CN110540212B - 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. Preparation of the low modulus sodium silicate solutionThe preparation method comprises the following steps: adding nano SiO into NaOH solution at normal temperature2And (4) stirring and dispersing the particles 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 nano SiO2The particles are quickly dissolved in strong alkali solution at normal temperature to form a monomer SiOn(OH)4‑n]n‑Principle of (1), nano SiO2The particles play a role in quickly supplementing soluble silicon in the solution, and quickly obtain the sodium silicate solution with the characteristics of low modulus, low viscosity and strong stability. The low modulus sodium silicate solution prepared by the preparation method of the invention can be used immediately after preparation or can be stored for a long time, and the nano SiO2The particles can exert their effect to improve the properties of the alkali-activated cementitious material.
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, high modulus (n ═ SiO)2/Na2O) water glass solution not only provides proper alkaline environment, but also supplies soluble silicon ((poly) silicate ion) enough to ensure the silica-alumina polymerization reaction to proceed smoothly. 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 taking fly ash as a raw material only has enough alkaline environment and is not enough to rapidly release silicon and aluminum monomers at normal temperature, namelyIts setting and hardening is extremely slow 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:
adding nano SiO into NaOH solution at normal temperature2And (4) stirring and dispersing the particles 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 aforementioned low modulusMethod for preparing sodium silicate solution, wherein the nano SiO2The addition amount of the particles satisfies formula (1):
m＝30×c×V×n (1)
in the formula (1), the reaction mixture is,
m is nano SiO in NaOH solution2The addition of the particles, in 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, the method for preparing the low modulus sodium silicate solution, wherein the nano SiO is2The specific surface area of the particles is 120-400 m2(ii)/g, the particle size D0.5 is 7 to 200 nm.
Preferably, the method for preparing the low modulus sodium silicate solution, wherein the nano SiO is2The particles are hydrophilic nano SiO2And (3) granules.
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, the preparation method of the low modulus sodium silicate solution is that when the modulus n is more than or equal to 0.6, the nano SiO is mixed2The particles are divided into two parts with similar mass and added in two times, so as to avoid the problem that the particles cannot be stirred due to 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 SiO is added into NaOH solution at normal temperature2The low-modulus sodium silicate solution can be obtained after the particles are mechanically stirred and ultrasonically dispersed, and can be prepared and used immediately without being aged, so that the method is simple and rapid.
2. The preparation method of the invention is used for preparing the ready-to-use low-modulus sodium silicate solution, namely nano SiO2Only part of the particles are dissolved, so that the particles can play a chemical role of providing soluble silicon, and the undissolved particles can play a physical filling role and a crystal nucleus role of ultrafine particles, so that the early strength of the alkali-activated cementing material is obviously improved; for low modulus sodium silicate solutions that have been aged for long periods of time, nano SiO2The particles have completely dissolved, at which point 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 be used for preparing the nano SiO whether the solution is ready to use or long-term aging2The particles can exert their effect to improve the properties of the alkali-activated cementitious material.
3. The nano SiO added in the method of the invention2Particles of highly reactive silicon monomer ([ SiO ] with high reactivity characteristics capable of rapidly replenishing the systemn(OH)4-n]n-) Further, the alkali-activated cementing material can be prepared from high-silicon and high-aluminum raw materials (such as fly ash) at normal temperatureHeating maintenance is avoided, so that the material not only has remarkable energy-saving significance, but 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. Added nano SiO2The particles dissolve rapidly and provide the monomer [ SiO ]n(OH)4-n]n-No polymerization and no change in solution characteristics.
6. The invention is based on nano SiO2The particles are quickly dissolved in strong alkali solution at normal temperature to form a monomer SiOn(OH)4-n]n-Principle of (1), nano SiO2The particles play a role in quickly supplementing soluble silicon in the solution, and quickly obtain the sodium silicate solution with the characteristics of low modulus, low viscosity and strong stability.
