CN106168587A - A kind of measure the method for iron content in fireworks and firecrackers firework medicament - Google Patents
A kind of measure the method for iron content in fireworks and firecrackers firework medicament Download PDFInfo
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Abstract
A kind of measure the method for iron content in fireworks and firecrackers firework medicament, comprise the following steps: prepare the ferrum working solution that many parts of concentration do not wait, with energy dispersion type Xray fluorescence spectrometer as detecting instrument, assuming that certain sample size, the intensity correction mathmetic correction using X fluorescence spectrum quantitative analysis sets up analysis method, many parts of ferrum working solutions of preparation will be converted into the mass percent concentration of Fe at the mass concentration of Fe, and record the fluorescence intensity of each sample introduction Fe, make calibration curve；By firework medicament preparation test liquid to be measured, the fluorescence intensity of the Fe of display on grapher, corresponding Fe mass percent concentration value is read according to the above-mentioned calibration curve determined with this fluorescence intensity, and calculate the content of ferrum in sample, the method of the invention eliminates or substantially eliminates the matrix effect in sample between each element, and simple to operate, the detection cycle is short, accuracy is good, and precision is high.
Description
Technical field
The present invention relates to analysis and testing technology field, be specifically related to energy dispersion type x-ray fluorescence spectrometry fireworks
The method of iron content in firecracker firework medicament.
Background technology
In prior art, in fireworks and firecrackers firework medicament, the detection method of iron content is based on traditional chemical analysis side
Method, the most conventional method standard is " mensuration of iron content in fireworks and firecrackers pyrotechnic composition " (GB/T 20617-2006).This mark
The ultimate principle of quasi-method: test portion, after suitable pretreatment, sinks with sodium hydroxide after first fully dissolving with dust technology, filter again
Form sediment, precipitation enrichment, filter after use dissolving with hydrochloric acid filtering residue, take a certain amount of filtrate after constant volume in conical flask, with hydrochloric acid and ammonia
Regulation pH value of solution 2.0-pH2.5, after adding a certain amount of hydrochloric acid buffer solution, heating in water bath adds sulfo group to 60 DEG C～70 DEG C while hot
Salicylic acid, as indicator solution, is titrated to the colour-fast terminal that is of ecru 30s with EDETATE SODIUM standard titration solution, and calculating is tapped a blast furnace
Amount.
Method described in this standard has the disadvantage that (1) detection cycle is longer, and general those of skill in the art need 2 works
Make day just to complete one-time detection.It addition, be easy in concrete process of the test because testing crew skilled operation degree draws not
Enter to cause the uncertainty of measuring result error.(2) operating procedure is relatively complicated, and sample priority dehydrated alcohol and acetone are repeatedly
After washing, filter with after dilute nitric acid dissolution, shift, precipitate, be enriched with, re-dissolved, constant volume, regulation pH value, heating in water bath, finally take
One random sample liquid, is titrated to the colour-fast terminal that is of ecru 30s with EDETATE SODIUM standard titration solution, calculates the amount tapped a blast furnace.(3)
Method requires height to experimenter, in operating procedure many places relate to washing, shift, dissolve, filter, reprecipitation, be enriched with, dissolve,
Regulation pH value and titration etc. are readily incorporated probabilistic operating procedure, and the necessary significant care of each test operation personnel is with thin
Cause, be otherwise very easy to introduce artificial uncertainty.
The method that energy dispersion type Xray fluorescence spectrometer is developed at present is used for the lossless qualitative analysis of sample.Pin
Detecting solid sample sxemiquantitative and quantitative elemental, most samples use nondestructive determination, powder pressing method and fusion method
Directly measure (such as: " the mensuration X-ray fluorescence spectroscopy of bullion content " (GB/T 18043-2008) uses lossless inspection
Survey method, " aluminium oxide chemical analysis method and method for measuring physical properties the 30th partial x-ray fluorescence spectrum method for measuring element contain
Amount " (GB/T6609.30 2009) use fusion method, and " EDXRF method directly measures W-Fe-Ni-Co alloy compound group
Point " (" nuclear electronics and Detection Techniques " 05 phase in 2007) use pressed disc method, " regulated substance lead in electronic and electrical equipment,
The rapid screening X-ray fluorescence spectroscopy of hydrargyrum, chromium, cadmium and bromine " (GB/Z 21277-2007) use pressed disc method or melted
Method).
