CN103439213A - System detection method for components in industrial silicon carbide - Google Patents
System detection method for components in industrial silicon carbide Download PDFInfo
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Abstract
The invention discloses a system detection method for components in industrial silicon carbide. According to the method, components such as silicon dioxide, free silicon, silicon carbide, aluminum oxide, titanium dioxide and ferric oxide in industrial silicon carbide are gradually separated and detected by performing measures such as high-temperature firing, acidic liquid treatment and filtration separation on an industrial silicon carbide test sample to be detected, and then the mass percentage content of the components in the industrial silicon carbide to be detected can be calculated according to the mass of all the determined components. According to the method, a concept of successive separation and systematic detection is adopted, the content of various components in the industrial silicon carbide can be systematically detected at one time; the method is easy to operate, and a result is high in accuracy.
Description
Technical field
The invention belongs to the chemical analysis technology field, specifically refer to a kind of system detecting method of industrial silit component.
Background technology
Industry silit has the characteristics such as fusing point is high, high temperature resistant, corrosion-resistant, and the wearing quality that has higher intensity to become reconciled is widely used in the aspects such as replacing the ferrosilicon deoxidation of dosing in material, furnace refractory and steel-making, continuous casting process of special refractories.The components such as the silicon dioxide contained in industry silit, free silica, silit, alundum (Al2O3), titania, di-iron trioxide, the composition difference of contained material in industrial silit, its purposes is also corresponding different.How to measure exactly the content of each component in industrial carbofrax material, to the research of industrial silit with apply most important.
The existing detection to various components in industrial silit, many employings first separate method for measuring again, first every kind in sample to be tested component is separated then single component is measured respectively.As once adopting supercharging, test of refractories center, Kweiyang sealed the content of leaching-spectrphotometric method for measuring industry silicon dioxide in silicon carbide; Steel research institute and eight manufacturing management sections of steel company of Baoshan Iron and Steel Group are climbed by Panzhihua iron and steel joint-stock company, by adopting NaOH, leach in industrial silit after free silica, use the colorimetric method for determining silicone content, have obtained effect preferably.Zhengzhou Abrasive Materials, Abrasive Tools, Grinding Inst. (CN) No.1 Huashan R of mechano-electronic section, adopt potassium fluoride volumetry to measure the SiO in deoxidizer silit
2the content of component.Also there is part body to carry out METHOD FOR CONTINUOUS DETERMINATION to each component concentration in industrial silit, but general maximum can only two kinds of components of wherein certain of single-time measurement, as the Benxi Iron and Steel Company technique center adopts hydrofluorite waved arching pushing METHOD FOR CONTINUOUS DETERMINATION silicon dioxide and carborundum content in the comprehensive silicon, but can't realize the METHOD FOR CONTINUOUS DETERMINATION of other component concentrations.For another example, in GB/T16555-2008, to the mensuration of di-iron trioxide, alundum (Al2O3) in industrial silit, be this two component of METHOD FOR CONTINUOUS DETERMINATION after decomposition samples, and in this standard, test solution acidity, temperature, rate of titration etc. are had to strict demand, regulate acidity and titration and back titration process operation too complicated, operative skill requirement to the testing staff is very high, and the final analysis resultant error is larger.
Summary of the invention
Purpose of the present invention is exactly the system detecting method that a kind of industrial silit component will be provided, and utilizes the method to carry out the systematicness detection by the disposable content by various ingredients in industrial silit, and this detection method is simple to operate and result precision is high.
For achieving the above object, the system detecting method of industrial silit component of the present invention comprises the following steps:
1) taking quality is m
1to be measured industrial silit sample, be placed in container through 700 ~ 800 ℃ of high temperature sinterings, eliminate uncombined carbon, then add the abundant dissolved samples of enough dilute sulfuric acids, then again through 700 ~ 800 ℃ of high temperature sinterings to constant weight, weighing container and sample, its gross mass is counted m
2;
2) to the mix acid liquor that adds enough dense hydrofluorite and dilute sulfuric acid in container, in described mix acid liquor, dense hydrofluorite and dilute sulfuric acid volume ratio are 5 ~ 10: 1, heating is smoldered volatilization fully 290 ~ 320 ℃ of isothermal reaction to acid solutions, again through 700 ~ 800 ℃ of high temperature sinterings to constant, weighing container and sample, its gross mass is counted m
3, described m
2with m
3difference be the quality of silicon dioxide in industrial silit sample to be measured;
3) to the mixed solution that adds enough red fuming nitric acid (RFNA)s, dense hydrofluorite and dilute sulfuric acid in container, in described mixed solution, the volume ratio of red fuming nitric acid (RFNA), dense hydrofluorite and dilution heat of sulfuric acid is 4 ~ 10: 10 ~ 20: 1 ~ 2, heating is smoldered volatilization fully 290 ~ 320 ℃ of isothermal reaction to acid solutions, again after 700 ~ 800 ℃ of high temperature sintering constants, weighing container and sample, its gross mass is counted m
4, described m
3with m
4difference be the quality of elemental silicon in industrial silit sample to be measured;
4) continue to add 5 ~ 10 times of m in crucible