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 shows the addition of nano SiO in NaOH solution according to the embodiment of the present invention2Heat release rate profile of the solution after granulation;
FIG. 2 shows the embodiment of the present invention in which nano SiO is added to NaOH solution2Change curve of shading degree of solution after granulation;
FIG. 3 shows the addition of nano SiO in NaOH solution according to the embodiment of the present invention2Viscosity profile of the post-granulation solution;
FIG. 4 shows the addition of nano SiO in NaOH solution according to the embodiment of the present invention2FTIR vibrational characteristic profiles of the post-particulate solution;
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:
adding nano SiO into NaOH solution at normal temperature2And (4) stirring and dispersing the particles to obtain the low-modulus sodium silicate solution with the set modulus.
In the embodiment of the invention, the nano SiO2The amount of the pellets added is determined by the set modulus and the concentration of the NaOH solution. After adding nano SiO2Before granulation, NaOH solution meeting the set water-cement ratio and concentration needs to be prepared in advance, which is more beneficial to nano SiO2The particles are dispersed and rapidly dissolved and the viscosity is kept low, so that the problem that the water in the solution is insufficient and additional water needs to be supplemented when the alkali-activated cementing material is formed is avoided, and the problem that the water in the solution is insufficient and the solution is too high in viscosity and even in a jelly shape to be used is avoided.
Preferably, the nano SiO2The addition amount of the particles satisfies formula (1):
m＝30×c×V×n (1)
in the formula (1), the reaction mixture is,
m is nano SiO in NaOH solution2The addition of the particles, in 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, the nano SiO is added2Before granulation, 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. Generally, 450g of powder raw material is needed in alkali-activated cementing material mortar experiments, and the mixing amount of the low-modulus sodium silicate solution is beta (%, Na thereof is used) on the assumption that the water-cement ratio is gamma2The content of O accounts for the mass percent of the powder raw materials in the alkali-activated cementing material), the water demand m' (unit g) of the NaOH solution with the required concentration prepared at the moment meets 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, expressed as percent, and is expressed by Na2The content of O accounts for the mass percentage of the powder raw material in the alkali-activated cementing 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; adding (15 × 9 × β × n/31) g of nano SiO into NaOH solution2The particles can meet the set modulus.
The method adds nano SiO into NaOH solution2Granular, rapidly obtainable low modulus sodium silicate solutionsIt has the characteristics of low viscosity and long-term storage.
For the ready-to-use low-modulus sodium silicate solution, nano SiO in the method2Only part of the particles are dissolved, so that the particles can play a chemical role of providing soluble silicon, and the undissolved particles can play a physical filling role and a crystal nucleus role of ultrafine particles, so that the early strength of the alkali-activated cementing material is obviously improved; for low modulus sodium silicate solutions that have been aged for long periods of time, nano SiO2The particles have completely dissolved, at which point 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 can be prepared and used immediately or stored for a long time, and the nano SiO2The particles can exert their effect to improve the properties of the alkali-activated cementitious material.
The nano SiO added in the method of the invention2Particles of highly reactive silicon monomer ([ SiO ] with high reactivity characteristics capable of rapidly replenishing the systemn(OH)4-n]n-) Further, the alkali-activated cementing material can be prepared from high-silicon and high-aluminum raw materials (such as fly ash) at normal temperature, and heating maintenance is avoided. The method has no influence on the pH value of the solution. Added nano SiO2The particles dissolve rapidly and provide the monomer [ SiO ]n(OH)4-n]n-No polymerization and no change in solution characteristics.
The examples of the present invention compare the modulus of the sodium silicate solution (0) of 0.5 or less with that of the existing commercial products<n is less than or equal to 0.5) is called as the sodium silicate solution with ultra-low modulus. 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 nanometer SiO2The particles are quickly dissolved in normal temperature strong alkali solution to form monomer SiOn(OH)4-n]n-Principle of (1), nano SiO2The particles play a role in quickly supplementing soluble silicon in the solution, and quickly obtain the sodium silicate solution with the characteristics of ultralow modulus, ultralow viscosity and strong stability.
