CN116143131A - Preparation method of boron modified acidic silica sol with low metal ion content - Google Patents
Preparation method of boron modified acidic silica sol with low metal ion content Download PDFInfo
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- C01B33/00—Silicon; Compounds thereof
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Abstract
The preparation method of the boron modified acidic silica sol with low metal ion content is characterized by comprising the following steps of: a. uniformly mixing a boron modifier solution and a sodium silicate solution, b, exchanging the mixed solution by cation resin to obtain a boron doped silicic acid solution, c, dropwise adding the silicic acid solution into an alkali solution to nucleate and grow nano silicon dioxide particles, d, and preserving heat for a period of time after the silicic acid solution is dropwise added; e. concentrating the obtained silica sol to obtain boron modified silica sol; f. and adjusting the boron modified silica sol by using organic acid to obtain the boron modified acidic silica sol with low metal ion content. The invention has the advantages that the boron in-situ modified silica particles are carried out in the particle synthesis process, the organic acid can be used for adjusting the silica sol to prepare the boron modified acidic silica sol with different particle diameters, uniform and stable low metal ion content, the metal ion content of the acidic silica sol is effectively controlled, the process is simple, and the large-scale production is easy.
Description
Technical Field
The invention relates to a preparation method of boron modified acidic silica sol, in particular to a preparation method of boron modified acidic silica sol with low metal ion content.
Background
Silica sols are colloidal solutions of silica in water and are prepared by a number of methods. The most commonly used methods are ion exchange, silica fume one-step hydrolysis, silane hydrolysis, and the like. The ion exchange method is to exchange water glass with ion exchange resin to remove cations, and then to granulate, concentrate and the like.
The silica sol has wide application, and the nano water-based silica sol material is an important component of the semiconductor polishing solution. The semiconductor polishing liquid is required to have no organic matters and metal impurity ions in the polishing material, and the particles are uniformly dispersed. The particle size, particle size distribution, concentration, ph and impurity content of the silica will directly affect the balance between the removal rate of the surface of the polishing material and the surface roughness or waviness, thereby affecting the polishing quality of the material surface.
Chemical mechanical polishing of semiconductors is a mechanical polishing process based on chemical reactions, and to obtain good polishing sheet quality, it is necessary to balance the chemical etching action and the mechanical grinding action in the polishing process. Therefore, the polishing solution not only needs the nano aqueous silica sol as an abrasive for mechanical grinding, but also needs to be added with a pH regulator, an oxidant, a catalyst and the like to carry out chemical reaction with silicon atoms on the surface of the semiconductor. Therefore, the added nano aqueous silica sol raw material needs to exist stably under the acidic or alkaline condition.
A series of factors affecting the stability of the silica sol, including pH, particle size, electrolyte, dispersant, etc. Silica sols containing very low electrolyte concentrations are relatively stable and can be left for months or even years without gelling. In order to prepare a more stable silica sol, the electrolyte content in the silica sol needs to be reduced to a certain value. Particle size is another important factor affecting silica sol stability, and the more uniform the particle size, the narrower the distribution range, and the better the stability. The polymer organic dispersing agent can generate repulsive force among silicon dioxide particles to prevent the particles from gathering. However, with the addition of the dispersing agent, interaction occurs between the silica particles and the processing surface to form surface active molecules, resulting in a reduction in friction and a reduction in polishing efficiency.
Similarly, silica sol is widely used in the investment casting industry as a high temperature binder, and is a main raw material for investment casting, and directly affects the quality, production cycle and manufacturing cost of shells and castings. For a long time, the silica sol binder is continuously improved and developed, but the rapid development of the silica sol binder is restricted due to the defects of low drying speed, low shell making efficiency, poor wettability to wax molds, poor stability and the like.
Patent CN1259238C discloses a preparation method of boron modified particle silica sol, after acidifying water glass with strong acid cation exchange resin, alkalizing, curing, ultrafiltering and concentrating to obtain high specific surface area particle silica sol, and adding boride such as magnesium borate or potassium borate, sodium borosilicate, sodium tetraborate, etc. to modify in the preparation process. However, the boron-modified silica sol requires additional stabilizer to stabilize the boron-modified silica sol, and the additional stabilizer such as quaternary ammonium bases including tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dodecyltrimethylammonium hydroxide, cetyltrimethylammonium hydroxide, and LiOH, monoethanolamine, diethanolamine, and triethanolamine or mixtures thereof, all of which result in long time for concentrating the boron-modified silica sol, such as incomplete modification; the particle size of the sol particles gradually increases with time during storage, which results in a gradual decrease in specific surface area.
