CN110540212A - Low modulus sodium silicate solution and method for preparing same - Google Patents
Low modulus sodium silicate solution and method for preparing same Download PDFInfo
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Abstract
The invention relates to a low modulus sodium silicate solution and a preparation method thereof. The preparation method of the low modulus sodium silicate solution comprises the following steps: and (3) adding nano SiO2 particles into the NaOH solution at normal temperature, stirring and dispersing to obtain the low-modulus sodium silicate solution with the set modulus. The invention also provides an alkali-activated cementing material prepared by using the low-modulus sodium silicate solution prepared by the method as an activator. The invention is based on the principle that nano SiO2 particles are quickly dissolved in strong alkali solution at normal temperature to form monomer [ SiOn (OH)4-n ] n-, nano SiO2 particles play a role in quickly supplementing soluble silicon in the solution, and sodium silicate solution with the characteristics of low modulus, low viscosity and strong stability is quickly obtained. The low-modulus sodium silicate solution prepared by the preparation method can play the effect of the nano SiO2 particles to improve the performance of the alkali-activated cementing material no matter the low-modulus sodium silicate solution is ready to use after being prepared or stored for a long time.
Description
Technical Field
The invention relates to the technical field of water glass, in particular to a low-modulus sodium silicate solution and a preparation method thereof.
Background
The alkali activator is the most important component of the alkali-activated cementing material, and dissolves the silicon-aluminum raw material particles and releases silicon and aluminum monomers. The release process of silicon and aluminum monomers is a controlled process of silicon-aluminum polymerization reaction, so that the alkali activator has a crucial influence on the setting and hardening performance, the microstructure development and the performance development of the cementing material. Different raw materials have different requirements on the characteristics of the alkali-activator. For high calcium, high silicon and low aluminum raw materials such as slag, the high modulus (n ═ SiO2/Na2O) water glass solution not only can provide a proper alkaline environment, but also the supply of soluble silicon ((poly) silicate ions) is enough to ensure the smooth progress of silicon-aluminum polymerization reaction. For low-calcium, high-aluminum and high-silicon raw materials such as fly ash, a strong enough alkaline environment material is needed to release silicon and aluminum monomers, so a high-concentration NaOH solution is usually selected. However, the gelled material system prepared by using the fly ash as the raw material only has enough alkaline environment and is not enough to enable the fly ash to quickly release silicon and aluminum monomers at normal temperature, namely the fly ash is abnormally slow in setting and hardening at normal temperature. In order to increase the reaction speed, the curing temperature is generally increased to promote the setting hardening process, promote the formation of microstructures, and increase the strength. The method not only has high energy consumption, but also is only suitable for prefabricated parts, so that the development of normal-temperature maintenance technology is urgently needed.
In order to realize normal temperature curing, additional supplement of silicon monomer in the form of soluble silicon in a cementing material system is a feasible method. The source of soluble silicon may be a sodium silicate solution (water glass). For the cementing material prepared by taking the fly ash as the raw material, because a strong enough alkaline environment is needed, a proper water glass solution (prepared by adding NaOH into a high-modulus water glass solution and needing to be aged for 24 hours to reach the balance) is bound to have the characteristic of low modulus (n is less than 1.0). For low-modulus water glass, the water glass has the characteristics of strong alkali and ionic soluble silicon, is extremely unstable, and can generate crystallization and delamination after being placed for several days. Therefore, the low-modulus water glass as the excitant brings a plurality of uncertain factors to the preparation of the material and the performance regulation thereof, which is extremely unfavorable for industrial production. Therefore, alternatives to soluble silicon supply are also sought.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a low-modulus sodium silicate solution (water glass), and aims to solve the technical problems that the low-modulus sodium silicate solution is ready to use (does not need to be stored for a long time) and has improved stability (can be stored for a long time) when being prepared, and the low-modulus sodium silicate solution has the characteristics of strong alkali and rapid soluble silicon supply.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides a preparation method of a low-modulus sodium silicate solution, which comprises the following steps:
and (3) adding nano SiO2 particles into the NaOH solution at normal temperature, stirring and dispersing to obtain the low-modulus sodium silicate solution with the set modulus.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
preferably, the method for preparing the low modulus sodium silicate solution, wherein the nano SiO2 particles are added in an amount satisfying formula (1):
m＝30×c×V×n (1)
In the formula (1), the reaction mixture is,
m is the addition amount of nano SiO2 particles in NaOH solution, unit g;
c is the concentration of NaOH solution, unit mol/L;
V is the volume of NaOH solution, unit L;
n is a set modulus, where 0< n <1.
Preferably, in the preparation method of the low-modulus sodium silicate solution, the specific surface area of the nano SiO2 particles is 120-400 m2/g, and the particle size D0.5 is 7-200 nm.
Preferably, in the preparation method of the low-modulus sodium silicate solution, the nano SiO2 particles are hydrophilic nano SiO2 particles.
Preferably, in the preparation method of the low-modulus sodium silicate solution, the stirring is mechanical stirring, the rotating speed of the stirring is 500-900 r/min, and the time is 10-30 min; the dispersion is ultrasonic dispersion, which is carried out after mechanical stirring, and the dispersion time is 5-10 min.
preferably, in the preparation method of the low modulus sodium silicate solution, when the modulus n is set to be more than or equal to 0.6, the nano SiO2 particles are divided into two parts with similar mass and added in two parts, so as to avoid the problem of incapability of stirring caused by one-time addition.
the object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides a low-modulus sodium silicate solution prepared by the preparation method of any one of the above-mentioned materials.
