3) measuring the calculus rate: putting the slurry II into a measuring cylinder, and sealing the measuring cylinder; the reading was observed every 2min until the slurry stabilized. Water extraction = volume of clear water extracted (ml)/volume of slurry (ml), expressed as a percentage, calculus rate = 1-water extraction rate.

e) Quickly filling the prepared slurry II into a test mold (a cylinder with the thickness of 50mm multiplied by 100 mm), uniformly vibrating the slurry from outside to inside in a spiral direction by using a vibrating rod if necessary, inserting and tamping the slurry along the mold wall for a plurality of times by using a scraper so as to prevent air holes from possibly being left after inserting and tamping the slurry with low consistency, wherein the slurry is 6 mm-8 mm higher than the top surface of the test mold, and scraping the slurry by using a scraper; forming 2 groups of test pieces for each sample; curing (24 +/-2) hours under standard test conditions after molding, and then demolding; and then continuously maintaining the test piece in water at the temperature of (20 +/-1) DEG for 7 days, taking out the test piece, absorbing free water visible on the surface by using soft cloth, and measuring the compressive strength by using a pavement material strength tester.

The test results are given in the following table:

test of	Initial setting time/min	Final setting time/min	Fluidity/mm	Calculus rate/%	7d compressive strength/MPa
						Results	0.7	1.33	220	100	0.823

Compared with the above examples, the cement-water glass quick setting material has short initial setting and final setting time, but the 7d compressive strength does not meet the standard requirement, the fluidity is small, the slurry diffusion distance is short, and the slurry formed by mixing pure cement and pure water glass has high cost and has defects in performance; the modified sodium silicate quick-setting material is low in cost, comprehensive in function and excellent in performance, can adjust the gel time and strength better, can quickly cure and consolidate, improves the flow resistance of the leakage-stopping slurry, and reduces the slurry leakage.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. The modified sodium silicate quick-setting material is characterized in that: comprises a component A and a component B;

the component A comprises ordinary portland cement and fly ash, and the component B comprises ethylene glycol, adipic acid and water glass;

the component A comprises the following components: 40-70 parts of ordinary portland cement, 30-60 parts of fly ash and inevitable impurities;

the component B comprises the following components: 0.6-1 part of ethylene glycol, 1-1.4 parts of adipic acid, 97.6-98.4 parts of water glass and inevitable impurities.

2. The preparation method of the modified sodium silicate quick-setting material is characterized by comprising the following steps:

(1) and (3) putting the prepared component A into a stirrer for stirring, keeping the stirring speed at 60-100 r/min, stirring for 20-25 minutes, and stirring while mixing according to the mass ratio of water to solid of 1: 1, adding water, and stirring and mixing uniformly to obtain a mixture I;

(2) according to the water: the mass ratio of the component B is 1: 2, heating water to 60-70 ℃, sequentially adding the ethylene glycol material and the adipic acid material in the component B, stirring by using a glass rod until the adipic acid is completely dissolved to obtain a transparent and clear mixture II, and standing and maintaining;

(3) when the temperature of the mixture II is reduced to room temperature, adding the water glass in the component B according to a proportion, stirring with a glass rod, uniformly stirring to obtain a mixture III, standing and maintaining for 5-10 min;

(4) mixing the mixture I and the mixture III according to a volume ratio of 1: putting the mixture into a high-stirring cup together in a ratio of 0.4-0.6, performing high stirring for 5-10 s at a stirring speed of 100r/min, uniformly mixing to obtain a finished product IV, and immediately performing indoor test or on-site grouting.