Patent CN101905472B discloses that the sol is prepared by using tetraethoxysilane as an initiator, hydrochloric acid as a catalyst, boric acid as an additive and a unique proportioning relationship. However, the modified cotton fiber is only used as an intermediate for treating poplar fibers, and has poor self application condition and stability.
Patent CN105837034B discloses that the silica-boron sol is obtained by using ethyl orthosilicate and tributyl borate as raw materials and under the actions of deionized water with pH of 3-5 and sub-stoichiometry at 60-70 ℃. However, the borosilicate sol prepared by the method is only an intermediate product doped with gel materials, and the stable sol gel is required to be supplemented.
Therefore, the existing boron modified silica sol preparation technology needs to be further improved and perfected.
Disclosure of Invention
The invention aims at providing a preparation method of boron modified acidic silica sol with low metal ion content.
The invention further aims at providing application of the boron modified acidic silica sol with low metal ion content in semiconductor polishing and precision casting.
In order to achieve the above object, the technical solution of the present invention is:
the preparation method of the boron modified acidic silica sol with low metal ion content is characterized by comprising the following steps of:
a. uniformly mixing the boron modifier solution and the sodium silicate solution at normal temperature to obtain a colorless and transparent mixed solution;
b. exchanging the mixed solution by cation resin to obtain boron doped silicic acid solution;
c. preparing an alkali solution in a stirring state, heating to a specified temperature, and then dropwise adding a silicic acid solution into the alkali solution to nucleate and grow nano silicon dioxide particles;
d. after the dropwise adding of the silicic acid solution is finished, continuing to keep the temperature for a period of time;
e. concentrating the obtained silica sol after heat preservation is finished to obtain 30-40% boron modified silica sol;
f. and adjusting the pH value of the boron modified silica sol to 2-6 by using organic acid to obtain the boron modified acidic silica sol with low metal ion content.
The preparation method of the boron modified acidic silica sol with low metal ion content can be further realized by adopting the following technical measures.
In the foregoing method, in the step (a), the boron modifier is one or more of boric acid, sodium tetraborate, potassium tetraborate, sodium metaborate, ammonium borate, lithium borate and magnesium borate.
In the foregoing method, in the step (a), the boron modifier is used in an amount such that the molar ratio of boron to silicon in the boron modifier solution to sodium silicate solution is 0.005-0.1.
The method as described above, wherein in step (a), the sodium silicate solution has a modulus of 3.3 and a silica content of 3 to 10%.
In the method, in the step (b), the cation exchange resin is H-type cation exchange resin, and the volume exchange capacity of the H-type cation exchange resin is more than or equal to 1.0mmol/ml.
The method as described above, wherein in step (b), the pH of the boron doped silicic acid solution is 2.2-2.8.
In the foregoing method, in the step (c), the alkali solution is one or more of potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution, tetramethylammonium hydroxide solution, tetraethylammonium hydroxide solution, tetrabutylammonium hydroxide solution, ethylenediamine solution, N-dimethylformamide, and ammonia water.
The method as described above, wherein in step (c), the pH of the alkaline solution is 9.0 to 13.0.
The method as described above, wherein in step (c), the specified temperature is 65 ℃ to 100 ℃.
The method as described above, wherein in step (e), the concentration is ultrafiltration concentration or distillation concentration by heating.
In the foregoing method, in step (f), the organic acid is one or more of formic acid, acetic acid, citric acid and oxalic acid.
The method, wherein the pH value of the boron modified acidic silica sol with low metal ion content is 2-6, and the average particle size is 5-50nm; the content of Ca, mg, al, fe ions of the boron modified acidic silica sol with low metal ion content is controlled within 20ppm except alkali metal ions, and the boron modified acidic silica sol can be stably stored for 30 days in an oven at 50 ℃.
The application of boron modified acidic silica sol with low metal ion content in polishing and precision casting of semiconductors.