Preferably, the nano SiO2The specific surface area of the particles is 120-400 m2(ii)/g, the particle size D0.5 is 7 to 200 nm.
Preferably, the nano SiO2The particles are hydrophilic nano SiO2And (3) granules.
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 SiO is used2The particles are divided into two parts with similar mass and added in two times, so as to avoid the problem that the particles cannot be stirred due to 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 high-activity nano SiO2The sodium silicate solution with low modulus 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 SiO2The particles can be in a strong alkaline solutionDissolving in strong alkaline NaOH solution or nano SiO2The granules can be quickly dissolved in the granules at normal temperature. The measurement was carried out by microcalorimetry on a 2.2g NaOH solution (containing 0.2g of Na)2O +2.0g of water) to 0.03g of nano SiO2The exotherm rate curve for the particles is shown in figure 1. The result shows that the solution has obvious long-time heat release process in the environment of 20 ℃, which indicates that the nano SiO2The particles are subjected to a certain chemical process with the NaOH solution. According to its exothermic history, the explanation is as follows: hydrophilic nano SiO2The surface of the particles is wetted by water and exothermically, which is represented by a violent exothermicity lasting for tens of minutes in the first stage; hydrophilic nano SiO2The particles dissolve in solution and release heat, releasing soluble silicon and forming [ SiO ]n(OH)4-n]n-Showing a slow exotherm with a second phase lasting several hours. The exothermic behavior described above confirms that the SiO nanoparticles are present2The particles are soluble in NaOH solution. The process is long, but whenever a formulated low modulus sodium silicate solution is used, the nano SiO2The particles can exert their modifying effect. If ready to use, the nano SiO in the solution2The particles are only partially dissolved, and the chemical action of providing solubility, the physical filling action of the superfine particles and the crystal nucleus action can be simultaneously exerted; if the solution is used after long-term aging, the nano SiO in the solution2The particles are completely dissolved, and chemical action for providing solubility can be performed to the maximum extent.
The adoption of a laser particle sizer can further prove that the nano SiO2Dissolution characteristics of the granules in NaOH solution. Characterization of nano SiO by using the parameter of opacity of laser particle analyzer2The dissolution characteristics of the particles. 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. Nano SiO2The particle size is small and reaches the nanometer level, and when the particle size is added into the solution in a small amount and is subjected to ultrasonic dispersion, the light shading degree of the solution is close to 20 percent quickly. If nano SiO2The particles are dispersed in the solution all the time, and the light shading degree of the solution is kept about 20%. Adding nano SiO into NaOH solution2Change of opacity of solution after granulationLine, as shown in fig. 2. The results show that the opacity of the solution drops rapidly within a few tenths of a minute, which means that nano-SiO is present2Dissolving the particles; the opacity then slowly diminishes and this trend is maintained up to several hundred minutes, which indicates that the nano SiO2The particles are gradually dissolved; after a sufficiently long time (200 minutes), the opacity had decreased from the initial about 20% to about 1%, indicating that again during this time most of the nanosilica had been removed2The particles are all dissolved. Duration of the process and nano SiO2The duration of the exotherm of the addition of the particles to the NaOH solution was nearly uniform, again indicating that the nano-SiO was present in the solution2Solubility of the particles in NaOH solution, i.e. nano-SiO2The particles do function to provide soluble silicon in the solution.