1natrium carbonicum calcinatum and the intermixture of boric acid, the mass ratio 1.5 ~ 3: 1 of natrium carbonicum calcinatum and boric acid in described intermixture, be heated to 1050 ~ 1200 ℃ of melting 30 ~ 60min, sample in container is that fusion and decomposition is complete, then be cooled to room temperature and obtain solid matter, adopt enough hydrochloric acid-saturated BAS that solid matter is fully dissolved under 80 ~ 100 ℃ of conditions, after the solution heating is concentrated to the state of a small amount of liquid of residue, add enough ethanol to make excessive acid reaction generate volatile borogen, finally heat evaporate to dryness, obtain the pressed powder thing;
5) fully dissolve to adding in the pressed powder thing after enough concentrated hydrochloric acids heating to boil to the pressed powder thing, then add appropriate gelatin solution, obtain filter residue and filtrate through stirring, cohesion, filtration, washing operation successively, filtrate is carried out to precise volume setting stand-by; By filter residue adopt 450 ~ 1000 ℃ carry out ashing, calcination is processed and is obtained silica solid, the quality of weighing silicon dioxide is counted m
5, in industrial silicon carbide sample, the quality of silit is 2m
5/ 3;
6) get the stand-by filtrate of a certain amount of step 5) constant volume, add excessive EDTA, then use the EDTA of zinc acetate standard solution overtitration, add a certain amount of villiaumite again in solution, heating is boiled, and fluorine replaces the EDTA with the aluminium complexing, finally with the titration of zinc acetate standard solution, replace the EDTA that, according to the zinc acetate standard solution volume consumed, can draw the quality of aluminium in got filtrate by calculating, and then can converse the quality of alundum (Al2O3) in industrial silicon carbide sample;
7) separately get the stand-by filtrate of a certain amount of step 5) constant volume, drip appropriate ascorbic acid solution existing colourless to filtrate, adopt watery hydrochloric acid to regulate the pH value to 4 of filtrate ~ 5, add appropriate diantipyrylmethane, form yellow [Ti (DAPM)
3]
4+complex compound, adopt spectrophotometric method to [Ti (DAPM) wherein
3]
4+ti content in complex compound is measured, and can extrapolate the quality of titania in industrial silicon carbide sample;
8) separately get again the stand-by filtrate of a certain amount of step 5) constant volume, drip appropriate ascorbic acid solution existing colourless to filtrate, regulating its pH to 4 ~ 5 with acetic acid-sodium acetate buffer solution adds phenanthrolene (1,10-phenanthrolene) to form orange red [Fe (Phen) in rear
2+] complex compound, adopt spectrophotometric method to [Fe (Phen)
2+] iron content in complex compound measured, can extrapolate in industrial silicon carbide sample in the quality of di-iron trioxide;
9), according to the quality of each component in determined, can calculate quality is m
1industrial silit in the quality percentage composition of each component.
Preferably, the hydrochloric acid in described step 4)-saturated BAS is that boric acid is dissolved in the hydrochloric acid solution that volume ratio is 1: 1, and maintains the boric acid solid in described hydrochloric acid-saturated BAS.
Again further, a kind of in the solid that the villiaumite in described step 6) is potassium fluoride, sodium fluoride, ammonium fluoride or aqueous solution.
Also further, the sulfuric acid solution that described dilute sulfuric acid is water and concentrated sulphuric acid volume ratio 1: 1 ~ 2, described dense hydrofluorite refers to that density is 1.15 ~ 1.10g/cm
3hydrofluoric acid solution, described red fuming nitric acid (RFNA) is that density is 1.42 ~ 1.40g/cm
3salpeter solution, described concentrated hydrochloric acid is that density is 1.19 ~ 1.15g/cm
3hydrochloric acid solution.
The present invention adopts aforesaid operations can progressively determine the content of each component in industrial silit to be measured.Wherein, the principle of each step process is:
Sample is through 700 ~ 800 ℃ of high temperature sinterings, and after eliminating uncombined carbon, after first with sulfuric acid, acid-soluble substance in sample being dissolved, high temperature sintering is to constant weight, and wherein in the time of 290 ~ 320 ℃, acid solution can be smoldered volatilization fully; Use hydrofluorite-sulfuric acid heat treated, the silicon dioxde reaction in industrial silit becomes silicon tetrafluoride volatilization again, then through high temperature sintering to can be according to the quality of the calculating silicon dioxide of poor quality before and after processing after constant.After separating treatment silicon dioxide in the sample of constant weight, carry out heat treated after adding the mixed solution of enough red fuming nitric acid (RFNA)s-dense hydrofluorite-dilute sulfuric acid to dissolve, elemental silicon reaction generates the silicon tetrafluoride volatilization, and calcination is to can be according to the quality of the calculating elemental silicon of poor quality before and after processing after constant.In sample after analyzing and processing silicon dioxide, elemental silicon, the intermixture that adds natrium carbonicum calcinatum and boric acid, heat abundant fusion and decomposition sample, then with appropriate hydrochloric acid-saturated BAS leaching fused mass, in low-temperature heat, be evaporated under the state of a small amount of solution of residue, add enough ethanol to make excessive acid reaction generate volatile borogen, thermal dehydration, to the dry volatile substances of removing, is fixed the powder thing; Then adopt the animal glue gravimetric method to be measured the content of silicon dioxide in described pressed powder thing, under concentrated hydrochloric acid is done solvent condition, add appropriate animal glue and stir fully cohesion silicon dioxide, process after filtration, that filtrate is carried out to precise volume setting is stand-by; Filter residue is through washing, and calcination is processed and obtained silicon dioxide (this silicon dioxide is that silit changes).In the stand-by filtrate of the constant volume obtained in said determination silit step, pipette respectively in right amount aluminium, iron, titanium wherein detected, concrete detection mode by: got aluminium content in solution with villiaumite displacement EDTA titration measuring; Got Ti content in solution with the diantipyrylmethane spectrophotometry; Got iron content in solution with the phenanthrolene spectrophotometry.Finally, according to the quality of each component in determined, can calculate quality is m
1industrial silit in the quality percentage composition of each component.