Preferably, the low-modulus sodium silicate solution has a viscosity of 10 to 20mPa · s.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the alkali-activated cementing material provided by the invention, the low-modulus sodium silicate solution is used as an alkali activator.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the alkali-activated binding material, wherein the low modulus sodium silicate solution is a clear solution, does not need to be aged after mechanical stirring and ultrasonic dispersion, and can be immediately used for preparing the alkali-activated binding material.
by the technical scheme, the low-modulus sodium silicate solution and the preparation method thereof provided by the invention at least have the following advantages:
1. The preparation method of the invention is that a certain amount of nano SiO2 particles are added into NaOH solution at normal temperature, and the sodium silicate solution with low modulus can be obtained after mechanical stirring and ultrasonic dispersion, and can be prepared and used immediately without aging, and is simple and rapid.
2. In the preparation method, only partial particles of the nano SiO2 particles are dissolved in the ready-to-use low-modulus sodium silicate solution, so that the nano SiO2 particles can play a chemical role in providing soluble silicon, and undissolved particles can play a physical filling role and a crystal nucleus role of ultrafine particles, so that the preparation method has an obvious effect of improving the early strength of the alkali-activated binding material; for the low modulus sodium silicate solution that has been aged for a long time, the nano SiO2 particles have completely dissolved, when they only play a chemical role of "providing soluble silicon". Despite the lack of physical filling and nucleation, the soluble silicon is supplied in greater amounts, i.e., the chemical action is exerted more fully, and the strength of the alkali-activated cementitious material is also significantly increased. Therefore, the low-modulus sodium silicate solution prepared by the method can exert the effect of the nano SiO2 particles to improve the performance of the alkali-activated cementing material no matter the low-modulus sodium silicate solution is ready to use after being prepared or is stored for a long time.
3. The nano SiO2 particles added in the method have the characteristic of high activity, can quickly supplement high-activity silicon monomer ([ SiOn (OH)4-n ] n-) of a system, further can realize the preparation of the alkali-activated cementing material from high-silicon and high-aluminum raw materials (such as fly ash) under the normal temperature condition, avoids heating and maintenance, has remarkable energy-saving significance, and also expands the application range of the material (can be used for prefabricated parts and cast-in-place structures).
4. The low-modulus sodium silicate solution prepared by the preparation method disclosed by the invention has the characteristic of low viscosity, the viscosity of the low-modulus sodium silicate solution is 10-20 mPa & s, and the low-modulus sodium silicate solution can be stored for a long time due to the change of the supply state of soluble silicon, so that the low-modulus sodium silicate solution is obviously beneficial to industrial production and application of alkali-activated cementing materials.
5. the method has no influence on the pH value of the solution. The added nano SiO2 particles dissolve rapidly and provide monomers [ SiOn (OH)4-n ] n-, without polymerization, without changing the solution characteristics.
6. The invention is based on the principle that nano SiO2 particles are quickly dissolved in strong alkali solution at normal temperature to form monomer [ SiOn (OH)4-n ] n-, nano SiO2 particles play a role in quickly supplementing soluble silicon in the solution, and sodium silicate solution with the characteristics of low modulus, low viscosity and strong stability is quickly obtained.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a graph of the exotherm rate of a solution after the addition of nano-sized particles of SiO2 to a NaOH solution according to an embodiment of the present invention;
FIG. 2 is a graph showing the change of opacity of a NaOH solution containing nano-SiO 2 particles according to an embodiment of the present invention;
FIG. 3 is a viscosity change curve of a solution after nano SiO2 particles are added into a NaOH solution according to an embodiment of the invention;
FIG. 4 is a FTIR vibration characteristic curve of a solution after adding nano SiO2 particles in NaOH solution according to an embodiment of the present invention;
Figure 5 is a graph of the hydration exotherm rate for a low modulus sodium silicate solution-excited sample according to an embodiment of the present invention.
Detailed Description
to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects of the low modulus sodium silicate solution and the preparation method thereof according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The embodiment of the invention provides a preparation method of a low-modulus sodium silicate solution, which comprises the following steps:
and (3) adding nano SiO2 particles into the NaOH solution at normal temperature, stirring and dispersing to obtain the low-modulus sodium silicate solution with the set modulus.
In the embodiment of the invention, the addition amount of the nano SiO2 particles is determined according to the set modulus and the concentration of NaOH solution. Before the nano SiO2 particles are added, NaOH solution meeting the set water-cement ratio and concentration needs to be prepared in advance, so that the nano SiO2 particles are more favorably dispersed and quickly dissolved, the low viscosity is kept, the problem that the water in the solution is insufficient, extra water needs to be supplemented when the alkali-activated cementing material is formed is avoided, and the phenomenon that the solution is too high in viscosity and even becomes jelly-shaped and cannot be used due to the fact that the water in the solution is insufficient is avoided.