Nano SiO2The dissolution process of the particles is necessarily accompanied by a change in the viscosity of the solution. If nano SiO2The solution is in a particle state, and the viscosity of the solution is obviously increased due to the hydrophilic property of the solution; the viscosity must drop significantly if it dissolves and becomes a component of the solution. Adding nano SiO into NaOH solution2The change in solution viscosity after granulation is shown in figure 3. The result shows that the nano SiO is added at normal temperature2The change rule of the viscosity of the later solution accords with the conjecture, the solution is changed from a turbid state to a clear state, the viscosity is close to that of the initial solution, and the description shows that the nano SiO2The soluble nature of the particles and little effect on solution viscosity.
Based on the nano SiO2The dissolubility of the particles in the normal-temperature NaOH solution is characterized in that the nano SiO is added into the NaOH solution2Granule, scheme for preparing low modulus sodium silicate 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 SiO into NaOH solution2The particles are prepared into low modulus sodium silicate solution with modulus of 0.15, 0.30 and 0.45.
Assuming a water cement ratio of 0.5 for the alkali-activated cement, the amount of activator used was 6.813% (based on its Na content)2The content of O is calculated by the mass percentage of the powder raw material in the alkali-activated cementitious material, the same applies below), and then various parameters of the solution required for meeting 450g of the powder raw material are prepared, as 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 | Nano 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 SiO2And (3) particle: hydrophilic type with particle size of 7-40nm (D0.5 ═ 14nm) and specific surface area of 400m2/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.
4.45g, 8.90g and 13.35g of nano SiO are respectively added at normal temperature2Adding the particles into NaOH solution, mechanically stirring for 10min under the condition that the rotating speed is 500r/min, and then ultrasonically dispersing for 5min to obtain the low-modulus sodium silicate solution for later use.
The result of FTIR spectrum is used for illustrating the nano SiO2The particles provide the function of soluble silicon. Adding nano SiO into NaOH solution2The variation curve of the FTIR vibration characteristics after the particles is shown in FIG. 4. From the results, when the nano SiO2Characteristic vibration band of O-Si-O (1108 cm) of the particles after addition to NaOH solution-1) And the characteristic vibration band of Si-OH (810 cm)-1) Disappearance, which indicates nano SiO2The particles are dissolved in this solution. Adding nano SiO2NaOH solution of pellets at wavenumber of 1000cm-1The obvious vibration band appears, which is nano SiO2The particles are dissolved to [ SiO ]n(OH)4-n]n-The corresponding O-Si-O vibrates. The sodium silicate solution with the comparative modulus of 0.15, 0.30 and 0.45 has almost no obvious difference, which shows that the nano SiO2The particles are soluble in solution regardless of the amount of the particles added, and no difference is provided in the soluble silicon.
The above results illustrate the use of nano-SiO2The particles "provide soluble silicon" asThe method for rapidly preparing the low-modulus sodium silicate solution 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 405 m)2Kg, the same applies below) as the powder raw material.
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 fact that the nano SiO2The granules provide soluble silicon, which not only promotes the early strength development, but also obviously promotes 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 nano-SiO in terms of structural features2The solubility of the particles and their effectiveness in providing soluble silicon was demonstrated. Example 2 the modulus range will be expanded to further verify the nano SiO2Modification effect of the particles on NaOH solution.
Nano SiO2And (3) particle: hydrophilic type, particle size of 16-50nm (D0.5 ═ 30nm), specific surface area 290m2/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.
Respectively adding 14.83g, 17.80g, 20.77g, 23.74g, 26.70g and 29.67g of nano SiO at normal temperature2Adding the granules into 0.225L of the NaOH solution, mechanically stirring for 30min at the rotation speed of 700r/min, and ultrasonically dispersing for 10min to obtain sodium silicate solution with modulus of 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 for later use. Due to the nanometer SiO2The addition of the particles is increased, so that the mechanical stirring is properly accelerated, and the stirring and ultrasonic time is prolonged.