Owing to the firework medicament chemical composition of different types of fireworks and firecrackers goods use is different and composition is the most multiple
Miscellaneous, by least five, six kind, ten multiple compounds mix at most.Firework medicament also exists between each element the matrix of complexity
Effect (includes absorption-enhancement effect and physical-chemical effect between element), it is impossible to utilize energy dispersion type X-ray fluorescence spectra
Method (EDXRF) directly uses powder pressing method and fusion method to measure the solid powder sample that matrix background is complicated and changeable.Furthermore, by
In fireworks and firecrackers firework medicament, there is inflammable and explosive characteristic, it is difficult to it is carried out tabletting or fusion method carries out pre-treatment.So far
Till also there are no energy dispersion type X-ray fluorescence spectroscopy based on collective effect targeting control technology (solwution method) detection cigarette
The open source literature report of iron content in flower firecracker firework medicament.
Summary of the invention
The technical problem to be solved in the present invention is to provide one, and the method is simple to operate, the detection cycle is short, and testing result
Accuracy is good, and what precision was high measures the method for iron content in fireworks and firecrackers firework medicament.
A kind of measure the method for iron content in fireworks and firecrackers firework medicament, comprise the following steps:
S1, drafting calibration curve
S11, prepare many parts of concentration ferrum working solution not etc., high-purity iron powder is dissolved with dust technology by process for preparation；
S12, with energy dispersion type Xray fluorescence spectrometer as detecting instrument, the sample supposed for calibration curve with 2.0g
Amount, (in this step, selected 2.0g is the sample size that calibration curve supposes, is to penetrate considering energy dispersion type X through applicant
On the basis of the matrix effect of line fluorescence spectrophotometer, having carried out what substantial amounts of test determined, changing this numerical value will affect test
The accuracy of result), use the mathmetic correction of the intensity correction of X fluorescence spectrum quantitative analysis to set up analysis method；Will step
In many parts of ferrum working solutions of rapid S11 preparation, the mass concentration of Fe is converted into the mass percent concentration of Fe, sample introduction the most one by one, note
Record the fluorescence intensity of the Fe of each sample introduction, the mass percent concentration of Fe in each ferrum working solution as abscissa, with above-mentioned Fe
Fluorescence intensity corresponding to mass percent concentration be vertical coordinate, make calibration curve；Wherein, by following formula, ironworker is made
In liquid, the mass concentration of Fe is converted into the mass percent concentration of Fe:
Wherein, Fe% represents the mass percent concentration of Fe in ferrum working solution, and unit is %；C represents Fe in ferrum working solution
Mass concentration, unit is g/L；0.5 represents the volume supposing sample size constant volume, and unit is L；2 represent what calibration curve supposed
Sample size, unit is g；
S2, the iron content measured in firework medicament:
S21, preparation test liquid: with firework medicament as sample, weigh the sample of 1.9g～2.1g, be accurate to when weighing
0.1mg, is placed in beaker, adds 30mL～50mL water, heats micro-boiling 7min～9min, filtered while hot, repeatedly wash with water, will
Residue collection, to another beaker, adds a certain amount of nitric acid, places and heats micro-boiling 20min on electric furnace, while hot with filter paper filtering, and will filter
Liquid is collected to volumetric flask, adds water and is settled to scale, it is ensured that the solution after constant volume is dense after the solution in volumetric flask is cooled to room temperature
Degree, in calibration curve scope, obtains test liquid；
S22, by the testing conditions of step S12, test liquid is loaded specimen cup, it is ensured that sample liquid thickness >=15mm, record energy
The fluorescence intensity of the Fe of display on chromatic dispersion quantity type Xray fluorescence spectrometer, bent according to the above-mentioned calibration determined with this fluorescence intensity
Line reads corresponding Fe mass percent concentration value；
The content of ferrum in S23, calculating sample:
The mass percent concentration of fe in calculating sample as follows:
Wherein, ω represents the mass percent concentration of fe in sample, and unit is %；ω0Represent according to calibration curve
The Fe mass percent concentration value read, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents sample
The actual quality weighed, unit is g；V represents the volume of constant volume after sample dissolution, it is ensured that the solution concentration after constant volume is at calibration song
Line scope, unit is mL；500 represent the volume supposing sample size constant volume, and unit is mL.