Each compound mensuration of native system analytic approach is not only interrelated but also separate.The fixed accuracy of silicon dioxide wherein, free silica, silit three pacings is interrelated, silicon dioxide, free silica measure in the volatilization completeness of each step silicon dioxide, influential to the accuracy of follow-up silicon composition measurement.From computing formula, the cubage of free silica need to be used the quality after back volatilization silicon dioxide constant weight.After silicon dioxide, free silica must volatilize fully in succession, carry out the mensuration of subsequent step, the accuracy of guarantee silit.The accuracy of alundum (Al2O3), titania, di-iron trioxide three components is not subject to the impact of other component analysis error in system.
The thinking that industrial silit component system detection method of the present invention is separated by adopting successively, system detects, obviously improved analysis speed, and the sensing range coverage rate is wider; And will originally repeatedly take the method that sample is analyzed respectively, and change into the method that once takes systematic analysis after sample, reduced the analysis difficulty, simplified analytic process.The accuracy of its analysis and precision also can meet the demand of each compound mensuration in industrial silit fully.
Embodiment
System detecting method below in conjunction with specific embodiment to industrial silit component of the present invention is described in further detail.
Embodiment 1
1) take industrial silicon carbide sample 0.5000g to be measured, in platinum crucible, through 700 ~ 800 ℃ of high temperature sinterings, eliminate uncombined carbon, add the sulfuric acid solution that the 1mL volume ratio is 1: 1, rock gently, then be heated to 290 ~ 320 ℃, make the sulfuric acid volatilization of smoldering, continue at 700 ~ 800 ℃ of high temperature sintering 30min of high temperature furnace to constant, taking crucible and sample mass, is 20.5971g;
2) to adding 5mL density in crucible, be 1.15g/cm
3hydrofluorite, the sulfuric acid solution that the 0.5mL volume ratio is 1: 1, be heated to 320 ℃ of reaction 1h on middle temperature electric hot plate, the silicon dioxide in decomposition samples, after the sulfuric acid cigarette emits to the greatest extent, be cooled to room temperature, again adding 3mL density is 1.15g/cm
3hydrofluorite, the sulfuric acid solution that the 0.5mL volume ratio is 1: 1, then be heated to 290 ~ 320 ℃, make the sulfuric acid volatilization of smoldering, continue 700 ~ 800 ℃ of calcinations, to constant, to take crucible and residue quality, be 20.5940g,
20.5971g deduct 20.5940g, be the quality that 0.0031g is silicon dioxide in industrial silit sample to be measured, in former industrial silit sample to be measured, the massfraction of silicon dioxide is that 0.0031g/0.5000g * 100% obtains 0.62%;
3) to adding 2mL density in crucible, be 1.42g/cm
3the mixed solution of red fuming nitric acid (RFNA), hydrofluorite that 5mL density is 1.15g/cm3 and the 0.5mL volume ratio sulfuric acid that is 1: 1, then be heated to 290 ~ 320 ℃, make the acid solution volatilization of smoldering, continue 700 ~ 800 ℃ of calcinations to constant, taking crucible and residue gross mass is 20.5919g
20.5940g be the quality of elemental silicon in industrial silit sample to be measured with the difference of 20.5919g, i.e. 0.0021g, in former industrial silit sample to be measured the massfraction of elemental silicon be 0.0021g/0.5000g * 100% 0.42%;
4) continue to add the mixed flux of 4g natrium carbonicum calcinatum and boric acid in crucible, in described intermixture, natrium carbonicum calcinatum and boric acid mass ratio are 2: 1, be heated to 1150 ℃ of melting 60min fusion and decomposition complete, take out crucible and be cooled to room temperature, solid matter in crucible is in filling the 250mL beaker of 80mL hydrochloric acid-saturated BAS, leach frit at 80 ~ 100 ℃, fully dissolve, described hydrochloric acid-saturated BAS is that boric acid is dissolved in the hydrochloric acid solution that volume ratio is 1: 1, maintain the boric acid solid in solution, when then heating is concentrated into about 20mL, add 20mL ethanol through stirring abundant dissolving, continue evaporation drying and obtain the pressed powder thing,
5) adopt the animal glue mass method to be measured the content of silicon dioxide in described pressed powder thing, concrete assay method is: in the pressed powder thing, add the 15mL concentrated hydrochloric acid, low-temperature heat is to boiling, adding while hot 15mL volume mass mark is the animal sol solution that 10g/L is warm, through stirring, condense, filter, washing, obtain filter residue and filtrate; Filtrate is carried out to precise volume setting stand-by in the 250mL volumetric flask; By filter residue adopt 450 ~ 1000 ℃ carry out ashing, calcination is processed and is obtained silicon dioxide, the quality of weighing silicon dioxide is 0.7359g, calculating converts and obtains silit quality in former industrial silit to be measured is 0.4906g, in former industrial silit to be measured, the massfraction of silit is 0.4906g/0.5000g * 100%, obtains 98.12%;
6) divide the filtrate 100.00mL that gets constant volume in step 5), add the 5mL(excessive) the volume mass mark EDTA solution that is 10g/L, (this solution of 1.0mL is equivalent to the 1.4mg alundum (Al2O3)), then use the EDTA of zinc acetate standard solution overtitration, add the 1g sodium fluoride again in filtrate, replace the EDTA with the aluminium complexing, by concentration, be finally that the titration of 0.01000mol/L zinc acetate standard solution replaces the EDTA that, consume zinc acetate standard solution 1.07mL, according to the zinc acetate standard solution volume consumed, by calculating the quality 0.54mg that can draw alundum (Al2O3) in got filtrate, and then can converse the quality percentage composition of alundum (Al2O3) in original sample to be tested, the computational data process is:
, result is 0.27%;
7) divide the filtrate 10.00mL that gets constant volume in step 5), dripping 2mL volume mass mark is that 20g/L ascorbic acid solution (slightly excessive) reduced iron is to colourless ferrous iron, avoid the interference of ferric ion to titanium complex, place 5min, add the hydrochloric acid that the 10mL volume ratio is 1: 1, the diantipyrylmethane that 10mL volume mass mark is 50g/L, form yellow [Ti (DAPM)
3]
4+complex compound, adopt spectrophotometric method at the 390nm place to [Ti (DAPM) wherein
3]
4+in complex compound, the titanium amount is measured, and with the titania standard solution, draws calibration curve, on calibration curve, calculate in 10.00ml filtrate containing titania 3 μ g, and then the quality percentage composition that can converse titania in original sample to be tested is 0.015%.