Preferably, the nano SiO2 particles are added in an amount satisfying formula (1):
m＝30×c×V×n (1)
in the formula (1), the reaction mixture is,
m is the addition amount of nano SiO2 particles in NaOH solution, unit g;
c is the concentration of NaOH solution, unit mol/L;
V is the volume of NaOH solution, unit L;
n is a set modulus, where 0< n <1.
it is important to note that the low modulus of the present invention is relative to current commercial products. The modulus of commercial products (water glass solution, i.e. water solution with dissolved sodium silicate) is usually 2.0-2.4 and 3.0-3.4, so the disclosed modulus range (0.0-1.0) is lower than that of commercial products.
in the embodiment of the invention, before the nano SiO2 particles are added, a NaOH solution meeting the set water-cement ratio of the alkali-activated cementing material and the required concentration of the alkali-activated cementing material is prepared. In general, 450g of powder raw materials are needed in an alkali-activated cementing material mortar experiment, and assuming that the water-cement ratio is gamma and the doping amount of the low-modulus sodium silicate solution is beta (%, in terms of the mass percentage of the Na2O content in the powder raw materials in the alkali-activated cementing material), the water demand m' (in g) for preparing the NaOH solution with the required concentration at the moment satisfies the formula (2):
m’＝450×γ (2)
in the formula (2), the reaction mixture is,
m' is the water demand of the NaOH solution with the required concentration, and the unit g is;
gamma is the set water-cement ratio (mass of water divided by mass of powder raw material) of the alkali-activated cement.
The desired concentration c of the NaOH solution satisfies formula (3):
c＝10×β/(31×γ) (3)
In the formula (3), the reaction mixture is,
c is the required concentration of NaOH solution, unit mol/L;
beta is the doping amount of the low-modulus sodium silicate solution, and is calculated by the mass percentage of the Na2O content in the powder raw material in the alkali-activated binding material;
gamma is the set water-cement ratio (mass of water divided by mass of powder raw material) of the alkali-activated cement.
Under the conditions of water demand and concentration, preparing (9 multiplied by gamma/20) L NaOH solution to meet the set water-cement ratio of the alkali-activated cementing material; the set modulus can be satisfied by adding (15X 9X beta X n/31) g of nano SiO2 particles into NaOH solution.
According to the method, the nano SiO2 particles are added into the NaOH solution, so that the sodium silicate solution with low modulus can be quickly obtained, and the sodium silicate solution has the characteristics of low viscosity and long-term storage.
In the method, for the low-modulus sodium silicate solution which is ready to be prepared, only partial particles of the nano SiO2 particles are dissolved, so that the chemical action of providing soluble silicon can be exerted, the undissolved particles can also exert the physical filling action and the crystal nucleus action of ultrafine particles, and the method has obvious effect on improving the early strength of the alkali-activated cementing material; for the low modulus sodium silicate solution that has been aged for a long time, the nano SiO2 particles have completely dissolved, when they only play a chemical role of "providing soluble silicon". Despite the lack of physical filling and nucleation, the soluble silicon is supplied in greater amounts, i.e., the chemical action is exerted more fully, and the strength of the alkali-activated cementitious material is also significantly increased. Therefore, no matter the low-modulus sodium silicate solution is prepared and used immediately or stored for a long time, the nano SiO2 particles can exert the effect to improve the performance of the alkali-activated cementing material.
The nano SiO2 particles added in the method have the characteristic of high activity, and can quickly supplement high-activity silicon monomer ([ SiOn (OH)4-n ] n-) of the system, thereby realizing the preparation of alkali-activated cementing material from high-silicon and high-aluminum raw materials (such as fly ash) under the condition of normal temperature and avoiding heating and maintenance. The method has no influence on the pH value of the solution. The added nano SiO2 particles dissolve rapidly and provide monomers [ SiOn (OH)4-n ] n-, without polymerization, without changing the solution characteristics.
Compared with the existing commercial products, the sodium silicate solution with the modulus of less than or equal to 0.5 (0< n ≦ 0.5) is called the ultra-low modulus sodium silicate solution in the embodiment of the invention. The method has more outstanding advantages in preparing the sodium silicate solution with the ultralow modulus and n less than or equal to 0.5: based on the principle that nano SiO2 particles are quickly dissolved in a normal-temperature strong alkali solution to form a monomer [ SiOn (OH)4-n ] n-, nano SiO2 particles play a role in quickly supplementing soluble silicon in the solution, and the sodium silicate solution with the characteristics of ultralow modulus, ultralow viscosity and strong stability is quickly obtained.
Preferably, the specific surface area of the nano SiO2 particles is 120-400 m2/g, and the particle size D0.5 is 7-200 nm.
Preferably, the nano SiO2 particles are hydrophilic nano SiO2 particles.
Preferably, the stirring is mechanical stirring, the rotating speed of the stirring is 500-900 r/min, and the time is 10-30 min; the dispersion is ultrasonic dispersion, which is carried out after mechanical stirring, and the dispersion time is 5-10 min.
Preferably, when the modulus n is more than or equal to 0.6, the nano SiO2 particles are divided into two parts with similar mass and added in two times, so as to avoid the problem of incapability of stirring caused by one-time addition.
The embodiment of the invention also provides a low-modulus sodium silicate solution which is prepared by the preparation method at normal temperature.
In the embodiment of the invention, the preparation method of the low-modulus sodium silicate solution is simple and quick, is carried out at normal temperature, is ready to use after preparation, and does not need to be stored for a long time to balance.