Further, the method preparing ferrum working solution in S11 is: weigh a certain amount of high-purity iron powder or other ferrum element ginseng
Examining material, add appropriate water and dust technology dissolves, be then settled to certain volume, the mass concentration of Fe is 0.08g/L
～0.67g/L, this concentration range through applicant at the base of the matrix effect considering energy dispersion type Xray fluorescence spectrometer
On plinth, having carried out what substantial amounts of test determined, changing this numerical value will affect the accuracy of test result.
Further, nitric acid described in S11 adds according to the amount of 30mL/g～40mL/g sample, the mass percent of nitric acid
Concentration is 40%～60%.
Further, the testing conditions of S12 is: the mathmetic correction of employing intensity correction sets up analysis method, aperture is
The X-ray light pipe collimator of 8.8mm～14mm, it is possible to filtering the filter of the energy X-ray less than 7.111KeV, arranging voltage is
16KV～24KV, analysis time is 30s～80s, and energy range is 0～40KeV, and during counting rate is, gaseous environment is air, electricity
Stream is automatic, and matrix effect is not for consider.
Preferably, in S12, the testing inspection condition of energy dispersion type Xray fluorescence spectrometer is: arranging voltage is 20KV,
Analysis time is 50s, and energy range is 0～20KeV.
Further, in S21 the volume mass of dust technology and the amount of sample than for 30mL/g～40mL/g.
Preferably, in S22, usual test liquid thickness is 15mm～30mm.
Further, in S23, the span of m is 1.9g～2.1g, and the determination of this interval is to exist through applicant
On the basis of considering the matrix effect of energy dispersion type Xray fluorescence spectrometer, carry out what substantial amounts of test determined, changed
This numerical value will affect the accuracy of test result.
The ultimate principle of this assay method: for the fireworks and firecrackers feature of firework medicament chemical composition, set up special
Mathematical model, global optimization can directly affect each factor of measurement result, including: dissolve the solvent species of test portion, change
Learn composition and volume number, test portion dissolution conditions, test solution constant volume, for setting up the matrix effect mathmetic correction of analysis method
Type, for make calibration curve test portion suppose sample size, series standard solution matrix composition, concentration range and standard molten
The matrix effect of the interval of liquid point value and quantity, the actual sample weighting amount of test portion and energy dispersion type X fluorescence spectrum instrument interacts
Work in every parameter and the samples such as form, voltage, electric current, the selection of filter, analysis time, counting rate, gaseous environment, energy range
The thickness etc. of test solution in product cup.First, first fully dissolve test portion with water, make the KClO in test portion4And KClO3Deng water solublity chemical combination
Thing separates with target-finding element of Fe, thus reduces the impact of matrix effect in sample test liquid；Secondly, dust technology is selected
On the one hand dissolve test portion as solvent, be the examining containing Fe elemental composition such as the iron powder that can sufficiently dissolve in test portion based on dust technology
On the other hand consider, be also based on the consideration of nitric acid solvent compositing characteristic, nitric acid contains only tri-kinds of light elements of H, N and O, and this three
The introducing planting element will not produce the interference of matrix effect to test；Again, global optimization test portion dissolution conditions, test solution constant volume body
Long-pending, for setting up the matrix effect mathmetic correction type of analysis method, making test portion supposition sample size, the series of calibration curve
Matrix composition, concentration range and the interval of standard solution point value of standard solution and quantity, the actual sample weighting amount of test portion and energy color
Dissipate the matrix effect interaction type of type X fluorescence spectrum instrument, voltage, electric current, the selection of filter, analysis time, counting rate,