8) divide the filtrate 10.00mL that gets constant volume in step 5), dripping 2mL volume mass mark is that 20g/L ascorbic acid solution (slightly excessive) is reduced into ferrous iron by the ferric iron in solution, mix, add again acetic acid-sodium acetate buffer solution that 20mL pH value is 4.7, the phenanthrolene solution that 2mL volume mass mark is 10 g/L, mix, regulate after its pH value is 4 ~ 5, form orange red [Fe (Phen)
2+] complex compound, adopt spectrophotometric method at the 510nm place to [Fe (Phen) wherein
2+] iron amount in complex compound measured, draw calibration curve with the di-iron trioxide standard solution, on calibration curve, calculate in 10.00mL filtrate containing di-iron trioxide 90.0 μ g, and then the quality percentage composition that can converse di-iron trioxide in original sample to be tested is 0.45%.
Embodiment 2
1) take industrial silicon carbide sample 1.0000g to be measured, in platinum crucible through 700 ~ 800 ℃ of high temperature sinterings, eliminate uncombined carbon, add the sulfuric acid solution that the 1mL volume ratio is 1: 1, rock gently, then be heated to 290 ~ 320 ℃, make the sulfuric acid volatilization of smoldering, continue, after 700 ~ 800 ℃ of high temperature sintering 30min constants of high temperature furnace, to take crucible and sample mass, for 37.8567g
2) to adding 10mL density in crucible, be 1.15g/cm
3hydrofluorite, the sulfuric acid solution that the 1mL volume ratio is 1: 1, be heated to 290 ~ 320 ℃ on middle temperature electric hot plate, the silicon dioxide in decomposition samples, after the sulfuric acid cigarette emits to the greatest extent, be cooled to room temperature, again adding 5mL density is 1.15g/cm
3hydrofluorite, the sulfuric acid solution that the 1mL volume ratio is 1: 1, then be heated to 290 ~ 320 ℃, make the sulfuric acid volatilization of smoldering, continue 700 ~ 800 ℃ of calcinations, to constant, to take crucible and residue quality, be 37.7756g;
37.8567g deduct 37.7756g, be the quality of silicon dioxide in industrial silit sample to be measured, i.e. 0.0811g, in former industrial silit sample to be measured the massfraction of silicon dioxide be 0.0811g/1.0000g * 100% 8.11%.
3) to adding 5mL density in crucible, be 1.42g/cm again
3red fuming nitric acid (RFNA), the sulfuric acid solution that the hydrofluorite that 10mL density is 1.15g/cm3 and 1mL volume ratio are 1: 1, then be heated to 290 ~ 320 ℃, make the sulfuric acid volatilization of smoldering, continue 700 ~ 800 ℃ of calcinations to constant, taking pot and residue gross mass is 37.7578g, weighing last time 37.7756g and its is poor, be the quality of elemental silicon in industrial silit sample to be measured, i.e. 0.0178g, in former industrial silit sample to be measured the massfraction of elemental silicon be 0.0178 g/1.000g * 100% 1.78%.
