CN113092306B - Method for effectively detecting purity of silicon tetraboride and silicon hexaboride - Google Patents
Method for effectively detecting purity of silicon tetraboride and silicon hexaboride Download PDFInfo
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Abstract
The invention provides a method for effectively detecting the purity of silicon tetraboride and silicon hexaboride, relates to the field of materials, and provides a method for effectively detecting B 4 Si and B 6 Method of Si purity. According to the invention, after the moisture of the sample is removed, hydrofluoric acid with different concentrations is adopted for treatment, and then the reaction with KOH is carried out, and the calculation is carried out after the filtration and the cleaning of the sand core funnel. Compared with the representation of the current instrument means, the invention has the advantage that the B can be accurately detected 4 Si and B 6 The phase purity can be obtained by simple calculation according to the content of the Si phase. The invention is applied to B 4 Si and B 6 The field of Si materials.
Description
Technical Field
The invention relates to the field of materials, in particular to a method for effectively detecting the purity of silicon tetraboride and silicon hexaboride.
Background
B 4 Si and B 6 Si is a special material, has higher thermal and chemical stability, and has important application value in the fields of electronics, aerospace and the like. B 4 Si and B 6 Si is prepared by high-purity B and Si simple substances through high-temperature solid-phase sintering under vacuum or argon protection, and the prepared B can be realized by controlling the proportion of reactants B and Si 4 Si and B 6 The yield and purity of Si are high, the impurity content is low, and the small amount of impurity components mainly comprise simple substance Si and B and a very small amount of SiO 2 And B 2 O 3 Oxides, and the like. While in use, B 4 Si and B 6 The purity of Si has an important influence on its properties and thus on B 4 Si and B 6 The accurate detection of the phase purity of the Si has very important practical significance.
At present, no simple and efficient detection method for B can be realized 4 And accurately detecting the content of the Si phase. Although it can be characterized by some special chemical analysis instrument (such as inductively coupled plasma-ICP method), what the instrument detects is the content of a certain element (including impurities such as free Si, siO) in the whole sample 2 B and B 2 O 3 Etc.) do not give B exactly 4 Si and B 6 The content and purity of Si phase greatly limit B 4 Si and B 6 The application of Si in some fields requiring high purity.
Disclosure of Invention
The invention aims to provide a method for effectively detecting the purity of silicon tetraboride and silicon hexaboride.
An efficient assay of the invention 4 Si and B 6 A method for the purity of Si, which is carried out in the following manner:
step one, taking B to be detected 4 Si or B 6 Drying Si sample to remove adsorbed water, and drying to obtain dried B 4 Si or B 6 Si as m 1 The total mass of the sand core funnel and the sample is m 2 Transferring the dried sample to a platinum dish, adding deionized water to wet the sample, and mixing the dried sample and the deionized water according to a mass volume ratio of 1-2 g: adding hydrofluoric acid with the volume percentage content of 50% into a sample according to the proportion of 1mL, then placing the sample on a sand bath, heating and evaporating the sample until the sample is dried, and then mixing the hydrofluoric acid with the sample according to the mass volume ratio of 1-2 g: adding 10 volume percent hydrofluoric acid into a sample according to the proportion of 1mL, placing the sample on a sand bath, heating and evaporating the sample until the sample is dried, cooling the sample, adding 1 to 3mol/L KOH solution, reacting the mixture at normal temperature for 15 to 25min, then performing suction filtration by using a sand core funnel after constant weight at 170 to 190 ℃, and washing a platinum dish and residues by using 5 volume percent hydrochloric acid solution for 7 to 8 times; collecting the cleaned cleaning liquid, pouring the cleaning liquid and the residues into a sand core funnel for suction filtration, and finally cleaning a filter cake by using deionized water until the filter cake is neutral; then continuously heating the sand core funnel at 170-190 ℃ for 4-6 h, cooling, repeatedly drying to constant weight, weighing the total mass of the reacted sample and the sand core funnel dried to constant weight, and recording the total mass as m 3 ；
Step two, calculating B according to the following formula 4 Si or B 6 Si content, expressed in w%, the formula is as follows:
in the formula:
m 1 -mass of the sample in grams;
m 2 -the total mass of the sand core funnel and the sample in grams;
m 3 the total mass of the sample and the sand core funnel after reaction is in grams;
obtaining B to be detected by the formula 4 Si or B 6 B in Si sample 4 Si or B 6 And the Si content is the content of Si, namely the method for effectively detecting the purity of the silicon tetraboride and the silicon hexaboride is completed.
Further, the mass-to-volume ratio of the raw materials is 1.5g: to the sample, hydrofluoric acid was added at a concentration of 50% by volume in a proportion of 1 mL.