Work in every parameter and the specimen cup pilot scale such as thickness of test solution in the work in every parameter such as gaseous environment, energy range and specimen cup
The thickness of liquid etc. directly affect each factor of measurement result, set up and are specifically designed for Fe element survey in fireworks and firecrackers firework medicament
Fixed calibration curve, in this test condition, owing to other concentration of element of Cu, Bi, Al, the Mg etc. in sample test solution are relatively low, H, O
Belong to, with elements such as N, the light element that Xray fluorescence spectrometer is insensitive, and the matrix effect of Fe element is in calibration curve standard
The interval concentration range of point is negligible, thus realizes the matrix effect that targeting controls in test solution between each element；Finally, can basis
The diversity of all kinds fireworks and firecrackers firework medicament sample determines whether to adjust sample size, carries out Fe based on this calibration curve
The quantitative analysis of element.
Compared with prior art, the having the beneficial effect that of the method for the invention
1, utilize solwution method eliminate or substantially eliminate matrix effect, thus can directly use energy dispersion type XRF
Spectrographic method Accurate Determining goes out the iron content in fireworks and firecrackers firework medicament；Solwution method is used to eliminate or substantially eliminate matrix effect
And advantage is in particular in: (1) liquor sample eliminates the intrinsic inhomogeneities of solid sample and physical-chemical effect,
The analysis result obtained more can represent whole analysis sample；(2) Macrodilution based on solvent, the composition of sample and standard specimen is close
The composition of solvent, and solvent is mainly made up of light element, absorption-enhancement effect becomes the least, and matrix effect is the most permissible
Do not consider；Being additionally, since X-ray penetration depth relatively deep, fluorescent radiation absorbs less, so can obtain higher the sensitiveest
Degree；(3) if solution made by the sample that standard specimen is difficult to obtain, calibration curve can use standard reagent to synthesize, and estimates background etc.
The blank sample of factor is readily made；(4) after water-soluble, constant volume is to certain volume, in test liquid in addition to Fe element for sample
The matrix effect that Fe element is produced by other light elements such as element and H, O, N such as Cu, Bi, Al, Mg is the least, is negligible.
2, the method for the invention is simple to operate, and the detection cycle is short, and after establishing calibration curve, whole mensuration process is only
Including sample weighing, dissolving, shift 4 easy steps such as constant volume, examination with computer, total time-consuming less than 2h, labor intensity is relatively low
And it is less demanding to operator.
3, using the method for the invention to detect, accuracy is good, and precision is high.
Accompanying drawing explanation
Fig. 1 is the calibration curve of the mass percent concentration-fluorescence intensity of the Fe that inventive embodiments 1 obtains, the most horizontal seat
Being designated as the mass percent concentration of Fe in each ferrum working solution, unit is %；Vertical coordinate is and the mass percent concentration of above-mentioned Fe
Corresponding fluorescence intensity, unit is cps/mA.
Detailed description of the invention
With specific embodiment, the invention will be further described below, but the invention is not limited in these embodiments.
Embodiment 1: make calibration curve
1) prepare many parts of ferrum working solutions and (require that in the ferrum working solution of gained, the mass concentration of Fe is 0.08g/L～0.67g/
L):
Concrete compound method is with reference to as follows:
Accurately weigh 0.83g high-purity iron powder (being accurate to 0.1mg), be placed in 300mL beaker, according to 30mL/g～40mL/g
The amount of sample adds dust technology, beaker is placed on electric furnace heating 15min～20min, is transferred to after solution is cooled to room temperature
500mL volumetric flask, adds water and is settled to scale；Wherein, described dust technology is HNO3Content is the nitric acid of 40%～60% mass.