4) continue to add the mixed flux of 6 g natrium carbonicum calcinatums and boric acid in crucible, in described intermixture, natrium carbonicum calcinatum and boric acid mass ratio are 2: 1, be heated to 1200 ℃ of melting 45min fusion and decomposition complete, take out crucible and be cooled to room temperature, solid matter in crucible is in the 250mL beaker that fills 80 mL hydrochloric acid-saturated BAS, leaching frit at 80 ~ 100 ℃ fully dissolves, described hydrochloric acid-saturated BAS is that boric acid is dissolved in the hydrochloric acid solution that volume ratio is 1: 1, maintain the boric acid solid in solution, when then heating is concentrated into approximately 20 mL, add the abundant stirring and dissolving of 20mL ethanol, continue evaporation drying and obtain the pressed powder thing,
5) according to the animal glue mass method, the content of silicon dioxide in described pressed powder thing is measured, concrete assay method is: in described pressed powder thing, add the 15mL concentrated hydrochloric acid, low-temperature heat is to boiling, adding while hot 15mL volume mass mark is 10g/L, warm animal sol solution, through stirring, condense, filter, washing, obtain filter residue and filtrate; Filtrate is carried out to precise volume setting stand-by in the 250mL volumetric flask; By filter residue adopt 450 ~ 1000 ℃ carry out ashing, calcination is processed and is obtained silicon dioxide, the quality of weighing silicon dioxide is 1.2775 g, calculating converts and obtains silit quality in former industrial silit to be measured is 0.8517g, in former industrial silit to be measured, the massfraction of silit is 0.8517g/1.0000g * 100%, obtains 85.17%;
6) divide the filtrate 50.00mL that gets constant volume in step 5), add the 10mL(excessive) EDTA solution (concentration of EDTA is that the volume mass mark is 20g/L, 1.0mL this solution is equivalent to the 2.75mg alundum (Al2O3)), then use the EDTA of zinc acetate standard solution overtitration, add a certain amount of villiaumite again in filtrate, this villiaumite can be sodium fluoride, ammonium fluoride or potassium fluoride 1.5g, replace the EDTA with the aluminium complexing, by concentration, be finally that the titration of 0.01000mol/L zinc acetate standard solution replaces the EDTA that, consume zinc acetate standard solution 6.95mL, according to the zinc acetate standard solution volume consumed, by calculating the quality 3.54mg that can draw alundum (Al2O3) in got filtrate, and then can converse the quality percentage composition of alundum (Al2O3) in original sample to be tested, the computational data process is:
, result is 1.77%;
7) divide the filtrate 10.00mL that gets constant volume in step 5), dripping 4mL volume mass mark is that 20g/L ascorbic acid solution (slightly excessive) reduced iron is to colourless ferrous iron, avoid the interference of ferric ion to titanium complex, place 5min, add the hydrochloric acid that the 10mL volume ratio is 1:1, the diantipyrylmethane that 10mL volume mass mark is 50g/L, form yellow [Ti (DAPM)
3]
4+complex compound, adopt spectrophotometric method at the 390nm place to [Ti (DAPM) wherein
3]
4+in complex compound, the titanium amount is measured.Draw calibration curve with the titania standard solution, calculate on calibration curve in 10.00ml filtrate containing titania 17.6 μ g, and then the quality percentage composition that can converse titania in original sample to be tested is 0.044%;
8) divide the filtrate 5.00mL that gets constant volume in step 5), dripping 2mL volume mass mark is 20g/L ascorbic acid solution (slightly excessive), ferric iron in solution is reduced into to ferrous iron, add again acetic acid-sodium acetate buffer solution that the 20mLpH value is 4.7, the phenanthrolene solution that 2mL volume mass mark is 10 g/L, mix, regulate after its pH value is 4 ~ 5, form orange red [Fe (Phen)
2+] complex compound, adopt spectrophotometric method at the 510nm place to [Fe (Phen) wherein
2+] iron amount in complex compound measured.Draw calibration curve with the di-iron trioxide standard solution, calculate on calibration curve in 5.00mL filtrate containing di-iron trioxide 378 μ g, and then the quality percentage composition that can converse di-iron trioxide in original sample to be tested is 1.89%.
Embodiment 3:
1) take industrial silicon carbide sample 0.8000g to be measured, in platinum crucible through 700 ~ 800 ℃ of high temperature sinterings, eliminate uncombined carbon, add the sulfuric acid solution that the 1mL volume ratio is 1: 1, rock gently, then be heated to 290 ~ 320 ℃, make the sulfuric acid volatilization of smoldering, continuation, after 700 ~ 800 ℃ of high temperature sintering 30min constants of high temperature furnace, takes crucible and sample mass, is 30.5315g;
2) to adding 8mL density in crucible, be 1.15g/cm
3hydrofluorite, the sulfuric acid solution that the 1mL volume ratio is 1: 1, be heated to 290 ~ 320 ℃ on middle temperature electric hot plate, the silicon dioxide in decomposition samples, after the sulfuric acid cigarette emits to the greatest extent, be cooled to room temperature, again adding 8mL density is 1.15g/cm
3hydrofluorite, the sulfuric acid solution that the 1mL volume ratio is 1: 1, then be heated to 290 ~ 320 ℃, make the sulfuric acid volatilization of smoldering, continue 700 ~ 800 ℃ of calcinations, to constant, to take crucible and residue quality, be 30.4233g;