The invention adopts the function of 'providing the compensating soluble silicon' of the high-activity nano SiO2, so that the obtained low-modulus sodium silicate solution has the characteristics of high activity, low viscosity and good stability.
The low-modulus sodium silicate solution of the invention not only has the characteristic of ultra-low viscosity, but also can be stored for a long time due to the change of the supply state of the soluble silicon, which is obviously beneficial to the industrial production and application of the alkali-activated cementing material.
Preferably, the viscosity of the low-modulus sodium silicate solution is 10-20 mPas.
The embodiment of the invention also provides an alkali-activated cementing material, which takes the low-modulus sodium silicate solution as an alkali activator, takes the low-modulus sodium silicate solution as a clear solution, does not need to be aged after mechanical stirring and ultrasonic dispersion, and can be immediately used for preparing the alkali-activated cementing material
The principle of the invention is as follows: under the condition of normal temperature, the nano SiO2 particles can be dissolved in a strong alkali solution, the NaOH solution is a strong alkali solution, and the nano SiO2 particles can be quickly dissolved in the strong alkali solution. The exotherm rate curve for the addition of 0.03g of nano-sized SiO2 particles to 2.2g of NaOH solution (containing 0.2g of Na2O +2.0g of water) was determined using a microcalorimeter, as shown in FIG. 1. The results show that the solution has a significant long-time exothermic process in the environment of 20 ℃, which indicates that the nano SiO2 particles and the NaOH solution have a certain chemical process. According to its exothermic history, the explanation is as follows: the surface of the hydrophilic nano SiO2 particle is wetted by water to release heat, and the violent heat release lasting for tens of minutes in the first stage is shown; the hydrophilic nano SiO2 particles dissolve in the solution and release heat, releasing soluble silicon and forming [ SiOn (OH)4-n ] n-, which shows a slow heat release lasting for hours in the second stage. The above exothermic behavior confirmed that the nano SiO2 particles were soluble in NaOH solution. The process is long, but the nano SiO2 particles exert their modifying effect whenever a formulated low modulus sodium silicate solution is used. If the nano SiO2 particles are used immediately, the nano SiO2 particles are only partially dissolved in the solution, and the chemical action of providing solubility and the physical filling action and the crystal nucleus action of the superfine particles can be simultaneously exerted; if the nano SiO2 particles are used after long-term aging, the nano SiO2 particles in the solution are completely dissolved, and the chemical effect of providing solubility can be exerted to the maximum extent.
The dissolution characteristics of the nano SiO2 particles in the NaOH solution can be further verified by using a laser particle size analyzer. The dissolution characteristic of the nano SiO2 particles is characterized by the parameter of the opacity of a laser particle sizer. The light-shielding degree refers to the optical concentration of the particles in the solution, and when the particles are finer and more well dispersed, the light-shielding degree of the solution is higher on the premise that the same mass of particles is added. The nano SiO2 particles have small size reaching the nanometer level, and when the nano SiO2 particles are added into a solution in a small amount and are subjected to ultrasonic dispersion, the light shading degree of the solution is close to 20 percent quickly. If the nano SiO2 is always dispersed in the solution in the form of particles, the light shielding degree of the solution is maintained at about 20%. The change curve of the opacity of the solution after adding nano SiO2 particles to the NaOH solution is shown in FIG. 2. The results show that the opacity of the solution drops rapidly within a few tenths of a minute, which means dissolution of the nano SiO2 particles; the shade then slowly diminishes and this trend is maintained to hundreds of minutes, which indicates that the nano SiO2 particles gradually dissolve; after a sufficiently long time (200 minutes) the opacity has decreased from the initial about 20% to about 1%, indicating that again during this time most of the nano-SiO 2 particles have dissolved. The duration of this process is almost identical to the duration of the exotherm of the addition of the nano SiO2 particles to the NaOH solution, which again indicates the solubility of the nano SiO2 particles in the NaOH solution, i.e. the nano SiO2 particles in this solution can indeed act to provide soluble silicon.
The dissolution process of the nano SiO2 particles is necessarily accompanied by the change of the viscosity of the solution. If the nano SiO2 is in a granular state, the solution viscosity is inevitably increased remarkably due to the hydrophilic property; the viscosity must drop significantly if it dissolves and becomes a component of the solution. The change curve of the solution viscosity after adding nano SiO2 particles into NaOH solution is shown in FIG. 3. The results show that the change rule of the viscosity of the solution after adding the nano SiO2 at normal temperature accords with the conjecture, and the solution changes from a turbid state to a clear state, the viscosity is close to that of the initial solution, which again shows the soluble characteristic of the nano SiO2 particles, and the solution viscosity is hardly influenced.
Based on the dissolubility of the nano SiO2 particles in the normal-temperature NaOH solution, the invention designs a scheme for preparing the low-modulus sodium silicate solution by adding the nano SiO2 particles in the NaOH solution. The low-modulus sodium silicate solution can be quickly obtained at normal temperature, and has the characteristics of high activity, low viscosity and high stability.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
Example 1
adding nano SiO2 particles into NaOH solution to prepare low-modulus sodium silicate solution with modulus of 0.15, 0.30 and 0.45.
assuming that the water-cement ratio of the alkali-activated cement is 0.5 and the amount of the exciting agent is 6.813% (based on the mass percentage of the Na2O in the powder raw material in the alkali-activated cement, the same applies below), the solution parameters required for meeting 450g of the powder raw material are prepared, and are shown in Table 1.