Prepare 8 parts of ferrum working solutions: pipette respectively the ferrum working solution 5mL after above-mentioned constant volume, 10mL, 15mL, 20mL, 25mL,
30mL, 35mL and 40mL, in one group of 100mL volumetric flask, are diluted with water to scale, mixing, respectively numbered work 1, work 2, work 3,
Work 4, work 5, work 6, work 7 and work 8, in them, Fe concentration is shown in Table 1；
2) calibration curve is drawn:
2a) with energy dispersion type Xray fluorescence spectrometer (power & light company of the U.S. (Thermo Electron
Corporation) producing, model is QUANT ' X EDXRY Analyzer) it is detecting instrument, suppose with 2.0g for calibration curve
Sample size, by step 1) mass concentration of Fe is become the percent mass of Fe by following formula scales in many parts of ferrum working solutions preparing
Specific concentration, the results are shown in Table 1；
Wherein, Fe% represents the mass percent concentration of Fe in ferrum working solution, and unit is %；C represents ferrum working solution
The mass concentration of middle Fe, unit is g/L；0.5 represents the volume supposing sample size constant volume, and unit is L；2 represent that calibration curve is false
Fixed sample size, unit is g.
Table 1:
2b) at energy dispersion type Xray fluorescence spectrometer, 8.8mm X-ray light pipe collimator is installed, it is ensured that detector
Temperature prepares to set up assay method after being down to 190K；Analysis method is set up with the intensity correction method of X fluorescence spectrum quantitative analysis,
Using thin Pd filter, arranging voltage is 20KV, and analysis time is 50s, and energy range is 0～20KeV, during counting rate is, and gas
Environment is air, and electric current is that matrix effect is not for consider automatically.The each method of described energy dispersion type Xray fluorescence spectrometer
Parameter is as shown in table 2；
Table 2:
2c) start sample introduction one by one with the Fe mass percent concentration after conversion in table 1 for initial data and adopt spectrum, each sample introduction
Sample liquid thickness be 15mm, record the fluorescence intensity of the Fe of each sample introduction, with the mass percent concentration of Fe in each ferrum working solution
For abscissa, with the fluorescence intensity corresponding with the mass percent concentration of above-mentioned Fe as vertical coordinate, make calibration curve, such as Fig. 1
Shown in.
Embodiment 2: use the method for the invention that fireworks and firecrackers firework medicament reference material and ferrum standard solution are entered
The controlled trial that row measures
Test with firework medicament reference material listed in table 3 and ferrum standard solution, wherein firework medicament reference substance
The ferrum nominal content of matter and ferrum standard solution is as shown in table 3；When using the method for the invention to measure, reference material is pressed
Iron content mensuration is carried out again after stating method preparation test liquid.
1) preparation test liquid:
Prepare test liquid with the reference material of numbering 1 for sample, weigh 3 parts of 1.9g～2.1g sample, be accurate to when weighing
0.1mg, the 1st part of sample is placed in 300mL beaker, adds 30mL～50mL water, heats micro-boiling about 8min, filtered while hot, uses
Water repeatedly washs, and by residue collection to another beaker, and the amount pressing 30mL/g～40mL/g sample adds nitric acid, places on electric furnace
Heat micro-boiling 20min, while hot with filter paper filtering, by filtrate collection to 500mL volumetric flask, treat that the solution in volumetric flask is cooled to room
Add water after temperature and be settled to scale and obtain the 1st part of test liquid；Repeat said method, obtain 3 parts of test liquids of No. 1 reference material；
2) mensuration of ferrum in reference material:
By embodiment 1 step 2b) testing conditions, by 3 parts of test liquid sample introductions one by one of the reference material of numbering 1, sample introduction
Sample liquid thickness be 15mm, the fluorescence intensity of Fe of display, the school determined according to embodiment 1 with this fluorescence intensity on grapher
Directrix curve reads corresponding Fe mass percent concentration value；
The mass percent concentration of ferrum in the reference material of calculating numbering 1 the most as follows:
Wherein, ω represents the mass percent concentration of fe in sample, and unit is %；ω0Represent according to calibration curve
The Fe mass percent concentration value read, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents sample
The actual quality weighed, unit is g, typically weighs 1.9g～2.1g；V represents the volume of constant volume after sample dissolution, and unit is mL；
500 represent the volume supposing sample size constant volume, and unit is mL.