30.5315g deduct 30.4233g, be the quality of silicon dioxide in industrial silit sample to be measured, i.e. 0.1082g, in former industrial silit sample to be measured the massfraction of silicon dioxide be 0.1082g/0.8000g * 100% 13.52%;
3) to adding 8mL density in crucible, be 1.42g/cm again
3red fuming nitric acid (RFNA), 8mL density be 1.15g/cm
3hydrofluorite and the 1mL volume ratio sulfuric acid solution that is 1: 1, then be heated to 290 ~ 320 ℃ of degree, make the sulfuric acid volatilization of smoldering, continuation 700 ~ 800 ℃ of calcinations to constant, taking pot and residue gross mass is 30.4009g, and weighing last time 30.4233g and its poor is the quality of elemental silicon in industrial silit sample to be measured, be 0.0224g, in former industrial silit sample to be measured, the massfraction of elemental silicon is that 0.0224 g/0.8000g * 100% obtains 2.80%;
4) continue to add the mixed flux of 5g natrium carbonicum calcinatum and boric acid in crucible, in described intermixture, natrium carbonicum calcinatum and boric acid mass ratio are 2: 1, be heated to 1050 ℃ of melting 30min fusion and decomposition complete, take out crucible and be cooled to room temperature, solid matter in crucible is in the 250mL beaker that fills 90 mL hydrochloric acid-saturated BAS, leaching frit at 80 ~ 100 ℃ fully dissolves, described hydrochloric acid-saturated BAS is that boric acid is dissolved in the hydrochloric acid solution that volume ratio is 1: 1, maintains the boric acid solid in solution.When then heating is concentrated into about 20mL, add the abundant stirring and dissolving of 20mL ethanol, continue evaporation drying and obtain the pressed powder thing;
5) according to the animal glue mass method, the content of silicon dioxide in described pressed powder thing is measured, concrete assay method is: in described pressed powder thing, add the 15mL concentrated hydrochloric acid, low-temperature heat is to boiling, adding while hot 15mL volume mass mark is 10g/L, warm animal sol solution, through stirring, condense, filter, washing, obtain filter residue and filtrate; Filtrate is carried out to precise volume setting stand-by in the 250mL volumetric flask; By filter residue adopt 450 ~ 1000 ℃ carry out ashing, calcination is processed and is obtained silicon dioxide, the quality of weighing silicon dioxide is 0.8767g, calculating converts and obtains silit quality in former industrial silit to be measured is 0.5845g, in former industrial silit to be measured, the massfraction of silit is 0.5845g/0.8000g * 100%, obtains 73.06%;
6) divide the filtrate 50.00mL that gets constant volume in step 5), add the 10mL(excessive) EDTA solution (concentration of EDTA is that the volume mass mark is 20g/L, 1.0mL this solution is equivalent to the 2.75mg alundum (Al2O3)), then use the EDTA of zinc acetate standard solution overtitration, add a certain amount of villiaumite again in filtrate, this villiaumite can be sodium fluoride, ammonium fluoride or potassium fluoride 2.0g, replace the EDTA with the aluminium complexing, by concentration, be finally that the titration of 0.01000mol/L zinc acetate standard solution replaces the EDTA that, consume zinc acetate standard solution 17.35mL, according to the zinc acetate standard solution volume consumed, by calculating the quality 3.54mg that can draw alundum (Al2O3) in got filtrate, and then can converse the quality percentage composition of alundum (Al2O3) in original sample to be tested, the computational data process is:
, result is 5.53%;
7) divide and get constant volume in the filtrate 5.00mL of 250mL volumetric flask, dripping 1mL volume mass mark is that 20g/L ascorbic acid solution (slightly excessive) reduced iron is to colourless divalence, avoid the interference of ferric ion to titanium complex, place 5min, add the hydrochloric acid that the 10mL volume ratio is 1: 1, the diantipyrylmethane that 10mL volume mass mark is 50g/L, form yellow [Ti (DAPM)
3]
4+complex compound, adopt spectrophotometric method at the 390nm place to [Ti (DAPM) wherein
3]
4+in complex compound, the titanium amount is measured.Draw calibration curve with the titania standard solution, calculate on calibration curve in 5.00ml filtrate containing titania 432 μ g, and then the quality percentage composition that can converse titania in original sample to be tested is 0.27%;
8) divide and get constant volume in the filtrate 5.00mL of 250mL volumetric flask, dripping 1mL volume mass mark is that 20g/L ascorbic acid solution (slightly excessive) is reduced into ferrous iron by the ferric iron in solution, mix, add again acetic acid-sodium acetate buffer solution that the 20mLpH value is 4.7, the phenanthrolene solution that 2mL volume mass mark is 10g/L, mix, regulate after its pH value is 4 ~ 5, form orange red [Fe (Phen)
2+] complex compound, adopt spectrophotometric method at the 510nm place to [Fe (Phen) wherein
2+] iron amount in complex compound measured.Draw calibration curve with the di-iron trioxide standard solution, calculate on calibration curve in 5.00mL filtrate containing di-iron trioxide 337.6 μ g, and then the quality percentage composition that can converse di-iron trioxide in original sample to be tested is 2.11%.