After the technical scheme is adopted, the preparation method of the boron modified acidic silica sol with low metal ion content has the following advantages:
1. mixing the boron modifier solution with the sodium silicate solution, and carrying out boron in-situ modification on silica particles in the particle synthesis process after passing through cation exchange resin;
2. the boron modified acidic silica sol with different particle diameters and uniform and stable low metal particle content can be prepared by adjusting the silica sol with organic acid;
3. the method has the advantages that the boron modifier solution and the sodium silicate solution synchronously pass through the cation exchange resin, so that metal ions in the boron modifier solution and the sodium silicate solution are removed, the metal ion content of the acidic silica sol can be effectively controlled, the process is simple, and the large-scale production is easy;
4. the pH value of the boron modified acidic silica sol with low metal ion content is between 2 and 6, the average grain diameter is between 5 and 50nm, besides alkali metal ions, ca, mg, al, fe ions can be controlled within 20ppm, and the boron modified acidic silica sol can be stably stored in an oven at 50 ℃ for 30 days;
5. the polishing slurry is applied to semiconductor polishing and precision casting, widens the application scenes of polishing liquid and casting slurry under different acidic conditions, has low content of residual metal ions at the semiconductor polishing interface and the precision casting interface, and can effectively improve the semiconductor yield and the surface effect of precision casting parts.
Drawings
FIG. 1 is a scanning electron microscope image of a boron modified acidic silica sol particle with low metal ion content according to example 3 of the present invention;
FIG. 2 is a silica sol particle scanning electron microscope image of comparative example 3.
Detailed Description
The invention is further described below with reference to examples and figures thereof.
Example 1
The embodiment provides a boron modified acidic silica sol with low metal ion content, which is prepared by the following steps:
(1) At normal temperature, 21 parts of 4% boric acid solution and 826 parts of sodium silicate solution with 5% silicon dioxide content are uniformly mixed, and the molar ratio of boron to silicon is 0.02, so as to obtain colorless and transparent mixed solution;
(2) After 413 parts of H-type strong acid cationic resin with volume exchange capacity of 1.2mmol/ml is exchanged, 762 parts of boron doped silicic acid solution with pH of 2.8 is obtained;
(3) Under the stirring state, 200 parts of potassium hydroxide solution with the pH of 10.5 is prepared, after the temperature is raised to 85 ℃, the solution of silicic acid is dripped, the dripping speed is 381 parts of the solution of silicic acid per hour, and the dripping time is 2 hours;
(4) After the dropwise adding of the silicic acid solution is finished, continuing to keep the temperature for 30 minutes;
(5) After the heat preservation is finished for 30 minutes, cooling to 50 ℃, and carrying out ultrafiltration concentration on the obtained silica sol to obtain 122 parts of 30% boron modified silica sol;
(6) The boron modified silica sol was adjusted with 50% acetic acid solution to obtain a low metal ion content boron modified acidic silica sol having a pH of 3.5.
The average particle size of the sol is 5nm, the content of Ca, mg, al and Fe elements is low, the thermal storage stability at 50 ℃ is good, and the specific metal ion content and stability are shown in table 1.
Example 2
The embodiment provides a boron modified acidic silica sol with low metal ion content, which is prepared by the following steps:
(1) At normal temperature, mixing 13 parts of 4% sodium tetraborate solution with 834 parts of sodium silicate solution with silicon dioxide content of 7.5%, wherein the molar ratio of boron to silicon is 0.01, and obtaining colorless and transparent mixed solution;
(2) Exchanging 625 parts of mixed solution by using strong acid cation resin with volume exchange capacity of 1.5mmol/ml H to obtain 762 parts of boron doped silicic acid solution with pH of 2.4;
(3) Under the stirring state, 200 parts of sodium hydroxide solution with the pH of 12.5 is prepared, after the temperature is raised to 95 ℃, the solution of silicic acid is dripped, the dripping speed is 127 parts of the solution of silicic acid per hour, and the dripping time is 6 hours;
(4) After the dropwise adding of the silicic acid solution is finished, continuing to keep the temperature for 30 minutes;
(5) After the heat preservation is finished for 30 minutes, cooling to 50 ℃, and carrying out ultrafiltration concentration on the obtained silica sol to obtain 138 parts of 40% boron modified silica sol;
(6) The boron modified silica sol was adjusted using a 40% citric acid solution to obtain a low metal ion content boron modified acidic silica sol having a pH of 4.5.