Take the iron content of the reference material that meansigma methods is numbering 1 of wherein three result of calculation values, result as indicated at 3, and
Calculate its response rate, the results are shown in Table 3.
By above-mentioned steps 1) and step 2) method, the test liquid of reference material of preparation numbering 2 and 3, calculates it respectively
Iron content and the response rate, the results are shown in Table 3.
The most directly carry out the above-mentioned 2nd as the ferrum standard solution in table 3) step, each ferrum titer do equally 3 parts parallel
Sample, takes the meansigma methods iron content as ferrum standard solution of three result of calculation values, and result as indicated at 3, and calculates its response rate,
The results are shown in Table 3.
Table 3:
As shown in Table 3, the method for the invention is molten to different iron content fireworks and firecrackers firework medicaments and iron series standard
In liquid, the ferrum element of different content measures and has good accuracy.
Embodiment 3: use the method for the invention precision test to the testing result of reference material
In the present embodiment, the firework medicament reference material with three different iron contents is tested for sample, and numbered 4,5
With 6.
1) preparation test liquid:
Prepare test liquid with the reference material of numbering 1 for sample, weigh 4 parts of 1.9g～2.1g sample, be accurate to when weighing
0.1mg, the 1st part of sample is placed in 300mL beaker, adds 30mL～50mL water, heats micro-boiling about 8min, filtered while hot, uses
Water repeatedly washs, and by residue collection to another beaker, and the amount pressing 30mL/g～40mL/g sample adds nitric acid, places on electric furnace
Heat micro-boiling 20min, while hot with filter paper filtering, by filtrate collection to 500mL volumetric flask, treat that the solution in volumetric flask is cooled to room
Add water after temperature and be settled to scale and obtain the 1st part of test liquid；Repeat said method, obtain 4 parts of test liquids of No. 4 reference materials.
2) mensuration of iron content in reference material:
By embodiment 1 step 2b) testing conditions, by 4 parts of test liquid sample introductions one by one of the reference material of numbering 4, every part
Test liquid measures 11 times, and each sample introduction makes sample liquid thickness be 15mm, and the fluorescence intensity of the Fe of display on grapher, with this fluorescence
The calibration curve that intensity determines according to embodiment 1 reads corresponding Fe mass percent concentration value；
Calculating the mass percent concentration of ferrum in the reference material of numbering 4 the most as follows, result is as shown in table 4.
Wherein, ω represents the mass percent concentration of fe in sample, and unit is %；ω0Represent according to calibration curve
The Fe mass percent concentration value read, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents sample
The actual quality weighed, unit is g；V represents the volume of constant volume after sample dissolution, and unit is mL；500 represent that supposition sample size is fixed
The volume held, unit is mL.
By above-mentioned steps 1) and step 2) method, the test liquid of reference material of preparation numbering 5 and 6 respectively, and calculating
Their iron content, the results are shown in Table 4.
Table 4:
As shown in Table 4, variety classes firework medicament ferrum element is measured by the method for the invention has good precision,
Maximum allowable difference is 0.4%.
Embodiment 4: the mensuration of iron content in actual fireworks and firecrackers firework medicament
1, for the fireworks and firecrackers firework medicament sample of detection:
The spraying decoration class fireworks that 1#: sample produces from Pubei County, Guangxi fireworks factory, the ferrum in its effect medicine derives from ferrum
Powder raw material.
3 cun of display shell class samples that 2#: sample produces from Lingshan County, Guangxi fireworks factory, the ferrum source in its effect medicine
In iron powder raw material.