TABLE 1 parameters for formulating low modulus sodium silicate solutions with modulus of 0.15, 0.30, 0.45
| water/g | Required NaOH solution concentration/(mol/L) | volume of NaOH solution required/L | 2Nano SiO2/g | Modulus of elasticity |
| 225 | 4.40 | 0.225 | 4.45 | 0.15 |
| 225 | 4.40 | 0.225 | 8.90 | 0.30 |
| 225 | 4.40 | 0.225 | 13.35 | 0.45 |
Nano SiO2 particles: hydrophilic type, particle size 7-40nm (D0.5 ═ 14nm), specific surface area 400m 2/g.
Water: 225g of tap water.
NaOH: 39.56g, technical grade flake caustic.
NaOH solution: dissolving flake caustic soda in 225g of water, stirring, sealing and cooling to obtain a NaOH solution with the concentration of 4.40 mol/L.
At normal temperature, respectively adding 4.45g, 8.90g and 13.35g of nano SiO2 particles into NaOH solution, mechanically stirring for 10min under the condition of the rotation speed of 500r/min, and then ultrasonically dispersing for 5min to obtain low-modulus sodium silicate solution for later use.
FTIR spectrum results show the effect of nanometer SiO2 particles in providing soluble silicon. The variation curve of FTIR vibration characteristics after adding nano SiO2 particles in NaOH solution is shown in FIG. 4. As a result, when the nano SiO2 particles were added into the NaOH solution, the characteristic vibration band of O-Si-O (1108cm-1) and the characteristic vibration band of Si-OH (810cm-1) disappeared, indicating that the nano SiO2 particles were dissolved in the solution. The NaOH solution added with the nano SiO2 particles has an obvious vibration band at the wave number of 1000cm < -1 >, which is the vibration of O-Si-O corresponding to the nano SiO2 particles after being dissolved into [ SiOn (OH)4-n ] n < - >. Compared with sodium silicate solutions with the modulus of 0.15, 0.30 and 0.45, the three solutions have almost no obvious difference, which shows that the nano SiO2 particles can be dissolved in the solution no matter the amount of the nano SiO2 particles is added, and the provided soluble silicon has no difference.
the above results demonstrate that a rapid preparation of low modulus sodium silicate solution using the "soluble silicon" effect of nano SiO2 particles is feasible.
And preparing a mortar sample of the alkali-activated cementing material by using a NaOH solution and the sodium silicate solution as exciting agents. When the mixing amount of the NaOH solution and the sodium silicate solution is 0.225L, the water-cement ratio of the mortar sample is just 0.5, and the dosage of the exciting agent is just 6.813%.
The fly ash and the slag powder are used as raw materials, and NaOH solution and the sodium silicate solution are respectively used as exciting agents to prepare the alkali-excited cementing material. The cementing material comprises the following components in percentage by weight: 90 percent of fly ash and 10 percent of slag powder (the specific surface area is 405m2/kg, the same below) are taken as powder raw materials.
Samples were prepared and tested for strength according to the cement mortar strength test method (ISO method) (GB/T17671), but the curing conditions were room temperature humid air (RH 95 ± 5%). The results of comparing the effects of NaOH solution and sodium silicate solution with modulus of 0.15, 0.30, 0.45 as the activator are shown in Table 2.
If the cementing material with the proportion takes a low-concentration (less than or equal to 3.0mol/L) NaOH solution as an excitant, the cementing material coagulates abnormally slowly at normal temperature, almost has no strength in the early stage, and the strength in the later stage does not exceed 10.0 MPa. Therefore, the concentration and the doping amount of the NaOH solution need to be increased. When the NaOH solution is more than or equal to 4.0mol/L and the doping amount is more than 5 percent, the sample can be normally condensed at normal temperature, and the sample has enough strength in early and later periods.
TABLE 2 comparison of the effects of NaOH solution and the sodium silicate solution described above as an activator
note: the modulus is 0, namely the excitant is NaOH solution
as is clear from Table 2, the 3-day strength and the 28-day strength of the sodium silicate solutions having moduli of 0.15, 0.30 and 0.45 as the trigger were improved as compared with those of the NaOH solutions, and the moduli increased gradually. This is due to the effect of the nano SiO2 particles in providing soluble silicon, which not only promotes the early strength development, but also significantly improves the later strength. For example, when sodium silicate solution with the modulus of 0.45 is used as an exciting agent, the compressive strength of a 28-day sample is improved by 17.1MPa compared with that of a NaOH solution excited sample, and the improvement range is obvious.
Example 2
example 1 demonstrates the solubility of nano-SiO 2 particles in terms of structural characteristics and its effectiveness in providing soluble silicon. Example 2 will expand the modulus range and further verify the modification effect of nano-SiO 2 particles on NaOH solution.
Nano SiO2 particles: hydrophilic type, particle size 16-50nm (D0.5 ═ 30nm), specific surface area 290m 2/g.
Water: 225g of tap water.
NaOH: 39.56g, technical grade flake caustic.