The average particle size of the sol is 50nm, the content of Ca, mg, al and Fe elements is low, the thermal storage stability at 50 ℃ is good, and the specific metal ion content and stability are shown in table 1.
Example 3
The embodiment provides a boron modified acidic silica sol with low metal ion content, which is prepared by the following steps:
(1) Uniformly mixing 4 parts of 5% sodium metaborate solution and 912 parts of sodium silicate solution with silicon dioxide content of 4.0% at normal temperature, wherein the molar ratio of boron to silicon is 0.005, and obtaining colorless and transparent mixed solution;
(2) After 365 parts of mixed solution is exchanged by strong acid cation resin with volume exchange capacity of 1.3mmol/ml H, 825 parts of boron doped silicic acid solution with pH of 2.5 is obtained;
(3) Under the stirring state, 200 parts of sodium hydroxide solution with the pH of 11.5 is prepared, after the temperature is raised to 90 ℃, the solution of silicic acid is dripped, the dripping speed is 206 parts of the solution of silicic acid per hour, and the dripping time is 4 hours;
(4) After the dropwise adding of the silicic acid solution is finished, continuing to keep the temperature for 30 minutes;
(5) After the heat preservation is finished for 30 minutes, cooling to 50 ℃, and carrying out ultrafiltration concentration on the obtained silica sol to obtain 107 parts of 30% boron modified silica sol;
(6) The boron modified silica sol was adjusted using a 40% citric acid solution to obtain a low metal ion content boron modified acidic silica sol having a pH of 6.0.
The average particle size of the sol is 30nm, the content of Ca, mg, al and Fe elements is low, the thermal storage stability at 50 ℃ is good, the particle monodispersity is good, and the content and the stability of specific metal ions are shown in table 1; the particle morphology of the low metal ion content boron modified acidic silica sol particle is shown in figure 1, and figure 1 is a scanning electron microscope image of the low metal ion content boron modified acidic silica sol particle of the embodiment 3 of the invention, which shows that the low metal ion content boron modified acidic silica sol particle has good dispersibility and no obvious adhesion condition.
Example 4
The embodiment provides a boron modified acidic silica sol with low metal ion content, which is prepared by the following steps:
(1) Uniformly mixing 29 parts of 4% potassium tetraborate solution with 795 parts of sodium silicate solution with silicon dioxide content of 7.5% at normal temperature, wherein the molar ratio of boron to silicon is 0.02, and obtaining colorless and transparent mixed solution;
(2) 596 parts of mixed solution is exchanged by strong acid cation resin with volume exchange capacity of 1.3mmol/ml H, and 742 parts of boron doped silicic acid solution with pH of 2.6 is obtained;
(3) Under the stirring state, 200 parts of tetramethyl ammonium hydroxide solution with the pH of 11.0 is prepared, after the temperature is raised to 95 ℃, the silicic acid solution is dropwise added, the dropwise adding rate is 148 parts of silicic acid solution per hour, and the dropwise adding time is 5 hours;
(4) After the dropwise adding of the silicic acid solution is finished, continuing to keep the temperature for 30 minutes;
(5) After the heat preservation is finished for 30 minutes, cooling to 50 ℃, and carrying out ultrafiltration concentration on the obtained silica sol to obtain 131 parts of 40% boron modified silica sol;
(6) The boron modified silica sol is regulated by using 50% acetic acid solution to obtain the boron modified acidic silica sol with low metal ion content and pH value of 5.0.
The average particle size of the sol is 40nm, the content of Ca, mg, al and Fe elements is low, the thermal storage stability at 50 ℃ is good, and the specific metal ion content and stability are shown in table 1.