2, use the method for the invention that above-mentioned fireworks sample is detected:
Because using the calibration curve that embodiment 1 determines, therefore, the step for of saving drafting calibration curve, directly carry out
Preparation test liquid carries out the step of upper machine mensuration, specific as follows:
2.1) preparation test liquid:
Weighing 1# firework medicament sample 1.9g～3 parts of 2.1g sample respectively, be accurate to 0.1mg when weighing, the 1st part of sample is put
In 300mL beaker, add 30mL～50mL water, heat micro-boiling about 8min, filtered while hot, repeatedly wash with water, by filtering residue
Collect to another beaker, and the amount pressing 30mL/g～40mL/g sample adds nitric acid, places and heats micro-boiling 20min on electric furnace, takes advantage of
Heat filter paper filtering, by filtrate collection to 500mL volumetric flask, adds water after the solution in volumetric flask is cooled to room temperature and is settled to carve
Degree obtains the 1st part of test liquid；Repeat said method, obtain 3 parts of test liquids of No. 1 reference material.
2.2) mensuration of iron content in firework medicament:
By embodiment 1 step 2b) testing conditions, by 3 parts of test liquid sample introductions one by one of 1# firework medicament sample, load sample
The sample path length of product cup is 15mm, and on grapher, the fluorescence intensity of the Fe of display, determines according to embodiment 1 with this fluorescence intensity
Calibration curve read corresponding Fe mass percent concentration value；
Calculating the mass percent concentration of ferrum in 1# firework medicament sample the most as follows, result is as shown in table 5.
Wherein, ω represents the mass percent concentration of fe in sample, and unit is %；ω0Represent according to calibration curve
The Fe mass percent concentration value read, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents sample
The actual quality weighed, unit is g, typically weighs 1.9g～2.1g；V represents the volume of constant volume after sample dissolution, and unit is mL；
500 represent the volume supposing sample size constant volume, and unit is mL.
By above-mentioned steps 1) and step 2) method, prepare the test liquid of 2# firework medicament sample respectively, and calculate its ferrum
Content, the results are shown in Table 5.
While measuring above-mentioned firework medicament sample by this method, it is also adopted by existing traditional chemical analysis method
Above-mentioned sample is detected by (" mensuration of iron content in fireworks and firecrackers pyrotechnic composition " (GB/T 20617-2006)), and result is such as
Shown in table 5 below.
Table 5:
Embodiment described above is only to be described the preferred embodiment of the present invention, the not model to the present invention
Enclose and be defined, on the premise of designing spirit without departing from the present invention, this area ordinary skill technical staff skill to the present invention
Various deformation that art scheme is made and improvement, within all should falling into the protection domain that claims of the present invention determines.
Claims (9)
1. one kind measures the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that comprise the following steps:
S1, drafting calibration curve
S11, prepare many parts of concentration ferrum working solution not etc., high-purity iron powder is dissolved with dust technology by process for preparation；
S12, with energy dispersion type Xray fluorescence spectrometer as detecting instrument, the sample size supposed for calibration curve with 2.0g, adopt
Analysis method is set up with the intensity correction mathmetic correction of X fluorescence spectrum quantitative analysis；The many parts of ironworkers that step S11 is prepared
Make the mass concentration of Fe in liquid and be converted into the mass percent concentration of Fe, the most one by one sample introduction, record Fe glimmering of each sample introduction
Light intensity, the mass percent concentration of Fe in each ferrum working solution is as abscissa, with the mass percent concentration pair with above-mentioned Fe
The fluorescence intensity answered is vertical coordinate, makes calibration curve；Wherein, by following formula, the mass concentration of Fe in ferrum working solution is changed
It is counted as the mass percent concentration of Fe:
Wherein, Fe% represents the mass percent concentration of Fe in ferrum working solution, and unit is %；C represents the matter of Fe in ferrum working solution
Amount concentration, unit is g/L；0.5 represents the volume supposing sample size constant volume, and unit is L；2 represent the sample that calibration curve supposes
Amount, unit is g；