Further, the mass volume ratio of the raw materials is 1.5g: hydrofluoric acid was added to the sample at a volume concentration of 10% in a proportion of 1 mL.
Further, the concentration of the KOH solution is 2mol/L.
Further, after cooling, adding KOH solution with the concentration of 1-3 mol/L, and reacting for 20min at normal temperature.
Further, the sand core funnel after constant weight at 180 ℃ is used for suction filtration.
Further, the reacted sand core funnel is continuously heated for 5 hours at 180 ℃.
Further, the dried sample is transferred to a platinum dish, and deionized water is added to wet the sample along the wall of the platinum dish.
Further, B is 4 Si or B 6 The calculation result of the Si content is accurate to 0.01.
The principle of the invention is as follows:
treating with hydrofluoric acid to make oxide of free Si generate volatile silicon tetrafluoride, removing boron oxide with KOH, leaching with hydrochloric acid to dissolve surface impurities, and determining residue as B 4 Si or B 6 The content of Si, the reaction equation is as follows:
SiO 2+ 4HF＝SiF 4 +2H 2 O (1)
B 2 O 3 +6KOH＝2K 3 BO 3 +3H 2 O (2)
the invention has the following beneficial effects:
the invention provides a method for accurately detecting B 4 Si and B 6 The method for measuring Si phase content (purity) is that the currently common instrumental analysis detects the content of certain element to give the element content, which not only includes the removal of B 4 Si and B 6 Impurity phases other than Si (Si, siO) 2 、B、B 2 O 3 Etc.) element content, and yet fail to give accurate B 4 Si and B 6 Si phase content or purity. The detection result B of the present invention 4 Si and B 6 The purities of Si phases are all basically stabilizedAbout 97 percent, and the measured result value is stable, which shows that the invention has high detection stability and reliability. Compared with the prior instrument means characterization, the invention has the advantage of accurately detecting B 4 Si and B 6 The phase purity can be obtained by simple calculation according to the content of the Si phase.
Detailed Description
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
To make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following detailed description clearly illustrates the spirit of the present disclosure, and any person skilled in the art who knows the embodiments of the present disclosure can make changes and modifications to the technology taught by the present disclosure without departing from the spirit and scope of the present disclosure.
Example 1
B of the present embodiment 4 The detection method of the Si purity comprises the following steps:
1) The drugs and reagents used in this example are shown in the following table:
TABLE 1 Experimental drugs and reagent table
In addition, other materials used in the experiment were from chemical agencies such as disposable plastic droppers, plastic graduated cylinders (500 mL and 250 mL), nitrile gloves, magnetic stirrers, buchner funnels, aqueous/organic microfiltration membranes, medium/slow quantitative analysis filters, sand core funnels, etc.; the prepared solution and the reaction are deionized water.
2) The apparatus used is shown in table 2:
TABLE 2 Experimental instruments
3) Purified B 4 Si sample process:
accurately weigh 5.0g of B 4 Placing Si raw powder in a polytetrafluoroethylene beaker, adding 30mL of hydrogen peroxide, 35% of hydrogen peroxide concentration and 0.15mL of concentrated hydrochloric acid, stirring for 30min, standing for reaction for 4h, adding 40mL of 4mol/L KOH solution, stirring for reaction for 6h in a 70 ℃ water bath kettle, performing suction filtration by using a 0.45 mu m organic microporous filter membrane while hot, washing with ultrapure water to neutrality, placing in a vacuum drying oven at 70 ℃ for drying for 8h to obtain dried powder, namely purified B 4 And (3) a Si sample.
4) Experimental procedures
An effective detection B of the present embodiment 4 The method for Si purity is carried out according to the following steps:
1. reagent
1. The hydrogen peroxide is more than 35 percent.
2. Hydrofluoric acid (1.
3. Hydrochloric acid: (5%).
KOH solution 2mol/L
2. Analytical procedure
Drying the sample in an oven at 120 deg.C for 5 hr to remove adsorbed water, accurately weighing about 5.0g of the sample, and accurately measuring to 0.0001g 1 The total mass of the sand core funnel and the sample is m 2 Placing the mixture into a platinum dish, slowly adding a small amount of water along the wall of the platinum dish for wetting, adding 3mL of hydrofluoric acid (1).
Heating the powder and sand core funnel at 180 deg.C for 5 hr, cooling, repeatedly burning to constant weight, weighing, and recording as m 3 。
3. Calculation of results
B 4 The percentage of Si content, expressed in w%, is calculated according to the following formula:
in the formula:
m 1 -mass of the sample in grams (g);
m 2 -the total mass of the sand core funnel and the sample in grams (g);
m 3 the total mass of the sample and the sand core funnel after the reaction is in grams (g). The calculation result is accurate to 0.01.