Claims (4)
1. the system detecting method of an industrial silit component, is characterized in that, it comprises the following steps:
1) taking quality is m
1to be measured industrial silit sample, be placed in container through 700 ~ 800 ℃ of high temperature sinterings, then add the abundant dissolved samples of enough dilute sulfuric acids, then again through 700 ~ 800 ℃ of high temperature sinterings to constant weight, weighing container and sample, its gross mass is counted m
2;
2) to the mix acid liquor that adds enough dense hydrofluorite and dilute sulfuric acid in container, dense hydrofluorite in described mix acid liquor and dilute sulfuric acid volume ratio are 5 ~ 10: 1, heating is smoldered volatilization fully 290 ~ 320 ℃ of isothermal reaction to acid solutions, again through 700 ~ 800 ℃ of high temperature sinterings to constant, weighing container and sample, its gross mass is counted m
3, described m
2with m
3difference be the quality of silicon dioxide in industrial silit sample to be measured;
3) to the mixed solution that adds enough red fuming nitric acid (RFNA)s, dense hydrofluorite and dilute sulfuric acid in container, in described mixed solution, the volume ratio of red fuming nitric acid (RFNA), dense hydrofluorite and dilution heat of sulfuric acid is 4 ~ 10: 10 ~ 20: 1 ~ 2, heating is smoldered volatilization fully 290 ~ 320 ℃ of isothermal reaction to acid solutions, again after 700 ~ 800 ℃ of high temperature sintering constants, weighing container and sample, its gross mass is counted m
4, described m
3with m
4difference be the quality of elemental silicon in industrial silit sample to be measured;
4) continue to add 5 ~ 10 times of m in crucible
1natrium carbonicum calcinatum and the intermixture of boric acid, the mass ratio 1.5 ~ 3: 1 of natrium carbonicum calcinatum and boric acid in described intermixture, be heated to 1050 ~ 1200 ℃ of melting 30 ~ 60min, sample in container is that fusion and decomposition is complete, then be cooled to room temperature and obtain solid matter, adopt enough hydrochloric acid-saturated BAS that solid matter is fully dissolved under 80 ~ 100 ℃ of conditions, after the solution heating is concentrated to the state of a small amount of liquid of residue, add enough ethanol fully to dissolve, finally heat evaporate to dryness, obtain the pressed powder thing;
5) fully dissolve to adding in the pressed powder thing after enough concentrated hydrochloric acids heating to boil to the pressed powder thing, then add appropriate gelatin solution, obtain filter residue and filtrate through stirring, cohesion, filtration, washing operation successively, filtrate is carried out to precise volume setting stand-by; By filter residue adopt 450 ~ 1000 ℃ carry out ashing, calcination is processed and is obtained silica solid, the quality of weighing silicon dioxide is counted m
5, in industrial silicon carbide sample, the quality of silit is 2m
5/ 3;
6) get the stand-by filtrate of a certain amount of step 5) constant volume, add excessive EDTA, then use the EDTA of zinc acetate standard solution overtitration, add a certain amount of villiaumite again in solution, heating is boiled, and fluorine replaces the EDTA with the aluminium complexing, finally with the titration of zinc acetate standard solution, replace the EDTA that, according to the zinc acetate standard solution volume consumed, can draw the quality of aluminium in got filtrate by calculating, and then can converse the quality of alundum (Al2O3) in industrial silicon carbide sample;
7) separately get the stand-by filtrate of a certain amount of step 5) constant volume, drip appropriate ascorbic acid solution existing colourless to filtrate, after adopting watery hydrochloric acid to regulate the pH value to 4 of filtrate ~ 5, add appropriate diantipyrylmethane, form yellow [Ti (DAPM)
3]
4+complex compound, adopt spectrophotometric method to [Ti (DAPM) wherein
3]
4+ti content in complex compound is measured, and can extrapolate the quality of titania in industrial silicon carbide sample;
8) separately get again the stand-by filtrate of a certain amount of step 5) constant volume, drip appropriate ascorbic acid solution existing colourless to filtrate, after regulating its pH value to 4 ~ 5 with acetic acid-sodium acetate buffer solution, add phenanthrolene to form orange red [Fe (Phen)
2+] complex compound, adopt spectrophotometric method to [Fe (Phen)
2+] iron content in complex compound measured, can extrapolate in industrial silicon carbide sample in the quality of di-iron trioxide;
9), according to the quality of determined each component, can calculate quality is m
1to be measured industrial silit sample in the quality percentage composition of each component.
2. the system detecting method of industrial silit component according to claim 1, it is characterized in that: the hydrochloric acid in described step 4)-saturated BAS is that boric acid is dissolved in the hydrochloric acid solution that volume ratio is 1: 1, and maintains the boric acid solid in described solution.
3. the system detecting method of industrial silit component according to claim 1 and 2 is characterized in that: a kind of in the solid that the villiaumite in described step 6) is potassium fluoride, sodium fluoride, ammonium fluoride or aqueous solution.