NaOH solution: dissolving flake caustic soda in 225g of water, stirring, sealing and cooling to obtain a NaOH solution with the concentration of 4.40 mol/L.
at normal temperature, 14.83g, 17.80g, 20.77g, 23.74g, 26.70g and 29.67g of nano SiO2 particles are respectively added into 0.225L of the NaOH solution, mechanically stirred for 30min under the condition of the rotating speed of 700r/min, and then ultrasonically dispersed for 10min to obtain sodium silicate solutions with the modulus of 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 for later use. Because the addition amount of the nano SiO2 particles is increased, the mechanical stirring is properly accelerated, and the stirring and ultrasonic time is prolonged.
it should be noted that when preparing sodium silicate solution with modulus of 0.7, 0.8, 0.9, 1.0, the nano SiO2 particles are added in two times, specifically as follows:
Sodium silicate solution with modulus 0.7: adding 10.77g of nano SiO2 particles for the first time, mechanically stirring for 30min under the condition that the rotating speed is 700r/min, and then ultrasonically dispersing for 10 min; immediately adding 10.00g of nano SiO2 particles after obtaining the clear solution, mechanically stirring for 30min under the condition of the rotating speed of 700r/min, and then ultrasonically dispersing for 10 min.
Sodium silicate solution with modulus 0.8: 12.74g of nano SiO2 particles are added for the first time, mechanically stirred for 30min under the condition that the rotating speed is 700r/min, and then ultrasonically dispersed for 10 min; immediately adding 11.00g of nano SiO2 particles after obtaining the clear solution, mechanically stirring for 30min under the condition of the rotating speed of 700r/min, and then ultrasonically dispersing for 10 min.
Sodium silicate solution with modulus 0.9: adding 13.70g of nano SiO2 particles for the first time, mechanically stirring for 30min under the condition that the rotating speed is 700r/min, and then ultrasonically dispersing for 10 min; and immediately adding 13.00g of nano SiO2 particles after obtaining the clear solution, mechanically stirring for 30min under the condition of the rotating speed of 700r/min, and then ultrasonically dispersing for 10 min.
Sodium silicate solution with modulus 1.0: adding 15.67g of nano SiO2 particles for the first time, mechanically stirring for 30min under the condition that the rotating speed is 700r/min, and then ultrasonically dispersing for 10 min; after obtaining the clear solution, 14.00g of nano SiO2 particles are added immediately, mechanically stirred for 30min under the condition of the rotating speed of 700r/min, and then ultrasonically dispersed for 10 min.
When the mixing amount of the NaOH solution and the sodium silicate solution is 0.225L, the water-cement ratio of the mortar sample is just 0.5, and the dosage of the exciting agent is just 6.813%.
The fly ash and the slag powder are used as raw materials, and NaOH solution and the sodium silicate solution are respectively used as exciting agents to prepare the alkali-excited cementing material. The cementing material comprises the following components in percentage by weight: 90 percent of fly ash and 10 percent of slag powder (the specific surface area is 405m2/kg, the same below) are taken as powder raw materials. The hydration heat release process of the gelled material was observed by a microcalorimeter and the results are shown in fig. 5. From the hydration exothermic results, it is understood that when NaOH solution is used as the activator, only the first distinct exothermic peak corresponding to wetting and dissolution is observed, while the characteristic exothermic (second exothermic peak) corresponding to the alkali-activated reaction (silicoalumina polymerization reaction) is not distinct, i.e., the hydration process is slow, which is the main reason for the low strength of the sample. When a sodium silicate solution with low modulus is used as an activator, an exothermic peak (a second exothermic peak) which is characteristic of the alkali-activated reaction is gradually obvious, and the reaction is obviously promoted by soluble silicon provided by the nano SiO2 particles.
Samples were prepared and tested for strength according to method for testing cement mortar strength (ISO method) (GB/T17671), but the curing conditions were room temperature humid air (RH 95 ± 5%), and the results are shown in table 3.
TABLE 3 comparison of the effects of NaOH solution and sodium silicate solution with modulus of 0.5-1.0 as activator
Note: the modulus is 0, namely the excitant is NaOH solution
As can be seen from table 3, as the modulus increases, the 3-day strength and the 28-day strength of the sample gradually increase, which indicates that the soluble silicon provided by the nano SiO2 particles has more and more obvious effect on the strength increase, which indicates that the method for preparing the low-modulus sodium silicate solution by dissolving the nano SiO2 particles in the NaOH solution is feasible.
Example 3
In order to further verify the effectiveness of the method, the excitation effect of the water glass solution obtained by the traditional method and the sodium silicate solution obtained by the method are compared, and the parameters such as viscosity, pH value and the like are compared.
(1) Obtaining low-modulus water glass solution by traditional method
The modulus is adjusted from high to low by adding caustic soda flakes for cooking.
initial water glass solution: the modulus was 2.4, the solids content was 45.7%, the pH was 12.8 and the viscosity was 345 mPas.
To 100g of an initial water glass solution having a modulus of 2.4, 24.84g of flake caustic and 102.5g of water were added, stirred, sealed, boiled, cooled and aged for 24 hours. The adjusted water glass solution had a solid content of 28.6% and a modulus of 1.0. When the adjusted water glass solution is used as an excitant of the alkali-activated cementing material, when the addition amount is 20% (calculated by the mass percentage of the solid in the powder, the conversion is Na2O, and the addition amount is 10.16%), the water-cement ratio of a cementing material mortar sample is just 0.5.
(2) the method of the invention obtains the water glass solution with low modulus
Nanometer SiO2 particles are added into NaOH solution, and the modulus is adjusted to be higher than zero.