The results are shown in table 1 below, which,
TABLE 1 purity test results for purified samples
For a given different batch B 4 The phase purity of each Si sample was measured by the method described in this example, and the results are shown in table 1 above. As can be seen from Table 1, the detection result B in this example 4 The purity of the Si phase is basically stabilized at about 97%, and the measured result is stable, which shows that the embodiment has high detection stability and reliability. In addition, the above table 1 also shows the biggest essential difference between this embodiment and the instrument analysis, that is, the detection object is B 4 Si phase content, the result obtained is the purity of the phase, not the content of the element measured by the instrument.
Example 2
B of the present example 6 The detection method of the Si purity comprises the following steps:
the apparatus and reagents used in this example were the same as those used in example 1.
1) Example purified B 6 Si sample process:
accurately weigh 5 groups of 5.0g of B 6 Placing Si raw powder in polytetrafluoroethylene beakers respectively, and adding 35% hydrogen peroxide 15mL and 0.15mL of concentrated hydrochloric acid, stirring for 30min, standing for reaction for 4h, adding 40mL of 4mol/L KOH solution, stirring for reaction for 4h in a 70 ℃ water bath, performing suction filtration by using a 0.45-micrometer organic microporous filter membrane while the solution is hot, washing with ultrapure water to be neutral, drying in a vacuum drying oven for 8h at 70 ℃, weighing the dried powder, and respectively calculating B 6 Purity of Si powder.
2) Procedure of experiment
An effective detection B of the present embodiment 6 The method for Si purity is carried out according to the following steps:
1. reagent
1. The hydrogen peroxide is more than 35 percent.
2. Hydrofluoric acid (1 mol/L).
3. Hydrochloric acid: (5%).
KOH solution 2mol/L
2. Analytical procedure
Drying the sample in an oven at 120 deg.C for 5 hr to remove adsorbed water, accurately weighing about 5.0g of the sample to 0.0001g, and recording as m 1 The total mass of the sand core funnel and the sample is m 2 Putting the mixture into a platinum dish, slowly adding a small amount of water along the wall of the platinum dish for wetting, adding 3mL of 1mol/L hydrofluoric acid, putting the platinum dish on a sand bath, heating and evaporating the mixture until the mixture is dried, covering a platinum crucible cover to avoid loss caused by powder brought out by generated gas, adding 3mL of 1mol/L hydrofluoric acid for continuous evaporation and drying, adding 5mL of 2mol/L KOH solution after cooling, reacting at normal temperature for 20min, performing suction filtration by using a sand core funnel after constant weight at 180 ℃ to obtain a filter core, washing the platinum dish and residues by using warm (40-60 ℃) dilute hydrochloric acid solution with the volume percentage content of 5% for 7-8 times, and finally washing a filter cake by using deionized water until the filter cake is neutral.
Heating the powder and sand core funnel at 180 deg.C for 5 hr, cooling, repeatedly burning to constant weight, weighing, and recording as m 3 。
3. Calculation of results
B 6 The percentage of Si content, expressed in w%, is calculated according to the following formula:
in the formula:
m 1 -mass of the sample in grams (g);
m 2 -the total mass of the sand core funnel and the sample in grams (g);
m 3 the total mass of the sample and the sand core funnel after the reaction is given in grams (g). The calculation result is accurate to 0.01.
The results are shown in Table 2 below,
TABLE 2 purity test results of purified samples
For given different batches B 6 The phase purity of each Si sample was measured by the method described in this example, and the results are shown in table 2 above. As can be seen from Table 2, the detection result B of this example 6 The purity of the Si phase is stable, and the measured result value is stable, which shows that the embodiment has high detection stability and reliability. In addition, the above table 2 also shows the biggest essential difference between this embodiment and the instrument analysis, that is, the detection object is B 6 Si phase content, the result is the purity of the phase, not the elemental content as measured by the instrument.