It should be noted that when sodium silicate solution with modulus of 0.7, 0.8, 0.9, 1.0 is prepared, nano SiO2The particles were added in two portions, as follows:
sodium silicate solution with modulus 0.7: the first time, 10.77g of nano SiO is added2Mechanically stirring the particles for 30min at the rotating speed of 700r/min, and then ultrasonically dispersing for 10 min; after obtaining a clear solution, 10.00g of nano SiO is added immediately2Mechanically stirring the particles for 30min at the rotation speed of 700r/min, and then ultrasonically dispersing for 10 min.
Sodium silicate solution with modulus 0.8: 12.74g of nano SiO are added for the first time2Mechanically stirring the granules for 30min at the rotation speed of 700r/min, and ultrasonically separatingDispersing for 10 min; after obtaining a clear solution, adding 11.00g of nano SiO immediately2Mechanically stirring the particles for 30min at the rotation speed of 700r/min, and then ultrasonically dispersing for 10 min.
Sodium silicate solution with modulus 0.9: adding 13.70g of nano SiO for the first time2Mechanically stirring the particles for 30min at the rotating speed of 700r/min, and then ultrasonically dispersing for 10 min; after obtaining a clear solution, 13.00g of nano SiO is added immediately2Mechanically stirring the particles for 30min at the rotation speed of 700r/min, and then ultrasonically dispersing for 10 min.
Sodium silicate solution with modulus 1.0: adding 15.67g of nano SiO for the first time2Mechanically stirring the particles for 30min at the rotating speed of 700r/min, and then ultrasonically dispersing for 10 min; after obtaining a clear solution, 14.00g of nano SiO is added immediately2Mechanically stirring the particles for 30min at the rotation speed of 700r/min, and then ultrasonically dispersing 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 405 m)2Kg, the same applies below) as the powder raw material. 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 sodium silicate solution with low modulus is used as the excitant, the exothermic peak (second exothermic peak) of the alkali-excited reaction is gradually obvious, which is obviously nano SiO2The soluble silicon provided by the particles promotes the reaction.
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, the 3-day strength and the 28-day strength of the sample gradually increased with the increase of the modulus, which indicates that the nano SiO2The effect of soluble silicon provided by the particles on the strength increase is more and more obvious, which indicates that nano SiO is adopted2The method for preparing the low-modulus sodium silicate solution by dissolving the 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, the addition amount is 20 percent (calculated by the mass percentage of the solid in the powder, and the conversion is Na)2O, the mixing amount is 10.16%), the water cement ratio of the cementing material mortar sample is just 0.5.
(2) The method of the invention obtains the water glass solution with low modulus
Adding nano SiO into NaOH solution2And (4) particles, and the modulus is adjusted to be higher from zero.
Nano SiO2And (3) particle: hydrophilic type, particle size of 150-200nm (D0.5-185 nm), specific surface area of 120m2/g。
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 SiO are added for the first time2Mechanically stirring the particles for 30min at the rotation speed of 900r/min, and then ultrasonically dispersing for 10 min; after obtaining a clear solution, 22.00g of nano SiO is added immediately2Mechanically stirring the particles for 30min at 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 405 m)2Kg, the same applies below) as the powder raw material. 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 introduced was 45.84g (as Na)2Calculated as O), the amount of silicon introduced was 44.26g (in terms of SiO)2Meter), 225g of water was introduced, 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 added, the amount of alkali charged was 45.72g (as Na)2Calculated as O), the amount of silicon taken in was 44.25g (as SiO)2Meter), 225g of water was introduced, 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: "/" means OH-The concentration exceeds the pH value characterization range and is strong alkaline. 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 viscosity of the latter is lower because the former is adjusted from high modulus to low modulus, the silicon part of the former is kept in a high polymerization state, and the latter is nano SiO2Obtained by dissolution of particles, mainly with highly reactive monomers ([ SiO ]n(OH)4-n]n-) Are present. In addition, OH in the latter-The concentration is beyond the range which can be represented by the pH value, namely the solution exists in an ionic state, so that stronger alkalinity can be provided, and the alkali-activated reaction is obviously facilitated; 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 ([ SiO ]n(OH)4-n]n-) The former has a limited ability to provide monomers because of 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 lower compressive strength of the excited sample than the former excited sample, but has lower flexural strengthHigher, it is the partially undissolved nano SiO2The particles are filled in the matrix to play a toughening role. 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 SiO2And (3) particle: hydrophilic type, particle size 40-100nm (D0.5 ═ 72nm), specific surface area 275m2/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 SiO are added2Mechanically stirring the particles for 10min at the rotation speed of 500r/min, and ultrasonically dispersing 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.