Nano SiO2 particles: hydrophilic type, particle size 150-.
Water: 225g of tap water.
NaOH: 58.99g, technical grade flake caustic soda.
NaOH solution: dissolving flake caustic soda in 225g of water, stirring, sealing and cooling to obtain a NaOH solution with the concentration of 6.55 mol/L.
At normal temperature, 22.25g of nano SiO2 particles are added for the first time, mechanically stirred for 30min under the condition that the rotating speed is 900r/min, and then ultrasonically dispersed for 10 min; immediately adding 22.00g of nano SiO2 particles after obtaining the clear solution, mechanically stirring for 30min under the condition of the rotation speed of 900r/min, and then ultrasonically dispersing for 10 min. A clear solution was obtained for use.
The fly ash and the slag powder are used as raw materials, and the water glass solution obtained by the traditional method and the sodium silicate solution obtained by the method are respectively used as an exciting agent to prepare the alkali-excited cementing material. The cementing material comprises the following components in percentage by weight: 90 percent of fly ash and 10 percent of slag powder (the specific surface area is 405m2/kg, the same below) are taken as powder raw materials. 450g of powder (containing 360g of fly ash and 90g of mineral powder) and samples were prepared and tested according to the cement mortar strength test method (ISO method) (GB/T17671), but the curing conditions were room temperature humid air (RH 95 ± 5%).
When 314.7g of a water glass solution having a modulus of 1.0 obtained by a conventional method was incorporated, the amount of alkali carried in was 45.84g (in terms of Na2O), the amount of silicon carried in was 44.26g (in terms of SiO 2), the amount of water carried in was 225g, and the water-to-ash ratio of the sample was exactly 0.5.
When 0.225L of the sodium silicate solution having a modulus of 1.0 obtained by the process of the present invention was incorporated, the amount of alkali carried in was 45.72g (calculated as Na2O), the amount of silicon carried in was 44.25g (calculated as SiO 2), the amount of water carried in was 225g, and the water-to-ash ratio of the sample was exactly 0.5.
it can be seen that the two different activators have a consistent liquid phase environment, which sets a reliable boundary condition for the comparison of the effects of the present example.
the results of comparison and solution parameters for NaOH solution, initial water glass solution with modulus 2.4, cooked water glass solution with modulus 1.0 and sodium silicate solution of the invention as an activator are shown in table 4.
TABLE 4 comparison of the effects of NaOH solution and the sodium silicate solution described above as activators with solution parameters
Note: "/" indicates that the OH-concentration is above the pH indicating range and is strongly basic. The water-cement ratio was 0.5 for all samples, and the amount of reduction of the exciting agent was kept uniform, so as to compare the exciting effects.
As can be seen from table 4, the low modulus sodium silicate solution obtained by the present invention (the latter) has more excellent excitation effect than the low modulus water glass solution obtained by cooking (the former): the intensity of the latter sample excited in 3 days and 28 days is much higher than that of the former sample excited in the former. The latter is less viscous because the former is obtained by high modulus adjustment to low modulus, with the silicon portion contained remaining in a highly polymerized state, while the latter is obtained by dissolution of nano-SiO 2 particles, mainly in the presence of highly reactive monomers ([ SiOn (OH)4-n ] n-). In addition, the OH concentration in the latter is already outside the range that can be characterized by the pH value, i.e. the solution exists in an ionic state, which can provide stronger alkalinity, which is obviously beneficial to alkali-activated reaction; the former still retains the polymerization state characteristic, so the alkalinity can be represented by pH value, namely, the alkalinity is weaker than the latter, the excitation effect is correspondingly poorer than the latter, and the strength of the sample at each age is lower. In addition to the influence of the strong and weak alkalinity, the latter can provide more highly reactive monomers ([ SiOn (OH)4-n ] n-), while the former has limited monomer providing capability due to the high polymerization characteristics, which is another reason for the low strength of the excited sample at each stage.
Compared with the initial water glass solution with the modulus of 2.4 (the former), the low-modulus sodium silicate solution obtained by the invention (the latter) has the advantages that the compressive strength of the excited sample is lower than that of the former excited sample, but the flexural strength is higher, and the effect that the matrix is filled with partial undissolved nano SiO2 particles to play a toughening role is achieved. It can be seen that the method of the present invention not only exerts a chemical effect of providing high-activity silicon, but also exerts a physical filling effect which is not negligible. It should be noted that the reason why the former excited sample has higher compressive strength than the latter excited sample is: although the former is in a highly polymerized character, it is generally able to provide more soluble silicon, after all with a silicon content of 2.4 times that of the latter.
The low modulus sodium silicate solution obtained by the present invention (the latter) not only shows stronger excitation effect, but also has similar solution properties such as viscosity, compared to NaOH solution (the former).
The above comparison results confirm the feasibility of the process of the invention and confirm that the low modulus sodium silicate solution obtained by the invention has the characteristics of high activity, low viscosity and strong basicity.
Example 4
This example will illustrate the effect of aging on the excitation effect, solution characteristics of the low modulus sodium silicate solution obtained in the present invention.
Nano SiO2 particles: hydrophilic type, particle size 40-100nm (D0.5 ═ 72nm), specific surface area 275m 2/g.
Water: 225g of tap water.
NaOH: 39.56g, technical grade flake caustic.