S2, the iron content measured in firework medicament:
S21, preparation test liquid: with firework medicament as sample, weigh a certain amount of sample and be placed in beaker, add a certain amount of water,
Heat micro-boiling 7min～9min, filtered while hot, repeatedly wash with water, by residue collection to another beaker, and add a certain amount of
Dust technology, places and heats micro-boiling several minutes on electric furnace, while hot with filter paper filtering, by filtrate collection to volumetric flask, treat in volumetric flask
Solution be cooled to room temperature after add water and be settled to scale, it is ensured that the solution Fe concentration of element after constant volume in calibration curve scope,
To test liquid；
S22, by the testing conditions of step S12, test liquid is loaded specimen cup, it is ensured that sample liquid thickness >=15mm, record energy color
Dissipate the fluorescence intensity of the Fe of display on type Xray fluorescence spectrometer, read according to the above-mentioned calibration curve determined with this fluorescence intensity
Go out corresponding Fe mass percent concentration value；
The content of ferrum in S23, calculating sample:
The mass percent concentration of ferrum in calculating sample as follows:
Wherein, ω represents the mass percent concentration of ferrum in sample, and unit is %；ω0Represent the Fe matter read according to calibration curve
Amount percent concentration value, unit is %；2 represent the sample size that calibration curve supposes, unit is g；M represents the actual weighing of sample
Quality, unit is g；V represents the volume of constant volume after sample dissolution, it is ensured that in the solution after constant volume, the concentration of Fe element is at calibration song
Line scope, unit is mL；500 represent the volume supposing sample size constant volume, and unit is mL.
The most according to claim 1 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
The method preparing ferrum working solution in S11 is: weigh a certain amount of high-purity iron powder or other ferrum element reference materials, according to certain examination
The amount of sample adds certain density nitric acid and dissolves, and is then settled to certain volume, the mass concentration of Fe be 0.08g/L～
0.66g/L。
The most according to claim 1 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
Nitric acid described in S11 adds according to the amount of 30mL/g～40mL/g sample, and the mass percent concentration of nitric acid is 40%～60%.
The most according to claim 1 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
The testing conditions of the energy dispersion type Xray fluorescence spectrometer of S12 is: use the mathmetic correction of intensity correction to set up analysis side
Method, aperture are the X-ray light pipe collimator of 8.8mm～14mm, it is possible to filter the filter of the energy X-ray less than 7.111KeV,
Arranging voltage is 16KV～24KV, and analysis time is 30s～80s, and energy range is 0～40KeV, during counting rate is, and Ring
Border is air, and electric current is that matrix effect is not for consider automatically.
The most according to claim 4 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
In S12, the testing inspection condition of energy dispersion type Xray fluorescence spectrometer is: arrange filter material be thin Pd, voltage be 20KV,
Analysis time is 50s, and energy range is 0～20KeV.
The most according to claim 1 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
When S21 prepares test liquid, when weighing a certain amount of sample, it is accurate to 0.1mg, is placed in beaker, and add dust technology, be placed on
Heat micro-boiling 15min～20min on electric furnace, while hot with filter paper filtering, by filtrate collection to volumetric flask, treat the solution in volumetric flask
Add water after being cooled to room temperature and be settled to scale, obtain test liquid.
The most according to claim 1 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
In S21, the volume mass of nitric acid and the amount of sample is than for 30mL/g～40mL/g, and the concentration of nitric acid is 40%～60%.
The most according to claim 1 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
In S22, test liquid thickness is 15mm～30mm.
The most according to claim 1 a kind of measure the method for iron content in fireworks and firecrackers firework medicament, it is characterised in that
In S23, the span of m is 1.9g～2.1g.
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| CN108195861A (en) * | 2017-12-27 | 2018-06-22 | 吴俊逸 | A kind of method of iron content in rapid semi-quantitative detection blind sample of fireworks and firecrackers pyrotechnic composition |
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