Using fly ash and slagThe powder is used as a raw material, and the sodium silicate solution aged for different times is used as an activator to prepare the alkali-activated 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 405 m)2Kg, the same applies below) as the powder raw material. 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: "/" means OH-The concentration exceeds the pH value characterization range and is strong alkaline. 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 material is aged for a short time, although the nano SiO2The particles can not be completely dissolved, namely, the particles can not be completely converted into soluble silicon, but the undissolved particles play the physical filling and crystal nucleus functions of ultrafine particles, and can make up the defect that chemical effects cannot be completely played to a certain extent, so that the sample still has the strength equivalent to that of the sample excited by a long-time aging solution; when the nano SiO is stored for a long time2The particles are almost completely dissolved, at which point the chemical effect of providing soluble silicon is fully exerted, and the phaseThe test specimen should exhibit a sufficiently high strength. It is because some undissolved nano SiO exists in the solution after the solution is aged for a short time2Particles, the viscosity of the solution is greater than that of a solution that is left for a long period of time. With the prolonging of the aging time, the nano SiO2The particles gradually dissolve and the viscosity of the solution gradually decreases and is maintained at a comparable 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 (9)
1. A method for preparing a low modulus sodium silicate solution, comprising:
adding nano SiO into NaOH solution at normal temperature2The particles are stirred and dispersed to obtain a low-modulus sodium silicate solution with a set modulus;
the nano SiO2The addition amount of the particles satisfies formula (1):
m＝30×c×V×n (1)
in the formula (1), the reaction mixture is,
m is nano SiO in NaOH solution2The addition of the particles, in 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;
after the nano SiO is added2Before granulation, preparing NaOH solution meeting the set water-cement ratio of the alkali-activated cementing material and the required concentration of the alkali-activated cementing material;
450g of powder raw materials are needed in an alkali-activated cementing material mortar experiment, and if the water-cement ratio is gamma, the water requirement m' for preparing the NaOH solution with the required concentration meets 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 of the alkali-activated cementing material;
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, expressed as percent, and is expressed by Na2The content of O accounts for the mass percentage of the powder raw material in the alkali-activated cementing material;
gamma is the set water-cement ratio of the alkali-activated cementing material;
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; adding (15X 9 x beta x n/31) g of nano SiO into NaOH solution2The particles can meet the set modulus.
2. The method for preparing a low modulus sodium silicate solution according to claim 1,
the nano SiO2The specific surface area of the particles is 120-400 m2(ii)/g, the particle size D0.5 is 7 to 200 nm.
3. The method for preparing a low modulus sodium silicate solution according to claim 1,
the nano SiO2The particles are hydrophilic nano SiO2And (3) granules.
4. 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.
5. 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 SiO is put into the reactor2The particles are divided into two parts with similar mass and added in two times, so as to avoid the problem that the particles cannot be stirred due to one-time addition.
6. A low modulus sodium silicate solution, characterized in that it is prepared by the preparation method according to any one of claims 1 to 5.
7. The low modulus sodium silicate solution according to claim 6, wherein the viscosity of said low modulus sodium silicate solution is 10 to 20 mPa-s.
8. An alkali-activated cementitious material, characterised in that it uses as alkali activator the low modulus sodium silicate solution according to claim 6 or 7.
9. The alkali-activated cementitious material of claim 8, 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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