NaOH solution: dissolving flake caustic soda in 225g of water, stirring, sealing and cooling to obtain a NaOH solution with the concentration of 4.40 mol/L.
At normal temperature, 14.83g of nano SiO2 particles are added, mechanical stirring is carried out for 10min under the condition that the rotating speed is 500r/min, and ultrasonic dispersion is carried out for 5min to obtain a clear solution with the modulus of 0.5 for later use.
When the mixing amount of the sodium silicate solution is 0.225L, the water-cement ratio of the mortar sample is just 0.5, and the dosage of the exciting agent is just 6.813%.
The aging time of the solution is 0min, 60min, 120min, 240min, 480min, 960min, 1920min, 3840min, 7680min and 259200min respectively.
The alkali-activated cementing material is prepared by taking fly ash and slag powder as raw materials and the sodium silicate solution aged for different times as an activator. The cementing material comprises the following components in percentage by weight: 90 percent of fly ash and 10 percent of slag powder (the specific surface area is 405m2/kg, the same below) are taken as powder raw materials. Samples were prepared and tested for strength according to the cement mortar strength test method (ISO method) (GB/T17671), but the curing conditions were room temperature humid air (RH 95 ± 5%). The comparison of the excitation effect and the change of the solution parameters after the sodium silicate solution with the modulus of 0.5 is aged for different times is shown in table 5.
TABLE 5 comparison of excitation effects and solution parameter changes after aging for different periods of time
Note: "/" indicates that the OH-concentration is above the pH indicating range and is strongly basic. 259200min is 180 days long.
As can be seen from Table 5, the solution was clear even after aging for a long period of time (7680min, about 5 days), and no demixing and clouding were observed. The solution was left to stand for a maximum of 259200min (180 days), the appearance characteristics of which remained unchanged. The above phenomena show that the low modulus sodium silicate solution obtained by the present invention has excellent stability and can be stored for a long time. Typically, the shelf life of cementitious materials such as cement does not exceed six months. Therefore, the low modulus sodium silicate solution obtained by the invention meets the requirement of the preparation period of the building industry.
As is clear from the results in Table 5, the solution showed no significant change in properties such as excitation effect and viscosity regardless of the aging time. When the sample is aged for a short time, although the nano SiO2 particles can not be completely dissolved, namely can not be completely converted into soluble silicon, the undissolved particles play the role of physical filling and crystal nucleus of ultrafine particles, and can make up the defect that chemical effect can not be completely played to a certain extent, so that the sample still shows the strength equivalent to that of the sample excited by the aged solution for a long time; when left standing for a long time, the nano SiO2 particles are almost completely dissolved, and at this time the chemical effect thereof to provide soluble silicon is fully exerted, and accordingly the specimen exhibits sufficiently high strength. The solution viscosity is higher than that of the solution aged for a long time just because the solution is aged for a short time and the nano SiO2 particles are partially undissolved in the solution. With the aging time, the nano SiO2 particles are gradually dissolved, and the viscosity of the solution is gradually reduced and maintained at a proper level.
The results show that the low-modulus sodium silicate solution obtained by the invention has excellent stability and the shelf life can reach 6 months.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing a low modulus sodium silicate solution, comprising:
And (3) adding nano SiO2 particles into the NaOH solution at normal temperature, stirring and dispersing to obtain the low-modulus sodium silicate solution with the set modulus.
2. The method for preparing a low modulus sodium silicate solution according to claim 1,
The addition amount of the nano SiO2 particles satisfies formula (1):
m＝30×c×V×n (1)
In the formula (1), the reaction mixture is,
m is the addition amount of nano SiO2 particles in NaOH solution, unit g;
c is the concentration of NaOH solution, unit mol/L;
V is the volume of NaOH solution, unit L;
n is a set modulus, where 0< n <1.
3. The method for preparing a low modulus sodium silicate solution according to claim 1,
The specific surface area of the nano SiO2 particles is 120-400 m2/g, and the particle size D0.5 is 7-200 nm.
4. The method for preparing a low modulus sodium silicate solution according to claim 1,
The nano SiO2 particles are hydrophilic nano SiO2 particles.
5. the method for preparing a low modulus sodium silicate solution according to claim 1,
The stirring is mechanical stirring, the rotating speed of the stirring is 500-900 r/min, and the time is 10-30 min; the dispersion is ultrasonic dispersion, which is carried out after mechanical stirring, and the dispersion time is 5-10 min.
6. The method for preparing a low modulus sodium silicate solution according to claim 1,
When the modulus n is set to be more than or equal to 0.6, the nano SiO2 particles are divided into two parts with similar mass and added in two times, so as to avoid the problem that stirring cannot be carried out due to one-time addition.
7. A low modulus sodium silicate solution, characterized in that it is prepared by the method of any one of claims 1 to 6.
8. The low modulus sodium silicate solution according to claim 7, wherein the viscosity of said low modulus sodium silicate solution is 10 to 20 mPa-s.
9. An alkali-activated cementitious material, characterised in that it uses as alkali activator the low modulus sodium silicate solution according to claim 7 or 8.
10. The alkali-activated cementitious material of claim 9, wherein the low modulus sodium silicate solution is a clear solution that can be used immediately to prepare the alkali-activated cementitious material without the need for aging after mechanical agitation and ultrasonic dispersion.
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