4. the system detecting method of industrial silit component according to claim 1 and 2, it is characterized in that: the sulfuric acid solution that described dilute sulfuric acid is water and concentrated sulphuric acid volume ratio 1: 1 ~ 2, described dense hydrofluorite refers to that density is 1.15 ~ 1.10g/cm
3hydrofluoric acid solution, described red fuming nitric acid (RFNA) is that density is 1.42 ~ 1.40g/cm
3salpeter solution, described concentrated hydrochloric acid is that density is 1.19 ~ 1.15g/cm
3hydrochloric acid solution.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103822841A (en) * | 2013-12-27 | 2014-05-28 | 四川德胜集团钒钛有限公司 | Method for detecting content of SiC in SiC |
| CN104101526A (en) * | 2014-07-17 | 2014-10-15 | 中国兵器工业集团第五三研究所 | SiC (silicon carbide) content standard substance and preparation method thereof |
| CN104359903A (en) * | 2014-11-17 | 2015-02-18 | 江南大学 | Novel method for measuring iron content in waste mortar |
| CN105223188A (en) * | 2014-05-29 | 2016-01-06 | 上海梅山钢铁股份有限公司 | A kind of steel-making assay method of elemental silicon content in siliceous exothermic mixture |
| CN106770921A (en) * | 2017-01-12 | 2017-05-31 | 长安大学 | The sensing equipment and its method of cement content in a kind of Cement treated material |
| CN109470693A (en) * | 2018-10-18 | 2019-03-15 | 中国人民解放军国防科技大学 | Test paper for detecting vitamin C and preparation method and application thereof |
| CN110160908A (en) * | 2019-05-13 | 2019-08-23 | 航天科工防御技术研究试验中心 | The mass fraction detection method of SiC reinforcement body in a kind of aluminum matrix composite |
| CN111678835A (en) * | 2020-06-22 | 2020-09-18 | 浙江天能电池(江苏)有限公司 | Method for measuring content of silicon dioxide in silica sol for storage battery |
| CN112179803A (en) * | 2020-09-29 | 2021-01-05 | 昆明理工大学 | Quantitative analysis method for content of elemental silicon in industrial silicon slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101839862A (en) * | 2010-03-29 | 2010-09-22 | 武钢集团昆明钢铁股份有限公司 | Method for determining total silicon content in silicon carbide refractory material |
| CN102243177A (en) * | 2011-04-20 | 2011-11-16 | 武汉钢铁(集团)公司 | Method for determining silicon dioxide in silicon carbide |
| CN102393369A (en) * | 2011-11-08 | 2012-03-28 | 平顶山易成新材料股份有限公司 | Temperature increment method for measuring content of ferric oxide in silicon carbide through adopting atomic absorption method |
| CN102998271A (en) * | 2012-12-10 | 2013-03-27 | 天津大学 | Determination method of silicon dioxide, silicon and silicon carbide in waste mortar from silicon wafer cutting |
| CN103196783A (en) * | 2013-03-28 | 2013-07-10 | 内蒙古包钢钢联股份有限公司 | Method for determining content of silicon carbide in temperature raising agent |
-
2013
- 2013-09-02 CN CN201310393798.6A patent/CN103439213B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101839862A (en) * | 2010-03-29 | 2010-09-22 | 武钢集团昆明钢铁股份有限公司 | Method for determining total silicon content in silicon carbide refractory material |
| CN102243177A (en) * | 2011-04-20 | 2011-11-16 | 武汉钢铁(集团)公司 | Method for determining silicon dioxide in silicon carbide |
| CN102393369A (en) * | 2011-11-08 | 2012-03-28 | 平顶山易成新材料股份有限公司 | Temperature increment method for measuring content of ferric oxide in silicon carbide through adopting atomic absorption method |
| CN102998271A (en) * | 2012-12-10 | 2013-03-27 | 天津大学 | Determination method of silicon dioxide, silicon and silicon carbide in waste mortar from silicon wafer cutting |
| CN103196783A (en) * | 2013-03-28 | 2013-07-10 | 内蒙古包钢钢联股份有限公司 | Method for determining content of silicon carbide in temperature raising agent |
Non-Patent Citations (4)
| Title |
|---|
| 中华人民共和国国家质量监督检验检疫总局: "《GB/T 16555-2008 含碳、碳化硅、氮化物耐火材料化学分析方法》", 26 June 2008, article "GB/T 16555-2008 含碳、碳化硅、氮化物耐火材料化学分析方法", pages: 1-32 * |
| 中华人民共和国国家质量监督检验检疫总局: "《GB/T 3045-2003 普通磨料 碳化硅化学分析方法》", 8 October 2003, article "GB/T 3045-2003 普通磨料 碳化硅化学分析方法", pages: 1-13 * |
| 中华人民共和国国家质量监督检验检疫总局: "《GB/T 6901-2008 硅质耐火材料化学分析方法》", 8 May 2008, article "GB/T 6901-2008 硅质耐火材料化学分析方法", pages: 1-24 * |
| 林炳熹 等: "氢氟酸挥散重量法连续测定游离二氧化硅、单质硅、碳化硅", 《耐火材料》, vol. 43, no. 3, 30 June 2009 (2009-06-30), pages 239 - 240 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103822841A (en) * | 2013-12-27 | 2014-05-28 | 四川德胜集团钒钛有限公司 | Method for detecting content of SiC in SiC |
| CN105223188A (en) * | 2014-05-29 | 2016-01-06 | 上海梅山钢铁股份有限公司 | A kind of steel-making assay method of elemental silicon content in siliceous exothermic mixture |
| CN104101526A (en) * | 2014-07-17 | 2014-10-15 | 中国兵器工业集团第五三研究所 | SiC (silicon carbide) content standard substance and preparation method thereof |
| CN104101526B (en) * | 2014-07-17 | 2016-07-06 | 中国兵器工业集团第五三研究所 | A kind of carborundum content standard substance and preparation method thereof |
| CN104359903A (en) * | 2014-11-17 | 2015-02-18 | 江南大学 | Novel method for measuring iron content in waste mortar |
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| CN109470693A (en) * | 2018-10-18 | 2019-03-15 | 中国人民解放军国防科技大学 | Test paper for detecting vitamin C and preparation method and application thereof |
| CN110160908A (en) * | 2019-05-13 | 2019-08-23 | 航天科工防御技术研究试验中心 | The mass fraction detection method of SiC reinforcement body in a kind of aluminum matrix composite |
| CN111678835A (en) * | 2020-06-22 | 2020-09-18 | 浙江天能电池(江苏)有限公司 | Method for measuring content of silicon dioxide in silica sol for storage battery |
| CN112179803A (en) * | 2020-09-29 | 2021-01-05 | 昆明理工大学 | Quantitative analysis method for content of elemental silicon in industrial silicon slag |
| CN112179803B (en) * | 2020-09-29 | 2022-03-01 | 昆明理工大学 | Quantitative analysis method for content of elemental silicon in industrial silicon slag |
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