Example 5
The embodiment provides a boron modified acidic silica sol with low metal ion content, which is prepared by the following steps:
(1) Uniformly mixing 10 parts of 4% sodium tetraborate solution with 795 parts of sodium silicate solution with silicon dioxide content of 6.0% at normal temperature, wherein the molar ratio of boron to silicon is 0.01, and obtaining colorless and transparent mixed solution;
(2) After 477 parts of strong acid cation resin with volume exchange capacity of 1.2mmol/ml H is exchanged, 725 parts of boron doped silicic acid solution with pH of 2.7 is obtained;
(3) Under the stirring state, 200 parts of potassium hydroxide solution with the pH of 11.5 is prepared, after the temperature is raised to 90 ℃, the solution of silicic acid is dripped, the dripping speed is 242 parts of the solution of silicic acid per hour, and the dripping time is 3 hours;
(4) After the dropwise adding of the silicic acid solution is finished, continuing to keep the temperature for 30 minutes;
(5) After the heat preservation is finished for 30 minutes, cooling to 50 ℃, and carrying out ultrafiltration concentration on the obtained silica sol to obtain 140 parts of 30% boron modified silica sol;
(6) The boron modified silica sol was adjusted with 50% acetic acid solution to obtain a low metal ion content boron modified acidic silica sol having a pH of 2.5.
The average particle size of the sol is 15nm, the content of Ca, mg, al and Fe elements is low, the thermal storage stability at 50 ℃ is good, and the specific metal ion content and stability are shown in table 1.
Comparative example 1
The comparative example provides an acidic silica sol which is not modified with boron, and the preparation method is different from example 1 in that the boron modification solution is not added in the step (1) and is mixed with a sodium silicate solution, and the other methods are consistent.
The average particle size of the sol is 5nm, and the specific metal ion content and stability are shown in Table 1.
Comparative example 2
The comparative example provides a conventional boron-modified acidic silica sol, which is prepared by mixing the sodium silicate solution with the boron-modified solution in the step (1), adding one step between the step (5) and the step (6), removing metal ions from 40% of silica sol by using cation exchange resin, adding 12 parts of 4% sodium tetraborate solution to modify the silica gel, and re-heating and concentrating until the solid content is 40%, wherein the other steps are consistent.
The average particle size of the sol is 50nm, and the specific metal ion content and stability are shown in Table 1.
Comparative example 3
This comparative example provides an acidic silica sol using a boron modifier in a molar ratio of boron to silicon of 0.03, prepared by a method differing from that of example 3 in that 24 parts of a 5% sodium metaborate solution and a sodium silicate solution were used for mixing in step (1), and the other were identical.
The average particle size of the sol is 30nm, and the particle morphology is shown in figure 2. FIG. 2 is a scanning electron microscope image of silica sol particles of comparative example 3, which shows that silica sol particles have poor dispersibility, larger particles exist, and adhesion exists between particles.
Comparative example 4
The comparative example provides an acidic silica sol using an H-type strongly acidic cationic resin having an insufficient volume exchange capacity, which is prepared by a method differing from example 4 in that the H-type strongly acidic cationic resin used in step (2) has a volume exchange capacity of 0.8mmol/ml, and the others are the same.
The sol is subjected to the step (2) to obtain a boron doped silicic acid solution with the pH value of 3.6, and the viscosity of the silicic acid solution is obviously increased after the silicic acid solution is dripped for 4 hours, so that the dripping is not smooth; the gel occurs during the ultrafiltration in step (5).
Comparative example 5
The comparative example provides an acidic silica sol having a reaction temperature of 60℃and is prepared by a method different from example 5 in that the step (3) is heated to 65℃and then the addition of a silicic acid solution is started, all the others being identical.
The 30% boron modified silica sol obtained in step (5) has a high viscosity.
The average particle size of the sol was 4nm, and the specific stability is shown in Table 1.
The boron-modified acidic silica sols having a low metal ion content obtained in examples 1 to 5 and comparative examples 1 to 5 were diluted to a silica content of 300ppm, and the particle size and PDI were measured by using a laser particle sizer Nano S90 from Markov, UK; after being digested by hydrofluoric acid, the content of calcium, magnesium, aluminum and iron ions is measured by adopting a plasma mass spectrometer XII of the Sieimer's femto company; the particle morphology was characterized using a field emission scanning electron microscope JSM-IT800 from japan electronics corporation; the above silica sol was subjected to a storage stability test at 50 ℃ using an electrothermal constant temperature forced air drying oven.