Claims (9)
1. A method for effectively detecting the purity of silicon tetraboride and silicon hexaboride is characterized by comprising the following steps of:
step one, taking B to be detected 4 Si or B 6 Drying Si sample to remove adsorbed water, and drying to obtain dried B 4 Si or B 6 Si sample as m 1 The total mass of the sand core funnel and the sample is m 2 Transferring the dried sample to a platinum dish, adding deionized water to wet the sample, and mixing the dried sample and the deionized water according to a mass volume ratio of 1-2 g: adding hydrofluoric acid with the volume percentage content of 50% into a sample according to the proportion of 1mL, then placing the sample on a sand bath, heating and evaporating the sample until the sample is dried, and then mixing the hydrofluoric acid and the sample according to the mass volume ratio of 1-2 g:1mL of hydrofluoric acid with the volume percentage content of 10 percent is added into the sample, and the sample is placed on a sand bath to be heated and evaporated until the temperature is increasedDrying, cooling, adding KOH solution with the concentration of 1-3 mol/L, reacting at normal temperature for 15-25 min, then performing suction filtration by using a sand core funnel with the constant weight of 170-190 ℃, and washing a platinum dish and residues for 7-8 times by using hydrochloric acid solution with the volume percentage of 5%; collecting the cleaned cleaning liquid, pouring the cleaning liquid and the residues into a sand core funnel for suction filtration, and finally cleaning a filter cake by using deionized water until the filter cake is neutral; then continuously heating the sand core funnel at 170-190 ℃ for 4-6 h, cooling, repeatedly drying to constant weight, weighing the total mass of the reacted sample and the sand core funnel dried to constant weight, and recording the total mass as m 3 ；
Step two, calculating B according to the following formula 4 Si or B 6 Si content, expressed in w%, the formula is as follows:
in the formula:
m 1 -mass of the sample in grams;
m 2 the total mass of the sand core funnel and the sample is gram;
m 3 the total mass of the sample and the sand core funnel after reaction is in gram;
obtaining B to be detected by the formula 4 Si or B 6 B in Si sample 4 Si or B 6 And the Si content is the content of Si, namely the method for effectively detecting the purity of the silicon tetraboride and the silicon hexaboride is completed.
2. The method for effectively detecting the purity of silicon tetraboride and silicon hexaboride according to claim 1, wherein the mass volume ratio of the silicon tetraboride to the silicon hexaboride is 1-2 g:1mL, adding 50% hydrofluoric acid by volume into a sample according to the mass-volume ratio of 1.5g: to the sample, hydrofluoric acid was added at a volume concentration of 50% in a proportion of 1 mL.
3. The method for effectively detecting the purity of silicon tetraboride and silicon hexaboride according to claim 1, wherein the mass volume ratio of the silicon tetraboride to the silicon hexaboride is 1-2 g:1mL, adding 10% hydrofluoric acid by volume into a sample according to the mass-volume ratio of 1.5g: hydrofluoric acid was added to the sample at a volume concentration of 10% in a proportion of 1 mL.
4. The method of claim 1, wherein the concentration of KOH solution is 2mol/L.
5. The method of claim 1, wherein the KOH solution with a concentration of 1 to 3mol/L is added after cooling, and the reaction is carried out at room temperature for 15 to 25min, specifically, the KOH solution with a concentration of 1 to 3mol/L is added after cooling, and the reaction is carried out at room temperature for 20min.
6. The method for effectively detecting the purity of silicon tetraboride and silicon hexaboride according to claim 1, wherein the filtration with a sand core funnel at a constant weight of 170-190 ℃ is specifically a filtration with a sand core funnel at a constant weight of 180 ℃.
7. The method for effectively detecting the purity of silicon tetraboride and silicon hexaboride according to claim 1, wherein the sand core funnel is continuously heated at 170-190 ℃ for 4-6 h, specifically, the reacted sand core funnel is continuously heated at 180 ℃ for 5h.
8. The method of claim 1, wherein the sample is transferred to a platinum dish after drying, and the deionized water is added to wet the sample along the wall of the platinum dish.
9. The method as claimed in claim 1, wherein B is selected from the group consisting of 4 Si or B 6 The calculation result of the Si content is accurate to 0.01.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106483243A (en) * | 2016-10-18 | 2017-03-08 | 桂林市产品质量检验所 | A kind of verification method of tetraphenylboron sodium reagent validity |
| CN111103377A (en) * | 2019-11-20 | 2020-05-05 | 中节能天融科技有限公司 | Soil volatile organic compounds flame ion detecting system |
| CN112125315A (en) * | 2020-09-25 | 2020-12-25 | 辽宁中色新材科技有限公司 | Low-cost high-purity silicon hexaboride production process |
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| US7799113B2 (en) * | 2004-09-02 | 2010-09-21 | Tekran Instruments Corporation | Conditioning system and method for use in the measurement of mercury in gaseous emissions |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106483243A (en) * | 2016-10-18 | 2017-03-08 | 桂林市产品质量检验所 | A kind of verification method of tetraphenylboron sodium reagent validity |
| CN111103377A (en) * | 2019-11-20 | 2020-05-05 | 中节能天融科技有限公司 | Soil volatile organic compounds flame ion detecting system |
| CN112125315A (en) * | 2020-09-25 | 2020-12-25 | 辽宁中色新材科技有限公司 | Low-cost high-purity silicon hexaboride production process |
Non-Patent Citations (1)
| Title |
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| C/SiC-SiB_4复合材料的制备及氧化行为;童长青等;《功能材料》;20081231;第39卷(第12期);全文 * |
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