From the test results, the boron modified acidic silica sol prepared by premixing the boron modified solution and the sodium silicate solution and then passing through the cation exchange resin has lower contents of calcium ions, magnesium ions, aluminum ions and iron ions than the acidic silica sol prepared by the traditional method (table 1); the stability of the boron modified acidic silica sol prepared using a cationic resin with low volume exchange capacity or a lower reaction temperature is somewhat inferior (table 1); the particle morphology of the boron modified acidic silica sol prepared using more boron modifier was poor (fig. 1, fig. 2).
TABLE 1 silica sol test results
The preparation method of the boron modified acidic silica sol with low metal ion content is applied to semiconductor polishing and precision casting, widens the application scenes of polishing solution and casting slurry under different acidic conditions, has low content of residual metal ions at the interface of semiconductor polishing and the interface of precision casting, and can effectively improve the yield of semiconductors and the surface effect of precision casting.
The preparation method of the low metal ion content boron modified acidic silica sol has substantial characteristics and obvious technical progress, and the technical scheme of the preparation method of the low metal ion content boron modified acidic silica sol proves that in the step (1), the boron modifier is one or a combination of more than two of boric acid, sodium tetraborate, potassium tetraborate, sodium metaborate, ammonium borate and the like. The boron modifier is used in an amount such that the molar ratio of boron to silicon is 0.005-0.02, for example 0.005, 0.01 and 0.02, and exceeding the range can cause excessive boron ions, thereby affecting the morphology and dispersity of particles, and when the boron modifier is smaller than the range, the boron modification effect of silica sol is affected, and the stability is deteriorated.
The technical scheme of the preparation method of the boron modified acidic silica sol with low metal ion content proves that in the step (1), the sodium silicate solution has a modulus of 3.3, a silica content of 4.0-7.5%, such as 4.0%, 5.0%, 6.0% and 7.5%, and the boron doped silicic acid prepared by exceeding the range has poor stability, does not meet the actual production requirement, and has lower silica content and poor economic benefit when being smaller than the range.
The technical scheme of the preparation method of the boron modified acidic silica sol with low metal ion content proves that in the step (2), the cation exchange resin is H-type strong acid cation exchange resin, the volume exchange capacity of the cation exchange resin is more than or equal to 1.2mmol/ml, such as 1.2mmol/ml, 1.3mmol/ml and 1.5mmol/ml, and if the volume exchange capacity exceeds the range, the efficiency of regenerating the cation exchange resin is lower, the required acid amount is more, the time is longer, and the economic benefit is poor; if the pH of the silicic acid solution is smaller than this range, the pH of the silicic acid solution prepared is higher, and the residual metal ions in the mixed solution are high.
The technical scheme of the preparation method of the boron-modified acidic silica sol with low metal ion content proves that in the step (2), the pH of the boron-doped silicic acid solution is between 2.4 and 2.8, for example, 2.4, 2.5, 2.6, 2.7 and 2.8, and the boron-doped silicic acid prepared by exceeding the range has poor stability, does not meet the actual production requirement, and the alkali amount required is increased when the pH is smaller than the range, so that the control of metal ions is unfavorable.
The technical scheme of the preparation method of the low metal ion content boron modified acidic silica sol proves that in the step (3), the alkali solution is one or more than two of potassium hydroxide solution, sodium hydroxide solution, tetramethylammonium hydroxide solution, ammonia water and the like, the pH of the alkali solution is between 10.5 and 12.5, for example, 10.5, 11.0, 11.5, 12.0 and 12.5, and particles grow too fast beyond the range, the monodispersity is poor, the growth of silica particles is slower when the alkali solution is smaller than the range, and the stability of the boron modified acidic silica sol is poor.
The technical scheme of the preparation method of the boron-modified acidic silica sol with low metal ion content also proves that in the step (3), the designated temperature is 85-95 ℃, such as 85 ℃, 90 ℃ and 95 ℃, more heat sources are needed when the designated temperature exceeds the range, the evaporation amount is increased, the economic benefit is poor, the growth of silica particles is slower when the designated temperature is smaller than the range, and the stability of the boron-modified acidic silica sol is poor.
The above embodiments are provided for illustrating the present invention only, and not for limiting the present invention, and various changes or modifications may be made by one skilled in the relevant art without departing from the spirit and scope of the present invention. Accordingly, all equivalent arrangements should be considered to be within the scope of the present invention as defined in the claims.
Claims (13)
1. The preparation method of the boron modified acidic silica sol with low metal ion content is characterized by comprising the following steps of:
a. uniformly mixing the boron modifier solution and the sodium silicate solution at normal temperature to obtain a colorless and transparent mixed solution;
b. exchanging the mixed solution by cation resin to obtain boron doped silicic acid solution;
c. preparing an alkali solution in a stirring state, heating to a specified temperature, and then dropwise adding a silicic acid solution into the alkali solution to nucleate and grow nano silicon dioxide particles;
d. after the dropwise adding of the silicic acid solution is finished, continuing to keep the temperature for a period of time;
e. concentrating the obtained silica sol after heat preservation is finished to obtain 30-40% boron modified silica sol;
f. and adjusting the pH value of the boron modified silica sol to 2-6 by using organic acid to obtain the boron modified acidic silica sol with low metal ion content.
2. The method for preparing a boron-modified acidic silica sol having a low metal ion content according to claim 1, wherein in the step (a), the boron modifier is one or more of boric acid, sodium tetraborate, potassium tetraborate, sodium metaborate, ammonium borate, lithium borate, and magnesium borate.
3. The method for preparing a boron-modified acidic silica sol having a low metal ion content as claimed in claim 1, wherein in the step (a), the boron modifier is used in an amount such that the molar ratio of boron to silicon in the boron modifier solution to sodium silicate solution is 0.005 to 0.1.
4. The method of preparing a boron-modified acidic silica sol having a low metal ion content according to claim 1, wherein in the step (a), the sodium silicate solution has a modulus of 3.3 and a silica content of 3 to 10%.
5. The method for preparing a boron-modified acidic silica sol having a low metal ion content as claimed in claim 1, wherein in the step (b), the cation exchange resin is an H-type cation exchange resin having a volume exchange capacity of not less than 1.0mmol/ml.
6. The method of preparing a boron-modified acidic silica sol having a low metal ion content according to claim 1, wherein in the step (b), the pH of the boron-doped silicic acid solution is 2.2 to 2.8.
7. The method for preparing a boron-modified acidic silica sol with low metal ion content according to claim 1, wherein in the step (c), the alkali solution is one or more of potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution, tetramethylammonium hydroxide solution, tetraethylammonium hydroxide solution, tetrabutylammonium hydroxide solution, ethylenediamine solution, N-dimethylformamide, and aqueous ammonia.
8. The method for preparing a boron-modified acidic silica sol having a low metal ion content according to claim 1, wherein the pH of the alkaline solution in the step (c) is 9.0 to 13.0.
9. The method of preparing a boron-modified acidic silica sol having a low metal ion content according to claim 1, wherein in the step (c), the prescribed temperature is 65 ℃ to 100 ℃.
10. The method for preparing a boron-modified acidic silica sol having a low metal ion content according to claim 1, wherein in the step (e), the concentration is ultrafiltration concentration or distillation-heating concentration.
11. The method for preparing a boron-modified acidic silica sol having a low metal ion content according to claim 1, wherein in the step (f), the organic acid is one or more of formic acid, acetic acid, citric acid and oxalic acid.
12. The method for preparing the low metal ion content boron-modified acidic silica sol according to claim 1, wherein the low metal ion content boron-modified acidic silica sol has a pH of 2 to 6 and an average particle diameter of 5 to 50nm; the content of Ca, mg, al, fe ions of the boron modified acidic silica sol with low metal ion content is controlled within 20ppm except alkali metal ions, and the boron modified acidic silica sol can be stably stored for 30 days in an oven at 50 ℃.
13. Use of the boron-modified acidic silica sol of low metal ion content according to claim 1 in semiconductor polishing and precision casting.
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| CN116515331A (en) * | 2023-05-27 | 2023-08-01 | 烟台凯多海洋生物研究院有限公司 | Preparation and application methods of apple bagging-free film agent |
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| CN116515331A (en) * | 2023-05-27 | 2023-08-01 | 烟台凯多海洋生物研究院有限公司 | Preparation and application methods of apple bagging-free film agent |
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